CN106008767A - Alcohol oxymethylene bridged bimetallic half-metallocene catalyst and preparation method and application - Google Patents

Alcohol oxymethylene bridged bimetallic half-metallocene catalyst and preparation method and application Download PDF

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CN106008767A
CN106008767A CN201610342348.8A CN201610342348A CN106008767A CN 106008767 A CN106008767 A CN 106008767A CN 201610342348 A CN201610342348 A CN 201610342348A CN 106008767 A CN106008767 A CN 106008767A
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alcohol
catalyst
oxymethylene
reaction
bimetallic
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黄启谷
何磊
石向辉
王静
杨万泰
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Beijing University of Chemical Technology
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Beijing University of Chemical Technology
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/02—Ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/02—Ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/04—Monomers containing three or four carbon atoms
    • C08F210/06—Propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2400/00—Characteristics for processes of polymerization
    • C08F2400/02—Control or adjustment of polymerization parameters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2410/00—Features related to the catalyst preparation, the catalyst use or to the deactivation of the catalyst
    • C08F2410/03—Multinuclear procatalyst, i.e. containing two or more metals, being different or not
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2420/00—Metallocene catalysts
    • C08F2420/04—Cp or analog not bridged to a non-Cp X ancillary anionic donor

Abstract

The invention provides an alcohol oxymethylene bridged bimetallic half-metallocene catalyst and a preparation method and application. The catalyst has the following structure, wherein M1 and M2 are the same or different and each represents a metal atom selected from the group consisting of IIIB, IVB, VB, and VIB; X and X 'are the same or different and are halogen atoms selected from the group consisting of Cl, Br and F; n is a positive integer greater than or equal to 1. The alcohol oxymethylene bridged bimetallic half-metallocene catalyst has a low cost and high activity at a temperature of 30 DEG C to 200 DEG C; a comonomer has a high insertion amount, and an olefin polymerization product has a low density and excellent performances.

Description

Alcohol Oxymethylene bridging bimetallic half cyclopentadienyl catalyst and preparation method and application
Technical field
The invention belongs to olefin polymerization catalysis and olefin coordination polymerization field, be particularly used for ethylene or propylene homo close, Alcohol Oxymethylene bridging bimetallic half cyclopentadienyl catalyst of ethylene/alpha-olefin combined polymerization or propylene/alpha-olefins combined polymerization and application.
Background technology
Metallocene catalyst is single because of its active center, the activity of catalyst, the stereoregularity of polymer, molecular weight and point Son amount distribution can obtain the characteristics such as control receive significant attention by changing ligand structure；And metallocene catalyst synthesizes The excellent properties of polymer obtained consistent accreditation.
Polyolefin products has many advantages, as easily processing, Heat stability is good, against weather is good, chemical resistance is good and Validity period limits for length etc., are welcome by market deeply.But polyolefin (such as PE, PP etc.) resistance to low temperature is poor, degree of crystallinity is high, Its range of application is caused to be restricted.If inserting a number of high alpha-olefin in molecular polyolefin chain (such as 1- Octene etc.) it is prepared as block copolymer, polyolefinic structure and performance significant change will occur: density polymer ratio can be made The most polyolefinic lower, density is 0.85～0.92g/cm3Between；Glass transition temperature is low, and resistance to low temperature is good, And dispersibility, weatherability, flexibility, pliability and good processability.The performance of ethylene/1-octene copolymer than ethylene/ Propylene copolymer and the superior performance of Ethylene/1-butene copolymer, ethylene/1-octene copolymer replace ethylene/propene copolymer and The epoch of Ethylene/1-butene copolymer are at hand.
Chien[Chien J,et al.Journal of Polymer Science,Part A:Polymer Chemistry,1991,29, 1603] rac-anti-Et (Me is used4C5)(Ind)TiCl2/rac-syn-Et(Me4C5)(Ind)TiCl2Equimolar mixture and rac-anti-Et(Me4C5)(Ind)TiMe2Asymmetric means of special bridged metallocene catalysts synthesizes and has crystallization-many blocks of amorphous solid The thermoplasticity PP elastomer of structure.Gauthier [Gauthier W J.Macromolecules, 1995,28,3779] uses Me2C(Cp)(Ind)TiCl2、Me2Si(Cp)(Ind)ZrCl2And Me2Si(Cp)(Ind)HfCl2Metallocene catalyst has synthesized PP bullet Gonosome.Resconi [Resconi L, etal.Chemical Reviews, 2000,100,1253] uses Me2Si(Flu)2ZrCl2With Me2Si(Flu)2ZrMe2C2vSymmetrical without chirality means of special bridged metallocene catalysts synthesize weight average relative molecular weight reach 100000～ 400000, elastic and that optical property is good completely amorphous type PP elastomer.
Patent [application number: DE 19850898] uses 1-(9-fluorenyl)-1,2,3,6-tetrahydrochysene-1,3,3-trimethyl pentalene zirconium two Chlorine compound/MAO catalyst system and catalyzing prepares ethylene/propene/5-ethylidene-2-norbornene copolymer, and polymerization temperature is 20～80 DEG C, Polymerization pressure is 0.3～3.0MPa, and the mass fraction of ethylene of copolymer is 0.4～0.9, and propylene mass fraction is 0.095～0.59, Non-conjugated diene hydrocarbon mass fraction is 0.005～0.12.Patent [application number: WO 2000022005] uses metallocene catalyst Synthetic molecular weight height, narrow molecular weight distribution and TgLow EPM, polymerization temperature is 30～80 DEG C, and polymerization pressure is 0.07～21 The mass fraction of ethylene of MPa, EPM is 0.35～0.8, and propylene mass fraction is 0.15～0.6.
Bergemann[Bergemann C,et al.Journal of Molecular Catalysis A:Chemical,1996,105, 87] Me is used2Si(H4Ind)2ZrCl2/ MAO at 0.1-150MPa, 120-220 DEG C compare ethylene and propylene, 1-butylene, 1-hexene and the combined polymerization of 1-decene, find that the alpha-olefin that carbon number is the highest is the most difficult with ethylene copolymer, ethylene and 1-butylene copolymerization Time reactivity ratio ratio be re/rb=53.45/0.02, when ethylene and 1-hervene copolymer, the ratio of reactivity ratio is re/rh=62.70/0.02, When ethylene and 1-decene copolymerization, the ratio of reactivity ratio is re/rd=80.02/0.01.Shan[Shan C L P,et al. Macromolecular chemistry and physics, 2000,201,2195] use carried metallocene catalyst Et(Ind)2ZrCl2Under pressure 10MPa, catalyzed ethylene closes with 1-hervene copolymer, catalysis activity up to 4341.7kg P/ (mol Zr.h), in copolymer, the molar content of 1-hexene is about 3%.Losio[Losio S,et al.Macromolecules,2008, 41,1104] using means of special bridged metallocene catalysts catalyzed ethylene and 4-methyl-1-pentene combined polymerization, comonomer insertion is 0.15 Between mol% to 5.59mol%.
The studies above result shows, metallocene catalyst (except constrained geometry) and high alpha-olefin are thrown despite the use of Material ratio, alpha-olefin (C4Above) the most relatively low with the copolymerized ability of ethylene.
But, patent [application number: US5218071] uses ethyl-bridged metallocenes/MAO catalyst system and catalyzing at normal pressure to 5.0MPa Under, make solvent with toluene, catalyzed ethylene closes with alpha-olefin copolymer, synthesis of polyolefins elastomer Tafmer, polymer molecular chain The molar content of middle alpha-olefin is high (reaching 9%), and the density of product is low, is 0.85～0.92g/cm3, molecular weight distribution is 1.2～4.0； This patent adds organo-silicon compound before being characterised by polymerization in metallocene catalyst.Lin[Lin S A,et al. Macromolecular chemistry and physics, 2001,202,1935] use single cyclopentadienyl titanium Cp*Ti (OR)3/ mMAO is catalyzed System synthesizes the Ethylene/1-butene copolymer elastomer of high degree of randomness and high molecular, competing poly-when ethylene and 1-butylene copolymerization The ratio of rate is re/rb=1.08/0.29, in copolymer, the molar content of 1-butylene reaches 25.4%.Dupont dow Elastomets company Constrained geometry metallocene catalyst is used to develop polyolefin elastomer Engage, including can blow molding and extrusion molding Deng 8 new varieties, belong to the Ethylene/1-butene of high fondant-strength, ethylene/1-hexene copolymer.
Patent 201510082857.7 disclose dicyclopentadiene metallic compound by the alkyl or derivatives thereof of abutment C3-C30, The cycloalkyl or derivatives thereof of C3-C30, the aryl or derivatives thereof of C6-C30 or the heterocyclic aryl of C6-C30 or its derive Internet of Things is connected into bimetallic half cyclopentadienyl catalyst, and catalysis activity is high, can the effectively equal (co) polymerization of catalyzed ethylene and propylene equal (being total to) Polymerization.But patent 201510082857.7 is without reference to bimetallic half cyclopentadienyl catalyst of alcohol Oxymethylene bridging.
In sum, in catalyst system, there was added organic silicon compound, electron donor or use Cp*M (OR)3Type metallocene Catalyst, metallocene catalyst (constrained geometry)/MAO (or other promoter) catalyst system and catalyzing catalyzed ethylene and C4Above Alpha-olefin copolymer time, alpha-olefin molar content in the copolymer can significantly improve, and the density of copolymer is low.
The most more with the report that alpha-olefin copolymer closes although with metallocene catalyst catalyzed ethylene, the molecular structure of metallocene is more Come the most complicated, be a challenge for commercial production cost.The invention discloses a kind of bimetallic half cyclopentadienyl catalyst, be to tie The simple single metallocene catalyst of structure combines with phenol epoxide or secondary amino group etc..At high temperature catalyst tool during catalysis in olefine polymerization There is catalysis activity high, also can improve alpha-olefin as comonomer insertion in the copolymer, improve polyolefin properties.
Summary of the invention
It is an object of the invention to provide bimetallic half cyclopentadienyl catalyst of a kind of alcohol Oxymethylene bridging, and it is for ethylene homo Close, propylene homo closes, ethylene and alpha-olefin copolymer close or propylene closes with alpha-olefin copolymer application and preparation method.
Olefinic polymerization alcohol Oxymethylene bridging bimetallic half cyclopentadienyl catalyst provided by the present invention, its structure meets formula (1)；
In formula (1), R1、R1＇, R2、R2＇, R3、R3＇, R4、R4＇, R5、R5＇ is identical or different, independently Selected from hydrogen atom, the alkyl of C1-C20, the cycloalkyl of C3-C20, the aryl of C6-C20, the halogenated aryl of C6-C20, The Heterocyclylalkyl of C2-C20 and the miscellaneous alkyl of the virtue of C6-C20；Wherein, substituent R1、R2、R3、R4、R5Or R1＇, R2＇, R3＇, R4＇, R5＇ is closed into monocycle or condensed ring each other or does not closes；Such as, monocycle is C3-C20 cycloalkane, C3-C20 Heterocycloalkane or phenyl ring；Condensed ring is the condensed ring of C8-C20, for example, naphthalene, pyrene；
Wherein, M1、M2It is identical or different metallic atom, is respectively selected from III B, IV B, VB, VIB or VIII One, preferably Ti, Zr, Hf, Sc, Y, Nd, La, Sm, Ru, Rh, Fe, Co, Ni or Pd；
Wherein, X, X ＇ is identical or different halogen atom, selected from Cl, Br, F；
Wherein, n is the positive integer more than or equal to 1；
Wherein, R6For the alkyl or derivatives thereof of C1-C30, the cycloalkyl or derivatives thereof of C3-C30, the virtue of C6-C30 Base or derivatives thereof, the Heterocyclylalkyl or derivatives thereof of C2-C30, or R6 do not exist；Derivant refer to wherein hydrogen atom or Atomic group is replaced and derivative more complicated product by other atoms or atomic group；Such as, R6Can be substituted or unsubstituted The alkyl of 0-C20, the cycloalkyl of C3-C20, the aryl of C6-C20, the Heterocyclylalkyl of C3-C20, substituent group can be C1-C20 Alkyl, the cycloalkyl of C3-C20, the aryl of C6-C20, the halogenated aryl of C6-C20, the alkoxyl of C1-C20, C3-C20 Cycloalkyloxy or the aryloxy group of C6-C20, or R6Can be the alkyl containing the heteroatomic C2-C20 such as N, S, O, C3-C20 Cycloalkyl, the aryl of C6-C20, the Heterocyclylalkyl of C3-C20；
In the one aspect of the present invention, described bimetallic half cyclopentadienyl catalyst is:
Cat.1
Cat.2
Cat.3
Cat.4
Cat.5
Cat.6
Cat.7
Cat.8
Cat.9
Cat.10
Cat.11
Cat.12
Cat.13
Cat.14
Cat.15
Cat.16
Cat.17
Cat.18
Cat.19
Present invention also offers a kind of catalyst for olefinic polymerization, be made up of major catalyst and promoter, its feature exists In: wherein major catalyst is above-mentioned alcohol Oxymethylene bridging bimetallic half cyclopentadienyl catalyst.
In the one aspect of the present invention, described promoter is alkyl aluminum, MAO (MAO) or modification MAO (mMAO) etc..
In an additional aspect of the present invention, described major catalyst is 1:(100-5000 with the mol ratio of promoter).
The invention provides the preparation method of described formula (1) alcohol Oxymethylene bridging bimetallic half cyclopentadienyl catalyst, its feature It is to comprise the following steps:
1) in organic solvent, will have and meet formula (2a) and the compound dissolution of (2b)；
Wherein, R1、R1＇, R2、R2＇, R3、R3＇, R4、R4＇, R5、R5＇ is identical or different substituent group, respectively The independent halo virtue representing hydrogen atom, the alkyl of C1-C20, the cycloalkyl of C3-C20, the aryl of C6-C20, C6-C20 The miscellaneous alkyl of virtue of base, the Heterocyclylalkyl of C2-C20 and C6-C20, wherein substituent R1、R2、R3、R4、R5Or R1＇, R2＇, R3＇, R4＇, R5＇ is closed into monocycle or condensed ring each other or does not closes；Meet formula (2a) or the chemical combination of (2b) Thing is preferably selected from cyclopentadiene and derivant, indenes and derivant thereof, fluorenes and derivant thereof；
At a temperature of-80 DEG C-120 DEG C, react 0.5h-12h, react formation anion with the n-BuLi added；Then, exist At a temperature of-50 DEG C-150 DEG C, with transition metal halide MXmReaction 1h-10h, obtains meeting the compound of formula (3),
Wherein M is metallic atom, selected from III B, IV B, VB, VIB or VIII race, preferably Ti, Zr, Hf, Sc, Y, Nd, La, Sm, Ru, Rh, Fe, Co, Ni or Pd；Wherein, X is halogen atom, selected from Cl, Br, F；
Wherein metal halide MXmIn, M is transition metal atoms, selected from III B, IV B, VB, VIB or VIII race, The preferably one in Ti, Zr, Hf, Sc, Y, Nd, La, Sm, Ru, Rh, Fe, Co, Ni or Pd；Wherein, X is halogen atom, selected from Cl, Br, F；M is 2,3 or 4.
Preferably, there is the compound meeting (2a) or (2b) structure and metal halide MXmMol ratio be 1: 0.4-1.6；
2) will have and meet the compound dissolution of formula (3) in organic solvent, adding carbon number is that C2 to C30 is special The diatomic alcohol compounds of fixed structure, at-20 DEG C-110 DEG C, reacts 0.5h-24h；It is dried to obtain after removing solvent and there is symbol Close the compound of aforementioned formula (1),
Carbon number is the preferred ethylene glycol of diatomic alcohol compounds of C2 to C20, propylene glycol, and butanediol, pentanediol, oneself is two years old Alcohol, decanediol, Isosorbide-5-Nitrae-cyclohexanedimethanol, 1,2-cyclohexanedimethanol, Isosorbide-5-Nitrae-terephthalyl alcohol, 1,3-isophthalic alcohol, 1,2- Phthalyl alcohol, 1,1 ＇-biphenyl-4,4 ＇-dimethanol, 1,1 ＇-biphenyl-3,4 ＇-dimethanol, 1,1 ＇-biphenyl-2,2 ＇-dimethanol.
In the one aspect of the present invention, the compound wherein meeting formula (3) is C2's to C20 with carbon number The mol ratio of diatomic alcohol compounds is 1.5-2.5:1.
Organic solvent used in the process of synthetic catalyst is saturated alkane, saturated rings alkane or aromatic hydrocarbons or their mixing Thing；Preferably normal hexane, normal heptane, n-decane, n-dodecane, oxolane, ether, toluene, dimethylbenzene, dichloromethane Alkane or their mixture.
The invention provides above-mentioned alcohol Oxymethylene bimetallic half cyclopentadienyl catalyst or the application of above-mentioned catalyst.Wherein, provided Bimetallic half cyclopentadienyl catalyst or catalyst be used for being catalyzed nonpolar olefinic and be all polymerized or combined polymerization.Wherein said nonpolar alkene Hydrocarbon is the alpha-olefin of C2-C20, optimal ethylene, propylene, 1-butylene, 1-hexene, 1-octene, 1-decene, 12-1-alkene, 18-1-alkene, styrene, cyclopentenes, 3-methyl-1-butene, 4-methyl-1-pentene, isoprene, 1,3-butadiene, α- Methyl styrene, norborene.
Alcohol Oxymethylene bridging bimetallic half cyclopentadienyl catalyst provided by the present invention or catalyst are used for being catalyzed nonpolar olefinic and gather Close, polymerizing condition be polymerization temperature be 30 DEG C-200 DEG C, olefinic polymerization pressure is 0.1MPa-30MPa, during polyreaction Between be 5min-240min.
Olefin polymerization catalysis provided by the present invention has the advantages that
The alcohol Oxymethylene bridging bimetallic half cyclopentadienyl catalyst low cost of the present invention, still has high activity under high-temperature；For When ethylene or propylene are with alpha-olefin or polarity vinyl monomer copolymerization, alpha-olefin or polarity vinyl monomer insertion rate are high；Polyolefin is close Spend low, performance is more excellent.
Below in conjunction with detailed description of the invention, the invention will be further described, but protection scope of the present invention is not limited only to following reality Execute example.
Detailed description of the invention
Embodiment 1
1) preparation of metallocene catalyst: under anhydrous and oxygen-free, nitrogen protection, add 100mL in 250mL reaction bulb Toluene, is sequentially added into 3.3mL (0.04mol) cyclopentadiene under room temperature (open system of standard atmosphere pressure, as follows), 3.8mL (0.04mol) n-BuLi, reacts 2h；It is warming up to 40 DEG C, reacts 4h.At 0 DEG C, add in this intermediate 4.4mL(0.04mol)TiCl4, and react 1h in 0 DEG C；Subsequently, room temperature reaction 3h；Sucking filtration, washs solid with normal hexane Material three times；Sucking filtration at 30 DEG C, obtains compound M1 (see formula (3)), and productivity is 95.6%.
2) preparation of alcohol Oxymethylene bridging bimetallic half cyclopentadienyl catalyst: under nitrogen protection to the dry reaction with magneton Add 100mL toluene in Ping, add 4.4g (0.02mol) compound M1 stirring and dissolving, at 10 DEG C, add 0.01mol Ethylene glycol, keep 10 DEG C reaction 30min, after be warming up to 40 DEG C reaction 3h.After reaction terminates, filter and use normal hexane 50mL washs repeatedly at 40 DEG C, sucking filtration；Resulting procatalyst Cat.1:
3) vinyl polymerization: under the conditions of anhydrous and oxygen-free, in 250mL reaction bulb, is sequentially added into 100mL toluene, 10mg Major catalyst (Cat.1), 3.8mL MAO solution (1.5mol/L).Take a breath after three times, be maintained at 180 DEG C and 2atm Polyase 13 0min under ethylene pressure, terminates reaction with the ethanol solution containing 10% (volume fraction, as follows) hydrochloric acid, filters, By washing with alcohol 3 times, polymer is vacuum dried 24h at 40 DEG C.
4) ethylene copolymerization: under the conditions of anhydrous and oxygen-free, in 250mL reaction bulb, is sequentially added into 100mL toluene, and 10 Mg major catalyst (Cat.1), 3.8mL MAO solution (1.5mol/L).Take a breath after three times, be maintained at 180 DEG C, 2atm Ethylene pressure and 2atm propylene under polyase 13 0min, with containing 10% hydrochloric acid ethanol solution terminate reaction, filter, use Washing with alcohol 3 times, polymer is vacuum dried 24h at 40 DEG C.
Embodiment 2
1) preparation of alcohol Oxymethylene bridging bimetallic half cyclopentadienyl catalyst: to magneton under anhydrous and oxygen-free and nitrogen are protected Dry reaction bottle in add 100mL toluene, add 4.4g (0.02mol) compound M1 stirring and dissolving, at 10 DEG C Add 0.01mol1,1 '-biphenyl-4,4 '-dimethanol, keeps 10 DEG C reaction 30min, after be warming up to 40 DEG C react 3h.Instead After should terminating, filter and wash repeatedly with normal hexane 50mL at 40 DEG C, sucking filtration；Resulting procatalyst component Cat. 2:
2) vinyl polymerization: under the conditions of anhydrous and oxygen-free, in 250mL reaction bulb, is sequentially added into 100mL toluene, 10mg Major catalyst (Cat.2), 4.0mL MAO solution (1.5mol/L).Take a breath after three times, be maintained at 160 DEG C and 2atm Polyase 13 0min under ethylene pressure, terminates reaction with the ethanol solution containing 10% (volume fraction, as follows) hydrochloric acid, filters, By washing with alcohol 3 times, polymer is vacuum dried 24h at 40 DEG C.
3) ethylene copolymerization: under the conditions of anhydrous and oxygen-free, in 250mL reaction bulb, is sequentially added into 100mL toluene, and 10 Mg major catalyst (Cat.2), 4.8mL MAO solution (1.5mol/L).Take a breath after three times, be maintained at 160 DEG C, 1atm Ethylene pressure and 2atm propylene under polyase 13 0min, with containing 10% hydrochloric acid ethanol solution terminate reaction, filter, use Washing with alcohol 3 times, polymer is vacuum dried 24h at 40 DEG C.
Embodiment 3
1) preparation of alcohol Oxymethylene bridging bimetallic half cyclopentadienyl catalyst: to magneton under anhydrous and oxygen-free and nitrogen are protected Dry reaction bottle in add 100mL toluene, add 4.4g (0.02mol) compound M1 stirring and dissolving, at 10 DEG C Add 0.01mol decanediol, keeps 10 DEG C reaction 30min, after be warming up to 40 DEG C react 3h.After reaction terminates, filter And wash repeatedly with normal hexane 50mL at 40 DEG C, sucking filtration；Resulting procatalyst component Cat.3:
2) ethylene copolymerization: under the conditions of anhydrous and oxygen-free, in 250mL reaction bulb, is sequentially added into 100mL toluene, and 10 Mg major catalyst (Cat.3), 4.5mL MAO solution (1.5mol/L), 5mL3-methyl isophthalic acid-butylene.Take a breath after three times, It is maintained under the ethylene pressure of 170 DEG C and 2atm and is polymerized 1h, terminate reaction with the ethanol solution containing 10% hydrochloric acid, filter, By washing with alcohol 3 times, polymer is vacuum dried 24h at 40 DEG C.
Embodiment 4
1) preparation of alcohol Oxymethylene bridging bimetallic half cyclopentadienyl catalyst: to magneton under anhydrous and oxygen-free and nitrogen are protected Dry reaction bottle in add 100mL toluene, add 4.4g (0.02mol) compound M1 stirring and dissolving, at 10 DEG C Add 0.01mol1,4-terephthalyl alcohol, keeps 10 DEG C reaction 1h, after be warming up to 50 DEG C react 3h.After reaction terminates, Filter and wash repeatedly with normal hexane 50mL at 30 DEG C, sucking filtration；Resulting procatalyst component Cat. 4:
2) ethylene copolymerization: under the conditions of anhydrous and oxygen-free, in 250mL reaction bulb, is sequentially added into 100mL toluene, and 10 Mg major catalyst (Cat.4), 6.7mL MAO solution (1.5mol/L), 5mL 1-hexene.Take a breath after three times, be maintained at It is polymerized 1h under the ethylene pressure of 180 DEG C and 2atm, terminates reaction with the ethanol solution containing 10% hydrochloric acid, filter, use ethanol Washing 3 times, polymer is vacuum dried 24h at 40 DEG C.
Embodiment 5
1) preparation of metallocene catalyst: under anhydrous and oxygen-free, nitrogen protection, add 100mL in 250mL reaction bulb Toluene, is sequentially added into 3.3mL (0.04mol) cyclopentadiene at 10 DEG C, 3.8mL (0.04mol) n-BuLi, anti-at 10 DEG C Answer 1h；It is warming up to 40 DEG C, reacts 4h.Under cryosel bath, in this intermediate, add 9.3g (0.04mol) ZrCl4, and in 1h is reacted under cryosel bath；Subsequently, 40 DEG C of reaction 4h；Sucking filtration, by normal hexane washed solid three times, at 40 DEG C Sucking filtration, obtains compound M2 (see formula (3)), and productivity is 93.8%.
2) preparation of alcohol Oxymethylene bridging bimetallic half cyclopentadienyl catalyst: under nitrogen protection to the dry reaction with magneton Add 100mL toluene in Ping, add 5.26g (0.02mol) compound M2 stirring and dissolving, at 20 DEG C, add 0.01mol1,2- Phthalyl alcohol, keep 20 DEG C reaction 30min, after be warming up to 50 DEG C reaction 3h.After reaction terminates, filter and with just Hexane 50mL washs repeatedly at 40 DEG C, sucking filtration；Resulting procatalyst component Cat. 5:
3) ethylene copolymerization: under the conditions of anhydrous and oxygen-free, in 250mL reaction bulb, is sequentially added into 100mL toluene, and 10 Mg major catalyst (Cat.5), 4.2mL MAO solution (1.5mol/L), 2g norborene.Take a breath after three times, be maintained at 180 DEG C, be polymerized 1h under the ethylene pressure of 2atm, terminate reaction with the ethanol solution containing 10% hydrochloric acid, filter, use ethanol Washing 3 times, polymer is vacuum dried 24h at 40 DEG C.
Embodiment 6
1) preparation of alcohol Oxymethylene bridging bimetallic half cyclopentadienyl catalyst: to magneton under anhydrous and oxygen-free and nitrogen are protected Dry reaction bottle in add 100mL toluene, add 0.01mol metallocene catalyst M1 and 0.01mol metallocene catalysis Agent M2, stirring and dissolving, add 0.01mol decanediol at 5 DEG C, keep 5 DEG C of reaction 60min, after be warming up to 50 DEG C instead Answer 3h.After reaction terminates, filter and wash repeatedly with normal hexane 50mL at 40 DEG C, sucking filtration；Resulting procatalyst group Point Cat.6:
2) ethylene copolymerization: under the conditions of anhydrous and oxygen-free, in 250mL reaction bulb, is sequentially added into 100mL toluene, and 10 Mg major catalyst (Cat.6), 10mL MAO solution (1.5mol/L), 5mL 12-1-alkene.Take a breath after three times, keep Under the ethylene pressure of 160 DEG C and 2atm, it is polymerized 1h, terminates reaction with the ethanol solution containing 10% hydrochloric acid, filter, use second Alcohol washs 3 times, and polymer is vacuum dried 24h at 40 DEG C.
Embodiment 7
1) preparation of metallocene catalyst: under anhydrous and oxygen-free, nitrogen protection, add 100mL in 250mL reaction bulb Toluene, is sequentially added into 3.3mL (0.04mol) cyclopentadiene, 3.8mL (0.04mol) n-BuLi, reacts at 5 DEG C at 5 DEG C 2h；It is warming up to 40 DEG C, reacts 5h.Under cryosel bath, in this intermediate, add 7.82g (0.04mol) YCl3, and in ice 1h is reacted under salt bath；Subsequently, 30 DEG C of reaction 4h；Sucking filtration, by normal hexane washed solid three times, takes out at 40 DEG C Filter, obtains compound M3 (see formula (3)), and productivity is 95.6%.
2) preparation of alcohol Oxymethylene bridging bimetallic half cyclopentadienyl catalyst: under nitrogen protection to anti-with being dried of magneton Answer addition 100mL toluene in bottle, add 4.5g (0.02mol) compound M3 stirring and dissolving, at 10 DEG C, add 0.01mol Isosorbide-5-Nitrae-terephthalyl alcohol, keep 10 DEG C reaction 30min, after be warming up to 50 DEG C reaction 3h.After reaction terminates, filter and use Normal hexane 50mL washs repeatedly at 40 DEG C, sucking filtration；Resulting procatalyst component Cat. 7:
3) ethylene copolymerization: under the conditions of anhydrous and oxygen-free, in 250mL reaction bulb, is sequentially added into 100mL toluene, and 10 Mg major catalyst (Cat.7), 7.8mL MAO solution (1.5mol/L), 5mL 1-octene.Take a breath after three times, be maintained at 180 DEG C, be polymerized 60min under the ethylene pressure of 3atm, terminate reaction with the ethanol solution containing 10% hydrochloric acid, filter, use second Alcohol washs 3 times, and polymer is vacuum dried 24h at 40 DEG C.
Embodiment 8
1) preparation of alcohol Oxymethylene bridging bimetallic half cyclopentadienyl catalyst: to magneton under anhydrous and oxygen-free and nitrogen are protected Dry reaction bottle in add 100mL toluene, add 4.4g (0.02mol) compound M3 stirring and dissolving, at 10 DEG C Add 0.01mol 1,1 '-biphenyl-2,2 '-dimethanol, keeps 10 DEG C reaction 60min, after be warming up to 50 DEG C react 3h.Reaction After end, filter and wash repeatedly with normal hexane 50mL at 40 DEG C, sucking filtration；Resulting procatalyst component Cat.8:
2) copolymerization of propylene: under the conditions of anhydrous and oxygen-free, in 250mL reaction bulb, is sequentially added into 100mL toluene, and 10 Mg major catalyst (Cat.8), 6.5mL MAO solution (1.5mol/L), 5mL 1,3-butadiene.Take a breath after three times, keep Polyase 13 0min under the propylene pressure of 170 DEG C and 3atm, terminates reaction with the ethanol solution containing 10% hydrochloric acid, filters, By washing with alcohol 3 times, polymer is vacuum dried 24h at 40 DEG C.
Embodiment 9
1) preparation of alcohol Oxymethylene bridging bimetallic half cyclopentadienyl catalyst: to magneton under anhydrous and oxygen-free and nitrogen are protected Dry reaction bottle in add 100mL toluene, add 0.01mol metallocene catalyst M2 and 0.01mol metallocene catalysis Agent M3, stirring and dissolving, add 0.01mol decanediol at 5 DEG C, keep 5 DEG C of reaction 60min, after be warming up to 50 DEG C instead Answer 3h.After reaction terminates, filter and wash repeatedly with normal hexane 50mL at 40 DEG C, sucking filtration；Resulting procatalyst component Cat.9:
2) copolymerization of propylene: under the conditions of anhydrous and oxygen-free, in 250mL reaction bulb, is sequentially added into 100mL toluene, and 10 Mg major catalyst (Cat.9), 6.5mL MAO solution (1.5mol/L), 5mL isoprene.Take a breath after three times, keep Polyase 13 0min under the propylene pressure of 170 DEG C and 3atm, terminates reaction with the ethanol solution containing 10% hydrochloric acid, filters, By washing with alcohol 3 times, polymer is vacuum dried 24h at 40 DEG C.
Embodiment 10
1) preparation of metallocene catalyst: under anhydrous and oxygen-free, nitrogen protection, add 100mL in 250mL reaction bulb Toluene, is sequentially added into 3.3mL (0.04mol) cyclopentadiene at 10 DEG C, 3.8mL (0.04mol) n-BuLi, anti-at 10 DEG C Answer 2h；It is warming up to 40 DEG C, reacts 5h.Under cryosel bath, in this intermediate, add 5.22g (0.04mol) NiCl2, and 1h is reacted under cryosel is bathed；Subsequently, 50 DEG C of reaction 4h；Sucking filtration, by normal hexane washed solid three times, at 40 DEG C Lower sucking filtration, obtains compound M4 (see formula (3)), and productivity is 95.6%.
2) preparation of alcohol Oxymethylene bridging bimetallic half cyclopentadienyl catalyst: under nitrogen protection to the dry reaction with magneton Add 100mL toluene in Ping, add 3.9g (0.02mol) compound M4 stirring and dissolving, at 10 DEG C, add 0.01mol Isosorbide-5-Nitrae-terephthalyl alcohol, keep 10 DEG C reaction 30min, after be warming up to 40 DEG C reaction 4h.After reaction terminates, filter also Wash repeatedly with normal hexane 50mL at 40 DEG C, sucking filtration；Resulting procatalyst component Cat. 10:
3) copolymerization of propylene: under the conditions of anhydrous and oxygen-free, in 250mL reaction bulb, is sequentially added into 100mL toluene, and 10 Mg major catalyst (Cat.10), 9.5mL MAO solution (1.5mol/L), 5mL 1-hexene.Take a breath after three times, be maintained at 180 DEG C, be polymerized 1h under the propylene pressure of 2atm, terminate reaction with the ethanol solution containing 10% hydrochloric acid, filter, use ethanol Washing 3 times, polymer is vacuum dried 24h at 40 DEG C.
Embodiment 11
1) preparation of metallocene catalyst: under anhydrous and oxygen-free, nitrogen protection, add 100mL in 250mL reaction bulb Toluene, is sequentially added into 5.5mL (0.04mol) fluorenes, 3.8mL (0.04mol) n-BuLi, room temperature reaction 1h under room temperature；Rise Temperature, to 50 DEG C, reacts 3h.Under cryosel bath, in this intermediate, add 4.4mL (0.04mol) TiCl4, and bathe in cryosel Lower reaction 1h；Subsequently, 50 DEG C of reaction 4h；Sucking filtration, by normal hexane washed solid three times, sucking filtration at 40 DEG C, Obtaining compound M5 (see formula (3)), productivity is 95.3%.
2) preparation of alcohol Oxymethylene bridging bimetallic half cyclopentadienyl catalyst: under nitrogen protection to the dry reaction with magneton Add 100mL toluene in Ping, add 6.39g (0.02mol) compound M5 stirring and dissolving, at 10 DEG C, add 0.01mol Butanediol, keep 10 DEG C reaction 30min, after be warming up to 40 DEG C reaction 4h.After reaction terminates, filter and use normal hexane 50mL washs repeatedly at 40 DEG C, sucking filtration；Resulting procatalyst component Cat 11:
3) copolymerization of propylene: under the conditions of anhydrous and oxygen-free, in 250mL reaction bulb, is sequentially added into 100mL toluene, and 10 Mg major catalyst (Cat.11), 8.3mL MAO solution (1.5mol/L), 5mL 18-1-alkene.Take a breath after three times, protect Hold 180 DEG C, be polymerized 1h under the propylene pressure of 3atm, terminate reaction with the ethanol solution containing 10% hydrochloric acid, filter, use Washing with alcohol 3 times, polymer is vacuum dried 24h at 40 DEG C.
Embodiment 12
1) preparation of alcohol Oxymethylene bridging bimetallic half cyclopentadienyl catalyst: to magneton under anhydrous and oxygen-free and nitrogen are protected Dry reaction bottle in add 100mL toluene, add 6.39g (0.02mol) compound M5 stirring and dissolving, at 10 DEG C Add 0.01mol Isosorbide-5-Nitrae-cyclohexanedimethanol, keeps 10 DEG C reaction 60min, after be warming up to 50 DEG C react 3h.Reaction terminates After, filter and wash repeatedly with normal hexane 50mL at 40 DEG C, sucking filtration；Resulting procatalyst component Cat. 12:
2) copolymerization of propylene: under the conditions of anhydrous and oxygen-free, in 250mL reaction bulb, is sequentially added into 100mL toluene, and 10 Mg major catalyst (Cat.12), 7.6mL MAO solution (1.5mol/L), 5mL styrene.Take a breath after three times, be maintained at Polyase 13 0min under the propylene pressure of 70 DEG C and 2atm, terminates reaction with the ethanol solution containing 10% hydrochloric acid, filters, uses second Alcohol washs 3 times, and polymer is vacuum dried 24h at 40 DEG C.
Embodiment 13
1) preparation of alcohol Oxymethylene bridging bimetallic half cyclopentadienyl catalyst: to magneton under anhydrous and oxygen-free and nitrogen are protected Dry reaction bottle in add 100mL toluene, add 6.39g (0.02mol) compound M5 stirring and dissolving, at 20 DEG C Add 0.01mol 1,1 '-biphenyl-4,4 '-dimethanol, keeps 20 DEG C reaction 1h, after be warming up to 50 DEG C react 3h.Reaction knot Shu Hou, filters and washs repeatedly with normal hexane 50mL at 40 DEG C, sucking filtration；Resulting procatalyst component Cat.13:
2) copolymerization of propylene: under the conditions of anhydrous and oxygen-free, in 250mL reaction bulb, is sequentially added into 100mL toluene, and 10 Mg major catalyst (Cat.13), 5.6mL MAO solution (1.5mol/L), 5mL1-octene.Take a breath after three times, be maintained at It is polymerized 1h under the propylene pressure of 60 DEG C and 3atm, terminates reaction with the ethanol solution containing 10% hydrochloric acid, filter, use ethanol Washing 3 times, polymer is vacuum dried 24h at 40 DEG C.
Embodiment 14
1) preparation of metallocene catalyst: under anhydrous and oxygen-free, nitrogen protection, add 100mL in 250mL reaction bulb Toluene, is sequentially added into 4.7mL (0.04mol) indenes, 3.8mL (0.04mol) n-BuLi, 10 DEG C of reaction 1h at 10 DEG C；Rise Temperature, to 40 DEG C, reacts 3h.Under cryosel bath, in this intermediate, add 9.35g (0.04mol) ZrCl4, and under cryosel is bathed Reaction 1h；Subsequently, 40 DEG C of reaction 4h；Sucking filtration, by normal hexane washed solid three times, sucking filtration at 40 DEG C, obtaining Compound M6 (see formula (3)), productivity is 96.8%.
2) preparation of alcohol Oxymethylene bridging bimetallic half cyclopentadienyl catalyst: under nitrogen protection to the dry reaction bottle with magneton Middle addition 100mL toluene, adds 6.32g (0.02mol) compound M8 stirring and dissolving, adds 0.01mol at 20 DEG C Butanediol, keep 30 DEG C reaction 30min, after be warming up to 50 DEG C reaction 3h.After reaction terminates, filter and use normal hexane 50mL washs repeatedly at 40 DEG C, sucking filtration；Resulting procatalyst component Cat.14:
3) ethylene copolymerization: under the conditions of anhydrous and oxygen-free, in 250mL reaction bulb, is sequentially added into 100mL toluene, and 10 Mg major catalyst (Cat.14), 9.3mL MAO solution (1.5mol/L), 5mL cyclopentenes.Take a breath after three times, be maintained at 30 DEG C, be polymerized 1h under the ethylene pressure of 3atm, terminate reaction with the ethanol solution containing 10% hydrochloric acid, filter, wash with ethanol Washing 3 times, polymer is vacuum dried 24h at 40 DEG C.
Embodiment 15
1) preparation of alcohol Oxymethylene bridging bimetallic half cyclopentadienyl catalyst: to magneton under anhydrous and oxygen-free and nitrogen are protected Dry reaction bottle in add 100mL toluene, add 6.32g (0.02mol) compound M6 stirring and dissolving, at 30 DEG C Add 0.01mol Isosorbide-5-Nitrae-terephthalyl alcohol, keep 30 DEG C of reaction 1h；After be warming up to 50 DEG C reaction 3h.After reaction terminates, Filter and wash repeatedly with normal hexane 50mL at 40 DEG C, sucking filtration；Resulting procatalyst component Cat.15:
2) ethylene copolymerization: under the conditions of anhydrous and oxygen-free, in 250mL reaction bulb, is sequentially added into 100mL toluene, and 10 Mg major catalyst (Cat.15), 8.8mL MAO solution (1.5mol/L), 5mL 1-hexene.Take a breath after three times, be maintained at Polyase 13 0min under the ethylene pressure of 160 DEG C and 2atm, terminates reaction with the ethanol solution containing 10% hydrochloric acid, filters, uses second Alcohol washs 3 times, and polymer is vacuum dried 24h at 40 DEG C.
Embodiment 16
1) preparation of alcohol Oxymethylene bridging bimetallic half cyclopentadienyl catalyst: to magneton under anhydrous and oxygen-free and nitrogen are protected Dry reaction bottle in add 100mL toluene, add 6.32g (0.02mol) compound M6 stirring and dissolving, under room temperature Add 0.01mol1,1 '-biphenyl-4,4 '-dimethanol, keep room temperature reaction 1h, after be warming up to 50 DEG C reaction 3h.Reaction terminates After, filter and wash repeatedly with normal hexane 50mL at 40 DEG C, sucking filtration；Resulting procatalyst component Cat.16:
2) ethylene copolymerization: under the conditions of anhydrous and oxygen-free, in 250mL reaction bulb, is sequentially added into 100mL toluene, and 10 Mg major catalyst (Cat.16), 9.3mL MAO solution (1.5mol/L), 5mL1-butylene.Take a breath after three times, be maintained at It is polymerized 1h under the ethylene pressure of 180 DEG C and 2atm, terminates reaction with the ethanol solution containing 10% hydrochloric acid, filter, use ethanol Washing 3 times, polymer is vacuum dried 24h at 40 DEG C.
Embodiment 17
1) preparation of metallocene catalyst: under anhydrous and oxygen-free, nitrogen protection, add 100mL in 250mL reaction bulb Toluene, is sequentially added into 4.7mL (0.04mol) indenes, 3.8mL (0.04mol) n-BuLi, 30 DEG C of reaction 1h at 30 DEG C；Rise Temperature, to 50 DEG C, reacts 2h.Under cryosel bath, in this intermediate, add 7.82g (0.04mol) YCl3, and under cryosel is bathed Reaction 1h；Subsequently, 50 DEG C of reaction 4h；Sucking filtration, by normal hexane washed solid three times, sucking filtration at 40 DEG C, obtaining Compound M7 (see formula (3)), productivity is 97.3%.
2) preparation of alcohol Oxymethylene bridging bimetallic half cyclopentadienyl catalyst: under nitrogen protection to the dry reaction with magneton Add 100mL toluene in Ping, add 5.62g (0.02mol) metallocene catalyst M7 stirring and dissolving, add at 20 DEG C 0.01mol 1,1 '-biphenyl-4,4 '-dimethanol, keep 20 DEG C reaction 30min, after be warming up to 50 DEG C reaction 3h.Reaction terminates After, filter and wash repeatedly with normal hexane 50mL at 40 DEG C, sucking filtration；Resulting procatalyst component Cat.17:
3) copolymerization of propylene: under the conditions of anhydrous and oxygen-free, in 250mL reaction bulb, is sequentially added into 100mL toluene, and 10 Mg major catalyst (Cat.17), 8.7mL MAO solution (1.5mol/L), 5g norborene.Take a breath after three times, be maintained at 130 DEG C, be polymerized 1h under the propylene pressure of 2atm, terminate reaction with the ethanol solution containing 10% hydrochloric acid, filter, use ethanol Washing 3 times, polymer is vacuum dried 24h at 40 DEG C.
Embodiment 18
1) preparation of alcohol Oxymethylene bridging bimetallic half cyclopentadienyl catalyst: to magneton under anhydrous and oxygen-free and nitrogen are protected Dry reaction bottle in add 100mL toluene, add 0.01mol metallocene catalyst M7 and 0.01mol metallocene catalysis Agent M6, stirring and dissolving, add 0.01mol1,1 '-biphenyl-4,4 '-dimethanol at 5 DEG C, keep 5 DEG C of reaction 60min, rise afterwards Temperature reacts 3h to 50 DEG C.After reaction terminates, filter and wash repeatedly with normal hexane 50mL at 40 DEG C, sucking filtration；? Main catalyst component Cat.18:
2) copolymerization of propylene: under the conditions of anhydrous and oxygen-free, in 250mL reaction bulb, is sequentially added into 100mL toluene, and 10 Mg major catalyst (Cat.18), 6.5mL MAO solution (1.5mol/L), 5mL cyclopentenes.Take a breath after three times, be maintained at Polyase 13 0min under the propylene pressure of 170 DEG C and 3atm, terminates reaction with the ethanol solution containing 10% hydrochloric acid, filters, uses second Alcohol washs 3 times, and polymer is vacuum dried 24h at 40 DEG C.
Embodiment 19
1) preparation of alcohol Oxymethylene bridging bimetallic half cyclopentadienyl catalyst: to magneton under anhydrous and oxygen-free and nitrogen are protected Dry reaction bottle in add 100mL toluene, add 0.01mol metallocene catalyst M7 and 0.01mol metallocene catalysis Agent M3, stirring and dissolving, add 0.01mol1,1 '-biphenyl-4,4 '-dimethanol at 5 DEG C, keep 5 DEG C of reaction 60min, rise afterwards Temperature reacts 3h to 50 DEG C.After reaction terminates, filter and wash repeatedly with normal hexane 50mL at 40 DEG C, sucking filtration；? Main catalyst component Cat.19:
2) copolymerization of propylene: under the conditions of anhydrous and oxygen-free, in 250mL reaction bulb, is sequentially added into 100mL toluene, and 10 Mg major catalyst (Cat.19), 6.5mL MAO solution (1.5mol/L), 5mL isoprene.Take a breath after three times, keep Polyase 13 0min under the propylene pressure of 170 DEG C and 3atm, terminates reaction with the ethanol solution containing 10% hydrochloric acid, filters, By washing with alcohol 3 times, polymer is vacuum dried 24h at 40 DEG C.
Embodiment 20
1) preparation of alcohol Oxymethylene bridging bimetallic half cyclopentadienyl catalyst: under nitrogen protection to the dry reaction with magneton Add 100mL toluene in Ping, add the silica-based pair of indenyl chlorination of 179.4mg (0.0004mol) metallocene catalyst dimethyl Zirconium, stirring and dissolving, at 20 DEG C add 0.0002mol Isosorbide-5-Nitrae-cyclohexanedimethanol, keeps 30 DEG C react 30min, after be warming up to 50 DEG C of reaction 3h.After reaction terminates, filter and wash repeatedly with normal hexane 50mL at 40 DEG C, sucking filtration；Obtain main catalytic Agent component Cat.20
2) ethylene copolymerization: under the conditions of anhydrous and oxygen-free, in 250mL reaction bulb, is sequentially added into 100mL toluene, and 10 Mg major catalyst (Cat.20), 9.3mL MAO solution (1.5mol/L), 5mL1-decene.Take a breath after three times, be maintained at 160 DEG C, be polymerized 1h under the ethylene pressure of 3atm, terminate reaction with the ethanol solution containing 10% hydrochloric acid, filter, use ethanol Washing 3 times, polymer is vacuum dried 24h at 40 DEG C.
Embodiment 21
1) preparation of alcohol Oxymethylene bridging bimetallic half cyclopentadienyl catalyst: to magneton under anhydrous and oxygen-free and nitrogen are protected Dry reaction bottle in add 100mL toluene, add 179.4mg (0.0004mol) metallocene catalyst dimethyl silica-based Double indenyl zirconium chlorides, add 0.0002mol decanediol, keep room temperature reaction 1h under stirring and dissolving room temperature；After be warming up to 50 DEG C Reaction 3h.After reaction terminates, filter and wash repeatedly with normal hexane 50mL at 40 DEG C, sucking filtration；Resulting procatalyst group Point Cat.21:
2) copolymerization of propylene: under the conditions of anhydrous and oxygen-free, in 250mL reaction bulb, is sequentially added into 100mL toluene, and 10 Mg major catalyst (Cat.21), 8.7mL MAO solution (1.5mol/L), 5mL 1-hexene.Take a breath after three times, be maintained at Polyase 13 0min under the propylene pressure of 180 DEG C and 2atm, terminates reaction with the ethanol solution containing 10% hydrochloric acid, filters, uses second Alcohol washs 3 times, and polymer is vacuum dried 24h at 40 DEG C.
Embodiment 22
1) preparation of alcohol Oxymethylene bridging bimetallic half cyclopentadienyl catalyst: to magneton under anhydrous and oxygen-free and nitrogen are protected Dry reaction bottle in add 100mL toluene, add 179.4mg (0.0004mol) metallocene catalyst dimethyl silica-based Double indenyl zirconium chlorides, add 0.0002mol 1,1 '-biphenyl-4,4 '-dimethanol, keep room temperature reaction 1h under stirring and dissolving room temperature, After be warming up to 40 DEG C reaction 4h.After reaction terminates, filter and wash repeatedly with normal hexane 50mL at 40 DEG C, sucking filtration； Resulting procatalyst component Cat.22:
2) copolymerization of propylene: under the conditions of anhydrous and oxygen-free, in 250mL reaction bulb, is sequentially added into 100mL toluene, and 10 Mg major catalyst (Cat.22), 9.6mL MAO solution (1.5mol/L), 5mL norborene.Take a breath after three times, keep Under the propylene pressure of 160 DEG C and 3atm, it is polymerized 1h, terminates reaction with the ethanol solution containing 10% hydrochloric acid, filter, use second Alcohol washs 3 times, and polymer is vacuum dried 24h at 40 DEG C.
Embodiment 23
1) preparation of alcohol Oxymethylene bridging bimetallic half cyclopentadienyl catalyst: to magneton under anhydrous and oxygen-free and nitrogen are protected Dry reaction bottle in add 100mL toluene, add 200mg metallocene catalyst (CGC), add under stirring and dissolving room temperature Enter 0.0002mol 1,1 '-biphenyl-4,4 '-dimethanol, keep room temperature reaction 1h, after be warming up to 80 DEG C of reaction 5h.Reaction terminates After, filter and wash repeatedly with normal hexane 50mL at 40 DEG C, sucking filtration；Resulting procatalyst component Cat.23:
3) copolymerization of propylene: under the conditions of anhydrous and oxygen-free, in 250mL reaction bulb, is sequentially added into 100mL toluene, and 10 Mg major catalyst (Cat.22), 9.6mL MAO solution (1.5mol/L), 5mL norborene.Take a breath after three times, keep Under the propylene pressure of 160 DEG C and 3atm, it is polymerized 1h, terminates reaction with the ethanol solution containing 10% hydrochloric acid, filter, use second Alcohol washs 3 times, and polymer is vacuum dried 24h at 40 DEG C.
In each embodiment polyreaction the results are shown in Table 1:
Table 1:

Claims (9)

1. for alcohol Oxymethylene bridging bimetallic half cyclopentadienyl catalyst for olefinic polymerization, major catalyst urge with helping Agent forms；It is characterized in that, the structure of described major catalyst meets formula (1):
In formula (1), R1、R1＇, R2、R2＇, R3、R3＇, R4、R4＇, R5、R5＇ is identical or different Substituent group, separately represent hydrogen, the alkyl of C1-C20, the cycloalkyl of C3-C20, the aryl of C6-C20, The miscellaneous alkyl of virtue of the halogenated aryl of C6-C20, the Heterocyclylalkyl of C2-C20 or C6-C20, wherein substituent R1、 R2、R3、R4、R5Or R1＇, R2＇, R3＇, R4＇, R5＇ is closed into monocycle or condensed ring each other or does not closes； M1Or M2It is identical or different metallic atom, is respectively selected from the one in III B, IV B, VB, VIB or VIII； X or X ＇ is identical or different halogen atom, selected from Cl, Br, F；N takes the positive integer more than or equal to 1；R6 It is the alkyl or derivatives thereof of C1-C20, the cycloalkyl or derivatives thereof of C3-C30, C6-C20 for carbon number Aryl or derivatives thereof, the Heterocyclylalkyl or derivatives thereof of C2-C30, or R6 do not exists.
2., for a catalyst for olefinic polymerization, it is made up of major catalyst and promoter, it is characterised in that: wherein Major catalyst is that described helping is urged according to alcohol Oxymethylene bridging bimetallic half cyclopentadienyl catalyst described in claim 1 Agent is alkyl aluminum or MAO；Major catalyst is 1:(100-5000 with the mol ratio of promoter).
3. the method preparing alcohol Oxymethylene bridging bimetallic half cyclopentadienyl catalyst as claimed in claim 1, its feature exists In comprising the following steps:
1) in organic solvent, will have and meet formula (2a) or the compound dissolution of (2b)；
Wherein, R1、R1＇, R2、R2＇, R3、R3＇, R4、R4＇, R5、R5＇ is identical or different substituent group, Separately represent hydrogen atom, the alkyl of C1-C20, the cycloalkyl of C3-C20, the aryl of C6-C20, C6-C20 The miscellaneous alkyl of virtue of halogenated aryl, the Heterocyclylalkyl of C2-C20 and C6-C20, wherein substituent R1、R2、R3、 R4、R5Or R1＇, R2＇, R3＇, R4＇, R5＇ is closed into monocycle or condensed ring each other or does not closes；Meet formula (2a) or the compound of (2b), selected from cyclopentadiene and derivant, indenes and derivant thereof, fluorenes and derivative Thing；
At a temperature of-80 DEG C-120 DEG C, react 0.5h-12h, react formation anion with the n-BuLi added；So After, at a temperature of-50 DEG C-150 DEG C, with transition metal halide MXmReaction 1h-10h, obtains meeting formula (3) Compound；
Wherein M represents metallic atom, selected from III B, IV B, VB, VIB or VIII race；X is halogen atom, is selected from Cl、Br、F；
Wherein metal halide MXmIn；M represents metallic atom, selected from III B, IV B, VB, VIB or VIII Race；X is halogen atom, selected from Cl, Br, F；M is 2,3 or 4；
There is the compound meeting formula (2a) or (2b) structure and metal halide MXmMol ratio be 1: 0.4-1.6；
2) will have and meet the compound dissolution of formula (3) in organic solvent, addition carbon number is C2-C30 Dihydroxylic alcohols, at-20 DEG C-110 DEG C, react 0.5h-24h；It is dried to obtain to have after removing solvent and meets formula (1) Catalyst, i.e. alcohol Oxymethylene bridging bimetallic half cyclopentadienyl catalyst；
In formula (1), R1、R1＇, R2、R2＇, R3、R3＇, R4、R4＇, R5、R5＇ is identical or different, point Represent hydrogen atom, the alkyl of C1-C20, the cycloalkyl of C3-C20, the aryl of C6-C20, C6-C20 the most independently The miscellaneous alkyl of virtue of halogenated aryl, the Heterocyclylalkyl of C2-C20 and C6-C20, wherein substituent R1、R2、R3、 R4、R5Or R1＇, R2＇, R3＇, R4＇, R5＇ is closed into monocycle or condensed ring each other or does not closes；M1With M2 Selected from III B, IV B, VB, VIB or VIII race's metallic atom；X Yu X ＇ is selected from Cl, Br, F；R6 is carbon atom Number be the alkyl or derivatives thereof of C1-C20, the cycloalkyl or derivatives thereof of C3-C30, the aryl of C6-C20 or its Derivant, the Heterocyclylalkyl or derivatives thereof of C2-C30, or R6 do not exists；N more than or equal to 1 is just Integer；
The mol ratio of the compound and diatomic alcohol compounds that meet formula (3) is 1.5-2.5:1.
The preparation method of alcohol Oxymethylene bridging bimetallic half cyclopentadienyl catalyst the most according to claim 3, its feature It is: solvent used in building-up process is saturated alkane, saturated rings alkane, aromatic hydrocarbons or their mixed solution.
The preparation method of alcohol Oxymethylene bridging bimetallic half cyclopentadienyl catalyst the most according to claim 3, it is special Levy and be: meet the compound of formula (2a) or (2b) be cyclopentadiene and derivant, indenes and derivant thereof, Or fluorenes and derivant thereof.
The preparation method of alcohol Oxymethylene bridging bimetallic half cyclopentadienyl catalyst the most according to claim 3, it is special Levy and be: dihydroxylic alcohols be carbon number be the fatty alcohol of C2-C30, the cyclic alkanol of C3-C30, the virtue of C6-C30 The Heterocyclylalkyl alcohol of base alcohol or C2-C30.
The preparation method of alcohol Oxymethylene bridging bimetallic half cyclopentadienyl catalyst the most according to claim 3, its feature It is: the M in formula (1)1、M2For Ti, Zr, Hf, Sc, Y, Nd, La, Sm, Ru, Rh, Fe, Co, Ni or Pd.
The application of alcohol Oxymethylene bridging bimetallic half cyclopentadienyl catalyst the most according to claim 1, it is characterised in that It is that catalysis nonpolar olefinic is all polymerized or combined polymerization；Wherein said nonpolar olefinic is the alkene of C2-C30.
Application the most according to claim 8, it is characterised in that described polymerizing condition is: polymerization temperature is 30 DEG C -200 DEG C, olefinic polymerization pressure is 0.1MPa-30MPa, and polymerization reaction time is 5min-300min.
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