JP2003238613A - Method for producing chloroprene copolymer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing an olefin-chloroprene copolymer by polymerizing olefins with chloroprene. <P>SOLUTION: This method for producing the olefin-chloroprene copolymer comprising olefin monomer units and chloroprene monomer units comprises using a transition metal compound of a specified structure with an auxiliary catalyst. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a process for producing a chloroprene copolymer comprising an olefin monomer unit and a 2-chloro-1,3-butadiene (hereinafter referred to as chloroprene) monomer unit. More specifically, the present invention relates to a method for producing a novel copolymer containing an olefin monomer unit and a chloroprene monomer unit having excellent cold resistance and solvent resistance.

[0002]

It is known that polymers of olefins are produced with heterogeneous Ziegler type catalysts. 1
Since 980, many methods for synthesizing polymers using a so-called homogeneous Ziegler-Natta catalyst system composed of a transition metal compound and an organoaluminum compound have been reported (Adv. Orga.
nomet.Chem., 18 , 99 (1980) etc.). Furthermore, recently, the synthesis of dienes has been attempted (Polym.Commun., 29 (1
0), 305 (1988)), but no successful example of a diene monomer containing a halogen in the molecule has been reported.

Chloroprene polymers are generally manufactured by aqueous radical polymerization. As one of the means for improving the properties of chloroprene polymers, there is a method of radically copolymerizing a comonomer component, and some chloroprene copolymers have been proposed. Known examples of comonomers include 2,3-dichloro-1,3-butadiene, 1-chloro-1,3-butadiene, acrylonitrile, methacrylic acid and their esters (Rubber Chemistry and
Technology, 49 , 670 (1976)).

[0004]

However, the chloroprene monomer has a very high radical polymerization rate as compared with other monomers, and the types of monomers to be copolymerized are limited in practical use. . Among the monomers to be copolymerized, sulfur, 2,3-dichloro-1,3-butadiene and 1-chloro-
Other monomers other than 1,3-butadiene had an essential problem that they were less likely to be incorporated into the molecule because they had lower copolymerizability than the chloroprene monomer.

On the other hand, olefins are known as basic raw materials for polymers, and it is well known that polymers such as polyethylene and polypropylene are widely used as general-purpose resins. However, since the radical polymerization reactivity of olefins is significantly lower than that of chloroprene, it has been recognized that it is impossible to obtain a copolymer of chloroprene and olefins up to now, and there are no reports of successful cases of these copolymers. Met.

[0006]

[Means for Solving the Problems] In order to overcome this situation, the present inventors have earnestly studied a method for obtaining a copolymer of olefins and chloroprene, and as a result, in the presence of a special catalyst system, olefins and chloroprene have been obtained. The inventors have found that the monomers are significantly copolymerized, and have completed the present invention.

That is, the present invention provides a method for producing a chloroprene copolymer comprising an olefin monomer unit and a chloroprene monomer unit, using a transition metal compound having a specific structure and a cocatalyst. is there.

The present invention will be described in detail below. The olefin used in the present invention refers to an olefin monomer having 2 to 10 carbon atoms, and as one example, ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene. , 1-heptene, 1-octene and the like. From the viewpoint of economy and reactivity, ethylene or propylene is preferably used. These are used as one kind or as a mixture of two or more kinds.

In the present invention, the chloroprene monomer may be used alone or the chloroprene monomer and 1-chloro-
It is used as a mixture with 1,3-butadiene monomer and / or 2,3-dichloro-1,3-butadiene monomer.

Furthermore, the chloroprene copolymer according to the present invention is copolymerized with a small amount of other chloroprene-copolymerizable monomers other than the above-mentioned monomers within a range not impairing the properties of the chloroprene copolymer described below. However, these are also included in the present invention. Examples of other monomers to be copolymerized include olefins having 11 to 20 carbon atoms, vinyl halide compounds such as vinyl chloride and vinylidene chloride,
Conjugated diene compounds such as butadiene and isoprene, styrene, p-chlorostyrene, pt-butylstyrene,
An aromatic compound such as p-methylstyrene or divinylbenzene can be used, and at least one kind can be used.

In the present invention, important points are the catalyst used for the polymerization and the polymerization operation. The method for producing the chloroprene copolymer according to the present invention will be described in detail below. First, the transition metal compound preferably used in the present invention is a transition metal compound represented by the following general formula (1).

[0012]

[Chemical 4]

Where A¹ And A²Is not replaced or replaced
Cyclopentadienyl group, unsubstituted or substituted 1-indene
Nyl group, unsubstituted or substituted benzo-1-indenyl group
Or an unsubstituted or substituted 9-fluorenyl group,³ 
And A^Four Is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or
Or an aryl group having 6 to 20 carbon atoms or an alkyl group, respectively.
Reel group, arylalkyl group or halogenated ant
Group or oxygen, nitrogen, sulfur or silicon
A hydrocarbon group having 1 to 20 carbon atoms containing a selected atom, or R
³ ₃Si (R³ Is an alkyl group having 1 to 5 carbon atoms),
Q is A¹ And A²Hydrocarbon having 2 to 10 carbon atoms connecting
C1 containing radical or silicon, germanium or tin
-10 hydrocarbon groups, or carbon, silicon, germanium
Alternatively, it is a tin atom, and A³ And A^FourAre connected to each other
Doing A³, A^Four And a ring structure is formed between Q and
Good, R¹ And R² Is a halogen atom, hydrogen atom, carbon
Alkyl group of number 1 to 10, alkylaryl group or
Arylalkyl group or -OR^Four (R^FourHas 1 carbon
-10 hydrocarbon groups, O is an oxygen atom), -NR^Five ₂(R^Five
Is a hydrocarbon group having 1 to 10 carbon atoms, N is a nitrogen atom)
And M is zirconium, titanium or hafnium
is there.

Specific examples of A ¹ and A ² include cyclopentadienyl group, methylcyclopentadienyl group, dimethylcyclopentadienyl group, 1-indenyl group, 2
-Methyl-1-indenyl group, tetrahydro-1-indenyl group, 4,5-benzo-1-indenyl group, 4-
(1-naphthyl) -1-indenyl group, 9-fluorenyl group, methyl-9-fluorenyl group, 2,7-di-tert-butyl-9-fluorenyl group and the like.

Specific examples of A3 and A4 include hydrogen atom, methyl group, ethyl group, propyl group, phenyl group, toluyl group, fluorophenyl group, methoxyphenyl group,
For example, a benzyl group.

Q has 2 to 10 carbon atoms connecting A1 and A2
Or a hydrocarbon group having 1 to 10 carbon atoms including silicon, germanium or tin, or a carbon, silicon, germanium or tin atom, preferably a hydrocarbon group having 2 to 10 carbon atoms, a carbon atom or a silicon atom. Is.

A3 and A4 are connected to each other to form A3,
A ring structure may be formed between A4 and Q, and in such a case, the group formed by A3, A4 and Q is a cyclopentylidene group, a cyclohexylidene group, a tetrahydropyran-4-ylidene group. And so on.

R1 and R2 represent a halogen atom, a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a silicon-containing alkyl group, an aryl group having 6 to 20 carbon atoms, an alkylaryl group or an arylalkyl group. Preferable specific examples of R1 and R2 include chlorine atom, methyl group, phenyl group, trimethylsilylmethyl group, methoxy group and dimethylamino group.

The transition metal compound represented by the general formula (1) in the present invention is characterized by having a crosslinkable ligand. By using such a transition metal compound, the copolymerization of the olefin monomer and the chloroprene monomer can be promoted.

Examples of the transition metal compound include the following compounds. Dimethylmethylenebis (1-indenyl) zirconium dichloride, diethylmethylenebis (1-indenyl)
Zirconium dichloride, di-n-propylmethylenebis (1-indenyl) zirconium dichloride, di-propylmethylenebis (1-indenyl) zirconium dichloride, methylethylmethylenebis (1-indenyl) zirconium dichloride, methyl n-propylmethylenebis ( 1-indenyl) zirconium dichloride,
Methyl i-propylmethylenebis (1-indenyl) zirconium dichloride, ethyl n-propylmethylenebis (1-indenyl) zirconium dichloride, ethyl i-propylmethylenebis (1-indenyl) zirconium dichloride.

Cyclohexylidenebis (1-indenyl) zirconium dichloride, cyclopentylidenebis (1-indenyl) zirconium dichloride, diphenylmethylenebis (1-indenyl) zirconium dichloride, dimethylmethylene (1-indenyl) (2-methyl-1) -Indenyl) zirconium dichloride, dimethylmethylene (1-indenyl) (2-ethyl-1-indenyl) zirconium dichloride, dimethylmethylene (1-indenyl) (2-phenyl-1-indenyl)
Zirconium dichloride, dimethylmethylene (1-indenyl) (2-methyl-4-phenyl-1-indenyl) zirconium dichloride, dimethylmethylene (1-
Indenyl) (4-phenyl-1-indenyl) zirconium dichloride, dimethylmethylene (1-indenyl) {4- (1-naphthyl) -1-indenyl} zirconium dichloride, dimethylmethylene (1-indenyl) (2,4-dimethyl) -1-Indenyl) zirconium dichloride, dimethylmethylene (1-indenyl)
{2-Methyl-4- (1-naphthyl) -1-indenyl} zirconium dichloride, dimethylmethylene (1-
Indenyl) (2,4-diphenyl-1-indenyl)
Zirconium dichloride, dimethylmethylene (1-indenyl) (4,5-benzo-1-indenyl) zirconium dichloride.

Dimethylmethylenebis (2-methyl-1-)
Indenyl) zirconium dichloride, dimethylmethylenebis (2-ethyl-1-indenyl) zirconium dichloride, dimethylmethylenebis (2-phenyl-1-)
Indenyl) zirconium dichloride, dimethylmethylenebis (2-methyl-4-phenyl-1-indenyl)
Zirconium dichloride, dimethyl methylene bis (2,
4-dimethyl-1-indenyl) zirconium dichloride, dimethylmethylenebis {2-methyl-4- (1-naphthyl) -1-indenyl} zirconium dichloride,
Dimethylmethylenebis (2,4-phenyl-1-indenyl) zirconium dichloride, dimethylmethylenebis (4-diphenyl-1-indenyl) zirconium dichloride, dimethylmethylenebis {4- (1-naphthyl)
-1-Indenyl} zirconium dichloride, dimethylmethylene (2-methyl-1-indenyl) (2-ethyl-1-indenyl) zirconium dichloride, dimethylmethylene (2-methyl-1-indenyl) (2-phenyl-1-indenyl) ) Zirconium dichloride, dimethylmethylene (2-methyl-1-indenyl) (4-phenyl-1-indenyl) zirconium dichloride, dimethylmethylene (2-phenyl-1-indenyl) (4-
Phenyl-1-indenyl) zirconium dichloride,
Dimethylmethylene (4-methyl-1-indenyl) (4
-Phenyl-1-indenyl) zirconium dichloride, dimethylmethylene (4-phenyl-1-indenyl) {4- (1-naphthyl) -1-indenyl} zirconium dichloride, dimethylmethylenebis (4,5-benzo-1-indenyl) ) Zirconium dichloride.

Dimethylsilylenebis (1-indenyl)
Zirconium dichloride, diethyl silylene bis (1-
Indenyl) zirconium dichloride, di-n-propylsilylene bis (1-indenyl) zirconium dichloride, di-propylpropylylene bis (1-indenyl) zirconium dichloride, methylethylsilylene bis (1
-Indenyl) zirconium dichloride, methyl n-propylsilylenebis (1-indenyl) zirconium dichloride, methyl i-propylsilylenebis (1-indenyl) zirconium dichloride, ethyl n-propylsilylenebis (1-indenyl) zirconium dichloride, ethyl i -Propylsilylenebis (1-indenyl) zirconium dichloride, cyclohexylsilylenebis (1-indenyl) zirconium dichloride, cyclopentylsilylenebis (1-indenyl) zirconium dichloride, diphenylsilylenebis (1-indenyl) zirconium dichloride, dimethylsilylene Bis (methylcyclopentadienyl) zirconium dichloride, dimethylsilylene bis (2,4-dimethylcyclopentadienyl) zirco Umujikurorido, dimethylsilylene bis (2,3,5-trimethyl cyclopentadienyl) zirconium dichloride.

Dimethylsilylene (1-indenyl) (2
-Methyl-1-indenyl) zirconium dichloride,
Dimethylsilylene (1-indenyl) (2-ethyl-1
-Indenyl) zirconium dichloride, dimethylsilylene (1-indenyl) (2-phenyl-1-indenyl) zirconium dichloride, dimethylsilylene (1-
Indenyl) (2-methyl-4-phenyl-1-indenyl) zirconium dichloride, dimethylsilylene (1
-Indenyl) (4-phenyl-1-indenyl) zirconium dichloride, dimethylsilylene (1-indenyl) {4- (1-naphthyl) -1-indenyl} zirconium dichloride, dimethylsilylene (1-indenyl) (2,4- Dimethyl-1-indenyl) zirconium dichloride, dimethylsilylene (1-indenyl)
{2-Methyl-4- (1-naphthyl) -1-indenyl} zirconium dichloride, dimethylsilylene (1-
Indenyl) (2,4-diphenyl-1-indenyl)
Zirconium dichloride, dimethyl silylene (1-indenyl) (4,5-benzo-1-indenyl) zirconium dichloride.

Dimethylsilylenebis (2-methyl-1-)
Indenyl) zirconium dichloride, dimethylsilylenebis (2-ethyl-1-indenyl) zirconium dichloride, dimethylsilylenebis (2-phenyl-1-)
Indenyl) zirconium dichloride, dimethylsilylene bis (2-methyl-4-phenyl-1-indenyl)
Zirconium dichloride, dimethyl silylene bis (2,
4-dimethyl-1-indenyl) zirconium dichloride, dimethylsilylene bis {2-methyl-4- (1-naphthyl) -1-indenyl} zirconium dichloride,
Dimethylsilylenebis (2,4-diphenyl-1-indenyl) zirconium dichloride, dimethylsilylenebis (4-diphenyl-1-indenyl) zirconium dichloride, dimethylsilylenebis {4- (1-naphthyl) -1-indenyl} zirconium dichloride , Dimethylsilylene (2-methyl-1-indenyl) (2-ethyl-1-indenyl) zirconium dichloride, dimethylsilylene (2-methyl-1-indenyl) (2-phenyl-1-indenyl) zirconium dichloride, dimethylsilylene ( 2-methyl-1-indenyl) (4-
Phenyl-1-indenyl) zirconium dichloride,
Dimethylsilylene (2-phenyl-1-indenyl)
(4-Phenyl-1-indenyl) zirconium dichloride, dimethylsilylene (4-methyl-1-indenyl) (4-phenyl-1-indenyl) zirconium dichloride, dimethylsilylene (4-phenyl-1-indenyl) {4- ( 1-naphthyl) -1-indenyl} zirconium dichloride, dimethylsilylene bis (4,5
-Benzo-1-indenyl) zirconium dichloride,
Dimethylsilylene bis (2-methyl-4,5-benzo-
1-indenyl) zirconium dichloride.

Dimethylmethylene (1-indenyl) (cyclopentadienyl) zirconium dichloride, cyclohexylmethylene (1-indenyl) (cyclopentadienyl) zirconium dichloride, diphenylmethylene (1-indenyl) (cyclopentadienyl) zirconium dichloride .

Dimethylmethylene (2-methyl-1-indenyl) (cyclopentadienyl) zirconium dichloride, dimethylmethylene (4-methyl-1-indenyl) (cyclopentadienyl) zirconium dichloride, dimethylmethylene (1-indenyl) (2-Methyl-1-cyclopentadienyl) zirconium dichloride, dimethylmethylene (1-indenyl) (2,4-dimethyl-1-cyclopentadienyl) zirconium dichloride.

Dimethylmethylene (cyclopentadienyl) (fluorenyl) zirconium dichloride, cyclohexylidene (cyclopentadienyl) (fluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (fluorenyl) zirconium dichloride, methylphenylmethylene ( Cyclopentadienyl) (fluorenyl) zirconium dichloride.

Dimethylmethylene (cyclopentadienyl) (2,7-ditert-butyl-9-fluorenyl) zirconium dichloride, dimethylmethylene (2
-Methyl-1-cyclopentadienyl) (fluorenyl) zirconium dichloride, dimethylmethylene (2,
4-Dimethyl-1-cyclopentadienyl) (fluorenyl) zirconium dichloride.

Ethylenebis (1-indenyl) zirconium dichloride, ethylenebis (4,5,6,7-tetrahydro-1-indenyl) zirconium dichloride,
Ethylenebis (4-methyl-1-indenyl) zirconium dichloride, ethylenebis (5-methyl-1-indenyl) zirconium dichloride, ethylenebis (6-
Methyl-1-indenyl) zirconium dichloride, ethylenebis (2,3-dimethyl-1-indenyl) zirconium dichloride and the like. Although the Zr complex has been exemplified above, the same compounds as described above are preferably used for the Ti complex and the Hf complex. When the above complex is a racemate, the racemate itself may be used, or only the D-form and the L-form may be separated and used.

In the present invention, an organoaluminum compound and / or a boron compound is used as a cocatalyst together with the above transition metal compound. Aluminoxane (also referred to as alumoxane) is suitable as the organoaluminum compound used as the cocatalyst. What is aluminoxane?
It is a cyclic or chain compound represented by the following general formulas (2) and (3).

[0032]

[Chemical 5]

Here, R6 is an alkyl group having 1 to 5 carbon atoms, an aryl group having 6 to 10 carbon atoms, or hydrogen, and m is 2
Is an integer of -100. Each R6 may be the same or different.

[0034]

[Chemical 6]

Here, R7, R8, R9 and R10 are alkyl groups having 1 to 5 carbon atoms, aryl groups having 6 to 10 carbon atoms,
Alternatively, hydrogen and n are integers of 2 to 100. R7 ~ R10
May be the same or different from each other. As the aluminoxane, methylalumoxane, ethylalumoxane, and triisobutylalumoxane are preferably used, and methylalumoxane is particularly preferably used.
If desired, a mixture of these different types of alumoxanes may be used. Further, these alumoxanes and alkylaluminums such as trimethylaluminum, triethylaluminum, triisobutylaluminum and alkylaluminum containing halogen such as dimethylaluminum chloride may be used in combination.

Examples of the ionized ionic compound containing boron used in the present invention include trimethylammonium tetraphenylborate, triethylammonium tetraphenylborate, tripropylammonium tetraphenylborate and tri (n-butyl) ammonium tetraphenyl. Borate, tri (n-butyl) ammonium tetra (p-tolyl) phenyl borate, tri (n-butyl) ammonium tetra (p-ethylphenyl) borate, tri (n-butyl) ammonium tetra (pentafluorophenyl) borate, trimethyl Ammonium tetra (p-tolyl) borate, trimethyl ammonium tetra (o-tolyl) borate, trimethyl ammonium tetrakis-3,5-dimethylphenyl borate, triethyl Nmo tetrakis-3,5
Dimethylphenyl borate, tributylammonium tetrakis-3,5-dimethylphenylborate, tributylammonium tetrakis-2,4-dimethylphenylborate, anilinium tetrakispentafluorophenylborate, N, N-dimethylanilinium tetraphenylborate, N, N -Diethylanilinium tetraphenylborate, N, N-dimethylanilinium tetrakis (p-tolyl) borate, N, N-dimethylanilinium tetrakis (m-tolyl) borate, N, N
-Dimethylanilinium tetrakis (2,4-dimethylphenyl) borate, N, N-dimethylanilinium tetrakis (3,5-dimethylphenyl) borate, N,
N-dimethylanilinium tetrakis (pentafluorophenyl) borate, N, N-diethylanilinium tetrakis (pentafluorophenyl) borate, N, N
-2,4,5-pentamethylanilinium tetraphenylborate, N, N-2,4,5-pentaethylanilinium tetraphenylborate, di- (isopropyl)
Ammonium tetrakis pentafluorophenyl borate, di-cyclohexyl ammonium tetraphenyl borate, triphenylphosphonium tetraphenyl borate, tri (methylphenyl) phosphonium tetraphenyl borate, tri (dimethylphenyl) phosphonium tetraphenyl borate, triphenylcarbenium tetrakis (pentafluoro Phenyl) borate, triphenylcarbenium tetrakis (p-tolyl) borate, triphenylcarbenium tetrakis (m-tolyl) borate, triphenylcarbenium tetrakis (2,4-dimethylphenyl) borate, triphenylcarbenium tetrakis (3) , 5-dimethylphenyl)
Borate, tropylium tetrakis pentafluorophenyl borate, tropylium tetrakis (p-tolyl)
Borate, tropylium tetrakis (m-tolyl) borate, tropylium tetrakis (2,4-dimethylphenyl) borate, tropylium tetrakis (3,5-dimethylphenyl) borate, and the like. These boron compounds and the above organoaluminum compounds may be used at the same time. Particularly when a boron compound is used as a cocatalyst, the addition of an alkylaluminum compound such as triisobutylaluminum is effective for removing impurities such as water contained in the polymerization system, which adversely affect the polymerization. By using the above-mentioned catalyst, it is possible to produce a copolymer composed of an olefin monomer unit and a chloroprene monomer unit, which has been heretofore unavailable.

In producing the copolymer of the present invention, the above-mentioned olefin monomer, chloroprene monomer,
In addition, if necessary, a copolymerizable monomer is brought into contact with a transition metal compound that is a metal complex and a cocatalyst. As the method, a method of polymerizing in a liquid monomer without using a solvent, pentane, hexane, heptane, cyclohexane, benzene, toluene, xylene, chloro-substituted benzene, chloro-substituted toluene, methylene chloride, saturated aliphatic such as chloroform or There is a method of polymerizing using an aromatic hydrocarbon or a halogenated hydrocarbon alone or in a mixed solvent.

The weight average degree of polymerization of the copolymer of the present invention is 10
˜100,000, preferably 20 to 10,000.
Further, from the viewpoint of expressing new properties different from those of the conventional chloroprene polymer or olefin polymer, the content ratio of the chloroprene monomer unit in the copolymer is 2 to 98 with respect to the copolymer of the present invention. Mol%, preferably 5-9
It is 5 mol%, more preferably 10 to 90 mol%.

The polymerization temperature is suitably -78 ° C to 120 ° C, preferably 0 ° C to 80 ° C. Polymerization temperatures lower than −78 ° C. are industrially disadvantageous, and temperatures above 120 ° C. are not suitable because dehydrochlorination from chloroprene units occurs. When an organoaluminum compound is used as a cocatalyst, the ratio of aluminum atom / complex metal atom is 0.1 to 100,000, preferably 10 to metal of the complex.
Used in a ratio of 10000. If it is less than 0.1, the metal complex cannot be effectively activated, and if it exceeds 100,000, it is economically disadvantageous. When a boron compound is used as the cocatalyst, the boron atom / complex metal atom ratio is 0.01 to 1
It is used in a ratio of 00, preferably 0.1 to 10, particularly preferably 1. If it is less than 0.01, the metal complex cannot be effectively activated, and if it exceeds 100, it is economically disadvantageous. The metal complex and the co-catalyst are mixed outside the polymerization tank,
They may be prepared or mixed in a tank at the time of polymerization.

Additives, auxiliaries and the like usually used for polymers can be added to the copolymer of the present invention within a range that does not impair the effects of the present invention. Suitable additives and auxiliaries include antioxidants, lubricants, vulcanizing agents, vulcanization accelerators, plasticizers, UV absorbers, stabilizers, pigments, colorants, fillers, foaming agents and the like.

[0041]

The present invention will be described below with reference to examples.
The present invention is not limited to the examples below. The degree of polymerization of the copolymer in the examples was calculated from the weight average molecular weight in terms of standard polystyrene using GPC (gel permeation chromatography).

The glass transition temperature of the copolymer was measured using a differential scanning calorimeter DSC-200 manufactured by Seiko Denshi KK by selecting the following temperature program. Step 1. After heating from room temperature to 120 ° C at a constant heating rate of 10 ° C / min, hold at 120 ° C for 1 minute. Step 2. After cooling from 120 ° C to -100 ° C at a constant cooling rate of 5 ° C / min, hold at -100 ° C for 2 minutes. Step 3. Heat from -100 ° C to 200 ° C at a constant heating rate of 10 ° C / min. The glass transition temperature was measured in step 3 above.

The solvent resistance was evaluated by immersing the copolymer in a specific organic solvent in an atmosphere of 25 ° C. for 48 hours, stirring and swelling or dissolving. The monomers and toluene used in the examples were dehydrated ones.

Example 1 10.5 m of dehydrated chloroprene monomer was placed in an autoclave equipped with a stirrer and having an internal volume of 100 ml which had been sufficiently replaced with nitrogen.
l and methylalumoxane (manufactured by Tosoh Akzo, MMA
O-3A) was charged in an amount of 9.0 mmol based on Al atom.
Next, while flowing ethylene at normal pressure, 20 m of a toluene solution containing 18 μmol of diphenylmethylene (cyclopentadienyl) (fluorenyl) zirconium dichloride.
1 with a syringe, and immediately with ethylene 5 kg / cm
The pressure was raised to 2 and the temperature was raised to 40 ° C. in about 5 minutes. After that, 4
Polymerization was carried out at 0 ° C. for 1 hour while maintaining the ethylene pressure at 5 kg / cm 2. After the completion of the polymerization, ethylene was gradually released, and the content was put into a large excess of dilute hydrochloric acid / methanol mixed solution to recover a polymer (hereinafter, a chloroprene copolymer is often referred to as a polymer). This at 25 ℃,
After drying under reduced pressure for 24 hours, 7.3 g of polymer was obtained.

Example 2 A polymer was obtained according to the method described in Example 1 except that dimethylmethylene (cyclopentadienyl) (fluorenyl) zirconium dichloride was used as the transition metal compound. The polymer yield was 6.8 g.

Example 3 A polymer was obtained according to the method described in Example 1 except that diphenylmethylene (1-indenyl) (cyclopentadienyl) zirconium dichloride was used as the transition metal compound. The polymer yield was 4.9 g.

Example 4 Except that dimethylsilylenebis (1-indenyl) zirconium dichloride was used as the transition metal compound.
A polymer was obtained according to the method described in Example 1. The polymer yield was 2.4 g.

Example 5 A polymer was obtained according to the method described in Example 1 except that dimethylsilylenebis (2-methyl-4,5-benzo-1-indenyl) zirconium dichloride was used as the transition metal compound. The polymer yield was 3.8 g.

Example 6 A polymer was obtained according to the method described in Example 1 except that ethylenebis (1-indenyl) zirconium dichloride was used as the transition metal compound. The polymer yield was 3.5 g.

Example 7 In a dehydrating atmosphere, 2.0 mmol of triisobutylaluminum was added to 50 ml of toluene and stirred for 10 minutes, and then 20 ml of a toluene solution containing 18 μmol of diphenylmethylene (cyclopentadienyl) (fluorenyl) zirconium dichloride, and then 18 μmol of triphenylcarbenium tetrakis (pentafluorophenyl) borate was added and stirred for 10 minutes. This solution was introduced into an autoclave having an internal volume of 250 ml which had been sufficiently replaced with nitrogen, and then chloroprene monomer 9.8.
I charged ml. Immediately, the pressure was raised to 5 kg / cm @ 2 with ethylene, and the temperature was raised to 40 DEG C. in about 5 minutes. Thereafter, polymerization was carried out at 40 ° C. for 1 hour while maintaining the ethylene pressure at 5 Kg / cm 2. After completion of the polymerization, ethylene was gradually released, and the contents were put into a large excess of dilute hydrochloric acid / methanol mixture,
The polymer was recovered. This was dried under reduced pressure at 25 ° C. for 24 hours to obtain 7.8 g of a polymer.

Example 8 In Example 1, the ethylene pressure during polymerization was changed to normal pressure (1 K).
g / cm @ 2 G) and the polymerization temperature was 50 DEG C. and the polymerization was carried out for 3 hours. The polymer yield was 6.7 g.

Example 9 9.9 ml of a mixture of chloroprene monomer and 1-chloro-1,3-butadiene monomer (content of 1-chloro-1,3-butadiene 5 mol%) was added, and the others were carried out. Example 1
Polymerization was performed according to the same procedure and apparatus as described above. The polymer yield was 7.0 g.

Example 10 10.0 ml of a mixture of chloroprene monomer and 2,3-dichloro-1,3-butadiene monomer (content of 2,3-dichloro-1,3-butadiene 5 mol%) was added. Polymerization was performed according to the same procedure and apparatus as in Example 1 except for the above. The polymer yield was 7.5 g.

Table 1 shows the degree of polymerization, the glass transition temperature as an index of cold resistance, and the solvent resistance of the chloroprene copolymers obtained in Examples 1 to 10. In addition, in Table 1, the glass transition temperature and the solvent resistance of the commercially available chloroprene polymer (Denkachloroprene M-40 manufactured by Denki Kagaku Kogyo) and the ethylene polymer (Sumikasen F403-1 manufactured by Sumitomo Chemical) are also shown. The results are shown as Comparative Example 1 and Comparative Example 2. Example 1
The glass transition temperatures of the polymers obtained in Nos. 10 to 10 are both values between the chloroprene polymer and the ethylene polymer, and the chloroprene monomer unit and the ethylene monomer unit are significantly copolymerized. It is shown that.

[0055]

[Table 1]

[0056]

The chloroprene copolymer comprising olefin monomer units and chloroprene monomer units according to the present invention can be expected to have excellent properties such as cold resistance and solvent resistance as compared with conventional chloroprene polymers. It is a polymer. In addition, the production method of the present invention can efficiently produce a chloroprene copolymer composed of an olefin monomer unit and a chloroprene monomer unit. Therefore, cold resistance,
Practical application can be expected for new applications where solvent resistance is required.

   ─────────────────────────────────────────────────── ─── Continued front page    F term (reference) 4J100 AA01Q AA02Q AA03Q AA04Q                       AA07Q AA15Q AA16Q AA17Q                       AA19Q AS06R AS07P BB01R                       CA04 CA05 DA01 FA10                 4J128 AA01 AB00 AB01 AC01 AC03                       AC10 AC23 AC28 AD05 AD06                       BA00A BA01B BA02B BB00A                       BB00B BB01B BC12B BC14B                       BC25B EA01 EB01 EB02                       EB03 EB04 EB05 EB07 EB08                       EB09 EB10 EB12 EC02 EC04                       FA01 FA02 GA01 GB01

Claims (6)

[Claims] 1. An olefin monomer having 2 to 10 carbon atoms and a 2-chloro-1,3-butadiene monomer using a transition metal compound represented by the following general formula (1) and a cocatalyst. A method for producing a chloroprene copolymer, which comprises polymerizing a body. [Chemical 1] (Wherein A ¹ and A ² are an unsubstituted or substituted cyclopentadienyl group, an unsubstituted or substituted 1-indenyl group, an unsubstituted or substituted benzo-1-indenyl group or an unsubstituted or substituted 9-fluorenyl group , A ³ and A ⁴ are a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 20 carbon atoms, an alkylaryl group,
An arylalkyl group or a halogenated aryl group, a hydrocarbon group having 1 to 20 carbon atoms containing an atom selected from oxygen, nitrogen, sulfur or silicon, or R ³ ₃ Si
(R ³ is an alkyl group having 1 to 5 carbon atoms) and Q is A ¹
And a hydrocarbon group having 2 to 10 carbon atoms which connects A ² and C ¹ to 10 or a hydrocarbon group containing silicon, germanium or tin, or a carbon, silicon, germanium or tin atom, and A ³ and A ⁴ may be linked to each other to form a ring structure between A ³ , A ⁴ and Q,
R ¹ and R ² are a halogen atom, a hydrogen atom, and a carbon number of 1 to 1.
0 alkyl group, alkylaryl group, arylalkyl group or -OR ⁴ (R ⁴ is a hydrocarbon group having 1 to 10 carbon atoms, O represents an oxygen _{^{atom), - NR 5 2 (R}} 5 is a carbon number 1 to 1
0 is a hydrocarbon group, N is a nitrogen atom), and M is zirconium, titanium or hafnium. ) 2. A transition metal compound represented by the above general formula (1) and a cocatalyst are used, (1) an olefin monomer having 2 to 10 carbon atoms, and (2) 2-chloro-1. , 3-Butadiene monomer, and (3) 1-chloro-1,3-butadiene monomer and / or 2,3-dichloro-1,3-butadiene monomer are polymerized. Method for producing copolymer. 3. The chloroprene copolymer has a weight average degree of polymerization of 10 to 100,000.
Or the method for producing the chloroprene copolymer according to 2. 4. The method for producing a chloroprene copolymer according to claim 1, wherein the olefin monomer is ethylene or propylene. 5. The chloroprene according to claim 1, wherein the cocatalyst is an aluminoxane represented by the following general formula (2) or (3) (also referred to as alumoxane). Method for producing copolymer. [Chemical 2] (Here, R6 is an alkyl group having 1 to 5 carbon atoms, and 6 carbon atoms.
-10 is an aryl group, or hydrogen, and an integer of m2-100. ) [Chemical 3] (Here, R7 to R10 are alkyl groups having 1 to 5 carbon atoms, aryl groups having 6 to 10 carbon atoms, or hydrogen, and n is 2 to 10
It is an integer of 0. R7 to R10 may be the same or different. ) 6. The method for producing a chloroprene copolymer according to claim 1, wherein the cocatalyst is an ionized ionic compound containing boron.