JPH0455224B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a resin composition formed by blending a bisphthalimide compound as a modifier with an aromatic polyetheramide resin. General formula () (In the formula, R ₁ to _{R 4} represent hydrogen, lower alkyl, lower alkoxy group, chlorine or bromine, and may be the same or different. _{R 5} and R ₆ represent hydrogen, methyl group, ethyl Aromatic polyamide can be obtained from an aromatic diamine containing an ether bond represented by a trifluoromethyl group, a trifluoromethyl group, or a trichloromethyl group, which may be the same or different, and an aromatic dicarboxylic acid halide. It is known from Japanese Patent Application Laid-Open No. 52-23198 and US Pat. No. 3,505,288. By the way, aromatic polyetheramides obtained from such special diamines have good mechanical properties such as tensile strength, bending strength, and impact strength.
Thermal properties such as heat distortion temperature and pyrolysis, arc resistance,
It maintains excellent electrical properties such as dielectric constant and dielectric loss, flame resistance, and dimensional stability, and is therefore widely used in general molded products, films, etc. made by injection molding, extrusion molding, press molding, etc. It is expected to have many uses. However, a drawback of this type of aromatic polyether amide is that it has poor moldability. In general, evaluation of moldability is extremely important for plastics, and even if the plastic itself has inherently excellent properties, if the moldability is poor, it will not be possible to economically manufacture the product. Therefore, it is not possible to fully demonstrate its excellent properties in products. For example, when making a product by injection molding using a polymer with a high softening temperature and high melting temperature, high plasticization temperature,
High injection pressure, high mold temperature, etc. are required, which not only causes high costs, but also high plasticization temperature induces thermal decomposition of the polymer, and high injection pressure causes distortion in the product. . Furthermore, if these strict conditions are not met, external defects such as short shots, sink marks, and flow marks may occur, and mechanical properties may deteriorate. Therefore, it has been desired to improve the moldability of aromatic polyetheramides as well. The present inventors have conducted intensive studies to improve moldability and processability while maintaining the excellent properties of aromatic polyetheramide, and as a result, have arrived at the present invention. That is, the present invention provides the general formula () (However, in formula (), R ₁ to _{R 4} represent hydrogen, a lower alkyl group, a lower alkoxy group, chlorine, or bromine, and may be the same or different from each other.
R ₅ and R ₆ are hydrogen, a methyl group, an ethyl group, a trifluoromethyl group or a trichloromethyl group, and may be the same or different.
100 parts by weight of an aromatic polyetheramide resin having a repeating unit represented by p-phenylene group, metaphenylene group, diphenylene ether group, diphenylene sulfone group, diphenylene group, or naphthylene group; (In formula (), X is -SO ₂ - or

The present invention relates to an aromatic polyetheramide resin composition containing 0.5 to 20 parts by weight of a bisphthalimide compound represented by the following formula. The aromatic polyetheramide resin used in the present invention is, for example, an aromatic diamine represented by the above general formula () and an aromatic dicarboxylic acid dihalide represented by the following general formula ('), XCO-Ar-COX (') (However, in the formula, Ar represents p-phenylene group, m-phenylene group, diphenylene ether group, diphenylene sulfone group, diphenylene group, naphthylene group, and X represents chlorine or bromine) through polycondensation reaction. You can get it. Aromatic diamines represented by the general formula () include 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[3-methyl-4-(4-aminophenoxy)phenyl]
Propane, 2,2-bis[3-chloro-4-(4
-aminophenoxy)phenyl]propane, 2,
2-bis[3-bromo-4-(4-aminophenoxy)phenyl]propane, 2,2-bis[3-
Ethyl-4-(4-aminophenoxy)phenyl]
Propane, 2,2-bis[3-propyl-4-
(4-aminophenoxy)phenyl]propane,
2,2-bis[3-isopropyl-4-(4-aminophenoxy)phenyl]propane, 2,2-
Bis[3-butyl-4-(4-aminophenoxy)
phenyl]propane, 2,2-bis[3-sec-
Butyl-4-(4-aminophenoxy)phenyl]
Propane, 2,2-bis[3-methoxy-4-
(4-aminophenoxy)phenyl]propane,
2,2-bis[3-ethoxy-4-(4-aminophenoxy)phenyl]propane, 2,2-bis[3,5-dimethyl-4-(4-aminophenoxy)phenyl]propane, 2,2-bis[ 3,5
-dichloro-4-(4-aminophenoxy)phenyl]propane, 2,2-bis[3,5-dibromo-4-(4-aminophenoxy)phenyl]propane, 2,2-bis[3,5-dimethoxy-4
-(4-aminophenoxy)phenyl]propane,
2,2-bis[3-chloro-4-(4-aminophenoxy)-5-methylphenyl]propane, 1,
1-bis[4-(4-aminophenoxy)phenyl]ethane, 1,1-bis[3-methyl-4-
(4-aminophenoxy)phenyl]ethane, 1,
1-bis[3-chloro-4-(4-aminophenoxy)phenyl]ethane, 1,1-bis[3-bromo-4-(4-aminophenoxy)phenyl]
Ethane, 1,1-bis[3-ethyl-4-(4-
aminophenoxy)phenyl]ethane, 1,1-
Bis[3-propyl-4-(4-aminophenoxy)phenyl]ethane, 1,1-bis[3-isopropyl-4-(4-aminophenoxy)phenyl]ethane, 1,1-bis[3-butyl-4-
(4-aminophenoxy)phenyl]ethane, 1,
1-bis[3-sec-butyl-4-(4-aminophenoxy)phenyl]ethane, 1,1-bis[3
-Methoxy-4-(4-aminophenoxy)phenyl]ethane,1,1-bis[3-ethoxy-4
-(4-aminophenoxy)phenyl]ethane,
1,1-bis[3,5-dimethyl-4-(4-aminophenoxy)phenyl]ethane, 1,1-bis[3,5-dichloro-4-(4-aminophenoxy)phenyl]ethane, 1,1- Screw [3,5
-dibromo-4-(4-aminophenoxy)phenyl]ethane, 1,1-bis[3,5-dimethoxy-4-(4-aminophenoxy)phenyl]ethane, 1,1-bis[3-chloro-4-( 4-aminophenoxy)phenyl-5-methylphenyl]ethane, bis[4-(4-aminophenoxy)
phenyl]methane, bis[3-methyl-4-(4
-aminophenoxy)phenyl]methane, bis[3-chloro-4-(4-aminophenoxy)phenyl]methane, bis[3-bromo-4-(4-aminophenoxy)phenyl]methane, bis[3-
Ethyl-4-(4-aminophenoxy)phenyl]
Methane, bis[3-propyl-4-(4-aminophenoxy)phenyl]methane, bis[3-isopropyl-4-(4-aminophenoxy)phenyl]methane, bis[3-butyl-4-(4-aminophenoxy)phenyl ]methane, bis[3-
sec-Butyl-4-(4-aminophenoxy)phenyl]methane, bis[3-methoxy-4-(4-
aminophenoxy)phenyl]methane, bis[3
-ethoxy-4-(4-aminophenoxy)phenyl]methane, bis[3,5-dimethyl-4-
(4-aminophenoxy)phenyl]methane, bis[3,5-dichloro-4-(4-aminophenoxy)phenyl]methane, bis[3,5-dibromo-4-(4-aminophenoxy)phenyl]methane, bis[3 ,5-dimethoxy-4-(4-aminophenoxy)phenyl]methane, bis[3,
5-chloro-4-(4-aminophenoxy)-5-
methylphenyl]methane, 1,1,1,3,3,
3-hexafluoro-2,2-bis[4-(4-
aminophenoxy)phenyl]propane, 1,
1,1,3,3,3,-hexachloro-2,2-
Bis[4-(4-aminophenoxy)phenyl]
Propane, 3,3-bis[4-(4-aminophenoxy)phenyl]pentane, 1,1-bis[4
-(4-aminophenoxy)phenyl]propane,
1,1,1,3,3,3-hexafluoro-2,
2-bis[3,5-dimethyl-4-(4-aminophenoxy)phenyl]propane, 1,1,1,
3,3,3-hexachloro-2,2-bis[3,
5-dimethyl-4-(4-aminophenoxy)phenyl]propane, 3,5-bis[3,5-dimethyl-4-(4-aminophenoxy)phenyl]
Pentane, 1,1-bis[3,5-dimethyl-4
-(4-aminophenoxy)phenyl]propane,
1,1,1,3,3,3-hexafluororo-
2,2-bis[3,5-dibromo-4(4-aminophenoxy)phenyl]propane, 1,1,
1,3,3,3-hexachloro-2,2-bis[3,5-dibromo-4-(4-aminophenoxy)phenyl]propane, 3,3-bis[3,5
-dibromo-4-(4-aminophenoxy)phenyl]pentane, 1,1-bis[3,5-dibromo-4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy) phenyl]butane, 2,2-bis[3-methyl-4-(4-aminophenoxy)phenyl]
Butane, 2,2-bis[3,5-dimethyl-4-
(4-aminophenoxy)phenyl]butane, 2,
2-bis[3,5-dibromo-4-(4-aminophenoxy)phenyl]butane, 1,1,1,
3,3,3-hexafluoro-2,2-bis[3
-Methyl-4-(4-aminophenoxy)phenyl]propane and the like. All known aromatic dicarboxylic acid dihalides represented by the general formula (') used in the present invention are useful. For example, terephthalic acid dichloride, terephthalic acid dibromide, isophthalic acid dichloride, isophthalic acid dibromide, diphenyl ether dicarboxylic acid dichloride-4,4', diphenyl ethercarboxylic acid dibromide-4,4', diphenyl sulfone dicarboxylic acid dichloride -4,4', diphenylsulfonedicarboxylic acid dibromide -4,4',
diphenyldicarboxylic acid dichloride-4,4',
diphenyldicarboxylic acid dipromide-4,4',
Naphthalene dicarboxylic acid dichloride-1,5 or naphthalene dicarboxylic acid dibromide-
1, 5, etc., and at least one of them is used. The blending ratio of the aromatic diamine and aromatic dicarboxylic acid dihalide is 1 equivalent of the former to 1 equivalent of the latter.
What is necessary is just to set it in the range of 0.9-1.2 equivalent. If it is out of the above-mentioned range, it will be difficult to obtain a high molecular weight product, and only an oligomer-like product that does not exhibit a resinous state will be obtained. The latter aromatic dicarboxylic acid dihalide is preferably in a range of 0.97 to 1.03 equivalents. In particular, when the amounts are equal, the maximum molecular weight of the target aromatic polyetheramide resin can be obtained. In the present invention, a part of the aromatic diamine can be replaced with other known aromatic diamines. Its amount should conveniently have an upper limit of 50 mol % (based on the total amount of aromatic diamines).
50 mol%. If it exceeds this, there is a risk that molding processability will be particularly impaired. Examples of other aromatic diamines include m-phenylenediamine, p-phenylenediamine, 4,4'-diaminodiphenylmethane,
4,4'-diaminodiphenyl ether, 4,4'-
Diaminodiphenyl sulfone, 4,4'-diaminodiphenylpropane-2,2,4,4'-diaminodiphenyl sulfide, 1,5-diaminonaphthalene, 4,4'-diaminodiphenylethane, m-
toluylene diamine, p-tolylene diamine,
3,4'-diaminobenzanilide, 1,4-diaminonaphthalene, 3,3'-dichloro-4,4'-diaminodiphenyl, benzidine, 4,4'-diaminodiphenylamine, 4,4'-diamino Diphenyl-N-methylamine, 4,4'-diaminodiphenyl-N-phenylamine, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyldiethylsilane, 4,4'-diaminodiphenyl There are silanes, and at least one of these is used. In addition, in the present invention, known aliphatic diamines such as piperazine, hexamethylene diamine, heptamethylene diamine, octamethylene diamine, nonamethylene diamine, decamethylene diamine, p-xylylene diamine, m-xylylene diamine, tetramethylene diamine, etc. Diamine, dodecamethylene diamine, 4,4-dimethylheptamethylene diamine, 3-methylheptamethylene diamine, 2,11-diaminododecane, 1,12-diaminooctadecane, etc. can also be used in combination. The combined use of aliphatic diamine has the effect of further improving the moldability of the target aromatic polyetheramide resin. However, as the amount of the compound increases, the heat resistance gradually decreases, so the amount of the compound should be set so as not to impair the purpose of the present invention.
In normal cases, it should be used in combination in a range of 30 mol% or less, preferably 10 mol% or less (based on the total amount of diamine). The aliphatic diamine may be used alone or in combination with the other aromatic diamine described above and the aromatic diamine represented by the general formula (). When the aforementioned various diamines are used in combination, the blending ratio of all the diamine components and the aromatic dicarboxylic acid dihalide can be set on exactly the same basis as described above. In the present invention, for the reaction, the method already used for the reaction between an amine and an acid can be directly adopted, and the various conditions etc.
It is not particularly limited. For example, this can be achieved by an interfacial polycondensation method, a solution polycondensation method, a solution polycondensation method, or the like. In the interfacial polycondensation reaction, a known water-soluble neutralizing agent described below is used.
In addition, in the case of solution polymerization method, triethylamine,
A neutralizing agent consisting of a known tertiary amine such as pyridine, tributylamine, pyridine, etc. is used.
A reaction solvent is used in the interfacial polycondensation method and solution polymerization method, but this solvent must be capable of dissolving at least one of aromatic diamine or aromatic dicarboxylic acid dihalide, preferably both. . A representative example of a particularly effective reaction solvent for use in the present invention is cyclohexanone. Some examples of other solvents that can be used include methylene chloride, trichlene, verkrene, ethane dichloride, nitrobenzene, chloroform, carbon tetrachloride, diisobutyl ketone, acetophenone, p-methylacetophenone, N,N-dimethylformamide, N,N-dimethylacetamide, N,N-diethylformamide, N,N-diethylacetamide, N,N-
Examples include dimethylmethoxyacetamide, dimethylsulfoxide, N-methyl-2-pyrrolidone, pyridine, dimethylsulfone, hexamethylphosphoramide, tetramethylenesulfone, dimethyltetramethylenesulfone, and the like. Two or more reaction solvents may be used in combination, if necessary, such as to facilitate the dissolution operation.
Furthermore, in order to obtain a product with as high a molecular weight as possible, it is preferable to use a highly dehydrated solvent for dissolving the aromatic dicarboxylic acid dihalide. especially,
When performing solution polycondensation using a polar solvent such as N,N-dimethylformamide, N,N-dimethylacetamide, or N-methyl-2-pyrrolidone, 5 to 10% by weight of lithium chloride, calcium chloride, Synthesis by adding rhodan calcium or the like is advantageous because the solubility increases significantly. In addition to this co-solvent, all other known co-solvents as described below are effective. Further, according to research conducted by the present inventors, the following effective reaction method was discovered. That is, unlike the usual interfacial polycondensation method in which diamines are dissolved in aqueous alkaline solutions, diamines are dispersed in aqueous alkaline solutions, and a solution of aromatic dicarboxylic acid dihalide dissolved in an organic solvent is added to this. This is a method of causing a reaction. By polymerizing in this method, the resulting halogenated aqueous solution is neutralized with a neutralizing agent and becomes water and a metal halide, which dissolves in water. Since no residue remains, this gives favorable results to various properties of the polymer. In this case, the amount of alkali used is at least 1.3 equivalents relative to the aromatic dicarboxylic acid halide, preferably from 1.0 to 1.1 equivalents. Examples of the neutralizing agent used here include, but are not limited to, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate, etc. which are dissolved in water. Further, the amount of water is sufficient as long as the above-mentioned neutralizing agent is sufficiently dissolved at room temperature. Of course, using more than that will not affect the reaction. Further, the reaction temperature is in a state where water is a liquid, that is, in the range of 0 to 100°C, preferably 5 to 60°C. The above polycondensation method can be carried out, for example, by the following procedure. First, a neutralizing agent is dissolved in an appropriate amount of water, and an aromatic diamine is added thereto. Furthermore, a solution of aromatic dicarboxylic acid halide dissolved in an organic solvent is added and reacted. At this time, it is preferable to carry out the reaction in a state where the aromatic diamine is dispersed in the alkaline aqueous solution by stirring. Next, only the organic phase is separated and placed in an organic solvent that does not dissolve the polymer and is easily compatible with the reaction solvent to precipitate the polymer. By filtering this, an aromatic polyetheramide resin is obtained. In the present invention, the aforementioned various aromatic diamines and aliphatic diamines can be used as neutralizing agents. In this case, the amount may be increased at a rate of 1 equivalent or less (an amount not involved in the reaction). It is also possible to use a known polyamide-forming reaction between an amide-forming derivative other than an aromatic dicarboxylic acid dihalide and an aromatic diamine represented by the general formula (), such as high-temperature polycondensation using a phosphorus catalyst or transesterification method. An aromatic polyetheramide resin having repeating units represented by the general formula () can be obtained. The aromatic polyetheramide resin of the present invention has a viscosity (concentration of 0.2 g/dl in dimethylformamide, 30
°C) is 0.2 to 1.5 dl/g, preferably 0.4 to 0.8
dl/g. If it is less than 0.2 dl/g, the strength will decrease;
If it exceeds 1.5 dl/g, moldability tends to be poor. In the present invention, specific examples of the bisphthalimide compound represented by the general formula () include bis[4-(3-phthaliminophenoxy)
phenyl]sulfone (in the general formula (), X is -SO ₂ -bisphthalimide compound), bis[4-
(4-phthaliminophenoxy)phenyl]propane and the like. In the present invention, the bisphthalimide compound represented by the general formula () can be mixed with the aromatic polyetheramide resin by various known methods. (1) Direct addition to aromatic polyetheramide resin powder; (2) Dissolving or swelling immersion of aromatic polyetheramide resin powder in a low boiling point solvent such as alcohol, ketone, or saturated hydrocarbon;
A method of impregnating or adhering the bisphthalimide compound to aromatic polyetheramide resin powder by dissolving the bisphthalimide compound therein, stirring and mixing, and distilling off the solvent, (3)
(4) In the production process of aromatic polyetheramide resin, the above-mentioned phthalimide compound is added before or during polymerization. The phthalimide compound can be added and mixed by a method such as a concentration solidification method or a solvent stripping method to obtain the bisphthalimide compound-containing aromatic polyetheramide resin powder. If the amount of the bisphthalimide compound added is too small, no effect will be observed, and if it is too large, moldability will be significantly improved, but mechanical strength such as tensile strength will be significantly reduced. Therefore, the amount of the bisphthalimide compound added is practically 0.5 to 20 parts by weight, preferably 2 to 15 parts by weight, per 100 parts by weight of the resin. Furthermore, by blending other types of polymers into the resin composition of the present invention, its properties can be improved, and by coexisting additives such as antioxidants, ultraviolet absorbers, lubricants, and flame retardants, Its properties can also be improved. EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited thereto. below,
"%" means "% by weight". Example 1 A 10% cyclohexanone solution of an acid chloride mixture with a mixing ratio of terephthalic acid dichloride and isophthalic acid dichloride of 1:1 (weight ratio) and 20% cyclohexanone solution of 2,2-bis[4-(4-aminophenoxy)phenylpropane] 10% cyclohesisanone solution
Aromatic polyether amide was produced by contacting and reacting in the presence of an aqueous solution of % caustic soda. However, the blending ratio of the acid chloride mixture and the aromatic diamine is equimolar. The reduced viscosity of this in dimethylformamide (0.2g/dl) is 0.94dl/
It was hot at g. To 100 parts by weight of this aromatic polyetheramide resin powder, bis[4-(3-phthaliminophenoxy)phenyl]sulfone was added as a bisphthalimide compound to 100 parts by weight of the polymer.
Parts by weight were added and pelletized at 300 to 320°C using an extruder. A test piece was molded from this pellet using an injection molding machine (340° C., 900 kg/cm ² ). Tensile strength 910Kg/cm ² , Impact strength 14Kg/cm ² , Heat distortion temperature 185
It was warm at ℃. Example 2 10 Separable flasks, stir bar, thermometer,
Set the dropping funnel and add 171.8g of NaOH to 800ml of water.
Dissolve it and put it in a flask. Next, 594 g of 2,2-bis[4-(4-aminophenoxy)phenyl]propane and 66 g of 4,4'-diaminodiphenyl ether were dissolved in 3.4 kg of cyclohexanone, poured into the flask, and cooled to -2°C. do.
Meanwhile, 182 g of terephthalic acid dichloride and 182 g of isophthalic acid dichloride were mixed with 2.4 g of cyclohexanone.
Dissolves in Kg. Pour the acid chloride solution through the dropping funnel, making sure that the reaction temperature does not exceed 10°C. Three hours after the dropwise addition, 18.9 g of benzoyl chloride was dissolved in 200 g of cyclohexanone and added. After another 2 hours, the reaction solution is poured into methanol to isolate the polymer. 2,2-bis[4-(4-phthaliminophenoxy)phenyl] was added as a bisphthalimide compound to 100 parts by weight of the aromatic polyetheramide resin powder obtained by drying.
Add propane in the amount shown in Table 1 and use an extruder to
It was pelletized at 300-320°C. Various test pieces were molded from the pellets by injection molding. The table shows the molding conditions and properties of each pellet.

【table】

Claims (1)

[Claims] 1 General formula () (However, in formula (), R ₁ to _{R 4} represent hydrogen, a lower alkyl group, a lower alkoxy group, chlorine, or bromine, and may be the same or different from each other.
R ₅ and R ₆ are hydrogen, a methyl group, an ethyl group, a trifluoromethyl group or a trichloromethyl group, and may be the same or different.
Arromatic polyether amide resin having a repeating unit represented by p-phenylene, metaphenylene, diphenylene ether, diphenylene sulfone, diphenylene, or naphthylene group.
100 parts by weight and general formula () (In formula (), X represents -SO ₂ - or [Formula]) An aromatic polyetheramide resin composition containing 0.5 to 20 parts by weight of a bisphthalimide compound.