JPH0142965B2 - - Google Patents

Description

Detailed Description of the Invention The present invention provides 2-chloro-1-phenylacetylenes that can be polymerized at a high reaction rate to obtain a chain polymer with a high molecular weight. The present invention relates to a method for producing a polymer.

Conventionally, various methods have been studied for producing acetylene polymers, but each method has the disadvantage that it is difficult to obtain a high polymer and that the reaction rate is difficult to increase. 2-chloro-1
- Phenylacetylenes are one of the disubstituted acetylenes.
Perhaps because it has lower reactivity than monosubstituted acetylene, there has been no research on the method for producing this polymer.

The present inventor previously proposed a method for producing polymers from aromatic acetylenes using a catalyst mainly composed of tungsten hexachloride (Japanese Patent Publication No. 37312/1983).
Japanese Patent Publication No. 52-20511, Japanese Patent Application No. 140145-1982, Japanese Patent Application No. 107967-1982, and Japanese Patent Application No. 1979-1912). The present inventor has further conducted extensive research into polymerization methods for obtaining high polymers from 2-chloro-1-phenylacetylenes, and has found that by using a specific polymerization catalyst, 2-chloro-1-phenyl We discovered that the polymerization of acetylenes progresses easily and the molecular weight of the resulting polymer is extremely large (molecular weight of 100,000 or more).
The present invention was achieved based on this knowledge.

That is, the present invention provides 2-chloro-1-phenylacetylene using a catalyst obtained by photoirradiating a mixture of a transition metal carbonyl selected from the group consisting of chromium carbonyl, molybdenum carbonyl, and tungsten carbonyl and a halogenated hydrocarbon. and a transition metal carbonyl selected from the group consisting of chromium carbonyl, molybdenum carbonyl, and tungsten carbonyl. 2-chloro-1
- A polymer of 2-chloro-1-phenylacetylenes, characterized in that a catalyst is prepared by irradiating a mixture with phenylacetylenes and 2-chloro-1-phenylacetylenes are simultaneously polymerized. (second invention).

2-chloro-1-phenylacetylenes in the present invention refer to compounds represented by the following general formula ().

A: alkyl group, aryl group, aralkyl group,
Indicates a substituent such as an alkoxy group or an aryloxy group, or a halogen atom. n: represents an integer from 0 to 5.

The Group 6 transition metal carbonyls used in the present invention are all in powder form and are stable in the air, so they are easy to handle. Examples of the Group 6 transition metal carbonyls include chromium carbonyl, molybdenum carbonyl, and tungsten carbonyl (see details). Published by Kyoritsu Shuppan Co., Ltd., Chemistry Dictionary, Volume 3, 201 pages,
It is described in Volume 9, page 294, and Volume 5, page 710. ) Molybdenum hexacarbonyl shows particularly high activity.

As the halogenated hydrocarbon used for catalyst preparation in the method of the present invention, carbon tetrachloride, carbon tetrabromide, etc. can be used. Carbon tetrachloride is preferred because it is inexpensive, easy to handle, and can also serve as a reaction solvent. Since the monomer 2-chloro-1-phenylacetylene itself has a chlorine atom, a mixed solution of the Group 6 transition metal carbonyl and the monomer can be prepared without separately adding an organic halide. It is also possible to advance the polymerization simultaneously with the preparation of the catalyst by irradiating the catalyst with light for a predetermined period of time. A method in which a mixed solution of a Group 6 transition metal carbonyl and an organic halide is irradiated and then polymerized by adding a monomer in the dark is a method in which a mixed solution of a metal carbonyl and a monomer is polymerized simultaneously with irradiation. This produces a polymer with a higher molecular weight. The amount of the organic halide to be used is equal to or more than the Group 6 transition metal carbonyl, and when used as a solvent like the above-mentioned carbon tetrachloride, a correspondingly large amount may be used.

In the polymerization of 2-chloro-1-phenylacetylenes, the amount of transition metal carbonyl used is suitably in the range of 0.1 to 10 mol % based on the monomer of the above formula (). The light used for irradiation is
Although near-ultraviolet light from a 100 W to 1 KW high-pressure mercury lamp is most preferred, simple exposure to sunlight produces catalytic species effective for polymerization. Light irradiation time is 10 minutes ~
A suitable temperature range for several hours is 0 to 100°C.
The intensity of the light is desirably equivalent to the amount of irradiation for 10 minutes or more, preferably 30 minutes to 2 hours, at a distance of 30 cm from a 100 W to 1 KW light source.

As a solvent for polymerization reaction, halogenated hydrocarbon,
It is preferable to use aromatic hydrocarbons and the like. The concentration of monomer in the polymerization reaction is 0.1 to 5 mol/
A range of is preferred. The temperature of polymerization reaction is usually 0 to 60
°C and time are selected from the range of several tens of minutes to several tens of hours.

According to the production method of the present invention, 2-chloro-1-
It is characterized in that it can obtain polymers from phenylacetylenes in high yields and that the molecular weight of the produced polymers is extremely large. The resulting polymer can be applied to gas adsorbents, separation membranes, photoresists, etc.

Next, the present invention will be explained in detail with reference to Examples.

Example 1 Under a dry nitrogen atmosphere, 30 mmol of molybdenum hexacarbonyl, 1.0 mole of 2-chloro-1-phenylacetylene and 25% by volume of tetralin based on the monomers were added as an internal standard for gas chromatography in 1 part of purified toluene. Add and 30 minutes at 30℃
Irradiation was performed using a 300W high-pressure mercury lamp. after that
Polymerization was carried out in the dark at 30°C for 23.5 hours.

When the amount of residual monomer was determined by gas chromatography, the reaction rate was 83%. The resulting polymer was precipitated by pouring the reaction solution into a large amount of methanol, and then dried separately. The amount of methanol-insoluble polymer produced was 72% of the amount of monomer charged.

The number average molecular weight of the resulting polymer is approximately 400,000 according to the osmotic pressure method, and the intrinsic viscosity measured at 30°C in toluene is
It was 2.69 dl/g.

The resulting polymer is a yellowish white solid;
It was soluble in toluene, carbon tetrachloride, ethylene dichloride, etc., and insoluble in n -hexane, ether, alcohol, etc. No softening point was observed below 300°C.

It was confirmed by the following analysis that the product was a polymer with the expected structure. Elemental analysis value [(C ₈ H ₅ Cl)
n] Calculated value C70.35%, H3.69%, Cl25.96% actual value
C70.86%, H3.67%, Cl25.30%. Infrared absorption spectrum 3100-3000 (m), 1650-1550 (W), 1495
(S), 1445 (S), 1090 (m), 825 (m), 755 (S)
),
690 (S), 545 (m) cm ^-1 .

Comparative Example 1 When the entire polymerization process was carried out in the dark without irradiation in Example 1, the yield of the produced polymer was 4%.
It was nothing more than

Example 2 Purified carbon tetrachloride 1 under dry nitrogen atmosphere
30 mmol of molybdenum hexacarbonyl was added thereto, and the mixture was irradiated with a 300W high-pressure mercury lamp at 30°C for 1 hour.

To the obtained catalyst solution was added 1.0 mol of 2-chloro-1-phenylacetylene and 25% by volume of chlorobenzene based on the monomer as an internal standard for gas chromatography, and the solution was incubated at 30°C for 24 hours in a dry nitrogen atmosphere. A polymerization reaction was carried out. Operations such as isolation of the polymer were the same as in Example 1.

The yield of methanol-insoluble polymer of 2-chloro-1-phenylacetylene was 83%. The intrinsic viscosity (in toluene, 30°C) was 4.88 dl/g.
The properties of the produced polymer were similar to those of the polymer obtained in Example 1.

Comparative Example 2 When irradiation was not performed in Example 2 and the entire process of catalyst preparation and polymerization was carried out in the dark, the yield of the resulting polymer was 5% or less.

Claims (1)

[Scope of Claims] 1. 2-
A method for producing a 2-chloro-1-phenylacetylene polymer, which comprises polymerizing chloro-1-phenylacetylene. 2. A catalyst is prepared by irradiating a mixture of a transition metal carbonyl selected from the group consisting of chromium carbonyl, molybdenum carbonyl, and tungsten carbonyl and 2-chloro-1-phenylacetylenes, and at the same time 2-chloro-1-phenyl is prepared. 2-, which is characterized by polymerizing acetylenes.
A method for producing a chloro-1-phenylacetylene polymer.