JPH0519569B2 - - Google Patents

Description

[Detailed description of the invention]

(Industrial Application Field) The present invention relates to copolyarylates with excellent heat resistance and flame retardancy, and more specifically,
It has excellent heat resistance and flame retardancy, and is obtained mainly from aromatic diols containing phosphorus atoms, aromatic diols, and aromatic dicarboxylic acids containing terephthalic acid.
This invention relates to a copolyarylate having sufficient strength. (Prior Art) Polyarylate has been known as a heat-resistant polymer. For example, 4-hydroxybenzoic acid homopolymer or copolymer (Sumitomo Chemical, trade name Econol), or bisphenol A
A polymer consisting of terephthalic acid (TPA) and isophthalic acid (IPA) (Unitika product name)
U polymer) was once proposed and is now commercially available. Such polymers inherently have (1) poor moldability due to a relatively high melting point or a decomposition temperature lower than the melting or softening point, (2) poor color tone, and (3) poor transparency. (4) insufficient heat resistance; and (5) poor flame retardancy. The present inventors previously discovered a heat-resistant polyarylate made of a specific phosphinate compound and TPA and/or IPA (Japanese Patent Application No. 59-96196); copolyarylate (patent application No. 138827, 1982),
Heat-resistant copolyarylate consisting of a specific phosphinic acid compound, resorcinol, and IPA (patent application 1983-
No. 202820), it has been found that most of these drawbacks can be solved. (Problems to be Solved by the Invention) However, in the prior art as described above, although it is possible to improve melt moldability, heat resistance, and flame retardance, the strength of polyester itself is low, so it is difficult to manufacture. The disadvantage remains that the resulting molded products have relatively deteriorated properties. The primary purpose of epoxies is therefore to provide heat-resistant copolyarylates that are particularly suitable for plasma spray coatings and molded articles used at high temperatures.
The object of the present invention is to provide a copolyarylate having good heat resistance, high flame retardancy, and sufficient strength. (Means for Solving the Problems) As a result of intensive research by the present inventors on a new heat-resistant copolyarylate that can be molded at a temperature of 350°C or lower and that can solve the above-mentioned problems,
We discovered that phosphorus-containing polyarylates having specific structural units have extremely excellent properties,
We have arrived at the present invention. The present invention has the following configuration. That is, it mainly consists of structural units shown by the following structural formulas () and (), and () and () are 99:1 to 1:
A heat-resistant copolyarylate with an intrinsic viscosity of 0.5 or more arranged irregularly in a molar ratio of 99. (In the formula, Ar ₁ is a phenylene group or a naphthylene group. Also, Ar ₂ and Ar ₃ are phenylene, of which 1 to 100 paraphenylene groups are
In mol%, the remainder is metaphenylene group. However, each hydrogen atom in the aromatic ring may be substituted with a halogen atom, a lower alkyl group having 1 to 20 carbon atoms, an aryl group, an alkoxy group, or an allyloxy group. ) The first essential structural unit of the heat-resistant copolyarylate of the present invention is a unit consisting of a phosphorus-containing aromatic diol represented by the above structural formula () and an aromatic dicarboxylic acid containing terephthalic acid. Specific examples of the phosphorus-containing aromatic diol include organic phosphorus compounds of the following formulas, (), (), (), (), and the like. The second essential structural unit of the present invention is a residue consisting of 2,2-bis(4'-hydroxyphenyl)propane (BA) represented by the above formula () and an aromatic dicarboxylic acid. The terephthalic acid component is indispensable as the aromatic dicarboxylic acid component that constitutes the essential structural units represented by the above structural formulas () and (), and if the terephthalic acid component is not included, the reactivity will be reduced during the production of the polymer. There are problems in that a polymer with a low and high degree of polymerization cannot be obtained, and the resulting polymer has relatively poor properties such as strength. Therefore, as the aromatic dicarboxylic acid component, for example, terephthalic acid (TPA) and isophthalic acid (IPA) are used in a molar ratio of TPA/IPA of 1/99 to 100/0, preferably 20/80 to 90/ Ten,
Optimally, the ratio is preferably 50/50 to 80/20. Other preferred compounds as copolymerization components include, for example, 4,4'-dicarboxydiphenyl, bis(4-carboxyphenyl)methane,
2,2-bis(4-carboxyphenyl)propane, bis(4-carboxyphenyl)ether,
naphthalic acid, hydroquinone, resorcinol, 6-
Examples include oxy-2-naphthoic acid and p-oxybenzoic acid. On the other hand, the ratio of structural units () to structural units () is usually 1/99 to 99/1 in molar ratio, preferably 20/80 to 90/10, and optimally 50/50 to 80/1.
It is 20. Outside these ranges, if the number of structural units () is too large, the strength will decrease, and if the number of structural units () is too large, the glass transition temperature will be low and the flame retardance will be poor. The intrinsic viscosity [η] of the heat-resistant copolyarylate of the present invention is 0.5 or more, preferably 0.5 to 1.5, optimally
It is 0.6-0.9. If [η] is less than 0.5, various physical, mechanical, and chemical property values including heat resistance will be inferior, which is not preferable. It should be noted that if [η] is larger than 0.9, the melt viscosity becomes too high, which may impair moldability, flowability, etc., which is not preferable. As a preferable example in which the heat-resistant copolyarylate of the present invention can be produced economically, the first essential structural unit is 9,10-dihydro-9-oxa-10-(2',
5'-dihydroxyphenyl)phosphaphenanthrene-10-oxide (PHQ) and a unit consisting of TPA/IPA, and a system using a unit consisting of bisphenol A (BA) and TPA/IPA as the second essential constituent unit. The manufacturing method will be explained. Equimolar moles of the acid component consisting of TPA/IPA and the diol component consisting of PHQ/BA, and more than twice the equivalent (preferably 1.05 to 1.25 times equivalent) of acetic anhydride (Ac ₂ O) of the diol component are charged into the reactor. , the esterification reaction is carried out at a temperature of about 150° C. for about 2 hours under normal pressure. Thereafter, the temperature is raised sequentially, and if necessary, acetic acid (AcOH) is distilled out while reducing the pressure, and an acid exchange reaction is performed. After that, the final step is usually at a temperature of 250 to 250℃ and under a high vacuum of less than 1 torr for several hours to several tens of hours.
The heat-resistant copolyarylate of the present invention can be produced by carrying out a polycondensation reaction in a melt phase or a solid phase. Further, although a catalyst is usually used in the polycondensation reaction, when producing the heat-resistant copolyarylate of the present invention, one or more compounds selected from various metal compounds or organic sulfonic acid compounds are used. It will be done. Such metal compounds include antimony, titanium, germanium, tin, zinc,
Compounds such as aluminum, magnesium, calcium, manganese or cobalt are used,
On the other hand, as the organic sulfonic acid compound, compounds such as sulfosalicylic acid and o-sulfobenzoic anhydride (OSB) are used, and dimethyltin malate (CS) and OSB are particularly preferably used. The amount of the catalyst added is usually 0.1 x 10 ^-4 to 100 x 10 ^-4 mol, per 1 mol of polyester structural unit.
It is preferably used in an amount of 0.5 to 10 ^-4 to 50 x 10 ^-4 mol, most preferably 1 x 10 ^-4 to 10 x 10 ^-4 mol. In addition, the details of the temperature conditions and reaction time of the polycondensation reaction are: first, usually at 180°C to 300°C under normal pressure for 4 to 12 hours, preferably at 200°C to 290°C for 6 to 10 hours, most preferably at 230°C to 280°C. It is preferable to set it as 8 to 10 hours at °C. Furthermore under reduced pressure (usually 0.01~1torr) 250℃~350
℃ for 1 to 10 hours, preferably 280℃ to 330℃ for 2 to 10 hours
8 hours, optimally 4 to 6 hours at 300°C to 330°C. In the process of such polycondensation reaction, depending on the type of structural unit of polyarylate, it solidifies,
Sometimes it becomes a solid state, and sometimes it can be polycondensed while it is in a molten state. (Examples) Hereinafter, the present invention will be explained in more detail by giving examples. In addition, the intrinsic viscosity of the polymer in the example was determined from the melt viscosity measured at 20° C. in a weight solvent such as phenol-tetrachloroethane. In addition, the glass transition temperature and melting point were determined using a differential calorimeter (manufactured by PerkinElmer).
DSC-2 model) was used for measurement at a heating rate of 20° C./min, and impact strength was measured at a thickness of 1/8 inch according to ASTM D256 standard. In addition, flame retardancy is determined by flame resistance according to UL-94 standard and limit oxygen index according to JIS-K7201 standard.
I judged it. On the other hand, the heat-resistant copolyarylate of the present invention was identified by infrared absorption spectrum, melting point, and elemental analysis. Example 1 PHQ, BA and acetic anhydride in a molar ratio of 7:3:22 and TPA in a molar amount equivalent to the sum of PHQ and BA.
and CS as a catalyst was added in an amount of 4 x 10 ^-4 mol per mol of polyester repeating unit, and the mixture was reacted with mixing at 150°C under nitrogen atmosphere for 2 hours.
This reaction product was further subjected to solid phase reaction at 250°C under normal pressure for 2 hours, and further at 320°C under reduced pressure of 0.1 torr for 3 hours. The obtained polyester has an intrinsic viscosity of 0.87, a melting point of 384°C, a UL-94 standard V-0 class, and a limiting oxygen index of 61.
It was a heat-resistant, flame-retardant crystalline polymer with excellent color tone and transparency. Further, when this polyester was analyzed by infrared absorption spectrum and elemental analysis, the following results were obtained, and it was confirmed that it was a heat-resistant copolyarylate having a repeating unit of the following structure. In other words, in the infrared absorption spectrum
1779κ is the absorption based on C=O of aromatic carboxylic acid ester, 735κ, 782κ is the absorption of para-substituted aromatics, 888κ is the absorption of asymmetric trisubstituted aromatics, 2950κ
Absorption based on methyl groups was observed. On the other hand, the results of elemental analysis show that C = 70.4% (theoretical value 70.8%), H = 3.71% (theoretical value 3.77%), P =
A result of 5.11% (theoretical value 5.09%) was obtained. Examples 2 to 11, Comparative Example 1 Heat-resistant copolyarylates were produced in the same manner as in Example 1, except that the molar ratios of PHQ, BA, TPA, and IPA were changed as shown in Table 1. The obtained heat-resistant copolyarylate was identified by infrared absorption spectrum and elemental analysis. Also, LOI value,
The UL-94 standard value and impact strength were measured in the same manner as in Example 1. The results of Examples 1 to 11 and Comparative Example 1 are shown in Table 1. From Table 1, it can be seen that the comparative examples have poor impact strength. Examples 12 to 14 Heat-resistant copolyarylates were produced in the same manner as in Example 1, except that another phosphorus compound was used in place of PHQ in Example 2. The obtained heat-resistant copolyarylate was identified by infrared absorption spectrum and elemental analysis. Also, LOI value, UL−
94 standard value and impact strength were measured in the same manner as in Example 1. The results of Examples 11 to 13 are listed in Table 2. In addition, (), (), () in Table 2
are the structural formulas () and
It is an organic phosphorus compound with () and ().

【table】

[Table] (Effects of the invention) The heat-resistant copolyarylate of the present invention has (1) a specific phosphorus-containing structural unit in its side chain, so it not only does not decompose even when used at high temperatures; It also has a high degree of flame retardancy, sometimes as a molded product. (2) Since the main chain is mainly composed of hydroquinone, bisphenol A, and TPA/IPA units, it has excellent properties such as strength, as well as excellent heat resistance and moldability. It has excellent physical properties as a heat-resistant polymer.
As described above, the heat-resistant copolyarylate of the present invention is useful as a film, fiber, or molding material used in applications requiring heat resistance and flame retardancy.

Claims (1)

[Scope of Claims] 1 Mainly composed of structural units represented by the following structural formulas () and (), where () and () are 99:
Intrinsic viscosity randomly arranged in a molar ratio of 1 to 1:99
Heat resistant copolyarylate of 0.5 or higher. (In the formula, Ar ₁ is a phenylene group or a naphthylene group. Also, Ar ₂ and Ar ₃ are phenylene, of which 1 to 100 paraphenylene groups are
In mol%, the remainder is metaphenylene group. However, the hydrogen atoms in the aromatic ring are halogen atoms and
It may be substituted with a lower alkyl group, aryl group, alkoxy group or allyloxy group having 1 to 20 carbon atoms. )