JPS63152622A - Production of soluble heat-resistant polyarylate - Google Patents

Abstract

PURPOSE:To obtain the titled novel polymer having excellent solubility, heat- resistance, self-supporting property, etc., by polymerizing a terephthaloyl chloride derivative, an isophthaloyl chloride derivative and a bis(hydroxyphenyl)fluorene using a specific method. CONSTITUTION:(A) A terephthaloyl chloride derivative and/or an isophthaloyl chloride derivative are dissolved in 1,2-dichloroethane. (B) A 9,9-bis(4- hydroxyphenyl)fluorene is dissolved in 1,2-dichloroethane at a temperature between 50 deg.C and the boiling point of the solvent and the obtained solution is added to the solution of the component A without cooling the solution at a ratio of attain an equimolar ratio of the component A to the component B. The objective polymer having an inherent viscosity of >=0.7dl/g can be produced by carrying out the polymerization of the above mixture.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention provides a method for producing polyarylate having heat resistance and solubility.

BACKGROUND OF THE INVENTION Aromatic polyesters, that is, polyarylates, have excellent properties based on their structure. In particular, polyarylates consisting of aromatic dicarboxylic acid residues, aromatic dihydroxy compound residues, and/or aromatic hydroxycarboxylic acid residues It has excellent heat resistance and can be used in compression molding, transfer molding, injection molding, etc., and has excellent mechanical and electrical properties, and is used in many fields such as mechanical parts, electrical, electronic parts, automobile parts, tableware, and medical equipment. It is used.

In general, polyester has good film-forming properties, and its physical properties such as mechanical strength and electrical properties are similar to those of polyimide C at around room temperature. However, at temperatures above 150° C., these physical properties rapidly deteriorate compared to polyimide.

If this polyester has physical properties such as mechanical strength equivalent to polyimide at high temperatures, it will also be colorless and transparent.
It is expected that its applications will further expand.

9. The fact that polyarylates can be obtained from 9-bis(4-hydroxyphenyl)fluorene and at least one of terephthalic acid chloride and isophthalic acid chloride is disclosed in U.S. Pat.
122,201 and JP-A-57-182432
It is disclosed in the publication No. In all of these methods, polyarylates are synthesized by an interfacial polymerization method or a low-temperature solution polymerization method in which the reaction is carried out while maintaining the reaction solution at 10°C.

The inventors of the present application carried out polymerization using terephthalic acid chloride as the acid chloride component according to the method described in the above-mentioned British patent specification, US patent specification, and Japanese Patent Application Laid-open No. 57-1!32432. In all of these methods, polyarylate had insufficient solubility in organic solvents and insufficient mechanical strength when formed into a film. In other words, regarding solubility, even if chloroform, which is a solvent with high solubility for polyarylates among commonly used organic solvents, is used, polyarylates synthesized by each of the above interfacial polymerization methods will have an insoluble portion remaining. The solution became cloudy.

Furthermore, when a film was produced, it had poor flexibility and was very brittle. That is, 8.8-bis(4-
The polyarylate obtained from hydroxyphenyl)fluorene and terephthalic acid chloride by interfacial polymerization was hardly soluble.

The above-mentioned defects are considered to be due to the polymerization method rather than defects in the polyarylate itself.

That is, in the interfacial polymerization method, polymerization proceeds at the interface between the wood and the organic solvent, but when a reactive compound such as acid chloride, which is conventionally used as a raw material, is used, hydrolysis by water also proceeds at the same time. As a result of hydrolysis, the activity of one polymerization terminal is lost and the molar balance of the raw materials is disrupted, so that the degree of polymerization cannot be improved.

Further, the above-mentioned insoluble cloudy part is considered to be a mer of terephthalic acid or a polymer, that is, an oligomer, and it is thought that this will hinder the transparency of the film when it is formed into a film.

Furthermore, methods for producing polyarylates using low-temperature solution polymerization methods include British Patent No. 1,122,201 and Austrian Patent No. 3.
60.7eO, but in the former 10°C
In the latter case, a polyarylate with a reduced viscosity of 0.58 a/g was obtained by carrying out low-temperature solution polymerization, and a polyarylate with an inherent viscosity of 0.52 di/g was obtained by conducting a similar polymerization at 30° C. in the latter case. Both of these have an inherent viscosity of 0.6
The degree of polymerization was somewhat low as there was no polymer with di: exceeding z'g.

Problems to be Solved by the Invention The present invention aims to improve the problems of the interfacial polymerization method and solution polymerization method described above by studying methods for improving the degree of polymerization and polymerization methods that do not contain insoluble oligomers. The aim is to develop a new polyarylate polymerization method that solves these problems.

The present invention provides a method for producing a polyarylate that completely dissolves in a specific organic solvent, forms a self-supporting film, and exhibits a high degree of polymerization and high heat resistance.

Means for Solving the Problems The present invention provides at least one of terephthalic acid chloride derivatives and isophthalic acid chloride derivatives and 9,9-bis(4
When carrying out solution polymerization in 1,2-dichloroethane using substantially equimolar amounts of -hydroxyphenyl)fluorenes, a solution in which an acid chloride derivative was dissolved in 1,2-dichloroethane was prepared in advance, and 1.2- Dissolve 9,9-his(4-hydroxyphenyl)fluorenes in dichloroethane at a temperature range from 50°C to the boiling point of the solvent, and cool the resulting solution of 9,9-bis(4-hydroxyphenyl)fluorenes. This is a method for producing a soluble heat-resistant polyarylate, which is characterized in that the acid chloride derivative is gradually added to a solution of the acid chloride derivative and polymerized to obtain a polyarylate having an inherent viscosity of 0.7 du/g or more.

In developing a new polyarylate polymerization method, the present invention specifically aimed to improve solvent solubility, self-supporting properties, and thermal properties.

Regarding solvent solubility, we aimed for +j7 solubility in polar organic solvents that generally have high solubility or organic halogen solvents that are good solvents for polyester.

In addition, the target physical properties of the polyarylate are that it forms a self-supporting film, that is, it does not break easily when handled;
The target was a tensile strength of several kg/1m2 that would not shatter. For this purpose, the intrinsic viscosity (ηin
h) 0.7a/g or more is required. Furthermore, regarding heat resistance, the target glass transition temperature is 250 to 350℃.
And so. This value is equivalent to the maximum temperature at which injection molding and compression molding can be performed, and accordingly, the thermal decomposition temperature is 4 C.
We aimed for a temperature of 50℃ or higher.

The terephthalic acid chloride derivatives and isophthalic acid chloride derivatives used as raw materials in the present invention include active ones such as acid chloride and acid chloride derivatives in which an alkyl group or the like is introduced into the benzene ring, and are widely used in polyester synthesis. Use what you have.

Examples of 9.9-bis(4-hydroxyphenyl)fluorenes include 9.9-bis(4-hydroxyphenyl)fluorene, 9.3-bis(3-methyl-4-hydroxyphenyl)fluorene, and 9.9-bis(4-hydroxyphenyl)fluorene. (3-ethyl-4-hydroxyphenyl)fluorene or the like is used.

The reaction involves at least one of a terephthalic acid chloride derivative and an isophthalic acid chloride derivative and 9,8-bis(4
-Hydroxyphenyl)fluorenes are used in substantially equal moles, and 1,2-dichloroethane is used as a polymerization solvent to ensure the solubility and reactivity of the resulting polymer.

That is, a solution in which the ugly chloride derivative component is dissolved in 1,2-dichloroethane is prepared in advance.

Next, 8,8-bis(4-hydroxyphenyl)fluorenes were dissolved in 1,2-dichloroethane at a temperature range of 50°C or higher and the boiling point of the solvent (83.5°C) or lower, and the resulting 3
, the solution of 9-bis(4-hydroxyphenyl)fluorenes was gradually added as it was to the solution of the acid chloride derivative without cooling.

Polymerization is carried out by a solution polymerization method, and the polymerization is stopped while the polymerization solution is in a homogeneous state before the produced polyarylate becomes too polymeric and becomes insolubilized.

In order to uniformly dissolve the starting materials and increase the polymerization degree of polyarylate, as mentioned above, fluorenes are dissolved in 1,2-dichloroethane at a temperature range of 50°C or higher and lower than the boiling point of the solvent, and the resulting solution is It is necessary to allow the polymerization reaction to proceed as is without cooling.

After stopping the polymerization reaction, the hydrochloride produced by reacting with a tertiary amine etc. added to remove by-produced hydrochloric acid is 1! ! After removing it by means such as The liquid is poured into a polyarylate-insoluble solvent such as acetone, and the polyarylate produced is precipitated to separate the polyarylate.

Furthermore, if necessary, the purity of the polyarylate obtained can be increased by dissolving the separated polyarylate in a solvent such as chloroform, pouring it into acetone, etc. again, reprecipitating it, and separating it for purification.

When using a mixture of terephthalic acid chloride derivatives and isophthalic acid chloride derivatives, the solubility of the produced polyarylate improves as the molar ratio approaches 1, so they should be selected appropriately depending on the required physical properties. The above-mentioned heat resistance, solubility, and moldability, which are the objectives of the present invention, are satisfied at any mixing ratio.

In addition, the reaction time until polyarylate becomes insolubilized is
In addition to the temperature of the reaction solution, it changes depending on the mixing ratio of the terephthalic acid chloride derivative and the isophthalic acid chloride derivative, and the closer the ratio of both is to 1, the more difficult it is for the polyarylate to become insolubilized, and the longer the reaction time until insolubilization becomes. .

The polyarylate obtained by the production method of the present invention is prepared by mixing 0.5 g of tetrachloroethane-phenol (4
The intrinsic viscosity (ηimh) measured at 30° C. when dissolved in a mixed solution of 8) is at least 0.7 dQ/g or more, and the preferred material L < 1. OdQ/g or more, and the tensile strength of the polyarylate is 1 kgf/m2 or more, moreover 512 f/ms2 or more, and in some cases 10 kgf/m
s2 or more.

In undeveloped II, 1,2-dichloroethane is used as a solvent and the reaction is carried out by a solution polymerization method, so water does not coexist and deactivation of phthalic acid chloride due to hydrolysis can be prevented compared to an interfacial polymerization method.

The resulting polyarylate may become colored due to oxidation at high temperatures. This is because the phenol group or acid chloride group at the end of the polymer is hydrolyzed by wood in the acetone used for purification and becomes a carboxyl group, but the phenol group is particularly easy to oxidize and is the cause of discoloration. If you want to avoid coloring, the terminal may be protected with an alkyl group or an acyl group.

Specifically, it is preferable to use an alkyl halide or an acyl halide, particularly an acetyl halide or a benzoyl halide.

The following will be described in detail based on examples.

Examples Example 1 8.3-bis(4-hydroxyphenyl)fluorene 3
．． Add 5g to 70d of 1,2-dichloroethane.

It was heated to 60°C to dissolve it. A solution obtained by adding 2.2 g of triethylamine to this solution was added dropwise over 5 minutes to a dichloroethane 30 solution containing 1.81 g of terephthalic acid chloride and 0.2 g of inphthalic acid chloride prepared in advance without cooling. Thereafter, when stirring was continued at room temperature, triethylamine hydrochloride was precipitated and the viscosity increased. 3～
After stirring for 5 hours, the filtered solution of triethylamine hydrochloride was poured into acetone.

The precipitated polyarylate was filtered, dissolved in chloroform, poured into acetone again, and reprecipitated twice for purification. The obtained polyarylate has a glass transition temperature of 30
The decomposition temperature was 505°C. Polyarylate 0.
5 g was dissolved in a mixed solution of tetrachloroethane-phenol (4:8) 100° C., and the intrinsic viscosity (ηinh) measured at 30° C. was 1.31 a/g.

The obtained polyarylate was dissolved in N-methylpyrrolidone and then sulfur-rolled onto a glass plate to obtain a colorless and transparent film. The tensile strength of the film was 19.8 kg/intestine II2.

In addition, the obtained polyarylate contains chloroform, 1.
It was completely dissolved in halogenated solvents such as 2-dichloroethane and 1,1,2.2-tetrachloroethane, and in solvents such as dimethylformamide, dimethylacetamide, dimethylsulfoxide, and tetrahydrofuran.

Examples 2 to 5 The reaction was carried out in exactly the same manner as in Example 1 except that the terephthalic acid chloride and isophthalic acid chloride used were changed as shown in Table 1. The obtained polyarylate also has first-class physical properties.
Shown in the table. Further, the solvent solubility was also the same as in Example 1.

Table 1 Example 6 In Example 1, instead of using terephthalic acid chloride and isophthalic acid chloride, 2.1 g of only terephthalic acid chloride was used. Further, the reaction time was set to within 2 hours. The other reactions were carried out in the same manner. The glass transition temperature of the obtained polyarylate was 308°C, the thermal decomposition temperature was 505°C,
Further, the intrinsic viscosity (ηinh) was 1.39 du/g. In addition, the tensile strength after film formation is 15.8 kgf.
/am2. Solvent solubility was the same as in Example 1.

Effects of the Invention The present invention provides a method for producing a new polyarylate that is highly heat resistant and soluble, and also has high strength film-forming performance.The polyarylate has excellent thermal properties similar to polyimide. Moreover, since it can provide a transparent and colorless film, it is widely used in industry, especially in the electrical and electronic sectors.

Furthermore, the polyarylate of the present invention not only exhibits physical properties equivalent to the only polyimide film with excellent high-temperature physical properties, but also
It improves some of the disadvantages of polyimide in terms of processing by imparting solubility in organic/\logenic solvents for ease of processability.

Claims (1)

[Claims] using substantially equimolar amounts of at least one of a terephthalic acid chloride derivative and an isophthalic acid chloride derivative and 9,9-bis(4-hydroxyphenyl)fluorenes,
When performing solution polymerization in 1,2-dichloroethane, a solution of an acid chloride derivative dissolved in 1,2-dichloroethane is prepared in advance, and 9,9-dichloroethane is dissolved in 1,2-dichloroethane.
-50 bis(4-hydroxyphenyl)fluorenes
9 obtained by dissolving in a temperature range of ℃ or higher and lower than the boiling point of the solvent.
, 9-bis(4-hydroxyphenyl)fluorenes was gradually added to the solution of the acid chloride derivative without cooling and polymerized to give an inherent viscosity of 0.7 d.
A method for producing a soluble heat-resistant polyarylate, characterized in that the polyarylate is 1/g or more.