JPS6049643B2 - 4-Hydroxy-4'-vinylbiphenyl polymer and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel 4-hydroxy-4''-vinylbiphenyl polymer and a method for producing the same.

The 4-hydroxy-4''-vinylbiphenyl polymer of the present invention has the general formula as a structural unit and has a number average molecular weight of about 560.
It is within the range of 0 to 60,000.

The polymer of the present invention has excellent heat resistance, and therefore is not only used as a heat-resistant resin for coating agents, films, and molded products, but also has high functionality by utilizing the reactivity of aromatic rings with hydroxyl groups. It can be used in a wide range of applications, including improving the heat resistance and chemical resistance of the so layer by using ion exchange resin as a molecule and further by phenol resin formation reaction.

The polymer of the present invention is produced by radical polymerization or cationic polymerization of 4-hydroxy-4''-vinylbiphenyl. 4-hydroxy-4''-vinylbiphenyl used as a starting material was discovered for the first time by the present inventor. This is a new compound, which is synthesized using p-phenylphenol, which has already been produced industrially, as a starting material.

That is, in the presence of an acid catalyst at room temperature, p-phenylphenol is converted to 4-acetoxybiphenyl with acetic anhydride, and then converted to 4-hydroxy-4''-acetylbiphenyl by Fries rearrangement. This is then converted into 4-hydroxy-4''-acetylbiphenyl in a methanol solvent. to obtain 4-,hydroxy-4″-(1-hydroxyethyl)biphenyl. When this product is subjected to a dehydration reaction at 180°C in the presence of zinc chloride and trichloroacetic acid in a dimethyl sulfoxide solvent, 4-hydroxy-4'-vinylbiphenyl is obtained in high yield (see Reference Examples below). The radical polymerization of 4-hydroxy-4''-vinylbiphenyl can be carried out under the same conditions as for the radical polymerization of ordinary vinyl monomers.

As the form of radical polymerization, any of bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization, etc. can be employed, and among these, solution polymerization is preferred. As the polymerization solvent, 4-hydroxy-4″-biphenylbiphenyl (
(hereinafter referred to as "monomer") and 4-hydroxy-4'
- those that dissolve vinyl biphenyl polymers are preferred;
For example, methanol, ethanol, tetrahydrofuran,
Examples include methylene chloride and chloroform. 7. As the polymerization initiator, a wide variety of conventionally known initiators can be used, such as peroxides such as cumene hydroperoxide and tert-butyl hydroperoxide, peroxides such as benzoyl peroxide and lauroyl peroxide, or azo Azo compounds such as bisisobutyronitrinor are used. The amount of these polymerization initiators to be used is not particularly limited and can be appropriately selected from a wide range.
It is usually preferable to use it within the range of 1 x 10-4 to 5 x 10-'' mol/e.The monomer concentration is not particularly limited, but is generally within the range of 0.05 to 3 mol/e. The polymerization temperature varies depending on the type of polymerization initiator and polymerization solvent used, but it is usually 0 to 1.
It is preferable to appropriately select the temperature within the range of 20°C. The above radical polymerization is preferably carried out under an inert gas atmosphere such as nitrogen gas.The polymerization time of the radical polymerization is generally about 3 to 8 hours.Cation of 4-hydroxy-4''-vinylbiphenyl Polymerization can be carried out under the same conditions as for cationic polymerization of ordinary vinyl monomers.
It is well known that in the case of cationic polymerization, a solvent should be selected that does not react with the growing carbon cation and reduce its activity, and it is also desirable to select a solvent that also dissolves the polymerization initiator and the produced polymer. In the case of cationic polymerization in the present invention, it is preferable to use a halogenated hydrocarbon such as methylene chloride or ethylene chloride, or a nitro compound such as nitrobenzene as a solvent. As the polymerization initiator, a wide variety of conventionally known initiators can be used, such as protonic acids such as phosphoric acid and sulfuric acid, boron trifluoride etherate, aluminum chloride, titanium tetrachloride, dichloride, etc.
Typical examples include metal halides such as tin, but organometallic compounds such as ethyldichloroaluminum can also be used. The amount of these polymerization initiators to be used is not particularly limited and can be appropriately selected from a wide range, but it is usually preferable to use it within the range of 1 x 10-4 to 5 x 10-1 mol/e. . Further, the monomer concentration is not particularly limited, but is generally preferably within the range of 0.01 to 1.5 mol/e. The polymerization temperature varies depending on the type of polymerization initiator and polymerization solvent used, so it cannot be generalized, but in general, polymerization proceeds more easily at lower temperatures than radical polymerization, and because carbon cations are unstable. It is preferable to carry out the polymerization reaction at low temperatures. In order to obtain the polymer of the present invention by cationic polymerization, it is preferable to polymerize at a temperature of O'C to 40C. The reaction time is shorter than that of radical polymerization. Preferably it is 1 to 18 pieces. Furthermore, unlike radical polymerization, cationic polymerization can be carried out in the atmosphere, but since a small amount of moisture affects the reaction, it is preferable to carry out the polymerization in a dry atmosphere and conditions. The polymer of the present invention produced by the above radical polymerization or cationic polymerization is isolated and purified by conventional separation means.

4-Hydroxy-4″ of the present invention thus obtained
-Vinyl biphenyl polymers can be prepared using alcohol solvents such as methanol and ethanol, halogenated hydrocarbon solvents such as methylene chloride and chloroform, tetrahydrofuran,
It is soluble in various organic solvents such as dimethylformamide, and can be used in various fields that require heat resistance, such as paints, adhesives, films, and molded products.

The present invention will be explained in more detail below by citing a method for synthesizing 4-hydroxy-4''-vinylbiphenyl monomer as a reference example, and further citing examples for producing the polymer of the present invention. The invention is not limited only to these examples.

Reference Example A mixture of 20y of aluminum chloride and 4y of common salt is placed in a flask equipped with a calcium chloride tube and heated to 180°C, melting it into a uniform liquid state.

This was cooled to 140 °C, 10 q of 4-acetoxybiphenyl (melting point 81-87 °C) was added, and the mixture was again heated to 18 °C with stirring.
Heat to 0°C and hold for 3 minutes. After the reaction mixture was cooled to room temperature, it was poured into ice water containing hydrochloric acid, and 60 ml of methylene chloride was added and stirred. Separate the methylene chloride layer, wash with water, dry, and then add hexane little by little to separate the tan oil. The remaining solution is concentrated and the resulting solid is recrystallized from a mixed solvent of acetone and hexane to obtain 4-hydroxy-4''-acetylbiphenyl with a melting point of 207.5-208.5°C. ''-acetylbiphenyl 15y is dissolved in 300 mt of tetrahydrofuran, and 3 g of lithium aluminum hydride is added little by little at room temperature.

When the reaction solution is concentrated and the remaining solution is poured into water, a yellowish white precipitate is produced. This precipitate is recrystallized from ethyl acetate to obtain 4-hydroxy-4''-(1-hydroxyethyl)biphenyl having a melting point of 145-146°C. 150 mt, add 10 q of zinc chloride, and heat to 180°C.

Add 10 y of trichloroacetic acid while stirring and react at 180° C. for 3 minutes. When the reaction solution is poured into water and the precipitated solid is recrystallized from a mixed solvent of acetone and hexane, 4-hydroxy-4''-vinylbiphenyl having a melting point of 190 to 191.5°C is obtained. Example 14-Hydroxy- 4
″-vinyl biphenyl 6q in tetrahydrofuran 20m
Dissolve in water and pour into a hard glass container.

After adding 0.025y of azobisisobutyronitrile to the mixture and purging it with nitrogen, a glass container was melt-sealed under high vacuum. This glass container was set in a shaking polymerization apparatus maintained at 60° C., and polymerization was carried out for 7.5 hours. The container was cooled to room temperature, opened, and the contents 5 were poured into about 200 ml of benzene to precipitate the formed polymer, which was thoroughly washed and dried under reduced pressure at room temperature. 2.0q of 4-hydroxy-4'-vinylbiphenyl polymer was obtained.

The viscosity of the obtained polymer was measured using an Ubbelohde viscometer in O-tetrohydrofuran solvent at 30 degrees Celsius.

The intrinsic viscosity [η] of the polymer determined from the results was 0.08
It was 4. The molecular weight was measured using gel permeation chromatography (GPC) using a tetrahydrofuran solvent at a flow rate of 1 ml/min, and the number average molecular weight of this polymer was found to be 32,000. The melting point of the polymer was measured using a differential scanning calorimeter (DSC) in a nitrogen stream at a heating rate of 80°C/min, and the melting point of the polymer obtained in Example 1 was 215°C. I got it. Furthermore, the heat resistance of the obtained polymer was evaluated by thermogravimetric analysis.

600 in air using a thermobalance at a heating rate of 10°C/min.
The relationship between the heating loss of the polymer measured up to ℃ and the temperature was as follows. Example 2 A solution of 60y of 4-hydroxy-4'-vinylbiphenyl in 300ml of tetrahydrofuran was charged into a flask equipped with a thermometer, a cooler, a stirrer, and a nitrogen inlet tube.

0.03y of benzoyl peroxide was added, nitrogen gas was blown into the mixture, and the mixture was heated in a nitrogen gas atmosphere to carry out a polymerization reaction at the reflux temperature of the solvent for 8 hours. After cooling to room temperature, the reaction product was concentrated under reduced pressure and poured into about 400 ml of benzene to precipitate the produced polymer, thoroughly washed, and then dried under reduced pressure. 34.5 g of 4-hydroxy-4''-vinylbiphenyl polymer was obtained as a light brown solid. The extreme viscosity [η] of the polymer was determined according to the measuring method described in Example 1. The extreme viscosity [η] was 0.31, and the number average Molecular weight is 60,000, melting point is 217℃
It was hot.

Example 3 A solution of 4-hydroxy-4''-vinylbiphenyl 6y in 200 ml of dichloromethane is placed in a dry glass container, and the container is covered with a neoprene rubber cap.

A solution of 0.7y of boron trifluoride etherate dissolved in 10ml of dichloromethane is gradually dripped from a microsyringe through a rubber cap.゛After the powder is polymerized at room temperature, the contents are poured into a large amount of benzene to precipitate the resulting polymer. After thorough washing, the product was dried under reduced pressure to obtain 5.0 y of light brown solid 4-hydroxy-4''-vinylbiphenyl polymer.The obtained polymer was prepared according to the method of Example 1. Gel permeation chromatography gave a number average molecular weight of 17,000.

Further, the melting point of the polymer measured by DSC was 211°C. Example 4 1.3y of stannic chloride was added to a solution of 5y of 4-hydroxy-45-vinylbiphenyl in 200ml of dichloromethane, being careful not to mix water.
was dissolved in 10 ml of dichloromethane and added dropwise.9
Polymerize at room temperature.

After reacting for 4 minutes, the resulting polymer was poured into benzene to precipitate it.

After purification and reprecipitation, a light brown solid 4-hydroxy-4''-vinylbiphenyl polymer was obtained almost quantitatively by drying under reduced pressure.7 The number average molecular weight of the polymer measured by the method of Example 1 was 16,000. The melting point was 211°C.

Example 54-hydroxy-4″-vinylbiphenyl 5y
was dissolved in 100 ml of nitrobenzene, 0.95 y of titanium tetrachloride was added, and the two powders were polymerized at room temperature.

The produced polymer was treated in the same manner as in Example 4 to obtain 3.5y of 4-hydroxy-4''-vinylbiphenyl polymer as a pale brown solid.The number average molecular weight of the polymer measured by the method of Example 1 was 15,000. and the melting point was 211°C.Example 6 4-Hydroxy-4'-vinylbiphenyl 1y was dissolved in 30ml of benzene and charged into a hard glass container.To this was added 0.03ml of azobisisobutyronitrile.
After adding y and purging with nitrogen, the glass container was melt-sealed under high vacuum. This glass sealed tube was set in a shaking polymerization apparatus maintained at 60° C., and a polymerization reaction was carried out for 7 hours. The sealed tube was cooled to room temperature, opened, and the benzene was concentrated. After repeatedly washing the resulting polymer with a small amount of benzene and drying it under reduced pressure at room temperature, 0.4y of a brownish 4-hydroxy-4''-vinylbiphenyl polymer was obtained. The molecular weight was measured by gel permeation chromatography (GCP) using tetrahydrofuran solvent, and a number average molecular weight of 5600 was obtained. The intrinsic viscosity [η] was 0.0005. The melting point was 208°C. 4-Hydroxy-4″ obtained in Examples 1 to 6 above
- All vinyl biphenyl polymers have the same infrared absorption spectra, with a hydroxyl group at 3350 cm and a hydroxyl group at 1600 cm.
-1, aromatic ring at 1520 cm-1 and 1500 cm-1, characteristic absorption of rose-substituted aromatic at 820 cm-1, and characteristic absorption at 1630 cm-1 based on the vinyl group that appeared in the infrared absorption spectrum of the monomer. absorption had disappeared.

Claims (1)

[Claims] 1 General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ is the constituent unit, and the number average molecular weight is about 5,600 to 6,000.
4-hydroxy-4'-vinylbiphenyl polymer within the range of 0. 2 A general formula characterized by polymerizing 4-hydroxy-4'-vinylbiphenyl in the presence of a radical polymerization catalyst ▲There are mathematical formulas, chemical formulas, tables, etc.▼ as the constituent unit, and the number average molecular weight is about 5,600 to 6,000
A method for producing a 4-hydroxy-4'-vinylbiphenyl polymer within the range of 0. 3 A general formula characterized by polymerizing 4-hydroxy-4'-vinylbiphenyl in the presence of a cationic polymerization catalyst ▲ There are mathematical formulas, chemical formulas, tables, etc.
A method for producing a 4-hydroxy-4'-vinylbiphenyl polymer within the range of 0.