CN101341176B - Ethylene polymer, catalyst for production of ethylene polymer, and process for production of ethylene polymer - Google Patents

Ethylene polymer, catalyst for production of ethylene polymer, and process for production of ethylene polymer Download PDF

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CN101341176B
CN101341176B CN2006800478765A CN200680047876A CN101341176B CN 101341176 B CN101341176 B CN 101341176B CN 2006800478765 A CN2006800478765 A CN 2006800478765A CN 200680047876 A CN200680047876 A CN 200680047876A CN 101341176 B CN101341176 B CN 101341176B
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polyvinyls
dimethyl
butyl
fluorenyl
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CN101341176A (en
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山田悟
稻富敬
若林保武
阿部成彦
佐藤守彦
田靡正雄
羽村敏
池田隆治
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Tosoh Corp
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Tosoh Corp
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Abstract

An object of the present invention relates to provide an ethylene polymer having excellent mechanical strength and excellent molding process ability in a wide molding processing temperature range. The invention relates to use an ethylene polymer comprising a repeating unit derived from ethylene, or a repeating unit derived from ethylene and a repeating unit derived from a C3-8alpha-olefin, the ethylene polymer being satisfied with the following (A) to (F). (A) Density (d (kg/m<3>)) is from 910 to 970, (B) MFR (g/10 min)) is from 0.01 to 50, (C) terminal vinyl number is 0.2 or less per 1,000 carbon atoms, (D) melt strength (MS 160 (mN)) measured at 160 DEG C and MFR are satisfied with MS 160 > 90-130 * log(MFR), (E) melt strength (MS 190 (mN) ) measured at 190 DEG C and MS 160 are satisfied with MS 160 /MS 190 < 1.8, and (F) fluidized activation energy (Ea (kJ/mol) ) and d are satisfied with 127-0.107d < Ea < 88-0.060d.

Description

Polyvinyls, the method that is used to prepare the catalyzer of polyvinyls and prepares polyvinyls
Technical field
The present invention relates to a kind of polyvinyls, be used to the method for preparing the catalyzer of polyvinyls and prepare polyvinyls with high fondant-strength.More specifically, the present invention relates to a kind ofly have excellent heat stability, under wide forming process temperature range, have the good forming process and the polyvinyls of high fondant-strength, relate to a kind of be used to the prepare catalyzer of the polyvinyls that has superior mechanical intensity and under wide forming process temperature range, have good forming process and the production method of using it.
Background technology
The new LDPE (film grade) of being produced by the high-pressure free radical method (LDPE) is a kind of polyvinyls with high fondant-strength (MS).But because mobile activation energy (Ea) is big, the temperature dependency of melt viscosity is big, and therefore, polymkeric substance only has high MS in specific forming process temperature range, and it must select a kind of treater that is suitable for polymkeric substance to be processed in moulding moulded.
In addition, the polyvinyls that uses Z-type catalyst or metalloscene catalyst to make has little Ea, but MS is low, therefore, has problems on moulding processability.
Polyvinyls as moulding processability with improvement, propose, for example, (a) under specific polymerizing condition, the ethene-alpha-olefin copolymer (for example seeing patent document 1) that uses specific metalloscene catalyst to make to have long-chain branch, (b) use specific metalloscene catalyst to make ethene-alpha-olefin copolymer (for example, seeing patent document 2) with 60kJ/ mole or higher Ea.But these ethene copolymers have the temperature dependency of big Ea and big melt viscosity, are similar to LDPE.Therefore, need be strict controlled in temperature in the forming process.
Has the polyvinyls of low Ea and high MS owing in wide forming process temperature range, have stable processing characteristics, so preferred.This polymkeric substance comprises the polyvinyls that uses Cr class Catalyst Production, but in present inventor's research, it has problems aspect thermally-stabilised, such as, flavescence when melt-processed, this is because the amount of terminal ethylenyl groups in polyvinyls is that per 1000 carbon atoms are 0.3 or bigger.Therefore expect a kind of have unsaturated link(age) and good thermostability such as a small amount of terminal ethylenyl groups, have low Ea in addition and the polyvinyls of good moulding processability is arranged in wide forming process temperature range.
In addition, use the polyvinyls of Cr class Catalyst Production to have the wide problem of molecular weight distribution, the result, the physical strength of moulding product is low.Wishing has a kind of catalyzer, and it is used to produce and has good mechanical strength and have the polyvinyls of good moulding processability under wide forming process condition, and the production method of using this catalyzer.
No. 5272236 specification sheetss of patent document 1:US patent
Patent document 2:JP-A-2004-292772
Summary of the invention
The problem to be solved in the present invention
The present invention has solved above-mentioned the problems of the prior art, and provides a kind of terminal ethylenyl groups number few and have good thermostability, and has the polyvinyls of low Ea and high MS.The present invention also provides a kind of and is used to produce the catalyzer that has superior mechanical intensity and have good moulding processability under wide molding technological condition, and the production method of using this catalyzer.
The method of dealing with problems
Through above-mentioned purpose is carried out extensive and careful research, the present invention has drawn result of study.Particularly, the present invention relates to a kind ofly comprise by the repeating unit of ethylene derivative or comprise by the repeating unit of ethylene derivative with by the polyvinyls of alpha-olefin derived repeating unit the condition that polyvinyls satisfies following (A)-(F) with 3-8 carbon atom:
(A) density (d (kg/m 3)) be 910～970,
(B) under load 2.16kg, be 0.01-50 in the solution flow velocity (MFR (g/10 minute)) of 190 ℃ of measurements,
(C) the terminal ethylenyl groups number is that per 1000 carbon atoms are 0.2 or still less,
(D) at the melt strength (MS of 160 ℃ of measurements 160(mN)) and MFR satisfy following formula (1):
MS 160＞90-130×log(MFR) (1)
(E) at the melt strength (MS of 190 ℃ of measurements 190And MS (mN)) 160Satisfy following formula (2):
MS 160/MS 190＜1.8 (2)
(F) flow-activation energy (Ea (kJ/mol)) and d satisfy following formula (3):
127-0.107d＜Ea＜88-0.060d (3)
In addition, the present invention relates to the transistion metal compound (composition (a)) that a kind of use has ad hoc structure and the transistion metal compound (composition (b)) with ad hoc structure is used for the catalyzer that polyvinyls is produced as Metallocenic compound, and a kind of method of using this Catalyst Production polyvinyls.
The invention effect
The polyvinyls that makes by the present invention has good thermostability and have good forming process in wide forming process temperature range.Moreover, be used for the catalyzer of polyvinyls production and polyvinyls that the inventive method is produced has superior mechanical intensity and has good moulding processability in wide forming process temperature range by use.
Embodiment
Polyvinyls of the present invention is to comprise by the polyvinyls of the repeating unit of ethylene derivative or comprise by the repeating unit of ethylene derivative with by the ethene-alpha-olefin copolymer of the alpha-olefin derived repeating unit of 3-8 carbon atom.
By the repeating unit of ethylene derivative be meant by monomer ethylene deutero-unit and be contained in polyvinyls or ethene-alpha-olefin copolymer in.Be meant by as the alpha-olefin derived unit of a monomeric 3-8 carbon atom and be contained in the ethene-alpha-olefin copolymer by alpha-olefin derived repeating unit with 3-8 carbon atom.Example with alpha-olefin of 3-8 carbon atom comprises propylene, 1-butylene, 1-hexene, 1-octene, 4-methyl-1-pentene and 3-methyl-1-butene.These have at least two kinds in the alpha-olefin of 3-8 carbon atom can use together.
(A) density (d (kg/m of polyvinyls of the present invention 3)) be according to JIS K6760 (1995) and the value that adopts the density gradient tube method to measure, and be 910 to 970kg/m 3, preferred 910～940kg/m 3If density is lower than 910, then the melt temperature of product is low, can only obtain the thermotolerance of difference.If density surpasses 970, then product has good thermotolerance and rigidity, but shock strength worsens.
(C) terminal ethylenyl groups number of polyvinyls of the present invention is the hot pressing polyvinyls by using Fourier transform infrared spectrometer (FT-IR), then with ice-cooled it, make film, at 4000-400cm -1Measure film in the scope and use following formula to calculate:
The terminal ethylenyl groups number of per 1000 carbon atoms (individual/10000)=a * A/L/d
Wherein, a is the absorbancy coefficient, and A is the 909cm that belongs to terminal ethylenyl groups -1Absorbancy, L is a film thickness, and d is a density.A passes through by the terminal ethylenyl groups number that uses wherein per 1000 carbon atoms 1H-NMR measures the made typical curve of determining of sample and obtains. 1The H-NMR measurement is to use the product G SX400 of JEOL company, is to carry out under 130 ℃ in the mixed solvent of deuterate benzene and orthodichlorobenzene.The terminal ethylenyl groups number of per 1000 carbon atoms calculates by the integration ratio at peak that belongs to methylene radical and the peak that belongs to terminal ethylenyl groups.Each peak uses tetramethylsilane as standard (0ppm), and wherein chemical shift is that the peak of 1.3ppm belongs to methylene radical, and chemical shift to be the peak of 4.8-5.0ppm belong to terminal ethylenyl groups.The terminal ethylenyl groups number (C) of per 1000 carbon atoms of polyvinyls of the present invention is 0.2 or still less, and is preferably 0.1 or still less.When the terminal ethylenyl groups number is 0.2 above per 1000 carbon atoms, when forming process, can cause the problem of the problem, particularly flavescence of thermal degradation when.
Melt strength (the MS of polyvinyls of the present invention 160(mN)) be to use that to have length be 8mm, diameter is that the mould of 2.095mm is that 90 °, shearing rate are 10.8s in fluid inlet angle -1And stretch ratio is under 47 the condition, the value of measuring under 160 ℃ measurement temperature.If the value that maximal draw ratio records less than 47 then with the maximal draw ratio before breaking is as MS 160By making temperature schedule 190 ℃ and the melt strength measured with the same manner as MS 190(mN).
(B) melt flow of polyvinyls of the present invention (MFR (g/10 minute)) be under the 2.16kg load in 190 ℃ of values that record, it is 0.01～50.If MFR is lower than 0.01, then the charge capacity of forcing machine increases when forming process, causes turnout to reduce, and this is not preferred.Moreover if MFR surpasses 50, melt strength reduces, and the intensity of product reduces, and this is not preferred.
(D) MS of polyvinyls of the present invention 160Satisfy following formula (1) with the relation of MFR
MS 160＞90-130×log(MFR) (1)
And preferably satisfy following formula (4)
MS 160＞110-130×log(MFR) (4)
If MS 160Then on forming process, can cause problem at (90-130 * log (MFR)) or lower scope.
(E) MS of polyvinyls of the present invention 190And MS 160Relation satisfy following formula (2):
MS 160/MS 190＜1.8 (2)
And preferably satisfy following formula (5):
MS 160/MS 190＜1.7 (5)
If MS 160/ MS 190Be that then melt strength changes with temperature significantly 1.8 or higher scope.As a result, essential strict control mold temperature causes narrow plastic scope.
(F) flow-activation energy of polyvinyls of the present invention (Ea (kJ/mol)) is the value that obtains by the shift factor substitution Arrhenius formula that the power viscoelasticity measurement under 160～230 ℃ is obtained, and satisfies following formula (3)
127-0.107d＜Ea＜88-0.060d (3)
And preferably satisfy following formula (6)
127-0.107d＜Ea＜87-0.060d (6)
If Ea is when (127-0.107d) is following, then can have problems on the property in processing.On the other hand, when Ea when (88-0.060d) is above, then the temperature dependency of melt viscosity increases.As a result, must strictly control the moulding processing temperature, cause narrow plastic scope.
The weight-average molecular weight (Mw) that (G) of polyvinyls of the present invention records by gel permeation chromatography (GPC) and the ratio (Mw/Mn) of number-average molecular weight (Mn) are preferably 2～6, and more preferably 2～5.When the descend physical strength of product then of Mw/Mn is improved.
Satisfy above-mentioned requirements (A) to (F) and the polyvinyls of the present invention of preferably also meet the demands (G) can be randomly working condition by following embodiment, or a small amount of variation of condition element prepares.Below the specific examples that condition element changes is described in.Optional polyvinyls can be by the prerequisite preparation of the relevant catalyst component of control, the structure of described condition such as used composition (a) and composition (b), composition (b) is with respect to the amount of composition (a) and the kind of used co-catalyst component, and polymerizing condition such as, polymerization temperature, ethylene partial pressure, the amount of the amount of the hydrogen equimolecular quantity conditioning agent of coexistence and adding comonomer.In addition, can be by enlarging the scope of physical property with multistage aggregate combinations.
More specifically, can reduce the terminal ethylenyl groups number by amount of comonomers that for example reduces ethylene partial pressure, minimizing adding or the structure that changes composition (a).In addition, melt strength can change the structure of composition (a) by for example, increases the terminal ethylenyl groups number, change the structure of composition (b), reduce ethylene partial pressure, increase long-chain side chain number, increase long-chain and prop up chain length, change the amount of composition (b), or increase Mw/Mn and strengthen with respect to composition (a).Flow-activation energy (Ea) can pass through structure, the terminal ethylenyl groups number of composition (a), the structure of composition (b), ethylene partial pressure, and long-chain side chain number, long-chain props up chain length, or composition (b) is with respect to the amount of composition (a) and control.
Polyvinyls of the present invention can be made by the following method: polymerising ethylene or copolymerization of ethylene make with the α-alkene of 3-8 carbon atom is arranged in the presence of metalloscene catalyst, described metalloscene catalyst uses for example crosslinked bicyclic pentadiene zirconium complex (composition (a)), wherein the crosslinking group of two cyclopentadienyls chain by containing two kinds or multiple atom carries out the crosslinking group crosslinked or chain by containing 2 or a plurality of atoms and carries out crosslinkedly, and cross-linking type (cyclopentadienyl) (fluorenyl) closes zirconium complex and/or crosslinked (indenyl) (fluorenyl) closes zirconium complex (composition (b)).
Gained polyvinyls of the present invention can be used for normally used field.The example in this field comprises injection moulding product, film, plate, blow-molded article (blow), laminated product, foam product and fiber etc.Polyvinyls can carry out moulding by common method for processing forming.Additive as stablizer can use any additive that can be used for the present technique field.In addition, polyvinyls can be by using described other resins with other general known mixed with resin, such as high density polyethylene(HDPE), linear low density polyethylene, new LDPE (film grade), polypropylene, poly-1-butylene, poly--4-methyl-1-pentene, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, the maleic anhydride graft product of polystyrene, these resins etc., perhaps rubber, such as ethylene-propylene rubber, ethene-divinyl rubber, or ethylene-propylene-elastoprene.Polyvinyls also can by with nucleator, mineral filler, fibers etc. are used in combination.In addition, polyvinyls can carry out such as modifications such as grafted maleic anhydride, be similar to common polyolefinic crosslinked etc.Polyvinyls of the present invention can contain common additive such as heat-resisting stabilizing agent, weather stablizer, static inhibitor, antifogging agent, anti, surface slip agent, lubricant, nucleator, mineral filler or strengthening agent, for example, pigment, carbon black, talcum, glass powder or glass fibre etc., organic filler or strengthening agent, fire retardant and neutron shield agent.
The transistion metal compound (composition (a)) that is used for the catalyzer of polyvinyls production of the present invention is the transistion metal compound with general formula (7) expression.
[Chemical formula 1]
In formula (7), M 1Expression titanium atom, zirconium atom or hafnium atom also is preferably titanium atom and zirconium atom.X 1Each represents hydrogen atom independently, halogen atom such as fluorine atom, chlorine atom, bromine atoms or iodine atom; C 1-20Alkyl such as methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, sec-butyl, the tertiary butyl, n-pentyl, isopentyl, 2-methyl butyl, neo-pentyl, tert-pentyl, n-hexyl, isohexyl, 3-methyl amyl, 4-methyl amyl, new hexyl, 2,3-dimethylbutyl, 2, the 2-dimethylbutyl, 4-methyl-2-amyl group, 3,3-dimethyl-2-butyl, 1,1-dimethylbutyl, 2,3-dimethyl-2-butyl, cyclohexyl, vinyl, propenyl, phenyl, tolyl or naphthyl; C 1-20The alkoxyl group that hydrocarbon replaces, such as, methoxyl group, oxyethyl group; C 1-20Amide group such as dimethylformamide base, diethylamide base or di amide group that hydrocarbon replaces; C 1-20Silyl such as trimethyl silyl, triethylsilyl, phenyl dimetylsilyl, diphenyl methyl silyl that hydrocarbon replaces; C 1-20Siliceous alkyl such as trimethyl silyl methyl, triphenyl silyl methyl, trimethyl silyl ethyl; The C that contains periodictable 15 family's atoms 1-20Alkyl such as, dimethyl aminoethyl, dimethylaminopropyl, dimethylaminophenyl or diphenylphosphine methyl (diphenylphosphinomethyl); The C that contains the atom of periodictable 16 families 1-20Alkyl such as methoxymethyl, 2-methoxy ethyl or sulfo-methoxymethyl; Or C 1-20Halogen-containing alkyl such as trifluoromethyl, pentafluorophenyl group, chloro methyl.A is 0 to 2 integer and preferred 2.Each independently represents tetrahydrofuran (THF), Anaesthetie Ether, 1 L, the coordinate bond compound of 4-diox, Trimethylamine, triethylamine, trimethyl-phosphine, triphenylphosphine, acetonitrile, benzonitrile, ethene, 1-propylene, 1-butylene, 1-hexene or tertiary butyl isocyanide (tert-butylisocyanide) etc.B is the integer of 0-6.Q 1And Q 2Represent by general formula (8) ligand and the Q of (9) or (10) independently of one another 1And Q 2With M 1Form sandwich structure together.
[Chemical formula 2]
R in formula (8)-(10) 1Each independently represents hydrogen atom; Halogen atom such as fluorine atom, chlorine atom, bromine atoms or iodine atom; C 1-20Alkyl such as methyl, ethyl, n-propyl, sec.-propyl, normal-butyl; Isobutyl-, sec-butyl, the tertiary butyl, n-pentyl, isopentyl, 2-methyl butyl, neo-pentyl, tert-pentyl, n-hexyl, isohexyl, 3-methyl amyl, 4-methyl amyl, new hexyl, 2,3-dimethylbutyl, 2, the 2-dimethylbutyl, 4-methyl-2-amyl group, 3,3-dimethyl-2-butyl, 1,1-dimethylbutyl, 2,3-dimethyl-2-butyl, cyclohexyl, vinyl, propenyl, phenyl, aminomethyl phenyl or naphthyl; C 1-20The alkoxyl group that hydrocarbon replaces is such as methoxyl group, oxyethyl group; C 1-20Amino such as dimethylamino, diethylamino or di amino that hydrocarbon replaces; C 1-20Silyl such as trimethyl silyl, triethylsilyl, phenyl dimetylsilyl or diphenyl methyl silyl that hydrocarbon replaces; C 1-20Hydrocarbyl silyl is such as the trimethyl silyl methyl, triphenyl silyl methyl or trimethyl silyl ethyl; The C that contains 15 family's atoms in the periodictable 1-20Alkyl such as dimethyl aminoethyl, dimethylaminopropyl, dimethylaminophenyl or diphenylphosphine ylmethyl; The C that contains 16 family's atoms in the periodictable 1-20Alkyl such as methoxymethyl, 2-methoxy ethyl or sulfo-methoxymethyl; C 1-20Halogen-containing alkyl such as trifluoromethyl, pentafluorophenyl group, chloromethyl.R 1But in bond Cheng Huan more than two.
Z in the formula (1) 1By general formula (11), (12), (13), (14) or (15) representative, and be used for crosslinked Q 1And Q 2
[chemical formula 3]
Figure DEST_PATH_S2006800478765D00081
Formula (11) arrives in (15), R 2Represent hydrogen atom independently of one another; Halogen atom such as fluorine atom, chlorine atom, bromine atoms, iodine atom; C 1-20Alkyl such as methyl, ethyl, n-propyl, sec.-propyl, normal-butyl; Isobutyl-, sec-butyl, the tertiary butyl, n-pentyl, isopentyl, 2-methyl butyl, neo-pentyl, tert-pentyl, n-hexyl, isohexyl, 3-methyl amyl, 4-methyl amyl, new hexyl, 2,3-dimethylbutyl, 2, the 2-dimethylbutyl, 4-methyl-2-amyl group, 3,3-dimethyl-2-butyl, 1,1-dimethylbutyl, 2,3-dimethyl-2-butyl, cyclohexyl, vinyl, propenyl, phenyl, aminomethyl phenyl or naphthyl; C 1-20Alkoxyl group such as methoxyl group, oxyethyl group that hydrocarbon replaces; C 1-20Amino such as dimethylamino, diethylamino or di amino that hydrocarbon replaces; C 1-20Silyl such as trimethyl silyl, triethylsilyl, phenyl dimetylsilyl or diphenyl methyl silyl that hydrocarbon replaces; C 1-20Hydrocarbyl silyl is such as the trimethyl silyl methyl, triphenyl silyl methyl or trimethyl silyl ethyl; The C that contains 15 family's atoms in the periodictable 1-20Alkyl such as, dimethyl aminoethyl, dimethylaminopropyl, dimethylaminophenyl or diphenylphosphine ylmethyl; The C that contains 16 family's atoms in the periodictable 1-20Alkyl such as methoxyl methyl, 2-methoxyethyl or sulfo-methoxymethyl; Or C 1-20Halogen-containing alkyl such as trifluoromethyl, pentafluorophenyl group or chloromethyl.E represents the atom of 16 families in the periodictable, such as oxygen, sulphur, selenium or tellurium, and preferred oxygen or sulphur.T represents C 1-5The hydrocarbon crosslinking group, such as methylene radical, ethane-1,2-two bases, propane-1,3-two bases, butane-1,4-two bases or pentane-1,5-two bases.D is 3 to 6 a integer and e is 2 to 6 integer.
The specific examples that is used for the composition (a) of the catalyzer that polyvinyls of the present invention produces comprises dichloride such as dichloro (1,1,3,3-tetramethyl disiloxane-1,3-two bases-bicyclic pentadiene) close zirconium, dichloro (1,1,3,3-tetra isopropyl disiloxane-1,3-two bases-bicyclic pentadiene) close zirconium, dichloro (1,1,3,3-tetraphenyl sily oxide-1,3-two bases-bicyclic pentadiene) close zirconium, dichloro (1,1-dimethyl-1-sila ethane (silaethane)-1,2-two bases-bicyclic pentadiene) close zirconium, dichloro (1,1-di-isopropyl-1-sila ethane-1,2-two bases-bicyclic pentadiene) close zirconium, dichloro (1,1-phenylbenzene-1-sila ethane-1,2-two bases-bicyclic pentadiene) close zirconium, dichloro (propane-1,3-two bases-bicyclic pentadiene) close zirconium, dichloro (1,1,3,3-tetramethyl-propane-1,3-two bases-bicyclic pentadiene) close zirconium, dichloro (2,2-dimethylpropane-1,3-two bases-bicyclic pentadiene) closes zirconium, dichloro (butane-1,4-two bases-bicyclic pentadiene) close zirconium, dichloro (pentane-1,5-two bases-bicyclic pentadiene) close zirconium, dichloro (suitable-2-butylene-1,4-two bases-bicyclic pentadiene) closes zirconium, dichloro (suitable-the 5-decylene-1,10-two bases-bicyclic pentadiene) closes zirconium, dichloro (1,1,2,2-tetramethyl-silicoethane (disilane)-1,2-two bases-bicyclic pentadiene) close zirconium, or dichloro (1,1,2,2-tetraphenyl silicoethane-1,2-two bases-bicyclic pentadiene) close zirconium, and the dimethide of above-mentioned transistion metal compound, diethylization thing, dihydride, phenylbenzene thing or dibenzyl thing.
Being used for the transistion metal compound (composition (b)) that the catalyzer of polyvinyls production of the present invention uses is Metallocenic compound (it is different from composition (a)), and it comprises titanium atom, and zirconium atom or hafnium atom are as central metal.This examples for compounds comprises transistion metal compound, and wherein at least one cyclopentadienyl that does not replace or replace, the indenyl that does not replace or replace, fluorenyl unsubstituted or that replace are coordinated on titanium atom, zirconium atom or the hafnium atom as central metal.
Wherein, transistion metal compound is represented by general formula (16).
[chemical formula 4]
Figure DEST_PATH_S2006800478765D00091
It has high polymerization activity, makes the processibility of the polyvinyls that obtains good, and is preferred therefore.
In the formula (16), M 2Represent titanium atom, zirconium atom or hafnium atom, and X 2Represent hydrogen atom, halogen atom, C independently of one another 1-20Alkyl, C 1-20Hydrocarbyl silyl, C 1-20Nitrogenous alkyl or C 1-20The oxygen-containing hydrocarbon base.
X 2In the example of halogen atom comprise chlorine atom, fluorine atom, bromine atoms and iodine atom.C 1-20The example of alkyl comprises methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, norcamphyl, phenyl, styryl, xenyl, naphthyl, tolyl, ethylphenyl, the propyl group phenyl, butyl phenyl, 3,5-dimethylphenyl, the diethyl phenyl, the dipropyl phenyl, the dibutyl phenyl, the phenylbenzene phenyl, trimethylphenyl, the triethyl phenyl, the tripropyl phenyl, the tributyl phenyl, benzyl, styroyl, hydrocinnamyl, the benzene butyl, diphenyl-methyl, two styroyls, two hydrocinnamyl, the hexichol butyl, vinyl, propenyl, butenyl, butadienyl, pentenyl, pentadienyl, hexenyl, hexadienyl.C 1-20Hydrocarbyl silyl comprises the methyl-silicane base, the ethyl silicane base, the propyl group silyl, the butyl silyl, the amyl group silyl, the hexyl silyl, the phenyl silyl, the benzyl silyl, dimetylsilyl, the diethylsilane base, the dipropyl silyl, the dibutyl silyl, the diphenylmethyl silylation, the dibenzyl silyl, trimethyl silyl, triethylsilyl, the tripropyl silyl, the tributyl silyl, the triphenyl silyl, the 3,5-dimethylphenyl silyl, methyldiphenyl base silyl, the trimethyl silyl methyl, the trimethyl silyl ethyl, the trimethyl silyl propyl group, the trimethyl silyl butyl, the trimethyl silyl phenyl, two (trimethyl silyl) methyl, two (trimethyl silyl) ethyl, two (trimethyl silyl) propyl group, two (trimethyl silyl) butyl, two (trimethyl silyl) phenyl, triphenyl silyl methyl.C 1-20Nitrogenous alkyl comprises methylamino-, ethylamino, third amino, fourth amino, penta amino, oneself is amino, phenylamino, benzyl amino, the benzene ethylamino, phenylpropyl alcohol amino, benzene fourth amino, naphthylamino, dimethylamino, diethylin, dipropyl amino, dibutylamino, diphenylamino, dibenzyl amino, dimethylaminomethyl, dimethyl aminoethyl, dimethylaminopropyl, the dimethylamino butyl, dimethylaminophenyl, two (dimethylamino) methyl, two (dimethylamino) ethyl, two (dimethylamino) propyl group, two (dimethylamino) butyl, two (dimethylamino) phenyl, the phenyl amino methyl, diphenyl amino methyl and diphenyl amino phenyl.C 1-20The example of oxygen-containing hydrocarbon base comprises methoxyl group, oxyethyl group, propoxy-, butoxy, phenoxy group, naphthyloxy, methylphenoxy, the ethyl phenoxy group, the propyl group phenoxy group, butyl phenoxy, biphenylyloxy, methoxymethyl, ethoxyl methyl, the propoxy-methyl, butoxymethyl, phenoxymethyl, methoxy ethyl, ethoxyethyl group, the propoxy-ethyl, butoxyethyl group, the phenoxy group ethyl, methoxy-propyl, ethoxycarbonyl propyl, the propoxy-propyl group, the butoxy propyl group, phenoxy propyl, the methoxyl group butyl, the oxyethyl group butyl, the propoxy-butyl, the butoxy butyl, the phenoxy group butyl, p-methoxy-phenyl, ethoxyl phenenyl, the propoxy-phenyl, butoxy phenyl and Phenoxyphenyl.
Q in the formula (16) 3Be ligand by general formula (17) or (18) expression:
[chemical formula 5]
Figure DEST_PATH_S2006800478765D00101
R 3Represent hydrogen, halogen, C independently of one another 1-20Alkyl, C 1-20Hydrocarbyl silyl, C 1-20Nitrogenous alkyl or C 1-20The oxygen-containing hydrocarbon base.R 3But in bond Cheng Huan more than two.
R in formula (17) or (18) 3The example of halogen atom comprise chlorine, fluorine, bromine and iodine.C 1-20The alkyl example comprises methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, the norborneol alkyl, phenyl, styryl, xenyl, naphthyl, tolyl, the ethylbenzene base, propyl phenyl; butylbenzene base; 3,5-dimethylphenyl; diethyl phenyl; dipropyl phenyl; dibutyl phenyl; phenylbenzene phenyl; trimethylphenyl; triethyl phenyl; tripropyl phenyl; tributyl phenyl; benzyl; styroyl; hydrocinnamyl; benzene butyl; diphenyl-methyl; two styroyls; two hydrocinnamyl; hexichol butyl; vinyl; propenyl; butenyl; butadienyl; pentenyl; pentadienyl; hexenyl; hexadienyl.C 1-20The example of hydrocarbyl silyl comprises the methyl-silicane base, the ethyl silicane base, the propyl group silyl, the butyl silyl, the amyl group silyl, the hexyl silyl, the phenyl silyl, the benzyl silyl, dimetylsilyl, the diethylsilane base, the dipropyl silyl, the dibutyl silyl, the diphenylmethyl silylation, the dibenzyl silyl, trimethyl silyl, triethylsilyl, the tripropyl silyl, the tributyl silyl, the triphenyl silyl, the 3,5-dimethylphenyl silyl, methyldiphenyl base silyl, the trimethyl silyl methyl, the trimethyl silyl ethyl, the trimethyl silyl propyl group, the trimethyl silyl butyl, the trimethyl silyl phenyl, two (trimethyl silyl) methyl, two (trimethyl silyl) ethyl, two (trimethyl silyl) propyl group, two (trimethyl silyl) butyl, two (trimethyl silyl) phenyl and triphenyl silyl methyl.C 1-20The example of nitrogenous alkyl comprises methylamino-, ethylamino, third amino, fourth amino, penta amino, oneself is amino, phenylamino, benzyl amino, the benzene ethylamino, phenylpropyl alcohol amino, benzene fourth amino, naphthylamino, dimethylamino, diethylin, dipropyl amino, dibutylamino, diphenylamino, dibenzyl amino, dimethylaminomethyl, dimethyl aminoethyl, dimethylaminopropyl, the dimethylamino butyl, dimethylaminophenyl, two (dimethylamino) methyl, two (dimethylamino) ethyl, two (dimethylamino) propyl group, two (dimethylamino) butyl, two (dimethylamino) phenyl, the phenylamino methyl, diphenyl amino methyl and diphenylamino phenyl.C 1-20The example of oxygen-containing hydrocarbon base comprises methoxyl group, oxyethyl group, propoxy-, butoxy, phenoxy group, naphthyloxy, tolyloxy, the second phenoxy group, third phenoxy group; fourth phenoxy group; biphenylyloxy; methoxymethyl; ethoxyl methyl; propoxy-methyl; butoxymethyl; phenoxymethyl; methoxy ethyl; ethoxyethyl group; propoxy-ethyl; butoxyethyl group; phenoxy group ethyl; methoxy-propyl; ethoxycarbonyl propyl; propoxy-propyl group; butoxy propyl group; phenoxy propyl; methoxyl group butyl; oxyethyl group butyl; propoxy-butyl; butoxy butyl; phenoxy group butyl; p-methoxy-phenyl; ethoxyl phenenyl; propoxy-phenyl; butoxy phenyl and Phenoxyphenyl.
The specific examples of general formula (17) or (18) comprises cyclopentadienyl, methyl cyclopentadienyl, the dimethyl cyclopentadienyl, the trimethylammonium cyclopentadienyl, the tetramethyl-ring pentadienyl, the ethyl cyclopentadienyl, the diethyl cyclopentadienyl, the triethyl cyclopentadienyl, tetrem alkene cyclopentadienyl, the propyl group cyclopentadienyl, the dipropyl cyclopentadienyl, the tripropyl cyclopentadienyl, the tetrapropyl cyclopentadienyl, the butyl cyclopentadienyl, the dibutyl cyclopentadienyl, the tributyl cyclopentadienyl, tetrabutyl cyclopentadienyl, the benzyl ring pentadienyl, the phenylbenzene cyclopentadienyl, the naphthyl cyclopentadienyl, the methoxyl group cyclopentadienyl, the trimethyl silyl cyclopentadienyl, indenyl, the methyl indenyl, the dimethyl indenyl, the trimethylammonium indenyl, the tetramethyl-indenyl, the pentamethyl-indenyl, the hexamethyl indenyl, ethyl-indenyl, the diethyl indenyl, the triethyl indenyl, the tetraethyl-indenyl, five ethyl-indenyls, the Hexaethyl indenyl, the propyl group indenyl, the dipropyl indenyl, the tripropyl indenyl, the tetrapropyl indenyl, the pentapropyl indenyl, six propyl group indenyls, the butyl indenyl, the dibutyl indenyl, the tributyl indenyl, tetrabutyl indenyl, five butyl indenyls, six butyl indenyls, phenyl indenyl, the phenylbenzene indenyl, benzo indenyl (benzoindenyl), the naphthyl indenyl, methoxyl group indenyl and trimethyl silyl indenyl.
Q in the formula (16) 4Be dentate by general formula (19) expression,
[chemical formula 6]
And substituent R 4Represent hydrogen atom, halogen atom, C independently of one another 1-20Alkyl, C 1-20Hydrocarbyl silyl, C 1-20Nitrogenous alkyl or C 1-20The oxygen-containing hydrocarbon base.R 4Specific examples comprise as R 3Described in same group.
The specific examples of general formula (19) comprises fluorenyl, methylfluorenyl, the dimethyl fluorenyl, the trimethylammonium fluorenyl, the tetramethyl-fluorenyl, the pentamethyl-fluorenyl, the hexamethyl fluorenyl, seven methylfluorenyl, the prestox fluorenyl, the ethyl fluorenyl, the diethyl fluorenyl, the triethyl fluorenyl, the tetraethyl-fluorenyl, five ethyl fluorenyls, the Hexaethyl fluorenyl, seven ethyl fluorenyls, the octaethyl fluorenyl, the propyl group fluorenyl, the dipropyl fluorenyl, the tripropyl fluorenyl, the tetrapropyl fluorenyl, the pentapropyl fluorenyl, six propyl group fluorenyls, seven propyl group fluorenyls, eight propyl group fluorenyls, the butyl fluorenyl, the dibutyl fluorenyl, the tributyl fluorenyl, tetrabutyl fluorenyl, five butyl fluorenyls, six butyl fluorenyls, seven butyl fluorenyls, eight butyl fluorenyls, the phenyl fluorenyl, the phenylbenzene fluorenyl, the benzyl fluorenyl, the dibenzyl fluorenyl, the benzo fluorenyl, the dimethylamino fluorenyl, two (dimethylamino) fluorenyl, the methoxyl group fluorenyl, with the dimethoxy fluorenyl.
Q in the general formula (16) 3And Q 4With M 1Form sandwich structure together.
Z in general formula (16) 2Be by general formula (20) expression, to play with crosslinked Q 3And Q 4Effect.
[chemical formula 7]
Figure DEST_PATH_S2006800478765D00131
R in the general formula (20) 5Represent hydrogen atom, halogen atom, C independently of one another 1-20Alkyl, C 1-20Hydrocarbyl silyl, C 1-20Nitrogenous alkyl or C 1-20The oxygen-containing hydrocarbon base, M 3Represent carbon atom, Siliciumatom, germanium atom or tin atom, wherein preferred carbon atom and Siliciumatom.F is 1 to 5 integer.
R in the general formula (20) 5Halogen atom, C 1-20Alkyl, C 1-20Hydrocarbyl silyl, C 1-20Nitrogenous alkyl or C 1-20The oxygen-containing hydrocarbon base comprises as R 3In identical atom or base.
The specific examples of general formula (20) comprising: methylene radical, ethylidene, ethylidene, propylidene, propylidene, the fourth fork, butylidene, pentylidene, pentylidene, oneself pitches, isopropylidene, the methylethyl methylene radical, the methyl-propyl methylene radical, the methyl butyl methylene radical, two (cyclohexyl) methylene radical, the aminomethyl phenyl methylene radical, the phenylbenzene methylene radical, phenyl (tolyl) methylene radical, two (tolyl) methylene radical, two (3,5-dimethylphenyl) methylene radical, two (trimethylphenyl) methylene radical, phenyl (ethylbenzene base) methylene radical, two (ethylbenzene base) methylene radical, two (diethyl phenyl) methylene radical, phenyl (propyl phenyl) methylene radical, two (propyl phenyl) methylene radical, two (dipropyl phenyl) methylene radical, phenyl (butyl phenyl) methylene radical, two (butyl phenyl) methylene radical, phenyl (naphthyl) methylene radical, two (naphthyl) methylene radical, phenyl (xenyl) methylene radical, two (xenyl) methylene radical, phenyl (trimethyl silyl phenyl) methylene radical, two (trimethyl silyl phenyl) methylene radical, two (pentafluorophenyl group) methylene radical, silane two bases, silicoethane two bases, Trisilicopropane two bases, tetrasilane two bases, dimethylsilane two bases, two (dimethylsilane) two bases, diethylsilane two bases, dipropyl silane two bases, dibutyl silane two bases, diphenyl silane two bases, sila cyclobutadiene base and silacyclohexadiene base.
Dichloro phenylbenzene methylene radical (5-phenyl-1-indenyl) (2,7-dimethyl-9-fluorenyl) closes zirconium, dichloro phenylbenzene methylene radical (6-phenyl-1-indenyl) (2,7-dimethyl-9-fluorenyl) close zirconium, dichloro phenylbenzene methylene radical (7-phenyl-1-indenyl) (2,7-dimethyl-9-fluorenyl) closes zirconium, dichloro phenylbenzene methylene radical (2,3-dimethyl-1-indenyl) (2,7-dimethyl-9-fluorenyl) closes zirconium, dichloro phenylbenzene methylene radical (2,4-dimethyl-1-indenyl) (2,7-dimethyl-9-fluorenyl) closes zirconium, dichloro phenylbenzene methylene radical (2,5-dimethyl-1-indenyl) (2,7-dimethyl-9-fluorenyl) closes zirconium, dichloro phenylbenzene methylene radical (2,6-dimethyl-1-indenyl) (2,7-dimethyl-9-fluorenyl) closes zirconium, dichloro phenylbenzene methylene radical (2,7-dimethyl-1-indenyl) (2,7-dimethyl-9-fluorenyl) closes zirconium, dichloro phenylbenzene methylene radical (3,4-dimethyl-1-indenyl) (2,7-dimethyl-9-fluorenyl) closes zirconium, dichloro phenylbenzene methylene radical (3,5-dimethyl-1-indenyl) (2,7-dimethyl-9-fluorenyl) closes zirconium, dichloro phenylbenzene methylene radical (3,6-dimethyl-1-indenyl) (2,7-dimethyl-9-fluorenyl) closes zirconium, dichloro phenylbenzene methylene radical (3,7-dimethyl-1-indenyl) (2,7-dimethyl-9-fluorenyl) closes zirconium, dichloro phenylbenzene methylene radical (4,5-dimethyl-1-indenyl) (2,7-dimethyl-9-fluorenyl) closes zirconium, dichloro phenylbenzene methylene radical (4,6-dimethyl-1-indenyl) (2,7-dimethyl-9-fluorenyl) closes zirconium, dichloro phenylbenzene methylene radical (4,7-dimethyl-1-indenyl) (2,7-dimethyl-9-fluorenyl) closes zirconium, dichloro phenylbenzene methylene radical (5,6-dimethyl-1-indenyl) (2,7-dimethyl-9-fluorenyl) closes zirconium, dichloro phenylbenzene methylene radical (5,7-dimethyl-1-indenyl) (2,7-dimethyl-9-fluorenyl) closes zirconium, dichloro phenylbenzene methylene radical (6,7-dimethyl-1-indenyl) (2,7-dimethyl-9-fluorenyl) closes zirconium, dichloro phenylbenzene methylene radical (2-methyl-4-phenyl-1-indenyl) (2,7-dimethyl-9-fluorenyl) closes zirconium, dichloro phenylbenzene methylene radical (2-methyl-4,5-phendioxin-indenyl) (2,7-dimethyl-9-fluorenyl) close zirconium, dichloro phenylbenzene methylene radical (2-methyl-5,6-phendioxin-indenyl) (2,7-dimethyl-9-fluorenyl) close zirconium, dichloro phenylbenzene methylene radical (2-methyl-4-(Alpha-Naphthyl)-1-indenyl) (2,7-dimethyl-9-fluorenyl) close zirconium, dichloro phenylbenzene methylene radical (2-methyl-4-(betanaphthyl)-1-indenyl) (2,7-dimethyl-9-fluorenyl) closes zirconium, dichloro phenylbenzene methylene radical (1-indenyl) (2,7-diethyl-9-fluorenyl) closes zirconium, dichloro phenylbenzene methylene radical (2-methyl isophthalic acid-indenyl) (2,7-diethyl-9-fluorenyl) close zirconium, dichloro phenylbenzene methylene radical (3-methyl isophthalic acid-indenyl) (2,7-diethyl-9-fluorenyl) closes zirconium, dichloro phenylbenzene methylene radical (4-methyl isophthalic acid-indenyl) (2,7-diethyl-9-fluorenyl) closes zirconium, dichloro phenylbenzene methylene radical (5-methyl isophthalic acid-indenyl) (2,7-diethyl-9-fluorenyl) close zirconium, dichloro phenylbenzene methylene radical (6-methyl isophthalic acid-indenyl) (2,7-diethyl-9-fluorenyl) closes zirconium, dichloro phenylbenzene methylene radical (7-methyl isophthalic acid-indenyl) (2,7-diethyl-9-fluorenyl) closes zirconium, dichloro phenylbenzene methylene radical (2-phenyl-1-indenyl) (2,7-diethyl-9-fluorenyl) close zirconium, dichloro phenylbenzene methylene radical (3-phenyl-1-indenyl) (2,7-diethyl-9-fluorenyl) closes zirconium, dichloro phenylbenzene methylene radical (4-phenyl-1-indenyl) (2,7-diethyl-9-fluorenyl) closes zirconium, dichloro phenylbenzene methylene radical (5-phenyl-1-indenyl) (2,7-diethyl-9-fluorenyl) close zirconium, dichloro phenylbenzene methylene radical (6-phenyl-1-indenyl) (2,7-diethyl-9-fluorenyl) closes zirconium, dichloro phenylbenzene methylene radical (7-phenyl-1-indenyl) (2,7-ethyl-9-fluorenyl) closes zirconium, dichloro phenylbenzene methylene radical (2,3-dimethyl-1-indenyl) (2,7-diethyl-9-fluorenyl) closes zirconium, dichloro phenylbenzene methylene radical (2,4-dimethyl-1-indenyl) (2,7-diethyl-9-fluorenyl) closes zirconium, dichloro phenylbenzene methylene radical (2,5 dimethyl-1-indenyl) (2,7-diethyl-9-fluorenyl) close zirconium, dichloro phenylbenzene methylene radical (2,6-dimethyl-1-indenyl) (2,7-diethyl-9-fluorenyl) closes zirconium, dichloro phenylbenzene methylene radical (2,7-dimethyl-1-indenyl) (2,7-diethyl-9-fluorenyl) closes zirconium, dichloro phenylbenzene methylene radical (3,4-dimethyl-1-indenyl) (2,7-diethyl-9-fluorenyl) closes zirconium, dichloro phenylbenzene methylene radical (3,5-dimethyl-1-indenyl) (2,7-diethyl-9-fluorenyl) close zirconium, dichloro phenylbenzene methylene radical (3,6-dimethyl-1-indenyl) (2,7-diethyl-9-fluorenyl) closes zirconium, dichloro phenylbenzene methylene radical (3,7-dimethyl-1-indenyl) (2,7-diethyl-9-fluorenyl) closes zirconium, dichloro phenylbenzene methylene radical (4,5-dimethyl-1-indenyl) (2,7-diethyl-9-fluorenyl) closes zirconium, dichloro phenylbenzene methylene radical (4,6-dimethyl-1-indenyl) (2,7-diethyl-9-fluorenyl) close zirconium, dichloro phenylbenzene methylene radical (4,7-dimethyl-1-indenyl) (2,7-diethyl-9-fluorenyl) closes zirconium, dichloro phenylbenzene methylene radical (5,6-dimethyl-1-indenyl) (2,7-diethyl-9-fluorenyl) closes zirconium, dichloro phenylbenzene methylene radical (5,7-dimethyl-1-indenyl) (2,7-diethyl-9-fluorenyl) closes zirconium, dichloro phenylbenzene methylene radical (6,7-dimethyl-1-indenyl) (2,7-diethyl-9-fluorenyl) close zirconium, dichloro phenylbenzene methylene radical (2-methyl-4-phenyl-1-indenyl) (2,7-diethyl-9-fluorenyl) closes zirconium, dichloro phenylbenzene methylene radical (2-methyl-4,5-phendioxin-indenyl) (2,7-diethyl-9-fluorenyl) closes zirconium, dichloro phenylbenzene methylene radical (2-methyl-5,6-phendioxin-indenyl) (2,7-diethyl-9-fluorenyl) close zirconium, dichloro phenylbenzene methylene radical (2-methyl-4-(Alpha-Naphthyl)-1-indenyl) (2,7-diethyl-9-fluorenyl) closes zirconium, dichloro phenylbenzene methylene radical (2-methyl-4-(betanaphthyl)-1-indenyl) (2,7-diethyl-9-fluorenyl) closes zirconium, dichloro phenylbenzene methylene radical (1-indenyl) (2,7-di-t-butyl-9-fluorenyl) closes zirconium, dichloro phenylbenzene methylene radical (2-methyl isophthalic acid-indenyl) (2,7-di-t-butyl-9-fluorenyl) closes zirconium, dichloro phenylbenzene methylene radical (3-methyl isophthalic acid-indenyl) (2,7-di-t-butyl-9-fluorenyl) closes zirconium, dichloro phenylbenzene methylene radical (4-methyl isophthalic acid-indenyl) (2,7-di-t-butyl-9-fluorenyl) closes zirconium, dichloro phenylbenzene methylene radical (5-methyl isophthalic acid-indenyl) (2,7-di-t-butyl-9-fluorenyl) closes zirconium, dichloro phenylbenzene methylene radical (6-methyl isophthalic acid-indenyl) (2,7-di-t-butyl-9-fluorenyl) closes zirconium, dichloro phenylbenzene methylene radical (7-methyl isophthalic acid-indenyl) (2,7-di-t-butyl-9-fluorenyl) closes zirconium, dichloro phenylbenzene methylene radical (2-phenyl-1-indenyl) (2,7-di-t-butyl-9-fluorenyl) closes zirconium, dichloro phenylbenzene methylene radical (3-phenyl-1-indenyl) (2,7-di-t-butyl-9-fluorenyl) closes zirconium, dichloro phenylbenzene methylene radical (4-phenyl-1-indenyl) (2,7-di-t-butyl-9-fluorenyl) closes zirconium, dichloro phenylbenzene methylene radical (5-phenyl-1-indenyl) (2,7-di-t-butyl-9-fluorenyl) closes zirconium, dichloro phenylbenzene methylene radical (6-phenyl-1-indenyl) (2,7-di-t-butyl-9-fluorenyl) closes zirconium, dichloro phenylbenzene methylene radical (7-phenyl-1-indenyl) (2,7-di-t-butyl-9-fluorenyl) closes zirconium, dichloro phenylbenzene methylene radical (2,3-dimethyl-1-indenyl) (2,7-di-t-butyl-9-fluorenyl) closes zirconium, dichloro phenylbenzene methylene radical (2,4-dimethyl-1-indenyl) (2,7-di-t-butyl-9-fluorenyl) close zirconium, dichloro phenylbenzene methylene radical (2,5-dimethyl-1-indenyl) (2,7-di-t-butyl-9-fluorenyl) closes zirconium, dichloro phenylbenzene methylene radical (2,6-dimethyl-1-indenyl) (2,7-di-t-butyl-9-fluorenyl) closes zirconium, dichloro phenylbenzene methylene radical (2,7-dimethyl-1-indenyl) (2,7-di-t-butyl-9-fluorenyl) closes zirconium, dichloro phenylbenzene methylene radical (3,4-dimethyl-1-indenyl) (2,7-di-t-butyl-9-fluorenyl) close zirconium, dichloro phenylbenzene methylene radical (3,5-dimethyl-1-indenyl) (2,7-di-t-butyl-9-fluorenyl) closes zirconium, dichloro phenylbenzene methylene radical (3,6-dimethyl-1-indenyl) (2,7-di-t-butyl-9-fluorenyl) closes zirconium, dichloro phenylbenzene methylene radical (3,7-dimethyl-1-indenyl) (2,7-di-t-butyl-9-fluorenyl) closes zirconium, dichloro phenylbenzene methylene radical (4,5-dimethyl-1-indenyl) (2,7-di-t-butyl-9-fluorenyl) close zirconium, dichloro phenylbenzene methylene radical (4,6-dimethyl-1-indenyl) (2,7-di-t-butyl-9-fluorenyl) closes zirconium, dichloro phenylbenzene methylene radical (4,7-dimethyl-1-indenyl) (2,7-di-t-butyl-9-fluorenyl) closes zirconium, dichloro phenylbenzene methylene radical (5,6-dimethyl-1-indenyl) (2,7-di-t-butyl-9-fluorenyl) closes zirconium, dichloro phenylbenzene methylene radical (5,7-dimethyl-1-indenyl) (2,7-di-t-butyl-9-fluorenyl) close zirconium, dichloro phenylbenzene methylene radical (6,7-dimethyl-1-indenyl) (2,7-di-t-butyl-9-fluorenyl) close zirconium, dichloro phenylbenzene methylene radical (2-methyl-4-phenyl-1-indenyl) (2,7-di-t-butyl-9-fluorenyl) closes zirconium, dichloro phenylbenzene methylene radical (2-methyl-4,5-phendioxin-indenyl) (2,7-di-t-butyl-9-fluorenyl) close zirconium, dichloro phenylbenzene methylene radical (2-methyl-5,6-phendioxin-indenyl) (2,7-di-t-butyl-9-fluorenyl) close zirconium, dichloro phenylbenzene methylene radical (2-methyl-4-(Alpha-Naphthyl)-1-indenyl) (2,7-di-t-butyl-9-fluorenyl) closes zirconium, dichloro phenylbenzene methylene radical (2-methyl-4-(betanaphthyl)-1-indenyl) (2,7-di-t-butyl-9-fluorenyl) closes zirconium.Example also comprises the wherein X of transistion metal compound 2By fluorine atom, the compound that bromine atoms or iodine atom are replaced, example also comprises the Z of transistion metal compound 2By the compound of replacements such as methylene radical, ethylidene, isopropylidene, aminomethyl phenyl methylene radical, dimethylsilane two bases, diphenyl silane two bases, sila tetramethylene two bases, Silinane two bases.Example also comprises the wherein M of transistion metal compound 2Compound with titanium atom or hafnium atom replacement.
Composition among the present invention (b) is not particularly limited with respect to the amount of composition (a), is preferably 0.0001 to 100 times of mole, is preferably 0.001 to 10 times of mole especially.
Containing composition (a) and composition (b) among the present invention comprises as the polyvinyls production of the principal constituent example with catalyzer: the catalyzer that comprises composition (a), composition (b) and active co catalyst and/or organometallic compound.
Below the catalyzer that comprises composition (a), composition (b) and active co catalyst and/or organometallic compound is described in.
This catalyzer comprises: comprise composition (a), composition (b) and the catalyzer of the modified clay mineral handled with organic compound (composition (c)).
The clay mineral that can be used as composition (c) in the present invention is to comprise the fine particle of microcrystal silicon hydrochlorate as principal constituent.Most of clay minerals have the characteristic of laminate structure and the negative charge of different sizes are arranged in layer on its structure.In this, clay mineral obviously is different from metal oxide such as silicon oxide or the aluminum oxide with three-dimensional structure.These clay minerals are categorized into agalmatolite usually, kaolin, dickite (deckite) and talcs (negative charge of every chemical formula is about 0), smectites (negative charge of every chemical formula is about 0.25-0.6), vermiculite class (negative charge of every chemical formula is about 0.6-0.9), mica group (negative charge of every chemical formula is about 1) and fragility mica group (negative charge of every chemical formula is about 2), this depends on the size of layer charge.Above-mentioned each class comprises different separately clay minerals.The example that belongs to the clay mineral of smectites comprises montmorillonite, beidellite, saponite and hectorite.The example of these clay minerals comprises naturally occurring clay mineral and derives from the clay minerals that contains small amount of impurities of synthetic.The present invention can use whole this paper to describe natural clay mineral and by the clay mineral of synthetic gained, and can use all material that belongs to the clay mineral definition in addition, even toply do not point out.The clay mineral that wherein belongs to smectites and mica group is preferred.These clay minerals all can its two kinds or more kinds of mixture uses.These clay minerals can directly use, and maybe can use by new interpolation and planar water, or handle the back at thermal dehydration and use.
Organic compound in composition (c) is handled to mean and is introduced organic ion to form a kind of ionic complex between the clay mineral layer.Compound by following general formula (21), (24) or (25) expression can be used as the organic compound that uses in organic compound is handled, and wherein the compound by general formula (21) expression is preferred especially the use.
[R 6R 7 g-1M 4H] h[A] i (21)
[C] h[A] i (24)
[M 5L 2 j] h[A] i (25)
By [A] in the compound of general formula (21), (24) and (25) representative is negatively charged ion, the example comprises fluorion, chlorion, bromide anion, iodide ion, sulfate ion, nitrate ion, phosphate anion, perchlorate, oxalate denominationby, citrate ion, succinate ion, tetrafluoroborate ion and hexafluorophosphoricacid acid ions.
Make the selected integer of charge balance by h and i in the compound of general formula (21), (24) and (25) representative.
[R in the compound of representing by general formula (21) 6R 7 G-1M 4H] be positively charged ion, M wherein 4Be to be selected from the element in the 15th family and 16 families in the periodictable, R 6Represent C 1-30Alkyl, R 7Represent hydrogen atom or C independently of one another 1-30Alkyl, and work as M 4When being the element of 15 families, then g is 3, and works as M 4Be 16 families element then g be 2.
M 4Be to be selected from the element in 15 families and 16 families in the periodictable, the example comprises oxygen, nitrogen, sulphur and phosphorus.Be used for R 6And R 7In C 1-30The example of alkyl comprises methyl, ethyl, n-propyl, sec.-propyl, allyl group, normal-butyl, isobutyl-, sec-butyl, the tertiary butyl, n-pentyl, isopentyl, the 2-methyl butyl, the 1-methyl butyl, the 1-ethyl propyl, neo-pentyl, tert-pentyl, cyclopentyl, n-hexyl, isohexyl, the 3-methyl amyl, the 4-methyl amyl, new hexyl, 2, the 3-dimethylbutyl, 2, the 2-dimethylbutyl, 4-methyl-2-amyl group, 3,3-dimethyl-2-butyl, 1, the 1-dimethylbutyl, 2, the 3-dimethylbutyl, cyclohexyl, n-heptyl, suberyl, the 2-methylcyclohexyl, the 3-methylcyclohexyl, the 4-methylcyclohexyl, n-octyl, iso-octyl, 1,5-dimethyl hexyl, the 1-methylheptyl, the 2-ethylhexyl, uncle's octyl group, 2, the 3-Dimethylcyclohexyl, 2-(1-cyclohexenyl) ethyl, n-nonyl, positive decyl, isodecyl, geranyl (geranyl), the n-undecane base, dodecyl, cyclo-dodecyl, the n-tridecane base, the n-tetradecane base, the Pentadecane base, n-hexadecyl, the n-heptadecane base, the Octadecane base, the NSC 77136 base, the NSC 62789 base, the heneicosane base, the n-docosane base, the n-tricosane base, oil base Shan Yu base (vehenyl), the phenyl o-tolyl, between tolyl, p-methylphenyl, 2-ethylbenzene base, 3-ethylbenzene base, 4-ethylbenzene base, the 3-isopropyl phenyl, the 2-isopropyl phenyl, the 4-isopropyl phenyl, the 2-tert-butyl-phenyl, the 4-n-butylphenyl, the 4-secondary butyl phenenyl, the 4-tert-butyl-phenyl, 2, the 3-xylyl, 2, the 4-xylyl, 2, the 5-xylyl, 2, the 6-xylyl, 3, the 4-xylyl, 3, the 5-xylyl, 2,6-diethyl phenyl, 2-sec.-propyl-6-tolyl, the 2-chloro-phenyl-, the 3-chloro-phenyl-, the 4-chloro-phenyl-, the 2-bromophenyl, the 3-bromophenyl, the 4-bromophenyl, the 2-p-methoxy-phenyl, the 3-p-methoxy-phenyl, the 4-p-methoxy-phenyl, the 2-ethoxyl phenenyl, the 3-ethoxyl phenenyl, the 4-ethoxyl phenenyl, the 1-naphthyl, the 2-naphthyl, the 1-fluorenyl, the 2-fluorenyl, the 3-fluorenyl, the 4-fluorenyl, 2,3-dihydro indenes-5-base, the 2-xenyl, 4-xenyl and right-trimethyl silyl phenyl.R 6And R 7Bond mutually.
In the particular compound by general formula (21) representative, work as M 4When being nitrogen-atoms, examples for compounds comprises that the aliphatic amine hydrochloride is such as methylamine hydrochloride, ethylamine hydrochloride, the Tri N-Propyl Amine hydrochloride, isopropylamine hydrochloride, the n-butylamine hydrochloride, the isobutylamine hydrochloride, the tert-butylamine salt hydrochlorate, the n-amylamine hydrochloride, the isoamylamine hydrochloride, 2-methyl butyl amine hydrochlorate, the neo-pentyl amine hydrochlorate, the tert.-amylamine hydrochloride, the n-hexyl amine hydrochlorate, the isohexyl amine hydrochlorate, the n-heptyl amine hydrochlorate, just-the octyl amine hydrochloride, just-the nonyl amine hydrochlorate, just-the decyl amine hydrochloride, just-the undecyl amine hydrochlorate, just-the dodecyl amine hydrochlorate, just-the tetradecyl amine hydrochlorate, just-the hexadecyl amine hydrochlorate, just-the octadecyl amine hydrochlorate, allylamine hydrochloride, the cyclopentyl amine hydrochlorate, the dimethyl amine hydrochloride, the diethylamide hydrochloride, the diallyl amine hydrochlorate, the Trimethylamine hydrochloride, the tri-n-butyl amine hydrochloride, triallyl amine hydrochloride, the hexyl amine hydrochloride, the 2-aminoheptane hydrochloride, the amino heptane hydrochloride of 3-, just-the heptyl amine hydrochloride, 1,5-dimethyl hexyl amine hydrochloride, 1-methylheptyl amine hydrochlorate, just-the octyl amine hydrochloride, uncle's octyl amine hydrochloride, the nonyl amine hydrochlorate, the decyl amine hydrochloride, the undecyl amine hydrochlorate, the dodecyl amine hydrochlorate, the tridecyl amine hydrochlorate, the tetradecyl amine hydrochlorate, the pentadecyl amine hydrochlorate, the hexadecyl amine hydrochlorate, the heptadecyl amine hydrochlorate, the octadecyl amine hydrochlorate, the nonadecyl amine hydrochlorate, cyclohexylamine hydrochloride, the cycloheptylamino hydrochloride, 2-methylcyclohexyl amine hydrochlorate, 3-methylcyclohexyl amine hydrochlorate, 4-methyl cyclohexane amine hydrochlorate, 2,3-dimethylcyclohexylamine hydrochloride, the cyclo-dodecyl amine hydrochlorate, 2-(1-cyclohexenyl) ethylamine hydrochloride, the geranyl amine hydrochloride, N-methyl hexyl amine hydrochloride, the dihexyl amine hydrochlorate, two (2-ethylhexyl) amine hydrochlorate, the dioctylamine hydrochloride, two decyl amine hydrochlorides, N-methylcyclohexyl amine hydrochlorate, N-ethyl cyclo-hexylamine hydrochloride, N-isopropylcyclohexyl-hydrochloride, N-tert-butylcyclohexyl amine hydrochlorate, N-allyl group cyclo-hexylamine hydrochloride, N, N-dimethyl octyl group amine hydrochlorate, N, N-dimethyl undecyl amine hydrochlorate, N, N-dimethyl dodecyl amine hydrochlorate, N, N-dimethyl-n-tetradecane base amine hydrochlorate, N, N-dimethyl-n-hexadecyl amine hydrochlorate, N, N-dimethyl n octadecyl amine hydrochlorate, N, N-dimethyl n eicosyl amine hydrochlorate, N, N-dimethyl n docosyl amine hydrochlorate, N, N-dimethyl oil base amine hydrochlorate, N, N-dimethyl Shan Yu base amine hydrochlorate, three hexyl amine hydrochlorides, three iso-octyl amine hydrochlorates, the trioctylphosphine amine hydrochlorate, three isodecyl amine hydrochlorates, the tridodecylamine hydrochloride, N-methyl-N-octadecyl-1-stearylamine hydrochloride, N, N-dimethylcyclohexylam,ne hydrochloride, N, N-Dimethylcyclohexyl methylamine hydrochloride, N, N-diethyl cyclo-hexylamine hydrochloride, N-methyldioctylamine hydrochloride, N-methyl two (undecyl) amine hydrochlorate, N-methyl two (dodecyl) amine hydrochlorate, N-methyl-two (n-tetradecane base) amine hydrochlorate, N-methyl-two (n-hexadecyl) amine hydrochlorate, N-methyl-two (Octadecane base) amine hydrochlorate, N-methyl-two (NSC 62789 base) amine hydrochlorate, N-methyl-two (n-docosane base) amine hydrochlorate, N-methyl two oil base amine hydrochlorates, N, N-methyl Er Shan Yu base amine hydrochlorate, pyrrolidine hydrochloride, piperidine hydrochlorate, 2,5-dimethyl pyrrolidine hydrochloride, the pipecoline hydrochloride, 3-methyl piperidine hydrochloride, 4-methyl piperidine hydrochloride, 2,6-lupetidine hydrochloride, 3,3-lupetidine hydrochloride, 3,5-lupetidine hydrochloride, 2-ethyl piperidine hydrochloride, 2,2,6,6-tetramethyl piperidine hydrochloride, 1-crassitude hydrochloride, 1-methyl piperidine hydrochloride, 1-ethyl piperidine hydrochloride, 1-butyl pyrrolidine hydrochloride and 1,2,2,6,6-pentamethyl-piperidine hydrochlorate; The aromatic amine hydrochloride is such as anilinechloride, the methylphenylamine hydrochloride, the N-ethylaniline hydrochloride, N-allyl benzene amine hydrochlorate, o-toluidine hydrochloride, the meta-aminotoluene hydrochloride, paratoluidine hydrochloride, N, the accelerine hydrochloride, N-methyl o-toluidine hydrochloride, N-methyl meta-aminotoluene hydrochloride, N-methyl paratoluidine hydrochloride, N-ethyl o-toluidine hydrochloride, the N-ethyl-m-toluidine hydrochloride, N-ethyl-p-toluidiine hydrochloride, N-allyl group o-toluidine hydrochloride, N-allyl group meta-aminotoluene hydrochloride, N-allyl group paratoluidine hydrochloride, N-propyl group o-toluidine hydrochloride, N-propyl group meta-aminotoluene hydrochloride, N-propyl group paratoluidine hydrochloride, 2, the 3-dimethylaniline dihydrochloride, 2, the 4-dimethylaniline dihydrochloride, 2, the 5-dimethylaniline dihydrochloride, 2, the 6-dimethylaniline dihydrochloride, 3, the 4-dimethylaniline dihydrochloride, 3, the 5-dimethylaniline dihydrochloride, the 2-ethyl aniline hydrochloride, the 3-ethyl aniline hydrochloride, the 4-ethyl aniline hydrochloride, N, N-diethylbenzene amine hydrochlorate, 2-isopropyl benzene amine hydrochlorate, 4-isopropyl benzene amine hydrochlorate, 2-tert.-butylbenzene amine hydrochlorate, 4-n-butylbenzene amine hydrochlorate, 4-sec-butylbenzene amine hydrochlorate, 4-tert.-butylbenzene amine hydrochlorate, 2,6-diethylbenzene amine hydrochlorate, 2-sec.-propyl-6-methylaniline hydrochloride, 2-chloroaniline hydrochloride, 3-chloroaniline hydrochloride, 4-chloroaniline hydrochloride, 2-bromaniline hydrochloride, 3-bromaniline hydrochloride, 4-bromaniline hydrochloride, the o-anisidine hydrochloride, the m-anisidine hydrochloride, the P-anisidine hydrochloride, the o-phenetidine hydrochloride, the m-phenetidine hydrochloride, the p-phenetidine hydrochloride, 1-amino naphthalenes hydrochloride, 2-amino naphthalenes hydrochloride, 1-aminofluorene hydrochloride, 2-aminofluorene hydrochloride, 3-aminofluorene hydrochloride, 4-aminofluorene hydrochloride, 5-aminoidan hydrochloride, 2-phenylaniline hydrochloride, 4-phenylaniline hydrochloride, N, 2,3-Three methyl Benzene amine hydrochlorate, N, 2,4-Three methyl Benzene amine hydrochlorate, N, 2,5-Three methyl Benzene amine hydrochlorate, N, 2,6-Three methyl Benzene amine hydrochlorate, N, 3,4-Three methyl Benzene amine hydrochlorate, N, 3,5-Three methyl Benzene amine hydrochlorate, N-methyl-2-ethyl aniline hydrochloride, N-methyl-3-ethyl aniline hydrochloride, N-methyl-4-ethyl aniline hydrochloride, N-methyl-6-ethyl o-toluidine hydrochloride, N-methyl-2-isopropyl benzene amine hydrochlorate, N-methyl-4-isopropyl benzene amine hydrochlorate, N-methyl-2-tert.-butylbenzene amine hydrochlorate, N-methyl-4-n-butylbenzene amine hydrochlorate, N-methyl-4-sec-butylbenzene amine hydrochlorate, N-methyl-4-tert.-butylbenzene amine hydrochlorate, N-methyl-2,6-diethylbenzene amine hydrochlorate, N-methyl-2-sec.-propyl-6-methylaniline hydrochloride, N-methyl P-anisidine hydrochloride, N-ethyl-2,3-methyl oxyaniline hydrochloride, N, N-dimethyl-p-toluidine hydrochloride, N, N-dimethyl meta-aminotoluene hydrochloride, N, N-dimethyl-p-toluidine hydrochloride, N, N, 2,3-tetramethyl-benzene amine hydrochlorate, N, N, 2,4-tetramethyl-benzene amine hydrochlorate, N, N, 2,5-tetramethyl-benzene amine hydrochlorate, N, N, 2,6-tetramethyl-benzene amine hydrochlorate, N, N, 3,4-tetramethyl-benzene amine hydrochlorate, N, N, 3,5-tetramethyl-benzene amine hydrochlorate, N, N-dimethyl-2-ethyl aniline hydrochloride, N, N-dimethyl-3-ethyl aniline hydrochloride, N, N-dimethyl-4-ethyl aniline hydrochloride, N, N-dimethyl-6-ethyl o-toluidine hydrochloride, N, N-dimethyl-2-isopropyl benzene amine hydrochlorate, N, N-dimethyl-4-isopropyl benzene amine hydrochlorate, N, N-dimethyl-2-tert.-butylbenzene amine hydrochlorate, N, N-dimethyl-4-n-butylbenzene amine hydrochlorate, N, N-dimethyl-4-sec-butylbenzene amine hydrochlorate, N, N-dimethyl-4-tert.-butylbenzene amine hydrochlorate, N, N-dimethyl-2,6-diethylbenzene amine hydrochlorate, N, N-dimethyl-2-sec.-propyl-6-methylaniline hydrochloride, N, N-dimethyl-2-chloroaniline hydrochloride, N, N-dimethyl-3-chloroaniline hydrochloride, N, N-dimethyl-4-chloroaniline hydrochloride, N, N-dimethyl-2-bromaniline hydrochloride, N, N-dimethyl-3-bromaniline hydrochloride, N, N-dimethyl-4-bromaniline hydrochloride, N, N-dimethyl o-anisidine hydrochloride, N, N-dimethyl m-anisidine hydrochloride, N, N-dimethyl P-anisidine hydrochloride, N, N-dimethyl o-phenetidine hydrochloride, N, N-dimethyl m-phenetidine hydrochloride, N, N-dimethyl p-phenetidine hydrochloride, N, N-dimethyl-1-amino naphthalenes hydrochloride, N, N-dimethyl-2-amino naphthalenes hydrochloride, N, N-dimethyl-1-aminofluorene hydrochloride, N, N-dimethyl-2-aminofluorene hydrochloride, N, N-dimethyl-3-aminofluorene hydrochloride, N, N-dimethyl-4-aminofluorene hydrochloride, N, N-dimethyl-5-aminoidan hydrochloride, N, N-dimethyl-2-phenylaniline hydrochloride, N, N-dimethyl-4-phenylaniline hydrochloride or N, the N-dimethyl-to the trimethyl silyl anilinechloride; And wherein the hydrochloride of above-claimed cpd with hydrofluoride, hydrobromate, hydriodate or vitriol alternate compound.
In the compound with general formula (21) expression, M 4Be that the compound that the examples of compounds of Sauerstoffatom comprises has such as methyl ether hydrochloride, ethyl ether hydrochloride, n-butyl ether hydrochloride, tetrahydrofuran (THF) hydrochloride and phenyl ether hydrochloride; And the hydrochloride of above-claimed cpd is with hydrofluoride, hydrogen bromine salt, hydrogen salt compounded of iodine or vitriol alternate compound.
In the compound by general formula (21) expression, M wherein 4The examples for compounds that is sulphur atom comprises diethyl sulfonium fluorochemical, diethyl sulfonium muriate, diethyl sulfonium bromide, diethyl sulfonium iodide, dimethyl sulfonium fluorochemical, dimethyl sulfonium muriate, dimethyl sulfonium bromide and dimethyl sulfonium iodide.
In the compound by general formula (21) expression, M wherein 4Be the compound that the examples for compounds of phosphorus atom comprises, such as triphenylphosphine hydrochloride, three (o-tolyl) phosphonium salt hydrochlorate, three (p-methylphenyl) phosphonium salt hydrochlorate and three methylsulfonyl phosphonium salt hydrochlorates; And wherein the hydrochloride of above-claimed cpd with hydrofluoride, hydrobromate, hydriodate or vitriol alternate compound.
By [C] in the compound of general formula (24) expression be carbocation (carbonium cation) or
Figure DEST_PATH_S2006800478765D00291
Positively charged ion (tropylium cation).With the specific examples of the compound of general formula (24) expression comprise trityl bromide, trityl chloride, Tetrafluoroboric acid trityl ester (trityl tetrafluoroborate), phosphofluoric acid trityl ester, Bromide (tropylium bromide), Muriate,
Figure DEST_PATH_S2006800478765D00294
A tetrafluoro borate (tropylium tetrafluoroborate) and Hexafluorophosphate.
With the M in the compound of general formula (25) expression 4Be positively charged ion such as lithium atom, iron atom or silver atoms, L 2Be Lewis base such as ether, aliphatic amine, aromatic amine, phosphine, perhaps replace or unsubstituted cyclopentadienyl, and j be 0≤j≤2.Specific examples with the compound of general formula (25) expression comprises ferrocene bromide, ferrocene muriate, ferrocene a tetrafluoro borate and ferrocene hexafluorophosphate.
It is that 0.1-30% weight and treatment temp are to carry out under 0-150 ℃ the condition that organic compound in composition (c) is handled preferably by the concentration of selecting clay mineral.Organic compound can use by being prepared into solid and solid being dissolved in solvent, perhaps can directly use by the solution for preparing organic compound with the chemical reaction in solvent.Reacting weight ratio between clay mineral and the organic compound preferably organic compound is to use with the equivalent or the more amount of the exchangeable cation in clay minerals.The example of operable processing solvent comprises aliphatic hydrocrbon such as pentane, hexane or heptane; Aromatic hydrocarbons such as benzene or toluene; Alcohol is such as ethanol or methyl alcohol; Ether such as ether or n-butyl ether; Halon such as methylene dichloride or trichloromethane; Acetone; 1, the 4-diox; Tetrahydrofuran (THF); And water.Wherein, alcohol or water can preferably use separately or use as a kind of composition of solvent.
Be used for the catalyzer that comprises composition (a), composition (b) and composition (c) of the present invention and be by for example, composition (a), composition (b) and composition (c) are contacted in organic solvent and make.Contact method comprises: composition (b) is added to the method in the product of contact of composition (a) and composition (c), composition (a) is added to the method in the product of contact of composition (b) and composition (c), composition (c) is added to the method in the product of contact of composition (a) and composition (b), the product of contact of composition (a) and composition (b) is added to method in the composition (c) and the method that composition (a), composition (b) and composition (c) are contacted simultaneously.
The example of used solvent comprises hydrocarbon such as butane, pentane, hexane, heptane, octane, nonane, decane, pentamethylene or hexanaphthene during contact; Aromatic hydrocarbons such as benzene, toluene or dimethylbenzene; Ether such as ether or n-butyl ether; Halon such as methylene dichloride, chloroform; 1,4-diox, acetonitrile; And tetrahydrofuran (THF).
Temperature during contact is preferably selected from 0-200 ℃.
The usage quantity of each composition is: the composition (a) that uses with respect to per 1 gram composition (c) is preferably 0.0001-100mmol, and the spy is preferably 0.001-10mmol.Use composition (b) to be preferably 0.0001-100mmol with respect to every 1g composition (c) in addition, and the spy is preferably 0.001-10mmol.
The product of contact of Zhi Bei composition (a), composition (b) and composition (c) can be not purified and be used like this, perhaps uses behind the purifying.When composition (a) or composition (b) are the dichloro type, then preferably add again by the represented organo-aluminium compound (composition (d)) of general formula (22) down.
AlR 8 3 (22)
In addition, in order to remove the impurity in composition (c), polymer solvent and the alkene, can add composition (d).
R in general formula (22) 8Represent C independently of one another 1-20Alkyl.Used C 1-20The example of alkyl comprises methyl, ethyl, n-propyl, sec.-propyl, normal-butyl; Isobutyl-, sec-butyl, the tertiary butyl, n-pentyl, isopentyl, 2-methyl butyl, neo-pentyl, tert-pentyl, n-hexyl, isohexyl, 3-methyl amyl, 4-methyl amyl, new hexyl, 2,3-dimethylbutyl, 2, the 2-dimethylbutyl, 4-methyl-2-amyl group, 3,3-dimethyl-2-butyl, 1,1-dimethylbutyl, 2,3-dimethyl-2-butyl, n-pentyl, isopentyl, n-octyl, n-nonyl, positive decyl, dodecyl, n-tetradecane base, n-hexadecyl, Octadecane base, phenyl and cyclohexyl.
The specific examples of composition (d) comprises trimethyl aluminium, hydrogenation dimethyl aluminium, triethyl aluminum, diethyl aluminium hydride, tri-n-n-propyl aluminum, hydrogenation di aluminium, triisopropylaluminiuand, hydrogenation di-isopropyl aluminium, three n-butylaluminum, hydrogenation di-n-butyl aluminium, triisobutyl aluminium, diisobutylaluminium hydride, tri-tert aluminium, hydrogenation di-t-butyl aluminium, tri-n-hexyl aluminum, hydrogenation di-n-hexyl aluminium, three isohexyl aluminium, hydrogenation two isohexyl aluminium, tri-n-octylaluminium, hydrogenation di-n-octyl aluminium, three iso-octyl aluminium and hydrogenation diisooctyl aluminium.
The catalyzer that comprises composition (a), composition (b), composition (c) and composition (d) is to make by composition (a), composition (b), composition (c) and composition (d) are contacted.Can enumerate following method: the product of contact of composition (a) and composition (d) is added the method that adds composition (b) in the composition (c) then; Composition (a) is added in the composition (c), adds the method for the product of contact of composition (b) and composition (d) then; The product of contact of composition (a) and composition (d) is added in the composition (c), adds the method for the product of contact of composition (b) and composition (d) then; Composition (a) is added to the product of contact of composition (c) and composition (d), adds the method for composition (b) then; Composition (a) and product of contact (d) are added in the product of contact of composition (c) and composition (d), add the method for composition (b) then; Composition (a) is added in the product of contact of composition (c) and composition (d), adds the method for the product of contact of composition (b) and composition (d) then; The product of contact of composition (a) and composition (d) is added in the product of contact of composition (c) and composition (d), adds the method for the product of contact of composition (b) and composition (d) then; Composition (b) is added in the product of contact of composition (a) and composition (d), adds the method for composition (c) then; The product of contact of composition (b) and composition (d) is added in the composition (a), adds the method for composition (c) then; The product of contact of composition (b) and composition (d) is added in the product of contact of composition (a) and composition (d), adds the method for composition (c) then; Composition (b) is added in the composition (a), adds the method for the product of contact of composition (c) and composition (d) then; Composition (b) is added in the product of contact of composition (a) and composition (d), adds the method for the product of contact of composition (c) and composition (d) then; The product of contact of composition (b) and composition (d) is added in the composition (a), adds the method for the product of contact of composition (c) and composition (d) then; The product of contact of composition (b) and composition (d) is added in the product of contact of composition (a) and composition (d), adds the method for the product of contact of composition (c) and composition (d) then; Composition (b) is added in the product of contact of composition (a) and composition (c), adds the method for composition (d) then; Composition (a) is added in the product of contact of composition (b) and composition (c), adds the method for composition (d) then; Composition (c) is added in the product of contact of composition (a) and composition (b) and adds the method for composition (d) then; The product of contact of composition (a) and composition (b) is added in the composition (c), adds the method for composition (d) then; The product of contact of composition (a) and composition (c) is added in the composition (b), add the method for composition (d) then; The product of contact of composition (b) and composition (c) is added in the composition (a), adds the method for composition (d) then; And the product of contact of composition (b) and composition (c) is added in the product of contact of composition (a) and composition (c), add the method for composition (d) then.
When the integral molar quantity of composition (a) and composition (b) was 1 mole, the amount that is used for composition of the present invention (d) was preferably the 0.1-10000 mole and especially is preferably the 1-1000 mole.
Composition (a) and the composition (b) of containing of the present invention, also comprises except the catalyzer that contains composition (a), composition (b) and composition (c) as the catalyzer example of principal constituent:
Contain the catalyzer of composition (a), composition (b) and composition (d), and further wrap aqueous catalyzer;
The catalyzer that comprises composition (a), composition (b) and organo-magnesium compound (composition (e)), organo-magnesium compound is by general formula (26) expression down
MgR 9 2 (26)；
The catalyzer of further inclusion compound (d);
Comprise composition (a), composition (b) and by the catalyzer of the organolithium compound (composition (f)) of general formula (27) expression down,
LiR 10 (27)
The catalyzer that further comprises composition (d);
Comprise composition (a), composition (b) and by general formula (28) expression down and/or by the catalyzer of the aikyiaiurnirsoxan beta (aluminooxane) (composition (g)) of general formula (29) expression:
[chemical formula 8]
[chemical formula 9]
Figure DEST_PATH_S2006800478765D00331
The catalyzer that further comprises composition (d), composition (e) and/or composition (f);
Comprise composition (a), composition (b) and at least a protic acid salt (composition (h)) that is selected from by following general formula (30) expression
[R 12R 13 m-1M 5H][M 6Ar 4] (30)
The lewis acid (composition (i)) of following formula (31) expression
[C][M 6Ar 4] (31)
Or by the metal-salt (composition (j)) that descends general formula (32) expression
[M 7L 3 n][M 6Ar 4] (32)
The catalyzer of salt, further comprise the catalyzer of composition (d) and/or composition (g);
Comprise composition (a) and by the following catalyzer of the Lewis acid (composition (k)) of general formula (33) expression,
M 8Ar 3 (33)
The catalyzer that further comprises composition (d) and/or composition (g);
Comprise composition (a), composition (b), composition (k) and at least a composition (h) that is selected from, the catalyzer of the salt of composition (i) and composition (j) further comprises the catalyzer of composition (d) and/or composition (g);
The catalyzer that comprises composition (a), composition (b) and magnesium chloride (composition (l)) further comprises the catalyzer of composition (d) and/or composition (g);
The catalyzer that comprises composition (a), composition (b) and sulfonate (composition (m)) further comprises the catalyzer of composition (d) and/or composition (g);
The catalyzer that comprises composition (a), composition (b) and carboxylic acid (composition (n)) further comprises the catalyzer of composition (d) and/or composition (g);
The catalyzer that contains composition (a), composition (b), composition (g) and inorganic oxide (composition (o)) further comprises the catalyzer of composition (d), composition (e) and/or composition (f);
Comprise composition (a), composition (b), composition (o) and at least a catalyzer that is selected from the salt of composition (h), composition (i) and composition (j), further contain the catalyzer of composition (d), composition (e) and/or composition (f);
Contain composition (a), composition (b) and inorganic halides (composition (p)) and at least a catalyzer that is selected from the salt of composition (h), composition (i) and composition (j), further contain the catalyzer of composition (d), composition (e) and/or composition (f);
And the catalyzer that contains composition (a), composition (b) and clay mineral (composition (q)) and composition (d).
The present invention use by the R in the composition (e) of general formula (26) expression 9Represent halogen atom or C independently of one another 1-20Alkyl, its condition are at least one R 9Be C 1-20Alkyl.
R in the composition (e) 9The example of employed halogen atom comprises fluorine atom, chlorine atom, bromine atoms and iodine atom.C 1-20The example of alkyl comprises methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, sec-butyl, the tertiary butyl, n-pentyl, isopentyl, the 2-methyl butyl, neo-pentyl, tert-pentyl, n-hexyl, isohexyl, the 3-methyl amyl, the 4-methyl amyl, new hexyl, 2, the 3-dimethylbutyl, 2, the 2-dimethylbutyl, 4-methyl-2-amyl group, 3,3-dimethyl-2-butyl, 1, the 1-dimethylbutyl, 2,3-dimethyl-2-butyl, n-pentyl, isopentyl, n-octyl, n-nonyl, positive decyl, dodecyl, the n-tetradecane base, n-hexadecyl, Octadecane base, phenyl and cyclohexyl.
The specific examples of composition (e) comprises dimethyl magnesium, magnesium ethide, dibutylmagnesium, ethyl-butyl magnesium, methylmagnesium-chloride, methylmagnesium-bromide, ethyl-magnesium-chloride, ethyl-magnesium-bromide, isopropyl-magnesium chloride, bromination isopropyl-magnesium, butyl magnesium chloride and butyl magnesium bromide.
When the mole total amount of composition (a) and composition (b) was 1 mole, the amount that is used for composition of the present invention (e) was preferably the 0.1-10000 mole, and was preferably the 1-1000 mole especially.
The R that is used for the composition (f) by general formula (27) expression of the present invention 10Be C 1-20Alkyl.
R in composition (f) 10Used C 1-20The example of alkyl comprises methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, sec-butyl, the tertiary butyl, n-pentyl, isopentyl, the 2-methyl butyl, neo-pentyl, tert-pentyl, n-hexyl, isohexyl, the 3-methyl amyl, the 4-methyl amyl, new hexyl, 2, the 3-dimethylbutyl, 2, the 2-dimethylbutyl, 4-methyl-2-amyl group, 3,3-dimethyl-2-butyl, 1, the 1-dimethylbutyl, 2,3-dimethyl-2-butyl, n-pentyl, isopentyl, n-octyl, n-nonyl, positive decyl, dodecyl, the n-tetradecane base, n-hexadecyl, Octadecane base, phenyl and cyclohexyl.
The specific examples of composition (f) comprises lithium methide, lithium ethide and butyllithium.
With respect to 1 mole of the integral molar quantity of composition (a) and composition (b), the amount of used composition (f) is preferably the 0.1-10000 mole among the present invention, and preferred especially 1-1000 mole.
The R that is used for the composition (g) by general formula (28) or (29) expression of the present invention 11Represent hydrogen atom or C independently of one another 1-20Alkyl, k are 0-60.
The R of composition (g) 11In used C 1-20The alkyl example comprises methyl, ethyl, propyl group, sec.-propyl, isobutyl-and the tertiary butyl.Composition (g) can contain monomer, dimer and the oligopolymer of organo-aluminium compound.
Composition (g) usually can be by reacting organo-aluminium compound and water or the hydrate of organo-aluminium compound and salt or oxide compound being reacted make in organic solvent in organic solvent.The material of being produced by usual method also can use.
With respect to 1 mole of the integral molar quantity of composition (a) and composition (b), the amount that is used for composition of the present invention (g) is preferably the 0.01-1000000 mole, is preferably the 1-100000 mole especially.
[the R that is used for the composition (h) by general formula (30) expression of the present invention 12R 13 K-1M 5H] be positively charged ion, and [M 6Ar 4] be negatively charged ion.
M in the composition (h) 5Be the element that is selected from 15 or 16 families in the periodictable, and R 12Be C 1-30Alkyl, R 13Be hydrogen atom or C independently of one another 1-30Alkyl, work as M 5When being the element of 15 families, m is 3, work as M 5When being the element of 16 families, m is 2, M 6Be boron, aluminium or gallium, Ar is C independently of one another 1-20Halogenated aryl.
The R of composition (h) 12And R 13Used C 1-30The example of alkyl comprises methyl, ethyl, n-propyl, sec.-propyl, allyl group, normal-butyl, isobutyl-, sec-butyl, the tertiary butyl, n-pentyl, isopentyl, the 2-methyl butyl, the 1-methyl butyl, the 1-ethyl propyl, neo-pentyl, tert-pentyl, cyclopentyl, n-hexyl, isohexyl, the 3-methyl amyl, the 4-methyl amyl, new hexyl, 2, the 3-dimethylbutyl, 2, the 2-dimethylbutyl, 4-methyl-2-amyl group, 3,3-dimethyl-2-butyl, 1, the 1-dimethylbutyl, 2,3-dimethyl-2-butyl, cyclohexyl, n-heptyl, suberyl, the 2-methylcyclohexyl, the 3-methylcyclohexyl, the 4-methylcyclohexyl, n-octyl, iso-octyl, 1,5-dimethyl hexyl, the 1-methylheptyl, the 2-ethylhexyl, uncle's octyl group, 2, the 3-Dimethylcyclohexyl, 2-(1-cyclohexenyl) ethyl, n-nonyl, positive decyl, isodecyl, geranyl, the n-undecane base, dodecyl, cyclo-dodecyl, the n-tridecane base, the n-tetradecane base, the Pentadecane base, n-hexadecyl, the n-heptadecane base, the Octadecane base, the NSC 77136 base, the NSC 62789 base, the heneicosane base, the n-docosane base, the n-tricosane base, oil base Shan Yu base, phenyl, neighbour-tolyl, between-tolyl, right-tolyl, the 2-ethylphenyl, the 3-ethylphenyl, the 4-ethylphenyl, the 2-isopropyl phenyl, the 3-isopropyl phenyl, the 4-isopropyl phenyl, the 2-tert-butyl-phenyl, the 4-n-butylphenyl, the 4-secondary butyl phenenyl, the 4-tert-butyl-phenyl, 2, the 3-xylyl, 2, the 4-xylyl, 2, the 5-xylyl, 2, the 6-xylyl, 3, the 4-xylyl, 3, the 5-xylyl, 2,6-diethyl phenyl, 2-sec.-propyl-6-aminomethyl phenyl, the 2-chloro-phenyl-, the 3-chloro-phenyl-, the 4-chloro-phenyl-, the 2-bromophenyl, the 3-bromophenyl, the 4-bromophenyl, the 2-p-methoxy-phenyl, the 3-p-methoxy-phenyl, the 4-p-methoxy-phenyl, the 2-ethoxyl phenenyl, the 3-ethoxyl phenenyl, the 4-ethoxyl phenenyl, the 1-naphthyl, the 2-naphthyl, the 1-fluorenyl, the 2-fluorenyl, the 3-fluorenyl, the 4-fluorenyl, 2,3-indenes-5-base, the 2-xenyl, 4-xenyl and to the trimethyl silyl phenyl.R 12And R 13Can be connected to each other.
Used C among the Ar of composition (h) 6-20Halogenated aryl comprises pentafluorophenyl group.
The specific examples of composition (h) comprises diethyl oxygen four (pentafluorophenyl group) borate, dimethyl oxygen four (pentafluorophenyl group) borate, tetramethylene oxygen four (pentafluorophenyl group) borate, hydronium(ion) (hydronium) four (pentafluorophenyl group) borate, trimethyl ammonium four (pentafluorophenyl group) borate, three (normal-butyl) ammonium four (pentafluorophenyl group) borate, N, N-dimethyl puratized agricultural spray four (pentafluorophenyl group) borate, diethyl oxygen four (pentafluorophenyl group) aluminate, dimethyl oxygen four (pentafluorophenyl group) aluminate, tetramethylene oxygen four (pentafluorophenyl group) aluminate, hydronium(ion) four (pentafluorophenyl group) aluminate, N, N-dimethyl puratized agricultural spray four (pentafluorophenyl group) aluminates and three (normal-butyl) ammonium four (pentafluorophenyl group) aluminate.
[C] in the composition (i) of the used general formula (31) of the present invention expression be carbocation or (tropilium) positively charged ion.
The specific examples of composition (i) comprise four (pentafluorophenyl group) boric acid trityl ester, four (pentafluorophenyl group) aluminic acid trityl ester, Four (pentafluorophenyl group) borate and
Figure DEST_PATH_S2006800478765D00363
Four (pentafluorophenyl group) aluminate.
The present invention used by the M in the represented composition (j) of general formula (32) 7It is the positively charged ion of lithium atom, iron atom and silver atoms.L 3Be Lewis base, such as, ether, aliphatic amine, aromatic amine or phosphine; Or replacement or unsubstituted cyclopentadienyl and m is 0≤m≤2.
The specific examples of composition (j) comprises that lithium salts is such as four (pentafluorophenyl group) lithium tetraborate, four (pentafluorophenyl group) lithium aluminates or their ether complexes; Ferrocene salt such as ferrocene four (pentafluorophenyl group) borate or ferrocene four (pentafluorophenyl group) aluminate; With silver salt such as four (pentafluorophenyl group) boric acid silver or four (pentafluorophenyl group) aluminic acid silver.
The M that is used for the composition (k) of general formula of the present invention (33) expression 9Be boron or aluminium.The specific examples of composition (k) comprises three (pentafluorophenyl group) borine, three (2,3,5,6-tetrafluoro phenyl) borine, three (2,3,4,5-tetrafluoro phenyl) borine, three (3,4, the 5-trifluorophenyl) borine, two (pentafluorophenyl group) borine and three (3,4, the 5-trifluorophenyl) aluminium of phenyl.
Being used for composition of the present invention (m) is sulfonate, and the example of sulfonate comprises the trifluoromethanesulfonic acid lithium, trifluoromethanesulfonic acid sodium, trifluoromethanesulfonic acid potassium, two (trifluoromethanesulfonic acid) calcium, two (trifluoromethanesulfonic acid) barium, three (trifluoromethanesulfonic acid) titanium, four (trifluoromethanesulfonic acid) titanium, four (trifluoromethanesulfonic acid) zirconium, four (trifluoromethanesulfonic acid) hafnium, five (trifluoromethanesulfonic acid) niobium, five (trifluoromethanesulfonic acid) tantalum, three (trifluoromethanesulfonic acid) iron, silver trifluoromethanesulfonate, three (trifluoromethanesulfonic acid) boron, three (trifluoromethanesulfonic acid) aluminium, three (trifluoromethanesulfonic acid) gallium, four (trifluoromethanesulfonic acid) tin, penta fluoro benzene sulfonic acid lithium, the penta fluoro benzene sodium sulfonate, the penta fluoro benzene potassium sulfonate, two (penta fluoro benzene sulfonic acid) magnesium, two (penta fluoro benzene sulfonic acid) calcium, two (penta fluoro benzene sulfonic acid) barium, three (penta fluoro benzene sulfonic acid) titanium, four (penta fluoro benzene sulfonic acid) zirconium, four (penta fluoro benzene sulfonic acid) hafnium, five (penta fluoro benzene sulfonic acid) niobium, five (penta fluoro benzene sulfonic acid) tantalum, three (penta fluoro benzene sulfonic acid) iron, penta fluoro benzene sulfonic acid silver, three (penta fluoro benzene sulfonic acid) boron, three (penta fluoro benzene sulfonic acid) aluminium, three (penta fluoro benzene sulfonic acid) gallium, four (penta fluoro benzene sulfonic acid) tin, two (trifluoromethanesulfonic acid) magnesium, five (trifluoromethanesulfonic acid) niobium, two (penta fluoro benzene sulfonic acid) magnesium, four (penta fluoro benzene sulfonic acid) titanium and five (penta fluoro benzene sulfonic acid) niobium.
Being used for composition of the present invention (n) is carboxylic acid.The example of carboxylic acid comprises trifluoroacetic acid, trichoroacetic acid(TCA), tribromoacetic acid, pentafluorobenzoic acid, tetrafluorobenzoic aid, 2,4-(trifluoromethyl) phenylformic acid and pentafluorophenyl group acetate.
With respect to 1 mole of the integral molar quantity of composition (a) and composition (b), the amount that is used for composition of the present invention (h), composition (i), composition (j), composition (k), composition (m) and composition (n) is preferably the 0.1-1000 mole, and preferred especially 0.3-100 mole.
Being used for composition of the present invention (o) is magnesium chloride.Magnesium chloride is to be prepared by usual method.With respect to 1 mole of the integral molar quantity of composition (a) and composition (b), the consumption of composition (o) is preferably 0.01-10000kg, preferred especially 0.1-1000kg.In addition, form in the system of magnesium chloride when the polymerization of using halo organoaluminum and organic-magnesium etc. or Preparation of Catalyst, and be used for polymerization.
Being used for composition of the present invention (p) is inorganic oxide.Inorganic oxide preferably has the granularity of 1-300 μ m.The multi-hole fine particle that particularly has 3-200 μ m granularity is preferred, because this particle is easy to handle in Preparation of Catalyst and polymerization technique.The specific examples of inorganic oxide comprises the oxide compound of typical element, such as silicon oxide, aluminum oxide or magnesium oxide; The inorganic oxide of transition metal such as titanium oxide or zirconium white; And such as silica-alumina or silicon oxide-magnesian mixture.These inorganic oxides contain the salt of basic metal and alkaline-earth metal usually such as Na 2O, K 2CO 3Or BaSO 4As impurity.The state that fine particulate inorganic oxides can contain above-mentioned impurity uses, but the inorganic oxide that preferably uses the operation of removing these impurity in advance to obtain.This porous fine-grannular inorganic oxide depends on its kind and has different character with production method.In the present invention, has specific surface area 10-1000m 2/ g, especially 50-800m 2The inorganic oxide of/g and pore volume 0.1-3ml/g is preferred, because this inorganic oxide can support the carrier components of a large amount of transistion metal compounds.On demand, these inorganic oxides use after the calcining down at 100-1000 ℃ under low pressure or air-flow.
The hydroxyl of these inorganic oxides can be replaced by halogen.Replace with halogen inorganic oxide hydroxyl method preferably with have and can react with the reagent of the halogen of surface hydroxyl exchange.The example of reagent comprises halogen, such as fluorine, chlorine, bromine or iodine; Hydrogen halide such as hydrogen fluoride, hydrogenchloride, hydrogen bromide or hydrogen iodide; And halide-containing, such as phosgene, thionyl chloride, Neutral ammonium fluoride, ammonium chloride, ammonium iodide, tetracol phenixin, chloroform or freonll-11, these mineral compound can be 100～1000 ℃ of following heat treated under low pressure or air-flow, and this is in order to remove the by product H of generation after partly or entirely hydroxyl is replaced by halogen 2O.
With before other catalyst component contacts, inorganic oxide in advance the metallizing thing to contact this be in order to carry out-aftertreatment of OH residue.Used metallic compound is not particularly limited, and preferably uses composition (d), composition (e) and/or composition (f).The contact method of inorganic oxide metallizing thing is not particularly limited.The example of method comprises: can not the dissolved oxygen thing and in can the organic solvent of dissolution of metals compound with the method for suspended state contact; The method that in oxide compound and metallic compound can both the dissolved organic solvents, contacts; And the method that under solvent-free substantially state, contacts by ball milling or similar method.
The example that preparation is used for the method for the catalyzer that comprises composition (a), composition (b), composition (g) and composition (p) of the present invention comprises: composition (g) and composition (p) are contacted, add the method for composition (a) and composition (b) then; Composition (a), composition (b) and composition (g) are contacted, add the method for composition (p) then; And composition (a) composition (g) and composition (p) are contacted, add the method for composition (b) then.
In the catalyzer that contains composition (a), composition (b), composition (g) and composition (p), with respect to 1 gram composition (p), the amount of composition (a) is preferably the 0.005-1 mmole, preferred especially 0.05-0.5 mmole.When the Al amount in being contained in composition (g) is the ratio of 10-200 mole with respect to a mol composition (a), then can obtain the better polymerization activity, this is preferred.
The present invention uses contain composition (a), composition (b), composition (p) and be selected from Preparation of catalysts method example at least a in composition (h), composition (i) and the composition (j) comprises, composition (p) is contacted with at least a salt that is selected from composition (h), composition (i) and the composition (j), add the method for composition (a) and composition (b) then; Composition (a), composition (b) and at least a salt that is selected from composition (h), composition (i) and composition (j) are contacted, add the method for composition (p) then; Composition (a), composition (p) and at least a salt that is selected from composition (h), composition (i) and composition (j) are contacted, add composition (b) then.
In containing composition (a), composition (b), composition (p) and at least a catalyzer that is selected from the salt in composition (h), composition (i) and the composition (j), at least a amount that is selected from the anionic component of the salt in composition (h), composition (i) and the composition (j) is the 0.01-1000 mole with respect to 1 mol composition (a), can obtain good polymerization activity like this, be preferred.Particularly preferred amount is the 0.2-500 mole.With respect to 1kg composition (p), the amount of composition (a) is preferably in the 0.001-1 molar range, is preferably the 0.001-0.5 mole especially, and further preferred 0.001-0.3 mole.
Being used for composition of the present invention (q) is inorganic halides.The example of inorganic halides comprises the halogenide of alkaline-earth metal, and such as magnesium chloride, and the halogenide of the element of periodictable 13 families is such as aluminum chloride.
Being used for composition (a), composition (b), composition (q) and at least a Preparation of catalysts method example that is selected from the salt of composition (h), composition (i) and composition (j) of containing of the present invention comprises: composition (q) and at least a salt that is selected from composition (h), composition (i) and composition (j) are contacted, add the method for composition (a) and composition (b) then; Composition (a) and composition (b) are contacted with at least a salt that is selected from composition (h), composition (i) and the composition (j), add the method for composition (q) then; And composition (a) and composition (q) are contacted with at least a salt that is selected from composition (h), composition (i) and the composition (j), add the method for composition (b) then.
In containing composition (a), composition (b), composition (q) and at least a catalyzer that is selected from the salt in composition (h), composition (i) and the composition (j), when at least a amount that is selected from the anionic component of the salt in composition (h), composition (i) and the composition (j) is the 0.01-1000 mole with respect to 1 mol composition (a), can obtain good polymerization activity, be preferred.Particularly preferred amount is the 0.2-500 mole.With respect to 1kg composition (q), the amount of composition (a) is preferably in the scope of 0.001-1 mole, is preferably the 0.001-0.5 mole especially, and 0.001-0.3 mole more preferably.
Composition in the present invention (q) is a clay mineral.Clay mineral is to contain the fine particle of microcrystal silicon hydrochlorate as principal constituent.Most of clay pits have the feature of laminate structure on its structure, and the negative charge of different sizes is arranged in layer.Clay mineral obviously is different from the metal oxide with three-dimensional structure in this, such as silicon oxide or aluminum oxide.These clay minerals can be divided into agalmatolite, kaolin, dickite and talcs (negative charge of each chemical formula is about 0), smectites (negative charge of each chemical formula is about 0.25-0.6) usually, vermiculite class (negative charge of each chemical formula is about 0.6-0.9), mica group (negative charge of every chemical formula is about 1) and fragility mica group (negative charge of each chemical molecular formula is about 2), this depends on the size of layer charge.Above-mentioned each class comprises various differed clay minerals.The clay minerals that belongs to smectites comprises montmorillonite, beidellite, saponite and hectorite.These clay minerals are naturally occurring, but also can make the clay mineral that contains small amount of impurities through the synthetic method.The clay mineral that the present invention can use all natural clay minerals described herein and artificial synthesis to make, and also can use all material that belongs to the clay mineral definition in addition, even the material of not pointing out in the above.These clay minerals can its two or more form of mixtures use.
Composition of the present invention (q) can directly use, or can use after newly adding entry and planar water, or uses after the hot processed carrying out.
Composition (q) preferably carries out chemical treatment such as acid treatment, and alkaline purification or salt are handled.Use the acid treatment of sour all example hydrochloric acids, sulfuric acid, nitric acid, acetate or oxalic acid to remove the lip-deep impurity of composition (q), increased surface-area by part or all of positively charged ion such as Al, Fe or the Mg of stripping in crystalline structure in addition.The alkaline purification of use alkali such as sodium hydroxide has destroyed the crystalline structure of composition (q) to cause structural modification.Use the salt of salt to handle and increase swelling property and interfloor distance, the salt of described use such as lithium chloride, sodium phosphate, sodium sulfate, sodium acetate, formyl sodium, Trisodium Citrate, SODIUMNITRATE, sodium oxalate, magnesium chloride, sal epsom, trimagnesium phosphate, magnesium perchlorate, magnesium oxalate, magnesium nitrate, magnesium acetate, Magnesium succinate, Tai-Ace S 150, aluminum phosphate, oxalic acid aluminium or aluminum nitrate by tradable ion with the interlayer of other ionic replacement composition (r).
Being used for the catalyzer that contains composition (a), composition (b), composition (q) and composition (d) of the present invention is to make by composition (a) is contacted at organic solvent with the product of contact of composition (q) and composition (d) with composition (b).The amount of used various compositions is that composition (a) is preferably the 0.0001-100 mmole, especially is preferably the 0.001-100 mmole in per 1 gram composition (q); The consumption of composition (b) is preferably 0.0001～100mmol according to every 1g composition (c) meter, is preferably 0.001～10mmol especially; The consumption of composition (d) is preferably the 0.1-10000 mole for 1 mole in the integral molar quantity of composition (a) and composition (b), and is preferably the 1-1000 mole especially.
In the present invention, the preparation of polyvinyls can be carried out by the following method, use the catalyst component contain composition (a) and composition (b) with single-stage polymerization or multistage polymerization polymerising ethylene and choose wantonly have 3 or the method (method 1) of the alkene of more a plurality of carbon atoms.On the other hand, the preparation of polyvinyls can be undertaken by following method: (step 1) use contain composition (a) as the catalyst component polymerising ethylene of principal constituent and the optional alkene that 3 or more a plurality of carbon atoms are arranged to produce polyvinyls, then (step 2) in the presence of the polyvinyls that obtains in 1 in steps, continue to add contain composition (b) as the catalyst component of principal constituent with polymerising ethylene and choose wantonly have 3 or the method (method 2) of the alkene of more carbon atoms.
In preparation method of the present invention used have 3 or the example of the alkene of more a plurality of carbon atoms comprise alpha-olefin such as propylene, 1-butylene, 1-hexene, 1-octene, 1-decene, 1-dodecylene, tetradecene, cetene, 1-vaccenic acid, 1-eicosylene, 4-methyl-1-pentene, 3-methyl-1-butene or vinyl cycloalkane; Cyclic olefin such as norbornylene or norbornadiene; Diene such as divinyl or 1, the 4-hexadiene; And vinylbenzene.These alkene can its two kinds or more kinds of mixture uses.
The embodiment of method 1 that is used for preparation method of the present invention is as described below.
Polymerizing condition in method 1 such as polymerization temperature, polymerization time, polymerization pressure and monomer concentration all are not particularly limited.Polymerization temperature is preferably-100～120 ℃.Special consideration productivity is preferably carried out polymerization in 20～120 ℃ of scopes, and more preferably 60～120 ℃.Polymerization time is preferably in 10 seconds～20 hours scopes.Polymerization pressure is preferably in common pressure-300MPa scope.Use hydrogen or analogue can control molecular weight at polymerization time.Polymerization arbitrarily interrupter method, semi-continuous process or continuous processing carry out and can be by changing polymerizing condition with two steps or more multistep carry out.Polyvinyls can be by separating from polymer solvent with usual method after finishing polymerization and reclaiming, and is dry then and make.
Polymerization in method 1 can solution state, suspended state or gaseous state carry out.Particularly, when polymerization is carried out with suspended state, can produce olefin polymer with steady state good efficiencies ground with equigranular.Solvent for use can be that any solvent is as long as it is general organic solvent.The specific examples of organic solvent comprises benzene,toluene,xylene, propane, Trimethylmethane, pentane, hexane, heptane, hexanaphthene and gasoline.Alkene such as propylene itself, 1-butylene, 1-hexene or 1-octene also can be used as solvent.
The embodiment of used method 2 is specified in down in the production method of the present invention.
Containing composition (a) comprises as the example of the catalyzer of principal constituent:
The catalyzer that contains composition (a) and composition (d) further contains the catalyzer of water;
The catalyzer that contains composition (a) and composition (e) further contains the catalyzer of composition (d);
The catalyzer that contains composition (a) and composition (g) further contains the catalyzer of composition (d);
Contain composition (a) and at least a catalyzer that is selected from the salt in composition (h) composition (i) and the composition (j), further contain the catalyzer of composition (d);
The catalyzer that contains composition (a) and composition (k) further contains the catalyzer of composition (d);
The catalyzer that contains composition (a) and magnesium chloride (composition (l)) further contains the catalyzer of composition (d);
The catalyzer that contains composition (a), composition (g) and composition (o) further contains the catalyzer of composition (d);
Contain composition (a), composition (l) and at least a catalyzer that is selected from the salt in composition (h), composition (i) and the composition (j), further contain the catalyzer of composition (d);
The catalyzer that contains composition (a), composition (q) and composition (d);
The catalyzer that contains composition (a) and composition (c); And the catalyzer that further contains composition (d).
Contain the catalyzer of composition (a) and composition (c), and the catalyzer that further contains composition (d) is preferred the use.
The catalyzer that contains composition (a) and composition (c) can make by composition (a) is contacted in organic solvent with composition (c).Can use composition (c) is added to the method in the composition (a) and composition (a) is added to method in the composition (c).
The example of solvent contact comprises aliphatic hydrocrbon such as butane, pentane, hexane, heptane, octane, nonane, decane, pentamethylene or hexanaphthene; Aromatic hydrocarbons such as benzene, toluene or dimethylbenzene; Ether such as ether or just-butyl ether; Halon such as methylene dichloride or chloroform; 1, the 4-diox; Acetonitrile or tetrahydrofuran (THF).
The contact temperature is preferably selected between 0-200 ℃.
The amount of every kind of used composition is: the composition (a) that every 1g composition (c) uses is the 0.0001-100 mmole, is preferably the 0.001-10 mmole.
So the product of contact of the composition (a) of preparation and composition (c) can directly be used and without purifying but also can use behind the purifying.(a) is dichloride when composition, then preferably adds composition (d) again.In addition, can add composition (d), remove impurity in polymer solvent and the alkene with from composition (c).
The catalyzer that contains composition (a), composition (c) and composition (d) can make by composition (a) composition (c) is contacted in organic solvent with composition (d).The example of contact method comprises composition (d) is added to method in the product of contact of composition (a) and composition (c); The product of contact of composition (a) and composition (c) is added to method in the composition (d); Composition (c) is added to the method in the product of contact of composition (a) and composition (d); The product of contact of composition (a) and composition (d) is added to method in the composition (c); The product of contact of composition (c) and composition (d) is added to the method in the product of contact of composition (a) and composition (d); Composition (a) is added to the method in the product of contact of composition (c) and composition (d); And the product of contact of composition (a) and composition (d) is joined method in the product of contact of composition (c) and composition (d).
In the first step of method 2, polymerization temperature is preferably between-100～120 ℃.Consider productivity especially, preferably in 20～120 ℃ of scopes, carry out polymerization, more preferably in 60～120 ℃, carry out polymerization.Polymerization time is preferably in 10 seconds-20 hours scopes.Polymerization pressure is preferably at normal pressure-300MPa.Ethene and have 3 or the reinforced ratio of the alkene of more carbon atoms be that to make the alkene (mol ratio) of ethene/have 3 or more carbon atoms be 0-200, preferably 3-100 is more preferred from 5-50.When polymerization, use hydrogen or analogue may command molecule amount.Polymerization can be any discontinuous method, semi-continuous process or continuation method are carried out, and can by change polymerizing condition with 2 or multistep carry out.
Polymerization can solution state in the step I of method 2, and suspended state or gas phase state carry out.Especially, when polymerization is when carrying out with suspended state, good efficiencies production that then can steady state has the long chain branching ethylene copolymer of single-size shape.Used solvent can be that any solvent is as long as it is general organic solvent.The specific embodiment of organic solvent comprises benzene,toluene,xylene, propane, Trimethylmethane, pentane, hexane, heptane, hexanaphthene and gasoline.Alkene such as propylene itself, 1-butylene, 1-hexene or 1-octene also can be used as solvent.
Containing composition (b) comprises as the example of the catalyzer of principal constituent: contain the catalyzer of composition (b) and composition (d), further contain the catalyzer of water;
The catalyzer that contains composition (b) and composition (e) further contains the catalyzer of composition (d);
The catalyzer that contains composition (b) and composition (g) further contains the catalyzer of composition (d);
Contain composition (b) and at least a catalyzer that is selected from the salt in composition (h), composition (i) and the composition (j), further contain the catalyzer of composition (d);
The catalyzer that contains composition (b) and composition (k) further contains the catalyzer of composition (d);
The catalyzer that contains composition (b) and composition (l) further contains the catalyzer of composition (d);
The catalyzer that contains composition (b), composition (g) and composition (o) further contains the catalyzer of composition (d);
Contain composition (b), composition (l) and at least a catalyzer that is selected from the salt of composition (h), composition (i) and composition (j), further contain the catalyzer of composition (d);
The catalyzer that contains composition (b), composition (q) and composition (d);
The catalyzer that contains composition (b) and composition (c), and the catalyzer that further contains composition (d).
The catalyzer that contains composition (b) and composition (d) can preferably use.
Can be used in the method for producing 2 of the present invention, after the polyvinyls of step I is produced, to comprise the above-mentioned composition (b) that contains is not particularly limited as the method that the catalyzer of the Step II of the above-mentioned composition of principal constituent is added to polymerization system, the example of aforesaid method is included in preparation and removes residual pressure in polymerization system behind the polyvinyls, replace system inside with non-active gas, add the method for each composition in the system separately then; Behind the preparation polyvinyls, remove the residual pressure in polymerization system,, contact each composition in advance, be added to the method in the system then with non-active gas displacement system inside; Behind the preparation polyvinyls, remove the residual pressure in the polymerization system, then every kind of composition is added to the method for replacing system inside in each individual system without non-active gas; Behind the preparation polyvinyls, remove the residual pressure in the polymerization system, contact each composition in advance, and, be added to the method in the system then without non-active gas displacement system inside; After preparing polyvinyls, directly each composition is joined the method for not removing residual gas in the system separately; Behind the preparation polyvinyls, do not remove residual gas and directly contact each composition, join the method in the system then.Temperature during interpolation is not particularly limited, and can add in the scope of-50 ℃～solvent boiling point.
In method 2, after in step I, preparing polyvinyls, after will containing composition (b) and adding in the polymerization system as the catalyzer of the Step II of principal constituent, up to polymerising ethylene and optional have 3 or time of the alkene of more carbon atoms be not particularly limited, be generally 1 second-24 hours.Add contain composition (b) as the catalyzer of principal constituent to polymerization system and immediately polymerising ethylene and choose wantonly have 3 or the method for the alkene of more carbon atoms; And add contain composition (b) as the catalyzer of principal constituent to polymerization system and through after the above-mentioned time, polymerising ethylene and choose wantonly have 3 or the method for the alkene of more carbon atoms.Temperature is not particularly limited in this case, and this method can be carried out under the scope of-50 ℃～solvent boiling point.
In Step II, polymerization temperature is preferably-100～120 ℃.Consider that especially the preferred polymerization of productivity is 20～120 ℃ of scopes and is more preferably under in 60～120 ℃ of scopes and carries out.Polymerization time is preferably between 10 seconds～20 hours.Polymerization pressure is preferably in normal pressure～300MPa scope.Ethene and have 3 or the charge proportion of the alkene of more carbon atoms be that the alkene (mol ratio) of ethene/have 3 or more carbon atoms be 0-200, preferably 0.05-100, more preferably 0.1-50.Use hydrogen or analogue can control molecular weight at polymerization time.Polymerization can adopt arbitrarily interrupter method, semi-continuous process or continuous processing to carry out, and can be undertaken by two steps or the multistep that change polymerizing condition.The polyvinyls of producing can be by finishing polymerization after usual method is separated and reclaimed from polymer solvent, dry then and make.
The composition (a) that in polyvinyls catalyst for preparing and preparation method of the present invention, uses, by copolymerization of ethylene in the presence of it or ethene with have 3 or the alkene of more carbon atoms, prepare the polyvinyls that weight-average molecular weight is big, molecular weight distribution is narrow and have terminal ethylenyl groups.Preferably be used as the high molecular macromonomer in the preparation at polyvinyls of the present invention at the polyvinyls that has this composition (a) to produce when existing.
In polyvinyls catalyst for preparing and the prepared polyvinyls of preparation method of the present invention, the polyvinyls that is made by composition (b) is preferably following polyvinyls, and it is by having the long-chain side chain in conjunction with the high molecular macromonomer that is made by composition (a) as comonomer.
Usually, when the molecular weight of macromonomer hanged down, the number of macromonomer increased.As a result, the amount of long-chain side chain increases, and excellent processability.But number-average molecular weight is low, and physical strength is low.On the other hand, when the molecular weight of macromonomer is high, the physical strength height, but do not form the long-chain side chain, and processing characteristics worsens.By the preferably following polyvinyls of polyvinyls that catalyst for preparing of the present invention and preparation method make, it has the long-chain branched structure, high number-average molecular weight and narrow molecular weight distribution, and have high physical strength and good processibility.
The polyvinyls that is made by the catalysis process of polyvinyls of the present invention has 890-980kg/m 3Density (kg/m 3), it is the value of measuring according to the density gradient tube method of JIS K6760 (1995).
The polyvinyls that is made by the catalysis process of polyvinyls of the present invention has 30000-10000000, preferred 40000-8000000, and the more preferably weight-average molecular weight of 50000-5000000 (Mw), Mw/Mn is 2-20, preferred 2-15, more preferably 2-10.
Melt strength (the MS of the polyvinyls that makes by the catalysis process of polyvinyls of the present invention 160(mN)) be measurement temperature at 160 ℃, fluid inlet angle is 90 °, and velocity of shear is 10.8S -1And stretch ratio is a value of using (L) 8mm that has length and diameter (D) to measure as the mould of 2.095mm under 47 the condition.Be lower than at 47 o'clock in maximal draw ratio, the value that will record when not producing the maximal draw ratio in when fracture is as MS 160
The melt flow (MFR (g/10 minute)) of the ethylene copolymer that is made by the catalyzer method of polyvinyls of the present invention is the value that records under 190 ℃, 2.16kg charge capacity, and is preferably 0.1-50.
The MS of the ethene copolymer that makes by the catalysis process of polyvinyls of the present invention 160Have following relation with MFR:
MFR satisfies following formula (23)
MS 160＞90-130×log(MFR) (23)
Preferably satisfy following formula (34)
MS 160＞110-130×log(MFR) (23)
More preferably satisfy following formula (35)
MS 160＞130-110×log(MFR) (23)
The powder accumulation density of the ethene copolymer that is made by the catalysis process of polyvinyls of the present invention is by recording by JIS K6760 method, being preferably 0.15-0.70g/cm 3, the spy is preferably 0.17-0.70g/cm 3, most preferably be 0.20-0.70g/cm 3
Preferably in the 2.5-100 scope, the spy is preferably 2.5-30 to the nonlinear parameter (λ) of the elongation viscosity of the ethene copolymer that is made by the catalysis process of polyvinyls of the present invention.λ is by being 0.07-0.1S in Deformation velocity (strain rate, askew speed) -1, the value of using under 160 ℃ the condition elongation viscosity maximum value that Meissner single shaft elongation viscosity instrumentation gets to obtain divided by the elongation viscosity of at that time linearity region, and can be by calculating at the dynamic viscoelastic described in people's such as M.Yamaguchi the PolymerJoumal 32,164 (2000) at the elongation viscosity of linear section.
The polyvinyls that is made by the catalysis process of polyvinyls of the present invention can contain general additive such as heat-resisting stabilizing agent, weather-resistant stablizer, static inhibitor, anti-fog agent, anti, slip(ping)agent, lubricant, nucleator, mineral filler or toughener such as pigment, carbon black, talcum, glass powder or glass fibre; Organic filler or toughener, flame-proofing agent or neutron shield agent.
The polyvinyls that produces among the present invention can use by mixing with other thermoplastic resin.For example, polyvinyls can with HDPE, LLDPE, LDPE, polypropylene, poly-1-butylene, poly--4-methyl-1-pentene, vinyl-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, polystyrene, their maleic anhydride graft product etc.
The present invention specifically describes in following by embodiment, but the present invention is not limited.Unless otherwise, used reagent etc. all is the commercially available prod.
The preparation of composition (c), the preparation of solid catalyst is used for the Preparation of catalysts that polyvinyls is produced, and the preparation of polyvinyls and solvent purification are all carried out under non-property atmosphere.In the preparation of composition (c), used solvent etc. all carries out purifying with universal method, drying and deoxidation in advance in the Preparation of Catalyst of polyvinyls production usefulness and the preparation of polyvinyls.Used composition (a) and composition (b) all synthesize by common method and identify.Toluene solution (the trade(brand)name: PMAO of hexane solution of used triisobutyl aluminium (0.714M) and methylaluminoxane; Al:2.39M) be the product of TosohFinechem company.
The various performances of polyvinyls are in an embodiment measured by following method.
The ratio (Mw/Mn) of weight-average molecular weight (Mw), number-average molecular weight (Mn) and weight-average molecular weight and number-average molecular weight is measured by permeation chromatography (GPC).Used GPC equipment is HLC-8121GPC/HT, and the product of Tosoh company, used post are TSKgel GMHhr-H (20) HT, the product of Tosoh company.Column temperature is set in 140 ℃, and with 1,2, the 4-trichlorobenzene is as eluent.With 1.0mg/ml prepared at concentrations measure sample, and injection 0.3ml sample is to measure.The typical curve of molecular weight is to use known polystyrene sample to proofread and correct.Mw and Mn are the value acquisitions according to linear polyethylene.
Density (d) is to measure by the density gradient tube of JIS K6760 (1995).
The terminal ethylenyl groups number is by using Fourier transform infrared spectrometer (FT-IR) SPECTRUMONE, Perkin Elmer product, the hot pressing polyvinyls, with ice-cooled with the preparation film, at 4000cm -1-400cm -1Scope is measured film, and uses following formula to calculate and obtain:
The terminal ethylenyl groups number of per 1000 carbon atoms (individual/1000C)=a * A/L/d
Wherein, a is the absorbancy coefficient, and A is for to belong to the 909cm of terminal ethylenyl groups -1Absorbancy, L is the thickness of film, d is a density.A is by the terminal ethylenyl groups number that uses wherein per 1000 carbon atoms 1H-NMR measures the made typical curve of determining of sample and obtains. 1The H-NMR measurement is to use among the GSX400 (product of JEOL company limited) at 130 ℃ to carry out in the mixed solvent of deuterated benzene and orthodichlorobenzene.The terminal ethylenyl groups number of per 1000 carbon atoms is than calculating by the peak that belongs to methylene radical and the integration at peak that belongs to terminal ethylenyl groups.Each peak is to use tetramethylsilane as standard (0ppm), and wherein chemical shift is that the peak of 1.3ppm is chosen to be methylene radical, is chosen to be terminal ethylenyl groups and chemical shift is the peak of 4.8-5.0ppm.
Be used to measure melt strength (MS 160, MS 190), maximum stretch ratio (DR), following the making of polyvinyls of elongation viscosity, tensile fracture nominal distortion (nominal tensile strain at break) and flow-activation energy (Ea): by using closed mixing tank (trade(brand)name: Laboplast Mill, the product of Toyo SeikiSeisaku-Sho company limited) under 190 ℃ is the Irganox 1010 as the 1500ppm of heat-resisting stabilizing agent that 30rpm will add in advance with the rotating speed in nitrogen gas stream TM(product of Ciba SpecialtyChemicals) and 1500ppm Irganox 168 TMThe mixture of (product of Ciba Specialty Chemicals) was mediated 30 minutes.
Flow-activation energy (Ea) is by using disk-disk rheometer (disc-disc rheometer) (trade(brand)name: MCR-300, the product of Anton Paar) in 150 ℃, 170 ℃ and 190 ℃ is the scope of 0.1-100rad/s at each temperature at circular frequency, obtain and shear storage elastic modulus (shear storage elasticmodulus) G ' and slitter loss Young's modulus (shear loss elastic modulus) G ", the shift factor (shift factor) that obtains transverse axis 150 ℃ of standard temperatures down also obtains by following Arrhenius formula (Arrhenius equation) calculating:
Viscosity (η 0)=Aexp (Ea/RT)
Wherein R is a gas law constant.
Do not carry out moving of the longitudinal axis.
Melt strength is assembled to have the capillary viscosimeter that pipe (barrel) diameter is 9.55mm (trade(brand)name Capillograph, the product of Toyo SeikiSeisaku-Sho company) and make fluid inlet angle be 90 ° by the mould that will have 8mm length and 2.095mm diameter and measures.With regard to MS 160, make temperature schedule 160 ℃, piston (piston) fall off rate fixes on 10mm/min and stretch ratio fixes at 47 o'clock, and the required load (mN) of pull-up is as MS 160Be lower than 47 as maximal draw ratio, do not producing the required load (mN) of pull-up under the disruptive maximal draw ratio as MS 160, be used as MS except temperature being arranged on the load (mN) of in kind measuring 190 ℃ 190
Elongation viscosity is to make temperature be arranged on 160 ℃, uses Meissner single shaft elongation viscosity meter (trade(brand)name Melten Rheometer, the product of Toyo Seiki Seisaku-Sho company) to measure.Nonlinear parameter (λ) is by will be at 0.07-0.1S -2The Deformation velocity condition under the maximum value of the elongation viscosity that records divided by the elongation viscosity of linearity region at that time and the value that obtains.The value that the elongation viscosity value of linearity region is to use the approximate expression that obtained at the dynamic viscoelastic of method described in the Palymer Journal 32,164 (2000) by people such as M.Yamagachi to calculate.
Tensile fracture nominal distortion (nominal tensile strain at break draws the broken bad of Zhang and exhales び ひ ず body) is to use tension test meter (TENSILON ATM-500) (Orientec Co, the product of Ltd), press the JISK6922-2 measurement.
The following assessment of the thermostability of polyvinyls.With the polyvinyls that do not add heat-resisting stabilizing agent in nitrogen gas stream in 190 ℃ of following use internal mixers (internal mixer) (trade(brand)name: Laboplast Mill; the product of Toyo Seiki Seisaku-Sho company) be that 30rpm mediated 30 minutes and granulating with the revolution; the particle that obtains was placed 96 hours in being set to 120 ℃ baking oven, and calculated the degree of flavescence (Δ YI) by the method for record among the JIS K 7105.Δ YI is that low more at Δ YI, thermostability is good more by the variable quantity of the yellow degree of following formula acquisition.
ΔYI＝YI-YI 0
(wherein YI is the yellow degree after the thermal treatment in baking oven, and YI 0Be the yellow degree before the thermal treatment in stove)
Embodiment 1
(preparation of composition (c))
37% concentrated hydrochloric acid of 60ml ethanol and 2.0ml is added in the 60ml water.With the N of 6.6g (0.022mol), N-dimethyl stearyl amine is added in the gained solution, and makes gained mixture heating up to 60 ℃ with preparation hydrochloride solution.The 20g hectorite is added in the solution, and gained suspension stirred 3 hours down at 60 ℃, removed supernatant liquor, followed the water washing with 1 liter 60 ℃.Material is 10 -3Torr, 60 ℃ dry 24 hours down, and the gained solid pulverized to obtain the having modified water pyroxene that mean particle size is 5.2 μ m (composition (c)) with jet mill.As the result of ultimate analysis, the ionic weight of every 1g modified water pyroxene is 0.85mmol.
(being used for the Preparation of catalysts that ethene copolymer is produced)
Propylene dichloride-1 with 53mg (160 μ mol), 3-two base two (cyclopentadienyl) closes zirconium (composition (a)) and is suspended in the 17.6ml hexane, and the hexane solution (0.714M) (composition (d)) of 22.4ml triisobutyl aluminium is added wherein to obtain the product of contact of composition (a) and composition (d).The hectorite (composition (c)) of 4.0g modification is added in the product of contact, and the gained mixture was stirred 3 hours at 60 ℃, after leaving standstill, remove supernatant liquor, with hexane solution (0.03M) washing of triisobutyl aluminium.The hexane solution (0.15M) that adds triisobutyl aluminium again, preparation catalyst pulp (100g/ liter).
Following solution is added in the catalyst pulp of above-mentioned preparation, the gained mixture was stirring at room 6 hours, described solution contain 3.3mg (4.9 μ mol) with respect to propylene dichloride-1,3-two bases two (cyclopentadienyl) close the hexane solution (0.714M) that the dichloro phenylbenzene methylene radical (1-cyclopentadienyl) that zirconium is 3mol% (2,7-di-t-butyl-9-fluorenyl) closes zirconium (compound (b)), 7.2ml hexane and 0.69ml triisobutyl aluminium.After leaving standstill, remove supernatant liquor, then the hexane solution (0.03M) with triisobutyl aluminium washs.Add the hexane solution (0.15M) of triisobutyl aluminium again, finally obtain catalyst pulp 100g/ liter.
(preparation of ethene copolymer)
The hexane solution (0.714M) of 1200ml hexane, 36g 1-butylene and 1.0ml triisobutyl aluminium imported in 2 liters the autoclave, the interior temperature of autoclave is brought up to 75 ℃.Add the catalyst pulp of the above-mentioned gained of 0.25ml in autoclave, the mixed gas (hydrogen that contains 700ppm) that imports ethene/hydrogen is 1.2MPa up to dividing potential drop, begins polymerization thus.Between polymerization period, continue to import ethene/hydrogen mixed gas so that it keeps the 1.2MPa dividing potential drop.Polymerization temperature is controlled at 75 ℃.After beginning 60 minutes by polymerization, discharge the interior pressure of autoclave, then the suction filtration inclusion.After the drying, make the 45g polymkeric substance.The density of the ethylene copolymer of gained, MFR, terminal ethylenyl groups number, Mw/Mn, MS 160, MS 190, Ea and Δ YI be shown in table 1.
Embodiment 2
(preparation of ethylene copolymer)
Except 1-butylene and the polymerization time that uses 72g changed into 25 minutes, carry out polymerization by method similar to Example 1.As a result, obtain the 46g polymkeric substance.The density of the ethene copolymer of gained, MFR, terminal ethylenyl groups number, Mw/Mn, MS 160, MS 190, Ea and Δ YI be shown in table 1.
Embodiment 3
(polyvinyls production Preparation of catalysts)
The dichloro 1 of 63mg (160 μ mol), 1,3,3-tetramethyl-second siloxanes-1,3-two bases two (cyclopentadienyl) close zirconium (composition (a)) and are suspended in the 17.6ml hexane, hexane solution (0.714M) 22.4ml of triisobutyl aluminium (composition (d)) is added wherein, to obtain the product of contact of composition (a) and composition (d).The modified water pyroxene (composition (c)) that 4.0g is prepared in embodiment 1 (prepared composition (c)) is added in the product of contact, and the gained mixture stirred 3 hours down at 60 ℃.After leaving standstill, remove supernatant liquid, and wash (0.03M) with the hexane solution of triisobutyl aluminium.The hexane solution that adds triisobutyl aluminium again is with preparation catalyst pulp (100g/ liter).
To contain 5.6mg (8.4 μ mol) with respect to dichloro 1,1,3,3-tetramethyl-second siloxanes-1,3-two base two (cyclopentadienyl) closes the dichloro phenylbenzene methylene radical (1-cyclopentadienyl) (2 of the 5mol% that zirconium is, 7-di-t-butyl-9-fluorenyl) hexane solution (0.714M) that closes zirconium (composition (b)), 6.7ml hexane and 1.18ml triisobutyl aluminium adds in the catalyst pulp of above-mentioned preparation, and the gained mixture was stirring at room 6 hours.After leaving standstill, remove supernatant liquor,, add the hexane solution (0.15M) of triisobutyl aluminium again, finally obtain the catalyst pulp that 100g/ rises then with hexane solution (0.03M) washing of triisobutyl aluminium.
The hexane solution (0.714M) of the triisobutyl aluminium of 1200ml hexane and 1.0ml is imported 2 liters autoclave, the internal temperature of autoclave is brought up to 85 ℃.The above-mentioned 0.075ml catalyst pulp that obtains is added in the autoclave, and the mixed gas (hydrogen that contains 1000ppm) that feeds ethene/hydrogen reaches 1.2MPa up to dividing potential drop, begins polymerization thus.Between polymerization period, the mixed gas that continues importing ethene/hydrogen will make its dividing potential drop remain on 1.2MPa.Controlled polymerization temperature to 85 ℃.After beginning 90 minutes from polymerization, press in discharging, and the suction strainer inclusion.After the drying, obtain 90 gram polymkeric substance.The density of the polyvinyls of gained, MFR, terminal ethylenyl groups number, Mw/Mn, MS 160, MS 190, Ea and Δ YI be shown in table 1.
Embodiment 4
(being used for the Preparation of catalysts that polyvinyls is produced)
Except adding contain 9.7mg (17.8 μ mol) with respect to dichloro 1,1,3,3-tetramethyl disiloxane-1,3-two bases two (cyclopentadienyl) close the dichloro isopropylidene that zirconium is 10mol% (1-cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) closes outside the hexane solution (0.714M) of zirconium (composition (b)), 5.4ml hexane and 2.5ml triisobutyl aluminium, by being prepared with embodiment 3 (being used for the Preparation of catalysts that polyvinyls is produced) same way as.
(polyvinyl preparation)
The hexane solution (0.714M) of 1200ml hexane and 1.0ml triisobutyl aluminium is imported in 2 liters of autoclaves, and the interior temperature of autoclave is brought up to 85 ℃.The catalyst pulp that 0.075ml is obtained above adds in the autoclave, feeds ethene/hydrogen mixed gas (hydrogen that contains 2500ppm) and reaches 1.2MPa up to dividing potential drop, begins polymerization thus.Between polymerization period, continue to feed ethene/hydrogen mixed gas, so that dividing potential drop remains on 1.2MPa.Polymerization temperature is controlled at 85 ℃.After beginning 90 minutes from polymerization, press in discharging, and the suction filtration inclusion, after the drying, obtain the 91g polymkeric substance.The density of polyvinyls, MFR, terminal ethylenyl groups number, Mw/Mn, MS 160, MS 190, Ea and Δ YI be shown in table 1.
(comparative example 1)
(preparation of polyvinyls)
The hexane solution (0.714M) of 1200ml hexane and 0.08ml triisobutyl aluminium imported in 2 liters the autoclave, improve the interior temperature to 90 ℃ of autoclave.With 72.5mg Cr catalyzer (EP350) (INEOSSilicas company product), add in the autoclave, feed hydrogen and reach 1.0MPa up to dividing potential drop, import ethylene gas then and reach 1.0MPa up to dividing potential drop, begin polymerization thus.Continue to import ethylene gas between polymerization period keeping ethylene partial pressure, controlled polymerization temperature to 90 ℃.After 90 minutes, discharge the interior pressure of autoclave from the beginning polymerization, and the suction filtration inclusion.Obtain the 143g polymkeric substance after the drying.The density of the polyvinyls that obtains, MFR, terminal ethylenyl groups number, Mw/Mn, MS 160, MS 190, Ea and Δ YI be shown in table 1.For surpassing 0.2, and the evaluation result of Δ YI, thermostability is poor to the terminal ethylenyl groups number of confirming polyvinyls with respect to 1000 carbon atoms.
(comparative example 2)
The metallocene-type catalyst ethene/density of 1-octene copolymer (AF1840), MFR, terminal ethylenyl groups number, Mw/Mn, MS by Dow Chemical Company sale 160, MS 190All be shown in table 1 with Ea.The prerequisite of this polyvinyls is not inconsistent box-like (1) and (3).
(comparative example 3)
Density, MFR, terminal ethylenyl groups number, Mw/Mn, MS available from the high pressure LDPE (Petrocene 176R) of Tosoh Corporation 160, MS 190All be shown in table 1 with Ea.This polyvinyls is not inconsistent box-like (2) and the prerequisite of formula (3).
(comparative example 4)
Density, MFR, terminal ethylenyl groups number, Mw/Mn, MS available from the high pressure LDPE (Petrocene 360) of Tosoh Corporation 160, MS 190All be shown in table 1 with Ea.This polyvinyls is not inconsistent box-like (2) and the prerequisite of formula (3).
Figure DEST_PATH_S2006800478765D00521
Embodiment 5
(preparation of composition (c))
37% concentrated hydrochloric acid of 60ml ethanol and 2.0ml is joined in the 60ml water.With the N of 6.6g (0.022mol), N-dimethyl stearyl amine joins in the gained solution, with gained mixture heating up to 60 ℃ with preparation hydrochloride solution.Add the 20g hectorite in solution.Gained suspension stirred 3 hours at 60 ℃.Remove supernatant liquor, follow water washing with 1 liter 60 ℃.Material is at 60 ℃, 10 -3Torr dry 24 hours down with jet mill efflorescence gained solid, has the modified water pyroxene that mean particle size is 5.2 μ m (composition (c)) to make.The result of ultimate analysis, the ionic weight of 1 gram modified water pyroxene is 0.85mmol.
(being used for the Preparation of catalysts that polyvinyls is produced)
Dichloro (1 with 63mg (160 μ mol), 1,3,3-tetramethyl-second siloxanes-1,3-two bases two (cyclopentadienyl) close zirconium (composition (a)) and are suspended in the 17.6ml hexane, and hexane solution (0.714M) 22.4ml of triisobutyl aluminium (composition (d)) added wherein, obtain the product of contact of composition (a) and composition (d).Add modified water pyroxene (composition (d)) that 4.0g obtains above and stirred the gained mixtures 3 hours at 60 ℃.Leave standstill, remove supernatant liquor then, and wash with the hexane solution (0.03M) of triisobutyl aluminium.The hexane solution (0.15M) that adds triisobutyl aluminium again is with preparation catalyst pulp (100g/ liter).
To contain with respect to dichloro (1,1,3,3-tetramethyl-second siloxanes-1,3-two bases two (cyclopentadienyl) close the dichloro phenylbenzene methylene radical (1-cyclopentadiene) (2 that zirconium is 5.3mol%, 7-di-t-butyl-9-fluorenyl) hexane solution (0.714M) that closes zirconium (compound (b)), 7.2ml hexane and 1.2ml triisobutyl aluminium is added in the catalyst pulp for preparing above, and in stirring at room gained mixture 6 hours.After leaving standstill, remove supernatant liquor, then the hexane solution (0.03M) with triisobutyl aluminium washs.The hexane solution (0.15M) that adds triisobutyl aluminium more finally makes the catalyst pulp that 100g/ rises.
(preparation of polyvinyls)
The hexane solution (0.714M) of 1200ml hexane and 1.0ml triisobutyl aluminium imported in 2 liters the autoclave and make the interior temperature of autoclave bring up to 85 ℃.Add catalyst pulp that 0.18ml obtains above in autoclave, and feed ethene and reach 1.2MPa, begin polymerization thus up to dividing potential drop.Continue between polymerization period to import ethene/hydrogen mixed gas (containing 1300ppm hydrogen) so that dividing potential drop remains on 1.2MPa.Polymerization temperature is controlled at 85 ℃.After 90 minutes, discharge the interior pressure of autoclave from the beginning polymerization, and the suction filtration inclusion.After the drying, obtain the 216g polyvinyls.The polyvinyls that obtains has 310kg/m 3Tap density, 960kg/m 3Density, 108000 Mw and 6.70 Mw/Mn.In addition, MFR is 1.0g/10 minute, MS 160Be 170mN.The measuring result of elongation viscosity, λ is 4.8.The tensile fracture nominal distortion is 690% or more.When measuring two key, it is 0.04 with respect to the terminal ethylenyl groups of 1000 carbon atoms with FT-IR.
(comparative example 5)
(being used for the Preparation of catalysts that polyvinyls is produced)
Dichloro (1 with 63mg (160 μ mol), 1,3,3-tetramethyl-second siloxanes-1,3-two bases-two (cyclopentadienyls)) close zirconium and be suspended in the 17.6ml hexane, and the hexane solution (0.714M) (composition (d)) that adds the triisobutyl aluminium of 22.4ml therein is to make the product of contact of composition (a) and composition (d).Add the modified water pyroxene (composition (c)) that 4.0g prepares in embodiment 1 (preparation of composition (c)), and stirred the gained mixture 3 hours down at 60 ℃.After leaving standstill, removing supernatant liquor, and wash with the hexane solution (0.03M) of triisobutyl aluminium.The hexane solution (0.15M) that adds triisobutyl aluminium again is with preparation catalyst pulp (100g/ liter).
(preparation of polyvinyls)
The hexane solution (0.714M) of 1200ml hexane and 1.0ml triisobutyl aluminium imported in 2 liters the autoclave, improve the temperature to 85 ℃ in the autoclave.The catalyst pulp that 0.10ml is made above adds in the autoclave, and imports ethene and reach 1.2MPa up to dividing potential drop, begins polymerization thus.Between polymerization period, continue to import the mixed gas (hydrogen that contains 1200ppm) of ethene/hydrogen so that dividing potential drop remains on 1.2MPa.The controlled polymerization temperature is 85 ℃.After beginning 90 minutes from polymerization, discharge the interior pressure in the autoclave, and the suction filtration inclusion.After the drying, obtain the 100g polyvinyls.The polyvinyls that obtains has 282kg/m 3Tap density, 952kg/m 3Density, 73400 Mw and 2.97 Mw/Mn.In addition, MFR is 5.2g/10min, and MS 160Be 11mN.The measuring result of elongation viscosity, λ is 2.2.
(comparative example 6)
(being used for the Preparation of catalysts that polyvinyls is produced)
Except using the dichloro phenylbenzene methylene radical (1-cyclopentadienyl) (2 of 107mg (160 μ mol), 7-di-t-butyl-9-fluorenyl) closes zirconium and replace dichloro (1,1,3,3-tetramethyl-second siloxanes-1,3-two base two (cyclopentadienyl) closes beyond the zirconium, by with comparative example 5 in (being used for the Preparation of catalysts that polyvinyls is produced) similarly mode prepare catalyzer, make 100g/ and rise catalyst pulp.
(preparation of polyvinyls)
The hexane solution (0.714M) of 1200ml hexane and 1.0ml triisobutyl aluminium introduced in 2 liters the autoclave, improve the interior temperature to 85 ℃ in the autoclave.Add catalyst pulp that 0.10ml makes above in autoclave, and import ethene and reach 1.2MPa, begin polymerization thus up to dividing potential drop.Between polymerization period, continue to import ethene/hydrogen mixed gas (containing 6000ppm hydrogen), so that dividing potential drop keeps 1.2MPa.Controlled temperature to 85 ℃.After beginning 90 minutes from polymerization, discharge the interior pressure in the autoclave, then the suction filtration inclusion.After the drying, obtain the 155g polyvinyls.The gained polyvinyls has 225kg/m 3Tap density, 954kg/m 3Density, 112000 Mw and 3.18 Mw/Mn.In addition, MFR is 0.88g/10min, MS 160Be 92mN.The measuring result of elongation viscosity, λ is 2.1.
Embodiment 6
(preparation of composition (c))
Except using the N of 7.8g (0.022mol), N-dimethyl-Shan Yu base amine replace N, outside N-dimethyl-octadecylamine, by with embodiment 5 in (preparation of composition (c)) similar mode prepared composition (c), obtain having the modified water pyroxene that mean particle size is 5.5 μ m (composition (c)).The result of ultimate analysis, the ionic weight in every 1g modified water pyroxene is 0.91mmol.
(being used for the Preparation of catalysts that polyvinyls is produced)
Propylene dichloride-1 with 53mg (160 μ mol), 3-two bases-two (cyclopentadienyls) close zirconium (composition (a)) and are suspended in the 17.6ml hexane, and the hexane solution (0.714M) of the triisobutyl aluminium (composition (d)) of adding 22.4ml obtains the product of contact of composition (a) and composition (d) in wherein.The modified water pyroxene (composition (c)) that 4.0g is obtained above adds in the product of contact, stirs the gained mixture 3 hours at 60 ℃, after leaving standstill, removes supernatant liquor, and washs with the hexane solution (0.03M) of triisobutyl aluminium.Add the catalyst pulp of the hexane solution (0.15M) of triisobutyl aluminium again with preparation 100g/ liter.
To contain with respect to propylene dichloride-1, it is that the hexane solution (0.714M) that 18mol% dichloro isopropylidene (1-cyclopentadienyl) (9-fluorenyl) closes zirconium (composition (b)) 12mg (2 μ mol), 7.2ml hexane and 1.2ml triisobutyl aluminium is added in the catalyst pulp that makes above that 3-two base two (cyclopentadienyl) closes zirconium, and in stirring at room mixture 6 hours.After leaving standstill, remove supernatant liquor, then the hexane solution (0.03M) with triisobutyl aluminium washs.The hexane solution (0.15M) that adds triisobutyl aluminium more finally obtains the catalyst pulp that 100g/ rises.
(preparation of polyvinyls)
The hexane solution (0.714M) of 1200ml hexane and 1.0ml triisobutyl aluminium imported in 2 liters the autoclave, improve the interior temperature to 85 ℃ of autoclave.The catalyst pulp that 0.18ml is made above adds in the autoclave, imports ethene and reaches 1.2MPa up to dividing potential drop, begins polymerization thus.Between polymerization period, import ethene/hydrogen mixed gas (containing 1000ppm hydrogen) continuously, to keep the dividing potential drop of 1.2MPa.Polymerization temperature is controlled at 85 ℃.After beginning 90 minutes from polymerization, discharge interior pressure and suction filtration inclusion in the autoclave.Obtain the 155g polyvinyls after the drying.The polyvinyls that obtains has 325kg/m 3Tap density, 958kg/m 3Density, 87500 Mw and 4.27 Mw/Mn.In addition, MFR is 3.4g/10 minute, MS 160Be 90mN.The measuring result λ of elongation viscosity is 5.1.The tensile fracture nominal distortion is 400%.When measuring two key with FT-IR, it is 0.04 with respect to the terminal ethylenyl groups of 1000 carbon atoms.
(comparative example 7)
(Preparation of catalysts that is used for the polyvinyls preparation)
Except the dichloro two (cyclopentadienyl) that uses 47mg (160 μ mol) closes the propylene dichloride-1 that zirconium replaces embodiment 6 (Preparation of catalysts that is used for the polyvinyls preparation), 3-two bases-two (cyclopentadienyls) close beyond the zirconium, prepare catalyzer by method similar to Example 2, make the catalyst pulp that 100g/ rises.
(preparation of polyvinyls)
The hexane solution (0.714M) of 1200ml hexane and 1.0ml triisobutyl aluminium is imported 2 liters autoclave, improve the interior temperature to 85 ℃ of autoclave.The catalyst pulp that 0.15ml is made above adds in the autoclave, imports ethene and reaches 1.2MPa up to dividing potential drop, begins polymerization thus.Between polymerization period, continue to import ethene/hydrogen mixed gas (hydrogen that contains 800ppm) so that keep the 1.2MPa dividing potential drop.Polymerization temperature is controlled at 85 ℃.After beginning 90 minutes from polymerization, discharge the interior pressure of autoclave, and the suction filtration inclusion.Obtain the 185g polyvinyls after the drying.The gained polyvinyls has 275kg/m 3Tap density, 961kg/m 3Density, 92000 Mw and 7.60 Mw/Mn.In addition, MFR is 2.2g/10min, and MS 160Be 46mN.The measuring result of elongation viscosity, λ is 2.1.
(comparative example 8)
(being used for the Preparation of catalysts that polyvinyls is produced)
Except using 63mg (160 μ mol) dichloro two (indenyl) to close the propylene dichloride-1 that zirconium replaces embodiment 2 (Preparation of catalysts that is used for polyvinyls) to use, 3-two bases two (cyclopentadienyl) close beyond the zirconium, prepare catalyzer by mode similar to Example 6, and obtain the catalyst pulp that 100g/ rises.
(preparation of polyvinyls)
The hexane solution (0.714M) of 1200ml hexane and 1.0ml triisobutyl aluminium is imported 2 liters autoclave, improve the interior temperature to 85 ℃ in the autoclave.The catalyst pulp that adding 0.15ml makes above imports ethene and reaches the 1.2MPa dividing potential drop up to dividing potential drop in autoclave, begins polymerization thus.Between polymerization period, continue to import the mixed gas (containing 1200ppm hydrogen) of ethene/hydrogen to keep the dividing potential drop of 1.2MPa.Polymerization temperature controls to 85 ℃.After beginning 90 minutes from polymerization, discharge the interior pressure in the autoclave, and the suction filtration inclusion.After the drying, obtain the 207g polyvinyls.The polyvinyls that obtains has 290kg/m 3Tap density, 960kg/m 3Density, 112000 Mw and 9.91 Mw/Mn.In addition, MFR is 0.95g/10 minute, and MS 160Be 92mN.The measuring result of elongation viscosity, λ is 2.0.
Embodiment 7
(preparation of composition (c))
37% concentrated hydrochloric acid of 60ml ethanol and 2.0ml is added in the 60ml water, and with the N of 6.6g (0.022mol), N-dimethyl stearyl amine is added in the gained solution then, and gained solution is heated to 60 ℃ with preparation hydrochloride solution.Add the 20g montmorillonite in solution.Gained suspension stirred 3 hours at 60 ℃.Remove supernatant liquor, follow water washing with 1 liter 60 ℃.Material is at 60 ℃, 10 -3Drying is 24 hours under the torr, and pulverizes the gained solid to obtain modified montmorillonite used (composition (c)) that mean particle size is 5.8 μ m with jet mill.The result of ultimate analysis is that the ionic weight of the montmorillonite of every 1g modification is 0.85mmol.
(being used for the Preparation of catalysts that polyvinyls is produced)
Dichloro (1 with 58mg (160 μ mol), 1-dimethyl-1-sila ethane-1,2-two base two (cyclopentadienyl)) closes zirconium (composition (a)) and be suspended in the 17.6ml hexane, hexane solution (0.714M) 22.4ml of triisobutyl aluminium (composition (d)) is added to wherein to obtain the product of contact of composition (a) and composition (b).Modified montmorillonite used (composition (c)) that 4.0g is obtained above is added in the product of contact, and the gained mixture was stirred 3 hours down at 60 ℃, after leaving standstill, removes supernatant liquor, with hexane solution (0.03M) washing of triisobutyl aluminium.The hexane solution (0.15M) that adds triisobutyl aluminium again is with preparation catalyst pulp (100g/ liter).
To contain with respect to dichloro (1,1-dimethyl-1-sila ethane-1, it is that the hexane solution (0.714M) that the dichloro phenylbenzene methylene radical (1-cyclopentadienyl) (9-fluorenyl) of 3.1mol% closes zirconium (composition (b)) 2.8mg (4.9 μ mol), 7.2ml hexane and 1.2ml triisobutyl aluminium is added in the catalyst pulp for preparing above that 2-two base two (cyclopentadienyl) closes zirconium, and in stirring at room gained mixture 6 hours.After leaving standstill, remove supernatant liquor, then the hexane solution (0.03M) with triisobutyl aluminium washs.The hexane solution (0.15M) that adds triisobutyl aluminium more finally obtains the catalyst pulp that 100g/ rises.
(preparation of polyvinyls)
The hexane solution (0.714M) of 1200ml hexane and 1.0ml triisobutyl aluminium imported in 2 liters the autoclave, improve the interior temperature to 85 ℃ in the autoclave.The catalyst pulp that adding 0.50ml makes above imports ethene and reaches 1.2MPa up to dividing potential drop in autoclave, begins polymerization thus.Between polymerization period, continue to import ethene/hydrogen mixed gas (hydrogen that contains 1000ppm) to keep the dividing potential drop of 1.2MPa.Polymerization temperature is controlled at 85 ℃.After beginning 90 minutes from polymerization, discharge the interior pressure in the autoclave, and the suction filtration inclusion.After the drying, obtain the 165g polyvinyls.The polyvinyls that obtains has 265kg/m 3Tap density, 957kg/m 3Density, 82000 Mw and 4.23 Mw/Mn.In addition, MFR is 5.2g/10 minute, MS 160Be 62mN.The measuring result of elongation viscosity, λ is 5.5.The tensile fracture nominal distortion is 320%.
Embodiment 8
(preparation of the product of contact of composition (o) and composition (j))
With 53g silicon-dioxide (Davison 948, in down calcining 5 hours of decompression, 200 ℃), (right-N, N-dimethylaminophenyl) Trimethoxy silane of 1 liter of toluene and 20g (91mmol) is added in 3 liters of flasks, and stirs the gained mixture 16 hours down at 110 ℃.After finishing reaction, use toluene wash mixture four times.The silicon-dioxide that passes through the silane compound modification that obtains (composition (o)) has the carbon content of 4.2wt%.18.7g is suspended in the 500ml ether through the silicon-dioxide of silane compound modification, at room temperature, was blown into hydrogen chloride gas 30 minutes.Then, suspension is with hexane wash and drying under reduced pressure.The material that makes like this is suspended in the dichloromethane solution (400ml) of four (pentafluorophenyl group) lithium tetraborate (composition (j)) that adds 6.0g (8.7mmol) in the 600ml methylene dichloride, then stirring at room 3 hours.With washed with dichloromethane mixture three times, and vacuum-drying is to obtain solid catalyst.Carbon content is 10.8wt% in the solid catalyst that obtains.
(being used for the Preparation of catalysts that polyvinyls is produced)
The composition (o) of the above-mentioned preparation of 1.0g and the product of contact of composition (j) are dispersed in the 100ml hexane, in dispersion liquid, add: the hexane solution of 1.4ml triisobutyl aluminium (0.714M), the dichloro (1 of (18.1mg 50 μ mol), 1-dimethyl-1-sila ethane-1,2-two bases-two (cyclopentadienyls)) close zirconium (composition (a)), and with respect to dichloro (1,1-dimethyl-1-sila ethane-1,2-two bases-two (cyclopentadienyls)) closing zirconium is that the dichloro phenylbenzene methylene radical (1-cyclopentadienyl) (9-fluorenyl) of 7.5mol% closes zirconium (composition (b)) 2.1mg (3.8 μ mol).The gained mixture stirring at room 1 hour with the preparation catalyst pulp.
(preparation of polyvinyls)
The hexane solution (0.714M) of 1200ml hexane and 1.0ml triisobutyl aluminium imported in 2 liters the autoclave, improve the interior temperature to 85 ℃ of autoclave.The solids component of the above-mentioned catalyst pulp that makes of 100mg is added in the autoclave, import ethene and reach 1.2MPa up to dividing potential drop.Continue to import ethene/hydrogen mixed gas (hydrogen that contains 850ppm) between polymerization period to keep the pressure of 1.2MPa.Polymerization temperature is controlled at 85 ℃.After beginning 90 minutes from polymerization, discharge the interior pressure in the autoclave, and the suction filtration inclusion.Obtain the 96g polymkeric substance after the drying.The gained polyvinyls has 232kg/m 3Tap density, 957kg/m 3Density, 90000 Mw and 4.25 Mw/Mn.In addition, MFR is 1.9g/10min, MS 160Be 128mN.The measuring result of elongation viscosity, λ is 4.5.The tensile fracture nominal distortion is 690% or more.
Embodiment 9
(preparation of the product of contact of composition (o) and composition (g))
With 30g silicon-dioxide (Davison 948, and calcining is 5 hours under 200 ℃, decompression), the toluene solution (trade(brand)name: PMAO of the methylaluminoxane of 1 liter of toluene and 250ml (0.60mol); Al:2.39M) join in 3 liters of flasks, and stirred the gained mixture 3 hours at 80 ℃.Finish toluene wash mixture four times of reaction back.The silicon-dioxide of the modification of alumoxanes that obtains (composition (o)) has the aluminium content of 6.5wt%.
(being used for the Preparation of catalysts method that polyvinyls is produced)
The composition (o) of the above-mentioned preparation of 1.0g and the product of contact of composition (g) are dispersed in the 100ml hexane, the dichloro (1 that adds hexane solution (0.714M) 1.4ml, the 14.5mg (40 μ mol) of triisobutyl aluminium, 1-dimethyl-1-sila ethane-1,2-two base two (cyclopentadienyl)) close zirconium (composition (a)), with respect to dichloro (1,1-dimethyl-1-sila ethane-1,2-two base two (cyclopentadienyl)) closing zirconium is that the dichloro phenylbenzene methylene radical (1-cyclopentadienyl) (9-fluorenyl) of 9.9mol% closes zirconium (composition (b)) 2.2mg (4.0 μ mol).In stirring at room gained mixture 2 hours with the preparation catalyst pulp.
(preparation of polyvinyls)
With the 1200ml hexane and the hexane solution (0.714M) of 1.0ml triisobutyl aluminium import in one 2 liters the autoclave, and improve the interior temperature to 85 ℃ of autoclave.The solids component of the catalyst pulp that adding 100mg makes above imports ethene and reaches 1.2MPa up to dividing potential drop in autoclave.Between polymerization period, continuing to import ethene/hydrogen mixed gas (containing 1200ppm hydrogen) is 1.2MPa to keep dividing potential drop.Polymerization temperature is controlled at 85 ℃.Begin to discharge after 90 minutes interior pressure the autoclave and suction filtration inclusion from polymerization.Make the 74g polymkeric substance after the drying.Resulting polymers has 228kg/m 3Tap density, 956kg/m 3Density, 105000 Mw and 6.75 Mw/Mn.MFR is 1.1g/10min in addition, MS 160Be 131mN.The measuring result of elongation viscosity, λ is 4.8.The tensile fracture nominal distortion is 690% or more.
Embodiment 10
(being used for the Preparation of catalysts that ethylene copolymer is produced)
Dichloro (1 with 58mg (160 μ mol), 1-dimethyl-1-sila ethane-1,2-two bases two (cyclopentadienyl)) close zirconium (composition (a)) and be suspended in the 17.6ml hexane, hexane solution (0.714M) 22.4ml that adds triisobutyl aluminium (composition (d)) therein is to obtain the product of contact of composition (a) and composition (d).The modified water pyroxene (composition (c)) that 4.0g is prepared in embodiment 5 (prepared composition (c)) joins in the product of contact, stirs the gained mixture 3 hours at 60 ℃.After leaving standstill, remove supernatant liquor, and wash with the hexane solution (0.03M) of triisobutyl aluminium.The hexane solution (0.15M) that adds triisobutyl aluminium again is with preparation catalyst pulp (100g/ liter).
To contain with respect to dichloro (1,1-dimethyl-1-sila ethane-1,2-two bases-two (cyclopentadienyls)) close the dichloro phenylbenzene methylene radical (1-cyclopentadienyl) (2 that zirconium is 2.0mol%, 7-di-t-butyl-9-fluorenyl) hexane solution (0.714M) that closes zirconium (composition (b)) 2.2mg (3.3 μ mol), 7.2ml hexane, 0.34ml triisobutyl aluminium is added in the catalyst pulp for preparing above, and in stirring at room gained mixture 6 hours.Behind the standing mixt, remove supernatant liquor, then the hexane solution (0.03M) with triisobutyl aluminium washs.The hexane solution (0.15M) that adds triisobutyl aluminium more finally obtains the catalyst pulp that 100g/ rises.
(preparation of polyvinyls)
The hexane solution (0.714M) of the 1.0ml1-butylene of 1200ml hexane, 36g and triisobutyl aluminium imported in 2 liters the autoclave, improve the interior temperature to 75 ℃ of autoclave.Add catalyst pulp that 0.25ml makes above in autoclave, and import ethene and reach 1.2MPa, begin polymerization thus up to dividing potential drop.Between polymerization period, continue to import ethene/hydrogen mixed gas (hydrogen that contains 300ppm) to remain the dividing potential drop of 1.2MPa.Polymerization temperature is controlled at 75 ℃.Begin to discharge after 35 minutes interior pressure the autoclave and suction filtration inclusion from polymerization.After the drying, obtain the 58g polymkeric substance.The polyvinyls that obtains has 924kg/m 3Density, 93000 Mw and 4.68 Mw/Mn.In addition, MFR is 1.8g/10min, and MS 160Be 138mN.The measuring result of elongation viscosity, λ is 4.7.When measuring two key with FT-IR, terminal ethylenyl groups is 0.08 with respect to 1000 carbon atoms.
Embodiment 11
(being used for the Preparation of catalysts that ethene copolymer is produced)
Propylene dichloride-1 with 53mg (160 μ mol), 3-two base two (cyclopentadienyl) closes zirconium (composition (a)) and is suspended in the 17.6ml hexane, and hexane solution (0.714M) 22.4ml that adds triisobutyl aluminium (composition (d)) is in wherein to obtain the product of contact of composition (a) and composition (d).4.0g is joined in the product of contact at the prepared modified water pyroxene (composition (c)) of embodiment 6 (preparation of composition (c)), and stirred the gained mixture 3 hours down at 60 ℃.After placing mixture, remove supernatant liquor, and wash with the hexane solution (0.03M) of triisobutyl aluminium.The hexane solution (0.15M) that adds triisobutyl aluminium again is with preparation catalyst pulp (100g/ liter).
To contain with respect to propylene dichloride-1,3-two bases two (cyclopentadienyl) close the dichloro phenylbenzene methylene radical (1-cyclopentadiene) (2 that zirconium is 3.1mol%, 7-two-tertiary butyl-9-fluorenyl) close zirconium (composition (b)) 3.3mg (4.9 μ mol), 7.2ml hexane and the hexane solution (0.714M) of 0.34ml triisobutyl aluminium be added in the catalyst pulp for preparing above, in stirring at room gained mixture 6 hours.After placing mixture, remove supernatant liquor, then the hexane solution (0.03M) with triisobutyl aluminium washs.The hexane solution (0.15M) that adds triisobutyl aluminium again is finally to produce the catalyst pulp that 100g/ rises.
(preparation of ethene copolymer)
The hexane solution (0.714M) of the 1-butylene of 1200ml hexane, 36g and 1ml triisobutyl aluminium imported in 2 liters the autoclave, and improve interior temperature to 75 ℃ in the autoclave.Add catalyst pulp that 0.25ml makes above in autoclave, and import ethene and reach 1.2MPa, begin polymerization thus up to dividing potential drop.Between polymerization period, continue to import ethene/hydrogen mixed gas to keep the dividing potential drop of 1.2MPa.Polymerization temperature is controlled at 75 ℃.After beginning 65 minutes from polymerization, discharge interior pressure and suction filtration inclusion in the autoclave.Obtain the 46g polymkeric substance after the drying.The polyvinyls that obtains has 929kg/m 3Density, 82000 Mw and 4.52 Mw/Mn.In addition, MFR is 6.2g/10 minute, and MS 160Be 47mN.The measuring result of elongation viscosity, λ is 5.6.When measuring two key with FT-IR, terminal ethylenyl groups is 0.06 with respect to 1000 carbon atoms.
Embodiment 12
(being used for the Preparation of catalysts that polyvinyls is produced)
Dichloro (1 with 63mg (160 μ mol), 1,3,3-tetramethyl-second siloxanes-1,3-two base two (cyclopentadienyl)) close zirconium and be suspended in the 17.6ml hexane, and the hexane solution (0.714M) that adds 22.4ml triisobutyl aluminium (composition (d)) is in wherein to obtain the product of contact of composition (a) and composition (d).4.0g synthetic modified water pyroxene (composition (c)) in embodiment 6 is joined in the product of contact, and stirred the gained mixture 3 hours at 60 ℃.Behind the standing mixt, remove supernatant liquor, with hexane solution (0.03M) washing of triisobutyl aluminium.The hexane solution (0.15M) that adds triisobutyl aluminium again is with preparation catalyst pulp (100g/ liter).
To contain with respect to dichloro (1,1,3,3-tetramethyl-second siloxanes-1,3-two base two (cyclopentadienyl)) closes that solution that the dichloro isopropylidene that zirconium is 7.5mol% (1-cyclopentadienyl) (9-fluorenyl) closes the hexane solution (0.714M) of zirconium (composition (b)) 5.2mg (12 μ mol), 7.2ml hexane and 1.2ml triisobutyl aluminium is added in the catalyst pulp for preparing above and in stirring at room gained mixture 6 hours.Behind the standing mixt, remove supernatant liquor, then the hexane solution (0.03M) with triisobutyl aluminium washs.The hexane solution (0.15M) that adds triisobutyl aluminium more finally makes the catalyst pulp that 100g/ rises.
(preparation of polyvinyls)
The hexane solution (0.714M) of 1200ml hexane and 1.0ml triisobutyl aluminium imported in 2 liters the autoclave, and improve interior temperature to 85 ℃ in the autoclave.The catalyst pulp that adding 0.1ml makes above imports ethene and reaches 1.2MPa up to dividing potential drop in autoclave, begins polymerization thus.Between polymerization period, continue to import ethene/hydrogen mixed gas (hydrogen that contains 600ppm) to keep the dividing potential drop of 1.2MPa.Polymerization temperature is controlled at 85 ℃.After beginning 90 minutes from polymerization, discharge the interior pressure of autoclave, and the suction filtration inclusion.After the drying, obtain the 100g polyvinyls.The gained polyvinyls has 316kg/m 3Tap density, 957kg/m 3Density, 175000 Mw and 3.30 Mw/Mn.In addition, MFR is 0.17g/10 minute, and MS 160Be 290mN.The measuring result of elongation viscosity, λ is 5.9.The tensile fracture nominal distortion is 690% or more.
Embodiment 13
(being used for the preparation of the catalyst component (I) of polyvinyls production)
Dichloro (1 with 63mg (160 μ mol), 1,3,3-tetramethyl-second siloxanes-1,3-two base two (cyclopentadienyl) closes zirconium and is suspended in the 17.6ml hexane, and the hexane solution (0.714M) that adds 22.4ml triisobutyl aluminium (composition (d)) is in wherein to produce the product of contact of composition (a) and composition (d).4.0g synthetic modified water pyroxene (composition (c)) in embodiment 6 is added in the product of contact, and stirred the gained mixture 3 hours down at 60 ℃.Standing mixt is removed supernatant liquor, and washs with the hexane solution (0.03M) of triisobutyl aluminium.The hexane solution (0.15M) that adds triisobutyl aluminium again is with preparation catalyst pulp (100g/ liter).(being used for the preparation of the catalyst component (II) of polyvinyls production)
Dichloro phenylbenzene methylene radical (1-cyclopentadienyl) (2 with 15.4mg (23 μ mol), 7-two-tertiary butyl-9-fluorenyl) close zirconium (composition (b)) and be suspended in the 111ml hexane, and the hexane solution (0.714M) that adds 4.5ml triisobutyl aluminium (composition (d)) is in wherein with the hexane solution (concentration of composition (b): the 0.2mmol/ liter) of the product of contact that makes composition (b) and composition (d).
(preparation of polyvinyls)
The hexane solution (0.714M) of 1200ml hexane and 1.0ml triisobutyl aluminium is imported in 2 liters of autoclaves, improve the interior temperature to 85 ℃ of autoclave.The catalyst component (I) that adding 0.1ml makes above imports ethene and reaches 1.2MPa up to dividing potential drop in autoclave, begins polymerization thus.Between polymerization period, continue to import ethene/hydrogen mixed gas (hydrogen that contains 2850ppm) to keep the dividing potential drop of 1.2MPa.Polymerization temperature is controlled at 85 ℃.After beginning 90 minutes from polymerization, cooling autoclave to 55 ℃, and with its inside of nitrogen replacement five times.Improve autoclave temp to 90 and ℃ add catalyzer (II) that 6ml makes above in autoclave, and import ethene therein and reach 0.3MPa, begin polymerization thus up to dividing potential drop.Between polymerization period, continue to import ethene/hydrogen mixed gas (containing 5200ppm hydrogen) to keep the dividing potential drop of 1.2MPa.Begin to discharge after 105 minutes the interior pressure of autoclave and suction filtration inclusion from polymerization.After the drying, obtain the 122g polyvinyls.The polyvinyls that obtains has 267kg/m 3Tap density, 960kg/m 3Density, 78000 Mw and 3.71 Mw/Mn.In addition, MFR is 4.1g/10 minute and MS 160Be 51mN.The measuring result of elongation viscosity, λ is 6.2.Tensile fracture nominal deformation is 690% or more.
Embodiment 14
(preparation of polyvinyls)
The hexane solution (0.714M) of 1200ml hexane and 1.0ml triisobutyl aluminium imported in 2 liters the autoclave, improve the interior temperature to 85 ℃ of autoclave.Add 0.1ml at the catalyst component (I) of embodiment 13 (being used for the preparation of the catalyst component (I) that polyvinyls produces) preparation in autoclave, and importing ethene reaches 1.2MPa up to dividing potential drop, begins polymerization thus.Between polymerization period, continue to import ethene/hydrogen mixed gas (containing 700ppm hydrogen) to keep the dividing potential drop of 1.2MPa.Polymerization temperature is controlled at 85 ℃.After polymerization begins 90 minutes, cooling autoclave to 55 ℃, and with nitrogen replacement autoclave inside five times.At this moment, collect 10g polymkeric substance and measure its molecular weight.Mw is 136000 as a result, and Mw/Mn is 2.98.Moreover when measuring two key with FT-IR, terminal ethylenyl groups is 0.04 with respect to 1000 carbon atoms.Afterwards, improve autoclave to 90 ℃.In autoclave, add the catalyst component (II) of 6ml, and import ethene, begin polymerization thus in wherein reaching 0.3MPa up to dividing potential drop in embodiment 13 (being used for the preparation of the catalyst component (II) of polyvinyls production) preparation.Between polymerization period, continue to import ethene/hydrogen mixed gas (containing 12000ppm hydrogen) to keep the dividing potential drop of 1.2MPa.After beginning 105 minutes from polymerization, discharge the interior pressure and the suction filtration inclusion of autoclave.After the drying, obtain the 128g polyvinyls.The polyvinyls that obtains has 313kg/m 3Tap density, 958kg/m 3Density, 173000 Mw and 3.49 Mw/Mn.In addition, MFR is 0.17g/10 minute, MS 160Be 690mN.The measuring result of elongation viscosity, λ is 6.6.The tensile fracture nominal distortion is 690% or more.
Gained the results are shown in table 2 in the foregoing description and Comparative Examples.
Figure DEST_PATH_S2006800478765D00641
, wherein can carry out various changes and improvements and do not break away from its spirit and scope with reference to its concrete scheme and when describing in detail in the present invention it will be apparent to those skilled in the art that.
The application is based on the Japanese patent application (number of patent application 2005-365428) of application on December 19th, 2005 and the Japanese patent application (number of patent application 2005-365430) of application on December 19th, 2005, and its full content is incorporated herein with for referencial use.
Industrial applicibility
Can make by the present invention the polyvinyls that has good heat endurance and good moulding processability in wide moulding processing temperature scope. The catalyst and the preparation method that are used for polyvinyls production of the application of the invention can prepare the polyvinyls with good mechanical strength and the good moulding processability in wide moulding processing temperature scope in addition. Industrial value of the present invention is remarkable.

Claims (2)

1. polyvinyls, it contains by the repeating unit of ethylene derivative with by C 3-8Alpha-olefin derived repeating unit, this ethene polymers satisfies the condition of following (A)-(G):
(A) density d is 910～970, and the unit of density is kg/m 3,
(B) be 0.01～50 in the melt flow MFR of 190 ℃ of measurements under the 2.16kg load, the unit of melt flow is g/10 minute,
(C) the terminal ethylenyl groups number is that per 1000 carbon atoms are 0.2 or are less than 0.2,
(D) at 160 ℃ of melt strength MS that measure down 160Satisfy following formula (1) with MFR:
MS 160＞90-130×log(MFR) (1)
Melt strength MS 160Unit be mN,
(E) at the melt strength MS of 190 ℃ of measurements 190With MS 160Satisfy following formula (2):
MS 160/MS 190＜1.8 (2)
Melt strength MS 190Unit be mN,
(F) flow-activation energy E aSatisfy following formula (3) with d:
127-0.107d＜E a＜88-0.060d (3)
Flow-activation energy E aUnit be kJ/mol,
(G) the ratio Mw/Mn of weight-average molecular weight Mw and number-average molecular weight Mn is 2～6.
2. by the polyvinyls of claim 1, wherein, (A) density d is 910～940.
CN2006800478765A 2005-12-19 2006-12-19 Ethylene polymer, catalyst for production of ethylene polymer, and process for production of ethylene polymer Expired - Fee Related CN101341176B (en)

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