WO2007102227A1

WO2007102227A1 - Olefin block copolymer

Info

Publication number: WO2007102227A1
Application number: PCT/JP2006/304648
Authority: WO
Inventors: Rieko Ohtani; Makoto Mitani; Junji Saito; Yasuhiko Suzuki; Seiichi Ishii; Hiroshi Terao; Terunori Fujita
Original assignee: Mitsui Chemicals, Inc.
Priority date: 2006-03-09
Filing date: 2006-03-09
Publication date: 2007-09-13

Abstract

Disclosed are a block copolymer having different segments bound to one another and showing various useful physical properties and a process for producing the block copolymer with good efficiency. An olefin block copolymer comprising (i) a polymer block which is produced from at least one olefin selected from olefins having 2 to 20 carbon atoms and (ii) a polymer block which is produced from at least one olefin selected from olefins having 2 to 20 carbon atoms and is different from the polymer block (i), any adjacent polymer blocks being different from each other, the olefin block copolymer having an Mn (number average molecular weight) of 500 or higher and a Mw/Mn value (molecular weight distribution) of 1.5 or lower.

Description

Specification

Olefin block copolymer

Technical field

[0001] The present invention relates to an olefin block copolymer.

Background art

[0002] A block copolymer in which different segments are bonded exhibits various useful physical properties, and thus is very important not only from an academic standpoint but also from an industrial standpoint.

As a method for producing a polymer having such a specific structure, it is generally well known that living polymerization in which a termination reaction and a chain transfer reaction do not substantially occur during the polymerization is an effective method.

[0003] However, when a polymer having a specific structure as described above is produced, it grows when polymerization is carried out under ordinary conditions using a general Zieglar catalyst or a metalocene catalyst as an olefin polymerization catalyst. Since chain transfer reactions of polymer chains occur frequently, it was very difficult to produce olefin polymers by living polymerization. For example, when trying to synthesize a block copolymer using a known catalyst system, the ability to produce a mixture of homo and random copolymers has been clarified by analysis of molecular weight distribution, composition distribution, etc. (Boor, rziegl ar -Natta Catalyst ana Polymerization J, Academic Press, 1979

[0004] Under such circumstances, there have been several reports on the study of block copolymerization of olefins.

For example, a method using a specific metallocene catalyst has been proposed (see International Publication Nos. W091Z1 2285, WO94 / 21700, etc.). These methods also require low activity and low temperature polymerization (_10 ° C to 0 ° C), and it is described that the blocking efficiency decreases to less than 10% just by raising the polymerization temperature to 10 ° C. ing. Therefore, it is impossible to produce a block copolymer at a polymerization temperature (50 ° C to 75 ° C) which is usually used industrially. Furthermore, even in the case of low-temperature polymerization, the molecular weight distribution (Mw / Mn) of the block copolymer, which is an indicator of living polymerizability, is not as narrow as 1.35 or more, and it is not a well-controlled living polymerization. . Therefore, the product is almost always a by-product of large amounts of unblocked polymer. However, there are many restrictions in the industry, such as separation of removing unnecessary polymers in the post-treatment process.

[0005] For this reason, if a method capable of living polymerizing olefins with a high polymerization activity and a high polymerization force that can be produced industrially appears, the industrial value is extremely high. Under such circumstances, the present applicant has found a transition metal compound having a salicylaldimine ligand as a new catalyst for olefin polymerization. Among these transition metal compounds having a salicylaldimine ligand, those having a specific structure can be used at an industrially high temperature and at a very high activity compared to conventionally known living polymerization. Living polymerisation has progressed and the present invention has been completed by finding that a block copolymer can be produced. In addition, the inventors have invented a method for efficiently producing such a block copolymer and have completed the present invention.

Patent Document 1: International Publication No. 91/12285

Patent Document 2: International Publication No.94 / 21700

Special 3pm Reference 1: Boor, Ziegler-Natta Catalyst and Polymerization, Academic Press, 1979

Disclosure of the invention

Problems to be solved by the invention

That is, an object of the present invention is to provide a block copolymer in which different segments are bonded and exhibit various useful physical properties.

Means for solving the problem

[0007] The olefin block copolymer according to the present invention comprises (i) a polymer block obtained from at least one olefin selected from olefins having 2 to 20 carbon atoms, and (ii) 2 carbon atoms. Olefin block copolymer, comprising at least one selected from the above-described polymer block (i), and a polymer block different from the polymer block (i) obtained, and any adjacent polymer block different from each other The Mn (number average molecular weight) is 500 or more and the MwZMn (molecular weight distribution) is 1.5 or less.

[0008] Further, in the olefin block copolymer of the present invention, the polymer block is (a) a polymer block obtained from ethylene, and (b) ethylene, and having 4 to 12 carbon atoms. Nohi-o It is characterized by being a random copolymer block obtained from refin.

The invention's effect

In the method for producing an olefin block copolymer according to the present invention, it is possible to efficiently obtain an olefin block copolymer having a segment containing a large amount of olefin and having a narrow molecular weight distribution.

BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, the catalyst for olefin polymerization in the present invention and the method for polymerizing olefin using the catalyst will be specifically described.

The olefin block copolymer according to the present invention comprises (i) a polymer block obtained from at least one olefin selected from olefin having 2 to 20 carbon atoms, and (ii) 2 to 20 carbon atoms. And a polymer block different from the polymer block (i) to be obtained, and any adjacent polymer block is an olefin block copolymer different from each other. .

In addition, the olefin block copolymer according to the present invention has an Mn (number average molecular weight) of 500 or more and an MwZMn (molecular weight distribution) of 1.5 or less, preferably 1.3 or less. .

In the olefin block copolymer according to the present invention, the polymer block is composed of (a) a polymer block obtained from ethylene, and (b) ethylene and a 4-olefin having 12 to 12 carbon atoms. It is a random copolymer block obtained.

[0012] The olefin block copolymer according to the present invention is preferably a diblock copolymer.

The polymer block (b) is preferably obtained from ethylene and one kind of olefins selected from α-olefins having 6 to 10 carbon atoms.

Such an olefin block copolymer is excellent in impact resistance, moldability, tensile strength, ductility, blocking resistance, elasticity, rigidity, and film-forming properties, so it can be used in films, sheets, professional molded products, etc. It is suitably used for various molding materials, various additives such as compatibilizers and modifiers, paints and adhesives.

[0013] Further, the olefin block copolymer according to the present invention comprises:

(Ii) a transition metal compound represented by the following general formula (I): (B) (Bl) organometallic compound,

(B-2) an organoaluminum compound, and

(B-3) transition metal compound (A) is polymerized by an olefin polymerization catalyst characterized by comprising at least one compound selected from compounds that react with (A) to form ion pairs. As a special lacquer floor

[Chemical 1]

(In the formula, 示し represents a titanium atom, m represents an integer of 1 to 2, R ¹ represents a fluorine-containing hydrocarbon group having 1 to 30 carbon atoms, and R ^{2 to} R ⁵ represent each other. R ⁶ represents a hydrocarbon group, a hydrogen atom or a hydrocarbon-substituted silyl group which may be the same or different, and two or more of these may be connected to each other to form a ring. A group selected from the following four groups: hydrogen, an aliphatic hydrocarbon group, a monocyclic alicyclic hydrocarbon group and an aromatic hydrocarbon group; and in the case of m force ¾, R ^{2 to} R ⁶ 2 may be linked among the groups represented by n is a number satisfying the valence of M, and X is a hydrogen atom, a halogen atom, a hydrocarbon group, an oxygen-containing group, or a x-containing group. Group, nitrogen-containing group, boron-containing group, aluminum-containing group, phosphorus-containing group, halogen-containing group, heterocyclic compound residue, silicon-containing group, germanium In the case where n is 2 or more, a plurality of groups represented by X may be the same as or different from each other, and a plurality of groups represented by X are bonded to each other. A ring may be formed. [(A) Transition metal compounds]

The (A) transition metal compound used in the present invention is a compound represented by the following general formula (I).

[Chemical 2]

[0017] (Note that N... M is generally a force indicating coordination. In the present invention, N may or may not be coordinated.)

In general formula (I), M is a titanium atom.

m represents an integer of 1 to 2, and is preferably 2. R ¹ represents a fluorine-containing hydrocarbon group having 1 to 30 carbon atoms, R ^{2 to} R ⁵ represent a hydrocarbon group, a hydrogen atom or a hydrocarbon-substituted silyl group which may be the same or different from each other, R ⁶ represents a group selected from the four basic forces of hydrogen, an aliphatic hydrocarbon group, a monocyclic alicyclic hydrocarbon group, and an aromatic hydrocarbon group, and two or more of these are selected. They may be connected to each other to form a ring.

[0018] Specific examples of the fluorine-containing hydrocarbon group having 1 to 30 carbon atoms of R ¹ include trifluoromethyl, perfluoroethyl, perfluoropropyl, perfluorobutyl, perfluoropentyl, Perfluoro mouth hexyl, monofluorophenyl, difluorophenyl, trifluorophenol, tetrafluorophenyl, pentafluorophenyl, (trifluoromethylenoyl) phenyl, trifluoromethylphenyl, bis (trifluoromethyl) phenyl, tris ( Trough Norreolomethinole) phenyl, tetrakis (trifluoromethyl) phenyl, pentakis (trifluoromethinole) phenyl, (trifluoromethyl) tetrafluorophenyl, perfluoroethenophenyl, bis (perfluoroethinole) phenyl, perfluoropropyl Enil, perfolenorobutinorefeninore, perfnoreo pentinorefueninore, nofnoreohexenorephenyl, bis (perfluohexahexenole) phenyl, perfluoronaphtyl, norfluoro-nantrenyl, perfluo And loanthracenyl.

[0019] Preferably, R ¹ is a C6-C30 aromatic hydrocarbon group having a fluorine substituent or a fluorine-containing hydrocarbon substituent, and specifically, monofluorophenyl, difluorophenyl, trifluoro Phenyl, tetrafluorophenyl, pentafluorophenyl, (trifluoromethylolenyl) phenyl, trifluoromethylphenyl, bis (trifluoromethinole) phenyl, tris (trifluoromethylenole) phenyl, tetrakis (trifluoromethyl) Tinole) phenyl, pentakis (trifluoromethyl) phenyl, (trifluoromethyl) tetrafluorophenyl, monofluorophenyl, bis (perfluoroethyl) phenyl, perfluoropropylphenyl, perfluoro Robutyl phenyl, perfluoropentyl phenyl, Cyclohexyl phenyl to Furuo port (Kishinore to Pafuruo port) bis phenyl, Pafuruorona Fuchiru, perfluoro phenanthrenyl, PA Full O Rohan tiger cell sulfonyl, and the like et be.

More preferably, R ¹ is an aromatic hydrocarbon group having 6 to 30 carbon atoms having two or more substituents selected from the group consisting of a fluorine substituent or a fluorine-containing hydrocarbon substituent, and specifically, Is difluorophenyl, trifluorophenyl, tetrafluorophenyl, pentafluororerophenyl, (trifluoromethyl) phenyl, bis (trifluoromethyl) phenyl, tris (trifluoromethylenole) phenyl, tetrakis (trifluoromethyl) Tinole) funil, pentakis (trifluoromethyl) phenyl, (trifluoromethyl) tetrafluorophenyl, bis (perfluoroethyl) phenyl, bis (perfluorohexyl) phenyl, and the like.

[0021] Particularly preferably, R ¹ is a difluorophenyl group, a trifluorophenyl group, a tetrafluorophenyl group, a pentafluorophenyl group, or (trifluoromethyl) tetrafluorophenyl. In this case, 2, 6-difluorophenyl group, 2, 4, 6_ trifluorophenyl group, pentafluorophenyl group, 4- (trifluoromethyl) -2, 3, 5, 6- Specific examples include tetrafluorophenyl.

[0022] Examples of the hydrocarbon group represented by R ^{2 to} R ⁵ include those having carbon numbers of! To 30. Specifically, the number of carbon atoms such as methinole, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s_butyl, t-butyl, neopentyl, n-hexyl, etc. is 1 to 30, preferably Is a linear or branched alkyl group having 1 to 20; a linear or branched alkenyl group having 2 to 30, preferably 2 to 20 carbon atoms, such as bur, aryl, i-propenyl; A straight chain or branched alkenyl group having 2 to 30 carbon atoms, preferably 2 to 20 carbon atoms such as ethur, pargyl, etc .; carbon atoms such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, norbornyl, adamantyl, etc. A cyclic saturated hydrocarbon group having 3 to 30, preferably 3 to 20 carbon atoms; a cyclic unsaturated hydrocarbon group having 5 to 30 carbon atoms such as cyclopentadenyl, indul, and fluorenyl; phenyl, benzyl, naphthyl, biphenyl Arylenoyl groups having 6-30 carbon atoms, preferably 6-20 carbon atoms such as phenyl, terphenyl, phenanthryl, anthracenyl; tolyl, i_propylphenyl, t-butylphenyl, dimethylphenyl, di-t-butylphenyl, etc. And alkyl-substituted aryl groups.

[0023] The hydrocarbon group may be substituted with another hydrocarbon group, and examples thereof include aryl group-substituted alkyl groups such as benzyl and Tamyl.

Examples of the hydrocarbon-substituted silyl group represented by R ^{2 to} R ⁵ include groups having a total carbon number of 1 to 30. Specific examples include methylsilyl, dimethylsilyl, trimethylsilyl, ethylsilinole, jetylsilyl, triethylsilyl, diphenylmethylsilyl, triphenylsilyl, dimethylphenylsilyl, dimethyl-t-butylsilyl, dimethyl (pentafluorophenyl) silyl, etc. Is mentioned. Among these, methylsilyl, dimethylsilyl, trimethylsilylole, ethylsilyl, jetylsilyl, triethynolesilyl, dimethylphenylsilyl, triphenylsilyl and the like are preferable. Particularly preferred are trimethylsilyl, triethylsilyl, triphenylsilyl, and dimethylphenylsilyl.

[0024] Examples of the aliphatic hydrocarbon group R ^6, for example, those having 1 to 4 carbon atoms. Specifically, straight chain having 1 to 4, preferably 1 to 3 carbon atoms such as methinole, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, etc. Or a branched alkyl group. Examples of the monocyclic alicyclic hydrocarbon group represented by R ⁶ include those having 3 to 30 carbon atoms. Specific examples thereof include monocyclic alicyclic hydrocarbon groups having 3 to 30, preferably 3 to 8, carbon atoms such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cyclooctyl.

[0025] Examples of the aromatic hydrocarbon group for R ⁶ include those having 6 to 30 carbon atoms. Specific examples include aromatic hydrocarbon groups having 6 to 30 carbon atoms, such as phenyl, naphthyl, biphenylyl, triphenylyl, fluorenyl, anthranolinole, phenanthryl.

n is a number satisfying the valence of M, specifically an integer of 2 to 4, and preferably 2.

[0026] X represents a hydrogen atom, a halogen atom, a hydrocarbon group, an oxygen-containing group, a thio-containing group, a nitrogen-containing group, a boron-containing group, an aluminum-containing group, a phosphorus-containing group, a halogen-containing group, a heterocyclic compound residue A group, a silicon-containing group, a germanium-containing group, or a tin-containing group. When n is 2 or more, a plurality of groups represented by X may be the same or different from each other, and a plurality of groups represented by X are bonded to each other to form a ring. Also good.

[0027] Examples of the hydrogen atom and the rogen atom include fluorine, chlorine, bromine and iodine.

Examples of the hydrocarbon group include the same groups as those exemplified above for R ^{2 to} R ⁵ . Specifically, alkyl groups such as methylol, ethyl, propyl, butyl, hexyl, octyl, noel, dodecyl, eicosyl; cycloalkyl having 3 to 30 carbon atoms such as cyclopentyl, cyclohexyl, norbornyl, and adamantyl Groups; alkenyl groups such as vinyl, propenyl, cyclohexenyl; arylalkyl groups such as benzyl, phenylethyl, phenylpropyl; phenyl, trinole, dimethylphenyl, trimethylphenyl, ethylphenyl, propylphenyl, biphenyl And allyl groups such as naphthyl, methylnaphthyl, anthryl, phenanthryl, and the like. These hydrocarbon groups also include halogenated hydrocarbons, specifically, groups in which at least one hydrogen of a hydrocarbon group having 1 to 20 carbon atoms is substituted with halogen.

[0028] The heterocyclic compound residue includes nitrogen-containing compounds such as pyrrole, pyridine, pyrimidine, quinoline and triazine, oxygen-containing compounds such as furan and pyran, and sulfur-containing compounds such as thiophene. Examples thereof include residues such as compounds, and groups obtained by further substituting substituents such as alkyl groups and alkoxy groups having carbon atoms:! To 30, preferably 1 to 20, to these heterocyclic compound residues.

[0029] Specific examples of the oxygen-containing group include hydroxy groups; alkoxy groups such as methoxy, ethoxy, propoxy, and butoxy; aryloxy groups such as phenoxy, methylphenoxy, dimethylphenoxy, and naphthoxy; phenylmethoxy, Forces including aryloxy groups such as phenylethoxy; acetoxy groups; carbonyl groups and the like.

[0030] Specific examples of the thio-containing group include methyl sulfonate, trifluoromethane sulfonate, phenyl sulfonate, benzyl sulfonate, p-toluene sulfonate, trimethylbenzene sulfonate, trimethyl sulfonate. Sulfonate groups such as i-butylbenzene sulfonate, p-chlorobenzene sulfonate, pentafluorobenzene sulfonate; methinores norefinate, phenenoles norefinate, pendinoles norefinate , Sulfinate groups such as p-tonolene sulfinate, trimethylbenzene sulfinate, pentafluorobenzene sulfinate; alkylthio groups; arylthio groups and the like, but not limited thereto.

[0031] Specific examples of nitrogen-containing groups include amino groups; alkylamino groups such as methylamino, dimethylamino, jetylamino, dipropylamino, dibutylamino, dicyclohexylamino, etc .; phenylamino, diphenylamino, ditolylamino, dinaphthylamino, methylphenylamino, etc. A force such as an arylarylamino group or an alkylarylamino group is not limited thereto.

[0032] Specific examples of the boron-containing group include BR (R represents hydrogen, an alkyl group, an aryl group which may have a substituent, a halogen atom, or the like).

Specific examples of phosphorus-containing groups include trialkylphosphine groups such as trimethylphosphine, tributylphosphine, and tricyclohexylphosphine; triarylphosphine groups such as triphenylphosphine and tolylphosphine; methyl phosphite, ethyl phosphite, phenyl Examples thereof include, but are not limited to, phosphite groups (phosphide groups) such as ruphosphite; phosphonic acid groups; phosphinic acid groups. [0033] Specific examples of the silicon-containing group include fuel silyl, diphenyl silyl, trimethylsilinole, triethinoresilinole, triprovirsilyl, tricyclohexylsilyl, triphenylsilyl, methyldiphenylsilyl, tritolylsilyl, tritriol. Examples thereof include hydrocarbon-substituted silanol groups such as naphthylsilyl; hydrocarbon-substituted silyl ether groups such as trimethylsilyl ether; silicon-substituted alkyl groups such as trimethylsilinolemethyl;

[0034] Specific examples of the germanium-containing group include groups obtained by substituting the silicon of the above-described group containing a group with germanium.

Specific examples of the tin-containing group include groups obtained by substituting the key of the above-mentioned key-containing group with tin.

Specific examples of halogen-containing groups include fluorine-containing groups such as PF and BF, ClO, and SbCl.

6 4 4 6 Which chlorine-containing groups, iodine-containing groups such as 10

Four

There is no.

[0035] Specifically, as the aluminum-containing group, AIR (R has hydrogen, an alkyl group, and a substituent.

Four

A force such as a aryl group or a halogen atom) is not limited thereto.

The preferred structure and structure of the transition metal compound (A) used in the present invention includes the general formula (I) wherein M is a titanium atom, m is 2, and R ¹ is at least two or more fluorine substituents. It is preferably an aromatic hydrocarbon group having 6 to 30 carbon atoms having R ¹ is a difluorophenyl group, a trifluorophenyl group, a tetrafluorophenyl group, or a pentafluorophenyl group, and R ⁶ is a linear or branched alkyl group of:! To 3 or 3 to 8 A monocyclic hydrocarbon group or an aromatic hydrocarbon group having 6 to 30 carbon atoms is particularly preferable.

[0036] Specific examples of the transition metal compound represented by the general formula (I) are shown below, but are not limited thereto.

[0037] [Chemical 3]

In the above examples, Me represents a methyl group, Et represents an ethyl group,! ”Represents an i-propyl group, ¾ιι represents a t-butyl group, and Ph represents a phenyl group.

The method for producing such a transition metal compound (A) is not particularly limited and can be produced, for example, as follows. First, the ligand constituting the transition metal compound (A) is a salicylaldehyde compound, a primary amin compound of the formula Ι ^ -ΝΗ (R ¹ is as defined above), for example, an aniline Conversion

2

It can be obtained by reacting with a compound or an alkylamine compound. Specifically, both starting compounds are dissolved in a solvent. As the solvent, those commonly used in such a reaction can be used, and among them, alcohol solvents such as methanol and ethanol, and hydrocarbon solvents such as toluene are preferable. The resulting solution is then stirred for about 1 to ₄₈ hours at room temperature to reflux conditions to give the corresponding ligand in good yield. When synthesizing the ligand compound, an acid catalyst such as formic acid, acetic acid or toluenesulfonic acid may be used as a catalyst. In addition, when molecular sieves, magnesium sulfate or sodium sulfate is used as a dehydrating agent, or dehydration is performed using a Dean-Stark trap, it is effective for the progress of the reaction.

Next, a corresponding transition metal compound can be synthesized by reacting the thus obtained ligand with a transition metal salt-containing compound. Specifically, the synthesized ligand is dissolved in a solvent and brought into contact with a base as necessary to prepare a phenoxide salt, and then mixed with a metal compound such as a metal halide or metal alkylate at a low temperature. Stir at _78 ° C to room temperature or under reflux conditions for about:! To 48 hours. As the solvent, among those capable of using ordinary solvents for such a reaction, polar solvents such as ether and tetrahydrofuran (THF), hydrocarbon solvents such as toluene and the like are preferably used. In addition, the base used in preparing the phenoxide salt is preferably a metal salt such as a lithium salt such as n-butyllithium, a sodium salt such as sodium hydride, or an organic base such as triethylamine or pyridine. Not as long.

[0040] Depending on the properties of the compound, the corresponding transition metal compound can be synthesized by directly reacting the ligand and the metal compound without going through the preparation of the phenoxide salt. It is also possible to exchange the metal M in the compound with another transition metal by a conventional method. Also for example! When any of ^ to is H, substituents other than H can be introduced at any stage of the synthesis.

[0041] Further, without isolating the transition metal compound, the reaction solution of the ligand and the metal compound is left as it is. It can also be used for polymerization.

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

[(B-1) Organometallic compounds]

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

[(B-2) Organoaluminum oxide compound]

The (B-2) organoaluminum compound used in the present invention may be a conventionally known aluminoxane or a benzene-insoluble organoaluminum compound as exemplified in JP-A-2-78687. Kissy compound may be used.

[(B-3) Compounds that react with transition metal compounds (A) to form ion pairs]

As the compound (B-3) (hereinafter referred to as “ionized ionic compound”) that reacts with the transition metal compound (A) used in the present invention to form an ion pair, 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. The ability to list Lewis acids, ionic compounds, borane compounds and carborane compounds. Furthermore, heteropoly compounds and isopoly compounds can also be mentioned.

[0042] Specific examples include ionized ionic compounds described in Japanese Patent Application No. 2002-311685.

When the transition metal compound (A) according to the present invention is used as a catalyst, when it is used in combination with an organoaluminum oxide compound (B-2) such as methyl aluminoxane as a promoter component, the olefin compound is greatly reduced. High polymerization activity. When an ionized ionic compound (B-3) such as triphenylcarbontetrakis (pentafluorophenyl) borate is used as a promoter component, an olefin polymer having good activity and a very high molecular weight can be obtained.

[0043] The olefin polymerization catalyst used for the polymerization of the olefin block copolymer according to the present invention may be (A) the transition metal compound represented by (I) may be used alone,

(A) the transition metal compound represented by (I),

(B) (B-1) an organometallic compound, (B-2) an organoaluminum compound, and

(B-3) Ionized ionic compounds

In this case, these compounds are formed in the polymerization system.

[Chemical 4]

Are formed.

(In the formula, shaku ¹ ~! ^ ⁶ , M, m, n, X are the same as (I), and Y is a so-called weakly coordinating anion.)

In this formula, the bond between metals M and Y can be covalently bonded, or can be ionic, or can be ionic bonded. Specific examples of 1 ^ to 1 ⁶ , M, m, n, and X in the formula are the same as (I). Examples of Y include Chemical Review Journal 88 卷 1405 (1988), Chemical Review Journal 93 卷 927 pages (1993), WO98 / 30612 6 page, weakly coordinating anions are mentioned. Specifically, AIR— (R can be one kind or two or more kinds of oxygen atoms, nitrogen atoms , Rinhara

Four

Oxygen atom, nitrogen atom, phosphorus atom, hydrogen atom, halogen atom in a hydrogen atom, a halogen atom or a substituent containing them, and an aliphatic hydrocarbon group, aromatic hydrocarbon group, alicyclic hydrocarbon group It has a substituent that contains les, may les,) BRR― (R is one or two

Four

Oxygen atom, nitrogen atom, phosphorus atom, hydrogen atom, halogen atom or so Substituents containing these, and aliphatic hydrocarbon groups, aromatic hydrocarbon groups, and alicyclic hydrocarbon groups having an oxygen atom, nitrogen atom, phosphorus atom, hydrogen atom, or halogen atom. Or PF-, SbF-, trifluoromethanesulfonate, p-tolu

6 5

Examples include ensulfonate.

[0046] Also, the catalyst for olefin polymerization according to the present invention includes the transition metal compound (A), (B-1) an organometallic compound, (B-2) an organoaluminum oxide compound, and (B-3). A carrier (C) as described later can be used as necessary together with at least one compound (B) selected from ionic compounds.

[(C) Carrier]

The carrier (C) used in the present invention is an inorganic or organic compound and is a granular or particulate solid.

[0047] Specific examples include inorganic or organic compounds described in Japanese Patent Application No. 2002-311685.

The catalyst for olefin polymerization used for the polymerization of the olefin block copolymer according to the present invention includes the transition metal compound (A), (B-1) an organometallic compound, (B-2) an organoaluminum oxy compound, And (B-3) at least one compound (B) selected from ionic and ionic compounds, and optionally a carrier (C) and, if necessary, specific organic compound components (D ) Can also be included.

[(D) Organic compound component]

In the present invention, the organic compound component (D) is used for the purpose of improving the polymerization performance and the physical properties of the produced polymer, if necessary. Such organic compounds include, but are not limited to, alcohols, phenolic compounds, carboxylic acids, phosphorus compounds and sulfonates.

[0048] Specific examples include organic compounds described in Japanese Patent Application No. 2002-311685.

FIG. 1 and FIG. 2 show steps for preparing the olefin polymerization catalyst according to the present invention. In the polymerization, the method of using each component and the order of addition are arbitrarily selected, and the following methods are exemplified.

(1) A method in which component (A) is added alone to the polymerization vessel.

(2) A method in which component (A) and component (B) are added to the polymerization vessel in any order. (3) A method in which the component (A) is supported on the carrier (C) and the component (B) is added to the polymerization vessel in any order.

(4) A method in which the component (B) is supported on the carrier (C) and the component (A) is added to the polymerization vessel in any order.

(5) A method of adding a catalyst component in which component (A) and component (B) are supported on a carrier (C) to a polymerization vessel

[0049] In each of the above methods (2) to (5), at least two or more of the catalyst components may be contacted in advance.

In each of the above methods (4) and (5) in which the component (B) is supported, the unsupported component (B) may be added in any order as necessary. In this case, the components (B) may be the same or different.

[0050] The solid catalyst component in which the component (A) is supported on the component (C) and the solid catalyst component in which the component (A) and the component (B) are supported on the component (C) A catalyst component may be further supported on the prepolymerized solid catalyst component that is polymerized and re-polymerized. The olefin block copolymer according to the present invention is a catalyst for olefin polymerization as described above. (A) polymerization of a polymer block obtained from ethylene, and then (b) copolymerization of ethylene and a random copolymer block obtained from α-olefin linker having 4 to 12 carbon atoms. Is obtained.

[0051] The polymerization of the olefin block copolymer according to the present invention includes (b) a random copolymer block obtained from ethylene and an α-olefin having 4 to 12 carbon atoms, and then (a) ) Polymerization of polymer blocks obtained from ethylene, then (b) ethylene and 4 to 4 carbon atoms

It may be carried out in the order of copolymerization of random copolymer blocks obtained from 12 olefins.

[0052] In the present invention, the polymerization can be carried out even if liquid phase polymerization methods such as solution polymerization and suspension polymerization or gas phase polymerization methods are used.

Specific examples of the inert hydrocarbon medium used in the liquid phase polymerization method include fats such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene. Aromatic hydrocarbons such as cyclopentane, cyclohexane, and methylcyclopentane; Aromatic hydrocarbons such as benzene, toluene, and xylene; Halogenated hydrocarbons such as ethylene chloride, chlorobenzene, and dichloromethane or these It is possible to use a mixture of these materials, and olefins themselves can be used as a solvent.

[0053] Using the Orefin polymerization catalyst as described above, when performing polymerization of Orefin, Ingredient (A) is, per liter of the reaction volume, usually 10- ¹² ~ 10- ² mol, preferably 10- ^1Q ~: used in an amount such that ^10-3 molar.

Component (B-1) is a molar ratio [(B-1) / M] force between component (B-1) and all transition metal atoms (M) in component (A). Usually 0.01 to 100000 Preferable <is used in an amount such that 0.05 to 50000. Component (B-2) is a monolayer of aluminum atom in component (B-2) and transition metal atom (M) in component (A): 匕 [(B_2) / M], usually 10 ~ The amount used is 500000, preferably 20 to 100000. Component (B-3) contains component (B-3) and component (transition metal atom (M) in A molar ratio [(B-3) / M] force usually:! -10, preferably 1 Used in such an amount that it becomes ~ 5.

[0054] When the component (B) is the component (B-1), the component (D) has a molar ratio [(D) / (B-1)] of usually 0 · 01 to 10, preferably 0. When component (B) is component (B-2) in such an amount as 1 to 5, monole]; 匕 [(D) / (B-2)] force S Normal 0.001 to 2 When the component (B) is the component (B-3), the molar ratio [(D) / (B-3)] is usually 0. It is used in an amount such that 01 :: 10, preferably 0 ·:!-5.

[0055] The polymerization temperature of olefin using such an olefin polymerization catalyst is usually in the range of -50 to + 200 ° C, preferably 0 to 170 ° C. The polymerization pressure is usually from normal pressure to 100 kg / cm ² , preferably from normal pressure to 50 kg / cm ² , and the polymerization reaction can be carried out in batch, semi-continuous, or continuous methods. You can do it.

EXAMPLES Hereinafter, the present invention will be described more specifically based on examples, but the present invention is not limited to these examples.

[0056] In this example, Mn (number average molecular weight) and Mw / Mn (molecular weight distribution) of the obtained copolymer were measured using GPC (gel permeation chromatography) and orthodichlorobenzene. It was measured at 140 ° C with a solvent. The molecular weight of the resulting copolymer is The molecular weight in terms of ethylene was converted into a polyethylene equivalent value by the universal method. Further, the melting point of the obtained polymer was measured using a differential thermal analyzer (DSC) under a nitrogen stream under a temperature rising condition of 10 ° C./min.

[Example 1]

A glass autoclave with an internal volume of 500 ml that had been thoroughly purged with nitrogen was charged with 250 ml of Tonolene, and the liquid phase and gas phase were saturated with ethylene, and then only the gas phase was purged with nitrogen. Polymerization was started by adding 2.5 mmol of methylaluminoxane in terms of aluminum atom, and subsequently adding 0.02 mmol of titanium compound (1) (a synthesis example is described in JP-A No. 2004-2640). After 5 minutes of reaction at 25 ° C and complete consumption, 10 ml of 1-hexene was added and reacted for 5 minutes while blowing ethylene gas (50 liters of Zh). A small amount of methanol was added to stop the reaction, and the reaction product was added to 1 liter of methanol containing a small amount of hydrochloric acid to precipitate the copolymer. The copolymer was filtered, washed with methanol, and dried under reduced pressure at 130 ° C. for 10 hours to obtain 2.193 g of copolymer. The resulting copolymer had an Mn (number average molecular weight) of 80,000, an Mw / Mn (molecular weight distribution) of 1.26, and a 1-hexene content measured by IR of 6.0 monole. %Met. 1 - (hexene copolymer component of ethylene '1) - molecular weight and the total copolymer first Niburo click component calculated from hexene content to 1 in hexene content was 10.4 mol ^_0/0 . The polymerization conditions and results are shown in (Table 1).

[Chemical 5]

[Examples 2 to 3]

Polymerization was carried out in the same manner as in Example 1 except that the polymerization time and the monomer were changed as shown in (Table 1). The polymerization conditions and results are shown in (Table 1).

[0059] [Table 1]

Industrial applicability

The olefin block copolymer of the present invention is excellent in impact resistance, moldability, tensile strength, ductility, blocking resistance, elasticity, rigidity and film-forming properties. It is expected to make significant industrial contributions in the field of seed additives, paints and adhesives.

Claims

The scope of the claims

[1] (i) a polymer block obtained from at least one olefin selected from olefins having 2 to 20 carbon atoms, and (ii) at least one olefin selected from olefins having 2 to 20 carbon atoms. An olefin block copolymer containing a polymer block different from the polymer block (i) obtained from the above, and any adjacent polymer blocks different from each other, and Mn (number average molecular weight) is An olefin block copolymer characterized by having a molecular weight distribution of 500 or more and a MwZMn (molecular weight distribution) of 1.5 or less.

[2] The polymer block is (a) a polymer block obtained from ethylene, and (b) a random copolymer block obtained from ethylene and α-olefin having 4 to 12 carbon atoms. 2. The olefin block copolymer according to claim 1, wherein