JPH03115324A - Amorphous polyarylate - Google Patents

Abstract

PURPOSE:To obtain an amorphous polyarylate having a high glass transition temperature and excellent heat resistance and moldability without detriment to its film-forming properties, transparency, dimensional stability, etc., by combining specified repeating structural units. CONSTITUTION:The purpose polyarylate comprises repeating structural units of formula I (wherein R and R' are each a 1-4C monovalent aliphatic hydrocarbon group; n is 0-2; and Ar is a bivalent aromatic group of any one of formulas II-VI). It can be formed by polycondensing a compound of formula VII with a compound of formula VIII.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a non-grade polyarylate which has excellent heat resistance and good moldability.

[Prior Art] Several non-grade polyarylates are already known. A non-grade polyarylate obtained by polycondensation of bisphenol-A and terephthalic acid dichloride (for example, U polymer manufactured by Unitika) has a glass transition temperature of 19
3°C1 It is known to have excellent flame retardancy, mechanical properties, and transparency.

Furthermore, polyarylate known under the trade name of Durel@ (manufactured by Celanese) is also known to have a heat distortion temperature of 171°C. Furthermore, Japanese Patent Application Laid-Open No. 57-73021
A polyarylate having a repeating structural unit (for example,
NAP resin manufactured by Kanebuchi Chemical Co., Ltd.) has a glass transition temperature of 184~
It is known to have a melting point of 280-320°C.

[Problems to be solved by the invention] Non-grade polyarylates have excellent molding processability, film formability by solution casting, flame retardancy, dimensional stability, mechanical properties, etc., and also have excellent transparency. Although it is known that a film having good properties can be obtained, it has not yet achieved a satisfactory value in terms of heat resistance. Also, the above-mentioned Unexamined Patent Publication No. 57-7
The polyarylate described in 3021 publication may exhibit crystallinity depending on the combination of m and n, so
Although heat resistance is improved to some extent, it has the disadvantage that properties such as moldability, dimensional stability, and transparency are impaired.

The object of the present invention is to produce non-grade polyarylates with excellent heat resistance and a higher glass transition temperature without impairing the properties of conventional non-grade polyarylates such as film formability, transparency, and dimensional stability. The aim is to provide arylate.

[Means for Solving the Problems] The present inventors have continued research on non-grade polyarylates containing various biphenols. As a result, a non-grade polyarylate composed of biphenol into which a -valent aliphatic hydrocarbon group has been introduced as a side chain and a certain type of aromatic dicarboxylic acid dichloride has a high glass transition temperature, and It was discovered that this material exhibits good molding processability, and the present invention was completed.

That is, the present invention is a non-quality polyarylate consisting of a repeating structural unit represented by the following formula.

(wherein R and R' are each independently selected from monovalent aliphatic hydrocarbon radicals having 1 to 4 carbon atoms, and n is each independently selected from integers having a value of O to 2.

Ar is a divalent aromatic group independently selected from the group consisting of. ) The non-quality polyarylate of the present invention is the following compound (A)
It can be formed by subjecting (B) to a polycondensation reaction.

(wherein R and R' are each independently selected from monovalent aliphatic hydrocarbon groups having 1 to 4 carbon atoms, and n is each independently selected from an integer from O to 2. 3,3'-dimethyl-4,4'-biphenol, 3,3'-di- Butyl-4,4'-biphenol, 3,315.5'-tetramethyl-4,4'-biphenol, 3.3'-dimethyl-5,5'-di-t-butyl-4,4'-biphenol, 3. 3′,5.5′-tetra-L
-Butyl-4,4'-biphenol, 2,2'3.3
', 5.5'-hexamethyl-4,4'-biphenol, their sodium salts, potassium salts, etc. can be exemplified, and particularly preferred are 3,3'5.5'-tetramethyl-4, 4'-biphenol, 2.2'
, 3.3', 5.5-hexamethyl-4,4'
Biphenols are preferred.

Examples of the compound represented by (B) below include terephthalic acid dichloride, isophthalic acid dichloride, 3-mo-butyl isophthalic acid dichloride, 4-diphenyl ether dicarboxylic acid dichloride, 5-chlorocarbonyl-5-(4'-
Examples include chlorocarbonylphenyl)-1,1,3-trimethylphenylindan, particularly preferably 3
-t-Butyl isophthalic acid dichloride, 4-diphenyl ether dicarboxylic acid dichloride, 5-chlorocarbonyl-3-(4-chlorocarbonylphenyl) 1.1.3
-1-limethylphenylindane is preferred.

A preferred method for producing the non-grade polyarylate in the present invention is already known. ``Phase Tra'' by W. P. Weber and G. W. Gobel.
nsferCatalysis in Organic
5ynthesis, (Japanese translation, Kuchita et al. "Phase Transfer Catalyst", Kagaku Doujin), Japanese Patent Application Laid-Open No. 5773021,
It is formed by the phase transfer catalytic polycondensation method disclosed in JP-A-57-111317 and the like. This is a method in which aromatic dicarboxylic acid dichloride dissolved in an organic solvent that is incompatible with water and biphenol dissolved in an alkaline aqueous solution are mixed and reacted in the presence of a phase transfer catalyst.

The organic solvent incompatible with water used here is a solvent inert to the reaction, such as methylene chloride, chloroform, 1,2-dichloroethane, Syn+-tetrachloroethane, monochlorobenzene, orthodichlorobenzene, etc. Preferred examples include halogenated hydrocarbon solvents, aromatic hydrocarbon solvents such as benzene, toluene, and xylene, and organic solvents having polar groups that are inert to reactions such as anisole, acetophenone, benzonitrile, and nitrobenzene. is preferably a halogenated hydrocarbon solvent, particularly preferably methylene chloride.

As the phase transfer catalyst, oil-soluble quaternary ammonium,
Class phosphonium salts and crown ethers are used. Examples of oil-soluble quaternary ammonium salts include tetrabutylammonium chloride, benzyltrimethylammonium chloride, benzyltriethylammonium chloride, cetyltrimethylammonium chloride, benzyltributylammonium chloride, trioctylmethylammonium chloride, N-laurylpyridinium chloride, etc. Examples of class phosphonium salts include tetrabutylphosphonium bromide, triethyl octadecylphosphonium bromide, benzyltriphenylphosphonium chloride, and cetyltributylphosphonium bromide; crown ethers include
All substances that form complexes with alkali metal ions, such as 8-crown-6, dibenzo-18-crown-6, and dicyclohexyl-18-crown-6, and have the effect of activating the paired ferulate anion. Examples include, preferably, oil-soluble quaternary phesphonium salts, particularly preferably:
Cetyltributylphonium bromide is preferred. The amount of these catalysts is desirably in the range of 0.1 to 20 mol%, more preferably 5 to 15 mol%, based on the aromatic dicarboxylic acid dichloride used.

Examples of the alkaline aqueous solution include a sodium hydroxide aqueous solution and a potassium hydroxide aqueous solution, with a sodium hydroxide solution being preferred. The concentration of the alkaline aqueous solution is preferably in the range of 1 to 6 normal concentration.

The reaction temperature of the phase transfer catalytic polycondensation in the present invention is usually desirably in the range of 0 to 100°C, and the reaction time is 2 to 5
Time is enough.

In the case of the non-quality polyarylate of the present invention, although several methods are known for measuring its molecular weight, the precision and reproducibility of the measured values may not be good. Instead of the molecular weight of the obtained non-quality polyarylate, the intrinsic viscosity ηinh (described later) at a constant temperature was used as an expression of the size of the molecular chain of the solvent-soluble resin in the solvent.

A resin with a low intrinsic viscosity indicates that the size of the molecule in the solvent is small, that is, the resin has a small molecular weight. The intrinsic viscosity of the non-grade polyarylate of the present invention is 0.5 to 5dj2/
g, preferably 0.6 to 4 dl/g. If the intrinsic viscosity is less than 5 dffi/g, the molecular weight is low, the heat resistance is poor, and the physical properties of the molded product may be insufficient. Further, many of those having an intrinsic viscosity exceeding 5 dA/g are difficult to mold.

The non-quality polyarylate according to the present invention can be used by being formed into films or products having various shapes by methods such as melt molding or solution molding, and has excellent transparency, heat resistance, flame retardancy, etc. have

[Examples] Examples of the present invention will be shown below, but the present invention is not limited thereto. The physical properties in the examples were measured as follows.

Intrinsic viscosity: 0.5g of sample resin was dissolved in 20ml of N-methylpyrrolidone, 10mf of it was placed in an Ostwald viscometer, and immersed in a constant temperature bath adjusted to 30 + 0.5°C to reach a sufficiently constant temperature. After that, the falling time t between the viscometer gauge lines is measured. Pre-measured solvent only fall time.

The intrinsic viscosity η, , h was determined from the solution concentration C and the following formula.

η = nh = In(t/lo) / C Glass transition temperature: Using a differential scanning calorimeter DSC-41 manufactured by Shimadzu Corporation, a sample resin film 5 created by the solvent casting method was heated in nitrogen. The starting temperature of the change in heat amount was determined as the glass transition temperature from the thermogram obtained when heating at a rate of 10° C./min.

Heavy M'$, Small: Weight when a sample resin film 5 ■ made by solvent casting method is heated in air at a heating rate of 10°C/min using a thermobalance TGA-40 manufactured by Shimadzu Corporation ■. The changes over time were measured. Further, from this measured value, the temperature at which the weight decrease rate was 10% with respect to the original weight was determined.

Softening temperature: Using a thermomechanical analyzer TMA40 manufactured by Shimadzu Corporation, a sample resin film 3 m x 3 mm made by solvent casting method is heated at a heating rate of 10°C/min in nitrogen at a constant load. Changes in needle penetration at the bottom over time were measured. From this measurement result, the temperature at which rapid penetration started due to softening of the sample resin was determined as the softening temperature.

Example 1 Under a nitrogen atmosphere, 0.5 mmol of 3.3',5.5'-tetramethyl-4,4'-biphenol is dissolved in 10IIN of a 1N aqueous sodium hydroxide solution. To this, 3-t-butyl isophthalic acid dichloride 0
．． 5 mmol of methylene chloride (Qmj2) in which 0.06 mmol of cetyltributylphosphonium bromide, a phase transfer catalyst, was dissolved was immediately added and stirred at room temperature for 3 hours to react. The resulting reaction solution was poured into a hot dilute hydrochloric acid aqueous solution (1000 n+1) to precipitate the polymer.

A polymer with an intrinsic viscosity ηin = 0.72 dj2/g was obtained in a yield of 95%. This polymer is soluble in chloroform, methylene chloride, tetrahydrofuran, etc., and a transparent and tough film was obtained by solution casting. The glass transition temperature of the polymer is 253°C, the softening point is 265°C, and the temperature at which the weight decreases by 10% relative to the original weight is 365°C.
It was °C.

Example 2 3.3', 5.5'-tetramethyl-4.4'
-biphenol 0.5 mmol, 5-chlorocarbonyl-3-(4'-chlorocarbonylphenyl) -1,
0.5 mmol of 1,3-trimethylphenylindane was used in the reaction as in the example. Intrinsic viscosity η1nh
=0.45df/g@polymer was obtained, which was soluble in chloroform, methylene chloride, tetrahydrofuran, etc., and a transparent and tough film was obtained.

The glass transition temperature of the polymer is 288°C, the softening temperature is 29
At 0°C, the temperature at which a weight reduction rate of 10% with respect to the original weight was achieved was 385°C.

Example 3 3.3', 5.5'-tetramethyl-4,4'
The reaction was carried out as in Example 1 using 0.5 mmol of -biphenol and 0.5 mmol of 4-diphenyletherdicarboxylic acid dichloride. Intrinsic viscosity ηinh −2,8
4 df/g, o-ri o o 7 f-/L/, soluble in tetrachloroethane, etc., and a transparent and tough film was obtained. The softening temperature was 260°C, and the temperature showing a 110% weight loss rate was 390°C.

Example 4 2.2-3.3', 5.5'-hexamethyl-
The reaction was carried out as in the example using 0.5 mmol of 4,4'biphenol and 0.5 mmol of 3-t-butyl isophthalic acid dichloride. Intrinsic viscosity η,,,, =0.3
46i! , 7 g, soluble in chloroform, methylene chloride, tetrahydrofuran, etc., and a transparent and tough film was obtained. Glass transition temperature of 220″C, 10% of 385°C
The weight showed a change in temperature.

Example 5 2.2', 3.3', 5.5'-hexamethyl-4,4'-hyphenol 0.5 mmol, 5-
Chlorocarbonyl-3-(4'-10locarponylphenyl)1.1.3-1-dimethylphenylindan 0
．． 5mi 9 viscosity η+, 1h = 0. 9 6, Soluble in chloroform, methylene chloride, tetrahydrofuran, etc.
A transparent and tough film was obtained. Softening temperature 285°c
,i.

The temperature showing the weight loss rate of % was 360°C.

Claims (1)

[Claims] An amorphous polyarylate consisting of a repeating structural unit represented by the following formula. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R and R' are each independently selected from monovalent aliphatic hydrocarbon groups having 1 to 4 carbon atoms, and each n is a value of 0 to 2. are independently selected from the integers having . Ar is a divalent aromatic group and has ▲ mathematical formulas, chemical formulas, tables, etc.
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼
, ▲There are mathematical formulas, chemical formulas, tables, etc.▼ ▲There are mathematical formulas, chemical formulas, tables, etc.▼ Independently selected from the group consisting of. )