JP2002053606A - Catalyst for copolymerization of styrene and olefin, and method for producing styrene-based copolymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a catalyst for copolymerization of styrene and an olefin easily synthesizable, having high polymerization activity in a wide temperature range, capable of controlling a styrene content, capable of performing random copolymerization in which styrene content exceeds 50 mol%, and hardly affected by impurities in the polymerization system. SOLUTION: The catalyst for copolymerization of styrene and an olefin comprising a titanium complex component (A) expressed by CpTiLmX3-m and an activating agent (B) consisting of an alkylaluminumoxy compound or a boron compound (in the formula, Cp is a group having a cyclopentadiene-type anionic skeleton; L is a chelating anionic ligand whose coordinated atom is oxygen; X is H, an alkyl, an alkoxy or the like; and m is an integer of 1-3). A method for producing a styrene-based copolymer by using the catalyst.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a styrene-olefin copolymerization catalyst and a method for producing a styrene-based copolymer using the same. For more information,
It is easy to synthesize and has a high polymerization activity in a wide temperature range from low to high temperatures. In addition, in the copolymerization of styrene and ethylene, the styrene content can be freely controlled, especially when the styrene content exceeds 50 mol%. A copolymerization catalyst of styrenes and olefins that can be polymerized and is less affected by impurities such as water in the polymerization system,
And a method for efficiently producing a styrenic copolymer using the catalyst.

[0002]

2. Description of the Related Art A copolymer of a styrene monomer and an olefin monomer obtained by using a catalyst system containing a transition metal complex as a main component and a method for producing the same have been known. For example, Japanese Patent No. 262070 describes a pseudorandom copolymer having no styrene chain, which is obtained by using a complex having a so-called constrained geometric structure (CGC). Since this copolymer does not have a styrene head-tail chain, there is no stereoregularity in the chain, and since there is no styrene chain, the styrene content cannot exceed 50 mol%. The polymerization activity was practically insufficient.

Further, the synthesis of a constrained geometry type metallocene compound involves a large number of synthesis routes of 2 to 5 steps or more, which not only complicates the synthesis method, but also has a low polymerization activity, especially at low temperatures, and furthermore, the polymerization system However, there is a problem that a large amount of an organometallic component is required because it is easily affected by impurities such as trace amounts of water.

Japanese Patent No. 2,840,605 discloses a copolymer of styrene chain with ethylene having high syndiotacticity. However, this copolymer has a melting peak based on syndiotactic polystyrene and polyethylene, which is observed by a differential scanning calorimeter, substantially contains a block structure of polystyrene and polyethylene, and further has a high glass transition temperature, heat resistance, and heat resistance. Although excellent in chemical properties and the like, properties such as flexibility and compatibility with other resins are not sufficient.

[0005] Japanese Patent Application Laid-Open No. 11-130808 discloses 2
Copolymers of styrene and olefins containing a head-to-tail chain of more than one styrene unit are described.
Although the head-tail chain of the styrene unit of this copolymer is mainly isotactic, a crystalline copolymer having a substantially low randomness, in which the melting point based on isotactic polystyrene is observed by a differential scanning calorimeter. Inferior in properties such as flexibility and compatibility with other resins.

Macromolecules 1997, 30, 685-693 describes copolymers of styrene and ethylene containing a head-tail chain of styrene units. Although the stereoregularity of the styrene chain of this copolymer is an isotactic structure, it does not include heterogeneous bonds such as tail-to-tail and head-to-head of styrene units.

[0007] Japanese Patent No. 2836188 describes a copolymer of styrene and ethylene having an isotactic structure of a styrene chain. Since this copolymer has a high degree of alternation, the contents of styrene and ethylene are each 50 mol%, which has the disadvantage that the monomer ratio of the copolymer cannot be changed substantially. Further, the polymerization activity is not practically sufficient.

JP-A-11-199614 describes a method for producing a styrene-olefin copolymer having a high styrene content using a metallocene catalyst having a crosslinked structure. However, the synthesis of organometallic complex catalysts which are compounds having two groups containing a cyclopentadienyl skeleton as ligands (metallocene compounds in a narrow sense) and have a cross-linked structure is very complicated. Is not practical for industrial implementation.

As described above, various copolymers of styrene and ethylene and methods for producing the same have been reported. However, a catalyst system which can be synthesized more easily in industrial practice and a styrene-based catalyst using the catalyst are described. The technique of obtaining a random copolymer while freely controlling the content has not yet been achieved.

[0010]

SUMMARY OF THE INVENTION In view of the above circumstances, the present invention has been developed to develop a catalyst system which can be synthesized more easily in industrial practice and a method for producing a substantially random copolymer using the catalyst. As a result of focusing, as shown in JP-A-11-199622, a group 1 containing a cyclopentadienyl skeleton was obtained.
A catalyst system comprising a group 4 transition metal complex having at least one dicarbonyl ligand, an alkylaluminum oxy compound and / or a cation generator as a styrene-ethylene copolymerization catalyst It was found to be excellent in long-term storage stability and reproducibility of activity. However, this method also has a problem that random copolymerization in which the styrene content exceeds 50 mol% is substantially difficult, and the polymerization activity at low temperatures is relatively low.

The present invention can be easily synthesized for industrial use, has a high polymerization activity in a wide temperature range from low to high temperatures, and freely controls the styrene content in the copolymerization of styrene and ethylene. Can,
In particular, random copolymerization with a styrene content exceeding 50 mol% is possible, and furthermore, it has been made to find a styrene-ethylene copolymerization catalyst system which is hardly affected by impurities such as water in the polymerization system. is there.

[0012]

DISCLOSURE OF THE INVENTION The present invention provides an asymmetric monovalent bidentate chelate anion in which one molecule of a ligand containing a cyclopentadienyl skeleton and two oxygen atoms are easily coordinated. Titanium complex having a neutral ligand has high polymerization activity over a wide temperature range from low to high temperature for copolymerization of styrenes and olefins, and styrene content in styrene and ethylene copolymerization Can be freely controlled, especially when the styrene content is 50%.
This is based on the surprising fact that random copolymerization of more than mol% is possible and that it is hardly affected by impurities such as water in the polymerization system.

That is, the present invention relates to a polymerization catalyst for olefins comprising a titanium complex component (A) represented by the following formula (1) and an activator (B) selected from an alkylaluminumoxy compound or a boron compound. It is. CpTiL _m X _3-m (1) (wherein Cp represents a group having a cyclopentadiene-type anion skeleton. L represents an asymmetric 1 in which oxygen is a coordinating atom.
Represents a divalent bidentate chelating anionic ligand. X is hydrogen,
Represents an alkyl group, an alkoxy group, an aryl group, an allyloxy group, an aralkyl group or a halogen having 1 to 20 carbon atoms. m represents an integer of 1 to 3. When there are a plurality of L or X, they may be independently the same or different. )

Further, according to the present invention, in the titanium complex component (A) represented by the above formula (1), L is the following formula (2)
The present invention relates to a polymerization catalyst for the above-mentioned olefins, which is an asymmetric monovalent bidentate chelating anionic ligand produced from the compound represented by the formula:

[0015]

Embedded image (Wherein R ¹ , R ² , and R ³ are hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkoxy group, an aryl group, an allyloxy group,
Represents an aralkyl group, an alkylamide group, or an arylamide group, wherein R ¹ and R ³ are not the same, R ¹ and R ² may be the same or different, and R ² and R ³ are the same They may be different or different. Further, R ¹ and R ² may be bonded to each other to form a ring. )

Further, the present invention relates to a method for producing a styrene copolymer, comprising copolymerizing at least one styrene and at least one olefin in the presence of the above-mentioned polymerization catalyst. is there.

In the present invention, the term "polymerization" means
The term "polymer" is used to include not only homopolymers but also copolymers, as well as homopolymerization.

The styrene and olefin copolymerization catalyst of the present invention and the method for producing a styrene copolymer using the same will now be described in detail. The titanium complex component (A) of the copolymerization catalyst of the present invention is represented by the above formula (1), wherein Cp represents a group having a cyclopentadiene type anion skeleton. In L, oxygen is a coordinating atom,
Represents an asymmetric monovalent bidentate chelating anionic ligand.
X represents hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkoxy group, an aryl group, an allyloxy group, an aralkyl group or a halogen. m represents an integer of 1 to 3. When there are a plurality of L or X, they may be independently the same or different.

Among them, an asymmetric one in which oxygen is a coordinating atom
Is a monovalent bidentate chelating anionic ligand L of the above formula
When produced from the compound represented by (2),
Is preferred, wherein R¹, R^Two, R^ThreeIs hydrogen, carbon number 1
To 20 alkyl groups, alkoxy groups, aryl groups, ants
Roxy, aralkyl, alkylamide, aryl
Represents an amide group;¹And R^ThreeAre not the same, R¹And R^TwoIs
May be the same or different;^TwoAnd R^ThreeIs
They may be the same or different. Also, R ¹When
R^TwoMay combine with each other to form a ring.

X and R in the above formulas (1) and (2)
¹ to R ³ alkyl group, alkoxy group, aryl group, aryloxy group, aralkyl group, an alkyl amide group, an alkyl arylamide group, an aryl, specific examples of the aralkyl moiety, methyl, ethyl, propyl, isopropyl, n- Butyl, isobutyl, t-butyl, sec-butyl, n-pentyl, isopentyl, 1-methylbutyl, 2-methylbutyl, 1,2-dimethylpropyl, neopentyl, cyclopentyl, n-hexyl, isohexyl, 1-methylpentyl, 2- Methylpentyl, 3-
Methylpentyl,

1,1-dimethylbutyl, 2,2-dimethylbutyl, 3,3-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 1,1-ethylmethylpropyl, 1-ethylbutyl, 2-ethylbutyl, cyclohexyl, n-heptyl, isoheptyl, 4-methylhexyl, 3-methylhexyl, 2-methylhexyl, 1-methylhexyl, 1,1-dimethylpentyl,
2,2-dimethylpentyl, 3,3-dimethylpentyl, 4,4-dimethylpentyl, 1,2-dimethylpentyl, 1,3-dimethylpentyl, 1,4-dimethylpentyl, 1-ethylpentyl, 1-propyl Butyl, 2
-Ethylpentyl, 3-ethylpentyl,

1,1-ethylmethylbutyl, 1,1-diethylpropyl, 2,3-dimethylpentyl, 2,4-
Dimethylpentyl, 3,4-dimethylpentyl, 1-ethyl-2-methylbutyl, 1-ethyl-3-methylbutyl, 4-methylcyclohexyl, 3-methylcyclohexyl, cycloheptyl, 1,1,2-trimethylbutyl, 1, 1,3-trimethylbutyl, 2,2,1-trimethylbutyl, 2,2,3-tylmethylbutyl, 3,
3,1-trimethylbutyl, 3,3,2-trimethylbutyl, 1,1,2,2-tetramethylpropyl, n-octyl, 1-methylheptyl, 2-methylheptyl, 3
-Methylheptyl, 4-methylheptyl, 5-methylheptyl,

Isooctyl, 1-ethylhexyl, 2-
Ethylhexyl, 3-ethylhexyl, 4-ethylhexyl, 1,1-dimethylhexyl, 2,2-dimethylhexyl, 3,3-dimethylhexyl, 4,4-dimethylhexyl, 5,5-dimethylhexyl, 1,2-dimethyl Hexyl, 1,3-dimethylhexyl, 1,4-dimethylhexyl, 1,5-dimethylhexyl, 2,3-dimethylhexyl, 2,4-dimethylhexyl, 3,4-
Dimethylhexyl, 2,5-dimethylhexyl, 3,5
-Dimethylhexyl, 1,1-methylethylpentyl,
1-ethyl-2-methylpentyl, 1-ethyl-3-methylpentyl, 1-ethyl-4-methylpentyl, 2-
Ethyl-1-methylpentyl,

2,2-ethylmethylpentyl, 3,3-
Ethyl methylpentyl, 2-ethyl-3-methylpentyl, 2-ethyl-4-methylpentyl, 3-ethyl-4
-Methylpentyl, 3-ethyl-2-methylpentyl,
1,1-diethylbutyl, 2,2-diethylbutyl,
1,2-diethylbutyl, 1,1-methylpropylbutyl, 2-methyl-1-propylbutyl, 3-methyl-1-
Propylbutyl, 4-ethylcyclohexyl, 3-ethylcyclohexyl, 3,4-dimethylcyclohexyl,
1,1,2-trimethylpentyl, 1,1,3-trimethylpentyl, 1,1,4-trimethylpentyl,

2,2,1-trimethylpentyl, 2,
2,3-trimethylpentyl, 2,2,4-trimethylpentyl, 3,3,1-trimethylpentyl, 3,3
2-trimethylpentyl, 3,3,4-trimethylpentyl, 1,2,3-trimethylpentyl, 1,2,4-
Trimethylpentyl, 1,3,4-trimethylpentyl, 1,2,3-trimethylpentyl, 1,2,4-trimethylpentyl, 1,3,4-trimethylpentyl,
1,1,2,2-tetramethylbutyl, 1,1,3,3
-Tetramethylbutyl, 1,1,2,3-tetramethylbutyl, 2,2,1,3-tetramethylbutyl, 1-ethyl-1,2-dimethylbutyl, 2-ethyl-1,2-
Dimethylbutyl, 1-ethyl-2,3-dimethylbutyl,

N-nonyl, isononyl, 1-methyloctyl, 2-methyloctyl, 3-methyloctyl, 4-methyloctyl
Methyloctyl, 5-methyloctyl, 6-methyloctyl, 1-ethylheptyl, 2-ethylheptyl, 3-
Ethylheptyl, 4-ethylheptyl, 5-ethylheptyl, 1,1-dimethylheptyl, 2,2-dimethylheptyl, 3,3-dimethylheptyl, 4,4-dimethylheptyl, 5,5-dimethylheptyl, 6, 6-dimethylheptyl, 1,2-dimethylheptyl, 1,3-dimethylheptyl, 1,4-dimethylheptyl, 1,5-dimethylheptyl, 1,6-dimethylheptyl, 2,3-dimethylheptyl
Dimethylheptyl, 2,4-dimethylheptyl, 2,5
-Dimethylheptyl, 2,6-dimethylheptyl,

3,4-dimethylheptyl, 3,5-dimethylheptyl, 3,6-dimethylheptyl, 4,5-dimethylheptyl, 4,6-dimethylheptyl, 5,6-dimethylheptyl
Dimethylheptyl, 1,1,2-trimethylhexyl,
1,1,3-trimethylhexyl, 1,1,4-trimethylhexyl, 1,1,5-trimethylhexyl, 2,
2,1-trimethylhexyl, 2,2,3-trimethylhexyl, 2,2,4-trimethylhexyl, 2,2
5-trimethylhexyl, 3,3,1-trimethylhexyl, 3,3,2-trimethylhexyl, 3,3,4-
Trimethylhexyl, 3,3,5-trimethylhexyl, 4,4,1-trimethylhexyl, 4,4,2-trimethylhexyl, 4,4,3-trimethylhexyl,
4,4,5-trimethylhexyl,

5,5,1-trimethylhexyl, 5,
5,2-trimethylhexyl, 5,5,3-trimethylhexyl, 5,5,4-trimethylhexyl, 1,2,2
3-trimethylhexyl, 2,3,4-trimethylhexyl, 3,4,5-trimethylhexyl, 1,3,4-
Trimethylhexyl, 1,4,5-trimethylhexyl, 2,4,5-trimethylhexyl, 1,2,5-trimethylhexyl, 1,2,4-trimethylhexyl,
1,1-ethylmethylhexyl, 2,2-ethylmethylhexyl, 3,3-ethylmethylhexyl, 4,4-ethylmethylhexyl, 5,5-ethylmethylhexyl,
1-ethyl-2-methylhexyl, 1-ethyl-3-methylhexyl, 1-ethyl-4-methylhexyl, 1-
Ethyl-5-methylhexyl,

2-ethyl-1-methylhexyl, 3-ethyl-1-methylhexyl, 3-ethyl-2-methylhexyl, 1,1-diethylpentyl, 2,2-diethylpentyl, 3,3-diethylpentyl , 1,2-diethylpentyl, 1,3-diethylpentyl, 2,3-diethylpentyl, 1,1-methylpropylpentyl, 2,
2-methylpropylpentyl, 1-methyl-2-propylpentyl, n-decyl, isodecyl, 1-methylnonyl, 2-methylnonyl, 3-methylnonyl, 4-methylnonyl, 5-methylnonyl, 6-methylnonyl, 7-methylnonyl, -Ethyloctyl, 2-ethyloctyl, 3-ethyloctyl, 4-ethyloctyl, 5-ethyloctyl, 6-ethyloctyl,

1,1-dimethyloctyl, 2,2-dimethyloctyl, 3,3-dimethyloctyl, 4,4-dimethyloctyl, 5,5-dimethyloctyl, 6,6-dimethyloctyl
Dimethyloctyl, 7,7-dimethyloctyl, 1,2
-Dimethyloctyl, 1,3-dimethyloctyl, 1,
4-dimethyloctyl, 1,5-dimethyloctyl,
1,6-dimethyloctyl, 1,7-dimethyloctyl, 2,3-dimethyloctyl, 2,4-dimethyloctyl, 2,5-dimethyloctyl, 2,6-dimethyloctyl, 2,7-dimethyloctyl, 3, , 4-dimethyloctyl, 3,5-dimethyloctyl, 3,6-dimethyloctyl, 3,7-dimethyloctyl, 4,5-dimethyloctyl, 4,6-dimethyloctyl, 4,7-dimethyloctyl, 5, 6-dimethyloctyl, 5,7-
Dimethyloctyl,

N-undecyl, n-dodecyl, phenyl, benzyl, p-tolyl, m-tolyl, xylyl, mesitylyl, 2,6-dimethylphenyl, 2,4,6-trimethylphenyl, 2,6-dimethoxyphenyl, 2,
4,6-trimethoxyphenyl, 2,6-diisopropylphenyl, 2,4,6-triisopropylphenyl,
Naphthyl, 2-methoxyphenyl, 2-isopropoxyphenyl, 2-tert-butoxyphenyl, 2,6
-Di-tert-butylphenyl, 2-methylphenyl, 2-isopropylphenyl, 2-tert-butylphenyl, 2-methyl-6-isopropylphenyl,
2-methyl-6-tert-butylphenyl and the like.

As described above, 1 in which oxygen is a coordinating atom
It is an essential requirement of the present invention that the divalent bidentate chelating anionic ligand L is asymmetric, and the monovalent bidentate chelating anionic ligand L in which oxygen is a coordinating atom is a symmetric type. In the case of adopting the structure, the effect of the present invention is not sufficiently exhibited.

The asymmetric monovalent bidentate chelating anionic ligand L having these substituents and represented by the formula (1) and the formula (2), in which oxygen is a coordinating atom, is formed. Specific compounds include, for example, 1-phenyl-
1,3-butanedione, 2-methyl-3,5-hexanedione, 2-acetylcyclopentanone, 2-acetylcyclohexanone, 2-acetyl-1-tetralone, 2
-Acetylcycloheptanone, 2-acetylcyclooctanone, 2-acetylcyclononanone, 2-methyl-4
-Tert-butylcyclohexanone, 2-methyl-6-tert-butylcyclohexanone, 2-methyl-4,6-ditert-butylcyclohexanone,

2-acetyl-1-decalone, 3-acetyl-2-decalone, 2-acetyl-3-tert-butylcyclopentanone, 2-acetyl-4-tert-butylcyclopentanone, 1-phenoxy-1 , 3-
Butanedione, 1-methoxy-1,3-butanedione,
1-ethoxy-1,3-butanedione, 1-dimethylamide-1,3-butanedione, 1-diethylamide-
1,3-butanedione, 1-diphenylamide-1,3
-Butanedione, 1-piperidine-1,3-butanedione, 1-pyrrolidine-1,3-butanedione and the like. These may be used alone or in combination.

As the alkylaluminum oxy compound of the activator (B), the following general formulas (3), (4) and (5)
And at least one of the organic aluminum oxy compounds represented by (6).

[0036]

Embedded image (In the formula, R ^{4 to} R ⁶ may be the same or different, each represents a hydrocarbon group having 1 to 8 carbon atoms, and n represents an integer of 1 to 50.)

[0037]

Embedded image (In the formula, R ^{7 to} R ⁹ may be the same or different, each represents a hydrocarbon group having 1 to 8 carbon atoms, and n represents an integer of 1 to 50.)

[0038]

Embedded image (Wherein, R ¹⁰ is a hydrocarbon group having 1 to 8 carbon atoms, and n is 1 to 5
Represents an integer up to 0. )

[0039]

Embedded image (In the formula, R ^{11 to} R ¹⁴ may be the same or different, each represents a hydrocarbon group having 1 to 8 carbon atoms, and n represents an integer of 1 to 50.)

Specific examples of these alkylaluminumoxy compounds include methylaluminoxane, ethylaluminoxane, propylaluminoxane, butylaluminoxane, isobutylaluminoxane, methylethylaluminoxane, methylbutylaluminoxane, methylisobutylaluminoxane and the like. Particularly, methylaluminoxane, isobutylaluminoxane, and methylisobutylaluminoxane can be preferably used.

These alkyl aluminum oxy compounds may include alkyl aluminum compounds such as trimethyl aluminum, triethyl aluminum and triisobutyl aluminum.

Examples of the organic boron compound of the activator (B) include at least one of the organic boron compounds represented by the following general formulas (7) and (8). (BR ¹⁵ R ¹⁶ R ¹⁷ ) _n (7) (wherein, R ^{15 to} R ¹⁷ may be the same or different, and represent a halogenated aryl group or a halogenated aryloxy group having 1 to 14 carbon atoms.) Containing hydrocarbon group, n represents an integer of 1 to 4.)

A (BR ¹⁸ R ¹⁹ R ²⁰ R ²¹ ) _n (8) (where A is a quaternary amine or a quaternary ammonium salt or a carbocation or a metal cation having a valence of +1 to +4, R ^{18 to} R ²¹ may be the same or different, and a hydrocarbon group containing a halogenated aryl group or a halogenated allyloxy group having 1 to 14 carbon atoms, and n represents an integer of 1 to 4.)

Specific examples of the hydrocarbon groups of the above formulas (7) and (8) include phenyl, benzyl, p-tolyl, m-tolyl, xylyl, mesitylyl, 2,6-dimethylphenyl, 2,4,6- Trimethylphenyl, 2,6-dimethoxyphenyl, 2,4,6-trimethoxyphenyl,
Examples include 2,6-diisopropylphenyl, 2,4,6-triisopropylphenyl, naphthyl, o-isopropoxyphenyl, pentafluorophenyl, pentafluorobenzyl, tetrafluorophenyl, tetrafluorotolyl, and the like.

Specific examples of A in the above formula (8) include pyridinium, 2,4-dinitro-N, N-diethylanilinium, p-nitroanilinium, 2,5-dichloroaniline, p-nitro- N, N-dimethylanilinium, quinolinium, N, N-dimethylanilinium, methyldiphenylammonium, N, N-diethylanilinium, 8-chloroquinolinium, trimethylammonium, tripropylammonium, triethylammonium, tributylammonium, Triphenylphosphonium, ammonium, triphenylmethyl, sodium, lithium, potassium, cesium, calcium, magnesium and the like.

Specific examples of these organic boron compounds include trimethylammonium tetrakis (pentafluorophenyl) borate, triethylammonium tetrakis (pentafluorophenyl) borate, and triphenylphosphonium tetrakis (pentafluorophenyl).
Borate, triphenylcarbenium tetrakis (pentafluorophenyl) borate and the like. Most preferred is triphenylcarbenium tetrakis (pentafluorophenyl) borate.

The catalyst suitable for use in the present invention is a mixture of the transition metal compound (A) and the alkylaluminum oxy compound or the organoboron compound (B) in any order and in any suitable manner. Manufactured by combining in a manner. A preferable catalyst composition ratio of the component (A) and the component (B) is (A) :( B) = 1: 0.0
1-1: 10000.

The catalyst may be prepared in advance by mixing in a suitable solvent under an atmosphere of an inert gas such as nitrogen or argon, or the components (A) and (B) may be separately mixed with a monomer. Into the reactor
It may be prepared in a reactor. Suitable solvents for preparing the catalyst include hydrocarbon solvents such as alkane such as hexane and cyclohexane, and aromatic solvents such as toluene, benzene and ethylbenzene. Further, it is preferable to remove water and the like in these solvents in the pretreatment. The preparation temperature of the catalyst is from -20 ° C to 150 ° C.
Is optimal.

The styrenes usable in the present invention include:
There is no particular limitation as long as it is generally called a styrene-based monomer. Examples of these styrene-based monomers include styrene, p-methylstyrene, m-methylstyrene, o-methylstyrene and 2,4-dimethylstyrene. Alkylstyrenes such as styrene, 2,5-dimethylstyrene, 3,4-dimethylstyrene and 3,5-dimethylstyrene, p-chlorostyrene, m-chlorostyrene, o-chlorostyrene, p-bromostyrene, m-bromo Halogenated styrene such as styrene, o-bromostyrene, α-
Methylstyrene and the like can be mentioned.

The olefins usable in the present invention include, for example, ethylene and α-olefins having 3 to 30 carbon atoms. Specific examples of α-olefins include propylene, 1-butene, 1-hexene,
Methyl-1-pentene, 1-heptene, 1-octene,
1-decene and the like can be mentioned.

The α-olefins of the present invention include olefins represented by the following general formula (9) (hereinafter referred to as polar olefins). CH ₂ ＣＲCR ²² -Y (9) (wherein, R ²² is hydrogen, halogen, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms or 1 to 1 carbon atoms) 20 is an alkylsilyl group, Y is an ester group, a carboxyl group, a hydroxyl group, an amino group, a cyano group,
It is at least one functional group selected from the group consisting of an amide group and a nitro group. )

Specific examples of polar olefins include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, and i-butyl (meth) acrylate. Butyl (meth) acrylate, sec-butyl (meth) acrylate, t-butyl (meth) acrylate, n-amyl (meth) acrylate, i-amyl (meth) acrylate, (meth) acrylic acid, crotonic acid,
Cinnamic acid, maleic acid, fumaric acid, itaconic acid, monomethyl maleate, monoethyl maleate,

Hydroxymethyl (meth) acrylate,
2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-dimethylaminoethyl (meth) acrylate, 2-diethylaminoethyl (meth) acrylate, 2-dimethylamino Propyl (meth) acrylate, (meth) acrylonitrile, α
-Chloroacrylonitrile, ethacrylonitrile, 2-
Cyanoethyl (meth) acrylate, 2-cyanopropyl (meth) acrylate, (meth) acrylamide, α
-Chloro (meth) acrylamide, ethacrylamide,
N-methyl (meth) acrylamide, N-vinyl-ε-
Caprolactam, N-vinylpyrrolidone, 2-nitroethyl (meth) acrylate, 3-nitropropyl (meth) acrylate and the like can be mentioned.

The olefins that can be copolymerized with styrenes using the catalyst of the present invention include cyclic olefins. The cyclic olefin is not particularly limited, and may have a hydrocarbon group having 1 to 20 carbon atoms, a halogen atom, an oxygen atom or a substituent containing a nitrogen atom, and is usually a monocyclic ring having 3 to 12 carbon atoms. Cycloalkenes, monocyclic cycloalkadienes, polycyclic cycloalkenes, polycyclic cycloalkadienes, and the like.

Among the substituents, examples of the hydrocarbon group having 1 to 20 carbon atoms include methyl, ethyl, n-propyl, isopropyl, t-butyl, hexyl, cyclohexyl, An alkyl group having 1 to 20 carbon atoms such as a cyclooctyl group, a phenyl group, a naphthyl group, a benzyl group, an aryl group having 6 to 20 carbon atoms such as a p-tolyl group, an alkylaryl group, an arylalkyl group, a methylidene group, 1 to 1 carbon atoms such as ethylidene and propylidene
Examples thereof include alkenyl groups having 2 to 20 carbon atoms such as 20 alkylidene groups, vinyl groups, and allyl groups.

Specific examples of the substituent containing a halogen atom include halogen groups having 1 to 20 carbon atoms, such as halogen groups such as fluorine, chlorine, bromine and iodine, and chloromethyl, bromomethyl and chloroethyl groups. Examples include a substituted alkyl group. Specific examples of the substituent containing an oxygen atom include a methoxy group, an ethoxy group, a propoxy group, a carbonyl group having 1 to 20 carbon atoms such as a phenoxy group, a methoxycarbonyl group, and a carbon atom having 1 to 1 carbon atoms such as an ethoxycarbonyl group.
And 20 alkoxycarbonyl groups.

Specific examples of the substituent containing a nitrogen atom include a C1-C20 alkylamino group such as a dimethylamino group and a diethylamino group, and a cyano group. These substituents are preferably bonded to a carbon atom other than a double-bonded carbon atom.

Specific examples of the monocyclic cycloalkene include, for example, cyclopropene, cyclobutene, cyclopentene, 3,5-dimethylcyclopentene, cyclohexene, 3-chlorocyclohexene, 3-methoxycyclohexene, cyclooctene, cyclododecene and the like. Is mentioned.

Specific examples of monocyclic cycloalkadienes include, for example, cyclobutadiene, 1,3-cyclopentadiene, 1,3-cyclohexadiene, 1,4-
Cyclohexadiene, 5-ethyl-1,3-cyclohexadiene, 1,3-cycloheptadiene, 1,4-cycloheptadiene, 1,5-cyclooctadiene, 1,7
-Cyclododecadienes and the like.

Specific examples of polycyclic cycloalkenes include, for example, norbornene, 5-methylnorbornene, 5-ethylnorbornene, 5-propylnorbornene, 5,6-dimethylnorbornene, 1-methylnorbornene, and 7-methylnorbornene. Methyl norbornene, 5,5,6-trimethylnorbornene, 5-phenylnorbornene, 5-benzylnorbornene, 5-ethylidene-2-norbornene, 5-vinylnorbornene, 1,2-dihydrodicyclopentadiene, 5-chloronorbornene, , 5-dichloronorbornene, 5-fluoronorbornene, 5,
5,6-trifluoro-6-trifluoromethylnorbornene, 5-methoxynorbornene, 5-dimethylaminonorbornene, 5-cyanonorbornene and the like can be mentioned.

Specific examples of the polycyclic cycloalkadienes include, for example, dicyclopentadiene, norbornadiene, dimethyldicyclopentadiene, 7,7-dimethylnorbornadiene, 1,1-bis (5-bicyclo [2. 2.1] Hept-2-enyl) methane, 1,2-bis (5-bicyclo [2.2.1] hepta-2-enyl) ethane, 1,6-bis (5-bicyclo [2.2. 1] Hept-2-enyl) hexane and the like.

The polymerization method of the present invention can be carried out in the presence of a monomer and a catalyst, under any of reduced pressure, atmospheric pressure and pressurized conditions, in any of bulk, solution and slurry methods. The preferred temperature range for carrying out the polymerization is from -30 ° C to
260 ° C., preferably 0 ° C. to 200 ° C. Further, the polymerization may be performed in an atmosphere of an inert gas such as nitrogen or argon, or may be performed in an atmosphere of ethylene. Also, a mixed atmosphere of ethylene and / or α-olefin and the above inert gas may be used.

Further, hydrogen may be allowed to coexist in addition to the above gas for controlling the molecular weight. Further, the catalyst component may be supported on a suitable carrier such as alumina, magnesium chloride or silica. If desired, a solvent can be used in the polymerization. Suitable solvents for use in the polymerization include hydrocarbon solvents such as alkanes such as hexane and cyclohexane, and aromatic solvents such as toluene, benzene and ethylbenzene.

The preferred amount of the catalyst in the polymerization is [(weight of polymer produced) Kg] / [1 mol of catalyst (A) component] = 10
It is an amount that gives a polymer of about kg / 1 mol to 1,000,000 kg / 1 mol. As a method for separating the polymer after polymerization in the present invention, for example, a method of adding a polar solvent which is a poor solvent such as acetone or an alcohol obtained by mixing an acid or an alkali to the polymerization solution to precipitate and recover the polymer, A method in which the mixture is poured into boiling water with stirring and then recovered by distillation together with the solvent, or a method in which the solvent is distilled off by directly heating the reaction solution can be used.

In the method for producing a styrenic copolymer of the present invention, the styrenic monomer unit and the olefinic monomer unit may each be composed of two or more components, and may be binary, ternary or quaternary. Production of copolymers is also possible.

The styrene copolymer obtained by the method for producing a styrene copolymer according to the present invention is, for example, a styrene / ethylene copolymer, a styrene / ethylene / propylene copolymer, a styrene / ethylene / hexene copolymer. ,
Styrene / ethylene / heptene copolymer, styrene / ethylene / octene copolymer, styrene / cyclohexadiene copolymer, styrene / norbornene copolymer, and the like. The composition of these copolymers is 1 to 100% by weight of styrene. The olefin can be copolymerized in the range of 99 to 0 parts by weight per part by weight. Preferably, the olefin content is 80 to 1 part by weight based on 20 to 99 parts by weight of styrene. More preferably, the olefin is 50 to 1 part by weight based on 50 to 99 parts by weight of styrene. Most preferably, the olefin content is 20 to 1 part by weight based on 80 to 99 parts by weight of styrene.

Further, the random styrene-based copolymer obtained in the method for producing a styrene-based copolymer of the present invention has a melting peak of a polystyrene portion and / or a polyethylene portion measured by a differential scanning calorimeter. It is necessary not to. In the case of a copolymer having low randomness, that is, a copolymer containing a block structure of polystyrene or polyethylene, each polymer shows a melting point peculiar to each polymer.
If the randomness is reduced to such an extent that the melting point is observed with a differential scanning calorimeter, the flexibility of the copolymer may be impaired, particularly in the region where the styrene content is high, or the compatibilization of other resins such as polyolefin / polystyrene blends may occur. Poor properties as an agent.

[0068]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The embodiments of the present invention will be specifically described below with reference to examples, but the present invention is not limited to these. In Examples and Comparative Examples, the polymerization activity was determined from the amount of the polymer obtained after the completion of the polymerization. The styrene content in the polymer was determined by ¹ H-NMR spectrum, and the chain structure of the styrene unit was confirmed by ¹³ C-NMR.
This was performed using an NMR spectrum. Each NMR measurement was performed at 25 ° C. in a chloroform-d solution. The melting point (Tm) and glass transition temperature (Tg) of the polymer were measured using a differential scanning calorimeter (DSC) at a heating rate of 20 ° C./min in a nitrogen atmosphere. The molecular weight of the polymer is 4 according to the GPC method.
At 0 ° C, chloroform / UV /
It was detected by RI and determined by polystyrene conversion.

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EXAMPLES Example 1 Synthesis of (Titanium Complex Component-1) NaH (2.25 mmol) previously cooled to −20 ° C.
Was dispersed in dehydrated diethyl ether (20 ml),
Acetylcyclohexanone (2.25 mmol) was slowly added dropwise, and the temperature was raised to 0 ° C. while stirring. To the resulting dispersion, a dehydrated toluene solution (20 ml) containing pentamethylcyclopentadienyltitanium trichloride (2.25 mmol) was added dropwise, and the mixture was stirred for 2 hours.
The solvent was distilled off, extracted with dehydrated toluene and filtered, and the filtrate was concentrated and then recrystallized to obtain the desired complex.

Example 2 Synthesis of (Titanium Complex Component-2) NaH (2.25 mmol) previously cooled to −20 ° C.
Was dispersed in dehydrated diethyl ether (20 ml),
Benzoyl acetone (2.25 mmol) was slowly added dropwise, and the temperature was raised to 0 ° C. while stirring. To the resulting dispersion, a dehydrated toluene solution (20 ml) containing pentamethylcyclopentadienyltitanium trichloride (2.25 mmol) was added dropwise, and the mixture was stirred for 2 hours. The solvent was distilled off, extracted with dehydrated toluene and filtered, and the filtrate was concentrated.
Recrystallization afforded the desired complex.

Example 3 700 ml of purified toluene and 500 ml of purified styrene were placed in a 2000 ml autoclave whose inside was degassed under vacuum and purged with nitrogen. Next, as the component (B), M
MAO (Methylaluminoxane manufactured by Tosoh Akzo) 1m
After 100 ml of a purified toluene solution containing mol was introduced into the autoclave, 0.8 MPa ethylene gas was introduced. The internal temperature of the autoclave was kept at 90 ° C., and 100 ml of a purified toluene solution containing 1 μmol of titanium complex component-1 as the component (A) was added to the autoclave to start the polymerization reaction. The polymerization was carried out for 60 minutes while maintaining the internal temperature of the autoclave and the ethylene pressure. Table 1 shows the polymerization results.

Example 4 Polymerization was carried out in the same manner as in Example 3 except that the titanium complex component-2 was used as the component (A). Table 1 shows the polymerization results.

Example 5 The polymerization was carried out in the same manner as in Example 3 except that the polymerization was carried out at 40 ° C. Table 1 shows the polymerization results.

Example 6 The polymerization was carried out in the same manner as in Example 4 except that the polymerization was carried out at 40 ° C. Table 1 shows the polymerization results.

Example 7 300 ml of purified toluene and 900 ml of purified styrene were placed in a 2000 ml autoclave whose inside was degassed under vacuum and purged with nitrogen. Thereafter, polymerization was carried out in the same manner as in Example 3. Table 1 shows the polymerization results.

Example 8 Polymerization was carried out in the same manner as in Example 7 except that titanium complex component-2 was used as the component (A). Table 1 shows the polymerization results.

Example 9 Example 3 except that toluene containing 10 ppm of water was used.
Polymerization was carried out in the same manner as described above. Table 1 shows the polymerization results.

Example 10 Example 4 except that toluene containing 10 ppm of water was used.
Polymerization was carried out in the same manner as described above. Table 1 shows the polymerization results.

Example 11 Polymerization was carried out in the same manner as in Example 3 except that 0.1 mmol of MMAO was used as the component (B). Table 1 shows the polymerization results.

Example 12 Polymerization was carried out in the same manner as in Example 4 except that 0.1 mmol of MMAO was used as the component (B). Table 1 shows the polymerization results.

Example 13 1000 ml of purified toluene and 200 ml of purified styrene were placed in a 2000 ml autoclave in which the inside was evacuated and purged with nitrogen. Thereafter, polymerization was carried out in the same manner as in Example 3. Table 1 shows the polymerization results.

Example 14 1000 ml of purified toluene and 200 ml of purified styrene were placed in a 2000 ml autoclave in which the inside was evacuated and purged with nitrogen. Thereafter, polymerization was carried out in the same manner as in Example 4. Table 1 shows the polymerization results.

Comparative Example 1 Polymerization was carried out in the same manner as in Example 3 except that (t-butylamido) dimethyl- (tetramethyl-η ⁵ -cyclopentadienyl) silanetitanium dichloride was used as the component (A). Table 1 shows the polymerization results.

Comparative Example 2 Polymerization was carried out in the same manner as in Example 5 except that (t-butylamido) dimethyl- (tetramethyl-η ⁵ -cyclopentadienyl) silanetitanium dichloride was used as the component (A). Table 1 shows the polymerization results.

Comparative Example 3 Polymerization was carried out in the same manner as in Example 7 except that (t-butylamido) dimethyl- (tetramethyl-η ⁵ -cyclopentadienyl) silanetitanium dichloride was used as the component (A). Table 1 shows the polymerization results.

Comparative Example 4 Polymerization was carried out in the same manner as in Example 9 except that (t-butylamido) dimethyl- (tetramethyl-η ⁵ -cyclopentadienyl) silanetitanium dichloride was used as the component (A). The polymerization result is shown in 1.

Comparative Example 5 Polymerization was carried out in the same manner as in Example 11 except that (t-butylamido) dimethyl- (tetramethyl-η ⁵ -cyclopentadienyl) silanetitanium dichloride was used as the component (A). The polymerization result is shown in 1.

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[Table 1]

[0089]

Industrial Applicability According to the present invention, it can be easily synthesized for industrial use, has a high polymerization activity in a wide temperature range from low to high temperatures, and furthermore, has a low styrene content in copolymerization of styrene and ethylene. It is possible to provide a styrene and olefin copolymerization catalyst system which can be freely controlled, in particular, can be randomly copolymerized with a styrene content exceeding 50 mol% and is not easily affected by impurities such as water in the polymerization system. did it.

 ────────────────────────────────────────────────── ─── Continuing on the front page F term (reference) 4J028 AA01A AB01A AC09A AC10A AC19A AC20A BA00A BA01B BB00A BB00B BB01B BC12B BC25B EB02 EB03 EB04 EB05 EB07 EB09 EB10 EB21 EC02 FA01 FA02 A19A01A03 A19A01A02A AB04P AB08P CA03 CA04 DA24 DA41 FA10

Claims (3)

[Claims] 1. A styrene-olefin copolymerization catalyst comprising a titanium complex component (A) represented by the following formula (1) and an activator (B) selected from an alkylaluminumoxy compound or a boron compound. CpTiL _m X _3-m (1) (wherein Cp represents a group having a cyclopentadiene-type anion skeleton. L represents an asymmetric 1 in which oxygen is a coordinating atom.
Represents a divalent bidentate chelating anionic ligand. X is hydrogen,
Represents an alkyl group having 1 to 20 carbon atoms, an alkoxy group, an aryl group, an allyloxy group, an aralkyl group, or halogen. m represents an integer of 1 to 3. When there are a plurality of L or X, they may be independently the same or different. ) 2. The method according to claim 1, wherein the titanium complex component (A) comprises L
Is an asymmetric monovalent bidentate chelating anionic ligand produced from a compound represented by the following formula (2):
The styrene and olefin copolymerization catalyst described. Embedded image (Wherein R ¹ , R ² , and R ³ are hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkoxy group, an aryl group, an allyloxy group,
Represents an aralkyl group, an alkylamide group, or an arylamide group, wherein R ¹ and R ³ are not the same, R ¹ and R ² may be the same or different, and R ² and R ³ are the same They may be present or different. R ¹ and R ² may be combined with each other to form a ring. ) 3. In the presence of the catalyst according to claim 1 or 2,
A method for producing a styrenic copolymer, comprising copolymerizing at least one styrene and at least one olefin.