Note: Descriptions are shown in the official language in which they were submitted.
13~)58~5
PROCESS FOR PRODUCTION OF STYRENE POLYMERS
/ BACKGROUND OF THE INVENTION
-
The present invention relates to a process for production
of styrene polymers and more particularly to a process for
producing styrene polymers in which polymer side chains are
mainly in the syndiotactic configuration.
As is well known, substituted vinyl compound polymers
can be divided into three groups, atactic, isotactic and syn-
diotactic, depending on the configuration of substituents
(side chains) in the polymers. A number of polymers having
O the isotactic and atactic configurations have been produced.
In connection with styrene polymers, it is known that
when usual radical polymerization initiators are used, almost
all of the styrene polymers formed are of the atactic
configuration although there can be obtained only a limited
~5~ number of styrene polymers rich in the syndiotactic configu-
ration, and that when Ziegler type catalysts are used, styrene
polymers having the isotactic configuration are obtained.
However, styrene polymers of high syndiotactic configuration
have not yet been produced by any conventionally used methods;
2~ that is, a method whereby styrene polymers of high syndiotactic
configuration can be obtained has not been known.
SUMMARY OF THE INVENTION
r
An object of the present invention is to provide a
process for producing styrene polymers in which polymer side
- 1 -- ~
~0~ 5
/ chains are mainly in the syndiotactic configuration.
It has been found that styrene polymers of high syn-
diotactic configuration can be obtained by polymerizing
styrene or its derivatives by the use of a catalyst compris-
ing specified transition metal compound and organoaluminum
compound components.
The present invention relates tc a process for producing
styrene polymers which comprises polymerizing styrene or
styrene derivatives by the use of a catalyst comprising:
~ (A) a titanium compound, and
(B) a contact product of an organoaluminum compound
and a condensation agent.
BRIEF DE~CRIPTION OF THE DRAWINGS_
Figs. l(a) to l(c) show aromatic ring Cl carbon signals
in 13C-NMR of the polymer obtained in Example 1, isotactic
polystyrene and atactic polystyrene, respectively;
Figs. 2(a) and 2(b) show X-ray diffraction patterns of
the polymer obtained in Example 1 and isotactic polystyrene,
respectively, wherein ~ indicates a Bragg angle ();
Figs. 3(a) and 3(b) show lH-NMRs of the polymer obtained
in Example 1 and isotactic polys yrene, respectively;
Fig. 4 shows an aromatic ring Cl carbon signal in 13C-NMR
of the polymer obtained in Example 35;
Figs. 5(a! and 5(b) show aromatic ring C1 carbon signals
2~ in C-NMR of the polymer obtained in Example 36 and atactic
poly(p-chlorostyrene), respectively; and
~.~0~25
/ Figs. 6, 7, 8 and 9 show aromatic ring C1 carbon
signals in 13C-NMR of the polymer obtained in Example 37,
the polymer obtained in Example 38, the polymer obtained in
Example 39 and the polymer obtained in Example 40, respectively.
DETAILED DESCRIPTION OF THE INVENTION
-
The catalyst which is used in the process of the present
invention contains as main components the following components
(A) and (B):
(A) a titanium compound, and
t~ (B) a contact product of an organoaluminum compound and
a condensation agent.
As the component (A), various titanium compounds can be
used. Preferred among these compounds are titanium compounds
and titanium chelate compounds represented by the following
general formulae (I) and (II):
General Formula (I)
TiRlaR2bR3cXl4-(a + b + c)
General Formula (II)
TiRldR2eXl3_(d + e)
2~ (wherein Rl, R2 and R3 each represent a hydrogen atom, an
alkyl group having 1 to 20 carbon atoms, an alkoxy group
having 1 to 20 carbon atoms, an aryl group having 6 to 20
carbon atoms, an alkylaryl group, an arylalkyl group, an
acyloxy group having 1 to 20 carbon atoms, a cyclopentadienyl
2~ group, a substituted cyclopentadienyl group or an indenyl
~3058~5
group, Xl represents a halogen atom, a, b and c each represent
an integer of 0 to 4, and d and e each represent an integer
of 0 to 3).
The symbols in the general formulae (I) and (II) are
described in detail.
Rl, R2 and R3 each represent a hydrogen atom, an alkyl
group having 1 to 20 carbon atoms (specifically a methyl
group, an ethyl group, a propyl group, a butyl group, an amyl
group, an isoamyl group, an isobutyl group, an octyl group
and a 2-ethylhexyl group), an alkoxy group having 1 to 20
carbon atoms (specifically a methoxy group, an ethoxy group,
a propoxy group, a butoxy group, an amyloxy group, a hexyloxy
group and a 2-ethylhexyloxy group), an aryl group having 6
to 20 carbon atoms, an alkylaryl group, an arylalkyl group
(specifically a phenyl group, a tolyl group, a xylyl group
and a benzyl group), an acyloxy group having 1 to 20 carbon
atoms (specifically a heptadecylcarbonyloxy group), a
cyclopentadienyl group, a substituted cyclopentadienyl
group (specifically a methylcyclopentadienyl group, a 1,2-
dimethylcyclopentadienyl group and a pentamethylcyclopenta-
dienyl group), or an indenyl group. These Rl, R2 and R3 may
be the same or different.
xl represents a halogen atom, such as chlorine,
bromine, iodine or fluorine r
~5 a, b and c each represent an integer of 0 to 4.
d and e each represent an integer of 0 to 3.
Representative examples of the tetravalent titanium
compounds and titanium chelate compounds represented by the
1305~
general formula (I) are methyltitanium trichloride, titanium
tetramethoxide, titanium tetraethoxide, titanium monoiSopropOXy
trichloride, titanium dilsopropoxy dichloride, titanium tri-
isopropoxy monochloride, tetra(2-ethylhexyloxy)titanium,
cyclopentadienyltitanium trichloride, biscyclopentadienyl
titanium dichloride, titanium tetrachloride, titanium tetra-
bromide, bis(2,4-pentanedionate)titanium oxide, bis(2,4-
pentanedionate)titanium dichloride, and bis(2,4-pentanedionate)-
titanium dibutoxide.
~O As the component (A), as ~ell as the above compounds,
condensed titanium compounds represented by the general
formula (III):
~ R4
- - Ti ~ t
R5 / m
(wherein R4 and R5 each represent a halogen atom, an alkoxy
group having 1 to 20 carbon atoms, or an acyloxy group having
1 to 20 carbon atoms, and m represents an integer of 2 to 20)
can be used.
The above titanium compounds may be used in the form
that they are adsorbed or deposited on a carrier, such as
magnesium compounds, silica and alumina, or in the form of
complexes with esters or ethers.
Typical examples of trivalent titanium compounds
represented by the general formula (II) to be used as the
component (A) are titanium trihalide such as titanium tri-
S chloride and cyclopentadienyl titanium compounds such ascyclopentadienyl titanium dichloride. In addition, trivalent
~.30~132S
,' titanium compounds resulting from reduction of tetravalent
titanium compounds can be used. These trivalent titanium
compounds can be used in the form of complexes with esters,
ehters and so forth.
The component (B) to be used in combination with the
component (A) is a contact product obtained by contacting
an organoaluminum compound with a condensation agent. Such
organoaluminum compounds include those represented by the
yeneral formula (IV):
~ C~ AlR63
~wherein R6 represents an alkyl group having 1 to 8 carbon
atoms). Representative examples of the organoaluminum com-
pounds represented by the general formula (IV) are trimethyl-
aluminum, triethylaluminum and triisobutylaluminum. Of these
compounds, trimethylaluminum is most preferred.
A typical example of the condensation agent to be
condensed with the above organoaluminum compound is water.
In addition, any compounds with which alkylaluminum undergoes
a condensation reaction can be used.
2~ Representative examples of the reaction product between
the alkylalumi~um compound and water, which is a typical
example of the component (B), are alkylaluminoxanes represented
by the general formula (V):
~ Al - O t n
R6
(wherein n=2 to 50). There are no special limitations to the
reaction between the organoaluminum compound and water; it
suffices that the organoaluminum compound and water are
-- 6 --
~30~32~5
J reacted by known techniques, such as (1) a method in which
the organoaluminum compound is previously dissolved in an
organic solvent, and then is contacted with water, (2) a
method in which the organoaluminum compound is previously
added at the time of polymerization, and then water is added,
and (3) a method in which water of crystallization contained
in metal salts and so forth, or water adsorbed on inorganic
or organic compounds is reacted.
In the process of the present invention, the component
,o (B) of the catalyst can be used alone. In addition, the
component (B) can be used as an admixture with organoaluminum
compounds (e.g., tnose represented by the general formula
(IV)) or other organometallic compounds, or in the state
that the component (B) is adsorbed or deposited on inorganic
substances and the like.
The catalyst to be used in the process of the present
invention contains the components (A) and (B) as main compo-
nents and, if desired, may further contain other catalytic
components. In use, the ratio of the component (A) to the
2c component (B) varies depending on conditions such as the
type of each component and the type of the starting material,
and thus cannot be determined unconditionally Usually the
components (A) and (B) are used in such a ratio that the
molar ratio of aluminum in the component (B) to titanium in
25~ the component (A), i.e., aluminum/titanium, is 1/1 to lx106/1,
with the range of 10/1 to lx104/1 being preferred.
The monomer to be poly~erized by the process of the
present invention is styrene or its derivatives. These
1305~
styrene derivatives include alkylstyrene such as methyl-
styrene, ethylstyrene, butylstyrene, p-tert-butylstyrene,
and dimethylstyrene, halogenated styrene such as chloro-
styrene, bromostyrene and fluorostyrene, halogen-substituted
alkylstyrene such as chloromethylstyrene, alkoxystyrene such
as methoxystyrene, carboxymethylstyrene, alkyletherstyrene,
alkylsilylstyrene, vinylbenzenesulfonic acid esters, and
vinylbenzyldialkoxy phosphide.
In accordance with the process of the present invention,
/o the above styrene or its derivative is polymerized in the
presence of a catalyst comprising the component (A) and (B)
as described above. This solution may be bulk polymerization
or solution polymerization using a solvent, e.g., aliphatic
hydrocarbons such as pentane, hexane and heptane, alicyclic
hydrocarbons such as cyclohexane, and aromatic hydrocarbons
such as benzene, toluene and xylene. The polymerization
temperature is not critical. In general, it is 0 to 90C
and preferably 20 to 70~C.
In accordance with the process of the present invention,
2~ styrene polymers (e.g., polystyrene, polyalkylstyrene, and
poly(halogenated styrene)) having a novel stereospecific
structure that side chains are mainly in the syndiotactic
configuration, or polystyrene polymers including the above
styrene polymers can be produced. These styrene polymers in
2~ which side chains are mainly in the syndiotactic configura-
tion mean that a degree of syndiotacticity at a racemidiad
in the nuclear magnetic resonance (NMR) spectrum is higher
than those in polymers obtained by conventional radical
-- 8 --
130~8X5
polymerization; for example, polystyrene having a methyl
ethyl ketone-insoluble polymer content of at least 75~, and
polymethylstyrene havin~ a methyl ethyl ketone-insoluble
polymer content of at least 85~.
The above styrene polymers in which side chains are
mainly in the syndiotactic configuration are either crystal-
line or amorphous. These crystalline styrene polymers are
higher in thermal resistance and better in solvent resistance
than commonly used atactic polystyrenes and, therefore, they
are useful as materials for use in fields where thermal
resistance and chemical resistance are required, or as modi-
fication materials to be blended with other resins. Even in
the case of amorphous styrene polymers, if various functional
groups are introduced in benzene rings as side chains, the
resulting polymers can be widely used as intermediate materials
for the production of functional polymers.
The present invention is described in greater detail
with reference to the following examples.
EXAMPLE 1
(1) Preparation of Aluminum Compound Component (B)
In 200 milliliters (ml) of a toluene solvent, 47.4 ml
(0.492 mol) of trimethylaluminum and 35.5 grams (g) (0.142
mol) of copper sulfate pentahydrate were reacted at 20C for
24 hours. Upon removal of a solid portion from the reaction
mixture, a toluene solution containing 12.4 g of methylalumino-
xane as the aluminum compound component (B) was obtained.
13058~5
/ (2) Polymerization of Styrene
A mixture of 100 ml of toluene, 0.05 millimole (mmol)
of titanium tetrachloride and 40 mmol (as aluminum atom) of
the methylaluminoxane obtained in (1) above was placed in a
500-milliliter reactor, and then 180 ml of styrene was intro-
duced in the reactor at 20C and polymerized for 1 hour.
After completion of the reaction, the reaction product was
washed with a hydrochloric acid/methanol mixture to decompose
the catalyst component and then dried to yield 7.0 g of a
~o polymer.
The polymer thus obtained was subjected to Soxlet
extraction using methyl ethyl ketone as a solvent. The
extraction residue was 95% by weight (wt~). For this polymer,
the weight average molecular weight was 350,000, the number
average molecular weight was 160,000, and in its thermal
differential analysis, the melting point was 270C and no
heat absorption peak was detected in the neighborhood of
220C; i.e., the melting point of isotactic polystyrene.
By comparison of a signal of Cl carbon of the aromatic
2~ ring (a phenyl group in the case of polystyrene) in 13C-NMR
(a nuclear magnetic resbnance spectrum using a carbon isotope)
(Fig. l(a)) and an X-ray diffraction pattern (Fig. 2(a)) of
the polymer with an aromatic ring Cl carbon signal in 13C-NMR
of isotactic polystyrene (Fig. l(b)), an aromatic ring Cl
2 ~ carbon signal in 13C-NMR of atactic polystyrene (Fig. l(c))
and an X-ray diffraction pattern of isotactic polystyrene
(Fig. 2(b)), and also of proton NMR (lH-NMR) of the polymer
(Fig. 3(a)) and lH-NMR of isotactic polystyrene (Fig. 3(b)),
-- 10 --
s~z~
,' it was found that the polymer was polystyrene of such high
syndiotacticconfigurat`ion that the tacticity as determined
in the racemic diad was at least 90%, which had not been
obtained.
EXA~SPLE 2
_ _
A mixture of 100 ml of toluene and 40 mmol of trimethyl-
aluminum was placed in a 500-milliliter polymerization vessel
at room temperature and then 0.72 ml of water was dropped and
reacted for 60 minutes. Then 0.05 mmol of titanium tetra-
fC~ chloride was added. After the mixture was raised in temperatureto 50C, 180 ml of styrene was introduced and polymerized for
2 hours. After completion of the reaction, the reaction
product was washed with a large amount of a hydrochloric acid/
methanol mixture and then dried to yield 1.0 g of a polymer.
The polymer thus obtained was extracted with methyl
ethyl ketone by the use of a Soxlet extractor. The extraction
residue was 98wt~. For the poly~er remaining after the methyl
ethyl ketone extraction, the weight average molecular weight
was 246,000 and the number average molecular weight was
10 117,000. The melting point was 269C. Both the X-ray dif-
fraction pattern and NMR pattern of the polymer were similar
to those in Example 1.
EXAMPLE 3
The procedure of (2) in Example 1 was repeated with the
exception that 0.05 mmol of titanium tetrabromide was used
as the titanium compound component.
-- 11 --
~ 305~
/ The yield of the polymer was 3.5 g and the residue after
the Soxlet extraction was 78 wt%. For the polymer, the weight
average molecular weight was 370,000 and the number av~rage
molecular weight was 160,000. The melting point and the
5~ results of the 13C-NM~ analysis of the polymer were similar
to those in Example 1.
EXAMPLE 4
The procedure of (2) in Example 1 was repeated with the
exception that 0.05 mmol of titanium tetraethoxide was used
~0 as the titanium compound component.
The yield of the polymer was 18.0 g, and the residue
after the Soxlet extraction was 97 wt~. For the polymer,
the weight average molecular weight was 430,000 and the number
average molecular weight was 210,000. The melting point and
the results of the 13C-NMR analysis of the polymer were
similar to those in Example 1.
EXAMPLE 5
The procedure of ( 2) in Example 1 was repeated with the
exceptions that 0.05 mmol of titanium tetraethoxide was used
as the titanium compound component, the amount as aluminum
atom of the methylaluminoxane used was 5 mmol, the amount of
the styrene introduced was 120 ml, the amount of the toluene
used was 20 ml, the polymerization temperature was 0C and
the polymerization time was 5 hours. In this way, 0.8 g of
a polymer was obtained.
The residue after the Soxlet extracticn was 92 wt%.
For the polymer, the weight average molecular weight was
- 12 -
~s~
f 3,085,000 and the number average molecular weight was
1,387,000. The melting point and the results of the 13C-NMR
analysis of the polymer were similar to those in Example 1.
EXAMPLE 6
The procedure of (2) in Example 1 was repeated with the
exceptions that 0.05 mmol of titanium tetraethoxide was used
as the titanium compound component, the amount as aluminum
atom of the methylaluminoxane used was 5 mmol, the amount of
the styrene introduced was 150 ml r the amount of the toluene
~0 used was 20 ml, the polymerization temperature was 20C and
the polymerization time was 9 hours. In this way, 3.0 g of
a polymer was obtained.
The residue after the Soxlet extraction was 84 wt%.
For the polymer, the weight average molecular weight was
- 2,480,000 and the number average molecular weight was 995,000.
The melting point and the results of the 13C-NMR analysis of
the polymer were similar to those in Example 1.
EXAMPLE 7
The procedure of (2) in Example 1 was repeated with
the exceptions that 0.05 mmol of titanium tetraethoxide was
used as the titanium compound component, the amount as aluminum
atom of the methylaluminoxane used was 25 mmol, the amount
of the styrene introduced was 50 ml, 100 ml of benzene was
used as the solvent, thepolymerization temperature was 50C
and the polymerization time was 4 hours. In this way, 1.9 g
of a polymer was obtained.
13058~5
/ The residue after the Soxlet extraction was 89 wt%.
~or the polymer, the weight average molecular weight was
301,000 and the number average molecular weight was 96,000.
The melting point and the results of the 13C-NMR analysis of
the polymer were similar to those in Example 1.
EXAMPLE 8
-
The procedure of Example 7 was repeated with the
exceptions that 100 ml of xylene was used as a polymerization
solvent and the polymerization time was 2 hours. In this
~C way, 1.8 g of a polymer was used.
The residue after the Soxlet extraction was 92 wt~.
For the polymer, the weight average ~olecular weight was
201,000 and the number average molecular weight was 101,000.
The melting point and the results of the 13C-NMR analysis of
the polymer were similar to those in Example 1.
EXAMPLE 9
The procedure of (2) in Example 1 was repeated with
the exceptions that 0.05 mmol of titanium tetraethoxide was
used as the titanium compound component, the amount (as
~5 aluminum atom) of the methylaluminoxane used was 5 mmol,
the amount of the styrene introduced was 150 ml, 50 ml of
hexane was used as the solvent, the polymerization temperature
was 50C and the polymerization time was 1.5 hours. In
this way, 8.2 g of a polymer was obtained.
The residue after the Soxlet extraction was 92.7 wt~.
Eor the polymer, the weight average molecular weight was
1 3~2~
756,000 and the number average molecular weight was 77,000.
The melting point and the results of the 13C-NMR analysis of
the polymer were similar to those in Example 1.
EXAMPLE 10
_ _
The procedure of (2) in Example 1 was repeated with the
exceptions that 1 mmol of titanium tetraisopropoxide was
used as a titanium compound, the amount as aluminum atom of
the methylaluminoxane used as 40 mmol, the amount of the
styrene introduced was 50 mol, the amount of the toluene
used was 200 ml, the polymerization temperature was 50C
and the polymerization time was 2 hours. In this way, 0.9 g
of a polymer was obtained.
The residue after the Soxlet extraction was 78 wt%.
The melting point of the polymer and the results of the
~5 13C-NMR analysis of the polymer were similar to those in
Example 1.
EXAMPLE 11
The procedure of (2) in Example 1 was repeated with
the exceptions that 0.01 mmol of titanium tetramethoxide was
used as a titanium compound, the amount as aluminum atom of
the methylaluminoxane used was 8 mmol, the amount of the
styrene introduced was 100 ml, the amount of the toluene
used was 100 ml, the polymerization temperature was 50C
and the polymerization time was 2 hours. In this way, 6.2
g of a polymer was obtained.
1305~S
The residue after the Soxlet extraction was 91 wt%.
The melting point and the results of the 13C-NMR analysis
of the polymer were similar to those in Example 1.
EXAMPLE 12
The procedure of (2) in Example 1 was repeated with the
exceptions that 1 mmol of titanium tetra-n-butoxide was used
as a titanium compound, the amount as aluminum atom of the
methylaluminoxane used was 40 mmol, the amount of the styrene
introduced was 180 ml, the amount of the toluene was 100 ml,
the polymerization temperature was 50C and the polymeriza-
tion time was 2 hours. In this way, 10.5 g of a polymer
were obtained.
The residue after the Soxlet extraction was 86 wt~.
The melting point and the results of the 13C-NMR analysis
of the polymer were similar to those in Example 1.
EXAMPLE 13
The procedure of (2) in Example 1 was repeated with
the exceptions that 1 mmol of tetra(octadecyloxy) titanium
was used as a titanium compound, the amount as aluminum
24 atom of the methylaluminoxane used was 40 mmol, the amount
of the styrene introduced was 100 ml, the amount of the
toluene used was 200 ml, the polymerization temperature
was 50C and the polymerization time was 2 hours. In this
way, 2.6 g of a polymer was obtained.
The residue after the Soxlet extraction was 87 wt%.
The melting point and the results of the 13C-NMR analysis of
~5~325
the polymer were similar to those in Example l.
EXAMPL~ 14
The procedure of (2) in Example l was repeated with
the exception that 0.05 mmol of tetra(2-ethylhexyloxy)-
~~ titanium was used as the titanium compound component.
The yield of the polymer was 20.0 g. The residue afterthe Soxlet extraction was 90 wt~. For the polymer, the
weight average molecular weight was 450,000 and the number
average molecular weight was 210,000. The melting point
'D and the results of the 13C-NMR analysis of the polymer were
similar to those in Example 1.
EXAMPLE 15
The procedure of (2) in Example 1 was repeated with
the exception that 0.05 mmol of titanium monoisopropoxy tri-
,~ chloride was used as the titanium compound component.
The yield of the polymer was lO.0 g, and the residueafter the Soxlet extraction was 97 wt%. For the polymer,
the weight average molecular weight was 360,000 and the
number average molecular weight was 160,000. The melting
z~ point and the results of the 13C-NMR analysis of the polymer
were similar to those in Example l.
EXAMPLE 16
The procedure of (2) in Example 1 was repeated with
the exception that 0.05 mmol of titanium diisopropoxy di-
2~ chloride was used as the titanium compound component.
- 17 -
Q58~S
t The yield of the polymer was 20.0 g, and the residue
after the Soxlet extraction was 97 wt%. For the polymer,
the weight average molecular weight was 400,000 and the
number average molecular weight was 210,000. The melting
point and the results of the 13C-NMR analysis of the
polymer were similar to those in Example 1.
EXAMPLE 17
The procedure of (2) in Example 1 was repeated with
the exception that 0.05 mmol of titanium triisopropoxy mono-
G chloride was used as the titanium compound component.
The yield of the polymer was 17.0 g, and the residue
after the Soxlet extraction was 97 wt~. For the polymer,
the weight average molecular weight was 380,000 and the
number average molecular weight was 170,000. The melting
point and the results of the 13C-NMR analysis of the polymer
were similar to those in Example 1.
EXAMPLE 18
The procedure of (2) in Example 1 was repeated with
the exceptions that 0.01 mmol of bis(2,4-pentanedionate)
~o titanium dibutoxide was used as the titanium compound compo-
nent and the amount (as aluminum atom) of the methylalumino-
xane used was 9 mmol.
The yield of the polymer was 1.5 g. The residue after
the Soxlet extraction was 55 wt%. For the polymer, the
- weight average molecular weight was 380,000 and the number
average molecular weight was 170.000. The melting point and
- 18 -
~OS8X5
the results of the 13C-NMR analysis of the polymer were
similar to those in Example 1.
EXAMPLE 19
The procedure of (2) in Example 1 was repeated with
the exceptions that 0.05 mmol of isopropoxytitaniu~ tristea-
rate was used as the titanium compound component, the amount
as aluminum atom of the methylaluminoxane used was 40 mmol,
the amount of the styrene introduced was 100 ml, the amount
of the toluene used was 200 ml, the polymerization temperature
~C was 50C and the polymerization time was 2 hours. In this
way, 1.1 g of a polymer was obtained.
The residue after the Soxlet extraction was 89 wt%.
The melting point and the results of the 13C-NMR analysis
of the polymer were similar to those in Example 1.
EXAMPLE 20
The procedure of (2) in Example 1 was repeated with
the exception that 0.05 mmol of methyltitanium trichloride
was used as the titanium compound component.
The yield of the polymer was 3.5 g, and the residue
after the Soxlet extraction was 75 wt%. For the polymer,
the weight average molecular weight was 360,000 and the
number average molecular weight was 150,000. The melting
point and the results of the 13C-NMR analysis of the polymer
were similar to those in Example 1.
-- 19 --
~3Q~8~S
/ EXAMPLE 21
. _
The procedure of (2) in Example 1 was repeated with the
exception $hat 0.05 mmol of biscyclopentadienyltitanium
dichloride was used as the titanium compound component.
The yield of the polymer was 3.0 g, and the residue
after the Soxlet extraction was 60 wt~. For the polymer,
the weight average molecular weight was 150,000 and the
number average molecular weight was 71,000. The melting
point and the results of the 13C-NMR analysis of the polymer
were similar to those in Example 1.
EXAMPLE 22
The procedure of (2) in Example 1 was repeated with the
exception that 0.05 mmol of cyclopentadienyltitanium tri-
chloride was used as the titanium compound component.
The yield of the polymer was 16. 5 g, and the residue
after the Soxlet extraction was 97 wt%. For the polymer, the
weight average molecular weight was 280,000 and the number
average molecular weight was 57,000. The melting point and
the results of the 13C-NMR analysis were similar to those
in Example 1.
EXAMPLE 23
A mixture of 100 ml of toluene and 40 mmol of tri-
methylaluminum was placed in a 500-milliliter polymerization
vessel, and then 0.72 ml of water was dropped and the result-
2~ ing mixture was stirred at room temperature for 40 minutes.
Then, 0.05 mmol of cyclopentadienyltitanium trichloride was
- 20 -
i30S~25
/ added. After the resulting mixture was raised in ~emperature
to 50C, 180 ml of styrene was introduced and polyme3-ized for
2 hours.
The yield of the polymer was 17.6 g, and the residue
after the Soxlet extraction was 96 wt%. For the po~ymer, the
weight average molecular weight was 110,000 and the number
average molecular weight was 49,000. The melting point and
the resul~s of the 13C-NMR analysis of the polymer were
similar to those in Example 1.
~o EXAMPLE 24
The procedure of Example 22 was repeated with the
exception that 100 ml of heptane was used as a polymerization
solvent in place of toluene.
The yield of the polymer was 16.3 g, and the residue
~5~ after the Soxlet extraction was 95 wt%. For the po]ymer, the
weight average molecular weight was 307,000 and the number
average molecular weight was 80,000. The melting point and
the 13C-NMR analysis of the polymer were similar to those in
Example 1.
2~ EXAMPLE 25
The procedure of Example 22 was repeated with the
exception that a mixture of 20 mmol (as aluminum atom) of
the methylaluminoxane obtained in (1) of Example 1 and 20
mmol (as aluminum atom) of trimethylaluminum was used as
the aluminum compound component.
- 21 -
1;~0~8~
The yield of the polymer was 16.3 g, a~d the residue
after the Soxlet extraction was 95 wt%. For the polymer,
the weight average molecular weight was 43,000 and the
number average molecular weightwas 22,000. The melting point
and the results of the 13C-NMR analysis of the polymer were
similar to those in Example 1.
EXAMPLE 26
. _
The procedure of Example 22 was repeated with the
exception that a mixture of 20 mmol (as aluminum atom) of
~C the methylaluminoxane obtained in (1) of Example 1 and 20
mmol (as aluminum atom) of triisobutylaluminum was used as
the aluminum compound component.
The yield of the polymer was 15.5 g, and the residue
after the Soxlet extraction was 84.3 wt~. For the polymer,
f~ the weight average molecular weight was 130,000 and the
number average molecular weight was 73, 000. The melting
point and the results of the 13C-NMR analysis of the polymer
were similar to those in Example 1.
EXAMPLE 27
The procedure of Example 22 was repeated with the
exception that the polymerization temperature was 0C.
The yield of the polymer was 11.6 g, and the residue
after the Soxlet extraction was 93 wt%. For the polymer,
the ~eight average molecular weight was 410,000 and the
25V number average molecular weight was 210,000. The melting
point and the results of the 13C-NMR analysis of the
- 22 -
~05&X5
polymer were similar to those in Example l.
EXAMPLE 28
_
The procedure of Example 22 was repeated with the
exceptions that in connection with the amount of the cata-
lyst component used, the amount of the cyclopentadienyl-
titanium trichloride used was 0.02 mmol and the amount as
aluminum atom of the methylaluminoxane used was 20 mmol.
The yield of the polymer was 23.8 g, and the residue
after the Soxlet extraction was 93 wt~. For the polymer,
fO the weight average molecular weight was 140,000 and the
number average molecular weight was 69,000. The melting
point and the results of the l3C-NMR analysis of the polymer
were similar to those in Example l.
EXAMP~E 29
,~ The procedure of (2) in Example l was repeated with
the exceptions that 0.02 mmol of a titanium tetrachloride/
ethyl benzoate complex was used as the titanium compound
component, the amount as aluminum atom of the methylaluminoxane
used was lO mmol, the amount of the styrene introduced
2~ was 50 ml, the amount of the toluene used was lO0 ml, the
polymerization temperature was 50C and the polymerization
time was 2 hours. In this way, 0.4 g of a polymer was
obtained. The residue after the Soxlet extraction was 63
wt~.
The melting point and the results of the l3C-NMR
analysis of the polymer were similar to those in Example l.
- 23 -
~0~2S
i EXAMPLE 30
The procedure of (2) in Example 1 was repeated with the
exceptions that 0. 2 mmol as titanium atom of titanium tetra-
chloride deposited on magnesium diethoxide (146 mg (as
titanium atom) of titanium tetrachloride per gram of
magnesium diethoxide) was used as the titanium compound
component, the amount as aluminum atom of the methylaluminoxane
used was 10 mmol, the amount of the styrene introduced was
50 ml, the amount of the toluene was 100 ml, the polymeriza-
tion temperature was 50C and the polymerization time was
2 hours. In this way, 0.5 g of a polymer was obtained.
The residue after the Soxlet extraction was 41 wt%.
The melting point and the results of the 13C-NMR analysis
of the polymer were similar to those in Example 1.
EXAMPLE 31
~ he procedure of (2) in Example 1 was repeated with
the exceptions that 0.02 mmol as titanium atom of titanium
tetrachloride deposited on magnesium chloride (80 mg (as
titanium atom) of titanium tetrachloride per gram of
magnesium dichloride) was used as the titanium compound
component, the amount as aluminum atom of the methyl-
aluminoxane used was 10 mmol, the amount of the styrene
introduced was 50 ml, the amount of the toluene used was
100 ml, the polymerization temperature was 50C and the
polymerization time was 2 hours. In this way, 1.2 g of a
polymer was obtained.
- 24 -
1305fi~:S
The residue after the Soxlet extraction was 88 wt%.
The melting point and the results of the 13C-NMR analysis
of the polymer were similar to those in Example 1.
EXAMPLE 32
The procedure of (2) in Example 1 was repeated with
the exceptions that 0.05 mmol as titanium atom of a magnesium
stearate/titanium tetrachloride (1/0.1 by mole) mixture was
used as the titanium compound component, the amount as
aluminum atom of the methylaluminoxane used was 40 mmol, the
,~ amount of the styrene introduced was 180 ml, the amount of
the toluene used was 100 ml, the polymerization temperature
was 50C and the polymerization time was 2 hours. In this
way, 3.8 g of a polymer was obtained.
The residue after the Soxlet extraction was 86 wt%.
The melting point and the results of the 13C-NMR analysis
of the polymer were similar to those in Example 1.
EXAMPLE 33
The procedure of (2) in Example 1 was repeated with
the exceptions that 0.05 mmol as titanium atom of a magnesium
23 stearate/titanium tetraethoxide (1/0.1 by mole) mixture was
used as the titanium compound component, the amount as
aluminum atom of the methylaluminoxane used was 40 mmol,
the amount of the styrene introduced was 180 ml, the
amount of the toluene used was 100 ml, the polymerization
temperature was 50C and the polymerization time was 2
hours. In this way, 1.2 g of a polymer was obtained.
- 25 -
~305825
i The residue after the Soxlet extraction was 20 wt%.
The melting point and the results of the 13C-NMR analysis
of the polymer were similar to those in Example 1.
EXAMPLE 34
The procedure of (2) in Example 1 was repeated with
the exceptions that 0.02 mmol of titanium trichloride was
used as the titanium compound component, the amount as
aluminum atom of the methylaluminoxane used was 20 mmol,
the amount of the styrene introduced was 50 ml, the amount
~-o of the toluene used was 100 ml, the polymerization temperature
was 50C and the polymerization time was 2 hours. In this
way, 0.41 g of a polymer was obtained.
The residue after the Soxlet extraction was 30 wt~.
For the polymer, the weight average molecular weight was
~S 871,000, the number average molecular weight was 413,000
and the melting point was 270C. Based on the aromatic
ring Cl carbon signal in 13C-NMR of the polymer, it was
determined that the tacticity as determined in the racemic
pendad was 58~.
~o EXAMPLE 35
The procedure of ~xample 22 was repeated with the
exception that 80 ml of p-methylstyrene was used as a start-
ing monomer in place of styrene.
The yield of the polymer was 16.0 g, and the residue
after the Soxlet extraction was 55 wt~. For the polymer,
the weight average molecular weight was 38,000, the number
- 26 -
130582S
/ average molecular weight was 2,000 and the melting point
was 168C, Based on the aromatic ring Cl carbon signal
in 13C-NMR of the polymer (Fig. 4), it was determined that
the polymer was of such syndiotactic configuration that
the tacticity as determined in the racemic pentad was at
least 90%.
EXA~LE 36
The procedure of Example 22 was repeated with the
exception that 40 ml of p-chlorostyrene was used as a start-
~;C ing monomer in place of the styrene.
The yield of the polymer was 3.0 g, and the residueafter the Soxlet extraction was 90 wt%. For the polymer,
the weight average molecular weight was 20,000, the number
average molecular weight was 2,000 and the melting point
~S was 295C. By comparison of the aromatic ring Cl carbon
signal in 13C-NMR of the polymer (Fig. 5(a)) and the aromatic
ring C1 carbon signal in 13NMR of atactic poly(p-chlorostyrene3
as a re~erence polymer (Fig. 5(b)), it was found that the
polymer was poly~p-chlorostyrene) of such high syndiotactic
2~ configuration that the tacticity as determined in the racemic
pentad was at least 90~, which had never been obtained.
EXAMPLE 37
The procedure of Example 2 was repeated with the
exceptions that 24.8 ml of m-chlorostyrene was used as a
25~ starting monomer and 0.05 mmol of tetraethoxytitanium was
used as a titanium compound. In this way, l.8 g of a
- 27 -
l~QS~X~
polymer was obtained.
The residue after the Soxlet extraction was 51 wt~.
For the polymer, the weight average molecular weight was
~7,000 and the number average molecular weight was 13,000.
Based on the aromatic ring Cl carbon signal in 13C-
NMR of the polymer (Fig. 6), it was determined that the
polymer was of such syndiotactic configuration that the
tacticity as determined at the racemic pentad was at
least 80%.
EXAMPLE 38
The procedure of Example 35 was repeated with the
exceptions that 17 ml of m-methylstyrene was used as a
starting monomer, the amount as aluminum atom of the
methylaluminoxane used was 30 mmol and the polymerization
time was 3 hours. In this way, 15.1 g of a polymer was
o~tained.
The residue after the Soxlet extraction was 98 wt%.
For the polymer, the weight average molecular weight was
59,000, the number average molecular weight was 26,000 and
the melting point was 206C. Based on the aromatic ring
Cl carbon signal in 13C-NM~ of the polymer (Fig. 7), it
was determined that the polymer was of such syndiotactic
configuration that the tacticity as determined at the
racemic pentad was at least 92~.
- 28 -
~3Q5~3X5
EXAMPLE 39
The procedure of Example 35 was repeated with the
exceptions that 23.9 ml of p-fluorostyrene was used as a
starting monomer, the amount as aluminum atom of the
methylaluminoxane used was 30 mmol and the polymerization
was conducted at 50C for 5 hours. In this way, 0.2 g of a
polymer was obtained.
For the polymer thus obtained, the weight average
molecular weight was 29,000 and the number average molecular
~-0 weight was 8,800. Based on the aromatic ring Cl carbon
signal in 13C-NMR of the polymer (Fig. 8), it was determined
that the polvmer was of such syndiotactic configuration that
the tacticity as determined at the racemic pentad was at
least 70~.
EXAMPLE 40
The procedure of Example 22 was repeated with the
exceptions that 27 g of p-tert-butylstyrene was used as a
starting monomer, the amount of the cyclopentadienyltitanium
trichloride used was 0.02 mmol, the amount as aluminum atom
2~ of the methylaluminoxane used was 30 mmol, and the polymeriza-
tion was conducted at 50C for 4 hours. In this way, 25.3
g of a polymer was obtained.
The residue after the Soxlet extraction was 99 wt%.
For the polymer, the weight average molecular weight was
z~ 71,000, the number average molecular weight was 21,000 and
the melting point was 310C. Based on the aromatic ring C
carbon signal in 13C-NMR of the polymer (Fig. 9), it was
- 29 -
1305825
determined that the polymer was of such syndiotactic configu-
ration that the tacticity as determined at the racemic pentad
was at least 94%.
EXAMPLE 41
The procedure of Example 22 was repeated with the
exceptions that a mixture of 29.5 ml of styrene and 26 ml of
p-methylstyrene was used as a starting monomer, the amount of
the cyclopentadienyltitanium trichloride used was 0.02 mmol,
the amount of the methylaluminoxane used was 10 mmol, and
the polymerization was conducted at 50C for 2 hours. In
this way, 7 g of a copolymer was obtained.
The residue after the Soxlet extraction was 70 wt%.
EXAMPLE 42
The procedure of Example 41 was repeated with the
exception that a mixture of 53.1 ml of styrene and 5.2 ml of
p-methylstyrene was used as a starting monomer. In this
way, 17.8 g of a copolymer was obtained.
The residue after the Soxlet extraction was 76 wt~.
Based on the 13C-NMR analysis of the copolymer, it was
determined that the polymer was of such syndiotactic confi-
guration that the polystyrene segment had a tacticity of 72
as determined at the racemic pentad.
EXAMPLE 43
The procedure of Example 35 was repeated with the
exceptions that 39.4 ml of p-methylstyrene was used as a
- 30 -
13~58~S
starting monomer, the amount as aluminum atom of the
methylaluminoxane used was 30 mmol, and the polymerization
was conducted at 50C for 3 hours. In this way, 34 g of
a polymer was obtained.
The residue after the Soxlet extraction was 56 wt%.
For the methyl ethyl ketone-extracted portion of the polymer,
the weight average molecular weight was 33,000, the number
average molecular weight was 14,000 and the meltin~ point was
168C. For the methyl ethyl ketone extraction residue, the
f D weight average molecular weight was 48,000, the number
average molecular weight was 23,000 and the melting point
was 173C.
EXAMPLE 44
The procedure of Example 23 was repeated with the
exception that ethylaluminoxane prepared using 40 mmol of
triethylaluminum was used in place of the trimethylaluminum.
In this way, 0.1 g of a polymer was obtained.
Based on the 13C-NMR analysis of the polymer, it
was determined that the polymer was of such syndiotactic
~ configuration that the tacticity as determined at the
racemic pentad was 80~.
EXAMPLE 45
-
The procedure of (2) in Example 1 was repeated with
the exceptions that 0.05 mmol of cyclopentadienyl titanium
dichloride was used as the titanium compound component, the
amount of the methylaluminoxane used was 30 mmol (as
- 31 -
13~)5~25
/ aluminum atom), the amount of the styrene introduced was
25 ml, the amount of the toluene used was 50 ml, the
polymerization temperature was 50~C and the polymerization
time was 2 hours. In this way, 9.2 g of a polymer was
~f obtained.
The residue after the Soxlet extraction was 93.6 wt%.
For the polymer, the weight average molecular weight was
41,000 and the number average molecular weight was 24,000.
The melting point and the results of the 13C-NMR analysis
,D of the polymer were similar to those in Example 1.
EXAMPLE 46
The procedure of (2) in Example 1 was repeated with the
exceptions that 0.05 mmol of bispentamethylcyclopentadienyl
titanium dichloride was used as the titanium compound
~S component, the amount of the methylaluminoxane used was 30
mmol (as aluminum atom), the amount of the styrene introduced
was 25 ml, the amount of the toluene used was 50 ml, the
polymerization temperature was 50C and the polymerization
time was 2 hours. In this way, 1.6 g of a polymer was
2~ obtained.
The residue after the Soxlet extraction was 95.3%.
For the polymer, the weight average molecular weight was
167,000 and the number average molecular weight was 94,000.
The melting point and the results of the 13C-NMR analysis
-- of the polymer were similar to those in Example 1.
