JPH07316386A - Polyphenylene ether resin composition - Google Patents

Abstract

PURPOSE:To obtain the composition, containing a polyphenylene ether resin and a specific modified block copolymer and excellent in impact, chemical and heat resistances, molding processability, tensile physical properties, etc. CONSTITUTION:This composition contains (A) a polyphenylene ether resin and (B) (i) a modified block copolymer having hydroxyl groups at terminals of a block copolymer containing a polymer block consisting essentially of an aromatic vinyl compound and/or a hydrogenated polybutadiene block prepared by hydrogenating a polybutadiene with <=20% content of 1,2-bonds and a hydrogenated polyisoprene block, a hydrogenated polybutadiene block obtained by hydrogenating a polybutadiene with 30-70% content of the 1,2-bonds and/or a random copolymer block of hydrogenated isoprene and hydrogenated butadiene and/or (ii) a modified block copolymer having hydroxyl groups at the terminals of a block copolymer containing a polymer block consisting essentially of the aromatic vinyl compound and polyisobutylene block.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a polyphenylene ether resin composition having excellent impact resistance and chemical resistance.

[0002]

2. Description of the Related Art In recent years, plastic materials have been generally used as casings, interiors, and exteriors of various equipment such as office equipment, audio equipment, and household electric appliances. Among them, polyphenylene ether (hereinafter sometimes abbreviated as PPE) resin has excellent mechanical properties and is a well-balanced material including creep and stress relaxation. Further, it is characterized by heat resistance, less deterioration of physical properties at low temperatures, and flame retardancy. However, the PPE resin has a problem in terms of moldability and causes internal cracks with the lapse of time. Due to this property, parts made of PPE resin have drawbacks such as insufficient impact strength, brittleness, and poor chemical resistance, and improvements thereof are demanded.

As a measure for improving the impact resistance of PPE resin,
Various improvements have been attempted so far, such as compounding or grafting of polystyrene, compounding of various rubbers, compounding of other resins such as polyolefin.

However, when polystyrene is blended and grafted, various physical properties such as heat resistance are deteriorated as compared with the PPE resin alone. Further, various rubbers and polyolefins and PPE resins are not compatible with each other, so that the mixture formed is inferior in homogeneity. Such mixtures undergo phase separation during molding, which results in delamination of the molded article. Due to such problems, the purpose of improving the impact resistance has not yet been achieved.

[0005]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a resin composition which improves impact resistance and chemical resistance of PPE resin composition without the above drawbacks.

[0006]

The present inventors have arrived at the present invention as a result of extensive studies to solve the above problems. That is, the present invention provides (a) a polyphenylene ether resin,
And (b) at least one block selected from the group consisting of a polymer block mainly containing an aromatic vinyl compound and a hydrogenated polybutadiene block obtained by hydrogenating a polybutadiene having a 1,2-bond content of 20% or less. A
And hydrogenated polyisoprene block, 1,2-
At least one block B selected from the group consisting of hydrogenated polybutadiene blocks obtained by hydrogenating polybutadiene having a bonding amount of 30 to 70% and hydrogenated random copolymer blocks of isoprene and butadiene.
At least one polymer block C mainly composed of a modified block copolymer (b-1) having a hydroxyl group at the terminal of a block copolymer containing and and / or an aromatic vinyl compound, and at least one polyblock. The present invention relates to a resin composition characterized by containing a modified block copolymer (b-2) having a hydroxyl group at the terminal of a block copolymer containing isobutylene block D.

The present invention will be described in detail below.

The PPE resin used as the component (a) in the resin composition of the present invention includes the PPE resin itself, a blend of PPE with polystyrene, high-impact polystyrene or the like for improving processability, or PPE resin. There are modified PPE resins such as those obtained by grafting polystyrene. These PPE resin and modified PPE resin can be manufactured by a conventionally known method, and the manufacturing method and the like are not particularly limited. The molecular weight, intrinsic viscosity, etc. of the PPE resin and the modified PPE resin may be within the usual range.

The modified block copolymer (b-1) which is another component in the present invention can be produced by an anionic polymerization method, and the modified block copolymer (b-2)
Can be produced by a cationic polymerization method.

Examples of the modified block copolymer (b-1) include those represented by the following formulas.

(AB) k-OH (BA) l-OH A- (BA) m-OH B- (AB) n-OH (In each formula, A is a polymer block A) And B represents the polymer block B, and k, l, m and n are each 1
It represents the above integer, and OH represents a hydroxyl group. ) The repeating numbers k, 1, m and n of the polymer block A and the polymer block B in the modified block copolymer (b-1) can be arbitrarily determined, but are usually preferably 5 or less. The modified block copolymer (b-1) used may be only one kind or two or more kinds.

As the aromatic vinyl compound constituting the polymer block A, styrene, α-methylstyrene, 3-
One or more kinds are selected from methylstyrene, 4-propylstyrene, 1-vinylnaphthalene, 2-vinylnaphthalene and the like, and styrene is particularly preferable.

The modified block copolymer (b-1)
Can be obtained by obtaining a living polymer by anionic living polymerization using an ordinary organic alkali metal catalyst, adding a hydroxyl group to the terminal, and then hydrogenating. For example, formula (AB ′) k or formula A- (B′-A) m (wherein A, k and m are as defined above, B ′
Represents a hydrogenated polyisoprene block. )
The hydrogenated precursor of the binary block copolymer among the block copolymers represented by is a saturated aliphatic carbonization such as hexane, heptane, cyclohexane using n-butyllithium, s-butyllithium or the like as a polymerization initiator. A living polymer is obtained by anionically polymerizing an aromatic vinyl compound monomer or a butadiene monomer under a temperature condition of 30 to 60 ° C. using a hydrogen compound or an aromatic hydrocarbon compound such as benzene or toluene as a solvent. It can be produced by obtaining and subsequently anionically polymerizing an isoprene monomer. In the production of such a binary block copolymer, a ternary block copolymer can be produced by subsequently anionically polymerizing an aromatic vinyl monomer or a butadiene monomer, and by repeating this polymerization operation, It is possible to produce block copolymers of original size or better.

(B'-A) l or B '-(AB')
Water of a binary block copolymer among the block copolymers represented by n (wherein A, l and n are as defined above and B ′ represents a hydrogenated polyisoprene block). The addition precursor can be produced by anionically polymerizing an isoprene monomer to obtain a living polymer, and subsequently anionically polymerizing an aromatic vinyl monomer or a butadiene monomer. Take 2
In the production of the original block copolymer, a ternary block copolymer can be produced by subsequently anionically polymerizing the isoprene monomer, and further, this polymerization operation is repeated to produce a quaternary block copolymer or more. can do.

In the production of the above block copolymer, a random copolymer block of isoprene and butadiene can be introduced by subjecting a mixed solution of a butadiene monomer and an isoprene monomer to anionic polymerization. In addition, a polybutadiene block having a 1,2-bond content of 30 to 70% can be introduced by anionically polymerizing a butadiene monomer in the presence of an appropriate amount of dioxane or tetrahydrofuran. Similarly, by subjecting the isoprene monomer to anionic polymerization in the presence of an appropriate amount of dioxane or tetrahydrofuran, 3,4-
A polyisoprene block having a bonding amount of 30 to 70% can be introduced.

When the block copolymer reaches a desired molecular structure and molecular weight, ethylene oxide or propylene oxide is added, and then an active hydrogen compound such as alcohols, carboxylic acids or water is added to terminate the polymerization.

Next, the obtained block copolymer is hydrogenated. As the hydrogenation catalyst, a homogeneous catalyst or a heterogeneous catalyst can be used. When a homogeneous catalyst is used, an organic transition metal catalyst (for example, nickel acetylacetonate, cobalt acetylacetonate, nickel naphthenate, cobalt naphthenate, etc.) and an alkyl compound of a metal such as aluminum, an alkali metal or an alkaline earth metal A Ziegler catalyst or the like in the combination of the above is used in a molar ratio of about 0.01 to 0.1% with respect to the carbon-carbon double bond contained in the block polymer subjected to the hydrogenation reaction. The hydrogenation reaction is usually carried out at room temperature to 150 ° C. and normal pressure to 50 kg / cm ² of hydrogen pressure, and is completed in about 1 to 50 hours. After completion of the reaction, acidic water is added to the reaction vessel and vigorously stirred to dissolve the hydrogenation catalyst in water. The target modified block copolymer (b-1) is obtained by removing the aqueous phase from the two phases that have been phase-separated and further distilling off the solvent.

The modified block copolymer (b-1) used in the present invention is preferably such that 50% or more of the carbon-carbon double bond based on the isoprene monomer or the butadiene monomer is hydrogenated. From the viewpoints of heat deterioration resistance and weather resistance, the hydrogenation rate is more preferably 80% or more.

Examples of the modified block copolymer (b-2) include those represented by the following formulas.

HO- (Y-Z-Y) p-OH HO- (Z-Y-Z) q-OH (wherein Y represents a polymer block C, Z represents a polymer block D, p and q each represent an integer of 1 or more, and OH represents a hydroxyl group.) Examples of the aromatic vinyl compound constituting the polymer block C include styrene, α-methylstyrene, p-methylstyrene and pt-butyl. One kind or two or more kinds are selected from styrene and p-chlorostyrene, and styrene is particularly preferable.

The modified block copolymer (b-2) is obtained by subjecting a living polymer to a living polymer by, for example, cationic living polymerization using ordinary 1,4-di (2-methoxy-2-propyl) benzene and adding a hydroxyl group to the terminal. Obtained by For example, in a solvent of cycloalkane such as cyclohexane or methylcyclohexane, or halogenated alkane such as methyl chloride or methylene chloride, 1,4-di (2-methoxy-2-propyl) benzene and titanium tetrachloride are used as an initiator. A living polymer is obtained by cationically polymerizing an isobutylene monomer under a temperature condition of 10 ° C to -90 ° C.
Subsequently, N, N-dimethylacetamide and 2,6-di-t-butylpyridine were added, and then a styrene-isobutylene-styrene triblock copolymer having a chlorine atom at a terminal was obtained by cationically polymerizing a styrene monomer. Then, the obtained block copolymer is dehydrochlorinated, hydroborated and oxidized to produce a styrene-isobutylene-styrene triblock copolymer having a hydroxyl group at the terminal. By repeating this polymerization operation, a block copolymer having 5 or more units and an odd number of repeating units can be produced.

The hydroxyl group in the modified block copolymer (b-1) and the hydroxyl group in the modified block copolymer (b-2) are the ends of the corresponding polymer block A and polymer block B, and the corresponding polymer block. It may be added to either the terminal of C or the polymer block D, but is preferably added to the terminals of the polymer block A and the polymer block C which are hard blocks, and is added to the terminal of the styrene block. The most preferable one is used. The concentration of such terminal OH groups is preferably 0.5 or more per molecule, and more preferably 0.7 or more.

The number average molecular weight of the polymer block A in the modified block copolymer (b-1) and the number average molecular weight of the polymer block C in the modified block copolymer (b-2) are both in the range of 4,000 to 50,000. Is preferred. The number average molecular weight of the polymer block B in the modified block copolymer (b-1) and the number average molecular weight of the polymer block D in the modified block copolymer (b-2) are both in the range of 10,000 to 100,000. Is preferred. Furthermore, the modified block copolymer (b-1)
Number average molecular weight and modified block copolymer (b-
The number average molecular weight of 2) is preferably in the range of 14,000 to 150,000.

The weight ratio of the polymer block A to the block B in the modified block copolymer (b-1) and the polymer block C in the modified block copolymer (b-2).
The weight ratio of the block D and the block D is not particularly limited, but both are preferably in the range of 1: 9 to 7: 3.

In the PPE resin composition of the present invention, PP
The E resin (a) and the modified block copolymer (b-1) and / or the modified block copolymer (b-2) are the PP
The weight ratio of the E resin / the modified block copolymer is 98.
It is preferably used in a ratio of / 2 to 40/60. P
If the proportion of the PE resin is less than 40% by weight, the excellent mechanical properties, heat resistance and flame retardancy originally possessed by the PPE resin will not be exhibited. If the proportion of the terminal hydroxyl group elastomer is less than 2% by weight, the effect of improving impact resistance cannot be obtained.

The resin composition of the present invention is, if necessary, a thermoplastic resin such as polyethylene, polypropylene, polycarbonate, polyamide, polyacetal, polyetherketone or polyimide, or a thermosetting resin such as epoxy resin or unsaturated polyester resin. Resins, other polymers such as liquid polyisoprene and its carboxylic acid modified products, and reinforcing agents such as glass fiber, silica, mica, talc and carbon black, antioxidants such as fillers, hindered phenols and amines Agent, release agent, colorant, UV absorber,
Various additives such as antistatic agents, crystal nucleating agents and flame retardants can be contained.

The PPE resin composition of the present invention comprises the above-mentioned 2
It can be produced by mixing different kinds of polymers and, if necessary, other additives simultaneously or sequentially and performing melt-kneading by a conventional method. Melt-kneading can be performed using a kneader such as a single-screw extruder, a twin-screw extruder, a kneader or a Banbury mixer. The type of equipment used, melt-kneading conditions and the like are not particularly limited, but are 300 to 350 ° C.
Can be kneaded in about 3 to 15 minutes.

The PPE resin composition of the present invention is produced by injection molding,
Extrusion molding, press molding, blow molding, extrusion blow molding,
It can be molded by any molding method such as calender molding, cast molding, etc., whereby electrical parts, electronic parts,
It is possible to manufacture a molded product of any shape and application such as machine parts, automobile parts, pipes, sheets, films and daily necessities.

[0029]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited thereto. In the following Examples and Comparative Examples, each polymer is shown by an abbreviation, and the specific contents are shown in Tables 1 and 2 below.

[0030]

[Table 1]

[0031]

[Table 2] (Examples 1 to 7, Comparative Examples 1 to 7) The polymers shown in Table 1 were mixed at a weight ratio shown in Tables 3 and 4 below using a Brabender to prepare respective PPE resin compositions. I adjusted things.

Using each PPE resin composition, a test piece was manufactured by a pressing method by the method described below. Tensile elongation was measured using a test piece to determine elasticity, and Izod impact test was used to determine impact resistance by the following method. Manufacture of test pieces and measurement of their tensile properties and impact resistance
Determination : The PPE resin compositions of Examples and Comparative Examples were kneaded with a Brabender at a temperature of 300 ° C to 350 ° C and shredded. Temperature 300 ℃ -350 ℃, Pressing pressure 100kg /
cm2, press-molded to measure the tensile elongation according to JIS K7113, and the temperature is 300 ° C to 350 ° C.
An Izod test piece with a v-notch was molded at a pressing pressure of 100 kg / cm 2, and the impact resistance was measured according to JIS K7110.

As a result, the results shown in Tables 3 and 4 below were obtained.

[0034]

[Table 3]

[0035]

[Table 4] From the results of Tables 3 and 4 described above, it can be seen that a molded product having a larger elongation and strength and a higher Izod impact resistance value than that of the PPE resin can be obtained.

[0036]

When the PPE resin composition of the present invention is used, the impact resistance is improved while maintaining various properties of the PPE resin such as excellent heat resistance, moldability and tensile properties. It is possible to obtain various molded products that are extremely effective in practice.

Claims (2)

[Claims] 1. A hydrogenated polybutadiene obtained by hydrogenating (a) a polyphenylene ether resin, and (b) a polymer block mainly containing an aromatic vinyl compound and polybutadiene having a 1,2-bond content of 20% or less. At least one block A selected from the group consisting of blocks
And hydrogenated polyisoprene block, 1,2-
At least one block B selected from the group consisting of hydrogenated polybutadiene blocks obtained by hydrogenating polybutadiene having a bonding amount of 30 to 70% and hydrogenated random copolymer blocks of isoprene and butadiene.
At least one polymer block C mainly composed of a modified block copolymer (b-1) having a hydroxyl group at the terminal of a block copolymer containing and and / or an aromatic vinyl compound, and at least one polyblock. A resin composition comprising a modified block copolymer (b-2) having a hydroxyl group at a terminal of a block copolymer containing an isobutylene block D. 2. The weight ratio of component (a) and component (b) is (a) / (b) = 98 / 2-40 / 60.
The polyphenylene ether resin composition described in 1.