JPH07116355B2 - Polyphenylene ether resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION 1) Background The present invention comprises an epoxy-modified polyphenylene ether and a polyphenylene ether or a styrene resin-diluted composition thereof, an acid-modified olefin polymer and an olefin polymer composition. Which is excellent in moldability, heat resistance, oil resistance and impact resistance.

Polyphenylene ether is an extremely useful thermoplastic resin that has excellent heat resistance, mechanical properties, water resistance, alkali resistance, self-extinguishing property, etc., and has many applications as an engineering plastics material. It's starting. However, it has a large defect that the melt viscosity is high and the moldability is poor in connection with the high glass transition temperature. Also, the mold releasability during injection molding is poor, the impact resistance of engineering plastics is poor, and the oil resistance is poor, and it cannot be used as a structural component material that comes into contact with gasoline, kerosene, various waxes, lubricating oil, etc. There are problems such as. The present inventors have conducted research to solve such problems within a range that does not significantly impair the excellent properties of polyphenylene ether, and have developed a specific modified polyphenylene ether and a specific modified olefin system. It has been found that the composition containing the polymer composition exhibits a good balance of physical properties.

That is, the present invention provides component (1): polyphenylene ether.
Resin (a) in an amount of 20 to 100% by weight, styrene resin 80 to 0% by weight, component (2): epoxy-modified polyphenylene ether 0.1 to 40% by weight, component (3): olefin The total amount with the polymer component (4) is 30 to 75% by weight
And a component (4): an acid-modified olefin polymer at 0.1 to 60% by weight, which provides a polyphenylene ether composition having improved moldability and oil resistance.

2) Prior Art For the purpose of improving the drawbacks of polyphenylene ether, especially molding processability, it is possible to blend a polyolefin or a styrene-based polymer such as polystyrene, rubber-modified polystyrene, or styrene-acrylonitrile-butadiene copolymer. It has been carried out and is disclosed in Japanese Patent Publication No. 42-7069, Japanese Patent Publication No. 43-17812, and U.S. Pat. No. 3,383,435.

However, styrenic resins have good compatibility with polyphenylene ether, and the blends of both have been widely put to practical use, but since both components have poor oil resistance, the resulting blends have poor oil resistance. It is sufficient and significant improvement in oil resistance is desired.

In the composition consisting of polyphenylene ether and polyolefin, the effect of improving oil resistance is great, but since the compatibility of both components is poor, the mixed composition has a coarse dispersion structure, and its phase interface is extremely high. Only weak affinity works. As a result, the resulting composition has a reduced impact strength.
In the molded product, a phenomenon in which each component is oriented in the resin flow direction, and a thin film is peeled off at the interface,
Since it is so-called delamination, it cannot be put to practical use. In order to improve this point, it has been proposed to use a low molecular weight crystalline polyolefin instead of the high molecular weight polyolefin (Japanese Patent Publication No. 48-39015), but the polyphenylene ether and the polyolefin are essentially compatible. The fact is that it does not lead to a fundamental problem solution because it does not have the above.

Further, by using the polyphenylene grafted polyolefin obtained by reacting with the modified polyphenylene ether and / or the polyolefin, the compatibility of the polyphenylene ether and the polyolefin is improved, and the polyphenylene ether and the styrene-based polymer are added. It has been proposed by the present inventors in JP-A-58-7448 to improve the molding processability and impact strength of a composition comprising a coalescence. Example 6 of JP-A-58-7448 discloses a reaction product composed of glycidylated polyphenylene ether and maleic anhydride-modified polypropylene.
The effect of improving the moldability and impact strength of a composition comprising 10 parts by weight, 50 parts by weight of polyphenylene ether, and 50 parts by weight of polystyrene is shown. However, for use in a wide range of applications, it is still necessary to improve such properties, especially,
Improvements in moldability and oil resistance are desired.

As a result of further research for the purpose, the present inventors have found that an appropriate amount of an olefin polymer having an unmodified propylene chain, an epoxy-modified polyphenylene ether, and an acid-modified olefin resin are used as a polyphenylene resin. It was found that the composition in which the olefin polymer formed a continuous phase was blended with ether and showed a suitable physical property balance,
The present invention was accomplished.

3) Detailed Description of the Invention The polyphenylene ether used as the component (a) in the present invention has the general formula (Wherein R _{1 to} R ₅ are selected from hydrogen, halogenated hydrocarbon, hydrocarbon group or substituted hydrocarbon group), and one or more of phenol compounds represented by oxidative coupling polymerization It is united.

Preferred as the phenol compound are 2,6-dimethylphenol, 2,6-diphenylphenol and 2,3,6.
-Trimethylphenol, 2,6-isopropylphenol, 2-methyl-6-isopropylphenol, 2-methyl-6-t-butylphenol and the like.
Also, cresol, 2,4,6-trimethylphenol, etc. can be selected as a small amount of the copolymerization component. It is also preferable that some of these constituent components are oxidized or modified by a catalytic species during the polymerization reaction. Further, a graft polymer in which a small amount of a styrene polymer or another polymer is bonded to polyphenylene ether can be used.

In the present invention, the styrene resin used for mixing with the polyphenylene ether is one or more selected from styrene derivatives, specifically styrene, p-methylstyrene, α-methylstyrene, and the like. Is a polymer or copolymer containing 25% by weight or more of the polymerized units. Specific examples include polystyrene, poly-α-methylstyrene, poly-p-methylstyrene, styrene-α-methylstyrene copolymer, styrene-maleic anhydride copolymer, styrene-acrylic acid copolymer, styrene-methyl. Methacrylate copolymer, styrene-glycidylmethacrylate copolymer, styrene-butadiene random copolymer and hydrogenated product of 70% or more of its diene component, styrene-butadiene block copolymer and 70% or more of its diene component Hydrogenated products, styrene-isoprene block copolymers and hydrogenated products containing 70% or more of the diene component thereof. Further, rubber-reinforced compositions of these polymers, specifically ABS resin and high-impact polystyrene, can also be used as the styrene resin in the present invention.

The ratio of the styrene resin to the total amount of the polyphenylene ether and the styrene resin is 0 to 80% by weight, preferably 0.
-60% by weight, most preferably 0-40% by weight. When the proportion of the styrene-based resin is increased, the moldability is improved, but the heat resistance characteristic of polyphenylene ether is lowered.

The epoxy-modified polyphenylene ether referred to in the present invention is one in which an epoxy group is introduced into a polyphenylene ether molecule by a chemical reaction, and the concentration of the epoxy group is 1 × 10 per 100 g of polyphenylene ether. ^-4 mol-1
It is in the range of × 10 ^-1 mol.

The concentration of the epoxy group can be determined by infrared analysis method or NMR analysis method. It is also possible to adopt the titration method used for epoxy resins.

The method of introducing an epoxy group into polyphenylene ether includes a reaction utilizing a phenolic hydroxyl group of polyphenylene ether, specifically, an addition reaction of epichlorohydrin, 2,2-bis (4-glycidylphenyl ether) propane. , Addition reaction of epoxy resin and the like can be used. It is also possible to introduce glycidyl methacrylate, monoglycidyl malate or the like by radical reaction using the alkyl side chain.

The ratio of epoxy modified polyphenylene ether is 0.1-40
% By weight, preferably 1 to 30% by weight, more preferably 2
~ 20% by weight. When the proportion of the epoxy modified product increases, the fluidity and mechanical strength of the final product decrease. It is presumed that the formation of a gel body was the cause. On the other hand, if the proportion is too small, the effect of improving dispersibility will not be exhibited, and preferable properties will not be obtained.

Suitable examples of the olefin polymer used in the present invention include:
Examples thereof include polypropylene and propylene-ethylene copolymer.

From the viewpoint of moldability and heat resistance, 30% by weight of a crystalline component having a crystalline propylene chain and a melting point of 120 ° C or higher.
It is also possible to use a mixed composition comprising a propylene-based polymer and another olefin-based polymer as long as the above-mentioned olefin-based polymer is used and the condition is satisfied.

The acid-modified olefin polymer referred to in the present invention is an olefin polymer or copolymer, and a modifier selected from a carboxylic acid or an acid anhydride is mainly formed by radical addition reaction or copolymerization reaction. It is introduced into a chain, a side chain or a molecular end. Specific examples thereof include maleic anhydride in the presence of a peroxide, a product obtained by reacting with polypropylene in a molten state or a solution state, and maleic anhydride instead of itaconic anhydride, acrylic acid, and methacrylic acid. The same modified product, a radical copolymer of ethylene and acrylic acid or methacrylic acid, etc. may be mentioned.

As described above, from the viewpoint of heat resistance and moldability, it is preferable to use an olefin polymer having a crystalline propylene unit as the olefin polymer, and in this case, the acid-modified olefin polymer is also used. Further, those composed of 30% by weight or more of a propylene monomer have good affinity with the olefin polymer and are preferable. The most preferable one is a propylene monomer content of 50% by weight or more, and crystallinity is recognized by differential thermal analysis or the like.

The content (modification degree) of the modifier is 0.01 to 40% by weight, preferably 0.1 to 40% by weight, and more preferably 0.5 to 20% by weight. As the degree of modification increases, the modified polymer itself agglomerates, and the effect of improving the dispersibility of the polyphenylene ether component and the olefin compound in the final composition decreases.

The proportion of the acid-modified olefin polymer is 0.1 to 60% by weight, preferably 1 to 50% by weight, more preferably 2 to 30% by weight.
Is. When the proportion of the acid-modified product increases, the fluidity and mechanical strength of the final composition decrease.

When all the components are melt-mixed at the same time, if the olefin resin component (the total amount of the component (3) and the component (4)) is 30% by weight or more, even if the amount of the olefin resin is unexpectedly less than half, the olefin resin The resin component forms a continuous phase, and as a result, the oil resistance improving effect is exhibited more and more.

The olefin resin component is in the range of 30 to 75% by weight, more preferably 50 to 70% by weight.

Further, as the proportion of the olefin resin component increases, the moldability improves, but at the same time, the heat resistance decreases, so the proportion of the olefin resin component is selected from the range of the above proportions according to the purpose. it can.

Further, if necessary, an elastomer component can be blended for the purpose of reinforcing the impact strength of the final composition. The amount of elastomer added is 0 based on 100 parts by weight of the final composition.
-40 parts by weight is preferred.

When the amount of the elastomer component exceeds 40 parts, the high temperature elastic modulus of the composition is lowered and the properties of the polyphenylene ether composition are lost. Specific examples of the elastomer include ethylene propylene copolymer, ethylene propylene diene terpolymer, ethylene butene copolymer, and other olefin elastomers, polybutadiene, polyisoprene, diene elastomers such as natural rubber, and styrene butadiene rubber. Examples thereof include diene-based copolymer elastomers such as styrene-butadiene block copolymers and styrene-isoprene-block copolymers, and hydrogenated diene-based copolymer elastomers in which 70% or more of the diene component is hydrogenated.

Examples will be given below to illustrate the present invention. The present invention is not limited in its scope by the examples. Depending on the practical purpose, glass fiber, inorganic filler,
Stabilizers, flame retardants, coloring agents and the like may be added.

4) Examples Hereinafter, the method for producing the modified polyphenylene ether and the modified olefin polymer used in the present invention will be illustrated as (Reference Example).

(Reference Example-1) Production of epoxy-modified polyphenylene ether (modified polyphenylene ether A) 10 l of epichlorohydrin was placed in a stainless steel autoclave having an internal volume of 30 l, and then poly-2,6-dimethyl-1,
300 g of 4-phenylene ether polymer powder (manufactured by Mitsubishi Petrochemical Co., Ltd., intrinsic viscosity in chloroform at 30 ° C. is 0.48 dl / g) is added. Then, while heating and heating from an external jacket and stirring, keep the polymer at 100 ° C for about 30 minutes to completely dissolve the polymer, add 50cc of 40% caustic soda aqueous solution, and react at 100 ° C for 3 hours under reflux dehydration under nitrogen atmosphere. Let After completion of the reaction, epichlorohydrin is distilled off under reduced pressure, and the obtained polymer is dissolved in 5 l of chloroform. After removing the solids (produced NaCl and excess NaOH) suspended in the polymer solution by filtration, a mixed solvent of methanol / water (50/50) was added to reprecipitate the polymer, and 10 l of the same solvent were used 3 times. After washing, it was dried at 100 ° C. for about 10 hours to obtain glycidylated polyphenylene ether. The polymer obtained by this operation was titrated by the perchloric acid-CTA · B method, and as a result, polymer 100 was obtained.
The amount of glycidyl groups contained in g was 4 × 10 ⁻³ mol.

From the polystyrene-reduced number average molecular weight of 20200 determined by the SEC method, it was confirmed that each molecule had one glycidyl group.

It is clear that the following reaction proceeded almost quantitatively.

Reference Example-2 Production of Epoxy-Modified Polyphenylene Ether (Modified Polyphenylene Ether B) Poly-2,6-dimethyl-phenylene ether polymer powder (Mitsubishi Oil Chemical's chloroform has an intrinsic viscosity of 0.48 dl at 30 ° C.). / g)
A solution prepared by dissolving 2 g of an epoxy resin (Epicoat 1002 made by Yuka Shell Epoxy 1002) in 10 ml of chloroform was uniformly mixed with 100 g, and kneaded at 280 ° C for 5 minutes with a Brabender Plastograph (Toyo Seiki) . Regarding the obtained composition, the method of E. Shchori et al. (Journal of Applied Polymer Science, Polymer Symposium 34
Vol., Page 103), the amount of phenolic end groups was measured by spectrophotometry, and it was reduced to about 1/2. It is considered that a part of the added epoxy resin undergoes an addition reaction as follows.

(Reference Example-3) Production of Maleic Anhydride Modified Polypropylene (Modified Polyolefin-A) Polypropylene Resin (Mitsubishi Noblene MA8 manufactured by Mitsubishi Yuka) 1
00 parts by weight and 3 parts by weight of maleic anhydride were dry blended with a super mixer. 0.2 parts by weight of t-butyl peroxypivalate was added to these and kneaded with a twin-screw extruder manufactured by Ikegai Tekko KK. The content of maleic anhydride residue after extraction of the obtained composition with acetone was 1.3% by weight.

(Reference Example-4) Production of Maleic Anhydride Modified Ethylene Propylene Copolymer (Modified Polyolefin-B) A polypropylene resin was used as an ethylene-propylene copolymer (EP-07 manufactured by Japan Synthetic Rubber Co., Ltd., propylene content 75%).
A modified polyolefin was obtained in the same manner as in Reference Example 3 except for the above.

(Examples 1 to 3) A composition having a predetermined mixing ratio was kneaded at 280 ° C for 5 minutes with a Prabender Plastograph (manufactured by Toyo Seiki) to obtain a final composition. A test piece having a thickness of 2 mm was prepared by press molding and used for physical property evaluation. The moldability was evaluated as a melt flow index by the outflow weight under the conditions of 290 ° C., 5 kg load and 10 minutes with a melt indexer conforming to JIS-K7210-1975. The oil resistance is the minimum strain of the stress cracking part when immersed in a 9: 1 mixed solvent of heptane and toluene for 3 minutes using Bergen's 1/4 elliptical jig (SPJ Journal, 1962, p. 667). Evaluated. Also, the impact strength is determined by the Dinstatt impact strength test method (BS-13
30-1946).

The results are shown in (Table-1).

The effect of adding an epoxy-modified polyphenylene ether and an acid-modified olefin polymer is shown.

(Examples 4 to 6) Table 2 shows the results of mixing in the proportions shown in Table-2.

It was clearly observed that the molding processability was improved when the acid-modified olefin polymer and the unmodified olefin polymer were used together.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Internal reference number FI Technical indication location C08L 23/26 LDA 63/00 (56) References JP-A-60-258253 (JP, A) Special features Kai 62-257953 (JP, A) Special Table 63-503392 (JP, A) Special Table 63-503388 (JP, A)

Claims (1)

[Claims] 1. A polyphenylene ether resin composition comprising the following components (1) to (4), wherein an olefin polymer forms a continuous phase, which has improved moldability and oil resistance. object. (1) Polyphenylene ether 20 to 100% by weight, styrene resin 80 to 0% by weight resin (a), 10 to 69% by weight (2) Polyphenylene ether modified with a compound having an epoxy group A modified polyphenylene ether having an amount of bound epoxy groups per 100 grams in the range of 1 × 10 ^-4 mol to 1 × 10 ^-1 mol, 0.1 to 40% by weight (3) having a crystalline propylene chain. And an olefin polymer containing 30% by weight or more of a crystalline component having a melting point of 120 ° C. or more, an amount such that the total amount of the component (4) and the component (4) is 30 to 75% by weight. An acid-modified olefin polymer having a modifier content of 0.01 to 40% by weight, which is a resin modified with a modifier selected from acids or carboxylic anhydrides, and 0.1 to 60% by weight.