JP2010222464A - Method for producing polymer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for easily producing a polymer wherein an olefin polymer segment is chemically bound to a radical polymer segment. <P>SOLUTION: A radically polymerizable monomer is polymerized in the presence of a halogen-free olefin polymer (A), a metal compound (B)containing a transition metal element selected from those in groups III to XI of the periodic table, and an activator (C) having a halogen-halogen or nitrogen-halogen bond in its molecule, to produce a polymer wherein an olefin polymer segment is chemically bound to a radical polymer segment. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a method for producing a polymer in which an olefin polymer segment and a radical polymer segment are chemically bonded.

  As a method for producing a polymer in which an olefin polymer segment and a radical polymer segment are chemically bonded, a boron-containing group of an alkylboron-containing polyolefin is converted into a peroxide, and a monomer such as methyl methacrylate is radically polymerized. A method for producing a block polymer is disclosed (for example, see Patent Document 1). Moreover, the polar group in the copolymer of the olefin and the polar group-containing monomer or the polar group in the polar group-containing olefin polymer obtained by modification of the unsaturated bond is converted into a radical polymerization initiator, A method of radical polymerization of a polar group-containing monomer such as methyl methacrylate is disclosed (see Patent Documents 2 and 3).

  In recent years, a method of producing a polymer in which an olefin polymer segment and a radical polymer segment are chemically bonded by performing radical polymerization using a halogen-modified polymer obtained by directly halogenating an olefin polymer. Has been reported (see Patent Document 4).

  In any of the conventional production methods, since an olefin polymer having a polymerization initiation point introduced into the molecule is used as a macroinitiator, a process of introducing a functional group into the olefin polymer before carrying out radical polymerization, Furthermore, a process such as separation and purification of the polymer was necessary.

International Publication No. 98/02472 Pamphlet JP 2004-131620 A JP 2007-169318 A International Publication No. 2006/088197 Pamphlet

  The present invention has been made in view of the above prior art, and aims to provide a method for producing a polymer in which an olefin polymer segment and a radical polymer segment are chemically bonded by a simpler method. To do. Specifically, the olefin polymer segment and the radical polymer segment were chemically bonded by simplifying the manufacturing process of the macroinitiator “olefin polymer with a polymerization initiation point introduced into the molecule”. The object is to produce the polymer in an industrially advantageous manner.

  As a result of diligent studies to solve the problem, the present inventors activated the olefin polymer using a specific activator and polymerized a radical polymerizable monomer, thereby The inventors have found that the problems can be solved and have reached the present invention.

  That is, the present invention is a method for producing a polymer in which an olefin polymer segment and a radical polymer segment are chemically bonded, and includes an olefin polymer (A) not containing a halogen element, a group 3 of the periodic table, A radical polymerizable monomer in the presence of a metal compound (B) containing a transition metal element selected from Group 11 and an activator (C) having a halogen-halogen bond or a nitrogen-halogen bond in the molecule. And a step of polymerizing.

  The present invention provides an improved method for producing a polymer in which an olefin polymer segment and a radical polymer segment are chemically bonded. According to the method of the present invention, an olefin polymer such as polyethylene or polypropylene, which is widely produced industrially, is used as a raw material, and the desired olefin polymer segment and radical polymer segment are obtained in a one-step reaction. It is possible to produce chemically bonded polymers. Therefore, the manufacturing process can be greatly simplified as compared with the prior art, which is very advantageous in terms of manufacturing cost and energy consumption.

Hereafter, the manufacturing method of the polymer of this invention is demonstrated concretely.
The present invention is a method for producing a polymer in which an olefin polymer segment and a radical polymer segment are chemically bonded. Olefin polymer containing no halogen element (A), metal compound (B) containing a transition metal element selected from Group 3 to Group 11 of the periodic table, and halogen-halogen bond or nitrogen-halogen bond in the molecule It is characterized by polymerizing a radically polymerizable monomer in the presence of an activator (C) having

  The olefin polymer (A) containing no halogen element used in the present invention is a polymer composed of a monoolefin compound having only one carbon-carbon double bond or a monoolefin compound having an aromatic ring. Preferably there is. A polymer of a compound having a plurality of carbon-carbon double bonds (for example, a linear diene compound such as hexadiene or octadiene, a styrene diene compound such as divinylbenzene, a cyclic diolefin compound such as vinyl norbornene or ethylidene norbornene), Or the copolymer which uses it as a copolymerization component may be unpreferable since the unsaturated bond derived from a diene compound bridge | crosslinks and gelatinizes in the step which superposes | polymerizes a radically polymerizable monomer.

Accordingly, examples of the olefin polymer (A) used in the present invention include polymers selected from the group consisting of the following (A1) to (A5). Two or more of these may be used in combination.
(A1): A homopolymer or copolymer of an α-olefin compound represented by CH ₂ ═CH—C _X H _{2X + 1} (x is 0 or a positive integer).
(A2): A copolymer of an α-olefin compound represented by CH ₂ ═CH—C _X H _{2X + 1} (x is 0 or a positive integer) and a monoolefin compound having an aromatic ring.
(A3): Co-weight of an α-olefin compound represented by CH ₂ ═CH—C _X H _{2X + 1} (x is 0 or a positive integer) and a cyclic monoolefin compound represented by the following general formula (1) Coalescence.
(A4): A random copolymer of an α-olefin compound represented by CH ₂ ═CH—C _X H _{2X + 1} (x is 0 or a positive integer) and an unsaturated carboxylic acid or a derivative thereof.
(A5): A polymer obtained by modifying any of the polymers (A1) to (A4) with an unsaturated carboxylic acid or a derivative thereof.

（一般式（１）における各記号の定義は後述する）

(The definition of each symbol in the general formula (1) will be described later)

About polymer (A1):
The polymer (A1) used in the present invention is a homopolymer or copolymer of an α-olefin compound represented by CH ₂ ═CH—C _X H _{2X + 1} (x is 0 or a positive integer).

Specific examples of the α-olefin compound represented by CH ₂ ═CH—C _X H _{2X + 1} (x is 0 or a positive integer), which is a constituent monomer of the polymer (A1), include ethylene, propylene, 1 − Butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, Linear or branched α-olefins having 4 to 20 carbon atoms such as 1-hexadecene, 1-octadecene, 1-eicosene and the like are included. Among these exemplified olefins, it is preferable to use at least one olefin selected from ethylene, propylene, 1-butene, 1-hexene, 4-methyl-1-pentene and 1-octene, more preferably Ethylene, propylene and 1-butene.

  The polymer (A1) is not particularly limited as long as it is obtained by homopolymerization or copolymerization of the α-olefin compound. Preferred specific examples of the polymer (A1) include ethylene polymers such as low density polyethylene, medium density polyethylene, high density polyethylene, linear low density polyethylene, and ultrahigh molecular weight polyethylene; propylene homopolymer, propylene random copolymer, Propylene polymers such as propylene block copolymer; polybutene, poly (4-methyl-1-pentene), poly (1-hexene), ethylene-propylene copolymer, ethylene-butene copolymer, ethylene-hexene copolymer , Ethylene-octene copolymer, ethylene- (4-methyl-1-pentene) copolymer, propylene-butene copolymer, propylene- (4-methyl-1-pentene) copolymer, propylene-hexene copolymer Polymers, propylene-octene copolymers and the like are included. Of these, ethylene polymers, propylene polymers, ethylene-propylene copolymers, and ethylene-butene copolymers are more preferable.

About polymer (A2):
The polymer (A2) used in the present invention is a copolymer of an α-olefin compound represented by CH ₂ ═CH—C _X H _{2X + 1} (x is 0 or a positive integer) and a monoolefin compound having an aromatic ring. It is a polymer.

Specific examples of the α-olefin compound represented by CH ₂ ═CH—C _X H _{2X + 1} (x is 0 or a positive integer), which is a constituent monomer of the copolymer (A2), include the above (A1). The α-olefin compound described in the item is included. On the other hand, specific examples of the monoolefin compound having an aromatic ring include styrene compounds such as styrene, vinyltoluene, and α-methylstyrene, vinylpyridine, and the like.

  The copolymer (A2) is not particularly limited as long as it is obtained by copolymerizing the α-olefin compound and a monoolefin compound having an aromatic ring. Preferred examples of the copolymer (A2) include an ethylene-styrene copolymer, a propylene-styrene copolymer, an ethylene-propylene-styrene terpolymer, an ethylene-butene-styrene terpolymer. It is. The content of the unit derived from the α-olefin compound contained in the copolymer (A2) is preferably 50 mol% or more, more preferably 60 mol% or more in order to maintain the properties as an olefin polymer. .

Regarding copolymer (A3):
The copolymer (A3) is composed of an α-olefin compound represented by CH ₂ ═CH—C _X H _{2X + 1} (x is 0 or a positive integer) and a cyclic monoolefin compound represented by the following general formula (1) And a copolymer.

Examples of the α-olefin compound represented by CH ₂ ═CH—C _X H _{2X + 1} (x is 0 or a positive integer), which is a constituent monomer of the copolymer (A3), include those in the section (A1) above. The described α-olefin compounds are included.

In the general formula (1) showing the cyclic monoolefin compound that is a constituent monomer of the copolymer (A3), n is 0 or 1, m is 0 or a positive integer, q is 0 or 1, When q is 1, R ^a and R ^b each independently represent the following atom or hydrocarbon group, and when q is 0, each bond is bonded to form a 5-membered ring. To do.

The hydrocarbon group represented by R ^{1 to} R ¹⁸ and R ^a and R ^b in the general formula (1) is usually an alkyl group having 1 to 20 carbon atoms or a cycloalkyl group having 3 to 15 carbon atoms. . More specifically, examples of alkyl groups include methyl, ethyl, propyl, amyl, hexyl, octyl, decyl, dodecyl and octadecyl groups; examples of cycloalkyl groups A cyclohexyl group.

Furthermore, R ¹⁵ and R ¹⁶ in the general formula (1) are R ¹⁷ and R ¹⁸ , R ¹⁵ and R ¹⁷ are R ¹⁶ and R ¹⁸ , R ¹⁵ and R ¹⁸ are R or R ¹⁶ and R ¹⁷ may be bonded to each other (in cooperation with each other) to form a monocyclic or polycyclic ring. Specific examples of the monocyclic or polycyclic ring formed here are shown below, but are not particularly limited.

In the monocyclic or polycyclic examples, the carbon atom numbered 1 represents the carbon atom to which R ¹⁵ and R ¹⁶ are bonded in the general formula (1); the carbon atom numbered 2 Represents a carbon atom to which R ¹⁷ and R ¹⁸ are bonded in the general formula (1).

Specific examples of the cyclic olefin represented by the general formula (1) include a bicyclo [2.2.1] hept-2-ene derivative, a tricyclo [4.3.0.1 ^2,5 ] -3-decene derivative, and a tricyclo [4.3. 0.1 ^2,5] -3-undecene derivatives, tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3-dodecene derivatives, pentacyclo [7.4.0.1 ^2,5 .1 ^9,12 .0 ^8,13] 3-pentadecene derivatives, pentacyclo ^{[6.5.1.1 3,6 .0 2,7 .0 9,13]} -4- pentadecene derivatives, pentacyclo [8.4.0.1 ^2,3 .1 ^9,12 .0 ^8,13] 3-hexadecene derivative, pentacyclo ^{[6.6.1.1 3,6 .0 2,7 .0 9,14]} -4- hexadecene derivatives, penta cyclopentadiene decadiene derivative, hexacyclo [6.6.1.1 ^3,6 .1 ^{10, 13.0 2,7} .0 ^9,14] -4-heptadecene derivatives, heptacyclo ^{[8.7.0.1 3,6 .1 10,17 .1 12,15 .0} 2,7 .0 11,16] -4- Eicosene derivatives, heptacyclo-5-eicosene derivatives, heptacyclo ^{8.8.0.1 4,7 .1 11,18 .1 13,16 .0 3,8} .0 12,17] -5- heneicosene derivatives, octacyclo [8.8.0.1 ^2,9 .1 ^4,7 .1 ^{11, 18.1 13,16} .0 ^3,8 .0 ^12,17] -5-docosene derivatives, Nonashikuro ^{[10.9.1.1 4,7 .1 13,20 .1 15,18 .0} 3,8 .0 2, ^{10.0 12,21} .0 ^14,19] -5-pentacosene derivatives, Nonashikuro ^{[10.10.1.1 5,8 .1 14,21 .1 16,19 .0} 2,11 .0 4,9 .0 13, ^{22.0 15,20]} -5-hexacosenoic derivatives, and the like.

  The cyclic monoolefin compound represented by the general formula (1) can be produced by subjecting cyclopentadiene and an olefin having a corresponding structure to Diels-Alder reaction. These cyclic olefins can be used alone or in combination of two or more.

The structural unit derived from the cyclic monoolefin compound represented by the general formula (1) is represented by the following general formula (2).

In the formula (2), n, m, q, R ^{1 to} R ^18, R ^a and R ^b have the same meaning as in the formula (1).

The copolymer (A3) is not particularly limited as long as it is obtained by copolymerizing the α-olefin compound and the cyclic monoolefin compound represented by the general formula (1). Preferably is ethylene and bicyclo [2.2.1] copolymers of hept-2-ene, or ethylene and tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene, copolymers .

  The content of the unit derived from the α-olefin compound contained in the copolymer (A3) is preferably 50 mol% or more, more preferably 60 mol% or more in order to maintain the properties as an olefin polymer. .

About the random copolymer (A4):
The random copolymer (A4) is a random copolymer of an α-olefin compound represented by CH ₂ ═CH—C _X H _{2X + 1} (x is 0 or a positive integer) and an unsaturated carboxylic acid or a derivative thereof. It is a coalescence.

Examples of the α-olefin compound represented by CH ₂ ═CH—C _X H _{2X + 1} (x is 0 or a positive integer), which is a constituent monomer of the random copolymer (A4), include the above-mentioned item (A1). The described α-olefin compounds are included.

  On the other hand, examples of unsaturated carboxylic acids or derivatives thereof include unsaturated monocarboxylic acids and derivatives thereof, unsaturated dicarboxylic acids and derivatives thereof, and vinyl esters. More specifically, (meth) acrylic acid, (meth) acrylic acid ester, (meth) acrylic acid amide, maleic acid, maleic anhydride, maleic acid ester, maleic acid amide, maleic acid imide, vinyl acetate and butyric acid Examples thereof include aliphatic vinyl esters such as vinyl.

  The random copolymer (A4) is not particularly limited as long as it is a random copolymer of the α-olefin compound and the unsaturated carboxylic acid or derivative thereof. Preferred examples of the random copolymer (A4) include an ethylene- (meth) acrylic acid copolymer, an ethylene- (meth) acrylic acid ester copolymer, an ethylene-maleic anhydride copolymer, and an ethylene-vinyl acetate copolymer. Polymers and the like are included.

  The content of the unit derived from the α-olefin compound contained in the random copolymer (A4) is preferably 50 mol% or more, more preferably 60 mol% or more in order to maintain the properties as an olefin polymer. is there.

About polymer (A5):
The polymer (A5) is obtained by modifying any of the polymers (A1) to (A4) with an unsaturated carboxylic acid or a derivative thereof.

  Specific examples of the unsaturated carboxylic acid or its derivative for modifying any of the polymers (A1) to (A4) include maleic acid, maleic anhydride, maleic ester, maleic amide, maleic imide Etc. are included. Of these, maleic anhydride is preferred.

  As a method of modifying any of the polymers represented by the polymers (A1) to (A4) with an unsaturated carboxylic acid or a derivative thereof, in the presence of a radical generator such as an organic peroxide, or Examples include a method in which an unsaturated carboxylic acid or a derivative thereof is reacted with the polymers (A1) to (A4) in the presence of ultraviolet rays or radiation.

  The conditions and method for producing the polymers (A1) to (A5) are not particularly limited. For example, coordination using a known transition metal catalyst such as a Ziegler-Natta catalyst, a metallocene catalyst, or a postmetallocene catalyst. Methods such as anionic polymerization and radical polymerization under high pressure or irradiation can be used. Moreover, what decomposed | disassembled the olefin type polymer manufactured by the said method with the heat | fever or a radical can also be used.

The olefin polymer (A) used in the present invention has a polystyrene-equivalent weight average molecular weight measured by gel permeation chromatography (GPC) of 1 × 10 ³ to 1 × 10 ⁷ , preferably 5 × 10 ^3. ˜1 × 10 ⁶ , more preferably 1 × 10 ^{4 to} 5 × 10 ⁵ .

  In the present invention, a radically polymerizable monomer is polymerized, and this polymerization reaction is performed using a metal compound (B) containing a transition metal element selected from Group 3 to Group 11 of the periodic table as a catalyst. The metal compound (B) is preferably a compound containing a metal selected from titanium, zirconium, molybdenum, rhenium, iron, ruthenium, rhodium, cobalt, nickel, palladium, copper; more preferably, zero-valent copper, Examples of the complex include monovalent copper, divalent ruthenium, divalent iron, and divalent nickel. Of these, a copper complex is preferable.

  Specific examples of the monovalent copper compound which is the metal compound (B) include cuprous chloride, cuprous bromide, cuprous iodide, cuprous cyanide, cuprous oxide, perchloric acid One cup etc. are included.

A tristriphenylphosphine complex of divalent ruthenium chloride (RuCl ₂ (PPh ₃ ) ₃ ) is also suitable as the metal compound (B). When using a metal compound (B) as a ruthenium compound, an aluminum alkoxide is used in combination as an activator.
Further, a divalent iron bistriphenylphosphine complex (FeCl ₂ (PPh ₃ ) ₂ ), a divalent nickel bistriphenylphosphine complex (NiCl ₂ (PPh ₃ ) ₂ ), and a divalent nickel bistributylphosphine complex (NiBr ₂ (PBu ₃ ) ₂ ) is also suitable as the metal compound (B) and acts as a catalyst.

  In order to enhance the catalytic activity of the metal compound (B), a compound that becomes a ligand of the metal compound (B) may be used in combination. Examples of the ligand compound include 2,2′-bipyridyl or a derivative thereof; 1,10-phenanthroline or a derivative thereof; or tetramethylethylenediamine, pentamethyldiethylenetriamine, hexamethyltriethylenetetramine, or hexamethyltris (2 -Polyamines such as -aminoethyl) amine. Of these, pentamethyldiethylenetriamine and hexamethyltriethylenetetramine are preferable.

  If the amount of these polyamines used is too small, the solubility of the metal compound (B) in the solvent or monomer may be low, so that the catalytic activity may be extremely reduced or not sustained; Residues may cause coloring and odor. Therefore, the usage-amount of polyamine is the range of 0.1-1,000 equivalent normally with respect to a metal compound (B), Preferably it is 1-800 equivalent, More preferably, it is the range of 10-300 equivalent. is there.

  The polymerization reaction of the radically polymerizable monomer in the present invention is performed in the presence of an activator (C). The activator (C) is homo-cleavable under light irradiation or high temperature conditions to generate radical species, attack the olefin polymer (A), and turn the olefin polymer (A) into a macro radical. To do. It is considered that the radical polymerizable monomer is polymerized by the catalytic action of the metal compound (B) present in the system using the olefin polymer (A) that has become a macro radical as an initiator.

  In addition, oxidized species of the metal compound (B) are generated by a reaction with a halogen radical generated by homo-cleavage of the activator (C). It is considered that the polymer in which the target olefin polymer segment and the radical polymer segment are chemically bonded is efficiently produced by controlling the radical polymerization by the oxidizing species of the metal compound (B).

  The activator (C) used in the present invention preferably has a halogen-halogen bond or a nitrogen-halogen bond in the molecule. Specific examples of the activator (C) include chlorine, bromine, iodine, N- Chlorosuccinimide, N-bromosuccinimide, N-iodosuccinimide, N-bromocaprolactam, N-bromophthalimide, 1,3-dibromo-5,5-dimethylhydantoin, N-chloroglutarimide, N-bromoglutarimide, N, N'-dibromoisocyanuric acid and the like are included. Preferred are bromine and compounds having an N-Br bond such as N-bromosuccinimide and 1,3-dibromo-5,5-dimethylhydantoin.

  Examples of the radical polymerizable monomer used in the present invention include a (meth) acrylic acid monomer, a styrene monomer, a (meth) acrylamide monomer, a maleic acid monomer, and a maleimide monomer. It may be a monomer, a vinyl ester monomer or the like.

  Specific examples of (meth) acrylic acid monomers include (meth) acrylic acid, potassium (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, (meth) acrylic acid-n- Propyl, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, n-pentyl (meth) acrylate, (meth) acryl Acid-n-hexyl, cyclohexyl (meth) acrylate, (meth) acrylic acid-n-heptyl, (meth) acrylic acid-n-octyl, (meth) acrylic acid-2-ethylhexyl, (meth) acrylate nonyl, Decyl (meth) acrylate, dodecyl (meth) acrylate, phenyl (meth) acrylate, toluyl (meth) acrylate, benzyl (meth) acrylate, (meth) 2-methoxyethyl acrylate, 3-methoxybutyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, stearyl (meth) acrylate, (meth ) Glycidyl acrylate, 2-aminoethyl (meth) acrylate, 2- (dimethylamino) ethyl (meth) acrylate, γ- (methacryloyloxypropyl) trimethoxysilane, ethylene oxide adduct of (meth) acrylic acid, (Meth) acrylic acid trifluoromethyl methyl, (meth) acrylic acid 2-trifluoromethyl ethyl, (meth) acrylic acid 2-perfluoroethyl ethyl, (meth) acrylic acid 2-perfluoroethyl-2-perfluorobutyl Ethyl, 2-perfluoroethyl (meth) acrylate, perfluoromethe (meth) acrylate Chill, diperfluoromethylmethyl (meth) acrylate, 2-perfluoromethyl-2-perfluoroethylmethyl (meth) acrylate, 2-perfluorohexylethyl (meth) acrylate, 2- (meth) acrylic acid 2- Examples include perfluorodecylethyl and 2-perfluorohexadecylethyl (meth) acrylate.

  Specific examples of the styrenic monomer include styrene, vinyl toluene, α-methyl styrene, chlorostyrene, styrene sulfonic acid and salts thereof.

  Specific examples of (meth) acrylamide monomers include (meth) acrylonitrile, (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N- Isopropyl (meth) acrylamide, N-butyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide and the like are included.

  Specific examples of the maleic monomer include maleic anhydride, maleic acid, maleic acid monoalkyl ester and dialkyl ester, and the like.

  Examples of the maleimide monomer include maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide, cyclohexylmaleimide and the like.

  Examples of vinyl ester monomers include vinyl acetate, vinyl propionate, vinyl pivalate, vinyl benzoate, vinyl cinnamate and the like.

  Of these, the radical polymerizable monomer used in the present invention is preferably a (meth) acrylic acid monomer, a styrene monomer, or (meth) acrylonitrile. These compounds may be used alone or in combination of two or more.

  In the present invention, the method for polymerizing the radical polymerizable monomer is not particularly limited, and bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization, bulk / suspension polymerization, and the like can be applied.

  The polymerization reaction of the present invention can be carried out in a solvent. Any solvent may be used as long as it does not inhibit the reaction. Specific examples of the solvent include aromatic hydrocarbon solvents such as benzene, toluene and xylene; aliphatic hydrocarbon solvents such as pentane, hexane, heptane, octane, nonane and decane; cyclohexane, methylcyclohexane and decahydronaphthalene. Such alicyclic hydrocarbon solvents; halogenated hydrocarbon solvents such as chlorobenzene, bromobenzene, dichlorobenzene, trichlorobenzene, methylene chloride, chloroform, carbon tetrachloride and tetrachloroethylene; methanol, ethanol, n-propanol, iso- Alcohol solvents such as 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, diethyl ether, di -n- amyl ether, and the like ether solvents such as tetrahydrofuran and dioxy anisole. The polymerization reaction of the present invention may be suspension polymerization or emulsion polymerization using water as a solvent. These solvents may be used alone or in admixture of two or more. Moreover, it is preferable that the reaction liquid becomes a homogeneous phase by using these solvents, but a plurality of non-uniform phases may be used.

  The reaction temperature of the polymerization reaction of the present invention may be any temperature at which the radical polymerization reaction proceeds, and is set according to the desired degree of polymerization of the polymer, the radical polymerization initiator used, and the type and amount of the solvent. The reaction temperature is, for example, usually −100 ° C. to 250 ° C., preferably −50 ° C. to 180 ° C., more preferably 0 ° C. to 160 ° C. In some cases, the polymerization reaction may be performed under reduced pressure, normal pressure, or pressurized conditions. The polymerization reaction is preferably performed in an inert gas atmosphere such as nitrogen or argon.

  The order of addition of each component in the polymerization reaction of the present invention is not particularly limited. Preferably, the olefin polymer (A) is dissolved or suspended in a solvent; the activator (C) is added thereto; There is a method in which a metal compound (B) and a radical polymerizable monomer are added and polymerized at a predetermined polymerization temperature. Also, the order of these may be changed according to the type and properties of the polymer (A), the metal compound (B), the activator (C), and the radical polymerizable monomer, or a part thereof may be premixed in advance. It is also possible to do.

  The polymer obtained by the production method of the present invention (a polymer in which an olefin polymer segment and a radical polymer segment are chemically bonded) is preferably purified and isolated. Purification / isolation is performed using a known method, for example, by distilling off the solvent or unreacted monomer used for the polymerization or reprecipitation with a poor solvent. Furthermore, by treating the obtained polymer with a polar solvent such as acetone or THF using a Soxhlet extraction apparatus, it is possible to remove the by-product homoradical polymer.

  EXAMPLES Hereinafter, although this invention is demonstrated further more concretely based on an Example, this invention is not limited to these Examples.

The physical properties in this example were measured as follows.
(i) Measurement of molecular weight and molecular weight distribution GPC (gel permeation chromatography) was used and measured under the following conditions.
Measuring device: alliance GPC2000 (manufactured by Waters)
Analysis device: Empower Professional (manufactured by Waters)
Column: TSKgel GMH6HT x 2 + TSKgel GMH6HTL x 2
Column temperature: 140 ° C
Mobile phase: o-dichlorobenzene (ODCB)
Detector: differential refractometer flow rate: 1 mL / min
Sample concentration: 30 mg / 20 mL-ODCB
Injection volume: 500 μL
Column calibration: monodisperse polystyrene (manufactured by Tosoh Corporation)

(ii) Polymer composition analysis
Measurement was performed under the following conditions using ¹ H-NMR.
Measuring device: JNMGSX-400 nuclear magnetic resonance apparatus (manufactured by JEOL)
Sample tube: 5mmφ
Measuring solvent: o-dichlorobenzene-d4
Measurement temperature: 120 ° C
Measurement width: 8000Hz
Pulse width: 7.7 μs (45 °)
Pulse interval: 6.0s
Number of measurements: ~ 8000 times

[Example 1]
A glass reactor with an internal volume of 500 mL that has been sufficiently purged with nitrogen is charged with 30 g of particulate polypropylene (PP) (Mn = 34,500) and 200 mL of butyl acetate, and is subjected to nitrogen bubbling at 100 ° C. for 2 hours with stirring to produce a slurry. Got. After adding 1.2 g of N-bromosuccinimide (NBS) to the obtained slurry and stirring at 100 ° C. for 2 hours, 100 mL of methyl methacrylate (MMA) was added and nitrogen bubbling was performed for 1 hour. Furthermore, after adding 114 mg of copper powder and 0.75 mL of N, N, N ′, N ″, N ″ -pentamethyldiethylenetriamine (PMDETA) to this slurry, polymerization was carried out at 100 ° C. for 3 hours. After cooling, the slurry was poured into 1.5 L of acetone, stirred, and filtered through a glass filter. Further, the polymer on the filter was washed with acetone and methanol, and then dried under reduced pressure to obtain 33.6 g of a pale yellow particulate polymer.

^{According to 1} H-NMR analysis, the obtained polymer contained a PP component and a PMMA component, and the composition ratio was PP / PMMA = 90/10 (wt%). The results are shown in Table 1.

[Example 2]
30 g of the same particulate PP as in Example 1 and 200 mL of butyl acetate were placed in a glass reactor having an internal volume of 500 mL sufficiently purged with nitrogen, and nitrogen bubbling was performed at 100 ° C. for 2 hours with stirring. After adding 1.2 g of NBS to this slurry and stirring at 100 ° C. for 2 hours, 160 mL of styrene (St) and 40 mL of acrylonitrile (AN) were added and nitrogen bubbling was performed for 1 hour. After adding 318 mg of copper powder and 2.09 mL of PMDETA to this slurry, polymerization was performed at 100 ° C. for 3 hours. After cooling, 150 mL of methanol was added, and the slurry was filtered through a glass filter. Further, the polymer on the filter was washed with acetone and methanol and then dried under reduced pressure to obtain 31.7 g of a white particulate polymer.

^{According to 1} H-NMR analysis, the obtained polymer contains a PP component and a styrene-acrylonitrile copolymer (AS) component, and the composition ratio is PP / St-AN = 95/5 (wt%). Met. The results are shown in Table 1.

[Example 3]
Into a glass reactor having an internal volume of 500 mL sufficiently purged with nitrogen, 15 g of the same particulate PP as in Example 1 and 200 mL of chlorobenzene were placed, and nitrogen bubbling was performed at 100 ° C. for 2 hours with stirring. NBS 1.2g was added to this slurry, and it stirred at 100 degreeC for 2 hours, Then, MMA100mL was added and nitrogen bubbling was performed for 1 hour. To this slurry, 114 mg of copper powder and 0.75 mL of PMDETA were added, followed by polymerization at 100 ° C. for 3 hours. After cooling, the slurry was poured into 1.5 L of acetone, stirred, and filtered through a glass filter. Further, the polymer on the filter was washed with acetone and methanol and then dried under reduced pressure to obtain 35.0 g of a light yellow particulate polymer.

^{According to 1} H-NMR analysis, the obtained polymer contained a PP component and a PMMA component, and the composition ratio was PP / PMMA = 43/57 (wt%). The results are shown in Table 1.

[Example 4]
16.6 g of white particulate polymer was obtained in the same manner as in Example 3 except that the solvent was anisole. ^{According to 1} H-NMR analysis, the obtained polymer contained a PP component and a PMMA component, and the composition ratio was PP / PMMA = 91/9 (wt%). The results are shown in Table 1.

[Comparative Example 1]
14.8 g of white particulate polymer was obtained in the same manner as in Example 3 except that NBS was not added. ^{From 1} H-NMR analysis, no MMA component was detected in the obtained polymer. The results are shown in Table 1.

[Comparative Example 2]
14.9 g of white particulate polymer was obtained in the same manner as in Example 3 except that copper powder and PMDETA were not added. ^{From 1} H-NMR analysis, no MMA component was detected in the obtained polymer. The results are shown in Table 1.

[Example 5]
Into a glass reactor with an internal volume of 500 mL sufficiently purged with nitrogen, 15 g of ethylene-propylene copolymer (EPR; Mn = 51,900) and 200 mL of chlorobenzene were placed, and nitrogen bubbling was performed at 100 ° C. for 2 hours with stirring. . After adding 0.15 mL of bromine to this solution and stirring at 100 ° C. for 2 hours, 90 mL of dodecyl methacrylate (DMA) was added and nitrogen bubbling was performed for 1 hour. To this solution, 215 mg of copper (I) bromide and 3.13 mL of PMDETA were added, followed by polymerization at 80 ° C. for 4 hours. After cooling, the reaction solution was poured into 1.5 L of methanol and stirred, and the supernatant was removed. After adding 1.5 L of methanol again and stirring, the precipitated rubber-like polymer was dried under reduced pressure at 120 ° C. to obtain 18.2 g of a brown rubber-like polymer.

^{According to 1} H-NMR analysis, the obtained polymer contained an EPR component and a PDMA component, and the composition ratio was EPR / PDMA = 82/18 (wt%). The results are shown in Table 2.

[Example 6]
25.6 g of a brown rubbery polymer was obtained in the same manner as in Example 5 except that the amounts of copper (I) bromide and PMDETA were changed as shown in Table 2. ^{From the 1} H-NMR analysis, the obtained polymer contained an EPR component and a PDMA component, and the composition ratio was EPR / PDMA = 59/41 (wt%). The results are shown in Table 2.

[Example 7]
37.0 g of a brown rubbery polymer was obtained in the same manner as in Example 6 except that the activator was changed from bromine to NBS 0.6 g. ^{From the 1} H-NMR analysis, the obtained polymer contained an EPR component and a PDMA component, and the composition ratio was EPR / PDMA = 41/59 (wt%). The results are shown in Table 2.

[Example 8]
Into a glass reactor having an internal volume of 500 mL sufficiently purged with nitrogen, 15 g of EPR as in Example 5 and 200 mL of butyl acetate were placed, and nitrogen bubbling was performed at 110 ° C. for 2 hours with stirring. NBS 0.6g was added to this suspension, and after stirring at 110 degreeC for 2 hours, DMA100mL was added and nitrogen bubbling was performed for 1 hour. After adding 381 mg of copper powder and 2.51 mL of PMDETA to this suspension, polymerization was performed at 110 ° C. for 4 hours. After cooling, the reaction solution was poured into 1.5 L of methanol and stirred, and the supernatant was removed. After adding 1.5 L of methanol again and stirring, the precipitated rubber-like polymer was dried under reduced pressure at 120 ° C. to obtain 56.3 g of a brown rubber-like polymer.

^{From the 1} H-NMR analysis, the obtained polymer contained an EPR component and a PDMA component, and the composition ratio was EPR / PDMA = 27/73 (wt%). The results are shown in Table 2.

[Examples 9 to 13]
Polymerization of dodecyl methacrylate was carried out in the same manner as in Example 8 except that the amounts of copper powder and PMDETA were changed as shown in Table 2. The results are shown in Table 2.

[Example 14]
A glass reactor having an internal volume of 500 mL sufficiently purged with nitrogen was charged with 15 g of EPR as in Example 5 and 200 mL of butyl acetate, and subjected to nitrogen bubbling at 100 ° C. for 2 hours with stirring. NBS 0.6g was added to this suspension, and it stirred at 100 degreeC for 2 hours, Then, DMA100mL was added and nitrogen bubbling was performed for 1 hour. After adding 95 mg of copper powder and 0.63 mL of PMDETA to this suspension, polymerization was performed at 100 ° C. for 4 hours. After cooling, the reaction solution was poured into 1.5 L of methanol and stirred, and the supernatant was removed. After adding 1.5 L of methanol again and stirring, the precipitated rubber-like polymer was dried under reduced pressure at 120 ° C. to obtain 58.1 g of a brown rubber-like polymer.

^{From the 1} H-NMR analysis, the obtained polymer contained an EPR component and a PDMA component, and the composition ratio was EPR / PDMA = 26/74 (wt%). The results are shown in Table 2.

[Example 15]
Into a glass reactor having an internal volume of 500 mL sufficiently purged with nitrogen, 15 g of EPR as in Example 5 and 200 mL of chlorobenzene were placed, and nitrogen bubbling was performed at 100 ° C. for 2 hours with stirring. NBS 0.6g was added to this solution, and it stirred at 100 degreeC for 2 hours, Then, DMA100mL was added and nitrogen bubbling was performed for 1 hour. After adding 95 mg of copper powder and 0.63 mL of PMDETA to this solution, polymerization was performed at 100 ° C. for 4 hours. After cooling, the reaction solution was poured into 1.5 L of methanol and stirred, and the supernatant was removed. After adding 1.5 L of methanol again and stirring, the precipitated rubber-like polymer was dried under reduced pressure at 120 ° C. to obtain 59.6 g of a brown rubber-like polymer.

^{From the 1} H-NMR analysis, the obtained polymer contained an EPR component and a PDMA component, and the composition ratio was EPR / PDMA = 25/75 (wt%). The results are shown in Table 2.

[Example 16]
Into a glass reactor having an internal volume of 1 L that was sufficiently purged with nitrogen, 50 g of ethylene-butene copolymer (EBR; Mn = 82,000) and 700 mL of butyl acetate were placed, and nitrogen bubbling was performed at 110 ° C. for 2 hours with stirring. . After adding 1.25g of NBS to this suspension and stirring at 110 degreeC for 2 hours, 50 mL of MMA and 7 mL of glycidyl methacrylate (GMA) were added, and nitrogen bubbling was performed for 1 hour. After adding 199 mg of copper powder and 1.30 mL of PMDETA to this suspension, polymerization was carried out at 110 ° C. for 2 hours. After cooling, the suspension was poured into 1.5 L of acetone and stirred, and the supernatant was removed. After adding 1.5 L of acetone again and stirring, the precipitated rubber-like polymer was dried under reduced pressure at 120 ° C. to obtain 64.0 g of a brown rubber-like polymer.

^{From the 1} H-NMR analysis, the obtained polymer contained an EBR component and an MMA-GMA copolymer component, and the composition ratio was EBR / MMA-GMA = 78/22 (wt%). . The results are shown in Table 3.

[Examples 17 to 19]
MMA and GMA were copolymerized in the same manner as in Example 16 except that the amount of NBS, copper powder, PMDETA, and GMA and the polymerization time were changed as shown in Table 3. The results are shown in Table 3.

[Example 20]
50 g of EBR and 700 mL of chlorobenzene as in Example 16 were placed in a 1 L glass reactor sufficiently purged with nitrogen, and nitrogen bubbling was performed at 110 ° C. for 2 hours with stirring. NBS 1.25g was added to this solution, and it stirred at 110 degreeC for 2 hours, Then, GMA30mL was added and nitrogen bubbling was performed for 1 hour. After adding 199 mg of copper powder and 1.30 mL of PMDETA to this solution, polymerization was performed at 110 ° C. for 1 hour. After cooling, the reaction solution was poured into 1.5 L of acetone and stirred, and the supernatant was removed. After adding 1.5 L of acetone again and stirring, the precipitated rubber-like polymer was dried under reduced pressure at 120 ° C. to obtain 51.6 g of a brown rubber-like polymer.

^{From the 1} H-NMR analysis, the obtained polymer contained an EBR component and a PGMA component, and the composition ratio was EBR / PGMA = 97/3 (wt%). The results are shown in Table 3.

[Example 21]
90 g of ethylene-butene copolymer (EBR; Mn = 131,000) and 1200 mL of chlorobenzene were placed in a 2 L glass reactor sufficiently purged with nitrogen, and nitrogen bubbling was performed at 100 ° C. for 2 hours with stirring. After adding NBS1.8g to this solution and stirring at 100 degreeC for 2 hours, MMA600mL was added and nitrogen bubbling was performed for 1 hour. After adding 286 mg of copper powder and 1.88 mL of PMDETA to this solution, polymerization was performed at 100 ° C. for 2 hours. After cooling, the solution was poured into 1.5 L of methanol and stirred, and the supernatant was removed. After adding 1.5 L of methanol again and stirring, the precipitated rubber-like polymer was dried under reduced pressure at 120 ° C. to obtain 91.2 g of a brown rubber-like polymer.

^{From the 1} H-NMR analysis, the obtained polymer contained an EBR component and a PMMA component, and the composition ratio was EBR / PMMA = 99/1 (wt%). The results are shown in Table 3.

[Example 22]
90 g of EBR and 1200 mL of chlorobenzene similar to those used in Example 21 were placed in a 2 L glass reactor sufficiently purged with nitrogen, and nitrogen bubbling was performed at 100 ° C. for 2 hours with stirring. After adding NBS1.8g to this solution and stirring at 100 degreeC for 2 hours, MMA600mL was added and nitrogen bubbling was performed for 1 hour. To this solution, 1.60 g of copper (I) chloride and 3.38 mL of PMDETA were added, followed by polymerization at 100 ° C. for 1 hour. After cooling, the solution was poured into 1.5 L of methanol and stirred, and the supernatant was removed. After adding 1.5 L of methanol again and stirring, the precipitated rubber-like polymer was dried under reduced pressure at 120 ° C. to obtain 133.7 g of a brown rubber-like polymer.

^{From the 1} H-NMR analysis, the obtained polymer contained an EBR component and a PMMA component, and the composition ratio was EBR / PMMA = 67/33 (wt%). The results are shown in Table 3.

[Example 23]
Except for setting the polymerization time to 3 hours, 233.3 g of a brown polymer was obtained in the same manner as in Example 22. From the 1H-NMR analysis, the obtained polymer contained an EBR component and a PMMA component, and the composition ratio was EBR / PMMA = 39/61 (wt%). The results are shown in Table 3.

[Comparative Example 3]
15 g of EBR and 200 mL of chlorobenzene similar to those used in Example 21 were placed in a glass reactor having an internal volume of 500 mL sufficiently purged with nitrogen, and nitrogen bubbling was performed at 100 ° C. for 2 hours with stirring. MMA100mL was added to this solution, and nitrogen bubbling was performed for 1 hour. To this solution, 267 mg of copper (I) chloride and 0.56 mL of PMDETA were added, followed by polymerization at 100 ° C. for 3 hours. After cooling, the solution was poured into 1.5 L of methanol and stirred, and the supernatant was removed. After adding 1.5 L of methanol again and stirring, the precipitated rubber-like polymer was dried under reduced pressure at 120 ° C. to obtain 14.7 g of a brown rubber-like polymer. ^{From 1} H-NMR analysis, it was found that no PMMA component was contained in the obtained polymer. The results are shown in Table 3.

[Example 24]
Into a glass reactor having an internal volume of 1 L sufficiently purged with nitrogen, 50 g of ethylene-butene copolymer (EBR; Mn = 51,000) and 700 mL of chlorobenzene were placed, and nitrogen bubbling was performed at 110 ° C. for 2 hours with stirring. After adding NBS0.625g to this solution and stirring at 110 degreeC for 2 hours, GMA30mL was added and nitrogen bubbling was performed for 1 hour. After adding 99 mg of copper powder and 0.65 mL of PMDETA to this solution, polymerization was performed at 110 ° C. for 1 hour. After cooling, the solution was poured into 1.5 L of methanol and stirred, and the supernatant was removed. After adding 1.5 L of methanol again and stirring, the precipitated rubber-like polymer was dried under reduced pressure at 120 ° C. to obtain 55.1 g of a brown rubber-like polymer. ^{From the 1} H-NMR analysis, the obtained polymer contained an EBR component and a PGMA component, and the composition ratio was EBR / PGMA = 91/9 (wt%). The results are shown in Table 3.

[Example 25]
GMA radical polymerization was performed in the same manner as in Example 24 except that the amounts of NBS, copper powder, and PMDETA were changed. From the 1H-NMR analysis, the obtained polymer contained an EBR component and a PGMA component, and the composition ratio was EBR / PGMA = 87/13 (wt%). The results are shown in Table 3.

  According to the present invention, a polymer in which an olefin polymer segment and a radical polymer segment are chemically bonded is produced in one step using olefin polymers such as polyethylene and polypropylene which are widely produced industrially as raw materials. Can do. Therefore, the manufacturing process can be greatly simplified as compared with the prior art, which is very advantageous in terms of manufacturing cost and energy consumption.

Claims (6)

A method for producing a polymer in which an olefin polymer segment and a radical polymer segment are chemically bonded,
Olefin polymer containing no halogen element (A), metal compound (B) containing a transition metal element selected from Group 3 to Group 11 of the periodic table, and halogen-halogen bond or nitrogen-halogen bond in the molecule A method for producing a polymer, wherein a radically polymerizable monomer is polymerized in the presence of an activator (C) having a hydrogen atom. The olefin polymer (A) is a polymer selected from the group consisting of the following (A1) to (A5), and the number average molecular weight (in terms of standard polystyrene) is in the range of 1 × 10 ³ to 1 × 10 ⁷ . The method for producing a polymer according to claim 1, wherein
(A1): A homopolymer or copolymer of an α-olefin compound represented by CH ₂ ═CH—C _X H _{2X + 1} (x is 0 or a positive integer).
(A2): A copolymer of an α-olefin compound represented by CH ₂ ═CH—C _X H _{2X + 1} (x is 0 or a positive integer) and a monoolefin compound having an aromatic ring.
(A3): Co-weight of an α-olefin compound represented by CH ₂ ═CH—C _X H _{2X + 1} (x is 0 or a positive integer) and a cyclic monoolefin compound represented by the following general formula (1) Coalescence.
(A4): A random copolymer of an α-olefin compound represented by CH ₂ ═CH—C _X H _{2X + 1} (x is 0 or a positive integer) and an unsaturated carboxylic acid or a derivative thereof.
(A5): A polymer obtained by modifying any of the polymers (A1) to (A4) with an unsaturated carboxylic acid or a derivative thereof.

(In Formula (1), n is 0 or 1, m is 0 or a positive integer, q is 0 or 1, and R ^{1 to} R ¹⁸ and R ^a and R ^b are each independently, And represents an atom or group selected from the group consisting of a hydrogen atom and a hydrocarbon group, and R ^{15 to} R ¹⁸ may combine with each other to form a monocyclic or polycyclic ring)   The method for producing a polymer according to claim 1 or 2, wherein the metal compound (B) contains a metal selected from titanium, zirconium, molybdenum, rhenium, iron, ruthenium, rhodium, cobalt, nickel, palladium, and copper.   The activator (C) is chlorine, bromine, N-chlorosuccinimide, N-bromosuccinimide, N-bromocaprolactam, N-bromophthalimide, 1,3-dibromo-5,5-dimethylhydantoin, N-chloroglutar The method for producing a polymer according to any one of claims 1 to 3, wherein the polymer is imide, N-bromoglutarimide, or N, N'-dibromoisocyanuric acid.   The radical polymerizable monomer is a (meth) acrylic acid monomer, styrene monomer, (meth) acrylonitrile, (meth) acrylamide monomer, maleic monomer, maleimide monomer The manufacturing method of the polymer as described in any one of Claims 1-4 which is an organic compound chosen from the group which consists of a body and a vinyl ester-type monomer.   The olefin polymer (A) is a polymer selected from (A1), the metal compound (B) is a copper compound, and the activator (C) is bromine or N-bromosuccinimide. The manufacturing method of the polymer as described in any one of Claims 2-5.