JP7128474B2 - Method for producing polar group-containing olefin copolymer - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for producing an olefinic copolymer containing a monomer having a polar group, particularly an olefinic copolymer containing a monomer having an acryl group or a styryl group.

Copolymers of ethylene, a non-polar monomer, and polar monomers such as acryl are widely known. As an example, ethylene-acrylic copolymers exhibit a higher affinity for polar paints or dyes than ethylene homopolymers and exhibit higher adhesion with polar adhesives.

Taking ethylene-acrylic copolymer as an example, the types of copolymers are alternating copolymers in which ethylene and acrylic are alternately connected, and graft copolymers in which acrylic polymer chains are connected to ethylene polymer chains like branches. There are coalescence, random copolymers in which acrylic monomers are randomly distributed in ethylene polymer chains, and block copolymers in which acrylic polymer chains are connected to the ends of ethylene polymer chains. Due to these differences, even if the same acrylic monomer is used, various copolymers exhibiting different physical properties can be obtained.

Radical polymerization and coordination polymerization using a transition metal catalyst are mainly used as polymerization methods for ethylene-acrylic copolymers.
As radical polymerization, free radical polymerization, organometallic mediated radical polymerization (OMRP), atom transfer radical polymerization (ATRP) and the like are mainly used.
In the case of free-radical polymerization, the reactivity of ethylene with respect to radical polymerization is much lower than that of acrylic monomers, so polymerization under high-temperature and high-pressure conditions is necessary. For example, in Patent Document 1, ethylene is 6.8 kg/h (about 242.4 mol/h), methyl acrylate is 0.8 kg/h (about 9.3 mol/h), and butyl acrylate is 1.3 kg/h. Polymerization was carried out under conditions of a pressure of 2180 kg/cm ² and a temperature of 165° C. while supplying at a rate of 32.8 wt % (67 mol %) of ethylene and 22.8 wt % of methyl acrylate. It is shown that a copolymer composed of 6% by weight (15 mol%) and 40.5% by weight (18 mol%) of butyl acrylate was obtained. It is generally known that such high temperature and high pressure conditions broaden the molecular weight distribution of polymers and form many branched structures. On the other hand, it is known that the ethylene content in the copolymer is low when not under high temperature and high pressure conditions. For example, in Non-Patent Document 1, using azobisisobutyronitrile, polymerization is performed under the conditions of ethylene 100 bar, methyl methacrylate 50 mL, and 50 ° C., and it is composed of ethylene 6 mol% and methyl methacrylate 94 mol%. It is shown that the obtained copolymer was obtained.

Complexes consisting of acetylacetone ligands and cobalt are mainly used in OMRP, and it is known that the ethylene content in the resulting copolymer is low, similar to free radical polymerization. For example, Non-Patent Document 2 discloses a method for producing a copolymer by substantially multistage polymerization using living polymerization. Specifically, using a complex composed of vinyl acetate oligomer, acetylacetone ligand and cobalt, polymerization was carried out under the conditions of ethylene 50 bar and acrylonitrile 40 mmol for 5 hours, then the pressure was released and then pressurized again with ethylene 10 bar. Polymerization was further carried out for 5 hours, and a copolymer composed of a random copolymer of 56 mol % ethylene and 44 mol % acrylonitrile and a random copolymer of 20 mol % ethylene and 80 mol % acrylonitrile was obtained. is shown.

ATRP mainly uses salts of monovalent copper and triamine-type ligands, and is known to have a low ethylene content in the resulting copolymers, similar to free radical polymerization and OMRP. For example, in Non-Patent Document 3, using copper (I) bromide, ethyl 2-bromopropionate, and pentamethyldiethylenetriamine, polymerization was carried out under the conditions of ethylene 900 psi and methyl acrylate 5.0 g, and ethylene 8.6. A random copolymer composed of 91.4 mol % acrylonitrile was obtained.

On the other hand, in coordination polymerization using transition metal catalysts, late transition metals having resistance to polar groups, especially group 10 and 11 metals, are used. As an example of using palladium among Group 10 metals, Patent Document 2 discloses an example in which a random copolymer of ethylene and acrylonitrile was obtained using a complex composed of a bisphosphine monooxide ligand and palladium. It is shown. Patent Document 3 shows an example in which a random copolymer of ethylene, methyl acrylate and acrylonitrile was obtained using a complex of palladium and a ligand having a dimenthylphosphine group and a sulfonate group in the molecule. ing. In addition, Non-Patent Document 4 describes an example in which a random copolymer of ethylene and methyl acrylate was obtained using a complex composed of palladium and a ligand having an N-heterocyclic carbene and a phosphine oxide group in the molecule. It is shown. In addition, Non-Patent Document 5 shows an example in which a random copolymer of ethylene and methyl methacrylate was obtained using a complex composed of an imidazoquinolinolatoylidene-type ligand and palladium. As an example of using nickel among Group 10 metals, Patent Document 4 discloses a complex of a salicylaldimine-type ligand, triphenylphosphine, and nickel, and a block of ethylene, butyl acrylate, and butyl methacrylate. Examples are given in which copolymers were obtained. However, in Non-Patent Document 6, when ethylene and methyl methacrylate were copolymerized under similar conditions, homopolymers of each of ethylene and acrylic were obtained, which contradicts the aforementioned results. there is

As an example in which a copper complex is mainly used as a Group 11 metal catalyst, Patent Document 5 discloses that a complex composed of a bisbenzimidazole-type ligand and copper and methylaluminoxane (MAO) are used to convert ethylene and methacrylic acid t An example is given in which a random copolymer with -butyl was obtained.

On the other hand, non-patent documents 7 to 11 show that a complex composed of a cyclopentadiene-type ligand and cobalt can cause coordination polymerization of ethylene, and non-patent document 12 shows that acrylonitrile and methyl methacrylate can be polymerized. It is shown.

U.S. Pat. No. 7,521,503 B2 Japanese Patent No. 6208657 Japanese Patent No. 6309206 Japanese Patent No. 5345693 U.S. Pat. No. 6,417,303 B1

Pure Appl. Chem. , 84, 2113 (2012) Nat. Chem. , 6, 179 (2014) J. Am. Chem. Soc. , 123, 12738 (2001) Chem. Commun. , 53, 2630 (2017) J. Am. Chem. Soc. , 140, 1876 (2018) J. Am. Chem. Soc. , 137, 14819 (2015) J. Am. Chem. Soc. , 107, 1443 (1985) J. Am. Chem. Soc. , 112, 5634 (1990) Organometallics, 11, 3920 (1991) Organometallics, 22, 4699 (2003) Inorg. Chem. Commun. , 9, 423 (2006) Polym. J. , 32,700 (2000)

As described above, there is a strong demand for copolymers such as combinations of polar monomers and non-polar monomers, and methods for producing such copolymers are being investigated. However, transition metal elements, such as palladium, which have been conventionally used in catalysts are expensive and ubiquitous on the earth, so they are not suitable for long-term stable supply. On the other hand, with cobalt complexes such as Non-Patent Documents 7 to 12, there is no report that, for example, a copolymer of ethylene and acrylic was obtained, and it was not clear whether copolymerization can be performed. It is known that the nickel complexes described in Patent Document 4 and Non-Patent Document 6 also have a plurality of contradictory results. Moreover, due to circumstances such as the need for a polymerization reaction in a multi-stage reaction, complicated devices and methods are required at the time of designing the polymerization apparatus and method, and in this respect, only methods that result in increased costs can be taken. In some cases. Thus, there is still a strong demand for construction of inexpensive and reliable polymerization systems. Furthermore, conventionally known methods are not preferable from the viewpoint of maintaining the properties of polyolefins due to the low ethylene content in the copolymer, and are still limited in terms of variations in the physical properties of the resulting copolymer. stays at something.

The subject of the present invention is a copolymer that can be synthesized in the coexistence of nonpolar and polar monomers, for example, a copolymer that can be synthesized in the coexistence of an olefin and a monomer having an acrylic group or a styryl group and has a high content of a nonpolar monomer (ethylene). An object of the present invention is to provide a method for producing a copolymer.

The present inventors have made intensive studies to solve the above problems, and as a result, have found that the problems can be solved by using a specific metal complex as a catalyst. Specifically, the present inventors have found that a copolymer with a high ethylene content can be provided by copolymerizing an acryl group- or styryl group-containing monomer with ethylene, and have completed the present invention.

（式中、Ｍは周期律表第９族の元素を表し、ＸはＮ、ＰまたはＡｓを表し、Ｌは中性の電子供与性配位子を表し、Ａ^－はカチオン性有機金属化合物の対イオンを表し、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^７、Ｒ^８及びＲ^９はそれぞれ独立して、水素原子；置換されていてもよい炭素数１～３０のアルキル基、脂環式基、アルコキシ基、アリール基もしくはアリールオキシ基；またはそれぞれ独立して炭素数１～３０の炭化水素で１つ以上の水素原子が置換されたアミノ基もしくはシリル基を表し、Ｒ^１～Ｒ^５のうちの２つは連結して環構造を形成していてもよく、Ｒ^１～Ｒ^５の中の１つとＲ^７～Ｒ^９の中の１つとは、一緒になってケイ素原子を骨格に有していてもよい炭素数１～３０の２価の炭化水素基を形成していてもよく、Ｒ^７とＲ^８は連結してヘテロ環構造を形成していてもよく、Ｒ^７、Ｒ^８及びＲ^９は、Ｘと一緒になって芳香族ヘテロ環構造を形成してもよく、Ｒ^６とＬは結合して環構造を形成してもよい。）

（式中、Ｍ、Ｌ、Ａ^－、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^７及びＲ^８は、前記一般式（Ｃ１）で定義されたとおりであり、ＹはＯ、ＳまたはＳｅを示し、Ｒ^１～Ｒ^５の中の１つとＲ^７またはＲ^８は一緒になってケイ素原子を骨格に有していてもよい炭素数１～３０の２価の炭化水素基を形成していてもよく、Ｒ^７及びＲ^８は、Ｙと一緒になってヘテロ環構造を形成してもよく、Ｒ^６とＬは結合して環構造を形成してもよい。）

（式中、Ｒ^１０は、水素原子または炭素数１～３の炭化水素基を表し、Ｒ^１１は－ＣＯＯＲ^１２（ここでＲ^１２は炭素原子数１～２０の炭化水素基を表す）、－ＣＯＮ（－Ｒ^１２’）_２（ここでＲ^１２’は水素原子または炭素原子数１～２０の炭化水素基を表す。）、シアノ基、または置換されていてもよいアリール基を表し、２つのＲ^１２’は同じでも異なっていてもよい） That is, according to the first aspect of the present invention, there is provided a method for producing a polar group-containing olefin copolymer, wherein a catalyst containing a metal complex represented by the following general formula (C1) or (C2) is used to produce a carbon- A method for producing a polar group-containing olefinic copolymer, which comprises copolymerizing a linear or branched hydrocarbon having one carbon double bond with a monomer represented by the following general formula (1): is provided.

(Wherein, M represents an element of Group 9 of the periodic table, X represents N, P or As, L represents a neutral electron-donating ligand, A ^- of a cationic organometallic compound represents a counter ion, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ are each independently a hydrogen atom; 30 alkyl groups, alicyclic groups, alkoxy groups, aryl groups or aryloxy groups; and two of R ¹ to R ⁵ may be linked to form a ring structure, and one of R ¹ to R ⁵ and one of R ⁷ to R ⁹ are together may form a divalent hydrocarbon group having 1 to 30 carbon atoms which may have a silicon atom in the skeleton, and R ⁷ and R ⁸ are linked to form a heterocyclic structure. R ⁷ , R ⁸ and R ⁹ may combine with X to form an aromatic heterocyclic structure, and R ⁶ and L may combine to form a ring structure.)

(Wherein, M, L, A ⁻ , R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are as defined in the general formula (C1); Y represents O, S or Se, and one of R ¹ to R ⁵ and R ⁷ or R ⁸ together are a divalent may form a hydrocarbon group, R ⁷ and R ⁸ may combine with Y to form a heterocyclic structure, and R ⁶ and L may combine to form a ring structure .)

(wherein R ¹⁰ represents a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms, R ¹¹ represents -COOR ¹² (wherein R ¹² represents a hydrocarbon group having 1 to 20 carbon atoms), - CON(—R ^12′ ) ₂ (wherein R ^12′ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms), a cyano group, or an optionally substituted aryl group, and two R ^12′ may be the same or different)

Palladium, which has hitherto been used as a polymerization catalyst, is expensive. On the other hand, the metal complexes of the present invention have cyclopentadiene-based ligands that are easy to handle and are consequently inexpensive. For these reasons, the method of the present invention is suitable for industrialization and useful in the field of polymer production. In addition, the method of the present invention can easily obtain a copolymer having a high non-polar monomer content, which normally requires severe conditions such as high temperature and high pressure.

1 shows the size exclusion chromatography measurement results of ethylene/methyl acrylate copolymer 1 obtained in Example 1. FIG. 1 is a ¹ H-NMR spectrum of ethylene/methyl acrylate copolymer 1 obtained in Example 1. FIG. 1 is a ¹³ C-NMR spectrum of ethylene/methyl acrylate copolymer 1 obtained in Example 1. FIG. 4 is an enlarged view near 50.8 ppm in FIG. 3. FIG. FIG. 4 is an enlarged view of the 26-40 ppm range in FIG. 3;

In one embodiment of the present invention, a catalyst containing a transition metal complex having a transition metal belonging to Group 9 of the periodic table, represented by general formula (C1) or (C2), converts carbon-carbon double bonds to 1 A method for producing a polar group-containing olefinic copolymer, characterized by copolymerizing a straight-chain or branched-chain hydrocarbon or alicyclic hydrocarbon having be. Constituent monomers of the polymer, catalyst components, production methods, and the like will be described in detail below.

In the following description, the term "polymerization" generically refers to homopolymerization of one type of monomer and copolymerization of multiple types of monomers, and in the present specification, copolymerization is simply referred to as "polymerization". I have something to do. In addition, although the present invention relates to polymers, the structures of polymers themselves cannot generally be uniquely determined by chemical formulas or the like. Therefore, in this specification, when describing a polymer, the polymer is described using the method for producing the polymer, if necessary.

1. Constituent Monomers of the Polymer Monomers to be subjected to polymerization reaction in the present invention are preferably linear or branched hydrocarbons or alicyclic hydrocarbons having one carbon-carbon double bond and the following general formula These are two types of monomers represented by (1). As one of the monomers to be copolymerized, "a straight-chain or branched-chain hydrocarbon or alicyclic hydrocarbon having one carbon-carbon double bond", an organic Compounds are applicable, and α-olefins are particularly exemplified. α-Olefins are molecules with a carbon-carbon double bond at the end of the carbon chain. The structure of the α-olefin preferably has 2 to 20 carbon atoms, and may have unsaturated bonds other than branches, rings and/or terminals. If the number of carbon atoms is more than 20, sufficient polymerization activity may not be exhibited. Therefore, α-olefins having 2 to 10 carbon atoms are more preferred. More preferred α-olefins include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 3-methyl-1-butene, 4-methyl-1-pentene and vinylcyclohexene. is mentioned.

Examples of "linear or branched hydrocarbons or alicyclic hydrocarbons having one carbon-carbon double bond" other than α-olefins include alkenes having a carbon-carbon double bond other than at the terminal, Cycloalkenes are mentioned. Preferred examples thereof include 2-butene, 2-pentene, 2-hexene, cyclopentene, cyclohexene, cycloheptene, norbornene, norbornadiene and the like. In addition, these monomers may use a single component, and may use multiple types together.

Another component to be polymerized in the present invention is a polar group-containing monomer represented by the general formula: CH ₂ =C(R ¹⁰ )(R ¹¹ ), preferably a (meth)acrylic acid ester. Here, R ¹⁰ represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, R ¹¹ represents —COOR ¹² (wherein R ¹² represents a hydrocarbon group having 1 to 20 carbon atoms), — CON(-R ^12' ) ₂ (where each R ^12' independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms), a cyano group, or an optionally substituted aryl group; . R ¹⁰ is preferably a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms, since more sufficient polymerization activity can be expressed. More preferably, R ¹⁰ is a hydrogen atom or a methyl group. R ¹¹ is not particularly limited as long as it is the above-described substituent, but it is preferably —COOR ¹² or an aryl group because there are a wide range of uses when it is used as a copolymer. At this time, when the number of carbon atoms in R ¹² exceeds 20, the polymerization activity tends to decrease. Therefore, R ¹² is preferably a hydrocarbon group having 1 to 12 carbon atoms, more preferably a hydrocarbon group having 1 to 8 carbon atoms.
The group R ¹² is preferably composed of carbon and hydrogen, and the group R ¹² may contain heteroatoms such as oxygen, sulfur, selenium, phosphorus, nitrogen, silicon, fluorine, boron, and the like. good too. Among these heteroatoms, oxygen, silicon and fluorine are preferred, and oxygen is more preferred. The preferred range and examples of R ^12′ when it is not a hydrogen atom are also the same as for R ¹² .

More preferred examples of the monomer represented by formula (1) include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, and (meth)acryl n-butyl acid, isobutyl (meth)acrylate, t-butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, cyclohexyl (meth)acrylate, octyl (meth)acrylate, ( 2-ethylhexyl meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, dodecyl (meth)acrylate, phenyl (meth)acrylate, toluyl (meth)acrylate, benzyl (meth)acrylate, Hydroxyethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, 2-aminoethyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, (meth)acrylate 3-methoxypropyl acrylate, glycidyl (meth) acrylate, trifluoromethyl (meth) acrylate, 3,3,3-trifluoropropyl (meth) acrylate, perfluoroethyl (meth) acrylate, ( meth)acrylamide, (meth)acryldimethylamide, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, acrylonitrile, styrene, vinylanisole and the like. More preferably, methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, t-butyl methacrylate, At least one selected from acrylonitrile, styrene, and vinylanisole. A single type of these monomers may be used, or a plurality of types may be used in combination.

The types of the above monomers can be appropriately selected according to the physical properties required for the resulting polymer. Optionally, it is also possible to copolymerize a composition of monomers consisting of two or more types of linear or branched hydrocarbons or alicyclic hydrocarbons with one carbon-carbon double bond. It is also possible to copolymerize a composition comprising two or more (meth)acrylic acid monomers. The amount of the monomers to be blended and the amount ratio between the monomers can be appropriately set according to the physical properties required for the resulting copolymer.

（各式における置換基等の定義は、先に述べたとおりである。なお、Ｒ^１～Ｒ^５を有する環は後述のとおり縮合環であることもできるが、当該環を指して単に「シクロペンタジエニル基」と称することがある。） 2. Metal Complex The catalyst used in the method of the present invention contains a transition metal complex represented by (C1) or (C2) below.

(The definition of substituents and the like in each formula is as described above. The ring having R ¹ to R ⁵ can be a condensed ring as described later, but the ring is simply referred to as “cyclo It is sometimes referred to as a "pentadienyl group".)

In the catalyst composition of the present invention, M in the above formula (C1) or (C2) is a transition metal belonging to Group 9 of the periodic table and is cobalt, rhodium or iridium, preferably cobalt.

Here, the valence of the central metal M in the metal complex represented by general formula (C1) or (C2) means the formal oxidation number used in organometallic chemistry. In other words, it refers to the number of charges remaining on an atom of an element when the electron pairs in the bond involved in that element are assigned to an element with high electronegativity. For example, in general formula (C1) or (C2), the valence of M is +3. Because, based on the definitions above, in these bonds the electron pairs are assigned to halogens, heteroatoms, and carbon, which are more electronegative than the Group 9 metals, and the charges are assigned to X or Y, as described below. element of group 15 or 16, the ligand denoted by L is 0, R ⁶ and the cyclopentadienyl group are −1, the complex is electrically +1 valent overall, and thus remains on the metal. This is because the charge is +3.

L in Formula (C1) or (C2) represents a neutral electron-donating ligand. A neutral electron-donating ligand is, for example, a ligand that is electrically neutral and capable of forming a coordinate bond by coordinating an unpaired electron to the central metal M. Molecules with paired electrons such as nitrogen, phosphorus, arsenic, oxygen, sulfur, and selenium. Yet another example is a molecule such as ethylene that forms a π-dative bond by donating a π-electron. Examples of L that can be used include molecules represented by XR ⁷ R ⁸ R ⁹ or YR ⁷ R ⁸ described below as ligands, as well as acetonitrile, isonitrile, carbon monoxide, ethylene, tetrahydrofuran, and the like. can also be used. Also, L may form a ring structure together with ^R6 as described later.

X in formula (C1) represents N, P or As. That is, the metal complex represented by formula (C1) has one group 15 element as a neutral ligand. X is preferably N or P because of the wide variety of compounds that can be used as ligands.

Y in formula (C2) represents O, S or Se. That is, the metal complex represented by formula (C2) has one group 16 element as a neutral ligand. Y is preferably O or S because of the wide variety of compounds that can be used as ligands.

R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , and R ⁹ in formula (C1) or (C2) are each independently a hydrogen atom; an alkyl group, alicyclic group, alkoxy group, aryl group or aryloxy group having 1 to 30 carbon atoms; or amino in which one or more hydrogen atoms are each independently substituted with a hydrocarbon having 1 to 30 carbon atoms group or a silyl group.

As used herein, "optionally substituted" means that one or more hydrogen atoms of the group may be replaced with any substituent. Examples of substituents include halogen, alkyl groups (preferably having 1 to 6 carbon atoms, more preferably methyl, ethyl, isopropyl and t-butyl), alkenyl groups (preferably having 2 to 6 carbon atoms), alkynyl groups (preferably has 2 to 6 carbon atoms), cycloalkyl group, alkoxy group, aryloxy group, ether group, thiol group, sulfide group, aryl group, heterocycle, amino group, amido group, alkylcarbonyl group, arylcarbonyl group, ketocarbonyl group , a carboxy group, a sulfonyl group, a sulfonic acid group, and the like. The position to be substituted is not particularly limited, and any number of substitutions may be made at any position.

Specific examples of R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ include hydride group (hydrogen atom), methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, n-hexyl group, n-octyl group, n-decyl group, n-dodecyl group, trifluoromethyl group, cyclopentyl group, cyclohexyl group, methoxy group, ethoxy group, t-butoxy group, cyclohexyloxy group, phenyl group, p-methylphenyl group, benzyl group, phenoxy group, dimethylamino group, diethylamino group, diphenylamino group, trimethylsilyl group, triethylsilyl group, triphenylsilyl group, etc. can be done.

R ¹ , R ² , R ³ , R ⁴ and R ⁵ bonded to the cyclopentadienyl group are particularly preferably a hydrogen atom, a methyl group and an ethyl group. R ⁶ bound to the metal M is preferably a group such as a methyl group, an ethyl group, or an n-butyl group that does not become too bulky around the metal center. Although it depends on the method of preparing the complex, a methyl group is particularly preferable because the one bonded to the Group 9 element used as the raw material can be used as it is. Preferred examples of R ⁷ , R ⁸ , and R ⁹ bonded to X or Y include groups corresponding to those included in the examples described later.

In (C1), one of R ¹ to R ⁵ and one of R ⁷ to R ⁹ are together a divalent C 1-30 divalent A hydrocarbon group may be formed. In this case, the cyclopentadienyl group and the neutral ligand having X are linked to form a bidentate ligand. Therefore, since it tends to function as a bidentate ligand, the divalent hydrocarbon group forms a chain with one to three atoms and connects the cyclopentadienyl ring and X. It is preferable to Examples include methylene groups, ethylene groups, --CH ₂ --Si(Me) ₂ --CH ₂ --, o-phenylene groups, and the like. Similarly, in (C2), one of R ¹ to R ⁵ and R ⁷ or R ⁸ together are divalent carbonized carbon atoms having 1 to 30 carbon atoms which may have a silicon atom in the skeleton. A hydrogen group may be formed.

Two groups of R ¹ to R ⁵ in formula (C1) or (C2) may be linked to form a ring structure. When having such a structure, the cyclopentadienyl group has a condensed ring structure. Two or more condensed rings may be present. That is, it can have a structure in which three rings are condensed.

Preferable examples of R ⁶ in formula (C1) or (C2) are as described above, and R ⁶ binds to neutral ligand L to form a ring structure containing metal M. may _In this case _, a _5- to _{7 -} membered ring is likely to form a ring structure. A structure such as a structure derived from (C ₆ H ₅ NHC(=O)CH ₃ ), in which L and R ⁶ as a whole forms a chain of 4 to 6 atoms, is preferred.

R ⁷ , R ⁸ and R ⁹ in formula (C1) are as defined above, R ⁷ and R ⁸ may be linked to form a heterocyclic structure, and R ⁷ , R ⁸ and ^R9 may form an aromatic heterocyclic structure together with X. That is, if a Group 15 element can be used as a neutral ligand, the portion represented by XR ⁷ R ⁸ R ⁹ in (C1) can have a heterocyclic compound as a ligand. Examples of those that can be utilized include piperidine, pyrimidine, morpholine, pyridine, imidazole, benzimidazole, and the like.

Examples of ligands used as the moiety represented by XR ⁷ R ⁸ R ⁹ in (C1) include trimethylamine, triethylamine, dimethylphenylamine, dimethyl t-butylamine, (cyclohexyl)(ethyl)(t-butyl) Amine, (butyl)(methyl)(norbornyl)amine, triphenylamine, N-methylmorpholine, pyridine, piperidine, imidazole, N-methylimidazole, benzimidazole, pyrrole, pyrazole, oxazole, triphenylphosphine, tri(t- butyl)phosphine, tri(p-tolyl)phosphine, dimethyl t-butylphosphine, (2-fluorophenyl)(4-methoxyphenyl)methylphosphine, 2-{bis(2-isopropylphenyl)phosphino}benzenesulfonic acid, 2 -{bis(2-t-butylphenyl)phosphino}benzenesulfonic acid, 2-{bis(2-methoxyphenyl)phosphino}benzenesulfonic acid, and the like, but are not limited thereto.

As with R ⁷ and R ⁸ in (C1), R ⁷ and R ⁸ in (C2) may combine with Y to form a heterocyclic structure. Examples of such structures include oxane, morpholine, tetrahydrofuran, oxazoline, coumarin, furan, thiophene, and the like.

Examples of ligands used as the moiety represented by YR ⁷ R ⁸ in (C2) include t-butyl (cyclohexyl) ether, t-butyl methyl ether, oxane, dioxane, methylphenyl sulfide, dimethyl sulfide, butyl Methylsulfide, N-methylmorpholine, morpholine, tetrahydrofuran, oxazoline, coumarin, furan, thiophene and the like.

A 1 ⁻ in formula (C1) or (C2) represents a counter ion of the cationic organometallic compound. A ⁻ Any chemical species having an overall charge of −1 can be used, such as an ion of an element such as a halogen, or a molecular species such as a borate. Examples of A ⁻ include fluoride ion, chloride ion, bromide ion, iodide ion, tetrafluoroborate, tetramethylborate, tetraphenylborate, tetrakis(perfluorophenyl)borate, tetrakis((3,5-bistri fluoromethyl)phenyl)borate, hexafluorophosphate, hexafluoroantimonate and the like.

Specific examples of the transition metal complex represented by (C1) or (C2) include the following complexes. However, these are examples, and the complex in the method of the present invention is not limited to these specific examples.

The transition metal complex represented by (C1) or (C2) used in the method of the present invention can be prepared by a known method. For example, it can be synthesized according to Organometallics 2003, 22(23), 4699-4704. It can be obtained by reacting with a nucleus. Alternatively, a cyclopentadienyl compound having a desired substituent and an appropriate ligand are reacted with octacarbonyl dicobalt and 1,3-cyclohexadiene, and then the resulting monovalent cobalt complex is oxidized with iodine. , it is also possible to obtain the desired cobalt complexes. A metal complex used in the method of the present invention can be prepared by a person skilled in the art making appropriate modifications such as changing raw materials based on a known complex preparation method.

3. Cocatalyst In the method of the present invention, a cocatalyst may be added in addition to the transition metal complex represented by (C1) or (C2) above. Examples of co-catalysts include organometallic compounds containing Group 1, 2 or 13 elements of the periodic table. In particular, a compound represented by the following general formula (2), a compound represented by the general formula (3), or an organoaluminumoxy compound can be mentioned. A plurality of types of these compounds may be contained in the catalyst composition.

The compound represented by general formula (2) is a boron or aluminum compound represented by QR ¹³ R ¹⁴ R ¹⁵ . (Wherein, Q represents boron (B) or aluminum (Al); R ¹³ , R ¹⁴ and R ¹⁵ are each independently a hydrogen atom; an optionally substituted alkyl group having 1 to 30 carbon atoms; An alicyclic group, an alkoxy group, an aryl group or an aryloxy group; or each independently represents an amino group or a silyl group in which one or more hydrogen atoms are substituted with a hydrocarbon having 1 to 30 carbon atoms.)
As R ¹³ to R ¹⁵ , the examples described in the explanation of R ¹ and the like are applicable, but from the viewpoint of the preparation and availability of the compound, a group belonging to hydrocarbon such as an alkyl group, an aryl group, or a tri- It is preferably an alkyl group or an aryl group substituted with a halogen (especially fluorine) such as a fluoromethyl group or a perfluorophenyl group.

Examples of compounds represented by general formula (2) include trimethylborane, trimethoxyborane, perfluoromethylborane, triphenylborane, tris(perfluorophenyl)borane, triphenoxyborane, tris(dimethylamino)borane, tris( diphenylamino)borane, trimethylaluminum, triethylaluminum, tri(n-propyl)aluminum, tri(n-butyl)aluminum, triisobutylaluminum, tri(n-hexyl)aluminum, tri(n-octyl)aluminum, tri(n) -decyl)aluminum, diethylaluminum hydride, diethylaluminum ethoxide, diethylaluminum dimethylamide, diisobutylaluminum hydride and the like, but are not limited thereto.

The compound represented by the general formula (3) is a salt of boron or aluminum with a carbocation represented by [CR ¹⁶ R ¹⁷ R ¹⁸ ][QR ¹⁹ R ²⁰ R ²¹ R ²² ]. (Wherein, Q is as defined in the general formula (2), R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ and R ²² are each independently R ¹³ and synonymous.)
As R ¹⁶ to R ²² , the examples described in the explanation of R ¹ and the like are applicable, but from the viewpoint of ease of preparation and availability of compounds, it is preferred that they are groups belonging to hydrocarbons such as alkyl groups and aryl groups. is preferable, and a bulky hydrocarbon group such as a t-butyl group or an aryl group is more preferable because it is easy to obtain a carbocation.

Examples of compounds represented by general formula (3) include trityltetramethylborate, trityltetrakis(perfluoromethyl)borate, trityltetraphenylborate, trityltetrakis(perfluorophenyl)borate, trityltetrakis(di(trifluoromethyl) phenyl)borate, and the like, but are not limited thereto.

As the compound represented by the general formula (2) or (3), a commercially available one can be used, or it can be obtained by appropriately modifying a known method depending on the substituents of the compound. can.

In addition to the compound represented by the general formula (2) or (3), an organoaluminumoxy compound can also be added to the catalyst composition in the method of the present invention. Examples of organic aluminum compounds include methylaluminoxane (MAO) and modified methylaluminoxane (MMAO), and commercially available products can be used. MMAO is preferred because it is readily available and easy to handle. Commercially available MAO and MMAO can be used, and there are no restrictions on the grade or the like.

In addition to the compounds having a group 13 element exemplified above, Group 1 metal-containing compounds such as alkyllithium such as methyllithium and n-butyllithium, Group 2 metal-containing compounds such as Grignard reagents, etc., as promoters Conventionally known organometallic compounds can also be used as promoters. Commercially available products can also be used for these compounds, and there is no restriction by grade or the like.

These cocatalysts can be used under the same conditions as the metal complex represented by (C1) or (C2) above, but they are preferably used in an inert gas atmosphere while avoiding oxygen and moisture. A person skilled in the art can appropriately set the amount to be used when it is added.

4. Polymerization Reaction In the process of the present invention, a catalyst composition containing the compounds described above can be used as a catalyst component for copolymerization. The metal complex represented by general formula (C1) or (C2) may be isolated or supported on a carrier. Such loading may be carried out in the presence or absence of these monomers in the reactor used for the polymerization of α-olefins or the copolymerization of α-olefins and (meth)acrylic acid esters, and the reaction You may carry out in a container different from a vessel.

Any carrier can be used as long as it does not impair the gist of the present invention. In general, inorganic oxides and polymeric supports are suitable for use. Specific examples include SiO ₂ , Al ₂ O ₃ , MgO, ZrO ₂ , TiO ₂ , B ₂ O ₃ , CaO, ZnO, BaO, ThO ₂ and mixtures thereof, and SiO ₂ —Al ₂ O ₃ , SiO ₂ —V ₂ O ₅ , SiO ₂ —TiO ₂ , SiO ₂ —MgO, SiO ₂ —Cr ₂ O ₃ can also be used, inorganic silicates, polyethylene supports, polypropylene supports, Polystyrene carriers, polyacrylic acid carriers, polymethacrylic acid carriers, polyacrylic acid ester carriers, polyester carriers, polyamide carriers, polyimide carriers and the like can be used. There are no particular restrictions on the particle size, particle size distribution, pore volume, specific surface area, etc. of these carriers, and any carrier can be used.

As the inorganic silicate, clay, clay mineral, zeolite, diatomaceous earth, etc. can be used. These may be synthetic products or naturally occurring minerals. Specific examples of clays and clay minerals include allophane groups such as allophane; kaolin groups such as dickite, nacrite, kaolinite and anoxite; halloysite groups such as metahalloysite and halloysite; Stone family, smectites such as montmorillonite, sauconite, beidellite, nontronite, saponite, and hectorite; vermiculite minerals such as vermiculite; Clay, gayrome clay, hisingerite, pyrophyllite, ryokudei stone group and the like. These may form a mixed layer. Artificial synthetics include synthetic mica, synthetic hectorite, synthetic saponite, synthetic teniolite, and the like.

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

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

In the method of the present invention, the polymerization reaction can be carried out in the presence or absence of known additives in addition to the co-catalyst. As the additive, an additive having an effect of stabilizing the produced copolymer is preferable. Examples of preferred additives include quinone derivatives and hindered phenol derivatives.
Specifically, monomethyl ether hydroquinone, 2,6-di-t-butyl 4-methylphenol (BHT), reaction products of trimethylaluminum and BHT, reaction products of tetravalent titanium alkoxide and BHT, etc. is available.
Inorganic and/or organic fillers may also be used as additives, and polymerization may be carried out in the presence of these fillers or with the addition of ionic liquids.

Preferred additives in the present invention include Lewis bases. By selecting a suitable Lewis base, the activity, molecular weight and copolymerizability of the acrylate can be improved. The amount of the Lewis base is 0.0001 equivalent to 1000 equivalents, preferably 0.1 equivalents to 100 equivalents, more preferably 0.3 equivalents to the transition metal M in the catalyst component present in the polymerization system. 30 equivalents. The method of adding the Lewis base to the polymerization system is not particularly limited, and any method can be used. For example, it may be added by mixing with the catalyst component of the present invention, may be added by mixing with the monomer, or may be added to the polymerization system independently of the catalyst component and the monomer. Moreover, you may use several Lewis bases together. Moreover, the same Lewis base as L1 according to the present invention may be used, or a different one may be used.

Lewis bases include aromatic amines, aliphatic amines, alkyl ethers, aryl ethers, alkylaryl ethers, cyclic ethers, alkylnitriles, arylnitriles, alcohols, amides, and aliphatic esters. , aromatic esters, phosphates, phosphites, thiophenes, thianthrenes, thiazoles, oxazoles, morpholines, and cyclic unsaturated hydrocarbons.
Among these, particularly preferred Lewis bases are aromatic amines, aliphatic amines, cyclic ethers, aliphatic esters and aromatic esters. Among them, preferred Lewis bases are pyridine derivatives, pyrimidine derivatives, piperidine derivatives, imidazole derivatives, aniline derivatives, piperidine derivatives, triazine derivatives, pyrrole derivatives, furan derivatives.

Specific Lewis base compounds include pyridine, pentafluoropyridine, 2,6-lutidine, 2,4-lutidine, 3,5-lutidine, pyrimidine, N,N-dimethylaminopyridine, N-methylimidazole, 2, 2'-bipyridine, aniline, piperidine, 1,3,5-triazine, 2,4,6-tris(trifluoromethyl)-1,3,5-triazine, 2,4,6-tris(2-pyridyl) -s-triazine, quinoline, 8-methylquinoline, phenazine, 1,10-phenanthroline, N-methylpyrrole, 1,8-diazabicyclo-[5.4.0]-undec-7-ene, 1,4 -diazabicyclo-[2,2,2]-octane, triethylamine, benzonitrile, picoline, triphenylamine, N-methyl-2-pyrrolidone, 4-methylmorpholine, benzoxazole, benzothiazole, furan, 2,5- dimethylfuran, dibenzofuran, xanthene, 1,4-dioxane, 1,3,5-trioxane, dibenzothiophene, thianthrene, triphenylphosphonium cyclopentadienide, triphenylphosphite, triphenylphosphate, tripyrrolidinophos fins and the like.

In the present invention, there are no particular restrictions on the polymerization method. Solution polymerization in which all the produced polymer dissolves in the medium, slurry polymerization in which at least a part of the produced polymer is a slurry in the medium, bulk polymerization in which the liquefied monomer itself is used as a medium, and gas phase polymerization conducted in the vaporized monomer Polymerization or high-pressure ionic polymerization in which at least part of the polymer produced is dissolved in a monomer liquefied at high temperature and high pressure is preferably used. Either batch polymerization or semi-batch polymerization may be used. As an environment for the polymerization reaction, it is preferable to use an inert gas atmosphere such as a nitrogen atmosphere. The transition metal complex represented by (C1) or (C2) is not particularly limited in terms of usage conditions as long as it is under general polymerization conditions. The amount of the transition metal complex represented by (C1) or (C2) to be used is not particularly limited as long as it is within a range suitable for use as a catalyst, and can be appropriately set by those skilled in the art.

In the polymerization reaction of the present invention, when a monomer that is preferably polymerized in a liquid phase is used, a hydrocarbon solvent such as n-butane, isobutane, n-hexane, n-heptane, toluene, xylene, cyclohexane, methylcyclohexane, or a liquefied Liquids such as α-olefins, halogenated hydrocarbon solvents such as chlorobenzene and 1,2-dichlorobenzene, diethyl ether, ethylene glycol dimethyl ether, tetrahydrofuran, dioxane, ethyl acetate, methyl benzoate, acetone, methyl ethyl ketone, formamide, acetonitrile , in the presence or absence of a polar solvent such as methanol, isopropyl alcohol, ethylene glycol and the like. Mixtures of the liquid compounds described herein may also be used as solvents. Liquefied α-olefins can also be used as monomers for bulk polymerization. Furthermore, ionic liquids can also be used as solvents. In order to obtain high polymerization activity and high molecular weight, the above-described hydrocarbon solvents and ionic liquids are more preferable.

Unreacted monomers and medium may be separated from the produced copolymer and recycled for use. Upon recycling, these monomers and media may be reused after purification, or may be reused without purification. Conventionally known methods can be used to separate the produced copolymer from unreacted monomers and medium. For example, methods such as filtration, centrifugation, solvent extraction, and reprecipitation using a poor solvent can be used.

There are no particular restrictions on the polymerization temperature, polymerization pressure and polymerization time, but usually the optimum settings can be made from the following ranges in consideration of productivity and process capability. That is, the polymerization temperature is usually -20°C to 290°C, preferably 0°C to 250°C, more preferably 0°C to 200°C, still more preferably 10°C to 150°C, and particularly preferably 20°C to 100°C. . The copolymerization pressure is 0.1 MPa to 300 MPa, preferably 0.3 MPa to 200 MPa, more preferably 0.5 MPa to 150 MPa, still more preferably 1.0 MPa to 100 MPa, particularly preferably 1.3 MPa to 50 MPa. The polymerization time can be selected from the range of 0.1 minutes to 100 hours, preferably 0.5 minutes to 70 hours, more preferably 1 minute to 60 hours.

In the present invention, polymerization is generally carried out under an inert gas atmosphere. For example, nitrogen or argon atmosphere can be used, and nitrogen atmosphere is preferably used. In addition, a small amount of oxygen or air may be mixed. However, in the case of using a monomer such as ethylene which is gaseous at room temperature, the polymerization can be carried out after filling the reaction system with ethylene.
There are no particular restrictions on the supply of the catalyst and monomers to the polymerization reactor, and various supply methods can be adopted depending on the purpose. For example, in the case of batch polymerization, it is possible to adopt a method in which a predetermined amount of monomer is supplied to a polymerization reactor in advance, and a catalyst is supplied there. In this case, additional monomer or additional catalyst may be fed to the polymerization reactor.

Regarding the control of the composition of the copolymer, a method of supplying a plurality of monomers to a reactor and changing the supply ratio thereof can generally be used. In addition, there are a method of controlling the copolymerization composition by utilizing the difference in the monomer reactivity ratio due to the difference in the structure of the catalyst, and a method of controlling the copolymerization composition by utilizing the polymerization temperature dependence of the monomer reactivity ratio. . In the method of the present invention, block copolymers can be obtained in which the content of non-polar monomers (ethylene) is particularly high relative to that of polar monomers. The amount ratio (molar ratio) of the total nonpolar monomer species in the total copolymer is preferably 70% or more, more preferably 80% or more, and particularly 90% or more. preferable. Although the upper limit varies depending on the physical properties to be imparted to the copolymer and can be adjusted as appropriate, it is preferably 99.99% or less, more preferably 99.95% or less, and 99.9%. 9% or less is particularly preferred. By adjusting the content within this range, it is possible to impart affinity and adhesiveness to paints without greatly impairing the inherent properties of polyolefin such as heat resistance, and to control the physical properties.

Conventionally known methods can be used to control the molecular weight of the polymer. That is, a method of controlling the polymerization temperature to control the molecular weight, a method of controlling the monomer concentration to control the molecular weight, a method of using a chain transfer agent to control the molecular weight, and a method of controlling the ligand structure in the transition metal complex to control the molecular weight. and the like. When using a chain transfer agent, a conventionally known chain transfer agent can be used. For example, hydrogen, metal alkyl, and the like can be used.

The method of the present invention is industrially very important in terms of cost reduction, etc., because it is possible to obtain a copolymer with an easy-to-handle catalyst. In addition, the copolymer obtained by the method of the present invention exhibits good paintability, printability, antistatic properties, inorganic filler dispersibility, adhesion to other resins, It can be used for various purposes because it exhibits compatibilizing ability with For example, it can be used as films, sheets, adhesive resins, binders, compatibilizers, waxes, and the like.

EXAMPLES 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.

[Method for analyzing structure of copolymer]
The structures of the copolymers obtained in Examples were determined by ¹ H-NMR and ¹³ C-NMR analyses, using Ascend 500 manufactured by BRUKER. NMR measurements were carried out at 120° C. using 1,1,2,2-tetrachloroethane-d2 as a solvent. A portion of the ¹³ C-NMR was measured using chromium (III) acetylacetonate as the relaxation reagent and the reverse gated decoupling method (90° pulse of 9.0 μs, spectral width: 31 kHz, relaxation time: 10 seconds, acquisition time: 10 seconds, the number of FID integration times: 5,000 to 10,000), and quantitative analysis was performed.

Representative examples of structures in polymers that can be identified by NMR spectroscopy are shown in the following figures.

The branched structure can be determined from the ¹³ C-NMR spectrum of tertiary carbon atoms. For example, the chemical shift value of a tertiary carbon atom (corresponding to z in the above figure) derived from an alkyl group branched structure having 2 or more carbon atoms appears within the range of 38.2 to 39.0 ppm. (Reference: Macromolecules 1999, 32, 1620.).
Similarly, the terminal structure can be analyzed by ¹³ C-NMR or ¹ H-NMR. For example, in the case of a carbon-carbon double bond structure, the ¹³ C-NMR spectrum appears at 114 ppm (corresponding to f in the above figure) and 139 ppm (corresponding to e in the above figure), and 13.6 ppm (corresponding to e in the above figure). It can be distinguished from the carbon-carbon single bond structure that appears in (corresponding to c in the above) (Reference: Chem. Commun., 53, 2630 (2017) (Non-Patent Document 4)).

The number-average molecular weight and weight-average molecular weight were measured using a high-temperature GPC apparatus manufactured by Tosoh Corporation equipped with a TSKgel GMHHR-H(S)HT column (2 columns of 7.8 mm I.D. × 30 cm in series) manufactured by Tosoh Corporation. It was calculated by size exclusion chromatography (solvent: 1,2-dichlorobenzene, temperature: 145° C.) using HLC-8321 GPC/HT and polystyrene as a molecular weight standard.
Productivity and catalytic activity were calculated by the following equations.

アルゴン雰囲気下、錯体１（３４．０ｍｇ，０．０２９１ｍｍｏｌ）を含む５０ｍＬオートクレープ中に、トルエン（１０ｍＬ）を加えた。その後、窒素雰囲気下、アクリル酸メチル（０．２０ｍＬ，０．１９ｇ，２．２ｍｍｏｌ）をトルエン（１０ｍＬ）に溶かした溶液を加えた。エチレン（２．５ＭＰａ）を充填した後、オートクレーブを３０℃で、１８時間撹拌した。オートクレーブ内部の液体をメタノール（３００ｍＬ）と１．０ｍｏｌ／Ｌ塩酸水溶液（５０ｍＬ）の混合液に注ぎ、室温で４時間撹拌した。生じた共重合体をろ過によって回収し、メタノールで洗浄した後に減圧下８０℃で乾燥して、共重合体１を得た。収量は２１ｍｇであった。これにより錯体１の触媒活性を０．７２ｋｇ／ｍｏｌと算出した。 [Example 1]
Copolymerization of methyl acrylate and ethylene (preparation of copolymer 1)
In Example 1, tetramethyl(2-methylthioethyl)cyclopentadienylcobaltmethyl(acetonitrile) (tetrakis(3,5-bis(trifluoromethyl)phenyl)borate) was used as catalyst. This is abbreviated as complex 1 below.

Toluene (10 mL) was added into a 50 mL autoclave containing Complex 1 (34.0 mg, 0.0291 mmol) under an argon atmosphere. After that, a solution of methyl acrylate (0.20 mL, 0.19 g, 2.2 mmol) dissolved in toluene (10 mL) was added under a nitrogen atmosphere. After charging with ethylene (2.5 MPa), the autoclave was stirred at 30° C. for 18 hours. The liquid inside the autoclave was poured into a mixture of methanol (300 mL) and 1.0 mol/L hydrochloric acid aqueous solution (50 mL) and stirred at room temperature for 4 hours. The resulting copolymer was collected by filtration, washed with methanol, and dried at 80° C. under reduced pressure to obtain copolymer 1. Yield was 21 mg. From this, the catalytic activity of complex 1 was calculated to be 0.72 kg/mol.

By size exclusion chromatography, the obtained copolymer 1 was calculated to have a number average molecular weight of 1,400 and a weight average molecular weight of 3,600, and Mw/Mn was 2.6. The ethylene:methyl acrylate molar ratio in the copolymer was determined by ¹ H-NMR analysis to be 98.2:1.8. Regarding the polymer terminal structure, the ¹ H-NMR signals of hydrogen atoms derived from carbon-carbon double bonds are around 5.89 ppm (e in the above figure) and around 5.04 ppm (f in the above figure). equivalent), the ¹³ C-NMR signal of the carbon atom derived from the saturated ester was observed at 50.9 ppm (corresponding to n in the above figure), and the ¹ H-NMR signal of the hydrogen atom derived from the unsaturated ester is observed around 7.01 ppm (corresponding to p in the above figure) and around 5.89 ppm (corresponding to q in the above figure), the carbon-carbon double bond or the end of the saturated ester or unsaturated ester It was confirmed to be a polymer having a structure. Regarding the internal structure of the polymer, the ¹³ C-NMR signal of the tertiary carbon atom (corresponding to z in the above figure) derived from the alkyl group branched structure with 2 or more carbon atoms is within the range of 38.2 to 39.0 ppm. It was found to be a linear polymer. In addition, the ¹ H-NMR signal of hydrogen atoms derived from the ethylene-acrylic-ethylene structure was observed at 3.72 ppm (corresponding to dd in the figure above), and the ¹³ C-NMR signal of carbon atoms was 50.7 ppm ( dd in the figure), 45.5 ppm (corresponding to cc in the figure), around 32.2 ppm (corresponding to bb in the figure) and 27.2 ppm (corresponding to aa in the figure). From the results, it was confirmed that it was a random copolymer having an ethylene-acrylic-ethylene structure.
FIG. 1 shows the results of size exclusion chromatography, FIG. 2 shows the results of ¹ H-NMR measurements, and FIGS. 3, 4 and 5 show the results of ¹³ C-NMR measurements.

Claims (4)

A method for producing a polar group-containing olefin-based copolymer, wherein a linear or branched hydrocarbon having one carbon-carbon double bond is produced by a catalyst containing a metal complex represented by the following general formula ( C2): and a monomer represented by the following general formula (1).

(Wherein, M represents a cobalt atom, L represents a neutral electron ^- donating ligand, A- represents a counterion of a cationic organometallic compound , R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently a hydrogen atom; optionally substituted alkyl group having 1 to 30 carbon atoms, alicyclic group, alkoxy group, aryl group or aryloxy group or each independently represents an amino group or a silyl group having one or more hydrogen atoms substituted with a hydrocarbon having 1 to 30 carbon atoms, and two of R ¹ to R ⁵ are linked to form a ring structure; Y represents O or S, and one of R ¹ to R ⁵ and R ⁷ or R ⁸ together may have a silicon atom in the skeleton. 30 may form a divalent hydrocarbon group, R ⁷ and R ⁸ may form a heterocyclic structure together with Y, R ⁶ and L combine to form a ring structure may form.)

(wherein R ¹⁰ represents a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms, R ¹¹ represents —COOR ¹² (wherein R ¹² represents a hydrocarbon group having 1 to 20 carbon atoms) or cyano represents a group. ) The polar group according to claim 1, wherein R ¹¹ in the general formula (1) is —COOR ¹² (wherein R ¹² represents a hydrocarbon group having 1 to 20 carbon atoms ). A method for producing an olefin-containing copolymer. The monomer represented by the general formula (1) is at least one monomer selected from methyl acrylate, ethyl acrylate, n-butyl acrylate, tert-butyl acrylate and acrylonitrile , The method for producing the polar group-containing olefinic copolymer according to claim 1. 4. The polar group-containing olefinic copolymer according to any one of claims 1 to 3, wherein the linear or branched hydrocarbon having one carbon-carbon double bond is ethylene. Combined manufacturing method.

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