WO2001004165A1 - Composants de catalyseurs pre-polymerises pour la polymerisation d'olefines - Google Patents

Composants de catalyseurs pre-polymerises pour la polymerisation d'olefines Download PDF

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Publication number
WO2001004165A1
WO2001004165A1 PCT/EP2000/006613 EP0006613W WO0104165A1 WO 2001004165 A1 WO2001004165 A1 WO 2001004165A1 EP 0006613 W EP0006613 W EP 0006613W WO 0104165 A1 WO0104165 A1 WO 0104165A1
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compound
catalyst
prepolymer
ticl
porosity
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PCT/EP2000/006613
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English (en)
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Licio Zambon
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Licio Zambon
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Priority to AU66924/00A priority Critical patent/AU6692400A/en
Publication of WO2001004165A1 publication Critical patent/WO2001004165A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/04—Monomers containing three or four carbon atoms
    • C08F110/06—Propene

Definitions

  • the present invention relates to components of catalysts for the polymerization of olefins
  • the catalysts obtained from said components are endowed with high polymer yield referred to the solid catalyst component present in the prepolymer (one or more times higher than the yield of catalysts obtained from the prepolymer not reacted with the Ti compound).
  • the polymer yield is not remarkably high if referred to the total prepolymerized solid component comprising the prepolymer.
  • the high content of polymer present in the solid catalyst component may create problems particularly regarding the feeding of the component into the polymerization plant.
  • the catalyst components of the present invention comprise the product obtained by contacting a compound of Ti, V, Zr or Hf or mixture thereof, containing at least a transition metal-halogen bond and optionally one or more transition metal- ⁇ bonds, with a prepolymer having porosity greater than 0.3 cm 3 /g (by mercury porosimetry) used in amount from 0.5 to 50 g per g of the solid component of the catalyst used in the preparation of the prepolymer.
  • a support selected from: a) inorganic porous oxides or porous polymers, having porosity of at least 0.5 cm 3 /g (by nitrogen porosimetry) and surface area of at least 100 m 2 /g (BET), containing supported therein a Mg dihalide, preferably Mg dichloride, formed in situ by conversion of a Mg compound different from the Mg halide, fixed on the support; b) Ti and/or V trihalides having surface area higher than 100 m 2 /g (BET) and porosity greater than 0.3 cm 3 /g (by nitrogen porosimetry), said trihalides being preferably supported on a porous support having porosity greater than 0.5 cm 3
  • the Ti, V, Zr or Hf compound used in the reaction with the prepolymer, as well as that supported on the solid component of the catalyst used for the prepolymer preparation, is preferably choose among TiCl , VOCl 3 , ZrCl and metalloce compounds of Ti, Zr and Hf containing two pentadienil rings coordinated with the transition metal, and optionally substituted with halogen, hydrocarbon radicals or other radicals and/or bridge-connected or condensed with other rings.
  • Ti(OR) n - y X y compounds wherein n is the valence of Ti and y is a number from 1 to n; X is halogen; is a hydrocarbon radical with 1-12 C.
  • Representatives compounds are Ti(OR) and the halogenated derivatives thereof, wherein R is an alkyl radical whit 1-8 C, such as Ti-tetrabutylate and Ti-mono and Ti-dichloroalcoholates.
  • Ti amides and chloro-Ti-amides are also suitable compounds.
  • the inorganic porous oxides have a porosity of preferably 1 to 3.5 cm 3 /g and surface area from 100 to 500 m 2 /g.
  • the oxide is selected from silica, silica-gel and alumina.
  • silica examples include Grace Devison 952 silica with surface area of 270 m 2 /g, porosity (by nitrogen) of 1.53 cm 3 /g and water content (Fischer method) of 4.3% by weight;
  • Grace 332 silica-gel surface area of 330 m /g, porosity of 2.0 cm /g - by nitrogen - and water content of 4% by weight
  • a silica gel with diameter of the particles from 20 to 45 micron, porosity (by nitrogen) of 1.75 cm /g and surface area of 320 m /g.
  • AKZO Ketijen B alumina (pseudo bohemite crystalline form with surface area of 266 m /g, porosity - by nitrogen - of 0.64 cm /g and water content of 17%> by weight (Fischer method), is an example of suitable aluminas.
  • the metal oxide support contains surface hydroxyls in quantity that can reach 3 m.mols and more per g of oxide.
  • chemically uncombined water is also present in quantity up to 20 m.mols per g of oxide.
  • the amount of OH groups is regulated by heating the oxides at temperatures from 150 to
  • the chemically uncombined water is added according to various procedures.
  • One of the preferred method consists in passing a stream of humidity - containing nitrogen over the oxide previously dried.
  • the quantity of hydroxyls is preferably comprised from 1 to 3 m.mols per g of oxide; water can be present in amount from 1 to 10 m.mol per g oxide.
  • the polymeric supports preferably are in form of microspheroidal particles with diameter of 20 to 200 micron.
  • a class of polymeric supports particularly suitable is represented by the styrene polymers partially cross-linked with monomers such as divinylbenzene.
  • a microspheroidal polystyrene support has surface are of 370 m /g, porosity
  • the supportation of the Mg halide, on the inorganic porous support is made according to various methods.
  • One of these (described in E-P-A-0437264) consists in reacting the metal oxide with a Mg alkyl compound such as CH 3 Mg Br, CH 3 Mg Cl, nC 4 H 9 Mg Cl, nC 3 H 7 Mg Cl and complexes thereof with ethers such as ethyl ether and tetrahydrofurane, in quantity of not causing reduction of the titanium compound in the subsequent reaction of the support with a compound of tetravalent Ti.
  • the Mg halide is formed in situ by reaction of the metalorganic Mg compound fixed on the metal oxide support with a halogenated compound of tetravalent Ti.
  • the reaction is carried out at 40°C - 130°C, preferably 80-130°C with a duration of 0.25 to
  • the treatment with TiCl is repeated one or more times and the solid washed as above indicated.
  • Any electron-donor capable of forming complexes with the Mg dichloride is usable.
  • Preferred compounds are the esters of aromatic acids, particularly dicarboxylic acids such as the phthalates e.g. dusobuthyl, dioctyl and diphenyl- phthalates and the esters of malonic, pivalic, succinic and carbonic acids.
  • Dieters such as 2.2-diisobutyl-1.3-dimethoxy-propane, 2-isopropyl-2-isopentyl-1.3- dimethoxy-propane, 1.1 bis (methoxy methyl) indene, and 9.9-bis-methoxy methyl - 2.3,
  • 6,7 tetrame hyl fluorene and derivatives thereof substituted with hydrocarbon radicals or halogens are examples of preferred compounds.
  • the quantity of electron-donor compound is from 0.1 to 1.5 mols, preferably 0.2-0.4 mols per Mg-g-atom.
  • the Mg content in the oxides is comprised from 0.5 to 20% by weight.
  • the ratio Mg/Ti ranges from 1.5 to 10; the electron-donor compound is present from 5-
  • the surface area of the catalyst components is from 100 to 300 m 2 /g and the porosity is greater than 0.5 cm 3 /g (by nitrogen).
  • silica gel previously dehydrated is treated whit alkyl Mg compounds such as Mg (butyl-octyl) and Mg dibutyl and thereafter with a chlorinating agent (HC1) to decompose the metalorganic compound to form Mg Cl 2 in situ.
  • An alkanol such as ethanol is thereafter reacted to form an adduct Mg Cl .3C 2 H 5 OH which is than dealcoholated by reaction with TiCl 4 .
  • a further method consists in dissolving MgCl in absolute ethanol, in adding a part of the obtained solution to a suspension in ethanol of silica gel (GRACE 332), in treating the suspension whit TiCl 4 in excess and containing an electron-donor compound, at temperatures from 100° to 120°C.
  • the treatment with TiCl is repeated one or more times and the solid is repeatedly washed with hexane.
  • the supportation of the Mg halide on the polymeric supports is carried out with methods similar to those used for the supportation on the metal oxides.
  • the polymeric support with a quantity of solution of Mg halide, preferably Mg Cl 2 , in an alcohol, such as ethanol and butanol, in quantity to fix from 1 to 20 g of Mg per 100 g of support and from 1 to 6 mols alcohol.
  • Mg halide preferably Mg Cl 2
  • alcohol such as ethanol and butanol
  • the adduct thus supported is thermally dealcoholated to form the Mg halide or is reacted with compounds such as SiCl and Al-trialkyls.
  • the Mg halide is formed by reaction with TiCl 4 in excess: this allows to obtain the Mg halide and contemporaneously of fixing the Ti compound on the halide.
  • the trihalide preferably TiCl 3 obtained from TiCl by reduction with hydrogen, or VC1 3
  • alkanol preferably ethanol or butanol
  • Ti or V per lOOg of support and from 1 to 6 mols, preferably 3 mols, of alcohol per g-atom of Ti or V.
  • the adduct is fhermically dealcoholated to form the Ti or V trihalide in active form or by reaction with compounds such as SiCl and Al-triethyl.
  • the adduct is dealcholated preferably by reaction with TiCl 4 in excess: this allows to directly fix the Ti compound on the Ti or V trihalide.
  • the trihalide is converted into the form having the required characteristics by thermally dealcoholating adducts with 1 -6 mols of alcanol, preferably 3 mols of ethanol or butanol per mol of trihalide, or by reaction with compounds such as SiCl 4 , TiCl 4 and Al- trialkyls.
  • the supportation of TiCl 4 or VOCl 3 and similar compounds on the porous support containing the Mg halide or on the Ti or V trihalide is carried out by reacting the Ti or V compound in excess, preferably operating in presence of an electron-donor compound such as an ether of the types above specified or an alkylphthalate, in quantity of 10-30%) by mols per g-atom of Ti or V of the trihalides.
  • an electron-donor compound such as an ether of the types above specified or an alkylphthalate, in quantity of 10-30%) by mols per g-atom of Ti or V of the trihalides.
  • the prepolymer preparation is carried out according to known methods operating at temperatures preferably from 0° to 25°C, in presence of an Al-alkyl compound, particularly Al-triethyl or triisobutyl, in molar ratio Al/transition metal compound present in the supported catalyst component preferably comprised form 10 to 50.
  • ethylene or propylene are the olefins preferably used.
  • the catalyst used in the prepolymerization of olefins different from ethylene is of preference stereospecific capable of providing polymers with isotacticity index higher than 80-90%.
  • an electron-donor compound fixed either on the solid catalyst component (inside donor) and partially complexed with the Al-alkyl compound (outside donor) or fixed only on the solid component allows to render sterospecific a catalyst comprising a Ti compound supported on a Mg halide.
  • the catalyst is per se sufficiently stereospecific: also in this case, however it is convenient to use an inside donor.
  • the preferred inside donors are the alkyl or isoalkylphthalates and the diethers as hereinbefore specified.
  • an inside donor and preferably also an outside donor is used.
  • the preferred inside donors are the ethers and the alkylphthalates as hereinbefore specified.
  • the phthalates are preferably used in combination with an outside donor such as a silane.
  • the molar ratio Al alkyl compound/transition metal compound present in the prepolymer is comprised in a wide range; preferably is greater than 10.
  • the Al-alkyl compound is an alumoxane, preferably methylpolyalumoxane.
  • the (co)polymerization of olefins with the new catalysts is carried out according to known methods operating in liquid phase or in suspension in an inert hydrocarbon solvent or in gas phase.
  • the new catalysts allow, besides other advantages, to eliminate the prepolymerization step which normally is used in the processes for the production of polyolefins and to obtain polymers with extremely low catalyst residues.
  • Example 1 of EP-A- 437264 is repeated obtaining polymerization results substantially corresponding to those reported in said example (TEST A).
  • the catalyst component prepared according to the Example of the European application is used in a prepolymerization test with propylene to obtain a weight ratio prepolymer/solid catalyst component of 3 : 1.
  • the prepolymerization was carried out in hexane using Al-triethyl (TEAL) in weight ratio with the solid catalyst component of 0.5, and 2-isopropyl-2-isopentyl-l,3- dimethoxypropane (DMP) as outside donor (molar ratio TEAL/DMP of 20).
  • TEAL Al-triethyl
  • DMP 2-isopropyl-2-isopentyl-l,3- dimethoxypropane
  • the prepolymerized catalyst component is used in a polymerization test of propylene under the conditions of Example 1 of the European application (TEST B).
  • the polymer yield referred to the prepolymer was of about 3 times less than that obtained with the catalyst of TEST A.
  • the prepolymer obtained according to Comparison Example 1 is suspended in TiCl containing DMP, in amount such as to have a ratio of 50 g prepolymer per 1000 ml of
  • the temperature is raised to 80°C and the mixture is maintained under stirring for 1 hour.
  • a polymer yield referred to the prepolymerized catalyst component is obtained higher than the yield of TEST B of Comparison Example 1.
  • Example 2 of USP 4.857.613 is repeated obtaining polymerization results substantially corresponding to those therein reported (TEST A).
  • the catalyst component prepared according to the above example is prepolymerized with propylene under the condition reported in Comparison Example 1 to obtain a weight ratio prepolymer/solid catalyst component of 3 : 1.
  • the prepolymer is then used in the polymerization of propylene under the conditions reported in Example 2 of USP 4.857.613.
  • the polymer yield referred to the prepolymer of the catalyst component (TEST B) was of about 3 times less than that of TEST A.
  • the polymeric solid component was thereafter used in a polymerization test of propylene under the conditions of Example 2 of USP 4.857.613.
  • the polymer yield referred to the prepolymerized catalyst component was higher than that obtained according to TEST B of Comparison Example 2.
  • a solution of MgCl in ethanol containing 10 g MgCl 2 is added to a suspension of silica gel (Grace 332) in ethanol, and maintained under stirring for 0.5 hour.
  • the suspension is dried at 50°Cunder vacuum to obtain a solid containing 4 mols of ethanol per mol of MgCl .
  • the solid is added to TiCl (weight ratio 1 :30 with respect to TiC14) and the mixture heated to 100°C.
  • di-n-butylphthalate(DNBF) is added in molar ratio Mg/DNBF of 4.
  • the mixture is maintained at 100°C for 2 hours and, after decantation, the treatment is repeated at 1 10°C for 1 hour.
  • Part of the solid catalyst component is used in a prepolymerization test with propylene at room temperature using Al-triethyl in weight ratio with the solid component of 0.05 and using DMP as outside donor in molar ratio TEAL/DMP of 20.
  • the polymerization is continued until 2 g polymer for 1 g of solid catalyst component are obtained.
  • the polymeric catalyst component is used in a test of propylene polymerization under the condition of TEST A.
  • the polymer yield referred to the prepolymer of the catalyst component is higher than that of TEST B of Comparison Example 3.
  • Example 3 to obtained 10 g polymer per g of solid component.
  • Part of the polymeric catalyst component is used in a propylene polymerization test carried out under the conditions of Comparison Example 3 obtaining a polymer yield of about 1 1 time lower that that of TEST A.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)

Abstract

L'invention concerne des composants de catalyseurs destinés à la polymérisation des oléfines CH2=CHR, où R désigne hydrogène ou un radical alkyle à 1-12 atomes de carbone ou un radical aryle, comprenant le produit obtenu par la mise en contact d'un composé Ti V, Zr ou Hf comportant au moins une liaison halogène métallique et éventuellement une liaison métal-π, avec un prépolymère ayant une porosité (porosimétrie au mercure) supérieure à 0,3 cm3/g obtenu à l'aide d'un catalyseur comprenant un composé Ti, V Zr ou Hf du type susmentionné, reposant sur un support poreux contenant un dihalogénure Mg formé in situ par conversion d'un composé Mg différent des dihalogénures Mg ou sur un support TiC1¿3? et/ou VC13 ayant une superficie supérieure à 100 m?3¿/g et une porosité supérieure à 0,5 cm3/g (porosimétrie à l'azote).
PCT/EP2000/006613 1999-07-14 2000-07-10 Composants de catalyseurs pre-polymerises pour la polymerisation d'olefines WO2001004165A1 (fr)

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IT1999MI001552A ITMI991552A1 (it) 1999-07-14 1999-07-14 Componenti di catalizzatori per la polimerizzazione di olefine

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017021454A1 (fr) * 2015-08-04 2017-02-09 Basell Poliolefine Italia S.R.L. Procédé en phase gazeuse de polymérisation du propylène

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EP0068799A2 (fr) * 1981-06-22 1983-01-05 Exxon Research And Engineering Company Composant catalytique à base de trichlorure de titane et son procédé de préparation
EP0673950A1 (fr) * 1994-03-23 1995-09-27 Elf Atochem S.A. Composante catalytique pour la polymérisation des oléfines obtenue par imprégnation d'un prépolymère par une solution d'une composante catalytique et polymère obtenue à partir de ladite composante catalytique
WO1995026369A1 (fr) * 1994-03-29 1995-10-05 Montell Technology Company Bv Constituants et catalyseurs destines a la polymerisation d'olefines
US5556893A (en) * 1993-05-25 1996-09-17 Solvay (Soci et e Anonyme) Catalyst support and catalyst for the polymerization of alpha-olefins; processes for obtaining them and polymerization of alpha-olefins in presence of the catalyst
US5589549A (en) * 1994-07-20 1996-12-31 Montell Technology Company Bv Multistage process for the (CO) polymerization of olefins
US5783645A (en) * 1994-09-29 1998-07-21 Union Carbide Chemicals & Plastics Technology Corporation Non-sticky prepolymerized catalyst, and use thereof in production of non-sticky resin
ITMI981823A1 (it) * 1998-08-03 2000-02-03 Licio Zambon Catalizzatori per la polimerizzazione delle olefine

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0068799A2 (fr) * 1981-06-22 1983-01-05 Exxon Research And Engineering Company Composant catalytique à base de trichlorure de titane et son procédé de préparation
US5556893A (en) * 1993-05-25 1996-09-17 Solvay (Soci et e Anonyme) Catalyst support and catalyst for the polymerization of alpha-olefins; processes for obtaining them and polymerization of alpha-olefins in presence of the catalyst
EP0673950A1 (fr) * 1994-03-23 1995-09-27 Elf Atochem S.A. Composante catalytique pour la polymérisation des oléfines obtenue par imprégnation d'un prépolymère par une solution d'une composante catalytique et polymère obtenue à partir de ladite composante catalytique
WO1995026369A1 (fr) * 1994-03-29 1995-10-05 Montell Technology Company Bv Constituants et catalyseurs destines a la polymerisation d'olefines
US5589549A (en) * 1994-07-20 1996-12-31 Montell Technology Company Bv Multistage process for the (CO) polymerization of olefins
US5783645A (en) * 1994-09-29 1998-07-21 Union Carbide Chemicals & Plastics Technology Corporation Non-sticky prepolymerized catalyst, and use thereof in production of non-sticky resin
ITMI981823A1 (it) * 1998-08-03 2000-02-03 Licio Zambon Catalizzatori per la polimerizzazione delle olefine
WO2000008065A2 (fr) * 1998-08-03 2000-02-17 Montell Technology Company B.V. Composants prepolymerises de catalyseurs pour la polymerisation d'olefines

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017021454A1 (fr) * 2015-08-04 2017-02-09 Basell Poliolefine Italia S.R.L. Procédé en phase gazeuse de polymérisation du propylène
WO2017021122A1 (fr) * 2015-08-04 2017-02-09 Basell Poliolefine Italia S.R.L. Composants de catalyseur prépolymérisé pour la polymérisation d'oléfines
KR20180028486A (ko) * 2015-08-04 2018-03-16 바셀 폴리올레핀 이탈리아 에스.알.엘 올레핀 중합용 예비 중합 촉매 성분
CN107873037A (zh) * 2015-08-04 2018-04-03 巴塞尔聚烯烃意大利有限公司 用于聚合丙烯的气相工艺
CN107873036A (zh) * 2015-08-04 2018-04-03 巴塞尔聚烯烃意大利有限公司 用于聚合烯烃的预聚合催化剂组分
US10435490B2 (en) 2015-08-04 2019-10-08 Basell Poliolefine Italia S.R.L. Prepolymerized catalyst components for the polymerization of olefins
KR102056017B1 (ko) 2015-08-04 2020-01-14 바셀 폴리올레핀 이탈리아 에스.알.엘 올레핀 중합용 예비 중합 촉매 성분
RU2721530C2 (ru) * 2015-08-04 2020-05-19 Базелл Полиолефин Италия С.Р.Л. Газофазный способ полимеризации пропилена
US10730974B2 (en) 2015-08-04 2020-08-04 Basell Poliolefine Italia S.R.L. Gas-phase process for the polymerization of propylene
CN107873036B (zh) * 2015-08-04 2021-03-30 巴塞尔聚烯烃意大利有限公司 用于聚合烯烃的预聚合催化剂组分

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