JPS6270449A - Polyphenylene ether composition - Google Patents

Abstract

PURPOSE:To obtain a polyphenylene ether compsn. having improved oil and impact resistance, by blending a polyphenylene ether or a mixture thereof with a styrene resin and modified ethylene copolymers. CONSTITUTION:A polyphenylene ether compsn. consists of the following component (a) and the following component (b) and/or the following component (c) in such a proportion that the quantity of component (a) is 95-40wt% and the combined quantity of components (b) and (c) is 5-60wt%. Component (a) is a polyphenylene ether or a compsn. consisting of said polyphenylene ether and a styrene resin. Component (b) is a modified ethylene copolymer (B) obtd. by polymerizing an ethylene copolymer (b) composed of 2-30wt% styrene and 98-70wt% ethylene or its derivative in the presence of an arom. vinyl monomer. Component (c) is a modified ethylene copolymer (C) obtd. by polymerizing an ethylene copolymer (c) composed of 2-30wt% vinyl compd. having a glycidyl group and 98-70wt% ethylene or its derivative in the presence of an arom. vinyl monomer.

Description

DETAILED DESCRIPTION OF THE INVENTION (Objectives) The present invention relates to a polyphenylene ether composition that simultaneously improves oil resistance and impact resistance.

(Prior Art) Polyphenylene ether is an engineering resin with excellent heat resistance and mechanical properties, but has the disadvantage of low fluidity and difficulty in molding. It cracked and its impact strength was also insufficient. For this reason, it is widely practiced to incorporate high-impact polystyrene, but polyphenylene ether compositions containing high-impact polystyrene have poor oil resistance, which is one of the important properties for engineering glasstics, so improvement is desired. ing.

On the other hand, as a method for improving oil resistance, it has been proposed to incorporate polyamide or olefin thread resin. However, polyamides and melefin resins have poor miscibility with polyphenylene ether and polystyrene, and have the disadvantage that impact strength decreases when optical components are added to improve oil resistance.

(Summary of the Invention) The present inventors conducted studies aimed at simultaneously improving the oil resistance and impact strength of polyphenylene ether compositions, and as a result, discovered the following improvement means.0 The following component (a) and , component (1)) or (and) component (
C), wherein component (a) is 95 to 40% by weight, and the total amount of component (b) and component (C) is 5 to 60% by weight.

Component (a): polyphenylene ether or polyphenylene ether and styrene resin.

Component (b): An ethylene copolymer (b) consisting of 2 to 30% by weight of an unsaturated carboxylic acid and 95 to 40% by weight of ethylene or ethylene and an ethylene derivative is subjected to polymerization conditions in the coexistence of a vinyl aromatic monomer. Modified ethylene copolymer (B) obtained by adding.

Component (C): Vinyl compounds 2 to 3 having a glycidyl group
0 weight ratio, ethylene or ethylene and ethylene derivatives 9
Ethylene copolymer (C) consisting of 8 to 70% by weight-1t%
A modified ethylene copolymer (C) obtained by subjecting the above to polymerization conditions in the coexistence of a vinyl aromatic monomer.

(Specific Description) Component (a) of the present invention consists of polyphenylene ether or polyphenylene ether and styrene resin.

The polyphenylene ether used in the present invention has a cyclic structural unit represented by the general formula, in which the ether oxygen atom of one unit is connected to the benzene nucleus of the next adjacent unit, and n is at least 50 and Q is independently hydrogen, no-roken, a hydrocarbon group not containing a tertiary σ-carbon atom, and at least two hydrogen atoms between the no-rogen atom and the phenyl nucleus.
A monovalent monovalent selected from the group consisting of a hydrocarbon group having 2 carbon atoms, a hydrocarbon oxy group, and a halohydrocarbon oxy group having at least 2 carbon atoms between the norogen atom and the phenyl nucleus. Indicates a substituent.

Poly(2,6-dimethyl-1,4-phenylene) ether 1. j-'IJ (2,6-diethyl-1,4-phenylene)ether, poly(2-methyl-6-ethyl-1,
4-phenylene) ether, poly(2-methyl-6-furopyru-1,4-phenylene) ether, poly(2,6
-Siglopyru 1.4-) Unishin) ether, Poly(
2-Ethyl-6-broby-1,4-phenylene)ether, poly(2,6-diphthylue).

4-phenylene)ether, poly(2,6-difurobé=
/l/-1,4-phenylene)ether, poly(2゜6
-dilauryl-1,4-phenylene)ether, poly(
2,6-siphenylene-1,4-phenylene) ether,
Poly(2,6-simethoxy-1,4-phenylene) ether, poly(2,6-jethoxy-1,4-phenylene) ether, poly(2-methoxy-6-nitoxy) 1.
4-phenylene) ether, poly(2-ethyl-6-methialyloxy-1,4-phenylene) ether, BoI
J (2,6-dichloro-1,4-phenylene) ether, poly(2-methyl-6-phenyl-1,4-phenylene) ether, poly(2,6-dipenzyl-1,4-
phenylene) ether, poly(2-ethoxy-1,4-
phenylene) ether1. l-'IJ (2-chloro-1
, 4-phenylene) ether, poly(2,5-dibromo-1,4-phenylene) ether and the like.

Also, copolymers of 2,6-dimethylphenol and 2.3.6-trimethylphenol, copolymers of 2,6-dimethylphenol and 2.3,5,6-titramethylphenol, 2,6- Mention may also be made of copolymers such as copolymers of dinitylphenol-2,3,6-trimethylphenol.

Furthermore, the polyphenylene ether used in the present invention is a polyphenylene ether defined by the above general formula that is modified by grafting a styrene monomer (for example, styrene, p-methylstyrene, α-methylstyrene, etc.). It also includes polyphenylene ethers.

Methods for producing polyphenylene ethers corresponding to the above are known, for example, U.S. Pat.
No. 06875, No. 3257357 and No. 32573
No. 58 specifications and Japanese Patent Publication No. 52-1788
No. 0 and Japanese Unexamined Patent Publication No. 50-51197.

A group of polyphenylene ethers which are preferred for the purposes of the present invention are those having alkyl substituents in the two positions ortho to the ether oxygen atom and copolymers of 2.6-dialkylfetoolt (2.3.6-) realkylphenols. Furthermore, it is a graft polymer obtained by grafting a styrene monomer onto these polyphenylene ether skeletons.

The styrenic resin used in the present invention includes homopolymers such as polystyrene, poly-α-methylstyrene, and poly-p-methylstyrene, and butadiene rubber, styrene-butadiene copolymer, ethylene-propylene copolymer, ethylene - High impact polystyrene modified with various rubbers such as propylene-dien terpolymer, styrene-butadiene copolymer, styrene-maleic anhydride copolymer, styrene-acrylonitrile copolymer, styrene-acrylonitrile-butadiene copolymer, styrene There are tatami methyl methacrylate copolymers, etc., and these styrene resins account for 0 to 95% by weight, preferably 5 to 5% by weight, based on the total amount with polyphenylene ether.
Component (b) of the present invention mixed in a range of 0% by weight is an unsaturated carboxylic acid of 2 to 30% by weight.
% and ethylene or ethylene and ethylene derivative 98-70
This is a modified ethylene copolymer (B) which can be modified by subjecting the ethylene copolymer (b) with -1 t% of ethylene to polymerization conditions in the coexistence of a vinyl aromatic monomer.

The unsaturated carboxylic acids used to form the ethylene copolymer (b) include acrylic acid, methacrylic acid,
Propionic acid and maleic acid are preferable. ○ Ethylene derivatives include α-olefins (propylene, butene-1, hexene-1,4-methylpentene-1
etc.), vinyl esters (vinyl acetate, vinyl propionate, etc.), unsaturated carboxylic acid esters (methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, acrylic Glycidyl acid, glycidyl methacrylate, etc. with about 4 to 10 carbon atoms), styrene derivatives (styrene, p-methylstyrene, α-methylstyrene, etc.)
You can choose one or more from.

The unsaturated carboxylic acid and ethylene can be polymerized by a method known per se, for example, by using a polyethylene high-pressure polymerization method.

The amount of unsaturated carboxylic acid units in the ethylene copolymer (b) ranges from 2 to 30% by weight, preferably from 3 to 25% by weight.

If the amount of unsaturated carboxylic acid is too large, the ability to impregnate the vinyl aromatic monomer will be reduced, and if it is too small, the effect of improving oil resistance will be poor.

Further, when adding an ethylene derivative, the ethylene derivative to ethylene derivative is used in an IT ratio of 0.39 or less, preferably 0.30 or less.

Furthermore, the crystallinity of the ethylene copolymer (b) is 10 to 50.
% is preferred. If the degree of crystallinity is high, the vinyl aromatic monomer will not be uniformly impregnated, making it difficult to obtain a desired modified ethylene polymer. Furthermore, if the degree of crystallinity is low, it will be excessively swollen or dissolved by the vinyl aromatic monomer, making it difficult to handle during production.

Since the content of the ethylene derivative and unsaturated carboxylic acid in the ethylene copolymer (b) is inversely proportional to the degree of crystallinity, there is a suitable range for the content of these comonomers, and the gold side of the comonomer has a content of 2 to 40% %, 86492, a vinyl aromatic monomer containing polymerization initiator gold is mixed into an aqueous suspension of powder or granular ethylene copolymer containing unsaturated carbon ek. It can be obtained by impregnating copolymer particles with a vinyl aromatic monomer and then raising the temperature to initiate polymerization.

Examples of the vinyl aromatic monomer include styrene or styrene derivatives such as α-methylstyrene and p-methylstyrene.

In order to uniformly modify the ethylene copolymer (b), it is desirable to impregnate the ethylene copolymer (b) with as much of the added vinyl aromatic monomer as possible before carrying out the polymerization.

As the polymerization initiator, those known as polymerization initiators for vinyl compounds can be used, such as cyclohexanone peroxide, t-butyl peroxybenzoate, methyl ethyl ketone peroxide, dicumyl peroxide, di-t-butyl Peroxide, 2,5
- Generation of radicals such as peroxides such as dimethyl-2゜5-dibenzoylba-oxyhexane, benzoyl peroxide, t-butyl peroxybivalate, or azo compounds such as azobisinbutyronitrile and azobisinvaleronitrile. agents can be used.

The proportion of the polymer obtained from the vinyl aromatic monomer in the modified ethylene copolymer (B) is preferably 20 to 70%. Vinyl aromatic polymers generally correspond to the presence of the 7-mer, but if the amount of monomer charged is too large, the modified ethylene-based Koia polymer gels and becomes unsuitable. However, if it is too small, the effect of improving compatibility with polyphenylene ether will not be sufficient.

The blending amount of component (b) is 0 to 60% by weight, preferably 5 to 60% by weight, based on the total amount of components (a) and L. 15-405-40% by weight
be. When the amount of component (b) exceeds the above range by 1, the heat resistance temperature, which is a characteristic of the polyphenylene ether composition, decreases.

Component (C) of the present invention is an ethylene copolymer (
This is a modified ethylene copolymer (C) obtained by subjecting C) to polymerization conditions in the coexistence of a vinyl aromatic monomer.

Suitable vinyl monomers containing glycidyl groups constituting the ethylene copolymer (C) include glycidyl acrylate, glycidyl methacrylate, and p-glycidylstyrene.

Moreover, all of the same ethylene derivatives and vinyl aromatic monomers as component (b) can be used.

Furthermore, the ratio of the total amount of comonomers to the ethylene copolymer (e) is 2 for the same reason as explained for component (b).
~40 fjk%. Further, the content of the vinyl compound bonded with glycidyl groups in the ethylene copolymer (C) is 2 to 30% by weight. Above this range, component (b)
gelation between the two is more likely to occur.

It is thought that gelation is caused by the formation of a chemical bond between the carboxylic acid group of component (b) and the glycidyl group of component (C).

Furthermore, an ethylene copolymer (C) below this range does not exhibit a sufficient effect in improving impact strength.

Component (b) and component (C) are blended with component (a) so that the total amount thereof is 5 to 60% by weight (based on the total of components (a), (b), and (C)). .

However, if the amount of component (C) is large, gelation tends to occur;
The amount of component (C) is desirably in the range of 0 to 20% by weight, preferably 5 to 15% by weight.

Component (b) and optionally component (
C) can be blended using any well-known method. For example, after dissolving these component resins in a common solvent and mixing them in a solution state, adding a precipitant and co-precipitating. In addition to physical blending methods such as mixing these component resins in a grinder and then extruding them from an extruder, or kneading the component resins using a Banbury mixer, kneader, etc., there are also methods for mixing component (b). A chemical compounding method is also used, such as a method in which a phenolic compound is oxidized and polycondensed in the presence of the compound, followed by coprecipitation.

The resin composition of the present invention may optionally include polymers other than the constituent components of the present invention, such as polyethylene, polypropylene, styrene-butadiene rubber, natural rubber, ethylene-propylene rubber, ethylene-glopylene-nonconjugated diene rubber, etc. It is also possible to add original copolymers, etc., and various additives such as heat stabilizers, lubricants, flame retardants, ultraviolet absorbers, pigments, and colorants can be appropriately added to form a molding material.

Furthermore, if desired, glass fiber, massbest fiber,
Inorganic reinforcing agents such as calcium carbonate and talc may also be added.

A modified ethylene copolymer obtained by copolymerizing an ethylene copolymer with an unsaturated carboxylic acid or a glycidyl group-containing vinyl compound under the polymerization conditions of the monomer in the coexistence of a vinyl aromatic monomer and a polymerization initiator. By blending into the polyphenylene ether composition,
Impact strength and secondary oiliness are improved at the same time.

Although the effect of modified polyethylene copolymers is not clear,
As a result of polymerization modification of the ethylene copolymer with a vinyl aromatic monomer that is considered to have good compatibility with polyphenylene ether, the ethylene copolymer and the vinyl aromatic polymer are
It can be considered that not only is the mixture more uniformly mixed, but also that a portion of the vinyl aromatic polymer undergoes a graft reaction with the ethylene copolymer to improve the compatibility of the modified ethylene resin with the polyphenylene ether. In the blended composition of the present invention, it was confirmed by scanning electron microscopy that the modified ethylene copolymer was uniformly and finely dispersed in the polyphenylene composition.

As well as improving the impact strength, a significant impact strength improvement effect is recognized.

Next, the performance of the resin composition of the present invention will be shown by examples. The measurement method used in the examples is as follows.

(1) Izot impact strength: JIS K 7110 (2
) Oil resistance: Measured by the Bergen quarter ellipse method. (SPE Journal, 6) In other words, a test piece with a plate thickness of 2fi, a long axis of 240 mm and a short axis of 8 t
The critical strain was determined as the minimum strain at which a crack would occur when the sample was fixed in a quarter-ellipse jig and immersed in a solvent containing a 9:1 mixture of di-normal hebutane and toluene for 5 minutes.

Examples (Example-1, Comparative Example-1, Comparative Example-2) Production of component (b) In a 10 J autoclave, pure water 3000F and suspending agent tricalcium phosphate 90? and 0.09 f'i of sodium dodecylbenzenesulfonate to form an aqueous medium, and to this was added an ethylene-acrylic acid copolymer (acrylic acid content 9.5% by weight, MFR=11, density 0.94?/
cd) 500 r was added and stirred to suspend.

Separately, t-butyl peroxypivalate (NOF Co., Ltd., 7
09! T product) 7.2F and benzoyl peroxide 2.5r'i Dissolved in styrene 500P, added this to the suspension system, replaced the system with nitrogen, and then raised the temperature in the autoclave to 50°C. The mustyrene containing the polymerization initiator was converted into ethylene by leaving it at this temperature for 3 hours with stirring.
It was impregnated into acrylic acid copolymer particles.

Next, the temperature of this suspension was raised to 75°C, and polymerization was carried out by leaving it at this temperature for 2 hours while stirring.Then, the temperature was further raised to 90°C and maintained for 3 hours, and the polymerization was completed. , After removing the solid contents and rinsing thoroughly with water,
It was dried in a vacuum dryer to obtain modified copolymer 9901 (modified ethylene copolymer (B-1)).

34.8% by weight of IJ-2,6-dimethyl-1,4-phenylene ether (manufactured by Mitsubishi Yuka Co., Ltd., intrinsic viscosity 45 in chloroform at 30°C), Z6 impact polystyrene ( Mitsubishi Monsando Co., Ltd., HT-76) 52.2% by weight and modified ethylene copolymer (B-1) 13% by weight were mixed, and using an Ikegai Tekko twin screw extruder (PCM-45), 2
The mixture was melt-kneaded at 60°C and pelletized. This pellet was molded into a predetermined test piece using an N-100B-II injection molding machine manufactured by Japan Steel Works, and its Izod impact strength and oil resistance were measured. The results are shown in Table-1.

In addition, 40% by weight of poly-2,6-dimethyl-1,4-phenylene ether and 60% by weight of high-impact polystyrene were mixed and molded in the same manner as in Example 1. The results (Comparative Example-1) are shown in Table 1. .

Furthermore, Example 1 was prepared using 37.4% by weight of poly-2,6-dimethyl-1.4-phenylene ether, 56.0% by weight of high-impact polystyrene, and 6.5% by weight of ethylene-acrylic acid copolymer. Results of similar operations (Comparative Example-2
) are shown in Table-1.

(Left below) (Example 2, Example 3) Production of component (c) The ethylene-acrylic acid copolymer was replaced with ethylene-vinyl acetate-glycidyl methacrylate copolymer (Sumitomo Chemical Co., Ltd.
Example-1 except for replacing with 2B)
Under the same conditions as for the production of ethylene copolymer (B-1),
A modified ethylene copolymer (C-1) was obtained. Yield is 960
It was t.

Table 2 shows the results obtained in the same manner as in Example 1 except that the blending amount was changed.

(Example-4, Comparative Example-3) Production ethylene-acrylic acid copolymer of component (b) was prepared using an ethylene-acrylic acid copolymer with an acrylic acid content of 13% by weight, an MFR of 26, and a density of 0.9597 m (Mitsubishi Yuka
Copolymer (manufactured by Co., Ltd.), and the amount of the copolymer was changed to 300 f.
Modified ethylene copolymer (B-2) 9301F was obtained in the same manner as in Example-1 except that 700t of styrene was used.

Replace the high-impact polystyrene with crystal polystyrene (HF-77 manufactured by Mitsubishi Monsanto), and use the same procedure as in the actual flow side-1 to adjust the amount of 2,6-dimethyl-1,4-phenylene ether 49.5 il 1%, crystal Polystyrene 4.5% by weight, ethylene copolymer (B-2) 28.6
Table 2 shows the results obtained in the same manner as in Example 1, using 6.4% by weight of ethylene copolymer (C-1) and 11% by weight of triphenyl phosphate. In addition, the results of mixing 2,6-dimethyl-1,4-phenylene nitrate of Example 4, crystal polystyrene, and polystyrene in the total amount of the copolymer are shown in Table 2 as Comparative Example 3. .

(Example-5, Comparative Example-4) Table 2 shows the results obtained by the same operation as Example-1 except for changing the formulation.

(Margin below)

Claims (1)

[Claims] The following component (a), component (b) or (and) component (c)
), component (a) is 95 to 40% by weight, component (
A polyphenylene ether composition in which the total amount of b) and component (c) is 5 to 60% by weight. Component (a): polyphenylene ether or a composition consisting of polyphenylene ether and styrene resin. Component (b): An ethylene copolymer (b) consisting of 2 to 30% by weight of an unsaturated carboxylic acid and 98 to 70% by weight of ethylene or ethylene and an ethylene derivative is subjected to polymerization conditions in the coexistence of a vinyl aromatic monomer. Modified ethylene copolymer (B) obtained by Component (c): Vinyl compounds 2 to 3 having a glycidyl group
0% by weight and ethylene or ethylene and ethylene derivative 9
A modified ethylene copolymer (C) obtained by subjecting an ethylene copolymer (c) consisting of 8 to 70% by weight to polymerization conditions in the coexistence of a vinyl aromatic monomer.