JPS5836017B2 - Aromatic polyetheramide resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a resin composition comprising an aromatic polyetheramide resin mixed with a modifier.

General formula (g) (wherein R1 to R4 represent hydrogen, lower alkyl, lower alkoxy group, chlorine or bromine, R5 and R6 are hydrogen, methyl group, ethyl group, trifluoromethyl group or trichloromethyl group; , may be the same or different.

) It is disclosed in JP-A-52-23198 and U.S. Pat.
, 5 0 5, 2 8 8 and the like.

By the way, the aromatic polyether amide obtained using such a special diamine as a raw material has mechanical properties such as tensile strength, bending strength, and impact strength, thermal properties such as heat distortion temperature and thermal decomposition, 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 excellent properties, if the moldability is poor, it will be difficult to economically manufacture the product. Not only is it not possible to do so, but also the excellent properties cannot be fully demonstrated in the product.

For example, when manufacturing products by injection molding using polymers with high softening and melting temperatures, high plasticizing temperatures, high injection pressures, and high mold temperatures are required, which only increases costs. However, high plasticization temperatures induce thermal decomposition of the polymer, and high injection pressures cause distortion in the product.

Furthermore, if such 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 shapeability of aromatic polyetheramides as well.

The present inventors have conducted intensive studies to improve the shapeability and processability of aromatic polyetheramide while maintaining its excellent properties, and as a result, they have arrived at the present invention.

That is, an object of the present invention is to provide a resin composition which lowers the melt viscosity and molding temperature of aromatic polyether amide, and which maintains excellent properties such as mechanical properties.

Therefore, the present invention provides a general formula (I) (formula CI), in which R1 to R4 represent hydrogen, a lower alkyl group, a lower alkoxy group, chlorine or bromine, and may be the same or different from each other. .

R and R6 are hydrogen, a methyl group, an ethyl group, a trifluoromethyl group, or a trichloromethyl group, and may be the same or different.

Ar represents p-phenylene, metaphenylene, diphenylene ether, diphenylene sulfone, diphenylene, or naphthylene group.

) to an aromatic polyetheramide resin having a repeating unit represented by the general formula (II) (wherein R and R' are an alkyl group or an aromatic group having 1 to 20 carbon atoms, and are the same as each other). may also be different.

Z is a group selected from -CH2-.

) The present invention relates to an aromatic polyether amide resin composition formed by blending the amide compound represented by the following formula in a ratio of 0.5 to 20 parts by weight to 100 parts by weight of the former.

Examples of the amide compound represented by the general formula (n) used in the present invention include 2,2-bis(4-(4benzoylaminophenoxy)phenyl)propane, bis(4-
(4-penzoylaminophenoxy)phenyl]methane, 2,2-bis(4-(4-stearylaminophenoxyphenyl)propane, bis(4-(4-acetylaminophenoxy)phenyl)propane, Di(4-(4-pensoylaminophenoxy)phenyl)sulfone, di[
4-(4-penzoylaminophenoxy)phenyl]ketone, diC4-(4-penzoylaminophenoxy)phenyl]ether, di[4-(4-penzoylaminophenoxy)phenyl]sulfide, di(4- (3-penzoylaminophenoxy)phenyl]sulfone, di(4
-(2-penzoylaminophenoxy)phenyl]sulfone and the like.

In the present invention, the amide compound represented by the general formula (I) can be mixed with the aromatic polyether amide 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 amide compound to aromatic polyether amide tree powder by dissolving the compound, stirring and mixing, and distilling off the solvent, (3) In the manufacturing process of aromatic polyether amide resin , a method of polymerizing by adding the amide compound to the amide compound before or during polymerization,
(4) In the manufacturing process, the amide compound is added to the aromatic polyetheramide resin solution after polymerization, and the amide compound-containing aromatic polyetheramide resin powder is obtained by a concentration solidification method or a solvent stripping method;
It can be mixed by etc.

If the amount of the amide 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 amide compound added is practically 0.5 to 20 parts by weight per 100 parts by weight of the resin.

The aromatic polyetheramide resin used in the present invention includes, for example, an aromatic diamine represented by the above-mentioned general formula (III) and an aromatic dicarboxylic acid dihalide represented by the following general formula (IV) (However, Ar is p- phenylene group, m-phenylene group,
It represents a diphenylene ether group, a diphenylene sulfone group, a diphenylene group, or a naphthylene group, and X represents chlorine or bromine.

) using known methods such as solution polymerization method or
It is obtained by reaction according to the method shown in Japanese Patent No. 8616.

Examples of the aromatic diamine represented by the general formula (g) include 2,2-bis(4-(4-aminophenoxy)phenyl)propane, bis(4-(4-aminophenoxy)phenyl)methane, 2,2- bis[3,5-dimethyl-4-(4-aminophenoxy)phenyl]propane,
There are 2,2-bis[3-methyl=4-(4-aminophenoxy)phenyl]propane, 2,2-bis[3,5-dibromo-4-(4-aminophenoxy)phenyl]propane, and these 1 More than one species is used.

Examples of the aromatic dicarboxylic acid dihalide represented by the general formula (IV) include terephthalic acid dichloride, isophthalic acid dichloride, diphenyl ether dicarboxylic acid dichloride, diphenyldicarboxylic acid dichloride, naphthalene dicarboxylic acid dichloride, etc. One or more types may be used, and a mixture of terephthalic acid dichloride and isophthalic acid dichloride is particularly preferably used.

It is also possible to perform 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 ([1), such as high-temperature polycondensation using a phosphorus catalyst or transesterification method. An aromatic polyetheramide resin having repeating units represented by general formula (I) can be obtained.

The aromatic polyetheramide resin of the present invention has a reduced viscosity of 0.
．． 3 ~1. 5dll'? , preferably 0.5~
It is 0.9dllV.

0. The strength decreases below 3 dllg, and the strength decreases to 1.5ηs.
If P//o is exceeded, the moldability will be poor.

Furthermore, by blending other types of polymers into the resin composition of the present invention, its properties can be improved, and additives such as antioxidants, ultraviolet absorbers, lubricants, and flame retardants can be made to coexist. It is also possible to improve its properties.

Hereinafter, the present invention will be explained in more detail with reference to Examples.
It is not limited to this.

*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 2,2-bis-(
20 of 4-(4-aminophenoxy)phenylpropane
% cyclohexanone solution in the presence of a 10% aqueous sodium hydroxide solution to produce an aromatic polyether amide.

However, the blending ratio of the acid chloride mixture and the aromatic diamine is equimolar.

This in dimethylformamide (0.2?/dl
) has a reduced viscosity of 0.94 dll'! ? Met.

To 100 parts by weight of this aromatic polyetheramide resin powder, 2,2-bis(4-(4-penzoylaminophenoxy)phenyl)propane was added in the amount shown in Table 1, and heated at 300 to 320°C using an extruder. Made into a beret.

Various test pieces were molded from this pellet using an injection molding machine.

Table 1 shows the molding conditions and various properties of each pellet.

Example 2 1 of an acid chloride mixture with a mixing ratio of terephthalic acid dichloride/isophthalic acid dichloride of 4=6 (weight ratio)
0% cyclohexanone solution and 2,2-bis(4-(4
An aromatic polyetheramide resin was produced from -aminophenoxy)phenyl]propane in the same manner as in Example 1.

After the polymerization was completed, the resulting polymer solution was separated from the aqueous phase and washed with water, and then 5 parts by weight of di(4-(4-penzoylaminophenoxy)phenyl)sulfone was added to 100 parts by weight of the polymer.

This was concentrated and solidified to obtain an amide compound-containing aromatic polyether amide resin composition.

The reduced viscosity is 0.88 dl/f? Met. This is 300
It was pelletized at ~310°C and molded into test pieces by injection molding.

Tensile strength: 980ky/i, impact strength: 1 2. 2k
gcm 2 /cyyt, and the heat distortion temperature was 178°C.

Example 3 An acid chloride mixture with a mixing ratio of terephthalic acid dichloride/isophthalic acid dichloride of 1:1 (weight ratio) and 2
,2-bis(4-(4-aminophenoxy)phenyl)
propane, reduced viscosity 0.77 dl/? by solution polymerization using N-methylpyrrolidone as a solvent. An aromatic polyetheramide resin was obtained.

To 100 parts by weight of this polymer, 3 parts by weight of di[4-(3-acetylaminophenoxy)phenyl]sulfone was added, pelletized at 300 to 310°C, and a test piece was molded by injection molding.

Tensile strength 9 6 0 kg/cti Impact strength 110-○
The final heat deformation temperature was 180°C.

Example 4 A stirring rod, a thermometer, and a dropping funnel were set in a 10-liter separable flask, and NaOH 1 7 1.8 ? water 8
00ml and put it in a flask.

Next, 594 g of 2,2-bis(4-(4-aminophenoxy)phenyl)propane and 66 P of 4,4'-diaminodiphenyl ether were dissolved in 3.4 kg of cyclohexanone and poured into a sagi flask. Cool to 2°C.

On the other hand, 182 grams of terephthalic acid dichloride and 1822 grams of isophthalic acid dichloride were mixed with 2 grams of cyclohexanone. 4
Dissolve in kg.

This acid chloride** solution is poured through the dropping funnel, making sure that the reaction temperature does not exceed 10°C.

Three hours after the dropwise addition, benzoyl chloride 18.9S' was dissolved in cyclohexanone 2001 and added.

After another 2 hours, the reaction solution is poured into methanol to isolate the polymer.

Aromatic polyetheramide resin powder 1 obtained by drying
00 parts by weight, 2,2-bis[4-(4-penzoylaminophenoxy)phenyl]propane was added in the amount shown in Table 2, and pelletized at 300 to 320°C using an extruder.

Various test pieces were formed from the pellets using an injection molding machine.

Table 2 shows the molding conditions and various properties of each pellet.

Example 5 Aromatic polyetheramide powder was obtained using the same equipment and method as in Example 4 using raw materials having the following composition.

10 parts by weight of di(4-(4-penzoylaminophenoxy)phenyl)ether was added to 100 parts by weight of the obtained resin powder, pelletized at 300°C, and by injection molding.
A test piece was molded.

Tensile strength 8 70 kg/crit1 Impact strength 1
4. The weight was 8 kgcm/CI1 yen, and the heat distortion temperature was 182°C.

Example 6 A polymer was obtained using the same equipment and method as in Example 4 using raw materials having the following composition.

5 parts by weight of bis[4-(4-stearylaminophenoxy)phenyl]methane was added to 100 parts by weight of the obtained resin powder, pelletized at 300°C, and a test piece was molded by injection molding.

Tensile strength 9 1 0 kg/cI? L, impact strength 1 2
．． 2kg/cry1 The heat distortion temperature was 184°C.

Claims (1)

[Claims] 1 General formula (I) (However, in formula (I), R1 to R4 represent hydrogen, a lower alkyl group, a lower alkoxy group, chlorine or bromine, and may be the same or different from each other. R5 and R6 are hydrogen, a methyl group, an ethyl group, a trifluoromethyl group, or a trichloromethyl group, and may be the same or different from each other. Ar is p-phenylene, metaphenylene, diphenylene. Ren ether, diphenylene sulfone, diphenylene,
Indicates a naphthylene group. ) to 100 parts by weight of an aromatic polyetheramide resin having repeating units represented by the general formula (I[) (wherein R and R' are an alkyl group or an aromatic group having 1 to 20 carbon atoms, and An aromatic polyether amide resin composition comprising 0.5 to 20 parts by weight of an amide compound represented by the following formula. The aromatic polyetheramide resin composition according to claim 1, which is a compound comprising: *