JPS5913546B2 - resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a mixture of terephthalic acid and isophthalic acid or their functional derivatives (provided that the molar ratio of terephthalic acid groups to isophthalic acid groups is 9:1 to 1.9) and a compound of the general formula R
1 R2R'1R2 Ku0HO□ X □OH R3R4R'3R! Bisphenols represented by 4 [However, -X- is -0
-, -5-, -50'', -Co-, Alkylidene group or alkylidene group (if necessary, the alkylene group or alkylidene group may contain one or more hydrocarbon groups, halogen atoms, or halogenated hydrocarbon groups) R1, R2, 30R3, R4, R'1, W2, R'
3. W4 is a hydrogen atom, ′゛.

selected from the group consisting of hydrogen atoms and hydrocarbon groups], and as a stabilizer, a compound of the general formula 95--R, (wherein R5, R6 and R7 are hydrogen, alkyl, [A cycloalkyl, alkenyl, phenyl or aralkyl group, which can be further substituted with an alkyl, alkoxy or amino group]
The present invention relates to a resin composition containing an organic phosphine compound shown in the following.

Aromatic polyester copolymers produced from terephthalic acid, isophthalic acid, or functional derivatives thereof, and divalent phenolic compounds (hereinafter referred to as bisphenols) or functional derivatives thereof have been known for a long time.

As a method for producing such an aromatic polyester copolymer, a so-called interfacial polymerization method (W. M.EarecksOn.J.POly.S
ci. XL399l959, Japanese Patent Publication No. 40-1959), a solution polymerization method (A.CO.
nix. Ind. Eng. Chem. ? 147195
9, Japanese Patent Publication No. 37-5599), a melt polymerization method in which aromatic dicarboxylic acids and bisphenols are heated in the presence of acetic anhydride, and a melt polymerization method in which phenyl esters of aromatic dicarboxylic acids and bisphenols are heated. Legal (Tokukō 1977-
15247) and a melt polymerization method in which aromatic dicarboxylic acid and bisphenol are heated in the presence of diaryl carbonate (Japanese Patent Publication No. 38-26299). It is also well known that aromatic daughter polyesters made of aromatic dicarboxylic acids and bisphenols obtained in this way, especially copolymers thereof, have excellent properties.

In other words, it has many excellent properties in terms of mechanical properties such as tensile strength and elongation, bending strength, bending recovery rate, and impact strength, heat distortion temperature, dimensional stability, electrical properties, and flame resistance. Therefore, it is also known that it can be used in a wide range of fields as various molded products such as extrusion molding and injection molding, films, fibers, and coating materials. It has been found that aromatic polyesters made by these methods often already have a yellow or brown color when produced, or become colored during storage.

It is also recognized that such aromatic polyesters become colored while being heated in air to be made into general molded articles, fibers or films by injection molding, extrusion molding or other methods. Such coloring is very inconvenient when it is important that the product be colorless, and when pigments are mixed in to obtain the desired color, the resulting coloration is often completely different from what was expected. . Furthermore, such coloring is thought to be accompanied by decomposition of the polymer, and it irregularly reduces the viscosity of the molded product, reducing the physical properties of the polymer, which has useful properties. This is a significant disadvantage. There have been few known attempts to improve such drawbacks. A slight amount of sodium dithionite
-11297 publication), or polyphenylene or activated anthracene (Japanese Patent Publication No. 45-123418), but the effect is not sufficiently satisfactory for resins with high processing temperatures such as the aromatic polyester used in the present invention. As a result of intensive research to improve this drawback, the present invention has developed an aromatic polyester copolymer with excellent heat resistance and less coloring by adding organic phosphines to the aromatic polyester copolymer. The present invention was achieved by discovering that this combination can be obtained.

Various copolymers can be obtained from the aromatic polyester copolymer used in the present invention depending on the combination of the quantitative ratio of terephthalic acid groups and isophthalic acid groups, and the type and quantitative ratio of bisphenols. The bisphenols used in the present invention include, for example, 2,2-bis(4-hydroxyphenyl)-pro? Gun, 2,2-bis(4-hydroxy-3,5-
dibromophenyl)-propane, 2,2-bis(4hydroxy-3,5 dichlorophenyl)-propane, 4,4
'-Dihydroxydiphenyl sulfone, 4,45-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenyl sulfide, 4,42-dihydroxydiphenyl ketone, 4,4'-dihydroxydiphenylmethane, 2,2 -bis(4hydroxy3,5dimethylphenyl)-propane, 1,1-bis(4hydroxyphenino(
c) Monoethane, 1,1-bis(4-hydroxyphenyl)
-cyclohexane, 4,4'-dihydroxydiphenyl-methylisobutylmethane, and the like.

As a method for producing the aromatic polyester copolymer used in the present invention, any of the above-mentioned interfacial polymerization method, solution polymerization method, and melt polymerization method may be used, but in particular organic solvents such as terephthalic acid chloride and isophthalic acid chloride are used. An interfacial polymerization method in which a solution and an alkaline aqueous solution of bisphenols are mixed and stirred is advantageous because it yields a polyester with relatively little coloring.

Examples of the organic phosphines of the present invention include the following.

Triethylphosphine, triisopropylphosphine, tri-n-butylphosphine, tricyclohexylphosphine, diphenylvinylphosphine, allyldiphenylphosphine, triphenylphosphine,
Diphenylphosphine, methylphenyl-P-methoxyphenylphosphine, tri-2,4-dimethylphenylphosphine, tri-m-aminophenylphosphine, tri-2,4,6-trimethylphenylphosphine, Examples include tri-0-tolylphosphine and tri-0-anisylphosphine. Methods for adding stabilizers include, for example, in the interfacial polycondensation method in which an organic solution in which dicarboxylic acid chloride is dissolved and an alkaline solution of bisphenols are stirred during the production of aromatic polyester.
The stabilizer can also be added before aromatic polyester polymerization, ie to any of the monomer components.

Further, when the polymer solution is isolated after completion of polymerization, it is also possible to add a stabilizer previously dissolved in the same solvent to the polymer solution. When the aromatic polyester is isolated as a solid, the stabilizer can be present in the aromatic polyester in the following manner instead of simply being added. That is, the polymer is immersed in a solution in which a stabilizer is dissolved in a solvent such as methanol or acetone. After immersion, the solvent is evaporated off. Furthermore, in the case of melt polymerization, it may be supplied together with the monomer during polymerization. In addition, it may be added to aromatic polyester chips during molding, for example during injection molding. One of the features of the present invention is that when it is added to powder or chips and molded, molded products with uniform color tone and properties can be obtained. The amount of stabilizer added to the aromatic polyester is 0.01 to 10% by weight based on the aromatic polyester.

If it exceeds 5% by weight, it may sometimes have an adverse effect on mechanical properties, so it is preferably used in an amount of 0.1 to 2% by weight, particularly preferably in a range of 0.1 to 1% by weight.

The effect of the present invention is, for example, an aromatic polyester (hereinafter referred to as aromatic polyester 0
). ) (However, the weight percentage of each group in the unit repeating unit is 18.401): 18.4 (
: L: 63.201)) by an interfacial polymerization method, methylphenyl-P-methoxyphenylphosphine is added to the aromatic polyester O) at a concentration of 0.5% by weight before polymerization. Then,
The obtained stabilizer-containing aromatic polyester (I [Co., Ltd.] 10
% APHA in the chloroform solution was found to be yellowish and more than 100 compared to the aromatic polyester 0) to which no stabilizer was added, while the former was almost colorless and less than 20. Furthermore, the above aromatic polyester O)
As a result of a one-week sun exposure test, the solution with the stabilizer added showed almost no increase in APHA (30), while the solution without the stabilizer changed color to more than 500. Regarding coloration during molding, the degree of coloration of the aromatic polyester with the addition of stabilizers is significantly lower than that of the stabilizer-added aromatic polyester. In addition, stabilizer-containing aromatic polyester (1) obtained by adding 0.5% by weight of triphenylfisphine to aromatic polyester (1)
) showed a remarkable difference in coloring deterioration and viscosity (η1nh) decrease during melt injection molding compared to the unadded aromatic polyester (1). The injection molding was carried out in an air atmosphere at a temperature of 300° C. or above, and the typical results are shown below. (ηIn
h is 6/4 of phenol/tetrachloroethane at 25°C
It is the logarithmic viscosity measured at a concentration of 1b x 1 in a mixed solvent of (weight ratio). ) Also, the molded product was placed in air at 170°C for 240°C.
It was found that even when left for a long time, the color deterioration and viscosity reduction of the molded product were significantly improved compared to when no stabilizer was added, and the heat resistance was improved.

For example, when 0.5% by weight of each of triphenylphosphine and methylphenylparamethoxyphenylphosphine was added to the aromatic polyester (1) during molding, the temperature was 170°C. The results of the 240 hour treatment are significantly improved as shown in the following table.The aromatic polyester thus obtained has many advantages including mechanical properties such as tensile strength, impact strength, electrical properties, It is expected to be used in many fields as various molded products, bristles, fibers, sheets and films.

Next, the present invention will be explained with examples, but the present invention is not limited thereto.

Example 1 2,2-bis(4-hydroxyphenyl)-probane 2
580t of aqueous sodium chloride solution containing 9.2f and 13f of isophthalic acid dichloride13 of terephthalic acid dichloride
A solution prepared by adding 0.25 t of triphenylphosphine to a methylene chloride solution containing 7 and 7 was mixed, stirred vigorously and reacted, and then the organic phase was separated.

The organic phase was added to acetone to obtain a powdered polymer. After drying this, aromatic polyester containing stabilizer 41.5
t was obtained. This stabilizer-containing aromatic polyester powder is made into a 1001) solution in chloroform.

The APHA of this solution was approximately 20 and the APHA of this polymer solution after 3 weeks of exposure to sunlight was 40. Example 2 500 tons of stabilizer-containing aromatic polyester powder obtained in the same manner as in Example 1 was further thoroughly dried under vacuum to obtain a powder with a diameter of 2.
Chipping was carried out at 320°C using a 2ml extruder.

The degree of coloration of the chips was significantly reduced compared to chips made from a polymer without any stabilizer added under the same conditions. Example
3 Strong soda aqueous solution 5.5k dissolved in 2.75k9
A methylene chloride solution of 21.0 t of methylphenyl-P-methoxyphenylphosphine was added to an aromatic polyester stock solution produced by an interfacial polymerization method using 1.21 kg of isophthalic acid dichloride, 1.21 k9 of terephthalic acid dichloride, and 25 t of methylene chloride. 55 tons were added and mixed.

After gradually evaporating methylene chloride, the mixture was pulverized in a second machine to obtain a stabilizer-containing aromatic polyester. Even when the obtained granular aromatic polyester was sufficiently dried and exposed to an air atmosphere at 170° C. for 240 hours, almost no coloration was observed and there was very little decrease in viscosity. Example 4 Diphenyl terephthalate 48t (0.15 monole),
A mixture of 43t (0.135 mol) diphenyl isophthalate and 3.56 t (0.016 mol) diphenyl carbonate and bisphenol A697 (0.3 mol)
Diphenylphosphine 0.5% by weight of the aromatic polyester produced by reacting with the polymer
After immersing the sample in a methanol solution in which 37 was dissolved, the methanol was evaporated under vacuum to obtain a stabilizer-containing aromatic polyester.

A film made from a methylene chloride solution was heated at 150°C.
Even after processing in an air atmosphere for 5 hours, there was almost no difference in the degree of coloration between the film and the film before processing. Example 5
2,2-bis(4-hydroxyphenyl)-propane 2
A methylene chloride solution containing 580 parts by weight of an aqueous solution of 9.2 parts by weight of sodium chloride dissolved therein, 13 parts by weight of isophthalic acid dichloride, 13 parts by weight of terephthalic acid dichloride, and 0.25 parts by weight of the phosphine compound shown in the table below. were mixed with vigorous stirring at 20° C. and stirred for 10 hours.

Stirring was stopped and the mixture was allowed to stand still to separate into a methylene chloride phase and an aqueous phase, and then the methylene chloride phase was taken out and purified water was added thereto for washing. Then, the methylene chloride was distilled off under heating to remove the phosphine compound. An aromatic polyester containing .5% by weight was obtained. The logarithmic viscosity of this aromatic polyester [in a 6/4 (weight ratio) mixed solvent of phenol/tetrachloroethane, 25° C., 1] was 0.65. This stabilizer-containing aromatic polyester was injection molded at 330°C to form a disc with a diameter of 50 mm and a thickness of 21 m1.

During molding, 1% by weight of titanium oxide was added to facilitate the subsequent yellowness test. The disc thus obtained was irradiated for 100 hours using a fade-o-meter, and the yellowness (yellow index: YI) of the surface of the disc before and after irradiation was measured according to JISK-7103, and the yellowness was measured with the naked eye. Observe the color of the board. The results are shown in the table below. For comparison (dimethyl terephthalate 6
00 parts by weight and 180 parts by weight of ethylene glycol.
0767% by weight of calcium acetate, stirred in a can with heating, followed by distillation of methanol to carry out the transesterification reaction, and at the end of the transesterification reaction, 2
2.98 parts by weight of the phosphine compound shown in the table below dissolved in ethylene glycol at a temperature of 15-250<0>C was added.

Claims (1)

[Claims] 1. A mixture of terephthalic acid and isophthalic acid or their functional derivatives (however, the molar ratio of terephthalic acid groups and isophthalic acid groups is 9:1 to 1:9) and a general formula ▲ mathematical formula, chemical formula, table etc. ▼ Bisphenols represented by (however, -X- is -O
-, -S-, SO_2-, -CO-, alkylene or alkylidene groups (if necessary, alkylene or alkylidene groups are substituted with one or more hydrocarbon groups, halogen atoms or halogenated hydrocarbon groups) ) selected from the group consisting of R_1, R_2, R_3, R
_4, R'_1, R'_2, R'_3, R'_4 are selected from the group consisting of a hydrogen atom, a halogen atom, and a hydrocarbon group). ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R_5, R_6 and R_7 are hydrogen, alkyl, cycloalkyl, alkenyl, phenyl or aralkyl groups, and these groups are further substituted with alkyl, alkoxy or amino groups. A resin composition containing an organic phosphine compound represented by