JPS60250064A - Polyphenylene ether composition having improved moldability - Google Patents

Abstract

PURPOSE:To provide the titled compsn. having excellent moldability and resistance to impact and heat, by mixing a specified diamide compd. with a polyphenylene ether or a mixture thereof with a styrene resin. CONSTITUTION:0.1-25wt% diamide compd. of formula II [wherein R<1> is a residue of an 11-20C straight-chain or branched (un)saturated linear, alicyclic or arom. hydrocarbon or its derivative; R<2>, R<3> are each a residue of a 1-10C straight-chain or branched (un)saturated linear, alicyclic or arom. hydrocarbon or its derivative] and having an m.p. of 105-350 deg.C and optionally 0.5-50wt% natural or synthetic rubber elastomeric polymer or polymer having a sensitivity imparted thereto by introducing polar groups, are blended with a compsn. consisting of 100pts.wt. polyphenylene ether resin contg. a repeating unit of formula I (wherein Q is H, halogen, hydrocarbon group contg. no tertiary alpha-C, halohydrocarbon group contg. at least two C atoms between the halogen atom and the phenyl nucleus; n is at least 50) and 0-200pts.wt. styrene resin.

Description

DETAILED DESCRIPTION OF THE INVENTION 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 resistance and is somewhat brittle. Furthermore, since this resin has a high melting temperature and high melt viscosity, high molding temperatures and pressures are required 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, Japanese Patent Publication No. 43-17812 Honebun IR describes blending high-impact polystyrene resin with polyphenylene ether.

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

Another method to improve the moldability of polyphenylene ether is the addition of a plasticizer to polyphenylene ether.
Publication No. 5220 describes aromatic organic acid esters having good or compatibility with polyphenylene ether resins, polyesters having aromatic groups, organic phosphate esters having aromatic groups, and chlorinated aromatic hydrocarbons. It has been shown that moldability can be improved by blending a compound selected from the following into polyphenylene ether or a composition of polyphenylene ether and styrenic mi.

However, plasticizers (
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 ether or a composition of polyphenylene ether and styrene resin. It is thought that the heat resistance decreases as a result.

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) At the time of molding, that is, under the fluid state of the system, it must have good compatibility with the IJ lux component and exhibit the same fluidity-improving effect as a plasticizer.

(2) During use, that is, under flow-stopping conditions (7 g of matrix
In the following temperature ranges), phase separation from the matrix components should occur and the Tg of the matrix should not be lowered.

However, 1. 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.

The present inventors have conducted extensive research from this perspective and have arrived at the present invention.

ra] Summary of the Invention The present invention provides means for improving the moldability of polyphenylene ether or a composition of polyphenylene ether and styrenic resin.

That is, a composition of wood-based polyphenylene ether, a composition of polyphenylene ether and a styrene resin,
The object of the present invention is to provide a polyphenylene ether composition having improved moldability, which is characterized by being mixed with a diamide compound represented by the following formula.

R1, a saturated or bent unsaturated chain hydrocarbon residue having a linear or bent side chain having 11 to 20 carbon atoms, an alicyclic hydrocarbon residue, an aromatic hydrocarbon residue, or this Derivative residues containing groups such as.

R11, R8: a saturated or bent unsaturated chain hydrocarbon i group having a linear or bent side chain having 1 to 10 carbon atoms, a #A hydrocarbon residue or an aromatic hydrocarbon residue, or , these derivative residues.

(R2, R" may be the same or different, 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, nitrogen, tertiary α-carbon. At least two hydrocarbon groups containing no atoms, between the norogen atom and the phenyl nucleus
one selected from the group consisting of a halohydrocarbon group having 2 carbon atoms, a hydrocarbon oxy group, and a no 2 hydrocarbon oxy group having at least 2 carbon atoms between the 2 carbon atoms and the phenyl nucleus. Indicates a valence substituent.

A typical example of polyphenylene ether is poly(
2,6-dimethyl-1,4-phenylene) ether, (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-diprobyl-1,4-phenylene) ether, poly(2-ethyl-6-brobyl-1,4-phenylene) ether, poly(2,6-cyphthyl-1゜4- phenylene) ether,
Poly(2,6-dipropenyl-1,4-phenylene) ether, yt'1J (2゜6-dilauryl-1,4-phenylene) ether, d'li(2+6 yphenyl-
1,4-phenylene) ether, poly(2,6-simethoxy 1,4-7 enylene) ether, poly(2,6
-jetoxy-1,4-phenylene)ether, poly(
2-Methoxy-6-ethoxy1.4-phenylene)motyl, poly(2-ethyl-6-methialyloxy-1)
, 4-phenylene) ether, BoIJ (2,6-dichloro□-1,4-phenylene) ether, poly(2-methyl-6-phenyl-1,4-phenylene) ether 1,
I-'su(2,6-dipendylu-1,4-phenylene)
Ether 1. t'1J (2-ethoxy-1,4-phenylene) ether, poly(2-chloro-1,4-phenylene) ether, poly(2,5-dibromo-1,4-phenylene) ether and the like. .

Also, a copolymer of 2,6-dimethylphenol and 2.3.6-)limethylphenol, a copolymer of 2.6-''dimethylfeshield 2.3,5.6-titramethylphenol, 2. Mention may also be made of copolymers such as those of 6-dinitylphenol and 2,3,6-trimethylphenol.

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 (NFIJ, tungsten, styrene, p-methylstyrene, α-methylstyrene, etc.).

Methods for producing the above-mentioned polyphenylene ethers are known, for example, US Pat. Nos. 3,306,874 and 33
No. 06875, No. 3257357 and No. 32573
58 specifications and Japanese Patent Publication No. 52-1788
No. 0 and JP-A-50-51197.

A group of polyphenylene ethers preferred for the purposes of the present invention are those with alkyl substituents in the two positions ortho to the ether oxygen atom and copolymers of 2.6-dialkylphenols and 2.3.6-)realkylphenols. (2) Styrenic resin The styrenic resin used in the present invention includes polystyrene, poly-methyl High-impact polystyrene modified with homopolymers such as styrene and poly-p-methylstyrene, and various rubbers such as butadiene rubber, styrene-butadiene copolymer, ethylene-propylene copolymer, and ethylene-propylene-genterpolymer FK; These include styrene/butadiene copolymer, styrene/maleic anhydride copolymer, styrene/acrylonitrile copolymer, styrene/acrylonitrile/butadiene copolymer, styrene/methyl methacrylate copolymer, etc. 0 to 2000 parts by weight per 100 parts by weight of polyphenylene ether resin,
mixed at the same time.

(3) Addition of other polymers If other polymers are added to polyphenylene ether or a composition of polyphenylene ether and styrene resin for the purpose of improving impact resistance, etc., problems occur.

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 K.

Further, a polymer imparted with sensitivity can also be obtained by block or random polymerization of ethylene with a vinyl monolayer 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 of the rubber component derived therefrom is 0.5 with respect to the total amount of all polymer components. -50 weight t*, preferably 2 to 40 weight % slenderness.

When using a shriveled and sensitive polymer, it is preferable to add an inorganic filler. When a sensitized polymer and an inorganic filler are used together, the sensitized polymer is dispersed in the matrix of polyphenylene ether or a composition of polyphenylene ether and styrene resin, and the inorganic filler is dispersed in the sensitized polymer. It forms a special structure in which the filler is selectively filled, and can obtain excellent physical properties such as 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 silica, can be used.

The inorganic filler preferably has an average particle diameter of 0.05 to 1.0 μm, and is present in an amount of 0.5 to 60% by weight, preferably 1 to 45% by weight, based on the entire composition obtained by mixing. is used.

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

Polyphenylene ether grafted polyolefin is a polyolefin that has a carboxyl group or silicate anhydride group in the main chain or side chain, such as ethylene/acrylic acid copolymer, ethylene/methacrylic acid, by reacting glycidylated polyphenylene ether with epichlorohydrin. Copolymerized maleic anhydride-modified polypropylene, maleic anhydride-modified polyethylene, maleic anhydride-modified ethylene/vinyl acetate copolymer, etc. can be obtained by crafting.

Polyphenylene ether grafted polyolefins can also be obtained 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. I can do it.

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 Polymer, styrene/asconitic anhydride copolymer, styrene/
Grafting polyolefins having glycidyl groups in the side chains, such as ethylene-glycidyl methacrylate copolymers, ethylene-vinyl acetate-glycidyl methacrylate copolymers, etc., to acrylic acid copolymers, styrene/methacrylic acid copolymers, etc. This can be obtained by

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 graft polyolefin, polyphenylene ether graft polyolefin accounts for 0.1 to 50% by weight, preferably 1 to 30% by weight, and polystyrene craft polyolefin accounts for 1 to 80% by weight, preferably 1 to 30% by weight. A range is used.

The grafted polyolefin can be added after graft polymerization in advance, but when using a polyolefin having a glycidyl group, it is necessary to add it to a styrene resin having a polyphenylene ether or anhydride group at 150°C. A graft reaction can be carried out by kneading at a high temperature above.

Therefore, by kneading the composition of glycidyl group-containing polyolefin and dJ cypolyphenylene ether or id ho IJ phenylene styrene resin at high temperature, each component is mixed uniformly, and at the same time, as the grafting reaction progresses, This is the most preferable method from an economical point of view, since it is possible to obtain a composition containing the polyphenylene ether grafted polyolefin and/or polystyrene grafted polyolefin at once.

(4) Diamide compound The diamide compound used in the present invention has the following formula % formula % R1, a saturated or unsaturated chain hydrocarbon residue having a linear or side chain having 11 to 20 carbon atoms, Cyclic hydrocarbon residues, aromatic hydrocarbon residues, or derivative residues containing these groups.

R2, R3, a saturated or unsaturated chain hydrocarbon residue having a linear or side chain having 1 to 10 carbon atoms, an alicyclic hydrocarbon residue, or an aromatic hydrocarbon residue, or a derivative thereof residue.

(R" and R" may be the same or different.) Examples of R1 include a dodecamethylene group, a biphenylene group, a diphenylenemethane group, or a plurality of groups such as a methylene group, an ethylene group, a trimethylene group, and a propylene group. , tetramethylene group, imbutylene group, pentamethylene group, cyclopentyl group, hexamethylene group, cyclohexylene group, octamethylene group, decamethylene group, phenylene group, naphthalene group, etc., are combined with, for example, the following derivatives. residue.

10-(oxy group) -8-(thio group) SOs (sulfonyl group) -C0-(carbonyl group) -COO-(carbonyloxy group) R*, R11 include, for example, methyl group, ethyl group, propyl group 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, naphthyl group, etc. It will be done.

R' r R'' and R1 may have one or more E substituents, for example, the following can be used as substituents.

R'(R': C1-Cto hydrocarbon content group)-X (
X: /% (ffgen)-OR' of ct, Br, F, etc.
(R': H or C1-CIO hydrocarbon group) -NR'
R'(R',R'': H or a hydrocarbon group of CI -CIO) -0COR''(R': a hydrocarbon group of C1 to Cto) -COOR''(R'': H or a hydrocarbon group of C1 to CI
O hydrocarbon group) COR10 (R”: C1-Cw hydrocarbon group) SOsR” (R”: OH or C~C
1o hydrocarbon group) N02CN.

CN The diamide compound of the present invention is intended to be compatible with the matrix component in a fluid state during molding, and crystallize and phase separate from the matrix component during use. Therefore, it is desirable that the melting point of the diamide 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, it is desirable that the diamide compound used in the present invention has a melting point in the range of 105 to 350°C, preferably 150 to 300°C.

However, if the molding temperature is outside the above range due to the addition of a stabilizer or plasticizer, a diamide compound with a different melting point can be used accordingly. The amount added is preferably 0.1 to 25 parts by weight, particularly preferably 0.5 to 20 parts by weight, and particularly preferably 2 to 10 parts by weight, based on a total of 100 parts by weight of all polymers.

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

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

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

Examples Hereinafter, the present invention will be specifically explained with reference to Examples. Intrinsic viscosity o
, so) 50 parts by weight of high-impact polystyrene (manufactured by Mitsubishi Yuka Co., Ltd., number average molecule 1155s, weight average molecule t205, microgel content 14.5wt5) so and 2 shown by the following structural formula: Melt 5 parts by weight of 2'-bis(phenylcarbamoyl)biphenyl (manufactured by Yamato Kagaku Co., Ltd., measured with melting point meter MP-1 model *melting point: 230°C) at 260°C for 7.5 minutes using a Brabender. Kneaded.

After the cross-crossing was completed, the melt index (250°C, 10Kf load), which indicates moldability (fluidity), was measured, and a prescribed test piece was produced using a press, and the heat distortion temperature was measured (18.6 Kp / cJ load). The results are shown in Table-1.

[Comparative Example-1] Table 1 shows the results obtained in the same manner as in Example-1 except that 2.2'-bis(phenylcarbamoyl)biphenyl was not used.

[Comparative Example-2] Example-1 except that 5 parts by weight of triphenyl phosphate (melting point: 50°C) as a plasticizer was used instead of 2.2'-bis(phenylcarbamoyl)pi The results obtained in the same manner as above are shown in Table 1. As is clear from Table 1, by using 2,2'-bis(phenylcarbamoyl)biphenyl, the fluidity (moldability) is significantly improved. , the decrease in heat resistance is suppressed. Although the plasticizer improves the fluidity, the heat resistance decreases significantly, and the effect of the present invention can be understood.

Table 1 [Example 2] Except for using 5 parts by weight of 2.4'-bis(phenylcarbamoyl)benzophenone (melting point: 227°C) in place of 2.2'-bis(phenylcarbamoyl)biphenyl. Table 2 shows the results obtained in the same manner as in Example-1.

(Leaving space below) Procedural amendment (voluntary) Manabu Shiga, Commissioner of the Patent Office1, Indication of the case 1982 Patent Application No. 106 (No. 1262, Name of invention Polyphenylene ether composition with improved moldability3, Amendment) Patent applicant Mitsubishi Yuka Co., Ltd. 2-5-2 Marunouchi, Chiyoda-ku, Tokyo (60s) 4, Agent: Mitsubishi Yuka Co., Ltd. 2-5-2 Marunouchi, Chiyoda-ku, Tokyo 100 5. Scope of Claims and Detailed Description of the Invention in the Specification Subject to Amendment Column 6. Contents of Amendment (1) The scope of claims shall be as shown in the attached sheet.

(2) On page 6, lines 1 to 12 of the specification, the statement “R1: number of carbon atoms may be different.” rR”: [ifl-like or structured side A saturated or unsaturated chain hydrocarbon residue having a chain, an alicyclic hydrocarbon residue, an aromatic hydrocarbon residue, or a derivative residue containing these groups.

However, the number of carbon atoms is 11 to 20.

at, R11: a saturated or pendant unsaturated chain hydrocarbon residue having a linear or side chain, an alicyclic hydrocarbon residue, or an aromatic hydrocarbon residue, or a derivative residue thereof.

However, the number of carbon atoms is 1 to 10.

(R2, R'' may be the same or different) shall be.

(3) From line 9 on page 16 to line 2 on page 17 of the specification, “R1:
[R1: saturated or unsaturated chain hydrocarbon residue having a straight chain or side chain, #Ru type carbonization] Hydrogen residues, aromatic hydrocarbon residues, or derivative residues containing these groups.

However, the number of carbon atoms is 11 to 20.

R'lR": a saturated or skew-unsaturated chain hydrocarbon residue having a linear or side chain, an alicyclic hydrocarbon residue, or an aromatic hydrocarbon residue, or a derivative residue thereof. Base.

However, the carbon number Fi is 1 to 10.

(R" and R' may be the same or different)" shall be.

(Mr. Bessha) (@Claims) A moldable product characterized by being formed by mixing polyphenylene ether or a composition of polyphenylene ether and styrene resin with a diamide compound represented by the following formula. Improved polyphenylene ether composition, R1: a saturated or pendant unsaturated chain hydrocarbon residue having a linear or pendant side chain, an alicyclic hydrocarbon residue, an aromatic hydrocarbon residue, or Derivative residues containing these groups.

However, the number of carbon atoms is 11 to 20.

R'', R': a saturated or bent unsaturated chain hydrocarbon residue having a linear or bent side chain, an alicyclic hydrocarbon residue or an aromatic hydrocarbon residue, or Derivative residue.

However, the number of carbon atoms is 1 to 10.

(R” and R” may be the same or different) JP-A-60-250064 (8)

Claims (1)

[Claims] A polyphenylene ether composition with improved moldability, characterized by mixing polyphenylene ether, a composition of polyphenylene ether and a styrene resin, and a diamide compound represented by the following formula. thing. R1: A saturated or pendant unsaturated chain hydrocarbon residue having a linear or side chain having 11 to 20 carbon atoms, an alicyclic hydrocarbon residue, an aromatic hydrocarbon residue, or the like. Derivative residues containing groups. R2+R": a saturated or unsaturated chain hydrocarbon residue having a linear or side chain having 1 to 100 carbon atoms, an alicyclic hydrocarbon residue, or an aromatic hydrocarbon residue, such as Derivative residue. (R", R" may be the same or different)