JPH02274725A - Heat-resistant polyester resin - Google Patents

Abstract

PURPOSE:To obtain a heat-resistant polyester resin improved in moldability by reacting a diol component with a mixed acid component comprising a diphenyl ether dicarboxylic acid and an aliphatic acid. CONSTITUTION:A diphenyl ether dicarboxylic acid of formula I (wherein R1-4 are each H or a 1 to 4C lower alkyl) is polycondensed with a mixed acid component comprising diphenyl ether dicarboxylic acid (e.g. diphenyl ether 4,4'- dicarboxylic acid) and an aliphatic acid (e.g. adipic acid) in a molar ratio of 1/99 to 99/1 at 20 to 80 deg.C for 2 to 6hr by interfacial polycondensation or solution polycondensation to obtain a heat-resistant polyester resin having a structure of formula II (wherein R is formula III; Y is IV; Z is formula V; (k) is 2-8; and (m) is the number of repeating units), a molar ratio of component Y to component Z of 1/99 to 99/1, and an inherent viscosity >=0.50dl/g.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a novel heat-resistant polyester resin with excellent moldability.

[Conventional technology]

Various polyesters made from 9.9-bis(4-hydroxyphenyl)fluorene have been proposed.

For example, polyesters obtained by polycondensation of 9.9-bis(4-hydroxyphenyl)fluorene and various acid chlorides have the following properties:
．． 536 (1970), and also contains 9°9-bis(4-hydroxyphenyl)fluorene and a terephthaloyl chloride-isophthaloyl chloride mixture (7:3 to
The copolymerized polyester with
It is disclosed in Japanese Patent No. 432.

Furthermore, single polyesters of 9,9-bis(4-hydroxyphenyl)fluorene and isophthaloyl chloride or fatty acid chloride, copolymerized polyesters with a mixture (2:8) of terephthaloyl chloride and isophthaloyl chloride, and polyesters copolymerized with a mixture (2:8) of terephthaloyl chloride and fatty acid chloride. Polyesters copolymerized with mixtures of chlorides are disclosed in US Pat. No. 3,546,165.

However, there is no description in the report regarding the moldability of the polyester.

The present inventors tried again to synthesize these polyesters,
The moldability was investigated.

As a result, it was found that these polyesters have drawbacks such as a small difference between the glass transition temperature and the thermal decomposition start temperature and a high melt viscosity, and thermal decomposition starts at the moldable temperature. Therefore, it is extremely difficult to obtain a molded product using these polyesters alone, and conventionally it has been necessary to blend them with other polymers and mold them.

For example, in JP-A-63-63718, a copolymerized polyester of 9,9-bis(4-human+:rcol-diphenyl)fluorene and a terephthalic acid isophthalic acid mixture (1:9 to 9:1) is disclosed. and hisphenol A polycarbonate=1 or polystyrene, and it is said that it can be molded by injection molding, extrusion molding, compression molding, etc.

[Problem to be solved by the invention]

As mentioned above, it has conventionally been difficult to mold polyester using 9,9-his(4-hydroxyphenyl)fluorene alone. The object of the present invention is to solve this problem and provide a one-heat polyester that has poor moldability.

[Failure to solve the problem]

The present invention relates to the formula -(X-Y-)ii-(X-Z-)-
i (However, in the formula, X is a molar ratio of l/99 to 99/
1.

The diols used in the present invention are represented by the following formula.

Z is -QC(CIl□)kCO-1 R,, R2, R3 and R4 each independently represent hydrogen or a lower alkyl group having 1 to 4 carbon atoms, k is an integer of 2 to 8, and m
, n indicates the number of repetitions), the molar ratio of the Y component to the Z component is 1/99 to 99/1, and the inherent viscosity is at least 0.50 a/g or more. Polyester resin.

The polyester of the present invention contains a diol component and a mixed acid component of diphenyl ether dicarboxylic acids and fatty acids. .9-bis(4-hydroxyphenyl)fluorene,
Examples include 9,9-bis(3,5-dimethyl-4-hydroxyphenyl)fluorene and 9,9-bis(3,5-diethyl4-hydroxyphenyl)fluorene.

When an alkyl group having 5 or more carbon atoms is introduced as R1-R4, the polymerizability is significantly lowered and a high molecular weight polymer cannot be obtained.

Examples of the fatty acid of the carboxylic acid component include adipic acid, sebacic acid, succinic acid, and superic acid, of which adipic acid is most suitable. This is because if the fatty chain is too long, the glass transition temperature will be low, but at the same time the thermal decomposition temperature will be too low, making molding difficult. Therefore -〇C(CI
+□), The k of CO- is preferably in the range of 2 to 8, and among these, adipic acid with -4 is optimal.

Examples of carboxylic acid components copolymerized with bilayer fatty acids include diphenyl ether-4,4'-dicarboxylic acid, diphenyl:[-thyl-3,4'-dicarboxylic acid, diphenyl ether-3,3'-dicarboxylic acid, etc. It will be done. Among these, diphenylether-4,4'-dicarboxylic acid is most suitable in consideration of the balance between moldability and heat resistance of the resulting polymer.

When these diphenyl ether dicarboxylic acids are used, compared to the use of other dicarboxylic acids such as terephthalic acid and isophthalic acid, the thermal properties are not much different, but the melt viscosity is considerably lower, so the molding temperature can be lowered. Can be set.

The copolymerization ratio of diphenyl ether dicarboxylic acids and fatty acids can be freely changed within the range of 1/99 to 99/1, but considering the injection moldability of the obtained polymer, it is 1/99 to 60.
/40 range is preferred. Details will be described later.

The degree of polymerization of the obtained polymer was evaluated by inherent viscosity. Inherent viscosity is 60% by weight of 0.5g of polymer
of phenol and 40% by weight of 112,2-tetrac+:ru:r-tane.

The measurement was carried out at 30°C on a solution dissolved in water.

The inherent viscosity of the polyester in the present invention can be freely controlled within the range of 0.20 to 2.00 a/g by changing the reaction time, but considering the mechanical properties of the molded product, the inherent viscosity of the polyester may be 0.50 dl/g or more. Preferably.

Furthermore, if the degree of polymerization is too large, the melt viscosity will increase and the injection moldability will decrease, so the preferred range of Inhesin 1 to viscosity is 0.50 to 1.50 d/g.

FIG. 1 is a graph showing an example of the results of thermal analysis of the polyester of the present invention. , and the glass transition temperature A and thermal decomposition temperature B are shown.

As shown in the drawings, the glass transition temperature (T9) of the polyester of the present invention ranges from 170 to 31 depending on the molar ratio of the mixed acid component.
It changes almost linearly between 0"C. Also, the thermal decomposition temperature (
Td) remains almost constant at 380°C during that time. Generally, for injection moldable resins, the difference between T9 and Td is 150°
It is said that a grade of C or higher is required. Therefore, compression molding is possible within the above molar ratio range, but injection molding is more preferably a molar ratio of 1/99 to 60/40.

Next, the method for producing the polyester resin of the present invention will be explained. The method for producing the polyester resin of the present invention includes:
Both interfacial polycondensation and solution polycondensation can be applied. In the case of interfacial polycondensation, diols serving as raw materials are dissolved in an alkaline aqueous solution to obtain a diol alkali aqueous solution. Although there are no particular restrictions on the alkali, it is preferable to use mono-lithium hydroxide, potassium hydroxide, and the like. When the concentration of the alkaline aqueous solution is 2.0% by weight or less, preferably about 0.8 to 1.5% by weight, a high molecular weight polymer is easily produced. The concentration of diols in the alkaline aqueous solution is usually 1.0 to 25.
0% by weight, more preferably 2.0 to 10.0% by weight. The molar ratio of alkali and diol hydroxyl group is 1:1 ~
It can vary within a wide range up to 4:1, but is preferably 1:1 to 2:1.

As the acid component, chloride of each carboxylic acid is preferably used. This acid chloride can be dissolved in an organic solvent immiscible with water, such as 1,2-dichloroethane, chloroform, trichloroethane, etc., and used as an acid chloride organic solvent solution.

The concentration of acid chloride in the organic solvent solution is 2.0 to 25.0
% by weight, more preferably 3.0 to 15.0% by weight.

Next, the diol alkali aqueous solution and the acid component organic solvent solution are mixed with stirring to effect interfacial polycondensation. Interfacial polycondensation is preferable because the reaction occurs at the interface between the aqueous phase and the organic phase, and adding a surfactant in an amount that does not cause emulsification accelerates the reaction. As the surfactant, it is preferable to use a surfactant that is resistant to alkali since it does not react with the diols or acid chloroforms that are the raw materials and is added to the alkaline aqueous solution.

Specific examples include trimethylhensylammonium chloride, triethylbenzylammonium chloride, trimethylcetylammonium bromide, and the like.

The concentration of these surfactants in an alkaline aqueous solution is 0.
5-10.0% by weight, preferably 1.0-5.0% by weight
It is.

The reaction temperature is not strictly limited, but -20 to 80°C
The temperature range is preferably 5 to 40°C, and more preferably 5 to 40°C.

A reaction time of 2 hours to about 6 hours at the most is sufficient.

After the reaction is completed, the reaction mixture is separated into, for example, an aqueous layer and an organic layer, and the organic layer is diluted with the same solvent to lower its viscosity and washed with water. Next, the polyester of the present invention can be obtained by pouring this solution into methanol or acetone, filtering off the precipitate, and drying.

In the case of solution polycondensation, diols and carboxylic acid chlorides as raw materials are combined with diols such as 1,2-dichloroethane, chloroform, trichloroethane, etc. Polycondensation can be carried out by mixing equimolar proportions in a solvent and stirring every 1 to 3 hours. This is usually carried out in the presence of a base, such as 1-ethylamine, which neutralizes the hydrogen chloride formed.

The concentration of diols and acid chlorides in a solvent is usually 1
．． 0 to 25.0% by weight, more preferably 2.0 to 10.
It is 0% by weight.

After completion of the reaction, the polyester of the present invention can be obtained by pouring the reaction mixture into, for example, methanol or acetone, filtering off the precipitate, and drying.

The present invention will be explained in more detail below with reference to Examples, but it goes without saying that the technical scope of the present invention is not limited to these Examples.

〔Example〕

(4-hydroxyphenyl)fluorene at 17.5 times
fi part, benzyltriethylammonium chloride 7.5
Parts by weight, 8.0 parts by weight of N a OI+, 60 parts by weight of distilled water
0 parts by weight was added and heated while stirring to dissolve the solid content.

7.3 parts by weight of adipic acid chloride, diphenyl ether
2.95 parts by weight of 4,4'-dicarboxylic acid chloride was added to 1,
It was dissolved in 190 parts by weight of 2-dichloroethane. This solution was poured into the aforementioned reaction container (three-lough flask), stirred vigorously for 2 hours, and then allowed to stand for a while.

Water in the upper layer was separated by gradient, and the lower layer (organic layer) was washed twice with water. This was poured into 4 to 6 times the amount of methanol in a high speed mixer to precipitate the polymer.

The obtained polymer was separated by suction filtration and dried under reduced pressure.

The yield was 92%, and the yield was measured at 30"C of a solution of 0.5 g of the obtained polymer dissolved in 100++4+ of a mixture of 60% by weight phenol and 40% by weight 1,1°2,2-tetrachloroethane. Hesin 1 - viscosity is 0.80d
It was l/g.

17.5 parts by weight of 9,9-bis(4-hydroxyphenyl)fluorene, 1,
190 parts by weight of 2-dichloroethane, 1 part by weight of triethylamine
2.0 parts by weight was added and heated while stirring to melt the solid content.

7.3 parts by weight of adipic acid chloride and 2.95 parts by weight of diphenyl ether-4,4'-dicarboxylic acid chloride were added, and the mixture was stirred at room temperature for 2 hours. The reaction mixture was poured into 4 to 6 times the amount of methanol in a high-speed mixer to precipitate the polymer. The polymer was filtered off with suction and dried under reduced pressure.

The yield was 91%, and the inherent viscosity was 0.75 a/g.

The physical properties of the obtained polymer were almost the same as in Example 1.

Tianshihua J- Diphenyl ether-4,4'-dicarboxylic acid 1:J
The molar ratio of sulfur and adipic acid r:l is 1/99.4.
0/60, 60/40, 80/20, 99/1
Synthesis was performed in the same manner as on the actual flow side 1, with the following changes. The yield is over 90% in all cases, and the inherent viscosity is 0.6.
It was 0 to 1.50.

Monthly total 14 - Instead of adipic acid chloride 1 in Example 1, sebacic acid chloride', succinic acid chloride, glutaric acid 1:
Synthesis was carried out in the same manner as in Example 1, using 6.35, 6.90, 8.05, and 8.60 parts by weight of 1:), pimelic acid chloride, and 1:) chloride, respectively.

The yield was 90% or higher in all cases, and the viscosity was 0.
It was 60-0.80a/g.

The physical properties of the obtained polyester were measured by the following method. The measurement results of physical properties are summarized in Table 1.

1. Tensile strength...Autograph NSS 2000
<Shimadzu Corporation) medium 1On+n+, length 100
+nm film was measured.

2. Tensile modulus... Same as above (3. Tensile elongation at break... Same as above 4. Soldering heat resistance... Measured according to JIS C6482.

5. Coefficient of linear expansion: Measured using a thermomechanical analyzer TMA 30 type (Shimadzu Corporation).

6. Volume resistivity Measured according to JIS C2318 using tin foil attached to the film as an electrode.

(2) Dielectric constant, dielectric loss tangent...8, Dielectric breakdown strength...Measured in accordance with JIS C2110.

9. Water absorption rate: After drying at 120'C for 10 hours or more, it was immersed in distilled water at 23°C for 2/1 hour to measure 1ζ.

10. Light transmittance: Measured according to JIS K7105.

11. Yellowness: Measured according to JIS K7103.

The resulting polyester was applicable to various molding methods such as injection, compression, and extrusion.

Table 2 shows the mechanical properties of the compression molded product. Compression molding is 2
Preheat at 80°C (+Iif heating for 4 minutes, same temperature, 200kg
This was done by applying pressure at f/C16 for 2 minutes.

〔Effect of the invention〕

The present invention is a heat-resistant polyester having a glass transition temperature of 170 to 310°C, a tensile strength of <g/mm2 or higher (film physical properties), and an inherent viscosity of 0.5 dl/g or higher, which cannot be processed by conventional molding. This is an epoch-making material that has made it possible to mold polyester, which was previously thought to be difficult.

Fields of its use include various mechanical parts, electrical parts, etc., but because it has a high refractive index and transparency, it can be used in various optical materials and is extremely meaningful industrially.

[Brief explanation of drawings]

FIG. 1 is a graph showing the relationship between the molar ratio of diphenyl ether-4,4'-dicarphonic acid chloride and adipic acid chloride, the glass transition temperature Δ, and the thermal decomposition temperature I3, as determined by thermal analysis of the polyester of the present invention.

Claims (1)

[Claims] 1. Formula -(X-Y)-_m-(X-Z)-_n (wherein X is ▲a mathematical formula, chemical formula, table, etc.▼Y is ▲a mathematical formula, a chemical formula, a table, etc.) etc. ▼, Z is -OC(CH_2)_kCO-, R_1, R_2, R_3 and R_4 each independently represent hydrogen or a lower alkyl group having 1 to 4 carbon atoms, k is an integer of 2 to 8, m, n indicates the number of repetitions), the molar ratio of the Y component and the Z component is 1/99 to 99/1,
A heat-resistant polyester resin having an isoherent viscosity of at least 0.50 dl/g. 2. The heat-resistant polyester resin according to claim 1, wherein the Y component is ▲a mathematical formula, a chemical formula, a table, etc.▼. 3. The heat-resistant polyester resin according to claim 1, wherein the Y component is ▲a numerical formula, a chemical formula, a table, etc.▼, and the Z component is -OC(CH_2)_4CO-. 4. The heat-resistant polyester resin according to claim 1, which is used for injection molding at a molar ratio of Y component to Z component of 1/99 to 60/40.