CN103819585A - Catalyst component for olefin polymerization, catalyst and application - Google Patents
Catalyst component for olefin polymerization, catalyst and application Download PDFInfo
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- CN103819585A CN103819585A CN201210465049.5A CN201210465049A CN103819585A CN 103819585 A CN103819585 A CN 103819585A CN 201210465049 A CN201210465049 A CN 201210465049A CN 103819585 A CN103819585 A CN 103819585A
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Abstract
The invention discloses a catalyst component for olefin polymerization. The catalyst component is prepared by the method including the following steps: enabling a magnesium compound to be contacted with an internal electron donor, then be contacted with a titanium compound, and be contacted with a silicone compound finally, and obtaining the catalyst component, wherein the general formula of the magnesium compound is XmMg(OR)n, where X is a halogen, R is an alkyl group from C1 to C20, and m+n=2; the general formula of the titanium compound is TiXm(OR6)4-m, where X is a halogen, R6 is a hydroxy group from C1 to C20, and m is an integer from 1 to 4; the general formula of the silicone compound is RnSi(OR1)4-n, where n is an integer from 0 to 4, R is selected from alkyl group, naphthenic base, aromatic group, halide alkyl group, halogen and hydrogen atom, and R1 is selected from alkyl group, naphthenic base, aromatic group and halide alkyl group; the internal electron donor is selected from alkyl ester, aliphatic ether, cycloaliphatic ether and aliphatic ketone of aliphatic carboxylic acid or aromatic carboxylic acid. The catalyst provided by the invention has the advantages of high activity and good hydrogen regulation performance, and can be used for preparing and obtaining polymers with less fine powder when being used for polymerization.
Description
Technical field
The present invention relates to field of olefin polymerisation, be specifically related to a kind of catalyst component for olefin and catalyzer.The invention still further relates to the application of described catalyzer.
Background technology
Have a magnesium compound for solid form, its general formula is X
mmg (OR)
n, in general formula, X is halogen, R is C
1~ C
20alkyl, m+n=2.The preparation method of above-mentioned magnesium compound is known, for example disclosed method in WO96/32427A1, WO01/23441A1, Chinese patent application 200580040424.X and 200780022099.3.The general formula that use has solid form is X
mmg (OR)
nalkoxy magnesium chloride compound to prepare catalyst component for olefin be known, the essentially consist of this type of catalyst component is magnesium-containing compound and carries titanium compound and electronic donor compound capable thereon.
The method that adopts alkoxy magnesium chloride compound to prepare polyolefin catalyst component discloses in WO96/32427A1 He in Chinese patent application 200580040424.X.According to the catalyst component that in WO96/32427A1 prepared by disclosed method, its activity is lower, and fine polymer powder is more, and the hydrogen regulation performance of catalyzer is bad.The disclosed method of Chinese patent application 200580040424.X, its preparation technology's flow process is longer, and cost is higher.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of catalyst component for olefin and catalyzer, this catalyst activity is higher, and hydrogen regulation performance is better, and during for polymerization, the fine powder of the polymkeric substance preparing is less.
According to an aspect of the present invention, provide a kind of catalyst component for olefin, it is prepared by the method that comprises following step: magnesium compound is contacted with internal electron donor, then contact with titanium compound, finally contact with silicon compound, obtain described catalyst component, wherein
The general formula of described magnesium compound is X
mmg (OR)
n, in general formula, X is halogen, R is C
1~ C
20alkyl, m+n=2;
The general formula of described titanium compound is TiX
m(OR
6)
4-m, wherein X is halogen, R
6for C
1-C
20alkyl, the integer that m is 1-4;
Described silicon compound general formula is R
nsi(OR
1)
4-n, in formula, n is 0 to 4 integer, R is selected from alkyl, cycloalkyl, aryl, halogenated alkyl, halogen and hydrogen atom, R
1be selected from alkyl, cycloalkyl, aryl and halogenated alkyl;
Described internal electron donor is selected from aliphatic series or aromatic carboxylic acid's alkyl ester, aliphatic ether, cyclic aliphatic ether and aliphatic ketone.
In above-mentioned catalyst component, in the gross weight of catalyzer, the content of titanium is 1 ~ 10wt%, and the content of magnesium is 10 ~ 20wt%, and the content of silicon is 0.01 ~ 0.5wt%, and the content of internal electron donor compound is 5 ~ 25wt%, and the content of halogen is 40 ~ 70wt%.Preferably, in described catalyst component, the content of titanium is 1 ~ 5wt%, and the content of magnesium is 15 ~ 20wt%, and the content of silicon is 0.05 ~ 0.2wt%, and the content of internal electron donor compound is 6 ~ 14wt%, and the content of halogen is 45 ~ 65wt%.
In above-mentioned catalyst component, described general formula is X
mmg (OR)
nthe preparation method of magnesium compound be known, described in WO-A-96/32427, WO-A-01/23441, Chinese patent application 200580040424.X and 200780022099.3, its preparation method comprises following two steps:
(1) MAGNESIUM METAL and Organohalogen compounds R
1x contact forms Grignard reagent MgR
1x, by the first reaction product Grignard reagent MgR of the dissolving of gained
1x separates with solid residual product, wherein R
1be the alkyl of 6 carbon atoms at the most, X is halogen atom;
(2) make the silane compound SiR containing alkoxyl group
2 m(OR
3)
nwith obtained Grignard reagent MgR
1x contact, by formed throw out purifying, obtains alkoxy magnesium chloride.Wherein R
2for halogen atom or C
1-C
20alkyl, R
3for C
1-C
20alkyl, 0≤m<4,0<n≤4, in silane compound and Grignard reagent, the mol ratio of magnesium is 1:2 ~ 1:8.
In above-mentioned catalyst component, described internal electron donor for example can be for being selected from C
1-C
4the C of aliphatic saturated monocarboxylic acid
1-C
4alkyl ester, C
7-C
8the C of aromatic carboxylic acid
1-C
4alkyl ester, C
2-C
6aliphatic ether, C
3-C
4cyclic ethers, C
3-C
6saturated fatty ketone.Specific examples comprises diisobutyl phthalate, n-butyl phthalate, dimixo-octyl phthalate, phthalic acid 1, 3 diamyl esters, methyl-formiate, ethyl formate, formic acid n-propyl, isopropyl formate, butyl formate, methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, butylacetate, methyl propionate, ethyl propionate, n propyl propionate, isopropyl propionate, butyl propionate, methyl-butyrate, ethyl butyrate, propyl butyrate, isopropyl butyrate, butyl butyrate, ether, propyl ether, butyl ether, amyl ether, hexyl ether, tetrahydrofuran (THF) (THF), acetone, butanone, 2 pentanone and methyl iso-butyl ketone (MIBK).Described internal electron donor is preferably selected from diisobutyl phthalate, n-butyl phthalate, phthalic acid 1,3 diamyl esters, ethyl formate, formic acid n-propyl, isopropyl formate, butyl formate, methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, butylacetate, methyl propionate, ethyl propionate, n propyl propionate, isopropyl propionate, butyl propionate, methyl-butyrate, ethyl butyrate, propyl butyrate, isopropyl butyrate and butyl butyrate, most preferably be dibutyl phthalate.
In above-mentioned catalyst component, described titanium compound is selected from titanium tetrachloride, titanium tetrabromide, titanium tetra iodide, four titanium butoxide, purity titanium tetraethoxide, a chlorine triethoxy titanium, dichloro diethoxy titanium and trichlorine one ethanolato-titanium, be preferably selected from titanium tetrachloride, titanium tetrabromide and titanium tetra iodide, more preferably titanium tetrachloride.
In above-mentioned catalyst component, described silicon compound is selected from silicon tetrachloride, a chlorine triethoxysilicane, dichloro diethoxy silicon, trichlorine one oxyethyl group silicon, four butoxy silanes, tetraethoxysilane, phenylbenzene diethoxy silane, dimethoxydiphenylsilane, propyl trimethoxy silicane, propyl-triethoxysilicane, Cyclohexyl Methyl Dimethoxysilane and cyclohexyl methyl diethoxy silane, is preferably silicon tetrachloride.
In above-mentioned catalyst component, preferably described temperature while contacting with titanium compound is 115 ~ 180 ℃.
In above-mentioned catalyst component, its feature exists, and described contact is carried out in organic solvent.Described solvent can be the conventional all kinds of SOLVENTS in this area, and one or more that concrete can be for example in hexane, heptane, toluene, dimethylbenzene, are wherein preferably toluene.
In a specific embodiment of above-mentioned catalyst component, the magnesium compound that by above-mentioned general formula is under agitation XmMg (OR) n contacts 0.5 ~ 6 hour with electron donor compound at 0 ~ 100 ℃ of temperature, be preferably at 30 ~ 80 ℃ of temperature and contact 1 ~ 4 hour, after filtration washing, contact with titanium compound; Reaction mixture is warming up to 100 ~ 200 ℃ again, under whipped state, contact 0.5 ~ 8 hour, be preferably 1 ~ 6 hour, elimination mother liquor, use again the halogenide of transition metals Ti and the mixture process of washing composition (for example toluene) 3 ~ 4 times, leach liquid, for example, with washing composition (hexane, toluene) washing solids, make solids contact 0.5 ~ 6 hour with silicon compound at 0 ~ 100 ℃ of temperature, filter and make olefin polymerization catalysis.
According to a further aspect in the invention, provide a kind of catalyst for olefines polymerizing, comprised following component:
A. the catalyst component described in any one in claim 1 ~ 9;
B. alkylaluminium cpd, its general formula is AlR'n'X'3-n', and R' is the alkyl of hydrogen, carbonatoms 1-20 or the aryl of carbonatoms 6-20, and X' is halogen, the integer that n' is 1-3.
In above-mentioned catalyzer, the mol ratio of described components b and component a is counted 5 ~ 5000:1 with aluminium/titanium, is preferably 20 ~ 500:1.
In above-mentioned catalyzer, described alkylaluminium cpd is preferably selected from trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, trioctylaluminum, a hydrogen diethyl aluminum, a hydrogen diisobutyl aluminum, aluminium diethyl monochloride, a chloro-di-isobutyl aluminum, sesquialter ethyl aluminum chloride and ethyl aluminum dichloride, more preferably triethyl aluminum.
In above-mentioned catalyzer, also can comprise amount of component b silicoorganic compound, the general formula of described silicoorganic compound is R
nsi(OR
1)
4-n, in formula, n is 0 to 3 integer, R is selected from alkyl, cycloalkyl, aryl, halogenated alkyl, halogen and hydrogen atom, R
1be selected from alkyl, cycloalkyl, aryl and halogenated alkyl.The specific examples of described silicoorganic compound comprises trimethylammonium methoxy silane, trimethylethoxysilane, trimethyl phenoxysilane, dimethyldimethoxysil,ne, dimethyldiethoxysilane, methyl-t-butyldimethoxysilane, dimethoxydiphenylsilane, phenylbenzene diethoxy silane, two cyclohexyl dimethoxy silane, phenyltrimethoxysila,e, phenyl triethoxysilane, vinyltrimethoxy silane, Cyclohexylmethyldimethoxysilane, dicyclopentyl dimethoxyl silane, 2-ethyl piperidine base-2-tertiary butyl dimethoxy silane, (1, 1, the fluoro-2-propyl group of 1-tri-)-2-ethyl piperidine base dimethoxy silane and (1, 1, the fluoro-2-propyl group of 1-tri-)-methyl dimethoxysilane, be preferably Cyclohexylmethyldimethoxysilane.The consumption of described silicoorganic compound can regulate according to real needs.
According to a further aspect in the invention, provide a kind of olefine polymerizing process, described alkene carries out polyreaction under the existence of above-mentioned catalyst component or catalyzer.
In above-mentioned polymerization process, described alkene can be various conventional alkene, for example, can be C
2~ C
6alkene, for example ethene, propylene, 1-n-butene, the positive amylene of 1-, 1-n-hexylene, the positive octene of 1-and 4-methyl-1-pentene.
In a specific embodiment of aforesaid method, described polymerization process is during for the homopolymerization of ethene or copolymerization, and described catalyzer comprises above-mentioned catalyst component and alkylaluminium cpd.
In above-mentioned polymerization process, the condition of described polyreaction can be the conventional olefinic polymerization condition in this area, and being generally temperature is 0 ~ 150 ℃, and the time is 0.5 ~ 5 hour, and pressure is 0.1 ~ 10MPa.
In a specific embodiment of above-mentioned polymerization process, described polyreaction is carried out in solvent; Described olefinic polymerization condition comprises: temperature is 0 ~ 150 ℃, and the time is 0.5 ~ 5 hour, and pressure is 0.1 ~ 10MPa, and in the titanium in olefin polymerization catalysis, the concentration of described olefin polymerization catalysis in solvent is 0.0001 ~ 1 mol/L.
In above-mentioned polymerization process, preferred described polyreaction is carried out under hydrogen exists.In a specific embodiment, the dividing potential drop of the hydrogen adding is 0.1 ~ 2MPa.
According to the present invention, by controlling the contact series of various reactants, the polymerization activity of the catalyzer finally obtaining is high, and hydrogen regulation performance is good.According to catalyzer provided by the invention, for olefinic polymerization, particularly when propylene polymerization, the melting index of the polymkeric substance obtaining is high, and fine polymer powder is few.Especially under high hydrogen concentration, the melting index of the polymkeric substance obtaining is higher.Catalyst component provided by the invention and catalyzer, the random copolymerization and the heterogeneous crushing-resistant copolymerization that are specially adapted to equal polymerization, propylene and the ethene of propylene close.
Embodiment
Describe the present invention by specific embodiment below, but do not form any limitation of the invention.
Melt index (MI): measure according to ASTM D1238-99.
Embodiment 1
A general formula X
mmg (OR)
nmagnesium compound preparation
In 250 milliliters of reactors that repeat displacement through high pure nitrogen, add 16 grams of magnesium powder, the lower 85 ℃ of heating of agitation condition 0.5 hour, add 113 milliliters of n-butyl ethers, 0.02 gram of iodine, at 76 ℃, drip 71 milliliters of chlorobutanes, and at this temperature, react 8 hours, leave standstill, after 10 hours, approximately 120 milliliters of taking-ups of supernatant liquid are placed in to another reactor, be cooled to-25 ℃, add 40 milliliters of tetraethoxy-silicanes, in 4 hours, be warming up to 60 ℃, constant temperature is with hexane washing 5 times after 1 hour, and then vacuum is drained and obtained 28 grams of white solids.
The preparation of B catalyst component
In 250 milliliters of reactors that repeat displacement through high pure nitrogen, add 5 grams of above-mentioned white solids, 60 milliliters of toluene, 2.0 milliliters of dibutyl phthalates, 40 ℃ maintain 0.5 hour after by liquid filtering, add 72 milliliters of titanium tetrachlorides, 48 milliliters of chlorobenzenes, be warming up to 130 ℃, after maintaining 1 hour by liquid filtering, add 48 milliliters of titanium tetrachlorides, 72 milliliters of chlorobenzenes, be warming up to 130 ℃, after maintaining 0.5 hour by liquid filtering, repeat with 48 milliliters of titanium tetrachlorides, 72 milliliters of chlorobenzenes are processed 2 times at 130 ℃ of constant temperature for 0.5 hour, filtering liquid, then use 120 milliliters of hexanes 55 ~ 60 ℃ of washings six times, after filtering filtrate, add 120 milliliters of hexanes, add 0.5 milliliter of silicon tetrachloride, 50 ℃ of constant temperature 1 hour, after filtering vacuum-drying, obtain catalyst component.
C olefinic polymerization
(1) polymerizing condition 1
5 liters of stainless steel autoclaves are after nitrogen is fully replaced, adding 5 ml concns is that the hexane solution of triethyl aluminum of 0.5 mol/L and 1 ml concn are 10 milligrams of the hexane solution of Cyclohexylmethyldimethoxysilane (CMMS) of 0.1 mol/L and catalyzer prepared by embodiment 1, then add 10 milliliters of hexanes to rinse charge line, add again 1 liter of (under standard state) hydrogen, with 2 liters of refining propylene, be warming up to 70 ℃, polyreaction 1 hour at this temperature.After reaction finishes, reactor lowered the temperature and stop stirring and discharge reaction product, obtaining olefin polymer, concrete outcome refers to table 1.
(2) polymerizing condition 2
Polymerization is with the polyreaction under polymerizing condition 1, and difference is to add 5 liters of (under standard state) hydrogen.Concrete outcome is in table 1.
Embodiment 2
A general formula X
mmg (OR)
nmagnesium compound preparation
With embodiment 1
The preparation of B catalyst component
With embodiment 1, difference is that dibutyl phthalate changes 4.0 milliliters into
C olefinic polymerization
With embodiment 1.Concrete data are in table 1.
Embodiment 3
A general formula X
mmg (OR)
nmagnesium compound preparation
With embodiment 1
The preparation of B catalyst component
With embodiment 1, difference is to add 1.0 milliliters of silicon tetrachlorides.
C olefinic polymerization
With embodiment 1.Concrete data are in table 1.
Embodiment 4
A general formula X
mmg (OR)
nmagnesium compound preparation
With embodiment 1
The preparation of B catalyst component
In 250 milliliters of reactors that repeat displacement through high pure nitrogen, add 5 grams of above-mentioned white solids, 60 milliliters of toluene, 2.0 milliliters of dibutyl phthalates, 40 ℃ maintain 0.5 hour after by liquid filtering, add 72 milliliters of titanium tetrachlorides, 48 milliliters of chlorobenzenes, be warming up to 130 ℃, add 2.0 milliliters of dibutyl phthalates, after maintaining 1 hour by liquid filtering, add 48 milliliters of titanium tetrachlorides, 72 milliliters of chlorobenzenes, be warming up to 130 ℃, after maintaining 0.5 hour by liquid filtering, repeat with 48 milliliters of titanium tetrachlorides, 72 milliliters of chlorobenzenes are processed 2 times at 130 ℃ of constant temperature for 0.5 hour, filtering liquid, add 120 milliliters of hexanes, add 0.5 milliliter of silicon tetrachloride, 50 ℃ of constant temperature 1 hour, then use 120 milliliters of hexanes 55 ~ 60 ℃ of washings six times, after filtering filtrate final vacuum is dry, obtain catalyst component.
C olefinic polymerization
With embodiment 1.Concrete data are in table 1.
Comparative example 1
A general formula X
mmg (OR)
nmagnesium compound preparation
With embodiment 1
The preparation of B catalyst component
In 250 milliliters of reactors that repeat displacement through high pure nitrogen, add 5 grams of above-mentioned white solids, 72 milliliters of titanium tetrachlorides, 48 milliliters of chlorobenzenes, be warming up to 115 ℃, after maintaining 1 hour by liquid filtering, add 48 milliliters of titanium tetrachlorides, 72 milliliters of chlorobenzenes, be warming up to 115 ℃, add 2.0 milliliters of dibutyl phthalates, after maintaining 0.5 hour by liquid filtering, repeat with 48 milliliters of titanium tetrachlorides, 72 milliliters of chlorobenzenes are processed 2 times at 115 ℃ of constant temperature for 0.5 hour, filtering liquid, then use 120 milliliters of hexanes 55 ~ 60 ℃ of washings six times, after vacuum-drying, obtain catalyst component.
C olefinic polymerization
With embodiment 1.Concrete data are in table 1.
Comparative example 2
A general formula X
mmg (OR)
nmagnesium compound preparation
With embodiment 1
The preparation of B catalyst component
In 250 milliliters of reactors that repeat displacement through high pure nitrogen, add 5 grams of above-mentioned white solids, 72 milliliters of titanium tetrachlorides, 48 milliliters of chlorobenzenes, be warming up to 115 ℃, add 2.0 milliliters of dibutyl phthalates, after maintaining 1 hour by liquid filtering, add 48 milliliters of titanium tetrachlorides, 72 milliliters of chlorobenzenes, be warming up to 115 ℃, after maintaining 0.5 hour by liquid filtering, repeat with 48 milliliters of titanium tetrachlorides, 72 milliliters of chlorobenzenes are processed 2 times at 115 ℃ of constant temperature for 0.5 hour, filtering liquid, then use 120 milliliters of hexanes 55 ~ 60 ℃ of washings six times, after vacuum-drying, obtain catalyst component.
C olefinic polymerization
With embodiment 1.Concrete data are in table 1.
Table 1
From table 1, data can be learnt, utilize catalyst component provided by the invention or catalyzer for propylene polymerization, and polymerization activity is high, and the melting index of polymkeric substance is high, and the fine polymer powder content obtaining is few.Even under high hydrogen concentration condition, the fine polymer powder obtaining is still considerably less.
It should be noted in the discussion above that above-described embodiment, only for explaining the present invention, does not form any limitation of the invention.By with reference to exemplary embodiments, invention has been described, be descriptive and explanatory vocabulary but should be understood to word wherein used, rather than limited vocabulary.Can in the scope of the claims in the present invention, modify the present invention in accordance with regulations, and the present invention be revised not deviating from scope and spirit of the present invention.Although the present invention who wherein describes relates to specific method, material and embodiment, and does not mean that the present invention is limited to wherein disclosed particular case, on the contrary, the present invention can extend to other all methods and applications with identical function.
Claims (11)
1. a catalyst component for olefin, it is prepared by the method that comprises following step: magnesium compound is contacted with internal electron donor, then contact with titanium compound, finally contact with silicon compound, obtain described catalyst component, wherein
The general formula of described magnesium compound is X
mmg (OR)
n, in general formula, X is halogen, R is C
1~ C
20alkyl, m+n=2;
The general formula of described titanium compound is TiX
m(OR
6)
4-m, wherein X is halogen, R
6for C
1-C
20alkyl, the integer that m is 1-4;
Described silicon compound general formula is R
nsi(OR
1)
4-n, in formula, n is 0 to 4 integer, R is selected from alkyl, cycloalkyl, aryl, halogenated alkyl, halogen and hydrogen atom, R
1be selected from alkyl, cycloalkyl, aryl and halogenated alkyl;
Described internal electron donor is selected from aliphatic series or aromatic carboxylic acid's alkyl ester, aliphatic ether, cyclic aliphatic ether and aliphatic ketone.
2. catalyst component according to claim 1, it is characterized in that, in described catalyst component, in the gross weight of catalyzer, the content of titanium is 1 ~ 10wt%, and the content of magnesium is 10 ~ 20wt%, and the content of silicon is 0.01 ~ 0.5wt%, the content of internal electron donor compound is 5 ~ 25wt%, and the content of halogen is 40 ~ 70wt%; Wherein preferably, the content of titanium is 1 ~ 5wt%, and the content of magnesium is 15 ~ 20wt%, and the content of silicon is 0.05 ~ 0.2wt%, and the content of internal electron donor compound is 6 ~ 14wt%, and the content of halogen is 45 ~ 65wt%.
3. catalyst component according to claim 1 and 2, it is characterized in that, described internal electron donor is selected from diisobutyl phthalate, n-butyl phthalate, phthalic acid 1, 3 diamyl esters, ethyl formate, formic acid n-propyl, isopropyl formate, butyl formate, methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, butylacetate, methyl propionate, ethyl propionate, n propyl propionate, isopropyl propionate, butyl propionate, methyl-butyrate, ethyl butyrate, propyl butyrate, isopropyl butyrate and butyl butyrate, be preferably dibutyl phthalate.
4. according to the catalyst component described in any one in claim 1 ~ 3, it is characterized in that, described titanium compound is selected from titanium tetrachloride, titanium tetrabromide, titanium tetra iodide, four titanium butoxide, purity titanium tetraethoxide, a chlorine triethoxy titanium, dichloro diethoxy titanium and trichlorine one ethanolato-titanium, be preferably selected from titanium tetrachloride, titanium tetrabromide and titanium tetra iodide, more preferably titanium tetrachloride.
5. according to the catalyst component described in any one in claim 1 ~ 4, it is characterized in that, described silicon compound is selected from silicon tetrachloride, a chlorine triethoxysilicane, dichloro diethoxy silicon, trichlorine one oxyethyl group silicon, four butoxy silanes, tetraethoxysilane, phenylbenzene diethoxy silane, dimethoxydiphenylsilane, propyl trimethoxy silicane, propyl-triethoxysilicane, Cyclohexyl Methyl Dimethoxysilane and cyclohexyl methyl diethoxy silane, is preferably silicon tetrachloride.
6. according to the catalyst component described in any one in claim 1 ~ 5, it is characterized in that, described contact is carried out at 115 ~ 180 ℃.
7. according to the catalyst component described in any one in claim 1 ~ 6, its feature exists, and described contact is carried out in organic solvent.
8. a catalyst for olefines polymerizing, comprises following component:
A. the catalyst component described in any one in claim 1 ~ 7;
B. alkylaluminium cpd, its general formula is AlR'n'X'3-n', and R' is the alkyl of hydrogen, carbonatoms 1-20 or the aryl of carbonatoms 6-20, and X' is halogen, the integer that n' is 1-3.
9. catalyzer according to claim 8, is characterized in that, the mol ratio of described components b and component a is counted 5 ~ 5000:1 with aluminium/titanium, is preferably 20 ~ 500:1.
10. catalyzer according to claim 8 or claim 9, is characterized in that, in described catalyzer, comprise amount of component b silicoorganic compound, the general formula of described silicoorganic compound is R
nsi(OR
1)
4-n, in formula, n is 0 to 3 integer, R is selected from alkyl, cycloalkyl, aryl, halogenated alkyl, halogen and hydrogen atom, R
1be selected from alkyl, cycloalkyl, aryl and halogenated alkyl.
11. 1 kinds of olefine polymerizing process, described alkene carries out polymerization under the existence of catalyzer described in any one in the catalyst component described in any one or claim 8 ~ 10 in claim 1 ~ 7.
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| CN116041585A (en) * | 2021-10-28 | 2023-05-02 | 中国石油化工股份有限公司 | Spherical magnesium halide adduct and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101065404A (en) * | 2004-11-26 | 2007-10-31 | 沙特基础工业公司 | Process for the preparation of a catalyst component for the polymerization of an olefin |
| US20090306315A1 (en) * | 2006-05-24 | 2009-12-10 | Yves Johann Elizabeth Ramjoie | Process for Preparing a Catalyst Component for Propylene Polymerization |
| CN102464734A (en) * | 2010-11-18 | 2012-05-23 | 中国石油化工股份有限公司 | Olefin polymerization catalyst and preparation method thereof and olefin polymerization method |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101065404A (en) * | 2004-11-26 | 2007-10-31 | 沙特基础工业公司 | Process for the preparation of a catalyst component for the polymerization of an olefin |
| US20090306315A1 (en) * | 2006-05-24 | 2009-12-10 | Yves Johann Elizabeth Ramjoie | Process for Preparing a Catalyst Component for Propylene Polymerization |
| CN102464734A (en) * | 2010-11-18 | 2012-05-23 | 中国石油化工股份有限公司 | Olefin polymerization catalyst and preparation method thereof and olefin polymerization method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116041585A (en) * | 2021-10-28 | 2023-05-02 | 中国石油化工股份有限公司 | Spherical magnesium halide adduct and preparation method and application thereof |
| CN116041585B (en) * | 2021-10-28 | 2024-06-04 | 中国石油化工股份有限公司 | Spherical magnesium halide adduct and preparation method and application thereof |
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