JP4274970B2 - Graft polymer having polyolefin side chain-containing graft polymer in the side chain - Google Patents

Description

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

Polyolefins such as polyethylene (PE) and polypropylene (PP) are lightweight and inexpensive, and have excellent physical properties and processability, but on the other hand, printability, paintability, heat resistance, impact resistance and other properties. From the viewpoint of imparting high functionality such as compatibility with a polar polymer, its high chemical stability is hindered.
To compensate for this drawback and to make the polyolefin functional, for example, a method of copolymerizing an olefin and a polar monomer such as vinyl acetate or methacrylate by a radical polymerization method, or an anhydrous maleic anhydride in the presence of a peroxide. Methods for grafting polar monomers such as acids are known. However, these methods are difficult to precisely control the structure of the polyolefin moiety in the obtained polymer, and are insufficient to maintain the excellent physical properties of the polyolefin.

As one form of the polymer structure having a polyolefin portion whose structure is precisely controlled and having a function that cannot be expressed only by the polyolefin, a graft polymer in which a plurality of polar polymer segments are present as side chains in the polyolefin segment can be mentioned. . As an example of the production of such a graft polymer, for example, in WO 98/02472, radical polymerization active species are formed by oxidizing polyethylene or polypropylene having an organic boron compound as a side chain, and then radical polymerization. Discloses a method for producing a graft polymer in which a polar polymer such as polymethyl methacrylate or polystyrene is present as a side chain. However, since the graft polymer obtained in this way has only one kind of main chain as a polyolefin segment, for example, it can be used as a compatibilizer for one kind of polyolefin and a polar polymer, As compatibilizers and modifiers for mixed systems of multiple polyolefins and polar polymers, there is a problem that they cannot be used because they are incompatible with each other, and the content and physical properties of the polyolefin segment in the graft polymer. It is also difficult to control.
WO 98/02472

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

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

[In the 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 or a halogen atom, and R ² has 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 as a side chain. ]

  By 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 obtained efficiently.

  The graft polymer according to the present invention includes 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 or the group containing a hetero atom represented by X is specifically a group containing a group selected from an ester group, an ether group, and an amide group. Specific structural formulas are exemplified as X below.

The graft polymer chain having a polyolefin chain represented by Y as a 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. In particular, poly (meth) acrylate polymer, polystyrene polymer, poly (meth) acrylamide polymer, poly (meth) acrylonitrile polymer, poly (meth) acrylic acid polymer, etc., as the side chain, CH ₂ ═CHR ⁵ (R ⁵ is a polymer chain obtained by homopolymerizing or copolymerizing an olefin represented by the formula (wherein R ⁵ is a hydrocarbon group having 1 to 20 carbon atoms, a group selected from a hydrogen atom or a halogen atom) Are 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, And propylene-based copolymers such as propylene-hexene copolymer and propylene-octene copolymer.

Below, the manufacturing method of the graft polymer which concerns on this invention is demonstrated concretely.
The graft polymer according to the present invention is produced, for example, by sequentially performing the following step 1, step 2 and step 3.
(Step 1) Synthesis of 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 the functional group contained in the olefin polymer obtained in the step 1 into a group having radical polymerization or anion polymerization initiating ability.
(Step 3) A macromonomer having a polyolefin chain represented by the following general formula (III) using the olefin polymer having a radical polymerization or anion polymerization initiating group obtained in the above step 2 as a polymerization initiator (C1), a macromonomer having a polyolefin chain represented by the following general formula (IV) (C2) and a macromonomer having a polyolefin chain represented by the following general formula (V) (C3)

[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, P ¹ is CH ₂ ═CHR ⁴ (R ⁴ is carbon It is a polymer chain formed 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 at least one macromonomer selected from (C1), (C2) and (C3) and at least one carbon-carbon unsaturated bond. The process of manufacturing a graft polymer by copolymerizing 1 or more types of monomers (D) chosen from the organic compound which has.

  Hereinafter, a preferable example is described about the manufacturing method of the graft polymer of this invention according to each process.

  Step 1 produces 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. It is a process to do.

The olefin polymer (E) having the functional group is copolymerized with an olefin represented by CH ₂ ═CHR ⁶ and an olefin having a functional group, using a known olefin polymerization catalyst such as a Ziegler-Natta catalyst or a metallocene catalyst. Can be manufactured. R ⁶ is a group or atom selected from a hydrocarbon group having 1 to 20 carbon atoms, a hydrogen atom, or a halogen atom.

Specific examples of such olefins represented by CH ₂ ═CHR 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, 10 -Unsaturated alcohols in which the hydrocarbon moiety is linear, such as undecen-1-ol, unsaturated compounds such as 5-hexenoic acid, 6-heptenoic acid, 7-octenoic acid, 8-nonenoic acid, 9-decenoic acid In the exemplification of unsaturated amines such as carboxylic acids, allylamine, 5-hexeneamine, 6-hepteneamine, (2,7-octadienyl) succinic anhydride, pentapropenyl succinic anhydride and compounds in the above unsaturated carboxylic acids , Unsaturated acid anhydrides such as compounds in which a carboxylic acid group is replaced with a carboxylic acid anhydride group, and compounds of the above unsaturated carboxylic acids In the figure, unsaturated carboxylic acid halides such as compounds in which the 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-hept-6-enyl-9-borabicyclo [3.3.1] nonane, 9-oct-7-e. Lu-9-borabicyclo [3.3.1] nonane, 9-non-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 olefin polymer (E) having a functional group obtained in Step 1 above to a group having radical polymerization or anionic polymerization initiating ability. As the group having radical polymerization initiating ability, for example, as disclosed in Chem. Rev., 101, 3661 (2001), a group having a nitroxide is bonded and a radical is generated by thermal cleavage, Chem. Rev., 101, 2921 (2001) and Chem. Rev., 101, 3689 (2001), etc. are bonded with a group having a terminal halogen atom, and ruthenium or copper chloride or the like. Examples include those that generate radicals 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 radical polymerization initiating ability, the group having the radical polymerization initiating ability and the olefin polymer having the above functional group can be used. The method of making the compound (F) which has both the functional group which can react with the functional group contained in (E) react with the olefin polymer (E) which has the said functional group is mentioned.

  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 figure below. A compound can be illustrated.

  In addition to the conversion method by reaction with the compound (F), it is converted into a functional group having 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 initiating ability can be introduced between the group 13 element and the carbon atom. The oxygen-oxygen bond thus obtained is thermally cleaved and functions as a radical polymerization initiator.

Examples of the method for converting the functional group of the olefin polymer (E) having the functional group into a compound having an anion polymerization initiating ability include, for example, converting an olefin polymer having a hydroxyl group to alkali metals such as metallic lithium and metallic potassium, hydrogen A method of preparing a metal alkoxide-containing olefin polymer by reacting with an alkali metal hydride such as lithium hydride or potassium hydride, an alkylaluminum compound such as trimethylaluminum, triethylaluminum, triisobutylaluminum, or trihexylaluminum. Can be mentioned.
Functionality 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 having radical polymerization or anionic polymerization initiating ability If the amount of the compound (F) having both the group having the radical polymerization initiating ability for 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, Since the conversion rate of the functional group contained in the olefin polymer (E) having a functional group is lowered, the yield of the graft polymer obtained in Step 3 is lowered, and if it is too much, an unreacted compound (F) remains. In step 3, a homopolymer may be by-produced. Therefore, the usage-amount of the said compound (F) is 0.1-100 times mole normally with respect to the functional group contained in the olefin polymer (E) which has the said functional group, Preferably 0.3-50 times. Mol, more preferably 0.5 to 10 times mol.

  Examples of the reaction solvent include aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, and tetradecane, and alicyclic hydrocarbons such as cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, cyclooctane, and cyclohexene. , Aromatic hydrocarbons such as benzene, toluene, xylene, halogenated hydrocarbons such as dichloromethane, chloroform, dichloroethane, dichloropropane, trichloroethylene, chlorobenzene, dichlorobenzene, 2,4-dichlorotoluene, methyl acetate, ethyl acetate , Esters such as butyl acetate, ketones such as acetone and methyl ethyl ketone, dioxane, tetrahydrofuran, acetonitrile, dimethylformamide, dimethyl sulfoxide, etc. . Each of these may be used alone, or a plurality may be used in appropriate combination.

  The reaction between the olefin polymer (E) having the functional group and the compound (F) is performed in the presence of a condensing agent or a basic catalyst, depending on the type of 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, and 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 triethylamine, diisopropylethylamine, N, N-dimethylaniline, piperidine, pyridine, 4-dimethylaminopyridine, 1,5-diazabicyclo [4,3,0] non-5- Ene, 1,8-diazabicyclo [5,4,0] undec-7-ene, organic amines such as tri-n-butylamine and N-methylmorpholine, alkali metal compounds such as sodium hydride and n-butyllithium Etc.

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

  In the case of the olefin polymer (E) having the above functional group, when it has a carboxyl group as a functional group, first, for example, it is reacted with phosphorus pentachloride, thionyl chloride or the like to form an acid chloride compound. It can also be prepared by reacting F) with an appropriate solvent in the presence of a base.

  Step 3 has a polyolefin chain represented by the following general formula (III) using the olefin polymer having a functional group having radical polymerization or anion polymerization initiating ability obtained in Steps 1 and 2 as a macroinitiator. 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, P ¹ is CH ₂ ═CHR ³ (R ³ is carbon It is a polymer chain formed 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 types, or at least one macromonomer selected from (C1), (C2) and (C3) and at least one carbon-carbon unsaturated bond. A graft polymer chain to the olefin polymer having a functional group having a radical polymerization or anion polymerization initiating ability obtained in the above step 2 by copolymerizing with one or more monomers (D) selected from organic compounds having one It is a process of giving.

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

[In 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. ]
A styrene derivative represented by the following general formula (VII)

[In Formula (VII), P ¹ is the same as in 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. It is obtained by reacting with a functional group-containing polyolefin represented by the 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, m- 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- Lomohexyl) halogen-containing styrenes such as styrene, m-hydroxystyrene, p-hydroxystyrene, m-hydroxymethylstyrene, p-hydroxymethylstyrene, p- (2-hydroxyethyl) styrene, p- (3-hydroxypropyl) Styrene, hydroxyl group-containing styrenes such as p- (4-hydroxybutyl) styrene, 3-vinylbenzoic acid, 4-vinylbenzoic acid, (3-vinylphenyl) acetic acid, (4-vinylphenyl) acetic acid, 3- (4 -Vinylphenyl) propionic acid, 4- (4-vinylphenyl) butanoic acid, 5- (4-vinylphenyl) pentanoic acid, carboxyl group-containing styrenes such as 6- (4-vinylphenyl) hexanoic acid, 3-vinyl Benzoic acid chloride, 4-vinyl benzoic acid chloride, 3-vinyl benzoic acid bromine 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 Acid halide group-containing styrenes 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 group-containing styrenes such as 5- (4-vinylphenyl) pentylamine, Epoxy group-containing styrenes such as sidyl- (3-vinylbenzyl) ether and glycidyl- (4-vinylbenzyl) ether, 3-isocyanate styrene, 4-isocyanate styrene, 3-isocyanate methylstyrene, 4-isocyanate Isocyanate group-containing styrenes such as methylstyrene, 4- (2-isocyanatoethyl) styrene, 4- (3-isocyanatopropyl) styrene, 4- (4-isocyanatobutyl) styrene, and the like.

  The functional group-containing polyolefin represented by the general formula (VII) includes, for example, a) a polyolefin having a group containing a group 13 element, and then a group having a group 13 element of the polyolefin and a compound having a functional group structure. Solvolysis after carrying out the substitution reaction, or b) solvation after carrying out the substitution reaction with a compound having a structure that forms a functional group by solvolysis of a group containing the group 13 element of the polyolefin. Although it can manufacture by decomposing | disassembling, in this invention, it is not limited to these methods at all. Hereinafter, the above manufacturing method will be described in detail.

Production of polyolefin having a group containing a group 13 element A method for producing a polyolefin having a group containing a group 13 element includes: (a) a method of olefin polymerization with a known polymerization catalyst in the presence of a compound containing a group 13 element; ) The method is roughly classified into a method of producing by reaction with a polyolefin having an unsaturated bond at the terminal and a compound containing a group 13 element. Each will be described below.

[(A) Method for olefin polymerization in the presence of a compound containing a group 13 element]
A polyolefin having a group containing a group 13 element is homopolymerized with an olefin represented by CH ₂ = CHR ⁷ in the presence of a compound containing a group 13 element using an olefin polymerization catalyst such as a known Ziegler-Natta catalyst or a metallocene catalyst. Or it is manufactured by copolymerization. R ⁷ is a group or atom selected from a hydrocarbon group having 1 to 20 carbon atoms, a hydrogen atom, or a halogen atom.

Specific examples of such olefins represented by CH ₂ ═CHR ⁷ include ethylene, propylene, butene, pentene, hexene, octene, and decene.

  Examples of the compound containing a group 13 element include an organoaluminum compound and an organoboron compound.

  As an organoaluminum compound, for example, an organoaluminum compound represented by the following formula (VIII) can be exemplified.

R ^a _n AlA _3-n ... (VIII)
[In Formula (VIII), ^Ra is a C1-C12 hydrocarbon group, A is a halogen or hydrogen, and n is 1-3. ]
R ^a is a hydrocarbon group having 1 to 12 carbon atoms, such as an alkyl group, a cycloalkyl group, or an aryl group, and specifically includes a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an isobutyl group. Pentyl group, hexyl group, octyl group, cyclopentyl group, cyclohexyl group, phenyl group, tolyl group and the like.

Specific examples of such organoaluminum compounds include trialkylaluminums such as trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, trioctylaluminum, and tri-2-ethylhexylaluminum; trialkenylaluminums such as triisoprenylaluminum. Dimethylaluminum chloride, diethylaluminum chloride, diisopropylaluminum chloride, diisobutylaluminum chloride, dialkylaluminum halides such as dimethylaluminum bromide, methylaluminum sesquichloride, ethylaluminum sesquichloride, isopropylaluminum sesquichloride, butylaluminum sesquichloride, ethylaluminum Alkylaluminum sesquihalides such as kibromide; alkylaluminum dihalides such as methylaluminum dichloride, ethylaluminum dichloride, isopropylaluminum dichloride, ethylaluminum dibromide; alkylaluminum hydrides such as diethylaluminum hydride, diisobutylaluminum hydride, ethylaluminum dihydride Can be mentioned.

  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 the same as above, and 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 ) AlR ^h ₂ group, n is 1 to 2, and R ^b , R ^c , R ^d and R ^h are methyl group, ethyl group, isopropyl group, isobutyl group, cyclohexyl group, phenyl group, etc. , R ^e is hydrogen, methyl group, ethyl group, isopropyl group, phenyl group, trimethylsilyl group and the like, and R ^f and R ^g are methyl group, ethyl group and the like.

Specific examples of such an organoaluminum compound include the following compounds.
_{^{(I) R a n Al (}} OR b) a compound represented by _3-n, e.g., dimethylaluminum methoxide, diethylaluminum ethoxide and diisobutylaluminum _{^{methoxide, (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), like _{(iso-Bu) 2 Al (} OSiEt 3), (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- compounds 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 , (v) ^{_{R a n Al (SiR f 3}} ) a compound represented by _3-n, e.g., (iso-Bu) ₂ AlSiMe Etc. ^{_{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 etc.

In addition, a compound similar to this, for example, an organoaluminum compound in which two or more aluminums are bonded through an oxygen atom or a nitrogen atom can be given. 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 aluminoxanes (organoaluminum oxy compounds) such as methylaluminoxane.

  Moreover, the organoaluminum compound of following formula (X) can also be used.

R ^a _n AlAB .... (X)
[R ^a , A and B are the same as in the above formula (VIII) or (IX). ]
An organic boron compound can also be used as the compound containing a group 13 element. Organic boron compounds 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, dicyamilborane, diisopinocanphenylborane, 9-borabicyclo [3.3.1] nonane, catechol Examples thereof include borane, B-bromo-9-borabicyclo [3.3.1] nonane, borane-triethylamine complex, and borane-methyl sulfide complex.

Moreover, you may use an ionic compound as an organoboron 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-dimethylanilinium tetra ( Phenyl) boron, dicyclohexylammonium tetra (phenyl) boron, triphenylcarbenium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl)
Examples thereof include borate, bis [tri (n-butyl) ammonium] nonaborate, and bis [tri (n-butyl) ammonium] decaborate.

  Moreover, the compound containing these group 13 elements may be used independently, and can also be used in combination of multiple.

[(B) Method for producing from polyolefin having unsaturated bond at terminal]
A polyolefin having a group containing a group 13 element can also be produced using a polyolefin having an unsaturated bond at the terminal. Specifically, it is a method of reacting a polyolefin having a terminal unsaturated bond with a compound containing a group 13 element, such as an organoaluminum compound or an organoboron compound, to obtain a polyolefin having a group containing a group 13 element. .

  Polyolefin having a terminal unsaturated bond (terminal unsaturated polyolefin) is obtained by polymerizing or copolymerizing an olefin having 2 to 20 carbon atoms in the presence of an olefin polymerization catalyst such as a known 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 be converted into a polyolefin having a group containing a group 13 element. In addition, even when the obtained polyolefin is a mixture of one having a group 13 element bonded to one end and one having an unsaturated bond end on one end, the one end is unsaturated bond, if necessary. You may convert the terminal of polyolefin which is a terminal into the terminal which group 13 element combined.

  As the compound containing a group 13 element used for the reaction, an organoaluminum compound or an organoboron compound is preferably used. Among them, a trialkylaluminum, a dialkylaluminum hydride, or a boron compound having one or more hydrogen-boron bonds is more preferable. As the organic aluminum, a dialkylaluminum hydride is particularly preferable. As an organic boron compound, 9-borabicyclo [3 , 3,1] nonane is particularly preferred.

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

Conversion to a functional group-containing polyolefin represented by the general formula (VII) A polyolefin having a group containing a group 13 element thus produced is
(Method a) Substitution of a group having a group 13 element of the polyolefin with a compound having a functional group structure
Conducting the reaction followed by solvolysis, or
(Method b) A functional group is formed by solvolysis of a group containing a group 13 element of the polyolefin.
By carrying out a substitution reaction with a compound having a structure, followed by solvolysis,
Polio represented by the following general formula (XI) wherein V in the general formula (VII) is a hydroxyl group
Can be converted to refine.

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 acid chloride. Moreover, oxygen, carbon monoxide, carbon dioxide, etc. are mentioned as a compound which has a structure which forms a functional group by solvolysis used in (Method b).

  Substitution reaction of a group containing a group 13 element of a polyolefin having a group containing a group 13 element obtained as described above with a compound having a functional group structure or a compound having a structure forming a functional group by solvolysis Is 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 50 hours. Examples of the solvent used for the solvolysis include methanol, ethanol, propanol, butanol, and water.

  Among the polyolefins having the functional group represented by the general formula (VII), a polyolefin in which V is an epoxy group is a terminal unsaturated polyolefin produced by the above method, for example, JP-A-63-305104. It can also be produced by epoxidizing unsaturated bonds using the method shown in FIG.

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

  Further, among the polyolefins having the functional group represented by the general formula (VII), the polyolefin in which V is an acid anhydride group is a terminal unsaturated polyolefin produced by the above method, for example, Makromol. Chem. Macromol. A method of introducing an acid anhydride at the terminal by, for example, thermal reaction with maleic anhydride using the method shown in Symp., 48/49, 317 (1991) or Polymer, 43, 6351 (2002), etc. Can be used.

  Of the polyolefins having the functional group represented by the general formula (VII), the polyolefin in which V is a carboxyl group is obtained by oxidizing the hydroxyl group having a hydroxyl group represented by the general formula (XI). It can manufacture using the method of converting into.

The polyolefin having the functional group represented by the general formula (VII) is a known olefin polymerization catalyst such as a Ziegler-Natta catalyst or a metallocene catalyst, and an olefin having a functional group and an olefin represented by CH ₂ = CHR ^8. Can also be produced by copolymerization. As a method for selectively introducing an olefin having a functional group at the terminal, for example, a method as 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, or a halogen atom.

Specific examples of such olefins represented by CH ₂ ═CHR 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, 10 -Unsaturated alcohols in which the hydrocarbon moiety is linear, such as undecen-1-ol, unsaturated compounds such as 5-hexenoic acid, 6-heptenoic acid, 7-octenoic acid, 8-nonenoic acid, 9-decenoic acid In the exemplification of unsaturated amines such as carboxylic acids, allylamine, 5-hexeneamine, 6-hepteneamine, (2,7-octadienyl) succinic anhydride, pentapropenyl succinic anhydride and compounds in the above unsaturated carboxylic acids , Unsaturated acid anhydrides such as compounds in which a carboxylic acid group is replaced with a carboxylic acid anhydride group, and compounds of the above unsaturated carboxylic acids In the figure, unsaturated carboxylic acid halides such as compounds in which the carboxylic acid group is replaced with a carboxylic acid halide group, 4-epoxy-1-butene, 5-epoxy-1-pentene, 6-epoxy-1-hexene, 7- Examples thereof include 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), the styrene derivative represented by the general formula (VI) and the general formula (VII) Examples of the combination with the polyolefin having a functional group include, but are not limited to, combinations shown below.
(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 the 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 the 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 the 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 the terminal in which 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 the terminal in which 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 the terminal in which V is an acid halogen group in the general formula (VII).
(7) In the general formula (VI), a styrene derivative in which W is a group containing an acid halogen group,
A polyolefin having a functional group at the terminal where V is a hydroxyl group in the general formula (VII).
(8) In the general formula (VI), a styrene derivative in which W is a group containing an acid halogen group,
In the general formula (VII), polyolefin having a functional group at the terminal where V is an amino group.
(9) A styrene derivative in which W is a group containing halogen in the general formula (VI), and a polyolefin having a functional group at the terminal where V is a hydroxyl group in the general formula (VII).
(10) In the general formula (VI), a styrene derivative in which W is a group containing an epoxy group;
A polyolefin having a functional group at the terminal where V is a hydroxyl group in the general formula (VII).
(11) 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 the terminal in which V is a carboxyl group in the general formula (VII).
(12) 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 the terminal in which V is an acid halogen group in the 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 the terminal in which 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 the terminal where V is a hydroxyl group in the general formula (VII).

  The amount of the styrene derivative represented by the general formula (VI) used for the polyolefin having the functional group represented by the general formula (VII) in the production of the polyolefin macromonomer having a styryl group at the terminal of the present invention is the functional group. It is 0.01-100 times mole normally with respect to the polyolefin which has this, Preferably it is 0.1-10 times mole.

  Examples of the reaction solvent include aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, and tetradecane, and alicyclic hydrocarbons such as cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, cyclooctane, and cyclohexene. , Aromatic hydrocarbons such as benzene, toluene, xylene, halogenated hydrocarbons such as dichloromethane, chloroform, dichloroethane, dichloropropane, trichloroethylene, chlorobenzene, dichlorobenzene, 2,4-dichlorotoluene, methyl acetate, ethyl acetate , Esters such as butyl acetate, ketones such as acetone and methyl ethyl ketone, dioxane, tetrahydrofuran, acetonitrile, dimethylformamide, dimethyl sulfoxide, etc. . Each of these may be used alone, or a plurality may be used in appropriate combination.

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

  Examples of the condensing agent include inorganic dehydrating condensing agents such as concentrated sulfuric acid, diphosphorus pentoxide, and anhydrous zinc chloride, and 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 of the styrene derivative represented by the general formula (VI) and the polyolefin having the 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, N-methylmorpholine, alkali metals such as sodium hydride, potassium hydride, lithium hydride and n-butyllithium Examples thereof include compounds.

  Of the styrene derivatives represented by the general formula (VI) and the polyolefin having the functional group represented by the general formula (VII), when having a carboxyl group as the functional group, first, for example, phosphorus pentachloride or chloride Reaction with thionyl and the like to form an acid chloride compound, which respectively reacts with a polyolefin having a functional group represented by the above general formula (VII) and a styrene derivative represented by the above general formula (VI) in a suitable solvent. Can also be manufactured.

  In the case where 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 be also produced by converting to an alkoxide with an alkoxide agent and reacting this with a styrene derivative represented by the above general formula (VI) having a group containing a halogen atom in an appropriate solvent. Examples of the metal alkoxide agent include metal sodium, metal potassium, sodium hydride, potassium hydride, sodaamide and the like.

  The polyolefin macromonomer (C2) having an acryloyl group or a methacryloyl group at the terminal represented by the general formula (IV) includes a polyolefin having a hydroxyl group at the terminal and an acrylic acid halide, methacrylic acid 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 that in which V is a hydroxyl group among the polyolefins having a functional group at the terminal represented by the general formula (VII). The reaction of the obtained polyolefin having a hydroxyl group at the terminal with acrylic acid halide, methacrylic acid halide, acrylic acid or methacrylic acid is performed, for example, as follows.
[1] A method of reacting a polyolefin having a hydroxyl group at the terminal with an acrylic acid halide or methacrylic acid halide such as acrylic acid chloride or methacrylic acid chloride in the presence of a base such as triethylamine.
[2] A method of reacting a polyolefin having a terminal hydroxyl group with acrylic acid or methacrylic acid in the presence of an acid catalyst.

  In 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 end of the polyolefin. The reaction temperature is usually −100 to 150 ° C., preferably 0 to 120 ° C., and the reaction time is usually 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 vinylidene group at the terminal represented by the general formula (V) is an olefin such as a known Ziegler-Natta catalyst or 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.
A low molecular weight polyolefin having a double bond at a part or all of molecular ends obtained by decomposing a polyolefin obtained by polymerization in the presence of the olefin polymerization catalyst with heat or a radical is also a polyolefin macromonomer. It can be used as (C3).

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

  The graft polymer according to the present invention is a polyolefin macromonomer (C1) (C2) and (C3) in the presence of an olefin polymer having a functional group having radical polymerization or anion polymerization initiating ability obtained by the steps 1 and 2. 1 type selected from an organic compound having at least one carbon-carbon unsaturated bond and at least one type of macromonomer selected from (C1), (C2) and (C3). 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. A 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, (meth) acrylate-n-propyl, isopropyl (meth) acrylate, (meth) Acrylic acid-n-butyl, (meth) acrylic acid isobutyl, (meth) acrylic acid-tert-butyl, (meth) acrylic acid-n-pentyl, (meth) acrylic acid-n-hexyl, (meth) acrylic acid cyclohexyl , (Meth) acrylic acid-n-heptyl, (meth) acrylic acid-n-octyl, (meth) acrylic acid-2-ethylhexyl, (meth) acrylic acid nonyl, (meth) acrylic acid decyl, (meth) acrylic acid Dodecyl, phenyl (meth) acrylate, toluyl (meth) acrylate, benzyl (meth) acrylate, (meth) acrylic acid -Methoxyethyl, (meth) acrylate-3-methoxybutyl, (meth) acrylate-2-hydroxyethyl, (meth) acrylate-2-hydroxypropyl, stearyl (meth) acrylate, glycidyl (meth) acrylate , (Meth) acrylic acid 2-aminoethyl, γ- (methacryloyloxypropyl) trimethoxysilane, (meth) acrylic acid ethylene oxide adduct, (meth) acrylic acid trifluoromethyl methyl, (meth) acrylic acid 2- Trifluoromethylethyl, 2-perfluoroethylethyl (meth) acrylate, 2-perfluoroethyl-2-perfluorobutylethyl (meth) acrylate, 2-perfluoroethyl (meth) acrylate, (meth) acrylic Perfluoromethyl acid, dimethafluoro (meth) acrylate Methylmethyl, 2-perfluoromethyl-2-perfluoroethylmethyl (meth) acrylate, 2-perfluorohexylethyl (meth) acrylate, 2-perfluorodecylethyl (meth) acrylate, (meth) acrylic acid (Meth) acrylic acid 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, nitrile group-containing vinyl monomers such as acrylonitrile and methacrylonitrile, acrylamide and methacrylamide Amide group-containing vinyl monomers such as vinyl acetate, vinyl propionate, vinyl pivalate, vinyl benzoate, vinyl cinnamate, etc., olefin monomers such as ethylene, propylene, butene, butadiene, isoprene, etc. 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. A compound having a polymerizable (meth) acryloyl group or styryl group at the end of a polymer obtained by polymerizing one or more of these organic compounds alone, 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 as necessary. Examples of such a catalyst include CuBr, CuCl, RuCl, RuCl ₂ , FeCl, FeCl _{2 and the} like. When the catalyst is used, the amount used depends on the amount of the functional group having the radical polymerization initiating ability present in the olefin polymer having a functional group, but is usually 0. 1 to 100 equivalents, preferably 0.5 to 50 equivalents. In addition, in order to increase the solubility of the catalyst in the reaction system, a coordinating aliphatic amine or aromatic amine can be added, or an alkoxyaluminum as a reaction accelerator can be added.

As the solvent that can be used in radical polymerization, any solvent that does not inhibit the reaction can be used. For example, as specific examples, aromatic hydrocarbon solvents such as benzene, toluene, and xylene, 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. Further, suspension polymerization and 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 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 solvent used, but is usually −100 ° C. ~ 250 ° C. 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.

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

  The graft polymer of this invention is manufactured by implementing the said processes 1-3 sequentially.

Moreover, the graft polymer based on this invention can be manufactured also by implementing sequentially the following process 4, the process 5, and the process 6, for example.
(Step 4) 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 (E ).
(Step 5) The following general formula (XII)

[In 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 as a side chain. ] The process of manufacturing the polyolefin side chain containing graft polymer which has a functional group at the terminal represented by this.
(Step 6) A step of bonding the functional group-containing olefin polymer (E) obtained in the step 4 and a polyolefin side chain-containing graft polymer having a functional group at the terminal represented by the general formula (XII).

  Hereinafter, a preferable example is described about the manufacturing method of the graft polymer of this invention according to each process.

  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 the terminal. As a method for producing such a graft polymer, both the group having radical polymerization initiating ability used in the step 2 and the functional group capable of reacting with the functional group contained in the functional group-containing olefin polymer (E) are used. The polyolefin macromonomer (C1) (C2) and (C3) used in the above step 3 is homopolymerized or copolymerized with two or more types using the compound (F) having an initiator as an initiator, or (C1) (C2) And at least one macromonomer selected from (C3) and one or more 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 end.

Step 6 includes a functional group-containing olefin polymer (E) obtained by the step 4 and a polyolefin side chain-containing graft having a functional group at the terminal represented by the general formula (XII) obtained by the step 5. This is a step of performing a coupling reaction with a polymer. Regarding 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 carrying out this step Examples include the combinations shown below, 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 group containing a hydroxyl group in the general formula (XII). Polyolefin side chain-containing graft polymer having
(2) 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 group containing an amino group in the general formula (XII). Polyolefin side chain-containing graft polymer having
(3) 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 in which S is a group containing an epoxy group in the general formula (XII). Polyolefin side chain-containing graft polymer having
(4) 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 a carboxyl group in the general formula (XII). 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 in the general formula (XII), S is a group containing an acid halogen group. Polyolefin side chain-containing graft polymer having
(6) Among the functional group-containing olefin polymer (E), an olefin polymer having an acid halogen group as a functional group, and in the general formula (XII), S is a group containing a hydroxyl group. Polyolefin side chain-containing graft polymer having a group.
(7) Among the functional group-containing olefin polymer (E), an olefin polymer having an acid halogen group as a functional group and a terminal in which S is a group containing an amino group in the general formula (XII). Polyolefin side chain-containing graft polymer having a functional group in
(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 the terminal where S is a halogen-containing group in the general formula (XII) Polyolefin side chain-containing graft polymer.
(9) Among 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). Polyolefin side chain-containing graft polymer.
(10) Among 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) Polyolefin side chain-containing graft polymer.
(11) Among 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 in which S is a group containing an acid halogen group in the general formula (XII) 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 functional group at the terminal represented by the general formula (XII) Each reaction condition such as an agent and a basic catalyst is obtained when the functional group-containing olefin polymer (E) and the compound (F) in Step 2 are converted into a group having radical polymerization or anion polymerization initiating ability. The same conditions as the reaction conditions can be applied.

  The graft polymer of this invention is manufactured by implementing the said process 4-6 sequentially.

  The graft polymer produced | generated by said method is isolated by using well-known methods, such as distillation of the solvent used for superposition | polymerization, the unreacted monomer, or reprecipitation by a non-solvent.

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

(1) Synthesis of macromonomer [synthesis of terminal Al-modified ethylene-propylene copolymer (EPR)]
800 ml of purified toluene was put into a 1 L glass autoclave sufficiently purged with nitrogen, and the liquid phase and the gas phase were saturated by blowing ethylene 20 liter / h and propylene 80 liter / h. Thereafter, at 50 ° C., MAO was added in an amount of 20 mmol in terms of Al and 0.02 mmol of dicyclopentadienylzirconium dichloride 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 5 times with 100 ml of 1N hydrochloric acid aqueous solution and further washed twice with 100 ml of water, and then the organic layer was dried over anhydrous magnesium sulfate and filtered through a glass filter (G3) to remove magnesium sulfate. The filtrate was concentrated, and the obtained oily substance was vacuum-dried for 10 hours to obtain 118.7 g of colorless and transparent oily EPR. Molecular weight of the polymer (EPR
As measured by GPC, Mw was 1690, Mn was 430, and Mw / Mn was 4.0. The propylene content of the polymer was 49 mol% by IR analysis, and 27.5 terminal vinylidene groups were contained per 1000 carbons. 100 g of the obtained terminal vinylidene group-containing EPR was placed in a 1 L glass reactor sufficiently purged with nitrogen, 500 ml of toluene and 50 ml of diisobutylaluminum hydride were added, and the mixture was heated and stirred at 110 ° C. for 6 hours. Thus, a toluene solution containing terminal Al-modified EPR was obtained.

[Synthesis of terminally OHated EPR]
The toluene solution obtained above was kept at 105 ° C., nitrogen gas was switched to dry air, and the supply was continued at a flow rate of 100 liters / h for 7 hours while maintaining the temperature, and then the solution was transferred to a separatory funnel, It was washed 3 times with 300 ml of 1N aqueous hydrochloric acid solution and further washed 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 vacuum-dried 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 deuterochloroform at 25 ° C. was analyzed using ¹ H-NMR (JEOL GSX-270 manufactured by JEOL Ltd.), and 3.3-3.6 ppm. A signal based on the methylene group adjacent to the hydroxyl group was observed. That is, it was confirmed that EPR having an end of the following structure (Chemical Formula 15) was present. Moreover, the OH group content was calculated with the integrated value as 2.8 mol%.

[Synthesis of EPR Macromonomer]
In a 200 ml two-necked flask sufficiently purged with nitrogen, 50 g of the terminally OHated EPR obtained above was added, 60 ml of dry toluene, 13.0 ml of triethylamine and 18.3 ml of methacrylic acid chloride were added, and the mixture was stirred at room temperature for 18 hours. The obtained reaction solution was washed with 200 ml of 1N hydrochloric acid aqueous solution three times, and further washed with 200 ml of water three times, and then 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 (EPR conversion) of the polymer was measured by GPC, Mw was 1400, Mn was 580, and Mw / Mn = 2.3.

A sample obtained by dissolving 100 mg of the polymer in 0.6 ml of deuterochloroform at 25 ° C. was analyzed using 1H-NMR (JEOL GSX-270 manufactured by JEOL Ltd.). Signal was 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, 1H; C H 2 =) , Δ 6.1 ppm (s, 1H; C H 2 =). That is, it was confirmed that an EPR macromonomer having an end having the following structure (Chemical Formula 16) was present. Moreover, the methacryl group content was calculated with the integrated value as 3.8 mol%.

(2) Synthesis of hydroxyl group-containing polyethylene (PE) [Synthesis of ethylene / 10-undecen-1-ol copolymer]
Into a 1 L glass polymerization vessel purged with nitrogen, 900 mL of toluene was introduced, and while passing ethylene gas (100 L / h), a stock solution of triethylaluminum (1.0 M toluene solution) 5.0 ml (5.0 mmol), 10 -0.80 ml (4.0 mmol) of undecen-1-ol was added, and it stirred at 50 degreeC for 5 minute (s). To another nitrogen-substituted 20 mL Schlenk flask, 17.6 mg of the following (chemical formula 17) metallocene was added, 1.14 ml of a toluene solution of methylalumoxane (MAO) (Al = 1.37 M) was added, and the mixture was stirred for about 10 seconds. Later, the solution was added to the polymerization solution. The mixture was stirred (600 rpm) at 50 ° C. for 3 minutes while flowing ethylene gas at 100 L / h. The reaction was stopped with isobutyl alcohol (15 ml) and concentrated hydrochloric acid (2 ml), and the mixture was 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 ethylene / 10-undecen-1-ol copolymer. It was. As a result of analysis by gel permeation chromatography (GPC), the molecular weight of the polymer was 109300 in terms of a weight-average molecular weight (Mw) in terms of polyylene, 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-undecen-1-ol) was 0.78 mol%.

(3) Conversion of hydroxyl-containing PE to polymerization initiation group [Synthesis of 2-bromoisobutyryl group-modified PE]
Ethylene / 10-undecen-1-ol copolymer (Mw: obtained above)
(109300, Mw / Mn: 3.04, comonomer content: 0.78 mol%) was placed in a 500 mL two-necked eggplant flask equipped with a mechanical slurryer, and the atmosphere was sufficiently substituted with nitrogen. Add 300 ml of dry toluene, heat and stir for 2 hours until the polymer is uniformly dispersed at 90 ° C., cool to 80 ° C., then add 1.78 ml of triethylamine and 1.32 ml of 2-bromoisobutyryl bromide, 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 through a glass filter. At this time, the polymer on the glass filter was washed successively with 100 ml of methanol three times, 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, δ = 4.05-4.09 ppm and terminal methylene (-
CH2-OCOCBr (CH3) 2) was identified as the result that a terminal methyl (-CH2-OCOCBr (2-bromoisobutyryl group-modified PE in which all hydroxyl groups were modified) was obtained at δ = 1.83 ppm. .

(4) Synthesis of PE-g-poly (EPR macromonomer) graft polymer In a 100 ml Schlenk flask purged with degassed nitrogen, 0.238 g of 2-bromoisobutyryl group-modified PE (terminal Br: 0.07 mmol), macromonomer (MAEPR) 2.12 g (2.09 mmol) was added, and deaeration with a vacuum pump and nitrogen substitution were repeated 5 times. 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 reacted for 7 hours with stirring. After cooling the Schlenk flask with ice water, about 5 ml of methanol was added to stop the reaction, and the mixture was further poured into 500 ml of methanol and stirred overnight. The precipitated polymer was filtered off with a glass filter, and the polymer was dried under reduced pressure conditions of 80 ° C. and 15 Torr for 10 hours to obtain 0.40 g of 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.

Into 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 with a vacuum pump and nitrogen replacement were repeated 5 times. Under a nitrogen stream, copper bromide (I) 10 mg (0.07 mmol), o-xylene 6.3 ml, N, N, N ′, N ′, N ″ -pentamethyldiethylenetriamine (0.5 M o-xylene solution) 0.28 ml (0.14 mmol) and methyl methacrylate (MMA) 0.37 ml (3.49 mmol) were sequentially added, and a septum cap was attached. The temperature was raised to 120 ° C. and reacted for 7 hours with stirring. After cooling the 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 filtered off 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 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 glass autoclave sufficiently purged with nitrogen, and the liquid phase and gas phase were saturated by blowing ethylene 40 liter / h and propylene 60 liter / h. . Thereafter, at 60 ° C., 12.5 mmol of MAO in terms of Al and 0.05 mmol of bis (1,3-dimethylcyclopentadienyl) zirconium dichloride were added 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 5 times with 200 ml of 1N hydrochloric acid aqueous solution and further washed 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 colorless and transparent oily EPR. Obtained. A sample obtained by dissolving 100 mg of the polymer in 0.6 ml of deuterochloroform at 25 ° C. was analyzed using ¹ H-NMR (JEOL GSX-270, manufactured by JEOL Ltd.), and 4.6 to 4.8 ppm. A signal based on the vinylidene group was observed. That is, it was confirmed that EPR having an end of the following structure (Chemical 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 2-bromoisobutyryl group-modified PE 0 synthesized in Example 1 in a degassed nitrogen-substituted 30 ml Schlenk flask .17 g (terminal Br: 0.05 mmol) and 4.12 g (2.5 mmol) of the vinylidene group-containing macromonomer (VdEPR) synthesized above were added, and degassing with a vacuum pump and nitrogen substitution were repeated 5 times. Under a nitrogen stream, copper bromide (I) 7.2 mg (0.05 mmol), o-xylene 4.3 ml, N, N, N ′, N ′, N ″ -pentamethyldiethylenetriamine (0.5 M o− Xylene solution) 0.2 ml (0.1 mmol) and t-butyl acrylate (tBuA) 0.73 ml (5.0 mmol) were sequentially added, and a septum cap was attached. The temperature was raised to 120 ° C. and reacted for 6 hours with stirring. After cooling the Schlenk flask with ice water, about 5 ml of methanol was added to stop the reaction, and the mixture was 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 and then filtered through a glass filter. The polymer was dried at 80 ° C. under a reduced pressure of 15 Torr for 10 hours to obtain 0.13 g of polymer. 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 method for producing a graft polymer comprising the following (Step 1), (Step 2), and (Step 3).
(Process 1)
An olefin (e-1) represented by CH ₂ = CHR ⁶ (R ⁶ is a group or atom selected from a hydrocarbon group having 1 to 20 carbon atoms, a hydrogen atom or a halogen atom);
Olefins 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 (e-2)
To synthesize a olefin polymer (E) having a functional group
(Process 2)
The olefin polymer (E);
At least one compound (F) selected from the following compounds (Chemical Formula 101)
Is a step of synthesizing an olefin polymer (E ′) in which the functional group of the olefin polymer (E) is converted to a group having radical polymerization initiating ability.

(Process 3)
In the olefin polymer (E ′),
Selected from the macromonomer (C2) having a polyolefin chain represented by the following general formula (IV) (Chemical Formula 3) and the macromonomer (C3) having a polyolefin chain represented by the following general formula (V) (Chemical Formula 4) Macromonomer
A step of homopolymerizing or copolymerizing two or more types to give a graft polymer chain

[In the formula (IV) (V) , R ³ is a hydrogen atom or a methyl group , P ¹ is CH ₂ ═CHR ⁴ (R ⁴ is a hydrocarbon group having 1 to 20 carbon atoms, a hydrogen atom or a halogen atom. Is a polymer chain formed by homopolymerization or copolymerization of an olefin represented by the following formula: ] The method for producing a graft polymer according to claim 1, wherein the olefin (e-1) is an olefin selected from ethylene, propylene, butene, pentene, hexene, octene, and decene. P in the general formulas (IV) and (V) ¹ Are polyethylene, polypropylene, polybutene, poly (4-methyl-1-pentene), ethylene-propylene copolymer, ethylene-butene copolymer, ethylene-hexene copolymer, ethylene-octene copolymer, propylene-butene. The method for producing a graft polymer according to any one of claims 1 to 2, wherein the polymer chain is selected from a copolymer, a propylene-hexene copolymer, and a propylene-octene copolymer. The method for producing a graft polymer according to any one of claims 1 to 3, wherein the (step 3) is the following (step 3 ').
(Step 3 ')
The olefin polymer (E ');
At least one macromonomer selected from the macromonomer (C2) having a polyolefin chain represented by the general formula (IV) and the macromonomer (C3) having a polyolefin chain represented by the general formula (V);
One or more monomers (D) selected from organic compounds having at least one carbon-carbon unsaturated bond
To graft the polymer chain The method for producing a graft polymer according to claim 4, wherein the monomer (D) is a (meth) acrylic acid monomer.