CA1250697A - Process for production of styrene polymers - Google Patents
Process for production of styrene polymersInfo
- Publication number
- CA1250697A CA1250697A CA000522291A CA522291A CA1250697A CA 1250697 A CA1250697 A CA 1250697A CA 000522291 A CA000522291 A CA 000522291A CA 522291 A CA522291 A CA 522291A CA 1250697 A CA1250697 A CA 1250697A
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- polymer
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F12/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F12/02—Monomers containing only one unsaturated aliphatic radical
- C08F12/04—Monomers containing only one unsaturated aliphatic radical containing one ring
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
- C08F4/65912—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound
Abstract
ABSTRACT OF THE DISCLOSURE
A process for production of styrene polymers of high syndiotactic configuration is disclosed, comprising poly-merizing styrene or styrene derivatives by the use of a catalyst comprising: (A) a titanium compound, e.g., at least one compound selected from those represented by the formulae: TiR1aR2bR3cX14-(a+b+c) and TiR1dR2eX13-(d+e) (all the symbols are as defined in the appended claims);
and (B) a contact product of an organoaluminum compound and a condensation agent, e.g., a product resulting from modification of trimethylaluminum with water. Because of such high syndiotactic configuration, the styrene polymers are greater in thermal resistance and solvent resistance than conventional atactic polystyrene.
A process for production of styrene polymers of high syndiotactic configuration is disclosed, comprising poly-merizing styrene or styrene derivatives by the use of a catalyst comprising: (A) a titanium compound, e.g., at least one compound selected from those represented by the formulae: TiR1aR2bR3cX14-(a+b+c) and TiR1dR2eX13-(d+e) (all the symbols are as defined in the appended claims);
and (B) a contact product of an organoaluminum compound and a condensation agent, e.g., a product resulting from modification of trimethylaluminum with water. Because of such high syndiotactic configuration, the styrene polymers are greater in thermal resistance and solvent resistance than conventional atactic polystyrene.
Description
PROCESS FOR PRODUCTION OF STYRENE POLYMERS
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 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 number of styrene pol~ners 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;
that is, a method whereby styrene polymers of high syndiotactic configllratiorl can be obtained has not been known.
SUMMARY OF THE INVEMTION
An object of the present invention is to provide a process for producing styrene polymers in which polymer side 6~7 1 chains are mainly in the syndiotactic configuration.
It has been found tha-t styrene polymers of high syn-diotac~ic configuration can be obtained by polymerizing styrene or its derivatives by the use of a catalyst compris-ing specified transition metal compound and organoaluminumcompound components.
The present invention relates to 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 DESCR _TION OF THE D~AWINGS
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 polystyrene, 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 Cl carbon signals 25 in C-NMRof the polymer obtained in Example 36 and atactic poly(p-chlorostyrene), respectively; and .
: . . -. .:
. . .
1 Figs. 6, 7, 8 and 9 show aromatic ring Cl 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.
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 (B) a contact produet of an organoaluminum compound and a condensation agent.
As the component (A), various titanlum compounds can be used. Preferred among these compounds are titanium compounds and titanium chelate compoundc represented by the following general formulae (I) and (II):
General Formula (I) TiRlaR2bR3cxl4-~a ~ b ~ c) General Formula (II) TlR dR eX 3-(d + e) (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 earbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group, an arylalkyl group, an a~yloxy group having 1 to 20 carbon atoms, a eyclopentadienyl group, a substituted cyclopentadienyl group or an indenyl 1 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 L5 (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 1,2-20 dimethylcyclopentadienyl group and a pentamethylcyclopenta-dienyl group), or an indenyl group. These Rl, R2 and R3 may be the same or different.
x1 represents a halogen atom, such as chlorine, bromine, iodine or fluorine.
a, b and c each xepresent 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 .
~Z~ i9~
1 general formula (I) are methyltitanium trichloride, titaniumtetramethoxide, titanium tetraethoxide, titanium monoisopropoxy trichloride, titanium diisopropoxy 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.
As the component (A), as well 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-chloride and cyclopentadienyl titanium compounds such ascyclopentadienyl titanium dichloride. In addition, trivalent l 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 ccntacting an organoaluminum compound with a condensation agent. Such organoaluminum compounds include those represented by the general formula (IV):
AlR63 (wherein R6 represents an alkyl group having 1 to 8 carbon atoms). Representative examples of the organoaluminum com-pounds represented ~y 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.
Representative examples of the reaction product between the alkylaluminum compound and water, which is a typical example of the component (B), are alkylaluminoxanes represented by the genexal formula (V):
t Al - O t n l6 (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 l reacted by known techniques, such as (l) 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 ln metal salts and so forth, or water adsorbed on inorganic or organic compounds is reacted.
In the process of the present invention, the component (B) of the catalyst can be used alone. In addition, the component (B) can be used as an admixture with organoaluminum compounds (e.g., those 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 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 the component (A), i.e., aluminum/titanium, is 1/1 to lx106/lr with the range of 10/l to lx104/l being preferred.
The monomer to be polymerized by the process of the present invention is styrene or its derivatives. These 1 styrene derivatives include alkyls~yrene 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, 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 i6 not critical. In general, it is 0 to 90C
and preferably 20 to 70C.
In accordance with the process of the present in~ention, styrene polymers (e.g., polystyrene, polyalkylstyrene, and polythalogenated 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 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 th~se in polymers obtained by conventional radical ~, - 8 -~2~636~
1 polymerization; for example, polystyrene having a methyl ethyl ketone-insoluble polymer content of at least 75%, and polymethylstyrene having 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.
EXAMPL~ 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.
g 1 (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 catalys-t component and then dried to yield 7.0 g of a 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 ring (a phenyl group in the case of polystyrene) in 13C-NMR
(a nuclear magnetic resonance 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 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~), 1 it was found that the polymer was polystyrene of such high syndiotacticcon~figura~ion that the tacticity as determined in the racemic diad was at least 90%, which had not been obtained.
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~
chloride was added. After the mixture was raised in temperature to 50C, 180 ml of styrene was introduced and polymerized for
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 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 number of styrene pol~ners 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;
that is, a method whereby styrene polymers of high syndiotactic configllratiorl can be obtained has not been known.
SUMMARY OF THE INVEMTION
An object of the present invention is to provide a process for producing styrene polymers in which polymer side 6~7 1 chains are mainly in the syndiotactic configuration.
It has been found tha-t styrene polymers of high syn-diotac~ic configuration can be obtained by polymerizing styrene or its derivatives by the use of a catalyst compris-ing specified transition metal compound and organoaluminumcompound components.
The present invention relates to 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 DESCR _TION OF THE D~AWINGS
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 polystyrene, 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 Cl carbon signals 25 in C-NMRof the polymer obtained in Example 36 and atactic poly(p-chlorostyrene), respectively; and .
: . . -. .:
. . .
1 Figs. 6, 7, 8 and 9 show aromatic ring Cl 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.
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 (B) a contact produet of an organoaluminum compound and a condensation agent.
As the component (A), various titanlum compounds can be used. Preferred among these compounds are titanium compounds and titanium chelate compoundc represented by the following general formulae (I) and (II):
General Formula (I) TiRlaR2bR3cxl4-~a ~ b ~ c) General Formula (II) TlR dR eX 3-(d + e) (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 earbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group, an arylalkyl group, an a~yloxy group having 1 to 20 carbon atoms, a eyclopentadienyl group, a substituted cyclopentadienyl group or an indenyl 1 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 L5 (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 1,2-20 dimethylcyclopentadienyl group and a pentamethylcyclopenta-dienyl group), or an indenyl group. These Rl, R2 and R3 may be the same or different.
x1 represents a halogen atom, such as chlorine, bromine, iodine or fluorine.
a, b and c each xepresent 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 .
~Z~ i9~
1 general formula (I) are methyltitanium trichloride, titaniumtetramethoxide, titanium tetraethoxide, titanium monoisopropoxy trichloride, titanium diisopropoxy 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.
As the component (A), as well 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-chloride and cyclopentadienyl titanium compounds such ascyclopentadienyl titanium dichloride. In addition, trivalent l 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 ccntacting an organoaluminum compound with a condensation agent. Such organoaluminum compounds include those represented by the general formula (IV):
AlR63 (wherein R6 represents an alkyl group having 1 to 8 carbon atoms). Representative examples of the organoaluminum com-pounds represented ~y 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.
Representative examples of the reaction product between the alkylaluminum compound and water, which is a typical example of the component (B), are alkylaluminoxanes represented by the genexal formula (V):
t Al - O t n l6 (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 l reacted by known techniques, such as (l) 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 ln metal salts and so forth, or water adsorbed on inorganic or organic compounds is reacted.
In the process of the present invention, the component (B) of the catalyst can be used alone. In addition, the component (B) can be used as an admixture with organoaluminum compounds (e.g., those 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 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 the component (A), i.e., aluminum/titanium, is 1/1 to lx106/lr with the range of 10/l to lx104/l being preferred.
The monomer to be polymerized by the process of the present invention is styrene or its derivatives. These 1 styrene derivatives include alkyls~yrene 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, 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 i6 not critical. In general, it is 0 to 90C
and preferably 20 to 70C.
In accordance with the process of the present in~ention, styrene polymers (e.g., polystyrene, polyalkylstyrene, and polythalogenated 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 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 th~se in polymers obtained by conventional radical ~, - 8 -~2~636~
1 polymerization; for example, polystyrene having a methyl ethyl ketone-insoluble polymer content of at least 75%, and polymethylstyrene having 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.
EXAMPL~ 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.
g 1 (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 catalys-t component and then dried to yield 7.0 g of a 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 ring (a phenyl group in the case of polystyrene) in 13C-NMR
(a nuclear magnetic resonance 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 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~), 1 it was found that the polymer was polystyrene of such high syndiotacticcon~figura~ion that the tacticity as determined in the racemic diad was at least 90%, which had not been obtained.
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~
chloride was added. After the mixture was raised in temperature to 50C, 180 ml of styrene was introduced and polymerized for
2 hours. After completion of the reaction, the reaction product was washed with a larye amount of a hydrochloric acid/
methanol mixture and then dried to yield 1.0 g o~ 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 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.
The procedure of (2) in Example 1 was repeated with the exception that 0.~5 mmol of titanium tetrabromide was used as the titanium compound component.
~ ~t~ 7 l The yleld 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 average molecular weight was 160,000. The melting point and the results of the 13C-NMR analysis of the polymer were similar to those in Example 1.
The procedure of (2) in Example l was repeated with the exception that 0.05 mmol of titanium tetraethoxide was used as the titanium compound component.
The yield of the polymer was l~.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,Q00. The melting point and the results of the l3C-NMR analysis of the polymer were similar to those in Example l.
The procedure of (2) in Example l 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 extraction was 92 wt~.
For the polymer, the weight average molecular weight was ~Z 5~ ~!97 l 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.
-The procedure of (2) in Example 1 was repeated with the exceptions that 0.05 mmol of titanium tetraethoxide was used as the titanium compountd component, the amount as aluminum atorn of the methylaluminoxane used was 5 mmol, the amount of the styrene introduced was 150 ml, the amount of the toluene used was 20 ml, the polymerization temperature was ~0C 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 welght 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.
The procedure of (2) in Example 1 was repeated with the ext~eptions 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, thepolymeriza`tion temperature was 50C
and the polymerization time was 4 hours. In this way, 1.9 g of a polymer was obtained.
9t7 1 The residue after the Soxlet extraction was 89 wt%.
For 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.
EX~MPLE 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 way, 1.8 g of a polymer was used.
The residue after the Soxlet extraction was 92 wt%.
For the polymer, the weight average molecular weight was 201,000 and the number average molecular weight was 101,000.
The meltin~ point and the results of the 13C-NMR analysis of the polymer were similar to those in Example 1.
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, 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~.
~or the polymer, the weight average molecular weight was 1 756,000 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.
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 10 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 13C-NMR analysis of the polymer were similar to those in Example 1.
. .
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 ~ of a polymer was obtained.
., - 15 ~2~
1 The residue after the Soxlet extraction was 91 wt%.
The mel-ting point and -the results of the 13C-NMR analysis of the polymer were similar to those in Example 1.
EX~MPLE 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 rèsidue 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.
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 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 resîdue after the Soxlet extraction was 87 wt%.
The melting point and the results of the 13C-NMR analysis of 1 the polymer were similar to those in Example 1.
The procedure of (2) in Example 1 was repeated with the exception that 0.05 mmol of tetra(2-ethylhexyloxy)-titanium was used as the titanium compound c~mponent.
The yield of the polymer was 20.0 g. The residue after the 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 and the results of the 13C-NMR analysis of the polymer were similar to those in Example 1.
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 10.0 g, and the residueafter the Soxlet extraction was 97 wt%. For the polymer, the weight a~erage molecular weight was 360,000 and the number average molecular weight was 160,000. The melting point and the results of the 13C~NMR analysis of the polymer were similar to those in Example 1.
The procedure of (2) in Example 1 was repeated with the exception that 0.05 mmol of titanium diisopropoxy di-chloride was used as the titanium compound component.
~2~
1 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 2xample lo _ The procedure of (2) in Example 1 was xepeated with the exception that 0.05 mmol of titanium triisopropoxy mono-chloride was used as the titanium compound component.
The yield of the polymer was 17.0 g, and the residueafter 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.
E~AMPLE 18 The procedure of (2) in Example 1 was repeated with the exceptions that 0.01 mmol of bist2,4-pentanedionate) 20 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 25 weight average molecular weight was 380,000 and the number average molecular weight was 170.000. The melting point and 1 the results of the 13C-NMR analysis of the polymer were similar to those in Example 1.
The procedure of (2) in Example 1 was repeated with the exceptions that 0.05 mmol of isopropoxytitanium 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 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.
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.
. .
The procedure of (2) in Example 1 was repeated with the exception that 0.05 mmol of biscyclopentadienyltitanium dichloride was used as the titanium compouncl component.
The yield of the polymer was 3.0 g, ancl the residue after the Soxlet extraction was S0 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.
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-ing mixture was stirred at room temperature for 40 minutes.
Then, 0.05 mmol of cyclopentadienyltitanium trichloride was 1 added. After the resulting mixture was raised in temperature to 50C, 1~0 ml of styrene was introduced and polymerlzed for 2 hours.
The yield of the polymer was 17.6 g, and the residue after the Soxlet extraction was 96 wt~. For the polymer, the weight average molecular weight was 110,000 and the number average molecular weight was 49,000. The melting point and the results of the 13C-NMR analysis of the polymer were similar to those in Example 1.
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 after the Soxlet extraction was 95 wt%. For the polymer, 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.
EXAMPLE ? 5 Th~ 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.
, .
1 The yield of the polymer was 16.3 g, and the residue after the Soxlet extraction was 95 wt%. For the polymer, the weight average molecular weight was 43,000 and the number average molecularweight was 22,000. The melting point and the results of the 13C~NMR analysis of the polymer were similar to those in Example 1.
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 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, 15 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.
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 25 number average molecular weight was 210,000. The melting point and the results of the 13C-NMR analysis of the l polymer were similar to those in Example 1.
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 resldue after the Soxlet extraction was 93 wt%. For the polymer, l~ 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 1.
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 10 mmol, the amount of the styrene introduce~
20 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, 0.4 g of a polymer was obtained. The residue after the Soxlet extraction was ~3 wt%.
The melting point and the results of the 13C-NMR
analysis of the polymer were similar to those in Example l.
,~.
g~
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 dîethoxide (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 o~ 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 was2 hoursO 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.
The 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.
1 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.
The procedure of (2) in Example 1 was repeated with the exceptions that 0.05 mmol as *itanium 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 o~ 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.
The procedure of (2) in Example 1 was repeated with the exceptions that 0.05 mmol as titanium atom of a magnesium 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 25 temperature was 50C and the polymerization time was 2 hours. In this way, 1.2 g of a polymer was obtained.
~L~ 7 1 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.
The procedure of (2) in Example 1 was repeated with the exceptions that 0,02 mmol of titanium trichloride was used as the titanium c~mpound co~ponent, the amount as aluminum atom of the methylaluminoxane used was 20 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, 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 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%.
The procedure of Example 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 25 after the Soxlet extraction was 55 wt%. For the polymer, the weight average molecular weight was 38,000, the number 1 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 (Eig. 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%.
The procedure of Example 22 was repeated with the exception that 40 ml of p-chlorostyrene was used as a start-ing monomer in place of the styrene.
The yield of the polymer was 3. O g, and the residueafter the Soxlet extraction was 90 w-t%. For the polymer, the weight average molecular weight was 20,000, the number average molecular weight was 2,000 and the melting point was 295C. By comparison of the aromatic ring Cl carbon signal in 13C-NMR of the polymer (Fig. 5(a)) and the aromatic ring Cl carbon signal in 13NMR of atactic poly(p-chlorostyrene) as a reference polymer (Fig. 5(b)), it was found that the polymer was poly(p-chlorostyrene) of such high syndiotactic configuration that the tacticity as determined in the racemic pentad was at least 90~, which had never been obtained.
The procedure of Example 2 was repeated with the exceptions that 24.8 ml of m-chlorostyrene was used as a 2~ starting monomer and 0.05 mmol of tetraethoxytitanium was used as a titanium compound. In this way, 1.8 g of a l polymer was obtained~
The residue after the Soxlet extraction was 51 wt%.
For the polymer, the weight average molecular weight was 47,000 and the number average molecular weight was 13,000.
sased on the aromatic ring C1 carbon signal in 13C-NMR of the polymer (Fig. 6), it was determined that the polym~r was of such syndiotactic configuration that the tacticity as determined at the racemic pentad was at least 80%.
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 obtained.
The residue after the Soxlet extraction was 98 wt~.
For the polymer, the weight average molecular weight was 59r000l the number average molecular weight was 26,000 and the melting point was 206C. Based on the aromatic ring Cl carbon signal in 13C-NMR 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%.
~æ~7 1 EXAMPI,E 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 weight was 8,800. sased on the aromatic ring Cl carbon signal in 13C-NMR of the polymer (Fig. 8), it was determined that the polymer was of such syndiotactic configuration that -the tacticity as determined at the racemic pentad was a-t least 70%.
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 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 extracti~n was 99 wt%.
For the polymer, the weight average molecular weight was 71,000, the number average molecular weight was 21,000 and the meltin~ point was 310C. Based on the aromatic ring C
carbon signal in l3C-NMR of the pol~ner (Fig. 9), it was 1 determined that the polymer was of such syndiotactic configu-ration that the tacticity as determined at the racemic pentad was at least 94%.
-The procedure of Example 22 was repeated with the exceptions that a mixture of 2g.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 aftex the Soxlet extraction was 70 wt%.
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 t~is 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.
=
The procedure of Example 35 was repeated with the exceptions that 39.4 ml of p-methylstyrene was used as a g~
1 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,G00 and the melting point was 168C. ~or the methyl ethyl ketone extraction residue, the weight average molecular weight was 48,000, the number average molecular weight was 23,000 and the melting point was 173C.
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~.
The procedure of (2) in Example 1 was repeated with the exceptions that 0.05 mmol of cyclopentadienyl titanium dichloride was used as the ti~anium compound component, the amount of the methy]aluminoxane used was 30 mmol (as 1 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, 9.2 g of a polymer was 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 10 of the polymer were similar to those in Example 1.
EXA~PLE 46 -The procedure of (2) i.n Example 1 was repeated with the exceptions that O.OS mmo3. of bispentamethylcyclopent.adi.enyl titanium dichloride was used as the titanium compound 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 obtained.
The residue after the Soxlet extraction was 95.3%.
For the polymer, the weight average molecular weight was 167~000 and the nu~ber 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
methanol mixture and then dried to yield 1.0 g o~ 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 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.
The procedure of (2) in Example 1 was repeated with the exception that 0.~5 mmol of titanium tetrabromide was used as the titanium compound component.
~ ~t~ 7 l The yleld 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 average molecular weight was 160,000. The melting point and the results of the 13C-NMR analysis of the polymer were similar to those in Example 1.
The procedure of (2) in Example l was repeated with the exception that 0.05 mmol of titanium tetraethoxide was used as the titanium compound component.
The yield of the polymer was l~.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,Q00. The melting point and the results of the l3C-NMR analysis of the polymer were similar to those in Example l.
The procedure of (2) in Example l 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 extraction was 92 wt~.
For the polymer, the weight average molecular weight was ~Z 5~ ~!97 l 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.
-The procedure of (2) in Example 1 was repeated with the exceptions that 0.05 mmol of titanium tetraethoxide was used as the titanium compountd component, the amount as aluminum atorn of the methylaluminoxane used was 5 mmol, the amount of the styrene introduced was 150 ml, the amount of the toluene used was 20 ml, the polymerization temperature was ~0C 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 welght 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.
The procedure of (2) in Example 1 was repeated with the ext~eptions 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, thepolymeriza`tion temperature was 50C
and the polymerization time was 4 hours. In this way, 1.9 g of a polymer was obtained.
9t7 1 The residue after the Soxlet extraction was 89 wt%.
For 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.
EX~MPLE 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 way, 1.8 g of a polymer was used.
The residue after the Soxlet extraction was 92 wt%.
For the polymer, the weight average molecular weight was 201,000 and the number average molecular weight was 101,000.
The meltin~ point and the results of the 13C-NMR analysis of the polymer were similar to those in Example 1.
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, 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~.
~or the polymer, the weight average molecular weight was 1 756,000 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.
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 10 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 13C-NMR analysis of the polymer were similar to those in Example 1.
. .
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 ~ of a polymer was obtained.
., - 15 ~2~
1 The residue after the Soxlet extraction was 91 wt%.
The mel-ting point and -the results of the 13C-NMR analysis of the polymer were similar to those in Example 1.
EX~MPLE 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 rèsidue 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.
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 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 resîdue after the Soxlet extraction was 87 wt%.
The melting point and the results of the 13C-NMR analysis of 1 the polymer were similar to those in Example 1.
The procedure of (2) in Example 1 was repeated with the exception that 0.05 mmol of tetra(2-ethylhexyloxy)-titanium was used as the titanium compound c~mponent.
The yield of the polymer was 20.0 g. The residue after the 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 and the results of the 13C-NMR analysis of the polymer were similar to those in Example 1.
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 10.0 g, and the residueafter the Soxlet extraction was 97 wt%. For the polymer, the weight a~erage molecular weight was 360,000 and the number average molecular weight was 160,000. The melting point and the results of the 13C~NMR analysis of the polymer were similar to those in Example 1.
The procedure of (2) in Example 1 was repeated with the exception that 0.05 mmol of titanium diisopropoxy di-chloride was used as the titanium compound component.
~2~
1 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 2xample lo _ The procedure of (2) in Example 1 was xepeated with the exception that 0.05 mmol of titanium triisopropoxy mono-chloride was used as the titanium compound component.
The yield of the polymer was 17.0 g, and the residueafter 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.
E~AMPLE 18 The procedure of (2) in Example 1 was repeated with the exceptions that 0.01 mmol of bist2,4-pentanedionate) 20 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 25 weight average molecular weight was 380,000 and the number average molecular weight was 170.000. The melting point and 1 the results of the 13C-NMR analysis of the polymer were similar to those in Example 1.
The procedure of (2) in Example 1 was repeated with the exceptions that 0.05 mmol of isopropoxytitanium 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 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.
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.
. .
The procedure of (2) in Example 1 was repeated with the exception that 0.05 mmol of biscyclopentadienyltitanium dichloride was used as the titanium compouncl component.
The yield of the polymer was 3.0 g, ancl the residue after the Soxlet extraction was S0 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.
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-ing mixture was stirred at room temperature for 40 minutes.
Then, 0.05 mmol of cyclopentadienyltitanium trichloride was 1 added. After the resulting mixture was raised in temperature to 50C, 1~0 ml of styrene was introduced and polymerlzed for 2 hours.
The yield of the polymer was 17.6 g, and the residue after the Soxlet extraction was 96 wt~. For the polymer, the weight average molecular weight was 110,000 and the number average molecular weight was 49,000. The melting point and the results of the 13C-NMR analysis of the polymer were similar to those in Example 1.
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 after the Soxlet extraction was 95 wt%. For the polymer, 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.
EXAMPLE ? 5 Th~ 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.
, .
1 The yield of the polymer was 16.3 g, and the residue after the Soxlet extraction was 95 wt%. For the polymer, the weight average molecular weight was 43,000 and the number average molecularweight was 22,000. The melting point and the results of the 13C~NMR analysis of the polymer were similar to those in Example 1.
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 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, 15 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.
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 25 number average molecular weight was 210,000. The melting point and the results of the 13C-NMR analysis of the l polymer were similar to those in Example 1.
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 resldue after the Soxlet extraction was 93 wt%. For the polymer, l~ 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 1.
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 10 mmol, the amount of the styrene introduce~
20 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, 0.4 g of a polymer was obtained. The residue after the Soxlet extraction was ~3 wt%.
The melting point and the results of the 13C-NMR
analysis of the polymer were similar to those in Example l.
,~.
g~
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 dîethoxide (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 o~ 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 was2 hoursO 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.
The 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.
1 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.
The procedure of (2) in Example 1 was repeated with the exceptions that 0.05 mmol as *itanium 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 o~ 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.
The procedure of (2) in Example 1 was repeated with the exceptions that 0.05 mmol as titanium atom of a magnesium 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 25 temperature was 50C and the polymerization time was 2 hours. In this way, 1.2 g of a polymer was obtained.
~L~ 7 1 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.
The procedure of (2) in Example 1 was repeated with the exceptions that 0,02 mmol of titanium trichloride was used as the titanium c~mpound co~ponent, the amount as aluminum atom of the methylaluminoxane used was 20 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, 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 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%.
The procedure of Example 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 25 after the Soxlet extraction was 55 wt%. For the polymer, the weight average molecular weight was 38,000, the number 1 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 (Eig. 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%.
The procedure of Example 22 was repeated with the exception that 40 ml of p-chlorostyrene was used as a start-ing monomer in place of the styrene.
The yield of the polymer was 3. O g, and the residueafter the Soxlet extraction was 90 w-t%. For the polymer, the weight average molecular weight was 20,000, the number average molecular weight was 2,000 and the melting point was 295C. By comparison of the aromatic ring Cl carbon signal in 13C-NMR of the polymer (Fig. 5(a)) and the aromatic ring Cl carbon signal in 13NMR of atactic poly(p-chlorostyrene) as a reference polymer (Fig. 5(b)), it was found that the polymer was poly(p-chlorostyrene) of such high syndiotactic configuration that the tacticity as determined in the racemic pentad was at least 90~, which had never been obtained.
The procedure of Example 2 was repeated with the exceptions that 24.8 ml of m-chlorostyrene was used as a 2~ starting monomer and 0.05 mmol of tetraethoxytitanium was used as a titanium compound. In this way, 1.8 g of a l polymer was obtained~
The residue after the Soxlet extraction was 51 wt%.
For the polymer, the weight average molecular weight was 47,000 and the number average molecular weight was 13,000.
sased on the aromatic ring C1 carbon signal in 13C-NMR of the polymer (Fig. 6), it was determined that the polym~r was of such syndiotactic configuration that the tacticity as determined at the racemic pentad was at least 80%.
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 obtained.
The residue after the Soxlet extraction was 98 wt~.
For the polymer, the weight average molecular weight was 59r000l the number average molecular weight was 26,000 and the melting point was 206C. Based on the aromatic ring Cl carbon signal in 13C-NMR 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%.
~æ~7 1 EXAMPI,E 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 weight was 8,800. sased on the aromatic ring Cl carbon signal in 13C-NMR of the polymer (Fig. 8), it was determined that the polymer was of such syndiotactic configuration that -the tacticity as determined at the racemic pentad was a-t least 70%.
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 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 extracti~n was 99 wt%.
For the polymer, the weight average molecular weight was 71,000, the number average molecular weight was 21,000 and the meltin~ point was 310C. Based on the aromatic ring C
carbon signal in l3C-NMR of the pol~ner (Fig. 9), it was 1 determined that the polymer was of such syndiotactic configu-ration that the tacticity as determined at the racemic pentad was at least 94%.
-The procedure of Example 22 was repeated with the exceptions that a mixture of 2g.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 aftex the Soxlet extraction was 70 wt%.
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 t~is 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.
=
The procedure of Example 35 was repeated with the exceptions that 39.4 ml of p-methylstyrene was used as a g~
1 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,G00 and the melting point was 168C. ~or the methyl ethyl ketone extraction residue, the weight average molecular weight was 48,000, the number average molecular weight was 23,000 and the melting point was 173C.
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~.
The procedure of (2) in Example 1 was repeated with the exceptions that 0.05 mmol of cyclopentadienyl titanium dichloride was used as the ti~anium compound component, the amount of the methy]aluminoxane used was 30 mmol (as 1 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, 9.2 g of a polymer was 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 10 of the polymer were similar to those in Example 1.
EXA~PLE 46 -The procedure of (2) i.n Example 1 was repeated with the exceptions that O.OS mmo3. of bispentamethylcyclopent.adi.enyl titanium dichloride was used as the titanium compound 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 obtained.
The residue after the Soxlet extraction was 95.3%.
For the polymer, the weight average molecular weight was 167~000 and the nu~ber 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
Claims (3)
1. A process for producing styrene polymers which com-prises 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.
(A) a titanium compound, and (B) a contact product of an organoaluminum compound and a condensation agent.
2. The process as claimed in Claim 1, wherein the titanium compound is at least one compound selected from titanium compounds and titanium chelate compounds represented by the general formulae:
TiR1aR2bR3cX14-(a + b + c) and TiR1dR2eX13-(d + e) (wherein R1, 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 group, a substituted cyclopentadienyl group or an indenyl group, X1 represents a halogen atom, a, b and c each repre-sent an integer of 0 to 4, and d and e each represent an integer of 0 to 3).
TiR1aR2bR3cX14-(a + b + c) and TiR1dR2eX13-(d + e) (wherein R1, 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 group, a substituted cyclopentadienyl group or an indenyl group, X1 represents a halogen atom, a, b and c each repre-sent an integer of 0 to 4, and d and e each represent an integer of 0 to 3).
3. The process as claimed in Claim 1, wherein the component (B) is a product resulting from modification of trimethylaluminum with water.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP252531/1985 | 1985-11-11 | ||
| JP25253185 | 1985-11-11 | ||
| JP61101927A JPS62187708A (en) | 1985-11-11 | 1986-05-06 | Production of styrene polymer |
| JP101927/1986 | 1986-05-06 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1250697A true CA1250697A (en) | 1989-02-28 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000522291A Expired CA1250697A (en) | 1985-11-11 | 1986-11-06 | Process for production of styrene polymers |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US4680353A (en) |
| EP (1) | EP0224097B1 (en) |
| JP (1) | JPS62187708A (en) |
| KR (1) | KR890004065B1 (en) |
| CA (1) | CA1250697A (en) |
| DE (1) | DE3677333D1 (en) |
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| US5189125A (en) * | 1985-07-29 | 1993-02-23 | Idemitsu Kosan Co., Ltd. | Process for producing syndiotactic styrene copolymer |
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| JP2531583B2 (en) * | 1987-01-28 | 1996-09-04 | 出光興産株式会社 | Styrene-based copolymer and method for producing the same |
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| US5166238A (en) * | 1986-09-22 | 1992-11-24 | Idemitsu Kosan Co., Ltd. | Styrene-based resin composition |
| EP0307488B1 (en) * | 1987-09-15 | 1992-07-22 | Idemitsu Kosan Company Limited | A polystyrene-based resin composition |
| US5891951A (en) * | 1987-09-14 | 1999-04-06 | Idemitsu Kosan Co., Ltd. | Styrene-based resin composition |
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| JPH082925B2 (en) * | 1986-11-10 | 1996-01-17 | 出光興産株式会社 | Method for producing styrenic polymer |
| IL84798A (en) * | 1986-12-15 | 1991-09-16 | Montedison Spa | Production of crystalline vinyl aromatic polymers having mainly a syndiotactic structure |
| IT1201715B (en) * | 1986-12-15 | 1989-02-02 | Montedison Spa | CRYSTALLINE STYRENE POLYMERS ESSENTIAL SYNDIOTACTIC AND PROCEDURE FOR THEIR PREPARATION |
| WO1988008432A1 (en) * | 1987-04-20 | 1988-11-03 | Mitsui Petrochemical Industries, Ltd. | Olefin polymerization catalyst and process for polymerizing olefin |
| JPH085929B2 (en) * | 1987-01-22 | 1996-01-24 | 出光興産株式会社 | Method for producing styrenic polymer |
| US6013726A (en) * | 1987-04-12 | 2000-01-11 | Idemitsu Kosan Co., Ltd. | Composition of styrene resin, thermoplastic resin and rubber |
| US5206199A (en) * | 1987-04-20 | 1993-04-27 | Mitsui Petrochemical Industries, Ltd. | Catalyst for polymerizing an olefin and process for polymerizing an olefin |
| US4774301A (en) * | 1987-06-08 | 1988-09-27 | The Dow Chemical Company | Zirconium containing catalysts and method of use |
| CA1312069C (en) * | 1987-06-17 | 1992-12-29 | Richard E. Campbell, Jr. | Catalyst and process for preparation of syndiotactic polystyrene |
| US5196490A (en) * | 1987-06-17 | 1993-03-23 | The Dow Chemical Company | Process for preparation of syndiotactic polystyrene |
| US5045517A (en) * | 1987-06-17 | 1991-09-03 | The Dow Chemical Company | Catalyst and process for preparation of syndiotactic polystyrene |
| JP2566889B2 (en) * | 1987-07-13 | 1996-12-25 | 出光興産株式会社 | Method for producing olefin polymer or styrene polymer |
| US6046275A (en) * | 1987-09-14 | 2000-04-04 | Idemitsu Kosan Co., Ltd. | Styrene resin with rubber polymer particles |
| US6093768A (en) * | 1987-09-14 | 2000-07-25 | Idemitsu Kosan Co., Ltd. | Syndiotactic styrene resin, thermoplastic resin and rubber |
| US6008293A (en) * | 1987-09-14 | 1999-12-28 | Idemitsu Kosan Co., Ltd. | Syndiotactic polystyrene and polycarbonate resin compositions |
| US6087435A (en) * | 1987-09-14 | 2000-07-11 | Idemitsu Kosan Co., Ltd. | Composition of styrene resin, thermoplastic resin and rubber particles |
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-
1986
- 1986-05-06 JP JP61101927A patent/JPS62187708A/en active Granted
- 1986-10-23 US US06/923,395 patent/US4680353A/en not_active Ceased
- 1986-11-06 CA CA000522291A patent/CA1250697A/en not_active Expired
- 1986-11-08 EP EP86115495A patent/EP0224097B1/en not_active Expired - Lifetime
- 1986-11-08 DE DE8686115495T patent/DE3677333D1/en not_active Expired - Fee Related
- 1986-11-11 KR KR1019860009480A patent/KR890004065B1/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| KR890004065B1 (en) | 1989-10-18 |
| KR870011157A (en) | 1987-12-21 |
| DE3677333D1 (en) | 1991-03-07 |
| US4680353A (en) | 1987-07-14 |
| JPS62187708A (en) | 1987-08-17 |
| EP0224097B1 (en) | 1991-01-30 |
| JPH0137403B2 (en) | 1989-08-07 |
| EP0224097A1 (en) | 1987-06-03 |
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