JP2002256028A - Method for producing vinyl chloride-olefin copolymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a novel method for producing a vinyl chloride-olefin copolymer. SOLUTION: The copolymerization of a vinyl chloride and an olefin is carried out using (A) an organoaluminum compound represented by the formula A1X<1> X<2> X<3> [X<1> , X<2> and X<3> are each independently a halogen atom, an alkyl group which may be substituted, an aryl group which may be substituted, an alkoxy group which may be substituted or an aryloxy group which may be substituted], (B) a metallocene compound containing a central metal selected from the group IV of the periodic table and (C) a halogenated hydrocarbon.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a copolymerization reaction between vinyl chloride and an olefin using a specific organoaluminum compound, a metallocene compound containing a central metal selected from Group IV of the periodic table, and a halogenated hydrocarbon. And a novel method for producing a vinyl chloride-olefin copolymer.

[0002]

2. Description of the Related Art The physicochemical properties of a polymer greatly affect the primary structure of the polymer. Among them, copolymers composed of two or more types of monomers exhibit different physicochemical properties from mixtures of homopolymers, and thus many copolymers have been synthesized and studied.

[0003] Polyvinyl chloride is a well-balanced material in terms of processability, physical properties, and price, and is used in a wide range of fields from soft to hard such as films and sheets.
However, polyvinyl chloride uses a large amount of plasticizer at the time of its processing, and its improvement is required due to environmental problems and the like.

As one of the methods, a copolymer of vinyl chloride and another monomer has been proposed. Such a copolymer is expected not only in terms of improving the processability of polyvinyl chloride but also in terms of reducing the amount of plasticizer.

[0005] As a copolymer of vinyl chloride and another monomer, a copolymer of ethylene, vinylidene chloride, vinyl acetate and the like is generally known. It is effective in reducing the properties and plasticizers.
And such a vinyl chloride-ethylene copolymer,
Generally, it can be easily obtained by a radical polymerization reaction with a radical polymerization initiator. As such a method, for example, azobisisobutyronitrile (R.
D. Burkhart, N .; L. Zutty, J .; Po
lym. Sci. , Part A-1, 1137 (19
63)) or benzoyl peroxide (T. Otsu, YK
inoshita, A .; Nakamachi, Makr
omol. Chem. , 66, 205 (1963)), trialkylboron (NL Zutty).
(UCC), U.S.A. S. O. 3051, 689 (1
962)) has been reported.

On the other hand, Ti (n-
BuO)_Four-EtAlCl_TwoOr Et _TwoFor AlCl-based catalyst
Copolymerization of vinyl chloride and ethylene has been reported
(A. Misono, Y. Uchida, K. Yama.
da, T .; Saeki, Bull. Chem. Soc.
Jpn. , 41, 2995 (1968)).

Further, it has been reported that a metallocene catalyst which has been remarkably developed in recent years is used for the polymerization of olefins and styrenes, and it is possible to control the three-dimensional structure of the obtained polymer and the composition distribution in the copolymerization. . However,
Regarding the polymerization of vinyl chloride, which is a non-conjugated monomer, using a metallocene catalyst, for example, Ento et al.
reprints, Japan 47 (8), 1651
(1998)), it is reported that the obtained polymer has higher syndiotacticity than the polymer obtained by ordinary radical polymerization, and that copolymerization with ethylene is possible. . However, this polymerization system requires expensive methylalumoxane, which is economically disadvantageous.

[0008]

The vinyl chloride-olefin copolymer is expected to have improved properties such as improved processability, improved physical properties, and reduced plasticizer during processing, as compared with polyvinyl chloride. Is done.

Accordingly, an object of the present invention is to provide a novel method for producing a vinyl chloride-olefin copolymer having excellent physical properties.

[0010]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that a specific organoaluminum compound, a metallocene compound containing a central metal selected from Group IV of the periodic table, The inventors have found that copolymerization of vinyl chloride and an olefin is possible by using a halogenated hydrocarbon, and have completed the present invention.

That is, the present invention relates to a compound represented by the general formula AlX ¹ X ² X
³ (wherein X ¹ , X ² and X ³ each independently represent a halogen atom, an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted alkoxy group or a substituted An aryloxy group which may be substituted), a metallocene compound (B) containing a central metal selected from Group IV of the periodic table, and a halogenated hydrocarbon (C). The present invention relates to a method for producing a vinyl chloride-olefin copolymer, which comprises performing a copolymerization reaction between vinyl and an olefin.

Hereinafter, the present invention will be described in more detail.

In the present invention, the aluminum compound (A)
The aluminum compound used for the general formula is AlX ¹
X ² X ³ (wherein X ¹ , X ² and X ³ each independently represent a halogen atom, an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted alkoxy group Or an aryloxy group which may be substituted.).

Here, when X ¹ , X ² and X ³ are a halogen atom, examples thereof include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Examples include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and an isobutyl group.When the aryl group is an optionally substituted aryl group, for example, a phenyl group, a naphthyl group, a phenyl chloride group,
Examples include a phenyl bromide group, a methylphenyl group and the like, and in the case of an optionally substituted alkoxy group, for example, methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group and the like. And
When it is an aryloxy group which may be substituted, examples thereof include a phenoxy group, a naphthoxy group, a phenoxy chloride group, a phenoxy bromide group, and a methylphenoxy group.

Examples of such an aluminum compound (A) include trimethylaluminum, triethylaluminum, tri-n-propylaluminum,
Triisopropylaluminum, tributylaluminum, triisobutylaluminum, methylaluminum bis (2,6-di-tert-butyl-4-methylphenoxide), dimethylaluminum chloride, methylaluminum dichloride, etc., and vinyl chloride with high production efficiency. -Trimethyl aluminum, triethyl aluminum, tri n-propyl aluminum,
Trialkylaluminums such as triisopropylaluminum, tributylaluminum and triisobutylaluminum are preferable, and among them, trimethylaluminum, triethylaluminum and / or triisobutylaluminum are particularly preferable.

In the present invention, as the metallocene compound (B) to be used, any metallocene compound containing a central metal selected from Group IV of the periodic table can be used. For example, the general formula S _n U _m MY
_l (wherein M represents a transition metal of Group IV of the periodic table;
Or U represents a monocyclic hydrocarbon group or a polycyclic hydrocarbon group which may be independently substituted, and S and U are directly bonded to M, and both are groups having the same structure. Or a group having a different structure.
Y represents hydrogen, a halogen group or a hydrocarbon group. And
n and m are 0, 1 or 2, n + m ≧ 1, n + m +
l = 4. ) Can be used, and a so-called half metallocene compound is also included in the category.

Here, M is a transition metal of Group IV of the periodic table, and examples of such a transition metal include titanium,
Zirconium and the like can be mentioned, and among them, titanium is particularly preferable. Examples of S or U include a cyclopentadienyl group, a pentamethylcyclopentadienyl group, a fluorenyl group, an indenyl group, and the like. Specific examples of the metallocene compound (B) include, for example, titanocene dichloride, dichlorobis ( Indenyl) titanium,
Trichloro (cyclopentadienyl) titanium, trichloro (pentamethylcyclopentadienyl) titanium, trimethoxy (pentamethylcyclopentadienyl) titanium, zirconocene dichloride, bis (pentamethylcyclopentadienyl) zirconium dichloride and the like can be mentioned. it can.

As the halogenated hydrocarbon (C) used in the present invention, any one can be used as long as it belongs to the category of halogenated hydrocarbons. For example, the general formula CClZ ¹ Z ² Z ³ (Where Z ¹ ,
Z ² and Z ³ each independently represent a halogen atom, an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted alkoxy group, or an optionally substituted aryloxy group . ) Can be used.

Here, when Z ¹ , Z ² and Z ³ are halogen atoms, for example, a fluorine atom, a chlorine atom, a bromine atom,
When an iodine atom is mentioned and it is an alkyl group which may be substituted, for example, a methyl group, an ethyl group, an n-propyl group,
Isopropyl group and the like, and when the aryl group may be substituted, for example, a phenyl group, a naphthyl group,
Examples thereof include a phenyl chloride group, a phenyl bromide group, and a methylphenyl group.In the case of an alkoxy group which may be substituted, examples thereof include a methoxy group, an ethoxy group, an n-propoxy group, and an isopropoxy group. When the aryloxy group may be, for example, a phenoxy group,
Naphthoxy group, phenoxy chloride group, phenoxy bromide group,
Methylphenoxy group and the like, and such halogenated hydrocarbons include, for example, carbon tetrachloride, chloroform, dichloromethane, chloromethane, dichloroethane,
Trichloroethane, carbon tetrabromide, methyl bromide and the like can be mentioned.

In the present invention, carbon tetrachloride and / or chloroform are preferred because a vinyl chloride-olefin copolymer can be produced particularly efficiently.

In the production method of the present invention, the ratio of vinyl chloride and olefin (hereinafter referred to as monomer) to aluminum compound (A), metallocene compound (B) and halogenated hydrocarbon (C) is optional. In particular, it is possible to produce a vinyl chloride-olefin copolymer with high production efficiency, so that monomer / aluminum compound (A) / metallocene compound (B) / halogenated hydrocarbon (C) = 150. / 6/1/250-320/3/35 /
It is desirable to use at a usage ratio (molar ratio) of 1. Further, the ratio of vinyl chloride to olefin as a monomer to be used is arbitrary, and among them, vinyl chloride / olefin =
The use ratio (molar ratio) of 30/1 to 1/1 is desirable.

The olefin used in the present invention may be any olefin as long as it belongs to the category of olefin, such as ethylene, propylene, butene,
Pentene-1 and the like can be mentioned, and among them, ethylene is particularly preferable since a vinyl chloride-ethylene block copolymer can be easily obtained.

In the present invention, it is also possible to use a third component monomer which can be copolymerized with vinyl chloride and an olefin, without departing from the object of the present invention. Examples of the monomer include butadiene, acrylonitrile, vinylidene chloride, vinylidene cyanide, N-vinylpyrrolidone, and vinylpyridine.

As the production method in the present invention, general polymerization reactions such as a bulk polymerization method, a suspension polymerization method, an emulsion polymerization method, and a solution polymerization method can be performed. The solvent used in the solution polymerization is not particularly limited, and a conventional solvent such as a hydrocarbon solvent such as hexane; ketones such as acetone and cyclohexane; ethers such as 1,4-dioxane and tetrahydrofuran; Examples thereof include aromatic solvents such as toluene and benzene, and among them, toluene is particularly preferable.

In carrying out the present invention, vinyl chloride, an organoaluminum compound (A), and a central metal selected from Group IV of the periodic table are placed in a reaction vessel under an inert atmosphere such as nitrogen or argon. A metallocene compound (B) containing
It is preferred that the halogenated hydrocarbon (C), the solvent and the olefin are mixed and adjusted to initiate the polymerization reaction. The conditions for carrying out the polymerization reaction are not particularly limited and can be appropriately selected and carried out. The polymerization reaction pressure may be either normal pressure or pressurized. Also, as the polymerization reaction temperature,
For example, a range of -78 ° C to 50 ° C can be selected.

The vinyl chloride-olefin copolymer obtained according to the present invention can be used for general vinyl chloride polymers such as films and sheets.

[0027]

The present invention will now be described by way of examples.
Although described in more detail, the present invention is not limited by these examples.

The reactions in the following examples were carried out in a dry nitrogen atmosphere unless otherwise specified.

Measurement of Molecular Weight of Vinyl Chloride-Olefin Copolymer The vinyl chloride-olefin copolymer obtained in the examples was subjected to gel permeation chromatography (manufactured by JASCO Corporation) as a solvent. Using tetrahydrofuran, the number average molecular weight (Mn) and the weight average molecular weight (Mw) in terms of polystyrene of the tetrahydrofuran-soluble portion were measured.

NM of vinyl chloride-olefin copolymer
R Measurement-The vinyl chloride-olefin copolymer obtained in the examples was used as a 5% by weight deuterated nitrobenzene solvent, and
MHz NMR (trade name: Varian Gemini)
NMR measurement was performed using a 2000 spectrometer) to determine the ratio (%) between the polyvinyl chloride segment and the polyolefin segment. As a specific method, for example, when ethylene is used as the olefin,
The ratio of the methine peak (56 to 58 ppm) of the polyvinyl chloride segment and the methylene peak (30 ppm) of the polyethylene segment in the carbon NMR chart was determined,
The value was defined as the ratio between the polyvinyl chloride segment and the polyethylene segment.

-Measurement of Melting Point of Vinyl Chloride-Olefin Copolymer- The vinyl chloride-olefin copolymer obtained in the examples was subjected to DSC (manufactured by Seiko Denshi) at a heating rate of 2 ° C / m
The measurement was performed under the measurement conditions of “in”, and the heat of fusion peak was measured.

Example 1 A stainless steel reaction vessel was placed at room temperature under a nitrogen atmosphere at room temperature.
0.498 g (2.0 mmol) of dichloride
Methyl aluminum (15 wt% hexane solution)
15 ml (2.4 mmol), 30 ml of carbon tetrachloride (3
00 mmol) and 30 ml of toluene without aging time
After quickly adding, at −78 ° C., 20 ml of vinyl chloride monomer
(288 mmol), and finally 5 kg of ethylene
f / cm ^Two(Equivalent to 44 mmol of ethylene)
After that, the temperature of the reaction vessel was raised to 30 ° C. to start polymerization.
When the reaction time has elapsed for 24 hours, the polymerization reaction system is
Cool to 8 ° C and add a small amount of methanol to
Was stopped. The obtained polymerization reaction solution was diluted with 5 vol of hydrochloric acid.
% By adding to a large amount of methanol containing
The vinyl chloride-ethylene copolymer was recovered.

Table 1 shows the evaluation results of the obtained vinyl chloride-ethylene copolymer.

FIG. 1 shows the carbon NMR of the tetrahydrofuran-soluble portion of the obtained vinyl chloride-ethylene copolymer.
The spectrum is shown. FIG. 2 shows a carbon NMR spectrum of a tetrahydrofuran-insoluble portion of the obtained vinyl chloride-ethylene copolymer.

FIG. 3 shows a DSC measurement chart of the tetrahydrofuran-soluble portion of the obtained vinyl chloride-ethylene copolymer. The tetrahydrofuran-soluble portion of the obtained vinyl chloride-ethylene copolymer had two heat peaks of fusion.

Example 2 0.498 g (2.0 mmol) of titanocene dichloride and trimethylaluminum (15 wt% hexane solution) were placed in a stainless steel reaction vessel at room temperature under a nitrogen atmosphere.
15 ml (2.4 mmol), 30 ml of carbon tetrachloride (3
00 mmol) and 30 ml of toluene were quickly added without aging time, and then 20 ml of a vinyl chloride monomer at -78 ° C.
(288 mmol) and finally 25 kg of ethylene
After injecting f / cm ² (equivalent to 220 mmol of ethylene) under pressure, the reaction vessel was heated to 30 ° C. to initiate polymerization. After a reaction time of 24 hours, the polymerization reaction system was cooled to −78 ° C., and the polymerization was stopped by adding a small amount of methanol. The obtained polymerization reaction solution is diluted with 5 v of hydrochloric acid.
By pouring into a large amount of methanol containing ol%, a vinyl chloride-ethylene copolymer was recovered.

The evaluation results of the obtained vinyl chloride-ethylene copolymer are shown in Table 1.

Example 3 Under a nitrogen atmosphere at room temperature in a stainless steel reaction vessel, 2.49 g (10 mmol) of titanocene dichloride and 11.5% of trimethylaluminum (15 wt% hexane solution) were added.
ml (12 mmol), 30 ml of carbon tetrachloride (300 m
mol) and 30 ml of toluene were quickly added without aging time, and then at −78 ° C., 20 ml of vinyl chloride monomer (28 ml).
8 mmol), and finally ethylene 5 Kg · f / c
After injecting m ² (equivalent to 44 mmol of ethylene) under pressure, the reaction vessel was heated to 30 ° C. to initiate polymerization. When the reaction time has elapsed for 24 hours, the polymerization reaction system is brought to -78 ° C.
And the polymerization was stopped by adding a small amount of methanol. By pouring the obtained polymerization reaction solution into a large amount of methanol containing 5 vol% of hydrochloric acid, a vinyl chloride-ethylene copolymer was recovered.

Table 1 shows the evaluation results of the obtained vinyl chloride-ethylene copolymer.

Example 4 0.30 g of trichloro (cyclopentadienyl) titanium in a stainless steel reaction vessel at room temperature under a nitrogen atmosphere.
(2.0 mmol), trimethylaluminum (15 w
1.15 ml (2.4 mmol of hexane solution of t%)
l), 30 ml (300 mmol) of carbon tetrachloride and 30 ml of toluene were quickly added without aging time, followed by -78.
At 20 ° C., 20 ml (288 mmol) of vinyl chloride monomer were charged, and finally 5 kgf · cm ^{2 of} ethylene (ethylene 4 kg) was added.
(Equivalent to 4 mmol) under pressure.
C. to raise the temperature to initiate polymerization. After a reaction time of 24 hours, the polymerization reaction system was cooled to −78 ° C., and the polymerization was stopped by adding a small amount of methanol. By pouring the obtained polymerization reaction solution into a large amount of methanol containing 5 vol% of hydrochloric acid, a vinyl chloride-ethylene copolymer was recovered.

Table 1 shows the evaluation results of the obtained vinyl chloride-ethylene copolymer.

Example 5 0.571 g (2.0 mmol) of trichloro (pentamethylcyclopentadienyl) titanium and 1.15 ml of trimethylaluminum (15 wt% hexane solution) were placed in a stainless steel reaction vessel at room temperature under a nitrogen atmosphere. .
4 mmol), 30 ml of carbon tetrachloride (300 mmol)
And 30 ml of toluene were quickly added without aging time, and then at -78 ° C., 20 ml of a vinyl chloride monomer (288 mm).
ol), and finally ethylene 5Kg · f / cm
² (equivalent to 44 mmol of ethylene)
The temperature of the reaction vessel was raised to 30 ° C. to initiate polymerization. After a reaction time of 24 hours, the polymerization reaction system was cooled to −78 ° C., and the polymerization was stopped by adding a small amount of methanol. By pouring the obtained polymerization reaction solution into a large amount of methanol containing 5 vol% of hydrochloric acid, a vinyl chloride-ethylene copolymer was recovered.

Table 1 shows the evaluation results of the obtained vinyl chloride-ethylene copolymer.

Example 6 0.547 g (2.0 mmol) of trimethoxy (pentamethylcyclopentadienyl) titanium and 1.15 ml of trimethylaluminum (15 wt% hexane solution) were placed in a stainless steel reaction vessel at room temperature under a nitrogen atmosphere. .
4 mmol), 30 ml of carbon tetrachloride (300 mmol)
And 30 ml of toluene were quickly added without aging time, and then at −78 ° C., 20 ml of a vinyl chloride monomer (288 mm).
ol), and finally ethylene 5Kg · f / cm
After pressure injection of ² (equivalent to 44 mmol of ethylene),
The temperature of the reaction vessel was raised to 30 ° C. to initiate polymerization. After a reaction time of 24 hours, the polymerization reaction system was cooled to −78 ° C., and the polymerization was stopped by adding a small amount of methanol. By pouring the obtained polymerization reaction solution into a large amount of methanol containing 5 vol% of hydrochloric acid, a vinyl chloride-ethylene copolymer was recovered.

The evaluation results of the obtained vinyl chloride-ethylene copolymer are shown in Table 1.

Example 7 0.691 g (2.0 m) of dichlorobis (indenyl) titanium was placed in a stainless steel reaction vessel at room temperature under a nitrogen atmosphere.
mol), 1.15 ml (2.4 mmol) of trimethylaluminum (15 wt% hexane solution), 30 ml (300 mmol) of carbon tetrachloride and 30 ml of toluene were added quickly without aging time, and then the vinyl chloride monomer was added at −78 ° C. They were charged 20 ml (288 mmol), and finally after ethylene 5Kg · f / cm ² (equivalent to ethylene 44 mmol) was injected under pressure, the temperature was raised polymerization was started and the reaction vessel 30 ° C.. After a reaction time of 24 hours, the polymerization reaction system was cooled to −78 ° C., and the polymerization was stopped by adding a small amount of methanol. By pouring the obtained polymerization reaction solution into a large amount of methanol containing 5 vol% of hydrochloric acid, a vinyl chloride-ethylene copolymer was recovered.

Table 1 shows the evaluation results of the obtained vinyl chloride-ethylene copolymer.

Example 8 2.49 g (10 mmol) of titanocene dichloride and triisobutylaluminum (a 15 wt% hexane solution) were placed in a stainless steel reaction vessel at room temperature under a nitrogen atmosphere.
5.9 ml (12 mmol), carbon tetrachloride 30 ml (3
00 mmol) and 30 ml of toluene were quickly added without aging time, and then at -78 ° C., 20 ml of a vinyl chloride monomer.
(288 mmol) and finally 5 kg of ethylene
After injecting f / cm ² (equivalent to 44 mmol of ethylene) under pressure, the reaction vessel was heated to 30 ° C. to initiate polymerization.
When the reaction time has elapsed for 24 hours, the polymerization reaction system is
The polymerization was stopped by cooling to 8 ° C. and adding a small amount of methanol. The obtained polymerization reaction solution was diluted with 5 vol of hydrochloric acid.
%, A vinyl chloride-ethylene copolymer was recovered.

Table 1 shows the evaluation results of the obtained vinyl chloride-ethylene copolymer.

Example 9 Titanose was placed in a stainless steel reaction vessel at room temperature under a nitrogen atmosphere.
Dichloride 2.49 g (10 mmol), triiso
Butyl aluminum (15 wt% hexane solution) 1
5.9 ml (12 mmol), carbon tetrachloride 30 ml (3
00 mmol) and 30 ml of toluene without aging time
After quickly adding, at −78 ° C., 20 ml of vinyl chloride monomer
(288 mmol), and finally 25 kg of ethylene
・ F / cm ^Two(Equivalent to 220 mmol of ethylene)
After the injection, the temperature of the reaction vessel was raised to 30 ° C. to start the polymerization.
Was. When the reaction time has passed 24 hours, the polymerization reaction system
Cool to -78 ° C and add a small amount of methanol.
The polymerization was stopped. The obtained polymerization reaction solution is diluted with 5 v of hydrochloric acid.
ol% of methanol
Thus, a vinyl chloride-ethylene copolymer was recovered.

Table 1 shows the evaluation results of the obtained vinyl chloride-ethylene copolymer.

Example 10 Titanose was placed in a stainless steel reaction vessel at room temperature under a nitrogen atmosphere.
0.498 g (2.0 mmol) of dichloride
Methyl aluminum (15 wt% hexane solution)
15 ml (2.4 mmol), 30 ml of carbon tetrachloride (3
00 mmol) and 30 ml of toluene without aging time
After quickly adding, at −78 ° C., 20 ml of vinyl chloride monomer
(288 mmol), and finally 5 kg of ethylene
f / cm ^Two(Equivalent to 44 mmol of ethylene)
After that, the temperature of the reaction vessel was raised to 50 ° C. to start polymerization.
When the reaction time has elapsed for 24 hours, the polymerization reaction system is
Cool to 8 ° C and add a small amount of methanol to
Was stopped. The obtained polymerization reaction solution was diluted with 5 vol of hydrochloric acid.
% By adding to a large amount of methanol containing
The vinyl chloride-ethylene copolymer was recovered.

Table 1 shows the evaluation results of the obtained vinyl chloride-ethylene copolymer.

[0054]

[Table 1]

According to the present invention, a copolymerization reaction between vinyl chloride and an olefin is carried out using a specific organoaluminum compound, a metallocene compound containing a central metal selected from Group IV of the periodic table, and a halogenated hydrocarbon. It relates to a novel method for producing a vinyl chloride-olefin copolymer,
Its industrial value is extremely high.

[Brief description of the drawings]

FIG. 1 is a carbon NMR of a tetrahydrofuran-soluble portion of a vinyl chloride-ethylene copolymer obtained in Example 1.
FIG. 4 is a spectrum, and the composition of the copolymer was determined from the methine peak (56 to 58 ppm) of the polyvinyl chloride segment and the methylene peak (30 ppm) of the polyethylene segment.

FIG. 2 is a carbon NMR of the tetrahydrofuran insoluble portion of the vinyl chloride-ethylene copolymer obtained in Example 1.
FIG. 4 is a spectrum, and the composition of the copolymer was determined from the methine peak (56 to 58 ppm) of the polyvinyl chloride segment and the methylene peak (30 ppm) of the polyethylene segment.

FIG. 3 is a DSC measurement chart of a tetrahydrofuran-soluble portion of the vinyl chloride-ethylene copolymer obtained in Example 1, which had two heat peaks of fusion.

 ──────────────────────────────────────────────────続 き Continuing from the front page (72) Inventor Junichiro Kanasaka 1-8 Kasumi, Yokkaichi-shi, Mie Tosoh Corporation Yokkaichi Research Laboratory F-term (reference) 4J026 HA03 HA27 HA32 HA33 HA34 HA35 HB09 HB27 HB32 HB33 HB34 HB35 HE01 4J028 AA01A AB01A AC01A AC10A AC28A BA00A BA01B BB00A BB01B BC15B BC16B BC17B BC18B BC20B BC24B CB11C CB12C CB14C EB02 EB03 EB04 EB05 EB08 EB22 EC02 FA01 FA02 FA03 GA26 4J100 AA02Q AA03Q AA04Q AA07Q AC03P CA04 FA10 4J128 AA01 AB01 AC01 AC10 AC28 AD00 BA00A BA01B BB00A BB01B BC15B BC16B BC17B BC18B BC20B BC24B CB11C CB12C CB14C EB02 EB03 EB04 EB05 EB08 EB22 EC02 FA01 FA02 FA03 GA26

Claims (6)

[Claims] A compound of the general formula AlX ¹ X ² X ^{3 wherein} X ¹ , X ² ,
X ³ is each independently a halogen atom, an alkyl group which may be substituted, an aryl group which may be substituted,
It represents an alkoxy group which may be substituted or an aryloxy group which may be substituted. ), A metallocene compound containing a central metal selected from Group IV of the Periodic Table (B), and a halogenated hydrocarbon (C) to carry out a copolymerization reaction between vinyl chloride and an olefin. A method for producing a vinyl chloride-olefin copolymer. 2. The method according to claim 1, wherein the aluminum compound (A) is trimethylaluminum, triethylaluminum and / or triisobutylaluminum.
3. The method for producing a vinyl chloride-olefin copolymer according to item 1. 3. The method according to claim 1, wherein the metallocene compound (B) has the general formula S _n U _m M
Y _l (wherein M represents a transition metal of Group IV of the periodic table,
S or U each independently represents a monocyclic hydrocarbon group or a polycyclic hydrocarbon group which may be substituted, and these S and U are directly bonded to M, and both have the same structure. Or a group having a different structure.
Y represents hydrogen, a halogen group or a hydrocarbon group. And
n and m are 0, 1 or 2, n + m ≧ 1, n + m +
l = 4. 3. The method for producing a vinyl chloride-olefin copolymer according to claim 1, wherein the metallocene compound is a metallocene compound represented by the following formula: 4. The method according to claim 3, wherein at least one of S and U is a hydrocarbon group selected from the group consisting of a cyclopentadienyl group, a fluorenyl group and an indenyl group. The method for producing a vinyl chloride-olefin copolymer according to any one of claims 1 to 3. 5. The method according to claim 1, wherein the halogenated hydrocarbon (C) is carbon tetrachloride and / or chloroform.
5. The method for producing a vinyl chloride-olefin copolymer according to any one of items 1 to 4. 6. The method for producing a vinyl chloride-olefin copolymer according to claim 1, wherein the vinyl chloride-olefin copolymer is a vinyl chloride-ethylene block copolymer.