JP6947535B2 - Olefin copolymer and its production method - Google Patents

Description

The present invention relates to an olefin copolymer and a method for producing the same. More specifically, it relates to a novel olefin copolymer having a unique structure, which is copolymerized from an ethylene and / or α-olefin monomer and a nitrogen-containing substituted olefin monomer.

Polyolefins typified by polyethylene and polypropylene are excellent in various properties such as physical properties and moldability among resin materials, are highly economical and compatible with environmental problems, and are extremely resource reusable. It is a versatile and important industrial material.
However, since polyolefins are usually non-polar, their adhesiveness to other materials, printability, and compatibility with fillers and the like are not sufficient.

Therefore, as a means for improving the physical properties, introduction of a polar functional group into polyolefin has been studied, and a method of grafting a polar group-containing monomer using an organic peroxide has been widely performed. Since intermolecular cross-linking of both olefin-based resins and molecular chain breakage of the olefin-based resin occur in parallel, the excellent physical properties of the olefin-based resin cannot be maintained in the graft-modified product.
Further, as a means for introducing a polar functional group, copolymerization of an olefin and a polar monomer is also performed, but the means for copolymerizing an olefin and a polar group-containing olefin monomer (polar comonomer) is limited to the high-pressure method. (Patent Document 1 and Patent Document 2). The copolymer has many branched structures, and only a copolymer having a low elastic modulus and low mechanical properties can be obtained.

On the other hand, in the conventional polymerization method using a metallocene catalyst, when ethylene and a polar group-containing monomer are copolymerized, the catalytic polymerization activity is lowered and it is difficult to carry out the polymerization. It has been reported that a polar comonomer is reacted with an equimolar or more organoaluminum compound (masking of a functional group) 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 formed, and it is not widely used in terms of the cost of the organoaluminum compound.

By the way, in recent years, an attempt to copolymerize an olefin and a polar comonomer by using a so-called post-metallocene, a late-period transition metal complex catalyst, without using a masking agent such as an organoaluminum compound has been energetically promoted. Has been done. So far, as polar comonomer, acrylic acid ester (Patent Documents 3 to 8), acrylonitrile (Non-Patent Document 1), vinyl ether (Non-Patent Document 2) and the like have been reported.

Considering the development status of olefin-based polar copolymers, even if a so-called post-metallocene, a late-period transition metal complex catalyst is used, the α, ω-terminal functionalized olefin has a non-polymerizable olefin moiety. Since it has a conjugated structure, it has low polymerizability and it is difficult to copolymerize with an olefin. Therefore, the present inventors have attempted to produce a copolymer of ethylene or α-olefin and α, ω-terminal functionalized olefin by using a late-period transition metal complex catalyst.

As a result, we have researched and developed a novel late-period transition metal complex catalyst having a specific structure, and found that the catalyst performance is significantly improved. Based on these research results, it was found that the olefin and the α, ω-terminal functionalized olefin can be copolymerized by using the developed catalyst, which was difficult to realize in the past. Then, the present inventors have already reported a technique for producing a copolymer of ethylene or α-olefin and α, ω-terminal functionalized olefin using a late-period transition metal complex catalyst (Patent Document 9). reference). That is, ethylene is 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 a triarylalkyne compound is coordinated with a palladium metal. And / or the invention of an olefin-based polar copolymer characterized by being composed of 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. 279292 Japanese Unexamined Patent Publication No. 3-229713 Special Table 2002-521534 Japanese Unexamined Patent Publication No. 6-184214 Japanese Unexamined Patent Publication No. 2008-22301 Japanese Unexamined Patent Publication No. 2010-150246 Japanese Unexamined Patent Publication No. 2010-150532 Japanese Unexamined Patent Publication No. 2010-20647 Japanese Unexamined Patent Publication No. 2013-213121

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 in order to expand the application range of the copolymer, the development of a new olefin-based polar copolymer is desired. rice field.
Further, it has been desired to develop an olefin-based polar copolymer that can be easily converted into a copolymer that has been difficult to directly synthesize. For example, it has been desired to develop a copolymer that can be easily decomposed and converted into a copolymer having an amino group.

An object of the present invention is to provide a novel olefin copolymer using a post-metallocene catalyst having an easily decomposable protecting group, and a method for producing the same.

As a result of intensive studies to solve the above problems, the present inventors have found that a nitrogen-containing substituted olefin having a specific substituent can be used for good copolymerization even with a post-metallocene catalyst. Based on the findings and these findings, the present invention has been completed.

That is, the first invention of the present invention is at least selected from the group consisting of 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. One type of structural unit (A) and
A structural unit derived from a nitrogen-containing substituted olefin (b-1) having a substituent represented by the following general formula (1), and a nitrogen-containing substituted olefin (b) having a substituent represented by the following general formula (2). It is an olefin copolymer characterized by having at least one structural unit (B) selected from the group consisting of structural units derived from -2).

[In the formula, R ¹ is a hydrocarbon group having 1 to 20 carbon atoms, and R ² is a hydrogen atom, a methyl group, an ethyl group, a benzyl group, or a trialkylsilyl group. ]

[In the formula, R ³ is a divalent organic group having 1 to 10 carbon atoms. ]

In the second invention of the present invention, at least one of the nitrogen-containing substituted olefin (b-1) and the nitrogen-containing substituted olefin (b-2) has a structure represented by the following general formula (3). The olefin copolymer according to the first invention.

[In the formula, R ⁴ is a hydrogen atom or a methyl group. ]

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

[In the formula, R ¹ is a hydrocarbon group having 1 to 20 carbon atoms, R ² is a hydrogen atom, a methyl group, an ethyl group, a benzyl group, or a trialkylsilyl group, and R ⁴ is a hydrogen atom. Alternatively, it is a methyl group, and Z is a divalent organic group. ]

The fourth invention of the present invention is the olefin copolymer according to the second invention, wherein the nitrogen-containing substituted olefin (b-2) has a structure of the following general formula (5). ..

[In the formula, R ³ is a divalent organic group having 1 to 10 carbon atoms, R ⁴ is a hydrogen atom or a methyl group, and Z is a divalent organic group. ]

In the fifth aspect of the present invention, Z in at least one of the general formula (4) and the general formula (5) is − (CH ₂ ) _n −, −COO (CH ₂ ) _m −, −O. (CH ₂ ) _{represented by m} − or −CO (CH ₂ ) _m −, n is an integer of 2 to 30, and m is an integer of 0 to 30. The olefin copolymer according to the invention.

In the sixth invention of the present invention, Z in at least one of the general formula (4) and the general formula (5) is − (CH ₂ ) _n −, −COO (CH ₂ ) _m − or −O. (CH ₂ ) _{The olefin copolymer according to the fifth invention, which is represented by m} −, n is an integer of 2 to 30, and m is an integer of 0 to 30.

In the seventh invention of the present invention, Z in at least one of the general formula (4) and the general formula (5) is represented by _{− (CH 2} ) _n − or −COO (CH ₂ ) _{m −.} , N is an integer of 2 to 30, and m is an olefin copolymer according to the sixth invention.

In the eighth invention of the present invention, Z in at least one of the general formula (4) and the general formula (5) _{is represented by −COO (CH 2} ) _m −, and m is an integer of 0 to 30. The olefin copolymer according to the seventh invention.

The ninth invention of the present invention is the olefin copolymer according to the eighth invention, wherein ^{R 1 in the general formula (4) is a tert-butyl group.}

The tenth invention of the present invention is described in the ninth invention, wherein Z in at least one of the general formula (4) and the general formula (5) is −COOCH ₂ CH _{2 −.} It is an olefin copolymer of.

The eleventh invention of the present invention includes the olefin according to the tenth invention, wherein ^{R 4} in at least one of the general formula (4) and the general formula (5) is a hydrogen atom. It is a polymer.

The twelfth invention of the present invention is described in any one of the first to eleventh inventions, wherein the number of methyl branches calculated by ^{13 C-NMR is 50 or less per 1,000 carbons.} It is an olefin copolymer of.

The thirteenth invention of the present invention is the olefin copolymer according to the twelfth invention, wherein the number of methyl branches is 5 or less per 1,000 carbons.

The fourteenth invention of the present invention includes at least one selected from the group consisting of ethylene (a-1) and α-olefin (a-2) having 3 to 20 carbon atoms.
It is composed of a nitrogen-containing substituted olefin (b-1) having a substituent represented by the following general formula (1) and a nitrogen-containing substituted olefin (b-2) having a substituent represented by the following general formula (2). At least one selected from the group,
A method for producing an olefin copolymer, which comprises polymerizing in the presence of a transition metal catalyst of a metal of Group 5 to 11 of the periodic table having a chelating ligand.

[In the formula, R ¹ is a hydrocarbon group having 1 to 20 carbon atoms, and R ² is a hydrogen atom, a methyl group, an ethyl group, a benzyl group, or a trialkylsilyl group. ]

[In the formula, R ³ is a divalent organic group having 1 to 10 carbon atoms. ]

The fifteenth invention of the present invention is the method for producing an olefin copolymer according to the fourteenth invention, wherein the transition metal catalyst is a transition metal catalyst of Group 10 of the periodic table.

According to the present invention, there is provided a novel olefin copolymer having a protecting group that can be easily decomposed. Since this 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 a protecting group that can be easily decomposed.
Further, according to the production method of the present invention, a novel olefin copolymer having a protecting group that can be easily decomposed can be easily and efficiently produced.

FIG. 1 (a) is an image diagram of the molecular structure of an olefin copolymer polymerized by a high-pressure radical method polymerization process, and FIG. 1 (b) is an olefin copolymer polymerized using a metal catalyst and has no long-chain branching. FIG. 1 (c) is an image diagram of the molecular structure of the case, which 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 a method for producing the same will be described 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. At least one structural unit (A) selected from the group and
A structural unit derived from a nitrogen-containing substituted olefin (b-1) having a substituent represented by the following general formula (1), and a nitrogen-containing substituted olefin (b) having a substituent represented by the following general formula (2). It has at least one structural unit (B) selected from the group consisting of structural units derived from -2).

[In the formula, R ¹ is a hydrocarbon group having 1 to 20 carbon atoms, and R ² is a hydrogen atom, a methyl group, an ethyl group, a benzyl group, or a trialkylsilyl group. ]

[In the formula, R ³ is a divalent organic group having 1 to 10 carbon atoms. ]

(2) Constituent unit (A) (2-1) Constituent unit (A)
The olefin copolymer of the present invention is at least one selected from the group consisting of 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. It is characterized by having a structural unit (A) of. The ethylene or α-olefin having 3 to 20 carbon atoms to be subjected to the polymerization is not particularly limited, but preferably contains ethylene (a-1) indispensably, and if necessary, the α-olefin having 3 to 20 carbon atoms ( a-2) may be further included. Ethylene (a-1) or α-olefin (a-2) having 3 to 20 carbon atoms to be subjected to polymerization may be used alone, or two or more kinds may be used. Further, a monomer containing no other polar group may be further subjected to polymerization as long as it does not deviate from the gist of the present invention. The proportion of structural units derived from ethylene (a-1) and α-olefin (a-2) is not particularly limited, but is usually 80 to 99 when the total amount of the olefin copolymer is 100 mol%. It is desirable to select from the range of .999 mol%, preferably 85 to 99.99 mol%, more preferably 90 to 99.98 mol%, and more preferably 95 to 99.97 mol%.

(2-2) α-olefin The α-olefin according to the present invention is an α-olefin having 3 to 20 carbon atoms represented by the _{structural formula: CH 2} = CHR ^{18 (R 18} has 1 to 18 carbon atoms). It is a hydrocarbon group and may have a linear structure or a branch). More preferably, it is an α-olefin having 3 to 12 carbon atoms, and even more preferably, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 3-methyl-1-butene and It is an α-olefin selected from 4-methyl-1-pentene, and more preferably an α-olefin selected from propylene, 1-butene, 1-hexene and 1-octene. The α-olefin to be subjected to the polymerization may be used alone or in combination of two or more.

(2-3) Monomer that does not contain a polar group The monomer that does not contain a polar group according to the present invention is a monomer that has one or more carbon-carbon double bonds in its molecular structure, and the elements that make up the molecule are It is not limited as long as it is only carbon and hydrogen, and examples thereof include diene, triene, aromatic vinyl monomer, cyclic olefin, and the like, and preferred are butadiene, isoprene, styrene, vinylcyclohexane, cyclohexene, vinylnorbornene, and norbornene.

(3) Constituent unit (B) (3-1) Constituent unit (B)
The structural unit (B) is a structural unit derived from a nitrogen-containing substituted olefin (b-1) having a substituent represented by the following general formula (1), and a substituent represented by the following general formula (2). It is selected from the group consisting of structural units derived from the nitrogen-containing substituted olefin (b-2) having.

[In the formula, R ¹ is a hydrocarbon group having 1 to 20 carbon atoms, and R ² is a hydrogen atom, a methyl group, an ethyl group, a benzyl group, or a trialkylsilyl group. ]

[In the formula, R ³ is a divalent organic group having 1 to 10 carbon atoms. ]

^{The hydrocarbon group having 1 to 20 carbon atoms in R 1} of the general formula (1) is not particularly limited, but is a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, or an iso-butyl. Examples thereof include a group, an n-butyl group, a tert-butyl group, an n-octyl group, an n-eicosyl group, a phenyl group, a benzyl group, an o-toluyl group, an m-toluyl group, a p-toluyl group and the like.

The trialkylsilyl group in R ² of the general formula (1) is not particularly limited, can be exemplified trimethylsilyl group, triethylsilyl group, a tert- butyldimethylsilyl group, and the like.

Examples of the divalent organic group having 1 to 10 carbon atoms in R ³ of the general formula (2) is not particularly limited, an alkylene group (e.g., methylene group, ethylene group, trimethylene group, propylene group, tetramethylene group, pentamethylene Methylene group, hexamethylene group, etc.), cycloalkylene group (eg, cyclohexylene group, etc.), aromatic hydrocarbon group (eg, phenylene group (o, m or p-phenylene group), methylphenylene group, dimethylphenylene group, etc.) , Naftylene group, etc.) are exemplified.

The nitrogen-containing substituted olefin (b-1) preferably has a structure represented by the following general formula (3).

[In the formula, R ⁴ is a hydrogen atom or a methyl group. ]

The nitrogen-containing substituted olefin (b-2) preferably has a structure represented by the following general formula (3).

[In the formula, R ⁴ is a hydrogen atom or a methyl group. ]

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

[In the formula, R ¹ is a hydrocarbon group having 1 to 20 carbon atoms, R ² is a hydrogen atom, a methyl group, an ethyl group, a benzyl group, or a trialkylsilyl group, and R ⁴ is a hydrogen atom. Alternatively, it is a methyl group, and Z is a divalent organic group. ]

The divalent organic group in Z of the general formula (4) is not particularly _{limited, - (CH 2) n -} , - COO (CH 2) m -, - O (CH 2) m - or -CO ( CH ₂ ) _{A group represented by m} − is preferable (where n is an integer of 2 to 30 and m is an integer of 0 to 30).
As a divalent organic group in Z, a more preferable embodiment is − (CH ₂ ) _n −, −COO (CH ₂ ) _m − or −O (CH ₂ ) _m − (where n is 2 to 30). Is an integer of, and m is an integer of 0 to 30.).
As a divalent organic group in Z, a particularly preferable embodiment is − (CH ₂ ) _n − or −COO (CH ₂ ) _m − (where n is an integer of 2 to 30 and m is 0 to 0. It is an integer of 30.).
As a divalent organic group in Z, the optimum embodiment is −COO (CH ₂ ) _m − (where m is an integer of 0 to 30), and the most preferable embodiment is −COOCH ₂ CH. _2- .

^{R 1} of the general formula (4) is a hydrocarbon group having 1 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 is a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, or an iso-butyl. Examples thereof include a group, an n-butyl group, a tert-butyl group, an n-octyl group, an n-eicosyl group, a phenyl group, a benzyl group, an o-toluyl group, an m-toluyl group, a p-toluyl group and the like. ^{As R 1} of the general formula (4), a tert-butyl group is particularly preferable.

^{R 2} of the general formula (4) is a hydrogen atom, a methyl group, an ethyl group, a benzyl group, or a trialkylsilyl group. The trialkylsilyl group in R ² of the general formula (4) is not particularly limited, can be exemplified trimethylsilyl group, triethylsilyl group, a tert- butyldimethylsilyl group, and the like.
R ⁴ in the general formula (4) is a hydrogen atom or a methyl group. A hydrogen atom is preferable as ^{R 4} of the general formula (4).

The nitrogen-containing substituted olefin (b-2) preferably has the structure of the following general formula (5).

[In the formula, R ³ is a divalent organic group having 1 to 10 carbon atoms, R ⁴ is a hydrogen atom or a methyl group, and Z is a divalent organic group. ]

The divalent organic group in Z of the general formula (5) is not particularly _{limited, - (CH 2) n -} , - COO (CH 2) m -, - O (CH 2) m - or -CO ( CH ₂ ) _{A group represented by m} − is preferable (where n is an integer of 2 to 30 and m is an integer of 0 to 30).
As a divalent organic group in Z, a more preferable embodiment is − (CH ₂ ) _n −, −COO (CH ₂ ) _m − or −O (CH ₂ ) _m − (where n is 2 to 30). Is an integer of, and m is an integer of 0 to 30.).
As a divalent organic group in Z, a particularly preferable embodiment is − (CH ₂ ) _n − or −COO (CH ₂ ) _m − (where n is an integer of 2 to 30 and m is 0 to 0. It is an integer of 30.).
As a divalent organic group in Z, the optimum embodiment is −COO (CH ₂ ) _m − (where m is an integer of 0 to 30), and the most preferable embodiment is −COOCH ₂ CH. _2- .

^{R 3} of the general formula (5) is a divalent organic group having 1 to 10 carbon atoms. Examples of the divalent organic group having 1 to 10 carbon atoms in R ³ in the general formula (5) is not particularly limited, an alkylene group (e.g., methylene group, ethylene group, trimethylene group, propylene group, tetramethylene group, pentamethylene Methylene group, hexamethylene group, etc.), cycloalkylene group (eg, cyclohexylene group, etc.), aromatic hydrocarbon group (eg, phenylene group (o, m or p-phenylene group), methylphenylene group, dimethylphenylene group, etc.) , Naftylene group, etc.) are exemplified.

R ⁴ in the general formula (5) is a hydrogen atom or a methyl group. A hydrogen atom is preferable as ^{R 4} of the general formula (5).

(3-2) Specific Examples of Nitrogen-Containing Substituents (b-1) Examples of nitrogen-containing substituted olefins (b-1) will be specifically described below.

(3-3) Specific Examples of Nitrogen-Containing Substituents (b-2) Examples of nitrogen-containing substituted olefins (b-2) will be specifically described below.

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

(5) Amount of structural units of nitrogen-containing substituted olefin The ratio of the total structural units of the structural units derived from the nitrogen-containing substituted olefin (b-1) and the structural units derived from the nitrogen-containing substituted olefin (b-2) is Although not particularly limited, when the total amount of the 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%. It is selected from the range, more preferably from the range of 5 to 0.03 mol%. From this range, if the total structural unit amount of the structural unit derived from the nitrogen-containing substituted olefin (b-1) and the structural unit derived from the nitrogen-containing substituted olefin (b-2) is small, the material with a highly polar dissimilar material can be used. If the adhesiveness is not sufficient and exceeds this range, sufficient mechanical properties may not be obtained.

(6) Method for measuring the structural unit derived from the nitrogen-containing substituted olefin (b-1) and the structural unit derived from the nitrogen-containing substituted olefin (b-2) The nitrogen-containing substituted olefin (nitrogen-containing substituted olefin) in the olefin copolymer of the present invention. The amount of structural unit derived from b-1) and the amount of structural unit derived from the nitrogen-containing substituted olefin (b-2) can be determined using a ^{1 H-NMR spectrum. 1 1} H-NMR spectrum was measured by the following method.
Sample 200-250 mg with o-dichlorobenzene / deuterated benzene (C ₆ D ₅ Br) = 4/1 (volume ratio) 2.4 ml and hexamethyldisiloxane, which is a reference substance for chemical shift, with an inner diameter of 10 mmφ. It was placed in an NMR sample tube, replaced with nitrogen, sealed, heated and dissolved, and subjected to NMR measurement as a uniform solution. The NMR measurement was performed at 130 ° C. using an AV400M type NMR apparatus of Bruker Biospin Co., Ltd. equipped with a 10 mmφ cryoprobe. ^{1 1} H-NMR was measured with a pulse angle of 1 °, a pulse interval of 1.8 seconds, and a total number of integrations of 512 times or more. For the chemical shift, the peak of the methyl proton of hexamethyldisiloxane was set to 0.088 ppm, and the chemical shift of the peak due to other protons was based on this.

The number of methyl branches in the olefin copolymer described later can be determined by ^{13 C-NMR. 13} C-NMR was measured by the proton complete decoupling method with a pulse angle of 90 °, a pulse interval of 20 seconds, and an integration number of 512 times or more. For the chemical shift, the peak of methyl carbon of hexamethyldisiloxane was set as 1.98 ppm, and the chemical shift of peaks due to other carbons was based on this.

(7) Molecular Structure of Olefin Copolymer The olefin copolymer according to the present invention is derived from a structural unit derived from ethylene (a-1) and an α-olefin (a-2) having 3 to 20 carbon atoms. From at least one structural unit (A) selected from the group consisting of structural units, a structural unit derived from the nitrogen-containing substituted olefin (b-1), and a structural unit derived from the nitrogen-containing substituted olefin (b-2). It is preferable that the random copolymer has at least one structural unit (B) selected from the above group.
An example of the molecular structure of the olefin copolymer of the present invention is shown in the following paragraph. A random copolymer is a type of structural unit adjacent to the A structural unit and B structural unit of the molecular structure example shown below, which have a probability of finding each structural unit at a position in an arbitrary molecular chain. It is an irrelevant copolymer. Further, the molecular chain terminal of the olefin copolymer may be ethylene or an α-olefin having 3 to 20 carbon atoms, and may be a nitrogen-containing substituted olefin (b-1) or a nitrogen-containing substituted olefin (b-2). There may be. As described below, in the molecular structure (example) of the olefin copolymer of the present invention, ethylene or an α-olefin having 3 to 20 carbon atoms and a nitrogen-containing substituted olefin form a random copolymer.

In addition, when the molecular structure (example) of the olefin copolymer by graft modification is also posted for reference, ethylene (a-1) and / or α-olefin (a-2) having 3 to 20 carbon atoms were copolymerized. A part of the olefin copolymer is graft-modified with a nitrogen-containing substituted olefin (b-1) and / or a nitrogen-containing substituted olefin (b-2).

The olefin copolymer of the present invention is preferably produced in the presence of a transition metal catalyst, and its molecular structure is preferably linear. An image of the olefin copolymer polymerized by the high-pressure radical polymerization process is shown in FIG. 1 (a), and an image of the olefin copolymer polymerized using a metal catalyst is shown in FIGS. 1 (b) and 1 (c). As illustrated above, the molecular structure differs depending on the production method. This difference in molecular structure can be controlled by selecting the manufacturing method. For example, as described in Japanese Patent Application Laid-Open No. 2010-150532, the complex elastic modulus measured by a rotary rheometer. The molecular structure can also be estimated by.

More specifically, when the phase angle δ (G * = 0.1 MPa) at the absolute value G * = 0.1 MPa of the complex elastic modulus measured by the rotary rheometer is 40 degrees or more, the molecular structure thereof is shown in FIG. A structure that does not contain any long-chain branches (FIG. 1 (b)) as shown in (b) and FIG. 1 (c), or a structure that contains a small amount of long-chain branches that does not affect the mechanical strength. (Fig. 1 (c)) is shown.
When the phase angle δ (G * = 0.1 MPa) at the absolute value G * = 0.1 MPa of the complex elastic modulus measured by the rotary rheometer is lower than 40 degrees, the molecular structure is shown in FIG. 1 (a). It shows a structure containing an excessive number of long-chain branches, and the mechanical strength is inferior.

The phase angle δ at the absolute value G * = 0.1 MPa of the complex elastic modulus measured by the rotary rheometer is affected by both the molecular weight distribution and the long chain branch, but Mw / Mn ≦ 4, more preferably Mw / Mn ≦. If it is limited to 3, it becomes an index of the amount of long-chain branching, and the more long-chain branching, the smaller the δ (G * = 0.1MPa) value. If Mw / Mn is 1.5 or more, the δ (G * = 0.1 MPa) value does not exceed 75 degrees even if there is no long chain branch.

(8) Weight average molecular weight (Mw) of olefin copolymer
The weight average molecular weight (Mw) of the olefin copolymer according to 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. It is desirable that the range is 000, preferably 31,000 to 800,000, and 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 having high polarity may be inferior. If Mw exceeds 2,000,000, the melt viscosity becomes very high, which may make molding difficult.

The copolymer of ethylene and / or α-olefin and polar group-containing olefin of the present invention usually has a ratio (Mw / Mn) of weight average molecular weight (Mw) to number average molecular weight (Mn) of 1.5 to 3. It is preferably in the range of 5.5, preferably 1.6 to 3.3, and more preferably 1.7 to 3.0. If Mw / Mn is less than 1.5, various processability tends to be insufficient, while if Mw / Mn exceeds 3.5, performance such as adhesiveness tends to be insufficient. In addition, Mw / Mn may be expressed as a molecular weight distribution parameter.

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

(9) Melting Point of Polar Group-Containing Olefin Copolymer The melting point of the olefin copolymer of the present invention is indicated by the maximum peak temperature of the heat absorption 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 when the vertical axis is the heat flow (mW) and the horizontal axis is the temperature (° C.) in the DSC measurement. Indicates the maximum peak temperature, and when there is one peak, it indicates the peak temperature.
Assuming polyethylene, the melting point is preferably 50 ° C. to 140 ° C., more preferably 60 ° C. to 138 ° C., and most preferably 70 ° C. to 135 ° C. If it is lower than this range, the heat resistance is not sufficient, and if it is higher than this range, the adhesiveness is inferior.

(10) olefin copolymer methyl branches number present invention calculated by ¹³ C-NMR of the olefin ^copolymer, methyl branches number calculated by 13 C-NMR, 50 or less per 1,000 carbon It is preferable to have. Of these, the number of methyl branches is particularly preferably 5 or less per 1,000 carbons. 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 the polymerization temperature. A reduction in the polymerization temperature is effective as a specific means for reducing the number of methyl branches of the copolymer. For example, it is required to regulate these factors to control the copolymer region of interest.

The number of methyl branches is measured as follows. _{The total I total} of the integrated intensity of the peaks of 2 to 60 ppm and 170 to 180 ppm of carbon is standardized to 1,000, and the integrated intensity of the signal of 20 ppm methyl-branched methyl carbon and the integrated of 33 ppm of methyl-branched methine carbon are integrated. the number of methyl branches per total 1000 carbon were calculated using the following equation using the values I _B1 divided by the sum of integrated intensity of the intensity and 37ppm signal with methylene carbon of methyl branch at 4.
Methyl branches number (number / Total _{1000C) = I B1 × 1000 /} I _Total
For the chemical shift, the peak of methyl carbon of hexamethyldisiloxane was set as 1.98 ppm, and the chemical shift of peaks due to other carbons was based on this.

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

[In the formula, R ¹ is a hydrocarbon group having 1 to 20 carbon atoms, and R ² is a hydrogen atom, a methyl group, an ethyl group, a benzyl group, or a trialkylsilyl group. ]

[In the formula, R ³ is a divalent organic group having 1 to 10 carbon atoms. ]

^{R 1} and ^{R 2} in general formula (1) in, ^{R 3} in the general formula (2) is << 1. Regarding the olefin copolymer, the description of R ¹ , R ² , and R ³ described in the item >> is applied as it is (including the preferable embodiment), and the description thereof is omitted.

(2) Polymerization catalyst of olefin copolymer The types of the polymerization catalyst according to the present invention are ethylene (a-1) and / or α-olefin (a-2) having 3 to 20 carbon atoms, and the above-mentioned general formula ( Selected from the group consisting of a nitrogen-containing substituted olefin (b-1) having a substituent represented by 1) and a nitrogen-containing substituted olefin (b-2) having a substituent represented by the above general formula (2). The method is not particularly limited as long as it can be copolymerized with at least one of these compounds, and for example, there is a method of polymerizing using a Group 5 to 11 transition metal compound having a chelating ligand as a catalyst. ..

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, and the like. Examples include copper atoms.
Among these, the transition metal of Group 8 to 11 is preferable, the transition metal of Group 10 is more preferable, and nickel (Ni) and palladium (Pd) are particularly preferable. These metals may be single or in combination of two or more.

Further, the transition metal of the transition metal complex of the present invention is an element in which M is selected from the group consisting of nickel (II), palladium (II), platinum (II), cobalt (II) and rhodium (III). Is preferable, and more preferably, it is a Group 10 element from the viewpoint of polymerization activity, and nickel (II) is particularly preferable from the viewpoint of price and the like.
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. A review by Brookhard et al. Illustrates its structure (Chem. Rev., 2000, 100, 1169).
Preferably, the bidentate anionic P, O ligand includes, for example, phosphorus sulfonic acid, phosphorus carboxylic acid, phosphophenol, phosphorus enolate, and other bidentate anionic N, O ligand, for example, salicyl. Examples include aldomynate 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 represented by the following structural formulas (α) and / or (β) coordinated with an arylphosphine compound, an arylarsine compound or an arylantimon compound which may have a substituent. expressed.

In the structural formula (α) and the structural formula (β), M represents a transition metal belonging to any of Group 5 to 11 of the periodic table of elements, that is, various transition metals as described above. X ¹ represents oxygen, sulfur, -SO _3- , or -CO _2- . Y ¹ represents carbon or silicon. n represents 0 or 1. E ¹ represents phosphorus, arsenic or antimony. R ³ and R ⁴ each independently represent a hydrocarbon group that may contain hydrogen or a heteroatom having 1 to 30 carbon atoms. R ⁵ represents a hydrocarbon group that may independently contain hydrogen, a halogen, and a heteroatom having 1 to 30 carbon atoms. R ⁶ and R ⁷ are each independently hydrogen, halogen, and a hydrocarbon group which may contain 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 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, and y represents an integer from 0 to 2. R ⁶ and R ⁷ may be linked to each other to form an alicyclic ring, an aromatic ring, or a heterocycle containing a hetero atom selected from oxygen, nitrogen, and sulfur. 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 hydrogen 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 a ligand coordinated to M. Further, R ³ and L ¹ may be combined with each other to form a ring.
The structure of the metal complex obtained from the 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 Group 5 to 11 of the periodic table of elements, that is, the above-mentioned transition metal. X ¹ represents oxygen, sulfur, -SO _3- , or -CO _2- . Y ¹ represents carbon or silicon. n represents 0 or 1. E ¹ represents phosphorus, arsenic or antimony. R ³ and R ⁴ each independently represent a hydrocarbon group that may contain hydrogen or a heteroatom having 1 to 30 carbon atoms. R ⁵ represents a hydrocarbon group that may independently contain hydrogen, a halogen, and a heteroatom having 1 to 30 carbon atoms. R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ are each independently hydrogen, halogen, hydrocarbon group which may contain 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' represents _{PO 3 M '2, P (} O) (oR 2) 2 M' or epoxy containing group. M'represents an alkali metal, alkaline earth metal, ammonium, quaternary ammonium or phosphonium, x represents an integer from 0 to 3, and y represents an integer from 0 to 2. Incidentally, connected appropriately selected plurality of groups with each other from R ⁸ to R ^11, alicyclic, aromatic ring, or oxygen, nitrogen, also form a heterocyclic ring containing a hetero atom selected from sulfur good. 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 hydrogen 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 a ligand coordinated to M. Further, R ³ and L ¹ may be combined with each other to form a ring.

Here, as a catalyst of the transition metal compounds of Groups 5 to 11 having a chelating ligand, so-called Shop-based and Drent-based catalysts are typically known. Shop-based catalysts are catalysts in which a phosphorus-based ligand having an aryl group, which may have a substituent, is coordinated to a nickel metal (see, for example, International Publication No. 2010-05256). The Drent system is a catalyst in which a phosphorus-based ligand having an aryl group, which may have a substituent, is coordinated to a palladium metal (see, for example, JP-A-2010-202647).

(3) Organic Metal Compound In the production of the olefin copolymer according to the present invention, at least one selected from the group consisting of the above-mentioned nitrogen-containing substituted olefin (b-1) and nitrogen-containing substituted olefin (b-2). After contacting with a small amount of the organic metal compound, in the presence of the above-mentioned transition metal catalyst, ethylene (a-1) and / or α-olefin (a-2) having 3 to 20 carbon atoms and nitrogen-containing substitution are performed. The polymerization activity can be further enhanced by copolymerizing with at least one selected from the group consisting of an olefin (b-1) and a nitrogen-containing substituted olefin (b-2).
The organic metal compound is an organic metal compound containing a hydrocarbon group which may have a substituent, and can be represented by the following structural formula (H).

(In the formula, R ³⁰ represents a hydrocarbon group which may have a substituent having 1 to 12 carbon atoms, and M ³⁰ is Group 1, Group 2, Group 12 and Group 13 of the periodic table. A metal selected from the group consisting of, X ^30, represents a halogen atom or a hydrogen atom, m'is a valence of ^{M 30, and n'is 1 to m'.)}

Examples of the organic metal compound represented by the structural formula (H) include alkylaluminums 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, and trialkylaluminum is preferably selected. More preferably, trialkylaluminum having a hydrocarbon group having 4 or more carbon atoms, more preferably trialkylaluminum having a hydrocarbon group having 6 or more carbon atoms, more preferably tri-n-hexylaluminum, tri. -N-octyl aluminum and tri-n-decyl aluminum are selected, and tri-n-octyl aluminum can be most preferably used.

^{The organic metal compound has a molar ratio of 10-5 to} 0.9, preferably ^{10-4 to} 0, with respect to the polar group-containing comonomer (nitrogen-containing substituted olefin (b-1) and nitrogen-containing substituted olefin (b-2)). It is preferable to bring in an amount of .2, more preferably 10 ^{-4 to} 0.1, from the viewpoint of polymerization activity and cost.

(4) Aluminum (Al) content remaining in 1g of the olefin copolymer according to the remaining amount present invention aluminum (Al) is preferably not more than 100,000 micrograms _Al / g, more or less 70,000μg _Al / g preferably, more preferably less 20,000 _Al / g, or less and particularly preferably 10,000 _[Al / g, a preferable less 5,000 micrograms _Al / g, and more preferably less 1,000 .mu.g _Al / g, 500 [mu] g _Al / g or less is most preferable. If the amount is more than this, the mechanical properties of the olefin copolymer are likely to be deteriorated, and the discoloration and deterioration of the polymerization product are likely to be promoted. Residual amounts of aluminum (Al) may have the smaller to the extent possible, for example, may be a very small amount of about 1 [mu] g _Al / g, it may be a 0 Pg _Al / g. In addition, μg _Al / g means that the amount of aluminum (Al) contained in 1 g of a polar group-containing olefin copolymer is expressed in μg units.

(5) Calculation of Aluminum (Al) Amount The amount of aluminum (Al) contained in the olefin copolymer according to the present invention is the amount of aluminum contained in the alkylaluminum used for polymerization, and the obtained olefin copolymer is obtained. It can be calculated as a value divided by the yield of.

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

(5-1) Fluorescent X-ray analysis Weigh 3 to 10 g of the measurement sample and mold it under heat and pressure with a heating press to prepare a flat sample with a diameter of 45 mm. The measurement is performed on a portion having a diameter of 30 mm at the center of the flat plate sample, and is measured under the following conditions using a scanning fluorescent X-ray analyzer "ZSX100e" (Rh tube 4.0 kW) manufactured by Rigaku Denki Kogyo Co., Ltd.
・ X-ray output: 50kV-50mA
-Spectroscopic crystal: PET
・ Detector: PC (proportional counter)
-Detection line: Al-Kα line The aluminum content can be obtained from the calibration curve prepared in advance and the result of measurement 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 further analyzing the polyethylene resins by fluorescent X-ray under the above conditions.

(5-2) Inductively coupled plasma atomic emission (ICP) analysis A measurement sample, 3 ml of special grade nitrate, and 1 ml of hydrogen peroxide solution (hydrogen peroxide content: 30% by weight) were placed in a container made of Teflon (registered trademark), and a microwave decomposition apparatus (microwave decomposition apparatus) was used. Using MLS-1200MEGA manufactured by Milestone General Co., Ltd., perform a thermal decomposition operation at a maximum of 500 W to liquefy the measurement sample. The aluminum content can be measured by subjecting the measured sample in solution to an ICP emission spectrophotometer (IRIS-AP manufactured by Thermogerel Ash). The aluminum content is quantified using a calibration curve prepared using a standard solution having a known aluminum element concentration.

(6) Polymerization method of olefin copolymer The polymerization method of the olefin copolymer according to the present invention is not limited. Slurry polymerization in which at least a part of the produced polymer becomes a slurry in a medium, bulk polymerization using the liquefied monomer itself as a medium, vapor phase polymerization performed in a vaporized monomer, or a polymer produced in a monomer liquefied at high temperature and high pressure. High-pressure ion polymerization or the like in which at least a part of the above is dissolved is preferably used.
The polymerization format may be any of batch polymerization, semi-batch polymerization, and continuous polymerization. Further, it may be a living polymerization, or the polymerization may be carried out while causing chain transfer. Further, a so-called chain shutdown agent (CSA) may be used in combination to carry out a chain shutdown reaction or a coordinative 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. About additives >>
The olefin copolymer according to the present invention includes antioxidants, ultraviolet absorbers, lubricants, antistatic agents, colorants, pigments, cross-linking agents, foaming agents, nucleating agents, and difficulties, as long as the gist of the present invention is not deviated. Additives such as flame retardants, conductive materials, and fillers may be blended.

<< 4. Use of the olefin copolymer of the present invention >>
(1) Adhesive Material The olefin copolymer of the present invention has a specific molecular structure and resin physical characteristics, so that it exhibits high adhesiveness to other base materials and enables the production of industrially useful laminates. I made it. In particular, the adhesive performance with various substrates is the structural unit derived from the nitrogen-containing substituted olefin (b-1) and the nitrogen-containing substituted olefin (b-2) in the olefin copolymer in the above-mentioned olefin copolymer. The total amount of the above 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%, and more preferably in the range of 5 to 0.03 mol%. If it is, it is fully expressed.

(2) Laminated body (2-1) Material of laminated body The olefin copolymer of the present invention can be used for the laminated body. Specifically, the laminate is a laminate containing a layer made of the olefin copolymer of the present invention and a base material layer, and the base material layer is an olefin resin such as polyethylene or polypropylene, a polyamide resin, or the like. Examples of substrates include polyester resins, highly polar thermoplastic resins such as ethylene-vinyl alcohol copolymers (EVOH), adhesive fluororesins, and metal materials such as aluminum and steel.

Specific examples of the base material include high-density polyethylene, medium-density polyethylene, low-density polyethylene, ethylene-vinyl acetate copolymer, ethylene-acrylic acid ester copolymer, ionomer, homopolypropylene resin, propylene and other α-olefins. Copolymer with, olefin resin such as poly-1-butene, poly-4-methyl-1-pentene, vinyl polymer such as polyvinyl chloride, polyvinylidene chloride, polystyrene, polyacrylate, polyacrylonitrile, nylon 6, Nylon 66, Nylon 10, Nylon 11, Nylon 12, Nylon 610, Polypolymer resin such as polymethoxylylen adipamide, Polyethylene terephthalate, Polyethylene terephthalate / isophthalate, Polybutylene terephthalate, Polylactic acid, Polybutylene succinate, Thermoplastic resin films or sheets (and) having film-forming ability such as polyester resins such as aromatic polyesters, polyvinyl alcohols, ethylene / vinyl alcohol copolymers, polycarbonate resins, adhesive fluororesins, and cellulose polymers such as cellophane. These stretched materials, printed materials), metal foils or metal plates such as aluminum, iron, copper, or alloys containing these as main components, vapor-deposited films of inorganic oxides such as silica-deposited plastic films and alumina-deposited plastic films, gold, Examples include vapor-deposited films such as metals such as silver and aluminum, or compounds other than oxides of these metals, high-quality paper, kraft paper, paperboard, glassin paper, synthetic paper and other papers, cellophane, woven fabrics, non-woven fabrics, etc. can.

The base material layer can be appropriately selected depending on the intended use and the type of the object to be packaged. For example, when the packaged product is a perishable food, it has transparency, rigidity, and gas permeation resistance such as polyamide, polyvinylidene chloride, ethylene-vinyl alcohol copolymer (EVOH), polyvinyl alcohol, and polyester. An excellent resin can be used. When the object to be packaged is confectionery or fiber, it is preferable to use polypropylene or the like having good transparency, rigidity and water permeation resistance. When adapted to fuel tanks of automobiles, tubes, hoses, pipes, etc. through which fuel passes, resins having excellent fuel permeation prevention performance such as EVOH, polyamides, and fluororesins can be used.
Barrier resins include polyamide resins, polyester resins, EVOH, polyvinylidene chloride resins, polycarbonate resins, stretched polypropylenes (OPPs), stretched polyesters (OPETs), stretched polyamides, alumina vapor-deposited films, silica vapor-deposited films, and the like. Examples thereof include vapor-deposited films of metals and inorganic oxides, metal-deposited films such as aluminum vapor-deposited, and metal foils.

(2-2) Use of Laminated Body The laminated body is suitable as, for example, a packaging material for foods. Specific examples of foods include snack foods such as potato chips, sweets such as biscuits, rice crackers and chocolate, powdered seasonings such as powdered soup, and foods such as bonito flakes and scented foods.
Further, the container can be formed by facing each other of the ethylene-based copolymer layer surfaces of the above-mentioned laminate and heat-sealing at least a part thereof. Specifically, for example, water packaging, bags, liquid soup packaging bags, liquid paper containers, lami raw fabrics, specially shaped liquid packaging bags (standing pouches, etc.), standard bags, heavy bags, semi-heavy bags, wrap films, sugar. It is suitably used for bags, oil packaging bags, various packaging containers for food packaging, infusion bags, and the like.

(2-3) Manufacture of laminated body As the processing method of the laminated body, ordinary press molding, air-cooled inflation molding, air-cooled two-stage cooling inflation molding, high-speed inflation molding, flat die molding (T-die molding), water-cooled inflation molding Examples thereof include previously known methods such as extrusion molding, extrusion laminating processing, sand laminating processing, laminating processing methods such as dry laminating processing, blow molding, pressure molding, injection molding, and rotary molding.

(2-4) Laminated Laminated Body The laminated laminated body is a laminated body that can be manufactured by a known laminating processing method such as extrusion laminating processing, sand laminating processing, dry laminating processing, etc., and the laminating laminated body is the present invention. It is a laminate that can be produced by laminating a laminate material containing the olefin copolymer of No. 1 and at least one or more base material layers. The laminating material in the present invention is a resin material containing the olefin copolymer of the present invention that can be used in various known laminating processing methods.

Extrusion laminating is a method of continuously coating and pressure-bonding a molten resin film extruded from a T-die onto a base material, and is a molding method in which coating and adhesion are performed at the same time. Further, the sand laminating process is a method in which a molten resin is poured between a film to be laminated with paper, and the molten resin acts like an adhesive to adhere and laminate. The dry laminating process dehumidifies the atmospheric humidity near the adhesive and / or the adhesive coating roll that adheres the film to be laminated with the base material, or heats the temperature of the adhesive and / or the adhesive coating roll. Alternatively, it is a method of drying the bonded surface of the film sheet.
In the sand laminating process and the dry laminating process, on the side where the layer containing the polar group-containing olefin copolymer of the base material used in the present invention is formed, between the base material and the layer containing the polar group-containing olefin copolymer. In addition, in order to improve the barrier property, it is easy to laminate the above aluminum foil, polyester film, various barrier properties and the like. As the base material layer to be laminated with the laminating material according to the present invention, various various materials as described above can be appropriately used.

(3) Extruded product The olefin copolymer of the present invention can be used for an extruded product. Here, the extrusion-molded product is an extrusion-molded product obtained by molding the olefin copolymer of the present invention by extrusion molding. Extruded products according to the present invention include various inflation moldings 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, deformed extrusion molding, tubular product molding, calendar molding, and the like. It can be manufactured by extrusion molding. Further, in a state where the extruded product obtained by extrusion molding is not completely solidified, it may be further shaped by various known methods such as sandwiching it in a mold or the like or applying deformation. Further, post-processing may be added to the obtained extruded product by various known methods such as bending, cutting, reheating and then shaping.

(4) Multi-layer coextruded product The olefin copolymer of the present invention can be used for a multi-layer co-extruded product. Here, the multi-layer co-extruded product is a multi-layer co-extruded product that can be molded by a known multi-layer co-extrusion molding, and is a multi-layer co-extruded product containing at least a layer containing the olefin copolymer of the present invention. It is a molded product.
A multi-layer coextruded product is a multi-layer structure that can be manufactured by simultaneously extruding a plurality of thermoplastic materials to composite a plurality of materials into layers and molding them by various shaping methods. It is a molded product with.

Methods for manufacturing multi-layer coextruded 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), and multi-layer tubular product molding. Known multi-layer coextrusion molding such as multi-layer corrugated pipe molding can be mentioned.

As the base material layer in the multi-layer coextruded product, various materials as described above can be appropriately used. A multi-layer coextruded product is a multi-layer film, multi-layer sheet, multi-layer pipe, multi-layer hose, multi-layer tube, by processing a layer containing the olefin copolymer of the present invention and an appropriate base material by an appropriate molding method. It can be manufactured as a known multi-layer coextruded product such as a multi-layer corrugated pipe. Further, in a state where the multi-layer co-extrusion molded product obtained by the multi-layer co-extrusion molding is not completely solidified, it may be further shaped by various known methods such as sandwiching it in a mold or the like or applying deformation. Further, post-processing may be added to the obtained multi-layer coextruded product by various known methods such as bending, cutting, reheating and then shaping.

(5) Multilayer film The olefin copolymer of the present invention can be used for a multilayer coextruded product. 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 material layer. be. As a method for manufacturing 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) are used. Can be used. As the base material layer of the multilayer film, various materials as described above can be appropriately used.

(6) Multi-layer blow-molded product The olefin copolymer of the present invention can be used for multi-layer blow-molded products. Here, the multi-layer blow-molded product is a multi-layer blow-molded product that can be manufactured by a known multi-layer blow molding, and includes at least a layer containing the olefin copolymer of the present invention and a base material layer. It is a multi-layer blow molded product. Examples of the method for manufacturing a multi-layer blow molded product include known blow molding methods such as multi-layer direct blow molding, multi-dimensional multi-layer blow molding, and multi-layer rotary blow molding. As the base material layer of the multilayer blow-molded product according to the present invention, various materials as described above can be appropriately used.

(7) Multi-layered tubular molded product The olefin copolymer of the present invention can be used for multi-layered tubular molded products. Here, the multi-layer tubular molded product is a multi-layer tubular molded product that can be molded by a known multi-layer tubular molding method, and at least a layer containing the olefin copolymer of the present invention and a base material layer are formed. It is a multi-layer tubular molded product including. In the multi-layer tubular molding method, for example, a plurality of thermoplastic materials are extruded at the same time to form a layered composite of the plurality of materials, and the plurality of materials are continuously ejected from a circular or irregularly shaped discharge port to form a shape conforming to the discharge port shape. Can be mentioned as a method in which a tubular molded product is formed, and a tubular molded product is obtained by molding and cooling and solidifying by an appropriate shaping method and a cooling method.

The discharge port shape of the multi-layer tubular molding method is not particularly limited, and a circular, elliptical, polygonal, or other known discharge port shape can be selected. The molding method of the multi-layer tubular molding method is not particularly limited, and the sizing plate method, the internal pressure sizing method, the inner diameter sizing method, the vacuum sizing method, and the extruded molten material are sandwiched between molds, and the air-cooled or mold side is pressed from the mandrel side. A known molding method such as a method of cooling while shaping by vacuuming from the mold can be used, and the cooling method can be appropriately used such as water cooling, air cooling, and sandwiching with a mold. Further, the multilayer tubular molded product once cooled and solidified can be reheated and further processed into another shape. As the base material layer of the multi-layer 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 for 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 containing at least a layer containing the olefin copolymer of the present invention and a base material layer. .. Various known methods can be used as a method for producing the multilayer sheet. For example, a plurality of thermoplastic materials are extruded at the same time to form a layered composite of the plurality of materials, and a known die such as a flat die or a circular die is used. A method of forming into a sheet by discharging can be mentioned. Further, in these methods, if necessary, the edge of the sheet may be slit or a circular sheet may be cut open. Further, in a state where the multilayer sheet is not cooled and solidified after extrusion molding, or is remelted by reheating the cooled and solidified multilayer sheet, various types such as vacuum forming, pressure forming, vacuum pressure forming, stamping molding, press molding, etc. Further shaping may be performed by a known molding method. As the base material layer of the multilayer sheet according to the present invention, various materials as described above can be appropriately used.

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

(10) Multi-layer injection molded product The olefin copolymer of the present invention can be used for a multi-layer injection molded product. Here, the multi-layer injection-molded product is a multi-layer injection-molded product that contains 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 multi-layer injection molded product may be a composite of two or more kinds of materials. For example, a layer containing two different olefin copolymers of the present invention may be laminated. The layer containing the olefin copolymer and the layer made of the base material may be multi-layered. Further, three or more kinds of layers may be multi-layered.

The multi-layer injection molded product can be molded by a known injection molding method. A multi-layer injection-molded product obtained by multi-layering two or more types of layers containing the olefin copolymer of the present invention may be used, but it is characterized by having high adhesiveness to different materials, which is a feature of the present invention. In consideration, it is preferable that the composite injection-molded product has a layer made of different materials and multiple layers.
As an injection molding method capable of producing a multi-layer injection molded product, a known method can be mentioned. For example, the olefin copolymer of the present invention is processed into a member by a known method such as injection molding, extrusion molding, press molding, or cutting in advance, and the base material is further added in a state where the member is inserted into the injection mold. A method of forming a multi-layer by injection, a method of processing a base material into a member in advance, and injecting the olefin copolymer of the present invention in a state where the member of the base material is inserted into an injection mold to form a multi-layer. Examples include a method in which the olefin copolymer of the present invention and the base material are sequentially injected into a mold in an appropriate order using a multicolor injection molding machine having a plurality of injection units to form multiple layers. .. In the multi-layer injection molded product, various base materials as described above can be appropriately used as the type of the member to be composited with the olefin copolymer of the present invention.

(11) Coated metal member The olefin copolymer of the present invention can be used as a coated metal member. 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 and coating the metal coating material with a metal. 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 in which the outer surface or the inner surface of the steel pipe is coated with a coating material via an undercoat or the like, if necessary, a coated metal wire coated with the metal coating material, and a metal coating material. Wires coated with, coated metal coated by the fluidized immersion method using a powder-like coating metal material, coating metal coated by an electrostatic coating method using a powder-like coating metal material, sheets, films, etc. in advance A coated metal or the like coated by heat-welding a metal coating material processed into a metal material for a metal material can be mentioned.

(12) Other Applications The olefin copolymer of the present invention is not only suitably used as the above-mentioned adhesive resin material, but also a polyolefin resin such as polypropylene resin, a polyamide resin, a polyester resin, a polycarbonate resin, an acrylic resin, and a poly. Also as a modifier for various resins such as vinyl chloride resin, or as a compatibilizer between polyolefin resin such as polypropylene and engineering plastics such as polycarbonate resin, polyphenylene ether resin, polyamide resin, polyester resin, polyphenylene sulfide resin, and liquid crystal resin. Suitablely applied.

Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples, and the rationality and significance of the configuration of the present invention and the prior art will be based on the data of each suitable Example and the comparison between each Example and each Comparative Example. Demonstrate excellence against. Various evaluation methods of the olefin copolymer produced in the present invention are as follows.

1. 1. Evaluation method (1) Melting point Tm
The melting point Tm of the produced olefin copolymer was determined by the following DSC measurement.
Using "EXSTAR6000" manufactured by Seiko Electronics Inc., 40 ° C for 1 minute isothermal, 10 ° C / min for 40 to 160 ° C, 160 ° C for 10 minute isothermal, 10 ° C / min for 160-10 ° C. The temperature was lowered to 10 ° C. for 5 minutes, and then the temperature was increased to 10 to 160 ° C. at 10 ° C./min.

(2) Molecular weight distribution parameter Mw / Mn: Measured by GPC.
Equipment: Alliance GPCV2000 type detector manufactured by Japan Waters Co., Ltd .: Differential refractometer detector with built-in GPCV2000 Sample preparation: 3 mg of sample and orthodichlorobenzene (0.1 mg / mL 1,2,4-trimethylphenol) in a 4 mL vial. (Including) 3 mL is weighed, covered with a resin screw cap and a Teflon (registered trademark) septum, and then dissolved for 2 hours using a Senshu Kagaku SSC-9300 high-temperature shaker set at a temperature of 150 ° C. went. After completion of dissolution, it was visually confirmed that there were no insoluble components.
Column: Showa Denko Shodex HT-806M x 2 + same HT-G
Calibration curve preparation: Prepare four 4 mL glass bottles, each weighing 0.2 mg of a monodisperse polystyrene standard sample or n-alkane of the combination of (i) to (iv) below, followed by orthodichlorobenzene (orthodichlorobenzene). Weigh 3 mL (including 0.1 mg / mL 1,2,4-trimethylphenol), cover with a resin screw cap and Teflon® septum, and then set the temperature to 150 ° C. manufactured by Senshu Kagaku. Melting was carried out for 2 hours using an SSC-9300 type high temperature shaker.
(I) Shodex S-1460, S-66.0, n-eicosane (ii) Shodex S-1950, S-152, n-tetracontane (iii) Shodex S-3900, S-565, S -5.05
(Iv) Shodex S-7500, S-1010, S-28.5
A vial containing the sample solution was set in the device, measurement was performed under the above conditions, and a chromatogram (data set of retention time and response 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 obtained chromatogram and plotted against the logarithmic value of the molecular weight. Here, the molecular weights of n-icosane and n-tetracontane were set to 600 and 1,200, respectively. The nonlinear least squares method was applied to this plot, and the obtained quadratic curve was used as the calibration curve.

Calculation of molecular weight: Measurement was performed under the above conditions, and chromatograms were recorded at a sampling interval of 1 s. Using this chromatogram, Sadao Mori, "Size Exclusion Chromatography" (Kyoritsu Shuppan), Chapter 4, p. The differential molecular weight distribution curve and the average molecular weight value (Mn, Mw and Mz) were calculated by the method 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 on which Microsoft OS, Windows (registered trademark), and XP were installed. ..
H'= H / [1.032 + 189.2 / M (PE)]
The following formula was used for the molecular weight conversion from polystyrene to polyethylene.
M (PE) = 0.468 x M (PS)
Measurement temperature: 145 ° C, concentration: 20 mg / 10 mL, injection volume: 0.3 ml
Solvent: orthodichlorobenzene, flow rate: 1.0 ml / min

(3) Content of constituent unit amount derived from nitrogen-containing substituted olefin (b-1)
^{1 From the 1} H-NMR spectrum, the comonomer content was determined by the following method.
The quantification was calculated by the following formula using the signal intensity of ^{1 H-NMR.}

Content of main chain type 2BOCAEA (mol%) = (I _α + I _br ) / 3 × 100 / ( _INCH2 + _IE )
Content of all 2 BOCAEA (mol%) = _INCH2 / 2 × 100 / ( _INCH2 + _IE )

The symbols in the formula are explained below.
Integral strength of α-methylene proton of I _{α = 1.62 to 1.78 ppm I br} = Integral strength of main chain methine proton of _{2.32 to} 2.50 ppm I NCH2 = Integral strength of methylene proton of 3.08 to 3.78 ppm Intensity _IE = 0.25 × (I _0-3- I _NCH2 × 9)
Integral intensity of proton signal detected from I _{0 to 3 = 0 ppm to 3 ppm}

2. The metal catalyst B-27DM / Ni complex and B-111 / Ni complex were synthesized according to the synthesis example described in JP2013-043871, and the ligands B-27DM and B-111 represented by the following chemical formulas were used. used. Also, according to the examples of International Publication No. 2010/050256, B-27DM and Ni (COD) are used using _{bis-1,5-cyclooctadiene nickel (0) (referred to as Ni (COD) 2). A nickel complex in which 2} and B-111 and Ni (COD) ₂ reacted 1: 1 was synthesized.

3. 3. Example and Comparative Example (Example 1)
Copolymerization of ethylene with 2- (t-butoxycarbonylamino) ethyl (BOCAEA) acrylate:
In an autoclave with a stirring blade with an internal volume of 2.4 liters, dry toluene (1.0 liters), tri-n-octyl aluminum (TNOA) 36.6 mg (0.1 mmol) and a predetermined amount of 2- (t) acrylic acid. -Butoxycarbonylamino) ethyl (BOCAEA) was charged in 2.2 g (10 mmol). The temperature of the autoclave was raised to 90 ° C. with stirring, nitrogen was supplied to 0.5 MPa, and then ethylene was supplied to the autoclave to adjust the pressure to 3.0 MPa. After completion of the adjustment, 12 ml (120 μmol) of the B-27DM / Ni catalyst was press-fitted with nitrogen to initiate copolymerization. After polymerizing for 14 minutes, the reaction was stopped by cooling and depressurizing. The reaction solution was poured into 1 liter of acetone to precipitate a polymer, which was then collected by filtration and washing, and further dried under reduced pressure until the amount became constant. The results are shown in Table 1.
In Table 1, "CM concentration" means a comonomer concentration, that is, a 2- (t-butoxycarbonylamino) ethyl acrylate concentration. The "content" of NMR means the content of a structural unit derived from 2- (t-butoxycarbonylamino) ethyl acrylate when the total structural unit of the olefin copolymer is 100 mol%.

(Example 2)
Ethylene-BOCAEA copolymerization was carried out in the same manner as in Example 1 except that the amount of BOCAEA was 4.3 g (20 mmol), the amount of B-27DM / Ni catalyst was 24 ml (240 μmol), and the polymerization time was 30 minutes. The results are shown in Table 1.

(Example 3)
Ethylene-BOCAEA copolymerization was carried out in the same manner as in Example 1 except that the amount of BOCAEA was 4.3 g (20 mmol), the amount of B-111 / Ni catalyst was 18 ml (180 μmol), and the polymerization time was 25 minutes. The results are shown in Table 1.

(Example 4)
Ethylene-BOCAEA copolymerization was carried out in the same manner as in Example 1 except that the amount of BOCAEA was 1.0 g (4.7 mmol), the amount of B-111 / Ni catalyst was 2.5 ml (25 μmol), and the polymerization time was 55 minutes. rice field. The results are shown in Table 1.

(Example 5)
The same as in Example 1 except that BOCAEA was 0.8 g (3.9 mmol), the amount of B-111 / Ni catalyst was 3.0 ml (30 μmol), the autoclave temperature was 110 ° C., and the polymerization time was 50 minutes. Ethylene-BOCAEA copolymerization was performed. The results are shown in Table 1.

(Example 6)
The same as in Example 1 except that BOCAEA was 0.7 g (3.3 mmol), the amount of B-111 / Ni catalyst was 3.0 ml (30 μmol), the autoclave temperature was 130 ° C., and the polymerization time was 45 minutes. Ethylene-BOCAEA copolymerization was performed. The results are shown in Table 1.

(Example 7)
The same as in Example 1 except that BOCAEA was 0.6 g (2.9 mmol), the amount of B-111 / Ni catalyst was 5.5 ml (55 μmol), the autoclave temperature was 150 ° C., and the polymerization time was 55 minutes. Ethylene-BOCAEA copolymerization was performed. The results are shown in Table 1.

(Comparative Example 1)
Copolymerization of ethylene with 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, nitrogen was supplied up to 0.8 MPa, and then ethylene was supplied to the autoclave and the pressure was increased. 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 the B-27DM / Ni catalyst was 30 ml (300 μmol) and the polymerization time was 120 minutes. The results are shown in Table 1.
In Table 1, "CM concentration" means a comonomer concentration, that is, an N-methylmaleimide concentration. The "content" of NMR means the content of a structural unit derived from N-methylmaleimide when the total structural unit of the olefin copolymer is 100 mol%.

4. As shown in the evaluation table 1, in Examples 1 to 7, the content of the structural unit derived from the comonomer (acrylic acid 2- (t-butoxy)) in each of Examples 1 to 7 was lower than that in Comparative Example 1. The content of structural units derived from carbonylamino) ethyl) is high. On the other hand, N-methylmaleimide cannot be copolymerized under the same conditions. Therefore, it was confirmed that the olefin copolymer of the present invention was efficiently produced. Then, it was found that this olefin copolymer was an excellent copolymer with a small number of methyl branches even under a polymerization temperature condition of 150 ° C.

The present invention is not limited to the embodiments detailed above, and various modifications or modifications can be made within the scope of the claims of the present invention.

According to the present invention, a novel olefin copolymer having a protecting group that can be easily decomposed is provided, and since this is a novel olefin-based polar copolymer, it can be used in a wide range of applications. This olefin copolymer can be produced by a simple and efficient polymerization method, and has high industrial applicability.

Claims (10)

At least one structural unit (A) selected from the group consisting of 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 derived from a nitrogen-containing substituted olefin (b-1) having a substituent represented by the following general formula (1), and a nitrogen-containing substituted olefin (b) having a substituent represented by the following general formula (2). -At least one structural unit (B) selected from the group consisting of structural units derived from 2), and
Have,
The nitrogen-containing substituted olefin (b-1) has a structure represented by the following general formula (4), and the nitrogen-containing substituted olefin (b-2) has a structure represented by the following general formula (5). Meet at least one of the
¹³ An olefin copolymer characterized in that the number of methyl branches calculated by C-NMR is 50 or less per 1,000 carbons.

[In the formula, R ¹ is a hydrocarbon group having 1 to 20 carbon atoms, and R ² is a hydrogen atom, a methyl group, an ethyl group, a benzyl group, or a trialkylsilyl group. ]

[In the formula, R ³ is a divalent organic group having 1 to 10 carbon atoms. ]

[In the formula, R ¹ is a hydrocarbon group having 1 to 20 carbon atoms, R ² is a hydrogen atom, a methyl group, an ethyl group, a benzyl group, or a trialkylsilyl group, and R ⁴ is a hydrogen atom. Alternatively, it is a methyl group, where Z is represented by − (CH ₂ ) _n −, −COO (CH ₂ ) _m −, −O (CH ₂ ) _m − or −CO (CH ₂ ) _m −, and n is 2. It is an integer of ~ 30, and m is an integer of 0 to 30. ]

[In the formula, R ³ is a divalent organic group having 1 to 10 carbon atoms, R ⁴ is a hydrogen atom or a methyl group, and Z is − (CH ₂ ) _n −, −COO (CH _2). ) _M −, −O (CH ₂ ) _m − or −CO (CH ₂ ) _m −, n is an integer of 2 to 30, and m is an integer of 0 to 30. ] Z in at least one of the general formula (4) and the general formula (5) is represented by − (CH ₂ ) _n −, −COO (CH ₂ ) _m − or −O (CH ₂ ) _m −. The olefin copolymer according to claim 1, wherein n is an integer of 2 to 30, and m is an integer of 0 to 30. Z in at least one of the general formula (4) and the general formula (5) is represented by − (CH ₂ ) _n − or −COO (CH ₂ ) _m −, and n is an integer of 2 to 30. The olefin copolymer according to claim 2, wherein m is an integer of 0 to 30. Claim that Z in at least one of the general formula (4) and the general formula (5) _{is represented by −COO (CH 2} ) _m −, and m is an integer of 0 to 30. The olefin copolymer according to 3. The olefin copolymer according to claim 4, ^{wherein R 1} in the general formula (4) is a tert-butyl group. The olefin copolymer according to claim 5, wherein Z in at least one of the general formula (4) and the general formula (5) is −COOCH ₂ CH _{2 −.} The olefin copolymer according to claim 6, wherein ^{R 4} in at least one of the general formula (4) and the general formula (5) is a hydrogen atom. The olefin copolymer according to any one of claims 1 to 7, wherein the number of methyl branches is 5 or less per 1,000 carbons. At least one selected from the group consisting of ethylene (a-1) and α-olefin (a-2) having 3 to 20 carbon atoms, and
It is composed of a nitrogen-containing substituted olefin (b-1) having a substituent represented by the following general formula (1) and a nitrogen-containing substituted olefin (b-2) having a substituent represented by the following general formula (2). At least one selected from the group,
Polymerized in the presence of a transition metal catalyst of Group 5-11 metals of the Periodic Table with a chelating ligand.
The nitrogen-containing substituted olefin (b-1) has a structure represented by the following general formula (4), and the nitrogen-containing substituted olefin (b-2) has a structure represented by the following general formula (5). Meet at least one of the
A method for producing an olefin copolymer, wherein the number of methyl branches of the obtained olefin copolymer ^{calculated by 13 C-NMR is 50 or less per 1,000 carbon atoms.}

[In the formula, R ¹ is a hydrocarbon group having 1 to 20 carbon atoms, and R ² is a hydrogen atom, a methyl group, an ethyl group, a benzyl group, or a trialkylsilyl group. ]

[In the formula, R ³ is a divalent organic group having 1 to 10 carbon atoms. ]

[In the formula, R ¹ is a hydrocarbon group having 1 to 20 carbon atoms, R ² is a hydrogen atom, a methyl group, an ethyl group, a benzyl group, or a trialkylsilyl group, and R ⁴ is a hydrogen atom. Or a methyl group, where Z is represented by − (CH ₂ ) _n −, −COO (CH ₂ ) _m −, −O (CH ₂ ) _m − or −CO (CH ₂ ) _m −, and n is 2. It is an integer of ~ 30, and m is an integer of 0 to 30. ]

[In the formula, R ³ is a divalent organic group having 1 to 10 carbon atoms, R ⁴ is a hydrogen atom or a methyl group, and Z is − (CH ₂ ) _n −, −COO (CH _2). ) _M −, −O (CH ₂ ) _m − or −CO (CH ₂ ) _m −, n is an integer of 2 to 30, and m is an integer of 0 to 30. ] The method for producing an olefin copolymer according to claim 9, wherein the transition metal catalyst is a transition metal catalyst of Group 10 of the periodic table.

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