U.S. patent application number 09/750048 was filed with the patent office on 2002-02-14 for graft copolymer of syndiotatic styrene copolymer.
Invention is credited to Chao, Wee-Pin, Chen, In-Mau, Chen, Joung-Yei, Chou, Huai-Mei, Li, Chi-Lan, Tsai, Jing-Cherng, Wang, Bor-Ping.
Application Number | 20020019494 09/750048 |
Document ID | / |
Family ID | 26666565 |
Filed Date | 2002-02-14 |
United States Patent
Application |
20020019494 |
Kind Code |
A1 |
Li, Chi-Lan ; et
al. |
February 14, 2002 |
Graft copolymer of syndiotatic styrene copolymer
Abstract
The present invention provides a graft copolymer of a
syndiotactic styrene/para-alkylstyrene copolymer, having the
formula of 1 wherein R.sup.1 and R.sup.2 are independently selected
from the group consisting of hydrogen, alkyl, and primary and
secondary haloalkyl; X is a functional group selected from a group
containing halogen, oxygen, sulfur, silicon, nitrogen, carbon,
phosphorus, and mixtures thereof; Y is an atactic polymer moiety; a
ranges from 10 to 30000; b ranges from 0 to 30000; c ranges from 0
to 30000; and d ranges from 1 to 30000. The compatibility of the
graft copolymer of syndiotactic styrene/para-alkylstyrene copolymer
of the present invention with other polymers is improved over a
syndiotactic styrene polymer. Also, the graft copolymer of the
present invention can serve as a compatibilizer for a polymer
blend.
Inventors: |
Li, Chi-Lan; (Hsinchu,
TW) ; Tsai, Jing-Cherng; (Hsinchu, TW) ; Chen,
Joung-Yei; (Hsinchu, TW) ; Chao, Wee-Pin;
(Hsinchu, TW) ; Wang, Bor-Ping; (Hsinchu, TW)
; Chen, In-Mau; (Hsinchu, TW) ; Chou,
Huai-Mei; (Hisnchu, TW) |
Correspondence
Address: |
SUGHRUE, MION, ZINN, MACPEAK & SEAS, PLLC
2100 Pennsylvania Avenue, N.W.
Washington
DC
20037-3213
US
|
Family ID: |
26666565 |
Appl. No.: |
09/750048 |
Filed: |
December 29, 2000 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
09750048 |
Dec 29, 2000 |
|
|
|
09211049 |
Dec 15, 1998 |
|
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|
Current U.S.
Class: |
525/333.3 ;
525/333.4; 525/333.5; 525/333.6; 525/360; 525/385; 525/386;
526/347 |
Current CPC
Class: |
C08F 257/02 20130101;
C08L 51/003 20130101 |
Class at
Publication: |
525/333.3 ;
525/333.4; 525/333.5; 525/333.6; 525/360; 525/385; 525/386;
526/347 |
International
Class: |
C08F 257/02; C08F
212/08 |
Claims
What is claimed is:
1. A graft copolymer of a syndiotactic styrene/para-alkylstyrene
copolymer, having the formula of 9wherein R.sup.1 and R.sup.2 are
independently selected from the group consisting of hydrogen,
alkyl, and primary and secondary haloalkyl, X is a functional group
selected from a group containing halogen, oxygen, sulfur, silicon,
nitrogen, carbon, phosphorus, and mixtures thereof, Y is an atactic
polymer moiety, a ranges from 10 to 30000, b ranges from 0 to
30000, c ranges from 0 to 30000, and d ranges from 1 to 30000.
2. The graft copolymer as claimed in claim 1, wherein X is a
halogen.
3. The graft copolymer as claimed in claim 1, wherein X is an
alkali or alkaline earth metal.
4. The graft copolymer as claimed in claim 1, wherein X is selected
from the group consisting of alkoxides, phenoxides and
carboxylates.
5. The graft copolymer as claimed in claim 1, wherein X is selected
from the group consisting of thiolates, thiophenolates, thioethers,
thiocarboxylates, dithiocarboxylates, thioureas, dithiocarbamates,
xanthates and thiocyanates.
6. The graft copolymer as claimed in claim 1, wherein X is selected
from the group consisting of silanes and halosilanes.
7. The graft copolymer as claimed in claim 1, wherein X is selected
from the group consisting of malonates, cyanides, and
CR.sup.3.sub.3, wherein each R.sup.3 is an organic radical.
8. The graft copolymer as claimed in claim 1, wherein X is selected
from the group consisting of amides, amines, carbazoles,
phthalimides, pyridines, maleimides and cyanates.
9. The graft copolymer as claimed in claim 1, wherein X is a
phosphine.
10. The graft copolymer as claimed in claim 1, wherein R.sup.1 and
R.sup.2 are independently selected from the group consisting of
hydrogen, C.sub.1 to C .sub.5 alkyl, and C.sub.1 to C.sub.5 primary
and secondary haloalkyl.
11. The graft copolymer as claimed in claim 1, which is obtained
from polymerization in the presence of a metallocene as a
catalyst.
12. The graft copolymer as claimed in claim 1, wherein said
copolymer has a number average molecular weight of at least about
1000.
13. The graft copolymer as claimed in claim 1, wherein Y is
selected from the group consisting of polymers and copolymers of
anionically polymerizable monomers, cationically polymerizable
monomers, anionically and cationically ring-openable monomers, and
free radical polymerizable monomers.
14. The graft copolymer as claimed in claim 1, wherein Y is a
polymer of anionically polymerizable monomers.
15. The graft copolymer as claimed in claim 14, wherein the
anionically polymerizable monomer is selected from the group
consisting of conjugated dienes, vinyl aromatic compounds, vinyl
unsaturated amides, acenaphthylene, 9-acrylcarbazole,
acrylonitrile, methacrylonitrile, organic isocyanates, acrylates,
methacrylates, alkyl acrylates, alkyl methacrylates, glycidyl
methacrylates, vinyl pyridines, and mixtures thereof.
16. The graft copolymer as claimed in claim 13, wherein the
cationically polymerizable monomer is selected from the group
consisting of vinyl aromatic compounds, vinyl ethers,
N-vinylcarbazole, isobutene, and mixtures thereof.
17. The graft copolymer as claimed in claim 13, wherein the
ring-openable monomer is selected from the group consisting of
cyclic ethers, sulfides, lactones, lactams, N-carboxyanhydrides,
cyclic anhydrides, and mixtures thereof.
18. The graft copolymer as claimed in claim 13, wherein the free
radical polymerizable monomer is selected from the group consisting
of vinyl aromatic compounds, conjugated dienes, acrylates,
methacrylates, alkyl acrylates, alkyl methacrylates, vinyl
acetates, and mixtures thereof.
Description
BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention:
[0002] The present invention relates to a graft copolymer of a
syndiotactic styrene/para-alkylstyrene copolymer.
[0003] 2. Description of the Prior Art:
[0004] Syndiotactic polystyrene (sPS) is very useful in many
commercial applications. However, it suffers from a major
deficiency: poor adhesion to other materials (for example, to the
copper of PC boards). In addition, sPS has poor compatibility with
other functional polymers. Therefore, there is a need to improve
the physical properties of the conventional syndiotactic
polystyrene.
[0005] Chung et al. in U.S. Pat. No. 5,543,484 have disclosed a
functionalized .alpha.-olefin/para-alkylstyrene copolymer. First,
.alpha.-olefin and para-alkylstyrene are copolymerized. The
incorporation of p-alkylstyrene into the .alpha.-olefin polymer
results in the generation of benzylic protons, which are readily
available for many chemical reactions, thereby introducing
functional groups at the benzylic position under mild reaction
conditions. Then, the olefin/p-alkylstyrene copolymer is
functionalized by the functionalization of benzylic protons in
p-alkylstyrene units. Such functionalization leads to improvement
in the physical properties of the original olefin polymers.
[0006] Powers et al. in U.S. Pat. No. 5,548,029 has disclosed graft
copolymers of para-alkylstyrene/isoolefin. In a similar manner,
isoolefin and para-alkylstyrene are copolymerized, and then the
p-alkylstyrene/isoolefin copolymer is functionalized by the
functionalization of benzylic protons in p-alkylstyrene units. By
such functionalization, the physical properties of the isoolefin
polymer can be improved.
[0007] In Powers et al., to improve compatibility of the
isoolefin/p-alkylstyrene copolymer with other polymers (for
example, with thermoplastic polymers), grafting technique can also
be used. That is, a thermoplastic polymer moiety is grafted onto
the functional copolymer. Moreover, such a graft copolymer can also
serve as a compatibilizer to compatibilize polymer blends.
[0008] To date, no one has ever provided a graft copolymer of
syndiotactic styrene/para-alkylstyrene copolymers.
SUMMARY OF THE INVENTION
[0009] The object of the present invention is to solve the
above-mentioned problems and to provide a graft copolymer of a
syndiotactic styrene/para-alkylstyrene copolymer. The compatibility
of the graft copolymer of syndiotactic styrene/para-alkylstyrene
copolymer of the present invention with other polymers is improved
over a syndiotactic styrene polymer. Moreover, the graft copolymer
of a syndiotactic styrene/para-alkylstyrene copolymer of the
present invention can serve as a compatibilizer for a polymer blend
so as to improve the compatibility of the polymer blend with other
polymers, and increase the impact resistance and elongation of the
polymer blend, while the physical properties of the original
polymers in the polymer blend can still be maintained.
[0010] To achieve the above-mentioned object, the graft copolymer
of a syndiotactic styrene/para-alkylstyrene copolymer of the
present invention has the formula of 2
[0011] wherein
[0012] R.sup.1 and R.sup.2 are independently selected from the
group consisting of hydrogen, alkyl, and primary and secondary
haloalkyl,
[0013] X is a functional group selected from a group containing
halogen, oxygen, sulfur, silicon, nitrogen, carbon, phosphorus, and
mixtures thereof,
[0014] Y is an atactic polymer moiety,
[0015] a ranges from 10 to 30000,
[0016] b ranges from 0 to 30000,
[0017] c ranges from 0 to 30000, and
[0018] d ranges from 1 to 30000.
DETAILED DESCRIPTION OF THE INVENTION
[0019] The present invention is the first time a graft-from
copolymer of a syndiotactic styrene/para-alkylstyrene copolymer has
been successfully provided.
[0020] The graft-from copolymer of a syndiotactic
styrene/para-alkylstyren- e copolymer has the formula of 3
[0021] wherein R.sup.1 and R.sup.2 are independently selected from
the group consisting of hydrogen, alkyl, and primary and secondary
haloalkyl.
[0022] X is a functional group selected from a group containing
halogen, oxygen, sulfur, silicon, nitrogen, carbon, phosphorus, and
mixtures thereof. Preferably, R.sup.1 and R.sup.2 are independently
selected from the group consisting of hydrogen, C.sub.1 to C.sub.5
alkyl, and C.sub.1 to C.sub.5, primary and secondary haloalkyl.
[0023] Y is an atactic polymer moiety.
[0024] a ranges from 10 to 30000, b ranges from 0 to 30000, c
ranges from 0 to 30000, and d ranges from 1 to 30000.
[0025] Preferably, the copolymer has a number average molecular
weight of at least 1000.
[0026] The general process for preparing the graft copolymer of a
syndiotactic styrene/para-alkylstyrene copolymer of the present
invention will be described below.
[0027] The grafting techniques can be classified into "graft-from"
and "graft-on". Graft-from technique involves the reaction of a
syndiotactic styrene/p-alkylstyrene copolymer and a monomer via
anionic polymerization, cationic polymerization, anionic or
cationic ring-open polymerization, or free radical polymerization.
A "graft-from" anionic polymerization is as follows: 4
[0028] The reaction of a functionalized (such as brominated)
syndiotactic styrene/p-alkylstyrene with a monomer via cationic
polymerization is as follows: 5
[0029] The reaction of a functionalized (such as brominated)
syndiotactic styrene/p-alkylstyrene with a monomer via free radical
polymerization is as follows: 6
[0030] The "graft-on" technique involves the reaction of a
functionalized syndiotactic styrene/p-alkylstyrene copolymer and a
polymer which can react with the functional group of such a
functionalized syndiotactic styrene/p-alkylstyrene copolymer, such
that the polymer bonds to the functionalized syndiotactic
styrene/p-alkylstyrene copolymer and grafting is achieved.
[0031] Therefore, Y in formula (I) is selected from the group
consisting of polymers and copolymers of anionically polymerizable
monomers, cationically polymerizable monomers, anionically and
cationically ring-openable monomers, and free radical polymerizable
monomers.
[0032] Representative examples of the anionically polymerizable
monomers include conjugated dienes, vinyl aromatic compounds, vinyl
unsaturated amides, acenaphthylene, 9-acrylcarbazole,
acrylonitrile, methacrylonitrile, organic isocyanates, acrylates,
methacrylates, alkyl acrylates, alkyl methacrylates, glycidyl
methacrylates, vinyl pyridines, and mixtures thereof.
[0033] Representative examples of the cationically polymerizable
monomers include vinyl aromatic compounds, vinyl ethers,
N-vinylcarbazole, isobutene, and mixtures thereof.
[0034] Representative examples of the ring-openable monomers
include cyclic ethers, sulfides, lactones, lactams,
N-carboxyanhydrides, cyclic anhydrides, and mixtures thereof.
[0035] Representative examples of the free radical polymerizable
monomers include vinyl aromatic compounds, conjugated dienes,
acrylates, methacrylates, alkyl acrylates, alkyl methacrylates,
vinyl acetates, and mixtures thereof.
[0036] As a result, after further grafting (e.g., graft-from or
graft-on), the syndiotactic styrene/para-alkylstryene copolymer of
the present invention has a grafted side chain (Y) that is an
atactic polymer, rather than a syndiotatic polymer.
[0037] The general process for preparing the functionalized
syndiotactic styrene/para-alkylstyrene copolymer of the present
invention will be described below.
[0038] We take the reaction of styrene and para-methylstyrene
monomers as an example. First, the two monomers are copolymerized
by using a metallocene as a catalyst. The catalyst system may also
include an activating cocatalyst such as methyl aluminoxane (MAO).
7
[0039] wherein each x and y is the molar ratio of the respective
monomer and x+y=100.
[0040] Suitable metallocene catalysts have a delocalized
.pi.-bonded moiety with a constrained geometry. The catalysts may
be further described as a metal coordination complex comprising a
metal of Groups IVB-VIB of the Periodic Table of the elements and a
delocalized .pi.-bonded moiety with a constrained geometry. Some of
them have been taught in U.S. Pat. Nos. 4,542,199; 4,530,914;
4,665,047; 4,752,597; 5,026,798; and 5,272,236. Preferred catalyst
complexes include zirconocene and titanocene coordination compounds
with single or double cyclopentadienyl derivatives which form the
constrained ligand geometry.
[0041] The activating cocatalyst can be methyl aluminoxane (MAO), a
trialkyl aluminum, a dialkyl aluminum, a salt of an inert and
non-coordinating anion, or a mixture thereof.
[0042] The trialkyl aluminum can be selected from the group
consisting of trimethyl aluminum, triethyl aluminum, tripropyl
aluminum, trisopropyl aluminum, tributyl aluminum, and triisobutyl
aluminum (TIBA).
[0043] The inert and non-coordinating anion can be a borate.
Borates that are suitable for use in the present invention include
N,N-dimethyl anilinium tetrakis(pentafluorophenyl)borate, triphenyl
carbenium tetrakis(pentafluorophenyl)borate, trimethyl ammnonium
tetrakis(pentafluorophenyl)borate, ferrocenium
tetrakis(pentafluorophenyl- )borate, dimethyl ferrocenium
tetrakis(pentafluorophenyl)borate, and silver
tetrakis(pentafluorophenyl)borate.
[0044] Preferably, the activating cocatalyst is methyl aluminoxane,
or a mixture of a trialkyl aluminum and a borate.
[0045] Suitable diluents for the monomers, catalyst components and
polymeric reaction products include the general group of aliphatic
and aromatic hydrocarbons, used singly or in a mixture, such as
propane, butane, pentane, cyclopentane, hexane, toluene, heptane,
isooctane, etc.
[0046] In general, the polymerization reaction of the present
invention is carried out by mixing styrene and p-methylstyrene in
the presence of the catalyst and diluent in a copolymerization
reactor, with thorough mixing at a temperature between 0.degree. C.
to 100.degree. C. The polymerization may be carried out in an inert
gas atmosphere and the substantial absence of moisture.
[0047] The advantage of the styrene/p-methylstyrene is that the
benzylic protons in the p-methylstyrene unit can be easily
converted to various functional groups, such as --COOH, --OH,
--NH.sub.2, -Cl, --Br, --M, COOM (M=metal, e.g. Li, Na, K and Ca),
under mild reaction conditions. Most functionalization reactions of
benzylic protons in organic compounds can be applied to those of
benzylic protons in p-methylstyrene.
[0048] The following equations, involving (but not limited to)
bromination and carboxylation reactions of the syndiotactic
styrene/p-methylstyrene copolymer are used to illustrate the
functionalization reactions of benzylic protons in the syndiotactic
styrene/p-methylstyrene copolymer. 8
[0049] Among the functionalization reactions of the benzylic
protons in the syndiotactic styrene/p-alkylstyrene copolymer,
halogenation and metallation are the most important. The
halogenation reaction results in a benzylic halogen, which
constitutes a very active electrophile that can be converted to
various functionalities via nucleophilic substitution reactions.
The metallation reaction results in a benzylic anion in the
p-alkylstyrene unit, which can be converted to many other
functionalities. In fact, halogenated and metallated syndiotactic
styrene/p-alkylstyrene copolymers significantly broaden the scope
of achievable function groups to include allmost all the desirable
organic functional groups.
[0050] Therefore, via the direct reaction of the unfunctionalized
syndiotactic styrene/p-alkylstyrene, or via the reaction of the
halogenated or metallated syndiotactic styrene/p-alkylstyrene, the
functional group X on formula (I) may be a group containing
halogen, metal, oxygen, sulfur, silicon, nitrogen, carbon,
phosphorus, or combinations thereof. The functional groups X on the
benzylic position have been taught in U.S. Pat. Nos. 5,543,484
(Chung, et al.); 5,548,029 (Powers et al.); and 5,162,445 (Powers,
et al.)
[0051] Representative examples of the functional group X containing
a metal include alkali and alkaline earth metals.
[0052] Examples of the functional group X containing oxygen, which
results in attachment of --0-- to the benzylic position from which
the halide ion is displaced, include alkoxides, phenoxides and
carboxylates.
[0053] Examples of the functional group X containing sulfur, which
results in attachment of --S-- to the benzylic position from which
the halide ion is displaced, include thiolates, thiophenolates,
thioethers, thiocarboxylates, dithiocarboxylates, thioureas,
dithiocarbamates, xanthates and thiocyanates.
[0054] Examples of the functional group X containing silicon, which
results in attachment of --Si--to the benzylic position from which
the halide ion is displaced, include silanes and halosilanes.
[0055] Examples of the functional group X containing carbon, which
results in attachment of --C-- to the benzylic position from which
the halide ion is displaced, include malonates, cyanides, and
CR.sup.3.sub.3 wherein each R.sup.3 is an organic group.
[0056] Examples of the functional group X containing nitrogen,
which results in attachment of --N-- to the benzylic position from
which the halide ion is displaced, include amides, amines,
carbazoles, phthalimides, pyridine, maleimide and cyanates.
[0057] Examples of the functional group X containing phosphorus,
which results in attachment of --P-- to the benzylic position from
which the halide ion is displaced, include phosphines.
[0058] The following examples are intended to illustrate the
process and advantages of the present invention more fully without
limiting its scope, since numerous modifications and variations
will be apparent to those skilled in the art.
Synthesis of Syndiotactic Poly(styrene-co-p-alkylstyrene)
EXAMPLE 1:
Synthesis of syndiotactic poly(styrene-co-p-methylstyrene)
[0059] 35 mL of the purified para-methylstyrene monomer
(hereinafter referred to as "pMS") and 315 mL of the purified
styrene monomer (hereinafter referred to as "SM") were charged in 1
L metal reaction vessel under nitrogen. Then, 2.8 mL of 10 wt %
methyl aluminoxane (MAO) was charged in the reaction vessel. The
reaction vessel was heated to 70.degree. C., then, 0.0208 mmol of
pentamethylcyclopentadienyl dimethoxy titanium (III)
[Cp*Ti(OMe).sub.2] was added. The reaction proceeded for 60 minutes
and was terminated by adding a sodium hydroxide/methanol solution.
The copolymer was isolated by the Soxhlet extraction method with
methanol for 24 hours. The product was 86 g. The composition,
melting point, and molecular weight of the copolymer were
determined by .sup.1H NMR, differential scanning calorimetry (DSC),
and gel permeation chromatography (GPC), respectively. The
copolymer contained about 12 mol % of pMS. The melting point was
239.degree. C. GPC results indicated a weight average molecular
weight (Mw) of 1,526,000, a number average molecular weight (Mn) of
741,000, and a molecular weight distribution of 2.06. The other
properties of the resulting copolymer are set forth in Table 1.
EXAMPLE b 2
[0060] The procedures as described in Example 1 were employed
except that the amounts of the catalyst and MAO added were changed.
The results are shown in Table 1.
EXAMPLE 3
[0061] The procedures as described in Example 1 were employed
except that the pentamethylcyclopentadienyl dimethoxy titanium
(III) [Cp*Ti(OMe).sub.2] catalyst was replaced by the catalyst
system used in U.S. Pat. No. 5,644,009. The results are shown in
Table 1.
EXAMPLE 4-6
[0062] The procedures as described in Example 3 were employed
except that the reaction was conducted in a 1 L glass reaction
vessel, and a hydrogen gas with a pressure of 0.1 kg/cm.sup.2G was
introduced into the vessel. The results are shown in Table 1.
EXAMPLE 7
[0063] The procedures as described in Example 1 were employed
except that the reaction was conducted in a 100 L reaction vessel,
and the amount of the reactants was changed. The results are shown
in Table 1.
EXAMPLE 8
[0064] The procedures as described in Example 1 were employed
except that a hydrogen gas with a pressure of 0.4 kg/cm.sup.2G was
introduced into the vessel. The results are shown in Table 1.
1TABLE 1 Reaction Melting pMS content in Catalyst MAO Time Point
the copolymer Example SM pMS (mmol) (ml) (min) (.degree. C.) Mw
Mw/Mn (mol %) 1 315 ml 35 ml 0.0208 2.8 60 239 1.53 .times.
10.sup.6 2.06 12 2 315 ml 35 ml 0.0384 6.2 60 232 3.4 .times.
10.sup.5 1.87 17 3 295 ml 5 ml 0.019 3.2 270 259 1.2 .times.
10.sup.5 6.1 5 4 397 ml 3 ml 0.0208 8.4 30 271 7.8 .times. 10.sup.5
1.68 1 5 315 ml 35 ml 0.0384 6.2 40 236 2.4 .times. 10.sup.5 9.32
15 6 200 ml 200 ml 0.0416 9.0 300 -- 1.12 .times. 10.sup.5 2.93 58
7 45 L 5 L 1.8 500 120 235 9.4 .times. 10.sup.5 2.04 7 8* 300 ml 33
ml 0.008 1.5 30 242.8 1.57 .times. 10.sup.5 2.4 10 *1.5 mL of 22 wt
% TIBA was used
Functionalization of Syndiotactic
Poly(styrene-co-p-alkystyrene)
EXAMPLE 9
Oxidation of syndiotactic poly(styrene-co-p-methylstyrene)
(sPS-pMS)
[0065] 20 g of the syndiotactic poly(styrene-co-p-methylstyrene)
(sPS-pMS) obtained from Example 2 was dissolved in 600 mL of
o-dichlorobenzene (ODCB) under an oil bath at 120.degree. C. 300 mL
of acetic acid was gradually added into the solution and the
reaction mixture was cooled to about 100.degree. C. After that, 20
mole % of cobalt (III) acetate tetrahydrate and 60 mole % of sodium
bromide, based on the pMS content of sPS-pMS, were added, and
oxygen was bubbled through at a rate of 1 L/min for 2 hours. After
cooling, the reaction was terminated with methanol, filtered,
washed with a hot water/methanol mixture twice, washed with
methanol twice, and extracted with methanol by the Soxhlet
extraction method for 20 hours. Both --CHO and --COOH groups were
observed by .sup.1H NMR spectrum. The results are shown in Table 2.
Total oxidation indicates the mole % of the oxidized functional
group based on the moles of the original polymer (sPS-pMS). PDI
refers to the polydispersity index.
EXAMPLES 10 and 11
[0066] The same procedures described in Example 9 were employed,
except that the amounts of the catalyst and sodium bromide added
were changed, and the reaction time was changed. The results are
shown in Table 2.
EXAMPLES 12 and 13
[0067] The same procedures described in Example 9 were employed
except that 20 g of syndiotatic poly(styrene-co-p-methylstyrene)
obtained from Example 7 was used, and the reaction time was changed
to control molecular weight. The results are shown in Table 2.
2TABLE 2 Co:NaBr Total Reaction (mole % of oxidation Tm Tg Example
Time pMS) (%) Mn PDI (.degree. C.) (.degree. C.) 9 2 hr 20:60 9.27
16000 2.29 185.28 98.74 10 1 hr 50 m 10:40 3.61 45000 2.28 225.82
96.92 11 1.5 hr 10:40 3.32 58000 1.98 223.45 95.26 12 3.0 hr 20:40
6.20 43000 1.76 228.0 93.67 13 1.5 hr 20:40 6.15 289000 2.32 235.5
93.22
EXAMPLE 14:
Bromination of syndiotactic poly(styrene-co-p-methylstyrene)
[0068] 35.9 g of syndiotactic poly(styrene-co-p-methylstyrene)
obtained from Example 6 was charged in a round bottom flask that
was wrapped with aluminum foil. 450 mL of chloroform, 49.6 g of
N-bromosuccinimide (NBS), and 1.7 g of benzoyl peroxide (BPO) were
added, then the mixture was stirred in an oil bath under nitrogen
for 43 hours. The polymer solution was precipitated by isopropanol,
and then washed with water and isopropanol. The brominated polymer
was dried under vacuum at 60.degree. C. and 49.3 g was obtained.
From .sup.1H NMR spectrum, it was observed that 75% of the chemical
shift of para--CH.sub.3 was converted to 4.4 ppm, the chemical
shift of --CH.sub.2Br.
EXAMPLE 15:
Bromination of syndiotactic poly(styrene-co-p-methylstyrene)
[0069] 2.5 g of syndiotactic poly(styrene-co-p-methylstyrene)
obtained from Example 2 was dissolved with 200 mL of
C.sub.6H.sub.5Cl in an oil bath at 120.degree. C. to ensure
complete dissolution. The solution was cooled to 75.degree. C., and
1 mL of 10% bromine in C.sub.6H.sub.5Cl under dark was added to the
round bottom flask charged with the polymer solution over a period
of 20 minutes. During the reaction, the flask was illuminated by a
90 W light bulb, and the bromine added was equal to 50% of the
content of the para--CH.sub.3. Subsequently, the polymer solution
was precipitated by methanol, and then washed with water and
methanol. The brominated polymer was dried under vacuum at
60.degree. C. and 2.58 g was obtained. From the .sup.1H NMR
spectrum, it was observed that about 43% of the chemical shift of
the para--CH.sub.3 was converted to 4.4 ppm, the chemical shift of
---CH.sub.2Br.
EXAMPLE 16:
Carboxylation of syndiotactic poly(styrene-co-p-methylstyrene)
[0070] 3 g of dried syndiotactic poly(styrene-co-p-methylstyrene)
obtained from Example 6 was added in 100 mL of purified and dried
cyclohexane under nitrogen at 60.degree. C. for dissolution. The
polymer solution was cooled to 0.degree. C., and a brownish red
solution of 10.4 mL of s-BuLi (1.3 M) and 4.1 mL of
tetramethylethylenediamine (TMEDA) was added. The reaction was
conducted at 60.degree. C. for 3 hours, and then cooled to room
temperature. 150 mL of THF saturated by CO.sub.2 was added, and the
bubbling of CO.sub.2 through the reaction mixture was continued for
1.5 hour for carboxylation. The reaction was terminated by
methanol, and the carboxylated polymer was precipitated by
methanol. The resulting polymer was re-dissolved with THF,
precipitated by IPA (isopropyl alcohol) and then dried. FT-IR
spectrum shows strong absorption of carboxyl group (C=O) at 1718
cm.sup.-1. From the DSC curve, it was found that the glass
transition temperature (Tg) was increased by 5.5.degree. C.
EXAMPLE17:
Silylation of syndiotactic poly(styrene-co-p-methylstyrene)
[0071] 0.5 g of the carboxylated polymer obtained from Example 15
was dissolved with 50 mL of THF. Then, 1 mL of (CH.sub.3).sub.3SiCl
and 0.5 mL of Et.sub.3N were added, and stirred under heating for
30 minutes. The reaction solution was precipitated by methanol. The
polymer was isolated by filtering, washing with methanol, and
drying. From the .sup.1H NMR spectrum, the chemical shift of the
--Si(CH.sub.3).sub.3 at 0.09 ppm was observed.
Preparation of Graft Copolymers
EXAMPLE 18:
Preparation of syndiotactic
poly(styrene-co-p-methylstyrene)-g-polystyrene
(sPS-pMS-g-polystyrene)
[0072] 1.04 g of syndiotactic
poly(styrene-co-p-methylstyrene)(sPS-pMS) obtained from Example 8
(containing 10 mol % of syndiotactic polystyrene) was charged in a
300 ml round-bottom flask and dissolved with 150 mL of the purified
and dried cyclohexane. Then, 30 mL of cyclohexane was removed by
distillation. 1.5 mL of TMEDA (tetramethylethylene diamine) and 3.8
mL of sec-butyl lithium (1.3 M in cyclohexane) were mixed and then
the dark brown solution was added to the sPS-pMS/cyclohexane
solution. The mixed solution was continuously stirred at 35.degree.
C. for 20 hours. The round-bottom flask was moved into the glove
box, and the reaction mixture was washed with n-pentane repeatedly,
filtered, and dried under reduced pressure. 100 mL of n-pentane was
added to the residue and the round-bottom flask was removed from
the glove box. 10 mL of the purified styrene was added to the flask
and stirred at room temperature for 30 minutes. A large quantity of
methanol was added to terminate the reaction. The resulting polymer
was filtered, collected, and extracted with methyl ethyl ketone
(MEK) at room temperature. The soluble and insoluble polymer
fractions were separated by centrifuge and dried under reduced
pressure to afford 6.2 g of sPS-pMS-g-polystyrene (insoluble in
MEK) and 3.3 g of homopolymer of styrene (soluble in MEK).
EXAMPLE 19:
Preparation of syndiotactic
poly(styrene-co-p-methylstyrene)-g-polybutadie- ne
(sPS-pMS-g-polybutadiene)
[0073] 2.0 g of syndiotactic
poly(styrene-co-p-methylstyrene)(sPS-pMS) obtained from Example 3
(containing 5 mol % of syndiotactic polystyrene) was charged in a
300 ml round-bottom flask and dissolved with 150 mL of the purified
and dried cyclohexane. Then, 50 mL of cyclohexane was removed by
distillation. 1.5 mL of TMEDA and 3.8 mL of sec-butyl lithium (1.3
M in cyclohexane) were mixed and then the dark brown solution was
added to the sPS-pMS/cyclohexane solution. The mixed solution was
continuously stirred at 55.degree. C. for 20 hours. The
round-bottom flask was moved into the glove box, and the reaction
mixture was washed with n-pentane repeatedly, filtered, and dried
under reduced pressure. 100 mL of n-pentane was added to the
residue and the round-bottom flask was removed from the glove box.
4.0 g of the purified 1,3-butadiene was added to the flask and
stirred at room temperature for 6 hours. The reaction was
terminated by methanol, and then a large quantity of methanol was
added to precipitate the polymer. The resulting polymer was
filtered, collected, and extracted with n-pentane at room
temperature. The soluble and insoluble polymer fractions were
separated by centrifuge and dried under reduced pressure to afford
3.08 g of sPS-pMS-g-polybutadiene (insoluble in n-pentane) and 1.83
g of homopolymer of butadiene (soluble in n-pentane). The .sup.1H
NMR analysis indicated that the sPS-pMS-g-polybutadiene contained
50.7 mol % of 1,3-butadiene.
EXAMPLE 20:
Preparation of syndiotactic
poly(styrene-co-p-methylstyrene)-g-polymethylm- ethyacrylate
(sPS-pMS-g-PMMA)
[0074] 2.0 g of syndiotactic
poly(styrene-co-p-methylstyrene)(sPS-pMS) obtained from Example 3
(containing 5 mol % of syndiotactic polystyrene) was charged in a
300 ml round-bottom flask and dissolved with 150 mL of the purified
and dried cyclohexane. Then, 50 mL of cyclohexane was removed by
distillation. 1.1 mL of TMEDA and 2.9 mL of sec-butyl lithium (1.3
M in cyclohexane) were mixed and then the dark brown solution was
added to the sPS-pMS/cyclohexane solution. The mixed solution was
continuously stirred at 55.degree. C. for 20 hours. The
round-bottom flask was moved into the glove box, and the reaction
mixture was washed with n-pentane repeatedly, filtered, and dried
under reduced pressure. 100 mL of n-pentane was added to the
residue and the round-bottom flask was removed from the glove box.
8 mL of the purified methyl methacrylate was added to the flask and
stirred at room temperature for 5 hours. A large quantity of
methanol was added to terminate the reaction. The resulting polymer
was precipitated, filtered, collected, and extracted with acetone
at room temperature. The soluble and insoluble polymer fractions
were separated by centrifuge and dried under reduced pressure to
afford 2.2 g of sPS-pMS-g-PMMA (insoluble in acetone) and 0.3 g of
homopolymer of methyl methacrylate (soluble in acetone). The
.sup.1H NMR analysis indicated that the sPS-pMS-g-PMMA contained
10.1 mol % of PMMA.
EXAMPLE 21:
Preparation of syndiotactic
poly(styrene-co-p-methylstyrene)-g-polyisopren- e
(sPS-pMS-g-polyisoprene)
[0075] 0.7 g of syndiotactic
poly(styrene-co-p-methylstyrene)(sPS-pMS) obtained from Example 6
(containing 15 mol % of syndiotactic polystyrene) was charged in a
300 ml round-bottom flask and dissolved with 150 mL of the purified
and dried cyclohexane. Then, 50 mL of cyclohexane was removed by
distillation. 2.4 mL of TMEDA and 5 mL of sec-butyl lithium (1.3 M
in cyclohexane) were mixed and then the dark brown solution was
added to the sPS-pMS/cyclohexane solution. The mixed solution was
continuously stirred at 75.degree. C. for 20 hours. The
round-bottom flask was moved into the glove box, and the reaction
mixture was washed with n-pentane repeatedly, filtered, and dried
under reduced pressure. 100 mL of n-pentane was added to the
residue and the round-bottom flask was removed from the glove box.
4 g of the purified isoprene was added to the flask and stirred at
room temperature for 48 hours. A large quantity of methanol was
added to terminate the reaction. The resulting polymer was
precipitated, filtered, collected, and extracted with n-pentane at
room temperature. The soluble and insoluble polymer fractions were
separated by centrifuge and dried under reduced pressure to afford
sPS-pMS-g-polyisoprene (insoluble in n-pentane) and a homopolymer
of isoprene (soluble in n-pentane). The high temperature gel
permeation chromatography (Waters GPC 150CV) showed that the
starting polymer (sPS-pMS) had a Mw of 240,600 and PDI of 9.3, and
the resulting polymer (sPS-pMS-g-polyisoprene) had a Mw of 556,400
and PDI of 8.1.
EXAMPLE 22:
Preparation of syndiotactic
poly(styrene-co-p-methylstyrene)-g-poly(t-buty- lmethacrylate)
(sPS-pMS-g-PtBMA)
[0076] 1.0 g of syndiotactic
poly(styrene-co-p-methylstyrene)(sPS-pMS) obtained from Example 8
was charged in a 250 ml round-bottom flask and dissolved with 50 mL
of the purified and dried cyclohexane. 1.4 mL of TMEDA and 1.1 mL
of n-butyl lithium (2.5 M in hexane) were mixed and then the mixed
solution was added to the sPS-pMS/cyclohexane solution. The mixed
solution was continuously stirred at 60.degree. C. for 4 hours. The
round-bottom flask was moved into the glove box, and the reaction
mixture was washed with n-pentane repeatedly, filtered, and dried
under reduced pressure. 20 mL of n-pentane and 1.0 g of
t-butylmethacrylate were added to the residue and the round-bottom
flask was removed from the glove box. The mixture was stirred at
room temperature for 48 hours. 10 mL of methanol was added to
terminate the reaction. The resulting polymer was precipitated,
filtered, collected, and extracted with acetone at room
temperature. The soluble and insoluble polymer fractions were
separated by centrifuge and dried under reduced pressure to afford
1.163 g of sPS-pMS-g-PtBMA (insoluble in acetone) and 0.158 g of a
homopolymer of PtBMA (soluble in acetone). The FT-IR spectrum
showed that sPS-pMS-g-PtBMA had absorption of carboxyl group (C=O)
at 1725 cm.sup.-1. The .sup.1H NMR analysis indicated that the
sPS-pMS-g-PtBMA contained 9.3 mol % of PtBMA.
EXAMPLE 23:
Preparation of syndiotactic
poly(styrene-co-p-methylstyrene)-g-poly(tetrah- ydrofuran)
(sPS-pMS-g-PTHF)
[0077] 1.0 g of sPS-pMS-Br (containing 2 mol % of bormine) was
charged in a 250 ml vessel and dissolved with 15 mL of the purified
and dried THF (tetrahydrofuran), then the mixture was cooled to
-15.degree. C. to -20.degree. C. In a glove box, 5 mL of THF and
8.76 mg of anhydrous silver tetrafluoroborate (AgBF.sub.4) was
mixed and was immediately removed from the glove box. The
AgBF.sub.4 solution was cooled by liquid nitrogen to -30.degree. C.
to -40.degree. C. and then sPS-pMS-Br/THF was added. The mixture
was stirred at -15.degree. C. to -20.degree. C. for 20 minutes, and
then stirred at -3.degree. C. for 24 hours. 3 mL of methanol was
added to terminate the reaction. The resulting polymer was
precipitated, filtered, collected, and extracted with ethanol at
room temperature. The soluble and insoluble polymer fractions were
separated by centrifuge and dried under reduced pressure to afford
2.34 g of sPS-pMS-g-PTHF (insoluble in ethanol) and a homopolymer
of PTHF (soluble in ethanol). The FT-IR analysis showed that the
sPS-pMS-g-PTHF had absorption of ether (--C--O--C--) at 1112
cm.sup.-1.
[0078] The foregoing description of the preferred embodiments of
this invention has been presented for purposes of illustration and
description. Obvious modifications or variations are possible in
light of the above teaching. The embodiments were chosen and
described to provide the best illustration of the principles of
this invention and its practical application to thereby enable
those skilled in the art to utilize the invention in various
embodiments and with various modifications as are suited to the
particular use contemplated. All such modifications and variations
are within the scope of the present invention as determined by the
appended claims when interpreted in accordance with the breadth to
which they are fairly, legally, and equitably entitled.
* * * * *