CN1152000A - Flame Retardant Styrenic Resin Composition - Google Patents

Abstract

A flame-retardant styrene resin composition comprises 100 parts by weight of a styrene resin and 5-40 parts by weight of an organic flame retardant having a halogen content of 40% by weight or more. Said styrene resin comprises 2 to 60 parts by weight of a graft copolymer ; 5 to 60 parts by weight of a graft copolymer (D); 0 to 80 parts by weight of a copolymer (E).

Description

Flame Retardant Styrenic Resin Composition

The present invention relates to a flame retardant styrenic resin composition with good flame retardancy, high heat resistance, excellent surface impact strength, resistance to gas burn marks, and excellent appearance of molded products.

Styrene-based resins have been widely used in daily life, especially in household appliances and commercial machinery, such as video recorders, televisions, computers, typewriters, etc., which are mostly made of styrene-based resins. Although these resin products have the advantages of low price, light weight, and appropriate mechanical strength, compared with metals, their disadvantage is that the resin is flammable. resulting in serious injury. For this reason, flame retardancy has always been an extremely important issue in the resin industry technology.

Generally speaking, there are two ways to make resin products flame retardant. One is to mix reactive flame retardant substances and reactive monomers into the resin, and carry out polymerization reaction together to endow the final resin product with flame retardant properties. . This method is more commonly used on thermosetting resins. Another way is to fully mix non-reactive flame retardant substances and resin bodies using kneading devices such as extruders, so that the resin has flame retardant properties. Characteristics, this method is more commonly used in thermoplastic resins.

In order to endow styrene-based resins with flame retardant properties, the flame retardants commonly used in the prior art generally belong to halogen-containing organic flame retardants, especially chlorine-containing or bromine-containing organic flame retardants, such as decabromodiphenyl decabromodiphenyl oxide, octabromodiphenyl oxide, tetrabromobisphenyl A, bis(tribromophenoxy)ethane [bis(tribromophenoxy)ethane], 1,2-bis (tetrabromophthalimide) ethane [ethylene bis (tetrabromophthalimide)], bis (hexachlorocyclopentadiene) cyclooctane [bis (hexachloro-cyclopentadiene) cyclooctane], decabromodiphenylmethane, decabromo Diphenylethane, etc. These flame retardants are usually used with an appropriate proportion of inorganic flame retardant additives to reduce the amount of halogen-containing organic compounds used, so as to avoid the reduction of the mechanical properties and durability of styrene-based resins due to the addition of halogen-containing organic flame retardants. Physical properties of raw materials such as thermal properties.

On the other hand, the impact of the addition of flame retardants in styrene-based resins on raw materials, the destruction of impact strength and the formation of burn marks on the surface of injection molded products (Gas burnnig) are the most concerned by the home appliance industry, business machines, and electronic information industries . When the impact strength of the resin is insufficient, the molded product will not be able to withstand the collision during transportation and installation due to the gap-like network structure (heat dissipation design), and even cause cracking and damage. In addition, during resin injection molding, due to the resin and It is flame retardant and easy to crack, and produces decomposing acidic substances, such as hydrobromic acid (HBr), hydrochloric acid (HCl), etc. Especially for the pin gate molds that are often used recently, the reduction of the diameter of the filling port is likely to generate greater frictional heat, so when the temperature of the resin itself increases during injection, the cracking of the resin will be more serious, which will also lead to a large amount of gas produce. The above-mentioned volatile and decomposed substances (i.e. the aforementioned hydrobromic acid, hydrochloric acid, etc.) will produce gas burn marks on the surface of the molded product after cooling, which will also affect the appearance of the finished product. The aforementioned deficiency will greatly affect the use of the resin. limits.

For example, in the U.S. Patent No. 3830766 case, it was mentioned that using tetrabromobisphenol A as a flame retardant, and using antimony trioxide, chlorinated polyethylene and other flame retardant additives containing flame retardant resins can improve The ductility and anti-aging properties of the resin, but when tetrabromobisphenol A is added to the styrene resin, it will obviously damage the physical properties of the raw material, such as heat resistance, surface impact strength, etc., and gas burn marks will occur on the injection molded product The situation cannot be improved, so it is limited in use.

In order to improve the aforementioned deficiencies, the inventors of the present case have found through research that by adding a halogen-containing organic flame retardant to a specific styrene-based resin, good flame retardancy and heat resistance can be obtained, and it has excellent surface impact strength, Flame retardant styrenic resin composition with appearance and gas burn resistance.

Therefore, the main purpose of the present invention is to provide a flame retardant styrene resin composition with good flame retardancy and heat resistance, excellent surface impact strength, appearance and resistance to gas burn marks.

The flame retardant styrenic resin composition of the present invention mainly comprises:

(1) 100 parts by weight of styrene-based resins, comprising:

(1) 2 to 60 parts by weight of the graft copolymer (C), the graft copolymer (C) is a rubber graft copolymer (A ), 2-25 parts by weight of diene rubber and 0.1-10 parts by weight of propylene-based copolymer (B) and 100 parts by weight of styrene-based monomers of 45-80 parts by weight, 15-50 parts by weight A graft copolymer obtained by bulk and/or solution polymerization of a monomer mixture composed of acrylonitrile-based monomers and 0 to 40 parts by weight of copolymerizable monomers;

(2) The graft copolymer (D) of 5～60 weight parts, this graft copolymer (D) is to be the rubber emulsion of 0.05～0.8 μm by the weight average particle diameter of 50～85 parts by weight and 15～50 weight parts A graft copolymer obtained by emulsification graft polymerization of a monomer mixture of styrene-based monomers, acrylonitrile-based monomers and other optional copolymerizable monomers;

(3) The copolymer (E) of 0～80 weight part, this copolymer (E) is by the styrene monomer of 50～80 weight part, the acrylonitrile monomer of 20～50 weight part and 0～40 A copolymer obtained by polymerizing optional other copolymerizable monomers in parts by weight; and

(2) 5-40 parts by weight of a halogen-containing organic flame retardant with a halogen content of 40% by weight or more.

According to the aforementioned composition, a flame retardant styrenic resin composition having good flame retardancy, high heat resistance, excellent surface impact strength and gas burn resistance, and excellent appearance of molded products can be obtained.

The rubber graft copolymer (A) of the present invention is obtained by emulsion polymerization, and the preferred production method is to connect diene monomers and other copolymerizable monomers with emulsion polymerization to polymerize the weight average particle diameter ( Weight average particle size) 0.05 ~ 0.8μm rubber emulsion, the above-mentioned monomers can also be made into a rubber emulsion with a small particle size of 0.05 ~ 0.2μm by emulsion polymerization, and then cryogenic agglomeration (cryogenic agglomeration) or mechanical agglomeration method Or additive agglomeration method, agglomerating the above-mentioned small particle size rubber emulsion into a rubber emulsion of 0.15-0.8 μm; wherein, the additive used in the additive agglomeration method can be: acetic anhydride, hydrogen chloride, sulfuric acid and other substances, or chlorine Sodium chloride, potassium chloride, calcium chloride and other salts, and (meth)acrylic acid-(meth)acrylate copolymers (such as methacrylic acid-butyl acrylate copolymer, methacrylic acid-acrylic acid ethyl Ester copolymer) and other polymer coagulants containing carboxylic acid groups.

The aforementioned rubber emulsion is mixed with 50-85 parts by weight of styrene-based monomers, 15-50 parts by weight of acrylonitrile-based monomers, 0-30 parts by weight of other copolymerizable monomers, and appropriate emulsifiers and initiators. Graft polymerization reaction; above-mentioned starter can use common starter in this area, for example: dibenzoyl peroxide (dibenzyl peroxide), diisopropyl benzene hydroperoxide (diisopropyl benzene hydroperoxide), tert-butyl Hydrogen peroxide (tert-butylhydropeoroxie), cumene hydroperoxide (cumene hydroperoxide), potassium persulfate (potassium persulfate), among which organic hydrogen peroxide is preferred.

The rubber graft copolymer (A) of the present invention can also use redox catalyst system activators during polymerization, or activators in known technologies such as iron ions, such as sodium pyrophosphate dextrose (sodium pyrophosphate dextrose), formaldehyde Sodium formal dehyde sulfoxylate, ascorbic acid, dihydroxyacetone, etc. can all be used. In addition, ethylene diamine tetraacetic acid salt can also be added to promote its effect ; And ferric ion source can use ferric chloride or ferrous sulfate.

The graft ratio of the aforementioned rubber graft copolymer (A) can be controlled by the polymerization reaction conditions, such as: the amount and type of polymerization temperature, initiator, emulsifier, chain transfer agent, the addition method of monomer, etc. Control; also can add chain transfer agent according to known technology and adjust the molecular weight of graft copolymer (A), and common chain transfer agent has: n-butyl mercaptan (n-butyl mercaptan), n-octyl Mercaptan (n-octyl mercaptan), n-dodecyl mercaptan (n-dodecyl mercaptan), tert-dodecyl mercaptan (tert-dodecyl mercaptan); molecular weight of the above-mentioned rubber graft copolymer (A) It can also be adjusted by changing the polymerization conditions such as the polymerization temperature, the type and amount of the initiator, and the method of adding the monomer. The reaction temperature of the graft polymerization is below 90°C, especially between 30°C and 80°C. The monomers for grafting can be added at one time, also can be added in batches, can also be added continuously or various monomers are grafted and polymerized in sections, so that the rubber graft copolymer emulsion can be obtained; then the aforementioned graft copolymer The emulsion undergoes traditional steps such as coagulation, dehydration, and drying to obtain the rubber graft copolymer (A) with a weight average particle diameter of 0.05-0.8 μm required by the present invention.

Although the rubber graft copolymer (A) of the present invention can be obtained by using the aforementioned various methods, based on the principle of shortening the polymerization time of the rubber emulsion to improve the production efficiency, it is better to use an agglomerated rubber emulsion. The uniformity of the particle size of the polymerization and the purpose of reducing coagulation, and the addition of a polymer coagulant containing carboxylic acid groups to agglomerate the rubber emulsion is better.

The styrene-based monomer used in the rubber graft copolymer (A) of the present invention can be styrene, α-methylstyrene, α-chlorostyrene, p-t-butylstyrene, p-methylstyrene , o-chlorostyrene, p-chlorostyrene, 2,5-dichlorostyrene, 3,4-dichlorostyrene, 2,4,6-tribromostyrene, 2,5-dibromostyrene etc. Among them, styrene or α-methylstyrene is preferable.

The acrylonitrile-based monomer used may be: acrylonitrile, α-methacrylonitrile, etc.; wherein acrylonitrile is preferred.

The copolymerizable monomers used in the rubber graft copolymer (A) of the present invention can be: (meth)acrylate monomers, maleimide monomers, etc.; wherein (meth)acrylate monomers The body can be: methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, benzyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, methyl Lauryl acrylate, 2-hydroxyethyl methacrylate, glycidyl methacrylate, and dimethylaminoethyl methacrylate, among which methyl methacrylate is preferred.

Maleimide monomers can be: maleimide, N-methylmaleimide, N-isopropylmaleimide, N-butylmaleimide, N-ha Alkylmaleimide, N-octylmaleimide, N-dodecylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide, N-2,3-tolylmaleimide, N-2,4-tolylmaleimide, N-2,3-ethylphenylmaleimide, N-2,4-ethyl Phenylmaleimide, N-2,3-butylphenylmaleimide, N-2,4-butylphenylmaleimide, N-2,6-tolylmaleimide Amine, N-2,3-chlorophenylmaleimide, N-2,4-chlorophenylmaleimide, N-2,3-bromophenylmaleimide, N-2 , 4-bromophenylmaleimide, etc., among which N-methylmaleimide is preferred.

The propylene-based copolymer (B) of the present invention is composed of: 10-100% (by weight) of at least one monomer selected from (meth)acrylate-based monomers and acrylonitrile-based monomers, 0-80% (weight) styrene-based monomers, and 0 to 30% (weight) other copolymerizable monomers; The same, but the difference is that other polymerizable monomers in the propylene-based copolymer (B) do not include maleimide-based monomers; and the polymerization methods can be various methods such as solution, bulk, emulsion or suspension polymerization. Polymerization methods, among which solution or bulk polymerization is preferred.

The diene rubber used in the graft copolymer (C) of the present invention is a polymer having a glass transition temperature below -20°C after ion polymerization of diene monomer components. Preferred diene rubbers are such as: butadiene rubber, isoprene rubber, chloroprene rubber, etc.; wherein, butadiene rubber has high cis (Hi-Cis) content and low cis (Low-Cis) content. Cis) content: in high cis rubber, the typical weight composition of cis (Cis)/vinyl (Vinyl) is 94-98%/1-5%, and the rest of the composition is trans (Trarns) structure; Mooney viscosity is between 20 and 120, and the molecular weight range is preferably 100,000 to 800,000; in low-cis rubber, the typical weight composition range of cis/vinyl is 20-40%/1-20%, and the rest is trans structure. Its Mooney viscosity is between 20 and 120. Other suitable rubber materials are: acrylonitrile rubber, styrene/butadiene rubber, or a mixture of the above-mentioned different rubbers. Styrene/butadiene rubber is commonly known as SBR. The styrene/butadiene copolymer rubber suitable for the present invention can be in the form of two-stage (di-block) copolymerization, three-stage (tri-block) copolymerization, random copolymer (random) or Star copolymerization (star type). The weight ratio of styrene/butadiene rubber is preferably in the range of 5/100 to 80/20, and the molecular weight is preferably in the range of 50,000 to 600,000. The aforementioned rubbers suitable for the present invention are preferably butadiene and styrene/butadiene rubber, among which butadiene rubber is more preferred.

The graft copolymer (C) of the present invention comprises 0.1 to 10 parts by weight of a rubber graft copolymer (A), 2 to 25 parts by weight of a diene rubber, and 0.1 to 10 parts by weight of a propylene-based copolymer (B), And a mixture of the following monomers with a total weight of 100 parts by weight: 45-80 parts by weight of styrene-based monomers, 15-50 parts by weight of acrylonitrile-based monomers and 0-40 parts by weight of copolymerizable monomers, in bulk And/or obtained by solution polymerization.

Specifically, in the present invention, the raw material solution formed by mixing and dissolving the aforementioned monomers, rubber graft polymer (A), diene rubber, propylene-based copolymer (B), and a solvent selected according to needs is fed into Polymerization in a reactor; or mix and dissolve part of the aforementioned monomers, rubber graft polymer (A), propylene-based copolymer (B), and a solvent selected as required to form an independent raw material solution, and then mix and dissolve the remaining monomers It is mixed and dissolved with diene rubber to form another raw material solution, and the two raw material solutions are respectively sent to the reactor for polymerization reaction.

The aforementioned raw material mixing can be dissolved in a traditional dissolution tank with high shear stress and high stirring speed. This dissolution tank can be used: a ribbon-shaped helical stirring blade, a propeller-type stirring blade, or other stirring blades that can generate high shear stress, etc. Under sufficient time, the above-mentioned diene rubber or rubber graft polymer (A), propylene-based copolymer (B) can be completely dissolved into the state of rubber solution, so as to facilitate the operation of pumping to the reactor; The above-mentioned raw material solution is respectively and continuously added to the first reactor and/or the second reactor, and/or its subsequent reactor, and the chain transfer agent, the free agent and the initiator are added together to carry out the reaction.

When the reaction mixture is continuously withdrawn from the first reactor at a rate corresponding to the feeding rate of the raw materials, the withdrawn reaction mixture is fed into the second or more subsequent reactors for one-step polymerization. There is no particular limitation on the form of the aforementioned first or more reactors, but based on factors such as the dispersion state of the graft copolymer (C), and the phase inversion of the diene rubber and the control of its particle size and distribution, The first reactor is preferably to adopt complete mixing type (CSTR) reactor; Through the reaction of aforementioned each reactor, make its conversion rate reach 40～90% (weight), finally the reaction mixture after the reaction is sent to A volatilization device is used to remove unreacted monomers and solvents to obtain the graft copolymer (C), whose weight average particle size is between 0.3-10 μm, preferably between 0.8-6 μm.

The usage amount of graft copolymer (C) of the present invention is 2～60 weight parts with respect to the styrenic resin of 100 weight parts, when wherein the usage amount of graft copolymer (C) is less than 2 weight parts, the resin's The heat resistance is poor, and the improvement effect of the surface impact strength and the anti-gas burn phenomenon is insufficient; if the usage amount of the graft copolymer (C) is greater than 60 parts by weight, high impact strength, especially the surface impact strength property, cannot be obtained.

The usage amount of the rubber graft copolymer (A) is 0.1 to 10 parts by weight, preferably 0.5 to 8 parts by weight relative to 100 parts by weight of the total monomer weight in the graft copolymer (C). When the usage amount of the rubber graft copolymer (A) in the graft copolymer (C) is higher than 10 parts by weight, the viscosity of the feed solution is too high, the dissolution and dispersion are difficult, and the pumping operation is difficult. The amount of the propylene-based copolymer (B) in the present invention is 0.1-10 parts by weight, preferably 0.5-8 parts by weight, based on 100 parts by weight of the total monomer weight in the graft copolymer (C). When the amount of the propylene-based copolymer (B) in the graft copolymer (C) is less than 0.1 parts by weight, the polymers tend to aggregate together and settle in the solution, but cannot be completely dispersed and dissolved in the solution, resulting in The pumping operation is difficult, the graft copolymer (C) produced after the reaction will contain coarse particles, and the finished resin composition will have fish eye (fish eye) surface defects, which is not good in appearance; if the propylene-based polymerization If the amount of the substance (B) used is higher than 10 parts by weight, the viscosity of the feed solution is too high, the operation is difficult, and the repeated polymerization and reprocessing of the excessive propylene-based polymer (B) is not economical. When the amount of the rubber graft copolymer (A) and the propylene-based copolymer (B) in the raw material solution of the graft copolymer (C) is less than 0.1 parts by weight, the surface impact strength of the resin is poor.

When the graft ratio of the rubber graft copolymer (A) of the present invention is 10-40%, and the molecular weight of the hard copolymer grafted on the rubber is between 40,000-120,000, the composition can have better impact Strength and mobility. The above-mentioned graft ratio refers to the ratio (%) of the hard copolymer grafted on the rubber to the rubber. The rigid copolymer in the present invention is a polymer of styrene-based monomers, acrylonitrile-based monomers and copolymerizable monomers.

The production method of the graft copolymer (D) of the present invention is similar to that of the rubber graft copolymer (A). The graft copolymer (D) and the rubber graft copolymer (A) may have the same composition or different compositions. But based on the balance of physical properties between preferred impact strength, rigidity and fluidity, the grafting rate of graft copolymer (D) is preferably between 18～80%, and the molecular weight of the hard copolymer of its grafting is preferably Between 40,000 and 200,000. When the grafting rate was lower than 18% or the molecular weight of the grafted rigid copolymer was lower than 40,000, the impact strength and rigidity of the resin were not good; and when the grafting rate was greater than 80%, and the molecular weight was higher than 200,000, the Poor liquidity. The usage-amount of the said graft copolymer (D) is 5-60 weight part with respect to 100 weight part of styrene-type resins. When the usage-amount of graft copolymer (D) is lower than 5 weight parts, the surface impact strength of resin composition is insufficient; And when the usage-amount of graft copolymer (D) is higher than 60% (weight), resin's Flame retardancy and heat resistance deteriorate.

The copolymer (E) of the present invention is polymerized by 50 to 80 parts by weight of styrene monomers, 20 to 50 parts by weight of acrylonitrile monomers, and 0 to 40 parts by weight of optional copolymerizable monomers. have to. The description of the styrene monomer, acrylonitrile monomer and copolymerizable monomer is the same as that of the rubber graft copolymer (A). Copolymer (E) can be prepared by bulk, solution, suspension, or emulsion polymerization, among which bulk or solution polymerization is preferred. The molecular weight of the copolymer (E) is between 60,000-400,000, preferably between 80,000-300,000. The amount used is 0 to 80 parts by weight relative to 100 parts by weight of the styrene resin.

The halogen-containing organic flame retardants used in the present invention are all prepared in styrene resin, and the halogen content thereof is preferably above 40% by weight, particularly preferably between 55-85% by weight. When said halogen content is less than 40% by weight, a styrenic resin composition excellent in flame retardancy cannot be obtained.

The halogen-containing organic flame retardant used in the present invention includes bromine-containing organic flame retardant, and its representative examples are decabromodiphenyl ether, octabromodiphenyl ether, tetrabromobisphenol A, brominated epoxy Resin, decabromodiphenylmethane, decabromodiphenylethane, tetrabromobisphenol A-bis(2,3-dibromopropyl ether), tetrabromobisphenol A-bis(allyl ether), Tetrabromobisphenol A, hexabromocyclododecane, pentabromodiphenyl ether, 2,4,6-tribromophenol, poly-dibromophenyl oxide, Bis(tribromophenoxy)ethane, tetrabromophthalic anhydride, diol tetrabromophthalate, tetrabromophthalate; N,N',-(oxygen-di- p-phenylene)-bis[3,4,5,6-tetrabromophthalimide]{N,N'-(oxy-di-p-phenylene)-bis[2,4,5,6- tetrabromophthalimide]}, N, N'-(methine-two-p-phenylene)-bis[3,4,5,6-tetrabromophthalimide {N, N'-(methylene-di- p-phenylene)-bis[3,4,5,6-tetrabromophthalimide]}, N,N'-(p,m-phenylene)-bis[3,4,5,6-tetrabromophthalimide ]{N, N'-(p and m-phenylene)-[3,4,5,6-tetrabromophthalimide]}, N, N'-(1,2-ethylene)-bis[3,4,5 , 6-tetrabromophthalimide] {N, N'-(1,2-ethylene)-bis[3,4,5,6-tetrabromophthalimide]} and N, N'-(1,2-butylene base)-bis[3,4,5,6-tetrabromophthalimide]{N,N'-(1,2-butylene)-bis[3,4,5,6-tetrabromophthalimide]}, decabromophthalimide Diphenylpropane, decabromodiphenylbutane, octabromodiphenylpropane, octabromodiphenylbutane and chlorine-containing organic flame retardants, representative examples of which are: 1, 2, 3, 4, 7, 8, 9, 10, 13, 13, 14, 14-Dodecachloro-1, 4, 4a, 5, 6, 6a, 7, 10a, 10a, 11, 12, 12a-Dodecahydro-1, 4,7,10-dimethoxydibenzoyl (a, e) cyclooctene; Among them, the preferred halogen organic flame retardants are decabromodiphenyl ether, octabromodiphenyl ether, tetrabromobisphenol A. Brominated epoxy resin, tetrabromophthalimide ethane, decabromodiphenylmethane and decabromodiphenylethane; the amount of general halogen-containing organic flame retardants used relative to styrene resin is 100 parts by weight is 5 to 40 parts by weight, preferably 10 to 30 parts by weight. When the amount of the halogen-containing organic compound used is less than 5 parts by weight, the flame retardancy is insufficient; when the amount of the halogen-containing organic compound used is more than 40 parts by weight, the impact resistance of the resin is insufficient.

In order to obtain sufficient flame retardancy, the present invention can further use inorganic flame retardant additives, such as antimony trioxide, antimony pentoxide, ferric oxide, borate, magnesium hydroxide, aluminum hydroxide, etc., among which Antimony trioxide is used in an amount of 1-30 parts by weight, preferably 2-20 parts by weight, particularly preferably 4-12 parts by weight, relative to 100 parts by weight of the styrene resin.

In order to further improve the impact strength of the resin, 1 to 20 parts by weight, preferably 2 to 15 parts by weight of chlorinated polyethylene ( cholopolyethylene). When the amount of chlorinated polyethylene used is less than 1 part by weight, the effect of improving impact properties will be lacking, and if the amount used exceeds 20 parts by weight, the tensile strength will be poor. As for the aforementioned chlorinated polyethylene, it is particularly preferable to improve the impact strength of the resin with a crystallinity of 0 to 45% and a chlorine content of 20 to 50% by weight.

Generally, organic flame retardants containing halogen atoms or chlorinated polyethylene tend to produce hydrogen halides when heated, and hydrogen halides will promote the deterioration of flame retardant styrene resins and cause obvious thermal discoloration. In order to suppress or prevent this phenomenon, 0.1 to 10 parts by weight of anti-dehydrohalogenation agents including metal soap salts, metal oxides, and organotin compounds are usually added as heat stabilizers to the styrene-based resin composition of the present invention.

Furthermore, 0.01 to 7 parts by weight of phenolic antioxidants often need to be added to the styrene resin composition of the present invention. Thio-ester-based antioxidants, phosphite-based antioxidants, lubricants and dispersants, etc.

The resin composition of the present invention is composed of styrene-based resin, flame retardant, and appropriate amount of light stabilizer, filler, colorant, plasticizer, antistatic agent and weather resistance agent for improving the moldability of thermoplastic resin may be added. and so on for deployment.

In order to obtain the resin composition of the present invention, the typical mixing method adopted is to mix the various components with a Henschel mixer commonly used in the field of synthetic resins, and then dry mix them with an extrusion mixer, kneading machine, etc. Mixers such as mixers or Banbury mixers are used for melt mixing. Among the above mixing methods, when using melt kneading or the molding method described later, if the resin composition of the present invention is subjected to high temperature action, it will cause thermal decomposition or dehydrohalogenation reaction, so it is suitable for mixing at a temperature of 150-230°C. implement.

When molding the resin composition of the present invention, molding methods such as injection molding, extrusion molding, compression molding, and hollow molding are generally applicable.

The present invention is described in further detail below with embodiment and physical property test. In the following examples, unless otherwise stated, the amounts of all components are expressed in weight percent or parts by weight. <Preparation Example 1> Preparation of rubber graft copolymer (A-1): Components 1,3-butadiene in parts by weight 150.00 Potassium persulfate solution (1%) 15.00 Sodium lauryl sulfate solution (10%) 20.00 Distilled water 190.00 Ethylene glycol dimethacrylate 0.13

According to the above formula, react at a reaction temperature of 65°C for 12 hours to obtain a synthetic rubber emulsion with a conversion rate of 94%, a solid content of about 40%, and a weight average particle size of 0.1 μm.

In addition, the polymer coagulant containing carboxylic acid groups is produced with the following ingredients; ingredients weight parts ethyl acrylate 90.0 acrylic acid 10.0 potassium persulfate solution (1%) 0.5 sodium lauryl sulfate solution (10 %) 0 0 2 distilled water

According to the above formula, react at a reaction temperature of 75°C for 5 hours to obtain a carboxylic acid group-containing polymer coagulant with a conversion rate of about 95% and a pH value of 6.0.

Afterwards, the synthetic rubber latex of 100 parts by weight is agglomerated using 3 parts by weight of carboxylic acid group-containing macromolecule coagulant (dry weight), and the pH value of the obtained agglomerated rubber latex is 8.5, and the weight average of its rubber particles The particle size is about 0.31 μm.

Finally, the aforementioned agglomerated rubber emulsion was used for graft polymerization according to the following formula to prepare the rubber graft copolymer (A-1). Ingredient weight attachment to the rubber emulsion (dry weight) 100.0 苯 成 25.0 acryline 8.3 uncle-duoliosteriol 2.0 isopopenenhe hydrogen hydrogen peroxide 3.0 iron solution (0.2 %) 3.0 sodium sulfate formaldehyde solution ( 10%) 0.9 EDTA solution (0.25%) 3.0

The rubber graft copolymer emulsion made according to the formula in the above table is then dehydrated and dried to less than 2% of the water content to obtain the required rubber graft copolymer (A-1) of the present invention (rubber content 75%) % (weight)), its rubber particle weight-average particle diameter is 0.31 μm, graft rate is 30.5%, and the molecular weight of the styrene-acrylonitrile copolymer grafted on the rubber is 63,000.

<preparation example 2> the preparation of rubber graft copolymer (A-2):

With the synthetic rubber emulsion (the weight average particle diameter of rubber particle is 0.1 μm) that <preparation example 1> makes, promptly do not pass through the agglomeration process of macromolecular flocculant, directly carry out graft polymerization reaction with following formula, with A rubber graft copolymer (A-2) was prepared. Ingredient weight synthetic rubber emulsion (0.1 μm) (dry weight) 100.0 苯 成 成 成 成 腈 腈 腈 成 成 成 成 成 成 成 成 成 成 成 成 成 成 成 成 成 5.0 uncle-duoliosate 2.0 diopenzenhexide 3.0 ferrite sulfate solution ( 0.2%) 3.0 sodium hyposulfate formaldehyde solution (10%) 0.9 ethylenediaminetetraacetic acid solution (0.25%) 3.0

The rubber graft copolymer emulsion that makes is treated with <Preparation Example 1>. The above-mentioned rubber graft copolymer (A-2) (rubber content 75% by weight) has a weight average particle diameter of 0.1 μm, a grafting rate of 26.8%, and the grafted styrene-acrylonitrile-methyl methacrylate copolymer The molecular weight is 58,000.

<Preparation example 3> preparation of propylene-based copolymer (B-1):

Mix the raw materials of 75 parts by weight of styrene, 18 parts by weight of acrylonitrile, and 32 parts by weight of methyl methacrylate at a rate of 12 kg/hour, and mix 3.0 grams/hour of ethylene distearamide, dibenzoyl Peroxide, tert-dodecyl mercaptan and the recovery liquid mentioned later are combined as a feed liquid, and the internal temperature is maintained at 108° C. and a volume of 45 liters is attached to a tank type polymerization tank with a stirrer, and the reaction is performed. The proportion of toluene in the liquid was kept at 15%, and the polymerization rate was kept at 55%.

After the reaction solution is passed through a volatilization device to remove volatile components, the particles of the propylene-based copolymer required by the present invention can be obtained. On the other hand, the removed volatile components are condensed by the condenser and recovered as recovery liquid, which is continuously mixed with the aforementioned raw materials for reuse. This method can adjust the reaction speed by the amount of dibenzoyl peroxide, or adjust the amount of tert-dodecyl mercaptan; finally make styrene-propylene with a melt flow index of 1 at a rate of about 12 kg/hour Nitrile-methyl methacrylate copolymer (B-1).

(preparation example 4> the preparation of propylene-based copolymer (B-2)

Directly adopt methyl methacrylate (trade name: ACRYREX CM-205) manufactured by the applicant company.

<Preparation Example 5> graft copolymer (C):

Use 7 parts by weight of polybutadiene (produced by Asahi Kasei, trade name--Asadene 55AS) as diene rubber, 0.1 parts by weight of tertiary-dodecyl mercaptan and 0.07 parts by weight of dibenzoyl Peroxide is used as initiator, and 1.4 parts by weight of rubber graft copolymer (A-1) (rubber content 75% (weight)) and 1.4 parts by weight of propylene-based polymer (B-1) are completely dissolved A feed solution was formed in 74.4 parts by weight of styrene, 25.6 parts by weight of acrylonitrile and 30 parts by weight of ethylbenzene. The aforementioned feed solution is continuously fed into the first reactor, the first reactor has a volume of 44 liters, a reaction temperature of 100° C., and a stirring speed of a spiral stirring device installed therein is 300 rpm. A cooling circulation pipe is provided in the stirring device, and the mixture after the first reaction is continuously taken out and sent into the second reactor, and the structure of the second reactor device is the same as that of the first reactor. When the conversion rate of the mixture reaches 60%, the mixture is taken out and sent to a volatilization device to remove unreacted monomers and volatile components, and then extruded and granulated to obtain a weight-average particle size of 1.1 μm Graft copolymer (C-1) particles.

Graft copolymers (C-2), (C-3), (C-4), (C-5), and (C-6) were prepared according to the aforementioned preparation method and the proportions listed in Table 1.

<preparation example 6> the preparation of graft copolymer (D):

The synthetic rubber emulsion is the same as Preparation Example 1, but the agglomeration treatment is changed to agglomerate the synthetic rubber emulsion of 100 weight parts with the polymer coagulant containing carboxylic acid groups of 3.5 parts by weight, and the pH value of the rubber emulsion obtained is 8.5, The weight average diameter of the rubber particles is about 0.28 μm, and the graft polymerization reaction is carried out according to the following formula to obtain the graft copolymer (D). Equipment weight Settlement rubber lotion (dry weight) 100.0 成 成 40.0 acryline 13.4 uncle-duoliosteriumanol 2.0 isopenopine hydrogen peroxide 3.0 ferrite sulfate (0.2 %) 3.0 sodium sulfate formaldehyde solution ( 10%) 0.9 EDTA solution (2.25%) 3.0

The above-mentioned graft copolymer (D) (rubber content 65% by weight) had a weight average particle diameter of 0.28 μm, a graft ratio of 42%, and a molecular weight of the grafted styrene-acrylonitrile copolymer of 80,000.

<preparation example 7> the preparation of copolymer (E):

With the raw material of styrene 76 weight parts, acrylonitrile 24 weight parts with the speed of 12 kilograms/hour mixing, then ethylene distearamide 3.0g/ hour, dibenzoyl peroxide, tert-dodecyl Alkyl mercaptans, and the recovery liquid formed after condensation of the volatile components removed by the reaction described later are combined as raw material liquids, and the styrene-acrylonitrile copolymer (E) with a melt flow index of 1.2 is obtained with the polymerization procedure of Preparation Example 3 .

The test standard of the measured material and molding appearance of following embodiment and comparative example is as follows:

*Surface impact strength: Measured according to ASTM D-3763 standard, expressed in kilograms.cm.

*Flame resistance test: according to the American standard UL-94 vertical burning test (thickness 1/16 inch) method, ○ indicates that the test is passed, and × indicates that the test is not passed.

*Heat resistance test: measured according to ASTM D-1525 standard.

*Gas burn mark resistance test: Under fixed conditions, the mold adopts a pin gate mold during injection molding, and the barrel temperature is set at 250°C. Observe the gas burn mark of the obtained molded product. The meaning of the symbols in Table 2 is: ○ means no gas burn mark, × means serious gas burn mark.

*Appearance of the finished product: The test piece of the molded product is visually inspected. Those with a flat appearance are indicated by ○, and those with grainy protrusions or fish eyes on the surface are indicated by ×. Example

<Example 1>

The graft copolymer (C-1) 30 weight parts that table 1 makes, graft copolymer (D) 25 weight parts, copolymer (E) 45 weight parts, and bromine content are the brominated ring of 59%. Oxygen resin flame retardant (Japan DIC company product, trade name is EC-14) 16.4 parts by weight, antimony trioxide (Sb ₂ O ₃ ) 8 parts by weight, chlorinated polyethylene 10 parts by weight, with Henschel mixer Dry blending, then set the cylinder temperature at 205°C and the die head at 220°C with a twin-screw extruder with a vent to produce granular flame retardant styrene resin, and conduct various physical property tests , and the measured results are shown in Table 2.

<Example 2>

The operating conditions are the same as in Example 1, and the formula in Table 2 is extruded, granulated, and shaped to obtain a test piece for testing. The measured physical properties are also listed in Table 2.

<Example 3>

With the operating condition of embodiment 1, but be that the tetrabromobisphenol A flame retardant (GREAT LAKES company product, trade name is BA-59P) of 59% with bromine content replaces the brominated epoxy resin of embodiment 1, and with The formulations in Table 2 were extruded, granulated and tested for various physical properties, and the measured physical properties are also listed in Table 2.

<Example 4>

With the operating condition of embodiment 1, but be that the tetrabromobisphenol A flame retardant (GREAT LAKES company product, trade name is BA-59P) of 59% with bromine content replaces the brominated epoxy resin of embodiment 1, and with The formula in Table 2 was extruded, granulated and subjected to various physical property tests. The measured physical properties are listed in Table 2.

<Example 5>

The same operating conditions as in Example 1, extruded with the formula in Table 2, granulated, and shaped to obtain a test piece for testing, the measured physical properties are also set out in Table 2.

<Example 6>

The same operating conditions as in Example 1, but the flame retardant is a brominated epoxy resin with a bromine content of 59% and decabromo diphenyl oxide (Deca bromodiphenyl oxide, referred to as Deca) and both are used together, and the finished product is then subjected to various physical properties. The physical properties measured are also listed in Table 2.

<Comparative example 1>

The same operating conditions as in Example 1, but without adding the graft copolymer (C), the finished product was also tested for various physical properties, and the results are also shown in Table 2.

<Comparative example 2>

The operating conditions are the same as in Example 1, but no propylene-based copolymer (B) is added to the graft copolymer (C), and the physical properties of the formed test piece are also measured, and are listed in Table 2.

<Comparative example 3>

With the operating conditions of Example 1, but rubber graft copolymer (A) and propylene-based copolymer (B) are not added in the graft copolymer (C), the finished product is also tested for various physical properties, and the results are also are presented in Table 2.

<Comparative example 4>

The same operating conditions as in Example 1, but without adding the graft copolymer (D), the finished product was also tested for various physical properties, and the results are also shown in Table 2.

<Comparative example 5>

The operating conditions are the same as in Example 1, but the amount of flame retardant added is less than 5 parts by weight. The finished product is also tested for various physical properties, and the results are also shown in Table 2.

<Comparative example 6>

The operating conditions are the same as in Example 1, but the added graft copolymer (C) is excessive, and the finished product is also tested for various physical properties, and the results are also shown in Table 2.

From the test results of Comparative Example 1, it can be seen that if the graft copolymer (C) is not added in the resin composition of the present invention, not only the heat resistance and surface impact strength of the resin are not good, but the gas burn mark of the molded product is also serious; The test results of 2 show that when the graft copolymer (C) does not contain the propylene-based copolymer (B), the appearance of the molded product is poor, and when the graft copolymer (C) does not add the rubber graft copolymer (A) and propylene-based copolymer (B), the surface impact strength of the resin is not good, as can be seen from the test results of Comparative Example 3; The surface impact strength is obviously insufficient, which can be proved by the test results of Comparative Example 4; and shown by the test results of Comparative Example 5, when the amount of flame retardant in the resin composition is insufficient, its flame retardancy cannot pass the test, and When the addition amount of the graft copolymer (C) exceeds 60% (weight), it will cause poor surface impact strength, which can be proved by the test results of Comparative Example 6.

Looking at Examples 1-6 again, the present invention can indeed make the resin have good flame retardancy, high heat resistance, and simultaneously have excellent surface impact strength, resistance to gas burn marks and The good appearance of molded products and other properties make the flame retardant styrene resin composition more perfect in physical properties and can be used in industry.

The above description is only to illustrate the present invention by way of example rather than to limit it. It will be apparent to those skilled in the art that modifications or variations of the present invention can be made within the spirit and scope of the present invention.

Table 1 (parts by weight) No. of graft copolymer (C) (C-1) (C-2) (C-3) (C-4) (C-5) (C-6) Rubber Graft Copolymer (A) (A-1) 1.4 (A-1) 1.4 (A-2) 5.6 (A-2) 2.9 -0 (A-1) 2.7 Diene rubber 7.0 7.0 4.2 5.8 11.6 5.5 Propylene-Based Copolymer (B) (B-1) 1.4 (B-1) 2.3 (B-2) 3.6 (B-1) 4.3 -0 -0 Styrene 74.4 70.4 70.0 76.0 74.4 76.0 Acrylonitrile 25.6 25.6 24.0 24.0 25.6 24.0 Methyl methacrylate 0 0 6.0 0 0 0 N-phenylmaleimide 0 4.0 0 0 0 0

Table 2 experiment number Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Comparative example 1 Comparative example 2 Comparative example 3 Comparative example 4 Comparative Example 5 Comparative example 6 ingredients Graft copolymer (C) parts by weight (C-1) 30.0 (C-2) 20.0 (C-3) 50.0 (C-4) 40.0 (C-1) 35.0 (C-1) 40.0 0 (CB)30.0 (C-5) 50.0 (C-1) 80.0 (C-1) 30.0 (C-1) 85.0 Graft copolymer (D) parts by weight 25.0 27.0 22.0 24.0 24.0 30.0 31.0 25.0 19.0 0 25.0 15.0 Copolymer (E) parts by weight 45.0 53.0 38.0 36.0 45.0 30.0 89.0 45.0 31.0 40.0 45.0 0 Flame retardant parts by weight (EC-14)16.4 (EC-14)16.4 (TBBA) 19.7 (TBBA) 19.7 (EC-14)16.4 8(DEcA)8.4(EC-14) (EC-14)16.4 (EC-14)16.4 (EC-14)16.4 (EC-14)16.4 (EC-14)4.0 (EC-14)46.4 Chlorinated polyethylene parts by weight 10.0 10.0 12.0 12.0 4.0 0 10.0 10.0 10.0 10.0 10.0 10.0 Physical property test Heat resistance (℃) 97 98.5 93 95.5 96 96.5 89.5 94.5 96.1 97.8 100 99 Surface impact strength (kg.cm) 300 320 350 340 310 290 260 290 250 250 340 240 Anti-gas burn ○ ○ ○ ○ ○ ○ x ○ ○ ○ ○ ○ Exterior ○ ○ ○ ○ ○ ○ ○ x ○ ○ ○ C Flammability ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ x ○ Note: 1.EC-14 is a brominated epoxy resin with a bromine content of 59%.

2. TBBA is tetrabromobisphenol A with a bromine content of 59%

3. DECA is Deca bromo diphenyl oxide.

Claims (3)

1, a kind of fireproof styrene resin composite mainly comprises:

(1) 100 parts by weight of styrene is a resin, and it comprises:

The graft copolymer of (1) 2～60 weight part (C), this graft copolymer (C) monomer mixture that to be the diene series rubber of rubber graft copolymer (A), 2～25 weight parts of 0.05～0.8 μ m and 0.1～10 weight part propenyl based copolymer (B) by 0.1～10 weight part weight average particle diameter be made up of the copolymerizable monomer of the acrylic monomer of the styrenic monomers of 45～80 weight parts, 15～50 weight parts and 0～40 weight part with 100 weight parts carries out the graft copolymer that body and/or solution polymerization obtain;

The graft copolymer of (2) 5～60 weight parts (D), this graft copolymer (D) are to be that styrenic monomers, acrylic monomer and the optional monomer mixture that other copolymerizable monomer mixed of the rubber latex of 0.05～0.8 μ m and 15～50 weight parts carries out the graft copolymer that the emulsification graft polymerization obtains by 50～85 weight part weight average particle diameter;

The multipolymer of (3) 0～80 weight parts (E), this multipolymer (E) are to be that monomer, 20～50 parts by weight of acrylonitrile are that other optional copolymerizable monomer of monomer and 0～40 weight part are carried out polymerization and the multipolymer that obtains by 50～80 parts by weight of styrene; And

The content of halogen of (two) 5～40 weight parts is the above organic incombustible agent that contains the fontanel element of 40% (weight).

2. composition as claimed in claim 1 wherein can further add the chlorinatedpolyethylene of 1～20 weight part.

3. composition as claimed in claim 1, wherein, the described organic incombustible agent that contains the fontanel element is decabrominated dipheny base ether, octabromodiphenyl base ether, tetrabromo-bisphenol, brominated epoxy resin, tetrabromo phthalimide ethane, decabrominated dipheny methylmethane, decabrominated dipheny base ethane.