CN102432702A - Alkene polymerization catalyst composition - Google Patents
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- CN102432702A CN102432702A CN201010502801XA CN201010502801A CN102432702A CN 102432702 A CN102432702 A CN 102432702A CN 201010502801X A CN201010502801X A CN 201010502801XA CN 201010502801 A CN201010502801 A CN 201010502801A CN 102432702 A CN102432702 A CN 102432702A
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Abstract
The invention provides an alkene polymerization catalyst composition comprising a transition metal compound as a catalyst, alkyl aluminoxane as a cocatalyst, and an organic zinc compound as a polymerization activity promoter, wherein the molar ratio of the transition metal compound to the organic zinc compound is 1:1 to 1:500. Compared with a traditional polymerization catalyzing system, with the polymerization catalyzing system provided by the invention, an activity can be multiplied by times.
Description
Technical field
The present invention relates to a kind of olefin Polymerization catalyst compositions, belong to catalysis and field of olefin polymerisation.
Technical background
Single central transition metal catalyzer of for olefines polymerization is the research focus of Organometallic Chemistry, catalysis, polymer chemistry and materialogy in nearly decades always.The most representative is metallocene catalysis system.Compare with traditional Ziegler-Natta catalystsystem; Metallocene catalyst has the characteristic at single-activity center; Catalyzed polymerization can obtain MWD and all well-proportioned olefin polymer of chemical constitution distribution, and traditional Z iegler-Natta catalyzer has a plurality of active site, and the chemical constitution of polymkeric substance distributes all inhomogeneous with the molecule interchain in molecular chain; And the MWD of polymkeric substance is also than broad, and this is very unfavorable to performance of products.In addition, when Ziegler-Natta catalyst catalyzed ethylene and alpha-olefin copolymer, as the Ti in active site
3+Maybe be by promotor triethyl aluminum (Al (C
2H
5)
3) be reduced into Ti
2+, Ti
2+Only ethene is had catalytic activity, other terminal olefin is not had activity, this can make the homopolymer that is mixed with ethene in the polymkeric substance, has influenced polymer properties (Polym.Bull., 1982,7,517).Use metallocene catalyst, the molecular structure of polymkeric substance and molecular weight can be controlled through adjustment catalyst structure height, and can obtain the olefin polymer that traditional Z iegler-Natta catalyzer can not obtain.
Understanding to metallocene can be traced back to the middle of last century.Wilkinson and Fischer have illustrated structure (J.Am.Chem.Soc., 1954,76,4281 of ferrocene at first; Angew.Chem., 1952,22,620).Natta and Breslow found respectively afterwards, at triethyl aluminum (Al (C
2H
5)
3) or diethyl aluminum chloride ((C
2H
5)
2When AlCl) existing, cyclopentadienyl titanium dichloride (Cp
2TiCl
2) can catalyzed ethylene polymerization, but polymerization activity quite low (Chim.Ind. (Millan), 1957,39,1032; J.Am.Chem.Soc., 1957,79,5072).
Because polymerization activity is too low, afterwards for a long time in, metallocene only is confined to theoretical investigation.1973, people's such as Reichert work showed, in luxuriant titanium-alkyl aluminum chloride polymerization system, introduces the water of very small amount, can make polymerization activity improve (Macromol.Chem., 1973,169,163).1980, human MAO substituted alkyl aluminium such as Sinn and Kaminsky showed high polymerization activity (Angew.Chem., 1980,92,296) as the promotor of metallocene catalyzed ethylene polymerization.After this, the research of metallocene catalysis olefinic polymerization constantly produces new breakthrough.Brintzinger is synthetic with Even and separated the bridging chiral metallocene, can the catalyzing propone polymerization produce isotatic polypropylene (Angew.Chem., 1985,97,507; J.Am.Chem.Soc., 1984,106,6355).1988, Even used the means of special bridged metallocene catalysts of ad hoc structure to synthesize syndiotactic polypropylene (J.Am.Chem.Soc., 1988,11O, 6255).Chien utilizes the luxuriant titanium of chirality, only synthesizes thermoplastic elastomer (J.Am.Chem.Soc., 1990,112,2030) with a kind of monomer propylene first.By 1991, the investigator generally believed that the catalytic active center of metallocene catalyst is monoalkyl cationic (Adv.Organomet.Chem., 1991,32,325).Nineteen ninety-five, Waymouth proposes the model in the rotation active site of non-bridged combined metal, and has synthesized stereoblock Vestolen PP 7052 (Science, 1995,267,217) with this type of catalyzer.
Can find out that discovery novel texture, that have the metallocene catalyst of new polymerization property has constantly advanced the process of metallocene catalyst research, is bringing in constant renewal in the notion of single-site catalysts catalysis in olefine polymerization.Simultaneously, it should be noted that in the polymerization system, except that transistion metal compound (like metallocene compound), other components (as be used as the MAO of " promotor ", MAO) polymerization activity and polymerization behavior are played crucial effects.Promotor from the aluminum alkyls to the MAO, has brought tremendous lifting for the polymerization activity of metallocene catalysis system.Organic boron co-catalyst system of finding has afterwards obtained great success equally, and (EP 427697; J.Am.Chem.Soc., 1991,113,3623).
In order to understand the polymerization process of single-site catalysts better, the investigator has set up various models.First proposes the motive force of growth model of homogeneous catalysis system Even, and this is a simplifying model, is applicable to the monomer low-conversion, long-pending and the rate of polymerization linear (J.Am.Chem.Soc., 1984,106,6355) of monomer concentration and catalyst concn.Chien has proposed the kinetic model of different catalysts catalyzed ethylene, propylene polymerization.There is more than one spike in model hypothesis, has the chain transfer to MAO, has β-H shift reaction, and the spike inactivation is first order reaction (J.Polym.Sci., A, 1990,28,15; 1991,29,459).Hamielec has proposed many active site kinetic model of catalyzed ethylene polymerization.Model is thought; Have the various active center in the polymerization system, the active site that produces low-molecular weight polymer irreversibly is converted into the active site that produces high-molecular weight polymer with first order reaction, and chainpropagation is first order reaction to monomer and active site; Exist in the system to monomeric shift reaction, to shift reaction and the β-H shift reaction (Polymer of MAO; 1994,35,808).Along with to dynamic (dynamical) further investigation, it is found that shift reaction plays an important role to controlled polymerization behavior and adjustment polymer architecture performance.
The 1950's, Ziegler etc. have reported so-called " Aufbaureaktion reaction ".Under HTHP, aluminum alkyls can cause ethylene oligomerization, and ethylene molecule is inserted into the Al-C key continuously; Thereby obtain long aliphatic chain aluminum compound (Angew.Chem.1952,64,323); Through the reaction of end group aluminium, can obtain having the functionalization product of long aliphatic chain.Be in the polymerization system of catalyzer with the transistion metal compound; If have a large amount of metallic bond transfering reagents; Polymeric chain can carry out reversible fast exchange between transition-metal catalyst and metallic bond transfering reagent, and the speed of chain transfer is much larger than the speed of chainpropagation, like this; The polymeric propagation process seems similarly to be on the chain transfer agents metal, to take place, the similar Aufbaureaktion reaction of result.This reaction process is called catalysis chainpropagation (Catalyzed chain growth, CCG) (J.Am.Chem.Soc., 2004,126,10701).1993, Ethyl company disclosed the patent of preparation chain alkyl aluminum compound, and in catalysis in olefine polymerization, (EP 0539876 to have effective chain transfer reaction between metallocene compound and the aluminum alkyls; EP 0574854), obtain the oligopolymer of Poisson's distribution.1994, Bochmann studied trimethylaluminium (Al (CH
3)
3) consumption to the influence of bridged combined metal compound for catalysis propylene polymerization, find Al (CH
3)
3/ Zr is 1: 1 o'clock, and polymerization activity is the highest, and polymericular weight is also maximum; Along with Al (CH
3)
3The increase of amount, polymerization activity and polymericular weight all diminish gradually, and molecular weight distribution narrow down gradually (Angew.Chem., Int.Ed., 1994,33,1634).Rytter has studied metallocene catalysis system Al (CH in ethylene polymerisation process
3)
3Effect.Along with Al (CH
3)
3The increase of concentration, the significant decrease of molecular weight of polymkeric substance, but to not obviously influence of polymerization activity, and the MWD of polymkeric substance can narrow down thereupon, is illustrated in high Al (CH
3)
3Under the concentration, chain transfer becomes the mode of main chain transfer to the reaction of aluminium, and under the lower concentration, then has chain transfer and β-H shift reaction dual mode (J.Polym.Sci., A, 2000,38,3106) to aluminum alkyls.Gibson has studied the situation of adding different aluminum alkylss in pyridine diimine iron/MAO catalystsystem, has proved that trimethylaluminium and triethyl aluminum all are effective chain transfer agents (J.Am.Chem.Soc., 2004,126,10701).
Gibson has also studied in pyridine diimine iron/MAO catalystsystem,, finds to compare with the general polymerization system as chain-transfer agent with zinc ethyl; The polymericular weight that has the polymerization system of zinc ethyl to obtain reduces greatly; Simultaneously, the polymkeric substance saturated chain is terminal sharply to be increased, when the zinc ethyl consumption is very big; It is very narrow that MWD also can become, and the polymkeric substance that obtains is Poisson's distribution, and (WO 03/014046; J.Am.Chem.Soc., 2004,126,10701).Recently; The researchist of Dow chemistry has proposed the notion of " chain shuttles back and forth "; In same polymerization system, use two kinds and have optionally catalyzer of different copolymer; With the zinc alkyl(s) is media, realizes the frequent exchange of the active growing chain on two kinds of active site, and (WO 2006/101595 can to obtain the polyolefine material of many blocks; CN 200680008452; Science, 2006,312,714).Sita uses single luxuriant hafnium-boron cpd catalyzing propone polymerization, adds zinc ethyl in the reaction system, and the molecular weight of polymkeric substance obviously diminishes, and it is very narrow that MWD becomes, similar living polymerization (J.Am.Chem.Soc.2008,130,442).Simultaneously, with this system catalyzed ethylene, 1-hexene, 1-octene and 1, the homopolymerization of 5-hexadiene and copolymerization also have similar phenomenon (Macromolecules 2008,41,7829).
Have patent to use zinc ethyl to handle silica-gel carrier, the specific indenoindole base of load metallocene then can obtain active higher supported olefin polymerization catalyst (CN 200480019367, WO2005/010064, US 6933353, EP 1641846).
Can find out from present document; General understanding is; The single-site catalysts that comprises metallocene catalyst has had advantages of high catalytic activity for catalysis in olefine polymerization, and for the active research report of the olefinic polymerization catalysis of further this type of raising catalyzer seldom.As the research to catalysis chainpropagation and chain transfer, dialkyl group zinc, particularly zinc ethyl have been used in quite a lot of research, and adopt consumption than higher zinc (with respect to transition-metal catalyst, such as WO 03/014046; J.Am.Chem.Soc., 2004,126,10701; J.Am.Chem.Soc., 2005,127; 9913, wherein the molar ratio of zinc and transition metal is greater than 500), its purpose is to study quick, the reversible exchange of polymerization growing chain between transition metal atoms and zinc atom; Thereby realize being similar to the reaction of propagation on zinc atom, reach the purpose of " accurate living polymerization ", and then obtain the material of functionalization.
In the present invention; Adopted the catalytic systems for polymerization of olefins of forming by transistion metal compound (like metallocene compound), alkylaluminoxane and dialkyl group zinc; Adopt lower zinc and the molar ratio of transition metal (being not more than 500), realized the active remarkable lifting of transition metal compound catalyst olefinic polymerization.
Summary of the invention
The purpose of this invention is to provide a kind of olefin Polymerization catalyst compositions, comprised transistion metal compound as catalyzer, as the organo-aluminium compound of promotor, and as the organic zinc compound of polymerization activity promotor.Compare with polymerization catalyst system in the past, polymerization catalyst system provided by the invention can obtain exceeding the catalyzed polymerization activity of several times.
A kind of catalyst composition that is used for olefinic polymerization of the present invention, it comprises
A) transistion metal compound;
B) alkylaluminoxane;
C) organic zinc compound;
Said transistion metal compound is the IVB family metallic compound that contains at least one cyclopentadienyl moiety or substituted cyclopentadienyl; One or more Wasserstoffatomss on the cyclopentadienyl moiety can be replaced by the aliphatic hydrocarbon group of 1～20 carbon atom or aromatic hydrocarbon group; Perhaps cyclopentadienyl moiety can condense with a phenyl ring and be indenyl; Perhaps cyclopentadienyl moiety and two phenyl ring condense and are fluorenyl, and the one or more Wasserstoffatomss on indenyl and the fluorenyl can be replaced by the aliphatic hydrocarbon group of 1～20 carbon atom or aromatic hydrocarbon group.
Said transition metal is preferably titanium, zirconium or the hafnium of IVB family.
In the transistion metal compound involved in the present invention, preferably contain the transistion metal compound of a cyclopentadienyl moiety or substituted cyclopentadienyl at least.The transistion metal compound that wherein contains two cyclopentadienyl moietys or substituted cyclopentadienyl is a metallocene compound.The transistion metal compound that wherein contains a cyclopentadienyl moiety or substituted cyclopentadienyl is the semi-metallocene compound, and used semi-metallocene compound also comprises one to the electronics part, like phenoxy among the present invention.
Alkylaluminoxane is a promotor in the catalyst composition of olefinic polymerization of the present invention, and its structure is:
Wherein R representes alkyl, is preferably methyl.N representes 4～30 integer, is preferably 10～30 integer.
The molar ratio scope of said transistion metal compound and alkylaluminoxane is 1: 50 to 1: 20000.
Also comprise a kind of organic zinc compound in the catalyst composition provided by the invention as polymerization activity promotor.Be preferably dialkyl group zinc, most preferably be zinc ethyl.
The consumption molar ratio of said transistion metal compound and organic zinc compound is 1: 1 to 1: 500.
Olefin Polymerization catalyst compositions provided by the present invention can be used for the homopolymerization and the copolymerization of alkene; Be particularly suitable for the copolymerization of terminal olefin of homopolymerization and ethene and one or more 3～50 carbon atoms of ethene, the preferred propylene of terminal olefin, 1-butylene, 1-amylene, 1-hexene, 1-octene, 4-methyl-1-pentene.
The catalyst composition transistion metal compound that the present invention is used for olefinic polymerization has adopted metallocene compound.
When using a kind of common bridged combined metal compound-ethylene bridge two indenyl zirconium dichlorides as ethylene rolymerization catalyst, the adding of a small amount of zinc ethyl has obviously improved polymerization activity (seeing table 1).Do not have the polymerization system of zinc ethyl, showed 2.28 * 10
6The activity of g-Polymer/mol-Zr/hr, and after adding a small amount of zinc ethyl, the active raising that all has 3 to 4 times.Along with the increase of zinc ethyl consumption, polymericular weight obviously descends, and at the zinc ethyl consumption seldom the time, this decline and not obvious (seeing table 1 and Fig. 1).Simultaneously, the adding of zinc ethyl narrows down molecular weight distribution.
Use ethylene bridge two indenyl zirconium dichlorides to be the catalyzer that ethene/the 1-hervene copolymer closes, also observed the obvious lifting (seeing table 2 and Fig. 2) of polymerization activity.Identical with ethylene homo, the adding of zinc ethyl makes the molecular weight and molecular weight (seeing table 2 and Fig. 3) of polymkeric substance.With the synizesis ratio that does not add zinc ethyl, in the amount Zn/Zr that uses zinc ethyl was 50 polymerization, polymerization activity was doubled, and polymericular weight has reduced by 1/4th.Under the condition of constant Zn/Zr ratio, reduce Al/Zr than the time, polymerization activity can descend.When not having MAO in the system, system does not have activity (seeing table 2 and Fig. 4) to olefinic polymerization.
The present invention also uses mono-metallocene compound-pentamethyl-cyclopentadienyl moiety-2, and 6-di-isopropyl phenoxy titanium dichloride is a catalyzer, has carried out the investigation of vinyl polymerization, finds that the adding of zinc ethyl can significantly promote polymerization activity (seeing table 3) equally.
Description of drawings
Fig. 1 is for being the polymericular weight GPC curve that the ethylene homo of catalyzer closes with ethylene bridge two indenyl zirconium dichlorides
Fig. 2 is for being the polymerization activity and the polymericular weight that ethene/the 1-hervene copolymer closes of catalyzer with ethylene bridge two indenyl zirconium dichlorides
Fig. 3 is for being the polymericular weight GPC curve that the ethene/1-hervene copolymer of catalyzer closes with ethylene bridge two indenyl zirconium dichlorides
Fig. 4 is for being the influence (Zn/Zr=50) of the Al/Zr ratio that ethene/the 1-hervene copolymer closes of catalyzer with ethylene bridge two indenyl zirconium dichlorides
Embodiment
Below through embodiment the present invention is further described, but should not be construed as qualification of the present invention.
Embodiment 1-4 is the ethylene homo of catalyzer with ethylene bridge two indenyl zirconium dichlorides
Fully the 250mL glass polymerization bottle of oven dry vacuumizes nitrogen wash, three times repeatedly.Vacuumize, solenoid control charges into ethene, under the design temperature, adds toluene, MAO toluene solution, zinc ethyl toluene solution, the catalyzer toluene solution of set amount successively, picks up counting.Behind the polymerization setting-up time, close ethene, pour reaction solution into beaker, add acidifying ethanol, stir more than 6 hours, filter and obtain polymkeric substance, vacuum-drying 24 hours, the calculated activity of weighing.Concrete reaction conditions and result are listed in the table 1.
Embodiment 5-11 is that the ethene/1-hervene copolymer of catalyzer closes with ethylene bridge two indenyl zirconium dichlorides
Fully the 250mL glass polymerization bottle of oven dry vacuumizes nitrogen wash, three times repeatedly.Vacuumize, solenoid control charges into ethene, under the design temperature, adds toluene, 1-hexene, MAO toluene solution, zinc ethyl toluene solution, the catalyzer toluene solution of set amount successively, picks up counting.Behind the polymerization setting-up time, close ethene, pour reaction solution into beaker, add acidifying ethanol, stir more than 6 hours, filter and obtain polymkeric substance, vacuum-drying 24 hours, the calculated activity of weighing.Concrete reaction conditions and result are listed in the table 2.
Embodiment 12 is with pentamethyl-cyclopentadienyl moiety-2, and 6-di-isopropyl phenoxy titanium dichloride is that the ethylene homo of catalyzer closes
Fully the 250mL glass polymerization bottle of oven dry vacuumizes nitrogen wash, three times repeatedly.Vacuumize, solenoid control charges into ethene, under the design temperature, adds toluene, MAO toluene solution, zinc ethyl toluene solution, the catalyzer toluene solution of set amount successively, picks up counting.Behind the polymerization setting-up time, close ethene, pour reaction solution into beaker, add acidifying ethanol, stir more than 6 hours, filter and obtain polymkeric substance, vacuum-drying 24 hours, the calculated activity of weighing.Concrete reaction conditions and result are listed in the table 3.
Comparative Examples 1 is the ethylene homo of catalyzer with ethylene bridge two indenyl zirconium dichlorides
Fully the 250mL glass polymerization bottle of oven dry vacuumizes nitrogen wash, three times repeatedly.Vacuumize, solenoid control charges into ethene, under the design temperature, adds toluene, MAO toluene solution, the catalyzer toluene solution of set amount successively, picks up counting.Behind the polymerization setting-up time, close ethene, pour reaction solution into beaker, add acidifying ethanol, stir more than 6 hours, filter and obtain polymkeric substance, vacuum-drying 24 hours, the calculated activity of weighing.Concrete reaction conditions and result are listed in the table 1.
Comparative Examples 2 is that the ethene/1-hervene copolymer of catalyzer closes with ethylene bridge two indenyl zirconium dichlorides
Fully the 250mL glass polymerization bottle of oven dry vacuumizes nitrogen wash, three times repeatedly.Vacuumize, solenoid control charges into ethene, under the design temperature, adds toluene, 1-hexene, MAO toluene solution, the catalyzer toluene solution of set amount successively, picks up counting.Behind the polymerization setting-up time, close ethene, pour reaction solution into beaker, add acidifying ethanol, stir more than 6 hours, filter and obtain polymkeric substance, vacuum-drying 24 hours, the calculated activity of weighing.Concrete reaction conditions and result are listed in the table 2.
Comparative Examples 3 is with pentamethyl-cyclopentadienyl moiety-2, and 6-di-isopropyl phenoxy titanium dichloride is that the ethylene homo of catalyzer closes
Fully the 250mL glass polymerization bottle of oven dry vacuumizes nitrogen wash, three times repeatedly.Vacuumize, solenoid control charges into ethene, under the design temperature, adds toluene, MAO toluene solution, the catalyzer toluene solution of set amount successively, picks up counting.Behind the polymerization setting-up time, close ethene, pour reaction solution into beaker, add acidifying ethanol, stir more than 6 hours, filter and obtain polymkeric substance, vacuum-drying 24 hours, the calculated activity of weighing.Concrete reaction conditions and result are listed in the table 3.
Table 1 is that the ethylene homo of catalyzer closes with ethylene bridge two indenyl zirconium dichlorides
| Zn/Zr | Polymkeric substance (g) | Active a | M n b | M w b | M w/M n b | |
| Comparative Examples 1 | 0 | ?0.38 | 2.28 | 55762 | 244963 | 4.39 |
| |
10 | ?1.48 | 8.88 | 55392 | 279323 | 5.01 |
| |
25 | ?1.22 | 7.32 | 34001 | 124982 | 3.68 |
| |
100 | ?1.82 | 10.92 | 15183 | 44147 | 2.91 |
| |
200 | ?1.32 | 7.92 | 8492 | 24886 | 2.93 |
System 30mL, solvent are toluene, normal pressure ethene, and polymerization time 20 minutes, 70 ℃ of polymerization temperatures, catalyst levels are 0.5 μ mol, Al/Zr molar ratio 3000.
A: active 10
6G-Polymer/mol-Zr/hr.
The b:GPC data.
Table 2 is that the ethene/1-hervene copolymer of catalyzer closes with ethylene bridge two indenyl zirconium dichlorides
System 30mL, solvent are toluene, normal pressure ethene, and polymerization time 20 minutes, 70 ℃ of polymerization temperatures, catalyst levels are 0.5 μ mol, 1-hexene consumption is 1.5mL.
A: active 10
6G-Polymer/mol-Zr/hr.
The b:GPC data.
Table 3 is with pentamethyl-cyclopentadienyl moiety-2, and 6-di-isopropyl phenoxy titanium dichloride is the ethylene homo of catalyzer
| Zn/Ti | Polymkeric substance (g) | Active a | M n b | M w b | M w/M n b | |
| Comparative Examples 3 | 0 | ?0.15 | 0.90 | 52193 | 190908 | 3.66 |
| Embodiment 12 | 25 | ?0.24 | 1.44 | 14345 | 31445 | 2.19 |
System 30mL, solvent are toluene, normal pressure ethene, and polymerization time 20 minutes, 30 ℃ of polymerization temperatures, catalyst levels are 5 μ mol, Al/Zr molar ratio 1000.
A: active 10
5G-Polymer/mol-Zr/hr.
The b:GPC data.
Claims (11)
1. a catalyst composition that is used for olefinic polymerization is characterized in that it comprises
A) transistion metal compound;
B) alkylaluminoxane;
C) organic zinc compound;
Said transistion metal compound is the IVB family metallic compound that contains at least one cyclopentadienyl moiety or substituted cyclopentadienyl; One or more Wasserstoffatomss on the cyclopentadiene are randomly replaced by the aliphatic group of 1～20 carbon atom or aryl radical; Perhaps cyclopentadienyl moiety randomly condenses with a phenyl ring and is indenyl; Perhaps cyclopentadienyl moiety and two phenyl ring condense and are fluorenyl, and the one or more Wasserstoffatomss on indenyl and the fluorenyl are randomly replaced by the aliphatic group of 1～20 carbon atom or aryl radical;
The consumption molar ratio of described transistion metal compound and organic zinc compound is 1: 1 to 1: 500.
2. the catalyst composition of olefinic polymerization according to claim 1 is characterized in that, described transistion metal compound is the IVB family metallocene compound that contains two cyclopentadienyl moietys or substituted cyclopentadienyl.
3. the catalyst composition of olefinic polymerization according to claim 1 is characterized in that, described transistion metal compound is ethylene bridge two indenyl zirconium dichlorides.
4. according to the catalyst composition of the olefinic polymerization of the said mistake of claim 1, it is characterized in that described transistion metal compound is to contain a cyclopentadienyl moiety or substituted cyclopentadienyl and an IVB family mono-metallocene compound of giving the electronics part.
5. the catalyst composition of olefinic polymerization according to claim 1 is characterized in that, described transistion metal compound is a pentamethyl-cyclopentadienyl moiety-2,6-di-isopropyl phenoxy titanium dichloride.
6. according to the catalyst composition of the olefinic polymerization of the said mistake of claim 1, it is characterized in that said alkylaluminoxane is a MAO.
7. according to the catalyst composition of the olefinic polymerization of the said mistake of claim 1, it is characterized in that described organic zinc compound is a dialkyl group zinc.
8. according to the catalyst composition of the olefinic polymerization of the said mistake of claim 1, it is characterized in that described organic zinc compound is a zinc ethyl.
9. the application of the catalyst composition of the described olefinic polymerization of one of claim 1～8 in olefinic polyreaction.
10. the application of the catalyst composition of olefinic polymerization according to claim 9 in olefinic polyreaction is characterized in that, described olefinic polyreaction is the equal polymerization of ethene.
11. the application of the catalyst composition of olefinic polymerization according to claim 9 in olefinic polyreaction; It is characterized in that; Described olefinic polyreaction is that ethene and alpha-olefin copolymer close, and terminal olefin is propylene, 1-butylene, 1-amylene, 1-hexene, 1-octene, 4-methyl-1-pentene.
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|---|---|---|---|---|
| CN104031188A (en) * | 2014-06-06 | 2014-09-10 | 浙江大学 | Method for continuously controlling molecular weight of metallocene polyethylene by utilizing aluminum alkyl |
| CN109422828A (en) * | 2017-09-05 | 2019-03-05 | 中国石油化工股份有限公司 | For olefinic polymerization catalyst system and prepare the catalyst system and method and low molecular weight polyethylene of low molecular weight polyethylene |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050090383A1 (en) * | 2001-10-12 | 2005-04-28 | Thiele Sven K. | Metal complex compositions and their use as catalysts to produce polydienes |
| CN1922220A (en) * | 2004-01-09 | 2007-02-28 | 切弗朗菲利浦化学公司 | Catalyst compositions and polyolefins for extrusion coating applications |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US20050090383A1 (en) * | 2001-10-12 | 2005-04-28 | Thiele Sven K. | Metal complex compositions and their use as catalysts to produce polydienes |
| CN1922220A (en) * | 2004-01-09 | 2007-02-28 | 切弗朗菲利浦化学公司 | Catalyst compositions and polyolefins for extrusion coating applications |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104031188A (en) * | 2014-06-06 | 2014-09-10 | 浙江大学 | Method for continuously controlling molecular weight of metallocene polyethylene by utilizing aluminum alkyl |
| CN109422828A (en) * | 2017-09-05 | 2019-03-05 | 中国石油化工股份有限公司 | For olefinic polymerization catalyst system and prepare the catalyst system and method and low molecular weight polyethylene of low molecular weight polyethylene |
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