JPH0355509B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for producing a resin composition. More specifically, the present invention relates to a method for producing a resin composition by intimately mixing a thermoplastic aromatic ether polymer and an aromatic polyester. In the past, many attempts have been made to melt and mix two or more types of polymers to bring out advanced performance that cannot be obtained with a single polymer.
There are many industrialized products such as ABS resin and HI-PS resin. In recent years, the excellent physical properties of wholly aromatic polyesters, particularly those capable of forming optically anisotropic melts, have attracted attention, and these wholly aromatic polyesters have been used as polyether sulfones (Japanese Patent Laid-Open No. 57-40555), polyethylene terephthalate, etc. (Unexamined Japanese Patent Publication No. 57-101020
No.) or polycarbonates (Unexamined Japanese Patent Publication No. 1983-
Attempts have been made to improve mechanical properties, such as strength, Young's modulus, flexural strength, and flexural modulus, by melt-mixing the elastomer (No. 40551). However, when trying to melt-mix aromatic polyesters, especially fully aromatic polyesters that have the ability to form optically anisotropic melts, with different polymers, they do not mix uniformly and separate to form independent phases. Clear boundaries are created between such phases. When a force is applied to a molded product made from a composition having such a boundary line, this boundary line acts as a defect and changes the desired mechanical properties, such as tensile strength, Young's modulus, flexural strength, and flexural modulus. The current situation is that it is not possible to achieve the expected effects in improving the above. Furthermore, in the conventional polymer blending method in which molten polymers are mixed with each other, there is a problem in that a high melting point polymer cannot be used as a blend material even if desired. Fully aromatic polyesters generally have high melting points. Particularly, when paying attention to physical properties such as Young's modulus and flexural modulus, it is expected that the use of a fully aromatic polyester with high rigidity will give preferable results. However, the higher the rigidity, the higher the melting point, which is a major limitation on its use. (For example, Japanese Patent Application Laid-Open No. 57-40555) The present inventor has proposed a method for mixing an aromatic polyether polymer with an aromatic polyester to form a composition and improving the mechanical properties of the aromatic polyether polymer. The present invention has been achieved as a result of intensive research aimed at eliminating the drawbacks and limitations of known methods. That is, the present invention combines an aryl ester of an aromatic dicarboxylic acid and an aromatic dihydroxy compound and/or an aryl ester of an aromatic oxycarboxylic acid into a thermoplastic aromatic ether polymer (A).
The aromatic polyester (B) produced per 100 parts by weight is
In the presence of the thermoplastic aromatic ether polymer (A) in a proportion of 0.1 to 30 parts by weight, at a temperature of the melting point of the thermoplastic aromatic ether polymer (A) or 280°C or higher, and at normal pressure or reduced pressure. A method for producing a resin composition, characterized in that a resin composition comprising a thermoplastic aromatic ether polymer (A) and an aromatic polyester (B) is obtained by performing a melt reaction under the following conditions. In the present invention, the thermoplastic aromatic ether polymer of component A is a polymer having a repeating unit represented by the following general formula (). general formula [In the formula, X: -SO ₂ - or

[Formula] Z: divalent alkylene group or O m: 0 or 1 n: 0 or 1] More specific examples of repeating units etc. can be mentioned. These may be used alone or in combination of two or more. In the present invention, the aromatic polyester as component B has as its main repeating unit an ester unit of an aromatic dicarboxylic acid and an aromatic dihydroxy compound and/or an aromatic oxycarboxylic acid unit. The aromatic dicarboxylic acids include terephthalic acid,
Isophthalic acid, naphthalene dicarboxylic acid, diphenyl dicarboxylic acid, diphenylsulfone dicarboxylic acid, diphenoxyethane dicarboxylic acid, diphenyl ether dicarboxylic acid, diphenyl ketone dicarboxylic acid, methyl terephthalic acid, phenoxy terephthalic acid, methyl isophthalic acid etc. can be exemplified. In addition, as aromatic dihydroxy compounds,
2,2-bis(4-hydroxyphenyl)propane, 1,1-bis(4-hydroxyphenyl)cyclohexane, bis(4-hydroxyphenyl)
Ether, 3,4'-dihydroxydiphenyl ether, 4,4'-dihydroxybenzophenone,
3,4'-dihydroxybenzophenone, hydroquinone, methylhydroquinone, butylhydroquinone, amylhydroquinone, benzylhydroquinone, α-methylbenzylhydroquinone,
Examples include αα-dimethylbenzylhydroquinone, chlorohydroquinone, and resorcinol. Furthermore, examples of aromatic oxycarboxylic acids include oxybenzoic acid and oxynaphthoic acid. The aromatic polyester (B) contains, in addition to the above-mentioned aromatic dicarboxylic acid, aromatic dihydroxy compound, and aromatic oxycarboxylic acid components, a small proportion (30 mol% or less,
Furthermore, 20 mol% or less), for example, aliphatic or alicyclic dicarboxylic acids such as adipic acid, sebacic acid, hexahydroterephthalic acid, etc.; ethylene glycol, neopentylene glycol, tetramethylene glycol, cyclohexane dimethylol, etc. aliphatic or cycloaliphatic diols such as;
It may be a copolymer of at least one oxycarboxylic acid such as β-hydroxyethoxybenzoic acid and ε-oxycaproic acid. Aromatic polyester (B) has the above-mentioned components, and is a thermoplastic aromatic ether polymer.
When the purpose is to improve the mechanical properties of (A), it is preferable that the polymer main chain skeleton be as rigid as possible and have a melting point or softening point as high as possible. The specific melting point or softening point is 200℃ or higher,
Furthermore, the temperature is preferably 250°C or higher, particularly 300°C or higher. Aromatic polyester (B) that satisfies these conditions is Those with repeating units such as, etc., and whose melting point is higher than the decomposition temperature It includes repeating units such as, etc., with a melting point of around 400°C, and even those with a lower melting point. The resin composition of the present invention comprises ester units of aromatic dicarboxylic acid and aromatic dihydroxy compound and/or
Alternatively, it can be obtained by producing an aromatic polyester (B) whose main repeating unit is an aromatic oxycarboxylic acid unit. That is, the thermoplastic aromatic ether polymer (A) does not substantially react.
When polycondensing the aromatic polyester (B) in the melt of the thermoplastic aromatic ether polymer (A), a lower aryl ester of an aromatic dicarboxylic acid, preferably polycondensed according to a conventionally known method. is preferred. Although the polycondensation reaction proceeds without a catalyst, it is preferably carried out using a conventionally known transesterification catalyst. Preferred examples of transesterification catalysts include compounds containing metals such as calcium, magnesium, strontium, barium, lanthanum, cerium, manganese, cobalt, zinc, germanium, tin, lead, antimony, and bismuth. Examples include magnesium acetate, calcium benzoate, strontium acetate, barium propionate, lanthanum carbonate, cerium oxide, manganese acetate, cobalt acetate, zinc acetate, germanium oxide, stannous acetate, lead oxide, antimony trioxide, bismuth trioxide, etc. can be exemplified. It is also preferred to use stabilizers with these transesterification (polycondensation) catalysts. Examples of preferred stabilizers include conventionally known trivalent or pentavalent phosphorus compounds or esters thereof, such as phosphorous acid, phosphoric acid, phenylphosphonic acid, methylphosphonic acid, ethylphosphonic acid, propylphosphonic acid,
Butylphosphonic acid, benzylphosphonic acid, trimethylphosphite, trimethylphosphate, triethylphosphate, tributylphosphate, triphenylphosphite, triphenylphosphate, diethylphenylphosphonate, dimethyl-(methyl)phosphonate, dimethyl-(ethyl ) phosphonate, dimethyl(benzyl)phosphonate, and the like. Such stabilizers improve the melt stability and color tone of the polymer, but depending on the type of catalyst, they may inactivate the polycondensation catalyst. Therefore, when the catalyst is to be inactivated, it is preferable to add the stabilizer after the polycondensation reaction is completed. Since polycondensation catalysts containing antimony or germanium are not inactivated by stabilizers,
When using this catalyst, the stabilizer can be added from the beginning of the polycondensation reaction. The amount of these catalysts used is from 0.005 to the total number of moles of aromatic dicarboxylic acid and aromatic oxycarboxylic acid.
It is preferably 0.5 mol%, more preferably 0.01 to 0.1 mol%, and the amount (P) of the stabilizer is 0.8<P/N<1.5 (however, P: mol of stabilizer) is preferably used. Such an amount of catalyst and optionally a stabilizer is added to the reaction system, and the reaction system is adjusted to the melting point of the thermoplastic aromatic ether polymer (A) or
The system is maintained at a temperature of 280°C or higher, whichever is higher (however, the upper limit of the reaction is 400°C, more preferably 380°C or lower), and the reaction is carried out under normal pressure to produce phenols, that is, monohydroxy aromatic compounds. It is distilled out of the system and allowed to proceed with polycondensation. The polycondensation reaction is first carried out under normal pressure and then under reduced pressure, and the resulting monohydroxy aromatic compound is distilled out of the system to proceed. In the reaction under normal pressure, it is preferable that the reaction temperature is gradually increased as the amount of aromatic monohydroxy compound distilled out. Such reaction under normal pressure is preferably carried out at a reaction temperature as low as possible so long as the aromatic monohydroxy compound can be distilled out. Once a predetermined amount of the aromatic monohydroxy compound has been distilled out of the system, the reaction system is reduced in pressure, and while the aromatic monohydroxy compound produced is further distilled out of the system, the degree of vacuum and reaction temperature are gradually increased to reach the final stage. 1mmHg to
Polymer (B) with a predetermined degree of polymerization by reacting at a reaction temperature of 320 to 340°C under a pressure of about 300 to 300°C or less.
It is preferable to obtain Regarding the reaction temperature, when the melting point or softening point of the thermoplastic aromatic ether polymer (A) is higher than this, a higher reaction temperature is adopted. The amount of aromatic polyester (B) mixed and dispersed in the thermoplastic aromatic ether polymer (A) is 0.1 per 100 parts by weight of the thermoplastic aromatic ether polymer.
-30 parts by weight, preferably 0.5-20 parts by weight. In this way, a uniform and intimately mixed resin composition can be obtained. Therefore, this resin composition has superior dispersibility compared to compositions obtained by conventionally known polymer blending methods, and its molded products have high tensile strength, Young's modulus, bending strength, bending elastic modulus, etc. and has satisfactory mechanical properties. Further, in the conventional polymer blending method, it is impossible to achieve a uniform blend when using a wholly aromatic polyester whose melting point is higher than the decomposition temperature, but according to the present invention, such a wholly aromatic polyester can also be blended sufficiently uniformly and tightly. Can be mixed with Furthermore, the resin composition of the present invention is not a copolymer of a thermoplastic aromatic ether polymer (A) and an aromatic polyester (B). The resin composition of the present invention can be molded by any molding method, and can be efficiently molded into, for example, sheets, fibers, films, etc., and furthermore, stretchability and the like are significantly improved. Their excellent moldability can be better understood when compared to the fact that conventional applications were mainly limited to injection molded products. Examples will be described below with reference to examples. Note that "parts" in the examples mean parts by weight. Example 1

100 parts of polyether sulfone (ICI; grade 300P) having repeating units of [formula], phenyl paraoxybenzoate
21.4 parts and 2.3 x 100 ^-3 parts of stannous acetate were charged into a reactor and reacted at 300°C under normal pressure for 30 minutes, then at 310°C for 30 minutes, at 330°C for 30 minutes, and then kept at the same temperature for 20 minutes. Phenol was distilled off while increasing the degree of vacuum in 100 mmHg increments, and finally a polycondensation reaction was carried out at 330° C. for 20 minutes under a high vacuum of about 1 mmHg or less. A slightly cloudy, translucent resin composition was obtained. Examples 2 to 3 Resin compositions having the polymer structure and composition shown in Table 1 were obtained in the same manner as in Example 1. However, in Example 2, diphenyl terephthalate (13.3 parts) and hydroquinone (5.0 parts) were used as aromatic polyester raw materials, and in Example 3, diphenyl isophthalate (13.3 parts) and hydroquinone (5.0 parts) were used. ) was used. Furthermore, the reaction temperature was 360°C.

[Table] Examples 4 to 8 As aromatic ether polymer A resin composition was produced by polycondensing a polyester having the structure shown below in the same manner as in Example 1 using a polymer having repeating units.

【table】

[Table] All the resin compositions produced by the method of the present invention were translucent, and the polyester was uniformly dispersed. Example 9 The resin compositions obtained in Examples 1 to 8 were molded at a Ruder temperature of 360°C, a back pressure of 500 kg/cm ² and a mold temperature of 120°C. The physical properties of the molded product are shown in Table 3, and it can be seen from this table that the elastic modulus-flexural modulus is greatly improved compared to the base polymer. All of the above molded products that do not exhibit a yield point have a breaking elongation of 10% or more, and have desirable properties as molded products.

【table】

[Table] Comparative Example The polymerization was carried out under the same conditions as in Example 3 except that the polymerization was carried out in the absence of polyether. The obtained polymer had a melting point of 350°C or higher and was in powder form. This polyester was melt mixed with polyether in the same proportions as in Example 3 and then injection molded as in Example 9. The physical properties of the obtained molded product are shown in Example 3.
The results are shown in Table 4.

【table】

Claims (1)

[Claims] 1 Aromatic polyester (B) produced by aryl ester of aromatic dicarboxylic acid, aromatic dihydroxy compound and/or aryl ester of aromatic oxycarboxylic acid per 100 parts by weight of thermoplastic aromatic ether polymer (A) is 0.1 In the presence of the thermoplastic aromatic ether polymer (A) in a proportion of ~30 parts by weight, the thermoplastic aromatic ether polymer (A)
or a temperature of 280°C or higher and under normal pressure or reduced pressure to obtain a resin composition consisting of a thermoplastic aromatic ether polymer (A) and an aromatic polyester (B). A method for producing a resin composition.