CN100478364C

CN100478364C - Ethylene polymer an molded object obtained therefrom

Info

Publication number: CN100478364C
Application number: CNB2003801077744A
Authority: CN
Inventors: 佐藤康雄; 高桥守; 板东秀树; 园部善穗; 中山康
Original assignee: Mitsui Chemical Industry Co Ltd
Current assignee: Mitsui Chemical Industry Co Ltd
Priority date: 2002-12-27
Filing date: 2003-12-25
Publication date: 2009-04-15
Anticipated expiration: 2023-12-25
Also published as: CN1732189A

Abstract

An ethylene/C4-10 alpha-olefin copolymer which is reduced in neck-in in T-die molding and is excellent in suitability for high-speed film formation and mechanical strength. The polymer is obtained through polymerization in the presence of an olefin polymerization catalyst which comprises a solid support and, deposited thereon, (A) a solid transition metal catalyst component obtained through contacting from (a) a compound of a Group 4 transition metal of the Periodic Table containing one or more ligands having a cyclopentadienyl skeleton, (b) an organic aluminumoxy compound, and (c) a polyfunctional organic halide and optionally from (d) an organoaluminum compound, and which optionally contains (B) an organoaluminum compound.

Description

Ethylene-based polymer and formed body therefrom

Technical field

The present invention relates to compare with existing known ethylene-based polymer, the novel ethylene-based polymer of formability excellence and physical strength excellence, with the thermoplastic resin composition of containing this ethylene-based polymer, and by this ethylene-based polymer and this thermoplastic resin composition's gained formed body, this formed body preferably relates to film.In addition, the invention still further relates to by the above-mentioned ethylene-based polymer of specific olefin polymerization catalysis gained.

Background technology

Ethylene-based polymer is used for many-sided purposes by various forming method moulding.According to the difference of these forming methods or purposes, the characteristic that ethylene-based polymer is required is also different.For example, in the T mold forming, when the moulding cast film, the necking phenomenon that shrink to center direction the film end can take place.In case the generation necking phenomenon, not only the film reductions is little, and film end thickness will be greater than the middle portion of film, so product percent of pass will reduce.For necking phenomenon is controlled at inferior limit, in molecular weight ratio, have to select the big material of fusion tension force as ethylene-based polymer.Same characteristic the sagging that is used for preventing slush molding broken or prevent in the blown film bubble shake or broken aspect be very important.

The high-pressure process new LDPE (film grade) is compared with the ethylene-based polymer that uses the Z-type catalyst manufacturing, because of its fusion tension force is big, good moldability, so be used for purposes such as film, hollow container.But because the high-pressure process new LDPE (film grade) has complicated long branched chain structure, so can predict bad mechanical strength such as its tensile strength, tear strength, resistance to impact shock.In addition, based on same reason, can predict the high speed film forming poor in processability in the T mold forming.

In addition, although in Z-type catalyst, physical strength excellences such as the tensile strength of the ethylene-based polymer that uses aromatic ring alkene metal derivative catalyzer system and get, tear strength, resistance to impact shock, but because of the fusion Tension Difference, so can predict the variation of formabilities such as necking phenomenon is big.

As good moldability and the good ethylene-based polymer of physical strength, have the high-pressure process new LDPE (film grade) that proposed in the Japanese kokai publication hei 6-65443 communique for example etc. with using aromatic ring alkene metal derivative catalyzer system the composition of ethylene-based polymer.But when the content of high-pressure process new LDPE (film grade) after a little while,, can predict the variation of formability such as the necking phenomenon in the T mold forming is big because of the fusion tensile improves insufficiently.And at the content of high-pressure process new LDPE (film grade) for a long time, can predict physical strength variation such as tensile strength, tear strength, resistance to impact shock.

For solving this class problem, the various ethylene-based polymers of introducing long-chain branch are disclosed.

In Japanese kokai publication hei 2-276807 communique, disclose in the presence of the catalyzer of two (indenyl) hafnium dichloride of vinyl and aluminium trimethide siloxanes (alumoxane) composition, by solution polymerization gained ethylene-based polymer; In Japanese kokai publication hei 4-213309 communique, disclose two (indenyl) hafnium dichloride of the vinyl that is being attached on the silicon-dioxide and aluminium trimethide siloxanes composition catalyzer in the presence of, by vapour phase polymerization gained ethylene-based polymer; In the WO93/08221 communique, disclose in the presence of contained geometry catalyst (constraint geometrical catalyst), by solution polymerization gained ethylene-based polymer; In Japanese kokai publication hei 8-311260 communique, disclose at the Me that is attached on the silicon-dioxide ₂Si (2-Me-Ind) ₂Racemize and mesoisomer and the existence of the catalyzer formed of aluminium trimethide siloxanes under, by vapour phase polymerization gained ethylene-based polymer; In Japanese kokai publication hei 8-34819 communique, disclose under the existence of the catalyzer that two (cyclopentadienyl) zirconium dichlorides on the montmorillonite that is attached to chemical treatment form, by slurry polymerization gained ethylene-based polymer; In Japanese kokai publication hei 8-319313 communique, disclose and used by Cp*Ti (OMe) ₃The catalyzer of forming with the aluminium trimethide siloxanes carries out polymerization and the gained ethylene-based polymer.

These ethylene-based polymers are compared with the straight chain shape ethylene-based polymer that does not have long-chain branch, and fusion tension force improves, the record of the advantage of formability excellence though have, and necking phenomenon is still bigger, and it is still insufficient to predict formability raising aspect.

In addition, for improving formability, the ethylene-based polymer of introducing a small amount of high molecular weight components is disclosed.

Open the vinylite composition that discloses use Z-type catalyst gained high molecular weight components and low molecular weight compositions composition in the flat 6-172594 communique the spy.Because this vinylite composition molecular weight is too high, can predict its insufficient formability.And because use as the Z-type catalyst of multidigit site catalyst, distributes wide so can predict its composition.

Open in the flat 11-166083 communique the spy, disclose and used Z-type catalyst gained high molecular weight components and low molecular weight compositions ethylene-based polymer of forming and the vinylite composition that uses Karen Phillips catalyzer gained ethylene-based polymer.Because this vinylite composition density is too high, so it is poor to predict low temperature seal.In addition, known, use the terminal ethylenyl groups of Karen Phillips catalyzer gained ethylene-based polymer many.Therefore, it is poor to predict this vinylite heat stability of composition.Also can predict, because use is as the Z-type catalyst of multidigit site catalyst, so it is wide to form distribution.

As mentioned above, according to existing known technology, be difficult to efficiently obtain the resin of formability excellence and physical strength excellence.In other words, in case the ethylene-based polymer of formability excellence and physical strength excellence occurs, we can say that its industrial value is very big.

Result after in view of the further investigation of this situation such as the inventor, by giving specific molecular structure and fusion rerum natura, found that necking phenomenon in the T mold forming is little, the ethylene-based polymer of high speed film forming excellent in workability and physical strength excellence, so far finish the present invention.

Summary of the invention

The objective of the invention is to, provide with existing known ethylene-based polymer and compare, the novel ethylene-based polymer of formability excellence and physical strength excellence, can efficiently make the polymerizing catalyst of this ethylene-based polymer, the thermoplastic resin composition of containing this ethylene-based polymer, and by this ethylene-based polymer and this thermoplastic resin composition's gained formed body, this formed body is preferably film.

Ethylene-based polymer of the present invention is the multipolymer of the alpha-olefin of ethene and carbonatoms 4～10, it is characterized in that, satisfies following condition [k1]～[k3] simultaneously:

Melt flow rate (MFR) (MFR) scope when [k1] 190 ℃ during the 2.16kg load is 1.0～50g/10 minute.

The LNR scope of the constriction gage degree when [k2] is defined as the film moulding is 0.6～1.4.

Breaking point coiling speed [DS (m/ branch)] when [k3] 160 ℃ satisfies following relational expression (Eq-1) with melt flow rate (MFR) (MFR).

12×MFR ^0.577≤DS≤165×MFR ^0.577......(Eq-1)

Ethylene-based polymer of the present invention except that above-mentioned condition, preferably also satisfies following condition [m1]～[m3] simultaneously.

[m1] density (d) is at 890～950kg/m ³Scope in.

Fusion tension force [MT (g)] when [m2] 190 ℃ and 200 ℃, the shear viscosity [η of circular frequency 1.0rad/ during second ^*(Poise)] ratio [MT/ η ^*(g/Poise)] 2.00 * 10 ^-4～9.00 * 10 ^-4Scope.

[m3] by ¹³The methyl branch number that C-NMR measures [A (/ 1000C)] and the ethyl branch number [B (/ 1000C)] sum [(A+B) (/ 1000C)] below 1.4.

And ethylene-based polymer of the present invention preferably satisfies any more than 1 of following condition [n1]～[n3] except that above-mentioned condition.

The Z-average molecular weight (Mz) that [n1] measures with GPC and the ratio (Mz/Mw) of weight-average molecular weight (Mw) are more than 10.

Per 1 molecule chain end ethene radix (V) that the terminal ethylenyl groups number of per 1000 carbon atoms that [n2] measured by IR [v (/ 1000C)] and the number-average molecular weight (Mn) that GPC measures are calculated is below 0.47/1 molecular chain.

Fusing point maximum peak among [n3] DSC (Tm (℃)) satisfy following relational expression (Eq-2) with density (d).

0.315×d-200≤Tm≤0.315×d-170......(Eq-2)

Comprising solid-state carrier, (A) polymerization under the existence of the olefin polymerization catalysis of solid-state transition metal catalyst component and (B) organo-aluminium compound as required, can efficiently make ethylene-based polymer of the present invention, should (A) solid-state transition metal catalyst component contain multi-functional Organohalogen compounds that the periodic table of elements the 4th group transition metal compound, (b) organoaluminum oxo-compounds, (c) of the dentate that has cyclopentadienyi skeleton more than 1 represent with general formula (I), contact with as required (d) organo-aluminium compound and obtain by (a).

In addition, ethylene-based polymer of the present invention, also can be by ethene or ethylene/alpha-olefin pre-polymerization, and by the Z-average molecular weight that GPC records is more than 6000000, and die swelling is than being the above-mentioned solid-state transition metal catalyst component that the solid-state transition metal catalyst component of every 1g more than 1.4 contains 0.01～1000g prepolymer, polymerization under the existence of the prepolymerization catalyst that forms with as required (B) organo-aluminium compound and efficient the manufacturing.

Preferred multi-functional Organohalogen compounds (c) are the compounds shown in the following general formula (1).

(Q ¹) _o-R-(Q ²) _p......(I)

In the formula (I), R is the base that contains (o+p) valency of 1 above halogen atom, and o, p are the positive integers of satisfied (o+p) 〉=2, Q ¹With Q ²Expression-OH ,-NH ₂Or-NLH, in-NLH, L is selected from C ₁～C ₂₀Alkyl, C ₁～C ₂₀Halogen-containing alkyl, contain silica-based, contain the oxygen base, contain sulfenyl, any base of nitrogenous base or phosphorous-containigroups groups, L also can interosculate into ring with R, N with N with R, N.

In addition, the transistion metal compound (a) that preferably contains the periodic table of elements the 4th family of the dentate that has cyclopentadienyi skeleton more than 1 is with following general formula (II), (III) or (IV) compound of expression.

Formula (II) with (III) in, R ¹～R ⁶Independent respectively expression is selected from hydrogen atom, halogen atom, C ₁～C ₂₀Alkyl, C ₃～C ₂₀Cycloalkyl, C ₂～C ₂₀Thiazolinyl, C ₆～C ₂₀Aryl, C ₇～C ₂₀The base of aralkyl, can contain silicon, halogen or germanium atom; R ³With R ⁴, R ⁴With R ⁵, R ⁵With R ⁶In one of them group can interosculate into ring.R ⁷Being the divalent base that combines 2 dentates, is C ₁～C ₂₀Alkyl, C ₁～C ₂₀Contain brine alkyl, contain the base of silica-based or germanic or tin, 2 substituting groups on same carbon, silicon, germanium, the tin atom also can interosculate into ring.t ¹With t ²Independent respectively expression is selected from hydrogen atom, halogen atom, C ₁～C ₂₀Alkyl, C ₁～C ₂₀Contain brine alkyl, contain silica-based, contain the oxygen base, contain sulfenyl, the base of nitrogenous base and phosphorous-containigroups groups.M is the transition metal that is selected from titanium, zirconium, hafnium.

In the formula (IV), R ⁷, t ¹, t ², M is identical with the definition of formula (II), R ⁸～R ¹⁹Independent respectively expression is selected from hydrogen atom, halogen atom, C ₁～C ₂₀Alkyl, C ₃～C ₂₀Cycloalkyl, C ₂～C ₂ ₀Thiazolinyl, C ₆～C ₂₀Aryl or C ₇～C ₂₀The base of aralkyl can contain silicon, halogen or germanium atom, is abutted to R ⁸～R ¹⁹Substituting group also can interosculate into ring.

In addition, by ethylene-based polymer of the present invention is mixed with other thermoplastic resin, can obtain formability excellence and physical strength thermoplastic resin excellent composition.By processing ethylene-based polymer of the present invention and the resin combination that contains ethylene-based polymer, can obtain the formed body of formability excellence and physical strength excellence, preferably obtain film.

Description of drawings

Fig. 1 is a synoptic diagram of observing the slit die be used to measure lab scale constriction ratio of the present invention from the top.

Fig. 2 is the synoptic diagram from the same slit die of transverse observation.

Fig. 3 is the same slit die A-B sectional view.

Fig. 4 is the synoptic diagram from top view cooling roller and air nozzle.

Fig. 5 is the synoptic diagram from transverse observation cooling roller and air nozzle.

Fig. 6 is a synoptic diagram of observing the capillary rheometer be used to measure mould of the present invention-die swelling ratio from the top.

Fig. 7 is a synoptic diagram of observing the same capillary rheometer from the side.

Embodiment

Below, be divided into that three parts (1) ethylene-based polymer of the present invention, (2) are used to make the polymerizing catalyst of this ethylene-based polymer and the purposes of (3) this ethylene-based polymer specifies preferred implementation of the present invention.

(1) ethylene-based polymer of the present invention

Ethylene-based polymer of the present invention is the multipolymer of the alpha-olefin of ethene and carbonatoms 4～10, the multipolymer of the alpha-olefin of optimal ethylene and carbonatoms 4～10, wherein, when using 1-butylene as comonomer, the alpha-olefin of carbonatoms 6～10 also is essential, more preferably the multipolymer of the alpha-olefin of ethene and carbonatoms 6～10.As the alpha-olefin that can be used for the carbonatoms 4～10 of ethylene copolymer, can enumerate 1-butylene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene etc.

Such ethylene-based polymer has characteristic shown in following [k1]～[k3].

[k1] melt flow rate (MFR) (MFR) scope is 1.0～50g/10 minute, is preferably 2.0～50g/10 minute, more preferably 4.0～50g/10 minute.

Melt flow rate (MFR) (MFR) is more than 1.0g/10 minute the time, and the shear viscosity of gained ethylene-based polymer can be not too high, good moldability.Melt flow rate (MFR) (MFR) is below 50g/10 minute the time, and the tensile strength of gained ethylene-based polymer is good.

Melt flow rate (MFR) (MFR) has very big dependency with molecular weight, and (MFR) is littler for melt flow rate (MFR), and molecular weight is bigger; Melt flow rate (MFR) (MFR) is bigger, and molecular weight is littler.Also known, the molecular weight of ethylene-based polymer is by the decision of the ratio of components (hydrogen/ethene) of hydrogen in the polymerization system and ethene (for example Kazuo Soga, KODANSHA " CATALYTIC OLEFIN POLYMERIZATION ", p376 (1990)).Therefore, by increase and decrease hydrogen/ethylene ratio, just can make the ethylene-based polymer of melt flow rate (MFR) (MFR) with above-mentioned upper and lower bound.

According to ASTM D1238-89, under 190 ℃, 2.16kg loading condition, measure melt flow rate (MFR) (MFR).

[k2] LNR scope is 0.6～1.4, is preferably 0.7～1.3, more preferably 0.8～1.2.

LNR is 1.4 when following, and the constriction of gained ethylene-based polymer is good.The wide minimizing value wide of goods when in the present embodiment, constriction is meant the T mold forming with respect to the die lip opening.

Shown in LNR and the embodiment 1 in the manufacture method＜leading portion〉molecular weight and the＜back segment of polymeric ethylene-based polymer〉ratio＜leading portion of molecular weight of polymeric ethylene-based polymer〉molecular weight/＜back segment〉molecular weight is in close relations, its trend is:＜leading portion〉molecular weight/＜back segment〉molecular weight is bigger, and LNR is littler;＜leading portion〉molecular weight/＜back segment〉molecular weight is littler, and LNR is bigger.Also known, the molecular weight of ethylene-based polymer is by the decision of the ratio of components (hydrogen/ethene) of hydrogen in the polymerization system and ethene (for example Kazuo Soga, KODANSHA " CATALYTIC OLEFIN POLYMERIZATION ", p376 (1990)).Therefore, by regulating hydrogen/ethylene ratio, increase and decrease＜leading portion〉molecular weight/＜back segment〉molecular weight, just can make the ethylene-based polymer of the LNR with above-mentioned upper and lower bound.

Constriction amount when LNR is shaped to film by the small-sized slit die of use with working sample is with (trade(brand)name: the ratio of the constriction amount in the time of MIRASON M11) determines according to the high-pressure free radical polymerization legal system polyethylene of selling with quadrat method moulding Mitsui Chemicals, Inc.LNR is measured by the device that comprises (a) capillary rheometer, (b) slit die, (c) cooling roller, air nozzle, (d) draw roll.

(a) capillary rheometer plays the effect of resin melt extrusion.Capillary rheometer uses the smart mechanism of Japan to make institute's corporate system capillary rheometer: Capillograph 1B (barrel diameter Φ 10mm), the condition of dividing with 200 ℃ of barrel temperatures, velocity of piston 50mm/ are carried out.In addition, working sample is that each mensuration used 20g, and the fusion time is 6 minutes.

(b) Fig. 1 represents that Fig. 2 represents the synoptic diagram from transverse observation from the synoptic diagram of the top observation of slit die, and Fig. 3 represents the A-B sectional view.In slit die, the nozzle of packing into (1) by being connected in the adapter of connector portions (1), is fixed under the cylindrical shell of capillary rheometer, heats ((3) of Fig. 2, thermopair insertion section) to 200 ℃ with plate heater.

(c) Fig. 4 represents the synoptic diagram of cooling roller, air nozzle frontal, and Fig. 5 represents the synoptic diagram that it is horizontal.Cooling roller (4), air nozzle (5) are located under the slit die, and the fixed distance of slit die lower end and cooling roller (4) upper end is 10mm.The long 26cm of air nozzle makes gas hole with interval, the diameter 1mm of 5.5mm.Under 501/ minute condition of cooling air delivery, implement.

Mold the working sample film by said apparatus, the film of getting film terminal 1.75m～1.95m is as sample.The constriction amount (C) of working sample is deducted as the wide value decision of the film of sample film by the Mould Breadth (40mm) of slit die.In addition, by Mitsui Chemicals, Inc sell (trade(brand)name: constriction amount (d) MIRASON M11) is also by method decision same as above by high-pressure free radical polymerization legal system polyethylene.LNR is determined by following formula (Eq-3).

LNR＝C/D......(Eq-3)

12×MFR ^0.577≤DS≤165×MFR ^0.577......(Eq-1)

Preferably satisfy following relational expression (Eq-4)

17×MFR ^0.577≤DS≤53×MFR ^0.577......(Eq-4)

More preferably satisfy following relational expression (eq-5)

17×MFR ^0.577≤DS≤40×MFR ^0.577......(Eq-5)

Breaking point coiling speed (DS) is 17 * MFR ^0.577When above, the high speed film forming excellent in workability of gained ethylene-based polymer.

Breaking point coiling speed (DS), be decided by in the manufacture method of embodiment 1 expression＜leading portion polymeric ethylene-based polymer group component and＜back segment the ratio＜leading portion of polymeric ethylene-based polymer group component group component/＜back segment〉group component, its trend is,＜leading portion〉group component/＜back segment〉group component is bigger, and the breaking point coiling speed (DS) under the same melt flow rate (MFR) (MFR) is littler;＜leading portion〉group component/＜back segment〉group component is littler, and same melt flow rate (MFR) (MFR) breaking point coiling speed (DS) down is more greatly.Therefore, regulate shown in the embodiment 1 in the manufacture method＜leading portion polymerization time and＜back segment polymerization time, by increase and decrease＜leading portion〉group component/＜back segment〉group component, just can make the ethylene-based polymer that satisfies breaking point coiling speed of the present invention (DS) and melt flow rate (MFR) (MFR) relation.

Breaking point coiling speed (DS) changes the speed limit of batching the fusion ethylene-based polymer by the limit batches the coiling speed decision the when stretching thing of ethylene-based polymer ruptures.In the mensuration, use the smart mechanism of Japan to make institute's corporate system capillary rheometer: Capillograph 1B, barrel diameter Φ 10mm.With 160 ℃ of resin temperatures, 6 minutes fusion times, barrel diameter Φ 10mm, extruded velocity 15mm/ branch, capillary caliber Φ 2.00mm, long capillary tube 10mm, coiling speed 15～400m/ branch, batch acceleration 100m/ branch ²Condition implement.When having bubble etc. in the ethylene-based polymer, breaking point coiling speed (DS) can become minimum.For this reason, carry out 7 times and measure, get wherein bigger 3 measurement result mean values as breaking point coiling speed (DS).

Ethylene-based polymer of the present invention preferably also satisfies following condition [m1]～[m3] except that above-mentioned condition.

The scope of [m1] density (d) is 890～950kg/m ³, preferred 900～940kg/m ³, 905～935kg/m more preferably ³

Density (d) is at 890kg/m ³When above, gained ethylene-based polymer good heat resistance, density (d) is at 950kg/m ³When following, the low temperature seal of gained ethylene-based polymer is good.

Density is relevant with the alpha-olefin content of ethylene-based polymer, and alpha-olefin content is fewer, and density is higher; Alpha-olefin content the more, density is lower.Also known, Walter Kaminsky for example, Makromol.Chem.193, p.606 in (1992), the alpha-olefin content in the ethylene-based polymer is by ratio of components alpha-olefin/ethene decision of alpha-olefin in the polymerization system and ethene.Therefore, by increase and decrease alpha-olefin/ethylene ratio, can make ethylene-based polymer with above-mentioned lower limit and upper limit density.

At 120 ℃, working sample is implemented thermal treatment in 1 hour, behind 1 hour slow cool to room temperature of straight line, measure density (d) with density gradient tube.

[m2] fusion tension force [MT (g)] and 200 ℃, the shear viscosity [η of circular frequency 1.0rad/ during second ^*(Poise)] ratio [MT/ η ^*(g/Poise)] scope is 2.00 * 10 ^-4～9.00 * 10 ^-4, preferred 2.30 * 10 ^-4～9.00 * 10 ^-4, more preferably 3.00 * 10 ^-4～9.00 * 10 ^-4

MT/ η ^*Be 2.00 * 10 ^-4When above, the constriction of gained ethylene-based polymer is good.

MT/ η ^*With in the manufacture method shown in the embodiment 1＜leading portion polymeric ethylene-based polymer molecular weight and＜back segment the ratio＜leading portion of polymeric ethylene-based polymer molecular weight molecular weight/＜back segment molecular weight is closely related, its trend is,＜leading portion〉molecular weight/＜back segment〉molecular weight is bigger, MT/ η ^*Bigger;＜leading portion〉molecular weight/＜back segment〉molecular weight is littler, MT/ η ^*Littler.Also known, the molecular weight of ethylene-based polymer is by the decision of the ratio of components (hydrogen/ethene) of hydrogen in the polymerization system and ethene, Kazuo Soga for example, KODANSHA " CATALYTIC OLEFIN POLYMERIZATION ", p376 (1990).Therefore, by regulating hydrogen/ethylene ratio, increase and decrease＜leading portion〉molecular weight/＜back segment〉molecular weight, just can make MT/ η with above-mentioned upper and lower bound ^*Ethylene-based polymer.

The stress decision of fusion tension force (MT) when measuring with certain speed stretching fused polymkeric substance.Measure and use the smart mechanism of Japan to make made MT mensuration machine.Condition with 190 ℃ of resin temperatures, 6 minutes fusion times, barrel diameter Φ 9.55mm, extruded velocity 15mm/ branch, coiling speed 10～20m/ branch, nozzle diameter Φ 2.095mm, nozzle length 8mm is implemented.

In addition, 200 ℃, the shear viscosity (η of circular frequency 1.0rad/ during second ^*) shear viscosity (η when in 0.02512≤ω≤400 scopes, measuring 200 ℃ of temperature ^*) circular frequency [ω (rad/ second)] disperse and determine.Use Rheometrix corporate system Rheometer RDS-II in the mensuration.Sample holder uses the parallel plate of Φ 25mm, and thickness of sample is about 1.8mm.Measuring point is that each ω is 5 points.In the measurement range that moment of torsion can be surveyed, and avoid moment of torsion to cross and in 10～30% scope, suitably select distortion greatly.Sample during shear viscosity is measured is to use the made pressure forming machine of refreshing rattan metal industry, at 190 ℃ of preheating temperatures, 5 minutes warm up time, 190 ℃ of Heating temperatures, 2 minutes heat-up times, heated pressure 100kg/cm ², 20 ℃ of cooling temperatures, 5 minutes cooling times, cooling pressure 100kg/cm ²The working sample of thickness 2mm of condition overdraft moulding.

[m3] by ¹³The methyl branch number that C-NMR measures [A (/ 1000C)] and ethyl branch number [B (/ 1000C)] sum [(A+B) (/ 1000C)] is below 1.4, be preferably below 1.0, more preferably below 0.6.In addition, the methyl branch number and the ethyl branch number of the present invention's definition as described later, define with per 1000 carbonatomss.

Known, because of when having short-chain branch such as methyl branch, ethyl branch in the ethylene-based polymer, short-chain branch will enter crystallization, cause crystal plane to enlarge at interval, so the resin physical strength (for example reduces, the big kind time youths in pool etc.: high molecular life prediction and life-span prolong technology, p481, NTS (2002)).Therefore, it is 1.4 when following that methyl branch number and ethyl branch are counted sum (A+B), and the physical strength of gained ethylene-based polymer is good.

The polymerization process of the methyl branch number in the ethylene-based polymer, ethyl branch number and ethylene-based polymer has much relations, by the ethylene-based polymer of high-pressure free radical polymerization gained with the polycoordination of using Ziegler-type catalyst ethylene-based polymer compare, methyl branch number, ethyl branch number are many.When polycoordination, the ratio of components (propylene/ethylene, 1-butylene/ethene) of the propylene in the methyl branch number in the ethylene-based polymer, ethyl branch number and the polymerization system, 1-butylene, ethene relation is very big.Therefore, by increase and decrease 1-butylene/ethene, can make and have the ethylene-based polymer that above-mentioned methyl branch number and ethyl branch are counted sum (A+B).

By ¹³The methyl branch number that C-NMR measures and the ethyl branch number is as described below determines.Measure and adopt NEC (strain) system ECP500 type nuclear magnetic resonance device (1H:500MHz), by integration 10,000～30,000 time mensuration.And, used main chain methylene peak (29.97ppm) as the chemical shift standard.Measure in the quartz glass tube at the commercially available NMR of diameter 10mm, the PE sample and 3ml and the superfine orthodichlorobenzene of the pure pharmaceutical worker's industry of light (strain) corporate system that add 250～400mg: ISOTEC corporate system benzene-d6=5: the mixed solution of 1 (volume ratio), at 120 ℃ of heating down, homodisperse.In the NMR spectrum each ownership that absorbs according to No. 141, chemical field supplementary issue " the NMR-summary is carried out with the standard of experiment guide [I], p132～p133.The methyl branch number of per 1000 carbon atoms can absorb (19.9ppm) according to the methyl that causes because of methyl branch and calculate with respect to the integrated intensity ratio of the absorption integration summation that occurs in 5～45ppm scope.And the ethyl branch number can be calculated with respect to the integrated intensity ratio of the absorption integration summation that occurs in 5～45ppm scope according to the ethyl absorption (10.8ppm) that ethyl branch causes.

And ethylene-based polymer of the present invention preferably also satisfies any more than 1 of following condition [n1]～[n3] except that above-mentioned condition.

The Z-average molecular weight (Mz) that [n1] measures with GPC is more than 10 with the ratio (Mz/Mw) of weight-average molecular weight (Mw), be preferably more than 20, more preferably more than 30.Mz/Mw is 10 when above, and that the fusion tension force of gained ethylene-based polymer becomes is big, formability is excellent.

In the manufacture method shown in embodiment 1＜leading portion the polymeric ethylene-based polymer molecular weight and＜back segment the difference of molecular weight of polymeric ethylene-based polymer enlarges, then Mz/Mw increases; Difference is dwindled, and then Mz/Mw reduces.Also known, the molecular weight of ethylene-based polymer is by the decision of hydrogen in the polymerization system and ethene ratio of components (hydrogen/ethene), Kazuo Soga for example, KODANSHA " CATALYTIC OLEFIN POLYMERIZATION ", p376 (1990).For this reason, by regulating hydrogen/ethene, increase and decrease＜leading portion〉polymeric ethylene-based polymer molecular weight and＜back segment〉polymeric ethylene-based polymer molecular weight, just can make ethylene-based polymer with above-mentioned Mz/Mw.

Use Waters corporate system GPC-150C, mensuration Z-average molecular weight as described below (Mz), weight-average molecular weight (Mw).Separator column is TSKgel GMH6-HT and TSKgel GMH6-HTL, column dimension is respectively internal diameter 7.5mm, long 600mm, column temperature is 140 ℃, mobile phase is used orthodichlorobenzene (with the pure pharmaceutical worker's industry of light), antioxidant uses 0.025 weight %BHT (military field medicine), divides with 1.0ml/ and moves, and sample solution concentration is 0.1 weight %, sample injects measures 500 μ l, and detector uses differential refractometer.Polystyrene standard, molecular weight Mw≤1000 and Mw 〉=4 * 10 ⁶Use east Cao company goods, 1000≤Mw≤4 * 10 ⁶Use Pressure Chemical company goods.Molecular weight is through the general gauged calculated value that converts and try to achieve as PE.

The terminal ethylenyl groups number (V) of per 1 molecular chain that the terminal ethylenyl groups number of per 1000 carbonatomss that [n2] measures with IR [v (/ 1000C)] and the number-average molecular weight (Mn) that GPC measures are calculated is that 0.47/1 molecular chain is following, preferred 0.30/1 molecular chain is following, more preferably below 0.16/1 molecular chain.The terminal ethylenyl groups number (V) of per 1 molecular chain is 0.47/1 molecular chain when following, the excellent heat stability the during forming process of gained ethylene-based polymer.

Hydrogen in the terminal ethylenyl groups number (V) of per 1 molecular chain and the polymerization system and the ratio of components (hydrogen/ethene) of ethene relation are very big, and hydrogen/ethene increases, and the terminal ethylenyl groups number (V) of then per 1 molecular chain reduces; And hydrogen/ethene reduces, and the terminal ethylenyl groups number (V) of then per 1 molecular chain increases.Therefore, by shown in the increase and decrease embodiment 1 in the manufacture method＜leading portion hydrogen/ethene, just can make ethylene-based polymer with above-mentioned per 1 molecule chain end ethene radix (V).

Per 1 molecule chain end ethene radix (V) adopts the number-average molecular weight (Mn) of GPC mensuration and the terminal ethylenyl groups number of per 1000 carbon atoms that IR measures (v), to be determined by following formula (Eq-6).

V＝Mn×v/14000......(Eq-6)

Number-average molecular weight (Mn) is used Waters corporate system GPC-150, measures by the same method.

The terminal ethylenyl groups number of per 1000 carbon atoms (v) uses the following mensuration of Japanese beam split corporate system infrared spectrophotometer FT-IR410 type.About 0.3g ethylene-based polymer is sandwiched polytetrafluoroethylene fiber plate (0.1mm is thick), aluminium sheet (0.1mm is thick), iron plate (2～3mm is thick) successively, at 180 ℃ of hydraulic molding machine Heating temperatures, 3 minutes heat-up times, forming pressure 50～100kg/cm ²Following mold pressing is then at room temperature, 0～50kg/cm ²Pressure cooled off 1 minute down, and sample is measured in preparation.Utilize the transmittance method, at measurement range 5000cm ^-1～400cm ^-1, measure under the resolving power 2cm, 4 times condition of accumulative total.With 910cm ^-1The bands of a spectrum that are absorbed as from terminal ethylenyl groups of following detection according to the typical curve that uses the polyethylene that do not contain unsaturated link(age) and a certain end to make as the polyethylene of vinyl entirely, carry out quantitatively the terminal ethylenyl groups number of per 1000 carbonatomss (v (/ 1000C)).

Fusing point maximum peak among [n3] DSC [Tm (℃)] satisfy following relational expression (Eq-2) with density (d).

(0.315×d)-200≤Tm≤(0.315×d)-170......(Eq-2)

Preferably satisfy following relational expression (Eq-7)

(0.315×d)-200≤Tm≤(0.315×d)-173......(Eq-7)

Fusing point maximum peak (Tm) is in that (0.315 * d)-170 when following, the low temperature seal excellence of gained ethylene-based polymer.

Fusing point maximum peak (Tm) is except that relevant with density (d), and also distribute with gained ethylene-based polymer molecule interchain alpha-olefin (form and distribute) is relevant.When density was identical, it was wide more to form distribution, had the few molecular chain of alpha-olefin to exist more and formed thick crystalline trend, so fusing point maximum peak (Tm) is high more; It is narrow more to form distribution, and each molecular chain of alpha-olefin exists more equably, can not form thick crystallization, so fusing point maximum peak (Tm) is low more.When catalyzer is Z-type catalyst, as can be known, because of active site inhomogeneous, broaden (for example loose Pu one hero etc.: polyethylene technology reader, p20, industrial research council (2001)) so the composition of gained ethylene-based polymer distributes.Therefore, when ethylene-based polymer density was identical, fusing point maximum peak (Tm) increased.When catalyzer is aromatic ring alkene metal derivative, because of active site even, so the gained ethylene-based polymer is formed distribution narrow, its result, when density is identical, fusing point maximum peak (Tm) step-down.Fusing point maximum peak (Tm) under the same density also can be changed by polymerization temperature.In case the raising polymerization temperature is just by the trend even, that form distribution narrow that becomes in the polymerization system.Fusing point maximum peak (Tm) step-down when its result, same density.In case the reduction polymerization temperature is just by becoming inhomogeneous in the polymerization system, forming the trend that distributes and broaden.Its result, the fusing point maximum peak (Tm) under the same density increases.Therefore, by shown in the increase and decrease embodiment 1 in the manufacture method＜back segment polymerization temperature, just can make the ethylene-based polymer of the relation that satisfies above-mentioned fusing point maximum peak (Tm) and density (d).

Use PERKIN ELMER corporate system Pyris1, following mensuration fusing point maximum peak (Tm).Use refreshing rattan metal industry corporate system pressure forming machine, at 190 ℃ of preheating temperatures, 5 minutes warm up time, 190 ℃ of Heating temperatures, 2 minutes heat-up times, heated pressure 100kg/cm ², 20 ℃ of cooling temperatures, 5 minutes cooling times, cooling pressure 100kg/cm ²Condition under, pressure forming is the working sample of thickness 2mm, is mixed with to measure used sample.The aluminium dish of will about 5mg working sample packing into, (nitrogen: the 20ml/ branch), under temperature condition 1.～3., implement to measure under nitrogen environment.

1. since 30 ℃, be warmed up to 200 ℃ with 10 ℃/minute

2. after 5 minutes, cool to 30 ℃ 200 ℃ of maintenances with 20 ℃/minute

3. since 30 ℃, be warmed up to 200 ℃ with 10 ℃/minute

With 3. mensuration and endothermic curve maximum peak temperature be fusing point maximum peak (Tm (℃)).

(2) be used to make the polymerizing catalyst of ethylene-based polymer

The both available single-stage polymerization methods of ethylene-based polymer of the present invention, the above multistage polymerization methods of also available two-stage makes.In addition, as mentioned above, in the multistage polymerization methods, adopt usually multistage, be preferably secondary or three grades of polyreaction modes.Multistage polymerization of the present invention comprises as the later back level polymerization in the prime polymerization of initial polymerization process (in the aftermentioned explanation, also being called " preceding poly-" or " pre-polymerization ") and the second stage (in aftermentioned illustrates, also be called " this polymerization ").And under given conditions gained prepolymer (in aftermentioned explanation, being also referred to as " prepolymer ") as polymerizing catalyst, make vinyl polymerization or make ethene with the alpha-olefin copolymer of carbonatoms 4～10 and must ethylene-based polymer also belong to a part of the present invention.Promptly, ethylene-based polymer of the present invention, in following 4 kinds of polymerizing catalysts (C-1)～(C-4) any in the presence of, (being total to) polymerization (this polymerization) of the alpha-olefin by ethene or ethene and carbonatoms 4～10 is made, wherein preferred the 3rd kind of olefin polymerization catalysis (C-3) and the 4th kind of olefin polymerization catalysis (C-4), particularly preferred catalyzer is the 4th a kind of olefin polymerization catalysis (C-4).

The 1st kind of olefin polymerization catalysis of the present invention (C-1) is characterised in that, comprise that periodictable the 4th group transition metal compound, (b) organoaluminum oxo-compounds that solid-state carrier, (A) (a) contain the dentate that has cyclopentadienyi skeleton more than 1 contact with multi-functional Organohalogen compounds component shown in (c) general formula (I) and solid-state transition metal catalyst component and (B) organo-aluminium compound as required.

(Q ¹) _o-R-(Q ²) _p......(I)

In the formula (I), R is the base that contains (o+p) valency of 1 above halogen atom, and o, p are the positive integers of satisfied (o+p) 〉=2, Q ¹With Q ²Expression-OH ,-NH ₂Or-NLH, among-the NLH, L is selected from C ₁～C ₂₀Alkyl, C ₁～C ₂₀Halogen-containing alkyl, contain silica-based, contain the oxygen base, contain sulfenyl, any base of nitrogenous base or phosphorous-containigroups groups, L can interosculate into ring with R, N with N with R, N.

The 2nd olefin polymerization catalysis of the present invention (C-2) is characterised in that, comprise that solid-state carrier, (A) (a) contain multi-functional Organohalogen compounds component shown in periodictable the 4th group transition metal compound, (b) organoaluminum oxo-compounds, (c) general formula (I) of the dentate that has cyclopentadienyi skeleton more than 1, contact with (d) organo-aluminium compound and solid-state catalyst component and (B) organo-aluminium compound as required.

The 3rd olefin polymerization catalysis of the present invention (C-3) is characterised in that, the solid-state transition metal catalyst component that constitutes above-mentioned olefin polymerization catalysis (C-1) is more than 6000000 by the Z-average molecular weight of ethene or ethylene/alpha-olefin pre-polymerization and GPC and the solid-state transition metal catalyst component of every 1g contains 0.01～1.000g, die swelling is formed than the prepolymer of the component more than 1.4 and (B) organo-aluminium compound as required.

The 4th olefin polymerization catalysis of the present invention (C-4) is characterised in that, the solid-state transition metal catalyst component that constitutes above-mentioned olefin polymerization catalysis (C-2) is more than 6000000 by the Z-average molecular weight of ethene or ethylene/alpha-olefin pre-polymerization and GPC and the solid-state transition metal catalyst component of every 1g contains 0.01～1.000g, die swelling is formed than the prepolymer of the component more than 1.4 and (B) organo-aluminium compound as required.

Below, specify olefin polymerization catalysis of the present invention and the olefine polymerizing process that uses this olefin polymerization catalysis.In addition, among the present invention, " polymerization " this term not only refers to single poly-, also comprises the meaning of copolymerization, and term " polymer " " not only refer to also comprise multipolymer by single polymers.

At first, spendable each component in the olefin polymerization catalysis of the present invention is described.Periodictable the 4th group transition metal compound (also claiming " component (a) " down) that spendable among the present invention (a) contains the dentate that has cyclopentadienyi skeleton more than 1 is a transistion metal compound shown in the following logical formula V.

MG ¹ _x......(V)

In the formula, M represents to be selected from the transition metal atoms of periodictable the 4th family, and G represents the dentate with transition-metal coordination, wherein at least 1 G ¹Be dentate, have the G outside the dentate of cyclopentadienyi skeleton with cyclopentadienyi skeleton ¹Be alkyl, alkoxyl group, aryloxy, trialkylsilkl, SO ₃J base, halogen atom or hydrogen atom, wherein, J is the alkyl that can have substituent carbonatomss 1～8 such as halogen, x represents the valence of transition metal.

In the above-mentioned logical formula V, M is the transition metal atoms that is selected from periodictable the 4th family, specifically can enumerate zirconium atom, titanium atom or hafnium atom, is preferably zirconium atom.

As dentate, can enumerate for example alkyl substituted cyclopentadienyls such as cyclopentadienyl, methyl cyclopentadienyl, dimethyl cyclopentadienyl, trimethylammonium cyclopentadienyl, tetramethyl-ring pentadienyl, pentamethyl-cyclopentadienyl, ethyl cyclopentadienyl, methylethyl cyclopentadienyl, propyl group cyclopentadienyl, methyl-propyl cyclopentadienyl, butyl cyclopentadienyl, methyl butyl cyclopentadienyl, hexyl cyclopentadienyl with cyclopentadienyi skeleton; Or indenyl, 2-methyl indenyl, 2-ethyl-indenyl, 2-n-propyl indenyl, 2-phenyl indenyl, 4-phenyl indenyl, 2-methyl-4-phenyl indenyl, 2-methyl-4,6-di-isopropyl indenyl, 2-methyl-4,5-benzo indenyl, 4,5,6,7-tetrahydroindenyl, fluorenyl, 9-methylfluorenyl, 2,7-dimethyl fluorenyl, 2,7-di-t-butyl fluorenyl etc.Replacements such as the also available halogen atom of these bases, trialkylsilkl.

When containing the dentate that has cyclopentadienyi skeleton more than 2 with the compound of above-mentioned general formula (V) expression, wherein 2 dentates with cyclopentadienyi skeleton can be passed through methylene radical between mutually, the di-isopropyl methylene radical, the methyl tertbutyl methylene radical, the dicyclohexyl methylene radical, the methyl cyclohexane methylene, the aminomethyl phenyl methylene radical, the phenylbenzene methylene radical, the methylnaphthalene methylene, the dinaphthyl methylene radical, ethylidene, propylidene, isopropylidene, the ring propylidene, the ring butylidene, the ring pentylidene, cyclohexylene, encircle inferior heptyl, two rings [3.3.1] are nonamethylene, the norborneol subunit, the Buddha's warrior attendant subunit, the tetraline subunit, chlorethylidene, the chlorine methylene radical, silicylene, the methyl silicylene, the dimethyl silicylene, the di-isopropyl silicylene, the methyl tertbutyl silicylene, the dicyclohexyl silicylene, the methylcyclohexyl silicylene, the aminomethyl phenyl silicylene, the phenylbenzene silicylene, methyl naphthyl silicylene, the dinaphthyl silicylene, ring dimethylene silicylene, ring trimethylene silicylene, ring tetramethylene silicylene, the cyclopentamethylene silicylene, the hexamethylene silicylene, ring heptamethylene silicylene, and silicon is become germanium in silica-based in above-mentioned containing, the germanic base of tin, contain tinbase etc. and combination.

As the dentate G beyond the dentate with cyclopentadienyi skeleton ¹, specifically can enumerate following base.As alkyl, can enumerate alkyl, cycloalkyl, aryl, aralkyl etc., more specifically, as alkyl, can enumerate methyl, ethyl, propyl group, sec.-propyl, butyl etc., as cycloalkyl, cyclopentyl, cyclohexyl etc. can be enumerated,, phenyl, tolyl etc. can be enumerated as aryl, as aralkyl, can enumerate benzyl, neophyl etc.

And, can enumerate methoxyl group, oxyethyl group, butoxy etc. as alkoxyl group, and as aryloxy, can enumerate phenoxy group etc., as halogen, can enumerate fluorine, chlorine, bromine, iodine etc.

As with SO ₃The dentate of J basis representation can be enumerated tosic acid ester group, methylsulphonic acid ester group, trifluoromethane sulfonic acid ester group etc.The transistion metal compound that comprises the dentate with such cyclopentadienyi skeleton, for example the transition metal atoms valency is 4 o'clock, more specifically available following general formula (Va) expression.

G ² _kG ³ _lG ⁴ _mG ⁵ _nM......(Va)

In the formula, M represents to be selected from the transition metal atoms of periodictable the 4th family, G ²The base (dentate) that expression has cyclopentadienyi skeleton, G ³, G ⁴With G ⁵Base (dentate), alkyl, cycloalkyl, aryl, aralkyl, alkoxyl group, aryloxy, trialkylsilkl, SO that expression has cyclopentadienyi skeleton ₃J base, halogen atom or hydrogen atom, k are integer, the k+l+m+n=4 more than 1.

In the transistion metal compound shown in the above-mentioned general formula of the present invention (Va), G ³, G ⁴With G ⁵In at least 1 be the compound of base (dentate) with cyclopentadienyi skeleton, for example can enumerate G ²With G ³It is the compound of base (dentate) with cyclopentadienyi skeleton.Under the situation of this compound, wherein 2 bases (dentate) with cyclopentadienyi skeleton can pass through methylene radical between mutually, ethylidene, alkylidene groups such as propylidene, the di-isopropyl methylene radical, the methyl tertbutyl methylene radical, the dicyclohexyl methylene radical, the methyl cyclohexane methylene, the aminomethyl phenyl methylene radical, the phenylbenzene methylene radical, the methylnaphthalene methylene, the dinaphthyl methylene radical, substituted alkylenes such as isopropylidene, the ring propylidene, the ring butylidene, the ring pentylidene, cyclohexylene, encircle inferior heptyl, two rings [3.3.1] are nonamethylene, the norborneol subunit, the Buddha's warrior attendant subunit, the tetraline subunit, ring such as dihydroxyl indane methylene radical alkylidene group, chlorethylidene, halogen-containing alkylidene groups such as chlorine methylene radical, silicylene, the methyl silicylene, the dimethyl silicylene, the di-isopropyl silicylene, the methyl tertbutyl silicylene, the dicyclohexyl silicylene, the methylcyclohexyl silicylene, the aminomethyl phenyl silicylene, the phenylbenzene silicylene, methyl naphthyl silicylene, the dinaphthyl silicylene, ring dimethylene silicylene, ring trimethylene silicylene, ring tetramethylene silicylene, the cyclopentamethylene silicylene, the hexamethylene silicylene, (replacement) silicylene such as ring heptamethylene silicylene, and silicon is become germanium in silica-based in above-mentioned containing, the germanic base of tin, contain tinbase etc. and combination.And at G ²With G ³When being base (dentate) with cyclopentadienyi skeleton, G ⁴With G ⁵Be base, alkyl, cycloalkyl, aryl, aralkyl, alkoxyl group, aryloxy, trialkylsilkl, SO with cyclopentadienyi skeleton ₃J, halogen atom or hydrogen atom.

In the present invention, in the transistion metal compound that contains the base (dentate) that has this cyclopentadienyi skeleton more than 2, the preferred use is selected from following compositions (a-1), (a-2) and at least a kind of composition (a-3).

Composition (a-1) with (a-2) be respectively transistion metal compound shown in general formula (II), (III).

Formula (II) with (III) in, R ¹～R ⁶Independent respectively expression is selected from hydrogen atom, halogen atom, C ₁～C ₂₀Alkyl, C ₃～C ₂₀Cycloalkyl, C ₂～C ₂₀Thiazolinyl, C ₆～C ₂₀Aryl, C ₇～C ₂₀Aralkyl can contain silicon, halogen or germanium atom, R ³With R ⁴, R ⁴With R ⁵And R ⁵With R ⁶In at least 1 group can interosculate into ring.R ⁷Being the divalent base in conjunction with 2 dentates, can be C ₁～C ₂₀Alkyl, C ₁～C ₂₀Contain brine alkyl, contain silica-based or germanic base or contain tinbase, same, 2 substituting groups on carbon, silicon, germanium, the tin atom can interosculate into ring.t ¹With t ²Independent respectively expression is selected from hydrogen atom, halogen atom, C ₁～C ₂₀Alkyl, C ₁～C ₂₀Contain brine alkyl, contain silica-based, contain the oxygen base, contain sulfenyl, the base of nitrogenous base and phosphorous-containigroups groups.M is the transition metal that is selected from titanium, germanium, hafnium.

General formula (II) with (III) in, as R ¹～R ⁶Halogen atom can be enumerated chlorine, bromine, fluorine, iodine atom, as C ₁～C ₂₀Alkyl can be enumerated methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, sec-butyl, the tertiary butyl, n-pentyl, neo-pentyl, n-hexyl, octyl group, nonyl, dodecyl, eicosyl, norborneol alkyl, adamantyl etc.; As C ₃～C ₂₀Cycloalkyl can be enumerated cyclopropyl, cyclobutyl, cyclopentyl.Cyclohexyl etc.; As C ₂～C ₂₀Thiazolinyl can be enumerated vinyl, propenyl, cyclohexenyl etc.; As C ₇～C ₂₀Aralkyl can be enumerated benzyl, styroyl, hydrocinnamyl etc.; As C ₆～C ₂₀Aryl can be enumerated phenyl, tolyl, 3,5-dimethylphenyl, trimethylphenyl, ethylphenyl, propyl group phenyl, xenyl, α-or betanaphthyl, methyl naphthyl, anthryl, phenanthryl, benzyl phenyl, pyrenyl, acenaphthenyl (acenaphthyl), phenarenyl, benzo acenaphthenyl, tetrahydro naphthyl, indanyl, biphenylyl etc.

As R ¹～R ⁶Contain halogen, can enumerate base that the hydrogen atom more than 1 of abovementioned alkyl, cycloalkyl, thiazolinyl, aralkyl, aryl replaces with silicon or germanium atom etc.

As containing silica-based or germanic base, the base that the carbon atom more than 1 that can enumerate abovementioned alkyl, cycloalkyl, thiazolinyl, aralkyl, aryl replaces with silicon or germanium atom etc.

This R ¹～R ⁶Can be identical or different mutually, and adjacent base, i.e. R ³With R ⁴, R ⁴With R ⁵, R ⁵With R ⁶In at least 1 group can interosculate into ring.As the indenyl that forms this ring, for example can enumerate 4,5-benzo indenyl, 5,6-benzo indenyl, 6, the alkyl substitution product of 7-benzo indenyl, α-acenaphthene and indenyl and carbonatoms 1～10 thereof etc.

R ⁷Be divalent base, as C wherein in conjunction with 2 dentates ₁～C ₂₀Alkyl, can enumerate alkylidene groups such as methylene radical, ethylidene, propylidene, substituted alkylenes such as di-isopropyl methylene radical, methyl tertbutyl methylene radical, dicyclohexyl methylene radical, methyl cyclohexane methylene, aminomethyl phenyl methylene radical, phenylbenzene methylene radical, methylnaphthalene methylene, dinaphthyl methylene radical, isopropylidene, ring propylidene, ring butylidene, ring pentylidene, cyclohexylene, the inferior heptyl of ring, two encircle ring alkylidene groups such as [3.3.1] is nonamethylene, norborneol subunit, Buddha's warrior attendant subunit, tetraline subunit, the inferior indanyl of dihydro (indane methylene radical) etc., as C ₁～C ₂₀Contain brine alkyl, the base that the hydrogen atom that can enumerate the above-mentioned alkyl more than 1 is replaced by suitable halogen atom etc.

As C ₁～C ₂₀Contain silica-based, can enumerate silicylene, the methyl silicylene, the dimethyl silicylene, the di-isopropyl silicylene, the methyl tertbutyl silicylene, the dicyclohexyl silicylene, the methylcyclohexyl silicylene, the aminomethyl phenyl silicylene, the phenylbenzene silicylene, methyl naphthyl silicylene, the dinaphthyl silicylene, ring dimethylene silicylene, ring trimethylene silicylene, ring tetramethylene silicylene, the cyclopentamethylene silicylene, the hexamethylene silicylene, (replacement) silicylene such as ring heptamethylene silicylene etc., as germanic, tinbase, can enumerate above-mentioned contain silica-based in, silicon is become germanium, the base of tin etc.

t ¹With t ²Be to be independently selected from hydrogen atom, halogen atom, C respectively ₁～C ₂₀Alkyl, C ₁～C ₂₀Contain brine alkyl, contain silica-based, contain the oxygen base, contain sulfenyl, the base of nitrogenous base and phosphorous-containigroups groups.As halogen atom, can enumerate chlorine, bromine, fluorine, iodine atom, as C ₁～C ₂₀Alkyl can be enumerated alkyl such as methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, n-hexyl, positive decyl, aryl such as phenyl, 1-naphthyl, 2-naphthyl, and aralkyl such as benzyl etc., and as C ₁～C ₂₀Contain brine alkyl, can enumerate the base that the hydrogen atom more than 1 in the above-mentioned alkyl is replaced by suitable halogen atom, for example trifluoromethyl etc.Silica-based as containing, can enumerate trimethyl silyl, dimethyl (tertiary butyl) silyl etc., as containing the oxygen base, methoxyl group, oxyethyl group etc. can be enumerated,, thiol group, sulfonic group etc. can be enumerated as containing sulfenyl, as nitrogenous base, dimethylamino etc. can be enumerated,, phosphenyl etc. can be enumerated as phosphorous-containigroups groups.t ¹With t ²Can be identical also can be different.

As with general formula (I) each composition (a-1) and (a-2) transistion metal compound, can enumerate for example Japanese kokai publication hei 4-268308 communique, spy and open flat 5-306304 communique, spy and open flat 6-100579 communique, spy and open flat 6-157661 communique, spy and open flat 6-184179 communique, spy and open flat 6-345809 communique, spy and open flat 7-149815 communique, spy and open the compound that flat 7-188318 communique, spy are opened record such as flat 7-258321 communique with (II) expression.

As concrete example, can enumerate ethylenebis (indenyl) zirconium dichloride, ethylenebis (2-methyl indenyl) zirconium dichloride, ethylenebis (tetrahydroindenyl) zirconium dichloride, ethylenebis (2-methyltetrahydro indenyl) zirconium dichloride, 1, two (indenyl) zirconium dichlorides of 3-propylidene, 1, two (the 2-methyl indenyl) zirconium dichlorides of 3-propylidene, 1, two (tetrahydroindenyl) zirconium dichlorides of 3-propylidene, 1, two (the 2-methyltetrahydro indenyl) zirconium dichlorides of 3-propylidene, 1, two (indenyl) zirconium dichlorides of 2-propylidene, 1, two (the 2-methyl indenyl) zirconium dichlorides of 2-propylidene, 1, two (tetrahydroindenyl) zirconium dichlorides of 2-propylidene, 1, two (the 2-methyltetrahydro indenyl) zirconium dichlorides of 2-propylidene, 2, two (indenyl) zirconium dichlorides of 3-butylidene, 2, two (the 2-methyl indenyl) zirconium dichlorides of 3-butylidene, 2, two (tetrahydroindenyl) zirconium dichlorides of 3-butylidene, 2, two (the 2-methyltetrahydro indenyl) zirconium dichlorides of 3-butylidene, two (indenyl) zirconium dichlorides of dimethyl silicylene, two (the 2-methyl indenyl) zirconium dichlorides of dimethyl silicylene, two (2-methyl-4-methyl indenyl) zirconium dichlorides of dimethyl silicylene, two (2-methyl-4-ethyl-indenyl) zirconium dichlorides of dimethyl silicylene, two (2-methyl-4-propyl group indenyl) zirconium dichlorides of dimethyl silicylene, two (2-methyl-4-phenyl indenyl) zirconium dichlorides of dimethyl silicylene, two (2-methyl-4-naphthyl indenyl) zirconium dichlorides of dimethyl silicylene, two (2-methyl-4-anthryl indenyl) zirconium dichlorides of dimethyl silicylene, two (2-methylbenzene [e] indenyl) zirconium dichlorides of dimethyl silicylene, two (2-methylbenzene [f] indenyl) zirconium dichlorides of dimethyl silicylene, two (2-ethyl-indenyl) zirconium dichlorides of dimethyl silicylene, two (2-ethyl-4-phenyl indenyl) zirconium dichlorides of dimethyl silicylene, two (2-ethylbenzene [e] indenyl) zirconium dichlorides of dimethyl silicylene, dimethyl silicylene two (2,5-dimethyl-4-methyl indenyl) zirconium dichloride, dimethyl silicylene two (2,5-dimethyl-4-ethyl-indenyl) zirconium dichloride, dimethyl silicylene two (2,5-dimethyl-4-propyl group indenyl) zirconium dichloride, dimethyl silicylene two (2,5-dimethyl-4-phenyl indenyl) zirconium dichloride, dimethyl silicylene two (2,5-dimethyl-4-naphthyl indenyl) zirconium dichloride, dimethyl silicylene two (2,5-dimethyl-4-anthryl indenyl) zirconium dichloride, dimethyl silicylene two (2,6-dimethyl-4-methyl indenyl) zirconium dichloride, dimethyl silicylene two (2,6-dimethyl-4-ethyl-indenyl) zirconium dichloride, dimethyl silicylene two (2,6-dimethyl-4-propyl group indenyl) zirconium dichloride, dimethyl silicylene two (2,6-dimethyl-4-phenyl indenyl) zirconium dichloride, dimethyl silicylene two (2,6-dimethyl-4-naphthyl indenyl) zirconium dichloride, dimethyl silicylene two (2,6-dimethyl-4-anthryl indenyl) zirconium dichloride, dimethyl silicylene two (2,7-dimethyl-4-methyl indenyl) zirconium dichloride, dimethyl silicylene two (2,7-dimethyl-4-ethyl-indenyl) zirconium dichloride, dimethyl silicylene two (2,7-dimethyl-4-propyl group indenyl) zirconium dichloride, dimethyl silicylene two (2,7-dimethyl-4-phenyl indenyl) zirconium dichloride, dimethyl silicylene two (2,7-dimethyl-4-naphthyl indenyl) zirconium dichloride, dimethyl silicylene two (2,7-dimethyl-4-anthryl indenyl) zirconium dichloride, two (indenyl) zirconium dichlorides of phenyl methyl silicylene, two (the 2-methyl indenyl) zirconium dichlorides of phenyl methyl silicylene, two (2-methyl-4-methyl indenyl) zirconium dichlorides of phenyl methyl silicylene, two (2-methyl-4-ethyl-indenyl) zirconium dichlorides of phenyl methyl silicylene, two (2-methyl-4-propyl group indenyl) zirconium dichlorides of phenyl methyl silicylene, two (2-methyl-4-phenyl indenyl) zirconium dichlorides of phenyl methyl silicylene, two (2-methyl-4-naphthyl indenyl) zirconium dichlorides of phenyl methyl silicylene, two (2-methyl-4-anthryl indenyl) zirconium dichlorides of phenyl methyl silicylene, two (2-methylbenzene [e] indenyl) zirconium dichlorides of phenyl methyl silicylene, two (2-methylbenzene [f] indenyl) zirconium dichlorides of phenyl methyl silicylene, two (2-ethyl-indenyl) zirconium dichlorides of phenyl methyl silicylene, two (2-ethyl-4-phenyl indenyl) zirconium dichlorides of phenyl methyl silicylene, two (2-ethylbenzene [e] indenyl) zirconium dichlorides of phenyl methyl silicylene, phenyl methyl silicylene two (2,5-dimethyl-4-methyl indenyl) zirconium dichloride, phenyl methyl silicylene two (2,5-dimethyl-4-ethyl-indenyl) zirconium dichloride, phenyl methyl silicylene two (2,5-dimethyl-4-propyl group indenyl) zirconium dichloride, phenyl methyl silicylene two (2,5-dimethyl-4-phenyl indenyl) zirconium dichloride, phenyl methyl silicylene two (2,5-dimethyl-4-naphthyl indenyl) zirconium dichloride, phenyl methyl silicylene two (2,5-dimethyl-4-anthryl indenyl) zirconium dichloride, phenyl methyl silicylene two (2,6-dimethyl-4-methyl indenyl) zirconium dichloride, phenyl methyl silicylene two (2,6-dimethyl-4-ethyl-indenyl) zirconium dichloride, phenyl methyl silicylene two (2,6-dimethyl-4-propyl group indenyl) zirconium dichloride, phenyl methyl silicylene two (2,6-dimethyl-4-phenyl indenyl) zirconium dichloride, phenyl methyl silicylene two (2,6-dimethyl-4-naphthyl indenyl) zirconium dichloride, phenyl methyl silicylene two (2,6-dimethyl-4-anthryl indenyl) zirconium dichloride, phenyl methyl silicylene two (2,7-dimethyl-4-methyl indenyl) zirconium dichloride, phenyl methyl silicylene two (2,7-dimethyl-4-ethyl-indenyl) zirconium dichloride, phenyl methyl silicylene two (2,7-dimethyl-4-propyl group indenyl) zirconium dichloride, phenyl methyl silicylene two (2,7-dimethyl-4-phenyl indenyl) zirconium dichloride, phenyl methyl silicylene two (2,7-dimethyl-4-naphthyl indenyl) zirconium dichloride, two (2, the 7-dimethyl-4-anthryl indenyl) zirconium dichlorides of phenyl methyl silicylene, dibromide with above-mentioned aromatic ring alkene metal derivative compound, the dialkyl group thing, two aralkyl things, the dimethyl silanyl thing, dialkoxy compound, two mercaptides, the disulfonic acid thing, the diamino thing, the central metal of diphosphine thing or above-claimed cpd is the aromatic ring alkene metal derivative compound of titanium or hafnium etc.

Composition (a-3) is the transistion metal compound with general formula (IV) expression

In the formula (IV), R ⁸～R ¹⁹Independent respectively expression is selected from hydrogen atom, halogen atom, C ₁～C ₂ ₀Alkyl, C ₃～C ₂₀Cycloalkyl, C ₂～C ₂₀Thiazolinyl, C ₆～C ₂₀Aryl, C ₇～C ₂₀Arylalkyl can contain silicon, halogen or germanium atom, to R ¹²～R ¹⁹Also can interosculate into ring in abutting connection with substituting group.R ⁷Being the divalent base in conjunction with 2 dentates, is C ₁～C ₂₀Alkyl, C ₁～C ₂₀Contain brine alkyl, contain silica-based, germanic base or contain tinbase, same, 2 substituting groups on carbon, silicon, germanium, the tin atom can interosculate into ring.t ¹With t ²Independent respectively expression is selected from hydrogen atom, halogen atom, C ₁～C ₂₀Alkyl, C ₁～C ₂₀Contain brine alkyl, contain silica-based, contain the oxygen base, contain sulfenyl, the base of nitrogenous base, phosphorous-containigroups groups.M is the transition metal that is selected from titanium, germanium, hafnium.

In the general formula (IV), as R ⁸～R ¹⁹In halogen atom, can enumerate chlorine, bromine, fluorine, iodine atom, as C ₁～C ₂₀Alkyl can be enumerated methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, sec-butyl, the tertiary butyl, n-pentyl, neo-pentyl, n-hexyl, octyl group, nonyl, dodecyl, eicosyl, norborneol alkyl, adamantyl etc.; As C ₃～C ₂₀Cycloalkyl can be enumerated cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl etc.; As C ₂～C ₂₀Thiazolinyl can be enumerated vinyl, propenyl, cyclohexenyl etc.; As C ₇～C ₂₀Aralkyl can be enumerated benzyl, styroyl, hydrocinnamyl etc.; As C ₆～C ₂₀Aryl can be enumerated phenyl, tolyl, 3,5-dimethylphenyl, trimethylphenyl, ethylphenyl, propyl group phenyl, xenyl, α-or betanaphthyl, methyl naphthyl, anthryl, phenanthryl, benzyl phenyl, pyrenyl, acenaphthenyl, phenarenyl, benzo acenaphthenyl, tetrahydro naphthyl, indanyl, biphenylyl etc.As R ⁸～R ¹⁹In contain halogen, can enumerate base that the hydrogen atom more than 1 of abovementioned alkyl, cycloalkyl, thiazolinyl, aralkyl, aryl replaces with suitable halogen atom etc.As containing silica-based or germanic base, the base that the carbon atom more than 1 that can enumerate abovementioned alkyl, cycloalkyl, thiazolinyl, aralkyl, aryl replaces with silicon or germanium atom etc.This R ⁸～R ¹⁹Between can be identical or different.

In addition, the R on the fluorenes ring ¹²～R ¹⁹Adjacent base at least 1 group also can interosculate into ring.As the fluorenyl that forms such ring, can enumerate for example benzo fluorenyl, dibenzo fluorenyl, eight hydroxyl dibenzo fluorenyls, prestox eight hydroxyl dibenzo fluorenyls etc.R ⁷, t ¹, t ²Identical with general formula (II) with the definition in (III), can enumerate same base.

Concrete example as such transistion metal compound (a-3) with above-mentioned general formula (IV) expression, can enumerate isopropylidene (cyclopentadienyl) (fluorenyl) zirconium dichloride, isopropylidene (cyclopentadienyl) (2,7-di-t-butyl fluorenyl) zirconium dichloride, isopropylidene (cyclopentadienyl) (3,6-di-t-butyl fluorenyl) zirconium dichloride, isopropylidene (cyclopentadienyl) (prestox octahydro dibenzo fluorenyl) zirconium dichloride, phenylbenzene methylene radical (cyclopentadienyl) (fluorenyl) zirconium dichloride, phenylbenzene methylene radical (cyclopentadienyl) (2,7-di-t-butyl fluorenyl) zirconium dichloride, phenylbenzene methylene radical (cyclopentadienyl) (3,6-di-t-butyl fluorenyl) zirconium dichloride, phenylbenzene methylene radical (cyclopentadienyl) (prestox octahydro dibenzo fluorenyl) zirconium dichloride, cyclohexylene (cyclopentadienyl) (fluorenyl) zirconium dichloride, cyclohexylene (cyclopentadienyl) (2,7-di-t-butyl fluorenyl) zirconium dichloride, cyclohexylene (cyclopentadienyl) (3,6-di-t-butyl fluorenyl) zirconium dichloride, cyclohexylene (cyclopentadienyl) (prestox octahydro dibenzo fluorenyl) zirconium dichloride, phenyl methyl methylene radical (cyclopentadienyl) (fluorenyl) zirconium dichloride, phenyl methyl methylene radical (cyclopentadienyl) (2,7-di-t-butyl fluorenyl) zirconium dichloride, phenyl methyl methylene radical (cyclopentadienyl) (3,6-di-t-butyl fluorenyl) zirconium dichloride, phenyl methyl methylene radical (cyclopentadienyl) (prestox octahydro dibenzo fluorenyl) zirconium dichloride, isopropylidene (3-tertiary butyl cyclopentadienyl) (2,7-di-t-butyl fluorenyl) zirconium dichloride, isopropylidene (3-tertiary butyl cyclopentadienyl) (fluorenyl) zirconium dichloride, isopropylidene (3-tertiary butyl cyclopentadienyl) (2,7-di-t-butyl fluorenyl) zirconium dichloride, isopropylidene (3-tertiary butyl cyclopentadienyl) (3,6-di-t-butyl fluorenyl) zirconium dichloride, isopropylidene (3-tertiary butyl cyclopentadienyl) (prestox octahydro dibenzo fluorenyl) zirconium dichloride, phenylbenzene methylene radical (3-tertiary butyl cyclopentadienyl) (fluorenyl) zirconium dichloride, phenylbenzene methylene radical (3-tertiary butyl cyclopentadienyl) (2,7-di-t-butyl fluorenyl) zirconium dichloride, phenylbenzene methylene radical (3-tertiary butyl cyclopentadienyl) (3,6-di-t-butyl fluorenyl) zirconium dichloride, phenylbenzene methylene radical (3-tertiary butyl cyclopentadienyl) (prestox octahydro dibenzo fluorenyl) zirconium dichloride, cyclohexylene (3-tertiary butyl cyclopentadienyl) (fluorenyl) zirconium dichloride, cyclohexylene (3-tertiary butyl cyclopentadienyl) (2,7-di-t-butyl fluorenyl) zirconium dichloride, cyclohexylene (3-tertiary butyl cyclopentadienyl) (3,6-di-t-butyl fluorenyl) zirconium dichloride, cyclohexylene (3-tertiary butyl cyclopentadienyl) (prestox octahydro dibenzo fluorenyl) zirconium dichloride, phenyl methyl methylene radical (3-tertiary butyl cyclopentadienyl) (fluorenyl) zirconium dichloride, phenyl methyl methylene radical (3-tertiary butyl cyclopentadienyl) (2,7-di-t-butyl fluorenyl) zirconium dichloride, phenyl methyl methylene radical (3-tertiary butyl cyclopentadienyl) (3,6-di-t-butyl fluorenyl) zirconium dichloride, phenyl methyl methylene radical (3-tertiary butyl cyclopentadienyl) (prestox octahydro dibenzo fluorenyl) zirconium dichloride, isopropylidene (the 3-tertiary butyl-5-methyl cyclopentadienyl) (fluorenyl) zirconium dichloride, isopropylidene (the 3-tertiary butyl-5-methyl cyclopentadienyl) (2,7-di-t-butyl fluorenyl) zirconium dichloride, isopropylidene (the 3-tertiary butyl-5-methyl cyclopentadienyl) (3,6-di-t-butyl fluorenyl) zirconium dichloride, isopropylidene (the 3-tertiary butyl-5-methyl cyclopentadienyl) (prestox octahydro dibenzo fluorenyl) zirconium dichloride, phenylbenzene methylene radical (the 3-tertiary butyl-5-methyl cyclopentadienyl) (fluorenyl) zirconium dichloride, phenylbenzene methylene radical (the 3-tertiary butyl-5-methyl cyclopentadienyl) (2,7-di-t-butyl fluorenyl) zirconium dichloride, phenylbenzene methylene radical (the 3-tertiary butyl-5-methyl cyclopentadienyl) (3,6-di-t-butyl fluorenyl) zirconium dichloride, phenylbenzene methylene radical (the 3-tertiary butyl-5-methyl cyclopentadienyl) (prestox octahydro dibenzo fluorenyl) zirconium dichloride, cyclohexylene (the 3-tertiary butyl-5-methyl cyclopentadienyl) (fluorenyl) zirconium dichloride, cyclohexylene (the 3-tertiary butyl-5-methyl cyclopentadienyl) (2,7-di-t-butyl fluorenyl) zirconium dichloride, cyclohexylene (the 3-tertiary butyl-5-methyl cyclopentadienyl) (3,6-di-t-butyl fluorenyl) zirconium dichloride, cyclohexylene (the 3-tertiary butyl-5-methyl cyclopentadienyl) (prestox octahydro dibenzo fluorenyl) zirconium dichloride, phenyl methyl methylene radical (the 3-tertiary butyl-5-methyl cyclopentadienyl) (fluorenyl) zirconium dichloride, phenyl methyl methylene radical (the 3-tertiary butyl-5-methyl cyclopentadienyl) (2,7-di-t-butyl fluorenyl) zirconium dichloride, phenyl methyl methylene radical (the 3-tertiary butyl-5-methyl cyclopentadienyl) (3,6-di-t-butyl fluorenyl) zirconium dichloride, phenyl methyl methylene radical (the 3-tertiary butyl-5-methyl cyclopentadienyl) (prestox octahydro dibenzo fluorenyl) zirconium dichloride, dibromide with above-mentioned aromatic ring alkene metal derivative compound, the dialkyl group thing, two aralkyl things, the dimethyl silanyl thing, the dialkoxy thing, two mercaptides, the disulfonic acid thing, the diamino thing, the central metal of diphosphine thing or above-claimed cpd is the aromatic ring alkene metal derivative compound of titanium or hafnium etc.

In the transistion metal compound with general formula (II), (III), (IV) expression, be with the transistion metal compound of general formula (II), (III) expression, be preferably compound especially with general formula (II) expression as preferred compound.

(b) organoaluminum oxo-compounds that uses among the present invention (following also be designated as " composition (b) ") can be existing known aluminium siloxanes, also can be that the spy opens the illustrational benzene-insoluble organoaluminum oxo-compounds of flat 2-78687 communique.

Existing known aluminium siloxanes can be made by for example following method (i)～(iii).

(i) at the compound that contains planar water or contain the salt of crystal water---for example add organo-aluminium compound such as trialkylaluminium in the hydrocarbon medium suspension liquids such as magnesium chloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate, single nickel salt hydrate, cerous chlorate hydrate and the method for reacting.

(ii) in media such as benzene, toluene, ether, tetrahydrofuran (THF), make water, ice, water vapor directly act on the method for organo-aluminium compounds such as trialkylaluminium.

(iii) in media such as decane, benzene, toluene, make the method for organo-aluminium compound reactions such as organotin oxides such as dimethyl tin oxide, Dibutyltin oxide and trialkylaluminium.

In addition, in aforesaid method, the aluminium siloxanes reclaims as hydrocarbon solution.Also can be from the above-mentioned aluminium siloxane solution that reclaims distillation remove desolvate or unreacted organo-aluminium compound after, in solvent, dissolve gained aluminium siloxanes again.

Spendable organo-aluminium compound during as preparation aluminium siloxanes specifically can be enumerated trialkylaluminiums such as trimethyl aluminium, triethyl aluminum, tri-propyl aluminum, triisopropylaluminiuand, three n-butylaluminum, triisobutyl aluminium, three sec-butyl aluminium, tri-tert aluminium, three amyl group aluminium, three hexyl aluminium, trioctylaluminum, three decyl aluminium; Tricyclic alkyl aluminium such as thricyclohexyl aluminium, three ring octyl group aluminium; Dialkyl aluminum halides such as dimethylaluminum chloride, diethyl aluminum chloride, diethyl aluminum chloride, diethyl aluminum bromide, diisobutyl aluminum chloride; Dialkyl aluminum hydride such as diethyl aluminium hydride, diisobutylaluminium hydride; Aluminum dialkyl alkoxide such as dimethyl methyl aluminium alcoholates, diethyl aluminum ethylate; Aluminum dialkyls such as diethyl aluminum phenates virtue oxonium salt etc.

Wherein, preferred especially trialkylaluminium, tricyclic alkyl aluminium.And spendable organo-aluminium compound during as preparation aluminium siloxanes also can use the isopentene aluminium of following general formula (VI) expression.

(i-C ₄H ₉) _xAl _y(C ₅H ₁₀) _z......(VI)

In the formula, x, y, z are positive numbers, z 〉=2x.

Aforesaid organo-aluminium compound can be used singly or in combination.Spendable solvent during as preparation aluminium siloxanes, can enumerate aromatic hydrocarbon such as benzene,toluene,xylene, isopropyl benzene, isopropyl toluene, aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, 12 carbon alkane, hexadecane, octodecane, alicyclic hydrocarbon such as pentamethylene, hexanaphthene, cyclooctane, methylcyclopentane, hydrocarbon such as petroleum fractions such as gasoline, kerosene, light oil or above-mentioned aromatic hydrocarbon, aliphatic hydrocarbon, alicyclic halogenide, muriate, bromide.Also can use ethers such as ether, tetrahydrofuran (THF) in addition.In these solvents, be preferably aromatic hydrocarbon especially.

In addition, the spendable benzene-insoluble organoaluminum oxo-compounds of the present invention can be by making the aluminium siloxane solution with water or contain the method that the compound that activates hydrogen contacts, or the method that above-mentioned organo-aluminium compound is contacted with water obtains.The dissolved Al composition in 60 ℃ benzene of benzene-insoluble organoaluminum oxo-compounds like this is scaled Al atom below 10%, is preferably below 5%, is preferably especially below 2%, and is insoluble or be insoluble in benzene.

Above-mentioned organoaluminum oxo-compounds (b) is sold or is handled with toluene solution usually.In addition, available organoaluminum oxo-compounds of the present invention (b) also can contain the organic compound ingredient of metal outside the small amount of aluminum.

The present invention spendable (c) (following also be designated as " component (c) ") is the multivalence functionality Organohalogen compounds with general formula (I) expression.

(Q ¹) _o-R-(Q ²) _p......(I)

In the general formula (I), with Q ¹With Q ²In-L in the substituted-amino that NLH represents, as halogen atom, can enumerate chlorine, bromine, fluorine, iodine atom, as C ₁～C ₂₀Alkyl can be enumerated alkyl such as methyl, ethyl, n-propyl, normal-butyl, isobutyl-, the tertiary butyl, n-hexyl, positive decyl, aryl such as phenyl, 1-naphthyl, 2-naphthyl, aralkyl such as benzyl etc.

And as C ₁～C ₂₀Halogen-containing alkyl, can enumerate the base that the above hydrogen atom of in the above-mentioned alkyl 1 is replaced by suitable halogen atom, for example trifluoromethyl etc.Silica-based as containing, can enumerate trimethyl silyl, dimethyl (tertiary butyl) silyl etc., as containing the oxygen base, methoxyl group, oxyethyl group etc. can be enumerated,, thiol group, sulfonic group etc. can be enumerated as containing sulfenyl, as nitrogenous base, dimethylamino etc. can be enumerated,, phenyl phosphino-etc. can be enumerated as phosphorous-containigroups groups.

As the concrete example of the multivalence functionality Organohalogen compounds of this above-mentioned general formula (I) expression, as OH-R-OH type compound, wherein, the definition of R is identical with general formula (I), can enumerate 3-fluoro catechol, 4-fluoro catechol, 3,4-two fluoro catechols, 3,5-two fluoro catechols, 3,6-two fluoro catechols, 3,4,5-three fluoro catechols, 3,4,6-three fluoro catechols, tetrafluoro is for catechol, 3-(three fluoro methyl) catechol, 4-(three fluoro methyl) catechol, 3,4-two (three fluoro methyl) catechol, 3,5-two (three fluoro methyl) catechol, 3,6-two (three fluoro methyl) catechol, 3,4,5-three (three fluoro methyl) catechol, 3,4,6-three (three fluoro methyl) catechol, four (three fluoro methyl) catechol, 2-fluoro Resorcinol, 4-fluoro Resorcinol, 5-fluoro Resorcinol, 2,4-two fluoro Resorcinols, 2,5-fluoro Resorcinol, 4,5-two fluoro Resorcinols, 4,6-two fluoro Resorcinols, 5,6-two fluoro Resorcinols, 2,4,5-three fluoro Resorcinols, 4,5,6-three fluoro Resorcinols, tetrafluoro is for Resorcinol, 2-(three fluoro methyl) Resorcinol, 4-(three fluoro methyl) Resorcinol, 5-(three fluoro methyl) Resorcinol, 2,4-two (three fluoro methyl) Resorcinol, 2,5-(three fluoro methyl) Resorcinol, 4,5-two (three fluoro methyl) Resorcinol, 4,6-two (three fluoro methyl) Resorcinol, 5,6-two (three fluoro methyl) Resorcinol, 2,4,5-three (three fluoro methyl) Resorcinol, 4,5,6-three (three fluoro methyl) Resorcinol, four (three fluoro methyl) Resorcinol, 2-fluoro Resorcinol, 3-fluoro Resorcinol, 2,3-two fluoro Resorcinol, 2,5-two fluoro Resorcinol, 2,6-two fluoro Resorcinol, 2,3,5-three fluoro Resorcinol, 2,3,6-three fluoro Resorcinol, tetrafluoro is for Resorcinol, 2-(three fluoro methyl) Resorcinol, 3-(three fluoro methyl) Resorcinol, 2,3-two (three fluoro methyl) Resorcinol, 2,5-two (three fluoro methyl) Resorcinol, 2,6-two (three fluoro methyl) Resorcinol, 2,3,5-three (three fluoro methyl) Resorcinol, 2,3,6-three (three fluoro methyl) Resorcinol, four (three fluoro methyl) Resorcinol, 1, two (the 2-hydroxyl hexafluoro-sec.-propyl) benzene of 3-, 1, two (the 2-hydroxyl hexafluoro-sec.-propyl) benzene of 4-, 2-fluoro-1, the 5-dihydroxy naphthlene, 3-fluoro-1, the 5-dihydroxy naphthlene, 4-fluoro-1, the 5-dihydroxy naphthlene, 2,3-two fluoro-1, the 5-dihydroxy naphthlene, 2,4-two fluoro-1, the 5-dihydroxy naphthlene, 2,6-two fluoro-1, the 5-dihydroxy naphthlene, 2,7-two fluoro-1, the 5-dihydroxy naphthlene, 2,8-two fluoro-1, the 5-dihydroxy naphthlene, 3,4-two fluoro-1, the 5-dihydroxy naphthlene, 3,8-two fluoro-1, the 5-dihydroxy naphthlene, 4,8-two fluoro-1, the 5-dihydroxy naphthlene, 2,3,4-three fluoro-1,5-dihydroxy naphthlene, 2,3,6-three fluoro-1, the 5-dihydroxy naphthlene, 2,3,7-three fluoro-1, the 5-dihydroxy naphthlene, 2,3,8-three fluoro-1, the 5-dihydroxy naphthlene, 2,3,6, the 7-tetrafluoro is for-1, the 5-dihydroxy naphthlene, hexafluoro--1, the 5-dihydroxy naphthlene, 1-fluoro-2, the 6-dihydroxy naphthlene, 3-fluoro-2, the 6-dihydroxy naphthlene, 4-fluoro-2, the 6-dihydroxy naphthlene, 1,3-two fluoro-2, the 6-dihydroxy naphthlene, 1,4-two fluoro-2, the 6-dihydroxy naphthlene, 1,5-two fluoro-2, the 6-dihydroxy naphthlene, 3,4-two fluoro-2, the 6-dihydroxy naphthlene, 3,5-two fluoro-2, the 6-dihydroxy naphthlene, 4,5-two fluoro-2, the 6-dihydroxy naphthlene, 1,3,4-three fluoro-2,6-dihydroxy naphthlene, 1,3,5-three fluoro-2, the 6-dihydroxy naphthlene, 3,4,5-three fluoro-2, the 6-dihydroxy naphthlene, 1,3,4, the 5-tetrafluoro is for-2, the 6-dihydroxy naphthlene, hexafluoro--2, the 6-dihydroxy naphthlene, 2,3,4, the 5-tetrafluoro is for bis-phenol, 2,2 ', 4,4 '-tetrafluoro generation-4,4 '-bis-phenol, 2,2 ', 3,3 ', 4,4 ', 5,5 ', 6,6 '-octafluoro generation-4,4 '-bis-phenol, 4,4 '-two (2-hydroxyl hexafluoro-sec.-propyl) phenylbenzene, two (2,3-two fluoro-4-hydroxyl) methane, two (2,6-two fluoro-4-hydroxyl) methane, two (3,5-two fluoro-4-hydroxyl) methane, two (tetrafluoro generation-4-hydroxyl) methane, 4,4 '-two (2-hydroxyl hexafluoro-sec.-propyl) diphenyl ether, 4,4 '-isopropylidene two (2,6-phenyl-difluoride phenol), tetrafluoro is for ethylene glycol, hexafluoro--1, ammediol, 2,2 ', 3,3 '-tetrafluoro generation-1, the 4-butyleneglycol, octafluoro is for-1, the 4-butyleneglycol, perfluoro-1, the 5-pentanediol, perfluoro-1, the 6-hexylene glycol, perfluoro-1, the 7-heptanediol, perfluoro-1, the fluorine atom of 8-ethohexadiol and above-mentioned OH-R-OH compound is by bromine atoms, the compound that the chlorine atom replaces etc.

As H ₂N-R-NH ₂Compound, the definition of R is identical with general formula (I), can enumerate 2-amino-3-fluoro aniline, 2-amino-4-fluoro aniline, 2-amino-5-fluoro aniline, 2-amino-3,4-phenyl-difluoride amine, 2-amino-3,5-phenyl-difluoride amine, 2-amino-3,6-phenyl-difluoride amine, 2-amino-3,4,5-trifluoro-benzene amine, 2-amino-3,4,6-trifluoro-benzene amine, 2-amino-tetrafluoro is for aniline, 2-amino-3 (three fluoro methyl) aniline, 2-amino-4 (three fluoro methyl) aniline, 2-amino-3,4-two (three fluoro methyl) aniline, 2-amino-3,5-two (three fluoro methyl) aniline, 2-amino-3,6-two (three fluoro methyl) aniline, 2-amino-3,4,5-three (three fluoro methyl) aniline, 2-amino-3,4,6-three (three fluoro methyl) aniline, 2-amino-four (three fluoro methyl) aniline, 3-amino-2-fluoro aniline, 3-amino-4-fluoro aniline, 3-amino-5-fluoro aniline, 3-amino-2,4-phenyl-difluoride amine, 3-amino-2,5-phenyl-difluoride amine, 3-amino-4,5-phenyl-difluoride amine, 3-amino-4,6-phenyl-difluoride amine, 3-amino-5,6-phenyl-difluoride amine, 3-amino-2,4,5-trifluoro-benzene amine, 3-amino-4,5,6-trifluoro-benzene amine, 3-amino-tetrafluoro is for aniline, 3-amino-2-(three fluoro methyl) aniline, 3-amino-4-(three fluoro methyl) aniline, 3-amino-5-(three fluoro methyl) aniline, 3-amino-2,4-two (three fluoro methyl) aniline, 3-amino-2,5-two (three fluoro methyl) aniline, 3-amino-4,5-two (three fluoro methyl) aniline, 3-amino-4,6-two (three fluoro methyl) aniline, 3-amino-5,6-two (three fluoro methyl) aniline, 3-amino-2,4,5-three (three fluoro methyl) aniline, 3-amino-4,5,6-three (three fluoro methyl) aniline, 3-amino-four (three fluoro methyl) aniline, 4-amino-2-fluoro aniline, 4-amino-3-fluoro aniline, 4-amino-2,3-phenyl-difluoride amine, 4-amino-2,5-phenyl-difluoride amine, 4-amino-2,6-phenyl-difluoride amine, 4-amino-2,3,5-trifluoro-benzene amine, 4-amino-2,3,6-trifluoro-benzene amine, 4-amino-tetrafluoro is for aniline, 4-amino-2-(three fluoro methyl) aniline, 4-amino-3-(three fluoro methyl) aniline, 4-amino-2,3-two (three fluoro methyl) aniline, 4-amino-2,5-two (three fluoro methyl) aniline, 4-amino-2,6-two (three fluoro methyl) aniline, 4-amino-2,3,5-three (three fluoro methyl) aniline, 4-amino-2,3,6-three (three fluoro methyl) aniline, 4-amino-four (three fluoro methyl) aniline, 2-amino-6-fluoro benzylamine, 1,5-diamino-2-naphthalene fluoride, 1,5-diamino-3-naphthalene fluoride, 1,5-diamino-4-naphthalene fluoride, 1,5-diamino-2,3-two naphthalene fluorides, 1,5-diamino-2,4-two naphthalene fluorides, 1,5-diamino-2,6-two naphthalene fluorides, 1,5-diamino-2,7-two naphthalene fluorides, 1,5-diamino-2,8-two naphthalene fluorides, 1,5-diamino-3,4-two naphthalene fluorides, 1,5-diamino-3,8-two naphthalene fluorides, 1,5-diamino-4,8-two naphthalene fluorides, 1,5-diamino-2,3,4-three naphthalene fluorides, 1,5-diamino-2,3,6-three naphthalene fluorides, 1,5-diamino-2,3,7-three naphthalene fluorides, 1,5-diamino-2,3,8-three naphthalene fluorides, 1,5-diamino-2,3,6,7-four naphthalene fluorides, 1,5-diamino-hexafluoro-naphthalene, 2,6-diaminostilbene-naphthalene fluoride, 2,6-diamino-3-naphthalene fluoride, 2,6-diamino-4-naphthalene fluoride, 2, the 6-diaminostilbene, 3-two naphthalene fluorides, 2,6-diaminostilbene, 4-two naphthalene fluorides, 2, the 6-diaminostilbene, 5-two naphthalene fluorides, 2,6-diamino-3,4-two naphthalene fluorides, 2,6-diamino-3,5-two naphthalene fluorides, 2,6-diamino-4,5-two naphthalene fluorides, 2, the 6-diaminostilbene, 3,4-three naphthalene fluorides, 2, the 6-diaminostilbene, 3,5-three naphthalene fluorides, 2,6-diamino-3,4,5-three naphthalene fluorides, 2, the 6-diaminostilbene, 3,4,5-four naphthalene fluorides, 2,6-diamino-hexafluoro-naphthalene, 4-amino-4 '-(N-methylamino)-2,3,4, the 5-tetrafluoro is for biphenyl, 4-amino-4 '-(N-methylamino)-2,2 ', 4,4 '-tetrafluoro is for biphenyl, 4-amino-4 '-(N-methylamino)-2,2 ', 3,3 ', 4,4 ', 5,5 ', 6,6 '-octafluoro is for biphenyl, 2,2 '-two (three fluoro methyl)-4,4 '-benzidine, 3,3 '-two (three fluoro methyl)-4,4 '-benzidine, 4,4 '-the diamino octafluoro is for biphenyl, two (4-amino-2,3-phenyl-difluoride base) methane, two (4-amino-2,6-phenyl-difluoride base) methane, two (4-amino-3,5-phenyl-difluoride base) methane, two (4-amino-tetrafluoro is for phenyl) methane, 2, two (3-amino-4-aminomethyl phenyl) hexafluoorpropanes of 2-, 2, two [4-(4-the aminophenyl)] hexafluoorpropanes of 2-, 2, two (4-aminophenyl) hexafluoorpropanes of 2-, 4,4 '-two (2-amino-hexafluoro-sec.-propyl) biphenyl ether, 4,4 '-isopropylidene two (2,6-phenyl-difluoride amine), 2,4-diamino-6-(4-fluoro phenyl) pyrimidine, 2,4-diamino-5-fluoro quinazoline, 4,4 '-the diamino octafluoro is for biphenyl, tetrafluoro is for succinic diamide, tetrafluoro is for quadrol, hexafluoro--1, the 3-propylene diamine, 2,2 ', 3,3 '-tetrafluoro generation-1, the 4-butanediamine, octafluoro generation-1, the 4-butanediamine, ten fluoro-1, the 5-pentamethylene diamine, perfluoro-1, the 6-hexanediamine, perfluoro-1, the 7-heptamethylene diamine, perfluoro-1,8-octamethylenediamine and above-mentioned H ₂N-R-NH ₂The compound that the fluorine atom of compound is replaced by bromine atoms, chlorine atom etc.

As HLN-R-NLH type compound, R is identical with general formula (I) with the definition of L, can enumerate 3-fluoro-1,2-two (N-methylamino) benzene, 4-fluoro-1,2-two (N-methylamino) benzene, 3,4-two fluoro-1,2-two (N-methylamino) benzene, 3,5-two fluoro-1,2-two (N-methylamino) benzene, 3,6-two fluoro-1,2-two (N-methylamino) benzene, 3,4,5-three fluoro-1,2-two (N-methylamino) benzene, 3,4,6-three fluoro-1,2-two (N-methylamino) benzene, tetrafluoro-1,2-two (N-methylamino) benzene, 2-fluoro-1,3-two (N-methylamino) benzene, 4-fluoro-1,3-two (N-methylamino) benzene, 5-fluoro-1,3-two (N-methylamino) benzene, 2,4-two fluoro-1,3-two (N-methylamino) benzene, 2,5-fluoro-1,3-two (N-methylamino) benzene, 4,5-two fluoro-1,3-two (N-methylamino) benzene, 4,6-two fluoro-1,3-two (N-methylamino) benzene, 5,6-two fluoro-1,3-two (N-methylamino) benzene, 2,4,5-three fluoro-1,3-two (N-methylamino) benzene, 4,5,6-three fluoro-1,3-two (N-methylamino) benzene, tetrafluoro-1,3-two (N-methylamino) benzene, 2-fluoro-1,4-two (N-methylamino) benzene, 3-fluoro-1,4-two (N-methylamino) benzene, 2,3-two fluoro-1,4-two (N-methylamino) benzene, 2,5-two fluoro-1,4-two (N-methylamino) benzene, 2,6-two fluoro-1,4-two (N-methylamino) benzene, 2,3,5-three fluoro-1,4-two (N-methylamino) benzene, 2,3,6-three fluoro-1,4-two (N-methylamino) benzene, tetrafluoro-1,4-two (N-methylamino) benzene, 2-fluoro-1,5-two (N-methylamino) naphthalene, 3-fluoro-1,5-two (N-methylamino) naphthalene, 4-fluoro-1,5-two (N-methylamino) naphthalene, 2,3-two fluoro-1,5-two (N-methylamino) naphthalene, 2,4-two fluoro-1,5-two (N-methylamino) naphthalene, 2,6-two fluoro-1,5-two (N-methylamino) naphthalene, 2,7-two fluoro-1,5-two (N-methylamino) naphthalene, 2,8-two fluoro-1,5-two (N-methylamino) naphthalene, 3,4-two fluoro-1,5-two (N-methylamino) naphthalene, 3,8-two fluoro-1,5-two (N-methylamino) naphthalene, 4,8-two fluoro-1,5-two (N-methylamino) naphthalene, 2,3,4-three fluoro-1,5-two (N-methylamino) naphthalene, 2,3,6-three fluoro-1,5-two (N-methylamino) naphthalene, 2,3,7-three fluoro-1,5-two (N-methylamino) naphthalene, 2,3,8-three fluoro-1,5-two (N-methylamino) naphthalene, 2,3,6,7-tetrafluoro-1,5-two (N-methylamino) naphthalene, hexafluoro-1,5-two (N-methylamino) naphthalene, 4,4 '-two (N-methylamino)-2,3,4, the 5-tetrafluoro is for biphenyl, 4,4 '-two (N-methylaminos)-2,2 ', 4,4 '-tetrafluoro is for biphenyl, 4,4 '-two (N-methylaminos)-2,2 ', 3,3 ', 4,4 ', 5,5 ', 6,6 '-octafluoro is for biphenyl, two (4-(N-methylamino)-2,3-phenyl-difluoride base) methane, two ((N-methylaminos)-2,6-phenyl-difluoride base) methane, two (4-(N-methylamino)-3,5-phenyl-difluoride base) methane, two (4-(N-methylamino)-tetrafluoro is for phenyl) methane, 4,4 '-two (2-(N-methylamino)-hexafluoro-sec.-propyl) biphenyl ether, tetrafluoro is for quadrol, hexafluoro--1, the 3-propylene diamine, 2,2 ', 3,3 '-hexafluoro--1, the 4-butanediamine, octafluoro is for-1, the 4-butanediamine, ten fluoro-1, the 5-pentamethylene diamine, perfluoro-1, the 6-hexanediamine, perfluoro-1, the 7-heptamethylene diamine, perfluoro-1, the 8-octamethylenediamine, 1,2-two (N-methylamino) tetrafluoro is for ethane, 1,3-two (N-methylamino) hexafluoorpropane, 1,4-two (N-methylamino)-2,2 ', 3,3 '-the hexafluoro-butane, 1,4-two (N-methylamino)-octafluoro is for butane, 1,5-two (N-methylamino)-Decafluoropentane, 1,6-two (N-methylamino)-perfluoro hexane, 1,7-two (N-methylamino)-perfluoro pentane, 1,8-two (N-methylamino)-perfluoro octane, the 5-fluorouracil, the 6-fluorouracil, 1-fluoro xanthine, 3-fluoro xanthine, 7-fluoro xanthine, 3-fluoro VITAMIN B4,5-fluoro 6-Methyl Uracil, 5-trifluoromethyl uridylic, 6-fluoro 6-Methyl Uracil, 1-fluoro methyl xanthine, 3-fluoro methyl xanthine, 7-fluoro methyl xanthine, the fluorine atom of 3-fluoro methyladenine and above-mentioned HLN-R-NLH type compound is by bromine atoms, the compound that the chlorine atom replaces etc.

As HO-R-NH ₂The type compound, R is identical with general formula (I) with the definition of L, can enumerate 2-amino-3-fluorophenol, 2-amino-4-fluorophenol, 2-amino-3,4-phenyl-difluoride phenol, 2-amino-3,5-phenyl-difluoride phenol, 2-amino-3,6-phenyl-difluoride phenol, 2-amino-3,4,5-trifluoro-benzene phenol, 2-amino-3,4,6-trifluoro-benzene phenol, 2-amino-tetrafluoro substituting phenol, 2-amino-3-(three fluoro methyl) phenol, 2-amino-4-(three fluoro methyl) phenol, 2-amino-3,4-two (three fluoro methyl) phenol, 2-amino-3,5-two (three fluoro methyl) phenol, 2-amino-3,6-two (three fluoro methyl) phenol, 2-amino-3,4,5-three (three fluoro methyl) phenol, 2-amino-3,4,6-three (three fluoro methyl) phenol, 2-amino-four (three fluoro methyl) phenol, 3-amino-2-fluorophenol, 3-amino-4-fluorophenol, 3-amino-5-fluorophenol, 3-amino-2,4-phenyl-difluoride phenol, 3-amino-2,5-phenyl-difluoride phenol, 3-amino-4,5-phenyl-difluoride phenol, 3-amino-4,6-phenyl-difluoride phenol, 3-amino-5,6-phenyl-difluoride phenol, 3-amino-2,4,5-trifluoro-benzene phenol, 3-amino-4,5,6-trifluoro-benzene phenol, 3-amino-tetrafluoro substituting phenol, 3-amino-2-(three fluoro methyl) phenol, 3-amino-4-(three fluoro methyl) phenol, 3-amino-5-(three fluoro methyl) phenol, 3-amino-2,4-two (three fluoro methyl) phenol, 3-amino-2,5-two (three fluoro methyl) phenol, 3-amino-4,5-two (three fluoro methyl) phenol, 3-amino-4,6-two (three fluoro methyl) phenol, 3-amino-5,6-two (three fluoro methyl) phenol, 3-amino-2,4,5-three (three fluoro methyl) phenol, 3-amino-4,5,6-three (three fluoro methyl) phenol, 3-amino-four (three fluoro methyl) phenol, 4-amino-2-fluorophenol, 4-amino-3-fluorophenol, 4-amino-2,3-phenyl-difluoride phenol, 4-amino-2,5-phenyl-difluoride phenol, 4-amino-2,6-phenyl-difluoride phenol, 4-amino-2,3,5-trifluoro-benzene phenol, 4-amino-2,3,6-trifluoro-benzene phenol, 4-amino-tetrafluoro substituting phenol, 4-amino-2-(three fluoro methyl) phenol, 4-amino-3-(three fluoro methyl) phenol, 4-amino-2,3-two (three fluoro methyl) phenol, 4-amino-2,5-two (three fluoro methyl) phenol, 4-amino-2,6-two (three fluoro methyl) phenol, 4-amino-2,3,5-three (three fluoro methyl) phenol, 4-amino-2,3,6-three (three fluoro methyl) phenol, 4-amino-four (three fluoro methyl) phenol, 5-amino-2-fluoro-1-hydroxyl naphthalene, 5-amino-3-fluoro-1-hydroxyl naphthalene, 5-amino-4-fluoro-1-hydroxyl naphthalene, 5-amino-2,3-two fluoro-1-hydroxyl naphthalene, 5-amino-2,4-two fluoro-1-hydroxyl naphthalene, 5-amino-2,6-two fluoro-1-hydroxyl naphthalene, 5-amino-2,7-two fluoro-1-hydroxyl naphthalene, 5-amino-2,8-two fluoro-1-hydroxyl naphthalene, 5-amino-3,4-two fluoro-1-hydroxyl naphthalene, 5-amino-3,8-two fluoro-1-hydroxyl naphthalene, 5-amino-4,8-two fluoro-1-hydroxyl naphthalene, 5-amino-2,3,4-three fluoro-1-hydroxyl naphthalene, 5-amino-2,3,6-three fluoro-1-hydroxyl naphthalene, 5-amino-2,3,7-three fluoro-1-hydroxyl naphthalene, 5-amino-2,3,8-three fluoro-1-hydroxyl naphthalene, 5-amino-2,3,6,7-tetrafluoro generation-1-hydroxyl naphthalene, 5-amino-hexafluoro--1-hydroxyl naphthalene, 2-amino-1-fluoro-6-hydroxyl naphthalene, 2-amino-3-fluoro-6-hydroxyl naphthalene, 2-amino-4-fluoro-6-hydroxyl naphthalene, 2-amino-1,3-two fluoro-6-hydroxyl naphthalene, 2-amino-1,4-two fluoro-6-hydroxyl naphthalene, 2-amino-1,5-two fluoro-6-hydroxyl naphthalene, 2-amino-3,4-two fluoro-6-hydroxyl naphthalene, 2-amino-3,5-two fluoro-6-hydroxyl naphthalene, 2-amino-4,5-two fluoro-6-hydroxyl naphthalene, 2-amino-1,3,4-three fluoro-6-hydroxyl naphthalene, 2-amino-1,3,5-three fluoro-6-hydroxyl naphthalene, 2-amino-3,4,5-three fluoro-6-hydroxyl naphthalene, 2-amino-1,3,4,5-tetrafluoro generation-6-hydroxyl naphthalene, 2-amino-hexafluoro--6-hydroxyl naphthalene, two (4-amino-2,3-phenyl-difluoride base) methane, two (4-amino-2,6-phenyl-difluoride base) methane, two (4-amino-3,5-phenyl-difluoride base) methane, two (4-hydroxyl tetrafluoro is for phenyl) methane, 4,4 '-two (2-amino-hexafluoro-sec.-propyl) biphenyl ether, 4,4 '-isopropylidene two (2,6-phenyl-difluoride amine), 3, two (three fluoro methyl) the benzoyl amidoximes of 5-, 5-(three fluoro methyl) pyridine-2-alumina amidoxime, 2-amino-tetrafluoro is for ethanol, 3-amino-hexafluoro--1-propyl alcohol, 4-amino-2,2 ', 3,3 '-tetrafluoro generation-1-butanols, 4-amino-octafluoro generation-1-butanols, 5-amino-perfluoro-1-amylalcohol, 6-amino-perfluoro-1-hexanol, 7-amino-perfluoro-1-enanthol, 8-amino-perfluoro-1-octanol and above-mentioned HO-R-NH ₂The compound that the fluorine atom of type compound is replaced by bromine atoms, chlorine atom etc.

As HO-R-NLH type compound, R is identical with general formula (I) with the definition of L, can enumerate 2-(N-methylamino)-3-fluorophenol, 2-(N-methylamino)-4-fluorophenol, 2-(N-methylamino)-3,4-phenyl-difluoride phenol, 2-(N-methylamino)-3,5-phenyl-difluoride phenol, 2-(N-methylamino)-3,6-phenyl-difluoride phenol, 2-(N-methylamino)-3,4,5-trifluoro-benzene phenol, 2-(N-methylamino)-3,4,6-trifluoro-benzene phenol, 2-(N-methylamino)-tetrafluoro substituting phenol, 3-(N-methylamino)-2-fluorophenol, 3-(N-methylamino)-4-fluorophenol, 3-(N-methylamino)-5-fluorophenol, 3-(N-methylamino)-2,4-phenyl-difluoride phenol, 3-(N-methylamino)-2,5-phenyl-difluoride phenol, 3-(N-methylamino)-4,5-phenyl-difluoride phenol, 3-(N-methylamino)-4,6-phenyl-difluoride phenol, 3-(N-methylamino)-5,6-phenyl-difluoride phenol, 3-(N-methylamino)-2,4,5-trifluoro-benzene phenol, 3-(N-methylamino)-4,5,6-trifluoro-benzene phenol, 3-(N-methylamino)-tetrafluoro substituting phenol, 4-(N-methylamino)-2-fluorophenol, 4-(N-methylamino)-3-fluorophenol, 4-(N-methylamino)-2,3-phenyl-difluoride phenol, 4-(N-methylamino)-2,5-phenyl-difluoride phenol, 4-(N-methylamino)-2,6-phenyl-difluoride phenol, 4-(N-methylamino)-2,3,5-trifluoro-benzene phenol, 4-(N-methylamino)-2,3,6-trifluoro-benzene phenol, 4-(N-methylamino)-tetrafluoro substituting phenol, 5-(N-methylamino)-2-fluoro-1-hydroxyl naphthalene, 5-(N-methylamino)-3-fluoro-1-hydroxyl naphthalene, 5-(N-methylamino)-4-fluoro-1-hydroxyl naphthalene, 5-(N-methylamino)-2,3-two fluoro-1-hydroxyl naphthalene, 5-(N-methylamino)-2,4-two fluoro-1-hydroxyl naphthalene, 5-(N-methylamino)-2,6-two fluoro-1-hydroxyl naphthalene, 5-(N-methylamino)-2,7-two fluoro-1-hydroxyl naphthalene, 5-(N-methylamino)-2,8-two fluoro-1-hydroxyl naphthalene, 5-(N-methylamino)-3,4-two fluoro-1-hydroxyl naphthalene, 5-(N-methylamino)-3,8-two fluoro-1-hydroxyl naphthalene, 5-(N-methylamino)-4,8-two fluoro-1-hydroxyl naphthalene, 5-(N-methylamino)-2,3,4-three fluoro-1-hydroxyl naphthalene, 5-(N-methylamino)-2,3,6-three fluoro-1-hydroxyl naphthalene, 5-(N-methylamino)-2,3,7-three fluoro-1-hydroxyl naphthalene, 5-(N-methylamino)-2,3,8-three fluoro-1-hydroxyl naphthalene, 5-(N-methylamino)-2,3,6,7-tetrafluoro generation-1-hydroxyl naphthalene, 5-(N-methylamino)-hexafluoro--1-hydroxyl naphthalene, 2-(N-methylamino)-1-fluoro-6-hydroxyl naphthalene, 2-(N-methylamino)-3-fluoro-6-hydroxyl naphthalene, 2-(N-methylamino)-4-fluoro-6-hydroxyl naphthalene, 2-(N-methylamino)-1,3-two fluoro-6-hydroxyl naphthalene, 2-(N-methylamino)-1,4-two fluoro-6-hydroxyl naphthalene, 2-(N-methylamino)-1,5-two fluoro-6-hydroxyl naphthalene, 2-(N-methylamino)-3,4-two fluoro-6-hydroxyl naphthalene, 2-(N-methylamino)-3,5-two fluoro-6-hydroxyl naphthalene, 2-(N-methylamino)-4,5-two fluoro-6-hydroxyl naphthalene, 2-(N-methylamino)-1,3,4-three fluoro-6-hydroxyl naphthalene, 2-(N-methylamino)-1,3,5-three fluoro-6-hydroxyl naphthalene, 2-(N-methylamino)-3,4,5-three fluoro-6-hydroxyl naphthalene, 2-(N-methylamino)-1,3,4,5-tetrafluoro generation-6-hydroxyl naphthalene, 2-(N-methylamino)-hexafluoro--6-hydroxyl naphthalene, two (4-(N-methylamino)-2,3-phenyl-difluoride base) methane, two (4-(N-methylamino)-2,6-phenyl-difluoride base) methane, two (4-hydroxyls-3,5-phenyl-difluoride base) methane, two (4-hydroxyl tetrafluoro is for phenyl) methane, 4,4 '-two (2-(N-methylamino)-hexafluoro-sec.-propyl) biphenyl ether, 4,4 '-isopropylidene two (2,6-phenyl-difluoride amine), 2-(N-methylamino)-tetrafluoro is for ethanol, 3-(N-methylamino)-hexafluoro--1-propyl alcohol, 4-(N-methylamino)-2,2 ', 3,3 '-tetrafluoro generation-1-butanols, 4-(N-methylamino)-octafluoro generation-1-butanols, 5-(N-methylamino)-perfluoro-1-amylalcohol, 6-(N-methylamino)-perfluoro-1-hexanol, 7-(N-methylamino)-perfluoro-1-enanthol, 8-(N-methylamino)-perfluoro-1-octanol, 2-(N-three fluoro methylaminos)-3-fluorophenol, 2-(N-three fluoro methylaminos)-4-fluorophenol, 2-(N-three fluoro methylaminos)-3,4-phenyl-difluoride phenol, 2-(N-three fluoro methylaminos)-3,5-phenyl-difluoride phenol, 2-(N-three fluoro methylaminos)-3,6-phenyl-difluoride phenol, 2-(N-three fluoro methylaminos)-3,4,5-trifluoro-benzene phenol, 2-(N-three fluoro methylaminos)-3,4,6-trifluoro-benzene phenol, 2-(N-three fluoro methylaminos)-tetrafluoro substituting phenol, 3-(N-three fluoro methylaminos)-2-fluorophenol, 3-(N-three fluoro methylaminos)-4-fluorophenol, 3-(N-three fluoro methylaminos)-5-fluorophenol, 3-(N-three fluoro methylaminos)-2,4-phenyl-difluoride phenol, 3-(N-three fluoro methylaminos)-2,5-phenyl-difluoride phenol, 3-(N-three fluoro methylaminos)-4,5-phenyl-difluoride phenol, 3-(N-three fluoro methylaminos)-4,6-phenyl-difluoride phenol, 3-(N-three fluoro methylaminos)-5,6-phenyl-difluoride phenol, 3-(N-three fluoro methylaminos)-2,4,5-trifluoro-benzene phenol, 3-(N-three fluoro methylaminos)-4,5,6-trifluoro-benzene phenol, 3-(N-three fluoro methylaminos)-tetrafluoro substituting phenol, 4-(N-three fluoro methylaminos)-2-fluorophenol, 4-(N-three fluoro methylaminos)-3-fluorophenol, 4-(N-three fluoro methylaminos)-2,3-phenyl-difluoride phenol, 4-(N-three fluoro methylaminos)-2,5-phenyl-difluoride phenol, 4-(N-three fluoro methylaminos)-2,6-phenyl-difluoride phenol, 4-(N-three fluoro methylaminos)-2,3,5-trifluoro-benzene phenol, 4-(N-three fluoro methylaminos)-2,3,6-trifluoro-benzene phenol, 4-(N-three fluoro methylaminos) tetrafluoro substituting phenol, 5-(N-three fluoro methylaminos)-2-fluoro-1-hydroxyl naphthalene, 5-(N-three fluoro methylaminos)-3-fluoro-1-hydroxyl naphthalene, 5-(N-three fluoro methylaminos)-4-fluoro-1-hydroxyl naphthalene, 5-(N-three fluoro methylaminos)-2,3-two fluoro-1-hydroxyl naphthalene, 5-(N-three fluoro methylaminos)-2,4-two fluoro-1-hydroxyl naphthalene, 5-(N-three fluoro methylaminos)-2,6-two fluoro-1-hydroxyl naphthalene, 5-(N-three fluoro methylaminos)-2,7-two fluoro-1-hydroxyl naphthalene, 5-(N-three fluoro methylaminos)-2,8-two fluoro-1-hydroxyl naphthalene, 5-(N-three fluoro methylaminos)-3,4-two fluoro-1-hydroxyl naphthalene, 5-(N-three fluoro methylaminos)-3,8-two fluoro-1-hydroxyl naphthalene, 5-(N-three fluoro methylaminos)-4,8-two fluoro-1-hydroxyl naphthalene, 5-(N-three fluoro methylaminos)-2,3,4-three fluoro-1-hydroxyl naphthalene, 5-(N-three fluoro methylaminos)-2,3,6-three fluoro-1-hydroxyl naphthalene, 5-(N-three fluoro methylaminos)-2,3,7-three fluoro-1-hydroxyl naphthalene, 5-(N-three fluoro methylaminos)-2,3,8-three fluoro-1-hydroxyl naphthalene, 5-(N three fluoro methylaminos)-2,3,6,7-tetrafluoro generation-1-hydroxyl naphthalene, 5-(N-three fluoro methylaminos)-hexafluoro--1-hydroxyl naphthalene, 2-(N-three fluoro methylaminos)-1-fluoro-6-hydroxyl naphthalene, 2-(N-three fluoro methylaminos)-3-fluoro-6-hydroxyl naphthalene, 2-(N-three fluoro methylaminos)-4-fluoro-6-hydroxyl naphthalene, 2-(N-three fluoro methylaminos)-1,3-two fluoro-6-hydroxyl naphthalene, 2-(N-three fluoro methylaminos)-1,4-two fluoro-6-hydroxyl naphthalene, 2-(N-three fluoro methylaminos)-1,5-two fluoro-6-hydroxyl naphthalene, 2-(N-three fluoro methylaminos)-3,4-two fluoro-6-hydroxyl naphthalene, 2-(N-three fluoro methylaminos)-3,5-two fluoro-6-hydroxyl naphthalene, 2-(N-three fluoro methylaminos)-4,5-two fluoro-6-hydroxyl naphthalene, 2-(N-three fluoro methylaminos)-1,3,4-three fluoro-6-hydroxyl naphthalene, 2-(N-three fluoro methylaminos)-1,3,5-three fluoro-6-hydroxyl naphthalene, 2-(N-three fluoro methylaminos)-3,4,5-three fluoro-6-hydroxyl naphthalene, 2-(N-three fluoro methylaminos)-1,3,4,5-tetrafluoro generation-6-hydroxyl naphthalene, 2-(N-three fluoro methylaminos) hexafluoro--6-hydroxyl naphthalene, two (4-(N-three fluoro methylaminos)-2,3-phenyl-difluoride base) methane, two (4-(N-three fluoro methylaminos)-2,6-phenyl-difluoride base) methane, two (4-(N-three fluoro methylaminos)-3,5-phenyl-difluoride base) methane, two (4-hydroxyl tetrafluoro is for phenyl) methane, 4,4 '-two (2-(N-three fluoro methylaminos)-hexafluoro-sec.-propyl) biphenyl ether, 4,4 '-isopropylidene two (2,6-phenyl-difluoride amine), 2-(N-three fluoro methylaminos)-tetrafluoro is for ethanol, 3-(N-three fluoro methylaminos)-hexafluoro--1-propyl alcohol, 4-(N-three fluoro methylaminos)-2,2 ', 3,3 '-tetrafluoro generation-1-butanols, 4-(N-three fluoro methylaminos)-octafluoro generation-1-butanols, 5-(N-three fluoro methylaminos)-perfluoro-1-amylalcohol, 6-(N-three fluoro methylaminos)-perfluoro-1-hexanol, 7-(N-three fluoro methylaminos)-perfluoro-1-enanthol, the fluorine atom of 8-(N-three fluoro methylaminos)-perfluoro-1-octanol and above-mentioned HO-R-NLH type compound is by bromine atoms, the compound that the chlorine atom replaces etc.

As H ₂N-R-NLH type compound, R is identical with general formula (I) with the definition of L, can enumerate 2-(N-methylamino)-3-fluoro aniline, 2-(N-methylamino)-4-fluoro aniline, 2-(N-methylamino)-3,4-phenyl-difluoride amine, 2-(N-methylamino)-3,5-phenyl-difluoride amine, 2-(N-methylamino)-3,6-phenyl-difluoride amine, 2-(N-methylamino)-3,4,5-trifluoro-benzene amine, 2-(N-methylamino)-3,4,6-trifluoro-benzene amine, 2-(N-methylamino)-tetrafluoro is for aniline, 3-(N-methylamino)-2-fluoro aniline, 3-(N-methylamino)-4-fluoro aniline, 3-(N-methylamino)-5-fluoro aniline, 3-(N-methylamino)-2,4-phenyl-difluoride amine, 3-(N-methylamino)-2,5-phenyl-difluoride amine, 3-(N-methylamino)-4,5-phenyl-difluoride amine, 3-(N-methylamino)-4,6-phenyl-difluoride amine, 3-(N-methylamino)-5,6-phenyl-difluoride amine, 3-(N-methylamino)-2,4,5-trifluoro-benzene amine, 3-(N-methylamino)-4,5,6-trifluoro-benzene amine, 3-(N-methylamino) tetrafluoro is for aniline, 4-(N-methylamino)-2-fluoro aniline, 4-(N-methylamino)-3-fluoro aniline, 4-(N-methylamino)-2,3-phenyl-difluoride amine, 4-(N-methylamino)-2,5-phenyl-difluoride amine, 4-(N-methylamino)-2,6-phenyl-difluoride amine, 4-(N-methylamino)-2,3,5-trifluoro-benzene amine, 4-(N-methylamino)-2,3,6-trifluoro-benzene amine, 4-(N-methylamino) tetrafluoro is for aniline, 5-amino-2-fluoro-1-(N-methylamino) naphthalene, 5-amino-3-fluoro-1-(N-methylamino) naphthalene, 5-amino-4-fluoro-1-(N-methylamino) naphthalene, 5-amino-2,3-two fluoro-1-(N-methylamino) naphthalene, 5-amino-2,4-two fluoro-1-(N-methylamino) naphthalene, 5-amino-2,6-two fluoro-1-(N-methylamino) naphthalene, 5-amino-2,7-two fluoro-1-(N-methylamino) naphthalene, 5-amino-2,8-two fluoro-1-(N-methylamino) naphthalene, 5-amino-3,4-two fluoro-1-(N-methylamino) naphthalene, 5-amino-3,8-two fluoro-1-(N-methylamino) naphthalene, 5-amino-4,8-two fluoro-1-(N-methylamino) naphthalene, 5-amino-2,3,4-three fluoro-1-(N-methylamino) naphthalene, 5-amino-2,3,6-three fluoro-1-(N-methylamino) naphthalene, 5-amino-2,3,7-three fluoro-1-(N-methylamino) naphthalene, 5-amino-2,3,8-three fluoro-1-(N-methylamino) naphthalene, 5-amino-2,3,6,7-tetrafluoro generation-1-(N-methylamino) naphthalene, 5-amino-hexafluoro--1-(N-methylamino) naphthalene, 2-amino-1-fluoro-6-(N-methylamino) naphthalene, 2-amino-3-fluoro-6-(N-methylamino) naphthalene, 2-amino-4-fluoro-6-(N-methylamino) naphthalene, 2-amino-1,3-two fluoro-6-(N-methylamino) naphthalene, 2-amino-1,4-two fluoro-6-(N-methylamino) naphthalene, 2-amino-1,5-two fluoro-6-(N-methylamino) naphthalene, 2-amino-3,4-two fluoro-6-(N-methylamino) naphthalene, 2-amino-3,5-two fluoro-6-(N-methylamino) naphthalene, 2-amino-4,5-two fluoro-6-(N-methylamino) naphthalene, 2-amino-1,3,4-three fluoro-6-(N-methylamino) naphthalene, 2-amino-1,3,5-three fluoro-6-(N-methylamino) naphthalene, 2-amino-3,4,5-three fluoro-6-(N-methylamino) naphthalene, 2-amino-1,3,4,5-tetrafluoro generation-6-(N-methylamino) naphthalene, 2-amino-hexafluoro--6-(N-methylamino) naphthalene, 4-amino-4 '-(N-methylamino)-2,3,4, the 5-tetrafluoro is for biphenyl, 4-amino-4 '-(N-methylamino)-2,2 ', 4,4 '-tetrafluoro is for biphenyl, 4-amino-4 '-(N-methylamino)-2,2 ', 3,3 ', 4,4 ', 5,5 ', 6,6 '-octafluoro is for biphenyl, (4-amino-2,3-phenyl-difluoride base) (4-(N-methylamino)-2,3-phenyl-difluoride base) methane, (4-amino-2,6-phenyl-difluoride base) (4-(N-methylamino)-2,6-phenyl-difluoride base) methane, (4-amino-3,5-phenyl-difluoride base) (4-(N-methylamino)-3,5-phenyl-difluoride base) methane, (4-amino-tetrafluoro is for phenyl) (4-(N-methylamino)-tetrafluoro is for phenyl) methane, (4-(2-amino-hexafluoro-sec.-propyl) (4-(4-(N-methylamino)-hexafluoro-sec.-propyl)) biphenyl ether, 1-amino-2-(N-methylamino) tetrafluoro is for ethane, 1-amino-3-(N-methylamino) hexafluoorpropane, 1-amino-4-(N-methylamino)-2,2 ', 3,3 '-the hexafluoro-butane, 1-amino-4-(N-methylamino)-octafluoro is for butane, 1-amino-5-(N-methylamino)-Decafluoropentane, 1-amino-6-(N-methylamino)-perflexane, 1-amino-7-(N-methylamino)-perflenapent, 1-amino-8-(N-methylamino)-PFO, (4-bromine tetrafluoro is for phenyl) hydrazine, 2-chloro-6-fluoro phenylhydrazine, 3-chloro-4-fluoro phenylhydrazine, 2-chloro-4-(three fluoro methyl) phenylhydrazine, 2-chloro-5-three fluoro procarbazines, 2,4-two chloro-6-(three fluoro methyl) phenylhydrazine, 2,6-two chloro-6-(three fluoro methyl) phenylhydrazine, 2,4-fluoro phenylhydrazine, 2,5-fluoro phenyl hydrazine, 5-fluoro-2-procarbazine, 4-fluoro phenylhydrazine, the phenyl-pentafluoride hydrazine, 4-(three fluoro methoxyl groups) phenylhydrazine, 2-(three fluoro methoxyl groups) phenylhydrazine, 2-amino-6-fluoro purine, 2-amino-6-three fluoro methyl purines and above-mentioned H ₂The compound that the fluorine atom of N-R-NLH type compound is replaced by bromine atoms, chlorine atom etc.

Wherein be preferably the tetrafluoro Resorcinol, the tetrafluoro Resorcinol, the tetrabromo Resorcinol, 1, two (the 2-hydroxyl hexafluoro-sec.-propyl) benzene of 4-, 4,4 '-two (2-hydroxyl hexafluoro-sec.-propyl) biphenyl, 4,4 '-two (2-hydroxyl hexafluoro-sec.-propyl) biphenyl ether, 2,2 ', 3,3 '-tetrafluoro generation-1, the 4-butyleneglycol, 2-amino-5-fluoro aniline, 2-amino-6-fluoro benzyl amine, 2,2 '-two (three fluoro methyl)-4,4 '-benzidine, 3,3 '-two (three fluoro methyl)-4,4 '-benzidine, 4,4 '-the diamino octafluoro is for biphenyl, 2, two (3-amino-4-aminomethyl phenyl) hexafluoorpropanes of 2-, 2, two [4-(4-aminophenyl)]-hexafluoorpropanes of 2-, 2, two (4-the aminophenyl)-hexafluoorpropanes of 2-, 4,4 '-the diamino octafluoro is for biphenyl, 5-three fluoro 6-Methyl Uracils, 4-amino-3-fluorophenol, be preferably the tetrafluoro Resorcinol especially, the tetrafluoro Resorcinol, the tetrabromo Resorcinol, 4,4 '-the diamino octafluoro is for biphenyl, 2,2 ', 3,3 '-tetrafluoro generation-1, the 4-butyleneglycol.

Among the present invention,, for example can enumerate the organo-aluminium compound example of following general formula (VII) expression as (d) organo-aluminium compound that uses as required (below be also referred to as " component (d) ").

R ^a _nAlT _3-n......(VII)

In the formula, R ^aBe the alkyl of carbonatoms 1～12, T is that halogen atom or hydrogen atom, n are 1～3.

In the above-mentioned general formula (VII), R ^aIt is the alkyl of carbonatoms 1～12, for example alkyl, cycloalkyl or aryl specifically can be enumerated methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, amyl group, hexyl, isohexyl, heptyl, nonyl, octyl group, cyclopentyl, cyclohexyl, phenyl, tolyl etc.As such organo-aluminium compound (d), specifically can enumerate the trialkylaluminium of trimethyl aluminium, triethyl aluminum, triisopropylaluminiuand, triisobutyl aluminium, trioctylaluminum, three-2-ethylhexyl aluminium etc.; Thiazolinyl aluminium such as isopentene aluminium; Dialkylaluminum halides such as dimethylaluminum chloride, diethyl aluminum chloride, di-isopropyl aluminum chloride, diisobutyl aluminum chloride, dimethyl aluminum bromide; Aluminum alkyls sesquihalide such as sesquialter methyl aluminum chloride, sesquialter ethyl aluminum chloride, sesquialter sec.-propyl chlorination aluminium, sesquialter butyl aluminum chloride, sesquialter ethyl aluminum bromide; Alkyllithium dihalides such as methylaluminum dichloride, ethylaluminum dichloride, sec.-propyl al dichloride, ethyl aluminum dibromide; Alkyl aluminum hydrides such as hydrogenation dimethyl aluminium, diethyl aluminium hydride, dihydroxy phenyl aluminium, hydrogenation di-isopropyl aluminium, hydrogenation di-n-butyl aluminium, diisobutylaluminium hydride, hydrogenation two isohexyl aluminium, hydrogenation phenylbenzene aluminium, hydrogenation dicyclohexyl aluminium thing, hydrogenation di-secondary heptyl aluminium, hydrogenation di-secondary nonyl aluminium etc.

In addition, as organo-aluminium compound (d), also can use the compound of following general formula (VIII) expression.

R ^a _nAlU _3-n......(VIII)

In the formula, R ^aSame as above, U is-OR ^bBase ,-OSiR ^c ₃Base ,-OAlR ^d ₂Base ,-NR ^e ₂Base ,-SiR ^f ₃The base or-N (R ^g) AlR ^h ₂Base, n are 1～2, R ^b, R ^c, R ^dWith R ^hBe methyl, ethyl, sec.-propyl, isobutyl-, cyclohexyl, phenyl etc., R ^eBe hydrogen atom, methyl, ethyl, sec.-propyl, phenyl, trimethyl silyl etc., R ^fWith R ^gBe methyl, ethyl etc.

As such organo-aluminium compound, specifically can use following compound.

(1) with R ^a _nAl (OR ^b) _3-nThe compound of expression is as dimethyl methyl aluminium alcoholates, diethyl aluminum ethylate, diisobutyl carbinol(DIBC) aluminium etc.; (2) with R ^a _nAl (OSiR ^c ₃) _3-nThe compound of expression is as Et ₂Al (OSiMe ₃), (iso-Bu) ₂Al (OSiMe ₃), (iso-Bu) ₂Al (OSiEt ₃) etc., (3) are with R ^a _nAl (OAlR ^d ₂) _3-nThe compound of expression is as Et ₂AlOAlEt ₂, (iso-Bu) ₂AlOAl (iso-Bu) ₂Deng, (4) are with R ^a _nAl (NR ^e) _3-nThe compound of expression is as Me ₂AlNEt ₂, Et ₂AlNHMe, Me ₂AlNHEt, Et ₂AlN (SiMe ₃) ₂, (iso-Bu) ₂AlN (SiMe ₃) ₂Deng, (5) are with R ^a _nAl (SiR ^f ₃) _3-nThe compound of expression is as (iso-Bu) ₂AlSiMe ₃Deng (6) with R ^a _nAl[N (R ^g) AlR ^h ₂] _3-nThe compound of expression is as Et ₂AlN (Me) AlEt ₂, (iso-Bu) ₂AlN (Et) Al (iso-Bu) ₂Deng.

With above-mentioned general formula (VII) with (VIII) expression organo-aluminium compound in, preferably with general formula R ^a ₃The compound that Al represents, preferred R ^aIt is the compound of the alkyl of carbonatoms 1～4.

Olefin polymerization catalysis of the present invention, above-mentioned each composition is attached to following solid-state carrier.Spendable solid-state carrier is inorganic or organic compound among the present invention, and the particulate state of using particle diameter 3～300 μ m, preferred 5～200 μ m is to particulate solid.Wherein, as inorganic carrier, preferred porous oxide specifically can be enumerated SiO ₂, Al ₂O ₃, MgO, ZrO ₂, TiO ₂, B ₂O ₃, CaO, ZnO, BaO, ThO ₂Deng or its mixture, for example can enumerate SiO ₂-MgO, SiO ₂-Al ₂O ₃, SiO ₂-TiO ₂, SiO ₂-V ₂O ₅, SiO ₂-Cr ₂O ₃, SiO ₂-TiO ₂-MgO etc.Wherein, be preferably selected from SiO ₂With Al ₂O ₃At least a kind of composition as main component.In addition, in above-mentioned inorganic oxide, can contain small amount of N a ₂CO ₃, K ₂CO ₃, CaCO ₃, MgCO ₃, Na ₂SO ₄, Al ₂(SO ₄) ₃, BaSO ₄, KNO ₃, Mg (NO ₃) ₂, Al (NO ₃) ₃, Na ₂O, K ₂O, Li ₂Carbonate such as O, vitriol, nitrate, oxide components.

Such solid-state carrier, proterties is different with manufacture method according to its kind, the solid-state carrier that the present invention preferably uses, specific surface area is 50～1000m ²/ g, be preferably 100～800m ²/ g, pore volume is preferably 0.3～2.5cm ³/ g.This solid-state carrier uses as required at 100～1000 ℃, the goods preferably fired under 150～700 ℃ temperature.

Such solid-state carrier, proterties is different with manufacture method according to its kind, the solid-state carrier that the present invention preferably uses, specific surface area is 50～1000m ²/ g, be preferably 100～700m ²/ g, pore volume is preferably 0.3～2.5cm ³/ g.This solid-state carrier uses as required at 100～1000 ℃, the goods preferably fired under 150～700 ℃ temperature.

As can be used for solid-state carrier of the present invention, the organic compound particulate state that also can enumerate particle diameter 3～300 μ m is to microgranular solid.As these organic compound, can enumerate alpha-olefin with carbonatomss 2～14 such as ethene, propylene, 1-butylene, 4-methyl-1-pentenes and be (be total to) polymkeric substance that main component generates or be the polymkeric substance or the multipolymer of main component generation with vinyl cyclohexane, vinylbenzene.

Below, solid catalyst for olefin polymerization of the present invention more specifically is described.The 1st solid catalyst for olefin polymerization of the present invention is characterised in that, comprise periodictable the 4th group transition metal compound, (b) organoaluminum oxo-compounds, (c) that solid-state carrier and (A) (a) comprise the dentate that contains cyclopentadienyi skeleton more than 1 contact with the multi-functional Organohalogen compounds composition of general formula (I) expression and must solid-state transition metal catalyst component and (B) organo-aluminium compound as required.

(Q ¹) _o-R-(Q ²) _p... general formula (I)

Above-mentioned solid-state transition metal catalyst component (A) can contact formulated by component (a), component (b), component (c) and solid-state carrier mixing in unreactive hydrocarbons.

At this moment, the order by merging of each composition is arbitrarily, preferably avoids component (a) directly to mix with component (c) and contacts.Directly might make component (a) decompose, go bad in the contact, the catalytic activity of final gained olefin polymerization catalysis might significantly descend.

Preferably engagement sequence is, for example

I) component (b) is mixed with solid-state carrier and contact, contact component (a) again, contact the method for component (c) then;

Component (b) is mixed with solid-state carrier contact, contact component (c) again, contact the method for component (a) then;

Component (a) is mixed with component (b) contact, contact with solid-state carrier then, again the method that contacts with component (c);

Component (b) is contacted with solid-state carrier with the mixture of component (c), mix the method that contacts with component (a) then;

Component (b) is mixed with solid-state carrier contact, contact with component (a) then, contact with component (c) then, and the method that contacts with component (b) once more;

Component (b) and solid-state carrier are mixed contact, contact with component (c) again, and then with component (b), contact the method for component (a) again;

Component (a) and component (b) are mixed contact, contact solid-state carrier again, contact component (c) then, again the method that contacts with component (b) mixing etc.

The 2nd olefin polymerization catalysis of the present invention (C-2) is characterised in that, comprise that multi-functional Organohalogen compounds composition that solid-state carrier and (A) (a) contain periodictable the 4th group transition metal compound, (b) organoaluminum oxo-compounds, (c) general formula (I) expression of the dentate that cyclopentadienyi skeleton is arranged more than 1 contacts with (d) organo-aluminium compound and must solid-state catalyst component and (B) organo-aluminium compound as required.

Above-mentioned solid-state transition metal catalyst component (A) can contact formulated by component (a), component (b), component (c), component (d) and solid-state carrier mixing in unreactive hydrocarbons.

At this moment, the order by merging of each composition is arbitrarily, preferably avoids component (a) directly to mix with component (c) and contacts, and reason is the same.

Preferably engagement sequence is, for example

I) component (b) is mixed with solid-state carrier and contact, contact component (a) again, then the method that contacts with the mixture of component (c), component (d) or component (c) and component (d);

Component (b) is mixed with solid-state carrier contact, contact component (c) again, then the method that contacts with component (a) or component (d);

Component (a) and component (b) are mixed contact, then the method that contacts with the mixture of component (d) with solid-state carrier, component (c), component (d) or component (c);

Component (b) is contacted with solid-state carrier with the contact mixture of component (c), mix the method that contacts with component (a) or component (d) then.

Among the present invention, (B) organo-aluminium compound that uses (following also note is made " component (B) ") can be enumerated and the same organo-aluminium compound of component (d) as required, wherein, is preferably general formula R ^a ₃Al, R ^a _nAl (OR ^b) _3-n, R ^a _nAl (OAlR ^d ₂) _3-nThe organo-aluminium compound of expression, preferred especially R ^aIt is the compound of iso-alkyl, n=2.

Among the present invention, when mixing above-mentioned each composition, every 1g solid-state carrier, the consumption of component (a) is 10 ^-6～5 * 10 ^-4The mole, be preferably 5 * 10 ^-6～2 * 10 ^-4Mole, the concentration range of component (a) is 10 ^-5～10 ^-2Moles per litre of solvent, be preferably 5 * 10 ^-5～5 * 10 ^-3Moles per litre of solvent.The consumption of component (b) is, making the aluminium (Al) from this composition is 10～1000, preferred 50～500 with atomic ratio (Al/ transition metal) from the transition metal of component (a).The consumption of component (c) is, is 0.01～5.0 mole, preferred 0.02～1.0 mole, more preferably 0.03～0.5 mole with respect to 1 moles, of aluminum per mole of titanium metal from component (b).And when using component (d), its consumption is, makes the grammeatom of the aluminium atom (Al-b) in aluminium atom (Al-d) and the component (b) in this component (d) be 0.01～2.0 than (Al-d/Al-b), be preferably 0.02～1.0.

Mixing temperature when mixing above-mentioned each composition for-50～150 ℃, be preferably-20～120 ℃, be 1～1000 minute, be preferably 5～600 minutes duration of contact.In addition, when mixing contact, also can change mixing temperature.

Among the present invention,, can enumerate and component (b) and component (c) are mixed contact as one of preferred contact form, be made into contain component (b) and component (c) mix contactant solution, the method that this solution is contacted with other composition mixing.Component (b) and component (c) are mixed when contacting, and the concentration range of component (b) is 0.01～5 moles per litre of solvent, be preferably 0.1～3 moles per litre of solvent.The consumption of component (c) is 0.01～5.0 mole, is preferably 0.02～1.0 mole, more preferably 0.03～0.5 mole with respect to 1 mole of aluminium from component (b).Component (b), the mixing temperature when component (c) is mixed contact are-90～150 ℃, are preferably-80～120 ℃, are 1～1000 minute, are preferably 5～600 minutes duration of contact.

As the unreactive hydrocarbons that use in the catalyst preparation of the present invention, specifically can enumerate aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, 12 carbon alkane, kerosene; Alicyclic hydrocarbon such as pentamethylene, hexanaphthene, methylcyclopentane; Aromatic hydrocarbon such as benzene,toluene,xylene; Halohydrocarbon or its mixtures such as ethylene dichloride, chlorobenzene, methylene dichloride.

In the 1st olefin polymerization catalysis of the present invention (C-1), every 1g solid-state carrier preferably carries attached 10 ^- ⁴～5 * 10 ^-2Grammeatom, be preferably 5.0 * 10 ^-4～2 * 10 ^-2The transition metal atoms from component (a) of grammeatom, 10 ^-4～1.0 grammeatom, be preferably 5 * 10 ^-3～5 * 10 ^-1The aluminium atom from component (b) of grammeatom, 5 * 10 ^-5～5 * 10 ^-2The mole, be preferably 10 ^-5～10 ^-2The component (c) of mole.And the consumption of the component of using as required (B) is to be below 500 moles, to be preferably 1～200 mole from the transition metal atoms of component (a) with respect to every 1g.

In the 2nd olefin polymerization catalysis of the present invention (C-2), every 1g solid-state carrier preferably carries attached 5 * 10 ^-5～5 * 10 ^-2Grammeatom, be preferably 10 ^-5～10 ^-2The transition metal atoms from component (a) of grammeatom, 10 ^-3～1.0 grammeatom, be preferably 5 * 10 ^-3～5 * 10 ^-1The aluminium atom from component (b) and component (d) of grammeatom, 5 * 10 ^-5～5 * 10 ^-2The mole, be preferably 10 ^-5～10 ^-2The component (c) of mole.And the consumption of the component of using as required (B) is to be below 500 moles, to be preferably 1～200 mole from the transition metal atoms of component (a) with respect to every 1g.

Can directly use the above-mentioned the 1st and the 2nd olefin polymerization catalysis (C-1), (C-2), use after also can making alkene and this olefin polymerization catalysis pre-polymerization form prepolymerization catalyst.The detailed description of pre-polymerization as described later.

The 3rd olefin polymerization catalysis of the present invention (C-3) is characterised in that, comprise that solid-state carrier and (A) (a) contain periodictable the 4th group transition metal compound of the dentate that cyclopentadienyi skeleton is arranged more than 1, (b) organoaluminum oxo-compounds, (c) the multi-functional Organohalogen compounds contact of general formula (I) expression and solid-state transition metal catalyst component, the catalyzer of (B) organo-aluminium compound as required contacts with the alhpa olefin of ethene or ethene and carbonatoms 4～10, and the solid-state transition metal catalyst component of average every 1g makes 0.01～1000g utilize the gel permeation chromatography Z-average molecular weight more than 6,000,000, and die swelling is than being that polymkeric substance pre-polymerization more than 1.4 forms.

Solid-state transition metal catalyst component of the present invention (A) can contact formulated by component (a), component (b), component (c) and solid-state carrier mixing in unreactive hydrocarbons.At this moment, the order by merging of each composition is arbitrarily, preferably avoids component (a) directly to mix with component (c) and contacts.Directly might make component (a) decompose, go bad in the contact, the catalytic activity of final gained olefin polymerization catalysis might significantly descend.Preferably engagement sequence is, for example

Solid-state carrier is contacted with the mixture of component (b) with component (c), mix the method that contacts with component (a) then;

Solid-state carrier is mixed with component (b) contact, contact with component (a) then, contact with component (c) again, once again the method that contacts with component (b);

Solid-state carrier is mixed with component (b) contact, contact with component (c) then, contact once more with component (b) again, again the method that contacts with component (a);

Vii) component (a) and component (b) are mixed and contact, contact solid-state carrier again, contact component (c) then, once more the method that contacts with component (b) mixing etc.

The 4th olefin polymerization catalysis of the present invention (C-4) is characterised in that, comprise that solid-state carrier and (A) (a) comprise periodictable the 4th group transition metal compound of the dentate that contains cyclopentadienyi skeleton more than 1, (b) organoaluminum oxo-compounds, (c) the multivalence functionality Organohalogen compounds of representing with general formula (I), (d) organo-aluminium compound contact and solid-state transition metal catalyst component, the catalyzer of (B) organo-aluminium compound as required, contact with the alhpa olefin of ethene or ethene and carbonatoms 4～10, the solid-state transition metal catalyst component of average every 1g makes 0.01～1000g utilize the molecular-weight average of gel permeation chromatography Z more than 6,000,000, and die swelling is than being that polymkeric substance pre-polymerization more than 1.4 forms.

Above-mentioned solid-state transition metal catalyst component can contact formulated by component (a), component (b), component (c), component (d) and solid-state carrier mixing in unreactive hydrocarbons.At this moment, the order by merging of each composition is arbitrarily, preferably avoids component (a) directly to mix with component (c) and contacts, and reason is the same.

Preferably engagement sequence is, for example

I) component (b) is mixed with solid-state carrier and contact, contact component (a) again, contact the method for the mixture of component (c), component (d) or component (c) and component (d) then;

Component (a) and component (b) are mixed contact, contact solid-state carrier then, then the method that contacts with the mixture of component (d) with component (c), component (d) or component (c);

Solid-state carrier is contacted with the mixture of component (b) with component (c), mix the method that contacts with component (a) or component (d) again.

About the compound method of solid catalytic component of the present invention, when mixing above-mentioned each composition, every 1g solid-state carrier, the consumption of component (a) is 10 ^-6～5 * 10 ^-4The mole, be preferably 5 * 10 ^-6～2 * 10 ^-4Mole, the concentration range of component (a) is 10 ^-5～10 ^-2Moles per litre of solvent, be preferably 5 * 10 ^-5～5 * 10 ^-3Moles per litre of solvent.The consumption of component (b) is, is 10～1000, preferred 50～500 from the aluminium (Al) of this component (b) with atomic ratio (Al/ transition metal) from the transition metal of component (a).The consumption of component (c) is, with respect to 1 moles, of aluminum per mole of titanium metal from component (b), is 0.01～5.0 mole, preferred 0.02～1.0 mole, more preferably 0.03～0.5 mole.And when using component (d), its consumption is, the aluminium atom (Al-d) that makes this component (d) is 0.01～2.0 than (Al-d/Al-b), is preferably 0.02～1.0 with the grammeatom of the aluminium atom (Al-b) of component (b).

Mixing temperature when mixing above-mentioned each composition is-50～150 ℃, is preferably-20～120 ℃, is 1～1000 minute, is preferably 5～600 minutes duration of contact.Also can change mixing temperature and mix when contacting.

In the compound method of solid catalytic component of the present invention, as one of preferred contact form, can enumerate component (b) is contacted with component (c) mixing, be made into contain component (b) and component (c) mix contactant solution, make this solution mix the method that contacts then with other composition.Component (b) and component (c) are mixed when contacting, and the concentration range of component (b) is 0.01～5 moles per litre of solvent, be preferably 0.1～3 moles per litre of solvent.The consumption of component (c) is 0.01～5.0 mole, is preferably 0.02～1.0 mole, more preferably 0.03～0.5 mole with respect to 1 mole of aluminium from component (b).Component (b), the mixing temperature when component (c) is mixed contact are-90～150 ℃, are preferably-80～120 ℃, are 1～1000 minute, are preferably 5～600 minutes duration of contact.

As the unreactive hydrocarbons that use in the solid-state catalyst component preparation of the present invention, specifically can enumerate aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, 12 carbon alkane, kerosene; Alicyclic hydrocarbon such as pentamethylene, hexanaphthene, methylcyclopentane; Aromatic hydrocarbon such as benzene,toluene,xylene; Halon or its mixtures such as ethylene dichloride, chlorobenzene, methylene dichloride.

In the 3rd solid catalytic component of the present invention (C-3), every 1g solid-state carrier preferably carries attached, and 10 ^-4～5 * 10 ^-2Grammeatom, be preferably 5.0 * 10 ^-4～2 * 10 ^-2The transition metal atoms from component (a) of grammeatom, 10 ^-4～1.0 grammeatom, be preferably 5 * 10 ^-3～5 * 10 ^-1The aluminium atom from component (b) of grammeatom, 5 * 10 ^-5～5 * 10 ^-2The mole, be preferably 10 ^-5～10 ^-2The component (c) of mole.

In the 4th solid catalytic component of the present invention (C-4), every 1g solid-state carrier preferably carries attached, and 5 * 10 ^-5～5 * 10 ^-2Grammeatom, be preferably 10 ^-5～10 ^-2The transition metal atoms from component (a) of grammeatom, 10 ^-3～1.0 grammeatom, be preferably 5 * 10 ^-3～5 * 10 ^-1The aluminium atom from component (b) and component (d) of grammeatom, 5 * 10 ^-5～5 * 10 ^-2The mole, be preferably 10 ^-5～10 ^-2The component (c) of mole.

The the 3rd, the 4th olefin polymerization catalysis (C-3) of the present invention, (C-4) are in the presence of relevant solid catalytic component, by the pre-polymerization manufacturing of ethene and alpha-olefin, should by the Z-average molecular weight that utilizes gel permeation chromatography of pre-polymerization gained prepolymer more than 6,000,000 and the die swelling ratio be more than 1.4.

The alpha-olefin that uses in the pre-polymerization of the present invention can be enumerated propylene, 1-butylene, 1-amylene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecylene, tetradecene, cetene, 1-vaccenic acid, 1-eicosylene etc.Wherein, be preferably ethene especially or the combination of the alpha-olefin that uses during with the ethene mass polymerization.Polymerized form can be any of intermittent type, semi continuous, continous way, the method for also can choosing any one kind of them from slurry polymerization process, gaseous polymerization, solution polymerization process etc.

The polymer solvent that uses during as slurry polymerization or solution polymerization can be enumerated for example aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, 12 carbon alkane, kerosene; Alicyclic hydrocarbon such as pentamethylene, hexanaphthene, methylcyclopentane; Aromatic hydrocarbon such as benzene,toluene,xylene; Halohydrocarbon or its mixtures such as ethylene dichloride, chlorobenzene, methylene dichloride, chloroform.These solvents can use separately, also can mix use more than 2 kinds.Also can be with alkene itself as solvent.

During pre-polymerization, every 1g solid-state carrier, component (a) consumption are as transition metal, to be 10 ^-6～5 * 10 ^-4Grammeatom, be preferably 5 * 10 ^-6～2 * 10 ^-4Grammeatom.Component (b) consumption is that the aluminium (Al) of this component (b) is 10～1000, is preferably 50～500 with the atomic ratio (Al/ transition metal) of the transition metal of component (a).Relative 1 molar constituent (b), component (c) consumption are 0.01～5.0 mole, preferred 0.02～1.0 mole, more preferably 0.03～0.5 mole.And when using component (d), its consumption is that the aluminium atom (Al-d) of this component (d) is 0.01～5.0, is preferably 0.02～1.0 with the atomic ratio (Al-d/Al-b) of the aluminium atom (Al-b) of component (b).

Used the concentration of the prepolymerization system of the solid catalytic component that transistion metal compound (a) or each composition form, the ratio in 1 liter of transition metal/polymerization volume is generally 10 ^-6～2 * 10 ^-1Mol, more preferably 5 * 10 ^-5～10 ^-1Mol.

The pre-polymerization temperature is-20～90 ℃, is preferably 0～80 ℃, and the pre-polymerization time is 0.5～100 hour, is preferably 1～80 hour.Pre-polymerization pressure is normal pressure～10MPa, be preferably normal pressure～5MPa.

Pre-polymerization is used and the same alkene of the used alkene of aftermentioned polymerization usually, and being preferably with ethene is the alkene of main component.Prepolymerization catalyst can be by importing alkene in the olefin polymerization catalysis suspension liquid that uses the unreactive hydrocarbons solvent preparation, also can be after from suspension liquid, separating the olefin polymerization catalysis that generates in the unreactive hydrocarbons solvent, outstanding more turbid in unreactive hydrocarbons, in the gained suspension liquid, import alkene.

By pre-polymerization, every 1g solid-state carrier is expected to generate 0.01～1000g, preferred 0.1～800g, the more preferably olefin polymer of 0.2～500g (prepolymer).

Be to improve the molecular weight of pre-polymerization gained prepolymer, slurry concentration is low more good more, but for taking into account productivity, and the solid catalytic component of per 1 liter of solvent is 0.5～500g/ml, be preferably 1～400g/ml.Pre-polymerization and the preferable range of Z-average molecular weight of one of feature of prepolymer be more than 6,000,000, below 10,000 ten thousand, be preferably especially more than 7,000,000, below 100,000,000.Another feature of prepolymer---expression exists the scope of the die swelling ratio of long-chain branch to be preferably more than 1.4, below 5.0, is preferably especially more than 1.7, below 3.0.

Number-average molecular weight (Mn), weight-average molecular weight (Mw), Z-average molecular weight (Mz) are calculated by Waters model " Alliance GPC2000 " gel permeation chromatography (the high temperature granularity is got rid of chromatogram) gained molecular weight distribution curve.In addition, operational condition is as follows:

" using appts and condition "

Determinator: gel permeation chromatography alliance GPC2000 type (Waters company)

Analysis software: chromatography data system Empower (Waters company)

Post: TSKgel GMH ₆-HT * 2+TSKgel GMH ₆-HTL * 2

(internal diameter 7.5mm * long 30cm, eastern Cao company)

Mobile phase: orthodichlorobenzene [=ODCB] (with the pure medicine special grade chemical of light)

Detector: differential refractometer (device built-in)

Column temperature: 140 ℃

Flow velocity: 1.0mL/min

Injection rate: 500 μ L

Acquisition time interval: 1 second

Sample solution concentration: 0.15% (w/v)

Molecular weight calibration: from molecular weight 2,060 ten thousand molecular weight distribution and the various molecular-weight average of monodisperse polystyrene (eastern Cao company)/molecular weight 495, the general correct operation order according to the document record is converted into the PE molecular weight.[name of document: Z.Crubisic, P.Rempp, H.Benoit, J.Polym.Sci., B5, 753 (1967)]

By the die swelling of pre-polymerization gained prepolymer than obtaining by following method.

[preparation of working sample]

Be the fluctuation of the physics value that suppresses the gained prepolymerization catalyst, melting mixing as follows.In the gained prepolymerization catalyst, add 0.1 weight %Irganox1076 (Ciba Specialty Chemicals), 0.1 weight %Irgafos 168 (Ciba Specialty Chemicals) as heat-resisting stabilizing agent, use the smart mechanism of Japan to make made laboratory pulverizer, melting mixing is 5 minutes under 180 ℃ of resin temperatures, rotating speed 50rpm..Use the made pressure forming machine of refreshing rattan metal industry again, at 20 ℃ of cooling temperatures, 5 minutes cooling times, pressure 100kg/cm ²Condition under the cooling this fusion prepolymerization catalyst.

[die swelling is than the mensuration of (SR)]

Use the smart mechanism of Japan to make made capillary rheometer: Capillograph 1B (barrel diameter Φ 10mm) measures die swelling than (SR).Behind 6 minutes 10g working samples of 190 ℃ of following fusions of temperature,, extrude with the extruded velocity of 5.0mm/ branch with Fig. 6 and kapillary shown in Figure 7.In the place of the extruding collection of about 30mm of the thigh material in bullet tubule exit, room temperature was cooled off 1 minute.Appoint and get 5 point measurement thigh material diameters, get its mean value and be a strand material diameter.Removing strand quotient of material diameter with capillary diameter (4.5mm) is that die swelling is than (SR).

Olefine polymerizing process of the present invention is described then.Among the present invention, in the presence of above-mentioned catalyst for olefines polymerizing, carry out olefinic polymerization.Polymerization can be adopted any method of liquid polymerizations such as suspension polymerization or gaseous polymerization.

In the liquid polymerization, can use used unreactive hydrocarbons are identical when making with above-mentioned olefin polymerization catalysis hydrocarbon as solvent, in addition, alkene itself also can be used as solvent.

When using catalyst for olefines polymerizing of the present invention to carry out olefinic polymerization, aforesaid catalyzer preferable amount is, making the concentration from the transition metal atoms of polymerization system component (a) is 10 ^-6～2 * 10 ^-2Mol (polymerization volume), be preferably 5 * 10 ^-5～10 ^-2Mol (polymerization volume).At this moment, according to hope, also can use the organoaluminum oxo-compounds.It is 0～500 mole that the consumption of organoaluminum oxo-compounds is preferably per 1 transition metal atoms that restrains from component (a).

The olefinic polymerization temperature when adopting slurry polymerization process, for-50～100 ℃, be preferably 0～90 ℃, be 0～250 ℃ when implementing liquid polymerization, be preferably 20～200 ℃.And when implementing gaseous polymerization, polymerization temperature is 0～120 ℃, is preferably 20～100 ℃.The polymerization pressure condition is normal pressure～10MPa, is preferably normal pressure～5MPa that polyreaction can adopt intermittent type, semi continuous, any method of continous way.The polymerization more than 2 grades that also available reaction conditions is different.

Whether the molecular weight of gained olefin polymer can be existed hydrogen or be changed polymerization temperature by polymerization system is regulated.As utilizing olefin polymerization catalysis polymeric alkene of the present invention, can enumerate the alpha-olefin of ethene and carbonatoms 4～10, for example 1-butylene, 1-amylene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene; The cyclic olefin of carbonatoms 5～20, for example cyclopentenes, suberene, norbornylene, 5-methyl-2-norbornylene, tetracyclododecane, 2-methyl isophthalic acid, 4,5,8-dimethano--1,2,3,4,4a, 5,8,8a-octalin etc.Also can use vinylbenzene, vinyl cyclohexane, diolefine etc.

The bulk density of gained olefin polymer is 0.2～0.6g/cc, is preferably 0.3～0.55g/ml especially.And bulk density is that standard is tried to achieve with JIS K-6721.

(3) purposes of ethylene-based polymer

With ethylene-based polymer of the present invention and other thermoplastic resin fusion, can obtain formability excellence and physical strength thermoplastic resin excellent composition.The mix proportions of ethylene-based polymer of the present invention and other thermoplastic resin is 99.1/0.1～0.1/99.9.

As other thermoplastic resin, can use crystalline thermoplastic resins such as polyolefine, polymeric amide, polyester, polyacetal; The amorphism thermoplastic resin of polystyrene, acrylonitrile butadient styrene (ABS), polycarbonate, polydiphenyl ether, polyacrylic ester etc.Also preferably use polyvinyl chloride.

As said polyolefins, specifically can enumerate ethylene-based polymer, acrylic polymer, butylene based polymer, 4-methyl-1-pentene based polymer, 3-methyl-1-butene based polymer, hexene based polymer etc.Wherein, optimal ethylene based polymer, acrylic polymer, 4-methyl-1-pentene based polymer, when adopting ethylene-based polymer, both can be ethylene-based polymer of the present invention, also can be existing ethylene-based polymer, both can be that ethene contains the ethylenic copolymer of polar group, more preferably existing ethylene-based polymer.

Above-mentioned polyester specifically can be enumerated aromatic polyesters such as polyethylene terephthalate, PEN, polybutylene terephthalate; Polycaprolactone, poly-hydroxyl fourth (acid) ester etc.

Polymeric amide specifically can be enumerated fatty polyamides such as nylon-6, nylon-66, nylon-10, PA-12, nylon-46, the aromatic polyamide of being made by aromatic binary carboxylic acid and aliphatie diamine etc.

As above-mentioned polyacetal, specifically can enumerate polyoxymethylene (poly-hydroxyl methylene radical), metaldehyde, poly-propionic aldehyde, poly-butyraldehyde etc., wherein, preferred especially polyoxymethylene.

As above-mentioned polystyrene, both can be cinnamic single polymers, also can be the copolymer of vinylbenzene and vinyl cyanide, methyl methacrylate, alpha-methyl styrene.

As above-mentioned ABS, preferred use contain 20～35 moles of % by vinyl cyanide deutero-structural unit, contain the ABS of 20～30 moles of % by vinylbenzene deutero-structural unit by divinyl deutero-structural unit, 40～60 moles of %.

As above-mentioned polycarbonate, can enumerate by two (4-hydroxy phenyl) methane, 1 two (4-hydroxy phenyl) ethane, 2 of 1-, two (4-hydroxy phenyl) propane, 2 of 2-, the polycarbonate that two (4-hydroxy phenyl) butane etc. of 2-obtain.Wherein, especially preferably by 2, the polycarbonate that two (4-hydroxy phenyl) propane of 2-obtain.

As above-mentioned polydiphenyl ether, the preferred use gathered (2,6-dimethyl-1,4-phenyl ether).

As above-mentioned polyacrylic ester, preferably use polymethylmethacrylate, butyl polyacrylate.

Above-mentioned thermoplastic resin can use separately, also use more than 2 kinds capable of being combined.Preferred thermoplastic resin is a polyolefine, special optimal ethylene based polymer.

In the scope of the object of the invention, ethylene-based polymer of the present invention also can cooperate additives such as weather-proof stablizer, heat-resisting stabilizing agent, antistatic agent, slipproofing agent, anti, antifogging agent, lubricant, pigment, dyestuff, nucleator, softening agent, antiaging agent, hydrochloric acid absorbent, antioxidant as required except that above-mentioned thermoplastic resin.

By processing ethylene-based polymer of the present invention and the resin combination that contains ethylene-based polymer, can obtain the formed body of formability excellence and physical strength excellence, preferably obtain film.

Vinyl copolymer of the present invention can utilize common film forming, blow molding, injection molding, extrusion moulding processing.Film forming can enumerate that extruding layer is molded, T mould film forming, blow molding (air cooling, water cooling, multistage cooling, High-speed machining) etc.Even gained film individual layer also can use, then can also be endowed various functions but make multilayer.Can enumerate the coetrusion in above-mentioned each method of forming under this situation.Can enumerate in the lamination of utilizing the molded methods of laminating layer such as extruding layer is molded, drying layer platen press and the paper, blocking layer that are difficult to coextrusion (aluminium foil, vapor-deposited film, film etc.) aspect certain.Utilize the making by the high functional product of multilayer of coetrusion manufacturing of blow molding, injection molding, extrusion moulding can adopt the mode same with film forming.

By processing ethylene-based polymer of the present invention and containing the formed body that the thermoplastic resin composition of ethylene-based polymer gets, can enumerate injection-molded articles such as film, blowing infusion bag, blow molded bottle, extrusion moulding pipe, pipeline, easy-open lid, household items product, fiber, rotoforming and large-scale moulding product etc.

As getting film by the thermoplastic resin composition who processes ethylene-based polymer of the present invention and contain ethylene-based polymer, be suitable for various film for packaging such as the pack for liquids (standard bag etc.), specification bag of clear soup packing bag, the pack of liquid steamed dumping, liquid paper container, lamination yardage roll, special shape, heavy bag, fresh-keeping film, granulated sugar bag, oily thing packing bag, used for packing foods, infusion bag, agricultural materials etc.In addition, also can fit, as multilayer film with base materials such as nylon, polyester.

Below, specify the present invention according to embodiment, but the present invention is not subject to embodiment.

Embodiment

The preparation ☆ of ☆ solid ingredient (S1)～(S3)

The preparation of solid ingredient (S1)

Logical nitrogen, outstanding turbid 30g is at 250 ℃ of dry down silicon-dioxide (SiO of 10 hours in 460mL toluene ₂), be cooled to 0 ℃ then.With 1 hour dropping 140ml aluminium trimethide siloxanes (components b: toluene solution (being scaled the Al atom is 1.52mmol/mL) the Mitsui Chemicals goods) in this suspension liquid.At this moment, temperature remains on 0～2 ℃ in the system.0 ℃ of reaction 30 minutes, be warmed up to 95 ℃ with 1.5 hours more then, reaction is 4 hours under this temperature.Cool to 60 ℃ then, decant is removed supernatant liquor.With toluene such gained solid ingredient is carried out 3 times and clean, add toluene then, the toluene slurry of preparation solid ingredient (S1).Collecting part gained solid ingredient (S1), after the mensuration concentration, the result is slurry concentration 0.124g/mL, Al concentration 0.463mmol/mL.

The preparation of solid ingredient (S2)

Logical nitrogen, outstanding turbid 13g is at 250 ℃ of dry down silicon-dioxide (SiO of 10 hours in 100mL toluene ₂), be cooled to 0 ℃ then.With 1 hour (components b: toluene solution (being scaled the Al atom is 1.75mmol/mL) the Albemarle goods) of Dropwise 5 2.6ml aluminium trimethide siloxanes in this suspension liquid.At this moment, temperature remains on 0～2 ℃ in the system.0 ℃ of reaction 30 minutes, be warmed up to 95 ℃ with 1.5 hours more then, reaction is 4 hours under this temperature.Cool to 60 ℃ then, decant is removed supernatant liquor.With toluene such gained solid ingredient is carried out 4 times and clean, add toluene then, the toluene slurry of preparation solid ingredient (S2).Collecting part gained solid ingredient (S), after the mensuration concentration, the result is slurry concentration 0.1216g/mL, Al concentration 0.575mmol/mL.The collecting part supernatant liquor, measure concentration after, Al concentration 0.001mmol/mL as a result.

The preparation of solid ingredient (S3)

Remove after the aluminium trimethide siloxane reactions, the number of times that cleans the gained solid ingredient with toluene is outside 2 times, according to the method preparation same with solid ingredient (S2).Collecting part gained solid ingredient (S3) is measured concentration, and the result is slurry concentration 0.1665g/mL, Al concentration 0.697mmol/mL.The collecting part supernatant liquor, after the mensuration concentration, the result is Al concentration 0.0042mmol/mL.

The preparation ☆ of ☆ solid catalytic component (X-1)～(X-4)

The preparation of solid catalytic component (X-1)

In the 200mL of nitrogen replacement glass flask, add 50mL toluene, stir the toluene slurry (it is 2.0g that solid part converts) that adds the above-mentioned solid ingredient for preparing (S1) down.(component is toluene solution (the Zr atom is scaled 0.0011mmol/mL) a), and reaction is 2 hours under the room temperature to drip two (indenyl) zirconium dichlorides of 33.9mL vinyl then.Decant is removed supernatant liquor then, cleans 3 times with toluene, makes 100mL toluene slurry.Under room temperature, add the 135.8mg tetrafluoro again for Resorcinol (amount of component b), be warmed up to 40 ℃ of afterreactions 30 minutes.Decant is removed supernatant liquor then, cleans 3 times with toluene, makes 50mL toluene slurry.Removed aluminium trimethide siloxanes (components b) toluene solution (being scaled Al atom 0.15mmol/mL) of trimethyl aluminium again with underpressure distillation under 15 minutes Dropwise 5 0mL room temperatures, reacted again 30 minutes after being warmed up to 40 ℃.Decant is removed supernatant liquor then, cleans for 3 times with toluene 3 times, hexane, adds the 100mL decane, preparation solid catalytic component (X-1) decane slurry.Collecting part gained solid catalytic component (X-1) decane slurry, after the mensuration concentration, the result is Zr concentration 0.0263mg/mL, Al concentration 3.61mg/mL.

The preparation of solid catalytic component (X-2)

In the 200mL of nitrogen replacement glass flask, add 50mL toluene, stir add down according to the toluene slurry (it is 2.0g that solid part converts, and it is 9.9mmol that the Al atom converts) of the solid ingredient of solid ingredient (S1) same recipe (temperature of reaction reaction times) preparation.(component is toluene solution (the Zr atom is scaled 0.001525mmol/mL) a), and reaction is 2 hours under the room temperature to drip two (indenyl) zirconium dichlorides of 32.6mL vinyl then.Decant is removed supernatant liquor then, cleans 3 times with toluene, makes 100mL toluene slurry.Under room temperature, add the 363.1mg tetrafluoro again for Resorcinol (amount of component b), be warmed up to 40 ℃ of afterreactions 30 minutes.Decant is removed supernatant liquor then, cleans 3 times with toluene, makes 50mL toluene slurry.Use 10 minutes Dropwise 5 0mL aluminium trimethide siloxanes (Albemarle goods again; Components b) toluene solution (being scaled Al atom 0.199mmol/mL) is warmed up to 40 ℃ of afterreactions 30 minutes.Decant is removed supernatant liquor then, cleans for 3 times with toluene 3 times, decane, adds the 75mL decane, preparation solid catalytic component (X-2) decane slurry.Collecting part gained solid catalytic component (X-2) decane slurry, after the mensuration concentration, the result is Zr concentration 0.0258mg/mL, Al concentration 2.88mg/mL.

The preparation of solid catalytic component (X-3)

In the 400mL of nitrogen replacement glass flask, add 208mL toluene, stir solid ingredient (S2) the toluene slurry (it is 8.0g that solid part converts) that adds preparation as mentioned above down.(component is toluene solution (the Zr atom is scaled 0.0015mmol/mL) a), and reaction is 2 hours under the room temperature to drip two (indenyl) zirconium dichlorides of 126mL vinyl then.Decant is removed supernatant liquor then, cleans 1 time with toluene, makes 250mL toluene slurry.Under room temperature, add 150mL again and be dissolved with the solution of 1.377g tetrafluoro, be warmed up to 40 ℃ of afterreactions 30 minutes for Resorcinol (amount of component b).Decant is removed supernatant liquor then, cleans 1 time with toluene, makes 250mL toluene slurry.Again with 10 minutes dropping 150mL aluminium trimethide siloxanes (Albemarle goods; Components b) toluene solution (being scaled Al atom 0.253mmol/mL) is warmed up to 40 ℃ of afterreactions 30 minutes.Decant is removed supernatant liquor then, cleans for 3 times with toluene 3 times, decane, adds the 150mL decane, preparation solid catalytic component (X-3) decane slurry.Collecting part gained solid catalytic component (X-3) decane slurry, after the mensuration concentration, the result is Zr concentration 0.0892mg/mL, Al concentration 11.2mg/mL.

The preparation of solid catalytic component (X-4)

In the 400mL of nitrogen replacement glass flask, add 100mL toluene, stir solid ingredient (S3) the toluene slurry (it is 4.0g that solid part converts) that adds preparation as mentioned above down.(component is toluene solution (the Zr atom is scaled 0.0015mmol/mL) a), and reaction is 2 hours under the room temperature for two (indenyl) zirconium dichlorides of Dropwise 5 5.7mL vinyl then.Decant is removed supernatant liquor then, cleans 1 time with toluene, makes 100mL toluene slurry.Under room temperature, add 100mL again and be dissolved with the solution of 608.1mg tetrafluoro, be warmed up to 40 ℃ of afterreactions 30 minutes for Resorcinol (amount of component b).Decant is removed supernatant liquor then, cleans 1 time with toluene, makes 100mL toluene slurry.Again with 10 minutes dropping 100mL aluminium trimethide siloxanes (Albemarle goods; Components b) toluene solution (being scaled Al atom 0.167mmol/mL) is warmed up to 40 ℃ of afterreactions 30 minutes.Decant is removed supernatant liquor then, cleans for 3 times with toluene 3 times, decane, adds the 75mL decane, preparation solid catalytic component (X-4) decane slurry.Collecting part gained solid catalytic component (X-4) decane slurry, after the mensuration concentration, the result is Zr concentration 0.069mg/mL, Al concentration 9.23mg/mL.

The preparation ☆ of ☆ prepolymerization catalyst

The preparation of prepolymerization catalyst (Q-1)

In the SUS of 1 liter of the abundant metathetical volume of nitrogen system autoclave, add the refining heptane of 500mL, feed ethene, utilize ethene to make liquid phase and gas phase saturated.Under 20 ℃, ethene environment, add 0.375mmol triisopropylaluminiuand (components b), solid catalytic component (X-3) (the Zr atom is scaled 0.0254mmol) successively.Ethylene pressure is 0.78MPaG, carries out putting pressure after the polymerization in 8 hours at 20 ℃, with the ethene in the nitrogen replacement autoclave.Content is moved liquid to the abundant metathetical 1L of nitrogen container, clean 3 times, add decane, preparation pre-polymerization catalyst component (Q-1) decane slurry with decane.The decane slurry of collecting part gained pre-polymerization catalyst component (Q-1) is measured slurry concentration, pre-polymerization amount, slurry concentration=0.1693g/mL, and the pre-polymerization amount of every 1g solid catalytic component is the 31g/g-solid catalytic component.And after measuring than (SR) with die swelling through the gel permeation chromatography (GPC) of pre-polymerization resulting polymers, the Mw of prepolymer is 75.4 * 10 ⁴, Mz is 735.6 * 10 ⁴, SR is 1.8.

[embodiment 1]

Polymerization (secondary polymerization)

＜prime〉in the SUS of 1 liter of the abundant metathetical volume of nitrogen system autoclave, add the refining heptane of 500mL, feed ethene, utilize ethene to make liquid phase and gas phase saturated.Under 20 ℃, ethene environment, add 0.375mmol triisobutyl aluminium (B component), the solid catalytic component (X-1) (the Zr atom is scaled 0.004mmol) of preparation as mentioned above successively.Ethylene pressure is 0.78MPaG, carries out putting pressure after the polymerization in 30 minutes at 20 ℃, with the ethene in the nitrogen replacement autoclave.

＜back level〉use then hydrogen-ethene mixed gas (hydrogen concentration: 0.55vol%) displacement system, add 1-hexene 10mL again, be warmed up to 80 ℃, carry out polymerization in 20 minutes at 0.78MPaG.With 10 hours vacuum-drying resulting polymers, obtain 35.6g ethene 1-hexene copolymer.

For sample is measured in preparation, in the gained ethylene-based polymer, add Irganox1076 (Ciba Specialty Chemicals) as 0.1 weight % of heat-resisting stabilizing agent, 0.1 weight %Irgafos168 (Ciba Specialty Chemicals), use the smart mechanism of Japan to make made laboratory pulverizer, melting mixing is 5 minutes under 180 ℃ of resin temperatures, rotating speed 50rpm..Use the made pressure forming machine of refreshing rattan metal industry again, this molten polymer of cooling under the condition of 20 ℃ of cooling temperatures, 5 minutes cooling times, pressure 100kg/cm2.Table 1, table 2 are measured the result of rerum natura for using this sample.

[embodiment 2]

Polymerization (secondary polymerization)

Except that back level polymerization time among the embodiment 1 was become 14 minutes by 20 minutes, carry out polymerization similarly to Example 1.Vacuum-drying resulting polymers 10 hours obtains 23.3g ethene 1-hexene copolymer.

Use the gained ethylene-based polymer, measure sample according to method preparation similarly to Example 1.Table 1, table 2 expression use this sample to measure the result of rerum natura.

[embodiment 3]

Polymerization (secondary polymerization)

Except that back level polymerization time among the embodiment 1 was become 27 minutes by 20 minutes, carry out polymerization similarly to Example 1.Vacuum-drying resulting polymers 10 hours obtains 46.7g ethene 1-hexene copolymer.

[embodiment 4]

In the SUS of 1 liter of the abundant metathetical volume of nitrogen system autoclave, add the refining heptane of 500mL, feed ethene, utilize ethene to make liquid phase and gas phase saturated.(hydrogen concentration: 0.45vol%) displacement system adds 1-hexene 60mL, 0.375mmol triisobutyl aluminium (B component), 1.5g pre-polymerization catalyst component (Q-1) more successively to use hydrogen-ethene mixed gas then.Be warmed up to 70 ℃, under 0.78MPaG, carry out polymerization in 90 minutes.Vacuum-drying resulting polymers 10 hours obtains 61.4g ethene 1-hexene copolymer.

[embodiment 5]

In the SUS of 1 liter of the abundant metathetical volume of nitrogen system autoclave, add the refining heptane of 500mL, feed ethene, utilize ethene to make liquid phase and gas phase saturated.(hydrogen concentration: 0.55vol%) displacement system adds 1-hexene 7.5mL, 0.375mmol triisobutyl aluminium (B component), 1.44g pre-polymerization catalyst component (Q-1) more successively to use hydrogen-ethene mixed gas then.Be warmed up to 90 ℃, under 0.78MPaG, carry out polymerization in 90 minutes.Vacuum-drying resulting polymers 10 hours obtains 15.6g ethene 1-hexene copolymer.

[embodiment 6]

In the SUS of 1 liter of the abundant metathetical volume of nitrogen system autoclave, add the refining heptane of 500mL, feed ethene, utilize ethene to make liquid phase and gas phase saturated.(hydrogen concentration: 0.83vol%) displacement system adds 1-hexene 15mL, 0.375mmol triisobutyl aluminium (B component), 1.5g pre-polymerization catalyst component (Q-1) then successively to use hydrogen-ethene mixed gas then.Be warmed up to 80 ℃, under 0.78MPaG, carry out polymerization in 270 minutes.Vacuum-drying resulting polymers 10 hours obtains 50.8g ethene 1-hexene copolymer.

[embodiment 7]

Polymerization (secondary polymerization)

＜prime〉in the SUS of 1 liter of the abundant metathetical volume of nitrogen system autoclave, add the refining heptane of 500mL, feed ethene, utilize ethene to make liquid phase and gas phase saturated.Under 20 ℃, ethene environment, add 0.375mmol triisobutyl aluminium (B component), the solid catalytic component (X-2) (the Zr atom is scaled 0.001mmol) of preparation as mentioned above successively.Ethylene pressure is 0.78MPaG, carries out putting pressure after the polymerization in 6 hours at 20 ℃, with the ethene in the nitrogen replacement autoclave.

＜back level〉use then hydrogen-ethene mixed gas (hydrogen concentration: 0.38vol%) displacement system, add 1-hexene 30mL again, be warmed up to 70 ℃, carry out polymerization in 160 minutes at 0.78MPaG.Vacuum-drying resulting polymers 10 hours obtains 44.8g ethene 1-hexene copolymer.

[embodiment 8]

In the SUS of 1 liter of the abundant metathetical volume of nitrogen system autoclave, add the refining heptane of 500mL, feed ethene, utilize ethene to make liquid phase and gas phase saturated.(hydrogen concentration: 0.54vol%) displacement system adds 1-hexene 15mL, 0.375mmol triisobutyl aluminium (B component), 1.5g pre-polymerization catalyst component (Q-1) then successively to use hydrogen-ethene mixed gas then.Be warmed up to 80 ℃, under 0.78MPaG, carry out polymerization in 110 minutes.Vacuum-drying resulting polymers 10 hours obtains 37.5g ethene 1-hexene copolymer.

[embodiment 9]

Polymerization (secondary polymerization)

＜prime〉in the SUS of 1 liter of the abundant metathetical volume of nitrogen system autoclave, add the refining heptane of 500mL, feed ethene, utilize ethene to make liquid phase and gas phase saturated.Under 20 ℃, ethene environment, add 0.375mmol triisobutyl aluminium (B component), the solid catalytic component (X-4) (the Zr atom is scaled 0.002mmol) of preparation as mentioned above successively.Ethylene pressure is 0.78MPaG, carries out putting pressure after the polymerization in 120 minutes at 20 ℃, with the ethene in the nitrogen replacement autoclave.

＜back level〉use then hydrogen-ethene mixed gas (hydrogen concentration: 0.83vol%) displacement system, add 1-hexene 15mL again, be warmed up to 80 ℃, carry out polymerization in 40 minutes at 0.78MPaG.Vacuum-drying resulting polymers 10 hours obtains 43.7g ethene 1-hexene copolymer.

[embodiment 10]

Polymerization (secondary polymerization)

＜prime〉in the SUS of 1 liter of the abundant metathetical volume of nitrogen system autoclave, add the refining heptane of 500mL, feed ethene, utilize ethene to make liquid phase and gas phase saturated.Under 20 ℃, ethene environment, add 1-hexene 20mL, 0.375mmol triisobutyl aluminium (B component), the solid catalytic component (X-2) (the Zr atom is scaled 0.002mmol) of preparation as mentioned above successively.Be warmed up to 80 ℃, carrying out putting pressure after the polymerization in 15 minutes under the ethylene pressure 0.78MPaG, with the ethene in the nitrogen replacement autoclave.

＜back level〉use then hydrogen-ethene mixed gas (hydrogen concentration: 1.25vol%) displacement system, add 1-hexene 10mL again, be warmed up to 80 ℃, carry out polymerization in 180 minutes at 0.78MPaG.Vacuum-drying resulting polymers 10 hours obtains 41.6g ethene 1-hexene copolymer.

[reference examples 1]

The preparation of solid ingredient (S)

Logical nitrogen, outstanding turbid 179g is at 250 ℃ of dry down silicon-dioxide (SiO of 10 hours in 2.75L toluene ₂) after, be cooled to 0 ℃.With 1 hour dropping 810ml aluminium trimethide siloxanes (components b) toluene solution (being scaled the Al atom is 1.52mmol/mL) in this suspension liquid.At this moment, temperature remains on 0～2 ℃ in the system.0 ℃ of reaction 30 minutes, be warmed up to 95 ℃ with 1.5 hours more then, reaction is 4 hours under this temperature.Cool to 60 ℃ then, decant is removed supernatant liquor.With toluene such gained solid ingredient is cleaned 3 times, add toluene then, making total amount is 1225mL, the toluene slurry of preparation solid ingredient (S).Collecting part gained solid ingredient (S), after the mensuration concentration, the result is slurry concentration 0.203g/mL, Al concentration 0.985mmol/mL.Measure composition in drying nest solid ingredient (S) back, the result is the Al atom that every 1g solid ingredient contains 131mg.

The preparation of solid catalytic component (X)

Then under 75 ℃, under agitation, Dropwise 5 .00 rises two (indenyl) zirconium dichlorides of vinyl (component is toluene solution (the Zr atom is scaled 1.21mmol/L) a) in solid ingredient (S) the toluene slurry of preparing as mentioned above with 30 fens clockwise, be warmed up to 80 ℃ again, under this temperature, reacted 2 hours then.Remove supernatant liquor then, clean 2 times with hexane, add hexane, making total amount is 3.32L, the hexane slurry of preparation solid catalytic component (X).Drying nest gained solid catalytic component (X) is measured it and is formed, and the result is the Zr atom that every 1g solid catalytic component contains 2.1mg.

The preparation of prepolymerization catalyst (X ')

With as mentioned above and the hexane slurry of solid catalytic component (X) be cooled to 10 ℃ after, under normal pressure, in system, supply with ethene continuously.During this time, temperature remains on 10～15 ℃ in the system.The 1-hexene that adds 133ml triisobutyl aluminium (B component) decane solution (the Al atom is scaled 1.0mmol/mL) and 16.6ml then, the beginning pre-polymerization.After 15 minutes, temperature rises to 35 ℃ in the system, keeps the interior temperature of system at 32～35 ℃ then.The beginning pre-polymerization adds the 1-hexene of 5.5ml after 70 minutes again.Then, after 160 minutes with 220 minutes after the same 1-hexene that adds 5.5ml.

Then, after 275 minutes, after in the nitrogen replacement system, stop pre-polymerization in the beginning pre-polymerization.Remove supernatant liquor again, clean 2 times, the prepolymerization catalyst (X ') of 3g polymkeric substance that obtained every 1g solid catalytic component (X) pre-polymerization with hexane.

Polymerization

Use continuous fluidized bed gas phase polymerization apparatus, at stagnation pressure 20kg/cm ²Make ethene and 1-hervene copolymer under the condition of-G, 80 ℃ of polymerization temperatures, gas line speed 0.8m/sec..The dry prepolymerization catalyst (X ') of preparation is as mentioned above supplied with continuously with the ratio of 10g/hr, between polymerization period, for keeping certain gas composition, supplies with (the gas composition: 1-hexene/ethene=1.1 * 10 of ethene, 1-hexene, hydrogen and nitrogen continuously ^-2, ethylene concentration=62%).Gained ethene 1-hexene copolymer yield is 6.1kg/hr.

[reference examples 2]

(trade(brand)name: pellet goods EVOLUE SP1520) serve as to measure sample to the vapour phase polymerization legal system ethene 1-hexene copolymer of selling with Mitsui Chemicals, Inc, carry out evaluation of physical property.Table 1, table 2 ecbatic.

[reference examples 3]

(trade(brand)name: pellet goods Affinity PF1140) serve as to measure sample to the gas phase solution polymerization legal system ethene 1-octene copolymer of selling with Dow Chemical Company, carry out evaluation of physical property.Table 1, table 2 ecbatic.

Reference examples 1, reference examples 2 do not meet and LNR, MT/ η with reference examples 3 ^*Relevant technical solution of the

present invention

1 and 2 described conditions.Therefore, contriver's deduction is compared with embodiment 1～9, and the constriction during its moulding is big.

[reference examples 4]

High-pressure free radical polymerization legal system polyethylene (trade(brand)name: MIRASON M11), serve as to measure sample to carry out evaluation of physical property with Mitsui Chemicals, Inc's sale with the pellet goods.Table 1, table 2 ecbatic.

The breaking point coiling speed (DS) of reference examples 4 does not meet technical solution of the present invention 1 described condition.Therefore, its high speed film forming poor in processability is compared in contriver's deduction with embodiment 1, embodiment 2, embodiment 4, embodiment 5 and embodiment 7.And methyl branch number and ethyl branch are counted sum (A+B) and are not met technical solution of the present invention 1 described condition.Therefore, its bad mechanical strength is compared in contriver's deduction with embodiment 1～9.

[reference examples 5]

(trade(brand)name: MarlexHHM5502) the pellet goods serve as to measure sample to carry out evaluation of physical property to the ethene 1-hexene copolymer of selling with Mitsui Chemicals, Inc.Table 1, table 2 ecbatic.

Reference examples 5 does not meet and LNR, MT/ η ^*Relevant technical solution of the

present invention

1 and 2 described conditions.Therefore, contriver's deduction is compared with embodiment 1～9, and the constriction during its moulding is big.In addition, its per 1 molecule chain end ethene radix (V) does not meet technical scheme 3 described conditions.Therefore, the poor heat stability during its forming process is compared in contriver's deduction with embodiment 1～9.

[reference examples 6]

(trade(brand)name: Toughsen TUF-2060) the pellet goods serve as that the mensuration sample carries out evaluation of physical property to the ethene 1-hexene copolymer of selling with Japanese Unica company.The results are shown in table 1, table 2.

[reference examples 7]

(trade(brand)name: Toughsen TUF-2070) the pellet goods serve as that the mensuration sample carries out evaluation of physical property to the ethene 1-hexene copolymer of selling with Japanese Unica company.The results are shown in table 1, table 2.

[reference examples 8]

(trade(brand)name: Sumikasen-α GZ701) the pellet goods serve as to measure sample to carry out evaluation of physical property to the ethene 1-hexene copolymer of selling with Sumitomo Chemical Co. Ltd..The results are shown in table 1, table 2.

Reference examples 6～8 does not meet and LNR, MT/ η ^*Relevant technical solution of the

present invention

1 and 2 described conditions.Therefore, contriver's deduction is compared with embodiment 1～9, and the constriction during its moulding is big.And the relation of its fusing point maximum peak (Tm) and density (d) does not meet technical solution of the present invention 3 described conditions.Therefore, contriver's deduction is compared with embodiment 1～9, and its low temperature seal is poor.

Table 1

^*1: detect below the lower limit (0.02/1000C)

^*2:12 * MFR ^0.577Value

^*3:165 * MFR ^0.577Value

Table 2

^*4:0.315 * d-200 value

^*5:0.315 * d-170 value

Industry is utilized possibility

Ethene of the present invention is polymer and contains the thermoplastic resin composition that ethene is polymer Be applicable to the formed body of good moldability and mechanical strength excellence, preferably be applicable to film.

Claims

1. ethylene-based polymer, it is the multipolymer of the alpha-olefin of ethene and carbonatoms 4～10, it is characterized in that, satisfies following condition [k1]～[k3] simultaneously:

Melt flow rate (MFR) MFR scope when [k1] 190 ℃ during the 2.16kg load is 1.0～50g/10 minute,

[k2] be defined as when using small-sized slit die that working sample is shaped to film the constriction amount with according to the LNR scope of the ratio of the constriction amount during as film is 0.6～1.4 with the polyethylene formation of the trade(brand)name MIRASON M11 of Mitsui Chemicals system with quadrat method,

[k3] is defined as in the time of 160 ℃ with the 100m/ branch ²The DS and the melt flow rate (MFR) MFR of coiling speed of the coiling speed of the scope of batching acceleration, dividing with the 15～400m/ breaking point when batching satisfy following relational expression (Eq-1):

12×MFR ^0.577≤DS≤165×MFR ^0.577......(Eq-1)

The unit of described DS is the m/ branch.

2. ethylene-based polymer according to claim 1 is characterized in that, satisfies following condition [m1]～[m3] simultaneously:

[m1] density d is at 890～950kg/m ³Scope in,

Fusion tension force MT and 200 ℃, the shear viscosity η of circular frequency 1.0rad/ during second when [m2] 190 ℃ ^*Than MT/ η ^*2.00 * 10 ^-4～9.00 * 10 ^-4Scope,

[m3] by ¹³The methyl branch of per 1000 carbon atoms that C-NMR measures count A (/ 1000C) with ethyl branch count B (/ 1000C) sum (A+B) (/ 1000C) below 1.4,

The unit of described fusion tension force MT is g, described shear viscosity η ^*Unit for the pool, described MT/ η ^*Unit be g/ pool.

3. ethylene-based polymer as claimed in claim 1 or 2 is characterized in that, satisfies any more than 1 of following condition [n1]～[n3]:

The Z-average molecular weight Mz that [n1] measures with GPC and the ratio Mz/Mw of weight-average molecular weight Mw be more than 10,

The terminal ethylenyl groups of per 1000 carbon atoms that [n2] measured by IR count v (the per 1 molecule chain end ethene radix V that/number-average molecular weight Mn that 1000C) measures with GPC calculates below 0.47/1 molecular chain,

Fusing point maximum peak Tm among [n3] DSC and density d satisfy following relational expression (Eq-2):

0.315×d-200≤Tm≤0.315×d-170......(Eq-2)

The unit of described Tm is ℃.

4. ethylene-based polymer according to claim 1 is characterized in that, use by solid-state carrier and (A) the olefin polymerization catalysis polymerization that forms of solid-state transition metal catalyst component and obtaining,

Described (A) solid-state transition metal catalyst component contains the periodic table of elements the 4th group transition metal compound, (b) organoaluminum oxo-compounds of the dentate that has cyclopentadienyi skeleton more than 1 and (c) by (a) and contacts with the multi-functional Organohalogen compounds of general formula (1) expression and obtain, wherein, in formula (I)

(Q ¹) _o-R-(Q ²) _p......(I)

R is the base that contains (o+p) valency of 1 above halogen atom, and o, p are the positive integers of satisfied (o+p) 〉=2, Q ¹With Q ²Expression-OH ,-NH ₂Or-NLH, in-NLH, L is selected from C ₁～C ₂₀Alkyl, C ₁～C ₂₀Halogen-containing alkyl, contain silica-based, contain the oxygen base, contain sulfenyl, any base of nitrogenous base or phosphorous-containigroups groups, and L and R, N and R, N and N can be incorporated into ring.

5. ethylene-based polymer according to claim 1 is characterized in that, use by solid-state carrier and (A) the olefin polymerization catalysis polymerization that forms of solid-state transition metal catalyst component and obtaining,

Described (A) solid-state transition metal catalyst component contains the dentate that has cyclopentadienyi skeleton more than 1 by (a) the periodic table of elements the 4th group transition metal compound, (b) organoaluminum oxo-compounds, (c) contacts with (d) organo-aluminium compound with the multi-functional Organohalogen compounds of general formula (1) expression and obtains, wherein, in formula (I)

(Q ¹) _o-R-(Q ²) _p......(I)

6. ethylene-based polymer according to claim 1 is characterized in that, use by solid-state carrier, (A) solid-state transition metal catalyst component and (B) the olefin polymerization catalysis polymerization that forms of organo-aluminium compound and obtaining,

(Q ¹) _o-R-(Q ²) _p......(I)

7. ethylene-based polymer according to claim 1 is characterized in that, use by solid-state carrier, (A) solid-state transition metal catalyst component and (B) the olefin polymerization catalysis polymerization that forms of organo-aluminium compound and obtaining,

(Q ¹) _o-R-(Q ²) _p......(I)

8. as ethylene-based polymer as described in each in the claim 4～7, it is characterized in that,

Described ethylene-based polymer obtains by using polymerization catalyst,

Described catalyzer is formed by the prepolymer after ethene or the ethylene/alpha-olefin pre-polymerization by described solid-state transition metal catalyst component,

In the described prepolymer, with respect to the solid-state transition metal catalyst component of every 1g to contain Z-average molecular weight that 0.01～1000g obtains by GPC be more than 6000000 and die swelling than being composition more than 1.4.

9. as ethylene-based polymer as described in each in the claim 4～7, it is characterized in that,

Described ethylene-based polymer obtains by using polymerization catalyst,

Described catalyzer by described solid-state transition metal catalyst component by the prepolymer after ethene or the ethylene/alpha-olefin pre-polymerization and (B) organo-aluminium compound form,

10. as ethylene-based polymer as described in each in the claim 4～7, it is characterized in that periodictable the 4th group transition metal compound (a) that contains the dentate that has cyclopentadienyi skeleton more than 1 is with general formula (II), (III) or (IV) compound of expression

Formula (II) with (III) in, R ¹～R ⁶Independent respectively expression is selected from hydrogen atom, halogen atom, C ₁～C ₂₀Alkyl, C ₃～C ₂₀Cycloalkyl, C ₂～C ₂₀Thiazolinyl, C ₆～C ₂₀Aryl, C ₇～C ₂₀The base of aralkyl, R ¹～R ⁶Contain or do not contain silicon, halogen or germanium atom;

R ³With R ⁴, R ⁴With R ⁵, R ⁵With R ⁶In one of them group can interosculate into ring;

R ⁷Being the divalent base that combines 2 dentates, is C ₁～C ₂₀Alkyl, C ₁～C ₂₀Contain brine alkyl, contain the base of silica-based or germanic or tin, 2 substituting groups on same carbon, silicon, germanium, the tin atom can interosculate into ring;

t ¹With t ²Independent respectively expression is selected from hydrogen atom, halogen atom, C ₁～C ₂₀Alkyl, C ₁～C ₂₀Contain brine alkyl, contain silica-based, contain the oxygen base, contain sulfenyl, the base of nitrogenous base and phosphorous-containigroups groups;

M is the transition metal that is selected from titanium, zirconium, hafnium,

In the formula (IV), R ⁷, t ¹, t ², the definition of M and formula (II) is identical, R ⁸～R ¹⁹Independent respectively expression is selected from hydrogen atom, halogen atom, C ₁～C ₂₀Alkyl, C ₃～C ₂₀Cycloalkyl, C ₂～C ₂₀Thiazolinyl, C ₆～C ₂₀Aryl or C ₇～C ₂₀The base of aralkyl, R ⁸～R ¹⁹Contain or do not contain silicon, halogen or germanium atom, be abutted to R ⁸～R ¹⁹Substituting group can interosculate into ring.

11. contain the thermoplastic resin composition of the described ethylene-based polymer of claim 1.

12. the formed body that obtains by the described ethylene-based polymer of claim 1.

13. the formed body that obtains by the described thermoplastic resin composition of claim 11.

14., it is characterized in that described formed body is a film as formed body as described in claim 12 or 13.