JPH0721052B2 - Method for producing modified polyphenylene ether resin - Google Patents

Description

BACKGROUND OF THE INVENTION 1. Technical Field The present invention relates to a method for producing a modified polyphenylene ether resin that is well dispersed in both a polyolefin resin and a polyphenylene ether.

Polyphenylene ether has many applications as an extremely useful thermoplastic resin having excellent heat resistance, mechanical properties, electrical properties, acid resistance, alkali resistance, self-extinguishing properties, and the like. However, this resin is expensive for general-purpose use, and has a major drawback that it has a high melt viscosity, poor moldability, and is easily attacked by an organic solvent.

(Prior Art) These drawbacks, particularly for the purpose of lowering the price and improving molding processability, it is possible to blend a polyolefin, or a styrene resin such as polystyrene, rubber-modified polystyrene, or styrene / acrylonitrile / butadiene copolymer. It was held in Japanese Patent Publication No. 42-7069 and Japanese Patent Publication No. 43.
-17812, U.S. Pat. No. 3,383,435 and the like.

However, in the composition consisting of polyphenylene ether and high molecular weight polyolefin, both polymers have poor compatibility with each other, resulting in fragility, mechanical strength,
Impact strength decreases. In order to improve this point, it has been proposed, for example, in Japanese Patent Publication No. Sho 48-39015 to use a low molecular weight crystalline polyolefin instead of a high molecular weight polyolefin, but the polyphenylene ether and the polyolefin are essentially in phase with each other. Since it has no solubility, it is not a fundamental solution to the problem.

On the other hand, there has been proposed a method for improving moldability, impact strength and the like by adding a polyphenylene ether-grafted polyolefin to a composition comprising a polyphenylene ether and a polystyrene resin (JP 58-
7448 publication). In this method, when producing a polyphenylene ether-grafted polyolefin, it is necessary to introduce an epoxy group into either the polyphenylene ether or the polyolefin, but it is presumed that the gel is based on the introduced epoxy group. However, it is not always easy to produce a composition having desired properties with good industrial reproducibility.

In addition, there is a method in which an epoxy resin is blended with polyphenylene ether in order to improve the adhesiveness (Japanese Patent Laid-Open No. Sho 49-49).
-28643), in addition to the above-mentioned drawbacks of having an epoxy group per se, since it is not compatible with the epoxy resin itself or polyolefin, as described above, the compounding of polyolefin does not contribute to any improvement in properties.

SUMMARY OF THE INVENTION (Summary) The present inventors have a good compatibility with both polyphenylene ether and polyolefin resin, can be produced at low cost with good industrial reproducibility, and further, with polyphenylene ether and polyolefin resin. As a result of intensive studies on a compatibilizing agent which can be added to a composition consisting of the above to improve impact strength, the present invention has been accomplished.

That is, the present invention, a polyphenylene ether having an aliphatic alcoholic hydroxyl group bonded, and a polyolefin resin or elastomer modified with maleic anhydride are reacted, and a modified polyphenylene ether resin characterized by the following: It provides a manufacturing method.

(Effect) According to the method of the present invention, a modified polyphenylene ether resin with suppressed gelation can be produced with good reproducibility. Moreover, since the modified polyphenylene ether resin has good compatibility with both the polyphenylene ether resin and the polyolefin resin, when it is blended in a composition composed of the both, a composition with extremely improved dispersion is obtained. Becomes

Therefore, it is possible to obtain a composition having both excellent moldability and solvent resistance of the polyolefin resin, high elastic modulus and dimensional stability of the polyphenylene ether, and high impact strength.

DETAILED DESCRIPTION OF THE INVENTION The polyphenylene ether used in the present invention has the general formula In the formula, one unit of the tetral oxygen atom is connected to the benzene nucleus of the next adjacent unit, n is at least 30, and usually 30 to 1,000, preferably 50. ~ 800, particularly preferably 100-500.

Q is independently hydrogen, halogen, a hydrocarbon group containing no tertiary α-carbon atom, a halohydrocarbon group having at least two carbon atoms between a halogen atom and a phenyl nucleus, a hydrocarbonoxy group and It represents a monovalent substituent selected from the group consisting of halohydrocarbonoxy groups having at least 2 carbon atoms between the halogen atom and the phenyl nucleus. Q
May be the same or different.

Representative examples of polyphenylene ethers include poly (2,6-dimethyl-1,4-phenylene) ether, poly (2,6-diethyl-1,4-phenylene) ether, poly (2-methyl-ether). 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-ether) 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-chloro-1,4-phenylene)
There are ethers, poly (2,5-dibromo-1,4-phenylene) ethers and the like.

Further, a copolymer of 2,6-dimethylphenol and 2,3,6-trimethylphenol, 2,6-dimethylphenol and 2,3,5,6
There may also be mentioned a copolymer of tetramethylphenol and a copolymer of 2,6-diethylphenol and 2,3,6-trimethylphenol.

A particularly preferred polyphenylene ether resin is poly (2,
6-dimethyl-1,4-phenylene) ether.

Further, the polyphenylene ether used in the present invention is
Modified polyphenylene ethers, such as those obtained by crafting styrene monomers (for example, styrene, p-methylstyrene, α-methylstyrene, etc.) into the polyphenylene ethers defined by the above general formula, are also included.

In addition, the range of the preferred molecular weight is 0.15 to 0.
The range is 70 dl / g, and more preferably 0.25 to 0.60 dl.
/ g, particularly preferably 0.40 to 0.60 dl / g.

The polyphenylene ether having an aliphatic alcoholic hydroxyl group bonded thereto can be produced, for example, by reacting a polyphenylene ether with an epoxy compound. The epoxy compound is preferably a compound having one epoxy group in the molecule, and examples thereof include ethylene oxide, propylene oxide, epichlorohydrin, styrene oxide, glycidyl acrylate, glycidyl methacrylate, phenyl glycidyl ether, and cyclohexene oxide. be able to. Of these examples, ethylene oxide and propylene oxide are particularly preferred.

The reaction between polyphenylene ether and epoxy compound is a general formula (M is an integer of about 1 to 20), and an aliphatic alcoholic hydroxyl group can be introduced at the end of the polyphenylene ether. During this reaction, a catalyst such as caustic soda, sodium acetate or tri-n-butylamine can be added to accelerate the reaction. The reaction is usually
It is carried out at a temperature of about room temperature to 200 ° C using a solvent, but when the boiling point of the epoxy compound is high, it is melt-kneaded together with polyphenylene ether at a temperature of 200 ° C or more by a kneader without using a solvent. It is also possible to do this.

Polyolefin resin or elastomer modified with maleic anhydride is one in which maleic anhydride reacts with polyolefin resin or elastomer (hereinafter collectively referred to as polyolefin) and is bonded as a succinic anhydride group or a succinic acid group. (Hereinafter, this polyolefin modified with maleic anhydride is referred to as modified polyolefin).

Examples of the polyolefin used for producing the modified polyolefin include low density polyethylene, medium density polyethylene,
High density polyethylene, ethylene-vinyl acetate copolymer,
Polyethylene resin such as ethylene / methyl acrylate copolymer, polypropylene resin, polybutene-1 resin, poly-4-methylpentene-1 resin, carbon number 2
Polyolefin resins such as unsaturated copolymer resins of 12 α-olefins and non-conjugated dienes, ethylene / propylene copolymer elastomers, ethylene / propylene / diene copolymer elastomers and other polyolefin elastomers, and styrene to these polyolefins. , Α-methylstyrene, p-methylstyrene, acrylic acid ester, methacrylic acid ester, acrylonitrile, and the like, which are block- or graft-polymerized with vinyl monomers. Regarding the method for producing an unsaturated copolymer resin, see JP-A-55-165907, JP-A-56-30413, and JP-A-56-3041.
4, 56-36508, 56-55409, and 59-155416. Among these examples, it is a copolymer of α-olefin having 2 to 12 carbon atoms and 1,4-diene, and the elastic modulus according to JIS K-7203 is 500 to 30,000 kg.
/ cm ² unsaturated copolymer resin and its styrene graft polymer are preferred, particularly preferably α-olefin selected from ethylene and propylene, and 4-methyl-
A copolymer with 1,4-hexadiene and 1,4-hexadiene selected from 5-methyl-1,4-hexadiene, wherein the elastic modulus is 1,000 to 20,000 kg / cm ² is an unsaturated copolymer. It is a styrene graft polymer of a resin.

A method for modifying the polyolefin with maleic anhydride is known, and the polyolefin is usually in the form of a solution or a melt without using a solvent, and is usually about 50 to 300 ° C., preferably 100 to 25.
At a temperature of about 0 ° C, 0.1 minutes to 20 hours, preferably 0.5 minutes to 1
It can be produced by contacting with maleic anhydride for about 0 hour. At this time, if necessary, a catalyst such as a peroxide can be used to accelerate the reaction. The method for producing this modified polyolefin is described in, for example, Japanese Patent Application Laid-Open No. 57-98508. Also,
When the polyolefin in the modified polyolefin is graft-polymerized with styrene or the like, the modification with maleic anhydride may be simultaneous with the graft polymerization of styrene or the like, and the modification with maleic anhydride and the graft polymerization of styrene or the like are performed in two steps. It can also be implemented separately.

The content of maleic anhydride unit in the modified polyolefin is usually 0.1 to 20% by weight, preferably 1 to 10% by weight. 0.1
If it is less than 10% by weight, the reaction with the polyphenylene ether having the aliphatic alcoholic hydroxyl group bonded thereto is difficult to proceed,
If the content exceeds 10% by weight, it is not preferable because the polyolefin may deteriorate or gel during the production of the modified polyolefin.

The modified polyphenylene ether resin which is the object of the present invention can be produced by reacting the above-mentioned polyphenylene ether having an aliphatic alcoholic hydroxyl group bonded with modified polyolefin. The amount ratio of the two is usually 5 for the modified polyolefin based on 100 parts by weight of polyphenylene ether having an aliphatic alcoholic hydroxyl group bonded.
˜1000 parts by weight, preferably 20 to 500 parts by weight, particularly preferably 50 to 200 parts by weight. Less than 5 parts by weight or 1000
If the amount is more than 1 part by weight, the property as a molded product is exhibited only by one of the two components, and when used in the composition described below, the dispersibility of the polyphenylene ether and the polyolefin resin is improved. It is difficult and not preferable.

The reaction between the two may be carried out in the form of a solution, or may be carried out in a molten state using a kneader or the like without using a solvent. The reaction conditions are usually 25 to 400 ° C for 0.1 minutes to 20 hours, preferably 50 to 350 ° C.
It takes about 0.5 minutes to 10 hours. At this time, in order to accelerate the reaction, a catalyst such as sodium acetate, tributylamine, and tertiary amines such as N, N-dimethylaniline can be used. The progress of the reaction can be confirmed by changing the alcoholic hydroxyl group into an ester group by a nuclear magnetic resonance spectrum or an infrared absorption spectrum.

The modified polyphenylene ether resin produced as described above can be used as various molded articles by itself, but as a composition with a polyphenylene ether and / or a polyolefin resin (modified polyphenylene ether resin composition). Available.

This composition contains 0 to 100 parts by weight of polyphenylene ether, preferably 20 to 80 parts by weight of polyphenylene ether resin.
To 100 parts by weight, preferably 20 to 80 parts by weight, and the total amount of polyphenylene ether and polyolefin resin 100
Modified polyphenylene ether resin 1 to 1 part by weight
200 parts by weight, preferably 3 to 100 parts by weight, particularly preferably 5 to 50 parts by weight.

In this composition, the polyphenylene ether and the polyolefin resin can be used those described above, but poly-2,6-dimethyl-1,4-phenylene ether as the polyphenylene ether, as the polyolefin resin. Polyethylene resin and polypropylene resin are preferably used.

As a method for producing this composition, there is also a method of dissolving the components in a solvent and thoroughly mixing them, and then removing the solvent, but preferably various kneaders, for example, a single-screw or twin-screw extruder, a Banbury mixer, a roll. A method of melt-kneading each component using a Brabender Plastograph or the like can be mentioned. The addition method or the order of addition of each component is not particularly limited, and for example, a method of simultaneously mixing all components, a method of first mixing two components and then mixing the remaining components, a first component and a part of the second component, There is a method in which the remaining amount of the second component and the third component are separately mixed and then both the mixtures are mixed.

Incidentally, depending on the practical purpose, styrene resin, elastomer, glass fiber, carbon fiber, reinforcing fiber such as wholly aromatic polyester fiber, carbon, mica, talc, inorganic filler such as titanium oxide, antioxidant, It goes without saying that stabilizers such as heat resistance stabilizers and light stabilizers, flame retardants, coloring pigments and the like can be added.

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

Example-1 (Production of modified polyphenylene ether) In a stainless steel autoclave with an internal volume of 10,
Xylene 5 and 500 g of polyphenylene ether (manufactured by Mitsubishi Petrochemical Co., Ltd., number average degree of polymerization: 100) were charged and the polyphenylene ether was dissolved with stirring. Then ethylene oxide
20 g was injected under pressure and reacted at 150 ° C. for 5 hours. After cooling, the content was poured into methanol 20 to remove the precipitated polymer,
After washing with methanol and drying, 495 g of polyphenylene ether having an aliphatic alcoholic hydroxyl group bonded thereto was obtained.

This is the result of analysis by nuclear magnetic resonance spectrum,
98% of the phenolic hydroxyl groups were converted to aliphatic alcoholic hydroxyl groups.

(Production of Modified Polyolefin) Propylene, ethylene and methylhexadiene (4-
A mixture of methyl-1,4-hexadiene and 5-methyl-1,4-hexadiene) having an ethylene content of 2.9% by weight and a 4-methyl-1,4-hexadiene content of 0.6. Mol%, the content of 5-methyl-1,4-hexadiene was 1.4 mol%, the flexural modulus measured according to JIS-K-7203 was 5,300 kg / cm ² and the measurement according to JIS-K-6758. 100 parts by weight of an unsaturated copolymer resin (made by Mitsubishi Petrochemical Co., Ltd.) having a melt flow rate of 1.6 g / 10 minutes and maleic anhydride 1
0 part by weight was kneaded using a twin-screw extruder at 210 ° C., and molded into pellets having an average particle size of 2 to 3 mm.

Next, in an autoclave with an internal volume of 1.3, 520 g of pure water, 15.6 g of tricalcium phosphate as a suspending agent, and a 1% aqueous solution of sodium dodecylbenzenesulfonate as a suspending agent.
1.56 g was added, and 100 g of the above pellet was added to this and stirred to suspend. In this suspension, as a radical polymerization catalyst, t-
Add a solution of 0.3 g of butyl peroxybenzoate in 100 g of styrene and adjust the temperature in the autoclave with stirring.
The temperature was raised to 90 ° C. and kept at that temperature for 3 hours, then raised to 105 ° C. and kept at this temperature for 1 hour, and further reacted at 125 ° C. for 5 hours.

After cooling to room temperature, the contents were taken out, diluted nitric acid was added until the pH of the aqueous layer became 2.5, and after stirring sufficiently, the product was washed with water and dried at 70 ° C and 1 mmHg for 5 hours to give maleic anhydride. 195 g of maleic anhydride-modified styrene-grafted unsaturated copolymer resin having a unit content of 4.1% by weight was obtained.

This resin is 210% using Brabender Plastograph.
After masticating at 5 ° C. for 5 minutes, it was used in the following experimental examples.

(Production method of modified polyphenylene ether resin) 50 parts by weight of aliphatic alcoholic hydroxyl group-bonded polyphenylene ether obtained as described above, and 100 parts by weight of maleic anhydride-modified styrene graft unsaturated copolymer resin And 2,6-di-t-butyl-4- as stabilizers
A modified polyphenylene ether resin was obtained by melt-kneading with 0.3 part of methylphenol at 280 ° C. for 6 minutes using a Brabender Plastograph.

Analysis of this modified polyphenylene ether resin by nuclear magnetic resonance spectroscopy showed that the aliphatic alcoholic hydroxyl group
It was confirmed that 82% had disappeared and ester bonds had been formed.

When the modified polyphenylene ether resin was extracted with boiling xylene for 7 hours, the extraction residue was 0%,
No gel formation was observed.

Example-2 In a stainless steel autoclave with a content of 10,
Xylene 6, 100 g of polyphenylene ether having an aliphatic alcoholic hydroxyl group bonded thereto obtained in Example-1, 100 g of maleic anhydride-modified polypropylene resin (manufactured by Mitsubishi Yuka, 2.3% by weight of maleic anhydride unit) and tri Butylamine (50 g) was charged, and the mixture was stirred and dissolved at 120 ° C., and further reacted at the same temperature for 10 hours with stirring.

After the reaction, the contents were poured into cold acetone 15 and the precipitated polymer was collected, washed with xylene and then with acetone, and then at 70 ° C for 1 m.
Modified polyphenylene ether resin 178 after drying under reduced pressure at mHg
got g.

When the modified polyphenylene ether resin was analyzed by a nuclear magnetic resonance spectrum, almost no aliphatic alcoholic hydroxyl group was observed and an ester bond was observed. Also,
No gel formation was observed as a result of extraction with boiling xylene.

Comparative Example-1 In place of the polyphenylene ether having an aliphatic alcoholic hydroxyl group bonded thereto, 50 parts by weight of polyphenylene ether (manufactured by Mitsubishi Petrochemical Co., Ltd., number average polymerization degree: 100) was used.
1 was repeated.

When this kneaded material was analyzed by a nuclear magnetic resonance spectrum,
The phenolic hydroxyl groups were almost unreacted.

(Reference Example) 50 parts by weight of polyphenylene ether (the same as that used in Example-1), polypropylene (MA6 manufactured by Mitsubishi Petrochemical Co., Ltd.) 5
0 parts by weight, 20 parts by weight of the modified polyphenylene ether resin obtained in Example-1, 0.2 parts by weight of 2,6-di-t-butyl-4-methylphenol as a stabilizer, and Irganox 1010 (trade name; Ciba Geigy) (Manufactured by Mitsui Chemical Co., Ltd.) was dry blended with a super mixer, and then melt-kneaded at 280 ° C. for 5 minutes using a Brabender Plastograph to obtain a modified polyphenylene ether resin composition.

When this composition was molded into a press sheet having a thickness of 2 mm and the cross section thereof was observed with an electron microscope, polyphenylene ether was found to be in an extremely fine dispersion of 0.2 to 0.8 µ.

Also, the impact strength of this press sheet was measured by the Deinstatt impact test method (BS1330-1946).
It was 1 kg · cm / cm ² .

Claims (1)

[Claims] 1. A process for producing a modified polyphenylene ether resin, which comprises reacting a polyphenylene ether having an aliphatic alcoholic hydroxyl group bonded with a polyolefin resin or elastomer modified with maleic anhydride. .