JP2007332389A - Epoxidized thermoplastic polymers and processes for their production - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To conquer the stickiness of epoxidized thermoplastic polymers and the troublesome handling by blocking nature or the like and to provide epoxidized thermoplastic polymers excellent in workability and processes for their production. <P>SOLUTION: An epoxidized granular thermoplastic polymer comprises a shell-like surface layer insoluble in toluene at 25°C formed on the polymer. The process for the production of the epoxidized granular thermoplastic polymer comprises: the first step of epoxidizing a granular thermoplastic polymer in a water medium in the presence of an epoxidizing agent or the epoxidizing agent and a solvent for accelerating an epoxidation reaction and a phosphoric acid series compound; the second step of the washing with water, or the neutralization and washing with water of the epoxidized granular thermoplastic polymer; and the third step, if necessary, of removing the solvent for accelerating epoxidation reaction which may be used in the first step. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

The invention of the first group comprises an epoxidized granular thermoplastic polymer having a solvent-resistant shell-like surface layer, which is mainly used as a modifier for coating compositions, synthetic resins, rubber compositions, adhesives and the like. It relates to the manufacturing method.
More specifically, when epoxidizing using a double bond in a molecular chain of a diene polymer or the like, the above-mentioned granular thermoplastic polymer is used, and the epoxy is dispersed and suspended in water. The present invention relates to an epoxidized granular thermoplastic polymer in which a shell-like surface layer insoluble in a solvent is formed on the granular thermoplastic polymer, and a method for producing the same.

The invention of the second group relates to a method for producing an epoxidized thermoplastic polymer used for paint components, resin modifiers, rubber modifiers, adhesive components and the like.
More specifically, the epoxidized thermoplastic used in the various applications described above is carried out in a state where the thermoplastic polymer is dispersed or suspended in water when epoxidizing the double bond in the molecule of the thermoplastic polymer. The present invention relates to a method for producing a polymer.
In addition, a dispersion system that prevents blocking in water is maintained by prescribing the properties, types, amounts, etc. of the reaction accelerator used, for example, a thermoplastic polymer in a dispersed state in a pellet form. Of epoxidized thermoplastic polymer that enables the epoxidation reaction to be carried out at a high solids concentration and recovered in the form of pellets, crumbs, powders, etc. It relates to a manufacturing method.

Conventionally, the following method is known as a method for obtaining an epoxidized diene polymer by oxidizing a diene polymer to be epoxidized.
(1) A percarboxylic acid is produced by reacting hydrogen peroxide with a lower carboxylic acid such as formic acid or acetic acid. The percarboxylic acid is added to the reaction system as an epoxidizing agent, and epoxy is added in the presence or absence of a solvent. A method of performing a chemical reaction.
(2) A method of epoxidation using hydrogen peroxide in the presence of a catalyst such as an osmium salt, a tungstic acid and a solvent.

The methods (1) and (2) are characterized in that the epoxidation target diene polymer is dissolved in a solvent in order to efficiently perform the epoxidation reaction.
However, there are complicated steps for dissolving in a solvent, washing with water for removing carboxylic acids, which are by-products after the epoxidation reaction, and desolvation operation steps, and it is extremely difficult to recover the product. In particular, when the diene polymer to be epoxidized is a rubber polymer, the epoxidized product has a high viscosity, and the workability during handling is extremely poor. Furthermore, regarding the form of the epoxidized polymer, there are cases where it becomes a bale form that cannot be used as a raw material for molding, such as powder, crumb, pellets, etc. after epoxidation, and the usage mode when added and kneaded as a modifier is limited. Often.

  Regarding the method for producing an epoxidized diene polymer, for example, in JP-A-8-120022, (1) a diene polymer or a partially hydrogenated product thereof is mixed with an organic solvent, and an organic solvent slurry of the polymer or A step of obtaining an organic solvent solution, (2) a step of epoxidizing unsaturated carbon-carbon bonds present in the diene polymer using an epoxidizing agent, and (3) neutralizing the solution after the epoxidation reaction and / or Or (4) a solution of an epoxidized block copolymer having a polymer concentration of 5 to 50% by weight in the presence of a surfactant at the boiling point of an organic solvent, and When boiling, a step of stripping at a temperature not lower than the azeotropic temperature and not higher than 120 ° C. to obtain a slurry in which the polymer is dispersed in water, (5) a epoxidized diene containing water obtained through the above steps Block copolymerization A step of dehydrating the crumb of the product to make the water content 1-30 wt%, and (6) drying the epoxidized diene block copolymer obtained through the above steps to make the water content 1 wt% or less. A method of obtaining an epoxidized diene polymer through a process has been proposed.

  JP-A-9-60479 discloses a method for producing an epoxidized diene polymer using a screw extruder type drawing dehydrator in the drying step (6), and JP-A-9-95512. Then, the manufacturing method of the epoxidized diene block copolymer which supplies the epoxidized block copolymer obtained at the said process (3) to an evaporator, and directly evaporates and removes an organic solvent is proposed. Japanese Patent Application Laid-Open No. 8-104709 proposes a method for improving the gel content. However, these methods are difficult to implement industrially because they are not economical because they require large-scale equipment.

  In addition, these methods are all inventions relating to epoxidized block copolymers by a homogeneous method in which a raw material polymer is dissolved in a solvent and then epoxidized, and the characteristics of these production methods are particularly low in gel content. The present invention relates to a method for producing a modified polymer having quality. In addition, the epoxidized block copolymers obtained by these methods have a relatively low softening point, so that, for example, epoxidized block copolymer pellets are mutually surfaced during manufacture, processing, transportation and use. There is a problem of blocking or sticking firmly to each other, which hinders handling.

Further, as an improvement method, JP-A-9-165418 proposes a method of dispersing or suspending organic polymer pellets or the like in an organic solvent system and epoxidizing in a heterogeneous system. Because it is an organic solvent that uses ethyl acetate, hexane, etc., and dissolves or swells the raw material resin, some of the pellets, etc., dissolve or swell, and the pellets are blocked in the reactor (bulk state) Therefore, there is a facility problem in the discharge process of the epoxidized product.
In addition, there is a polymer raw material that dissolves in a solvent as the epoxidation progresses, and the problem that the pellets block together as the epoxidation progresses as described above. A large amount of organic solvent is used as the solvent used in the reaction system, and there is a problem from the viewpoint of the recovery work.

Japanese Patent Laid-Open No. 9-67502 proposes a method of adding an antiblocking agent to the obtained epoxidized copolymer in a subsequent step.
In JP-A-9-208617, a chemically modified diene polymer composition, and a method for producing a composition by epoxidizing a polymer in a fine particle state of 0.05 to 10 μm in water as a production method thereof, are proposed. However, it is a production method as a composition, and no mention is made regarding the point regarding the recoverability of the epoxidized polymer or the improvement of the blocking property of the epoxidized polymer.
In JP-A-10-316715, an aqueous dispersion of an isoprene-based polymer in which isoprene units in a polymer are bonded by a trans-1,4 bond is epoxidized with peracetic acid to provide mechanical stability as a dispersion. It is described that an aqueous dispersion of a polymer containing an epoxy-modified isoprene-based polymer having excellent properties and coating film adhesion is obtained.
In JP-A-2000-44708, the surface layer of an unvulcanized or vulcanized rubber product is treated with an aqueous solution containing a peracid to epoxidize the surface layer of the rubber product, thereby making it non-adhesive, slippery, other An invention relating to a method for surface treatment of a rubber product imparting a barrier effect is described.

JP-A-8-120022 Japanese Patent Laid-Open No. 9-60479 JP-A-9-95512 JP-A-8-104709 JP-A-9-165418 JP-A-9-67502 JP-A-9-208617 JP 10-316715 A JP 2000-44708 A

In view of the above-mentioned problems in the prior art, the first group of inventions epoxidizes thermoplastic polymers such as diene polymers, and as general modifiers for synthetic resins and as a component of synthetic resin compositions. It is an object of the present invention to provide an epoxidized granular thermoplastic polymer that can be used and overcome the complexity of handling based on the tackiness and the like that the conventional epoxidized compounds usually have, and a method for producing the same.
In addition, with respect to the above production method, an attempt is made to provide an alternative to the conventional epoxy modification method, that is, a method in which a thermoplastic polymer such as the diene polymer is dissolved in a solvent to perform epoxidation. Is.

  Further, in the invention of the second group, when the thermoplastic polymer to be epoxidized is oxidized to obtain the epoxidized thermoplastic polymer, there are various problems when the thermoplastic polymer to be epoxidized is dissolved in a solvent. It is an object to provide a method for epoxidation reaction, production, and purification in a solid state of a thermoplastic polymer to be epoxidized, more specifically, on the premise of avoiding the occurrence.

  In addition, although this invention is invention of 1st group, in this specification, 2nd group invention is described in detail for reference.

The inventors of the first group of the inventions have intensively studied to solve the above problems, and as a result, in the epoxidation reaction stage, by imparting solvent resistance to the surface of the thermoplastic polymer, blocking, adhesion, etc. We have found a method for producing an epoxidized granular thermoplastic polymer that solves the problem.
Specifically, in a system in which granular materials such as thermoplastic polymer pellets and powder are dispersed or suspended in water as they are, they are epoxidized using peracetic acid, a phosphoric acid compound and preferably a reaction accelerator, In addition, by forming a shell-like surface layer that is solvent-resistant to the granular material, specifically insoluble in toluene at 25 ° C., the epoxidation reaction in water can proceed in a dispersed form, Epoxidation in which the shell-like surface layer is formed on the final modified granular thermoplastic polymer, and a blocking state is unlikely to occur between the granular materials. The inventors have found that a thermoplastic polymer can be produced, and have completed the present invention (the first group of inventions). The gist of the invention of the first group is as follows.

  The first of the present invention relates to an epoxidized granular thermoplastic polymer characterized in that a shell-like surface layer insoluble in toluene at 25 ° C. is formed.

  A second aspect of the present invention relates to the epoxidized granular thermoplastic polymer according to the first aspect, wherein the thermoplastic polymer has a spherical equivalent particle diameter in the range of 0.05 to 7 mm.

  The third of the present invention relates to the epoxidized granular thermoplastic polymer of the first or second invention, wherein the thermoplastic polymer is a diene polymer.

  According to a fourth aspect of the present invention, the diene polymer is at least one selected from the group consisting of a butadiene polymer, a styrene-butadiene copolymer, an isoprene polymer, a styrene-isoprene copolymer, and an acrylonitrile-butadiene copolymer. The epoxidized granular thermoplastic polymer of the third invention, which is a diene polymer.

  5th of this invention is related with the epoxidized granular thermoplastic polymer of any one of the said 1st-4th invention whose oxirane oxygen concentration of an epoxidized granular thermoplastic polymer is 0.3 to 5.0 weight%.

  6th of this invention is related with the epoxidized granular thermoplastic polymer of any one of the said 1st-5th invention whose gel content of an epoxidized granular thermoplastic polymer is 0.1 weight% or more.

  According to a seventh aspect of the present invention, a granular thermoplastic polymer is epoxidized in an aqueous medium in the presence of an epoxidizing agent, an epoxidizing agent, an epoxidation reaction accelerating solvent, and a phosphoric acid compound, to obtain an epoxidized granular heat. A first step of making a plastic polymer, a second step for water washing or neutralization and water washing of the epoxidized granular thermoplastic polymer, and an epoxidation reaction accelerating solvent that may be used in the first step The present invention relates to a method for producing an epoxidized granular thermoplastic polymer according to the first aspect of the present invention, comprising a third step provided as necessary for removal.

  The eighth aspect of the present invention relates to a method for producing an epoxidized granular thermoplastic polymer according to the seventh aspect of the present invention, wherein peracetic acid is used as an epoxidizing agent in the first step.

  9th of this invention is related with the manufacturing method of the epoxidized granular thermoplastic polymer of the said 7th or 8th invention whose SP value of the solvent for epoxidation reaction acceleration | stimulation which may be used at a 1st process is 10 or less. .

  The tenth aspect of the present invention is the epoxidized granular thermoplastic according to the seventh aspect, wherein the water washing in the second step or the neutralization and water washing is a solid-liquid separation operation for separating the polymer supplied to the third step. The present invention relates to a method for producing a polymer.

  In an eleventh aspect of the present invention, the removal of the solvent in the third step is performed by drying while maintaining the granular shape of the polymer obtained in the second step. The present invention relates to a method for manufacturing coalescence.

  A twelfth aspect of the present invention is the epoxidized granular thermoplastic polymer according to any one of the seventh to eleventh aspects, wherein the oxirane oxygen concentration in the epoxidized granular thermoplastic polymer is 0.3 to 5.0% by weight. It relates to a manufacturing method.

  13th of this invention is related with the manufacturing method of the epoxidized granular thermoplastic polymer of any one of the said 7th-12th invention whose gel content of an epoxidized granular thermoplastic polymer is 0.5 weight% or more.

The inventors of the second group of inventions have intensively studied to solve the above problems. As a result, the diene polymer is preferably dispersed or suspended in water in the form of solids such as pellets and powders. In the system in which the solubility parameter value (SP value) is defined for the raw diene polymer, the epoxidation reaction in water is allowed to proceed without causing blocking of pellets, In addition, the inventors have found that the epoxidized diene polymer can be obtained in a solid state such as pellets, crumbs, and powders, and have completed the invention of the second group. The gist of the invention of the second group is as follows.
In the first invention of the second group, a peroxide (C) is used in a state where the solid thermoplastic polymer (A) is dispersed or suspended in water (B), and the dispersion or suspension is used. The present invention relates to a method for producing an epoxidized thermoplastic polymer, wherein the thermoplastic polymer (A) is epoxidized while maintaining a turbid state.
2nd of invention of 2nd group is related with the manufacturing method of the 1st epoxidized thermoplastic polymer of this invention whose spherical conversion particle diameter of a thermoplastic polymer (A) is the range of 0.05-7 mm.
According to a third invention of the second group, the thermoplastic polymer (A) is a butadiene polymer, a styrene-butadiene copolymer, an isoprene polymer, a styrene-isoprene copolymer, an acrylonitrile-butadiene copolymer, an ethylene- The first or second epoxidized thermoplastic heavy polymer of the present invention, which is at least one polymer selected from the group consisting of propylene-diene terpolymers and partially hydrogenated products of these diene polymers or copolymers. The present invention relates to a method for manufacturing coalescence.
The present invention relates to a method for producing any one of the first to third epoxidized thermoplastic polymers of the present invention using a reaction accelerator (D) in addition to the fourth peroxide (C) of the second group of the invention.
The fifth group invention of the present invention is the fourth epoxidation heat of the present invention using one or more organic solvents capable of dissolving or swelling the thermoplastic polymer (A) as the reaction accelerator (D). The present invention relates to a method for producing a plastic polymer.
A sixth invention of the second group uses an organic solvent having a solubility parameter of less than 9.0 as the reaction accelerator (D), and water is added to 100 parts by weight of the thermoplastic polymer (A). (B) It is related with the manufacturing method of the 4th or 5th epoxidized thermoplastic polymer of this invention which uses 50-1000 weight part and reaction accelerator (D) 0.5-20 weight part.
The seventh invention of the second group is the sixth epoxidized thermoplastic polymer of the present invention, wherein the reaction accelerator (D) is one or more single or mixed solvents selected from the group consisting of cyclohexane, toluene and xylene. It relates to the manufacturing method.
In an eighth aspect of the invention of the second group, the thermoplastic polymer (A) is a styrene-butadiene copolymer, and the general formula a- (ba) _n (where n ≧ 1, a is polystyrene, b Is a linear or branched polymer represented by polybutadiene or a partially hydrogenated product thereof), and water (B) is 50 to 1000 weights with respect to 100 weight parts of the thermoplastic polymer (A). The present invention relates to a method for producing the fourth or fifth epoxidized thermoplastic polymer of the present invention using 0.5 to 30 parts by weight of a reaction accelerator (D) which is an organic solvent having a part and solubility parameter of 9.0 or more.
In the ninth aspect of the invention of the second group, the thermoplastic polymer (A) is (i) general formula (ab) _m (where m ≧ 2, a is polystyrene, b is polybutadiene or its partial water. (Ii) General formula a- (ba) _n (where n ≧ 1) and the above general formula (ab) a mixture of styrene-butadiene copolymers each represented by _m , (iii) butadiene polymer, (iv) isoprene polymer, (v) styrene-isoprene copolymer, (vi) acrylonitrile-butadiene copolymer, ( vii) an ethylene-propylene-diene terpolymer and (ix) at least one polymer selected from the group consisting of one or more partially hydrogenated products arbitrarily selected from these (i) to (vii), copolymer Coalescence Reaction accelerator which is an organic solvent having 50 to 1000 parts by weight of water (B) and a solubility parameter of 9.0 or more with respect to 100 parts by weight of the thermoplastic polymer (A) (D) It is related with the manufacturing method of the 4th or 5th epoxidized thermoplastic polymer of this invention which uses 0.5-100 weight part.
A tenth aspect of the invention of the second group is that the reaction accelerator (D) is one or more single or mixed solvents selected from the group consisting of ethyl acetate, tetrahydrofuran, benzene, methyl ethyl ketone and chloroform. The present invention relates to a method for producing an epoxidized thermoplastic polymer.
The eleventh aspect of the present invention is the epoxidized thermoplastic according to any one of the first to tenth aspects of the present invention using peracetic acid as the peroxide (C) or other percarboxylic acid derived using hydrogen peroxide. The present invention relates to a method for producing a polymer.
The twelfth invention of the second group relates to the eleventh epoxidized thermoplastic polymer production process of the present invention using peracetic acid as the peroxide (C).
A thirteenth aspect of the invention of the second group relates to a process for producing an epoxidized thermoplastic polymer according to any one of the third to twelfth aspects of the invention, wherein the peroxide (C) is diluted with a reaction accelerator (D). .
14th of invention of 2nd group is related with the manufacturing method of the epoxidized thermoplastic polymer in any one of 1st-13th of this invention whose epoxidation reaction temperature of a thermoplastic polymer (A) is 10-70 degreeC. .
A fifteenth aspect of the invention of the second group is that the oxirane oxygen concentration derived from the epoxy group in the epoxidized thermoplastic polymer is controlled within the range of 0.1 to 5.0% by weight, and the first to the 14th aspects of the present invention. To an epoxidized thermoplastic polymer.
16th of invention of 2nd group is the manufacturing method of the epoxidized thermoplastic polymer in any one of 1-15 of this invention performed by controlling the gel content of an epoxidized thermoplastic polymer to 5 weight% or less About.

The epoxidized granular thermoplastic polymer and the production method thereof according to the first group of the invention have the following particularly advantageous effects, and their industrial utility value is extremely large. That is, the epoxidized granular thermoplastic polymer according to the present invention has a unique structure having a shell-like surface layer insoluble in toluene at 25 ° C., and this structure is the same as that of the epoxidized thermoplastic polymer itself. It solves problems such as handling and workability based on adhesiveness and blocking properties. Moreover, since it is the formation of the above specific surface structure, blocking between the granular materials can be avoided, and it can be used as a granular material for the purpose of other resin modification, etc. A uniform dispersion state with the resin can be obtained without any trouble.
According to the production method of the epoxidized thermoplastic polymer of the invention of the second group, the heat to be epoxidized such as a diene resin or rubber polymer having a double bond in the molecule which is solid at room temperature It is only necessary to epoxidize the plastic polymer by dispersing or suspending it in water, and it is not necessary to dissolve it in a solvent, and it is advantageous that it can be easily epoxidized without causing blocking in a heterogeneous system. The industrial utility value is extremely large.

Hereinafter, the contents of the first group of the invention will be described in detail.
The thermoplastic polymer to be epoxidized according to the production method of the present invention may be either a solid resin or a solid rubber polymer, but the rubber polymer is more difficult by the conventional method of dissolving in a solvent. In view of the above points, the present invention is particularly preferable in that the application effect of the present invention is large. The thermoplastic polymer to be epoxidized is not particularly limited as long as it has a double bond based on a diene monomer in the molecule.

  Specific examples of the homopolymer among the thermoplastic polymers to be epoxidized according to the present invention include dicyclopentadiene (DCPD) which is a polymer of polybutadiene (BR), polyisoprene rubber, and alicyclic diene monomer. ) Resin, cyclopentadiene (CPD) resin, and the like. A typical example of the copolymer among the thermoplastic polymers is a random copolymer obtained from a mixture of two or more diene monomers, and a block copolymer of two or more diene homopolymers. In addition to the polymer, a copolymer of at least one diene monomer and another copolymerizable monomer such as a vinyl aromatic hydrocarbon compound or an olefin compound may be used.

Specific examples of the copolymer among the thermoplastic polymers will be described.
As typical examples of the monomer constituting the thermoplastic polymer according to the present invention, butadiene and isoprene can be mentioned. The thermoplastic polymer will be described below with a focus on both.
Examples of other monomers copolymerized with butadiene or isoprene include other conjugated dienes and vinyl compounds.
Other conjugated dienes that can be copolymerized with butadiene include, for example, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene, 3-butyl-1,3-octadiene, phenyl-1, 3-butadiene etc. can be mentioned. These other conjugated dienes can be used alone or in admixture of two or more.
Other conjugated dienes that can be copolymerized with isoprene include, for example, butadiene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene, 3-butyl-1,3-octadiene, phenyl- Examples include 1,3-butadiene. These other conjugated dienes can be used alone or in admixture of two or more.

  Furthermore, examples of the vinyl compound that can be copolymerized with butadiene or isoprene include α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-tertiary butylstyrene, etc. in addition to styrene. Alkyl-substituted styrenes; alkoxy-substituted styrenes such as o-methoxystyrene, m-methoxystyrene, and p-methoxystyrene; vinyl aromatic compounds such as divinylbenzene and 1,1-diphenylstyrene; methyl (meth) acrylate, (meta ) Ethyl acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, sec-butyl (meth) acrylate, T-butyl (meth) acrylate, lauryl (meth) acrylate, crotonic acid Unsaturated monocarboxylic acid esters such as chill, ethyl crotonate, methyl cinnamate and ethyl cinnamate; 2,2,2-trifluoroethyl (meth) acrylate, 3,3,3,2,2-penta Fluoroalkyl (meth) acrylates such as fluoropropyl (meth) acrylate and 4,4,4,3,3,2,2-heptafluorobutyl (meth) acrylate; 3- (trimethylsiloxanyldimethylsilyl) propyl ( (Meth) acryloyl group-containing siloxanyl compounds such as (meth) acrylate, 3- [tris (trimethylsiloxanyl) silyl] propyl (meth) acrylate, di- [3- (meth) acryloylpropyl] dimethylsilyl ether; ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,6-hexa Mono- or di- (meth) acrylates of alkylene glycols such as ethylene diol; 2-methoxyethylene (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 3-methoxypropyl (meth) acrylate, 3-ethoxypropyl (meth) ) Alkoxyalkyl (meth) acrylates such as acrylate; Cyanoalkyl (meth) acrylates such as 2-cyanoethyl (meth) acrylate and 3-cyanopropyl (meth) acrylate; Glycerin, 1,2,4-butanetriol, penta (1) Oligo (meth) acrylates such as di-, tri- or tetra (meth) acrylates of trihydric or higher polyhydric alcohols such as erystol and trimethylolalkane (alkane has a carbon number of, for example, 1 to 3); (Meth) acrylonitrile, α-chloro Cyanide vinyl compounds such as acrylonitrile and vinylidene cyanide; non-metabolites such as (meth) acrylamide, N-methylol (meth) acrylamide, N, N′-methylenebis (meth) acrylamide, N, N′-ethylenebis (meth) acrylamide, etc. Saturated amides; hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate; 2-hydroxyethyl crotonic acid, 2-hydroxypropyl crotonic acid, cinnamic acid 2- Hydroxyethyl, hydroxyalkyl esters of unsaturated monocarboxylic acids such as 2-hydroxypropyl cinnamate; unsaturated alcohols such as (meth) allyl alcohol; (meth) acrylic acid, crotonic acid, cinnamic acid, etc. Saturated monocarboxylic acids; Water) unsaturated polycarboxylic acids (anhydrides) such as maleic acid, fumaric acid, (anhydrous) itaconic acid, citraconic acid; mono- or di-esters of said unsaturated polycarboxylic acids; (meth) allyl glycidyl ether In addition to epoxy group-containing unsaturated compounds such as glycidyl (meth) acrylate, vinyl chloride, vinyl acetate, sodium isoprenesulfonate, dicyclopentadiene, ethylidene norbornene and the like can be mentioned. These vinyl compounds can be used alone or in admixture of two or more.

The copolymer of butadiene and the copolymer of isoprene, which are representative examples of the copolymer belonging to the thermoplastic polymer according to the present invention, as already described as a representative form of the copolymer, are random copolymers, A block copolymer may be used.
However, the thermoplastic polymer to be epoxidized in the present invention includes a random copolymer of butadiene and styrene, a random copolymer of butadiene and (meth) acrylonitrile, a block copolymer of butadiene and styrene, and isoprene. Of these, a random copolymer of styrene and styrene, a random copolymer of isoprene and (meth) acrylonitrile, a block copolymer of isoprene and styrene, and a copolymer of butadiene and isoprene are preferred. The copolymer of butadiene and isoprene can optionally contain a vinyl compound such as styrene or (meth) acrylonitrile.

The content of butadiene in the copolymer of butadiene and the content of isoprene in the copolymer of isoprene are usually 0.5 to 99.5% by weight, preferably 1 to 95% by weight, more preferably 5 to 90% by weight. %. In the copolymer of butadiene and isoprene as a specific copolymer, the content of butadiene is usually 0.5 to 99.5% by weight, preferably 1 to 95% by weight, and more preferably 5 to 90%. The content of isoprene is usually 0.5 to 99.5% by weight, preferably 1 to 95% by weight, more preferably 5 to 90% by weight. The content is usually 0 to 99% by weight, preferably 0 to 95% by weight, more preferably 0 to 90% by weight.
The weight average molecular weight of the butadiene homopolymer or copolymer and the isoprene copolymer as the epoxidation target polymer according to the present invention is preferably 1,000 to 5,000,000, particularly preferably 5, 000-500,000.

  As described above, when the polymer to be epoxidized according to the present invention is a copolymer, it may be a random copolymer or a block copolymer, and may be a copolymer with another copolymerizable monomer. However, when the copolymer is a random copolymer, an ethylene-propylene-diene terpolymer (EPDM) is preferable, and the physical properties of the copolymer are wide from those having an iodine value of about 10 to about 500. It can be suitably used as a plastic polymer.

  When the polymer to be epoxidized according to the present invention is a block copolymer, the composition of the copolymer is, for example, polystyrene-polybutadiene block copolymer, polystyrene-polybutadiene-polystyrene block copolymer (SBS), polystyrene-polyisoprene. -Polystyrene block copolymer (SIS), polyacrylonitrile-polybutadiene block copolymer (NBR), etc. are mentioned. For these diene polymers, partially hydrogenated products in which a part of the diene component is hydrogenated may be used. The molecular structure of these block copolymers may be any structure such as linear, branched, and radial. Further, the average molecular weight of the block copolymer is not particularly limited, but is preferably such that it does not dissolve in low molecular weight organic solvents. In general, the number average molecular weight is preferably in the range of 10,000 to 300,000. There is no restriction | limiting in particular about the terminal group of resin or rubber polymer used as the epoxidation object thermoplastic polymer.

  The resin or rubber-based polymer that is the thermoplastic polymer to be epoxidized according to the present invention needs to be solid at the epoxidation reaction temperature. Here, the solid state at the epoxidation reaction temperature means that the reaction temperature is in a state of being in the form of powder or granules without substantially changing its shape by stirring, and conversely, this reaction temperature. This means that the liquid does not change in shape or paste.

  The thermoplastic polymer to be epoxidized is preferably in the form of a commercially available pellet from the viewpoint of handling and easiness of solid-liquid separation in the second step of the present invention relating to the production method. As the size of the pellet, the average particle diameter is preferably in the range of 0.05 to 7 mm, and more preferably in the range of 0.1 to 7 mm, on a sphere conversion basis. Here, the sphere equivalent particle diameter is defined as the diameter of a sphere having the same volume as the average volume of the thermoplastic resin. In order to efficiently perform the epoxidation reaction, the surface area of the thermoplastic polymer to be epoxidized may be increased by pulverization. The pulverization method may be a method of pulverizing with a normal pulverizer, but when the organic polymer to be epoxidized is a rubber-based polymer, it is preferable to pulverize by a freeze pulverization method. Even in this case, it is preferable that the average particle diameter of the granular material is 0.05 mm or more from the same point as described above. The shape of the pellet is not particularly limited, and various shapes such as a spherical shape, a cubic shape, a rectangular parallelepiped shape, a cylindrical shape, a prismatic shape, a conical shape, a pyramidal shape, a hemispherical shape, a rugby ball shape, an egg shape, and a bowl shape, or these It may be a combination. In any shape, the average particle diameter based on the sphere is preferably in the above range.

A manufacturing method according to the invention of the first group will be described.
In the production process of the present invention, a granular thermoplastic polymer is epoxidized in an aqueous medium in the presence of an epoxidizing agent such as peracid or the epoxidizing agent and an epoxidation reaction accelerating solvent to epoxidize the granular thermoplastic polymer. The first step of coalescence, the water washing of the epoxidized granular thermoplastic polymer, or the second step for neutralization and water washing, and the removal of the epoxidation reaction accelerating solvent that may be used in the first step. For producing a epoxidized granular thermoplastic polymer comprising a third step provided as necessary.
In the epoxidation reaction step in the first step, water is used as a dispersion medium for the granular thermoplastic polymer, but as the epoxidizing agent, peracetic acid is preferably used alone or in combination with an organic solvent thereof. Further, an organic solvent is preferably used as a reaction accelerator. In addition, the organic solvent which is a solvent of peracetic acid may serve as the organic solvent as a reaction accelerator.
The second step includes water washing or neutralization and water washing steps, and the polymer is separated by solid-liquid separation and supplied to the third step.
In the subsequent third step, the granular modified thermoplastic polymer having an epoxidized shell-like surface layer is recovered by drying while maintaining the granular outer shape of the polymer obtained in the second step.
In addition, in the epoxidation reaction by addition of peracid in the first step, at least on the surface of the granular polymer, the ring opening of the epoxy group accompanying the reaction with the byproduct carboxylic acid, the subsequent crosslinking of the hydroxyl group and the epoxy group, and Alternatively, a crosslinking reaction presumed to be radical crosslinking by a peracid of a diene component occurs, and a shell-like surface layer excellent in solvent resistance (for example, resistance to toluene at 25 ° C.) and chemically stable is formed. Yes. This shell-like surface layer suppresses blocking between the granular materials and the like, and contributes to an improvement in handling properties of the epoxidized granular thermoplastic polymer.
Since the phosphoric acid compound has an effect on the formation of the shell-like surface layer of the epoxidized granular thermoplastic polymer, it is preferably used in the epoxidation reaction.

  A feature of the present invention is that an epoxidized granular thermoplastic polymer obtained by forming a shell-like surface layer insoluble in toluene at 25 ° C. obtained as described above is obtained. The formation of such a shell-like surface layer prevents blocking between the particulate thermoplastic polymers during the epoxidation reaction in an aqueous dispersion, and also blocks the particulate thermoplastic polymer during the drying process, and further the product It is considered that blocking during transportation, storage and use can also be prevented.

  The organic solvent that is preferably used as a reaction accelerator during the epoxidation reaction varies depending on the type of polymer to be epoxidized and the reaction conditions for epoxidation, but the epoxidizing peroxide is a diene in a solid state. It has the function of penetrating and transporting to the inside of a polymer, etc., and epoxidizing to the inside, and as a selection criterion, it is an organic solvent that can dissolve and swell the polymer to be epoxidized and penetrate to the inside, and dissolve An organic solvent having a property parameter (SP) value of 10 or less is preferably selected. An organic solvent having a solubility parameter value exceeding 10 has a small ability to dissolve, swell, and penetrate into a polymer to be epoxidized, and does not function as a reaction accelerator.

  Examples of the organic solvent that is preferably used in the epoxidation reaction include linear or branched hydrocarbons such as hexane and octane, or alkyl-substituted derivatives thereof; alicyclic hydrocarbons such as cyclohexane and cycloheptane Or alkyl-substituted derivatives thereof; aromatic hydrocarbons or alkyl-substituted aromatic hydrocarbons such as benzene, naphthalene, toluene and xylene; aliphatic carboxylic acid esters such as methyl acetate and ethyl acetate; chloroform and the like Heterocyclic compounds such as halogenated hydrocarbons and tetrahydrofuran are mentioned. Of these, cyclohexane, ethyl acetate, chloroform, toluene, from the viewpoints of being able to be used by dissolving peroxide as an epoxidizing agent, the solubility of the polymer to be epoxidized and the subsequent ease of organic solvent recovery, etc. , Benzene, xylene, hexane, tetrahydrofuran and the like are preferred, but one or a mixture of two or more of these can also be used.

  Since the reaction accelerator for carrying out the epoxidation reaction has a dissolving, swelling and penetrating action with respect to the polymer to be epoxidized as described above, blocking of the polymer occurs when the amount used is increased. It becomes impossible to proceed the reaction in the aqueous dispersion which is a feature. That is, dissolution of the pellet surface occurs, blocking between the organic polymers occurs, stirring is impossible, and the product cannot be removed from the reaction vessel. The occurrence of blocking is also affected by the type of the granular thermoplastic polymer, the ratio of water to the granular thermoplastic polymer, and the reaction temperature, and does not depend only on the reaction accelerator. Therefore, the amount of use is determined in consideration of the condition where blocking does not occur. The proportion of water used with respect to 100 parts by weight of the granular thermoplastic polymer is usually in the range of 50 to 1000 parts by weight. In this case, the proportion of the reaction accelerator used is generally 100 parts by weight or less, particularly 80 parts by weight or less. A range is preferred.

Examples of the peroxide used as the epoxidizing agent include percarboxylic acid compounds such as performic acid, peracetic acid, and perpropionic acid. These peroxides can be epoxidized even in a system using a peroxide containing water derived from hydrogen peroxide. Among these, peracetic acid is preferable from the viewpoint of efficiently proceeding with epoxidation.
When using percarboxylic acids as epoxidizing agents, it is preferable to use them by dissolving them in a solvent. Examples of the percarboxylic acid solvent include hydrocarbons such as hexane, organic acid esters such as ethyl acetate, and aromatic hydrocarbons such as toluene. The effect of these solvents on the epoxidation reaction is the same as that of the above-mentioned reaction accelerator, and penetrates inside the thermoplastic polymer to be epoxidized to promote the epoxidation reaction. It is desirable to use it. However, when the organic solvent used as the peroxide solvent here is an organic solvent that also functions as a reaction accelerator, the amount used is considered in addition to the amount of the reaction accelerator of the present invention. There is a need.

  In a system using hydrogen peroxide or a peroxide derived from hydrogen peroxide, a percarboxylic acid is produced by previously reacting hydrogen peroxide with a lower carboxylic acid such as formic acid or acetic acid. A method of performing epoxidation reaction by adding carboxylic acid as a epoxidizing agent to a reaction system comprising a solid thermoplastic polymer, an aqueous medium and a solvent for promoting epoxidation reaction, and a catalyst and solvent such as osmium salt and tungstic acid There is a method of epoxidation using hydrogen peroxide in the presence of. As the solvent that can be used in this case, the same solvents as mentioned above can be used.

  In the present invention, the phosphoric acid compound preferably used in the epoxidation reaction includes inorganic phosphoric acid and organic phosphoric acid and salts thereof, preferably acidic phosphoric acid ester or salt thereof. Inorganic phosphoric acid includes hypophosphorous acid, metaphosphorous acid, orthophosphorous acid, metaphosphoric acid, orthophosphoric acid, pyrophosphorous acid, pyrophosphoric acid, tripolyphosphoric acid, tetrapolyphosphoric acid, hexametaphosphoric acid and their salt compounds. Can be mentioned. Examples of suitable acidic phosphate esters include monomethyl phosphate, monoisopropyl phosphate, monobutyl phosphate, monoamyl phosphate, mono 2-ethylhexyl phosphate, monononyl phosphate, monoisodecyl phosphate, monocetyl phosphate, monophosphate Examples include myristyl, monophenyl phosphate and monobenzyl phosphate, dialkyl phosphates such as dibutyl phosphate and di-2-hexyl phosphate, and dibutyl hydrogen phosphite. The phosphoric acid useful herein includes hydrated phosphoric acid to pure phosphoric acid, i.e., about 70% to about 100% phosphoric acid, preferably about 85% or more, due to industrial availability. Of phosphoric acid. Various condensed forms of phosphoric acid equivalents such as polymerized partial anhydrides or esters of phosphoric acid, pyrophosphoric acid, tripolyphosphoric acid and the like are used. Among these, tripolyphosphoric acid sodium salt, phosphoric acid ester and salts thereof are preferably used. The amount of these phosphoric acid compounds used is preferably 0.005 to 1 part by weight, more preferably 0.01 to 0.5 part by weight, with respect to 100 parts by weight of the granular thermoplastic polymer.

When epoxidizing by the production method according to the present invention, the oxirane oxygen concentration of the obtained epoxidized product is adjusted by changing the reaction molar ratio of the double bond amount of the thermoplastic polymer to be epoxidized and the epoxidizing agent. It is possible. The reaction molar ratio is preferably selected in the range of 1.0 to 3.0, particularly preferably in the range of 1.1 to 2.5. The oxirane oxygen concentration in the epoxidized granular thermoplastic polymer obtained by the production method of the present invention is preferably 0.3 to 5.0% by weight.
In addition, when epoxidized by the production method according to the present invention, the gel derived from the epoxidized product is often generated on the surface of the granular material because the epoxidation by the production method proceeds from the surface, and the shell is formed on the surface. A surface layer is formed. The gel content is evaluated as a ratio of an insoluble component with respect to toluene at 25 ° C. (a ratio with respect to the entire epoxidized granular thermoplastic polymer sample. The same applies hereinafter). The gel content is preferably 0.1% by weight or more, more preferably 0.3% by weight or more, and particularly preferably 0.5% by weight or more. Since the epoxidized product of the present invention is used as a modified resin for other resins, the upper limit is adjusted to the following epoxidation conditions so that it is preferably 30% by weight or less, more preferably 20% by weight or less.

According to the production method of the present invention, the reaction temperature when epoxidizing the thermoplastic polymer to be epoxidized is the type of thermoplastic polymer to be epoxidized, the size of the surface area, the type of solvent, the type and amount of the epoxidizing agent. Depending on the reaction time, it can be selected in the range of 10 to 70 ° C. When the reaction temperature is less than 10 ° C., the reaction rate is slow and not practical. On the other hand, if it exceeds 70 ° C., the self-decomposition of the peroxide becomes remarkable, which is not preferable. Further, there is a problem because dissolution of the surface of the thermoplastic polymer to be epoxidized with an organic solvent proceeds and blocking occurs. A particularly preferred reaction temperature is in the range of 30-60 ° C.
The pressure of the reaction system is usually atmospheric pressure, but may be slightly reduced pressure or slightly increased pressure.

  According to the production method of the present invention, the reaction time when epoxidizing the thermoplastic polymer to be epoxidized is the type of thermoplastic polymer to be epoxidized, the size of the surface area, the type of solvent, the type and amount of the epoxidizing agent. Depending on the reaction temperature, it can usually be selected within the range of 1 to 24 hours. When the reaction time is less than 1 hour, the conversion rate of double bonds is low and impractical. Conversely, when the reaction time is 24 hours or more, for example, when peracetic acid is used as the peroxide, Since a side reaction of coalescence occurs, it causes a decrease in yield and is not preferable. The epoxidizing agent and / or reaction accelerator may be charged all at once, but it is preferable to divide into several times and continuously (including dripping).

  According to the production method of the present invention, the reaction liquid after completion of the epoxidation reaction is a state in which the product epoxidized thermoplastic polymer is dispersed or suspended in water or an organic solvent, usually water, as a particulate solid, Further, a shell-like surface layer insoluble in a specific organic solvent is formed on the surface of the granular solid, and the suspension is obtained as a suspension in which carboxylic acid is dissolved in water or a solvent. In order to separate and recover the epoxidized product that exhibits a particulate solid from the suspension, a method such as filtration or centrifugation may be used. The product epoxidized product exhibiting the separated and recovered granular solid is washed with water to remove the solvent, carboxylic acid, and the like attached to the surface.

It is preferable to add the heat stabilizer to the particulate solid epoxidized thermoplastic polymer separated by the above method and then move to the solvent removal step which is the next step. This is because the polymer is effective in preventing oxidative degradation and thermal degradation when removing the solvent. These heat stabilizers may be added to the granular solid product as they are, or may be added after being dissolved in a hydrocarbon solvent.
Conventional heat-resistant stabilizers such as phenol-based and phosphorus-based stabilizers can be used. These heat stabilizers are preferably used in an amount of 0.01 to 3 parts by weight with respect to 100 parts by weight of the polymer, more preferably 0.05 to 3 parts by weight, and particularly preferably 0.1 to 2 parts by weight. Part range.
Two or more of the above phenol-based stabilizers can be used in combination. When the amount of the phenol-based stabilizer used is less than 0.01 parts by weight, the effect of improving the thermal stability and the color tone is low. Conversely, when the amount exceeds 3 parts by weight, the effect exceeding the range of the present invention is not exhibited.

Next, the obtained product is dried to obtain an epoxidized granular thermoplastic polymer having a cross-linked shell-like surface layer whose surface is resistant to a specific organic solvent. It is said that the organic solvent is directly removed from the obtained granular thermoplastic polymer by using at least one dryer such as a vacuum dryer or a hot air dryer, and the water content is reduced to less than 1% by weight. The production method according to the invention is not particularly limited as long as it is a method of drying while maintaining the granular form of the polymer.
In the method for producing a crosslinked epoxy-modified granular thermoplastic polymer according to the present invention, various additives depending on the purpose of the polymer, for example, softeners such as oil, plasticizer, antistatic agent, lubricant UV absorbers, flame retardants, pigments, inorganic fillers, organic or inorganic fibers, reinforcing agents such as carbon black, other thermoplastic resins, etc. are added, but these additives are added before entering the drying step. It is preferable to be added.

Next, the invention of the second group will be described.
The production method according to the present invention preferably uses a peroxide (C) as an epoxidizing agent in a state where the solid thermoplastic polymer (A) is dispersed or suspended in water (B). Further, a reaction accelerator (D) is used to maintain the dispersion state of the solid polymer during the epoxidation reaction, and without causing blocking of the polymer before or after the reaction or during the reaction. It is a method to convert.

  The thermoplastic polymer (A) used in the present invention can be applied as described in the first group of inventions as the thermoplastic polymer to be epoxidized. Further, the reaction accelerator (D) optionally used in carrying out the epoxidation reaction varies depending on the type of the epoxidation target thermoplastic polymer (A) and the reaction conditions of the epoxidation, but the above-mentioned first group. The reaction accelerator described in the invention can be used. Moreover, the peroxide (C) as an epoxidizing agent used in the present invention may be the same as the peroxide as an epoxidizing agent used in the first group of inventions in the same usage mode. Water (B) is used as a dispersion medium in the epoxidation reaction system. Although there is no restriction | limiting in particular, Preferably it is deionized water.

  In the present invention, the charging ratio of the thermoplastic polymer (A), water (B) and reaction accelerator (D) is (B) 50 to 1000 parts by weight with respect to (A) 100 parts by weight, (D) It is preferable that it is 0.5-20 weight part. In this case, if the component (B) is less than 50 parts by weight, the thermoplastic polymer to be epoxidized cannot be sufficiently dispersed or suspended, and if it exceeds 1000 parts by weight, the concentration of peroxide in the system is increased. The epoxidation reaction time is long and may not be efficient.

  In the reaction accelerator (D), the peroxide (C) as an epoxidizing agent can be dissolved and used, the solubility of the thermoplastic polymer to be epoxidized, and the organic solvent that is the operation after the epoxidation reaction From the viewpoint of easy recovery of the (reaction accelerator), for example, cyclohexane (solubility parameter value, SP value 8.2), ethyl acetate (SP value 9.1), chloroform (SP value 9.3). ), Toluene (SP value 8.9), xylene (SP value 8.8), methyl ethyl ketone (SP value 9.3), benzene (SP value 9.2), tetrahydrofuran (SP value 9.1) and the like are preferable. Moreover, the mixed solvent which consists of 1 type or 2 types or more of these can also be used. Moreover, it is preferable that the organic solvent as these reaction accelerators (D) is selected according to the kind of thermoplastic polymer to be epoxidized. The organic solvent penetrates into the inside of the thermoplastic polymer in a solid state, and at the same time, carries the peroxide of the epoxidizing agent to the inside, and has the function of epoxidizing to the inside of the thermoplastic polymer, As a selection criterion, an organic solvent capable of dissolving, swelling, and penetrating the thermoplastic polymer is selected.

  The amount of reaction accelerator (organic solvent) (D) used at the time of carrying out the epoxidation reaction is 100 wt. Of the thermoplastic polymer (A) when the solubility parameter value is less than 9.0. It is preferable that it is 0.5-20 weight part with respect to a part. In this case, when the charged amount of the reaction accelerator (D) is less than 0.5 parts by weight, the amount as a reaction accelerator for the reaction between the thermoplastic polymer (A) and the peroxide (C) is insufficient. It is sufficient and the epoxidation reaction takes a long time and is not efficient. On the other hand, when the amount exceeds 20 parts by weight, the surface of the epoxidized reaction polymer pellet or powder (hereinafter simply referred to as “pellet” except for the examples) is dissolved, and the thermoplastic polymer pellets Blocking may occur and dispersion by stirring during the epoxidation reaction may be difficult, epoxidation reaction in a dispersed state tends to be insufficient, and it is difficult to take out the epoxidation product from the reaction vessel May be.

When the solubility parameter value of the reaction accelerator is 9.0 or more, depending on the type of the thermoplastic polymer (A), a blocking phenomenon occurs even if the amount of the reaction accelerator (D) is increased as described later. The reaction can proceed without any delay.
For example, the thermoplastic polymer (A) is a styrene-butadiene copolymer, and has a general formula a- (ba) _n (where n ≧ 1, a is polystyrene, b is polybutadiene or a partially hydrogenated product thereof. In the case of a linear or branched polymer represented by: 50 to 1000 parts by weight of water (B) and a reaction accelerator (100 parts by weight with respect to 100 parts by weight of the thermoplastic polymer (A)). D) It is preferably carried out in a system using 0.5 to 30 parts by weight.
In this case, when the charged amount of the reaction accelerator (D) is less than 0.5 parts by weight, the amount as a reaction accelerator for the reaction between the thermoplastic polymer (A) and the peroxide (C) is insufficient. It is sufficient and the epoxidation reaction may take a long time and impair efficiency.
On the other hand, when the amount exceeds 30 parts by weight, dissolution of the pellet surface of the epoxidation reaction polymer occurs, blocking between the thermoplastic polymers occurs, and dispersion by a stirring operation during the epoxidation reaction becomes difficult. In some cases, the epoxidation reaction in a dispersed state tends to be insufficient, and it may be difficult to take out the epoxidation product from the reaction vessel.

The thermoplastic polymer used is a styrene-butadiene copolymer and is a polymer represented by the general formula (ab) _m (where m ≧ 2, a and b are the same as described above). In some cases, or in the case of being composed of a mixture of the same general formulas (ab) _m and a- (ba) _n (where n ≧ 1, a and b are the same as above) The water (B) is preferably 50 to 1000 parts by weight and the reaction accelerator (D) is 0.5 to 100 parts by weight with respect to 100 parts by weight of the thermoplastic polymer (A).
This is because, as shown in the general formula, it has a diblock structure of (ab) _m (where m ≧ 2, a is polystyrene, and b is polybutadiene or a partially hydrogenated product thereof). In the case of the triblock structure of the general formula a- (b-a) _n (where n ≧ 1, a and b are the same as described above), the molecular end is a polystyrene structure, whereas the molecular end is It has a polybutadiene structure. That is, in the case of a triblock structure, since both terminal structures are polystyrene structures, in the case of a diblock structure, since one terminal is a butadiene structure, the solubility by the reaction accelerator (D) is different. As a result, it is possible to increase the reaction accelerator.

Considering this reason, in view of the relationship between the molecular structure and the SP value, the SP value is 8.4 when the molecular end has a polybutadiene structure and has a structure of the general formula (ab) _m . When using a reaction accelerator having an SP value of 9.0 or more, the SP value difference between the two is large, resulting in poor solubility and no blocking, so increase the amount of reaction accelerator used. Is considered possible.
On the contrary, when the molecular terminal has a structure of general formula a- (ba) _n and the molecular terminal is a polystyrene structure, the SP value is 9.1, and the SP value is 9.0 or more as a reaction accelerator. When using, it is considered that blocking is caused because the difference in SP value between the two is small and as a result, the solubility is high. Therefore, in this case, the upper limit of the amount of reaction accelerator used is small.

  The thermoplastic polymer (A) used is a butadiene polymer, isoprene polymer, styrene-isoprene copolymer, acrylonitrile-butadiene copolymer, ethylene-propylene-diene terpolymer, and partial hydrogen of these thermoplastic polymers. Even in the case of at least one polymer selected from the group consisting of additives, the SP value has a large SP value difference with an organic solvent having an SP value of 9.0 or more, and 100 parts by weight of the thermoplastic polymer (A), It is considered that 50 to 1000 parts by weight of water (B) and 0.5 to 100 parts by weight of reaction accelerator (D) can be used.

When epoxidizing by the production method according to the present invention, the oxirane oxygen concentration of the obtained epoxidized product is adjusted by changing the reaction molar ratio of the double bond amount of the thermoplastic polymer to be epoxidized and the epoxidizing agent. It is possible. This reaction molar ratio varies depending on the level of the oxirane oxygen concentration of the resulting epoxidized product, but the reaction molar ratio of the pure peroxide to the amount of double bonds contained in the thermoplastic polymer to be epoxidized is 1.0 to It can be selected in the range of 3.0, and is particularly preferably selected in the range of 1.1 to 2.5. In addition, it is preferable that the oxirane oxygen concentration in the epoxidized thermoplastic polymer obtained is controlled in the range of 0.1 to 5.0% by weight.
The gel condition of the resulting epoxidized thermoplastic polymer is such that the insoluble content in toluene at 25 ° C. (ratio to the entire epoxidized thermoplastic polymer sample) is 5 wt% or less. Control is preferably performed. In addition, regarding the reaction conditions regarding manufacture, the reaction temperature, the pressure of the reaction system, and the reaction time described in the first group of the invention can be applied.

  According to the production method of the present invention, the reaction liquid after completion of the epoxidation reaction is a state in which the product epoxidized thermoplastic polymer is dispersed or suspended in water in a solid state, and the organic solvent or carboxylic acid is water. It is obtained as a suspension dissolved in In order to separate and recover the epoxidized product in a solid form from the dispersion or suspension, a method such as filtration or centrifugation may be used. The separated and recovered solid product epoxidized product is washed with water to remove surface adhering solvent, carboxylic acid and the like.

  It is preferable to add the heat stabilizer to the solid polymer separated by the above method and then move to the solvent removal step which is the next step. This is because it is effective to prevent the polymer from undergoing oxidative degradation or thermal degradation when the solvent is removed. The heat stabilizer may be added to the solid product as it is, or may be added after being dissolved in a hydrocarbon solvent. Conventional heat-resistant stabilizers such as phenol-based stabilizers and phosphorus-based stabilizers can be used.

  These heat stabilizers are used in the range of 0.01 to 3 parts by weight, preferably 0.05 to 3 parts by weight, and more preferably 0.1 to 2 parts by weight with respect to 100 parts by weight of the polymer. Further, two or more of the above phenol-based stabilizers can be used in combination. When the amount of the phenol-based stabilizer used is less than 0.01 part by weight, the effect of improving the thermal stability and the color tone is not recognized. Conversely, when the amount exceeds 3 parts by weight, the effect within the above range of the present invention. The above effects are not exhibited.

  Next, the obtained product is dried and commercialized. Here, drying the product means that the moisture content of the product is less than 1% by weight using at least one of a screw extruder type dryer, a kneader type dryer, an expander dryer and a hot air dryer. To do. Among the above-mentioned dryers, a particularly preferable dryer is a screw extruder type dryer, and among them, a multi-screw screw vent extruder type dryer such as a single screw or a twin screw is preferable.

  The dehydration step and the drying step in the present invention can also be performed by an apparatus in which a dehydrator and a dryer are integrated. A suitable device such as this is a biaxial or more shaft having at least one, preferably 2 to 4, slits for dehydration and at least one, preferably 2 to 4 vent portions for deaeration. A vent extruder may be mentioned.

  In the method of the present invention, various additives can be added to the polymer depending on the purpose. For example, softeners such as oils, plasticizers, antistatic agents, lubricants, ultraviolet absorbers, flame retardants, pigments, inorganic fillers, organic fibers / inorganic fibers, carbon black, and other thermoplastic resins Etc. can also be used as additives. These additives are preferably added before being added to the drying step.

EXAMPLES Hereinafter, although this invention is demonstrated based on an Example, this invention is not limited to the following description content, unless the summary is exceeded. In the following description, both “parts” and “%” are based on weight.
In addition, the oxirane oxygen concentration and gel content about the epoxidized product were measured by the method as described below.
Oxirane oxygen concentration: measured according to ASTM-1652.
Gel content: About 0.1 g of epoxidized thermoplastic copolymer is added to 10 ml of toluene, and after stirring and dissolving at 25 ° C. for 3 hours, the resulting solution is passed through a 200-mesh wire mesh and does not pass through the wire mesh. The dry weight of the water was measured, and the weight percentage with respect to the weight of the epoxidized thermoplastic copolymer was determined.

Example 1
A block copolymer of polystyrene-polybutadiene-polystyrene (SBS) [manufactured by Nippon Synthetic Rubber Co., Ltd .; product; a three-liter four-necked round bottom flask equipped with a stirrer, thermometer, dropping funnel and reflux condenser. No. TR2000] pellets (sphere equivalent particle diameter 3.5 mm) 300 g and water 500 g were charged, mixed well by stirring, and the SBS pellets were well dispersed in water. The temperature inside the flask was heated to 40 ° C., and a mixed solution of 42 g of ethyl acetate solution of 30% peracetic acid and 0.02 g of sodium tripolyphosphate was continuously added dropwise to the flask over 0.5 hour. The epoxidation was carried out for 4 hours (measured from the start of the dropwise addition of the peracetic acid solution.
Subsequently, 42 g of ethyl acetate solution of 30% peracetic acid was continuously added dropwise over 0.5 hours, and after the completion of addition, epoxidation reaction was performed for 2 hours, and 84 g of ethyl acetate solution of 30% peracetic acid was added over 1 hour. The reaction was continued for 10 hours. These reactions proceeded without causing blocking between the pellets.
After completion of the reaction, the solid matter was filtered and collected from the reaction solution, and washed with deionized water. Water and remaining solvent were removed from the collected solid under reduced pressure at 120 ° C. to obtain 300 g of epoxy-modified SBS. Each pellet of the modified SBS thus obtained has a structure covered with a shell-like surface layer insoluble in 25 ° C. toluene (when the pellet is slowly dissolved in toluene at 25 ° C., the pellet surface In other words, the gel content derived from the shell-like surface layer was 12.0% by weight, and the dissolved portion had an oxirane oxygen concentration of 1.5% by weight. Further, the oxirane oxygen concentration after the kneading of the pellets was 1.74% (showing the average value of the oxirane oxygen concentration of the whole pellet).

(Example 2)
To the same four-necked round bottom flask used in Example 1, polystyrene-polybutadiene-polystyrene (SBS) block copolymer [manufactured by Nippon Synthetic Rubber Co., Ltd .; trade name TR2000] pellets (sphere equivalent particle diameter 3.5 mm) ) 300 g and 600 g of water were charged and mixed well by stirring to disperse SBS. The temperature inside the flask was heated to 40 ° C., and a mixed solution of 42 g of ethyl acetate solution containing 30% peracetic acid and 0.02 g of sodium tripolyphosphate was continuously added dropwise to the flask over 0.5 hour. Epoxidation was carried out at 40 ° C. for 4 hours.
Subsequently, a mixed solution of 42 g of ethyl acetate solution of 30% peracetic acid and 0.02 g of sodium tripolyphosphate was continuously added dropwise over 0.5 hour, followed by epoxidation reaction for 2 hours after completion of the addition, and further peracetic acid. 84 g of 30% ethyl acetate solution was continuously added dropwise over 1 hour, and the reaction was carried out for 10 hours after the completion of the addition, but the reaction proceeded without blocking the pellets.
A particulate solid was filtered and collected from the reaction solution after the reaction was completed, and then washed with deionized water. Water and remaining solvent were removed from the collected solid under reduced pressure at 120 ° C. to obtain 300 g of epoxy-modified SBS having a shell-like surface layer insoluble in toluene at 25 ° C. The modified SBS has a structure covered with a shell-like surface layer insoluble in toluene (confirmed in the same manner as in Example 1), has a gel component content of 7.8% by weight, The oxirane oxygen concentration was 2.1% by weight. Moreover, the oxirane oxygen concentration after kneading was 2.23%.

(Example 3)
To the same four-necked round bottom flask used in Example 1, polystyrene-polybutadiene-polystyrene (SBS) block copolymer [manufactured by Asahi Kasei Co., Ltd .; trade name Asaflex 810] pellets (sphere equivalent particle diameter: 3. 8 mm) 300 g and water 500 g were charged, stirred and mixed well to disperse the SBS pellets. The temperature inside the flask was heated to 40 ° C., and a mixed solution of 63 g of 30% peracetic acid in ethyl acetate and 0.03 g of sodium tripolyphosphate was continuously added dropwise thereto over 0.5 hours. After completion of the dropping, epoxidation was carried out at 40 ° C. for 5 hours with stirring. At that time, 54 g of ethyl acetate was continuously added dropwise over 0.5 hours, and the reaction was performed for a total of 12 hours. The reaction proceeded without blocking the pellets.
The solid pellet was filtered and collected from the reaction solution after completion of the reaction, and then washed with deionized water. Water and remaining solvent were removed from the recovered pellets at 120 ° C. under reduced pressure, and 300 g of epoxy-modified SBS pellets having a shell-like surface layer insoluble in toluene at 25 ° C. (confirmed in the same manner as in Example 1) was obtained. It was. The SBS had a gel content of 3.2% by weight and an oxirane oxygen concentration in the dissolved portion of 1.0% by weight. The oxirane oxygen concentration after kneading was 1.11%.

Example 4
In the same four-necked round bottom flask used in Example 1, polystyrene-polyisoprene-polystyrene (SIS) block copolymer [manufactured by Shell Co., Ltd .; trade name Kraton D1117] pellets (sphere equivalent particle size: 3 0.9 mm) and 300 g of water and 600 g of water were added, and the mixture was stirred and mixed well to disperse the SIS pellets. The temperature inside the flask was heated to 40 ° C., and a mixed solution of 164 g of a 30% ethyl acetate solution of peracetic acid and 0.09 g of sodium tripolyphosphate was continuously added dropwise to the flask over 2 hours. Epoxidation was performed for 6 hours. The reaction proceeded without blocking the pellets.
The solid pellet was filtered and collected from the reaction solution after completion of the reaction, and then washed with deionized water. The recovered pellets were heated to 120 ° C. under reduced pressure to remove water and remaining solvent, and a shell-like surface layer whose surface was insoluble in toluene at 25 ° C. was formed (checked in the same manner as in Example 1). ) 300 g of epoxy-modified SIS polymer pellets were obtained. The gel content of the modified pellet was 14.5% by weight, and the oxirane oxygen concentration in the dissolved portion was 1.4% by weight. Moreover, the oxirane oxygen concentration after kneading was 1.72%.

(Example 5)
In the same four-necked round bottom flask used in Example 1, 300 g of pellets (sphere equivalent particle diameter: 3.4 mm) of polyacrylonitrile-polybutadiene (NBR) [manufactured by Nippon Zeon Co., Ltd .; Nipol NBR DN214], 600 g of water. Were mixed with stirring well to disperse the pellets. The temperature inside the flask was heated to 40 ° C., and a mixed solution of 63 g of a 30% ethyl acetate solution of peracetic acid and 0.03 g of sodium tripolyphosphate was continuously added dropwise to the flask over 1 hour. Time epoxidation was performed. The reaction proceeded without blocking the pellets.
From the reaction solution after completion of the reaction, solid pellets were filtered and collected, and then washed with deionized water. Water and remaining solvent were removed from the recovered pellets under reduced pressure, and a shell-like surface layer insoluble in toluene at 25 ° C. was formed on the surface (confirmed in the same manner as in Example 1). Epoxy-modified NBR polymer 299 g was obtained. The NBR polymer had a gel component content of 2.5% by weight and an oxirane oxygen concentration in the dissolved portion of 1.1% by weight. The oxirane oxygen concentration after kneading was 1.21%.

(Reference Example 1)
A pulverized product of ethylene-propylene-diene terpolymer (EPDM) pellets having an iodine value of 10 in a 1-liter four-necked round bottom flask equipped with a stirrer, thermometer, dropping funnel and reflux condenser, A 7.5 mesh pass product (number average molecular weight 5300 by GPC method) 100 g and 200 g of water as a solvent were charged and mixed well by stirring to disperse the EPDM pulverized product. While maintaining the internal temperature of the flask at 40 ° C. and maintaining this temperature, 12.0 g of 30% pure ethyl acetate solution and 10 g of cyclohexane were dropped into the flask over about 30 minutes using a dropping funnel and reacted. Further, the reaction was carried out at this temperature for 8 hours (the SP value of the accelerator was 8.6 as a weighted average value of both solvents, and the amount used was equivalent to 18.4 parts by weight with respect to 100 parts by weight of the starting polymer. The same calculation was performed in the case of the mixed solvent in the Examples and Comparative Examples). The reaction proceeded without forming a lump. After the reaction was completed, the solid was collected by filtration and washed with deionized water in the same amount as the reaction solution. Furthermore, in order to remove water and the like, it was dried under reduced pressure to obtain 99.0 g of epoxidized EPDM. The resulting epoxidized EPDM had an oxirane oxygen concentration of 0.5% and a gel content of 0.1%. Further, the oxirane oxygen concentration after kneading (indicating the average value of the oxirane oxygen concentration of the whole particle) was 0.52%.

(Reference Example 2)
In the same four-necked round bottom flask used in Reference Example 1, a commercially available pellet product of ethylene-propylene-diene terpolymer (EPDM) having an iodine value of 10 (number average molecular weight 5300 by GPC method) (sphere-converted particle diameter) : 2.3 mm) and 200 g of water as a solvent were charged, and mixed well by stirring to disperse EPDM pellets. While maintaining the temperature inside the flask at 40 ° C. and maintaining this temperature, 12.0 g of an ethyl acetate solution of 30% purity and 10 g of cyclohexane were dropped and reacted over about 30 minutes using a dropping funnel. The reaction was carried out at this temperature for 8 hours (the SP value of the accelerator was 8.6, and the amount used was 18.4 parts by weight). The reaction proceeded without blocking the pellets.
After completion of the reaction, the solid was collected by filtration and washed with deionized water in the same amount as the reaction solution. Furthermore, in order to remove water etc., it was dried under reduced pressure to obtain 100 g of epoxidized EPDM (substantially the same weight as the raw material). The resulting epoxidized EPDM had an oxirane oxygen concentration of 0.5% and a gel content of 0.08%. Moreover, the oxirane oxygen concentration after kneading was 0.2%.

(Reference Example 3)
A block copolymer of polystyrene-polybutadiene-polystyrene (SBS) [manufactured by Nippon Synthetic Rubber Co., Ltd .; product; a three-liter four-necked round bottom flask equipped with a stirrer, thermometer, dropping funnel and reflux condenser. Name TR2000] 300 g of pellets (sphere equivalent particle diameter: 3.5 mm) and 500 g of water were charged, mixed well by stirring, and SBS pellets were dispersed. The flask was warmed to 40 ° C, and 42 g of 30% peracetic acid in ethyl acetate was continuously added dropwise over 0.5 hour. After completion of the addition, epoxidation was carried out at 40 ° C for 8 hours with stirring. (The SP value of the accelerator is 9.1, and the amount used is 9.8 parts by weight). The reaction proceeded without blocking the pellets.
From the reaction solution after completion of the reaction, a solid was collected by filtration and then washed with deionized water. Water and remaining solvent were removed from the collected solid under reduced pressure to obtain 300 g of epoxidized SBS. The resulting epoxidized SBS had an oxirane oxygen concentration of 0.70% and a gel content of 0.36%. Moreover, the oxirane oxygen concentration after kneading was 0.75%.

(Reference Example 4)
To the same four-necked round bottom flask used in Reference Example 3, polystyrene-polybutadiene-polystyrene (SBS) block copolymer [manufactured by Nippon Synthetic Rubber Co., Ltd .; trade name TR2000] pellets (sphere equivalent particle diameter: 3. 5 mm) 300 g of water and 500 g of water were charged and mixed well by stirring to disperse the SBS pellets. The flask was warmed to 30 ° C and 42 g of 30% peracetic acid in ethyl acetate was continuously added dropwise over 0.5 hour. After completion of the addition, epoxidation was performed at 30 ° C for 9 hours with stirring. (The SP value of the accelerator is 9.1, and the amount used is 9.8 parts by weight). The reaction proceeded without blocking the pellets.
From the reaction solution after completion of the reaction, a solid was collected by filtration and then washed with deionized water. Water and remaining solvent were removed from the collected solid under reduced pressure to obtain 300 g of epoxidized SBS. The resulting epoxidized SBS had an oxirane oxygen concentration of 0.55% and a gel content of 0.04%. The oxirane oxygen concentration after kneading was 0.56%.

(Reference Example 5)
To the same four-necked round bottom flask used in Reference Example 3, polystyrene-polybutadiene-polystyrene (SBS) block copolymer [manufactured by Nippon Synthetic Rubber Co., Ltd .; trade name TR2000] pellets (sphere equivalent particle diameter: 3. 5 mm) 300 g of water and 500 g of water were charged and mixed well by stirring to disperse the SBS pellets. The flask was warmed to 40 ° C., and 168 g of a 15% aqueous solution of peracetic acid was continuously added dropwise over 2 hours. Further, 30 g of cyclohexane was added dropwise over 0.25 hours. Epoxidation was carried out at 40 ° C. for 6 hours (the accelerator had an SP value of 8.2 and the amount used was 10 parts by weight). The reaction proceeded without blocking the pellets.
From the reaction solution after completion of the reaction, a solid was collected by filtration and then washed with deionized water. Water and remaining solvent were removed from the collected solid under reduced pressure to obtain 300 g of epoxidized SBS. The resulting epoxidized SBS had an oxirane oxygen concentration of 1.0% and a gel content of 0.88%. The oxirane oxygen concentration after kneading was 1.10%.

(Reference Example 6)
To the same four-necked round bottom flask used in Reference Example 3, a polystyrene-polybutadiene-polystyrene (SBS) block copolymer [manufactured by Asahi Kasei Co., Ltd .; trade name Asaflex 810] pellets (sphere equivalent particle diameter: 3. 8 mm) 300 g and water 500 g were charged, stirred and mixed well to disperse the SBS pellets. The flask was heated to 40 ° C., and 84 g of 30% peracetic acid ethyl acetate solution was continuously added dropwise thereto over 1 hour. After completion of the dropwise addition, epoxidation was carried out at 40 ° C. for 7 hours with stirring ( The SP value of the accelerator is 9.1, and the amount used is 19.6 parts by weight). The reaction proceeded without blocking the pellets.
From the reaction solution after completion of the reaction, a solid was collected by filtration and then washed with deionized water. Water and remaining solvent were removed from the collected solid under reduced pressure to obtain 300 g of epoxidized SBS. The resulting epoxidized SBS had an oxirane oxygen concentration of 0.89% and a gel content of 0.3%. Moreover, the oxirane oxygen concentration after kneading was 0.91%.

(Reference Example 7)
In the same four-necked round bottom flask used in Reference Example 3, a polystyrene-polybutadiene-polystyrene (SBS) block copolymer [manufactured by Shell Co., Ltd .; trade name Kraton D1118, diblock content 80%] crumb (sphere (Equivalent particle size: 4.3 mm) 300 g and 600 g of water were charged, mixed well with stirring, and SBS pellets were dispersed. The flask was warmed to 40 ° C., and 42 g of a 30% ethyl acetate solution of peracetic acid was continuously added dropwise over 0.5 hours. After completion of the addition, epoxidation was carried out at 40 ° C. for 6 hours with stirring. (The SP value of the accelerator is 9.1, and the amount used is 9.8 parts by weight). The reaction proceeded without blocking the pellets.
From the reaction solution after completion of the reaction, a solid was collected by filtration and then washed with deionized water. Water and remaining solvent were removed from the collected solid under reduced pressure to obtain 300 g of an epoxidized SBS polymer. The resulting epoxidized SBS had an oxirane oxygen concentration of 0.75% and a gel content of 0.03%. The oxirane oxygen concentration after kneading was 0.77%.

(Reference Example 8)
In the same four-necked round bottom flask used in Reference Example 3, polystyrene-polybutadiene-polystyrene (SBS) block copolymer [manufactured by Shell Co., Ltd .; trade name Clayton D1118] crumb (sphere equivalent particle diameter: 4.3 mm) ) 300 g and 600 g of water were charged and mixed with stirring to disperse the SBS pellets. The flask was heated to 40 ° C., and 126 g of a 30% ethyl acetate solution of peracetic acid was continuously added dropwise over 15 hours. After completion of the dropwise addition, epoxidation was performed at 40 ° C. for 6 hours with stirring ( The SP value of the accelerator is 9.1, and the amount used is 29.4 parts by weight). The reaction proceeded without blocking the pellets.
From the reaction solution after completion of the reaction, a solid was collected by filtration and then washed with deionized water. Water and remaining solvent were removed from the collected solid under reduced pressure to obtain 300 g of an epoxidized SBS polymer. The resulting epoxidized SBS had an oxirane oxygen concentration of 2.2% and a gel content of 1.1%. Moreover, the oxirane oxygen concentration after kneading was 2.35%.

(Reference Example 9)
To the same four-necked round bottom flask used in Reference Example 4, a polystyrene-polyisoprene-polystyrene (SIS) block copolymer [manufactured by Shell Co., Ltd .; trade name Clayton D1117] pellets (sphere equivalent particle diameter: 3. 9 mm) 300 g and 600 g of water were charged and mixed well by stirring to disperse the SIS pellets. The temperature inside the flask was heated to 40 ° C., and 164 g of a 30% ethyl acetate solution of peracetic acid was continuously added dropwise over 2 hours. After completion of the addition, epoxidation was performed at 40 ° C. for 6 hours with stirring ( The SP value of the accelerator is 9.1, and the amount used is 38.2 parts by weight). The reaction proceeded without blocking the pellets.
From the reaction solution after completion of the reaction, a solid was collected by filtration and then washed with deionized water. Water and remaining solvent were removed from the collected solid under reduced pressure to obtain 300 g of an epoxidized SIS polymer. The resulting epoxidized SIS had an oxirane oxygen concentration of 2.2% and a gel content of 3.5%. The oxirane oxygen concentration after kneading was 2.41%.

(Reference Example 10)
To the same four-necked round bottom flask used in Reference Example 3, a polystyrene-polyisoprene-polystyrene (SIS) block copolymer [manufactured by Shell Co., Ltd .; trade name Kraton D1117] pellets (sphere equivalent particle diameter: 3. 9 mm) 300 g and 600 g of water were charged and mixed well by stirring to disperse the SIS pellets. The flask was warmed to 40 ° C., and 168 g of a 15% aqueous solution of peracetic acid was continuously added dropwise over 2 hours. Further, 30 g of cyclohexane was added dropwise over 0.25 hours. Epoxidation was carried out at 40 ° C. for 6 hours (the accelerator had an SP value of 8.2 and the amount used was 10 parts by weight). The reaction proceeded without blocking the pellets.
From the reaction solution after completion of the reaction, a solid was collected by filtration and then washed with deionized water. Water and remaining solvent were removed from the collected solid under reduced pressure to obtain 300 g of an epoxidized SIS polymer. The resulting epoxidized SIS had an oxirane oxygen concentration of 1.3% and a gel content of 1.5%. Moreover, the oxirane oxygen concentration after kneading was 1.42%.

(Reference Comparative Example 1)
To the same four-necked round bottom flask used in Reference Example 3, polystyrene-polybutadiene-polystyrene (SBS) block copolymer [manufactured by Nippon Synthetic Rubber Co., Ltd .; trade name TR2000] pellets (sphere equivalent particle diameter: 3. 5 mm) 300 g of water and 500 g of water were charged and mixed well by stirring to disperse the SBS pellets. The flask was heated to 40 ° C., and 168 g of a 30% peracetic acid ethyl acetate solution was continuously added dropwise over 2 hours. After completion of the addition, the pellets blocked each other, and the agitator stopped. (The SP value of the accelerator was 9.1, and the amount used was 39.2 parts by weight).

(Reference Comparative Example 2)
To the same four-necked round bottom flask used in Reference Example 3, a polystyrene-polybutadiene-polystyrene (SBS) block copolymer [manufactured by Asahi Kasei Co., Ltd .; trade name Asaflex 810] pellets (sphere equivalent particle diameter: 3. 8 mm) 300 g and water 500 g were charged, stirred and mixed well to disperse the SBS pellets. The flask was heated to 40 ° C., and 168 g of a 30% peracetic acid ethyl acetate solution was continuously added dropwise over 2 hours. After completion of the addition, the pellets blocked each other, and the agitator stopped. (The SP value of the accelerator was 9.1, and the amount used was 39.2 parts by weight).

Claims (13)

  An epoxidized granular thermoplastic polymer comprising a shell-like surface layer insoluble in toluene at 25 ° C.   2. The epoxidized granular thermoplastic polymer according to claim 1, wherein the spherical particle diameter of the thermoplastic polymer is in the range of 0.05 to 7 mm.   The epoxidized granular thermoplastic polymer according to claim 1 or 2, wherein the thermoplastic polymer is a diene polymer.   The diene polymer is at least one diene polymer selected from the group consisting of butadiene polymers, styrene-butadiene copolymers, isoprene polymers, styrene-isoprene copolymers, and acrylonitrile-butadiene copolymers. The epoxidized granular thermoplastic polymer according to claim 3.   The epoxidized granular thermoplastic polymer according to any one of claims 1 to 4, wherein an oxirane oxygen concentration of the epoxidized granular thermoplastic polymer is 0.3 to 5.0% by weight.   The epoxidized granular thermoplastic polymer according to any one of claims 1 to 5, wherein the gel content of the epoxidized granular thermoplastic polymer is 0.1% by weight or more.   A first epoxidized granular thermoplastic polymer is obtained by epoxidizing a granular thermoplastic polymer in an aqueous medium in the presence of an epoxidizing agent, an epoxidizing agent, an epoxidation reaction-promoting solvent, and a phosphoric acid compound. As needed for the removal of the epoxidation reaction-promoting solvent that may be used in the second step for neutralization and water washing, and the epoxidized granular thermoplastic polymer. The method for producing an epoxidized granular thermoplastic polymer according to claim 1, comprising a third step.   The method for producing an epoxidized granular thermoplastic polymer according to claim 7, wherein peracetic acid is used as an epoxidizing agent in the first step.   The method for producing an epoxidized granular thermoplastic polymer according to claim 7 or 8, wherein the SP value of the epoxidation reaction accelerating solvent that may be used in the first step is 10 or less.   The method for producing an epoxidized granular thermoplastic polymer of the seventh invention, wherein the water washing in the second step, or neutralization and water washing is a solid-liquid separation operation for separating the polymer supplied to the third step.   The eleventh aspect of the present invention is the epoxidized granular thermoplastic polymer according to claim 7, wherein the solvent is removed in the third step by drying while maintaining the granular shape of the polymer obtained in the second step. Manufacturing method.   The method for producing an epoxidized granular thermoplastic polymer according to any one of claims 7 to 11, wherein the oxirane oxygen concentration in the epoxidized granular thermoplastic polymer is 0.3 to 5.0 wt%.   The method for producing an epoxidized granular thermoplastic polymer according to any one of claims 7 to 12, wherein the gel content of the epoxidized granular thermoplastic polymer is 0.5% by weight or more.