US20030195109A1 - Catalytic systems for the polimerisation and copolimerisation of alpha-olefins - Google Patents

Catalytic systems for the polimerisation and copolimerisation of alpha-olefins Download PDF

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US20030195109A1
US20030195109A1 US08/961,956 US96195697A US2003195109A1 US 20030195109 A1 US20030195109 A1 US 20030195109A1 US 96195697 A US96195697 A US 96195697A US 2003195109 A1 US2003195109 A1 US 2003195109A1
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catalyst component
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Jose Sancho Royo
Gerardo Hidalgo Llinas
Antonio Munoz-Escalona Lafuente
M. Francisca Martinez Nunez
Carlos Martin Marcos
Pilar Lafuente Canas
Begona Pena Garcia
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Repsol Quimica SA
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Assigned to REPSOL QUIMICA S.A. reassignment REPSOL QUIMICA S.A. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: CANAS, PILAR LAFUENTE, GARCIA, BEGONA PENA, LAFUENTE, ANTONIO MUNOZ-ESCALONA, LLINAS, GERARDO HIDALGO, MARCOS, CARLOS MARTIN, NUNEZ, M. FRANCISCA MARTINEZ, ROYO, JOSE SANCHO
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F17/00—Metallocenes
    • 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
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • 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
    • C08F110/02—Ethene
    • 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
    • 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
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/619—Component covered by group C08F4/60 containing a transition metal-carbon bond
    • C08F4/61912—Component covered by group C08F4/60 containing a transition metal-carbon bond in combination with an organoaluminium compound
    • 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
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/619—Component covered by group C08F4/60 containing a transition metal-carbon bond
    • C08F4/61916—Component covered by group C08F4/60 containing a transition metal-carbon bond supported on a carrier, e.g. silica, MgCl2, polymer
    • 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
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/619—Component covered by group C08F4/60 containing a transition metal-carbon bond
    • C08F4/6192—Component covered by group C08F4/60 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
    • C08F4/61922—Component covered by group C08F4/60 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not

Definitions

  • the present invention relates to new metallocene catalysts which can be easily heterogenized on an inorganic support.
  • hemogeneous catalytic systems present a disadvantage: when they are used in suspension polymerization processes, a part of the produced polymer adheres to the reactor walls; this effect is technically called “reactor fouling”. Besides, in most cases, the particle size of the obtained polymer is very small and the apparent density is low, thus the industrial production is reduced. In order to prevent the reactor from fouling and to control the size and the morphology of the polymer particles which are formed, the homogeneous system can be supported on an inorganic oxide.
  • U.S. Pat. No. 4,939,217 and U.S. Pat. No. 5,064,797 patents describe a heterogenization process based on the preparation “in situ” of aluminoxane on the support.
  • the method consists in bubbling, an inert humidified gas directly inside a solution of an aluminium alkyl in the presence of the support.
  • an organocomplex solution is added to this heterogenized cocatalyst, the catalyst is heterogenized.
  • Patents EP 323716, EP 361866, EP 336593, EP 367503, EP 368644 and U.S. Pat. No. 5,057,475 describe a different process from the previous one.
  • the cocatalyst is heterogenized through direct reaction of the aluminium alkyl with the superficial hydration water molecules of the support.
  • the organocomplex fixation is then obtained through close contact of an organocomplex solution with a suspension of the modified support.
  • EP 293815 describes the metallocene fixation according to the reactivity of the alcoxysilane functional group (Me 2 (EtO)Si) with superficial hydroxy groups of the inorganic oxide.
  • the activity in polymerization is not very high, probably because a high percentage of the organocomplex is deactivated.
  • An additional disadvantage are the low yields obtained in the preparation of this type of functionalized organometallic compounds.
  • the object of the present invention is to avoid these disadvantages through a process for synthesizing supported catalysts for (co)polymerization of ethylene and alpha-olefins with 3 or more carbon atoms, such as propene, 1-butene, 1-pentene, 1-hexene 4-methyl-1-pentene and 1-octene.
  • this heterogenization process is based on the reactivity of OSiR′′ 3 functional groups of the organo-complexes with the superficial reactive groups of the catalytic support.
  • the fixation of this type of metallocenes, functionalized with groups OSiR′′ 3 is due, as it is described in FIG. IV, to the reaction between the groups OSiR′′ 3 of the organometallic complexes and the reactive groups of the support.
  • Another object of the present invention is the use of the organometallic complexes of formula I and II and homogeneous catalysts for olefins homopolymerization and copolymerization.
  • heterogeneous catalysts can be obtained; they allow to effectively control the morphology and the distribution of particle sizes, with a regular growth of the polymer around the catalyst particles.
  • the present invention relates to homogeneous and heterogeneous catalytic systems containing metallocene complexes of transition metals with at least one group R-OSiR′′ 3 potentially reactive to support.
  • the catalytic system at least includes one metallocene complex of general formula I or II.
  • R is hydrogen or a radical which contains from 1 to 20 carbon atoms; this group optionally contains heteroatoms of groups 14 to 16 of the periodic table of the elements and boron; at least one group R contains a group OSiR′′ 3 ; preferably it is: hydrogen, C 1 -C 20 alkyl, C 3 -C 20 cycloalkyl, C 6 -C 20 aryl,C 7 -C 20 alkenyl, c 7 -C 20 arylalkyl, C 7 -C 20 arylalkenyl or alkylaryl, linear or branched or a group SiR′ 3 wherein R′ is C 1 -C 20 alkyl, C 3 -C 20 cycloalkyl, C 6 -C 20 aryl, C 7 -C 20 alkenyl, C 7 -C 20 arylalkyl, C 7 -C 20 arylalkenyl or alkylaryl, linear or banched or
  • Non limitative examples of R containing the group OSiR′′ 3 are:
  • the group R that contains OSiR′′ 3 is selected from the group comprising: —CH 2 —CH 2 —OSiMe 3 , —CH 2 —CH 2 —CH 2 —OSiMe 3 , —CH 2 —O—CH 2 —OSiMe 2 , —O—CH 2 —CH 2 —OSiMe 3 , —SiMe 2 —CH 2 —CH 2 —OSiMe 3 .
  • Q is selected from a group comprising: boron or an element from groups 14 or 16 of the periodic table; when m>1, the groups Q are qual to or different from each other; the free valences of every Q are filled with groups R according to the value of c index; two groups R are optionally united to form a ring from 5 to 8 atoms, m value can vary from 1 to 4 and it preferably is 1 or 2.
  • L is a cyclic organic group united to M through a ⁇ bond; it contains a cyclopentadienyl ring, that optionally is fused with one or more other rings to form for example: tetrahydroindenyl, indenyl, fluorenyl or octahidrofluorenyl group; or it is an atom from groups 15 or 16 of the periodic table; when it is an atom from groups 15 or 16 of the periodic table (heteroatom), it preferably is an oxygen or nitrogen atom, directly bonded to the metal.
  • L 1 and L 2 equal to or different from each other, have the same meaning of L;
  • M is a metal from groups 3, 4, 10 of the periodic table, lanthamide or actinide; preferably it is Ti, Zr or Hf;
  • X is selected from a group comprising: halogen, hydrogen, OR′′′, N(R′′′) , C 1 -C 20 alkyl or C -C aryl; wherein R′′′is selected from the group comprising: C -C 20 alkyl, C -C 20 cycloalkyl, C -C 20 aryl, C -C 20 alkenyl, C -C 20 arylalkyl, C 7 -C 20 arylalkenyl or alkylaryl, linear or branched;
  • x is 1 or 2
  • y is 2 or 3 in such a way that x+y 4
  • d ranges from 0 to 2;
  • a, b and c are integers from 0 to 10, in such a way that a+b+c>1, the maximum value for a and b depends on the available positions in or ; for example, for the cyclopentadiene, in general formula 1, 5 is the maximum value for a, on the contrary in nthe general formula II, for cyclopentadiene, 4 is the maximum value for a or b; for nitrogen in the general formula II, a or b is 1, for oxygen it is 0; the value of c index depends on the gree valences of group Q, for example, if Q is equal to a silicon atom or carbon atom the value of c is 2; if Q is a boron atom the value of c is 1.
  • Examples of [(R) c Q] m when m is equal to 2 and c is equal to 2 are: R 2 Si—CR 2 , R 2 C—CR 2 , R 2 Si—SiR 2 .
  • Examples of [(R) c Q] m when m is equal to 3 and c is equal to 2 or 1 are: R 2 Si—O—SiR 2 , R 2 Si—O—CR 2 , RB—O—BR.
  • M′ is an alkali metal, preferably Li, Na or K.
  • the preferred compound of the transition metal is tetrachloride and sometimes, when the metal is titanium, it is trichloride or its aduct with a cyclic ether such as tetrahydrofurane.
  • the reaction between the metal compound and the alkali metal derivative is preferably carried out in a dry nitrogen atomosphere, by using anhydrous solvents such as linear or cyclic ethers such as dietylether, tetrahydrofurane or dioxane, or aromatic hydrocarbon such as toluene.
  • anhydrous solvents such as linear or cyclic ethers such as dietylether, tetrahydrofurane or dioxane, or aromatic hydrocarbon such as toluene.
  • the alkali metal compound of formula [(L(r) a )]M′ can be prepared from the compound of formula L(R) a H ghrough reaction with a lithium alkyl, with a sodium or potassium hydride or directly with the metal.
  • the ligand L(r),H when L is or contains a cyclopentadienyl ring, can preferably be obtained from cyclopenadiene or indene through reaction of its sodium salts in the first case and potassium salt in the second case, with a compound R—S, where R has previously been defined and S is a proper leaving group such as halide or alkyl or aryl sulphonate.
  • R—S a proper leaving group such as halide or alkyl or aryl sulphonate.
  • the alkali metal compound [(R) —[(R) c Q] m —L (R) b ]M′ 2 can be obtained through reaction of two equivalents of a metallizing agent such as lithium alkyl, e.g. MeLi or BuLi, or alternatively sodium or potassium hydride, with a compound of formula ((R) a HL —[(R) c Q] m —L 2 H(R) b ).
  • a group L is an oxygen or nitrogen atom
  • the preferred metallizing agent is lithium alkyl.
  • the compound of formula [(R) a HL —((R) c Q) 2 (R) ] cand be obtained through reaction of the alkali metal compound [L H(R) a ]M′ or [L H(R) a ]M′ or mixtures thereof with a compound of formula S—[(R) c Q] m —S, where S is a proper leaving group, such as halogen (Cl, Br, l), or aryl or alkyl sulphonate.
  • S is a proper leaving group, such as halogen (Cl, Br, l), or aryl or alkyl sulphonate.
  • M is zirconium
  • R is C 1 -C 4 alkyl, wherein at least one hydrogen of one R is substituted with OSiR′′ 3 , wherein R′′ is selected from the group comprising: methyl, ethyl, propyl
  • L is a cyclopentadienyl or indenyl group
  • M is zirconium
  • L 1 and L 2 are cyclopentadienyl or indenyl groups
  • R is hydrogen, a C 1 -C 4 alkyl wherein at least one hydrogen of one R is substituted with group OSiR′′ 3 or a group SiR′ 2 —OSiR′′ 3 , wherein R′′ is selected from the group comprising: methyl, ethyl, propyl
  • [(R) c Q] m is selected from the group comprising: H 2 C—CH 2 , CRH—CH 2 , RHC—SiR′ 2 , R 2 C—SiR′ 2 or SiRR′.
  • the other group L 1 or L 2 is a cyclopentadienyl, indenyl or fluorenyl ring
  • M is titanium
  • —[(R) r Q] m is H 2 C—CH 2 , CRH—CH 2 ,R C—SiR′ R C—SiR′ or SiRR′.
  • the compounds of formula I or II can be supported on a proper inorganic support.
  • any type of inorganic oxides can be used, for example inorganic oxides, such as: silica, alumina, silica alumina, aluminium phosphates and mixtures thereof, obtaining supported catalysts with contents in transition metals between 0.01 and 10% by weight, preferably between 1 and 4%.
  • a method that can be fit for preparing supported catalysts according to this invention consists in the impregnation, under anhydrons conditions and inert atmosphere, of the solution of any metallocene of formula I or II, or a mixture thereof, on the supporting material at a proper temperature, preferably between ⁇ 20° C. and 90° C.
  • the supported catalyst that contains the metallocene can be obtained through filtration and washing with a proper solvent, preferably an aliphatic or aromatic hydrocarbon without polar groups.
  • Another method that can properly be used consists in depositing the metallocene on the support by using a solution of the compound that has to be heterogenized, eliminating the solvent through evaporation and then warming the solid residue at a temperature between 25 and 150° C. Besides, the resulting residue, obtained by this process, can be subjected to washing and subsequent filtration.
  • the process can also be carried out in the presence of a cocatalyst that for example can be mixed with a metallocene in a proper solvent and then the resulting solution can be put in contact with the support.
  • a cocatalyst that for example can be mixed with a metallocene in a proper solvent and then the resulting solution can be put in contact with the support.
  • the amount of the organometallic complex which can be anchored in these conditions directly depends on the concentration of the reactive groups present in the support. For this reason silica, for example, should preferably have been calcinated at a temperature between 600° C. and 800° C.
  • An advantageous aspect of this invention is that the fixation method, as a consequence of the reaction of groups R, which contain the —OSiR′′ 3 entity with reactive groups of the support surface, prevents the desorption of the supportedmetallocene complexes.
  • This type of interaction represents the main difference between the organocomplexes heterogenization mechanism and other conventional methods, where the metallocene complex generally remains physisorbed on the support surface.
  • the organocomplex fixation to the inorganic support is based on the reaction of the reactive groups of the support with the group —OSiR′′ 3 or groups of the metallocene, as it is described in FIG. IV.
  • Metallocene complexes of formula I or II can be used in the presence of a cocatlyst for olefins polymerization or copolymerization, either in solution or suspension process.
  • the preferred cocatalysts are alkylaluminoxane, especially methylaluminoxane compounds
  • X is hydrogen or alkyl
  • the preferred cocatalysts is a Lewis acid such as B(C F ) 3 .
  • mixtures of both aluminoxane and boron derivatives can be used as cocatalysts.
  • the most proper polymerization procedure can change according to the chosen type of polymerization process (solution, suspension or gas phase).
  • the cocatalyst can bemixed with a solution of a metallocene of formula I or II and a supplementary quantity of it can be added to the solution; or the catalyst can directly be added to the polymerization medium, which contains the cocatalyst.
  • the cocatalyst can previously be mixed with the supported solid catalyst, can be added to the polymerization medium before the supported catalyst, or both operations can be sequentially carried out.
  • the process consists in putting in contact the monomer, or, in certain cases, the monomer and the comonomer, with a catalytic composition according to the present invention, that includes at least one metallocene complex of formula I or II, at a proper temperature and pressure.
  • the alpha-olefins that can be used as comonomers to obtain ethylene copolymers can be propylene, butene, hexene, octene or branched ones such as the 4-methyl-1-pentene and can be used in proportions from 0,1 to 70% by weight of the total of the monomers.
  • the density of polymers range between 0,950 and 0,9565 g/cm 3 in the case of copolymerization of ethylene the density is as low as 0,900 g/cm .
  • hydrogen can optionally be used as chain transfer agent in such proportions that the hydrogen partial pressure, with respect to the olefin one, is from 0.01 to 50%.
  • the used temperature will be between 30° and 100° C., the same which is typically used in gas phase, while for the solution process the usual temperature will be between 120° and 250° C.
  • the used pressure changes according to the polymerization technique; it ranges from atmospheric pressure to 350 MPa.
  • FIG. I shows examples of compounds according to formula I;
  • FIG. II shows examples of compounds according to formula II, wherein both L 1 and L 2 contain a cyclopentadienyl derivative.
  • FIG. III there are examples of compounds according to formula II, wherein as group L is an oxygen or nitrogen atom and the other group contains a cyclopentadienyl derivative.
  • FIG. IV shows the reaction between the siloxane groups of the supports and the groups —OSiR′′ 3 of the organo-metallic complexes.
  • the solid is washed with various fractions of toluene, up to a total volume of 500 ml and dried under vacuum for 18 hours.
  • the Zr content in the sample was determined through ICP and resulted to be 1.7%.
  • reaction mixture was maintained under stirring at 25° C. for about 18 hours.
  • the solid was separated from the solution through filtration. Then, the resulting solid was washed with a total volume of 500 ml of toluene and dried under vacuum for 12 hours.
  • the zirconium analysis through ICP gave 1.7% in the sample.
  • the solid was washed with three different fractions of toluene, up to a total volume of 500 ml and dried under vacuum for 18 hours.
  • the Zr content in the sample was determined through ICP and gave 2.79% of zirconium.
  • the ethylene polymerization ractions were completed in a 1 litre-capacity Buchi reactor in anhydrous conditions.
  • the reactor charged with 600 ml of dry and degassed heptane, was conditioned at 70° C. Before pressurising the reactor with ethylene the cocatalyst was injected at a pressure of 1 atm. Then, the reactor was pressurised up to 3.75 atm. At the end, the catalyst was injected by using 0.25 atm of ethylene extra pressure. The polymerization reactions is maintained at these pressure (4 atm) and temperature (70° C.) conditions. The suspension was stirred with the help of a stirring bar at 1200 rpm for 15 or 30 minutes.
  • the copolymerization reaction is carried out in the same conditions as those described for ethylene polymerization, after the comonomer initial addition in the reactor.
  • Ethylene and 1-hexene were copolymerized. To do this, the same method as the previous example (numer 12) is used, but with the proviso that once the solvent is added and before pressurising the reactor, 4 ml of dry and recently distilled 1-hexene (12% of hexene in the feeding) is added. 13 ml of a MAO solution in toluene (1.5 M of total aluminium) and 0.1 g of catalyst catalyst prepared according to the description in example 8 are used. After 30 minutes of polymerization 1.47 g of polymer is obtained (1.65 ⁇ 10 g PE/mol Zr*h*atm). The 1-hexene content in the copolymer, determined by 13 C-RMN, was 0.49% molar, distributed at random.
  • Ethylene and 1-hexene were copolymerized. To do this, the same method as example n 12 was used, but with the proviso that once the solvent is added and before pressurising the reactor, 16 ml of dry and recently distilled 1-hexene (33.7% of hexene in the feeding) is added. 13 ml of a MAO solution in toluene (1.5 M of total aluminium) and 0.1 g of the catalyst are used. After 30 minutes of polymerization 1.80 g of polymer were obtained (2.02 ⁇ 10 8 g PE/mol Zr*h*atm). The 1-hexene content in the copolymer, determined by 13 C-NMR, was 1.33% molar, distributed at random.
  • the solid is separated through filtration and washed with consecutive fractions of toluene up to a total volume of 1 l.
  • the heterogeneous catalyst is finally dried under vacuum for 24 hours.
  • the Zr and Al content determined through ICP is 1.15% and 0.7% respectively.
  • the polymerization reaction is carried out according to the method and the conditions described in example 11, but the reactor temperature is 90° C. 10 ml of a 10% MAO solution in toluene (commercialized by Witco) (15 mmol of Al) and 0.079 g (0.01 mmol of Zr) of the heterogeneous catalyst prepared according to example 16 are injected in the reacor. The polymerization reaction is maintained at a temperature of 90° C. and at an ethylene pressure of 4 atm for 15 minutes. At the end of the reaction the reactor pressure is reduced and acdified methanol is added. 2.4 grams of polymer with Mw 165.600 is obtained.
  • the polymerization reaction is carried out according to the method and the conditions described in example 18. 10 ml of a 10% MAO solution in toluene (commercialized by Witco) (15 mmol of Al) and 0.075 g (0,01 mmol of Zr) of the heterogeneous catalyst prepared according to example 17 are injected in the reactor. The polymerization reaction is maintained at a temperature of 90° C. and at an ethylene pressure 4 atm for 15 minutes. At the end of the reaction the reactor pressure is reduced and acidified methanol is added. 2.8 g of polymer is obtained.

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US7211538B2 (en) 1996-10-31 2007-05-01 Repsol Quimica S.A. Catalytic systems for the polimerization and copolimerization of alpha-olefins
US20050065018A1 (en) * 1998-04-29 2005-03-24 (1) Repsol Quimica S.A. Preparation and use of heterogeneous catalyst components for olefins polymerization
US6723675B1 (en) * 2000-05-25 2004-04-20 Univation Technologies, Llc Catalyst for the production of olefin polymers
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US8124557B2 (en) * 2004-09-03 2012-02-28 Lg Chem, Ltd. Supported metallocene catalyst, method of preparing the catalyst and method of preparing polyolefin using the catalyst
CN1910207B (zh) * 2004-09-03 2013-03-27 Lg化学株式会社 载体茂金属催化剂、制备该催化剂的方法以及使用该催化剂制备聚烯烃的方法

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EP0839836B1 (en) 2000-12-20
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NO975049D0 (no) 1997-10-31
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NO318716B1 (no) 2005-05-02
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DE69703728T2 (de) 2001-06-28

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