JPS60245666A - Polyphenylene ether composition having improved moldability - Google Patents

Abstract

PURPOSE:To provide a compsn. having improved flow characteristics while inhibiting lowering in heat resistance, by mixing a specified carboxylic acid amide with a polyphenylene ether or a mixture thereof with a styrene resin. CONSTITUTION:The titled compsn. is obtd. by mixing a carboxylic acid amide having a m.p. of 105-350 deg.C, an MW of 100-1,500, the ratio of inorganic to organic character of 0.6-1.7, inorganic character of 230 or above and organic character of 2,000 or below in the organic conceptual diagram, e.g., N,N'-diheptanoyl-p-phenylenediamine of the formula (m.p.: 211 deg.C, MW:322, inorganic to organic character ratio: 1.04, inorganic character: 415, organic character: 400), with a polyphenylene ether, e.g., poly(2,6-dimethyl-1,4-phenylene)ether, or a compsn. consisting of the polyphenylene ether and a styrene resin. By mixing said amide, a polyphenylene ether compsn. having greatly improved flow characteristics (moldability) can be obtd. without causing lowering in heat resistance.

Description

DETAILED DESCRIPTION OF THE INVENTION m 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, high molding temperatures and pressures are required during molding, making molding by melting difficult.

As one method of improving the molding process ht of polyphenylene ether, a method of blending it with other resins has been attempted. For example, Japanese Patent Publication No. 13-17812 describes blending a 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 to add a plasticizer to polyphenylene ether.
No. 5220 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 hydrocarbons. It has been shown that blending selected compounds into polyphenylene ethers or compositions of polyphenylene ethers and styrenic resins improves moldability.

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

The present inventors believed that in order to improve molding processability (fluidity) while suppressing this decline in thermal performance (thermal properties), it is desirable for additives to have the following properties. .

(During 1,1 molding, that is, under the flow state of the system, M) It must be highly compatible with the IJ lux 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), the phase separation from the matrix components should not occur and the weight of the matrix should not decrease by 1゛g.

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.

The inventors of the present invention conducted studies from this viewpoint and filed a patent application for a dicarboxylic acid amide compound represented by the following formula (Japanese Patent Application No. 152,208/1982).

R2-NHC-R1-CNH-R2 H, saturated or unsaturated chain hydrocarbon residue having a linear or side chain having 1 to 10 carbon atoms, alicyclic hydrocarbon residue or aromatic hydrocarbon residue groups or derivative residues thereof.

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 Derivative residue.

(R2 and R3 may be the same or different.) The present invention was arrived at as a result of more extensive studies.

(Ill) Summary of the Invention The present invention provides means for improving the moldability of polyphenylene ether, polyphenylene ether, and compositions of polyphenylene ether and styrene resin.

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 carboxylic acid amide having the following properties (1) to (3).

(1) Melting point 7105-350°C (2) Molecular weight: 100-1500 (3) Inorganic/organic ratio in organic conceptual diagram -0.6-1.7 Inorganic: 230 or more Organic: 2000 or less [1111 invention Detailed description of (1) Polyphenylene ether The polyphenylene ether used in the present invention has a cyclic structural unit represented by the general formula, in which one ether oxygen atom at the m position connects to the benzene nucleus of the next adjacent unit. connected, n is at least 50, and Q is independently hydrogen, no-rogen, a hydrocarbon group containing no tertiary α-carbon atom, at least one group between the no-rogen atom and the phenyl nucleus. 2
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 monovalent substituent.

A typical example of polyphenylene ether is poly(
2,6-Simethyl-1,4-phenylene) ether, Ho1J (2,6-siethyl-1,4-phenylene) ether, Poly(2-methyl-6-ethyl-1,4-phenylene) ether, Poly(2-methyl-6-ethyl-1,4-phenylene) ether, -Methyl-6-furopyru1.
4-phenylene) ether, poly(2,6-diprobyl-1,4-phenylene) ether, poly(2-ethyl-
6-brobyl-1.4-)22-ether, poly(
2,6-diphthyl-114-phenylene) ether, poly(2,6-sifuronyl-1,4-phenylene) ether, fo17 (2゜6-dilauryl-1,4-phenylene) ether, folJ (2,6 -Sipheniru 1,4
-phenylene) ether, poly(2,6-simethoxy-1,4-phenylene) ether, poly(2,6-jethoxy-1,4-phenylene) ether, 7t"J (2
j TOIF C(i-:f-) xy-1,4-phenylene) ether, poly(2-ethyl-6-methylallyloxy-1,4-phenylene) ether, poly(2,
6-cyclo1,4-phenylene)ether, poly(
2-Methyl-6-phenyl-1,4-phenylene)ether 1,]-”1j(2,6--dibenzyl-1,4-
phenylene) ether, poly(2-ethoxy-1,4-
phenylene) ether, poly(2-chloro-1,4-phenylene) ether, poly(2,5-dibromo-1,4)
-phenylene) ethers and equivalents.

Also, copolymers of 2,6-cyphthylphenol and 2.3.6-trimethylphenol, copolymers of 2,6-cyphthylphenol and 2.3.5.6-titramethylphenol, 2.6- Mention may also be made of copolymers such as those of 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 (eg, 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
No. 58 Meihi-sho and Japanese Patent Publication No. 52-17880
No. 50-51197 and JP-A-50-51197.

A group of polyphenylene ethers which are preferred for the purposes of the present invention are those with alkyl substituents in the two positions ortho to the ether oxygen atom and also copolymers of 2,6-dialkylphenols and 2,3,6-trialkylphenols. are graft polymers obtained by grafting a styrene monomer onto these polyphenylene ether skeletons.

(2) Styrenic resin The styrene resin used in the present invention includes homopolymers such as polystyrene, poly-α-methylstyrene, poly-p-methylstyrene, butadiene rubber, styrene-butadiene copolymer, ethylene- High impact polystyrene modified with various rubbers such as propylene copolymer, ethylene-propylene-diene terpolymer, styrene-butadiene copolymer, styrene-maleic anhydride copolymer, styrene-acrylonitrile copolymer, styrene-acrylonitrile - There are butadiene copolymers, styrene-methyl methacrylate copolymers, etc., and these styrene resins are mixed at a ratio of 0 to 2000 parts by weight with respect to 100 parts by weight of the polyphenylene ether resin.

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

Polymers to be added include natural or +d-synthesized rubbery elastic polymers, such as natural rubber, polyisoprene, polybutadiene, copolymers of styrene and conjugated dienes such as butadiene (including block copolymers). , ethylene-propylene copolymer, ethylene-propylene-nonconjugated diene terpolymer, etc. can be used.

In addition, it is also possible to use polymers that have been made sensitive by introducing polar groups into them, and polymers that have been made sensitive to rubber-like elastic polymers are also used, as well as polyethylene, ethylene-vinyl acetate copolymers, It is also possible to use a polymer obtained by imparting sensitivity to a polyolefin polymer such as polypropylene.

As a means of imparting sensitivity, the above-mentioned polymer may be treated with an unsaturated organic acid or its anhydride (for example, acrylic acid, methacrylic acid, maleic acid, itaconic acid, or anhydride thereof, etc.) or an unsaturated silane compound (for example, , vinyltrimethoxinelan, vinyltrimethoxysilane, vinyltriacetoxysilane, γ-methacryloxyprobyltrimethoxysilane, propenyltrimethoxysilane, etc.).

In addition, a polymer imparted with sensitivity can also be obtained by block or random polymerization of ethylamine 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. be able to.

When using rubber-modified polystyrene, the amount of the rubber-like elastic polymer or polymer imparted with sensitivity added is such that the total amount including the rubber content derived from it is 0.5 to 0.5 to the total amount of all polymer components. It is about 50% by weight, preferably about 2 to 40% by weight.

Moreover, when using a polymer imparted with sensitivity, it is preferable to add an inorganic filler. When using a sensitized polymer and an inorganic filler together, the sensitized polymer is dispersed in the matrix of the composition of polyphenylene ether or polyphenylene ether and styrene resin, and the sensitized polymer is dispersed in the sensitized polymer. By forming a special structure in which the inorganic filler is selectively filled, it is possible to 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 average particle size of the inorganic filler is preferably about 0.05 to 1.0μ, and the amount is 0.5 to 60% by weight, preferably 1 to 45% by weight, based on the entire composition obtained by mixing. Additionally, other polymers that may be used include polyphenylene ether,
Alternatively, a polyolefin graft polymerized with a styrene resin can also be used.

Polyphenylene ether grafted polyolefin is produced by reacting glycidylated polyphenylene ether with epichlorohydrin, and then converts it into a polyolefin having a carboxyl group or d-acid anhydride group in the main chain and side chains, such as ethylene-acrylic acid copolymer, ethylene-acrylic acid copolymer, ethylene- It can be obtained by grafting onto a methacrylic acid copolymer, maleic anhydride-modified polypropylene, maleic anhydride-modified polyethylene, maleic anhydride-modified ethylene/vinyl acetate copolymer, or the like.

Polyphenylene ether-grafted polyolefins are polyphenylene ether grafted onto polyolefins having glycidyl groups in their side chains, such as ethyl l/n/glycidyl methacrylate copolymer, ethylene/vinyl acetate/glycidyl methacrylate copolymer, etc. It can also be obtained by doing.

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/
Acrylic acid copolymer, styrene/methacrylic acid copolymer, etc., polyolefin with glycidyl group in the side chain,
For example, it can be obtained by grafting ethylene/glycidyl methacrylate copolymer, ethyl/vinyl acetate/glycidyl methacrylate copolymer, or the like.

The amount added is polyphenylene ether, and ma/ζ is 0.1 of polyphenylene ether grafted polyolefin based on the composition of polyphenylene ether and styrene resin, and the total amount of polyphenylene ether grafted polyolefin and/or polystyrene grafted polyolefin. ~50% by weight, preferably 1-30% by weight, 1-80% by weight of polystyrene kraft polyolefin,
Preferably a range of 1 to 30% by weight is used.

The grafted polyolefin can be added after graft polymerization in advance, but when using a polyolefin having a glycidyl group, polyphenylene ether or a styrene resin having a carboxylic acid or its anhydride group can be added. The graft reaction can be carried out by kneading at a high temperature of .degree. 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 polyolefin produced by the progress of the graft reaction,
A composition containing polystyrene graft polyolefin and/or polystyrene graft polyolefin can be obtained all at once, and is the most preferable method from an economical point of view.

(4) Carboxylic acid amide The carboxylic acid amide used in the present invention is represented by the following.

(1) Melting point: 105-350°C (2) Molecular weight: 100-1500 (3) Inorganic/organic ratio in organic conceptual diagram -0.6-1.7 Inorganic: 230 or more Organic: 2000 or less (1 ), (2), and (3).

If the melting point is below 105°C, phase separation from polyphenylene ether will be insufficient, and if the melting point is above 350°C,
A homogeneous phase is not formed during melt molding, and the effect of improving fluidity cannot be obtained.

Furthermore, the molecular weight of carboxylic acid amide is 100 to 1500.
Preferably, it is selected from those within the range of 130 to 1000.

If the molecular weight is less than 100, phase separation will occur.<<If the molecular weight is more than 1,500, the fluidity improving effect will be reduced. 130
-1000 is preferable □ Also, in the organic conceptual diagram, the carboxylic acid amide has an inorganic/organic ratio of -0.6 to 1.7, inorganicity: 230 or more,
Organic: Selected from those within the range of 2000 or less.

If the compatibility between the carboxylic acid amide and the matrix component is too good, the carboxylic acid amide will not undergo phase separation from the matrix component due to crystallization during use, and if the compatibility is too poor, the carboxylic acid amide will fail during molding. In a fluidized state, it is not compatible with M) and L) and neither of them exhibits the effects of the present invention.

Therefore, the carboxylic acid amide of the present invention is selected from those having appropriate compatibility with the matrix component, and in the present invention, an organic conceptual diagram is used to indicate compatibility.

Organic conceptual diagram is Fuji 1) Mu: Area of Chemistry, vol. 1
1. .

A10, 1957.

In other words, the organic conceptual diagram divides ordinary organic compounds into organic and inorganic compounds (or rather, the part based on the London dispersion force and the part based on the dipole force of their cohesive force), and divides them into two groups according to the size of their properties. It is represented by one point on a dimensional diagram.

In organic conceptual diagrams, the horizontal axis shows the London dispersion force, and since the intermolecular force based on the dispersion force increases in proportion to the number of carbons in the compound, the horizontal axis is proportional to the number of carbons. In hydrocarbons, it is all dispersion force, so the position is determined on the horizontal axis. However, since water is one of the non-organic molecules with the largest dipole force, the partition ratio of organic matter to water and petroleum ether, that is, polar and non-polar solvents (this is the same as methanol and petroleum ether). (It may be measured by the distribution ratio to If we know the inorganic nature of K, we can quantitatively determine the number of various functional groups including -OH. Table 1 shows examples of average evaluation values determined from a large number of substances based on experiments and experience.

As a standard, -OH is inorganic (100) and -CH2 is organic (20).

(Left below) In the organic conceptual diagram, those with the same or close inorganic/organic ratio are compatible, and the farther apart they are, the lower the compatibility.

The inorganic/organic ratio of Ho-1J (2,6-dimethyl-1,4-phenylene) ether is 0.28, and the inorganic/organic ratio of polystyrene is 0.10, so they can be mixed at any ratio. The H/organic ratio of Tabo IJ (2,6-dimethyl-1,4-phenylene)ethertopolystyrene is 0.2.
Exists between 8 and 0100. If the inorganic/organic i ratio of the carboxylic acid amide of the present invention is Q, or less than 6, the compatibility between the carboxylic acid amide and the matrix component is too good, and the carboxylic acid amide may undergo phase separation from the matrix component due to crystallization during use. Furthermore, if the inorganic/organic ratio is 1.7 or more, the carboxylic acid amide is not compatible with the matrix component under the fluid state during molding, and neither exhibits the effects of the present invention. Even if the inorganic/organic ratio is in the range of 0.6 to 1.7, if the inorganicity is 230 or less, the compatibility is too good, and
When the organicity is 2,000 or more, the number of carbon atoms is large and the molecular weight is therefore too high, and the effects of the present invention are not exhibited.

The carboxylic acid amide can have the following structural units: 1 0.0,0. -C.

1 For example, it is expressed by the following formula.

R: Contains 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 groups thereof. Derivative residue.

n: An integer selected from 1 to 4 m: A number selected from 2 to 15, and when it has a distribution,
A number whose average value is selected from 2 to 15.

As R, for example, a methyl group, a methylene group, an ethyl group,
Ethylene group, ethenylene group, trimethylene group, propylene group, propanetriyl group, butyl group, tetramethylene group, butanetriyl group, pentyl group, pentamethylene group, pentantriyl group, hexyl group, cyclohexyl group, hexamethylene group, cyclohexyl group Silene group, hexanetriyl group, cyclohexanetriyl group, heptyl group, octyl group, octamethylene group, decamethylene group, phenyl group, phenylene group, benzenetriyl group, naphthyl group, naphthylene group, naphthalenetriyl group, biphenylene group , and derivative residues obtained by bonding a plurality of these groups with, for example, the following.

10-(oxy group) -8-(thio group) 18O2-(sulfonyl group) -CO-'(carbonyl group) -COO-C carbonyloxy group) R has one or more substituents It is possible,
As the substituent, for example, the following can be used.

-R'(R,': C1-Coo hydrocarbon group)-
X (X: halogen such as α, ■, F, etc.) -OR2 (R2:
H or C1-Cl0 hydrocarbon group)-NR3R' (R
3, R': H or C1-C1o hydrocarbon group) -〇〇0R5 (R5: C1-C1o hydrocarbon group) -COO
R6 (R6: H or Ci-C1o hydrocarbon group) -CO
R7 (R': Ci to C1o hydrocarbon group) -8O
2R8 (R8: OH or C1 to C1o hydrocarbon group) N
02-N.

CN The amount of the carboxylic acid amide of the present invention added is 10 in total for all polymers.
0.1 to 25 parts by weight, preferably 0.5 parts by weight
~20 parts by weight, particularly preferably 2 to 10 parts by weight.

(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.

Leap example Hereinafter, the present invention will be specifically explained with reference to Examples.

[Example-1] 50 parts by weight of HoIJ-2,6-dimethyl-1,4-phenylene ether (manufactured by Mitsubishi Yuka Co., Ltd., intrinsic viscosity 0.50 in chloroform at 25°C) and high impact polystyrene (Mitsubishi Yuka Co., Ltd.) 50 parts by weight (manufactured by Kasha, number average molecular weight 55,000, weight average molecular weight 200,000, microgel content 14.5% by weight) and O N, N'-diheptanoyl-P-phenylenediamine (
Melting point: 211°C, molecular weight: 322, inorganic/organic ratio:
1. R4, inorganic: 415, organic: 400) 5 weights were melt-kneaded at 260° C. for 7.5 minutes using a Brabender.

After the cross-crossing was completed, the melt index (250°C, 1oKq 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 Kg/ rtl load). The results are shown in Table-2.

[Comparative Example-1] Table 2 shows the results obtained in the same manner as in Example-1 except that N,N'-diheptanoyl-P-phenylenediamine was not used.

[Comparison 1, 11-2] Benzamide (melting point: 128°C, molecular weight: 121, inorganic/organic ratio: 1.54, inorganic: 2) in place of N,N'-shihephtanoyl-P-phenyleneethylenediamine
15. Organic: 140) The results were obtained in the same manner as in Example 1, except that 5 parts by weight was used, and the results are shown in Table 2.

[Comparative Example-3] Sepacic acid diamide (melting point: 210°C
, molecular weight: 200. Table 2 shows the results obtained in the same manner as in Example 1, except that 5 parts by weight (inorganic/organic ratio: 2.01, inorganic: 400, organic: 200) was used.

[Comparative Example-4] Stearic acid amide (melting point = 109°C,
Molecular weight = 283, inorganic/organic ratio: 0.56, inorganic: 200, organic: 360) except for using 5 parts by weight.
Table 2 shows the results obtained in the same manner as in Example-1.

(Left below) H2NCO (: CH2'j8 C0NH23)
As is clear from CH3+CH2+, 6C1)N)I2-2, by using N,N'-di,butanoyl-P-phenylenediamine, flow (formability) is significantly improved, and heat resistance is reduced. suppressed.

The effects of the present invention can be understood by looking at the results in Table 2 together with the organic conceptual diagram shown in Figure 2.

[Example-2] P-nitrobenzamide (melting point = 200
C, molecular weight: 166, inorganic/organic ratio = 1.4, inorganic = 285, organic: 210) except that 5 parts by weight were used. -3.

[Example-3] N-phenyl-3-hydroxy-2-naphthoic acid amide (melting point: 243°C, molecular weight: 263, inorganic: raw/organic 1 raw ratio) in place of N,N-shihephtanoyl-P-phenyleneethylenediamine Table 3 shows the results obtained in the same manner as in Example 1, except that 5 parts by weight of 1.1, inorganic: 375, organic: 340) were used.

[Shou7if! Example i ~ 4] NlN-Shihefurinoyl P-phenylene ethylenedi7
N-phenyl-δ-penzoylamino- instead of minni
n-valeramide (melting point: 177°C, molecular weight: 296
Table 3 shows the results obtained in the same manner as in Example 1, except that 5 parts by weight of inorganic/organic ratio = 1, 2, inorganic: 430, organic + 360) were used.

[Example-5] Phthalimide (melting point: 238°C, molecular weight =
147, inorganic/organic ratio: 1. ri, inorganicity = 245,
Organic: 160) Example row-1 except that 5 parts by weight is used
Table 3 shows the results obtained in the same manner as above.

(Margin below)

[Brief explanation of the drawing]

FIG. 1 is a diagram showing inorganic/organic values of carboxylic acid amides used in Examples and Comparative Examples. Patent applicant Mitsubishi Yuka Co., Ltd. Agent Patent attorney Hidetoshi Furukawa (and 1 other person) Figure 1 Inorganic properties

Claims (1)

[Scope of Claims] Polyphenylene ether, mataha, a composition of polyphenylene ether and styrene resin, and the following (1) to (3)
) A polyphenylene ether composition with improved moldability, characterized in that it is made by mixing with a carboxylic acid amide having the following characteristics. (1) Melting point: 105-350°C (2) Molecular weight: 100-1500 (3) Inorganic/organic ratio in the organic conceptual diagram -0.6-1.7 Inorganic: 230J, organic: 2000 or less