Polar group-containing olefin copolymer

Abstract

To provide a polar group-containing olefin copolymer excellent in balance of crystallinity, rigidity and toughness.SOLUTION: There is provided a multinary polar group-containing olefin copolymer which comprises: a structural unit (A) derived from ethylene or α-olefin; a structural unit (B) having a carboxy group or a structure which produces a carboxy group in the elimination reaction by heat or an acid; and a structural unit (C) derived from acrylic acid which does not cause a heat or acid elimination reaction under the same conditions where a heat or acid elimination reaction produces a carboxy group in the structural unit (B).SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a polar group-containing olefin copolymer, in particular a copolymer that can be used to prepare an ionomer and has an excellent balance of physical properties such as tensile modulus, tensile stress at break, tensile elongation at break, tensile impact strength, crystallinity, and phase angle, and a method for producing the same. [Background technology]

[0002] Ethylene-based ionomers are resins that use ethylene-unsaturated carboxylic acid copolymers as the base resin and are intermolecularly bonded by metal ions such as sodium and zinc. They are strong, elastic, flexible, abrasion-resistant, and transparent (Patent Document 1). Commercially available ethylene-methacrylic acid copolymers include "Nucrel (registered trademark)" developed by DuPont, and ethylene-based ionomers include "Surlyn (registered trademark)," a sodium or zinc salt of ethylene-methacrylic acid copolymer also developed by DuPont.

[0003] Specifically, the ethylene-unsaturated carboxylic acid copolymer that serves as the base resin for this conventionally known ethylene-based ionomer is an ethylene-unsaturated carboxylic acid copolymer obtained by polymerizing ethylene and a polar group-containing monomer such as (meth)acrylic acid by high-pressure radical polymerization (Patent Documents 2 to 4). However, the molecular structure of the ethylene-unsaturated carboxylic acid copolymer produced by high-pressure radical polymerization has many long-chain branches and short-chain branches arranged irregularly, and has the drawback of being insufficient in terms of strength.

[0004] On the other hand, as another method for producing an ethylene-unsaturated carboxylic acid copolymer, which is the base resin of an ethylene-based ionomer, a method has been reported in which a copolymer of ethylene and t-butyl acrylate is produced using a late transition metal catalyst (Patent Document 5), and the resulting polar group-containing olefin copolymer is then subjected to heat or acid treatment to modify it into an ethylene-acrylic acid copolymer (Patent Document 6).

[0005] In addition, a method for producing an ethylene-unsaturated carboxylic acid copolymer, which serves as the base resin for a highly rigid ionomer, has also been reported in which maleic anhydride is graft-modified onto an ethylene-cyclic olefin copolymer (COC) (Patent Document 7). [Prior art documents] [Patent documents]

[0006] [Patent Document 1] U.S. Patent No. 3,264,272 [Patent Document 2] Japanese Patent Application Publication No. 47-23490 [Patent Document 3] Japanese Unexamined Patent Publication No. 11388 / 1983 [Patent Document 4] Japanese Patent Application Laid-Open No. 63-186710 [Patent Document 5] Japanese Patent Application Laid-Open No. 2015-163691 [Patent Document 6] Japanese Patent Application Laid-Open No. 2016-79408 [Patent Document 7] International Publication No. 2009 / 123138 Summary of the Invention [Problem to be solved by the invention]

[0007] Ionomers generally tend to have good moldability, compatibility with pigments, rigidity, transparency, and other physical properties. Because they are advantageous as materials for packaging, for example, methods for synthesizing copolymers for producing ionomers have been studied. However, the method described in Patent Document 6 uses an α-olefin-unsaturated carboxylic acid copolymer produced using a transition metal catalyst as the base resin. While this method produces ionomers with excellent thermal properties and mechanical strength, it poses a problem of low transparency due to the high degree of crystallinity of the resulting polymer. In the ethylene-based ionomers using an ethylene-acrylic acid copolymer as the base resin, as described in the examples of Patent Document 6, the transparency can be controlled by the crystallinity. However, since there is a trade-off between crystallinity and rigidity, lowering the crystallinity to increase transparency results in a decrease in rigidity, making it difficult to balance transparency, rigidity, and toughness.

[0008] The method described in Patent Document 7 has the drawback of low acid content in the α-olefin-unsaturated carboxylic acid copolymer because it is extremely difficult to produce an α-olefin-unsaturated carboxylic acid copolymer containing a large amount of maleic anhydride by graft modification. In fact, the maleic anhydride content of the copolymer described in the examples of Patent Document 7 is approximately 0.7 to 1.4 wt% (0.5 to 1 mol%). Therefore, ethylene-based ionomers using graft-modified copolymers as the base resin have few polar moieties, resulting in an insufficient balance of rigidity, toughness, and transparency. Furthermore, the lack of reactive sites with metal ions is thought to prevent the expected toughness and elasticity of ionomers from being fully realized. Furthermore, the base resin of the ethylene-based ionomer used in the examples of Patent Document 7 contains 21 to 35 mol% of cyclic olefins, resulting in a high glass transition temperature (Tg) and excessive hardness.

[0009] Because ionomers generally inherit the properties of their base resin, α-olefin-unsaturated carboxylic acid copolymers (acid copolymers), obtaining an acid copolymer or a polar group-containing olefin copolymer before modification that has excellent physical properties also leads to obtaining an ionomer that has excellent physical properties. However, such copolymers that have excellent physical properties in themselves and can be used as ionomers have not yet been obtained. Therefore, an object of the present invention is to provide an α-olefin-unsaturated carboxylic acid copolymer or a polar group-containing olefin copolymer that has an excellent balance of physical properties such as crystallinity, rigidity, and toughness. [Means for solving the problem]

[0010] In order to solve the above problems, the inventors conducted extensive research and discovered that by introducing into a polymer structural units derived from polar group-containing olefin monomers that do not undergo elimination reactions due to heat or acid, and by forming a multi-component copolymer based on components that have at least three types of properties, the balance of tensile modulus, tensile stress at break, tensile elongation at break, tensile impact strength, crystallinity, and phase angle can be improved, leading to the present invention.

[0011] That is, a first aspect of the present invention is a multi-component polar group-containing olefin copolymer, characterized by comprising a structural unit (A) derived from ethylene or an α-olefin, a structural unit (B) having a carboxy group or a structure that generates a carboxy group upon a thermal or acid-induced elimination reaction, and a structural unit (C) derived from acrylic acid that does not have a carboxy group and does not undergo a thermal elimination reaction under the same conditions as those under which the structural unit (B) generates a carboxy group through a thermal or acid-induced elimination reaction. [Effects of the Invention]

[0012] The present invention can provide a copolymer having an improved balance of tensile modulus, tensile stress at break, tensile elongation at break, tensile impact strength, crystallinity, and phase angle. The multi-component polar group-containing olefin copolymer of the present invention is a useful material that can be used not only as a material itself but also for preparing ionomers with better physical properties than conventional copolymers. [Brief explanation of the drawings]

[0013] [Figure 1] FIG. 1 is a graph showing the balance between rigidity and toughness in the copolymers of Examples and Comparative Examples. [Figure 2] FIG. 1 is a graph showing the balance between rigidity and strength in the copolymers of Examples and Comparative Examples. DETAILED DESCRIPTION OF THE INVENTION

[0014] One aspect of the present invention is a multi-component polar group-containing olefin copolymer, characterized by comprising structural units (A) derived from ethylene or an α-olefin, structural units (B) having a carboxy group or a structure that generates a carboxy group upon thermal or acid-induced elimination reaction, and structural units (C) derived from acrylic acid that do not have a carboxy group and do not undergo thermal elimination reaction under the same conditions as the thermal or acid-induced elimination reaction that generates a carboxy group from structural units (B). The constituent monomers of the polymer, catalyst components, production method, etc. are described in detail below.

[0015] In the following description, the term "polymerization" collectively refers to homopolymerization of one type of monomer and copolymerization of multiple types of monomers, and copolymerization may be referred to simply as "polymerization" in this specification. Furthermore, although the present invention relates to a polymer, the structure of a polymer itself cannot generally be uniquely determined by a chemical formula or the like. Therefore, in this specification, when describing a polymer, the polymer may be described using its production method, as necessary. In this specification, the symbol "to" indicating a numerical range is used to mean that the numerical values ​​before and after it are included as the lower and upper limits. Furthermore, in this specification, hydrocarbon groups may be represented as "R" or other symbols without a subscript, as necessary. Hydrocarbon groups include general groups composed of carbon and hydrogen, such as linear or branched alkyl groups (e.g., methyl, ethyl, t-butyl), groups with unsaturated bonds (e.g., vinyl), cyclic groups (e.g., cyclopentyl, cyclohexyl, norbornyl), and aromatic groups (e.g., phenyl, naphthyl). However, if any of these groups is specifically excluded in a particular context, this will be clearly stated. Furthermore, unless otherwise specified, a "hydrocarbon group" refers to a monovalent substituent such as an alkyl group or a phenyl group. However, if the context clearly indicates the valence, the valence of the hydrocarbon group follows that description.

[0016] (1) Structural unit (A) The structural unit (A) is at least one structural unit selected from the group consisting of structural units derived from ethylene and structural units derived from α-olefins. Among the α-olefins according to the present disclosure, more preferred are those having the structural formula: CH═CHR d (wherein R d is a hydrocarbon group having 1 to 18 carbon atoms, which may have a linear or branched structure.) More preferably, it is an α-olefin having 3 to 12 carbon atoms.

[0017] Specific examples of the monomer from which the structural unit (A) is derived include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 3-methyl-1-butene, and 4-methyl-1-pentene, and may also be ethylene. The structural unit may be of one type or of multiple types.

[0018] Examples of combinations of two types of structural units (A) include ethylene-propylene, ethylene-1-butene, ethylene-1-hexene, ethylene-1-octene, propylene-1-butene, propylene-1-hexene, and propylene-1-octene.

[0019] Examples of combinations of the three types of structural units (A) include ethylene-propylene-1-butene, ethylene-propylene-1-hexene, ethylene-propylene-1-octene, propylene-1-butene-hexene, and propylene-1-butene-1-octene.

[0020] In the present disclosure, the monomer from which the structural unit (A) is derived preferably contains ethylene as an essential component and may further contain, as necessary, one or more α-olefins having 3 to 20 carbon atoms. In this case, the proportion of ethylene contained in the monomer from which the structural unit (A) is derived may be 65 to 100 mol % or 70 to 100 mol % based on the total moles of the structural unit (A).

[0021] (2) Structural unit (B) The structural unit (B) is a structural unit derived from a monomer having a carboxy group or a structure that generates a carboxy group upon elimination reaction with heat or acid. Here, the carboxy group or the structure that generates a carboxy group upon thermal or acid-induced elimination reaction is bonded to a carbon atom that forms the main chain of the multi-component polar group-containing olefin copolymer of the present invention at any location other than the molecular chain terminal. Therefore, the monomer from which the structural unit (B) is derived is a monomer having a structure that serves as a polymerization reaction site, such as a carbon-carbon double bond, and a carboxy group bonded to a carbon atom of the structure or a structure that generates a carboxy group upon thermal or acid-induced elimination reaction. The structure that serves as the polymerization reaction site is preferably a carbon-carbon double bond, and more preferably a vinyl group (HC=CH-). Furthermore, in the multi-component polar group-containing olefin copolymer of the present invention, the carboxy group possessed by the structural unit (B) or the structure that generates a carboxy group upon thermal or acid-induced elimination reaction is located in the side chain of the copolymer.

[0022] The structural unit (B) contains a structure that generates a carboxyl group upon an elimination reaction due to heat or acid. The "elimination reaction" here is preferably a deprotection reaction of an ester. This allows an α-olefin-unsaturated carboxylic acid copolymer, which serves as the base resin for an ionomer, to be obtained from the multi-component polar group-containing olefin copolymer of the present invention. From the above, there are no particular limitations on the reaction conditions used to obtain an α-olefin-unsaturated carboxylic acid copolymer, as long as they are the reaction conditions commonly used for deprotecting an ester. Commonly used conditions and reagents can be used as the reaction conditions for the elimination reaction, such as heat or acid. The conditions for the elimination reaction, such as temperature and reagents, are well known to those skilled in the art and can be appropriately combined and used with reference to the examples below. The reaction temperature when thermally eliminating the multi-component polar group-containing olefin copolymer of the present invention may be any temperature at which the structural unit (B) becomes a carboxylic acid. If the heating temperature is too low, the ester will not be converted to a carboxylic acid, and if it is too high, decarbonylation and decomposition of the copolymer will proceed. Therefore, the heating temperature of the present invention is preferably in the range of 80°C to 350°C, more preferably 100°C to 340°C, even more preferably 150°C to 330°C, and even more preferably 200°C to 320°C. The reaction time varies depending on the heating temperature, the reactivity of the structural unit (B), etc., but is usually 1 minute to 50 hours, more preferably 2 minutes to 30 hours, even more preferably 2 minutes to 10 hours, still more preferably 2 minutes to 3 hours, and particularly preferably 3 minutes to 2 hours. In the above process, the reaction atmosphere is not particularly limited, but it is generally preferable to carry out the reaction under an inert gas stream. Examples of inert gases that can be used include nitrogen, argon, and carbon dioxide atmospheres, and small amounts of oxygen and air may be mixed in. A solvent can also be used as the reaction medium. Any solvent can be used without particular limitations as long as it is inert under the conditions of this reaction. When a solvent is used, the upper limit of the reaction temperature is preferably the boiling point of the solvent used. Toluene is preferably used because its boiling point is within the above-mentioned preferred reaction temperature range. The reactor used in the above step is not particularly limited, and any method can be used as long as it can stir the copolymer substantially uniformly. A glass vessel or autoclave (AC) equipped with a stirrer may be used, or any conventionally known kneader such as a Brabender Plastograph, a single-screw or twin-screw extruder, a high-intensity screw kneader, a Banbury mixer, a kneader, or a roll may be used. A conventionally known acid-base catalyst may be used as an additive to promote the thermal elimination reaction. The acid-base catalyst is not particularly limited, but examples include alkali metal or alkaline earth metal hydroxides such as sodium hydroxide, potassium hydroxide, and lithium hydroxide; alkali metal or alkaline earth metal carbonates such as sodium bicarbonate and sodium carbonate; solid acids such as montmorillonite; inorganic acids such as hydrochloric acid, nitric acid, and sulfuric acid; and organic acids such as formic acid, acetic acid, benzoic acid, citric acid, paratoluenesulfonic acid, trifluoroacetic acid, and trifluoromethanesulfonic acid. From the viewpoints of reaction promotion effect, cost, and equipment corrosiveness, sodium hydroxide, potassium hydroxide, sodium carbonate, and paratoluenesulfonic acid are preferred, with paratoluenesulfonic acid being more preferred.

[0023] When the multi-component polar group-containing olefin copolymer of the present invention is subjected to an elimination reaction with an acid, a conventionally known acid can be used. The acid catalyst is not particularly limited, and examples thereof include solid acids such as montmorillonite, inorganic acids such as hydrochloric acid, nitric acid, and sulfuric acid, and organic acids such as formic acid, acetic acid, benzoic acid, citric acid, paratoluenesulfonic acid, trifluoroacetic acid, and trifluoromethanesulfonic acid. From the viewpoints of reaction acceleration effect, cost, corrosion resistance of equipment, etc., paratoluenesulfonic acid is preferred, and paratoluenesulfonic acid is more preferred.

[0024] The temperature during the elimination reaction with an acid may be any temperature at which the ester becomes a carboxylic acid, but if the temperature is too low, the ester will not be converted to a carboxylic acid, and if the temperature is too high, decarbonylation and decomposition of the copolymer will proceed. Therefore, the heating temperature in the present invention is preferably 20°C to 250°C, more preferably 50°C to 200°C, even more preferably 60°C to 150°C, particularly preferably 70°C to 140°C, even more preferably 80°C to 130°C, and even more particularly preferably 90°C to 120°C.

[0025] The reaction time for the elimination reaction with an acid varies depending on the temperature, the reactivity of the ester group moiety, etc., but is usually 1 minute to 50 hours, more preferably 2 minutes to 30 hours, even more preferably 2 minutes to 10 hours, still more preferably 2 minutes to 7 hours, and particularly preferably 3 minutes to 5 hours.

[0026] In the above steps, the reaction atmosphere is not particularly limited, but it is generally preferable to carry out the reaction under a stream of inert gas. Examples of inert gases that can be used include nitrogen, argon, and carbon dioxide. Note that a small amount of oxygen or air may be present.

[0027] The reactor used in the above step is not particularly limited, and any method can be used as long as it can stir the copolymer substantially uniformly. A glass vessel or autoclave (AC) equipped with a stirrer may be used, or any conventionally known kneader such as a Brabender Plastograph, a single-screw or twin-screw extruder, a high-intensity screw kneader, a Banbury mixer, a kneader, or a roll may be used.

[0028] A preferred embodiment of the structural unit (B) is at least one selected from the group consisting of structural units (b-1) derived from a polar group-containing olefin monomer represented by the following general formula (1) and structural units (b-2) derived from a polar group-containing olefin monomer represented by the following general formula (2). H2C=CH-T 1 ···(1) [In general formula (1), T 1 teeth, carboxyl group, an alkoxycarbonyl group having 2 to 20 carbon atoms substituted with one or more carboxy groups; a hydrocarbon group having 1 to 30 carbon atoms substituted with one or more carboxy groups; an alkoxy group having 1 to 20 carbon atoms substituted with one or more carboxy groups; an acyloxy group having 1 to 20 carbon atoms substituted with one or more carboxy groups; a substituted amino group having 1 to 12 carbon atoms substituted with one or more carboxy groups; Substituted silyl group having 1 to 18 carbon atoms substituted with one or more carboxy groups ] In general formula (1), T 1 is a carboxyl group structure. H2C=CH-X-COOT 2 ···(2) [In general formula (2), T 2 teeth, t-butyl group, Allyl group benzyl group -CR a R b -OR c (where R a is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and R b , R c are each a hydrocarbon group having 1 to 10 carbon atoms, and R b and R c are substituents selected from the group consisting of groups represented by the formula (which together may be a divalent hydrocarbon group having 1 to 8 carbon atoms, in which one or more methylene groups may be replaced by an ether group or an ester group, and each group may have a hydrocarbon substituent having 1 to 4 carbon atoms); X is a direct bond or -COO-R'- (where R' is a divalent hydrocarbon group having 1 to 30 carbon atoms). In general formula (2), T 2 is a structure that generates a carboxyl group by an elimination reaction caused by heat or acid.

[0029] T other than the carboxy group in the monomer represented by the general formula (1) 1That is, the alkoxycarbonyl group having 2 to 20 carbon atoms, the hydrocarbon group having 1 to 30 carbon atoms, the alkoxy group having 1 to 20 carbon atoms, the acyloxy group having 1 to 20 carbon atoms, the substituted amino group having 1 to 12 carbon atoms, or the substituted silyl group having 1 to 18 carbon atoms, which are substituted with one or more carboxy groups, are not particularly limited in structure as long as they are substituted with one or more carboxy groups and satisfy the carbon number requirement. Furthermore, the position at which the carboxy group is substituted in the above structure is also not particularly limited. However, since reaction with metal ions tends to occur more easily when forming an ionomer, it is preferable that the terminal of the above structure be substituted with a carboxy group.

[0030] T 1 The carbon skeleton of the alkoxycarbonyl group, hydrocarbon group, alkoxy group, acyloxy group, substituted amino group, and substituted silyl group may have a branched structure, a ring, and / or an unsaturated bond. Here, the ring may be an aromatic ring. The carbon skeleton may be substituted with one or more halogen atoms such as chlorine, fluorine, or bromine, a hydroxyl group, a silyl group, or an amino group, and may contain one or more groups having a heteroatom such as an ether bond (—O—), an ester bond, a carbonyl group (C═O), or an amino group. T 1 The lower limit of the number of carbon atoms in the alkoxycarbonyl group (—COOR) in the above formula may be 2 or more, and the upper limit may be 20 or less, or may be 15 or less. T 1 The lower limit of the number of carbon atoms in the hydrocarbon group (R-) in the above formula may be 1 or more, and the upper limit may be 30 or less, or may be 10 or less. T 1 The lower limit of the number of carbon atoms in the alkoxy group (RO-) in the above formula may be 1 or more, and the upper limit may be 20 or less, or may be 10 or less. Here, R may be an aromatic ring, and therefore, T 1 The alkoxy group in the above also includes a phenol structure. T 1 The lower limit of the number of carbon atoms in the acyloxy group (RCOO-) may be 2 or more, and the upper limit may be 20 or less, or may be 10 or less.

[0031] T 1 In the substituted amino group described above, the number of carbon atoms in the amino group (RN-) not substituted with a carboxy group may be 2 or more, provided that the total of the two Rs is 1 or more, and may be 2 or more. The upper limit may be 12 or less, provided that the total of the two Rs is 9 or less. For example, one of the two Rs may be an undecyl group (11 carbon atoms) and the other a methyl group (1 carbon atom). In the amino group, the two Rs may each independently be a substituent having 1 to 6 carbon atoms, and the substituents may have the same or different carbon skeletons, or one may be a hydrogen atom. Furthermore, oxygen may be directly bonded to the nitrogen atom, resulting in a hydroxylamine or hydroxylamine derivative structure. That is, the amino group may contain a hydroxyl group or an alkoxy group as R. Non-limiting examples of amino groups not substituted with a carboxy group include dimethylamino, diethylamino, di-n-propylamino, cyclohexylamino, dodecylamino, and N,O-dimethylhydroxylamino.

[0032] T 1In the substituted silyl group described above, the number of carbon atoms in the silyl group (R3Si-) not substituted with a carboxy group may be 3 or more, provided that the total of the three Rs is 1 or more, and may be 3 or more. The upper limit may be 18 or less, provided that the total of the three Rs is 12 or less. For example, one of the three Rs may be a hexadecyl group (16 carbon atoms) and the remaining two may each be a methyl group (1 carbon atom). In the substituted silyl group, the three Rs may each independently be a substituent having 1 to 6 carbon atoms, and the substituents may have the same or different carbon skeletons. As long as at least one R has a substituent having 1 to 6 carbon atoms, the other Rs may be hydrogen atoms. Furthermore, the silyl group may have a structure in which oxygen is directly bonded to silicon to form a hydroxysilyl or alkoxysilyl group. That is, the silyl group may contain a hydroxyl group or an alkoxy group as R. Non-limiting examples of silyl groups that are not substituted with a carboxy group include a trimethylsilyl group, a triethylsilyl group, a tri-n-propylsilyl group, a dimethylphenylsilyl group, a methyldiphenylsilyl group, and a triphenylsilyl group.

[0033] Non-limiting examples of preferred monomers from which the structural unit (b-1) is derived include the following compounds. Based on these examples and the above definitions, a person skilled in the art would be able to determine the structure of the monomer from which the structural unit (b-1) is derived without being bound by the following examples. [ka] [ka]

[0034] One preferred embodiment of the structural unit (B) is the structural unit (b-2) derived from a polar group-containing olefin monomer represented by the general formula (2). 2 where T 2is a t-butyl group, an allyl group, a benzyl group, -CR a R b -OR c (where R a , R b , R c is as defined above), and X is a direct bond or -COO-R'- (where R' is a divalent hydrocarbon group having 1 to 30 carbon atoms). That is, the structural unit (b-2) as one of the preferred embodiments is a structural unit (b-3) in which the group T 2 is a monomer derived from acrylic acid, in which the above group T 2 A more preferred embodiment of the structural unit (B) is a monomer derived from acrylic acid substituted with T in the general formula (2). 2 is a t-butyl group, -CR a R b -OR c (where R a ~R c is as defined above), and X is a substituent that is a direct bond. An even more preferred structural unit (B) is a structural unit derived from a polar group-containing olefin monomer, wherein T in the general formula (2) is 2 is a t-butyl group and X is a direct bond, that is, a structural unit derived from t-butyl acrylate.

[0035] T 2 The t-butyl, allyl, and benzyl groups in the above formula are functional groups used as protecting groups for esters. The t-butyl group can be removed under strong acid conditions, the allyl group in the presence of a Pd catalyst, and the benzyl group under ester hydrolysis conditions.

[0036] T 2 The group -CR a R b -OR c (R a ~R cis as defined above) is used as an acetal-based ester protecting group, and can be deprotected under hydrolysis conditions. If a chemical species can protect and deprotect a carboxy group, R a ~R c There are no particular limitations on the structure of each. R is a good choice because the reagents that serve as protecting groups are readily available. a is a methyl group, or R b and R c In a preferred embodiment, these are combined together to form a divalent hydrocarbon group having 1 to 8 carbon atoms in which one or more methylene groups may be replaced by an ether group or an ester group. T 2 In the group -CR a R b -OR c Examples of reagents known to form the above, i.e., to introduce a protecting group for the carboxy group, include 3,4-dihydro-2H-pyran, 2,3-dihydrofuran, allyl alkyl ethers such as allyl ethyl ether and allyl isobutyl ether, and chloromethyl methyl ether.

[0037] X is a direct bond or a group represented by -COO-R'- (where R' is a divalent hydrocarbon group having 1 to 30 carbon atoms). R' in the -COO-R'- group is a divalent hydrocarbon group, and includes alkylene groups such as methylene group (-CH2-), ethylene group (-CH2CH2-), propylene group (-CH2CH2CH2-), and butylene group (-CH2CH2CH2CH2-), and arylene groups such as 1,4-phenylene group (-CH4-). R' is preferably a linear alkylene group. X is preferably a direct bond.

[0038] Non-limiting examples of preferred monomers from which the structural unit (b-2) is derived include t-butyl acrylate, allyl acrylate, and benzyl acrylate, as well as the following compounds: Based on these examples and the above definitions, a person skilled in the art would be able to determine the structure of the monomer from which the structural unit (b-2) is derived without being bound by the following examples. [ka]

[0039] (3) Structural unit (C) The structural unit (C) is a structural unit derived from an acrylic acid derivative that does not have a carboxyl group and does not undergo an elimination reaction due to heat or acid under the same conditions as the structural unit (B) undergoes an elimination reaction due to heat or acid to generate a carboxyl group. Therefore, the monomer from which the structural unit (C) is derived is an acrylic acid ester (HC=CHC(=O)OR), but unlike the structural unit (B), the R does not have a carboxyl group as a substituent and does not undergo an elimination reaction. As long as this condition is met, the chemical species of the monomer from which the structural unit (C) is derived is not particularly limited, and those skilled in the art can appropriately select it based on the reactivity of the monomer and the physical properties to be imparted to the copolymer. In this specification, the phrase "does not undergo an elimination reaction" regarding the structural unit (C) means that the structural unit (C) does not undergo an elimination reaction due to heat or acid under the same conditions as the structural unit (B) undergoes an elimination reaction due to heat or acid to generate a carboxyl group.

[0040] A preferred monomer from which the structural unit (C) is derived is a polar group-containing olefin monomer represented by the following general formula (3). H2C=CH-COOCHZ 1 Z 2 ···(3) [In general formula (3), Z 1 and Z 2 are each independently hydrogen atoms, hydroxyl groups, a hydrocarbon group having 1 to 10 carbon atoms substituted with a hydroxyl group; an alkyl group having 1 to 30 carbon atoms; a hydrocarbon group having 3 to 20 carbon atoms substituted with an alkoxycarbonyl group having 2 to 10 carbon atoms; a hydrocarbon group having 3 to 20 carbon atoms substituted with an acyloxy group having 2 to 10 carbon atoms; a hydrocarbon group having 2 to 20 carbon atoms substituted with a substituted amino group having 1 to 12 carbon atoms; a hydrocarbon group having 4 to 30 carbon atoms substituted with a substituted silyl group having 3 to 18 carbon atoms; an alkoxycarbonyl group having 2 to 20 carbon atoms; an acyloxy group having 2 to 10 carbon atoms; amino group, a substituted amino group having 1 to 12 carbon atoms, a substituted silyl group having 3 to 18 carbon atoms, and halogen-substituted hydrocarbon groups having 1 to 20 carbon atoms. is a substituent selected from the group consisting of 1 and Z 2 may be bonded to each other to form a ring]

[0041] In general formula (3), the alkyl group, alkoxycarbonyl group, acyloxy group, substituted amino group, substituted silyl group, and hydrocarbon group may have the same number of carbon atoms as those described above in relation to general formula (1). In general formula (3), Z 1 or Z 2 When one of the groups is a hydroxyl group or an amino group, the other is preferably a hydrogen atom. Therefore, the substituent bonded to the oxygen atom derived from acrylic acid is preferably a methyl group, a hydroxymethyl group, a (substituted) aminomethyl group, a substituted silylmethyl group, or a group having at least two consecutive carbon atoms.

[0042] Non-limiting examples of preferred monomers from which the structural unit (C) is derived are listed below. These are merely examples, and there is no limitation on the type of monomer from which the structural unit (C) is derived as long as it satisfies the above-mentioned conditions. A person skilled in the art would be able to determine the structure of the monomer based on these examples and the above definitions without being bound by the following examples. [ka] [ka]

[0043] (4) Multicomponent polar group-containing olefin copolymer As described above, the multi-component polar group-containing olefin copolymer of the present disclosure is characterized by comprising a structural unit (A) derived from ethylene or an α-olefin, a structural unit (B) having a carboxy group or a structure that generates a carboxy group upon a thermal or acid-induced elimination reaction, and a structural unit (C) derived from acrylic acid that does not have a carboxy group and does not undergo a thermal or acid-induced elimination reaction under the same conditions as those under which the structural unit (B) generates a carboxy group through a thermal or acid-induced elimination reaction.

[0044] The multi-component polar group-containing olefin copolymer of the present disclosure contains at least one type of each of the structural units (A), (B), and (C) described above, and contains a total of three or more types of monomer units. The structural units and amounts of the structural units in the multi-component polar group-containing olefin copolymer according to the present disclosure will be described. A structure derived from one molecule of each of ethylene or α-olefin, a monomer having a carboxy group or a structure that generates a carboxy group upon thermal or acid-induced elimination reaction, and an acrylic acid monomer that does not have a carboxy group and does not undergo thermal elimination reaction is defined as one structural unit in the multi-component polar group-containing olefin copolymer. The ratio of each structural unit in the multi-component polar group-containing olefin copolymer expressed in mol % is the amount of structural unit.

[0045] Amount of structural units of ethylene or α-olefin (A): The structural unit amount of the structural unit (A) according to the present disclosure has a lower limit of 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, even more preferably 87.000 mol% or more, and particularly preferably 91.400 mol% or more, and an upper limit of 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, even more preferably 96.900 mol% or less, and particularly preferably 94.300 mol%. If the amount of structural units derived from ethylene and / or an α-olefin having 3 to 20 carbon atoms is less than the above range, the toughness will be poor, and if it is more than the above range, the crystallinity will be high and the transparency will tend to be poor.

[0046] Amount of structural units of monomer (B) having a carboxyl group or a structure that generates a carboxyl group upon elimination reaction with heat or acid: The structural unit amount of the structural unit (B) according to the present disclosure has a lower limit of 2.000 mol% or more, preferably 2.900 mol% or more, and an upper limit of 20.000 mol% or less, preferably 15.000 mol% or less, more preferably 10.000 mol% or less, even more preferably 8.000 mol%, and particularly preferably 6.100 mol% or less. If the amount of structural units derived from the olefin monomer is less than the above range, the adhesion to highly polar dissimilar materials tends to be insufficient, and if it is more than the above range, sufficient mechanical properties tend to be insufficient.

[0047] Amount of structural units of acrylic acid-derived monomer (C) that does not have a carboxy group and does not undergo an elimination reaction by heat or acid under the same conditions as those in which the structural unit (B) undergoes an elimination reaction by heat or acid to produce a carboxy group: The structural unit amount of the structural unit (C) according to the present disclosure has a lower limit of 0.001 mol% or more, preferably 0.010 mol% or more, more preferably 0.100 mol% or more, even more preferably 0.500 mol% or more, and most preferably 1.900 mol% or more, and an upper limit of 20.000 mol% or less, preferably 15.000 mol% or less, more preferably 10.000 mol% or less, even more preferably 7.000 mol% or less, and particularly preferably 4.800 mol% or less. If the structural unit amount derived from the olefin is less than the above range, the rigidity is insufficient, and if it is more than the above range, the balance between rigidity and toughness tends to be lost.

[0048] The total amount of the structural unit (A), the structural unit (B), and the structural unit (C) must be 100 mol %, but it is preferable to set the amount of the structural unit (A) so that the amounts of the structural units (B) and (C) are within the above ranges.

[0049] Measurement method for the amount of structural units of polar group-containing monomers in multi-component polar group-containing olefin copolymers: The amount of structural units of the polar group in the multi-component polar group-containing olefin copolymer according to the present disclosure is 13 It can be determined using C-NMR spectroscopy. 13 The C-NMR spectrum is measured, for example, by the following method. 200-250 mg of sample is placed in an NMR sample tube with an inner diameter of 10 mm together with 2.4 ml of o-dichlorobenzene / deuterated bromide benzene (CDBr) = 4 / 1 (volume ratio) and hexamethyldisiloxane, a chemical shift reference substance, and the tube is purged with nitrogen, sealed, heated to dissolve, and the resulting homogeneous solution is used for NMR measurement. NMR measurements are carried out at 120°C using a Bruker Biospin AV400M NMR instrument equipped with a 10 mm diameter cryoprobe. 13 C-NMR measurements are performed using the inverse gate decoupling method with a pulse angle of 90°, a pulse interval of 51.5 seconds, and an accumulation count of 512 or more. The chemical shift is set to 1.98 ppm for the methyl carbon peak of hexamethyldisiloxane, and the chemical shifts of peaks due to other carbons are based on this. obtained 13 In C-NMR, the content of each comonomer in a copolymer can be analyzed by identifying signals specific to the substituents of the copolymer and comparing their intensities. The positions of the substituents and signals can be determined by reference to publicly available materials, or can be independently identified depending on the sample. Such analytical techniques are commonly known to those skilled in the art.

[0050] Weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn): The weight-average molecular weight (Mw) of the multi-component polar group-containing olefin copolymer according to the present disclosure is usually in the range of 1,000 to 2,000,000, preferably 10,000 to 1,500,000, more preferably 20,000 to 1,000,000, suitably 31,000 to 800,000, and even more suitably 35,000 to 800,000. If Mw is less than 1,000, physical properties such as mechanical strength and impact resistance are insufficient, while if Mw exceeds 2,000,000, the melt viscosity becomes very high, which may make molding difficult.

[0051] The ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the multi-component polar group-containing olefin copolymer according to the present disclosure is preferably in the range of 1.5 to 4.0, more preferably 1.6 to 3.3, and even more preferably 1.7 to 3.0. If Mw / Mn is less than 1.5, various processability including moldability may be insufficient, while if it exceeds 4.0, the mechanical properties may be poor. In the present disclosure, (Mw / Mn) may also be referred to as the molecular weight distribution parameter.

[0052] The weight average molecular weight (Mw) in the present disclosure is determined by gel permeation chromatography (GPC), and the molecular weight distribution parameter (Mw / Mn) is calculated by determining the number average molecular weight (Mn) by gel permeation chromatography (GPC) and then calculating the ratio of Mw to Mn, Mw / Mn.

[0053] An example of a GPC measurement method according to the present disclosure is also described in the Examples section, but measurements can be performed using commercially available equipment and measurement conditions. Molecular weight calculations are performed using the standard polystyrene method, and conversion from retention volume to molecular weight can be performed using a calibration curve prepared in advance using standard polystyrene. The standard polystyrenes used are, for example, all Tosoh Corporation brands (F380, F288, F128, F80, F40, F20, F10, F4, F1, A5000, A2500, A1000). A calibration curve is created by injecting 0.2 mL of a solution in which each of the polystyrenes is dissolved in ODCB (containing 0.5 mg / mL of BHT) to a concentration of 0.5 mg / mL. The calibration curve uses a cubic equation obtained by approximation using the least squares method. The viscosity equation [η] = K × Mα used for conversion to molecular weight uses the following values: PS:K = 1.38 × 10 -4 , α=0.7 PE:K = 3.92 × 10 -4 , α=0.733 PP:K = 1.03 × 10 -4 , α=0.78

[0054] Melting point (℃): In the multi-component polar group-containing olefin copolymer of the present disclosure, it is more preferable that the melting point (Tm, °C) observed by differential scanning calorimetry (DSC) and the total content [Y] (mol%) of the structural unit (B) and the structural unit (C) satisfy the following formula (I): 50 <Tm<-3.74×[Y]+130···(I) In addition to the total content [Y] (mol%) of the structural units (B) and (C) in the copolymer, the melting point of the copolymer has a significant effect on the mechanical properties of the copolymer, and a copolymer with a lower melting point can exhibit better mechanical properties. However, for example, in the case of a binary copolymer of ethylene and (B) as (A), the melting point of the copolymer depends on the content of (B), and it is extremely difficult to lower the melting point below −3.74 × [Y] + 130 (°C) (where [Y] is the content (mol%) of the structural unit (B)), and sufficient improvement in mechanical properties may not be expected. Therefore, when the melting point of the copolymer according to the present disclosure exceeds −3.74 × [Y] + 130 (° C.), improvement in mechanical properties cannot be expected, and sufficient mechanical properties may be difficult to exhibit. Also, when the melting point is less than 50° C., it may be difficult to maintain the minimum heat resistance required for an ethylene copolymer.

[0055] The melting point can be determined, for example, using an "EXSTAR6000" manufactured by Seiko Electronics Co., Ltd., by measuring the temperature at 40°C for 1 minute, increasing the temperature from 40°C to 160°C at 10°C / min, isothermal at 160°C for 10 minutes, decreasing the temperature from 160°C to 10°C at 10°C / min, isothermal at 10°C for 5 minutes, and then increasing the temperature from 10°C to 160°C at 10°C / min.

[0056] The melting point Tm of the multi-component polar group-containing olefin copolymer according to the present disclosure more preferably satisfies the relationship of formula (I) above, but assuming polyethylene, the melting point is more preferably more than 50° C. and less than 130° C., particularly preferably 60° C. to 128° C., and most preferably 70° C. to 126° C. If it is lower than this range, the heat resistance may be insufficient, and if it is higher than this range, the impact resistance may be poor.

[0057] Crystallinity (%): In the multi-component polar group-containing olefin copolymer of the present disclosure, the crystallinity observed by differential scanning calorimetry (DSC) is not particularly limited, but is preferably greater than 0% and not greater than 30%, more preferably greater than 0% and not greater than 25%, and most preferably greater than 5% and not greater than 25%. If the crystallinity is lower than this range, the toughness is insufficient, and if it is higher than this range, the transparency is poor. Note that the crystallinity is an index of transparency, and it can be determined that the lower the crystallinity, the better the transparency. The degree of crystallinity can be determined, for example, by using an "EXSTAR6000" manufactured by Seiko Instruments Inc. to determine the heat of fusion from the area of ​​the melting endothermic peak obtained when the temperature is raised from room temperature to 160°C, and dividing the heat of fusion by the heat of fusion of perfectly crystalline polyethylene (HDPE), 293 J / g.

[0058] Molecular structure of multi-component polar group-containing olefin copolymer: The multi-component polar group-containing olefin copolymer according to the present disclosure may be a random copolymer, block copolymer, graft copolymer, etc. of structural units (A), (B), and (C). Among these, a random copolymer capable of containing a large amount of polar groups may be used. The molecular chain terminal of the multi-component polar group-containing olefin copolymer according to the present disclosure may be any of the structural units (A), (B), and (C).

[0059] The multi-component polar group-containing olefin copolymer according to the present disclosure may be produced in the presence of a transition metal catalyst in order to make its molecular structure linear. It is known that the molecular structure varies depending on the production method, such as polymerization by a high-pressure radical polymerization process or polymerization using a metal catalyst. The difference in molecular structure can be controlled by selecting the manufacturing method. For example, as described in JP 2010-150532 A, the molecular structure can be estimated from the complex modulus measured with a rotational rheometer.

[0060] · Absolute value of complex elastic modulus G * Phase angle δ at 0.1 MPa In the multi-component polar group-containing olefin copolymer of the present disclosure, the absolute value G of the complex modulus measured by a rotational rheometer * The phase angle δ at pressure = 0.1 MPa may be 50 degrees to 75 degrees. More specifically, the absolute value of the complex modulus G measured with a rotational rheometer * = 0.1MPa at the phase angle δ(G * = 0.1 MPa) is 50 degrees or higher, the molecular structure is a linear structure that does not contain any long chain branches or a structure that contains a small amount of long chain branches that does not affect the mechanical strength. Absolute value of complex modulus G measured by a rotational rheometer * = 0.1MPa at the phase angle δ(G *= 0.1 MPa) is lower than 50 degrees, the molecular structure contains an excessive amount of long chain branches, and the mechanical strength tends to be poor. Absolute value of complex modulus G measured by a rotational rheometer * The phase angle δ at 0.1 MPa is affected by both the molecular weight distribution and long chain branching, but it is an index of the amount of long chain branching when limited to those with Mw / Mn≦4, more preferably Mw / Mn≦3. The more long chain branching there is, the higher the δ(G * = 0.1 MPa) value is small. If Mw / Mn is 1.5 or more, the δ(G * =0.1MPa) value never exceeds 75 degrees.

[0061] The complex elastic modulus is measured as follows. The sample is placed in a 1.0 mm thick heat press mold and preheated for 5 minutes in a heat press at a surface temperature of 180°C. Residual gas in the molten resin is degassed by repeatedly applying and depressurizing pressure. The sample is then pressurized to 4.9 MPa and held for 5 minutes. The sample is then transferred to a press at a surface temperature of 25°C and cooled by holding at 4.9 MPa for 3 minutes to create a pressed plate made of the sample with a thickness of approximately 1.0 mm. The pressed plate made of the sample is cut into a 25 mm diameter circle to serve as the sample. A Rheometrics ARES rotational rheometer is used to measure dynamic viscoelastic properties under the following conditions in a nitrogen atmosphere. Plate: φ25mm parallel plate ·Temperature: 160℃ Distortion: 10% Measurement angular frequency range: 1.0 x 10 -2 ~1.0×10 2 rad / s Measurement interval: 5 points / decade Absolute value of complex modulus G * Common logarithm logG of (Pa) * Plot the phase angle δ against logG * = 5.0, the value of δ (degrees) is * = 0.1 MPa). LogG in the measurement point *If there is no point corresponding to =5.0, logG * Using two points around =5.0, logG * The δ value at logG = 5.0 is calculated by linear interpolation. * <5, logG * Using the three largest values, logG is calculated using a quadratic curve. * The δ value at =5.0 is extrapolated.

[0062] Molecular structure of multi-component polar group-containing olefin copolymer: The multi-component polar group-containing olefin copolymer according to the present disclosure may be a random copolymer. An example of the molecular structure (1) of a typical ternary olefin copolymer containing a polar group is shown below. A random copolymer is a copolymer of the structural unit (A) of ethylene or an α-olefin having 3 to 20 carbon atoms, the structural unit (B) of a polar group-containing monomer, and the structural unit (C) of a non-polar cyclic olefin, as shown in the molecular structure example (1) below, in which the probability of finding each structural unit at any position in a molecular chain is independent of the type of the adjacent structural unit. Furthermore, the molecular chain terminal of the polar group-containing olefin copolymer may be a structural unit (A) of ethylene or an α-olefin having 3 to 20 carbon atoms, a structural unit (B) of a polar group-containing monomer, or a structural unit (C) of a non-polar cyclic olefin. As shown below, the molecular structure example (1) of the polar group-containing olefin copolymer is a random copolymer formed by structural units (A) of ethylene and / or an α-olefin having 3 to 20 carbon atoms, structural units (B) of a polar group-containing monomer, and structural units (C) of a non-polar cyclic olefin. [ka] For reference, an example of the molecular structure (2) of an olefin copolymer into which a polar group has been introduced by graft modification is also shown. A part of the olefin copolymer in which structural units (A) of ethylene and / or an α-olefin having 3 to 20 carbon atoms and structural units (C) of a non-polar cyclic olefin are copolymerized is graft-modified with structural units (B) of a polar group-containing monomer. [ka]

[0063] Methyl branching The polymer obtained by the polymerization reaction usually forms a molecular chain that serves as the main chain by linearly linking the monomers as described above. In the present invention, the olefin moieties (C=C) of the structural units (A), (B) and (C) are usually linked in a straight line to form a polyethylene chain. In this case, the saturated hydrocarbon chain when the structural unit (A) contains an α-olefin, the group T of the structural unit (B) 1 Ya-X 1 -COOT 2 The structural unit (C) of -COOCHZ 1 Z 2Moieties such as those indicated by the symbol "B" will exist as side chains of the polyethylene chain. However, in some cases, the olefin moiety does not form a linear molecular chain but rather branches. In this case, a structure in which methyl groups exist as side chains is created, which is referred to as methyl branching. It is generally known that the number of branches in a polyethylene chain is inversely proportional to the melting point; the greater the number of branches, the lower the melting point, and this is independent of the branching group (Skupov, KM; Piche, L.; Claverie, JP Macromolecules 2008, 41, pp. 2309-2310. Please refer to these for further information). In other words, the more structural units (B) and (C) or methyl branches a copolymer contains, the lower the copolymer's melting point, and the lower its heat resistance and strength tend to be. Furthermore, given the same content of structural units (B) and (C), the functionality of polar groups is expected to be expressed at the same level. The fewer methyl branches, the higher the melting point and the higher its heat resistance and strength. Copolymers produced by radical polymerization have a structure with many long-chain branches and short-chain branches at irregular intervals, resulting in insufficient strength. In the present invention, the number of methyl branches is preferably 50 or less per 1,000 carbon atoms, more preferably 5 or less, even more preferably 3.0 or less, and particularly preferably 1.0 or less per 1,000 carbon atoms; the lower limit is not particularly limited, and the lower the better. A smaller number of methyl branches is preferable because it improves heat resistance and strength. The method for measuring the number of methyl branches in a polymer is as described below, and a method commonly known by those skilled in the art can be used.

[0064] (5) Production of multi-component polar group-containing olefin copolymers The multi-component polar group-containing olefin copolymer according to the present disclosure may be produced in the presence of a transition metal catalyst in order to make its molecular structure linear.

[0065] Polymerization catalyst The type of polymerization catalyst used in the production of the multi-component polar group-containing olefin copolymer according to the present disclosure is not particularly limited as long as it is capable of copolymerizing the monomers from which the structural units (A), (B), and (C) are derived. For example, examples include Group 5 to 11 transition metal compounds having a chelating ligand. Specific examples of preferred transition metals include vanadium atom, niobium atom, tantalum atom, chromium atom, molybdenum atom, tungsten atom, manganese atom, iron atom, platinum atom, ruthenium atom, cobalt atom, rhodium atom, nickel atom, palladium atom, and copper atom. 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. Chelating ligands have at least two atoms selected from the group consisting of P, N, O, and S, and include bidentate or multidentate ligands, and are electronically neutral or anionic. Exemplary structures are provided in the review by Brookhart et al. (Chem. Rev., 2000, 100, 1169). Preferred examples of bidentate anionic P,O ligands include phosphorus sulfonic acid, phosphorus carboxylic acid, phosphorus phenol, and phosphorus enolate. Other preferred examples of bidentate anionic N,O ligands include salicylaldiminate and pyridinecarboxylic acid, as well as diimine ligands, diphenoxide ligands, and diamide ligands.

[0066] The structure of the metal complex obtained from the chelating ligand is represented by the following structural formula (A) and / or (B) in which an arylphosphine compound, an arylarsine compound, or an arylantimony compound, which may have a substituent, is coordinated.

[0067] [ka] [ka] [In structural formulas (A) and (B), M represents a transition metal belonging to any of Groups 5 to 11 of the periodic table of the elements, that is, various transition metals as described above.] X 1 represents oxygen, sulfur, -SO3-, or -CO2-. Y 1 represents carbon or silicon. n represents an integer of 0 or 1. E 1 represents phosphorus, arsenic or antimony. R 1 represents hydrogen or a hydrocarbon group having 1 to 20 carbon atoms. R 2 represents a hydrocarbon group having 1 to 20 carbon atoms. R 3 and R 4 each independently represents hydrogen or a hydrocarbon group having 1 to 30 carbon atoms which may contain a heteroatom. R 5 each independently represents hydrogen, halogen, or a hydrocarbon group having 1 to 30 carbon atoms which may contain a heteroatom. R 6 and R 7 each independently represents hydrogen, halogen, a hydrocarbon group having 1 to 30 carbon atoms which may contain a heteroatom, OR 2 , CO2R 2 , CO2M', C(O)N(R 1 )2, C(O)R 2 , S.R. 2 , SO2R 2 , SOR 2 , OSO2R 2 , P(O)(OR 2 ) 2-y (R 1 ) y , CN, NHR 2 , N(R 2 )2, Si(OR 1 ) 3-x (R 1 ) x , OSi(OR 1 ) 3-x (R 1 ) x, NO2, SO3M', PO3M'2, P(O)(OR 2 )2M' or an epoxy-containing group. M' represents an alkali metal, an alkaline earth metal, ammonium, a quaternary ammonium, or a phosphonium; x represents an integer of 0 to 3; and y represents an integer of 0 to 2. In addition, R 6 and R 7 may be linked to each other to form an alicyclic ring, an aromatic ring, or a heterocyclic ring containing a heteroatom selected from oxygen, nitrogen, and sulfur, in which case the ring has 5 to 8 members and may or may not have a substituent on the ring. L 1 represents a ligand coordinated to M. Also, R 3 and L 1 may be bonded to each other to form a ring. Here, the phrase "may contain a heteroatom" means that the presence of a structure in which a carbon or methylene group (-CH-) of a hydrocarbon is replaced by a heteroatom such as oxygen, nitrogen, or sulfur, or a hydrogen atom of a hydrocarbon is replaced by a heteroatom, such as an ether structure or a carbonyl group, is permitted.

[0068] The catalyst used in the preparation of the copolymer of the present invention is more preferably a transition metal complex represented by the following structural formula (C). [ka] [In structural formula (C), M represents a transition metal belonging to any of Groups 5 to 11 of the periodic table of the elements, that is, various transition metals as described above.] X 1 represents oxygen, sulfur, -SO3-, or -CO2-. Y 1 represents carbon or silicon. n represents an integer of 0 or 1. E 1 represents phosphorus, arsenic or antimony. R 3 and R 4each independently represents hydrogen or a hydrocarbon group having 1 to 30 carbon atoms which may contain a heteroatom. R 5 each independently represents hydrogen, halogen, or a hydrocarbon group having 1 to 30 carbon atoms which may contain a heteroatom. R 8 , R 9 , R 10 and R 11 each independently represents hydrogen, halogen, a hydrocarbon group having 1 to 30 carbon atoms which may contain a heteroatom, OR 2 , CO2R 2 , CO2M', C(O)N(R 1 )2, C(O)R 2 , S.R. 2 , SO2R 2 , SOR 2 , OSO2R 2 , P(O)(OR 2 ) 2-y (R 1 ) y , CN, NHR 2 , N(R 2 )2, Si(OR 1 ) 3-x (R 1 ) x , OSi(OR 1 ) 3-x (R 1 ) x , NO2, SO3M', PO3M'2, P(O)(OR 2 )2M' or an epoxy-containing group. M' represents an alkali metal, an alkaline earth metal, ammonium, a quaternary ammonium, or a phosphonium; x represents an integer of 0 to 3; and y represents an integer of 0 to 2. In addition, R 8 ~R 11 A plurality of groups appropriately selected from the above may be linked to each other to form an alicyclic ring, an aromatic ring, or a heterocyclic ring containing a heteroatom selected from oxygen, nitrogen, and sulfur, in which case the ring has 5 to 8 members and may or may not have a substituent on the ring. L 1 represents a ligand coordinated to M. Also, R 3 and L1 may be bonded to each other to form a ring.

[0069] Here, catalysts known as the so-called SHOP-based and Drent-based catalysts are representative examples of catalysts made of transition metal compounds of Groups 5 to 11 having a chelating ligand. The SHOP catalyst is a catalyst in which a phosphorus-based ligand having an aryl group which may have a substituent is coordinated to nickel metal (see, for example, WO2010-050256). The Drent system is a catalyst in which a phosphorus-based ligand having an aryl group which may have a substituent is coordinated to palladium metal (see, for example, JP-A-2010-202647).

[0070] ·Organometallic compounds: In the production of the multi-component polar group-containing olefin copolymer according to the present disclosure, the polymerization activity can be further increased by contacting a polar group-containing olefin monomer with a small amount of an organometallic compound, and then copolymerizing the monomers from which the structural units (A), (B), and (C) are derived in the presence of the transition metal catalyst. The organometallic compound is an organometallic compound containing a hydrocarbon group which may have a substituent, and can be represented by the following structural formula (H). R 30 nM 30 X 30 mn Structural formula (H) (In the formula, R 30 represents a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, and M 30 is a metal selected from the group consisting of Groups 1, 2, 12 and 13 of the periodic table; X 30 represents a halogen atom or a hydrogen atom, and m represents M 30 The valence, n, is 1 to m.

[0071] Examples of the organometallic compound represented by the structural formula (H) include alkyl aluminums such as tri-n-butyl aluminum, tri-n-hexyl aluminum, tri-n-octyl aluminum, and tri-n-decyl aluminum, and alkyl aluminum halides such as methyl aluminum dichloride, ethyl aluminum dichloride, dimethyl aluminum chloride, diethyl aluminum chloride, and diethyl aluminum ethoxide, with trialkyl aluminum being preferred. More preferably, trialkylaluminums having a hydrocarbon group with 4 or more carbon atoms are selected, and even more preferably, trialkylaluminums having a hydrocarbon group with 6 or more carbon atoms are selected. Even more preferably, tri-n-hexylaluminum, tri-n-octylaluminum, and tri-n-decylaluminum are selected, and tri-n-octylaluminum is most preferably used. The organometallic compound is used in a molar ratio of 10 to the polar group-containing olefin comonomer. -5 ~0.9, preferably 10 -4 ~0.2, more preferably 10 -4 It is preferable to bring into contact an amount of about 0.1 to about 0.1 from the viewpoint of polymerization activity and cost.

[0072] Polymerization method for multi-component polar group-containing olefin copolymer: The method for polymerizing the multi-component polar group-containing olefin copolymer according to the present disclosure is not limited. Examples of polymerization methods are as will be made clear in the examples below, and include slurry polymerization in which at least a portion of the polymer produced becomes a slurry in a medium, bulk polymerization in which liquefied monomer itself is used as a medium, gas phase polymerization carried out in vaporized monomer, and high pressure ionic polymerization in which at least a portion of the polymer produced is dissolved in monomer liquefied at high temperature and pressure. The polymerization method may be any of batch polymerization, semi-batch polymerization, and continuous polymerization. Furthermore, living polymerization may be used, or polymerization may be carried out while chain transfer occurs simultaneously. Furthermore, a so-called chain shuttling agent (CSA) may be used in combination to carry out a chain shuttling reaction or coordinated chain transfer polymerization (CCTP). Specific production processes and conditions are disclosed, for example, in JP-A-2010-260913 and JP-A-2010-202647. When a transition metal catalyst such as the one described above is used in the polymerization reaction, the catalyst is removed by well-known methods such as filtration or reprecipitation during polymerization of the multi-component polar group-containing olefin copolymer. However, trace amounts of metal derived from the catalyst may remain in the resulting copolymer. The presence of such metal elements indicates that the copolymer was prepared using a transition metal catalyst. One aspect of the present invention relates to a multi-component polar group-containing olefin copolymer characterized by containing a transition metal element of Group 10 of the periodic table, particularly nickel or palladium, used as the polymerization catalyst. The content can be measured, for example, by means such as ICP-OES. When a transition metal element is contained, its content is 20,000 μg / g or less, preferably 10,000 μg / g or less, more preferably 5,000 μg / g or less, particularly preferably 2,000 μg / g or less, and most preferably 1,000 μg / g or less. The metal content is inversely proportional to the polymerization activity, and decreases as the activity increases. In other words, as the activity increases, the metal content approaches zero.

[0073] (6) Additives The multi-component polar group-containing olefin copolymer according to the present disclosure may be blended with additives such as antioxidants, light stabilizers, ultraviolet absorbers, metal soaps, hydrochloric acid absorbers, lubricants, antistatic agents, antiblocking agents, colorants, pigments, crosslinking agents, foaming agents, nucleating agents, flame retardants, conductive materials, and fillers, within the scope of the present disclosure.

[0074] The multi-component polar group-containing olefin copolymer of the present invention has excellent physical properties, such as transparency and compatibility, derived from each structural unit, and is useful as a material for packaging and the like. Furthermore, the multi-component polar group-containing olefin copolymer of the present invention can be used to obtain a copolymer that can be used as a base resin for ionomers under typical deprotection reaction conditions. The deprotection reaction can generate a carboxyl group from the structure of the structural unit (B) contained in the multi-component polar group-containing olefin copolymer, which generates a carboxyl group upon thermal or acid-induced elimination reaction. The conditions for temperature, reagents, reaction atmosphere, solvent, additives, reactor, etc., described above for the structural unit (B), can be the same as those described above for the structural unit (B). The multi-component polar group-containing olefin copolymer of the present invention is also useful as a raw material for the base resin for ionomers. [Example]

[0075] 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 the following examples.

[0076] [Evaluation method for copolymers] (1) Melting point Tm, heat of fusion ΔH, degree of crystallinity The melting point Tm of the produced olefin copolymer was determined by the following DSC measurement. Using an "EXSTAR6000" manufactured by Seiko Electronics Co., Ltd., the melting point (Tm) was determined by measurements at 40°C for 1 minute isothermally, heated at 10°C / min from 40 to 160°C, isothermally at 160°C for 10 minutes, cooled at 10°C / min from 160 to 10°C, isothermally at 10°C for 5 minutes, and then heated at 10°C / min from 10 to 160°C. The crystallinity was determined by calculating the heat of fusion ΔH from the area of ​​the melting endothermic peak obtained when the temperature was raised from room temperature to 160°C, and dividing ΔH by the heat of fusion of perfectly crystalline polyethylene (HDPE), 293 J / g.

[0077] (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 Japan Waters Detector: GPCV2000 built-in differential refractometer detector Sample preparation: 3 mg of sample and 3 mL of orthodichlorobenzene (containing 0.1 mg / mL of 1,2,4-trimethylphenol) were weighed into a 4 mL vial, and the vial was sealed with a plastic screw cap and a Teflon (registered trademark) septum. Dissolution was carried out for 2 hours using a Senshu Scientific SSC-9300 high-temperature shaker set to 150°C. After dissolution was complete, the absence of insoluble components was confirmed visually. Column: Showa Denko Shodex HT-806M x 2 + Showa Denko Shodex HT-G x 1 Preparation of HT-G calibration curve: Four 4 mL glass bottles were prepared, and 0.2 mg of the monodisperse polystyrene standard samples or n-alkanes of the combinations (i) to (iv) below were weighed into each bottle. Subsequently, 3 mL of orthodichlorobenzene (containing 0.1 mg / mL of 1,2,4-trimethylphenol) was weighed out and placed in each bottle. The bottles were then capped with a resin screw cap and a Teflon (registered trademark) septum, and the bottles were dissolved for 2 hours in a Senshu Scientific SSC-9300 high-temperature shaker set to 150°C. (i) Shodex S-1460, S-66.0, n-Eicosane (ii) Shodex S-1950, Shodex S-152, n-tetracontane (iii) Shodex S-3900, Shodex S-565, Shodex S-5.05 (iv)Shodex S-7500, Shodex S-1010, Shodex S-28.5 The vial containing the sample solution was placed in the instrument, and measurements were performed under the conditions described above. Chromatograms (data sets of retention time and differential refractometer detector response) were recorded at sampling intervals of 1 s. The retention times (peak apexes) of each polystyrene standard sample were read from the resulting chromatograms and plotted against the logarithmic molecular weights. Here, the molecular weights of n-eicosane and n-tetracontane were set to 600 and 1,200, respectively. A nonlinear least-squares method was applied to this plot, and the resulting quartic curve was used as the calibration curve.

[0078] Molecular weight calculation: Measurements were performed under the aforementioned conditions, and chromatograms were recorded at sampling intervals of 1 s. Using these chromatograms, the differential molecular weight distribution curve and average molecular weight values ​​(Mn, Mw, and Mz) were calculated according to the method described in Chapter 4, pages 51-60, of "Size Exclusion Chromatography" by Sadao Mori (Kyoritsu Shuppan). However, to correct for the molecular weight dependence of dn / dc, the height H from the baseline in the chromatogram was corrected using the following formula (H' = corrected H). Chromatogram recording (data acquisition) and average molecular weight calculation were performed using a proprietary program (written in Microsoft Visual Basic 6.0) on a PC with Microsoft Windows XP installed. H' = H / [1.032 + 189.2 / M(PE)] The molecular weight conversion from polystyrene to polyethylene was carried out using the following formula. M(PE) = 0.468 × M(PS) Measurement temperature: 145℃ Concentration: 20mg / 10mL Injection amount: 0.2ml Solvent: orthodichlorobenzene Flow rate: 1.0ml / min

[0079] (3) Comonomer content The comonomer content of the produced olefin copolymer was determined by the following measurement. Measurement method for 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 according to the present invention is 13 It can be determined using C-NMR spectroscopy. 13 C-NMR spectra are measured by the following method. 1) 200-250 mg of sample is placed in an NMR sample tube with an inner diameter of 10 mm together with 2.4 ml of o-dichlorobenzene / deuterated bromide benzene (CDBr) = 4 / 1 (volume ratio) and hexamethyldisiloxane, a chemical shift reference substance, and the tube is purged with nitrogen, sealed, heated to dissolve, and the resulting homogeneous solution is subjected to NMR measurement. NMR measurements were performed using an AV400 NMR instrument manufactured by Bruker Japan Ltd. equipped with a 10 mmφ cryoprobe. 13 The C-NMR measurement conditions were a sample temperature of 120°C, a pulse angle of 90°, a pulse interval of 51.5 seconds, and an accumulation count of 512 or more, using the inverse gate decoupling method. The chemical shifts are those of hexamethyldisiloxane. 13 The C signal was set to 1.98 ppm, and the other 13 The chemical shift of the C signal was based on this.

[0080] 4) Analysis method for comonomer content <e tba> The quaternary carbon signal of the t-butyl acrylate group of tBA is 13 It is detected at 79.6 to 78.8 in the C-NMR spectrum. Using these signal intensities, the amount of comonomer was calculated according to the following formula. Total amount of tBA (mol%) = I (tBA) ×100 / 〔I (tBA) +I (E) 〕 where I (tBA) , I (E) are the quantities shown in the following equations, respectively. 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 nba> The quaternary carbon signal of the t-butyl acrylate group of tBA is 13 The methylene signal of the butoxy group of nBA is detected at 64.1 to 63.4 ppm in the C-NMR spectrum. Using these signal intensities, the amount of comonomer was calculated using the following formula. Total amount of tBA (mol%) = I (tBA) ×100 / 〔I (tBA) +I (nBA) +I (E) 〕 Total amount of nBA (mol%) = I (nBA) ×100 / 〔I (tBA) +I (nBA) +I (E) 〕 where I (tBA) , I (nBA) , I (E) are the quantities shown in the following equations, respectively. I (tBA) =I 79.6~78.8 I (nBA) =I 64.1~63.4 I (E) =(I 180.0~135.0 +I 120.0~2.0 -I (nBA) ×7-I (tBA) ×7) / 2 <e tba iba> The quaternary carbon signal of the t-butyl acrylate group of tBA is 13 The methylene signal of the isobutoxy group of iBA is detected at 70.5 to 69.8 ppm, and the methyl signal of the isobutoxy group is detected at 19.5 to 18.9 ppm in the C-NMR spectrum. Using these signal intensities, the amount of comonomer was calculated using the following formula. Total amount of tBA (mol%) = I (tBA) ×100 / 〔I (tBA) +I (iBA) +I (E) 〕 Total amount of iBA (mol%) = I (iBA) ×100 / 〔I (tBA) +I (iBA) +I (E) 〕 where I (tBA) , I (iBA) , I (E) are the quantities shown in the following equations, respectively. I (tBA) =I 79.6~78.8 I (iBA) =(I 70.5~69.8 +I 19.5~18.9 ) / 3 I (E) =(I 180.0~135.0 +I 120.0~2.0 -I (iBA) ×7-I (tBA) ×7) / 2 <e tba ma> The quaternary carbon signal of the t-butyl acrylate group of tBA is 13 The methyl carbon signal of the methoxy group of methyl acrylate (MA) is detected at 51.1 to 50.4 ppm in the C-NMR spectrum. Using these signal intensities, the amount of comonomer was calculated using the following formula. Total amount of tBA (mol%) = I (tBA) ×100 / 〔I (tBA) +I (MA) +I (E) 〕 Total amount of MA (mol%) = I (MA) ×100 / 〔I (tBA) +I (MA) +I (E) 〕 where I (tBA) , I (MA) , I (E) are the quantities shown in the following equations, respectively. I (tBA) =I 79.6~78.8 I (MA) =I 51.1~50.4 / 2 I(E)=(I 180.0~135.0 +I 120.0~2.0 -I (MA) ×4-I (tBA) ×7) / 2 <e tba ea> The quaternary carbon signal of the t-butyl acrylate group of tBA is 13 The C-NMR spectrum shows a signal between 79.6 and 78.8 ppm, the methyl carbon signal of the ethoxy group of ethyl acrylate (EA) is detected between 14.7 and 14.1 ppm, and the methylene carbon signal is detected between 60.0 and 59.3 ppm. Using these signal intensities, the amount of comonomer was calculated using the following formula: Total amount of tBA (mol%) = I (tBA) ×100 / 〔I (tBA) +I (EA) +I (E) 〕 Total amount of EA (mol%) = I (EA) ×100 / 〔I (tBA) +I (EA) +I (E) 〕 where I (tBA) , I (EA) , I (E) are the quantities shown in the following equations, respectively. I (tBA) =I 79.6~78.8 I (EA) =(I 14.7~14.1 +I 60.0~59.3 ) / 2 I (E) =(I 180.0~135.0 +I 120.0~2.0 -I (EA) ×5-I (tBA) ×7) / 2 <e tba c6> The quaternary carbon signal of the t-butyl acrylate group of tBA is 13 The methylene signal of 1-hexene was detected at 23.4 to 23.1 ppm in the C-NMR spectrum. Using these signal intensities, the amount of comonomer was calculated using the following formula: Total amount of tBA (mol%) = I (tBA) ×100 / 〔I (tBA) +I (C6) +I (E) 〕 Total C6 (mol%) = I (C6) ×100 / 〔I (tBA) +I (C6) +I (E) 〕 where I (tBA) , I (C6) , I (E) are the quantities shown in the following equations, respectively. I (tBA) =I 79.6~78.8 I (C6) =I 23.4~23.1 I (E) =(I 180.0~135.0 +I 120.0~2.0 -I (C6) ×6-I (tBA) ×7) / 2 <e tba va> The quaternary carbon signal of the t-butyl acrylate group of tBA is 13 The C-NMR spectrum detects signals from 79.6 to 78.8 ppm, and the vinyl acetate methyl signal from 20.9 to 20.2 ppm. Using these signal intensities, the comonomer amount was calculated using the following formula: Total amount of tBA (mol%) = I (tBA) ×100 / 〔I (tBA) +I (VA) +I (E) 〕 Total VA content (mol%) = I (VA) ×100 / 〔I (tBA) +I (VA) +I (E) 〕 where I (tBA) , I (VA) , I (E) are the quantities shown in the following equations, respectively. I (tBA) =I 79.6~78.8 I (VA) =I 20.9~20.2 I (E) =(I 180.0~135.0 +I 120.0~2.0 -I (VA) ×4-I (tBA) ×7) / 2 <e tba mma> The quaternary carbon signal of the t-butyl acrylate group of tBA is 13 The C-NMR spectrum detects the signal at 79.6 to 78.8 ppm, and the methoxy signal of methyl methacrylate at 52.5 to 49.5 ppm. Using these signal intensities, the amount of comonomer was calculated using the following formula. Total amount of tBA (mol%) = I (tBA) ×100 / 〔I (tBA) +I (MMA) +I (E) 〕 Total amount of MMA (mol%) = I (MMA) ×100 / 〔I (tBA) +I (MMA) +I (E) 〕 where I (tBA) , I (MMA) , I (E) are the quantities shown in the following equations, respectively. I (tBA) =I 79.6~78.8 I (MMA) =I 52.5~49.5 I (E) =(I 180.0~135.0 +I 120.0~2.0 -I (MMA) ×5-I (tBA) ×7) / 2 In the following description, when the amount of each copolymer is indicated by "<0.1" including an inequality sign, this means that the copolymer is present as a structural unit in the copolymer but in an amount of less than 0.1 mol % taking into account significant digits.

[0081] (4) Tensile test Using the resins of each example and comparative example, a 1 mm thick sheet was prepared by the method described in JIS K7151 (1995) (cooling method A), and this was punched out to prepare a small 5B type test piece described in JIS K7162 (1994). A tensile test was performed at a temperature of 23°C according to JIS K7161 (2014), and the tensile modulus, tensile stress at break, and tensile elongation at break were measured. The test speed was 10 mm / min.

[0082] (5) Tensile impact strength test 1) Preparation method for tensile impact strength test samples The resins of each example and comparative example were placed in a 1 mm thick heat press mold and preheated for 5 minutes in a heat press at a surface temperature of 180 °C. The resin was melted and degassed by repeatedly applying pressure and depressurizing pressure. The mold was then pressurized to 4.9 MPa and held for 5 minutes. The mold was then gradually cooled at a rate of 10 °C / min under a pressure of 4.9 MPa. When the temperature had dropped to near room temperature, the molded plate was removed from the mold. The resulting molded plate was conditioned for at least 48 hours in an environment of 23 ± 2 °C and 50 ± 5 °C humidity. Test specimens in the shape of ASTM D1822 Type-S were punched out of the conditioned press plate to prepare tensile impact strength test samples.

[0083] 2) Tensile impact strength test conditions Using the resins of each example and comparative example, the tensile impact strength was measured with reference to Method B of JIS K 7160-1996. Note that the only difference from JIS K 7160-1996 is the shape of the test piece. Regarding other measurement conditions, the test was conducted according to the method in accordance with JIS K 7160-1996, and the tensile impact strength was measured.

[0084] (6) Absolute value of complex elastic modulus G * = 0.1MPa at the phase angle δ(G * =0.1MPa) The resins of each example and comparative example were placed in a 1.0 mm thick heat press mold and preheated for 5 minutes in a heat press at a surface temperature of 180°C. Residual gas in the molten resin was removed by repeatedly applying and depressurizing pressure, and the mold was then pressurized to 4.9 MPa and held for 5 minutes. The mold was then transferred to a press at a surface temperature of 25°C and cooled by holding the mold at 4.9 MPa for 3 minutes to produce a pressed plate made of a sample with a thickness of approximately 1.0 mm. The pressed plate made of the sample was cut into a circular shape with a diameter of 25 mm to serve as a sample. Dynamic viscoelasticity was measured under the following conditions in a nitrogen atmosphere using an ARES rotational rheometer manufactured by Rheometrics. Plate: φ25mm parallel plate ·Temperature: 160℃ Distortion: 10% Measurement angular frequency range: 1.0 x 10 -2 ~1.0×10 2 rad / s Measurement interval: 5 points / decade Absolute value of complex modulus G * Common logarithm logG of (Pa) * Plot the phase angle δ against logG * = 5.0, the value of δ (degrees) is * = 0.1 MPa). * If there is no point corresponding to =5.0, logG * Using two points around =5.0, logG * The δ value at logG = 5.0 was calculated by linear interpolation. * <5, logG * Using the three largest values, logG is calculated using a quadratic curve. * The δ value at δ = 5.0 was extrapolated.

[0085] (7) Transformation from ester structure to carboxylic acid structure by IR spectrum analysis The copolymer was melted at 180°C for 3 minutes and compression molded to prepare a film with a thickness of about 50 µm. This film was analyzed by Fourier transform infrared spectroscopy to obtain the infrared absorption spectrum of the copolymer. Product name: FT / IR-6100 manufactured by JASCO Corporation Measurement method: transmission method Detector: TGS Accumulation count: Auto (16-64 times) Resolution: 4.0cm -1 Measurement wavelength: 5000~500cm -1

[0086] (8) Number of methyl branches per 1,000 carbon atoms To quantify the number of methyl branches, 13 C-NMR was used. 13 The C-NMR measurement conditions were a sample temperature of 120°C, a pulse angle of 90°, a pulse interval of 51.5 seconds, and an accumulation count of 512 or more, using the inverse gate decoupling method. The chemical shifts are those of hexamethyldisiloxane. 13 The C signal was set to 1.98 ppm, and the other 13 The chemical shift of the C signal was used as a reference, and the number of methyl branches was quantified by the integral ratio of the signal of the methyl group derived from the methyl branch. 13 The method for quantifying the number of methyl branches by C-NMR is known to those skilled in the art.

[0087] (9) Metal content in copolymer ICP-OES was used to quantify the metal content. Approximately 0.1 to 0.3 g of sample was placed in a Kelder flask, and sulfuric acid was added and heated for wet decomposition. The decomposition solution was transferred to a measuring flask. The volume was adjusted to a constant value, and the Ni in the solution was measured using ICP-OES. Product name: ICP-OES, Thermo Fisher Scientific, iCAP6500DUO

[0088] (10)Vp activity The productivity (Vp activity) of the produced olefin copolymer was calculated by the following formula. Productivity (Vp activity) = {yield of olefin copolymer produced (kg)} ÷ {amount of catalyst (mol) × polymerization time (h)}

[0089] [Metal complexes] The B-27DM / Ni complex was synthesized according to the synthesis example described in JP 2013-043871 A, using the ligand B-27DM represented by the following chemical formula: Also, according to the example in WO 2010 / 050256 A, a nickel complex was synthesized in which B-27DM and Ni(COD)2 reacted in a 1:1 (molar ratio) using bis-1,5-cyclooctadiene nickel(0) (referred to as Ni(COD)2). In the formula, "Me" represents a methyl group and "C6F5" represents a pentafluorophenyl group. [ka]

[0090] The B-423 / Ni catalyst used the ligand B-423, which has the following chemical formula: Ni(acac)2 (51.4 mg) was weighed into a 50 ml recovery flask and dissolved in toluene (10 ml) to prepare a 20 mM Ni(acac)2 toluene solution. The resulting solution was clear blue. The Ni(acac)2 toluene solution (10 ml) was added to the recovery flask containing B-423 (111.7 mg) and stirred at room temperature for 1 minute, resulting in a clear purple solution. The concentration of the reaction product was calculated assuming that B-423 and Ni(acac) reacted in a 1:1 ratio to form a nickel complex. In the formula, "Me" represents a methyl group and "iPr" represents an isopropyl group. [ka]

[0091] Examples and Comparative Examples Example 1 1) Preparation of ethylene / t-butyl acrylate (tBA) / n-butyl acrylate (nBA) terpolymer (E / tBA / nBA): A 2.4-liter autoclave equipped with a stirring blade was charged with dry toluene (1.0 liter), 55 mg (0.15 mmol) of tri-n-octylaluminum (TNOA), 8.7 ml (60 mmol) of a predetermined amount of t-butyl acrylate (tBA: comonomer 1), and 4.3 ml (30 mmol) of a predetermined amount of n-butyl acrylate (nBA: comonomer 2). The temperature of the autoclave was raised to 90°C while stirring, and nitrogen was supplied until the pressure reached 0.2 MPa. Then, ethylene was supplied to the autoclave to adjust the pressure to 1.0 MPa. After the adjustment was completed, 10 ml (200 μmol) of B-27DM / Ni catalyst was injected with nitrogen to initiate copolymerization. After polymerization for 38 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 recovered by filtration and washing, and further dried under reduced pressure until a constant weight was reached, yielding E / tBA / nBA resin 1. The results are shown in Tables 1 and 2. The Ni quantitative analysis result by ICP-OES was 980 μg / g.

[0092] 2) Preparation of ethylene / acrylic acid (AA) / n-butyl acrylate (nBA) terpolymer (E / AA / nBA) by modification: A 50 ml separable flask was charged with 4 g of Resin 1, 0.08 g of paratoluenesulfonic acid monohydrate, and 18.5 ml of toluene, and the mixture was stirred at 105°C for 4 hours. 18.5 ml of ion-exchanged water was added, stirred, and allowed to stand, after which the aqueous layer was extracted. Subsequently, the addition and extraction of ion-exchanged water was repeated until the pH of the extracted aqueous layer reached 5 or higher. The solvent was removed from the remaining solution by distillation under reduced pressure, and the solution was dried to a constant weight, yielding E / AA / nBA Resin I. The results of physical property measurements are shown in Table 3. In the IR spectrum of Resin I, a carbonyl group at 1730 cm -1 The peak around 850 cm originating from the t-butyl group of the t-butyl ester decreased. -1 The peak around 1700 cm originating from the carbonyl group of the carboxylic acid (dimer) has disappeared. -1 The peak around this region increased. This confirmed the decomposition of t-butyl ester and the generation of carboxylic acid. The Ni quantitative analysis result by ICP-OES was 960 μg / g.

[0093] Example 2 1) Preparation of ethylene / t-butyl acrylate (tBA) / isobutyl acrylate (iBA) terpolymer (E / tBA / iBA): A 2.4-liter autoclave equipped with a stirring blade was charged with dry toluene (1.0 liter), 55 mg (0.15 mmol) of TNOA, 8.7 ml (60 mmol) of a predetermined amount of t-butyl acrylate (tBA: comonomer 1), and 4.3 ml (30 mmol) of a predetermined amount of isobutyl acrylate (iBA: comonomer 2). The temperature of the autoclave was raised to 90°C while stirring, and nitrogen was supplied until the pressure reached 0.2 MPa. Then, ethylene was supplied to the autoclave to adjust the pressure to 1.0 MPa. After the adjustment was completed, 10 ml (200 μmol) of B-27DM / Ni catalyst was injected with nitrogen to initiate copolymerization. After polymerization 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 recovered by filtration and washing, and further dried under reduced pressure until a constant weight was reached, yielding E / tBA / iBA Resin 2. The results are shown in Tables 1 and 2. The Ni quantitative analysis result by ICP-OES was 1130 μg / g.

[0094] 2) Preparation of ethylene / acrylic acid (AA) / isobutyl acrylate (iBA) terpolymer (E / AA / iBA) by modification: Using the resin 2, E / AA / iBA resin II was obtained in the same manner as in 2) of Example 1. The results of measuring the physical properties are shown in Table 3. In the IR spectrum of Resin II, the carbonyl group of the ester at 1730 cm -1 The peak around 850 cm originating from the t-butyl group of the t-butyl ester decreased. -1 The peak around 1700 cm originating from the carbonyl group of the carboxylic acid (dimer) has disappeared. -1 The peaks around it increased. This confirmed the decomposition of t-butyl ester and the generation of carboxylic acid. The Ni quantitative analysis result by ICP-OES was 960 μg / g.

[0095] Example 3 1) Preparation of ethylene / t-butyl acrylate (tBA) / methyl acrylate (MA) terpolymer (E / tBA / MA): A 2.4 L autoclave equipped with a stirring blade was charged with dry toluene (1.0 L), 73 mg (0.20 mmol) of TNOA, 8.7 mL (60 mmol) of a predetermined amount of t-butyl acrylate (tBA: comonomer 1), and 2.7 mL (30 mmol) of a predetermined amount of methyl acrylate (MA: comonomer 2). The temperature of the autoclave was raised to 90°C while stirring, and nitrogen was supplied until the pressure reached 0.2 MPa. Then, ethylene was supplied to the autoclave to adjust the pressure to 1.0 MPa. After the adjustment was completed, 10 ml (200 μmol) of B-27DM / Ni catalyst was injected with nitrogen to initiate copolymerization. After polymerization for 75 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, washed, and recovered, and then dried under reduced pressure until it reached a constant weight, yielding E / tBA / MA Resin 3. The results are shown in Tables 1 and 2. The Ni quantitative analysis result by ICP-OES was 960 μg / g.

[0096] 2) Preparation of ethylene / acrylic acid (AA) / methyl acrylate (MA) terpolymer (E / AA / MA) by modification: Using the resin 3, an E / AA / MA resin III was obtained in the same manner as in 2) of Example 1. The results of the physical property measurements are shown in Table 3. In the IR spectrum of Resin III, the carbonyl group of the ester at 1730 cm -1 The peak around 850 cm originating from the t-butyl group of the t-butyl ester decreased. -1 The peak around 1700 cm originating from the carbonyl group of the carboxylic acid (dimer) has disappeared. -1 The peaks around it increased. This confirmed the decomposition of t-butyl ester and the generation of carboxylic acid. The Ni quantitative analysis result by ICP-OES was 950 μg / g.

[0097] Example 4 1) Preparation of ethylene / t-butyl acrylate (tBA) / ethyl acrylate (EA) terpolymer (E / tBA / EA): A 2.4-liter autoclave equipped with a stirring blade was charged with dry toluene (1.0 liter), 73 mg (0.20 mmol) of TNOA, 8.7 ml (60 mmol) of a predetermined amount of t-butyl acrylate (tBA: comonomer 1), and 3.3 ml (30 mmol) of a predetermined amount of ethyl acrylate (EA: comonomer 2). The temperature of the autoclave was raised to 90°C while stirring, and nitrogen was supplied until the pressure reached 0.2 MPa. Then, ethylene was supplied to the autoclave to adjust the pressure to 1.0 MPa. After the adjustment was completed, 10 ml (200 μmol) of B-27DM / Ni catalyst was injected with nitrogen to initiate copolymerization. After polymerization for 49 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, washed, and recovered, and then dried under reduced pressure until it reached a constant weight, yielding E / tBA / EA Resin 4. The results are shown in Tables 1 and 2. The Ni quantitative analysis result by ICP-OES was 1,000 μg / g.

[0098] 2) Preparation of ethylene / acrylic acid (AA) / methyl acrylate (EA) terpolymer (E / AA / EA) by modification: Using the resin 4, E / AA / EA resin IV was obtained in the same manner as in 2) of Example 1. The results of measuring the physical properties are shown in Table 3. In the IR spectrum of Resin IV, the carbonyl group of the ester at 1730 cm -1 The peak around 850 cm originating from the t-butyl group of the t-butyl ester decreased. -1 The peak around 1700 cm originating from the carbonyl group of the carboxylic acid (dimer) has disappeared. -1 The peaks around it increased. This confirmed the decomposition of t-butyl ester and the generation of carboxylic acid. The Ni quantitative analysis result by ICP-OES was 930 μg / g.

[0099] (Comparative Example 1) 1) Preparation of ethylene / t-butyl acrylate (tBA) / 1-hexene (C6) terpolymer (E / tBA / C6): A 2.4-liter autoclave equipped with a stirring blade was charged with dry toluene (1.0 liter), 55 mg (0.15 mmol) of TNOA, 8.7 ml (60 mmol) of a predetermined amount of t-butyl acrylate (tBA: comonomer 1), and 3.8 ml (30 mmol) of a predetermined amount of 1-hexene (C6: comonomer 2). The temperature of the autoclave was raised to 90°C while stirring, and nitrogen was supplied until the pressure reached 0.2 MPa. Then, ethylene was supplied to the autoclave to adjust the pressure to 1.0 MPa. After the adjustment was completed, 10 ml (200 μmol) of B-27DM / Ni catalyst was injected with nitrogen to initiate copolymerization. After polymerization for 22 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, washed, and recovered, and then dried under reduced pressure until it reached a constant weight, yielding E / tBA / C6 Resin 5. The results are shown in Tables 1 and 2. The Ni quantitative analysis result by ICP-OES was 770 μg / g.

[0100] 2) Preparation of ethylene / acrylic acid (AA) / 1-hexene (C6) terpolymer (E / AA / C6) by modification: Using the resin 5, E / AA / C6 resin V was obtained in the same manner as in 2) of Example 1. The results of the physical property measurements are shown in Table 3. In the IR spectrum of the resin V, a carbonyl group at 1730 cm -1 The peaks around 850 cm originate from the t-butyl group of the t-butyl ester. -1 The peak around 1700 cm originating from the carbonyl group of the carboxylic acid (dimer) has disappeared. -1 The peak around 1000μg / g increased. This confirmed that the ester had been thermally decomposed. The Ni quantitative analysis result by ICP-OES was 750μg / g.

[0101] (Comparative Example 2) 1) Preparation of ethylene / t-butyl acrylate (tBA) / vinyl acetate (VA) terpolymer (E / tBA / VA): A 2.4-liter autoclave equipped with a stirring blade was charged with dry toluene (1.0 liter), 55 mg (0.15 mmol) of TNOA, 8.7 ml (60 mmol) of a predetermined amount of t-butyl acrylate (tBA: comonomer 1), and 2.8 ml (30 mmol) of a predetermined amount of vinyl acetate (VA: comonomer 2). The temperature of the autoclave was raised to 90°C while stirring, and nitrogen was supplied until the pressure reached 0.2 MPa. Then, ethylene was supplied to the autoclave to adjust the pressure to 1.0 MPa. After the adjustment was completed, 10 ml (200 μmol) of B-27DM / Ni catalyst was injected with nitrogen to initiate copolymerization. After polymerization for 52 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 recovered by filtration and washing, and further dried under reduced pressure until a constant weight was reached to obtain E / tBA / VA Resin 6. The results are shown in Tables 1 and 2. The Ni quantitative analysis result by ICP-OES was 880 μg / g.

[0102] 2) Preparation of ethylene / acrylic acid (AA) / vinyl acetate (VA) terpolymer (E / AA / VA) by modification: Using the resin 6, E / AA / VA resin VI was obtained in the same manner as in 2) of Example 1. The results of measuring the physical properties are shown in Table 3. In the IR spectrum of the resin VI, the carbonyl group of the ester at 1730 cm -1 The peaks around 850 cm originate from the t-butyl group of the t-butyl ester. -1 The peak around 1700 cm originating from the carbonyl group of the carboxylic acid (dimer) has disappeared. -1 The peak around 1000μg / g increased. This confirmed that the ester had been thermally decomposed. The Ni quantitative analysis result by ICP-OES was 860μg / g.

[0103] (Comparative Example 3) 1) Preparation of ethylene / t-butyl acrylate (tBA) / methyl methacrylate (MMA) terpolymer (E / tBA / MMA): A 2.4 L autoclave equipped with a stirring blade was charged with dry toluene (1.0 L), 55 mg (0.15 mmol) of TNOA, 8.7 mL (60 mmol) of a predetermined amount of t-butyl acrylate (tBA: comonomer 1), and 3.2 mL (30 mmol) of a predetermined amount of methyl methacrylate (MMA: comonomer 2). The temperature of the autoclave was raised to 90°C while stirring, and nitrogen was supplied until the pressure reached 0.2 MPa. Then, ethylene was supplied to the autoclave to adjust the pressure to 1.0 MPa. After the adjustment was completed, 10 ml (200 μmol) of B-27DM / Ni catalyst was injected with nitrogen to initiate copolymerization. After polymerization for 23 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 recovered by filtration and washing, and further dried under reduced pressure until a constant weight was reached to obtain E / tBA / MMA Resin 7. The results are shown in Tables 1 and 2. The Ni quantitative analysis result by ICP-OES was 800 μg / g.

[0104] 2) Preparation of ethylene / acrylic acid (AA) / methyl methacrylate (MMA) terpolymer (E / AA / MMA) by modification: Using the resin 7, E / AA / VA resin VII was obtained in the same manner as in 2) of Example 1. The results of measuring the physical properties are shown in Table 3. In the IR spectrum of Resin VII, the carbonyl group of the ester at 1730 cm -1 The peaks around 850 cm originate from the t-butyl group of the t-butyl ester. -1 The peak around 1700 cm originating from the carbonyl group of the carboxylic acid (dimer) has disappeared. -1 The peak around 1000μg / g increased. This confirmed that the ester had been thermally decomposed. The Ni quantitative analysis result by ICP-OES was 780μg / g.

[0105] Example 5 1) Preparation of ethylene / t-butyl acrylate (tBA) / n-butyl acrylate (nBA) terpolymer (E / tBA / nBA): A 2.4-liter autoclave equipped with a stirring blade was charged with dry toluene (1.0 liter), 55 mg (0.15 mmol) of TNOA, 29.1 ml (200 mmol) of a predetermined amount of t-butyl acrylate (tBA: comonomer 1), and 8.6 ml (60 mmol) of a predetermined amount of n-butyl acrylate (nBA: comonomer 2). The temperature of the autoclave was raised to 90°C while stirring, and nitrogen was supplied until the pressure reached 0.3 MPa. Then, ethylene was supplied to the autoclave to adjust the pressure to 3.3 MPa. After the adjustment was completed, 24 ml (480 μmol) of B-27DM / Ni catalyst was injected with nitrogen to initiate copolymerization. After polymerization for 92 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, washed, recovered, and dried under reduced pressure until it reached a constant weight, yielding E / tBA / nBA Resin 8. The results are shown in Tables 4 and 6. The Ni quantitative analysis result by ICP-OES was 210 μg / g. Note that "no data" in the tables means that it was not measured.

[0106] 2) Preparation of ethylene / acrylic acid (AA) / n-butyl acrylate (nBA) terpolymer (E / AA / nBA) by modification: Using Resin 8, E / AA / nBA Resin VIII was obtained in the same manner as in Example 1, item 2). The results of physical property measurements are shown in Table 8. In the table, "no data" means that measurements were not performed. In the IR spectrum of the resin VIII, a carbonyl group at 1730 cm -1 The peak around 850 cm originating from the t-butyl group of the t-butyl ester decreased. -1 The peak around 1700 cm originating from the carbonyl group of the carboxylic acid (dimer) has disappeared. -1 The peak around this region increased. This confirmed the decomposition of t-butyl ester and the generation of carboxylic acid. The Ni quantitative analysis result by ICP-OES was 210 μg / g.

[0107] Example 6 1) Preparation of ethylene / t-butyl acrylate (tBA) / n-butyl acrylate (nBA) terpolymer (E / tBA / nBA): A 2.4-liter autoclave equipped with a stirring blade was charged with dry toluene (1.0 liter), 55 mg (0.15 mmol) of TNOA, 29.1 ml (200 mmol) of a predetermined amount of t-butyl acrylate (tBA: comonomer 1), and 11.4 ml (80 mmol) of a predetermined amount of n-butyl acrylate (nBA: comonomer 2). The temperature of the autoclave was raised to 80°C while stirring, and nitrogen was supplied until the pressure reached 0.3 MPa. Then, ethylene was supplied to the autoclave to adjust the pressure to 3.3 MPa. After the adjustment was completed, 24 ml (480 μmol) of B-27DM / Ni catalyst was injected with nitrogen to initiate copolymerization. After polymerization for 180 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 recovered by filtration and washing, and further dried under reduced pressure until a constant weight was reached, yielding E / tBA / nBA Resin 9. The results are shown in Tables 4 and 6. The Ni quantitative analysis result by ICP-OES was 210 μg / g.

[0108] 2) Preparation of ethylene / acrylic acid (AA) / n-butyl acrylate (AA) terpolymer (E / BA / nBA) by modification: E / AA / nBA Resin IX was obtained in the same manner as in 2) of Example 1, except that Resin 9 was used. The results of measuring the physical properties are shown in Table 8. In the IR spectrum of the resin IX, a carbonyl group at 1730 cm -1 The peak around 850 cm originating from the t-butyl group of the t-butyl ester decreased. -1 The peak around 1700 cm originating from the carbonyl group of the carboxylic acid (dimer) has disappeared. -1 The peak around this region increased. This confirmed the decomposition of t-butyl ester and the generation of carboxylic acid. The Ni quantitative analysis result by ICP-OES was 210 μg / g.

[0109] Example 7 Preparation of ethylene / t-butyl acrylate (tBA) / n-butyl acrylate (nBA) terpolymer (E / tBA / nBA): A 2.4 L autoclave equipped with a stirring blade was charged with dry toluene (1.0 L), 55 mg (0.15 mmol) of TNOA, 29.1 mL (200 mmol) of a predetermined amount of t-butyl acrylate (tBA: comonomer 1), and 7.1 mL (50 mmol) of a predetermined amount of n-butyl acrylate (nBA: comonomer 2). The temperature of the autoclave was raised to 90°C while stirring, and nitrogen was supplied until the pressure reached 0.3 MPa. Then, ethylene was supplied to the autoclave to adjust the pressure to 3.3 MPa. After the adjustment was completed, 18 ml (360 μmol) of B-27DM / Ni catalyst was injected with nitrogen to initiate copolymerization. After polymerization for 88 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 recovered by filtration and washing, and further dried under reduced pressure until a constant weight was reached, yielding E / tBA / nBA resin 10. The results are shown in Tables 4 and 6. The Ni quantitative analysis result by ICP-OES was 164 μg / g.

[0110] 2) Preparation of ethylene / acrylic acid (AA) / n-butyl acrylate (nBA) terpolymer (E / BA / nBA) by modification: Using the resin 10, an E / AA / nBA resin X was obtained in the same manner as in 2) of Example 1. The results of measuring the physical properties are shown in Table 8. In the IR spectrum of the resin X, a carbonyl group at 1730 cm -1 The peak around 850 cm originating from the t-butyl group of the t-butyl ester decreased. -1 The peak around 1700 cm originating from the carbonyl group of the carboxylic acid (dimer) has disappeared. -1 The peak around this region increased. This confirmed the decomposition of t-butyl ester and the generation of carboxylic acid. The Ni quantitative analysis result by ICP-OES was 160 μg / g.

[0111] Example 8 Preparation of ethylene / t-butyl acrylate (tBA) / isobutyl acrylate (iBA) terpolymer (E / tBA / iBA): A 2.4-liter autoclave equipped with a stirring blade was charged with dry toluene (1.0 liter), 55 mg (0.15 mmol) of TNOA, 17.0 ml (115 mmol) of a predetermined amount of t-butyl acrylate (tBA: comonomer 1), and 14.0 ml (100 mmol) of a predetermined amount of isobutyl acrylate (iBA: comonomer 2). The temperature of the autoclave was raised to 90°C while stirring, and nitrogen was supplied until the pressure reached 0.3 MPa. Then, ethylene was supplied to the autoclave to adjust the pressure to 3.3 MPa. After the adjustment was completed, 24 ml (480 μmol) of B-27DM / Ni catalyst was injected with nitrogen to initiate copolymerization. After polymerization for 120 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 recovered by filtration and washing, and further dried under reduced pressure until a constant weight was reached, yielding E / tBA / iBA resin 11. The results are shown in Tables 4 and 6. The Ni quantitative analysis result by ICP-OES was 240 μg / g.

[0112] 2) Preparation of ethylene / acrylic acid (AA) / isobutyl acrylate (iBA) terpolymer (E / BA / iBA) by modification: E / AA / iBA Resin XI was obtained in the same manner as in 2) of Example 1, using Resin 11. The results of measuring the physical properties are shown in Table 8. In the IR spectrum of the resin XI, a carbonyl group at 1730 cm -1 The peak around 850 cm originating from the t-butyl group of the t-butyl ester decreased. -1 The peak around 1700 cm originating from the carbonyl group of the carboxylic acid (dimer) has disappeared. -1 The peak around this region increased. This confirmed the decomposition of t-butyl ester and the generation of carboxylic acid. The Ni quantitative analysis result by ICP-OES was 230 μg / g.

[0113] Example 9 Preparation of ethylene / t-butyl acrylate (tBA) / isobutyl acrylate (iBA) terpolymer (E / tBA / iBA): A 2.4-liter autoclave equipped with a stirring blade was charged with dry toluene (1.0 liter), 55 mg (0.15 mmol) of TNOA, 28.0 ml (190 mmol) of a predetermined amount of t-butyl acrylate (tBA: comonomer 1), and 3.0 ml (22 mmol) of a predetermined amount of isobutyl acrylate (iBA: comonomer 2). The temperature of the autoclave was raised to 90°C while stirring, and nitrogen was supplied until the pressure reached 0.3 MPa. Then, ethylene was supplied to the autoclave to adjust the pressure to 3.3 MPa. After the adjustment was completed, 24 ml (480 μmol) of B-27DM / Ni catalyst was injected with nitrogen to initiate copolymerization. After polymerization for 55 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 recovered by filtration and washing, and further dried under reduced pressure until a constant weight was reached, yielding E / tBA / iBA resin 12. The results are shown in Tables 4 and 6. The Ni quantitative analysis result by ICP-OES was 200 μg / g.

[0114] 2) Preparation of ethylene / acrylic acid (AA) / isobutyl acrylate (iBA) terpolymer (E / BA / iBA) by modification: Using the resin 12, E / AA / iBA resin XII was obtained in the same manner as in 2) of Example 1. The results of measuring the physical properties are shown in Table 8. In the IR spectrum of the resin XII, a carbonyl group of the ester at 1730 cm -1 The peak around 850 cm originating from the t-butyl group of the t-butyl ester decreased. -1 The peak around 1700 cm originating from the carbonyl group of the carboxylic acid (dimer) has disappeared. -1 The peak around this region increased. This confirmed the decomposition of t-butyl ester and the generation of carboxylic acid. The Ni quantitative analysis result by ICP-OES was 190 μg / g.

[0115] Example 10 Preparation of ethylene / t-butyl acrylate (tBA) / isobutyl acrylate (iBA) terpolymer (E / tBA / iBA): A 2.4-liter autoclave equipped with a stirring blade was charged with dry toluene (1.0 liter), 55 mg (0.15 mmol) of TNOA, 27.5 ml (189 mmol) of a predetermined amount of t-butyl acrylate (tBA: comonomer 1), and 1.0 ml (7 mmol) of a predetermined amount of isobutyl acrylate (iBA: comonomer 2). The temperature of the autoclave was raised to 100°C while stirring, and nitrogen was supplied until the pressure reached 0.3 MPa. Then, ethylene was supplied to the autoclave to adjust the pressure to 3.3 MPa. After the adjustment was completed, 24 ml (480 μmol) of B-27DM / Ni catalyst was injected with nitrogen to initiate copolymerization. After polymerization for 29 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 recovered by filtration and washing, and further dried under reduced pressure until it reached a constant weight, yielding E / tBA / iBA resin 13. The results are shown in Tables 4 and 6. The Ni quantitative analysis result by ICP-OES was 210 μg / g.

[0116] 2) Preparation of ethylene / acrylic acid (AA) / isobutyl acrylate (iBA) terpolymer (E / BA / iBA) by modification: Using the resin 13, an E / AA / iBA resin XIII was obtained in the same manner as in 2) of Example 1. The results of the physical property measurements are shown in Table 8. In the IR spectrum of the resin XIII, a carbonyl group of the ester at 1730 cm -1 The peak around 850 cm originating from the t-butyl group of the t-butyl ester decreased. -1 The peak around 1700 cm originating from the carbonyl group of the carboxylic acid (dimer) has disappeared. -1 The peak around this region increased. This confirmed the decomposition of t-butyl ester and the generation of carboxylic acid. The Ni quantitative analysis result by ICP-OES was 210 μg / g.

[0117] Example 11 1) Preparation of ethylene / t-butyl acrylate (tBA) / isobutyl acrylate (iBA) terpolymer (E / tBA / iBA): Internal volume 1.6m 3 An autoclave equipped with a stirring blade was charged with dry toluene (1000 L), 0.0375 kg (0.256 mol) of TNOA, and predetermined amounts of 4.4 kg (35 mol) of t-butyl acrylate (tBA: comonomer 1) and 1.6 kg (12 mol) of isobutyl acrylate (iBA: comonomer 2). The autoclave was heated to 95°C with stirring, and then ethylene was supplied to the autoclave to adjust the pressure to 0.8 MPa. After the adjustment was completed, copolymerization was carried out by supplying B-423 / Ni catalyst (3 mmol / min). The temperature was maintained at 95°C during the reaction, and ethylene was supplied to maintain the pressure. tBA and iBA were supplied so that the molar ratio of ethylene:tBA:iBA was 92.0:5.4:2.6. After 515 minutes of polymerization, the reaction was stopped, yielding E / tBA / iBA resin 14. The results are shown in Tables 5 and 7.

[0118] 2) Preparation of ethylene / acrylic acid (AA) / isobutyl acrylate terpolymer (E / AA / iBA) by modification: Using the resin 14, E / AA / iBA resin XIV was obtained in the same manner as in 2) of Example 1. The results of measuring the physical properties are shown in Table 8. In the IR spectrum of the resin XIV, a carbonyl group of the ester at 1730 cm -1 The peak around 850 cm originating from the t-butyl group of the t-butyl ester decreased. -1 The peak around 1700 cm originating from the carbonyl group of the carboxylic acid (dimer) has disappeared. -1 The peak around the peak increased, confirming the decomposition of the t-butyl ester and the production of a carboxylic acid.

[0119] Comparative Example 4 Comparative material: ethylene-methacrylic acid copolymer (E / MAA) A polar group-containing olefin copolymer (manufactured by DuPont-Mitsui Polychemicals Co., Ltd., brand: Nucrel N1560), which is a copolymer of ethylene and methacrylic acid and produced by a high-pressure radical process, was used as a comparative raw material. The results of physical property measurements are shown in Table 8.

[0120] (Comparative Example 5) Preparation of ethylene / t-butyl acrylate (tBA) copolymer (E / tBA): Internal volume 1.6m 3 Into a stirring blade-equipped autoclave, dry toluene (1000 liters), 50 g (0.14 mol) of TNOA, and a predetermined amount of 6.3 kg (49 mol) of t-butyl acrylate (tBA: comonomer 1) were charged. The autoclave was heated to 100° C. with stirring, and then ethylene was supplied to the autoclave to adjust the pressure to 0.8 MPa. After the adjustment was completed, B-27DM / Ni catalyst (160 mmol) was fed to initiate copolymerization. The temperature was maintained at 100°C during the reaction, and B-27DM / Ni catalyst (160 mmol) was added in several portions. Ethylene was added to maintain the pressure, and tBA was added so that the ethylene:tBA molar ratio was 94.4:5.6. After 240 minutes of polymerization, the reaction was stopped to obtain E / tBA resin 15. The results are shown in Tables 5 and 7.

[0121] 2) Preparation of ethylene / acrylic acid (AA) copolymer (E / AA): E / AA resin XV was obtained in the same manner as in 2) of Example 1 using resin 15. The results of measuring the physical properties are shown in Table 8. In the IR spectrum of the resin XV, a carbonyl group at 1730 cm originating from the ester is observed. -1 The peaks around 850 cm originate from the t-butyl group of the t-butyl ester. -1 The peak around 1700 cm originating from the carbonyl group of the carboxylic acid (dimer) has disappeared. -1 The peak around 1000 ppm increased, confirming that the ester had been thermally decomposed.

[0122] (Comparative Example 6) Ethylene-methacrylic acid-isobutyl acrylate copolymer (E / MAA / iBA): The copolymer of ethylene, methacrylic acid, and isobutyl acrylate (Resin XVI) was a polar group-containing olefin copolymer (methacrylic acid content = 4 wt%, isobutyl acrylate content = 16 wt%) produced by a high-pressure radical process. The results of physical property measurements are shown in Table 8.

[0123] [Table 1]

[0124] [Table 2]

[0125] [Table 3]

[0126] [Table 4]

[0127] [Table 5]

[0128] [Table 6]

[0129] [Table 7]

[0130] [Table 8]

[0131] From Table 2, it can be seen that Resins 1 to 4, which are copolymers using an acrylic acid ester as comonomer 2 in Examples 1 to 4, have significantly lower crystallinity and higher transparency under the same preparation conditions than Resins 5 to 7, which are copolymers using an α-olefin, vinyl ester, or methyl methacrylate as comonomer 2 in Comparative Examples 1 to 3. If an attempt is made to achieve transparency equivalent to that of Resins 1 to 4 using an α-olefin, vinyl ester, or methyl methacrylate as comonomer 2, a large amount of comonomer is required, making it less economical than acrylic acid ester. Table 3 shows that Resins I to IV, which are acid copolymers of Resins 1 to 4 in Examples 1 to 4, have significantly lower crystallinity and higher transparency than Resins V to VII, which are acid copolymers of Resins 5 to 7 in Comparative Examples 1 to 3. This suggests that Resins 1 to 4 maintain high transparency even after being acid copolymerized. Furthermore, Resins I to IV have a larger phase angle δ than Resins V to VII, suggesting that they exhibit superior mechanical strength. From the above, Resins I to IV have achieved improvements in not only mechanical strength but also transparency compared to known resins. In Table 8, compared to Comparative Example 4, which was produced by radical polymerization, Resins VIII to XII and XIV, which are acid copolymers obtained from Examples 5 to 9 and 11, have higher tensile elongation at break and tensile impact strength. Furthermore, Resins VIII, IX, X, XII and XIV also have higher tensile stress at break. Furthermore, Resins IX and XIV have low crystallinity and high transparency. Furthermore, Resin XIII, which is an acid copolymer obtained from Example 10, has a significantly higher tensile modulus than Comparative Example 4, demonstrating an excellent balance of physical properties. Resins VIII to XIV have a larger phase angle than Comparative Example 4, which is likely to indicate excellent mechanical strength. From the above, Examples 5 to 11 have a relatively better balance of rigidity, toughness and transparency than Comparative Example 4. In Table 8, acid copolymer resins VIII to XIV obtained from Examples 5 to 11 have higher tensile stress at break, tensile elongation at break, and tensile impact strength, lower crystallinity, and larger phase angle than acid copolymer resin XV obtained from Comparative Example 5. From the above, Examples 5 to 11 have a relatively better balance of rigidity, toughness, and transparency than Comparative Example 5. In Table 8, compared with Resin XVI of Comparative Example 6, which was produced by radical polymerization, Resins VIII to XIV, which are acid copolymers obtained from Examples 5 to 11, have higher tensile modulus and tensile breaking stress, and larger phase angles. Furthermore, Resins VIII to XII also have high tensile impact strength. Resins VIII, IX, XI, and XIV also have low crystallinity and good transparency. Therefore, Examples 5 to 11 have a better balance of elasticity, rigidity, and transparency than Comparative Example 6.

[0132] The results of measuring the physical properties of the copolymers obtained in the Examples and Comparative Examples are summarized in Figures 1 and 2. According to these figures, the samples of the Comparative Examples are significantly inferior to the other samples in terms of stiffness, strength, or toughness, while the samples of the Examples show well-balanced values ​​in all physical properties. This demonstrates that the copolymers of the present invention are easy to use and have well-balanced physical properties.< / e> < / e> < / e> < / e> < / e> < / e> < / e> < / e>

Claims

1. A structural unit (A) derived from ethylene, A structural unit (B) consisting of a structural unit (b-1) derived from a polar group-containing olefin monomer represented by the following general formula (1), and a structural unit (C) derived from acrylic acid that does not have a carboxy group and does not undergo an elimination reaction due to heat or acid under the same conditions as those in which t-butyl acrylate undergoes an elimination reaction due to heat or acid to produce a carboxy group; and the number of methyl branches per 1,000 carbon atoms is 5 or less. H ２ C=CH-T １ ・・・(1) [In general formula (1), T １ is a carboxy group.

2. 2. The multi-component polar group-containing olefin copolymer according to claim 1, wherein the structural unit (C) is a structural unit (C) derived from a polar group-containing olefin monomer represented by the following general formula (3): H ２ C=CH-COOCHZ １ Z ２ ・・・(3) [In general formula (3), Z １ and Z ２ are each independently hydrogen atoms, hydroxyl groups, a hydrocarbon group having 1 to 10 carbon atoms substituted with a hydroxyl group; Alkyl groups having 1 to 30 carbon atoms a hydrocarbon group having 3 to 20 carbon atoms substituted with an alkoxycarbonyl group having 2 to 10 carbon atoms; a hydrocarbon group having 3 to 20 carbon atoms substituted with an acyloxy group having 2 to 10 carbon atoms; A hydrocarbon group having 2 to 20 carbon atoms substituted with a substituted amino group having 1 to 12 carbon atoms A hydrocarbon group having 4 to 30 carbon atoms substituted with a substituted silyl group having 3 to 18 carbon atoms Alkoxycarbonyl group having 2 to 20 carbon atoms Acyloxy group having 2 to 10 carbon atoms amino group Substituted amino group having 1 to 12 carbon atoms Substituted silyl group having 3 to 18 carbon atoms and a hydrocarbon group having 1 to 20 carbon atoms substituted with halogen. is a substituent selected from the group consisting of １ and Z ２ may be bonded to each other to form a ring.

3. Z in the general formula (3) １ and Z ２ However, each independently, hydrogen atoms, Alkyl groups having 1 to 30 carbon atoms a hydrocarbon group having 3 to 20 carbon atoms substituted with an alkoxycarbonyl group having 2 to 10 carbon atoms; Alkoxycarbonyl group having 2 to 20 carbon atoms Acyloxy group having 2 to 10 carbon atoms and a hydrocarbon group having 1 to 20 carbon atoms substituted with halogen. The multi-component polar group-containing olefin copolymer according to claim 2, wherein the substituent is selected from the group consisting of:

4. Absolute value of complex modulus G measured by a rotational rheometer ＊ The multi-component polar group-containing olefin copolymer according to any one of claims 1 to 3, wherein the phase angle δ at σ = 0.1 MPa is 50 degrees to 75 degrees.

5. 5. The multi-component polar group-containing olefin copolymer according to claim 1, comprising 0.1 to 20.0 mol % of the structural unit (B).

6. The multi-component polar group-containing olefin copolymer according to any one of claims 1 to 5, characterized in that it contains 0.5 to 20.0 mol% of the structural unit (C).

7. The multi-component polar group-containing olefin copolymer according to any one of claims 1 to 6, characterized in that the weight average molecular weight / number average molecular weight (Mw / Mn) measured by gel permeation chromatography (GPC) is 1.5 or more and 4.0 or less.

8. The multi-component polar group-containing olefin copolymer according to any one of claims 1 to 7, characterized in that the melting point (Tm, ° C.) observed by differential scanning calorimetry (DSC) and the total content [Y] (mol %) of the structural unit (B) and the structural unit (C) derived from the polar group-containing olefin monomer satisfy the following formula (I): 50<Tm<-3.74×[Y]+130...(I)

9. The multi-component polar group-containing olefin copolymer according to any one of claims 1 to 8, further comprising 20,000 μg / g or less of a transition metal element of Group 10 of the periodic table as measured by ICP-OES.

10. 10. The multi-component polar group-containing olefin copolymer according to claim 9, wherein the transition metal of Group 10 of the periodic table is nickel or palladium.

11. 2. The method for producing the multi-component polar group-containing olefin copolymer according to claim 1, wherein the multi-component polar group-containing olefin copolymer comprises: The method comprises a step of thermally decomposing at 80 to 350°C or a step of hydrolyzing with an acid catalyst a multi-component polar group-containing olefin copolymer, the multi-component polar group-containing olefin copolymer comprising at least one structural unit (B) selected from the group consisting of structural units (b-2) derived from polar group-containing olefin monomers represented by the following general formula (2) and the structural unit (C), and the multi-component polar group-containing olefin copolymer having 5 or less methyl branches per 1,000 carbon atoms: H ２ C=CH-X-COOT ２ ・・・(2) [In general formula (2), T ２ teeth, t-butyl group, Allyl group benzyl group -CR ａ R ｂ -O-R ｃ (where R ａ is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and R ｂ , R ｃ are each a hydrocarbon group having 1 to 10 carbon atoms, and R ｂ and R ｃ may be taken together to be a divalent hydrocarbon group having 1 to 8 carbon atoms in which one or more methylene groups may be replaced by an ether group or an ester group, and each group may have a hydrocarbon substituent having 1 to 4 carbon atoms) is a substituent selected from the group consisting of: X is a direct bond.

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