JP3000679B2 - Method for producing polyene structure-containing polymer - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a polyene structure-containing polymer, and more particularly to a method for easily producing a polyene structure-containing polymer by subjecting a halogen-containing polymer to a dehydrohalogenation treatment. In addition, the present invention relates to a method for producing a polymer having a polyene structure, which is effective for producing an excellent lightweight conductive material.

[0002]

2. Description of the Related Art Conventionally, it has been known that an organic polymer compound is very suitable as a lightweight conductive material, and organic polymer compounds such as polyacetylene, polythienylene, and polypyrrole have already attracted attention as a lightweight conductive material. I am collecting.

Of these, polymers having a polyene structure such as polyacetylene are produced by subjecting a halogen-containing polymer to a dehydrohalogenation reaction. Conventionally, as a method for producing a light-weight conductive material as a polyene structure-containing polymer by subjecting a halogen-containing polymer to a dehydrohalogenation reaction, a method of irradiating the halogen-containing polymer with ionizing radiation (Japanese Patent Application Laid-Open No. 60-1985) 168703), and a method of reacting by heating using an aqueous alkali solution and tetrabutylammonium bromide (Japanese Patent Application Laid-Open No. 58-142905).
No.), UV irradiation in the presence of oxygen or nitrogen (Pure
Appl. Chem. 53, 549; 1981).

[0004]

Among the above-mentioned conventional methods, the method using ionizing radiation has various problems in handling the radiation, and furthermore, depending on the irradiation amount, the polymer chains may be fragmented or ionized, and plastics may be produced. In addition to the risk of impairing the physical properties as well, it is economically disadvantageous.

In the method using an alkaline aqueous solution,
The reaction in an alkaline aqueous solution requires a long time under high temperature and high pressure, and the dehydrohalogenating agent used is expensive and toxic, which is industrially disadvantageous. The method of irradiating ultraviolet rays under an oxygen or nitrogen stream has a low reaction efficiency and cannot obtain a polyene structure-containing polymer in a sufficient yield.

An object of the present invention is to solve the above-mentioned conventional problems and to provide a method for producing a polyene structure-containing polymer from a halogen-containing polymer by a dehydrohalogenation reaction, which is inexpensive, efficient and safe. An object of the present invention is to provide a method for producing a polyene structure-containing polymer having excellent properties.

[0007]

The process for producing a polyene structure-containing polymer according to the present invention is characterized in that the halogen-containing polymer is dehydrohalogenated by irradiating it with ultraviolet rays in an atmosphere containing water vapor and hydrogen gas. The halogen-containing polymer is a polyene structure-containing polymer.

Hereinafter, the present invention will be described in detail.

In the method of the present invention, the halogen-containing polymer as a raw material is a high-molecular-weight halogen-containing polymer or copolymer having halogen and hydrogen bonded to carbon,
For example, vinyl chloride, vinyl bromide, vinyl fluoride, vinylidene chloride, vinylidene bromide, vinylidene fluoride or the like, or a homopolymer of vinylidene halide or a copolymer thereof, or the above vinyl halide or Copolymers with other monomers copolymerizable with vinylidene halide, specifically, vinyl chloride-vinyl acetate, vinyl chloride-acrylonitrile, vinyl chloride-ethylene, vinyl chloride-propylene, vinyl chloride-styrene , Vinyl chloride-butadiene, vinyl chloride-isoprene, vinyl chloride-vinylidene chloride, vinyl chloride-acrylic acid, vinyl chloride-methyl acrylate, vinyl chloride-
Methyl methacrylate, vinyl chloride-ethylene trifluoride,
Vinyl bromide-vinyl acetate, vinyl bromide-acrylonitrile, vinyl bromide-ethylene, vinyl bromide-propylene,
Vinyl bromide-vinylidene chloride, vinyl bromide-styrene,
Vinyl bromide-acrylic acid, vinyl bromide-methyl acrylate, vinyl bromide-methyl methacrylate, vinyl chloride-vinyl acetate-vinyl alcohol, vinyl chloride-vinylidene chloride-methyl acrylate, vinyl chloride-vinyl fluoride-
Copolymers such as ethylene tetrafluoride, vinyl bromide-styrene-methyl acrylate, vinylidene chloride-acrylonitrile, or those obtained by modifying these polymers or copolymers within a range that does not inhibit polyene formation (eg, chlorinated products) ).

[0010] These polymers or copolymers may be used alone or as a mixture of two or more. In addition, various additives such as a plasticizer, a stabilizer, a lubricant, and a coloring agent can be added to these halogen-containing polymers as needed.

In the present invention, the shape of the halogen-containing polymer is not particularly limited, and may be in the form of powder, film, fiber, or the like.
The shape may be any of a plate shape and the halogen-containing polymer may be used after being dissolved in an appropriate solvent.
In this case, examples of the solvent include tetrahydrofuran, dioxane, methyl ethyl ketone, cyclohexanone, acetone, dimethylformamide, dimethylacetamide, diethylformamide, dimethylsulfoxide, dichloroethane, methylene dichloride, trichloroethane, and the like. Used as a mixed solvent of more than one species.

The dehydrohalogenation reaction in the present invention is carried out by irradiating ultraviolet rays with a low-pressure mercury lamp or the like in a stream of steam and hydrogen. Here, the amount of steam and hydrogen used is not particularly limited, but the amount of steam is 20% with respect to the amount of hydrogen halide to be dehydrohalogenated.
To 70 ° C., preferably 20 to 30 ° C., hydrogen is 0.01 to 1 gram equivalent, preferably 0.1
Preferably it is ~ 0.5 gram equivalent.

The reaction time varies depending on the type of the halogen-containing polymer used as a raw material, the degree of dehydrohalogenation thereof, the intensity of ultraviolet rays to be irradiated, and the like.
In the case of an ultraviolet light source of about 00 W, the duration is 10 minutes to 3 hours, preferably about 30 to 120 minutes. In addition, the reaction temperature is generally in the range of 20 to 120 ° C, preferably 90 to 100 ° C.

[0014] The degree of dehydrohalogenation of the halogen-containing polymer is appropriately determined according to the intended use of the resulting polyene structure-containing polymer.

By subjecting the halogen-containing polymer to a dehydrohalogenation reaction in this manner, a polyene-structure-containing polymer having a polyene structure in which the corresponding halogen-containing structural skeleton is converted into-(CH = CH)- Is obtained. For example, when polyvinyl halide is converted to a polyene structure-containing polymer by a dehydrohalogenation reaction,-(CH = CH)
_A polyacetylene polymer consisting of _n- can be obtained. Such a polymer having a polyene bond has conductivity due to continuation of conjugate bonds, and can be effectively used as a conductive material for a conductive polymer, an electrode, a semiconductor element, or the like.

In the present invention, when the halogen-containing polymer is subjected to a dehydrohalogenation reaction, it is extremely advantageous to treat the halogen-containing polymer in the form of a film, since the post-treatment can be facilitated. That is, a film-like polyene structure-containing polymer produced from a film-like halogen-containing polymer can facilitate the molding process in the subsequent step. For example, a polarizing film can be easily manufactured by stretching a film-like polyene structure-containing polymer in one direction. The polarizing film thus obtained is an anti-reflection plate, sunglasses, a liquid crystal display,
It can be effectively used for various optical devices and window glass. In addition,
In order to form the halogen-containing polymer into a film, for example, the halogen-containing polymer may be dissolved in the above-mentioned appropriate solvent, and then flown onto a substrate such as a glass plate to form a film.

[0017]

By irradiating a halogen-containing polymer with ultraviolet rays in a steam and hydrogen atmosphere, under mild conditions without using an expensive and harmful dehalogenating agent,
The corresponding polyene structure-containing polymer can be obtained in high yield.

[0018]

The present invention will be described more specifically with reference to examples and comparative examples, but the present invention is not limited to the following examples unless it exceeds the gist.

Example 1 A polyvinyl chloride (PVC) powder (2 g) was dissolved in tetrahydrofuran (100 mg) and allowed to flow on a glass plate to form a film (5 μm in thickness). This glass plate (8) is made of a Pyrex tube shown in FIG.
and a 100 W low-pressure mercury lamp (inner diameter 10 mm, length 1000 mm) (3) was used as a light source. After degassing, hydrogen from the hydrogen inlet (1) was introduced into the reaction tube at a rate of 7 ml · min ⁻¹ through water (2). A vapor pressure of water was always present in the reaction tube. The temperature was controlled by a ribbon heater wound around the reaction tube. For example, the reaction was performed at 90 ° C. for 1 hour. In FIG. 1, reference numeral 4 denotes a thermometer, 5 denotes a water tank for capturing generated HCl, and 6 denotes a waste hydrogen storage tank.

After the completion of the reaction, the film was washed several times with purified methanol and dried under reduced pressure. When the infrared spectrum (FT-IR spectrum, ATR method) of this product was measured, it was 980 to 1010 cm and 1550 to 16 cm.
The absorption based on C = C was recognized at the position of 00 cm. X-ray diffraction measurement clearly showed a crystallization pattern due to the polyene structure.

FIGS. 2 and 3 show infrared spectrum charts of the raw material PVC and the produced polyene, and FIG. 4 shows an X-ray diffraction chart.

Example 2 A dehydrohalogenation reaction was carried out in the same manner as in Example 1 except that the reaction time was changed to 4 hours.
And the same result was obtained. FIG. 4 shows an X-ray diffraction chart.

Comparative Example 1 The procedure of Example 1 was repeated, except that UV irradiation was performed at 90 ° C. for 4 hours under a nitrogen stream. The infrared spectrum and the X-ray diffraction pattern were as follows. Same as vinyl, no change was observed. An X-ray diffraction chart is shown in FIG.

[0024]

As described in detail above, according to the method for producing a polyene structure-containing polymer of the present invention, a polyene structure-containing polymer useful as a lightweight conductive material can be easily, efficiently, inexpensively, and excellently manufactured. It can be manufactured with safety.

[Brief description of the drawings]

FIG. 1 is a system diagram showing a reaction apparatus used in Example 1.

FIG. 2 is an infrared spectrum chart of raw material PVC.

FIG. 3 is an infrared spectrum chart of a produced polyene in Example 1.

FIG. 4 is an X-ray diffraction chart of a raw material PVC and products of Examples 1, 2 and Comparative Example 3.

[Explanation of symbols]

 Reference Signs List 1 hydrogen inlet 2 water 3 low-pressure mercury lamp 4 thermometer 6 gas reservoir 7 reaction tube 8 glass plate coated with PVC

──────────────────────────────────────────────────の Continued on the front page (58) Field surveyed (Int.Cl. ⁷ , DB name) C08F 8/26 WPI (DIALOG)

Claims (1)

(57) [Claims] 1. A halogen-containing polymer is dehydrohalogenated by irradiating it with ultraviolet rays in an atmosphere containing water vapor and hydrogen gas, whereby the halogen-containing polymer is converted into a polyene structure-containing polymer. A method for producing a polyene structure-containing polymer.