CN1098284C - Metallocene catalysis system for olefin polymerization and copolymerization and its preparation method - Google Patents

Metallocene catalysis system for olefin polymerization and copolymerization and its preparation method Download PDF

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CN1098284C
CN1098284C CN97116451A CN97116451A CN1098284C CN 1098284 C CN1098284 C CN 1098284C CN 97116451 A CN97116451 A CN 97116451A CN 97116451 A CN97116451 A CN 97116451A CN 1098284 C CN1098284 C CN 1098284C
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catalysis system
metallocene
metallocene catalysis
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CN1211579A (en
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郑莹
邱波
姚辉
王熙
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Beijing Institute Of Chemical Technology Ministry Of Chemcial Industry
China Petrochemical Corp
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Beijing Institute Of Chemical Technology Ministry Of Chemcial Industry
China Petrochemical Corp
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Abstract

The present invention relates to a metallocene catalysis system for olefin polymerization and copolymerization and a preparation method thereof. The metallocene catalysis system mainly comprises non-loaded metallocene and loaded MAO. The catalysis system has the characteristics of high polymerization activity, good shape of polymer particles and high apparent density; the catalysis system overcomes the defect of easy kettle sticking of a homogeneous catalysis system for polymerization and prevents metallocene from being wasted.

Description

Olefinic polymerization and copolymerization metallocene catalysis system and preparation method thereof
The present invention relates to a kind of metallocene catalysis system that is used for olefinic polymerization and copolymerization and preparation method thereof.
In recent years, metallocene/aikyiaiurnirsoxan beta (MAO) catalyst system of Kaminsky invention, caused people's extensive concern, this catalyst system has the advantage of following uniqueness,: 1, the monomer polymerization that almost can make all contain vinyl, wherein many monomers are that traditional Ziegler-Natta catalyst system can not carry out polymeric; 2, catalyst system has single active centre, makes the polymkeric substance that obtains have chain length than homogeneous; 3, adopt different metallocenes, can obtain the polymkeric substance of different tacticities, for example can obtain traditional Ziegler-Natta catalyst system can not getable rule PP, a rule PS etc.; 4, resulting polymers often contains terminal ethylenyl groups, thereby has improved the impressionability of polymkeric substance, covering with paint property, consistency etc.; 5, the means of effective polymer design are provided for people.
But when having above-mentioned series of advantages, still there are some shortcomings in this catalyst system, has therefore hindered its application and development.These shortcomings are mainly two aspects, and the first costs an arm and a leg because the most complex structure of Primary Catalysts metallocene is synthetic relatively more difficult, and the requirement of expensive promotor aikyiaiurnirsoxan beta is also bigger simultaneously, so the cost of this catalyst system is higher; It is two when being to use this catalyst system to carry out polymerization in homogeneous phase, and sticking still phenomenon is serious, and the particle form of polymkeric substance is bad, is unsuitable for suitability for industrialized production.
In order to improve the particle form of polymkeric substance, people adopt the method with support of the catalystization, and the method for loading with is a lot.The carrying method of Gong Buing (Makromol.Chem.Rapid Commun.14 the earliest, 239-243,1993) be at first metallocene compound to be loaded on the silica gel of handling, silica gel is handled for a long time through metallocene compound solution, fixing than behind the jail with solvent wash again to the metallocene compound of loading with, drain and be used for olefinic polymerization; Or the silica gel of load cyclopentadinyl compound contacted with MAO (aikyiaiurnirsoxan beta) again, MAO is loaded with up again, experiment showed, this kind carrying method, the charge capacity of metallocene is all higher, but the polymerization activity during polymerization is all lower, therefore is difficult to realize industrialization.
Another loads with method (J.Polym.Sci.PartA.Polym.Chem 29) is that the silica gel that will handle well is loaded with MAO earlier, and then load with metallocene compound, though this to load with the method polymerization activity higher, but the polymer beads form is bad, the sticking still phenomenon of polymkeric substance does not obviously alleviate, and in loading with the metallocene process, 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.
EXXON company discloses a kind of catalyst system that is used for the alkene polymerization in homogeneous phase in WO 95/07939, it is to be used for polymerization after metallocene and MAO are carried on carrier respectively, the polymer beads form that obtains is better, but this catalyst system only can be used for the vapour phase polymerization of alkene, and loading with of its metallocene only is that physics is loaded with, be easy to break away from, therefore can not be used for slurry polymerization or solution polymerization.
The present invention is in order to overcome the shortcoming that above-mentioned prior art exists, a kind of metallocene catalysis system that is used for olefinic polymerization and copolymerization and preparation method thereof has been proposed, it mainly is made up of with the MAO that loads with the non-metallocene of loading with, the characteristics of this catalyst system are that polymerization activity is higher, the polymer beads form is good, the apparent density height, the shortcoming of very easily sticking still when having overcome the homogeneous catalysis system polymerization, and the problem that does not exist metallocene to be wasted.
The metallocene catalysis system that is used for olefinic polymerization and copolymerization of the present invention comprises following component:
(1) at least a general formula is
Figure C9711645100051
Metallocenes,
Wherein M is transition metal Ti or Zr or Hf,
X is alkyl or halogen,
L, L 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 In a kind of, R, R ' are the straight-chain low-carbon alkyl, its can be identical can be inequality.
(2) aikyiaiurnirsoxan beta of loading with through carrier;
(3) at least a organo-aluminium compound;
The mol ratio of the middle transition metal of Al and component (1) is 30～2000 in the said components (2), is preferably 30～200, and the best is 50～100; The mol ratio of the middle transition metal of Al and component (1) is 30～200 in the component (3).
Metallocenes described in the catalyst system of the present invention can be following Compound C p 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, (NmCp) 2ZrCl 2, (C 5Me 4Et) 2ZrCl 2, [O (SiMe 2Cp) 2] ZrCl 2, [O (SiMe 2TBuCp) 2] ZrCl 2, [En (Ind) 2] ZrCl 2, [En (Ind) 2] HfCl 2, [En (2,4,7Me 3Ind) 2] ZrCl 2, [En (IndH 4) 2] 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-4,6BenzInd) 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 2C (Flu) is (Cp)] HfCl 2, [Me 2Ge (2-Me-4Ph-Ind) 2] ZrCl 2
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, the method that 762 disclosed employing metal inorganic salts are 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.
Organo-aluminium compound described in the catalyst system of the present invention can be selected from trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, tri-butyl aluminum, three hexyl aluminium, aluminium diethyl monochloride, dichloro one basic aluminium, and the best is a kind of in trimethyl aluminium, the triethyl aluminum or their mixture.
The preparation method of catalyst system of the present invention is:
(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 above-mentioned promotor of loading with and Primary Catalysts metallocene compound, under 0～40 ℃, pre-complex reaction 0.3～2 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) owing to saved the step that Primary Catalysts is loaded with, only carry out loading with of promotor, this has just saved the consumption of expensive metallocene compound widely, because any process of loading with, all can not reach and absolutely load with, the loading with in the process of prior art metallocene, the metallocene compound that must have the not load of suitable vast scale will be washed off by solvent like this, cause great waste, catalyst system of the present invention has then been avoided this waste;
(2) in the prior art, industrialized homogeneous catalyst is to be used for vapour phase polymerization or solution polymerization basically, and catalyst system of the present invention not only can be used for above-mentioned polymerization, and can be used for slurry polymerization, has therefore opened up its Application Areas widely.
(3) after catalyst system of the present invention is used for olefinic polymerization, the polymer beads form that obtains is fine, apparent density is higher, during in particular for the slurry polymerization of alkene, the shortcoming of very easily sticking still when having overcome homogeneous catalysis system slurry polymerization in the prior art, and polyvinyl apparent density all can reach 0.36～0.40g/cm 3
(4) in catalyst system of the present invention, can adjust the kind of metallocene compound neatly according to the polymer properties requirement.
Embodiment
Example 1:
(1) preparation of promotor:, add the Al of 52g successively blowing through nitrogen in row's the reaction flask 2(SO 4) 318H 2The toluene of O, 80ml is cooled to-4 ℃ under stirring, and the toluene solution (78ml trimethyl aluminium and 320ml toluene) that begins to drip trimethyl aluminium dropwised in about 3～4 hours, naturally be warming up to 40 ℃, isothermal reaction 24 hours, vacuum is drained, and promptly gets the methylaluminoxane pressed powder.
(2) loading with of promotor: get the silica gel (Davision 955) of 10g, at N 2Under the air-flow, 400 ℃ of roastings 4 hours vacuumized under 120 ℃ 16 hours again.
At one through N 2In the reaction flask that air-blowing was arranged, add 7g through the above-mentioned silica gel of dehydroxylation, the methylaluminoxane and the 100ml toluene of 3g method for preparing handled, be warming up to 50 ℃, stirring reaction 4 hours, use the 50ml toluene wash then 5 times, vacuum-drying obtains mobile white solid promotor.
(3) the pre-complexing of catalyzer: in reaction flask, add the Et (Ind) of above-mentioned promotor of 0.2g and 4ml 2ZrCl toluene solution (concentration is the 0.3mgZr/ml toluene solution, is equivalent to 1.2mgZr) and 20ml hexane stirred 30 minutes.
(4) vinyl polymerization: in the stainless steel autoclave of 2L, blow row through nitrogen, after ethene was repeatedly replaced, the hexane of adding 1000ml, above-mentioned catalyzer and the triethyl aluminum of 1mmol fed ethene and also maintain 1.5MPa, and 70 ℃ were reacted 2 hours.Cooling after-filtration, drying obtain polyethylene powders.
Example 2:
Only with the metallocene compound in the example 1 by Et (Ind) 3ZrCl 2Change Me into 2Ge (2-Me-4ph-Ind) 2ZrCl 2, add-on is counted 2.6mg with Zr, and other Preparation of Catalyst conditions and vinyl polymerization condition are all constant.
Example 3:
Only with the metallocene compound in the example 1 by Et (Ind) 3ZrCl 2Change Cp into 2ZrCl 2, add-on is counted 2.6mg with Zr, and triethyl aluminum changes trimethyl aluminium into, and add-on is 1mmol, and other Preparation of Catalyst conditions and vinyl polymerization condition are all constant.
Embodiment Catalyst system Al/Zr * Polymerization activity gPE/molZr Apparent density g/cm 3
Example 1 Et(Ind) 2ZrCl 2、MAO/SO 2、AlEt 3 38 1.2×10 7 0.35
Example 2 Me 2Ge(2-Me-4ph-Ind) 2ZrCl 2、MAO/SO 2、AlEt 3 133 8.3×10 6 0.36
Example 3 Cp 2ZrCl 2、MAO/SO 2、AlMe 3 68 6.2×10 6 /
* with MAO/SiO 2In Al meter (following examples all with)
Example 4: only with the metallocene compound Et (Ind) in the example 1 3ZrCl 2Add-on change 0.6mg into by 1.2mg, other Preparation of Catalyst conditions and vinyl polymerization condition are all constant.
Example 5: only with the metallocene compound Et (Ind) in the example 1 3ZrCl 2Add-on change 0.6mg into by 1.2mg, triethyl aluminum changes trimethyl aluminium into, add-on is 1mmol, other Preparation of Catalyst conditions and vinyl polymerization condition are all constant.
Example 6: only change the triethyl aluminum in the example 1 into aluminium diethyl monochloride, add-on is 1mmol, and other Preparation of Catalyst conditions and vinyl polymerization condition are all constant.
Example 7: only with the metallocene compound Et (Ind) in the example 1 3ZrCl 2Add-on change 0.6mg into by 1.2mg, triethyl aluminum changes triisobutyl aluminium into, add-on is 1mmol, other Preparation of Catalyst conditions and vinyl polymerization condition are all constant.
Embodiment Catalyst system Al/Zr * Polymerization activity gPE/molZr Apparent density g/cm 3
Example 4 Et(Ind) 2ZrCl 2、MAO/SO 2、AlEt 3 985 6.1×10 7 0.36
Example 5 Et(Ind) 2ZrCl 2、MAO/SO 2、AlMe 3 975 2.1×10 7 /
Example 6 Et(Ind) 2ZrCl 2、MAO/SO 2、AlEt 2Cl 144 Very low /
Example 7 Et(Ind) 2ZrCl 2、MAO/SO 2、Al(i-Bu) 3 955 1.4×10 7 /
Example 8～example 11: only with the carrier S iO in the example 1 2Treatment condition change, other Preparation of Catalyst conditions and vinyl polymerization condition are all with example 1.
Embodiment SiO 2Treatment condition Al/Zr * Polymerization activity gPE/molZr Apparent density g/cm 3
Example 8 N 2Following 400 ℃ of roasting 4h, 120 ℃ of vacuum baking 16h 56 1.8×10 7 0.39
Example 9 N 2Following 300 ℃ of roasting 4h, 120 ℃ of vacuum baking 16h 100 1.2×10 7 0.36
Example 10 N 2Following 400 ℃ of roasting 4h 88 1.8×10 7 0.38
Example 11 N 2Following 400 ℃ of roasting 8h 193 3.0×10 7 0.35
Example 12:
Preparation of catalysts is with example 1.
The copolymerization of ethene and hexene-1: method and condition are closed with the ethylene homo of example 1, only add comonomer before adding catalyzer.
Example 13: only change the add-on of hexene, other conditions are with example 12.
Example 14: change the add-on of catalyst system and hexene, other conditions are with example 12.
Embodiment Catalyst system Hexene-1 concentration M Polymerization activity PE/molZr Density g/cm 3 Hexene in the polymkeric substance-1 content (%)
Example 12 Et(Ind) 2ZrCl 2、MAO/SO 2、AlMe 3 0.57 2.1×10 7 0.9348 2.2
Example 13 Et(Ind) 2ZrCl 2、MAO/SO 2、AlMe 3 1.53 0.64×10 7 0.9126 5.8
Example 14 Me 2Ge(2-Me-4ph-Ind) 2ZrCl 2、MAO /SiO 2、AlMe 3 0.76 0.40×10 7 0.9214 5.0
Example 15
Preparation of catalysts is with example 1.
The mass polymerization of propylene: in 21 high pressure stainless steel still, through N 2After blowing row, propylene and repeatedly replacing, add triethyl aluminum, the 400ml liquid propene of 1mmol, open and stir, N 2Protection adds 0.3mg Et (Ind) down in the high-pressure charging pipe 2ZrCl 2Toluene solution and the promotor 0.8g that loads with reacted after 20 minutes, with the 400ml liquid propene catalyzer were poured in the still again.Heat up 70 ℃, polymerization 2 hours, the recovering liquid propylene is put pressure, discharging, obtains the white polypropylene powder.
Embodiment Catalyst system Al/Zr * Polymerization activity gPE/molZr Apparent density g/cm 3
Example 15 Et(Ind) 3ZrCl 2、MAO/SO 2、AlEt 3 1376 2.3×10 7 0.34
Example 16 Me 2Si(Ind) 2ZrCl 2、MAO/SO 2、AlEt 3 1354 1.5×10 7 0.34
Example 17 Me 2Ce(2-Me-4ph-Ind) 2ZrCl 2、MAO/SO 2、AlEt 3 1958 3.0×10 7 0.26

Claims (7)

1, a kind of metallocene catalysis system that is used for olefinic polymerization and copolymerization comprises following component: (1) at least a general formula is Metallocenes,
Wherein M is transition metal Ti or Zr or Hf,
X is alkyl or halogen
L, L ' they are dentate, are 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-Si-,-Ge-,-C-,
A kind of among the-Si-O-Si-, R, R ' they are the straight-chain low-carbon alkyl, its can be identical can be inequality,
(2) aikyiaiurnirsoxan beta of loading with through carrier;
(3) at least a organo-aluminium compound;
The mol ratio of the middle transition metal of Al and component (1) is 30～2000 in the said components (2), and the mol ratio of the middle transition metal of Al and component (1) is 30～200 in the component (3).
2, metallocene catalysis system according to claim 1 is characterized in that, described metallocenes is following Compound C p 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, (C 5Me 4Et) 2ZrCl 2, [O (SiMe 2Cp) 2] ZrCl 2, [O (SiMe 2TBuCp) 2] ZrCl 2, [En (Ind) 2] ZrCl 2, [En (Ind) 2] HfCl 2, [En (2,4,7Me 3Ind) 2] ZrCl 2, [En (IndH 4) 2] 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-4,6BenzInd) 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 2C (Flu) is (Cp)] HfCl 2, [Me 2Ge (2-Me-4Ph-Ind) 2] ZrCl 2In a kind of.
3, metallocene catalysis system according to claim 1 is characterized in that, described carrier is inorganic oxide, butter, polymkeric substance or their mixture.
4, metallocene catalysis system according to claim 1 is characterized in that, the general formula of described aikyiaiurnirsoxan beta is (R-Al-O) n, wherein R is C 1～C 12Alkyl, n is 1～20.
5, metallocene catalysis system according to claim 1 is characterized in that, described organo-aluminium compound is selected from a kind of of trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, tri-butyl aluminum, three hexyl aluminium, aluminium diethyl monochloride, or their mixture.
6, metallocene catalysis system according to claim 1 is characterized in that, the mol ratio of Al and the middle transition metal of component (1) is for being 50～100 in the described component (2).
7, the preparation method of the described metallocene catalysis system of one of claim 1～6 comprises the steps:
(1) processing of carrier: with carrier at N 2Roasting under the condition, maturing temperature are 200～800 ℃, and 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, stirring reaction 1～10 hour, then with solvent wash for several times, vacuum-drying obtains mobile solid cocatalyst, and wherein solvent adopts aromatic hydrocarbons or aliphatic hydrocarbon;
(3) complexing of master, promotor; Will be in solvent through the above-mentioned promotor of loading with and Primary Catalysts metallocene compound, under 0～40 ℃, pre-complex reaction 0.3～2 hour, solvent adopts aromatic hydrocarbons, aliphatic hydrocarbon or its mixture.
CN97116451A 1997-09-18 1997-09-18 Metallocene catalysis system for olefin polymerization and copolymerization and its preparation method Expired - Lifetime CN1098284C (en)

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US6608149B2 (en) 2000-12-04 2003-08-19 Univation Technologies, Llc Polymerization process
US6605675B2 (en) 2000-12-04 2003-08-12 Univation Technologies, Llc Polymerization process
RU2258712C2 (en) 2000-12-04 2005-08-20 Юнивейшн Технолоджиз, Ллс Polymerization process
EP1814922A1 (en) * 2004-11-22 2007-08-08 Basell Polyolefine GmbH Propylene based terpolymers
JP5124938B2 (en) * 2005-12-19 2013-01-23 東ソー株式会社 Olefin polymerization catalyst and process for producing olefin polymer
JP2020050615A (en) * 2018-09-27 2020-04-02 三井化学株式会社 Transition metal compound, olefin polymerization catalyst, and olefin polymer production method

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WO1995007939A1 (en) * 1993-09-17 1995-03-23 Exxon Chemical Patents Inc. Polymerization catalyst systems, their production and use
CN1134160A (en) * 1993-11-05 1996-10-23 博里利斯控股公司 Supported olefin polymerization catalyst, its preparation and use

Patent Citations (2)

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Publication number Priority date Publication date Assignee Title
WO1995007939A1 (en) * 1993-09-17 1995-03-23 Exxon Chemical Patents Inc. Polymerization catalyst systems, their production and use
CN1134160A (en) * 1993-11-05 1996-10-23 博里利斯控股公司 Supported olefin polymerization catalyst, its preparation and use

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100339402C (en) * 2003-01-28 2007-09-26 托塔尔石油化学产品研究弗吕公司 Group III bridged ionic metallocene based on cyclopentadienyl-fluorenyl ligands

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