CN1151184C - Metallocene catalyst for polymerizing or copolymerizing ethylene and its preparing process and application - Google Patents

Metallocene catalyst for polymerizing or copolymerizing ethylene and its preparing process and application Download PDF

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CN1151184C
CN1151184C CNB001303880A CN00130388A CN1151184C CN 1151184 C CN1151184 C CN 1151184C CN B001303880 A CNB001303880 A CN B001303880A CN 00130388 A CN00130388 A CN 00130388A CN 1151184 C CN1151184 C CN 1151184C
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metallocene
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catalysis system
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CN1353120A (en
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波 邱
邱波
王熙
刘长城
胡青
姚辉
郑莹
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
China Petrochemical Corp
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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Abstract

The present invention relates to a metallocene catalyst system for the polymerization or the copolymerization of olefine, a preparing process thereof and an application thereof. Two or more than two non-carried metallocene compounds are mainly combined with aluminoxane carried on a silca gel carrier, and the catalyst is used for the polymerization or the copolymerization of ethylene to obtain polymers. The obtained polymers have wider molecular weight distribution than ethylene polymers produced by a monometallocene catalyst, and obtained copolymers have more suitable comonomer distribution. Moreover, the catalyst system has the advantages of high polymerization activity, good shape of polymer particles and high apparent density.

Description

Vinyl polymerization or copolymerization metallocene catalyst and its production and application
The present invention relates to a kind of catalyst for olefines polymerizing and its production and application, more particularly, relate to a kind of metallocene catalyst and this Preparation of catalysts method and the application in alpha-olefine polymerizing or copolymerization of multiple active components.
As everyone knows, the processing characteristics of the performance of Alathon and ethene and the formed multipolymer of one or more alpha-olefin comonomer and its product performance, depend on flowability, melt strength of polymkeric substance etc., just depend on the molecular weight and the molecular weight distribution of polymkeric substance.In the field of using these polymkeric substance,, require these polymkeric substance to have wider molecular weight distribution usually as the system film.
In recent years, metallocene/aikyiaiurnirsoxan beta (MAO) catalyst system of Kaminsky invention has caused people's extensive concern.Compare with traditional Ziegler-Natta catalyst, this catalyst system has the advantage of a lot of uniquenesses: higher as activity of such catalysts, polymkeric substance has the chain length than homogeneous, comonomer is evenly distributed on main chain, can obtain traditional Ziegler-Natta catalyst system can not getable rule PP, between advise PS, improved the impressionability of polymkeric substance, covering with paint property, consistency etc., but because this catalyzer has single active centre, therefore the ethene polymers of its gained has narrower molecular weight distribution, general its weight-average molecular weight is 2～3 with the ratio of number-average molecular weight, the processing characteristics that this has just restricted it widely can not satisfy the requirement of some Industrial products.
In order to improve above-mentioned polyvinyl processing characteristics, generally adopt following two kinds of methods; The one, two or more ethene polymerss with obvious different molecular weight are mixed, the 2nd, the polymkeric substance that directly changes the used catalyzer generation wide molecular weight distribution of polymerization is widened the molecular weight distribution of the finished product, improves physics, mechanical property and the processing characteristics of product.In order to obtain the more excellent polymkeric substance of mechanical property, generally believe providing a kind of catalyzer that produces than wide molecular weight distribution is ideal method comparatively.
For example: Chinese patent CN1131953A discloses a kind of catalyst system that is used for olefinic polymerization, it is selected at and has two to five substituent metallocene compounds on the cyclopentadienyl rings, adopt three or more mixture of isomers to load on the silica-gel carrier, can produce a kind of wider molecular weight distribution that has, the ethene polymers that high molecular and narrow composition distribute, the characteristics of described catalyzer be three kinds or multiple metallocene mixture of ingredients makes in a reaction rather than make separately after mix, also just because of this characteristics that generate mixture simultaneously, ratio between its each component is unmanageable, therefore causes the molecular weight distribution of resulting polymers, mechanical property all is difficult to control.
European patent EP 128,045 discloses a kind of catalyzer that is used to produce polyethylene with wide molecular weight distribution, this catalyst system is to adopt two or more metallocene compounds with different polyreactions growths and termination constant to combine with aikyiaiurnirsoxan beta, be used for ethylene polymerization, the ethene polymers that obtains has bimodal or multimodal molecular weight distributes, its disclosed weight-average molecular weight is generally 3.9～7.8 with the ratio of number-average molecular weight, but this catalyzer is not loaded with, and therefore is difficult to obtain having the polymkeric substance of better particle form.
The inventor is through research repeatedly, a kind of metallocene catalysis system that is used for olefinic polymerization or copolymerization has been proposed, it mainly is to adopt two or more the non-metallocene compound of loading with to combine with aikyiaiurnirsoxan beta on loading on silica-gel carrier, it is used for vinyl polymerization or copolymerization obtains polymkeric substance, ethene polymers than single metallocene catalyst production has wideer molecular weight distribution, comonomer distribution preferably is arranged in the gained multipolymer, and the polymerization activity of this catalyst system is higher, the polymer beads form is good, the apparent density height, and the problem that does not exist metallocene to be wasted, and can adjust the kind and the amount ratio of used metallocene compound neatly, to reach the purpose that resulting polymers molecular weight and molecular weight distribution are regulated.
A kind of metallocene catalysis system that is used for olefinic polymerization or copolymerization of the present invention comprises following component:
(1) two or more unsupported metallocene compound, wherein the general formula of metallocene compound is:
Figure C0013038800051
Wherein M is transition metal Ti or Zr or Hf,
X is alkyl or halogen
L, L ' they are dentate, can be selected from a kind of in the fluorenyl of indenyl, fluorenyl, replacement of cyclopentadienyl, indenyl, the replacement of cyclopentadienyl, replacement, and L, L ' can be identical, also can be different,
B is for linking the bridge of L, L ' two dentates, and according to the difference of L, L ' dentate, this bridge can exist and also can not exist, and the form of bridge is-SiRR '-,-GeRR '-,-CRR '-,-SiR 2-O-SiR 2'-in a kind of, R, R ' are C 1～C 20Straight chained alkyl, its can be identical can be inequality,
(2) through carrier loaded aikyiaiurnirsoxan beta.
Ratio between said components component (2) and the component (1) is 30～2000 with the molar ratio computing of Al in the component (2) and the middle transition metal summation of component (1), is preferably 30～200, and the best is 50～100.
Metallocenes described in the catalyst system of the present invention, can select in the following compound two or more:
Cp 2ZrCl 2, Me 2SiCp 2ZrCl 2, Cp 2TiCl 2, Cp 2HfCl 2, Cp 2TiMeCl, Cp 2ZrMe 2, Cp 2TiMe 2, (C 5Me 5) 2ZrCl 2, (MeC 5H 4) 2ZrCl 2, (EtC 5H 4) 2ZrCl 2, (nC 3H 7C 5H 4) 2ZrCl 2, (iC 3H 7C 5H 4) 2ZrCl 2, (nBuC 5H 4) 2ZrCl 2, (iBuC 5H 4) 2ZrCl 2, (tBuC 5H 4) 2ZrCl 2, (1.2-dimethyl C 5H 3) 2ZrCl 2, (1.3-dimethyl C 5H 3) 2ZrCl 2, (1.2.3-trimethylammonium C 5H 2) 2ZrCl 2, (1.3.4-trimethylammonium C 5H 2) 2ZrCl 2, (1.2-diethyl C 5H 3) 2ZrCl 2, (1.3-diethyl C 5H 3) 2ZrCl 2, (NmCp) 2ZrCl 2, [O (SiMe 2Cp) 2] ZrCl 2, [O (SiMe 2TBuCp) 2] ZrCl 2, [Et (Ind) 2] ZrCl 2, [Et (2,4,7Me 3Ind) 2] ZrCl 2, [Et (IndH 4) 2] ZrCl 2, [Me 2Si (Cp) (Me 4Cp)] ZrCl 2, (Cp) (Me 4Cp)] ZrCl 2, [Me 2Si (Ind) 2] ZrCl 2, [Ph 2Si (Ind) 2] ZrCl 2, [Bz 2Si (Ind) 2] ZrCl 2, [Me 2Si (2,4,7Me 3Ind) 2] ZrCl 2, [Me 2Si (IndH 4) 2] ZrCl 2, [Me 2Si (2Me-4,6iPr 2Ind) 2] ZrCl 2, [Me 2Si (2Me-4Ph-Ind) 2] ZrCl 2, [Me 2Si (2Me-4,6BEtzInd) 2] ZrCl 2, [Ph 2C (Ind) is (Cp)] ZrCl 2, [Me 2C (Ind) is (Cp)] ZrCl 2, [Me 2C (Ind) is (3MeCp)] ZrCl 2, [Ph 2C (Flu) is (Cp)] ZrCl 2, [Me 2C (Flu) is (Cp)] ZrCl 2, [Me 2Ge (2-Me-4Ph-Ind) 2] ZrCl 2, (MeC 5H 4) 2HfCl 2, (EtC 5H 4) 2HfCl 2, (nC 3H 7C 5H 4) 2HfCl 2, (iC 3H 7C 5H 4) 2HfCl 2, (nBuC 5H 4) 2HfCl 2, (iBuC 5H 4) 2HfCl 2, (tBuC 5H 4) 2HfCl 2, [Et (Ind) 2] HfCl 2, [Me 2C (Flu) is (Cp)] HfCl 2, [Me 2Si (Cp) (Me 4Cp)] HfCl 2
It is worthy of note in catalysis in olefine polymerization, can both show institute's inherent catalysis characteristics of the metallocene compound of this kind structure for each metallocene compound, molecular weight and molecular weight distribution as obtained polymkeric substance, the hydrogen of polymkeric substance is transferred sensitivity, the monomeric copolymerization performance of different copolymer, comonomer distribution situation on main polymer chain or the like, the metallocene compound of different structure exists bigger difference in nature above-mentioned, therefore when the metallocene compound of selecting two or more mates, can carry out according to the characteristics of required preparation polymkeric substance.
For ethene polymers or the multipolymer of preparation than wide molecular weight distribution, generally can select the metallocene compound of different transition metal to make up, for example can adopt zirconium metallocene and metallocene hafnium, can be identical for the part of two transition metal, also can be different.Equally also can select the compound of identical transition metal to mate, but then should adopt structure to differ bigger, for example can adopt non-bridged part and bridgingligand to make up for its part.The collocation of two kinds of metallocene compounds or multiple metallocene compound is preferably in the present invention:
Et (Ind) 2ZrCl 2And Et (Ind) 2HfCl 2
Me 2Si (Cp) (Me 4Cp) ZrCl 2And Me 2Si (Cp) (Me 4Cp)] HfCl 2
Me 2Si (Cp) (Me 4Cp) ZrCl 2(Cp) (Me 4Cp) ZrCl 2
Et (Ind) 2ZrCl 2(Cp) (Me 4Cp) ZrCl 2
Et (Ind) 2HfCl 2And Me 2Si (Cp) (Me 4Cp) ZrCl 2
Et (Ind) 2ZrCl 2(n-BuCp) 2ZrCl 2
Et (Ind) 2HfCl 2(n-BuCp) 2ZrCl 2
Me 2Si (Cp) (Me 4Cp) ZrCl 2(n-BuCp) 2ZrCl 2
(Cp) (Me 4Cp) ZrCl 2(n-BuCp) 2ZrCl 2
Me 2Si (Cp) (Me 4Cp) ZrCl 2, (Cp) (Me 4Cp) ZrCl 2(n-BuCp) 2ZrCl 2
Me 2Si (Cp) (Me 4Cp) ZrCl 2, Et (Ind) 2ZrCl 2(n-BuCp) 2ZrCl 2
In the component (1) two or more metallocene compounds between ratio, adopt 0.3～10 so that the molar ratio computing between transition metal is general, be preferably 0.5～5, mol ratio such as be preferably.
It is worthy of note that especially the process of loading with of catalyst system of the present invention is to finish by the aikyiaiurnirsoxan beta that adopts load.At the disclosed supported catalyst of most of metallocene catalyst patents all is to adopt the carrier of handling well to load with MAO earlier, and then be used for polymerization after loading with metallocene compound or metallocene and MAO being carried on carrier respectively, no matter be the former or the latter, because the amount of loading with of metallocene is certain, caused waste so there is relatively large metallocene not load with up, and the price of metallocene is expensive, so cost is higher.When directly being carried on metallocene compound on the carrier simultaneously, loading with of its metallocene only is that physics is loaded with, and is easy to break away from, and therefore can not be used for slurry polymerization or solution polymerization.
Carrier described in the catalyst system of the present invention is inorganic oxide, butter, polymkeric substance or their mixture.For example: can adopt SiO 2, Al 2O 3, anhydrous MgCl 2
The general formula of the aikyiaiurnirsoxan beta described in the catalyst system of the present invention is (R-Al-O) n, wherein R is C 1～C 12Alkyl, for example: methyl, ethyl, propyl group, butyl, amyl group, hexyl, octyl group, the best is a methyl; N is 1～20; The best is 15～20.This aluminium alkoxide compound mainly is to obtain by alkyl aluminum hydrolysis, and for example U.S. Pat 4,544, and the hydrate of 762 disclosed employing metal inorganic salts is the method for water source hydrolysis aluminum alkyls; U.S. Pat 4,968, the method that 827 disclosed employing deionized waters are water source hydrolysis aluminum alkyls; The method that Chinese patent 94119050.1 disclosed employing cyclodextrin compounds are water source hydrolysis aluminum alkyls.
Can also add organo-aluminium compound in the catalyst system of the present invention, this organo-aluminium compound can be selected from trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, tri-butyl aluminum, three hexyl aluminium, aluminium diethyl monochloride, dichloro one aluminium triethyl, and the best is a kind of in trimethyl aluminium, the triethyl aluminum or their mixture.The mol ratio of transition metal is 30～200 in the add-on of organoaluminum and the component (1), is preferably 40～100.
The preparation of catalyst system of the present invention generally is earlier carrier to be carried out activation treatment, then aikyiaiurnirsoxan beta is loaded on the carrier, the promotor and two or more the metallocene compound of load carry out complex reaction in solvent, can also add a certain amount of alkylaluminium cpd in case of necessity.
The preparation method is preferably:
(1) processing of carrier: with carrier at N 2Roasting under the condition, maturing temperature is 200～800 ℃, is preferably 300～500 ℃, roasting time is 1～24 hour.Carrier after the roasting can directly use, and also can carry out vacuum-treat, 50～200 ℃ of vacuum-treat temperature, vacuum processing time 1～24 hour.
(2) loading with of promotor: at a N 2Under the condition, add carrier, aikyiaiurnirsoxan beta and solvent, be warming up to 30～80 ℃ through above-mentioned processing, be preferably 40～60 ℃, stirring reaction 1～10 hour is preferably 3～6 hours, then with solvent wash for several times, vacuum-drying obtains mobile solid cocatalyst.Wherein solvent can adopt aromatic hydrocarbons or aliphatic hydrocarbon, and for example toluene, benzene, dimethylbenzene, ethylbenzene, hexane, heptane, hexanaphthene etc. are the best to select toluene.
(3) complexing of master, promotor; Will be in solvent through the metallocene compound of the above-mentioned promotor of loading with and two or more, under 0～40 ℃, pre-complex reaction 0.1～2 hour is preferably 0.3～0.6 hour.Solvent adopts aromatic hydrocarbons, aliphatic hydrocarbon or its mixture, and for example toluene, benzene, dimethylbenzene, ethylbenzene, hexane, heptane, hexanaphthene etc. are the best to select toluene, hexane or the mixture of the two.
Catalyst system of the present invention can be used for the polymerization and the copolymerization of alkene, and described alkene can be ethene, propylene, butylene, and the comonomer of copolymerization can be selected 1-butylene, 1-hexene, 1-octene; Polymerized form can adopt slurry process, solution method, vapor phase process.
Catalyst system of the present invention compared with prior art has the following advantages and effect:
(1) catalyst system of the present invention has the advantage that single metallocene catalysis system has, as the polymerization activity height, characteristics such as comonomer is evenly distributed on main polymer chain, overcome the shortcoming of single metallocene catalysis system narrow molecular weight distribution simultaneously, by selecting different types of metallocene compound to mate and controlling ratio between it, can easily control the molecular weight distribution of resulting polymers, and obtain Alathon or multipolymer than wide molecular weight distribution, therefore improve the processing characteristics of polymkeric substance widely, widened the Application Areas of polymkeric substance.Can be applied in different fields according to different multipolymer density ranges, for example various packaging films, replacement ethylene-propylene rubber(EPR) are used to produce bumper, plastics toughening agent etc.
(2) catalyst system of the present invention adopts many active centre, multiple metallocene compound is combined with the distinctive method of loading with, overcome that the common polymer morphology of metallocene catalyst is poor, apparent density low and still wall construction structure important disadvantages, the good fluidity of resulting polymers, particle form is good, apparent density is high, not withered still wall.
(3), and there be not loading with of metallocene catalyst owing to only the promotor aikyiaiurnirsoxan beta is loaded with, thus the kind of metallocene compound can be adjusted neatly, and avoid the waste of metallocene.
(4) because in the catalyst system of the present invention, aluminium lower in transition metal and the aikyiaiurnirsoxan beta in the metallocene compound, so reduced the consumption of aikyiaiurnirsoxan beta widely, thus reduced the cost of catalyzer.
The test condition of relevant polymkeric substance is as follows in following examples:
MI 2.16, MI 10, MI 21.6: according to the method for ASTM D-1238-98;
MFR＝MI 21.6/MI 2.16；MFR’＝MI 10/MI 2.16
Density: according to the method for ASTM D-1505-98;
Tap density: according to the method for ASTM D1895.
Embodiment
Preparation of catalysts:
(1) activation of carrier:
At N 2Under the air-flow, with commercially available silica-gel carrier (Grace 955#), 400 ℃ of roastings 8 hours, the cooling back was at N 2Gas bottling down is stand-by.
(2) loading with of aikyiaiurnirsoxan beta: at N 2Under the gas activatory silica gel 4g under the above-mentioned condition is added in the reaction flask, add the toluene 40ml that has refluxed with sodium Metal 99.5 simultaneously, (contain the 1.7g aikyiaiurnirsoxan beta at 25 ℃, aikyiaiurnirsoxan beta/toluene solution of adding 10ml under stirring, n～20), be warming up to 50 ℃ after half an hour, keep reaction 4 hours, use the 50ml toluene wash 5 times at every turn, suction filtration final vacuum drying, bottling.
(3) Preparation of catalysts: at N 2Add in the reaction flask of gas shiled and loaded with the toluene solution that contains two or more metallocene compound under the aikyiaiurnirsoxan beta on the silica gel stirs, at room temperature stirring reaction is 15～30 minutes, obtains catalyst solution.
Vinyl polymerization or copolymerization:
In 2L stainless steel polymeric kettle, N 2Under the gas shiled; the hexane solution that adds the triethyl aluminum of 800ml exsiccant hexane, 0.1～1ml (2mmol/ml); with above-mentioned catalyst solution; add hydrogen, feed ethene, under agitation be warming up to polymeric reaction temperature; keep certain polymerization pressure; polyreaction 2 hours stops to feed ethene, lowers the temperature, emits discharging behind the unnecessary ethene.
During the copolymerization of ethene, comonomer adds in the catalyst reaction still together with catalyst solution, and it is constant that other make condition.
Example 1:
The preparation of catalyst solution: adopting two kinds of metallocene compounds is rac-ethyl bridge two indenyl zirconium dichloride Et (Ind) 2ZrCl 2(consumption is 0.3mgZr), dimethylsilyl (cyclopentadienyl) (tetramethyl-ring pentadienyl) zirconium dichloride Me 2Si (Cp) (Me 4Cp) ZrCl 2, (consumption is 0.3mgZr), the silica gel of load aikyiaiurnirsoxan beta is 81.6mg, wherein aluminium content is 10wt%.
The copolymerization of ethene and hexene-1: hexene-1 monomer 18.7ml, hydrogen 250ml, under the 1.5MPa ethylene pressure (gauge pressure), 80 ℃ of polymerizations 2 hours obtain ethylene copolymer 223g, and activity is 2732g polymkeric substance/gcat, apparent density=0.35g/ml, MI 2.16=0.871, MI 21.6=38.33, MFR (MI 21.6/ MI 2.16)=44.01.
Comparative example 1:
Only adopt a kind of metallocene compound rac-ethyl bridge two indenyl zirconium dichlorides (consumption is 0.6mgZr) in the preparation of catalyst solution, other operational conditions are identical with embodiment 1.
The copolymerization of ethene and hexene-1: operational condition obtains ethylene copolymer 200g with example 1, and activity is 2631g polymkeric substance/gcat, apparent density=0.33g/ml, MI 2.16=0.83, MI 21.6=24.07, MFR=29.
Embodiment 2
The preparation of catalyst solution: adopting two kinds of metallocene compounds is rac-ethyl bridge two indenyl zirconium dichlorides (consumption is 0.3mgZr), (cyclopentadienyl) (tetramethyl-ring pentadienyl) zirconium dichloride, (consumption is 0.3mgZr), the silica gel of load aikyiaiurnirsoxan beta is 92.4mg, and wherein aluminium content is 10wt%.
Ethylene homo closes: except not adding comonomer, polymerizing condition is with embodiment 1.Obtain ethene polymers 473g, activity is 5119g polymkeric substance/gcat, apparent density=0.40g/cm 3, MI 2.16=0.36, MI 10=3.05, MFR ' (MI 10/ MI 2.16)=8.47.
Comparative example 2:
Only adopt a kind of metallocene compound rac-ethyl bridge two indenyl zirconium dichlorides (consumption is 0.6mgZr) in the preparation of catalyst solution, the silica gel of load aikyiaiurnirsoxan beta is 89.6mg, and other operational conditions are identical with polymerizing condition embodiment 2.Obtain ethene polymers 377g, activity is 4200g polymkeric substance/gcat, apparent density=0.40g/ml, MI 2.16=0.28, MI 10=1.68, MFR '=6.02.
Embodiment 3
The preparation of catalyst solution: adopting two kinds of metallocene compounds is rac-ethyl bridge two indenyl zirconium dichlorides (consumption is 0.45mgZr), dimethylsilyl (cyclopentadienyl) (tetramethyl-ring pentadienyl) zirconium dichloride, (consumption is 0.15mgZr), the silica gel of load aikyiaiurnirsoxan beta is 82.9mg, and wherein aluminium content is 10wt%.
The copolymerization of ethene: hydrogen 400ml, under the 1.5MPa ethylene pressure (gauge pressure), 80 ℃ of polymerizations 2 hours obtain ethene polymers 498g, and activity is 6007g polymkeric substance/gcat, apparent density=0.41g/ml, MI 2.16=0.75, MI 21.6=21.19, MFR (MI 21.6/ MI 2.16)=28.25.
Embodiment 4～embodiment 8:
It is rac-ethyl bridge two indenyl zirconium dichlorides that catalyzer all adopts two kinds of metallocene compounds, dimethylsilyl (cyclopentadienyl) (tetramethyl-ring pentadienyl) zirconium dichloride, catalyst preparation step and converging operation are all with example 1, only the content of hydrogen in the consumption of the silica gel of the ratio between two kinds of metallocene compounds, load aikyiaiurnirsoxan beta, the polymerization, the content of comonomer are changed, it the results are shown in Table 1.
Embodiment 9～embodiment 14:
Catalyst preparation step and converging operation be all with example 1, only the content of hydrogen in the consumption of the silica gel of two kinds of metallocene compound kinds and the ratio between the two, load aikyiaiurnirsoxan beta, the polymerization, the content of comonomer changed, and it the results are shown in Table 2.
Embodiment 15,16
Adopt three kinds of metallocene compounds, all with example 1, it the results are shown in Table 2 for catalyst preparation step and converging operation.
Table 1
Embodiment Main catalyst component The ratio of metallocene compound The silica gel weight (mg) of load aikyiaiurnirsoxan beta Amounts of hydrogen (ml) Hexene-1 content (ml) Catalyst activity gPE/gcat Apparent density (g/cm 3) MI 2.16 MI 21.6 MFR
Example 1 Et(Ind) 2ZrCl 2/Me 2Si(Cp) (Me 4Cp)ZrCl 2 0.3/0.3 81.6 250 18.7 2732 0.35 0.871 38.33 44.01
Compare 1 Et(Ind) 2ZrCl 2 0.6 81.6 250 18.7 2631 0.33 0.83 24.07 29.00
Example 4 Et(Ind) 2ZrCl 2/Me 2Si(Cp) (Me 4Cp)ZrCl 2 0.15/0.45 86.4 400 0 4630 0.41 0.34 16.13 47.44
Example 5 The same 0.45/0.15 83.6 650 0 4222 0.41 0.93 25.68 27.61
Example 6 The same 0.3/0.3 82.3 400 12 4301 0.28 1.22 31.76 26.03
Example 7 The same 0.3/0.3 92.0 150 12 3174 0.27 0.56 20.84 37.21
Example 8 The same 0.3/0.3 91.7 250 12 3468 0.26 0.704 28.25 40.10
Table 2
Embodiment Main catalyst component The ratio of metallocene compound The silica gel weight (mg) of load aikyiaiurnirsoxan beta Amounts of hydrogen (ml) Hexene-1 content (ml) Catalyst activity gPE/gcat Apparent density (g/cm 3) MI 2.16 MI 10 MFR’
Example 2 Et(Ind) 2ZrCl 2/ (Cp)(Me 4Cp)ZrCl 2 0.3/0.3 92.40 250 0 5119 0.40 0.36 3.05 8.47
Compare 2 Et(Ind) 2ZrCl 2 0.6 89.6 250 0 4200 0.40 0.28 1.68 6.02
Example 9 Et(Ind) 2ZrCl 2/ (Cp)(Me 4Cp)ZrCl 2 0.15/0.45 91.5 250 0 3071 0.39 0.40 3.20 8.00
Example 10 The same 0.15/0.45 93.6 500 0 3269 0.39 0.24 3.09 12.88
Example 11 The same 0.45/0.15 89.4 500 0 3479 0.41 0.939 7.36 7.84
Example 12 Me 2Si(Cp)(Me 4Cp)ZrCl 2/ (n-BuCp) 2ZrCl 2 0.3/0.3 111 0 18.7 2279 0.37 0.988 6.49 6.57
Example 13 (Cp)(Me 4Cp)ZrCl 2/(n- BuCp) 2ZrCl 2 0.3/0.3 112 0 0 3642 0.37 0.187 1.155 6.18
Example 14 Et(Ind) 2ZrCl 2/ (n-BuCp) 2ZrCl 2 0.3/0.3 84 0 0 6285 0.38 0.152 0.975 6.41
Example 15 Me 2Si(Cp)(Me 4Cp)ZrCl 2/ (Cp)(Me 4Cp)ZrCl 2/ (n-BuCp) 2ZrCl 2 0.2/0.2/0.2 97 0 0 3732 0.32 0.176 1.093 6.21
Example 16 Me 2Si(Cp)(Me 4Cp)ZrCl 2/ Et(Ind) 2ZrCl 2/ (n-BuCp) 2ZrCl 2 0.2/0.2/0.2 92 0 0 2391 0.38 0.176 1.25 7.13

Claims (12)

1, a kind of metallocene catalysis system that is used for olefinic polymerization or copolymerization comprises following component:
(1) two or more unsupported metallocene compound, wherein the general formula of metallocene compound is:
Wherein M is transition metal Ti or Zr or Hf,
X is alkyl or halogen
L, L ' they are dentate, can be selected from a kind of in the fluorenyl of indenyl, fluorenyl, replacement of cyclopentadienyl, indenyl, the replacement of cyclopentadienyl, replacement, and L, L ' can be identical, also can be different,
B is for linking the bridge of L, L ' position base, and according to the difference of L, L ' dentate, this bridge can exist and also can not exist, and the form of bridge is-SiRR ' ,-GeRR ' ,-CRR ' ,-SiR 2-O-SiR ' 2-in a kind of, R, R ' are C 1～C 20Straight chained alkyl, its can be identical can be inequality,
(2) through carrier loaded aikyiaiurnirsoxan beta.
2, metallocene catalysis system according to claim 1 is characterized in that, the ratio between described component (2) and the component (1) is 30～2000 with the molar ratio computing of Al in the component (2) and the middle transition metal summation of component (1).
3, metallocene catalysis system according to claim 1 is characterized in that, the ratio between described component (2) and the component (1) is 30～200 with the molar ratio computing of Al in the component (2) and the middle transition metal summation of component (1).
4, metallocene catalysis system according to claim 1 is characterized in that, described component (1) is selected arbitrary group in the following compounds:
Et (Ind) 2ZrCl 2And Et (Ind) 2HfCl 2
Me 2Si (Cp) (Me 4Cp) ZrCl 2And Me 2Si (Cp) (Me 4Cp)] HfCl 2
Me 2Si (Cp) (Me 4Cp) ZrCl 2(Cp) (Me 4Cp) ZrCl 2
Et (Ind) 2ZrCl 2(Cp) (Me 4Cp) ZrCl 2
Et (Ind) 2HfCl 2And Me 2Si (Cp) (Me 4Cp) ZrCl 2
Et (Ind) 2ZrCl 2(n-BuCp) 2ZrCl 2
Et (Ind) 2HfCl 2(n-BuCp) 2ZrCl 2
Me 2Si (Cp) (Me 4Cp) ZrCl 2(n-BuCp) 2ZrCl 2
(Cp) (Me 4Cp) ZrCl 2(n-BuCp) 2ZrCl 2
Me 2Si (Cp) (Me 4Cp) ZrCl 2, (Cp) (Me 4Cp) ZrCl 2(n-BuCp) 2ZrCl 2
Me 2Si (Cp) (Me 4Cp) ZrCl 2, Et (Ind) 2ZrCl 2(n-BuCp) 2ZrCl 2
5, metallocene catalysis system according to claim 1 is characterized in that, in the described component (1) two or more metallocene compounds between ratio, be 0.3～10 with the molar ratio computing between transition metal.
6, metallocene catalysis system according to claim 1 is characterized in that, in the described component (1) two or more metallocene compounds between ratio, be 0.5～5 with the molar ratio computing between transition metal.
7, metallocene catalysis system according to claim 1 is characterized in that, in the described component (1) two or more metallocene compounds between ratio, with mol ratios such as the molar ratio computing between transition metal are.
8, metallocene catalysis system according to claim 1 is characterized in that, the general formula of described component (2) aikyiaiurnirsoxan beta is (R-Al-O) n, wherein R is C 1～C 12Alkyl.
9, metallocene catalysis system according to claim 1, it is characterized in that, also can add in the following organo-aluminium compound one or more: trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, tri-butyl aluminum, three hexyl aluminium, aluminium diethyl monochloride, dichloro one aluminium triethyl.
10, metallocene catalysis system according to claim 9 is characterized in that, the mol ratio of transition metal is 30～200 in organoaluminum and the component (1).
11, the preparation method of the metallocene catalysis system of one of claim 1～10 carries out activation treatment with carrier earlier, then aikyiaiurnirsoxan beta is loaded on the carrier, the aikyiaiurnirsoxan beta and two or more the metallocene compound of load carry out complex reaction in solvent, randomly add a certain amount of alkylaluminium cpd.
12, the application of the metallocene catalysis system of one of claim 1～10 in vinyl polymerization or copolymerization.
CNB001303880A 2000-11-03 2000-11-03 Metallocene catalyst for polymerizing or copolymerizing ethylene and its preparing process and application Expired - Lifetime CN1151184C (en)

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