JPH01217064A - Polyphenylene sulfide-based resin composition - Google Patents

Abstract

PURPOSE:To obtain a resin composition having extremely improved heat resistance and mechanical strength in addition to the properties of polyphenylene sulfide, by mixing a polyphenylene sulfide with a specific amount of specific polyether imide resin. CONSTITUTION:(A) 100 pts.wt. polyphenylene sulfide consisting of the repeating unit expressed by formula I is blended with (B) 1-100 pts.wt. polyether imide resin consisting of the repeating unit expressed by formula II (R is tetrafunctional group selected from >=2C aliphatic group, alicyclic group and monocyclic aromatic group) obtained by dehydration and cyclization of polyamic acid prepared by reaction of 4,4'-bis[3-(4-aminophenoxy) benzoyl] diphenylether and tetracarboxylic acid dianhydride. For instance, powder of A is dry-blended with powder of B and meltblended by twin-screw extruder, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a molded wood am sole. More specifically, the present invention relates to a polyphenylene sulfide resin composition that has excellent heat resistance, chemical resistance, mechanical strength, etc., and excellent moldability.

[Conventional technology]

Polyphenylene sulfide has traditionally had excellent heat resistance, chemical resistance, water resistance, moldability, and electrical properties, and has been used in fields such as electrical and electronic equipment, aerospace equipment, and transportation equipment. It is expected to be widely used in fields where heat resistance is required.

However, polyphenylene sulfide has the drawback of poor mechanical strength, particularly tensile strength, tensile elongation, and impact resistance.

[Problem that the invention seeks to solve]

An object of the present invention is to obtain a polyphenylene sulfide resin composition that has improved mechanical strength, particularly tensile strength, tensile elongation, and impact resistance, in addition to the excellent properties of polyphenylene sulfide.

[Means for solving problems]

The present inventors conducted intensive research to solve the above problems, and found that a resin composition consisting of polyphenylene sulfide and a specific amount of a new polyetherimide is particularly effective for the above purpose. completed.

That is, the present invention provides polyphenylene sulfide 100q) (wherein R is an aliphatic group having 2 or more carbon atoms, a cycloaliphatic group, a monocyclic aromatic group, a fused polycyclic aromatic group, an aromatic group directly or Polyetherimide 1 having a repeating unit represented by
It is a polyphenylene sulfide resin composition consisting of at least 100 parts by weight.

The method for producing polyphenylene sulfide used in the present invention is disclosed in, for example, U.S. Pat. No. 3,354,129 and Japanese Patent Publication No. 45-3368, and
It is commercially available as "RYTON" (trademark of Petroleum Corporation, Philips, USA). According to it, polyphenylene sulfide has a temperature of 160 to 250'C in N-methylpyrrolidone solvent.

p-chlorobenzene and sodium sulfide・l under pressure conditions
It is produced by reacting with water salt.

Polyphenylene sulfide can be freely produced with various degrees of polymerization, from those with no cross-linking to those with partial cross-linking, by subjecting it to a post-heat treatment step. Further, these materials are commercially available, and therefore, one having melt viscosity characteristics suitable for the desired blend can be arbitrarily manufactured or selected from the market.

In the present invention, the polyetherimide resin used in combination for the purpose of improving the chemical resistance, heat resistance, and/or mechanical strength of polyphenylene sulfide is a repeating unit of the following formula (1) (wherein R is the same as before) The present inventor first discovered it as a polyimide that has excellent mechanical properties, thermal properties, electrical properties, solvent resistance, etc., and is heat resistant (Japanese Patent Application Laid-Open No. 62-076095). It's a thing 1
, which uses ether diamine represented by formula (III) as the diamine component, that is, 4,4°-bis(3-(4-aminophenoxy)benzoyl)diphenyl ether, and - or more tetracarboxylic acids. It is a polyetherimide obtained by cyclodehydration of a polyamic acid obtained by reacting it with a dianhydride. In addition, known diamines used for producing other polyimides may be used in combination with each other as long as the properties of the polyetherimide used in the present invention are not impaired. Diamines that can be used in combination include: , for example, metaphenylenediamine, paraphenylenediamine, orthophenylenediamine, m-aminobenzylamine, p-aminobenzylamine, 3,3'-diaminodiphenylmethane, 3,4°-
Diaminodiphenylmethane, 4.4'-diaminodiphenylmethane, 1.3-his(4-aminophenoxy)benzene, 1゜1-bis(3-aminophenoxy)benzene, 1.4-bis(4-aminophenoxy)benzene,
3.3'-diaminodiphenyl ether, 3.4''-diaminodiphenyl ether, 4.4''-diaminodiphenyl ethyl, 3.3'-diaminodiphenyl sulfide, 3.4''-diaminodiphenyl sulfide, 4.4
"-Diamino diphenyl sulfide, 3.3"-diaminodiphenylsulfone, 3.3°-diaminodiphenylsulfoxide, 3.4"-diaminodiphenylsulfoxide, 3.4'-diaminodiphenylsulfone, 4,4
゛-Diamino diphenyl sulfone, 4.4'-diaminodiphenylsulfoxide, 3.31-diaminobenzophenone, 3.4°-diaminobenzophenone, 4.
4°-Diaminobenzophenone, bis(4-(3-aminophenoxy)phenylcomethane, bis[4-(4-aminophenoxy)phenylcomethane, 1,1-bis(4
-(3-aminophenoxy)phenyl]ethane, 1.1
-Bis(4-(4-aminophenoxy)phenyl]ethane, 1.2-bis[4-(3-aminophenoxy)phenyl]ethane, 1.2-bis(4-(4-aminophenoxy)phenyl)ethane , 2.2-bis(4-(3-aminophenoxy)phenyl)propane, 2.2-bis(
4-(4-aminophenoxy)phenyl]propane, 2
．． 2-bis[4-(3-aminophenoxy)phenylcobutane, 2.2-bis(4-(4-aminophenoxy)
Phenylcobutane, 2.2-bis(4-(3-aminophenoxy)phenyl)-1,1,1,3,3,3-hexafluoropropane, 2.2-bis(4-(4-aminophenoxy)phenyl)-1,1,1,3,3,3-hexafluoropropane, ) phenyl)-1,1,1,3,3,3-hexafluoropropane, 1.3-bis(3-aminophenoxy)benzene, 4.4''-bis(3-aminophenoxy)biphenyl, 4. 4'-bis(4-aminophenoxy)biphenyl, bis(4-(3-aminophenoxy)phenylkoketone, bis(4-(4-aminophenoxy)phenylkoketone, bis(4-(3-aminophenoxy)) phenyl] sulfide, bis[4-(4-aminophenoxy)phenyl] sulfide, bis(4-(
3-aminophenoxy)phenyl]sulfoxide, bis(4-(4-aminophenoxy)phenyl)sulfoxide, bis[4-(3-aminophenoxy)phenyl]sulfone, bis(4-(4-aminophenoxy)phenyl)sulfone , bis(4-(3-aminophenoxy)phenyl)ether, bis(4-(4-aminophenoxy)
phenyl]ether, 1,4-bis(4-(3-aminophenoxy)benzoyl)benzene, 1,3-bis(4
-(3-aminophenoxy)benzoyl]benzene, 4
．． 4°-bis(3-(3-aminophenoxy)benzoyl]diphenyl ether, 4°4°-bis(4-(4-
Amino-α,α-dimethylbenzyl)phenoxy]benzophenone, bis[4-(4-(4-amino-α,α-
dimethylbenzyl)phenoxy)phenyl]sulfone,
Examples include bis(4-(4-aminophenoxy)phenoxyphenyl)sulfone.

The polyetherimide used in the present invention is obtained by reacting the diamine and tetracarboxylic dianhydride in an organic solvent, followed by dehydration and ring closure.

The tetracarboxylic dianhydride used at this time is (in the formula,
R is a tetracarboxylic dianhydride represented by (same as above).

That is, the tetracarboxylic dianhydride used is:
Ethylenetetracarboxylic dianhydride, butanetetracarboxylic dianhydride, cyclopentanecarboxylic dianhydride,
and romellitic dianhydride, 3.3', 4.4°-benzophenonetetracarboxylic dianhydride, 2.2°, 3.3
'-benzophenonetetracarboxylic dianhydride, 3,
3", 4.4°-biphenyltetracarboxylic dianhydride, 2.2°, 3,3"-biphenyltetracarboxylic dianhydride, 2.2-bis(3,4-dicarboxyphenyl)propanihydride 2.2-bis(2,3-dicarboxyphenyl)propanihydride, bis(3,4-dicarboxyphenyl)ether dianhydride, bis(3,4-
dicarboxyphenyl) sulfone dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride,
Bis(2,3-dicarboxyphenyl)methanidianhydride, bis(3,4-dicarboxyphenyl)methanidianhydride, 4;4"-(p-phenylenedioxy)diphthalic dianhydride, 4.4° -(m-phenylenedioxy)cyphthalic dianhydride, 2.3.6.7-naphthalenetetracarboxylic dianhydride, 1.4.5.8-naphthalenetetracarboxylic dianhydride, 1.2. 5.6-naphthalenetetracarboxylic dianhydride, 1,2.3.4-benzenetetracarboxylic dianhydride, 3.4.9.10-perylenetetracarboxylic dianhydride, 2.3.6. These include 7-anthracenetetracarboxylic dianhydride, 1.2.7.8-phenanthrenetetracarboxylic dianhydride, and the like, and these tetracarboxylic dianhydrides may be used alone or in a mixture of two or more.

The polyphenylene sulfide resin composition of the present invention is used in an amount of 1 part by weight or more and less than 100 parts by weight of the polyetherimide based on 100 parts by weight of the polyphenylene sulfide.

In order to improve the physical properties of polyphenylene sulfide, especially its heat resistance, it is effective to use polyetherimide in an amount of 1 part by weight or more, preferably 5 parts by weight or more, per 100 parts by weight of polyphenylene sulfide. However, if 100 parts by weight or more is used, the good moldability of polyphenylene sulfide will be lost, so it is preferable to use less than 100 parts by weight.

In addition, compared to conventional polyimide, the polyetherimide used in the present invention has poor heat resistance and physical properties, but it has excellent fluidity properties, so when used in combination with polyphenylene sulfide, the above effects can be achieved. It is something that can be changed.

The composition according to the present invention can be mixed and prepared by commonly known methods, but the following methods are preferred, for example.

(1) Preliminarily kneading polyphenylene sulfide powder and polyetherimide powder using a mortar, Henschel mixer, drum blender, tumbler blender, ball mill, ribbon blender, etc. to form a powder.

(2) Polyetherimide powder is dissolved or suspended in an organic solvent in advance, polyphenylene sulfide is added to this solution or suspension, and after uniformly dispersing or dissolving, the solvent is removed to form a powder.

(3) After dissolving or suspending polyphenylene sulfide in an organic solvent solution of polyamic acid, which is a precursor of the polyetherimide of the present invention, heat treatment is performed at 100 to 400°C, or a commonly used imidizing agent is used. After chemical imidization using , the solvent is removed to form a powder.

The powdered resin composition thus obtained can be used as it is for various molding purposes, such as injection molding, compression molding, transfer molding, and extrusion molding, but it is more preferable to use it after melt-blending. be. In particular, when preparing the above composition by mixing powders,
Comrade Left, or melting powder and pellets,
This is a simple and effective method.

Melt blending involves equipment used to melt blend conventional rubbers or plastics, such as hot rolls,
A Banbury mixer, Brabender, extruder, etc. can be used. The melting temperature is set above the temperature at which the blended system can be melted and below the temperature at which the blended system begins to thermally decompose, and the temperature is usually 300 to 420°C, preferably 320 to 400°C.

As a method for molding the resin composition of the present invention, extrusion molding or extrusion molding, which forms a homogeneous melt blend and has high productivity, is suitable, but other methods such as transfer molding, compression molding, and sintering are suitable. There is no problem in applying shapes, extrusion film molding, etc.

In addition, one or more solid lubricants such as molybdenum disulfide, graphite, boron nitride, lead oxide, lead powder, etc. can be added to the resin composition of the present invention. It is also possible to add one or more types of reinforcing agents, such as glass fibers, carbon fibers, aromatic polyamides, silicon carbide fibers, potassium titanate fibers, and glass peas.

In addition, to the resin composition of the present invention, antioxidants, heat stabilizers, ultraviolet absorbers, flame retardants, flame retardant aids, antistatic agents, lubricants, One or more conventional additives such as colorants can be added.

〔Example〕

Hereinafter, the present invention will be explained in more detail with reference to Production Examples, Examples, and Comparative Examples.

Production Example 1 4,4°-bis[3-(4-aminophenoxy)
5.92 kg (10 mol) of benzoyl]diphenyl ether and 18.8 kg of N,N-dimethylacetamide were charged, and 2.14 kg (9.8 mol) of romellitic dianhydride was added to the solution at room temperature under a nitrogen atmosphere. The mixture was added while being careful not to increase the amount of water, and stirred at room temperature for about 24 hours to obtain a polyamic acid solution.

Add 11. N-dimethylacetamide 5
．． 37 kg of triethylamine and 4.08 kg (40 mol) of triethylamine and 6
0.3 kg (60 mol) of acetic anhydride was added dropwise. After further stirring at room temperature for about 24 hours, the solution was poured into 250 Il of water with strong stirring, and the precipitate was filtered off, washed with methanol, and dried under reduced pressure at 150°C for 24 hours to give a 7°4
7 kg (97.0% yield) of pale yellow polyetherimide powder was obtained.

The logarithmic viscosity of this polyetherimide powder is 0.71 dl
/g. Here, the logarithmic viscosity is a value measured by heating and dissolving 0.5 g of polyetherimide powder in a mixed solvent of P-chlorophenol and phenol (90,710 weight ratio) and then cooling the solution to 35°C.

In addition, the glass transition temperature of this polyetherimide powder is 2
The temperature was 27°C (measured by the DSC method), and the degree of 5% weight loss was 540°C (measured by the DTA-TG method).

Examples 1 to 3 After tri-blending the polyetherimide powder obtained in Production Example 1 and polyphenylene sulfide powder 1' Rydon P-4'' (manufactured by Philips) at various composition ratios as shown in Table 1. , 340 ~ using a two-wheel melt extruder
It was extruded and granulated at 380″C.

Next, this pellet is put into an injection molding machine (cylinder temperature: 34
0 to 380°C and a mold temperature of 150°C) to obtain test pieces, and their thermal and mechanical properties were measured. The results are shown in Table-1.

In Table 1, tensile strength and elongation at break are ASTM 0-6.
38, bending strength and bending modulus are ASTM D-790
, Izod impact value is ASTM D-256, glass transition temperature is THA needle method, heat distortion temperature is ASTM 0-6.
48. Moldability was based on the lowest injection pressure.

Comparative Examples 1 to 2 Using compositions outside the scope of the present invention, the thermal and mechanical properties of molded products obtained by the same mechanism as Examples 1 to 3 were measured, and the results are shown in Table 1 for comparison. Shown as an example.

Production Examples 2 to 5 Combinations of 4.4°-bis(3-(4-aminophenoxy)benzoyl]diphenyl ether and various tetracarboxylic dianhydrides, and 4.4°-bis(3-(4-
When other amines were used in combination with aminophenoxy)benzoyl diphenyl ether, various polyetherimide powders were obtained in the same manner as in Production Example 1.Table 2 shows the synthesis conditions, logarithmic viscosity, and glass of the polyetherimide. Indicates transition temperature.

Table-1 Examples 4 to 11 and Comparative Examples 2 to 5 Using the various polyetherimide powders obtained in Production Examples 2 to 5, uniform blended pellets were obtained in the same manner as in Examples 1 to 3, and then in the same manner. The physical and thermal properties of each molded product were measured by injection molding.

Table 3 shows the results of compositions within the scope of the present invention as Examples 4 to 11, and the results of compositions outside the range as Comparative Examples 2 to 5.
Shown below.

〔Effect of the invention〕

In addition to the inherent properties of polyphenylene sulfide, the polyphenylene sulfide resin composition of the present invention has
It has significantly improved heat resistance and mechanical strength, and is useful in a wide range of fields such as aerospace equipment, electronic/electrical equipment, automobiles, precision equipment, and general equipment, and its industrial effects are significant.

Patent applicant: Mitsui Toatsu Chemical Co., Ltd.

Claims (2)

[Claims] (1) For 100 parts by weight of polyphenylene sulfide,
Formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I) (In the formula, R is an aliphatic group with 2 or more carbon atoms, a cycloaliphatic group, a monocyclic aromatic group, a fused polycyclic aromatic group) Polyetherimide resin 1 having a repeating unit represented by (representing a tetravalent group selected from the group consisting of non-fused polycyclic aromatic groups in which aromatic groups are interconnected directly or through a crosslinking member) A polyphenylene sulfide resin composition comprising at least 100 parts by weight. (2) The resin composition according to claim 1, in which the polyphenylene sulfide is composed of repeating units of formula (II) (which has a mathematical formula, chemical formula, table, etc.).