JPS6116924A - Heat-resistant copolyarylate - Google Patents

Abstract

PURPOSE:A phosphorus-containing copolyarylate that is obtained from a phosphorus-containing aromatic diol, bisphenol-A, isophthalic acid and so on, thus showing high heat resistance, flame retardation, clearity and color tone with a specifically repeated structural unit and a specific average polymerization degree. CONSTITUTION:The objective copolyarylate contains structural units of formula I (R1, R2 are H, halogen, 1-8C alkyl; n<1>, n<2> are 1-4) and formula II at a molar ratio of 99/1-1/99 linearly and randomly and has an average polymerization degree of 10-300. For example, the polycondensation between isophthalic acid, a carboxylic acid ester derivative of phosphinic acid having aromatic diol groups of formula III, and a carboxylic ester of bisphenol-A of formula IV is effected at elevated temperatures under high vacuum to go give the objective copolyarylate.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a novel copolyarylate with excellent heat resistance. More specifically, the present invention relates to a novel copolyarylate with excellent heat resistance and flame retardancy obtained from an aromatic diol containing a phosphorus atom, bisphenol A, and isophthalic acid.

BACKGROUND OF THE INVENTION Polyarylates have been known as heat-resistant polymers. For example, 4-hydroxybenzoic acid homopolymer and 4-hydroxybenzoic acid copolymer (Sumitomo Chemical, trade name Econol),
Alternatively, Polymer (Unitika, trade name: U polymer) consisting of bisphenol A, terephthalic acid and isophthalic acid was proposed and is now commercially available.

Such polymers have a relatively high melting point or a decomposition temperature below the melting or softening point.

Poor moldability.

(2) Poor color tone.

(3) Poor transparency.

(4) Heat resistance is insufficient.

(5) Poor flame retardancy.

It had such drawbacks.

The problem that the invention aims to solve The main object of the present invention is to provide a plasma spray coating.

The purpose of the present invention is to provide a heat-resistant copolyarylate that is particularly suitable for molded products used at high temperatures and has good heat resistance.

Moreover, it also had a high degree of flame retardancy. An object of the present invention is to provide a new heat-resistant copolyarylate.

The present inventors have conducted intensive research into a new heat-resistant copolyarylate that does not have the above-mentioned problems.

The inventors of the present invention have discovered that phosphorus-containing polyarylates having repeating units having the structure described above have extremely excellent properties.

Means to solve problems The present invention has a 9-order configuration.

That is, the present invention mainly consists of structural units represented by the following structural formulas (I) and (n), and (I) and (n) are 9
They were arranged irregularly in a linear manner at a molar ratio of 9:1 to 1:99.

It is a heat-resistant copolyarylate having an average degree of polymerization of 10 to 300.

(However, R1 and R2 are the same or different groups,
Each of them is selected from a hydrogen atom, a halogen atom, and a lower alkyl group having 1 to 8 carbon atoms. Also, nt
, fi2 each represent an integer from 1 to 4. ) CI (3 Action) The heat-resistant copolyarylate of the present invention is composed of isophthalic acid (hereinafter abbreviated as IPA) or its ester-forming derivative and phosphinic acid (hereinafter referred to as P-H) having an aromatic diol group.
It can be produced by utilizing various ester-forming methods in which bisphenol A (hereinafter abbreviated as BA) or an ester-forming derivative thereof is reacted with bisphenol A (hereinafter abbreviated as BA) or an ester-forming derivative thereof.

Examples of ester-forming derivatives of IPA include isophthalic acid dialkyl ester, isophthalic acid diaryl ester, and isophthalic acid civalide.

Examples of ester-forming derivatives of P-HCA or BA include derivatives having a diacyloxy group or a dialkali metal oxy group.

The copolyarylate of the present invention may be produced by mixing the above raw materials from the raw material stage to produce a copolymer, or the above structural unit (I) (hereinafter abbreviated as HCA to IPA) and the structural unit (■) (hereinafter It can also be produced by melt-mixing homopolymers consisting of (abbreviated as BA to IPA).

The structural formulas of P-HCA and BA referred to in the present invention are shown in column (i) and column.

0=P-0(I)H3 As an economically preferable example for obtaining the copolyarylate of the present invention, IPA and a carboxylic acid ester derivative of HCA represented by the following formula M (abbreviated as p-HCA-2A) and the following One example is a method of condensing BA with a carboxylic acid ester derivative represented by formula (2) (abbreviated as BA-2A) at high temperature and under reduced pressure.Hereinafter, the production method of the present invention will be explained in detail according to this method. .

0 CH30 (However, R is the same or different group, each being a lower alkyl group having 1 to 8 carbon atoms.) In addition, p-HC
A-2A and B A-2A are each represented by the above formula (I
), (IV) can be produced by esterifying HCA and BA shown in the corresponding carboxylic acid anhydride (eg, acetic anhydride) under reflux. At this time, IPA may be present, and the process may then proceed to the polyarylate production step.

On the other hand, P-HCA can be produced by reacting a phosphinic acid represented by the following formula (1) with p-benzoquinone in a suitable solvent such as ethyl cellosolve.

When producing copolyarylate by mixing the three at the raw material stage, IPA, P-HCA-2A and BA-2A
The molar ratio of the sum of these is usually 0.8 to 1.2. Preferably 0.9
~1,1. Equimolar amounts are optimally preferred.

In addition, a catalyst is usually used in the linear combination reaction.

In order to obtain the copolyarylate of the present invention, for example,
One or more compounds selected from various metal compounds or organic sulfosic acid compounds can be used.

Such metal compounds include antimony, titanium, kermanium, tin, zinc, and aluminum.

Compounds such as magnesium, calcium, manganese or cobalt are used, while compounds such as sulfosalicylic acid and 0-sulfobenzoic anhydride are used as the organic sulfonic acid compound.

Dimethyltin malate (hereinafter abbreviated as C8) is particularly preferably used. The amount of the catalyst added is usually 1x10-5 to 1x per mole of the polyarylate structural unit.
162 mol, preferably 5 x 10 to 5 x 10 mol, optimally 1 x 10 to 1 x 10 mol are used.

In addition, the temperature conditions and reaction time of the condensation reaction are usually 180 to 40 hours under normal pressure (4 to 12 hours on PC, especially 250 hours).
~360°C for 6-10 hours, optimally 280-320°C
It is preferable to set it as 8 to 10 hours.

Further under reduced pressure (usually 0.01 to 10 torr) 1
80-400℃ for 1-10 hours, especially 250-360℃
C. for 2 to 8 hours, optimally 280 to 340.degree. C. for 4 to 6 hours.

Here, the range of the molar ratio of P-HCA:F3A is.

99:1-1:99. Preferably 80:20-40
:60, optimally 80:20 to 60:40.

When HCA p content increases, strength 2 elasticity decreases and B
A If the acid component increases, transparency may deteriorate.

It is not preferable because it has poor flame retardancy.

On the other hand, the copolyarylate of the present invention can also be obtained by melt mixing HCA-IPA and BA-IPA. The mixing conditions for HCA-IPA and BA-IPA in the present invention are 0.1 to 2 hours at 180 to 400°C under normal pressure, preferably 02 to 1 hour at 250 to 360°C.

Furthermore, if necessary, under reduced pressure (usually 0.01 to 10 to
rr) The reaction may be carried out at 180 to 400°C to achieve a predetermined degree of polymerization.

The average degree of polymerization (n) of the heat-resistant copolyarylate of the present invention is 10 to 300. Preferably 30-200. Optimally 5
Must be between 0 and 150. The average degree of polymerization.

If it is less than 10, various physical, mechanical and chemical property values including the heat resistance described above will be poor.

On the other hand, if the average degree of polymerization is greater than 300, the melt viscosity will become too high and moldability, fluidity, etc. will be impaired.

effect According to the invention.

(I) No decomposition occurs even when used at high temperatures.

(2) Preferred glass transition temperature range (I50-230℃
) and within the preferred melting point temperature range (280 to 420°C), and has excellent heat resistance.

(3) Excellent color tone and transparency.

(4) Excellent flame retardancy.

A new copolyarylate having excellent physical properties as a heat-resistant polymer can be obtained. Also.

The copolyarylate of the present invention is particularly suitable for films and fibers used in applications requiring heat resistance and flame retardancy.

Useful as a molding material.

Example Hereinafter, the present invention will be explained in more detail using Examples.

Note that the average degree of polymerization of the polymer referred to in the present invention is:

The number average molecular weight measured at a temperature of 39°C using a chloroform solution containing 2.5 units of hexafluoroisopropanol as a solvent using Kel permeation chromatography (Model HLC801A manufactured by Toyo Soda Co., Ltd.) is expressed as the molecular weight of the repeating unit. It was found by dividing.

Further, the glass transition temperature and melting point were measured using a differential calorimeter (Model DSC-2, manufactured by PerkinElmer).

On the other hand, one copolyarylate of the present invention was identified by infrared absorption spectrum, NMR spectrum, glass transition temperature, and elemental analysis.

Reference Example 1 p-HCA represented by the above formula (Ill') was produced by reacting the phosphinic acid represented by the above formula glaze with p-benzoquinone at a temperature of 90°C in an ethyl selonp solvent.
was manufactured.

This p-HCA and acetic anhydride are charged into an esterification reactor at a molar ratio of 1:40, and esterified under reflux in acetic anhydride to produce diacetate, that is, p-HCA and acetic anhydride.
CA-2A was manufactured.

Condensation reactor [p-HCA-2A and IPA in a molar ratio of 1]
Dimethyltin maleate (C8) was added as a catalyst at a ratio of 10 to
0'' mole of Xl was added and reacted under nitrogen atmosphere at normal pressure at 280° C. for 8 hours with mixing.

Based on the weight of distilled acetic acid, the esterification reaction rate was approximately 93%.

This reaction product was further heated at 280°C under a reduced pressure of 0.1 torr.
Finally, the temperature was raised to 340°C and condensation was carried out for a total of 10 hours to obtain polyarylate of HCA-IPA.

In addition, during the reduced pressure reaction, p-I (CA-2A, etc.) of the raw material.

No sublimation of IPA was observed.

Infrared absorption spectrum of this polyarylate.

When analyzed by NMR spectrum and elemental analysis, the following results were obtained.

That is, in the infrared absorption spectrum, the absorption based on C=0 of the aromatic carboxylic acid ester is at 1780k.
736, 781k K para-substituted aromatic absorption.

An asymmetric trisubstituted aromatic absorption was observed at 878k.

In addition, in the NMR spectrum, the absorption of hydrogen atoms of methyl groups based on the raw material acetate (I, 5 ppm and 2.3
p, pm) were not observed.

In the results of elemental analysis, C = 68.6% (theoretical value 68.7 coefficient), H = 3.37 coefficient (theoretical value 3.33 coefficient),
The result was P=6.79Li6 (theoretical value 6.82%).

Reference Example 2 A diacetate ester, i.e., 13A-2A, was prepared by charging BA represented by the above formula (1) and acetic anhydride in an esterification reactor at a molar ratio of 1:4, and esterifying the mixture under reflux in acetic anhydride. Manufactured.

Condensation reactor ICBA-2A and IPA were charged at a molar ratio of 1:1, and dimethyltin malate (
C8) per mole of polyarylate structural unit, lX
10 mol was added and reacted under nitrogen atmosphere at normal pressure at 280C for 8 hours with mixing.

Based on the weight of distilled acetic acid, the esterification reaction rate is approximately 95%.
Met.

This solid reactant was further subjected to a solid phase reaction at 280°C under a reduced pressure of 0.1 torr, and finally the temperature was raised to 300°C and condensed for a total of 10 hours to obtain polyarylates of BA to IPA. .

It should be noted that no sublimation of raw material BA-2A or IPA was observed during the reduced pressure reaction.

Example 1 HCA-IPA and B obtained in Reference Example 1 and Reference Example 2
The polyarylate of A-7IPA was charged into a condensation reactor at a molar ratio of 1:1, and mixed for 1 hour at 280° C. under a nitrogen atmosphere at normal pressure.

This reaction product was further heated at 300°C under a reduced pressure of 0.1 torr.
The reaction was carried out at a final K of 320°C and then
The copolyarylate was mixed for a total of 2 hours and the results listed in Table 1 were obtained.

It was confirmed that this copolyarylate had the following structural formula units in a composition ratio of 1:1 based on the area ratio of methyl group protons to aromatic ring protons in its NMR spectrum.

In addition, the obtained polymer was molded into a string shape at 300C, and when the string was ignited and the fire source was moved away, the fire immediately extinguished, indicating that it had good flame retardant performance. In addition, when observed in a transparent state, one color tone was slightly yellow, and the transparency was extremely good.

Examples 2 to 7 Experiments were carried out in the same manner as in Example 1, except that the molar ratios of HCA-IPA and BA to IPA were changed as shown in Table 1.
The results listed in Table 1 were obtained.

In addition, the polymers obtained in Examples 2, 3, and 7 were
At 0°C, the polymers obtained in Examples 4 to 6 were molded into a string shape at 350°C, and when the string was ignited and the fire source was moved away, it immediately extinguished and had good flame retardant performance. I understand.

In addition, when observed in a transparent state, the color tone was light brown-yellow, and the transparency was extremely good.

When the average degree of polymerization of the polymers of Examples 4 to 6 was measured after being molded into a string shape, n = 79.81°80, respectively.
Almost no thermal decomposition occurred.

Table 1 * Became an amorphous polymer.

Reference Examples 1 and 2 As reference examples, the characteristic values of polyethylene terephthalate and U polymer (Unitika, trade name U-100) are shown in Table 2.

Polyethylene terephthalate has nine colors and good transparency, but once the tegus was ignited, it continued to burn until it burned out even if the fire source was moved away. Further, it can be seen that the Tg is lower than that of the polymer of the present invention, and the heat resistance is inferior.

In addition, U-polymer has a brown color, and if you ignite the tegus and move the fire source away, it will continue to burn for several seconds.

It can be seen that the flame retardance is slightly inferior to that of the polymer of the present invention.

In addition, Econol (Sumitomo Chemical, trade name E2000')
Although it has excellent heat resistance with a heat distortion temperature of 293C, it continues to burn for several seconds when ignited, indicating that its flame retardance is slightly inferior to that of the polymer of the present invention.

Table 2

Claims (1)

[Claims] Consists mainly of structural units represented by the following structural formulas (I) and (II), in which (I) and (II) are 99:1 to 1:99.
average degree of polymerization 10~
300 heat-resistant copolyarylate. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I) (However, R1 and R2 are the same or different groups, each selected from a hydrogen atom, a halogen atom, and a lower alkyl group having 1 to 8 carbon atoms. Also, n1, n2
each represents an integer from 1 to 4. ) ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼ (II)