JPH07116356B2 - Polyphenylene ether resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [I] Background of the Invention In the present invention, a ring-opening polymer of a polyphenylene ether and a norbornene derivative having a polar group is blended with a resin composition in which a vinyl aromatic compound is impregnated and polymerized. And a polyphenylene ether resin composition having improved impact resistance.

Polyphenylene ether has high heat resistance and is excellent in strength, electrical characteristics, and dimensional characteristics, but since it is poor in moldability, it does not easily become a molded product by itself and has low impact resistance.

As a method for improving the moldability of polyphenylene ether, a method of diluting with a polystyrene resin has been proposed. Although this method improves the moldability, the impact resistance itself can hardly be improved. When rubber containing styrene is compounded, the impact resistance is certainly improved, but the rigidity is lowered.

In order to improve the moldability of polyphenylene ether and improve the impact resistance without lowering the rigidity, it is considered to add a ring-opening polymer of a norbornene derivative having a polar group. Even when the ether and the ring-opening polymer of the norbornene derivative having a polar group are mixed, both are non-uniformly dispersed and the impact resistance is not improved.

In order to solve such a problem, the present inventors impregnated a ring-opening polymer of a norbornene derivative having a polar group with a vinyl aromatic compound having good compatibility with polyphenylene ether, and obtained a resin The present invention has been achieved as a result of intensive studies, paying attention to the fact that if the composition and polyphenylene ether are blended, both can be finely dispersed uniformly.

[II] Outline of the Invention The present invention is a ring-opening polymer 1 of a polyphenylene ether of 10 to 97% by weight and a norbornene derivative having a polar group and an intrinsic viscosity of 0.30 to 1.5 at 30 ° C. in tetrahydrofuran.
The present invention relates to a resin composition having improved impact resistance in which 90 to 3% by weight of a resin composition obtained by impregnating and polymerizing 9 to 0.25 parts by weight of a vinyl aromatic compound is added.

Such a resin composition has improved the impact resistance and moldability of polyphenylene ether without lowering the heat resistance, rigidity, electrical characteristics, etc., which are the characteristics of polyphenylene ether, and has achieved the object.

[III] Detailed Description of the Invention Polyphenylene ether The polyphenylene ether used in the present invention is a single or copolymerized polyphenylene ether obtained by oxidative polymerization of one or more monocyclic phenols represented by the general formula (I). It is a coalesced product and includes a fluff copolymer in which a vinyl aromatic compound is grafted onto a polyphenylene ether skeleton.

General formula (I) (In the formula, R ^{1 to} R ⁵ are selected from hydrogen, halogenated hydrocarbons, hydrocarbon groups or substituted hydrocarbon groups) As a preferable monocyclic phenol compound,
2,6-dimethylphenol, 2,6-diphenylphenol, 2,3,6-trimethylphenol, 2,6-diisopropylphenol, 2-methyl-6-isopropylphenol, 2-methyl-6-butylphenol, etc. can give. Also, cresol, 2,4,6-trimethylphenol and the like can be selected as a small amount of the copolymerization component. Further, a graft copolymer in which a small amount of a styrene polymer as a vinyl aromatic compound is bonded to polyphenylene ether can also be used.

The polyphenylene ether used in the present invention has an intrinsic viscosity of 0.15 to 30 measured at 30 ° C. using chloroform as a solvent.
Those in the range of 0.65 are used, and particularly preferably 0.30 to
It is in the range of 0.60. Those having an intrinsic viscosity of less than 0.15 are not preferable because the obtained composition is brittle and the mechanical strength is lowered. Further, when using a polyphenylene ether having an intrinsic viscosity of more than 0.65, the viscosity difference from the thermoplastic polyester resin is too large, good dispersion cannot be obtained, and the object of the present invention is reached. I can't.

The resin composition obtained by impregnating and polymerizing a ring-opening polymer of a norbornene derivative having a polar group with a vinyl aromatic compound, which is used in the present invention, is produced by using the method described below.

Polar norbornene ring-opening polymer The norbornene derivative having a polar group used in the present invention includes ester, carboxyl, nitrile, amide,
Norbornene having an imide, a halogen and an acid anhydride is represented by the following general formula.

(However, when the polar substituent X is ester, carboxyl, nitrile, amide, or halogen, R ⁶ , R ⁷ and Y represent hydrogen or a hydrocarbon group having 1 to 20 carbon atoms, and X represents — (CH ₂ ) _n. C
OOR ⁸ ,-(CH ₂ ) _n OCOR ⁹ ,-(CH ₂ ) _n COOM,-(CH ₂ ) _n CN,-
(CH ₂ ) _n CONR ¹⁰ R ¹¹ − (CH ₂ ) _n Z, where n is 0
To R 17, R ^{8 to} R ¹¹ are hydrocarbon groups having 1 to 20 carbon atoms, M is hydrogen or an alkali or alkaline earth metal, and Z is halogen. When the polar substituents X and Y are imide and acid anhydride, R ⁶ and R ⁷ are hydrogen or have 1 carbon atom.
~ 20 hydrocarbon groups, In this case, R ¹² represents a hydrocarbon group having 1 to ¹² carbon atoms. The norbornene derivative having these polar substituents can be ring-opened (co) polymerized by a metathesis catalyst described in JP-A-49-77999.

It is also possible to copolymerize the above norbornene derivative with olefin which is copolymerizable with these norbornene derivatives.

As these olefins, cycloolefin is preferable, and cyclopentene, cyclooctene, norbornene,
1,5,9-Cyclododecatoluene, 1,5-cyclooctadiene and the like can be used.

The copolymer composition of the norbornene derivative and cycloolefin is in a molar ratio of 100: 0 to 60:40, preferably 100: 0 to 70.
It is a pair 30. When the content of cycloolefin exceeds 40%, the rigidity of the polymer is lowered, which is not suitable for the purpose of the present invention.

Among these ring-opening (co) polymers, the norbornene derivative having a carboxylic acid group is 0 to 85%, preferably 0 to 70%.
A copolymer of a norbornene derivative having a carboxylic acid group in the range of% and a norbornene derivative having an ester group is particularly preferable.

The intrinsic viscosity of these ring-opening (co) polymers at 30 ° C. in tetrahydrofuran is 0.30 to 1.5, particularly preferably 0.32 to
It is necessary to have 1.2. If it is less than 0.30, the heat resistance is poor, and if it exceeds 1.5, the flowability after impregnation polymerization is poor.

Impregnation Polymerization of Vinyl Aromatic Compound into Polar Norbornene Ring-Opening Polymer As the vinyl aromatic compound referred to in the present invention, for example,
Examples thereof include styrene, nucleus-substituted styrene such as methylstyrene, dimethylstyrene, ethylstyrene, isopropylstyrene, chlorostyrene, α-substituted styrene such as α-methylstyrene, α-ethylstyrene.
Further, a copolymerization system in which two or more kinds of these monomers are used in combination can also be used.

Further, the addition amount of the vinyl aromatic compound monomer to the polymer such as the norbornene polymer is 9 to 0.25 with respect to the norbornene polymer 1 by weight.
When the amount of the monomer exceeds 9 times, the ratio of impregnation into the norbornene-based polymer and the like decreases, and a uniform composition cannot be obtained.

As the radical polymerization initiator, an oil-soluble one is used. The decomposition temperature of the radical polymerization initiator used is such that the temperature for obtaining a half-life of 10 hours is 90 to 130 ° C, particularly 95 to 110 ° C.

Specific examples of such a polymerization initiator are as follows (the temperature in the cutlet is 0.1 mol of the polymerization initiator in benzene 1 and the mixture is left at that temperature for 10 hours to obtain the polymerization initiator). The decomposition rate is 50%).

Cyclohexanone peroxide (97 ° C), t-butylperoxybenzoate (104 ° C), methylethylketone peroxide (109 ° C), dicumyl peroxide (117 ° C), di-t-butylperoxide (124 ° C),
2,5-Dimethyl-2,5-dibenzoylperoxyhexane (100 ° C), di-t-butyl-di-peroxyphthalate (105 ° C).

The amount of the polymerization initiator used is appropriately 0.01 to 0.8 parts by weight, preferably 0.1 to 0.5 parts by weight, per 100 parts by weight of the total amount of the added monomers.

The feature of the present invention is that a polymerizable monomer and a polymerization initiator are added to an aqueous suspension of a powder or granules of a norbornene-based polymer, and the polymer particles are impregnated with these, followed by a rise. It is to start and complete the polymerization reaction by heating.

The preparation of the aqueous suspension is essentially the same as the aqueous suspension preparation when carrying out the aqueous suspension polymerization of vinyl aromatic monomers, except that the norbornene-based polymer is present in the system. does not change.

Accordingly, a norbornene-based polymer and a monomer in which a polymerization initiator is preferably dissolved in advance are used as a suspending agent that can be used in aqueous suspension polymerization, such as a water-soluble polymer such as polyvinyl alcohol, polyvinylpyrrolidone, methylcellulose, or the like. Stir-dispersed in an aqueous medium in the presence of a poorly soluble inorganic substance such as calcium phosphate, magnesium oxide and the like. The aqueous medium may be one in which various water-soluble substances are dissolved.

The concentration of the polymer such as norbornene-based polymer and the monomer in the aqueous suspension is arbitrary as long as the stirring of the system is easily performed, but generally, the norbornene-based polymer and the vinyl aroma are added to 100 parts by weight of water. It is carried out with 5 to 100 parts by weight of the group monomer.

This aqueous suspension is heated under conditions in which the decomposition of the polymerization initiator used does not substantially occur to impregnate the polymer particles with the monomer.

The impregnation is performed until 80% by weight or more, preferably 90% by weight or more of the vinyl aromatic monomer is impregnated or attached to the polymer particles, that is, 20% by weight of free monomer droplets, preferably 10% by weight.
The aqueous suspension is preferably left under agitation to the extent that it is less than wt%.

In the impregnation step, less than 20% by weight of the free vinyl aromatic monomer is impregnated into the polymer in the next polymerization step or adheres to the surface of the polymer to be polymerized. It is virtually unrecognized that the polymer particles exist independently of the polymer particles such as the norbornene-based polymer.

From the viewpoint of promoting impregnation, the heating temperature should be higher for the impregnation conditions, but the monomer before impregnation will polymerize alone due to premature decomposition of the polymerization initiator. The lower the temperature, the better. In the present invention using the above-mentioned specific polymerization initiator and polymer particles, preferable conditions are a temperature of 75 to 10
The stirring time at 0 ° C. is about 2 to 6 hours.

The amount of free monomer can be known by the following method. That is, an arbitrary amount of the aqueous suspension is sampled, this is quickly filtered using a wire mesh of about 300 mesh to separate into polymer particles and a liquid phase, and the monomer in the liquid phase is measured. Then, the ratio of the free monomer is calculated from the charged amount of the monomer.

The aqueous suspension thus prepared is heated, preferably under stirring, to a high temperature to polymerize the monomers.

The heating temperature should be a temperature at which sufficient decomposition of the polymerization initiator used occurs. However, it is preferable not to exceed 150 ° C. If the temperature exceeds 150 ° C, an intermolecular crosslinking reaction of the polymer occurs, and the inherent properties of the polymer are significantly impaired.
Generally, temperatures of 100-130 ° C are suitable. The temperature during the polymerization need not be constant as long as it is 150 ° C. or lower,
It is also possible to change the properties of the composite resin produced by suspension polymerization in two or more steps.

The polymerization time is generally 5 to 20 hours.

The compounding amount of the resin composition in which the vinyl aromatic compound is impregnated and polymerized in the ring-opening polymer of the polyphenylene ether and the polar group-containing norbornene derivative in the present invention is 10 to 97% by weight of the polyphenylene ether, preferably 15 to It is 95% by weight, and 90 to 3% by weight, preferably 85 to 5% by weight, of a resin composition obtained by impregnating and polymerizing a ring-opening polymer of a norbornene derivative having a polar group with a vinyl aromatic compound. A resin composition obtained by impregnating a ring-opening polymer of a norbornene derivative having a polar group with a vinyl aromatic compound and impregnating it with a vinyl aromatic compound in an amount of more than 3% by weight cannot improve the moldability and impact resistance of polyphenylene ether. .

The composition of the present invention further comprises an antioxidant, an ultraviolet absorber, a plasticizer, a lubricant, a flame retardant, a flame retardant aid, an antistatic agent, a conductivity-imparting agent, a colorant, a polyfunctional crosslinking agent, depending on the purpose. Additives such as fibrous reinforcing agents such as glass fiber and impact resistance improving agents such as rubber can be added.

The method for producing the composition of the present invention is not particularly limited as long as each component is melt-kneaded, and may be any method. For example, an extruder, roll mill, Banbury mixer, Brabender, etc. are used.

The kneading temperature for obtaining the resin composition in the present invention is 200 to 320.
℃, preferably 210 ~ 310 ℃, particularly preferably 220 ~ 300 ℃
Is. If the temperature is lower than 200 ° C, the polyphenylene ether is difficult to melt, and if the temperature exceeds 320 ° C, the resin composition obtained by impregnating the ring-opening polymer of the norbornene derivative having a polar group with the vinyl aromatic compound is deteriorated by heat, Good impact resistance cannot be obtained.

The production examples of resin compositions obtained by impregnating and polymerizing a ring-opening polymer of a norbornene derivative having a polar group with a vinyl aromatic compound used in Examples are shown below.

Production Example 1 200 parts by volume of water was placed in a flask, 6 parts by weight of tricalcium phosphate and 0.001 parts by weight of sodium dodecylbenzenesulfonate were placed therein, and the mixture was stirred for 5 minutes. Next, 25 parts by volume of styrene was added, and then 75 parts by weight of a carbomethoxynorbornene ring-opening polymer (30 ° C., an intrinsic viscosity of 0.50 in a tetrahydrofuran solution), 0.125 parts by weight of benzoyl peroxide and 0.35 part by weight of perbutylpiperate. Charge 50
The temperature is raised to ℃ and impregnated for 3 hours. Then at 75 ℃ for 2 hours, 90 ℃
After 3 hours of polymerization to complete the reaction, the polymerization system is cooled and filtered. The filtered polymer was washed with water, filtered again, and dried under reduced pressure at 60 ° C. for 8 hours to obtain a polymer (A).

Production Example 2 Instead of the ring-opening polymer of carbomethoxynorbornene used in Production Example 1, this polymer was partially hydrolyzed, and the portion having a methyl ester group was 60 mol% and the portion having a carboxyl group was 40 mol%. A polymer (B) was obtained in the same manner as in Production Example 1 except that the above copolymer was used.

Production Example 3 The charged amount of the ring-opening copolymer, which is a partial hydrolyzate of the carbomethoxynorbornene ring-opening polymer used in Production Example 2, was adjusted.
By the same procedure as in Production Example 2, except that the amount of styrene was changed from 75 parts by weight to 50 parts by weight and the amount of styrene was changed from 25 parts by weight to 50 parts by weight.
A polymer (C) was obtained.

Example The intrinsic viscosity measured at 30 ° C. with a chloroform solution is shown in the table.
1, polyphenylene ether (manufactured by Mitsubishi Yuka) and the polymer (A) shown in Production Examples 1, 2 and 3.
(B) and (C) at the specified amount in Table-1 at 240 ℃ or 280
The mixture was placed in a Brabender set at 0 ° C., and premixed for 2 minutes and kneaded for 4 minutes, and melted and kneaded for 6 minutes. The results are shown in Table 1. A test piece was prepared from the obtained resin composition by a press molding method, and each test piece was measured based on the following evaluation methods.

Heat distortion temperature JIS K-7207-1974 Izod impact strength JIS K-7110-1971 Three-point bending elastic modulus JIS K-7203-1973

 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Michiharu Kihira 1 Toho-cho, Yokkaichi-shi, Mie Resin Research Laboratory, Mitsubishi Petrochemical Co., Ltd. (72) Inventor Tetsuji Kakizaki 1-ho, Toho-cho, Yokkaichi-shi, Mie (56) References JP-A-52-13548 (JP, A)

Claims (1)

[Claims] 1. A ring-opening polymer containing 10 to 97% by weight of polyphenylene ether and a norbornene derivative having a polar group and an intrinsic viscosity of 0.30 to 1.5 at 30 ° C. in tetrahydrofuran. A resin composition having improved impact resistance, which is obtained by blending 90 to 3% by weight of a resin composition obtained by impregnating and polymerizing 0.25 part by weight.