JP4139341B2 - High modulus polyolefin fiber, method for producing the same, and stretch-molded body - Google Patents

Description

The present invention relates to a method for producing an olefin-based polymer for obtaining solid-phase extrusion drawing or high-strength, high-modulus fiber by drawing after rolling. More specifically, an olefin polymerization catalyst containing a transition metal compound and a specific organoaluminum oxy compound, a method for producing an ultrahigh molecular weight olefin polymer using the catalyst, and an ultrahigh molecular weight olefin polymer thus obtained are solidified. The present invention relates to phase extrusion stretching, a method for producing high-strength and high-modulus fibers that are stretched after rolling, and the resulting high-strength and high-modulus fibers. The rolling referred to here includes roll rolling industrially.

Conventionally, ultra-high molecular weight polyethylene has the highest impact strength among polyolefins, and has excellent wear resistance, chemical resistance, and low specific gravity. Industrial materials and industrial materials, various guides and spacers, linings, sports It is used for articles, especially high-strength fiber applications. Previously, Smith et al. Found that high-strength polyethylene fibers were obtained by extruding at low temperature using a so-called polyethylene virgin polymer. Thereafter, polyethylene materials for high-strength fibers were invented by JP-A-63-41512, JP-A-63-66207, etc., but Ti and V were also used as the central metal. On the other hand, recent research results on polyolefin polymerization catalysts having high activity and high stereoregularity include already industrialized metallocene catalysts and post-metallocene catalysts described in JP-A-2000-128931, among which olefins have high polymerization activity. As a catalyst capable of producing a polymer or an olefin copolymer, an olefin polymerization catalyst comprising a transition metal compound such as zirconocene and an organic aluminum oxy compound (aluminoxane) is known (Patent Documents 1 to 3).

As a result of intensive studies under these circumstances, the present inventors have found that the catalyst and polymerization method in the present invention are excellent as a resin for high-strength, high-modulus polyethylene fibers, and have been identified as a specific catalyst. The present invention has been completed by using this polymerization method. Furthermore, it became clear that the use of the ultrahigh molecular weight polyethylene having a narrow molecular weight distribution by using the polymerization method according to the present invention makes it possible to achieve higher strength than that of conventional polyethylene. It has been found that this is an excellent method for obtaining high-strength fibers.

JP-A-63-41512 JP-A 63-66207 JP 2000-128931 A

The present invention provides a high-strength, high-modulus ultrahigh-molecular-weight polyolefin resin for fibers, films, or sheets characterized by solid-phase extrusion stretching at a temperature lower than the melting point of the polymer, and further stretching after rolling. It is an object to provide a method and a method for producing a fiber as well as a fiber.

The high modulus polyolefin fiber according to the present invention is
In the particulate carrier,
(A) a transition metal compound represented by the following general formula (I);
(B) an organic aluminum oxy-compound is obtained by using an olefin polymerization catalyst comprising a solid catalyst component comprising supported, intrinsic viscosity is obtained from the ultra-high molecular weight olefin polymer 5~50dl / g, modulus Is 120 GPa or more .

（ 式中、Ｍはチタン、ジルコニウムまたはハフニウムを示し、ｍは、２を示し、Ｒ¹〜
Ｒ⁶は、互いに同一でも異なっていてもよく、水素原子または炭化水素基を示し、ｎは、
Ｍの価数を満たす数であり、Ｘは、水素原子、ハロゲン原子または炭化水素基を示し、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く、また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い。）
本発明に係る高強度、超弾性率ポリオレフィン繊維の製造方法は、上記オレフィン重合用触媒を用いて得られる、極限粘度が５〜５０ｄｌ／ｇ、融解熱量が２００Ｊ／ｇ以上である超高分子量オレフィン系重合体をその重合体の融点未満の温度で固相押出延伸や、圧延の後、更に延伸して、強度が３．５ＧＰａ以上、弾性率が１２０ＧＰａ以上のポリオレフィン繊維を得ることを特徴としている。また、本発明のポリオレフィン繊維の製造方法は、上記オレフィン重合用触媒を用いて得られる、極限粘度が５〜５０ｄｌ／ｇの超高分子量オレフィン系重合体を、溶媒に加熱混合し、該混合物を一旦結晶マット化後に延伸して、３ＧＰａ以上の強度を有するポリオレフィン繊維を得ることを特徴としている。
本発明に係る延伸成形体は、上記オレフィン重合用触媒を用いて得られる、分子量分布（Ｍｗ／Ｍｎ）が４以下であり、極限粘度が５〜５０ｄｌ／ｇの超高分子量オレフィン系重合体から得られ、Ｘ線回折により測定された配向係数が０．５以上且つ、長周期が３０ｎｍ以上であることを特徴としている。

(In the formula, M represents titanium, zirconium or hafnium , m represents 2 , R ¹ to R
R ⁶ may be the same as or different from each other, and represents a hydrogen atom or a hydrocarbon group , n is
X is a number satisfying the valence of M, X represents a hydrogen atom, a halogen atom or a hydrocarbon group, and when n is 2 or more, a plurality of groups represented by X may be the same or different from each other; A plurality of groups represented by X may be bonded to each other to form a ring. )
The method for producing a high-strength, superelastic modulus polyolefin fiber according to the present invention is an ultrahigh molecular weight olefin having an intrinsic viscosity of 5 to 50 dl / g and a heat of fusion of 200 J / g or more, obtained using the above-mentioned catalyst for olefin polymerization. It is characterized by obtaining a polyolefin fiber having a strength of 3.5 GPa or more and an elastic modulus of 120 GPa or more by solid-phase extrusion drawing at a temperature lower than the melting point of the polymer or further rolling after rolling the polymer. . Further, the method for producing a polyolefin fiber of the present invention comprises heating and mixing an ultrahigh molecular weight olefin polymer having an intrinsic viscosity of 5 to 50 dl / g obtained using the above-mentioned catalyst for olefin polymerization in a solvent, It is characterized by obtaining a polyolefin fiber having a strength of 3 GPa or more by once stretching after crystal matting.
The stretched molded product according to the present invention is an ultrahigh molecular weight olefin polymer having a molecular weight distribution (Mw / Mn) of 4 or less and an intrinsic viscosity of 5 to 50 dl / g, obtained using the above olefin polymerization catalyst. It is obtained, characterized by having an orientation coefficient measured by X-ray diffraction of 0.5 or more and a long period of 30 nm or more .

By the olefin polymerization catalyst and method of the present invention, excellent polymerization activity and suitable for obtaining high strength and high elastic modulus fibers by solid phase stretching below the melting point using polymer powder, rolling and stretching. A polymer is obtained. For molding using this polymer, JP-A-55-107506, JP-A-1-92207, JP-A-63-41512, JP-A-7-238416, JP-A-59-216912, Patent 1890838, Patent 1965445, Patent There are known methods such as 2081450, and further, after these methods are used, by further drawing, it is possible to obtain high strength fibers that have not been obtained conventionally.

The present invention will be described in detail below.
The present invention relates to a method for producing an ultrahigh molecular weight polyolefin resin for obtaining polyolefin fibers having high strength and high elastic modulus. Here, polyethylene and polypropylene are used as the polyolefin, but polyethylene is particularly preferable. As the polyethylene, homopolyethylene or a copolymer of ethylene and a small amount of α-olefin of 10% by mass or less, preferably 5% by mass or less is suitable. Here, propylene, 1-butene, 1-hexene, 1-octene and 1-decene are used as the α-olefin, and propylene is particularly preferable. Unlike the extruder and so-called gel spinning disclosed in Japanese Examined Patent Publication No. 60-47922, this polyethylene fiber and film molding method uses a large amount of heat energy and a large amount of solvent consumed for melting exceeding the melting point of the resin. Therefore, the energy used for recovering the solvent is unnecessary, and the fiber manufacturing method has high efficiency and can simplify the manufacturing process.

  The intrinsic viscosity ([η]) of the polyolefin used in the present invention is 5 to 50 dl / g, preferably 10 to 40 dl / g, more preferably 15 to 30 dl / g (but 15 is not included), and 5 dl / g. If it is less than g, the strength of the drawn fiber is insufficient, and if it exceeds 50 dl / g, joining of the grain boundaries of the polyolefin powder is insufficient by press and solid phase drawing, and uniform drawing becomes difficult. Further, at 50 dl / g or more, in order to keep the viscosity of the solution at a workable viscosity, it is necessary to reduce the concentration of the solution, and the productivity is lowered.

  The molecular weight distribution Mw / Mn is measured by high temperature GPC, and Mw / Mn is preferably 4 or less, more preferably Mw / Mn is 3.5 or less. Furthermore, the heat of fusion measured by DSC of the polyolefin used in the present invention is 200 J / g or more, preferably 200 to 293 J / g, more preferably 205 to 293 J / g, more preferably 210 to 293 J / g. is there. In the fiber molding using the polymer of the present invention, in the molded body stretched as shown in JP-A-59-216914 and JP-A-59-216912, a long period considered to be derived from a lamella is observed by orientation crystallization. It will not be done. In addition, although the crystallinity and the orientation coefficient are improved, it has been confirmed that the orientation coefficient is increased by stretching in the present invention. The orientation coefficient is preferably 0.5 or more, more preferably 0.7 or more, more preferably 0.9 or more. The long period is preferably 30 nm or more, more preferably 40 nm or more, and more preferably 60 nm or more, and an unobservable level is good.

  The polyolefin resin obtained in the present invention can be spun by solid phase coextrusion stretching, gel stretching, and single crystal mat stretching. In the solid-phase coextrusion stretching, a polyolefin resin powder is pressed once below the melting point and processed into a plate shape, and then solid-phase coextrusion stretching (material integration, vol. 15 No. 3 (2002)). The average particle size of the powder is 50 to 500 μm. If the particle size is smaller than this, the powder becomes hard and difficult to flow, and if the particle size is larger than this, the powder particles are bonded to each other at the time of pressing and solid phase stretching. It becomes difficult and uniform stretching cannot be realized. The particle size is preferably 50 to 400 μm, more preferably 100 to 250 μm.

In the case of gel stretching, if the particle size is smaller than this, the powder is aggregated and uniform dissolution becomes difficult, and even if it is large, dissolution of the powder having a large particle size is delayed and uniform dissolution becomes difficult.
For the single crystal mat stretching, the method described in Macromolecules 1988, 21, 470-477 can be used.

  For gel stretching, known methods such as those described in JP-A-59-216914, JP-A-62-41341, JP-A-7-238416, and Japanese Patent No. 2557461 and 2601868 can be used. Are aliphatic hydrocarbon solvents such as octane, decane, dodecane, decalin, liquid paraffin, and aromatic solvents such as benzene, toluene, xylene, etc., as described in Japanese Patent Nos. 2557461 and 2601868, or hydrogenated systems thereof. Examples thereof include mineral oils such as solvents, halogenated hydrocarbon solvents, paraffinic, naphthenic and aromatic process oils and kerosene. Specifically, as the wax as the diluent, a compound called a paraffinic wax having an aliphatic hydrocarbon compound as a main component and usually having a mass average molecular weight of 2000 or less, preferably 1000 or less, more preferably 800 or less is used. .

  The draw ratio is usually 10 to 400 times, preferably 20 to 400 times. The elastic modulus of the stretched polyolefin fiber is 50 GPa or more, preferably 100 GPa or more, more preferably 120 GPa or more. The strength of the drawn polyolefin fiber is 1.0 GPa or more, preferably 2.0 GPa or more, more preferably 3.5 GPa or more.

  In the case of solid-phase stretching, the press molding temperature is 20 ° C. or higher and lower than the melting point, preferably 90 ° C. or higher and lower than the melting point, more preferably 110 ° C. or higher and lower than the melting point. The temperature for solid-phase stretching or roll rolling is 20 ° C. or higher and lower than the melting point, preferably 90 ° C. or higher and lower than the melting point, more preferably 110 ° C. or higher and lower than the melting point.

  A known method can be used for stretching, and the temperature during stretching is 20 ° C. or more and less than 170 ° C., preferably 90 ° C. or more and less than 160 ° C., more preferably 130 ° C. or more and less than 160 ° C.

Hereinafter, the olefin polymerization catalyst and the olefin polymerization method using the olefin polymerization catalyst in the present invention will be described in detail.
In the present specification, the term “polymerization” is sometimes used in the meaning including not only homopolymerization but also copolymerization, and the term “polymer” refers not only to homopolymer but also to copolymerization. Sometimes used in the meaning of including a coalescence.

The catalyst for olefin polymerization according to the present invention is a fine particle carrier,
(A) a transition metal compound represented by the following general formula (I);
(B) It is formed from a catalyst component on which an organoaluminum oxy compound (B) having a molar ratio of an alkyl group to an aluminum atom in a specific range is supported, and, if necessary, an organometallic compound (C).
Each catalyst component that forms the olefin polymerization catalyst of the present invention will be described.

(A) Transition metal compound

（なお、Ｎ……Ｍは、一般的には配位していることを示すが、本発明においては配位していてもしていなくてもよい。）
一般式（Ｉ）中、Ｍは周期表第３〜１１族の遷移金属原子（３族にはランタノイドも含まれる）を示し、好ましくは３〜９族（３族にはランタノイドも含まれる）の金属原子であり、より好ましくは３〜５族および９族の金属原子であり、特に好ましくは４族または５族の金属原子である。具体的には、スカンジウム、チタン、ジルコニウム、ハフニウム、バナジウム、ニオブ、タンタル、コバルト、ロジウム、イットリウム、クロム、モリブデン、タングステン、マンガン、レニウム、鉄、ルテニウムなどであり、好ましくはスカンジウム、チタン、ジルコニウム、ハフニウム、バナジウム、ニオブ、タンタル、コバルト、ロジウムなどであり、より好ましくは、チタン、ジルコニウム、ハフニウム、コバルト、ロジウム、バナジウム、ニオブ、タンタルなどであり、特に好ましくはチタン、ジルコニウム、ハフニウムである。ｍは、１〜６、好ましくは１〜４の整数を示す。

(Note that N... M generally indicates coordination, but may or may not be coordinated in the present invention.)
In general formula (I), M represents a transition metal atom of Group 3 to 11 of the periodic table (Group 3 includes lanthanoids), preferably Group 3 to 9 (Group 3 also includes lanthanoids). It is a metal atom, More preferably, it is a metal atom of a 3-5 group, and a 9 group, Most preferably, it is a 4 or 5 group metal atom. Specifically, scandium, titanium, zirconium, hafnium, vanadium, niobium, tantalum, cobalt, rhodium, yttrium, chromium, molybdenum, tungsten, manganese, rhenium, iron, ruthenium, etc., preferably scandium, titanium, zirconium, Hafnium, vanadium, niobium, tantalum, cobalt, rhodium, etc., more preferably titanium, zirconium, hafnium, cobalt, rhodium, vanadium, niobium, tantalum, etc., particularly preferably titanium, zirconium, hafnium. m represents an integer of 1 to 6, preferably 1 to 4.

R ^{1 to} R ⁶ may be the same or different from each other, and are a hydrogen atom, a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, a sulfur-containing group, phosphorus A containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group, and two or more of these may be linked to each other to form a ring. Examples of the halogen atom include fluorine, chlorine, bromine and iodine. Specifically, the hydrocarbon group has 1 to 30 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, neopentyl, n-hexyl, preferably 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 vinyl, allyl, isopropenyl, etc .; ethynyl, propargyl, etc. A linear or branched alkynyl group having 2 to 30 carbon atoms, preferably 2 to 20 carbon atoms; cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl and the like having 3 to 30 carbon atoms, preferably 3 to 20 carbon atoms A cyclic saturated hydrocarbon group; a cyclic hydrocarbon group having 5 to 30 carbon atoms such as cyclopentadienyl, indenyl, fluorenyl, etc. Sum hydrocarbon group; aryl group having 6-30 carbon atoms, preferably 6-20 carbon atoms, such as phenyl, benzyl, naphthyl, biphenyl, terphenyl, phenanthryl, anthracenyl; tolyl, iso-propylphenyl, t-butylphenyl, Examples thereof include alkyl-substituted aryl groups such as dimethylphenyl and di-t-butylphenyl.

  In the above hydrocarbon group, a hydrogen atom may be substituted with a halogen. For example, a halogenated hydrocarbon group having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms such as trifluoromethyl, pentafluorophenyl, chlorophenyl and the like. Can be mentioned.

  Moreover, the said hydrocarbon group may be substituted by other hydrocarbon groups, for example, aryl group substituted alkyl groups, such as benzyl and cumyl, etc. are mentioned.

  Furthermore, the hydrocarbon group is a heterocyclic compound residue; alkoxy group, aryloxy group, ester group, ether group, acyl group, carboxyl group, carbonate group, hydroxy group, peroxy group, carboxylic anhydride group, etc. Oxygen-containing group: amino group, imino group, amide group, imide group, hydrazino group, hydrazono group, nitro group, nitroso group, cyano group, isocyano group, cyanate ester group, amidino group, diazo group, amino group is ammonium salt Nitrogen-containing groups such as those; boron-containing groups such as boranediyl group, boranetriyl group, diboranyl group; mercapto group, thioester group, dithioester group, alkylthio group, arylthio group, thioacyl group, thioether group, thiocyanate group , Isothiocyanate ester group, sulfone ester group, Sulfur-containing groups such as sulfonamide groups, thiocarboxyl groups, dithiocarboxyl groups, sulfo groups, sulfonyl groups, sulfinyl groups, sulfenyl groups; phosphorus-containing groups such as phosphide groups, phosphoryl groups, thiophosphoryl groups, phosphato groups, silicon-containing groups , A germanium-containing group, or a tin-containing group.

  Of these, in particular, 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, neopentyl, n-hexyl, etc. Linear or branched alkyl groups; aryl groups having 6 to 30 carbon atoms, preferably 6 to 20 carbon atoms such as phenyl, naphthyl, biphenyl, terphenyl, phenanthryl, anthracenyl; halogen atoms and carbon atoms for these aryl groups A substituted aryl group substituted with 1 to 5 substituents such as an alkyl group or an alkoxy group having 1 to 30, preferably 1 to 20 carbon atoms, an aryl group or an aryloxy group having 6 to 30 carbon atoms, preferably 6 to 20 carbon atoms, etc. Is preferred.

  Examples of the oxygen-containing group, nitrogen-containing group, boron-containing group, sulfur-containing group and phosphorus-containing group are the same as those exemplified above.

  Heterocyclic compound residues include residues such as nitrogen-containing compounds such as pyrrole, pyridine, pyrimidine, quinoline, and triazine, oxygen-containing compounds such as furan and pyran, sulfur-containing compounds such as thiophene, and heterocyclic groups thereof. Examples thereof include a group further substituted with a substituent such as an alkyl group or alkoxy group having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, in the compound residue.

  Examples of silicon-containing groups include silyl groups, siloxy groups, hydrocarbon-substituted silyl groups, hydrocarbon-substituted siloxy groups, such as methylsilyl, dimethylsilyl, trimethylsilyl, ethylsilyl, diethylsilyl, triethylsilyl, diphenylmethylsilyl, triphenyl. Examples include phenylsilyl, dimethylphenylsilyl, dimethyl-t-butylsilyl, dimethyl (pentafluorophenyl) silyl and the like. Among these, methylsilyl, dimethylsilyl, trimethylsilyl, ethylsilyl, diethylsilyl, triethylsilyl, dimethylphenylsilyl, triphenylsilyl and the like are preferable. In particular, trimethylsilyl, triethylsilyl, triphenylsilyl, and dimethylphenylsilyl are preferable. Specific examples of the hydrocarbon-substituted siloxy group include trimethylsiloxy and the like.

  Examples of the germanium-containing group and tin-containing group include those obtained by substituting silicon of the silicon-containing group with germanium and tin.

Next, the examples of R ^{1 to} R ⁶ described above will be described more specifically.
Among the oxygen-containing groups, the alkoxy group includes methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, and the like, and the aryloxy group includes phenoxy, 2,6-dimethylphenoxy, 2, 4,6-trimethylphenoxy and the like are acyl groups such as formyl group, acetyl group, benzoyl group, p-chlorobenzoyl group and p-methoxybenzoyl group, and ester groups are acetyloxy, benzoyloxy and methoxy. Preferred examples include carbonyl, phenoxycarbonyl, p-chlorophenoxycarbonyl and the like.

  Among the nitrogen-containing groups, amide groups include acetamido, N-methylacetamide, N-methylbenzamide, etc., amino groups include dimethylamino, ethylmethylamino, diphenylamino, etc., and imide groups include acetamido, benzimide. Preferred examples of the imino group include methylimino, ethylimino, propylimino, butylimino, and phenylimino.

  Among the sulfur-containing groups, the alkylthio group includes methylthio, ethylthio, etc., the arylthio group includes phenylthio, methylphenylthio, naltylthio, etc., and the thioester group includes acetylthio, benzoylthio, methylthiocarbonyl, phenylthiocarbonyl, and the like. Preferred examples of the sulfone ester group include methyl sulfonate, ethyl sulfonate, and phenyl sulfonate, and examples of the sulfonamide group include phenylsulfonamide, N-methylsulfonamide, and N-methyl-p-toluenesulfonamide. It is done.

R ⁶ is preferably a substituent other than hydrogen. That is, R ⁶ is preferably a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a boron-containing group, a sulfur-containing group, a silicon-containing group, a germanium-containing group or a tin-containing group.
In particular, R ⁶ is a halogen atom, a hydrocarbon group, a heterocyclic compound residue, a hydrocarbon-substituted silyl group, a hydrocarbon-substituted siloxy group, an alkoxy group, an alkylthio group, an aryloxy group, an arylthio group, an acyl group, an ester group, a thioester Group, amide group, amino group, imide group, imino group, sulfone ester group, sulfonamide group, cyano group, nitro group or hydroxy group, and more preferably a halogen atom, a hydrocarbon group or a hydrocarbon-substituted silyl group. Preferably there is.

Preferred hydrocarbon groups as R ⁶ include 1 to 30 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, neopentyl, n-hexyl, etc. Is a linear or branched alkyl group having 1 to 20; a cyclic saturated hydrocarbon group having 3 to 30, preferably 3 to 20 carbon atoms such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl; phenyl, benzyl Aryl groups having 6 to 30 carbon atoms, preferably 6 to 20 carbon atoms, such as naphthyl, biphenylyl and triphenylyl; and alkyl groups or alkoxy groups having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, in these groups A halogenated alkyl group having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, carbon Child number 6-30, preferably 6-20 aryl group or an aryloxy group, a halogen, a cyano group, a nitro group, a group having a substituted group is further substituted, such as hydroxy groups are preferably exemplified.

Preferred hydrocarbon-substituted silyl groups as R ⁶ include methylsilyl, dimethylsilyl, trimethylsilyl, ethylsilyl, diethylsilyl, triethylsilyl, diphenylmethylsilyl, triphenylsilyl, dimethylphenylsilyl, dimethyl-t-butylsilyl, dimethyl (pentafluorophenyl). ) Cyril and the like. Particularly preferred are trimethylsilyl, triethylphenyl, diphenylmethylsilyl, isophenylsilyl, dimethylphenylsilyl, dimethyl-t-butylsilyl, dimethyl (pentafluorophenyl) silyl and the like.

In the present invention, R ⁶ is particularly a branched alkyl group having 3 to 30, preferably 3 to 20 carbon atoms, such as isopropyl, isobutyl, sec-butyl, tert-butyl, neopentyl, etc., and hydrogen of these groups Groups having 3 to 30 carbon atoms, such as groups substituted with aryl groups having 6 to 30 carbon atoms, preferably 6 to 20 carbon atoms (cumyl group, etc.), adamantyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc., preferably It is preferably a group selected from 3 to 20 cyclic saturated hydrocarbon groups, or an aryl group having 6 to 30 carbon atoms, preferably 6 to 20 carbon atoms, such as phenyl, naphthyl, fluorenyl, anthranyl and phenanthryl, or a hydrocarbon A substituted silyl group is also preferred.

R ^{1 to} R ⁶ are two or more of these groups, preferably adjacent groups connected to each other to form an aliphatic ring, an aromatic ring, or a hydrocarbon ring containing a hetero atom such as a nitrogen atom. These rings may further have a substituent.

When m is 2 or more, two groups out of the groups represented by R ^{1 to} R ⁶ may be linked. Further, when m is 2 or more, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , and R ⁶ may be the same or different from each other.

  n is a number satisfying the valence of M, specifically 0 to 5, preferably 1 to 4, more preferably an integer of 1 to 3.

  X is a 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, silicon-containing Group, germanium-containing group, or tin-containing group. When n is 2 or more, they may be the same or different. Examples of the halogen atom include fluorine, chlorine, bromine and iodine.

Examples of the hydrocarbon group include the same groups as those exemplified for R ^{1 to} R ⁶ . Specifically, alkyl groups such as methyl, ethyl, propyl, butyl, hexyl, octyl, nonyl, dodecyl, and eicosyl; cycloalkyl groups having 3 to 30 carbon atoms such as cyclopentyl, cyclohexyl, norbornyl, adamantyl; vinyl, Alkenyl groups such as propenyl and cyclohexenyl; arylalkyl groups such as benzyl, phenylethyl, and phenylpropyl; phenyl, tolyl, dimethylphenyl, trimethylphenyl, ethylphenyl, propylphenyl, biphenyl, naphthyl, methylnaphthyl, anthryl, phenanthryl, and the like Examples include, but are not limited to, an aryl group. 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. Of these, those having 1 to 20 carbon atoms are preferred.

Examples of the heterocyclic compound residue include the same ones as exemplified for R ^{1 to} R ⁶ . Examples of the oxygen-containing group include the same groups as those exemplified above for R ^{1 to} R ⁶ , specifically, a hydroxy group; an alkoxy group such as methoxy, ethoxy, propoxy, butoxy; phenoxy, methylphenoxy, dimethyl Examples include, but are not limited to, aryloxy groups such as phenoxy and naphthoxy; arylalkoxy groups such as phenylmethoxy and phenylethoxy; acetoxy groups; carbonyl groups and the like.

Examples of the sulfur-containing group include the same groups as those exemplified for R ^{1 to} R ⁶ , specifically, methyl sulfonate, trifluoromethane sulfonate, phenyl sulfonate, benzyl sulfonate, Sulfonate groups such as p-toluene sulfonate, trimethylbenzene sulfonate, triisobutylbenzene sulfonate, p-chlorobenzene sulfonate, pentafluorobenzene sulfonate; methyl sulfinate, phenyl sulfinate, benzyl Examples thereof include, but are not limited to, sulfinate groups such as sulfinate, p-toluene sulfinate, trimethylbenzene sulfinate, pentafluorobenzene sulfinate; alkylthio group; arylthio group.

Specific examples of the nitrogen-containing group include the same groups as those exemplified above for R ^{1 to} R ⁶ , and specific examples include amino groups; methylamino, dimethylamino, diethylamino, dipropylamino, dibutylamino, Examples thereof include, but are not limited to, alkylamino groups such as dicyclohexylamino; arylamino groups such as phenylamino, diphenylamino, ditolylamino, dinaphthylamino, methylphenylamino, and alkylarylamino groups.

Specific examples of the boron-containing group include BR ₄ (R represents hydrogen, an alkyl group, an aryl group which may have a substituent, a halogen atom, or the like).

  Specific examples of the phosphorus-containing group include trialkylphosphine groups such as trimethylphosphine, tributylphosphine, and tricyclohexylphosphine; triarylphosphine groups such as triphenylphosphine and tolylphosphine; methyl phosphite, ethyl phosphite, and phenyl phosphite Examples thereof include, but are not limited to, phosphite groups (phosphide groups); phosphonic acid groups; phosphinic acid groups.

Specific examples of the silicon-containing group include the same groups as those exemplified above for R ^{1 to} R ⁶ , and specifically, phenylsilyl, diphenylsilyl, trimethylsilyl, triethylsilyl, tripropylsilyl, tricyclohexylsilyl. Hydrocarbon substituted silyl groups such as triphenylsilyl, methyldiphenylsilyl, tolylsilylsilyl, trinaphthylsilyl; hydrocarbon substituted silyl ether groups such as trimethylsilyl ether; silicon substituted alkyl groups such as trimethylsilylmethyl; silicon substitution such as trimethylsilylphenyl An aryl group etc. are mentioned.

Specific examples of the germanium-containing group include the same groups as those exemplified above for R ^{1 to} R ⁶ , and specific examples include a group in which silicon in the silicon-containing group is replaced with germanium.

Specific examples of the tin-containing group include the same groups as those exemplified above for R ^{1 to} R ⁶ , and more specifically, a group in which silicon in the silicon-containing group is substituted with tin.

Specific examples of the halogen-containing group include fluorine-containing groups such as PF ₆ and BF ₄ , chlorine-containing groups such as ClO ₄ and SbCl _6, and iodine-containing groups such as IO ₄ , but are not limited thereto. Absent.

Specific examples of the aluminum-containing group include, but are not limited to, AlR ₄ (R represents hydrogen, an alkyl group, an aryl group which may have a substituent, a halogen atom, etc.).

  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 may be bonded to each other to form a ring.

  Specific examples of the transition metal compound represented by the general formula (I) are described in JP-A 2000-128931 as [Compound 6] to [Compound 16].

(B) Organoaluminum oxy compound The organoaluminum oxy compound is mainly composed of an alkylaluminumoxy compound represented by the following formula (i) or (ii) and contains a small amount of an organoaluminum compound such as trialkylaluminum. It is thought that Therefore, in the present invention, the alkyl group in the organoaluminum oxy compound is the total of the alkyl group in the alkylaluminum oxy compound and the alkyl group in the organoaluminum compound, and the aluminum atom in the organoaluminum oxy compound is alkyl. This is the total of aluminum atoms in the aluminum oxy compound and aluminum atoms in the organoaluminum compound.

（式中、Ｒはアルキル基を示し、ｎはｎ≧１である。）本発明で用いられる有機アルミニウムオキシ化合物は、該有機アルミニウムオキシ化合物中のアルキル基（Ｒ）とアルミニウム原子（Ａｌ）とのモル比（Ｒ／Ａｌ比）が１．８以下、好ましくは１．８ないし１．２、より好ましくは１．７ないし１．４の範囲にあることが望ましい。

(In the formula, R represents an alkyl group, and n is n ≧ 1.) The organoaluminum oxy compound used in the present invention includes an alkyl group (R), an aluminum atom (Al) in the organoaluminum oxy compound, and It is desirable that the molar ratio (R / Al ratio) is 1.8 or less, preferably 1.8 to 1.2, more preferably 1.7 to 1.4.

Next, how to determine the R / Al ratio will be described by taking the case where R is a methyl group as an example.
A sufficiently nitrogen-substituted flask is charged with 2 mmol of an organoaluminum oxy compound solution in terms of aluminum atoms. At this time, toluene is added and adjusted so that the total amount of the solution becomes 40 ml. After cooling the system to 10 ° C., 10 ml of 0.5N aqueous sulfuric acid solution is added dropwise. Methane gas generated by this operation is collected by a gas burette. After confirming that the generation of methane gas has completely stopped, the amount of methane gas generated (a milliliter) and the temperature of the gas (t ° C.) are measured and determined by the following formula 1. The amount of aluminum atoms in the organoaluminum oxy compound is measured by plasma emission spectroscopy.
[Formula 1]
R / Al = (a × 273) / {22.4 × (t + 273) × 2} Equation 1
Such an organoaluminum oxy compound can be prepared, for example, by the following method. (A) A method of adjusting the R / Al ratio by bringing water into contact with a conventionally known organoaluminum oxy compound such as a commercially available aluminoxane. (B) A method of adjusting the R / Al ratio by contacting a conventionally known organoaluminum oxy compound such as a commercially available aluminoxane with an inorganic compound not containing water. (C) A method of adjusting the R / Al ratio by once evaporating a solvent from a solution of a conventionally known organoaluminum oxy compound, for example, a commercially available aluminoxane, allowing the organoaluminum oxy compound to dry, and again dissolving in the solvent. Among these, the method (c) is most preferable.

  In addition, although aluminoxane is usually marketed as a solution, in this case, this solution can be used as it is. The aluminoxane solution may contain other components as long as the reaction is not adversely affected.

  Hereinafter, the organoaluminum oxy compound for adjusting the R / Al ratio may be referred to as a raw material organoaluminum oxy compound. In the method (a), since the organoaluminum compound in the raw material organoaluminum oxy compound reacts with water by bringing the raw material organoaluminum oxy compound into contact with water, the R / Al ratio can be adjusted. In this case, a raw material organoaluminum oxy compound having an R / Al ratio of 1.8 or less can be prepared by bringing a raw material organoaluminum oxy compound having an R / Al ratio of more than 1.8 and water into contact with each other. The R / Al ratio may be adjusted to a specific value of 1.8 or less by bringing an organoaluminum oxy compound and water adjusted to have an Al ratio of 1.8 or less and water.

  The water to be brought into contact with the raw material organoaluminum oxy compound can be used in a liquid, vapor or solid state. Specifically, for example, adsorbed water adsorbed on inorganic compounds or polymers such as silica, alumina and aluminum hydroxide, hydrocarbon solvents such as benzene, toluene and hexane, ether solvents such as tetrahydrofuran, amine solvents such as triethylamine, etc. Examples include water dissolved or dispersed in water, crystal water of magnesium chloride, magnesium sulfate, aluminum sulfate, copper sulfate, nickel sulfate, iron sulfate, and cerium chloride. Of these, it is desirable to use adsorbed water adsorbed on an inorganic compound.

  Moreover, the adsorbed water of the particulate carrier described later can also be used as water for contacting the raw material organoaluminum oxy compound. When adsorbed water or crystallization water is used as the water to be brought into contact with the raw material organic aluminum oxy compound, the contact between the raw material organic aluminum oxy compound and water is usually carried out in an organic medium.

  Examples of the organic medium used here include aromatic hydrocarbons such as benzene, toluene, xylene, cumene, and cymene; aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, hexadecane, and octadecane; cyclopentane, Cycloaliphatic hydrocarbons such as cyclohexane, cyclooctane and methylcyclohexane; hydrocarbon solvents such as petroleum fractions such as gasoline, kerosene and light oil; or halogens of the above aromatic hydrocarbons, aliphatic hydrocarbons and alicyclic hydrocarbons Among them, halogenated hydrocarbons such as chlorinated products and brominated products; ethers such as ethyl ether and tetrahydrofuran can be mentioned.

Of these organic media, aromatic hydrocarbons are particularly preferred. The water used for the contact between the raw material organic aluminum oxy compound and water is 0.01 to 0.3 mol, preferably 0.02 to 0.2 mol, relative to 1 mol of aluminum atoms in the raw material organic aluminum oxy compound. More preferably, it is used in an amount of 0.03 to 0.15 mol. The concentration of the raw material organic aluminum oxy compound in the reaction system is usually 1 × 10 ^{−3 to} 5 mol / liter (solvent), preferably 1 × 10 ⁻² to, in terms of aluminum atoms in the raw material organic aluminum oxy compound. The range of 3 mol / liter (solvent) is desirable, and the concentration of water in the reaction system is usually 0.01 to 1 mol / liter (solvent), preferably 0.02 to 0.5 mol / liter. The concentration of (solvent) is desirable.

  The contact between the raw material organoaluminum oxy compound and water is usually carried out at a temperature of -50 to 150 ° C, preferably 0 to 120 ° C, more preferably 20 to 100 ° C. The contact time varies greatly depending on the contact temperature, but is usually 0.5 to 300 hours, preferably about 1 to 150 hours.

In order to bring the raw material organoaluminum oxy compound into contact with water, specifically, the following may be performed. (1) A method in which a raw material organic aluminum oxy compound and a compound containing adsorbed water are mixed and the raw material organic aluminum oxy compound and adsorbed water are brought into contact with each other. (Note that the compound containing adsorbed water includes the following particulate carrier) (2) A raw material organoaluminum oxy compound and a compound containing crystallization water are mixed, How to contact.
(3) A method of bringing a raw material organoaluminum oxy compound into contact with a hydrocarbon solvent containing (dissolved or dispersed) water. (4) A method of bringing the raw material organic aluminum oxy compound and water vapor into contact with each other by blowing water vapor into the solution of the raw material organic aluminum oxy compound. (5) A method in which the raw material organoaluminum oxy compound is directly brought into contact with water or ice.

  In the method (b), an organoaluminum oxy compound having an R / Al ratio of 1.8 or less by contacting a raw material organoaluminum oxy compound having an R / Al ratio exceeding 1.8 and an inorganic compound substantially free of water. Compounds can be prepared. In the present specification, “substantially not containing water” means that the amount of adsorbed water of the inorganic compound is 0.1% by mass or less.

  By bringing the inorganic compound substantially free of water into contact with the raw material organic aluminum oxy compound, a specific component in the raw material organic aluminum oxy compound, for example, an alkylaluminum oxy compound having a specific R / Al ratio is converted into the inorganic compound. It is considered that the R / Al ratio changes due to the adsorption and separation. Therefore, an inorganic compound that does not substantially contain water is used. Among these inorganic compounds, those having a surface hydroxyl group can change the R / Al ratio by the action of the hydroxyl group. In this case, specific examples of the inorganic compound to be brought into contact with the raw material organic aluminum oxy compound include silica, alumina, aluminum hydroxide and the like. The surface hydroxyl group amount of this inorganic compound is 1.0% by mass or more, preferably 1.5 to 4.0% by mass, particularly preferably 2.0 to 3.5% by mass, and the amount of adsorbed water is 0.1%. It is desirable that the content is not more than mass%, preferably not more than 0.01 mass%.

The inorganic compound has a particle size of 10 to 300 μm, preferably 20 to 200 μm, and a specific surface area of 50 to 1000 m ² / g, preferably 100 to 700 m ² / g. .

Here, the amount of adsorbed water (% by mass) and the amount of surface hydroxyl group (% by mass) of the inorganic compound are determined as follows. [Amount of adsorbed water] This is a value indicating the weight loss when dried at a temperature of 200 ° C. for 4 hours under normal pressure and nitrogen flow as a percentage of the weight before drying. [Amount of surface hydroxyl group] The weight of the inorganic compound obtained by drying for 4 hours at 200 ° C. under normal pressure and nitrogen flow is X (g), and the inorganic compound is further calcined at 1000 ° C. for 20 hours. The weight of the obtained baked product from which the surface hydroxyl group has disappeared is calculated by the following formula 2 as Y (g).
[Formula 2]
Surface hydroxyl group content (% by weight) = [(XY) / X] × 100 Formula 2
Contact between the raw material organic aluminum oxy compound and the inorganic compound is usually carried out in an organic medium. Examples of the organic medium used at this time include the above hydrocarbons, halogenated hydrocarbons, ethers and the like. Of these organic media, aromatic hydrocarbons are particularly preferred.

The inorganic compound used for the contact with the raw material organic aluminum oxy compound is 1 to 50 mol%, preferably 5 to 45 mol%, more preferably 10 to 40 mol% with respect to aluminum atoms in the raw material organic aluminum oxy compound. Used in quantity. The concentration of the raw material organic aluminum oxy compound in the reaction system is usually 1 × 10 ^{−3 to} 5 gram atom / liter (solvent), preferably 1 × 10 ⁻² in terms of aluminum atoms in the raw material organic aluminum oxy compound. Desirably, it is in the range of ~ 3 gram atoms / liter (solvent).

  The contact between the raw material organic aluminum oxy compound and the inorganic compound not containing water is usually carried out at a temperature of -50 to 150 ° C, preferably 0 to 120 ° C, more preferably 20 to 100 ° C. The contact time varies greatly depending on the contact temperature, but is usually 0.5 to 300 hours, preferably about 1 to 150 hours.

  In the method (c), the solvent is temporarily evaporated from the solution of the raw material organoaluminum oxy compound having an R / Al ratio exceeding 1.8, and the organoaluminum oxy compound is dried and then dissolved again in the solvent. An organoaluminum oxy compound having a / Al ratio of 1.8 or less can be prepared. Alternatively, the R / Al ratio may be adjusted to a specific value of 1.8 or less by using (raw material) an organic aluminum oxy compound having an R / Al ratio of 1.8 or less. The temperature for evaporating the solvent is 10 to 100 ° C., preferably 20 to 50 ° C., and the pressure is 2 to 100 mmHg, preferably 5 to 40 mmHg. Examples of the solvent for dissolving the dried organic aluminum oxy compound include the organic medium used in the method (a), and aromatic hydrocarbons are preferable.

  Furthermore, in this invention, you may prepare the organoaluminum oxy compound whose R / Al ratio is 1.8 or less combining the method of (a), the method of (b), and the method of (c).

  Specifically, for example, the R / Al ratio of the (raw material) organoaluminum oxy compound whose R / Al ratio is adjusted to 1.8 or less by the method (a) is 1.8 or less by the method (c). The R / Al ratio of the (raw) organoaluminum oxy compound whose R / Al ratio is adjusted to 1.8 or less by the method (b) can be adjusted by the method (c). The R / Al ratio may be adjusted to a specific value of 1.8 or less.

(C) Organometallic compound As the (C) organometallic compound used in the present invention, specifically, organometallic compounds of Groups 1, 2 and 12, 13 of the periodic table as described below are used.

(C-1) the general formula _{^{R a m Al (OR b)}} n H p X q
(In the formula, R ^a and R ^b may be the same or different from each other, each represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, X represents a halogen atom, and m represents 0. <M ≦ 3, n is 0 ≦ n <3, p is a number of 0 ≦ p <3, q is a number of 0 ≦ q <3, and m + n + p + q = 3).

(C-2) General formula M ² AlR ^a ₄
(Wherein M ² represents Li, Na or K, and R ^a represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms) Complex alkylated product with aluminum.

(C-3) General formula R ^a R ^b M ³
(In the formula, R ^a and R ^b may be the same or different from each other, and each represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, and M ³ is Mg, Zn or Cd. A dialkyl compound of a metal of Group 2 or Group 12 of the periodic table represented by:

  Examples of the organoaluminum compound belonging to (C-1) include the following compounds.

General formula R ^a _m Al (OR ^b ) _3-m
(In the formula, R ^a and R ^b may be the same or different from each other and each represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, and m is preferably 1.5 ≦ m ≦ An organoaluminum compound represented by the following formula:
General formula R ^a _m AlX _3-m
(Wherein R ^a represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, X represents a halogen atom, and m is preferably 0 <m <3). Organoaluminum compounds,
General formula R ^a _m AlH _3-m
(Wherein R ^a represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, and m is preferably 2 ≦ m <3),
General formula R ^a _m Al (OR ^b ) _n X _q
(In the formula, R ^a and R ^b may be the same or different from each other, each represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, X represents a halogen atom, and m represents 0. <M ≦ 3, n is a number 0 ≦ n <3, q is a number 0 ≦ q <3, and m + n + q = 3).

More specifically, examples of the organoaluminum compound belonging to (C-1) include trimethylaluminum, triethylaluminum, tri-n-butylaluminum, tripropylaluminum, tripentylaluminum, trihexylaluminum, trioctylaluminum, and tridecylaluminum. Tri-n-alkylaluminum;
Triisopropylaluminum, triisobutylaluminum, trisec-butylaluminum, tritert-butylaluminum, tri-2-methylbutylaluminum, tri-3-methylbutylaluminum, tri-2-methylpentylaluminum, tri-3-methylpentylaluminum, tri-4 A tri-branched alkylaluminum such as methylpentylaluminum, tri-2-methylhexylaluminum, tri-3-methylhexylaluminum, tri-2-ethylhexylaluminum;
Tricycloalkylaluminum such as tricyclohexylaluminum, tricyclooctylaluminum;
Triarylaluminums such as triphenylaluminum and tolylylaluminum;
Dialkylaluminum hydrides such as diisobutylaluminum hydride;
_{(I-C 4 H 9)} x Al y (C 5 H 10) z ( wherein, x, y, z are each a positive number, and z ≧ 2x.) Tri isoprenylaluminum represented by like Trialkenyl aluminum such as;
Alkyl aluminum alkoxides such as isobutyl aluminum methoxide, isobutyl aluminum ethoxide, isobutyl aluminum isopropoxide;
Dialkylaluminum alkoxides such as dimethylaluminum methoxide, diethylaluminum ethoxide, dibutylaluminum butoxide;
Alkylaluminum sesquialkoxides such as ethylaluminum sesquiethoxide and butylaluminum sesquibutoxide;
Partially alkoxylated alkylaluminum having an average composition such as R ^a _2.5 Al (OR ^b ) _0.5 ;
Diethylaluminum phenoxide, diethylaluminum (2,6-di-t-butyl-4-methylphenoxide), ethylaluminum bis (2,6-di-t-butyl-4-methylphenoxide), diisobutylaluminum (2,6- Dialkylaluminum aryloxides such as di-t-butyl-4-methylphenoxide), isobutylaluminum bis (2,6-di-t-butyl-4-methylphenoxide);
Dialkylaluminum halides such as dimethylaluminum chloride, diethylaluminum chloride, dibutylaluminum chloride, diethylaluminum bromide, diisobutylaluminum chloride;
Alkylaluminum sesquichlorides such as ethylaluminum sesquichloride, butylaluminum sesquichloride, ethylaluminum sesquibromide;
Partially halogenated alkylaluminums such as alkylaluminum dihalides such as ethylaluminum dichloride, propylaluminum dichloride, butylaluminum dibromide;
Dialkylaluminum hydrides such as diethylaluminum hydride, dibutylaluminum hydride;
Other partially hydrogenated alkylaluminums such as alkylaluminum dihydrides such as ethylaluminum dihydride, propylaluminum dihydride;
Examples include partially alkoxylated and halogenated alkylaluminums such as ethylaluminum ethoxychloride, butylaluminum butoxychloride, and ethylaluminum ethoxybromide.

A compound similar to (C-1) can also be used, and examples thereof include an organoaluminum compound in which two or more aluminum compounds are bonded via a nitrogen atom. Specific examples of such a compound include (C ₂ H ₅ ) ₂ AlN (C ₂ H ₅ ) Al (C ₂ H ₅ ) ₂ .

Examples of the compound belonging to (C-2) include LiAl (C ₂ H ₅ ) ₄ and LiAl (C ₇ H ₁₅ ) ₄ .

  In addition, (C-1) organometallic compounds include methyl lithium, ethyl lithium, propyl lithium, butyl lithium, methyl magnesium bromide, methyl magnesium chloride, ethyl magnesium bromide, ethyl magnesium chloride, propyl magnesium bromide, propyl magnesium. Chloride, butyl magnesium bromide, butyl magnesium chloride, dimethyl magnesium, diethyl magnesium, dibutyl magnesium, butyl ethyl magnesium and the like can also be used.

  A compound that can form the organoaluminum compound in the polymerization system, for example, a combination of aluminum halide and alkyllithium, or a combination of aluminum halide and alkylmagnesium can also be used.

  (C) Among organometallic compounds, organoaluminum compounds are preferred.

  The above (C) organometallic compounds are used singly or in combination of two or more.

(D) Compound that reacts with transition metal compound (A) to form an ion pair Compound (D) that reacts with transition metal compound (A) used in the present invention to form an ion pair (hereinafter referred to as "D") "Ionized ionic compound") is a compound that reacts with the transition metal compound (A) to form an ion pair. Therefore, what forms an ion pair by making it contact with at least the said transition metal compound (A) is contained in this compound. Examples of such compounds include JP-A-1-501950, JP-A-1-502036, JP-A-3-179905, JP-A-3-179006, JP-A-3-207703, and JP-A-3. And Lewis acids, ionic compounds, borane compounds and carborane compounds described in US Pat. No. 207704, US Pat. No. 5,321,106, and the like. Furthermore, heteropoly compounds and isopoly compounds can also be mentioned.

Specifically, as the Lewis acid, a compound represented by BR ₃ (R is a phenyl group which may have a substituent such as fluorine, methyl group, trifluoromethyl group or fluorine) is exemplified. For example, trifluoroboron, triphenylboron, tris (4-fluorophenyl) boron, tris (3,5-difluorophenyl) boron, tris (4-fluoromethylphenyl) boron, tris (pentafluorophenyl) boron, Examples thereof include tris (p-tolyl) boron, tris (o-tolyl) boron, and tris (3,5-dimethylphenyl) boron.

  Examples of the ionic compound include compounds represented by the following general formula (II).

式中、Ｒ²²としては、Ｈ+、カルボニウムカチオン、オキソニウムカチオン、アンモニウムカチオン、ホスホニウムカチオン、シクロヘプチルトリエニルカチオン、遷移金属を有するフェロセニウムカチオンなどが挙げられる。Ｒ²³〜Ｒ²⁶は、互いに同一でも異なっていてもよい有機基、好ましくはアリール基または置換アリール基である。

In the formula, R ²² includes H +, carbonium cation, oxonium cation, ammonium cation, phosphonium cation, cycloheptyltrienyl cation, ferrocenium cation having a transition metal, and the like. R ^{23 to} R ²⁶ are organic groups which may be the same as or different from each other, preferably an aryl group or a substituted aryl group.

Specific examples of the carbonium cation include trisubstituted carbonium cations such as triphenylcarbonium cation, tri (methylphenyl) carbonium cation, and tri (dimethylphenyl) carbonium cation.
Specific examples of the ammonium cation include trialkylammonium cation, triethylammonium cation, tripropylammonium cation, tributylammonium cation, and tri (n-butyl) ammonium cation; N, N-dimethylanilinium cation; N, N-diethylanilinium cation, N, N-2,4,6-pentamethylanilinium cation, etc., N, N-dialkylanilinium cation; di (isopropyl) ammonium cation, dicyclohexylammonium cation, etc. dialkylammonium cation Etc.
Specific examples of the phosphonium cation include triarylphosphonium cations such as triphenylphosphonium cation, tri (methylphenyl) phosphonium cation, and tri (dimethylphenyl) phosphonium cation.

R ²² is preferably a carbonium cation, an ammonium cation or the like, and particularly preferably a triphenylcarbonium cation, an N, N-dimethylanilinium cation or an N, N-diethylanilinium cation.

  Examples of the ionic compound include trialkyl-substituted ammonium salts, N, N-dialkylanilinium salts, dialkylammonium salts, and triarylphosphonium salts.

  Specific examples of the trialkyl-substituted ammonium salt include triethylammonium tetra (phenyl) boron, tripropylammonium tetra (phenyl) boron, tri (n-butyl) ammonium tetra (phenyl) boron, and trimethylammonium tetra (p-tolyl). Boron, trimethylammonium tetra (o-tolyl) boron, tri (n-butyl) ammonium tetra (pentafluorophenyl) boron, tripropylammonium tetra (o, p-dimethylphenyl) boron, tri (n-butyl) ammonium tetra ( m, m-dimethylphenyl) boron, tri (n-butyl) ammonium tetra (p-trifluoromethylphenyl) boron, tri (n-butyl) ammonium tetra (3,5-ditrifluoromethylphenol) Le) boron, tri (n- butyl) ammonium tetra (o-tolyl) and boron and the like.

  Specific examples of N, N-dialkylanilinium salts include N, N-dimethylanilinium tetra (phenyl) boron, N, N-diethylanilinium tetra (phenyl) boron, N, N-2,4,6. -Pentamethylanilinium tetra (phenyl) boron and the like. Specific examples of the dialkylammonium salt include di (1-propyl) ammonium tetra (pentafluorophenyl) boron and dicyclohexylammonium tetra (phenyl) boron.

  Further, as ionic compounds, triphenylcarbenium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, ferrocenium tetra (pentafluorophenyl) borate, triphenylcarbenium pentaphenyl Examples thereof include a cyclopentadienyl complex and an N, N-diethylanilinium pentaphenylcyclopentadienyl complex.

Particulate carrier The particulate carrier used in the present invention is an inorganic or organic compound, and is a granular or particulate solid.

  Among these, as the inorganic compound, porous oxides, inorganic chlorides, clays, clay minerals or ion-exchangeable layered compounds are preferable.

As the porous oxide, specifically, SiO ₂ , Al ₂ O ₃ , MgO, ZrO, TiO ₂ , B ₂ O ₃ , CaO, ZnO, BaO, ThO ₂ or the like, or a composite or mixture containing these is used. For example, natural or synthetic zeolite, SiO ₂ —MgO, SiO ₂ —Al ₂ O ₃ , SiO ₂ —TiO ₂ , SiO ₂ —V ₂ O ₅ , SiO ₂ —Cr ₂ O ₃ , SiO ₂ —TiO ₂ —MgO, etc. Can be used. Of these, those containing SiO ₂ and / or Al ₂ O ₃ as main components are preferred.

The inorganic oxide includes a small amount of Na ₂ CO ₃ , K ₂ CO ₃ , CaCO ₃ , MgCO ₃ , Na ₂ SO ₄ , Al ₂ (SO ₄ ) ₃ , BaSO ₄ , KNO ₃ , Mg (NO ₃ ). ₂ , Al (NO ₃ ) ₃ , Na ₂ O, K ₂ O, Li ₂ O and other carbonates, sulfates, nitrates, and oxide components may be contained.

Such porous oxides have different properties depending on the type and production method, but the carrier preferably used in the present invention has a particle size of 10 to 300 μm, preferably 20 to 200 μm, and a specific surface area of 50 to 1000 m. ² / g, preferably in the range of 100 to 700 m ² / g, and the pore volume is in the range of 0.3 to 3.0 cm ³ / g. Such a carrier is used after being calcined at 100 to 1000 ° C., preferably 150 to 700 ° C., if necessary.

In the polymerization, the method of using each component and the order of addition are arbitrarily selected, and the following methods are exemplified.
(1) Component (A) and at least one component selected from (C) an organometallic compound, (B) an organoaluminum oxy compound, and (D) an ionized ionic compound are added to the polymerization vessel in any order. Method.
(2) A method in which the component (A), the catalyst component in which the component (C) is contacted in advance, and the component (D) are added to the polymerization vessel in an arbitrary order.
(3) A method in which the component (A), the catalyst component in which the component (C) is previously contacted, and the component (C) and the component (D) are added to the polymerization vessel in an arbitrary order. In this case, component (C) may be the same or different.
(4) A method in which component (A), component (C) and component (D) are contacted in advance, and component (C) is added to the polymerization vessel in any order. In this case, component (C) may be the same or different.
(5) A method in which a catalyst in which the component (A) and the component (B) are contacted in advance is added to the polymerization vessel.
(6) A method in which the catalyst component in which the component (A) and the component (B) are previously contacted, and the component (C) or (B) are added to the polymerization vessel in an arbitrary order. In this case, the component (B) may be the same or different. Among these, the methods (2), (3) and (4) are particularly preferable.

  In the method for producing an ultrahigh molecular weight olefin polymer according to the present invention, for example, an olefin polymer is obtained by copolymerizing an olefin in a solution in the presence of the olefin polymerization catalyst as described above.

  In the present invention, the polymerization can be carried out by a liquid phase polymerization method such as solution polymerization or suspension polymerization. Specific examples of the inert hydrocarbon medium 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. Alicyclic hydrocarbons such as benzene, toluene, xylene and the like aromatic hydrocarbons; halogenated hydrocarbons such as ethylene chloride, chlorobenzene, dichloromethane and the like, and mixtures thereof. The olefin itself is used as a solvent. You can also.

Using the above-mentioned olefin polymerization catalyst, when performing the polymerization of olefins, Component (A) is generally 1 × ^{10 -12} ~1 × ^{10 -2} mol per liquid 1 liter is preferably 1 × 10 ^- It is used in such an amount that it is ¹⁰ to 1 × 10 ⁻³ mol.

  Component (C) has a molar ratio [(C) / M] of component (C) and transition metal atom (M) in component (A) of usually 0.01 to 100,000, preferably 0.05 to The amount used is 50,000. Component (B) has a molar ratio [(B) / M] of the aluminum atom in component (B) and the transition metal atom (M) in component (A) of usually 10 to 500,000, preferably 20 to The amount used is 100,000. Component (D) is such that the molar ratio [(D) / M] of component (D) to transition metal atom (M) in component (A) is usually 1 to 10, preferably 1 to 5. Used in various amounts.

Moreover, the polymerization temperature of the 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 any of batch, semi-continuous and continuous methods. it can. Furthermore, the polymerization can be performed in two or more stages having different reaction conditions.

  The molecular weight of the resulting olefin polymer can be adjusted by the presence of hydrogen in the polymerization system or by changing the polymerization temperature. Furthermore, it can also adjust by the difference in the component (B) (C) (D) to be used.

  In the present invention, the olefin polymerization catalyst may contain other components useful for olefin polymerization in addition to the above components.

  In the olefin polymerization catalyst according to the present invention, the particulate carrier (A) transition metal compound [component (A)] and the molar ratio of (B) alkyl group to aluminum atom (alkyl group / aluminum atom). ) Is preferably loaded with an organoaluminum oxy compound [component (B)] of 1.8 or less.

  Such an olefin polymerization catalyst (solid catalyst component) can be prepared by mixing and contacting the particulate carrier, component (A) and component (B) in an inert hydrocarbon solvent. Further, when the components are brought into contact with each other, the organoaluminum compound (C) [component (C)] can be further added.

The order of mixing at this time is arbitrarily selected. Preferably, the particulate carrier and the component (B) are mixed and contacted, and then the component (A) is mixed and contacted, or the component (B) and the component (A) are mixed. It is selected to mix and contact the mixture of and the fine particle carrier.
Specific examples of the inert hydrocarbon solvent used in the preparation of the catalyst for olefin polymerization in the present invention include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; cyclopentane, Examples thereof include alicyclic hydrocarbons such as cyclohexane and methylcyclopentane; aromatic hydrocarbons such as benzene, toluene and xylene; halogenated hydrocarbons such as ethylene chloride, chlorobenzene and dichloromethane, or mixtures thereof.

When mixing the above components, the component (A) is usually in an amount of 5 × 10 ^{−6 to} 5 × 10 ⁻⁴ mol, preferably 1 × 10 ⁻⁶ to 2 × 10 ⁻⁴ mol, per 1 g of the particulate carrier. The concentration of the component (A) is about 1 × 10 ⁻⁴ to 2 × 10 ⁻² mol / liter (solvent), preferably 2 × 10 ⁻⁴ to 1 × 10 ⁻² mol / liter (solvent). Range. The component (B) is usually 1 × 10 ^{−4 to} 0.1 mol, preferably 5 × 10 ^{−4 to} 5 × 10 ⁻ in terms of aluminum atoms (Al) in the component (B) per 1 g of the particulate carrier. Used in an amount of ² moles. The atomic ratio (Al / M) of the aluminum atom (Al) in the component (B) and the transition metal atom (M) in the component (A) is usually 10 to 600, preferably 20 to 400.

  The mixing temperature at the time of mixing each said component is -50-150 degreeC normally, Preferably it is -20-120 degreeC, and contact time is 1-1000 minutes, Preferably it is 5-600 minutes. Further, the mixing temperature may be changed during the mixing contact.

  The olefin polymerization catalyst according to the present invention may be a prepolymerization catalyst in which an olefin is prepolymerized on the solid catalyst component.

  In the olefin polymerization method according to the present invention, an olefin polymer is obtained by polymerizing or copolymerizing an olefin in the presence of the olefin polymerization catalyst as described above.

  In the present invention, the 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 the inert hydrocarbon medium 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. Alicyclic hydrocarbons such as benzene, toluene, xylene and the like aromatic hydrocarbons; halogenated hydrocarbons such as ethylene chloride, chlorobenzene, dichloromethane and the like, and mixtures thereof. The olefin itself is used as a solvent. You can also.

When the olefin polymerization is performed using the olefin polymerization catalyst as described above, the amount of the transition metal atom in the component (A) in the polymerization system is usually 1 × 10 ⁻¹⁰ to 1 liter per reaction volume. The amount used is 1 × 10 ⁻² mol, preferably 1 × 10 ⁻⁸ to 1 × 10 ⁻³ mol. At this time, an organometallic compound (component (C)) can be used as necessary. In this case, the amount of the organometallic compound is desirably 2000 mol or less, preferably 50 to 1000 mol, per 1 mol of the transition metal atom in the component (A). In addition to the component (C), an organoaluminum oxy compound may be added separately from the component supported on the carrier.

The polymerization temperature is usually in the range of −50 to 100 ° C., preferably 0 to 90 ° C. when the slurry polymerization method is carried out, and is usually 0 to 250 when the liquid phase polymerization method is carried out. It is desirable that the temperature be in the range of 20 ° C., preferably 20 to 200 ° C. In carrying out the gas phase polymerization method, the polymerization temperature is usually 0 to 120 ° C., preferably 20 to 100 ° 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 is carried out in any of batch, semi-continuous and continuous methods. Can do. Furthermore, the polymerization can be performed in two or more stages having different reaction conditions.

  The molecular weight of the resulting olefin polymer can be adjusted by the presence of hydrogen in the polymerization system or by changing the polymerization temperature. Furthermore, it can also adjust by the difference in the component (B) (C) (D) to be used.

  Examples of the olefin that can be polymerized by such an olefin polymerization catalyst include ethylene and propylene, 1 to 3 linear, branched α-olefins having 3 to 30 carbon atoms, preferably 3 to 20 carbon atoms. Butene, 2-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, cyclic olefins having 3 to 30 carbon atoms, preferably 3 to 20 carbon atoms, or dienes or polyenes can also be used.

  These olefins can be used alone or in combination of two or more, but ethylene and / or propylene are preferable, and ethylene is particularly preferable.

  The following known stabilizers and additives may be appropriately added to the obtained polymer to improve the expected performance of each.

Metal deactivators, UV absorbers, HALS, phenolic antioxidants, phosphorus antioxidants, sulfur antioxidants, fatty acid metal salts, phosphate esters, fatty acid esters and other esters, silica, carbon, fullerene, carbon The above-mentioned fine particles used for obtaining the nanotube or carbon nanohorn polymer may be appropriately blended and used.

EXAMPLES Hereinafter, although this invention is demonstrated further more concretely based on an Example, this invention is not limited to these Examples.

[Method for measuring physical properties]
(Mass average molecular weight (Mw), number average molecular weight (Mn))
Measurement was performed as follows using GPC-2000 manufactured by Waters. The separation columns are TSKgel GMH6-HT and TSKgel GMH6-HTL, the column size is 7.5 mm in inner diameter and the length is 600 mm, the column temperature is 140 ° C., the mobile phase is o-dichlorobenzene (Wako Pure Chemical Industries, Ltd.) ) And 0.025% BHT (Takeda Pharmaceutical) as the antioxidant, moved at 1.0 ml / min, the sample concentration was 0.15 mass%, the sample injection volume was 500 microliters, and the detector A differential refractometer was used. The standard polystyrene used was manufactured by Tosoh Corporation for molecular weights of Mw <1000 and Mw> 4 × 10 ⁶ , and used by Pressure Chemical Co. for 1000 ≦ Mw ≦ 4 × 10 ⁶ .

(Intrinsic viscosity ([η]))
It is a value measured at 135 ° C. using a decalin solvent. That is, about 15 mg of the polymer powder is dissolved in 15 ml of decalin, and the specific viscosity ηsp is measured in an oil bath at 135 ° C. After adding 5 ml of decalin solvent to the decalin solution for dilution, the specific viscosity ηsp is measured in the same manner. This dilution operation is further repeated twice, and the value of ηsp / C when the concentration (C) is extrapolated to 0 is obtained as the intrinsic viscosity.
[Η] = lim (ηsp / C) (C → 0)
(Heat of fusion)
Using Pyris (I) manufactured by PerkinElmer, the amount of heat of fusion was measured at a heating rate of 10 ° C./min in a nitrogen stream.

(Strength, elastic modulus)
The strength and elastic modulus were measured according to the chemical fiber filament yarn test method (JIS L1013).

[Preparation of solid component (A)]
After suspending 30 g of silica gel (SiO ₂ ) dried at 150 ° C. for 5 hours under nitrogen flow in 466 mL of toluene, 134.3 mL of methylalumoxane toluene solution (3.08 mmol / mL in terms of Al atom) was added at 25 ° C. For 30 minutes. After completion of dropping, the temperature was raised to 114 ° C. over 30 minutes, and the reaction was carried out at that temperature for 4 hours. Thereafter, the temperature was lowered to 60 ° C., and the supernatant was removed by decantation. The solid component thus obtained was washed three times with toluene, and then toluene was added to prepare a toluene slurry of the solid component (A). A part of the obtained solid component (A) was collected and examined for concentration. As a result, the slurry concentration was 0.150 g / mL and the Al concentration was 1.179 mmol / mL.

[Preparation of solid catalyst component (B)]
150 mL of toluene was put into a 300 mL glass flask purged with nitrogen, and the toluene slurry of the solid component (A) prepared above (0.95 g in terms of solid part) was charged with stirring. Next, 50.0 mL of a toluene solution of the transition metal compound (1) (0.0006 mmol / mL in terms of Zr atom) was added dropwise over 15 minutes, and reacted at room temperature for 1 hour. Thereafter, the supernatant was removed by decantation, washed 3 times with heptane, and 100 mL of heptane was added to prepare a heptane slurry of the solid catalyst component (B). When a portion of the resulting heptane slurry of the solid catalyst component (B) was collected to examine the concentration, the Zr concentration was 0.0026 mmol / mL and the Al concentration was 0.66 mmol / mL.

[Example 1]
[polymerization]
A 1-liter autoclave made of SUS with sufficient nitrogen substitution was charged with 500 ml of decane, and the liquid phase and gas phase were saturated with ethylene. While adding 0.5 mmol of triisobutylaluminum in terms of atom and 0.001 mmol of the following compound 1 as a solid catalyst component (B), supplying ethylene so that the total pressure becomes 7 kg / cm ² -G, at 85 ° C. for 3 hours. Polymerization was performed. The obtained polymer was washed with hexane and then dried under reduced pressure at 80 ° C. for 10 hours. The obtained polyethylene was 187.7 g, the polymerization activity was 187.7 kg / mmol-Zr, [η] was 21.6 dl / g, and the heat of fusion was 220 J / g.

[固相延伸]
得られた重合体を１３０℃で１２ＭＰａでプレスして厚さ０．５ｍｍのシートを得た。それを用い、１３０℃で６倍の固相延伸を行い更に、空気中で１４５℃で引張延伸し、固相延伸分と合わせ７９倍迄延伸できた。

[Solid phase stretching]
The obtained polymer was pressed at 130 ° C. and 12 MPa to obtain a sheet having a thickness of 0.5 mm. Using this, it was subjected to solid phase stretching 6 times at 130 ° C., and was further stretched in air at 145 ° C. and could be stretched up to 79 times, including the solid phase stretching.

[Example 2]
A 1-liter autoclave made of SUS with sufficient nitrogen substitution was charged with 500 ml of heptane, and the liquid phase and gas phase were saturated with ethylene at room temperature. 0.5 mmol of methylalumoxane in terms of atom and 0.002 mmol of the following compound 2 in terms of Zr atom as a transition metal compound dissolved in toluene are added, and ethylene is supplied so that the total pressure is 8 kg / cm ² -G. The polymerization was carried out at 30 ° C. for 15 minutes.
The obtained polymer slurry was added to 2 L of methanol, stirred, filtered, washed with methanol, and dried under reduced pressure at 80 ° C. for 10 hours. The obtained polyethylene was 24.59 g, the polymerization activity was 123.0 kg / mmol-Zr, [η] was 16.9 dl / g, Mw / Mn = 3.1, and the heat of fusion was 220 J / g. It was.

[成形]
得られた重合体を１３５℃キシレン中に０．０５ｗｔ％で溶解後、８５℃に２０時間保温し、析出した単結晶を濾過、減圧乾燥した。
得られた単結晶を１３０℃で１２ＭＰａでプレスして厚さ０．５ｍｍのシートを得た。それを用い、１２０℃で６倍の固相延伸を行い更に、空気中で１３０℃で引張延伸した。延伸倍率と、ＪＩＳ Ｌ１０１３に基づき測定した弾性率、強度を表１に示す。
[配向係数]
理学電機製ＲＩＮＴ２５５０、Ｃｕターゲットを使用し、管電圧４０ｋＶ，電流３５０ｍＡで基準軸を繊維の長さ方向とし、基準軸方向に揃えて試料をホルダーに貼り付けて測定した。
[長周期]
理学電機製ＲＩＮＴ２５００、Ｃｕターゲットを使用し、管電圧５０ｋＶ，電流３００ｍＡで試料ホルダーに貼り付けて測定した。小角Ｘ線散乱散乱強度のチャートを描きそのピーク位置から算出した。

[Molding]
The obtained polymer was dissolved in xylene at 135 ° C. at 0.05 wt%, and kept at 85 ° C. for 20 hours, and the precipitated single crystal was filtered and dried under reduced pressure.
The obtained single crystal was pressed at 130 ° C. and 12 MPa to obtain a sheet having a thickness of 0.5 mm. Using this, it was subjected to solid-phase stretching 6 times at 120 ° C. and further stretched at 130 ° C. in air. Table 1 shows the draw ratio and the elastic modulus and strength measured according to JIS L1013.
[Orientation coefficient]
Using a RINT2550, Cu target manufactured by Rigaku Corporation, a tube voltage of 40 kV and a current of 350 mA, the reference axis was set to the fiber length direction, and the sample was attached to the holder in alignment with the reference axis direction.
[Long cycle]
Using RINT 2500 manufactured by Rigaku Corporation and a Cu target, measurement was performed by attaching the sample to a sample holder at a tube voltage of 50 kV and a current of 300 mA. A chart of small angle X-ray scattering intensity was drawn and calculated from the peak position.

[Preparation of solid catalyst component (C)]
Under a nitrogen atmosphere, anhydrous magnesium chloride (4.76 g), 2-ethylhexyl alcohol (18.1 ml) and decane (15 ml) were heated at 120 ° C. for 2 hours to form a homogeneous solution. Further, ethyl benzoate (0.84 ml) was added. After stirring for a period of time, cool to room temperature. This solution was added dropwise to 200 ml of titanium tetrachloride cooled to 0 ° C. with stirring over 1 hour, and the temperature was maintained for 1 hour. This solution was heated to 80 ° C. and stirred as it was for 2 hours, and then the produced solid portion was collected by filtration, suspended again in 100 ml of titanium tetrachloride, and heated and stirred at 90 ° C. for 2 hours. The solid substance produced by filtration was collected, washed with hexane until no free titanium compound was detected in the washing solution, and a decane slurry of solid component (C) was prepared. A portion of the resulting decane slurry of the solid catalyst component (C) was collected to examine the concentration, and the Ti concentration was 0.00217 mmol / mL.

[Comparative Example 1]
[polymerization]
A 1-liter autoclave made of SUS with sufficient nitrogen substitution was charged with 500 ml of heptane, and the liquid phase and gas phase were saturated with ethylene. While adding 0.5 mmol of triisobutylaluminum in terms of atom and 0.004 mmol of solid catalyst component (C) in terms of Ti atom and supplying ethylene so that the total pressure becomes 7 kg / cm ² -G, at 70 ° C. Polymerization was performed for 3 hours. The obtained polymer was washed with hexane and then dried under reduced pressure at 80 ° C. for 10 hours. The obtained polyethylene was 84.4 g, the polymerization activity was 21.1 kg / mmol-Zr, [η] was 21.0 dl / g, and the heat of fusion was 198 J / g.

[Solid phase stretching]
The same operation as in Example 1 was performed except that the polymer obtained in Comparative Example 1 was used. Tensile stretching was not possible.

[Comparative Example 2]
[polymerization]
4850 L of n-decane was injected into a SUS container purged with nitrogen, and the gas phase and liquid phase were saturated with ethylene. Triisobutylaluminum is added at 1 mmol / L in terms of atom and the solid catalyst component (C) is added at 0.0117 mmol / L in terms of Ti atom so that the total pressure is 6.3 kg / cm ² -G. Polymerization was carried out at 75 ° C. for 14 hours while supplying ethylene. After decanting the polymerization solution, the powder was dried. [Η] was 17 dl / g, Mw / Mn = 10.8, and the heat of fusion was 195 J / g. Using this polymer, the same operation as in Example 2 was performed, except that the polymer obtained in Comparative Example 2 was used. The results are shown in Table 1.

Claims (7)

For particulate carrier
(A) a transition metal compound represented by the following general formula (I);
(B) With organoaluminum oxy compound
A high elastic modulus polyolefin fiber having an elastic modulus of 120 GPa or more obtained from an ultrahigh molecular weight olefin polymer having an intrinsic viscosity of 5 to 50 dl / g, obtained using an olefin polymerization catalyst comprising a supported solid catalyst component .

(In the above formula, M represents titanium, zirconium or hafnium, m represents 2, R ¹ to R
R ⁶ may be the same as or different from each other, and represents a hydrogen atom or a hydrocarbon group, and n is
X is a number satisfying the valence of M, X represents a hydrogen atom, a halogen atom or a hydrocarbon group, and when n is 2 or more, a plurality of groups represented by X may be the same or different from each other; A plurality of groups represented by X may be bonded to each other to form a ring. ) In the general formula (I), R ¹ ~ R ⁶ Is a linear or branched alkyl group having 1 to 20 carbon atoms, a cyclic saturated hydrocarbon group having 3 to 20 carbon atoms which may be substituted with a hydrocarbon group, and an alkyl-substituted aryl. The high modulus polyolefin fiber according to claim 1, which is selected from a group. (A) a transition metal compound represented by the general formula (I) according to claim 1,
(B) With organoaluminum oxy compound
An ultrahigh molecular weight olefin polymer having an intrinsic viscosity of 5 to 50 dl / g and a heat of fusion of 200 J / g or more, obtained using an olefin polymerization catalyst comprising a supported solid catalyst component, has a melting point of the polymer. A method for producing a high-strength, high-modulus polyolefin fiber having a strength of 3.5 GPa or more and an elastic modulus of 120 GPa or more, which is further stretched after solid-phase extrusion stretching or rolling at a temperature lower than (A) a transition metal compound represented by the general formula (I) according to claim 1,
(B) With organoaluminum oxy compound
Obtained by using the olefin polymerization catalyst comprising a solid catalyst component comprising supported, ultra high molecular weight olefin polymer having an intrinsic viscosity of 5~50dl / g, heated and mixed in a solvent, once crystallized matted mixture A method for producing a polyolefin fiber having a strength of 3 GPa or more , which is stretched later. A high-strength, high-modulus polyethylene fiber obtained by the method according to claim 3. Polyethylene fiber obtained by the method according to claim 4 . (A) a transition metal compound represented by the general formula (I) according to claim 1,
(B) With organoaluminum oxy compound
Obtained from an ultrahigh molecular weight olefin polymer having a molecular weight distribution (Mw / Mn) of 4 or less and an intrinsic viscosity of 5 to 50 dl / g, obtained by using an olefin polymerization catalyst comprising a supported solid catalyst component. A stretched molded article having an orientation coefficient measured by X-ray diffraction of 0.5 or more and a long period of 30 nm or more.