JP2013079347A - Polar group-containing allyl monomer terpolymer, and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polar group-containing allyl copolymer having a novel structure and having a high molecular weight and a high rigidity, which is conventionally difficult to synthesize; and to provide a method for producing the same.SOLUTION: The polar group-containing allyl copolymer having a crosslinked structure and a high molecular weight is obtained by polymerizing an allyl monomer together with an olefin compound and a hydrocarbon compound having a specific structure and two carbon-carbon double bonds, by using a periodic table group 10 metal complex as a catalyst component, wherein the allyl monomer has as a polar group -OH, -OCOR(Ris a 1-5C hydrocarbon group), -N(R)2 (Ris a hydrogen atom, a 1-5C hydrocarbon group, a 6-18C aromatic residue or -COOR(Ris a 1-10C hydrocarbon group or a 6-10 aromatic residue), and two Rmay be identical or different), or a halogen atom. The method for producing the same is also provided.

Description

  The present invention relates to a novel polar group-containing allyl monomer copolymer and a method for producing the same.

  Polymerization of a monomer having an allyl group is difficult as compared with a vinyl monomer, and its polymer is hardly known. The main reason is that when an allyl group-containing monomer is radically polymerized, the degenerative chain transfer to the monomer suppresses the polymer growth reaction, and only oligomers with a low degree of polymerization are obtained (Chem. Rev. ., 58, 807 (1958) (Non-Patent Document 1)).

  JP-A-58-49792 (Patent Document 1) discloses ethylene / allyl acetate copolymers and ethylene / allyl acetate / vinyl acetate terpolymers as hydrocarbon oil compositions. The synthesis method is a radical polymerization method, which is a low molecular weight substance having an intrinsic viscosity of about 0.12 dl / g.

  J. Am. Chem. Soc., 133, 1232 (2011) (Non-Patent Document 2) describes copolymers of ethylene and allyl compounds such as allyl alcohol, allyl acetate, allylamine, and allyl chloride. However, their molecular weight (Mn) is less than 7,000, and the molecular weight is small for use as a polymer compound.

JP 58-49792 A

Chem. Rev., 58, 807 (1958) J. Am. Chem. Soc., 133, 1232 (2011)

  An object of the present invention is to provide a high-molecular-weight, high-rigidity polar group-containing allyl copolymer having a novel structure, which has been considered difficult to synthesize in other polymerization modes such as radical polymerization, and a method for producing the same. It is in.

  As a result of intensive studies to solve the above problems, the present inventors have used a group 10 metal complex of the periodic table as a catalyst component, an allylic monomer containing a polar group, a carbon having a specific structure, and an olefin compound. -It has been found that by polymerizing with a hydrocarbon compound having two carbon double bonds, a high molecular weight polar group-containing allyl monomer copolymer having a crosslinked structure can be obtained, and the present invention has been completed.

（式中、Ｒ¹は水素原子または炭素原子数１〜６のアルキル基を表し、Ｒ²は−ＯＨ、−ＯＣＯＲ^2-1（Ｒ^2-1は炭素原子数１〜５の炭化水素基を表す。）、−Ｎ（Ｒ^2-2）₂（Ｒ^2-2は水素原子、炭素原子数１〜５の炭化水素基、炭素原子数６〜１８の芳香族残基、または−ＣＯＯＲ^2-3（Ｒ^2-3は炭素原子数１〜１０の炭化水素基、または炭素原子数６〜１０の芳香族残基を表す。）を表し、２つのＲ^2-2は同じでも異なっていてもよい。）、またはハロゲン原子を表し、複数のＲ³はそれぞれ独立して、水素原子または炭素原子数１〜５の炭化水素基を表し、ｐは０または１〜４の整数を表し、ｎ、ｍ、及びｋはそれぞれのモノマーユニットのモル比を表す数値である。）
で示されるモノマーユニットを有する極性基含有アリルモノマー共重合体。
［２］一般式（１）、一般式（２）、及び一般式（３）のモノマーユニットのモル比ｎ、ｍ、及びｋが次式

を満足する前項［１］に記載の共重合体。
［３］ポリスチレン換算の数平均分子量Ｍｎが７，０００〜１，０００，０００である前項［１］または［２］に記載の共重合体。
［４］一般式（１）、一般式（２）、及び一般式（３）で示されるモノマーユニットのみを有する前項［１］〜［３］のいずれかに記載の共重合体。
［５］一般式（３）において、ｐ＝０である前項［１］〜［４］のいずれかに記載の共重合体。
［６］一般式（３）で示されるモノマーユニットが、式中すべてのＲ³が水素原子を表し、ｐが０である２，５−ノルボルナジエンに由来する前項［１］〜［５］のいずれかに記載の共重合体。
［７］一般式（１）で示されるモノマーユニットが、式中のＲ¹が水素原子を表すエチレンに由来し、一般式（２）で示されるモノマーユニットが、式中のＲ²が−Ｏ−Ｃ（＝Ｏ）ＣＨ₃を表す酢酸アリルに由来し、一般式（３）で示されるモノマーユニットが、式中のすべてのＲ³が水素原子を表し、ｐが０である２，５−ノルボルナジエンに由来する前項［１］〜［６］のいずれかに記載の共重合体。
［８］一般式（Ｃ１）

（式中、Ｍは周期律表第１０族の金属原子を表し、Ｘはリン原子（Ｐ）または砒素原子（Ａｓ）を表し、Ｒ⁵は水素原子、またはハロゲン原子、アルコキシ基、アリールオキシ基及びアシロキシ基から選ばれる１つ以上の基で置換されていてもよい炭素原子数１〜３０の炭化水素基を表し、Ｙ、Ｒ⁶及びＲ⁷はそれぞれ独立して、水素原子、アルコキシ基、アリールオキシ基、シリル基、アミノ基、またはハロゲン原子、アルコキシ基、及びアリールオキシ基から選ばれる１つ以上の基で置換されていてもよい炭素原子数１〜３０の炭化水素基を表し、Ｒ⁶とＲ⁷は結合して環構造を形成してもよく、ＱはＺ［−Ｓ（＝Ｏ）₂−Ｏ−］Ｍ、Ｚ［−Ｃ（＝Ｏ）−Ｏ−］Ｍ、Ｚ［−Ｐ（＝Ｏ）（−ＯＨ）−Ｏ−］ＭまたはＺ［−Ｓ−］Ｍの「［ ］」の中に示される２価の基を表し（ただし、両側のＺ、Ｍは基の結合方向を示すために記載している。）、Ｚは水素原子、またはハロゲン原子、アルコキシ基、及びアリールオキシ基から選ばれる１つ以上の基で置換されていてもよい炭素原子数１〜４０の炭化水素基を表し、ＹとＺは結合して環構造を形成してもよく、Ｒ⁶及び／またはＲ⁷はＹと結合して環構造を形成してもよい。また、Ｌは電子供与性配位子を表し、ｑは０、１／２、１または２である。）
で示される金属錯体を触媒として使用し、一般式（４）

（式中、Ｒ¹は水素原子または炭素原子数１〜６のアルキル基を表す。）
で示されるオレフィン、一般式（５）

（式中、Ｒ²は−ＯＨ、−ＯＣＯＲ^2-1（Ｒ^2-1は炭素原子数１〜５の炭化水素基を表す。）、−Ｎ（Ｒ^2-2）₂（Ｒ^2-2は水素原子、炭素原子数１〜５の炭化水素基、炭素原子数６〜１８の芳香族残基、または−ＣＯＯＲ^2-3（Ｒ^2-3は炭素原子数１〜１０の炭化水素基、または炭素原子数６〜１０の芳香族残基を表す。）を表し、２つのＲ^2-2は同じでも異なっていてもよい。）、またはハロゲン原子を表す。）
で示されるアリル化合物、及び一般式（６）

（式中、複数のＲ³はそれぞれ独立して、水素原子または炭素原子数１〜５の炭化水素基を表し、ｐは０または１〜４の整数を表す。）
で示される２つの炭素‐炭素二重結合を有する炭化水素化合物を共重合することを特徴とする極性基含有アリルモノマー共重合体の製造方法。
［９］一般式（Ｃ１）で示される触媒が、一般式（Ｃ３）

（式中、４個のＲ⁸はそれぞれ独立して、水素原子、炭素原子数１〜８のアルキル基、炭素原子数１〜８のアルコキシ基、炭素原子数６〜１８のアリールオキシ基、またはハロゲン原子を表し、Ｍ、Ｒ⁵、Ｒ⁶、Ｒ⁷、Ｌ、及びｑは前項［８］の記載と同じ意味を表す。）
で示される前項［８］に記載の共重合体の製造方法。
［１０］一般式（Ｃ３）中のＲ⁶及びＲ⁷が共にイソプロピル基を表し、Ｒ⁸がすべて水素原子を表し、Ｌが２，６−ジメチルピリジンを表し、ｑが１であり、ＭがＰｄを表す前項［９］に記載の共重合体の製造方法。 That is, the present invention relates to the following [1] to [10].
[1] General formula (1), general formula (2), and general formula (3)

(In the formula, R ¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R ² represents —OH, —OCOR ^2-1 (R ^2-1 represents a hydrocarbon group having 1 to 5 carbon atoms, ^{represented), -. N (R 2-2} ) 2 (R 2-2 is a hydrogen atom, a hydrocarbon group having 1 to 5 carbon atoms, an aromatic residue having 6 to 18 carbon atoms, or -COOR, ^{2- 3} (R ^2-3 represents a hydrocarbon group having 1 to 10 carbon atoms or an aromatic residue having 6 to 10 carbon atoms), and two R ^2-2 may be the same or different. Or a halogen atom, each of the plurality of R ³ independently represents a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms, p represents 0 or an integer of 1 to 4, n, m and k are numerical values representing the molar ratio of each monomer unit.)
A polar group-containing allyl monomer copolymer having a monomer unit represented by:
[2] The molar ratios n, m, and k of the monomer units of general formula (1), general formula (2), and general formula (3) are

The copolymer according to item [1], which satisfies the following.
[3] The copolymer according to item [1] or [2], wherein the number average molecular weight Mn in terms of polystyrene is 7,000 to 1,000,000.
[4] The copolymer according to any one of [1] to [3] above, having only monomer units represented by general formula (1), general formula (2), and general formula (3).
[5] The copolymer according to any one of [1] to [4], wherein p = 0 in the general formula (3).
[6] Any of the aforementioned items [1] to [5], wherein the monomer unit represented by the general formula (3) is derived from 2,5-norbornadiene in which all R ³ represent hydrogen atoms and p is 0. A copolymer according to any one of the above.
[7] The monomer unit represented by the general formula (1) is derived from ethylene in which R ^{1 in} the formula represents a hydrogen atom, and the monomer unit represented by the general formula (2) is represented by R ^{2 in} the formula being —O. A monomer unit derived from allyl acetate representing —C (═O) CH ₃ , represented by the general formula (3), wherein all R ³ in the formula represents a hydrogen atom, and p is 0, The copolymer according to any one of [1] to [6] above, which is derived from norbornadiene.
[8] General formula (C1)

(In the formula, M represents a metal atom of Group 10 of the periodic table, X represents a phosphorus atom (P) or an arsenic atom (As), R ⁵ represents a hydrogen atom, or a halogen atom, an alkoxy group, an aryloxy group. And a hydrocarbon group having 1 to 30 carbon atoms which may be substituted with one or more groups selected from acyloxy groups, Y, R ⁶ and R ⁷ are each independently a hydrogen atom, an alkoxy group, An aryloxy group, a silyl group, an amino group, or a hydrocarbon group having 1 to 30 carbon atoms that may be substituted with one or more groups selected from a halogen atom, an alkoxy group, and an aryloxy group; ⁶ and R ⁷ may combine to form a ring structure, and Q represents Z [—S (═O) ₂ —O—] M, Z [—C (═O) —O—] M, Z [ “[]” Of —P (═O) (— OH) —O—] M or Z [—S—] M Represents a divalent group shown in the formula (wherein Z and M on both sides are described to indicate the bonding direction of the group), and Z represents a hydrogen atom, or a halogen atom, an alkoxy group, and an aryloxy group. Represents a hydrocarbon group having 1 to 40 carbon atoms which may be substituted with one or more groups selected from: Y and Z may combine to form a ring structure, and R ⁶ and / or R ⁷ may combine with Y to form a ring structure, L represents an electron-donating ligand, and q is 0, 1/2, 1 or 2.)
And a metal complex represented by the general formula (4)

(In the formula, R ¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.)
Olefin represented by general formula (5)

(Wherein R ² represents —OH, —OCOR ^2-1 (R ^2-1 represents a hydrocarbon group having 1 to 5 carbon atoms), —N (R ^2-2 ) ₂ (R ^2-2 Is a hydrogen atom, a hydrocarbon group having 1 to 5 carbon atoms, an aromatic residue having 6 to 18 carbon atoms, or -COOR ^2-3 (R ^2-3 is a hydrocarbon group having 1 to 10 carbon atoms, Or an aromatic residue having 6 to 10 carbon atoms), and two R ^2-2 may be the same or different.), Or a halogen atom.)
And an allyl compound represented by the general formula (6)

(In the formula, each of R ³ independently represents a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms, and p represents 0 or an integer of 1 to 4).
A method for producing a polar group-containing allyl monomer copolymer, which comprises copolymerizing a hydrocarbon compound having two carbon-carbon double bonds represented by formula (1).
[9] The catalyst represented by the general formula (C1) is represented by the general formula (C3).

(Wherein, four R ^{8 s} are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an aryloxy group having 6 to 18 carbon atoms, or Represents a halogen atom, and M, R ⁵ , R ⁶ , R ⁷ , L, and q have the same meaning as described in [8] above.)
[10] The method for producing a copolymer according to [8] above.
[10] R ⁶ and R ⁷ in the general formula (C3) both represent an isopropyl group, R ⁸ represents a hydrogen atom, L represents 2,6-dimethylpyridine, q is 1, M is The method for producing a copolymer according to [9], wherein Pd is represented.

  A book in which a metal complex of Group 10 of the Periodic Table is used as a catalyst component, and a hydrocarbon compound having two carbon-carbon double bonds having a specific structure is added to a polar group-containing allyl monomer and olefin for copolymerization By the method of the invention, a high molecular weight polar group-containing allyl monomer copolymer can be obtained.

  The copolymer of the present invention has a polar functional structure such as an ester structure or a hydroxyl group, and is added to a polyolefin or the like to improve a surface property such as adhesiveness or printability. They can be used as compatibilizers with other resins, dispersants such as pigments, paints, inks, adhesives, binders, plasticizers, lubricants, lubricants, surfactants, and the like. In addition, since the copolymer of the present invention is easily increased in molecular weight due to a crosslinked structure, it can be easily formed into a film or a sheet, and can be applied to food packaging agents, gasoline tanks, and the like. Further, due to the presence of the third monomer unit, high rigidity, high strength, and dimensional stability can be expected.

  In addition, the presence of long-chain branching due to the cross-linked structure gives the polymer excellent molding processability, and is expected to develop into unprecedented materials that have processing characteristics, mechanical properties, and various characteristics due to polar functional groups. it can.

3 is a ¹³ C-NMR spectrum of the polymer 2 obtained in Example 2. 3 is an enlarged view of ¹³ C-NMR spectrum (20 to 50 ppm) of polymer 2 obtained in Example 2. FIG. FIG. 4 is a correspondence diagram for carbon identification of an ethylene / allyl acetate / norbornadiene copolymer. 2 is an infrared absorption spectrum of the polymer 1 obtained in Example 1. 2 is an infrared absorption spectrum of the polymer 2 obtained in Example 2. 2 is a differential thermothermal weight simultaneous measurement (TG-DTA) chart of the polymer 1 obtained in Example 1. FIG. 3 is a differential thermothermal weight simultaneous measurement (TG-DTA) chart of the polymer 2 obtained in Example 2. FIG.

（式中、Ｒ¹は水素原子または炭素原子数１〜６の炭化水素基を表す。）
で示されるオレフィン、一般式（５）

（式中、Ｒ²は−ＯＨ、−ＯＣＯＲ^2-1（Ｒ^2-1は炭素原子数１〜５の炭化水素基を表す。）、−Ｎ（Ｒ^2-2）₂（Ｒ^2-2は水素原子、炭素原子数１〜５の炭化水素基、炭素原子数６〜１８の芳香族残基、または−ＣＯＯＲ^2-3（Ｒ^2-3は炭素原子数１〜１０の炭化水素基、または炭素原子数６〜１０の芳香族残基を表す。）を表し、２つのＲ^2-2は同じでも異なっていてもよい。）、またはハロゲン原子を表す。）
で示されるアリル化合物、一般式（６）

（式中、複数のＲ³はそれぞれ独立して、水素原子または炭素原子数１〜５のアルキル基、ｐは０または１〜４の整数を表す。）
で示される炭素−炭素二重結合を２つ有する炭化水素化合物、及び必要に応じて他のモノマーを共重合することにより得られる。 Polar group-containing allyl monomer copolymer having a crosslinked structure:
The polar group-containing allyl monomer copolymer having a crosslinked structure of the present invention has the general formula (4)

(In the formula, R ¹ represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms.)
Olefin represented by general formula (5)

(Wherein R ² represents —OH, —OCOR ^2-1 (R ^2-1 represents a hydrocarbon group having 1 to 5 carbon atoms), —N (R ^2-2 ) ₂ (R ^2-2 Is a hydrogen atom, a hydrocarbon group having 1 to 5 carbon atoms, an aromatic residue having 6 to 18 carbon atoms, or -COOR ^2-3 (R ^2-3 is a hydrocarbon group having 1 to 10 carbon atoms, Or an aromatic residue having 6 to 10 carbon atoms), and two R ^2-2 may be the same or different.), Or a halogen atom.)
An allyl compound represented by the general formula (6)

(In the formula, each of R ³ is independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and p is 0 or an integer of 1 to 4)
It is obtained by copolymerizing a hydrocarbon compound having two carbon-carbon double bonds represented by formula (II) and, if necessary, other monomers.

（式中、Ｒ¹、Ｒ²、Ｒ³、及びｐは上記と同様の意味を表す。ｎ、ｍ、及びｋはそれぞれのモノマーユニットのモル比を表す数値である。）
で示されるモノマーユニットを有する共重合体であり、必要に応じて、一般式（１）、一般式（２）、及び一般式（３）で示されるモノマーユニット以外のモノマーユニットを有していてもよい。 The polar group-containing allyl monomer copolymer of the present invention has general formula (1), general formula (2), and general formula (3).

(In the formula, R ¹ , R ² , R ³ , and p represent the same meaning as described above. N, m, and k are numerical values representing the molar ratio of each monomer unit.)
And a monomer unit other than the monomer units represented by the general formula (1), the general formula (2), and the general formula (3), if necessary. Also good.

を満足する。 The polar group-containing allyl monomer copolymer of the present invention preferably has the following structures (A) and (B).
(A) In a portion composed of monomer units other than the monomer unit represented by the general formula (3), 1 or less per 1,000 carbon atoms in which the branch having 2 or more carbon atoms in the main chain constitutes the main chain The two main chains are cross-linked by the monomer unit represented by the general formula (3). In addition, one main chain may be cross-linked at two or more locations.
(B) The molar ratios n, m, and k of the monomer units represented by the general formula (1), the general formula (2), and the general formula (3) are as follows:

Satisfied.

を満足する。 Furthermore, it is preferable that the following requirements (C), (D), and (E) are satisfied.
(C) The number average molecular weight Mn in terms of polystyrene is 7,000 or more and 1,000,000 or less.
(D) It has a carbon-carbon double bond at least at one end of the main chain.
(E) The molar ratios n, m, and k of the monomer units represented by general formula (1), general formula (2), and general formula (3) are as follows:

Satisfied.

  The polymer of the present invention is represented by the monomer units represented by the general formula (1) and the general formula (2), and further represented by the general formula (1), the general formula (2), and the general formula (3) as necessary. It has a structure in which a linear copolymer with very few branches composed of monomer units other than the monomer unit is crosslinked with the monomer unit represented by the general formula (3).

  First, in the copolymer having a crosslinked structure of the present invention, a portion excluding the monomer unit represented by the general formula (3), that is, the monomer unit represented by the general formula (1) and the general formula (2). The copolymer will be described.

As the polymer chain structure, a linear structure and a branched structure are generally known. It is known that an ethylene polymer obtained by a radical polymerization method can obtain a branched structure by a back biting mechanism. As the branched structure, there are short chain branches having 5 or less carbon atoms by back biting and long chain branches starting from radicals generated in the main chain. On the other hand, out of the structure of the copolymer obtained by the method of the present invention, the polymer chain excluding the monomer unit represented by the general formula (3), that is, the monomer unit represented by the general formula (1) and the general formula (2) The copolymer composed of is linear with very few branches, and there are 1 or less branches per 1,000 carbon atoms constituting the main chain. Here, the number of branches per 1,000 carbon atoms can be calculated by measuring the number of tertiary carbons in the main chain to which branches having 2 or more carbon atoms are bonded by ¹³ C-NMR.
In the present invention, the term “branch” means a group having 2 or more carbon atoms, and is a side chain derived from a monomer (corresponding to R ¹ in the general formula (1) and —CH ₂ in the general formula (2)). -Corresponding to -R ² ) and the monomer units represented by the general formula (3) do not count as branches. For example, when 1-butene is copolymerized as an olefin compound, the ethyl group is a side chain, but this is not branched. The same applies to the case where monomer units other than the monomer units represented by general formula (1), general formula (2), and general formula (3) are included.

式中、Ｒは、一般式（１）または一般式（２）における、Ｒ¹またはＣＨ₂Ｒ²を表し、Polymerはポリマー鎖を表す。 One of the terminal structures of the copolymer of the present invention can be a carbon-carbon double bond, unlike the structure of the main chain. The terminal structure can be considered by dividing it into a starting end formed at the start of polymerization and a stopping end formed at the end of polymerization. The starting end is a saturated bond because an olefin is inserted in the bond between the catalytic metal and hydrogen atom or the bond between the catalytic metal and alkyl group, but the terminal end is a saturated bond and an unsaturated bond depending on the reaction mechanism. It is classified in the case of. It has been reported that when a chain transfer agent having an alkyl group such as organoaluminum is used in the reaction system, the molecular chain is chain-transferred to an aluminum atom, and the reaction is terminated to become a saturated terminal. When using a titanium trichloride-based Ziegler-Natta catalyst or a metal complex of a Group 4 element of the periodic table as the catalyst, allyl compounds having polar groups are copolymerized using organoaluminum, so that the terminal structure is saturated. Become. On the other hand, since organic aluminum is not used in the present invention, polymer chain growth is stopped by the β-hydrogen elimination mechanism, and at least one terminal structure can be an unsaturated double bond.

In the formula, R represents R ¹ or CH ₂ R ² in the general formula (1) or the general formula (2), and Polymer represents a polymer chain.

  Unsaturated double bonds can be confirmed by NMR analysis of the copolymer. The terminal unsaturated bond is highly reactive and can be modified with a functional group, formed into a block copolymer, converted into a star polymer, and the like, so the copolymer of the present invention is extremely useful.

  According to the method for producing a polar group-containing allyl monomer copolymer having a crosslinked structure according to the present invention, the polar group-containing allyl monomer copolymer having a number average molecular weight Mn in terms of polystyrene of 7,000 or more and 1,000,000 or less. Coalescence can be obtained. Such a copolymer can be subjected to various molding methods. The number average molecular weight Mn is more preferably from 7000 to 500,000, and even more preferably from 10,000 to 300,000, from the balance between moldability and strength.

  The content of the monomer unit represented by the general formula (3) (mol% = {k / (m + n + k)} × 100) is preferably 0.1 mol% or more and 10 mol% or less. By the monomer unit represented by the general formula (3), the monomer unit represented by the general formula (1) and the general formula (2), and if necessary, the general formula (1), the general formula (2), and the general formula ( The molecular weight is further increased by cross-linking a very little branched linear copolymer comprising monomer units other than the monomer unit shown in 3). When there are too few monomer units shown by General formula (3), the effect which increases molecular weight will be small. If the amount is too large, the cross-linking becomes complicated (network structure), and the effect of increasing the molecular weight relative to the amount added becomes small. In this respect, 0.2 to 5.0 mol% is more preferable. When there are a plurality of types of monomer units represented by the general formula (3), the total value of these monomer units is k.

  The content of the monomer unit represented by the general formula (2) (mol% = {m / (m + n + k)} × 100) is preferably 0.1% mol or more and 50 mol% or less. The content of the monomer unit represented by the general formula (2) is more preferably 0.5 to 15.0 mol%, and preferably 1.0 to 10.0 mol from the viewpoint of melt viscosity and molding conditions similar to those of polyethylene. % Is more preferable. When a plurality of types of monomer units represented by the general formula (2) are present, the total value of these monomer units is m.

（式中、ｒはモノマーユニットのモル比を表す数値であり、Ｒ³及びｐは上記と同様の意味を表す。）
で示されるモノマーユニットが存在していてもよい。この場合、「ｋ＋ｒ」を前記のｋと読み替えるものとする。 Moreover, the 4th monomer unit may be contained other than the compound monomer unit shown by General formula (1), General formula (2), and General formula (3). Specific examples of the fourth monomer unit include monomer units derived from acrylic acid, acrylic acid ester, methacrylic acid ester, acrylonitrile, vinyl acetate, styrene, vinyl ether and the like. Furthermore, a monomer unit formed by inserting only one of the two carbon-carbon double bonds of the hydrocarbon compound represented by the general formula (6), that is, the general formula (7)

(In the formula, r is a numerical value representing the molar ratio of the monomer units, and R ³ and p have the same meaning as described above.)
A monomer unit represented by may be present. In this case, “k + r” is read as k.

（式中、ｍ¹及びｍ²は、それぞれのモノマーユニットのモル比を表す数値である。） In the copolymer of the present invention, R ² of the monomer unit represented by the general formula (2) For -OCOR ^2-1, a part of R ² or all of them may be hydrolyzed. When the monomer unit represented by the general formula (2) is derived from allyl acetate, the monomer unit derived from allyl acetate represented by the following formula (2-2) is saponified in the copolymer after the saponification reaction. The monomer unit is derived from allyl alcohol represented by -1) and has a structure of m ₁ + m ₂ = m.

(In the formula, m ¹ and m ² are numerical values representing the molar ratio of each monomer unit.)

When all the monomer units represented by the general formula (2) are saponified, m ₂ = 0. The ratio between m ₁ and m ₂ can be adjusted by the degree of saponification. In the saponification reaction of the copolymer of the present invention, the copolymer is dissolved or dispersed in a solvent in the same manner as the saponification reaction of polyvinyl acetate or ethylene / vinyl acetate copolymer, and in the presence of water or alcohol, It can be performed by treatment with acid or alkali.

The copolymer can be formed into a pellet shape, a film shape, a sheet shape, or the like under the same conditions as those of a normal thermoplastic resin.
The obtained copolymer can be made into a product by a molding method such as injection molding, extrusion molding or film molding. Alternatively, it can be used as a modifier for surface properties such as adhesion and printability, a compatibilizer between nonpolar polyolefin and other highly polar resins, and a dispersant such as pigment by adding to polyolefin. Alternatively, it can be used as a paint, ink, adhesive, binder, plasticizer, lubricant, lubricating oil, surfactant, and the like.

で示される。 monomer:
The olefin which is the monomer that is the base of the monomer unit represented by the general formula (1) of the copolymer of the present invention is represented by the general formula (4).

Indicated by

In general formula (4), R ¹ represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. Specific examples of the olefin represented by the general formula (4) include ethylene, propylene, 1-butene, 1-pentene, 1-hexene and the like, and ethylene and propylene are preferable in terms of reactivity and raw material availability. More preferred is ethylene. Moreover, these can be used individually by 1 type or in combination of 2 types.

で示される。 The allyl compound having a polar group, which is a monomer serving as a base of the monomer unit represented by the general formula (2) of the copolymer of the present invention, has the general formula (5).

Indicated by

In the general formula (5), R ² represents —OH, —OCOR ^2-1 (R ^2-1 represents a hydrocarbon group having 1 to 5 carbon atoms), —N (R ^2-2 ) ₂ ( R ^2-2 is a hydrogen atom, 1 to 5 carbon atoms hydrocarbon group, an aromatic residue having 6 to 18 carbon atoms or -COOR ^2-3 (R ^2-3 is 1 to 10 carbon atoms, Represents a hydrocarbon group or an aromatic residue having 6 to 10 carbon atoms.), And two R ^2-2 may be the same or different.), Or represents a halogen atom. R ^2-1 is preferably an alkyl group having 1 to 3 carbon atoms, and particularly preferably a methyl group. R ^2-2 is preferably a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or a phenyl group. R ^{2-3 in} —COOR ^2-3 is preferably a linear or branched alkyl group having 1 to 4 carbon atoms, a phenyl group, a benzyl group, or the like. As the halogen atom for R ² , chlorine and bromine are preferable.

  Specific examples of the allyl compound having a polar group represented by the general formula (5) include allyl acetate, allyl alcohol, allylamine, N-allylaniline, Nt-butoxycarbonyl-N-allylamine, N-benzyloxycarbonyl- N-allylamine, N-allyl-N-benzylamine, allyl chloride, allyl bromide and the like can be mentioned. Among these, allyl acetate and allyl alcohol are particularly preferable, and allyl acetate is more preferable. These can be used alone or in combination of two or more.

で示される。 The hydrocarbon compound having two carbon-carbon double bonds having a specific structure as a base of the monomer unit represented by the general formula (3) of the copolymer of the present invention is represented by the general formula (6).

Indicated by

In General formula (6), several R < ³ > represents a hydrogen atom or a C1-C5 alkyl group each independently, and p represents 0 or the integer of 1-4.
The alkyl group having 1 to 5 carbon atoms represented by R ³ may have a branch. R ³ is preferably a hydrogen atom, a methyl group, or an ethyl group. The value of p is preferably 0 or 1 and more preferably 0 in terms of availability and cost.

Specific examples of the compound represented by the general formula (6) include 2,5-norbornadiene, 7-methyl-2,5-norbornadiene, 7-ethyl-2,5-norbornadiene, 7,7-dimethyl-2,5. -Norbornadiene, 1-methyl-2,5-norbornadiene, 1-ethyl-2,5-norbornadiene, 4-methyl-2,5-norbornadiene, 4-ethyl-2,5-norbornadiene, tetracyclo [4.4.0 .1, ^2,5 . 1 ^7,10 ] -3,8-dodecadiene and the like. Among these, 2,5-norbornadiene is particularly preferable. These can be used alone or in combination of two or more.

（式中、Ｒ³、ｐ、及びｒは上記と同様の意味を表す。）
で示されるモノマーユニットが生成する可能性がある。 When the compound represented by the general formula (6) is copolymerized, only one of the two carbon-carbon double bonds is inserted in a part thereof, and the general formula (7)

(In the formula, R ³ , p and r represent the same meaning as described above.)
There is a possibility that a monomer unit represented by

  In addition, the compound represented by the general formula (4), the general formula (5), and the general formula (6) is added with one or more other monomers to be copolymerized to be derived from other monomers in the polymer. Functions can be added. Examples of the other monomer include polar group-containing monomers other than olefin compounds having 9 or more carbon atoms, styrene, or allyl monomers. Examples of the olefin compound having 9 or more carbon atoms include 1-nonene and 1-decene. Examples of polar group-containing monomers other than allyl monomers include acrylic acid, acrylic acid ester, methacrylic acid, methacrylic acid ester, acrylonitrile, vinyl acetate, and vinyl ether.

で示される。 catalyst:
The catalyst comprising a Group 10 metal complex of the periodic table used in the present invention has the general formula (C1)

Indicated by

In the formula, M represents a metal atom of Group 10 of the Periodic Table. X represents a phosphorus (P) atom or an arsenic atom (As). R ⁵ represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms which may be substituted with one or more groups selected from a halogen atom, an alkoxy group, and an aryloxy group. Y, R ⁶ and R ⁷ are each independently substituted with one or more groups selected from a hydrogen atom, an alkoxy group, an aryloxy group, a silyl group, an amino group, or a halogen atom, an alkoxy group and an aryloxy group. Represents a hydrocarbon group having 1 to 30 carbon atoms which may be used. R ⁶ and R ⁷ may combine to form a ring structure. Q is Z [—S (═O) ₂ —O—] M, Z [—C (═O) —O—] M, Z [—P (═O) (— OH) —O—] M, or Z [—S—] represents a divalent group shown in “[]” of M (however, Z and M on both sides are described to indicate the bonding direction of the group). Z represents a hydrogen atom or a hydrocarbon group having 1 to 40 carbon atoms which may be substituted with one or more groups selected from a halogen atom, an alkoxy group, and an aryloxy group. Y and Z may combine to form a ring structure. R ⁶ and / or R ⁷ may combine with Y to form a ring structure. L represents an electron-donating ligand, and q is 0, 1/2, 1 or 2. In the present specification, “hydrocarbon” includes saturated and unsaturated aliphatic hydrocarbons and aromatic hydrocarbons.

Hereinafter, the structure of the general formula (C1) will be described.
M represents an element of Group 10 of the periodic table. Examples of the elements of Group 10 of the periodic table include Ni, Pd, and Pt, and Ni and Pd are preferable and Pd is more preferable from the viewpoint of catalytic activity and the molecular weight obtained.
X is a phosphorus atom (P) or an arsenic atom (As) and is coordinated to M by two electrons. X is preferably a phosphorus atom in terms of availability and catalyst cost.
Y, R ⁶ , and R ⁷ are each independently one or more groups selected from a hydrogen atom, an alkoxy group, an aryloxy group, a silyl group, an amino group, or a halogen atom, an alkoxy group, and an aryloxy group. Represents a hydrocarbon group having 1 to 30 carbon atoms which may be substituted with. The alkoxy group is preferably one having 1 to 20 carbon atoms, and examples thereof include a methoxy group, an ethoxy group, a propoxy group, and an isopropoxy group. As the aryloxy group, those having 6 to 24 carbon atoms are preferable, and examples thereof include a phenoxy group. Examples of the silyl group include a trimethylsilyl group, and examples of the amino group include an amino group, a methylamino group, and a dimethylamino group. R ⁶ and R ⁷ may be the same or different. R ⁶ and R ⁷ may combine to form a ring structure. R ⁶ and / or R ⁷ may combine with Y to form a ring structure. 1 carbon atom in the hydrocarbon group having 1 to 30 carbon atoms which may be substituted with one or more groups selected from halogen atoms, alkoxy groups, and aryloxy groups of Y, R ⁶ and R ⁷ Examples of the hydrocarbon group of ˜30 include an alkyl group, an aryl group, a cycloalkyl group, and a furyl group. Specific examples of the alkoxy group and aryloxy group in the hydrocarbon group having 1 to 30 carbon atoms which may be substituted with one or more groups selected from a halogen atom, an alkoxy group, and an aryloxy group The same thing is mentioned. The halogen atom is preferably fluorine. In particular, an alkyl group and an aryl group are preferable from the viewpoint of catalytic activity.

の具体例を挙げる。なお、ＰとＭとの結合は省略している。 Hereinafter, when X is P (phosphorus atom), YX-R ⁶ and R ⁷ sites, that is,

Specific examples are given below. Note that the connection between P and M is omitted.

の具体例としては、

が挙げられる。 When X is As (arsenic atom), YX-R ⁶ , R ⁷ site,

As a specific example of

Is mentioned.

R ⁵ represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms which may be substituted with one or more groups selected from a halogen atom, an alkoxy group, an aryloxy group, and an acyloxy group. As a hydrocarbon group having 1 to 30 carbon atoms in a hydrocarbon group having 1 to 30 carbon atoms which may be substituted with one or more groups selected from a halogen atom, an alkoxy group, an aryloxy group, and an acyloxy group Is preferably an alkyl group having 1 to 6 carbon atoms. The halogen atom is preferably chlorine or bromine. The alkoxy group is preferably a methoxy group or an ethoxy group. The aryloxy group is preferably a phenoxy group. As the acyloxy group, an acetoxy group and a pivaloxy group are preferable. Particularly preferred examples of R ⁵ include a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a methoxymethyl group, a phenoxymethyl group, a 1-acetoxyphenyl group, and a 1-pivaloxypropyl group. .

Q represents a divalent group represented by —S (═O) ₂ —O—, —C (═O) —O—, —P (═O) (— OH) —O—, or —S—. , M is a site that coordinates one electron. The left side of each formula is bonded to Z, and the right side is bonded to M. Among these, -S (= O) _2- O- is particularly preferable from the viewpoint of catalytic activity.

Z represents a hydrogen atom or a hydrocarbon group having 1 to 40 carbon atoms which may be substituted with one or more groups selected from a halogen atom, an alkoxy group, and an aryloxy group. Y and Z may combine to form a ring structure. Specific examples of the halogen atom, alkoxy group and aryloxy group in the “hydrocarbon group having 1 to 40 carbon atoms which may be substituted with one or more groups selected from a halogen atom, an alkoxy group and an aryloxy group” Include those described for Y, R ⁶ and R ⁷ . Examples of the hydrocarbon group having 1 to 40 carbon atoms include methyl group, ethyl group, isopropyl group, t-butyl group, isobutyl group, cyclohexyl group, cyclopentyl group, phenyl group, 2-isopropylphenyl group, and 2,6-diisopropyl. A phenyl group etc. are mentioned.

  The ZQ site is an oxygen atom or sulfur atom having a high electronegativity and is coordinated with the metal atom M by one electron. Since the bond electrons between ZQM move from M to ZQ, it is possible to express ZQ as an anion state and M as a cation state.

式中、Ｙ¹はハロゲン原子、アルコキシ基、及びアリールオキシ基から選ばれる１つ以上の基で置換されていてもよい炭素原子数１〜７０の２価の炭化水素基を表す。Ｑ、Ｍ、Ｘ、Ｒ⁵、Ｒ⁶、Ｒ⁷、Ｌ、及びｑは一般式（Ｃ１）と同じ意味を表す。 In the general formula (C1), the Y site and the Z site can be bonded. In this case, the general formula (C1) is represented by the general formula (C2). In the general formula (C2), the YZ portion is shown as Y ¹ as a unit. Here, Y ¹ represents a cross-linked structure between Q and X.

In the formula, Y ¹ represents a divalent hydrocarbon group having 1 to 70 carbon atoms which may be substituted with one or more groups selected from a halogen atom, an alkoxy group, and an aryloxy group. Q, M, X, R ⁵ , R ⁶ , R ⁷ , L, and q represent the same meaning as in the general formula (C1).

Specific examples of the halogen atom, alkoxy group, and aryloxy group in Y ¹ are the same as those described for Y. Examples of the hydrocarbon group having 1 to 70 carbon atoms include an alkylene group and an arylene group. Particularly preferred is an arylene group.

When X is P (phosphorus atom), specific examples of the [(R ⁶ ) (R ⁷ ) P] moiety include the following structures. In the following structural formula, the bond between P, M, and Y ¹ is omitted. In the structural formulas, Me represents a methyl group, iPr represents an isopropyl group, and tBu represents a t-butyl group.

The cross-linked structure Y ¹ is a cross-linked site that connects X and Q sites. Specific examples of the crosslinked structure Y ^{1 in} which X is a P atom are shown below. Here, several R <^9> may be same or different and is a hydrogen atom, a halogen atom, a C1-C20 hydrocarbon group, or a C1-C20 hydrocarbon group substituted by the halogen atom. Represents.

The substituents R ⁶ and R ⁷ may combine with the Y ¹ site to form a ring structure. Specific examples include the following structures.

式中、４個のＲ⁸はそれぞれ独立して、水素原子、炭素原子数１〜８のアルキル基、炭素原子数１〜８のアルコキシ基、炭素原子数６〜１８のアリールオキシ基、またはハロゲン原子を表し、Ｍ、Ｒ⁵、Ｒ⁶、Ｒ⁷、Ｌ、及びｑは一般式（Ｃ１）と同じ意味を表す。 Among the catalysts represented by the general formula (C2), those represented by the following general formula (C3) are particularly preferable.

In the formula, each of four R ^{8 s} independently represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an aryloxy group having 6 to 18 carbon atoms, or a halogen atom. Represents an atom, and M, R ⁵ , R ⁶ , R ⁷ , L, and q represent the same meaning as in formula (C1).

In the formula (C3), R ⁵ is preferably an alkyl group having 1 to 6 carbon atoms, particularly preferably a methyl group. R ⁶ and R ⁷ are preferably both a cyclohexyl group, a cyclopentyl group, or an isopropyl group. M is preferably Pd.

The metal complex of the catalyst represented by the general formula (C1) and the general formula (C2) can be synthesized according to a known document (for example, J. Am. Chem. Soc. 2007, 129, 8948). That is, a metal complex is synthesized by reacting a zero-valent or divalent M source with a ligand in the general formula (C1) or the general formula (C2).
The compound represented by the general formula (C3) can be synthesized by changing Y ¹ and Q in the general formula (C2) to a specific group corresponding to the general formula (C3).

Examples of the zero-valent M source include tris (dibenzylideneacetone) dipalladium (0) and tetrakis (triphenylphosphine) palladium (0) as the palladium source, and tetracarbonylnickel (0): Ni ( CO) ₄ and bis (1,5-cyclooctadiene) nickel (0).

Divalent M source is (1,5-cyclooctadiene) (methyl) palladium chloride (II), palladium chloride (II), palladium acetate (II), bis (acetonitrile) dichloropalladium (II) as a palladium source. : PdCl ₂ (CH ₃ CN) ₂ , bis (benzonitrile) dichloropalladium (II): PdCl ₂ (PhCN) ₂ , (N, N, N ′, N′-tetramethylethylenediamine) dichloropalladium (II): PdCl ₂ (TMEDA), (N, N, N ′, N′-tetramethylethylenediamine) dimethylpalladium (II): PdMe ₂ (TMEDA), bis (acetylacetonato) palladium (II): Pd (acac) ₂ , trifluoro Palladium (II) methanesulfonate: Pd (OCOCF ₃ ) ₂ is used as nickel source, (allyl) chloride nickel (II), (allyl) nickel bromide (II), nickel chloride (II), nickel acetate (II), bis (acetylacetonato) nickel (II): Ni (acac) ₂ , (1,2-dimethoxy ethane) dichloronickel _{(II): NiCl 2 (DME} ), trifluoromethanesulfonic acid nickel _{(II): Ni (OSO 2} CF 3) 2 and the like.

The metal complex represented by the general formula (C1) or the general formula (C2) can be isolated and used, but the metal source containing M and the ligand precursor can be used in the reaction system without isolating the complex. And can be subjected to polymerization in situ. In particular, when R ^{5 in} general formula (C1) and general formula (C2) is a hydrogen atom, the metal source containing zero-valent M is reacted with the ligand precursor, and then the complex is not isolated. It is preferable to use for polymerization as it is.

（式中の記号は前記と同じ意味を表す。）、及び一般式（Ｃ１−２）

（式中の記号は前記と同じ意味を表す。）
で示される。 In this case, the ligand precursor is represented by the general formula (C1-1) in the case of the general formula (C1).

(The symbols in the formula represent the same meaning as described above), and the general formula (C1-2)

(The symbols in the formula have the same meaning as described above.)
Indicated by

（式中の記号は前記と同じ意味を表す。）
で示される。 In the case of general formula (C2), the following formula (C2-1)

(The symbols in the formula have the same meaning as described above.)
Indicated by

  Ratio (X / M or Z / M) of M source (M) and ligand precursor (C1-1) (X) or ligand precursor (C1-2) (Z) in the general formula (C1) ) Or M source (M) and the ligand precursor (C2-1) (C2 ligand) ratio ((C2 ligand) / M) is in the range of 0.5 to 2.0, Furthermore, it is preferable to select in the range of 1.0 to 1.5.

  When isolating the metal complex of the general formula (C1) or the general formula (C2), it is also possible to use one that has been previously stabilized by coordination with the electron donating ligand (L). In this case, q is 1/2, 1 or 2. When q is 1/2, it means that one divalent electron-donating ligand is coordinated to two metal complexes. q is a meaning which stabilizes a metal complex catalyst, and 1/2 or 1 is preferable. In addition, when q is 0, it means that there is no ligand.

  L represents a neutral electron donating ligand. The neutral electron-donating ligand (L) is a compound having an electron-donating group and capable of stabilizing the metal complex by coordinating two electrons to the metal atom M. Can be isolated.

  As a neutral electron-donating ligand (L), dimethyl sulfoxide (DMSO) is mentioned as what has a sulfur atom. As those having a nitrogen atom, trialkylamines having 1 to 10 carbon atoms, dialkylamines, pyridine, 2,6-dimethylpyridine, quinoline, 2-methylquinoline, aniline, 2,6-dimethylaniline, 2,6- Examples include diisopropylaniline, N, N, N ′, N′-tetramethylethylenediamine (TMEDA), 4- (N, N-dimethylamino) pyridine (DMAP), acetonitrile, and benzonitrile. Examples of phosphorus atoms include trimethylphosphine, triisopropylphosphine, tributylphosphine, tri (t-butyl) phosphine, triphenylphosphine, tris (o-tolyl) phosphine, and trifurylphosphine. Examples of those having an oxygen atom include diethyl ether, tetrahydrofuran, 1,4-dioxane, 1,2-dimethoxyethane and the like. From the viewpoint of the synthesis method, those having a nitrogen atom and those having a phosphorus atom are preferred, and those having a nitrogen atom are particularly preferred.

  The metal complex represented by the general formula (C1) or the general formula (C2) can be supported on a carrier and used for polymerization. The carrier in this case is not particularly limited, and examples thereof include inorganic carriers such as silica gel and alumina, and organic carriers such as polystyrene, polyethylene and polypropylene. Examples of the method for supporting a metal complex include a physical adsorption method in which a carrier is impregnated with a solution of the metal complex and drying, a method in which a metal complex and a carrier are chemically bonded and supported.

Polymerization method:
The method for polymerizing the monomers represented by the general formula (4), the general formula (5), and the general formula (6) using a metal complex as a catalyst is not particularly limited and can be polymerized by a generally used method. is there. That is, processes such as a solution polymerization method, a suspension polymerization method, and a gas phase polymerization method are possible, but a solution polymerization method and a suspension polymerization method are particularly preferable. The polymerization mode can be a batch mode or a continuous mode. Further, it can be carried out by single-stage polymerization or multi-stage polymerization.

  Two or more kinds of metal complex catalysts represented by the general formula (C1), the general formula (C2), or the general formula (C3) may be mixed and used for the polymerization reaction. It is possible to control the molecular weight of the polymer, the molecular weight distribution, the content of the monomer unit represented by the general formula (2) and the general formula (3) by using the mixture, and the weight suitable for the desired use can be controlled. Coalescence can be obtained. The molar ratio of the total amount of the metal complex catalyst and the monomer represented by the general formula (C1), the general formula (C2), or the general formula (C3) is in the range of 1 to 10,000,000 in terms of the monomer / metal complex ratio. , Preferably in the range of 10 to 1,000,000, more preferably in the range of 100 to 100,000.

The polymerization temperature is not particularly limited. Usually, it is -30-200 degreeC, Preferably it is 0-180 degreeC, More preferably, it is the range of 20-150 degreeC.
The polymerization pressure in which the pressure of the olefin represented by the general formula (4) occupies most of the internal pressure is within the range of normal pressure to 20 MPa, preferably within the range of normal pressure to 10 MPa.
The polymerization time can be appropriately adjusted depending on the process mode and the polymerization activity of the catalyst, and can be as short as several minutes or as long as several thousand hours.

  The atmosphere in the polymerization system is preferably filled with an inert gas such as nitrogen or argon so that air, oxygen, moisture, etc. other than the monomer does not enter in order to prevent the activity of the catalyst from decreasing. In the case of solution polymerization, it is possible to use an inert solvent in addition to the monomer. The inert solvent is not particularly limited, but is aliphatic hydrocarbon such as isobutane, pentane, hexane, heptane, cyclohexane, aromatic hydrocarbon such as benzene, toluene, xylene, chloroform, methylene chloride, carbon tetrachloride, dichloroethane, tetra Halogenated aliphatic hydrocarbons such as chloroethane, halogenated aromatic hydrocarbons such as chlorobenzene, dichlorobenzene and trichlorobenzene, aliphatic esters such as methyl acetate and ethyl acetate, aromatic esters such as methyl benzoate and ethyl benzoate, etc. Is mentioned.

  The polar group-containing allyl monomer copolymer of the present invention is a copolymer obtained by adding one or more other monomers to the compounds represented by general formula (4), general formula (5), and general formula (6). Thus, a function derived from another monomer can be added to the polymer. The monomers that can be used are as described above.

The polymer of the present invention can be converted into various polymers using the reactivity of the functional group. For example, if R ² is a hydroxyl group, the primary hydroxyl group is substituted with a halogen to serve as the starting point for living radical polymerization, and various polar group-containing monomers are polymerized by radical polymerization to produce two or more types of polymers. It is also possible to produce a graft polymer in which is bonded. Examples of radically polymerizable monomers in this case include acrylic acid, acrylic acid ester, methacrylic acid ester, acrylonitrile, vinyl acetate, and styrene.

  The charging ratio of the monomers represented by the general formula (4), the general formula (5), and the general formula (6) is appropriately adjusted according to the composition ratio of the target copolymer. The same applies when using the fourth monomer.

When the monomer represented by the general formula (4) is a gas at the polymerization reaction temperature, it is adjusted by controlling the pressure. Moreover, although the monomer shown by General formula (5) and General formula (6) can be used as it is, it can also dilute with an inert solvent and can adjust a monomer preparation ratio.
After completion of the polymerization reaction, the product copolymer can be isolated by known operations and post-treatment methods (for example, neutralization, solvent extraction, water washing, liquid separation, solvent distillation, reprecipitation, etc.). .

  EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated in detail, this invention is not limited to the following example.

[Method of analyzing polymer structure]
The structure of the copolymer obtained in the examples was determined by various NMR analyzes using JNM-ECS400 manufactured by JEOL Ltd. In the copolymer, a monomer unit derived from the olefin compound represented by the general formula (1), a monomer unit derived from the allyl compound represented by the general formula (2), and two carbons represented by the general formula (3) The content and terminal structure of the monomer unit derived from the hydrocarbon compound having a carbon double bond were 1,1,2,2-tetrachloroethane (0.55 mL) as a solvent and Cr (acac) ₃ (10 mg as a relaxation reagent). ¹³ C-NMR (9.0 microsecond 90 ° pulse, spectral width: 31 kHz, relaxation time: 10 seconds, uptake time: 10 seconds, FID) at 120 ° C. 5,000 to 10,000 times).

The terminal structure can be analyzed by ¹³ C-NMR. Particularly when having a terminal double bond, because the spectrum appearing in the vicinity of 114ppm and 139ppm in ¹³ C-NMR spectrum, a distinction can be made between saturated terminal structure appearing in 10~40ppm in ¹³ C-NMR spectrum (ref: Chem Commun. 2002, 744-745).

  The number average molecular weight and the weight average molecular weight were measured by using a high temperature GPC apparatus manufactured by Showa Denko KK, equipped with an AT-806MS column (two in series), HLC-8121 GPC / HT, and polystyrene with a molecular weight standard. It was calculated by size exclusion chromatography (solvent: 1,2-dichlorobenzene, temperature: 145 ° C.) as a substance.

The infrared absorption spectrum was measured using a FT-IR apparatus NICOLET6700 manufactured by Thermo Fisher. When the monomer unit represented by the general formula (2) is derived from allyl acetate, a strong absorption band due to CO stretching vibration of the carbonyl group is observed at 1,740 to 1,750 cm ⁻¹ (FIGS. 4 and 5). See).

Differential thermothermal weight simultaneous measurement (TG-DTA) was measured using a DTA-60A apparatus manufactured by Shimadzu Corporation. Α-Alumina was used as a standard substance, and the measurement was performed at a heating rate of 10 ° C./min under a nitrogen stream.
The melting point and the crystallization temperature were measured under a nitrogen stream using a DSC-60 apparatus manufactured by Shimadzu Corporation.

（ａ）化合物１ａの合成
窒素雰囲気下、ベンゼンスルホン酸（Sigma−Aldrich社製、２１．７ｇ，１３７ｍｍｏｌ）のテトラヒドロフラン（ＴＨＦ）溶液（４００ｍＬ）に、ｎ−ブチルリチウム（関東化学製、１．５７Ｍヘキサン溶液，１７４ｍＬ，２７４ｍｍｏｌ）を０℃で加え、室温で３時間撹拌した。反応容器を−７８℃に冷却した後にクロロジイソプロピルホスフィン（Sigma-Aldrich社製，１９．０ｇ，１２５ｍｍｏｌ）を−７８℃で加え、室温で２．５時間撹拌した。反応をトリフルオロ酢酸（東京化成工業製、１５．６ｇ，１３７ｍｍｏｌ）で停止した後に、生じた沈殿をろ過によって回収し、減圧下乾燥して２−（ジイソプロピルホスフィノ）ベンゼンスルホン酸（2-(diisopropylphosphino)benzenesulfonic acid；化合物１ａ）を得た。収量は２６．８ｇ（７８％）であった。
¹Ｈ−ＮＭＲ（４００ＭＨｚ，ＣＤＣｌ₃）：δ 1.25 (d, J = 18.0 Hz, 6H), 1.53 (dd, J = 21.0, 6.6 Hz, 6H), 3.45 (br, 2H), 5.72 (br d, ¹J_PH = 380 Hz, 1H), 7.62-7.65 (m, 2H), 7.85 (br s, 1H), 8.29 (br s, 1H)。 [Synthesis of Metal Complex Catalyst 1]
Metal complex catalyst 1 was synthesized according to the following reaction scheme.

(A) Synthesis of Compound 1a Under a nitrogen atmosphere, n-butyllithium (manufactured by Kanto Chemical Co., Ltd., 1.57M) was added to a tetrahydrofuran (THF) solution (400 mL) of benzenesulfonic acid (Sigma-Aldrich, 21.7 g, 137 mmol). Hexane solution, 174 mL, 274 mmol) was added at 0 ° C., and the mixture was stirred at room temperature for 3 hours. After cooling the reaction vessel to −78 ° C., chlorodiisopropylphosphine (Sigma-Aldrich, 19.0 g, 125 mmol) was added at −78 ° C., and the mixture was stirred at room temperature for 2.5 hours. After the reaction was stopped with trifluoroacetic acid (Tokyo Chemical Industry Co., Ltd., 15.6 g, 137 mmol), the resulting precipitate was collected by filtration, dried under reduced pressure, and 2- (diisopropylphosphino) benzenesulfonic acid (2- ( diisopropylphosphino) benzenesulfonic acid; compound 1a) was obtained. The yield was 26.8 g (78%).
¹ H-NMR (400 MHz, CDCl ₃ ): δ 1.25 (d, J = 18.0 Hz, 6H), 1.53 (dd, J = 21.0, 6.6 Hz, 6H), 3.45 (br, 2H), 5.72 (br d, ¹ J _PH = 380 Hz, 1H), 7.62-7.65 (m, 2H), 7.85 (br s, 1H), 8.29 (br s, 1H).

(B) Synthesis of Complex 1b In an argon atmosphere, 2- (diisopropylphosphino) benzenesulfonic acid (Compound 1a) (16.3 g, 59.3 mmol) and diisopropylethylamine (Wako Pure Chemical Industries, Ltd.) (38.3 g, 296 mmol) in methylene chloride solution (200 mL), synthesized according to (cod) PdMeCl (“Rulke, RE et.al., Inor. Chem., 1993, 32, 5769-5778”. Cod = 1) , 5-cyclooctadiene, 16.3 g, 61.5 mmol) in methylene chloride (75 mL) was added, and the mixture was stirred at room temperature for 2.5 hours. After the solution was concentrated, the precipitate was removed by filtration and the solution was added into hexane. The resulting precipitate was collected by filtration, washed with hexane, and then dried under reduced pressure to obtain Complex 1b. Yield was 33.7 g (> 99%). The structure of Complex 1b was determined by ¹ H-NMR spectrum.
¹ H-NMR (400 MHz, CDCl ₃ ): δ 0.69 (s, 3H, PdCH ₃ ), 1.19-1.45 (m, 27H), 2.53 (sept, J = 7.1 Hz, 2H), 3.18 (br., 2H, HNCH ₂ CH ₃ ), 3.82 (br., 2H, HNCH (CH ₃ ) ₂ ), 7.42-7.59 (m, 3H), 8.22 (d, J = 3.6 Hz, 1H), 9.37 (br s, 1H, NH ).

(C) Synthesis of Metal Complex Catalyst 1 To a methylene chloride suspension (500 mL) of potassium carbonate (80.8 g, 585 mmol) and 2,6-lutidine (Tokyo Chemical Industry, 62.7 g, 585 mmol) in a nitrogen atmosphere. Then, a methylene chloride solution (200 mL) of complex 1b (33.7 g, 58.5 mmol) was added, and the mixture was stirred at room temperature for 2.5 hours. The solvent was distilled off under reduced pressure, and the remaining solid was extracted with methylene chloride. The extract was filtered through celite (dry diatomaceous earth) and slowly added into hexane (200 mL). The resulting precipitate was collected by filtration, washed with hexane, and then dried under reduced pressure to obtain metal complex catalyst 1. The yield was 27.6 g (94%).
¹ H-NMR (400 MHz, CDCl ₃ ): δ 0.35 (s, 3H, PdCH ₃ ), 1.28 (dd, J = 14.8, 6.8 Hz, 6H), 1.36 (dd, J = 17.4, 6.6 Hz, 6H), 2.54-2.63 (m, 2H), 3.18 (s, 6H, CH 3 of lutidine), 7.13 (d, J = 7.2 Hz, 2H), 7.45-7.61 (m, 4H), 8.31 (m, 1H).

Example 1: Copolymerization of ethylene / allyl acetate / 2,5-norbornadiene (Preparation of polymer 1)
In a nitrogen atmosphere, metal complex catalyst 1 (0.050 mmol) was dissolved in allyl acetate (75 mL, 70 g, allyl acetate 700 mmol and 2,5-norbornadiene 0.5 mmol) containing 750 ppm 2,5-norbornadiene, The solution was put into a 120 mL autoclave. After filling ethylene gas to a pressure of 4.0 MPa, the autoclave was stirred at 80 ° C. for 5 hours. After completion of the reaction, ethylene was depressurized and the polymerization reaction solution was cooled to room temperature, whereby a polymer was precipitated from the reaction solution. The reaction liquid, which is a polymer slurry solution, was suction filtered to recover the polymer 1 and dried under reduced pressure. The yield of the polymer 1 was 5.1 g, and the polymerization activity per unit time per catalyst was 20 g / (mmol-cat · h). The allyl acetate content of the polymer was calculated to be 4.1 mol% by ¹³ C-NMR spectrum using a reverse-coupled decoupling method. Moreover, it was number average molecular weight (Mn) 11,000, weight average molecular weight (Mw) 37,000, and polydispersity (Mw / Mn) 3.5 by size exclusion chromatography. The melting point was 102 ° C. and the crystallization temperature was 90 ° C. by DSC measurement. The infrared absorption spectrum of the polymer 1 is shown in FIG. 4, and the differential thermothermal weight simultaneous measurement (TG-DTA) chart is shown in FIG.
The catalytic activity was calculated by the following formula.

Example 2 Molecular Weight Fractionation of Polymer 1 by Soxhlet Extraction Polymer 1 obtained in Example 1 was subjected to molecular weight fractionation by a Soxhlet extraction method. That is, Soxhlet extraction was performed on polymer 1 (2.5 g) under heating and reflux of allyl acetate (200 mL). After heating and refluxing for 11 hours, the polymer (polymer 2) remaining without extraction was recovered and dried under reduced pressure. Its weight was 1.2 g. The infrared absorption spectrum of the polymer 2 is shown in FIG. 5, and the differential thermothermal weight simultaneous measurement (TG-DTA) chart is shown in FIG.
According to size exclusion chromatography, the number average molecular weight (Mn) was 43,000, the weight average molecular weight (Mw) was 90,000, and the polydispersity (Mw / Mn) was 2.1. ^{In the 13} C-NMR spectrum (FIGS. 1 and 2), peaks derived from the norbornane skeleton were observed at 48.0 ppm and 48.3 ppm, which revealed that the copolymer was incorporated with norbornadiene. In addition, in the infrared absorption spectrum (FIG. 5), absorption derived from a carbonyl group was observed at 1744 cm ⁻¹ , and it was found that the polymer 2 had units derived from allyl acetate equivalent to the polymer 1. Moreover, it is calculated from the ¹³ C-NMR spectrum using the decoupled method with a reverse gate that the unit derived from allyl acetate is 3.1% in molar ratio and the unit derived from norbornadiene is 0.26% in the polymer 2. It was done. The melting point was 93 ° C. and the crystallization temperature was 87 ° C. by DSC measurement.
From the above, it was confirmed that the polymers 1 and 2 obtained in Example 1 and Example 2 were ethylene / allyl acetate / 2,5-norbornadiene terpolymer.

Comparative Example 1 Copolymerization of Ethylene / Allyl Acetate Using the same method as in Example 1, ethylene and allyl acetate were copolymerized without adding 2,5-norbornadiene. Under a nitrogen atmosphere, a solution of metal complex catalyst 1 (0.050 mmol) in allyl acetate (75 mL, 70 g, 700 mmol) was charged into a 120 mL autoclave. After filling ethylene to 4.0 MPa, the autoclave was stirred at 80 ° C. for 5 hours. After completion of the reaction, ethylene was depressurized and the polymerization reaction solution was cooled to room temperature, whereby a polymer was precipitated from the reaction solution. The polymer was recovered by suction filtration of the reaction solution, which was a slurry solution of the polymer, and dried under reduced pressure. The yield of the polymer was 4.2 g, and the polymerization activity per unit time per catalyst was 17 g / (mmol-cat · h). The allyl acetate content of the polymer was calculated to be 4.5 mol% by ¹³ C-NMR spectrum using a reverse-coupled decoupling method. Moreover, it was number average molecular weight (Mn) 10,000, weight average molecular weight (Mw) 22,000, and polydispersity (Mw / Mn) 2.2 by size exclusion chromatography.

  From the above results, in the copolymerization of ethylene and allyl acetate, by adding 2,5-norbornadiene as the third monomer (Example 1), the polymerization activity is improved, and further the molecular weight of the copolymer obtained Was shown to increase.

Claims (10)

General formula (1), general formula (2), and general formula (3)

(In the formula, R ¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R ² represents —OH, —OCOR ^2-1 (R ^2-1 represents a hydrocarbon group having 1 to 5 carbon atoms, ^{represented), -. N (R 2-2} ) 2 (R 2-2 is a hydrogen atom, a hydrocarbon group having 1 to 5 carbon atoms, an aromatic residue having 6 to 18 carbon atoms, or -COOR, ^{2- 3} (R ^2-3 represents a hydrocarbon group having 1 to 10 carbon atoms or an aromatic residue having 6 to 10 carbon atoms), and two R ^2-2 may be the same or different. Or a halogen atom, each of the plurality of R ³ independently represents a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms, p represents 0 or an integer of 1 to 4, n, m and k are numerical values representing the molar ratio of each monomer unit.)
A polar group-containing allyl monomer copolymer having a monomer unit represented by: The molar ratios n, m, and k of the monomer units of general formula (1), general formula (2), and general formula (3) are:

The copolymer according to claim 1 satisfying   The copolymer according to claim 1 or 2, wherein the number average molecular weight Mn in terms of polystyrene is 7,000 to 1,000,000.   The copolymer in any one of Claims 1-3 which have only a monomer unit shown by General formula (1), General formula (2), and General formula (3).   In general formula (3), it is p = 0, The copolymer in any one of Claims 1-4. The monomer unit represented by the general formula (3) is derived from 2,5-norbornadiene in which all R ³ 's represent hydrogen atoms and p is 0. Coalescence. The monomer unit represented by the general formula (1) is derived from ethylene in which R ¹ represents a hydrogen atom, and the monomer unit represented by the general formula (2) is represented by R ^{2 in} the formula being —O—C ( = O) Derived from allyl acetate representing CH ₃ , the monomer unit represented by the general formula (3) is derived from 2,5-norbornadiene in which all R ³ in the formula represents a hydrogen atom and p is 0 The copolymer according to any one of claims 1 to 6. Formula (C1)

(In the formula, M represents a metal atom of Group 10 of the periodic table, X represents a phosphorus atom (P) or an arsenic atom (As), R ⁵ represents a hydrogen atom, or a halogen atom, an alkoxy group, an aryloxy group. And a hydrocarbon group having 1 to 30 carbon atoms which may be substituted with one or more groups selected from acyloxy groups, Y, R ⁶ and R ⁷ are each independently a hydrogen atom, an alkoxy group, An aryloxy group, a silyl group, an amino group, or a hydrocarbon group having 1 to 30 carbon atoms that may be substituted with one or more groups selected from a halogen atom, an alkoxy group, and an aryloxy group; ⁶ and R ⁷ may combine to form a ring structure, and Q represents Z [—S (═O) ₂ —O—] M, Z [—C (═O) —O—] M, Z [ “[]” Of —P (═O) (— OH) —O—] M or Z [—S—] M Represents a divalent group shown in the formula (wherein Z and M on both sides are described to indicate the bonding direction of the group), and Z represents a hydrogen atom, or a halogen atom, an alkoxy group, and an aryloxy group. Represents a hydrocarbon group having 1 to 40 carbon atoms which may be substituted with one or more groups selected from: Y and Z may combine to form a ring structure, and R ⁶ and / or R ⁷ may combine with Y to form a ring structure, L represents an electron-donating ligand, and q is 0, 1/2, 1 or 2.)
And a metal complex represented by the general formula (4)

(In the formula, R ¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.)
Olefin represented by general formula (5)

(Wherein R ² represents —OH, —OCOR ^2-1 (R ^2-1 represents a hydrocarbon group having 1 to 5 carbon atoms), —N (R ^2-2 ) ₂ (R ^2-2 Is a hydrogen atom, a hydrocarbon group having 1 to 5 carbon atoms, an aromatic residue having 6 to 18 carbon atoms, or -COOR ^2-3 (R ^2-3 is a hydrocarbon group having 1 to 10 carbon atoms, Or an aromatic residue having 6 to 10 carbon atoms), and two R ^2-2 may be the same or different.), Or a halogen atom.)
And an allyl compound represented by the general formula (6)

(In the formula, each of R ³ independently represents a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms, and p represents 0 or an integer of 1 to 4).
A method for producing a polar group-containing allyl monomer copolymer, which comprises copolymerizing a hydrocarbon compound having two carbon-carbon double bonds represented by formula (1). The catalyst represented by the general formula (C1) is represented by the general formula (C3).

(Wherein, four R ^{8 s} are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an aryloxy group having 6 to 18 carbon atoms, or Represents a halogen atom, and M, R ⁵ , R ⁶ , R ⁷ , L, and q have the same meaning as described in claim 8.)
The manufacturing method of the copolymer of Claim 8 shown by these. In general formula (C3), R ⁶ and R ⁷ both represent an isopropyl group, R ⁸ all represents a hydrogen atom, L represents 2,6-dimethylpyridine, q is 1, and M represents Pd. The method for producing a copolymer according to claim 9.

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