JP2004300412A - Graft polymer having polyolefin side chain-containing graft polymer as side chain - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a graft polymer having a new structure in which a polyolefin having functional group as its side chain and a graft polymer containing polyolefin side chains are combined, and to provide a method for producing the same. <P>SOLUTION: This graft polymer contains structural units (A) expressed by general formula (I) (R<SP>1</SP>is a 1-20C hydrocarbon group, H or a halogen) and structural units (B) expressed by general formula (II) (R<SP>2</SP>is a 1-20C hydrocarbon group; X is a hetero atom or a hetero atom-containing group; and Y is a graft polymer having a polyolefin chain as its side chain). <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a graft polymer having a polyolefin side chain-containing graft polymer chain in a side chain.

Polyolefins such as polyethylene (PE) and polypropylene (PP) are lightweight and inexpensive and have excellent physical properties and workability, but they also have printability, paintability, heat resistance, impact resistance and other properties. From the viewpoint of imparting high functionality such as compatibility with a polar polymer, high chemical stability is hindered.
As a method of compensating for this defect and giving the polyolefin functionality, for example, a method of copolymerizing an olefin with a polar monomer such as vinyl acetate or methacrylic acid ester by a radical polymerization method, or a method of adding a maleic anhydride to a polyolefin in the presence of peroxide A method of grafting a polar monomer such as an acid is known. However, it is difficult to precisely control the structure of the polyolefin portion in the obtained polymer by these methods, and it is insufficient to maintain the original excellent physical properties of the polyolefin.

One form of a polymer structure having a polyolefin moiety whose structure is precisely controlled and having a function that cannot be expressed only by polyolefin is a graft polymer in which a polyolefin segment has a plurality of polar polymer segments as side chains. . As an example of the production of such a graft polymer, for example, WO 98/02472 discloses that a radical polymerization active species is formed by oxidizing polyethylene or polypropylene having an organic boron compound as a side chain, followed by radical polymerization. Discloses a method for producing a graft polymer in which a polar polymer such as polymethyl methacrylate or polystyrene exists as a side chain. However, since the graft polymer thus obtained has only one type of polyolefin segment as the main chain, it can be used as a compatibilizer for one type of polyolefin and a polar polymer, for example. As a compatibilizer or modifier for a mixed system of a plurality of polyolefins and a polar polymer, there is a drawback that the polyolefins cannot be used because of their poor compatibilizing ability, and the content and physical properties of the polyolefin segment in the graft polymer Is also difficult to control.
WO98 / 02472

  In view of this situation, the present inventors have conducted intensive studies and as a result, a graft polymer having a novel structure in which a polyolefin having a functional group in a side chain is bonded to a graft polymer having a polyolefin side chain, and a method for producing the same. Invented. Since the graft polymer of the present invention has a plurality of polyolefin segments in the molecule, a sufficient compatibilizing ability and modifying ability can be expected even in a mixed system of a polyolefin and a polar polymer which are not compatible with each other, and As a method for controlling the content and the physical properties of the polyolefin segment, the content and the physical properties of the polyolefin side chain can be controlled, so that the present invention can be applied to a field having higher versatility.

  The graft polymer according to the present invention is characterized by containing a structural unit (A) represented by the following general formula (I) and a structural unit (B) represented by the following general formula (II).

[In formulas (I) and (II), R ¹ is a group or atom selected from a hydrocarbon group having 1 to 20 carbon atoms, a hydrogen atom and a halogen atom, and R ² is a group having 1 to 20 carbon atoms. X is a hetero atom or a group containing a hetero atom, and Y is a graft polymer having a polyolefin chain in a side chain. ]

  According to the method of the present invention, a novel graft polymer having a polyolefin side chain-containing graft polymer chain in the side chain can be efficiently obtained.

  The graft polymer according to the present invention is characterized by containing a structural unit (A) represented by the following general formula (I) and a structural unit (B) represented by the following general formula (II).

  The hetero atom represented by X or a group containing a hetero atom is specifically a group containing a group selected from an ester group, an ether group, and an amide group. Hereinafter, specific structural formulas are exemplified as X.

The graft polymer chain having a polyolefin chain represented by Y in the side chain is not particularly limited as long as the main chain is a polymer chain produced by addition polymerization and the side chain is a polyolefin chain. Specifically, poly (meth) acrylate-based polymer, polystyrene-based polymer, poly (meth) acrylamide-based polymer, poly (meth) acrylonitrile-based polymer, poly (meth) acrylic-acid-based polymer and the like are used, and the side chain is CH ₂ ＣＨCHR. ⁵ (R ⁵ is a polymer chain obtained by homopolymerizing or copolymerizing an olefin represented by the formula (1), wherein R ⁵ is a group or atom selected from a hydrocarbon group having 1 to 20 carbon atoms, a hydrogen atom and a halogen atom. Is polyethylene, polypropylene, polybutene, poly (4-methyl-1-pentene), polyhexene, etc. α-olefin homopolymer, ethylene-propylene copolymer, ethylene-butene copolymer, ethylene-hexene copolymer, ethylene-based copolymer such as ethylene-octene copolymer, propylene-butene copolymer, Propylene copolymer such as propylene-hexene copolymer and propylene-octene copolymer

Hereinafter, the method for producing the graft polymer according to the present invention will be specifically described.
The graft polymer according to the present invention is produced, for example, by sequentially performing the following steps 1, 2, and 3.
(Step 1) Synthesize a functional group-containing olefin polymer containing at least one functional group selected from a group containing a Group 13 element, a hydroxyl group, an amino group, an epoxy group, a carboxyl group, an acid halogen group, and an acid anhydride group. Process.
(Step 2) A step of converting a functional group contained in the olefin polymer obtained in the above step 1 into a group having a radical polymerization or anion polymerization initiation ability.
(Step 3) A macromonomer having a polyolefin chain represented by the following general formula (III), using the olefin polymer having a group capable of initiating radical polymerization or anionic polymerization obtained in Step 2 as a polymerization initiator. (C1) a macromonomer (C2) having a polyolefin chain represented by the following general formula (IV) and a macromonomer (C3) having a polyolefin chain represented by the following general formula (V)

[In the formulas (III), (IV), and (V), R ³ is a hydrogen atom or a methyl group, Z is a hetero atom or a group containing a hetero atom, and P ¹ is CH ₂ ＣＨCHR ⁴ (R ⁴ is a carbon atom.) A polymer chain obtained by homopolymerizing or copolymerizing an olefin represented by a hydrocarbon group having 1 to 20 atoms, a group or atom selected from a hydrogen atom or a halogen atom). ]
Or a copolymer of two or more macromonomers selected from the group consisting of (C1), (C2) and (C3), and at least one carbon-carbon unsaturated bond. A step of producing a graft polymer by copolymerizing one or more monomers (D) selected from organic compounds having the same.

  Hereinafter, preferred examples of the method for producing the graft polymer of the present invention for each step will be described.

  Step 1 comprises producing an olefin polymer (E) having at least one functional group selected from a group containing a Group 13 element, a hydroxyl group, an amino group, an epoxy group, a carboxyl group, an acid halogen group, and an acid anhydride group. This is the step of doing.

The olefin polymer having a functional group (E) is obtained by copolymerizing an olefin represented by CH ₂ ＣＨCHR ⁶ with an olefin having a functional group using a known olefin polymerization catalyst such as a Ziegler-Natta catalyst or a metallocene catalyst. It is possible to manufacture by. R ⁶ is a group or atom selected from a hydrocarbon group having 1 to 20 carbon atoms, a hydrogen atom and a halogen atom.

Specific examples of such an olefin represented by CH ₂ ＣＨCHR ⁶ include ethylene, propylene, butene, pentene, hexene, octene, and decene.

Examples of olefins having a functional group used for copolymerization include allyl alcohol, 4-penten-1-ol, 5-hexen-1-ol, 6-hepten-1-ol, 8-nonen-1-ol, Unsaturated hydrocarbons in which the hydrocarbon moiety is linear, such as -undecen-1-ol, unsaturated acids such as 5-hexenoic acid, 6-heptenoic acid, 7-octenoic acid, 8-nonenoic acid, and 9-decenoic acid; Examples of the carboxylic acids, unsaturated amines such as allylamine, 5-hexenamine and 6-hepteneamine, (2,7-octadienyl) succinic anhydride, pentapropenylsuccinic anhydride and the compounds in the unsaturated carboxylic acids , An unsaturated acid anhydride such as a compound in which a carboxylic acid group is replaced with a carboxylic acid anhydride group, and a compound in the above unsaturated carboxylic acid. 2, unsaturated carboxylic acid halides such as compounds in which a carboxylic acid group is replaced with a carboxylic acid halide group, 4-epoxy-1-butene, 5-epoxy-1-pentene, 6-epoxy-1-hexene, 7- Unsaturated epoxy compounds such as epoxy-1-heptene, 8-epoxy-1-octene, 9-epoxy-1-nonene, 10-epoxy-1-decene, 11-epoxy-1-undecene, 9-allyl-9 -Borabicyclo [3.3.1] nonane, 9-but-3-enyl-9-borabicyclo [3.3.1] nonane, 9-pent-4-enyl-9-borabicyclo [3.3.1] nonane , 9-hex-5-enyl-9-borabicyclo [3.3.1] nonane, 9-hepta-6-enyl-9-borabicyclo [3.3.1] nonane, 9-oct-7-e Le-9-borabicyclo [3.3.1] nonane, 9-nona-8-enyl-9-borabicyclo [3.3.1] nonane, 9-dec-9-enyl-9-borabicyclo [3.3. 1] unsaturated boron compounds such as nonane;

  Step 2 is a step of converting the functional group in the functional group-containing olefin polymer (E) obtained in Step 1 into a group having an ability to initiate radical polymerization or anionic polymerization. Examples of the group having a radical polymerization initiating ability include, as disclosed in Chem. Rev., 101, 3661 (2001), a group having a nitroxide-containing group, which generates a radical by thermal cleavage, As disclosed in Chem. Rev., 101, 2921 (2001) and Chem. Rev., 101, 3689 (2001), a group having a terminal halogen atom is bonded, and ruthenium or copper chloride or And the like which generate a radical by adding a complex having a transition metal atom.

  As a method for converting the terminal functional group contained in the olefin polymer (E) having the above functional group into a group having the above radical polymerization initiating ability, a group having a radical polymerization initiating ability and an olefin polymer having the above functional group can be used. A method of reacting the compound (F) having both a functional group and a functional group capable of reacting with the functional group contained in (E) with the olefin polymer (E) having the above functional group is exemplified.

  Specific examples of the compound (F) having both a group capable of initiating radical polymerization and a functional group capable of reacting with the functional group contained in the olefin polymer (E) having the above functional group include, for example, those shown in the following figure. Compounds can be exemplified.

  In addition to the conversion method by reaction with the compound (F), the compound is converted into a functional group having a radical polymerization initiating ability by a method disclosed in, for example, Prog. Polym. Sci., 27, 39 (2002). You can also. That is, by oxidizing an olefin polymer having a group containing a Group 13 element, an oxygen-oxygen bond having radical polymerization initiation ability can be introduced between the Group 13 element and a carbon atom. The oxygen-oxygen bond thus obtained is thermally homocleaved and functions as a radical polymerization initiator.

As a method for converting the functional group of the olefin polymer having a functional group (E) into a compound having an anionic polymerization initiating ability, for example, an olefin polymer having a hydroxyl group is converted into an alkali metal such as metallic lithium or metallic potassium, hydrogen, or the like. A method of forming a metal alkoxide-containing olefin polymer by reacting with an alkali metal hydride such as lithium halide or potassium hydride, or an alkyl aluminum compound such as trimethylaluminum, triethylaluminum, triisobutylaluminum, or trihexylaluminum. No.
The function contained in the olefin polymer (E) having the functional group when the functional group contained in the olefin polymer (E) having the functional group is converted into a group capable of initiating radical polymerization or anionic polymerization. When the amount of the compound (F) having both the group having the radical polymerization initiating ability with respect to the group and the functional group capable of reacting with the functional group contained in the olefin polymer (E) having the functional group is too small, the amount used is too small. Since the conversion rate of the functional group contained in the olefin polymer (E) having a functional group is low, the yield of the graft polymer obtained in the step 3 is reduced. If the amount is too large, the unreacted compound (F) remains. In step 3, a homopolymer may be by-produced. Therefore, the amount of the compound (F) to be used is generally 0.1 to 100 times, preferably 0.3 to 50 times, the molar amount of the functional group contained in the olefin polymer (E) having the functional group. Mol, more preferably 0.5 to 10 times mol.

  As the reaction solvent, for example, aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, tetradecane, cycloaliphatic hydrocarbons such as cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, cyclooctane, cyclohexene , Aromatic hydrocarbons such as benzene, toluene, xylene, halogenated hydrocarbons such as dichloromethane, chloroform, dichloroethane, dichloropropane, trichloroethylene, chlorobenzene, dichlorobenzene, 2,4-dichlorotoluene, methyl acetate, and ethyl acetate , Esters such as butyl acetate, ketones such as acetone and methyl ethyl ketone, dioxane, tetrahydrofuran, acetonitrile, dimethylformamide, dimethyl sulfoxide and the like. . These may be used alone or in combination of two or more.

  In the reaction between the olefin polymer (E) having the functional group and the compound (F), the reaction is performed in the presence of a condensing agent or a basic catalyst, depending on the type of the functional group involved in the reaction. Is preferred.

  Examples of the condensing agent include inorganic dehydrating condensing agents such as concentrated sulfuric acid, diphosphorus pentoxide, and anhydrous zinc chloride; carbodiimides such as dicyclohexylcarbodiimide, diisopropylcarbodiimide, and 1-ethyl-3- (3-dimethylaminopropylcarbodiimide) hydrochloride; , Polyphosphoric acid, acetic anhydride, carbonyldiimidazole, p-toluenesulfonyl chloride and the like.

  Specific examples of the basic catalyst include, for example, triethylamine, diisopropylethylamine, N, N-dimethylaniline, piperidine, pyridine, 4-dimethylaminopyridine, 1,5-diazabicyclo [4,3,0] non-5- Organic amines such as ene, 1,8-diazabicyclo [5,4,0] undec-7-ene, tri-n-butylamine and N-methylmorpholine; alkali metal compounds such as sodium hydride and n-butyllithium And the like.

  The reaction temperature is generally -100 to 200C, preferably -50 to 150C. The reaction time varies depending on the reaction temperature and the type and amount of the compound (F) to be used and the olefin polymer (E) having the above functional group, but is usually 1 to 48 hours.

  In the case where the olefin polymer (E) having a functional group has a carboxyl group as a functional group, it is first reacted with, for example, phosphorus pentachloride or thionyl chloride to form an acid chloride compound. And F) in a suitable solvent in the presence of a base.

  Step 3 comprises using the olefin polymer having a functional group capable of initiating radical polymerization or anion polymerization obtained in Steps 1 and 2 above as a macroinitiator and having a polyolefin chain represented by the following general formula (III). Macromonomer (C1), macromonomer (C2) having a polyolefin chain represented by the following general formula (IV), and macromonomer (C3) having a polyolefin chain represented by the following general formula (V)

[In the formulas (III), (IV) and (V), R ³ is a hydrogen atom or a methyl group, Z is a hetero atom or a group containing a hetero atom, and P ¹ is CH ₂ ＣＨCHR ³ (R ³ is a carbon atom. A polymer chain obtained by homopolymerizing or copolymerizing an olefin represented by a hydrocarbon group having 1 to 20 atoms, a group or atom selected from a hydrogen atom or a halogen atom). ]
Or a copolymer of two or more macromonomers selected from (C1), (C2) and (C3), and at least one carbon-carbon unsaturated bond. By grafting one or more monomers (D) selected from organic compounds having one or more organic compounds, a graft polymer chain is formed on the olefin polymer having a functional group capable of initiating radical polymerization or anionic polymerization obtained in the above step 2. This is the step of providing.

Polyolefin macromonomers used in this process (C1), (C2) and of (C3), polyolefin macromonomer (C1) having a styryl group at the terminal of the polyolefin chain P ¹ represented by the general formula (III) , The following general formula (VI)

[In the formula (V), W is a group containing an atom or a functional group selected from a halogen atom, a hydroxyl group, a carboxyl group, an acid halogen group, an epoxy group, an amino group, and an isocyanate group. ]
And a styrene derivative represented by the following general formula (VII)

[In the formula (VII), P ¹ is the same as the formula (III), and V is a functional group selected from a hydroxyl group, an amino group, an epoxy group, a carboxyl group, an acid halogen group, and an acid anhydride group. And a functional group-containing polyolefin represented by the following formula:

Specific examples of the styrene derivative represented by the general formula (VII) include, for example, m-chlorostyrene, p-chlorostyrene, m-bromostyrene, p-bromostyrene, m-iodostyrene, p-iodostyrene, and m-chlorostyrene. Chloromethylstyrene, p-chloromethylstyrene, m-bromomethylstyrene, p-bromomethylstyrene, m-iodomethylstyrene, p-iodomethylstyrene, p- (2-chloroethyl) styrene, p- (2-bromoethyl) Styrene, p- (3-chloropropyl) styrene, p- (3-bromopropyl) styrene, p- (4-chlorobutyl) styrene, p- (4-bromobutyl) styrene, p- (5-chloropentyl) styrene, p- (5-bromopentyl) styrene, p- (6-chlorohexyl) styrene, p- (6- Halogen-containing styrenes such as lomohexyl) styrene, m-hydroxystyrene, p-hydroxystyrene, m-hydroxymethylstyrene, p-hydroxymethylstyrene, p- (2-hydroxyethyl) styrene, p- (3-hydroxypropyl) Hydroxyl-containing styrenes such as styrene and p- (4-hydroxybutyl) styrene, 3-vinylbenzoic acid, 4-vinylbenzoic acid, (3-vinylphenyl) acetic acid, (4-vinylphenyl) acetic acid, 3- (4 Carboxyl group-containing styrenes such as -vinylphenyl) propionic acid, 4- (4-vinylphenyl) butanoic acid, 5- (4-vinylphenyl) pentanoic acid and 6- (4-vinylphenyl) hexanoic acid, 3-vinyl Benzoic acid chloride, 4-vinylbenzoic acid chloride, 3-vinylbenzoic acid bromide , 4-vinylbenzoic acid bromide, 3-vinylbenzoic acid iodide, 4-vinylbenzoic acid iodide, (3-vinylphenyl) acetic acid chloride, (4-vinylphenyl) acetic acid chloride, 3- (4-vinylphenyl) propionic acid Styrenes containing acid halide groups such as chloride, 4- (4-vinylphenyl) butanoic acid chloride, 5- (4-vinylphenyl) pentanoic acid chloride, 6- (4-vinylphenyl) hexanoic acid chloride, 3-vinyl Aniline, 4-vinylaniline, 3-vinylbenzylamine, 4-vinylbenzylamine, 2- (4-vinylphenyl) ethylamine, 3- (4-vinylphenyl) propylamine, 4- (4-vinylphenyl) butylamine, Amino-containing styrenes such as 5- (4-vinylphenyl) pentylamine; Epoxy group-containing styrenes such as sidyl- (3-vinylbenzyl) ether and glycidyl- (4-vinylbenzyl) ether, 3-isocyanatostyrene, 4-isocyanatostyrene, 3-isocyanatomethylstyrene, 4-isocyanate Isocyanate group-containing styrenes such as methylstyrene, 4- (2-isocyanatoethyl) styrene, 4- (3-isocyanatopropyl) styrene, and 4- (4-isocyanatobutyl) styrene.

  The functional group-containing polyolefin represented by the general formula (VII) can be obtained, for example, by producing a) a polyolefin having a group containing a group 13 element, and then forming a polyolefin containing a group 13 element and a compound having a functional group structure. Solvolysis after the substitution reaction, or b) solvolysis after the substitution reaction with a compound having a structure capable of forming a functional group by solvolysis of a group containing a group 13 element of the polyolefin. It can be produced by decomposition, but the present invention is not limited to these methods at all. Hereinafter, the above manufacturing method will be described in detail.

Production of Polyolefin Having Group Containing Group 13 Element The production method of polyolefin having group 13 element-containing group includes (a) a method of polymerizing olefin with a known polymerization catalyst in the presence of a compound containing a group 13 element; ) A method of producing a polyolefin having an unsaturated bond at a terminal by a reaction with a compound containing a Group 13 element. Hereinafter, each will be described.

[(A) Olefin polymerization in the presence of a compound containing a group 13 element]
The polyolefin having a group containing a group 13 element can be obtained by homopolymerizing an olefin represented by CH ₂ ＣＨCHR ⁷ in the presence of a compound containing a group 13 element using a known olefin polymerization catalyst such as a Ziegler-Natta catalyst or a metallocene catalyst. Alternatively, it is produced by copolymerization. R ⁷ is a group or atom selected from a hydrocarbon group having 1 to 20 carbon atoms, a hydrogen atom and a halogen atom.

Specific examples of such an olefin represented by CH ₂ ＣＨCHR ⁷ include ethylene, propylene, butene, pentene, hexene, octene, and decene.

  Examples of the compound containing a Group 13 element include an organic aluminum compound and an organic boron compound.

  Examples of the organoaluminum compound include an organoaluminum compound represented by the following formula (VIII).

^{_{R a n AlA 3-n ··}} ... (VIII)
[In the formula (VIII), ^Ra is a hydrocarbon group having 1 to 12 carbon atoms, A is halogen or hydrogen, and n is 1 to 3. ]
^Ra is a hydrocarbon group having 1 to 12 carbon atoms, for example, an alkyl group, a cycloalkyl group or an aryl group, specifically, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an isobutyl group. Pentyl, hexyl, octyl, cyclopentyl, cyclohexyl, phenyl and tolyl groups.

Specific examples of such an organoaluminum compound include trialkylaluminums such as trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, trioctylaluminum, and tri-2-ethylhexylaluminum; and trialkenylaluminums such as triisoprenylaluminum. A dialkylaluminum halide such as dimethylaluminum chloride, diethylaluminum chloride, diisopropylaluminum chloride, diisobutylaluminum chloride, dimethylaluminum bromide, methylaluminum sesquichloride, ethylaluminum sesquichloride, isopropylaluminum sesquichloride, butylaluminum sesquichloride, ethylaluminum chloride Alkyl aluminum sesquihalides such as kibromide; alkyl aluminum dihalides such as methyl aluminum dichloride, ethyl aluminum dichloride, isopropyl aluminum dichloride, and ethyl aluminum dibromide; alkyl aluminum hydrides such as diethyl aluminum hydride, diisobutyl aluminum hydride, and ethyl aluminum dihydride. No.

  Further, as the organoaluminum compound, a compound represented by the following formula (IX) can also be used.

^{_{R a n AlB 3-n ··}} ... (IX)
In the above formula (IX), R ^a is as defined above, B is -OR ^b group, -OSiR ^c ₃ group, -OAlR ^d ₂ group, -NR ^e ₂ group, -SiR ^f ₃ group or -N ( R ^g) is AlR ^h ₂ group, n is ^{1~2, R b, R c,} R d and R ^h are each methyl, ethyl, isopropyl, isobutyl, cyclohexyl group, a phenyl group , ^Re are hydrogen, methyl, ethyl, isopropyl, phenyl, trimethylsilyl, etc., and ^Rf and ^Rg are methyl, ethyl, etc.

Specific examples of such an organic aluminum compound include the following compounds.
(I) compounds represented by R ^a _n Al (OR ^b ) _3-n , for example, dimethyl aluminum methoxide, diethyl aluminum ethoxide, diisobutyl aluminum methoxide and the like; (ii) R ^a _n Al (OSiR ^c ) ₃ compounds represented by _-n , for example, Et ₂ Al (OSiMe ₃ ), (iso-Bu) ₂ Al (OSiMe ₃ ), (iso-Bu) ₂ Al (OSiEt ₃ ), and (iii) R ^a _n Al (OAlR ^d ₂₎ a compound represented by _{3-n, e.g., Et 2 AlOAlEt 2, (iso} -Bu) 2 AlOAl etc. _{(iso-Bu) 2, (} iv) R a n Al (NR e 2) 3- a compound represented by _n , for example, Me ₂ AlNEt ₂ , Et ₂ AlNHMe, Me ₂ AlNHEt, Et ₂ AlN (Me ₃ Si) ₂ , (iso-Bu) ₂ AlN (Me ₃ Si) _2, etc. _{^{R a n Al (SiR f 3}} ) a compound represented by _3-n, e.g., (iso-Bu) ₂ AlSiMe Such as _{^{3, (vi) R a n}} Al [N (R ^g) -AlR ^h _2] A compound represented by _{3-n, e.g., Et 2 AlN (Me) -AlEt} 2, (iso-Bu) 2 AlN ( Et) Al (iso-Bu) _{2 and the} like.

Further, there may be mentioned a compound similar to this, for example, an organic aluminum compound in which two or more aluminum atoms are bonded via an oxygen atom or a nitrogen atom. More specifically, (C ₂ H ₅ ) ₂ AlOAl (C ₂ H ₅ ) ₂ , (C ₄ H ₉ ) ₂ AlOAl (C ₄ H ₉ ) ₂ , (C ₂ H ₅ ) ₂ AlN (C ₂ H ₅ ) Al (C ₂ H ₅ ) ₂ and the like, and aluminoxanes such as methylaluminoxane (organoaluminumoxy compounds).

  Further, an organoaluminum compound represented by the following formula (X) can also be used.

R ^a _n AlAB ・ ・… (X)
[R ^a , A and B are the same as those in the above formula (VIII) or (IX). ]
As the compound containing a Group 13 element, an organic boron compound can also be used. Examples of the organic boron compound include triphenylboron, tris (4-fluorophenyl) boron, tris (3,5-difluorophenyl) boron, tris (4-fluoromethylphenyl) boron, tris (pentafluorophenyl) boron, tris ( p-tolyl) boron, tris (o-tolyl) boron, tris (3,5-dimethylphenyl) boron, texylborane, dicyclohexylborane, disiamylborane, diisopinocanphenylborane, 9-borabicyclo [3.3.1] nonane, catechol Examples include borane, B-bromo-9-borabicyclo [3.3.1] nonane, borane-triethylamine complex, and borane-methylsulfide complex.

Further, an ionic compound may be used as the organic boron compound. Such compounds include triethylammonium tetra (phenyl) boron, tripropylammonium tetra (phenyl) boron, trimethylammonium tetra (p-tolyl) boron, trimethylammonium tetra (o-tolyl) boron, tri (n-butyl) Ammonium tetra (pentafluorophenyl) boron, tripropylammonium tetra (o, p-dimethylphenyl) boron, tri (n-butyl) ammonium tetra (p-trifluoromethylphenyl) boron, N, N-dimethylaniliniumtetra ( Phenyl) boron, dicyclohexylammonium tetra (phenyl) boron, triphenylcarbeniumtetrakis (pentafluorophenyl) borate, N, N-dimethylaniliniumtetrakis (pentafluorophenyl)
Borate, bis [tri (n-butyl) ammonium] nonaborate, bis [tri (n-butyl) ammonium] decaborate, and the like.

  These compounds containing a Group 13 element may be used alone or in combination.

[(B) Method for producing from polyolefin having terminal unsaturated bond]
Further, the polyolefin having a group containing a group 13 element can also be produced using a polyolefin having an unsaturated bond at a terminal. Specifically, this is a method of reacting a polyolefin having an unsaturated bond at a terminal with a compound containing a group 13 element, for example, an organic aluminum compound or an organic boron compound to obtain a polyolefin having a group containing a group 13 element. .

  A polyolefin having an unsaturated bond at one end (terminally unsaturated polyolefin) is obtained by polymerizing or copolymerizing an olefin having 2 to 20 carbon atoms in the presence of a known olefin polymerization catalyst such as a Ziegler-Natta catalyst or a metallocene catalyst. Can be manufactured. As the olefin having 2 to 20 carbon atoms, ethylene, propylene, 1-butene, 3-methyl-1-butene, 3-methyl-1-pentene, 4-methyl-1-pentene and the like are preferably used.

  The terminal unsaturated polyolefin thus obtained is reacted with a compound containing a Group 13 element to convert it into a polyolefin having a group containing a Group 13 element. If the obtained polyolefin is a mixture of one having a group 13 element bonded to one end and one having an unsaturated bond terminal at one end, if necessary, one end may have an unsaturated bond. The terminal of the terminal polyolefin may be converted to a terminal to which a group 13 element is bonded.

  As the compound containing a Group 13 element used in the reaction, an organic aluminum compound or an organic boron compound is preferably used. Among them, a trialkylaluminum, a dialkylaluminum hydride or a boron compound having at least one hydrogen-boron bond is more preferable. As the organic aluminum, a dialkylaluminum hydride is particularly preferable, and as the organic boron compound, 9-borabicyclo [3 [3,1] nonane is particularly preferred.

The reaction between a polyolefin having one terminal of an unsaturated bond and a compound containing a Group 13 element is performed, for example, as follows.
(i) A mixture of 0.1 to 50 g of polypropylene having a vinylidene group at the end and 5 to 1000 ml of a 0.01 to 5 mol / liter-octane solution of diisobutylaluminum hydride is refluxed for 0.5 to 6 hours. .
(ii) 0.1 to 50 g of polypropylene having a vinylidene group at the end, 5 to 1000 ml of anhydrous tetrahydrofuran, and 0.05 to 10 mol / of 0.1 to 50 ml of 9-borabicyclo [3.3.1] nonane. Liter-tetrahydrofuran solution and stir at 20-65 ° C for 0.5-24 hours. As described above, a polyolefin having a group containing a Group 13 element is produced.

Conversion to functional group-containing polyolefin represented by general formula (VII) The polyolefin having a group containing a Group 13 element produced in this manner is
(Method a) Substitution of a group containing a Group 13 element of the polyolefin with a compound having a functional group structure
Reaction and then solvolysis, or
(Method b) Forming a functional group by solvolysis of a group containing a Group 13 element of the polyolefin
By performing a substitution reaction with a compound having a structure, and then solvolysis,
A polio represented by the following general formula (XI) wherein V in the general formula (VII) is a hydroxyl group.
Can be converted to fins.

In the formula, P ¹ is the same as described above.

  Examples of the compound having a functional group structure used in (method a) include halogen gas, methyl chloroformate, and phthalic chloride. Examples of the compound having a structure that forms a functional group by solvolysis used in (method b) include oxygen, carbon monoxide, and carbon dioxide.

  Substitution reaction between the group 13 element-containing group of the polyolefin having a group 13 element-containing group obtained as described above and a compound having a functional group structure or a compound having a structure that forms a functional group by solvolysis Is carried out at a temperature of usually 0 to 300 ° C, preferably 10 to 200 ° C, for 0 to 100 hours, preferably 0.5 to 50 hours. After performing the substitution reaction, the temperature for solvolysis is usually 0 to 100 ° C, preferably 10 to 80 ° C, and the solvolysis time is 0 to 100 hours, preferably 0.5 to 100 ° C. 50 hours. Solvents used for solvolysis include methanol, ethanol, propanol, butanol, water and the like.

  Further, among the polyolefins having a functional group represented by the above general formula (VII), those in which V is an epoxy group include terminal-unsaturated polyolefins produced by the above method, for example, JP-A-63-305104. Also, it can be produced by epoxidizing an unsaturated bond using a method shown in, for example.

  Specifically, the terminally unsaturated polyolefin produced by the above method is reacted with a mixture of 1) an organic acid such as formic acid and acetic acid and hydrogen peroxide, or 2) a mixture of m-chloroperbenzoic acid and the like. It can be produced by reacting an organic peroxide.

  Further, among the polyolefins having a functional group represented by the general formula (VII), those in which V is an acid anhydride group include terminally unsaturated polyolefins produced by the above method, for example, Makromol. Chem. Macromol. Symp., 48/49, 317 (1991), or Polymer, 43, 6351 (2002), for example, a method of introducing an acid anhydride into a terminal by thermally reacting with maleic anhydride or the like. Can be manufactured.

  Further, among the polyolefins having a functional group represented by the above general formula (VII), those in which V is a carboxyl group are obtained by oxidizing the polyolefin having a hydroxyl group represented by the above general formula (XI) to convert the hydroxyl group into a carboxyl group. It can be manufactured by using a method of converting to.

The polyolefin having a functional group represented by the general formula (VII) can be obtained by using a known olefin polymerization catalyst such as a Ziegler-Natta catalyst or a metallocene catalyst, and an olefin represented by CH ₂ ＣＨCHR ⁸ and an olefin having a functional group. Can also be produced by copolymerizing As a method for selectively introducing a functional group-containing olefin into a terminal, for example, a method shown in J. Am. Chem. Soc., 124, 1176 (2002) can be exemplified. R ⁸ is a group or atom selected from a hydrocarbon group having 1 to 20 carbon atoms, a hydrogen atom and a halogen atom.

Specific examples of such an olefin represented by CH ₂ ＣＨCHR ⁸ include ethylene, propylene, butene, pentene, hexene, octene, and decene.
Examples of olefins having a functional group used for copolymerization include allyl alcohol, 4-penten-1-ol, 5-hexen-1-ol, 6-hepten-1-ol, 8-nonen-1-ol, Unsaturated hydrocarbons in which the hydrocarbon moiety is linear, such as -undecen-1-ol, unsaturated acids such as 5-hexenoic acid, 6-heptenoic acid, 7-octenoic acid, 8-nonenoic acid, and 9-decenoic acid; Examples of the carboxylic acids, unsaturated amines such as allylamine, 5-hexenamine and 6-hepteneamine, (2,7-octadienyl) succinic anhydride, pentapropenylsuccinic anhydride and the compounds in the unsaturated carboxylic acids , An unsaturated acid anhydride such as a compound in which a carboxylic acid group is replaced with a carboxylic acid anhydride group, and a compound in the above unsaturated carboxylic acid. 2, unsaturated carboxylic acid halides such as compounds in which a carboxylic acid group is replaced with a carboxylic acid halide group, 4-epoxy-1-butene, 5-epoxy-1-pentene, 6-epoxy-1-hexene, 7- Unsaturated epoxy compounds such as epoxy-1-heptene, 8-epoxy-1-octene, 9-epoxy-1-nonene, 10-epoxy-1-decene and 11-epoxy-1-undecene.

When producing a polyolefin macromonomer having a styryl group at the end of the polyolefin chain P ¹ represented by the general formula (III), a styrene derivative represented by the general formula (VI) and a styrene derivative represented by the general formula (VII) Examples of the combination with a polyolefin having a functional group include the following combinations, but are not particularly limited thereto.
(1) A styrene derivative in which W is a group containing a carboxyl group in the general formula (VI), and a polyolefin having a functional group at a terminal where V is a hydroxyl group in the general formula (VII).
(2) A styrene derivative in which W is a group containing a carboxyl group in the general formula (VI), and a polyolefin having a functional group at a terminal where V is an amino group in the general formula (VII).
(3) A styrene derivative in which W is a group containing a hydroxyl group in the general formula (VI), and a polyolefin having a functional group at a terminal where V is an epoxy group in the general formula (VII).
(4) A styrene derivative in which W is a group containing a hydroxyl group in the general formula (VI), and a polyolefin having a functional group at a terminal where V is a carboxyl group in the general formula (VII).
(5) A styrene derivative in which W is a group containing a hydroxyl group in the general formula (VI), and a polyolefin having a functional group at a terminal where V is an acid anhydride group in the general formula (VII).
(6) A styrene derivative in which W is a group containing a hydroxyl group in the general formula (VI), and a polyolefin having a functional group at a terminal where V is an oxyhalogen group in the general formula (VII).
(7) In the above general formula (VI), W is a styrene derivative wherein the group is a group containing an acid halogen group;
In the above general formula (VII), a polyolefin having a functional group at a terminal where V is a hydroxyl group.
(8) In the above general formula (VI), W is a styrene derivative wherein the group is a group containing an acid halogen group;
In the above general formula (VII), a polyolefin having a functional group at a terminal where V is an amino group.
(9) A styrene derivative in which W is a group containing halogen in the above general formula (VI), and a polyolefin having a functional group at a terminal where V is a hydroxyl group in the above general formula (VII).
(10) In the above general formula (VI), W is a styrene derivative in which W is a group containing an epoxy group;
In the above general formula (VII), a polyolefin having a functional group at a terminal where V is a hydroxyl group.
(11) A styrene derivative in which W is a group containing an amino group in the above general formula (VI), and a polyolefin having a functional group at a terminal where V is a carboxyl group in the above general formula (VII).
(12) A styrene derivative in which W is a group containing an amino group in the above general formula (VI), and a polyolefin having a functional group at a terminal where V is an acid halogen group in the above general formula (VII).
(13) A styrene derivative in which W is a group containing an amino group in the general formula (VI), and a polyolefin having a functional group at a terminal where V is an acid anhydride group in the general formula (VII).
(14) A styrene derivative in which W is a group containing an isocyanate group in the general formula (VI), and a polyolefin having a functional group at a terminal where V is a hydroxyl group in the general formula (VII).

  The amount of the styrene derivative represented by the above general formula (VI) relative to the polyolefin having a functional group represented by the above general formula (VII) when producing the polyolefin macromonomer having a styryl group at the terminal of the present invention is determined by the amount of the functional group Is usually 0.01 to 100 moles, preferably 0.1 to 10 moles, per mole of the polyolefin having

  As the reaction solvent, for example, aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, tetradecane, cycloaliphatic hydrocarbons such as cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, cyclooctane, cyclohexene , Aromatic hydrocarbons such as benzene, toluene, xylene, halogenated hydrocarbons such as dichloromethane, chloroform, dichloroethane, dichloropropane, trichloroethylene, chlorobenzene, dichlorobenzene, 2,4-dichlorotoluene, methyl acetate, and ethyl acetate , Esters such as butyl acetate, ketones such as acetone and methyl ethyl ketone, dioxane, tetrahydrofuran, acetonitrile, dimethylformamide, dimethyl sulfoxide and the like. . These may be used alone or in combination of two or more.

  In the reaction between the styrene derivative represented by the general formula (VI) and the polyolefin having a functional group represented by the general formula (VII), a condensing agent is added as necessary in order to efficiently advance the reaction. be able to.

  Examples of the condensing agent include inorganic dehydrating condensing agents such as concentrated sulfuric acid, diphosphorus pentoxide, and anhydrous zinc chloride; carbodiimides such as dicyclohexylcarbodiimide, diisopropylcarbodiimide, and 1-ethyl-3- (3-dimethylaminopropylcarbodiimide) hydrochloride; , Polyphosphoric acid, acetic anhydride, carbonyldiimidazole, p-toluenesulfonyl chloride and the like.

  The reaction between the styrene derivative represented by the general formula (VI) and the polyolefin having a functional group represented by the general formula (VII) is preferably performed in the presence of a basic catalyst. Specifically, for example, triethylamine, diisopropylethylamine, N, N-dimethylaniline, piperidine, pyridine, 4-dimethylaminopyridine, 1,5-diazabicyclo [4,3,0] non-5-ene, 1,8- Organic amines such as diazabicyclo [5,4,0] undec-7-ene, tri-n-butylamine and N-methylmorpholine, and alkali metals such as sodium hydride, potassium hydride, lithium hydride and n-butyllithium And the like.

  When the styrene derivative represented by the general formula (VI) and the polyolefin having a functional group represented by the general formula (VII) have a carboxyl group as a functional group, for example, phosphorus pentachloride or chloride Reaction with thionyl or the like to form an acid chloride compound, which is reacted with a corresponding polyolefin having a functional group represented by the above general formula (VII) and a styrene derivative represented by the above general formula (VI) in an appropriate solvent It can also be manufactured by performing the above.

  When the styrene derivative represented by the general formula (VI) has a group containing a halogen atom, first, a polyolefin having a functional group represented by the general formula (VII) in which V is a hydroxyl group is converted to a metal. It can also be produced by converting into an alkoxide with an alkoxide agent and reacting the alkoxide with a styrene derivative represented by the above general formula (VI) having a group containing a halogen atom in a suitable solvent. Examples of the metal alkoxide agent include metal sodium, metal potassium, sodium hydride, potassium hydride, soda amide and the like.

  The polyolefin macromonomer (C2) having an acryloyl group or a methacryloyl group at the terminal represented by the general formula (IV) is a polyolefin having a hydroxyl group at a terminal and an acrylic acid halide, a methacrylic halide, acrylic acid or methacrylic acid. It is obtained by reacting.

The polyolefin having a hydroxyl group at the terminal is produced by the same method as the polyolefin having a functional group at the terminal represented by the general formula (VII) wherein V is a hydroxyl group. The reaction between the obtained polyolefin having a hydroxyl group at the terminal and acrylic acid halide, methacrylic acid halide, acrylic acid or methacrylic acid is performed, for example, as follows.
[1] A method in which a polyolefin having a terminal hydroxyl group is reacted with an acrylic acid halide such as acrylic acid chloride or methacrylic acid chloride or a methacrylic acid halide in the presence of a base such as triethylamine.
[2] A method in which a polyolefin having a terminal hydroxyl group is reacted with acrylic acid or methacrylic acid in the presence of an acid catalyst.

  At the time of the reaction, acrylic acid halide, methacrylic acid halide, acrylic acid or methacrylic acid is used in an amount of 0.1 to 100 mol, preferably 0.2 to 50 mol, per 1 mol of the hydroxyl group at the terminal of the polyolefin. The reaction temperature is generally -100 to 150C, preferably 0 to 120C, and the reaction time is generally 0.1 to 48 hours, preferably 0.5 to 12 hours.

Among the polyolefin macromonomers used in this step, the polyolefin macromonomer (C3) having a vinyl group or a vinylidene group at the terminal represented by the general formula (V) is, for example, a known olefin such as a Ziegler-Natta catalyst or a metallocene catalyst. It can be produced by polymerizing or copolymerizing an olefin having 2 to 20 carbon atoms in the presence of a polymerization catalyst. As the olefin having 2 to 20 carbon atoms, ethylene, propylene, 1-butene, 3-methyl-1-butene, 3-methyl-1-pentene, 4-methyl-1-pentene and the like are preferably used.
Further, polyolefins obtained by polymerizing in the presence of the olefin polymerization catalyst, obtained by decomposing the polyolefin by heat or radicals, low-molecular-weight polyolefins having double bonds at some or all of the molecular terminals are also polyolefin macromonomers It can be used as (C3).

  Thus, the polyolefin macromonomers (C1), (C2) and (C3) represented by the general formulas (III), (IV) and (V) are produced.

  The graft polymer according to the present invention is obtained by subjecting the polyolefin macromonomers (C1), (C2) and (C3) to the presence of the olefin polymer having a functional group capable of initiating radical polymerization or anionic polymerization obtained in the steps 1 and 2. Or one or more selected from (C1), (C2) and (C3) at least one macromonomer selected from organic compounds having at least one carbon-carbon unsaturated bond. It is produced by copolymerizing the above monomer (D).

The monomer (D) is selected from organic compounds having at least one carbon-carbon unsaturated bond. The carbon-carbon unsaturated bond is a carbon-carbon double bond or a carbon-carbon triple bond. Examples of such organic compounds include (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and (meth) acrylate. N-butyl acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate N-heptyl (meth) acrylate, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, (meth) acrylic acid Dodecyl, phenyl (meth) acrylate, toluyl (meth) acrylate, benzyl (meth) acrylate, (meth) acrylic acid- -Methoxyethyl, 3-methoxybutyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, stearyl (meth) acrylate, glycidyl (meth) acrylate , 2-aminoethyl (meth) acrylate, γ- (methacryloyloxypropyl) trimethoxysilane, ethylene oxide adduct of (meth) acrylic acid, trifluoromethylmethyl (meth) acrylate, 2- (meth) acrylate Trifluoromethylethyl, 2-perfluoroethylethyl (meth) acrylate, 2-perfluoroethyl-2-perfluorobutylethyl (meth) acrylate, 2-perfluoroethyl (meth) acrylate, (meth) acrylic Perfluoromethyl acid, diperfluoro (meth) acrylate Methyl methyl, 2-perfluoromethyl-2-perfluoroethylmethyl (meth) acrylate, 2-perfluorohexylethyl (meth) acrylate, 2-perfluorodecylethyl (meth) acrylate, (meth) acrylic acid (Meth) acrylic monomers such as 2-perfluorohexadecylethyl, styrene monomers such as styrene, vinyltoluene, α-methylstyrene, chlorostyrene, styrenesulfonic acid and salts thereof, perfluoroethylene, perfluoropropylene, Fluorine-containing vinyl monomers such as vinylidene fluoride, silicon-containing vinyl monomers such as vinyltrimethoxysilane and vinyltriethoxysilane, maleic anhydride, maleic acid, monoalkyl and dialkyl esters of maleic acid, fumaric acid, and fumaric acid mono Alkyl ester and dialkyl ester, maleimide, methyl maleimide,
Maleimide monomers such as ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide, and cyclohexylmaleimide; vinyl monomers containing acrylonitrile and methacrylonitrile; Amide group-containing vinyl monomers such as vinyl acetate, vinyl propionate, vinyl pivalate, vinyl benzoate and vinyl cinnamate; olefin monomers such as ethylene, propylene and butene; butadiene and isoprene. Diene monomers, vinyl ether monomers such as ethyl vinyl ether and isopropyl vinyl ether, N-vinylcarbazole, indene, Butene, vinyl chloride, vinylidene chloride, allyl chloride, allyl alcohol and the like. Further, a compound having a polymerizable (meth) acryloyl group or styryl group at the terminal of a polymer obtained by polymerizing one or a plurality of these organic compounds, that is, a macromonomer can also be used as the component (D). These organic compounds may be used alone or in combination of two or more as the component (D).

The radical polymerization according to the present invention is carried out in the presence of a catalyst if necessary. Examples of such a catalyst include CuBr, CuCl, RuCl, RuCl ₂ , FeCl, and FeCl ₂ . When a catalyst is used, the amount used depends on the amount of the functional group having a radical polymerization initiating ability present in the olefin polymer having a functional group. It is 1 to 100 equivalents, preferably 0.5 to 50 equivalents. In order to increase the solubility of the catalyst in the reaction system, a coordinating aliphatic amine or aromatic amine may be added, or alkoxyaluminum may be added as a reaction accelerator.

As a solvent that can be used in the radical polymerization, any solvent can be used as long as it does not inhibit the reaction.For example, benzene, toluene, xylene and other aromatic hydrocarbon solvents, pentane, hexane, Aliphatic hydrocarbon solvents such as heptane, octane, nonane and decane, alicyclic hydrocarbon solvents such as cyclohexane, methylcyclohexane and decahydronaphthalene, chlorobenzene, dichlorobenzene, trichlorobenzene, methylene chloride, chloroform, Chlorinated hydrocarbon solvents such as carbon tetrachloride and tetrachloroethylene, alcohol solvents such as methanol, ethanol, n-propanol, iso-propanol, n-butanol, sec-butanol and tert-butanol, acetone, methyl ethyl ketone and methyl Ketone solvents such as isobutyl ketone; ester solvents such as ethyl acetate and dimethyl phthalate, dimethyl ether, diethyl ether, di -n- amyl ether, may be mentioned tetrahydrofuran and ether solvents such as dioxy anisole and the like. Also, suspension polymerization and emulsion polymerization can be performed using water as a solvent. These solvents may be used alone or in combination of two or more. In addition, it is preferable that the reaction liquid be a homogeneous phase by using these solvents, but the reaction liquid may be a plurality of non-uniform phases.

  The reaction temperature may be any temperature as long as the radical polymerization reaction proceeds, and is not uniform depending on the degree of polymerization of the desired polymer, the type and amount of the radical polymerization initiator and the solvent to be used, but is usually -100 ° C. ２５０250 ° C. The temperature is preferably from -50 ° C to 180 ° C, and more preferably from 0 ° C to 160 ° C. The reaction may be carried out under reduced pressure, normal pressure or increased pressure as the case may be. The polymerization reaction is preferably performed in an atmosphere of an inert gas such as nitrogen or argon.

  In the anionic polymerization, usable solvents include, for example, hexane, aliphatic hydrocarbons such as heptane, cyclopentane, alicyclic hydrocarbons such as cyclohexane, benzene, aromatic hydrocarbons such as toluene, diethyl ether, dioxane, Ether solvents such as tetrahydrofuran (THF), monoglyme and diglyme are used. These solvents can be used alone or in combination of two or more. Among them, aromatic hydrocarbons and ether solvents are preferably used. The polymerization is usually carried out at a polymerization temperature of -100C to 100C, preferably -80C to 80C, more preferably -70C to 70C, for 1 minute to 500 hours, preferably 10 minutes to 300 hours, more preferably Is carried out for 15 minutes to 150 hours.

  By sequentially performing the above steps 1 to 3, the graft polymer of the present invention is produced.

Further, the graft polymer according to the present invention can also be produced, for example, by sequentially carrying out Step 4, Step 5, and Step 6 shown below.
(Step 4) A functional group-containing olefin polymer (E) containing at least one functional group selected from a group containing a Group 13 element, a hydroxyl group, an amino group, an epoxy group, a carboxyl group, an acid halogen group, and an acid anhydride group. ).
(Step 5) The following general formula (XII)

[In the formula (XII), S is a hetero atom or a group containing a hetero atom, and P ² is a graft polymer chain having a polyolefin chain in a side chain. Producing a polyolefin side chain-containing graft polymer having a functional group at the terminal represented by the formula:
(Step 6) a step of bonding the functional group-containing olefin polymer (E) obtained in the above step 4 with the polyolefin side chain-containing graft polymer having a functional group at a terminal represented by the general formula (XII).

  Hereinafter, preferred examples of the method for producing the graft polymer of the present invention for each step will be described.

  In step 4, the same method as in step 1 can be used.

  Step 5 is a step of producing a polyolefin side chain-containing graft polymer having a functional group at a terminal. As a method for producing such a graft polymer, both the group capable of initiating radical polymerization and the functional group capable of reacting with the functional group contained in the functional group-containing olefin polymer (E) used in Step 2 are used. Using the compound (F) having the above as an initiator, the polyolefin macromonomers (C1), (C2) and (C3) used in the step 3 are homopolymerized or copolymerized with two or more kinds, or (C1) (C2) And (C3), by copolymerizing at least one kind of macromonomer selected from (C3) and one or more kinds of monomers (D) selected from organic compounds having at least one carbon-carbon unsaturated bond. The obtained polyolefin side chain-containing graft polymer represented by the above general formula (VIII) has a functional group derived from an initiator at its terminal.

In step 6, the functional group-containing olefin polymer (E) obtained in the step 4 and the polyolefin side chain-containing graft having a functional group at the terminal represented by the general formula (XII) obtained in the step 5 are used. This is a step of performing a coupling reaction with a polymer. About the combination of the functional group contained in the functional group-containing olefin polymer (E) and the terminal functional group S contained in the graft polymer represented by the general formula (XII) when performing this step. Are, for example, the following combinations, but are not particularly limited thereto.
(1) Among the functional group-containing olefin polymer (E), an olefin polymer having a carboxyl group as a functional group and a functional group at the terminal where S is a hydroxyl group-containing group in the general formula (XII) A polyolefin side chain-containing graft polymer having:
(2) Of the functional group-containing olefin polymer (E), an olefin polymer having a carboxyl group as a functional group and a functional group at the terminal where S is a group containing an amino group in the general formula (XII) A polyolefin side chain-containing graft polymer having:
(3) Of the functional group-containing olefin polymer (E), an olefin polymer having a hydroxyl group as a functional group, and a functional group at the terminal where S is an epoxy group-containing group in the general formula (XII). A polyolefin side chain-containing graft polymer having:
(4) Of the functional group-containing olefin polymer (E), an olefin polymer having a hydroxyl group as a functional group, and a functional group at the terminal where S is a group containing a carboxyl group in the general formula (XII). A polyolefin side chain-containing graft polymer having:
(5) Among the functional group-containing olefin polymer (E), an olefin polymer having a hydroxyl group as a functional group and a functional group at the terminal where S is a group containing an oxyhalogen group in the general formula (XII) A polyolefin side chain-containing graft polymer having:
(6) Among the functional group-containing olefin polymers (E), an olefin polymer having an acid halogen group as a functional group and a functional group at the terminal where S is a group containing a hydroxyl group in the general formula (XII) Polyolefin side chain-containing graft polymer having a group.
(7) Of the functional group-containing olefin polymer (E), an olefin polymer having an acid halogen group as a functional group, and a terminal where S in the general formula (XII) is a group containing an amino group. A polyolefin side chain-containing graft polymer having a functional group.
(8) Among the functional group-containing olefin polymer (E), an olefin polymer having a hydroxyl group as a functional group and a functional group at a terminal where S is a halogen-containing group in the general formula (XII) Polyolefin side chain-containing graft polymer.
(9) Of the functional group-containing olefin polymer (E), an olefin polymer having an epoxy group as a functional group and a functional group at the terminal where S is a group containing a hydroxyl group in the general formula (XII) Having a polyolefin side chain-containing graft polymer.
(10) Of the functional group-containing olefin polymer (E), an olefin polymer having an amino group as a functional group and a functional group at the terminal where S is a group containing a carboxyl group in the general formula (XII) Having a polyolefin side chain-containing graft polymer.
(11) Of the functional group-containing olefin polymer (E), an olefin polymer having an amino group as a functional group, and a functional group at a terminal where S is a group containing an oxyhalogen group in the general formula (XII). A polyolefin side chain-containing graft polymer having:

  Reaction solvent, reaction temperature, reaction time, condensation used in the reaction between the functional group-containing olefin polymer (E) and the polyolefin side chain-containing graft polymer having a terminal functional group represented by the general formula (XII) The reaction conditions such as the agent and the basic catalyst are the same as those described above in the case where the reaction between the functional group-containing olefin polymer (E) and the compound (F) in the step 2 is performed to convert the functional group-containing olefin polymer into a group having a radical polymerization or anionic polymerization initiation ability. The same conditions as the above can be applied.

  By sequentially performing the above steps 4 to 6, the graft polymer of the present invention is produced.

  The graft polymer produced by the above method is isolated by using a known method such as distillation of the solvent used for the polymerization and unreacted monomers or reprecipitation with a non-solvent.

  Hereinafter, the present invention will be described more specifically based on examples, but the present invention is not limited to these examples.

(1) Synthesis of macromonomer [Synthesis of terminally-Al-terminated ethylene-propylene copolymer (EPR)]
800 ml of purified toluene was placed in a 1 L glass autoclave sufficiently purged with nitrogen, and the liquid phase and the gas phase were saturated by blowing ethylene 20 l / h and propylene 80 l / h. Thereafter, at 50 ° C., 20 mmol of MAO in terms of Al and 0.02 mmol of dicyclopentadienyl zirconium dichloride were added to initiate polymerization. After polymerization at 50 ° C. for 120 minutes under normal pressure, a small amount of isobutyl alcohol was added to terminate the polymerization. The reaction solution was washed five times with 100 ml of a 1N aqueous hydrochloric acid solution and twice with 100 ml of water, and the organic layer was dried over anhydrous magnesium sulfate and filtered with a glass filter (G3) to remove magnesium sulfate. The filtrate was concentrated, and the obtained oily substance was dried under vacuum for 10 hours to obtain 118.7 g of a colorless and transparent oily EPR. The molecular weight of the polymer (EPR
When measured by GPC, Mw was 1690, Mn was 430, and Mw / Mn was 4.0. According to IR analysis, the propylene content of the polymer was 49 mol%, and 27.5 terminal vinylidene groups were contained per 1000 carbon atoms. 100 g of the obtained terminal vinylidene group-containing EPR was placed in a 1 L glass reactor which was sufficiently purged with nitrogen, 500 ml of toluene and 50 ml of diisobutylaluminum hydride were added, and the mixture was heated with stirring at 110 ° C. for 6 hours. Thus, a toluene solution containing the terminally EPR was obtained.

[Synthesis of EPR with terminal OH]
The toluene solution obtained above was kept at 105 ° C., the nitrogen gas was switched to dry air, and the solution was kept supplied at a flow rate of 100 liter / h for 7 hours while keeping the temperature, and then the solution was transferred to a separating funnel. The plate was washed three times with 300 ml of a 1N aqueous hydrochloric acid solution and twice with 200 ml of water. The organic layer was dried over anhydrous magnesium sulfate, filtered through a glass filter (G3), and the filtrate was concentrated. The resulting yellow oily substance was dried under vacuum for 10 hours to obtain 107.9 g of an oily polymer. Obtained.

A sample obtained by dissolving 100 mg of the polymer in 0.6 ml of deuterated chloroform at 25 ° C. was analyzed using ¹ H-NMR (JEOL GSX-270, manufactured by JEOL Ltd.). A signal based on the methylene group adjacent to the hydroxyl group was observed. That is, it was confirmed that an EPR having the terminal of the following structure (Formula 15) was present. The OH group content was calculated to be 2.8 mol% from the integrated value.

[Synthesis of EPR macromonomer]
A 200 ml two-necked flask sufficiently purged with nitrogen was charged with 50 g of the terminally OH-terminated EPR obtained above, and 60 ml of dry toluene, 13.0 ml of triethylamine and 18.3 ml of methacrylic acid chloride were added thereto, followed by stirring at room temperature for 18 hours. The obtained reaction solution was washed three times with 200 ml of a 1N aqueous hydrochloric acid solution and three times with 200 ml of water, and the organic layer was dried over anhydrous magnesium sulfate. Magnesium sulfate was filtered off with a glass filter (G3), and the obtained filtrate was concentrated to obtain 57.2 g of a tan oily polymer. 32.4 g of this polymer was dissolved in hexane and purified by column chromatography to obtain 22.4 g of a slightly yellow oily polymer. When the molecular weight (in terms of EPR) of the polymer was measured by GPC, Mw was 1,400, Mn was 580, and Mw / Mn was 2.3.

A sample obtained by dissolving 100 mg of the polymer in 0.6 ml of heavy chloroform at 25 ° C. was analyzed using 1H-NMR (JEOL GSX-270 manufactured by JEOL Ltd.). Signals were detected. δ 1.95 ppm (s, 3H; = C-C H 3), δ 3.8-4.1 ppm (m, 2H; -COO-C H 2-), δ 5.55 ppm (s, 1 H; C H 2 =) , Δ 6.1 ppm (s, 1H; C H 2 =). That is, it was confirmed that an EPR macromonomer having a terminal of the following structure (Formula 16) was present. The methacryl group content was calculated to be 3.8 mol% from the integrated value.

(2) Synthesis of hydroxyl group-containing polyethylene (PE) [Synthesis of ethylene / 10-undecene-1-ol copolymer]
900 mL of toluene is put into a 1 L glass-made polymerization vessel purged with nitrogen, and while flowing ethylene gas (100 L / h), 5.0 ml (5.0 mmol) of a stock solution of triethylaluminum (1.0 M toluene solution), 10 ml 0.80 ml (4.0 mmol) of -undecene-1-ol was added, and the mixture was stirred at 50 ° C for 5 minutes. Into another nitrogen-substituted 20 mL Schlenk flask, 17.6 mg of the following metallocene (Formula 17) was added, and 1.14 ml of a toluene solution of methylalumoxane (MAO) (Al = 1.37M) was added, followed by stirring for about 10 seconds. Thereafter, the solution was added to the polymerization solution. The mixture was stirred at 50 ° C. for 3 minutes (600 rpm) while flowing ethylene gas at 100 L / h. The reaction was stopped with isobutyl alcohol (15 ml) and concentrated hydrochloric acid (2 ml), and poured into 2 L of methanol to precipitate a polymer. After stirring overnight, the mixture was filtered through a glass filter, and the obtained polymer was dried at 80 ° C. under a reduced pressure of 10 Torr for 10 hours to obtain 10.09 g of an ethylene / 10-undecene-1-ol copolymer. Was. As a result of analysis by gel permeation chromatography (GPC), the molecular weight of the present polymer was 109300 in terms of weight average molecular weight (Mw) in terms of polylene, and the molecular weight distribution (Mw / Mn) was 3.04.
^From the result of ¹ H-NMR measurement, the content of the introduced comonomer (10-undecene-1-ol) was 0.78 mol%.

(3) Conversion of hydroxyl group-containing PE to polymerization initiation group [Synthesis of 2-bromoisobutyryl group-modified PE]
The ethylene / 10-undecene-1-ol copolymer (Mw:
109300, Mw / Mn: 3.04, comonomer content: 0.78 mol%) in a 500 mL two-necked eggplant flask equipped with a mechanical stirrer, and sufficiently purged with nitrogen. 300 ml of dry toluene was added, and the mixture was heated and stirred at 90 ° C. for 2 hours until the polymer was uniformly dispersed. After the temperature was lowered to 80 ° C., 1.78 ml of triethylamine and 1.32 ml of 2-bromoisobutyryl bromide were added, respectively. The mixture was heated and stirred at 80 ° C. for 3 hours. The reaction solution was poured into 2 L of methanol, and the precipitated polymer was filtered with a glass filter. At this time, the polymer on the glass filter was sequentially washed three times with 100 ml of methanol, once with 100 ml of 1N hydrochloric acid, and twice with 100 ml of methanol. The polymer was dried at 50 ° C. under a reduced pressure of 10 Torr for 10 hours. From the result of 1H-NMR, it was found that the terminal methylene (-
CH2-OCOCBr (CH3) 2) was identified as having obtained a terminal methyl (-CH2-OCOCBr (2-bromoisobutyryl group-modified PE in which all the hydroxyl groups of CH were modified) at δ = 1.83 ppm. .

(4) Synthesis of PE-g-poly (EPR macromonomer) graft polymer 0.238 g of 2-bromoisobutyryl group-modified PE (Terminal Br: 0.07 mmol) in a degassed nitrogen-substituted 100 ml Schlenk flask, macromonomer (MAEPR) 2.12 g (2.09 mmol) was added, and degassing and nitrogen replacement were repeated 5 times by a vacuum pump. Under a nitrogen stream, copper bromide 10 mg (0.07 mmol), o-xylene 6.7 ml, N, N, N ', N', N "-pentamethyldiethylenetriamine (0.5M o-xylene solution) 0.28 ml (0.14 mmol) was added sequentially, and a septum cap was attached. The temperature was raised to 120 ° C., and the mixture was reacted for 7 hours while stirring. After cooling the reaction Schlenk flask with ice water, about 5 ml of methanol was added to stop the reaction, and the mixture was poured into 500 ml of methanol and stirred overnight. The precipitated polymer was separated by filtration with a glass filter, and the polymer was dried at 80 ° C. under a reduced pressure of 15 Torr for 10 hours to obtain 0.40 g of a polymer.
^{From 1} H-NMR measurement, a polyethylene-g-poly (EPR macromonomer) graft polymer having a composition of ethylene: MAEPR (wt%) = 60:40 was obtained.

In a 100 ml Schlenk flask purged with degassed nitrogen, 0.238 g (terminal Br: 0.07 mmol) of 2-bromoisobutyryl group-modified PE synthesized in Example 1 and 0.71 g (0.70 mmol) of macromonomer (MAEPR) were added. Then, deaeration and nitrogen replacement were repeated 5 times with a vacuum pump. Under a nitrogen stream, 10 mg (0.07 mmol) of copper (I) bromide, 6.3 ml of o-xylene, N, N, N ', N', N "-pentamethyldiethylenetriamine (0.5M o-xylene solution) 0.28 ml (0.14 mmol) and 0.37 ml (3.49 mmol) of methyl methacrylate (MMA) were sequentially added, and a septum cap was attached. The temperature was raised to 120 ° C., and the mixture was reacted for 7 hours while stirring. After cooling the Schlenk flask with ice water, the reaction was stopped by adding about 5 ml of methanol, and further poured into 500 ml of methanol and stirred overnight. The precipitated polymer was separated by filtration with a glass filter, and the polymer was dried at 80 ° C. under a reduced pressure of 15 Torr for 10 hours to obtain 0.48 g of a polymer.

^{From 1} H-NMR measurement, a PE-g- (MMA-g-EPR) graft polymer having a composition of ethylene: MMA: MAEPR (wt%) = 52:18:30 was obtained.

(1) Synthesis of Macromonomer 250 ml of purified toluene was placed in a 500 ml-volume glass autoclave sufficiently purged with nitrogen, and the liquid phase and the gas phase were saturated by blowing 40 l / h of ethylene and 60 l / h of propylene. . Thereafter, at 25 ° C., 12.5 mmol of MAO in terms of Al and 0.05 mmol of bis (1,3-dimethylcyclopentadienyl) zirconium dichloride were added at 60 ° C. to initiate polymerization. After polymerization at 60 ° C. for 180 minutes under normal pressure, a small amount of isobutyl alcohol was added to terminate the polymerization. The reaction solution was washed five times with 200 ml of a 1N aqueous hydrochloric acid solution and twice with 200 ml of water, and the filtrate was concentrated. The obtained oily substance was vacuum-dried for 10 hours to obtain 201.8 g of a colorless and transparent oily EPR. Obtained. A sample obtained by dissolving 100 mg of the polymer in 0.6 ml of deuterated chloroform at 25 ° C. was analyzed using ¹ H-NMR (JEOL GSX-270, manufactured by JEOL Ltd.). A signal based on a vinylidene group was observed. That is, it was confirmed that an EPR having the terminal of the following structure (Formula 18) was present. From the integrated value, the composition ratio of each unit was calculated as ethylene / propylene / vinylidene group = 51/47 / 2.1 mol%.

(2) Synthesis of PE-g- (t-butyl polyacrylate-g-EPR) graft polymer A 2-bromoisobutyryl group-modified PE synthesized in Example 1 was placed in a 30 ml Schlenk flask purged with degassed nitrogen. .17 g (Terminal Br: 0.05 mmol) and 4.12 g (2.5 mmol) of the vinylidene group-containing macromonomer (VdEPR) synthesized above were subjected to degassing and nitrogen substitution by a vacuum pump five times. Under a nitrogen stream, 7.2 mg (0.05 mmol) of copper (I) bromide, 4.3 ml of o-xylene, N, N, N ′, N ′, N ″ -pentamethyldiethylenetriamine (0.5 M o- 0.2 ml (0.1 mmol) of xylene solution and 0.73 ml (5.0 mmol) of t-butyl acrylate (tBuA) were sequentially added, and a septum cap was attached. The temperature was raised to 120 ° C., and the reaction was performed for 6 hours while stirring. After cooling the Schlenk flask with ice water, the reaction was stopped by adding about 5 ml of methanol, and further poured into 300 ml of methanol and stirred overnight. The supernatant was removed by decantation, 300 ml of hexane was added to the precipitated polymer, and the mixture was stirred. The mixture was filtered with a glass filter, and the polymer was dried at 80 ° C. under a reduced pressure of 15 Torr for 10 hours. Obtained. ^{From 1} H-NMR measurement, a PE-g- (PtBuA-g-EPR) graft polymer having a composition of ethylene: propylene: tBuA (mol%) = 70:19:11 was obtained.

Claims (5)

A graft polymer comprising a structural unit (A) represented by the following general formula (I) and a structural unit (B) represented by the following general formula (II).

[In formulas (I) and (II), R ¹ is a group or atom selected from a hydrocarbon group having 1 to 20 carbon atoms, a hydrogen atom and a halogen atom, and R ² is a group having 1 to 20 carbon atoms. X is a hetero atom or a group containing a hetero atom, and Y is a graft polymer having a polyolefin chain in a side chain. ] The graft polymer according to claim 1, wherein the graft polymer contains at least two or more structural units (B) represented by the general formula (II) in a molecule. In the above general formula (II), the graft polymer represented by Y is a macromonomer (C1) having a polyolefin chain represented by the following general formula (III), and a polyolefin chain represented by the following general formula (IV) (C2) having a polyolefin chain and a macromonomer (C3) having a polyolefin chain represented by the following general formula (V)

[In the formulas (III), (IV), and (V), R ³ is a hydrogen atom or a methyl group, Z is a hetero atom or a group containing a hetero atom, and P ¹ is CH ₂ ＣＨCHR ⁴ (R ⁴ is a carbon atom.) A polymer chain obtained by homopolymerizing or copolymerizing an olefin represented by a hydrocarbon group having 1 to 20 atoms, a group or atom selected from a hydrogen atom or a halogen atom). ]
Or a copolymer of two or more macromonomers selected from the group consisting of (C1), (C2) and (C3), and at least one macromonomer selected from (C1), (C2) and (C3) and at least one carbon-carbon unsaturated bond. 3. The graft polymer according to claim 1, wherein the graft polymer is obtained by copolymerizing the monomer having the monomer (D). 4. 4. The graft according to claim 1, wherein in the general formula (III), the group represented by Z includes a group selected from a carboxylate group, an amide group, an ether group, and a carbamic acid ester group. 5. polymer. 5. The graft polymer according to claim 1, wherein in the general formula (I), the group represented by X includes a group selected from an ester group, an amide group, and an ether group.