KR100361159B1 - High impact resin composition based on sulfone - Google Patents

Abstract

PURPOSE: Provided is a high impact resin composition based on sulfone which has improved compatibility, tensile strength, mechanical strength, and performance. CONSTITUTION: The high impact resin composition comprises (a) 100wt% of a base resin containing 30 to 75 wt% of a polyarylene ether mixed with 10 to 40 wt% of a polycarbonate and 15 to 30 wt% of a styrene copolymer or an acrylic copolymer; and (b) 0.5 to 20 wt% of a polyhydroxyether based on 100 parts by weight of the base resin. The resin composition, if desired, may further comprise a lubricant, a pigment, a thermal stabilizer, a UV stabilizer, a flame retardant, a processing aid and an impact reinforcing agent.

Description

High impact sulfone resin composition

Field of invention

The present invention relates to a high-impact sulfone resin composition and a method of manufacturing the same. More specifically, the present invention relates to a high impact sulfone resin composition comprising a polyarylene ether, a styrene copolymer or an acrylic copolymer, a polycarbonate and a polyhydroxy ether.

Background of the Invention

Among the polyarylene ethers, in particular, polysulfone is a high rigidity and high toughness resin having a use temperature of -100 ° C to 160 ° C and a continuous use temperature of 150 ° C. In addition, it has high resistance to hydrolysis, has excellent mechanical performance, electrical performance and chemical resistance, and has been used for various purposes. However, polysulfone is difficult to process due to its poor fluidity, and various methods have been studied to improve the polysulfone. U.S. Patent Nos. 3,555,119 and 3,636,140 describe blends of polysulfones and ABS (acrylonitrile-butadiene-styrene copolymer) resins, which blends improve the processability of polysulfone and provide high heat resistance. It is shown to have. However, the blend of polysulfone and ABS has a disadvantage in that the compatibility of the molding is insufficient and the strength of the weld line is very low.

Therefore, US Patent No. 4,231,922 proposes a method of using a graft copolymer made of a vinyl aromatic compound, an acrylate, an unsaturated nitrile, or a mixture thereof as an impact modifier to reinforce the impact strength. In the US patent, the impact modifier was grafted to an unsaturated elastomer having a tensile strength of 15,000 to 100,000 psi (ASTM D-638). The unsaturated elastomeric polymer serves as a main chain polymer and is selected from the group consisting of polybutadiene, butadiene-styrene copolymer, butadiene-acrylonitrile copolymer or polyisoprene. Examples of the impact modifier include vinyl aromatic compounds selected from the group consisting of styrene, alphamethyl styrene, alkyl styrene, and mixtures thereof; Acrylic ester monomers selected from the group consisting of methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate and mixtures thereof; And unsaturated nitriles selected from the group consisting of acrylonitrile, methacrylonitrile and mixtures thereof. The above-mentioned US patent describes only a method of improving impact strength by using an impact modifier, but does not describe a technique for improving compatibility and appearance performance.

Therefore, the present inventors added a polyhydroxy ether to a blend of polyarylene ether, styrene-based or acrylic copolymer, and polycarbonate to prepare a high-impact sulfone resin composition having improved weld line strength and mechanical strength as well as compatibility and appearance performance. To manufacture.

Purpose of the Invention

An object of the present invention is to provide a sulfone resin composition having improved compatibility by injecting polyhydroxy ether into a blend of polyarylene ether, polycarbonate, and styrene or acrylic copolymer.

Another object of the present invention is to provide a high impact sulfone resin composition having improved tensile strength and mechanical strength.

Still another object of the present invention is to provide a sulfone resin composition having improved appearance performance.

Summary of the Invention

The resin composition of the present invention is polyhydroxy to 100 parts by weight of the base resin mixed with 30 to 75% by weight of polyarylene ether, 10 to 40% by weight of polycarbonate and 15 to 30% by weight of a styrene copolymer or an acrylic copolymer. It is a sulfone-based resin composition improved by adding 0.5 to 20 parts by weight of ether to improve compatibility, impact strength and appearance performance.

According to the purpose, a lubricant, a pigment, a heat stabilizer, an ultraviolet stabilizer, a flame retardant, a processing aid and an impact modifier are added to the resin composition of the present invention in an appropriate amount.

Detailed Description of the Invention

The resin composition of the present invention relates to a polyarylene ether, a styrene copolymer or an acrylic copolymer, and a resin composition for injection molding or extrusion, wherein the polyhydroxy ether is added to a blend of polycarbonate and commercialized. Hereinafter, each component of the resin composition of the present invention will be described in detail.

Polyarylene ether

Polyarylene ether refers to an aromatic polyether as a linear thermoplastic resin in which arylene units are bonded by ether (-O-) ketone (-CO-) or sulfone (-SO _2- ). In general, polyarylene ether is prepared by reacting a dihydric phenol alkali metal salt with a dihalobenzonoid or dibenzonoid compound having a sulfone or ketone bond between arylene groups, and the basic structure thereof is as follows.

In the above formula, E and E 'are structures derived from dihydric phenol and dibenzonoid compounds, respectively, and serve to attract inert electrons at ortho or para positions of a covalent bond. E and E 'of the two structures are bonded to a carbon atom of an ether group via an aromatic carbon atom. The aromatic polyether is divided into polyarylene polyester.

As the dihydric phenol, a weakly acidic dihydric dinuclear phenol is preferable, and a dihydroxy diphenyl alkane or a derivative in which the nucleus thereof is substituted with halogen may be more preferably used. Examples include 2,2-bis (4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) 2-phenylethane, bis (4-hydroxyphenyl) methane or hydrogen in their benzene rings. And derivatives in which one or two of them are replaced with chlorine. Materials having such symmetric or asymmetric linkages are collectively called bisphenols. Linkages linking these include hydrocarbon residues in which ether oxygen (-O-), carbonyl, sulfone or dinuclear phenol is linked to carbon.

In general, the most common repeating unit for polyarylene ether is

The polyarylene ether used in the present invention is made by reacting an alkali metal salt of dihydric polynuclear phenol and a dibenzonoid compound once in the same molar ratio in the presence of a high temperature liquid organic sulfoxide or sulfone solvent in a state where water is completely removed. Get It can also be prepared in a two step process in which dihydric phenol is converted to a metal salt and then reacted with a dibenzonoid compound. In other words, the dihydric polynuclear phenol is reacted in-situ with alkali metal anhydride, alkali metal hydroxide or alkali metal alkoxide compound in a reaction solvent to convert to alkali metal, and then the water produced is made anhydrous. A dialkali metal salt of dihydric phenol is prepared. It is obtained by making a dibenzonoid compound react with chemical equivalent in the dialkali metal salt of dihydric phenol on conditions similar to the above. In order to secure a high molecular weight, it is preferable that the inside of the reactor is certainly anhydrous to maintain a water content of 0.5% or less in the reaction mixture. The reduced viscosity of the resulting poly arylene ether is 0.3-1.5 at 25 ° C. under methylene chloride.

Dihydric polynuclear phenol that can be used in the production of polyarylene ether includes a compound having the following structural formula, derivatives substituted with inert groups thereof may also be used, and two or more kinds thereof may be mixed and used.

Wherein R represents hydrogen, lower alkyl, allyl or halogen substituents, respectively.

Styrene Copolymer or Acrylic Copolymer

Styrene-based resin that can be used in the present invention has a high molecular weight of a homopolymer or copolymer can also be used ABS type. The styrene resin used in the present invention is synthesized by reacting a conjugated diene such as butadiene and a conjugated diene monomer such as styrene copolymerizable therefrom. In order to synthesize the graft copolymer, once the main chain is synthesized, at least one or more types of graftable monomers are reacted in the presence of the already synthesized main chain polymer. Main chain polymers used in the grafting reaction are mainly conjugated diene-based polymers such as copolymers made from polybutadiene, polyisoprene, butadiene-styrene and butadiene-acrylonitrile.

One type of monomer that can be grafted to a backbone polymer synthesized with diene-based monomers is an aromatic monovinyl hydrocarbon. These monomers generally have the following structure.

Wherein X is hydrogen, halogen or difluorobenzoquinone substituted with halogen or nitrogen group, or 1,4-, 1,5- or 1,8-difluoroanthraquinone.

Examples of the aromatic monovinyl hydrocarbon include alkyl-, cycloalkyl-, aryl-, alkali-, allalkyl-, aralkyl-, alkoxy-, aryloxy- and the like, and substituted styrene, 3- Methylstyrene, 3,5-diethylstyrene, 4-propylstyrene, alphamethyl styrene, alphamethyl vinyltoluene, alpha chloro styrene, alpha bromo styrene, dichloro styrene, dibromo styrene, pt-butyl styrene, tetrachloro styrene And mixtures thereof. Of these, styrene and alphamethyl styrene are most preferred.

Other types of monomers that can be grafted to main chain polymers synthesized with diene monomers are also acrylonitrile, substituted acrylonitrile, maleic anhydride and acrylic esters as acrylic monomers. Acrylic acid esters are alkyl esters, and ethyl acrylate and methyl methacrylate are frequently used.

When preparing the graft polymer, the conjugated diene olefin polymer or 1,3-butadiene polymer or their copolymers is made to be about 40 to 60% of the total graft polymer weight. Styrene and acrylonitrile grafted to the backbone polymer are 40 to 60% of the total graft polymer weight. Among the monomers grafted to the main chain of the graft polymer, a homopolymer is formed without being grafted to the main chain. Therefore, the graft polymer of the present invention refers to a mixture of grafts formed in the main chain and ungrafted free copolymers, and the grafted free copolymers and their contents account for up to 90% of the total graft polymer weight. .

As the backbone of the graft polymer, acrylate rubbers may also be used, such as n-butyl acrylate, ethyl acrylate, 2-ethyl acrylate, 2-ethylhexyl acrylate, and also ethylen-propylene-diene rubber and iso Butylene-isoprene copolymers may also be used. The acrylate copolymer is a copolymer of methyl methacrylate with a vinyl monomer and alkyl acrylate or methacrylate having 1 to 8 carbon atoms in the alkyl group. The vinyl monomers include acrylonitrile, N-allyl maleimide, vinyl chloride, N-vinyl maleimide and the like, and the methacrylates include methacrylate, ethyl acrylate and butyl acrylate. The proportion of methyl methacrylate in the weight of the graft polymer is 70% or more, and in some cases, 100% of methyl methacrylate.

Alkylacrylate resins may also be grafted onto the backbone of unsaturated elastomeric polymers (e.g. polybutadiene, polyisoprene, or butadiene-isoprene copolymers) where the alkylacrylate content is at least 50% of the total graft polymer. . Specific methods of synthesizing these resins are known facts and commercial products are readily available. The acrylate resin used in the present invention has a reduced viscosity of 0.1 to 2.0 dl / g in a 25% chloroform 1% solution.

Polycarbonate resin

The polycarbonate resin may be prepared by reacting dihydric phenol with phosgene in the presence of a molecular weight modifier and a catalyst or by using an ester interchange reaction of a carbonate precursor such as dihydric phenol and diphenylcarbonate.

The dihydric phenol that can be preferably used is bisphenol, of which bisphenol A, 2,2-bis (4-hydroxy phenyl) propane, is most preferred. Other dihydric phenols that may be preferably used include hydroquinone, 4,4'-dihydroxydiphenyl, bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 2 , 2-bis (3,5-dimethyl-4-hydroxyphenyl) propane, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) sulfoxide, Halogenated bisphenols such as bis (4-hydroxyphenyl) ketone, bis (4-hydroxyphenyl) ether and 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane.

The polycarbonate resin may be a homopolymer, a copolymer of two or more dihydric phenols, or a mixture thereof. These include linear polycarbonates, branched polycarbonates and polyestercarbonates. The linear polycarbonate is preferably bisphenol A-based polycarbonate, and the branched polycarbonate is preferably a resin prepared by reacting a polyfunctional aromatic compound such as trimellitic anhydride and trimellitic acid with dihydric phenol and a carbonate precursor. The ester carbonate is preferably a resin prepared by reacting a bifunctional carboxylic acid with a dihydric phenol and a carbonate precursor.

Polycarbonate that can be preferably used in the present invention is a bisphenol A-based polycarbonate resin, the molecular weight is not particularly limited, but considering the mechanical properties and workability of the resin composition, the weight average molecular weight is preferably 20,000 to 80,000. Do.

Polyhydroxy ether

The thermoplastic polyhydroxyether used in the present invention has the following structure.

Where E is a radical moiety of the dihydric phenol and E ″ is one or two hydroxyl groups selected from monoepoxy or diepoxy. N is the degree of polymerization and should be at least 20 or greater and 80 or greater is suitable.

Thermoplastic polyhydroxyethers are generally produced by the reaction of dihydric phenols with epoxides during polymerization. At this time, the number of epoxy groups of the epoxide is determined according to a general method and having 1 to 2 epoxy groups for the same mole.

As for the composition of the polyarylene ether used for this invention, 40-65 weight% is preferable as 30-75 weight%. The content of the polycarbonate is 10 to 40% by weight, preferably 20 to 30% by weight. The content of styrene or acrylic copolymer is 15 to 30% by weight, preferably 20 to 25% by weight. Moreover, polyhydroxy ether is 0.5-20 weight part with respect to 100 weight part of base resin which consists of the said polyaryl ether + polycarbonate + styrene or an acryl-type copolymer, and 1-10 weight part is preferable. In addition, lubricants, pigments, heat stabilizers, ultraviolet stabilizers, flame retardants, processing aids and impact modifiers may be used as appropriate additives.

The present invention will be embodied by the following examples, which are only illustrative of the present invention and do not limit or limit the scope of the present invention.

Example

Example 1

A high impact sulfone resin composition according to the present invention was prepared. The properties of each component used are shown in Table 1 below.

Table 1

Flow index of the polymer was measured according to ASTM D-1238 conditions.

50 parts by weight of the polysulfone; 30 parts by weight of polycarbonate; 20 parts by weight of acrylate / butadiene / styrene polymer (Starex SD-0150 manufactured by Cheil Industries); And 2 parts by weight of a polyhydroxyether (25 DEG C, PKHH of Union Carbide as having a reduced viscosity of 0.43 dl / g at THF of 0.2 g / 100 mL); Extruded with a screw extruder. The extrudate was pelleted and the specimens were molded using an Arberg 2-oz screw injection machine.

Tensile strength, elongation at break, tensile modulus (ASTM D-638) and notched Izod impact strength (ASTM D-256) were measured and measured in the injection molded specimens.

The polyhydroxyether was prepared by reacting bisphenol A with epichlorohydrin.

Example 2

A resin composition was prepared in the same manner as in Example 1, except that 4 parts by weight of polyhydroxyether was used.

Tensile strength, elongation at break, tensile modulus (ASTM D-638) and notched Izod impact strength (ASTM D-256) were measured and measured in the injection molded specimens.

Example 3

A resin composition was prepared in the same manner as in Example 1, except that 6 parts by weight of polyhydroxyether was used.

Tensile strength, elongation at break, tensile modulus (ASTM D-638) and notched Izod impact strength (ASTM D-256) were measured and measured in the injection molded specimens.

Example 4

A resin composition was prepared in the same manner as in Example 1, except that 10 parts by weight of polyhydroxyether was used.

Tensile strength, elongation at break, tensile modulus (ASTMD-638) and notched Izod impact strength (ASTM D-256) were measured for the injection molded specimens.

Example 5

A resin composition was prepared in the same manner as in Example 1, except that 20 parts by weight of polyhydroxyether was used.

Tensile strength, elongation at break, tensile modulus (ASTM D-638) and notched Izod impact strength (ASTM D-256) were measured and measured in the injection molded specimens.

Comparative Example 1

A mixture of 50 parts by weight of polysulfone, 20 parts by weight of acrylonitrile / butadiene / alphamethylstyrene polymer (StarexSR-0150) and 30 parts by weight of polycarbonate was extruded at 280 ° C. with a twin screw extruder having a diameter of 30 mm and L / D = 30. . The extrudate was pelleted and the specimens were molded using an Arberg 2-oz screw injection machine. Tensile strength, elongation at break, tensile modulus (ASTM D-638) and notched Izod impact strength (ASTMD-256) were measured and measured in the injection molded specimens.

By using the polyhydroxy ether in Table 2 it can be seen that the Izod impact strength, elongation at break and tensile strength is improved.

Simple modifications and variations of the present invention can be easily made by those skilled in the art, and all such modifications or changes can be seen to be included in the scope of the present invention.

Claims (5)

(A) 30 to 75% by weight of polyarylene ether; (B) 10 to 40% by weight of polycarbonate; 15 to 30% of (C) styrene-based copolymer or acrylic copolymer; And (D) 0.5 to 20 parts by weight of a polyhydroxy ether based on 100 parts by weight of the base resin (A) + (B) + (C); A high impact sulfone resin composition, characterized in that consisting of. The high-impact sulfone-based resin composition according to claim 1, wherein the polyarylene ether has the following structure.

E is a residue of dihydric phenol, E 'is a benzonoid compound in the above structure. The repeating unit of claim 1 or 2, wherein the repeating unit of the polyarylene ether

, or

A high impact sulfone resin composition, which is characterized by the above-mentioned. The high-impact sulfone-based resin composition according to claim 1, wherein the polyhydroxy ether has the following structure.

Wherein E is a radical moiety of the dihydric phenol, E ″ is one or two hydroxyl groups selected from monoepoxy or diepoxy. N is at least 20 degrees of polymerization. The high-impact sulfone-based resin composition according to claim 1 or 4, wherein the polyhydroxy ether has a repeating unit of the following structural formula.