JPS6178832A - Heat-resistant copolyarylate - Google Patents

Abstract

PURPOSE:A heat-resistant copolyarylate having excellent heat resistance and high flame retardancy, obtained from a phosphorus-containing aromatic diol, resorcinol and isophthalic acid and comprising specified structural units. CONSTITUTION:A copolyarylate consisting mainly of structural units of formulas I and II, wherein the units of formulas I and II are linearly and randomyl ar ranged at a molar ratio of 99:1-1:99, and the average degree of polymerization is 10-300. In formula I, R<1> and R<2> are each H, a halogen or a 1-8C lower alkyl and n1 and n2 are each 1-4. Said polyarylate can be obtained by reacting isophthalic acid or its esterifiable derivative with an aromatic diol group- containing phosphinic acid or its esterifiable derivative and resorcinol or its esterifiable derivative. It is necessary that the average degree of polymerization of said arylate is 10-300, most suitably 50-150.

Description

[Detailed description of the invention]

(Industrial Field of Application) The present invention relates to a novel copolyarylate which has poor thermal properties. More specifically, the present invention relates to a novel copolyarylate obtained from an aromatic diol containing a phosphorus atom, resorcinol, and isophthalic acid, which has high heat resistance and has been difficult to solve. (Prior Art) Polyarylates have been known as thermoplastic polymers. For example, 4-hydroxybenzoic Gl homopolymer and copolymer (Sumitomo Chemical, trade name Econol)
, or a polymer consisting of bisphenol A, terephthalic acid, and isophthalic acid (Unitika product name U polymer)
It was once proposed. It is now commercially available. Such polymers inherently have l) relatively high melting points or decomposition degrees below their melting or softening points. Poor moldability. 2) Poor color tone. 3) Poor transparency. 4) Heat resistance is insufficient. 5) Inferior flammability by $1. It had such drawbacks. (Problems to be Solved by the Invention) The main object of the present invention is to provide a heat-resistant copolyarylate which is particularly suitable for plasma spray coatings and molded articles used at high temperatures, and which has good heat resistance. Moreover, it also had high flammability. The present invention provides a novel heat-resistant copolyarylate. As a result of intensive research into new heat-resistant copolyarylates that do not have the above-mentioned problems, the present inventors found that phosphorus-containing polyarylates having repeating units with a specific structure,
It has excellent properties. find out,
t'Achieved with invention C. (Means for solving the problems) The present invention has a first-order configuration. That is, the present invention mainly consists of structural units represented by the following structural formulas (1) and (ll), and (I) and (II).
were irregularly arranged linearly at a molar ratio of 99:1 to 1:99. It is a heat-resistant copolyarylate having an average degree of polymerization of 10 to 300. ]1 (However, RL 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, nt
, fi2 each represent an integer from 1 to 4. ) The heat-resistant copolyarylate of the present invention is a combination of isophthalic acid (hereinafter referred to as IPA) or its ester-forming derivative and phosphinic acid (hereinafter referred to as P-HC) having an aromatic diol group.
It will be abbreviated as A. ) or its ester-forming derivatives and resorcinol (hereinafter abbreviated as RA) or its ester-forming derivatives can be reacted using various ester-forming methods. Examples of ester-forming derivatives of IPA include inphthalic acid dialkyl ester, isophthalic acid diaryl ester, and isophthalic acid civalide. Ester-forming derivatives of P-HCA or RA

[
Examples include derivatives having a dianluoquine group and a dialkali gold group. The uninvented copolyarylate 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 position (■) (hereinafter abbreviated as RA to IPA) can also be produced by melt-mixing homopolymers consisting of RA to IPA. The structural formulas of P-HCA and RA according to the present invention are shown by (@) and [F]. O As an economically preferable example for obtaining the uninvented copolyarylate, IPA and a carboxylic acid ester derivative of HCA represented by the following formula M (hereinafter abbreviated as p-HCA-2A) and the following One example of this method is to increase the content of a carboxylic acid ester derivative of RA (hereinafter abbreviated as RA-2A) at high temperature and under reduced pressure. (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-F (
CA-2A and RA-2A are based on the above formula (1).
), ([V) It can be produced by esterifying the h6 P-HCA Oyohi RA shown in TE in the corresponding carboxylic acid anhydride (eg, anhydrous vinegar) under reflux. At this time, rPA 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 a phosphinic acid represented by the following formula (1) with p-benzoquinone in a suitable solvent such as ethyl selonprop. ! When producing copolyarylate by mixing the three at the raw material stage, IPA, P-HCA-2A and RA-2A
The molar ratio of the sum of 1 is usually 0.8 to 1.2. Preferably 0.
9-1.1. Equimolar amounts are optimally preferred. 9Although 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 sulfonic acid compounds are used. Such metal compounds include antimony, titanium, kermanium, tin, zinc, and fluminilum. Compounds such as macanenium, calcium, manganese aluminum 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 1 x 10 to 1 mol of the polyarylate structural unit (for each mol of polyarylate structural unit).
x10 mol, especially 5 x 10 to 5 x = 310 mol, optimally 1 x 10 to 1 x 10 mol. The temperature conditions and reaction time for the condensation reaction are usually 4 to 12 hours at 180 to 400°C under normal pressure, preferably 250 to 400°C.
~360°C for 6-10 hours, optimally 280-320°C
It is preferable to set it as 8 to 10 hours. Furthermore, under reduced pressure (usually 0.01 to 10 torr), 1
at 80-400°C for ~10 hours, especially at 250-360°C
C. for 2 to 8 hours, optimally 280 to 340.degree. C. for 4 to 6 hours. Here, the molar ratio range of P-HCA:RA is 99; 1
~1:'l)9. Preferably 80:20 to 40:6
0° is optimally 80:20 to 60:40. When the P-HCA component increases, strength 9 elasticity decreases,
If the RA acid component increases, the color tone will worsen. 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 RA-IPA. The conditions for mixing HCA-IPA and RA to IPA in the present invention are under normal pressure at 180 to 400°C for 0.1 to 2 hours. Preferably, the temperature is 250 to 360°C for 0.2 to 1 hour. Furthermore, if necessary, under reduced pressure (usually α0.1 to 10 to
rr) The reaction may be carried out at 180 to 400°C to obtain a predetermined degree of polymerization. Average degree of polymerization (n
) is 10-300. Preferably 30-200. Optimally, it needs to be between 50 and 150. If the average degree of polymerization is less than 10, various physical, mechanical and chemical properties 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 becomes too high, impairing moldability, fluidity, etc. (Examples) 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 as follows. The molecular weight of the repeating unit is the number average molecular weight measured at a temperature of 39°C using a chloroform solution containing 2.5 units of hexafluoroinpropanol as a solvent using Gel Permini 7g chromatography (Model HLC8OJA manufactured by Toyo Soda). It is calculated by dividing by. 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 Go to the above formula! By reacting the phosphinic acid represented by (2) with p-benzoquinone in an ethylcelonorb solvent at a temperature of 90°C, p-HCA represented by the formula (1) was produced. In the esterification reactor, this p-HCA and acetic anhydride were charged at a molar ratio of 1:4, and diacetate, that is, p-HCA-2A, was produced by esterifying the mixture with anhydrous vinegar under reflux. . Condensation reaction apparatus (p-HCA-2A and IPA were charged at a molar ratio of 1:10, and dimethyl tin maleate (C8) was added as a catalyst in an amount of 10 moles per mole of polyarylate structural unit, and the mixture was heated under a nitrogen atmosphere. Normal pressure 280℃
The mixture was allowed to react while being mixed for 8 hours. The esterification reaction rate is determined by the weight of distilled acetic acid. There were approximately 93 people in charge. This reaction product was further heated at 280°C under a reduced pressure of 0.1 torr.
The temperature was finally raised to 340° C. and condensation was carried out for a total of 10 hours to obtain polyarylates of HCA to IPA. In addition, the raw material p-HCA-2A is contained in the vacuum core. 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=O of aromatic carboxylic acid ester is at 1780k.
The absorption of para-substituted aromatics at 736k and 781k is
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 (1.5 ppm and 2.3 ppm)
pI)m) was not observed. According to the results of elemental analysis, C = 68.6 coefficient (theoretical f coefficient 687
%). The results were obtained: H=3.37chi (theoretical value: 3.33%) and P=6.79ch (theoretical value: 6.82%). Reference Example 2 RA represented by the above formula (1v') and acetic anhydride were charged into an esterification reaction c'5 apparatus at a molar ratio of 1:4, and anhydrous i! vi: A diacetate ester, namely J(A-2A), was produced by esterification under reflux in an acid. Tokikin Reactor KRA-2A and IPA were charged in a molar ratio of 1 to 2, '4. fi11! Dimethyltin maleate (C8) was added as a medium to 1 mole of polyarylate structural unit, and 1X10-4 mole was added, and the mixture was heated under nitrogen atmosphere at normal pressure 2.
The mixture was mixed and reacted at 80C for 8 hours. The esterification reaction rate is determined by the weight of distilled acetic acid. It was about 95%. This reaction product was further heated at 280 °C under a reduced pressure of 0.1 torr.
Finally, the temperature was raised to 300° C. and condensation was carried out for a total of 10 hours to obtain polyarylates of RA to IPA. In addition, during the Josan reaction, no sublimation of the raw material RA-2A or IPA was observed. Example 1 HCA~IP obtained in Reference i:f:l 1 and Reference Example 2
Polyarylates A and RA to PA were charged into a condensation reactor at a molar ratio of 1:1, and the mixture was heated under normal pressure 2 in a nitrogen atmosphere.
Mixed at 60°C for 1 hour. This reactant was further added to 0.1
The reaction was carried out at 280℃ under the pressure of torr, and the final temperature was 30℃.
The temperature was raised to 0 DEG C. and mixed for a total of 2 hours to obtain a pale brown-yellow copolyarylate with the results shown in Table 1. In addition, it was confirmed from the area ratio of methyl group protons and aromatic ring protons in the NMR spectrum that the following structural units were in a 1:1 composition ratio. In addition, the obtained 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 immediately extinguished, indicating that it had good flame retardant performance. In addition,
The transparency was extremely good when observed with a tapered paper. 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 RA to IPA were changed as shown in Table 1, and the results shown in Table 1 were obtained. The color tone of the obtained polymer was light brown-yellow. Furthermore, the polymers obtained in Examples 2, 3 and 7 were 32
At 0°C, the polymers obtained in Examples 4 to 6 were molded into a string shape at 300°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. Note that the transparency was extremely good when observed in the form of a strip. When the average degree of polymerization of the polymers of Examples 2, 3 and 7 was measured after being molded into a string shape, n=60 and 73.6, respectively.
6, and almost no thermal decomposition occurred. Comparative Reference Examples 1 and 2 As pain relief 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 when the terephthalate was ignited, it continued to burn until it burned out even if the fire source was moved away. Furthermore, the Tg was lower than that of the polymer of the present invention, indicating that the heat resistance was inferior. In addition, the U polymer has a brown coloration, and it will continue to burn for a few seconds when the flame ignites and the flame source is moved away. It can be seen that the flammability is slightly inferior to that of the polymer of the present invention. In addition, Econol (Sumitomo Chemical, trade name E 2000)
Although it has a heat distortion temperature of 293°C and excellent M 1i-IE resistance. When ignited, combustion continued for several seconds, indicating that the combustibility was slightly inferior to that of the polymer of the present invention. Table 2 (Effects of the invention) According to the present invention. (11) No decomposition occurs even when used at high temperatures. (2) Preferred glass transition temperature range (150-230℃
) 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.

Claims (1)

[Claims] (1) Mainly composed of structural units represented by the following structural formulas (I) and (II), in which (I) and (II) are 99:1 to
A heat-resistant copolyarylate having an average degree of polymerization of 10 to 300, arranged irregularly in a linear manner in a molar ratio of 1:99. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I) (However, R_1 and R_2 are the same or different groups, and each has a hydrogen atom, a halogen atom, and a carbon number of 1 to 8.
is selected from lower alkyl groups. Also, n^
1 and n^2 each represent an integer from 1 to 4. ) ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼ (II)