JPH072959A - High-impact styrene resin composition and its production - Google Patents

Abstract

PURPOSE:To provide a high-impact styrene resin composition being halogen-free, excelling in heat stability, storage stability and gloss and having sufficient impact resistance-by using a specified coupling agent and using a conjugated diene rubber having a specified branched structure. CONSTITUTION:The resin composition is produced by radicalpolymerizing 2-25wt.% branched structure conjugated diene rubber prepared by polymerizing a conjugated diene monomer with optionally a comonomer in a hydrocarbon solvent in the presence of an organolithium compound as an initiator, coupling the obtained living polymer with an alkoxysilane of the formula (wherein R is 1-10C alkyl or aryl; and x is 0 or 1) at 70-120 deg.C and treating the coupled polymer with an inorganic acid or an organic acid and satisfying the properties: (A) the coupled polymer has three specified peak molecular weights, (B) the Mooney viscosity at 100 deg.C is 20-90, and (C) the 5% styrene solution viscosity at 25 deg.C is 20-300cps with 98-75wt.% styrene monomer (mixture) by a bulk polymerization process, a bulk/suspension polymerization process or a solution polymerization process.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a shock-resistant and glossy resin reinforced by a conjugated diene polymer which has a specific branched structure with a specific coupling agent and is excellent in thermal stability and storage stability. The present invention relates to an impact-resistant styrene resin composition having excellent balance and a method for producing the same.

[0002]

2. Description of the Related Art Polystyrene is widely used in various applications because it has excellent rigidity, transparency, luster and the like and has good moldability. However, this polystyrene has a major drawback of being inferior in impact resistance, and various unvulcanized rubbers are used as a toughening agent in order to improve this drawback. Among them, impact-resistant styrene-based resin compositions in which a styrene-based monomer is radically polymerized in the presence of unvulcanized rubber and a styrene-based polymer is graft-polymerized on a rubber-like polymer are industrially widely produced. As unvulcanized rubber used for this purpose, there are polybutadiene rubber and styrene-butadiene copolymer rubber, and in particular, polybutadiene rubber is widely used for imparting excellent impact resistance.

Conventionally, as this butadiene rubber used for imparting impact resistance, a branched rubber coupled with a polyhalogenated silicon compound such as tetrachlorosilane is generally used, but after the coupling reaction. ,
Since a chlorine-containing compound such as LiCl is produced as a by-product, it is desired to reduce the amount of halogen compounds present in rubber in the production of the impact resistant styrene resin.

Therefore, various halogen-free coupling agents have been proposed. For example, a method of reacting a polycarboxylic acid diester such as adipic acid diester [eg, US Pat. No. 3,594,452 (Japanese Patent Publication No.
No. 14132)] is proposed, but there is a problem that the performance of the polymer is inferior because the coupling efficiency is low and the molecular weight does not increase uniformly. Further, a method of reacting with a polyepoxy compound such as epoxidized liquid polybutadiene or epoxidized vegetable oil [eg, US Pat.
81383 Specification (Japanese Patent Publication No. 49-36957)
However, uniform coupling is not performed, and the performance of the obtained polymer is not sufficient.

In addition to these, polyisocyanates, polyimines, polyaldehydes, polyketones, polycarboxylic acid anhydrides, etc. have been proposed, but all of them have unstable compounds, low coupling efficiency, and heat There are practical problems such as poor stability. As described above, at present, a branched conjugated diene rubber that does not contain halogen and has excellent thermal stability and storage stability of the polymer and excellent performance for imparting impact resistance has not yet been found. is there.

[0006]

SUMMARY OF THE INVENTION The present invention is reinforced with a branched conjugated diene rubber which does not contain halogen and is excellent in thermal stability and storage stability, and has an excellent balance of physical properties of impact resistance and gloss. It is an object of the present invention to provide a high impact styrene resin composition.

[0007]

The inventors of the present invention have studied the impact-resistant styrenic resin which is reinforced with a halogen-free rubber and has an excellent balance of gloss and impact resistance. The inventors have found that the above object can be achieved by using a specific coupling agent that has not been studied as an agent and a conjugated diene rubber having a specific branched structure, thereby completing the invention.
That is, the present invention was obtained by polymerizing at least one type of conjugated diene monomer and optionally at least one type of copolymerizable monomer in a hydrocarbon solvent using organolithium as an initiator. The living polymer is represented by the following general formula

[0008]

[Chemical 3] (Wherein R represents the same or different C1-10 alkyl group or aryl group, x is an integer of 0 or 1), and the reaction temperature is in the range of 70 to 120 ° C. (A) is a polymer which is further treated with at least one kind of inorganic acid or organic acid after being coupled with, and the coupled polymer has a peak molecular weight in terms of polystyrene measured by GPC of the polymer before coupling ( Mwp) 1.5-2.
5-40% by weight of rubber having 5 times the molecular weight, 2.5
25-80% by weight of rubber having a molecular weight of ~ 3.5 times,
Containing 3 to 40% by weight of a rubber having a molecular weight of 5 times or more, (B) Mooney viscosity (M
L _{1 + 4} , 100 ° C) is 20 to 90 (C) 5 at 25 ° C
Weight% styrene solution viscosity (5% SV) is 20-300c
Impact-resistant styrene-based resin composition containing 2 to 25% by weight of branched conjugated diene-based rubber of ps, at least one conjugated diene-based monomer, and optionally at least one copolymerizable monomer And are polymerized in a hydrocarbon solvent using organolithium as an initiator, and the resulting living polymer is represented by the following general formula:

[0009]

[Chemical 4] (Wherein R represents the same or different C1-10 alkyl group or aryl group, x is an integer of 0 or 1), and the reaction temperature is in the range of 70 to 120 ° C. Is a polymer further treated with at least one kind of inorganic acid or organic acid after being coupled with, and the (A) coupled polymer is a polystyrene-equivalent peak molecular weight (Mwp measured by GPC of the polymer before coupling). ) 1.5-2.5
5-40% by weight of rubber having a double molecular weight, 2.5-
25 to 80% by weight of rubber having a molecular weight of 3.5 times,
Containing 3 to 40% by weight of a rubber having a molecular weight of 5 times or more, (B) Mooney viscosity at 100 ° C. (ML _{1 + 4} ,
2 to 25% by weight of a branched conjugated diene rubber having a viscosity of 5% by weight styrene solution (5% SV) at 20 to 90 ° C. (20 ° C.) of 20 to 300 (C) and 20 to 300 cps, and a styrene monomer. Or 98 to 75% by weight of a mixture of a styrene monomer and a copolymerizable monomer is radically polymerized by a bulk polymerization method, a bulk suspension polymerization method or a solution polymerization method. A method for producing a resin composition is provided.

The present invention will be described in detail below. The branched conjugated diene-based polymer used in the present invention has at least 1
A type of conjugated diene-based monomer and, if necessary, at least one type of copolymerizable monomer are polymerized in a hydrocarbon solvent using organic lithium as an initiator, and the resulting living polymer is specified. It can be produced by coupling with the alkoxysilane compound of.

The organolithium compound used in the present invention may be a monoorganolithium compound or a polyfunctional organolithium compound, or a mixture of a monoorganolithium compound and a polyfunctional organolithium compound.
Examples of the organic monolithium compound include n-propyllithium, iso-propyllithium, n-butyllithium, sec-butyllithium, tert-butyllithium, benzyllithium and the like, but preferably n-butyllithium and sec-butyl. Lithium or the like is used.

As the polyfunctional organolithium compound, for example, dilithiomethane, 1,4-dilithiobutane, 1,6
-Dilithiohexane, 1,4-dilithiocyclohexene, 1,4-dilithio-2-ethylcyclohexane,
1,3-dilithio-4-phenylbutane, 1,2-dilithio-1,2-diphenylethane, 1,10-dilithiodecane, 1,20-dilithioeicosane, 1,1-dilithiodiphenylene, 1, 4-dilithiobenzene, 1,5
-Dilithionaphthalene, dilithiopolybutadiene, dilithioisoprene, dilithiodiisoprene, dilithiopolyisoprene, 2,2'-2 "-trilithio-p-ta-phenyl, 1,3,5-trilithiobenzene, 1 , 3, 5
-Trilithio-2,4,6-triethylbenzene and the like.

In addition to the above, an organolithium compound containing a substantially polyfunctional organolithium compound obtained by reacting a monoorganolithium compound with another compound may be used. Of these examples, a particularly representative catalyst is a reaction product containing a monoorganolithium compound and a polyvinylaromatic compound.

For example, a reaction product of a monoorganolithium compound and a polyvinyl aromatic compound (Japanese Patent Application Laid-Open No. 48-103).
690), a reaction product obtained by reacting a monoorganolithium compound with a conjugated diene or a monovinylaromatic compound and then reacting with a polyvinylaromatic compound, a monoorganolithium compound, a conjugated diene or a monovinylaromatic compound, and polyvinyl. A reaction product (West German Patent No. 2,003,384) obtained by simultaneously reacting the three aromatic compounds is used.

Further, as shown in Japanese Patent Publication No. 37078/1975, a reaction product of a monoorganolithium compound and a monovinylaromatic compound is reacted with a polyvinylaromatic compound, and then a monovinylaromatic compound is further added. The catalyst obtained by the reaction is also effective.

As the hydrocarbon catalyst, aliphatic hydrocarbons such as butane, pentane and hexane, alicyclic hydrocarbons such as cyclopentane and cyclohexane, and aromatic hydrocarbons such as benzene, toluene and xylene are used. Hexane and cyclohexane are preferred examples.

Further, polar compounds such as Lewis basic compounds generally used as a microstructure modifier for conjugated diene units or randomizers such as tetrahydrofuran, N, N, N ', N'-tetramethylethylenediamine, etc. You may use what was added to the hydrocarbon solvent.

The conjugated diene-based monomer used in the present invention is
1,3-butadiene, isoprene, 2,3-dimethyl-
1,3-butadiene, 1,3-pentadiene, 3-methyl-1,3-pentadiene, 1,3-heptadiene,
Examples of the conjugated diene such as 1,3-hexadiene and the monomer copolymerizable with these conjugated dienes include styrene, α-methylstimen, p-methylstyrene, divinylbenzene, methyl acrylate, methyl methacrylate and acrylonitrile. Yes, these are used alone or in combination of two or more. Preferred conjugated diene-based monomers are 1,3-butadiene and isoprene. Styrene is a preferred example of the monomer copolymerizable with the conjugated diene.

When the polymer having an active lithium terminal of the present invention is a copolymer comprising the conjugated diene and a monomer copolymerizable therewith as described above, the content of the copolymerizable monomer, or The chain distribution of the copolymerizable monomer in the copolymer chain is not particularly limited. Further, regarding the composition distribution of the conjugated diene and the copolymerizable monomer in the copolymer chain, the composition may be uniform in the molecular chain, or may be unevenly distributed in the molecular chain. It may exist as a block. The coupling agent used in the present invention has the following general formula:

[0020]

[Chemical 5] (In the formula, R represents an alkyl group or an aryl group having 1 to 10 carbon atoms which are the same or different, and x is an integer of 0 or 1), and examples thereof include tetramethoxysilane and tetraethoxysilane. , Methyltrimethoxysilane, ethyltrimethoxysilane, tetrabutoxysilane, tetraphenoxysilane, and the like, and these can be used alone or in combination of two or more. Tetramethoxysilane is mentioned as a preferable coupling agent.

The amount of these coupling agents to be used is 0.05 mol times or more, preferably 0 mol, per mol of the organolithium compound catalyst used when producing a polymer having an active lithium terminal. It is in the range of 0.1 to 0.4 times mol.

The reaction between the polymer having an active lithium terminal and the compound takes place immediately when they come into contact with each other, so that the reaction time can be adjusted over a wide range, but the reaction time is usually 1 minute to 3 hours, preferably 1 minute. ~ 60 minutes.

These compounds may be used as they are or may be used by dissolving them in a solvent, but when a solvent is used, a hydrocarbon solvent which is inactive to active lithium is used. Examples of hydrocarbon solvents are benzene, toluene,
Cyclohexane, n-hexane, etc. can be mentioned. Further, the method of adding the compound is not particularly limited, but a method of adding in a batch system or a continuous system is generally used.

The reaction temperature of the polymer having an active lithium terminal and the compound is in the range of 70 ° C to 120 ° C, preferably 80 ° C to 115 ° C. When the reaction temperature exceeds 120 ° C., the coupling efficiency is remarkably reduced and the branched rubber having the specific structure of the present invention cannot be obtained. On the other hand, if the temperature is lower than 70 ° C., the reactivity with the compound is remarkably lowered and the branched rubber having the specific structure of the present invention cannot be obtained.

The treating agent added after the coupling used in the present invention is at least one compound selected from inorganic acids and organic acids. Examples of inorganic acids include sulfuric acid, nitric acid, phosphoric acid, boric acid, and other carbonic acids.

The organic acid is an organic compound having acidity in a broad sense, and examples thereof include compounds such as carboxylic acid, sulfonic acid, and sulfinic acid, and the organic compound having a carboxyl group is preferable. For example, propionic acid, benzoic acid, caprylic acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, oxalic acid, glutaric acid, adipic acid, malonic acid, oleic acid,
Examples thereof include linoleic acid and the like or a mixture thereof. Of these, sulfuric acid, carbonic acid, and stearic acid are particularly preferable.

The amount of the inorganic acid or organic acid used is preferably 0.05 to 5 mol, more preferably 0.1 to 1 mol, per 1 mol of the organolithium compound catalyst used when producing a polymer having an active lithium terminal. It is in the range of 3 to 3 moles. When the amount is less than 0.05 mol, the resulting branched polymer is inferior in storage stability and thermal stability, which causes a decrease in surface gloss of the impact-resistant styrene-based resin and a fish eye, which is not preferable. In addition, the color tone of the rubber also deteriorates. On the other hand, if the amount exceeds 5 mols, the storage stability and the thermal stability are greatly deteriorated, which is not preferable.

The method of adding the compound is not particularly limited, but a method of adding it to the polymer solution in a batch system or a continuous system after completion of the coupling reaction is generally used.

Recovery of the polymer from the polymer solution is carried out by adding a stabilizer to prevent the polymer from oxidative deterioration or thermal deterioration when the solvent is removed, and then using a known polymer separation method. For example, the branched polymer used in the present invention can be obtained through steam stripping and drying steps. The stabilizer may be any known stabilizer that has been used conventionally, such as 2,6-di-tert-butyl-4-methylphenol, n-octadecyl-3- (3 ', 5'.
-Di-tert-butyl-4'-hydroxyphenyl)
Phenolic compounds such as propionate, Tris-
Organic phosphite compounds such as (2,4-di-tert-butylphenyl) phosphite, sulfur-containing phenol compounds such as 2,4-bis [(octylthio) methyl] -0-cresol, or n-octadecyl-
3- (3 ', 5'-di-tert-butyl-4'-hydroxyphenyl) propionate and tris- (2,4
Various known antioxidants such as a combination of phenol-based compounds such as -di-tert-butylphenyl) phosphite and organic phosphite-based compounds are used.

In the rubber-like polymer used in the present invention, the coupled polymer is the polymer G before coupling.
5 to 40% by weight of a rubber having a molecular weight of 1.5 to 2.5 times the polystyrene-converted peak molecular weight (Mwp) measured by PC, and 25 to a rubber having a molecular weight of 2.5 to 3.5 times. 80% by weight, 3 to 40% by weight of a rubber having a molecular weight of 5 times or more, is a conjugated diene polymer having a specific branched structure, and preferably a branched rubber:
5 to 30% by weight of branched rubber: 30 to 65% by weight,
Branched rubber: 5 to 25% by weight.

If the branched rubber exceeds 40% by weight, the cold flow during storage is extremely large and there are problems in storage and transportation, and the desired impact resistant styrene resin cannot be obtained. Is out of the range of 25 to 80% by weight, the impact-resistant styrenic resin of the present invention having an excellent balance of impact resistance and gloss physical properties cannot be obtained. Also,
If the content of the branched rubber is less than 3% by weight, the impact resistance is insufficiently improved, and if it exceeds 40% by weight, the gloss of the resulting impact-resistant styrene resin is greatly reduced, which is not preferable.

The Mooney viscosity (ML _{1 + 4} , 100 ° C.) of the branched conjugated diene rubber used in the present invention is 20 to 90, preferably 25 to 70, and 5% by weight measured at 25 ° C.
Styrene solution viscosity (5% SV) is 20-300 cp
s, preferably 20 to 150 cps.

The Mooney viscosity (ML _{1 + 4} , 100 ° C.) is
Less than 20 or 5wt% styrene solution viscosity is 20cp
When a conjugated diene rubber having a s of less than s is used, the impact resistance of the resulting impact resistant styrene resin is not sufficient. If the Mooney viscosity (ML _{1 + 4} , 100 ° C) exceeds 90,
Alternatively, when a conjugated diene rubber having a 5 wt% styrene solution viscosity of more than 300 cps is used, it is often used for dissolving the conjugated diene rubber in the styrene monomer and transferring the solution during industrial production. And the increase in the viscosity of the polymerization solution lowers the heat transfer efficiency, making it difficult to control the polymerization temperature and making it difficult to obtain a homogeneous composition.

The conjugated diene rubber in the present invention has some influence on the impact resistance of the resulting impact resistant styrene resin composition due to its microstructure. For example, when polybutadiene is used as the conjugated diene rubber. Is
The 1,2-vinyl content is preferably 10 to 80%, and the cis-1,4 content is preferably in the range of 10 to 85%. In particular, the 1,2-vinyl content is 10 to 40%. More preferably, 10 to 25% is more preferable, and when a polybutadiene having a 1,2-vinyl content outside this range is used, the resulting impact-resistant styrene resin has poor impact resistance.

There are no particular restrictions on the method for adjusting the 1,2-vinyl content, and any conventionally known method can be used. For example, when polymerizing a conjugated diene rubber, dimethyl ether, diethyl ether, It is achieved by adding ethers such as tetrahydrofuran (THF); amines such as dimethylamine; thioethers such as dimethyl sulfide and diethyl sulfide to carry out polymerization.

Further, hexamethylphosphoramide (H
MPA) is added (Japanese Patent Publication No. 43-5904), tetramethylethylenediamine (TMEDA) is added (Japanese Patent Publication No. 42-17199), and diethylene glycol dimethyl ether is added. The 1,2-vinyl bond may be polymerized so as to be uniform in the molecular chain, or may be polymerized so as to gradually change along the molecular chain (Japanese Patent Publication No. 48-875). (U.S. Pat. No. 3,301,840), and further polymerized so as to be bound in blocks (US Pat.
You may.

In order to polymerize the 1,2-vinyl bond so as to be uniform in the molecular chain, the polymerization initiation temperature is usually 30 to 90.
℃, the method of low temperature polymerization as possible is adopted, and in order to polymerize the 1,2-vinyl bond so as to gradually change along the molecular chain, a method of performing the polymerization at elevated temperature, That is, a method in which the polymerization initiation temperature is usually 30 to 80 ° C. and the polymerization termination temperature is 85 to 120 ° C. is adopted.

The impact-resistant polystyrene resin composition of the present invention is a styrene resin composition containing 2 to 25% by weight of the above-mentioned conjugated diene rubber, and when the amount of rubber used is less than 2% by weight, the present invention can be used. The target effect of improving impact resistance is insufficient. On the other hand, when the amount used exceeds 25% by weight, the impact resistance is improved, but the original characteristics of polystyrene resin, such as tensile strength / rigidity, gloss, etc. Is unfavorable because the appearance of the product is impaired.

The method for obtaining the impact resistant styrene resin composition of the present invention is not particularly limited as long as it is considered so as to satisfy the requirements of the present invention, and a known method can be used. Usually, a mixture of 2 to 25% by weight of the conjugated diene rubber of the present invention and a styrene monomer or a monomer copolymerizable with the styrene monomer is 98 to 75% by weight.
Is subjected to radical polymerization by a bulk polymerization method, a bulk-suspension polymerization method or a solution polymerization method to produce an impact resistant styrene resin.

Bulk polymerization, which is one of the preferred methods for obtaining the impact-resistant polystyrene resin composition of the present invention, generally involves first dissolving the conjugated diene rubber of the present invention in styrene, and if necessary, Diluents such as toluene and ethylben, liquid paraffin, mineral oil, internal lubricants such as organic polysiloxane, antioxidants, mercaptans and α-methylstyrene dimer, etc. are added.
In the catalytic polymerization using a radical initiator as a catalyst, the polymerization operation of styrene is continued at a lower temperature than usual, for example, a temperature of 60 to 180 ° C.

In the case of catalytic polymerization, 1,1 is used as an initiator.
-Bis (t-butylperoxy) cyclohexane, 1,
Peroxyketals such as 1-bis (t-butylperoxy) 3,3,5-trimethylcyclohexane; di-t
-Butyl peroxide, 2,5-dimethyl-2,5-
Dialkyl peroxides such as di (t-butylperoxy) hexane and dicumyl peroxide; diacyl peroxides such as benzoyl peroxide, m-toluoyl peroxide and lauroyl peroxide;
Peroxydicarbonates such as dimyristyl peroxydicarbonate and diisopropyl peroxydicarbonate; t-butyl peroxyisopropyl carbonate, t-butyl peroxyacetate, di-t-butyl diperoxy isophthalate, t-butyl percarbonate Peroxyesters such as oxybenzoate; Ketone peroxides such as cyclohexanone peroxide and methyl ethyl ketone peroxide; Hydroperoxides such as p-mentha hydroperoxide, t-butyl hydroperoxide and cumene hydroperoxide; Azobis Azo compounds such as isobutyronitrile and azobiscyclohexanecarbonitrile are used.

These are used alone or in combination of two or more, and if necessary, chain transfer agents such as mercaptans, α-methylstyrene linear dimer,
Terpinolene or the like can be used. Further, in this bulk polymerization method, an organic polysiloxane as an internal lubricant, for example, polydimethylsiloxane may be added in an amount of 0.005 to 10 parts by weight based on 100 parts by weight of the polymer, if desired.

If the unreacted styrene is contained in the polymer after completion of the polymerization, the styrene is removed by a known method, for example, a method of removing under reduced pressure or an extruder designed for the purpose of removing volatile matter. It is desirable to do.

Stirring can be carried out during the bulk polymerization, if necessary. However, after the conversion of styrene into a polymer, that is, the polymerization rate has reached 60% or more, the stirring may be stopped or alleviated. Desirably, excessive stirring may reduce the strength of the obtained polymer, and if necessary, the polymerization is carried out in the presence of a small amount of a diluent such as toluene or ethylbenzene, and after the completion of the polymerization, these diluents are added together with unreacted styrene. It may be removed by heating.

The bulk suspension polymerization method is also useful in the production of the impact-resistant styrene resin composition of the present invention. In this method, the first half of the polymerization is carried out by the bulk polymerization and the second half of the reaction is suspended. It is carried out by polymerization. That is, the styrene solution of the conjugated diene rubber of the present invention, as in the case of the bulk polymerization,
Usually, 50% or less, particularly preferably 10 to 40% of styrene is partially polymerized by a bulk polymerization method by carrying out heat polymerization or catalyst-added polymerization without a catalyst, and then this partially polymerized mixture is suspended. In the presence of a turbidity stabilizer or a combination of this and a surfactant, the suspension is dispersed in an aqueous medium while stirring, and the second half of the reaction is completed by a suspension polymerization method.

The produced polymer is washed, dried and, if necessary, pelletized or powdered before use. In addition to the above, a useful impact-resistant polystyrene resin composition can be obtained by a conventionally known method that is an improvement or improvement of these methods.

Further, a part of styrene forming the impact resistant styrene resin composition together with the conjugated diene rubber of the present invention may be replaced with a monomer capable of radical polymerization with styrene other than styrene. Such a monomer is used in the range of 50% by weight or less in the monomer containing styrene, and as the copolymerizable monomer other than styrene, for example, α-
Examples include monovinyl aromatic hydrocarbons such as methylstyrene, vinyltoluene, vinylethylbenzene, vinylxylene, and vinylnaphthalene; conjugated dienes such as butadiene and isoprene; acrylonitrile; methyl methacrylate; You may use 2 or more types.

The gel content (toluene insoluble content) in the impact-resistant styrene resin composition thus obtained is preferably in the range of 10 to 40% by weight, and the gel content in the resin composition is Swelling index in toluene is 7 to 13
Further, the weight average molecular weight of the resin portion is preferably 100,000 to 400,000, and more preferably 150,000 to 300,000.

Since the amount of the styrene oligomer remaining in the resin affects the heat resistance, it is usually preferably 1% by weight or less, and particularly 0.5% by weight or less when heat resistance is required.

The impact-resistant styrenic resin composition of the present invention can be molded into a wide variety of practically useful products by a molding method such as injection molding and extrusion molding. Accordingly, various additives such as antioxidants, ultraviolet absorbers, flame retardants, lubricants, release agents, fillers, organic polysiloxanes, and other thermoplastic resins such as polystyrene for general use, methacrylic resin, polyphenylene ether, polycarbonate , Styrene / butadiene block copolymer resin, methyl methacrylate / styrene copolymer resin, maleic anhydride / styrene copolymer resin, polyamide resin, polyester resin, etc.

[0051]

The impact-resistant styrenic resin of the present invention thus obtained does not contain halogen as compared with the conventional impact-resistant styrenic resin, and has heat stability, storage stability and gloss. As it is excellent and has sufficient impact resistance, it can be used in electronic devices such as TVs and VTRs, household electric appliances such as air conditioners and refrigerators, general equipment such as office automation equipment, stationery, toys, leisure sports goods, and household items. It has an industrially excellent effect that it can be used in a wide variety of applications such as goods, building materials / household parts, and food containers.

[0052]

EXAMPLES Hereinafter, specific examples of the present invention will be shown by examples, but this is for more specifically explaining the gist of the present invention and does not limit the present invention.
Various measurements were made by the following methods.

(Moonie viscosity) It is a value of ML _{1 + 4} (100 ° C.). (5 wt% styrene solution viscosity) The viscosity was measured at 25 ° C. using a Canon Fenske viscometer.

(Cold flow property) A cube having one side of 50 mm was prepared from the polymer, a weight of 1 kg was applied from the upper part of the cube, and the rate of change in height after 60 minutes at 25 ° C. was measured. For the determination of cold flow property, the rate of change in height is 0 to 5%: ⊚, 5 to 15%: ∘, 15 to 25%: Δ, 2
5% or more: Poor

(Microstructure) Using an infrared spectrophotometer,
For polybutadiene, the morelo method [La chimi
ca EL'industria 41 , 758 (19
58)] and the styrene-butadiene copolymer by the Hapton method [Analytical Chemis].
try, 21 , 923 (1949)].

(Measurement of Polymer Constituents) Molecular weight is GPC
It is a value measured and calculated by (gel permeation chromatography). GPC measurement conditions Measurement model Waters M-8000 type solvent THF (tetrahydrofuran) column DuPont Zolbax (ZORBAX) PSM 1000S 2 Zolbax (ZORBAX) PSM 60S 1 column temperature 35 ° C Liquid flow rate 0.7 ml / min Liquid sending pressure 800 psi Sample concentration 0.1 wt% Sample liquid amount 0.1 ml Detector Differential refractometer.

Under the above conditions, standard polystyrene (manufactured by Waters; monodisperse polystyrene, molecular weight 1,440,47)
10,000, 110,000, 35,000, 8500, 2350) GPC
It was measured to obtain the retention capacity of the peak position (hereinafter abbreviated as V _R), to construct a correlation curve between the molecular weight and V _R.
Mwp was measured by GPC of the polymer, and V _{R at the} peak position was measured.
Was obtained from the correlation curve. From the GPC chart for which Mwp was obtained, V _R corresponding to the molecular weight range of ,,, was obtained from the correlation curve, and the respective area ratios were calculated.
% Of the molecular weight part of

(Static Thermal Stability Test) A stabilizer-prepared polymer composition sheet having a length and width of 5 cm and a thickness of 0.5 cm was placed in an oven heated to 80 ° C., and the test time was 5 hours, 10 hours, and 15 hours. The coloring property and toluene insoluble content of each sheet were measured after 20 hours. The coloring property was represented by the following coloring degree rank. Coloring rank: No change (white) = 0, pale yellow = 1, pale yellow = 2, yellow = 3, toluene insoluble matter (wt%) is obtained by dissolving 5 g of the polymer composition after heating in 100 g of toluene,
It was rubbed with a 100-mesh wire net and the residue of the wire net was dried and then calculated as a toluene insoluble content.

(Heat stability during shearing) Using a Labo Plastomill (LPM-2500-200) manufactured by Toyo Seiki Co., Ltd.
Test temperature (cylinder temperature) 80 ° C, rotor rotation 10
At 50 rpm, 50 g of the polymer composition was added for 2 minutes, and pre-kneading was performed for 5 minutes, then immediately set to 150 rpm, the torque value gradually decreased, and then gelation started and torque increase started. The lowest point of the torque value was measured as the gelation start time. Further, the butadiene-styrene block copolymer has a test temperature (cylinder temperature) of 190 ° C.
After pre-kneading at a rotor rotation of 10 rpm for 20 minutes, the rotation speed was immediately increased to 120 rpm for measurement. Fig. 1 shows a Labo Plastomill kneading test chart.

(Izod impact strength) The obtained composition was compression-molded to prepare a test piece having a thickness of 3.2 mm, which was measured by JIS.
-Measured according to K-7110. (Gloss) Using a dumbbell test piece injection-molded according to ASTM D-638, the glossiness (incident angle 60 °) of the gate portion and the end gate portion was measured and averaged according to ASTM D-523. (Rubber particle diameter) It was measured using a Coulter counter method and expressed as a 50% median diameter.

Examples 1 to 11 and Comparative Examples 1 to 3 (1) Production of branched polymer sample An autoclave equipped with a stirrer and a jacket having an internal volume of 10 l was washed and dried, and after purging with nitrogen, purified and dried in advance 1 , 3-butadiene 700g and cyclohexane 5000
g, then tetrahydrofuran as a 1,2-vinyl modifier, and n as an organolithium initiator.
A 10 wt% n-hexane solution of -butyllithium was added to initiate polymerization at 65 ° C.

Then, tetramethoxysilane or tetraethoxysilane was added to the rigging polymer at the temperature shown in Table 1 and reacted for 30 minutes. Further, the amount of stearic acid or carbon dioxide shown in Table 1 was added to the polymer solution. Carbon dioxide is 3 kg / cm ² (gauge pressure)
5 mol of water was brought into contact with 1 mol of the organolithium compound under pressure, and this was added to the polymer solution.

To the polymer solution thus obtained, 100 parts by weight of the polymer were added 2,6-di-tert-butyl-4-methylphenol and tris- (2,4-di-tert-butylphenyl) phosphite as stabilizers. 0.5 parts by weight and 0.1 parts by weight, respectively, were added, and the solvent was removed by steam stripping. After dehydration, the polymer was dried with a hot roll (110 ° C.). Got

[0064]

[Table 1]

[0065]

[Table 2]

[0066]

[Table 3]

(Static Thermal Stability Test, Shear Thermal Stability Test) Sample No. Static thermal stability tests and thermal stability tests under shear were carried out using the branched polymers of 3, 5, 6, 8, 10, and 11. The results are shown in Tables 2 and 3. It can be seen that the acid-treated polymer has excellent gel suppression during heating and resistance to discoloration (yellowing resistance), and also has excellent shear heat stability.

[0068]

[Table 4]

[0069]

[Table 5]

(2) Production of high impact polystyrene High impact polystyrene was obtained by bulk polymerization described below using various branched rubbers shown in Table 1. Solvents, monomers, etc. were added to the stirrer and the reactor with jacket in the types and proportions shown in Table 4, and then the conjugated diene rubber sample No. 1 shown in Table 1 was added. Of polybutadiene rubber and n-octadecyl-3- (4'-hydroxy-
0.3 parts by weight of 3,5'-di-tert-butylphenol) propionate was added and dissolved by stirring.

To this, di-tert-butyl peroxide was added in an amount of 1 × 10 ^-4 mol per 1 mol of the monomer, and 1
Polymerization was carried out at 10 ° C. for 3 hours, 140 ° C. for 5 hours, and 180 ° C. for 2 hours. After further heating at 230 ° C. for 30 minutes, the unreacted product was removed under reduced pressure, and the obtained polymer was pulverized,
In some cases mineral oil and polydimethylsiloxane having a viscosity of 500 centistokes at 25 ° C. were added and pelletized in an extruder.

During the reaction, the average particle size of the rubber particle phase is 1-1.
The stirring number was controlled so as to be 7 μm. Table 4 shows the physical properties of the obtained impact resistant styrene resin. It can be seen that the impact-resistant polystyrene produced by using the rubber having the composition of the present invention is excellent in the balance between Izod impact strength and gloss.

[0073]

[Table 6]

[0074]

[Table 7]

[Brief description of drawings]

FIG. 1 shows a Labo Plastomill kneading test chart.

Claims (2)

[Claims] 1. Obtained by polymerizing at least one conjugated diene-based monomer and optionally at least one copolymerizable monomer in a hydrocarbon solvent using organolithium as an initiator. The living polymer is represented by the following general formula: (Wherein R represents the same or different C1-10 alkyl group or aryl group, x is an integer of 0 or 1), and the reaction temperature is in the range of 70 to 120 ° C. Is a polymer treated with at least one kind of inorganic acid or organic acid after being coupled with, and (A) the coupled polymer is a polystyrene-equivalent peak molecular weight (Mwp) measured by GPC of the polymer before coupling. 5 to 40% by weight of a rubber having a molecular weight of 1.5 to 2.5 times, and 2.5 to 3.
Containing 25 to 80% by weight of rubber having 5 times the molecular weight, 3 to 40% by weight of rubber having the 5 times or more molecular weight, (B) Mooney viscosity at 100 ° C. (ML _{1 +} 4,10)
Impact-resistant styrene containing 2 to 25 wt% of a branched conjugated diene rubber having a 5 wt% styrene solution viscosity (5% SV) at 20 ° C. of 20 to 90 (C) 25 ° C. of 20 to 300 cps. -Based resin composition. 2. A living body obtained by polymerizing at least one conjugated diene monomer and optionally at least one copolymerizable monomer in a hydrocarbon solvent using organolithium as an initiator. The polymer is represented by the following general formula: (Wherein R represents the same or different C1-10 alkyl group or aryl group, x is an integer of 0 or 1), and the reaction temperature is in the range of 70 to 120 ° C. (A) is a polymer which is further treated with at least one kind of inorganic acid or organic acid after being coupled with, and the coupled polymer has a peak molecular weight in terms of polystyrene measured by GPC of the polymer before coupling ( Mwp) 1.5-2.
5-40% by weight of rubber having 5 times the molecular weight, 2.5
25-80% by weight of rubber having a molecular weight of ~ 3.5 times,
Containing 3 to 40% by weight of a rubber having a molecular weight of 5 times or more, (B) Mooney viscosity (M
L _{1 + 4} , 100 ° C) is 20 to 90 (C) 5 at 25 ° C
Weight% styrene solution viscosity (5% SV) is 20-300c
2 to 25% by weight of a branched conjugated diene rubber having a ps of 98 to 75% by weight of a mixture of a styrene monomer or a monomer copolymerizable with the styrene monomer is subjected to a bulk polymerization method or a bulk suspension. A method for producing an impact-resistant styrene-based resin composition, characterized in that radical polymerization is carried out by a turbid polymerization method or a solution polymerization method.