JP2661715B2 - Heat resistant unsaturated polyester - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a novel heat-resistant polyester.

2. Related Art Various polyesters using 9,9-bis (4-hydroxyphenyl) fluorene as a raw material have been conventionally proposed.

For example, a polymer obtained by giving a polymer an organic solvent solubility for the purpose of improving the moldability of polyester is a polyester obtained by reacting with a terephthalic acid / isophthalic acid mixed (3/7 to 7/3) system. This is reported in JP-A-57-192432.

A single polyester of 9,9-bis (4-hydroxyphenyl) fluorene and isophthalic acid or a fatty acid is reported in U.S. Pat. No. 3,546,165. Polyester obtained by reacting with terephthalic acid / adipic acid (1 / 99-60 / 40) system has excellent moldability due to the large difference between glass transition temperature and decomposition temperature. I have.

PROBLEM TO BE SOLVED BY THE INVENTION When a conventional soluble heat-resistant polyester is formed into a molded product such as a film, there is a disadvantage that the chemical resistance is poor. Chemical resistance is an important property in terms of the use environment and processing steps of a plastic film. Generally, plastics are strong against acids and alkalis but weak against organic solvents.

The present invention is to produce a chemically stable polyester which is soluble before heat treatment, insoluble in all organic solvents after heat treatment, while maintaining the moldability and other properties as conventional products. Aim.

That means for solving the problems, the present invention provides (1) has a structure represented by the general formula _{(I), X-Y m} X-Z n ··· (I) ( In the formula, X is Y is -OC-CH = CH-CO- Z is R in X is hydrogen or a lower alkyl group, and m and n indicate the number of repetitions. A) a polyester having a molar ratio of the Y component to the Z component of 10/90 to 99/1, and a solution obtained by dissolving 0.5 g of the polyester in 100 ml of dimethylformamide having an inherent viscosity (η inh) of at least 0.4 measured at 30 ° C. (2) a polyester obtained by curing the unsaturated polyester according to claim 1 by heat treatment, wherein the degree of crosslinking is 250 to 300 ° C. for 25 to 30 minutes. Solvent-insoluble polyester, which is comparable to the heat-treated polyester.

 Hereinafter, the present invention will be described in more detail.

The polyester of the present invention comprises a diol component (X component)
And an acid mixture component consisting of a terephthalic acid component (Z component) and a fumaric acid or maleic acid component (Y component, hereinafter sometimes referred to as fumaric acid component).

The diol component (component X) contained in the polyester of the present invention is represented by the following formula.

Here, R is hydrogen, a lower alkyl group such as a methyl group or an ethyl group. These diol components are derived from diols used as raw materials, and diols that provide such diol components include 9,9-bis (4
-Hydroxyphenyl) fluorene, 9,9-bis (3-
Methyl-4-hydroxyphenyl) fluorene, and 9,
9-bis (3-ethyl-4-hydroxyphenyl) fluorene and the like.

Also, of the acid mixture components, terephthalic acid component (Z component)
Is based on terephthalic acids used as a raw material, and examples of such terephthalic acids include terephthalic acid chloride.

Note that a part of the terephthalic acid component may be replaced with isophthalic acid. In this case, from the viewpoint of heat resistance, the proportion of isophthalic acid is 50 mol% or less of the terephthalic acid component, preferably 20 mol% or less.
Mol% or less.

The fumaric acid component (Y component) is derived from fumaric acids and maleic acids used as raw materials, and examples of such raw materials include chlormaleic acid. Among them, fumaric acids are preferred because they are inexpensive and do not impair heat resistance, and the polymer is soluble in chloroform and tetrahydrofuran, which are particularly low-boiling solvents. In some cases, a part of the fumaric acid and maleic acid components (Y component) may be replaced with another unsaturated aliphatic dicarboxylic acid component such as itaconic acid.

Further, regarding the ratio of the terephthalic acid component (Z component) and the fumaric acid component (Y component), in the present invention, the olefin portion of fumaric acid is insoluble in an organic solvent by crosslinking by heat treatment, and the polymer has a chemical resistance. Is improved. This phenomenon occurs because
Since the ratio of the fumaric acid component to the phthalic acid component is between 10/90 and 99/1, it is necessary to be within this range.

The present invention is a heat-resistant polyester which skillfully utilizes the difference in solubility between a polymer before and after molding in an organic solvent. When the molar ratio of the fumaric acid component is less than 10%, the chemical resistance is not significantly improved even by performing the heat treatment.

Since this polyester has an unsaturated bond, it can be cured by heat treatment or the like. Temperature condition of heat treatment is
25-30 minutes at 250-300 ° C is sufficient. Fumaric acid or
When the content of maleic acid is less than 10%, safe chemical resistance cannot be obtained even if heat treatment is performed.

The polyester of the present invention has an inherent viscosity of 0.4 dl /
High polymerization degree at g or more.

Next, an example of the method for producing the polyester of the present invention will be described.

An alkali is added to diols as raw materials to obtain an aqueous alkali solution. The alkali is not particularly limited, but is preferably caustic soda. Diols are added to the aqueous alkali solution and dissolved by heating. The amount of the alkali is suitably 1.2 to 2.0 times the equivalent of the diols.

Chloride of each carboxylic acid is suitably used as the acid component. This acid chloride is dissolved in 1,2-dichloroethane, chloroform, and 1,1,2,2-tetrachloroethane to form an acid component organic solvent solution.

Next, the above-mentioned acid component organic solvent solution is dropped into an aqueous alkali solution that is being vigorously stirred, and is subjected to interfacial polycondensation. In addition, since interfacial polycondensation is performed at the interface, it is preferable to add an appropriate amount of a phase transfer catalyst to an aqueous solution because the reaction is promoted. Specific examples of the catalyst include tetraethylammonium chloride and triethylbenzylammonium chloride, which are common surfactants. The amount added is sufficient to be used for interfacial polycondensation,
The amount is such that an aqueous solution of 2% or less is obtained. It is not preferred because too much emulsification is used and the degree of polymerization of the polymer does not increase.

The reaction temperature is 10 to 50 ° C, preferably 20 to 30 ° C, and the reaction time is about 15 to 20 minutes.

After completion of the reaction, the obtained aqueous phase and organic phase are separated, and the organic phase is washed with a small amount of water. After washing, chloroform is added to the organic phase to reduce the viscosity.

Next, this is poured into methanol or acetone, and the precipitate is separated by filtration and dried to obtain the polyester of the present invention.

This polyester can be used as a raw material for paints, films, molded products and the like. Further, by heating and curing the unsaturated polyester, it becomes a chemically stable polyester.

Examples Hereinafter, the present invention will be described in more detail with reference to Examples.

Example 1 (molar ratio of fumaric acid / terephthalic acid = 10/90) 18.27 g of terephthalic acid chloride, fumaric acid chloride
Dissolve 1.52 g in 300 ml 1,2-dichloroethane.

100 ml of 4N sodium hydroxide is added to 1000 ml of water, and 35 g of 9,9-bis (4-hydroxyphenyl) fluorene and 15 g of triethylbenzylammonium chloride are dissolved therein.
The acid component organic solvent solution was added to this solution at a time with vigorous stirring, and the mixture was reacted for 15 to 20 minutes. After the reaction, the aqueous phase was discarded, and the organic phase was washed twice with 500 ml of water. After washing
200 ml of 1,2-dichloroethane was added to the organic phase to reduce the viscosity. This is poured into acetone, the precipitate is filtered off,
Dried to obtain polyester.

The properties of the obtained polyester have an intrinsic viscosity of 0.9 dl / g,
Glass transition temperature was 335 ° C.

Next, a 10% polyester solution of 1,1,2,2-tetrachloroethane was cast on a glass plate and dried under reduced pressure to obtain a polyester film. This film had a tensile strength of 9.0 kg / mm ² and a tensile modulus of 320 kg / mm ² . Next, the film was heat-treated in an inert oven at 250 ° C. for 30 minutes. Even if this film was immersed in an organic solvent for several days, no change was observed, and the mechanical properties before the heat treatment were almost the same.

Example 2 (molar ratio of fumaric acid / terephthalic acid 20/80) 16.24 g of terephthalic acid chloride, fumaric acid chloride
Dissolve 3.04 g in 300 ml of 1,2-dichloroethane. The acid component organic solvent solution was added to the 9,9-bis (4-hydroxyphenyl) fluorene aqueous solution of Example 1 at a time with vigorous stirring to cause a reaction.

 Hereinafter, it carried out similarly to Example 1.

The properties of the obtained polyester have an intrinsic viscosity of 1.0 dl / g,
The glass transition temperature was 360 ° C. The tensile strength of this polyester film is 8.7 kg / mm ² , and the tensile modulus is 310 kg
It was / mm ^2.

Other physical properties are volume resistivity (23 ℃) 1.6 × 10 ¹⁴ Ωcm, dielectric constant 2.61, dielectric loss tangent 0.012 (23 ℃, 1MHz), dielectric strength 69KV / mm, total light transmittance 90.3%, yellowness 3.05% Met.

Next, the film was heat-treated at 250 ° C. for 30 minutes in an inert oven and became insoluble in all organic solvents. The properties of the insolubilized film were almost the same as those before the heat treatment.

Example 3 100 mmol of a terephthalic acid chloride-fumaric acid chloride mixture (acid molar ratio of 50/50, 20/80, 1/99) was added to 1,2-
After dissolving in 300 ml of dichloroethane, the solution was added to the aqueous solution of 9,9-bis (4-hydroxyphenyl) fluorene of Example 1 and stirred vigorously. Hereinafter, it carried out similarly to Example 1.

The properties of the obtained polyester have an intrinsic viscosity of 0.9 d each.
l / g, 1.1dl / g, 0.8dl / g, glass transition temperature 330 ° C,
320 ° C and 315 ° C. The film heat-treated at 250 ° C. became insoluble in all organic solvents.

Comparative Example 1 (molar ratio of fumaric acid / terephthalic acid 5/95) 19.28 g of terephthalic acid chloride, fumaric acid chloride
760 mg are dissolved in 300 ml of 1,2-dichloroethane. The above-mentioned organic solvent solution of the acid component is added to the 9,9-bis (4-hydroxyphenyl) fluorene aqueous solution of Example 1, and the mixture is vigorously stirred and reacted. Hereinafter, it carried out similarly to Example 1.

The properties of the obtained polyester have an intrinsic viscosity of 1.0 dl / g,
Glass transition temperature was 325 ° C. The tensile strength of this polyester film is 8.8 kg / mm ² and the tensile modulus is 315 kg / m
It was m ^2.

Next, this film was treated at 250 ° C. for 30 minutes in the same manner as in Example 1.
Although heat treatment was performed for a minute, it was dissolved in m-cresol, N-methylpyrrolidone, dimethylformamide, dimethylacetamide, dimethylsulfoxide, chloroform, and tetrachloroethane. In addition, it took a long time to dissolve in dioxane and tetrahydrofuran.

The results of examining the solubility of the above Examples 1 to 3 and Comparative Example 1 are shown in Table 1.

Effects of the Invention The polyester of the present invention has heat resistance and is soluble in an organic solvent, and becomes insoluble in an organic solvent by further appropriate heat treatment. This is excellent in workability before processing,
It is characterized in that after processing, the chemical resistance, which is a drawback of polyester, can be improved.

Glass transition point of 300 ℃ or higher, and dielectric constant comparable to Teflon
It can be 2.6, so it is suitable for electrical insulation field for heat resistant applications, paints, adhesives, etc.

The polyester of the present invention is excellent in chemical resistance in addition to heat resistance, solubility and processability. Further, since there is no coloring, it is useful when used as a paint or film.

 ────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-57-192432 (JP, A) JP-A-60-138542 (JP, A) JP-B-4-22931 (JP, B2)

Claims (2)

(57) [Claims] 1. A general formula (I) in the structure _{X-Y m X-Z n} ...... represented (I) (In the formula, X is Y represents -OC-CH = CH-CO-, and Z represents Wherein R in the above X is hydrogen or a lower alkyl group, and m and n indicate the number of repetitions. ), Y component and Z
A polyester having a molar ratio of components of 10/90 to 99/1, and a solution obtained by dissolving 0.5 g of the polyester in 100 ml of dimethylformamide has an inherent viscosity (η _inh ) measured at 30 ° C. of at least 0.4 dl / g. Is a heat-resistant unsaturated polyester. 2. A polyester obtained by curing the unsaturated polyester of claim 1 by heat treatment, wherein the degree of crosslinking is the same as that of heat treatment at 250 to 300 ° C. for 25 to 30 minutes. Some solvent-insoluble polyesters.