Catalyst components and catalysts for olefins polymerization
Abstract
Catalyst components for the polymerization of olefins comprising a titanium halide or alkoxyhalide and an electron-donor compound selected from ethers having two or more ether groups and containing at least one heteroatom selected from the group consisting of N, S, P, Si, non-ether O and halogen atoms or at least one double bond, or both at least one heteroatom and at least one double bond, supported on a magnesium halide in active form. Catalysts obtained from said catalyst components and an Al-alkyl compound, as well as catalysts obtained by the reaction of an Al-alkyl compound and an ether having the above defined characteristics with a solid catalyst component comprising a titanium halide or alkoxyhalide and an electron-donor compound having particular characteristics of extractability with Al-triethyl, supported on activated magnesium halide.

Term
No projected expiry on record.
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2 claims: 2 independent, 0 dependent
- 1a strukturální vlastnosti, které jsou vhodné pro přípravu katalyzátorů a katalyzátorových komponentů pro ’ and structural properties that are suitable for the preparation of catalysts and catalyst components for p.oly.merizaci výše zmíněných . olefinů. í. p.oly.merization of the above. olefins. and. Podstata vynálezu r1' j*. The essence of the invention r1'j *. • *5 • *5 Ij Ij A new group of ethers has now been unexpectedly discovered which is suitable for the preparation of highly active or stereospecific catalysts and catalysts. Nyní byla neočekávaně zjištěna nová skupina etherů, která je vhodné pro přípravu vysoce aktivních ή a stereospecifických katalyzátorů a katalyzátorových > components for the polymerization of these olefins. f /. Ř1 r! komponentů pro polýmerizaci těchto olefinů. f / . Ř 1 r! In fact, the ethers of the present invention together with Al-alkyl compounds and in combination with solids. | catalyst components having the properties described? Ve skutečnosti ethery tohoto vynálezu společ- £ ně s Al-alkylovými sloučeninami a v kombinaci s tuhými . | katalyzátorovými komponenty, majícími vlastnosti popsané ? In the patent, highly specific catalysts. Ethers of the present invention having i? VUS patentu vysoce ^řtTvňí^těrěo^ specifické katalyzátory. Ethery.tohoto vynálezu mající i? appropriate structure, in addition when present in solid '| catalyst components containing an isane halide or a titanium alkoxy halide deposited on a magnesium halide in active form can form highly active | and stereospecific catalysts even without use and'; příslušnou strukturu,navíc když jsou přítomny v tuhých ' | katalyzátorových komponentech, obsahujících halogenid £ is nebo alkoxyhalogenid titanu, uložených na halogenidu hořečnatém v aktivní formě, mohou vytvořit vysoce aktivní | a stereospecifické katalyzátory dokonce bez použití | i’; electron donor compounds added to the Al-alkyl E compound. c $ elektrondonorových sloučenin, přidaných k Al-akylové £ sloučenině. c $ Ethery tohoto vynálezu obsahují alespoň 2 j nebo více etherových skupin a alespoň jeden heteroatom vybraný ze skupiny zahrnující N,S,P,Ši, neetherický 0 a ' ΐ atomy halogenů, nebo alespoň jednu dvojnou vazbu, nebo i obsahují jak alespoň jeden heteroatom výše definovaný, / tak alespoň jednu dvojnou vazbu. í; The ethers of the present invention contain at least 2 or more ether groups and at least one heteroatom selected from the group consisting of N, S, P, Si, non-etheric O and halogen halogen atoms, or at least one double bond, or even contain at least one heteroatom as defined above. , / so at least one double bond. and; - 4 Representativní ethery, které jsou zvlášt výhodné, když jsou přítomné v tuhém katalyzátorovém komponentu pro vytvoření vysoce aktivních a stereospecifických katalyzátorů, dokonce bez použití přídavných elektrondonorových sloučenin, přidaných k Al-alkylové sloučenině, jsou 1,3-diethery vzorce Representative ethers that are particularly preferred when present in a solid catalyst component to form highly active and stereospecific catalysts, even without the use of additional electron donor compounds added to the Al-alkyl compound, are 1,3-diethers of the formula X X R 1 -O-CH2- C-CH2-O -R2 R|- 0-CH2- C-CH2-O -R2 Y kde R1 a R2 jsou totožné nebo rozdílné a jsou to uhlo'vodíkové skupiny s T až 6 atomy uhlíku, případně nenasycené a/nebo obsahující atomy halogenu; Y where R1 and R2 are identical or different and are hydrocarbon groups with T to 6 carbon atoms, optionally unsaturated and / or containing halogen atoms; X is a hydrocarbon group having 1 to 18 carbon atoms, containing at least one heteroatom which is not directly attached to the central carbon atom / in the 2 / 1,3-diether position, the heteroatom being selected from the group consisting of N, S, P, Si , nonetheric O and halogen atoms, or?. X je uhlovodíková skupina s 1 až 18 atomy uhlíku, obsahující alespoň jeden heteroatom, který není přímo vázán na centrální atom uhlíku /v poloze 2/ 1 ,3-dietherových molekul, přičemž heteroatom je vybrán ze skupina zahrnující N, S, P, Si, neetherický O a atomy halogenů, nebo ?. X is a halogen atom or a heteroatom-containing group, where one heteroatom is attached directly to the central carbon atom of the 1,3-diether above. X je atom halogenu nebo skupina- obsahující heteroatom, kde jeden heteroatom je vázán přímo na centrální atom uhlíku 1,3-dietheru výše “ 5 - R ', R,,R 1 are hydrocarbon groups, optionally unsaturated, having up to 18 carbon atoms and R’,R,,,R’** jsou uhlovodíkové skupiny, případně nenasycené, které mají i až'18 atomů uhlíku a R 'a R *1 together, in the case of NR'R ', they can also form an epalephilic cyclic structure and R’ a R*1 společně, v případě NR’R”, mohou také tvořit epaleěfiě cyklickou strukturu a R * or R '* or both, in the case of -Si ^ R'R' *) m (OR '' *)n and R* nebo R’* nebo oba, v případě -Si^R’R’*) m (OR’’ *)n a - 6 Reprezentativní příklady 1,3-dietherů obsahujících halogenové atomy jsou:. Representative examples of 1,3 - diethers containing halogen atoms are:.
- 22-isopropyl-2-trifluormethyl-1,3-dimethoxypropan;) 2-isopropyl-2-trifluoromethyl-1,3-dimethoxypropane;) 2-isopropyl-2-trifluormethyl-1,3-diethoxypropan;. 2-isopropyl-2-trifluoromethyl-1,3-diethoxypropane;2 - iso-propyl-1-yl-methyl-1,3-dibuthoxypropane;2 - i s o pro pyl -2 -1 r if 1 uo rm e thyl-1,3-dibuthoxypro pan;2-isobutyl-2-trifluormethyl-1 ,3-dimethoxypropan;2-isobutyl-2-trifluoromethyl-1,3-dimethoxypropane;2- (2-chloro-n-propyl) -2-n-propyl-1,3-dimethoxypropane;2-(2-chlor-n-propyl)-2-n-propyl-1 ,3-dimethoxypropan;
Independent claims2
19 paragraphs in 1 section, as filed
(541 Catalyst components and catalysts for olefin polymerisation (57) Catalyst components for polymerisation i. olefins comprising a titanium halide or a titanium alkoxy halide and an electron donor compound selected from ethers having at least 2 ether groups and containing at least one heteroatom selected from the group consisting of N, S, P, Si, non-ethereal Oa halogen atoms, or at least one double bond, or both at least one heteroatom and at least one double bond deposited on the magnesium halide in active form. Catalysts obtained from these catalyst components and an Al-alkyl compound, as well as catalysts obtained by reacting an Al-alkyl compound and an ether having the above-defined properties with a solid catalyst component comprising a titanium halide or titanium alkoxy halide and an electron donor compound having The respective properties of the extrudate properties of the activated magnesium halide are deposited on the activated magnesium halide.
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AND
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Field of technology
The invention relates to catalyst components and catalysts for the polymerization of olefins and their use, in particular in the polymerization of CH 2 -CHR olefins, where R is an alkyl group, an aryl group, preferably a phenyl group, or a hydrogen atom.
Prior art
Catalysts containing titanium compounds deposited on magnesium halides in active form are well known. Catalysts of this type are described, for example, in U.S. Pat. No. 4,278,718.
These catalysts, although highly effective in the polymerization of both ethylene and alpha-olefins such as propylene, do not have adequate stereospecificity.
This stereospecificity is increased by adding the electron donor compound to the solid component containing the titanium compound. (U.S. Pat. No. 4,544,73).
Further improvements are obtained by using either an electron donor compound added to the solid component (internal donor) or added to the Al-alkyl compound (external donor); U.S. Patent 4,107,414. '
Higher quality in terms of efficiency as well as in terms of. stereospecificity is obtained with the catalysts described in European Patent No. 0045977. The solid component of these catalysts comprises magnesium halide in active form on which a titanium halide (TiCl 4) and an electron donor compound selected from certain groups of carboxylic acid esters are deposited. whose representative examples are phthalates. The cocatalyst used is an Al-alkyl compound to which a silicon compound containing at least one Si-OR bond (R is a hydrocarbon group) is added. ')
V ů
U.S. Pat. No. 4,522,930 discloses catalysts wherein the solid catalyst component comprises an electron donor compound, at least 70 mol% of which can be extracted with an N-triethyl compound under
standard extraction conditions and has, with extraction, specific:
in 2 * 'surface at least 20 m / g. Said catalysts contain as cocatalysts an Al-trialkyl compound to which an electron-donor compound is added which does not undergo complex reactions with the Al-triethyl compound which are detectable by potentiometric titration under defined reaction conditions. »
Examples of the above-mentioned electron donor compounds are?
silicon compounds having Si-OR bonds, wherein R is a hydrocarbon group; 2,2,6,6-tetramethylpiperidine, 2,2,5,5- <
tetramethylpyridine, N-diethyl-2,2,6,6-tetramethylpiperidide and dichloromophenoxyaluminum.
2 published European patent applications 0361494 and 0362705 describe ethers having respective reaction
2 sheets
Sheet 1 Sheet 2
48 members in 24 offices
Priority claims4
| Document | Office | Kind | Date |
|---|---|---|---|
| 1989190 | Italy | A | |
| 1989190 | Italy | A | |
| 9019891 | – | – | – |
| IT19900019891 | – | – | – |
Members48
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|---|---|---|---|
| IT9019891D0 | Italy | D0 | |
| NO911238D0 | Norway | D0 | |
| IT9019891A1 | Italy | A1 | |
| CA2039443A1 | Canada | A1 | |
| FI911507A | Finland | A | |
| NO911238L | Norway | L | |
| NO952325L | Norway | L | |
| AU7386091A | Australia | A | |
| EP0451645A2 | European Patent Office (EPO) | A2 | |
| HU911057D0 | Hungary | D0 | |
| BR9101279A | Brazil | A | |
| KR910016778A | Republic of Korea | A | |
| CN1055933A | China | A | |
| CS87891A2This record | Czechoslovakia (until 1993) | A2 | |
| US5068213A | United States of America | A | |
| HUT57800A | Hungary | A | |
| PT97208A | Portugal | A | |
| IL97679D0 | Israel | D0 | |
| EP0451645A3 | European Patent Office (EPO) | A3 | |
| ZA912288B | South Africa | B | |
| CN1019580B | China | B | |
| TW198043B | Taiwan Province of China | B | |
| AU633712B2 | Australia | B2 | |
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| IT1241093B | Italy | B | |
| JPH0687921A | Japan | A | |
| YU56391A | Yugoslavia, later Serbia and Montenegro (until 2006) | A | |
| IL97679A | Israel | A | |
| NO952325D0 | Norway | D0 | |
| NO178153B | Norway | B | |
| NO178153C | Norway | C | |
| RU2087485C1 | Russian Federation | C1 | |
| EP0891988A2 | European Patent Office (EPO) | A2 | |
| KR0169489B1 | Republic of Korea | B1 | |
| EP0451645B1 | European Patent Office (EPO) | B1 | |
| AT179996T | Austria | T | |
| ATE179996T1 | Austria | T1 | |
| DE69131219D1 | Germany | D1 | |
| ES2132075T3 | Spain | T3 | |
| DK0451645T3 | Denmark | T3 | |
| DE69131219T2 | Germany | T2 | |
| EP0891988A3 | European Patent Office (EPO) | A3 | |
| FI106382B | Finland | B | |
| JP3307658B2 | Japan | B2 | |
| EP0891988B1 | European Patent Office (EPO) | B1 | |
| DE69133274D1 | Germany | D1 | |
| ES2200252T3 | Spain | T3 | |
| DE69133274T2 | Germany | T2 |
Numbers
- Publication, DOCDB
- 87891
- Publication, EPODOC
- CS87891
- Application
- 91878
- Application, DOCDB
- 87891
- Application, EPODOC
- CS19910000878
Titles
- English
- CATALYST COMPONENTS AND CATALYSTS FOR OLEFINS POLYMERIZATION
Classification
- CPC, 2
- C08F10/00
- C08F4/10
- IPC, 8
- C08F4 658
- C08F4 60
- C08F4 646
- C08F4 649
- C08F4 652
- C08F4 654
- C08F10 00
- C08F110 06