JPS63128063A - Polyphenylene ether resin composition - Google Patents

Abstract

PURPOSE:To obtain a resin composition having improved solvent and impact resistance, by blending a composition of a polyphenylene ether and a thermoplastic polyester resin with a specific resin having excellent compatibility with both as well as high impact resistance. CONSTITUTION:A composition obtained by blending (A) 10-80wt% polyphenylene ether having 0.15-0.65, preferably 0.30-0.60 intrinsic viscosity in chloroform as a solvent at 30 deg.C, (B) 10-80wt% thermoplastic polyester resin having >=0.5, preferably >=0.55 intrinsic viscosity in a 1:1 mixed solvent of phenol and tetrachloroethane at 30 deg.C and (C) 80-5wt% resin prepared by adding a vinyl aromatic compound and polymerization initiator, e.g. cyclohexanone peroxide, etc., into an aqueous suspension of a (co)polymer obtained by ring opening (co)polymerization of a norbornene derivative having a polar group in the presence of a metathesis catalyst and carrying out impregnation and polymerization.

Description

Detailed Description of the Invention (I) Background of the Invention The present invention involves blending a resin composition obtained by impregnating and polymerizing a vinyl aromatic compound with a ring-opening polymer of polyphenylene ether, polyester, and a norbornene derivative having a polar group. The present invention relates to a polyphenylene ether resin composition with improved solvent resistance and impact resistance.

Polyphenylene ether has high heat resistance, excellent mechanical strength, electrical properties, and dimensional accuracy, but it is easily attacked by solvents such as aromatic hydrocarbons such as benzene and halogenated hydrocarbons such as trichlene, and is difficult to mold. At present, it is difficult to form a molded body by itself due to its poor properties.

As a method for improving the moldability of polyphenylene ether, a method of diluting it with a polystyrene resin has been proposed. However, although this method improves moldability, the polystyrene resin itself is also attacked by aromatic hydrocarbons such as benzene and halogenated hydrocarbons such as trichloride, so it is resistant even when polystyrene resin is added. Solvent properties cannot be improved.

Adding a polyester resin may be considered to improve moldability and solvent resistance, but even if polyphenylene ether and polyester are mixed, the two will be non-uniformly dispersed9, and mechanical strength resulting in a decrease in

In order to solve this problem, the present inventors added a ring-opened polymer to the composition of polyphenylene ether and polyester, which is a norbornene derivative having a polar group that is highly compatible with both polyphenylene ether and has high moisture absorption properties. Contains vinyl aromatic compounds in the combination! ! Paper making by blending a polymerized resin composition,
Focusing on the fact that uniform fine dispersion of polyphenylene ether and polyester is possible, the present invention was arrived at as a result of intensive studies.

[■] Summary of the Invention The present invention provides a polyphenylene ether resin prepared by blending a resin composition obtained by impregnating and polymerizing a vinyl aromatic compound with a ring-opening polymer of polyphenylene ether, polyester, and a norbornene derivative having a polar group. Regarding the composition.

Such a resin composition can improve the solvent resistance and impact resistance, which were disadvantages of polyphenylene ether, without significantly reducing the heat resistance, strength, electrical properties, etc., which are the characteristics of polyphenylene ether, and achieve the purpose. did.

■Detailed description of the invention Polyphenylene ether The polyphenylene ether used in the present invention is a homopolymer or a copolymer obtained by oxidative polymerization of one or more monocyclic phenols represented by the general formula (1), and Contains a graft copolymer in which a vinyl aromatic compound is grafted onto polyphenylene ether.

General formula (D (wherein, R1-R5 are hydrogen,... rogenated hydrocarbon,
(selected from hydrocarbon groups or substituted hydrocarbon groups) Preferred monocyclic phenol compounds include:
2,6-dimethylphenol, 2,6-diphenylphenol, 2sL6-)'J)'f-ruphenol,
2.6-cyinprovirphenol, 2-methyl-6-
Examples include pyruphenol, 2-methyl-6-t-butylphenol, and the like. Also, cresol, 2.4
．． 6-) Limethylphenol and the like can be selected as a small portion of the copolymerization component. Furthermore, a graft copolymer in which a small amount of a styrene polymer is bonded to polyphenylene ether as a vinyl aromatic compound can also be used.

The polyphenylene ether used in the present invention has an intrinsic viscosity of 0.0001 measured at 30°C using chloroform as a solvent.
A value in the range of 15 to 0.65 is used, and a value in the range of 0.30 to 0.60 is particularly preferred. If the intrinsic viscosity is 0.15, the resulting composition will be brittle and its mechanical strength will decrease, so it is not preferable. In addition, when polyphenylene ether having an intrinsic viscosity exceeding 0.65 is used, the difference in viscosity from the thermoplastic polyester resin is too large, making it impossible to obtain good dispersion, and the object of the present invention cannot be achieved. No.

Thermoplastic polyester The thermoplastic polyester resin used in the present invention has an ester end metal in the main chain of the molecule, and specifically contains a dicarboxylic acid or a derivative thereof, a dihydric alcohol, or a dihydric phenolated metal. polycondensation polyester obtained from dicarboxylic acid or its derivative and a cyclic ether compound, polycondensation polyester obtained from a metal salt of dicarboxylic acid and a dihalogen compound, polyester obtained by ring-opening polymerization of a cyclic ester compound I'm disappointed. Here, it refers to acid anhydrides, esters, and acid chlorides. The dicarboxylic acid may be aliphatic or aromatic, and examples include terephthalic acid, inphthalic acid, phthalic acid, tetraluphthalic acid, oxalic acid, succinic acid, adipic acid, etc., but preferably dicarboxylic acid , aromatic dicarboxylic acids, particularly preferably terephthalic acid, inphthalic acid, or phthalic acid.

Examples of the dihydric alcohol include ethylene glycol, propylene glycol, phytane-1,4-diol, hexamethylene glycol, etc. Preferably, ethylene glycol and phytane-1,4-diol can be mentioned. Examples of the dihydric phenol compound include bisphenol A sorcinol. Examples of the cyclic ether compound include ethylene oxide and propylene oxide.

Moreover, as a cyclic compound, 1-caprolactone etc. can be mentioned. The dihalogen compound to be reacted with the dicarboxylic acid metal salt refers to a compound obtained by replacing two hydroxyl groups of the dihydric alcohol or dihydric phenol compound with halogen atoms such as chlorine or bromine.

The thermoplastic polyester resin used in the resin composition of the present invention is produced by a known method using the above-mentioned raw materials, and its molecular weight is determined by using a 1=1 weight ratio mixture of phenol and tetrachloroethane as a solvent. , those having an intrinsic viscosity measured at 30° C. of 0.50 or more, particularly preferably 0.55 or more are used. Intrinsic viscosity is 0.
If it is less than 50, uniform fine dispersibility is impaired and good mechanical properties cannot be obtained even when melt-kneaded with polyphenylene ether.

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

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

(However, when the polar substituent X is ester, carboxyl, nitrile, amide, /%rogen, Rt R' and Y represent hydrogen or a hydrocarbon group having 1 to 20 carbon atoms, and X is -
(CHz)ncOOR', -(C)h)nOCOR'
, -(CH2)n000M1-(CH2)nCN1-(
CH2)ncO plate 10R1, -(CHz)nZ, in which case n is an integer from 0 to 17, R8-R11 is a hydrocarbon group having 1 to 20 carbon atoms, and M is hydrogen, alkali, or alkaline earth. 2 represents a metal, and 2 represents a halogen. When the polar substituents X and Y are imides and acid anhydrides, R6 and R7 represent hydrogen or a hydrocarbon group having 1 to 20 carbon atoms, and in this case R12 represents a hydrocarbon group having 1 to 20 carbon atoms. ) Norbornene derivatives having these polar substituents can be ring-opening (co)polymerized using a metathesis catalyst described in JP-A-49-77999 and the like.

It is also possible to copolymerize the above norbornene derivative with an olefin that can be copolymerized with these norbornene derivatives.

As these olefins, cyclooctenka is preferable, cyclopentene, cyclooctene, norbornene,
, 5.9-cyclododecatoluene, 1.5-cyclooctadiene, etc. can be used.

The copolymer composition of norbornene derivative and cycloolefin is in a molar ratio of 100:0 to 60:40. Preferably 100
It's 70-30 from 0 to 70. 40% cycloolefin
If it exceeds this, the rigidity of the polymer will decrease and the object of the present invention will not be met.

Among these ring-opening (co)polymers, norbornene derivatives having a carboxylic acid group, 0 to 85%, preferably 0 to 85%,
Particularly preferred are copolymers of norbornene derivatives with carboxylic acid groups and norbornene derivatives with ester groups in the range of 70%.

Tetrahydrofuran of these ring-opened (co)polymers, 30℃
It is necessary to have an intrinsic viscosity of 0.30 to 1.5%, preferably 0.32 to 1.2.

If it is less than 0.30, heat resistance will be poor, and if it exceeds 1.5, flowability after impregnation polymerization will be poor.

As the vinyl aromatic compound referred to in the present invention, for example,
Styrene, nuclear substituted styrene such as methylstyrene, dimethylstyrene, ethylstyrene, isopropylstyrene, chlorstyrene, α-substituted styrene such as α-methylstyrene, α-ethylstyrene and the like.

A copolymerization system in which two or more of these monomers are used in combination can also be used.

Further, the amount of the monomer to be added to form a polymer such as a norbornene polymer is 9 times to 0.25 times by weight. If the amount of the simple compound exceeds 9 times, the impregnation ratio into the norbornene polymer etc. will decrease and a uniform composition will not be obtained, and if the amount is less than 0.25 times, the improvement effect will be small.

As the radical polymerization initiator, an oil-soluble one is used. In addition, the decomposition temperature of the radical polymerization initiator is 90 to 130°C, especially 95°C to obtain a half-life of 10 hours.
A temperature within the range of ~110°C is used.

Specific examples of such polymerization initiators are as follows (the temperature in parentheses indicates that if 0.1 mol of the polymerization initiator is added to benzene lt and left at that temperature for 10 hours, polymerization will start). This is the temperature at which the decomposition rate of the agent is 50%).

Cyclohexanone peroxide (97°C), t-butylperoxybenzony) (104°C), methyl ethyl ketone peroxide (109°C), dicumyl peroxide (117°C), di-1-butyl peroxide (
124°C), 2,5-dimethyl-2,5-cyhenzoylveroxyhexane (100°C), and di-t-butyldiveroxyphthalate (105°C).

The amount of the polymerization initiator used is 0.01 to 0.8 parts by weight, preferably 0.1 to 0.0 parts by weight, per 100 parts by weight of the total amount of monomers added.
．． 5 parts by weight is suitable.

A feature of the present invention is that a polymerization agent and a polymerization initiator are added to an aqueous suspension of a powder or granular material of a norbornene polymer, and after impregnating these into the polymer ligand, The polymerization reaction is initiated and completed by heating.

The preparation of an aqueous suspension is essentially the same as the preparation of an aqueous suspension when carrying out an aqueous suspension polymerization of vinyl aromatic monomers, except for the presence of a norbornene polymer in the system. does not change.

Therefore, the norbornene polymer and preferably the monomer in which the polymerization initiator is predissolved are mixed with a suspending agent used in aqueous suspension polymerization, such as a water-soluble polymer such as polyvinyl alcohol, polyvinylpyrrolidone, methylcellulose, etc. Because vinyl aromatic polymer particles are impregnated into the polymer or adhered to the surface of the polymer and polymerized, it is virtually impossible for vinyl aromatic polymer particles to exist independently from polymer particles such as norbornene polymers in the product. .

Regarding the conditions for impregnation, the higher the heating temperature, the better from the point of view of promoting impregnation, but since the monomer before impregnation will polymerize alone due to premature decomposition of the polymerization initiator, the heating temperature should be set to prevent this from occurring. Lower is better. In the present invention using the above-mentioned specific polymerization initiator and polymer particles, the preferred conditions are a temperature of 75 to
ioo°C, and the stirring time is about 2 to 6 hours.

Note that the amount of free monomer can be determined by the following method. That is, take a sample of an aqueous suspension, quickly filter it using a wire mesh of about 300 mesh to separate it into polymer particles and a liquid phase, measure the monomer in the liquid phase, and calculate this value. The proportion of free monomer is calculated from the amount of monomer and the amount of monomer charged.

The aqueous suspension thus prepared is stirred and dispersed in an aqueous medium in the presence of a single soluble inorganic substance such as calcium phosphate, magnesium oxide, etc., preferably by stirring and heating to a high temperature. The aqueous medium may be one in which various water-soluble substances are dissolved.

The concentration of polymers such as norbornene polymers and monomers in the aqueous suspension is arbitrary as long as the system can be easily stirred, but in general, the concentration of norbornene polymers and vinyl monomers per 100 parts by weight of water. The aromatic monomer is used in an amount of 5 to Zoo0 parts by weight.

This aqueous suspension is heated under conditions that do not substantially cause decomposition of the polymerization initiator used to impregnate the monomer into the polymer particles.

Impregnation, until at least 80% by weight, preferably at least 90% by weight, of the vinyl aromatic monomer is impregnated or adhered to the polymer particles, i.e. 20% by weight, preferably 10% by weight, of the free monomer droplets. The aqueous suspension is preferably left under stirring to an extent of less than % by weight.

Note that less than 20% free vinyl aromatic monomer in the impregnation step is polymerized in the next polymerization step.

The heating should be at a temperature that causes sufficient decomposition of the polymerization initiator used. However, it is preferable not to exceed 150°C. If the temperature exceeds 150° C., intermolecular crosslinking reaction of the polymer occurs, significantly impairing the properties originally possessed by the polymer. - Temperatures of 100 to 130°C are suitable. The temperature during polymerization does not necessarily have to be constant as long as it is 150° C. or lower, and can be changed to two or more stages depending on the properties of the composite resin produced by suspension polymerization.

Polymerization time is generally 5 to 20 hours.

In the present invention, the blending amount of the resin composition obtained by impregnating and polymerizing an open monopolymer of polyphenylene ether, polyester, and a norbornene derivative having a polar group with a vinyl aromatic compound is 10 to 80% by weight of polyphenylene ether, preferably 15 to 75% by weight. , polyester 10-80% by weight
The amount is preferably 15 to 75% by weight, and 80 to 5% by weight, preferably 70 to 8% 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. In 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, good uniform fine dispersion of polyphenylene ether and polyester cannot be obtained unless the amount exceeds 5% by weight. , l1iIt cannot improve the resilience.

Depending on the purpose, the composition of the present invention may further contain antioxidants, ultraviolet absorbers, plasticizers, lubricants, flame retardants, flame retardant aids, antistatic agents, conductivity imparting agents, colorants, and polyfunctional crosslinking agents. , a fibrous reinforcing agent such as glass fiber, and an impact resistance modifier such as rubber.

The method for producing the composition of the present invention is not particularly limited as long as each component is melted and kneaded, and any method may be used. For example, an extruder, a roll mill, a Banbury mixer-1 Brabender, etc. are used.

The crosstalk temperature for obtaining the resin composition in the present invention is 260 to 3
The temperature is 20°C, preferably 270-310°C, particularly preferably 280-300'C. If the temperature is lower than 260°C, polyester is difficult to melt, and if the temperature exceeds 320°C, 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 will deteriorate due to heat and will not have good resistance. Impact resistance cannot be obtained.

An example of manufacturing a resin composition in which a ring-opening polymer of a norbornene derivative having a polar group used in Examples is impregnated with a vinyl aromatic compound will be shown below.

Production Example L: Put 200 parts by volume of water into a flask, then add 0.125 parts by volume of water.
Add tricalcium phosphate for the electric resistance stitching part and 0.35 parts by weight of sodium dodecylbenzenesulfonate, and stir for 5 minutes. Next, 25 parts by volume of styrene was added, and then 75 parts by weight of a ring-opened polymer of carbomethoxynorbornene (polymer) was added.
A)) 0.125 parts by weight of benzoyl peroxide and 0.35 parts by weight of perbutyl pivalate are charged, the temperature is raised to 50°C, and the mixture is impregnated for 3 hours. Then at 75℃ for 2 hours and at 90℃ for 3 hours.
After polymerizing for a period of time and completing the reaction, the polymerization system is cooled,
Filter. The filtered polymer was washed with water, filtered again, and then dried under reduced pressure at 60° C. for 8 hours to obtain polymer (2).

Production Example 2 In a strange way, the ring-opening polymer of carbomethoxynorbornene used in Production Example 1 was partially hydrolyzed to yield 60 moles of the portion having a methyl ester group and 40 moles of the portion having a carboxyl group. Polymer ① was obtained in the same manner as in Production Example 1, except that the copolymer was used as a % copolymer.

Production Example: The amount of the ring-opened copolymer, which is a partial hydrolyzate of the carbomethoxy7-norbornene open-term polymer used in Production Example 2, was changed from 75 parts by weight to 50 parts by weight, and the amount of styrene was changed from 25 parts by volume to 50 parts by weight. Polymer Ω was obtained by the same method as in Production Example 2, except that Ω was changed to .

Examples Borifuenylether (manufactured by Mitsubishi Yuka Co., Ltd.) whose intrinsic viscosity measured at 30°C is as shown in Table 1, was prepared using a solution of phenol and tetrachloroethane in a 1:1 weight ratio at 30°C. A thermoplastic polyester (manufactured by Kuraray Co., Ltd.) whose intrinsic viscosity measured by 280℃ for quantitative measurement
The mixture was melted and kneaded for a total of 6 minutes, including 2 minutes of preheating and 4 minutes of kneading. A portion of the obtained blend was sampled and the dispersion state was measured using a scanning electron microscope at a magnification of 2,000 times, and the results are shown in Table 1. In addition, a sheet with a thickness of 3.2 mm was made by press molding, and a test piece was made by cutting, and the Izot impact strength was measured. Further, this test piece was immersed in benzene at room temperature, and the surface condition was observed after 1 hour. The results are shown in Table 1.

Claims (1)

[Claims] A blend of 10-80% by weight of polyphenylene ether, 10-80% by weight of thermoplastic polyester resin, and 80-5% by weight of a resin obtained by impregnating and polymerizing a vinyl aromatic compound with a ring-opening polymer of a norbornene derivative having a polar group. Resin composition with improved solvent resistance and impact resistance