JP2000191736A - Graft polymerization of thermoplastic polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method by which a graft polymerization can be carried out with a high efficiency while suppressing crosslinking and decomposing reactions when conducting the graft polymerization of a radically polymerizable monomer with a thermoplastic polymer. SOLUTION: (A) A thermoplastic polymer is brought into contact with (C) a radical initiator and (D-1) a radical-containing compound of oxygen, nitrogen, phosphorus, sulfur, carbon or silicon or (D-2) a radical-producing compound capable of producing the radical-containing compound (D-1) at a temperature for enabling the radical initiator (C) to produce the radical before adding (B) a radically polymerizable monomer in a method for carrying out a graft polymerization of the radically polymerizable monomer (B) with the thermoplastic polymer (A) in the presence of the radical initiator (C).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for graft-polymerizing a thermoplastic polymer with a functional monomer. More specifically, the present invention relates to a method for suppressing side reactions such as decomposition and cross-linking when grafting a functional monomer to a thermoplastic polymer, and for performing graft polymerization with high graft efficiency.

[0002]

BACKGROUND OF THE INVENTION As a method for introducing various functional groups into a thermoplastic polymer such as polyolefin,
A method of graft-polymerizing a radical polymerizable monomer in the presence of a radical generator is generally performed. However, this method involves coupling of radicals, cross-linking and decomposition of the polymer due to side reactions such as β-cleavage, etc., and the melting characteristics (melt flow rate) of the obtained graft polymer
(MFR) and the like (physical properties related to the structure such as the molecular weight of the polymer).

In order to solve such a problem, Japanese Patent Application Laid-Open No. H10-130308 describes a method of performing graft polymerization on a thermoplastic polymer in the presence of a stable nitroxide radical. However, this publication only exemplifies a method in which a thermoplastic polymer, a radical initiator, a monomer having a functional group, and a stable nitroxide radical are collectively added from one end of an extruder to carry out a reaction. Further, as for the monomer having a functional group to be used, specifically, only maleic anhydride is exemplified, and the graft reaction amount is also in a low range of 0.8 to 1.7%.

That is, when a relatively small amount of a monomer having a relatively low self-polymerization property such as maleic anhydride exemplified in the above-mentioned publication is grafted, problems such as cross-linking and decomposition of the polymer due to side reactions become apparent. Because of this, the effect of suppressing side reactions by this method is unknown. On the other hand, when a large amount of a monomer having a high self-polymerization property such as (meth) acrylic acid and a derivative thereof or an aromatic vinyl compound is to be graft-reacted, the graft polymerization reaction is performed simply by allowing a stable nitroxide radical to exist in the system. However, it is difficult to suppress the occurrence of side reactions such as crosslinking and decomposition and the decrease in graft efficiency by simply performing the above steps.

[0005]

DISCLOSURE OF THE INVENTION The present invention has been made under the above-mentioned background.
An object of the present invention is to provide a method capable of performing graft polymerization with high efficiency while suppressing a decomposition reaction.

[0006]

Means for Solving the Problems The present inventors have conducted intensive studies in order to achieve the above object, and as a result, after contacting a thermoplastic polymer with a radical initiator and a specific radical compound in advance, the radical polymerizable The inventors have found that the above problems can be solved by adding a monomer, and have accomplished the present invention.

The method for graft polymerization of a thermoplastic polymer according to the present invention is a method for graft-polymerizing a radical polymerizable monomer (B) to a thermoplastic polymer (A) in the presence of a radical initiator (C). Before the addition of the monomer (B), at a temperature at which the radical initiator (C) can generate radicals, the thermoplastic polymer (A), the radical initiator (C) and oxygen, nitrogen, phosphorus, sulfur, carbon or It is characterized by contacting with a radical-containing compound (D-1) of silicon or a radical-forming compound (D-2) capable of producing the radical-containing compound (D-1).

In a preferred embodiment of the present invention, the radical-containing compound (D-1) is preferably a compound represented by the following general formula (I).

Embedded image (Wherein, Z represents nitrogen, sulfur or phosphorus, X represents an optional substituent, and n is an integer of 1 to 4 that satisfies the valence of Z.)

[0009] In a preferred embodiment of the present invention,
It is preferable that the radical-containing compound (D-1) is a nitroxide radical-containing compound in which Z in the formula (I) is a nitrogen atom.

[0010] In a preferred embodiment of the present invention,
The nitroxide radical-containing compound has the following general formula (I
Desirably, the compound is represented by I) or (III).

Embedded image (In the above formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , and R ⁶ each independently represent a halogen atom such as chlorine or bromine;
Represents a linear or branched or cyclic saturated or unsaturated hydrocarbon group or an aryl group, which may be the same or different, and ^one of R ¹ , R ² , R ³ and R ⁴ , R ⁵ and R ⁶ may be linked to form a cyclic structure. )

Embedded image (In the above formula, R ⁷ and R ⁸ are each independently a halogen atom such as chlorine or bromine, a linear or branched or cyclic saturated or unsaturated hydrocarbon group or an aryl group having 1 to 10 carbon atoms. Represents the same or different from each other,
R ⁷ and R ⁸ may be linked to form a cyclic structure. )

[0011] In a preferred embodiment of the present invention,
It is desirable that the radical generating compound (D-2) is a secondary amine.

In a preferred embodiment of the present invention,
It is desirable that the secondary amine is a compound represented by the following general formula (IV).

Embedded image (In the above formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , and R ⁶ each independently represent a halogen atom such as chlorine or bromine;
Represents a linear or branched or cyclic saturated or unsaturated hydrocarbon group or an aryl group, which may be the same or different, and ^one of R ¹ , R ² , R ³ and R ⁴ , R ⁵ and R ⁶ may be linked to form a cyclic structure. )

[0013] In a preferred embodiment of the present invention,
The number of moles of radicals derived from the radical-containing compound (D-1) or the theoretical number of moles of radicals that can be generated from the radical-forming compound (D-2) is equal to the number of moles of radicals that can be generated in the radical initiator (C). It is desirable to use 0.01 to 2.0 times the theoretical mole number.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, when a radical polymerizable monomer (B) is graft-polymerized to a thermoplastic polymer (A), the thermoplastic polymer (A) is previously reacted with a radical initiator (C), oxygen, It was brought into contact with a radical-containing compound (D-1) of nitrogen, phosphorus, sulfur, carbon or silicon, or a radical-forming compound (D-2) capable of producing the radical-containing compound (D-1) at a predetermined temperature. Thereafter, a graft polymerization method for a thermoplastic polymer, characterized by adding a radical polymerizable monomer (B). First, a thermoplastic polymer (A), a radical polymerizable monomer (B), a radical initiator (C), a radical-containing compound of oxygen, nitrogen, phosphorus, sulfur, carbon or silicon (D-
1) or the radical-forming compound (D-2) capable of producing the radical-containing compound (D-1) will be described.

Thermoplastic Polymer (A) The thermoplastic polymer used in the present invention is not particularly limited as long as it can be graft-polymerized by a radical reaction. Polyester, polyacetal,
From polystyrene, acrylonitrile-butadiene-styrene copolymer (ABS), polymethacrylate, polycarbonate, polyphenylene oxide, polyvinyl chloride, polyvinylidene chloride, polyvinyl acetate and ethylene- (meth) acrylate copolymer, diene rubber At least one type of thermoplastic polymer selected from the group consisting of polyolefins, polyesters, polyamides, polystyrenes, and diene rubbers is particularly preferable.

Polyolefins include polyethylene,
Olefin homopolymer such as polypropylene, poly-1-butene, polymethylpentene, polymethylbutene, ethylene-α-olefin random copolymer, propylene-
Olefin copolymers such as an ethylene random copolymer and an ethylene-propylene-diene terpolymer can be mentioned. Among them, polyethylene, polypropylene, ethylene-α-olefin random copolymer, and ethylene-propylene-diene terpolymer are preferred. In addition,
When the polyolefin is a polyolefin obtained from an olefin having 3 or more carbon atoms, it may be an isotactic polymer, a syndiotactic polymer, or an atactic polymer. As these polyolefins, those produced in the presence of either a Ziegler-Natta type catalyst or a metallocene catalyst can be used.

Examples of the polyamide include aliphatic polyamides such as nylon 6, nylon 66, nylon 10, nylon 12, and nylon 46, and aromatic polyamides prepared from aromatic dicarboxylic acids and aliphatic diamines. Among them, nylon 6 is preferable.

Examples of the polyester include aromatic polyesters such as polyethylene terephthalate, polyethylene naphthalate, and polybutylene terephthalate, polycaprolactone, and polyhydroxybutyrate, and polyethylene terephthalate is preferred.

Examples of the polyacetal include polyformaldehyde (polyoxymethylene), polyacetaldehyde, polypropionaldehyde, polybutyraldehyde, and the like. Of these, polyformaldehyde is preferred.

The polystyrene may be a homopolymer of styrene or a binary copolymer of styrene with acrylonitrile, methyl methacrylate, α-methylstyrene, etc., for example, an acrylonitrile-styrene copolymer. .

The ABS contains a structural unit derived from acrylonitrile in an amount of 20 to 35 mol%, a structural unit derived from butadiene in an amount of 20 to 30 mol%, and is derived from styrene. Structural unit 40 ~
Those containing in an amount of 60 mol% are preferably used.

As the polymethacrylate, polymethyl methacrylate (PMMA) is preferable. As polycarbonate, bis (4-hydroxyphenyl) methane,
Examples thereof include those obtained from 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyphenyl) butane, and the like. Among them, polycarbonate obtained from 2,2-bis (4-hydroxyphenyl) propane is preferable.

As the polyphenylene oxide, poly (2,6-dimethyl-1,4-phenylene oxide) is preferable. The polyvinyl chloride may be a homopolymer of vinyl chloride or a copolymer with vinylidene chloride, acrylate, acrylonitrile, propylene, or the like. Polyvinylidene chloride is usually composed of vinyl chloride, acrylonitrile,
Copolymers with (meth) acrylates, allyl esters, unsaturated ethers, styrene and the like are used.

The polyvinyl acetate may be a homopolymer of vinyl acetate or a copolymer of ethylene and vinyl chloride. Of these, an ethylene-vinyl acetate copolymer is preferred. As the ethylene- (meth) acrylate copolymer, ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer,
Ethylene-methyl methacrylate copolymer, ethylene-
Ethyl methacrylate copolymer is preferred.

Examples of the diene rubber include polybutadiene,
Mention may be made of conjugated polydienes such as polyisoprene or elastomeric styrene-butadiene copolymers, also known as SBR (styrene-butadiene rubber).

The above-mentioned thermoplastic polymers can be used alone or in combination of two or more. Among these thermoplastic polymers, polyolefins, polyesters, polyamides, polystyrenes, diene rubbers and the like can be preferably mentioned, and it is more preferable to use polyolefins.

Radical polymerizable monomer (B) The radical polymerizable monomer (B) used in the present invention comprises:
It is not particularly limited as long as it is a monomer containing at least one double bond capable of radical polymerization in the molecule, but a hydroxyl group-containing ethylenically unsaturated compound and an amino group-containing compound can be used because the reaction can be performed with higher grafting efficiency. At least one selected from the group consisting of ethylenically unsaturated compounds, epoxy group-containing ethylenically unsaturated compounds, aromatic vinyl compounds, unsaturated carboxylic acids and derivatives thereof, vinyl ester compounds, nitrile group-containing unsaturated compounds, and vinyl chloride Is preferred.

Specific examples of the hydroxyl group-containing ethylenically unsaturated compound include hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and 2-hydroxypropyl (meth) acrylate.
-3-phenoxy-propyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, glycerin mono (meth) acrylate, pentaerythritol mono (meth) acrylate, trimethylolpropane mono (meth) acrylate, tetramethylol (Meth) acrylic acid esters such as ethane mono (meth) acrylate, butanediol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate and 2- (6-hydroxyhexanoyloxy) ethyl acrylate; 10-undecene-1- All, 1-octen-3-ol, 2-methanol norbornene, hydroxystyrene,
Hydroxyethyl vinyl ether, hydroxybutyl vinyl ether, N-methylolacrylamide, 2- (meth) acryloyloxyethyl acid phosphate,
Glycerin monoallyl ether, allyl alcohol, allyloxyethanol, 2-butene-1,4-diol, glycerin monoalcohol and the like can be mentioned.

The amino group-containing ethylenically unsaturated compound is
A compound having an ethylenic double bond and an amino group. Examples of such a compound include a vinyl monomer having at least one kind of an amino group and a substituted amino group represented by the following formula (V). Can be.

Embedded image (In the above formula, R ¹¹ represents a hydrogen atom, a methyl group or an ethyl group, and R ¹² represents a hydrogen atom, an alkyl group having 1 to 12, preferably 1 to 8 carbon atoms, or a carbon atom having 6 to 1 carbon atoms.
It shows 2, preferably 6 to 8 cycloalkyl groups, and the above-mentioned alkyl groups and cycloalkyl groups may further have a substituent. )

Specific examples of such an amino group-containing ethylenically unsaturated compound include aminoethyl (meth) acrylate, propylaminoethyl (meth) acrylate,
Alkyl ester derivatives of acrylic acid or methacrylic acid such as dimethylaminoethyl methacrylate, aminopropyl (meth) acrylate, phenylaminoethyl methacrylate and cyclohexylaminoethyl methacrylate; N-vinyldiethylamine and N-acetylvinylamine Vinylamine derivatives: allylamine, methacrylamine, N-methylacrylamine, N, N-
Allylamine derivatives such as dimethylacrylamide and N, N-dimethylaminopropylacrylamide; acrylamide derivatives such as acrylamide and N-methylacrylamide; aminostyrenes such as p-aminostyrene; 6-aminohexylsuccinimide; Aminoethyl succinimide and the like are used.

The epoxy group-containing ethylenically unsaturated compound is a compound having at least one polymerizable unsaturated bond and at least one epoxy group in one molecule. Examples of such an epoxy group-containing ethylenically unsaturated compound include: Specifically, glycidyl acrylate, glycidyl methacrylate, mono and di glycidyl esters of maleic acid, mono and di glycidyl esters of fumaric acid, mono and di glycidyl esters of crotonic acid, mono and di glycidyl esters of tetrahydrophthalic acid, itaconic acid Mono- and glycidyl esters of butenetricarboxylic acid, mono- and diglycidyl esters of citraconic acid, endo-cis-bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylic acid (nadic acid mono- and di ^TM) Glycidyl esters, end - cis - bicyclo [2.2.1] hept-5-ene-2-methyl-2,
3-dicarboxylic acid mono and diglycidyl esters, (1 to 12 carbon atoms in the alkyl group in the case of monoglycidyl ester) dicarboxylic acid mono and alkyl glycidyl esters, such as mono- and glycidyl esters of allyl succinic acid (methylnadic acid ^TM) , Alkyl glycidyl ester of p-styrenecarboxylic acid, allyl glycidyl ether, 2-methylallyl glycidyl ether, styrene-p-glycidyl ether, 3,4-epoxy-1-butene, 3,
4-epoxy-3-methyl-1-butene, 3,4-epoxy-1-pentene, 3,4-epoxy-3-methyl-1-pentene, 5,6-epoxy-1-hexene, vinylcyclohexene monoxide And the like.

As the aromatic vinyl compound, the following formula (V
Compounds represented by I) are mentioned.

Embedded image (In the above formula, R ¹³ and R ¹⁴ may be the same or different from each other, and have a hydrogen atom or a carbon atom number of 1 to 3.
R ¹⁵ represents a hydrocarbon group having 1 to 3 carbon atoms or a halogen atom, and n is an integer of 0 to 5. )

Specific examples of the alkyl group of R ¹³ and R ¹⁴ include a methyl group, an ethyl group, a propyl group and an isopropyl group. Further, specific examples of R ¹⁵ include a methyl group, an ethyl group, a propyl group and an isopropyl group, a chlorine atom, a bromine atom and an iodine atom. N is usually an integer of 0 to 5, preferably an integer of 1 to 5.

Specific examples of such aromatic vinyl compounds include styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, m-methylstyrene, p-chlorostyrene, m-chlorostyrene and p-chloromethylstyrene, 4-vinylpyridine, 2-vinylpyridine, 5-ethyl-2-vinylpyridine, 2-methyl-5-vinylpyridine,
Examples thereof include 2-isopropenylpyridine, 2-vinylquinoline, 3-vinylisoquinoline, N-vinylcarbazole, and N-vinylpyrrolidone.

As unsaturated carboxylic acids, acrylic acid,
Methacrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, norbornene dicarboxylic acid, bicyclo [2,
2,1] unsaturated carboxylic acids such as hept-2-ene-5,6-dicarboxylic acid, or acid anhydrides or derivatives thereof (eg, acid halides, amides, imides, esters, etc.).

Examples of specific compounds include maleenyl chloride, maleenyl imide, maleic anhydride, itaconic anhydride, citraconic anhydride, tetrahydrophthalic anhydride, bicyclo [2,2,1] hept-2-ene-5, 6-dicarboxylic anhydride, dimethyl maleate, monomethyl maleate, diethyl maleate, diethyl fumarate, dimethyl itaconate, diethyl citrate, dimethyl tetrahydrophthalate, bicyclo [2,2,1] hept-2-ene- 5,6-dicarboxylic acid dimethyl, acrylic acid, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate,
2-ethylhexyl acrylate, acryloyl chloride,
Acrylamide, methacrylic acid, methyl methacrylate,
Ethyl methacrylate, propyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, methacryloyl chloride, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, glycidyl (meth) acrylate, aminoethyl methacrylate and amino methacrylate Examples thereof include propyl, tetrahydrofurfuryl acrylate, and tetrahydrofurfuryl methacrylate. Among these, acrylic acid, methyl acrylate, ethyl acrylate, methacrylic acid, methyl methacrylate, ethyl methacrylate, acrylamide, methacrylamide, maleic anhydride, hydroxyethyl acrylate, hydroxyethyl methacrylate, glycidyl methacrylate, amino methacrylate Propyl, tetrahydrofurfuryl acrylate, tetrahydrofurfuryl methacrylate are preferred.

Examples of vinyl ester compounds include vinyl acetate, vinyl propionate, vinyl n-butyrate, vinyl isobutyrate, vinyl pivalate, vinyl caproate, vinyl versatate, vinyl laurate, vinyl stearate, and benzoic acid. Vinyl, vinyl pt-butyl benzoate, vinyl salicylate, vinyl cyclohexanecarboxylate and the like can be mentioned.

Examples of the nitrile group-containing unsaturated compound include acrylonitrile, methacrylonitrile, fumaronitrile, allyl cyanide, cyanoethyl acrylate and the like.

Among the radically polymerizable monomers (B) exemplified above, hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, aminoethyl (meth) acrylate, propylaminoethyl (meth) acrylate, glycidyl (Meth) acrylate, styrene, (meth) acrylic acid, methyl (meth) acrylate,
It is preferable to use ethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, (meth) acrylamide, and (meth) acrylonitrile.

The above radical polymerizable monomer (B) is usually added to 100 parts by weight of the thermoplastic polymer (A).
It is used in an amount of 0.1 to 100 parts by weight, preferably 0.5 to 80 parts by weight, more preferably 1 to 50 parts by weight.

Radical initiator (C) Examples of the radical initiator (C) used in the present invention include organic peroxides and azo compounds. Specific examples of organic peroxides include dicumyl peroxide [2], di-t-butyl peroxide [2], 2,5-dimethyl-2,5-bis (t-butylperoxy) hexane (4), 2,5-dimethyl-2,5-bis (t-butylperoxy) hexyne-3 [4], 1,3-bis (t-butylperoxyisopropyl) benzene [4], 1,1 -Bis (t-butylperoxy) baralate [4], benzoyl peroxide [2], t-butylperoxybenzoate [2], acetyl peroxide [2], isobutyryl peroxide [2], octanoyl peroxide [2], decanoyl peroxide [2], lauroyl peroxide [2], 3,5,5-trimethylhexanoyl peroxide [2] and 2,4-dichlorobenzoyl peroxide [2], m-toluylperoxide Oxide [2] and the like can be mentioned. As the azo compound, azoisobutyronitrile [2], dimethylazoisobutyronitrile [2]
And the like. Here, the numbers in the brackets [] added to the specific examples of the above-mentioned organic peroxides are the theoretical moles of radicals that can be generated from 1 mole of the compound. The theoretical number of moles of a radical that can be generated in the radical initiator (C) used in the present invention is, in the case of an organic peroxide, a compound 1
This is twice the number of moles of -OO- groups present per mole. In the case of an azo compound, the number of moles of -N = N- groups present per mole of the compound is doubled.

Such a radical initiator (C) is usually used with respect to 100 parts by weight of the thermoplastic polymer (A).
It is desirable to use 0.001 to 10 parts by weight, preferably 0.005 to 8 parts by weight, more preferably 0.01 to 5 parts by weight.

As the radical initiator (C), the thermoplastic polymer (A) and the radical-containing compound (D-1) or the radical-containing compound (D-
The compound (1) can be used as a mixture with the compound (D-2) which can generate the compound, or can be used by dissolving it in a small amount of an organic solvent. As the organic solvent used here, any organic solvent that can dissolve the radical initiator can be used without particular limitation.

As such an organic solvent, benzene,
Aromatic hydrocarbon solvents such as toluene and xylene; aliphatic hydrocarbon solvents such as pentane, hexane, heptane, octane, nonane and decane; cyclohexane,
Alicyclic hydrocarbon solvents such as methylcyclohexane and decahydronaphthalene; chlorinated hydrocarbons such as chlorobenzene, dichlorobenzene, trichlorobenzene, methylene chloride, chloroform, carbon tetrachloride and tetrachloroethylene; methanol, ethanol, alcoholic solvents such as n-propynol, iso-propanol, n-butanol, sec-butanol and tert-butanol;
Ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone; ester solvents such as ethyl acetate and dimethyl phthalate; dimethyl ether;
Examples include ether solvents such as diethyl ether, di-n-amyl ether, tetrahydrofuran and dioxyanisole.

Radical-containing compound (D-1) The radical-containing compound (D-1) used in the present invention is:
It is a compound containing radicals of oxygen, nitrogen, phosphorus, sulfur, carbon and silicon. These compounds preferably contain a radical which is stable at room temperature.

Further, in the graft polymerization reaction of the present invention, these radical-containing compounds have some effect on such radicals, such as capturing radicals that induce side reactions such as polymer decomposition and cross-linking reactions in the reaction system. As a result, it is estimated that graft polymerization can be performed with high efficiency while suppressing side reactions. Therefore, it is preferable that these compounds can capture radicals generated in the reaction system.

Preferred examples of the radical-containing compound (D-1) of the present invention include compounds containing radicals of oxygen, nitrogen, phosphorus and sulfur. In particular, compounds containing oxygen radicals are preferred. The compound represented by the following general formula (I) can be mentioned.

Embedded image (Wherein, Z represents nitrogen, sulfur or phosphorus, X represents an optional substituent, and n is an integer of 1 to 4 that satisfies the valence of Z.)

The substituents X in the general formula (I) may be the same or different from each other and include a hydrogen atom, a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group,
It may be a nitrogen-containing group, a boron-containing group, a sulfur-containing group, a phosphorus-containing group, or a silicon-containing group, and two or more of these may be linked to each other to form a ring.

The halogen atom includes fluorine, chlorine, bromine and iodine. Specific examples of the hydrocarbon group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, neopentyl, and n-hexyl having 1 to 30 carbon atoms, preferably A linear or branched alkyl group having 1 to 20 carbon atoms, such as vinyl, allyl, and isopropenyl;
30, preferably 2 to 20 linear or branched alkenyl groups; ethynyl, propargyl and the like having 2 carbon atoms
A linear or branched alkynyl group having a carbon number of 3 to 30, preferably 2 to 20; a cyclic saturated hydrocarbon group having a carbon number of 3 to 30, preferably 3 to 20, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and adamantyl. A cyclic unsaturated hydrocarbon group having 5 to 30 carbon atoms such as cyclopentadienyl, indenyl and fluorenyl; phenyl, benzyl, naphthyl, biphenyl, terphenyl,
6 carbon atoms such as phenanthryl and anthracenyl
To 30, preferably 6 to 20 aryl groups;

The above-mentioned hydrocarbon group may have a hydrogen atom substituted by a halogen atom. For example, a halogenated carbon atom having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms such as trifluoromethyl, pentafluorophenyl and chlorophenyl. And a hydrogen group.

The hydrocarbon group may be substituted with the other hydrocarbon groups described above, for example, an aryl-substituted alkyl group such as benzyl and cumyl, tolyl,
Examples include alkyl-substituted aryl groups such as iso-propylphenyl, t-butylphenyl, dimethylphenyl, and di-t-butylphenyl, and substituted aryl groups in which an aryl group is substituted with a substituent such as an alkoxy group, an aryl group, or an aryloxy group. Can be The hydrocarbon group may further include a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, a sulfur-containing group, a phosphorus-containing group, and a silicon-containing group described below.

Particularly preferred hydrocarbon groups are, among others, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, neopentyl, n-hexyl and the like. 1-30, preferably 1-20, linear or branched alkyl groups;
6 to 3 carbon atoms such as phenyl, naphthyl, biphenyl, terphenyl, phenanthryl and anthracenyl
0, preferably 6 to 20 aryl groups; these aryl groups include halogen atoms, alkyl groups or alkoxy groups having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, and 6 to 30 carbon atoms, preferably 6 to 20 carbon atoms. Is a substituted aryl group in which 1 to 5 substituents such as an aryl group or an aryloxy group are substituted.

Examples of the heterocyclic compound residue include nitrogen-containing compounds such as pyrrole, pyridine, pyrimidine, quinoline and triazine; oxygen-containing compounds such as furan and pyran;
Residues such as sulfur-containing compounds such as thiophene, and groups in which these heterocyclic compound residues are further substituted with a substituent such as an alkyl group or an alkoxy group having 1 to 30, preferably 1 to 20 carbon atoms. Is mentioned.

Examples of the oxygen-containing group include an alkoxy group, an aryloxy group, an ester group, an acyl group, a carboxyl group,
Examples thereof include a carbonate group, a hydroxy group, a peroxy group, and a carboxylic anhydride group. Among them, the alkoxy group includes an alkoxy group having 1 to 30 carbon atoms, specifically, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy and the like. As the aryloxy group, an aryloxy group having 6 to 30 carbon atoms, specifically, phenoxy, 2,6-dimethylphenoxy, 2,4,6-trimethylphenoxy and the like can be mentioned. Examples of the ester group include an ester group having 1 to 30 carbon atoms, specifically, acetyloxy, benzoyloxy, methoxycarbonyl, phenoxycarbonyl, p-chlorophenoxycarbonyl and the like. Examples of the acyl group include an acyl group having 1 to 30 carbon atoms, specifically, a formyl group, an acetyl group, a benzoyl group, a p-chlorobenzoyl group, a p-methoxybenzoyl group, and the like.

Examples of the nitrogen-containing group include an amino group, an imino group, an amide group, an imide group, a hydrazino group, a hydrazono group, a nitro group, a nitroso group, a cyano group, an isocyano group,
Examples include those in which a cyanate ester group, an amidino group, a diazo group, and an amino group have become ammonium salts. Examples of the amino group include those having 0 to 30 carbon atoms, such as dimethylamino, ethylmethylamino, and diphenylamino. Examples of the imino group include an imino group having 1 to 30 carbon atoms, specifically, methylimino, ethylimino, propylimino, butylimino, phenylimino and the like. Examples of the amide group include an amide group having 1 to 30 carbon atoms, specifically, acetamido, N-methylacetamido, N-methylbenzamide, and the like. The imide group may have 2 to 30 carbon atoms.
Imide groups, specifically, acetoimide, benzimide and the like.

As the boron-containing group, a borandiyl group,
Examples include a boranthryl group and a diboranyl group.

Examples of the sulfur-containing group include a mercapto group, a thioester group, a dithioester group, an alkylthio group, an arylthio group, a thioacyl group, a thioether group, a thiocyanate ester group, an isothiocyanate ester group, a sulfone ester group, a sulfonamide group, and a thioamide group. Carboxyl group,
Examples include a dithiocarboxyl group, a sulfo group, a sulfonyl group, a sulfinyl group, and a sulfenyl group. Among them, the thioester group includes a thioester group having 1 to 30 carbon atoms, specifically, acetylthio, benzoylthio, methylthiocarbonyl, phenylthiocarbonyl and the like. As the alkylthio group, an alkylthio group having 1 to 30 carbon atoms, specifically, methylthio,
Ethylthio and the like. Examples of the sulfonamide group include a sulfonamide group having 0 to 30 carbon atoms, specifically, phenylsulfonamide, N-methylsulfonamide, N-methyl-p-toluenesulfonamide and the like. Examples of the arylthio group include an arylthio group having 6 to 30 carbon atoms, specifically, phenylthio, methylphenylthio, naphthylthio and the like. Examples of the sulfone ester group include a sulfone ester group having 1 to 30 carbon atoms, specifically, methyl sulfonate, ethyl sulfonate, and phenyl sulfonate.

Examples of the phosphorus-containing group include a phosphide group, a phosphoryl group, a thiophosphoryl group and a phosphato group.

Examples of the silicon-containing group include a silyl group, a siloxy group, a hydrocarbon-substituted silyl group, a hydrocarbon-substituted siloxy group, and the like. Silyl, triphenylsilyl, dimethylphenylsilyl, dimethyl-t-butylsilyl, dimethyl (pentafluorophenyl) silyl and the like. Among them, methylsilyl, dimethylsilyl, trimethylsilyl, ethylsilyl, diethylsilyl, triethylsilyl, dimethylphenylsilyl, triphenylsilyl and the like are preferable. Particularly, trimethylsilyl, triethylsilyl, triphenylsilyl and dimethylphenylsilyl are preferred. Specific examples of the hydrocarbon-substituted siloxy group include trimethylsiloxy.

Specific examples of the compound of the general formula (I) include, but are not limited to, the following.

Embedded image

In the formula (I), examples of the nitroxide radical-containing compound having Z as a nitrogen atom include compounds represented by the following formula (II) or (III).

Embedded image (In the above formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , and R ⁶ each independently represent a halogen atom such as chlorine or bromine;
Represents a linear or branched or cyclic saturated or unsaturated hydrocarbon group or an aryl group, which may be the same or different, and ^one of R ¹ , R ² , R ³ and R ⁴ , R ⁵ and R ⁶ may be linked to form a cyclic structure. )

Embedded image (In the above formula, R ⁷ and R ⁸ are each independently a halogen atom such as chlorine or bromine, a linear or branched or cyclic saturated or unsaturated hydrocarbon group or an aryl group having 1 to 10 carbon atoms. Represents the same or different from each other,
R ⁷ and R ⁸ may be linked to form a cyclic structure. )

The compound represented by the formula (II) can be selected from the compounds represented by the following general formulas.

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In the above formula, R¹, R^Two, R^Three, R^Four, R¹'And
And R^TwoIs a halogen atom such as chlorine or bromine, and has 1 to 1 carbon atoms.
0 has a straight or branched chain or a cyclic saturated or
Is an unsaturated hydrocarbon group such as an alkyl group, a cycloalkyl
Group, phenyl group, ester (-COOR) group, alcohol
Xy (-OR) group or phosphate (-P (O) (OR)
_Two) Group (where R is a saturated aliphatic group having 1 to 3 carbon atoms)
And may be the same or different from each other;^Five,
R⁶, R⁷, R⁸, R⁹, R^TenIs R¹, R^Two, R^Three, R ^Four, R
¹'And R^TwoHas the same meaning as', or a hydrogen atom, water
Acid group, -COOH, -P (O) (OH)_TwoOr -SO_ThreeH etc.
And may be the same or different from each other.

In the present invention, as the nitroxide radical-containing compound, in the above formula (II), R ¹ , R ² , R ³
One of R ⁴ , R ⁵ , and R ⁶ is linked to form a cyclic structure, and the others are all alkyl groups, which are stable at room temperature and are preferred. Specific examples thereof include the following compounds.

[0065]

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[0066]

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[0067]

Embedded image (In the above formula, Me is a methyl group, Et is an ethyl group,
Ph represents a phenyl group. Hereinafter, the same applies to the present invention. Also, p
And q each represent an integer of 0 to 30. )

Among the nitroxide radical-containing compounds represented by the above formula (II), preferred examples which are stable at room temperature and suitable are:
The following (a) to (i) can be mentioned. (a) 2,2,2,5-tetramethyl-1-pyrrolidiniloxy (PR
OXYL), (b) 2,2,6,6-tetramethyl-1-piperidinyloxy (commercially available under the name TEMPO), (c) N-tert-butyl-1-phenyl-2-methylpropyl Nitroxide, (d) N-tert-butyl-1- (2-naphthyl) -2
-Methylpropyl nitroxide, (e) N-tert-butyl-1-
Diethylphosphono-2,2-dimethylpropyl nitroxide, (f) N-tert-butyl-1-dibenzylphosphono-2,2-dimethylpropyl nitroxide, (g) N-phenyl-1-diethylphosphono-2 , 2-dimethylpropyl nitroxide, (h)
N-phenyl-1-diethylphosphono-1-methylethyl nitroxide, (i) N- (1-phenyl-2-methylpropyl) -1-diethylphosphono-1-methylethyl nitroxide TEMP
O.

Among the radical-containing compounds (D-1) of the present invention, specific examples of compounds containing a nitrogen radical include, but are not limited to, the following.

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Among the radical-containing compounds (D-1) of the present invention, specific examples of the compound containing a phosphorus radical include, but are not limited to, the following.

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Among the radical-containing compounds (D-1) of the present invention, specific examples of the compound containing a sulfur radical include, but are not limited to, the following.

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Among the radical-containing compounds (D-1) of the present invention, specific examples of the compound containing a carbon radical include the following, but are not limited thereto.

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Among the radical-containing compounds (D-1) of the present invention, specific examples of the compound containing a silicon radical include, but are not limited to, the following.

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In the present invention, among the above-mentioned radical-containing compounds (D-1), the compounds containing oxygen radicals represented by the above-mentioned general formula (I) are preferable, and further, the compounds of the formula (I-1) ) Is preferably a nitroxide radical-containing compound having Z as a nitrogen atom,
Particularly, a compound represented by the above general formula (II) or (III) is preferable.

Such a radical-containing compound (D-1)
Is usually from 0.001 to 10 parts by weight, preferably from 0.01 to 10 parts by weight, based on 100 parts by weight of the thermoplastic polymer (A).
It is preferably used in an amount of from 0.5 to 8 parts by weight, more preferably from 0.01 to 5 parts by weight. The molar number of the radical derived from the radical-containing compound (D-1) is 0.01 to 2.0 times the theoretical molar number of the radical that can be generated in the radical initiator (C). It is preferably used. When the radical-containing compound (D-1) is a nitroxide radical-containing compound, the number of moles of the NO—group of the nitroxide radical-containing compound is based on the theoretical number of moles of a radical that can be generated in the radical initiator (C). , 0.01 to 2.0 times.

Radical-forming compound (D-2) In the present invention, instead of or in combination with the radical-containing compound (D-1), the radical-containing compound (D-
A radical-forming compound (D-2) capable of producing 1) may be used. The radical-forming compound (D-2) of the present invention comprises a thermoplastic polymer (A) and a radical initiator (C) under a graft polymerization reaction condition, that is, at a temperature at which the radical initiator (C) can generate a radical. C) under the conditions of contacting the radical-containing compound (D-1) or the radical-forming compound (D-2) with the radical-polymerizable monomer (B) followed by the graft polymerization. , Radical-containing compound (D-1)
Is a compound capable of producing

Such a radical-forming compound (D-2)
And a secondary amine. As the secondary amine, for example, those shown below can be exemplified.

Embedded image

Preferred secondary amines are represented by the following general formula (IV)
It is a compound shown by these.

Embedded image (In the above formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , and R ⁶ each independently represent a halogen atom such as chlorine or bromine;
Represents a linear or branched or cyclic saturated or unsaturated hydrocarbon group or an aryl group, which may be the same or different, and ^one of R ¹ , R ² , R ³ and R ⁴ , R ⁵ and R ⁶ may be linked to form a cyclic structure. )

Of these, one of R ¹ , R ² , and R ³ is connected to one of R ⁴ , R ⁵ , and R ⁶ to form a cyclic structure, and the other is an alkyl group. Is preferred. Specific examples thereof include the following compounds.

[0080]

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[0081]

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Such a radical-forming compound (D-2)
Preferred examples include piperidine compounds. Specific examples of the piperidine compound include 4-hydroxy-2,2,6,6-tetramethylpiperidine, 1-allyl-4-hydroxy-2,2,6,6-tetramethylpiperidine, 1-benzyl-
4-hydroxy-2,2,6,6-tetramethylpiperidine, 1- (4-
(t-butyl-2-butenyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine, 4-stearoyloxy-2,2,6,6-tetramethylpiperidine, 4-methacryloyloxy-1,2 , 2,
6,6-pentamethylpiperidine; 1-benzyl-2,2,6,6-tetramethyl-4-piperidyl maleate, bis (2,2,6,6-
Tetramethyl-4-piperidyl) adipate, bis (2,2,6,6
-Tetramethyl-4-piperidyl) sebacate, bis (2,2,6,
6-tetramethyl-4-piperidyl) fumarate, bis (1,2,
3,6-tetramethyl-2,6-diethyl-4-piperidyl) sebacate, bis (1-allyl-2,2,6,6-ethramethyl-4-piperidyl) phthalate, bis (1,2,2,6 , 6-Pentamethyl-4-piperidyl) sebacate;

1-propargyl-4-β-cyanoethyloxy-
2,2,6,6-tetramethylpiperidine, 1-acetyl-2,2,6,6
-Tetramethyl-4-piperidyl-acetate, trimellitic acid-tri- (2,2,6,6-tetramethyl-4-piperidyl) ester, 1-acryloyl-4-benzyloxy-2,2,6,6 -Tetramethylpiperidine, bis (1,2,2,6,6-pentamethyl-4-
Benzyloxy-2,2,6,6-tetramethylpiperidine; bis (1,2,2,6,6-pentamethyl-4-piperidyl) dibutylmalonate, bis (1,2,2,6,6-pentamethyl -4-piperidyl) dibenzyl-malonate, bis (1,2,3,6-tetramethyl-2,6-diethyl-4-piperidyl) dibenzyl-malonate, hexane-1 ', 6'-bis-4-carbamoyloxy -1-n-
Butyl-2,2,6,6-tetramethylpiperidine), toluene-
2 ', 4'-bis- (4-carbamoyloxy-1-n-butyl-2,2,6,
6-tetramethylpiperidine); dimethyl-bis (2,2,6,6-
Tetramethylpiperidine-4-oxy) -silane, phenyl-
Tris- (2,2,6,6-tetramethylpiperidine-4-oxy)-
Silane; tris- (1-propyl-2,2,6,6-tetramethyl-4-
Piperidyl) -phosphite, tris- (1-propyl-2,
2,6,6-tetramethyl-4-piperidyl) -phosphate,
Phenyl- [bis- (1,2,2,6,6-pentamethyl-4-piperidyl)]-phosphonate; tetrakis (2,2,6,6-tetramethyl-4-piperidyl) 1,2,3 , 4-butanetetracarboxylate, tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, di (tridecyl) bis (2,2 , 6,6-tetramethyl-4-piperidyl)-
1,2,3,4-butanetetracarboxylate, di (tridecyl) bis (1,2,2,6,6-pentamethyl-4-piperidyl) -1,2,
3,4-butanetetracarboxylate; 2,2,4,4-tetramethyl-7-oxa-3,20-diazaspiro [5,1,11,2] heneicosan-21-one;

3,9-bis [1,1-dimethyl-2-ditris (2,2,
6,6-tetramethyl-4-piperidyloxycarbonyl) butylcarbonyloxydiethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane, 3,9-bis [1,1-dimethyl- 2-
{Tris (1,2,2,6,6-pentamethyl-4-piperidyloxycarbonyl) butylcarbonyloxydiethyl] -2,4,8,
10-tetraoxaspiro [5,5] undecane, dimethylsuccinate-2- (4-hydroxy-2,2,6,6-tetramethylpiperidyl) ethanol condensate; poly [hexamethylene} (2,2,6 , 6-Tetramethyl-4-piperidyl) imino｝),
Poly (ethylene) (2,2,6,6-tetramethyl-4-piperidyl) imino hexamethylene (2,2,6,6-tetramethyl-4
-Piperidyl) imino｝), poly [[6-{(1,1,3,3, -tetramethylbutyl) amino} -1,3,5-triazine-2,4-diyl] [(2,2, 6,6-tetramethyl-4-piperidyl) imino)
Hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) imino]], poly [(6-morpholino-1,3,5-triazine-2,4-diyl) [(2,2, 6,6-tetramethyl-4-piperidyl) imino] hexamethylene [(2,2,6,6-tetramethyl-4
-Piperidyl) imino]], poly [[6-{(ethylacetyl) amino} -1,3,5-triazine-2,4-diyl] [(2,2,6,
6-tetramethyl-4-piperidyl) imino] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) imino]] and poly [[6-｛(2,2,6,6-tetra Methyl-4-piperidyl) butylamino {-1,3,5-triazine-2,4-diyl]
[(2,2,6,6-tetramethyl-4-piperidyl) imino] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) imino]] and the like.

In particular, tetrakis (2,2,6,6-tetramethyl-
4-piperidyl) -1,2,3,4-butanetetracarboxylate, 3,9-bis [1,1-dimethyl-2-ditris (1,2,2,6,6-pentamethyl-4-piperidyl (Oxycarbonyl) butylcarbonyloxy {ethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane, poly [[6-{(1,1,3,3, -tetramethylbutyl) amino} -1,3,5-triazine-2,4-diyl)
[(2,2,6,6-tetramethyl-4-piperidyl) imino] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) imino]], poly [(6-morpholino-1 , 3,5-triazine-
2,4-diyl) ((2,2,6,6-tetramethyl-4-piperidyl)
[Imino] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) imino]] and mixtures of two or more thereof are preferred.

Such a radical-forming compound (D-2)
Is usually from 0.001 to 10 parts by weight, preferably from 0.01 to 10 parts by weight, based on 100 parts by weight of the thermoplastic polymer (A).
It is preferably used in an amount of from 0.5 to 8 parts by weight, more preferably from 0.01 to 5 parts by weight. Further, the theoretical mole number of the radical that can be generated from the radical-forming compound (D-2) is 0.01 to 2.0 times the theoretical mole number of the radical that can be generated in the radical initiator (C). It is preferable to use them in proportions. Radical generating compound (D
When -2) is a secondary amine, the number of moles of the NH group of the secondary amine is 0.01 to 2.0 times the theoretical number of moles of the radical that can be generated in the radical initiator (C). It is preferred that they be used.

In the present invention, the radical-forming compound (D
-2) may be directly contacted with the thermoplastic polymer (A) and the radical initiator (C), or may be used after previously contacting with a peroxide. Examples of the peroxide used at this time include the organic peroxides, hydrogen peroxide, and peroxy acids exemplified as the radical initiator (C).
Examples of the peracid used herein include formic acid, peracetic acid, and perbenzoic acid.

Method for Graft Polymerization of Thermoplastic Polymer In the method of the present invention, when the radical polymerizable monomer (B) is graft-polymerized to the thermoplastic polymer (A) in the presence of the radical initiator (C), A polymer (A), at least one radical initiator (C),
At least one compound (D) selected from the radical-containing compound (D-1) and the radical-generating compound (D-2) was previously contacted at a temperature at which the radical initiator (C) could generate a radical. Thereafter, the radical polymerizable monomer (B) is added to perform graft polymerization.

The temperature at which the thermoplastic polymer (A), the radical initiator (C), and the radical-containing compound (D-1) or the radical-generating compound (D-2) are brought into contact with each other is controlled by the radical initiator (C) Is not particularly limited as long as it is a temperature at which radicals can be generated.
° C, preferably 70-350 ° C, more preferably 80 ° C.
３００300 ° C.

In order to bring these components into contact with each other at the above-mentioned radical generation temperature, a method in which all the components are charged into the reaction system at room temperature and then the temperature is raised to that temperature, a thermoplastic polymer is charged at room temperature and the temperature is raised to that temperature Any method may be used, such as a method of adding the remaining components after the temperature is raised, or a method of charging the thermoplastic polymer at room temperature and continuously adding the remaining components while raising the temperature to the temperature.

In the present invention, the radical polymerizable monomer (B) may be added immediately after the components (A), (C) and (D) have come into contact at the above-mentioned radical generation temperature. It is preferably added after a lapse of a predetermined time from the contact at the temperature. The time at that time is usually 0.02 to 120 minutes, preferably 0.02 to 120 minutes.
It is 5 to 90 minutes, more preferably 0.1 to 60 minutes.

When the radical polymerizable monomer (B) is added, the entire amount of the radical polymerizable monomer (B) may be added all at once, or may be added continuously or dividedly during the reaction time. The temperature at that time may be the same as or different from the temperature at which the components (A), (C) and (D) are brought into contact, and is usually 50 to 400 ° C, preferably 70 to 350 ° C, and furthermore Preferably it is 80-300 degreeC. The reaction time with the radical polymerizable monomer is usually 0.5 to 10 hours, preferably 1 to 8 hours.

In the graft polymerization of the present invention, at least a part of the thermoplastic polymer (A) is converted into any of a solid state, a molten state, and a state dissolved in an organic solvent, as long as the object of the present invention is not impaired. A reaction may be performed.

The organic solvent used when reacting in a state where at least a part of the thermoplastic polymer (A) is dissolved in an organic solvent may be any organic solvent capable of dissolving the thermoplastic polymer (A). Although not particularly limited, when using a polyolefin as the thermoplastic polymer, benzene, toluene, aromatic hydrocarbon solvents such as xylene, pentane, hexane, aliphatic hydrocarbon solvents such as heptane and the like as the organic solvent. No. When the graft polymerization is performed in a state where at least a part of the thermoplastic polymer is dissolved in an organic solvent, the reaction temperature is usually 70 to 200 ° C, preferably 80 to 190 ° C.

When the graft polymerization is performed in a state where at least a part of the thermoplastic polymer (A) is molten, the reaction temperature is usually equal to or higher than the melting point of the thermoplastic polymer. When a polyolefin is used as the thermoplastic polymer, the reaction temperature is usually in the range of 80 to 300C, preferably 80 to 250C. When an extruder is used for graft polymerization, for example, (A)
A mixture obtained by previously mixing the components (C) and (D) is supplied from a hopper, and the above-mentioned component (B) is supplied from a supply port provided in an intermediate portion of the extruder.
There is a method of supplying the components. Further, the above (C),
The component (D) may be provided with a supply port near the hopper, and supplied separately therefrom.

Other Additives In the present invention, a reducing substance may be used in graft polymerization of a thermoplastic polymer as long as the object of the present invention is not impaired. The reducing substance has an effect of improving the graft reaction amount in the obtained graft-polymerized thermoplastic polymer.

Examples of usable reducing substances include iron (II) ion, chromium ion, cobalt ion, nickel ion, palladium ion, sulfite, hydroxylamine, hydrazine, etc., as well as -SH, -SO ₃ H,- N
Examples include compounds containing groups such as HNH ₂ and —COCH (OH) —.

Specific examples of such a reducing substance include:
Ferrous chloride, potassium dichromate, cobalt chloride, cobalt naphthenate, palladium chloride, ethanolamine,
Examples include diethanolamine, N, N-dimethylaniline, hydrazine, ethyl mercaptan, benzenesulfonic acid, p-toluenesulfonic acid and the like.

The reducing substance is used in an amount of usually 0.001 to 5 parts by weight, preferably 0.1 to 3 parts by weight, based on 100 parts by weight of the thermoplastic polymer (A).

The amount of the radically polymerizable monomer contained in the graft polymer obtained by the graft polymerization method of the present invention is usually 0.1 to 50% by weight, preferably 0.2 to 30% by weight. It is in.

[0101]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples. (Example) Chlorobenzene 700 m as a reaction solvent
1, ethylene-propylene-ethylidene norbornene copolymer (ethylene content 72 mol%, iodine value 22 g-I ₂
/ 100g, MRF (190 ° C, 5kgf load) 32g /
10 minutes) 50 g, dicumyl peroxide 0.09 g
(0.33 mmol, theoretical mole number of radicals that can be generated 0.66 mmol), 0.052 g of 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO) (0.33 mmol
l) was placed in a 1 liter autoclave under a nitrogen atmosphere. The temperature was raised to 140 ° C. while stirring the system, and stirring was continued at that temperature for 1 hour, and then 14.4 g of acrylic acid was continuously supplied over 4 hours. 14 more after the end of supply
The reaction was continued at 0 ° C. for 2 hours, and then cooled to room temperature to precipitate a polymer. The precipitated polymer was filtered, washed repeatedly with acetone, and dried under reduced pressure at 80 ° C. all day and night to obtain a target graft polymer. Elemental analysis was performed on the graft polymer to measure the amount of acrylic acid grafted. As a result, 22.1 g of acrylic acid was graft-polymerized per 100 g of the graft polymer. The MFR of the graft polymer (190 ° C., 5 kgf load) is 1
0.8 g / 10 min.

[0102]

According to the graft polymerization method of the present invention, the amount of graft reaction can be increased while suppressing side reactions such as crosslinking and decomposition of a thermoplastic polymer, and a graft polymer can be obtained with high graft efficiency.

 ──────────────────────────────────────────────────続 き Continued on front page F-term (reference) 4J011 BA04 PA34 PA38 PA40 PA43 PA44 PA45 PA46 PA47 PA63 PA83 PB30 4J026 AA11 AA17 AA24 AA25 AA38 AA45 AA67 AB07 AB17 AB18 AB22 AB28 AC07 AC10 BA06 BA20 BA21 BA24 BA30 BA30 BA33 BA35 BA39 BA40 CA01 CA04 CA05 CA07 DB12 DB15 DB40 GA02 GA06

Claims (7)

[Claims] 1. A method for graft-polymerizing a radical polymerizable monomer (B) onto a thermoplastic polymer (A) in the presence of a radical initiator (C), wherein the radical polymerizable monomer (B) is subjected to radical polymerization before addition of the radical polymerizable monomer (B). At a temperature at which the agent (C) can generate a radical, a thermoplastic polymer (A), a radical initiator (C), a radical-containing compound (D-1) of oxygen, nitrogen, phosphorus, sulfur, carbon or silicon; Alternatively, a method for graft polymerization of a thermoplastic polymer, comprising contacting a radical-forming compound (D-2) capable of forming the radical-containing compound (D-1). 2. The method for graft polymerization of a thermoplastic polymer according to claim 1, wherein the radical-containing compound (D-1) is a compound represented by the following general formula (I): 1) (Wherein, Z represents nitrogen, sulfur or phosphorus, X represents an optional substituent, and n is an integer of 1 to 4 that satisfies the valence of Z.) 3. The radical-containing compound (D-1) is a nitroxide radical-containing compound in which Z is a nitrogen atom in the general formula (I).
3. The method for graft polymerization of a thermoplastic polymer according to item 1. 4. The method according to claim 1, wherein the nitroxide radical-containing compound is
4. The method according to claim 3, wherein the compound is a compound represented by the following general formula (II) or (III): (In the above formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , and R ⁶ each independently represent a halogen atom such as chlorine or bromine;
Represents a linear or branched or cyclic saturated or unsaturated hydrocarbon group or an aryl group, which may be the same or different, and ^one of R ¹ , R ² , R ³ and R ⁴ , R ⁵ and R ⁶ may be linked to form a cyclic structure. ) (In the above formula, R ⁷ and R ⁸ are each independently a halogen atom such as chlorine or bromine, a linear or branched or cyclic saturated or unsaturated hydrocarbon group or an aryl group having 1 to 10 carbon atoms. Represents the same or different from each other,
R ⁷ and R ⁸ may be linked to form a cyclic structure. ) 5. The method according to claim 1, wherein the radical-forming compound (D-2) is 2
The method for graft polymerization of a thermoplastic polymer according to claim 1, which is a secondary amine. 6. The graft polymerization method for a thermoplastic polymer according to claim 5, wherein the secondary amine is a compound represented by the following general formula (IV): (In the above formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , and R ⁶ each independently represent a halogen atom such as chlorine or bromine;
Represents a linear or branched or cyclic saturated or unsaturated hydrocarbon group or an aryl group, which may be the same or different, and ^one of R ¹ , R ² , R ³ and R ⁴ , R ⁵ and R ⁶ may be linked to form a cyclic structure. ) 7. The radical initiator (C) is characterized in that the number of moles of radicals derived from the radical-containing compound (D-1) or the theoretical number of moles of radicals that can be generated from the radical-forming compound (D-2) is in the radical initiator (C). The method for graft polymerization of a thermoplastic polymer according to claim 3 or 4, wherein the method is used in an amount of 0.01 to 2.0 times the theoretical number of moles of a radical that can be generated.