JP2010222532A - Method for producing polymer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polymer wherein an olefin polymer segment containing less metallic residue derived from a polymerization catalyst and less discolored is chemically bound to a radial polymer segment. <P>SOLUTION: The method for producing a polymer, wherein an olefin polymer segment is chemically bound to a radical polymer segment, includes a step of polymerizing a radically polymerizable monomer in the presence of a halogen-modified 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 a nitrogen-containing compound (C), wherein the molar ratio of the nitrogen-containing compound (C) to the metal compound (B) is ≥10. <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.

  Development of living radical polymerization is advancing as one method for precise polymerization of radically polymerizable monomers. Living radical polymerization has the characteristics that a polymer with a narrow molecular weight distribution and a precisely controlled monomer sequence can be obtained. Atom transfer radical polymerization, nitroxide-mediated radical polymerization, reversible addition cleavage Chain transfer polymerization has been reported.

  Among them, the atom transfer radical polymerization method using an organic halide as an initiator and a transition metal compound as a catalyst can introduce a specific functional group at the end of the molecular chain in addition to the above characteristics, In recent years, research has been actively carried out because topology control of graft structure, star structure, etc. is easy.

  In particular, the atom transfer radical polymerization method is effective for producing a polymer in which different segments such as a block polymer and a graft polymer are chemically bonded to each other. For example, a method for producing a block-graft polymer comprising a polyolefin segment and a polar segment by carrying out atom transfer radical polymerization from a polymerization initiation point introduced into the terminal or main chain of the polyolefin has been disclosed (for example, patents) Reference 1 to Patent Document 3). However, in the atom transfer radical polymerization method, since a transition metal compound is used as a polymerization catalyst, metal residues derived from the polymerization catalyst remain in the obtained polymer, causing problems such as coloring and deterioration of the polymer. There is a fear. Therefore, studies such as efficient catalyst removal and reduction of polymerization catalyst to be used have been actively conducted.

  Examples of the method for removing the polymerization catalyst after the atom transfer radical polymerization include a method of purifying the polymer by contacting with an adsorbent such as activated carbon, activated alumina, aluminum silicate, silicon dioxide, and subsequently removing the adsorbent. (See Patent Document 4). In addition, a method of directly adding a solid organic acid to destroy the complex and insolubilizing and removing the metal has also been reported (see Patent Document 5). However, in the former method, there are cases where the adsorbent is expensive, takes time for adsorption, or is incompletely adsorbed. In the latter method, the solubility of the solid acid in the solvent is low, and it is necessary to add the solid acid to the complex excessively, and the catalyst deactivation reaction may take a long time. Furthermore, the insolubilized copper is in the form of a fine powder and floats in the polymer-containing solution, and much time is required to remove the catalyst by solid-liquid separation.

  In addition, a method has been studied for facilitating or omitting the deashing / purification step after polymerization by minimizing the amount of polymerization catalyst added in the atom transfer radical polymerization reaction. For example, it is disclosed that by adding a specific reducing agent, atom transfer radical polymerization proceeds even if the copper catalyst concentration in the polymerization system is greatly reduced, and a polymer having a narrow molecular weight distribution is obtained ( (See Patent Document 6). However, a typical reducing agent in this method is an alkyl tin compound, which is by no means a preferable method in terms of adding another metal species to the system in addition to the polymerization catalyst.

JP 2004-131620 A JP 2007-169318 A International Publication No. 2006/088197 Pamphlet JP-A-11-193307 JP 2003-147015 A Special table 2007-527463 gazette

  An object of the present invention is to provide a polymer in which an olefin polymer segment and a radical polymer segment are chemically bonded, with a small amount of metal residue derived from a polymerization catalyst and little coloration.

  In the presence of a halogen atom-containing olefin polymer, the present inventors present a transition metal compound used as a catalyst and a nitrogen-containing compound in the polymerization system when performing atom transfer radical polymerization of a radical polymerizable monomer. And the amount of nitrogen-containing compound added to the catalyst was adjusted. It has been found that atom transfer radical polymerization proceeds even when the catalyst concentration in the polymerization system is greatly reduced by appropriately controlling the amount added. Furthermore, it has been found that a polymer with little metal residue derived from the polymerization catalyst and less coloring can be obtained, and the present invention has been completed.

  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: a halogen-modified olefin polymer (A), and periodic groups 3 to 11 in the periodic table. Including the step of polymerizing a radical polymerizable monomer in the presence of a metal compound (B) containing a transition metal element selected from the group and a nitrogen-containing compound (C), and containing the nitrogen with respect to the metal compound (B) It is a manufacturing method of a polymer whose molar ratio of a compound (C) is 10 or more.

  According to the present invention, a polymer in which a metal residue derived from a polymerization catalyst is small and an uncolored olefin polymer segment and a radical polymer segment are chemically bonded can be obtained. Furthermore, according to the method of the present invention, the amount of catalyst used can be greatly reduced, and the post-treatment step after polymerization is simplified, which is very advantageous in terms of production cost.

Hereafter, the manufacturing method of the polymer of this invention is demonstrated concretely.
The present invention provides a halogen-modified olefin polymer (A), a metal compound (B) containing a transition metal element selected from Groups 3 to 11 of the periodic table, and a nitrogen-containing compound (C). In the production of a polymer in which the olefin polymer segment and the radical polymer segment are chemically bonded by polymerizing the radical polymerizable monomer, the molar ratio of the nitrogen-containing compound (C) to the metal compound (B) is 10 It is characterized by the above.

  The halogen-modified olefin polymer (A) is obtained by reacting an olefin polymer with a halogenating agent. The reaction of the olefin polymer with the halogenating agent will be described in detail later.

  The olefin polymer to be reacted with the halogenating agent is preferably composed of a monoolefin compound having only one carbon-carbon double bond or a monoolefin compound having an aromatic ring. 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), When a copolymer having such a copolymer component is halogenated, unsaturated bonds derived from the diene compound may be cross-linked and gelled, which may be undesirable.

  The halogen-modified olefin polymer (A) used in the present invention is a polymer obtained by halogenating, for example, an olefin polymer selected from the group consisting of the following (A1) to (A5). Two or more olefin polymers selected from the group consisting of the following (A1) to (A5) may be used in combination.

_{(A1): CH 2 = CH} -CxH 2X + 1 (x is 0 or a positive integer) homopolymer of α- olefin compound represented by or a copolymer.
(A2): A copolymer of an α-olefin compound represented by CH ₂ ═CH—CxH _{2X + 1} (x is 0 or a positive integer) and a monoolefin compound having an aromatic ring.
(A3): Copolymer of an α-olefin compound represented by CH ₂ ═CH—CxH _{2X + 1} (x is 0 or a positive integer) and a cyclic monoolefin compound represented by the following general formula (1) .
(A4): A random copolymer of an α-olefin compound represented by CH ₂ ═CH—CxH _{2X + 1} (x is 0 or a positive integer) and an unsaturated carboxylic acid or a derivative thereof.
(A5) A polymer obtained by modifying the polymers (A1) to (A4) with an unsaturated carboxylic acid or a derivative thereof.

（式（１）における記号の定義は後述する）

(Definition of symbols in formula (1) will be described later)

About the olefin polymer (A1):
The first example of the olefin polymer to be halogenated is a homopolymer or copolymer (A1) of an α-olefin compound represented by CH ₂ ═CH—CxH _{2X + 1} (x is 0 or a positive integer). It is.

Specific examples of the α-olefin compound represented by CH ₂ ═CH—CxH _{2X + 1} (x is 0 or a positive integer) include ethylene, propylene, 1-butene, 1-pentene, and 3-methyl-1-butene. 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, etc. A linear or branched α-olefin having 4 to 20 carbon atoms is 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. Are ethylene, propylene and 1-butene.

  The olefin polymer (A1) is not particularly limited as long as it is obtained by homopolymerization or copolymerization of the α-olefin compound. Preferred examples of the olefin 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 copolymers; polybutene, poly (4-methyl-1-pentene), poly (1-hexene), ethylene-propylene copolymer, ethylene-butene copolymer, ethylene-hexene copolymer Polymer, 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 the olefin polymer (A2):
A second example of the olefin polymer to be halogenated is a mixture of an α-olefin compound represented by CH ₂ ═CH—CxH _{2X + 1} (x is 0 or a positive integer) and a monoolefin compound having an aromatic ring. It is a copolymer (A2).

Examples of the α-olefin compound represented by CH ₂ ═CH—CxH _{2X + 1} (x is 0 or a positive integer) include the α-olefin compounds described in the above section (A1). Specific examples of the monoolefin compound having an aromatic ring include styrene compounds such as styrene, vinyltoluene, α-methylstyrene, chlorostyrene, styrenesulfonic acid and salts thereof, and vinylpyridine.

  The olefin polymer (A2) is not particularly limited as long as it is obtained by copolymerizing the above α-olefin compound and a monoolefin compound having an aromatic ring. Preferred examples of the olefin polymer (A2) include ethylene-styrene copolymer, propylene-styrene copolymer, ethylene-propylene-styrene terpolymer, and 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. .

About the olefin polymer (A3):
A third example of the olefin polymer to be halogenated is represented by the α-olefin compound represented by CH ₂ ═CH—CxH _{2X + 1} (x is 0 or a positive integer) and the following general formula (1). It is a copolymer (A3) with a cyclic monoolefin compound.

Examples of the α-olefin compound represented by CH ₂ ═CH—CxH _{2X + 1} (x is 0 or a positive integer) include the α-olefin compounds described in the above section (A1).

In the general formula (1) representing a cyclic monoolefin, n is 0 or 1, m is 0 or a positive integer, and q is 0 or 1. R ^{1 to} R ¹⁸ and R ^a and R ^b each independently represent an atom or group selected from the group consisting of a hydrogen atom, a halogen atom and a hydrocarbon group. R ^{15 to} R ¹⁸ may be bonded to each other to form a monocycle or polycycle. When q is 0, each bond joins to form a 5-membered ring.

The halogen atom represented by R ^{1 to} R ¹⁸ and R ^a and R ^b in the general formula (1) is a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. The hydrocarbon group represented by R ^{1 to} R ¹⁸ and R ^a and R ^b is usually an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, or 3 to 15 carbon atoms. It may be a cycloalkyl group. More specifically, examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an amyl group, a hexyl group, an octyl group, a decyl group, a dodecyl group and an octadecyl group; And a group in which at least a part of the hydrogen atoms forming the alkyl group is substituted with a fluorine atom, a chlorine atom, a bromine atom or an iodine atom: Examples of the cycloalkyl group include a cyclohexyl group and the like .

Further, in the general formula (1), R ¹⁵ and R ¹⁶ 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 include the following.

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 numbered 2 The atom represents a carbon atom to which R ¹⁷ and R ¹⁸ are bonded.

Specific examples of the cyclic olefin represented by the general formula (1) include bicyclo [2.2.1] hept-2-ene derivative, tricyclo [4.3.0.1 ^2,5 ] -3-decene derivative, 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.

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

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

The olefin polymer (A3) is not particularly limited as long as it is obtained by copolymerizing the α-olefin compound and the cyclic monoolefin compound. Preferred examples of the olefin polymer (A3), a copolymer of ethylene and bicyclo [2.2.1] hept-2-ene, ethylene and tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3 -A copolymer with dodecene.

  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 olefin polymer (A4):
A fourth example of the halogenated olefin polymer is an α-olefin compound represented by CH ₂ ═CH—CxH _{2X + 1} (x is 0 or a positive integer) and an unsaturated carboxylic acid or a derivative thereof. It is a random copolymer (A4).

Examples of the α-olefin compound represented by CH ₂ ═CH—CxH _{2X + 1} (x is 0 or a positive integer) include the α-olefin compounds described in the above section (A1). The unsaturated carboxylic acid or derivative thereof is, for example, an unsaturated monocarboxylic acid and derivative thereof, unsaturated dicarboxylic acid and derivative thereof, or vinyl ester; specifically, (meth) acrylic acid, (meth) Fats such as acrylic esters, (meth) acrylic halides, (meth) acrylic amides, maleic acid, maleic anhydride, maleic esters, maleic halides, maleic amides, maleic imides, vinyl acetate and vinyl butyrate Group vinyl esters and the like.

  The olefin polymer (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 olefin polymer (A4) include ethylene- (meth) acrylic acid copolymer, ethylene- (meth) acrylic acid ester copolymer, ethylene-maleic anhydride copolymer, ethylene-vinyl acetate copolymer. Polymers and the like are included.

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

About the olefin polymer (A5):
A fifth example of the halogenated olefin polymer is a polymer (A5) obtained by modifying the polymers (A1) to (A4) with an unsaturated carboxylic acid or a derivative thereof.

  Specific examples of unsaturated carboxylic acids or derivatives thereof for modifying the polymers (A1) to (A4) include maleic acid, maleic anhydride, maleic ester, maleic halide, maleic amide, maleic imide Of these, maleic anhydride is preferred.

  As a method for modifying the polymers (A1) to (A4) with an unsaturated carboxylic acid or a derivative thereof, for example, in the presence of a radical generator such as an organic peroxide, or in the presence of ultraviolet rays or radiation, A method of reacting a carboxylic acid or a derivative thereof with the polymers (A1) to (A4) is included.

  There are no particular restrictions on the conditions and method for producing the olefin polymer (preferably, the olefin polymers (A1) to (A5)). Coordination anion polymerization using a transition metal catalyst, radical polymerization under high pressure or irradiation, and the like 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.

  As described above, the halogen-modified olefin polymer (A) used in the present invention is obtained by reacting an olefin polymer (for example, the above-mentioned olefin polymers (A1) to (A5)) with a halogenating agent. can get. Specific examples of halogenating agents used for halogenation include chlorine, bromine, iodine, phosphorus trichloride, phosphorus tribromide, phosphorus triiodide, phosphorus pentachloride, phosphorus pentabromide, phosphorus pentaiodide, thionyl chloride. , Sulfuryl chloride, thionyl bromide, N-chlorosuccinimide, N-bromosuccinimide, N-bromocaprolactam, N-bromophthalimide, 1,3-dibromo-5,5-dimethylhydantoin, N-chloroglutarimide, N-bromo Glutarimide, N, N′-dibromoisocyanuric acid, N-bromoacetamide, N-bromocarbamic acid ester, dioxane dibromide, phenyltrimethylammonium tribromide, pyridinium hydrobromide perbromide, pyrrolidone hydrotribromide, hypochlorous acid t -Butyl, t-butyl hypobromite, copper (II) chloride, copper (II) bromide Iron chloride (III), oxalyl chloride, and the like IBr.

  Of these, preferred halogenating agents are chlorine, bromine, N-chlorosuccinimide, N-bromosuccinimide, N-bromocaprolactam, N-bromophthalimide, 1,3-dibromo-5,5-dimethylhydantoin, N-chloro. Glutarimide, N-bromoglutarimide, N, N′-dibromoisocyanuric acid; more preferably bromine and N-bromosuccinimide, N-bromocaprolactam, N-bromophthalimide, 1,3-dibromo-5, It is a compound having an N-Br bond such as 5-dimethylhydantoin, N-bromoglutarimide, N, N′-dibromoisocyanuric acid.

  The reaction between the olefin polymer (preferably the olefin polymers (A1) to (A5)) and the halogenating agent is preferably performed in an inert gas atmosphere. Examples of the inert gas include inert gases such as nitrogen, argon, and helium. The reaction with the halogenating agent can be performed in a solvent as necessary, and any solvent that does not inhibit the reaction can be used. Specific examples of solvents that can be used 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 decahydro. Alicyclic hydrocarbon solvents such as naphthalene; chlorinated hydrocarbon solvents such as chlorobenzene, dichlorobenzene, trichlorobenzene, methylene chloride, chloroform, carbon tetrachloride and tetrachloroethylene, tetrachloroethane; methanol, ethanol, n-propanol, Alcohol solvents such as iso-propanol, n-butanol, sec-butanol and tert-butanol; ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone; S such as ethyl acetate and dimethyl phthalate Ter solvents; ether solvents such as dimethyl ether, diethyl ether, di-n-amyl ether, tetrahydrofuran and dioxyanisole are included. Examples of preferred solvents include aliphatic hydrocarbon solvents such as pentane, hexane, heptane, octane, nonane and decane; alicyclic hydrocarbon solvents such as cyclohexane, methylcyclohexane and decahydronaphthalene; chlorobenzene, dichlorobenzene And chlorinated hydrocarbon solvents such as trichlorobenzene, methylene chloride, chloroform, carbon tetrachloride, tetrachloroethylene and tetrachloroethane. 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.

  In order to accelerate the reaction between the olefin polymer (preferably the olefin polymers (A1) to (A5)) and the halogenating agent, a radical initiator may be added as necessary. The radical initiator may be, for example, an azo initiator, a peroxide initiator, a redox initiator, or the like.

  Examples of azo initiators include azobisisobutyronitrile, azobis-2,4-dimethylvaleronitrile, azobiscyclohexanecarbonitrile, azobis-2-amidinopropane hydrochloride, azobisisobutyric acid dimethyl, azobisisobutylamidine hydrochloride Salt, or 4,4′-azobis-4-cyanovaleric acid.

  Examples of peroxide based initiators include benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, di-tert-butyl peroxide, lauroyl peroxide, acetyl peroxide, diisopropyl dicarbonate, cumene hydroperoxide, tert-butyl hydroperoxide, dicumyl peroxide, p-menthane hydroperoxide, pinane hydroperoxide, methyl ethyl ketone peroxide, cyclohexanone peroxide, diisopropyl peroxydicarbonate, tert-butyl peroxylaurate, di-tert-butyl peroxyphthalate, dibenzyl oxide Alternatively, 2,5-dimethylhexane-2,5-dihydroperoxide and the like are included.

  Examples of the redox initiator include benzoyl peroxide-N, N-dimethylaniline or peroxodisulfuric acid-sodium hydrogen sulfite.

  Of these radical initiators, azo initiators or peroxide initiators are preferred; more preferably, benzoyl peroxide, di-tert-butyl peroxide, lauroyl peroxide, acetyl peroxide, diisopropyl peroxide. Carbonate, cumene hydroperoxide, tert-butyl hydroperoxide, dicumyl peroxide, azobisisobutyronitrile, azobis-2,4-dimethylvaleronitrile, azobiscyclohexanecarbonitrile, dimethyl azobisisobutyrate. These radical initiators can be used alone or in combination of two or more simultaneously or sequentially.

  Various conventionally known methods can be applied to the procedure of reacting the olefin polymer (preferably, the olefin polymers (A1) to (A5)) with the halogenating agent. For example, the olefin polymer is suspended or dissolved in a solvent, usually at a temperature of −80 ° C. to 250 ° C., preferably at a temperature not lower than room temperature and not higher than the boiling point of the solvent. A method of adding and mixing an initiator and the like; or contacting a halogenating agent and, if necessary, a radical initiator while melt-kneading the olefin polymer at a melting point or higher (for example, 180 to 300 ° C.). The method of letting it be mentioned.

The halogen-modified 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 to 1 × 10 ⁶ ; more preferably 1 × 10 ^{4 to} 5 × 10 ⁵ .

  The halogen content of the halogen-modified olefin polymer (A) used in the present invention is 0.01 to 20% by weight, preferably 0.02 to 10% by weight, more preferably 0.05 to 5% by weight. . The halogen atom to be introduced may be any of fluorine, chlorine, bromine and iodine, preferably chlorine and bromine, more preferably bromine. Moreover, the combination of these some halogen may be sufficient. The content of halogen atoms present in the halogen-modified olefin polymer (A) can be measured by a method such as elemental analysis or ion chromatography.

  In the method for producing a polymer of the present invention, one or more monomers selected from radically polymerizable monomers are atom-transferred radically polymerized using the halogen-modified olefin polymer (A) as a macroinitiator. Transfer radical polymerization is performed in the presence of a metal compound (B) containing a transition metal element selected from Groups 3 to 11 of the periodic table and a nitrogen-containing compound (C).

  The macroinitiator means a polymer having the ability of initiating atom transfer radical polymerization, and means a polymer having a site that can serve as an initiation point for atom transfer radical polymerization in the molecular chain.

  In general, atom transfer radical polymerization is one of living radical polymerization, in the presence of a catalyst composed of a metal complex having a transition metal as a central metal with an organic halide or a sulfonyl halide compound as an initiator. This is a method of radical polymerization of a polymerizable monomer. Atom transfer radical polymerization is described in, for example, Matyjaszewski et al., Chem. Rev., 101, 2921 (2001); WO96 / 30421; WO97 / 18247; WO98 / 01480; WO98 / 40415; WO00 / 15695. Or Sawamoto et al., Chem. Rev., 101, 3689 (2001); JP-A-8-411117; JP-A-9-208616: JP-A 2000-264914; JP-A-2001-316410 Disclosed in Japanese Patent Application Laid-Open No. 2002-80523; Japanese Patent Application Laid-Open No. 2004-307872, and the like can be referred to.

  Initiators used for atom transfer radical polymerization can be, for example, organic halides or sulfonyl halide compounds; in particular, they are present at the alpha position of the carbon-carbon double bond or the alpha position of the carbon-oxygen double bond. A structure in which a carbon-halogen bond or a plurality of halogen atoms are added on one carbon atom is suitable as the initiator structure.

  The halogen-modified olefin polymer (A) of the present invention preferably also has a carbon-halogen bond present at the α-position of the carbon-carbon double bond, or a structure in which a plurality of halogens are added on one carbon atom. It can be used as an initiator structure.

  The method for producing a polymer in which an olefin polymer segment and a radical polymer segment are chemically bonded by using the halogen-modified olefin polymer (A) according to the present invention as a macroinitiator is basically the above halogen. Radical polymerizable monomer in the presence of the modified olefin polymer (A) using a metal compound (B) containing a transition metal element selected from Groups 3 to 11 of the periodic table and a nitrogen-containing compound (C) as catalysts. The body is subjected to atom transfer radical polymerization.

  As the metal compound (B) containing a transition metal element selected from Group 3 to Group 11 of the periodic table, preferably from titanium, zirconium, molybdenum, rhenium, iron, ruthenium, rhodium, cobalt, nickel, palladium, copper It is a compound containing a selected metal. More preferable examples include a complex of zero-valent copper, monovalent copper, divalent ruthenium, divalent iron, and divalent nickel. Among these, a copper complex is preferable.

Specific examples of the monovalent copper compound include cuprous chloride, cuprous bromide, cuprous iodide, cuprous cyanide, cuprous oxide, cuprous perchlorate and the like. A tristriphenylphosphine complex of divalent ruthenium chloride (RuCl ₂ (PPh ₃ ) ₃ ) is also suitable as the metal compound (B). When a ruthenium compound is used as the metal compound (B), an aluminum alkoxide is added 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).

  The nitrogen-containing compound (C) is preferably a compound having an amino group in the molecule. Examples of the nitrogen-containing compound (C) include monoamine compounds such as triethylamine and tributylamine; polyamine compounds such as tetramethylethylenediamine, pentamethyldiethylenetriamine and hexamethyltriethylenetetraamine. These may be used alone or in combination of two or more. In appropriately controlling the polymerization reaction, the nitrogen-containing compound (C) is preferably a polyamine compound, and particularly preferably pentamethyldiethylenetriamine.

  The amount of the nitrogen-containing compound (C) in the atom transfer radical polymerization reaction system of the radical polymerizable monomer in the present invention is 10 times or more in molar ratio with respect to the metal compound (B). To do. When the amount of the nitrogen-containing compound (C) in the polymerization reaction system is less than 10 times (molar ratio) with respect to the metal compound (B), the polymerization activity per unit time and per unit metal becomes extremely low. Therefore, it is necessary to increase the amount of the metal compound (B) in the polymerization reaction system. As a result, the resulting polymer contains a large amount of metal residue, and the deashing / washing step after polymerization becomes complicated. Moreover, since it is difficult to sufficiently remove the metal residue, the polymer tends to be colored.

  On the other hand, when there is too much quantity of the nitrogen-containing compound (C) in a polymerization system, a nitrogen-containing compound (C) will remain in the polymer obtained and will cause coloring and an odor. Therefore, the upper limit of the molar ratio of the nitrogen-containing compound (C) to the metal compound (B) in the polymerization reaction system is preferably 1000 times, more preferably 800 times, and even more preferably 640 times.

  The amount of the metal compound (B) used in the atom transfer radical polymerization reaction system according to the present invention includes the type of halogen-modified olefin polymer (A) and its halogen content; the type of radical polymerizable monomer; It is determined according to the content of the radical polymer segment contained in the polymer. In any case, in order to reduce the amount of metal residue contained in the obtained polymer and to suppress the coloring and deterioration of the polymer, it is preferable to reduce the amount used as much as possible. Specifically, the amount of transition metal contained in the metal compound (B) added as a catalyst is preferably less than 0.4 wt% with respect to the halogen-modified olefin polymer (A). More preferably, the content is less than 1 wt%.

  Examples of the radical polymerizable monomer polymerized according to the present invention include (meth) acrylic acid monomers, styrene monomers, (meth) acrylamide monomers, maleic monomers, maleimide monomers. 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.

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

  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.

  Examples of maleic monomers include maleic anhydride, maleic acid, maleic monoalkyl esters and dialkyl esters.

  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, (meth) acrylic acid monomers, styrene monomers, and (meth) acrylonitrile are preferred. 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 atom transfer radical polymerization reaction in the present invention can be carried out in a solvent, and any solvent that does not inhibit the reaction can be used. Specific examples of solvents that can be used 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 decahydro. Alicyclic hydrocarbon solvents such as naphthalene; chlorinated hydrocarbon solvents such as chlorobenzene, 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; Ether, diethyl ether, di -n- amyl ether, and the like ether solvents such as tetrahydrofuran and dioxy anisole. Further, suspension polymerization or emulsion polymerization can be performed 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 is not limited as long as the radical polymerization reaction proceeds, and is set according to the desired degree of polymerization of the polymer, the type and amount of the radical polymerization initiator and solvent to be used. Although it is not uniform, it is -100 degreeC-250 degreeC normally, Preferably it is -50 degreeC-180 degreeC, More preferably, it is 0 degreeC-160 degreeC. In some cases, the reaction can be performed under reduced pressure, normal pressure, or increased pressure. The polymerization reaction is preferably performed in an inert gas atmosphere such as nitrogen or argon.

  Arbitrary order can be selected as an addition order of each component in radical polymerization of the present invention. As a preferred example, the halogen-modified olefin polymer (A) is dissolved or suspended in a solvent and / or a radical polymerizable monomer, and then the metal compound (B) and the nitrogen-containing compound (C) are added. And a method of starting the polymerization at a predetermined polymerization temperature. However, depending on the type and properties of the polymer (A), the metal compound (B), the nitrogen-containing compound (C), and the radical polymerizable monomer, the order may be changed or a part of the polymer may be premixed in advance. It can also be used.

  The polymer in which the olefin polymer segment and the radical polymer segment obtained by the production method of the present invention are chemically bonded can be purified and isolated. For example, it can be purified and isolated using a known method such as a solvent used in the polymerization reaction, distillation of unreacted monomers, 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 for measurement 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

(iii) Analysis of halogen content The sample was precisely weighed in a quartz sample boat and burned and decomposed at 900 ° C. in an Ar / O ₂ stream. The generated gas was absorbed into the absorbing solution and the volume was adjusted with pure water. The amount of halogen contained in this test solution was quantified by ion chromatography.
Ion chromatograph: DX-500 (Dionex)
Column: IonPacAS12A (manufactured by Dionex)

(Iv) Cu content analysis After the sample was wet-decomposed, the sample was made up to a constant volume, and quantitative analysis of Cu was performed by ICP emission spectrometry.
ICP emission spectroscopic analyzer: VISTA-PRO (manufactured by SII)

[Example 1]
(1) Synthesis of halogen-modified polypropylene (PP) 75 g of polypropylene (PP) (S119 manufactured by Prime Polymer Co., Ltd.) and 1.5 L of chlorobenzene were placed in a 2 L glass reactor sufficiently purged with nitrogen and stirred at 120 ° C. Was bubbled with nitrogen for 2 hours. Thereafter, 1.9 g of N-bromosuccinimide was added, and the mixture was heated and stirred at 100 ° C. for 2 hours. The reaction solution was cooled and the precipitated solid was filtered through a glass filter, washed with acetone, and then dried under reduced pressure to obtain 74 g of white modified polypropylene powder.

  The content of bromine atoms contained in the obtained polymer was 0.43 wt% from ion chromatography analysis. Moreover, when the molecular weight (PP conversion) of this polymer was measured by GPC, it was Mw = 104,000, Mn = 41,400, Mw / Mn = 2.5.

(2) Styrene / acrylonitrile copolymer Into a glass reactor having an internal volume of 500 mL that has been sufficiently purged with nitrogen, 15 g of the halogen-modified polypropylene obtained in (1) above, 160 mL of styrene (St), and 40 mL of acrylonitrile (AN) are added and stirred. Nitrogen bubbling was performed at room temperature for 2 hours. To this slurry, 4.0 mg of copper (I) bromide and 0.058 mL of N, N, N ′, N ″, N ″ -pentamethyldiethylenetriamine (PMDETA) were added, followed by heating to 95 ° C. Time polymerization was performed. During the polymerization, the reaction solution was not colored and was in a white slurry state. After cooling, the slurry obtained by adding 100 mL of methanol was filtered through a glass filter, and the white polymer on the filter was dried as it was under reduced pressure to obtain 19.3 g of a white polymer.

^{From the 1} H-NMR analysis, the obtained polymer contained a PP component and a styrene / acrylonitrile copolymer (AS) component, and the composition ratio was PP / AS = 88/22 (wt%). It was. Moreover, Cu content in the obtained polymer was 5 ppm or less from the ICP emission analysis. The results are shown in Table 1.

[Examples 2 to 12]
Copolymerization of styrene and acrylonitrile was carried out in the same manner as in Example 1 except that the amount of PMDETA and monomers charged, the polymerization temperature, and the polymerization time were changed as shown in Table 1. In all examples, there was no coloration during polymerization, and the polymer after filtration through a glass filter was also white. Moreover, all the Cu contents in the obtained polymer were 5 ppm or less. The results are shown in Table 1.

[Comparative Examples 1-3]
Copolymerization of styrene and acrylonitrile was carried out in the same manner as in Example 1 except that copper bromide (I), PMDETA, monomer charge, polymerization temperature, and polymerization time were changed as shown in Table 1. At any level, the slurry during polymerization was colored from dark green to yellow brown, and the polymer after filtration through a glass filter was also colored blue.

  In Comparative Example 3, the Cu content contained in the brown polymer obtained by drying the polymer immediately after filtration under reduced pressure was 580 ppm. In the white polymer obtained by washing once with 400 mL of methanol after filtration and drying under reduced pressure. The Cu content contained in was 38 ppm. Even when the polymer was washed three times and four times with 400 mL of methanol, the Cu content was 23 ppm and 22 ppm, and the Cu content did not decrease even after repeated washing. The results are shown in Table 1.

[Comparative Examples 4 to 6]
Styrene and acrylonitrile were copolymerized in the same manner as in Example 1 except that the amount of PMDETA was changed. There was no coloring during polymerization, and the polymer after filtration through a glass filter was also white. ^{From 1} H NMR analysis, it was found that the obtained polymer contained almost no AS, and the polymerization hardly proceeded. The results are shown in Table 1.

[Example 13]
Into a glass reactor having an internal volume of 500 mL sufficiently purged with nitrogen, 15 g of the halogen-modified polypropylene obtained in Example 1 (1), 39 mL of methyl methacrylate (MMA), and 112 mL of toluene were placed, and nitrogen bubbling was performed at room temperature for 2 hours with stirring. Went. To this slurry, 4.0 mg of copper (I) bromide and 0.92 mL of PMDETA were added, followed by polymerization at 80 ° C. for 3 hours. During the polymerization, the reaction solution was not colored and was in a white slurry state. After cooling, the slurry obtained by adding 100 mL of methanol was filtered through a glass filter, and the white polymer on the filter was dried as it was under reduced pressure to obtain 16.0 g of a white polymer.

^{From the 1} H-NMR analysis, the obtained polymer contained a PP component and a PMMA component, and the composition ratio was PP / PMMA = 93/7 (wt%). Moreover, Cu content in the obtained polymer was 5 ppm or less from the ICP emission analysis. The results are shown in Table 2.

[Examples 14 to 17]
MMA was polymerized in the same manner as in Example 13 except that the amount of PMDETA and the polymerization temperature were changed. There was no coloring during polymerization, and the polymer after filtration through a glass filter was also white. Moreover, all the Cu contents in the obtained polymer were 5 ppm or less. The results are shown in Table 2.

[Example 18]
(1) Synthesis of halogen-modified ethylene / propylene copolymer (EPR) In a glass reactor having an internal volume of 2 L sufficiently substituted with nitrogen, 100 g of EPR (ethylene content = 80 mol%, [η] = 0.99) and chlorobenzene 2000 ml was added and stirred with heating at 100 ° C. for 2 hours. Thereafter, 4 g of N-bromosuccinimide was added, and the reaction was performed in a solution state at 100 ° C. for 2 hours. The reaction solution was poured into 4 L of acetone, and the precipitated polymer was dried under reduced pressure to obtain 101.1 g of a brown rubber-like modified EPR.

  The content of bromine atoms contained in the obtained polymer was 0.55 wt% from ion chromatography analysis. Moreover, when the molecular weight (EPR conversion) of this polymer was measured by GPC, it was Mw = 68,200, Mn = 33,100, Mw / Mn = 2.06.

(2) Polymerization of dodecyl methacrylate Into a glass reactor having an internal volume of 500 mL sufficiently purged with nitrogen, the halogen-modified EPR (15 g) obtained in (1) above, 200 mL of ethylbenzene and 90 mL of dodecyl methacrylate were placed, and stirred for 2 hours at room temperature. Nitrogen bubbling was performed. To this slurry, 4.3 mg of copper (I) bromide and 1.0 mL of PMDETA were added, and then heated to 110 ° C. for polymerization for 4 hours. After cooling, the reaction solution was poured into 2 L of methanol and stirred, and the precipitated white polymer was directly dried under reduced pressure to obtain 21.0 g of a white rubbery polymer.

By ¹ H-NMR analysis, in the resulting polymers are included EPR component and poly dodecyl methacrylate (PDMA) component, the composition ratio was EPR / PDMA = 70/30 ( wt%). Moreover, Cu content in the obtained polymer was 5 ppm or less from the ICP emission analysis.

  According to the present invention, a polymer in which a metal residue derived from a polymerization catalyst is small and an uncolored olefin polymer segment and a radical polymer segment are chemically bonded can be obtained. Furthermore, according to the present invention, the amount of catalyst used can be greatly reduced, and the post-treatment step after polymerization is simplified, which is very useful in terms of production cost.

Claims (6)

A method for producing a polymer in which an olefin polymer segment and a radical polymer segment are chemically bonded,
Radical polymerizability in the presence of a halogen-modified olefin polymer (A), a metal compound (B) containing a transition metal element selected from Groups 3 to 11 of the periodic table, and a nitrogen-containing compound (C). Including the step of polymerizing the monomer,
The method for producing a polymer, wherein the molar ratio of the nitrogen-containing compound (C) to the metal compound (B) is 10 or more. The halogen-modified olefin polymer (A) is a halide of olefin polymer selected from the group consisting of the following (A1) ~ (A5), the weight average molecular weight (standard polystyrene equivalent) 1 × 10 ³ ~ The method for producing a polymer according to claim 1, wherein the polymer content is 1 × 10 ⁷ and the halogen content is in the range of 0.01 to 20% by weight.
(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—CxH _{2X + 1} (x is 0 or a positive integer) and a monoolefin compound having an aromatic ring.
(A3): A copolymer of an α-olefin compound represented by CH ₂ ═CH—CxH _{2X + 1} (x is 0 or a positive integer) and a cyclic monoolefin compound represented by the following general formula (1).
(A4): A random copolymer of an α-olefin compound represented by CH ₂ ═CH—CxH _{2X + 1} (x is 0 or a positive integer) and an unsaturated carboxylic acid or a derivative thereof.
(A5): A polymer obtained by modifying 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, a halogen atom and a hydrocarbon group, and R ^{15 to} R ¹⁸ may be bonded to 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 manufacturing method of the polymer as described in any one of Claims 1-3 whose said nitrogen-containing compound (C) is a compound which has an amino group in a molecule | numerator.   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 halogen-modified olefin polymer (A) is a halide of the polymer (A1), the metal compound (B) is a copper compound, and the nitrogen-containing compound (C) is pentamethyldiethylenetriamine. And the manufacturing method of the polymer as described in any one of Claims 2-5 whose molar ratio of the said nitrogen-containing compound (C) with respect to the said metal compound (B) exists in the range of 10-640.