JPH07258538A - Polyphenylene ether resin composition - Google Patents

Abstract

(57) [Summary] [Structure] Components (a) and (b) containing the following components (a) and (b) and measured in chloroform at 30 ° C.
Intrinsic viscosity [η] _a dl / g and [η] _b dl / g of the polyphenylene ether resin composition satisfying the following formula (1). [Η] _a− [η] _b ≧ 0.05 (1) (a) First polyphenylene ether (b) 2,3,6-substituted obtained by oxidative coupling polymerization of a 2,6-substituted phenol derivative Second polyphenylene ether obtained by oxidative coupling polymerization of phenol derivative [Effect] A polyphenylene ether resin composition having excellent moldability, rigidity, and balance between heat resistance and impact resistance.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyphenylene ether (hereinafter referred to as "PPE") resin composition having an excellent balance between moldability, rigidity, heat resistance and impact resistance. Alternatively, the present invention relates to a PPE resin composition which is a material suitable as a polymer blend with another resin in the fields of automobiles, OA equipment, home appliances, and the like.

[0002]

2. Description of the Related Art Conventionally, PPE obtained by oxidative coupling polymerization of 2,6-dimethylphenol has been widely known as a thermoplastic resin having excellent heat resistance, mechanical properties and electrical properties. However, the above-mentioned PPE has the drawbacks of poor moldability because it has a high melting temperature and poor melt fluidity. In order to improve such a defect, various methods have been carried out, for example, a method of adding another resin to PPE, that is, a method of adding a styrene resin to PPE (US Pat. No. 3,383,435). Or a method of blending PPE with another polymer such as polyamide, polyethylene terephthalate or polybutylene terephthalate (Japanese Patent Publication No. 45-997, Japanese Patent Publication No. 59-159847 or Japanese Patent Publication No. 49-75662). Of 2,2,6-dimethylphenol and 2,3,6-trimethylphenol
No. 11765, etc.), a method of adding a plasticizer, etc.,
Methods for reducing the molecular weight of polymers have been proposed. However, in the method (1), the original properties (especially heat resistance) of the final composition are often impaired, and it is difficult to obtain sufficient moldability in the method (2), and There has been a problem that bleed-out of agents, low molecular weight substances, etc. causes poor appearance and lowers mechanical strength.

[0003]

SUMMARY OF THE INVENTION It is an object of the present invention to solve the above problems and provide a PPE resin composition having excellent moldability, rigidity, and a good balance between heat resistance and impact resistance. .

[0004]

[Means for Solving the Problems] As a result of intensive studies, the inventors of the present invention have found that the first and second PPE on the high molecular weight side obtained by oxidative coupling polymerization of a 2,6-substituted phenol derivative and 2 Second P on the low molecular weight side obtained by oxidative coupling polymerization of a 3,3,6-substituted phenol derivative
P composed of a blend with PE and having a difference in intrinsic viscosity between the high molecular weight PPE and the low molecular weight PPE of 0.05 dl / g or more
The PE-based resin composition was found to be a resin composition having an improved balance between moldability, rigidity, heat resistance and impact resistance, and arrived at the present invention.

That is, according to the present invention, the intrinsic viscosity [η] _a dl / g of the components (a) and (b) containing the following components (a) and (b) and measured in chloroform at 30 ° C. [Η] _b dl / g is a PPE resin composition characterized by satisfying the following mathematical expression (1). [Η] _a − [η] _b ≧ 0.05 (1) (a) General formula (I)

[0006]

[Chemical 3]

(In the formula, Q ¹ and Q ² each represent a primary or secondary alkyl group, an aminoalkyl group, a hydrocarbon oxy group or a halohydrocarbon oxy group, and Q ¹ and Q ² are the same or different. The first polyphenylene ether obtained by oxidative coupling polymerization of a 2,6-substituted phenol derivative represented by the formula (II)

[0008]

[Chemical 4]

(Wherein Q ³ , Q ⁴ and Q ⁵ each represent a halogen atom, a primary or secondary alkyl group, an aryl group, an aminoalkyl group, a hydrocarbonoxy group or a halohydrocarbonoxy group, Q ³ , Q ⁴ and Q ⁵ may be the same or different) The second polyphenylene ether obtained by oxidative coupling polymerization of a 2,3,6-substituted phenol derivative represented by

The present invention will be described in detail below.

<First PPE (a)> The first PPE (a) used in the present invention is represented by the general formula (I).

[0012]

[Chemical 5]

(In the formula, Q ¹ and Q ² each represent a primary or secondary alkyl group, an aminoalkyl group, a hydrocarbon oxy group or a halohydrocarbon oxy group, and Q ¹ and Q ² are the same or different. Which may be present) is a homopolymer or a copolymer obtained by oxidative coupling polymerization of at least one 2,6-substituted phenol derivative selected from compounds having a structure represented by

Preferred examples of the primary alkyl group for Q ¹ and Q ² include methyl, ethyl, n-propyl, n-butyl and n.
-Amyl, isoamyl, 2-methylbutyl, n-hexyl, 2,3-dimethylbutyl, 2-, 3- or 4-
Methyl pentyl or heptyl. Suitable examples of secondary alkyl groups are isopropyl, sec-butyl or 1-ethylpropyl. In many cases, Q ¹ and Q ² are alkyl groups, especially alkyl groups having 1 to 4 carbon atoms.

Suitable homopolymers of 2,6-substituted phenol derivatives include, for example, 2,6-dimethyl-1,4.
-Consisting of phenylene ether units. Many suitable homopolymers or random copolymers are described in the patents or literature. Also suitable are PPE containing molecular moieties that improve properties such as, for example, molecular weight, melt viscosity and / or impact strength.

The PPE (a) obtained from the 2,6-substituted phenol derivative used here was 30% in chloroform.
Those having an intrinsic viscosity measured at 0 ° C of 0.15 to 0.85 dl / g are preferable. More preferably, the intrinsic viscosity is 0.25 to
It has a viscosity of 0.75 dl / g, and particularly preferably has an intrinsic viscosity of 0.35 to 0.65 dl / g. When the intrinsic viscosity is less than 0.15 dl / g, the impact resistance of the composition is insufficient, and
If it exceeds 85 dl / g, the moldability of the composition is unsatisfactory.

<Second PPE (b)> The second PPE (b) used in the present invention has the general formula (II)

[0018]

[Chemical 6]

(Wherein Q ³ , Q ⁴ and Q ⁵ each represent a halogen atom, a primary or secondary alkyl group, an aryl group, an aminoalkyl group, a hydrocarbonoxy group or a halohydrocarbonoxy group, Q ³ , Q ⁴ and Q ⁵ may be the same or different) and is obtained by oxidative coupling polymerization of at least one 2,3,6-substituted phenol derivative selected from the compounds having the structure It is a homopolymer or a copolymer.

Suitable examples of the primary alkyl group for Q ³ , Q ⁴ and Q ⁵ include methyl, ethyl, n-propyl, n-butyl, n-amyl, isoamyl, 2-methylbutyl and n-.
Hexyl, 2,3-dimethylbutyl, 2-, 3- or 4-methylpentyl or heptyl. Suitable examples of secondary alkyl groups are isopropyl, sec-butyl or 1-ethylpropyl. In many cases, Q ³ , Q ⁴ and Q ⁵ are alkyl or phenyl groups, especially 1 to 4 carbon atoms
Is an alkyl group.

A preferred homopolymer of a 2,3,6-substituted phenol derivative is, for example, one composed of 2,3,6-trimethyl-1,4-phenylene ether units. Many suitable homopolymers or random copolymers are described in the patents or literature. For example, the molecular weight,
Also suitable are PPEs that contain molecular moieties that improve properties such as melt viscosity and / or impact strength.

The PPE (b) obtained from the 2,3,6-substituted phenol used herein preferably has an intrinsic viscosity of 0.10 to 0.80 dl / g at 330 ° C. measured in chloroform. More preferably the intrinsic viscosity is 0.20
˜0.70 dl / g, and most preferably the intrinsic viscosity is 0.30 to 0.60 dl / g. If the intrinsic viscosity is less than 0.10 dl / g, the impact resistance of the composition will be insufficient,
If it exceeds 0.80 dl / g, there is a problem in moldability of the composition.

Also, the intrinsic viscosity [η] _a dl / g and [η] measured at 30 ° C. in chloroform of the components (a) and (b).
The difference in _b dl / g is 0.05 dl / g or more, preferably 0.1 dl / g or more, and more preferably 0.15 dl / g or more. The difference between [η] _a dl / g and [η] _b dl / g is 0.05 dl / g
If it is less than 1, the moldability, rigidity, heat resistance and impact resistance of the composition are unbalanced, which is not preferable.

<Composition Ratio of Constituent Components> The composition ratio of the components (a) and (b) in the PPE resin composition of the present invention is as follows with the total amount of the components (a) and (b) being 100% by weight. It is as follows. Component (a): 5-95 wt% is preferable, 15-85 wt% is more preferable, 30-70 wt% is particularly preferable. If the content of the component (a) is less than 5% by weight, the impact strength of the final composition will be unsatisfactory, and if it exceeds 95% by weight, the moldability, rigidity and heat resistance will be unsatisfactory. Component (b): 95 to 5% by weight is preferable, more preferably 85 to 15% by weight, and particularly preferably 70 to 30% by weight. If the component (b) is less than 5% by weight, moldability, rigidity and heat resistance are unsatisfactory, and if it exceeds 95% by weight, impact resistance is unsatisfactory.

<Additional component> Other additional components can be added to the PPE resin composition of the present invention. For example, various thermoplastic resins such as styrene resins such as ABS and HIPS; olefin resins such as polyethylene and polypropylene; polyesters such as polyethylene terephthalate and polybutylene terephthalate; polyamides;
Polycarbonate, polyphenylene sulfide, polymethylmethacrylate, polyoxymethylene, thermoplastic elastomers and the like; well-known antioxidants, weather resistance improvers, nucleating agents, flame retardants, impact resistance improvers, plasticizers, fluidity Addition of improving agents; addition of organic / inorganic fillers and reinforcing agents, especially glass fiber, mica, talc, wollastonite, potassium titanate, calcium carbonate, silica, etc., to improve rigidity, heat resistance, dimensional accuracy, etc. It is valid. For practical use, various colorants and dispersants thereof may be known ones.

The PPE polymer used in the present invention is
It may be modified with a modifying monomer. Examples of the monomer used for modification include acid anhydrides such as maleic anhydride; imide compounds such as maleimide anhydride; acrylic acid,
Examples thereof include unsaturated carboxylic acids such as methacrylic acid and epoxy compounds such as glycidyl methacrylate. These modifying monomers may be used alone or in combination of two or more.

<Production and molding method of composition> PP of the present invention
As a melt-kneader for obtaining the E-based resin composition, a kneader generally used for thermoplastic resins can be applied. For example, it can be kneaded by a single-screw or multi-screw kneading extruder, roll, Banbury mixer and the like. The kneading order may be such that all the components may be kneaded at the same time, or a method of kneading using a blended product that has been pre-kneaded in advance, and the components may be sequentially fed from the middle of the cylinder of the extruder and kneaded. Good. The molding method of the thermoplastic resin composition of the present invention is not particularly limited, and molding methods generally used for thermoplastic resins, that is, injection molding, hollow molding, extrusion molding, sheet molding, thermoforming, rotation Various molding methods such as molding, lamination molding, and press molding can be applied.

[0028]

EXAMPLES The present invention will be described in detail below with reference to examples.

Examples 1 to 7 and Comparative Examples 1 to 8 The components used are as follows. Component (a): (a-1) Poly (2,6-dimethyl-1,4-phenylene ether) (Nippon Polyether Co., Ltd., intrinsic viscosity 0.52 dl / g measured in chloroform at 30 ° C.) (a -2) Poly (2,6-dimethyl-1,4-phenylene ether) (Nippon Polyether Co., Ltd., intrinsic viscosity 0.35 dl / g measured in chloroform at 30 ° C) (a-3) Poly (2,2) 6-dimethyl-1,4-phenylene ether) (Nippon Polyether Co., intrinsic viscosity 0.80 dl / g measured in chloroform at 30 ° C.)

Component (b): (b-1) Poly (2,3,6-trimethyl-1,4-phenylene ether) (Nippon Polyether Co., Ltd., intrinsic viscosity 0.50 dl measured in chloroform at 30 ° C.) /
g) (b-2) Poly (2,3,6-trimethyl-1,4-phenylene ether) (manufactured by Nippon Polyether Co., intrinsic viscosity 0.33 dl / measured in chloroform at 30 ° C.)
g) (b-3) poly (2,3,6-trimethyl-1,4-phenylene ether) (manufactured by Nippon Polyether Co., intrinsic viscosity 0.15 dl / measured in chloroform at 30 ° C.)
g)

Others: HIPS: High-impact polystyrene (manufactured by Mitsubishi Kasei, trade name: Dialex HT76) PBT: polybutylene terephthalate (manufactured by Kanebo, trade name: PBT128) PA: nylon 6 (manufactured by BASF, trade name: Ultramid B-3) SEBS: Hydrogenated substance of aromatic vinyl compound-conjugated diene block copolymer (manufactured by Shell Chemical Co., trade name: Kraton G1651) Maleic anhydride: Commercial reagent grade phosphorous acid compound: bis ( 2,6-di-tert-butyl-4
-Methylphenyl) pentaerythritol diphosphite (manufactured by Asahi Denka Co., Ltd., trade name: MARK PEP-36)

The components shown in Table 1 were thoroughly mixed and stirred with a super mixer at the compounding ratio shown in the same table. Then, using a twin-screw type extruder (manufactured by Japan Steel Works, TEX44), this is set at a temperature of 180 to 230 ° C. and the screw rotation speed is
The mixture was melt-kneaded under a kneading condition of 50 to 350 rpm to prepare a composition, and then pelletized.

From the above pellets, an in-line screw type injection molding machine (manufactured by Toshiba Machine Co., Ltd., IS-90B type)
Was used for injection molding at a cylinder temperature of 260 to 300 ° C. and a mold cooling temperature of 60 to 80 ° C. to prepare a test piece. For injection molding, a vacuum dryer was used immediately before that, and drying was performed for 48 hours under the conditions of 0.1 mmHg and 80 ° C. The injection-molded test pieces were placed in a desiccator immediately after molding, allowed to stand at 23 ° C. for 4 to 6 days, and then evaluated, and the results are shown in Table 1.

Each physical property value and various characteristics were measured by the following methods. (1) Flexural modulus ISO R178-1974 Procedure 12 (JIS
In accordance with K7203), using an Instron tester,
It was measured. (2) Izod impact strength ISO R180-1969 (JIS K 7110)
According to the Izod impact test with a notch, it measured using the Izod impact tester (made by Toyo Seiki Seisaku-sho, Ltd.). (3) Heat distortion temperature Using an HDT tester (manufactured by Toyo Seiki Seisakusho), JI
It was evaluated according to SK 7207 under a load of 18.6 kg. (4) Melt flow rate (MFR) ISO R1133-1981 (JIS K 721)
According to 0), it was measured at 280 ° C. and a load of 5 kg.

[0035]

[Table 1]

[0036]

From the results of the above evaluation test, the PP of the present invention is obtained.
It can be seen that the E-based resin composition has an excellent balance between moldability, rigidity, heat resistance and impact resistance. Therefore, it has a wide range of uses and becomes an industrially useful material.

Claims (1)

[Claims] 1. Containing the following components (a) and (b):
In addition, the intrinsic viscosities [η] _a dl / g and [η] _b dl / g of the components (a) and (b) measured in chloroform at 30 ° C. satisfy the following formula (1). Polyphenylene ether resin composition. [Η] _a − [η] _b ≧ 0.05 (1) (a) General formula (I) (In the formula, Q ¹ and Q ² each represent a primary or secondary alkyl group, an aminoalkyl group, a hydrocarbon oxy group or a halohydrocarbon oxy group, and Q ¹ and Q ² may be the same or different. The first polyphenylene ether obtained by oxidative coupling polymerization of a 2,6-substituted phenol derivative represented by the formula (b) the general formula (II) (In the formula, Q ³ , Q ⁴ and Q ⁵ each represent a halogen atom, a primary or secondary alkyl group, an aryl group, an aminoalkyl group, a hydrocarbonoxy group or a halohydrocarbonoxy group, and Q ³ , Q ⁴ and Q ⁵ second polyphenylene ether is obtained by the 2,3,6-substituted phenol derivatives represented by each may be the same or different) is oxidative coupling polymerisation