JPH0530864B2 - - Google Patents

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, a high heat distortion temperature, and self-extinguishing properties, and 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 for improving the moldability of polyphenylene ether, attempts have been made to blend it with other resins. For example, Tokuko Sho 43-17812
The publication 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.
For example, Japanese Patent Publication No. 49-5220 describes an aromatic organic acid ester having good compatibility with polyphenylene ether resin, a polyester having an aromatic group, an organic phosphate ester having an aromatic group, and It has been shown that moldability can be improved by blending a compound selected from chlorinated aromatic hydrocarbons into polyphenylene ether or a composition of polyphenylene ether and styrenic resin. However, when a plasticizer (for example, an organic phosphate ester having an aromatic group) is blended with polyphenylene ether or a composition of polyphenylene ether and styrene resin, moldability is improved, but performance will be significantly reduced. 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, the glass transition temperature (Tg) of the matrix is ) is considered to decrease, 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 matrix components and exhibit the same fluidity-improving effect as a plasticizer. (2) During use, i.e. under flow stopped conditions (matrix
(temperature range below Tg), it should phase separate from the matrix components and do not lower the Tg of the matrix. 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 present inventors have arrived at the present invention as a result of intensive studies from this viewpoint. [] Summary of the invention The present invention provides polyphenylene ether, or
The object of the present invention is to provide a means for improving the moldability of a composition of polyphenylene ether and styrene resin. That is, the present invention is made by mixing polyphenylene ether or a composition of polyphenylene ether and styrene resin with a diamide compound represented by the following formula, and the diamide compound is mixed with 100 parts by weight of the polymer. The present invention provides a polyphenylene ether composition with improved moldability, characterized in that the compound is contained in an amount of 0.5 to 20 parts by weight. R ¹ : A saturated chain hydrocarbon residue or aromatic hydrocarbon residue having a linear or side chain having 11 to 20 carbon atoms, or two aromatic hydrocarbon residues bonded by the following groups. R ² , R ³ : Saturated chain hydrocarbon residue or aromatic hydrocarbon residue having a linear or side chain having 1 to 10 carbon atoms. (R ² and R ³ may be the same or different) [] Specific description of the invention (1) Polyphenylene ether The polyphenylene ether used in the present invention has the general formula 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, Hydrocarbon groups containing no tertiary α-carbon atoms, halohydrocarbon groups having at least two carbon atoms between the halogen atom and the phenyl nucleus, hydrocarbonoxy groups and between the halogen atom and the phenyl nucleus Indicates a monovalent substituent selected from the group consisting of halohydrocarbonoxy groups having at least 2 carbon atoms. Typical examples of polyphenylene ether include poly(2,6-dimethyl-1,4-phenylene) ether, poly(2,6-diethyl-1,4
-phenylene)ether, poly(2-methyl-6)
-ethyl-1,4-phenylene) ether, poly(2-methyl-6-propyl-1,4-phenylene) ether, poly(2,6-dipropyl-1,
4-phenylene)ether, poly(2-ethyl-
6-propyl-1,4-phenylene) ether,
Poly(2,6-dibutyl-1,4-phenylene)
Ether, poly(2,6-dipropenyl-1,4
-phenylene) ether, poly(2,6-dilauryl-1,4-phenylene) ether, poly(2,6-diphenyl-1,4-phenylene) ether, poly(2,6-dimethoxy-1,4-phenylene) ) ether, poly(2,6-diethoxy-1,4-phenylene) ether, poly(2-methoxy-6-ethoxy-1,4-phenylene) ether, poly(2-ethyl-6-stearyloxy-1, 4-phenylene)ether, poly(2,
6-dichloro-1,4-phenylene)ether,
Poly(2-methyl-6-phenyl-1,4-phenylene) ether, poly(2,6-dibenzyl-
1,4-phenylene) ether, poly(2-ethoxy-1,4-phenylene) ether, poly(2-phenylene) ether,
-chloro-1,4-phenylene) ether, poly(2,5-dibromo-1,4-phenylene) ether and the like. Also, 2,6-dimethylphenol and 2,3,6
-Copolymer of trimethylphenol, copolymer of 2,6-dimethylphenol and 2,3,5,6-tetramethylphenol, copolymer of 2,6-diethylphenol and 2,3,6-trimethylphenol Mention may also be made of copolymers such as polymers. Furthermore, the polyphenylene ether used in the present invention is a polyphenylene ether defined by the above general formula grafted with a styrenic monomer (for example, styrene, p-methylstyrene, α-methylstyrene, etc.). Also included are modified polyphenylene ethers. Methods for producing polyphenylene ethers corresponding to the above are known, for example, US Pat. No. 3,306,874;
It is described in each specification of No. 3306875, No. 3257357, and No. 3257358, and the specification of Japanese Patent Publication No. 17880/1988 and Japanese Patent Application Publication No. 51197/1989. Preferred groups of polyphenylene ethers for the purposes of the present invention are those with alkyl substituents in the two ortho positions to the ether oxygen atom and co-containers of 2,6-dialkylphenols and 2,3,6-trialkylphenols. Further, the polymer is a graft polymer obtained by grafting a styrene monomer onto the polyphenylene ether skeleton. (2) Styrenic resin The styrene resin used in the present invention includes homopolymers such as polystyrene, poly-α-methylstyrene, and poly-p-methylstyrene, butadiene rubber, styrene-butadiene copolymer, and ethylene-propylene. copolymers, high-impact polystyrene modified with various rubbers such as ethylene-propylene-dient terpolymers, styrene-butadiene copolymers, styrene-butadiene copolymers,
Maleic anhydride copolymer, styrene/acrylonitrile copolymer, styrene/acrylonitrile/
There are butadiene copolymers, styrene/methyl methacrylate copolymers, etc., and these styrene resins are mixed in a proportion 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 polyphenylene ether or a composition of polyphenylene ether and styrene resin for the purpose of improving impact resistance. Polymers to be added 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-nonconjugated 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 Furthermore, a polymer imparted with sensitivity can also be obtained by block or random polymerization of ethylene with 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 elastic polymer or the polymer imparted with sensitivity is such that the total amount including the rubber content derived from it is 0.5 to 50% by weight based on the total amount of all polymer components. %, preferably about 2 to 40% by weight. Further, when using a polymer imparted with sensitivity, 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, imparting sensitivity. Forms a special structure in which inorganic filler is selectively filled in the polymer.
Excellent physical properties such as mechanical strength can be obtained. 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 size of about 0.05 to 1.0 μm, and is used in an amount of 0.5 to 60% by weight, preferably 1 to 45% by weight, based on the entire composition obtained by mixing. Furthermore, as other polymers, polyphenylene ether or polyolefin graft-polymerized with a styrene resin can also be used. Polyphenylene ether grafted 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. - Can be obtained by grafting onto methacrylic acid copolymer, maleic anhydride-modified polypropylene, maleic anhydride-modified polyethylene, maleic anhydride-modified ethylene/vinyl acetate copolymer, etc. In addition, polyphenylene ether grafted polyolefin is obtained by grafting polyphenylene ether to a polyolefin having a glycidyl group in the side chain, such as ethylene/glycidyl methacrylate copolymer, ethylene/vinyl acetate/glycidyl methacrylate copolymer, etc. It can also be obtained by Polystyrene-grafted polyolefins include styrene-based 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, etc. Union,
Styrene/itaconic anhydride copolymer, styrene/itaconic anhydride copolymer,
Asconitic acid anhydride copolymer, styrene/acrylic acid copolymer, styrene/methacrylic acid copolymer, etc., polyolefins having a glycidyl group in the side chain, such as ethylene/glycidyl methacrylate copolymer, ethylene/vinyl acetate/methacrylate It can be obtained by grafting an acid glycidyl copolymer or the like. The amount added is polyphenylene ether or
Based on the composition of polyphenylene ether and styrene resin, and the total amount of polyphenylene ether grafted polyolefin and/or polystyrene grafted polyolefin, the amount of polyphenylene ether grafted polyolefin is 0.1 to 50% by weight, preferably 1 to 50% by weight. 30% by weight, polystyrene-grafted polyolefin in a range of 1 to 80% by weight, preferably 1 to 30% by weight. The grafted polyolefin can be added after graft polymerization in advance, but when using a polyolefin having a glycidyl group, it can be added to a polyphenylene ether or a styrene resin having a carboxylic acid or its anhydride group. The graft reaction can be carried out by kneading at a high temperature of .degree. C. or higher. Therefore, a glycidyl group-containing polyolefin,
By kneading polyphenylene ether or a composition of polyphenylene ether and styrene resin at high temperature, each component is mixed uniformly, and at the same time, the polyphenylene ether produced by the progress of the graft reaction. This is the most preferable method from an economical point of view, since a composition containing a graft polyolefin and/or a polystyrene graft polyolefin can be obtained all at once. (4) Diamide compound The diamide compound used in the present invention is represented by the following formula. R ¹ : A saturated chain hydrocarbon residue or aromatic hydrocarbon residue having a linear or side chain having 11 to 20 carbon atoms, or two aromatic hydrocarbon residues bonded by the following groups. R ² , R ³ : Saturated chain hydrocarbon residue or aromatic hydrocarbon residue having a linear or side chain having 1 to 10 carbon atoms. (R ² and R ³ may be the same or different.) R ¹ is, for example, a dodecamethylene group, a biphenylene group, a diphenylenemethane group, or
A plurality of examples include a methylene group, an ethylene group, a trimethylene group, a propylene group, a tetramethylene group, an isobutylene group, a pentamethylene group, a hexamethylene group, an octamethylene group, a decamethylene group, a phenylene group, a naphthalene group, and the like. Examples of R ² and R ³ include methyl group, ethyl group,
Examples include propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, pentyl group, isopentyl group, hexyl group, isohexyl group, heptyl group, octyl group, decyl group, phenyl group, and naphthyl group. The diamide compound of the present invention is intended to be compatible with the matrix component under the fluid state during molding, and crystallize and phase separate from the matrix component when used. 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 the polyphenylene ether composition is 105-350°C, preferably 200-300°C. Therefore, the diamide compound used in the present invention has a melting point of 105 to 350°C, preferably 150°C to
It is desirable that the temperature be within the range of 300℃. However, when the molding temperature is outside the above range due to the addition of a stabilizer or plasticizer, a diamide compound having a different melting point can be used accordingly. The amount added is 100 parts by weight of all polymers,
0.5 to 20 parts by weight, 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. [] Examples The present invention will be specifically described below with reference to Examples. Example 1 50 parts by weight of poly-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 (manufactured by Mitsubishi Yuka Co., Ltd., several parts by weight) Average molecular weight 50,005
1,000, weight average molecular weight 200,000, microgel content 14.5% by weight) 50 parts by weight, and is represented by the following structural formula. Melt 5 parts by weight of 2,2'-bis(phenylcarbamoyl)biphenyl (manufactured by Yamato Kagaku Co., Ltd., melting point measured with melting point meter MP-1 model: 230°C) at 260°C for 7.5 minutes using a Brabender. Kneaded. After kneading, the melt index (250℃, 10Kg load) indicating moldability (fluidity) was measured, and a specified test piece was made using a press, and the heat distortion temperature was measured (18.6Kg/cm ² loads).
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 Except for using 5 parts by weight of triphenyl phosphate (melting point: 50°C) as a plasticizer in place of 2,2′-bis(phenylcarbamoyl)biphenyl.
Table 1 shows the results obtained in the same manner as in Example 1. As is clear from Table 1, by using 2,2'-bis(phenylcarbamoyl)biphenyl, the fluidity (moldability) is significantly improved and the decrease in heat resistance is suppressed. Although the plasticizer improves the fluidity, the heat resistance is greatly reduced, and the effect of the present invention can be understood.

[Table] Example 2 Example except that 5 parts by weight of 2,4'-bis(phenylcarbamoyl)benzophenone (melting point: 227°C) was used instead of 2,2'-bis(phenylcarbamoyl)biphenyl. Table 2 shows the results obtained in the same manner as in Example 1.

【table】

Claims (1)

[Scope of Claims] 1. Polyphenylene ether or a composition of polyphenylene ether and styrene resin;
It is made by mixing a diamide compound represented by the following formula, and the diamide compound is mixed with 100 parts by weight of the polymer.
A polyphenylene ether composition with improved moldability, characterized in that the amount is 0.5 to 20 parts by weight. R ¹ : Saturated chain hydrocarbon residue or aromatic hydrocarbon residue having a linear or side chain having 11 to 20 carbon atoms, or two aromatic hydrocarbon residues bonded by the following groups: . R ² , R ³ : A linear hydrocarbon residue having 1 to 10 carbon atoms or a saturated chain hydrocarbon residue having a side chain, or an aromatic hydrocarbon residue. (R ² and R ³ may be the same or different)