CN105622800A - Catalyst component for olefin polymerization, and catalyst system thereof - Google Patents
Catalyst component for olefin polymerization, and catalyst system thereof Download PDFInfo
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Abstract
The present invention provides a catalyst for an olefin polymerization reaction. The catalyst contains the reaction product of the following components: (1) a titanium-containing solid catalyst component, wherein a titanium compound represented by a general formula (II) Ti(OR[w])[4-k]X[k] and at least a carboxylic acid ester compound are loaded on magnesium chloride alcohol compound particles represented by a general formula (I) MgX2.m(R<'>OH).nE.qH2O so as to obtain the catalyst component; (2) an alkyl aluminum compound; (3) ether ester; and (4) hydrocarbonyl dioxyl silane. According to the present invention, in the case of the substantially-unchanged catalyst polymerization activity and the substantially-unchanged isotactic index of the polymer, the melt index can be changed by regulating the ratio of the electron donor.
Description
Technical field
The present invention relates to a kind of catalyst for olefinic polyreaction, more specifically, relate to a kind of based on titanium compound, and the catalytic systems for polymerization of olefins using carboxylate to be the spherical catalyst components of internal electron donor, promoter and composite external electron donor compositions ether diester compound and alkyl two hydrocarbyloxysilane.
Background technology
Catalyst containing the titanium compound being loaded in magnesium halide in active and electron donor compound is well known in the prior art. All being polymerized for alpha-olefin or catalyst system in copolymerization is generally made up of three parts, they are: the external donor compound added when (1) major catalyst (solid catalyst), (2) promoter (being generally alkyl aluminum compounds) and (3) polymerization.
In major catalyst, transition metal is generally the compound of titanium, zirconium or vanadium, and preferred titanium compound, and in practice it has been found that titanium is a kind of particularly excellent transition metal. These compounds typically have halogenide or oxyhalide or alkoxide, alcoholates, halogenohydrin salt. Transistion metal compound can represent by below formula:
(R'O)nR"mMXp-m-n
Here, M is the transition metal of 4-8 subgroup, it is preferable that Ti, Zr or V, R' and R, and " be good for the identical or different organic group of composition for the master of 1-20 carbon, M is transition metal, and X is halogen, it is preferred that for chlorine. R' and R is " preferably and be generally simple alkyl, it is preferable that alkyl. P is the oxidation state of metal M, and it is the integer between 0-p that p is generally 4 or 5, n and m. Suitable titanium compound includes the halogenide, particularly TiBr of titanium tetramethoxide, purity titanium tetraethoxide, four titanium propanolates, four titanium butoxide and similar oxide, wherein 1-3 the alcohol oxygen base halogenohydrin salt by halogen, the particularly corresponding titanium of chlorine replacement and titanium4And TiC14. Compound the most frequently used in these compounds is TiCl4. It is obvious that two or more transistion metal compounds can be used by different form of mixtures.
Promoter is generally made up of the organic compound of the main group metal of 1-3. Although frequently with the compound of aluminum, but also having adopted boron, zinc and alkali-metal compound. The compound of aluminum can represent with such as following formula:
RnAlX3-n
Here, R is organic alkyl preferably C1-C20Alkyl, X is halogen, and n is the integer from 1 to 3. Different promoters can be used by various form of mixtures simultaneously. The organic compound being typically used as promoter is trialkylaluminium, it is preferable that triethyl aluminum or triisobutyl aluminium.
It addition, catalyst system also includes the component improving and improving catalyst performance. Major catalyst can select type and/or activity with the so-called internal electron donor compound complexation being provided that electronics to improve catalyst system solid. The exoelectron compound donator of type can be selected improve the final performance of catalyst further with being intended to improve end product solid in the course of the polymerization process.
Using one or more External Electron Donor Compound in polymerization process is that those skilled in the art are in common knowledge to control the stereoregularity of polymer and form. External electron donor, except the stereoregularity affecting polymer, also tends to have influence on to some extent the performance of catalyst other side. Although known have perhaps multiple compounds can as external electron donor, but specific catalyst uses different external donor compounds may produce different polymer performances. Select the suitable external electron donor can be compatible especially with specific catalyst, that is, one group find a kind of applicable external electron donor can be significantly improved the performance of some aspect of polymeric articles, consequently found that can make the external electron donor that polymer has outstanding properties in some aspects be very favorable for special catalyst.
US Patent No. 4544717 is pointed out, by being added to electron compound (i.e. internal electron donor compound) in the solid constituent containing titanium compound, it is possible to improve the stereoselectivity of catalyst. European patent EP 0045977 discloses a kind of catalyst with significantly high activity and stereoselectivity, and the solid constituent of described catalyst includes carrying halogenated titanium (TiCl4) and the magnesium halide of activated form of electron donor compound selected from phthalate. Promoter used is the alkyl aluminum compound of the silicon compound (i.e. external donor compound) wherein adding and at least containing Si OR key (R represents alkyl).
The present inventor is surprised to find that in research work, ether ester type compound is added when olefinic polymerization and alkyl two hydrocarbyloxysilane is composite as external donor compound at the solid spherical catalytic component being internal electron donor using carboxylate compound, when the polymerization activity of catalyst and the isotactic index of polymer are basically unchanged, its melt index can be changed by the proportioning of adjustment external electron donor.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of catalyst system for olefinic polyreaction, use this catalyst system, when the polymerization activity of catalyst and the isotactic index of polymer are basically unchanged, its melt index can be changed by the proportioning of adjustment external electron donor.
A kind of catalyst for olefinic polyreaction of the present invention, comprises the product of following component: (1) a kind of solids containing titanium catalytic component, this catalytic component is at logical formula I MgX2.m(R��OH).nE.qH2Magnesium chloride alcohol adduct granule shown in O is loaded with logical formula II Ti (ORw)4-kXkShown titanium compound and at least one carboxylate compound; (2) alkyl aluminum compound; (3) ether ester; (4) alkyl two hydrocarbyloxysilane;
The formula of described ether ester isWherein R1��R2For the alkyl of carbon number 1��20 straight or branched, cycloalkyl, aralkyl, alkaryl, fused ring aryl, alkylene, R1��R2Optionally identical or different; R3��R4For the alkyl of carbon number 1��20 straight or branched, cycloalkyl; R5For the alkyl of carbon number 1��20 straight or branched, cycloalkyl, aralkyl, alkaryl, fused ring aryl;
The formula of described alkyl two hydrocarbyloxysilane isWherein R1��R2��R3��R4For the alkyl or cycloalkyl of carbon number 1��20 straight or branched, R1��R2Optionally identical or different; R3��R4Optionally identical or different;
Described carboxylate compound is unitary or polyhydric aliphatic race carboxylate, aromatic carboxylic acid esters's compound.
Specifically, described ether ester is selected from methoxymethylene dimethyl malenate, ethoxy methylene diethyl malonate, ethoxymeyhylene dimethyl malenate, methoxymethylene diethyl malonate, 2-methoxymethylene-1,4-dimethyl succinate, 2-ethoxymeyhylene-1,4-diethyl succinate, 2-ethoxymeyhylene-1,4-dimethyl succinate, 2-methoxymethylene-1,4-diethyl succinate, 3-methoxymethylene-1,4-dimethyl succinate, 3-ethoxymeyhylene-1,4-diethyl succinate, 3-ethoxymeyhylene-1,4-dimethyl succinate, 3-methoxymethylene-1,4-diethyl succinate, 2-methoxymethylene-1,5-Glutaric Acid Dimethyl ester, 2-ethoxymeyhylene-1,5-ethyl glutarate, 2-ethoxymeyhylene-1,5-Glutaric Acid Dimethyl ester, 2-methoxymethylene-1,5-ethyl glutarate, 3-methoxymethylene-1,5-Glutaric Acid Dimethyl ester, 3-ethoxymeyhylene-1,5-ethyl glutarate, 3-ethoxymeyhylene-1,5-Glutaric Acid Dimethyl ester, 3-methoxymethylene-1,5-ethyl glutarate, 4-methoxymethylene-1,5-Glutaric Acid Dimethyl ester, 4-ethoxymeyhylene-1,5-ethyl glutarate, 4-ethoxymeyhylene-1,5-Glutaric Acid Dimethyl ester, 4-methoxymethylene-1,5-ethyl glutarate, methoxymethylene malonic acid bicyclo-pentyl ester, ethoxymeyhylene malonic acid bicyclo-pentyl ester, ethoxymeyhylene malonic acid dicyclohexyl maleate, methoxymethylene malonic acid dicyclohexyl maleate, methoxymethylene malonic acid dibenzoate, ethoxymeyhylene malonic acid dibenzoate, phenyoxymethylene dimethyl malenate, phenyoxymethylene diethyl malonate, ethyleneoxy methylene dimethyl malenate, ethyleneoxy diethyl methylenemalonate, allyloxy methylene dimethyl malenate, allyloxy diethyl methylenemalonate, 3-methoxymethylene dimethyl phthalate, 3-ethoxymeyhylene diethyl phthalate, 3-ethoxymeyhylene dimethyl phthalate, 3-methoxymethylene diethyl phthalate, 4-methoxymethylene dimethyl phthalate, 4-ethoxymeyhylene diethyl phthalate, 4-ethoxymeyhylene dimethyl phthalate, 4-methoxymethylene diethyl phthalate, 5-methoxymethylene dimethyl phthalate, 5-ethoxymeyhylene diethyl phthalate, 5-ethoxymeyhylene dimethyl phthalate, 5-methoxymethylene diethyl phthalate, 2-methoxymethylene dimethyl terephthalate (DMT), 2-ethoxymeyhylene diethyl terephthalate, 2-ethoxymeyhylene dimethyl terephthalate (DMT), 2-methoxymethylene diethyl terephthalate, 3-methoxymethylene dimethyl terephthalate (DMT), 3-ethoxymeyhylene diethyl terephthalate, 3-ethoxymeyhylene dimethyl terephthalate (DMT), 3-methoxymethylene diethyl terephthalate.
Described alkyl two hydrocarbyloxysilane is selected from Cyclohexylmethyldimethoxysilane, diisopropyl dimethoxy silane, second, isobutyl dimethoxy silane, Dicyclohexyldimethoxysilane, dicyclopentyl dimethoxyl silane, methylcyclohexyl diethoxy silane, diisopropyldiethoxysilane, diisobutyl diethoxy silane, dicyclohexyl diethoxy silane, bicyclopentyl diethoxy silane, methylcyclohexyl dipropoxy silane, diisopropyl dipropoxy silane, diisobutyl dipropoxy silane, dicyclohexyl dipropoxy silane, bicyclopentyl dipropoxy silane, methylcyclohexyl dibutoxy silane, diisopropyl dibutoxy silane, diisobutyl dibutoxy silane, dicyclohexyl dibutoxy silane, bicyclopentyl dibutoxy silane etc., one in preferred Cyclohexylmethyldimethoxysilane, dicyclopentyl dimethoxyl silane, diisopropyl dimethoxy silane, second, isobutyl dimethoxy silane, Dicyclohexyldimethoxysilane.
Described alkyl two hydrocarbyloxysilane can adopt conventional synthetic method to be prepared at laboratory, it is possible to is buying on the market by general chemistry product purchasing way.
The consumption of described compound external donor compound ether ester is every mole aluminium compound 0.001��1.0 mole; The consumption of described alkyl dialkoxy silicane is every mole aluminium compound 0.001��1.0 mole; The two can add after mixing, it is also possible to is separately added into; The mol ratio of ether ester and alkyl dialkoxy silicane is 1:100��100:1.
Described carboxylate is unitary or polyhydric aliphatic race carboxylate, aromatic carboxylic acid esters's compound. such as: benzoate, phthalic acid ester, malonate, succinate, glutarate etc. concrete such as ethyl benzoate, diethyl phthalate, diisobutyl phthalate, n-butyl phthalate, diisooctyl phthalate, dinoctyl phthalate, diethyl malonate, malonic acid di-tert-butyl ester, 2, 3-diisopropyl diethyl succinate, 2, 3-diisopropyl di-iso-octyl succinate, 2, 3-diisopropyl dibutyl succinate, 2, 3-diisopropyl succinic acid dimethyl esters, 2, 2-dimethyl succinate diisobutyl ester, 2-Ethyl-2-Methyl di-iso-octyl succinate, 2-Ethyl-2-Methyl diethyl succinate, diethylene adipate, dibutyl adipate, ethyl sebacate, dibutyl sebacate, diethyl maleate, maleic acid n-butyl, naphthalene dicarboxylic acids diethylester, naphthalene dicarboxylic acids dibutyl ester, triethyl trimellitate, tributyl trimellitate, benzene-1,2,3-tricarboxylic acid triethyl, benzene-1,2,3-tricarboxylic acid tributyl, PMA tetra-ethyl ester, PMA four butyl ester etc.
Described titanium compound can be selected for a kind of in titanium tetrachloride, titanium tetrabromide, titanium tetra iodide, four titanium butoxide, purity titanium tetraethoxide, a chlorine triethoxy titanium, dichlorodiethyl oxygen base titanium, trichlorine one ethanolato-titanium, titanous chloride. or their mixture, it is preferable that titanium tetrachloride.
Component (1) catalytic component of the present invention can be prepared according to the preparation method of solid catalyst disclosed in Chinese patent CN93102795.0. Magnesium halide alcohol adduct formula of the present invention is MgX2.m(R��OH).nE.qH2O, it is preferable that the alcohol cpd of magnesium chloride is disclosed in Chinese patent CN1091748, CN00109216.2 and CN101050245, and related content disclosed in it is fully incorporated the present invention as reference.
The concrete preparation method of magnesium halide alcohol adduct carrier is anhydrous magnesium halide and low-carbon alcohols to be mixed, temperature reaction generates magnesium halide alcohol adduct melt, reaction temperature is 90��140 DEG C, disperse medium is put into after high shear forces in the inert media of cooling, form spherical magnesium halide alcohol polymer granule, scrubbed, obtain ball type carrier after drying. High shear forces can adopt the method for routine to obtain, such as high-speed mixing method (such as CN00109216.2), nebulization (such as US6020279) and high-gravity rotating bed (such as CN1580136A) and mulser method (CN1463990A) etc. Dispersant system adopts hydro carbons atent solvent, such as kerosene, white oil, silicone oil, paraffin oil, vaseline wet goods. Cooling medium is selected from pentane, hexane, heptane, petroleum ether, raffinates oil.
The synthetic method of instant component (1) catalytic component is to be suspended in by magnesium halide alcohol adduct obtained above in the titanium compound of pre-cooling or the mixture of titanium compound and atent solvent, atent solvent is hexane, heptane, octane, decane, toluene etc. such as, temperature is-30 DEG C��0 DEG C, it is preferable that-20 DEG C��-10 DEG C; Then said mixture is heated to 80 DEG C��130 DEG C, temperature-rise period adds electron donor compound. Then add titanium compound and process one or many. Finally, repeatedly wash with atent solvent and obtain ingredient of solid catalyst.
Component (2) alkyl aluminum compound of the present invention, its formula is AlR " 'nX3-n, R " ' for C that is identical or that differ1-8Alkyl, 1��n��3, it is possible to select one or more alkyl aluminum mixing use, it is preferable that triethyl aluminum, triisobutyl aluminium, three n-butylaluminum, tri-n-hexyl aluminum, chlorination alkyl aluminum, Al (n-C6H13)3��Al(n-C8H17)3��AlEt2Cl etc., generally use abovementioned alkyl aluminium compound with Al/Ti mol ratio for 1��1000.
Component (2) alkyl aluminum compound can contact with component (1) catalytic component individually or as the mixture of two constituents with component (3) external donor compound.
Above-mentioned catalyst system is suitable for alkene CH2=CHRy, wherein RyIt is hydrogen or the alkyl or aryl of 1��6 carbon) and the polyreaction of mixture containing (if necessary) a small amount of alkadienes.
The polymerization of alkene carries out according to known methods, in liquid monomer or monomer in the liquid phase of the solution in atent solvent, or in the gas phase, or is operated by the polymerization mix technique in liquid phase. Polymerization temperature is generally 0 DEG C��150 DEG C, it is preferred to 60 DEG C��100 DEG C. Polymerization pressure is normal pressure or higher.
The invention provides a kind of catalyst system for olefinic polyreaction, use this catalyst system, when the polymerization activity of catalyst and the isotactic index of polymer are basically unchanged, its melt index can be changed by the proportioning of adjustment external electron donor.
Detailed description of the invention
Following example are that present invention citing specifically is described, but the invention is not limited in these embodiments.
Method of testing
1, melt index: measure according to ASTMD1238-99.
2, polymer isotacticity: adopt heptane extraction process to measure (heptane boiling extracting 6 hours), namely the 2g polymer samples dried is taken, it is placed in extractor with boiling heptane extracting 6 hours, afterwards, residue is dried to constant weight, resulting polymers weight (g) with 2 ratio be isotacticity.
Embodiment 1
1A, solids containing titanium catalytic component A preparation
In the 300ml being sufficiently displaced from through the high pure nitrogen glass reaction bottle with stirring, add the titanium tetrachloride of 100ml, it is cooled to-20 DEG C, add spherical magnesium chloride alcohol adduct (preparation method is referring to Chinese patent CN1330086A), it is to slowly warm up to 110 DEG C stage by stage, temperature-rise period adds dibutyl phthalate 3.9mmol, after 110 DEG C of constant temperature 0.5h, elimination liquid, add titanium tetrachloride and process secondary, then wash five times with hexane, after vacuum drying, obtain solids containing titanium catalytic component A (major catalyst).
1B, propylene polymerization
In 5 liters of autoclaves; stream of nitrogen gas is adopted to purge 1 hour at 70 DEG C; then with gas-phase propene, polymeric kettle is replaced 3 times, introduce the hexane solution (concentration of triethyl aluminum is 0.5mmol/ml) of 5ml triethyl aluminum, the hexane solution (concentration of external electron donor is 0.1mmol/ml) of compound external electron donor, 8ml anhydrous hexane and 8��12mg solids containing titanium catalytic component A (major catalyst) under nitrogen protection. Close autoclave, introduce the liquid propene of appropriate hydrogen and 1.0��1.2Kg; Under agitation quickly interior temperature is risen to 70 DEG C. At 70 DEG C, polyreaction is after 1 hour, stops stirring, removes unpolymerized propylene monomer, collected polymer, vacuum drying 2 hours at 70 DEG C, calculated activity of weighing (AC).
Embodiment 2��8
By the solid catalyst of preparation in the 1A of embodiment 1 according to the method for propylene polymerization in the 1B of embodiment 1, add hydrogen amount carry out polymerization result by different external electron donor additions and difference respectively. The hexane solution that compound external electron donor is ethoxy methylene diethyl malonate and Cyclohexylmethyldimethoxysilane added during polymerization, polymerization and test result are in Table 1.
Embodiment 9��13
By the solid catalyst of preparation in the 1A of embodiment 1 according to the method for propylene polymerization in the 1B of embodiment 1, add hydrogen amount carry out polymerization result by different external electron donor additions and difference respectively. The hexane solution that compound external electron donor is methoxymethylene dimethyl malenate and Cyclohexylmethyldimethoxysilane added during polymerization, polymerization and test result are in Table 1.
Comparative example 1��2
The external electron donor of addition, with embodiment 2��11, is simply changed into the hexane solution (concentration of CHMMS is 0.1mmol/ml) of 1ml Cyclohexyl Methyl Dimethoxysilane (CHMMS) by polymerization, and polymerization and test result are in Table 1.
Comparative example 3
The external electron donor of addition, with embodiment 2��11, is simply changed into the hexane solution (concentration of EMME is 0.1mmol/ml) of 1ml ethoxy methylene diethyl malonate (EMME) by polymerization, and polymerization and test result are in Table 1.
Table 1 experimental result
Wherein EMME: ethoxy methylene diethyl malonate, DMMMM: methoxymethylene dimethyl malenate, C-donor: Cyclohexylmethyldimethoxysilane
As it can be seen from table 1 when the polymerization activity of catalyst and the isotactic index of polymer are basically unchanged, its melt index can be changed by the proportioning of adjustment external electron donor.
Claims (9)
1. for a catalyst for olefinic polyreaction, including the product of following components:
(1) a kind of solids containing titanium catalytic component, this catalytic component is at logical formula I MgX2.m(R��OH).nE.qH2Magnesium chloride alcohol adduct granule shown in O is loaded with logical formula II Ti (ORw)4-kXkShown titanium compound and at least one carboxylate compound;
(2) alkyl aluminum compound;
(3) ether ester;
(4) alkyl two hydrocarbyloxysilane;
The formula of described ether ester isWherein R1��R2For the alkyl of carbon number 1��20 straight or branched, cycloalkyl, aralkyl, alkaryl, fused ring aryl, alkylene, R1��R2Optionally identical or different; R3��R4For the alkyl of carbon number 1��20 straight or branched, cycloalkyl; R5For the alkyl of carbon number 1��20 straight or branched, cycloalkyl, aralkyl, alkaryl, fused ring aryl;
The formula of described alkyl two hydrocarbyloxysilane isWherein R1��R2��R3��R4For the alkyl or cycloalkyl of carbon number 1��20 straight or branched, R1��R2Optionally identical or different; R3��R4Optionally identical or different;
Described carboxylate compound is unitary or polyhydric aliphatic race carboxylate, aromatic carboxylic acid esters's compound.
2. a kind of catalyst for olefinic polyreaction according to claim 1, it is characterized in that in every mole aluminium compound, the consumption of ether ester is 0.001��1.0 mole, the consumption of alkyl dialkoxy silicane is 0.001��1.0 mole, and the mol ratio of ether ester and alkyl dialkoxy silicane is 1:100��100:1; Al/Ti mol ratio is 1��1000.
3. a kind of catalyst for olefinic polyreaction according to claim 1, it is characterised in that described ether ester is selected from ethoxy methylene diethyl malonate and methoxymethylene dimethyl malenate.
4. a kind of catalyst for olefinic polyreaction according to claim 1, it is characterised in that described alkyl dialkoxy silicane one in Cyclohexylmethyldimethoxysilane, dicyclopentyl dimethoxyl silane, diisopropyl dimethoxy silane, second, isobutyl dimethoxy silane, Dicyclohexyldimethoxysilane.
5. a kind of catalyst for olefinic polyreaction according to claim 1, it is characterised in that described carboxylate compound is selected from benzoate, phthalic acid ester, malonate, succinate, glutarate.
6. a kind of catalyst for olefinic polyreaction according to claim 1, it is characterised in that described carboxylate compound selected from ethyl benzoate, diethyl phthalate, diisobutyl phthalate, n-butyl phthalate, diisooctyl phthalate, dinoctyl phthalate, diethyl malonate, malonic acid di-tert-butyl ester, 2,3-diisopropyl diethyl succinates, 2,3-diisopropyl di-iso-octyl succinates, 2,3-diisopropyl dibutyl succinates, 2,3-diisopropyl succinic acid dimethyl esters, 2,2-dimethyl succinate diisobutyl esters, 2-Ethyl-2-Methyl di-iso-octyl succinate, 2-Ethyl-2-Methyl diethyl succinate, diethylene adipate, dibutyl adipate, ethyl sebacate, dibutyl sebacate, diethyl maleate, maleic acid n-butyl, naphthalene dicarboxylic acids diethylester, naphthalene dicarboxylic acids dibutyl ester, triethyl trimellitate, tributyl trimellitate, benzene-1,2,3-tricarboxylic acid triethyl, benzene-1,2,3-tricarboxylic acid tributyl, PMA tetra-ethyl ester, at least one in PMA four butyl ester.
7. a kind of catalyst for olefinic polyreaction according to claim 1, it is characterised in that described titanium compound is selected from the one in titanium tetrachloride, titanium tetrabromide, titanium tetra iodide, four titanium butoxide, purity titanium tetraethoxide, a chlorine triethoxy titanium, dichlorodiethyl oxygen base titanium, trichlorine one ethanolato-titanium, titanous chloride. or its mixture.
8. a kind of catalyst for olefinic polyreaction according to claim 1, it is characterised in that the formula of described alkyl aluminum compound is AlR " 'nX3-n, R " ' for C that is identical or that differ1-8Alkyl, 1��n��3.
9. a kind of catalyst for olefinic polyreaction according to claim 1, it is characterised in that described alkyl aluminum compound is selected from triethyl aluminum, triisobutyl aluminium, three n-butylaluminum, tri-n-hexyl aluminum, chlorination alkyl aluminum, Al (n-C6H13)3��Al(n-C8H17)3��AlEt2At least one in Cl.
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| US20050288460A1 (en) * | 2004-06-28 | 2005-12-29 | Zhidong Zhu | High activity and good hydrogen response Ziegler-Natta polyethylene catalyst |
| CN103304691A (en) * | 2012-03-08 | 2013-09-18 | 中国石油化工股份有限公司 | Catalyst system used for alkene polymerization |
| CN103819586A (en) * | 2012-11-16 | 2014-05-28 | 中国石油化工股份有限公司 | Catalyst system for alkene polymerization reaction |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050288460A1 (en) * | 2004-06-28 | 2005-12-29 | Zhidong Zhu | High activity and good hydrogen response Ziegler-Natta polyethylene catalyst |
| CN103304691A (en) * | 2012-03-08 | 2013-09-18 | 中国石油化工股份有限公司 | Catalyst system used for alkene polymerization |
| CN103819586A (en) * | 2012-11-16 | 2014-05-28 | 中国石油化工股份有限公司 | Catalyst system for alkene polymerization reaction |
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