CN1730498A - A vanadium catalyst and its preparation method - Google Patents
A vanadium catalyst and its preparation method Download PDFInfo
- Publication number
- CN1730498A CN1730498A CN 200410070449 CN200410070449A CN1730498A CN 1730498 A CN1730498 A CN 1730498A CN 200410070449 CN200410070449 CN 200410070449 CN 200410070449 A CN200410070449 A CN 200410070449A CN 1730498 A CN1730498 A CN 1730498A
- Authority
- CN
- China
- Prior art keywords
- acid
- compound
- vanadium
- organophosphate
- vanadyl
- 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 provides a novel vanadium catalyst, its preparing process and use of the catalyst in ethane, alpha-alkene, dialkene copolymerization. The catalyst can be dissolved into non-polar solvent, and is not sensitive to air, water, acid and alkali. The synthesis method is simple, thus can be applied into mass production.
Description
Technical field
The present invention relates to a kind of new vanadium catalyst and easy, the application of preparation method, and this catalyzer efficiently in ethene, alpha-olefin, diolefine copolymerization thereof that alkene is had greater activity.
Background technology
Often vanadium system Ziegler-Natta catalyst is used for ethene, alpha-olefin, diolefine terpolymerization in the industrial production and prepares rubber elastomer.Representative Primary Catalysts has VOCl
3, VCl
3, VCl
4, V (acac)
3Deng, promotor is an I-III family organometallic compound (as aluminum alkyls), these V-alkyl aluminum systems have been brought into play vital role on synthetic EPDM elastomerics.But this type of catalyzer also exists many shortcomings simultaneously, the first, lower to the unexpectedly poly-rate of propylene, diolefine than ethene, therefore in industrial production, must make propylene etc. excessive greatly, if obtain ideal diene and propylene insertion rate, will recycle excessive propylene and diolefine; The second, the terpolymer activity is not high enough; The 3rd, therefore these compounds are being produced storage and are being used and can bring many problems sensitivities such as air, water, acid, alkali; The 4th, the building-up reactions once through yield is low.
US5086023 is by change center surrounding environment, promptly with group (imino-) substituted oxy with different characteristic electrons, solved the insertion problem of propylene, diolefine, its polymerization activity is better, but employed complex compound is still to sensitivities such as air, water, acid, alkali.US4598132 discloses a kind of vanadium catalyst system that contains the ester group polymkeric substance, can only improve the gel problem with the system that this catalyzer and aluminum alkyls form in synthetic EPDM process; As vulcanize problem.What solved among the US5122493 is the molecular weight distribution problem, by using branching dihydroxyl hydrocarbon, makes polymericular weight form narrow distribution, employed VO (acac)
2Though catalyzer is insensitive to air, water etc.,, have difficulties when therefore using because it is insoluble to inert solvent (as hexane).
Summary of the invention
The object of the present invention is to provide a kind of stable, active height of copolymerization, new vanadium catalyst easy to use and preparation method thereof, and the application of this catalyzer in ethene, alpha-olefin, diolefine terpolymer.
A kind of vanadium catalyst provided by the present invention, its structural formula is:
VALL′
Wherein: V is vanadium 4 valency ions;
A is oxygen, sulphur, selenium;
L, L ' are part, and L, L ' are organophosphate, and L, L ' can be identical, also can be inequality.
Organophosphate in the catalyzer that invention is provided can be dialkyl phosphate, dialkyl group thiophosphatephosphorothioate, dialkyl dithiophosphate, seleno phosphoric acid ester, two seleno phosphoric acid ester, annular phosphate, ring-type thiophosphatephosphorothioate, heterocycle Hypophosporous Acid, 50, heterocycle sulfo-Hypophosporous Acid, 50, condensed ring phosphoric acid ester, condensed ring thiophosphatephosphorothioate, preferred dialkyl phosphate.
Because the phosphoryl in the organophosphate wherein has the sub-property of power supply, exactly the oxygen of phosphoryl has the sub-property of power supply, thereby easily forms hydrogen bond and extremely strong metal complex ability is arranged at vanadium catalyst provided by the present invention; Easy and the Cl of hydrogen in the while bisphosphate hydroxyl
-And SO
4 2-Form acid (forming salt), and make bisphosphate become covalent linkage with the central atom V-arrangement, make bisphosphate and halogenation vanadium or halogenation vanadyl can form stable complex compound if add alkali.
Preparation of catalysts step provided by the present invention is as follows:
(A) under the condition that alcohol compound, carboxylic acid or carbonyl compound exist, pentavalent vanadium compound and inorganic acid reaction, obtain intermediate product 4 valency vanadyl compounds, pentavalent vanadium compound: mineral acid: alcohol compound, carboxylic acid or carbonyl compound (mol ratio)=1: 2～100: 1～20;
(B) after the cooling, 4 valency vanadyl compounds and organophosphate react pentavalent vanadium compound in non-polar solvent: organophosphate (mol ratio)=1: 1～3, stir, and drip alkaline inorganics, obtain catalyzer.
Or rather, the pentavalent vanadium compound in the Preparation of catalysts method provided by the present invention can Vanadium Pentoxide in FLAKES; Mineral acid can be hydrochloric acid or sulfuric acid; Nonmetallic reduction agent is as using alcohol compound, preferred alcohol, as be the carboxylic acid preferable formic acid, as be the preferred acetone of carbonyl compound; The alkalescence inorganics can be sodium carbonate solution; Non-polar solvent can be straight-chain paraffin or naphthenic hydrocarbon, preferred hexane.
New vanadium catalyst preferably provided by the invention is as follows:
(two (di (isooctyl) phosphate base)) vanadyl, (two O-(2-ethylhexyl)-ethylhexyl dihydrogen phosphate base) vanadyl, (O-di (isooctyl) phosphate O-(2-ethylhexyl)-ethylhexyl dihydrogen phosphate base) vanadyl, (two (diisoamyl phosphate base)) vanadyl, (two (O, O-diethyl phosphorothioate base)) vanadyl, (two (dibutyl phosphate base)) vanadyl, (two (p diethylaminobenzoic acid ester group)) vanadyl, (oxidation hydroxyl-1,3,2-benzo dioxy phospha five rings base) vanadyl, (two (O, O-encircles third phosphorodithioate)) vanadyl, (two (O, S-diisooctyl phosphoric acid ester group)) vanadyl, (oxidation hydroxyl phospha cyclohexane base) vanadyl, (two (oxidation hydroxy benzo phospholane base)) vanadyl, (two (dimethyl phosphate base)) vanadyl, (two (dibutyl phosphate base)) vanadyl, (two (p diethylaminobenzoic acid ester group)) vanadyl, (two (O, O-Methyl disulfide substituted phosphate base)) vanadyl.
The present invention also provides the application of described catalyzer in the terpolymerization of ethene, alpha-olefin, diolefine.In the terpolymerization of ethene, alpha-olefin, diolefine, can use catalyzer provided by the present invention to be Primary Catalysts, promotor is an aluminum alkyls.Aluminum alkyls can be triisobutyl aluminium, a chloro-di-isobutyl aluminum, aluminium diethyl monochloride, trichlorine triethyl two aluminium, dichloro one aluminium triethyl or triethyl aluminum; Preferred trichlorine triethyl two aluminium; Solvent is a non-polar solvent, can be straight-chain paraffin or naphthenic hydrocarbon, preferred hexane.
Alpha-olefin can be C
3～C
8Alkene, preferred propylene; Diolefine can be cyclopentadiene, dicyclopentadiene, ethylidene norbornene, 1,4-hexadiene, 5-vinyl-2-norbornylene etc., preferred ethylidene norbornene.
Polymerization temperature is 10～50 ℃, and polymerization pressure is 0.1～1.0Mpa, polymerization time 0.5～3.0 hour.
The application concrete operations of described catalyzer in the terpolymerization of ethene, alpha-olefin, diolefine are as follows:
Adopt the solution polymerization process polymerization.Reactor is a 5L Stainless Steel Band jacket reactor.The effect of chuck is a control reaction temperature.Unstripped gas is the mixed gas of ethene, propylene, hydrogen, ethene: propylene: hydrogen (mol ratio) is 1: 1.5～4.5: 0.15～0.45.In reactor, add solvent in proportion.Feed unstripped gas by certain speed in reactor, control unstripped gas air inlet speed prevents the excessive hexane of carrying secretly of tolerance.Emptying adds a certain amount of Primary Catalysts, promotor after 10 minutes, temperature of reaction is remained between 10～50 ℃, control reaction pressure 0.3～0.6Mpa, the middle interruption adds diolefine, use the cooling water control temperature of reaction, polymerization 1 hour adds ethanol and makes reaction terminating.Add 20%NaOH solution then and carry out repetitive scrubbing several times, the product static layering with obtaining bleeds off water layer, and remaining upper strata glue obtains terpolymer EPDM 50 ℃ of following vacuum-dryings 48 hours.
The present invention adopts two-step approach synthesizing new vanadium ziegler-natta catalyzer, and total yield reaches 90%～100%, and synthetic method is simple, and is workable, is easy to industrialization.Advantage of the present invention is that the new vanadium catalyst that is provided contains heteroatom phosphate, be dissolved in non-polar solvent (for example hexane)-better solvent of the second third glue industrialization, and this catalyzer is all insensitive to air, water, acid, alkali, therefore gives and uses and the synthetic great convenience of bringing.This catalyzer demonstrates high reactivity in ethene, alpha-olefin, diolefine terpolymerization.
Embodiment
The invention will be further described below by embodiment.
Embodiment 1
Synthesizing of dichloro vanadyl
Get the 250ml there-necked flask and reinstall flow condenser, electromagnetism heated and stirred (Gong Yi of Henan Province city).Accurately take by weighing 5gV
2O
5(27.5mmol), pack in the there-necked flask, measure 18ml (18.5mmol) concentrated hydrochloric acid (36%) then, add 15ml water, 5ml reagent alcohol, heated sealed stirring and refluxing, half hour internal reaction liquid by brick red to yellowish green, become mazarine at last, react half an hour again, get mazarine dichloro vanadyl solution.
B.[two (diisooctyl phosphoric acid ester group)] vanadyl synthetic
Get that 1000ml there-necked flask installation tool stirs, minim pipette, above-mentioned synthetic dichloro vanadyl is packed in the there-necked flask, add the 300ml industrial hexane, stirring adds 95.5% industrial diisooctyl phosphoric acid ester 38ml down again, stir 10% the sodium carbonate solution of slowly dripping, restir 10 minutes, stop to stir and pour the quantizer layering into, get oil phase, it is inferior to give a baby a bath on the third day after its birth with 1000ml distilled water again, gets the blue vanadium complexes of 325ml at last, concentration is 17.6% by analysis, and yield is 99%.
Embodiment 2
Synthesizing of vanadylic sulfate
Get the 250ml there-necked flask, reinstall flow condenser, the electromagnetism heated and stirred.Accurately take by weighing 5gV
2O
5(27.5mmol) pack in the there-necked flask, measure the vitriol oil of 8ml98% then, slowly add 12.5ml distilled water again, add the 10ml dehydrated alcohol again, sealed reactor, heated and stirred refluxes, half an hour internal reaction liquid by brick red to blackish green, be mazarine at last.React half an hour again, get mazarine vanadylic sulfate solution.
B.[two (diisooctyl phosphoric acid ester group)] vanadyl synthetic
Get the 1000ml there-necked flask, installation tool stirring, minim pipette, above-mentioned synthetic vanadylic sulfate is packed in the there-necked flask, add the 300ml industrial hexane and stir and add 95.5% industrial diisooctyl phosphoric acid ester 38ml down, stir, slowly drip 10% sodium carbonate solution, when reaction solution water PH=6～7, stop to drip sodium carbonate solution, restir 10 minutes, stop to stir, pour quantizer into, get oil phase, it is inferior to give a baby a bath on the third day after its birth with 1000ml distilled water again, get the blue vanadium complexes of 305ml at last, yield 92%.
Embodiment 2
Elementary operation is with embodiment 1.The diisooctyl phosphoric acid ester is replaced with O-(2-ethylhexyl)-ethylhexyl dihydrogen phosphate, get 310 blue solution, yield 96%.
Ultimate analysis: C theoretical value 56.65, measured value 55.66; H theoretical value 10.03, measured value 9.56; P theoretical value 14.17, measured value 14.00; V theoretical value 11.66, measured value 9.65.
Synthesizing of embodiment 3 (two O-(2-ethylhexyl)-ethylhexyl dihydrogen phosphate base) vanadyl
Elementary operation is with embodiment 1.The diisooctyl phosphoric acid ester is replaced with the different ester of defending of di(2-ethylhexyl)phosphate, get the blue hexane solution of 295ml, yield 90%.
Ultimate analysis: C theoretical value 44.31, measured value 44.60; H theoretical value 8.12, measured value 8.19; P theoretical value 7.58, measured value 7.33; V theoretical value 9.42, measured value 9.00.
Synthesizing of embodiment 4 (oxidation hydroxyl-1,3,2-benzo dioxy phospha five rings base) vanadyl
Elementary operation is with embodiment 1.The diisooctyl phosphoric acid ester is replaced with oxidation hydroxyl-1,3,2-benzo dioxy phospha five rings, get the blue hexane solution of 300ml, yield 91%.
Ultimate analysis: C theoretical value 17.60, measured value 16.95; H theoretical value 1.22, measured value 1.23; P theoretical value 7.58, measured value 7.33; V theoretical value 12.47, measured value 10.69.
Synthesizing of embodiment 5 (oxidation hydroxyl-1,3,2-benzo dioxy phospha five rings base) vanadyl
Elementary operation is with embodiment 2.The diisooctyl phosphoric acid ester is replaced with oxidation hydroxyl-1,2,2-benzo dioxy phospha five rings, get the blue hexane solution of 310ml, yield 98%.
Ultimate analysis: C theoretical value 17.60, measured value 16.80; H theoretical value 1.22, measured value 1.20; P theoretical value 7.58, measured value 7.37; V theoretical value 12.47, measured value 11.69.
Embodiment 6 (two (O, O-encircle third phosphorodithioate)) vanadyl
Elementary operation is with embodiment 1.Different is with two different hot phosphoric acid ester with O, and O '-ring third phosphorodithioate substitutes, final the blue hexane solution of 280ml, yield 85%.
Ultimate analysis: C theoretical value 8.89, measured value 8.70; H theoretical value 1.73, measured value 1.56; P theoretical value 7.65, measured value 7.63; V theoretical value 12.59, measured value 11.76.
Embodiment 7 (two (O, O-encircle third phosphorodithioate)) vanadyl
Elementary operation is with embodiment 2.Different is with two different hot phosphoric acid ester with O, and O '-ring third phosphorodithioate substitutes, final the blue hexane solution of 290ml, yield 88%.
Ultimate analysis: C theoretical value 8.89, measured value 8.77; H theoretical value 1.73, measured value 1.68; P theoretical value 7.65, measured value 7.56; V theoretical value 12.59, measured value 11.87.
Synthesizing of embodiment 8 (two (oxidation hydroxy benzo phospholane base)) vanadyl
Elementary operation is with embodiment 1.Different is that di (isooctyl) phosphate is substituted the blue hexane solution of the final 290ml of getting, yield 90% with oxidation hydroxy benzo phospha five rings.
Ultimate analysis: C theoretical value 23.94, measured value 23.65; H theoretical value 2.24, measured value 2.31; P theoretical value 7.73, measured value 7.68; V theoretical value 12.72, measured value 12.13.
Synthesizing of embodiment 9 (two (oxidation hydroxy benzo phospholane base)) vanadyl
Elementary operation is with embodiment 2.Different is that di (isooctyl) phosphate is substituted the blue hexane solution of the final 295ml of getting, yield 92% with oxidation hydroxy benzo phospha five rings.
Ultimate analysis: C theoretical value 23.94, measured value 23.90; H theoretical value 2.24, measured value 2.26; P theoretical value 7.73, measured value 7.23; V theoretical value 12.72, measured value 11.89.
Embodiment 10
Adding the 2000ml hexane in the 5L polymeric kettle stirs, in polymeric kettle, feed ethene under the normal temperature, propylene, hydrogen mixed gas, [two (di (isooctyl) phosphate the base)] vanadyl that adds 0.04mmol, and the alkyl aluminum halide of 0.8mmol, ethene: propylene: hydrogen=1: 2.5: 0.2, polymerization pressure 0.5Mpa, polymerization 1 hour, stop to stir, add the ethanol termination reaction, use the 20%NaOH solution washing for several times then, static layering, get the glue layer, reclaim solvent, product got product 85.2g, molecular weight 47500 in 24 hours 50 ℃ of following vacuum-dryings, molecular weight distribution 2.5, ethylene content 52%.
Embodiment 11
In the 5L polymeric kettle, add the 2000ml hexane, stir, in polymeric kettle, feed ethene under the normal temperature; propylene; hydrogen mixed gas; [two (the oxidation hydroxyls-1 that add 0.02mmol; 3,2-benzo dioxy phospha five rings)] alkyl aluminum halide of vanadyl and 1mmol, ethene: propylene: hydrogen=1: 2.5: 0.2; polymerization pressure 0.6Mpa; polymerization 1 hour stops gas mixture, stops to stir; add the ethanol termination reaction; use the 20%NaOH solution washing then three times, static layering is got the glue layer; reclaim hexane; product gets product 46g, molecular weight 56000 at 60 ℃ of following vacuum-drying 24h; molecular weight distribution 2.8, ethylene content 62%.
Claims (8)
1. vanadium catalyst, its structural formula is:
VALL′
Wherein: V is vanadium 4 valency ions;
A is oxygen, sulphur, selenium;
L, L ' are part, and L, L ' are organophosphate, and L, L ' can be identical, also can be inequality.
2. vanadium catalyst according to claim 1 is characterized in that organophosphate is dialkyl phosphate, dialkyl group thiophosphatephosphorothioate, dialkyl dithiophosphate, seleno phosphoric acid ester, two seleno phosphoric acid ester, annular phosphate, ring-type thiophosphatephosphorothioate, heterocycle Hypophosporous Acid, 50, heterocycle sulfo-Hypophosporous Acid, 50, condensed ring phosphoric acid ester or condensed ring thiophosphatephosphorothioate.
3. the described Preparation of catalysts method of claim 1, step is as follows:
(A) under alcohol compound, carboxylic acid or carbonyl compound existence condition, pentavalent vanadium compound and inorganic acid reaction, obtain intermediate product 4 valency vanadyl compounds, pentavalent vanadium compound: mineral acid: alcohol compound, carboxylic acid or carbonyl compound (mol ratio)=1: 2～100: 1～20;
(B) after the cooling, 4 valency vanadyl compounds and organophosphate react pentavalent vanadium compound in non-polar solvent: organophosphate (mol ratio)=1: 1～3, stir, and drip alkaline inorganics, obtain catalyzer.
4. Preparation of catalysts method according to claim 3, it is characterized in that pentavalent vanadium compound wherein is a Vanadium Pentoxide in FLAKES, mineral acid is hydrochloric acid or sulfuric acid, and organophosphate is a dialkyl phosphate, the alkalescence inorganics is a sodium carbonate solution, and non-polar solvent is a hexane.
5. Preparation of catalysts method according to claim 3 is characterized in that wherein alcohol compound, carboxylic acid or carbonyl compound can be ethanol, formic acid or acetone.
6. the application of the catalyzer of a claim 1 in the terpolymerization of ethene, alpha-olefin, diolefine is characterized in that promotor is an aluminum alkyls.
7. Application of Catalyst according to claim 6 is characterized in that aluminum alkyls is triisobutyl aluminium, a chloro-di-isobutyl aluminum, aluminium diethyl monochloride, trichlorine triethyl two aluminium, dichloro one aluminium triethyl or triethyl aluminum.
8. Application of Catalyst according to claim 6 is characterized in that terpolymerization temperature wherein is 10～50 ℃, and polymerization pressure is 0.1～1.0Mpa, polymerization time 0.5～3.0 hour.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100704491A CN100429239C (en) | 2004-08-04 | 2004-08-04 | A vanadium catalyst and its preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100704491A CN100429239C (en) | 2004-08-04 | 2004-08-04 | A vanadium catalyst and its preparation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1730498A true CN1730498A (en) | 2006-02-08 |
| CN100429239C CN100429239C (en) | 2008-10-29 |
Family
ID=35962923
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2004100704491A Expired - Fee Related CN100429239C (en) | 2004-08-04 | 2004-08-04 | A vanadium catalyst and its preparation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100429239C (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102558414A (en) * | 2010-12-10 | 2012-07-11 | 中国石油天然气股份有限公司 | Synthesis method of bimodal-distribution ethylene-propylene-nonconjugated diene random copolymer |
| CN104418964A (en) * | 2013-08-23 | 2015-03-18 | 中国石油天然气股份有限公司 | Preparation method for ethylene-propylene-unconjugated dialkene random copolymer |
| CN108889319A (en) * | 2018-07-23 | 2018-11-27 | 贵州大学 | A kind of composite modified vanadium catalyst of efficient H2O2/Se and preparation method thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5086023A (en) * | 1991-06-13 | 1992-02-04 | Akzo N.V. | Catalyst for EPDM polymerization |
| IT1303771B1 (en) * | 1998-11-19 | 2001-02-23 | Enichem Spa | VANADIUM CATALYSTS, THEIR PREPARATION AND USE IN THE (CO) POLYMERIZATION OF ALFA-OLEFINE. |
| JP2001064316A (en) * | 1999-08-27 | 2001-03-13 | Ube Ind Ltd | Production of conjugated diene polymer |
-
2004
- 2004-08-04 CN CNB2004100704491A patent/CN100429239C/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102558414A (en) * | 2010-12-10 | 2012-07-11 | 中国石油天然气股份有限公司 | Synthesis method of bimodal-distribution ethylene-propylene-nonconjugated diene random copolymer |
| CN102558414B (en) * | 2010-12-10 | 2013-11-06 | 中国石油天然气股份有限公司 | Synthesis method of bimodal-distribution ethylene-propylene-nonconjugated diene random copolymer |
| CN104418964A (en) * | 2013-08-23 | 2015-03-18 | 中国石油天然气股份有限公司 | Preparation method for ethylene-propylene-unconjugated dialkene random copolymer |
| CN108889319A (en) * | 2018-07-23 | 2018-11-27 | 贵州大学 | A kind of composite modified vanadium catalyst of efficient H2O2/Se and preparation method thereof |
| CN108889319B (en) * | 2018-07-23 | 2021-05-07 | 贵州大学 | Efficient H2O2/Se composite modified vanadium catalyst and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100429239C (en) | 2008-10-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Clawson et al. | Olefin insertion in a metal alkyl in a Ziegler polymerization system | |
| CN1108967A (en) | Olefin production | |
| CN1248979A (en) | Process for polymerizing olefins | |
| CN105008409B (en) | Alpha-olefin polymer and method for producing hydrogenated alpha-olefin polymer | |
| CN1068330C (en) | Metallocene compound and its use as catalyst component | |
| CN1730498A (en) | A vanadium catalyst and its preparation method | |
| CN1887918A (en) | Catalyst for olefin polymerization or copolymerization at high temperature | |
| CN112830934A (en) | Unsaturated spiro orthocarbonate expansion monomer and synthesis method and application thereof | |
| EP4182366A1 (en) | Hydrocarbyl-modified methylaluminoxane cocatalysts for bis-phenylphenoxy metal-ligand complexes | |
| CN101885795B (en) | Electron donor catalyst and preparation and application | |
| CN111606941A (en) | Novel fluorosilicone rubber auxiliary agent and preparation method and application thereof | |
| CN102558414B (en) | Synthesis method of bimodal-distribution ethylene-propylene-nonconjugated diene random copolymer | |
| CN1008909B (en) | Ethylene polymerization catalyst | |
| CN101029096A (en) | Neutral non-bridged combined metal chromium catalyst and its use | |
| CN1188434C (en) | Polymerization catalyst for olefin monomers | |
| CN1079091C (en) | Process for the dimerization of lower olefins | |
| CN1288175C (en) | Catalyst for olefin high-temperature polymerization and preparation and use thereof | |
| CN1096286A (en) | The method for preparing the alkadiene alcohol compound | |
| CN1222549C (en) | Improved process for preparing butyl rubber using alkyllithium dihalide and aluminoxane | |
| CN1672793A (en) | Beta-diimide nickel compound/alkyl aluminium catalyst system and its application | |
| CN1284960A (en) | 'Pi' complex compounds | |
| CN106478844B (en) | Catalyst carrier, catalyst component and catalyst for olefin polymerization | |
| CN1208339C (en) | Single metallocene catalyst with naphthalene ring ligand and its prepn | |
| CN102875709B (en) | Preparation method of catalyst component for ethylene polymerization reaction and catalyst thereof | |
| CN1593763A (en) | Furan contained metallic catalyst, preparation method and application thereof |
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 | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20081029 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |