阅读说明：本技术 多元系含极性基团的烯烃共聚物 (Olefin copolymer containing polar group in multi-component system ) 是由 佐藤智彦 小林稔 上松正弘 山田芳佳 于 2018-12-17 设计创作，主要内容包括：提供一种透明性、刚性、和韧性之间的平衡优异的多元系含极性基团的烯烃共聚物。所述多元系含极性基团的烯烃共聚物的特征在于,其包括：选自由源自乙烯的结构单元和源自碳数为3至20的α-烯烃的结构单元组成的组的至少1种结构单元(A)、由含极性基团的烯烃单体组成的至少1种结构单元(B)、以及源自非极性环状烯烃的结构单元(C)。(Disclosed is a polar group-containing olefin copolymer of a multicomponent system, which is excellent in the balance among transparency, rigidity and toughness, and which is characterized by comprising at least 1 structural unit (A) selected from the group consisting of a structural unit derived from ethylene and a structural unit derived from an α -olefin having 3 to 20 carbon atoms, at least 1 structural unit (B) consisting of a polar group-containing olefin monomer, and a structural unit (C) derived from a nonpolar cyclic olefin.)

1. A multi-system polar group-containing olefin copolymer comprising:

at least 1 structural unit (A) selected from the group consisting of a structural unit derived from ethylene and a structural unit derived from α -olefin having a carbon number of 3 to 20,

a structural unit (B) derived from a polar group-containing olefin monomer represented by the following general formula (1), and

a structural unit (C) derived from a nonpolar cyclic olefin represented by the following general formula (2):

wherein T is¹To T³Each independently a substituent selected from the group consisting of a hydrogen atom, a hydrocarbon group having a carbon number of 1 to 20, a silyl group having a carbon skeleton having a carbon number of 1 to 18, an alkoxy group having a carbon number of 1 to 20, a halogen group, and a cyano group;

T⁴is a substituent selected from the group consisting of:

ester group with carbon number of 2 to 30, carboxyl group, carboxylate group,

an alkoxycarbonyl group having a carbon number of 2 to 30 and in which a part of the carbon skeleton is substituted with at least 1 substituent selected from the group consisting of an ester group, a carboxyl group and a carboxylate group,

a hydrocarbon group having a carbon number of 2 to 20 in which a part of the carbon skeleton is substituted with at least 1 substituent selected from the group consisting of an ester group, a carboxyl group and a carboxylate group,

an alkoxy group having a carbon number of 1 to 20 in which a part of the carbon skeleton is substituted with at least 1 substituent selected from the group consisting of an ester group, a carboxyl group and a carboxylate group,

an acyloxy group having a carbon number of 2 to 20 and in which a part of the carbon skeleton is substituted with at least 1 substituent selected from the group consisting of an ester group, a carboxyl group and a carboxylate group,

a substituted amino group having a carbon number of 1 to 12, wherein a part of the carbon skeleton is substituted with at least 1 substituent selected from the group consisting of an ester group, a carboxyl group and a carboxylate group, and

a substituted silyl group having a carbon number of 1 to 18, in which a part of the carbon skeleton is substituted with at least 1 substituent selected from the group consisting of an ester group, a carboxyl group, and a carboxylate group;

the carboxylate group is a carboxylate group containing a metal ion of group 1, group 2 or group 12 of the periodic table; and is

T¹、T²、T³And T⁴Optionally in combination to form a ring,

wherein R is¹To R¹²Each of which is optionally the same or different and each is selected from the group consisting of a hydrogen atom, a halogen atom and a hydrocarbon group having a carbon number of 1 to 20;

R⁹and R¹⁰Optionally integrated to form a divalent organic group, and R¹¹And R¹²Optionally integrated to form a divalent organic group; r⁹Or R¹⁰Optionally with R¹¹Or R¹²Forming a ring; and is

n is 0 or a positive integer, and when n is 2 or more, R⁵To R⁸Each is optionally the same or different in each repeat unit.

2. The multi-system polar-group-containing olefin copolymer according to claim 1, wherein T⁴Is a substituent selected from the group consisting of:

ester group with carbon number of 2 to 30, carboxyl group, carboxylate group,

an alkoxycarbonyl group having a carbon number of 2 to 30 in which a part of the carbon skeleton is substituted with at least 1 substituent selected from the group consisting of an ester group, a carboxyl group and a carboxylate group, and

a hydrocarbon group having a carbon number of 2 to 20 in which a part of the carbon skeleton is substituted with at least 1 substituent selected from the group consisting of an ester group, a carboxyl group and a carboxylate group.

3. The multi-system polar group-containing olefin copolymer according to claim 1 or 2, wherein T⁴Is an ester group, a carboxyl group or a carboxylate group having a carbon number of 2 to 30.

4. The multi-system polar group-containing olefin copolymer according to any one of claims 1 to 3, wherein T⁴Is a carboxyl or carboxylate group.

5. The multi-system polar group-containing olefin copolymer according to any one of claims 1 to 4, wherein T¹And T²Each is a hydrogen atom, T³Is a hydrogen atom or a methyl group.

6. The polar group-containing olefin copolymer of any one of claims 1 to 5, wherein the content of the structural unit (C) derived from a nonpolar cyclic olefin is from 0.1 mol% to 20 mol%.

7. The polar group-containing olefin copolymer of any one of claims 1 to 6, wherein the content of the structural unit (B) derived from the polar group-containing olefin monomer is from 2 mol% to 20 mol%.

8. The polar group-containing olefin copolymer of any one of claims 1 to 7, wherein the weight average molecular weight/number average molecular weight (Mw/Mn) as determined by gel permeation chromatography is 1.5 or more and 4.0 or less.

9. The multi-system polar group-containing olefin copolymer according to any one of claims 1 to 8, wherein a melting point (Tm) (C) observed by differential scanning calorimetry and a total content [ Z ] (mol%) of the structural unit (B) and the structural unit (C) satisfy the following formula (I):

50< Tm < -3.74 × [ Z ] +130.

10. The multi-system polar group-containing olefin copolymer according to any one of claims 1 to 9, wherein the absolute value of the complex modulus G as measured by a rotational rheometer^*Is 0.1MPa (G)^*0.1MPa) of 50 to 75 degrees.

11. The multi-system polar group-containing olefin copolymer according to any one of claims 1 to 10, wherein the copolymer is obtained by¹³The number of methyl branches calculated by C-NMR is 5 or less per 1,000 carbon atoms.

12. The multi-system polar group-containing olefin copolymer according to any one of claims 1 to 11, wherein the multi-system polar group-containing olefin copolymer is a multi-system polar group-containing olefin copolymer produced by using a transition metal catalyst containing a transition metal of group 10 of the periodic table.

13. The polar group-containing olefin copolymer of claim 12, wherein the transition metal of group 10 of the periodic table is nickel or palladium.

Technical Field

The present invention relates to a multi-system polar group-containing olefin copolymer.

Background

The ethylene based ionomer is a resin containing AN ethylene-unsaturated carboxylic acid copolymer as a base resin and in which intermolecular bonding is formed by metal ions such as sodium and zinc, and is characterized by toughness, high elasticity, high flexibility, abrasion resistance, transparency, and the like (patent document 1) commercially available ionomer products are known to include "SUR L YN (trade name)" (sodium and zinc salts produced by copolymerization of ethylene-methacrylic acid developed by DuPont) and "HIMI L AN (trade name)" (commercially available from DuPont-Mitsui polychemics co., L td.).

Specifically, as an ethylene-unsaturated carboxylic acid copolymer used for conventionally known ethylene based ionomers, a polar group-containing olefin copolymer produced by polymerizing polar group-containing monomers such as ethylene and (meth) acrylic acid by a high-pressure radical polymerization method is used. However, for the polar group-containing olefin copolymer produced by the high-pressure radical polymerization method, the molecular structure is a structure containing many long-chain branches and short-chain branches irregularly, and the structure has a problem of insufficient strength.

There are reports of another production method of a polar group-containing olefin copolymer used as a base resin of an ethylene-based ionomer, in which a copolymer of ethylene and t-butyl acrylate is produced by using a late transition metal catalyst; modifying the thus obtained polar group-containing olefin copolymer into an ethylene-acrylic acid based copolymer by heating or acid treatment; then, an ethylene-acrylic acid copolymer is reacted with a metal ion to produce an ethylene ionomer (patent document 2).

Since the polar group-containing olefin copolymer produced by using the transition metal catalyst is used as a base resin, the resulting ionomer is excellent in thermal properties, mechanical strength, and the like. However, the ionomer has a problem of low transparency due to high crystallinity of the ionomer.

With respect to the ethylene based ionomer described in "example" of patent document 2 in which an ethylene-acrylic acid based copolymer is used as a base resin, the transparency thereof can be controlled by the crystallinity thereof. However, since the ionomer has a trade-off relationship between crystallinity and rigidity, once the crystallinity is decreased to improve transparency, the rigidity is decreased and it is difficult to balance transparency, rigidity and toughness of the ethylene based ionomer.

There is a report of a method for producing a highly rigid ionomer, in which a maleic anhydride is introduced into an ethylene-Cyclic Olefin Copolymer (COC) by graft modification, and then the copolymer is reacted with a metal ion to produce an ethylene ionomer (patent document 3).

However, the ionomer production method has the following problems: since it is extremely difficult to produce a copolymer containing a large amount of maleic anhydride by graft modification, the acid content of the copolymer is small. Actually, the maleic anhydride content of the copolymer described in "example" of patent document 3 is only 0.7 to 1.4% by weight (0.5 to 1 mol%). Therefore, the vinyl ionomer containing the graft-modified copolymer as a base resin is poor in adhesion because the number of polar moieties in the copolymer is small.

Further, the ethylene type ionomer is considered to be unable to exhibit desired toughness and elasticity because the number of reaction sites between the ethylene type ionomer and metal ions is small.

In addition, the ethylene-based ionomer used in "example" of patent document 3 has a problem of high glass transition temperature (Tg) and being excessively hard because the content of cyclic olefin in the base resin is large and 21 to 35 mol%.

Disclosure of Invention

Problems to be solved by the invention

In view of the above-described circumstances in the prior art, an object of the present invention is to provide a multi-component polar group-containing olefin copolymer having a good balance among transparency, rigidity and toughness.

Means for solving the problems

The multi-component polar group-containing olefin copolymer of the present invention is a multi-component polar group-containing olefin copolymer comprising:

at least 1 structural unit (A) selected from the group consisting of a structural unit derived from ethylene and a structural unit derived from α -olefin having a carbon number of 3 to 20,

a structural unit (B) derived from a polar group-containing olefin monomer represented by the following general formula (1), and

a structural unit (C) derived from a nonpolar cyclic olefin represented by the following general formula (2):

wherein T is¹To T³Each independently selected from hydrogen atom, hydrocarbon group with carbon number of 1-20, and carbon skeleton with carbon number of 1-18A silyl group of a skeleton, an alkoxy group having a carbon number of 1 to 20, a halogen group, and a cyano group;

T⁴is a substituent selected from the group consisting of:

ester group with carbon number of 2 to 30, carboxyl group, carboxylate group,

an alkoxycarbonyl group having a carbon number of 2 to 30 and in which a part of the carbon skeleton is substituted with at least 1 substituent selected from the group consisting of an ester group, a carboxyl group and a carboxylate group,

a hydrocarbon group having a carbon number of 2 to 20 in which a part of the carbon skeleton is substituted with at least 1 substituent selected from the group consisting of an ester group, a carboxyl group and a carboxylate group,

an alkoxy group having a carbon number of 1 to 20 in which a part of the carbon skeleton is substituted with at least 1 substituent selected from the group consisting of an ester group, a carboxyl group and a carboxylate group,

an acyloxy group having a carbon number of 2 to 20 and in which a part of the carbon skeleton is substituted with at least 1 substituent selected from the group consisting of an ester group, a carboxyl group and a carboxylate group,

a substituted amino group having a carbon number of 1 to 12, wherein a part of the carbon skeleton is substituted with at least 1 substituent selected from the group consisting of an ester group, a carboxyl group and a carboxylate group, and

a substituted silyl group having a carbon number of 1 to 18, in which a part of the carbon skeleton is substituted with at least 1 substituent selected from the group consisting of an ester group, a carboxyl group, and a carboxylate group;

the carboxylate group is a carboxylate group containing a metal ion of group 1, group 2 or group 12 of the periodic table; and is

T¹、T²、T³And T⁴Optionally in combination to form a ring,

wherein R is¹To R¹²Each of which is optionally the same or different and each is selected from the group consisting of a hydrogen atom, a halogen atom and a hydrocarbon group having a carbon number of 1 to 20;

R⁹and R¹⁰Optionally integrated to form a divalent organic group, and R¹¹And R¹²Optionally integrated to form a divalent organic group; r⁹Or R¹⁰Optionally with R¹¹Or R¹²Forming a ring; and is

n is 0 or a positive integer, and when n is 2 or more, R⁵To R⁸Each is optionally the same or different in each repeat unit.

In the polar group-containing olefin copolymer of the multicomponent system of the invention, T⁴May be a substituent selected from the group consisting of:

ester group with carbon number of 2 to 30, carboxyl group, carboxylate group,

an alkoxycarbonyl group having a carbon number of 2 to 30 in which a part of the carbon skeleton is substituted with at least 1 substituent selected from the group consisting of an ester group, a carboxyl group and a carboxylate group, and

a hydrocarbon group having a carbon number of 2 to 20 in which a part of the carbon skeleton is substituted with at least 1 substituent selected from the group consisting of an ester group, a carboxyl group and a carboxylate group.

In the polar group-containing olefin copolymer of the multicomponent system of the invention, T⁴May be an ester group having a carbon number of 2 to 30, a carboxyl group or a carboxylate group.

In the polar group-containing olefin copolymer of the multicomponent system of the invention, T⁴May be a carboxyl or carboxylate group.

In the polar group-containing olefin copolymer of the multicomponent system of the invention, T¹And T²Each may be a hydrogen atom, T³May be a hydrogen atom or a methyl group.

In the polar group-containing olefin copolymer of the multi-component system of the present invention, the content of the structural unit (C) derived from the nonpolar cyclic olefin may be 0.1 to 20 mol%.

In the polar group-containing olefin copolymer of the multi-component system of the present invention, the content of the structural unit (B) derived from the polar group-containing olefin monomer may be 2 to 20 mol%.

In the polar group-containing olefin copolymer of the present invention, the weight average molecular weight/number average molecular weight (Mw/Mn) as measured by gel permeation chromatography may be 1.5 or more and 4.0 or less.

In the polar group-containing olefin copolymer of the multicomponent system of the present invention, the melting point (Tm) (. degree. C.) and the total content [ Z ] (mol%) of the structural unit (B) and the structural unit (C) as observed by differential scanning calorimetry may satisfy the following formula (I):

50< Tm < -3.74 × [ Z ] +130

In the polar group-containing olefin copolymer of the multicomponent system of the invention, the absolute value G of the complex modulus measured by a rotational rheometer^*Is 0.1MPa (G)^*0.1MPa) may be 50 to 75 degrees.

In the polar group-containing olefin copolymer of the invention, by¹³The number of methyl branches calculated by C-NMR is 5 or less per 1,000 carbon atoms.

The multi-component polar group-containing olefin copolymer of the present invention may be a multi-component polar group-containing olefin copolymer produced by using a transition metal catalyst containing a transition metal of group 10 of the periodic table.

In the polar group-containing olefin copolymer of the multicomponent system of the invention, the transition metal of group 10 of the periodic table may be nickel or palladium.

ADVANTAGEOUS EFFECTS OF INVENTION

The multi-component polar group-containing olefin copolymer of the present invention containing the nonpolar cyclic olefin of the general formula (2) as the third component has a good balance of transparency, rigidity and toughness, as compared with a binary polymer such as an ethylene-acrylic acid copolymer.

Drawings

In the drawings, there is shown in the drawings,

FIG. 1 is a graph showing the relationship between the degree of neutralization and the degree of crystallinity of the base resins or ionomer of examples 4 to 15 and comparative examples 6 to 12, and

fig. 2 is a graph showing the relationship (balance) between the tensile modulus (rigidity) and the tensile impact strength (toughness) of the base resins or ionomers of examples 4 to 15 and comparative examples 6 to 12.

Detailed Description

The multi-component polar group-containing olefin copolymer of the present invention is a multi-component polar group-containing olefin copolymer comprising:

at least 1 structural unit (A) selected from the group consisting of a structural unit derived from ethylene and a structural unit derived from α -olefin having a carbon number of 3 to 20,

structural units (B) derived from a polar group-containing olefin monomer represented by the general formula (1), and

a structural unit (C) derived from a nonpolar cyclic olefin represented by the general formula (2).

Hereinafter, the multi-system polar group-containing olefin copolymer of the present invention and its use are explained in detail. In the present description, the term "(meth) acrylate" is used to mean the term "acrylate" or "methacrylate". Also in the present specification, "to" showing a numerical range is used to describe a range in which the numerical values before and after "to" represent a lower limit and an upper limit. Also, in the present specification, the multi-component polar group-containing olefin copolymer means a terpolymer or a multi-component copolymer containing at least 1 structural unit (a), at least 1 structural unit (B), and at least 1 structural unit (C).

(1) Structural unit (A)

The structural unit (a) is at least 1 structural unit selected from the group consisting of a structural unit derived from ethylene and a structural unit derived from α -olefin having a carbon number of 3 to 20.

The α -olefin of the present invention is α -olefin having a carbon number of 3 to 20 and is represented by the following structural formula CH₂＝CHR¹⁸(wherein R is¹⁸Is a hydrocarbon group having a carbon number of 1 to 18 and optionally has a linear or branched structure), α -olefin has a carbon number of 3 to 12 more preferably.

Examples of the structural unit (A) include, but are not limited to, ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 3-methyl-1-butene and 4-methyl-1-pentene. The structural unit (a) may be ethylene.

As the structural unit (A), such structural units can be used singly or in combination of 1 or 2 or more.

Examples of combinations of 2 of such structural units include, but are not limited to, ethylene-propylene, ethylene-1-butene, ethylene-1-hexene, ethylene-1-octene, propylene-1-butene, propylene-1-hexene, and propylene-1-octene.

Examples of combinations of 3 of such structural units include, but are not limited to, ethylene-propylene-1-butene, ethylene-propylene-1-hexene, ethylene-propylene-1-octene, propylene-1-butene-hexene, and propylene-1-butene-1-octene.

In the present invention, the structural unit (A) preferably contains ethylene as an essential component, and the structural unit (A) may further contain 1 or more α -olefins each having 3 to 20 carbon atoms, as required.

The ethylene in the structural unit (a) may be 65 to 100 mol% with respect to the total mol of the structural unit (a), or may be 70 to 100 mol%.

(2) Structural unit (B)

The structural unit (B) is a structural unit derived from a polar group-containing olefin monomer represented by the following general formula (1):

wherein T is¹To T³Each independently a substituent selected from the group consisting of a hydrogen atom, a hydrocarbon group having a carbon number of 1 to 20, a silyl group having a carbon skeleton having a carbon number of 1 to 18, an alkoxy group having a carbon number of 1 to 20, a halogen group, and a cyano group;

T⁴is a substituent selected from the group consisting of:

an ester group (-COOR) having a carbon number of 2 to 30⁴⁰) A carboxyl group (-COOH), a carboxylate group (-COOM wherein M is a monovalent or divalent metal ion of a group selected from the group consisting of groups 1,2 and 12 of the periodic Table),

alkoxycarbonyl group (-COOR) having a carbon number of 2 to 30, wherein a part of the carbon skeleton is substituted with at least 1 substituent selected from the group consisting of an ester group, a carboxyl group and a carboxylate group⁴¹)，

Having a carbon number of 2 to 20, wherein a part of the carbon skeleton is selected from the group consisting of ester group, carboxyl group and carboxylateHydrocarbyl (R) substituted with at least 1 substituent of the group consisting of⁴²-)，

Alkoxy group having a carbon number of 1 to 20 in which a part of the carbon skeleton is substituted with at least 1 substituent selected from the group consisting of an ester group, a carboxyl group and a carboxylate group (R)⁴³O-)，

Acyloxy (R) having a carbon number of 2 to 20, wherein a part of the carbon skeleton is substituted with at least 1 substituent selected from the group consisting of an ester group, a carboxyl group and a carboxylate group⁴⁴COO-)，

Substituted amino ((R)⁴⁵)₂N-where two R⁴⁵Each independently optionally being a functional group having a carbon number of from 1 to 6; the functional groups optionally have the same carbon backbone or different carbon backbones; and any of them is optionally a hydrogen atom), the carbon number thereof is 1 to 12 and wherein a part of the carbon skeleton is substituted with at least 1 substituent selected from the group consisting of an ester group, a carboxyl group and a carboxylate group, and

substituted silyl ((R)⁴⁶)₃Si-, in which three R are⁴⁶Each independently optionally being a functional group having a carbon number of 1 to 6, and the functional groups optionally having the same carbon skeleton or different carbon skeletons), having a carbon number of 1 to 18 and wherein a part of the carbon skeleton is substituted with at least 1 substituent selected from the group consisting of an ester group, a carboxyl group, and a carboxylate group;

the carboxylate group is a carboxylate group containing a metal ion of group 1, group 2 or group 12 of the periodic table; and is

T¹、T²、T³And T⁴Optionally joined to form a ring.

In the polar group-containing olefin copolymer of the multicomponent system of the invention, T⁴May be a substituent selected from the group consisting of:

ester group with carbon number of 2 to 30, carboxyl group, carboxylate group,

an alkoxycarbonyl group having a carbon number of 2 to 30 in which a part of the carbon skeleton is substituted with at least 1 substituent selected from the group consisting of an ester group, a carboxyl group and a carboxylate group, and

a hydrocarbon group having a carbon number of 2 to 20 in which a part of the carbon skeleton is substituted with at least 1 substituent selected from the group consisting of an ester group, a carboxyl group and a carboxylate group.

In particular, T⁴May be an ester group having a carbon number of 2 to 30, a carboxyl group or a carboxylate group. And, T⁴May be a carboxyl or carboxylate group.

T¹And T²Each may be a hydrogen atom, T³May be a hydrogen atom or a methyl group.

In the present invention, wherein T is represented by the general formula (1)⁴The polar group-containing olefin monomer in which the substituent is a carboxylate group is an ionomer of the present invention described later.

For T¹To T³The carbon skeleton of the hydrocarbon group, alkoxy group and silyl group may contain branched, cyclic and/or unsaturated bonds.

For T¹To T³Hydrocarbyl radical (R)⁴⁷-) the number of carbon atoms may be as follows: the lower limit is 1 or more and the upper limit is 20 or less or 10 or less.

For T¹To T³Alkoxy (R)⁴⁸The number of carbon atoms of O-) may be as follows: the lower limit is 1 or more and the upper limit is 20 or less or 10 or less.

For T¹To T³The number of carbon atoms of the silyl group may be as follows: the lower limit is 1 or more or 3 or more and the upper limit is 18 or less or 12 or less. Examples include, but are not limited to, trimethylsilyl, triethylsilyl, tri-n-propylsilyl, triisopropylsilyl, dimethylphenylsilyl, methyldiphenylsilyl and triphenylsilyl as the silyl group.

For T⁴The carbon skeleton of the alkoxycarbonyl, hydrocarbyl, alkoxy, acyloxy, substituted amino and substituted silyl groups contains at least 1 functional group selected from the group consisting of an ester group, a carboxyl group and a carboxylate group.

For T⁴The carbon skeleton of the ester group, alkoxycarbonyl group, hydrocarbon group, alkoxy group, acyloxy group, substituted amino group, and substituted silyl group may contain a branched, cyclic, and/or unsaturated bond.

For T⁴Ester group (-COOR)⁴⁰) The number of carbon atoms (including the carbon atom of the carbonyl group in the ester group) of (a) may be as follows: the lower limit is 2 or more, and the upper limit is 30 or less, 29 or less, 28 or less, 20 or less, 19 or less, 18 or less, 12 or less, 11 or less, 10 or less, 9 or less, or 8 or less.

For T⁴Alkoxycarbonyl (-COOR)⁴¹) The number of carbon atoms (including the carbon atom of the carbonyl group in the alkoxycarbonyl group) of (a) may be as follows: the lower limit is 2 or more and the upper limit is 30 or less or 20 or less. When a part of the carbon skeleton of the alkoxycarbonyl group is substituted with an ester group, the number of carbon atoms of the ester group is not particularly limited as long as it is within a range not exceeding the upper limit of the number of carbon atoms of the alkoxycarbonyl group.

For T⁴Hydrocarbyl radical (R)⁴²-) the number of carbon atoms may be as follows: the lower limit is 2 or more and the upper limit is 20 or less or 10 or less. When a part of the carbon skeleton of the hydrocarbon group is substituted with an ester group, the number of carbon atoms of the ester group is not particularly limited as long as it is within a range not exceeding the upper limit of the number of carbon atoms of the hydrocarbon group.

For T⁴Alkoxy (R)⁴³The number of carbon atoms of O-) may be as follows: the lower limit is 1 or more and the upper limit is 20 or less or 10 or less. When a part of the carbon skeleton of the alkoxy group is substituted with an ester group, the number of carbon atoms of the ester group is not particularly limited as long as it is within a range not exceeding the upper limit of the number of carbon atoms of the alkoxy group.

For T⁴Acyloxy (R)⁴⁴The number of carbon atoms of COO- (including the carbon atom of the carbonyl group in the acyloxy group) may be as follows: the lower limit is 2 or more and the upper limit is 20 or less or 10 or less. When a part of the carbon skeleton of the acyloxy group is substituted with an ester group, the number of carbon atoms of the ester group is not particularly limited as long as it is within a range not exceeding the upper limit of the number of carbon atoms of the acyloxy group.

For T⁴The number of carbon atoms of the substituted amino group may be as follows: the lower limit is 1 or more or 2 or more, and the upper limit is 12 or less or 9 or less. When a part of the carbon skeleton of the substituted amino group is substituted with an ester group, the number of carbon atoms of the ester group is not particularly limited as long as it is within a range not exceeding the upper limit of the number of carbon atoms of the substituted amino groupAnd (4) finishing. At the substituted amino group ((R)⁴⁵)₂N-) in two R⁴⁵Each independently optionally a substituent having a carbon number of 1 to 6; the substituents optionally have the same carbon skeleton or different carbon skeletons; and any of them is optionally a hydrogen atom. Examples of the amino group to be substituted by a substituent selected from the group consisting of an ester group, a carboxyl group and a carboxylate group include, but are not limited to, a dimethylamino group, a diethylamino group, a di-n-propylamino group and a cyclohexylamino group.

For T⁴The number of carbon atoms of the substituted silyl group may be as follows: the lower limit is 1 or more or 3 or more and the upper limit is 18 or less or 12 or less. When a part of the carbon skeleton of the substituted silyl group is substituted with an ester group, the number of carbon atoms of the ester group is not particularly limited as long as it is within a range not exceeding the upper limit of the number of carbon atoms of the substituted silyl group. In the substituted silyl radical ((R)⁴⁶)₃Si-) in three R⁴⁶Each independently optionally a substituent having a carbon number of 1 to 6; the substituents optionally have the same carbon skeleton or different carbon skeletons; and if at least 1R⁴⁶Containing substituents having 1 to 6 carbon atoms, other R⁴⁶Each may be a hydrogen atom. Examples of the silyl group to be substituted by a substituent selected from the group consisting of an ester group, a carboxyl group and a carboxylate group include, but are not limited to, a trimethylsilyl group, a triethylsilyl group, a tri-n-propylsilyl group, a triisopropylsilyl group, a dimethylphenylsilyl group, a methyldiphenylsilyl group and a triphenylsilyl group.

As the polar group-containing olefin monomer, examples include, but are not limited to, (meth) acrylic acid and/or (meth) acrylic acid esters.

The (meth) acrylate of the present invention is a compound represented by the following structural formula: CH (CH)₂＝C(R²¹)CO₂(R²²) Wherein R is²¹Is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms and optionally contains a branch, a ring and/or an unsaturated bond; r²²Is a hydrocarbon group having a carbon number of 1 to 30 and optionally contains a branch, a ring and/or an unsaturated bond; and at R²²Optionally containing a heteroatom.

As the (meth) acrylic acid ester, examples include those wherein R is²¹(meth) acrylate of a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms, wherein R²¹An acrylate of a hydrogen atom, and wherein R²¹A methacrylate of methyl group.

Examples of the (meth) acrylate include, but are not limited to, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, phenyl (meth) acrylate, tolyl (meth) acrylate, benzyl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxybutyl (meth) acrylate, 1, 4-cyclohexanedimethanol mono (meth) acrylate, ethyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, octyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth), 4-hydroxybutyl (meth) acrylate glycidyl ether (4-HBAGE), 2-methoxyethyl (meth) acrylate, 3-methoxypropyl (meth) acrylate, glycidyl (meth) acrylate, ethylene oxide (meth) acrylate, trifluoromethyl (meth) acrylate, 2-trifluoromethylethyl (meth) acrylate and perfluoroethyl (meth) acrylate.

As the (meth) acrylate, examples include, but are not limited to, compounds such as methyl acrylate, ethyl acrylate, n-butyl acrylate, t-butyl acrylate (tBA), (4-hydroxybutyl) acrylate glycidyl ether, t-butyl methacrylate and the like. Wherein the (meth) acrylate may be t-butyl acrylate.

As the polar group-containing olefin monomer, such (meth) acrylates may be used singly or in combination of 1 or 2 or more.

Examples of the metal ion (M) as the carboxylate group include a monovalent or divalent metal selected from one group consisting of groups 1,2 and 12 of the periodic Table, specifically, examples include lithium (L i), sodium (Na), potassium (K), rubidium (Rb), magnesium (Mg), calcium (Ca) and zinc (Zn) ions.

Carboxylate groups can be obtained, for example, as follows: after or simultaneously with hydrolysis or thermal decomposition of the ester groups of the copolymer, the ester groups are reacted with a compound containing a metal ion of group 1, group 2 or group 12 of the periodic table to convert the ester group portion of the copolymer to a metal-containing carboxylate salt, thereby obtaining carboxylate salt groups.

(3) Structural unit (C)

The structural unit (C) is a structural unit derived from a nonpolar cyclic olefin represented by the following general formula (2):

wherein R is¹To R¹²Each of which is optionally the same or different and each is selected from the group consisting of a hydrogen atom, a halogen atom and a hydrocarbon group having a carbon number of 1 to 20;

R⁹and R¹⁰Optionally integrated to form a divalent organic group, and R¹¹And R¹²Optionally integrated to form a divalent organic group; r⁹Or R¹⁰Optionally with R¹¹Or R¹²Forming a ring; and is

n is 0 or a positive integer, and when n is 2 or more, R⁵To R⁸Each is optionally the same or different in each repeat unit.

As the nonpolar cyclic olefin, examples include, but are not limited to, norbornene-based olefins and olefins containing, for example, norbornene, vinylnorbornene, ethylidene norbornene, norbornadiene, tetracyclododecene, tricyclodecene [4.3.0.1 ]^2,5]And tricyclo [4.3.0.1^2,5]And cyclic olefin skeleton compounds such as dec-3-ene. The nonpolar cyclic olefin can be 2-Norbornene (NB), or tetracyclo [6.2.1.1^3,6.0^2,7]Dodecyl-4-ene (tetracyclo [ 6.2.1.1)^3,6.0^2,7]dodeca-4-en), and the like.

(4) Olefin copolymer containing polar group in multi-component system

The multi-component polar group-containing olefin copolymer of the present invention comprises the following:

at least 1 structural unit (A) selected from the group consisting of a structural unit derived from ethylene and a structural unit derived from α -olefin having a carbon number of 3 to 20,

a structural unit (B) derived from a polar group-containing olefin monomer represented by the following general formula (1), and

a structural unit (C) derived from a nonpolar cyclic olefin represented by the following general formula (2).

The multi-component polar group-containing olefin copolymer of the present invention is required to contain 1 or more kinds of the structural unit (a), 1 or more kinds of the structural unit (B), and 1 or more kinds of the structural unit (C). That is, the multi-component polar group-containing olefin copolymer of the present invention needs to contain 3 or more monomer units in total.

Hereinafter, the structural units and the amount of structural units (structural unit amount) of the polar group-containing olefin copolymer of the multi-system of the present invention will be described.

The structure of 1 molecule derived from ethylene and/or α -olefin (a) having a carbon number of 3 to 20, the structure of 1 molecule derived from polar group-containing olefin monomer (B), and the structure of 1 molecule derived from nonpolar cyclic olefin (C) are each defined as 1 structural unit of the multi-system polar group-containing olefin copolymer.

When the total structural unit of the polar group-containing olefin copolymer of the multicomponent system is defined as 100 mol%, the mol percentage (mol%) of each structural unit is the amount of the structural unit.

Amount of structural units of ethylene and/or α -olefin (A) having 3 to 20 carbon atoms

With respect to the structural unit amount of the structural unit (a) of the present invention, the lower limit is 60.000 mol% or more, preferably 70.000 mol% or more, more preferably 80.000 mol% or more, even more preferably 85.000 mol% or more, still more preferably 87.000 mol% or more, and particularly preferably 91.400 mol% or more, and the upper limit is 97.999 mol% or less, preferably 97.990 mol% or less, more preferably 97.980 mol% or less, even more preferably 96.980 mol% or less, still more preferably 96.900 mol% or less, and particularly preferably 94.300 mol% or less.

When the amount of the structural unit derived from ethylene and/or α -olefin (A) having a carbon number of 3 to 20 is less than 60.000 mol%, the multi-system polar group-containing olefin copolymer is poor in toughness, and when the amount of the structural unit is more than 97.999 mol%, the multi-system polar group-containing olefin copolymer is high in crystallinity and poor in transparency.

Amount of structural units of the polar group-containing olefin monomer (B)

With respect to the structural unit amount of the structural unit (B) of the present invention, the lower limit is 2.0 mol% or more, and preferably 2.9 mol% or more, and the upper limit is 20.0 mol% or less, preferably 15.0 mol% or less, more preferably 10.0 mol% or less, even more preferably 8.0 mol% or less, and particularly preferably 6.1 mol% or less.

When the amount of the structural unit derived from the polar group-containing olefin monomer (B) is less than 2.0 mol%, the adhesion of the polar group-containing olefin copolymer of the multi-system to different kinds of highly polar materials is insufficient. When the amount of the structural unit is more than 20.0 mol%, the polar group-containing olefin copolymer of the multi-system cannot obtain sufficient mechanical properties.

The polar group-containing olefin monomer used may be 1 polar group-containing olefin monomer, or it may be a combination of 2 or more polar group-containing olefin monomers.

Amount of structural units of the nonpolar cyclic olefin (C)

With respect to the structural unit amount of the structural unit (C) of the present invention, the lower limit is 0.001 mol% or more, preferably 0.010 mol% or more, more preferably 0.020 mol%, even more preferably 0.100 mol% or more, and particularly preferably 1.200 mol% or more, and the upper limit is 20.000 mol% or less, preferably 15.000 mol% or less, more preferably 10.000 mol% or less, even more preferably 5.000 mol% or less, and particularly preferably 2.900 mol% or less.

When the amount of the structural unit derived from the nonpolar cyclic olefin (C) is less than 0.001 mol%, the rigidity of the polar group-containing olefin copolymer of the multicomponent system is insufficient. When the amount of the structural unit is more than 20.000 mol%, the balance between rigidity and toughness of the polar group-containing olefin copolymer of the multi-system is poor.

The nonpolar cyclic olefin used may be 1 nonpolar cyclic olefin, or may be a combination of 2 or more nonpolar cyclic olefins.

Method for measuring the amount of structural units of polar group-containing monomers in a multimodal polar group-containing olefin copolymer

For the quantification of the comonomer in the polar group-containing olefin copolymer of the invention, use is made of¹³C-NMR。¹³The C-NMR measurement conditions were as follows.

Sample temperature: 120 deg.C

Pulse angle: 90 degree

Pulse interval: 51.5 seconds

And (4) accumulating times: 512 or more

The measuring method comprises the following steps: inverse gated decoupling (Inverse gated decoupling)

Of hexamethyldisiloxane¹³The C signal is set to 1.98ppm, others¹³The chemical shift of the C signal is based on this.

<E/tBA>

In that¹³The quaternary carbon signal of the tert-butyl acrylate group of tBA was detected at 79.6 to 78.8 of the C-NMR spectrum. Using these signal intensities, the comonomer amount was calculated from the following formula.

Total tBA (mol%)

＝I_(tBA)×100/[I_(tBA)+I_(E)]

In the formula, I_(tBA)And I_(E)Is an amount represented by the following formula.

I_(tBA)＝I_79.6-78.8

I_(E)＝(I_180.0-135.0+I_120.0-2.0-I_(tBA)×7)/2

<E/tBA/NB>

In that¹³The quaternary carbon signal of the tert-butyl acrylate group of tBA was detected at 79.6 to 78.8 of the C-NMR spectrum. The methine carbon signal of Norbornene (NB) was detected at 41.9ppm to 41.1 ppm. Using these signal intensities, the comonomer amount was calculated from the following formula.

Total tBA (mol%)

＝I_(tBA)×100/[I_(tBA)+I_(NB)+I_(E)]

Total amount of NB (mol%)

＝I_(NB)×100/[I_(tBA)+I_(NB)+I_(E)]

In these formulae, I_(tBA)、I_(NB)And I_(E)Is an amount represented by the following formula.

I_(tBA)＝I_79.6-78.8

I_(NB)＝I_41.9-41.1/2

I_(E)＝(I_180.0-135.0+I_120.0-2.0-I_(NB)×7-I_(tBA)×7)/2

<E/tBA/TCD>

In that¹³The quaternary carbon signal of the tert-butyl acrylate group of tBA was detected at 79.6ppm to 78.8ppm in the C-NMR spectrum. Methylene and methine signals of Tetracyclododecene (TCD) were detected at 45.0ppm to 38.0ppm and 37.3ppm to 34.5ppm, respectively. Using these signal intensities, the comonomer amount was calculated from the following formula.

Total tBA (mol%)

＝I_(tBA)×100/[I_(tBA)+I_(TCD)+I_(E)]

Total amount of TCD (mol%)

＝I_(TCD)×100/[I_(tBA)+I_(TCD)+I_(E)]

In the above formula, I_(tBA)、I_(TCD)And I_(E)Is an amount represented by the following formula.

I_(tBA)＝I_79.6-78.8

I_(TCD)＝(I_45.0-38.0+I_37.3-34.5)/6

I_(E)＝(I_180.0-135.0+I_120.0-2.0-I_(TCD)×12-I_(tBA)×7)/2

In the above formula, "I" represents integrated intensity, and the numerical subscript following "I" represents chemical shift range. For example, "I_180.0-135.0"denotes the integrated intensity of the carbon signal detected between 180.0ppm and 135.0 ppm.

Number of methyl branches per 1,000 carbon atoms

For the polar group-containing olefin copolymer of the multi-component system of the present invention, by¹³C-NMR calculated the number of methyl branches. The upper limit of the number of methyl branches may be 5 or less per 1,000 carbon atoms, or it may be 0.8 or less per 1,000 carbon atoms. The lower limit is not particularly limited and may be as small as possible.

For quantifying the number of methyl branches, use¹³C-NMR。¹³The C-NMR measurement conditions were as follows.

Sample temperature: 120 deg.C

Pulse angle: 90 degree

Pulse interval: 51.5 seconds

And (4) accumulating times: 512 or less

The measuring method comprises the following steps: inversion gating decoupling

Of hexamethyldisiloxane¹³The C signal is set to 1.98ppm, others¹³The chemical shift of the C signal is based on this.

Weight average molecular weight (Mw) and molecular weight distribution (Mw/Mn)

As for the weight average molecular weight (Mw) of the polar group-containing olefin copolymer of the present invention, the lower limit is usually 1,000 or more, and preferably 6,000 or more, and the upper limit is usually 2,000,000 or less, preferably 1,500,000 or less, more preferably 1,000,000 or less, particularly preferably 800,000 or less, and most preferably 39,000 or less.

When the Mw is less than 1,000, the physical properties (e.g., mechanical strength and impact resistance) of the polar group-containing olefin copolymer of the multi-system are insufficient. When the Mw is more than 2,000,000, the melt viscosity of the polar group-containing olefin copolymer of the multi-system is very high, and the molding processing of the polar group-containing olefin copolymer of the multi-system is difficult.

The ratio (Mw/Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the polar group-containing olefin copolymer of the present invention is usually in the range of 1.5 to 4.0, preferably 1.6 to 3.3, and more preferably 1.6 to 2.3. When the ratio Mw/Mn is less than 1.5, various processability (e.g., moldability) of the polar group-containing olefin copolymer of the multicomponent system is insufficient. When the ratio Mw/Mn is more than 4.0, the mechanical properties of the polar group-containing olefin copolymer of the multicomponent system are poor.

In the present invention, the ratio Mw/Mn can be referred to as a molecular weight distribution parameter.

In the present invention, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are obtained by Gel Permeation Chromatography (GPC). The molecular weight distribution parameter (Mw/Mn) was calculated as follows: in addition to the weight average molecular weight (Mw), the number average molecular weight (Mn) was obtained by Gel Permeation Chromatography (GPC) and the ratio of Mw to Mn (Mw/Mn) was calculated.

Examples of the GPC measurement method are as follows.

(measurement conditions)

The device comprises the following steps: 150C manufactured by Waters Corporation

A detector: "MIRAN 1A-IR" (measurement wavelength: 3.42 μm) manufactured by FOXBORO

Measuring the temperature: 140 deg.C

Solvent: ortho-dichlorobenzene (ODCB)

Column: AD806M/S manufactured by Showa Denko K.K. (number of columns: 3)

Flow rate 1.0m L/min

Injection quantity 0.2m L

(preparation of sample)

As a sample, ODCB (containing 0.5mg/m L BHT (2, 6-di-tert-butyl-4-methylphenol)) was used to prepare a 1mg/m L solution and dissolved at 140 deg.C for about 1 hour.

(calculation of molecular weight (M))

The molecular weight was calculated by a standard polystyrene method. The conversion of the retention volume to the molecular weight was performed by using a calibration curve prepared in advance from standard polystyrene.

The standard polystyrenes used were products manufactured by Tosoh Corporation of F380, F288, F128, F80, F40, F20, F10, F4, F1, a5000, a2500 and a 1000. solutions were prepared by dissolving each of the standard polystyrenes to 0.5mg/M L in ODCB (containing 0.5mg/M L BHT). then, a solution of 0.2M L was injected to generate a calibration curve.

Polystyrene (PS): K ═ 1.38 × 10^-4,α＝0.7

Polyethylene (PE) K3.92 × 10^-4,α＝0.733

Polypropylene (PP): K1.03 × 10^-4,α＝0.78

Melting Point (. degree.C.)

For the polar group-containing olefin copolymer of the multi-component system of the present invention, the melting point (Tm) (. degree. C.) and the total content [ Z ] (mol%) of the structural unit (B) and the structural unit (C) as observed by differential scanning calorimetry may satisfy the following formula (I):

50< Tm < -3.74 × [ Z ] +130.

It was found that factors affecting the mechanical properties of the polar group-containing olefin copolymer of the multi-system include the total content (Z) of the structural units (B) and (C) of the polar group-containing olefin copolymer of the multi-system and the melting point of the polar group-containing olefin copolymer of the multi-system. It has also been found that the multi-system polar group-containing olefin copolymer exhibits better mechanical properties as the melting point decreases.

However, as a result of the studies by the present inventors, it was found that, for example, in the case of a binary system polymer of the structural unit (A) (ethylene) and the structural unit (B), the melting point of the copolymer depends on the content of the structural unit (B), and it is very difficult to lower the melting point to less than-3.74 × [ Z ] +130 (. degree. C.) and the improvement of mechanical properties is limited.

Therefore, when the melting point of the copolymer of the present invention is higher than-3.74 × [ Z ] +130 (. degree. C.), no improvement in mechanical properties is expected and it is difficult to sufficiently exert the mechanical properties.

For example, using "EXSTAR 6000" (manufactured by Seiko Instruments, Inc.), the temperature of the copolymer was maintained at 40 ℃ for 1 minute, increased from 40 ℃ to 160 ℃ at a rate of 10 ℃/minute, maintained at 160 ℃ for 10 minutes, decreased from 160 ℃ to 10 ℃ at a rate of 10 ℃/minute, and maintained at 10 ℃ for 5 minutes. The melting point can then be determined by measuring the temperature of the copolymer as it is raised from 10 ℃ to 160 ℃ at a rate of 10 ℃/minute.

The melting point Tm of the polar group-containing olefin copolymer of the present invention is not particularly limited as long as it satisfies the relationship represented by the above-described formula (I). In the case of polyethylene, the melting point is preferably greater than 50 ℃ and 140 ℃ or less, more preferably from 60 ℃ to 138 ℃, and most preferably from 70 ℃ to 135 ℃. When the melting point is 50 ℃ or lower, the heat resistance of the polar group-containing olefin copolymer of the multicomponent system is insufficient. When the melting point is higher than 140 ℃, the impact resistance of the polar group-containing olefin copolymer of the multicomponent system is poor.

Degree of crystallinity (%)

With respect to the polar group-containing olefin copolymer of the multi-component system of the present invention, the crystallinity observed by Differential Scanning Calorimetry (DSC) is not particularly limited. The crystallinity is preferably more than 0% and 30% or less, more preferably more than 0% and 25% or less, particularly preferably more than 5% and 25% or less, and most preferably 7% or more and 24% or less.

When the crystallinity is 0%, the toughness of the polar group-containing olefin copolymer of the multicomponent system is insufficient. When the crystallinity is more than 30%, the transparency of the polar group-containing olefin copolymer of the multicomponent system is poor. The crystallinity is an index of transparency. As the crystallinity of the polar group-containing olefin copolymer of the multicomponent system decreases, it can be determined that the transparency is better.

For example, the crystallinity can be obtained as follows: the heat of fusion (Δ H) of the copolymer was obtained from the area of the melting endothermic peak of the copolymer obtained when the temperature of the copolymer was raised from room temperature to 160 ℃ using "EXSTAR 6000" (manufactured by Seiko Instruments, inc.), and the heat of fusion was divided by the heat of fusion (293J/g) of complete crystallization of High Density Polyethylene (HDPE), thereby obtaining the crystallinity.

Molecular Structure of a multimodal polar group-containing olefin copolymer

As the polar group-containing olefin copolymer of the multi-component system of the present invention, examples include, but are not limited to, random copolymers, block copolymers and graft copolymers of the structural units (A), (B) and (C). Among them, the multi-system polar group-containing olefin copolymer may be a random copolymer which may contain many polar groups.

The molecular chain ends of the multi-component polar group-containing olefin copolymer of the present invention may be the structural units (A), (B) and (C).

The multi-component polar group-containing olefin copolymer of the present invention can be produced in the presence of a transition metal catalyst from the viewpoint of making the molecular structure a linear molecular structure.

The molecular structure of the polar group-containing olefin copolymer of the multicomponent system is known to vary depending on the production method, for example, polymerization by a high-pressure radical polymerization method, polymerization using a metal catalyst, and the like.

The difference in molecular structure can be controlled by the choice of the manufacturing method. For example, as described in japanese patent laid-open No.2010-150532, the molecular structure can be estimated by the complex modulus measured by a rotational rheometer.

Absolute value of complex modulus G^*Is 0.1MPa (G)^*0.1MPa) phase angle

For the polar group-containing olefin copolymer of the multicomponent system of the invention, the absolute value G of the complex modulus as measured by a rotational rheometer^*Is 0.1MPa (G)^*0.1MPa), the following can be given: the lower limit is 50 degrees or more or 51 degrees or more, and the upper limit is 75 degrees or less or 63 degrees or less.

More specifically, the absolute value G of the complex modulus as measured by a rotational rheometer^*Is 0.1MPa (G)^*0.1MPa) is 50 degrees or more, the molecular structure of the multi-component polar group-containing olefin copolymer is a linear structure, which does not contain long-chain branches or which contains a small amount of long-chain branches within a range not affecting mechanical strength.

Absolute value of complex modulus G as measured by rotational rheometer^*Is 0.1MPa (G)^*0.1MPa) is less than 50 degrees, the molecular structure of the multi-component polar group-containing olefin copolymer is a structure containing an excessive amount of long-chain branches, and the mechanical strength is poor.

Absolute value of complex modulus G measured by rotational rheometer^*Is 0.1MPa (G)^*0.1MPa) is influenced by both molecular weight distribution and long chain branching. However, only the polar group-containing polyvalent system having a ratio Mw/Mn of 4 or less, more preferably 3 or lessIn the case of olefin copolymers, the phase angle is used as an index of the amount of long-chain branches, and the value (G) increases as the amount of long-chain branches contained in the molecular structure increases^*0.1MPa) was decreased. When the ratio Mw/Mn of the polar group-containing olefin copolymer of the multicomponent system is 1.5 or more, the value (G) is obtained even in the case where the molecular structure does not contain a long chain branch^*0.1MPa) also does not exceed 75 degrees.

The complex modulus was measured as follows.

The sample was placed in a 1.0mm thick hot press mold and preheated for 5 minutes in a hot press with a surface temperature of 180 ℃. Then, the pressurization and depressurization of the sample are repeated to degas the residual gas in the molten resin. Further, the sample was pressurized at 4.9MPa and held for 5 minutes. Thereafter, the sample was transferred to a press having a surface temperature of 25 ℃ and held at a pressure of 4.9MPa for 3 minutes to be cooled, thereby producing a pressed sheet made of the sample having a thickness of about 1.0 mm. The pressed plate made of the sample was formed into a circular shape having a diameter of 25mm and used as a sample. The dynamic viscoelasticity of the sample was measured under the following conditions in a nitrogen atmosphere using an ARES type rotational rheometer (manufactured by Rheometrics) as a dynamic viscoelasticity measuring apparatus.

Plate: parallel plates (25mm diameter)

Temperature: 160 deg.C

Amount of distortion (distortion amount): 10 percent of

Measurement angular frequency range 1.0 × 10^-2rad/s to 1.0 × 10²rad/s

Measurement interval: 5 dots/decimal (decade)

Absolute value G relative to the complex modulus^*Common logarithm of (Pa) logG^*The phase angle is plotted. Will correspond to logG^*The (degree) value of the point of 5.0 is determined as (G)^*0.1 MPa). If the measuring point does not include the corresponding logG^*Point 5.0, logG is used^*Two points before and after 5.0, logG is obtained by linear interpolation^*The value at 5.0. When all the measurement points correspond to logG^*<At 5, using a large logG^*The log G in the quadratic curve is obtained by extrapolation of 3 points of the values^*＝5The value at 0.

Infrared absorption spectrum

The copolymer was melted at 180 ℃ for 3 minutes and then compression-molded to produce a film having a thickness of about 50 μm.

The film was analyzed by fourier transform infrared spectroscopy to obtain an infrared absorption spectrum of the copolymer.

Product name: FT/IR-6100(JASCO Corporation)

The measuring method comprises the following steps: transmission method

A detector: sulfuric acid Triglycine (TGS)

And (4) accumulating times: 16 to 64

Resolution ratio: 4.0cm^-1

Measuring wavelength: 5000cm-¹To 500cm-¹

Molecular Structure of a multimodal polar group-containing olefin copolymer

The multi-component polar group-containing olefin copolymer of the present invention may be a random copolymer.

An example of the molecular structure of a conventional ternary polar group-containing olefin copolymer (1) is shown below.

The random copolymer refers to a copolymer in which the probability that ethylene or a structural unit (a) (α -olefin having 3 to 20 carbon atoms), a structural unit (B) (polar group-containing monomer), and a structural unit (C) (nonpolar cyclic olefin) in the molecular structure example (1) shown below find each structural unit at any position in any molecular chain is independent of the type of the adjacent structural unit.

The molecular chain end of the polar group-containing olefin copolymer may be ethylene or a structural unit (a) (α -olefin having a carbon number of 3 to 20), may be a structural unit (B) (polar group-containing monomer), or may be a structural unit (C) (nonpolar cyclic olefin).

As shown below, in the molecular structure example (1) of the polar group-containing olefin copolymer, a random copolymer is formed from ethylene and/or a structural unit (a) (α -olefin having 3 to 20 carbon atoms), a structural unit (B) (polar group-containing monomer), and a structural unit (C) (nonpolar cyclic olefin).

-ABCAAABBCBAABACCAA-

Example of molecular Structure (1)

For reference, an example of the molecular structure of an olefin copolymer (2) in which a polar group is introduced by graft modification will be shown below as shown in the example, a part of an olefin copolymer obtained by copolymerization of ethylene and/or a structural unit (a) (α -olefin having a carbon number of 3 to 20) and a structural unit (C) (nonpolar cyclic olefin) is graft-modified with a structural unit (B) (polar group-containing monomer).

(5) Production of multi-system polar group-containing olefin copolymer

The multi-component polar group-containing olefin copolymer of the present invention may be a multi-component polar group-containing olefin copolymer produced in the presence of a transition metal catalyst, from the viewpoint of making the molecular structure a linear structure.

Polymerization catalyst

The multi-system polar group-containing olefin copolymer of the present invention is produced using a polymerization catalyst. The type of the polymerization catalyst is not particularly limited as long as it can copolymerize the structural units (A), (B) and (C). As the polymerization catalyst, examples include, but are not limited to, transition metal compounds of groups 5 to 11 of the periodic table having chelating ligands.

Examples of preferred transition metals include a vanadium atom, a niobium atom, a tantalum atom, a chromium atom, a molybdenum atom, a tungsten atom, a manganese atom, an iron atom, a platinum atom, a ruthenium atom, a cobalt atom, a rhodium atom, a nickel atom, a palladium atom and a copper atom. Among them, transition metals of groups 8 to 11 of the periodic table are preferable; more preferably a transition metal of group 10 of the periodic table; and nickel (Ni) and palladium (Pd) are particularly preferable. These metals may be used alone in 1 kind, or in combination of 2 or more kinds.

The chelating ligand contains at least 2 atoms selected from the group consisting of P, N, O and S. It includes bidentate and multidentate ligands, and it is electrically neutral or anionic. A review by Brookhart et al (chem. rev.,2000,100,1169) illustrates examples of structures of chelating ligands.

As the chelating ligand, a bidentate anionic P, O ligand is preferable. Examples of bidentate anionic P, O ligands include, but are not limited to, phosphosulfonic acid, phosphocarboxylic acid, phosphophenol, and phosphoenolate. Examples include, but are not limited to, bidentate anionic N, O ligands as chelating ligands. Examples also include, but are not limited to, salicylaldimine and pyridine carboxylic acid as bidentate anionic N, O ligands. Examples also include, but are not limited to, a diimine ligand, a diphenyl oxide (diphenoxide) ligand, and a diamide ligand as the chelating ligand.

The structure of the metal complex obtained from the chelating ligand is represented by the following structural formula (a) or (b), wherein an arylphosphine, arylarsine or arylantimony compound optionally having a substituent is coordinated:

wherein M is a transition metal of any one of groups 5 to 11 of the periodic Table, i.e., the above-mentioned various transition metals; x¹Is an oxygen atom, a sulfur atom, -SO₃-or-CO₂-；Y¹Is a carbon atom or a silicon atom; n is an integer of 0 or 1; e¹Is a phosphorus atom, an arsenic atom or an antimony atom; r⁵³And R⁵⁴Each independently is a hydrogen atom or a hydrocarbon group having a carbon number of 1 to 30 optionally containing a hetero atom; r⁵⁵Each independently is a hydrogen atom, a halogen atom or a hydrocarbon group having a carbon number of 1 to 30 optionally containing a hetero atom; r⁵⁶And R⁵⁷Each independently is a hydrogen atom, a halogen atom, a C1-30 hydrocarbon group optionally containing a hetero atom, OR⁵²、CO₂R⁵²、CO₂M’、C(O)N(R⁵¹)₂、C(O)R⁵²、SR⁵²、SO₂R⁵²、SOR⁵²、OSO₂R⁵²、P(O)(OR⁵²)_2-y(R⁵¹)_y、CN、NHR⁵²、N(R⁵²)₂、Si(OR⁵¹)_3-x(R⁵¹)_x、OSi(OR⁵¹)_3-x(R⁵¹)_x、NO₂、SO₃M’、PO₃M’₂、P(O)(OR⁵²)₂M' or an epoxy-containing group; r⁵¹Hydrogen atom or hydrocarbon group having 1 to 20 carbon atoms; r⁵²A hydrocarbon group having 1 to 20 carbon atoms; m' is an alkali metal, an alkaline earth metal, ammonium, quaternary ammonium or phosphonium; x is an integer of 0 to 3; y is an integer of 0 to 2; r⁵⁶And R⁵⁷Optionally combined to form an alicyclic ring, an aromatic ring, or a heterocyclic ring containing a hetero atom selected from an oxygen atom, a nitrogen atom and a sulfur atom, the ring being a 5-to 8-membered ring optionally having a substituent thereon, L¹Is a ligand coordinated to M; and R is⁵³And L¹Optionally joined to form a ring.

More preferably, the metal complex is a transition metal complex represented by the following structural formula (c):

wherein M is a transition metal of any one of groups 5 to 11 of the periodic Table, i.e., the above-mentioned various transition metals; x¹Is an oxygen atom, a sulfur atom, -SO₃-or-CO₂-；Y¹Is a carbon atom or a silicon atom; n is an integer of 0 or 1; e¹Is a phosphorus atom, an arsenic atom or an antimony atom; r⁵³And R⁵⁴Each independently is a hydrogen atom or a hydrocarbon group having a carbon number of 1 to 30 optionally containing a hetero atom; r⁵⁵Each independently is a hydrogen atom, a halogen atom or a hydrocarbon group having a carbon number of 1 to 30 optionally containing a hetero atom; r⁵⁸、R⁵⁹、R⁶⁰And R⁶¹Each independently is a hydrogen atom, a halogen atom, a C1-30 hydrocarbon group optionally containing a hetero atom, OR⁵²、CO₂R⁵²、CO₂M’、C(O)N(R⁵¹)₂、C(O)R⁵²、SR⁵²、SO₂R⁵²、SOR⁵²、OSO₂R⁵²、P(O)(OR⁵²)_2-y(R⁵¹)_y、CN、NHR⁵²、N(R⁵²)₂、Si(OR⁵¹)_3-x(R⁵¹)_x、OSi(OR⁵¹)_3-x(R⁵¹)_x、NO₂、SO₃M’、PO₃M’₂、P(O)(OR⁵²)₂M' or an epoxy-containing group; r⁵¹Hydrogen atom or hydrocarbon group having 1 to 20 carbon atoms; r⁵²A hydrocarbon group having 1 to 20 carbon atoms; m' is an alkali metal, an alkaline earth metal, ammonium, quaternary ammonium or phosphonium; x is an integer of 0 to 3; y is an integer of 0 to 2; is suitably selected from R⁵⁸To R⁶¹Are optionally combined to form an alicyclic ring, an aromatic ring, or a heterocyclic ring containing a hetero atom selected from an oxygen atom, a nitrogen atom and a sulfur atom, and the ring formed is a 5-to 8-membered ring optionally having a substituent thereon, L¹Is a ligand coordinated to M; and R is⁵³And L¹Optionally joined to form a ring.

As catalysts of transition metal compounds of groups 5 to 11 of the periodic table having a chelating ligand, catalysts such as so-called SHOP-type catalysts and so-called Drent-type catalysts are generally known.

The SHOP-based catalyst is a catalyst in which a phosphorus-based ligand containing an aryl group optionally having a substituent is coordinated to a nickel metal (for example, see WO 2010/050256).

The Drent-based catalyst is a catalyst in which a phosphorus-based ligand containing an aryl group optionally having a substituent is coordinated to palladium metal (see, for example, Japanese patent laid-open No. 2010-202647).

An organometallic compound

In the production of the polar group-containing olefin copolymer of the present invention, the polymerization activity is improved by bringing a polar group-containing olefin monomer into contact with a small amount of an organometallic compound and then copolymerizing the structural units (a), (B) and (C) in the presence of a transition metal catalyst.

The organometallic compound is an organometallic compound containing a hydrocarbon group optionally having a substituent. Which is represented by the following structural formula (d):

structural formula (d)

R³⁰nM³⁰X³⁰m-n

Wherein R is³⁰Is a hydrocarbon group having a carbon number of 1 to 12, which may optionally contain a substituent; m³⁰Is a metal selected from the group consisting of groups 1,2, 12 and 13 of the periodic table; x³⁰Is a halogen atom or a hydrogen atom; m is M³⁰A valence of (c); and n is 1 to m.

As the organometallic compound represented by the structural formula (d), examples include, but are not limited to, alkylaluminum such as tri-n-butylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, and tri-n-decylaluminum, and alkylaluminum halides such as methylaluminum dichloride, ethylaluminum dichloride, dimethylaluminum chloride, diethylaluminum chloride, and diethylaluminum ethoxide. Among them, trialkylaluminum is preferable.

The organometallic compound is more preferably trialkylaluminum containing a hydrocarbon group having a carbon number of 4 or more, even more preferably trialkylaluminum containing a hydrocarbon group having a carbon number of 6 or more, still more preferably tri-n-hexylaluminum, tri-n-octylaluminum or tri-n-decylaluminum, and most preferably tri-n-octylaluminum.

The amount of the organometallic compound contacted with the polar group-containing olefin monomer is preferably 10 relative to the polar group-containing olefin comonomer from the viewpoint of polymerization activity and cost^-5To 0.9, preferably 10^-4To 0.2, more preferably 10^-4To a molar ratio of 0.1.

Polymerization method of multi-component polar group-containing olefin copolymer

The polymerization method of the multi-component polar group-containing olefin copolymer of the present invention is not particularly limited.

As the polymerization method, examples include, but are not limited to, the following methods: slurry polymerization in which at least a part of the produced polymer is made into slurry in a medium, bulk polymerization in which the liquefied monomer itself serves as a medium, gas phase polymerization carried out in a vaporized monomer, and high pressure ionic polymerization in which at least a part of the produced polymer is dissolved in a monomer liquefied at high temperature and high pressure.

The polymerization method may be any of batch polymerization, semi-batch polymerization and continuous polymerization.

Further, living polymerization may be carried out, or polymerization may be carried out with chain transfer.

In the polymerization, chain shuttling reaction (chain shuttling reaction) or Coordination Chain Transfer Polymerization (CCTP) can be performed by using so-called Chain Shuttling Agent (CSA).

Detailed production processes and conditions are disclosed in, for example, japanese patent laid-open publication nos. 2010-260913 and 2010-202647.

Method for introducing polar groups into a multimodal polar group-containing olefin copolymer

The method for introducing a polar group into the multi-system polar group-containing olefin copolymer of the present invention is not particularly limited.

The specific polar group may be introduced by various methods without departing from the scope of the present invention.

As a method for introducing a polar group, examples include, but are not limited to, the following methods: a method of directly copolymerizing a monomer with a polar group-containing comonomer containing a specific polar group, and a method of copolymerizing a monomer with a comonomer containing a different polar group and then introducing a specific polar group by modification.

As a method for introducing a specific polar group by modification, examples include, but are not limited to, the following methods: in the case of introducing a carboxylic acid, a method of copolymerizing a monomer with t-butyl acrylate and then converting the copolymer into a carboxylic acid by thermal decomposition.

(6) Additive agent

For the polar group-containing olefin copolymer of the multi-component system of the present invention, conventionally known additives such as antioxidants, ultraviolet absorbers, lubricants, antistatic agents, colorants, pigments, crosslinking agents, foaming agents, nucleating agents, flame retardants, conductive materials, fillers, and the like may be added without departing from the scope of the present invention.

(7) Ionically crosslinked polymers

The ionomer of the present invention has the following structure: at least a part of the polar groups of the multi-component polar group-containing olefin copolymer of the present invention are neutralized with metal ions.

That is, the ionomer of the present invention is represented by the general formula (1) wherein T⁴The substituent(s) of (a) is a carboxylate group.

Therefore, when the multi-component polar group-containing olefin copolymer of the present invention is an ionomer, T in the general formula (1)⁴May be a substituent selected from the group consisting of:

a carboxylate group, a carboxyl group,

an alkoxycarbonyl group having a carbon number of 2 to 20 in which a part of the carbon skeleton is substituted with a carboxylate group,

a hydrocarbon group having a carbon number of 2 to 20 in which a part of the carbon skeleton is substituted with a carboxylate group,

an alkoxy group having a carbon number of 1 to 20 in which a part of the carbon skeleton is substituted with a carboxylate group,

an acyloxy group having a carbon number of 2 to 20 and having a carbon skeleton in which a part of the carbon skeleton is substituted with a carboxylate group,

a substituted amino group having a carbon number of 1 to 12 in which a part of the carbon skeleton is substituted with a carboxylate group, and

a substituted silyl group having a carbon number of 1 to 18, in which a part of the carbon skeleton is substituted with a carboxylate group.

Metal ion

The ionomer may contain metal ions suitable for conventionally known ionomers, the metal ions are preferably metal ions of group 1, group 2 or group 12 of the periodic table, and more preferably selected from L i⁺、Na⁺、K⁺、Rb⁺、Cs⁺、Mg²⁺、Ca²⁺、Sr²⁺、Ba²⁺And Zn²⁺At least 1 of the group consisting of. The ionomer may contain a combination of 2 or more of these metal ions as necessary.

Degree of neutralization (mol%)

The content of the metal ion is preferably such a content that at least a part or all of the polar groups in the multi-system polar group-containing olefin copolymer (base polymer) are neutralized. The degree of neutralization (average degree of neutralization) is preferably 5 to 95 mol%, more preferably 10 to 90 mol%, and even more preferably 20 to 80 mol%.

When the neutralization degree is high, the tensile strength and tensile breaking stress of the ionomer are high and the tensile breaking distortion is small. However, the Melt Flow Rate (MFR) of ionomers tends to be high. On the other hand, if the neutralization degree is low, the ionomer attains a suitable MFR. However, the tensile modulus and tensile stress at break of the ionomer tend to be low, and the tensile distortion at break tends to be high.

The degree of neutralization can be calculated from the content of the polar group-containing olefin monomer (polar group-containing comonomer) and the molar ratio of the metal ion added.