JP4770010B2 - Method for producing high syndiotactic vinyl chloride polymer - Google Patents

Description

【００７３】
【表２】

【００７４】
【発明の効果】
本発明は、高シンジオタクチック塩化ビニル系重合体の新規な製造方法を提供するものであり、その工業的価値は極めて高いものである。
【図面の簡単な説明】
【図１】実施例1により得られた塩化ビニル重合体のカーボン１３−ＮＭＲスペクトル測定によるメチン部分のスペクトルであり、低磁場側より３連子の立体規則性がｒｒ，ｍｒ，ｍｍと帰属される。
【図２】比較例２により得られた塩化ビニル重合体のカーボン１３−ＮＭＲスペクトル測定によるメチン部分のスペクトルであり、低磁場側より３連子の立体規則性がｒｒ，ｍｒ，ｍｍと帰属される。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for producing a high syndiotactic vinyl chloride polymer, and in particular, polymerizes a vinyl chloride monomer in the presence of an organoaluminum compound, titanium tetrachloride and a halogenated hydrocarbon. The present invention relates to a method for producing a syndiotactic vinyl chloride polymer.
[0002]
[Prior art]
In general, the physicochemical properties of a polymer greatly depend on the primary structure (eg, molecular weight, molecular weight distribution, steric structure, etc.) of the polymer. Among them, the three-dimensional structure of the polymer is closely related to the thermal characteristics of the polymer, and various studies have been conducted on the control of the three-dimensional structure of the polymer.
[0003]
Vinyl chloride polymers are well-balanced materials in processability, physical properties, price, and the like, and are used in a wide range of fields such as films and sheets. However, the vinyl chloride polymer is generally used as a compound to which a reinforcing material or the like is added in a field where mechanical strength is low and impact resistance is required as compared with polyethylene, polypropylene and the like. As a cause of the low mechanical strength, a general vinyl chloride polymer has low crystallinity. Vinyl chloride polymers have irregular structures such as branches and head-to-head bonds in the molecular main chain. By reducing these irregular structures, new vinyl chloride polymers with excellent crystallinity are synthesized. It is expected to be possible.
[0004]
As a method for controlling the three-dimensional structure of the polymer, it is already known that the syndiotacticity in the polymer is improved by lowering the polymerization temperature during the polymerization reaction. Even in the case of vinyl chloride polymer, low temperature such as a method of performing polymerization using uranyl nitrate in methanol in Japanese Patent Publication No. 34-2898 and a redox polymerization method using hydrogen peroxide etc. in Japanese Patent Publication No. 35-7588. A method for producing a vinyl chloride polymer rich in syndiotacticity by polymerization has been proposed.
[0005]
Other methods for obtaining a highly stereoregular vinyl chloride polymer include polymerization in an aldehyde (P. H. Burleigh, J. Am. Chem. Soc., 82, 749 (1960)), urea. A method of performing radiation polymerization in an adduct (Ichiro Sakurada, Keiichi Nambu, Nikka, 80, 307 (1959)) has been reported, but none has been put into practical use.
[0006]
Furthermore, with respect to the polymerization of a vinyl chloride polymer using a Ziegler catalyst used for the polymerization of olefins such as polyethylene and polypropylene, for example, a method of producing a vinyl chloride polymer with Ti (O-nBu) _{4 having} a low Lewis acidity ( Yamazaki Hayao, Kogyo Kagaku, 70 (11), 1989 (1967)), a method of producing a vinyl chloride polymer by adding carbon tetrachloride to a Ti (O-nBu) ₄ / AlCl ₂ (C ₂ H ₅ ) system. (Satoshi Yamazaki, Industrial Chemistry, 68 (5), 881 (1965)) has been reported.
[0007]
[Problems to be solved by the invention]
However, the methods proposed in Japanese Patent Publication Nos. 34-2989 and 35-7588 are extremely disadvantageous industrially because it is necessary to carry out the polymerization reaction under a special condition of low temperature. In addition, since it is difficult to control the three-dimensional structure of the vinyl chloride monomer at room temperature, there has been no report on the control of the three-dimensional structure of the vinyl chloride polymer at room temperature, and vinyl chloride using a Ziegler catalyst is not yet available. The stereoregularity of the polymer is the same as that of the vinyl chloride polymer obtained by ordinary radical polymerization, and no report has been made on the stereoregularity control of the vinyl chloride polymer using a Ziegler catalyst.
[0008]
Therefore, an object of the present invention is to provide a method for producing a highly syndiotactic vinyl chloride polymer having excellent physical properties.
[0009]
[Means for Solving the Problems]
As a result of intensive investigations to solve the above problems, the inventors of the present invention obtained a vinyl chloride polymer obtained by polymerizing a vinyl chloride monomer in the presence of a specific compound. I found out that it was a city and completed the present invention.
[0010]
That is, the present invention is a highly syndiotactic characterized in that a vinyl chloride monomer is polymerized in the presence of an organoaluminum compound (A), titanium tetrachloride (B) and a halogenated hydrocarbon (C). The present invention relates to a method for producing a vinyl chloride polymer.
[0011]
Hereinafter, the present invention will be described in more detail.
[0012]
The present invention provides a high syndiotactic vinyl chloride characterized by polymerizing a vinyl chloride monomer in the presence of an organoaluminum compound (A), titanium tetrachloride (B) and a halogenated hydrocarbon (C). The present invention relates to a method for producing a polymer.
[0013]
As the organoaluminum compound (A) used in the present invention, any organoaluminum compound (A) can be used as long as it belongs to the category of the organoaluminum compound. For example, the general formula AlX ¹ X ² X ³ (wherein X ¹ , X ² and X ³ are each independently a halogen atom, an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted alkoxy group or an optionally substituted aryloxy group. It is possible to use an organoaluminum compound represented by
[0014]
Here, as X ¹ , X ² , and X ^{3, when} it is a halogen atom, for example, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are exemplified. When it is an optionally substituted alkyl group, for example, methyl Group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, etc., and when it is an aryl group which may be substituted, for example, phenyl group, naphthyl group, phenyl chloride group, bromide Examples thereof include a phenyl group and a methylphenyl group, and examples of the alkoxy group which may be substituted include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, and an isobutoxy group. In the case of an aryloxy group which may be substituted, for example, phenoxy group, naphthoxy group, phenoxy chloride group, phenoxy group bromide, methyl Examples of the organoaluminum compound (A) include trimethylaluminum, triethylaluminum, triisobutylaluminum, methylaluminum bis (2,6-di-tert-butyl-4-methylphenoxide), Examples thereof include dimethylaluminum chloride and methylaluminum dichloride.
[0015]
In the present invention, it is possible to produce a highly syndiotactic vinyl chloride polymer having particularly high production efficiency and excellent crystallinity. As the organoaluminum compound (A), trimethylaluminum, triethylaluminum can be used. One or more selected from the group consisting of triisobutylaluminum is preferred.
[0016]
As titanium tetrachloride (B) used in the present invention, generally known titanium tetrachloride can be used.
[0017]
Any halogenated hydrocarbon (C) may be used as long as it belongs to the category of halogenated hydrocarbons. For example, the general formula CClZ ¹ Z ² Z ³ (wherein Z ¹ , Z ² and Z ³ are each independently a halogen atom, a hydrogen atom, an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted alkoxy group or a substituted group. It is possible to use a halogenated hydrocarbon represented by the following:
[0018]
Here, examples of Z ¹ , Z ² , and Z ³ include a halogen atom, for example, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and an alkyl group that may be substituted, for example, methyl Group, ethyl group, n-propyl group, isopropyl group and the like, and in the case of an aryl group which may be substituted, for example, phenyl group, naphthyl group, phenyl chloride group, phenyl bromide group, methylphenyl group, etc. In the case of an optionally substituted alkoxy group, for example, a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, etc., and in the case of an optionally substituted aryloxy group, for example, a phenoxy group , Naphthoxy groups, phenoxy chloride groups, phenoxy bromide groups, methylphenoxy groups, and the like, and such halogenated hydrocarbons (C) It is then may include, for example, carbon tetrachloride, chloroform, dichloromethane, chloromethane, dichloroethane, trichloroethane, carbon tetrabromide, methyl bromide and the like.
[0019]
In the present invention, carbon tetrachloride and / or chloroform are particularly preferable as the halogenated hydrocarbon (C) because it is a production method of a highly syndiotactic vinyl chloride polymer having high production efficiency and excellent crystallinity. .
[0020]
Further, the use ratio of the vinyl chloride monomer, the organoaluminum compound (A), titanium tetrachloride (B) and the halogenated hydrocarbon (C) in the production method of the present invention is arbitrary. Since a tic vinyl chloride polymer can be produced with high production efficiency, vinyl chloride monomer / organoaluminum compound (A) / titanium tetrachloride (B) / halogenated hydrocarbon (C) = 50/1/1/1 It is preferable to use within a ratio (molar ratio) range of 150/5/1/250.
[0021]
As the vinyl chloride monomer used in the present invention, a vinyl chloride monomer alone or another vinyl monomer capable of copolymerization of a vinyl chloride monomer and a vinyl chloride monomer is used. Mention may be made of mixtures. Examples of other vinyl monomers that can be copolymerized with vinyl chloride monomer include ethylene, propylene, butene, pentene-1, butadiene, acrylonitrile, vinylidene chloride, vinylidene cyanide, N-vinylpyrrolidone, vinyl Examples thereof include pyridine.
[0022]
As the production method in the present invention, general polymerization reactions such as bulk polymerization, suspension polymerization, emulsion polymerization, and solution polymerization can be performed. And there is no restriction | limiting in particular as a solvent at the time of performing solution polymerization, Conventional solvents, For example, hydrocarbon solvents, such as hexane; Ketones, such as acetone and cyclohexane; Ethers, such as 1, 4- dioxane, tetrahydrofuran; Aromatic solvents such as toluene and benzene can be mentioned, and among them, hexane and toluene are particularly preferable.
[0023]
Moreover, when implementing this invention, it is preferable to perform a polymerization reaction in inert atmosphere, such as nitrogen and argon. The conditions for carrying out the polymerization reaction are not particularly limited and can be appropriately selected. The polymerization reaction pressure may be under normal pressure or under pressure. In addition, the polymerization reaction temperature can be selected, for example, in the range of −78 ° C. to 50 ° C. In particular, in the present invention, the reaction temperature can be easily controlled. Even if the polymerization reaction is carried out in the range of −20 ° C. to 40 ° C., especially 0 to 20 ° C., which has been considered difficult to control, a highly syndiotactic vinyl chloride polymer can be produced.
[0024]
The high syndiotactic vinyl chloride polymer obtained by the present invention can be used for general vinyl chloride polymers such as films, sheets and paints.
[0025]
【Example】
EXAMPLES The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples.
[0026]
The reactions in the following examples were conducted under a dry nitrogen atmosphere unless otherwise specified.
[0027]
-Measurement of number average molecular weight and weight average molecular weight of vinyl chloride polymer-
The vinyl chloride polymers obtained in Examples and Comparative Examples were subjected to gel permeation chromatography (manufactured by JASCO Corporation) using tetrahydrofuran as a solvent, and the number average molecular weight (Mn) in terms of polystyrene and The weight average molecular weight (Mw) was measured.
[0028]
-NMR measurement of vinyl chloride polymer-
Using the vinyl chloride polymer obtained in Examples and Comparative Examples as a deuterated nitrobenzene solvent of 5% by weight, NMR measurement was performed using 100 MHz NMR (trade name: Varian Gemini 2000 spectrometer), and triplet (rr / mr). Rr ratio (% by weight) of / mm) was determined from the following formula, and the stereoregularity was evaluated using the rr ratio as the value of the syndiotacticity of the triplet.
[0029]
rr ratio (%) = rr peak / (rr peak + mr peak + mm peak) × 100
Example 1
In a stainless steel reaction vessel, 0.02 ml (0.20 mmol) of titanium tetrachloride, 0.12 ml (0.24 mmol) of trimethylaluminum (15 wt% hexane solution), and 3 ml (30 mmol) of carbon tetrachloride at room temperature in a nitrogen atmosphere. After rapidly adding without aging time, 2 ml (28.8 mmol) of vinyl chloride monomer was charged at −78 ° C., and immersed in a constant temperature bath prepared at 20 ° C. to initiate the polymerization reaction. When the reaction time reached 24 hours, the polymerization reaction system was cooled to −78 ° C., and a small amount of methanol was added to terminate the polymerization. The obtained polymerization reaction solution was put into a large amount of methanol containing 5 vol% hydrochloric acid to recover a vinyl chloride polymer.
[0030]
The evaluation results of the obtained vinyl chloride polymer are shown in Table 1.
[0031]
The measurement result of the NMR measurement of the obtained vinyl chloride polymer is shown in FIG.
[0032]
The number average molecular weight of the obtained vinyl chloride polymer was 11100, and the rr ratio was 40%.
[0033]
Example 2
In a stainless steel reaction vessel, 0.02 ml (0.20 mmol) of titanium tetrachloride, 0.18 ml (0.24 mmol) of triethylaluminum (15 wt% hexane solution), and 3 ml (30 mmol) of carbon tetrachloride at room temperature in a nitrogen atmosphere. After rapidly adding without aging time, 2 ml (28.8 mmol) of vinyl chloride monomer was charged at −78 ° C., and immersed in a constant temperature bath prepared at 20 ° C. to initiate the polymerization reaction. When the reaction time reached 24 hours, the polymerization reaction system was cooled to −78 ° C., and a small amount of methanol was added to terminate the polymerization. The obtained polymerization reaction solution was put into a large amount of methanol containing 5 vol% hydrochloric acid to recover a vinyl chloride polymer.
[0034]
The evaluation results of the obtained vinyl chloride polymer are shown in Table 1.
[0035]
The number average molecular weight of the obtained vinyl chloride polymer was 13000, and the rr ratio was 40%.
[0036]
Example 3
In a stainless steel reaction vessel, at room temperature under a nitrogen atmosphere, 0.02 ml (0.20 mmol) of titanium tetrachloride, 0.32 ml (0.24 mmol) of triisobutylaluminum (15 wt% hexane solution), and 3 ml (30 mmol) of carbon tetrachloride Was quickly added without aging time, and then 2 ml (28.8 mmol) of vinyl chloride monomer was charged at −78 ° C. and immersed in a thermostatic bath prepared at 20 ° C. to initiate the polymerization reaction. When the reaction time reached 24 hours, the polymerization reaction system was cooled to −78 ° C., and a small amount of methanol was added to terminate the polymerization. The obtained polymerization reaction solution was put into a large amount of methanol containing 5 vol% hydrochloric acid to recover a vinyl chloride polymer.
[0037]
The evaluation results of the obtained vinyl chloride polymer are shown in Table 1.
[0038]
The number average molecular weight of the obtained vinyl chloride polymer was 17300, and the rr ratio was 41%.
[0039]
Example 4
In a stainless steel reaction vessel, 0.08 ml (0.80 mmol) of titanium tetrachloride, 0.48 ml (0.96 mmol) of trimethylaluminum (15 wt% hexane solution), and 3 ml (30 mmol) of carbon tetrachloride at room temperature in a nitrogen atmosphere. After rapidly adding without aging time, 2 ml (28.8 mmol) of vinyl chloride monomer was charged at −78 ° C., and immersed in a constant temperature bath prepared at 20 ° C. to initiate the polymerization reaction. When the reaction time reached 24 hours, the polymerization reaction system was cooled to −78 ° C., and a small amount of methanol was added to terminate the polymerization. The obtained polymerization reaction solution was put into a large amount of methanol containing 5 vol% hydrochloric acid to recover a vinyl chloride polymer.
[0040]
The evaluation results of the obtained vinyl chloride polymer are shown in Table 1.
[0041]
The number average molecular weight of the obtained vinyl chloride polymer was 10300, and the rr ratio was 41%.
[0042]
Example 5
In a stainless steel reaction vessel, 0.02 ml (0.20 mmol) of titanium tetrachloride, 0.12 ml (0.24 mmol) of trimethylaluminum (15 wt% hexane solution), and 5 ml (50 mmol) of carbon tetrachloride at room temperature in a nitrogen atmosphere. After rapidly adding without aging time, 2 ml (28.8 mmol) of vinyl chloride monomer was charged at −78 ° C., and immersed in a constant temperature bath prepared at 20 ° C. to initiate the polymerization reaction. When the reaction time reached 24 hours, the polymerization reaction system was cooled to −78 ° C., and a small amount of methanol was added to terminate the polymerization. The obtained polymerization reaction solution was put into a large amount of methanol containing 5 vol% hydrochloric acid to recover a vinyl chloride polymer.
[0043]
The evaluation results of the obtained vinyl chloride polymer are shown in Table 1.
[0044]
The number average molecular weight of the obtained vinyl chloride polymer was 8100, and the rr ratio was 40%.
[0045]
Example 6
In a stainless steel reaction vessel, 0.02 ml (0.20 mmol) of titanium tetrachloride, 0.12 ml (0.24 mmol) of trimethylaluminum (15 wt% hexane solution) and 1 ml (10 mmol) of carbon tetrachloride at room temperature in a nitrogen atmosphere. After rapidly adding without aging time, 2 ml (28.8 mmol) of vinyl chloride monomer was charged at −78 ° C., and immersed in a constant temperature bath prepared at 20 ° C. to initiate the polymerization reaction. When the reaction time reached 24 hours, the polymerization reaction system was cooled to −78 ° C., and a small amount of methanol was added to terminate the polymerization. The obtained polymerization reaction solution was put into a large amount of methanol containing 5 vol% hydrochloric acid to recover a vinyl chloride polymer.
[0046]
The evaluation results of the obtained vinyl chloride polymer are shown in Table 1.
[0047]
The number average molecular weight of the obtained vinyl chloride polymer was 13500, and the rr ratio was 39%.
[0048]
Example 7
In a stainless steel reaction vessel, at room temperature under a nitrogen atmosphere, 0.02 ml (020 mmol) of titanium tetrachloride, 0.12 ml (0.24 mmol) of trimethylaluminum (15 wt% hexane solution), 3 ml of toluene and 3 ml (30 mmol) of carbon tetrachloride Was quickly added without aging time, and then 2 ml (28.8 mmol) of vinyl chloride monomer was charged at −78 ° C. and immersed in a thermostatic bath prepared at 20 ° C. to initiate the polymerization reaction. When the reaction time reached 24 hours, the polymerization reaction system was cooled to −78 ° C., and a small amount of methanol was added to terminate the polymerization. The obtained polymerization reaction solution was put into a large amount of methanol containing 5 vol% hydrochloric acid to recover a vinyl chloride polymer.
[0049]
The evaluation results of the obtained vinyl chloride polymer are shown in Table 1.
[0050]
The number average molecular weight of the obtained vinyl chloride polymer was 8500, and the rr ratio was 39%.
[0051]
Example 8
In a stainless steel reaction vessel, 0.02 ml (0.20 mmol) of titanium tetrachloride, 0.12 ml (0.24 mmol) of trimethylaluminum (15 wt% hexane solution), and 3 ml (30 mmol) of carbon tetrachloride at room temperature in a nitrogen atmosphere. After quickly adding without aging time, 2 ml (28.8 mmol) of vinyl chloride monomer was charged at −78 ° C., and immersed in a thermostatic bath prepared at 30 ° C. to initiate the polymerization reaction. When the reaction time reached 24 hours, the polymerization reaction system was cooled to −78 ° C., and a small amount of methanol was added to terminate the polymerization. The obtained polymerization reaction solution was put into a large amount of methanol containing 5 vol% hydrochloric acid to recover a vinyl chloride polymer.
[0052]
The evaluation results of the obtained vinyl chloride polymer are shown in Table 1.
[0053]
The number average molecular weight of the obtained vinyl chloride polymer was 10200, and the rr ratio was 37%.
[0054]
Example 9
In a stainless steel reaction vessel, 0.02 ml (0.20 mmol) of titanium tetrachloride, 0.12 ml (0.24 mmol) of trimethylaluminum (15 wt% hexane solution), and 3 ml (30 mmol) of carbon tetrachloride at room temperature in a nitrogen atmosphere. After rapidly adding without aging time, 2 ml (28.8 mmol) of vinyl chloride monomer was charged at −78 ° C., and immersed in a constant temperature bath prepared at −20 ° C. to initiate the polymerization reaction. When the reaction time reached 24 hours, the polymerization reaction system was cooled to −78 ° C., and a small amount of methanol was added to terminate the polymerization. The obtained polymerization reaction solution was put into a large amount of methanol containing 5 vol% hydrochloric acid to recover a vinyl chloride polymer.
[0055]
The evaluation results of the obtained vinyl chloride polymer are shown in Table 1.
[0056]
The number average molecular weight of the obtained vinyl chloride polymer was 28400, and the rr ratio was 43%.
[0057]
Example 10
A stainless steel reaction vessel was charged with 0.02 ml (0.20 mmol) of titanium tetrachloride, 0.12 ml (0.24 mmol) of trimethylaluminum (15 wt% hexane solution) and 2.5 ml (30 mmol) of chloroform at room temperature under a nitrogen atmosphere. After rapidly adding without aging time, 2 ml (28.8 mmol) of vinyl chloride monomer was charged at −78 ° C., and immersed in a constant temperature bath prepared at 20 ° C. to initiate the polymerization reaction. When the reaction time reached 24 hours, the polymerization reaction system was cooled to −78 ° C., and a small amount of methanol was added to terminate the polymerization. The obtained polymerization reaction solution was put into a large amount of methanol containing 5 vol% hydrochloric acid to recover a vinyl chloride polymer.
[0058]
The evaluation results of the obtained vinyl chloride polymer are shown in Table 1.
[0059]
The number average molecular weight of the obtained vinyl chloride polymer was 10500, and the rr ratio was 40%.
[0060]
Comparative Example 1
In a stainless steel reaction vessel, in a nitrogen atmosphere, at −78 ° C., 2.6 ml (38.1 mmol) of vinyl chloride monomer and 0.4 ml of tributylboron (1 mol / L THF solution) as a radical polymerization initiator (0. 42 mmol) was charged and immersed in a constant temperature bath adjusted to 30 ° C., a small amount of air was added to the reaction system to initiate the polymerization reaction. When the reaction time passed 24 hours, the polymerization reaction system was cooled to −78 ° C., and hydroquinone as a radical polymerization inhibitor was added to terminate the polymerization. The obtained polymerization reaction solution was put into a large amount of methanol to recover a vinyl chloride polymer.
[0061]
The evaluation results of the obtained vinyl chloride polymer are shown in Table 2.
[0062]
The number average molecular weight of the obtained vinyl chloride polymer was 13600, and the rr ratio was 32%.
[0063]
Comparative Example 2
In a stainless steel reaction vessel, in a nitrogen atmosphere, at −78 ° C., 2.6 ml (38.1 mmol) of vinyl chloride monomer and 0.4 ml of tributylboron (1 mol / L THF solution) as a radical polymerization initiator (0. 42 mmol) was charged and immersed in a constant temperature bath adjusted to 20 ° C., and a small amount of air was added to the reaction system to initiate the polymerization reaction. When the reaction time passed 24 hours, the polymerization reaction system was cooled to −78 ° C., and hydroquinone as a radical polymerization inhibitor was added to terminate the polymerization. The obtained polymerization reaction solution was put into a large amount of methanol to recover a vinyl chloride polymer.
[0064]
The evaluation results of the obtained vinyl chloride polymer are shown in Table 2.
[0065]
The measurement result of the NMR measurement of the obtained vinyl chloride polymer is shown in FIG.
[0066]
The number average molecular weight of the obtained vinyl chloride polymer was 19000, and the rr ratio was 34%.
[0067]
Comparative Example 3
After rapidly adding 0.02 ml (0.20 mmol) of titanium tetrachloride and 0.12 ml (0.24 mmol) of trimethylaluminum (15 wt% hexane solution) to a stainless steel reaction vessel at room temperature in a nitrogen atmosphere without aging time Then, 2 ml (28.8 mmol) of vinyl chloride monomer was charged at −78 ° C. and immersed in a constant temperature bath prepared at 20 ° C. to initiate the polymerization reaction. When the reaction time reached 24 hours, the polymerization reaction system was cooled to −78 ° C., and a small amount of methanol was added to terminate the polymerization. Recovery of the vinyl chloride polymer was attempted by putting the obtained polymerization reaction solution into a large amount of methanol containing 5 vol% hydrochloric acid, but no vinyl chloride polymer was obtained.
[0068]
The polymerization reaction of the vinyl chloride monomer did not proceed.
[0069]
Comparative Example 4
In a stainless steel reaction vessel, 0.07 ml (0.20 mmol) of tetrabutoxytitanium, 0.12 ml (0.24 mmol) of trimethylaluminum (15 wt% hexane solution) and 3 ml (30 mmol) of carbon tetrachloride at room temperature in a nitrogen atmosphere. After rapidly adding without aging time, 2 ml (28.8 mmol) of vinyl chloride monomer was charged at −78 ° C., and immersed in a constant temperature bath prepared at 20 ° C. to initiate the polymerization reaction. When the reaction time reached 24 hours, the polymerization reaction system was cooled to −78 ° C., and a small amount of methanol was added to terminate the polymerization. The obtained polymerization reaction solution was put into a large amount of methanol containing 5 vol% hydrochloric acid to recover a vinyl chloride polymer.
[0070]
The evaluation results of the obtained vinyl chloride polymer are shown in Table 2.
[0071]
The number average molecular weight of the obtained vinyl chloride polymer was 18700, and the rr ratio was 34%.
[0072]
[Table 1]

[0073]
[Table 2]

[0074]
【The invention's effect】
The present invention provides a novel method for producing a highly syndiotactic vinyl chloride polymer, and its industrial value is extremely high.
[Brief description of the drawings]
FIG. 1 is a spectrum of a methine moiety measured by carbon 13-NMR spectrum of a vinyl chloride polymer obtained in Example 1, and the stereoregularity of a triplet is assigned as rr, mr, mm from the low magnetic field side. The
FIG. 2 is a spectrum of a methine moiety by carbon 13-NMR spectrum measurement of the vinyl chloride polymer obtained in Comparative Example 2, and the stereoregularity of the triplet is assigned as rr, mr, mm from the low magnetic field side. The

Claims (4)

General formula AlX ¹ X ² X ³ (wherein X ¹ , X ² and X ³ are each independently a halogen atom, an optionally substituted alkyl group, an optionally substituted aryl group, In the presence of an organoaluminum compound (A), titanium tetrachloride (B) and halogenated hydrocarbon (C) represented by A method for producing a highly syndiotactic vinyl chloride polymer, comprising polymerizing a monomer. The halogenated hydrocarbon (C) has the general formula CClZ ¹ Z ² Z ³ (wherein Z ¹ , Z ² and Z ³ are each independently a halogen atom, a hydrogen atom, an optionally substituted alkyl group, a substituted group) which may be an aryl group, as claimed in claim 1, characterized in that the halogenated hydrocarbon represented by.) showing the optionally substituted alkoxy group or an optionally substituted aryloxy group A method for producing a high syndiotactic vinyl chloride polymer. The high syndiotactic chloride according to claim 1 or 2 , wherein the organoaluminum compound (A) is at least one organoaluminum compound selected from the group consisting of trimethylaluminum, triethylaluminum, and triisobutylaluminum. A method for producing a vinyl polymer. The method for producing a highly syndiotactic vinyl chloride polymer according to any one of claims 1 to 3 , wherein the halogenated hydrocarbon (C) is carbon tetrachloride and / or chloroform.

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