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INFORMATION TO USERS This manuscript has been reproduced from the microfilm master. UMI films the text directly from the original or copy submitted. Thus, some thesis and dissertation copies are in typewriter face, while others may be from any type of computer printer. The quality of this reproduction is dependent upon the quality of the copy submitted. Broken or indistinct print, colored or poor quality illustrations and photographs, print bleed through, substandard margins, and improper alignment can adversely affect reproduction. In the unlikely event that the author did not send UMI a complete manuscript and there are missing pages, these will be noted. Also, if unauthorized copyright material had to be removed, a note will indicate the deletion. Oversize materials (e.g., maps, drawings, charts) are reproduced by sectioning the original, beginning at the upper left-hand comer and continuing from left to right in equal sections with small overlaps. Each original is also photographed in one exposure and is included in reduced form at the back of the book. Photographs included in the original manuscript have been reproduced xerographically in this copy. Higher quality 6" x 9" black and white photographic prints are available for any photographs or illustrations appearing in this copy for an additional charge. Contact UMI directly to order. A Bell & Howell Information Company 300 North Z eeb Road. Ann Arbor. Ml 48106-1346 USA 313/761-4700 800/521-0600 SYNTHESIS AND CHARACTERIZATION OF FUNCTIONAL SILICON POLYMERS USING RUTHENIUM AND PLATINUM CATALYSTS BY HONGJIE GUO A DISSERTION PRESENTED TO THE FACULTY OF THE GRADUATE SCHOOL UNIVERSITY OF SOUTHERN CALIFORNIA IN PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR THE DEGREE DOCTOR OF PHILOSOPHY (CHEMISTRY) AUGUST 1995 COPYRIGHT 1995 HONGJIE GUO UMI Number: 9617101 UMI Microform 9617101 Copyright 1996, by UMI Company. All rights reserved. This microform edition is protected against unauthorized copying under Title 17, United States Code. UMI 300 North Zeeb Road Ann Arbor, MI 48103 UNIVERSITY OF SOUTHERN CALIFORNIA THE GRADUATE SCHOOL UNIVERSITY PARK LOS ANGELES, CALIFORNIA 90007 This dissertation, written by Hongj-Lt Gao under the direction of h.& & ...... Dissertation Committee, and approved by all its members, has been presented to and accepted by The Graduate School, in partial fulfillment of re quirements for the degree of DOCTOR OF PHILOSOPHY Dean of Graduate Studies Date ... August.1A a-J99.5 DISSERTATION COMMITTEE Chairperson fn to my lovely husband and twin children Acknowledgements I wish to express my sincere thanks to Professor William P. Weber for the opportunity to work with him. I am very grateful for his guidance, encouragement, friendship, and enthusiasm throughout my graduate study at the University of Southern California. I would also like to thank my committee members: Nobel laureate Professor G. A. Olah, Professor S. G. K. Prakash, Professor R. Bau, Professor R. Salovey, and Professor M. M. Appleman. My thanks also go to Ms. Terri Drought, Mrs. Reiko Choy, Ms. Lori Hay, and Ms Michele Dea for their assistance. I am very grateful to all the members in Dr. Weber's group for their help and cooperation. Finally, my deepest appreciation and thanks go to my lovely husband for his support and understanding, to my parents and all of the people who helped me physically and spiritually through the years. Abstract A novel ruthenium catalyzed highly efficient regioselective step-growth copolymerization reaction between aromatic ketones and a,Ci>-dienes has been developed. This reaction involves the ruthenium catalyzed regioselective Anti-Markovnikov insertion of the carbon-carbon double bonds of the a,co-dienes into the aromatic carbon-hydrogen bonds which are ortho to the carbonyl group of aromatic ketones. The copolymerization between anthrone, fluorenone or xanthone, and a,co-dienes gives the functional copolymers which incorporate in a regular manner anthrone, fluorenone or xanthone into the copolymer backbones. The p-substituted acetophenones, such as p-dialkylam inoacetophenones, p- methoxyacetophenone, p-phenoxyacetophenone or p-phenylacetophenone react with 0,0)- dienes under the same reaction conditions to yield a variety of novel functional copolymers with respectable molecular weights. Reaction of dihydridocarbonyltm(triphenylphosphine)ruthenium with a stoichiometric amount of an alkene such as styrene prior to addition of a 1:1 molar ratio acetophenone and a,to-diene produces ethylbenzene and high molecular weight copolymers of acetophenone and the a,co-diene. Chemical modification of unsaturated polycarbosilanes with pendant Si-vinyl groups has been achieved by this novel ruthenium cataly zed reaction. Dihydridocarbonylrm(triphenylphosphine)ruthenium catalyzes the addition of the ortho C-H bond of 2'-methylacetophenone across the C-C double bond of pendant vinyl groups of polymers such as copoly(vinylmethylsilylene/l,4-phenylene). Synthesis of functionally substituted polycarbosilanes with saturated and unsaturated backbones nas been carried out by platinum catalyzed hydrosilation graft reactions between poly(l-phenyl-1-silabutane), poly(methylsilylene/l,4-phenylene) and appropriate functionally substituted alkenes. Table of Contents D edication................................................................................................................... ii A cknow ledgem ents.................................................................................................. iii A b stract........................................................................................................................ iv List of Figures....................................................................................................... ix List of Tables........................................................................................................ xxiii Chapter 1. Ruthenium Catalyzed Regioselective Copolymerization of Anthrone, Fluorenone, or Xanthone with a,co-Dienes. 1.1 Sum m ary................................................................................. 1 1.2 Introduction........................................................................... 1 1.3 Results and Discussion..................................................... 3 1.4 Experim ental Section........................................................ 11 1.5 R eferences............................................................................. 17 Chapter 2. Ruthenium Catalyzed Regioselective Step-growth Copolymerization of p-Dialkylaminoacetophenones, p-Methoxyacetophenone, p-Phenoxyacetophenone or p-Phenylacetophenone and a,to-Dienes. 2.1 Sum m ary................................................................................. 29 2.2 Introduction........................................................................... 29 2.3 Results and Discussion..................................................... 31 2.4 C onclusion.............................................................................. 41 2.5 Experimental section......................................................... 42 2.6 R eferences............................................................................. 53 Chapter 3. Synthesis of High Molecular Weight Copolymers by Ruthenium Catalyzed Step-growth Copolymerization of Acetophenone with a,co-Dienes. 3.1 Sum m ary.................................................................................... 100 3.2 In tro d u ctio n .............................................................................. 100 3.3 Results and D iscussion........................................................ 101 3.4 Experim ental Section.......................................................... 106 3.5 R eferences................................................................................ 112 Chapter 4. Ruthenium Catalyzed Chemical Modification of Unsaturated Polycarbosilane. 4.1 S um m ary................................................................................... 121 4.2 In tro d u ctio n ............................................................................. 121 4.3 Results and D iscussion........................................................ 123 4.4 Experim ental Section........................................................... 128 4.5 R eferences................................................................................ 132 Chapter 5. Synthesis and Characterization of Polycarbosilanes with Saturated Backbones: Chemical Modification of Poly(l-phenyl-l-silabutane). 5.1 S um m ary.................................................................................... 140 5.2 In tro d u ctio n .............................................................................. 140 5.3 Results and D iscussion....................................................... 142 5.4 Experim ental Section.......................................................... 149 5.5 R eferences................................................................................ 155 Chapter 6. Synthesis and Characterization of Polycarbosilanes with Unsaturated Backbones: Chemical Modification of Copoly(methylsilylene/ 1,4-phenylene). 6.1 S um m ary................................................................................... 170 6.2 In tro d u ctio n ............................................................................. 170 6.3 Results and D iscussion...................................................... 172 6.4 Experim ental Section......................................................... 182 6.5 R eferen ces.............................................................................. 189 List of Figures Chapter 1 Figure 1. NMR of copoly(l,8-anthronylene/3,3,6,6- tetram ethyl-3,6-disila-1,8-octanylene).......................................... 4 Figure 2. 13c NMR of copoly(l,8-fluorenonylene/3,3,5,5- tetramethyl-4-oxa-3,5-disila-l,7-heptanylene)............................. 5 Figure 3. !h NMR of copoly(l,8-xanthonylene/3,3,5,5-tetramethyl- 4-oxa-3,5-disila-1,7-heptanylene)................................................ 6 Figure 4a. TGA ofcopoly(l,8-anthronylene/3,3,6,6-tetramethyl-3,6- d isila-l,8 -o ctan y len e)...................................................................... 8 Figure 4b. TGA of copoly(l,8-anthronylene/3,3,5,5-tetramethyl-4- oxa-3,5-disila-l,7-heptanylene)..................................................... 8 Figure 4c. TGA of copoly( 1,8-fluorenonylene/3,3,5,5-tetramethyl-4- oxa-3,5-disila-1,7-heptanylene)..................................................... 9 Figure 4d. TGA of copoly(l,8-xanthonylene/3,3,5,5-tetramethyl-4- oxa-3,5-disila-1,7-heptanylene)..................................................... 9 Figure 5. 1H NMR of copoly(1,8-fluorenonylene/3,3,5,5- tetramethyl-4-oxa-3,5-disila-l,7-heptanylene)............................. 18 Figure 6. 29§i NMR of copoly(l,8-fluorenonylene/3,3,5,5- tetramethyl-4-oxa-3,5-disila-l,7-heptanylene)............................... 18 Figure 7. FT-IR of copoly( 1,8-fluorenonylene/3,3,5,5-tetramethyl-4- oxa-3,5-disila-l,7-heptanylene)...................................................... 19 Figure 8. UV spectrum of copoly(l,8-fluorenonylene/3,3,5,5- tetramethyl-4-oxa-3,5-disila-l,7-heptanylene)............................... 19 Figure 9. DSC of copoly(l,8-fluorenonylene/3,3,5,5- tetramethyl-4-oxa-3,5-disila-l,7-heptanylene).............................. 20 Figure 10. *H NMR of copoly(l,8-anthronylene/3,3,6,6-tetramethyl-3,6- d isila-l,8 -o ctan y len e)........................................................................ 20 Figure 11. 29§i NMR of copoly( 1,8-anthronylene/3,3,6,6-tetramethyl-3,6- d isila-l,8 -o ctan y len e)........................................................................ 21 Figure 12. UV spectrum of copoly(l,8-anthronylene/3,3,6,6-tetramethyl-3,6- d isila-l,8 -o ctan y len e)....................................................................... 21 ix Figure 13. FT-IRofcopoly(l,8-anthronylene/3,3,6,6-tetramethyl-3,6- d isila-l,8 -o ctan y len e)...................................................................... 22 Figure 14. DSC of copoly(l,8-anthronylene/3,3,6,6-tetramethyl-3,6- d isila-l,8 -o ctan y len e)...................................................................... 22 Figure 15. NMR of copoly(l,8-anthronylene/3,3,5,5-tetramethyl-4- oxa-3,5-disila-1,7-heptanylene)..................................................... 23 Figure 16. 13 c NMR of copoly( 1,8-anthronylene/3,3,5,5-tetramethyl-4- oxa-3,5-disila-l,7-heptanylene)..................................................... 23 Figure 17. ^ S i NMR of copoly(l,8-anthronylene/3,3,5,5-tetramethyl-4- oxa-3,5-disila-1,7-heptanylene)..................................................... 24 Figure 18. UV spectrum of copoly(l,8-anthronylene/3,3,5,5-tetramethyl-4- o xa-3,5-disila-1,7-heptanylene)..................................................... 24 Figure 19. FT-IR ofcopoly(l,8-anthronylene/3,3,5,5-tetramethyl-4- oxa-3,5-disila-1,7-heptanylene)..................................................... 25 Figure 20. DSC of copoly( 1,8-anthronylene/3,3,5,5-tetramethyl-4- oxa-3,5-disila-1,7-heptanylene)..................................................... 25 Figure 21. ^ C NMR of copoly(l,8-xanthonylene/3,3,5,5-tetramethyl-4- oxa-3,5-disila-1,7-heptanylene)..................................................... 26 Figure 22. 29§i NMR of copoly(l,8-xanthonylene/3,3,5,5-tetramethyl-4- oxa-3,5-disila-l,7-heptanylene)..................................................... 26 Figure 23. FT-IR of copoly(l,8-xanthonylene/3,3,5,5-tetramethyl-4- oxr„-3,5-disila-1,7-heptanylene)..................................................... 27 Figure 24. UV spectrum of copoly(l,8-xanthonylene/3,3,5,5-tetramethyl-4- oxa-3,5-disila-l,7-heptanylene)..................................................... 27 Figure 25. DSC of copoly(l,8-xanthonylene/3,3,5,5-tetramethyl-4- oxa-3,5-disila-1,7-heptanylene)..................................................... 28 Chapter 2 Figure 1. *H, and ^ S i NMR of copoly(3,3,5,5-tetramethyl-4-oxa-3,5- disila-l,7-heptanylene/2-aceto-5-piperidino-l,3-phenylene) 34 Figure 2. ^H, 13c and 29si NMR of copoly(3,3,6,6-tetramethyl- 3,6-disila-1,8octanylene/2-aceto-5-piperidino-1,3-phenylene) 35 Figure 3. *H NMR of 4'-(N'-benzyl)piperazinoacetophenone.................. 55 Figure 4. l^C NMR of 4'-(N'-benzyl)piperazinoacetophenone.................... 55 Figure 5. FT-IR of 4'-(N'-benzyl)piperazinoacetophenone.......................... 56 Figure 6. UV spectrum of 4'-(N'-benzyl)piperazinoacetophenone................ 56 Figure 7. DSC of copoly(3,3,5,5-tetramethyl-4-oxa-3,5-disila-1,7- heptanylene/2-aceto-5-piperidino-1,3-phenylene)......................... 57 Figure 8. TGA of copoly(3,3,5,5-tetramethyl-4-oxa-3,5-disila-l,7- heptanylene/2-aceto-5-piperidino-1,3-phenylene)........................ 57 Figure 9. FT-IR of copoly(3,3,5,5-tetramethyl-4-oxa-3,5-disila-l,7- heptanylene/2-aceto-5-piperidino-1,3-phenylene)......................... 58 Figure 10. UV spectrum of copoly(3,3,5,5-tetramethyl-4-oxa-3,5-disila- 1.7-heptanylene/2-aceto-5-piperidino-l,3-phenylene )................... 58 Figure 11. DSC of copoly(3,3,6,6-tetramethyl-3,6-disila-1,8-octanylene/ 2-aceto-5-piperidino- 1,3-phenylene)............................................ 59 Figure 12. TGA of copoly(3,3,6,6-tetramethyl-3,6-disila-l,8-octanylene/ 2-aceto-5-piperidino-1,3-phenylene).................................. %..... 59 Figure 13. UV spectrum of copoly(3,3,6,6-tetramethyl-3,6-disila-l,8- octanylene/2-aceto-5-piperidino-1,3-phenylene).......................... 60 Figure 14. FT-IR of copoly(3,3,6,6-tetramethyl-3,6-disila-l,8-octanylene/ 2-aceto-5-piperidino-1,3-phenylene)............................................ 60 Figure 15. NMR of copoly(3,3,5,5-tetramethyl-4-oxa-3,5-disila- 1.7-heptanylene/2-aceto-5-morpholino-1,3-phenylene )................ 61 Figure 16. ^ C NMR of copoly(3,3,5,5-tetramethyl-4-oxa-3,5-disila- 1.7-heptanylene/2-aceto-5-morpholino-1,3-phenylene )................ 61 Figure 17. 29§j NMR of copoly(3,3,5,5-tetramethyl-4-oxa-3,5-disila- 1.7-heptanylene/2-aceto-5-morpholino-1,3-phenylene )................ 62 Figure 18. TGA of copoly(3,3,5,5-tetramethyl-4-oxa-3,5-disila-l,7- heptanylene/2-aceto-5-morpholino-1,3-phenylene)...................... 62 Figure 19. DSC of copoly(3,3,5,5-tetramethyl-4-oxa-3,5-disila-l,7- heptanylene/2-aceto-5-morpholino-1,3-phenylene)...................... 63 Figure 20. UV spectrum of copoly(3,3,5,5-tetramethyl-4-oxa-3,5- disila-1,7-heptanylene/2-aceto-5-morpholino-l,3-phenylene) 63 Figure 21. FT-IR of copoly(3,3,5,5-tetramethyl-4-oxa-3,5-disila-l,7- heptanylene/2-aceto-5-morpholino-1,3-phenylene)...................... 64 Figure 22. NMR of copoly(3,3,6,6-tetramethyl-3,6-disila-l,8-octanylene/ 2-aceto-5-m orpholino- 1,3-phenylene)........................................... 64 Figure 23. NMR of copoly(3,3,6,6-tetramethyl-3,6-disila-l,8- octanylene/2-aceto-5-morpholino-1,3-phenylene)....................... 65 Figure 24. 29 Si NMR of copoly(3,3,6,6-tetramethyl-3,6-disila-l,8- octanylene/2-aceto-5-morpholino-1,3-phenylene)........................ 65 Figure 25. DSC of copoly(3,3,6,6-tetramethyl-3,6-disila-1,8- octanylene/2-aceto-5-morpholino- 1,3-phenylene)........................ 66 Figure 26. TGA of copoly(3,3,6,6-tetramethyl-3,6-disila-1,8- octanylene/2-aceto-5-morpholino-1,3-phenylene)........................ 66 Figure 27. UV spectrum of copoly(3,3,6,6-tetramethyl-3,6-disila- 1,8-octanylene/2-aceto-5-morpholino-1,3-phenylene) 67 Figure 28. FT-IR of copoly(3,3,6,6-tetramethyl-3,6-disila-l,8- octanylene/2-aceto-5-morpholino-1,3-phenylene)........................ 67 Figure 29. NMR of copoly(3,3,5,5-tetramethyl-4-oxa-3,5-disila-l,7- heptanylene/2-aceto-5-(N'-benzyl)-piperazino-1,3-phenylene) 68 Figure 30. NMR of copoly(3,3,5,5-tetramethyl-4-oxa-3,5-disila-l,7- heptanylene/2-aceto-5-(N'-benzyl)-piperazino-1,3-phenylene) 68 Figure 31. 29§j n m R of copoly(3,3,5,5-tetramethyl-4-oxa-3,5-disila-1,7- heptanylene/2-aceto-5-(N'-benzyl)-piperazino-1,3-phenylene) 69 Figure 32. DSC of copoly(3,3,5,5-tetramethyl-4-oxa-3,5-disila-l,7- heptanylene/2-aceto-5-(N’ -benzyl)-piperazino-1,3-phenylene) 69 Figure 33. TGA of copoly(3,3,5,5-tetramethyl-4-oxa-3,5-disila-l,7- heptanylene/2-aceto-5-(N’ -benzyl)-piperazino-1,3-phenylene) 70 Figure 34. FT-IR of copoly(3,3,5,5-tetramethyl-4-oxa-3,5-disila-l,7- heptanylene/2-aceto-5-(N'-benzyl)-piperazino-1,3-phenylene) 70 Figure 35. UV spectrum of copoly(3,3,5,5-tetramethyl-4-oxa-3,5-disila-l,7- heptanylene/2-aceto-5-(N'-benzyl)-piperazino-1,3-phenylene) 71 Figure 36. NMR of copoly(3,3,6,6-tetramethyl-3,6-disila-1,8-octanylene /2-aceto-5-(N'-benzyl)-piperazino- 1,3-phenylene)...................... 71 Figure 37. NMR of copoly(3,3,6,6-tetramethyl-3,6-disila-l,8-octanyl- ene/2-aceto-5-(N'-benzyl)-piperazino-1,3-phenylene)................. 72 Figure 38. 29si NMR of copoly(3,3,6,6-tetramethyl-3,6-disila-l,8-octanyl- ene/2-aceto-5-(N'-benzyl)-piperazino-1,3-phenylene)................. 72 Figure 39. DSC of copoly(3,3,6,6-tetramethyl-3,6-disila-l,8-octanylene/ 2-aceto-5-(N'-benzyl)-piperazino-1,3-phenylene)....................... 73 Figure 40. TGA of copoly(3,3,6,6-tetramethyl-3,6-disila-1,8-octanylene/ 2-aceto-5-(N'-benzyl)-piperazino-1,3-phenylene)....................... 73 Figure 41. FT-IR of copoly(3,3,6,6-tetramethyl-3,6-disila-1,8-octanylene/ 2-aceto-5-(N'-benzyl)-piperazino-1,3-phenylene)....................... 74 Figure 42. UV spectrum of copoly(3,3,6,6-tetramethyl-3,6-disila-l,8-octanyl- ene/2-aceto-5-(N’ -benzyl)-piperazino-1,3-phenylene)................. 74 Figure 43. NMR of copoly(3,3,5,5-tetramethyl-4-oxa-3,5-disila- 1.7-heptanylene/10-methyl-1,8-acrid-9-onylene )........................ 75 Figure 44. NMR of copoly(3,3,5,5-tetramethyl-4-oxa-3,5-disila- 1.7-heptanylene/l 0-methyl-1,8-acrid-9-onylene)........................ 75 Figure 45. 29sj NMR of copo!y(3,3,5,5-tetramethyl-4-oxa-3,5-disila- 1.7-heptanylene/10-methyl-l,8-acrid-9-onylene )........................ 76 Figure 46. TGA of copoly(3,3,5,5-tetramethyl-4-oxa-3,5-disila-l,7- heptanylene/10-methyl-l,8-acrid-9-onylene)............................... 76 Figure 47. DSC of copoly(3,3,5,5-tetramethyl-4-oxa-3,5-disila-1,7- heptanylene/10-methyl-l,8-acrid-9-onylene)............................... 77 Figure 48. UV spectrum of copoly(3,3,5,5-tetramethyl-4-oxa-3,5- disila-l,7-heptanylene/10-methyl-l,8-acrid-9-onylene).............. 77 Figure 49. FT-IR of copoly(3,3,5,5-tetramethyl-4-oxa-3,5-disila-l,7- heptanylene/10-methyl-l,8-acrid-9-onylene)............................... 78 Figure 50. NMR of copoly(3,3,5,5-tetramethyl-4-oxa-3,5- disila-l,7-heptanylene/2-aceto-5-methoxy-l,3-phenylene) 78 Figure 51. NMR of copoly(3,3,5,5-tetramethyl-4-oxa-3,5- disila-1,7-heptanylene/2-aceto-5-methoxy-1,3-phenylene) 79 Figure 52. 29$i NMR of copoly(3,3,5,5-tetramethyl-4-oxa-3,5- disila-1,7-heptanylene/2-aceto-5-methoxy-1,3-phenylene) 79 Figure 53 . TGA of copoly(3,3,5,5-tetramethyl-4-oxa-3,5-disila-l,7- heptanylene/2-aceto-5-methoxy-1,3-phenylene)............................ 80 Figure 54. DSC of copoly(3,3,5,5-tetramethyl-4-oxa-3,5-disila-l,7- heptanylene/2-aceto-5-methoxy-1,3-phenylene)............................ 80 Figure 55. FT-IR of copoly(3,3,5,5-tetramethyl-4-oxa-3,5-disila- 1.7-heptanylene/2-aceto-5-methoxy-1,3-phenylene )..................... 81 Figure 56. UV spectrum of copoly(3,3,5,5-tetramethyl-4-oxa-3,5-disila- 1.7-heptanylene/2-aceto-5-methoxy-1,3-phenylene )..................... 81 Figure 57. *H NMR of copoly(3,3,6,6-tetramethyl-3,6-disila-l,8- octanylene/2-aceto-5-methoxy-1,3-phenylene).............................. 82 Figure 58. 1 ^C NMR of copoly(3,3,6,6-tetramethyl-3,6-disila-1,8 octanylene/2-aceto-5-methoxy-1,3-phenylene).............................. 82 Figure 59. 29si NMR of copoly(3,3,6,6-tetramethyl-3,6-disila-1,8- octanylene/2-aceto-5-methoxy-1,3-phenylene).............................. 83 Figure 60. TGA of copoly(3,3,6,6-tetramethyl-3,6-disila-l,8- octanylene/2-aceto-5-methoxy-1,3-phenylene).............................. 83 Figure 61. DSC of copoly(3,3,6,6-tetramethyl-3,6-disila-l,8- octanylene/2-aceto-5-methoxy-1,3-phenylene).............................. 84 Figure 62. UV spectrum of copoly(3,3,6,6-tetramethyl-3,6-disila- 1.8-octanylene/2-aceto-5-methoxy-1,3-phenylene )........................ 84 Figure 63. FT-IR of copoly(3,3,6,6-tetramethyl-3,6-disila-l,8- octanylene/2-aceto-5-methoxy-1,3-phenylene)............................. 85 Figure 64. NMR of copoly(3,3,5,5-tetramethyl-4-oxa-3,5-disila- 1.7-heptanylene/2-aceto-5-phenoxy-1,3-phenylene ).................... 85 Figure 65. NMR of copoly(3,3,5,5-tetramethyl-4-oxa-3,5-disila- 1.7-heptanylene/2-aceto-5-phenoxy-1,3-phenylene ).................... 86 Figure 66. 29§i NMR of copoly(3,3,5,5-tetramethyl-4-oxa-3,5-disila- 1.7-heptanylene/2-aceto-5-phenoxy-l,3-phenylene ).................... 86 Figure 67. DSC of copoly(3,3,5,5-tetramethyl-4-oxa-3,5-disila-l,7- heptanylene/2-aceto-5-phenoxy-1,3-phenylene).......................... 87 Figure 68. TGA of copoly(3,3,5,5-tetramethyl-4-oxa-3,5-disila-l,7- heptanylene/2-aceto-5-phenoxy-1,3-phenylene).......................... 87 xiv Figure 69. FT-IR of copoly(3,3,5,5-tetramethyl-4-oxa-3,5-disila-l,7- heptanylene/2-aceto-5-phenoxy-1,3-phenylene)............................ 88 Figure 70. UV spectrum of copoly(3,3,5,5-tetramethyl-4-oxa-3,5-disila- 1.7-heptanylene/2-aceto-5-phenoxy-1,3-phenylene )..................... 88 Figure 71. NMR of copoly(3,3,6,6-tetramethyl-3,6-disila-l,8- octanylene/2-aceto-5-phenoxy-1,3-phenylene).............................. 89 Figure 72. NMR of copoly(3,3,6,6-tetramethyl-3,6-disila-l,8- octanylene/2-aceto-5-phenoxy-1,3-phenylene).............................. 89 Figure 73. ^ S i NMR of copoly(3,3,6,6-tetramethyl-3,6-disila-l,8- octanylene/2-aceto-5-phenoxy-1,3-phenylene).............................. 90 Figure 74. TGA of copoly(3,3,6,6-tetramethyl-3,6-disila-l,8-octanylene/ 2-aceto-5-phenoxy-1,3-phenylene)................................................ 90 Figure 75. DSC of copoly(3,3,6,6-tetramethyl-3,6-disila-l,8-octanylene/ 2-aceto-5-phenoxy-1,3-phenylene)................................................ 91 Figure 76. UV spectrum of copoly(3,3,6,6-tetramethyl-3,6-disila-l,8- octanylene/2-aceto-5-phenoxy-1,3-phenylene).............................. 91 Figure 77. FT-IR of copoly(3,3,6,6-tetramethyl-3,6-disila-1,8-octanylene/ 2-aceto-5-phenoxy-1,3-phenylene)................................................ 92 Figure 78. NMR of copoly(3,3,5,5-tetramethyl-4-oxa-3,5-disila- 1.7-heptanylene/2-aceto-5-phenyl-1,3-phenylene )......................... 92 Figure 79. NMR of copoly(3,3,5,5-tetramethyl-4-oxa-3,5-disila- 1.7-heptanylene/2-aceto-5-phenyl-1,3-phenylene )......................... 93 Figure 80. ^^Si NMR of copoly(3,3,5,5-tetramethyl-4-oxa-3,5-disila- 1.7-heptanylene/2-aceto-5-phenyl-1,3-phenylene )......................... 93 Figure 81. TGA of copoly(3,3,5,5-tetramethyl-4-oxa-3,5-disila-l,7- heptanylene/2-aceto-5-phenyl-1,3-phenylene)............................... 94 Figure 82. DSC of copoly(3,3,5,5-tetramethyl-4-oxa-3,5-disila-l,7- heptanylene/2-aceto-5-phenyl- 1,3-phenylene)............................... 94 Figure 83. FT-IR of copoly(3,3,5,5-tetramethyl-4-oxa-3,5-disila-l,7- heptanylene/2-aceto-5-phenyl-1,3-phenylene)............................... 95 Figure 84. UV spectrum of copoly(3,3,5,5-tetramethyl-4-oxa-3,5- disila-1,7-heptanylene/2-aceto-5-phenyl-1,3-phenylene)............... 95 XV Figure 85. NMR of copoly(3,3,6,6-tetramethyl-3,6-disila-l,8- octanylene/2-aceto-5-phenyl-1,3-phenylene)............................... 96 Figure 86. NMR of copoly(3,3,6,6-tetramethyl-3,6-disila-l,8- octanylene/2-aceto-5-phenyl-1,3-phenylene)............................... 96 Figure 87. 29§j NMR of copoly(3,3,6,6-tetramethyl-3,6-disila-1,8- octany!ene/2-aceto-5-phenyl-1,3-phenylene)............................... 97 Figure 88. TGA of copoly(3,3,6,6-tetramethyl-3,6-disila-1,8- octanylene/2-aceto-5-phenyl-1,3-phenylene)............................... 97 Figure 89. DSC of copoly(3,3,6,6-tetramethyl-3,6-disila-l,8- octanylene/2-aceto-5-phenyl-1,3-phenylene)............................... 98 Figure 90. FT-IR of copoly(3,3,6,6-tetramethyl-3,6-disila-l,8- octanylene/2-aceto-5-phenyl-1,3-phenylene)............................... 98 Figure 91. UV spectrum of copoly(3,3,6,6-tetramethyl-3,6-disila-l,8- octanylene/2-aceto-5-phenyl-1,3-phenylene)............................... 99 Chapter 3 Figure 1. NMR spectra of high molecular weight copoly-I and low molecular weight copoly-1................................................... 103 Figure 2. NMR spectra of the reaction between styrene and "Ru" cataly st.................................................................................... 104 Figure 3. TGA of high molecular weight copoly-1 (1) and low molecular weight copoly-I (2)...................................................................... 105 Figure 4. NMR o f copoly-I................................................................. 113 Figure 5. 2 9 si NMR o f copoly-I.................................................................. 113 Figure 6. UV spectrum o f copoly-I............................................................ 114 Figure 7. FT-IR o f copoly-I........................................................................ 114 Figure 8. DSC of low molecular weight copoly-I..................................... 115 Figure 9. DSC of high molecular weight copoly-II.................................... 115 Figure 10. *H NMR o f copoly-II................................................................. 116 Figure 11. ^ C NMR of copoly-II............................................................... 116 xvi Figure 12. 2 9 si NMR o f copoly-II............................................................. 117 Figure 13. UV spectrum o f copoly-II.......................................................... 117 Figure 14. FT-IR o f copoly-II....................................................................... 118 Figure 15. TGA of low molecular weight copoly-II............................. 118 Figure 16. TGA of high molecular weight copoly-II............................ 119 Figure 17. DSC of low molecular weight copoly-II...................................... 119 Figure 18. DSC of high molecular weight copoly-II...................................... 120 Chapter 4 Figure 1. FT-IR of copoly(vinylmethylsilylene/l,4-phenylene)................. 123 Figure 2. NMR of copoly[2-(2'-acetyl-3'-methylphenyl)ethyl- m ethylsilylene/l,4-phenylene]....................................................... 124 Figure 3. UV spectrum of copoly[2-(2'-acetyl-3'-methylphenyl)ethyl- m ethylsilylene/l,4-phenylene]....................................................... 125 Figure 4. NMR of copoly(vinylmethylsilylene/l ,4-phenylene)............. 134 Figure 5. NMR of copoly(vinylmethylsilylene/l,4-phenylene) 134 Figure 6. 29si NMR of copoly(vinylmethylsilylene/l,4-phenylene) 135 Figure 7. UV spectrum of copoly(vinylmethylsilylene/l,4-phenylene) 135 Figure 8. DSC of copoly(vinylmethylsilylene/l,4-phenylene)...................... 136 Figure 9. TGA of copoly(vinylmethylsilylene/l,4-phenylene)...................... 136 Figure 10. ^ C NMR of copoly[2-(2'-acetyl-3'-methylphenyl)ethyl- m ethylsilylene/1,4-phenylene]....................................................... 137 Figure 11. 29§i NMR of copoly [2-(2'-acetyl-3'-methylphenyl)ethyl- m ethylsilylene/1,4-phenylene]....................................................... 137 Figure 12. FT-IR of copoly[2-(2'-acetyl-3'-methylphenyl)ethyl- m ethylsilylene/l,4-phenylene]....................................................... 138 Figure 13. DSC of copoly[2-(2'-acetyl-3'-methylphenyl)ethyl- m ethylsilylene/l,4-phenylene]....................................................... 138 xvii Figure 14. TGA of copoly[2-(2'-acetyl-3'-methylphenyl)ethyl- m ethylsilylene/l,4-phenylene]....................................................... 139 Chapters Figure 1. NMR of poly(l-phenyl-1-silabutane).................................... 143 Figure 2. FT-IR of poly[l-(3’-cyanopropyl)-l-phenyl-1-silabutane] 144 Figure 3. FT-IR of poly[l-(4',7',10',13'-tetraoxatetradecanyl)-l- phenyl-1-silabutane]........................................................................ 145 Figure 4. DSC of poly[l-(4',7',10\13'-tetraoxatetradecanyl)-l- phenyl-1-silabutane]........................................................................ 148 Figure 5. DSC of poly[l-(3'-biphenoxypropyl)-l-phenyl-1-silabutane] 148 Figure 6. FT-IR of poly(l-phenyl-1-silabutane)......................................... 157 Figure 7. *H NMR of poly[l-(3'-cyanopropyl)-l-phenyl-l-silabutane] 157 Figure 8. ^ C NMR of poly[l-(3'-cyanopropyl)-l-phenyl-1-silabutane] 158 Figure 9. ^9si NMR of poly[l-(3'-cyanopropyl)-l-phenyl-1-silabutane] 158 Figure 10. UV spectrum of poly[ 1 -(3'-cyanopropyl)-1 -phenyl- 1-silabutane]...................................................................................... 159 Figure 11. DSC of poly[l-(3'-cyanopropyl)-l-phenyl-1-silabutane]............. 159 Figure 12. NMR of poly[l-(4',7',10',13'-tetraoxatetradecanyl)-l- phenyl-1-silabutane]........................................................................ 160 Figure 13. 29§j NMR of poly[l-(477',10',13’-tetraoxatetradecanyl)-l- phenyl-1-silabutane]........................................................................ 160 Figure 14. UV spectrum of poly[l-(4’ ,7',10\13'-tetraoxatetradecanyl)-l- p h en y l-l-silab u tan e]........................................................................ 161 Figure 15. NMR of poly[l-(3'-ethoxypropyl)-l-phenyl- 1-silabutane]...................................................................................... 161 Figure 16. ^ C NMR of poly[ 1 -(3’ -ethoxypropyl)-1 -phenyl- 1 -silabutane]...................................................................................... 162 Figure 17. 29§j NMR of poly[l-(3'-ethoxypropyl)-l-phenyl- 1-silabutane]...................................................................................... 162 Figure 18. FT-IR of poly[l-(3'-ethoxypropyl)-l-phenyl- 1-silabutane]...................................................................................... 163 Figure 19. UV spectrum of poly[l-(3'-ethoxypropyl)-l-phenyl- 1-silabutane]...................................................................................... 163 Figure 20. DSC of poly[l-(3'-ethoxypropyl)-1-phenyl-1-silabutane] 164 Figure 21. *H NMR of poly[l-(3'-biphenoxypropyl)-l-phenyl- 1 -silabutane]...................................................................................... 164 Figure 22. NMR of poly[ 1 -(3'-biphenoxypropyl)-1 -phenyl- 1-silabutane]...................................................................................... 165 Figure 23. ^ S i NMR o f poly[l-(3'-biphenoxypropyl)-l-phenyl- 1-silabutane]...................................................................................... 165 Figure 24. FT-IR of poly[l-(3'-biphenoxypropyl)-l-phenyl- 1-silabutane]...................................................................................... 166 Figure 25. UV spectrum of poly[l-(3'-biphenoxypropyl)-l-phenyl- 1-silabutane]...................................................................................... 166 Figure 26. 1H NMR of poly [ 1 -(3'-phenoxypropyl)-1 -phenyl- 1-silabutane]...................................................................................... 167 Figure 27. NMR of poly[ 1 -(3'-phenoxypropyl)-1 -phenyl- 1-silabutane]...................................................................................... 167 Figure 28. ^9gi NMR of poly[l-(3'-phenoxypropyl)-l-phenyl- 1-silab u tan ej...................................................................................... 168 Figure 29. UV spectrum of poly[l-(3'-phenoxypropyl)-l-phenyl- 1-silabutane]...................................................................................... 168 Figure 30. FT-IR of poly[l-(3'-phenoxypropyl)-l-phenyl-1-silabutane] 169 Figure 31. DSC of poly[l-(3'-phenoxypropyl)-l -phenyl- 1-silabutane] 169 Chapter 6 Figure 1. FT-IR of poly(methylsilylene/l ,4-phenylene)............................ 173 Figure 2. ^H, NMR of poly(methylsilylene/l,4-phenylene)................ 174 Figure 3. 29gj NMR of copoly(methyl-3'-ethoxypropylsilylene/ 1,4-phenylene) 175 xix Figure 4. FT-IR of copoly(methyl-3'-cyanopropylsilylene/ 1.4-phenylene ) .................................................................................. 176 Figure 5a. TGA of copoly(methyI-3'-biphenoxypropylsilylene/ 1.4-phenylene ) .................................................................................. 178 Figure 5b. TGA of copoly(methyl-3'-phenoxypropylsilylene/ 1.4-phenylene ) .................................................................................. 179 Figure 5c. TGA of copoly(methyl-3’ -cyanopropylsilylene/ 1.4-phenylene ) .................................................................................. 179 Figure 5d. TGA of copoly(methyl-4',7',10',13'-tetraoxatetradecanyl- sily lene/l,4-phenylene)................................................................... 180 Figure 6. 29§i NMR of poly(methylsilylene/l,4-phenylene)..................... 191 Figure 7. UV spectrum of poly(methylsilylene/l ,4-phenylene)................... 191 Figure 8. DSC of poly(methylsilylene/l,4-phenylene)............................... 192 Figure 9. NMR of copoly(methyl-3'-cyanopropylsilylene/ 1.4-phenylene ) .................................................................................. 192 Figure 10. NMR of copoly(methyl-3'-cyanopropylsilylene/ 1.4-phenylene ) .................................................................................. 193 Figure 11. 29§i NMR of copoly(methyl-3'-cyanopropylsilylene/ 1.4-phenylene ) .................................................................................. 193 Figure 12. UV spectrum of copoly(methyl-3'-cyanopropylsilylene/ 1.4-phenylene ) .................................................................................. 194 Figure 13. DSC of copoly(methyl-3'-cyanopropylsilylene/ 1.4-phenylene ).................................................................................. 194 Figure 14. NMR of copoly(methyl-3'-ethoxypropylsilylene/ 1.4-phenylene ).................................................................................. 195 Figure 15. ^ C NMR of copoly(methyl-3'-ethoxypropylsilylene/ 1.4-phenylene ) .................................................................................. 195 Figure 16. ^ S i NMR of copoly(methyl-3'-ethoxypropylsilylene/ 1.4-phenylene ).................................................................................. 196 Figure 17. FT-IR of copoly(methyl-3'-ethoxypropylsilylene/ 1.4-phenylene ).................................................................................. 196 xx Figure 18. UV spectrum of copoly(methyl-3'-ethoxypropylsilylene/ 1.4-phenylene ).................................................................................. 197 Figure 19. DSC of copoly(methyl-3’ -ethoxypropylsilylene/ 1.4-phenylene ).................................................................................. 197 Figure 20. TGA of copoly(methyl-3'-ethoxypropylsilylene/ 1.4-phenylene ).................................................................................. 198 Figure 21. NMR of copoly (methyl-4’ ,7', 10', 13'-tetraoxatetradecanyl- sily lene/l,4-phenylene)................................................................... 198 Figure 22. 13c NMR of copoly(methyl-4',7',10',13'-tetraoxatetradecanyl- silylen e/l,4 -p h en y len e).................................................................. 199 Figure 23. 29§i NMR of copoly(methyl-4',7',10',13'-tetraoxatetradecanyl- sily len e/l,4 -p h en y len e)................................................................... 199 Figure 24. FT-IR of copoly(methyl-4',7',10',13'-tetraoxatetradecanyl- sily len e/l,4 -p h en y len e)................................................................... 200 Figure 25. UV spectrum of copoly(methyl-4',7',10',13'-tetraoxatetradecanyl- sily lene-/l,4-phenylene)..................................................................200 Figure 26. DSC of copoly(methyl-4',7',10',13'-tetraoxatetradecanylsilylene/ 1.4-phenylene ) .................................................................................. 201 Figure 27. NMR of copoly(methyl-3'-phenoxypropylsilylene/ 1.4-phenylene ) .................................................................................. 201 Figure 28. 13 c NMR of copoly(methyl-3'-phenoxypropylsilyIene/ 1.4-phenylene ) .................................................................................. 202 Figure 29. ^9§i NMR of copoly(methyl-3’ -phenoxypropylsilylene/ 1.4-phenylene ).................................................................................. 202 Figure 30. FT-IR of copoly(methyl-3'-phenoxypropylsilylene/ 1.4-phenylene ) .................................................................................. 203 Figure 31. UV spectrum of copoly(methyl-3'-phenoxypropylsilylene/ 1.4-phenylene ) .................................................................................. 203 Figure 32. DSC of copoly(methyl-3'-phenoxypropylsilylene/ 1.4-phenylene ) .................................................................................. 204 Figure 33. *H NMR of copoly(methyl-3'-biphenoxypropylsilylene/ 1.4-phenylene ).................................................................................. 204 xxi Figure 34. 13C NMR of copoly(methyl-3'-biphenoxypropylsilylene/ 1.4-phenylene ).................................................................................. 205 Figure 35. 29§j NMR of copoly(methyl-3'-biphenoxypropylsilylene/ 1.4-phenylene ) .................................................................................. 205 Figure 36. FT-IR of copoly(methyl-3’ -biphenoxypropylsilylene/ 1.4-phenylene ).................................................................................. 206 Figure 37. UV spectrum of copoly(methyl-3’ -biphenoxypropylsilylene/ 1.4-phenylene ).................................................................................. 206 Figure 38 DSC of copoly(methyl-3'-biphenoxypropylsilylene/ 1.4-phenylene ) .................................................................................. 207 xxii List of Tables Chapter 1 Table 1. Chapter 2 Table 1. Chapter 5 Table 1. Chapter 6 Table 1. Comparison of the reactivity of fluorenone, anthrone, and xanthone with 1,3-divinyltetramethyldisiloxane........................... 10 Yields, glass transition temperatures (Tgs), polymer molecular weights (Mw/Mn), and resonances in 29§i NMR spectra of the product copolym ers................................................................. 37 Glass transition temperatures of poly[l-(3’ -substitutopropyl)- 1 -phenyl-1 -silabutane], poly[ 1 -(3'-substitutopropy 1)-1 - m ethyl-1-silabutane]........................................................................ 147 Glass transition temperatures in °C of poly[l-phenyl-l-substituted- 1-silabutanes], poly[l-methyl-1-substituted-1-silabutanes] and copoly[ 1 -methyl-1 -substituted- 1-silylene/l ,4-phenylenes] 181 xxiii CHAPTER 1 Ruthenium Catalyzed Regioselective Copolymerization of Anthrone, Fluorenone, or Xanthone with a,co-Dienes 1.1 Summary: This chapter reports a novel ruthenium catalyzed regioselective step-growth copolymerization reaction between anthrone, fluorenone or xanthone and a,co-dienes such as 1,3-divinyltetramethyldisiloxane and 3,3,6,6-tetram ethyl-3,6-disila-l,7- octadiene. This reaction involves the ruthenium catalyzed regioselective Anti- Markovnikov insertion of the carbon-carbon double bonds of the a,co-dienes into the aromatic carbon-hydrogen bonds which are ortho to the carbonyl group of anthrone, fluorenone or xanthone. The structures and thermal stabilities of these polymers are discussed. Similar ruthenium catalyzed copolymerization reactions between acetophenone and a,G)-dienes 1 have been reported as have reactions between acetophenone and alkenes to yield monomeric orr/w-alkyl substituted a c e t o p h e n o n e s . 2 - 4 1.2 Introduction: While Ziegler-Natta transtion metal catalyzed polymerizations of ethylene and propylene to yield high density polyethylene and polypropylene are among the largest scale commercial processes, transition metal catalyzed copolymerization reactions have attracted much less attention. For example, only few examples of Ziegler-Natta statistically random copolymerization of ethylene and various a-olefins have been r e p o r t e d . 5-8 The ruthenium catalyzed copolymerization of anthrone, fluorenone and xanthone with a,o>-dienes reported herein maybe related mechanistically to the palladium 1 catalyzed Heck reaction of aryl halides with a l k e n e s . 8 - 1 3 The Heck reaction has in recent years been applied to the synthesis of polymers. Insertion of palladium into the carbon- halogen bond of an aryl halide leads to reactive aryl-palladium species which is the key intermediate in this reaction. Apparently, the carbonyl group of anthrone, fluorenone or xanthone directs insertion of a coordinately unsaturated ruthenium into adjacent ortho carbon-hydrogen bonds which leads to an aryl ruthenium hydride intermediate. Coordination of a carbon-carbon double bond of the a,G)-dienes to the ruthenium center followed by regioselective anti-Markovnikov addition of the aryl-ruthenium and hydrogen-ruthenium bonds across the coordinated carbon-carbon bond yields the product and regenerates the catalytically active ruthenium species. Of particular note, this novel ruthenium catalyzed copolymerization reaction results in copolymers which incorporate in a regular manner anthrone, fluorenone and xanthone into the copolymer backbones. The utilization of these aromatic ketones as reactive difunctional monomers which can be incorporated into polymer systems has not been previously reported.(Scheme 1) Xylene Scheme 1. Synthesis of copoly(l,8-xanthonylene/3,3,5,5-tetramethyl-4-oxa-3,5- disila-1,7-heptanylene). 1.3 Results an d Discussion: We should like to report the preparation and characterization of these copolymers by the ruthenium catalyzed regioselective copolymerization of anthrone, fluorenone or 2 xanthone with either 1,3-divinyltetramethyldisiloxane or 3,3,6,6-tetramethyl-3,6-disila- 1,7-octadiene. This reaction is remarkable in a number of ways. Neither anthrone, fluorenone nor xanthone has been previously utilized as a difunctional monomer and thereby incorporated into the backbone of a polymer system. Only the ortho carbon- hydrogen bonds which are adjacent to the carbonyl groups are activated for this insertion copolymerization process. Further, unlike the Heck reaction, activation of the aromatic ring by halogenation is not required. There is a major effort to eliminate halogen in the chemical process industry. This copolymerization process is therefore potentially environmentally friendly. 14 Only catalytic amounts, one to three mole percent, of ruthenium are necessary to obtain high yields of copolymer. This implies that the catalyst has a turn over number of at least thirty. The reaction proceeds by heating a 1:1 ratio of aromatic ketone and the a,co-diene at 150°C for 24 to 72 h. Solvent is only necessary when the solid aromatic ketone fails to dissolve in the oc,co-dienes at 150°C. Unfortunately, the molecular weight of the copolymers obtained is often low. This is not unexpected for a step-growth addition copolymerization - where exact stoichiometry is required in order to obtain high molecular weight polymers. The low molecular weight of the copolymers permits spectroscopic observation of end groups. 13c NMR signals have been detected consistent with anthrone, and fluorenone terminal groups. No NMR signals consistent with xanthone end groups have been observed. This may result from the higher molecular weights of the xanthone containing copolymers. For example, in the l ^ c NMR spectrum (Figure 1) of copoly[l,8- anthronylene/3,3,6,6-tetram ethyl-3,6-disila-l,8-octanylene], in addition to the resonances reported above, five low intensity signals (33.50, 126.37, 127.51, 129.31, 131.90 ppm) are observed. We believe, that these should be assigned to anthrone end groups (Scheme 2a). For comparison, the l ^ c NMR spectrum of anthrone itself has 3 eight signals: 32.23, 126.90. 12T45, 128.38, 131.89, 132.07, 140.37 and 184.16 ppm. The intensities of the signals at 132.07, 140.37. and 184.16 ppm, which are assigned to the two ipso and the carbonyl carbon are quite low. -1______ I............, 1 ........ I.— . 60 40 20 0 200 180 160 140 120 100 80 PPM Figure 1. NMR of copoly(l,8-anthronylene/3,3,6,6-tetramethyl-3,6-disila-l,8- octanylene). Similarly, in the NMR spectrum (Figure 2) o f c o p o ly (l,8 - fluorenonylene/3,3,5,5-tetramethyl-4-oxa-3,5-disila-l,7-heptanylene), in addition to the resonances reported in the experiment section, six low intensity signals are detected (119.84, 123.67, 128.73, 134.13, 144.60, 194.00 ppm). We believe that these may be assigned to fluorenone end groups (Scheme 2b). For comparison, the NMR spectrum of fluorenone itself has seven signals: 120.26, 124.19, 128.99, 134.02, 134.62, 144.34 and 193.83 ppm. The intensities of the signals at 134.02, 144.34, and 193.83 ppm which are assigned to the two ipso carbons and the carbonyl carbon are quite low. 4 - L . IAj j .Vm 1 200 180 160 140 120 100 PPM 8 0 60 40 2 0 Figure 2. 13c NMR of copoly(l,8-fluorenonylene/3,3,5,5-tetramethyl-4-oxa-3,5- disila-1,7-heptanylene). Scheme 2. Observed end groups 5 In the case of copoly(l,8-xanthonylene/3,3,5,5-tetramethyl-4-oxa-3,5-disila-l,7- heptanylene) a second type of terminal group has been detected. Specifically signals in the lH NMR [0.52(q, J = 13.8 Hz) and 1.26 (t, J = 13.8 Hz) ppm] (Figure 3) and 13c NMR [6.83 and 10.50 ppm] are observed. These are consistent with an ethyl group attached to silicon (Scheme 2c). This may be formed by hydrogenation of one of the carbon-carbon double bonds of 1,3-divinyltetramethyldisiloxane to yield l-ethyI-3-vinyl- te tra m e th y ld isilo x a n e . In fa c t, the clo se ly re la te d com plex dihydridofcrra&/s(triphenylphosphine)ruthenium is known to catalyze the transfer hydrogenation of alkenes. 15 Clearly, the hydrogen for this catalytic reduction must come from the catalyst itself. This reduction process may, in fact, be involved in the formation of the coordinately unsaturated catalytically active ruthenium species needed for copolymerization. If this interpretation is correct, decreasing the concentration of catalyst should lead to higher molecular weight polymers - albeit longer reaction times. T T T T 5 . 0 T I 6.0 1 9 .0 7 .0 0.0 4 .0 3 .0 FFM Figure 3. ^H NMR of copoly(l,8-xanthonylene/3,3,5,5-tetramethyl-4-oxa-3,5-disila- 1,7-heptanylene). 6 The thermal stability of these polymers has been determined by TGA. (Figure 4a-d) They are all stable to at least 200°C. Between 220 and 300°C copoly(l,8- anthronylene/3,3,6,6-tetramethyl-3,6-disila-l,8-octanylene) loses eight percent of its initial weight. Above 300°C, more rapid weight loss occurs. By 400°C, almost fifty percent of initial sample weight has been lost. Between 400 and 700°C the rate of weight loss is slower. By 700°C, only sixteen percent of the initial sample weight remains. No further weight loss is observed. Between 220 and 300°C copoly(l,8-anthronylene/3,3,5,5-tetramethyl-4-oxa-3,5- disila-l,7-heptanylene) loses five percent of the initial sample weight. Above 300°C more rapid weight loss occurs. By 420°C, only forty-seven percent of the initial weight remains. Above this temperature the rate of weight loss is slower. By 780°C, thirty-five percent of the initial weight still remains. Copoly(l,8-fluorenonylene/3,3,5,5-tetramethyl-4-oxa-3,5-disila-l,7-heptanylene) is thermally stable to 235°C. Between 235 and 370°C seven percent of the initial sample weight is lost. Above this temperature more rapid weight loss occurs. By 500°C, only forty-two percent of the original sample weight remains. Above this temperature, weight loss occurs more slowly. By 780°C, thirty-three percent of the initial sample weight still remains. Poly( 1,8-xanthonylene/3,3,5,5-tetramethyl-4-oxa-3,5-disila-1,7-heptanylene) loses thirteen percent of its initial weight between 220 and 380°C. Above this latter temperature more rapid weight loss occurs. By 460°C, forty-five percent of the original sample wight remains. Above this temperature weight loss occurs more slowly. By 700°C, a black glassy residue amounting to thirty-two percent of the initial weight is found. 7 1 0 0 .0 0 FROM: 1 8 2 .9 3 TO: 3 9 3 .3 7 ONSET AT 3 0 5 .5 5 X NT- 101 3 0 0 .M S T o o 220.00 460.00 620.00 700.00 140.00 780.00 TEMPERATURE (C) Figure 4a. TGA of copoly(l,8-anthronylene/3,35 6,6-tetram ethyl-3,6-disila-l,8- octanylene). 100.00 FftOK 1 6 0 .7 4 TO: 3 7 1 .3 8 ONSET AT 3 0 7 .5 8 X NT- 1 0 0 .6 4 300.00 L O O 1 . 0 0 220.00 620.00 700.00 1 . 0 0 140.00 760.00 TEMPERATURE (C) Figure 4b. TGA of copoly(l,8-anthronylene/3,3,5,5-tetramethyl-4-oxa-3,5-disila-l,7- heptanylene) 8 100.00 FftOK 2 0 1 .6 5 TO: 4 1 4 .6 3 ONSET AT 3 6 9 .4 5 X NT- 9 9 .3 7 r-j s o .o o 1.00 300.00 1 . 0 0 140.00 L O O TEMPERATURE (C) Figure 4c. TGA of copoly(l,8-fluorenonylene/3,3,5,5-tetramethyl-4-oxa-3,5-disila- 1,7-heptanylene). 100.00 FRO* 2 2 9 .7 2 TO: 4 3 3 .3 3 ONSET AT 3 6 6 .6 7 X WT- 9 7 .6 2 H X C O M U i 2 7& .00 300.00 300.00 700.00 1 . 0 0 TEMPERATURE (C) Figure 4d. TGA of copoly(l,8-xanthonylene/3,3,5,5-tetramethyl-4-oxa-3,5-disila- 1,7-heptanylene). 9 As has been reported, the reactivity of cyclic ketones varies considerably. (Table 1) Xanthone and anthrone require a considerably shorter reaction time than that for the reaction with fluorenone. Anthrone is less reactive than xanthone. This may be due to electronic effects. The ether oxygen of xanthone may be considered as an electron- donating group at ortho position. Interestingly, fluorenone, a five-membered ring ketone, did undergo the coupling reaction with a,o>-dienes. On the contrary, 1-indanone has been reported not to react at all.2 Ketone Time (h) Terminal D ouble Bond (determ ined by NMR) 0 60 S o m e of double b ond s 60 No double bond 48 No double bond Mole Number: Ketone : 1,3-divinyltetram ethyldisiloxane : "Ru" catalyst = 1:1: 0.03 Table 1. Comparison of the reactivity of fluorenone, anthrone, and xanthone with 1,3- divinyltetramethyldisiloxane. 10 1.4 Experimental Section: Spectroscopic lH and NMR spectra were obtained on either a Bruker AC-250 or a AM-360 spectrometer operating in the Fourier Transform mode. 29si NMR spectra were recorded on an IBM-Bruker WP-270-SY spectrometer. Five percent weight/volume solutions of copolymer in chloroform-d were used to obtain NMR spectra, NMR spectra were run with broad band proton decoupling. A heteronuclear gated decoupling pulse sequence (NONOE) with a 20 sec delay was used to acquire 29si NMR spectra. 16 These were externally referenced to TMS. Chloroform was used as an internal standard for and 13c NMR spectra. IR spectra of neat films on NaCl plates were recorded on an IBM FT- IR spectrometer. UV spectra of cyclohexane solutions were acquired on a Shimadzu UV- 260 ultraviolet visible spectrometer. Molecular Weight Distribution Gel permeation chromatographic (GPC) analysis of the molecular weight distribution of these polymers was performed on a Waters system comprised of a U6K injector, a 510 HPLC solvent delivery system, a R401 refractive index detector and a model 820 Maxima control system. A Waters 7.8mm x 30cm Ultrastyragel linear column packed with less than 10 |im particles of mixed pore size crosslinked styrene divinylbenzene copolymer maintained at 20°C was used for the analysis. The eluting solvent was HPLC grade THF at a flow rate of 0.6 mL/min. The retention times were calibrated against those of known monodisperse polystyrene standards: Mp 612,000, 114,200, 47,500, 18,700, 5,120, 2200 and 794 whose Mw/M n are less than 1.09. 1 1 T herm ogravim etric Analysis (TGA) TGA of the polymers was carried out on a Perkin-Elmer TGS-2 instrument with a nitrogen flow rate of 40 cc/min. The temperature program for the analysis was 50°C for 10 min followed by an increase of 4°C/min to 750°C. D ifferential Scanning C alorim etry(D SC ) The glass transition temperatures (Tg's) of the copolymers were determined by DSC on a Perkin-Elmer DSC-7 instrument. The melting point of indium (mp 165°C) was used to calibrate the DSC. The program for the analysis was -100°C for 10 min followed by an increase in temperature of 20°C/min to 150°C. Elem ental Analysis was performed by Oneida Research Services Inc., Whitesboro, NY. M onom ers and C atalyst 1,3-Divinyltetramethyldisiloxane, and 3,3,6,6-tetramethyl-3,6-disila-l,7-octadiene were obtained from United Chemical Technologies. Anthrone, fluorenone, and xanthone were obtained from Aldrich. The latter three were purified by recrystallizatoin from 95% ethanol. Dihydridocarbonylrm(triphenylphosphine)ruthenium (Ru-catalyst) was prepared from ruthenium trichloride following literature procedures. 1? Hydrated ruthenium trichloride (0.26 g) in ethanol, aqueous formaldehyde (10 mL), and sodium borohydride (0.19 g) in ethanol were added in rapid succession to a stirred solution of triphenylphosphine (1.57 g) in boiling ethanol. The mixture was heated under reflux for 15 min, and then cooled; the resultant precipitate was filtered off, washed with ethanol, water, and ethanol, 1 2 and dried in vacuo. Recrystallisation from benzene-hexane gave the pure catalyst as white microcrystals in 75% yield. Copoly( 1,8-fIuorenony lene/3,3,5,5-tetram ethyl-4-oxa-3,5-disiIa-1,7- heptanylene) Fluorenone(0.45 g, 2.5 mmol), l,3-divinyltetramethyldisiloxane(0.47 g, 2.5 mmol) and Ru-catalyst (0.15 g, 0.075 mmol), 3 mL xylene and a Teflon-covered magnetic stirring bar were placed in a glass tube (10 mm in diameter, 12 cm long, which was partially constricted 10 cm from the bottom). The tube and its contents were cooled in a dry-ice/isopropanol bath. After two ffeeze-thaw cycles to remove oxygen, the tube was sealed under vacuum. The reaction mixture was stirred for 72 h at 150°C. The color of the reaction mixture changed from colorless to black. The solvent was removed by evaporation under reduced pressure. After worked up as above, 0.85 g, 92.3% yield of crude copolymer was obtained. The crude copolymer was dissolved in a minimum amount of THF and was precipitated from methanol. This process was repeated three times. In this way, 0.67 g, 73% yield, Mw/Mn = 3010/1670; Tg = -6.7°C was obtained. TGA onset at 369.5°C, 50% at decomposition 476°C, 30% residue; NMR 8: 0.20(s, 12H), 0.92(br.s, 4H), 3.06(br.s, 4H), 7.06(br.s, 2H), 7.25(br.s, 4H). NMR 8: 0.35, 19.54, 24.75, 117.24, 123.66, 130.01, 134.13, 144.40, 146.64, 195.38. 29Si NMR 8: 7.52. IR x > : 3053, 2955, 2924, 2884, 1701, 1593, 1482, 1452, 1434, 1409, 1326, 1289, 1253, 1206, 1179, 1146, 1054(Si-O-Si), 929, 841, 783, 756, 695, 663 c m 'l UV Xmax nm (e): 214(61,000), 256(88,500), 299(6,100), 308(6,400), 323(6,770), 338(5,730), 381(1,920). Elemental Anal. Calcd for C 2lH 2602Si2: C, 68.85; H, 7.10. Found: C,68.56; H,7.00. The material which did not precipitate was shown by GPC and NMR to be lower molecular weight cooligomers. C opoly(l,8-anthronylene/3,3,6,6-tetram ethyl-3,6-disila-l,8-octanylene) Anthrone(0.49 g, 2.5 mmol), 3,3,6,6-tetramethyl-3,6-disila-l,7-octadiene(0.50 g, 2.5 mmol) and Ru-catalyst (0.15 g, 0.075 mmol), 3 mL xylene and a Teflon-covered magnetic stirring bar were placed in a glass tube (10 mm in diameter, 12 cm long, which was partially constricted 10 cm from the bottom). The tube and its contents were cooled in a dry-ice/isopropanol bath. After two freeze-thaw cycles to remove oxygen, the tube was sealed under vacuum. The reaction mixture was stirred for 72 h at 150°C. The color of the reaction mixture changed from colorless to black. The solvent was removed by evaporation under reduced pressure. After work-up, 0.82 g, 82% yield of crude copolymer was obtained. After purification, 0.7 g, 70% yield of copolymer, Mw/M n = 3580/1520; Tg = 2.6°C was obtained. TGA onest at 305.6°C, 50% at decomposition 433°C, 28% residue. *H NMR 8: 0.05(s, 12H), 0.40-0.52(br.s, 4H), 0.90(br.s, 4H), 3.06(br.s, 4H), 4.13(br.s, 2H), 7.20(br.s 4H), 7.31(br.s, 2H). 13C NMR 5: -3.84, 7.29, 17.59, 28.52, 34.76, 125.08, 128.72, 130.95, 133.22, 139.97, 147.21. 2 9 si NMR 8: 11.86. IR u: 3064, 3023, 2953, 2904, 1946, 1665, 1594, 1574, 1469, 1451, 1411, 1355, 1292, 1247, 1176, 1157, 1133, 1075, 1054, 978, 941, 910, 832, 778, 734, 650 c m '1. UV X max nm (e): 215(32,000,), 259(26,400), 308(5,280), 348(2,140). Elemental Anal. Calcd for C24H320Si2: C, 73.47; H, 8.16. Found: C,70.63; H,7.54. Copoly (1,8-anthronylene/3,3,5,5-tetram ethyl-4-oxa-3,5-disila-l,7- heptanylene) Anthone(0.49 g, 2.5 mmol), l,3-divinyltetramethyldisiloxane(0.47 g, 2.5 mmol) and Ru-catalyst (0.15 g, 0.075 mmol), 3 mL xylene and a Teflon-covered magnetic stirring bar were placed in a glass tube (10 mm in diameter, 12 cm long, which was partially constricted 10 cm from the bottom). The tube and its contents were cooled in a dry- 1 4 ice/isopropanol bath. After two ffeeze-thaw cycles to remove oxygen, the tube was sealed under vacuum. The reaction mixture was stirred for 72 h at 150°C. The color of the reaction mixture changed from colorless to black. The solvent was removed by evaporation under reduced pressure. After work-up, 0.78 g, 81% yield of crude copolymer was obtained. After purification, 0.65 g, 68% yield of copolymer Mw/Mn = 3010/1220; Tg = 1°C, was obtained. TGA onset at 307.6°C, 50% at decomposition 406.7°C, 33% residue; NMR 5: 0.04-0.24(m, 12H), 0.95(s, 4H), 3.07(s, 4H), 4.11 (s, 2H), 7.17-7.71(m, 4H). NMR 8: 0.51, 21.24, 28.05, 34.74, 125.10, 128.58, 130.97, 133.23, 139.98, 147.06, 189.83. 29Si NMR 8: 7.65. IR u: 3063, 2957, 2055, 1766, 1671, 1590, 1577, 1483, 1468, 1450, 1438, 1410, 1327, 1291, 1254, 1227, 1179, 1120, 1059, 911, 841, 795, 733, 710, 695, 648 c m '1. UV Xmax nm (e): 213(37,460), 253(31,810), 310(4,730), 340(3,720). Copoly (1,8-xanthonyIene/3,3,5,5-tetram eth y l-4 -o x a-3 ,5 -d isila-l,7- heptanylene) Xanthone(0.25 g, 1.25 mmol), l,3-divinyltetramethyldisiloxane(0.25 g, 1.25 mmol) and Ru-catalyst (0.08 g, 0.075 mmol), 3 mL xylene and a Teflon-covered magnetic stirring bar were placed in a glass tube (10 mm in diameter, 12 cm long, which was partially constricted 10 cm from the bottom). The tube and its contents were cooled in a dry-ice/isopropanol bath. After two ffeeze-thaw cycles to remove oxygen, the tube was sealed under vacuum. The reaction mixture was stirred for 72 h at 150°C. The color of the reaction mixture changed from colorless to black. The solvent was removed by evaporation under reduced pressure. After work-up, 0.40 g, 80% yield of crude copolymer was obtained. After purification, 0.32 g, 64% yield o f copolymer Mw/Mn = 3490/1700, Tg = -1.9°C, was obtained. TGA onset at 388.7°C, 50% at decomposition 1 5 447°C , 30% residue; *H NMR 8: 0.13(s,12H), 0.91(br.s, 4H), 3.26(br.s, 4H), 7.03(br.s, 2H), 7.19(br.s, 2H), 7.41(br.s, 2H). NMR 5: 0.48, 20.72, 29.05, 115.18, 120.71, 124.96, 133.03, 149.09, 156.62, 179.75. 29Si NMR 5: 7.62. IR v: 3072, 2957, 2930, 1703, 1687, 1651, 1615, 1597, 1568, 1532, 1472, 1446, 1432, 1412, 1347, 1312, 1253, 1179, 1154, 1132, 1060, 984, 963, 909, 843, 785, 735, 651, 613 cm-1. UV Xmax nm (e) 243(15,600), 274(4,460), 290(1,620), 332(2,780), 345(3,130). Elemental Anal. Calcd for C 2lH 2603Si2: C, 65.97; H, 6.81. Found: C, 63.68; H, 6.67. 1.4 References: 1. H. Guo, W. P. Weber. Polymer Bull., 1994,32, 525. 2. S. Murai, F. Kakiuchi, S. Sekine, Y. Tanaka, A. Kamatani, M. Sonoda, N. Chatani, Nature, 1993, 366, 529. 3. S. Mural, F. Kakiuchi, S. Sekine, Y. Tanaka, A. Kamatani, M. Sonoda, N. Chatani, Pure & Applied Chem., 1994, < 5 6 , 1527. 4. F. Kakiuchi, S. Sekine, Y. Tanaka, M. Sonoda, N. Chatani, S. Murai, Bull. Chem. Soc. Jpn., 1995, 68, 62. 5. F. P. Baldwin, G. Ver Strate, Rubber Chem. Technology 1972, 45, 709. 6. I. Pasquon, A. Valvassori, G. Sartori. "The Copolymerization o f Olefins by Ziegler- Natta Catalysts"-, in "Stereochemistry o f Macromolecules" Vol. 1, A. D. Ketley Ed., Marcel Dekker, New 1967. 7. J. C. Randall, Macromolecules, 1978,11, 592. 8. R. F. Heck, Org. React., 1982, 27, 345. 9. H. P. Weitzel, K. Mullen, Makromol. Chem., 1990,191, 2837. 10. Z. N. Bao, Y. M. Chen, R. B. Cai, L. P. Yu, Macromolecules, 1993,26, 5281. 11. M. Suzuki, J. C. Lim, T. Saegusa, Macromolecules, 1990,23, 1574. 12. H. Martelock, A. Geiner, W. Heitz, Makromol. Chem., 1991,192, 967. 13. W. Heitz, W. Brugging, L. Freund, M. Gailberger, A. Greiner, H. Jung, U. Kapschulte, N. Nieber, F. Osan, Makromol. Chem., 1988,189, 119. 14. B. Hileman, Chem. Eng. News, 1993, 71, 11. 15. H. Imai, T. Nishiguchi, K. Fukuzumi, J .Org. Chem., 1976, 41, 665. 16. R. Freeman, H. D. W. Hill, R. Kaptein, J. Magn. Reson., 1972,7, 327. 17. J. J. Levison, S. D. Robinson, J. Chem. Soc., 1970, A: 2947. 1 7 I l l 9 .0 6 .0 7 .0 6 .0 5 .0 . 4 .0 3 .0 2 .0 1 .0 0 .0 PPM Figure5. NMR of copoly(l,8-fluorenonylene/3,3,5,5-tetramethyl-4-oxa-3,5- disila-1,7-heptanylene). 'iii] i i i i r"i i i i | " i n f | i i i i ] i i i i - ] T " ! — i — r y n — i ~t j" 7 ' — i — r'pr 40 30 20 to o PPM •to -20 -30 -40 Figure 6. 29§i NMR of copoly(l,8-fluorenonylene/3,3,5,5-tetramethyl-4-oxa-3,5- disila-1,7-heptanylene). 1 8 S U M • JS f.J U J s g N M - IM Figure 7. FT-IR of copoly(l,8-fluorenonylene/3,3,5,5-tetramethyl-4-oxa-3,5-disila- 1,7-heptanylene). u r \ j > KJ CV S3 Figure 8. UV spectrum of copoly(l,8-fluorenonylene/3,3,5,5-tetramethyl-4-oxa 3,5 disila-1,7-heptanylene). 1 9 60 T(| f ro K - 1 7 .9 9 to : 1 0 .1 4 O noot— 1 0 .6 7 Tfl— 6 .7 1 a 0 " 4 5 1 5 : S T o o * 0 6 j O o t o w Figure 9. DSC of copo!y(l,8-fluorenonylene/3,3,5,5-tetramethyl-4-oxa-3,5-disila- 1,7-heptanylene). PPM Figure 10. NMR of copoly(l,8-anthronylene/3,3,6,6-tetramethyl-3,6-disila-l,8- octanylene). 20 Figure 11. 29§j NMR of copoly(l,8-anthronylene/3,3,6,6-tetramethyl-3,6-disila-l,8- octanylene). O Figure 12. UV spectrum of copoly(l,8-anthronylene/3,3.6,6-tetramethyl-3,6-disila- 1,8-octanylene). 2 1 K M I M j 6 M .il ■ j J c x > _ U I M Figure 13. FT-IR of copoly(l,8-anthronylene/3,3,6,6-tetramethyl-3,6-disila-1,8- octanylene). 37.9 Tg f r o K - 1 1 .7 9 to : 3 4 .0 1 O n i o t - l . i a T o - 2 .6 4 X e x o u. ► - < U J Z 12.9 Figure 14. DSC of copoly(l,8-anthronylene/3,3,6,6-tetram ethyl-3,6-disila-l,8- octanylene). 22 11 I I1 T M I I I | » TTTTTTp 3 0 8 .0 7 .0 6 . 0 5 . 0 4 * 0 PEN T t t ■ i | i ■ t ■ i i . | ■ ■ . i , i ,i ■ i ■ ■ ■ ■ | , ■ r i j .. .. | , , ,, | ,., .) ,, t , 3 ,0 2 . 0 1 ,0 0 .0 Figure 15. NMR of copoly(l,8-anthronylene/3,3,5,5-tetramethyl-4-oxa-3,5- disila-1,7-heptanylene). i t i w . " I 'I I " I i ' I I " I I'" " " I I 20 0 100 160 140 120 100 6 0 6 0 40 20 PPM Figure 16. NMR of copoly(l,8-anthronylene/3,3,5,5-tetramethyl-4-oxa-3,5- disila-1,7-heptanylene). 2 3 1 0 00 Figure 17. 29$i NMR of copoly(l,8-anthronylene/3,3,5,5-tetramethyl-4-oxa“3 disila-1,7-heptanylene). O Figure 18. UV spectrum of copoly(l,8-anthronylene/3,3,5,5-tetramethyl-4-oxa-3, disila-1,7-heptanylene). . 000 W I N - W d a l CE 40 - 2 0 - 2010 IfflVF.NUM BfcR icffl-tl Figure 19. FT-IR of copoly(l,8-anthronylene/3,3,5,5-tetramethyl-4-oxa-3,5-disila- 1,7-heptanylene). 22.5 X e x o u. 7.5 Figure 20. DSC of copoly(l,8-anthronyIene/3,3,5,5-tetramethyl-4-oxa-3,5-disila-l,7- heptanylene). 2 5 i l l J I 200 100 S60 140 120 I 100 PPM I 60 I 60 I 40 I 20 Figure 21. l^C NMR of copoly(l,8-xanthonylene/3,3,5,5-tetramethyl-4-oxa-3,5- disila-1,7-heptanylene). MO -1 5 25 -3 0 -3 5 *40 40 Figure 22. 29$j NMR of copoly(l,8-xanthonylene/3,3,5,5-tetramethyl-4-oxa-3,5- disila-1,7-heptanylene). 2 6 » - U l y cr 3 ? £ S k* u - N 20 - 59 M A M U WHVtNUHfltR ( f H - n Figure 23. FT-IR of copoly(l,8-xanthonylene/3,3,5,5-tetramethyl-4-oxa-3,5-disila- 1,7-heptanylene). 0 0 Figure 24. UV spectrum of copoly(l,8-xanthonylene/3,3,5,5-tetramethyl-4-oxa-3,5- disila-1,7-heptanylene). 2 7 13 T ® f r o K -1 7 .8 7 to : 8 .6 5 On«0 t —6 .9 1 Tg— 1 .85 x ■ 10 x o d •?— s « A ) .o o T a a p a r a tu r a (C) 'O o Figure 25. DSC of copoly(l,8-xanthonylene/3,3,5,5-tetramethyI-4-oxa-3,5-disila- 1,7-heptanylene). 2 8 CHAPTER 2 Ruthenium Catalyzed Regioselective Step-growth Copolymerization of p-D ialkylam inoacetophenones, p-Methoxyacetophenone, p-Phenoxyacetophenone or p-Phenylacetophenone and a,co-Dienes. 2.1 Summary: Ruthenium catalyzed step growth copolymerization of p-dialkylaminoacetophenones, p-methoxyacetophenone, p-phenoxyacetophenone or p-phenylacetophenone with oc,co- dienes such as 1,3-divinyltetramethyldisiloxane or 3,3,6,6-tetramethyl-3,6-disila-l,7- octadiene gives copolymers which have respectable molecular weights. The synthesis and characterization of these copolymers is reported. 2.2 Introduction: In late 1993, Murai et al. reported the dihydridocarbonylrm(triphenylphosphine)- ruthenium (Ru) catalyzed addition of the ortho C-H bonds of acetophenone across the C- C double bonds of olefins to yield ortho alkyl substituted acetophenones.1'3 We have shown that this new reaction can be applied to achieve step-growth copolymerization (cooligomerization) of aromatic ketones and a,co-dienes. For example, reaction of 1,3- divinyldimethylsilane and acetophenone catalyzed by Ru at 150°C yields copoly(3,3- dimethyl-3-sila-l,5-pentanylene/2-aceto-l,3-phenylene), Mw/Mn = 3,500/2,430, in 70% yield.^ (Scheme 1) We have carried out similar copolymerization reactions between anthrone, fluorenone or xanthone and a,co-dienes such as 3,3,6,6-tetramethyl-3,6-disila-l,7-octadiene or 1,3- 2 9 Scheme 1. Synthesis of copoly(3,3-dimethyl-3-sila-l,5-pentanylene/2-acetyl-l,3- phenylene). divinyltetramethyldisiloxane.5 (Scheme 2) The molecular weights of the copolymers (cooligomers) are generally low (Mw/Mn ~ 3,000/1,600). This is not unexpected since exact stoichiometry is essential to achieve high molecular weights in step-growth co polymerization reactions.^ The occurrence of even minor unknown side reactions will destroy the required balance of stoichiometry. S k ^ "Ru" catalyst Scheme 2. Synthesis of copoly(l,8-anthronylene/3,3,6,6-tetramethyl-3,6-disila-l,8- octanylene). In this chapter, we report the ruthenium catalyzed step-growth copolymerization of p-dialkylaminoacetophenones, p-methoxyacetophenone, p-phenoxyacetophenone or p- phenylacetophenone with a,o>-dienes.(Scheme 3) These reactions proceed more readily and yield significantly higher molecular weight copolymers than previously reported examples. "Ru" catalyst 0 0 Schem e 3. Synthesis of copoly(3,3,5,5-tetram ethyl-4-oxa-3,5-disila-l,7- heptanylene/2-aceto-5-piperidino-l,3-phenylene). 2.3 Results an d Discussion: Murai has suggested that the ruthenium catalyzed ortho alkylation reaction of acetophenone with alkenes proceeds by insertion of a carbonyl complexed coordinately unsaturated Ru species into an adjacent ortho C-H bond to yield an aryl-Ru-H intermediate. ^‘3 The well known insertion of palladium species into aromatic C-H bonds which are ortho to activating groups, such as N,N-dimethylaminomethyl may be similar.7’8 The ruthenium catalyzed reactions of aromatic ketones and alkenes or a,to- dienes maybe related mechanistically to the palladium catalyzed Heck reaction of aryl halides with alkenes.^ Insertion of palladium into the C-X bond of the aryl halide leads to a reactive aryl palladium species which is the key intermediate in this reaction. The Heck reaction has also been applied to the synthesis of polymers. 10-14 Attempts to carry out ruthenium catalyzed copolymerization reaction between 4- acetylpyridine and 1,3-divinyltetramethyldisiloxane under conditions which were successful with acetophenone and 1,3-divinyltetramethyldisiloxane met with f a i l u r e . 1 5 3 1 This may be rationalized on the basis that much of the chemistry of pyridine is analogous to that of nitrobenzene. For example, pyridine undergoes aromatic electrophilic substitution reactions with d i f f i c u l t y . 16 This analysis suggests that the insertion of the complexed coordinately unsaturated Ru species into the ortho C-H bond might have some of the characteristics of an aromatic electrophilic substitution r e a c t io n . 17 Based on this assumption, acetophenones substituted with electron donating groups in the para position should undergo this reaction with greater facility and might lead to higher molecular weight copolymers. To test this concept, we have carried out Ru catalyzed copolym erization reactions between 4'-piperidinoacetophenone, 4'-morpho- linoacetophenone, 4'-(N'-benzyl)piperazinoacetophenone, 10-methyl-(10H)acridinone, 4'-methoxyacetophenone, 4'-phenoxyacetophenone or 4'-phenylacetophenone and 1,3- divinyltetramethyldisiloxane or 3,3,6,6-tetramethyl-3,6-disila-l,7-octadiene. In fact, the molecular weights of the copolymers obtained are significantly higher, with the exception of that obtained with 10-methyl-9(10H)acridinone. Although 4'-phenyl is not a typical electron donating group, the 4'-phenylacetophenone also gave the higher molecular weight polymers. Further, the reactions proceed significantly faster. For example, reaction time at 150°C may be decreased to 4 h with 4'-piperidinoacetophenone from 24 h with acetophenone. The yields of these copolymers are also high (around 70-90%). (Table 1) The structure of the copolymers reported herein was determined by lH, 13c, and 29si NMR spectroscopy is consistent with predominant regioselective addition of the C- H bonds, which are ortho to the carbonyl group of 4'-piperidinoacetophenone, 4'- m orpholinoacetophenone, 4'-(N '-benzyl)piperazinoacetophenone, 10-methyl- 9(10H)acridinone, 4'-m ethoxyacetophenone, 4'-phenoxyacetophenone or 4'- phenylacetophenone across the C-C double bonds of 1,3-divinyltetramethyldisiloxane or 32 3,3,6,6-tetramethyl-3,6-disila-l,7-octadiene such that the hydrogens becomes attached to the more substituted end of the double bond. (Figure 1) 2 9 si NMR is highly characteristic for both polycarbosilane and polysiloxane, such as the signal at ~7.20 ppm assigned to the O-Si-O groups, and the resonance of ~4.20 ppm assigned to the C-Si-C groups. (Table 1) However, in addition to these major resonances, minor signals are observed which may be assigned to units in which the C-H bond ortho to the dialkylamino group has added in a similar regioselective manner across the C-C double bond of 1,3-di- vinyltetramethyldisiloxane or 3,3,6,6-tetramethyl-3,6-disila-l,7-octadiene. Specifically, in the ^H NMR of copoly(3,3,6,6-tetramethyl-3,6-disila-l,8-octanylene/2-aceto-5-piperi- dino-l,3-phenylene) additional resonances are detected at 0.024, 0.41, 2.49, 2.86-2.94, 3.30, 6.66, 7.68 and 7.71 ppm. Similarly in the l^C NMR addition signals are detected at -4.03, 29.00 and 30.20 ppm and finally a 29si NMR signal at 4.80 ppm. See Figure 2 for assignments. On the basis of NMR integration, addition across the C-H bond which is ortho to the carbonyl group is favored by a factor of at least ten over the addition of the C-H bond which is ortho to the dialkylamino groups, although this ratio is sensitive to experimental conditions. 3 3 0 : H NMR L O l J L l i i 3 4 PPM t 0 'C NMR 200 I ‘ .S O I ISO 1 4 0 T 1 2 0 I ICO PPM n — 1 — i — 1 — i — 1 — i — t 8 0 80 40 20 '3 Si N M R T' 1 i i . . . I • i • ■ • ■ t l i i i | j i i 20.0 15.0 10.0 5 .0 - .0 - 5 .0 -u) g - I S .0 P P M Figure 1. *H, and ^ S i NMR of copoly(3,3,5,5-tetramethyl-4-oxa-3,5-disila- 1,7-heptanylene/2-aceto-5-piperidino-1,3-phenylene). 34 H NMR I \ / I3C NMR m T 200 T to T I 120 O, I f t * \ 9 — | j | j. 00 90 fO 30 £9 n r 1 0 1 t r 3 - 2 0 - J O - 4 0 Figure 2. ^H, 13C and 29Si NMR of copoly(3,3,6,6-tetramethyl-3,6-disila-l,8- octanylene/2-aceto-5-piperidino-1,3-phenylene). 3 5 The choice of 1,3-divinyltetramethyldisiloxane and 3,3,6,6-tetramethyl-3,6-disila- 1,7-octadiene as a.to-dienes is not random. Based on our previous work, it is apparent that most a,co-dienes are NOT suitable substrates for this reaction. 18 The ruthenium catalyst not only catalyzes the insertion of C-C double bonds of oc,co-dienes into the ortho C-H bonds of aromatic ketones - but also the isomerization of terminal C-C double bonds to internal double bonds which are much less reactive. 1,3-Divinyltetramethyldisiloxane and 3,3,6,6-tetramethyl-3,6-disila-l,7-octadiene have been utilized because isomerization of their C-C double bonds is blocked by the silicon atoms. Higher molecular weights are important since many polymer properties change rapidly until a minimum threshold molecular weight is achieved. Frequently, this minimum polymer molecular weight for constant polymer properties occurs at about a molecular weight of 10,000.19 All of the copolymers reported herein with the exception of that obtained with on 10-methyl-9(10H)acridinone have molecular weights greater than 15,000. The molecular weights, glass transition temperatures are listed in Table 1. The low molecular weight of the 10-methyl-9(10H)acridinone copolymer may result from electronic factors. Specifically, 10-methyl-9(10H)acridinone is more like an alkylarylaminoacetophenone than a dialkylaminoacetophenone and hence the nitrogen is less electron donating in this system. In this regard, aniline is well known to be less basic than aliphatic amines. 3 6 Structures of C opolym ers 0 ,o \ / Si''s/ \ S U / \ 0 \ / \ / S i \ Q ^ S 0 \ / 0 c h3 Yield (%) 91 80 86 80 64 Tg (°C) 14 2.7 19 M*,/ Mr 29 Si(ppm) 2 0 8 8 0 /95 4 0 7 .2 2 2 6 0 0 0 /1 500C 4 .1 4 1 6 4 7 0 /8 0 5 0 7 .22 3 8 0 0 0 /2 5 0 0 0 4 .1 6 3 9 0 0 /23 6 0 7 .7 2 3 7 Structures of C opolym ers Yield (%) Tg (°C) Mw / Mn 29Si(ppm) c N) V CH, 6 8 5 25 5 1 2 5 0 /1 6540 7.1 6 ' ^ X ^ s C - v s i ^ ; f t Y c h 2 6 9 2 2 3 2 5 7 9 0 /7 4 9 0 4 .1 7 o c h 3 86 -24 1 3 8 6 0 /6 7 0 0 7.21 t i X ^ s!W sc i r o c h 3 77 -6 2 9 7 0 0 /1 1 9 0 0 4 .2 0 - ^ O s C 0 > s C / - ^ OPh 8 7 -12 19 5 5 0 /1 0 4 9 0 7 .29 3 8 Structures of C opolym ers Yield (%) Tg (°C) Mw/M n 29Si(ppm) OPh 70 -1.5 1 7 5 0 0 /1 0 5 5 0 4.2 3 . Y° \ / \ / Ph 80 2.5 1 7 3 9 0 /9 9 3 0 7.28 Ph 72 7 1 1 0 0 0 /5 8 7 0 4 .2 7 Table 1. Yields, glass transition temperatures (Tgs), polymer molecular weights (Mw/Mn). and resonances in 29s i NMR spectra of the product copolymers. The TGA of copoly(3,3,5,5-tetramethyl-4-oxa-3,5-disila-l,7-heptanylene/2-aceto-5- p ip eridino-l,3-phenylene), co p o ly (3 ,3 ,5 ,5 -tetram ethyl-4-oxa-3,5-disila-l,7- heptanylene/2-aceto-5-morpholino-l,3-diphenylene) and copoIy(3,3,5,5-tetramethyl-4- oxa-3,5-disila-l,7-heptanylene/2-aceto-5-(N'-benzyl)-piperazino-l,3-phenylene) are quite similar. These polymers are thermally stable to about 210°C. Between 210°C and 385°C the former copolymer loses six percent of its initial weight. Above 385°C, rapid weight loss occurs. By 520°C fifty percent of the initial sample weight remains. Between 520°C and 700°C an additional five percent weight is lost. The TGAs of copoly(3,3,5,5-tetramethyl-4-oxa-3,5-disila-l,7-heptanylene/2-aceto-5- m ethoxy-l,3-phenylene) and copoly(3,3,5,5-tetram ethyl-4-oxa-3,5-disila-l,7- 3 9 heptanylene/2-aceto-5-phenoxy-l,3-phenylene) are similar. Both are thermally stable to about 240°C. Between 240°C and 440°C, the former copolymer loses six percent of its initial weight. Above 440°C, rapid weight loss occurs. By 500°C fifty percent of the initial sample weight remains. Between 500°C and 530°C an additional thirty-four percent weight is lost. The residues of copolymers are both about twelve percent. The TGA of copoly(3,3,5,5-tetramethyI-4-oxa-3,5-disila-l,7-heptanylene/2-aceto-5- phenyl-l,3-phenylene) is thermally stable to 240°C. Between 240°C and 380°C the copolymer loses six percent of its initial weight. Above 380°C, rapid weight loss occurs. By 460°C fifty percent of the initial sample weight remains. Between 460°C and 600°C an additional thirty-seven percent weight is lost. The residues of this copolymer is twelve percent. The TGAs of copoly(3,3,6,6-tetramethyl-3,6-disila-l,8-octanylene/2-aceto-5- piperidino-l,3-phenylene), copoly(3,3,6,6-tetramethyl-3,6-disila-l,8-octanylene/2-aceto- 5-m orpholino-l,3-phenylene) and copoly(3,3,6,6-tetram ethyl-3,6-disila-l,8- octanylene/2-aceto-5-(N'-benzyl)piperzino-l,3-phenylene) are similar. These polymers are stable to 200°C. Between 200 and 400°C, they slowly loses about six percent of their initial weight. Above 400°C rapid weight loss occurs. By 480°C about forty percent of the initial polymer weight remains. Above this temperature slower weight loss occurs. By 700°C a residue between twenty-five and thirty percent of the initial sample remains. The TGAs of copoly(3,3,6,6-tetramethyl-3,6-disila-l,8-octanylene/2-aceto-5- methoxy-l,3-phenylene) and copoly(3,3,6,6-tetramethyl-3,6-disila-l,8-octanylene/2- aceto-5-phenoxy-l,3-phenylene) are quite similar. These polymers are both stable to 270°C. Between 270°C and 430°C, the former polymer slowly loses about six percent of its initial weight. Above 430°C rapid weight loss occurs. By 500°C about fifty 4 0 percent of the initial weight remains. Between 500°C and 530°C an additional thirty- three percent weight is lost. Above 530°C slower weight loss occurs. By 700°C a residue about eight percent of the initial sample remains. The TGA of copoly(3,3,6,6-tetramethyl-3,6-disila-l,8-octanylene/2-aceto-5-phenyl- 1,3-phenylene) is stable to 220°C. Between 220°C and 390°C the polymer slowly loses about six percent of its initial weight. Above 390°C rapid weight loss occurs. By 460°C about fifty percent of the initial weight remains. Between 460°C and 500°C an additional forty-two percent weight is lost. After this temperature slower weight loss occurs. By 700°C a residue about six percent of the initial sample remains. The effect of molecular weight on the thermal stability of copoly(3,3,6,6-tetramethyl- 3.6-disila-l,8-octanylene/2-aceto-5-piperidino-l,3-phenylene) has been studied. Low molecular weight copolymers have been prepared by carrying out the copolymerization with a non-stoichiometric balance of reactants. In one case, a three percent excess of 3.3.6.6-tetramethyl-3,6-disila-l,7-octadiene was utilized (Mw/Mn = 4,000/3,000) while in the other a three percent excess of 4'-piperidinoacetophenone was employed (Mw/Mn = 9,000/3,000). The thermal stability of these lower molecular weight copolymers was significantly lower than higher molecular weight c o p o l y m e r .20 2.4 Conclusion: The ruthenium catalyzed copolymerization of acetophenones with a,co-dienes is sensitive to electronic effects in the acetophenone. Specifically electron donating groups, such as p-dialkylam ino, p-m ethoxy, p-phenyloxy, or p-phenyl, facilitate the copolymerization and result in high molecular weight polymers. In these systems the molecular weights are sufficiently high to warrant legitimate use of the word copolymers rather than cooligomers. 4 1 2.5 Experimental Section: Spectroscopic lH and NMR spectra were obtained on either a Bruker AC250 or an AM-360 spectrometer operating in the Fourier Transform mode. 29Si NMR spectra were recorded on an IBM Bruker WP-270-SY spectrometer. Five percent weight/volume solutions of copolymer in chloroform-d were used to obtain NMR spectra. 13c NMR spectra were run with broad band proton decoupling. A heteronuclear gated decoupling pulse sequence (NONOE) with a 20 sec delay was used to acquire 29si NMR spectra.^l These were externally referenced to TMS. Chloroform was used as an internal standard for and 13c NMR spectra. Ir spectra of neat films on NaCl plates were recorded on an IBM FT- IR spectrometer. UV spectra of cyclohexane solutions were acquired on a Shimadzu UV- 260 ultraviolet visible spectrometer. Molecular Weight Distribution Gel permeation chromatographic (GPC) analysis of the molecular weight distribution of these polymers was performed on a Waters system comprised of a U6K injector, a 510 HPLC solvent delivery system, a R401 refractive index detector and a model 820 Maxima control system. A Waters 7.8mm x 30cm Ultrastyragel linear column packed with less than 10 p.m particles of mixed pore size crosslinked styrene divinylbenzene copolymer maintained at 20°C was used for the analysis. The eluting solvent was HPLC grade THF at a flow rate of 0.6 mL/min. The retention times were calibrated against those of known monodisperse polystyrene standards: Mp 612,000, 114,200, 47,500, 18,700, 5,120, 2200 and 794 whose Mw/M n are less than 1.09. Thermogravimetric Analysis (TGA) TGA of the polymers was carried out on a Perkin-Elmer TGS-2 instrument with a nitrogen flow rate of 40 cc/min. The temperature program for the analysis was 50°C for 10 min followed by an increase of 4°C/min to 750°C. Differential Scanning Calorimetry(DSC) The glass transition temperatures (Tg's) of the copolymers were determined by DSC on a Perkin-Elmer DSC-7 instrument. The melting point of indium (mp 165°C) was used to calibrate the DSC. The program for the analysis was -100°C for 10 min followed by an increase in temperature of 20°C/min to 150°C. Elemental Analysis was performed by Oneida Research Services Inc., Whitesboro, NY. Chemicals and Glassware Dihydridocarbonyl/m(triphenylphosphine)ruthenium (Ru-catalyst) was prepared from ruthenium trichloride following literature p r o c e d u r e s .22 Hydrated ruthenium trichloride (0.26 g) in ethanol, aqueous formaldehyde (10 mL), and sodium borohydride (0.19 g) in ethanol were added in rapid succession to a stirred solution of triphenylphosphine (1.57 g) in boiling ethanol. The mixture was heated under reflux for 15 min, and then cooled; the resultant precipitate was filtered off, washed with ethanol, water, and ethanol, and dried in vacuo. Recrystallisation from benzene-hexane gave the pure catalyst as white microcrystals in 75% yield. 1,3-Divinyltetramethyldisiloxane, 3,3,6,6-tetramethyl-3,6-disila-1,7-octadiene were purchased from United Chemical Technologies. 4'-Piperidinoacetophenone, 4'- 4 3 morpholinoacetophenone, 4’-piperizinoacetophenone, 10-methyl-9(10H)acridinone, 4'- methoxyacetophenone, 4'-phenoxyacetophenone and 4'-phenylacetophenone were obtained from Aldrich. The latter six were purified by recrystallizatoin from 95% ethanol. 4'-Methoxyacetophenone was purified by redistillation under reduced pressure. All reactions were conducted in flame dried glassware under an atmosphere of purified argon. 4 '-(N '-b e n zy l)p ip eraz in o a ce to p h e n o n e 4'-Piperazinoacetophenone (0.61 g, 3 mmol), benzyl chloride (0.38 g, 3 mmol), and potassium carbonate(0.21 g, 1.5 mmol) and a Teflon-covered magnetic stirring bar were put in a 100 mL flame dried round-buttom flask. The flask was sealed with a rubber stopper. The reaction mixture was stirred for 24 h. The reaction mixture was poured into 100 mL water. The precipitate was filtered and recrystallized from ethanol/water. In this way, 0.7 g, 68% yield of product mp 97.5-99°C was obtained. NMR 8: 2.49(s, 3H), 2.57(m, 4H), 3.34(m, 4H), 3.54(s, 2H), 6.81-6.84(m, 2H), 7.27-7.33(m, 5H), 7.83-7.86(m, 2H). NMR 5: 26.05, 47.31, 52.68, 62.95, 113.31, 127.24, 127.53, 128.31, 129.13, 130.33, 137.69, 154.17, 196.40. IR I): 2820, 2777, 1664, 1598, 1555, 1518, 1455, 1327, 1388, 1361, 1303, 1285, 1245, 1230, 1195, 1148, 1008, 926, 906, 824, 744, 737, 733 c m 'l. UV Xmax nm(e): 311(25,870), 261(4,930), 255(5,110). C o p o ly (3 ,3 ,5 ,5 -tetram e th y l-4 -o x a-3 ,5 -d isila -l,7 -h e p ta n y Ien e /2 -ac eto -5 - p ip e rid in o -l,3 -p h e n y le n e ) 4'-Piperidinoacetophenone (0.51 g, 2.5 mmol), 1,3-divinyltetramethyldisiloxane (0.47 g, 2.5 mmol), xylene (2 mL) and Ru catalyst (0.07 g, 0.076 mmol) and a Teflon- 4 4 covered magnetic stirring bar were placed in an Ace pressure tube (15 mL, 10.2 cm long). A stream of argon was bubbled through the solution for 5 min. The tube and its contents were sealed with a Teflon bushing and FETFE "0"-ring. The reaction mixture was stirred for 48 h at 150°C. The color of the reaction mixture changed from colorless to black. The tube and its contents were cooled to rt and pentane(5 mL) was added. The reaction mixture was stirred for several min. This caused the catalyst to precipitate. After filtration, the pentane was removed from the crude polymer by evaporation under reduced pressure. The copolymer was purified three times by precipitation from tetrahydrofuran and methanol. In this way, 0.90 g, 91% of copolymer, Mw/M n = 20,880/9,540, Tg = 2°C , was obtained. ! H NMR 5: 0.064(s, 12H), 0.82(m, 4H), 1.55(s, 2H), 1.66(s, 4H), 2.42(s, 3H), 2.47(m, 4H), 3.13(s, 4H), 6.58(s, 2H). 13C NMR 5: 0.22, 21.03, 24.29, 25.78, 27.27, 33.27, 50.25, 113.77, 132.21, 141,31, 152.44, 208.17. 29Si NMR 5: 7.22. IR u: 2940, 2859, 2809, 1690, 1598, 1563, 1557, 1467, 1453, 1444, 1413, 1385, 1352, 1256, 1224, 1183, 1121, 1062, 982,911,842, 791,738,649 cm -1. UV Xmax nm (e): 216(20,200), 243(8,950), 287(6,320). Elemental Anal. Calcd for C2lH35N02Si2: C, 64.78; H, 9.00; N, 3.60. Found: C, 64.02; H, 8.90; N, 3.49. Copoly (3,3,6,6-tetramet hyl-3,6-disila-l, 8-octanylene/2-aceto-5- piperidino-l,3-phenylene) 4'-Piperidinoacetophenone (0.61 g, 3.0 mmol), 3,3,6,6-tetramethyl-3,6-disila-l,7- octadiene (0.59 g, 3.0 mmol), xylene (2 mL), Ru catalyst (0.07 g, 0.076 mmol) and a Teflon-covered magnetic stirring bar were placed in an Ace pressure tube as above. In this way, 0.9 g, 75% yield of copolymer, Mw/M n = 26,000/15,000, Tg = -5°C, was obtained. JH NMR 8: -0.04(br.s, 12H), 0.37-0.41(br.s, 4H), 0.76-0.83(m, 4H), 1.56(s, 2H), 1.65(s, 4H), 2.42(s, 3H), 2.45(m,4H), 3.14(s, 4H), 3.56(s, 2H), 6.58(s, 4 5 2H). 13c NMR 8: -4.15, 6.97, 17.62, 24.26, 25.79, 27.90, 33.27, 50.30, 113.79, 133.19, 141.61, 152.43, 208.1. 29Si NMR 5: 4.14. IR u: 2942, 2811, 1688, 1682, 1597, 1552, 1479, 1467, 1452, 1445, 1422, 1414, 1385, 1353, 1274, 1256, 1237, 1186, 1132, 1055, 967, 928, 888, 834, 781, 705, 655, 646 c m '1. UV ^ max nm (e): 215(24,300), 243(9,150), 291(7,430). Elemental Anal. Calcd for C23H390NSi2: C, 68.82; H, 9.73; N, 3.49. Found: C, 68.04; H, 9.41; N, 3.43. Copoly (3,3,5,5-tetramethy l-4-oxa-3,5-disila-l, 7-heptanylene/2-aceto-5- morpholino-l,3-phenylene) 4'-Morpholinoacetophenone (0.52 g, 2.5 mmol), 1,3-divinyltetramethyldisiloxane (0.47 g, 2.5 mmol), xylene (2 mL) and Ru catalyst (0.07 g, 0.076 mmol) and a Teflon- covered magnetic stirring bar were placed in an Ace pressure tube as above. In this way, 0.85 g, 86% yield of copolymer, Mw/Mn =16,470/8,050, Tg = 14°C, was obtained. *H NMR 5: 0.07(s, 12H), 0.8l(m , 4H), 2.42(s, 3H), 2.47(m, 4H), 3.14(s, 4H), 3.8l(s, 4H), 6.56(s, 2H). l3 C NMR 5: 0.25, 21.06, 27.27, 33.27, 48.98, 66.85, 113.00, 133.09, 141.50, 151.53, 208.00. 29Si NMR 5: 7.22. IR o: 2956, 2893, 2858, 1953, 1778, 1721, 1692, 1651, 1600, 1564, 1538, 1511, 1451, 1414, 1379, 1352, 1305, 1252, 1184, 1125, 1058, 906, 840, 788, 733, 707, 686, 647 cm"1. UV Xmax nm (e): 216(21,270), 241(3,220), 287(6,390). Elemental Anal. Calcd for C20H33NO3Si2: C, 61.38; H, 8.44; N, 3.60. Found: C, 60.90; H, 8.29; N, 3.47. Copoly(3,3,6,6-tetramethyl-3,6-disila-l,8-octanylene/2-aceto-5- morpholino-l,3-phenylene) 4'-Morpholinoacetophenone (0.62 g, 3.0 mmol), 3,3,6,6-tetramethyl-3,6-disila-l,7- octadiene (0.59 g, 3.0 mmol), xylene(2 mL), Ru catalyst (0.07 g, 0.076 mmol) and a 4 6 Teflon-covered magnetic stirring bar were placed in an Ace pressure tube as above. In this way, 0.96 g, 80% yield of copolymer, Mw/Mn = 38,000/25,000, Tg = 2.7°C, was obtained. ! H NMR 8: -0.04(br.s, 12H), 0.37(br.s, 4H), 0.75-0.82(m, 4H), 2.42(m, 4H), 2.43(s,3H), 3.15(s, 4H), , 3.82(s, 4H), 6.56(s, 2H). 13C NMR 5: -4.19, 6.91, 17.61, 27.85, 33.21, 48.95, 66.79, 112.93, 132.96, 141.72, 151.45, 207.94. 2^Si NMR 8: 4.16. IR \): 2955, 2901, 1691, 1599, 1452, 1380, 1353, 1257, 1187, 1133, 1122, 910, 834, 782, 737, 647 c m '1. UV Xmax nm (e): 215(24,600), sh243( 10,900), 283(6,500). Elemental Anal. Calcd for C22H37C>2NSi2: C, 65.51; H, 9.18; N, 3.47. Found: C, 64.98; H, 8.88; N, 3.37. Copoly (3,3,5,5-tetramethy l-4-oxa-3,5-disila-l,7-heptanyIene/2-aceto-5- (N'-benzyl)-piperazino-l,3-phenylene) 4'-(N '-B enzyl)piperazinoacetophenone (0.41 g, 1.4 mmol), 1,3- divinyltetramethyldisiloxane (0.26 g, 1.4 mmol), xylene (2 mL), Ru catalyst (0.04 g, 0.038 mmol) and a Teflon-covered magnetic stirring bar were placed in an Ace pressure tube as above. In this way, 0.57 g, 85% yield of copolymer, Mw/Mn = 51,250/16,540; Tg = 25°C, was obtained. ! H NMR 8: 0.07(s, 12H), 0 .8 l(m , 4H), 2.42(s, 3H), 2.45(m, 4H), 2.60(s, 4H), 3.21 (s, 4H), 3.58(s, 2H), 6.56(s, 2H), 7.34(m, 5H). 13C NMR 8: 0.18, 20.94, 27.17, 33.20, 48.52, 52.79, 62.78, 113.31, 127.22, 128.23, 129.22, 132.68, 137.22, 141.32, 151.42, 208.01. 29Si NMR 8: 7.16. IR u: 2977, 2869, 1693, 1600, 1456, 1385, 1352, 1255, 1180, 1147, 1069, 913, 843, 790, 734, 700, 647 c m '1. UV Xmax nm (e): 215(22,100), 243(7,210), 288(5,270). Elemental Anal. Calcd for C27H40N2O2Si2: C, 67.54; H, 8.33; N, 5.83. Found: C, 65.66; H, 7.97; N, 5.61. 4 7 Copoly(3,3,6,6-tetramethyl-3,6-disila-l,8-octanylene/2-aceto-5-(N'- benzyl)-piperazino-l,3-phenylene) 4'-(N'-Benzyl)piperazinoacetophenone (0.88 g, 3.0 mmol), 3,3,6,6-tetramethyl-3,6- disila-l,7-octadiene (0.59 g, 3.0 mmol), xylene (2 mL), Ru catalyst (0.07 g, 0.076 mmol) and a Teflon-covered magnetic stirring bar were placed in an Ace pressure tube as above. In this way, 1.35 g, 92% yield of copolymer, Mw/Mn = 25,790/7,490, Tg = 23°C, was obtained. NMR 8: -0.02(s, 12H), 0.39(s, 4H), 0.80(m, 4H), 2.42(s, 3H), 2.45(m, 4H), 2.60(s, 4H), 3.2 l(s, 4H), 3.56(s, 2H), 6.58(s, 2H), 7.34(s, 5H). !3 c NMR 5: -4.16, 6.93, 17.57, 27.86, 33.24, 48.75, 52.94, 62.93, 113.32, 127.08, 128.19, 129.11, 132.58, 137.75, 141.61, 151.54, 208.08. 29Si NMR 5: 4.17. IR 2954, 2873, 1692, 1599, 1495, 1455, 1385, 1352, 1302, 1248, 1188, 1134, 1103, 1067, 997, 911, 832, 782, 735, 699, 647 c m '1. UV >.max nm (e): 214(25,740), 243(8,950), 290(6,330). Elemental Anal. Calcd for C29H44N20Si2: C, 70.73; H, 8.92; N, 5.69. Found: C, 68.98; H, 8.84; N, 5.48. Copoly (3,3,5,5-tetra met hyI-4-oxa-3,5-disila-l,7-heptany lene/10-methyl- l,8-acrid-9-onylene) 10-Methyl-9(10H)-acridone (0.42 g, 2 mmol), 1,3-divinyItetramethyldisiloxane (0.37 g, 2 mmol), xylene (2 mL), Ru catalyst (0.04 g, 0.038 mmol) and a Teflon- covered magnetic stirring bar were placed in an Ace pressure tube as above. In this way, 0.50 g, 64% yield of copolymer, Mw/Mn = 3,900/2,360, Tg = 19°C, was obtained. NMR 5: 0.18(s, 12H), 1.03(br.s, 4H), 3.32(br.s, 4H), 3.65(s, 3H), 7.00-7.39(m, 6H). !3 c NMR 8: 0.55, 21.06, 28.92, 35.50, 111.89, 122.64, 131.74, 143.64, 148.47, 182.18. 29Si NMR 8: 7.72. IR u: 2958, 1630, 1595, 1494, 1467, 1373, 1272, 1253, 1155, 1059, 910, 843, 785, 734, 687, 651 c m '1. UV Xmax (e): 218(24,200), 4 8 258(43,960), 304(4,880), 378(7,410), 395(11,000). Elemental Anal. Calcd for C22H29NC>2Si2: C, 66.84; H, 7.34; N, 3.54. Found: C, 64.91; H, 7.31; N, 3.29. C opoly (3,3,5,5 -te tra m e th y l-4 -o x a -3 ,5 -d isila -1,7-h ep tan y len e/2 -aceto -5 - m e th o x y -l,3 -p h en y le n e ) 4’ -Methoxyacetophenone (0.50 g, 3.3 mmol), 1,3-divinyltetramethyIdisiloxane (0.62 g, 3.3 mmol), toluene (1 mL), Ru catalyst (0.06 g, 0.066 mmol) and a Teflon covered magnetic stirring bar were placed in an Ace pressure tube (15 mL, 10.2 cm long). The tube and its contents were kept in a argon atmosphere, and sealed with Teflon bushing and FETFE "0"-ring. The reaction mixture was stirred for 24 h at 150°C. The color of the reaction mixture changed from colorless to black. Pentane, 5 mL, was added and the mixture was stirred for several min to extract the polymer. This process repeated for several times. After the combination of the extractum, the pentane was removed by evaporation under reduced pressure, the crude copolymer was obtained. The crude copolymer was purified three times by precipitation from THF and methanol. In this way, 0.95 g, 86% yield of pure copolymer Mw/M n = 13,860/6,700, Tg = -24°C was obtained. TGA, Onset at 465°C. *H NMR 5: 0.07(s, 12H), 0.82(m, 4H), 2.43(s, 3H), 2.47(m, 4H), 3.77(s, 3H), 6.58(s, 2H). 13C NMR g : 0.25, 20.73, 26.92, 33.26, 55.10, 111.33, 133.93, 141.86,160.78, 207.95. 29Si NMR 8: 7.21. IR \): 3000, 2955, 2838, 1940, 1737, 1694, 1650, 1638, 1602, 1538, 1511, 1469, 1442, 1414, 1255, 1179, 1153, 1125, 1045, 954, 901, 788, 704, 623 c m '1. UV Xm ax nm (e): 250(7,360), 256(7,850), 261(7,930). Elemental Anal. Calcd for Ci7H28C>3Si2: C, 60.71; H, 8.33. Found: C, 59.82; H, 8.00. 4 9 Copoly(3,3,6,6-tetramethyl-3,6-disiIa-l,8-octanyIene/2-aceto-5-inethoxy- 1,3-phenylene) 4'-Methoxyacetophenone (0.50 g, 3.3 mmol), 3,3,6,6-tetramethyI-3,6-disila-l,7- octadiene (0.65 g, 3.3 mmol), toluene (1 mL), Ru catalyst (0.06 g, 0.066 mmol) and a Teflon covered magnetic stirring bar were placed in an Ace pressure tube. The procedure was the same as above. In this way, 0.89 g, 77% yield of copolymer Mw/M n = 29,700/11,900, Tg = -6°C was obtained. TGA, Onset at 460°C. NMR 8: -0.04(s, 12H), 0.37(s, 4H), 0.79(m, 4H), 2.40(m, 4H), 2.43(s, 3H), 3.77(s, 3H), 6.57(s, 2H). 13C NMR 8: -4.20, 6.92, 17.31, 27.54, 33.25, 55.09, 111.26, 133.63, 142.14, 159.61, 207.96. 29Si NMR 8: 4.20. IR 2951, 2900, 2838, 1702, 1698, 1694, 1682, 1674, 1619, 1600, 1574, 1468, 1455, 1441, 1422, 1414, 1350, 1327, 1293, 1246, 1192, 1176, 1152, 1133, 1075, 1054, 1037, 996, 953, 900, 828, 781 c m '1. UV A .max nm (e): 250(5,710), 255(6,010), 261(5,990). Elemental Anal. Calcd for Ci9H3202Si2: C, 65.52; H, 9.20. Found: C, 64.95; H, 9.27. Copoly (3,3,5,5-tetramet hyl-4-oxa-3,5-disila-l, 7-heptanylene/2-aceto-5- phenoxy-l,3-phenylene) 4'-Phenoxyacetophenone (0.65 g, 3.0 mmol), 1,3-divinyltetramethyldisiloxane (0.56 g, 3.0 mmol), xylene (2 mL) and Ru catalyst (0.07 g, 0.076 mmol) and a Teflon covered magnetic stirring bar were placed in an Ace pressure tube. The procedure was the same as above. In this way, 0.98 g, 87% yield of copolymer, Mw/M n = 20,100/10,750, Tg = -12°C was obtained. TGA, Onset at 432°C. ! H NMR 8: 0.04(s, 12H), 0.78(m, 4H), 2.44(m, 4H), 2.48(s, 3H), 6.70(s, 2H), 6.97(d, 2H, J=7.5Hz), 7.07(t, 1H, J=7.5Hz), 7.31 (t, 2H, J=7.5Hz). 13C NMR 8: 0.18, 20.51, 26.70, 33.16, 116.19, 118.74, 123.19, 129.71, 136.22, 142.12, 156.93, 157.26, 207.77. 29Si NMR 8: 7.29. IR \): 5 0 2955, 1699, 1588, 1492, 1255, 1058, 840 c m '1. UV Xm ax nm (e): 246(8,070), 255(7,340), 261(6,600), 276(3,910). Elemental Anal. Calcd for C22H30O3Si2: C, 66.33; H, 7.54. Found: C, 66.24; H, 7.24. Copoly (3,3,6,6-tetramethy 1-3,6-disiIa-l, 8-octanylene/2-aceto-5-phenoxy- 1,3-phenylene) 4'-Phenoxyacetophenone (0.65 g, 3.0 mmol), 3,3,6,6-tetramethyl-3,6-disila-l,7- octadiene (0.59 g, 3.0 mmol), xylene (2 mL), Ru catalyst (0.07 g, 0.076 mmol) and a Teflon covered magnetic stirring bar were placed in an Ace pressure tube. The procedure was the same as above. In this way, 0.87 g, 70% yield of copolymer, Mw/M n = 17,500/10,550, Tg = -1.5°C was obtained. TGA, Onset at 435°C. l U NMR 8: -0.04(s, 12H), 0.36(s, 4H), 0.77(m, 4H), 2.39(m, 4H), 2.47(s, 3H), 6.71(s, 2H), 6.98(d, 2H, J=7.5Hz), 7.08(t, 1H, J=7.5Hz), 7.32(t, 2H, J=7.5Hz). 13C NMR 5: -4.20, 6.88, 17.15, 27.37, 33.18, 116.27, 118.63, 123.11, 129.69, 136.22, 142.44, 157.03, 157.15, 207.90. 29Si NMR 5: 4.23. IR u: 2953, 2903, 1696, 1587, 1491, 1460, 1417, 1353, 1288, 1248, 1217, 1177, 1165, 1134, 1055, 832, 783, 695 c m '1. UV Xmax nm (e): 248(10,640), 255(10,160), 261(9,360), 276(5,770). Elemental Anal. Calcd for C24H3402Si2: C, 70.24; H, 8.29. Found: C, 69.94; H, 7.98. Copoly(3,3,5,5-tetramet hyl-4-oxa-3,5-disila-l, 7-heptanylene/2-aceto-5- phenyl-l,3-phenylene) 4'-Phenylacetophenone (0.59 g, 3.0 mmol), 1,3-divinyltetramethyldisiloxane (0.56 g, 3.0 mmol), xylene (2 mL), Ru catalyst (0.07 g, 0.076 mmol) and a Teflon-covered magnetic stirring bar were placed in an Ace pressure tube. The procedure was the same as above. In this way, 0.92 g, 80% yield of copolymer, Mw/M n = 17,390/9,930, Tg = 2.5 5 1 OC was obtained. TGA, Onset at 420°C. JH NMR 8: 0.11(s, 12H), 0.90(m, 4H), 2.49(s, 3H), 2.58(m, 4H), 7.28(s, 2H), 7.40(m, 3H), 7.54(m, 2H). 13C NMR 8: 0.24, 20.92, 26.85, 33.01, 124.94, 127.12, 127.36, 128.67, 139.88, 140.31, 140.86, 141.75, 208.04. 29Si NMR 8: 7.28. IR u: 2956, 1965, 1697, 1601, 1500, 1412, 1353, 1254, 1179,1057, 840, 797, 697 cm -1. UV Xmax nm (e): 256(18,190), 258(17,830). Elemental Anal. Calcd for C22H30O2Si2: C, 69.11; H, 7.85. Found: C, 68.40; H, 7.49. C opoly (3,3 ,6 ,6 -te tra m e th y l-3 ,6 -d isila -l, 8 -o ctan y len e/2 -aceto -5 -p h en y l- I,3 -p h en y le n e ) 4'-Phenylacetophenone (0.59 g, 3.0 mmol), 3,3,6,6-tetramethyl-3,6-disila-l,7- octadiene (0.59 g, 3.0 mmol), xylene(2 mL), Ru catalyst (0.07 g, 0.076 mmol) and a Teflon covered magnetic stirring bar were placed in an Ace pressure tube. The procedure was the same as above. In this way, 0.85 g, 72% yield of copolymer, Mw/M n = II,000/5,870, Tg = 7 °C was obtained. TGA, Onset at 422°C. NMR 8: -0.003(s, 12H), 0.42(s, 4H), 0.87(m, 4H), 2.49(s, 3H), 2.55(m, 4H), 7.27(s, 2H), 7.43(m, 3H), 7.58(m, 2H). 13C NMR 8: -4.16, 6.97, 17.54, 27.48, 33.11, 124.92, 127.14, 127.36, 128.67, 139.77, 140.60, 140.91, 141.73, 208.08. 29Si NMR 8: 4.27. IR u: 3033, 2952, 2902, 1697, 1599, 1558, 1500, 1411, 1353, 1248, 1177, 1134, 1083, 1054, 831, 697 cm’ 1. UV X .max nm (e): 259(16,600), 271(16,510). Elemental Anal. Calcd for C24.H34.Osi2 : C, 73.10; H, 8.63. Found: C, 72.28; H, 8.14. 5 2 2.6 References: 1. S. Mural, F. Kakiuchi, S. Sekine, Y. Tanaka, M. Sonoda, N. Chatani, Nature, 1993, 366, 529. 2. S. Murai, F. Kakiuchi, S. Sekine, Y. Tanaka, A. Kamatani, M. Sonoda, N. Chatani, Pure & Applied Chem., 1994, 66, 1527. 3. S. Mural, F. Kakiuchi, S. Sekine, Y. Tanaka, A. Kamatani, M. Sonoda, N. Chatani, Pure & Applied Chem., 1994, 66, 1527. 4. H. Guo, W. P. Weber, Polymer Bull., 1994, 32, 525. 5. H. Guo, M. Tapsak, W. P. Weber, Polymer Bull., 1994, 34, 49. 6. G. Odian, Principles o f Polymerization; J. Wiley & Sons: New York, NY, 1981, p 8296. 7. A. C. Cope, R. W. Siekman, J. Am. Chem. Soc., 1965, 87, 3272. 8. A. C. Cope, E. C. Friedrich,/. Am. Chem. Soc., 1968, 90, 909. 9. R. F. Heck,Org. React., 1982,27, 345. 10. H. P. Weitzel, K. Mullen, Makromol. Chem., 1990,191, 2837. 11. Z. N. Bao, Y. N. Chen, R. B. Cai, L. P. Yu, Macromolecules, 1993,26, 5281. 12. M. Suzuki, J. C. Lim, T. Saegusa, Macromolecules, 1990,23, 1574. 13. H. Martelock, A. Geiner, W. Heitz, Makromol. Chem., 1991,192, 967. 14. W. Heitz, W. Brugging, L. Freund, M. Gailberger, A. Greiner,H. Jung, U. Kampschulte, N. Nieber, F. Osan, Makromol. Chem., 1988,189, 119. 15. J. Q. Lu, unpublished results 1995. 16. R. M. Acheson, An Introduction to the Chemistry o f Heterocyclic Compounds, J. Wiley & Sons: New York, NY, 1976, p 236-238. 17. An alternative hypothesis suggested is that acetylpyridine poisons the catalyst by coordination of the unsaturated ruthenium center by the pyridinyl nitrogen. 18. H. Guo, M. A. Tapsak, W. P. Weber, Polymer Bull., 1994, 33, 417. 19. G. Odian, Principles o f Polymerization; J. Wiley & Sons: New York, NY, 1981, p 54. 20. H. Guo, M. A. Tapsak, W. P. Weber, Macromolecules, 1995, in press. 21. F. Freeman, H. D. W. Hill, R. Kaptein, J. Magn. Reson., 1972, 7, 327. 22. J. J. Levison, S. D. Robinson, J. Chem. Soc., 1970, A, 2947. 5 4 T ^ T 8.0 T r r r T r-rr I I I 4.0 i 6.0 9.0 3 Figure 3. >HNMR o f4 ' -(N'-benzyl)piperazinoacetophenone. rTni|iinimmnnin»|»m»miimunrrtTiniii|iuiiiiu|immiifiiiiuiii|uiM iiinimmn |ii i|m iin n |i im u u j i nn m i p im m piim u m wi 2 0 0 1 6 0 1 6 0 1 4 0 1 2 0 1 0 0 6 0 6 0 4 0 2 0 PPW Figure 4. 13C NMR of 4'-(N'-benzyl)piperazinoacetophenone. 5 5 i rw w K m w cE 1 1 0 .0 9 0 - W - 4 0 0 0 S S M 2 S 0 0 2 0 0 0 WflVeNUHBKR ( C « - 1 ) Figure 5. FT-IR of 4’-(N'-benzyl)piperazinoacetophenone. Figure 6. UV spectrum of 4'-(N'-benzyl)piperazinoacetophenone. 5 6 37.5 x e x o -J u. ► - < Ui X 12.5 “f e T o o iO o T a a p a r a t u r a (C) ■feoo ldo.oo do.oo Figure 7. DSC of copoly(3,3,5,5-tetramethyl-4-oxa-3,5-disila-l,7-heptanyIene/2- aceto-5-piperidino-1,3-phenylene). (n> 1 0 0 To* 400. 44 C 0 2 . 5 .. On*at a t i 3 8 0 .8 0 8 h- X u UJ X 47.5 liioo aiaoo ztew ifeoo T— poratuf <C) Figure 8. TGA of copoly(3,3,5,5-tetramethyl-4-oxa-3,5-disila-l,7-heptanylene/2- aceto-5-piperidino-1,3-phenylene). 5 7 1 3 0 . 0 IB B 2 8 0 0 WflVCNUHBKK Figure 9. FT-IR of copoly(3,3,5,5-tetramethyl-4-oxa-3,5-disila-l,7-heptanylene/2- aceto-5-piperidino-1,3-phenylene). O o o o o Figure 10. UV spectrum of copoly(3,3,5,5-tetram ethyI-4-oxa-3,5-disiIa-l,7- heptanylene/2-aceto-5-piperidino-l,3-phenylene). 5 8 1.5 Tg from : - 1 4 .4 0 to : 5 .7 3 O n a a t— 9 .1 6 Tg— 5 .2 1 x e 1 x o .5 0 '5 3 T “ T tB p s r a tu rB (C) Figure 11. DSC of copoly(3,3,6,6-tetramethyl-3,6-disila-l,8-octanylene/2-aceto-5- piperidino-1,3-phenylene). 1 0 0 4 0 9 . 0 3 2 F r o m 1 0 9 .9 9 C Tot 4 37. 13 C O n a a t o t i 4 0 9 .0 3 82.3 0 \ / / \ /* I- s O J X 47.5 T afw w otura (O Figure 12. TGA of copoly(3,3,6,6-tetramethyl-3,6-disila-l,8-octanylene/2-aceto-5- piperidino-1,3-phenylene). 5 9 o o o o o o o o Figure 13. UV spectrum of copoly(3,3,6,6-tetramethyl-3,6-disila-l,8-octanylene/2- aceto-5-piperidino-1,3-phenylene). 3 ex 1000 Figure 14. FT-IR of copoly(3,3,6,6-tetramethyl-3,6-disila-l,8-octanylene/2-aceto-5- piperidino-1,3-phenylene). 6 0 9 . 0 6.0 S .O 3 .0 2.0 0.0 PPM F igure 15. *H NMR o f copoly(3,3,5,5-tetram ethyl-4-oxa-3,5-disila-l,7- heptanylene/2-aceto-5-morpholino-1,3-phenylene). ""I"*’’"" * I —" " I.................. I...................I................. T""..............I...................I '........ I...................I................... 3 0 0 ISO 160 14 0 130 100 80 60 40 30 0 PPM F igure 16. NMR of copoly(3,3,5,5-tetram ethyl-4-oxa-3,5-disila-l,7- heptanylene/2-aceto-5-morpholino-1,3-phenylene). 6 1 -.0 - 5 . 0 - 1 5 .0 P O .O 1 5 .0 5 . 0 - 10.0 PPM Figure 17. 29$i NMR of copoly(3,3,5,5-tetram ethyl-4-oxa-3,5-disila-l,7- heptanylene/2-aceto-5-morpholino-1,3-phenylene). (n o ) 100 3 7 1 . 1 7 4 1 Onest ati 371. 17 82.5 » w 5 t u 47.5 Figure 18. TGA of copoly(3,3,5,5-tetramethyl-4-oxa-3,5-disila-l,7-heptanylene/2- aceto-5-morpholino-1,3-phenylene). 6 2 37.5 Tg f r o m :- 2 .3 8 to : 3 4 .4 6 O n s e t - 1 3 .0 9 TO- 17.32-3= 14-31. X e x a . j u. ► - * < Ui X 12.5 A ) .o o J o .o o te o o few ld o .o o ife o o iJ o j m T e n p e ra tu re (C ) ’ o T o o Figure 19. DSC of copoly(3,3,5,5-tetramethyl-4-oxa-3,5-disila-l,7-heptanylene/2- aceto-5-morpholino-1,3-phenylene). r\» o Figure 20. UV spectrum of copoly(3,3,5,5-tetram ethyl-4-oxa-3,5-disila-l,7- heptanylene/2-aceto-5-morpholino-1,3-phenylene). 6 3 g g M - 2 J - IS* Figure 21. FT-IR of copoly(3,3,5,5-tetramethyl-4-oxa-3,5-disila-l,7-heptanylene/2- aceto-5-morpholino-l,3-phenyIene). w 9 . 0 8 . 0 7 . 0 6 . 0 5 . 0 4 . 0 3 . 0 8 . 0 1 .0 0 . 0 Figure 22. NMR of copoly(3,3,6,6-tetramethyl-3,6-disila-l,8-octanylene/2-aceto- 5-morpholino-1,3-phenylene). 6 4 M w |iimiifT|Tliiiin i| iiiiiiii>pi'u iiiMniiiiu in " M iliri|H n iiilHii»iiiiii|l‘l>iiiii|iiu iiiiiririiiilln n il|| | | l| |M in in |M |ii| » jii, ||i| M | || | | | | | i|| | | | | | | |M|lf| | | | | »lj|» » m »»pTi,w» ,jl|i|» » »|| | M»||||»| | | | i.|T - 2 0 0 1B0 160 140 120 100 BO 60 40 20 0 PPM Figure 23. 13c NMR of copoly(3,3,6,6-tetramethyl-3,6-disila-l,8-octanylene/2- aceto-5-morpholino-1,3-phenylene). 60 ■ t " " 1 — r 40 3C r-p — ' i i i i i ' | 'i i i i i i i i i | i i r i ' i M m | i i 20 10 PPM -1 0 - 2 0 -30 Figure 24. 29 §i NMR of copoly(3,3,6,6-tetramethyl-3,6-disila-l,8-octanylene/2- aceto-5-morpholino-1,3-phenylene). 6 5 3 Tg f r o n t - 7 .4 0 to : 1 7 .3 2 O n s e t - 1 .S 6 T g - 2 .6 7 x e 2 K - < ui X 1 0 few ------ T a a p ir s tu r e ( C ) Figure 25. DSC of copoly(3,3,6,6-tetramethyl-3,6-disila-l,8-octanylene/2-aceto-5- morpholino-l,3-phenylene). 100 4 0 0 . 7 6 2 3 F r o m 1 8 2 .5 0 C To. 4 3 6 . 12 C O n v s t o t* 4 00. 78 0 0 60 40 2 0 Figure 26. TGA of copoly(3,3,6,6-tetramethyl-3,6-disila-l,8-octanylene/2-aceto-5- morpholino-1,3-phenylene). 66 U 1 9 % c n o o o o C f l o o o o o Figure 27. UV spectrum of copoly(3,3,6,6-tetramethyl-3,6-disila-l,8-octanylene/2- aceto-5-morpholino-1,3-phenylene). 2 0 0 - £ ar ♦J - 2UBB Figure 28. FT-IR of copoly(3,3,6,6-tetramethyl-3,6-disila-l,8-octanylene/2-aceto-5- morpholino-1,3-phenylene). 6 7 6.0 9 . 0 9 . 0 4 . 0 2.0 0.0 PPM F ig u re 29. *H NMR o f copoly(3,3,5,5-tetram ethyl-4-oxa-3,5-disila-l,7- heptanylene/2-aceto-5-(N'-benzyl)-piperazino-l,3-phenylene). •4 pn iiiiinn in n ii|»wwim piitinitjiM iwwf[itiTmwpH*w»nn' m iM ipm t 2 0 0 190 160 140 ii|ininni|iim I 100 PPM " " l'n I .. 40 80 60 F ig u re 30. NMR of copoly(3,3,5,5-tetram ethyl-4-oxa-3,5-disila-l,7- heptanylene/2-aceto-5-(N'-benzyl)-piperazino-1,3-phenylene). 68 _ ................ ....................................... ....................... " " ■ r~—» | 1 ■ " i . . ................................... ■ ■ i | -------- ■ ■ ■ ■ ............... ' '- p ............. . "’ 60 SO 40 30 30 10 0 - 1 0 - 2 0 - 3 0 PPM Figure 31. 29$, n m R of copoly(3,3,5,5-tetram ethyl-4-oxa-3,5-disila-l,7- heptanylene/2-aceto-5-(N’-benzyl)-piperazino-1,3-phenylene). 60 (nno2) 60 x 6 40 20 lo T o o 4u>6 4 5 7 5 5 i S T o o i4 o 7 6 5 E & T o o d o T o o T tu p e ratu ra (C ) o f o 7 o o Figure 32. DSC of copoly(3,3,5,5-tetramethyl-4-oxa-3,5-disila-l,7-heptanylene/2- aceto-5-(N'-benzyl)-piperazino-1,3-phenylene). 6 9 100 , 3 3 0 . 0 1 7 1 82.5 3 K 5 UJ 47.5 Figure 33. TGA of copoly(3,3,5,5-tetramethyi-4-oxa-3,5-disila-l,7-heptanylene/2- aceto-5-(N'-benzyl)-piperazino-1,3-phenylene). 19.1 m m S 5 ► - s st ub Figure 34. FT-IR of copoly(3,3,5,5-tetramethyl-4-oxa-3,5-disila-l,7-heptanylene/2- aceto-5-(N'-benzyl)-piperazino-1,3-phenylene). 7 0 F igure 35. UV spectrum of copoly(3,3,5,5-tetram ethyl-4-oxa-3,5-disila-l,7- heptany lene/2-aceto-5-(N'-benzyl)-piperazino-1,3-phenylene). Figure 36. NMR of copoly(3,3,6,6-tetramethyl-3,6-disila-l,8-octanylene/2-aceto- 5-(N'-benzyl)-piperazino-1,3-phenylene). 7 1 Figure 37. 13c NMR of copoly(3,3,6,6-tetramethyl-3,6-disila-l,8-octanylene/2- aceto-5-(N'-benzyl)-piperazino-1,3-phenylene). to 60 50 40 30 2 0 PPM -to -ao -30 -40 Figure 38. 29si NMR of copoly(3,3,6,6-tetramethyl-3,6-disila-l,8-octanylene/2- aceto-5-(N'-benzyl)-piperazino-1,3-phenylene). 37.5 Tfl from : 0 .2 3 t o : 9 2 .3 1 o n a a t - 2 1 .0 9 TO- 2 6 .4 0 x e ► - < i u X 12.5 A ) . 0 0 io M f c j O O T e n p s r a tu r a (C) ldo.oo dO o iteoo 1 . 0 0 Figure 39. DSC of copoIy(3,3,6,6-tetramethyl-3,6-disila-l,8-octanylene/2-aceto-5- (N'-benzyl)-piperazino-1,3-phenylene). < h J n n o ) 100 3 7 7 .0 9 2 7 8 UJ jm Figure 40. TGA of copoly(3,3,6,6-tetramethyl-3,6-disila-l,8-octanylene/2-aceto-5- (N'-benzyl)-piperazino-1,3-phenylene). 7 3 SM I I MlVtflUlM* t+ m -il Figure 41. FT-IR of copoly(3,3,6,6-tetramethyl-3,6-disila-l,8-octanyIene/2-aceto-5- (N'-benzyl)-piperazino-1,3-phenylene). Figure 42. UV spectrum of copoly(3,3,6,6-tetramethyl-3,6-disila-l,8-octanylene/2- aceto-5-(N'-benzyl)-piperazino-l,3-phenylene). 7 4 2 - 0 5.0 F igure 43. *H NMR o f copoly(3,3,5,5-tetram ethyl-4-oxa-3,5-disila-l,7- heptanylene/10-methyl-l,8-acrid-9-onylene). " I .... |.... ...... 140 120 100 8 0 8 0 40 vtwjHwwwfpnmwnfHW* * * * * !* * * * * * * 1 20 0 200 180 160 F igure 44. l^ C NMR of copoly(3,3,5,5-tetram ethyl-4-oxa-3,5-disila-l,7- heptany lene/10-methyl-1,8-acrid-9-onylene). 7 5 p I I I | i ' 1 I [ I ! ' I | I '■ 'I"T ~ p > I I | 1 ! I I | | 1 I I | ! M I | t ' I I ~| 1 ' I I ) ! I I | | I I I | - 25 20 15 10 5 0 -5 -10 -15 -20 -25 PPM F igure 45. 2 9 si NMR of copoly(3,3,5,5-tetram ethyl-4-oxa-3,5-disila-l,7- heptanylene/10-methyl-l,8-acrid-9-onylene). 100 F ro * . 1 7 1 .8 5 C To. 3 8 5 .0 7 C O naae o t i 342. 32 82.5 ► - 5 UJ 47.5 i jam akoo zfam alaoo Warn t~ p sratura(O Figure 46. TGA of copoly(3,3,5,5-tetramethyl-4-oxa-3,5-disila-l,7-heptanylene/10- methyl-l,8-acrid-9-onylene). 7 6 22.9 Tg from : 7 .7 8 to : 3 8 .0 0 O n s e t- 1 7 .6 2 T g - 2 1 .9 1 x e X O U. h- < Ui £ 7.5 l o o to. T a m p e ra tu re (C) to. o o ido'.oo iij.oo 1 . 0 0 Figure 47. DSC of copoly(3,3,5,5-tetramethyl-4-oxa-3,5-disila-l,7-heptanyIene/10- methyl-1,8-acrid-9-onylene). O O o o F igure 48. UV spectrum o f copoly(3,3,5,5-tetram ethyI-4-oxa-3,5-disila-l,7- heptanylene/10-methyl-1,8-acrid-9-onylene). 7 7 1 0 J “ 1003 Figure 49. FT-IR of copoly(3,3.5,5-tetramethyl-4-oxa-3,5-disila-l,7-heptanylene/10- methyl-1,8-acrid-9-onylene). x 5.0 5 .0 3.0 a.o 7.0 1.0 0.0 F igure 50. NMR o f copoly(3,3,5,5-tetram ethyl-4-oxa-3,5-disila-l,7- heptanylene/2-aceto-5-methoxy-1,3-phenylene). 7 8 JL I i I— J L » X - JJL A ■ ■ 1 I .........................................ml,.....■■■f,.,...,,.!.. 200 190 J 6 0 140 120 100 SO 60 40 20 PPM F igure 51. NMR of copoly(3,3,5,5-tetram ethyl-4-oxa-3,5-disila-l,7- heptanylene/2-aceto-5-methoxy-1,3-phenylene). " j 11111 n 1111 ' ii i " ' 1 [ 11111' ' 1' | * ii'*11 n 1111 ii 1111 n it i i i 1111p n 111 m |— 45 40 35 30 25 20 I? 10 5 0 - S -|0 -1 5 -20 -2 5 PPM F igure 52. NMR of copoly(3,3,5,5-tetram ethyl-4-oxa-3,5-disila-l,7- heptanylene/2-aceto-5-methoxy-1,3-phenylene). 7 9 100 From i 2 3 2 . 00 C Tot 4 0 5 .3 1 C □ n aae a t* 404. 01 9 < 5 Figure 53. TGA of copoly(3,3,5,5-tetramethyl-4-oxa-3,5-disila-l,7-heptanylene/2- aceto-5-methoxy-1,3-phenylene). 37.3 X e u . 12.5 J o . 0 0 T e « p a r a tu r e (C) 306 ' - l o . o o il.oo rfOo lil.oo Figure 54. DSC of copoly(3,3,5,5-tetramethyl-4-oxa-3,5-disila-l,7-heptanylene/2- aceto-5-methoxy-1,3-phenylene). 8 0 i r a - E I M - T o m Figure 55. FT-IR of copoly(3,3,5,5-tetramethyl-4-oxa-3,5-disila-l,7-heptanylene/2- aceto-5-methoxy-1,3-phenylene). w o o o o o Figure 56. UV spectrum of copoly(3,3,5,5-tetram ethyl-4-oxa-3,5-disila-l,7- heptanylene/2-aceto-5-methoxy-1,3-phenylene). 8 1 I Ji j_A_ 9 .0 8 .0 7 .0 6 .0 6 .0 4 .0 3 .0 2 .0 1.0 0 .0 PPM Figure 57. NMR of copoly(3,3,6,6-tetramethyl-3,6-disila-l,8-octanylene/2-aceto- 5-methoxy-1,3-phenylene). J L 1 ■■i. i i - ■ ' £80 140 100 PPM SO 20 Figure 58. NMR of copoly(3,3,6,6-tetramethyl-3,6-disila-l,8-octanylene/2- aceto-5-methoxy-1,3-phenylene). 82 A 11 n 111111 [ 111111111111 1 1 11111 1 1111 111111111111111) 11111111 1 pi 111 1 it t' i n 1 1 1 1 1 1 1 - 45 40 35 3 0 * 25 20 15 10 5 0 -5 -10 -15 -20 -25 P P M Figure 59. 29§i NMR of copoly(3,3,6,6-tetramethyl-3,6-disila-l,8-octanylene/2- aceto-5-methoxy-1,3-phenylene). 100 F ro « i 2 7 2 .2 8 C Too 4 0 0 .4 4 C 0 n » * t a t i 4 5 9 .8 2 8 ► - 5 £ Figure 60. TGA of copoly(3,3,6,6-tetramethyl-3,6-disila-l,8-octanylene/2-aceto-5- methoxy-1,3-phenylene). 8 3 37.5 Tg f r o * - 2 0 .7 1 to : 2 0 .7 7 O ns0 t “ - 8 . 46 To— 6 .0 8 x E X o u. 12.5 -Jo.oo -lo.oo lo.oo io.oo Jo.oo JOo rfoT oo doToo------ liToo T a a p e r a tu r e (C) Figure 61. DSC of copoly(3,3,6,6-tetramethyl-3,6-disila-l,8-octanylene/2-aceto-5- methoxy-1,3-phenylene). r\> Figure 62. UV spectrum of copoly(3,3,6,6-tetramethyI-3,6-disila-l,8-octanylene/2- aceto-5-methoxy-1,3-phenylene). 8 4 JMJN - 0 0 - IU 79 - £ ■x S8 - Figure 63. FT-IR of copoly(3,3,6,6-tetramethyl-3,6-disila-l,8-octanylene/2-aceto-5- methoxy-1,3-phenylene). F igure 64. *H NMR of copoly(3,3,5,5-tetram ethyl-4-oxa-3,5-disila-l,7- heptanylene/2-aceto-5-phenoxy-l ,3-phenylene). 8 5 I I I 1 0 0 6 0 6 0 PPM F ig u re 65. NMR o f copoly(3,3,5,5-tetram ethyl-4-oxa-3,5-disila-l,7- heptanylene/2-aceto-5-phenoxy-1,3-phenylene). eo 30 < J 0 — T " 30 PPM T " 10 -to -ao . - p - r -30 F ig u re 66. 2 9 si NMR of copoly(3,3,5,5-tetram ethyl-4-oxa-3,5-disila-l,7- heptanylene/2-aceto-5-phenoxy-1,3-phenylene). 86 7g fro w i -2 0 . "4 t o i 4. 34 U n * « t“ - 1 3 . 49 “g— 12. 30 s 3 » a a. t— < Ui X 7.5 Figure 67. DSC of copoly(3,3,5,5-tetramethyl-4-oxa-3,5-disila-l,7-heptanylene/2- aceto-5-phenoxy-1,3-phenylene). (o p h o ) too 432. 230 2 9 § UJ * Figure 68. TGA of copoly(3,3,5,5-tetramethyl-4-oxa-3,5-disila-l,7-heptanylene/2- aceto-5-phenoxy-1,3-phenylene). 8 7 g g M - w - 2 a - I0» 8000 Figure 69. FT-IR of copoly(3,3,5,5-tetramethyI-4-oxa-3,5-disila-l,7-heptanylene/2- aceto-5-phenoxy-1,3-phenylene). Figure 70. UV spectrum of copoly(3,3,5,5-tetram ethyl-4-oxa-3,5-disila-l,7- heptanylene/2-aceto-5-phenoxy-1,3-phenylene). 88 V |..M |..................................... q 'o a 0 7 0 6 .0 5 .0 4 .0 3 .0 2 .0 1.0 0 .0 3 pp>1 Figure 71. ]H NMR of copoly(3,3,6,6-tetramethyl-3,6-disila-l,8-octanylene/2-aceto- 5-phenoxy-1,3-phenylene). .......... nm .n.......I..........||...... I...........I ........ | .......... I..........i;...........I...........|........... I...........j...........I" .......7 " ' 200 180 160 140 120 1°° 00 60 ‘ t') P P M 20 0 Figure 72. NMR of copoly(3,3,6,6-tetramethyl-3,6-disila-l,8-octanylene/2- aceto-5-phenoxy-1,3-phenylene). 8 9 T - r 50 •30 10 -40 T -to T 1 ao T T 0 0 60 30 7 ' PPM Figure 73. ^9si NMR of copoIy(3,3,6,6-tetramethyl-3,6-disila-l,8-octanylene/2- aceto-5-phenoxy-1,3-phenylene). f— < h jo p h o > 1 ® 4 3 4 .8 2 3 F ro m 2B0. 30 C Toi 450. 14 C O n a a t a t* 434. 62 0 h- X u U J Figure 74. TGA of copoly(3,3,6,6-tetramethyl-3,6-disila-l,8-octanylene/2.-aceto-5- phenoxy-1,3-phenylene). 9 0 22.5 s ■ S 7.5 ■ fe ta tea fcar T «iparatura(C ) Figure 75. DSC of copoly(3,3,6,6-tetramethyl-3,6-disila-l,8-octanylene/2-aceto-5- phenoxy-1,3-phenylene). r o Figure 76. UV spectrum of copoly(3,3,6,6-tetramethyl-3,6-disila-l,8-octanylene/2- aceto-5-phenoxy-l ,3-phenylene). 9 1 XHJM - KHAX m tz » - 4 J - Figure 77. FT-IR of copoly(3,3,6,6-tetramethyl-3,6-disila-l,8-octanylene/2-aceto-5 phenoxy-1,3-phenylene). s Figure 78. NMR of copoly(3,3,5,5-tetram ethyl-4-oxa-3,5-disila-l,7 heptanylene/2-aceto-5-phenyl-1,3-phenylene). 9 2 Tifniuiiini' 20 0 1B0 160 140 120 100 PPM 60 60 40 20 F ig u re 79. NMR of copoly(3,3,5,5-tetram ethyl-4-oxa-3,5-disila-l,7- heptanylene/2-aceto-5-phenyl-1,3-phenylene). 30 10 T 0 ' ! ' -10 f - p SO 40 PPM Figure 80. 2 9 si NMR of copoly(3,3,5,5-tetram ethyl-4-oxa-3,5-disila-l,7- heptanylene/2-aceto-5-phenyl-1,3-phenylene). 9 3 1 0 0 1 4 2 0 .D313 F ro m 243. 84 C Toi 457. 87 C C n » o t a t i 420. C3 73 8 ► - 5 U J 3» S O 2 5 0 Figure 81. TGA of copoly(3,3,5,5-tetramethyl-4-oxa-3,5-disila-l,7-heptanylene/2- aceto-5-phenyl-1,3-phenylene). 22.5 fg from i -9 . 01 O rm o t* -. 02 Tg- 2 .5 7 7.5 to® to® Tamparatura (C) to® ito ® rto® Figure 82. DSC of copoly(3,3,5,5-tetramethyl-4-oxa-3,5-disila-l,7-heptanylene/2- aceto-5-phenyl-1,3-phenylene). 9 4 g t ¥ . g 3 0 - E 0 O Figure 83. FT-IR of copoly(3,3,5,5-tetramethyl-4-oxa-3,5-disila-l,7-heptanylene/2- aceto-5-phenyl-1,3-phenylene). ho 'O Cl a a a Figure 84. UV spectrum o f copoly(3,3,5,5-tetram ethyl-4-oxa-3,5-disila-l,7- heptany lene/2-aceto-5-phenyl-1,3-phenylene). 9 5 A _ _ J u U l I I I I I I I i I I I 9 .0 0 .0 7 .0 6 . 0 5 .0 4 .0 3 .0 2 . 0 1 ,0 0 .0 PPM Figure 85. NMR of copoly(3,3,6,6-tetramethyl-3,6-disila-l,8-octanylene/2-aceto- 5-phenyl-1,3-phenylene). w 1 m > w w h I I ' I • I I I ■ I ■ I ■ i ■ 1 i 1 ' .......... 200 160 160 140 120 100 SO 60 40 20 0 P P M Figure 86. NMR of copoly(3,3,6,6-tetramethyl-3,6-disila-l,8-octanylene/2- aceto-5-phenyl-l,3-phenylene). 9 6 T T T T i TT TT T -rrrrr Tl I " " 1 " 2 0 -20 PPM Figure 87. 29<jj NMR of copoly(3,3,6,6-tetramethyl-3,6-disila-l,8-octanylene/2- aceto-5-phenyl-1,3-phenylene). C h jp h o ) 1 0 0 H t— g 52.5 ■ f e r n ifeo z f e o o zh. oo Figure 88. TGA of copoly(3,3,6,6-tetramethyl-3,6-disila-l,8-octanylene/2-aceto-5- phenyl-1,3-phenylene). 9 7 22.5 7g f r o m - 7 . 64 to i 29. U n ftat- 1 .3 0 7 g - T .3 2 ¥ Figure 89. DSC of copoly(3,3,6,6-tetramethyl-3,6-disila-l,8-octanylene/2-aceto-5- phenyl-1,3-phenylene). aa - 4tJ - ig m Figure 90. FT-IR of copoIy(3,3,6,6-tetramethyl-3,6-disila-l,8-octanylene/2-aceto-5- phenyl-1,3-phenylene). 9 8 r \ i Figure 91. UV spectrum of copoly(3,3,6,6-tetramethyl-3,6-disila-l,8-octanylene/2- aceto-5-phenyl-1,3-phenylene). 9 9 CHAPTER 3 Synthesis of High Molecular Weight Copolymers by Ruthenium Catalyzed Step-Growth Copolymerization of Acetophenone with a,co-Dienes. 3.1 Summary: Reaction of dihydridocarbonyltm(triphenylphosphine)ruthenium (Ru) with a stoichiometric amount of an alkene such as styrene prior to addition of a 1:1 molar ratio acetophenone and a,co-diene yields ethylbenzene and high molecular weight copolymers of acetophenone and the oc,co-diene. Low molecular weight copolymers are synthesized by Ru-catalyzed reaction directly with acetophenone and a,£0-dienes. Both high and low molecular weight copolymers are characterized by ^H, and 29si FT-NMR as well as by FT-IR and UV-vis spectroscopy. The molecular weight distributions of these polymers have been determined by gel permeation chromatography (GPC) and their glass transition temperatures (Tg's) by differential scanning calorimetry (DSC). 3.2 Introduction: Murai et al. have reported that dihydridocarbonyltm(triphenylphosphine)ruthenium (Ru) catalyzes the addition of the ortho C-H bonds of acetophenone across the C-C double bonds of olefins such as trimethylvinylsilane to yield ortho alkyl substituted acetophenones.1'3 We have shown that this reaction can be applied to achieve step- growth copolymerization of aromatic ketones and a , c o - d i e n e s A 5 Unfortunately, the molecular weights of these copolymers are generally low. This is not unexpected since exact stoichiometry is essential to achieve high molecular weights in step-growth 100 copolymerization reactions.^ The occurrence of minor unknown side reactions will destroy the required balance of stoichiometry. While significantly higher molecular weight copolymers have been obtained with /7-dialkylamino, /7-methoxy, and p- phenoxyacetophenones, this is not a general solution.7-9 Higher molecular weights are important since many polymer properties change rapidly until a minimum threshold value is achieved. Frequently this minimum molecular weight for constant polymer properties occurs at about a molecular weight of 10,000.10 We have previously reported the Ru catalyzed step-growth copolymerization of xanthone and 1,3-divinyltetramethyldisiloxane to yield copoly(l,8-xanthonylene/3,3,5,5- tetramethyl-4-oxa-3,5-disila-l,7-heptanylene) Mw/M n = 3500/1700. Resonances consistent with an ethyl group attached to silicon were detected by NMR spectroscopic end group analysis. We have noted that Ru catalyzed reaction of l-ethyl-3- vinyltetramethyldisiloxane, formed in-situ by hydrogenation of one of the C-C double bonds of the 1,3-divinyltetramethyldisiloxane, with acetophenone would yield such an end group. Further, we have suggested that the hydrogen needed for this reduction may come from the catalyst itself. This reduction may, in fact, be involved in the formation of the coordinately unsaturated catalytically active ruthenium species needed for copolymerization.^ A closely related complex, dihydridorerrafo'.s(triphenylphosphine)- ruthenium, is known to catalyze the transfer hydrogenation of alkenes. 11 3.3 Results and Discussion: Based on this analysis, we have treated the Ru catalyst with a stoichiometric amount of an alkene such as styrene or vinyltrimethoxysilane. After heating this mixture at 135°C for a few minutes, a 1:1 molar ratio solution of the acetophenone and a,to-diene was 101 added. In this way, significantly higher m olecular weight copolymers were obtained.(Scheme 1) 135°C (Ph3P)3RuH2CO + P h -C H = C H 2 -------- - P h - C H 2-C H 3 + (Ph3P)3RuCO Active Catalyst (Ph3P)3RuCO + | Scheme 1. Synthesis of high molecular weight copoly(3,3,6,6-tetramethyl-3,6-disila- 1,8-octanylene/2-acetyl-1,3-phenylene) (copoly-II) For example, copolymerization of acetophenone and 1,3-divinyltetramethyldisiloxane with Ru catalyst which had been previously activated with an equal molar amount (stoichiometric) of vinyltrimethoxysilane gave copoly(3,3,5,5-tetramethyl-4-oxa-3,5- disila-l,7-heptanylene/2-acetyl-l,3-phenylene) (copoly-1) Mw/Mn = 40,600/14,800, Tg = -33°C. Previous preparation of copoly-I without prior activation of the catalyst gave low molecular weight copoly-I with Mw/Mn = 8,300/6,700 and Tg = -45°C. NMR spectra of both high molecular weight and low molecular weight copoly-I are compared in Figure 1. ^H NMR spectrum of the low molecular weight copoly-I reveals quartet (J = 7.5 Hz), and triplet (J = 7.5 Hz) low density singals at 0.49, and 0.89 ppm, which may be attributed to the ethyl groups attached to silicon atoms. It indicated that the hydrogen from the catalyst itself reducted the vinyl group at first to form l-ethyl-3- vinyltetramethyldisiloxane before the copolymerization reaction. This side reaction can destroy the stoichiometry of the monomers, further decrease the molecular weight of the product copoly-I, and lead to the glass transition temperature decreased. 102 high molecular wt copolymer-l r r r r i-o _______A i t low molecular wt copolym er-l T I I i j J I i " i ■ ’ 1 1 ' i ■ ■ ■ 1 i - 1 i j , 1 * 4 • # » .0 4 .0 S .» 4 .0 3 .0 * .0 r o 0 .0 Figure 1. NMR spectra of high molecular weight copoly-I and low molecular weight copoly-I. Similarly, copolymerization of acetophenone and 3,3,6,6-tetramethyl-3,6-disila-l,7- octadiene catalyzed by Ru catalyst which had been previously activated by treatment with a stoichiometric amount of styrene gave copoly(3,3,6,6-tetramethyl-3,6-disila-l,8- octanylene/2-acetyl-l,3-phenylene) (copoly-II) Mw/Mn = 22,900/21,300^2 with a Tg = -17°C, while preparation of copoly-II without prior activation of the Ru catalyst gave copoly-II with Mw/Mn = 7,800/4,800 with a Tg = -20.5°C. The detection by GC/MS of 1 0 3 ethylbenzene in the copolymerization reaction in which styrene was used for catalyst activation provides confirmation of our hypothesis. In control experiments, the Ru catalyst was treated with stoichiometric amounts of styrene at 135°C for 3 min. Using toluene as an internal standard, a quantititive yield of ethylbenzene was observed. No unreacted styrene was detected.(Figure 2b-d) Styrene and ethylbenzene were observed in experiments conducted with excess styrene.(Figure 2a) (Ph3P)3RuH2CO + c h 3 c h 2- c h 3 130°C 5min Ratios of starting materials Styrene "Ru" a 1.5 1 b 1 1 c 1 Toluene 13 22 5 .4 2.3 a.o I 6.0 r T T ~ 4 .0 2.0 Figure 2. NMR spectra of the reaction between styrene and "Ru" catalyst. Using toluene as internal standard. 1 0 4 Catalyst activation by reaction with a stoichiometric amount of alkene provides a significant improvement in copolymer molecular weight, thermal stability, and Tg. For example, TGA indicates that the high molecular weight copoly-I (1) has much higher thermal stability than the low molecular weight copoly-I (2).(Figure 3) I C D 9 >- 5 U l T < Figure 3. TGA of high molecular weight copoly-I (1) and low molecular weight copoly-I (2). 105 3.4 Experimental Section: Spectroscopic lH and 13c NMR spectra were obtained on either a Bruker AC-250 or a AM-360 spectrometer operating in the Fourier Transform mode. 29si NMR spectra were recorded on an IBM-Bruker WP-270-SY spectrometer. Five percent weight/volume solutions of copolymer in chloroform-^ were used to obtain NMR spectra. 13q NMR spectra were run with broad band proton decoupling. A heteronuclear gated decoupling pulse sequence (NONOE) with a 20 sec delay was used to acquire 29s j NMR spectra. 13 These were externally referenced to TMS. Chloroform was used as an internal standard for lH and 13c NMR spectra. IR spectra of neat films on NaCl plates were recorded on an IBM FT- IR spectrometer. UV spectra of cyclohexane solutions were acquired on a Shimadzu UV- 260 ultraviolet visible spectrometer. Molecular Weight Distribution Gel permeation chromatographic (GPC) analysis of the molecular weight distribution of these polymers was performed on a Waters system comprised of a U6K injector, a 510 HPLC solvent delivery system, a R401 refractive index detector and a model 820 Maxima control system. A Waters 7.8 mm x 30 cm Ultrastyragel linear column packed with less than 10 pm particles of mixed pore size crosslinked styrene divinylbenzene copolymer maintained at 20°C was used for the analysis. The eluting solvent was HPLC grade THF at a flow rate of 0.6 mL/min. The retention times were calibrated against those of known monodisperse polystyrene standards: Mp 612,000, 114,200, 47,500, 18,700, 5,120, 2200 and 794 whose Mw/M n are less than 1.09. 1 0 6 T herm ogravim etric Analysis (TGA) TGA of the polymers was carried out on a Perkin-Elmer TGS-2 instrument with a nitrogen flow rate of 40 cc/min. The temperature program for the analysis was 50°C for 10 min followed by an increase of 4°C/min to 750°C. D ifferential Scanning C alorim etry(D SC ) The glass transition temperatures (Tg's) of the copolymers were determined by DSC on a Perkin-Elmer DSC-7 instrument. The melting point of indium (mp 165°C) was used to calibrate the DSC. The program for the analysis was -100°C for 10 min followed by an increase in temperature of 20°C/min to 150°C. G C/M S Analysis GC/MS Analysis was performed on a Hewlett-Packard 5871A equipped with a MSD. The GC inlet was furnished with a 30 m x 0.25 pm film thickness DB-5 column. The temperature program was 60°C for 3 min, followed by an increase of 15°C/min to 249°C. Elem ental Analysis was performed by Oneida Research Services Inc., Whitesboro, NY Chem icals and G lassw are Dihydridocarbonylrm(triphenylphosphine)ruthenium (Ru-catalyst) was prepared from ruthenium trichloride following literature procedures.^ Hydrated ruthenium trichloride (0.26 g) in ethanol, aqueous formaldehyde (10 mL), and sodium borohydride (0.19 g) in ethanol were added in rapid succession to a stirred solution of 1 0 7 triphenylphosphine (1.57 g) in boiling ethanol. The mixture was heated under reflux for 15 min, and then cooled; the resultant precipitate was filtered off, washed with ethanol, water, and ethanol, and dried in vacuo. Recrystallisation from benzene-hexane gave the pure catalyst as white microcrystals in 75% yield. 1,3-Divinyltetramethyldisiloxane and 3,3,6,6-tetramethyl-3,6-disila-l,7-octadiene were obtained from United Chemical Technologies. All reactions were conducted in flame dried glassware under an atmosphere of purified argon. Copoly (3,3,5,5-tetramethyl-4-oxa-3,5-disila-l, 7-heptanylene/2-acety I- l,3-phenylene)(Low Molecular Weight Copoly-I) A 25 mL flame dried round bottom flask was equipped with a Teflon covered magnetic stirring bar and an efficient reflux condenser. 1,3-Divinyltetramethyldisiloxane (0 .9 7 g, 5 .2 mmol), acetophenone (0.6 g, 5 mmol), dihydridocarbonylrm(triphenylphosphine)ruthenium(0.4 g, 0.44 mmol) and 5 mL of xylene were placed in the flask. Purified nitrogen was bubbled through the solution for five minutes. The mixture was refluxed with stirring for 24 h at 150°C under nitrogen. The color of the mixture changed from colorless to black. The solvent was removed by evaporation under reduced pressure. Pentane, 5 ml, was added and the mixture was stirred for several minutes. This caused the catalyst to precipitate. After filtration, the pentane was removed by evaporation under reduced pressure, 1.5 g, 100% yield of crude copolymer was obtained. The copolymer was purified three times by precipitation from tetrahydrofuran and methanol. In this way, 1.28 g, 85% yield of pure copolymer I was obtained. It had the following properties. Mw/Mn = 8310/6720, Tg = -45°C. TGA, onset 300°C, 50% decomposition at 390°C, 19% residue; NMR 5: 0.0-0. l(m, 1 0 8 12H), 0.78-0.86(m, 4H), 2.40-2.50(m, 7H), 7.0-7.23(m, 3H); 13C NMR 5: 0.19, 20.87, 26.66, 33.05, 125.95, 128.78, 139.59, 140.93, 208.14; 2$Si NMR 8: 7.23; IR u: 3061, 2955, 2888, 1834, 1700, 1594, 1460, 1434, 1414, 1352, 1252, 1179, 1059, 962, 904, 842, 791, 757, 722, 697 cm’ 1; UV Xmax nm(e): 221(7330), 268(764). Elemental Anal. Calcd for C i6H 2602Si2: C, 62.75; H, 8.50. Found: C, 62.28; H, 8.53. Copoly(3,3,5,5-tetramethyl-4-oxa-3,5-disila-l,7-heptanylene/2-acetyl- l,3-pheny!ene)(High Molecular Weight Copoly-I) Ru catalyst (0.11 g, 0.12 mmol) and toluene(l mL) were placed in a 50 mL three neck round bottom flask which was equipped with a reflux condenser and a magnetic stirring bar. The other two neck of the flask were sealed with rubber septa. Vinyltrimethoxysilane (0.016 mL, 0.018 g, 0.12 mmol) was added via syringe. The flask and its contents were heated to 135oC for 1 min. At this time, a mixture of acetophenone (0.48 g, 4 mmol) and 1,3-divinyltetramethyldisiloxane (0.74 g, 4 mmol) was added. The color of the reaction mixture changed to black immediately. The reaction was heated at 135°C for 12 h. Toluene was removed by evaporation under reduced pressure. Pentane (5mL) was added to precipitate the catalyst. After filtration, the pentane was removed by evaporation and the copolymer was purified three times by precipitation from a mixture of THF and methanol. In this way, 0.9 g, 74% yield of copoly-I Mw/Mn = 40,600/14,800, Tg = -33°C was obtained. It had spectral properties in complete agreement with low molecular weight copoly-I previously reported. 1 0 9 Copoly(3,3,6,6-tetramethyl-3,6-disiIa-l,8-octanylene/2-acetyl-l,3- phenylene)(Low Molecular Weight Copoly-II) Acetophenone (0.3 g, 2.5 mmol), 3,3,6,6-tetramethyl-3,6-disila-l,7-octadiene(0.5 g, 2.5 mmol) and Ru-catalyst (0.15 g, 0.16 mmol) were reacted as above. In this manner, copoly-II, 0.72 g, 90% yield, Mw/Mn = 7800/4800, Tg = -20.5°C was obtained. NMR 5: -0.015(s, 12H), 0.40(s, 4H), 0.79-0.86(m, 4H), 2.42-2.56(m, 7H), 7.07(d, 2H, J=7.5Hz), 7.2l(t, 1H, 7.5Hz). NMR 8: -4.19, 6.90, 17.42, 27.29, 33.02, 125.89, 128.72, 139.87, 140.79, 208.11. 29Si NMR 5: 4.17. IR \): 3060, 2951, 2900, 1929, 1702, 1699, 1682, 1593, 1461, 1455, 1439, 1422, 1414, 1351, 1247, 1177, 1133, 1089, 1053, 995, 961, 902, 832, 780, 757, 695 c m '1. UV Xm ax nm(e): 217(18,600), 264(2,020). Elemental Anal. Calcd for Ci8H3()OSi2: C, 67.92; H, 9.43. Found: C, 67.19; H, 8.87. Copoly (3,3,6,6-tetramethyl-3,6-disila-l,8-octanylene/2-acetyl-l,3- phenylene)(High Molecular Weight Copoly-II) Ru-catalyst (0.07 g, 0.08 mmol) was placed in a 50 mL three neck round bottom flask as above. Styrene(0.009 mL, 0.008 g, 0.008 mmol) was added via a syringe. This mixture was heated at 135°C for three min. At this time, a mixture of acetophenone (0.48 g, 4 mmol) and 3,3,6,6-tetramethyl-3,6-disila-l,7-octadiene (0.79 g, 4 mmol) was added. The reaction mixture was heated at 135°C for 12 h. After work-up, 1.12 g, 88% yield of copoly-II, Mw/Mn = 22,900/21,300, Tg = -17°C was obtained. It had spectral properties identical to those reported above. Ethylbenzene was detected by GC/MS analysis of the solution by both its retention time and base peak which was found at m/e = 91. 110 Control Reaction of Styrene with Ru-Catalyst Ru catalyst (46.3 mg, 0.05 mmol), styrene (5.2 mg, 0.05 mmol) and toluene (25.6 mg, 0.28 mmol) were placed in a 5 mm NMR tube. The tube and its contents were heated at 135°C for three min., after rapidly cooling the tube to room temperature NMR analysis indicated a quantitive yield of ethylbenzene by integration of the ethyl group 1.37 (t, 3H, J = 7.5 Hz) and 2.76 (q, 4H, J = 7.5 Hz) ppm versus the methyl group 2.47 (s, 3H) ppm of the internal standard toluene. 3.5 R eferences: 1. S. Murai, F. Kakiuchi, S. Sekine, Y. Tanaka, M. Sonoda, N. Chatani, Nature, 1993, 366, 529. 2. S. Murai, F. Kakiuchi, S. Sekine, Y. Tanaka, A. Kamatani, M. Sonoda, N. Chatani, Pure & Applied Chem., 1994, 66, 1527. 3. F. Kakiuchi, S. Sekine, Y. Tanaka, M. Sonoda, N. Chatani, S. Murai, Bull. Chem. Soc. Jpn., 1995, 68, 62. 4. H. Guo, W. P. Weber, Polymer Bull., 1994,32, 525. 5. H. Guo, M. Tapsak, W. P. Weber, Polymer Bull., 1994, 34, 49. 6. G. Odian, Principles o f Polymerization; J. Wiley & Sons: New York, NY, 1981; p 82-96. 7. H. Guo, M. A. Tapsak, W. P. Weber, Polymer Preprints, 1995,56-7,705. 8. H. Guo, M. A. Tapsak, W. P. Weber, Macromolecules, Submitted 1995. 9. H. Guo, W. P. Weber, Polymer Bull., 1995, in press. 10. G. Odian, Principles o f Polymerization; J. Wiley & Sons: New York, NY, 1981, P 54. 11. H. Imai, T. Nishiguchi, K. Fukuzumi, J. Org. Chem., 1976, 41, 665. 12. The very low PDI detected is probably anamolous. 13. R. Freeman, H. D. W. Hill, R. Kaptein, J. Magn. Reson., 1972, 7, 327. 14. J. J. Levison, S. D. Robinson,/. Chem. Soc., 1970,-4, 2947. 112 * 0 0 if lo m i j i i i M K i i j i i M M M i j i i r r I S O U O t n i j r i M i i M i | i r i i i i i i i | n n i W O 100 d o ,,n|................. I '"1 40 JO Figure 4. NMR of copoly-I. i it ITT 11i • 111 mrjn v v v nn p"<"i 1 r ' -20 .0 .0 I I I I 40 . K 2 0 .0 0 . 0 F F n Figure 5. 29§i NMR of copoly-I. 1 1 3 .. O or O Figure 6. UV spectrum of copoly-I. 1 0 a ea - to £ 5 £ G ft - z ; A f l - rs; WfiVkNUHfiee (cm -Ii Figure 7. FT-IR of copoly-I. 1 1 4 22.9 To f r o * : - 3 8 .9 9 to : - p g . 16 on«at—9 0 * 7 4 . Ta— 4 4 .6 3 s § u. ► — < U J z 7.3 > o .d o T t a p i r a t u r * (C) Figure 8. DSC of low molecular weight copoly-I. 37.5 Tg frc.sc -'3 8 .2 9 to : - 1 7 .0 6 O n s e t- - 3 S . O .^ i TO— 3 3 . in x e x o _j u. t — < ■ Li X 12.5 lo .O O T e n p a r o t u r e (C) r O o Figure 9. DSC of high molecular weight copoly-II. 115 Figure 10. *H NMR of copoly-II. w Jl M. 200 180 160 140 120 100 FPM 80 60 40 2 0 Figure 11. 13c NMR of copoly-II. Figure 12. 29Si NMR of copoly-II. rv m Figure 13. UV spectrum of copoly-II. 500. 0 I rR M tS H IU ffiK X 6 0 - 9 0 - 2SM 2*99 WRVENUHBER Figure 14. FT-IR of copoly-II. T r a c e W T: 5 . 5 8 4 4 mg RATE: 4 . 0 0 d e g /m l n 100.00 pAOH t Ta ,5 b TO( 4 4 2 .6 9 ONSFT AT V C V n rr- 9 T .3 4 . K I X to ” 50.00 f UJ z 0.00 140.00 300.00 220.00 60.00 360.00 460.00 540.00 620.00 780.00 700.00 TEMPERATURE (C) Figure 15. TGA of low molecular weight copoly-II. 1 1 8 (gooa-a) 100 c m te e .g c c To. 407. 35 c 2natt «e> 472-72 H 3 ui X Figure 16. TGA of high molecular weight copoly-II. 15 x E 1 0 x o .J u. < U i I 5 0 S ir Tem perature (C ) T o7oo 1 . 0 0 Figure 17. DSC of low molecular weight copoly-II. 1 H E A T F L O W [fflM ) a (a c a c -2 ) 21 Tg f ro to: .96 0 n s e t v l 9 . 6 0 Tg— 1 7 .1 1 14 7 ^ tn io -io.oo 0 “te r o o irsr T e m p e ra tu re (C) Figure 18. DSC of high molecular weight copoly-II. 120 CHAPTER 4 Ruthenium Catalyzed Chemical Modification of Unsaturated Polycarbosilane 4.1 Summary: Chemical modification of unsaturated polycarbosilanes with pendant Si-vinyl groups has been achieved by a novel ru th en iu m catalyzed reactio n . Dihydridocarbonyl/m(triphenylphosphine)ruthenium catalyzes the addition of the ortho C-H bond of 2'-methylacetophenone across the C-C double bond of pendant vinyl groups of polym ers such as copoly(vinylm ethylsilylene/l,4-phenylene). Copoly(vinylmethylsilylene/l,4-phenylene) has been prepared by a polycondensation reaction between vinylmethyldichlorosilane and the di-Grignard reagent derived from p- dibromo benzene. 4.2 Introduction: There is significant current interest in the chemical modification of polymers This often permits the preparation of polymers which cannot be prepared by direct polymerization of monomers. While the use of selective transition metal catalyzed reactions in organic synthesis has become r o u t i n e , the use of such reactions for chemical modification of polymers has received considerably less attention. Nevertheless, successful homogeneous rhodium catalyzed [(Ph3P)3RhCl] hydrogenation, hydrosilation and hydroformylation of unsaturated polymers with pendant vinyl groups, such as 1,2- polybutadiene, have been reported.^.? 121 In this chapter, we report the dihydridocarbonyl/m(triphenylphosphine)ruthenium catalyzed addition of the ortho C-H bond of 2'-methylacetophenone across C-C double bonds of pendant vinyl groups of polymers. In this manner, addition of 2'- methylacetophenone across the C-C double bonds of pendant Si-vinyl groups of co p o ly (v in y lm eth y lsily len e/l ,4-phenylene) yields cop o ly [2 -(2 '-acety l-3 '- methylphenyl)ethylmethylsilylene/l,4-phenylene].(Scheme 1) Mg/THF Scheme 1. Synthesis of copoly[2-(2'-acetyl-3'-methylphenyl)ethylmethylsilylene/l,4- phenylene]. Likewise, modifications of unsaturated polysiloxanes can be achieved in the same way. ^ (Scheme 2) Scheme 2. Synthesis of copoly[dimethylsiloxane/2-(2'-acetyl-3'-methylphenyl)ethyl- methylsiloxane]. 122 4.3 Results and Discussion: Copoly(vinylmethylsilylene/l,4-phenylene) has been prepared by condensation polymerization reaction. Treatment of vinylmethyldichlorosilane with 1.04 equiv of p- phenylenedimagnesium dibromide in THF, followed by hydrolysis with ice-water, gave copoly(vinylmethylsilylene/l,4-phenylene) in 69% yield. The polymer was purified three times by precipitation from THF-methanol. The molecular weight of this polymer was determined to be Mw/Mn = 6280/1520 by GPC, relative to polystyrene standards. Exact stoichiometry is essential in such reactions to achieve high molecular weight. In fact, the synthesis was carried out with an excess of the di-Grignard reagent. For this reason, it is not surprising that the molecular weight of poly(methylsilylene/l,4-phenylene) is not high. The structure of this polymer was verified spectroscopically by ^H, 29gj NMR, IR, UV. The excess di-Grignard reagent was used to insure that there were no Si- C1 end groups which would hydrolyze to Si-OH groups and condense to yield Si-O-Si bonds. Consistent with this interpretation no strong bands between 1100 and 1000 cm-1 due to Si-O-Si linkages can be seen in the IR of copoly(vinylmethylsilylene/l,4- phenylene). (Figure 1) ui m _ ¥ a r J 9 - < K ae n - Figure 1. FT-IR of copoly(vinylmethylsilylene/l,4-phenylene). 123 The ruthenium catalyzed addition of the ortho C-H bond of 2'-methylacetophenone across the pendant Si-vinyl groups of the polycarbosilane reported herein is regiospecific. The ortho hydrogen of 2'-methylacetophenone becomes attached to the more substituted vinyl carbon while the 2'-acetyl-3’ -methylphenyl group becomes attached to the terminal vinyl carbon. This regiospecificity can be seen in the NMR of copoly[2-(2'-acetyl-3’ - methylphenyl)ethylmethylsilylene/l,4-phenylene] (Figure 2). I " ' " ' T < | , | i — , , • ■ ■ i ■ j — | ...... ft.o 6 . 0 7 .0 6 0 5 . 0 4 .0 3 0 2 . 0 1 .0 0 0 Q B t s Figure 2. NMR of copoly[2-(2'-acetyl-3’-methylphenyl)ethylmethylsilylene/l,4- phenylene]. 29si NMR is highly characteristic for both the starting unsaturated polycarbosilanes and the m odified p ro d u ct p o ly carb o silan es. The 29§i NMR of copoly(vinylmethylsilylene/l,4-phenylene) has two resonances at -14.50 and -14.60 ppm. The latter is most intense. The major signal in the 29si NMR of the product carbosilane copolymer is at -7.43 ppm. The small resonance at -21.84 ppm is also seen. 1 2 4 The signal at -21.84 ppm occurs in tandem with a signal at -1.01 ppm in the NMR. Both are probably related to siloxane formation which occurs by cleavage of the phenyl- Si bond by protodesilation during work-up unless care is taken to quench traces of acid. Alternatively, it also may be due to the end group of low molecular weight polymer. The UV absorptivities reported are calculated based on the average molar weight of a single polym er unit. The UV spectrum o f co p o ly [2 -(2 '-acety l-3 '- methylphenyl)ethylmethylsilylene/l ,4-phenylene] is shown in Figure 3. C O .. * * o o o Q Figure 3. UV spectrum of copoly[2-(2'-acetyl-3’-methylphenyl)ethyImethyl- silylene/1,4-phenylene]. 125 As expected, the molecular weight of the product polymer (Mw/Mn = 8050/1660) is higher than that of the starting unsaturated polymer (Mw/M n = 6,280/1,520), and the ratio of Mw /M n for the product polym er co p o ly [2 -(2 '-a c ety l-3 ’- methylphenyl)ethylmethylsilylene/l,4-phenylene] (-4.8) is approximately equal to that of the starting polymer copoly(vinylmethylsilylene/l,4-phenylene) (-4.0). These reactions are related to the ruthenium catalyzed regioselective copolymerization of acetophenone and a ,o > -d ie n e s.9 In these polymerization reactions acetophenone acts as a difunctional monomer. The acetyl group activates both C-H bonds ortho to itself. Ruthenium catalyzed reactions between acetophenone and terminal alkenes to yield monomeric ortho alkyl substituted acetophenones have also been recently reported. 10-12 Similar reactions between unsaturated polymers substituted with pendant vinyl groups and acetophenone leads to crosslinked thermoset materials. 13 (Scheme 3) This is reasonable if acetophenone acts as a difunctional crosslinking reagent. These crosslining reactions and the materials thereby produced are under active investigation. 2'- Methylacetophenone permits successful chemical modification of unsaturated polymers because it only has a single ortho C-H bond which can undergo reaction. Scheme 3. Synthesis of crosslinking material with polybutyldiene and acetophenone. Cured Product 1 2 6 This novel method of chemical modification of unsaturated polymers is not without its problems. Attempts to carry out ruthenium catalyzed reactions between 2'- methylacetophenone and polybutadiene with a high percentage (85%) of pendant 1,2- vinyl units resulted in only very low incorporation of 2'-methylacetophenone units. In this case, the pendant 1,2-vinyl groups were isomerized to internal trisubstituted C-C double bonds. Mechanistically these reactions may be related to the palladium catalyzed Heck reactions of aryl halides with alkenes.14,15 insertion of palladium into the C-X bond of the aryl halide leads to a reactive Aryl-Pd-X species which is the key intermediate in these reactions. Apparently, in the reaction reported herein the acetyl group directs the insertion of the coordinately unsaturated ruthenium into the adjacent C-H bond. This leads to an aryl ruthenium hydride intermediate. Coordination of a pendant or terminal C-C double bond of the polymer to the ruthenium center followed by regioselective addition of the Aryl-Ru and Ru-H bonds across the coordinated C-C double bond followed by reductive elimination of the product serves to regenerate the coordinately unsaturated catalytic ruthenium species and complete the catalytic cycle. The attachment of 2'-methylacetophenone units to the polymer provides a chromophore which absorbs UV light between 265 and 240 nm. Monomeric ortho- alkylacetophenones have been previously shown to undergo photoenolization. This occurs when the photo-excited triplet state of the carbonyl abstracts a hydrogen from the ortho-alkyl group via a cyclic six-membered ring transition state to yield the enol. 1,3- Tautomerization of the enol regenerates the acetophenone. 16-18 This process accounts for the unusual UV photostability of ortho alkylacetophenones. This reversible photochemical process may permit polycarbosilane chemically modified with 2'- methylacetophenone units to serve as UV protective coatings. 1 2 7 4.4 Experimental Section: Spectroscopic and NMR spectra were obtained on either a Bruker AC-250 or a AM-360 spectrometer operating in the Fourier Transform mode. 29si NMR spectra were recorded on an IBM-Bruker WP-270-SY spectrometer. Five percent weight/volume solutions of copolymer in chloroform-d were used to obtain NMR spectra. *3q NMR spectra were run with broad band proton decoupling. A heteronuclear gated decoupling pulse sequence (NONOE) with a 20 sec delay was used to acquire 29si NMR spectra. 19 These were internally referenced to TMS. Chloroform was used as an internal standard for and 13c NMR spectra. IR spectra of neat films on NaCl plates were recorded on an IBM FT- IR spectrometer. UV spectra of cyclohexane solutions were acquired on a Shimadzu UV- 260 ultraviolet visible spectrometer. Molecular Weight Distribution Gel permeation chromatographic (GPC) analysis of the molecular weight distribution of these polymers was performed on a Waters system comprised of a U6K injector, a 510 HPLC solvent delivery system, a R401 refractive index detector and a model 820 Maxima control system. A Waters 7.8 mm x 30 cm Ultrastyragel linear column packed with less than 10 (im particles of mixed pore size crosslinked styrene divinylbenzene copolymer maintained at 20°C was used for the analysis. The eluting solvent was HPLC grade THF at a flow rate of 0.6 mL/min. The retention times were calibrated against those of known monodisperse polystyrene standards: Mp 612,000, 114,200, 47,500, 18,700, 5,120, 2200 and 794 whose Mw/M n are less than 1.09. 12 8 T herm ogravim etric Analysis (TGA) TGA of the polymers was carried out on a Perkin-Elmer TGS-2 instrument with a nitrogen flow rate of 40 cc/min. The temperature program for the analysis was 50°C for 10 min followed by an increase of 4°C/min to 750°C. D ifferential Scanning C alorim etry(D SC ) The glass transition temperatures (Tg's) of the copolymers were determined by DSC on a Perkin-Elmer DSC-7 instrument. The melting point of indium (mp 165°C) was used to calibrate the DSC. The program for the analysis was -100°C for 10 min followed by an increase in temperature of 20°C/min to 150°C. Elemental Analysis was performed by Oneida Research Services Inc., Whitesboro, NY. C atalyst Chem ical and G lassw are Dihydridocarbonylrr«(triphenylphosphine)ruthenium was prepared from ruthenium trichloride following literature procedures.20 Hydrated ruthenium trichloride (0.26 g) in ethanol, aqueous formaldehyde (10 mL), and sodium borohydride (0.19 g) in ethanol were added in rapid succession to a stirred solution of triphenylphosphine (1.57 g) in boiling ethanol. The mixture was heated under reflux for 15 min, and then cooled; the resultant precipitate was filtered off, washed with ethanol, water, and ethanol, and dried in vacuo. Recrystallisation from benzene-hexane gave the pure catalyst as white microcrystals in 75% yield. 1 2 9 THF was distilled immediately prior to use from a deep blue solution of sodium benzophenone ketyl. All reactions were conducted in flame dried glassware under an atmosphere of purified argon. Copoly (vinylmethylsilylene/l,4-phenylene) A 2 L three necked round bottom flask was equipped with a pressure equalizing addition funnel, an efficient reflux condenser and a Tru-bore stirrer equipped with a Teflon paddle. Magnesium turnings (24.3 g, 1 mol), 1,2-dibromoethane (0.2 g, 1 mmol) and THF (500 mL) were placed in the flask. A solution of l,4-dibromobenzene(l 17.9 g, 0.5 mol) dissolved in THF (200 mL) was placed in the addition funnel and was slowly added to the well stirred slurry of magnesium turnings in THF. After the the addition was complete (3 h), the mixture was stirred for an additional 14 h. A solution of vinylmethyldichlorosilane (62 mL, 0.48 mol) and THF (100 mL) was placed in the addition funnel and was added to the solution of di-Grignard reagent over 3 h. The reaction was stirred for an additional 24 h. After aqueous work-up, the organic solution was dried over anhydrous magnesium sulfate, filtered and the volatile solvents removed by evaporation under reduced pressure. The crude polymer was dissolved in a minimum amount of THF and was precipitated from methanol. This process was repeated three times. In this way, 40 g, 69% yield of polymer Mw/M n = 6,280/1,520, Tg = 8°C was obtained. *H NMR 8: 0.75(s, 3H), 5.92(dd, 1H, J=20.0, 3.3 Hz), 6.31(dd, 1H, J=14.5, 3.3Hz), 6.60(dd, 1H, J=20.0, 3.3Hz), 7.49(s, 1.5H), 7.65(s, 3.5H). 1 3 c NMR 5: -4.36, -4.26, 127.81, 129.31, 133.18, 133.74, 134.08, 134.40, 134.79, 134.98, 135.02, 135.29, 135.48, 135.62, 136.00, 136.49, 137.22, 137.39. 29 si NMR 8: -14.50, -14.60. IR o: 3051, 3001, 2961, 1592, 1429, 1404, 1381, 1253, 1133, 1 3 0 1112, 1068, 1008, 959, 910, 782, 752, 733, 700, 649, 634 c n r 1. UV Xmax (e): 266(1,344), 230(6,590). Copoly [methyl-2-(2'-acetyl-3'-met hylphenyl)ethylmethylsilylene/l,4- phenylene] Copoly(vinylmethylsilylene/l,4-phenylene) (0.3 g, 2 mmol), dihydridocarbonyl- rm (triphenylphosphine)ruthenium com plex (40 mg, 0.04 mmol), 2'- methylacetophenone (Aldrich) (0.4 g, 3 mmol), xylene(5 mL) and a Teflon covered magnetic stirring bar were placed in a 15 cc high pressure tube which was sealed under vacuum. The tube and its contents were heated in an oil bath at 140°C for 48 h. The color of the reaction mixture changed from colorless to black. The tube was opened and the solvent and excess 2'-methylacetophenone were removed by evaporation under reduced pressure. Ether (5 mL) was added to extract the product from the catalyst residue. This was repeated three times. After filtration, the ether was removed by evaporation under reduced pressure. The copolymer was purified three times by precipitation from a minimum amount of THF with methanol. In this way, 0.48 g, 80% yield, Mw/Mn = 8050/1660, Tg = 26°C was obtained. JH NMR 8: 0.55(br.s, 3H), 1.31-1.36(br.s, 2H), 2.19(s, 3H), 2.28(s, 3H), 2.45-2.52(br.s, 2H), 6.99-7.03(br.s, 1H), 7.1 l-7.14(br.s, 1H), 7.34(br.s, 1H), 7.48(s, 4H). 13C NMR 8: -4.79, 17.00, 19.09, 27.34, 32.35, 126.15, 127.74, 127.89, 128.65, 129.31, 132.06, 133.28, 133.80, 134.43, 137.58, 139.52, 141.79, 208.34. 2^Si NMR 8: -7.43, -9.96(s). IR v: 3055. 3000, 2957, 1698, 1594, 1501, 1462, 1429, 1415, 1381, 1353, 1256, 1177, 1134, 1112, 1096, 1054, 1020, 998, 962, 910, 782, 735, 700 c m '1. UV ^max (e): 265(4,500), 240(16,000). 13 1 4.5 R eferences: 1. C.E. Carraher Jr, J. A. Moore, Modification o f Polymers, Plenum Press, New York, 1983. 2. L. J. Mathias, C. E. Carraher Jr, Crown Ethers and Phase Transfer Catalysis in Polymer Science, Plenum Press, New York, 1984. 3. J. L. Benham, J. F. Kinstle, Chemical Reactions on Polymers, ACS Symposium Series 363, American Chemical Society, Washington, D.C. 1988. 4. S. G. Davies, Organotransition Metal Chemistry: Applications to Organic Synthesis, Pergamon Press, Oxford, England, 1982. 5. E. L. Negishi, Organometallics in Organic Synthesis, J. Wiley & Sons, New York, 1980. 6. X. Guo, R. Farwaha, G. L. Rempel, Macromolecules, 1990, 23, 4047. 7. N. A. Mohammadi, G. L. Rempel, in Chemical Reactions on Polymers, Ed. by J. L. Benham, J. F. Kinstle, ACS Symposium Series 364, American Chemical Society, Washington, D.C. 1988. 8. H. Guo, M. A. Tapsak and W. P. Weber, Polymer Bull., 1994,33, 417. 9. H. Guo, W. P. Weber, Polymer Bull., 1994,32, 525. 10. S. Murai, F. Kakiuchi, S. Sekine, Y. Tanaka, A. Kamatani, M. Sonoda, N. Chatani, Nature, 1993, 366, 529. 11. S. Mural, F. Kakiuchi, S. Sekine, Y. Tanaka, A. Kamatani, M. Sonoda, N. Chatani, Pure & Applied Chem., 1994, 66, 1527. 12. F. Kakiuchi, S. Sekine, Y. Tanaka, M. Sonoda, N. Chatani, S. Murai, Bull. Chem. Soc. Jpn., 1995, 68, 62. 13. H. Guo, unpublished results 1994. 14. R. F. Heck, Organic Reactions, 1982, 27, 345. 1 3 2 15. Z. N. Bao, Y. M. Chen, R. B. Cai, L. P. Yu, Macromolecules, 1993,26, 5281. 16. K. R. Huffman, M. Loy, E. F. Ullman, J. Am. Chem. Soc., 1965, 87, 5417. 17. W. A. Jr Henderson, E. F. Ullman, J. Am. Chem. Soc., 1965, 87, 5424. 18. N. C. Yang, C. Rivas, J. Am. Chem. Soc., 1961, 83, 2213. 19. R. Freeman, H. D. W. Hill, R. Kaptein, J. Magn. Reson., 1972, 7, 327. 20. J. J. Levison, S. D. Robinson, J. Chem. Soc., 1970, A, 2947. 1 3 3 ) L a U ______________________________________J L i 1 — ' 1 " i ...... — r — — • ■ i * i 1 i ■ 9 0 3 0 7 .0 6 . 0 6 . 0 4 . 0 3 0 2 . 0 J , 0 PPk( Figure 4. NMR of copoly(vinylmethylsilylene/l ,4-phenylene). 100 140 60 PPM 160 0 40 60 ao Figure 5. NMR of copoly(vinylmethylsilylene/l ,4-phenylene). 1 3 4 0 . 0 -10.0 prn -»— r~ » i » i i | i -20 .0 ”i — i — i — r — i — r- -3© *0 Figure 6. 29gj NMR of copoly(vinylmethylsilylene/l,4-phenylene). Figure 7. UV spectrum of copoly(vinylmethylsilylene/l ,4-phenylene). 135 ( h j v i n ) Tg from : - I B . -40 to : 3 3 .9 1 O n o e t— 7 .10 T g - 2 .0 4 +C.t 1 k c s i L ► - ■ < * ■ & T 5 o T«npgr»tur« (C ) 0.00 60.00 Figure 8. DSC of copoly(vinylmethylsilylene/l,4-phenylene). 3 . 4 6 6 2 mg RATE: 4 . 0 0 d e g / m l n 100.00 FflOM: U 7 .4 6 ONSET AT 9 9 8 .6 5 X WT- 8 0 .8 8 - 60.00 20.00 140.00 300.00 60.00 220.00 380.00 460.00 940.00 620.00 780.00 700.00 TEMPERATURE (C) Figure 9. TGA of copoly(vinylmethylsilylene/l,4-phenylene). 1 3 6 I — r ’ """i P ~ ™ 1 ■ ' i : — i “ r 1 1 i 1 1 i 1 i"'"""1 i r ’ ”n r ?00 100 160 140 120 100 BO 60 40 30 0 r * n Figure 10. 13c NMR of copoly [2-(2’ -acetyl-3'-methylphenyl)ethylmethylsilylene/l,4- phenylene]. - . 0 - 5 . 0 - 1 0 . 0 - 1 5 . 0 - 2 0 . 0 - 2 5 . 0 - 3 0 . 0 - 3 5 . 0 PFW 15.0 10.0 5 .0 Figure 11. ^ S i NMR of copoly[2-(2,-acetyl-3’-methylphenyl)ethylmethylsilylene- /1,4-phenylene]. 1 3 7 m - X £ N 200* WRVENUHBF.R [ * * - ! ) Figure 12. FT-IR of copoly[2-(2'-acetyl-3'-methylphenyl)ethylmethylsilylene/l,4- phenylene]. Tg from : - S . 99 to: 3 4 .3 9 O n s e t- SO.14 i 7.5 ■ ^ n s r T » m p e ra -.jre 1C ) Figure 13. DSC of copolyf2-(2'-acetyl-3'-methylphenyl)ethylmethylsilylene/l,4- phenylene]. 1 38 HJPM W T: 2 .1 1 8 7 ng RATE: 4 .0 0 d e g /m in 100.00 PROM: 1 3 6 .1 2 TO: 4 3 3 . 3 3 ONSET * Wf- 9 9 . 0 5 ? 6 ? .82 i.O O 20.00 300.00 3 B 0 .0 0 140.00 220.00 460.00 60.00 940.00 620.00 700.00 TEMPERATURE (C) Figure 14. TGA of copoly[2-(2'-acetyl-3,-methylphenyl)ethylmethylsilylene/l,4- phenylene]. 1 3 9 C H A PTER 5 Synthesis and Characterization of Polycarbosilanes with Saturated Backbones: Chemical Modification of Poly(l-phenyl-l-silabutane) 5.1 Summary: Poly[ 1 -(3'-biphenoxypropyl)-1 -phenyl-1 -silabutane], poly[ 1 -(3'-cyanopropyl)-1 - phenyl-1 -silabutane], poly[ 1 -(3'-ethoxypropyl)-1 -phenyl-1 -silabutane], poly[ 1 -(3*- phenoxypropyl)-l-phenyl-1-silabutane], and poly[l-(4',7',10',13'-tetraoxatetradecanyl)- 1-phenyl-1-silabutane] have been prepared by the platinum catalyzed hydrosilation graft reaction between poly(l-phenyl-1-silabutane) and the appropriate functionally substituted alkenes. These polymers have been characterized by ^H, and 29si FT-NMR as well as by FT-IR and UV-vis spectroscopy. The molecular weight distributions of these polymers have been determined by gel permeation chromatography (GPC) and their glass transition temperatures (Tg's) by differential scanning calorimetry (DSC). 5.2 Introduction: Polycarbosilanes are a broad class of polymers in which the polymer backbone contains Si-C bonds. ^ The backbone of regular polycarbosilanes can incorporate diverse types of organic groups which alternate with silylene or disilylene units. Variation is possible not only in the organic units but also in the substituents bonded to silicon. The combination of these factors makes tremendous structural variation possible. While polycarbosilanes have received less attention than either p o l y s i l a n e s 2 . 3 o r the commercially important silicone p o l y m e r s ,4.5 there has been rapidly growing interest in 1 4 0 these polymers over the last fifteen years. The report by Yajima that thermal decomposition of copoly(methyl-silylene/methylene) [C H 3SiH -C H 2]n results in formation of P-silicon carbide by loss of methane and hydrogen provided the impetus for many of these s t u d i e s A 7 In this chapter, we report the preparation of polycarbosilanes in which the organic group of the polymer backbone is a saturated propyl group. These polycarbosilanes have Si- functionally substituted pendant alkyl chains. (Scheme 1) These have been prepared by platinum catalyzed hydrosilation graft reactions between functionally substituted terminal alkenes and the reactive Si-H bonds of poly(l -phenyl-1 -silabutane).8 There is considerable interest in the chemical modification of intact polymers since these methods often permit the synthesis of polymers which cannot be prepared d i r e c t l y . 9 - 1 2 Related functionally substituted p o l y c a r b o s i l a n e ^ 3 - 1 5 ancj s i l o x a n e ! 6 - 1 9 graft copolymers have been prepared. For example, commercially important surfactant polysiloxanes substituted with hydrophilic nonionic oligo(oxyethylene) pendant groups are prepared by platinum catalyzed hydrosilation reaction between the reactive Si-H bonds of poly(methylsiloxane) and the terminal C-C double bonds of oligo(ethylene glycol) allyl methyl ethers.16 These graft siloxane polymers are also of scientific interest due to their ability to form solvent free polymer electrolytes which have reasonable ionic c o n d u c t i v i t i e s .2 0 - 2 3 \ / \ / S i - O — Si Ph "> Ph — - H ^ ~ y ^ y Scheme 1. Synthesis of polyfl-(3'-biphenoxypropyl)-l-phenyl-1-silabutane]. 141 5.3 R esults and Discussion: Poly(l -phenyl-1 -silabutane) has been prepared by anionic ring opening polymerization of 1-phenyl-1-silacyclobutane with low molecular weights. We believe that the anionic polymerization proceeds by nucleophilic attack of n-butyllithium at the silyl center with formation of a pentacoordinate siliconate anion intermediate. Ring opening of the silacyclobutane ring results in relief of ring strain (26 kcal/moI)27 and formation of a primary carbanion which attacks the silyl center of another molecule of silacyclobutane to yield a new hypervalent siliconate intermediate as outlined below. (Scheme 2) Since hydride can serve as a leaving group in nucleophilic substitution reactions at silyl centers to terminate the c h a i n - p r o p a g a t i n g , 2 8 , 2 9 the greater ease of displacement of a hydride from a silyl center compared to that of a methylene anion may account for such low molecular weghts [Mw/M n = 4500/2300 (A) or Mw/M n = 1 9 7 0 / 1 1 4 0 ( B ) ] . H M P A /T H F H H H H Scheme 2. The mechanism of anionic ring-opening polymerization of 1-phenyl-1- silacyclobutane. 1 4 2 The silyl centers of poly(l-phenyl-1-silabutane) are chiral. The chirality of adjacent silyl centers affect ^H, and 29n m R spectra. The three resonances due to the Si- H bonds (Figure 1) can be accounted for in terms of a triad analysis. (Scheme 3) ..| — , — , — , — , — t ■ , — | — . — | — , — .. 9.0 6.0 7.0 6.0 5 .0 4.0 3 0 2.0 1.0 PPM Figure 1. *H NMR of poly(l-phenyl-1-silabutane) 0 . 0 . 0 Si —^ — Si —^ — Si i I I H H H ? A _ V - S i - 7 — Si — S i- I J I H H O Si- I H — Si— — Ci— — 6 _ I j v £ a 4 - 6 " 1 Scheme 3. The triad analysis of the chiral silyl centers in poly(l-phenyl-1-silabutane). 143 The desired polymers have been prepared by the Pt-complex catalyzed reaction of poly(l-phenyl-1 -silabutane) with functional substituted terminal alkenes. No evidence for unreacted Si-H bonds in the product polymers was detected by infrared spectroscopy (Si- H band is found at 2100 cm 'l). For this reason, we believe that the graft hydrosilation reactions proceed quantitatively. Yields have been calculated on this basis. For example, poly[l-(3’ -cyanopropyl)-l-phenyl-1-silabutane] has been prepared by platinum catalyzed hydrosilation graft reaction between poly(l-phenyl-1-silabutane) and allyl cyanide. (Figure 2) Similarly, poly[l-(3’-phenoxypropyl)-l-phenyl-l-silabutane], poIy[l-(3!- biphenoxypropyl)-1 -phenyl-1 -silabutane], poly[ 1 -(3'-ethoxypropyl)-1 -phenyl-1 - silabutane] and poly[l-(4',7',lO', 13'-tetraoxatetradecanyl)-l-phenyl-1-silabutane] have been prepared by platinum-catalyzed hydrosilation graft reactions between poly(l-phenyl- 1-silabutane) and allyl phenyl ether, allyl biphenyl ether, allyl ethyl ether and allyl triethylene glycol methyl ether, respectively. u «• - z <r • — X g W - a: c* 71 - 190# ISO# Figure 2. FT-IR of poly[l-(3'-cyanopropyl)-l -phenyl-1 -silabutane]. 1 4 4 The 29si NMR spectrum of each product polymers shows several peaks except poly[l-(3'-biphenoxypropyl)-l-phenyl-1-silabutane] which only have one resounce at -2.77 ppm. It may be due to 3-biphenoxypropyl group, a big mesogenic group which could form liquid crystallinity and hences no chirality effect detected in poly[l-(3'- biphenoxypropyl)-1 -phenyl-1 -silabutane]. In every case the elemental analysis results for carbon are low. This may result from a platinum catalyzed side reaction between adventitious water and Si-H bonds of poiy(l- phenyl-1 -silabutane). This would result in formation of silanol Si-OH bonds which undergo dehydration to form siloxane bonds.30,31 Bands observed in the infrared spectrum between 1100 and 1000 c m 'l may be due to S i-0 bonds. (Figure 3) Alternatively, it also could be due to low molecular weight, ie end group effects. UJ £ k . X in T . IX or. i- I I - <000 2090 WAVENlMBfcR F igure 3. FT-IR of p o ly [l-(4 ',7 ',1 0 ’,13'-tetraoxatetradecanyl)-l-phenyl-l- silabutane]. 1 4 5 The saturated polycarbosilanes substituted with pendant functional groups reported here are, from an architectural view point, comb polymers. The key difference between these polymers and the corresponding siloxane polymers is the polymer backbone. A saturated carbosilane backbone (Si-C) is chemically quite inert. On the other hand, the Si- O bonds of siloxane are susceptible to both acid and base catalyzed hydrolysis as well as to thermal redistribution r e a c t i o n s . 13 Further, the glass transition temperatures of functionally substituted polycarbosilanes are expected to be higher than the corresponding functionally substituted polysiloxanes, since the glass transition temperature of poly(l- methyl-1-silabutane) (Tg = -85°C) is higher than that of poly(methylhydrosiloxane) (Tg = -120°C). O f particular interest, phenyl substitution on silicon increases the Tg of both polycarbosilane and polysiloxanes. For example, the Tg of poly(l-phenyl-1-silabutane) is -46°C while that for poly(l-m ethyl-1-silabutane) is -89°C.^ Similarly, the Tg of dimethyl siloxane is -128°C while that for methylphenylsiloxane is -86°C. Therefore, glass transition temperature of Si-functionally substituted poly(l -phenyl- 1-silabutanes) are expected to be higher than the corresponding Si-functionally substituted poly(l- methyl-1-silabutanes) (See Table 1). 1 4 6 X : ' v - V Glass Trans* ion CH* Temperatures Tg(*C) CN 2 -82 OCHjCHj •35 OtCHjCHaOJaCHj -58 -84 OCHjQH^Hj -36 -84 o - O -9 •29 o - O - O 8 Table 1. Glass transition temperatures of poly[l-(3'-substitutopropyl)-l -phenyl-1- silabutane], poIy[l-(3'-substitutopropyl)-l-methyl-l-silabutane]. We have found that the Tg's depend strongly on the nature of the particular functional group. For example, the glass transition temperature (Tg = -58°C) (Figure 4) of poly[l- (4',7’,10',13'-tetraoxatetradecanyl)-l-phenyl-l-silabutane] which has more flexible pendant oligo(oxyethylene) group is lower than that of the polymers which contain the other functionally substituted groups in Table 1. On the contrary, poly[l-(3'- biphenoxypropyl)-l-phenyl-1-silabutane] has the highest Tg (8°C) (Figure 5). This results firm the fact that 3-biphenyloxypropyl is the most rigid pendant group among the pendant functional groups. 1 47 . a.s Tg f r o c -g 4 .B S to : - 4 7 . g j O n a « t— S l . g l Tg— 8 7 . gg o g ! 7.1 =*38---- T g g p g r g t u r g (Cl Figure 4. DSC of polyf l-(4',7',10',13'-tetraoxatetradecanyl)-l-phenyl-l-silabutane]. Tg r r o « - g . n * k n . n O n M t- g .g g T g - g .0 0 I ; . g 3 in r i n Tgwggrgturt (O Figure 5. DSC of polyf l-(3'-biphenoxypropyl)- 1-phenyl-1-silabutane]. 1 4 8 5.4 Experimental Section: Spectroscopic lH and * NMR spectra were run on a Bruker AM-250 spectrometer operating the Fourier transform (FT) mode. 2^Si NMR spectra were recorded on a Bruker 270-SY spectrometer, NMR spectra were run with broad band proton decoupling. 2^Si NMR spectra were obtained by use of a heteronuclear gated decoupling pulse sequence (INVGATE) with a pulse delay of 15-20 s.24 Ul, ^ C and 29$i NMR spectra were obtained using 10-15% solutions in chloroform-d. Chloroform was utilized as an internal standard for and NMR spectra. 29si NMR spectra were externally referenced to TMS. IR spectra were recorded on an IBM FT-IR spectrometer. These spectra were taken of neat films on sodium chloride plates. UV-vis spectra were recorded on a Shimadzu UV260 spectrometer. Spectral quality ethyl ether was used to prepare solutions for UV-vis spectra. Molecular Weight Distributions The molecular weight distribution of these polymers were determined by gel permeation chromatography (GPC) on a Waters system. This is comprised of a U6 K injector, a 510 HPLC solvent delivery system, an R401 differential refractometer, and a Maxima 820 control system. A Waters 7.8 mm x 30 cm Ultrastyragel linear column packed with < 10pm particles of mixed pore size cross-linked styrene-divinylbenzene copolymer was utilized at room temperature for the analysis. The eluting solvent was HPLC grade THF at a flow rate of 0.7 mL/min. The retention times were calibrated against known monodisperse polystyrene standards: 612,000, 114,000, 47,500, 18,700, 5,120, and 2,200 whose Mw/M n values are < 1.09. 1 4 9 D ifferential Scanning C alorim etry (DSC) The glass transition temperatures (Tg) of these polymers were determined by differential scanning calorimetry (DSC) on a Perkin-Elmer DSC-7 instrument. The melting point of indium (156°C) was utilized to calibrate the DSC. The temperature scans were begun at -100°C for 5 min. The temperature was then increased at a rate of 20°C/min to 200°C. Elem ental analysis was carried out by Oneida Research Services Inc., Whitesboro, New York. C hem icals and Glassware Tetrahydrofuran was distilled immediately prior to use from a deep blue solution of sodium benzophenone ketyl. Hexamethylphosphoramide (HMPA) was distilled from calcium hydride and was stored over activated 4 A0 molecular sieves. Platinum divinyltetramethyldisiloxane complex ( 2-3% platinum concentration in xylene) was obtained from Huls America Inc. All glassware was dried overnight in an oven at 120°C and was flame dried immediately prior to use. All reactions were conducted under an atmosphere of argon. Poly(l-phenyl-1-silabutane), Mw/Mn = 4500/2300 (A) or Mw/Mn = 1970/1140 (B), Tg = -46°C, was prepared by anionic ring opening polymerization of l-phenyl-l-silacyclobutane.8’25 They had spectral and other physical properties in agreement with those previously reported.8 P o ly [l-(3 '-b ip h e n o x y p ro p y l)-l-p h e n y I-l-sila b u ta n e ] Poly(l -phenyl- 1-silabutane A) (0.2 g, 1.35 mmol), allyl biphenyl ether26 (0.5 g, 2.7 mmol), Pt complex 3 |iL, 10 mL of THF and a Teflon covered magnetic stirring bar were 1 5 0 placed in a 50 mL round bottom flask equipped with an efficient reflux condenser. The mixture was heated to reflux with stirring for 48 h. During this time the color of the reaction mixture turned to black. The flask was allowed to cool and the mixture was filtered and the volatile solvents were removed by evaporation under reduced pressure. The residue was dissolved in a minimum amount of THF and the polymer was precipitated from pentane. This process was repeated twice. The polymer was dried under high vacuum. In this way, a solid material, Mw/Mn = 8040/2740, Tg = 8°C, 0.42 g, 93% yield was obtained. *H NMR 8 : 1.03 (m, 6H), 1.26(m, 2H), 1.69(m, 2H), 3.81(m, 2H), 6.84(s, 2H), 7.24-7.50(br.m, 12H). NMR 8 : 17.05, 17.61, 18.46, 23.75, 70.45, 114.66, 126.54, 126.62, 127.73, 127.81, 128.01, 128.66, 128.93, 133.34, 133.96, 134.79, 140.74, 158.54. 29Si NMR 5 . .2.77. i r v: 3068, 3032, 2919, 2874, 1610, 1519, 1488, 1472, 1428, 1290, 1269, 1245, 1176, 1140, 1111, 1048, 833, 764, 700 cm- ', UV Xmax nm (e): 261(2,360). Elemental Anal. Calcd. for C24H2 6 0 Si: C, 80.40; H, 7.30. Found: C, 80.00; H, 7.10. Poly [l-(3'-cyanopropyl)-1-phenyl-1-silabutane] Poly(l -phenyl- 1-silabutane, B) (0.2 g, 1.35 mmol), allyl cyanide (Aldrich) 0.8 g, 11.5 mmol), 3 pL of Pt complex and 10 mL of THF were placed in a 50 mL round bottom flask equipped with an efficient reflux condenser. The mixture was heated to reflux with stirring for 48 h. During this time the color of the reaction mixture turned to black. The flask was allowed to cool and the mixture was filtered and the volatile solvents were removed by evaporation under reduced pressure. The residue was dissolved in a minimum amount of THF and the polymer was precipitated from pentane. This process was repeated twice. The polymer was dried under high vacuum. In this way, a sticky material, Mw/M n = 3780/1730, Tg = 2°C, 0.23 g, 79 % yield was obtained. ^H NMR 151 8 . 0.8l(s, 6H), 1.44(m, 4H), 2.19(m, 2H), 7.30(s, 5H). 13C NMR 8 : 16.37, 16.73, 17.19, 18.05, 20.62, 119.62, 127.69, 127.82, 129.07, 133.27, 133.80, 136.03. 29Si NMR 5: -4.11, -4.01, -3.60, -3.45. IR u: 3088, 3069, 3048, 3020, 2920, 2874, 2245, 1428, 1342, 1235, 1175, 1144, 1116, 975, 928, 897, 720, 619 c m '1. UV Xmax nm (e): 259(1,398). Elemental Anal. Calcd for. C n H n S iN : C, 72.48; H, 7.90. Found: C, 71.30; H, 7.17. Poly[l-(3'-ethoxypropyI)-l-phenyl-1-silabutane] Poly(l-phenyl- 1-silabutane B) (0.2 g, 1.35 mmol), allyl ethyl ether (Aldrich) (0.23 g, 2.7 mmol), 3 (iL of Pt complex and 10 mL were placed in a 50 mL round bottom flask equipped with an efficient reflux condenser. The mixture was heated to reflux with stirring for 48 h. During this time the color of the reaction mixture turned to black. The flask was allowed to cool and the mixture was filtered and the volatile solvents were removed by evaporation under reduced pressure. The residue was dissolved in a minimum amount of THF and the polymer was precipitated from pentane. This process was repeated twice. The polymer was dried under high vacuum. In this way, a sticky material, Mw/Mn = 1900/1170, Tg = -35°C, 0.26 g, 82% yield was obtained. NMR 8 : 0.80(s, 6H), 1.15(m, 2H), 1.25(m, 2H), 1.48(m, 3H), 3.30(m, 2H), 3.37(m, 2H), 7.30(s, 5H). 13C NMR 8 : 17.16, 17.48, 18.23, 21.12, 24.00, 65.87, 73.51, 127.60, 128.66, 129.24, 133.37, 133.78, 133.98. 29Si NMR 8 : -2.92(s), -2.56. IR 3069, 3049, 2998, 2975, 2920, 2869, 2796, 1428, 1413, 1375, 1261, 1184, 1110, 1024, 999, 987, 899, 799, 737, 701 cm**. UV A.max nm (e): 259(1,530). Elemental Anal. Calcd. for C i4H2 2SiO: C, 71.80; H, 9.40. Found: C, 70.26; H,8.91. 1 5 2 Poly [l-(3'-phenoxy propyl)-1-phenyl-1-silabutane] Poly(l -phenyl- 1-silabutane B) (0.46 g, 3 mmol), allyl phenyl ether (Aldrich) (0.8 g, 6 mmol), 3 p.L of Pt complex, and 10 mL of THF was placed in a 50 mL round bottom flask equipped with an efficient reflux condenser. The mixture was heated to reflux with stirring for 48 h. During this time the color of the reaction mixture turned to black. The flask was allowed to cool and the mixture was filtered and the volatile solvents were removed by evaporation under reduced pressure. The residue was dissolved in a minimum amount of THF and the polymer was precipitated from pentane. This process was repeated twice. The polymer was dried under high vacuum. In this way, a sticky material, Mw/Mn = 2260/1450, Tg = -9°C, 0.6 g, 71% yield was obtained. lH NMR 8: 0.86(s, 6H), 1.31(m, 2H), 1.72(m, 2H), 3.85(m, 2H), 6.90(s, 2H), 7.29(s, 8H). 13C NMR 5: 16.80, 16.88, 17.09, 18.25, 23.71, 70.24, 114.36, 120.38, 127.71, 128.80, 129.35, 133.94. 29si NMR 8 : -4.09, -3.91(s), -3.27. IR u: 3069, 3048, 2998, 2975, 2920, 2869, 2796, 1428, 1413, 1375, 1261, 1184, 1110, 1024, 999, 987, 899, 799, 737, 701 c m '1. UV Xmax nm (e): 259(1,830), 271(2,245). Elemental Anal. Calcd. for C l8H 2 2SiO: C, 76.60; H, 7.78. Found, 75.71; H, 8.00. Poly[l-(4',7',10',13'-tetraoxatetradecanyl)-l-phenyl-l-silabutane] Poly(l-phenyl- 1-silabutane A) (0.46 g, 3 mmol), allyl triethylene glycol methyl ether (Aldrich) (1.22 g, 6 mmol), Pt complex 3 |iL was placed in a 50 mL round bottom flask equipped with an efficient reflux condenser. The mixture was heated to reflux with stirring for 48 h. During this time the color of the reaction mixture turned to black. The flask was allowed to cool and the mixture was filtered and the volatile solvents were removed by evaporation under reduced pressure. The residue was dissolved in a minimum amount of THF and the polymer was precipitated from pentane. This process 15 3 was repeated twice. The polymer was dried under high vacuum. In this way, a sticky material, Mw/M n = 3470/2170, Tg = -58°C, 0.8 g, 76% yield was obtained. !H NMR 8 : 0.90(m, 6H), 1.32(m, 2H), 1.45(m, 2H), 3.34(s, 3H), 3.53(m, 2H), 3.62(s, 12H), 7.26(s, 5H). 13C NMR 8 : 16.73, 17.03, 18.29, 23.75, 58.95, 69.82, 70.42, 70.49, 71.82, 74.17, 127.57, 128.63, 133.91, 137.20. 29Si NMR 8 : -4.01, -2.96 (s), -2.35. IR u: 3069, 2916, 2873, 1730, 1455, 1428, 1414, 1350, 1328, 1301, 1246, 1199, 1110, 1030, 998, 989, 943, 885, 853, 738, 702 c m '1. UV Xmax nm (£): 259(2,280). Elemental Anal. Calcd. for C i9H 3 2 0 4 Si: C, 64.78; H, 9.10. Found: C, 63.73; H, 8.80. 1 5 4 5.5 References: 1. W. P. Weber,Trends in Polymer Sci., 1993, 7,356. 2. R. West, Polysilanes in The Chemistry o f Organic Silicon Compounds S. Patai and Z. Rappoport, (Eds) J. Wiley & Sons, Chichester, England, 1989, p. 1206-1240. 3. R. West J . Organomet. Chem., 1986,300, 327. 4. N. Noll, Chemistry and Technology o f Silicones, Academic Press: New York, 1968. 5. T. C. Kendrick, B. Parbhoo, and J. W. White, Siloxane Polymers and Copolymers in The Chemistry o f Silicon Compounds; S. Patai and Z. Rappoport,(Eds) J. Wiley & Sons, Chichester, England, 1989. 6. S. Yajima, J. Hayashi and M. Omori, Chem. Lett., 1975, 9312. 7. S. Yajima, K. Okamura and J. Hayashi, Chem. Lett., 1975, 1209. 8. C. X. Liao and W. P. Weber, Polymer Bull., 1992,28, 281. 9. C. E. Jr. Carraher, and J. A. Moore, (Eds) Modification o f Polymers, Plenum Press: New York, 1983. 10. J. L. Benham and J. F. Kinstle, (Eds) Chemical Reactions on Polymers, ACS Symposium Series 364, American Chemical Society: Washington, DC, 1988. 11. E. M. Fettes, (Ed.) Chemical Reactions o f Polymers; Interscience Publishers: New York, 1964. 12. L. J. Mathias and C. E. Jr. Carraher (Eds) Crown Ethers and Phase Transfer Catalysis in Polymer Science, Plenum Press: New York 1984. 13. C. X. Liao and W. P. Weber, Macromolcules, 1993,26, 563. 14. R. J. P. Corriu, W. E. Douglas, E. Layher and R. Shankar, /. Inorg. Organomet. Polym., 1993,3 , 129. 15. S. J. Sargeant and W. P. Weber, Macromolcules, 1993,26, 2400. 16. B. Kanner, W. G. Reid, and I. H. Petersen, Ind. Eng. Prod. Res. Dev., 1967, 6, 1 5 5 88. 17. E. Wu, I.M. Khan and J. Staid, Polym. Bull., 1988,20, 455. 18. L. Lestel, S. Boileau, H. Cheradame, Polym. Prepr., (Am. Chem. Soc., Div. Polym. Chem.) 1989,30A , 133. 19. L. Lestel, H. Cheradame and S. Boileau, Polymer, 1990, 31, 1154. 20. D. Fish, I.M. Khan, E. Wu and J. Smid, Br. Polym. J., 1988,20, 281. 21. D. Fish, I. M. Khan and J. Smid, Makromol. Chem. Rapid Commun., 1986, 7, 115. 22. P. G. Hall, G. R. Davies, J. E. McIntyre, I. M. Ward, D. J. Bannister and K. M. F. LeBrocq, Polym. Commun., 1988, 27, 98. 23. R. Spindler and D. F. Shriver, Macromolecules, 1988,21, 648. 24. R. Freeman, H. D. W. Hill and R. Kaptein, /. Magn. Reson., 1972, 37, 4070. 25. N. Auner and J. Grobe, J. Organomet. Chem., 1980,188, 25. 26. M. Itoh and R. W. Lenz, J. Polym. Sci, Part A: Polym. Chem., 1991,29, 1407. 27. M. G. Voronkov, V. A. Klyuchnikov, E. V. Sokolova, T. F. Danilova, G. N. Shvets, A. N. Korchagina, L. E. Gusel'nikov, V. V. Volkova, J. Organometal. Chem., 1991, 401, 245. 28. J. S. Peake, W. H. Nebergall, T. T. Chen, J. Am. Chem. Soc., 1952, 74, 1526. 29. H. Gilman, E. A. Zeuch, J. Am. Chem. Soc., 1957, 79, 4560. 30. H. Guo, R. Volkle, W. P. Weber, Polymer Preprint, 1995, (I), 457. 31. L. Lestel, H. Cheradame and S. Boileau, Polym., 1990,5/, 1154. 32. L. Lestel, S. Boileau and H. Cheradame, Polym. Prepr., (Am. Chem. Soc., Div. Polym. Chem. ) 1989, 30A, 133. 1 5 6 too 00 - 00 - 40 - N 5000 2SO0 M V EN U M BER lr»-li 1 5 0 0 T O M 4000 Figure 6. FT-IR of poly(l-phenyl- 1-silabutane). y m ■ 11 n ■ 11 > if | e.o ttjti 9 .0 10 Z .O Figure 7. JH NMR of poly[l-(3'-cyanopropyl)-l-phenyl-1-silabutane]. 157 1 x 5 o i« n o i2c no ;qq ao ^ 7 0 e o e b « » » w 6 Figure 8. 13C NMR of poly[l-(3'-cyanopropyl)-l-phenyl-1-silabutane]. 0 0 . 0 ->10 - 0 Figure 9. 29si NMR of poly[l-(3’-cyanopropyl)-l-phenyl-l-silabutane]. 15 8 A b s 0 r b a n c e 1 - 0.656 2 5 9 u F 'I 1 I » F i | I >1 1 f riTI M I I I I I I | | | | | I I I I I »- r I ■ r11 IT I T I T-| J 300 300 400 560 ttanoaeters 666 Figure 10. UV spectrum of poly[l-(3’ -cyanopropyl)-l-phenyl- 1-silabutane]. i Tg f r o s -1 4 .2 8 to: 16.17 On .BO TO- 1.78 4 x o u . 2 TBBpBPBtUPB (C) Figure 11. DSC of poly[l-(3'-cyanopropyl)-l-phenyl- 1-silabutane]. 1 5 9 A A J I * I » | 1 1 I I | 1 I I 1 P > 1 I | I » I » | * * *■' [ T' l T I | I I < »1 I I I I | I I I I j I t I I | I I | | | T I I ' | > I I I j I I I I [ | | | | j I I I I | I I I I 8.0 7 0 8.0 S.O 4.0 3.0 2.0 1,0 P P N Figure 12. NMR of p oly[l-(4’,7',10',13'-tetraoxatetradecanyl)-l-phenyl-l- silabutane]. t a-a -19*0 -*®.3 PPM Figure 13. NMR of poIy[l-(4',7', 10', 13'-tetraoxatetradecanyl)-l-phenyl-1- silabutane]. 1 6 0 ft b s 0 r b A n c 0.564 259 e 600 700 500 300 400 200 Figure 14. UV spectrum of polytM ^JU O '.B '-tetraoxatetradecanylH -phenyl-l- silabutane]. 9.0 ppn Figure 15. *H NMR of poly[l-(3'-ethoxypropyl)-l-phenyl-l-silabutane]. 161 Figure 16. NMR of poly[l-(3'-ethoxypropyl)- 1-phenyl- 1-silabutane]. > 0 .0 0.0 0> » W — 10 .0 Figure 17. 29gi NMR of poly[l-(3'-ethoxypropyl)-l-phenyl-l-silabutane]. XMIN - 6 N . I m - L U u X <r x < /» z d oe 2 t - IBM Figure 1 8 . F T - I R o f p o ly [ l- ( 3 '- e th o x y p r o p y l) - l - p h e n y l- 1 - s il a b u ta n e ] . A b s o r b & " h e e J - I- 0.346 259 200 300 ■ i ............ ' i ' 400 S C O M & Jio n eters I i i i u i m i | i r < 6 00 700 Figure 19. UV spectrum of poly[l-(3'-ethoxypropyl)-l-phenyl-l-silabutane]. 1 6 3 11.29-■ 7.9 S g! 9.79 ■ ■ T« f ro * -4 1 .4 3 ta s - M .M OnM t—M .H T*—S4.90 - 3 n r ■^rtr 3 n r ~ 3 rtr " n S T J O T*ap*r«tup« ( C ) Figure 20. DSC of polyf l-(3'-ethoxypropyl)-l-phenyl- 1-silabutane]. 1111|im j i n n i ' n | ' ' ' i |'i r n -ji i u | i n i'j 11 m | m i j i m n 111 7.0 6 0 6-0 4-.0 1 1 1 1 1 1 1 I | T I I l|1 1 1 l|1 1 I I j I I I I | II I I | 3 .0 3 .0 e.o 0.0 Figure 21. NMR of poly[l-(3'-biphenoxypropyl)-l-phenyl-l-silabutane]. 1 6 4 I I l l JLy«— *y' * » * » — ^ f r * » V r ^J^\i/M p Ti>f! M1 1 m n im n n | n n n rTTrn n iMM| n m n H | im i iiii|in i iiMi| u n iin ipM iin ii| n iiM ni | mi| ih h iiii| hmimii|th i ■40 1 20 to o p 8 ^ 00 <0 30 Figure 22. NMR of poly[l-(3'-biphenoxypropyl)-l-phenyl-1-silabutane]. iff . m — 10 *0 i»pn Figure 23. 29$j NMR of polyf l-(3'-biphenoxypropyl)-l-phenyl-l-silabutane]. 1 6 5 XMN - m . t i f l e m i j z tr x in ae ISM Figure 24. FT-IR of poly[l-(3'-biphenoxypropyl)-l-phenyl-l-silabutane]. 1.315 261 300 500 400 Manometers Figure 25. UV spectrum of polyf l-(3'-biphenoxypropyl)-l -phenyl- 1-silabutane]. 1 6 6 Ill n 1111'r m n 11 m 11111 ['fn 11111' 11 1 n p 11111111111 n 11111111 1 1 [ 1111111111 n 111111' 111111' irq-nrr S ' j 8 0 r . 5 1 .0 6 . 5 6 . 0 5 . 5 5 0 4 .5 4 0 3 .5 3 .0 2 . 5 2 . 0 1 .5 I 0 l| 5 0 0 - 0 5 PPM Figure 26. NMR of poly[l-(3'-phenoxypropyl)-l-phenyl-l-silabutane]. 1 JLi m ■ | i m i j- r r r r p r r ij i ■ l i | i ■ r ry riT i p i n j ■ n >[ m i j 1 1 1 1 1 1 m j I ll I |riT T | Mll|H A ju tt p n i | m i | T n T t r t , . j t . i t - lie 1 3 0 1 2 0 U0 1 0 0 S O a o 70 6 0 so 4 0 3 0 20 1 0 roi Figure 27. 13c NMR of polyf l-(3'-phenoxypropyI)-l-phenyl-l-silabutane]. 1 67 k — 10 • m Figure 28. 29Si NMR of polyf l-(3'-phenoxypropyl)-l-phenyl-l-silabutane]. A b S * o r b Q 5- i n 2-j c j 1 200 0 .7 9 6 271 V , i i . i i )■ | ' i ; i i i , i i | i i i i i i i ' i | i i~n -7 500 300 400 nanometers Figure 29. UV spectrum of poly[ l-(3'-phenoxypropyl)-l-phenyl-1-silabutane]. 1 6 8 % 7RRN5MITTPNCE 6 1 1 - « - ISM I N * 2M0 I MM 2SM HflVtNUMBER (eo-ll Figure 30. FT-IR of poly[l-(3'-phenoxypropyl)-l-phenyl-l-silabutane]. a (PH0-P9) IS 1 0 9 ------- * 09--- To«p*r*tur« (C) 0 Figure 31. DSC of polyf l-(3'-phenoxypropyl)-l-phenyl-1-silabutane]. 1 6 9 CHAPTER 6 Synthesis and Characterization of Polycarbosilanes with Unsaturated Backbones: Chemical Modification of Copoly(methyIsilylene/l,4-phenylene). 6.1 Sum m ary: Copoly(methyl-3'-biphenoxypropylsilylene/l,4-phenylene), copoly(methyl-3'- cyanopropylsilylene/l,4-phenylene), copoly(m ethyl-3'-ethoxypropylsilylene/l,4- phenylene), copoly(methyl-3'-phenoxypropylsilylene/l,4-phenylene) and copoly(methyl- 4',7',10',13'-tetraoxatetradecanylsilylene/l,4-phenylene) have been prepared by platinum catalyzed hydrosilation graft reactions between poly(methylsilylene/l,4- phenylene) and appropriate functionally substituted alkenes. These polymers have been characterized by ^H, and ^ S i NMR as well as by FT-IR and UV-vis spectroscopy. The molecular weight distribution of these polymers has been determined by gel permeation chromatography (GPC), their glass transition temperatures (Tg) by differential scanning calorimetry (DSC), and their thermal stability by thermogravimetric analysis (TGA). Poly(l-m ethylsilylene/l,4-phenylene) has been prepared by a polycondensation reaction between dichlorosilane and the di-Grignard reagent. 6.2 Introduction: While polycarbosilanes have received less attention than either p o ly s i la n e s 1^ or commercially significant silicone p o ly m e r s ,3.4 there has been growing interest in these polymers over the last fifteen years. The reports by Yajima that thermal decomposition of copoly(methylsilylene/methylene) [CH3SiH-CH2]n results in the formation of (3-silicon 1 7 0 carbide by loss of methane and hydrogen provided the stimulus for many of these s t u d i e s .5.6 Polycarbosilanes are a broad class of polymers in which the polymer backbone contains Si-C bonds.7 The backbone of these polymers can incorporate diverse types of organic groups which alternate with silylene or disilylene units. Variation is possible not only in the organic unit but also in the substitutents bonded to silicon. The combination of these factors makes tremendous structural variation possible. There is considerable concern with chemical modification of intact polymers since these methods often permits the synthesis o f polymers which cannot be prepared directly.8-11 In this chapter, we report the preparation of a novel class of unsaturated polycarbosilanes. The backbone of these polymers is made up of a regular alternation of 1,4-phenylene units and silylene units which have both a methyl group and a functionally substituted pendant propyl chain attached to silicon. These have been prepared by platinum catalyzed hydrosilation graft reactions between functionally substituted terminal alkenes and the reactive Si-H bonds of copoly(methylsilylene/l,4-phenylene). Many papers concerning the preparations of poly(silylene/phenylene) have been p u b l i s h e d . ^ 2-1 4 por example, J. O hshita has reported the synthesis of poly(methylsilylene/l,4-phenylene) from the reaction of dichloromethylsilane with p - dilithiobenzene in a low yield (11 %)J4 Herein the parent polym er, poly(methylsilylene/l,4-phenylene) was prepared by condensation polymerization reaction of methyldichlorosilane with the di-Grignard reagent prepared from 1,4- dibromobenzene. (Scheme 1) This method is more convenient and gives a higher yield (55 %). Related Si-substituted polycarbosilanes and polysiloxanes have been prepared by platinum catalyzed graft hydrosilation reactions on p o l y ( l - m e t h y l - l - s i l a b u t a n e ) , 1 5 171 poly(l-methyl-l-sila-c/s-pent-3-ene)16, poly(l-methyl- l-silapropane)1? and as well as numerous examples on poly(methylsiloxane). For example, commercially important CH3SiHCI2 CHo H R' H Scheme 1. Synthesis of copoly(methyl-3'-phenoxypropylsilylene/l,4-phenylene). surfactant polysiloxanes substituted with hydrophilic nonionic oligo(oxyethylene) pendant groups are prepared by platinum catalyzed hydrosilation reaction between the reactire Si-H bonds of poly(methylsiloxane) and the terminal C-C double bonds of oligo different glass transition temperatures and thermal stabilities because of variation of their backbones and substituted pendant g r o u p s .18 6.3 Results and Discussion: Poly(methylsilylene/l,4-phenylene) has been prepared by a condensation reaction. Treatment of dichloromethylsilane with 1.1 equiv of p-phenylenedimagnesium dibromide in THF, followed by hydrolysis with ice-water, gave poly(methylsilylene/l,4-phenylene) in 55 % yield, after three times precipitation from THF-methanol. The molecular weight of this polymer was determined to be Mw/M n = 4430/1300 by GPC, relative to polystyrene standards. Exact stoichiometry is essential in such reactions to achieve high molecular weight. In fact, the synthesis was carried out with an excess of the di-Grignard (ethylene glycol) allyl methyl ethers.15 These polycarbonsilanes, polysiloxanes have 1 7 2 reagent prepared from 1,4-dibromobenzene. For this reason, it is not surprising that the molecular weight of poly(methylsilylene/l,4-phenylene) is low. The structure of this polymer was verified by spectroscopic methods. The IR spectrum shows an absorption band at 2127 c n r 1 due to stretching frequencies of Si-H bonds. The excess di-Grignard reagent was used to insure that there were no Si-Cl end groups which would hydrolyze to Si-OH groups and condense to yield Si-O-Si bonds. Consistent with this interpretation no strong bands between 1100 and 1000 cnr* due to Si-O-Si linkages can be seen in the IR of poly(methylsilylene/l,4-phenylene) (Figure 1). iii u T t r h- § 60 - cr w 2 m V A V E N U H 8E R U .- l) 1 5 0 0 Figure 1. FT-IR of poly(methylsilylene/l,4-phenylene). NMR spectrum of poly(methylsilylene/l,4-phenylene) reveals a doublet (J = 2.6 Hz), quartet (J = 3.9 Hz), and singlet signal at 0.63, 4.94, and 7.56 ppm, due to MeSi, HSi and phenylene protons. The NMR spectrum shows a silyl methyl signal at -5.23 ppm and phenylene signals at 134.25 and 136.61 ppm. in addition to signals with 173 low intensities attributed to an terminal phenyl or 4-bromophenyl group, which is probably produced from the excess of di-Grignard reagent. The additional resonances are detected in both lH NMR and 13c NMR (Figure 2) spectrum consistent with terminal phenyl or 4-bromophenyl groups. V . J 11 11 11 11111 III 111 11'| '[ ■ n * | i ' I i j i n n 'n - r r j i I I I | | I I i j I I I I [ II I | | I I | I | I i i i j i n i | n r r | m m 111 1 tj 1111 p m | i 1111111 0 .0 0 .0 7 .0 0 .0 S.O 4 .0 3 .0 2 .0 1 0 0 0 PPM UUt. |iiiiitiiiHin iMM|iiiiiiiii|rniiin i| iiiim ii| | in |im i H Tip ii 140 120 100 00 MijMiMNM|HMrmi|iiTnnii|MMiHii|iiiininipninin|nmn' | 00 40 20 0 Figure 2. lH, 13c NMR of poly(methylsilylene/l,4-phenylene). 1 7 4 Its 29si NMR spectrum displays one major signal at -17.54 ppm, a second resonance of low intensity is observed at -11.0 ppm. We.believe this latter resonance is due to silicon atoms connected to end groups. The intensity ratio of these is 10:1. This is consistent with a polymer which would have a molecular weight of about 2400 in approximate agreement with the molecular weight determined by GPC. It should be noted that in the 29si NMR of each of the product polymers a low intensity signal between -11.1 and -11.4 is observed, in addition to the major resonance for each particular product polymer. This can be seen for example in the 29si NMR of poly(methyl-3'- ethoxypropylsilylene/l,4-phenylene) (Figure 3). These results clearly indicated that this polymer must have a regular alternating arrangement of a methylsilylene group and p- .phenylene unit. ' 1 1 ■ — " i i r — ........................... ' ■ ■ ■ | 10 .0 0 . 0 -10.0 -200 - 3 0 . 0 p p m Figure 3. 29gi NMR of copoly(methyl-3'-ethoxypropylsilylene/l,4-phenylene). 175 The graft modified polycarbosilanes have been prepared by platinum catalyzed hydrosilation reactions between the Si-H bonds of poly(methylsiIylene/l,4-phenylene) and various functionally subsitituted alkenes. After removal of any platinum salts by treatment of the reaction mixtures with silica gel chromatography under an inert atmosphere, the concentrated mixtures were precipitated from THF-methanol to give corresponding modified polymers in around 80 % yields. No evidence for unreacted Si- H (2127 c m 'l) bonds in the product polymers was detected by infrared spectroscopy. Further integration of the NMR spectra of the product polymers is consistent with stoichiometric reactions. Finally the absence of strong bands in the IR of poly(methyl-3’ - cyanopropylsilylene/l,4-phenylene) between 1100 and 1000 cm'* characteristic of Si-0 bonds suggests that the graft hydrosilation reactions proceed essentially quantitatively (Figure 4). All the other product polymers contain ether linkages which will absorb in the same region of the IR spectrum. 100 - < -> z c c u - X CD 7 T . cr o r 60 - 2S00 W A V E N U M B E R tcn-l) Figure 4. FT-IR of copoly(methyl-3’ -cyanopropylsilylene/l,4-phenylene). 1 7 6 As expected, the molecular weight of the product polymers are greater than the starting polymer. In general, the ratio of Mw/M n for the product polymers should be approximately equal to that of the starting polymer(l-methylsilylene/l,4-phenylene) (M w/M n = 1.7). The high values for the ratio of Mw/Mn (~ 3.0) suggest that the platinum complex catalyze side reaction between adventitious water and Si-H bonds of poly(methylsilylene/l,4-phenylene) to yield silanol (Si-OH) bonds which undergo dehydration to form siloxane b o n d $ 2 2 a n d would lead to unexpectedly high molecular weights. (Scheme 2) Although it's not a major problem, this is certainly at least a minor problem since the elemental analytical results for every product polymer are low for the percent carbon. This has been previously observed in graft hydrosilation reactions carried out on s im ila r S i-H p o ly c a r b o s ila n e s .1 4 ,1 5 OH Schem e 2. The side reaction to form siloxane bonds during the Pt catalyzed hydrosilation reaction. Thermogravimetric analysis (TGA) for product polymers was examined in a nitrogen atmosphere. The results are shown in Figures 5a-d. The onsets of thermal decomposition of these polymers occur around 330-400°C. Interestingly, Copoly(methyl-3'- Pt H O 177 biphenoxypropylsilylene/l,4-phenylene) has the highest onset temperature. Based on TGA spectrum, the weight of this polymer remains almost unchanged up to about 220°C and then decreases slowly around 400°C. After that the weight decreases continuously and rapidly to reach a constant value of 72% loss of the initial weight at 620°C. TGA for Copoly(methyl-3'-phenoxypropylsilylene/l,4-phenylene) shows its weight loss with two distinguishable steps. One is a rapid decrease at about 190°C and the other is continuous weight loss starting at about 360°C. Total weight loss at 700°C is found to be 74% of the initial weight. a u .o e 481.l i T O C CM8T A T 4 1 I IT T * 87.17 H X (9 U i X M (E 5 f lo f lo a&.OO S T m 1 .0 0 TEMPERATURE (C) Figure 5a. TGA of copoly(methyl-3'-biphenoxypropylsilylene/l,4-phenylene). 178 Ot 1 1 *. M Tft M 8.M H T A T » 1.47 TEMPERATURE (C) Figure 5b. TGA of copoly(methyl-3? -phenoxypropylsilylene/l,4-phenylene). TE M P E flA T U H E ( C J Figure 5c. TGA of copoly(methyl-3'-cyanopropylsilylene/l,4-phenylene). 179 T ft M T E M P E R A T U R E (C ) Figure 5d. TGA of copoly(methyl-4',7',10',13'-tetraoxatetradecanylsilylene/l,4- phenylene). The unsaturated polycarbosilanes substituted with pendant functional groups reported here are, from an architectural viewpoint, comb polymers. The key difference between these polymers and the corresponding siloxane polymers is the polymer backbone. The aromatic 1,4-phenylene units in the polymer backbone provide rigidity to the systems. Thus the Tgs of these copoly(l-m ethyl-1 -substituted-l-silylene/l,4-phenylenes) are significantly higher than comparable p o l y ( l - m e t h y l - l - s u b s t i t u t e d - l - s i l a b u t a n e s ) ^ , 1 9 and even than Si-substituted poly(l -phenyl-1 -substituted-1-silabutanes).20 The major exception to this trend is found for co p o ly (l-m eth y l-4 ',7 ',1 0 ',1 3 '- tetraoxatetradecanylsilylene/1,4-phenylene). Clearly, the pendant oligo oxyethylene chain is controlling the Tg for this polymer (See Table 1 ). Interestingly, compared with Copoly(methyl-3'-phenoxypropylsilylene/l ,4-phenylene) (Tg = 8°C), Tg ( = 33°C) of 180 Copoly(methyl-3'-biphenoxypropylsilylene/l ,4-phenylene) is much more high than that of poly(l -phenyl-1 -substituted- 1-silabutanes) (Tg = -9°C, 8°C, respectively). It maybe because biphenyl is a more rigid functional group. X: Ph ^ X ch3 S r + J c h 3 -H -46 -89 18 -(C H 2)3CN 2 -53 56 -<C H 2)3OCH2CH3 -35 -7 -(C H 2)30(CH jCH20 )3CH3 -58 -84 -87 -(C H 2)3OCH2CHCH2 Nd -36 -64 —(CH2)30 - ^ ^ -9 -29 8 -(C H 2)3 O—( 3 “ O 8 33 Table 1. Glass transition temperatures in °C of poly[l-phenyl-l-substituted-l- silabutanes], poly[l-m ethyl-l-substituted-l-silabutanes] and copoly[l-m ethyl-l- substituted-1 -silylene/1,4-phenylenes]. 181 6.4 Experimental Section: Spectroscopic lH and NMR spectra were run on a Bruker AM-250 spectrometer operating in the Fourier transform (FT) mode. 29gi NMR spectra were recorded on a Bruker 270-SY spectrometer. 13c NMR spectra were run with broad band proton decoupling. 29Si NMR spectra were obtained by use of a heteronuclear gated decoupling pulse sequence (INVGATE) with a pulse delay of 15-20 s.21 lH , l^C and 29si NMR spectra were obtained using 10-15% solutions in chloroform-d. Chloroform was utilized as an internal standard for lH and l^C NMR spectra. 29si NMR spectra were externally referenced to TMS. IR spectra were recorded on an IBM FT-IR spectrometer. These spectra were taken of neat films on sodium chloride plates. UV-vis spectra were recorded on a Shimadzu UV-260 spectrometer. Spectral quality ethyl ether was used to prepare solutions for UV-vis spectra. Molecular Weight Distributions The molecular weight distribution of these polymers were determined by gel permeation chromatography (GPC) on a Waters system. This is comprised of a U6K injector, a 510 solvent delivery system, an R401 differential refractometer, and a Maxima 820 control system. A Waters 7.8 mm x 30 cm Ultrastyragel linear column packed with <10 pm particles of mixed pore size cross-linked styrene-divinylbenzene copolymer was utilized at room temperature for the analysis. The eluting solvent was HPLC grade THF at a flow rate of 0.7 mL/min. The retention times were calibrated against known monodisperse polystyrene standards: 612,000; 11,400; 47,500; 18,700; 5,120, and 2,200 whose Mw/Mn values are < 1.09. 182 Differential Scanning Calorimetry (DSC) The glass transition temperatures (Tg) of these polymers were determined by differential scanning calorimetry (DSC) on a Perkin-Elmer DSC-7 instrument. The melting point of indium (156°C) was utilized to calibrate the DSC. The temperature scans were begun at -100°C for 5 min. The temperature was then increased at a rate of 20°C/min. to 200°C. Thermogravimetric Analysis (TGA) TGA of the polymers was carried out on a Perkin-Elmer TGS-2 instrument with a nitrogen flow rate of 40 cc/min. The temperature program for the analysis was 50°C for 10 min followed by an increase of 4°C/min to 750°C. Elemental analysis was carried out by Oneida Research Services Inc., Whitesboro, New York. Chemicals and Glassware Tetrahydrofuran (THF) was distilled immediately prior to use from a deep blue solution of sodium benzophenone ketyl. Hexamethylphosphoramide (HMPA) was distilled from calcium hydride and was stored over activated 4 A ° molecular sieves. Platinum divinyltetramethyldisiloxane complex (Pt complex) 2-3% in xylene was obtained from Huls America Inc. All glassware was dried overnight in an oven at 120°C and was flame dried immediately prior to use. All reactions were conducted under an atmosphere of argon. 183 Copoly (methylsilylene/l,4-phenylene) A 2 L three neck round bottom was equipped with a pressure equalizing addition funnel, an efficient reflux condenser and a Tru-bore stirrer equipped with a Teflon paddle. Magnesium turnings (81.6 g, 3.4 mol), THF (500 mL) and two drops of 1,2- dibromoethane were placed in the flask. A solution of 1,4-dibromobenzene (354 g, 1.5 mol) dissolved in THF (500 mL) was placed in the addition funnel and was slowly added to the stirred slurry of magnesium turnings. After the addition was complete, the reaction was stirred for an additional 14 h at rt. A solution of methyldichlorosilane (138 g, 1.2 mol) in THF (200 mL) was placed in the addition funnel and was slowly added to the solution of 1,4-di-Grignard reagent maintained below 20°C. The reaction temperature was maintained by immersing the flask in a bucket of ice/water. After the addition was complete, the reaction was heated to 60°C for 4 h. The reaction was worked up by addition of ice water. The aquous layer was extracted three times by ethyl ether. The organic layer was combined and dried over anhydrous magnesium sulfate, filtered and the volatile solvents were removed by evaporation under reduced pressure. The residue was taken up in a minimum amount of THF. The polymer was purified by precipitation from methanol three times. In this way, 80 g, 55% yield of polymer M w/Mn = 4300/2500, Tg = 18°C was obtained. ] H NMR 5: 0.63(d, 3H, J = 4.3 Hz), 4.92(m, 1H), 7.43(s, 4H). 13C NMR 5: -5.2, 128.0, 129.6, 131.1, 134.2, 136.6. 29si NMR 5: -11.0, -17.5. IR u: 3049, 2998, 2962, 2126, 1479, 1428, 1380, 1254, 1134, 1114, 1068, 1012, 910, 876, 831, 801, 734, 671, 650 c m '1. UV X max nm(e): 237(10,200). Copoly (met hyl-3'-biphenoxypropylsilylene/l,4-phenyIene) Copoly(methylsilylene/l ,4-phenylene) (0.32 g, 2.67 mmol), allyl biphenyl ether (0.6 g, 2.86 mmol), 5 |lL of Pt complex and 10 mL of THF were placed in a 25 mL round 184 bottom flask, equipped with a Teflon covered magnetic stirring bar and an efficient reflux condenser. The reaction was stirred for 50 h at 80°C. The flask was allowed to cool and the mixture was filtered and the volatile solvents were removed by evaporation under reduced pressure. The residue was dissolved in a minimum amount of THF and the polymer was precipitated from pentane. This process was repeated twice. The polymer was dried under high vacuum. In this way, chemically modified polymer, 0.65 g, 74% yield, Mw/Mn = 10,200/4,100, Tg = 33°C was obtained, NMR 8 : 0.54(s, 3H), 1.16(m, 2H), 1.84(m, 2H), 3.90(m, 2H), 6.87(s, H), 7.47(s, 9H). 13C NMR 8 : -4.66, 10.11, 23.74, 70.28, 114.68, 126.62, 128.04, 128.67, 131.04, 133.77, 134.45, 137.75, 140.75, 158.49. 29Si NMR 6 : -7.00, -11.1. IR u: 3069, 3059, 2980, 2890, 1610, 1519, 1486, 1269, 1245, 1176, 1134, 910, 835, 778, 765, 738, 699, 651 c m '1. UV Xmax nm(e): 238(12,600), 261(14,470). Elemental Anal. Calcd for C22H220Si: C, 79.95; H, 6.71. Found: C, 75.78; H, 7.13. Copoly (methyI-3'-cyanopropylsiIylene/l,4-phenyIene) The reaction of copoly(methylsilylene/l ,4-phenylene) (0.5 g, 4.2 mmol), allyl cyanide (Aldrich) (0.4 g, 5.9 mmol), and 5 |iL of Pt complex in 10 mL of THF were placed in a 25 mL round bottom flask, equipped with a Teflon covered magnetic stirring bar and an efficient reflux condenser. The reaction mixture was refluxed with stirring for 72 h. The flask was allowed to cool and the mixture was filtered and the volatile solvents were removed by evaporation under reduced pressure. The residue was dissolved in a minimum amount of THF and the polymer was precipitated from pentane. This process was repeated twice. The polymer was dried under high vacuum. In this way, product polymer, Mw/M n = 14,700/4,050, Tg = 56°C, 0.6 g, 77% yield was obtained. ^H NMR 5: 0.54(s, 3H), 1.19(m, 2H), 1.69(m, 2H), 2.34(m, 2H), 7.35(s, 4H). 13C 185 NMR 8 : -4.78, 13.83, 20.52, 20.69, 119.61, 127.99, 129.53, 131.19, 133.79, 134.61, 135.88, 137.18. 29Si NMR 8 : -7.1, -7.7(s), -11.3. IR o: 3053, 2959, 2254, 1257, 1134, 908, 779, 735, 651 cm '1. UV Xmax nm(e): 234(11,000), 265(1,020). Elemental Anal. Calcd. for C l lH B N Si: C, 70.48; H, 7.00. Found: C, 67.66; H, 6.58. Copoly (methyl-3'-ethoxypropylsilylene/l, 4-phenylene) The reaction of copoly(methylsilyienel/l,4-phenylene) (0.8 g, 6.7 mmol), allyl ethyl ether (0.7 g, 8.1 mmol), and 5 JJ.L of Pt complex in 10 mL of THF were placed in a 25 mL round bottom flask, equipped with a Teflon covered magnetic stirring bar and an efficient reflux condenser. The reaction was stirred for 72 h at 80°C. The flask was allowed to cool and the mixture was filtered and the volatile solvents were removed by evaporation under reduced pressure. The residue was dissolved in a minimum amount of THF and the polymer was precipitated from pentane. This process was repeated twice. The polymer was dried under high vacuum. In this way, 1.2 g, 88% yield of product polymer Mw/M n = 12,100/3,450, Tg = -7°C was isolated. *H NMR 8 : 0.50(s, 3H), 1.03(m, 2H), 1.14(m, 3H), 1.62(m, 2H), 3.35(m, 4H), 7.43(s, 5H). 13C NMR 5: -4.69, 10.16, 15.19, 24.07, 65.98, 73.22, 127.76, 129.11, 130.94, 133.15, 133.70, 134.46, 136.02, 137.83. 29Si NMR 8 : -7.01 (s), -1.2. IR o: 3049, 2975, 2933, 2866, 2797, 1429, 1411, 1377, 1355, 1253, 1184, 1133, 1067, 1021, 1011, 911, 833, 778, 735, 700, 683 c m 'l UV ^-max nm(e): 236(12,500), 265(1,090). Elemental Anal. Calcd. for C l2H l80S i: C, 69.84; H, 8.79. Found: C, 67.62; H, 7.92. Copoly (methyl-3'-phenoxy propylsilylene/1,4-phenylene) The reaction of copoly(methylsilylene/l ,4-phenylene) (0.5 g, 4.2 mmol), allyl phenyl ether (Aldrich) (0.6 g, 4.5 mmol), and 5 (iL of Pt complex in 10 mL of THF were placed 186 in a 25 mL round bottom flask, equipped with a Teflon covered magnetic stirring bar and an efficient reflux condenser. The reaction was stirred for 48 h at 80°C. The flask was allowed to cool and the mixture was filtered and the volatile solvents were removed by evaporation under reduced pressure. The residue was dissolved in a minimum amount of THF and the polymer was precipitated from pentane. This process was repeated twice. The polymer was dried under high vacuum. In this way, 0.9 g, 80% yield of product polymer, Mw/Mn = 10,400/3,520, Tg = 8°C was obtained. NMR 8 : 0.30(s, 3H), 0.92(m, 2H), 1.59(m, 2H), 3.64(m, 2H), 6.59(m, 3H), 6.98(s, 2H), 7.24(s, 4H). 13c NMR 8 : -4.65, 10.15, 23.74, 70.10, 114.39, 120.45, 129.35, 133.76, 134.54, 159.09. 29Si NMR 8 : -11.19, -6.87(s), -6.31. IR v: 3051, 2942, 2877, 1601, 1587, 1498, 1472, 1382, 1244, 1173, 1134, 1068, 1049, 1035, 1012, 910, 778, 757, 734, 692 cn r 1. UV Xmax nm(e): 235(12,530), 265(1,830), 271(1,950), 275(1,500). Elemental Anal. Calcd. for C ^H ig O S i: C, 75.54; H, 7.13. Found: C, 73.50; H, 7.18. Copoly (methy 1-4',7', 1 O', 13'-tetraoxatetradecanylsiIylene/l, 4-phenylene) The reaction of copoly(methylsilylene/l ,4-phenylene) (0.5 g, 4.2 mmol), allyl triethylene glycol methyl ether (Aldrich) (1.0 g, 4.9 mmol), and 5 |iL of Pt complex in 10 mL of THF were placed in a 25 mL round bottom flask, equipped with a Teflon covered magnetic stirring bar and an efficient reflux condenser. The reaction was stirred for 50 h at 80°C. The flask was allowed to cool and the mixture was filtered and the volatile solvents were removed by evaporation under reduced pressure. The residue was dissolved in a minimum amount of THF and the polymer was precipitated from pentane. This process was repeated twice. The polymer was dried under high vacuum. In this way, 1.2 g, 80% yield of a sticky material, Mw/M n = 13,290/4,460, Tg = -87°C was isolated. *H NMR 8 : 0.50(s, 3H), 1.01(m, 2H), 1.62(m, 2H), 3.33(s, 3H), 3.40(m, 187 2H), 3.51(m, 4H), 3.62(m, 8H), 7.32(s, 5H). 13 c NMR 8 : -4.69, 10.04, 23.88, 58.97, 69.94, 70.50, 71.84, 74.04, 127.75, 129.10, 130.92, 133.67, 134.42, 135.98, 137.76. 29Si NMR 5: -11.85, -11.37, -7.03(s), -6.46. IR v: 2876, 1254, 1134, 1109, 910, 778, 733, 647 cm '1. UV Xmax nm(e): 235(14,290), 267(1,190). Elemental Anal. Calcd. for C i7H2 8 0 4 Si: C, 62.92; H, 8.70. Found: C, 62.60; H, 8.13. 188 6.5 References: 1. R. West, in The Chemistry o f Organic Silicon Compounds, S. Patai and Z. Rappo port, eds. (J. Wiley & Sons, Chichester, England, 1989). 2. R. West, J. Organomet. Chem., 1986, 300, 327. 3. N. Noll, Chemistry and Technology o f Silicones, (Academic Press, New York, 1968). 4. T.C. Kendrick, B. Parbhoo and J.W. White, in The Chemistry o f Organic Silicon Compounds, S. Patai and Z. Rapporort, eds. (J. Wiley & Sons, Chichester, England, 1989). 5. S. Yajima, J. Hayashi and M. Omori, Chem. Lett., 1975, 931. 6. S. Yajima, K. Okamura and J. Hayashi, Chem. Lett., 1975,1209. 7. W. P. Weber, Trends in Polymer Sci., 1993, /, 356. 8. E. M. Fettes, Ed. Chemical Reactions o f Polymers (Interscience Publishers, New York 1964). 9. C. E. Carraher, Jr. and J. A. Moore, Eds., Modification o f Polymers (Plenum, New York 1983). 10. J. L. Benham and J. F. Kinstle, Eds., Chemical Reactions on Polymers (ACS Sym posium Series 364, American Chemical Society, Washington, DC 1988). 11. L. J. Mathias and C.E. Carraher, Jr., Eds. Crown Ethers and Phase Transfer Ca talysis in Polymer Science (Plenum Press, New York, 1984). 12. H. G. Woo, J. F. Walzer, T. D. Tilley. Macromolecules, 1991,24, 6863. 13. T. Imori, H. G. Woo, J. F. Walzer, T. D. Tilley. Chem. Mater., 1993,5, 1487. 14. J. Ohshita, M. Ishii, Y. Ueno, A. Yamashita and M. Ishikawa, M acromolcules, 1994,27, 5583. 15. C. X. Liao and W.P. Weber, Macromolecules , 1993, 26, 563. 189 16. S.J. Sargeant and W.P. Weber, Macromolecules, 1993, 26, 2400. 17. R. J. P. Corriu, W. E. Douglas, E. Layher and R. Shankar, J. Inorg. Organomet. Polym., 1993, 3, 129. 18. B. Kanner, W. G. Reid and I. H. Petersen, Ind. Eng. Prod. Res. Dev., 1967, 6, 88 . 19. C.X. Laio and W.P. Weber, Polym. Bull., 1992, 28, 218. 20. H. Guo and R. Volkle, Polymer Preprint, 1995, (I), 457. 21. R. Freeman, H. D. W. Hill and R. Kaptein, J. Magn. Reson.,1972,37, 4070. 22. L. Lestel, H. Cheradame and S Boileau, Polym., 1990, 31, 1154. 190 J w , i r .m - i ® .0 r r n Figure 6. 29§j NMR of poly(methylsilylene/l,4-phenylene). a b s 0 r b 300 290 flanoneters Figure 7. UV spectrum of poly(methylsilylene/l,4-phenylene). 3 0 1 2 0 M O S 1 0 rfos riO o riO S ffoo T a n p a r a tu r a (C) Figure 8. DSC of poly(methylsilylene/l,4-phenylene). 6 .0 5 . 5 5 .0 6.5 4 .0 Figure 9. NMR of copoly(methyl-3'-cyanopropylsilylene/l,4-phenylene). 1 9 2 i n *^1 ^ W \* r iTip i i i H T H n u m m | M i i H H i m r m niTTiTTim n i » H H i H p M i u » it|T T iu i u i | i m iTm H i M i i M i | i n » H M H u n n i » | u m i i i i | m n u » f n i n m i t m i m » r 60 60 p P rt 40 4 0 1 4 0 1 4 0 1 0 0 Figure 10. NMR of copoly(methyl-3'-cyanopropylsilylene/l,4-phenylene). 10.0 0.0 ' 10-2 ' 20.0 - 3 0 r m Figure 11. 29$j NMR of copoly(methyl-3’-cyanopropylsilylene/l,4-phenylene). 1 9 3 H E A T FLO* A b s 0 2 .7 0 4 Z34 6. 2 0 0 XO 600 500 70a Figure 12. UV spectrum of copoly(methyl-3'-cyanopropylsilylene/l,4-phenylene). *■* ' ’ T v fraa: 34.M to: M .39 On«at- 00.38 T v 8 8 .2 7 I 7 . 1 1m T a a p a r a tu r a (Cl inn rira tfnr nr Figure 13. DSC of copoly(methyl-3'-cyanopropylsilylene/l ,4-phenylene). 1 9 4 h ! 1 1 [ 1 1 1 1 1 1 n ijmrjp- '' | r | r |'r m T n n pHrpn r » i 1 1 ipn iriT v iym i*f''htj ■ ithIitit- ...5 0 .0 T .S o.o f..5 6 .0 M s.o o.I tJ> j.S i.o J .5 o .o i.5 1 ,0 0.5 Figure 14. *H NMR of copoly(methyl-3'-ethoxypropylsilylene/l,4-phenylene). k j T T i)^im irr T puiTtirn)Trninnin in n nttrni»ii)>iiiiim |u ir»m^Tiiiiuii|T it 14fl .jo lOP * 0 ^ & Figure 15. NMR of copoly(methyl-3'-ethoxypropylsilylene/l,4-phenylene). 1 9 5 > ■ I .......................‘ ■ I— ' ■ I—" ................................I ....................., p.. . . . . . . ..... 1 0 . 0 0 . 0 -10.0 -'20'0 - 3 0 . 0 PPM Figure 16. 29$j NMR of copoly(methyl-3'-ethoxypropylsilylene/l,4-phenylene). I.tf - X N H K 129.0- t- X 2 60 - a K M 20 - 3090 3590 2080 V R V E N U H B E R Ice,-I) 1500 Figure 17. FT-IR of copoly(methyl-3'-ethoxypropylsilylene/l,4-phenylene). 1 9 6 A b s 0 r b & n c e 761 600 300 500 400 2 0 0 fUnoneters Figure 18. UV spectrum of copoly(methyl-3'-ethoxypropylsilylene/l,4-phenylene). IS 7.S 1m 1m > . 0 0 Figure 19. DSC of copoly(methyl-3'-ethoxypropylsilylene/l,4-phenylene). 1 9 7 100.00 not oo.oo Ttt 400.72 0NK7 A T 949.29 S r r - 67.9 H X (!) ► H 00.00 U j X " “ io lo lio'.'oo sic. 00 Wo.00 W o.O O slo.oo W o.C O 700.00 7^.00 220.00 TEMPERATURE (C) Figure 20. TGA of copoly(methyl-3'-ethoxypropylsilylene/l,4-phenylene). T T I T r 8 0 7.0 2.0 0.0 Figure 21. NMR of copoly(methyl-4’,7',10',13'-tetraoxatetradecanylsilylene/l,4- phenylene). 1 9 8 J 2D 1 4 0 Figure 22. 13c NMR of copoly(methyl-4',7',10',13'-tetraoxatetradecanylsilylene- /1,4-phenyIene). 0 . 0 10.0 -2 0 . 0 - 10.0 rrri Figure 23. NMR of copoly(methyl-4',7',10',13'-tetraoxatetradecanylsilylene- /1,4-phenylene). 1 9 9 I •c M - H u - wm 1508 V R V E N U M B E R ( • • - ! ) Figure 24. FT-IR of copoly (methyl-4',7', 1 O', 13'-tetraoxatetradecanylsilylene/l,4- phenylene). A b s 1.321 Z?5 & 300 b O O 500 700 200 nanometers Figure 25. UV spectrum of copoly(methyl-4',7',10',13'-tetraoxatetradecanylsilylene- /1,4-phenylene). 2 0 0 n'% " T ( frMi-ioa.oe t a c - 8 1 .0 8 O M t t - 4 4 . 7 7 TB-4S.lt I OJ''> F igure 26. DSC of copoly(methyl-4',7\10',13'-tetraoxatetradecanylsilylene/l,4- phenylene). AJli. n 11 n 111 it111 m i j1 1 1 1 |1 1 rr|1 1 1 1 |n 1111111111111111111111111111n 11 j 1111|1111 j r r r i | i l l 11 n 11, . ! ■ > p i M ■ 1111 j i 9.0 8.0 7.0 6.0 5.0 4.0 PPM Figure 27. NMR of copoly(methyl-3'-phenoxypropylsilylene/l,4-phenylene). 2 0 1 I l l * 4 0 m iiim ii> p n im i|in in n > | iinin H ii»i|iiMnin m n m iijHHiu ii|in H m i|» n wm t ^ 00 4) ao o Figure 28. NMR of copoIy(methyl-3’ -phenoxypropylsilylene/l,4-phenylene). ............................................ ■ — i ---------- — -----1 --------------- 10.0 0 .0 - 1 0 .0 -CO .0 ppm Figure 29. 29$i NMR of copoly(methyl-3'-phenoxypropylsilylene/l,4-phenylene). 2 0 2 Z TRRNSHirTRfCE I.!•* X H R X IM - 5» - : sn Figure 30. FT-IR of copoly(methyl-3'-phenoxypropylsilylene/l,4-phenylene). 300 Manometers Figure 31. UV spectrum of copoly(methyl-3’-phenoxypropylsilylene/l,4-phenylene). 2 0 3 H E A T aOM I I .B - T( fraat • ! . Z M U id.7 * O M I f t . M T«- 7.11 I 7.1 1.71 ir»--------- Taaparatura (0 Figure 32. DSC of copoly(methyl-3'-phenoxypropylsilylene/l,4-phenylene). ».« d.fl T. t S-o 4.o j o * o i.o o.o P P » t Figure 33. NMR of copoly(methyl-3'-biphenoxypropylsilylene/l,4-phenylene). 2 0 4 ’ ’ T ” 160 T 140 "'" I .....!"" 120 100 SO PPM U1 1 " 2 0 0 Figure 34. 13c NMR of copoly(methyl-3'-biphenoxypropylsilylene/l,4-phenylene). M v v r M r ' w / < * H r W v \ A / v * ^ / v1 A ti v> v > i -------- • ■ ' I — ■ " ■ i .... - ' ■ r —- ......... ■ ...................p—■ • ■ 1 0 . 0 0 . 0 - I Q . 0 . ^ 0 - 0 - 3 0 . 0 PPM Figure 35. 29$i NMR of copoly(methyl-3'-biphenoxypropylsilylene/l,4-phenylene). 2 0 5 MIN « MM a M - ar t r 2 8 - ISM IMI 2 tM I Figure 36. FT-IR of copoly(methyl-3'-biphenoxypropylsilylene/l,4-phenylene). Z O O Figure 37. UV spectrum o f copoly(m ethyl-3'-biphenoxypropylsilylene/l,4- phenylene). 2 0 6 H EA T F L O W t»H) 19 Tg f r o K 2 .7 9 to : 6 3 .6 2 Q n iO t- 2 6 .0 4 T g - 3 3 .1 1 1 0 5 T a a p o r o t u r o (C) 1 .0 0 Figure 38. DSC of copoly(methyl-3'-biphenoxypropylsilylene/l,4-phenylene). 2 0 7
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