JP7132087B2 - Olefin copolymer and method for producing the same - Google Patents

Description

TECHNICAL FIELD The present invention relates to an olefin copolymer and a method for producing the same. More particularly, the present invention relates to a novel olefin copolymer having a unique structure obtained by copolymerizing ethylene and/or α-olefin monomers and nitrogen-containing substituted olefin monomers.

Among resin materials, polyolefins represented by polyethylene and polypropylene have excellent properties such as physical properties and moldability. They are also highly economical and environmentally friendly. It is widely used and an important industrial material.
However, since polyolefins are usually non-polar, their physical properties such as adhesiveness with other materials, printability, and compatibility with fillers and the like are insufficient.

Therefore, introduction of polar functional groups into polyolefins has been studied as a means for improving the physical properties, and a method of grafting a polar group-containing monomer using an organic peroxide has been widely practiced. However, in this method, intermolecular cross-linking between olefin-based resins and molecular chain scission of the olefin-based resin occur in parallel with the grafting reaction, so the excellent physical properties of the olefin-based resin are maintained in the graft-modified product. not.

As a means for introducing a polar functional group, copolymerization of an olefin and a polar group-containing olefin monomer (polar comonomer) is also performed. was limited by law (see Patent Document 1 and Patent Document 2). The copolymer has many branched structures, and only copolymers with low elastic modulus and low mechanical properties can be obtained.

On the other hand, in the conventional polymerization method using a metallocene catalyst, it has been believed that the catalytic polymerization activity is lowered and the copolymerization is difficult when an olefin and a polar comonomer are copolymerized. On the other hand, a technique has been reported in which a polar comonomer is reacted with an equimolar or more organoaluminum compound using a metallocene catalyst (functional group masking) and then copolymerized with an olefin. However, in this method, a large amount of aluminum salt is precipitated at the same time as the copolymer is produced, and this method is not popular because of the cost of the organoaluminum compound.

By the way, in recent years, vigorous attempts have been made to copolymerize an olefin and a polar comonomer using a late transition metal complex catalyst, which is called a so-called post-metallocene catalyst, without using a masking agent such as an organoaluminum compound. is underway. So far, as polar comonomers, acrylic acid esters (see Patent Documents 3 to 8), acrylonitrile (see Non-Patent Document 1), vinyl ethers (see Non-Patent Document 2), etc. have been reported.

Considering the development status of olefin-based polar copolymers, α,ω-terminally functionalized olefins are not polymerizable even with late transition metal complex catalysts because the polymerizable olefin sites have a non-conjugated structure. was low and it was difficult to copolymerize with olefins. Accordingly, the present inventors have attempted to produce copolymers of ethylene or α-olefins and α,ω-terminally functionalized olefins using late transition metal complex catalysts.

As a result, we have researched and developed new late transition metal complex catalysts with specific structures, and have found that their catalytic performance is greatly improved. Based on these research results, it was found that by using the developed catalyst, it is possible to copolymerize olefins and α,ω-terminally functionalized olefins, which has been difficult to achieve in the past.

The present inventors have already reported a technique for producing a copolymer of ethylene or an α-olefin and an α,ω-terminally functionalized olefin using a late transition metal complex catalyst (Patent Document 9). reference).

That is, ethylene polymerized in the presence of a Group 5-10 transition metal catalyst having a chelating ligand, particularly a transition metal catalyst in which a triarylphosphine or triarylarsine compound is coordinated to palladium metal. and/or an olefin-based polar copolymer characterized by comprising an α-olefin having 3 to 10 carbon atoms and a polar group-containing olefin monomer selected from a specific monomer group.

Japanese Patent No. 2792982 JP-A-3-229713 Japanese Patent Publication No. 2002-521534 JP-A-6-184214 Japanese Patent Application Laid-Open No. 2008-223011 JP 2010-150246 A JP 2010-150532 A JP 2010-202647 A JP 2013-213121 A

K. Nozaki et al. , J. Am. Chem. Soc. , 2007, 129, 8948-8949. R. Jordan et al. , J. Am. Chem. Soc. , 2007, 129, 8946-8947.

However, the technique described in Patent Document 9 only shows an example using a post-metallocene catalyst, and the development of novel polar olefinic copolymers is desired in order to expand the range of applications of copolymers. was

In addition, it has been desired to develop a polar olefinic copolymer that can be easily converted into a copolymer that has been difficult to synthesize directly. For example, it has been desired to develop a copolymer that can be easily decomposed and converted into a copolymer having an amino group.

SUMMARY OF THE INVENTION It is an object of the present invention to provide novel olefin copolymers with readily degradable protective groups. Another object of the present invention is to provide a method for producing the novel olefin copolymer using a post-metallocene catalyst.

In order to solve the above problems, the present inventors have made intensive studies and found that at least one of ethylene and α-olefin can be obtained by using a nitrogen-containing substituted olefin having a specific substituent even if a post-metallocene catalyst is used. Furthermore, the inventors have found that the nitrogen-containing substituted olefins can be copolymerized satisfactorily. The present inventors have completed the present invention based on these findings.

That is, the first aspect of the present invention provides at least a structural unit (A) containing one
and a structural unit (B) derived from a nitrogen-containing substituted olefin (b-1) represented by the following general formula (3).

[In the general formula (3), X ¹ to X ¹² may be the same or different, a substituent represented by the following general formula (1), a substituent represented by the following general formula (2), A hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 20 carbon atoms, provided that at least one of X ¹ to X ¹² is a substituent represented by the general formula (1) or a substituent represented by the general formula ( It is a substituent represented by 2).
X ⁹ and X ¹⁰ , and X ¹¹ and X ¹² may each be combined to form a divalent organic group, and X ⁹ or X ¹⁰ and X ¹¹ or X ¹² may be combined with each other A ring may be formed.
n represents 0 or a positive integer, and when n is 2 or more, a plurality of X ⁵ to X ⁸ may be the same or different. ]

[In general formula (1), R ¹ is a hydrocarbon group having 1 to 20 carbon atoms, a trichloroalkyl group having 1 to 20 carbon atoms, or a trialkylsilyl group having 3 to 20 carbon atoms, and R ² is A hydrogen atom, a methyl group, an ethyl group, a benzyl group, or a trialkylsilyl group having 3 to 18 carbon atoms, and Z is a divalent organic group having 1 to 30 carbon atoms. ]

[In general formula (2), R ³ is a divalent organic group having 1 to 10 carbon atoms, and Z is a divalent organic group having 1 to 30 carbon atoms. ]

A second aspect of the present invention is characterized in that the nitrogen-containing substituted olefin (b-1) represented by the general formula (3) has a structure represented by the following general formula (4). It is an olefin copolymer according to the invention of.

[In the general formula (4), X ¹ to X ⁴ , X ⁹ , X ¹¹ and X ¹² are respectively the same as X ¹ to X ⁴ , X ⁹ , X ¹¹ and X ¹² in the general formula (3); , Z, R ¹ and R ² are respectively the same as Z, R ¹ and R ² in the general formula (1). ]

A third aspect of the present invention is the nitrogen-containing substituted olefin (b-1) represented by the general formula (3), wherein the nitrogen-containing substituted olefin (b-1) has a structure represented by the following general formula (5). It is an olefin copolymer.

[In general formula (5), X ¹ to X ⁴ , X ⁹ , X ¹¹ and X ¹² are respectively the same as X ¹ to X ⁴ , X ⁹ , X ¹¹ and X ¹² in general formula (3); , Z and R3 ^are respectively the same as Z and R3 in the general formula ( ² ). ]

A fourth _aspect of the present invention is the _second or It is the olefin copolymer according to the third invention.

A fifth aspect of the present invention is the olefin covalent compound according to the first or second aspect, wherein R ¹ in the general formula (1) or (4) is a hydrocarbon group having 1 to 15 carbon atoms. It is a polymer.

A sixth invention of the present invention is the olefin copolymer according to the first or second invention, wherein R ¹ in the general formula (1) or (4) is a tert-butyl group.

A seventh aspect of the present invention is any one of the first to sixth aspects, wherein the number of methyl branches calculated by ¹³ C-NMR is 50 or less per 1,000 carbon atoms. is an olefin copolymer.

An eighth aspect of the present invention is the olefin copolymer according to the seventh aspect, wherein the number of methyl branches is 5 or less per 1,000 carbon atoms.

A ninth invention of the present invention is at least one selected from the group consisting of ethylene (a-1) and an α-olefin having 3 to 20 carbon atoms (a-2),
a nitrogen-containing substituted olefin (b-1) represented by the following general formula (3),
A process for producing an olefin copolymer characterized by polymerizing in the presence of a transition metal catalyst of metals of Groups 5 to 11 of the periodic table having chelating ligands.

[In the general formula (3), X ¹ to X ¹² may be the same or different, a substituent represented by the following general formula (1), a substituent represented by the following general formula (2), A hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 20 carbon atoms, provided that at least one of X ¹ to X ¹² is a substituent represented by the general formula (1) or a substituent represented by the general formula ( It is a substituent represented by 2).
X ⁹ and X ¹⁰ , and X ¹¹ and X ¹² may each be combined to form a divalent organic group, and X ⁹ or X ¹⁰ and X ¹¹ or X ¹² may be combined with each other A ring may be formed.
n represents 0 or a positive integer, and when n is 2 or more, a plurality of X ⁵ to X ⁸ may be the same or different. ]

[In general formula (1), R ¹ is a hydrocarbon group having 1 to 20 carbon atoms, a trichloroalkyl group having 1 to 20 carbon atoms, or a trialkylsilyl group having 3 to 20 carbon atoms, and R ² is A hydrogen atom, a methyl group, an ethyl group, a benzyl group, or a trialkylsilyl group having 3 to 18 carbon atoms, and Z is a divalent organic group having 1 to 30 carbon atoms. ]

[In general formula (2), R ³ is a divalent organic group having 1 to 10 carbon atoms, and Z is a divalent organic group having 1 to 30 carbon atoms. ]

A tenth invention of the present invention is the process for producing an olefin copolymer according to the ninth invention, wherein the transition metal catalyst is a transition metal catalyst of group 10 of the periodic table.

INDUSTRIAL APPLICABILITY According to the present invention, novel olefin copolymers with easily degradable protective groups are provided. Since this olefin copolymer is a novel olefin-based polar copolymer, it can be used in a wide range of applications. This olefin copolymer is a novel olefin-based polar copolymer produced by a simple and efficient polymerization method and having easily decomposable protective groups.

Moreover, according to the method for producing an olefin copolymer of the present invention, a novel olefin copolymer having an easily decomposable protective group can be produced easily and efficiently.

FIG. 1(a) is an image diagram of the molecular structure of an olefin copolymer polymerized by a high-pressure radical polymerization process. FIG. 1(b) is an image diagram of the molecular structure of an olefin copolymer polymerized using a metal catalyst and having no long chain branch. FIG. 1(c) is an image diagram of the molecular structure of an olefin copolymer polymerized using a metal catalyst and having a small amount of long-chain branches.

Hereinafter, the olefin copolymer of the present invention and the method for producing the same will be described specifically and in detail for each item.

<<1. About Olefin Copolymer>>
(1) Olefin Copolymer The olefin copolymer of the present invention comprises a structural unit derived from ethylene (a-1) and a structural unit derived from an α-olefin (a-2) having 3 to 20 carbon atoms. a structural unit (A) containing at least one selected from the group;
and a structural unit (B) derived from a nitrogen-containing substituted olefin (b-1) represented by the following general formula (3).

[In the general formula (3), X ¹ to X ¹² may be the same or different, a substituent represented by the following general formula (1), a substituent represented by the following general formula (2), A hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 20 carbon atoms, provided that at least one of X ¹ to X ¹² is a substituent represented by the general formula (1) or a substituent represented by the general formula ( It is a substituent represented by 2).
X ⁹ and X ¹⁰ , and X ¹¹ and X ¹² may each be combined to form a divalent organic group, and X ⁹ or X ¹⁰ and X ¹¹ or X ¹² may be combined with each other A ring may be formed.
n represents 0 or a positive integer, and when n is 2 or more, a plurality of X ⁵ to X ⁸ may be the same or different. ]

[In general formula (1), R ¹ is a hydrocarbon group having 1 to 20 carbon atoms, a trichloroalkyl group having 1 to 20 carbon atoms, or a trialkylsilyl group having 3 to 20 carbon atoms, and R ² is A hydrogen atom, a methyl group, an ethyl group, a benzyl group, or a trialkylsilyl group having 3 to 18 carbon atoms, and Z is a divalent organic group having 1 to 30 carbon atoms. ]

[In general formula (2), R ³ is a divalent organic group having 1 to 10 carbon atoms, and Z is a divalent organic group having 1 to 30 carbon atoms. ]

(2) Structural unit (A) (2-1) Structural unit (A)
The olefin copolymer of the present invention is at least one selected from the group consisting of structural units derived from ethylene (a-1) and structural units derived from α-olefins (a-2) having 3 to 20 carbon atoms. It is characterized by having a structural unit (A) containing

Structural unit (A) is not particularly limited as long as it contains at least one selected from the group consisting of structural units derived from ethylene (a-1) and structural units derived from α-olefin (a-2). Structural unit (A) preferably essentially contains a structural unit derived from ethylene (a-1), and may further contain a structural unit derived from α-olefin (a-2), if necessary.

Ethylene (a-1) or α-olefin (a-2) may be used alone, or two or more of them may be used. Further, the structural unit (A) may further contain a structural unit derived from another monomer containing no polar group, as long as it does not deviate from the spirit of the present invention.

The content ratio of the structural unit derived from ethylene (a-1) and the structural unit derived from α-olefin (a-2) is not particularly limited. 80 to 99.999 mol% in total, preferably 85 to 99.99 mol% in total, more preferably 90 to 99.98 mol% in total, and particularly preferably 95 to 99.97 mol% in total.

(2-2) α-olefin (a-2)
The α-olefin (a-2) involved in the present invention is an α-olefin having 3 to 20 carbon atoms represented by the structural formula: CH ₂ ═CHR ¹⁸ (R ¹⁸ is a carbonized α-olefin having 1 to 18 carbon atoms. is a hydrogen group, and may have a straight chain structure or a branched structure).

The α-olefin (a-2) is more preferably an α-olefin having 3 to 12 carbon atoms, more preferably propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1- α-olefins selected from decene, 3-methyl-1-butene and 4-methyl-1-pentene, particularly preferably α-olefins selected from propylene, 1-butene, 1-hexene and 1-octene is an olefin. The α-olefin (a-2) to be polymerized may be used singly or in combination of two or more.

(2-3) Other Monomers Not Containing Polar Groups Monomers not containing other polar groups that may be subjected to polymerization as the structural unit (A) of the present invention have one carbon-carbon double bond in the molecular structure. It is not limited as long as it is a monomer having one or more, and the elements constituting the molecule are only carbon and hydrogen. Examples include dienes, trienes, aromatic vinyl monomers, cyclic olefins, etc., preferably butadiene and isoprene. , styrene, vinylcyclohexane, cyclohexene, vinylnorbornene, and norbornene.

(3) Structural unit (B) (3-1) Structural unit (B)
The olefin copolymer of the present invention is characterized by having a structural unit (B) derived from a nitrogen-containing substituted olefin (b-1) represented by the following general formula (3).

[In the general formula (3), X ¹ to X ¹² may be the same or different, a substituent represented by the following general formula (1), a substituent represented by the following general formula (2), A hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 20 carbon atoms, provided that at least one of X ¹ to X ¹² is a substituent represented by the general formula (1) or a substituent represented by the general formula ( It is a substituent represented by 2).
X ⁹ and X ¹⁰ , and X ¹¹ and X ¹² may each be combined to form a divalent organic group, and X ⁹ or X ¹⁰ and X ¹¹ or X ¹² may be combined with each other A ring may be formed.
n represents 0 or a positive integer, and when n is 2 or more, a plurality of X ⁵ to X ⁸ may be the same or different. ]

[In general formula (1), R ¹ is a hydrocarbon group having 1 to 20 carbon atoms, a trichloroalkyl group having 1 to 20 carbon atoms, or a trialkylsilyl group having 3 to 20 carbon atoms, and R ² is A hydrogen atom, a methyl group, an ethyl group, a benzyl group, or a trialkylsilyl group having 3 to 18 carbon atoms, and Z is a divalent organic group having 1 to 30 carbon atoms. ]

［一般式（２）中、Ｒ^３は、炭素数１～１０の２価の有機基であり、Ｚは、炭素数１～３０の２価の有機基である。］

[In general formula (2), R ³ is a divalent organic group having 1 to 10 carbon atoms, and Z is a divalent organic group having 1 to 30 carbon atoms. ]

Examples of the halogen atoms for X ¹ to X ¹² in formula (3) include fluorine, chlorine, bromine and iodine atoms.

Examples of the hydrocarbon group having 1 to 20 carbon atoms in X ¹ to X ¹² in general formula (3) include methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group and iso-butyl. group, tert-butyl group, n-octyl group, n-eicosyl group, phenyl group, benzyl group, o-toluyl group, m-toluyl group, p-toluyl group and the like. Among them, a methyl group is preferable from the viewpoint of post-treatment.

The hydrocarbon group having 1 to 20 carbon atoms in R ¹ of the general formula (1) is not particularly limited, but methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, tert-butyl group, n-octyl group, n-eicosyl group, phenyl group, benzyl group, o-toluyl group, m-toluyl group, p-toluyl group and the like. Among them, a hydrocarbon group having 1 to 15 carbon atoms is preferred from the viewpoint of treatment of by-products after decomposition, and a tert-butyl group is preferred from the viewpoint of ease of treatment of gas by-products.

Examples of trichloroalkyl groups having 1 to 20 carbon atoms include, but are not limited to, trichloromethyl and trichloromethyl groups.

Examples of the trialkylsilyl group having 3 to 20 carbon atoms include, but are not particularly limited to, a trimethylsilyl group, a triethylsilyl group, and the like.

The trialkylsilyl group having 3 to 18 carbon atoms in R ² of general formula (1) is not particularly limited, but trimethylsilyl group, triethylsilyl group, tert-butyldimethylsilyl group and the like can be exemplified.

The divalent organic group having 1 to 30 carbon atoms in Z of general formula (1) is not particularly limited, but an alkylene group (e.g., methylene group, ethylene group, trimethylene group, propylene group, tetramethylene group, pentamethylene group, hexamethylene group, heptylene group, octylene group, nonylene group, decylene group, undecylene group, dodecylene group, tridecylene group, tetradecylene group, pentadecylene group, hexadecylene group, heptadecylene group, octadecylene group, etc.), cycloalkylene group (e.g. , cyclopentylene group, cyclohexylene group, etc.), aromatic hydrocarbon groups (e.g., phenylene group [o, m or p-phenylene group], methylphenylene group, dimethylphenylene group, naphthylene group, etc.), etc. be able to.

The divalent organic group having 1 to 10 carbon atoms in R ³ of general formula (2) is not particularly limited, but an alkylene group (e.g., methylene group, ethylene group, trimethylene group, propylene group, tetramethylene group, penta methylene group, hexamethylene group, etc.), cycloalkylene group (e.g., cyclohexylene group, etc.), aromatic hydrocarbon group (e.g., phenylene group [o, m or p-phenylene group], methylphenylene group, dimethylphenylene group , naphthylene group, etc.).

Examples of the divalent organic group having 1 to 30 carbon atoms in Z of general formula (2) include the same divalent organic groups having 1 to 30 carbon atoms in Z of general formula (1). .

The nitrogen-containing substituted olefin (b-1) preferably has a structure represented by the following general formula (4).

[In the general formula (4), X ¹ to X ⁴ , X ⁹ , X ¹¹ and X ¹² are respectively the same as X ¹ to X ⁴ , X ⁹ , X ¹¹ and X ¹² in the general formula (3); , Z, R ¹ and R ² are respectively the same as Z, R ¹ and R ² in the general formula (1). ]

The divalent organic group having 1 to 30 carbon atoms for Z in the general formula (4) is not particularly limited, but is -(CH ₂ ) _p -, -COO(CH ₂ ) _p -, -OCO(CH ₂ ). _m -, -O(CH ₂ ) _m - or -CO(CH ₂ ) _m - is preferred (where p is an integer of 1-30 and m is an integer of 1-30).

A more preferred embodiment of the divalent organic group for Z is -(CH ₂ ) _p - or -O(CH ₂ ) _m - (where p is an integer of 1 to 30, m is 1 ~30 integers).
A particularly preferred embodiment of the divalent organic group for Z is —(CH ₂ ) _p — (where p is an integer of 1 to 30).
The most preferred embodiment of the divalent organic group for Z is —CH ₂ —.

R ¹ in general formula (4) is a hydrocarbon group having 1 to 20 carbon atoms, a trichloroalkyl group having 1 to 20 carbon atoms, or a trialkylsilyl group having 3 to 20 carbon atoms.

The hydrocarbon group having 1 to 20 carbon atoms in R ¹ of the general formula (4) is not particularly limited, but methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, tert-butyl group, n-octyl group, n-eicosyl group, phenyl group, benzyl group, 9-fluorenylmethyl group, allyl group and the like.

Examples of trichloroalkyl groups having 1 to 20 carbon atoms include, but are not limited to, trichloromethyl and trichloromethyl groups.

Examples of the trialkylsilyl group having 3 to 20 carbon atoms include, but are not particularly limited to, a trimethylsilyl group, a triethylsilyl group, and the like.

R ¹ in the general formula (4) is preferably a hydrocarbon group having 1 to 15 carbon atoms from the viewpoint of treatment of by-products after decomposition. -Butyl groups are preferred.

R ² in general formula (4) is a hydrogen atom, a methyl group, an ethyl group, a benzyl group, or a trialkylsilyl group having 3 to 18 carbon atoms.

The trialkylsilyl group having 3 to 18 carbon atoms in R ² of the general formula (4) is not particularly limited, but trimethylsilyl group, triethylsilyl group, tert-butyldimethylsilyl group and the like can be exemplified.

Also, the nitrogen-containing substituted olefin (b-1) preferably has a structure represented by the following general formula (5).

[In general formula (5), X ¹ to X ⁴ , X ⁹ , X ¹¹ and X ¹² are respectively the same as X ¹ to X ⁴ , X ⁹ , X ¹¹ and X ¹² in general formula (3); , Z and R3 ^are respectively the same as Z and R3 in the general formula ( ² ). ]

Although the divalent organic group having 1 to 30 carbon atoms in Z of the general formula (5) is not particularly limited, -(CH ₂ ) _p -, -COO(CH ₂ ) _p -, -OCO(CH ₂ ) _m -, -O(CH ₂ ) _m - or -CO(CH ₂ ) _m - is preferred (where p is an integer of 1-30 and m is an integer of 1-30).

A more preferred embodiment of the divalent organic group for Z is -(CH ₂ ) _p - or -O(CH ₂ ) _m - (where p is an integer of 1 to 30, m is 1 ~30 integers).
A particularly preferred embodiment of the divalent organic group for Z is —(CH ₂ ) _p — (where p is an integer of 1 to 30).
The most preferred embodiment of the divalent organic group for Z is —CH ₂ —.

The divalent organic group having 1 to 10 carbon atoms in R ³ of the general formula (5) is not particularly limited, but an alkylene group (e.g., methylene group, ethylene group, trimethylene group, propylene group, tetramethylene group, penta methylene group, hexamethylene group, etc.), cycloalkylene group (e.g., cyclohexylene group, etc.), aromatic hydrocarbon group (e.g., phenylene group [o, m or p-phenylene group], methylphenylene group, dimethylphenylene group , naphthylene group, etc.).

(3-2) Specific Examples of the Nitrogen-Containing Substituted Olefin (b-1) Specific examples of the nitrogen-containing substituted olefin (b-1) are described below. In the formula, tBu represents a tert-butyl group and Me represents a methyl group.

(4) Structural Unit of Olefin Copolymer The structural unit and the amount of structural units of the olefin copolymer of the present invention will be described.
A structure derived from one molecule each of ethylene (a-1), an α-olefin having 3 to 20 carbon atoms (a-2), and a nitrogen-containing substituted olefin (b-1) is regarded as one structure in the olefin copolymer. Define as a unit. The structural unit amount is the ratio of each structural unit in the olefin copolymer expressed in mol %.

(5) Structural Unit Amount of Structural Unit (B) Derived from Nitrogen-Containing Substituted Olefin (b-1) Although the ratio of the structural unit (B) derived from the nitrogen-containing substituted olefin (b-1) is not particularly limited, When the total olefin copolymer is 100 mol%, it is usually in the range of 20 to 0.001 mol%, preferably in the range of 15 to 0.01 mol%, more preferably in the range of 10 to 0.02 mol%, still more preferably It is selected from the range of 5 to 0.03 mol%. If the structural unit amount of the structural unit (B) is less than this range, the adhesiveness to different materials having high polarity may not be sufficient. Mechanical properties may not be obtained.

(6) Method for measuring amount of structural unit derived from nitrogen-containing substituted olefin (b-1) The amount of structural unit (B) in the olefin copolymer of the present invention is determined using ¹³ C-NMR spectrum. . A ¹³ C-NMR spectrum is measured by the following method.

200 to 250 mg of a sample was added to o-dichlorobenzene/deuterobrominated benzene (C ₆ D ₅ Br) = 4/1 (volume ratio) of 2.4 ml and hexamethyldisiloxane, which is a reference substance for chemical shift, in an inner diameter of 10 mmφ. The solution is placed in an NMR sample tube, purged with nitrogen, sealed, heated and dissolved with a block heater at 130° C., and subjected to NMR measurement as a homogeneous solution. NMR measurement is performed at 120° C. using an AV400M type NMR apparatus (Bruker Biospin Co., Ltd.) equipped with a 10 mmφ cryoprobe. ¹³ C-NMR is measured by a reverse gate decoupling method with a pulse angle of 90°, a pulse interval of 51.5 seconds, and an accumulation number of 512 times. Chemical shifts are set at 1.98 ppm for the methyl carbon peak of hexamethyldisiloxane, and the chemical shifts for peaks due to other carbons are referenced to this.

Further, the number of methyl branches in the olefin copolymer described later can be determined by ¹³ C-NMR.

(7) Molecular Structure of Olefin Copolymer The olefin copolymer of the present invention has a structural unit derived from ethylene (a-1) and a structure derived from an α-olefin (a-2) having 3 to 20 carbon atoms. It is preferably a random copolymer having a structural unit (A) containing at least one selected from the group consisting of units and a structural unit (B) derived from a nitrogen-containing substituted olefin (b-1). .

Examples of molecular structures of olefin copolymers of the present invention are shown in the following paragraphs. A random copolymer is a structural unit (A) and a structural unit (B) in the molecular structure examples shown below, and the probability of finding each structural unit at any position in the molecular chain It is a copolymer independent of the type of unit.

Further, the molecular chain end of the olefin copolymer of the present invention may be ethylene (a-1) or an α-olefin having 3 to 20 carbon atoms (a-2), a nitrogen-containing substituted olefin (b-1 ). As shown below, an example of the molecular structure of the olefin copolymer of the present invention is ethylene (a-1) or an α-olefin having 3 to 20 carbon atoms (a-2) and a nitrogen-containing substituted olefin (b-1). forms a random copolymer.

An example of the molecular structure of an olefin copolymer obtained by graft modification is also shown for reference. Part of the olefin copolymer obtained by copolymerizing the structural unit (A) is graft modified with the structural unit (B).

The olefin copolymer of the present invention is preferably produced in the presence of a transition metal catalyst and preferably has a linear molecular structure. Fig. 1(a) shows an image of the molecular structure of an olefin copolymer polymerized by a high-pressure radical polymerization process, and Fig. 1(b) shows an image of the molecular structure of an olefin copolymer polymerized using a metal catalyst. As illustrated in FIG. 1(c), the molecular structure differs depending on the manufacturing method. This difference in molecular structure can be controlled by selecting the manufacturing method. Molecular structure can be deduced.

More specifically, when the phase angle δ at the absolute value of the complex elastic modulus G ^* =0.1 MPa measured with a rotational rheometer is 40 degrees or more, the molecular structure does not contain any long-chain branches (Fig. 1(b)) or a structure containing a small amount of long-chain branching that does not affect the mechanical strength ((c) of FIG. 1).

When the phase angle δ at the absolute value of the complex elastic modulus G ^* =0.1 MPa measured by a rotational rheometer is lower than 40 degrees, the molecular structure exhibits long-chain branching, as shown in FIG. It shows a structure containing too much, and the mechanical strength is inferior.

The phase angle δ at the absolute value of the complex elastic modulus G ^* =0.1 MPa measured with a rotational rheometer is affected by both the molecular weight distribution parameter (Mw/Mn) and long chain branching, but Mw/Mn≦4, More preferably, Mw/Mn≦3 is an index of the amount of long-chain branching, and the more long-chain branching, the smaller the δ (G ^* =0.1 MPa) value. If Mw/Mn is 1.5 or more, the δ (G ^* =0.1 MPa) value does not exceed 75 degrees even when there are no long chain branches.

(8) Weight average molecular weight (Mw) of olefin copolymer
The weight average molecular weight (Mw) of the olefin copolymer of the present invention is usually 1,000 to 2,000,000, preferably 10,000 to 1,500,000, more preferably 20,000 to 1,000, 000, more preferably 31,000 to 800,000, even more preferably 33,000 to 800,000. If the Mw is less than 1,000, the physical properties such as mechanical strength and impact resistance are not sufficient, and the adhesiveness to different materials with high polarity may be inferior. If the Mw exceeds 2,000,000, the melt viscosity becomes very high, and molding may become difficult.

The olefin copolymer of the present invention has a weight average molecular weight (Mw) to number average molecular weight (Mn) ratio (Mw/Mn) of usually 1.5 to 3.5, preferably 1.6 to 3.3, It is more preferably in the range of 1.7 to 3.0. When Mw/Mn is less than 1.5, various workability tends to be insufficient, while when Mw/Mn exceeds 3.5, performance such as adhesion tends to be insufficient.

The weight average molecular weight (Mw) of the olefin copolymer of the present invention is determined by gel permeation chromatography (GPC). Further, the molecular weight distribution parameter (Mw/Mn) is obtained by further determining the number average molecular weight (Mn) by GPC and calculating the ratio (Mw/Mn) between Mw and Mn.

(9) Melting Point of Olefin Copolymer The melting point of the olefin copolymer of the present invention is indicated by the maximum peak temperature of the endothermic curve measured by a differential scanning calorimeter (DSC). The maximum peak temperature is the height from the baseline when multiple peaks are shown in the endothermic curve obtained by taking heat flow (mW) on the vertical axis and temperature (°C) on the horizontal axis in DSC measurement. indicates the temperature of the maximum peak, and if there is one peak, the temperature of that peak is indicated.

The melting point of the olefin copolymer of the present invention is preferably 50°C to 140°C, more preferably 60°C to 138°C, most preferably 70°C to 135°C. If the melting point is lower than this range, the heat resistance is not sufficient, and if the melting point is higher than this range, the adhesion is inferior.

(10) The number of methyl branches calculated by ¹³ C-NMR of the olefin copolymer The olefin copolymer of the present invention has a number of methyl branches calculated by ¹³ C-NMR of 50 or less per 1,000 carbon atoms. is preferably Among these, the number of methyl branches is particularly preferably 5 or less per 1,000 carbon atoms. When the number of methyl branches satisfies this value, the elastic modulus is high and the mechanical strength of the molded product is also high.

The number of methyl branches can be controlled by selecting the transition metal catalyst to be used and adjusting the polymerization temperature. Lowering the polymerization temperature is effective as a specific means for lowering the number of methyl branches in the olefin copolymer of the present invention. In addition, reducing the number of methyl branches, for example, requires the adjustment of these factors to control the desired copolymer region.

The number of methyl branches was determined using the spectrum obtained under the ¹³ C-NMR measurement conditions described in the item "(6) Method for measuring the amount of structural units derived from the nitrogen-containing substituted olefin (b-1)". calculate.

20.0-19.8 ppm methyl carbon, 33.2-33.0 ppm methine carbon, and 37.5-37.3 ppm methylene carbon in the ¹³ C-NMR spectrum. Using the value I divided by 4 _(B1) , the number of methyl branches per 1,000 total carbon atoms (1000 C total) is calculated using the following formula.

Number of methyl branches (number/total 1000C) = I _(B1) x 1000/I _(total)

Here, I _(B1) and I _(total) are quantities represented by the following formulas.
I _(B1) = (I _20.0-19.8 +I _33.2-33.0 +I _37.5-37.3 )/4
I _(total) = I _{180.0 to 135.0} + I _{120.0 to 2.0}
In addition, I indicates the integrated intensity, and the numerical value with the subscript of I indicates the range of the chemical shift. For example, I _180.0-135.0 indicates the integrated intensity of signals detected between 180.0 ppm and 135.0 ppm.

<<2. About the production method of the olefin copolymer>>
(1) Method for producing an olefin copolymer The method for producing an olefin copolymer of the present invention is selected from the group consisting of ethylene (a-1) and an α-olefin having 3 to 20 carbon atoms (a-2). At least one species and a nitrogen-containing substituted olefin (b-1) represented by the following general formula (3) are covalently combined in the presence of a transition metal catalyst of a metal of Groups 5 to 11 of the periodic table having a chelating ligand. It is characterized by polymerizing.

[In the general formula (3), X ¹ to X ¹² may be the same or different, a substituent represented by the following general formula (1), a substituent represented by the following general formula (2), A hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 20 carbon atoms, provided that at least one of X ¹ to X ¹² is a substituent represented by the general formula (1) or a substituent represented by the general formula ( It is a substituent represented by 2).
X ⁹ and X ¹⁰ , and X ¹¹ and X ¹² may each be combined to form a divalent organic group, and X ⁹ or X ¹⁰ and X ¹¹ or X ¹² may be combined with each other A ring may be formed.
n represents 0 or a positive integer, and when n is 2 or more, a plurality of X ⁵ to X ⁸ may be the same or different. ]

[In general formula (1), R ¹ is a hydrocarbon group having 1 to 20 carbon atoms, a trichloroalkyl group having 1 to 20 carbon atoms, or a trialkylsilyl group having 3 to 20 carbon atoms, and R ² is A hydrogen atom, a methyl group, an ethyl group, a benzyl group, or a trialkylsilyl group having 3 to 18 carbon atoms, and Z is a divalent organic group having 1 to 30 carbon atoms. ]

[In general formula (2), R ³ is a divalent organic group having 1 to 10 carbon atoms, and Z is a divalent organic group having 1 to 30 carbon atoms. ]

X ¹ to X ¹² , n, R ¹ to R ³ and Z in general formulas (1) to (3) are <<1. The descriptions of X ¹ to X ¹² , n, R ¹ to R ³ and Z described in the section >> regarding the olefin copolymer are applied as they are, and the description thereof is omitted.

(2) Olefin Copolymer Polymerization Catalyst In the method for producing an olefin copolymer of the present invention, a transition metal catalyst of metals of Groups 5 to 11 of the periodic table having a chelating ligand is used.

Specific examples of preferred transition metals include vanadium atom, niobium atom, tantalum atom, chromium atom, molybdenum atom, tungsten atom, manganese atom, iron atom, platinum atom, ruthenium atom, cobalt atom, rhodium atom, nickel atom, palladium atom, A copper atom etc. are mentioned.

Among these, vanadium atom, iron atom, platinum atom, cobalt atom, nickel atom, palladium atom and rhodium atom are preferred, and platinum atom, cobalt atom, nickel atom and palladium atom are particularly preferred. Optimal ones are platinum, nickel and palladium atoms which are transition metals of group 10 of the periodic table. These metals may be used singly or in combination.

Furthermore, the transition metal is preferably an element selected from the group consisting of nickel (II), palladium (II), platinum (II), cobalt (II) and rhodium (III), and is of group 10 of the periodic table. An element is more preferable from the viewpoint of polymerization activity, and nickel (II) is particularly preferable from the viewpoint of price and the like.

Chelating ligands have at least two atoms selected from the group consisting of P, N, O, and S and are bidentate or multidentate It contains ligands and is electronically neutral or anionic. A review by Brookhart et al. exemplifies its structure (Chem. Rev., 2000, 100, 1169).

Preferred chelating ligands include bidentate anionic P,O ligands and bidentate anionic N,O ligands. Examples of bidentate anionic P,O ligands include phosphorus sulfonic acid, phosphorus carboxylic acid, phosphorus phenol, and phosphorus enolate. Bidentate anionic N,O ligands include, for example, salicylaldiminate and pyridinecarboxylic acid, as well as diimine ligands, diphenoxide ligands and diamide ligands.

The structure of the metal complex obtained from the chelating ligand is an arylphosphine compound which may have a substituent, an arylarsine compound which may have a substituent, or an arylantimony compound which may have a substituent. It is represented by the following coordinated structural formula (α) and/or structural formula (β).

In structural formulas (α) and (β), M represents a transition metal belonging to any of groups 5 to 11 of the periodic table of the elements, ie various transition metals as described above. X' ¹ represents an oxygen atom, a sulfur atom, -SO ₃ -, or -CO ₂ -. Y ¹ represents a carbon atom or a silicon atom. t represents 0 or 1; E ¹ represents a phosphorus atom, an arsenic atom or an antimony atom. r ³ and r ⁴ each independently represent a hydrogen atom or a hydrocarbon group optionally containing a heteroatom having 1 to 30 carbon atoms. Each r ⁵ independently represents a hydrogen atom, a halogen atom or a hydrocarbon group optionally containing a heteroatom having 1 to 30 carbon atoms. r ⁶ and r ⁷ are each independently a hydrogen atom, a halogen atom, a hydrocarbon group optionally containing a heteroatom having 1 to 30 carbon atoms, Or ² , CO ₂ r ² , CO ₂ M′, C ( O)N(r ¹ ) ₂ , C(O)r ² , Sr ² , SO ₂ r ² , SOr ² , OSO ₂ r ² , P(O)(Or ² ) ₂ -y(r ¹ )y, CN , NHr ² , N(r ² ) ₂ , Si(Or ¹ ) ₃ -x(r ¹ )x, OSi(Or ¹ ) ₃ -x(r ¹ )x, NO ₂ , SO ₃ M′, PO ₃ M ' ₂ , P(O)(Or ² ) ₂ M' or represents an epoxy-containing group. M' represents an alkali metal, alkaline earth metal, ammonium, quaternary ammonium or phosphonium; x represents an integer from 0 to 3; y represents an integer from 0 to 2; Note that ^r6 and ^r7 may be linked together to form an alicyclic ring, an aromatic ring, or a heterocyclic ring containing a heteroatom selected from an oxygen atom, a nitrogen atom, and a sulfur atom. At this time, the number of ring members is 5 to 8, and the ring may or may not have a substituent. r ¹ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms; r ² represents a hydrocarbon group having 1 to 20 carbon atoms. L ¹ represents the ligand coordinated to M; Also ^, r3 and L1 may combine with ^each other to form a ring.

A metal complex obtained from a chelating ligand is more preferably a transition metal complex represented by the following structural formula (γ).

In the structural formula (γ), M represents a transition metal belonging to any of Groups 5 to 11 of the periodic table of the elements, that is, the transition metal described above. X' ¹ represents an oxygen atom, a sulfur atom, -SO ₃ -, or -CO ₂ -. Y ¹ represents a carbon atom or a silicon atom. t represents 0 or 1; E ¹ represents a phosphorus atom, an arsenic atom or an antimony atom. r ³ and r ⁴ each independently represent a hydrogen atom or a hydrocarbon group optionally containing a heteroatom having 1 to 30 carbon atoms. Each r ⁵ independently represents a hydrogen atom, a halogen atom, or a hydrocarbon group optionally containing a heteroatom having 1 to 30 carbon atoms. r ⁸ to r ¹¹ each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group optionally containing a heteroatom having 1 to 30 carbon atoms, Or ² , CO ₂ r ² , CO ₂ M′, C( O)N(r ¹ ) ₂ , C(O)r ² , Sr ² , SO ₂ r ² , SOr ² , OSO ₂ r ² , P(O)(Or ² ) ₂ -y(r ¹ )y, CN , NHr ² , N(r ² ) ₂ , Si(Or ¹ ) ₃ -x(r ¹ )x, OSi(Or ¹ ) ₃ -x(r ¹ )x, NO ₂ , SO ₃ M′, PO ₃ M ' ₂ , P(O)(Or ² ) ₂ M' or represents an epoxy-containing group. M' represents an alkali metal, alkaline earth metal, ammonium, quaternary ammonium or phosphonium; x represents an integer from 0 to 3; y represents an integer from 0 to 2; In addition, a plurality of groups appropriately selected from r ⁸ to r ¹¹ are linked to each other to form an alicyclic ring, an aromatic ring, or a hetero ring containing a hetero atom selected from an oxygen atom, a nitrogen atom, and a sulfur atom. You may At this time, the number of ring members is 5 to 8, and the ring may or may not have a substituent. r ¹ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms; r ² represents a hydrocarbon group having 1 to 20 carbon atoms. L ¹ represents the ligand coordinated to M; Also ^, r3 and L1 may combine with ^each other to form a ring.

As catalysts for transition metal compounds of Groups 5 to 11 of the periodic table having chelating ligands, so-called Shop-based and Drent-based catalysts are typically known.
A Shop-based catalyst is a catalyst in which a phosphorus-based ligand having an optionally substituted aryl group is coordinated to nickel metal (see, for example, International Publication No. 2010/050256). Also, the Drent system is a catalyst in which a phosphorus-based ligand having an aryl group which may have a substituent is coordinated to palladium metal (see, for example, JP-A-2010-202647).

(3) Organometallic compound In the production of the olefin copolymer of the present invention, at least one of the nitrogen-containing substituted olefins (b-1) described above is brought into contact with a small amount of an organometallic compound, and then the transition metal Polymerization activity is increased by copolymerizing ethylene (a-1) and/or an α-olefin having 3 to 20 carbon atoms (a-2) with a nitrogen-containing substituted olefin (b-1) in the presence of a catalyst. be heightened.

The organometallic compound is an organometallic compound containing a hydrocarbon group which may have a substituent, and can be represented by the following structural formula (H).
R ³⁰ _n' M ³⁰ X ³⁰ _m'-n' structural formula (H)
(In Structural Formula (H), R ³⁰ represents a hydrocarbon group which may have a substituent of 1 to 12 carbon atoms, and M ³⁰ represents groups 1, 2, 12 of the periodic table metal selected from the group consisting of group and group 13, X ³⁰ represents a halogen atom or a hydrogen atom, m' is the valence of M ³⁰ , n' is 1 to m'.)

Examples of the organometallic compound represented by the above structural formula (H) include alkylaluminum compounds such as tri-n-butylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum and tri-n-decylaluminum, and methylaluminum. Examples thereof include alkylaluminum halides such as dichloride, ethylaluminum dichloride, dimethylaluminum chloride, diethylaluminum chloride and diethylaluminum ethoxide, preferably trialkylaluminum.

More preferably trialkylaluminum having a hydrocarbon group with 4 or more carbon atoms, more preferably trialkylaluminum having a hydrocarbon group with 6 or more carbon atoms, particularly preferably tri-n-hexylaluminum, tri- n-octylaluminum, tri-n-decylaluminum are selected and tri-n-octylaluminum is most preferably used.

From the viewpoint of polymerization activity and cost, the organometallic compound can be brought into contact in an amount such that the molar ratio to the polar group-containing comonomer (corresponding to the nitrogen-containing substituted olefin (b-1)) is 10 ^-5 to 0.9. Preferably, the contact amount is 10 ⁻⁴ to 0.2, and more preferably 10 ⁻⁴ to 0.1.

(4) Residual amount of aluminum (Al) The amount of aluminum (Al) remaining in 1 g of the olefin copolymer of the present invention (hereinafter sometimes simply referred to as "the amount of Al") is 100,000 µg _Al / g or less is preferable, 70,000 μg _Al /g or less is more preferable, 20,000 μg _Al /g or less is still more preferable, 10,000 μg _Al /g or less is even more preferable, and 5,000 μg _Al /g or less is even more preferable. , 1,000 μg _Al /g or less is particularly preferred, and 500 μg _Al /g or less is most preferred.

If the amount of Al is more than this, the mechanical properties of the olefin copolymer are likely to deteriorate, and the discoloration and deterioration of the polymerized product are likely to be accelerated. The amount of Al should be as small as possible. For example, it may be as small as 1 μg _Al /g or 0 μg _Al /g. In addition, μg _Al /g means that the amount of aluminum (Al) contained in 1 g of the polar group-containing olefin copolymer is expressed in units of μg.

(5) Calculation of Aluminum (Al) Amount The amount of Al can be calculated as a value obtained by dividing the amount of aluminum contained in the alkylaluminum subjected to polymerization by the yield of the obtained olefin copolymer.

The amount of Al is calculated from the amount of alkylaluminum polymerized, but may be measured by fluorescent X-ray analysis or inductively coupled plasma emission (ICP) analysis. When using fluorescent X-ray analysis or ICP analysis, it can be measured by, for example, the following method.

(5-1) Fluorescent X-ray Analysis 3 to 10 g of a sample to be measured is weighed and molded under heat and pressure using a hot press to prepare a flat sample with a diameter of 45 mm. Measurement is performed on a portion of the plate-like sample having a central diameter of 30 mm, using a scanning fluorescent X-ray spectrometer "ZSX100e" (Rh tube 4.0 kW) manufactured by Rigaku Denki Kogyo Co., Ltd. under the following conditions.

・X-ray output: 50kV-50mA
・Analyzing crystal: PET (pentaerythritol)
・Detector: PC (proportional counter)
・Detection line: Al-Kα line

The aluminum content can be obtained from the calibration curve prepared in advance and the results measured under the above conditions. A calibration curve can be prepared by measuring the aluminum content of a plurality of polyethylene resins by ICP analysis, and then subjecting these polyethylene resins to fluorescent X-ray analysis under the above conditions.

(5-2) Inductively Coupled Plasma Emission (ICP) Analysis A measurement sample, 3 ml of special grade nitric acid, and 1 ml of hydrogen peroxide solution (hydrogen peroxide content: 30% by weight) are placed in a Teflon (registered trademark) container and subjected to a microwave decomposition apparatus. (MLS-1200MEGA manufactured by Milestone General Co., Ltd.), heat decomposition operation is performed at a maximum of 500 W, and the measurement sample is dissolved. The aluminum content can be measured by subjecting the solutionized measurement sample to an ICP emission spectrometer (IRIS-AP manufactured by Thermo Jarrel Ash). The aluminum content is quantified using a calibration curve prepared using a standard solution with a known aluminum element concentration.

(6) Method for Polymerizing Olefin Copolymer The method for polymerizing the olefin copolymer of the present invention is not limited. Slurry polymerization in which at least a part of the produced polymer becomes a slurry in the medium, bulk polymerization in which the liquefied monomer itself is used as the medium, gas-phase polymerization conducted in the vaporized monomer, or polymer produced in the liquefied monomer at high temperature and high pressure. High-pressure ion polymerization or the like in which at least a part of is dissolved is preferably used. Moreover, the polymerization system may be any of batch polymerization, semi-batch polymerization, and continuous polymerization. Further, living polymerization may be used, or polymerization may be performed while chain transfer occurs simultaneously. Furthermore, a so-called chain shuttling agent (CSA) may be used together to perform chain shuttling reaction or coordinated chain transfer polymerization (CCTP). For specific manufacturing processes and conditions, for example, JP-A-2010-260913 and JP-A-2010-202647 can be referred to.

<<3. Additives>>
The olefin copolymer of the present invention contains antioxidants, ultraviolet absorbers, lubricants, antistatic agents, coloring agents, pigments, cross-linking agents, foaming agents, nucleating agents, and flame retardants within the scope of the present invention. , a conductive material, a filler, and other additives may be added.

<<4. Applications of the Olefin Copolymer of the Present Invention>>
(1) Adhesive The olefin copolymer of the present invention has a specific molecular structure and resin physical properties, so that it exhibits high adhesiveness with other substrates, making it possible to manufacture industrially useful laminates. to In particular, the adhesion performance to various substrates is such that in the above-mentioned olefin copolymer, the amount of structural units derived from the nitrogen-containing substituted olefin (b-1) in the olefin copolymer is usually 20 to 0.001 mol%. The range, preferably 15 to 0.01 mol%, more preferably 10 to 0.02 mol%, still more preferably 5 to 0.03 mol%, is sufficiently expressed.

(2) Laminate (2-1) Material of Laminate The olefin copolymer of the present invention can be used in a laminate. Specifically, the laminate is a laminate containing a layer comprising the olefin copolymer of the present invention and a substrate layer.

Specific examples of the substrate in the substrate layer include high-density polyethylene, medium-density polyethylene, low-density polyethylene, ethylene-vinyl acetate copolymer, ethylene-acrylate copolymer, ionomer, homopolypropylene resin, and propylene. and other α-olefins, olefin resins such as poly-1-butene and poly-4-methyl-1-pentene, polyvinyl chloride, polyvinylidene chloride, polystyrene, polyacrylate, polyacrylonitrile, etc. Vinyl polymers, nylon 6, nylon 66, nylon 10, nylon 11, nylon 12, nylon 610, polyamide resins such as polymetaxylylene adipamide, polyethylene terephthalate, polyethylene terephthalate/isophthalate, polybutylene terephthalate, polylactic acid , polybutylene succinate, polyester resins such as aromatic polyesters, polyvinyl alcohol, ethylene-vinyl alcohol copolymers, polycarbonate resins, adhesive fluororesins, thermoplastics with film-forming properties such as cellulose polymers such as cellophane Resin films or sheets (and stretched or printed products thereof), metal foils or plates such as aluminum, iron, copper, or alloys containing these as main components, inorganic oxides such as silica-deposited plastic films, alumina-deposited plastic films, etc. vapor deposition films of metals such as gold, silver, and aluminum, or metal vapor deposition films of compounds other than oxides of these metals, high-quality paper, kraft paper, cardboard, glassine paper, synthetic paper, cellophane, woven fabric, A nonwoven fabric etc. can be mentioned.

The base material in the base material layer can be appropriately selected depending on the application and the type of the article to be packaged. For example, when the package is a perishable food, a material having transparency, rigidity, and gas permeation resistance such as polyamide, polyvinylidene chloride, ethylene-vinyl alcohol copolymer (EVOH), polyvinyl alcohol, and polyester may be used. Excellent resins can be used. Moreover, when the object to be packaged is confectionery or fiber, it is preferable to use polypropylene or the like, which has good transparency, rigidity, and water permeation resistance. When applied to fuel tanks of automobiles, tubes, hoses, pipes, etc. through which fuel passes, resins with excellent fuel permeation prevention performance such as EVOH, polyamides, and fluororesins can be used.

The laminate may further include a barrier layer. The barrier layer contains a barrier resin.
Barrier resins include polyamide-based resins, polyester-based resins, EVOH, polyvinylidene chloride-based resins, polycarbonate-based resins, oriented polypropylene (OPP), oriented polyester (OPET), oriented polyamide, alumina-deposited films, silica-deposited films, and the like. Metal and inorganic oxide vapor deposition films, metal vapor deposition films such as aluminum vapor deposition, metal foils, and the like can be used.

(2-2) Use of Laminate The laminate is suitably used as a food container, for example. Specific examples of foods include snacks such as potato chips, confectionery such as biscuits, rice crackers and chocolates, powdered seasonings such as powdered soups, dried bonito flakes and smoked foods.

Also, the container can be formed, for example, by placing the ethylene-based copolymer layer surfaces of the above-mentioned laminate face-to-face and heat-sealing at least a part of them. Specifically, for example, the laminate can be used for liquid packaging, bags, liquid soup packets, liquid paper containers, laminated original fabrics, special-shaped liquid packaging bags (standing pouches, etc.), standard bags, heavy bags, semi-heavy bags, It is suitably used for wrap films, sugar bags, oil packaging bags, various packaging containers for food packaging, infusion bags, and the like.

(2-3) Laminate production Laminate processing methods include normal press molding, air-cooling inflation molding, air-cooling two-stage cooling inflation molding, high-speed inflation molding, flat die molding (T-die molding), and water-cooling inflation molding. conventionally known methods such as extrusion molding, extrusion lamination processing, sand lamination processing, lamination processing such as dry lamination processing, blow molding, pressure molding, injection molding, and rotational molding.

(2-4) Laminate Laminate The laminate laminate is a laminate that can be produced by a known lamination method such as extrusion lamination, sand lamination, dry lamination, etc. The laminate laminate is the present invention. It is a laminate that can be produced by laminating a laminate material containing an olefin copolymer and at least one or more base layers. The laminate material in the present invention is a resin material containing the olefin copolymer of the present invention that can be subjected to various known laminating methods.

Extrusion lamination is a method of continuously coating and press-bonding a base material with a molten resin film extruded from a T-die, and is a molding method in which coating and adhesion are simultaneously performed. Sand lamination is a method in which melted resin is poured between paper and a film to be laminated, and the melted resin acts like an adhesive to adhere and laminate. In the dry lamination process, the adhesive for laminating the film to be laminated with the base material and / or the atmospheric humidity in the vicinity of the application roll of the adhesive is dehumidified, or the temperature of the adhesive and / or the application roll of the adhesive is heated. Alternatively, the bonding surface of the film sheet is dried.

In sand lamination and dry lamination, the substrate and the layer containing the olefin copolymer of the present invention are formed on the side of the substrate used in the present invention on which the layer containing the olefin copolymer of the present invention is formed. In order to improve the barrier property, it is easy to laminate the aluminum foil, polyester film, various barrier films, etc. between them. As the base material in the base material layer to be laminated with the laminate material related to the present invention, various materials as described above can be appropriately used.

(3) Extruded Products The olefin copolymer of the present invention can be used for extruded products. Here, the extruded product is an extruded product formed by extruding the olefin copolymer of the present invention. Extruded products related to the present invention include various types of inflation molding such as air-cooled inflation molding, air-cooled two-stage cooling inflation molding, high-speed inflation molding, and water-cooled inflation molding, flat die molding, profile extrusion molding, tubular product molding, calendar molding, and the like. It can be manufactured by extrusion molding.

In addition, in a state in which the extruded article obtained by extrusion molding is not completely solidified, it may be further shaped by various known methods such as being sandwiched between metal molds or the like, or being deformed. Further, the extruded product obtained may be post-processed by various known methods such as bending, cutting, shaping after reheating, and the like.

(4) Multilayer co-extrusion product The olefin copolymer of the present invention can be used in a multilayer coextrusion product. Here, the multilayer coextrusion product is a multilayer coextrusion product that can be molded by known multilayer coextrusion molding, and includes at least a layer containing the olefin copolymer of the present invention. It is an extruded product.
A multi-layer co-extrusion product is a multi-layer structure that can be manufactured by extruding a plurality of thermoplastic materials at the same time to combine them into layers and molding them by various shaping methods. It is a molded product with

Methods for manufacturing multi-layer co-extruded products include multi-layer air-cooled inflation molding, multi-layer air-cooled two-stage cooling inflation molding, multi-layer high-speed inflation molding, multi-layer water-cooled inflation molding, multi-layer flat die molding (T-die molding), multi-layer tubular product molding, Known multilayer co-extrusion molding such as multilayer corrugated pipe molding can be mentioned.

As the substrate in the substrate layer in the multi-layer coextruded product, various materials as described above can be appropriately used. A multilayer co-extrusion molded product can be produced by processing a layer containing the olefin copolymer of the present invention and a suitable base material by a suitable molding method to produce a multilayer film, a multilayer sheet, a multilayer pipe, a multilayer hose, a multilayer tube, It can be produced as a known multi-layer co-extrusion product such as a multi-layer corrugated pipe.

In addition, in a state in which the multilayer co-extruded product obtained by the multilayer co-extrusion molding is not completely solidified, it may be further shaped by various known methods such as being sandwiched between metal molds or the like, or being deformed. Further, the multilayer coextruded product thus obtained may be post-processed by various known methods such as bending, cutting, shaping after reheating, and the like.

(5) Multilayer film The olefin copolymer of the present invention can be used for a multilayer film. Here, the multilayer film is a multilayer film that can be produced by a known multilayer film molding method, and is a multilayer film containing at least a layer containing the olefin copolymer of the present invention and a base layer. be. As a method for producing a multilayer film, known multilayer film molding methods such as multilayer air-cooled inflation molding, multilayer air-cooled two-stage cooling inflation molding, multilayer high-speed inflation molding, multilayer water-cooled inflation molding, and multilayer flat die molding (T-die molding) can be used. can be used. As the substrate in the substrate layer of the multilayer film, various materials as described above can be appropriately used.

(6) Multilayer blow-molded article The olefin copolymer of the present invention can be used for multilayer blow-molded articles. Here, the multilayer blow-molded article is a multilayer blow-molded article that can be produced by known multilayer blow molding, and includes at least a layer containing the olefin copolymer of the present invention and a substrate layer. It is a multi-layer blow molded product. Examples of the method for producing a multilayer blow-molded product include known blow molding methods such as multilayer direct blow molding, multidimensional multilayer blow molding, and multilayer rotary blow molding. As the substrate in the substrate layer of the multilayer blow-molded product related to the present invention, various materials as described above can be appropriately used.

(7) Multilayer Tubular Molded Article The olefin copolymer of the present invention can be used for a multilayer tubular molded article. Here, the multilayer tubular molded article is a multilayer tubular molded article that can be molded by a known multilayer tubular molding method, and comprises at least a layer containing the olefin copolymer of the present invention and a substrate layer. A multi-layer tubular molded article containing In the multi-layer tubular molding method, for example, a plurality of thermoplastic materials are extruded at the same time to combine a plurality of materials into layers, which are then discharged from a circular or irregularly shaped discharge port. By doing so, a tubular molded product having a shape conforming to the shape of the discharge port is continuously molded, and a method of obtaining a tubular molded product by molding by an appropriate shaping method and cooling method and cooling and solidifying is mentioned. can.

The shape of the discharge port in the multi-layer tubular molding method is not particularly limited, and a circular, elliptical, polygonal, or other known shape of the discharge port can be selected. In addition, the molding method of the multilayer tubular molding method is not particularly limited, and includes a sizing plate method, an internal pressure sizing method, an inner diameter sizing method, a vacuum sizing method, an extruded molten material sandwiched between molds, and compressed air from the mandrel side or from the mold side. It is possible to use a known molding method such as a method of cooling while shaping by drawing a vacuum from an empty space or the like. As for the cooling method, a known cooling method such as water cooling, air cooling, sandwiching between metal molds, or the like can be appropriately used. Furthermore, the multi-layered tubular molded article that has once been cooled and solidified can be reheated and further processed into another shape. As the base material in the base material layer of the multilayer tubular molded product, various materials as described above can be appropriately used.

(8) Multilayer Sheet The olefin copolymer of the present invention can be used as a multilayer sheet. Here, the multilayer sheet is a multilayer sheet that can be produced by known multilayer sheet molding, and is a multilayer sheet that includes at least a layer containing the olefin copolymer of the present invention and a substrate layer. . Various known methods can be used as the method for producing the multilayer sheet. For example, a plurality of thermoplastic materials are simultaneously extruded to form a layered composite, followed by a known die such as a flat die or a circular die. A method of molding into a sheet by discharging can be mentioned.

In these methods, if necessary, the edge of the multilayer sheet may be slit, or the circular multilayer sheet may be cut open. Furthermore, after extrusion molding, various processes such as vacuum molding, air pressure molding, vacuum pressure molding, stamping molding, press molding, etc. It may be further shaped by a known molding method. As the substrate in the substrate layer of the multilayer sheet according to the present invention, various materials as described above can be appropriately used.

(9) Injection Molded Articles The olefin copolymer of the present invention can be used for injection molded articles. Here, the injection-molded article is an injection-molded article obtained by molding the olefin copolymer of the present invention by injection molding. A known method can be used to manufacture the injection molded product.

(10) Multilayer injection molded article The olefin copolymer of the present invention can be used for multilayer injection molded articles. Here, the multilayer injection-molded article is a multilayer injection-molded article that includes at least a layer containing the olefin copolymer of the present invention and can be produced by combining a plurality of layers using injection molding. The multilayer injection-molded article may be a composite of two or more materials. For example, layers containing two different olefin copolymers of the present invention may be laminated. A layer comprising an olefin copolymer and a layer comprising a substrate may be multilayered. Furthermore, three or more layers may be multilayered.

A multilayer injection molded article can be molded by a known injection molding method. The multilayer injection-molded article may be a multilayer injection-molded article obtained by multilayering two or more layers containing the olefin copolymer of the present invention. Considering the adhesiveness, it is preferable to use a composite injection-molded article in which a layer containing the olefin copolymer of the present invention and a layer made of a different material are multi-layered.

Known methods can be mentioned as injection molding methods capable of producing multilayer injection molded articles. For example, the olefin copolymer of the present invention is processed into a member in advance by a known method such as injection molding, extrusion molding, press molding, cutting, etc., and the member is inserted into an injection mold, and the substrate material is further added. A method of forming multiple layers by injection, a method of forming layers by injecting the olefin copolymer of the present invention in a state in which a substrate is processed into a member in advance and the member of the substrate is inserted into an injection mold, A multi-layered method can be mentioned by using a multicolor injection molding machine having a plurality of injection units and injecting the olefin copolymer of the present invention and a substrate material into a mold sequentially in an appropriate order. . In the multi-layer injection-molded article, various types of substrates as described above can be appropriately used as the type of member to be combined with the olefin copolymer of the present invention.

(11) Coated metal member The olefin copolymer of the present invention can be used for coated metal members. Here, the coated metal member is a coated metal member that can be produced by using the olefin copolymer of the present invention as a metal coating material on a metal and coating the metal with the metal coating material. The coated metal member can be manufactured by a known metal coating method. Examples of the coated metal member include, for example, a coated steel pipe obtained by coating the outer surface or inner surface of a steel pipe with a coating material via an undercoat or the like as necessary, a coated metal wire coated with a metal coating material, and a metal coating material. Electric wire coated with, Coated metal coated by fluidized dipping method using powder-like coating metal material, Coated metal coated by electrostatic coating method using powder-like coating metal material, Sheets and films in advance, etc. For example, a coated metal coated by heat-sealing a metal coating material processed into a metal material can be exemplified.

(12) Other uses The olefin copolymer of the present invention is not only suitable for the above uses, but also polyolefin resins such as polypropylene resins, polyamide resins, polyester resins, polycarbonate resins, acrylic resins, and polyvinyl chloride resins. or as a compatibilizer for polyolefin resins such as polypropylene and engineering plastics such as polycarbonate resins, polyphenylene ether resins, polyamide resins, polyester resins, polyphenylene sulfide resins, and liquid crystal resins. be done.

In the following, the present invention will be specifically described by examples and comparative examples, and the rationality and significance of the configuration of the present invention and the prior art will be explained by comparing the data of each preferred example and each example and each comparative example. demonstrate excellence in Various evaluation methods for the olefin copolymer of the present invention are as follows.

1. Evaluation method (1) Melting point Tm and heat of fusion ΔH
The melting point Tm and heat of fusion ΔH of the produced olefin copolymer were obtained by the following DSC measurement.
Using "EXSTAR 6000" manufactured by Seiko Electronics Industry Co., Ltd., isothermal at 40 ° C. for 1 minute, increasing temperature from 40 to 160 ° C. at 10 ° C./min, isothermal at 160 ° C. for 10 minutes, 160 to 10 ° C. at 10 ° C./min After the temperature was lowered to 10° C. for 5 minutes, the melting point Tm and the heat of fusion ΔH were obtained by measuring when the temperature was raised from 10 to 160° C. at 10° C./min.

(2) Molecular weight distribution parameter Mw/Mn
The melting point molecular weight distribution parameter Mw/Mn of the produced olefin copolymer was measured by GPC.
Apparatus: Alliance GPCV2000 type manufactured by Nippon Waters Co., Ltd. Detector: Differential refractometer detector with built-in GPCV2000 Sample preparation: 3 mg of sample and orthodichlorobenzene (0.1 mg/mL of 1,2,4-trimethylphenol are added to a 4 mL vial bottle. ) was weighed out, covered with a resin screw cap and a Teflon (registered trademark) septum, and dissolved for 2 hours using a Senshu Scientific SSC-9300 high-temperature shaker set at a temperature of 150 ° C. gone. After the dissolution was completed, it was visually confirmed that there was no insoluble component.
Column: Showa Denko Shodex HT-806M × 2 + same HT-G

Preparation of a calibration curve: Prepare four 4 mL glass bottles, and weigh 0.2 mg each of monodisperse polystyrene standard samples or n-alkanes of the following combinations (i) to (iv) in each, followed by orthodichlorobenzene ( 0.1 mg / mL of 1,2,4-trimethylphenol) is weighed out, covered with a resin screw cap and a Teflon (registered trademark) septum, and then set to a temperature of 150 ° C. Made by Senshu Scientific Melting was carried out for 2 hours using a SSC-9300 high temperature shaker.

(i) Shodex S-1460, Shodex S-66.0, n-Eicosane (ii) Shodex S-1950, Shodex S-152, n-Tetracontane (iii) Shodex S-3900, Shodex S-565, Shodex S -5.05
(iv) Shodex S-7500, Shodex S-1010, Shodex S-28.5

A vial bottle containing the sample solution was set in the apparatus, measurement was performed under the conditions described above, and a chromatogram (retention time and response data set of the differential refractometer detector) was recorded at a sampling interval of 1 s. The retention time (peak apex) of each polystyrene standard sample was read from the resulting chromatogram and plotted against the logarithmic value of the molecular weight. Here, the molecular weights of n-eicosane and n-tetracontane were 600 and 1,200, respectively. A nonlinear least squares method was applied to this plot, and the resulting quartic curve was used as a calibration curve.

Calculation of molecular weight: Measurement was performed under the conditions described above, and a chromatogram was recorded at a sampling interval of 1 s. Using this chromatogram, "Size Exclusion Chromatography" written by Sadao Mori (Kyoritsu Shuppan), Chapter 4, p. A differential molecular weight distribution curve and average molecular weight values (Mn, Mw and Mz) were calculated by the methods described in 51-60. However, in order to correct the molecular weight dependence of dn/dc, the height H from the baseline in the chromatogram was corrected by the following formula. Chromatogram recording (data acquisition) and average molecular weight calculation were performed using an in-house program (created with Microsoft Visual Basic 6.0) on a PC installed with Microsoft OS Windows (registered trademark) XP. .
H′=H/[1.032+189.2/M(PE)]
However, H' represents H after correction, and M(PE) represents the molecular weight of polyethylene (peak top of differential molecular weight distribution).

The following formula was used for molecular weight conversion from polystyrene to polyethylene.
M(PE) = 0.468 x M(PS)
However, M(PS) represents the molecular weight of polystyrene (peak top of differential molecular weight distribution).

Measurement temperature: 145°C
Concentration: 20 mg/10 mL
Injection volume: 0.3ml
Solvent: 0.5 mL-DBU/1 L-orthodichlorobenzene DBU: diazabicycloundecene Flow rate: 1.0 ml/min

(3) Content of structural units derived from nitrogen-containing substituted olefin (b-1)
The comonomer content was obtained from the ¹³ C-NMR spectrum by the following method.
The quaternary carbon signal of the t-butoxycarbonyl group of 5-norbornene-2-methylamine Boc protected form (NBCH ₂ NHBoc), which is the nitrogen-containing substituted olefin (b-1) synthesized below, is shown in the ¹³ C-NMR spectrum. of 78.5 to 78.3 ppm. Quantification was determined by the following formula using signal intensity I of ¹³ C-NMR. "NB" means norbornene, and "Boc" means a t-butoxycarbonyl group.
Using these signal intensities, the content of structural units derived from NBCH ₂ NHBoc was calculated from the following formula.

Content (mol%) of structural units derived from all NBCH ₂ NHBoc = I _{(total NBCH2NHBoc)} × 100/(I _{(total NBCH2NHBoc)} + I _(E) )

The symbols in the formula are explained below.
I _{(total NBCH2NHBoc)} = I _78.5-78.3
I _(E) = (I _180.0-135.0 + I 120.0-2.0 _- I _{(total NBCH2NHBoc)} x 13)/2
I _y∼x = integrated intensity of proton signals detected from yppm to xppm

(4) Number of methyl branches calculated by ¹³ C-NMR of olefin copolymer
20.0-19.8 ppm methyl carbon, 33.2-33.0 ppm methine carbon, and 37.5-37.3 ppm methylene carbon in the ¹³ C-NMR spectrum. Using the value I divided by 4 _(B1) , the number of methyl branches per 1,000 total carbon atoms (total 1000C) was calculated using the following formula.

Number of methyl branches (number/total 1000C) = I _(B1) x 1000/I _(total)

Here, I _(B1) and I _(total) are quantities represented by the following formulas.
I _(B1) = (I _20.0-19.8 +I _33.2-33.0 +I _37.5-37.3 )/4
I _(total) = I _{180.0 to 135.0} + I _{120.0 to 2.0}
In addition, I indicates the integrated intensity, and the numerical value with the subscript of I indicates the range of the chemical shift. For example, I _180.0-135.0 indicates the integrated intensity of signals detected between 180.0 ppm and 135.0 ppm.

(5) Productivity (Vp activity)
The productivity (Vp activity) of the produced olefin copolymer was calculated by the following formula.
Productivity (Vp activity) = {yield of produced olefin copolymer (kg)} ÷ {catalyst amount (mol) x polymerization time (h)}

2. A metal catalyst was synthesized according to the synthesis example described in Japanese Patent Application Laid-Open No. 2013-043871, and a ligand B-27DM represented by the following chemical formula was prepared. Further, according to the examples of WO 2010/050256, using bis-1,5-cyclooctadiene nickel (0) (referred to as Ni(COD) ₂ ), B-27DM and Ni(COD) A nickel complex (B-27DM/Ni complex) in which ₂ reacted in a one-to-one ratio was synthesized. The B-27DM/Ni complex was used as the metal catalyst in the following examples and comparative examples.
In the chemical formulas below, "Me" represents a methyl group.

3. Examples and Comparative Examples (Method for synthesizing 5-norbornene-2-methylamine Boc protected form)
5-Norbornene-2-methylamine (NBCH ₂ NH ₂ ) (3.9 mL, 30 mmol) was mixed with water (45 mL) and cooled with ice water. Di-t-butyl dicarbonate ((Boc) ₂ O) 30% tetrahydrofuran (THF) solution (24.0 g, 33 mmol) and sodium hydroxide (1N) (30 mL) were added thereto, and stirred at room temperature for 16 hours. got the target. The end point of the reaction was confirmed using an unmodified silica gel TLC plate manufactured by Merck & Co., Ltd. In order to recover the desired product, the extract was extracted with ethyl acetate and then concentrated to obtain crystals (6.68 g, 29.9 mmol). Yield was 99.7%.

(Example 1)
Copolymerization of ethylene with 5-norbornene-2-methylamine Boc protected (NBCH ₂ NHBoc):
Dry toluene (1.0 L), 36.6 mg (0.1 mmol) of tri-n-octylaluminum (TNOA) and 4.5 g (20 mmol) of NBCH ₂ NHBoc were charged into an autoclave with an internal volume of 2.4 L and equipped with a stirring blade. is. The temperature of the autoclave was raised to 90° C. while stirring, nitrogen was supplied to 0.5 MPa, and then ethylene was supplied to the autoclave so that the ethylene partial pressure was 2.5 MPa, and the pressure was adjusted to 3.0 MPa. .

After completion of adjustment, 5 ml (10 μmol) of B-27DM/Ni catalyst toluene solution (concentration: 20 mmol/L) was injected with nitrogen to initiate copolymerization. After polymerizing for 10 minutes, the reaction was terminated by cooling and releasing the pressure. The reaction solution was poured into 1 L of acetone to precipitate a polymer, filtered and washed, recovered, and dried under reduced pressure until the weight became constant. The yield (g) of the obtained olefin copolymer was measured. In addition, the evaluation described in the above "Evaluation method" was performed. Table 1 shows the results.

In Table 1, "comonomer concentration" means the concentration of 5-norbornene-2-methylamine Boc protector in Example 1, for example. The "content" of NMR is the content of structural units derived from the comonomer (5-norbornene-2-methylamine Boc protected body in Example 1) when the entire structural units of the olefin copolymer are 100 mol%. means quantity. NMR "Me branches" means the number of methyl branches per 1000 carbon atoms in an olefin copolymer.

(Example 2)
Ethylene-NBCH ₂ NHBoc copolymerization was carried out in the same manner as in Example 1, except that the charged amount of NBCH ₂ NHBoc was 8.9 g (40 mmol) and the polymerization time was 7 minutes. The yield (g) of the obtained olefin copolymer was measured. In addition, the evaluation described in the above "Evaluation method" was performed. Table 1 shows the results.

(Example 3)
The amount of TNOA charged was 183 mg (0.5 mmol), the amount of NBCH ₂ NHBoc charged was 16.9 g (76 mmol), the ethylene partial pressure was 1.0 MPa, the catalyst toluene solution amount was 240 μmol, and the polymerization time was 60 minutes. Ethylene-NBCH ₂ NHBoc copolymerization was carried out in the same manner as in Example 1, except that The yield (g) of the obtained olefin copolymer was measured. In addition, the evaluation described in the above "Evaluation method" was performed. Table 1 shows the results.

(Example 4)
The amount of TNOA charged was 183 mg (0.5 mmol), the amount of NBCH ₂ NHBoc charged was 22.3 g (100 mmol), the ethylene partial pressure was 1.0 MPa, the catalyst toluene solution amount was 260 μmol, and the polymerization time was 60 minutes. Ethylene-NBCH ₂ NHBoc copolymerization was carried out in the same manner as in Example 1, except that The yield (g) of the obtained olefin copolymer was measured. In addition, the evaluation described in the above "Evaluation method" was performed. Table 1 shows the results.

(Comparative example 1)
Copolymerization of ethylene with 5-norbornene-2-methylamine (NBCH ₂ NH ₂ ):
37 mg (0.1 mmol) of tri-n-octylaluminum (TNOA) and 12.3 g (100 mmol) of 5-norbornene-2-methylamine (NBCH ₂ NH ₂ ) were charged, nitrogen was supplied to 0.5 MPa, and then ethylene was supplied to the autoclave so that the ethylene partial pressure was 2.5 MPa, and the pressure was adjusted to 3.0 MPa.

After completion of the adjustment, ethylene-NBCH ₂ NH ₂ copolymerization was carried out in the same manner as in Example 1 except that 25 ml (500 μmol) of B-27DM/Ni catalyst toluene solution (concentration: 20 mmol/L) was used and the polymerization time was set to 50 minutes. . The yield (g) of the obtained olefin copolymer was measured. In addition, the evaluation described in the above "Evaluation method" was performed. Table 1 shows the results.

(Comparative example 2)
Copolymerization of ethylene and N-methylmaleimide (NMM):
183 mg (0.5 mmol) of tri-n-octylaluminum (TNOA) and 5.6 g (50 mmol) of N-methylmaleimide (NMM) were charged, and nitrogen was supplied to 0.8 MPa. 0 MPa, and the pressure was adjusted to 2.8 MPa.

After completion of the adjustment, ethylene-NMM copolymerization was carried out in the same manner as in Example 1 except that 30 ml (300 μmol) of B-27DM/Ni catalyst toluene solution (concentration: 10 mmol/L) was used and the polymerization time was 120 minutes. The yield (g) of the obtained olefin copolymer was measured.

In Comparative Example 2, since the yield (g) of the olefin copolymer was small, DSC measurement, NMR measurement, and GPC measurement could not be performed. Therefore, only the productivity (Vp activity) was calculated. Table 1 shows the results.

4. Evaluation As shown in Table 1, in Examples 1 to 4, productivity (Vp activity) is higher than in Comparative Examples 1 and 2. Moreover, in Examples 1 to 4, compared with Comparative Example 1, it can be seen that a polymer having a higher weight average molecular weight (Mw) and a narrower molecular weight distribution (Mw/Mn) can be obtained. Moreover, in Example 2, as compared with Comparative Example 1, the content of the structural unit derived from the comonomer is increased although the comonomer concentration is low.

Therefore, it was confirmed that the olefin copolymer of the present invention was produced efficiently. It was also found that this olefin copolymer has a small number of methyl branches and is an excellent copolymer.

The present invention is not limited to the embodiments detailed above, and various modifications and changes are possible within the scope of the claims of the present invention.

INDUSTRIAL APPLICABILITY According to the present invention, a novel olefin copolymer having an easily decomposable protective group is provided, and this olefin copolymer is a novel olefin-based polar copolymer, and therefore can be used in a wide range of applications. can. This olefin copolymer can be produced by a simple and efficient polymerization method, and has high industrial applicability.

Claims (6)

A structural unit derived from ethylene (a-1);
and a structural unit (B) derived from a nitrogen-containing substituted olefin (b-1) represented by the following general formula (4) .

[In general formula (4), X ¹ to X ⁴ , X ⁹ , X ¹¹ and X ¹² are hydrogen atoms, and R ¹ is a hydrocarbon group having 1 to 20 carbon atoms, or a trialkyl group having 3 to 6 carbon atoms. is a silyl group, R2 ^is a hydrogen atom, methyl group, or ethyl group, and Z is a methylene group, ethylene group, or propylene group. ] 2. The olefin copolymer according to claim 1, wherein R ¹ in the general formula ( 4) is a tert-butyl group. 3. The olefin copolymer according to claim 1, wherein the number of methyl branches calculated by ¹³ C-NMR is 50 or less per 1,000 carbon atoms. 4. The olefin copolymer according to claim 3 , wherein the number of methyl branches is 5 or less per 1,000 carbon atoms. ethylene (a-1 ) ;
a nitrogen-containing substituted olefin (b-1) represented by the following general formula (4) ,
including ligands that have at least two atoms selected from the group consisting of P, N, O, and S and are bidentate or multidentate, electronically A method for producing an olefin copolymer, comprising polymerizing in the presence of a transition metal catalyst of a Group 10 metal of the periodic table having a neutral or anionic chelating ligand.

[In general formula (4), X ¹ to X ⁴ , X ⁹ , X ¹¹ and X ¹² are hydrogen atoms, and R ¹ is a hydrocarbon group having 1 to 20 carbon atoms, or a trialkyl group having 3 to 6 carbon atoms. is a silyl group, R2 ^is a hydrogen atom, methyl group, or ethyl group, and Z is a methylene group, ethylene group, or propylene group. ] 6. The method for producing an olefin copolymer according to claim 5 , wherein the transition metal catalyst is a transition metal catalyst of nickel or palladium .

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