JPS6155140A - Polyphenylene ether composition - Google Patents

Abstract

PURPOSE:The titled polyphenylene ether composition having high heat resistance and improved moldability, comprising a polyphenylene ether resin and a p-methylstyrene/maleic anhydride copolymer. CONSTITUTION:A polyphenylene ether composition comprising 70-20wt% polyphenylene ether resin of the formula (wherein R<1> and R<2> are the same or different and each represents a 1-6C alkyl, 6-8C aryl, a halogen or hydrogen and n is 50-400), e.g., poly(2,6-dimethyl-1,4-phenylene)ether and 30-80wt% copolymer comprising p-methylstyrene (with a p-isomer content >=about 80%) with maleic anhydride in a ratio of 60-99:40-1wt% (weight-average MW of about 1,000- about 1,000,000 and MW distribution of about 1.5-4.0).

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a polyphenylene ether composition, and more particularly to a composition comprising a polyphenylene ether resin and a P-methylstyrene copolymer.

Conventional technology Polyphenylene ether resin has mechanical properties.

Although it is a polymer with excellent heat resistance, it has the disadvantage of poor moldability. In order to compensate for this drawback, compositions containing various styrenic polymers are known.

Examples: Eva, a composition in which polyphenylene ether resin is blended with polystyrene or rubber-modified polystyrene (Japanese Patent Publication No. 4!l-17812, Japanese Unexamined Patent Application Publication No. 49-98858), polyphenylene ether resin and substantially styrene A composition comprising a copolymer of a vinyl aromatic compound which is , a composition consisting of a vinyl aromatic compound which is essentially styrene and an α,β-unsaturated dicarboxylic acid anhydride which is essentially maleic anhydride (JP-A-58-4)
No. 2648) and the like have been proposed.

Although the above proposal improves the moldability of polyphenylene ether resin to some extent, it is not satisfactory, and there is also the problem that the heat resistance, which is a feature of polyphenylene ether resin, is significantly reduced.

An object of the present invention is to improve moldability of polyphenylene ether resin while minimizing deterioration in heat resistance.

SUMMARY OF THE INVENTION As a result of intensive studies to achieve the object of the present invention, the present inventors have discovered that, in place of the above-mentioned copolymer of styrene and maleic anhydride, P-methylstyrene and maleic anhydride are used. The present invention was completed based on the discovery that a polyphenylene ether resin composition containing a copolymer of the above surprisingly has high heat resistance and greatly improved moldability.

That is, the present invention uses polyphenylene ether resin 70~
20% by weight and 30 to 80% by weight of a copolymer of P-methylstyrene and maleic anhydride.

Composition component (1) Polyphenylene ether resin Polyphenylene ether resin (hereinafter referred to as PPQ) used in the present invention
) is expressed by the following general formula.

[However, R* and R1 are the same or different alkyl groups having 1 to 6 carbon atoms, aryl groups having 6 to 8 carbon atoms, halogen atoms or hydrogen atoms, and n is a number of 50 to 400. ] As a specific example of PPQ, poly(2,6-cymethyl-1
．． 4-phenylene) ether, poly(2,6-dinityl-1,4-)unisine) ether, poly(2-methyl-
6-ethyl-1,4-phenylene)ether, poly(2
-Methyl-6-itsuprobyl-1,4-)unisine) ether, poly(2-methyl-1,4-phenylene) ether, poly(2,6-dichrome-1,4-)unisine)
Ether, poly(2-ethyl-6-promu-1.4-
) unishin) ether, yt'1J (2-phenyl-1
, 4-722lene) ether, and the like.

It is also possible to use these PPQs mixed with polystyrene or rubber-modified polystyrene up to about 30X by weight. Rubber-modified polystyrene is obtained by emulsion polymerization of styrene in the presence of a rubbery polymer. Examples of the rubbery polymer include polybutadiene, butadiene-styrene copolymer, and the like. The proportion of rubbery polymer in the rubber-modified polystyrene is usually up to 20% by weight.

(2) Copolymer of P-methylstyrene and maleic anhydride The copolymer of P-methylstyrene and maleic anhydride (hereinafter referred to as PMEIM) used in the present invention has a para position of at least 80X. , preferably 90% or more, more preferably 95% or more, of P-methylstyrene and maleic anhydride, and the proportion of P-methylstyrene and maleic anhydride in the copolymer is less than P-methylstyrene and maleic anhydride. 60-9
9% by weight, preferably 80-95% by weight, maleic anhydride 40-1% by weight, preferably 20-5% by weight.

PMSM has a weight average molecular weight (UW) of about 1.
The molecular weight distribution (fly/n) is 1.5 to 4.0.

Such PMEIM can be obtained by mixing and stirring P-methylstyrene and maleic anhydride under heating, but in order to obtain a copolymer with hydrophilic properties, radicals can be prepared in a solvent such as a hydrocarbon or ketone. A method of copolymerization in the presence or absence of a generator is desirable.

Composition The composition of the present invention consists of 070-20% by weight of PP, preferably 60-30% by weight, and 1 x 30-80% by weight of PM8M, preferably 40-70% by weight. If the weight of PPQ is less than 20 weight and the weight of PMSM is less than 30 weight, the object of the present invention cannot be achieved.

The composition of the present invention is based on the above formulation, and when up to 10 parts by weight, preferably 0.1 to 5 parts by weight of acid anhydride is blended with respect to 100 parts by weight of the above formulation, The moldability of the resulting composition is further improved, which is desirable. Examples of the acid anhydride include succinic anhydride, benzoic anhydride, maleic anhydride, and the like.

The composition of the present invention is obtained by mixing PPQ, PMEIM, and an optional ingredient acid anhydride in the above-mentioned mixing ratio, and the composition has the ability to evenly disperse the king of both, and has palatable properties. For this purpose, it is desirable to use melt kneading using a mixer such as a Brabender, extruder, Banbury mixer, or mixing roll, or solution kneading using a solvent that can dissolve both or the king.

The compositions of the present invention contain various additives, such as heat stabilizers,
Ultraviolet absorber, nucleating agent, antistatic agent.

Coloring agents, etc. and various fillers, such as inorganic fillers.

It is possible to add a enamel agent and the like. These additives, etc.
They may be mixed during or after preparation of the composition.

Effects of the Invention The composition of the present invention has significantly improved heat resistance and excellent moldability compared to the already proposed composition consisting of PPQ, styrene, maleic anhydride, and copolymer. It shows the effect of In particular, compositions obtained by blending acid anhydrides have a more remarkable effect of improving moldability.

The composition of the present invention exhibits the above-mentioned excellent properties and can be used as a molding material for various industrial products such as automobiles and electrical appliances, and can be easily applied to ordinary plastic molding methods for these molded products. It can be formed into.

Example Hereinafter, the present invention will be explained in detail using examples.

In the examples, X and parts are by weight.

Example 1 Synthesis of PMSM A polymer with a purity of 97. 100 parts of OX's P-methylstyrene (the remainder was OX-methylstyrene) was added and heated to 100'C.

To this, 5 parts of maleic anhydride, 0.2 parts of azobisisobutyronitrile, and 20 parts of methyl ethyl ketone were continuously added over 8 hours with stirring, and copolymerization was carried out while maintaining the temperature at 100°C.

After the addition of maleic anhydride was completed, stirring was continued at the same temperature for an additional 2 hours. Next, 200 parts of methyl ethyl ketone was added and cooled, and the entire solution was poured into 20 times the volume of methanol to separate the polymer. The polymer was dried to have a maleic anhydride moiety of 8X, a weight average molecular weight of 224,000, and a number average molecular weight of 98. OOO(PAW/112n = 2.
PMEIM of 29) was synthesized.

Preparation of Composition 70 parts of PMSM obtained above and po! J (2,6-dimethyl-1.4-)unilene) ether, [manufactured by General Electric Co., intrinsic viscosity = O, aS (chloroform solution, 30°C], glass transition temperature 210°C]! 10 parts, Toyo Seiki Seisakusho ■ At 250℃ in Uboplasto mill
, 100r.

Mixing was conducted for 4 minutes under the conditions of P*Tn* to obtain a composition.

A test piece was molded from the obtained composition using a hot press, and its physical properties were measured using the following test method. The results are shown in Table 1.

M7R (Mel) 70-Vi)) :AEI'rM
])-1238 (230tl:, 2160p load) Flexural modulus: 187M I)-790 Tensile yield strength:
187M D-458 impact strength (tensile impact breaking strength)
: (!uatom 5clentif1cengineeringst
Measured using a M I n 1-Maw tester manufactured by Rumenta Co., Ltd. Heat: , / ) Softening point: A8'rM D-152
5 (5Kf load) Example 1 except that the blending ratio of PM8M and pp□ was changed.
A composition was prepared in the same manner. Their physical properties were measured and shown in Table 1.

Comparative Example 3 The physical properties of PPQ used in Example 1 were measured and shown in Table 1.

Comparative Example 4.5 In place of the PMSM obtained in Example 1, a styrene-maleic anhydride copolymer (manufactured by Sekisui Co., Ltd., Mayler Coup 23) was used.
2. To f8 containing maleic anhydride.

ivy 222. A composition was prepared in the same manner as in Example 1 or Example 2, except that Goo (EIMA) was used.

The physical properties of these compositions were measured and shown in Table 1. Example 5 Maleic anhydride moiety 15X,
MY 99,000, Mn 59. QQQ PMSM was synthesized.

A composition was prepared in the same manner as in Example 1, except that this PMSM was used, and its physical properties are shown in Table 1. Example 6.7 Rubber-modified polystyrene (butadiene) was used in place of PPQ used in Example 1. PPQ (manufactured by General Electric Company, PPO53) containing approximately 2 ON
A composition was prepared in the same manner as in Example 1, except that the mixture ratio of PM8M and PPQ was as shown in Table 2. Their physical properties were measured and shown in Table 2.

A composition was prepared in the same manner as in Example 6 or 7, except that 8MA used in Comparative Example 4 was used in place of PMSM used in Example 6 or 7. Their physical properties were measured and shown in Table 2.

Comparative Example 8 The physical properties of PPQ used in Example 6 were measured and shown in Table 2.

Example Day When preparing the composition in Example 1, a composition was prepared by adding PMSM, 100 parts of PP0, and 1 part of succinic anhydride. The physical properties of the obtained composition were measured and the third
Shown in the table.

Examples 9-11. Comparative Examples 9-10 Example 8 except that the blending ratio of PM8M and PPQ was changed.
A composition was prepared in the same manner. The physical properties of these compositions were measured and shown in Table 3.

Comparative example 11.12

Claims (1)

[Claims] 70-20% by weight of polyphenylene ether resin and P-
Copolymer of methylstyrene and maleic anhydride 30-8
A polyphenylene ether composition consisting of 0% by weight.