JPS59147046A - Aromatic polyether amide resin composition - Google Patents

Abstract

PURPOSE:To provide the titled composition having improved moldability and processability without lowering the original characteristics of the base resin, by compounding a bisphthalimide compound to the resin. CONSTITUTION:The objective composition is prepared by compounding (A) 100pts.wt. of an aromatic polyether amide resin having the recurring unit of formula I (R1-4 are H, lower alkyl, etc.; R5 and R6 are H, methyl, trifluoromethyl, etc.; Ar is p-phenylene, m-phenylene, etc.) with (B) 0.5-20pts.wt., preferably 2- 15pts.wt. of a bisphthalimide compound of formula II (X is -O-, -SO2-, -CO, etc.; R7 and R10 are 1-4C alkyl; R8 and R9 are 1-4C alkyl or halogen; p, q, r and s are 0 or 1-4; t is 1-25). Addition of an aliphatic diamine to the composition is preferable.

Description

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

General formula (IlIl (in the formula, r R1-R4 represent hydrogen, lower alkyl, lower alkoxy group, chlorine or bromine2, and may be the same or different from each other. R5 and FLs are hydrogen, methyl group, ethyl It is possible to obtain an aromatic polyamide from an aromatic diamine containing an ether bond represented by a group, a trifluoromethyl group or a trichloromethyl group, which may be the same or different from each other, 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 polyether amide can be obtained using such a special diamide as a raw material.

Mechanical properties such as tensile strength 2 bending strength and impact strength, thermal properties such as heat distortion temperature and thermal decomposition, arc resistance, dielectric constant,
Electrical properties such as dielectric loss.

It maintains excellent properties such as flame resistance and dimensional stability,
For this reason, general molded products, films, etc. made by injection molding, extrusion molding, press molding, etc. are expected to have a wide range of 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 in glass materials, and even if fc itself has inherently excellent properties, if moldability is poor, it will be difficult to economically manufacture the product. It is impossible to make full use of its excellent properties in a product.

For example, when a product is made 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 This causes distortion inside. In addition, if such strict conditions are not met, external defects such as short shots, sink marks, and flow marks occur; (1) mechanical properties 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 polyether amide, and as a result, have arrived at the present invention.

That is, 1 the present invention is based on the general formula (1) ((9 formula (in Il + R1 to FL4 represent hydrogen, a lower alkyl group, a lower alkoxy group, chlorine or bromine).

They may be the same or different.几5 and R6 are hydrogen, a methyl group, an ethyl group, a trifluoromethyl group, or a trichloromethyl group, and may be the same or different.

A and r are p-phenylene group and metaphenylene group.

100 parts by weight of aromatic polyether amide resin having repeating units represented by diphenylene ether group, diphenylene sulfone group, diphenylene group, f-ethylene group) and general formula ('') (however, 2 (I[) where,
p, q, r and S are 0 or an integer of 1 to 4, t is 1 to
is an integer of 25, R7 and 几10 may be the same or different from each other, and R8 and R9 may be the same or different from each other <, p, q.

The present invention relates to an aromatic polyetheramide resin composition containing 0.5 to 20 parts by weight of a bisphthalimide compound (r and S may be the same or different).

The aromatic polyetheramide resin used in the present invention is, for example, an aromatic diamine represented by the above-mentioned general formula +110 and an aromatic dicarboxylic acid cybaride represented by the following general formula.

XCO-Ar-COX (I[I) (however,
In the formula, Ar is p-phenylene group + m-phenylene group,
It is obtained by polycondensation reaction of a diphenylene ether group, a diphenylene sulfone group, a diphenylene group, a naphthylene group, and X represents chlorine or bromine.

The aromatic diamino represented by the general formula (I
Aminophenoxy)phenyl]furopane, 2.2-bis[3-chloro-4-(4-aminophenoxy)phenyl]propane, 2.2-bis[3-bromo-4-(4-aminophenoxy)phenyl]propane , 2.2-bis [
3-F-4-(4-aminophenoxy)phenyl]
Propane, 2+2-bis[3-globyl-4-(4-aminophenoxy)phenyl]propane, 2,2-bis[
3-isopropyl-4-(4-aminophenoxy)phenyl]furopane, 2. .

2-bis[3-butyl-4-(4-aminophenoxy)
phenyl]propane, 2-bis[3-5ec-butyl-4-(4-aminophenoxy)phenyl]propane,
2.2-bis[3-methquin-4-(4-aminoenoxy)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]glo, pan, 1 .1-bis[4-(4-aminoneenoxy)phenyl]ethane, 1.1-bis[3-mef-4-(4-a is nophdinoxy)7enyl]ethane, 1.
1-bis[3-chloro-4-(4-aminophenoxy)
phenyl]ethane, l11-bis[3-bromo-4-(
4-aminophenoxy)phenyl]ethane, 1.1-bis[3-functionalfk-4-(4-aminophenoxy)phenyl]ethane, 1. l-bis[3-globyl-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(
3-5ec-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, l,1-bis(3,5-dimethyl-4-
(4-Aminophenolic)phenyl]ethane, 1.1-
Bis[315-dichloro-4-(4-aminophenoxy)phenyl]ethane, 1,1-bis[3,5-dibromo-4-(4-aminophenoxy)phenyl]ethane, 1
．． 1-bis[3,5-dimethoxy-4-(4-aminophenolic)phenyl]ethane, 1.1-bis[3-chloro-4-(4-aminophenolic)phenyl-5-methylphenyl]ethane , bis[4-(4-aminophenoxy)phenylcomethane.

Bis[3-methyl-4-(4-aminophenoxy)phenylcomethane, bis[3-70 rho-4-(4-aminophenoxy)phenylcomethane.

Bis[3-bromo-4-(4-aminophenoxy)phenylcomethane, bis[3-ethyl-4-(4-aminophenoxy)phenylcomethane.

Bis[3-propyl-4-(4-aminophenoxy)phenylcomethane, bis[3-ingrovir-4-(4-
aminophenoxy) phenylcomethane, bis[3-butyl-4-(4-aminophenoxy)phenylcomethane,
Bis(3-sec-butyl-4-(4-aminophenolic)phenylcomethane, bis[3-methoxy-4-(4
-aminophenoxy)phenylcomethane, bis[3-ethoxy-4-(4-aminophenoxy)phenylcomethane, bis[3,5-dimethyl-4=(4-aminophenoxy)phenylcomethane.

Bis[3,5-dichloro-4-(4-aminophenoxy)phenylcomethane, bis[3,5-dibromo-4-(
4-aminophenoxy)phenylcomethane, bis[3,
5-dimethoxy-4-(4-aminophenoxy)fe,
Nylcomethane, bis(3-chloro-4-(4-aminophenoxy)-5-methylphenylcomethane, 1,1
,1,3,3.3-hexafluoro-starbis(4-
(4-aminoneenoxy)phenyl]propane, 1,1
,1゜3,3.3-hexachloro-2,2-bisl:4
-(4-aminophenoxy)phenyl]propane, 3°3-bis[4-(4-aminophenoxy)7enyl]pentane, 1. l-bis(4-(4-aminoneenoxy)
phenyl]propane, 1,1,1,3゜3.3-hexafluoro-2,2-bis[3,5-dimethyl-4-(4
-Abanophenoxy)phenyl]propane, 1,1,1
,3. Formula 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. l-bis[
a5-dimethyl-4-(4-abanophenoxy)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-λ2-bis[he5-sifuromo-4-(4-aminophenoxy)phenyl]propane,
3.3-bis[3,5-schif'romo4-(4-aminophenoxy)phenyl]pentane, 1,1-bis[3,
5-dibromo-4-(4-aminophenyl)phenyl pan.

2.2-bis(4-(4-aminophenoxy)phenylcobutane), 2.2-bis[3-methyl-4-(4-aminophenoxy)phenylcobutane.

2.2-bis[3,5-dimethyl-4-(4-aminophenoxy)phenyl]buta;y, 2.2-bis[3,5
-dibromo-4-(4-aminophenoxy)phenylcobutane, 1.1.1.3.3.3-hexafluoro-
There is 2,2-bis[3-methyl-4-(4-aminophenoxy)phenyl]chloroha/nato.

As the aromatic dicarboxylic acid civalide expressed in the general formula (ml) used in the present invention, all known aromatic dicarboxylic acid civalides belonging to this are useful. For example, terephthalic acid dichloride 2. Terephthalic acid dibromide, isophthalic acid dichloride, inphthalic acid dichloride Bromide, diphenyl ether dicarboxylic acid dichloride-4,4', diphenyl ether carboxylic acid dichloride-4,4', diphenyl sulfone dicarboxylic acid dichloride-4,4', diphenyl sulfone dicarboxylic acid dichloride-4,4'
, diphenyldicarboxylic acid dichloride ~4.4',
Examples include diphenyldicarboxylic acid siglomite-4,4', naphthalenedicarboxylic acid dichloride-1,5,fi, and naphthalenedicarboxylic acid dichloride-1,5, and at least one of them is used.

The blending ratio of the aromatic diamine and the aromatic dicarboxylic acid sybaride may be set in a range of 0.9 to 1.2 equivalents of the latter to 1 equivalent of the former. If it is out of the above range, it will be difficult to obtain a product with a molecular weight similar to that of an oligomer that does not have a resinous appearance. The latter aromatic dicarboxylic acid cybaride 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. The amount should conveniently have an upper limit of 50-11 nyl% (based on the total amount of aromatic diamine). If it exceeds 50 molti, 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'-diaminodiphenylsulfone.

4,4'-cyaminodiphenylpropane-2,2,4
゜4'-diaminodiphenyl sulfide, 1,5-diaminonaphthalene, 4,4'-diaminodiphenylethane, m-) lylene diamine, p-tolylene diamine,
3.4'-diaminobenzanilide.

1.4-thia epsilon nonaphthalene, 3.3'-dichloro-4
, 4'-diaminodiphenyl, benzidine, 4.4'-
Diamino 7-phenylamine, 4.4'-diaminodiphenyl-N-methylamine, 4.4'-diaminodiphenyl-N-phenylamine, 3.3'-cya, monodiphenyl sulfone, 4.4'-diaminodiphenyl ale There are silane, 4,4'-diaminodiphenylsilane, etc., 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 cyanide, p-xylylene diamine, m-xylylene diamine, Tetramethylene diamine, dodecamethylene diamine, 4,4-dimethyl hebutamethylene diamine, 3-methyl hebutamethylene diamine, λ11-diaminododecane.

1.12-diaminophtathecan and the like 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. (based on the total amount of diamine). The aliphatic diamine is used alone or in combination with an aromatic diamine having the above-mentioned properties and an aromatic diamine represented by the general formula (1).

When the various diamines mentioned above are used in combination, the blending ratio of all the diamine components to the aromatic dicarboxylic acid dinolide can be set on exactly the same basis as mentioned above.

In the present invention, for the 9 reaction, a method already used for the reaction between an amine and an acid can be directly adopted, and the conditions are 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,
Pyridine, tributylamine.

A known neutralizing agent consisting of a tertiary amine such as pyridine is used. A reaction solvent is used in the interfacial polycondensation method and the solution polymerization method, but this solvent must be capable of dissolving at least one of aromatic diamines and aromatic dicarboxylic acid dino-rides, preferably both. Must be. A representative example of a particularly effective reaction solvent for use in the present invention is cyclohexynone.

Some other solvents that may be used include methylene chloride, trichlene, perchlorene, ethane dichloride, nitrobenzene, chloroform, carbon tetrachloride, and diisobutyl ketone.

Acetophenone, p-methylacetophenone.

N,N-dimethylformamide, N,N-dimethylacetamide, N,N-diethylformamide.

N,N-dimethylacetamide, N,N-dimethylmethoxyacetamide, dimethylsulfoxide.

N-methyl-2-pyrrolidone, pyridine, dimethylsulfone, hexamethylphosphoramide.

Examples include tetramethylene sulfone and dimethyltetramethylene sulfone.

Two or more reaction solvents may be used in combination, if necessary, 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 cybaride. Particularly when solution polycondensation is carried out using a polar solvent such as N,N-dimethylformamide, N,N-dimethylacetamide, or N-methyl-2-pyrrolidone.

5 to 10 weight percent lithium chloride as a co-solvent.

Synthesis by adding calcium chloride, calcium rhodan, etc. is advantageous as it significantly increases solubility.

In addition to this co-solvent, all other known co-solvents as described below are effective. Further, according to the research conducted by the two inventors, the following effective reaction method was discovered.

That is, it is like the usual interfacial polycondensation method.

This method is different from the method of dissolving diami/in an alkaline aqueous solution.
Disperse diamine in alkaline aqueous solution.

This is a method in which a solution of an aromatic dicarboxylic acid dihydride dissolved in an organic solvent is added to the mixture and reacted. By polymerizing in this method, the halogenated aqueous solution produced is neutralized with a neutralizing agent and becomes water and a metal halide, which dissolves in water.When the polymer is precipitated from the organic phase, the polymer is Since no Japanese additive remains, this method gives favorable results to various polymer products. 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. Here, the neutralizing agent used is sodium hydroxide that dissolves in water.

Examples include, but are not limited to, potassium hydroxide, sodium carbonate, and sodium hydrogen carbonate.

Further, the amount of water is sufficient as long as the above-mentioned neutralizing agent is sufficiently dissolved at the temperature. Of course, even if you use more than that, it will not affect the 7 reactions. Also, the reaction temperature is the state where water is a liquid.

That is, it 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, preferably,
It is preferable to stir the aromatic diamine to disperse it in the alkaline aqueous solution before reacting. Then only the organic phase is separated.

The polymer is precipitated by pouring it into an organic solvent that does not dissolve the polymer and is easily compatible with the reaction solvent. 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 by 1 equivalent or less (it not involved in the reaction).

In addition, known polyamide-forming reactions between amide-forming derivatives other than aromatic dicarboxylic acid dino-rides and aromatic diamines represented by the general formula (m) may be carried out, for example, by high-temperature polycondensation or transesterification using a 9-based catalyst. Also, an aromatic polyetheramide resin having repeating units represented by the general formula (I) can be obtained.

The aromatic polyetheramide resin of the present invention has a viscosity (concentration of 0.2y-/di in dimethylformamide, 30°C)
is 0.2 to 1. sdl/11-, preferably.

0°4~0.8 dll? There is. 0.2dll/9
If it is less than -, the strength will decrease, and if it exceeds 1.5 tie/P, the moldability will tend to be poor.

In the present invention, specific examples of the bisphthalide compound represented by general formula (n) include:

Li
Mixing can be carried out by adding the bis-7 curimide compound to a U aromatic polyetheramide resin solution and obtaining the bisphthalimide compound-containing aromatic polyetheramide resin powder by a concentration solidification method or a solvent stripping method.

If the amount of the bisphthalimide compound added is too small, no effect will be observed.

If the amount 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 to be added is practically 1
0.5 to 20 parts by weight per 00 parts by weight, 2
~15 parts by weight are used.

Furthermore, by blending other types of polymers into the resin composition of the present invention, its properties can be improved, such as antioxidants, ultraviolet absorbers, and lubricants.

By allowing additives such as flame retardants to coexist.

Its properties can also be improved.

Hereinafter, the present invention will be explained in more detail with reference to Examples.
It is not limited to this. Hereinafter, Example 1 A 10-cyclohexanone solution of an acid chloride mixture with a mixing ratio of terephthalic acid dichloride and isphthalic acid dichloride of 1:1 (weight ratio) and 2,2-bis(4-
An aromatic polyether amide was produced by contacting and reacting 10 parts of a 20% solution of (4-aminophenoxy)phenylpropane in cyclohexanone in the presence of an aqueous solution of caustic soda. However, the blending ratio of the acid chloride mixture and the aromatic diamide is equimolar. This in dimethylformamide (0,2f!-/dl) (D reduced viscosity is 0
．． It was 94 dl/f. To 100 parts by weight of this aromatic polyetheramide resin powder, 5 parts by weight of bisphthalimide compound bis[:4-(3-7thaliminophenoxy)phenyl]sulfone (1/lj parts by weight of polymer) was added. The mixture was pelletized at 300 to 320°C using an extruder. A test piece was molded from this pellet using an injection molding machine (340°C, 9ooK2/crr12). Tensile strength 91 Q Kg/Cm2. Impact strength 14 kg
cm/cm2. The heat distortion temperature was 185°C.

Example 2 106 Separable flask, stirring bar, thermometer.

Set the dropping funnel, dissolve 171,8'if of NaOH in 800 rrLl of water and put it into the flask. Next 2
,2-bis(4-(4-aminophenoxy)phenyl)
Propane 5949- and 4,4'-diaminodiphenyl ether 669- are dissolved in cyclohexanone 3.4 Kp, poured into the previous flask, and cooled to -2°C. On the other hand, terephthalic acid dichloride 1822 and isophthalic acid dichloride 182y- were mixed with cyclohexanone 2.
4 Dissolve in K9. This acid chloride solution is poured from the dropping funnel, making sure that the temperature of the two reactions does not exceed 10°C. 3 hours after dropping, benzoyl chloride 18
．． 97 is dissolved in cyclohexanone zo of P and added. Another two hours later.

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- as a bisphthalimide compound
Bis(4-(4-phthaliminophenoxy)phenyl)
Add propane in the amount shown in Table 1 and use an extruder to
It was pelletized at ~320°C. This pellet is made by injection molding.

Various test pieces were molded.Table 0 shows the molding conditions and properties of each pellet.

Example 3 An acid chloride mixture with a mixing ratio of terephthalic acid dichloride/isophthalic acid dichloride of 426 (weight ratio) and 2
．． 2-bis(4-(4-aminophenoxy)phenyl)
Propane was polymerized by solution polymerization using N-methylpyrrolidone as a solvent, and the resulting polymer was isolated and dried to obtain an aromatic polyetheramide resin with a reduced viscosity of 0.78 dl19. To 100 parts by weight of this polymer, 5 parts by weight of 1 as a bisphthalimide compound was added, pelletized at 300 to 320'C, and molded into a test piece by injection molding (34°C,'
90 oKy/α2). Tensile strength 930Kr/c
m2. Impact strength 12 to 7/cm2. Heat distortion temperature 190℃
There was a go.

Claims (1)

[Claims] 1. General formula (I) ll (However, 2 In formula (1), IRI to R4 represent hydrogen, a lower alkyl group, a lower alkoxy group, chlorine or bromine, and may be the same or different) 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, di- Phenylene ether, diphenylene sulfone,
100 parts by weight of an aromatic polyetheramide resin having a repeating unit represented by diphenylene or naphthylene group) and general formula (II) (wherein X is 10-, -SO□). R7 and R1o are alkyl groups having 1 to 4 carbon atoms. R8 and R9 are alkyl groups having 1 to 4 carbon atoms or halogen IpIqIr and S are o''!, an integer of 1 to 4, and t is an integer of 1 to 25. Yes. R7 and RIIO may be the same or different.
R8 and R9 may be the same or different from each other<, p,
An aromatic polyetheramide resin composition in which q, r and S are the same.