TW201518371A - Vinyl aromatic hydrocarbon polymer composition and method for producing vinyl aromatic hydrocarbon polymer composition - Google Patents

Abstract

The present invention provides a vinyl aromatic hydrocarbon polymer composition which comprises a linear vinyl aromatic hydrocarbon polymer (A) and a branched vinyl aromatic hydrocarbon polymer (B). In addition, in the present vinyl aromatic hydrocarbon polymer composition, the linear vinyl aromatic hydrocarbon polymer (A) and the branched vinyl aromatic hydrocarbon polymer (B) contain specific components, the branched vinyl aromatic hydrocarbon polymer (B) is branched from, as a start point, a conjugated diene compound unit in a block copolymer constituted by the vinyl aromatic hydrocarbon and a conjugated diene, the amount of the block copolymer contained in the vinyl aromatic hydrocarbon polymer composition is, calculated by conjugated diene, 0.1 mass % or more and 2.0 mass % or less.

Description

Method for producing ethylene aromatic hydrocarbon polymer composition and ethylene aromatic hydrocarbon polymer composition

The present invention relates to a method for producing a vinyl aromatic hydrocarbon polymer composition and a vinyl aromatic hydrocarbon polymer composition.

Since styrene-based resin has excellent transparency, moldability, and rigidity, it is widely used as a molding material or food packaging material for home appliances, office products, accessories, and residential equipment. In recent years, from the viewpoint of resource saving and energy saving, it is required to have a thinner, lighter, and more productive product, and therefore it is required to have a material having high strength, rigidity, and moldability as a resin property.

Further, when the above-mentioned molding material is molded, a free surface such as a blow molding, a vacuum molding, an extrusion molding, a T stamper can be formed without being restricted by a stamper or a mold during the molding process using a molten resin. In the molding method such as molding or inflation molding, it is known that the higher the elongational viscosity (Elongational Viscosity) of the molding material, the better. When the elongational viscosity is increased, the molding stability of the molding material can be improved, that is, the finished product The thickness uniformity is increased. As a result, it can be easily formed into a complicated product shape, which is also advantageous for the strength of the molded article.

In general, methods for increasing the Extensional Viscosity are known to have ultrahigh molecular weight components. However, the inclusion of only the ultrahigh molecular weight component increases the tensile viscosity, but deteriorates the fluidity and workability of the resin. Therefore, in the molding processing such as blow molding, vacuum molding, extrusion molding, T compression molding, and inflation molding, a material having excellent adhesion, workability (flowability), and rigidity balance is required.

On the other hand, in the case of the patent document 1, the styrene resin composition which has the molecular weight component of 1 million or more in a predetermined range, and can improve fluidity and impact resistance, and the manufacturing method are proposed. Further, in Patent Document 2, a styrene resin composition in which a high molecular weight component obtained by anionic polymerization is mixed with a styrene polymer obtained by radical polymerization is proposed.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2-170806

[Patent Document 2] Japanese Patent Laid-Open Publication No. Hei 9-316261

However, in the technique described in Patent Document 1, a method of producing an ultrahigh molecular weight component uses a polyfunctional vinyl compound, especially When divinylbenzene is used, the formation of an ultrahigh molecular weight component can be achieved. However, in a long period of production, gelation occurs in the reactor or the like, which is not preferable. Further, in the technique described in Patent Document 2, since the resin obtained by the different production methods is mixed after the fact, it is industrially cumbersome, which is not preferable.

The present invention has been made in view of the problems of the prior art described above, and an object thereof is to provide a vinyl aromatic hydrocarbon polymer composition excellent in stretch viscosity, workability (flowability), and rigidity balance, and is suitable for production thereof. A method for producing a vinyl aromatic hydrocarbon polymer composition.

The inventors of the present invention have intensively studied to solve the above-mentioned problems, and have found that a conventional linear ethylene aromatic hydrocarbon polymer contains a copolymer having a specific structure, thereby obtaining stretch viscosity and workability (fluidity). The ethylene aromatic hydrocarbon polymer composition excellent in balance is thus completed in the present invention.

That is, the present invention is as follows.

[1]

A vinyl aromatic hydrocarbon polymer composition comprising a linear aromatic hydrocarbon polymer (A) and a branched ethylene aromatic hydrocarbon polymer (B), wherein: The chain ethylene aromatic hydrocarbon polymer (A) and the branched ethylene aromatic hydrocarbon polymer (B) comprise a copolymer selected from a homopolymer of one type of ethylene aromatic hydrocarbon or a copolymer of two or more kinds of ethylene aromatic hydrocarbons. a copolymer of a vinyl aromatic hydrocarbon and an unsaturated carboxylic acid, a copolymer of a vinyl aromatic hydrocarbon and an unsaturated carboxylic acid and/or an alkyl ester of an unsaturated carboxylic acid, and a vinyl aromatic hydrocarbon and an unsaturated carboxylic acid At least one of a group consisting of an acid anhydride or a copolymer of maleimide; the branched ethylene aromatic hydrocarbon polymer (B) is composed of a vinyl aromatic hydrocarbon and a conjugated diene. The unit of the conjugated diene compound in the block copolymer is branched from the starting point; the content of the block copolymer contained in the ethylene aromatic hydrocarbon polymer composition is 0.1% by mass in terms of conjugated diene. The above 2.0% by mass or less.

[2]

The ethylene aromatic hydrocarbon polymer composition according to [1], wherein the Z average molecular weight (Mz1) before the oxidative decomposition is carried out when oxidative decomposition is carried out by using ruthenium tetroxide as a catalyst and by hydroperoxidation of the third butyl group. The ratio (Mz2/Mz1) of the Z average molecular weight (Mz2) after the oxidative decomposition is 0.30 or more and 0.90 or less.

[3]

The ethylene aromatic hydrocarbon polymer composition according to [1] or [2], wherein the branched ethylene aromatic hydrocarbon polymer (B) is dispersed in the linear ethylene aromatic hydrocarbon polymer (A), and is expanded to In the electron micrograph of 100,000 times, the number of spot particles of 50 nm or less of the granules per 4 μm ² is 0 to 1000.

[4]

The ethylene aromatic hydrocarbon polymer composition according to any one of [1] to [3] wherein the weight average molecular weight is 150,000 or more and 500,000 or less.

[5]

A vinyl aromatic hydrocarbon polymer composition according to any one of [1] to [4], which The branching degree of the medium ethylene aromatic hydrocarbon polymer composition is 0.30 or more and less than 0.90.

[6]

The ethylene aromatic hydrocarbon polymer composition according to any one of [1] to [5] wherein the molecular weight component of 1,000,000 or more of the ethylene aromatic hydrocarbon polymer composition is 2.0% or more and 20% or less.

[7]

The ethylene aromatic hydrocarbon polymer composition according to any one of [1] to [6] wherein the amount of the component derived from the conjugated diene compound unit in the block copolymer is 5% by mass or more and 40% by mass or less. The amount of the component derived from the unit of the ethylene aromatic hydrocarbon compound in the block copolymer is 60% by mass or more and 95% by mass or less, and the amount of the ethylene bond in the block copolymer is 7% or more and 70% or less.

[8]

The method for producing a vinyl aromatic hydrocarbon polymer composition according to any one of [1] to [7], wherein the method comprises the steps of: a step of dissolving in a monomer capable of undergoing radical polymerization, and a step of performing radical polymerization after the dissolution; and a polymer obtained from the monomer capable of undergoing radical polymerization, comprising: selected from a vinyl aromatic group a homopolymer of a hydrocarbon or a copolymer of two or more kinds of ethylene aromatic hydrocarbons, a copolymer of a vinyl aromatic hydrocarbon and an unsaturated carboxylic acid, an alkyl aromatic hydrocarbon and an alkyl ester of an unsaturated carboxylic acid and/or an unsaturated carboxylic acid Copolymers, as well as ethylene aromatic hydrocarbons with unsaturated carboxylic anhydrides or maleic anhydride At least one of the group consisting of copolymers of imines.

The ethylene aromatic hydrocarbon polymer composition of the present invention is excellent in balance of rigidity, tensile viscosity, and processability (flowability). Therefore, the ethylene aromatic hydrocarbon polymer composition of the present invention can be widely used in applications such as blow molding, vacuum molding, extrusion molding, T compression molding, and inflation molding.

Fig. 1 is a photograph of a composition of a vinyl aromatic hydrocarbon polymer obtained in Example 6 by a transmission electron microscope.

Fig. 2 is a graph showing the relationship between the melt flow rate (MFR) and the elongational viscosity of the compositions of Comparative Examples 1 to 5 and Comparative Examples 8 to 9 and Examples 1 to 9 by comparison of Examples and Comparative Examples.

Hereinafter, the form for carrying out the invention (hereinafter also referred to as "this embodiment") will be described in detail. The present invention is not limited to the embodiment, and various modifications can be made without departing from the spirit and scope of the invention.

<ethylene aromatic hydrocarbon polymer composition>

The ethylene aromatic hydrocarbon polymer composition of the present embodiment is a vinyl aromatic hydrocarbon polymer composition comprising a linear ethylene aromatic hydrocarbon polymer (A) and a branched ethylene aromatic hydrocarbon polymer (B). In the present specification, only the linear ethylene aromatic hydrocarbon polymer may be simply referred to as "(A)", and the branched ethylene aromatic hydrocarbon polymer may be referred to simply as "(B)". In addition, in the embodiment B In the olefinic aromatic hydrocarbon polymer composition, the above (A) and (B) are selected from the group consisting of a homopolymer of one type of ethylene aromatic hydrocarbon or a copolymer of two or more kinds of ethylene aromatic hydrocarbons, a vinyl aromatic hydrocarbon, and a copolymer of an unsaturated carboxylic acid, a copolymer of a vinyl aromatic hydrocarbon and an alkyl ester of an unsaturated carboxylic acid and/or an unsaturated carboxylic acid, and a vinyl aromatic hydrocarbon with an unsaturated carboxylic anhydride or maleimide At least one of the group consisting of the copolymers, the above (B) is branched by starting from the unit of the conjugated diene compound in the block copolymer composed of the ethylene aromatic hydrocarbon and the conjugated diene, and the ethylene The content of the block copolymer contained in the aromatic hydrocarbon polymer composition is 0.1% by mass or more and 2.0% by mass or less based on the amount of the conjugated diene. According to the above configuration, the ethylene aromatic hydrocarbon polymer composition of the present embodiment is excellent in balance of rigidity, tensile viscosity, and workability (fluidity).

That is, since the ethylene aromatic hydrocarbon polymer composition of the present embodiment contains a block copolymer composed of a vinyl aromatic hydrocarbon and a conjugated diene, it can be conjugated by the block copolymer. The detachment of a hydrogen atom caused by a diene moiety, or by bonding a vinyl aromatic hydrocarbon chain to a vinyl group, can simultaneously obtain a branched ethylene aromatic hydrocarbon polymer (B) and a linear ethylene which form a high molecular weight component. Aromatic hydrocarbon polymer (A).

As described above, the "including a block copolymer" in the ethylene aromatic hydrocarbon polymer composition of the present embodiment means that the component (B) derived from the block copolymer is contained in the ethylene aromatic group of the present embodiment. In a hydrocarbon polymer composition. Further, "(A) and (B) include: a copolymer selected from a homopolymer of one type of ethylene aromatic hydrocarbon or a copolymer of two or more kinds of ethylene aromatic hydrocarbons, a copolymer of a vinyl aromatic hydrocarbon and an unsaturated carboxylic acid; Vinyl aromatic At least one of a group consisting of a copolymer of a hydrocarbon and an alkyl ester of an unsaturated carboxylic acid and/or an unsaturated carboxylic acid, and a copolymer of a vinyl aromatic hydrocarbon and an unsaturated carboxylic anhydride or maleimide The component (A) means "a copolymer selected from a homopolymer of one type of ethylene aromatic hydrocarbon or a copolymer of two or more kinds of ethylene aromatic hydrocarbons, a copolymer of a vinyl aromatic hydrocarbon and an unsaturated carboxylic acid, a copolymer of a vinyl aromatic hydrocarbon and an alkyl ester of an unsaturated carboxylic acid and/or an unsaturated carboxylic acid, and a copolymer of a vinyl aromatic hydrocarbon and an unsaturated carboxylic anhydride or maleimide At least one of the components (B) is contained in the ethylene aromatic hydrocarbon polymer composition of the present embodiment, and the component (B) is derived from "a homopolymer selected from one type of ethylene aromatic hydrocarbon or 2 a copolymer of the above ethylene aromatic hydrocarbon, a copolymer of a vinyl aromatic hydrocarbon and an unsaturated carboxylic acid, a copolymer of a vinyl aromatic hydrocarbon and an unsaturated carboxylic acid and/or an alkyl ester of an unsaturated carboxylic acid, and a vinyl aromatic a copolymer of a hydrocarbon and an unsaturated carboxylic anhydride or maleimide At least one component group "is contained in the block copolymer bonded to the vinyl aromatic hydrocarbon-conjugated diene portion of the chain.

The content of the block copolymer contained in the ethylene aromatic hydrocarbon polymer composition of the present embodiment is 0.1% by mass or more and 2.0% by mass or less based on the amount of the conjugated diene. By setting the amount of the conjugated diene in the above range, good elongational viscosity, fluidity, and rigidity can be exhibited. The amount of the conjugated diene is preferably 0.2% by mass or more, more preferably 0.3% by mass or more, and still more preferably 0.4% by mass or more from the viewpoint of elongation viscosity and rigidity. On the other hand, from the viewpoint of fluidity, it is preferably 1.5% by mass or less, and particularly preferably 1.3% by mass or less. When the above conjugated diene is converted When the amount is less than 0.1% by mass, the probability of the ethylene aromatic hydrocarbon chain being bonded to the conjugated diene moiety is lowered, and the polymer (B) cannot be obtained, so that a composition having a high elongation viscosity cannot be formed. Further, when the amount of the conjugated diene is more than 2.0% by mass, the processability (flowability) or rigidity of the ethylene aromatic hydrocarbon polymer composition is lowered. The amount of the conjugated diene to be converted can be measured by the method described in the examples below.

The component (A) in the present embodiment may contain a monomer capable of radical polymerization as a constituent unit. The monomer capable of undergoing radical polymerization is not limited as follows, and examples thereof include a vinyl aromatic hydrocarbon monomer. Further, an unsaturated carboxylic acid, an alkyl ester of an unsaturated carboxylic acid, an unsaturated carboxylic anhydride, a maleimide or the like may be used in combination with the above-mentioned ethylene aromatic hydrocarbon monomer.

It is preferred to use a monomer capable of radical polymerization to obtain a copolymer comprising a homopolymer selected from one type of ethylene aromatic hydrocarbon or two or more kinds of ethylene aromatic hydrocarbons, a vinyl aromatic hydrocarbon and an unsaturated carboxylic acid. a copolymer of an acid, a copolymer of a vinyl aromatic hydrocarbon and an alkyl ester of an unsaturated carboxylic acid and/or an unsaturated carboxylic acid, and a copolymer of a vinyl aromatic hydrocarbon and an unsaturated carboxylic anhydride or maleimide At least one polymer of the group consisting of. In other words, the ethylene aromatic hydrocarbon polymer composition of the present embodiment preferably contains a copolymer selected from a homopolymer of one type of ethylene aromatic hydrocarbon or a copolymer of two or more kinds of ethylene aromatic hydrocarbons, and a vinyl aromatic hydrocarbon. Copolymer with unsaturated carboxylic acid, copolymer of ethylene aromatic hydrocarbon with unsaturated carboxylic acid and/or unsaturated carboxylic acid alkyl ester, and ethylene aromatic hydrocarbon with unsaturated carboxylic anhydride or maleimide Polymerization of at least one of the groups consisting of copolymers The substance is the component (A) and the component (B). The copolymer of the above ethylene aromatic hydrocarbon and the unsaturated carboxylic acid and/or the alkyl ester of the unsaturated carboxylic acid may be a binary copolymer or a terpolymer.

The above ethylene aromatic hydrocarbon monomer is not limited to the following, and for example, styrene, α-styrene, o-, m- and p-methylstyrene, ethylstyrene, propylstyrene, butylstyrene, chlorobenzene can be used. Ethylene, dichlorostyrene, bromostyrene, dibromostyrene, and the like. Among them, styrene is preferably used. One type of the ethylene aromatic hydrocarbon monomer or two or more types may be used in combination.

Specific examples of other unsaturated monomers which can be used in combination (copolymerizable) with a vinyl aromatic hydrocarbon monomer within the range which does not impair the object of the present embodiment can be exemplified as follows. In other words, the unsaturated carboxylic acid is not limited to the following, and examples thereof include acrylic acid, methacrylic acid, and maleic acid. Further, the alkyl ester of the above unsaturated carboxylic acid is not limited to the following, and examples thereof include an alkyl acrylate of methyl acrylate, ethyl acrylate, butyl acrylate, and 2-ethylhexyl acrylate, and methyl methacrylate. An alkyl ester of methacrylic acid such as ethyl methacrylate, butyl methacrylate or cyclohexyl methacrylate. In addition, the unsaturated carboxylic acid anhydride is not limited to the following, and examples thereof include maleic anhydride and the like. Further, the above-mentioned maleimide is not limited to the following, and examples thereof include N-methyl maleimide and phenyl maleimide. The ethylene aromatic hydrocarbon polymer composition of the present embodiment preferably contains 50% by mass or less of an unsaturated monomer copolymerizable with the above-mentioned ethylene aromatic hydrocarbon monomer. Specifically, the amount of the unsaturated carboxylic acid to be used is preferably from 0 to 30% by mass, particularly preferably from 1 to 20% by mass. With respect to the amount of the alkyl ester of the above unsaturated carboxylic acid, it is preferred It is 0 to 45% by mass, particularly preferably 1 to 40% by mass. The amount of the unsaturated carboxylic acid anhydride and the above-mentioned maleimide is preferably from 0 to 30% by mass, particularly preferably from 1 to 20% by mass. When the amount of the unsaturated monomer copolymerizable with the above-mentioned ethylene aromatic hydrocarbon monomer is 50% by mass or less, it is possible to sufficiently ensure good heat resistance and moldability.

The ethylene aromatic hydrocarbon polymer composition of the present embodiment preferably has a weight average molecular weight of 150,000 or more and 500,000 or less. It is more than 200,000 to 400,000, and more preferably 250,000 to 350,000. When the weight average molecular weight is 150,000 or more, the product strength tends to be sufficiently ensured, and when it is 500,000 or less, it tends to sufficiently ensure good moldability. The above weight average molecular weight can be obtained by gel permeation chromatography (GPC: Gel Permeation Chromatography).

The ethylene aromatic hydrocarbon polymer composition of the present embodiment contains a linear ethylene aromatic hydrocarbon polymer (A) and a branched ethylene aromatic hydrocarbon polymer (B) as described above, and is a conventional ethylene aromatic hydrocarbon. When compared to a linear polymer of a hydrocarbon monomer, a high molecular weight polymer can be easily obtained. Regarding the above "high molecular weight", it can be evaluated by the following means. In other words, the molecular weight component of 1,000,000 or more of the styrene resin composition of the present embodiment is preferably 2.0% or more and 20% or less, more preferably 3.0% or more and 18% or less, and still more preferably 4.0% or more and 15% or less. When the molecular weight component of the above 1,000,000 or more is 2.0% or more, the amount of the high molecular weight component can be sufficiently formed, and when compared with the same weight average molecular weight, it has a linear polymer similar to the conventional ethylene aromatic hydrocarbon monomer. A tendency to form a composition having a good stretch viscosity can be formed. In addition, when the above molecular weight component of 1 million or more is 20% In the following, there is a tendency to sufficiently ensure good moldability.

Further, the branched ethylene aromatic hydrocarbon polymer (B) in the ethylene aromatic hydrocarbon polymer composition of the present embodiment is made of, for example, a mixed decomposing agent of a ruthenium tetroxide solution and a hydroperoxy third butyl group. The conjugated diene block in the inside was oxidatively decomposed to confirm the presence. That is, when the branched ethylene aromatic hydrocarbon polymer (B) is formed, the ethylene aromatic hydrocarbon chain bonded to the conjugated diene portion of the block copolymer of the ethylene aromatic hydrocarbon and the conjugated diene is oxidatively decomposed. It is cut, so the Z average molecular weight is lowered. Here, in the styrene resin composition of the present embodiment, the ratio (Mz2/Mz1) of the Z average molecular weight (Mz1) before oxidative decomposition to the Z average molecular weight (Mz2) after oxidative decomposition is from the viewpoint of fluidity. In view of the above, it is preferably 0.30 or more, more preferably 0.40 or more, still more preferably 0.60 or more. On the other hand, from the viewpoint of elongational viscosity, it is preferably 0.90 or less, more preferably 0.85 or less, still more preferably 0.80 or less. When the ratio of the Z average molecular weight is 0.90 or less, the amount of the ethylene aromatic hydrocarbon chain bonded to the conjugated diene portion can be sufficiently ensured, so that sufficient polymer concentration can be achieved, and it is sufficient. The tendency of a composition of high stretch viscosities. In addition, when the ratio of the Z average molecular weight is 0.30 or more, sufficient fluidity can be ensured, and the balance between the excellent elongational viscosity and the workability (fluidity) tends to be excellent.

The degree of branching of the ethylene aromatic hydrocarbon polymer composition of the present embodiment is preferably 0.30 or more, more preferably 0.40 or more, and still more preferably 0.60 or more from the viewpoint of fluidity. On the other hand, from the viewpoint of elongational viscosity, it is preferably less than 0.90, and particularly preferably 0.85 or less. When the branching degree is less than 0.90, the number of branches in the molecule can ensure a sufficient amount, so A tendency to have a composition with a sufficiently high stretch of viscosity. Further, when the degree of branching is 0.30 or more, sufficient fluidity can be ensured, and there is a tendency to achieve excellent balance between stretch viscosity and workability (flowability). The degree of branching can be expressed by the logarithmic ratio of the intrinsic viscosity when the weight average molecular weight = 100,000 measured by the multiplex detector GPC/SEC system (for example, Viscotec TDAmax manufactured by Spectris Co., Ltd.).

In the present embodiment, the dispersed particles having a particle diameter of 50 nm or less are expanded to 100,000 times in the point particles in which the branched ethylene aromatic hydrocarbon polymer (B) is dispersed in the linear ethylene aromatic hydrocarbon polymer (A). In the area of 4 μm ² of the subsequent electron micrograph, it is preferable to have 0 or more and 1000 or less dot-like particles. The number of the above-mentioned spotted particles in an area of 4 μm ² is particularly preferably 0 or more and 800 or less, more preferably 0 or more and 600 or less, more preferably 0 or more and 400 or less, and particularly preferably 0 or less. Above 200 or less. The best is 0 (no point particles). When the above-mentioned dot-like particles are not present and the number of the dot-like particles in an area of 4 μm ² is 1000 or less, the rigidity tends to be sufficiently ensured. The number of dispersed particles having a particle diameter of 50 nm or less in each of 4 μm ² can be dyed by ultra-thin sections of 80 nm cut from the ethylene aromatic hydrocarbon polymer composition of the present embodiment by citric acid. It is taken from a photograph taken by a transmission electron microscope. Here, the point-like particles are particles which do not have an inner structure, that is, are not core-shell particles or sac-containing particles. In addition, the term "encapsulated particles" refers to polybutadiene rubber in which a plurality of smaller polystyrene particles are filled, and the so-called core-shell particles refer to polybutadiene rubber containing one polystyrene particle inside. . When the shape of the point particle is agglomerated, the number of the point particles in the agglomerated form is calculated separately. When a plurality of core-shell particles and occluded particles are present in the ethylene aromatic hydrocarbon polymer composition, the rigidity tends to decrease, but in the ethylene aromatic hydrocarbon polymer composition of the present embodiment, the effect is not impaired. The core shell particles and the occluded particles may also be contained. The above particle diameter can be measured by the method described in the examples below.

(block copolymer)

The block copolymer of the present embodiment is composed of a vinyl aromatic hydrocarbon and a conjugated diene, and may also be referred to as an aromatic ethylene-conjugated diene block copolymer. The block copolymer can be produced, for example, by a solution polymerization method of at least one conjugated diene monomer and at least one aromatic vinyl monomer in the presence of a living anionic polymer.

The conjugated diene monomer is not particularly limited, and examples thereof include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, and 1,3-pentane. The olefin, 3-methyl-1,3-pentadiene, 1,3-heptadiene, 1,3-hexadiene or the like may be used alone or in combination of two or more. Preferred examples of the monomer include 1,3-butadiene and isoprene.

Further, the above aromatic vinyl monomer is not particularly limited, and examples thereof include styrene, p-methylstyrene, α-styrene, 3,5-dimethylstyrene, propylstyrene, and vinylethylbenzene. Further, one type or two or more types may be used, such as vinyl toluene and vinyl naphthalene. Particularly preferred is styrene. Examples of the hydrocarbon solvent used for the solution polymerization include aliphatic hydrocarbons such as butane, pentane, and hexane, alicyclic hydrocarbons such as cyclopentane and cyclohexane, and benzene, toluene, and dimethyl. An aromatic hydrocarbon such as benzene. Preferable examples include hexane and cyclohexane.

A more detailed production method of the block copolymer in the present embodiment can be exemplified as follows. Alternatively, by preparing a living anionic polymer, followed by adding a conjugated diene monomer, after the polymerization of the monomer, adding an aromatic vinyl monomer and continuing the polymerization reaction; or preparing a living anionic polymerization The material is then produced by adding a conjugated diene monomer and an aromatic vinyl monomer, and continuing the polymerization reaction. Further, a method in which a living anionic polymer is added to a hydrocarbon-based solvent in which a conjugated diene monomer is present, and an aromatic vinyl monomer is added after the polymerization of the monomer is completed, and a polymerization reaction is continued; Further, it is produced by adding a living anionic polymer to a hydrocarbon solvent in which a conjugated diene monomer and an aromatic vinyl monomer are present, and continuing the polymerization reaction.

The polymer used in the present embodiment is not limited to the following, and may be, for example, a linear block copolymer or a radiation block copolymer represented by the following general formulas (1) to (8), or any of these polymerized structures. mixture.

(1)c-(A-B)n

(2) c-(B-A)n

(3) c-(B-A-B)n

(4) c-(A-B-A)n

(5) c-(A-B)n-A

(6) c-(A-B)n-B

(7)c-(B-A-A-B)n

(8) c-(A-B-B-A)n (In any of the general formulae (1) to (8), B represents a conjugated diene polymerization And a disordered copolymer of a conjugated diene and an aromatic vinyl compound, and may have a tapered block in which the ratio of the aromatic vinyl compound is gradually increased. A represents a polymer block mainly composed of an aromatic vinyl compound. c represents the residue of the living anionic polymer or the residue of the coupling agent. n is an integer from 1 to 10, and the structure of a plurality of polymer chains bonded to c may be the same or different. The above "as the main body" means more than 50%. )

In the present embodiment, the amount of the component derived from the conjugated diene of the block copolymer is preferably 5% by mass or more and 40% by mass or less, and the amount of the component derived from the ethylene aromatic hydrocarbon in the block copolymer is preferably 60% by mass or more and 95% by mass or less. The amount of the constituent component derived from the conjugated diene of the block copolymer is particularly preferably 7% by mass or more and 38% by mass or less, and more preferably 10% by mass or more and 35% by mass or less. Further, the amount of the component derived from the ethylene aromatic hydrocarbon in the above block copolymer is preferably 62% by mass or more and 93% by mass or less, more preferably 65% by mass or more and 90% by mass or less. When the amount of the constituent component derived from the conjugated diene of the block copolymer is 5% by mass or more, hydrogen having a conjugated diene moiety is detached or a bond of a vinyl aromatic hydrocarbon chain to a vinyl group is sufficient. There is a tendency to have a high molecular weight component which is easy to obtain. In addition, when the amount of the constituent component derived from the conjugated diene is 40% by mass or less, it is possible to effectively prevent aggregation of the above-mentioned block copolymers, even if the branched ethylene aromatic hydrocarbon polymer (B) exists in a straight line. In the chain ethylene aromatic hydrocarbon polymer (A), the present state is uniform and does not become particles, or even if it is a particle, it tends to maintain a dot-like form. Further, the amount of ethylene bond in the block copolymer is preferably 7% or more and 70% or less. Furthermore, the above ethylene bond amount is particularly preferably 10% or more and 65% or less, more preferably 13% or more and 60% or less. When the amount of the ethylene bond is 7% or more, there is a tendency that the high molecular weight component for the purpose can be sufficiently ensured. In addition, when the amount of the ethylene bond is 70% or less, it is easy to control the amount of formation of the high molecular weight component to an appropriate range, and it is possible to ensure sufficient moldability. The amount of the constituent component derived from the conjugated diene, the amount of the component derived from the ethylene aromatic hydrocarbon, and the amount of the ethylene bond can be measured by the method described in the examples below. In other words, the amount of the component derived from the conjugated diene, the amount of the component derived from the ethylene aromatic hydrocarbon, and the amount of the ethylene bond are obtained before the branched ethylene aromatic hydrocarbon polymer (B) of the present embodiment is obtained. The block copolymer as a raw material was measured for the object.

The ethylene aromatic hydrocarbon polymer composition of the present embodiment can be used as an additive which is conventionally used in the field of styrene resins, such as an antioxidant, a lubricant, and a flame retardant, within the range not impairing the object of the present embodiment. A styrene resin composition is used in combination with a coloring agent, a coloring agent, and the like. The above-mentioned additives are not particularly limited, and examples thereof include plasticizers such as fluid paraffin and white mineral oil, and lubricants such as stearic acid, palmitic acid, zinc stearate, calcium stearate, and magnesium stearate, and hexabromo. A flame retardant such as cyclododecane, a coloring agent such as titanium oxide or carbon black. Further, the styrene-based resin may be formed into granules, and ethylene bis-lipidamine, zinc stearate, magnesium stearate or the like may be used as an external lubricant of the granules to be mixed with the granules.

The antioxidant is used to stabilize peroxide radicals such as hydrogen peroxide radicals generated during thermoforming or light irradiation, or to decompose peroxides such as hydrogen peroxide generated. . That is, the antioxidant is not particularly limited, and is, for example, a hindered phenol-based antioxidant or a peroxide decomposing agent. The former acts as a free radical chain inhibitor, which further decomposes the peroxide formed in the system into stable alcohols to prevent auto-oxidation. Specific examples of the hindered phenol-based antioxidant as the above antioxidant are not limited to the following, and examples thereof include 2,6-di(t-butyl)-4-methylphenol, styrenated phenol, and n-octadecyl-3. -(3,5-di(t-butyl)-4-hydroxyphenyl)propionate, 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 2- Tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl acrylate, 2-[1-(2-hydroxy-3,5- Di(tris-pentyl)phenyl)ethyl]-4,6-di(tri-pentyl)phenyl acrylate, 4,4'-butyl-butyl bis(3-methyl-6-tributyl) Phenol), 4,4'-thiobis(3-methyl-6-tert-butylphenol), alkylated bisphenol, hydrazine [methylene-3-bis(t-butyl)-4 -hydroxyphenyl)propionate]methane, 3,9-bis{2-[3-(3-t-butyl-4-hydroxy-5-methylphenyl)-propenyloxy]-1, 1-Dimethylethyl}-2,4,8,10-tetraoxyspiro[5,5]undecane, and the like. Further, specific examples of the peroxide decomposing agent as the above antioxidant are not limited to the following, and examples thereof include tridecylphenylphosphite, triphenylphosphite, and bis(2,4-di(t-butyl). An organophosphorus peroxide decomposing agent such as phenyl)phosphite, or bis(dodecyl)-3,3'-thiodipropionate or di(tetradecyl)-3,3 '-Thiodipropionate, di(octadecyl)-3,3'-thiodipropionate, neopentyl pentoxide (3-dodecylthiopropionate), two ( An organic sulfur-based peroxide decomposing agent such as tridecyl-3,3'-thiodipropionate or dimercaptobenzimidazole. The amount of the antioxidant added is preferably 0.01 parts by mass or more and 1 part by mass or less, and particularly preferably 0.1 parts by mass or more and 0.5 parts by mass or less based on 100 parts by mass of the ethylene aromatic hydrocarbon polymer composition.

<Method for Producing Vinyl Aromatic Hydrocarbon Polymer Composition>

The method for producing a vinyl aromatic hydrocarbon polymer composition according to the present embodiment includes a step of dissolving the block copolymer in a monomer capable of radical polymerization, and a step of performing radical polymerization after the dissolution. Further, in the method for producing a vinyl aromatic hydrocarbon polymer composition of the present embodiment, the polymer obtained from the monomer capable of radical polymerization includes a homopolymer selected from one type of ethylene aromatic hydrocarbon or a copolymer of two or more kinds of ethylene aromatic hydrocarbons, a copolymer of a vinyl aromatic hydrocarbon and an unsaturated carboxylic acid, a copolymer of a vinyl aromatic hydrocarbon and an unsaturated carboxylic acid and/or an alkyl ester of an unsaturated carboxylic acid, and ethylene At least one of the group consisting of a copolymer of an aromatic hydrocarbon and an unsaturated carboxylic anhydride or maleimide. According to the method for producing a vinyl aromatic hydrocarbon polymer composition of the present embodiment, the ethylene aromatic hydrocarbon polymer composition of the present embodiment can be efficiently produced, and The polymer obtained by performing the radical polymerization monomer may, for example, be a polymer as described above as a specific example.

Specific examples of the method for producing the ethylene aromatic hydrocarbon polymer composition are not limited to the following. For example, a block copolymer composed of a vinyl aromatic hydrocarbon and a conjugated diene is dissolved in a vinyl aromatic hydrocarbon monomer. The latter solution is produced by using general bulk polymerization, solution polymerization, suspension polymerization, or the like. In the present embodiment, in order to adjust the molecular weight of the linear ethylene aromatic hydrocarbon polymer (A) and the molecular weight of the branched ethylene aromatic hydrocarbon polymer (B), a polymerization initiator, a solvent, a transfer agent, etc. may be used. .

The polymerization initiator is not particularly limited, and for example, an organic peroxide can be used. The organic peroxide is not particularly limited, and examples thereof include 1,1-bis(t-butylperoxy)cyclohexane and 1,1-bis(t-butylperoxy)3,3. a peroxy ketal such as 5-trimethylcyclohexane, di(tert-butyl) peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy) a peroxy ester such as a dialkyl peroxide such as alkane, a benzamidine peroxide, a perylene dicarbonyl group such as a toluene peroxide, or a peroxy ester such as a di(tetradecyl)peroxy dicarbonate. Peroxy ketones such as cyclohexanone peroxide, hydrogen peroxides such as menthol hydrogen peroxide, 2,2-bis(4,4-di(t-butyl)peroxycyclohexyl)propane, 2 , 2-bis(4,4-di(tripentyl)peroxycyclohexyl)propane, 2,2-bis(4,4-di(t-butyl)peroxycyclohexyl)butane, A polyfunctional starter such as 2,2-bis(4,4-dipentylperoxycyclohexyl)propane. Among the above, from the viewpoint of increasing the stretching viscosity, 2,2-bis(4,4-di(t-butyl)peroxycyclohexyl)propane is preferred.

The organic peroxide may be added to the polymerization system (polymerization raw material solution or solution in the middle of polymerization) in any step of polymerization of the styrene monomer. These organic peroxides may be added to the polymerization raw material solution or may be added to the solution in the middle of the polymerization as necessary. The amount of the organic peroxide to be added is preferably 0.0005 parts by mass or more and 0.2 parts by mass or less, more preferably 0.01 parts by mass or more and 0.1 parts by mass or less, more preferably 0.03 parts by mass or more and 0.08 parts or more based on 100 parts by mass of the polymerization raw material solution. Below the mass. When the amount of the organic peroxide added is 0.2 parts by mass or less, the reaction heat generated during the polymerization tends to be favorably controlled, and it is preferable from the viewpoint of controlling the polymerization reaction.

The solvent is not limited as follows, and for example, toluene, ethylbenzene, xylene or the like can be used. The amount of the solvent to be used is not particularly limited, and is preferably from 0% by mass to 50% by mass based on 100% by mass of the polymerization raw material solution. Further, as the above-mentioned transfer agent, for example, n-dodecyl mercaptan mercaptan, tertiary dodecyl mercaptan mercaptan, α-methylstyrene dimer or the like can be used. The amount of the above-mentioned transfer agent to be used is preferably 0.01% by mass or more and 2% by mass or less based on 100% by mass of the polymerization raw material solution, and particularly preferably 0.1% by mass or more and 1% by mass or less, more preferably 0.2% by mass. The range of % or more and 0.8% by mass or less. The reaction temperature in the method for producing a vinyl aromatic hydrocarbon polymer composition of the present embodiment is preferably in the range of 80 ° C to 200 ° C, and more preferably in the range of 90 ° C to 180 ° C. When the reaction temperature is 80° C. or more, the productivity is sufficiently ensured, and conditions suitable for industrial use can be formed. On the other hand, when the reaction temperature is 200 ° C or lower, it is preferred to control the amount of formation of the low molecular weight polymer to an appropriate range. When the target molecular weight is adjusted, not only the above reaction temperature (polymerization temperature) but also the initial dose, the amount of the solvent, the chain transfer amount, and the like can be controlled. In addition, the reaction time in the method for producing a vinyl aromatic hydrocarbon polymer composition of the present embodiment can be generally 0.5 hours or more and 20 hours or less, preferably 2 hours or more and 10 hours or less. When the reaction time is 0.5 hours or longer, it is preferably from the viewpoint of easiness of the polymerization reaction, and when the reaction time is 20 hours or shorter, it is preferably from the viewpoint of productivity.

In the present embodiment, the polymerization conversion ratio of the ethylene aromatic hydrocarbon monomer is not particularly limited, and from an industrial viewpoint, Good for more than 40%. The polymerization solution thus obtained can be separated from the intended ethylene aromatic hydrocarbon polymer composition by removing unreacted monomers or solvents, and can be directly supplied to the next step during suspension polymerization.

[Examples]

In the following, the embodiments of the present invention are shown by way of examples, comparative examples, and reference examples. However, the present invention is not intended to limit the scope of the embodiments.

Various measurement evaluations of the ethylene aromatic hydrocarbon polymer composition in each of the examples were carried out according to the following methods.

[Measurement, evaluation method]

(1) Contents of ethylene aromatic hydrocarbons and conjugated dienes in a block copolymer composed of a vinyl aromatic hydrocarbon and a conjugated diene

The 1H-NMR was measured, and the peak area of the aromatic ring derived from the ethylene aromatic hydrocarbon and the peak area of the ethylene bonded portion derived from the conjugated diene were used and calculated. JEOL-ECA500 manufactured by JEOL Ltd. was used for the measurement device. The content of the conjugated diene in the vinyl aromatic hydrocarbon polymer composition is also determined by the same method as described above.

When determining the content of the conjugated diene in the ethylene aromatic hydrocarbon polymer composition, a composition having a content of each of the previously prepared conjugated diene of 0, 2.0% by mass, or 4.0% by mass is used, and The same method as the above (1) is performed by calculating the calibration curve prepared by the obtained conjugated diene content.

(2) Ethylene bond amount

After completely dissolving 0.1 g of the sample for measurement in 10 mL of carbon disulfide, a unit of 0.5 mm was used, and an infrared spectrophotometer (Shimadzu Corporation) was used. The company system, "FTIR-8400S") was used to measure the spectrum. Next, based on the obtained spectrum, the ethylene bond amount was determined by the Hampton method [R., R.,: AnaLyt. Chem., 21 (1949), p. 923].

(3) Melt flow rate (MFR)

The particles of each example were supplied to a melt flow rate measurement according to ISO 1133 at a temperature of 200 °C. The melt flow rate is set as an indicator of fluidity.

(4) stretch viscosity

Using a double capillary rheometer, the shear viscosity and elongational viscosity data were collected with respect to the shear rate of 40 to 1000 sec-1, and a graph of shear viscosity and elongational viscosity was prepared, and the ethylene fragrance at a shear viscosity of 2500 Pa·sec was calculated. The tensile viscosity of the hydrocarbon polymer composition. The detailed conditions at this time are as follows.

Use device: RASAND PRECISION company double capillary rheometer (type RH7-2)

Long size: 1mm ×16mmL

Short size: 1mm ×0.25mmL

Temperature: 200 ° C

Preheating time: After the piston was lowered, it was preheated for 6 minutes at a long side pressure of 5 MPa. It was then preheated for 3 minutes at a long side pressure of 3 MPa.

(5) Decomposition of tannic acid

The following method is used, that is, a mixed decomposing agent of a ruthenium tetroxide solution and a third butyl hydroperoxide is used, and the polymer in the chloroform solution is heated to 90 ° C for oxidative decomposition (IMKOLTHOFF, etal. , Method described in J. Polym. Sci. 1, 429 (1946), by oxidation of methanol The polymer after the solution was precipitated and recovered, and the ratio of the Z average molecular weight before and after the oxidative decomposition was calculated. Specifically, about 0.07 g of a sample of the ethylene aromatic hydrocarbon polymer composition is dissolved in 10 mL of chloroform, and a mixed decomposing agent of a third butanol solution and a third butanol solution of a third butyl hydroperoxide is added. 20 mL and 6 mL of a 0.05% chloroform solution of osmium tetroxide were decomposed in a bath at 90 ° C under reflux for 12 minutes. After cooling this, 200 mL of methanol was added to the solution while stirring to precipitate a polystyrene component. This was separated by a glass filter, and the separated polystyrene component was dissolved in tetrahydrofuran (THF) to obtain a sample for gel permeation chromatography (GPC) measurement. The sample for GPC measurement was measured for the Z average molecular weight before and after oxidative decomposition by the following formula according to the molecular weight measurement method (6) described later.

Ratio of Z average molecular weight before and after oxidative decomposition = (Z average molecular weight after oxidative decomposition) / (Z average molecular weight before oxidative decomposition)

(6) Molecular weight determination

Each average molecular weight (Mn: number average molecular weight, Mw: weight average molecular weight, Mz: Z average molecular weight) was measured under the following conditions. Namely, 20 mL of a methyl ethyl ketone/methanol mixed solvent (mixing mass ratio of 90/10) was added to about 1 g of a vinyl aromatic hydrocarbon polymer composition, and the mixture was shaken for 60 minutes with a shaker to dissolve. Subsequently, the mixture was centrifuged at 20,000 rpm for 60 minutes at 0 ° C and 20,000 rpm using a himac CR20 centrifugal separator equipped with a rotor of the R20A2 type, and then the soluble fraction was collected by decantation of the supernatant. Methanol is then added to recover the residue. It was then vacuum dried at room temperature to remove the solvent. The recovered sample was then measured under the following conditions. The ratio of molecular weight components of 1 million or more is determined by the above measurement. In the peak value of the polystyrene-equivalent relative molecular weight on the horizontal axis and the peak of the ultraviolet absorption luminosity on the vertical axis, the content of the component having a relative molecular weight of 1,000,000 or more is calculated by integration.

Use device: HLC8020 manufactured by Tosoh

Separation column: TSK-gel-GMHXL manufactured by Tosoh

Determination of solvent: tetrahydrofuran

Sample concentration: 5 mg of the ethylene aromatic hydrocarbon polymer composition was dissolved in 10 mL of the solvent

Measuring temperature: 40 ° C

Flow rate: 0.35 mL/min

(7) Branching degree

First, the intrinsic viscosity at a weight average molecular weight = 1,000,000 was measured under the following conditions.

Equipment: Spectris, Inc. Absolute Molecular Weight Determination Multiple Detector GPC/SEC System Viscotec TDA305

Light Scattering Detector Wavelength: 670nm

String: Tosoh, TSK-gel G6000, 5000, 4000HXL

Determination of solvent: tetrahydrofuran

Measuring temperature: 40 ° C

Flow rate: 1.0 mL / min

Based on the intrinsic viscosity obtained above, the degree of branching was calculated by the following formula.

Branching degree = log (inherent viscosity of the composition) / log (intrinsic viscosity of standard PS) (standard PS: TOSOH, TSKstandard, POLYSTYRENE, F-80 (TS-201), molecular weight = 7.06 × 10 ⁵ )

(8) Particle size determination

By taking a photograph of a transmission electron microscope by an ultrathin sectioning method, the particle diameter of the dispersed particles specified in the following manner was measured in the dispersed particles observed in the region of 4 μm ² in the photograph, whereby the particle diameter of the dispersed particles specified in the following manner was measured. Find the particle size. As the measuring apparatus, a transmission electron microscope HT7700 manufactured by Hitachi High Technologies Co., Ltd. was used. The number of particles of the dispersed particles is specified in the following manner. In other words, the ethylene aromatic hydrocarbon polymer composition of each example was cut into ultra-thin sections of 80 nm, and after dyeing with ruthenium tetroxide, it was photographed by a transmission electron microscope to obtain a magnification of 100,000 times. Photo (refer to Figure 1). From the photograph shown in Fig. 1, the number of dispersed particles having a particle diameter of 50 nm or less existing in an area of 4 μm ² was determined. Here, the particle size is a particle diameter when the circular equivalent diameter is obtained from the particle area in the photograph. When the shape of the point particle is agglomerated, the number of the point particles in the agglomerated form is calculated separately. In the measurement, the photograph was read by a scanner at a resolution of 1000 dpi, and the particle analysis software (image analysis software manufactured by Asahi Kasei Engineering Co., Ltd., trade name "A Zoukun") was used for measurement.

(9) Flexural modulus

Using an injection molding machine EC60N (manufactured by Toshiba Machine Co., Ltd.), the pellets obtained in each example were molded under a cylinder temperature of 220 ° C and a mold temperature of 45 ° C (according to ISO 294-1), and the flexural modulus was measured in accordance with ISO 178. As an indicator of rigidity.

[Manufacture of Block Copolymer B-1]

A vinyl aromatic hydrocarbon-conjugated diene copolymer (B-1) composed of a vinyl aromatic hydrocarbon content of 90% by mass and a conjugated diene content of 10% by mass was produced in the following manner. That is, a stirring apparatus having a volume of 10 L which was previously washed and dried, and a jacketed autoclave were formed in a nitrogen atmosphere, and 0.095 parts by mass of n-butyllithium was added to contain styrene 30 at a concentration of 25% by mass. A portion by mass of a cyclohexane solution was polymerized at 50 °C. Next, a cyclohexane solution containing 30 parts by mass of styrene and 10 parts by mass of 1,3-butadiene was added at a concentration of 25% by mass, and reacted for 60 minutes. Then, a cyclohexane solution containing 30 parts by mass of styrene at a concentration of 25% by mass was further added and reacted for 30 minutes. Then, in order to completely stop the polymerization, ethanol equivalent to isobutyllithium is added to the reactor, and 2-[1-(2-hydroxy-3) is added to 100 parts by mass of the polymer. 0.3 parts by mass of 5-bis(tris-pentyl)phenyl)ethyl]-4,6-di(triamylpentyl)phenyl acrylate as a stabilizer, the solvent is removed, thereby recovering the intended linear ethylene Aromatic hydrocarbon-conjugated diene copolymer (B-1). The block copolymer thus obtained was a block copolymer of an S1-(S/B)-S2 structure having a styrene content of 90% by mass. The above S, B, and S/B in the formula representing the block structure respectively represent the ethylene aromatic hydrocarbon block (S), the conjugated diene polymer block (B), and the disorder in the block copolymer. The block copolymer (S/B) of the copolymer is similarly shown below.

[Manufacture of Block Copolymer B-2]

A vinyl aromatic hydrocarbon-conjugated diene copolymer (B-2) composed of a vinyl aromatic hydrocarbon content of 80% by mass and a conjugated diene content of 20% by mass was produced in the following manner. That is, a stirring device having a volume of 10 L which has been previously washed and dried, and a jacketed autoclave are configured as a nitrogen atmosphere, and 0.095 parts by mass of a base lithium and 300 ppm of tetrahydrofuran were added to a cyclohexane solution containing 10 parts by mass of 1,3-butadiene at a concentration of 25% by mass, and polymerization was carried out at 50 °C. Then, 80 parts by mass of styrene was added and reacted for 5 minutes. Then, 10 parts by mass of 1,3-butadiene was further added and reacted for 10 minutes. Then, in order to completely stop the polymerization, ethanol equivalent to isobutylene was added to the reactor, and 2-tert-butyl-6-(3) was added with respect to 100 parts by mass of the block copolymer. 0.15 parts by mass of t-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl acrylate as a heat stabilizer. The solvent is then removed, thereby recovering the block copolymer. The block copolymer thus obtained was a linear block copolymer of a B-S-B structure having a styrene content of 80% by mass.

[Manufacture of block copolymers B-3 to B-7]

A vinyl aromatic hydrocarbon-conjugated diene copolymer (B-3 to B-7) composed of the ethylene aromatic hydrocarbon content and the conjugated diene content shown in Table 1 in the same manner as the block copolymer B-2. The amount of n-butyllithium and tetrahydrofuran added was adjusted so as to be the amount of ethylene bond defined in Table 1, and linear block copolymers B-3 to B-7 having a BSB structure were obtained, respectively.

[Example 1] [Manufacture of ethylene aromatic hydrocarbon polymer composition]

First, a mixed liquid of 87% by mass of styrene, 8% by mass of ethylbenzene, and 5% by mass of block copolymer B-1 was prepared. 0.015 parts by mass of 2,2-bis(4,4-di(t-butyl)peroxycyclohexyl)propane was added to 100 parts by mass of the mixed liquid (hereinafter, simply referred to as "PTA" in Table 2). The polymerization raw material liquid obtained in the same manner as in Table 3 was continuously supplied to a 4.6 L fully mixed reactor at 0.78 L/Hr, and adjusted to 103 °C. Solid concentration at the outlet of the reactor It is 39% by mass. The solid content concentration described above was calculated by the following method. That is, first, the polymerization liquid of w1 (g) was collected in an aluminum cup, and subjected to distillation at 230 ° C for 15 minutes under reduced pressure to volatilize volatile components such as unreacted monomers in the polymerization liquid. Then, it is calculated using the following formula with respect to the remaining solid content (reaction product) w2 (g).

(solid content concentration) = w2 / w1 × 100 (%)

Next, the polymer solution of the fully mixed reactor was continuously supplied to a 1.5 L laminar flow type reactor-1 capable of temperature control in Zone 3, and arranged in series therewith to perform temperature control in Zone 3. 1.5 L of laminar flow reactor-2. The temperature of the laminar flow reactor-1 was adjusted to 129 ° C / 134 ° C / 139 ° C, and the temperature of the laminar flow reactor - 2 was adjusted to 150 ° C / 155 ° C / 165 ° C.

The polymer solution continuously discharged from the polymerization reactor is continuously supplied to the single-stage ventilating hole having a ventilation pressure of 240 ° C and 1.333 kPa connected to remove volatile components such as unreacted monomers and polymerization solvents. The devolatilizer of the shaft extruder modulates the resin. The final solids concentration was 79%. The polymerization conditions are shown in Table 2. Further, the obtained ethylene aromatic hydrocarbon polymer composition was subjected to molecular weight measurement by GPC (before and after decomposition of citric acid), measurement of branching degree, measurement of melt flow rate, measurement of particle diameter, measurement of flexural modulus, and measurement of tensile viscosity. The results are shown in Table 5.

The amount of constituent components derived from the conjugated diene (the amount of rubber in terms of butadiene) of the ethylene aromatic hydrocarbon polymer composition obtained in Example 1 was 0.6% by mass, and the ratio of the Z average molecular weight before and after the oxidative decomposition was 0.6. The branching degree was 0.77, the molecular weight component amount of 1,000,000 or more was 8.2% by mass, and the melt flow rate was 0.9 g/10 minutes. The tensile viscosity measured at 200 ° C and 2500 Pa sec was 495,000 Pa ‧ sec. There are no point particles.

[Examples 2 to 13]

A vinyl aromatic hydrocarbon polymer composition was produced in the same manner as in Example 1 except that the type of the block copolymer, the type and amount of each raw material, and the polymerization temperature were changed as shown in Table 2 (Example 2) To 13). Methyl methacrylate used in Table 2 was manufactured by Asahi Kasei Chemicals Co., Ltd., butyl acrylate was manufactured by Toagosei Co., Ltd., and α-methylstyrene dimer was manufactured by Wako Pure Chemical Industries, Ltd. The physical properties of these are shown in Table 5.

[Comparative Example 1] [Manufacture of styrene resin]

0.015 parts by mass of 2,2-bis(4,4-di(t-butyl)peroxycyclohexyl)propane was added to 100 parts by mass of a mixed liquid of 92% by mass of styrene and 85% by mass of ethylbenzene. The raw material liquid was polymerized, and then the polymerization raw material liquid was continuously supplied to a 4.6 L fully mixed type reactor at 0.78 L/Hr, and adjusted to 103 °C. Otherwise, the ethylene aromatic hydrocarbon polymer of Comparative Example 1 was produced in the same manner as in Example 1. Its physical properties are shown in Table 5.

[Comparative Examples 2 to 5, 9 to 10]

A vinyl aromatic hydrocarbon polymer composition was produced in the same manner as in Comparative Example 1, except that the type of the block copolymer, the amount of each raw material added, and the polymerization conditions were changed as shown in Table 3 (Comparative Example). 2 to 5, 9 to 10). The methyl methacrylate used in Table 3 was manufactured by Asahi Kasei Chemicals Co., Ltd., and the butyl acrylate was manufactured by Toagosei Co., Ltd., α-methylstyrene II. The polymer was manufactured by Wako Pure Chemical Industries, Ltd. The physical properties of these are shown in Table 5.

[Comparative Example 6]

A three-stage 5L-7L-7L laminar flow reactor equipped with a stirrer was connected in series, and then a vinyl aromatic hydrocarbon polymer composition was produced using a polymerization apparatus equipped with a biaxial extruder equipped with two vent holes. 90 parts by mass of styrene, 5 parts by mass of the linear ethylene aromatic hydrocarbon polymer B-6 described in Table 1, and 1,1-bis(t-butylperoxy)cyclohexane (slightly in Table 4) This is called "PHC". The same applies to the second to third tables.) 0.04 parts by mass of the raw material solution is supplied to a polymerization machine for polymerization. In the first stage polymerization machine, the stirrer was rotated at 120 ° C and 30 prm to carry out polymerization for 2 hours. After the rubber particles were precipitated, the polymerization was continued for 3 hours at 135 ° C in the second stage polymerization machine to obtain the rubber particles. After the stabilization, the polymerization was carried out for 3 hours at 145 ° C in the third-stage polymerization machine to make the final polymerized solid component 69%, and a single-stage ventilating hole was attached at 220 ° C and 2.666 kPa. After the polymerization solution was subjected to devolatilization by a shaft extruder, a vinyl aromatic hydrocarbon polymer composition of Comparative Example 6 was obtained. Its physical properties are shown in Table 5.

[Comparative Example 7]

The ethylene aromatic hydrocarbon polymer composition of Comparative Example 7 was produced in the same manner as in Comparative Example 6, except that the amount of each raw material added and the polymerization conditions were changed as shown in Table 4. The physical properties and the like are shown in Table 5.

[Comparative Example 8]

Using a biaxial extruder (TEM26SS-12-2V) manufactured by Toshiba Machine Co., Ltd., 5 parts by mass of the block copolymer B-1 shown in Table 1 at 220 ° C and 150 rpm, and manufactured by PS Japan Co., Ltd. Polystyrene G9305 (melting Flow rate = 1.5 g/10 min) 95 parts by mass of granulation, and a vinyl aromatic hydrocarbon polymer composition of Comparative Example 8 was produced. The physical properties and the like are shown in Table 5. The ethylene aromatic hydrocarbon polymer composition of the present example is a compound in which polystyrene and a block copolymer are simply blended, so that the unit of the conjugated diene compound in the block copolymer is not formed as a starting point. Molecular weight component. That is, the desired branched vinyl aromatic hydrocarbon polymer (B) of the present embodiment is not obtained.

In the above-mentioned Table 1, the amount of input of styrene is described as "St amount", and the amount of input of 1,3-butadiene is described as "amount of Bd", and is represented by a content ratio.

In the photograph of Fig. 1, the particles dyed in black are dispersed particles of a branched ethylene aromatic hydrocarbon polymer. From Figure 1, you can see The particle size of the desired ethylene aromatic hydrocarbon polymer composition of the present embodiment is slightly smaller than 50 nm.

From Tables 5 and 2, the ethylene aromatic hydrocarbon polymer compositions of Comparative Examples 1 to 4 and Comparative Examples 7 to 8 can be seen, and the values of the tensile viscosity and the workability (fluidity: melt flow rate) are compared. Examples 1 to 9 and Examples 12 to 13 were low. Further, in Comparative Examples 5 to 7, since the aggregation of the branched ethylene aromatic hydrocarbon polymer (B) was caused, the rigidity (bending modulus) was lowered. The ethylene aromatic hydrocarbon polymer compositions of Examples 1 to 9 and Examples 12 to 13 were excellent in the balance of the tensile viscosity, workability (flowability), and rigidity.

The present application is based on Japanese Patent Application No. 2013-196190, filed on Sep. 20, 2013, which is hereby incorporated by reference.

[Industrial Applicability]

The ethylene aromatic hydrocarbon polymer composition of the present embodiment retains excellent physical properties of the existing styrene resin, and has excellent properties such as rigidity, stretch viscosity, and workability (fluidity). Therefore, it can be widely used in blow molding, vacuum molding, extrusion molding, T compression molding, and inflation molding.

Claims (8)

A vinyl aromatic hydrocarbon polymer composition comprising a linear aromatic hydrocarbon polymer (A) and a branched ethylene aromatic hydrocarbon polymer (B), wherein: The chain ethylene aromatic hydrocarbon polymer (A) and the branched ethylene aromatic hydrocarbon polymer (B) comprise a copolymer selected from a homopolymer of one type of ethylene aromatic hydrocarbon or a copolymer of two or more kinds of ethylene aromatic hydrocarbons. a copolymer of a vinyl aromatic hydrocarbon and an unsaturated carboxylic acid, a copolymer of a vinyl aromatic hydrocarbon and an unsaturated carboxylic acid and/or an alkyl ester of an unsaturated carboxylic acid, and a vinyl aromatic hydrocarbon and an unsaturated carboxylic anhydride or cis. At least one of the group consisting of copolymers of enediamines; the branched ethylene aromatic hydrocarbon polymer (B) is a block copolymer composed of a vinyl aromatic hydrocarbon and a conjugated diene The unit of the conjugated diene compound is branched at the starting point, and the content of the block copolymer contained in the ethylene aromatic hydrocarbon polymer composition is 0.1% by mass or more and 2.0% by mass based on the amount of the conjugated diene. the following. The ethylene aromatic hydrocarbon polymer composition according to claim 1, wherein the Z average before the oxidative decomposition is carried out by oxidative decomposition using ruthenium tetroxide as a catalyst and a third butyl hydroperoxide. The ratio (Mz2/Mz1) of the molecular weight (Mz1) to the Z average molecular weight (Mz2) after the oxidative decomposition is 0.30 or more and 0.90 or less. The ethylene aromatic hydrocarbon polymer composition according to claim 1 or 2, wherein the branched ethylene aromatic hydrocarbon polymer (B) is dispersed in the linear ethylene aromatic hydrocarbon polymer (A), There are 0 to 1000 point particles having a particle diameter of 50 nm or less in an area of 4 μm ² in an electron microscope photograph enlarged to 100,000 times. The ethylene aromatic hydrocarbon polymer composition according to claim 1, wherein the weight average molecular weight is 150,000 or more and 500,000 or less. The ethylene aromatic hydrocarbon polymer composition according to claim 1, wherein the ethylene aromatic hydrocarbon polymer composition has a degree of branching of 0.30 or more and less than 0.90. The ethylene aromatic hydrocarbon polymer composition according to claim 1, wherein the molecular weight component of 1,000,000 or more of the ethylene aromatic hydrocarbon polymer composition is 2.0% or more and 20% or less. The ethylene aromatic hydrocarbon polymer composition according to claim 1, wherein the amount of the component derived from the conjugated diene compound unit in the block copolymer is 5% by mass or more and 40% by mass or less. The amount of the component derived from the unit of the ethylene aromatic hydrocarbon compound in the segment copolymer is 60% by mass or more and 95% by mass or less, and the amount of the ethylene bond in the block copolymer is 7% or more and 70% or less. A method for producing a vinyl aromatic hydrocarbon polymer composition, which is a method for producing a vinyl aromatic hydrocarbon polymer composition according to claim 1, comprising: dissolving the block copolymer in a process capable of performing a step of radically polymerizing the monomer, and a step of performing radical polymerization after the aforementioned dissolution; The polymer obtained from the monomer capable of radical polymerization includes a copolymer selected from a homopolymer of one type of ethylene aromatic hydrocarbon or a copolymer of two or more kinds of ethylene aromatic hydrocarbons, a vinyl aromatic hydrocarbon, and an unsaturated group. a copolymer of a carboxylic acid, a copolymer of a vinyl aromatic hydrocarbon and an alkyl ester of an unsaturated carboxylic acid and/or an unsaturated carboxylic acid, and a copolymer of a vinyl aromatic hydrocarbon and an unsaturated carboxylic anhydride or maleimide At least one of the groups formed.