WO2010043355A1 - Catalyseur pour la fabrication de polyéthylène linéaire basse densité - Google Patents

Catalyseur pour la fabrication de polyéthylène linéaire basse densité Download PDF

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Publication number
WO2010043355A1
WO2010043355A1 PCT/EP2009/007311 EP2009007311W WO2010043355A1 WO 2010043355 A1 WO2010043355 A1 WO 2010043355A1 EP 2009007311 W EP2009007311 W EP 2009007311W WO 2010043355 A1 WO2010043355 A1 WO 2010043355A1
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WO
WIPO (PCT)
Prior art keywords
catalyst
compound
magnesium
reacting
catalyst according
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PCT/EP2009/007311
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English (en)
Inventor
Wei Xu
Atieh Aburaqabah
Sirajudeen Mohamed
Srikant Hazra
Original Assignee
Saudi Basic Industries Corporation
Sabic Petrochemicals B.V.
Priority date (The priority date 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 date listed.)
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Application filed by Saudi Basic Industries Corporation, Sabic Petrochemicals B.V. filed Critical Saudi Basic Industries Corporation
Priority to EP09778885A priority Critical patent/EP2350137A1/fr
Publication of WO2010043355A1 publication Critical patent/WO2010043355A1/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
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers

Definitions

  • the present invention relates to a catalyst for the production of linear low density polyethylene.
  • the invention is also directed to a process for the production of linear low density polyethylene in the presence catalyst according to the invention.
  • Dall'Occo et al. disclose in "Transition Metals and Organometallics as Catalysts for Olefin Polymerization” (Springer, 1988, at page 209 ) that the main requirements of industrial catalysts for the polymerisation of ethylene are high productivity, proper kinetic, no reactor fouling , control of morphology , average particle size and bulk density of the polymer particles.
  • the bulk density of the polyethylene powder particles is important because the obtained powder has to be stored and to be transported. A higher bulk density may decrease clogging at its transportation and it is possible to increase a storable amount per unit volume. By increasing the bulk density, the weight of the polyethylene per unit volume present in a polymerization vessel will be increased and the concentration of the polyethylene powder in the polymerization vessel can be enhanced.
  • Polyethylenes and their polymerization processes are disclosed at pages 27-67 of Handbook of Polyethylene by Peacock (ISBN 0-8247-9546-6).
  • Polyethylenes such as for example linear low density polyethylene (LLDPE) and high density polyethylene (HDPE) are substantially linear polymers with numbers of short branches.
  • LLDPE or HDPE can be initiated by the use of transition metal based catalysts for example Ziegler catalysts and Philips catalysts.
  • the polymerization process can take place in for example a solution phase reactor, a, slurry phase reactor or a gas phase reactor. In solution phase reactions octene is often applied as the co monomer while in slurry phase or gas phase reactions in general butene and hexene are copolymerized with ethylene.
  • LLDPE possesses properties that distinguish it from other ethylene polymers.
  • Ethylene copolymers are used in for example blown and cast films, injection molding, rotational molding, blow molding, pipe, tubing, and wire and cable applications.
  • LLDPE can be used to make thinner films with improved environmental stress cracking resistance.
  • LLDPE has good resistance to chemicals and to ultraviolet radiation and good electrical properties.
  • a huge amount of publications is directed to the use of Ziegler-Natta type polymerisation catalysts. In general Ziegler Natta catalysts have as a disadvantage that in the case that the activity of the catalyst is relatively high the bulk density of the resulting polymer is relatively low. It is highly desirable to obtain a Ziegler-Natta catalyst which can be manufactured easily with the same or better productivity and at the same time produces higher bulk density LLDPE.
  • This catalyst has also to result in other desired properties of the obtained polymer and the polymerisation process such as for example a lower density and reduced resin stickiness, reduced chunk formation and reduced reactor fouling in the fluid bed gas-phase process, especially at high production rates.
  • the catalyst according to the invention is obtained by an one pot process comprising the steps:
  • step (3) reacting the product obtained in step (2) with a compound containing a group IV (of Mendeleev's Periodic System of Chemical Elements ) transition metal component wherein the titanium loading of the catalyst ranges between 1.2 % by weight and 6.0 % by weight relative to the total weight of the catalyst.
  • a group IV of Mendeleev's Periodic System of Chemical Elements
  • the alkyl, cycloalkyl, aryl and/or alkaryl group in step (1 ) comprises 1 -50 carbon atoms.
  • the process according to the present invention wherein all process steps are performed in one vessel results in catalyst particles with a controlled and consistent particle size, shape and size distribution.
  • the catalyst also has a good hydrogen response.
  • LLDPE obtained with the catalyst according to the invention results in LLDPE having the desired bulk density, good co monomer incorporation and high polymer productivity.
  • LLDPE obtained with the catalyst according to the invention has a density ranging between 900 kg/m 3 and 929 kg/m 3 ; a melting point ranging between 95 0 C and 135 0 C and a bulk density ranging between 290 kg/m 3 and 500 kg/m 3
  • the titanium loading of the catalyst ranges between 1.2 % by weight and 3.0 % by weight relative to the total weight of the catalyst.
  • step (3) reacting the product obtained in step (2) with a compound containing a group IV transition metal component and
  • Suitable support material include inorganic oxides, magnesium chloride, clays and zeolites, polystyrene, polyethylene, polypropylene, graphite and/or layered silicates.
  • materials include for example oxides of silica, alumina, magnesia, titanium and/or zirconium.
  • the support includes silica and/or alumina. According to a further preferred embodiment of the invention the support is based on silica.
  • the carrier has been dehydrated by fluidizing with nitrogen and heating.
  • the support material particles may have any shape. Preferably the shape is approximately spherical and porous.
  • RMgX X is preferably chlorine.
  • Preferred compounds having the formula RMgX or MgR 1 R 2 include magnesium dialkyl and magnesium alkyl chloride.
  • the alkyl group contains 1 -8 carbon-atoms.
  • the alkyl groups may be substituted.
  • Suitable examples of non-polar solvents in all preparation steps include hydrocarbons.
  • Suitable hydrocarbons include for example iso butane, iso pentane, hexane and heptane.
  • Preferred compounds which are able to react with unreacted magnesium units are chlorine containing components and/or heteroatom containing components. These compounds prevent by the reaction with alkyl magnesium moieties that the Ti-compound in the third step is reduced.
  • the chlorine containing component may be (C 1 -Ci 0 ) alkyl chloride or a silicon compound of formula R m SiCI 4-m wherein 0 ⁇ m ⁇ 2 and R is a hydrocarbon radical containing 1 - 10 carbon atoms.
  • the chlorine containing component is (CrCe) alkyl chloride.
  • the alkyl chloride is tertiary butyl chloride.
  • Suitable heteroatom containing components include alcohols, aldehydes, CU 2 , H 2 O, amines, sulfonates and/or a compound with antistatic properties.
  • Suitable compound with antistatic properties or antistatic agents include organic compounds or mixture containing at least one electron rich heteroatom from Group IV, V and/or Vl , preferably O or N , and a hydrocarbyl moiety where the hydrocarbyl group is a branched or straight, substituted or un- substituted hydrocarbyl group.
  • Suitable group IV transition metal components include Ti, Zr and Hf.
  • the compound containing a group IV transition metal is TiCI 4
  • the compound containing a group IV transition metal component may additionally be based on a group 16 element for example O and S.
  • the group IV transition metal component with a group 16 element is an organic oxygen containing titanium compound.
  • Suitable organic oxygen containing titanium compound may be represented by the general formula [TiO x (OR). 4 - 2x ].n in which R represents an organic radical, x ranges between 0 and 1 and n ranges between 1 and 6.
  • organic oxygen-containing titanium compounds include alkoxides, phenoxides, oxyalkoxides, condensed alkoxides, carboxylates and enolates.
  • the organic oxygen-containing titanium compounds is a titanium alkoxide.
  • Suitable alkoxides include for example Ti (OC 2 H 5 ) 4 , Ti (OC 3 Hy) 4 ,
  • the organic oxygen containing titanium compound is Ti (OC 2 Hs) 4 . Also mixtures of TiCI 4 and organic oxygen containing titanium compounds may be applied.
  • Suitable donors include for example tetrahydrofuran, di methyl formamide and/or ethyl acetate.
  • the preferred co catalyst is an organo aluminium compound having the formula AIR 3 in which R is a hydrocarbon radical containing 1 - 10 carbon atoms
  • organo aluminium compound of the formula AIR 3 include for example triethylaluminium alkyl, triisobutyl aluminium alkyl, tri-n-hexyl aluminium and tri octyl aluminium.
  • the resulting activated catalyst composition results in substantially higher productivity in polymerizing alpha-olefins and in substantially improved higher comonomer incorporation properties.
  • the preferred promoter is an organo alkyl chloride containing 1 -10 carbon atoms or an organo aluminium chloride having the formula AIR n X 3 - n wherein X is a halogen and R is a hydrocarbon radical containing 1 - 10 carbon atoms and
  • Suitable examples include ethyl aluminium dichloride, propyl aluminium dichloride, n- butyl aluminium dichloride, iso butyl aluminium dichloride, diethyl aluminium chloride, diisobutyl aluminium chloride and CHCI 3.
  • the molar ratio of tetravalent titanium: organo magnesium ranges between 0.2:1 and 3:1.
  • the molar ratio of magnesium: halogenide ranges between 2:1 and 1 :2. More preferably the molar ratio of magnesium: halogenide ranges between 1.2:1 and 1 : 1.2.
  • the molar ratio Al: Ti ranges between 0.1 : 1 and 10:1.
  • the average particle size of the catalyst ranges between 20 ⁇ m and 70 ⁇ m.
  • the catalyst is obtained by a process comprising the following steps:
  • the titanium loading of the catalyst ranges between 1.2 % by weight and 6.0 % by weight relative to the total weight of the catalyst.
  • the titanium loading of the catalyst ranges between 1.2 % by weight and 3.0 % by weight relative to the total weight of the catalyst
  • the catalyst is obtained by a process comprising the following steps: (1 ) reacting a silica support with a dialkyl magnesium or a magnesium alkyl chloride having the formula RMgX or MgR 1 R 2 wherein the alkyl groups contain 1 -8 carbon atoms
  • the titanium loading of the catalyst ranges between 1.2 % by weight and 3.0 % by weight relative to the total weight of the catalyst. Additional advantages of the catalyst used in the process according to the invention are the easy catalyst preparation procedures, the high catalyst productivity, the low amount of fines, less reactor sheeting and excellent polymer morphology.
  • the modification of the catalyst may take place with a compound with antistatic properties such as for example Atmer ® Octastats ® or Stadis ® .
  • the Ziegler-Natta catalysts obtained with the process according to the invention may be used to produce ethylene homo- and/or copolymers with either a gas phase process or a slurry process under the general conditions.
  • LLDPE also high density polyethylene and bimodal polyethylene may be produced.
  • the obtained particle morphology is excellent, which will be beneficial to all particle forming polymerization processes.
  • HDPE produced with the present catalyst has a density ranging between 910 kg/m 3 and 970 kg/m 3 ; a melting point ranging between 95 0 C and 135 0 C and a bulk density ranging between 290 kg/m 3 and 500 kg/m 3
  • WO03004537 discloses a method for the two step preparation of a procatalyst for an olefin polymerization comprising the steps: a) treating silica by successively contacting said silica with a pair of compounds comprising a moderator compound and a magnesium alkyl compound, wherein said moderator compound is able of being reduced in a controlled manner by said magnesium alkyl compound, to obtain a modified silica ; b) contacting said modified silica with a chlorine containing titanium compound to obtain a solid procatalyst.
  • the moderator compound serves for moderating the reductive power of the magnesium alkyl compound
  • the moderator compound is a chlorine containing compound such as SiCI 4 , TiCI 4 , ZrCI 4 , HfCI 4 or SnCI 4 Or a gas which contains oxygen.
  • the present invention does not require the treatment of the support with a mixture that must comprise a moderator compound and a magnesium alkyl compound as required by the process according to WO03004537.
  • the process as disclosed in Example 3 of WO03004537 uses both a specific aluminium alkyl-magnesium alkyl compound and air.
  • WO03004537 does not disclose the preparation of LLDPE.
  • US2008/058198 discloses a high activity magnesium-based supported catalyst component useful in a catalyst system for the compolymerization of ethylene and alpha-olefin.
  • alkoxysilane ester is contacted with a halogen-substituted silane to form an organic silicon complex.
  • the organic silicon complex is contacted with an aminosilane compound to form an organic silicon complex containing nitrogen.
  • the process according to the present invention does not use an aminosilane. Furthermore this process does not use a silicon complex containing nitrogen.
  • the organic silicon complex containing nitrogen or the organic silicon complex is contacted with a transition metal compound to form an organic silicon complex containing transition metal.
  • the organic silicon complex containing transition metal is then contacted with a substituted aromatic ring nitrogen compound to form a fourth reaction complex, which is then contacted with a magnesium-based composite support that has been prepared in situ by reacting metallic magnesium with an alkyl or aromatic halide to form the catalyst component.
  • a magnesium-based composite support that has been prepared in situ by reacting metallic magnesium with an alkyl or aromatic halide to form the catalyst component.
  • US 5424263 discloses a catalyst component useful in the polymerization of olefins especially propylene.
  • the catalyst component comprises the product obtained by steps of (a) contacting silica with at least one hydrocarbon soluble magnesium-containing compound; (b) contacting the product of step (a) with component (1), a heterocyclic fused ring compound substituted with at least one oxygen atom, and component (2), a modifying compound selected from the group consisting of silicon halides, boron halides, aluminum halides, alkyl silicon halides and mixtures thereof, with the proviso that components (1 ) and (2) be present such that the molar ratio of component (2) to component (1 ) is at least about 4:1 ; and (c) contacting the product of step (b) with a titanium-containing compound having the structural formula TiXm(OR) n , where X is halogen; R is hydrocarbyl; m is an integer of 1 to 4; and n is 0 or an integer of 1 to 3 with the pro
  • US 5424263 An essential difference between US 5424263 and the present invention is the presence of a heterocyclic fused ring compound substituted with at least one oxygen atom in the process according to US 5424263 which is not present in the process according to the present invention.
  • US 5424263 is directed to the use of the catalyst in the preparation of polypropylene.
  • US 5424263 does not disclose a polymerisation to obtain LLDPE.
  • EP2003151 discloses a process for preparing a catalyst useful in gas phase polymerization of olefins wherein the hydrogen response of the catalyst can be improved by using a ketone as the electron donor in the catalyst.
  • the catalyst consists of compounds of Ti, Mg, Al and a ketone. In the process according to the present invention no keton is present to manufacture a copolymer having an Ml greater than that prepared in the absence of a ketone.
  • the invention will be illustrated by the following non-limiting examples.
  • the density (kg/m 3 ) was determined as specified in ASTM D 1505-68 with the exception that the density measurement was taken 4 hours instead of 24 hours after the sample was placed in the density column.
  • the calibration of the HT-GPC uses a Hamielec type calibration with broad standard and fresh calibration with each sample set.
  • the FT-IR calibration is based on 10 samples of defined branching type and branching frequency available form Polymer Labs. •
  • the poured bulk density (BD) of the polyethylene powder was determined by measuring the bulk density of the polymer powder according to the procedure outlined in ASTM D1895/A.
  • the obtained slurry was kept at 5O 0 C for 0.5 hours.
  • the slurry polymerisation process to prepare ethylene-1 -butene copolymer was carried out in deoxygenated isopentane in a two-liter stirred autoclave with use of the catalyst according to Examples l-lll.
  • the catalyst was added in an amount of 50 mg.
  • Comparative Examples A-C Preparation of the catalyst in a one pot process The preparations as described in the Examples l-lll were repeated with the exception that the titanium loading was outside the range between 1.2 % by weight and 3.0 % by weight relative to the total weight of the catalyst.
  • Gas phase polymerizations were carried out in a fluidized bed reactor at a production rate of 10 kg/hr in the presence of ethylene and 1 - butene comonomer.
  • the fluidized bed of reactor was made up of HDPE polyethylene granules.
  • the reactor was passivated with aluminum alkyl.
  • ethylene and 1 -butene comonomer were introduced before the reactor bed.
  • the individual flows of ethylene, hydrogen and 1 -butene comonomer were controlled to maintain target reactor conditions wherein the H 2 /C 2 ratio was 10%, the C 4 /C 2 ratio was 35% and the C 2 partial pressure was 7 bar (7.1O 6 MPa).
  • the concentrations of ethylene and 1 -butene were measured by an on-line chromatograph.
  • the examples are directed to samples taken from a 2 days polymerization run on a single gas phase fluidized bed reactor.
  • a catalyst according to Examples l-lll was injected directly into the fluidized bed using purified nitrogen wherein the catalyst injection rates were adjusted to maintain a production rate of 10 kg/hr.
  • the reacting bed of growing polyethylene particles was maintained in a fluidized state by a continuous flow of the make-up feed and recycle gas through the reaction zone.
  • Each polymerization run utilized a reactor temperature of 87 0 C.
  • the reactor temperature was maintained at a constant level by adjusting up or down the temperature of the recycle gas to accommodate any changes in the rate of heat generation due to the polymerization.

Abstract

L'invention porte sur un catalyseur pour la fabrication de polyéthylène linéaire basse densité. Le catalyseur est obtenu par un procédé monotope comportant les étapes (1) de réaction d'un support avec un composé représenté par la formule RMgX ou MgR1R2, dans laquelle R, R1 et R2 sont choisis dans le groupe constitué par alkyle, cycloalkyle, aryle ou alkylaryle et X est choisi dans le groupe constitué par halogène, OR3 ou OC(O)R4, R3 et R4 étant des groupes alkyles contenant 2 à 50 atomes de carbone, (2) de réaction du support traité par le magnésium avec un composé qui peut réagir avec des unités du magnésium n'ayant pas réagi et (3) de réaction du produit obtenu dans l'étape (2) avec un composé contenant un composant de métal de transition du groupe IV, la charge en titane du catalyseur allant de 1,2 % en poids à 6,0 % en poids par rapport au poids total du catalyseur.
PCT/EP2009/007311 2008-10-15 2009-10-12 Catalyseur pour la fabrication de polyéthylène linéaire basse densité WO2010043355A1 (fr)

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Application Number Priority Date Filing Date Title
EP09778885A EP2350137A1 (fr) 2008-10-15 2009-10-12 Catalyseur pour la fabrication de polyéthylène linéaire basse densité

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EP08075826.1 2008-10-15
EP08075826 2008-10-15

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WO2010043355A1 true WO2010043355A1 (fr) 2010-04-22

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104066685A (zh) * 2011-08-08 2014-09-24 巴斯夫欧洲公司 制备超纯氢氧化镁和氧化镁的方法
US9540457B1 (en) 2015-09-24 2017-01-10 Chevron Phillips Chemical Company Lp Ziegler-natta—metallocene dual catalyst systems with activator-supports
US9718907B2 (en) 2015-07-08 2017-08-01 Chevron Phillips Chemical Company Lp Ziegler-Natta—metallocene dual catalyst systems with activator-supports
US9758599B2 (en) 2015-09-24 2017-09-12 Chevron Phillips Chemical Company Lp Heterogeneous Ziegler-Natta catalysts with fluorided silica-coated alumina
US9845367B2 (en) 2015-09-24 2017-12-19 Chevron Phillips Chemical Company Lp Heterogeneous Ziegler-Natta catalysts with fluorided silica-coated alumina

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EP2003151A1 (fr) * 2007-06-15 2008-12-17 Nova Chemicals Corporation Réaction améliorée à l'hydrogène par modification du catalyseur
CN101565473A (zh) * 2008-04-25 2009-10-28 中国石油化工股份有限公司 用于乙烯聚合的催化剂组分、制备及应用

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US5424263A (en) * 1993-04-23 1995-06-13 Quantum Chemical Corporation Supported polymerization catalyst
WO2003004537A1 (fr) * 2001-07-02 2003-01-16 Borealis Technology Oy Procede de preparation d'un procatalyseur destine a la polymerisation d'olefine
US20080058198A1 (en) * 2006-08-31 2008-03-06 Formosa Plastics Corporation, U.S.A. Highly active alpha-olefin copolymerization catalyst system
CN101134790A (zh) * 2006-09-01 2008-03-05 中国石油化工股份有限公司 用于乙烯聚合反应的催化剂组分及催化剂
EP2003151A1 (fr) * 2007-06-15 2008-12-17 Nova Chemicals Corporation Réaction améliorée à l'hydrogène par modification du catalyseur
CN101565473A (zh) * 2008-04-25 2009-10-28 中国石油化工股份有限公司 用于乙烯聚合的催化剂组分、制备及应用

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104066685A (zh) * 2011-08-08 2014-09-24 巴斯夫欧洲公司 制备超纯氢氧化镁和氧化镁的方法
US9718907B2 (en) 2015-07-08 2017-08-01 Chevron Phillips Chemical Company Lp Ziegler-Natta—metallocene dual catalyst systems with activator-supports
US9926393B2 (en) 2015-07-08 2018-03-27 Chevron Phillips Chemical Company Lp Ziegler-natta—metallocene dual catalyst systems with activator-supports
US10435492B2 (en) 2015-07-08 2019-10-08 Chevron Phillips Chemical Company Lp Ziegler-natta—metallocene dual catalyst systems with activator-supports
US9540457B1 (en) 2015-09-24 2017-01-10 Chevron Phillips Chemical Company Lp Ziegler-natta—metallocene dual catalyst systems with activator-supports
US9758599B2 (en) 2015-09-24 2017-09-12 Chevron Phillips Chemical Company Lp Heterogeneous Ziegler-Natta catalysts with fluorided silica-coated alumina
US9845367B2 (en) 2015-09-24 2017-12-19 Chevron Phillips Chemical Company Lp Heterogeneous Ziegler-Natta catalysts with fluorided silica-coated alumina

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