CN102190687B - Configuration-limited carbon-bridged single metallocene compound and preparation and application thereof - Google Patents

Configuration-limited carbon-bridged single metallocene compound and preparation and application thereof Download PDF

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CN102190687B
CN102190687B CN201010120089.7A CN201010120089A CN102190687B CN 102190687 B CN102190687 B CN 102190687B CN 201010120089 A CN201010120089 A CN 201010120089A CN 102190687 B CN102190687 B CN 102190687B
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CN102190687A (en
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米普科
王斯晗
许胜�
钱锦华
陈谦
郭翔
黄付玲
阎修维
杨俊凤
江玲
屈良端
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East China University of Science and Technology
Petrochina Co Ltd
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Petrochina Co Ltd
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Abstract

The invention relates to a configuration-limited carbon-bridged half-metallocene compound, and a preparation method and an application thereof; the structural general formula is as follows: wherein: r ═ H, allyl or tert-butyl containing 1 to 10 carbon atoms; r1，R2H, alkyl, allyl, aryl or silicon group containing 1-10 carbon atoms; m ═ Ti or Zr; cp is a metallocene, a substituted metallocene, indene or a substituted indene; is suitable for catalyzing the copolymerization of ethylene/hexene-1 and ethylene/octene-1, and has the polymerization activity of 2.76 multiplied by 10 under the conditions that the reaction temperature is 70 ℃, the reaction time is 0.5 hour, the aluminum/zirconium ratio is 1000, the concentration of octene-1 is 0.6mol/L and the ethylene pressure is 0.1MPa6Cat.h., the octene-1 content in the polymer is 19.07%, the catalytic activity is high during copolymerization, and the insertion rate of long-chain alpha-olefin is high.

Description

A kind of constrained geometry carbon-bridged single metallocene compound and preparation thereof and application
Technical field
The present invention relates to a kind of constrained geometry carbon-bridged single metallocene compound and preparation thereof and the application in ethene/1-hexene, ethene/1-octene, the copolymerization of ethene/decene.
Background technology
The metallocene catalyst being comprised of cyclopentadiene titanium compound and boron compound, organo-aluminium compound, has the features such as adjustable comonomer insertion amount and microtexture; As a kind of in CN1083846C invention cyclopentadiene titanium compound C of how much new limiting structures 13h 6r 1r 2r 3nR 4ti (R 5):
Synthetic through polystep reaction by benzindene or replacement benzindene, can form catalyzer with boron compound and organo-aluminium compound, for ethylene/octene one 1 copolymerization, ethylene/styrene copolymerization.
CN1049849 (US 5272236 and 5278272) has reported a kind of cyclopentadiene titanium compound Me of how much limiting structures 2si (C 5me 4) (NCMe 3) TiCl 2, the catalyst system that forms of organoaluminum and boron compound, for ethylene/octene one 1 copolymerizations, can obtain that a kind of narrow molecular weight distribution, comonomer insertion amount are high and adjustable, copolymerization composite distribution homogeneous, there are New Type of Ethylene/octene one 1 multipolymers of long-chain branched polyethylene chain structure; These patents are silyl-bridged, and on luxuriant ring side chain, containing can coordination nitrogen-atoms, and cyclopentadienyl is that tetramethylene is luxuriant; The type compound is suitable for homogeneous phase and the under high pressure copolymerization of supported catalyst ethylene ' alpha '-olefin, and activity is 10 6g Polymer/molMetalh, alpha-olefin insertion rate is 5～8%mol.Structure is as follows:
M＝Ti，Zr，Hf
R1～R4＝alkyl，allyl，ph?et?al.
But blemish in an otherwise perfect thing is these catalyst system less stable, and activity and octene insertion rate are lower, or with high costsly limit its application.
In USP 4892851,5155080 and 5132381, disclose the single carbon or the methylene-bridged group that are suitable for the replacement of the metallocene of making olefin polymerization catalysis, it is suitable especially that isopropylidene, list and Diarylmethylidene are confirmed as.WO 9200333, US 08999214, US09042378 disclose containing heteroatomic metallocene catalyst; Use non-carbon wherein the 13rd, 14,15Huo 16 family's atomic substitutions a ring carbon atom containing heteroatomic ring or condensed ring.CN1328580 discloses the bridge metallocenes that a kind of olefin-copolymerization share, and this metallocene catalyst is the organo-metallic catalyst containing the bridging part of aryl replacement.This title complex contains and comprises the substituent solubilising covalency of at least one alkyl silyl bridging part.General formula is:
These compounds are applied to catalyzed ethylene-octene copolymer, and catalytic activity and catalytic efficiency are still not high, from the requirement of practical application in industry, still have certain gap.
Summary of the invention
The object of the invention is to provide a kind of constrained geometry carbon-bridged single metallocene compound and preparation and application.
Constrained geometry carbon-bridged single metallocene compound structure of the present invention is as follows:
Wherein: R is H or the allyl group that contains 1～10 carbon atom or the tertiary butyl;
R 1, R 2for H or the alkyl that contains 1～10 carbon atom, allyl group or aromatic base;
Methyl is preferred group;
M=Ti or Zr;
Cp=is luxuriant, it is luxuriant to replace, indenes or replace indenes.
This class constrained geometry carbon-bridged single metallocene compound includes, but are not limited to following compounds:
[t-BuNC(Me) 2(η 5-C 5H 4)](TiCl 2)
[t-BuNC(Me) 2(η 5-C 5H 4)](ZrCl 2)
[t-BuNC(CH 2) 5(η 5-C 5H 4)](ZrCl 2)
[t-BuNCH(H 2C＝CHCH 2)(η 5-C 5H 4)](TiCl 2)
[t-BuNC(H 2C＝CHCH 2) 2(η 5-C 5H 4)](TiCl 2)
[t-BuNC(H 2C＝CHCH 2) 2(η 5-C 5H 4)](ZrCl 2)
[H 2C＝CHCH 2NC(Me) 2(η 5-C 5H 4)](ZrCl 2)
[t-BuNC(Me) 2(η 5- nBuC 5H 3)](TiCl 2)
[H 2C＝CHCH 2NC(Me) 2(η 5- nBuC 5H 3)](Zr?Cl 2)
[t-BuNC(Me) 2(η 5- nBuC 5H 3)](ZrCl 2)
[t-BuNC(Me) 2(η 5-H 2C＝CHCH 2C 5H 3)](Zr?Cl 2)。
The typical production of this compounds is as follows:
Get in the tetrahydrofuran (THF) (THF) that 20mmol TERTIARY BUTYL AMINE or allyl amine be dissolved in 30～60mL, under-50～50 ℃ of conditions, stir, the hexane solution 12mL that adds the n-Butyl Lithium (n-BuLi) of 1.67M, react 4～40 hours, removal of solvent under reduced pressure, 10～20mL normal hexane washing for remaining solid, obtains white powder A; With 15～40mL tetrahydrofuran (THF) (THF), dissolve above-mentioned white powder A, add 20mmol 6,6-dimethyl fulvene, 6,6-diaryl fulvene or 6,6-diallyl fulvene, white suspension becomes clarification at once, reacts removal of solvent under reduced pressure after 10～50 hours, 10～20mL normal hexane washing for remaining solid, obtains white powder B; Add 15～40mL tetrahydrofuran (THF) (THF) to dissolve white powder B, the hexane solution 12mL that adds again the n-Butyl Lithium (n-BuLi) of 1.67M, reacts removal of solvent under reduced pressure 10～40 hours, 10～15mL normal hexane washing for remaining solid, obtains the two lithium salts C of white powder; Add 15～40mL tetrahydrofuran (THF) (THF) to dissolve white powder C, at-50～50 ℃, stir, slowly add the zirconium tetrachloride (ZrCl of 20mmol 4) or titanium tetrachloride (TiCl 4), react 10～72 hours, standing, remove by filter white solid lithium chloride (LiCl), filtrate decompression is except desolventizing, and gained solid is drained after with 40～60mL normal hexane or washed with dichloromethane, and the solid obtaining is constrained geometry carbon-bridged single metallocene compound.
The present invention is on carbon bridge and luxuriant ring, particularly on carbon bridge, introduce different substituting groups as alkyl, allyl group, aryl base, obtain the carbon bridging mono-metallocene compound that contains different substituents, can change the chemistry of central metal, three-dimensional environment, effectively improve catalyst performance, when catalyzed ethylene and long-chain alpha-olefin copolyreaction are closed as ethene/1-hexene, ethene/1-octene copolymer, olefin polymerizating activity is high, the rate of long-chain alpha-olefin insertion is simultaneously higher, and molecular weight distribution is wider.For example, take toluene as solvent, with [the t-BuNC (Me) of embodiment 2 2(η 5-C 5h 4)] (ZrCl 2) be catalyzer, MAO is promotor, and in the 0.5 hour reaction times at 70 ℃ of temperature of reaction, the copolymerization of catalyzed ethylene/octene-1, is 1000 at aluminium/zirconium ratio, and octene-1 concentration is 0.6mol/L, and during ethylene pressure 0.1MPa, polymerization activity is 2.76 * 10 6gPE/mol.cat.h., octene-1 content 19.07% in polymkeric substance.
The present invention adopts carbon bridging mono-metallocene compound/MAO catalyst system, alpha-olefin copolymer is closed to acquisition high reactivity, applicable to homopolymerization or the copolymerization of the alpha-olefins such as ethene, be specially adapted to the copolymerization of the ethene such as catalyzed ethylene/hexene-1, catalyzed ethylene/octene-1 and long-chain alpha-olefin.
Practical application from above-mentioned public technology scheme, the said carbon means of special bridged metallocene catalysts of the present invention has many advantages, its synthetic route is reasonable, product yield is higher, separation and purification is easy, during for the copolymerization of catalyzed ethylene and long-chain alpha-olefin, catalytic activity is high, and long-chain alpha-olefin insertion rate is high.
Embodiment
Metallocene compound is synthetic
Embodiment 1
[t-BuNC (Me) 2(η 5-C 5h 4)] (TiCl 2) synthetic
Get 20mmol (1.46g) TERTIARY BUTYL AMINE and be dissolved in the THF of 55mL, under 0 ℃ of condition, stir, add the hexane solution 12mL of the n-BuLi of 1.67M, react and within 30 hours, obtain white opacity suspension, removal of solvent under reduced pressure, 15mL normal hexane washing for remaining solid, obtains white powder A; With 15mLTHF, dissolve above-mentioned white powder A, add 6 of 20mmol (2.14g), 6-dimethyl fulvene, white suspension becomes clarification at once, reacts removal of solvent under reduced pressure after 50 hours, and 15mL normal hexane washing for remaining solid, obtains white powder B; Add 30mL THF to dissolve white powder B, then add the hexane solution 12mL of the n-BuLi of 1.67M, react 30 hours, removal of solvent under reduced pressure, 15mL normal hexane washing for remaining solid, obtains the two lithium salts C of white powder; Add 30mL THF to dissolve white powder C, at-30 ℃, stir, slowly add the TiCl of 20mmol 42THF, reacts 50 hours (automatic heating to 25 ℃ in reaction process), and solution becomes olive-green, removes by filter white solid, and removal of solvent under reduced pressure adds the excessive n-BuLi of 50mL n-hexane extraction, and remaining solid is drained, and obtains olive-green solid.Fusing point is 103～105 ℃. 1HNMR(DCCl 3，δ)：1.540(s，6H，Me 2CCp)，1.915(s，9H，Me 3C-N)，6.367(s，2H，CpH)，6.583(s，2H，CpH)；。EI-MS(m/e)：292(43，M )，223(100，[M -N t-Bu] +)，187(46，[Me 2C(C 5H 4)Ti] +)。Ultimate analysis value C 12h 19cl 2nTi:C, calculated value 48.68%, observed value 46.50%; H, calculated value 6.47%, observed value 7.21%.
Embodiment 2
[t-BuNC (Me) 2(η 5-C 5h 4)] (ZrCl 2) synthetic
Get 20mmol (1.46g) TERTIARY BUTYL AMINE and be dissolved in the THF of 30mL, under 0 ℃ of condition, stir, add the hexane solution 12mL of the n-BuLi of 1.67M, react and within 40 hours, obtain white opacity suspension, removal of solvent under reduced pressure, 10mL normal hexane washing for remaining solid, obtains white powder A; With 15mLTHF, dissolve above-mentioned white powder A, add 6 of 20mmol (2.14g), 6-dimethyl fulvene, solution becomes clarification at once, reacts removal of solvent under reduced pressure after 50 hours, and 10mL normal hexane washing for remaining solid, obtains white powder B; Add 25mL THF to dissolve white powder B, then add the hexane solution 12mL of the n-BuLi of 1.67M, react 40 hours, obtain white opacity suspension, removal of solvent under reduced pressure, 15mL normal hexane washing for remaining solid, obtains the two lithium salts C of white powder; Add 15mL THF to dissolve white powder C, at 0 ℃, stir, slowly add the ZrCl of 20mmol 4, to react 72 hours, solution upper strata becomes clarification, and removal of solvent under reduced pressure, to drain after washed with dichloromethane, obtains yellow solid 3.45g, and fusing point is 111～114 ℃. 1HNMR(DCCl 3，δ)：6.512(t，2H，J＝7.0Hz，CpH)，6.315(t，2H，J＝7.0Hz，CpH)，1.509(s，6.0H，Me 2CCp)，1.461(s，9H，Me 3C-N)。EI-MS(m/e)：334(28，M )，265(100，[M -N t-Bu] +)，229(37，[Me 2C(C 5H 4)ZrCl] +)。Ultimate analysis value C 12h 19cl 2nZr:C, calculated value 42.46%, observed value 40.13%; H, calculated value 5.64%, observed value 6.24%.
Embodiment 3
[t-BuNC (CH 2) 5(η 5-C 5h 4)] (ZrCl 2) synthetic
Get 20mmol (1.46g) TERTIARY BUTYL AMINE and be dissolved in the THF of 35mL, under 0 ℃ of condition, stir, add the hexane solution 12mL of the n-BuLi of 1.67M, react and within 40 hours, obtain white opacity suspension, removal of solvent under reduced pressure, 10mL normal hexane washing for remaining solid, obtains white powder A; With 15mLTHF, dissolve above-mentioned white powder A, add 6 of 20mmol (2.48g), 6-pentamethylene fulvene, solution becomes clarification, reacts removal of solvent under reduced pressure after 48 hours, and 10mL normal hexane washing for remaining solid, obtains white powder B; Add 15mL THF to dissolve white powder B, then add the hexane solution 12mL of the n-BuLi of 1.67M, react 24 hours, obtain white opacity suspension, removal of solvent under reduced pressure, 10mL normal hexane washing for remaining solid, obtains the two lithium salts C of white powder; Add 15mL THF to dissolve white powder C, at 0 ℃, stir, slowly add the ZrCl of 18.8mmol 4, react 72 hours, standing, remove by filter white LiCl, filtrate decompression, except desolventizing, with dry after 50mL washed with dichloromethane, obtains faint yellow solid product, and fusing point is 121～124 ℃. 1H?NMR(DCCl 3，δ)：6.404(t，2H，J＝7.0Hz，CpH)，6.270(t，2H，J＝7.0Hz，CpH)，，2.268(br，2H，(CH 2) 5)，1.239(br，3H，(CH 2) 5)，1.733(br，5H，(CH 2) 5)，1.461(s，9H，Me 3C-N-)。EI-MS(m/e)：378(12，M )，306(88，[M - t-BuNH] +)，267(38，[(CH 2) 5(C 5H 4)ZrCl] +)。Ultimate analysis C 15h 23cl 2nZr:C theoretical value 47.48%, observed value 46.45%; H theoretical value 6.11%, observed value 7.64%.
Embodiment 4
[t-BuNCH (ph) (η 5-C 5h 4)] (TiCl 2) synthetic
Get 20mmol (1.46g) TERTIARY BUTYL AMINE and be dissolved in the THF of 40mL, stir at ambient temperature, add the hexane solution 12mL of the n-BuLi of 1.67M, react and within 12 hours, obtain white opacity suspension, removal of solvent under reduced pressure, 10mL normal hexane washing for remaining solid, obtains white powder A; With 15mLTHF, dissolve above-mentioned white powder A, 6-hydrogen-6-phenyl the fulvene that adds 20mmol (3.10g), transparent yellow liquid becomes red liquid, reacts removal of solvent under reduced pressure after 48 hours, 10mL normal hexane washing for remaining solid, obtains white powder B; Add 30mLTHF to dissolve white powder B, then add the hexane solution 12mL of the n-BuLi of 1.67M, react 24 hours, obtain white opacity suspension, removal of solvent under reduced pressure, 10mL normal hexane washing for remaining solid, obtains the two lithium salts C of white powder; Add 30mL THF to dissolve white powder C, at 0 ℃, stir, slowly add the TiCl of 19.8mmol 42THF, reacts 70 hours, standing, remove by filter white LiCl, and filtrate decompression, except desolventizing, with 50mL petroleum ether, obtains brown powder solid.
Embodiment 5
[t-BuNC (ph) 2(η 5-C 5h 4)] (TiCl 2) synthetic
Get 20mmol (1.46g) TERTIARY BUTYL AMINE and be dissolved in the THF of 50mL, stir at ambient temperature, add the hexane solution 12mL of the n-BuLi of 1.67M, react and within 10 hours, obtain white opacity suspension, removal of solvent under reduced pressure, 10mL normal hexane washing for remaining solid, obtains white powder A; With 27.5mLTHF, dissolve above-mentioned white powder A, add 6 of 20mmol (5.31g), 6-phenylbenzene fulvene, solution deepens blue solution at once, reacts removal of solvent under reduced pressure after 50 hours, and 15mL normal hexane washing for remaining solid, obtains white powder B; Add 35mL THF to dissolve white powder B, then add the hexane solution 12mL of the n-BuLi of 1.67M, react 30 hours, removal of solvent under reduced pressure, 15mL normal hexane washing for remaining solid, obtains the two lithium salts C of white powder; Add 35mL THF to dissolve white powder C, at 0 ℃, stir, slowly add the TiCl of 19.15mmol 42THF, reacts 72 hours, standing, remove by filter white LiCl, and filtrate decompression, except desolventizing, with removal of solvent under reduced pressure after 50mL washed with dichloromethane, obtains reddish-brown solid.
Embodiment 6
[t-BuNC (ph) 2(η 5-C 5h 4)] (ZrCl 2) synthetic
Get 20mmol (1.46g) TERTIARY BUTYL AMINE and be dissolved in the THF of 33mL, stir at ambient temperature, add the hexane solution 12mL of the n-BuLi of 1.67M, react and within 32 hours, obtain white opacity suspension, removal of solvent under reduced pressure, 15mL normal hexane washing for remaining solid, obtains white powder A; With 35.5mLTHF, dissolve above-mentioned white powder A, add 6 of 20mmol (5.31g), 6-phenylbenzene fulvene, solution deepens blue solution at once, reacts removal of solvent under reduced pressure after 50 hours, and 15mL normal hexane washing for remaining solid, obtains white powder B; Add 35mL THF to dissolve white powder B, then add the hexane solution 12mL of the n-BuLi of 1.67M, react 24 hours, removal of solvent under reduced pressure, 15mL normal hexane washing for remaining solid, obtains the two lithium salts C of white powder; Add 35mL THF to dissolve white powder C, at 0 ℃, stir, slowly add the ZrCl of 20mmol 4, react 48 hours, standing, remove by filter white LiCl, filtrate decompression, except desolventizing, with removal of solvent under reduced pressure after 45mL washed with dichloromethane, obtains red powder.
Embodiment 7
[H 2c=CHCH 2nC (Me) 2(η 5-C 5h 4)] (ZrCl 2) synthetic
Get 20mmol (1.66mL) allyl amine and be dissolved in the THF of 33mL, under 0 ℃ of condition, stir, add the hexane solution 12mL of the n-BuLi of 1.67M, react and within 6 hours, obtain white opacity suspension, removal of solvent under reduced pressure, 15mL normal hexane washing for remaining solid, obtains white powder A; With 25mLTHF, dissolve above-mentioned white powder A, add 6 of 20mmol (2.14g), 6-dimethyl fulvene, reacts removal of solvent under reduced pressure after 20 hours, and 15mL normal hexane washing for remaining solid, obtains white powder B; Add 35mL THF to dissolve white powder B, then add the hexane solution 12mL of the n-BuLi of 1.67M, react 20 hours, removal of solvent under reduced pressure, 15mL normal hexane washing for remaining solid, obtains the two lithium salts C of white powder; Add 30mL THF to dissolve white powder C, at-20 ℃, stir, slowly add the ZrCl of 20mmol 4, react 12 hours, standing, remove by filter white LiCl, filtrate decompression, except desolventizing, to drain after 45mL washed with dichloromethane, obtains yellow powder.
Under normal pressure, homogeneous catalysis ethene and 1-octene copolymer close
Embodiment 8
In being equipped with the 100ml there-necked flask of magnetic agitation, add successively toluene, 1-octene 3.9mL, MAO 2.5ml (1.50M) [Al/M=1000], [t-BuNC (Me) of embodiment 1 2(η 5-C 5h 4)] (TiCl 2) 3.75 μ mol, control cumulative volume 50mL, be warming up to 70 ℃, pass into ethylene gas reaction 30min, after completion of the reaction, by 10% acidic alcohol termination reaction, polymkeric substance is transferred in beaker, standing, filter, washing with alcohol is to neutral, and 80 ℃ of constant-temperature vacuums are dry, weigh polymer quality, conversion activity is 2.29 * 10 6gPE/molCath.135 ℃ of surveys 13it is 5.34%mol that C NMR obtains 1-octene insertion rate, 1-octene content 17.60% in multipolymer.
Embodiment 9
Working method is with embodiment 8, and catalyzer is the [t-BuNC (Me) of embodiment 2 2(η 5-C 5h 4)] (ZrCl 2) 3.75 μ mol.The polymer quality that weighing obtains, conversion activity is 2.76 * 10 6gPE/mol.cat.h., 135 ℃ of surveys 13c NMR obtains octene-1 content 19.07% in polymkeric substance.
Embodiment 10
Working method is with embodiment 8, and catalyzer is the [t-BuNC (CH of embodiment 3 2) 5(η 5-C 5h 4)] (ZrCl 2).The polymer quality that weighing obtains, conversion activity is 2.48 * 10 6gPE/molCath.135 ℃ of surveys 13it is 5.64%mol that C NMR obtains 1-octene insertion rate.
Embodiment 11
Working method is with embodiment 8, and catalyzer is the [t-BuNC (Me) of embodiment 1 2(η 5-C 5h 4)] (TiCl 2), 1-octene 4.5mL.The polymer quality that weighing obtains, conversion activity is 1.21 * 10 6gPE/molCath.135 ℃ of surveys 13c NMR obtains 1-octene content 18.30% in multipolymer.
Embodiment 12
Working method is with embodiment 11, and catalyzer is the [t-BuNC (Me) of embodiment 2 2(η 5-C 5h 4)] (ZrCl 2), 1-octene 4.5mL.The polymer quality that weighing obtains, conversion activity is 1.42 * 10 6gPE/molCath.135 ℃ of surveys 13c NMR obtains 1-octene content 19.15% in multipolymer.
Embodiment 13
Working method is with embodiment 8, and catalyzer is the [t-BuNC (Me) of embodiment 2 2(η 5-C 5h 4)] (ZrCl 2), 1-octene 6.0mL.The polymer quality that weighing obtains, conversion activity is 1.10 * 10 6gPE/molCath.135 ℃ of surveys 13c NMR obtains 1-octene content 21.32% in multipolymer.
Embodiment 14
Working method is with embodiment 13, and catalyzer is the [t-BuNCHph (η of embodiment 4 5-C 5h 4)] (TiCl 2).The polymer quality that weighing obtains, conversion activity is 1.029 * 10 6gPE/molCath.135 ℃ of surveys 13c NMR obtains 1-octene content 18.60% in multipolymer.
Embodiment 15
Working method is with embodiment 13.Catalyzer is embodiment's 6 [t-BuNC (ph) 2(η 5-C 5h 4)] (ZrCl 2).The polymer quality that weighing obtains, conversion activity is 0.85 * 10 6gPE/molCath.135 ℃ of surveys 13c NMR obtains 1-octene content 20.74% in multipolymer.
Embodiment 16
Working method is with embodiment 13, and catalyzer is the [t-BuNC (CH of embodiment 1 3) 2(η 5-C 5h 4)] (TiCl 2), 1-hexene 0.4ml.The polymer quality that weighing obtains, conversion activity is 1.02 * 10 6gPE/molCath.135 ℃ of surveys 13c NMR obtains 1-hexene content 15.04% in multipolymer.
Embodiment 17
Working method is with embodiment 13, and catalyzer is the [t-BuNC (CH of embodiment 1 3) 2(η 5-C 5h 4)] (TiCl 2), 1-hexene 0.6ml.The polymer quality that weighing obtains, conversion activity is 0.65 * 10 6gPE/molCath.135 ℃ of surveys 13c NMR obtains 1-hexene content 16.41% in multipolymer.

Claims (1)

1. an application for constrained geometry carbon-bridged single metallocene compound, is characterized in that: as ethene/1-octene, ethene/1-hexene, ethene/decene copolymerization catalyst, the promotor of described copolymerization catalyst is MAO catalyzer;
Described compound is:
[t-BuNC(Me) 2(η 5-C 5H 4)](TiCl 2)
[t-BuNC(CH 2) 5(η 5-C 5H 4)](ZrCl 2)
[t-BuNCH(C 6H 5)(η 5-C 5H 4)](ZrCl 2)。
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