JPS60252655A - Polyphenylene ether composition having improved moldability - Google Patents

Abstract

PURPOSE:To obtain the titled composition having improved fluidity while suppressing the lowering of heat-resistance, by compounding a triamide compound to a composition composed mainly of polyphenylene ether. CONSTITUTION:The objective composition can be prepared by compounding (A) a composition composed mainly of 100pts.(wt.) of a polyphenylene ether [e.g. poly(2,6-dimethyl-1,4-phenylene)ether] and 0-2,000pts. of a styrene resin with (B) 0.1-25pts., especially 2-10pts. (based on 100pts. of the whole polymer) of a triamide compound of formula I or formula II (R<1> is 1-20C, and R<2>, R<3> and R<4> are 1-10C straight or branched saturated or unsaturated chain hydrocarbon residue, alicyclic hydrocarbon residue, aromatic hydrocarbon residue, or residure of these derivative). The triamide compound dissolves in the matrix component in molding and crystallizes in use to effect the phase-separation from the matrix component. The melting point of the triamide compound is preferably somewhat lower than the molding temperature, usually 150-300 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION (1) Background of the Invention The present invention relates to polyphenylene ether compositions, particularly polyphenylene ether compositions with improved moldability.

Polyphenylene ether has excellent electrical and mechanical properties, high heat distortion temperature, and self-extinguishing properties.
It is attracting attention as an extremely useful engineering plastic material. However, it has low impact strength and is somewhat brittle. Furthermore, since this resin has a high melting temperature and high melt viscosity, it requires high molding temperatures and pressures during molding, making molding by melting difficult.

As one method for improving the moldability of polyphenylene ether, attempts have been made to blend it with other resins. For example, in Special Publication No. 43-17812,
Blending high-impact polystyrene resin with polyphenylene ether has been described.

Although this composition has improved moldability and impact resistance, it is said that the moldability is still insufficient.

Another method for improving the moldability of polyphenylene ether is the addition of a plasticizer to polyphenylene ether.
No. 220 discloses aromatic organic acid esters having good compatibility with polyphenylene ether resins, polyesters having aromatic groups, organic phosphate esters having aromatic groups, and chlorinated aromatic carbonized esters. It has been shown that moldability can be improved by blending a compound selected from hydrogen into polyphenylene ether or a composition of polyphenylene ether and styrenic resin.

However, a plasticizer (
For example, blending organic phosphate esters with aromatic groups improves molding processability, but significantly lowers thermal performance. This is because the blended plasticizer is extremely uniformly dispersed (molecularly dispersed) in a matrix made of polyphenylene 1 nonether or a composition of polyphenylene ether and styrene resin. It is thought that Tg) decreases, resulting in a decrease in heat resistance.

The present inventors considered that it is desirable for the additive to have the following properties in order to suppress this decrease in thermal performance (heat resistance) and improve moldability (fluidity).

(1) During molding, that is, under the fluid state of the system, it must have good compatibility with the matrix component and exhibit the same fluidity-improving effect as a plasticizer.

(2) During use, that is, under flow stopped conditions (matrix Tg
In the following temperature ranges), phase separation from the matrix components should occur and the Tg of the matrix should not be lowered.

However, in order to prevent a decrease in mechanical strength, the interfacial adhesive force with the matrix must be strong to a certain extent even when phase separation occurs, and the material must have affinity with the matrix.

As a result of intensive studies from this perspective, the present inventors found that
This has led to the present invention.

[0] Summary of the Invention The present invention relates to polyphenylene ether, or polyphenylene ether and styrenic resin! The present invention provides a means for improving the molding processability of the composition of (1).

That is, the present invention provides polyphenylene ether or a composition of polyphenylene ether and styrene resin;
The object of the present invention is to provide a polyphenylene ether composition with improved moldability, which is characterized by being mixed with a triamide compound represented by the following formula.

R1: Saturated or unsaturated chain hydrocarbon residue having a linear or bent side chain having 1 to 20 carbon atoms, alicyclic hydrocarbon residue, aromatic hydrocarbon residue, or this Derivative residues containing groups such as.

R", R', E': Saturated or 7< or unsaturated chain hydrocarbon residue having a linear or side chain having 1 to 10 carbon atoms, alicyclic hydrocarbon residue -! or Aromatic hydrocarbon residues, or derivative residues thereof.

(R"J R"l R' may be the same or different) [111] Detailed description of the invention (1) Polyphenylene ether The polyphenylene ether used in the present invention has a circulatory structure represented by the general formula units, in which the ether oxygen atom of one unit is connected to the benzene nucleus of the next adjacent unit, n is at least 50, and Q is each independently hydrogen, halogen, tertiary α-carbon. A hydrocarbon group containing no atoms, a halohydrocarbon group having at least two carbon atoms between the halogen atom and the phenyl nucleus, a hydrocarbon oxy group having at least two carbon atoms between the halogen atom and the phenyl nucleus Indicates a monovalent substituent selected from the group consisting of halohydrocarbonoxy groups having carbon atoms.

A typical example of polyphenylene ether is poly(
2,6-dimethyl-1,4-phenylene) ether;
f? +) (2,6-ethyl-1,4-phenylene)
Ether, poly(2-methyl-6-ethyl-1,4-phenylene) ether, poly(2-methyl-6-furopylene-1,4-phenylene) ether, poly(2,6-diprobyl-1,4-phenylene) ether, poly(2-ethyl-6-broby-1,4-phenylene)ether,
(L6-cyphthyl-1゜4-phenylene)ether, borj (z, e -sifuroinyl-1,4-
phenylene) ether, poly(2゜6-dilauryl-1)
, 4-phenylene) ether, po'J (216-diphenyl-1,4-phenylene) ether, poly(2,6
-Simethoxy1,4-phenylene)ether, poly(
2,6-jethoxy-1,4-phenylene) ether,
Poly(2-methoxy-6-ethoxy-1,4'-phenylene) ether, poly(2-niethyl-6-stearyloxy-1,4-phenylene) ether, yN') (2
, 6-cyclo-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. t'1J (2-chloro-1,4-phenylene) ether, poly(2,5-dibromo-1,4-
phenylene) ether and equivalents.

Also, copolymers of 2,6-dimethylphenol and 2.3.6-)limethylphenol, copolymers of 2,6-dimethylphenol and 2.3.5.6-titramethylphenol, 2, Copolymers such as a copolymer of 6-ethylphenol and 2.3.6-triphthylphenol may also be mentioned. Furthermore, the polyphenylene ether used in the present invention is
It also includes modified polyphenylene ethers such as polyphenylene ethers defined by the above general formula grafted with styrenic monomers (eg, tii', styrene, p-methylstyrene, α-methylstyrene, etc.).

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

Preferred groups of polyphenylene ethers for the purposes of the present invention are those with alkyl substituents in the two orno positions to the ether oxygen atom and copolymers of 2,6-dialkylphenols and 2,3,6-)realkylphenols. Furthermore, these are graft polymers obtained by crafting a styrene monomer onto a polyphenylene ether skeleton.

(2) Styrenic resin The styrene resin used in the present invention includes homopolymer resins such as polystyrene, poly-α-methylstyrene, and poly-p-methylstyrene. - and high-impact polystyrene, styrene-butadiene copolymer, styrene modified with m-f- and butadiene rubber, styrene-butadiene copolymer, ethylene-propylene copolymer, ethylene-propylene-diene terpolymer.・There are maleic anhydride copolymers, styrene/acrylonitrile copolymers, styrene/acrylonitrile/butadiene copolymers, styrene/methyl methacrylate copolymers, etc. These styrene resins are based on 100 parts by weight of polyphenylene ether resin. It is mixed at a ratio of 0 to 2000 parts by weight.

(3) Addition of other polymers Other polymers can be added to the polyphenylene ether or the composition of polyphenylene ether and styrene resin for the purpose of improving impact resistance and the like.

Added polymers include natural or synthetic rubber-like elastomeric polymers, such as natural rubber, polyisoprene,
Polybutadiene, copolymers of styrene and conjugated dienes such as butadiene (including block copolymers), ethylene-propylene copolymers, ethylene-propylene-non-conjugated diene terpolymers, etc. can be used.

In addition, polymers that have been imparted with sensitivity by introducing polar groups can also be used, such as rubber-like elastic polymers that have been imparted with sensitivity, as well as polyethylene, ethylene-vinyl acetate copolymers, polypropylene, etc. It is also possible to use a polymer obtained by imparting sensitivity to the polyolefin polymer described above.

As a means of imparting sensitivity, it is possible to graft an unsaturated organic acid or its anhydride (for example, acrylic acid, methacrylic acid, maleic acid, itaconic acid, or anhydride thereof) or an unsaturated silane compound to the above polymer. This can be done by

The polymer imparted with sensitivity can also be obtained by block or random polymerization of ethylene and a vinyl monomer or vinyl silane having a polar group such as an unsaturated organic acid such as acrylic acid or an ester thereof.

When using rubber-modified polystyrene, the amount of the rubber-like elastomeric polymer or the polymer that has imparted sensitivity is such that when using rubber-modified polystyrene, the total amount including the rubber component derived therefrom is 0.5 to the total amount of all polymer components. ~50% by weight, preferably about 2~40% by weight.

Furthermore, when using a polymer imparted with sensitivity, it is preferable to add an inorganic filler. In the case of using a sensitized polymer and an inorganic filler in combination, the sensitized polymer is dispersed in a matrix of polyphenylene ether or a composition of polyphenylene ether and styrene resin, and It forms a special structure that is selectively filled with inorganic filler, and can obtain physical properties with excellent mechanical strength.

As the inorganic filler, inorganic powders known as fillers for synthetic resins, such as titanium oxide, zinc oxide, talc, clay, calcium carbonate, and 7-liquor, can be used.

The average particle size of the inorganic filler is preferably about 0.05 to 1.0 μm, and the average particle size of the inorganic filler is about 7 μm to the entire composition obtained by mixing.
It is used in an amount of 0.5 to 60% by weight, preferably 1 to 45% by weight.

Furthermore, as other polys, polyphenylene ether,
Alternatively, a polyolefin graft polymerized with a styrene resin can also be used.

Polyphenylene ether graft polyolefin is a polyolefin that has a carboxyl group or an acid anhydride group in the main chain or side chain, such as ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer, by reacting glycidylated polyphenylene ether with epichlorohydrin. It can be obtained by grafting onto acid copolymers, maleic anhydride-modified polypropylene, maleic anhydride-modified polyethylene, maleic anhydride-modified ethylene/vinyl acetate copolymers, and the like.

Polyphenylene ether grafted polyolefins can also be produced by grafting polyphenylene ether onto polyolefins having glycidyl groups in their side chains, such as ethylene/glycidyl methacrylate copolymers, ethylene/vinyl acetate/glycidyl methacrylate copolymers, etc. Obtainable.

In addition, as polystyrene craft polyolefin,
Styrenic copolymers having a carboxylic acid group or cyclic acid anhydride group in the main chain or side chain of polystyrene, such as styrene/maleic anhydride copolymer, styrene/citraconic anhydride copolymer, styrene/itaconic anhydride Copolymer, styrene/asconitic anhydride copolymer, styrene/
Grafting a polyolefin having a glycidyl group in the side chain, such as ethylene/glycidyl methacrylate copolymer, ethylene/vinyl acetate/glycidyl methacrylate copolymer, etc., to acrylic acid copolymer, styrene/methacrylic acid copolymer, etc. You can get it by doing this.

The amount added is based on polyphenylene ether or a composition of polyphenylene ether and styrene resin, and
Polyphenylene ether grafted polyolefin and/or
Or, based on the total amount of polystyrene-grafted polyolefin, polyphenylene ether-grafted diolefin is preferably 0.1-5.0% by weight, preferably 1-30% by weight, polystyrene-crafted polyolefin is 1-so% by weight,
A range of 1 to 30% by weight is preferably used.

The grafted polyolefin can be added after graft polymerization in advance, but 1. When a polyolefin having a glycidyl group is used, a graft reaction can be carried out by kneading it with a styrene resin having a polyphenylene ether or a carboxylic acid or its anhydride group at a high temperature of 150° C. or higher.

Therefore, by kneading a composition of glycidyl group-containing polyolefin and polyphenylene ether or polyphenylene and styrene resin at high temperature, each component is mixed uniformly, and at the same time, the polyphenylene ether graft produced by the progress of the graft reaction polyolefin,
From an economical point of view, it is the most preferred method to obtain a composition containing polystyrene and/or polystyrene craft polyolefin all at once.

(4) Triamide compound The triamide compound used in the present invention is represented by the following formula.

R1: a saturated or unsaturated chain hydrocarbon residue having a linear or side chain having 1 to 20 carbon atoms, an alicyclic hydrocarbon residue, an aromatic hydrocarbon residue, or a group thereof. Derivative residues containing.

n*, R11, R4: a saturated or unsaturated chain hydrocarbon residue having a straight chain or side chain having 1 to 10 carbon atoms, a cylindrical hydrocarbon residue, or an aromatic hydrocarbon residue; , these derivative residues.

(R", R", R'R1 may be the same or different) Examples of R1 include methanetriyl group, ethanetriyl group, propanetriyl group, butanetriyl group, pentantriyl group, cyclopentantriyl group, hexane Triyl group, cyclohexanetriyl group, octanetriyl group, decanetriyl group, benzenetriyl group, and derivative residues containing these groups.

Examples of R11, R11, and R4 include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, pentyl group, isopentyl group,
cyclopentyl group, hexyl group, isohexyl group, cyclohexyl group, heptyl group, octyl group, decyl group, phenyl group, etc.;
It can have one or more substituents, and the following can be used as the substituents, for example.

R' (R5: hydrocarbon group of C1 to CIG) -x <x
: halogen such as ct, Br, F)-OR'(R':H
Hydrocarbon group of C1 to CIG) -NR7R8 (R7,
R': H or Jd (hydrocarbon group of C1 to Qo) -0COR
” (R': Cs-Cl□ hydrocarbon group) -COO
R” (R”: H or Cl-Cff1 hydrocarbon group)-
COR” (R”: C1 to C1o hydrocarbon group)S
OzR" (R12: OH or C1 to CIO hydrocarbon group) Not -N.

CN The triamide compound of the present invention is intended to be compatible with the matrix component in a fluid state during molding, and to crystallize and phase separate from the matrix component during use. Therefore, it is desirable that the melting point of the triamide compound of the present invention is slightly lower than the molding temperature.

Generally, the molding temperature of polyphenylene ether compositions is 1
The temperature is 05-350°C, preferably 200-300°C.

Therefore, the triamide compound used in the present invention has a melting point of 105 to 350°C, preferably 150 to 300°C.
It is desirable that it be within the range of .

However, if the molding temperature is outside the above range due to the addition of a stabilizer or plasticizer, a triamide compound having a different melting point can be used accordingly. The amount added is 0.1 to 25 parts by weight, preferably 0.5 to 20 parts by weight, particularly preferably 2 to 10 parts by weight, per 100 parts by weight of all polymers.
Parts by weight are preferred.

(5) Additives In the present invention, other additives may be used depending on the purpose.

Examples of additives include stabilizers, plasticizers, flame retardants, various inorganic fillers, mold release agents, and colorants.

The polyphenylene ether composition of the present invention has the advantage of improved fluidity, and has the advantage of being easy to mold even when other additives are added.

OV) Example Hereinafter, the present invention will be explained in a different manner with reference to Examples.

[Example-1] Ho 1J-2,6-dimethyl-1,4-phenylene ether (manufactured by Mitsubishi Yuka Co., Ltd., intrinsic viscosity o, so in chloroform at 25°C) parts by weight of so and high impact polystyrene (Mitsubishi Manufactured by Yukasha, number average molecular weight 55,000, weight average molecular weight 200,000, microgel content 14.5% by weight) 50
N-triphenyl-1,2,3-propanetricarboxylic acid triamide (manufactured by Yamato Kagaku Co., Ltd., melting point measured with melting point analyzer MP-1 model; 252°C ) 5 parts by weight, 2 parts by weight using Prabender.
The mixture was melt-kneaded at 70° C. for 5.5 minutes.

The obtained composition suppresses a decrease in heat resistance and has good fluidity (
The moldability was improved.

[Example-2] N, N', N"-) in place of Nyl-1,2,3-propanetricarboxylic acid triamide on the riff
The composition obtained in the same manner as in Example 1 except for using 5 parts by weight of lipenzoyl-1,2,4-)riaminobenzene (melting point: 260°C) suppressed the decrease in heat resistance,
The fluidity (moldability) was improved.

[Example-3] In place of N,N,N-)rifenyl-1,2,3-propanetricarboxylic acid triamide, N,N,N-)rifhenyl-2-hydroxy-1,2,3-- The composition obtained in the same manner as in Example 1, except for using 5 parts by weight of y'lopanetricarboxylic acid triamide (melting point: 199°C), exhibited suppressed deterioration in heat resistance and good fluidity (moldability). It was an improvement.

Claims (1)

[Scope of Claims] A polyphenylene ether composition with improved moldability, characterized by being formed by mixing polyphenylene ether or a composition of polyphenylene ether and styrene resin with a triamide compound represented by the following formula: . R1: a saturated or wedge-unsaturated chain hydrocarbon residue having a linear or side chain having 1 to 20 carbon atoms, ll! Cyclic hydrocarbon residues, aromatic hydrocarbon residues, or derivative residues containing these groups. R21R"lR": a saturated or unsaturated chain hydrocarbon residue having a linear or side chain having 1 to 10 carbon atoms, an alicyclic hydrocarbon residue, an aromatic hydrocarbon residue, or the like. Derivative residue. (R2, R'', R' may be the same or different)