JP7224212B2 - Olefin polymer and method for producing the same - Google Patents

Description

TECHNICAL FIELD The present invention relates to an olefin polymer containing a large number of olefin polymers having unsaturated bonds at one end.

Polyolefins (olefin polymers) represented by polyethylene and polypropylene require little energy for production, are lightweight, and have excellent recyclability. Reuse, Recycle) is gaining more attention. Polyolefins are used in various fields such as daily necessities, kitchen utensils, packaging films, home electric appliances, machine parts, electric parts, and automobile parts.

By introducing functional groups such as double bonds, hydroxyl groups, and carboxyl groups to the main chain and ends of polyolefins to add reactivity with other monomers and polymers, development of new applications that take advantage of the characteristics of polyolefins. can be expected. In particular, polyolefins having terminal functional groups are expected to create new substances having various functionalities while making the most of the properties of the polymer main chain.

A polymer decomposition method is known as a method for producing linear polyolefins having terminal functional groups. For example, it has been reported that a polypropylene oligomer having vinylidene groups at both ends can be obtained by pyrolyzing polypropylene under appropriate conditions (see, for example, Patent Documents 4 and 5, Non-Patent Documents 2 and 3, etc.). ). As another decomposition method, a method of synthesizing a polymer having vinyl groups at both ends by decomposing polybutadiene or the like in the presence of a functional group-containing olefin with a metathesis catalyst is also known (see, for example, Non-Patent Documents 4 to 6). . However, in such a polymer decomposition method, a polyolefin having one terminal functional group cannot be obtained, and if an attempt is made to increase the introduction rate of the functional group, only a low molecular weight in the oligomer region can be obtained, and the bulk properties of polyolefin can be fully exhibited. There was a drawback that it did not reach.

Furthermore, in both the polymer decomposition method and the metathesis polymerization method, the molecular weight distribution (Mw/Mn) was around 2, and a polyolefin with a narrow molecular weight distribution (Mw/Mn) could not be synthesized.

As a method for producing a linear polyolefin having a functional group at one end, the present applicant has proposed a method for producing a novel copolymer containing a vinyl group at one end by using a transition metal compound having a salicylaldimine ligand. has been proposed (Patent Document 6). However, the obtained polyolefin had a number molecular weight of less than 3,000 and a molecular weight distribution (Mw/Mn) of 1.5 or more, and it was not possible to synthesize a polyolefin having a high molecular weight and a narrow molecular weight distribution (Mw/Mn). As another production method, Non-Patent Document 7 discloses vinyl end group-containing polyethylene, but it has the drawback that only low molecular weight oligomer regions with a number average molecular weight of 2,000 or less can be obtained.

It is generally well known that a method utilizing living polymerization is effective as a method for producing a polymer having a high molecular weight and a narrow molecular weight distribution (Mw/Mn). In the case of highly controlled living polymerization, the propagating terminal of the polymer retains reactivity quantitatively. Polymers can be made with functional groups at terminal positions.

However, when olefins are polymerized by living polymerization, the chain transfer reaction of growing polymer chains frequently occurs under normal conditions, making it extremely difficult to produce olefin polymers by living polymerization. Several examples of living polymerization of α-olefins have been reported so far, but in order to control the chain transfer reaction, the polymerization was carried out at extremely low temperatures, the polymerization activity was low, and the molecular weight was low. It was in the tens of thousands at most. In addition, in many cases, the number of polymerizable monomers is limited, and it has been difficult to produce industrially important ethylene-based (co)polymers and block copolymers (for example, see Non-Patent Document 1, etc.). ).

Under such circumstances, the present applicant has already disclosed a transition metal compound having a salicylaldimine ligand as a new olefin polymerization catalyst (see Patent Document 1), and furthermore, using the transition metal compound, living polymerization is performed. have proposed a method for producing a novel polyolefin containing a single terminal functional group (see Patent Documents 1 and 2). However, the above two publications do not disclose a polymer having a vinyl group at one end or a production method thereof.

JP-A-11-315109 JP 2005-097588 A JP 2009-155655 A International Publication No. 2013/039152 pamphlet WO 2002/042340 pamphlet JP 2003-073412 A

"Polymers", 1988, (2), 74-77 Macromolecules, 28, 7973 (1995) Polymer Journal, 28, 817 (1996) Macromolecules, 28, 1333 (1995) Macromol. Chem. Phys. , 215, 1140 (2014) Makromol. Chem. Rapid Commun. , 14, 323 (1993) Angew. Chem. Int. Ed. , 54, 4631 (2015)

The problem to be solved by the present invention is that the above problems are solved, that is, the introduction rate of terminal groups is high and the content of olefin chains (molecules) having an unsaturated bond at one end is high, and further, An object of the present invention is to provide an olefin-based polymer having a high molecular weight and a narrow molecular weight distribution (Mw/Mn) and useful in various applications.

That is, the present invention is an olefin polymer containing 80% or more of the total number of molecules of the olefin polymer (V) having an unsaturated bond at one end, which is useful in various applications, and has the following requirements ( The present invention relates to an olefin polymer characterized by satisfying 1) to (4).
(1) containing an olefin polymer (V) having an unsaturated bond at one end represented by general formula (I),
PX (I)
[In the above formula (I), P represents an olefin-derived polymer chain composed only of carbon atoms and hydrogen atoms, X represents a structure containing a structural unit derived from a non-conjugated polyene, and is bound to the end of P. ing. ]
(2) the number of molecules of the olefin polymer (V) represented by the general formula (I) is 80 mol% or more with respect to the total number of molecules contained in the olefin polymer;
(3) the number average molecular weight (Mn) of the olefinic polymer determined by gel permeation chromatography (GPC) is 3,000 or more;
(4) The molecular weight distribution (Mw/Mn) of the olefinic polymer determined by gel permeation chromatography (GPC) is 1.5 or less.

According to the present invention, it is possible to provide an olefin polymer containing a large number of olefin polymers (V) having a high molecular weight and a narrow molecular weight distribution and having an unsaturated bond at one end, and a method for producing the olefin polymer. can.

The present invention will be described in detail below.
The present invention is an olefin polymer that satisfies the following requirements (1) to (4).
(1) PX containing an olefin polymer (V) having an unsaturated bond at one end represented by general formula (I) (I)
[In the above formula (I), P represents an olefin-derived polymer chain composed only of carbon atoms and hydrogen atoms, X represents a structure containing a structural unit derived from a non-conjugated polyene, and is bound to the end of P. ing. ]
(2) the number of molecules of the olefin polymer (V) represented by the general formula (I) is 80 mol% or more with respect to the total number of molecules contained in the olefin polymer;
(3) the number average molecular weight (Mn) of the olefinic polymer determined by gel permeation chromatography (GPC) is 3,000 or more;
(4) The molecular weight distribution (Mw/Mn) of the olefinic polymer determined by gel permeation chromatography (GPC) is 1.5 or less.

In the present invention, "olefin polymer" is a general term including various "olefin polymers", and the olefin polymer of the present invention is "olefin polymer (V)" having an unsaturated bond at one end. contains a large number of and partly contains an "olefin polymer" that does not have a functional group at the end.

These requirements (1) to (4) will be specifically described below.
Requirement (1)
In general formula (I), X is a group showing a structure containing structural units derived from non-conjugated polyene, and X is bonded to the terminal of P. The non-conjugated polyene is preferably a non-conjugated polyene having one or more carbon-carbon double bonds in one molecule that can be polymerized by an olefin polymerization catalyst. More specifically, the following aliphatic polyenes and alicyclic family polyenes.

Examples of aliphatic polyenes include 1,4-hexadiene, 1,4-pentadiene, 1,5-hexadiene, 1,5-heptadiene, 1,6-heptadiene, 1,6-octadiene, 1,7-octadiene, 1,7-nonadiene, 1,8-nonadiene, 1,8-decadiene, 1,9-decadiene, 1,10-undecadiene, 1,11-dodecadiene, 1,12-tridecadiene, 1,12-tetradecadiene, 1,13-tetradecadiene, 3-methyl-1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 4-ethyl-1,4-hexadiene, 3, 3-dimethyl-1,4-hexadiene, 5-methyl-1,4-heptadiene, 5-ethyl-1,4-heptadiene, 5-methyl-1,5-heptadiene, 6-methyl-1,5-heptadiene, 5-ethyl-1,5-heptadiene, 4-methyl-1,4-octadiene, 5-methyl-1,4-octadiene, 4-ethyl-1,4-octadiene, 5-ethyl-1,4-octadiene, 5-methyl-1,5-octadiene, 6-methyl-1,5-octadiene, 5-ethyl-1,5-octadiene, 6-ethyl-1,5-octadiene, 6-methyl-1,6-octadiene, 7-methyl-1,6-octadiene, 6-ethyl-1,6-octadiene, 6-propyl-1,6-octadiene, 6-butyl-1,6-octadiene, 4-methyl-1,4-nonadiene, 5-methyl-1,4-nonadiene, 4-ethyl-1,4-nonadiene, 5-ethyl-1,4-nonadiene, 5-methyl-1,5-nonadiene, 6-methyl-1,5-nonadiene, 5-ethyl-1,5-nonadiene, 6-ethyl-1,5-nonadiene, 6-methyl-1,6-nonadiene, 7-methyl-1,6-nonadiene, 6-ethyl-1,6-nonadiene, 7-ethyl-1,6-nonadiene, 7-methyl-1,7-nonadiene, 8-methyl-1,7-nonadiene, 7-ethyl-1,7-nonadiene, 5-methyl-1,4-decadiene, 5-ethyl-1,4-decadiene, 5-methyl-1,5-decadiene, 6-methyl-1,5-decadiene, 5-ethyl-1,5-decadiene, 6-ethyl-1,5-decadiene, 6-methyl-1,6-decadiene, 6-ethyl-1,6-decadiene, 7-methyl-1,6-decadiene, 7-ethyl-1,6-decadiene, 7-methyl-1,7- Decadiene, 8-methyl-1,7-decadiene, 7-ethyl-1,7-decadiene, 8-ethyl-1,7-decadiene, 8-methyl-1,8-decadiene, 9-methyl-1,8- Decadiene, 8-ethyl-1,8-decadiene, 6-methyl-1,6-undecadiene, 9-methyl-1,8-undecadiene, α,ω such as 1,7-octadiene and 1,9-decadiene - contains a diene.

Examples of alicyclic polyenes include tetrahydroindene; 5-methylene-2-norbornene, 5-ethylidene-2-norbornene, 5-propylidene-2-norbornene, 5-butylidene-2-norbornene, 5-vinyl-2- norbornene; 5-alkenyl-2-norbornenes such as 5-allyl-2-norbornene; 2,5-norbornadiene, dicyclopentadiene (DCPD), bicyclo-(2.2.1)-hepta-2,5-diene ( 2,5-norbornadiene), tetracyclo[4,4,0,12.5,17.10]deca-3,8-diene, 2-methyl-2,5-norbornadiene, 2-ethyl-2,5-norbornadiene , vinylcyclohexene, 1,4-cyclohexadiene, 1,5-cyclooctadiene, 1,7-cyclododecadiene and the like.

These non-conjugated polyenes include 1,4-pentadiene, 1,5-hexadiene, 1,6-heptadiene, 1,7-octadiene, 1,8-nonadiene, 1,9-decadiene, 1,10-undecadiene, 1 , 11-dodecadiene, 1,12-tridecadiene, 1,13-tetradecadiene, tetrahydroindene, bicyclo-(2.2.1)-hepta-2,5-diene, dicyclopentadiene, 5-methylene-2- More preferred are norbornene, 5-ethylidene-2-norbornene, 5-vinyl-2-norbornene, vinylcyclohexene, 1,4-cyclohexadiene, 1,5-cyclooctadiene, and 1,7-cyclododecadiene.

In particular, 5-vinyl-2-norbornene and 5-ethylidene-2-norbornene are more preferable from the viewpoint of reactivity.
In the general formula (I), the polymer chain P represents a polymer chain mainly composed of olefin composed only of carbon atoms and hydrogen atoms. In such an olefin polymer chain, all repeating units composed of structural units derived from at least one selected from ethylene and olefins having 3 to 20 carbon atoms, preferably ethylene-derived repeating units are contained in the main chain 50 to 100 mol%, more preferably 70 to 95 mol%, relative to the unit, and 0 to 50 mol%, more preferably 0 to 50 mol%, relative to all repeating units containing olefin-derived repeating units having 3 to 20 carbon atoms in the main chain is preferably 5 to 30 mol % of the polyolefin polymer chain [provided that the total olefin content is 100 mol %].

Examples of olefins having 3 to 20 carbon atoms include propylene, 1-butene, 2-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3- Linear or branched α having 3 to 20 carbon atoms such as methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene and 1-eicosene - olefins; cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclododecene, 2-methyl 1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a - Cyclic olefins having 3 to 20 carbon atoms such as octahydronaphthalene; vinylcyclohexane can also be mentioned as olefins having 3 to 20 carbon atoms.

The olefins used in the present invention are preferably olefins having 3 to 10 carbon atoms, more preferably olefins having 3 to 8 carbon atoms, still more preferably 3 to 4 carbon atoms, particularly preferably 3 carbon atoms. is an olefin of Specifically, linear olefins such as propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, and 1-decene, 4-methyl-1-pentene, 3-methyl-1-pentene, Branched olefins such as 3-methyl-1-butene can be mentioned, among which propylene, 1-butene, 1-pentene, 1-hexene and 1-octene are preferred, propylene and 1-butene are more preferred, and propylene is Especially preferred.

Furthermore, as olefins, aromatic vinyl compounds such as styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, o,p-dimethylstyrene, o-ethylstyrene, m-ethylstyrene, p-ethylstyrene, etc. mono- or polyalkylstyrenes; and 3-phenylpropylene, α-methylstyrene, and the like. These olefins can be used alone or in combination of two or more.

Requirement (2)
In the olefinic polymer of the present invention, the number of molecules of the olefinic polymer (V) represented by the general formula (I) having an unsaturated bond at one end is 80 mols with respect to the total number of molecules contained in the olefinic polymer. % or more, preferably 90 mol% or more, and 20 mol% or less, preferably 10 mol% or less, of the total number of molecules contained in the olefin polymer is an olefin polymer having no terminal functional group. is. The content of the olefin polymer (V) having terminal unsaturated bonds can be measured using ¹ H-NMR and high temperature gel permeation chromatography (GPC)-viscosity method.

Satisfying the above range means that the olefinic polymer of the present invention contains an olefinic polymer (V) having an unsaturated bond at one end represented by the general formula (I) in a sufficient proportion. The desired effect can be obtained sufficiently. By using an olefin polymerization catalyst containing a preferable transition metal compound (A) described later, the terminal unsaturated bond derived from X does not contribute to the reaction during the polymerization reaction, and it is easy to adjust the above range.

[Calculation of content of olefin polymer (V) having unsaturated bond at one end]
The signals around 4.8 and 5.7 ppm in ¹ H-NMR originate from hydrogens bonded to the α and β carbons of the terminal vinyl groups, the 0.8 ppm signal originates from the side chain methyl group of propylene, Signals between 0.8 and 1.6 ppm are from ethylene. Each signal intensity was corrected to the absolute molecular weight, and the content of the olefin polymer having an unsaturated bond at one end was calculated from the signal intensity of the terminal vinyl group with respect to the main chain. The absolute molecular weight can be calculated by high temperature gel permeation chromatography (GPC)-viscosity method or the like.

Requirement (3)
The olefin polymer of the present invention has a number average molecular weight (Mn) of 3,000 or more, preferably 5,000 or more, more preferably 10,000 or more, particularly preferably 30,000 or more.

An olefinic polymer having a number average molecular weight of less than 3,000 has little entanglement of molecular chains and does not exhibit properties as a polymer. Weight average molecular weight and number average molecular weight can be measured using a high temperature gel permeation chromatography (GPC)-viscosity method.

In the high-temperature gel permeation chromatography (GPC)-viscosity method, monodisperse polystyrene with a molecular weight of 590 to 3,840,000 is used as a standard sample, and standard polystyrene (IV = 1.01) is used for viscosity calibration. The number average molecular weight Mn was calculated by analyzing the chromatogram by the method of No.

Requirement (4)
The olefinic polymer of the present invention has a molecular weight distribution (Mw/Mn) determined by gel permeation chromatography (GPC) in the range of 1.0 to 1.5, preferably 1.0 to 1.3. is. When the molecular weight distribution (Mw/Mn) is within the above range, it can be said that the polymer has a uniform molecular weight. Mn) can be said to be in a relatively small range, so that the reactivity of the terminal functional groups is uniform. The molecular weight distribution (Mw/Mn) can be measured using the high temperature gel permeation chromatography (GPC)-viscosity method described above. By using an olefin polymerization catalyst containing the preferred transition metal compound (A) described later, the terminal unsaturated bond derived from X does not contribute to the reaction during the polymerization reaction, and the molecular weight distribution (Mw/Mn) is within the above range. Easy to adjust.

Method for Producing Olefin Polymer The method for producing an olefin polymer of the present invention comprises the steps described below in the presence of an olefin polymerization catalyst containing a transition metal compound (A) represented by the following general formula (II): can be obtained efficiently by sequentially performing

（式中、Ｍは周期表第４～５族から選ばれる遷移金属原子を示し、ｍは１または２を示し、Ｒ₁は芳香族炭化水素基、脂肪族炭化水素基または脂環族炭化水素基であって、フェニル基の場合には、窒素に結合した炭素原子の位置を１位としたときに、２位および６位の少なくとも１箇所にヘテロ原子もしくはヘテロ原子含有基から選ばれる１種以上の置換基を有しているか、または３位、４位および５位の少なくとも１箇所にフッ素原子を除くヘテロ原子、１個の炭素原子および２個以下のフッ素原子を含有するフッ素含有基、２個以上の炭素原子を含有するフッ素含有基、フッ素原子を除くヘテロ原子を含有する基から選ばれる少なくとも１種の置換基を有しており、フェニル基以外の芳香族炭化水素基、脂肪族炭化水素基または脂環族炭化水素基の場合には、ヘテロ原子、ヘテロ原子含有基から
選ばれる少なくとも１種の置換基を有しており、Ｒ₂～Ｒ₅は、互いに同一でも異なっていてもよく、水素原子、ハロゲン原子、ハロゲン含有基、炭化水素基、炭化水素置換シリル基、酸素含有基、窒素含有基またはイオウ含有基を示し、Ｒ₆は１つまたは複数の置換基を有していてもよいフェニル基、１つまたは複数の置換基を有していてもよいナフチル基、１つまたは複数の置換基を有していてもよいビフェニル基、１つまたは複数の置換基を有していてもよいターフェニル基および１つまたは複数の置換基を有していてもよいフェナントリル基から選ばれる基を示し、ｎは、Ｍの価数を満たす数であり、Ｘは、酸素原子、水素原子、ハロゲン原子、炭化水素基、酸素含有基、イオウ含有基、窒素含有基、ホウ素含有基、アルミニウム含有基、リン含有基、ハロゲン含有基、ヘテロ環式化合物残基、ケイ素含有基、ゲルマニウム含有基またはスズ含有基を示し、Ｘで示される複数の基は互いに結合して環を形成してもよく、またｎが２以上の場合は、Ｘで示される複数の基は互いに同一でも異なっていてもよい。）
以下に、上記一般式（ＩＩ）で表される遷移金属化合物（Ａ）の具体的な例を示すが、これら化合物に限定されるものではない。

(Wherein, M represents a transition metal atom selected from Groups 4 and 5 of the periodic table, m represents 1 or 2, R ₁ represents an aromatic hydrocarbon group, an aliphatic hydrocarbon group or an alicyclic hydrocarbon In the case of a phenyl group, one selected from heteroatoms or heteroatom-containing groups at least one of the 2- and 6-positions when the position of the carbon atom bonded to nitrogen is the 1-position. a fluorine-containing group having the above substituents or containing a hetero atom other than a fluorine atom at at least one of the 3-, 4- and 5-positions, 1 carbon atom and 2 or less fluorine atoms; It has at least one substituent selected from a fluorine-containing group containing two or more carbon atoms and a group containing a heteroatom excluding a fluorine atom, and has an aromatic hydrocarbon group other than a phenyl group, an aliphatic A hydrocarbon group or an alicyclic hydrocarbon group has at least one substituent selected from heteroatoms and heteroatom-containing groups, and R ₂ to R ₅ may be the same or different. may also represent a hydrogen atom, a halogen atom, a halogen-containing group, a hydrocarbon group, a hydrocarbon-substituted silyl group, an oxygen-containing group, a nitrogen -containing group or a sulfur-containing group, and R ₆ has one or more substituents . a phenyl group optionally having one or more substituents, a naphthyl group optionally having one or more substituents , a biphenyl group optionally having one or more substituents , one or more substituents a group selected from a terphenyl group optionally having substituents and a phenanthryl group optionally having one or more substituents , n is a number satisfying the valence of M, X is an oxygen atom, hydrogen atom, halogen atom, hydrocarbon group, oxygen-containing group, sulfur-containing group, nitrogen-containing group, boron-containing group, aluminum-containing group, phosphorus-containing group, halogen-containing group, heterocyclic compound residue; , a silicon-containing group, a germanium-containing group or a tin-containing group, and a plurality of groups represented by X may be bonded to each other to form a ring, and when n is 2 or more, a plurality of groups represented by X The groups may be the same or different.)
Specific examples of the transition metal compound (A) represented by the general formula (II) are shown below, but are not limited to these compounds.

以上のような遷移金属化合物（Ａ）は、１種単独または２種以上組み合わせて用いられる。

The above transition metal compounds (A) are used singly or in combination of two or more.

[Compound (B)]
[(B-1) Organometallic compound]
As the organometallic compound (B-1) used in the present invention, specifically, organometallic compounds of Groups 1 and 2 and Groups 12 and 13 of the periodic table described in Japanese Patent Application No. 2002-311685 are used.

[(B-2) Organic aluminum oxy compound]
The organoaluminumoxy compound (B-2) used in the present invention may be a conventionally known aluminoxane, or a benzene-insoluble organoaluminumoxy compound as exemplified in JP-A-2-78687. may

[(B-3) Compound that forms an ion pair by reacting with transition metal compound (A)]
As the compound (B-3) (hereinafter referred to as "ionized ionic compound") that reacts with the transition metal compound (A) to form an ion pair used in the present invention, JP-A-1-501950, JP-A-1-502036, JP-A-3-179005, JP-A-3-179006, JP-A-3-207703, JP-A-3-207704, USP-5321106, etc. Examples include Lewis acids, ionic compounds, borane compounds and carborane compounds. In addition, heteropolycompounds and isopolycompounds may also be mentioned. Specific examples include the ionized ionic compound described in Japanese Patent Application No. 2002-311685.

Conventionally known aluminoxanes can be produced, for example, by the following method, and are usually obtained as a solution in a hydrocarbon solvent.
(1) Compounds containing adsorbed water or salts containing water of crystallization, such as magnesium chloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate, nickel sulfate hydrate, cerous chloride hydrate, etc. A method of adding an organoaluminum compound such as trialkylaluminum to the hydrocarbon medium suspension of (1) and reacting the adsorbed water or water of crystallization with the organoaluminum compound.
(2) A method in which water, ice or steam is directly acted on an organoaluminum compound such as trialkylaluminum in a medium such as benzene, toluene, ethyl ether or tetrahydrofuran.
(3) A method of reacting an organoaluminum compound such as trialkylaluminum with an organotin oxide such as dimethyltin oxide or dibutyltin oxide in a medium such as decane, benzene or toluene.

Specific examples of organoaluminum compounds used for preparing aluminoxanes include tri-n-alkyls such as trimethylaluminum, triethylaluminum, tri-n-butylaluminum, tripropylaluminum, tripentylaluminum, trihexylaluminum and trioctylaluminum. Aluminum; tri-branched alkylaluminum such as triisopropylaluminum, triisobutylaluminum, trisec-butylaluminum, tri-2-ethylhexylaluminum; tricycloalkylaluminum such as tricyclohexylaluminum, tricyclooctylaluminum; triphenylaluminum, tritolyl triarylaluminum _such as aluminum; represented by (i- _C4H9 )xAly( _C5H10 )z (wherein x, y, and z are positive numbers and z≧2x) _; Among them, trialkylaluminum and tricycloalkylaluminum are preferred, and trimethylaluminum is particularly preferred. Also, the above organoaluminum compounds may be used singly or in combination of two or more.

In the production method according to the present invention, the transition metal compound (A), the organometallic compound (B-1), the organoaluminumoxy compound (B-2), and the transition metal compound (A) are reacted to form an ion pair. It is also possible to coexist with at least one selected from a compound (B-3) that forms a, a carrier, and an organic compound.

In the present invention, polymerization can be carried out by either a liquid phase polymerization method such as solution polymerization or suspension polymerization, or a gas phase polymerization method.
Specific examples of inert hydrocarbon media used in the liquid phase polymerization method include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; cyclopentane, cyclohexane, and methylcyclopentane. Aromatic hydrocarbons such as benzene, toluene, and xylene; Halogenated hydrocarbons such as ethylene chloride, chlorobenzene, and dichloromethane, or mixtures thereof. can also

When producing the terminally functionalized polyolefins according to the present invention in the presence of the aforementioned catalysts, the operations consisting of steps 1 and 2 are usually carried out without isolating the products of each step. In addition, the catalyst is generally charged all at once when the first step 1 is started. The transition metal compound (A) is generally used in an amount of 10 ^-12 to 1 mol, preferably 10 ^-10 to 10 ^-1 mol, per liter of reaction volume. The organoaluminumoxy compound (B) has a molar ratio (Al/M) of aluminum atoms in the component (B) to transition metal atoms (M) in the transition metal compound (A), which is usually 10 to 500,000. , preferably from 50 to 100,000.

When an organometallic compound, a compound that reacts with the transition metal compound (A) to form an ion pair, a carrier, and an organic compound as optional components are used in combination, the amount used is determined in the above-mentioned JP-A-11-315109. The amount described in is charged.

The olefinic polymer of the present invention is obtained by performing the following steps 1 and 2 in an arbitrary order in the presence of an olefin polymerization catalyst. That is, the olefinic resin of the present invention can be obtained by [i] performing steps 1 and 2 in this order, or [ii] performing steps 2 and 1 in this order.
[Step 1] A step of contact-mixing a non-conjugated polyene.
[Step 2] A step of contact-mixing ethylene and at least one olefin selected from olefins having 3 to 20 carbon atoms.

The amount of the non-conjugated polyene added in step 1 is not particularly limited, but when performing steps 1 and 2 in this order, an excess of 1.0 to 1.2 equivalents is added to the number of moles of the polymerization catalyst. A molar amount is sufficient. If the amount of non-conjugated polyene added is less than 1.0 equivalent, the terminal functionalization rate will be low. If the amount of the non-conjugated polyene added exceeds 1.2 equivalents, it is not preferable because unsaturated bonds may be introduced not only at the terminals but also at the side chains of the polymer chains. When step 2 and step 1 are carried out in this order, it is preferably 10 equivalents or more, more preferably 50 equivalents or more, relative to the number of moles of the polymerization catalyst. If the amount of the non-conjugated polyene added is less than 10 equivalents, the terminal functionalization rate will be low, which is not preferred.

Step 1 can be completed by contacting at -20 to 50°C, preferably 0 to 40°C, for 1 to 300 minutes, preferably 5 to 200 minutes.
In step 2, the polymerization reaction proceeds by contacting at -20 to 50°C, preferably 0 to 40°C, for 1 to 600 minutes, preferably 3 to 180 minutes. The pressure in step 2 is usually normal pressure to 100 kg/cm ² , preferably normal pressure to 50 kg/cm ² , and the polymerization reaction can be carried out either batchwise or continuously. When a continuous system is employed, a tubular flow reactor is preferable from the viewpoint of controlling the molecular weight distribution, and a batch system is particularly preferable in the present invention. Furthermore, the polymerization can be carried out in two or more stages with different reaction conditions.

The olefinic polymer containing a large number of olefinic polymers (V) having unsaturated bonds at one end of the present invention can be used in various applications. For example, it is expected to be applied as a raw material for functionalization, as a macromonomer for synthesizing graft polymers, block polymers, and poly(macromonomers), and as a material for controlling physical properties of crosslinked products.

EXAMPLES The present invention will be specifically described below based on examples, but the present invention is not limited to these examples.
The structures of the polymers obtained in the examples were determined using ¹ H-NMR, high temperature GPC-viscometry. Various measurement and calculation methods are described.

[Composition ratio of each monomer]
The composition ratio of each monomer was measured using a Bruker Biospin AVANCE IIIcryo-500 nuclear magnetic resonance apparatus under the following conditions. The main measurement conditions are as follows.
・Solvent: ortho-dichlorobenzene- _d4
- Sample concentration: ca. 33 g/l-solvent
・Pulse repetition time: 7.0 seconds ・Integration times: 64 times ・Measurement temperature: 120°C
・Measurement nucleus: ¹ H (500 MHz)

In the above ¹ H-NMR spectrum, the 0.8 ppm signal originates from the side chain methyl group of propylene, and the 0.8-1.6 ppm signal originates from ethylene. The composition ratio of each monomer was quantified from each signal intensity.

[Molecular weight measurement]
Molecular weights and molecular weight distributions were determined using high temperature GPC-viscometry. The main measurement conditions are as follows.
Apparatus: high-temperature GPC apparatus PL-GPC220 type (manufactured by Polymer Laboratories)
Detector: Bridge type viscometer PL-BV400 type with built-in differential refractometer/GPC device (manufactured by Polymer Laboratories)
Column: TSKgel GMHHR-H (S) HT × 2 + TSKgel GMHHR-M (S) × 1 (manufactured by Tosoh Corporation, inner diameter 7.8 mmφ × length 300 mm per column)
Temperature: 140°C
Mobile phase: 1,2,4-trichlorobenzene (containing 0.025% BHT)
Injection volume: 0.5 mL
Sample concentration: 1.0 mg/mL
Sample filtration: Filtration with a sintered filter with a pore size of 1.0 μm

In the above, as a standard sample necessary for determining the absolute molecular weight, monodisperse polystyrene (manufactured by Tosoh Corporation, molecular weight 590 to 3,840,000) as a standard sample, standard polyethylene (NIST1475a IV = 1.01) for viscosity calibration. Using.

[Calculation of content of olefin polymer (V) having unsaturated bond at one end]
The signals around 4.8 and 5.7 ppm in ^{the 1} H-NMR are derived from hydrogens bonded to the α and β carbons of the terminal vinyl groups, and the 0.8 ppm signal is derived from the side chain methyl group of propylene. , 0.8-1.6 ppm signals originate from ethylene. From each signal intensity, the strength ratio of the terminal vinyl group to the main chain is determined, and the absolute molecular weight measured by the high-temperature GPC-viscometry is used to determine the content of the olefin polymer (V) having an unsaturated bond at one end. was calculated.

[Example 1]
250 mL of toluene and 3.0 mmol of methylaluminoxane in terms of aluminum atoms were charged into a glass reactor having an internal volume of 500 mL which was sufficiently purged with nitrogen. 0.010 mmol of 5-vinyl-2-norbornene was added thereto. 0.010 mmol of a titanium compound whose structural formula is represented by the following formula was added and reacted at 25° C. for 10 minutes. After that, a mixed gas of ethylene, propylene and nitrogen at normal pressure (gas flow rate ethylene: 15 L/h; propylene: 15 L/h; nitrogen: 70 L/h) was blown into the reactor and reacted at 25°C for 5 minutes, Polymerization was stopped by adding methanol. After stopping the polymerization, the reactant was poured into 750 mL of methanol containing a small amount of hydrochloric acid to precipitate the entire amount of the polymer, and the polymer was collected by filtration. The polymer was dried under reduced pressure at 80° C. for 12 hours to obtain 0.172 g of polymer. The polymerization activity per 1 mmol of titanium was 17.2 g, and the ratio of propylene-derived structures in the polymer determined by ¹ H-NMR was 18 mol %. Other analysis results are shown in Table 1.

[Comparative Example 2]
0.135 g of polymer was obtained in the same manner as in Example 1 except that the catalyst was changed to a titanium compound represented by the following structural formula and the polymerization conditions were changed to 25° C. for 2 minutes. The polymerization activity per 1 mmol of titanium was 13.5 g. Also, the ratio of propylene-derived structures in the polymer determined by ¹ H-NMR was 6 mol %. Other analysis results are shown in Table 1.

As shown in Table 1, the olefin polymer of Example 1 has a content of the olefin polymer (V) having an unsaturated bond at one end of 80% or more, and the number average molecular weight (Mn) of the olefin polymer is 3,000 or more, and the molecular weight distribution (Mw/Mn) of the olefinic polymer is 1.5 or less, so that it can be applied to various uses. The olefinic polymer of Comparative Example 1 showed inferior results in terms of the content of the olefinic polymer (V) having an unsaturated bond at one end and the narrow molecular weight distribution (Mw/Mn).

An olefin polymer containing a large number of polymers having a functional group at one end can be used for various purposes as it is, and the vinyl group at one end is highly reactive. Useful in a variety of applications.

Claims (6)

An olefin polymer characterized by satisfying the following requirements (1) to (4).
(1) containing an olefin polymer (V) having an unsaturated bond at one end represented by general formula (I),
PX (I)
[In the above formula (I), P represents an olefin-derived polymer chain composed only of carbon atoms and hydrogen atoms, and X represents a structural unit derived from 5-ethylidene-2-norbornene or 5-vinyl-2-norbornene. , attached to the P end. ]
(2) the number of molecules of the olefin polymer (V) represented by the general formula (I) is 80 mol% or more with respect to the total number of molecules contained in the olefin polymer;
(3) the number average molecular weight (Mn) of the olefinic polymer determined by gel permeation chromatography (GPC) is 3,000 or more;
(4) The molecular weight distribution (Mw/Mn) of the olefinic polymer determined by gel permeation chromatography (GPC) is 1.5 or less. 2. The olefin polymer according to claim 1, wherein the polymer chain (P) is composed of at least one olefin selected from ethylene and olefins having 3 to 20 carbon atoms. A transition metal compound (A) represented by the following general formula (II), (B-1) an organometallic compound, (B-2) an organoaluminum oxy compound, and (B-3) a transition metal compound (A) 3. An olefin characterized by producing the olefin polymer according to claim 1 or 2 in the presence of an olefin polymerization catalyst containing at least one compound (B) selected from compounds that react to form an ion pair. A method for producing a system polymer.

(Wherein, M represents a transition metal atom selected from Groups 4 and 5 of the periodic table, m represents 1 or 2, R ₁ represents an aromatic hydrocarbon group, an aliphatic hydrocarbon group or an alicyclic hydrocarbon In the case of a phenyl group, one selected from heteroatoms or heteroatom-containing groups at least one of the 2- and 6-positions when the position of the carbon atom bonded to nitrogen is the 1-position. a fluorine-containing group having the above substituents or containing a hetero atom other than a fluorine atom at at least one of the 3-, 4- and 5-positions, 1 carbon atom and 2 or less fluorine atoms; It has at least one substituent selected from a fluorine-containing group containing two or more carbon atoms and a group containing a heteroatom excluding a fluorine atom, and has an aromatic hydrocarbon group other than a phenyl group, an aliphatic A hydrocarbon group or an alicyclic hydrocarbon group has at least one substituent selected from heteroatoms and heteroatom-containing groups, and R ₂ to R ₅ may be the same or different. may also represent a hydrogen atom, a halogen atom, a halogen-containing group, a hydrocarbon group, a hydrocarbon-substituted silyl group, an oxygen-containing group, a nitrogen -containing group or a sulfur-containing group, and R ₆ has one or more substituents . a phenyl group optionally having one or more substituents, a naphthyl group optionally having one or more substituents , a biphenyl group optionally having one or more substituents , one or more substituents a group selected from a terphenyl group optionally having substituents and a phenanthryl group optionally having one or more substituents , n is a number satisfying the valence of M, X is an oxygen atom, hydrogen atom, halogen atom, hydrocarbon group, oxygen-containing group, sulfur-containing group, nitrogen-containing group, boron-containing group, aluminum-containing group, phosphorus-containing group, halogen-containing group, heterocyclic compound residue; , a silicon-containing group, a germanium-containing group or a tin-containing group, and a plurality of groups represented by X may be bonded to each other to form a ring, and when n is 2 or more, a plurality of groups represented by X The groups may be the same or different.) In the transition metal compound (A) represented by the general formula (II), M is a titanium atom, m is 2, and R ₆ is a phenyl group optionally having one or more substituents. The method for producing an olefin polymer according to claim 3 . In the transition metal compound (A) represented by the general _formula (II), a hetero atom or 5. The method for producing an olefin polymer according to claim 3 , wherein the phenyl group has one or more substituents selected from heteroatom-containing groups. The olefin-based polymer according to claim 1 or 2 obtained by performing the following steps 1 and 2 in any order in the presence of the olefin polymerization catalyst according to any one of claims 3 to 5 . A method for producing an olefinic polymer, characterized by producing a coalescence.
[Step 1] A step of contact-mixing 5-ethylidene-2-norbornene or 5-vinyl-2-norbornene .
[Step 2] A step of catalytically mixing ethylene and at least one olefin selected from olefins having 3 to 20 carbon atoms.