JP7453843B2 - Polar group-containing olefin copolymer and method for producing the same - Google Patents

Description

The present invention relates to a polar group-containing olefin copolymer and a method for producing the same. In particular, the present invention relates to a linear olefin copolymer containing an oxetanyl group and a polar group, and a method for producing the same.

Polymers with structures consisting of many monomer units have been extensively developed for a long time because they have physical properties that cannot be obtained from monomer units alone, and their physical properties can be controlled by selecting and designing the monomers used. This is the material that is used. Polyester is one of the useful materials used for sheets, machine parts, etc. as a resin material exhibiting excellent performance in rigidity and chemical resistance (Patent Documents 1 and 2). While polyester resin has excellent rigidity and chemical resistance, it has an ester bond in the polymer main chain, so it undergoes hydrolysis under high temperature and high humidity conditions. This causes a problem in that the molecular weight decreases and the impact resistance, tensile properties, etc. deteriorate over time. Patent Documents 1 and 2 discuss techniques for imparting hydrolysis resistance to polyester, but these techniques involve many complicated operations, such as the need for kneading operations.

On the other hand, a polymer material into which epoxide, which is a cyclic ether group, is introduced is known as a material that has chemical resistance and the like like polyester. Polymer materials containing epoxides have excellent heat resistance, chemical resistance, electrical insulation properties, etc., and have useful aspects such as exhibiting a variety of reactivities due to their highly strained three-membered ring structures. Due to its high price, storage stability is a problem. Therefore, it is known to substitute a four-membered ring oxetane, which is a more stable cyclic ether group (Patent Documents 3 and 4).

Patent No. 4404524 JP 2019-183033 Publication Japanese Patent Application Publication No. 11-63381 Patent No. 4643295

Oxetane as a method for introducing chemical resistance is advantageous in that it is less likely to be hydrolyzed compared to esters, but Patent Document 3, which discloses a polymer into which an oxetane ring is introduced, does not disclose any mechanical properties. Not done. Further, Patent Document 4 does not change the fact that the molecular skeleton has an ester bond, so it does not provide a fundamental solution to the hydrolysis resistance. Furthermore, since the substance described in Patent Document 4 has a special structure in which an oxetane ring is introduced into the polymer main chain, there is a problem that the degree of freedom in molecular design is low and it is unsuitable for the synthesis of inexpensive polymers. ing.

One method for increasing the degree of freedom in polymer design and the ease of synthesis is to select monomers that have a structure that provides desired physical properties to the side chains of the polymer. For example, copolymerization of ethylene and an olefin having a functional group such as an unsaturated carboxylic acid is known. However, although the high-pressure radical polymerization method commonly used in this method has the advantage of being able to polymerize relatively any type of polar group-containing monomer at a low cost, the molecule of the obtained polar group-containing olefin copolymer The structure is one that has many long and short chain branches in a random manner. For example, it is known that even in simple polyethylene, linear polyethylene is more advantageous in terms of strength than branched polyethylene, and olefin resins obtained by high-pressure radical polymerization are superior to polyester resins. The disadvantage is that it is insufficient in terms of strength, such as rigidity.
In order to improve the drawbacks of polar group-containing olefin copolymers obtained by high-pressure radical polymerization, methods have been sought to polymerize polar group-containing olefin copolymers with linear molecular structures using catalysts. However, since polar group-containing monomers generally poison the catalyst, polymerization using a catalyst is difficult. Therefore, it has been difficult to obtain a polar group-containing olefin copolymer having desired physical properties by an industrially inexpensive and stable method.

As described above, in the design of polymers, there are various demands from a practical standpoint from the production scene, such as simplicity of the method, degree of freedom in design, and various physical properties. However, these factors are often in a trade-off relationship between multiple physical properties and practicality in manufacturing, and a solution to this point has been desired. Therefore, an object of the present invention is to provide a resin that has higher hydrolysis resistance than polyester resin and also has excellent strength.

In recent years, by using a new catalyst and a new production method developed by the applicant and others, it is possible to produce an olefin copolymer containing a polar group with a substantially linear molecular structure at an industrially low cost and stably. A method was proposed to obtain this. The inventors of the present invention conducted intensive studies on the design using the new catalyst, and succeeded in obtaining a substantially linear copolymer using a monomer having an oxetanyl group, leading to the present invention. Ta.

［式中、
Ｚは、非置換であるか、又は水酸基、炭素数１～１０のアルコキシ基、炭素数２～１０のエステル基、炭素数３～１８の置換シリル基若しくはハロゲン原子で置換された、炭素数１～２０の直鎖状、分岐鎖状若しくは環状の二価の炭化水素基を表し、該炭化水素基の炭素鎖は、場合により酸素原子、硫黄原子又は基－ＮＲ－（ここで、Ｒは水素原子又は炭素数１～１０の炭化水素基を表す）で１回以上中断されていてもよく、該炭化水素基は、オキセタニル基に結合する酸素原子、硫黄原子又は基－ＮＲ－を有していてもよく、
Ｔは、水素原子、又は炭素数１～２０の直鎖状、分岐鎖状若しくは環状の炭化水素基を表す］
で表されるアクリレートに由来する構造単位（Ｂ）を有し、示差走査熱量測定（ＤＳＣ）により観測される融点（Ｔｍ、℃）と、該構造単位（Ｂ）の含有量［Ｙ］（ｍｏｌ％）とが下記式（Ｉ）：
－３．７４×［Ｙ］＋１１３．５＜Ｔｍ （Ｉ）
を満たすことを特徴とする、極性基含有オレフィン共重合体が提供される。
また、第二の発明によれば、第一の発明において、さらに、示差走査熱量測定（ＤＳＣ）により観測される融点（Ｔｍ、℃）と、該構造単位（Ｂ）の含有量［Ｙ］（ｍｏｌ％）とが下記式（ＩＩ）を満たすことを特徴とする、極性基含有オレフィン共重合体が提供される。
－３．７４×［Ｙ］＋１１３．５＜Ｔｍ＜－３．７４×［Ｙ］＋１３０ （ＩＩ）
第三の発明によれば、前記第一又は第二の発明において、^１３Ｃ－ＮＭＲにより算出されるメチル分岐数が、炭素１，０００個当たり５０個以下であることを特徴とする、極性基含有オレフィン共重合体が提供される。
第四の発明によれば、前記第一～第三のいずれかの発明において、前記構造単位（Ｂ）を０．１～２０．０ｍｏｌ％含むことを特徴とする、極性基含有オレフィン共重合体が提供される。
第五の発明によれば、前記第一～第四のいずれかの発明において、ゲルパーミエイションクロマトグラフィー（ＧＰＣ）で測定した重量平均分子量と数平均分子量の比（Ｍｗ／Ｍｎ）が１．５以上４．０以下であることを特徴とする、極性基含有オレフィン共重合体が提供される。
第六の発明によれば、前記第一～第五のいずれかの発明に係る極性基含有オレフィン共重合体の製造方法であって、後期遷移金属錯体触媒を用いることを特徴とする、極性基含有オレフィン共重合体の製造方法が提供される。
第七の発明によれば、前記第六の発明において、前記後期遷移金属錯体触媒が周期表第１０族の遷移金属を含むことを特徴とする、極性基含有オレフィン共重合体の製造方法が提供される。
第八の発明によれば、前記第七の発明において、前記周期表第１０族の遷移金属がニッケル又はパラジウムを含むことを特徴とする、極性基含有オレフィン共重合体の製造方法が提供される。 That is, according to the first aspect of the present invention, a structural unit (A) derived from ethylene and/or an α-olefin having 3 to 20 carbon atoms;
General formula (1) below:

[In the formula,
Z is unsubstituted or substituted with a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, an ester group having 2 to 10 carbon atoms, a substituted silyl group having 3 to 18 carbon atoms, or a halogen atom, and has 1 carbon atom ~20 linear, branched, or cyclic divalent hydrocarbon groups, and the carbon chain of the hydrocarbon group may optionally be an oxygen atom, a sulfur atom, or a group -NR- (where R is hydrogen (representing an atom or a hydrocarbon group having 1 to 10 carbon atoms), and the hydrocarbon group has an oxygen atom, a sulfur atom, or a group -NR- bonded to the oxetanyl group. It's okay,
T represents a hydrogen atom, or a linear, branched, or cyclic hydrocarbon group having 1 to 20 carbon atoms]
It has a structural unit (B) derived from acrylate represented by the melting point (Tm, °C) observed by differential scanning calorimetry (DSC) and the content [Y] (mol %) is the following formula (I):
-3.74×[Y]+113.5<Tm (I)
Provided is a polar group-containing olefin copolymer that satisfies the following.
According to the second invention, in the first invention, the melting point (Tm, °C) observed by differential scanning calorimetry (DSC) and the content [Y]( mol %) satisfies the following formula (II).
-3.74×[Y]+113.5<Tm<-3.74×[Y]+130 (II)
According to a third invention, the polar group according to the first or second invention, characterized in that the number of methyl branches calculated by ¹³ C-NMR is 50 or less per 1,000 carbons. An olefin-containing copolymer is provided.
According to a fourth invention, the polar group-containing olefin copolymer according to any one of the first to third inventions, characterized in that it contains 0.1 to 20.0 mol% of the structural unit (B). is provided.
According to a fifth invention, in any one of the first to fourth inventions, the ratio of weight average molecular weight to number average molecular weight (Mw/Mn) measured by gel permeation chromatography (GPC) is 1. Provided is a polar group-containing olefin copolymer characterized by a polar group-containing olefin copolymer having a polar group content of 5 or more and 4.0 or less.
According to a sixth invention, there is provided a method for producing a polar group-containing olefin copolymer according to any one of the first to fifth inventions, characterized in that a late transition metal complex catalyst is used. A method for producing an olefin-containing copolymer is provided.
According to a seventh invention, there is provided a method for producing a polar group-containing olefin copolymer according to the sixth invention, wherein the late transition metal complex catalyst contains a transition metal of Group 10 of the periodic table. be done.
According to an eighth invention, there is provided a method for producing a polar group-containing olefin copolymer according to the seventh invention, wherein the transition metal of Group 10 of the periodic table contains nickel or palladium. .

According to the present invention, in the first aspect, a resin composition having excellent mechanical properties such as hydrolysis resistance and rigidity can be obtained.
In the second invention, the copolymer has high randomness and a resin composition with excellent mechanical properties can be obtained.
In the third invention, the molecular structure of the copolymer has high linearity, and a resin composition that is superior in terms of rigidity and the like can be obtained.
In the fourth invention, by controlling the content of oxetanyl groups, a resin composition with better heat resistance can be obtained while maintaining transparency.
In the fifth invention, by controlling the molecular weight distribution parameters of the copolymer, a resin composition with better tensile strength and impact resistance can be obtained.
In the sixth invention, it is possible to produce a resin composition having a good balance of suitable physical properties that the resin compositions according to the first to fifth inventions have.
In the seventh or eighth invention, by using a transition metal catalyst, a linear copolymer can be produced more easily.

One embodiment of the present invention includes as essential structural units a structural unit (A) derived from ethylene and/or an α-olefin having 3 to 20 carbon atoms, and a structural unit (B) derived from an acrylate having an oxetanyl group. , these are substantially linearly copolymerized, preferably randomly copolymerized (P).
Hereinafter, the copolymer of the present invention will be explained in detail for each item. Note that in this specification, "~" indicating a numerical range is used to include the numerical values written before and after it as a lower limit value and an upper limit value. In addition, "hydrocarbon group" means a group with a chemical structure composed of carbon and hydrogen, including aliphatic chain groups such as alkyl, alicyclic groups such as cycloalkyl, vinyl, cyclooctadienyl, etc. It includes aliphatic unsaturated groups such as, and aromatic groups such as aryl. Further, the term "heteroatom" means an element other than carbon and hydrogen, especially an atom belonging to Groups 15 to 17 of the Periodic Table, unless specifically specified by example.

(1) Structural unit (A)
The structural unit (A) constituting the polar group-containing olefin copolymer of the present invention is a structural unit derived from ethylene and/or an α-olefin having 3 to 20 carbon atoms. The α-olefin related to the present invention is represented by the structural formula: CH ₂ =CHR ¹⁸ and has 3 to 20 carbon atoms. Here, R ¹⁸ is a hydrocarbon group having 1 to 18 carbon atoms, and may have a linear structure or a branched structure. The α-olefin preferably has 3 to 12 carbon atoms.
Specific examples of the structural unit (A) include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 3-methyl-1-butene, and 4-methyl-1-pentene. etc., and ethylene may also be used. As ethylene, ethylene derived from petroleum raw materials as well as non-petroleum raw materials such as vegetable raw materials can be used.

Further, the structural unit (A) may be one type or multiple types.
Examples of the combination of the two types include ethylene-propylene, ethylene-1-butene, ethylene-1-hexene, ethylene-1-octene, propylene-1-butene, propylene-1-hexene, and propylene-1-octene. It will be done.
Examples of the three combinations include ethylene-propylene-1-butene, ethylene-propylene-1-hexene, ethylene-propylene-1-octene, propylene-1-butene-hexene, and propylene-1-butene-1-octene. Can be mentioned.

The olefin from which the structural unit (A) is derived preferably essentially contains ethylene, and may further contain one or more α-olefins having 3 to 20 carbon atoms, if necessary.

Ethylene in the olefin from which the structural unit (A) is derived may be 65 to 100 mol%, or 70 to 100 mol%, based on the total mol of the structural unit (A).

［式中、
Ｚは、非置換であるか、又は水酸基、炭素数１～１０のアルコキシ基、炭素数２～１０のエステル基、炭素数３～１８の置換シリル基若しくはハロゲン原子で置換された、炭素数１～１０の直鎖状、分岐鎖状若しくは環状の二価の炭化水素基を表し、該炭化水素基の炭素鎖は、場合により酸素原子、硫黄原子又は基－ＮＲ－（ここで、Ｒは水素原子又は炭素数１～１０の炭化水素基を表す）で１回以上中断されていてもよく、該炭化水素基は、オキセタニル基に結合する酸素原子、硫黄原子又は基－ＮＲ－を有していてもよく、
Ｔは、水素原子、又は炭素数１～２０の直鎖状若しくは分岐鎖状の炭化水素基を表す］
で表されるアクリレートに由来する構造単位である。上記構造単位に由来する、オキセタニル基を含有する構造を有することで、本発明の極性基含有オレフィン共重合体は、優れた剛性、耐薬品性等を備えることができる。 (2) Structural unit (B)
The structural unit (B) constituting the polar group-containing olefin copolymer of the present invention has the following general formula (1):

[In the formula,
Z is unsubstituted or substituted with a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, an ester group having 2 to 10 carbon atoms, a substituted silyl group having 3 to 18 carbon atoms, or a halogen atom, and has 1 carbon atom ~10 linear, branched, or cyclic divalent hydrocarbon groups, and the carbon chain of the hydrocarbon group may optionally be an oxygen atom, a sulfur atom, or a group -NR- (where R is hydrogen (representing an atom or a hydrocarbon group having 1 to 10 carbon atoms), and the hydrocarbon group has an oxygen atom, a sulfur atom, or a group -NR- bonded to the oxetanyl group. It's okay,
T represents a hydrogen atom or a linear or branched hydrocarbon group having 1 to 20 carbon atoms]
It is a structural unit derived from acrylate represented by By having a structure containing an oxetanyl group derived from the above structural unit, the polar group-containing olefin copolymer of the present invention can have excellent rigidity, chemical resistance, and the like.

Z in the general formula (1) is a linker that connects the oxetanyl group and the acrylic group. Z represents a linear, branched or cyclic divalent hydrocarbon group having 1 to 10 carbon atoms. The hydrocarbon group is unsubstituted or substituted with a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, an ester group having 2 to 10 carbon atoms, a substituted silyl group having 3 to 18 carbon atoms, or a halogen atom. Good too. In addition, the carbon chain of the hydrocarbon group represented by Z may optionally be an oxygen atom, a sulfur atom, or a group -NR- (here, R represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms). It may be interrupted more than once and the hydrocarbon group may have an oxygen atom, a sulfur atom or a group -NR- bonded to the oxetanyl group. That is, the hydrocarbon group may have a heteroatom selected from an oxygen atom, a sulfur atom, or a nitrogen atom at any position other than the part directly bonded to the ester bond of the acrylic group.

Examples of the group Z include unsubstituted hydrocarbons such as methylene (-CH ₂ -), ethylene (-CH ₂ CH ₂ -), 1,3-propylene (-CH ₂ CH ₂ CH ₂ -), 1, 4-butylene (-CH ₂ CH ₂ CH ₂ CH ₂ -), 1,5-pentylene (-CH ₂ CH ₂ CH 2 CH _{2 CH 2 -} ), 1,6-hexylene (-CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ -), 1-methyl-1,2-ethylene (-CH(CH ₃ )CH ₂ -), 2,2-dimethyl-1,3-propylene (-CH ₂ C(CH ₃ ) ₂ CH ₂ -), 3-methyl-1,5-pentylene (-CH ₂ CH ₂ CH(CH ₃ )CH ₂ CH ₂ -), 1,4-cyclohexylene, cyclohexane-1,4-dimethylene (-CH ₂ -C ₆ H ₁₀ -CH ₂ -) and the like. Hydrocarbons having substituents include 1-methoxy-ethylene (-CH(OCH ₃ )CH ₂ -), trimethylsilylmethylene (-CH(Si(CH ₃ ) ₃ )-), difluoromethylene (-CF ₂ -), etc. can be mentioned. A group having a heteroatom consisting of oxygen, sulfur or nitrogen is represented by -CH ₂ CH ₂ NHCH ₂ CH ₂ -, -CH ₂ CH ₂ OCH ₂ CH ₂ -, -CH ₂ CH ₂ OCH ₂ CH ₂ O- Examples include groups. Among these, preferred groups are unsubstituted hydrocarbon groups, and particularly preferred groups are methylene or ethylene.

T represents a hydrogen atom or a linear, branched or cyclic hydrocarbon group having 1 to 20 carbon atoms. Examples of hydrocarbon groups include methyl group, ethyl group, 1-propyl group, 1-butyl group, 1-pentyl group, 1-hexyl group, 1-heptyl group, 1-octyl group, 1-nonyl group, -decyl group, t-butyl group, isopropyl group, 1-dimethylpropyl group, 1,1,2-trimethylpropyl group, 1,1-diethylpropyl group, isobutyl group, 1,1-dimethylbutyl group, 2-pentyl group group, 3-pentyl group, 2-hexyl group, 3-hexyl group, 2-ethylhexyl group, 2-heptyl group, 3-heptyl group, 4-heptyl group, 2-propylheptyl group, 2-octyl group, 3- Nonyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, methylcyclopentyl group, cyclohexyl group, methylcyclohexyl group, tricyclohexylmethyl group, cycloheptyl group, cyclooctyl group, cyclododecyl group, 1-adamantyl group, 2-adamantyl group , exo-norbornyl group, endo-norbornyl group, 2-bicyclo[2.2.2]octyl group, nopinyl group, decahydronaphthyl group, menthyl group, neomenthyl group, neopentyl group, and 5-decyl group. Among these, preferable groups include ethyl group, 1-propyl group, 1-butyl group, 1-pentyl group, 1-hexyl group, 1-heptyl group, 1-octyl group, 1-nonyl group, 1- It is a decyl group. Particularly preferred substituents are ethyl group or 1-propyl group.

As the acrylate represented by the general formula (1), commercially available acrylates can be used. Commercially available compounds include (3-ethyloxetan-3-yl)methyl acrylate, (3-methyloxetan-3-yl)methyl acrylate, and the like. Acrylates having a desired structure can be synthesized using other commercially available raw materials, and these can also be used. Furthermore, only one type of acrylate may be used alone, or two or more types of acrylate may be used in combination.

(3) Other structural units (C)
The copolymer (P) of the present invention contains a structural unit (C) (hereinafter sometimes referred to as "arbitrary monomer (C)") other than the structural unit (A) and the structural unit (B). You can stay there. As the monomer providing the structural unit (C), any monomer can be used as long as it is not the same as the monomer providing the structural unit (A) and the structural unit (B). The arbitrary monomer providing the structural unit (C) is not limited as long as it is a compound having one or more carbon-carbon double bonds in its molecular structure, but for example, an acyclic monomer represented by the following general formula (2), Examples include cyclic monomers represented by the following general formula (3).

［一般式（２）中、Ｔ^１～Ｔ^３はそれぞれ独立して、水素原子、炭素数１～２０の炭化水素基、水酸基で置換された炭素数１～２０の炭化水素基、炭素数１～２０のアルコキシ基で置換された炭素数２～２０の炭化水素基、炭素数２～２０のエステル基で置換された炭素数３～２０の炭化水素基、ハロゲン原子で置換された炭素数１～２０の炭化水素基、炭素数１～２０のアルコキシ基、炭素数６～２０のアリール基、炭素数２～２０のエステル基、炭素数炭素数３～２０のシリル基、ハロゲン原子、又は、シアノ基からなる群より選択される置換基であり、
Ｔ^４は、水酸基で置換された炭素数１～２０の炭化水素基、炭素数１～２０のアルコキシ基で置換された炭素数２～２０の炭化水素基、炭素数２～２０のエステル基で置換された炭素数３～２０の炭化水素基、ハロゲン原子で置換された炭素数１～２０の炭化水素基、炭素数１～２０のアルコキシ基、炭素数６～２０のアリール基、炭素数２～２０のエステル基、炭素数炭素数３～２０のシリル基、ハロゲン原子、又は、シアノ基からなる群より選択される置換基である。] ・Acyclic monomer

[In general formula (2), T ¹ to T ³ each independently represent a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms substituted with a hydroxyl group, or 1 to 20 carbon atoms; A hydrocarbon group having 2 to 20 carbon atoms substituted with an alkoxy group of ~20, a hydrocarbon group having 3 to 20 carbon atoms substituted with an ester group having 2 to 20 carbon atoms, a 1 carbon group substituted with a halogen atom -20 hydrocarbon group, C1-20 alkoxy group, C6-20 aryl group, C2-20 ester group, C3-20 silyl group, halogen atom, or a substituent selected from the group consisting of cyano group,
^T4 is a hydrocarbon group having 1 to 20 carbon atoms substituted with a hydroxyl group, a hydrocarbon group having 2 to 20 carbon atoms substituted with an alkoxy group having 1 to 20 carbon atoms, or an ester group having 2 to 20 carbon atoms. Substituted hydrocarbon group having 3 to 20 carbon atoms, halogen atom-substituted hydrocarbon group having 1 to 20 carbon atoms, alkoxy group having 1 to 20 carbon atoms, aryl group having 6 to 20 carbon atoms, 2 carbon atoms The substituent is selected from the group consisting of an ester group having 1 to 20 carbon atoms, a silyl group having 3 to 20 carbon atoms, a halogen atom, or a cyano group. ]

In the copolymer of the present invention, T ¹ and T ² may be hydrogen atoms, T ³ may be a hydrogen atom or a methyl group, and T ⁴ may be an ester group having 2 to 20 carbon atoms. You can.

The carbon skeletons of the hydrocarbon groups, substituted alkoxy groups, substituted ester groups, alkoxy groups, aryl groups, ester groups, and silyl groups related to T ¹ to T ⁴ may have branches, rings, and/or unsaturated bonds. good.
The lower limit of the number of carbon atoms in the hydrocarbon group related to T ¹ to T ⁴ may be 1 or more, and the upper limit may be 20 or less, and may be 10 or less.
The lower limit of the number of carbon atoms in the substituted alkoxy group for T ¹ to T ⁴ may be 1 or more, and the upper limit may be 20 or less, and may be 10 or less.
The lower limit of the number of carbon atoms in the substituted ester group regarding T ¹ to T ⁴ may be 2 or more, and the upper limit may be 20 or less, and may be 10 or less.
The lower limit of the number of carbon atoms in the alkoxy group related to T ¹ to T ⁴ may be 1 or more, and the upper limit may be 20 or less, and may be 10 or less.
The lower limit of the number of carbon atoms in the aryl group related to T ¹ to T ⁴ may be 6 or more, and the upper limit may be 20 or less, and may be 11 or less.
The lower limit of the number of carbon atoms in the ester group for T ¹ to T ⁴ may be 2 or more, and the upper limit may be 20 or less, and may be 10 or less.
The lower limit of the number of carbon atoms in the silyl group related to T ¹ to T ⁴ may be 3 or more, and the upper limit may be 18 or less, and may be 12 or less. Examples of the silyl group include trimethylsilyl group, triethylsilyl group, trin-propylsilyl group, triisopropylsilyl group, dimethylphenylsilyl group, methyldiphenylsilyl group, and triphenylsilyl group.

Specific examples of the acyclic monomer include (meth)acrylic acid esters and the like.
The (meth)acrylic ester related to the present invention is a compound represented by the structural formula: CH ₂ =C(R ²¹ )CO ₂ (R ²² ). Here, R ²¹ is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and may have a branch, a ring, and/or an unsaturated bond. R ²² is a hydrocarbon group having 1 to 20 carbon atoms, and may have a branch, a ring, and/or an unsaturated bond, provided that it does not form an oxetanyl group, and may have a branch, a ring, and/or an unsaturated bond at any position within R ²² . May contain heteroatoms.

Examples of (meth)acrylic esters include (meth)acrylic esters in which R ²¹ is a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms. Further examples include acrylic esters in which R ²¹ is a hydrogen atom or methacrylic esters in which R ²¹ is a methyl group.
Specific examples of (meth)acrylic acid esters include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, and n-(meth)acrylate. -Butyl, isobutyl (meth)acrylate, t-butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, cyclohexyl (meth)acrylate, octyl (meth)acrylate, (meth) 2-ethylhexyl acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, dodecyl (meth)acrylate, octadecyl (meth)acrylate, phenyl (meth)acrylate, tolyl (meth)acrylate, (meth)acrylate ) benzyl acrylate, etc.

Specific compounds include methyl acrylate, ethyl acrylate, n-butyl acrylate (nBA), isobutyl acrylate (iBA), t-butyl acrylate (tBA), and 2-ethylhexyl acrylate. In particular, n-butyl acrylate (nBA), isobutyl acrylate (iBA), and t-butyl acrylate (tBA) may be used.
Note that one type of acyclic monomer may be used, or a plurality of types may be used.

［一般式（３）中、Ｒ^１～Ｒ^１２は、それぞれ同一でも異なっていてもよく、水素原子、ハロゲン原子、及び、炭素数１～２０の炭化水素基からなる群より選ばれるものであり、Ｒ^９及びＲ^１０、並びに、Ｒ^１１及びＲ^１２は、各々一体化して２価の有機基を形成してもよく、Ｒ^９又はＲ^１０と、Ｒ^１１又はＲ^１２とは、互いに環を形成していてもよい。
また、ｎは、０又は正の整数を示し、ｎが２以上の場合には、Ｒ^５～Ｒ^８は、それぞれの繰り返し単位の中で、それぞれ同一でも異なっていてもよい。］ ・Cyclic monomer

[In general formula (3), R ¹ to R ¹² may be the same or different, and are selected from the group consisting of a hydrogen atom, a halogen atom, and a hydrocarbon group having 1 to 20 carbon atoms. , R ⁹ and R ¹⁰ , and R ¹¹ and R ¹² may each be combined to form a divalent organic group, and R ⁹ or R ¹⁰ and R ¹¹ or R ¹² each have a ring. It may be formed.
Further, n represents 0 or a positive integer, and when n is 2 or more, R ⁵ to R ⁸ may be the same or different in each repeating unit. ]

Examples of the cyclic monomer include norbornene-based olefins, such as norbornene, vinylnorbornene, ethylidene norbornene, norbornadiene, tetracyclododecene, tricyclo[4.3.0.1 ^2,5 ]dec-1-ene, and tricyclo[4 Examples include compounds having a cyclic olefin skeleton such as 2 ^- norbornene (NB) and tetracyclo[6.2.1.1 ^{3, 6} . 0 ^2,7 ] dodec-4-ene, etc.

(4) Copolymer The polar group-containing olefin copolymer (P) of the present invention comprises a structural unit (A) derived from ethylene and/or an α-olefin having 3 to 20 carbon atoms, and the above general formula (1). It is characterized in that it contains a structural unit (B) derived from an acrylate represented by as an essential structural unit, and these are substantially linearly copolymerized, preferably randomly copolymerized. "Substantially linear" refers to a state in which the copolymer has no branching or a branched structure appears infrequently, so that the copolymer can be considered to be linear. Specifically, it refers to a state in which the composition and melting point of the copolymer satisfy the above formula (I).

The copolymer of the present invention must contain one or more types of structural units (A) and one or more types of structural units (B), and must contain two or more types of monomer units in total, and other structural units (C). May contain.
The structural units and amount of structural units of the copolymer related to the present invention will be explained.
A copolymer with a structure derived from one molecule each of ethylene and/or an α-olefin having 3 to 20 carbon atoms (A), an acrylate represented by the general formula (1) (B), and an arbitrary monomer (C). It is defined as one structural unit inside.
The amount of structural units is the ratio of each structural unit expressed in mol% when the total structural units in the copolymer are 100 mol%.

- Structural unit amount of ethylene and/or α-olefin (A) having 3 to 20 carbon atoms:
The lower limit of the structural unit amount of the structural unit (A) in the copolymer of the present invention is 60.000 mol% or more, preferably 70.000 mol% or more, more preferably 80.000 mol% or more, and even more preferably 85.000 mol%. Above, even more preferably 90.000 mol% or more, particularly preferably 91.200 mol% or more. The upper limit of the amount of the structural unit (A) is 99.900 mol% or less, preferably 99.750 mol% or less, more preferably 99.500 mol% or less, even more preferably 99.400 mol%, even more preferably 96. It is selected from 900 mol% or less, particularly preferably 96.500 mol% or less.
If the amount of structural units derived from ethylene and/or α-olefin (A) having 3 to 20 carbon atoms is less than 60.000 mol%, the copolymer will not have sufficient rigidity, and if it is more than 99.750 mol%, the stiffness will be poor. Chemical effects may be insufficient.

・Amount of structural units derived from acrylate (B) represented by general formula (1):
The lower limit of the structural unit amount of the structural unit (B) in the copolymer of the present invention is 0.1 mol% or more, preferably 0.25 mol% or more, more preferably 0.5 mol% or more, and even more preferably It is 0.6 mol% or more. The upper limit of the structural unit (B) 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, particularly preferably 5.4 mol% or less. selected.
If the amount of structural units derived from acrylate (B) represented by general formula (1) is less than 0.25 mol%, effects such as chemical resistance may be insufficient, and if it is more than 20.0 mol%, olefin In some cases, sufficient mechanical properties of the polymer cannot be obtained.

・Amount of structural units of arbitrary monomer (C):
The lower limit of the structural unit amount of the structural unit (C) related to the present invention is 0.001 mol% or more, preferably 0.010 mol% or more, more preferably 0.020 mol% or more, when the structural unit (C) is included. More preferably 0.100 mol% or more, even more preferably 1.000 mol% or more, particularly preferably 1.900 mol% or more, and the upper limit is 20.000 mol% or less, preferably 15.000 mol% or less, more preferably is selected from 10.000 mol% or less, more preferably 5.000 mol% or less, particularly preferably 3.600 mol% or less.
Furthermore, the arbitrary monomers used may be used alone or in combination of two or more types.

・Number of branches per 1,000 carbons of copolymer:
In the molecular structure of polyolefins, short carbon chains with about 1 to 4 carbon atoms, such as methyl, ethyl, and butyl, may appear as branches. The copolymer of the present invention has no branching or a branched structure appears infrequently, and has a structure that can be considered to be linear.
In copolymers, in order to increase the elastic modulus and obtain sufficient mechanical properties, even if the number of methyl branches calculated by ¹³ C-NMR is 50 or less per 1,000 carbons, Often, the number may be 5.0 or less, 3.0 or less, 1.0 or less, or 0.5 or less. The lower limit of the number of methyl branches is not particularly limited, and the smaller the number, the better. The upper limit of the number of ethyl branches per 1,000 carbon atoms may be 3.0 or less, 2.0 or less, 1.0 or less, or 0.5 The number may be less than 1. The lower limit of the number of ethyl branches is not particularly limited, and the smaller the number, the better. Furthermore, the upper limit of the number of butyl branches per 1,000 carbons may be 7.0 or less, 5.0 or less, 3.0 or less, or 0.5 The number may be less than 1. The lower limit of the number of butyl branches is not particularly limited, and the smaller the number, the better.

Method for measuring each structural unit and number of branches in the copolymer:
The number of branches per 1,000 carbon atoms in each structural unit in the copolymer of the present invention is determined using a ¹³ C-NMR spectrum. ¹³ C-NMR is measured by the following method.
200 to 300 mg of the sample was dissolved in a mixed solvent of o-dichlorobenzene (C ₆ H ₄ Cl ₂ ) and deuterated bromide benzene (C ₆ D ₅ Br) (C ₆ H ₄ Cl ₂ /C ₆ D ₅ Br=2/ 1 (volume ratio)) 2.4 ml and hexamethyldisiloxane, which is a reference substance for chemical shift, are placed in an NMR sample tube with an inner diameter of 10 mmφ, purged with nitrogen, sealed, and heated to dissolve as a homogeneous solution as an NMR measurement sample. shall be.
NMR measurements are carried out at 120° C. using an AV400M NMR apparatus manufactured by Bruker Japan Co., Ltd. equipped with a 10 mmφ cryoprobe.
¹³ C-NMR is measured using a reverse gate decoupling method at a sample temperature of 120° C., a pulse angle of 90°, a pulse interval of 51.5 seconds, and an integration count of 512 or more times.
For the chemical shift, the ¹³ C signal of hexamethyldisiloxane is set at 1.98 ppm, and the chemical shifts of other ¹³ C signals are based on this.
In the obtained ^13C -NMR, the amount of structural units of each monomer in the copolymer and the number of branches can be analyzed by identifying signals specific to the monomers or branches possessed by the copolymer and comparing their intensities. can do. The positions of signals specific to monomers or branches can be determined with reference to known materials, or can be independently identified depending on the sample. Such analysis techniques can be commonly performed by those skilled in the art.

・Weight average molecular weight (Mw) and molecular weight distribution (Mw/Mn):
The lower limit of the weight average molecular weight (Mw) of the copolymer of the present invention is usually 1,000 or more, preferably 6,000 or more, and the upper limit is usually 2,000,000 or less, preferably 1,000 or more, and preferably 6,000 or more. It is 500,000 or less, more preferably 1,000,000 or less, particularly preferably 800,000 or less, and most preferably 56,000 or less.
If Mw is less than 1,000, the physical properties such as mechanical strength and impact resistance of the copolymer will not be sufficient, and if Mw exceeds 2,000,000, the melt viscosity of the copolymer will be extremely high, and the copolymer will have insufficient physical properties such as mechanical strength and impact resistance. It may be difficult to form the combined product.

The ratio of weight average molecular weight (Mw) to number average molecular weight (Mn) (Mw/Mn) of the copolymer of the present invention is usually 1.5 to 4.0, preferably 1.6 to 3.5, more preferably ranges from 1.9 to 2.3. If Mw/Mn is less than 1.5, the copolymer will not have sufficient processing properties including molding, and if it exceeds 4.0, the mechanical properties of the copolymer may be poor. Moreover, (Mw/Mn) may be expressed as a molecular weight distribution parameter.

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

An example of a GPC measurement method is as follows.
(Measurement condition)
Model used: Waters 150C
Detector: FOXBORO MIRAN1A IR detector (measurement wavelength: 3.42 μm)
Measurement temperature: 140℃
Solvent: Orthodichlorobenzene (ODCB)
Column: Showa Denko AD806M/S (3 columns)
Flow rate: 1.0mL/min Injection volume: 0.2mL
(Sample preparation)
For the sample, a 1 mg/mL solution was prepared using ODCB (containing 0.5 mg/mL BHT (2,6-di-t-butyl-4-methylphenol)) and heated at 140°C for about 1 hour. and dissolve.
(Calculation of molecular weight (M))
The standard polystyrene method is used, and the retention capacity is converted to molecular weight using a standard polystyrene calibration curve prepared in advance. The standard polystyrenes used are all brands (F380, F288, F128, F80, F40, F20, F10, F4, F1, A5000, A2500, A1000) manufactured by Tosoh Corporation. A calibration curve is created by injecting 0.2 mL of a solution dissolved in ODCB (containing 0.5 mg/mL BHT) so that each concentration is 0.5 mg/mL. The calibration curve uses a cubic equation obtained by approximation using the least squares method. The following numerical value is used for the viscosity formula [η]=K×Mα used for conversion to molecular weight (M).
Polystyrene (PS): K=1.38×10 ⁻⁴ , α=0.7
Polyethylene (PE): K=3.92×10 ⁻⁴ , α=0.733
Polypropylene (PP): K=1.03×10 ⁻⁴ , α=0.78

・Melting point (Tm, °C):
The melting point of the copolymer of the present invention is indicated by the maximum peak temperature of the endothermic curve measured by differential scanning calorimetry (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 heat flow (mW) and the horizontal axis is temperature (℃) in DSC measurement. Indicates the temperature of the peak where is the maximum, and if there is one peak, indicates the temperature of that peak.
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 will not be sufficient, and if it is higher than this range, the rigidity may be poor.
The melting point of the copolymer can be determined, for example, by using a DSC (DSC7020) manufactured by SII Nanotechnology Co., Ltd., packing approximately 5.0 mg of a sample into an aluminum pan, heating it at a rate of 10°C/min to 200°C; It can be determined from the absorption curve when the temperature is maintained isothermally at ℃ for 5 minutes, lowered to 20℃ at a rate of 10℃/min, held isothermally at 20℃ for 5 minutes, and then raised again to 200℃ at a rate of 10℃/min. .

・Crystallinity (%):
In the copolymer of the present invention, the degree of crystallinity observed by differential scanning calorimetry (DSC) is not particularly limited, but preferably exceeds 0%. It is more preferable that it exceeds 5%, and even more preferably that it is 7% or more. If the crystallinity is 0%, the copolymer may not have sufficient toughness. Further, the degree of crystallinity is an index of transparency, and it can be judged that the lower the degree of crystallinity of a copolymer, the better its transparency. In applications requiring transparency, the crystallinity of the copolymer is preferably 30% or less, more preferably 25% or less, particularly preferably 25% or less, and 24% or less. The following is most preferable.
The degree of crystallinity of a copolymer can be determined, for example, by determining the heat of fusion (ΔH) from the area of the endothermic melting peak obtained by DSC measurement using the same procedure as for measuring the melting point above, and then calculating the heat of fusion using It can be determined by dividing by the heat of fusion of the crystal, 293 J/g.

・Molecular structure of copolymer:
The molecular chain terminal of the copolymer related to the present invention may be a structural unit (A) of ethylene and/or an α-olefin having 3 to 20 carbon atoms, and the acrylate structure represented by the general formula (1) above. The unit (B) may be a structural unit (C) of any optional monomer included.

Furthermore, the copolymer of the present invention comprises a structural unit (A) of ethylene and/or an α-olefin having 3 to 20 carbon atoms, a structural unit (B) of acrylate represented by the general formula (1), and any Examples include random copolymers, block copolymers, and graft copolymers of the monomer structural unit (C). Among these, random copolymers that can contain a large amount of the structural unit (B) may be used.

An example (1) of the molecular structure of a common ternary copolymer is shown below. In addition, in the case of a binary copolymer that does not contain any optional monomer structural unit (C), it can be expressed by removing "C" from the following formula.
A random copolymer is a structural unit of ethylene and/or an α-olefin having 3 to 20 carbon atoms (A) of the molecular structure example (1) shown below, and a structural unit of an acrylate shown by the general formula (1). (B) and an arbitrary monomer structural unit (C) are copolymers in which the probability of finding each structural unit at a certain arbitrary position in a molecular chain is independent of the type of adjacent structural unit.
As shown below, the molecular structure example (1) of the copolymer includes a structural unit (A) of ethylene and/or an α-olefin having 3 to 20 carbon atoms, and a structural unit of an acrylate represented by the above general formula (1). (B) and the structural unit (C) of an arbitrary monomer form a random copolymer.

For reference, molecular structure example (2) of a copolymer into which an acrylate structural unit (B) represented by general formula (1) is introduced by graft modification shows that ethylene and/or α having 3 to 20 carbon atoms - A part of the polymer or copolymer copolymerized with the structural unit (A) of the olefin and optionally the structural unit (C) of an arbitrary monomer is the structural unit of the acrylate represented by the general formula (1) ( B) is graft-modified.

Additionally, the random copolymerizability of a copolymer can be confirmed by various methods, but a method for determining random copolymerizability from the relationship between the comonomer content and the melting point of the copolymer is the one described in ``Unexamined Japanese Patent Publication No. 2015- 163691 Publication” and “Japanese Unexamined Patent Publication No. 2016-079408”. From the above literature, if the melting point (Tm, °C) of the copolymer is higher than -3.74 x [Z] + 130 (here, [Z] is comonomer content/mol%), it is judged that randomness is low. can do.

The copolymer according to the present invention, which is a random copolymer, has a melting point (Tm, °C) observed by differential scanning calorimetry (DSC), an acrylate structural unit (B) represented by general formula (1), and an arbitrary It is preferable that the total content [Z] (mol%) of the structural unit (C) of the monomer satisfies the following formula (I').
50<Tm<-3.74×[Z]+130...(I')
If the melting point (Tm, °C) of the copolymer is higher than -3.74 x [Z] + 130 (°C), the random copolymerizability is low, resulting in poor mechanical properties such as impact strength, and the melting point is higher than 50 °C. If it is low, heat resistance may be poor.

Further, the copolymer related to the present invention is preferably produced in the presence of a transition metal catalyst from the viewpoint of having a linear molecular structure.
It is known that the molecular structure of a copolymer differs depending on the production method, such as polymerization using a high-pressure radical polymerization process or polymerization using a metal catalyst.
Although this difference in molecular structure can be controlled by selecting the manufacturing method, the approximate molecular structure can be estimated from the relational expression between the composition of the copolymer and the melting point, as shown in the above equation. Specifically, the melting point (Tm, °C) observed by differential scanning calorimetry (DSC) and the content [Y] (mol%) of the structural unit (B) are expressed by the following formula (I).
-3.74×[Y]+113.5<Tm (I)
If the following is satisfied, the copolymer is judged to be linear. When combined with the above formula (I') regarding randomness, in the copolymer of the present invention, the melting point (Tm, °C) and the content [Y] (mol%) of the structural unit (B) are expressed by the following formula: It is preferable that (II) is satisfied.
-3.74×[Y]+113.5<Tm<-3.74×[Y]+130 (II)
If the content and melting point of the structural unit (B) in the copolymer satisfy the above formula (II), the copolymer is substantially linear and a random copolymer, and has rigidity. Desired properties such as the following can be provided in a better balance.

(5) Production of olefin copolymer The polar group-containing copolymer of the present invention comprises ethylene and/or an α-olefin having 3 to 20 carbon atoms, an acrylate represented by the general formula (1), and optionally other optional materials. It can be obtained by copolymerizing the following monomers using a transition metal catalyst. In particular, from the viewpoint of making the molecular structure of the copolymer linear, it is preferable that the copolymer be produced in the presence of a late transition metal catalyst. Therefore, one embodiment of the present invention is a method for producing the polar group-containing olefin copolymer, which is characterized by using a late transition metal complex catalyst.

・Polymerization catalyst for olefin copolymer The type of polymerization catalyst related to the present invention is capable of copolymerizing ethylene and/or α-olefin having 3 to 20 carbon atoms and acrylate represented by general formula (1). Although there is no particular limitation as long as it is a catalyst, for example, a method of polymerization using a group 5 to 11 transition metal compound having a chelating ligand, which is known as a post-metallocene catalyst, is preferred.
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, and palladium atom. , copper atoms, etc. Among these, transition metals of Groups 8 to 11 are preferred, transition metals of Group 10 are more preferred, and nickel (Ni) and palladium (Pd) are particularly preferred. These metals may be used alone or in combination.
The chelating ligand has at least two atoms selected from the group consisting of P, N, O, and S, and is bidentate or multidentate. Contains a ligand and is electronically neutral or anionic. Structures of chelating ligands are illustrated in a review by Brookhart et al. (Chem. Rev., 2000, 100, 1169).
Preferably, the chelating ligand includes a bidentate anionic P, O ligand. Examples of bidentate anionic P, O ligands include phosphorus sulfonic acid, phosphorus carboxylic acid, phosphorus phenol, and phosphorus enolate. Other examples of the chelating ligand include bidentate anionic N, O ligands. Examples of the bidentate anionic N, O ligand include salicylaldoiminate and pyridinecarboxylic acid. Other chelating ligands include diimine ligands, diphenoxide ligands, diamide ligands, and the like.

The structure of the metal complex obtained from the chelating ligand is represented by the following structural formula (c1) or (c2) in which an arylphosphine compound, an arylarsine compound, or an arylantimony compound that may have a substituent is coordinated. Ru.

[In structural formula (c1) and structural formula (c2),
M represents a transition metal atom belonging to any of Groups 5 to 11 of the periodic table of elements, ie, various transition metal atoms as described above.
X ¹ represents an oxygen atom, a sulfur atom, -SO ₃ -, or -CO ₂ -.
Y ¹ represents a carbon atom or a silicon atom.
n represents an integer of 0 or 1.
E ¹ represents a phosphorus atom, an arsenic atom, or an antimony atom.
R ⁵³ and R ⁵⁴ each independently represent hydrogen or a hydrocarbon group which may contain a hetero atom having 1 to 30 carbon atoms.
^R55 each independently represents a hydrogen atom, a halogen atom, or a hydrocarbon group which may contain a C1 to C30 heteroatom.
R ⁵⁶ and R ⁵⁷ are each independently hydrogen, halogen, a hydrocarbon group which may contain a heteroatom having 1 to 30 carbon atoms, OR ⁵² , CO ₂ R ⁵² , CO ₂ M', C(O) N(R ⁵¹ ) ₂ , C(O)R ⁵² , SR ⁵² , SO ₂ R ⁵² , SOR ⁵² , OSO ₂ R ⁵² , P(O)(OR ⁵² ) _2-y (R ⁵¹ ) _y , CN, NHR ⁵² , N(R ⁵² ) ₂ , Si(OR ⁵¹ ) _3-x (R ⁵¹ ) _x , OSi(OR ⁵¹ ) _3-x (R ⁵¹ ) _x , NO ₂ , SO ₃ M', PO ₃ M' ₂ , P(O)(OR ⁵² ) ₂ M' or an epoxy-containing group.
R ⁵¹ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.
R ⁵² represents a hydrocarbon group having 1 to 20 carbon atoms.
M' represents an alkali metal, an 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.
Note that R ⁵⁶ and R ⁵⁷ may be connected to each other to form an alicyclic ring, an aromatic ring, or a heterocycle containing a heteroatom selected from an oxygen atom, a nitrogen atom, or a sulfur atom. At this time, the number of ring members is 5 to 8, and the ring may or may not have a substituent.
L ¹ represents a ligand coordinated to M.
Furthermore, R ⁵³ and L ¹ may be combined with each other to form a ring. ]

More preferably, the complex serving as a polymerization catalyst is a transition metal complex represented by the following structural formula (c3).

[In structural formula (c3),
M represents a transition metal atom belonging to any of Groups 5 to 11 of the periodic table of elements, ie, various transition metal atoms as described above.
X ¹ represents an oxygen atom, a sulfur atom, -SO ₃ -, or -CO ₂ -.
Y ¹ represents a carbon atom or a silicon atom.
n represents an integer of 0 or 1.
E ¹ represents a phosphorus atom, an arsenic atom, or an antimony atom.
R ⁵³ and R ⁵⁴ each independently represent a hydrogen atom or a hydrocarbon group which may contain a hetero atom having 1 to 30 carbon atoms.
R ⁵⁵ each independently represents a hydrogen atom, a halogen atom, or a hydrocarbon group which may contain a C 1 to 30 hetero atom.
R ⁵⁸ , R ⁵⁹ , R ⁶⁰ and R ⁶¹ are each independently a hydrogen atom, a halogen atom, a hydrocarbon group which may contain a C 1 to 30 hetero atom, OR ⁵² , CO ₂ R ⁵² , CO ₂ M', C(O)N(R ⁵¹ ) ₂ , C(O)R ⁵² , SR ⁵² , SO ₂ R ⁵² , SOR ⁵² , OSO ₂ R ⁵² , P(O)(OR ⁵² ) _2-y ( R ⁵¹ ) _y , CN, NHR ⁵² , N(R ⁵² ) ₂ , Si(OR ⁵¹ ) _3-x (R ⁵¹ ) _x , OSi(OR ⁵¹ ) _3-x (R ⁵¹ ) _x , NO ₂ , SO ₃ M', PO ₃ M' ₂ , P(O)(OR ⁵² ) ₂ M' or an epoxy-containing group.
R ⁵¹ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.
R ⁵² represents a hydrocarbon group having 1 to 20 carbon atoms.
M' represents an alkali metal, an 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.
In addition, a plurality of groups appropriately selected from R ⁵⁸ to R ⁶¹ are connected to each other, and a heterocyclic ring containing an alicyclic ring, an aromatic ring, or a heteroatom selected from an oxygen atom, a nitrogen atom, or a sulfur atom is may be formed. At this time, the number of ring members is 5 to 8, and the ring may or may not have a substituent.
L ¹ represents a ligand coordinated to M.
Furthermore, R ⁵³ and L ¹ may be combined with each other to form a ring. ]

Here, as catalysts for Groups 5 to 11 transition metal compounds having chelating ligands, catalysts such as so-called SHOP catalysts and Drent catalysts are typically known.
A SHOP-based catalyst is a catalyst in which a phosphorus-based ligand having an aryl group that may have a substituent is coordinated to nickel metal (see, for example, WO2010-050256).
Further, the Drent-based catalyst is a catalyst in which a phosphorus-based ligand having an aryl group that may have a substituent is coordinated to palladium metal (see, for example, JP-A-2010-202647).

The metal catalyst can be used in combination with an activator, a carrier, etc., if necessary. Examples of the activator include alkylalumoxane and boron-containing compounds, which are cocatalysts used in common metallocene catalysts. The transition metal complex may be used in combination with an activator, a carrier, etc., if necessary.

Moreover, any carrier can be used as the carrier. In general, inorganic oxides and polymer carriers can be suitably used. Specific examples of inorganic oxides include SiO ₂ , Al ₂ O ₃ , MgO, ZrO ₂ , TiO ₂ , B ₂ O ₃ , CaO, ZnO, BaO, ThO ₂ and mixtures thereof, and SiO ₂ Mixed oxides, inorganic silicates such as -Al ₂ O ₃ , SiO ₂ -V ₂ O ₅ , SiO ₂ -TiO ₂ , SiO ₂ -MgO, SiO ₂ -Cr ₂ O ₃ can also be used. As the polymer carrier, polyethylene carrier, polypropylene carrier, polystyrene carrier, polyacrylic acid carrier, polymethacrylic acid carrier, polyacrylic ester carrier, polyester carrier, polyamide carrier, polyimide carrier, etc. can be used. These carriers are not particularly limited in particle size, particle size distribution, pore volume, specific surface area, etc., and any carrier can be used.

As the inorganic silicate, silica, alumina, clay, clay minerals, zeolite, diatomaceous earth, etc. can be used. These may be synthetic products or naturally occurring minerals.
Specific examples of clay and clay minerals include allophane group such as allophane, kaolin group such as dickite, nacrite, kaolinite, and anoroxite, halloysite group such as metahalloysite and halloysite, and serpentine such as chrysotile, lizardite, and antigorite. Stone family, smectite family such as montmorillonite, sauconite, beidellite, nontronite, saponite, hectorite, vermiculite minerals such as vermiculite, mica minerals such as illite, sericite, glauconite, attapulgite, sepiolite, pygorskite, bentonite, wood. Examples include knot clay, gairome clay, hisingerite, pyrophyllite, and Ryokudei stone group. These may form a mixed layer. Examples of artificial compounds include synthetic mica, synthetic hectorite, synthetic saponite, and synthetic taeniolite.

Among these specific examples, preferred are kaolin group such as dickite, nacrite, kaolinite, and anoroxite, hallosite group such as metahalosite and hallosite, serpentine group such as chrysotile, lizardite, and antigorite, montmorillonite, Examples include smectite family such as sauconite, beidellite, nontronite, saponite, and hectorite, vermiculite minerals such as vermiculite, mica minerals such as illite, sericite, and glauconite, synthetic mica, synthetic hectorite, synthetic saponite, and synthetic teniolite. Particularly preferred are smectite minerals such as montmorillonite, sauconite, beidellite, nontronite, saponite, and hectorite, vermiculite minerals such as vermiculite, synthetic mica, synthetic hectorite, synthetic saponite, and synthetic teniolite.

These carriers may be used as they are, but they may be acid-treated with hydrochloric acid, nitric acid, sulfuric acid, etc. and/or treated with LiCl, NaCl, KCl, CaCl ₂ , MgCl ₂ , Li ₂ SO ₄ , MgSO ₄ , ZnSO ₄ , Ti( Salt treatment such as SO ₄ ) ₂ , Zr(SO ₄ ) ₂ , Al ₂ (SO ₄ ) ₃ may be performed. In this treatment, the treatment may be performed by mixing the corresponding acid and base to generate a salt in the reaction system. Further, shape control such as pulverization or granulation or drying treatment may be performed.

In the method for producing a copolymer of the present invention, there are no particular limitations on the polymerization format. Slurry polymerization in which at least a part of the produced polymer becomes a slurry in a medium, bulk polymerization in which the liquefied monomer itself is used as a medium, gas phase polymerization in a vaporized monomer, or polymerization in which the produced polymer is carried out in a liquefied monomer at high temperature and high pressure. High-pressure ionic polymerization in which at least a portion of the polymer is dissolved is preferably used.
Further, any type of polymerization such as batch polymerization, semi-batch polymerization, or continuous polymerization may be used. Living polymerization may be used, or polymerization may be performed while chain transfer occurs.

Although there are no particular restrictions on the copolymerization temperature, copolymerization pressure, and copolymerization time, optimal settings can usually be made from the following ranges in consideration of productivity and process capacity. That is, the copolymerization temperature is usually -20°C to 290°C, preferably 0°C to 250°C, the copolymerization pressure is 0.1 MPa to 100 MPa, preferably 0.3 MPa to 90 MPa, and the copolymerization time is 0. The time can be selected from the range of 1 minute to 10 hours, preferably 0.5 minutes to 7 hours, and more preferably 1 minute to 6 hours.

Copolymerization is generally carried out under an inert gas atmosphere. For example, a nitrogen, argon, or carbon dioxide atmosphere can be used, with a nitrogen atmosphere being preferably used. Note that a small amount of oxygen or air may be mixed in.

The method of supplying the catalyst and monomer to the copolymerization reactor is not particularly limited, and various methods can be used depending on the purpose. For example, in the case of batch polymerization, a predetermined amount of monomer is supplied to a copolymerization reactor in advance, a small amount of an organometallic compound containing a metal element of group 1, 2, 12, or 13 of the periodic table is added, and then, It is possible to adopt a method of copolymerizing by supplying a catalyst. Examples of organometallic compounds include alkylaluminums such as tri-n-butylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, and tri-n-decylaluminum, methylaluminum dichloride, ethylaluminum dichloride, and dimethylaluminum chloride. , diethylaluminum chloride, diethylaluminum ethoxide and the like, and trialkylaluminum is preferably selected. Additional monomers and/or additional catalysts may be fed to the copolymerization reactor. Further, in the case of continuous polymerization, a method can be adopted in which a predetermined amount of monomer and catalyst are continuously or intermittently supplied to a copolymerization reactor, and the copolymerization reaction is continuously performed.

Regarding the control of the composition of the copolymer, a method for controlling the composition can generally be used by supplying a plurality of monomers to a reactor and changing the supply ratio thereof. In addition, there are methods to control the copolymerization composition by taking advantage of differences in the monomer reactivity ratio due to differences in catalyst structure, and methods to control the copolymerization composition by taking advantage of the polymerization temperature dependence of the monomer reactivity ratio. Can be mentioned.

Conventionally known methods can be used to control the molecular weight of the copolymer. In other words, there are methods to control molecular weight by controlling polymerization temperature, methods to control molecular weight by controlling monomer concentration, methods to control molecular weight by using a chain transfer agent, and methods to control molecular weight by controlling the ligand structure in a metal catalyst. Examples include controlling.
When using a chain transfer agent, a conventionally known chain transfer agent can be used. For example, hydrogen, metal alkyl, etc. can be used. Furthermore, the monomer of the structural unit (B) itself may serve as a type of chain transfer agent due to its polar group. In this case, the molecular weight can also be adjusted by controlling the blending ratio and concentration of each structural unit.
When adjusting the molecular weight by controlling the ligand structure in the metal catalyst, bulky substituents may be placed around the transition metal M, or aryl groups or heteroatoms that may have substituents on the transition metal M may be used. Electron-donating groups such as contained substituents can be arranged so as to be able to interact with each other.

(6) Resin composition containing polar group-containing olefin copolymer The polar group-containing olefin copolymer of the present invention is a copolymer consisting of at least the above-mentioned structural units (A) and (B). Within a range that does not deviate from the above, the composition may contain other resins and the like in order to introduce other physical properties. Examples of resins that can be blended include polyolefin resins such as high molecular weight polyethylene, homopolymers of ethylene alone, ethylene/α-olefin copolymers, and polypropylene.

In addition, the polar group-containing olefin copolymer of the present invention may include conventionally known antioxidants, ultraviolet absorbers, lubricants, antistatic agents, colorants, pigments, crosslinking agents, etc., without departing from the gist of the present invention. A resin composition may be prepared by blending additives such as a foaming agent, a nucleating agent, a conductive material, and a filler. Those skilled in the art can use appropriate amounts of these other resins, additives, and the like.

The resin composition containing the polar group-containing olefin copolymer of the present invention can be produced using a single screw extruder, a twin screw extruder, a super mixer, a Henschel mixer, etc. by blending the above-mentioned components in the above-mentioned mixing ratio in any order. It can be produced by kneading and granulating using a conventional kneading machine such as a Banbury mixer, a roll mixer, a Brabender Plastograph, or a kneader. In this case, it is preferable to select a kneading and granulation method that can improve the dispersion of each component, and it is particularly preferable to use a twin-screw extruder to perform kneading and granulation from the viewpoint of economical efficiency. The kneading machine may be used for multi-stage kneading using a plurality of machines with different kneading methods.

One aspect of the present invention is a resin composition containing the above polar group-containing olefin copolymer, and a molded article using the resin composition. Since the resin composition of the present invention has high rigidity and chemical resistance, it can be effectively used for packaging materials such as food films and products such as infusion packs.

The present invention will be described in more detail below with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples. Note that measurements and evaluations of physical properties in Examples and Comparative Examples were carried out by the methods shown below.

[Evaluation method of copolymer]
(1) Melting point Tm, heat of fusion ΔH, crystallinity The melting point Tm of the produced olefin copolymer was determined by the following DSC measurement.
Using "EXSTAR 6000" manufactured by Seiko Electronics Co., Ltd., isothermal at 40°C for 1 minute, temperature increase from 40 to 160°C at 10°C/min, isothermal at 160°C for 10 minutes, and 160 to 10°C at 10°C/min. The melting point Tm was determined by lowering the temperature to 10°C, isothermal for 5 minutes at 10°C, and then increasing the temperature from 10 to 160°C at a rate of 10°C/min.
In addition, the degree of crystallinity can be calculated by calculating the heat of fusion ΔH from the area of the endothermic peak of melting obtained when the temperature is raised from room temperature to 160°C, and dividing ΔH by the heat of fusion of 293 J/g of polyethylene (HDPE) perfect crystals. The degree of compatibility was determined.

(2) Molecular weight distribution parameter Mw/Mn
The molecular weight distribution parameter Mw/Mn of the produced olefin polymer was measured by GPC.
Equipment: Alliance GPCV2000 manufactured by Nippon Waters
Detector: GPCV2000 built-in differential refractometer detector
Preparation of sample: Weigh out 3 mg of the sample and 3 mL of orthodichlorobenzene (containing 0.1 mg/mL of 1,2,4-trimethylphenol) into a 4 mL vial, and add a resin screw cap and a Teflon (registered trademark) septum. After the mixture was covered with a lid, dissolution was carried out for 2 hours using a high temperature shaker model SSC-9300 manufactured by Senshu Scientific Co., Ltd., set at a temperature of 150°C. After the dissolution was completed, it was visually confirmed that there were no insoluble components.
Column: Showa Denko Shodex HT-806M x 2 + Showa Denko Shodex HT-G x 1 Creation of HT-G calibration curve: Prepare 4 4mL glass bottles and apply the following combinations (i) to (iv) to each Weigh out 0.2 mg of monodispersed polystyrene standard sample or n-alkane, then weigh out 3 mL of orthodichlorobenzene (containing 0.1 mg/mL of 1,2,4-trimethylphenol), and After covering with a screw cap and a septum made of Teflon (registered trademark), dissolution was performed for 2 hours using a high temperature shaker model SSC-9300 manufactured by Senshu Scientific Co., Ltd. set at a temperature of 150°C.
(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, Shodex S-1010, Shodex S-28.5
A vial containing a sample solution was set in the apparatus, and measurements were performed under the above-mentioned conditions, and a chromatogram (data set of retention time and differential refractometer detector response) 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 logarithm of the molecular weight. Here, the molecular weights of n-eicosane and n-tetracontane were 600 and 1,200, respectively. A nonlinear least squares method was applied to this plot, and the resulting quartic curve was used as a calibration curve.
Calculation of molecular weight: Measurement was performed under the conditions described above, and chromatograms were recorded at sampling intervals of 1 s. Using this chromatogram, we used the data from Sadao Mori, "Size Exclusion Chromatography" (Kyoritsu Shuppan), Chapter 4, p. The differential molecular weight distribution curve and average molecular weight values (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 using the following formula (H'=H after correction). Chromatogram recording (data import) and average molecular weight calculation were performed using an in-house program (created with Microsoft Visual Basic 6.0) on a PC installed with Microsoft OS Windows (registered trademark) XP. . H'=H/[1.032+189.2/M(PE)]
The following formula was used to convert the molecular weight from polystyrene to polyethylene.
M(PE)=0.468×M(PS)
Measurement temperature: 145℃
Concentration: 20mg/10mL
Injection volume: 0.2ml
Solvent: Orthodichlorobenzene Flow rate: 1.0ml/min

(3) Comonomer content The comonomer content of the produced olefin copolymer was determined by the following measurements.
Method for measuring the amount of structural units of polar group-containing monomers in multi-component polar group-containing olefin copolymers:
The amount of structural units of polar groups in the multi-component polar group-containing olefin copolymer related to the present invention is determined using ¹³ C-NMR spectrum. ¹³ C-NMR spectrum is measured by the following method.
(3-1) Sample preparation and measurement conditions 200 mg of sample was mixed with o-dichlorobenzene/deuterated bromide benzene (C ₆ D ₅ Br) = 4/1 (volume ratio) 2.4 ml and chemical shift reference material. The mixture was placed in an NMR sample tube with an inner diameter of 10 mm along with hexamethyldisiloxane, the tube was purged with nitrogen, the tube was sealed, and the mixture was heated and dissolved to obtain a uniform solution.
For NMR measurement, an AV400 NMR apparatus manufactured by Bruker Japan Co., Ltd. equipped with a 10 mmφ cryoprobe was used.
¹³ C-NMR was used to quantify the comonomer. The measurement conditions for ¹³ C-NMR were a sample temperature of 100° C., a pulse angle of 90°, a pulse interval of 51.5 seconds, and a number of integrations of 512 or more times, using a reverse gate decoupling method.
For chemical shifts, the ¹³ C signal of hexamethyldisiloxane was set at 1.98 ppm, and the chemical shifts of other ¹³ C signals were based on this.
(3-2) Calculation method of OXA comonomer amount <E/OXA>
The amount of comonomer was calculated from the following formula using the signal intensity of the 3-ethyloxetane ring of OXA.
Total amount of OXA (mol%) = I _(OXA) × 100/[I _(OXA) + I _(E) ]
Here, I _(OXA) and I _(E) are quantities represented by the following formulas, respectively.
I _(OXA) = (I _8.2~7.8 +I _27.3~27.1 +I _43.3~43.0 +I _66.4~66.1 +I _77.4~77.1 )/6
I _(E) = (I _180.0~135.0 +I _120.0~2.0 -I _(OXA) ×9)/2
Here, I indicates the integrated intensity, and the numerical value of the subscript of I indicates the range of chemical shift. For example, I _180.0-135.0 indicates the integrated intensity of the ¹³ C signal detected between 180.0 ppm and 135.0 ppm.

(4) Number of methyl branches per 1,000 carbons (number/1000C)
¹³ C-NMR was used to quantify the number of methyl branches. The measurement conditions for ¹³ C-NMR were a sample temperature of 120° C., a pulse angle of 90°, a pulse interval of 51.5 seconds, and a number of integrations of 512 or more times, using a reverse gate decoupling method.
For the chemical shift, the ¹³ C signal of hexamethyldisiloxane is set at 1.98 ppm, and the chemical shifts of other ¹³ C signals are based on this. The number was quantified. Methods for quantifying the number of methyl branches by ¹³ C-NMR are known to those skilled in the art.

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

[Metal complex]
The B-27DM/Ni complex was synthesized according to the synthesis example described in JP-A-2013-043871, and the ligand B-27DM represented by the following chemical formula was used. In addition, according to the example of International Publication WO 2010/050256, B-27DM and Ni(COD) ₂ were combined using bis-1,5-cyclooctadiene nickel (0) (referred to as Ni(COD) ₂ ). A nickel complex was synthesized by reacting with and in a 1:1 (molar ratio).
In the formula, "Me" represents a methyl group, and "C ₆ F ₅ " represents a pentafluorophenyl group.

攪拌しながらオートクレーブを９０℃に昇温し、窒素を０．５ＭＰａまで供給した後、エチレンをオートクレーブに供給し、圧力が３．０ＭＰａになるように調整した。
調整終了後、Ｂ－２７ＤＭ／Ｎｉ触媒１．５ｍｌ（３０μｍｏｌ）を窒素で圧入して共重合を開始させた。
３０分間重合させた後、冷却、脱圧して反応を停止した。
反応溶液は、１リットルのアセトンに投入してポリマーを析出させた後、ろ過洗浄を行い回収し、さらに減圧下で恒量になるまで乾燥を行ないＥ／ОＸＡ共重合体を得た。結果を表１に示す。 [Example 1]
Production of ethylene/(3-ethyloxetan-3-yl)methyl acrylate (OXA) copolymer (E/OXA):
In an autoclave with an internal volume of 2.4 liters and equipped with stirring blades, dry toluene (1.0 liters), 37 mg (0.10 mmol) of tri-n-octyl aluminum (TNOA), and a predetermined amount of acrylic acid (3-ethyloxetane) were placed. 1.7 ml (10 mmol) of -3-yl)methyl (OXA) was charged. OXA is a compound represented by the following formula.

The temperature of the autoclave was raised to 90° C. while stirring, nitrogen was supplied to 0.5 MPa, and then ethylene was supplied to the autoclave and the pressure was adjusted to 3.0 MPa.
After completion of the adjustment, 1.5 ml (30 μmol) of B-27DM/Ni catalyst was introduced under pressure with nitrogen to start copolymerization.
After polymerizing for 30 minutes, the reaction was stopped by cooling and depressurizing.
The reaction solution was poured into 1 liter of acetone to precipitate the polymer, which was then filtered and washed, recovered, and further dried under reduced pressure to a constant weight to obtain an E/OXA copolymer. The results are shown in Table 1.

[Example 2]
Production of ethylene/acrylic acid OXA copolymer (E/OXA):
In an autoclave with an internal volume of 2.4 liters and equipped with stirring blades, dry toluene (1.0 liters), 74 mg (0.20 mmol) of tri-n-octyl aluminum (TNOA), and a predetermined amount of acrylic acid (3-ethyloxetane) were placed. 4.9 ml (30 mmol) of -3-yl)methyl (OXA) was charged.
The temperature of the autoclave was raised to 90° C. while stirring, nitrogen was supplied to 0.5 MPa, and then ethylene was supplied to the autoclave and the pressure was adjusted to 3.0 MPa.
After completion of the adjustment, 15 ml (300 μmol) of B-27DM/Ni catalyst was introduced under pressure with nitrogen to start copolymerization.
After polymerizing for 26 minutes, the reaction was stopped by cooling and depressurizing.
The reaction solution was poured into 1 liter of acetone to precipitate the polymer, which was then filtered and washed, recovered, and further dried under reduced pressure to a constant weight to obtain an E/OXA copolymer. The results are shown in Table 1.

[Example 3]
Production of ethylene/OXA copolymer (E/OXA):
In an autoclave with an internal volume of 2.4 liters and equipped with stirring blades, dry toluene (1.0 liters), 74 mg (0.20 mmol) of tri-n-octyl aluminum (TNOA), and a predetermined amount of acrylic acid (3-ethyloxetane) were placed. 8.2 ml (50 mmol) of -3-yl)methyl (OXA) was charged.
The temperature of the autoclave was raised to 90° C. while stirring, nitrogen was supplied to 0.5 MPa, and then ethylene was supplied to the autoclave and the pressure was adjusted to 3.0 MPa.
After completion of the adjustment, 20 ml (400 μmol) of B-27DM/Ni catalyst was introduced under pressure with nitrogen to start copolymerization.
After polymerizing for 45 minutes, the reaction was stopped by cooling and depressurizing.
The reaction solution was poured into 1 liter of acetone to precipitate the polymer, which was then filtered and washed, recovered, and further dried under reduced pressure to a constant weight to obtain an E/OXA copolymer. The results are shown in Table 1.

As shown in Table 1, an olefin copolymer having an oxetanyl group could be obtained. Applying the comonomer concentration of these copolymers to the aforementioned formula (II) regarding linear and random molecular structures, it is found that the melting point of each resin is greater than -3.74×[Y]+113.5 and Takes a value of -3.74×[Y]+130 or less. Therefore, it was shown that each copolymer had a substantially linear molecular structure, and it was also revealed that the copolymers were highly random. Furthermore, it is clear from the molecular weight distribution parameter (Mw/Mn<3.5 in each Example) and the value of the number of methyl branches that the copolymers of the Examples of the present application have a linear structure. Therefore, each copolymer was shown to have a structure with excellent mechanical strength.

The copolymer of the present invention has excellent hydrolysis resistance and can form molded articles with high strength. Therefore, the present invention can be used in applications that require water resistance and strength, such as packaging materials such as food films and products such as infusion packs.

Claims (7)

A structural unit (A) derived from ethylene and/or an α-olefin having 3 to 20 carbon atoms;
General formula (1) below:

[In the formula,
Z is unsubstituted or substituted with a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, an ester group having 2 to 10 carbon atoms, a substituted silyl group having 3 to 18 carbon atoms, or a halogen atom, and has 1 carbon atom ~20 linear, branched, or cyclic divalent hydrocarbon groups, and the carbon chain of the hydrocarbon group may optionally be an oxygen atom, a sulfur atom, or a group -NR- (where R is hydrogen (representing an atom or a hydrocarbon group having 1 to 10 carbon atoms), and the hydrocarbon group has an oxygen atom, a sulfur atom, or a group -NR- bonded to the oxetanyl group. It's okay,
T represents a hydrogen atom, or a linear, branched, or cyclic hydrocarbon group having 1 to 20 carbon atoms]
It has a structural unit (B) derived from acrylate represented by the melting point (Tm, °C) observed by differential scanning calorimetry (DSC) and the content [Y] (mol %) is the following formula (I):
-3.74×[Y]+113.5<Tm (I)
A polar group-containing olefin copolymer that satisfies the following. Furthermore, the melting point (Tm, °C) observed by differential scanning calorimetry (DSC) and the content [Y] (mol%) of the structural unit (B) satisfy the following formula (II). The polar group-containing olefin copolymer according to claim 1.
-3.74×[Y]+113.5<Tm<-3.74×[Y]+130 (II) The polar group-containing olefin copolymer according to claim 1 or 2, wherein the number of methyl branches calculated by ¹³ C-NMR is 50 or less per 1,000 carbons. The polar group-containing olefin copolymer according to any one of claims 1 to 3, characterized in that the structural unit (B) is contained in an amount of 0.1 to 20.0 mol%. Any one of claims 1 to 4, characterized in that the ratio of weight average molecular weight to number average molecular weight (Mw/Mn) measured by gel permeation chromatography (GPC) is 1.5 or more and 4.0 or less. The polar group-containing olefin copolymer according to item 1. 6. A method for producing a polar group-containing olefin copolymer according to any one of claims 1 to 5, characterized in that a transition metal complex catalyst containing a transition metal of Group 10 of the periodic table is used. A method for producing a group-containing olefin copolymer. 7. The method for producing a polar group-containing olefin copolymer according to claim 6 , wherein the transition metal of Group 10 of the periodic table contains nickel or palladium.