CN101798362B - Ziegler-Natta olefin polymerization catalysts with single-site center property - Google Patents
Ziegler-Natta olefin polymerization catalysts with single-site center property Download PDFInfo
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- WZZYRYUYXRCKJT-BUVRLJJBSA-N CC(C)(C)c(cc1C(C)(C)C)cc(/C=N/c(cccc2)c2O[SiH](C)C)c1O Chemical compound CC(C)(C)c(cc1C(C)(C)C)cc(/C=N/c(cccc2)c2O[SiH](C)C)c1O WZZYRYUYXRCKJT-BUVRLJJBSA-N 0.000 description 1
- QHTKUAACSNJYHL-WOJGMQOQSA-N Oc1ccccc1/C=N/c(ccc1c2cccc1)c2OS Chemical compound Oc1ccccc1/C=N/c(ccc1c2cccc1)c2OS QHTKUAACSNJYHL-WOJGMQOQSA-N 0.000 description 1
Abstract
The invention relates to novel Ziegler-Natta olefin polymerization catalysts with single-site center property. The catalysts are characterized in that the catalysts are obtained by adopting a one-pot method and adding novel multidentate ligands (I), magnesium compounds, metal compounds and carriers to tetrahydrofuran solution for treatment. Under the action of alkylaluminium or alkylaluminoxane and other cocatalysts, the catalysts can obtain ethylene copolymer and homopolymer products with controllable molecular weight distribution (1.6-40) and uniformly distributed comonomers through high activity. The catalysts can realize catalytic ethylene polymerization, as well as the slurry-process or gas-phase-process homopolymerization or copolymerization of ethylene and 1-olefin, annular olefin, polar monomer and the like.
Description
Technical field
The invention relates to one type of novel Z-N (Ziegler-Natta) olefin polymerization catalysis with single active center's character.This catalyzer has used one type of novel polydentate ligand as organic electron donor.Under the effect of promotor, utilize the copolymerization of equal polymerization that this catalyzer can catalyzed ethylene or ethene and terminal olefin to obtain the olefin polymer of controllable structure.
Background technology
Along with the fast development of polyolefin industry, the production of high-performance poly olefin material more and more receives people's extensive attention.Present international research thinks that the production of high-performance poly olefin material mainly can realize through dual mode: 1) utilize Ziegler-Natta catalyst, rely on the improvement of chemical technique; 2) utilize novel single site catalysts to comprise metallocene catalyst and non-luxuriant type of catalyzer.Ziegler-Natta catalyst is since finding the fifties in last century; Brought into play important effect in polyolefin field; But because its many active site cause the particularly poly structure of polymkeric substance can not be controlled effectively the molecular weight distribution broad; The skewness of comonomer in polymer chain, these problems are restricted it when the synthesized high-performance polyolefin resin.Through in the preparation process of Ziegler-Natta ethylene rolymerization catalyst, adding the electron donor compound, can improve activity of such catalysts, polymer stacks density, can also regulate the MWD with controlling polymers, the existing report of the research of this respect.Employed electron donor compound comprises alcohol, ether, organic amine, organic carboxyl acid, organic acyl chlorides, ester class and type siloxane etc.; Can be with reference to U.S. Pat 4330649,5106807,4816433,4829037,4847227,4970186,5130284,5260245,5336652 and 5561091, European patent EP 0389173A2 and Chinese patent CN 1050389A and CN 1510055A etc.But in general, utilize above-mentioned Preparation of Catalyst molecular weight distribution broad, still remain to be improved.
The catalyzer of novel single active center can obtain narrow molecular weight distributions polyolefine (about 2) because catalyst active center is identical; Can effectively realize ethene and other monomeric copolymerizations; And can reach the purpose of the polymkeric substance of preparation different molecular weight and MWD through regulating the Primary Catalysts chemical structure as required, thereby obtain multiple high-performance poly olefin material.But these new catalysts because exist the stability of Primary Catalysts lower, synthetic difficulty, be difficult for preserving, a large amount of expensive promotors of needs and problem such as be difficult on present polymerization technique device, turn round, cause its exploitation and application to receive very big restriction.
Utilize Ziegler-Natta catalyst to realize regulation and control, highly actively obtain narrow molecular weight distribution (1.6-3.8), the comonomer distribution homogeneous polymer is not also appeared in the newspapers polymer architecture and performance.
Summary of the invention
The purpose of this invention is to provide a kind of Z-N with single active center's character (Ziegler-Natta) olefin polymerization catalysis with high catalytic activity.
The present invention also provides above-mentioned preparation method with Ziegler-Natta catalyst of single active center's character.
Another object of the present invention has provided utilizes above-mentioned Ziegler-Natta catalyst purposes with single active center's character, in particular for the olefin polymer of synthetic molecular weight narrowly distributing (1.5-3.8).
The present invention prepares novel Z-N (Ziegler-Natta) olefin polymerization catalysis with single active center's character through introducing one type of polydentate ligand as novel organic electron donor.Under the promotor effect, this kind catalyzer can highly active catalysis in olefine polymerization, and can control polyolefinic structure and comprise molecular weight and MWD; Described alkene is ethene, 1-alkene, cycloolefin and verivate thereof, various olefin(e) acid and verivate, enol and verivate, diolefine etc.Wherein 1-alkene is meant C
3-C
20Alkene, for example propylene, 1-butylene, 1-amylene, 1-hexene, 1-octene, 1-decene, 4-methyl-1-pentene and composition thereof etc.; The main finger ring amylene of cycloolefin, tetrahydrobenzene, norbornylene etc. and have the verivate of polar group.
One type of Z-N olefin polymerization catalysis with single active center's character provided by the invention is to obtain by containing polydentate ligand (I), metallic compound, magnesium compound and carrier prepared in reaction; The described mol ratio that contains polydentate ligand (I), metallic compound and magnesium compound is 0.001-50: 1: 1-300; The weight ratio 1 of magnesium compound and carrier: 0.1-20;
Described polydentate ligand (I) has following structural formula:
Wherein:
Be Wasserstoffatoms, halogen atom, C
1-C
30Alkyl, C
1-C
30Contain group, C
1-C
30Sulfur-containing group, C
1-C
30Oxy radical, C
1-C
30Phosphorus-containing groups, C
1-C
30Silicon-containing group and other safing function property group, above-mentioned group is identical or different to each other, wherein adjacent group Cheng Jiancheng ring or Cheng Jiancheng ring not each other;
R
z: be identical or different the containing heteroatoms or do not contain heteroatomic R group of z, adjacent group Cheng Jiancheng ring or Cheng Jiancheng ring not each other wherein, R such as above-mentioned definition, z is 1,2 or 3;
D: be oxygen, boron, aluminium, silicon, carbon, germanium or tin;
A and b: be 1,2,3,4,5,6,7 or 8;
Described C
1-C
30Alkyl refer to contain C
1-C
30Alkyl, C
3-C
30Cyclic group, C
2-C
30Group, the C of carbon-carbon double bonds
2-C
30Carbon-carbon triple-linked group, C
6-C
30Aryl radical or C
6-C
30Substituted aryl radical, C
8-C
30Condensed ring alkyl or C
4-C
30Heterogeneous ring compound;
Described C
6-C
30The substituted aroma alkyl refer to contain on the aryl radical one or more C
1-C
10Alkyl, halogen, C
1-C
10Alkoxyl group, C
1-C
10Amido, C
1-C
10Silica-based as substituted radical, contain in the process of compound of substituted hydrocarbon radical in use, these substituting groups are inert, promptly these substituting groups do not have substantial interference to related reaction process; Described halogen refers to fluorine, chlorine, bromine or iodine.
R
1-R
10Represented C
1-C
30Alkyl, can be exemplified below particularly:
C such as methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, sec.-butyl, the tertiary butyl
1-C
30, preferred C
1-C
20Straight chain or have the alkyl of side chain;
C such as vinyl, propenyl
1-C
30, preferred C
1-C
20Straight chain or have the thiazolinyl of side chain;
C such as ethynyl, proyl
1-C
30, preferred C
1-C
20Straight chain or have the alkynyl of side chain;
Cyclopropyl, cyclobutyl, cyclopentyl, C such as cyclohexyl, cyclobutadiene base, cyclopentadienyl moiety
1-C
30, preferred C
1-C
20Contain substituting group or do not contain substituent naphthenic base, cycloalkenyl group;
C such as phenyl, xenyl, naphthyl, phenanthryl, anthryl
6-C
30, preferred C
6-C
20Contain substituting group or do not contain substituent aromatic group;
The Wasserstoffatoms of above-mentioned alkyl also can be replaced by halogen, for example C such as trifluoromethyl, trifluoroethyl, pentafluorophenyl group
1-C
30, preferred C
1-C
20Straight chain or have the halo alkyl of side chain;
In addition, above-mentioned alkyl can also be replaced by following groups: alkoxyl group, aryloxy, ester group, ether, carboxyl, carboxylic acid ester groups, hydroxyl, peroxy, acid anhydride, and heterogeneous ring compound residue etc. contains the oxygen base; Nitrogen-containing groups such as amino, imino-, carboxamido-group, diazanyl, hydrazono-, nitro, nitroso-group, cyanic acid, isocyano-, cyanate ester based, diazo, azido-, amidino groups, ammonium, ammonium salt; Boron-containing groups such as borane base, diborane base; Sulfur-containing groups such as sulfydryl, thioic acid sulfoacid ester group, dithio perester radical, alkylthio, arylthio; Phosphino-, phosphorus-containing groups such as phosphate-based; Silicon-containing group such as trimethyl silicon based, that triethyl is silica-based, triethoxy is silica-based; And germanic or stanniferous group.
Described C
1-C
30Substituted alkyl refer to contain on the alkyl one or more substituted radical, contain in the process of compound of substituted hydrocarbon radical in use, these substituting groups should not have substantial interference to related reaction process; Described halogen refers to fluorine, chlorine, bromine or iodine;
Oxy radical refers to that substituting group contains alkoxyl group, like OMe, and OEt, O (CH)
5CH
3, CH
2OC
4H
9Deng;
Sulfur-containing group refers to contain sulfide based structural in the substituting group, like SMe, and SBu
i, CH
2SPr
i
C
1-C
30Boron-containing group refer to contain boron in the substituting group, and alkyl carbon number summation is no more than 30, like (C
6F
5)
4B
-
Contain aluminium base group and refer to contain in the substituting group aluminium element;
Phosphorus-containing groups refers to contain phosphine groups in the substituting group, like PPh
2, CH
2PPh
2
Nitrogen-containing group refers to contain in the substituting group nitrogen element;
Silicon-containing group refers to contain in the substituting group element silicon;
Contain element Ge in the germanic group substituting group;
Contain tin group and refer to contain in the substituting group tin element.
Described alkyl comprises alkyl, alkylene and alkynes base;
The molecular formula of described metallic compound is MX
nY
m,
Wherein M is meant the 3rd or 4 family's metal, preferably group-4 metals.Can enumerate scandium, titanium, zirconium, hafnium particularly, preferably titanium, zirconium, hafnium, best is titanium, zirconium;
X is meant halogen, preferred chlorine or bromine;
Y is meant OR
14, N (R
15)
2, R
16, THF, Et
2O, wherein R
14, R
15Be meant C
1-C
6Alkyl; R
16Be meant C
1-C
16Alkyl;
N and m are respectively 0,1,2,3 or 4, and condition is that to satisfy described metallic compound be electroneutral for n and m sum;
Said magnesium compound is magnesium halide, alkyl magnesium, alkoxyl group magnesium halide, alkoxyl magnesium, or their mixture;
Described carrier is selected from the oxide compound of the 2nd, 4,13,14 group elements at interior inorganic oxide and oxidation mixture and mixed oxide; The oxidation material for preparing through the pyrohydrolysis process by gaseous metal oxide compound or silicon compound, or organic high molecular polymer.
Preparation of catalysts method involved in the present invention comprises the steps:
1) under noble gas protection or the reduced pressure, will be as the organic or inorganic solid of carrier or both mixture 100-1000 ℃ of following drying or roasting 1-24 hour;
2) under room temperature to 100 ℃ condition, magnesium compound is dissolved in forms solution in the THF; In above-mentioned solution, add successively carrier described in the step 1, metallic compound and polydentate ligand (I), reaction is 2-48 hour under room temperature to 100 ℃ condition, removes solvent, washing and vacuum-drying; Preferable reaction temperature is 50-95 ℃; The preferred reaction time is 4-24 hour.
Wherein, Described solid as carrier for the oxide compound that is selected from the 2nd, 4,13,14 group elements at interior inorganic oxide and oxidation mixture and mixed oxide, the oxidation material for preparing through the pyrohydrolysis process by gaseous metal oxide compound or silicon compound; Comprise silica gel; Polynite, aluminum oxide or clay, or molecular sieve etc.; Solid as carrier can also be an organic high molecular polymer, comprises PS, Vilaterm etc.The preferred silica gel of described carrier, its particle diameter are 1-100 μ m, specific surface area 50-500m
2/ g, pore volume 0.4-3mL/g, mean pore size 5-50nm;
Said magnesium compound is magnesium halide, alkyl magnesium, alkoxyl group magnesium halide, alkoxyl magnesium, or their mixture; Preferred magnesium chloride;
The molecular formula of described metallic compound is MX
nY
m, wherein M is meant the 3rd or 4 group 4 transition metals, preferably the 4th group 4 transition metal. and can be scandium, titanium, zirconium, hafnium particularly, preferably titanium, zirconium, hafnium, best is titanium, zirconium; X is meant chlorine or bromine; Y is meant OR
11, N (R
12)
2, R
13, THF, Et
2O, wherein R
11, R
12Be meant C
1-C
6Alkyl; R
13Be meant C
1-C
16Alkyl; N and m are respectively 0,1,2,3 or 4, and condition is that to satisfy described metallic compound be electroneutral for n and m sum; The preferred TiCl of described metallic compound
4, TiCl
4(THF)
2Or TiCl
4(Et
2O)
2
The used solvent of washing catalyst is C
5-C
10Alkane or C
6-C
8Aromatic hydrocarbons, preferred hexane or toluene;
The ratio of magnesium compound and THF is 10-200mL THF/gram magnesium compound, preferred 30-100mL THF/gram magnesium compound;
The mass ratio 1 of magnesium compound and carrier: 0.1-20; Preferred 1: 0.5-10;
The mol ratio of magnesium compound metallizing thing is 1-300: 1, and preferred 1-100: 1; More preferably 1-40: 1;
The mol ratio that contains heteroatomic organic cpds metallizing thing is 0.001-50: 1, and preferred 0.01-20: 1, more preferably 0.1-10: 1.
Employed all kinds of SOLVENTS all needs strict anhydrous and oxygen-free to handle among the preparation method of the Ziegler-Natta catalyst with single active center's character of the present invention; All operations all carries out under the condition of anhydrous and oxygen-free, explanation no longer in addition in following embodiment.
Ziegler-Natta catalyst with single active center's character of the present invention is applicable to that ethylene homo closes and ethene/1-alkene, ethene/cycloolefin copolymerization; Needing with aluminum alkyls or alkylaluminoxane during polymerization is promotor, and suitable promotor comprises triethyl aluminum (AlEt
3), triisobutyl aluminium (Al (i-Bu)
3), aluminium diethyl monochloride (AlEt
2Cl), three hexyl aluminium (Al (n-Hex)
3) wait or their mixture preferred AlEt
3Al/Ti mol ratio suitable during polymerization is 10-3000, preferred 20-500; Described 1-alkene is C
3-C
20Alkene, for example propylene, 1-butylene, 1-hexene, 1-heptene, 4-methyl-1-pentene, 1-octene, 1-decene, hendecene or laurylene; Described cycloolefin is cyclopentenes, tetrahydrobenzene, norbornylene or the substituted cyclopentenes of alkyl, tetrahydrobenzene, norbornylene is arranged.
Purposes with Ziegler-Natta olefin polymerization catalysis of single active center's character of the present invention can be slurry polymerization or vapour phase polymerization; Wherein, slurry polymerization conditions is that 0.1-10.0MPa, hydrogen pressure are 0-1.0MPa, polymerization temperature 50-120 ℃ for the polymerization total pressure; Slurry polymerization can carry out under overcritical or subcritical state, and the medium of employing is propane, Trimethylmethane or hexane, and polymerization reactor is stirring tank or annular-pipe reactor; The vapour phase polymerization condition is that 1.0-10.0MPa, polymerization temperature are 40-100 ℃, and polymerization can be carried out in gas fluidized bed or gas phase stirring tank.
Utilize this equal polymerization of Ziegler-Natta catalyst catalyzed ethylene, can guarantee under the highly active prerequisite, well the molecular weight of controlling polymers and MWD with single active center's character;
Catalyzer of the present invention not only preparation method is easy, is fit to suitability for industrialized production, and can high reactivity ground catalyzed ethylene and the copolymerization of other alkene, and multipolymer has comparatively ideal common monomer insertion rate.
Embodiment
Among the following embodiment, titanium in the loaded catalyst (Ti) assay carries out on the OPTRMA-3000 inductive coupling plasma emission spectrograph at ICP-AES.
Polymericular weight (M
w, M
n) and MWD (PDI=M
w/ M
n) utilize Waters Alliance GPC2000 1,2, under 135 ℃, be that standard specimen is measured in the 4-trichlorobenzene (flow velocity 1.0mL/min) with the PS.
Polymkeric substance
13C-NMR composes on Varian XL-400MHz NMR with D
4-o-dichlorobenzene is a solvent, measures down at 110 ℃.Altogether monomer insertion rate according to document (J C Randall, JMS-Rev.Maromol.Chem.Phys.1989, C29 (2&3), method 201-317) calculates.
Following embodiment will further specify the present invention, but the present invention never only limits to content that this several embodiment explains.
The preparation of embodiment 1 catalyzer 1:
(1) thermal treatment of carrier
Get ES70 type silica gel (Pq Corp.'s product) roasting under nitrogen atmosphere.Its roasting condition is: in 200 ℃ of processing 2h, be warming up to 400 ℃ then and handle 2, handle 4h, naturally cooling under nitrogen atmosphere at 600 ℃ again.Be designated as the ES70 carrier.
(2) electron donor is:
The 1.0g Magnesium Chloride Anhydrous is joined in the 40mL THF (hereinafter to be referred as THF), stir 2h down at 60 ℃; Drip the TiCl of 3.4mmol
4, at 60 ℃ of following reaction 4h, add ES70 carrier after the above-mentioned thermal treatment of 1.0g then, at 60 ℃ of reaction 4h down; The electron donor L1 that adds the above-mentioned preparation of 4.0mmol at last reacts 12h down at 60 ℃.Reaction removes solvent under reduced pressure after finishing, and (3 * 20mL) washings, drying under reduced pressure obtains catalyzer 1 to product then with hexane.Ti content: 3.50wt-%
The preparation of embodiment 2 catalyzer 2
Electron donor is:
The 1.0g Magnesium Chloride Anhydrous is joined in the 40mL THF (hereinafter to be referred as THF), stir 2h down at 60 ℃; Drip the TiCl of 3.4mmol
4, at 60 ℃ of following reaction 4h, add ES70 carrier after the above-mentioned thermal treatment of 1.0g then, at 60 ℃ of reaction 4h down; The electron donor L2 that adds the above-mentioned preparation of 4.0mmol at last reacts 12h down at 60 ℃.Reaction removes solvent under reduced pressure after finishing, and (3 * 20mL) washings, drying under reduced pressure obtains catalyzer 2 to product then with hexane.Ti content: 2.81wt-%
The preparation of embodiment 3 catalyzer 3
Electron donor is:
The 1.0g Magnesium Chloride Anhydrous is joined in the 40mL THF (hereinafter to be referred as THF), stir 2h down at 60 ℃; Drip the TiCl of 3.4mmol
4, at 60 ℃ of following reaction 4h, add the ES70 carrier after the above-mentioned thermal treatment of 1.0g then, at 60 ℃ of reaction 4h down; The electron donor L3 that adds the above-mentioned preparation of 4.0mmol at last reacts 12h down at 60 ℃.Reaction removes solvent under reduced pressure after finishing, and (3 * 20mL) washings, drying under reduced pressure obtains catalyzer 3 to product then, Ti content: 3.57wt-% with hexane.
The preparation of embodiment 4 catalyzer 4
Electron donor is:
The 1.0g Magnesium Chloride Anhydrous is joined in the 40mL THF (hereinafter to be referred as THF), stir 2h down at 60 ℃; Drip the TiCl of 3.4mmol
4, at 60 ℃ of following reaction 4h, add ES70Y carrier after the above-mentioned thermal treatment of 1.0g then, at 60 ℃ of reaction 4h down; The electron donor LL1 that adds the above-mentioned preparation of 4.0mmol at last reacts 12h down at 60 ℃.Reaction removes solvent under reduced pressure after finishing, and (3 * 20mL) washings, drying under reduced pressure obtains catalyzer 4 to product then with hexane.Ti content: 3.36wt-%.
The preparation of embodiment 5 catalyzer 5
Electron donor is:
The 1.5g Magnesium Chloride Anhydrous is joined in the 60mL THF (hereinafter to be referred as THF), stir 2h down at 60 ℃; Drip the TiCl of 3.4mmol
4, at 60 ℃ of following reaction 4h, add ES70 carrier after the above-mentioned thermal treatment of 1.0g then, at 60 ℃ of reaction 4h down; The electron donor LL1 that adds the above-mentioned preparation of 4.0mmol at last reacts 12h down at 60 ℃.Reaction removes solvent under reduced pressure after finishing, and (3 * 20mL) washings, drying under reduced pressure obtains catalyzer 5 to product then with hexane.Ti content: 2.wt-%.
The preparation of embodiment 6 catalyzer 6
Electron donor is:
The 1.0g Magnesium Chloride Anhydrous is joined in the 40mL THF (hereinafter to be referred as THF), stir 2h down at 60 ℃; Drip the TiCl of 3.4mmol
4, at 60 ℃ of following reaction 4h, add ES757 carrier after the above-mentioned thermal treatment of 1.0g then, at 60 ℃ of reaction 4h down; The electron donor L1 that adds the above-mentioned preparation of 4.0mmol at last reacts 12h down at 60 ℃.Reaction removes solvent under reduced pressure after finishing, and (3 * 20mL) washings, drying under reduced pressure obtains catalyzer 12 to product then with hexane.Ti content: 2.65wt-%.
The preparation of embodiment 7 catalyzer 7
Electron donor is:
The 1.0g Magnesium Chloride Anhydrous is joined in the 40mL THF (hereinafter to be referred as THF), stir 2h down at 60 ℃; Drip the TiCl of 4.1mmol
4, at 60 ℃ of following reaction 4h, add ES70 carrier after the above-mentioned thermal treatment of 1.0g then, at 60 ℃ of reaction 4h down; The electron donor L1 that adds the above-mentioned preparation of 4.0mmol at last reacts 12h down at 60 ℃.Reaction removes solvent under reduced pressure after finishing, and (3 * 20mL) washings, drying under reduced pressure obtains catalyzer 7 to product then with hexane.Ti content: 3.2wt-%.
The preparation of embodiment 8 catalyzer 8
Electron donor is:
The 1.0g Magnesium Chloride Anhydrous is joined in the 40mL THF (hereinafter to be referred as THF), stir 2h down at 60 ℃; Drip the TiCl of 3.4mmol
4, at 60 ℃ of following reaction 4h, add ES70Y carrier after the above-mentioned thermal treatment of 1.0g then, at 60 ℃ of reaction 4h down; The electron donor L2 that adds the above-mentioned preparation of 4.0mmol at last reacts 12h down at 60 ℃.Reaction removes solvent under reduced pressure after finishing, and (3 * 20mL) washings, drying under reduced pressure obtains catalyzer 8 to product then with hexane.Ti content: 2.53wt-%.
The preparation of embodiment 9 catalyzer 9
Electron donor is:
The 1.0g Magnesium Chloride Anhydrous is joined in the 40mL THF (hereinafter to be referred as THF), stir 2h down at 60 ℃; Drip the TiCl of 3.4mmol
4, at 60 ℃ of following reaction 4h, add ES757 carrier after the above-mentioned thermal treatment of 1.0g then, at 60 ℃ of reaction 4h down; The electron donor L2 that adds the above-mentioned preparation of 4.0mmol at last reacts 12h down at 60 ℃.Reaction removes solvent under reduced pressure after finishing, and (3 * 20mL) washings, drying under reduced pressure obtains catalyzer 9 to product then with hexane.Ti content: 3.00wt-%.
The preparation of embodiment 10 catalyzer 10
Electron donor is:
The 1.0g Magnesium Chloride Anhydrous is joined in the 40mL THF (hereinafter to be referred as THF), stir 2h down at 60 ℃; The TiCl of Dropwise 5 .1mmol
4, at 60 ℃ of following reaction 4h, add ES70Y carrier after the above-mentioned thermal treatment of 1.0g then, at 60 ℃ of reaction 4h down; The electron donor L2 that adds the above-mentioned preparation of 4.0mmol at last reacts 12h down at 60 ℃.Reaction removes solvent under reduced pressure after finishing, and (3 * 20mL) washings, drying under reduced pressure obtains catalyzer 10 to product then with hexane.Ti content: .wt-%.
The preparation of embodiment 11 catalyzer 11
Electron donor is:
The 1.0g Magnesium Chloride Anhydrous is joined in the 40mL THF (hereinafter to be referred as THF), stir 2h down at 60 ℃; Drip the TiCl of 3.4mmol
4, at 60 ℃ of following reaction 4h, add ES70Y carrier after the above-mentioned thermal treatment of 1.0g then, at 60 ℃ of reaction 4h down; The electron donor L3 that adds the above-mentioned preparation of 4.0mmol at last reacts 12h down at 60 ℃.Reaction removes solvent under reduced pressure after finishing, and (3 * 20mL) washings, drying under reduced pressure obtains catalyzer 11 to product then with hexane.Ti content: 3.45wt-%.
The preparation electron donor of embodiment 12 catalyzer 12 is:
The 1.0g Magnesium Chloride Anhydrous is joined in the 40mL THF (hereinafter to be referred as THF), stir 2h down at 60 ℃; Drip the TiCl of 4.1mmol
4, at 60 ℃ of following reaction 4h, add ES70 carrier after the above-mentioned thermal treatment of 1.0g then, at 60 ℃ of reaction 4h down; The electron donor L3 that adds the above-mentioned preparation of 4.0mmol at last reacts 12h down at 60 ℃.Reaction removes solvent under reduced pressure after finishing, and (3 * 20mL) washings, drying under reduced pressure obtains catalyzer 12 to product then with hexane.Ti content: 3.wt-%.
The preparation of embodiment 13 catalyzer 13
Electron donor is:
The 1.0g Magnesium Chloride Anhydrous is joined in the 40mL THF (hereinafter to be referred as THF), stir 2h down at 60 ℃; The TiCl of Dropwise 5 .1mmol
4, at 60 ℃ of following reaction 4h, add ES70 carrier after the above-mentioned thermal treatment of 1.0g then, at 60 ℃ of reaction 4h down; The electron donor L3 that adds the above-mentioned preparation of 4.0mmol at last reacts 12h down at 60 ℃.Reaction removes solvent under reduced pressure after finishing, and (3 * 20mL) washings, drying under reduced pressure obtains catalyzer 13 to product then with hexane.Ti content: 4.wt-%.
Embodiment 14 ethene slurry polymerizations
The 0.5L stainless steel is stirred polymeric kettle use N
2Replace three times, ethene displacement twice just contains AlEt
3180mL hexane solution (0.015M) add in the still, start stirring (rotating speed=150rpm), and temperature in the kettle is preheating to about 60 ℃ with water bath with thermostatic control.At N
2Protection joins a certain amount of monomer (not having other common monomers during ethylene homo) altogether and 10mg catalyzer (with the above-mentioned hexane solution flushing of 20mL) in the polymeric kettle down successively, sheds the still internal pressure then; Treat that temperature in the kettle rises to about 80 ℃; Feed 0.2MPa hydrogen, feed ethylene gas again, make the still internal pressure reach 1.0MPa; After five minutes, mixing speed is risen to 250rpm.Bath temperature transfers to 85 ℃.Stop to feed ethene behind the polymerization 1h, with recirculated cooling water temperature in the kettle is reduced to below 50 ℃, gas in the emptying system and discharging obtain granulated polymer after the drying.
Concrete experiment condition, catalytic activity (g polymkeric substance/g catalyzer), polymericular weight M
w(g/mol), molecular weight distribution polymerization result data such as (PDI) are listed in table 1.
Table 1
| Catalyzer | Be total to monomer | Be total to monomer consumption (g) | Catalytic activity (g polymkeric substance/g catalyzer) | M w (10 4g/mol) | PDI | Be total to monomer insertion rate (mol-%) |
| 1 | - | 0 | 2200 | 36.2 | 2.1 | - |
| 1 | The 1-hexene | 10 | 1300 | 12.7 | 2.3 | 1.0 |
| 1 | The 1-hexene | 20 | 960 | 10.8 | 2.4 | 1.5 |
| 2 | - | 0 | 1500 | 12.1 | 3.1 | - |
| 3 | - | 0 | 1600 | 13.3 | 2.2 | - |
| 4 | The 1-hexene | 10 | 1700 | 9.4 | 2.5 | 2.2 |
| 5 | - | 0 | 2300 | 11.3 | 2.1 | - |
| 6 | - | 0 | 1200 | 14.6 | 2.3 | - |
| 7 | - | 0 | 980 | 15.6 | 2.6 | |
| 8 | - | 0 | 530 | 27.1 | 2.3 | |
| 9 | - | 0 | 720 | 20.5 | 2.6 | |
| 10 | - | 0 | 1900 | 16.7 | 2.2 | - |
| 10 | The 1-hexene | 20 | 1500 | 11.2 | 2.4 | 1.9 |
| 11 | - | 0 | 2200 | 14.7 | 2.7 | |
| 12 | - | 0 | 1700 | 12.3 | 2.4 | |
| 13 | - | 0 | 1300 | 19.4 | 2.1 |
Embodiment 15 vapour phase polymerizations
Polymeric kettle is used N
2Replace three times, ethene displacement twice, and carry out water cycle with thermostatic water-circulator bath temperature in the kettle is preheating to about 60 ℃.At N
2Protection down, with 30mg catalyzer, 10g sodium-chlor as nucleator and 2.1mLAlEt
3(0.88M hexane solution) joins in the feed pot, and shake well also is connected feed pot on the polymerization system.Use N
2Gas is pressed into the mixture in the feed pot in the polymeric kettle, treats that temperature in the kettle rises to about 70 ℃, feeds ethylene gas (H
2Telomerize the fashionable H that feeds earlier
2), make the interior total pressure of still reach 2.0, under the copolymerization situation, after polymerization begins 20min, lead to comonomer steam in certain pressure.Polymerization 10h stops to feed ethene, with recirculated cooling water temperature in the kettle is reduced to below 50 ℃, and gas in the emptying system and discharging obtain granulated polymer after the drying.
Concrete experiment condition, catalytic activity (g polymkeric substance/g catalyzer), polymericular weight M
w(g/mol), molecular weight distribution polymerization result data such as (PDI) are listed in table 2.
Table 2
| Catalyzer | Be total to monomer | Be total to monomer consumption (g) | Catalytic activity (g polymkeric substance/g catalyzer) | M w (10 4 g/mol) | PDI | Be total to monomer insertion rate (mol-%) |
| 1 | - | 0 | 3000 | 39.2 | 2.1 | - |
| 1 | The 1-hexene | 60 | 7000 | 17.6 | 3.2 | 1.6 |
| 5 | - | 0 | 6800 | 56.3 | 2.1 | - |
| 5 | The 1-hexene | 30 | 10 | 19.8 | 2.6 | 1.3 |
| 6 | - | 3 | 38.7 | 2.3 | ||
| 7 | - | 50 | 45.3 | 2.3 |
Claims (17)
1. the Z-N olefin polymerization catalysis that has single active center's character is characterized in that described catalyzer adopts following preparation method to obtain:
The 1.0g Magnesium Chloride Anhydrous is joined in the 40mL THF, stir 2h down at 60 ℃; Drip the TiCl of 3.4mmol
4, at 60 ℃ of following reaction 4h, add the carrier ES70 after the 1.0g thermal treatment then, at 60 ℃ of reaction 4h down; The electron donor L1 that adds 4.0mmol at last reacts 12h down at 60 ℃; Reaction removes solvent under reduced pressure after finishing, and product is with hexane 3 * 20mL washing, and drying under reduced pressure obtains catalyzer then;
Wherein said electron donor L1 is a structure as follows:
The thermal treatment of ES70 is to adopt following manner: get the roasting under nitrogen atmosphere of ES70 type silica gel; Its roasting condition is: in 200 ℃ of processing 2h, be warming up to 400 ℃ then and handle 2, handle 4h, naturally cooling under nitrogen atmosphere at 600 ℃ again.
2. the Z-N olefin polymerization catalysis that has single active center's character is characterized in that described catalyzer adopts following preparation method to obtain:
The 1.0g Magnesium Chloride Anhydrous is joined in the 40mL THF, stir 2h down at 60 ℃; Drip the TiCl of 3.4mmol
4, at 60 ℃ of following reaction 4h, add ES70 carrier after the 1.0g thermal treatment then, at 60 ℃ of reaction 4h down; Add 4.0mmol electron donor L2 at last, react 12h down at 60 ℃; Reaction removes solvent under reduced pressure after finishing, and product is with hexane 3 * 20mL washing, and drying under reduced pressure obtains then; The heat treatment mode of ES70 carrier is said with claim 1;
Described electron donor is a following structures:
3. the Z-N olefin polymerization catalysis that has single active center's character is characterized in that described catalyzer adopts following preparation method to obtain:
The 1.0g Magnesium Chloride Anhydrous is joined in the 40mL THF, stir 2h down at 60 ℃; Drip the TiCl of 3.4mmol
4, at 60 ℃ of following reaction 4h, add the ES70 carrier after the 1.0g thermal treatment then, at 60 ℃ of reaction 4h down; Add 4.0mmol electron donor L3 at last, react 12h down at 60 ℃; Reaction removes solvent under reduced pressure after finishing, and product is with hexane 3 * 20mL washing, and drying under reduced pressure obtains catalyzer then;
Wherein the heat treatment mode of ES70 carrier is said with claim 1;
Described electron donor is a following structures:
4. the Z-N olefin polymerization catalysis that has single active center's character is characterized in that described catalyzer adopts following preparation method to obtain:
The 1.0g Magnesium Chloride Anhydrous is joined in the 40mL THF, stir 2h down at 60 ℃; Drip the TiCl of 3.4mmol
4, at 60 ℃ of following reaction 4h, add ES70Y carrier after the 1.0g thermal treatment then, at 60 ℃ of reaction 4h down; Add 4.0mmol electron donor L1 at last, react 12h down at 60 ℃; Reaction removes solvent under reduced pressure after finishing, and product is with hexane 3 * 20mL washing, and drying under reduced pressure obtains then; Wherein the heat treatment mode of ES70Y carrier is said with claim 1 with the structure of the processing of ES70 described in the claim 1, L1.
5. the Z-N olefin polymerization catalysis that has single active center's character is characterized in that described catalyzer adopts following preparation method to obtain:
The 1.5g Magnesium Chloride Anhydrous is joined in the 60mL THF, stir 2h down at 60 ℃; Drip the TiCl of 3.4mmol
4, at 60 ℃ of following reaction 4h, add ES70 carrier after the 1.0g thermal treatment then, at 60 ℃ of reaction 4h down; Add 4.0mmol electron donor L1 at last, react 12h down at 60 ℃; Reaction removes solvent under reduced pressure after finishing, and product is with hexane 3 * 20mL washing, and drying under reduced pressure obtains then; Wherein the structure of the heat treatment mode of ES70 carrier, L1 is said with claim 1.
6. the Z-N olefin polymerization catalysis that has single active center's character is characterized in that described catalyzer adopts following preparation method to obtain:
The 1.0g Magnesium Chloride Anhydrous is joined in the 40mL THF, stir 2h down at 60 ℃; Drip the TiCl of 3.4mmol
4, at 60 ℃ of following reaction 4h, add ES757 carrier after the 1.0g thermal treatment then, at 60 ℃ of reaction 4h down; Add 4.0mmol electron donor L1 at last, react 12h down at 60 ℃; Reaction removes solvent under reduced pressure after finishing, and product is with hexane 3 * 20mL washing, and drying under reduced pressure obtains then; Wherein the heat treatment mode of ES757 carrier is with the processing of ES70 described in the claim 1; The structure of L1 is said with claim 1.
7. the Z-N olefin polymerization catalysis that has single active center's character is characterized in that described catalyzer adopts following preparation method to obtain:
The 1.0g Magnesium Chloride Anhydrous is joined in the 40mL THF, stir 2h down at 60 ℃; Drip the TiCl of 4.1mmol
4, at 60 ℃ of following reaction 4h, add ES70 carrier after the 1.0g thermal treatment then, at 60 ℃ of reaction 4h down; Add 4.0mmol electron donor L1 at last, react 12h down at 60 ℃; Reaction removes solvent under reduced pressure after finishing, and product is with hexane 3 * 20mL washing, and drying under reduced pressure obtains then; Wherein the structure of the heat treatment mode of ES70 carrier, L1 is said with claim 1.
8. the Z-N olefin polymerization catalysis that has single active center's character is characterized in that described catalyzer adopts following preparation method to obtain:
The 1.0g Magnesium Chloride Anhydrous is joined in the 40mL THF, stir 2h down at 60 ℃; Drip the TiCl of 3.4mmol
4, at 60 ℃ of following reaction 4h, add ES70Y carrier after the 1.0g thermal treatment then, at 60 ℃ of reaction 4h down; Add 4.0mmol electron donor L2 at last, react 12h down at 60 ℃; Reaction removes solvent under reduced pressure after finishing, and product is with hexane 3 * 20mL washing, and drying under reduced pressure obtains then; Wherein the heat treatment mode of ES70Y carrier is with ES70 described in the claim 1; Structure such as the claim 2 of L2 are said.
9. the Z-N olefin polymerization catalysis that has single active center's character is characterized in that described catalyzer adopts following preparation method to obtain:
The 1.0g Magnesium Chloride Anhydrous is joined in the 40mL THF, stir 2h down at 60 ℃; Drip the TiCl of 3.4mmol
4, at 60 ℃ of following reaction 4h, add ES757 carrier after the 1.0g thermal treatment then, at 60 ℃ of reaction 4h down; Add 4.0mmol electron donor L2 at last, react 12h down at 60 ℃; Reaction removes solvent under reduced pressure after finishing, and product is with hexane 3 * 20mL washing, and drying under reduced pressure obtains then; Wherein the heat treatment mode of ES757 is with the processing of ES70 described in the claim 1; Structure such as the claim 2 of L2 are said.
10. the Z-N olefin polymerization catalysis that has single active center's character is characterized in that described catalyzer adopts following preparation method to obtain:
The 1.0g Magnesium Chloride Anhydrous is joined in the 40mL THF, stir 2h down at 60 ℃; The TiCl of Dropwise 5 .1mmol
4, at 60 ℃ of following reaction 4h, add ES70Y carrier after the 1.0g thermal treatment then, at 60 ℃ of reaction 4h down; Add 4.0mmol electron donor L2 at last, react 12h down at 60 ℃; Reaction removes solvent under reduced pressure after finishing, and product is with hexane 3 * 20mL washing, and drying under reduced pressure obtains then; Wherein the heat treatment mode of ES70Y is with the processing of ES70 described in the claim 1; Structure such as the claim 2 of L2 are said.
11. have the Z-N olefin polymerization catalysis of single active center's character, it is characterized in that described catalyzer adopts following preparation method to obtain:
The 1.0g Magnesium Chloride Anhydrous is joined in the 40mL THF, stir 2h down at 60 ℃; Drip the TiCl of 3.4mmol
4, at 60 ℃ of following reaction 4h, add ES70Y carrier after the 1.0g thermal treatment then, at 60 ℃ of reaction 4h down; Add 4.0mmol electron donor L3 at last, react 12h down at 60 ℃; Reaction removes solvent under reduced pressure after finishing, and product is with hexane 3 * 20mL washing, and drying under reduced pressure obtains then; Wherein the heat treatment mode of ES70Y is with the processing of ES70 described in the claim 1; Structure such as the claim 3 of L3 are said.
12. have the Z-N olefin polymerization catalysis of single active center's character, it is characterized in that described catalyzer adopts following preparation method to obtain:
The 1.0g Magnesium Chloride Anhydrous is joined in the 40mL THF, stir 2h down at 60 ℃; Drip the TiCl of 4.1mmol
4, at 60 ℃ of following reaction 4h, add ES70 carrier after the 1.0g thermal treatment then, at 60 ℃ of reaction 4h down; Add 4.0mmol electron donor L3 at last, react 12h down at 60 ℃; Reaction removes solvent under reduced pressure after finishing, and product is with hexane 3 * 20mL washing, and drying under reduced pressure obtains then; Wherein the heat treatment mode of ES70 is with described in the claim 1; Structure such as the claim 3 of L3 are said.
13. have the Z-N olefin polymerization catalysis of single active center's character, it is characterized in that described catalyzer adopts following preparation method to obtain:
The 1.0g Magnesium Chloride Anhydrous is joined in the 40mL THF, stir 2h down at 60 ℃; The TiCl of Dropwise 5 .1mmol
4, at 60 ℃ of following reaction 4h, add ES70 carrier after the 1.0g thermal treatment then, at 60 ℃ of reaction 4h down; Add 4.0mmol electron donor L3 at last, react 12h down at 60 ℃; Reaction removes solvent under reduced pressure after finishing, and product is with hexane 3 * 20mL washing, and drying under reduced pressure obtains then; Wherein the heat treatment mode of ES70 is with described in the claim 1; The structure of L3 is said with claim 3.
14. to the described purposes of one of claim 13, it is characterized in that adopting this catalyzer to be used for olefinic polymerization with Z-N olefin polymerization catalysis of single active center's character like claim 1.
15. the purposes with Z-N olefin polymerization catalysis of single active center's character as claimed in claim 14; It is characterized in that described polymerization is a promotor with aluminum alkyls, alkylaluminoxane, promotor is selected from triethyl aluminum, triisobutyl aluminium, aluminium diethyl monochloride, three hexyl aluminium or their mixture; The Al/Ti mol ratio is 10-3000 during polymerization.
16. the purposes with Z-N olefin polymerization catalysis of single active center's character as claimed in claim 14 is characterized in that described catalyzer is used for the olefin polymer of synthetic molecular weight distribution 1.5-3.8.
17. the purposes with Z-N olefin polymerization catalysis of single active center's character as claimed in claim 14 is characterized in that described polymerization can be slurry polymerization or vapour phase polymerization; Wherein, Described slurry polymerization carries out under overcritical or subcritical state; The polymerization total pressure is that 0.1-10.0MPa, hydrogen pressure are 0-1.0MPa, polymerization temperature 50-120 ℃, and medium is propane, Trimethylmethane, hexane or solvent oil, and polymerization reactor is stirring tank or annular-pipe reactor; Described vapour phase polymerization is carried out in gas fluidized bed or gas phase stirring tank, and pressure is that 1.0-10.0MPa, polymerization temperature are 40-100 ℃.
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| CN1884253A (en) * | 2006-05-22 | 2006-12-27 | 中国科学院上海有机化学研究所 | Organic compound containing heteroatoms and its use in Zigler-Natta catalyst |
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| CN1884253A (en) * | 2006-05-22 | 2006-12-27 | 中国科学院上海有机化学研究所 | Organic compound containing heteroatoms and its use in Zigler-Natta catalyst |
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