CN1884311A - Mono-active center Ziegler-Natta catalyst for olefinic polymerization - Google Patents
Mono-active center Ziegler-Natta catalyst for olefinic polymerization Download PDFInfo
- Publication number
- CN1884311A CN1884311A CN 200610026765 CN200610026765A CN1884311A CN 1884311 A CN1884311 A CN 1884311A CN 200610026765 CN200610026765 CN 200610026765 CN 200610026765 A CN200610026765 A CN 200610026765A CN 1884311 A CN1884311 A CN 1884311A
- Authority
- CN
- China
- Prior art keywords
- alkyl
- group
- compound
- magnesium
- replacement
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
The invention relates to a new catalyst for single active central Ziegler-Natta alkene polymerization. Said catalyst takes salicylal containing dentate or substituted salicylal derivatives as electrons, and is prepared by adding pretreated carrier, metallic compound and electrons into magnesium compound/ tetrahydrofuran solution. The catalyst can produce ethane homopolymer and copolymer with narrow molecular weight distribution (1.6-3.8) and even comonomer distribution, with high activity and under action of adjuvant catalyst of alkyl aluminium and alkyl aluminoxanes. The ethane polymerization, homopolymerization or combined polymerization of ethane and 1- olefin, ring olefin and polar monomer through slurry method or gas phase method by using said catalyst can be realized.
Description
Technical field
The invention relates to the novel single active center of class Z-N (Ziegler-Natta) olefin polymerization catalysis.This catalyzer has used the salicylaldehyde derivatives of the salicylic aldehyde that contains coordinating group or replacement as organic electron donor.Under the effect of promotor, utilize the copolymerization of equal polymerization that this catalyzer can catalyzed ethylene or ethene and alpha-olefin to obtain the ethene polymers of controllable structure.
Background technology
Along with the fast development of polyolefin industry, the production of high-performance poly olefin material more and more is subjected to people's extensive attention.Present international research thinks that the production of high-performance poly olefin material mainly can realize by 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 class catalyzer.Ziegler-Natta catalyst is since finding the fifties in last century, brought into play important effect in polyolefin field, but because the characteristics in its many active centre, cause the particularly poly structure of polymkeric substance to 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.By 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 molecular weight distribution 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 CN1510055A etc.But in general, utilize above-mentioned Preparation of Catalyst molecular weight distribution broad, still remain to be improved.For example, patent US 5459116 has reported by making the magnesium solution that contains ester (having at least one hydroxyl as electron donor) and the method for titanium compound prepared in reaction solids containing titanium catalyzer, this catalyzer has very high catalytic activity, but the molecular weight distribution of polymkeric substance wide (PDI is 7.38～10.04).It is the carrier model Ziegler-Natta ethylene rolymerization catalyst of electron donor preparation that Chinese patent CN1510055A has reported with a small amount of alcohol, has only an embodiment to provide poly molecular weight distribution data, and PDI is 4.79, and activity of such catalysts is not high.
Patent WO 2004072121A2, US 6734134B1, WO 2001092345 (CN 1189487C), WO200238624 (CN1478102A) have reported that respectively several classes contain amine or contain alcohols simultaneously, have the ester class of hydroxyl and the carrier model Ziegler-Natta catalyst of alkoxy-silicon compound, can be with highly active catalytic ethylene homo and copolymerization, narrow molecular weight distribution (PDI is 3.6～5.3), but do not provide the information of comonomer distribution.Patent US 5,106, and 807 and 4,330,649 by coming the activity of control catalyst and the molecular weight of polymkeric substance in system to adding ester compound; CN1189487C (PCT/KR2000/001549) provides a kind of preparation method who prepares the Alathon and the multipolymer of narrow molecular weight distributions, and molecular weight distribution is 3.6-4.3; Terano has reported the homogeneous phase Ziegle-Natta catalyzer that utilizes ethylene-propylene-diene elastomer (EPDM) load and surface-functionalized silicon dioxide carried catalyst vinyl polymerization, obtain the polymkeric substance (1.6-30) that different molecular weight distributes by changing promotor, this is with Ziegler-Natta catalyst the narrowest resulting molecular weight distribution.(Terano, M., Catalysis Commun.2003,4,657-662; Macromol.Chem.Phys.1998,199,1765), but the activity of polymkeric substance or molecular weight significantly descend.The chemical composition that need add during the method for preparing catalyzer is many, preparation process is numerous and diverse, and catalytic species still belongs to the Ziegler-Natta catalyst with many active centre character.
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 molecular weight distribution by 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 be very restricted.
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 yet there are no report polymer architecture and performance.
Summary of the invention
The purpose of this invention is to provide a kind of single active center's Z-N (Ziegler-Natta) olefin polymerization catalysis with high catalytic activity.
The object of the invention also provides the preparation method of above-mentioned single active center Ziegler-Natta catalyst.
Another object of the present invention has provided the Ziegler-Natta catalyst purposes of utilizing above-mentioned single active center, in particular for the olefin polymer of synthetic molecular weight narrowly distributing (1.5-3.8).
The present invention contains the salicylic aldehyde of coordinating group or the salicylaldehyde derivatives of replacement prepares novel single active center Z-N (Ziegler-Natta) olefin polymerization catalysis as novel organic electron donor by introducing.Under the promotor effect, this single active center Z-N (Ziegler-Natta) olefin polymerization catalysis can highly active catalysis in olefine polymerization, and can control polyolefinic structure and comprise molecular weight and molecular weight distribution; Described alkene is ethene, 1-alkene, cycloolefin and derivative thereof, various olefin(e) acid and derivative, enol and derivative, 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 derivative of polar group.
A class single active center Z-N olefin polymerization catalysis provided by the invention is to be obtained by the salicylaldehyde derivatives I of salicylic aldehyde that contains coordinating group or replacement, metallic compound, magnesium compound and carrier prepared in reaction; The mol ratio of salicylaldehyde derivatives I, metallic compound and the magnesium compound of described salicylic aldehyde that contains coordinating group or replacement is 0.001～50: 1: 1～300; The weight ratio of magnesium compound and carrier 1: 0.5～20;
The described salicylic aldehyde that contains coordinating group or the salicylaldehyde derivatives I of replacement have following structural formula:
Wherein:
→: refer to singly-bound or two key;
R
1, R
2, R
3, R
4, R
5: hydrogen, C
1～C
30Alkyl or halogen atom, above-mentioned group is identical or different to each other, wherein when above-mentioned group is respectively alkyl, adjacent group becomes ring or Cheng Jiancheng ring not each other in key;
R
6And R
7Can be respectively: C
1～C
30Alkyl, C
5～C
50Aromatic group and the aromatic group of replacement, and when N atom and adjacent carbons are formed imine group, have only a substituent group R on the nitrogen-atoms
6Or R
7
Z: oxy radical OR
8, sulfur-containing group SR
9, nitrogen-containing group NR
10R
11, phosphorus-containing groups PR
12R
13Or P (O) R
14R
15, or contain the SeR of seleno group
16
R
8, R
9, R
10, R
11, R
12, R
13, R
14, R
15, R
16Be hydrogen, C
1～C
30Alkyl, C
5～C
50Aromatic group and the aromatic group of replacement;
G: be bridged group with following structure I I, III, IV or V
Wherein:
R
17, R
18, R
19And R
20Be respectively hydrogen, C
1～C
30Alkyl or the alkyl of replacement, adjacent group R
17And R
18, R
19And R
20, and R
17And R
19Become ring or Cheng Huan not;
R
21And R
22Be respectively hydrogen, C
1～C
30Alkyl or the alkyl of replacement, R
21And R
22Be independent substituent group or R
21And R
22Form aromatic nucleus together with two keys;
R
23, R
24, R
25, R
26, R
27, R
28, R
31And R
32Be respectively hydrogen, C
1～C
30Alkyl or the alkyl of replacement; Adjacent group Cheng Jiancheng ring or Cheng Jiancheng ring not;
R
29And R
30Be respectively hydrogen, C
1～C
30Alkyl or the alkyl of replacement, and R
29And R
30Be independent substituent group or R
21And R
22Form aromatic nucleus together with two keys;
Described aromatic group is meant phenyl, naphthyl, anthryl or phenanthryl;
The alkyl of described replacement is meant and contains silica-based SiR on the alkyl
33Or halogen;
The aromatic group of described replacement is that aromatic group contains alkyl, silica-based SiR
33Or halogen;
Described halogen is fluorine, chlorine, bromine or iodine;
Described alkyl comprises alkyl, alkene and alkynes base;
R
33Be meant C
1～C
30Alkyl;
The molecular formula of described metallic compound is MX
nY
m,
Wherein M is meant Ti, Zr, Cr or V;
X is meant chlorine or bromine;
Y is meant OR
34, N (R
35)
2, R
36, THF, Et
2O, wherein R
34, R
35Be meant C
1-C
6Alkyl; R
36Be 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 electric neutrality for n and m sum;
Described 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 by the pyrohydrolysis process by gaseous metal oxide compound or silicon compound, or organic high molecular polymer.
The preparation method of the Ziegler-Natta of single active center olefin polymerization catalysis of 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 100～1000 ℃ of following dryings of both mixtures or roasting 1～24 hour;
2) under room temperature to 100 ℃ condition, magnesium compound is dissolved in forms solution in the tetrahydrofuran (THF); In above-mentioned solution, add carrier described in the step 1, metallic compound successively and contain the salicylic aldehyde of coordinating group or the salicylaldehyde derivatives I of replacement, under room temperature to 100 ℃ condition, reacted 2～48 hours, remove solvent, washing and vacuum-drying; Preferable reaction temperature is 50～70 ℃; The preferred reaction time is 4～24 hours.
Wherein, described solid as carrier is for being selected from the 2nd, 4,13, the oxide compound of 14 group elements is at interior inorganic oxide and oxidation mixture and mixed oxide, the oxidation material for preparing by 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 polystyrene, polyethylene etc.The preferred silica gel of described carrier, its particle diameter are 1～50 μ m, specific surface area 100～300m
2/ g, pore volume 0.5～3mL/g, mean pore size 10～50nm;
Described 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 Ti, Zr, Cr or V; X is meant chlorine or bromine; Y is meant OR
34, N (R
35)
2, R
36, THF, Et
2O, wherein R
34, R
35Be meant C
1-C
6Alkyl; R
36Be 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 electric neutrality 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 tetrahydrofuran (THF) is 20～100mL tetrahydrofuran (THF)/gram magnesium compound, preferred 40～80mL tetrahydrofuran (THF)/gram magnesium compound;
The mass ratio of magnesium compound and carrier 1: 0.5～20; Preferred 1: 0.5～10;
The mol ratio of magnesium compound metallizing thing is 1～300: 1, preferred 1～100: 1; More preferably 1～40: 1;
The mol ratio that contains heteroatomic organic compound metallizing thing is 0.001～50: 1, preferred 0.01～20: 1, more preferably 0.1～10: 1.
Employed all kinds of SOLVENTS all needs the strict deoxygenation that dewaters to handle among the preparation method of the novel Ziegler-Natta catalyst of single active center of the present invention, and all operations all carries out under the condition of anhydrous and oxygen-free, in the following embodiments explanation no longer in addition.
Single active center of the present invention Ziegler-Natta catalyst 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 20～3000, 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 cyclopentenes, tetrahydrobenzene, the norbornylene that the alkyl replacement is arranged.
The class Ziegler-Natta of novel single active center olefin polymerization catalysis 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 50～120 ℃ of 0～1.0MPa, polymerization temperatures 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 the equal polymerization of this single active center's Ziegler-Natta catalyst catalyzed ethylene, can guarantee under the highly active prerequisite, well the molecular weight of controlling polymers and molecular weight distribution;
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 molecular weight distribution (PDI=M
w/ M
n) utilize Waters AllianceGPC2000 1,2, under 135 ℃, be that standard specimen is measured in 4 trichlorobenzene (flow velocity 1.0mL/min) with the polystyrene.
Polymkeric substance
13C-NMR composes on Varian XL-300MHz nuclear magnetic resonance analyser with D
4-o-dichlorobenzene is a solvent, measures down at 110 ℃.Monomer insertion rate is according to document (J C Randall, JMS-Rev.Maromol.Chem.Phys.1989, C29 (2﹠amp altogether; 3), method 201-317) calculates.
The synthetic method reference of organic electron donor: patent 01126323.7,02110844.7, Hu et.al., Organometallics 2004,23,1684-1688; Wang, C.et.al.Macromol.Rapid Commun.2005,26,1609-1614.
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:
Electron donor is:
(1) thermal treatment of carrier
Get ES70 type silica gel (Ineos company product) roasting under nitrogen atmosphere.Its roasting condition is: in 200 ℃ of processing 2h, be warming up to 400 ℃ then and handle 4h, naturally cooling under nitrogen atmosphere.Be designated as the ES70 carrier.
(2) preparation of catalyzer 1
The 1.0g Magnesium Chloride Anhydrous is joined in the 40mL tetrahydrofuran (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: 3.20wt-%, Mg content: 3.74wt-%.
The preparation of embodiment 2 catalyzer 2:
The 1.0g Magnesium Chloride Anhydrous is joined in the 40mL tetrahydrofuran (THF) (hereinafter to be referred as THF), stir 2h down at 60 ℃; Drip the TiCl of 15mmol
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 2 to product then with hexane.Ti content: 5.23wt-%
The preparation of embodiment 3 catalyzer 3:
The 1.0g Magnesium Chloride Anhydrous is joined in the 40mL tetrahydrofuran (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 10mmol 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 with hexane.Ti content: 2.60wt-%
The preparation of embodiment 4 catalyzer 4:
Electron donor is:
The 1.0g Magnesium Chloride Anhydrous is joined in the 40mL tetrahydrofuran (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 ES70X 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 4 to product then with hexane.Ti content: 3.50wt-%
The preparation of embodiment 5 catalyzer 5:
Electron donor is:
The 1.0g Magnesium Chloride Anhydrous is joined in the 40mL tetrahydrofuran (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 under 60 ℃ of C.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: 3.81wt-%
The preparation of embodiment 6 catalyzer 6:
Electron donor is:
The 1.0g Magnesium Chloride Anhydrous is joined in the 40mL tetrahydrofuran (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 molecular sieve (MCM41) carrier after the above-mentioned thermal treatment of 1.0g then, at 60 ℃ of reaction 4h down; The electron donor L4 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 6 to product then with hexane.
The preparation of embodiment 7 catalyzer 7:
Electron donor is:
The 1.0g Magnesium Chloride Anhydrous is joined in the 40mL tetrahydrofuran (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 L5 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.
The preparation of embodiment 8 catalyzer 8:
Electron donor is:
The 1.0g Magnesium Chloride Anhydrous is joined in the 40mL tetrahydrofuran (THF) (hereinafter to be referred as THF), stir 2h down at 60 ℃; Drip the TiCl of 3.4mmol
4, react 4h down at 60 ℃, add the above-mentioned thermal treatment rear oxidation of 1.0g aluminium (neutrality) carrier then, react 4h down at 60 ℃; The electron donor L6 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: 1.60wt-%.
The preparation of embodiment 9 catalyzer 9:
Electron donor is:
The 1.0g Magnesium Chloride Anhydrous is joined in the 40mL tetrahydrofuran (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 polynite (MMT) carrier after the above-mentioned thermal treatment of 1.0g then, at 60 ℃ of reaction 4h down; The electron donor L7 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: 2.74wt-%.
The preparation of embodiment 10 catalyzer 10:
Electron donor is:
The 1.0g Magnesium Chloride Anhydrous is joined in the 40mL tetrahydrofuran (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 L8 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: 3.36wt-%.
The preparation of embodiment 11 catalyzer 11:
Electron donor is:
The 1.0g Magnesium Chloride Anhydrous is joined in the 40mL tetrahydrofuran (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 L9 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: 3.20wt-%.
The preparation of embodiment 12 catalyzer 12:
Electron donor is:
The 1.0g Magnesium Chloride Anhydrous is joined in the 40mL tetrahydrofuran (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 L10 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 13 catalyzer 13:
Electron donor is:
The 1.0g Magnesium Chloride Anhydrous is joined in the 40mL tetrahydrofuran (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 L11 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: 3.22wt-%.
The preparation of embodiment 14 catalyzer 14:
Electron donor is:
The 1.0g Magnesium Chloride Anhydrous is joined in the 40mL tetrahydrofuran (THF) (hereinafter to be referred as THF), stir 2h down at 60 ℃; Drip the TiCl of 3.4mmol
4, react 4h down at 60 ℃, add the spherical crosslinked polystyrene of 1.0g then, react 4h down at 60 ℃; The electron donor L12 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 14 to product then with hexane.Ti content: 1.53wt-%.
The preparation of embodiment 15 catalyzer 15:
Electron donor is:
The 1.0g Magnesium Chloride Anhydrous is joined in the 40mL tetrahydrofuran (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 L13 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 15 to product then with hexane.Ti content: 3.00wt-%.
The preparation of embodiment 16 catalyzer 16:
Electron donor is:
The 1.0g Magnesium Chloride Anhydrous is joined in the 40mL tetrahydrofuran (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 L14 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 16 to product then with hexane.Ti content: 2.65wt-%.
The preparation of embodiment 17 catalyzer 17:
Electron donor is:
The 1.0g Magnesium Chloride Anhydrous is joined in the 40mL tetrahydrofuran (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 L15 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 17 to product then with hexane.Ti content: 3.45wt-%.
The preparation of embodiment 18 catalyzer 18:
Electron donor L16's is synthetic:
According to as Wang, C.et.al.Macromol.Rapid Commun.2005,26, it is corresponding 2 that the method described in the 1609-1614 has, and the 4-di-tert-butyl salicylaldehyde is synthetic with corresponding amine.
1H?NMR(300MHz，CDCl
3)：δ13.63(s，1H)；8.38(s，1H)；7.38(d，1H)；7.10(d，1H)；3.80(t，2H)；2.83(t，2H)；2.16(s，3H)；1.44(s，9H)；1.31(s，9H)。
The 1.0g Magnesium Chloride Anhydrous is joined in the 40mL tetrahydrofuran (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 L16 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 18 to product then with hexane.Ti content: 3.52wt-%.
The preparation of embodiment 19 catalyzer 19
Electron donor L17's is synthetic:
According to as Wang, C.et.al.Macromol.Rapid Commun.2005,26, it is corresponding 2 that the method described in the 1609-1614 has, and the 4-di-tert-butyl salicylaldehyde is synthetic with corresponding amine.
1H?NMR(300MHz，CDCl
3)：δ13.80(s，1H)；8.38(s，1H)；7.37(d，2H)；7.08(d，2H)；3.69(t，3H)；2.93(m，1H)；2.62(d，2H)；1.99(pent，2H)；1.44(s，9H)；1.31(s，9H)；1.28(s，3H)；1.26(s，3H)。
The preparation of catalyzer 19:
The 1.0g Magnesium Chloride Anhydrous is joined in the 40mL tetrahydrofuran (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 L17 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 19 to product then with hexane.Ti content: 3.50wt-%.
The preparation of embodiment 20 catalyzer 20
Electron donor L18's is synthetic:
According to Wang, C.et.al.Macromol.Rapid Commun.2005,26, method has 2 among the 1609-1614, and the 4-di-tert-butyl salicylaldehyde obtains with corresponding anils condensation.
Ultimate analysis (theoretical value): C, 77.63 (77.91), H, 7.69 (7.71), N, 3.30 (3.25)
1H?NMR(300MHz，CDCl
3)：δ13.35(s，1H)；8.67(s，1H)；7.41-6.98(m，10H)；2.35(s，3H)；1.41(s，9H)；1.31(s，9H)。
The preparation of catalyzer 20:
The 1.0g Magnesium Chloride Anhydrous is joined in the 40mL tetrahydrofuran (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 L16 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 19 to product then with hexane.Ti content: 3.11wt-%.
Embodiment 21 ethene slurry polymerizations
The 0.5L stainless steel is stirred polymeric kettle 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 down; successively 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) are joined in the polymeric kettle; shed the still internal pressure then; treat that temperature in the kettle rises to about 80 ℃; feed ethylene gas; 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 | 2100 | 36.2 | 2.1 | - |
| 1 | The 1-hexene | 10 | 1100 | 12.7 | 2.3 | 1.0 |
| 1 | The 1-hexene | 20 | 930 | 10.8 | 2.4 | 1.5 |
| 2 | - | 0 | 1700 | 12.1 | 3.1 | 0.5 |
| 3 | - | 0 | 1200 | 13.3 | 2.2 | 0.8 |
| 4 | The 1-hexene | 10 | 1900 | 9.4 | 2.5 | 2.2 |
| 5 | - | 0 | 2300 | - | - | - |
| 6 | - | 0 | 1200 | - | - | - |
| 7 | - | 0 | 980 | 15.6 | 2.6 | |
| 8 | - | 0 | 530 | 27.1 | 2.3 | |
| 9 | - | 0 | 720 | 20.5 | 2.6 | |
| 10 | - | 0 | 2000 | 16.7 | 2.2 | - |
| 10 | The 1-hexene | 20 | 1300 | 11.2 | 2.4 | 1.9 |
| 11 | - | 0 | 2300 | 14.7 | 2.7 | - |
| 12 | - | 0 | 1900 | 12.3 | 2.4 | - |
| 13 | - | 0 | 1200 | 19.4 | 2.1 | - |
| 14 | - | 0 | 900 | |||
| 15 | - | 0 | 1300 | |||
| 16 | - | 0 | 1200 | |||
| 17 | - | 0 | 1200 | |||
| 18 | - | 0 | 500 | |||
| 19 | - | 0 | 600 | |||
| 20 | - | 0 | 1600 |
Embodiment 22 vapour phase polymerizations
The 2L stainless steel is stirred polymeric kettle N
2Replace three times, ethene displacement twice adds the 400g hexane in the still, starts stirring (rotating speed=150rpm), and carry out water cycle with thermostatic water-circulator bath temperature in the kettle is preheating to about 60 ℃.At N
2Under the protection, with 30mg catalyzer, 200g hexane 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, sheds the still internal pressure then, 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 0.8MPa, after five minutes, mixing speed is risen to 250rpm, bath temperature transfers to 85 ℃.Under the copolymerization situation, after polymerization begins 20min, add a certain amount of comonomer.Stop to feed ethene behind the polymerization 2h, 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 2.
Table 2
| 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 | 18000 | 36.2 | 2.1 | - |
| 1 | The 1-hexene | 30 | 9000 | 31.3 | 2.3 | 1.2 |
| 1 | The 1-hexene | 60 | 6000 | 17.6 | 3.2 | ？ |
| 10 | The 1-hexene | 30 | 10000 | 19.8 | 2.6 | ？ |
Claims (9)
1, one class single active center ziegler-natta olefin polymerization catalysis, it is characterized in that this catalyzer with the salicylaldehyde derivatives of the salicylic aldehyde that contains coordinating group or replacement as organic electron donor; This catalyzer is obtained by salicylaldehyde derivatives, metallic compound, magnesium compound and the carrier prepared in reaction of salicylic aldehyde that contains coordinating group or replacement; The mol ratio of described organic electron donor, metallic compound and magnesium compound is 0.001～50: 1: 1～300; The weight ratio of magnesium compound and carrier 1: 0.5～20;
Describedly contain the salicylic aldehyde of coordinating group or the salicylaldehyde derivatives of replacement has following structural formula:
Wherein:
→: refer to singly-bound or two key;
R
1, R
2, R
3, R
4, R
5: hydrogen, C
1～C
30Alkyl or halogen atom, above-mentioned group is identical or different to each other, wherein when above-mentioned group is respectively alkyl, adjacent group becomes ring or Cheng Jiancheng ring not each other in key;
R
6And R
7Can be respectively: C
1～C
30Alkyl, C
5～C
50Aromatic group and the aromatic group of replacement, and when N atom and adjacent carbons are formed imine group, have only a substituent group R on the nitrogen-atoms
6Or R
7
Z: oxy radical OR
8, sulfur-containing group SR
9, nitrogen-containing group NR
10R
11, phosphorus-containing groups PR
12R
13Or P (O) R
14R
15, or contain the SeR of seleno group
16
R
8, R
9, R
10, R
11, R
12, R
13, R
14, R
15, R
16Be hydrogen, C
1～C
30Alkyl, C
5～C
50Aromatic group and the aromatic group of replacement;
G: be bridged group with following structure I I, III, IV or V
Wherein:
R
17, R
18, R
19And R
20Be respectively hydrogen, C
1～C
30Alkyl or the alkyl of replacement, adjacent group R
17And R
18, R
19And R
20, and R
17And R
19Become ring or Cheng Huan not;
R
21And R
22Be respectively hydrogen, C
1～C
30Alkyl or the alkyl of replacement, R
21And R
22Be independent substituent group or R
21, R
22Form aromatic nucleus together with two keys;
R
23, R
24, R
25, R
26, R
27, R
28, R
31And R
32Be respectively hydrogen, C
1～C
30Alkyl or the alkyl of replacement; Adjacent group Cheng Jiancheng ring or Cheng Jiancheng ring not;
R
29And R
30Be respectively hydrogen, C
1～C
30Alkyl or the alkyl of replacement, and R
29And R
30Be independent substituent group or R
21, R
22Form aromatic nucleus together with two keys;
Described aromatic group is meant phenyl, naphthyl, anthryl or phenanthryl;
The alkyl of described replacement is meant and contains silica-based SiR on the alkyl
33Or halogen;
The aromatic group of described replacement is that aromatic group contains alkyl, silica-based SiR
33Or halogen;
Described halogen is fluorine, chlorine, bromine or iodine;
Described alkyl comprises alkyl, alkene and alkynes base;
R
33Be meant C
1～C
30Alkyl;
The molecular formula of described metallic compound is MX
nY
m
Wherein M is meant Ti, Zr, Cr or V;
X is meant chlorine or bromine;
Y is meant OR
34, N (R
35)
2, R
36, THF, Et
2O, wherein R
34, R
35Be meant C
1-C
6Alkyl; R
36Be 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 electric neutrality for n and m sum;
Described 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 by the pyrohydrolysis process by gaseous metal oxide compound or silicon compound, or organic high molecular polymer.
2, a kind of preparation of a class single active center ziegler-natta olefin polymerization catalysis as claimed in claim 1 is characterized in that comprising the steps:
1) under noble gas protection or reduced pressure, will be as the organic or inorganic solid of carrier or both mixtures 100～1000 ℃ of following dryings or roasting 1～24 hour;
2) under room temperature to 100 ℃ condition, magnesium compound is dissolved in forms solution in the tetrahydrofuran (THF); In above-mentioned solution, add carrier described in the step 1, metallic compound successively and contain the salicylic aldehyde of coordinating group or the salicylaldehyde derivatives I of replacement, under room temperature to 100 ℃ condition, reacted 2～48 hours, remove solvent, washing and vacuum-drying;
Wherein, described carrier is to be selected from the oxide compound of the 2nd, 4,13,14 group elements at interior inorganic oxide and oxidation mixture and mixed oxide, the solid of the oxidation material for preparing by the pyrohydrolysis process by gaseous metal oxide compound or silicon compound, or organic high molecular polymer;
Described magnesium compound is magnesium halide, alkyl magnesium, alkoxyl group magnesium halide, alkoxyl magnesium, or their mixture;
The molecular formula of described metallic compound is MX
nY
m,
Wherein M is meant Ti, Zr, Cr or V;
X is meant chlorine or bromine;
Y is meant OR
34, N (R
35)
2, R
36, THF, Et
2O, wherein R
34, R
35Be meant C
1-C
6Alkyl; R
36Be 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 electric neutrality for n and m sum;
The used solvent of washing catalyst is C
5～C
10Alkane or C
6～C
8Aromatic hydrocarbons;
The ratio of magnesium compound and tetrahydrofuran (THF) is 20～100mL tetrahydrofuran (THF)/gram magnesium compound, preferred 40～80mL tetrahydrofuran (THF)/gram magnesium compound;
The mass ratio of magnesium compound and carrier 1: 0.5～20;
The mol ratio of magnesium compound metallizing thing is 1～300: 1;
The mol ratio that contains the salicylaldehyde derivatives I metallizing thing of the salicylic aldehyde of coordinating group or replacement is 0.001～50: 1.
3, the preparation of a class single active center ziegler-natta olefin polymerization catalysis as claimed in claim 2 is characterized in that described magnesium compound is a magnesium chloride; Described metallic compound is TiCl
4, TiCl
4(THF)
2Or TiCl
4(Et
2O)
2Described carrier is a silica gel.
4, the preparation of a class single active center ziegler-natta olefin polymerization catalysis as claimed in claim 2 is characterized in that described magnesium compound and vehicle weight ratio are 1: 0.5～10; The mol ratio of magnesium compound metallizing thing is 1～100: 1; The mol ratio of electron metallizing thing is 0.01～20: 1.
5, the preparation of a class single active center ziegler-natta olefin polymerization catalysis as claimed in claim 2 is characterized in that described temperature of reaction is 50 to 70 ℃; Reaction times is 2～24 hours.
6, the purposes of the novel single active center of a class as claimed in claim 1 or 2 ziegler-natta olefin polymerization catalysis is characterized in that described catalyzer is used for that ethylene homo closes, ethene/1-alpha-olefinic copolymerization and ethene/cycloolefin copolymerization.
7, the purposes of the novel single active center of a class as claimed in claim 6 ziegler-natta olefin polymerization catalysis is characterized in that described 1-alkene is C
3～C
20Alkene; Described cycloolefin is cyclopentenes, tetrahydrobenzene, norbornylene or cyclopentenes, tetrahydrobenzene, the norbornylene that the alkyl replacement is arranged.
8, the purposes of the novel single active center of a class as claimed in claim 6 ziegler-natta olefin polymerization catalysis, when it is characterized in that adopting this catalyzer to be used for polymerization, with aluminum alkyls, alkylaluminoxane is promotor, and suitable promotor is selected from triethyl aluminum, triisobutyl aluminium, aluminium diethyl monochloride, three hexyl aluminium or their mixture; The Al/Ti mol ratio is 20～3000 during polymerization.
9, the purposes of the novel single active center of a class as claimed in claim 6 ziegler-natta olefin polymerization catalysis 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 50～120 ℃ of 0～1.0MPa, polymerization temperatures, and medium is propane, Trimethylmethane or hexane, 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 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100267658A CN100482697C (en) | 2006-05-22 | 2006-05-22 | Mono-active center Ziegler-Natta catalyst for olefinic polymerization |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100267658A CN100482697C (en) | 2006-05-22 | 2006-05-22 | Mono-active center Ziegler-Natta catalyst for olefinic polymerization |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1884311A true CN1884311A (en) | 2006-12-27 |
| CN100482697C CN100482697C (en) | 2009-04-29 |
Family
ID=37582626
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2006100267658A Active CN100482697C (en) | 2006-05-22 | 2006-05-22 | Mono-active center Ziegler-Natta catalyst for olefinic polymerization |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100482697C (en) |
Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101798362A (en) * | 2010-02-10 | 2010-08-11 | 中国科学院上海有机化学研究所 | Ziegler-Natta olefin polymerization catalysts with single-site center property |
| US8193288B2 (en) | 2007-10-16 | 2012-06-05 | Sinopec Yangzi Petro-Chemical Ltd. | Supported nonmetallocene catalyst and preparation thereof |
| US8716416B2 (en) | 2007-10-16 | 2014-05-06 | Sinopec Yangzi Petrochemical Company Ltd. | Magnesium-compound supported nonmetallocene catalyst and preparation thereof |
| US8952112B2 (en) | 2009-10-26 | 2015-02-10 | China Petroleum & Chemical Corp. | Supported nonmetallocene catalyst, preparation and use thereof |
| US8952113B2 (en) | 2009-11-13 | 2015-02-10 | China Petroleum & Chemical Corp. | Supported nonmetallocene catalyst, preparation and use thereof |
| US8957169B2 (en) | 2009-11-13 | 2015-02-17 | China Petroleum & Chemical Corp. | Supported nonmetallocene catalyst, preparation and use thereof |
| CN104371046A (en) * | 2013-08-16 | 2015-02-25 | 中国石油化工股份有限公司 | Catalyst system used for olefin polymerization and propylene copolymer |
| US8981023B2 (en) | 2009-10-26 | 2015-03-17 | China Petroleum & Chemical Corp. | Supported nonmetallocene catalyst, preparation and use thereof |
| WO2015161827A1 (en) * | 2014-04-24 | 2015-10-29 | 中国石油化工股份有限公司 | Catalyst component for olefin polymerization and catalyst thereof |
| CN105085729A (en) * | 2014-04-24 | 2015-11-25 | 中国石油化工股份有限公司 | Catalyst component for olefin polymerization, and catalyst for olefin polymerization |
| CN105085726A (en) * | 2014-04-24 | 2015-11-25 | 中国石油化工股份有限公司 | Catalyst component for olefin polymerization, and catalyst for olefin polymerization |
| CN105085749A (en) * | 2014-04-24 | 2015-11-25 | 中国石油化工股份有限公司 | Catalyst component for propylene polymerization, and catalyst thereof |
| CN105085728A (en) * | 2014-04-24 | 2015-11-25 | 中国石油化工股份有限公司 | Method for preparing catalyst component for olefin polymerization, and catalyst for olefin polymerization |
| CN105085746A (en) * | 2014-04-24 | 2015-11-25 | 中国石油化工股份有限公司 | Catalyst component for propylene polymerization, and catalyst thereof |
| CN105085732A (en) * | 2014-04-24 | 2015-11-25 | 中国石油化工股份有限公司 | Catalyst component for olefin polymerization, and catalyst thereof |
| CN106317264A (en) * | 2015-07-01 | 2017-01-11 | 中国石化扬子石油化工有限公司 | Supported MgCl2/TiCl4 catalyst modified by using salicylaldimine, and preparation method and application thereof |
| CN106699947A (en) * | 2015-07-23 | 2017-05-24 | 中国石化扬子石油化工有限公司 | Preparation method for polyethylene with wide molecular weight distribution |
| EP3135699A4 (en) * | 2014-04-24 | 2017-10-04 | China Petroleum&Chemical Corporation | Catalyst component for propylene polymerization, preparation method therefor and catalyst having same |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1218970C (en) * | 2002-02-09 | 2005-09-14 | 中国科学院上海有机化学研究所 | New olefine polymerization catalyst |
| CN1256351C (en) * | 2001-07-23 | 2006-05-17 | 中国科学院上海有机化学研究所 | Catalyst for polymerization and copolymerization of olefine and its synthesis and use |
-
2006
- 2006-05-22 CN CNB2006100267658A patent/CN100482697C/en active Active
Cited By (29)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8193288B2 (en) | 2007-10-16 | 2012-06-05 | Sinopec Yangzi Petro-Chemical Ltd. | Supported nonmetallocene catalyst and preparation thereof |
| US8716416B2 (en) | 2007-10-16 | 2014-05-06 | Sinopec Yangzi Petrochemical Company Ltd. | Magnesium-compound supported nonmetallocene catalyst and preparation thereof |
| US8952112B2 (en) | 2009-10-26 | 2015-02-10 | China Petroleum & Chemical Corp. | Supported nonmetallocene catalyst, preparation and use thereof |
| US8981023B2 (en) | 2009-10-26 | 2015-03-17 | China Petroleum & Chemical Corp. | Supported nonmetallocene catalyst, preparation and use thereof |
| US8952113B2 (en) | 2009-11-13 | 2015-02-10 | China Petroleum & Chemical Corp. | Supported nonmetallocene catalyst, preparation and use thereof |
| US8957169B2 (en) | 2009-11-13 | 2015-02-17 | China Petroleum & Chemical Corp. | Supported nonmetallocene catalyst, preparation and use thereof |
| CN101798362A (en) * | 2010-02-10 | 2010-08-11 | 中国科学院上海有机化学研究所 | Ziegler-Natta olefin polymerization catalysts with single-site center property |
| CN101798362B (en) * | 2010-02-10 | 2012-07-11 | 中国科学院上海有机化学研究所 | Ziegler-Natta olefin polymerization catalysts with single-site center property |
| CN104371046A (en) * | 2013-08-16 | 2015-02-25 | 中国石油化工股份有限公司 | Catalyst system used for olefin polymerization and propylene copolymer |
| CN104371046B (en) * | 2013-08-16 | 2016-12-28 | 中国石油化工股份有限公司 | Catalyst system and catalyzing and a kind of propylene copolymer for olefinic polymerization |
| CN105085746A (en) * | 2014-04-24 | 2015-11-25 | 中国石油化工股份有限公司 | Catalyst component for propylene polymerization, and catalyst thereof |
| CN105085746B (en) * | 2014-04-24 | 2017-09-29 | 中国石油化工股份有限公司 | Catalytic component and its catalyst for propylene polymerization |
| CN105085749A (en) * | 2014-04-24 | 2015-11-25 | 中国石油化工股份有限公司 | Catalyst component for propylene polymerization, and catalyst thereof |
| CN105085728A (en) * | 2014-04-24 | 2015-11-25 | 中国石油化工股份有限公司 | Method for preparing catalyst component for olefin polymerization, and catalyst for olefin polymerization |
| CN105085729A (en) * | 2014-04-24 | 2015-11-25 | 中国石油化工股份有限公司 | Catalyst component for olefin polymerization, and catalyst for olefin polymerization |
| CN105085732A (en) * | 2014-04-24 | 2015-11-25 | 中国石油化工股份有限公司 | Catalyst component for olefin polymerization, and catalyst thereof |
| WO2015161827A1 (en) * | 2014-04-24 | 2015-10-29 | 中国石油化工股份有限公司 | Catalyst component for olefin polymerization and catalyst thereof |
| RU2690192C2 (en) * | 2014-04-24 | 2019-05-31 | Чайна Петролеум Энд Кемикэл Корпорейшн | Catalyst component for polymerisation of propene, method for production thereof and catalyst containing thereof |
| US10208145B2 (en) | 2014-04-24 | 2019-02-19 | China Petroleum & Chemical Corporation | Catalyst component for olefin polymerization, and catalyst containing the same |
| CN105085726A (en) * | 2014-04-24 | 2015-11-25 | 中国石油化工股份有限公司 | Catalyst component for olefin polymerization, and catalyst for olefin polymerization |
| EP3135699A4 (en) * | 2014-04-24 | 2017-10-04 | China Petroleum&Chemical Corporation | Catalyst component for propylene polymerization, preparation method therefor and catalyst having same |
| CN105085726B (en) * | 2014-04-24 | 2017-11-07 | 中国石油化工股份有限公司 | A kind of catalytic component and catalyst for olefinic polymerization |
| CN105085732B (en) * | 2014-04-24 | 2017-11-07 | 中国石油化工股份有限公司 | A kind of catalytic component and its catalyst for olefinic polymerization |
| CN105085749B (en) * | 2014-04-24 | 2017-12-19 | 中国石油化工股份有限公司 | Catalytic component and its catalyst for propylene polymerization |
| CN105085729B (en) * | 2014-04-24 | 2018-01-23 | 中国石油化工股份有限公司 | A kind of catalytic component and catalyst for olefinic polymerization |
| CN105085728B (en) * | 2014-04-24 | 2018-10-16 | 中国石油化工股份有限公司 | A kind of method and its catalyst preparing catalyst component for olefin |
| CN106317264B (en) * | 2015-07-01 | 2018-11-30 | 中国石化扬子石油化工有限公司 | A kind of support type MgCl2/TiCl4 catalyst and its preparation method and application with salicylic alidehyde imine type modifier modification |
| CN106317264A (en) * | 2015-07-01 | 2017-01-11 | 中国石化扬子石油化工有限公司 | Supported MgCl2/TiCl4 catalyst modified by using salicylaldimine, and preparation method and application thereof |
| CN106699947A (en) * | 2015-07-23 | 2017-05-24 | 中国石化扬子石油化工有限公司 | Preparation method for polyethylene with wide molecular weight distribution |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100482697C (en) | 2009-04-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1884311A (en) | Mono-active center Ziegler-Natta catalyst for olefinic polymerization | |
| CN1068337C (en) | Process for the gas phase polymerization of alpha-olefins | |
| CN1301271C (en) | Dual-site olefin polymerisation catalyst composition | |
| CN101065404A (en) | Process for the preparation of a catalyst component for the polymerization of an olefin | |
| CN1884253A (en) | Organic compound containing heteroatoms and its use in Zigler-Natta catalyst | |
| CN1038754C (en) | Process for the preparation of a ziegler-natta type catalyst | |
| CN1351615A (en) | Method of polymerization | |
| CN1089622A (en) | The catalyst component and the catalyzer that are used for olefinic polyreaction | |
| CN1044822A (en) | Olefin polymerization catalysis | |
| CN1050025A (en) | The method for preparing vanadium/titanium based catalyst suitable for olefin polymerisation | |
| CN1834116A (en) | Catalyst for olefin polymerization | |
| CN1137905C (en) | Metallocene compounds and their use for olefin polymerization | |
| CN1137902C (en) | Supported polymerization catalysts | |
| CN1088220A (en) | The deactivator of olefin polymerization catalysis | |
| CN1789292A (en) | Application of supported non-metallocene catalyst in ethene polymerization process by slurry method | |
| CN1789290A (en) | Highly active supporting method of non-metallocene catalyst | |
| CN1662564A (en) | Catalyst composition and polymerization process using mixtures of electron donors | |
| CN1181105C (en) | High activity silica gel carrier catalyst component for ethylene polymerisation or copolymerisation and its catalyst and use of said catalyst | |
| CN1231500C (en) | Catalyst for polymerization and copolymerization of ethylene | |
| CN1324055C (en) | Ethene polymerization catalyst, its production and polymerization kinetic behaviour control | |
| CN1279069C (en) | Polyethylene catalyst and its preparation method | |
| KR20120061029A (en) | Method for preparing supported hybride metallocene catalyst | |
| CN1177873C (en) | Catalyst component for ethylene polymerization or copolymerization, and catalyst and use thereof | |
| CN1636023A (en) | Method for preparing a catalyst support for polymerising ethylene and a-olefins, resulting support and corresponding catalyst | |
| CN1337413A (en) | Carrier catalyst of high productivity and greatly reducing fouling for producing meta-styrene polymers |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |