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Characterization of the copolymer of styrene and butylmethacrylate

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Characterization of the copolymer of styrene and butylmethacrylate

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Content CHARACTERIZATION OF THE COPOLYMER
OF STYRENE AND BUTYLMETHACRYLATE
by
Soonja Choe
A Thesis Presented to the
FACULTY OF THE SCHOOL OF ENGINEERING
UNIVERSITY OF SOUTHERN CALIFORNIA
In partial Fulfillment of the
Requirements for the Degree
MASTER OF SCIENCE IN CHEMICAL ENGINEERING
December 1982
UMI Number: EP41809
All rights reserved
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a note will indicate the deletion.
UMI
‘ Dissertation Publishing
UMI EP41809
Published by ProQuest LLC (2014). Copyright in the Dissertation held by the Author.
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This thesis, w ritten by
C 'h o e . ( Soonja Ghoe)
under the guidance of / ? * * - F a cu lty Comm ittee
and approved by a ll its members, has been
presented to and accepted by the School of
Engineering in p a rtia l fu lfillm e n t o f the re
quirements fo r the degree of
Master of Science in Chemical Engineering
D a te ...1982
F a cu lty C om m ittee
P . ? . • . . . Salovey¥^
Chairman
Dr. Chang
Mc.
Dr. Yortsos
(
TABLE OF CONTENTS
page
Synopsis 1
Introduction • 2
Experimental
Column Selection
Sample Preparation for GPC 5
Calibration and Universal Calibration
Curve 6
Intrinsic Viscosity 1^
Elemental Analysis 1^
Results and Discussion 17
References
LIST OF TABLES
Table page
1. Polystyrene Standard Sample 6
2. Copolymer Sample 8
3. The Data for Calibration and Universal
Calibration Curve by PS 11 .
4. Calculation of Molecular Weight of Sample A 20
5. Calculation of Molecular Weight of Sample B 22
6. Calculation of Molecular Weight of Sample C 24
7. Calculation of Molecular Weight of Sample D 26
8. Calculation of Molecular Weight of Sample E s28
9. Calculation of Molecular Weight of Sample F 30
10. Calculation of Molecular Weight of Sample G 32
11. Molecular Weight of Seven Copolymers
12. T of Copolymer Estimated from DSC Thermograms 36
§
13* Intrinsic Viscosity Results for Seven Copolymers
38-39
14. Composition of Copolymers by DSC and Elemental
Analysis 43
_____________________________________________________________iii
LIST OF FIGURES
page
Calibration*. Curve of Mono disperse PS 9
Universal Calibration Curve 10
Conventional Presentation of Thermal
Analysis Data 12
T of Sample A 13
o
Ubelholde Viscometer 16
Differential Distribution Curve for Sample A 17
Integral Distribution Curve for Sample A 18
Intrinsic Viscosity of Sample A,B and C ^0
Intrinsic Viscosity of Sample D,E,F and G ^1
Synopsis
The characterization of various polystyrene-co-poly-
butylmethacrylate copolymer by gel permeation chromatogra-
phy(GPC) provided a means for obtaining M , Mw> polydis-
persity, and cumulative molecular weight distribution
curve. The copolymer composition was determined by diff
erential scanning calorimetry(DSC) and elemental anlysis.
M , of seven copolymers were determined to be in
the range of 6,600 to 15»300, ^9i700 to 97»700> respecti
vely, by GPC and the data obtained from DSC and elemental
analysis method was in good agreement.
INTRODUCTION
I
Gel Permeation Chromatography was introduced by
John Moore to describe the technique of molecular size
separation accomplished on a gel column, using liquid
chromatography apparatus. The term gel permeation is
derived -from the method of separation on a column consist
ing of highly crosslinked polystyrene gel with a liquid
structure. Separation occurs on the basis of the permea
bility of the gel. Molecules larger than the maximum
pore size pass through the column in the interstitial
volumn. Molecules smaller than the maximum pore size
enter the gel and are size-separated. The smaller mole
cules require more solvent to elute them through the
column.
In previous publications on the techniques of gel
2 3 4
permeation chromatography, * the method of universal
calibration to obtain the molecular weight distribution
of various sample was reported. Preliminary results
showed that such measurements were possible and useful,
despite the very low concentrations of polymer. Similar
results have been published by other workers.^
To properly characterize a copolymer, the composition
2
distribution should be specified as well as the molecular
weight(MW) and molecular weight distribution(MWD), GPC
has greatly increased the speed and accuracy with which
' O Q .
this can be done. Historically, most workers ’ have
used bulk fractionation techniques based on solubility to
obtain fractions which were then characterized for compo
sition by spectrocopic means(e.g. NMR, UV,^ IR, and X-
ray) and thermal methods(such as DTA, DSC10 and TGA).^
Polymer characterization by Differential Scanning
Calorimetry(DSC) is one of the major applications. The
application of DSC to polymer studies has generally led
to a much greater appreciation and understanding of the
effects of thermal history on polymer.
In order to get accurate composition, an elemental
analysis method was used for seven copolymers.
The present study describes that MW, MWD, and compo
sition of high copolymer are required to characterize the
samples.
EXPERIMENTAL
Column Selection:
Experiments were initially carried out with a
standard 5-column system of 10^, 10^, 10^, leP, and 500 A.
These five columns were connected in series and run as a
set to cover an extremely wide molecular weight range.
By combining several columns in series like this, it is
possible to get good resolution from several million mole
cular weight to a few thousand molecular weight.
The packing material in column is jul -styragel par
ticle from Waters Associate. If the linear velocity or
viscosity becomes too high, some of the surface gel can be
sheared from the particle. This is one of the reasons
why there are maximum flow rate limitations placed on the
styragel particles. Temperature was selected to be room
temperature of 25°C ± 1°C to maintain same condition for
viscosity. Tetrahydrafuran(THF) was used as a solvent by
Burdick and Jackson Laboratories, Inc., which properties
are 210nm in UV cutoff, 0.55 cp in viscosity at 20°C,
3.0ml/min. of maximum flow rate. Flow rate of solvent
was controlled to be 2cc/min., sensitivity was 8X, and
chart speed was 0.1 in/min.
Sample Preparation for GPC;
Polystyrene standards samples for calibration were
monodisperse, and tabulated in table 1. Polystyrene(PS)
and polybutylmethaerylate(PBMA) copolymers with different
compositions are quite soluble in THF. The samples were
shaked for 24 hours at room temperature to dissolve them
in THF solvent.
Typical viscosity limiting concentration for GPC is
as follows^ up to 20000 MW is 0.25$, 34000 MW to 200000
MW is 0.10$. And injection volume according to sample
concentration was changed to obtain appropriate elution
volume and load. Filt-ration of the samples before injec
tion is usually recommended for the protection of the
columns, so that all the samples reported here were fil
tered by Millipore Filter.
The polymer used are tabulated in table 2. Their
concentration was 0.1$, and injection volume was 0.5 ml.
This injection volume was higher than recommended volume
for better result in analytical method.
5
Table Is Polystyrene Standard Sample
PS MW Concentration(^) Injection Vol.(ran)
2200
0.25 0.05
4000
0.25 0.05
9000
0.25 0.0 5
•17500
0.25 0.05
37000 0.10 0.1
110000 0.10 0.1
233000 0.10 0.1
390000
0.05 0.5
2000000
0.05 0.5
Calibration and Universal Calibration Curve;
The data for calibration and universal calibration
curve are shown table 3•
A GPC calibration curve for standard PS in Figure 1
is plotted as molecular weight versus elution volume(V)
which is obtained from Gel Permeation Chromatograms.
*
The elution volume represents the highest peak in the
chromatogram because standard PS has very narrow molecu
6
lar weight distribution. Plots for the various polysty
rene standards were linear enough. However, the standards
with molecular weight of 2,000,000 and 2,200 were out of
straight line slightly.
For monodisperse PS, intrinsic viscosity if is given
by eq. (1) in THF solvent at 25°G.1:L
= 1.6 x 10-1+ Mw0,706 (1) -
Therefore, the universal calibration curve can be obtained
by using eq. (2).
(11 Mw = *M,a+1 (2)
The universal calibration curve for standard PS was
plotted in Figure 2.
DSC s
Differential Scanning Calorimeter(Perkin Elmer
Model DSC-2) was used to measure the glass transition
temperature(T) of various copolymers. The T of each
§ O
polymer depends on the heating rate. The higher the-
heating rate is, the higher the T becomes. However,
o
here, the heating rate was fixed 20°/min. Fig. 3 shows
conventional presentation of Thermal Analysis Data.
Sensitivity was chosen 20 millicalories/sec. Refer-
7
ence sample pass was used gold, and the amounts of each
sample was fixed about 10 mg. Purge gas was at 10
*
cc/min.
Table 2 s Copolymer Sample
Sample Trade Name MW Range (xlOOO) Source
A Picotonor 1200
65-75
Hercules
B XRP-70 90-110 Ionac S.C
C X-242 56-60 Ionac S.C
D X-230 65-80 Ionac S.0
E
X-231
60-70 Ionac S.0
F X-211 80-100 Ionac S.C
G sp2 50/50 Over 100
p 2
Molecular weight range was given by the company.
8
Calibration Curve of Monodisperse PS
Fig
-p
•H
o PF"
Elution Volume
Fig. 2: Universal Calibration Curve
28
Elution Volume
10
Table 3s The Data for Calibration and Universal
Calibration Curve by PS
PS MW(xlO 3) Elution Vol.* p ! | ] at 25°C ty] M
2.2 U r 5 .8 3.66xl0“2 8.05x10
4 45.0 5.59xl0“2 2.24x 102
9
42 .8 9.90xl0"2 8.91xl02
17.5
41.0 1.58xlO_1 2.77x 103
37 39-0 2 .69x10-1 9.95x 103
110 35.8 5.80xl0_1 6.38x10^
233
33.8 9.85x 10_1 2.30xl05
390
32.5
1.42 5.54x10-5
2000 31.6 4.49 8.9Sxl06
* 5 f *
Elution volume was selected at the highest peak.
Glass transition temperature(T ) is sometimes diffi-
o
cult to detect in highly crystallized polymers because
they have free volume effect. As shown in Fig. 4, when
the polymer was heated first time, the curve occured
dashed line, and the curve was a black line when it was
heated second time.
In order to obtain accurate T , each sample was
quenched from the melt in DSC by cooling at the maximum
11
rate, 320°/min.
Fig, 3: Conventional Presentation of Thermal Analysis
Data
Fusion Peak
Endotherm
Glass Transition
rH
Ending
^Transient
Starting
Transien
Isothermal
Isothermal
-1 Crystallization
Peak
rH
-2
-p
Exotherm
400
200
600
300 500
Temperature K
12
Fig. ki T of Sample A
o
Picotonor 1200
Weights 10 mg
Scan Rates 20 deg/min.
to 76.59
Onset Points 67*59
Cal/degs i J-.76xlO“2
Mid- Points 71*23
2.0
^ Transition Temperature
(Mid- Point)
.0
onset point
80
Temperature °C
13 -
Intrinsic Viscosity:
Viscosity measurements for seven copolymers of PS and
PBMA were carried out with a Ubelholde - cannon viscome
ter. The apparatus essentially consists of the viscometer
which is connected to a reservoir containing THF to main
tain an atmosphere of THF and to prevent the evaporation
of THF from solutions. The solution of the different
tonors is prepared in THF at 4 different concentrations
5$» 2.5#, 1.25% and 0.625$. The experiment essentially
consists of measuring the time taken for solution to flow
down through bulb B between points 1 and 2. This is the
efflux time taken for solution. Similarly, the efflux
time for pure solvent THF is noted. The experiment is
repeated for solutions at different concentrations.
Ubelholde viscometer is shown in Fig. 5*
Elemental Analysis;
Seven copolymers were dissolved in THF solvent and
precipitated in a large amount of methanol(non-solvent)
to eliminate the possible impurities(or additives) in
tonors. The precipitates were, then, dried in vaccum at
1 M r
60°C for a week. Carbon and hydrogen contents of the
purified tonors were determined by use of elemental
analyzer at Galbraith Laboratories, Inc. (Knoxville, TN).
-IS-
Fig. 5s Ubeholde Viscometer
Upper mark
Lower mark
B
RESULTS AND DISCUSSION
The Gel Permeation Chromatogram results for picotonor
1200(Sample A) are in table and its differential and
integral distribution curves are shown in Fig. 6 and 7>
respectively.
Fig. 6: Differential Distribution Curve for Sample A
r - ’i
-P
•rH
c
C D
-p
£
PH
0
38.2
Elution Volume
17
Fig. 7
Integral Distribution Curve for Sample A
100
80
60
20
0
10 10 10
Molecular Weight
18
Mn and M^ were calculated by the following equations.
n.M. h.
Mn = ru = TT/WT
1 l' 1
n.M.2 h.M.
M = — ™ (^)
w n.M. h.
11 l
Polydispersity = Mw / Mn (5)
where n^ is mole fraction of each molecular weight
corresponding to elution volume(V^), M^ is molecular
weight and in is a height of
l
By eq. (3), (» and (5), Mn , Mw and polydispersity
for sample A were obtained 15•3x10-^, 97*7x10^, and 6.5,
respectively.
The data for seven copolymers are given in table 11.
It shows there are two sets of M and M . M and M of
n w n w
column A were obtained from calibration curve under
assumption of copolymers being pure polystyrene, and Mn
and Mw of column B were calculated by analytical method
from universal curve.
19
Table 4; Calibration of Molecular Weight for Sample A
i
h i
V.
i
M.a
X
h.M. c
1 1
hi/M^J6
1 0.7 33.2
29.5
0.02
20.7
35.0 0.02 24.5
2
2.9
34.2 20.0
0.15
58.0 19.0 0.15 55.1
3
6.8 35.2 14.0 0.49 95.2
10.5
0.65 71.4
4
12.3
36.2 9.4
1.31
115.6 5.6 2.20
68.9
5
16.4 37-2 6.8 2.41
111.5
3.0 5.47 49.2
6
17-5
38.2 3.8 3.80
80.5 1.65
10.61
28.9
7
15.0 39-2 3.2 4.69 48.0 0.9
16.67 13.5
8 10.8 40.2 2.2
4.91
23.8 0.48 22.50 5.2
9
6.8 41.2
1.55 ^•39 10.5
0.26 26.15 1.8
10 4.2 42.2 1.1 3.82 4.6 0.13
32.31 0.5
11
2.9
43.2 0.76 3.82 2*2
00
0
«
0
36.71
0.2
12 1.1 44.2 0.52 2.12 0.6 0.04 27.50 0.1
13 0.1 45.2
0.35 0.57
0.1 0.02 9.09 0.0
urn 97.6
32.5 571.3
190.0
319.3
_4
a,e,d and f imply multiplying by 10 and b and e should
4
multiply by 10 in Tables 4 through 10.
20
1. M = ------- rr— = 30.0X103
n 32.5x10
2. Mw = = 58.5x1 o3
3 M “ ~— ------- = 15.3X103
n 190x10 xO.335
l \ . M - 319 » 3x10 qr p > 7 X^q3
w 97.6x0.335 y/*/xiu
— k -
r' M 1.9x10 p.3
5. _ _ _ _ _ _ _ 56.7x10
Here, 1 and 2 were calculated if the copolymer was assumed
pure PS. And 3 and ^ were calculated by Universal Calibra
tion Curve.
3
6. Polydispersity = 97.7x10 = 6.
15.3x10J
•■21
Table 5 s Calculation of Molecular Weight for Sample B
i h.
X
v.
X
M.a
X
h j / V
hiMi°
h./M.ty]6
1 o. 6 33.4 28 0.02 16.8
31
0.02 18.6
2 3.0 34.,4
18.5
0.16
55.5 17
0.18 51.6
3
8.0 35.4
12.5
0.64 105.0 9*2 0.87 73.6
4 14.8 36.4
8.9 1.67 131.7
5-0 2.96 74.0
5
20.7 37.4 6.3
3.29
130.4
2.7 7.67 55.9
6 22.6 38.4
4.3
5.26 97-2 1.43 15.80
32.3
7
20.0 39.4
3.5 5.71
70.0
0.79
25.32 15.8
8 .14.4 40.4 2.0 7.20 28.8 0.43 33.49
6.2
9
8.8 41.4 I.45
■ 6.07
12.8
0.23
38-26 2.0
10 5.4 42.4
0.99
5.45 5.3
0.12
0
0
- 3 -
0.6
11
3.1
43.4
0.7 4.43 2.2
0.07 44.29
0.2
12 1.2 44.4 0.49 2.45 0.6 o.o4
0
0
•
0
0.1
13 0.3
45.4
0.35
0.86 0.1 0.02
15.03
0.0
Sum
122.9
43.21 651.4 258.86
330.3
22
- i
1. M = — 122^2--- = 28.^xl03
n ^3•21x10 4
o M = ^-51 ‘^10 = 33 OxlO3
2. Mw 122.9 iJ-UXiU
3 . = — 2-' = 16
n
258.86x10 xO.29
k. M = — 33Q.- 3. xiO __ = 92.7xio3
W 122.9x0.29
5. M = — = ^2.1xl03
v w 0.29
6. Polydispersity = 92. 7, xl 0 _ _
l6.^xl0-?
.ilxlO3
5-7
22
Table 6: Calculation of Molecular Weight for Sample C
i h.
i
V.
1
M.a
l
h./M.b
1 1
h.M. G
i i
Mi[7|]d h./M-tf
1 1.6
35
15.0 0.11 24.0 11.8 0.14
18.9
2 2.8 36
10.3 0.27 28.8
6.7
0.42 18.8
3
*6.2
37 7.1
0.86
^3-3 3.5 1.7 k 21.3
4
10.5 38 5.0 2.1
52.5 1.9 5-53
20.0
5 14.3 39 3-5 4.09
50.1 1.0 14.30
14.3
6
15.3
40 2.8 5.46 42.8 ' 0.58 27.32 8.6
7
13.0 41
1.65 7.88
21.5 0.3 k3.3 3-9
8
9.0 42 1.18
7.63
10.6 0.16
56.25
1.4
9 6.7 k3
0.82
8.17 5.5
0.086
77.91
0.6
10 3.8 44
0.55
6.91 2.1 0.046 82.61 0.2
11 1.6 45 0.38 4.21 0.6 0.028
57.1^
0.1
12
0.5
46 0.27
1.85
0.1
0.013
38.46 0.0
Sum 00
N>
49.5
281.0 ^05.2 110.0
24
1. M = --- ^ _ 2-- _ 17.23
n ^9.5x10“
2. Mw = — 28U ° f 0^ = 33.0X103
3. M =----------— JT------ = 8 . 2x10 3
n ^05.2x10" xO.26
k ’
« . = ag.So .26 = ^ 9 . 7 x l 0 3
S- “w = - 6t 3 M — = 26. lxlO3
6. Polydispersity = ^9«7x10. _
8.2x10^
25
Table 7s Calculation of Molecular Weight for Sample D
i h.
1
V.
X
M.a
X
h./M.b
x/ X
h.M. C
X X
VM-bP
8 h.M.ty1
1
0.3 33-3 28.5
0.01 8.6 33-0 0.01
9.9
2
1,9 34.3
m
O
0.15 24.7
10.0
0.19
19.0
3 5.5 35.3
9.2 0.60 50.6 5.4 1.02
29.7
4
10.9 36.3
6.5 1..68 70.9 2.9
3.76 31.6
5
16.7
37.3 4.5 3.71
75-2
1.5 11.13 25.1
6
19.7 38.3
3.2 6.16 63.0' 0.84
23.45 16.5
7 19.5 39-3
2.1
9.29 41.0 0.46
42.39
9.0
8 15.8
40.3 1.5 10.53 23.7 0.25
63.20 4.0
9 10.7 41.3 1.0
10.7 10.7 0.13 82.31
1.4
10
7.1
42.3 0.72 9.86
5.1
0.078
91.03
0.6
11 4.9
43.3
0.50 9.80
2.5
0.044 111.36 0.2
12 3.0 44.3
0.37
8.11 1.1 0.023 130.43 0.1
13 1.5 45.3
0.1 15.00 0.2 0.01 150.0 0.0
Sum
117.5
CD
•
ON
O
377.3
710.28 147.1
26
1. M = — ±±2^5. — _ = 13.7XIO3
n 85.6x10“
2. M = = 32.1X103
w 11/.,3
3. M = 117 ' = lO.OxlO3
n 710.3x10 xO. l6'5
*• «w ■ ■ 75.9X103
5- . “w = . '"o3 fgr~ = 9°-9xl°3
6. Polydispersity = 75»9x10 . . _
10.0x10
2Zi
Table 8: Calculation of Molecular Weight for Sample E
i h.
l
V.
i
M. a
l h iM i°
1 0.3 33-9 23
0.01 6:. 9 22 0.01 6.6
2
1.3 34.9
16 0.08 20.8 12 0.11 15.6
3
3.6
35-9
11
0.33
39.6 6.6
0.55
23.8
4
7.5 36.9
7.4 1.01
55-5 3.5
2.14 26.3
5 11.5 37-9 5.1 2.25
•
00
1.9 6.05
11.6
6
13.9 38.9 3.5 3.97
0-
•
CO
- 3 -
1.05
13.24 14.6
7 13.3 39.9
2.4 5.54
31.9
0.56
23.75 7.5
8 10.2
40.9 1.7
6.00
17.3 0.31
32.90 3.2
9
7-0 41.9 1.2
5.83
8.4
0.165
42.42 1.2
10
4.7 42.9
0.86
5.47
4.0
0.089
52.81 0.4
11 2.8
43.9
0.54
5.19 1.5
0.048
58.33
0.1
12 1.0
44.9
0.26
3.85 0.3 0.039
25.64 0.04
13
0.2
45.9 0.13 1.54 0.02
0.027
7.41 0.01
Sum
77-3
41.1 293.6 265.4 111 .0
28
1. M = — T h l = I8.8xl03
n ^1.1x10"^
2. M = — — = ^O.OxlO3
w 77 o
3. M = ----1IU2.---E------ = 13.5XIO3
n 265.^x10 ^xo.zis
'*■ MW = - ^ # t § i 5 7 H 5 ' = 66l8xl°3
5- “w - = '*°'9xl°3
6. Polydispersity = = ^.9
13.5xl0J
2_9 -
Table 9: Calculation of Molecular Weight for Sample
F
i h.
l
V.
i
M. a
1
h./M.b
1' 1
h.M. c
1 1
9
Vijbpf
•V"
$ 0.5
34.2 20
0.03
10.0
35
0.01
17.5
2 ■: '
'•2.5
35.2 14 0.18 35-0
19 0.13 47.5
3
8.0 36.2 9.4 0.85 75.2 10.5 0.76 84.0
4
15.5
37.2 6.8 2.28 105.4 5.6
2.77
86.8
5
26 38.2 4.6
5.65
119.6 3.0 8.67 78.0
6 32 39.2 3.2 10.00 102.4
1.65 19.39
52.8
7 32.5
40.2 2.2 14.77
71.5 0.9
36.11
29.25
8 26 41.2
1.55 16.77 40.3
0.48
54.17
12.48
9 17
42.2 1.1
15.45 18.7
0.2 6 65.38 4.42
10
12.5
43.2 0.76
16.45 9-5 0.13 96.15
1.63
11 8 44.2 0.52 15.38 4.2 O.079
101.27 O.63
12 4 45.2
0.35 11.43
1.4 o.o4 100.0 0.16
13 1.5
46.2 0.12
12.5
O'. 2 0.022 68.18
0.03
Sum 186.0 122.0 593.4 553.0 415.2
30
186 _
122x10"
1. Mn = --if- = 15.3x10
2- “w = g9?8g:o°--= 31.9X103
3. M =-- — --7 7----- = l^.OxlO3
n 553x10 3c0.2ij-
«w = 186x0. I P — = 93.0xl03
5- Mw = 6- i 2 .zi°— = 25.8X103
6. Polydispersity = , 93 ., , 0x1, 0 — _
1*1.0x10
31
Table 10; Calculation of Molecular Weight for Sample G
i h.
i
V.
l
M.a
1 V Mib
h.M. c
X X
hi/fcff
1 1.1 34.2 20 0.06 22.0 19.0 0.06
20.9
2
3-9
35.2 14 0.28 54.6
10.5 0.37
41.0
3 7.9
36.2 9.4 0.84
74.3
5.6 1.41 44.2
11.7
37.2 6 i t 8 1.72 79.6 3.0 3.90
35.-1-
5
1*4-. 0 38.2 4.6 3.04 64.4 I.65 8.48 23.I
6
13-7
39.2 3.2 4.28 43.8
0.9
15.22
12.3
7
11.4 40.2 2.2 5.18
25.1
0.48
23.75 5.5
8 8.2 41.2
1.55 5.29 12.7
0.26 31.54 2.1
9
: 5.0 42.2 1.1
4.55 5.5
0.13 38.46
0.7
10 3.0 43.2 O.76
3.95 2.3 0.079 37-97
0.2
11 1.8 44.2 0.52 3.46
0.9
0.04 45.00 0.1
12 1.1 45.2
0.35
4
3.14 0.4 0.022 50.00 0.0
13
0.4 46.2 0.2 5 1.60 0.1
0.015 26.67 0.0
Sum 83.2
37.39 385.7 282.83
185.2
32
1. M = ^ 2 — _ 22.2x 103
n 37.^xlO-
2. M = — I81r7xl0^_ = i | , 6. -^xl03
w 03 •
3. M = ----^ 2 — JT = 6.6xl03
n 2 8 2 .8 3 x 1 0 x O .445
4 jy j - _^ .Q .r S .ii ..2 x lO ___ £„ qx iq 3
w 83.2x0.445 7U.0X1U
5. M = — = 27.0xl03
^ w 0.445
6. Polydispersity = 50.0x10 _ ^ ^
6.6xlOJ
33
Table 11: Molecular Weight of Seven Copolymers
Sample MW Range
(xl0~3)
A B
- *
M xlO '
w
MnxlO~3 Mwxl0'3 M xlO"3
n
M xlO~3
w
M M
w n
A
0.335 65
-
75
30.0
58.5 15.3 97.7
6.4-
56.7
B 0.290 90 - 110 28.4- 23.0 16.4-
92.7 5.7
4-2.1
C 0.260 50 - 60
17.5
33.0 8.2
4-9.7
6.1 26.1
D 0.165
65
-
80
13.7 32.1 10.0
75.9
7.6
90.9
E 0.24-0 80 - 100
15.3 31.9
14-.0 93.0 6.6 25.8
T 0.215 60 -
70 18.8 4-0.0
.13.5
66.8
4-.9 4-0.9
G 0.445 Over 100 22.2 4-6.4- 6.6 50.0 7.6
27.9 _
* Molecular Weight from the highest peak of Universal Calibration Curve.
The accurate determination of molecular weight distri
bution of the copolymers was very difficult because the
exact reproducibility in the elution volume from GPG of a
sample along with molecular weight was not obtained. So,
here, the average value was taken. As shown in table 11,
molecular weights for sample B,C,D,E and P were fitted in
the data which given from company, however, molecular
weights of sample A and G were quite different. Here, it
was not found any relationship between viscosity and
molecular weight.
T of various copolymers were measured, and eq. (6)
O
was used to estimate the copolymer composition from T
g
given literature.^
1 , / v Wi , W0
tt + m (6)
gm xgl xg2
where T ^ and T ^ are “ the glass transition temperatures of
pure polystyrene and polybutylmethacrylate, respectively,
and they represent 373°K for PS and 293°K for PMBA}^
and W2 are respectively the weight fractions of PS and
FBMA-.
A DSC thermogram for picotonor 1200 is shown in Fig.
^ and here midpoint was taken as a T instead of onset
point. The estimated T are tabulated in table 12.
g
35
Table 12: T of Copolymer Estimated from ESC Thermograms
Sample T^C) Weight % of PS
A 72 69.1
B
73 71.2
C 72 70.3
D
63 59.7
E 68 65.6
F 78 77.0
G 56 50.3
The equation for intrinsic viscosity is given by
eq. (7) which is Huggins equation.
t sp = [ 0 1 ] + k'C (7)
c
where ^ sp = SP00!1 ^ 0 viscosity
c = concentration gm/dl
efflux time of solution
now, relative =-
efflux time of pure solvent
anc^ V . specific - rel ” ^
A plot of % p/o vs. concentrations in a straight line
with slope k' and intercept^]. The results for various
36
copolymer according to concentration tabulated in table
13 and their figures are shown in Figure 8 and 9.
37
Table 13: Intrinsic Viscosity Results for Seven Copolymers
Sample Consentration g/dl
^sp/°(dl/g)
(^](dl/g)
A
5 2.7609
0.5522
0.335
2.5
I.1061 0.4419
1.25
0.^902 0.3922
0.62 5 0.2243 0.3590
B
5
2.5730 0.5146 0.290
2.5 1.0315
0.4126
1.25
0.4450 0.3560
0.625
0.2024
0.3239
C
5
1.9065
0.3813
0.260
2.5 0.8107
0.3243
I.25 0.3595 0.2875
0.625 0.1732
0.2771
D' ~
5
2.8150 0.5658 0.165
2.5 0.9145 0.3658
1.25
0.3975
0.3180
0.625 0.1365 0.2185
38
Table 13 continued.
E
5
2.4090 0.4-819 0.215
2.5
0.8437
0.3375
1.25
0.3536 0.2829
0.625 0.1585 0.2536
F
5 1.9605 0.3921 0.240
2.5
0.8092 0.3221
1.25 0.3530 0.2824
0.625
0.1640
0.2625
G
5
4.0890
0.8187
0.445
2.5 1.6145 0.6458
1.25 0.6803
0.54-4-3
0.625
0.2926 0.4683
39
Fig. 8: Intrinsic Viscosity of Sample A,B,C
.80
.70
.60
.30
.20
.10
Concentration gm/dl
^0
Fig. 9: Intrinsic Viscosity of Sample D,E,F and G
.90
.80
• 70
.60
.50
^ .40
ft
ra
.30
.20
.10
00
4
5 3
1 0 2
Concentration(g/dl)
41
The composition data of seven copolymers by DSC and
elemental analysis are tabulated table 1*K At the elemen
tal analysis, the percentage of styrene in each copolymer
can be evaluated as follows.
96x + 96y
% carbon = ------------- x 100 (8)
104x + 1^3y
where, x and y denote moles of styrene and butylmethacry-
late in copolymer, respectively.
x + y = 1 (9)
Weight fo of polystyrene
= iM-g __ x 100 (10)
10te + l^3y
Here, 96, 10^4- and 1^-3 represent carbon weight in styrene-
and butylmethacrylate, styrene molar mass, and butylmetha-
crylate molar mass, respectively.
Table 1^ shows that copolymer composition obtained
from DSC and elemental analysis was in good agreement.
Therefore, T values of styrene and butylmethacrylate
which chosen from reference are accurate enough to obtain
good results.
k2
Table 1^: Composition of copolymer by DSC and
Elemental Analysis
.f,
By DSC By Elemental Analysis
Sample
T (°C)
g
PS wt<- % carbon fo hydrogen PS Wt%
A 72 69.1
83.88
8.9^
66.5
B
73
71.2 85.00 8.56 71.0
C 72 70.3 8^.75
8.92 70.0
D
63 59.7
81.86 9.10
58.5
E 68 65.6 83.78 8.77
66.1
F 78 77.0 86. 3^ 8.30
76.3
G 56 52.3 79.67
9.20 ^9.8
REFERENCES
1. Moore, J.C, J. Polym. Sci. A-2,.page 835 (1964).
2. Grubisic, Z., P. Repp, and H. Benoit, J. Polym. Sci.
B. £, page 753 (1967).
3. H. Benoit, Fifth International Seminar on GPC,
London(1968)•
4. Sixth International Seminar on GPC, Miami(1968b).
5. D. Goedhart, and A. Opschoor, J. Polym. Sci A-2 8,
page 1227 (1970).
6. J.M. Evans, Polym. Eng. Sci., 12, page 401(1973).
7. Prouder, T. Rosen E.M. Sep. Sci., 2* Page 437(1970).
8. Yau, Kirkland, Bly, In Mordern Size-Exclusion Liquid
Chromatography. A Wiley Publication, page 405(1979).
9. T. Ogawa, S. Tanaka, and T. Inaba, J. Polym. Sci.
Vol. 17, page 319-331(1973).
10. Groeninekx, G., Berghmans, H. and Smets, G., In
Abstracts of the IUPAC Macromolecular Symposium,
Leiden, Holland, Sept., page 742(1970).
11. Manual of DSC from Perkin Elmer.
12. Manual of GPC from Waters Associate.
13- Polymer Handbook.
44

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Creator Choe, Soonja (author)

Core Title Characterization of the copolymer of styrene and butylmethacrylate

Degree Master of Science

Degree Program Chemical Engineering

Publisher University of Southern California (original), University of Southern California. Libraries (digital)

Tag engineering, chemical,OAI-PMH Harvest

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Advisor Salovey, Ronald (committee chair), Chang, Wenji Victor (committee member), Yortsos, Yanis C. (committee member)

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