JP6007142B2 - Polar olefin multi-component copolymer with excellent adhesion performance - Google Patents

Description

  The present invention relates to a polar olefin multi-component copolymer having excellent adhesion performance, and more specifically, a nonpolar monomer unit selected from ethylene and an α-olefin having 3 to 10 carbon atoms, and a polar monomer unit having a norbornene skeleton And, optionally, other polar monomer units, and relates to a multi-component polar olefin copolymer having improved adhesion at each stage.

  Polyolefins typified by polyethylene and polypropylene are very widely used because of their excellent properties such as physical properties and moldability among resin materials, as well as high economic efficiency and compatibility with environmental problems, as well as resource reusability. And important industrial materials.

However, since polyolefins are usually nonpolar, their adhesion to other materials, printability, and compatibility with fillers have not been sufficient.
Therefore, in order to improve the adhesion with different polar materials, a method of grafting polar group-containing monomers using an organic peroxide has been widely performed, but in this method, in parallel with the grafting reaction. As a result, intermolecular crosslinking of both olefinic resins and molecular chain scission of the olefinic resins occur, so that there is a problem that the excellent physical properties of the olefinic resins are not maintained in the graft modified product.
In addition, the introduction of polar functional groups by copolymerization techniques has been studied as means for improving adhesion, but conventionally, means for copolymerizing olefins and comonomers having polar functional groups (polar comonomers) are limited to radical polymerization methods. (Patent Document 1 and Patent Document 2). In the copolymer, only a copolymer having many branched structures, a low elastic modulus and low mechanical properties could be obtained, and its application range was limited.

On the other hand, in the conventional polymerization method using a metallocene catalyst, when copolymerizing ethylene and a polar group-containing monomer, it has been said that the catalytic polymerization activity is reduced and the copolymerization is difficult. Attempts to improve physical properties by producing linear copolymers with few branches by copolymerization of olefins and polar comonomers using post-transition metal complex catalysts called postmetallocenes. It has been.
So far, acrylic acid esters (patent documents 3 to 8), acrylonitrile (non-patent document 1), vinyl ether (non-patent document 2) and the like have been reported as polar comonomers. Copolymerization using a polar comonomer having a norbornene skeleton has also been reported (Non-Patent Document 3). However, as a result of evaluation by the inventors of the present application, their performance was insufficient (particularly in terms of adhesion, See Examples). In addition, although the manufacturing method of the multi-component copolymer by a norbornene polar comonomer is reported (patent document 9), it is restricted to manufacture of the acrylate copolymer with a low olefin content by a radical polymerization catalyst.

  In addition, a large number of special reaction aids are required for introducing a polar group, a unique and complicated reaction route is used, and a method using a special expensive unsaturated monomer has been proposed. In either case, the production process is not economical, and the adhesiveness of the polyolefin is not improved.

  In view of the above prior art, development of a polar group-containing olefin copolymer produced by a simple and efficient polymerization method and having sufficiently improved adhesive performance without impairing mechanical properties and other physical properties has been developed. The desire is clear.

Japanese Patent No. 2792982 JP-A-3-229713 Special table 2002-521534 gazette JP-A-6-184214 Japanese Patent Laid-Open No. 2008-223011 JP 2010-150246 A JP 2010-150532 A JP 2010-202647 A Special table 2009-535444

K. Nozaki et al. , J .; Am. Chem. Soc. 2007, 129, 8948-8949. R. Jordan et al. , J .; Am. Chem. Soc. 2007, 129, 8946-8947. A. Sen et al. , Organometallics, 2007, 26, 210-216.

  The problem to be solved by the present invention is based on the background art, is produced by a simple and efficient polymerization method, and the adhesive properties are sufficiently improved without impairing mechanical properties and other physical properties. It is to provide an olefin copolymer.

With the aim of solving the problems of the present invention described above, the present inventors have attempted to produce the copolymer by a simple and efficient production method in the production of the polar group-containing olefin copolymer, and a method for introducing the polar group In addition, various verifications and searches were conducted on the selection of a polymerization catalyst, a polar monomer, and a multi-element monomer.
As a result, a multi-component monomer including a specific polar comonomer as a monomer component is selected, and a multi-component copolymer including a polar comonomer having a norbornene skeleton as the polar monomer component is found to solve the above problem. The invention has been completed.
Moreover, it has also been found that the use of a complex having a specific structure as a polymerization catalyst makes it possible to easily obtain the above-mentioned multi-component copolymer, leading to the creation of an invention as a production method.

  In the present invention created as described above, the multi-component polar olefin copolymer having the specific structure is a novel compound constituting the first invention (basic invention) of the present invention, and has ethylene and / or 3 carbon atoms. 10-α-olefin (nonpolar monomer; X1) and two or more kinds of monomers Z1 and Z2 represented by the following formula. (However, there are 3 or more types of monomer units used as X1, Z1, and Z2.) The expression “consisting of” does not exclude monomers other than the above three types of monomers.

  The outline of each subordinate invention, which is an embodiment invention that follows the above-mentioned basic invention of the present invention or an invention of a supplementary manufacturing method, is described in order, the second invention specifies the amounts of monomers Z1 and Z2, The third invention specifies the molecular weight of the copolymer, the fourth invention specifies the degree of methyl branching per 1,000 carbons of the copolymer, the fifth invention defines X1, the sixth and seventh inventions Defines T1 and T2 in the monomer Z1, the eighth invention specifies the monomer Z2, the ninth invention defines the molar ratio of the monomers Z1 and Z2, and the tenth and eleventh inventions The Mw / Mn and melting point of the polymer are defined, the twelfth to fourteenth inventions relate to transition metal catalysts, and the fifteenth invention relates to a method for producing a copolymer.

  The present invention is a polar group-containing olefin copolymer having a novel structure which is produced by a simple and efficient polymerization method and has sufficiently improved adhesion performance without impairing mechanical properties and other physical properties. Such a feature cannot be obtained from the conventional patent literature.

In the above, the background of the creation of the present invention and the basic configuration and features of the invention have been described in general. Here, the overall configuration of the present invention will be summarized and summarized as follows. ] To [15] invention unit group.
Here, the multi-component polar olefin copolymer having a specific structure in [1] is configured as a basic invention [1], and [2] each of the following inventions adds an additional requirement to the basic invention, or The embodiment is shown. The inventions [12] to [15] define additional requirements for the production method of the multi-component polar olefin copolymer having the specific structure of the present invention. All invention units are collectively referred to as an invention group.

  [1] One or two or more nonpolar monomer (X1) units selected from ethylene and an α-olefin having 3 to 10 carbon atoms and one or two or more selected from a compound represented by the general formula (1) And a polar monomer (Z1) unit, and optionally, one or more polar monomer (Z2) units selected from the compound represented by the general formula (2). Copolymer (however, the number of monomer units used as X1, Z1, and Z2 is 3 or more).

  [Monomer Z1 is selected from the group consisting of general formula (1). In general formula (1), T1 and T2 are a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydroxyl group, and a hydroxyl group. A substituted hydrocarbon group having 1 to 10 carbon atoms, a hydrocarbon group having 2 to 20 carbon atoms substituted with an alkoxy group having 1 to 10 carbon atoms, and 3 carbon atoms substituted with an ester group having 2 to 10 carbon atoms Hydrocarbon group having 1 to 20 carbon atoms, hydrocarbon group having 4 to 20 carbon atoms substituted with a silyl group having 3 to 18 carbon atoms, hydrocarbon group having 1 to 10 carbon atoms substituted with a halogen atom, 1 to 10 carbon atoms Alkoxy group, carbon number 6-20 aryloxy group, carboxyl group, carbon number 2-10 ester group, carbon number 2-10 acyloxy group, amino group, carbon number 1-12 substituted amino group, carbon number 3 ~ 18 silyl group and halogen? A substituent selected from the group consisting of: a hydroxyl group, a C 1-10 hydrocarbon group substituted with a hydroxyl group, and a C 2-20 substituted with a C 1-10 alkoxy group A hydrocarbon group, a hydrocarbon group having 3 to 20 carbon atoms substituted with an ester group having 2 to 10 carbon atoms, a hydrocarbon group having 4 to 20 carbon atoms substituted with a silyl group having 3 to 18 carbon atoms, a halogen atom A hydrocarbon group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, a carboxyl group, an ester group having 2 to 10 carbon atoms, and an ester group having 2 to 10 carbon atoms. The substituent selected from the group which consists of an acyloxy group, an amino group, a C1-C12 substituted amino group, a C3-C18 silyl group, and a halogen is shown. T1 and T2 may be connected to form an annular structure.

  The monomer Z2 is selected from the group consisting of the general formula (2). In the general formula (2), T3 is a hydrocarbon group having 1 to 10 carbon atoms substituted with a hydroxyl group, or 1 to 10 carbon atoms. Substituted with an alkoxy group of 2 to 20 carbon atoms, a hydrocarbon group of 3 to 20 carbon atoms substituted with an ester group of 2 to 10 carbon atoms, and a silyl group of 3 to 18 carbon atoms. Hydrocarbon group having 4 to 20 carbon atoms, hydrocarbon group having 1 to 10 carbon atoms substituted with a halogen atom, alkoxy group having 1 to 10 carbon atoms, aryloxy group having 6 to 20 carbon atoms, carboxyl group, carbon number Substituents selected from the group consisting of 2 to 10 ester groups, C2 to C10 acyloxy groups, amino groups, C1 to C12 substituted amino groups, C3 to C18 silyl groups, and halogens Indicates. ]

[2] The multi-component polar olefin copolymer according to [1], wherein the total amount of monomer units derived from Z1 and Z2 is 0.001 to 10.000 mol%.
[3] The multiple according to claim 1 or 2, wherein the weight average molecular weight (Mw) determined by gel permeation chromatography (GPC) is in the range of 20,000 to 1,000,000. Polar olefin copolymer.
[4] The multi-component polar olefin copolymer in [1] to [3], wherein the methyl branching degree calculated by ¹³ C-NMR is 5.0 or less per 1,000 carbons of the copolymer.
[5] The multi-component polar olefin copolymer in [1] to [4], wherein X1 is a kind of nonpolar monomer.
[6] The multi-component polar olefin copolymer in [1] to [5], wherein T1 and T2 in Z1 are acid anhydride groups linked to each other by T1 and T2 to form a cyclic structure .

[7] The multi-component polar olefin copolymer in [1] to [6], wherein in Z1, T1 and T2 are both carboxyl groups.
[8] The multi-component polar olefin copolymer in [1] to [7], wherein Z2 is contained as an essential monomer unit, and T3 is an ester group having 2 to 10 carbon atoms in Z2.
[9] The multi-component polar olefin copolymer in [1] to [8], wherein the molar ratio of the monomer Z1 to the monomer Z2 in the copolymer is 0.001 to 10.000.
[10] The ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) determined by gel permeation chromatography (GPC) is in the range of 1.5 to 3.5, [1 ] The multi-component polar olefin copolymer in [9].
[11] The multi-component polar olefin copolymer in [1] to [10], wherein the melting point is 50 ° C to 140 ° C.

[12] The multi-component polar olefin copolymer according to [1] to [11], which is polymerized in the presence of a Group 5-10 transition metal catalyst having a chelating ligand.
[13] The multi-component polar olefin copolymer according to [12], wherein the transition metal catalyst is a transition metal catalyst in which a triarylphosphine or a triarylarsine compound is coordinated to palladium metal.
[14] The multipolar polar olefin copolymer according to [13], wherein the triarylphosphine or the triarylarsine compound has a phenyl group substituted with at least one secondary or tertiary alkyl group .
[15] The multi-component polar olefin copolymer according to any one of [1] to [11], which is polymerized in the presence of a Group 5-10 transition metal catalyst having a chelating ligand Manufacturing method.

  In the present invention, it is possible to provide a polar group-containing olefin copolymer which is produced by a simple and efficient polymerization method and has sufficiently improved adhesive performance without impairing mechanical properties and other physical properties.

  In the following, the multi-component polar olefin copolymer and the ternary monomer of the present invention, and the production method and use of the copolymer will be described specifically and in detail for each item.

1. Monomer (1) Nonpolar Monomer X1 of the Present Invention
The nonpolar monomer X1 used in the present invention is selected from ethylene and / or an α-olefin having 3 to 10 carbon atoms.
Preferable specific examples include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 3-methyl-1-butene and 4-methyl-1-pentene. A specific example is ethylene. Moreover, X1 may use 1 type and may use 2 or more types together.
Examples of the two combinations include ethylene / propylene, ethylene / 1-butene, ethylene / 1-hexene, ethylene / 1-octene, propylene / 1-butene, propylene / 1-hexene, propylene / 1-octene and the like. . Preferably, the combination containing ethylene is mentioned.
Examples of the three combinations include ethylene / propylene / 1-butene, ethylene / propylene / 1-hexene, ethylene / propylene / 1-octene, propylene / 1-butene / hexene, propylene / 1-butene / 1-octene, and the like. It is done. Preferably, the combination containing ethylene is mentioned.

(2) Monomer Z1
The monomer Z1 used in the present invention is a polar comonomer selected from the compound represented by the general formula (1).

  In general formula (1), T1 and T2 are a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydroxyl group, a hydrocarbon group having 1 to 10 carbon atoms substituted with a hydroxyl group, and an alkoxy group having 1 to 10 carbon atoms. C 2-20 hydrocarbon group substituted with, C 3-20 hydrocarbon group substituted with C 2-10 ester group, carbon number substituted with C 3-18 silyl group 4-20 hydrocarbon group, C1-C10 hydrocarbon group substituted with a halogen atom, C1-C10 alkoxy group, C6-C20 aryloxy group, carboxyl group, C2-C10 A substituent selected from the group consisting of an ester group, an acyloxy group having 2 to 10 carbon atoms, an amino group, a substituted amino group having 1 to 12 carbon atoms, a silyl group having 3 to 18 carbon atoms, and a halogen; At least one is a hydroxyl group or a hydroxyl group A substituted hydrocarbon group having 1 to 10 carbon atoms, a hydrocarbon group having 2 to 20 carbon atoms substituted with an alkoxy group having 1 to 10 carbon atoms, and 3 carbon atoms substituted with an ester group having 2 to 10 carbon atoms Hydrocarbon group having 1 to 20 carbon atoms, hydrocarbon group having 4 to 20 carbon atoms substituted with a silyl group having 3 to 18 carbon atoms, hydrocarbon group having 1 to 10 carbon atoms substituted with a halogen atom, 1 to 10 carbon atoms Alkoxy group, carbon number 6-20 aryloxy group, carboxyl group, carbon number 2-10 ester group, carbon number 2-10 acyloxy group, amino group, carbon number 1-12 substituted amino group, carbon number 3 The substituent selected from the group which consists of -18 silyl groups and a halogen is shown. T1 and T2 may form a ring structure. Z1 may use 1 type, or may use 2 or more types.

(3) Monomer Z2
Monomer Z2, which is an optional component, is a polar comonomer selected from the group consisting of compounds represented by formula (2). Z2 may use a plurality of monomer components.

  In the general formula (2), T3 is a hydrocarbon group having 1 to 10 carbon atoms substituted with a hydroxyl group, a hydrocarbon group having 2 to 20 carbon atoms substituted with an alkoxy group having 1 to 10 carbon atoms, or 2 carbon atoms. 3 to 20 hydrocarbon groups substituted with 10 to 10 ester groups, 4 to 20 hydrocarbon groups substituted with 3 to 18 silyl groups, 1 carbon atom substituted with halogen atoms -10 hydrocarbon group, C1-C10 alkoxy group, C6-C20 aryloxy group, carboxyl group, C2-C10 ester group, C2-C10 acyloxy group, amino group, carbon A substituent selected from the group consisting of a substituted amino group having 1 to 12 carbon atoms, a silyl group having 3 to 18 carbon atoms, and a halogen is shown.

(4) Specific description of each monomer T1, T2, and T3 in Z1 and Z2 are described in detail below. T1 and T2 which are hydrocarbon groups having 1 to 20 carbon atoms are preferably an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, and 6 carbon atoms. ˜20 aryl groups.

  Here, examples of the alkyl group having 1 to 20 carbon atoms and the cycloalkyl group having 3 to 20 carbon atoms include a methyl group, an ethyl group, a 1-propyl group, a 1-butyl group, a 1-pentyl group, and a 1-hexyl group. 1-heptyl group, 1-octyl group, 1-nonyl group, 1-decyl group, t-butyl group, tricyclohexylmethyl group, isopropyl group, 1-dimethylpropyl group, 1,1,2-trimethylpropyl group, 1,1-diethylpropyl group, isobutyl group, 1,1-dimethylbutyl group, 2-pentyl group, 3-pentyl group, 2-hexyl group, 3-hexyl group, 2-ethylhexyl group, 2-heptyl group, 3 -Heptyl group, 4-heptyl group, 2-propylheptyl group, 2-octyl group, 3-nonyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, methylcyclopentyl group, Chlohexyl group, methylcyclohexyl group, cycloheptyl group, cyclooctyl group, cyclododecyl group, 1-adamantyl group, 2-adamantyl group, exo-norbornyl group, endo-norbornyl group, 2-bicyclo [2.2.2] octyl Group, nopinyl group, decahydronaphthyl group, menthyl group, neomenthyl group, neopentyl group, 5-decyl group and the like. Among these, preferred substituents are a methyl group and an ethyl group.

  Examples of the alkenyl group having 2 to 20 carbon atoms include vinyl group, allyl group, butenyl group, cinnamyl group, and styryl group. Among these, preferred substituents are a vinyl group and a styryl group, and particularly preferred is a styryl group.

  Examples of the aryl group having 6 to 20 carbon atoms include a phenyl group, a naphthyl group, an anthracenyl group, and a fluorenyl group. Examples of the substituent that can be present in the aromatic ring of these aryl groups include an alkyl group, an aryl group, A fused aryl group, a phenylcyclohexyl group, a phenylbutenyl group, a tolyl group, a xylyl group, a p-ethylphenyl group, and the like. Of these, a preferred aryl group is a phenyl group.

T1, T2, and T3 which are hydrocarbon groups having 1 to 10 carbon atoms substituted with a hydroxyl group are preferably the aforementioned alkyl groups having 1 to 10 carbon atoms, cycloalkyl groups having 1 to 10 carbon atoms, and 1 carbon atom. -10 alkenyl groups and hydroxyl group-substituted products of aryl groups having 1 to 10 carbon atoms.
Preferred examples are hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group, 1-hydroxy-n-propyl group, 2-hydroxy-n-propyl group, 3-hydroxy-n-propyl group, 1- Hydroxy-isopropyl group, 2-hydroxy-isopropyl group, 2,2′-dihydroxy-isopropyl group, 1-hydroxy-n-butyl group, 2-hydroxy-n-butyl group, 3-hydroxy-n-butyl group, 4 -Hydroxy-n-butyl group, 1-hydroxy-1-methyl-propyl group, 1-hydroxy-2-methyl-propyl group, 2-hydroxy-1-methyl-propyl group, 2-hydroxy-2-methyl-propyl group Group, 3-hydroxy-1-methyl-propyl group, 3-hydroxy-2-methyl-propyl group, 3-hydroxy-3-methyl group Of these, a hydroxymethyl group, a 1-hydroxyethyl group, and a 2-hydroxyethyl group are preferable, and a hydroxymethyl group and a 1-hydroxyethyl group are particularly preferable.

T1, T2, and T3, which are hydrocarbon groups having 2 to 20 carbon atoms substituted with an alkoxy group having 1 to 10 carbon atoms, are preferably the above-mentioned alkyl group, cycloalkyl group, alkenyl group, and aryl group are substituted with methoxy. Group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, or a t-butoxy group.
More preferably, it is a C2-C6 hydrocarbon group substituted by a methoxy group or an ethoxy group, and specifically includes 1- (methoxymethyl) ethyl group, 1- (ethoxymethyl) ethyl group, 1- ( Phenoxymethyl) ethyl group, 1- (methoxyethyl) ethyl group, 1- (ethoxyethyl) ethyl group, di (methoxymethyl) methyl group, di (ethoxymethyl) methyl group, di (phenoxymethyl) methyl group .
Particularly preferred are 1- (methoxymethyl) ethyl group and 1- (ethoxymethyl) ethyl group.

  T1, T2, and T3, which are hydrocarbon groups having 3 to 20 carbon atoms substituted with an ester group having 2 to 10 carbon atoms, are preferably the above-described alkyl group, cycloalkyl group, alkenyl group, and aryl group. It is a substituent substituted with a carbonyl group, an ethoxycarbonyl group, an isopropoxycarbonyl group, a 1-propoxycarbonyl group, a 1-butoxycarbonyl group, a t-butoxycarbonyl group, or a phenoxycarbonyl group. More preferably, it is a C3-C5 hydrocarbon group substituted by a methoxycarbonyl group or an ethoxycarbonyl group, specifically, a 1- (methoxycarbonyl) methyl group, 2- (methoxycarbonyl) ethyl group, 1 -(Ethoxycarbonyl) methyl group, 2- (ethoxycarbonyl) ethyl group may be mentioned. More preferably, it is a 1- (methoxycarbonyl) methyl group or a 1- (ethoxycarbonyl) methyl group.

  Preferred specific examples of T1, T2, and T3 which are hydrocarbon groups having 4 to 20 carbon atoms substituted with silyl groups having 3 to 18 carbon atoms are (trimethylsilyl) methyl group, ((dimethyl) (phenyl) silyl) methyl Group, ((diphenyl) (methyl) silyl) methyl group, (triphenylsilyl) methyl group, bis (trimethylsilyl) methyl group. Among these, more preferred substituents include (trimethylsilyl) methyl group and bis (trimethylsilyl) methyl group.

  T1, T2, and T3, which are hydrocarbon groups having 1 to 10 carbon atoms substituted with a halogen atom, are preferably substituents having 1 to 6 carbon atoms substituted with fluorine, chlorine, or bromine. Specific preferred examples include a monochloromethyl group, a dichloromethyl group, a trifluoromethyl group, or a pentafluorophenyl group. Among these, more preferred substituents include a monochloromethyl group and a dichloromethyl group.

  T1, T2, and T3, which are alkoxy groups having 1 to 10 carbon atoms, are preferably alkoxy groups having 1 to 6 carbon atoms, and specific examples are methoxy group, ethoxy group, n-propoxy group, and isopropoxy group. , N-butoxy group, t-butoxy group and the like. Among these, a more preferred substituent is a methoxy group, an ethoxy group, or an isopropoxy group, and particularly preferably a methoxy group.

  T1, T2 and T3 which are aryloxy groups having 6 to 20 carbon atoms are preferably aryloxy groups having 6 to 12 carbon atoms, and preferred specific examples thereof are phenoxy group, 4-methylphenoxy group and 4-methoxyphenoxy group. 2,6-dimethylphenoxy group, and 2,6-di-t-butylphenoxy group. Among these, a more preferable substituent is a phenoxy group or a 2,6-dimethylphenoxy group, and a phenoxy group is particularly preferable.

  T1, T2, and T3, which are ester groups having 2 to 10 carbon atoms, are preferably ester groups having 2 to 8 carbon atoms, and preferred specific examples are methoxycarbonyl group, ethoxycarbonyl group, n-propoxycarbonyl group, Examples include an isopropoxycarbonyl group, an n-butoxycarbonyl group, a t-butoxycarbonyl group, a (4-hydroxybutoxy) carbonyl group, a (4-glycidylbutoxy) carbonyl group, and a phenoxycarbonyl group. Among these, more preferred substituents include a methoxycarbonyl group, an ethoxycarbonyl group, a (4-hydroxybutoxy) carbonyl group, and a (4-glycidylbutoxy) carbonyl group, and particularly preferably a methoxycarbonyl group, ( 4-glycidylbutoxy) carbonyl group.

  T1, T2, and T3, which are acyloxy groups having 2 to 10 carbon atoms, are preferably acyloxy groups having 2 to 8 carbon atoms, and preferred specific examples thereof include an acetyl group, a propionyl group, butyryl ( butyryl) group.

  Preferable specific examples of T1, T2 and T3 which are substituted amino groups having 1 to 12 carbon atoms include monomethylamino group, dimethylamino group, monoethylamino group, diethylamino group, monoisopropylamino group, diisopropylamino group and monophenylamino. Group, diphenylamino group, bis (trimethylsilyl) amino group, morpholinyl group. Of these, more preferred substituents are a diphenylamino group and a bis (trimethylsilyl) amino group.

  Preferable specific examples of T1, T2 and T3 which are silyl groups having 3 to 18 carbon atoms are trimethylsilyl group, (dimethyl) (phenyl) silyl group, (diphenyl) (methyl) silyl group and triphenylsilyl group. Of these, a more preferred substituent is a trimethylsilyl group.

  T1, T2 and T3 which are halogens preferably include fluorine, chlorine and bromine. Of these, a more preferred substituent is chlorine.

T1 and T2 may be connected to form an annular structure. Preferable specific examples include a cyclic dicarboxylic acid anhydride structure, a cyclic lactone structure, a cyclic lactam structure, and a cyclic succinimide structure. Among these, more preferable substituents are a cyclic dicarboxylic acid anhydride structure and a cyclic lactone structure, and a cyclic dicarboxylic acid anhydride structure is particularly preferable.
In a copolymer using an unsaturated dicarboxylic acid anhydride as a monomer, a dicarboxylic acid anhydride group contained therein may react with moisture in the air to open a ring, and a part thereof may be a dicarboxylic acid. As long as it does not depart from the gist of the present invention, the dicarboxylic anhydride group may be ring-opened.

2. Copolymer (1) Type of Copolymer The copolymer of the present invention is a copolymer comprising three or more monomer units selected from X1, Z1, and optionally Z2.
Specifically, ethylene / propylene / norbornene-2,3-dicarboxylic acid anhydride, ethylene / 1-butene / norbornene-2,3-dicarboxylic acid anhydride, ethylene / 1-pentene / norbornene-2,3-dicarboxylic acid Acid anhydride, ethylene / 1-hexene / norbornene-2,3-dicarboxylic acid anhydride, ethylene / 1-octene / norbornene-2,3-dicarboxylic acid anhydride, ethylene / 1-decene / norbornene-2,3- Dicarboxylic acid anhydride, ethylene / 3-methyl-1-butene / norbornene-2,3-dicarboxylic acid anhydride, ethylene / 4-methyl-1-pentene / norbornene-2,3-dicarboxylic acid anhydride, ethylene / acrylic Acid methyl / norbornene-2,3-dicarboxylic anhydride, ethylene / ethyl acrylate / norbornene 2,3-dicarboxylic acid anhydride, ethylene / n-butyl acrylate / norbornene-2,3-dicarboxylic acid anhydride, ethylene / isobutyl acrylate / norbornene-2,3-dicarboxylic acid anhydride, ethylene / acrylic acid t -Butyl / norbornene-2,3-dicarboxylic acid anhydride, ethylene / glycidyl acrylate / norbornene-2,3-dicarboxylic acid anhydride, ethylene / acrylic acid (4-glycidyloxybutyl) / norbornene-2,3- Examples include dicarboxylic acid anhydride, ethylene / hydroxyethyl acrylate / norbornene-2,3-dicarboxylic acid anhydride, and the like.

  Further, ethylene / propylene / norbornene-2,3-dicarboxylic acid, ethylene / 1-butene / norbornene-2,3-dicarboxylic acid, ethylene / 1-pentene / norbornene-2,3-dicarboxylic acid, ethylene / 1-hexene / Norbornene-2,3-dicarboxylic acid, ethylene / 1-octene / norbornene-2,3-dicarboxylic acid, ethylene / 1-decene / norbornene-2,3-dicarboxylic acid, ethylene / 3-methyl-1-butene / Norbornene-2,3-dicarboxylic acid, ethylene / 4-methyl-1-pentene / norbornene-2,3-dicarboxylic acid, ethylene / methyl acrylate / norbornene-2,3-dicarboxylic acid, ethylene / ethyl acrylate / norbornene -2,3-dicarboxylic acid, ethylene / n-butyl acrylate / nor Runene-2,3-dicarboxylic acid, ethylene / isobutyl acrylate / norbornene-2,3-dicarboxylic acid, ethylene / t-butyl acrylate / norbornene-2,3-dicarboxylic acid, ethylene / glycidyl acrylate / norbornene-2 , 3-dicarboxylic acid, ethylene / acrylic acid (4-glycidyloxybutyl) / norbornene-2,3-dicarboxylic acid, ethylene / hydroxyethyl acrylate / norbornene-2,3-dicarboxylic acid, and the like.

  Preferred examples include ethylene / 1-hexene / norbornene-2,3-dicarboxylic acid anhydride, ethylene / methyl acrylate / norbornene-2,3-dicarboxylic acid anhydride, ethylene / ethyl acrylate / norbornene- 2,3-dicarboxylic acid anhydride, ethylene / glycidyl acrylate / norbornene-2,3-dicarboxylic acid anhydride, ethylene / acrylic acid (4-glycidyloxybutyl) / norbornene-2,3-dicarboxylic acid anhydride, etc. Is mentioned.

(2) Controlling the amount of polar monomer The copolymer in the present invention preferably has a structural unit amount derived from monomers of Z1 and Z2 in the copolymer of 0.001 to 10.000 mol%. Among these, it is preferable to select in the range of 0.010-5.000 mol%. Moreover, it is preferable that the molar ratio of the monomer Z1 and the monomer Z2 in the copolymer is in the range of 0.001 to 10.000. Of these, the range of 0.001 to 1.000 is more preferable, and the range of 0.001 to 0.500 is particularly preferable.
In the copolymer of the present invention, the amount of structural units derived from the monomers Z1 and Z2 contained in the molecular chain is preferably larger than the amount of structural units derived from the monomers Z1 and Z2 contained at the ends of the molecular chain. .

When the copolymer in the present invention satisfies the above-described conditions, a material having excellent adhesive strength can be provided. As will be described later, in order to have sufficient adhesiveness, it is preferable to have a molecular weight in a specific range and make the molecular weight and the polar monomer content compatible. For that purpose, it is preferable that the amount of the polar monomer structural unit is larger in the molecular chain than in the molecular chain terminal.
In controlling the amount of the polar monomer structural unit, the molar ratio of the monomers Z1 and Z2 should be controlled by the amount ratio of the monomers Z1 and Z2 added during the polymerization, the selection of the transition metal catalyst, and the pressure and temperature during the polymerization. Is possible.

(3) Physical Properties The copolymer in the present invention preferably has a methyl branching degree calculated by ¹³ C-NMR of 5.0 or less per 1,000 carbons of the copolymer. Among these, 3.0 or less per 1,000 carbons of the copolymer is particularly preferable. When the methyl branch satisfies this value, the elastic modulus is high and the mechanical strength of the molded body is also high.
This methyl branching degree can be controlled by selection of the transition metal catalyst to be used and the polymerization temperature. As a specific means for reducing the degree of methyl branching of the copolymer, it is effective to lower the polymerization temperature. For example, these factors can be adjusted to control the desired copolymer region.

The copolymer in the present invention has a weight average molecular weight (Mw) to number average molecular weight (Mn) ratio (molecular weight distribution) determined by gel permeation chromatography (GPC) in the range of 1.5 to 3.5. Preferably there is. Among these, the range of 1.6 to 3.3 is more preferable, and the range of 1.7 to 3.0 is particularly preferable.
The copolymer in the present invention preferably has a weight average molecular weight (Mw) determined by gel permeation chromatography (GPC) of 20,000 to 1,000,000. Of these, the range of 45,000 to 500,000 is more preferable, and the range of 50,000 to 300,000 is particularly preferable.
When the molecular weight of the copolymer in the present invention satisfies the above-mentioned conditions, various workability including the molding of a laminate is sufficient, and further, a material having superior adhesive strength by being compatible with the above-mentioned polar monomer structural unit amount. Can be provided. The molecular weight and molecular weight distribution can be controlled by selection of the transition metal catalyst and the pressure and temperature during polymerization.

The copolymer in the present invention preferably has a melting point of 50 ° C to 140 ° C. Among these, 60 to 138 ° C. is particularly preferable, and 70 to 135 ° C. is more preferable. When this range is satisfied, heat resistance and adhesiveness are excellent.
This melting point can be controlled by selecting the transition metal catalyst to be used and the amount of monomer added during polymerization.

3. Production method of copolymer (1) Transition metal catalyst As an example of the production method of the polar group-containing olefin copolymer of the present invention, a group 5-10 transition metal compound having a chelating ligand is used as a catalyst. There is a way to polymerize.
Specific examples of preferable transition metals include vanadium atom, niobium atom, tantalum atom, chromium atom, molybdenum atom, tungsten atom, manganese atom, iron atom, ruthenium atom, cobalt atom, rhodium atom, nickel atom, palladium atom and the like. . Among these, vanadium atom, iron atom, cobalt atom, nickel atom and palladium atom are preferable, and nickel atom and palladium atom are particularly preferable. These metals may be single or plural.

  The chelating ligand has at least two atoms selected from the group consisting of P, N, O, and S and is bidentate or multidentate. It contains a ligand and is electronically neutral or anionic. The structure is illustrated in a review by Brookhart et al. (Chem. Rev., 2000, 100, 1169).

  Preferably, examples of the bidentate anionic P and O ligand include phosphorus sulfonic acid, phosphorus carboxylic acid, phosphorus phenol, and phosphorus enolate, and other examples of the bidentate anionic N and O ligand include salicyl. Examples include aldoiminate and pyridinecarboxylic acid, and other examples include diimine ligands, diphenoxide ligands, and diamide ligands.

Here, as a representative group 5-10 transition metal compound having a chelating ligand, for example, so-called phosphine phenolate and phosphine sulfonate catalysts are known. The phosphine phenolate catalyst is a catalyst in which a phosphorus ligand having an aryl group which may have a substituent is coordinated to nickel metal (for example, JP-A-201 201
0-260913). The phosphine phenolate-based catalyst is also used in the examples of the present invention, and is a catalyst in which a phosphorus-based ligand having an aryl group which may have a substituent is coordinated to nickel or palladium metal (for example, a special catalyst). Open 2010-20264
In particular, it is preferable that at least one of the triarylphosphine or the triarylarsine compound has a phenyl group substituted with a secondary or tertiary alkyl group (for example, JP 2010-150246 A). Issue no.).

(2) Use Mode of Polymerization Catalyst The polymerization catalyst of the present invention may be used alone or may be used by being supported on a carrier. As a usable carrier, any carrier can be used as long as the gist of the present invention is not impaired.
In general, inorganic oxides and polymer carriers can be preferably used. Specific examples include SiO ₂ , Al ₂ O ₃ , MgO, ZrO ₂ , TiO ₂ , B ₂ O ₃ , CaO, ZnO, BaO, ThO ₂ , or a mixture thereof, and SiO ₂ —Al ₂ O _3. , SiO ₂ —V ₂ O ₅ , SiO ₂ —TiO ₂ , SiO ₂ —MgO, SiO ₂ —Cr ₂ O ₃ and other mixed oxides can also be used, inorganic silicate, polyethylene carrier, polypropylene carrier, A polystyrene carrier, polyacrylic acid carrier, polymethacrylic acid carrier, polyacrylic acid ester carrier, polyester carrier, polyamide carrier, polyimide carrier and the like can be used.
These carriers are not particularly limited in particle size, particle size distribution, pore volume, specific surface area, etc., and any one can be used.

  The catalyst component may be prepolymerized in the presence of olefin in the polymerization tank or outside the polymerization tank. Olefin means a hydrocarbon containing at least one carbon-carbon double bond, and examples thereof include ethylene, propylene, 1-butene, 1-hexene, 3-methylbutene-1, styrene, divinylbenzene, and the like. There is no restriction | limiting, You may use the mixture of these and another olefin. Preferred are olefins having 2 or 3 carbon atoms. The olefin can be supplied by any method, such as a supply method for maintaining the olefin at a constant speed or in a constant pressure state, a combination thereof, or a stepwise change.

(3) Copolymerization reaction The copolymerization reaction in the present invention may be carried out using hydrocarbon solvents such as propane, n-butane, isobutane, n-hexane, n-heptane, toluene, xylene, cyclohexane, methylcyclohexane, and liquefied α-olefins. Liquid or in the presence or absence of polar solvents such as diethyl ether, ethylene glycol dimethyl ether, tetrahydrofuran, dioxane, ethyl acetate, methyl benzoate, acetone, methyl ethyl ketone, formylamide, acetonitrile, methanol, isopropyl alcohol, ethylene glycol, etc. Done below. Moreover, you may use the mixture of the liquid compound described here as a solvent. In addition, in order to obtain high polymerization activity and high molecular weight, the above-mentioned hydrocarbon solvent is more preferable.

In the copolymerization in the present invention, the copolymerization can be carried out in the presence or absence of a known additive. As the additive, a radical polymerization inhibitor or an additive having an action of stabilizing the produced copolymer is preferable. Examples of preferable additives include quinone derivatives and hindered phenol derivatives.
Specifically, monomethyl ether hydroquinone, 2,6-di-t-butyl 4-methylphenol (BHT), reaction product of trimethylaluminum and BHT, reaction product of alkoxide of tetravalent titanium and BHT, etc. Can be used.
Further, as an additive, inorganic and / or organic fillers may be used and polymerization may be performed in the presence of these fillers.

In the present invention, the polymerization mode is not particularly limited. Slurry polymerization in which at least a part of the produced polymer becomes a slurry in the medium, bulk polymerization using the liquefied monomer itself as a medium, gas phase polymerization performed in the vaporized monomer, or a polymer produced in the monomer liquefied at high temperature and high pressure High-pressure ionic polymerization in which at least a part of the polymer is dissolved is preferably used.
Further, the polymerization mode may be any of batch polymerization, semi-batch polymerization, and continuous polymerization.

  Unreacted monomers and media may be separated from the produced copolymer and recycled. In recycling, these monomers and media may be purified and reused, or may be reused without purification. Conventionally known methods can be used to separate the produced copolymer from the unreacted monomer and medium. For example, methods such as filtration, centrifugation, solvent extraction, and reprecipitation using a poor solvent can be used.

There are no particular restrictions on the copolymerization temperature, copolymerization pressure, and copolymerization time, but usually optimum settings can be made in consideration of productivity and process capability from the following ranges.
That is, the copolymerization temperature is usually −20 ° C. to 290 ° C., preferably 0 ° C. to 250 ° C., the copolymerization pressure is 0.1 MPa to 100 MPa, preferably 0.3 MPa to 90 MPa, and the copolymerization time is 0.00. It can be selected from the range of 1 minute to 10 hours, preferably 0.5 minutes to 7 hours, more preferably 1 minute to 6 hours.
In the present invention, the copolymerization is generally performed in an inert gas atmosphere. For example, a nitrogen or argon atmosphere can be used, and a nitrogen atmosphere is preferably used. A small amount of oxygen or air may be mixed.

  There are no particular limitations on the supply of catalyst and monomer to the copolymerization reactor, and various supply methods can be employed depending on the purpose. For example, in the case of batch polymerization, it is possible to take a technique in which a predetermined amount of monomer is supplied to a copolymerization reactor in advance and a catalyst is supplied thereto. In this case, an additional monomer or an additional catalyst may be supplied to the copolymerization reactor. In the case of continuous polymerization, a method in which a predetermined amount of monomer and catalyst are continuously or intermittently supplied to the copolymerization reactor to carry out the copolymerization reaction continuously can be employed.

  Regarding the control of the copolymer composition, a method of controlling a copolymer by supplying a plurality of monomers to a reactor and changing the supply ratio thereof can be generally used. Other methods include controlling the copolymer composition using the difference in monomer reactivity ratio due to the difference in catalyst structure, and controlling the copolymer composition using the polymerization temperature dependence of the monomer reactivity ratio. .

A conventionally known method can be used for controlling the molecular weight of the copolymer. That is, a method for controlling the molecular weight by controlling the polymerization temperature, a method for controlling the molecular weight by controlling the monomer concentration, a method for controlling the molecular weight by using a chain transfer agent, and a control of the ligand structure in the transition metal complex. For example, controlling the molecular weight.
When a chain transfer agent is used, a conventionally known chain transfer agent can be used. For example, hydrogen, metal alkyl, etc. can be used.

4). Use Mode of Copolymer (1) Additive The multi-component copolymer of the present invention includes an antioxidant, an ultraviolet absorber, a lubricant, an antistatic agent, a colorant, a pigment, a crosslinking agent, a foaming agent, a nucleating agent, a difficult agent. You may mix | blend additives, such as a flame retardant and a filler.

(2) Products used The multi-component copolymer of the present invention can be produced by, for example, injection molding, extrusion molding, blow molding, foam molding, injection molding, film and laminated film, sheet and laminated sheet, fiber, hollow molded article. And can be formed into molded articles such as foam sheets. Among them, since the multi-component copolymer of the present invention has excellent adhesiveness, a layer containing the multi-component copolymer of the present invention and a polyolefin resin such as polyethylene and polypropylene, or a polyamide resin, a polyester resin, ethylene / vinyl acetate. A laminate with other layers such as a thermoplastic resin having a high polarity such as a copolymer resin saponified product (EVOH) and a metal material such as aluminum or steel can also be used.

(3) Modifying agent and compatibilizing agent The polar olefin copolymer of the present invention is a modification of various resins such as polyolefin resin such as polypropylene resin, polyamide resin, polyester resin, polycarbonate resin, acrylic resin, and polyvinyl chloride resin. It can also be suitably used as a compatibilizer for materials or engineering plastics such as polyolefin resins such as polypropylene and polycarbonate resins, polyphenylene ether resins, polyamide resins, polyester resins, polyphenylene sulfide resins, and liquid crystal resins.

(4) Coating material In addition, as other uses, it is used as a coating material for coating a steel pipe coating, a wire coating, a wire coating, a drum can and a tank inner wall coating, or a flame retardant.

  In the following, the present invention will be described in detail by way of examples, and in contrast with comparative examples, the rationality and significance of the configuration of the present invention and the superiority over the prior art will be demonstrated. The ligand structures used in the examples are shown below.

1. Evaluation method (1) Molecular weight and molecular weight distribution (Mw, Mn, Q value)
(Measurement conditions) Model used: 150C manufactured by Waters Inc. Detector: MIRAN1A / IR detector manufactured by FOXBORO (measurement wavelength: 3.42 μm) Measurement temperature: 140 ° C. Solvent: Orthodichlorobenzene (ODCB) Column: AD806M manufactured by Showa Denko KK / S (3) Flow rate: 1.0 mL / min Injection volume: 0.2 mL
(Preparation of sample) A sample was prepared by preparing a 1 mg / mL solution using ODCB (containing 0.5 mg / mL BHT (2,6-di-tert-butyl-4-methylphenol)) at 140 ° C. It took about 1 hour to dissolve.
(Calculation of molecular weight) The standard polystyrene method was used, and the conversion from the retention capacity to the molecular weight was performed using a calibration curve prepared in advance with standard polystyrene. Standard polystyrenes used are brands manufactured by Tosoh Corporation, and are F380, F288, F128, F80, F40, F20, F10, F4, F1, A5000, A2500, and A1000. A calibration curve was prepared by injecting 0.2 mL of a solution dissolved in ODCB (containing 0.5 mg / mL BHT) so that each would be 0.5 mg / mL. The calibration curve used was a cubic equation obtained by approximation by the least square method. The following numerical values were used for the viscosity formula [η] = K × M ^α used for conversion to molecular weight.
PS: K = 1.38 × 10 ⁻⁴ , α = 0.7
PE: K = 3.92 × 10 ⁻⁴ , α = 0.733
PP: K = 1.03 × 10 ⁻⁴ , α = 0.78

(2) Melting point (Tm)
Using a DSC6200 differential scanning calorimeter manufactured by Seiko Instruments Inc., the sheet-like sample piece was packed in a 5 mg aluminum pan, heated from room temperature to 200 ° C. at a heating rate of 100 ° C./min, and held for 5 minutes. Thereafter, the temperature was lowered to 20 ° C. at 10 ° C./min for crystallization, and then the temperature was raised to 200 ° C. at 10 ° C./min to obtain a melting curve.
The peak top temperature of the main endothermic peak in the final temperature increase step performed to obtain the melting curve was defined as the melting point Tm, and the peak area of the peak was defined as ΔHm.

(3) NMR analysis As a solvent, a mixed solvent of orthodichlorobenzene / heavy bromobenzene (4/1) was used. The sample concentration was 150 mg / 2.4 mL. After introducing the sample into the NMR sample tube, the sample was sufficiently purged with nitrogen, and then dissolved in a 130 ° C. heat block to obtain a uniform solution. Measurement was performed at 130 ° C. using a Bruker Avance III Cryo-NMR, 10 mmφ cryoprobe.
Measurement conditions are as follows: ¹ H-NMR: solvent presaturation method, 18 ° pulse, total 256 times; ¹³ C-NMR, proton complete decouple condition, 90 ° pulse, total 512 times.

When using the integrated intensity of ¹ H-NMR spectrum, the quantification of various partial structures is performed by standardizing the integrated intensity of the peak due to the PE main chain of 2 ppm or less to 1,000, and when using the ¹³ C-NMR spectrum, 28 The integrated intensity of the peak due to the PE main chain of ˜31.5 ppm was normalized to 1,000, and calculation was performed according to the following procedure using the integrated intensity values of various characteristic peaks at this time.

[I] A value I _MA obtained by multiplying the methoxy group methyl strength of 3.6 ppm methyl acrylate (MA) by 2/3 in ¹ H-NMR spectrum was determined. Since the total amount of MA was present in an isolated form in the chain, this is approximately the number of MA in the main chain 1,000C.
[Ii] 3 methylene protons single-bonded to oxygen in 3 ppm, 3.3-3.5 ppm, 4.1 ppm (4-glycidyloxybutyl) acrylate (4-HBAGE) in ¹ H-NMR spectrum And a value I _HBAGE obtained by multiplying the sum of peak intensities by one methine proton by 2/7. Since the total amount of 4-HBAGE was isolated in the chain, this was approximately the number of 4-HBAGE in the main chain 1,000C.
[Iii] In the ¹ H-NMR spectrum, I _NB-DCA was determined from the methine proton adjacent to the carbonyl group of 3.1 ppm norbornene-2,3-dicarboxylic anhydride (NB-DCA). This is approximately the number of NB-DCs incorporated into the copolymer for the main chain of 1,000 C (the sum of the isolated type in the main chain and the unsaturated terminal type).
[Iv] The norbornene content is calculated by 3 peaks (33.1, 44.8, and 47.3 ppm) of norbornene when the PE main peak intensity of 28.5 to 31.5 ppm is normalized to 1,000. ) Divided by 5 to obtain _INB . This is approximately the main chain of 1,000
The number of norbornene incorporated in the copolymer relative to 0C.
[V] In the ¹³ C-NMR spectrum, the signal integrated intensity I _Hex by methylene carbon adjacent to the methyl group of 23.4 ppm 1-hexene was determined. This is approximately the main chain of 1,000
The number of 1-hexene incorporated in the copolymer for 0C.
[Vi] The integrated intensity I _Methyl of the signal due to 20.0 ppm methyl-branched methyl carbon was determined by ¹³ C-NMR spectrum. This is the number of methyl branches per 1,000 carbons of the copolymer.

(4) MFR and FR
The MFR was measured at 190 ° C. and a 2.16 kg load according to JIS K6760. The FR (flow rate ratio) was calculated from the ratio of MFR _{10 kg} and MFR (= MFR _{10 kg} / MFR), which was MFR similarly measured at 190 ° C. under a load of 10 kg.

(5) Density The density was measured by a density gradient tube method after the strand obtained at the time of MFR measurement was heat-treated at 100 ° C. for 1 hour and further left at room temperature for 1 hour in accordance with JIS K7112.

(6) Adhesive strength Adhesive strength is measured through the following steps.
[I] A copolymer press plate and an EVOH film are prepared.
[Ii] A laminate is prepared by superposing and pressing a copolymer press plate and an EVOH film.
[Iii] A peel test of the laminate is performed.
Each step will be described below.

(Preparation method of polar group-containing olefin copolymer resin plate)
The copolymer is placed in a hot press mold having dimensions of 50 mm × 60 mm and a thickness of 1 mm, preheated for 5 minutes in a hot press with a surface temperature of 180 ° C., and then remains in the molten resin by repeating pressurization and decompression. The gas was degassed and further pressurized at 4.9 MPa and held for 5 minutes. Then, it transferred to the press machine with a surface temperature of 25 degreeC, it cooled by hold | maintaining for 3 minutes with the pressure of 4.9 Mpa, and produced the copolymer resin board about 0.9 mm thick.

(Method for preparing EVOH film)
Using a multilayer T-die molding machine, a single layer film of EVOH having a thickness of 150 μm was prepared by molding a two-layer three-layer film having EVOH as the center layer and LLDPE as both outer layers, and then peeling the LLDPE as the outer layer. The film forming conditions are as follows.
Molding machine: 2 types, 3 layers T die Molding temperature: 200 ° C. Layer structure: LLDPE / EVOH / LLDPE Film thickness: 350 μm (100 μm / 150 μm / 100 μm) Outer layer: LLDPE (manufactured by Nippon Polyethylene Co., Ltd. Brand: Novatec UF943, MFR = 2.0 g / 10 min, density = 0.937 / cm ³ ) Intermediate layer: EVOH (manufactured by Kuraray Co., Ltd. Brand: EVAL F101B)

(Method for preparing laminate)
The copolymer resin plate obtained by the above resin plate preparation method and the EVOH film obtained by the above EVOH film preparation method cut into 50 mm × 60 mm dimensions are superposed, dimensions: 50 mm × 60 mm, It put into the mold for 1 mm thick hot presses, and it pressurized for 4 minutes at 4.9 MPa using the hot press machine with the surface temperature of 200 degreeC. Then, it transferred to the press machine with a surface temperature of 25 degreeC, it cooled by hold | maintaining for 3 minutes with the pressure of 4.9 Mpa, and the laminated body of the polar group containing olefin copolymer and EVOH was prepared.

(Measurement method of adhesive strength of laminate)
The laminate obtained by the laminate preparation method is cut to a width of 10 mm, and the adhesive strength is measured by T-peeling at a speed of 50 mm / min using a Tensilon (Toyo Seiki Co., Ltd.) tensile tester. did. The unit of adhesive strength is indicated by gf / 10 mm.

2. Ligand synthesis The ligands obtained in the following synthesis examples were used. Unless otherwise specified in the following synthesis examples, the operation was performed in a purified nitrogen atmosphere, and the solvent used was dehydrated and deoxygenated.
Synthesis Example 1 Synthesis of Ligand (I) To a solution of benzenesulfonic anhydride (2 g, 12.6 mmol) in tetrahydrofuran (50 mL) was added a normal butyl lithium hexane solution (2.5 M, 10 mL, 25.3 mmol) to 0. The solution was slowly added dropwise at 0 ° C. and stirred for 1 hour while raising the temperature to room temperature. The reaction solution was cooled to −78 ° C., phosphorus trichloride (1.0 mL, 12.6 mmol) was added, and the mixture was stirred for 2 hours (reaction solution A).
To a solution of 1-bromo-2-cyclohexylbenzene (6 g, 25.3 mmol) in tetrahydrofuran (50 mL), t-butyllithium hexane solution (1.6 M, 31.6 mL, 50.6 mmol) was slowly added dropwise at 0 ° C. Stir for 1 hour. This solution was added dropwise to the previous reaction solution A at −78 ° C. and stirred overnight at room temperature. LC-MS purity 50% / water (200 mL) was added and acidified with hydrochloric acid (PH <3). Extract with methylene chloride (1
00 mL × 3) and drying with sodium sulfate, the solvent was distilled off. Purification by silica gel column chromatography (dichloromethane / methanol = 50/1) gave 1.0 g of a white target product.
¹ H-NMR (CDCl ₃ , ppm): 7.86 (m, 1H), 7.30 (dt, J = 1.2, 7.6 Hz, 1H), 7.24-7.15 (m, 5H ), 6.96 (m, 21H), 6.83 (m, 1H), 6.57 (m, 2H), 3.21 (br, 2H), 1.55 (br, 8H), 1.31 (br, 4H), 1.14 (br, 8H). ³¹ P-NMR (CDCl ₃ , ppm): −28.
7.

Synthesis Example 2 Synthesis of Phosphorussulfonic Acid Ligand (II) To a solution of anhydrous benzenesulfonic acid (2 g, 12.6 mmol) in tetrahydrofuran (20 mL), a normal butyllithium hexane solution (2.5 M, 10 mL, 25.3 mmol). ) Was slowly added dropwise at 0 ° C. and stirred for 1 hour while raising the temperature to room temperature. The reaction solution was cooled to −78 ° C., phosphorus trichloride (1.0 mL, 12.6 mmol) was added, and the mixture was stirred for 2 hours (reaction solution B1).
Magnesium was dispersed in tetrahydrofuran (20 mL), 1-bromo-2-methoxybenzene (2.3 g, 12.6 mmol) was added, and the mixture was stirred at room temperature for 3 hours. This solution was added dropwise to the previous reaction liquid B1 at −78 ° C. and stirred for 1 hour (reaction liquid B2).
To a solution of 1-bromo-2-isopropylbenzene (2.5 g, 12.6 mmol) in diethyl ether (20 mL), slowly add normal butyl lithium hexane solution (2.5 M, 5.0 mL, 12.6 mmol) at −30 ° C. And stirred at room temperature for 2 hours. This solution was added dropwise to the previous reaction solution B2 at −78 ° C. and stirred overnight at room temperature. LC-MS purity 60% / water (50 mL) was added and acidified with hydrochloric acid (PH <3). After extraction with methylene chloride (100 mL) and drying with sodium sulfate, the solvent was distilled off. By recrystallization from methanol, 1.1 g of a white target product was obtained.
¹ H-NMR (CDCl ₃ , ppm): 8.34 (t, J = 6.0 Hz, 1H), 7.7-7.6 (m, 3H), 7.50 (t, J = 6.4 Hz) , 1H), 7.39 (m, 1H), 7.23 (m, 1H), 7.1-6.9 (m, 5H), 3.75 (s, 3H), 3.05 (m, 1H), 1.15 (d, J = 6.8 Hz, 3H), 1.04 (d, J = 6.4 Hz, 3H). ³¹ P-NMR (CDCl ₃ , ppm): −10.5.

3. Polymerization [Example 1] (Ethylene / norbornene-2,3-dicarboxylic anhydride (NB-DCA) / methyl acrylate terpolymer)
In a 30 mL flask thoroughly purged with nitrogen, 200 μmol of bis (dibenzylideneacetone) palladium and phosphorus sulfonic acid ligand (II) were weighed and dehydrated toluene (1
0 mL) was added, and then this was treated with an ultrasonic vibrator for 20 minutes to prepare a catalyst slurry. Next, the inside of the stainless steel autoclave with an induction stirrer with an internal volume of 2.4 L was replaced with purified nitrogen, and methyl acrylate (comonomer concentration 0.2 mol / L), norbornene-2,3-dicarboxylic acid anhydride (comonomer concentration) 0.2 mol / L), purified toluene was introduced into the autoclave under a purified nitrogen atmosphere (total amount 800 mL). The previously prepared catalyst solution was added, and polymerization was started at a polymerization temperature of 80 ° C. and an ethylene pressure of 1 MPa. During the reaction, the temperature was kept constant, and ethylene was continuously supplied so that the pressure was maintained.
After the polymerization was completed, ethylene was purged, the autoclave was cooled to room temperature, the obtained polymer was reprecipitated with acetone (1 L), and the precipitated polymer was filtered. The solid polymer obtained by filtration was washed with acetone and then dried under reduced pressure at 60 ° C. for 3 hours to finally recover the polymer.
Vp · 3.54 × 10 ⁵ g / mol / h; Mw · 87,000; Mw / Mn (Q value) 1.9; Tm · 122.6 ° C .; MFR (2 kg) 1.90 / (10 kg) 12 .6
0; Density • 0.9501; Comonomer content • (Norbornene-2,3-dicarboxylic anhydride) 0.07 mol%, (methyl acrylate) 0.72 mol%; Methyl branching • 0.46

[Example 2] to [Example 5 ], [Reference Example 1] to [Reference Example 2], [Comparative Example 1] to [Comparative Example 3]
A copolymer was produced according to Example 1 except that the conomomer species, comonomer concentration, and polymerization temperature shown in Table 1 were changed. Table 2 summarizes the physical properties evaluation results of the polymer.

4). Consideration of results of Examples and Comparative Examples In Tables 1 and 2, in Examples 1 to 5 , a multi-component (ternary) copolymer containing a polar comonomer as a monomer component, and having a norbornene skeleton as a polar monomer component thereof It was clarified that multi-component copolymers containing polar comonomers can be obtained.
In addition, as a result of the adhesive evaluation, the present invention clearly shows that the adhesiveness is significantly improved with respect to Comparative Examples 1 to 3 that do not use the ternary comonomer of the present invention, and the copolymer according to the present invention is useful. Showed sex.

According to the present invention, it is possible to obtain a multi-component copolymer containing a polar comonomer as a monomer component, and a multi-component copolymer containing a polar comonomer having a norbornene skeleton as the polar monomer component.
Thus, it is possible to provide a novel copolymer that is exceptionally excellent in adhesive performance, and is particularly useful in the industrial field of polyolefin copolymers.

Claims (15)

One or two or more non-polar monomer (X1) units selected from ethylene and an α-olefin having 3 to 10 carbon atoms and one or two or more polar monomers selected from a compound represented by the general formula (1) A multi-component polar olefin copolymer (provided that the unit comprises (Z1) units and one or more polar monomer (Z2) units selected from the compound represented by formula (2)) There are three or more types of monomer units used as X1, Z1, and Z2.)

[Monomer Z1 is selected from the group consisting of general formula (1). In general formula (1), T1 and T2 are a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydroxyl group, and a hydroxyl group. A substituted hydrocarbon group having 1 to 10 carbon atoms, a hydrocarbon group having 2 to 20 carbon atoms substituted with an alkoxy group having 1 to 10 carbon atoms, and 3 carbon atoms substituted with an ester group having 2 to 10 carbon atoms Hydrocarbon group having 1 to 20 carbon atoms, hydrocarbon group having 4 to 20 carbon atoms substituted with a silyl group having 3 to 18 carbon atoms, hydrocarbon group having 1 to 10 carbon atoms substituted with a halogen atom, 1 to 10 carbon atoms Alkoxy group, carbon number 6-20 aryloxy group, carboxyl group, carbon number 2-10 ester group, carbon number 2-10 acyloxy group, amino group, carbon number 1-12 substituted amino group, carbon number 3 ~ 18 silyl group and halogen? A substituent selected from the group consisting of: a hydroxyl group, a C 1-10 hydrocarbon group substituted with a hydroxyl group, and a C 2-20 substituted with a C 1-10 alkoxy group A hydrocarbon group, a hydrocarbon group having 3 to 20 carbon atoms substituted with an ester group having 2 to 10 carbon atoms, a hydrocarbon group having 4 to 20 carbon atoms substituted with a silyl group having 3 to 18 carbon atoms, a halogen atom A hydrocarbon group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, a carboxyl group, an ester group having 2 to 10 carbon atoms, and an ester group having 2 to 10 carbon atoms. The substituent selected from the group which consists of an acyloxy group, an amino group, a C1-C12 substituted amino group, a C3-C18 silyl group, and a halogen is shown. T1 and T2 may be connected to form an annular structure.
The monomer Z2 is selected from the group consisting of the general formula (2). In the general formula (2), T3 is a hydrocarbon group having 1 to 10 carbon atoms substituted with a hydroxyl group, or 1 to 10 carbon atoms. Substituted with an alkoxy group of 2 to 20 carbon atoms, a hydrocarbon group of 3 to 20 carbon atoms substituted with an ester group of 2 to 10 carbon atoms, and a silyl group of 3 to 18 carbon atoms. Hydrocarbon group having 4 to 20 carbon atoms, hydrocarbon group having 1 to 10 carbon atoms substituted with a halogen atom, alkoxy group having 1 to 10 carbon atoms, aryloxy group having 6 to 20 carbon atoms, carboxyl group, carbon number Substituents selected from the group consisting of 2 to 10 ester groups, C2 to C10 acyloxy groups, amino groups, C1 to C12 substituted amino groups, C3 to C18 silyl groups, and halogens Indicates. ] The multi-component polar olefin copolymer according to claim 1, wherein the total amount of monomer units derived from Z1 and Z2 is 0.001 to 10.000 mol%. The multi-component polar olefin according to claim 1 or 2, wherein the weight average molecular weight (Mw) determined by gel permeation chromatography (GPC) is in the range of 20,000 to 1,000,000. Copolymer. The multi-component polar olefin copolymer according to any one of claims 1 to 3, wherein the methyl branching degree calculated by ¹³ C-NMR is 5.0 or less per 1,000 carbons of the copolymer. The multi-component polar olefin copolymer according to any one of claims 1 to 4, wherein X1 is a kind of nonpolar monomer. The multi-component polar olefin copolymer according to any one of claims 1 to 5, wherein in Z1, T1 and T2 are acid anhydride groups linked by T1 and T2 to form a cyclic structure. Polymer. The multi-component polar olefin copolymer according to any one of claims 1 to 5, wherein in Z1, T1 and T2 are both carboxyl groups. Oite to Z2, T3 is equal to or is an ester group having 2 to 10 carbon atoms, multi-polar olefin copolymer according to any one of claims 1 to 7. The multi-component polar olefin copolymer according to any one of claims 1 to 8, wherein a molar ratio of the monomer Z1 to the monomer Z2 in the copolymer is 0.001 to 10.000. Coalescence. The ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) determined by gel permeation chromatography (GPC) is in the range of 1.5 to 3.5, The multi-component polar olefin copolymer according to any one of the above. The multi-component polar olefin copolymer according to any one of claims 1 to 10, wherein the melting point is 50 ° C to 140 ° C. The multi-component polar olefin copolymer according to any one of claims 1 to 11, which is polymerized in the presence of a Group 5-10 transition metal catalyst having a chelating ligand. The multi-component polar olefin copolymer according to claim 12, wherein the transition metal catalyst is a transition metal catalyst in which a triarylphosphine or a triarylarsine compound is coordinated to palladium metal. The multi-component polar olefin copolymer according to claim 13, wherein at least one of the triarylphosphine or the triarylarsine compound has a phenyl group substituted with a secondary or tertiary alkyl group. The multipolar polar olefin copolymer according to any one of claims 1 to 11, which is polymerized in the presence of a Group 5-10 transition metal catalyst having a chelating ligand. Production method.