JPS6031203B2 - 4-Hydroxy-4'-vinylbiphenyl copolymer and method for producing the same - Google Patents

Description

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

4-Hydroxy-vinylbiphenyl of the present invention has a repeating unit represented by the formula, and a repeating unit represented by the formula [where RI represents a hydrogen atom or a methyl group].

R2 represents a phenyl group, a carboxyl group, a lower alkoxycarbonyl group, a cyano group or a carbamoyl group. ]
It has a repeating unit represented by and/or a repeating unit represented by the formula, and has a number average molecular weight of about 2400 to
186,000, and the unit represented by formula (1) is 8 to
It is contained in the proportion of Satoshi mole%.

The copolymer used in the present invention has good solubility in organic solvents and excellent heat resistance, and can be imparted with a wide range of properties such as mechanical strength and processability depending on the copolymer composition. It can be used in heat-resistant paints, adhesives, films, and molded products.

The copolymer of the present invention is 4-hydroxy-4'-vinylbiphenyl and has the formula [where RI and R2 are the same as above.

It is produced by radical copolymerization of the compound represented by ] and/or maleic anhydride. 4-Hydroxy-4'-vinylbiphenyl, which is used as a co-generated raw material, is a new compound that was first seen and developed by the present inventor, and this compound was synthesized using p-phenylphenol, which has already been produced industrially, as a starting material. be done.

That is, p-phenylphenol is converted into 4-acetoxybiphenyl with acetic anhydride at room temperature in the presence of an acid catalyst, and then converted into 4-hydroxy-4'-acetylbiphenyl by Fries rearrangement. This product is further reduced using sodium borohydride in methanol solvent to obtain 4-hydroxy-4'-(1-hydroxyethyl)biphenyl. Zinc chloride,
When the dehydration reaction is carried out at 180° C. in the presence of trichloroacetic acid, 4-hydroxy-vinylbiphenyl can be obtained in high yield (see Reference Examples below). The compounds of formula (N) used as another starting material in the present invention are all known compounds, specifically styrene, Q-methylstyrene, etc.
Examples include acrylic acid, methyl acrylate, ethyl acrylate, methacrylic acid, methyl methacrylate, ethyl methacrylate, acrylonitrile, methacrylonitrile, acrylamide, and methacrylamide.

The radical copolymerization of the present invention can be carried out under the same conditions as those for conventional radical copolymerization of vinyl monomers.

The forms of radical copolymerization include bulk polymerization, solution polymerization,
Although suspension polymerization, emulsion polymerization, etc. can be employed, solution polymerization is preferred among these. The polymerization solvent is preferably one that dissolves monomers such as 4-hydroxy-4-vinylbiphenyl, the compound of formula (N), and the copolymer of the present invention, such as tetrahydrofuran,
Examples include dimethylformamide. Furthermore, as the polymerization initiator, a wide variety of conventionally known ones can be used.
For example, peroxides such as cumene hydroperoxide and tert-butyl hydroperoxide, peroxides such as penzoyl peroxide and lauroyl peroxide, or azo compounds such as azobissuisobutyronitrile are used. The amount of these polymerization agents to be used is not particularly limited and can be appropriately selected from a wide range, but is usually 1 x 10
-4 to 1 x 10-1 mol/mole is preferably used within that range. Further, the monomer concentration is not particularly limited, but is generally preferably within a range of 0.1 to 5 mol/mole. The amount of 4-hydroxy-4-vinylbiphenyl in the monomer is usually about 10-95 mol%, preferably 40-95 mol%.
The content is preferably about 0 mol%. Other monomers of the formula (W
) and maleic anhydride may be used alone or in combination. The polymerization temperature varies depending on the type of polymerization initiator and polymerization solvent used and cannot be unconditionally determined, but it is usually preferably selected as appropriate from within the range of 0 to 120°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 1 to 16 hours. The copolymer of the present invention produced by the above radical copolymerization is isolated and purified by conventional separation means.

For example, a copolymer obtained by solution polymerization can be used as it is as a base for paints and adhesives, or the copolymer can be separated and purified according to conventional methods and used.
The composition of the copolymer monomer to be used in the above radical copolymer can be arbitrarily selected over a wide range depending on the properties of the copolymer, but the composition of the copolymer produced depends on the composition of the monomers. Regulated by reactivity ratio. 4-hydroxy-4
- Copolymerizing vinyl biphenyl and the compound of formula (W) with various monomer compositions, analyzing the composition of each copolymer produced, and determining the reactivity ratio of the various monomers obtained from the results. is as follows.

Table 1 r,: Reactivity ratio of 4-hydroxy-4'-vinylbiphenyl r2: Reactivity ratio of each monomer Based on these reactivities, copolymers containing 4-hydroxy-4'-vinylbiphenyl are It can be said that the copolymerizability is high.

Furthermore, in the copolymer of 4-hydroxy-4'-vinylbiphenyl and maleic anhydride, a copolymer with a nearly constant 1:1 composition is obtained regardless of the monomer composition, indicating that alternating copolymerization is occurring. has become clear. The copolymer of the present invention thus obtained has a number average molecular weight of about 2400 to 1860.
00, and 4-hydroxy-4'-vinyl biphenyl is contained in a proportion of 8 to 98 mol%. The 4-hydroxy-4'-vinylbiphenyl copolymer obtained by the present invention has excellent solubility and heat resistance, and has a high carbon residual rate at 600 qC. Therefore, it can be used as paints, adhesives, films, and molded products in various fields where heat resistance is required. 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 of producing the copolymer of the present invention as examples. However, the present invention is not limited to these examples.

Reference Example: A mixture of 20 parts of aluminum chloride and 4 parts of common salt is placed in a flask equipped with a calcium chloride tube and heated to 8,000 ℃ to melt it into a uniform liquid.

Cool this to 14,000, add 4-acetoxybiphenyl (melting point 81-8〆○) for 10 minutes, and pour it under Nawa Azusa again to 18
Heat to 000 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 g 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 was concentrated and the resulting solid was recrystallized from a mixed solvent of acetone-hexane to give 4-hydroxy-4' with a melting point of 207.5-208.5q0.
- Acetyl biphenyl is obtained. Next, 4-hydroxy-4'-acetylbiphenyl (15%) was dissolved in 300% of tetrahydrofuran, and 3% of lithium aluminum hydride was 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)piphenyl having a melting point of 145-146 oo. Dissolve 50 parts of 4-hydroxy-4'-(1-hydroxyethyl)biphenyl in 150 parts of dimethyl sulfoxide, add 10 parts of zinc chloride, and heat to 180 parts.

Add 10 quarts of trichloroacetic acid under the fly water and add 180 qo for 3 minutes.
React with. 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'-vinyl bifenyl having a melting point of 190 to 191.5°C is obtained. Example: Into a flask equipped with a thermometer, a cooling tube, a stirrer, and a nitrogen gas inlet tube, 300% of tetrahydrofuran was charged, and the molar fractions of each monomer to be copolymerized with 4-hydroxy-4'-vinylpiphenyl were measured. Charge the monomeric mixture so that the total amount corresponds to about 1 mole.

Blow nitrogen gas to replace the air and maintain the temperature at 60qC. A solution of 1.6 parts of azobisisobutyronitrile dissolved in 10 parts of tetrahydrofuran was gradually added dropwise to carry out a polymerization reaction for 1 to 1 hour under a nitrogen gas atmosphere. After the reaction was completed, the contents were poured into a large amount of benzene or ether, and the precipitated polymer was collected, purified and reprecipitated several times, and dried under reduced pressure. A white to pale pink solid 4-hydroxy-4'-vinylbiphenyl copolymer was obtained. Based on this example, various copolymers of the present invention were synthesized and the compositions of the copolymers were analyzed.

In addition, each of the obtained copolymers was dissolved in tetrahydrofuran and the viscosity was measured at 30 qo using an Ubbelohde viscometer,
Find the limiting viscosity. The number average molecular weight of each copolymer was determined by gel permeation chromatography (GP
It was calculated using a universal calibration curve from the results of C) and the results of the intrinsic viscosity. The melting point is measured using a differential scanning calorimeter (DSC) in a nitrogen stream at a heating rate of 30°C/min.
This was determined from the results. The heat resistance of some copolymers is
Heating rate: 10 C/min, heating loss curve in air: 6
The amount of residual carbon at 0000 was measured and evaluated. 4-hydroxy-4'-vinylpiphenyl (HVB) and styrene (
Table 2 shows the results of copolymerization with St), and Table 3 shows the results of copolymerization with HVB and methyl methacrylate (MMA).
Table 4 shows the results of copolymerization of TVB and acrylonitrile (AN).
Table 5 shows the results of copolymerization with HVB and methacrylic acid (MA), and Table 6 shows the results of copolymerization with HVB
Table 7 shows the results of copolymerization of HVB and maleic anhydride (MAN), and Table 8 shows the results of copolymerization of HVB, MMA, and AN.

Table 2 Table 3 Table 4 Table 5 Table 6 Table 7 Table 8

Claims (1)

[Claims] 1 A repeating unit represented by the formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ and the formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, R^1 represents a hydrogen atom or a methyl group] . R^2 represents a phenyl group, a carboxyl group, a lower alkoxycarbonyl group, a cyano group or a carbamoyl group.
] Repeating unit and/or formula ▲ Numerical formula,
There are chemical formulas, tables, etc. ▼ It is characterized by having a repeating unit represented by , a number average molecular weight of approximately 2400 to 186000, and containing units represented by formula (I) at a ratio of 8 to 98 mol% A 4-hydroxy-4'-vinylbiphenyl copolymer. 2 4-Hydroxy-4'-vinylbiphenyl and the formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, R^1 represents a hydrogen atom or a methyl group. R^2 represents a phenyl group, a carboxyl group, a lower alkoxycarbonyl group, a cyano group or a carbamoyl group.
] A compound represented by the formula and/or maleic anhydride is copolymerized in the presence of a radical polymerization catalyst to form a repeating unit represented by the formula ▲ mathematical formula, chemical formula, table, etc. ▼ and the formula ▲ mathematical formula, chemical formula, table, etc. etc.▼ [In the formula, R^1 and R^2 are the same as above. ] Repeating unit and/or formula ▲ Numerical formula,
There are chemical formulas, tables, etc. ▼ 4-hydroxy having a repeating unit represented by , a number average molecular weight of about 2400 to 186000, and containing 8 to 98 mol% of units represented by formula (I) -A method for producing a 4-hydroxy-4'-vinylbiphenyl copolymer, which comprises obtaining a 4'-vinylbiphenyl copolymer.