JPH07324106A - Production of copolymer - Google Patents

Abstract

PURPOSE:To obtain a high-impact copolymer by copolymerizing an alpha-olefin with an arom. vinyl compd. polymer having unsatd. bonds at the terminals of the molecular chain thereof and prepd. by polymn. using an anionic polymn. initiator represented by a specific formula. CONSTITUTION:An arom. vinyl compd. monomer such as styrene is polymerized in a solvent such as n-hexane under ordinary pressure at about -100 to +200 deg.C while using an anionic polymn. catalyst of the formula (wherein R<1> is a 3-20C hydrocarbon; and M is an alkali metal atom) such as 4-pentenyllithium to form an arom. vinyl polymer having unsatd. bonds at the molecular terminals thereof and a number-average mol.wt. of about 500 to 1,000,000. Subsequently, this polymer is copolymerized with an alpha-olefin such as ethylene in a solvent such as n-hexane at about -78 to +200 deg.C while using a Ziegler-Natta catalyst comprising an almoxane and a transition metal compd. having a conjugated 5-membered ring ligand to obtain a copolymer excellent in impact resistance.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a process for producing a copolymer in which an aromatic vinyl compound polymer having an unsaturated bond at the terminal of a molecular chain and an .alpha.-olefin are copolymerized.

The copolymer thus obtained is a thermoplastic resin which itself has excellent impact resistance, and also an excellent modifier for polyolefin, polystyrene or polyphenylene ether, and polyphenylene ether and polyolefin or polyolefin. It is also an excellent compatibilizer with high-impact polystyrene.

[0003]

2. Description of the Related Art Homopolymers of α-olefins (including ethylene in the present invention) or copolymers thereof are inexpensive and have excellent mechanical strength, gloss and transparency. Since it has moldability, moisture resistance and chemical resistance, it is widely used alone or as a polymer blend component. However, since the α-olefin polymer has a non-polar molecular structure, it has a poor affinity with other substances, and has a markedly poor adhesiveness, printability, or compatibility with polymer blends.

In order to improve this, many methods for producing a modified polymer by graft-polymerizing a radical-polymerizable monomer to an α-olefin polymer have been tried for a long time.

However, in general, the radical graft polymerization method does not have a sufficiently high graft ratio or graft efficiency, and in many cases, a radical polymerization initiator such as an organic or inorganic peroxide is used. There are many problems such as molecular cleavage of the trunk polymer and easy crosslinking reaction.

Various proposals have been made for the purpose of solving such a point. For example, JP-A-57-985
No. 08 and JP-A-2-269110 disclose α-
It is disclosed that the reactivity of the unsaturated bond of the copolymer of the olefin and the non-conjugated diene monomer is utilized to suppress the molecular cutting and cross-linking of the trunk polymer to increase the graft ratio of the monomer.

However, this unsaturated copolymer is a non-conjugated diene monomer which does not necessarily have a high copolymerizability, and the radical graft reaction of this unsaturated copolymer is not limited to the monomer graft ratio, the graft efficiency or the graft efficiency. From the viewpoint of molecular cleavage of the trunk polymer, it cannot be said that it has been practically completed.

As a method other than the radical graft polymerization method, a halogen which is obtained by Kaminsky type Ziegler-Natta catalyst is added to a double-bonded double bond at the molecular chain end of the polyolefin, and a coupling reaction between it and living polystyryllithium gives α-. Method for obtaining block copolymer of olefin and styrene (JP-A-62-158709)
No. publication) is known.

However, since unreacted halogen remains in the copolymer produced by this method, when the mixture is melt-kneaded as in extrusion molding or injection molding, coloring or deterioration of the copolymer is likely to occur.

Further, an anionic polymerization active point and Ziegler
By the so-called active point conversion method with the Natta type polymerization active point,
Method for obtaining block copolymer of polyolefin and polystyrene or polybutadiene (JP-A-60-20918)
Publication, Eur. Polym. J. 17, 1175, 1981, Makromol. C
hem. 181, 1815, 1980) is also known.

However, in these methods, the efficiency of conversion of active sites is low (about 10%), so that the block copolymerization efficiency is lowered, and it is difficult to obtain a target copolymer having a controlled molecular weight. Has the problem of.

Further, α-having an unsaturated bond at the end of the molecular chain
A method of obtaining a block copolymer from an olefin polymer and an anion-polymerizable monomer (Japanese Patent Laid-Open No. 5-39331) is also known, but it is necessary to dissolve the polyolefin in a polymerization solvent under anion-polymerizable conditions. The molecular weight and stereoregularity of the resulting polyolefins are limited.

[0013]

SUMMARY OF THE INVENTION It is an object of the present invention to solve the above problems and to provide a method for producing a copolymer which is free from molecular cleavage or gelation and has a high copolymerization efficiency.

[0014]

According to the present invention, an aromatic vinyl compound monomer is represented by the following general formula (I) CH ₂ = CH-R ¹ -M (I) (wherein R ¹ has 3 to ¹⁰ carbon atoms). 20 hydrocarbon groups, M
Represents an alkali metal atom) and is subjected to a copolymerization step with an aromatic vinyl compound polymer having an unsaturated bond at a molecular chain terminal and an α-olefin, which are obtained by polymerization using an anionic polymerization initiator. It is a method for producing a characteristic copolymer.

The present invention will be described in detail below.

(1) Anionic Polymerization Initiator The anionic polymerization initiator used in the present invention has the general formula (I)
Is a compound represented by.

CH ₂ = CH-R ¹ -M (I)

(In the formula, R ¹ represents a hydrocarbon group having 3 to 20 carbon atoms, and M represents an alkali metal atom.)

In the above formula, the carbon number of R ¹ is preferably 3 to 15, more preferably 3 to 10.

Specific examples of M include metal atoms such as lithium, sodium and potassium. Of these, lithium atom is preferable.

The method for synthesizing the anionic polymerization initiator (I) is not particularly limited, but it can be usually obtained by reacting a compound represented by the following general formula (II) with an alkali metal.

CH ₂ = CH-R ¹ -X (II)

(In the formula, R ¹ represents a hydrocarbon group having 3 to 20 carbon atoms, and X represents a halogen atom.)

Specific examples of the anionic polymerization initiator (I) include 4-pentenyllithium, 5-hexenyllithium, 7-octenyllithium, 4-pentenylsodium, 5-hexenylsodium, 4-pentenylpotassium, Although 5-hexenyl potassium and the like can be mentioned, 4-pentenyl lithium is preferable.

(2) Aromatic vinyl compound monomer Specific examples of the aromatic vinyl compound monomer include, for example, styrene, α-methylstyrene, α-methoxystyrene, methylstyrene, dimethylstyrene, 2,4,6.
-Trimethylstyrene, chlorostyrene, dichlorostyrene, bromostyrene, nitrostyrene, chloromethylstyrene, cyanostyrene, t-butylstyrene, vinylnaphthalene and the like are mentioned, and among them, styrene, α-methylstyrene and methylstyrene are preferable. These can be used alone or in combination of two or more.

Further, a monomer copolymerizable with these aromatic vinyl compound monomers may be copolymerized and used within a range not exceeding 50 mol%. These monomers may be copolymerized in any form such as random or block. Specifically, it is butadiene, isoprene, methacrylic acid ester, hexamethylcyclotrisiloxane, or the like.

(3) Production of Aromatic Vinyl Compound Polymer Having Unsaturated Bond at End of Molecular Chain The conditions for polymerizing the aromatic vinyl compound monomer by using the anionic polymerization initiator (I) are -100 to 200 ° C.
Preferably -90 to 150 ° C, more preferably -80 to
It can be carried out at a temperature of 100 ° C. under normal pressure, reduced pressure or increased pressure.

Examples of the solvent that can be used in the above polymerization include aliphatic hydrocarbons such as n-hexane and n-heptane; alicyclic hydrocarbons such as cyclohexane and decahydronaphthalene; benzene, toluene, o- , M
-Or p-xylene and other aromatic hydrocarbons; teratohydrofuran, dioxane, ethyl ether, pyridine,
An aprotic polar solvent such as diglyme; or the like can be used. These solvents may be used alone or as a mixture.

Although the molecular weight of the aromatic vinyl compound polymer (a) having an unsaturated bond at the terminal of the molecular chain is arbitrary, it is generally the number average molecular weight measured by gel permeation chromatography (hereinafter referred to as "GPC"). (Hereinafter referred to as “Mn”) 500 to 1,000,00
0, preferably 500 to 500,000, more preferably 1,000 to 100,000.

(4) α-Olefin Specific examples of the α-olefin used in the present invention include ethylene, propylene, 1-butene, 1-hexene and 3-.
Methyl-1-butene, 3-methyl-1-pentene, 4-
Methyl-1-pentene, 3,3-dimethyl-1-butene, 4,4-dimethyl-1-pentene, 3-methyl-1
-Hexene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 5-methyl-1-hexene, allylcyclopentane, allylcyclohexane, allylbenzene, 3-cyclohexyl-1-butene, vinylcyclopropane , Vinylcyclohexane, 2-vinylbicyclo [2,2,1] -heptane, and the like.
Among these, preferred examples are ethylene, propylene, 1-butene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, 4-methyl-1-pentene, 3-methyl-1-. Hexene and the like can be mentioned, and ethylene, propylene, 1-butene, 1-hexene, 3-methyl-1-butene or 4-methyl-1-pentene are particularly preferable. These α-olefins may be used alone or in combination of two or more. When two or more α-olefins are used, these α-olefins may be randomly distributed in the unsaturated polymer,
Alternatively, they may be distributed in blocks.

(5) Catalyst In order to copolymerize an α-olefin with an aromatic vinyl compound polymer having an unsaturated bond at a molecular chain end in the present invention,
Usually a Ziegler-Natta type catalyst is used. The Ziegler-Natta type catalyst used is known and is not particularly limited, but preferably the following components (i) and (i
i) a catalyst.

Component (i) Component (i) is a transition metal compound of Groups IVB to VIB of the Periodic Table having at least one conjugated five-membered ring ligand. Specifically, it is represented by the following general formula (III) or general formula (IV).

Q _a [C ₅ H _5-ab (R ² ) _b ] [C ₅ H _5-ac (R ³ ) _c ] MeXY (III)

S _a [C ₅ H _5-ad (R ⁴ ) _d ] ZMeXY (IV)

Here, Q represents a bonding group bridging the two conjugated five-membered ring ligands, and S represents a bonding group bridging the conjugated five-membered ring ligand and the Z group. In particular,

(A) Lower alkylene, or lower alkyl or phenyl substituted derivative thereof, preferably methylene, ethylene, isopropylene, phenylmethylmethylene, diphenylmethylene, cyclohexylene, etc. (b) silylene or oligosilylene, or lower alkyl or Phenyl-substituted derivatives, preferably silylene, dimethylsilylene, phenylmethylsilylene, diphenylsilylene, disilylene, tetramethyldisilylene, etc. (C) Hydrocarbon group containing germanium, phosphorus, nitrogen, boron or aluminum [specifically (CH ₃ ) ₂ Ge,
_{(C 6 H 5) 2 Ge} , (CH 3) P, (C 6 H 5) P, (C 4
H ₉ ) N, (C ₆ H ₅ ) N, (CH ₃ ) B, (C ₄ H ₉ ) B,
(C ₆ H ₅ ) B, (C ₆ H ₅ ) Al, (CH ₃ O) Al, etc.]
Etc. Of these, an alkylene group or a silylene group is preferable. a is 0 or 1.

In the above general formula, [C ₅ H _5-ab (R ² )
_b ], [C ₅ H _5-ac (R ³ ) _c ] or [C ₅ H _5-ad (R ⁴ )]
_The conjugated five-membered ring ligand represented by _d ] is defined separately, but b, c and d, and R ² , R
It is needless to say that the three conjugated five-membered ring groups may be the same or different because the definitions of ³ and R ⁴ are the same (details will be given later).

One specific example of this conjugated five-membered ring group is b =
0 (c = 0 or d = 0) cyclopentadienyl group (no substituent other than the bridging group Q or S). When this conjugated five-membered ring group is b ≠ 0 (c ≠ 0 or d ≠ 0) and has a substituent, one specific example of R ² (R ³ or R ⁴ ) is a hydrocarbon group. (C _{1 to} C ₂₀ , preferably C ₁ to C ₂₀
C ₁₂ ), even if this hydrocarbon group is bonded to the cyclopentadienyl group as a monovalent group, and when there are a plurality of these, the two are bonded to each other at their other ends. Then, a ring, that is, a condensed ring with a cyclopentadiene ring may be formed together with a part of the cyclopentadienyl group. A typical example of the latter is one in which R ² (R ³ or R ⁴ ) shares a double bond of the cyclopentadienyl group to form a condensed 6-membered ring, that is, the conjugated 5-membered ring group is indenyl. A group or a fluorenyl group.
That is, a representative example of the conjugated five-membered ring group is a substituted or unsubstituted cyclopentadienyl group, indenyl group or fluorenyl group.

R ² , R ³ and R ⁴ are each a halogen atom (for example, fluorine, chlorine, bromine) in addition to the above C _{1 to} C ₂₀ , preferably C _{1 to} C ₁₂ hydrocarbon group, Alkoxy groups (for example, C _{1 to} C ₁₂ ), silicon-containing hydrocarbon groups [for example, silicon atom to -Si (R) (R
′) (R ″) group containing about 1 to 24 carbon atoms], a phosphorus-containing hydrocarbon group [for example, a phosphorus atom is —P (R) (R
′) Group having about 1 to 18 carbon atoms], a nitrogen-containing hydrocarbon group [for example, a group having a nitrogen atom in the form of —N (R) (R ′) and having about 1 to 18 carbon atoms] or A boron-containing hydrocarbon group (for example, a group having a carbon atom in the form of -B (R) (R ') and having about 1 to 18 carbon atoms). When b (c or d) is 2 or more and a plurality of R ² (R ³ or R ⁴ ) are present, they may be the same or different.

B, c and d are 0 ≦ b ≦ when a is 0.
5, 0 ≦ c ≦ 5, 0 ≦ d ≦ 5, 0 ≦ b when a is 1
It represents an integer satisfying ≦ 4, 0 ≦ c ≦ 4, and 0 ≦ d ≦ 4.

Me is a transition metal of Group IVB to VIB of the Periodic Table, preferably titanium, zirconium or hafnium.
Particularly preferred is zirconium.

Z is oxygen (-O-), sulfur (-S-),
An alkoxy group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms,
A thioalkoxy group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms, a silicon-containing hydrocarbon group having 1 to 40 carbon atoms, preferably 1 to 18 carbon atoms, and a nitrogen-containing hydrocarbon group having 1 to 40 carbon atoms, preferably 1 to 18 carbon atoms Group having 1 to 40 carbon atoms, preferably 1 to 1
8 is a phosphorus-containing hydrocarbon group. When a = 1, part of the Z group is bonded to the S group which is a bonding group.

X and Y are each a hydrogen atom; a halogen atom; a hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms; an alkoxyl group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms; amino group; carbon Number 1-20, preferably 1-12
A phosphorus-containing hydrocarbon group (specifically, for example, diphenylphosphine group); or a silicon-containing hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms [specifically, for example, trimethylsilyl group, bis (trimethylsilyl) group] Methyl group]. X and Y may be the same or different.
Of these, a halogen atom and a hydrocarbon group are preferable.

Specific examples of this transition metal compound when Me is zirconium are as follows.

(A) A transition metal having no conjugated bridging group and two conjugated five-membered ring ligands, for example,

Bis (cyclopentadienyl) zirconium dichloride, bis (methylcyclopentadienyl) zirconium dichloride, bis (dimethylcyclopentadienyl) zirconium dichloride, bis (trimethylcyclopentadienyl) zirconium dichloride, bis (tetramethyl Cyclopentadienyl) zirconium dichloride,

Bis (pentamethylcyclopentadienyl) zirconium dichloride, bis (n-butylcyclopentadienyl) zirconium dichloride, bis (indenyl) zirconium dichloride, bis (fluorenyl) zirconium dichloride, bis (cyclopentadienyl) zirconium Monochrome lid monohydride,

Bis (cyclopentadienyl) methylzirconium monochloride, bis (cyclopentadienyl)
Ethyl zirconium monochloride, bis (cyclopentadienyl) phenyl zirconium monochloride, bis (cyclopentadienyl) zirconium dimethyl, bis (cyclopentadienyl) zirconium diphenyl,

Bis (cyclopentadienyl) zirconium dineopentyl, bis (cyclopentadienyl) zirconium dihydride, (cyclopentadienyl)
(Indenyl) zirconium dichloride, (cyclopentadienyl) (fluorenyl) zirconium dichloride and the like.

(B) A transition metal compound having two five-membered ring ligands bridged by an alkylene group, for example,

Methylenebis (indenyl) zirconium dichloride, ethylenebis (indenyl) zirconium dichloride, ethylenebis (indenyl) zirconium monohydride monochloride, ethylenebis (indenyl) methylzirconium monochloride, ethylenebis (indenyl) zirconium monomethoxide monochloride ,

Ethylenebis (indenyl) zirconium diethoxide, ethylenebis (indenyl) zirconium dimethyl, ethylenebis (4,5,6,7-tetrahydroindenyl) zirconium dichloride, ethylenebis (2-methylindenyl) zirconium dichloride ,
Ethylene bis (2-ethylindenyl) zirconium dichloride,

Ethylene bis (2,4-dimethylindenyl) zirconium dichloride, ethylene (2,4-dimethylcyclopentadienyl) (3 ', 5'-dimethylcyclopentadienyl) zirconium dichloride, ethylene (2-methyl) -4-tert-butylcyclopentadienyl) (3'-tert-butyl-5'-methylcyclopentadienyl) zirconium dichloride, ethylene (2,
3,5-trimethylcyclopentadienyl) (2 ', 4
′, 5′-Trimethylcyclopentadienyl) zirconium dichloride, isopropylidene bis (indenyl)
Zirconium dichloride,

Isopropylidene (2,4-dimethylcyclopentadienyl) (3 ', 5'-dimethylcyclopentadienyl) zirconium dichloride, isopropylidene (2-methyl-4-tert-butylcyclopentadienyl) ( 3'-tert-butyl-5'-methylcyclopentadienyl) zirconium dichloride, methylene (cyclopentadienyl) (3,4-dimethylcyclopentadienyl) zirconium dichloride, methylene (cyclopentadienyl) (3,3 4-dimethylcyclopentadienyl) zirconium chloride hydride, methylene (cyclopentadienyl) (3,4-dimethylcyclopentadienyl) zirconium dimethyl,

Methylene (cyclopentadienyl) (3,
4-dimethylcyclopentadienyl) zirconium diphenyl, methylene (cyclopentadienyl) (trimethylcyclopentadienyl) zirconium dichloride, methylene (cyclopentadienyl) (tetramethylcyclopentadienyl) zirconium dichloride, isopropylidene (cyclo Pentadienyl) (3,4-dimethylcyclopentadienyl) zirconium dichloride, isopropylidene (cyclopentadienyl) (2,3,4,5
-Tetramethylcyclopentadienyl) zirconium dichloride,

Isopropylidene (cyclopentadienyl) (3-methylindenyl) zirconium dichloride, isopropylidene (cyclopentadienyl) (fluorenyl) zirconium dichloride, isopropylidene (2-methylcyclopentadienyl) (fluorenyl)
Zirconium dichloride, isopropylidene (2,5-
Dimethylcyclopentadienyl) (3 ′, 4′-dimethylcyclopentadienyl) zirconium dichloride, isopropylidene (2,5-dimethylcyclopentadienyl) (fluorenyl) zirconium dichloride,

Ethylene (cyclopentadienyl) (3,
5-dimethylcyclopentadienyl) zirconium dichloride, ethylene (cyclopentadienyl) (fluorenyl) zirconium dichloride, ethylene (2,5-dimethylcyclopentadienyl) (fluorenyl) zirconium dichloride, ethylene (2,5-diethylcyclo) Pentadienyl) (fluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl)
(3,4-Diethylcyclopentadienyl) zirconium dichloride, cyclohexylidene (cyclopentadienyl) (fluorenyl) zirconium dichloride, cyclohexylidene (2,5-dimethylcyclopentadienyl) (3 ', 4'- Dimethylcyclopentadienyl) zirconium dichloride and the like.

(C) Transition metal compounds having a silylene group-bridged five-membered ring ligand, for example,

Dimethyl silylene bis (indenyl) zirconium dichloride, dimethyl silylene bis (4,5,5
6,7-Tetrahydroindenyl) zirconium dichloride, dimethylsilylenebis (2-methylindenyl)
Zirconium dichloride, dimethyl silylene bis (2,
4-dimethylindenyl) zirconium dichloride, dimethylsilylenebis (2-methyl-4,5,6,7-tetrahydroindenyl) zirconium dichloride,

Dimethylsilylene (2,4-dimethylcyclopentadienyl) (3 ', 5'-dimethylcyclopentadienyl) zirconium dichloride, phenylmethylsilylenebis (indenyl) zirconium dichloride,
Phenylmethylsilylene bis (4,5,6,7-tetrahydroindenyl) zirconium dichloride, phenylmethylsilylene (2,4-dimethylcyclopentadienyl) (3 ′, 5′-dimethylcyclopentadienyl) zirconium dichloride, Phenylmethylsilylene (2,
3,5-trimethylcyclopentadienyl) (2 ', 4
′, 5′-Trimethylcyclopentadienyl) zirconium dichloride,

Phenylmethylsilylenebis (tetramethylcyclopentadienyl) zirconium dichloride, diphenylsilylenebis (indenyl) zirconium dichloride, tetramethyldisilylenebis (indenyl) zirconium dichloride, tetramethyldisilylenebis (cyclopentadienyl) zirconium Dichloride, tetramethyldisilylene (3-methylcyclopentadienyl) (indenyl) zirconium dichloride,

Dimethylsilylene (cyclopentadienyl) (3,4-dimethylcyclopentadienyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (trimethylcyclopentadienyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) ) (Tetramethylcyclopentadienyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (3,4-diethylcyclopentadienyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (triethylcyclopentadienyl) zirconium Dichloride,

Dimethylsilylene (cyclopentadienyl) (tetraethylcyclopentadienyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (fluorenyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (2,7-di- t
-Butylfluorenyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (octahydrofluorenyl) zirconium dichloride, dimethylsilylene (2-methylcyclopentadienyl) (fluorenyl) zirconium dichloride,

Dimethylsilylene (2,5-dimethylcyclopentadienyl) (fluorenyl) zirconium dichloride, dimethylsilylene (2-ethylcyclopentadienyl) (fluorenyl) zirconium dichloride, dimethylsilylene (2,5-diethylcyclopentadiene) (Enyl) (fluorenyl) zirconium dichloride, diethylsilylene (2-methylcyclopentadienyl) (2
′, 7′-Di-t-butylfluorenyl) zirconium dichloride, dimethylsilylene (2,5-dimethylcyclopentadienyl) (2 ′, 7′-di-t-butylfluorenyl) zirconium dichloride,

Dimethylsilylene (2-ethylcyclopentadienyl) (2 ', 7'-di-t-butylfluorenyl) zirconium dichloride, dimethylsilylene (diethylcyclopentadienyl) (2', 7'-di -T-butylfluorenyl) zirconium dichloride, dimethylsilylene (methylcyclopentadienyl) (octahydrofluorenyl) zirconium dichloride, dimethylsilylene (dimethylcyclopentadienyl) (octahydrofluorenyl) zirconium dichloride, dimethyl Silylene (ethylcyclopentadienyl) (octahydrofluorenyl) zirconium dichloride, dimethylsilylene (diethylcyclopentadienyl) (octahydrofluorenyl) zirconium dichloride and the like.

(D) Transition metal compounds having a 5-membered ring ligand bridged by a hydrocarbon group containing germanium, aluminum, boron, phosphorus or nitrogen, for example,

Dimethyl germanium bis (indenyl)
Zirconium dichloride, dimethyl germanium (cyclopentadienyl) (fluorenyl) zirconium dichloride, methyl aluminum bis (indenyl) zirconium dichloride, phenyl aluminum bis (indenyl) zirconium dichloride, phenylphosphinobis (indenyl) zirconium dichloride,

Ethylholanobis (indenyl) zirconium dichloride, phenylaminobis (indenyl) zirconium dichloride, phenylamino (cyclopentadienyl) (fluorenyl) zirconium dichloride,
Etc. are illustrated.

(E) Transition metal compounds having one five-membered ring ligand, for example

Pentamethylcyclopentadienylbis (phenyl) amide zirconium dichloride, indenylbis (phenyl) amide zirconium dichloride, pentamethylcyclopentadienylbis (trimethylsilyl) amide zirconium dichloride, pentamethylcyclopentadienylphenoxyzinium dichloride, Dimethylsilylene (tetramethylcyclopentadienyl)
Phenylamide zirconium dichloride,

Dimethylsilylene (tetramethylcyclopentadienyl) -tert-butylamide zirconium dichloride, dimethylsilylene (indenyl) cyclohexylamide zirconium dichloride, dimethylsilylene (tetrahydroindenyl) decylamide zirconium dichloride, dimethylsilylene (tetrahydroindenyl) Examples include (trimethylsilyl) amidozirconium dichloride, dimethylgermane (tetramethylcyclopentadienyl) (phenyl) amidozirconium dichloride, and the like.

(F) Further, it is also possible to use the compounds of (a) to (e) in which chlorine is replaced by bromine, iodine, hydride, methyl, phenyl or the like.

Further, in the present invention, as the component (i), compounds in which the central metal of the zirconium compounds exemplified in the above (a) to (f) are changed from zirconium to titanium, hafnium, niobium, molybdenum or tungsten can also be used. it can.

Of these, zirconium compounds, hafnium compounds and titanium compounds are preferable. More preferred are titanium compounds, zirconium compounds or hafnium compounds crosslinked with an alkylene group or a silylene group.

Component (ii) is component (ii) aluminum oxy compound, (b) Lewis acid, or (iii) component (i).
It is an ionic compound capable of reacting with and converting the component (i) into a cation.

Some Lewis acids can be regarded as "ionic compounds capable of reacting with the component (i) to convert the component (i) into a cation". Therefore, it is understood that the compounds belonging to both of the “Lewis acid” and the “ionic compound capable of reacting with the component (i) to convert the component (i) into a cation” belong to either one. And

Specific examples of the aluminum oxy compound include compounds represented by the following general formula (V), (VI) or (VII).

[0078]

[Chemical 1]

[0079]

[Chemical 2]

[0080]

[Chemical 3]

(In the formula, p is 0 to 40, preferably 2 to 3
Is an integer of 0, and R ⁵ , R ⁶ , R ⁷ and R ⁸ each represent a hydrogen atom or preferably a hydrocarbon group having 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms).

The compounds of the general formulas (V) and (VI) are compounds also called alumoxanes, which are products obtained by the reaction of one kind of trialkylaluminum or two or more kinds of trialkylaluminum with water. is there.
Specifically, (a) methylalumoxane, ethylalumoxane, propylalumoxane, butylalumoxane, isobutylalumoxane obtained from one kind of trialkylaluminum and water, and (b) two kinds of trialkylaluminum and water. Examples thereof include methyl ethyl alumoxane, methyl butyl alumoxane, and methyl isobutyl alumoxane. Of these, particularly preferred is methylalumoxa or methylisobutylalumoxane.

A plurality of these alumoxanes can be used in combination in each group and between each group, and they can be used in combination with other alkylaluminum compounds such as trimethylaluminum, triethylaluminum, triisobutylaluminum and dimethylaluminum chloride. It is also possible to do so.

These alumoxanes can be prepared by various known methods, and specifically the following methods are exemplified.

(A) A method in which a trialkylaluminum is directly reacted with water using a suitable organic solvent such as toluene, benzene or ether, (b) a salt hydrate having trialkylaluminum and water of crystallization, for example, copper sulfate, A method of reacting with a hydrate of aluminum sulfate, (c) a method of reacting trialkylaluminum with water impregnated in silica gel, etc., (d) a mixture of trimethylaluminum and triisobutylaluminum, toluene, benzene,
A method of directly reacting with water using a suitable organic solvent such as ether,

(V) A method of mixing trimethylaluminum and triisobutylaluminum and reacting with a salt hydrate having water of crystallization by heating with a hydrate such as copper sulfate or aluminum sulfate; (f) impregnating silica gel with water Then, after treatment with triisobutylaluminum, a method of additionally treating with trimethylaluminum, (to) methylalumoxane and isobutylalumoxane are synthesized by a known method, a predetermined amount of these two components are mixed, and a reaction by heating is performed, (H) Add a salt having crystal water such as copper sulfate pentahydrate to an aromatic hydrocarbon solvent such as benzene or toluene, and
A method of reacting with trimethylaluminum under a temperature condition of 0 to 40 ° C. In this case, the amount of water used is usually 0.5 to 1.5 in molar ratio with respect to trimethylaluminum. The methylalumoxane thus obtained is
It is a linear or cyclic polymer of organoaluminum.

The compound represented by the general formula (VII) is one kind of trialkylaluminum, or two or more kinds of trialkylaluminum and the following general formula (VIII).

R ⁹ -B- (OH) ₂ (VIII)

An alkylboronic acid represented by the formula (in the formula, R ⁹
Is an alkyl group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms) in a molar ratio of 10: 1 to 1: 1. Specifically, (a) a 2: 1 reaction product of trimethylaluminum and methylboronic acid, (b) a 2: 1 reaction product of triisobutylaluminum and methylboronic acid, (c) trimethylaluminum, triisobutylaluminum and methylboronic acid. 1: 1: 1 reaction of
(D) Trimethylaluminum and ethylboronic acid 2:
The reaction product of 1 and the reaction product of (f) triethylaluminum and butylboronic acid in the ratio of 2: 1 are exemplified. These compounds of the general formula (VII) can be used in a plurality of kinds, and alumoxane represented by the general formula (V) or (VI), trimethylaluminum, triethylaluminum, triisobutylaluminum, dimethylaluminum chloride, etc. It is also possible to use in combination with the other alkylaluminum compound.

Further, as an ionic compound capable of reacting with the component (i) and converting the component (i) into a cation, there is a compound represented by the general formula (IX).

[K] ^{e +} [Z] ^e- (IX)

Here, K is an ionic cation component such as carbonium cation, tropylium cation, alumonium cation, oxonium cation,
Examples thereof include sulfonium cations and phosphonium cations. In addition, cations of metals, which are themselves easily reduced, and cations of organic metals are also included. Specific examples of these cations include (a) triphenylcarbonium, diphenylcarbonium, cycloheptatrienium, indenium, triethylammonium, tripropylammonium, tributylammonium, N, N.
-Dimethylanilinium, dipropylammonium, dicyclohexylammonium, triphenylphosphonium, trimethylphosphonium, tri (dimethylphenyl) phosphonium, tri (methylphenyl) phosphonium, triphenylsulfonium, triphenyloxonium, triethyloxonium, pyrylium, and silver There are ions, gold ions, platinum ions, copper ions, palladium ions, mercury ions, ferrocenium ions and the like.

Z in the above general formula (IX) is an ionic anion component, and the component (i) is a component (generally non-coordinated) which becomes a counter anion with respect to the converted cation species. Examples thereof include an organic boron compound anion, an organic aluminum compound anion, an organic gallium compound anion, an organic phosphorus compound anion, an organic arsenic compound anion, and an organic antimony compound anion. Specifically, (a) tetraphenylboron, tetrakis (3,4,5-trifluorophenyl) boron, tetrakis (3,5-di (trifluoromethyl) phenyl) boron, tetrakis (3,5-di ( t-butyl) phenyl) boron, tetrakis (pentafluorophenyl) boron, (b) tetraphenylaluminum, tetrakis (3,4,5-trifluorophenyl) aluminum, tetrakis [3,5-di (trifluoromethyl))
Phenyl] aluminum, tetrakis [3,5-di (t
-Butyl) phenyl] aluminum, tetrakis (pentafluorophenyl) aluminum, (c) tetraphenylgallium, tetrakis (3,4,5-trifluorophenyl) gallium, tetrakis [3,5-di (trifluoromethyl) phenyl] Gallium, tetrakis [3
5-di (t-butyl) phenyl] gallium, tetrakis (pentafluorophenyl) gallium, (d) tetraphenylphosphorus, tetrakis (pentafluorophenyl) phosphorus, (v) tetraphenylarsenic, tetrakis (pentafluorophenyl) arsenic, (F) Tetraphenyl antimony, tetrakis (pentafluorophenyl) antimony, (to) decaborate, undecaborate, carbadodecaborate, decachlorodecaborate, etc. are exemplified.

Examples of Lewis acids, particularly Lewis acids capable of converting the component (i) into cations, include various organic boron compounds, metal halogen compounds, and solid acids. Specifically, (i) triphenylboron, tris (3,5-difluorophenyl) boron, tris (pentafluorophenyl) boron, and other organoboron compounds;
(B) Aluminum chloride, aluminum bromide, aluminum iodide, magnesium chloride, magnesium bromide, magnesium iodide, magnesium bromine chloride, magnesium chloride iodide, magnesium bromide iodide, magnesium chloride hydride, magnesium chloride hydroxide, odor Metal halide compounds such as magnesium hydroxide, magnesium chloride alkoxide and magnesium bromide; or (c) solid acids such as silica-alumina and alumina.

These ionic compounds and Lewis acids can be used alone as the component (ii) or can be used in combination with the aluminum oxy compound of the general formula (V), (VI) or (VII). Further, trialkylaluminum, dialkylaluminum monohalide, monoalkylaluminum dihalide and alkylaluminum sesquihalide, and those in which some of these alkyl groups are replaced with phenoxy groups, and specific examples thereof are trimethylaluminum and triethylaluminum. It is also possible to use together with an organic aluminum compound such as triisobutylaluminum, diethylaluminum phenoxide, dimethylaluminum chloride.

(Iii) In the preferred catalyst of the present invention, the above-mentioned component (i) and component (ii) are contacted in the polymerization tank or outside the polymerization tank in the presence or absence of the monomer to be polymerized. Can be obtained.

Component (i) and component (i used in the present invention
The amount of i) used is arbitrary. For example, in the case of solvent polymerization, the amount of component (i) used is 10 ⁻⁷ to 10 ² as a transition metal atom.
More preferably, it is in the range of 10 millimol / liter and 10 ⁻⁴ to 1 millimol / liter. In the case of aluminum oxy compounds, the Al / transition metal molar ratio is usually 10-100,000.
0, 100-20,000 is preferable, 100-10,
The range of 000 is more preferable. On the other hand, when an ionic compound or a Lewis acid is used as the component (ii), the molar ratio to the transition metal is 0.1 to 1,000, preferably 0.5 to.
It is used in the range of 100, more preferably 1 to 50.

As described above, the catalyst of the present invention may contain other components in addition to the components (i) and (ii), but it may be added to the components (i) and (ii). Examples of the possible third component (optional component) include active hydrogen-containing compounds such as H ₂ O, methanol, ethanol and butanol; electron-donating compounds such as ethers, esters and amines; phenyl borate, dimethylmethoxyaluminum,
Examples thereof include alkoxy-containing compounds such as phenyl phosphite, tetraethoxysilane, and diphenyldimethoxysilane.

(6) Manufacture of Copolymer A method of copolymerizing an aromatic vinyl compound polymer having an unsaturated bond at the molecular chain terminal with an α-olefin using the above Ziegler-Natta type catalyst is a conventional slurry polymerization method. As a matter of course, a legal method can be adopted, but a liquid phase solventless polymerization method, a solution polymerization method or a gas phase polymerization method which does not substantially use a solvent can be adopted. Further, for these steps, a system such as continuous polymerization, batch polymerization or preliminary polymerization can be applied. As a polymerization solvent in the case of slurry polymerization, saturated aliphatic or aromatic hydrocarbons such as hexane, heptane, pentane, cyclohexane, benzene, and toluene are used alone or as a mixture. Polymerization temperature is -78 to 20
The temperature is about 0 ° C., preferably 0 to 150 ° C., and hydrogen can be supplementarily used as a molecular weight regulator at that time.

Α other than ethylene polymerized here is used.
-The stereoregularity of the olefin polymer is isotactic,
It may be either syndiotactic or atactic, and is not particularly limited.

When the copolymer obtained according to the present invention is used for ordinary purposes, the copolymer may contain a polymer having an unsaturated bond at the terminal of an unreacted molecular chain or an α-olefin polymer other than the copolymer. Coalescence may be included.

[0102]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto.

Reference Example 1: Production of 4-pentenyllithium The following production was carried out under high vacuum using the break seal method. That is, 5 g of metallic lithium and 5-bromo-1-
6 g of pentene was added to 120 ml of n-heptane, and the mixture was reacted at room temperature for 3 days. Next, 40 ml of diethyl ether was added to the reaction solution, the mixture was stirred at 0 ° C. for 24 hours and then filtered, and the solvent of the filtrate was distilled off. ^{By 1} H-NMR analysis, peaks derived from a vinyl group and a methyl anion were observed, and it was confirmed that 4-pentenyllithium was obtained. Yield 7
It was 0%.

Reference Example 2: Synthesis of polystyrene having an unsaturated bond at the end It was carried out in the same manner as in Reference Example 1 under high vacuum using the break seal method. That is, 0.14 g of 4-pentenyllithium obtained in Reference Example 1 was diluted with 9.3 ml of n-heptane,
This was added dropwise to a solution prepared by mixing 6.2 g of styrene and 200 ml of benzene under stirring and allowed to polymerize at room temperature for 2 hours, and then 2 ml of methanol was added to terminate the polymerization. The reaction solution was poured into 1 L of methanol, and the precipitated polymer was separated by filtration and dried. The obtained polymer (hereinafter referred to as "resin A") was 6.2 g, and the result of GPC measurement was that Mn was 3,33.
0, weight average molecular weight (hereinafter referred to as "Mw") is 3,48
It was 0. ^{From 1} H-NMR analysis, it was confirmed from the ratio of the peak intensity derived from the polystyrene main chain of Resin A to the peak intensity derived from the terminal vinyl group that a vinyl group was introduced at all one ends of the polymer.

Reference Example 3: Synthesis of polystyrene having unsaturated bond at the terminal In Reference Example 2, the amount of 4-pentenyllithium was 0.0.
4g, styrene amount 7.0g, benzene amount 300ml
The same procedure as in Reference Example 2 was repeated except that The obtained polymer (hereinafter referred to as “resin B”) was 6.9 g, and GP
As a result of measurement of C, Mn is 14,400 and Mw is 15,6.
It was 00. It was found from ¹ H-NMR analysis that vinyl groups were all introduced into the terminals of Resin B.

Reference Example 4: Synthesis of polystyrene having an unsaturated bond at the terminal In Reference Example 2, the amount of 4-pentenyllithium was 0.02 g,
The procedure of Reference Example 2 was repeated except that the amount of styrene was changed to 8.5 g and the amount of benzene was changed to 300 ml. The amount of the obtained polymer (hereinafter referred to as "resin C") was 8.3 g, and as a result of GPC measurement, Mn was 33,400 and Mw was 36,000.
Met. It was found from the analysis of ¹ H-NHR that vinyl groups were all introduced into the terminals of Resin C.

Reference Example 5 (comparative): Synthesis of polypropylene having unsaturated bond at the terminal (1) Production of ethylenebis (indenyl) zirconium dichloride A 300 ml glass flask thoroughly purged with nitrogen was charged with bis (indenyl) ethane 5. 16 g and 150 ml of tetrahydrofuran were charged and the mixture was cooled to -78 ° C. 25 ml of butyllithium (manufactured by Aldrich) (concentration: 1.6 mol /
Liter) was added dropwise over 1 hour, the temperature was gradually raised to the reflux temperature, and then the mixture was refluxed for 2 hours.

On the other hand, 100 ml of tetrahydrofuran was charged into a 200 ml glass flask sufficiently purged with nitrogen, and then-
Cooled to 78 ° C, and 4.7 g of zirconium tetrachloride
Was added and the temperature was gradually raised to room temperature. This zirconium tetrachloride solution was added all at once to the lithium salt solution of bis (indenyl) zirconium at 0 ° C., then the temperature was raised to the reflux temperature and the reaction was continued at the reflux temperature for 16 hours. The yellow solid formed was filtered off, washed with methanol and dried under reduced pressure. 1.9 g of ethylenebis (indenyl) zirconium dichloride was obtained.

(2) Manufacture of methylalumoxane To 565 ml of a toluene solution containing 48.2 g of trimethylaluminum, 50 g of copper sulfate pentahydrate was stirred at 0 ° C. for 5 hours.
It was added every 5 minutes at intervals of 5 minutes. After the completion, the temperature of the solution was slowly raised to 25 ° C, and the reaction was allowed to proceed at 25 ° C for 2 hours.
The temperature was raised to 2, and the reaction was performed for 2 days. The remaining copper sulfate solid was separated to obtain a toluene solution of alumoxane. The concentration of methylalumoxane was 27.3 mg / ml (2.7 w / v%).

(3) Production of Resin D In a stainless steel autoclave with an internal volume of 1.0 L equipped with a stirrer and a temperature control device, 400 ml of fully dehydrated and deenzymed toluene, 580 mg of methylalumoxane and ethylenebis (indenyl) were prepared. ) 0.418 mg (0.001 mmol) of zirconium cyclolide was introduced, and polymerization was carried out at a propylene pressure of 7 kg / cm ² G and 40 ° C. for 4 hours. After the completion of the polymerization, the polymerization solution was extracted into 3 L of methanol, the polymer was filtered and dried, and 180 g of a resin (hereinafter referred to as “resin D”) was recovered. As a result of GPC measurement, this was Mn18,700, molecular weight distribution (Mw / Mn)
It was 1.99.

¹³ C-NMR (manufactured by JEOL Ltd., trade name: J
EOL. FX-200) analysis showed that triad [m
The [m] fraction was 0.888, and vinylidene bonds were all at one end (0.79 per 1000 carbon atoms).

Example 1 50 ml of fully dehydrated and deoxygenated toluene, 3.8 g of resin A, 550 mg of methylalumoxane and ethylenebis (indenyl) zirconium dichloride were placed in a stainless steel autoclave having an internal volume of 100 ml equipped with a stirring and temperature control device. Introduce 2 mg, propylene pressure 0 kg / cm ² G,
Polymerization was carried out at 50 ° C. for 1 hour.

After the completion of the polymerization, 20 ml of hebutanol was added to the polymerization solution under a nitrogen atmosphere and the mixture was stirred at 70 ° C. for 1 hour. 100 ml of water and 1 g of sodium hydroxide were added thereto, and further 70
After stirring at 0 ° C. for 2 hours, the whole amount was added to 1 L of methanol to precipitate the produced copolymer, which was then filtered, dried and recovered to obtain 6.0 g of the copolymer.

After 2 g of this copolymer was dissolved in 100 ml of xylene under heating, it was added to 500 ml of methyl ethyl ketone, and the precipitated copolymer was separated by filtration and dried. The recovered copolymer was 1.95 g, and the styrene content in the copolymer was 62.7% by weight by infrared spectroscopy. GPC
As a result of the measurement of Mn10,700, Mw1
It was 9,300.

Example 2 In Example 1, resin B8.2 was used instead of resin A3.8 g.
The same procedure as in Example 1 was carried out except that g was used to obtain 10.0 g of a copolymer. Then, it was treated with xylene in the same manner as in Example 1 to obtain 1.66 g of a purified copolymer. The styrene content of this product was 76.3% by weight, and the Mn was 18,500.
And Mw was 38,900.

Example 3 In Example 1, resin C2.5 was used instead of resin A 3.8 g.
3.5 g of a copolymer was obtained in the same manner as in Example 1 except that the amount of g was used and the polymerization was performed at 40 ° C. for 5 hours. Then, it was treated with xylene in the same manner as in Example 1 to obtain 3.5 g of a purified copolymer. The styrene content of this product is 69.9.
% By weight, Mn was 46,100 and Mw was 91,100.

Comparative Example 1 5 g of resin D and 200 ml of carbon tetrachloride were placed in a round bottom flask which had been sufficiently replaced with nitrogen, and the temperature was raised to 70 ° C.
After stirring for 0 minutes, the mixture was cooled to room temperature with stirring. After adding 0.18 g of bromine thereto and reacting for 1 hour, the temperature was raised to 60 ° C. and further reacted for 30 minutes.

Then, the content in the flask was added to 2 L of methanol, the mixture was stirred for 1 hour, and suction filtration was carried out to separate a solid product by filtration. 3. The operation of adding the solid product to methanol and filtering is repeated 4 times, and then the solid product is dried to obtain 4.
98 g of brominated polymer was obtained. As a result of measuring the bromine content by ion chromatography, it was 3.3% by weight.

In the flask, 6.7 g of styrene and 115 ml of xylene were added, and 49 mg of n-butyllithium was added thereto to synthesize living polystyryl anion.

Into another flask 1.0 of the above brominated polymer
g, 120 ml of xylene was added, and the mixture was stirred at 50 ° C. Add the living polystyryl anion there,
The mixture was reacted at 50 ° C. for 144 hours with stirring.

Then, this was poured into a large excess of methanol to cause precipitation, and the solid product was recovered and dried. This solid product was dissolved in 1,4-dioxane by refluxing for 2 hours and then left overnight at 20 ° C., and then the insoluble portion was collected by filtration and dried.

The amount of the polymer obtained was 1.01 g, and the polystyrene content determined by infrared absorption spectrum was 6.5% by weight. The bromine content measured by ion chromatography was 1.5% by weight.
Met.

Application Examples 1 and 2 The copolymer obtained in Example 2, polypropylene (manufactured by Mitsubishi Petrochemical Co., Ltd., trade name: MA8) and poly (2,6-dimethyl-) were used.
1,4-phenylene ether) (manufactured by Nippon Polyether Co., intrinsic viscosity measured at 30 ° C. in chloroform: 0.4 dl / g) with the composition shown in Table 1, and an internal volume of 60 ml of plastomill (manufactured by Toyo Seiki Seisakusho Co., Ltd.). ) Was melt-kneaded at 230 ° C. for 5 minutes at a rotation speed of 180 rpm. Physical properties of the obtained resin composition were evaluated by the following, and the results are shown in Table 1.

(1) Bending elastic modulus A test piece having a width of 25 mm and a length of 80 mm was cut and processed in accordance with JIS.
It measured using the Instron tester according to K7203.

(2) Izod impact strength A test piece having a length of 31.5 mm, a width of 6.2 mm, and a thickness of 3.2 mm was injection-molded, and the Izod impact tester (Minimax CS-138TI, manufactured by Custom Scientific Co., Ltd.) was used.
Type) was used to measure the Izod impact strength with a notch.

[0126]

[Table 1]

[0127]

EFFECTS OF THE INVENTION According to the production method of the present invention, a thermoplastic resin having excellent impact resistance itself and excellent mechanical strength can be obtained, and it can be used for polyolefin, polystyrene, polyphenylene ether and the like. An excellent modifier and an excellent compatibilizer of polyphenylene ether and polyolefin or polyolefin and high-impact polystyrene are obtained.

Claims (1)

[Claims] 1. An aromatic vinyl compound monomer represented by the following general formula (I) CH ₂ ═CH—R ¹ —M (I) (wherein R ¹ represents a hydrocarbon group having 3 to 20 carbon atoms, M
Represents an alkali metal atom) and is subjected to a copolymerization step with an aromatic vinyl compound polymer having an unsaturated bond at a molecular chain terminal and an α-olefin, which are obtained by polymerization using an anionic polymerization initiator. A method for producing a characteristic copolymer.