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WO2000073359A1 - Syntheses catalysees au magnesium d'alkyl de polymeres d'ethylene et d'alpha-olefine - Google Patents

Syntheses catalysees au magnesium d'alkyl de polymeres d'ethylene et d'alpha-olefine Download PDF

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WO2000073359A1
WO2000073359A1 PCT/US2000/015117 US0015117W WO0073359A1 WO 2000073359 A1 WO2000073359 A1 WO 2000073359A1 US 0015117 W US0015117 W US 0015117W WO 0073359 A1 WO0073359 A1 WO 0073359A1
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group
catalyst system
formula
lewis acid
ethylene
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PCT/US2000/015117
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English (en)
Inventor
Ayusman Sen
Jang Sub Kim
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Exxonmobil Research And Engineering Company
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Priority to AU53125/00A priority Critical patent/AU5312500A/en
Publication of WO2000073359A1 publication Critical patent/WO2000073359A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M107/00—Lubricating compositions characterised by the base-material being a macromolecular compound
    • C10M107/02—Hydrocarbon polymers; Hydrocarbon polymers modified by oxidation
    • C10M107/04—Polyethene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
    • B01J31/122—Metal aryl or alkyl compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
    • B01J31/128—Mixtures of organometallic compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
    • B01J31/14—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
    • C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
    • C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
    • C07C2/08—Catalytic processes
    • C07C2/26—Catalytic processes with hydrides or organic compounds
    • C07C2/30—Catalytic processes with hydrides or organic compounds containing metal-to-carbon bond; Metal hydrides
    • 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
    • C08F10/02—Ethene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/10—Magnesium; Oxides or hydroxides thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/10—Polymerisation reactions involving at least dual use catalysts, e.g. for both oligomerisation and polymerisation
    • B01J2231/12—Olefin polymerisation or copolymerisation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/20—Olefin oligomerisation or telomerisation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • C07C2531/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • C07C2531/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • C07C2531/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • C07C2531/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
    • C07C2531/14—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron
    • 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
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
    • C10M2205/022—Ethene
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/14—Synthetic waxes, e.g. polythene waxes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Definitions

  • the present invention relates to the oligomerization an polymerrzation of ethylene and ⁇ -olefins using a two part catalyst system comprising an alkyl magnesium component and a Lewis acid.
  • the products range from highly linear, high molecular weight, solid polymers to highly branched, lower molecular weight oils.
  • Catalysts used in polyolefin preparation can be classified into a limited number of types.
  • Ziegler-Natta type catalysts for polymerization of unsaturated hydrocarbons, such as ⁇ -olefins. have long been the state of the art catalysts for such reactions.
  • Ziegler-Natta type catalysts are composed of transition metal salts and aluminum alkyl compounds. While these catalysts are very effective and have a long-established record of use, they are not without drawbacks. For example, transition metals are expensive, potentially present some toxicity hazards, and to some extent are environmentally objectionable. Therefore, continuing efforts towards development of other suitable olefin polymerization catalysts have occurred.
  • metallocene catalysts have been developed for use in ⁇ -olefin polymerizations.
  • non-transition metal catalysts like Al compounds.
  • combinations of non-transition metal catalysts e.g. Mg and Al for these purposes were unknown.
  • polyethylene and ⁇ -olefins typically leads to the formation of highly linear polymers.
  • polymerization of ethylene, the most widely available and least expensive of the olefins, by transition metal catalysts usually leads to the formation of solid polymers.
  • polyethylene is commonly used to make plastic containers such as milk jugs and for plastic films.
  • polyethylene is generally not suitable for use as soft materials or lubricants for most applications.
  • significant research continues to be performed to discover improved methods for synthesizing liquid polyolefins, especially polyethylene.
  • synthetic lubricants are more desirable as they tend to provide lower friction and increased mechanical efficiency across the full spectrum of mechanical loads and do so over a wider range of operating conditions relative to traditional oil lubricants.
  • the objective of industrial research on synthetic lubricants is, in general, to achieve a polymeric fluid that exhibits a useful viscosity over a wide range of temperature, i.e., has a good viscosity index (VI), while also exhibiting good lubricity, and a pour point equal to or better than mineral oil.
  • VI viscosity index
  • One characteristic of the molecular structure of the polymeric fluids has been found to correlate very well with all of these desirable lubricant properties. This characteristic is the polymer's branching index, BI.
  • BI is the ratio of methyl protons to total non-aromatic, aliphatic group protons in the polymer product.
  • the BI of a polymer is easily determined from proton NMR spectra by calculating the ratio of non-aromatic methyl hydrogens centered around 0.85 ppm, to the total non-aromatic aliphatic hydrogens in the range of 0.5 to 2.1 ppm.
  • the pour point of the polymer fluid i.e., the temperature at which the composition changes from a liquid to a solid
  • BI has a negative effect on the viscosity index of a polyethylene oil; it is well- known in the art that the viscosity index of polyethylene fluids decreases as the branching index increases. This is an undesirable effect because a lower viscosity index indicates a poor viscosity-temperature performance.
  • the challenge in synthesizing polyethylene fluids is to achieve an amount of branching sufficient to maintain the polyethylene in a liquid state such that the polyethylene fluid has a good viscosity index.
  • the PCT application discloses, for example, polyolefins having about 80 to about 150 branches per 1000 methylene groups, wherein for every 100 branches that are methyl branches, there are about 30 to about 90 ethyl branches, about 4 to about 20 propyl branches, about 15 to about 50 butyl branches, about 3 to about 15 amyl branches, and about 30 to about 140 hexyl or longer branches.
  • the olefin polymers described in the PCT application are said to be useful as elastomers, molding resins, in adhesives, etc.
  • Polymers containing monomer units derived other than from olefins are also disclosed in the PCT application; and polymers which contain olefin and olefinic ester monomer units, particularly copolymers of ethylene and methyl methacrylate and/or other acrylic esters, are said to be useful as viscosity modifiers for lubricating oils.
  • the basis for the above PCT Application is believed to be an article by Johnson et al, published in the Journal of the American Chemical Society (New Pd(H)and Ni(II)-Based Catalysts for Polymerization.. of Ethylene and a-Ole ⁇ ns, J. Am. Chem. Soc. 1995, 117, 6414-6415). In these systems, however, the degree of branching is only 20 to 150 branches per 1,000 CH 2 groups.
  • Such highly branched polymers have a VI that typically is too low to be used as, for example, a lube basestock. See also WO 98/33823 titled “Metal Catalyzed Synthesis of Hyperbranched Ethylene and/or ⁇ - olefin Polymers”.
  • PCT Application No. WO 97/02298 relates to the preparation of polyolefins by coordination polymerization of ethylene, styrene or norbornene using a catalyst comprising (a) a zerovalent tricoordinate or tetracoordinate nickel compound which has at least one labile ligand, (b) an acid of the formula HX, where X is a noncoordinating anion, and (c) at least one bulky ligand selected from a specified group thereof.
  • a catalyst comprising (a) a zerovalent tricoordinate or tetracoordinate nickel compound which has at least one labile ligand, (b) an acid of the formula HX, where X is a noncoordinating anion, and (c) at least one bulky ligand selected from a specified group thereof.
  • Moderately branched ethylene polymers are also disclosed by de Souza et al in an article published in September 1997 ([ ⁇ 3-methallyl-nickel-dad] PF, Complex: New Catalyst Precursor For Ethylene Polymerization, Macromol. Rapid Commun., 1997, 18, 795-800).
  • [ ⁇ 3 -methallylnickel-dad] PF 6 is active as an ethylene polymerization catalyst when used in the presence of usual organoaluminum compounds such as diethylaluminum chloride, at low Al/Ni ratios and under mild reaction conditions.
  • Yet another object is to prepare viscous, oily, branched hydrocarbon compositions that are useful as lubricants and lubricant components by homopolymerizing or copolymerizing ⁇ -olefins in the presence of a non-transition metal containing catalyst.
  • Yet another object of the invention is to supply a catalyst system that produces little or no discoloration in the polymerization product thus eliminating or reducing an extra, costly clean-up step.
  • the present invention comprises a novel catalyst system containing (a) an alkyl magnesium component and (b) a Lewis acid component.
  • the invention also includes the use of the catalyst system for the oligomerization, homopolymerization and copolymerization of ⁇ -olefins to form homopolymers and copolymers thereof.
  • the reactions are performed in the presence of a solvent and/or reaction promoters.
  • the present invention comprises a catalyst system for the oligomerization or polymerization of ethylene and/or ⁇ -olefins to prepare homopolymers or copolymers thereof.
  • the catalyst system contains two components: (a) an alkyl magnesium compound having the formula MgR 2 wherein R can be any aliphatic group and (b) a Lewis acid component such as FeCl 3 or A1C1 3 .
  • the reactions are preferably done in the presence of a halogenated or non-halogenated hydrocarbon solvent.
  • the molar ratio of component a:b is in the range of 10:1 to 1 :100, preferably about 2:1 to 1 :10, and most preferably about 1 :1 to 1 :6.
  • the Lewis acid is present at 1 molar equivalent or less.
  • the molecular weight range for these linear solid polymers is generally in the range of about 30,000 up to about 2,500,000; preferably in the range of 50,000 - 1.500,000 and most preferably they are in the range of about 100,000 - 1,000,000.
  • a Lewis acid is added to the reaction mixture in an amount greater than 1 molar equivalent relative to the alkyl magnesium component. Preferably it is added in an amount of about 2 to about 10 molar equivalent and most preferably in the range of 3 - 6 molar equivalent.
  • the molecular weight of the viscous oils are generally in the range of from about 300 to about 30,000; preferably they are within the range of about 500 to about 10,000; and most preferably they are within the range of about 700 to about 3,000. This preferred embodiment may be used as a synthetic lubricant basestock.
  • the term "basestock”, as used herein, refers to a hydrocarbon oil without additives or, in the alternative, the primary component in a lubricant formulation.
  • the synthetic lubricant basestock may be combined with additional lubricating oil additives including, but not limited to, antioxidants, anti-wear additives, extreme pressure antioxidants, anti-wear additives, high pressure additives, friction modifiers, viscosity index improvers, pour point depressants, detergents, dispersants, corrosion inhibitors, metal deactivators, seal compatibility additives, demulsifiers, anti-foam additives, and mixtures thereof.
  • linear solid polymers and branched viscous liquid polymers are prepared from ethylene as the sole monomer.
  • ethylene may be replaced with or used in combination with other olefins such as propylene, butene, 1-pentene, 1-hexene, 1-dodecene and the like.
  • the polymerization preferably is carried out in the liquid phase using a halogenated or non-halogenated hydrocarbon solvent.
  • a halogenated or non-halogenated hydrocarbon solvent any solvent known to those skilled in the art of olefin polymerization can be used. If a solvent is employed, it is preferred that the solvent is either a halogenated compound (preferably aromatic), an aliphatic hydrocarbon comprising from about 5 to about 20 carbons, or a mixture thereof.
  • halogenated solvents examples include chlorobenzene, methylene chloride (CH 2 C1 2 ), tetrachloroethane (C 2 H 2 C1 4 ), dichlorobenzene (C 6 H 4 C1 2 ), trichlorobenzene, bromobenzene, dibromobenzene, tribromobenzene. and alkylated halobenzenes having C1-C10 alkyl groups, such as, for example, p-chlorotoluene, and the like.
  • Especially preferred halogenated solvents are chlorobenzene and dichlorobenzene.
  • aliphatic hydrocarbon solvents comprising from about 5 to about 20 carbons are toluene, xylenes, pentane, hexane, heptane, decane, and dodecane. These are non-limiting examples however and any halogenated or non-halogenated hydrocarbon solvent that effectively assists the polymerization is acceptable.
  • the catalyst system of the present invention comprises two components (a) an alkyl magnesium and (b) a Lewis acid.
  • the alkyl magnesium component of the present invention is defined as MgR 2 where R is any hydrocarbyl group attached to the magnesium.
  • Suitable R. groups include lower alkyls (e.g. methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, etc.) and cyclic alkyls (e.g. cyclopentyl, cyclohexyl, etc.).
  • Other suitable R groups are aryls and fluorinated alkyls and aryls. Mixtures of the above can also be used.
  • Preferred alkyl magnesium compounds are diethylmagnesium [Mg(C 2 H 5 ) 2 ], dibutylmagnesium [Mg(C 4 H 9 ) 2 ] and dineopentylmagnesium [Mg(Np) 2 ].
  • the second component of the catalyst system is a Lewis acid.
  • the Lewis acid component of the present catalyst system may be any Lewis acid known to those skilled in the art.
  • the preferred Lewis acids are B(C 6 F 5 ) 3 , A1C1 3 , and AlBr 3 . Additionally, these Lewis acids can be used in combination.
  • the total amount of the Lewis acid component used in the catalyst system is not particularly limited. However, to obtain liquid polymers, the Lewis acid component should be used in substantial molar excess relative to the alkyl magnesium component. Typically, the Lewis acid component should be used in an amount of from about 2 to about 50 moles per mole of alkyl magnesium component. Preferably, the Lewis acid should be used in an amount of from about 3 to about 10 moles per mole of alkyl magnesium component, and more preferably about 6 moles per mole of alkyl magnesium component.
  • the catalyst system can contain other optional components known to those skilled in the art.
  • One such group of compounds are promoters including acidic metal oxides (e.g., Al 2 O 3 , ZrO 2 ) and organic molecules with oxygen and nitrogen functionalities (e. g.. C 6 F 5 OH).
  • the polymerization in accordance with this invention may be carried out at temperatures ranging from about 0°C to about 200°C. Typically, however, the polymerization will be carried out at a temperature of from about 20°C to about 80°C.
  • the pressure at which the polymerization is carried out is not critical, with pressures ranging ficm 15 psi to 1500 psi being suitable. Typically, we used pressures ranging from 300 to 900 psi.
  • At least one component of the catalyst system is supported by an inert support.
  • inert supports are well known to those skilled in the art such as, for example, silica, alumina, carbon, zirconia, magnesia, diatomatious earth, kieselgur, and mixtures thereof. Supporting the components of the catalyst system to such inert support is accomplished by techniques well known to those skilled in the art such as, for example, impregnation.
  • a highly pure Np 2 Mg was obtained by sublimation of crude product twice at 100°C/60 mtorr.
  • Diethylmagnesium was prepared from diethylmercury and magnesium as described in J. Organomet. Chem. 14, 1 , 1968. Dibutylmagnesium.
  • Examples I B through 1J followed the basic procedure for Example 1A above, except that ethylene was added in a single charge at 700 psi and FAB was added at 1 molar equivalent.
  • the alkyl group on the dialkyl magnesium was either butyl, ethyl, or neopentyl and the solvent was either chlorobenzene or toluene.
  • the amount of alkyl magnesium varied from 20 to 200 ⁇ mol and the amount of solvent used was either 15 or 50 ml.
  • the reaction time varied from 0.5 to 4.0 hours and the reaction temperature was either room temperature or 60°C.
  • Table 1 also gives the results including the yield of solid polymer in grams and the reaction productivity. Table 1: Conditions and Results for Example 1 - MgR, + FAB - Solid Polymer
  • Example 2B the resulting polyethylene was treated as in example 1.
  • Example 2A yielded 1.27 g and had a reaction productivity of 15.5 kg/mol»hr.
  • Example 2B yielded 2.50 g and had a reaction productivity of 1 1.1 kg/mol»hr.
  • Examples 2A and 2B are summarized in Table 2. These examples illustrate the use of an organic promoter.
  • Table 2 Conditions and Results for Example 2 - MgR, + C,.F «OH + FAB -» Solid Polymer
  • Example 3A yielded 1.15 g and had a reaction productivity of 14.4 kg/mol*hr.
  • Example 3B yielded 1.56 g and had a reaction productivity of 15.6 kg/mol «hr. Examples 3 A and 3B are summarized in Table 3.
  • This example demonstrates the production of highly branched viscous liquid polyethylene especially useful in lubricant applications.
  • a 50 ml glass liner equipped with a magnetic stirrer containing 64.8 mg (480 ⁇ mol) of A1C1 3 in 15 ml of chlorobenzene 80 ⁇ mol (1.0 M heptane solution) of Mg(C 4 H 9 ) 2 was added.
  • the liner was placed in 125 ml Parr reactor.
  • the reaction mixture was stirred under N 2 for 20 min without ethylene at 60°C.
  • the reactor was filled and degassed with ethylene once and then pressurized with 700 psi of ethylene.
  • Examples 4B through 4H followed the basic procedure for Example 4A above. All examples used 700 psi of ethylene in a single charge; the solvent used was 15 ml C 6 H 5 C1 and the reaction time was 1 hr. The MgR 2 , reaction temperature, and equivalents of A1C1 3 was varied as given in Table 4. Table 4 also gives the results in terms of product yield, reaction productivity, molecular weight, Poly Dispersity Index (PDI), and branching index where the branching index (Me/Total) is defined as the ratio of methyl protons (at 0.85 ppm)/total alkyl protons (by 'H-NMR integration). In Table 4, Cp is "cyclopentadienyl". These examples illustrate the use of a range of temperatures and different amounts of Lewis acid. Table 4; Conditions and Results for Examples 4A-4H - MeR, + AICI, (>1 equiv.) -» Branched Liquid Polymer
  • Examples 41 through 4L followed the basic procedure for Example 4A above. All examples used: a constant feed of ethylene; 6 equivalents of A1C1 3 ; 15 ml of C 6 H 5 C1; a reaction temperature of 60°C; and a reaction time of 1 hr. The amount of ethylene charge was varied from 300 psi to 900 psi as given in Table 5. Table 5 also gives the results in terms of product yield, reaction productivity, molecular weight, PDI, and branching index where the branching index (Me/Total) is defined as the ratio of methyl protons (at 0.85 ppm)/total alkyl protons (by "H-NMR integration). These examples indicates an increase in reaction productivity with increasing ethylene pressure.

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Abstract

L'invention concerne un système catalyseur à deux composés contenant (a) un composé de magnésium d'alkyl (MgR2) et (b) un composé d'acide Lewis. Le système catalyseur est utilisé pour catalyser l'oligomérisation et la polymérisation d'éthylène et/ou d'α-oléfines afin de constituer des homopolymères et des copolymères. Les produits vont des polymères solides, à poids moléculaire élevé, extrêmement linéaires à des huiles de poids moléculaire inférieur, pourvues de très nombreuses ramifications.
PCT/US2000/015117 1999-06-02 2000-06-02 Syntheses catalysees au magnesium d'alkyl de polymeres d'ethylene et d'alpha-olefine WO2000073359A1 (fr)

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AU53125/00A AU5312500A (en) 1999-06-02 2000-06-02 Alkyl magnesium catalyzed synthesis of ethylene and alpha-olefin polymers

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US60/137,199 1999-06-02

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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EP0003716A1 (fr) * 1978-01-26 1979-08-22 Battelle Memorial Institute Procédé de polymérisation d'oléfines, système catalytique utilisé et sa préparation
US5561095A (en) * 1994-03-31 1996-10-01 Exxon Chemical Patents Inc. Supported lewis acid catalysts for hydrocarbon conversion reactions
US5880241A (en) * 1995-01-24 1999-03-09 E. I. Du Pont De Nemours And Company Olefin polymers

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3737393A (en) * 1969-06-04 1973-06-05 Stamicarbon Process for the preparation of a dialkyl magnesium compound
EP0003716A1 (fr) * 1978-01-26 1979-08-22 Battelle Memorial Institute Procédé de polymérisation d'oléfines, système catalytique utilisé et sa préparation
US5561095A (en) * 1994-03-31 1996-10-01 Exxon Chemical Patents Inc. Supported lewis acid catalysts for hydrocarbon conversion reactions
US5880241A (en) * 1995-01-24 1999-03-09 E. I. Du Pont De Nemours And Company Olefin polymers

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