JPH045048B2 - - Google Patents

Description

[Detailed description of the invention]

INDUSTRIAL APPLICATION FIELD 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 ART Polyarylates have been known as heat-resistant polymers. For example, 4-hydroxybenzoic acid homopolymer or copolymer (Sumitomo Chemical, trade name Econol), or bisphenol A
A polymer consisting of terephthalic acid and isophthalic acid (Unitika, trade name U Polymer) was proposed in the past, and is now commercially available. Such polymers inherently have poor moldability because (1) they have relatively high melting points, and their decomposition temperatures are lower than their melting or softening points; (2) Poor color tone. (3) Poor transparency. (4) Insufficient heat resistance. (5) Poor flame retardancy. It had the following drawbacks. Problems to be Solved by the Invention The main purpose of the present invention is to provide plasma sprayed coatings,
The object of the present invention is to provide a heat-resistant copolyarylate that is particularly suitable for molded products used at high temperatures, and to provide a new heat-resistant copolyarylate that has good heat resistance and high flame retardancy. As a result of intensive research into new heat-resistant copolyarylates that do not have the above-mentioned problems, the present inventors discovered that phosphorus-containing polyarylates having repeating units with a specific structure have extremely excellent properties. Reached. Means for Solving the Problems The present invention has the following configuration. That is, the present invention mainly consists of structural units represented by the following structural formulas () and (),
It is a heat-resistant copolyarylate in which ( ) and ( ) are arranged irregularly in a linear manner in a molar ratio of 99:1 to 1:99, and has an average degree of polymerization of 10 to 300. (However, R ₁ and R ₂ are the same or different groups, each selected from a halogen atom and a lower alkyl group having 1 to 8 carbon atoms.
n ₁ and n ₂ each represent an integer from 0 to 4. ) Effect The heat-resistant copolyarylate of the present invention comprises isophthalic acid (hereinafter abbreviated as IPA) or its ester-forming derivative, and phosphinic acid having an aromatic diol group (hereinafter abbreviated as P-HCA) or its ester-forming derivative. , bisphenol A (hereinafter
(abbreviated as BA) or its ester-forming derivative using various ester-forming methods. Ester-forming derivatives of IPA include isophthalic acid dialkyl ester, isophthalic acid diaryl ester, isophthalic acid dihalide, while P
Examples of the ester-forming derivatives of -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 structural units () (hereinafter abbreviated as HCA to IPA) and the structural units () (hereinafter referred to as BA to IPA
It can also be produced by melt-mixing homopolymers consisting of (abbreviated as ). The structural formulas of P-HCA and BA referred to in the present invention are shown in () and (). As an economically preferable example for obtaining the copolyarylate of the present invention, IPA and a carboxylic acid ester derivative of HCA (p-
(abbreviated as HCA-2A) and the carboxylic acid ester derivative of BA (BA-2A) represented by the following formula ().
2A) under high temperature and high reduced pressure.The production method of the present invention will be described in detail below according to this method. (However, R is a group of the same kind or a different kind, and each is a lower alkyl group having 1 to 8 carbon atoms.) In addition, p-HCA-2A and BA-2A are the above-mentioned formulas () and (), respectively. HCA and
BA can be prepared by esterification under reflux in the corresponding carboxylic acid anhydride (eg acetic anhydride). At this time, IPA may be present, and the process may then proceed to the polyarylate production process. On the other hand, P-HCA can be produced by reacting phosphinic acid represented by the following formula () 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
The molar ratio of the sum of BA-2A is usually 0.8 to 1.2, preferably 0.9 to 1.1, and optimally equimolar. In addition, a catalyst is usually used in the condensation reaction, but
In order to obtain the copolyarylate of the present invention, for example, one or more compounds selected from various metal compounds or organic sulfonic acid compounds are used. Such metal compounds include antimony, titanium, germanium, tin, zinc, aluminum,
Compounds such as magnesium, calcium, manganese or cobalt are used, while organic sulfonic acid compounds include sulfosalicylic acid, o-
Compounds such as sulfobenzoic anhydride are used, but dimethyl tin malate (hereinafter abbreviated as CS)
is particularly preferably used. The amount of the catalyst added is usually 1 x 10 ^-5 to 1 x 10 ^-2 mol, preferably 5 x 10 ^-5 per mol of the structural unit of polyarylate.
~5×10 ⁻³ mol, optimally 1×10 ⁻⁴ to 1×10 ⁻³ mol is used. In addition, the temperature conditions and reaction time of the condensation reaction are usually 4 to 12 hours at 180 to 400°C under normal pressure, especially
Preferably, the temperature is 250-360°C for 6-10 hours, optimally 280-320°C for 8-10 hours. Further under reduced pressure (usually 0.01-10torr) 180-400℃
for 1 to 10 hours, especially at 250 to 360℃ for 2 to 8 hours,
Optimally, the temperature is preferably 280-340°C for 4-6 hours. Here, the range of molar ratio of P-HCA:BA is:
99:1 to 1:99, preferably 80:20 to 40:60, optimally 80:20 to 60:40. If the HCA component increases, the strength and elasticity will decrease, and if the BA component increases, the transparency will deteriorate and the flame retardance will deteriorate, which is not preferable. 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 0.2 to 1 hour at 250 to 360°C. Furthermore, if necessary, under reduced pressure (usually 0.01 ~
10 torr) 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 must be 10-300, preferably 30-200, optimally 50-150. Average degree of polymerization is 10
If it is smaller, various physical, mechanical, and chemical property values including the heat resistance described above will be inferior. 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. Effects According to the present invention: (1) Decomposition does not occur even when used at high temperatures. (2) Preferred glass transition temperature range (150-230℃)
It falls within the preferred melting point temperature range (280-420°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. In addition, the copolyarylate of the present invention has particularly high heat resistance,
Films used for applications requiring flame retardancy,
Useful as fiber and molding material. Examples Hereinafter, the present invention will be explained in more detail using examples. In addition, the average degree of polymerization of the polymer referred to in the present invention is
By dividing the number average molecular weight measured at a temperature of 39°C using gel permeation chromatography (Model HLC801A manufactured by Toyo Soda Co., Ltd.) using a chloroform solution containing 2.5% hexafluoroisopropanol as the solvent by the molecular weight of the repeating unit. It's what I asked for. In addition, the glass transition temperature (Tg) and melting point (Tm) are measured using a differential calorimeter (manufactured by PerkinElmer).
DSC-2 type) was used for measurement. On the other hand, the copolyarylate of the present invention was identified by infrared absorption spectrum, NMR spectrum, glass transition temperature, and elemental analysis. Reference Example 1 p-HCA shown by the above formula () was produced by reacting phosphinic acid shown by the above formula () with p-benzoquinone at a temperature of 90° C. in an ethyl cellosolve solvent. This p-HCA and acetic anhydride were charged into an esterification reactor at a molar ratio of 1:4 and esterified in acetic anhydride under reflux to produce diacetate, ie, p-HCA-2A. P-HCA-2A and IPA were charged in a condensation reactor at a molar ratio of 1:1, and 1 x 10 ^-4 mol of dimethyl tin maleate (CS) was added as a catalyst per 1 mol of the constituent unit of polyarylate. The reaction was carried out under a nitrogen atmosphere at normal pressure of 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 reacted at 280° C. under a reduced pressure of 0.1 torr, and finally the temperature was raised to 340° C. and condensed for a total of 10 hours to obtain polyarylates of HCA to IPA. In addition, during the reduced pressure reaction, the raw material p-HCA-2A
No sublimation of IPA was observed. This polyarylate has an infrared absorption spectrum,
When analyzed by NMR spectrum and elemental analysis, the following results were obtained. In other words, in the infrared absorption spectrum, it is 1780k.
absorption based on C=O of aromatic carboxylic acid ester, absorption of para-substituted aromatics at 736k and 781k,
Absorption of asymmetric trisubstituted aromatics was observed at 878k. Furthermore, in the NMR spectrum, no absorption of hydrogen atoms of methyl groups (1.5 ppm and 2.3 ppm) based on the raw material acetate ester was observed. According to the results of elemental analysis, C = 68.6% (theoretical value 68.7
%), H = 3.37% (theoretical value 3.33%), P = 6.79%
(Theoretical value 6.82%) was obtained. Reference example 2 The esterification reaction device is shown by the above formula ()
BA and acetic anhydride were charged in a molar ratio of 1:4 and esterified in acetic anhydride under reflux to produce diacetate, ie, BA-2A. BA-2A and IPA were charged in a condensation reactor at a molar ratio of 1:1, and 1 x 10 ^-4 mol of dimethyl tin maleate (CS) was added as a catalyst per 1 mol of the constituent unit of polyarylate, and nitrogen was added. Normal pressure under atmosphere
The reaction was carried out at 280°C for 8 hours with mixing. Based on the weight of distilled acetic acid, the esterification reaction rate was approximately 95%. This solid reactant was further removed under reduced pressure of 0.1 torr.
A solid phase reaction was carried out at 280°C, and the temperature was finally raised to 300°C for a total of 10 hours of condensation to obtain polyarylates of BA to IPA. In addition, during the reduced pressure reaction, the raw materials BA-2A and IPA
No sublimation was observed. Example 1 The HCA-IPA and BA-IPA polyarylates obtained in Reference Example 1 and Reference Example 2 were charged into a condensation reactor at a molar ratio of 1:1, and mixed for 1 hour at 280°C under nitrogen atmosphere at normal pressure. did. This reaction product was further reacted at 300° C. under a reduced pressure of 0.1 torr, and the temperature was finally raised to 320° C. and mixed for a total of 2 hours to obtain a copolyarylate, and the results shown in Table 1 were obtained. This copolyarylate has the following structural formula unit based on the area ratio of methyl group protons and aromatic ring protons in its NMR spectrum. and It was confirmed that the composition ratio was 1:1. In addition, the resulting polymer was molded into a string shape at 300°C, and when the string was ignited and the fire source was moved away, the fire extinguished immediately, indicating that it had good flame retardant properties. In addition, when observed in a transparent state, the 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 to IPA and BA to IPA were changed as shown in Table 1, and the results shown in Table 1 were obtained. In addition, the polymers obtained in Examples 2, 3, and 7 were molded at 300°C, and the polymers obtained in Examples 4 to 6 were molded into a string shape at 350°C, and after igniting the string, the fire source was moved away. The fire was extinguished immediately, and it was found that it had good flame retardant performance. In addition, when observed in a sticky 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 molding into a string shape, n = 79, 81, and 80, respectively.
Therefore, almost no thermal decomposition occurred.

[Table] * 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 a good color tone and transparency, but when it 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, the U polymer has a brown color, and when the flame source is ignited and the fire source is moved away, the U polymer continues to burn for several seconds, indicating 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 293°C, 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】

Claims (1)

[Claims] 1 Mainly composed of structural units represented by the following structural formulas () and (), where () and () are 99:1
A heat-resistant copolyarylate having an average degree of polymerization of 10 to 300, linearly and irregularly arranged in a molar ratio of ~1:99. (However, R1 and R2 are the same or different groups, and each has a halogen atom and a carbon number of 1 to 8
is selected from lower alkyl groups. Further, n ₁ and n ₂ each represent an integer of 0 to 4. )