CN1122675C - 含亚乙烯基的聚合物及其制备方法和用途 - Google Patents

含亚乙烯基的聚合物及其制备方法和用途 Download PDF

Info

Publication number
CN1122675C
CN1122675C CN00100180A CN00100180A CN1122675C CN 1122675 C CN1122675 C CN 1122675C CN 00100180 A CN00100180 A CN 00100180A CN 00100180 A CN00100180 A CN 00100180A CN 1122675 C CN1122675 C CN 1122675C
Authority
CN
China
Prior art keywords
polymkeric substance
vinylidene
ethene
butylene
alpha
Prior art date
Legal status (The legal status 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 status listed.)
Expired - Fee Related
Application number
CN00100180A
Other languages
English (en)
Other versions
CN1297949A (zh
Inventor
威廉姆·海尔曼
邱一清
宋卫
钱庆文·詹姆斯
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
PENNOZOIL PRODUCTS CO
Original Assignee
PENNOZOIL PRODUCTS CO
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.)
Filing date
Publication date
Application filed by PENNOZOIL PRODUCTS CO filed Critical PENNOZOIL PRODUCTS CO
Publication of CN1297949A publication Critical patent/CN1297949A/zh
Application granted granted Critical
Publication of CN1122675C publication Critical patent/CN1122675C/zh
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

Links

Images

Classifications

    • 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
    • C10M143/00—Lubricating compositions characterised by the additive being a macromolecular hydrocarbon or such hydrocarbon modified by oxidation
    • C10M143/10—Lubricating compositions characterised by the additive being a macromolecular hydrocarbon or such hydrocarbon modified by oxidation containing aromatic monomer, e.g. styrene
    • 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
    • C08F114/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
    • C08F114/02—Monomers containing chlorine
    • C08F114/04—Monomers containing two carbon atoms
    • C08F114/08—Vinylidene chloride
    • 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
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/04—Monomers containing three or four carbon atoms
    • C08F210/08—Butenes
    • C08F210/10—Isobutene
    • 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
    • C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
    • C08F297/06—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the coordination type
    • C08F297/08—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the coordination type polymerising mono-olefins
    • 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
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/04—Reduction, e.g. hydrogenation
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
    • C09K23/003—Organic compounds containing only carbon and hydrogen
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/16—Hydrocarbons
    • C10L1/1625—Hydrocarbons macromolecular compounds
    • C10L1/1633—Hydrocarbons macromolecular compounds homo- or copolymers obtained by reactions only involving carbon-to carbon unsaturated bonds
    • C10L1/1641—Hydrocarbons macromolecular compounds homo- or copolymers obtained by reactions only involving carbon-to carbon unsaturated bonds from compounds containing aliphatic monomers
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/16—Hydrocarbons
    • C10L1/1625—Hydrocarbons macromolecular compounds
    • C10L1/1633—Hydrocarbons macromolecular compounds homo- or copolymers obtained by reactions only involving carbon-to carbon unsaturated bonds
    • C10L1/165—Hydrocarbons macromolecular compounds homo- or copolymers obtained by reactions only involving carbon-to carbon unsaturated bonds from compounds containing aromatic monomers
    • 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
    • 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
    • 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
    • C10M107/06—Hydrocarbon polymers; Hydrocarbon polymers modified by oxidation containing propene
    • 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
    • C10M107/08—Hydrocarbon polymers; Hydrocarbon polymers modified by oxidation containing butene
    • 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
    • C10M107/10—Hydrocarbon polymers; Hydrocarbon polymers modified by oxidation containing aliphatic monomer having more than 4 carbon atoms
    • 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
    • C10M107/12—Hydrocarbon polymers; Hydrocarbon polymers modified by oxidation containing aromatic monomer, e.g. styrene
    • 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
    • C10M143/00—Lubricating compositions characterised by the additive being a macromolecular hydrocarbon or such hydrocarbon modified by oxidation
    • 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
    • C10M171/00—Lubricating compositions characterised by purely physical criteria, e.g. containing as base-material, thickener or additive, ingredients which are characterised exclusively by their numerically specified physical properties, i.e. containing ingredients which are physically well-defined but for which the chemical nature is either unspecified or only very vaguely indicated
    • C10M171/04—Specified molecular weight or molecular weight distribution
    • 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
    • C08F210/02—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
    • C08F210/04—Monomers containing three or four carbon atoms
    • C08F210/06—Propene
    • 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
    • C08F2800/00—Copolymer characterised by the proportions of the comonomers expressed
    • C08F2800/20—Copolymer characterised by the proportions of the comonomers expressed as weight or mass percentages
    • 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
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65908—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+
    • 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
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65912—Component covered by group C08F4/64 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
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
    • 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
    • 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
    • C10M2205/0206—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers used as base material
    • 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
    • C10M2205/0225—Ethene used as base material
    • 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
    • C10M2205/024—Propene
    • C10M2205/0245—Propene used as base material
    • 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
    • C10M2205/026—Butene
    • C10M2205/0265—Butene used as base material
    • 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
    • C10M2205/028—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms
    • C10M2205/0285—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms used as base material
    • 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
    • C10M2205/04—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing aromatic monomers, e.g. styrene
    • 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
    • C10M2205/04—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing aromatic monomers, e.g. styrene
    • C10M2205/043—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing aromatic monomers, e.g. styrene used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • General Chemical & Material Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Developing Agents For Electrophotography (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Sealing Material Composition (AREA)
  • Lubricants (AREA)
  • Paints Or Removers (AREA)

Abstract

一种含亚乙烯基的聚合物及其制备方法和用途，含亚乙烯基的聚合物在单中心催化剂存在下获得，这些聚合物包括乙烯/异丁烯共聚物、乙烯/丙烯/异丁烯三元聚合物、乙烯/苯乙烯/异丁烯三元聚合物、乙烯/α-甲基苯乙烯/异丁烯三元聚合物、丙烯/异丁烯共聚物、苯乙烯/异丁烯共聚物和α-甲基苯乙烯/异丁烯共聚物。这些聚合物可用于配制润滑油。

Description

含亚乙烯基的聚合物及其制备方法和用途
技术领域
本发明涉及含亚乙烯基的聚合物和制备这些聚合物的方法。本发明还涉及这些含亚乙烯基聚合物的用途，特别在配制润滑油中的用途。
背景技术
合成烃已用作汽车、航空和工业领域的润滑剂。在汽车工业中，润滑油包括机油、刹车油和润滑油脂。用于汽车的机油包括2-冲程油、4-冲程油和齿轮油。在航空工业中，润滑油包括燃汽轮机滑油、活塞式发动机润滑油、液压油和润滑油酯。在工业领域，润滑油用作汽轮机油、齿轮油、轴承和循环油、压缩机油、液压油、金属加工油、传热和绝缘油和润滑油脂。
聚异丁烯和聚-α-烯烃是两种公知的用作润滑油的合成烃。聚-α-烯烃在低温下具有良好的流动性、相当高的热和氧化稳定性、高温下低的蒸发损失、高粘度指数、良好的摩擦性能、良好的水解稳定性和良好的耐腐蚀性。聚α-烯烃无毒并与矿物油和酯混溶。此外，聚-α-烯烃适合用于机油、压缩机油、液压油、齿轮油和润滑油脂。然而，聚-α-烯烃存在有限的生物降解性和有限的与添加剂混溶性。因此，它不适合用作高性能齿轮油和很快生物降解的油。结构上聚-α烯烃包括容易氧化的叔氢。因此，需要消除存在的叔氢以改进合成烃的耐氧化性。
聚异丁烯是另一类已用作润滑油的合成烃。聚异丁烯提供良好的润滑性和良好的耐腐蚀性。聚异丁烯无毒并与矿物油混溶。然而，聚异丁烯存在相当低的氧化稳定性和相当差的低温流动性。它们还存在相当高的蒸发损失和相当低的粘度指数。因此，聚异丁烯适合用作2-冲程机油、压缩机油、金属加工润滑剂、润滑油脂和钢丝绳润滑油；但它们不适合用作大多数循环体系的润滑剂。此外，已知聚异丁烯在高温下解聚，这种现象称为“解缀合”[unzipping]。通常，解聚在高于250℃时出现。这种解缀合现象排除了聚异丁烯在高温下使用。因此需要克服聚异丁烯“解缀合”的缺陷，同时保持聚异丁烯具有的其他益处。
α-烯烃/异丁烯共聚物可以替代聚异丁烯和聚-α-烯烃。因为，乙烯/异丁烯共聚物不含有叔氢、因此，这种共聚物可具有改进的耐氧化性。此外，引入乙烯单元可防止或减轻聚异丁烯具有的“解缀合”现象。然而，这些共聚物还未制得，因为很多亚乙烯基烯烃(如异丁烯)在Ziegler-Natt催化剂存在下不能共聚。因此，为了满足各种用途，还需要寻找制备含亚乙烯基的聚合物的可能性。
发明内容
本发明描述的实施方案通过提供优选在单中心催化剂存在下，获得的各种含亚乙烯基的聚合物满足上述需要。本发明还提供制备和使用这些含亚乙烯基的聚合物的方法。本发明实施方案涉及的性能和优点通过下面的描述显而易见。
附图说明
图1为根据实施例1中描述的方法获得的乙烯与异丁烯的共聚产品的13C NMR光谱图。51.2ppm处的化学位移说明在所得乙烯/异丁烯共聚物中存在异丁烯二单元组[isobutene diad]。
图2为通过实施例3中描述的方法获得的丙烯与异丁烯的共聚产品的13C NMR光谱图。
图3为通过实施例10中描述的方法获得的苯乙烯与异丁烯的共聚产品的13C NMR光谱图。
图4为通过实施例11中描述的方法获得的α-甲基苯乙烯与异丁烯的共聚产品的13C NMR光谱图。
具体实施方式
本发明实施方案提供各种α-烯烃/亚乙烯基的聚合物和亚乙烯基/亚乙烯基的聚合物。这些聚合物包括共聚物、三元聚合物、四元聚合物等。本发明的α-烯烃/亚乙烯基的聚合物分为两组：乙烯/亚乙烯基聚合物和高级α-烯烃/亚乙烯基聚合物，其中“高级α-烯烃”是指每个分子中具有3或多个碳原子的α-烯烃。
乙烯/亚乙烯基聚合物的一个特征是，该聚合物在其链内包括至少一个亚乙烯基烯烃的二单元组。在某些实施方案中，乙烯/亚乙烯基聚合物可在该聚合物链内还包括乙烯的重复单元。该聚合物通常包括一种或多种单体的很多重复单元。一个聚合物单元是指在整个聚合物链中重复的聚合物链的一个链段或一部分。二单元组是指在聚合物链内存在两个相邻的同一种单体。因此，亚乙烯基烯烃(“V”)的二单元组是指在聚合物链内的一个[-V-V-]单元。乙烯/亚乙烯基聚合物的例子包括乙烯/异丁烯共聚物、乙烯/异丁烯/丙烯三元聚合物、乙烯/异丁烯/苯乙烯三元聚合物和乙烯/异丁烯/α-甲基苯乙烯三元聚合物，但不限于此。
与乙烯/亚乙烯基聚合物相反，亚乙烯基二单元组可存在于或不存在于本发明实施方案的高级α-烯烃/亚乙烯基聚合物和亚乙烯基/亚乙烯基聚合物中。高级α-烯烃/亚乙烯基聚合物的例子包括丙烯/异丁烯共聚物、苯乙烯/异丁烯共聚物等，但不限于此。亚乙烯基/亚乙烯基聚合物的例子为异丁烯/α-甲基苯乙烯共聚物。
合适的亚乙烯基烯烃由如下通式表示：
       R1-CH＝CR2R3
其中R1为氢或烃基，R2和R3独立地选自烷基、芳基和芳烷基。R1优选为具有1至12个碳原子的直链或支链饱和烃基。R1最优选为氢。R2和R3可为具有1至100个碳原子的直链、支链或环状烃基。烃基可为取代或未取代的。R2和R3可非必要地连接形成环状结构。因此，术语“亚乙烯基烯烃”可包括单体如异丁烯，和符合上述代表性结构的大单体。尽管R1、R2和R3基本上为烃基，允许包括一个杂原子如O、S、N、P、Si、卤素等，其中这些杂原子应足以从双键中除去，以便不干扰配位聚合反应。具体地，合适的亚乙烯基烯烃包括但不限于异丁烯、3-三甲基甲硅烷基-2-甲基-1-丙烯、2-甲基-1-丁烯、2-甲基-1-戊烯、2-乙基-1-戊烯、2-甲基-1-己烯、2-甲基-1-庚烯、6-二甲氨基-2-甲基-1-己烯、α-甲基苯乙烯、2，4-二甲基戊烯等。
除了乙烯与亚乙烯基烯烃的共聚物外，本发明的实施方案还提供含亚乙烯基的三元聚合物、四元聚合物等。这些聚合物通过乙烯单体、亚乙烯基烯烃单体和一种或多种不同于乙烯和亚乙烯基烯烃的另外的烯烃单体共聚获得。
对于合适的另外的烯烃单体，可使用任何烯烃单体。它们包括但不限于脂族烯烃、环烯烃和芳烃。能够共聚的合适环烯烃包括但不限于环戊烯、降冰片烯、烷基取代降冰片烯、环己烯、环庚烯等。另一些合适的烯烃的例子还包括一种或多种C3和高级α-烯烃、苯乙烯、和其中取代基位于芳环上的烃基取代苯乙烯单体，C4和高级内烯烃，C4和高级二烯烃、C5和高级环烯烃和二烯烃，C6和高级取代α-烯烃。合适的C6和高级取代α-烯烃包括含至少一个与取代α-烯烃的碳原子键合的IIIA族至VIIA族原子的那些α-烯烃。例子包括烯丙基三甲基硅烷、4，4，4-三氟-1-丁烯等。当含官能团的α-烯烃按与其α-烯烃类似物相同的方式引入时，使用这些烯烃也在本发明范围内。此外，还可使用US 5,153,282中公开的掩蔽α-烯烃单体，该专利公开的内容这里作为参考引入。
优选的高级α-烯烃包括具有3至30个碳原子，优选3至20个碳原子的α-烯烃，但也可类似地使用具有30个以上碳原子的1-烯烃大单体。通常，合适的α-烯烃由如下通式表示：
        CH2＝CHR4其中R4可为任何烃基，如烷基、芳基或烷芳基。优选的α-烯烃的某些具体例子包括但不限于丙烯、1-丁烯、1-戊烯、1-己烯、1-庚烯、1-辛烯、1-壬烯、1-癸烯、1-十二碳烯、4-甲基-1-戊烯、5-甲基-1-壬烯、3-甲基-1-戊烯、3，5，5-三甲基-1-己烯和乙烯基环己烯。苯乙烯和对-甲基苯乙烯是优选的苯乙烯系烯烃。
除了单烯烃外，二烯烃或多烯还可与一种或多种亚乙烯基烯烃共聚。合适的二烯烃的例子包括直链无环二烯烃、支链无环二烯烃、单环脂环二烯烃、多环脂环稠合和桥连环二烯烃，及环链烯基取代的烯烃。优选的例子为1，4-己二烯、二环戊二烯、5-亚乙烯基-2-降冰片烯、乙烯基环己烯5-乙烯基-2-降冰片烯、4-亚乙基-降冰片烯和1，4-降冰片二烯。
在本发明实施方案中获得的含亚乙烯基聚合物通常具有如下一种或多种特性。首先，这些聚合物具有相当窄的分子量分布(“MWD”)，由Mw/Mn表示。MWD通常低于约3.5，优选低于约2.5，更优选低于约2。第二，共聚物或三元聚合物具有基本上无规共聚单体分布。换言之，加入聚合物中的共聚单体基本上符合Bernoullian统计模式。因此，这些聚合物具有基本上均匀共聚单体组成。第三，这些聚合物不包括明显量的低分子量分布。其它性能和特征是本领域熟练技术人员显而易见的。
本发明实施方案的聚合物可在单中心催化剂存在下获得。已知某些金属茂化合物为单中心催化剂。这些金属茂化合物可包括来自元素周期表IVB和VIIIB族的金属。单中心催化剂可非必要地包括助催化剂，如铝氧烷化合物。例如，US 5,001,244、5,272,236和5,278,272公开了各种单中心催化剂，上述专利中公开的所有内容这里作为参考全部引入。US 5,866,655公开了可用于本发明实施方案各种单中心催化剂。US 5,866,665第6栏，22行至50行描述的合适催化剂这里作为参考引入。其它合适的单中心催化剂公开于US专利申请08/880,151中，其相关部分这里作为参考引入。
在优选的实施方案中，单中心催化剂包括IVB族过渡金属络合物、生成阳离子的助催化剂和烷基铝化合物。IVB族过渡金属络合物优选由如下通式表示：
       (C5Rm)nYsXpMLz其中R独立地为1至20个碳原子的直链或环状烃基；m＝1，2，3，4或5；n＝1，2，或3；Y或X独立地为含至少一个选自-Si(R′R″)-、-N(R′)-、-P(R′)-、-O-、-S-或-C(R′R″)-的基团的杂原子部分，其中R′或R″独立地为1至20个碳原子的烃基；s或p独立地为0或1；M为IVB族金属原子；和L为1至20个碳原子的烃基；z＝4-n-p。C5Rm(为取代的或未取代的环戊二烯基)和X(不是环戊二烯基)直接与过渡金属M键合，而Y桥连两个C5Rm基团或一个C5Rm基团和一个X基团。
助催化剂优选为具有通式B(C6F5)3或(C6H5)3C+B-(C6F5)4的强路易氏[Lewis]酸。这些方法描述于US申请08/880,151中，公开的涉及这些方法的相关部分这里作为参考引入。本发明的聚合物经由裂解、氢化或加氢异构化获得的聚合物产品可用作润滑油的组分。
下面的实施例说明本发明的实施方案，但本发明不受这里的描述限制。应强调的是，这里公开的任何数值都是大约数值，不应被绝对化。一般性实验步骤
所有气态单体通过将其通过Matheson气体纯化器(Model6406-A)纯化。将带有磁搅拌棒的250ml压力反应容器用氩气彻底清洗，并加入50ml干燥甲苯(在钾上蒸馏的)、将烯烃单体在7立升的圆筒中按所需比例预混并加热至约70℃过夜。将该单体混合物在某一温度下及压力约10或约20psig下加入反应瓶中，然后将三异丁基铝(TIBA)甲苯溶液用注射器注入反应瓶中，接着加入金属茂甲苯溶液。然后加入四(五氟苯基)硼酸三苯基碳鎓盐(Ph3CB(C6F5)4)的甲苯溶液作为助催化剂。TIBA消除聚合中的湿气并使金属茂前体烷基化。使用的金属茂与助催化剂的摩尔比为约1∶1。注入催化剂溶液后引发乙烯与异丁烯的聚合。在反应期间，温度通过带有循环器恒温浴保持。H2用于控制共聚物的分子量。将过量单体和氢气以速率约10～20ml/min连续排空以使反应瓶中的气体浓度保持恒定。1小时后，通过将10ml 2％酸式甲醇注入反应瓶中使聚合作用停止。将所得溶液再搅拌1小时，然后将其用200ml去离子水在500ml分液漏斗中洗涤三次。将有机层经硅藻土过滤得到透明溶液，然后在旋转蒸发器上除去甲苯。将该液态共聚物产品在真空中在约75℃下进一步干燥过夜，然后称重，并通过核磁共振(“NMR”)和凝胶渗透色谱(“GPC”)分析。当异丁烯与液体单体共聚时，优选在注入催化剂之前将这些单体预混。
重均分子量(Mw)和数均分子量(Mn)通过使用装有微分折射率检测器的Waters 150CV GPC光谱仪并用聚苯乙烯标准物校准的凝胶渗透色谱测量。将三个Shodex KF-806M和一个Shodex KF-801柱串联连接，测定Mw在3,000,000至1,000之间。
聚合物样品的13C NMR光谱在CDCl3中在环境温度下用场强度50MHZ或在三氯苯/苯-d6的混合物中在约80℃下用场强度约500MHZ测定。乙烯/异丁烯共聚物的异丁烯含量即IB百分比由如下通式计算：
IB％＝100×2A/(2B+A)其中A为甲基共振峰的积分，B为亚甲基共振峰的积分。为有助于确定NMR峰，使用软件模拟乙烯-异丁烯共聚物的13C NMR化学位移。使用的软件为ACD/ChemSketch软件，Version 3.50/09 Apr1998(由Advanced Development Inc.开发)。按照该软件的模拟，化学位移[chemical shift]约51.2PPM，说明聚合物链中存在-E-IB-IB-E-结构。(E表示乙烯，IB表示异丁烯)。
                           实施例1
将带有磁搅拌棒的250ml压力反应容器用氩气彻底清洗，并加入50ml干燥甲苯(在钾上蒸馏的)。将乙烯、异丁烯和氢气分别按比例约8％、82％和10％在7立升圆筒中预混，并加热至约70℃过夜。将该气体混合物加入温度约25℃及压力约10psig的反应瓶中，然后将约1.5ml的0.05M三异丁基铝(TIBA)甲苯溶液用注射器注入反应瓶中，接着加入1ml的3.75×10-3M Dow Insite催化剂[二甲基甲硅烷基(四甲基环戊二烯基)(叔丁基酰胺基)]二氯化钛(即[(C5Me4)SiMe2N(t-Bu)]TiCl2)的甲苯溶液，最后加入约1ml3.75×10-3M四(五氟苯基)硼酸三苯基碳鎓盐(Ph3CB(C6F5)4)的甲苯溶液作为助催化剂。注入催化剂溶液后引发乙烯与异丁烯的聚合。在反应期间，温度通过带有循环器的恒温浴保持。将过量单体和氢气以速率约10ml/min连续排空以使反应瓶中的气体浓度保持恒定。
1小时后，通过将10ml的2％酸性甲醇注入反应瓶中使聚合反应停止。将所得溶液再搅拌1小时。将产品与甲苯一起用200ml去离子水在500ml分液漏斗中洗涤三次。将有机层经硅藻土过滤得到透明溶液。然后在旋转蒸发器上除去甲苯，得到无色粘性液体。聚合活性为约1.97×105g聚合物/(molTi-Hr)。13C-NMR分析生成的产品为约22.8％聚异丁烯均聚物和约77.2％乙烯-异丁烯共聚物的混合物。图1为乙烯异丁烯共聚物产品的13C-NMR谱图。该乙烯/异丁烯共聚物含约58.5％乙烯和约41.5％异丁烯。该聚合产品的13C-NMR中δ51.2ppm处的峰值[isolated signal]，显示共聚物中存在[-E-IB-IB-E-]序列。
                        实施例2
步骤基本上与实施例1相同，不同的是使用1立升的压力反应器和不同的聚合条件。反应条件概列于表1中。获得粘性油产品。13C-NMR分析显示生成的产品为约23.0％聚异丁烯均聚物和约77.0％乙烯-异丁烯共聚物的混合物。该共聚物含有约75.2％的乙烯和约24.8％异丁烯。聚异丁烯的重均分子量Mw约780和Mw/Mn约1.42。该乙烯-异丁烯共聚物的重均分子量Mw约8,147，和Mw/Mn约1.51。同样，该聚合产品的13C-NMR中δ51.2ppm处的峰值显示共聚物中存在-E-IB-IB-E-序列。
                             表1
                             聚合条件
  实施例 1  2
  反应器尺寸 250ml  1L
  原料中的乙烯％ 8  10
  原料中的异丁烯％ 82  80
  原料中的氢气 10  10
  聚合温度℃ 25  40
  聚合压力，psig 10  20
  聚合时间，hr 1  0.5
  甲苯，ml 50  300
  TIBA 1ml，浓度为0.05M  2ml，浓度为1M
  Insite催化剂 1ml，浓度为3.75×10-3M  8ml，浓度为0.03.75M
  Ph3CB(C6F5)4 1ml，浓度为3.75×10-3M  8ml，浓度为0.03.75M
  活性，聚合物g/(molTi-Hr) 1.97×105  3.7×105
                       实施例3
步骤基本上与实施例1相同。将原料比例分别为约9％、82％和9％的丙烯、异丁烯与氢气的混合物装入装有约50ml甲苯约60℃下的反应瓶中。用约2ml的0.05M TiBA，4ml的15×10-3Minsite催化剂和4ml的15×10-3M Ph3CB(C6F5)4溶液引发聚合。将反应体系的气相以约20ml/min的速率连续排空。反应约1小时后，获得透明液体，其活性为0.73×105g聚合物/(molTi-Hr)。制成液体的重均分子量Mw约3,316，和Mw/Mn约3.00。该液体的13C-NMR分析显示形成丙烯-异丁烯共聚物。图2为丙烯与异丁烯的共聚产品的13C-NMR光谱图。
                        实施例4
步骤基本上与实施例3相同。不同的是将原料比例分别为约26％、65％和9％的丙烯、异丁烯与氢气的混合物加入反应瓶中，并用约3ml 0.05M TiBA引发聚合。反应约1小时后，获得透明液体，其活性为0.53×105g聚合物/(molTi-Hr)。该液体具有Mw约4,900，和Mw/Mn约5.77。该液体的13C-NMR分析显示形成丙烯-异丁烯共聚物。
                        实施例5
步骤基本上与实施例1相同。将原料比例分别为约9％、4％、78％和9％的乙烯、丙烯、异丁烯与氢气的混合物下加入装有约50ml甲苯约40℃的反应瓶中。用约2ml的0.05M TiBA，2ml的3.75×10-3Minsite催化剂和2ml的3.755×10-3M Ph3CB(C6F5)4溶液引发聚合。将反应体系的气相以约20ml/min的速率连续排空。反应约1小时后，获得透明液体，其活性为4.89×105g聚合物/(molTi-Hr)。该液体的13C-NMR分析显示形成丙乙烯-丙烯-异丁烯的三元聚合物。
                         实施例6
步骤基本上与实施例5相同，但单体混合物中乙烯、丙烯、异丁烯和氢气的比例分别为约13.4％、18％、55.2％和13.4％。反应约1小时后，获得透明液体，其活性为3.47×105g聚合物/(molTi-Hr)。生成的液体的13C-NMR分析，显示形成丙乙烯-丙烯-异丁烯的三元聚合物。
                        实施例7
步骤基本上与实施例1相同。将约50ml干燥甲苯和约10ml苯乙烯投入反应瓶中。将乙烯和异丁烯比例分别为约10％和90％，压力约10psig气体混合物加入约50℃的反应器中。用约3ml 0.05MTiBA，4ml 0.015Minsite催化剂和4ml 0.015M Ph3CB(C6F5)4溶液引发聚合。将反应体系的气相以约10ml/min的速率连续排空。反应约1小时后，获得半固体的产品，其活性为2.42×105g聚合物/(molTi-Hr)。该产品具有Mw约3,127，和Mw/Mn约3.06。聚合物的差式扫描量热(“DSC”)研究显示形成了乙烯-苯乙烯-异丁烯三元聚合物。
                        实施例8
步骤基本上与实施例7相同。将乙烯和异丁基比例分别为约10％和90％的约10psig气体混合物加入装有约1.04×10-4mol(C5Me5)TiCl3和约10mlα-甲基苯乙烯约25℃的反应器中。用约3ml0.05M TiBA和5ml0.02M Ph3CB(C6F5)4溶液引发聚合。将反应体系的气相以约10ml/min的速率连续排空。反应约1小时后，获得固体产品，其活性为0.24×105g聚合物/(molTi-Hr)。聚合物的DSC研究显示形成了乙烯-α-甲基苯乙烯-异丁烯三元聚合物。
                        实施例9
步骤基本上与实施例8相同。但用于1.04×10-4mol Insite催化剂代替(C5Me5)TiCl3作为聚合催化剂。反应约1小时后，获得固体，其活性为0.41×105g聚合物/(molTi-Hr)。该产品的DSC研究显示形成了乙烯-α-甲基苯乙烯-异丁烯三元聚合物。
                        实施例10
步骤基本上与实施例1相似。将装有磁搅拌器的250ml压力反应瓶用氩气彻底清洗，并投入约50ml干燥甲苯和10ml苯乙烯。然后将约10psig异丁烯加入约50℃下反应瓶中。用约3ml0.05MTiBA、4ml0.0152M(C5Me5)TiCl3甲苯溶液和4ml0.0152MPh3CB(C6F5)4引发聚合。反应约1小时后，获得透明液体，其活性为约1.21×105g聚合物/(molTi-hr)。该液体的13C-NMR分析显示形成基本上无规苯乙烯-异丁基共聚物，它含有约67％异丁烯和约33％苯乙烯。图3为苯乙烯和异丁烯共聚产品的13C-NMR光谱图。该液体产品的重均分子量Mw约2,755，和Mw/Mn约3.62。
                        实施例11
步骤基本上与实施例10相似。将装有磁搅拌器的250ml压力反应瓶用氩气彻底清洗，并投入约1.04×10-4mol(C5Me5)TiCl3和约10mlα-甲基苯乙烯。将约10psig异丁烯加入约25℃下反应瓶中。用约3ml 0.05M TiBA和5ml0.02M Ph3CB(C6F5)4溶液引发聚合。反应约1小时后，获得透明液体，其活性为约0.51×105g聚合物/(molTi-hr)。该液体的13C-NMR分析显示形成基本上无规α-甲基苯乙烯-异丁烯共聚物，它含有约59％异丁烯和约41％α-甲基苯乙烯。图4为该α-甲基苯乙烯和异丁烯共聚产品的13C-NMR光谱图。该液体产品具有Mw约1,211，和Mw/Mn约3.85。
                        实施例12
本实施例是比较市购的聚-α-烯烃基料与用实施例2中获得的氢化乙烯-异丁烯共聚物配制的基础油。市购聚-α-烯烃以商品名Mobil 1001并称为PAO 100。两个由市购聚-α-烯烃制备的样品：第一种样品包括PAO100作为主组分和约0.25wt％抗氧剂；第二种样品包括PAO100和约0.50wt％抗氧剂。使用的抗氧剂为2，6-二叔丁基-4-甲基苯酚。
两种另外的样品由实施例2获得的氢化乙烯/异丁烯共聚物制备。将该氢化乙烯/异丁烯共聚物分别与约0.25wt％和约0.50wt％2，6-二叔丁基-4-甲基苯酚作为抗氧剂混合，由此制备编号为第三和第四种样品。
通过DSC研究这四种样品的抗氧化性。本方法中，将该样品放入填充氧气至约500psi的样品室中。将该样品加热至温度约175℃。用DSC仪器检测并记录样品在这些条件下氧化所需的诱导时间。该诱导时间为样品氧化稳定性的一般指标。通常，诱导时间越长，样品的耐氧化性越好。表2给出测量的四种样品的平均诱导时间。
                           表2
样品编号                组成  平均诱导时间(min)
    1   PAO100和0.25wt％抗氧剂     27.8
    2   PAO100和0.50wt％抗氧剂     30.1
    3   乙烯/异丁烯与0.25wt％抗氧剂     31.7
    4   乙烯/异丁烯与0.50wt％抗氧剂     42.7
令人吃惊的是，对于相同量的抗氧剂，乙烯/异丁烯共聚物基本上具有比PAO100更好的耐氧化性。因此，本发明实施方案中获得的乙烯/异丁烯共聚物可用作润滑油的组分。
按照本发明实施方案获得的含亚乙烯基的聚合物约0.1wt％至约99wt％用作润滑油。这些润滑油还可含有提供各种功能所需量的多种常规添加剂。这些添加剂包括但不限于无灰分散剂、金属或高碱性金属洗涤剂、二硫代磷酸二烃基锌、抗磨蚀添加剂、抗氧剂、倾点抑制剂、防锈剂、节油剂或摩擦降低剂等。
合适的无灰分散剂包括但不限于聚链烯基或硼酸化的聚链烯基丁二酰亚胺，其中链烯基衍生至C3-C4烯烃，特别是具有数均分子量约7,090至5,000的聚异丁烯。其它公知的分散剂包括烃取代丁二酸酐的油溶性多醇酯，例如聚异丁烯基丁二酸酐，及衍生自烃取代丁二酸酐和二取代氨基醇的油溶性噁唑啉和内酯噁唑啉分散剂。润滑油通常含有约0.5至约5wt％的无灰分散剂。
合适的金属洗涤剂添加剂是本领域已知的，可包括一种或多种高碱性油溶性钙、镁和钡的酚盐，硫化酚盐，及磺酸盐(特别是具有总碱值约80至300的C16-C50烷基取代苯或甲苯磺酸的磺酸盐)。这些高碱性物质可单独使用金属洗涤剂添加剂或与中性的同类添加剂并用；但总的金属洗涤剂添加剂应具有上述总碱值表示的碱度。对于高碱性硫化酚盐与中性钙硫化酚盐(由C9或C20烷基苯酚获得)的混合物，它们的使用量为约3至6wt％。
合适的抗磨蚀添加剂为具有总计至少5个碳原子的油溶性二烃基二硫代磷酸锌，其用量总计为约1-6wt％。
合适的常规粘度指数改进剂或粘度改性剂为烯烃聚合物，如聚丁烯、氢化的苯乙烯与异戊二烯和/或丁二烯的聚合物及共聚物和三元聚合物，丙烯酸烷基酯或甲基丙烯酸烷基酯的聚合物，甲基丙烯酸烷基酯与N-乙烯基吡咯烷酮或甲基丙烯酸酯二甲氨基烷基的共聚物，乙烯、丙烯与具有可与醇或亚烷基多胺进一步反应的活性单体如马来酸酐的接枝聚合物，与醇和胺等反应的苯乙烯-马来酸酐聚合物。这些改进剂可根据提供成品油中所需的粘度范围的要求，按照已知配料技术使用。
合适的氧化抑制剂的例子为受阻酚类，如2，6-二叔丁基对甲酚、胺、硫化苯酚和烷基吩噻酮。润滑油根据其效力通常可含约0.01至3wt％氧化抑制剂。
防锈剂可以非常小的比例如约0.1至1wt％使用，其中合适的防锈剂可列举C9-C30脂族丁二酸或酸酐如十二碳烯丁二酸酐。消泡剂通常为聚硅氧烷硅酮聚合物，其用量为约0.01至1wt％。
对于很多润滑粘度的矿物油基料，倾点抑制剂的用量通常为约0.01至约10.0wt％，优选约0.1至约1wt％。通常用于润滑油组合物的倾点制剂的例子为甲基丙烯酸正烷基和丙烯酸烷基酯的聚合物和共聚物，富马酸二正烷基酯和乙酸乙烯酯的共聚物，α-烯烃共聚物，烷基萘，α-烯烃和苯乙烯和/或烷基苯乙烯的共聚物或三元聚合物，苯乙烯二烷基马来酸共聚物等。
按照本发明实施方案获得的聚合物可用于很多领域，取决于聚合物的类型和其组成。这些聚合物可为液体、半固体或固体形式。这些聚合物可为弹性体、塑料或塑性体。聚合物的分子量可为约200至2,000,000以上。该聚合物可被裂解、氢化或加氢异构化。通过裂解、氢化或加氢异构化获得的聚合物产品可用作润滑油和其它合适产品的组分。
根据本发明的实施方案，含脂族α-烯烃的亚乙烯基共聚物和三元聚合物可用作压敏胶和热熔胶。本发明含苯乙烯的产品具有可打印或可排版涂料所需的性能。含亚乙烯基的具有非共轭二烯烃共聚单体的聚合物可用作密封剂、弹性体和粘度改进剂。注意到，亚乙烯基/乙烯共聚物基本上无叔氢，因此耐氧化和耐过渡金属催化降解。由于不存在活性叔氢，由这些聚合物配制的润滑油具有改进的高温氧化稳定性。
如上所述，本发明的实施方案提供各种含亚乙烯基的聚合物。其中有亚乙烯基/α-烯烃聚合物和亚乙烯基/亚乙烯基聚合物。这些聚合物可非必要地包括与亚乙烯基烯烃和α-烯烃不同的另一种烯烃单体。对于乙烯/亚乙烯基聚合物，它包括至少一种亚乙烯基二单元组。对于其它类型的聚合物，可存在或无亚乙烯基烯烃二单元组。当用作润滑油组分时，这些聚合物可提供一种或多种如下优点：改进的耐氧化稳定性、改进的热稳定性、所需的粘度、低倾点、低冷龟裂粘度、较高的燃点和低成本效益。
重要的是，含亚乙烯基聚合物的用途不只限于润滑油。该含亚乙基的聚合物还具有多种用途：可用于制造空气清洁产品(air careproduct)、护肤产品、护发产品、化妆品、家用产品、清洁剂、抛光剂、织物防护产品、纺织涂敷剂、纺织润滑剂、汽车产品、汽车清洗和抛光剂、燃料添加剂、油添加剂、蜡烛、药物、悬浮剂、防晒产品、杀虫剂、凝胶、液压油、传导流体、聚合物的改性剂、生物降解产品、机油等。另一些用途可包括热熔粘合剂、打印涂料、密封剂、弹性体和粘度改进剂。
尽管本发明已结合有限数量的实施方案进行了详细描述，但存在对这些实施方案的各种替换和变化。例如，不含有α-烯烃的包括两种或多种亚乙烯基的聚合物可用这里描述的方法生产。此外，可按相同方式合成仅包括亚乙烯基烯烃的共聚物、三元聚合物和四元聚合物。虽然可在单中心催化剂存在下制备本发明实施方案的聚合物，但也可使用其它催化剂体系，只要可生产具有这里描述的类似特性的聚合物即可。所附的权利要求拟覆盖落入本发明范围内的所有这些变化和替换。

Claims (17)

1.一种聚合物，包括乙烯单体和亚乙烯基烯烃单体的聚合单元，其中该聚合物具有包括重复单元[-E-V-]和至少一个单元[-V-V]的聚合物链，其中E表示乙烯单体，V表示亚乙烯基烯烃单体，并且所述聚合物的分子量分布低于3.5。
2、如权利要求1所述的聚合物，其中聚合物链还包括[-E-]的重复单元。
3、如权利要求1所述的聚合物，其中亚乙烯基单体选自脂族亚乙烯基烯烃、环亚乙烯基烯烃和芳族亚乙烯基烯烃。
4、如权利要求1所述的聚合物，其中亚乙烯基烯烃具有通式R1-CH＝CR2R3，其中R1为氢、烷基、芳基或芳烷基，R2和R3独立地选自烷基、芳基和芳烷基。
5、如权利要求1所述的聚合物，其中亚乙烯基烯烃单体选自2-甲基-1-丙烯、2-甲基-1-丁烯、2-甲基-1-戊烯、2-甲基-1-己烯和α-甲基苯乙烯。
6、如权利要求1所述的聚合物，其中该聚合物为乙烯与异丁烯的共聚物或乙烯与α-甲基苯乙烯的共聚物。
7、如权利要求1所述的聚合物，其中该聚合物还包括第三种烯烃单体的三元聚合物，该第三种烯烃单体与乙烯单体和亚乙烯基烯烃单体不同。
8、如权利要求7所述的聚合物，其中第三种烯烃单体选自脂族烯烃、芳族烯烃和环烯烃。
9、如权利要求7所述的聚合物，其中第三种烯烃单体选自丙烯、1-丁烯、1-戊烯、1-己烯、1-庚烯、1-辛烯、1-壬烯、1-癸烯和苯乙烯。
10、如权利要求7所述的聚合物，其中该聚合物为乙烯、丙烯和异丁烯的三元聚合物，乙烯、苯乙烯和异丁烯的三元聚合物，或乙烯、α-甲基苯乙烯和异丁烯的三元聚合物。
11、一种通过裂解权利要求1的聚合物获得的裂解聚合物。
12、一种通过氢化权利要求1的聚合物获得的氢化聚合物。
13、一种通过氢化权利要求11的裂解聚合物获得的氢化聚合物。
14、一种通过加氢异构化权利要求1的聚合物获得的加氢异构化聚合物。
15、一种包括权利要求1的聚合物的制成品。
16、如权利要求15所述的制成品，其中该制成品为润滑剂、热熔粘合剂、可打印涂料、密封剂、弹性体、塑料或粘度改进剂。
17、一种制备润滑油的方法，其中包括将权利要求1的聚合物与添加剂混合，制备润滑油。
CN00100180A 1999-11-24 2000-01-14 含亚乙烯基的聚合物及其制备方法和用途 Expired - Fee Related CN1122675C (zh)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US09/448707 1999-11-24
US09/448,707 US6586646B1 (en) 1997-06-20 1999-11-24 Vinylidene-containing polymers and uses thereof
US09/448,707 1999-11-24

Publications (2)

Publication Number Publication Date
CN1297949A CN1297949A (zh) 2001-06-06
CN1122675C true CN1122675C (zh) 2003-10-01

Family

ID=23781358

Family Applications (1)

Application Number Title Priority Date Filing Date
CN00100180A Expired - Fee Related CN1122675C (zh) 1999-11-24 2000-01-14 含亚乙烯基的聚合物及其制备方法和用途

Country Status (11)

Country Link
US (1) US6586646B1 (zh)
EP (1) EP1103568A1 (zh)
JP (1) JP2001151820A (zh)
KR (1) KR20010049193A (zh)
CN (1) CN1122675C (zh)
AR (2) AR022132A1 (zh)
CA (1) CA2292360C (zh)
HK (1) HK1034982A1 (zh)
MY (1) MY121130A (zh)
NO (1) NO20000194L (zh)
ZA (1) ZA200000038B (zh)

Families Citing this family (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100518425B1 (ko) * 2001-11-01 2005-09-29 미쯔이카가쿠 가부시기가이샤 윤활유용 첨가제 및 윤활유 조성물
WO2004031250A1 (en) 2002-10-02 2004-04-15 Dow Global Technologies Inc. Liquid and gel-like low molecular weight ethylene polymers
KR20020089272A (ko) * 2002-11-04 2002-11-29 주식회사엔에스오 수용성접착이 가능하며 pvc 및 국내산스티렌대체용합성수지 및 제조방법
WO2007011462A1 (en) 2005-07-19 2007-01-25 Exxonmobil Chemical Patents Inc. Lubricants from mixed alpha-olefin feeds
DE102005038283A1 (de) * 2005-08-12 2007-02-22 Basf Ag Solvensstabilisierte Metallkomplexe mit schwach koordinierenden Gegenanionen als Polymerisationskatalysatoren
JP5390738B2 (ja) 2005-11-15 2014-01-15 出光興産株式会社 内燃機関用潤滑油組成物
JP5368706B2 (ja) * 2005-12-28 2013-12-18 出光興産株式会社 金属加工用潤滑剤
US8168838B2 (en) * 2009-01-21 2012-05-01 Shell Oil Company Hydrocarbon compositions useful as lubricants
US8530712B2 (en) 2009-12-24 2013-09-10 Exxonmobil Chemical Patents Inc. Process for producing novel synthetic basestocks
US10584297B2 (en) 2016-12-13 2020-03-10 Afton Chemical Corporation Polyolefin-derived dispersants
US10858599B2 (en) 2018-08-22 2020-12-08 Exxonmobil Research And Engineering Company Manufacturing hydrocarbons
US10815439B2 (en) 2018-08-22 2020-10-27 Exxonmobil Research And Engineering Company Manufacturing hydrocarbons
US11015131B2 (en) 2018-08-22 2021-05-25 Exxonmobil Research And Engineering Company Manufacturing hydrocarbons
US10858600B2 (en) 2018-08-22 2020-12-08 Exxonmobil Research And Engineering Company Manufacturing a base stock
US10843980B2 (en) 2018-08-22 2020-11-24 Exxonmobil Research And Engineering Company Manufacturing a base stock from ethanol
US10889769B2 (en) 2018-08-22 2021-01-12 Exxonmobil Research And Engineering Company Manufacturing a base stock from ethanol
CN110407965A (zh) * 2019-06-10 2019-11-05 河南省君恒实业集团生物科技有限公司 一种低碳烯烃一步法聚合制备pao的方法
US11555086B2 (en) * 2019-07-30 2023-01-17 Korea Advanced Institute Of Science And Technology Method of synthesizing hydrocarbon polymers using deoxygenation

Family Cites Families (72)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1033456A (en) 1964-03-23 1966-06-22 Shell Int Research Hydrogenated copolymers
US3442839A (en) 1964-11-23 1969-05-06 Ppg Industries Inc Coating compositions comprising an unsaturated glyceride and a nonrubbery,unsaturated hydrocarbon polymer
US3345426A (en) 1964-12-04 1967-10-03 Exxon Research Engineering Co Preparation of tetraalkyl benzene
US3600451A (en) 1965-03-16 1971-08-17 Cosden Oil & Chem Co Polymer alkylation of aromatics
DE1939037B2 (de) 1967-07-31 1980-02-07 Exxon Research And Engineering Co., Linden, N.J. (V.St.A.) Athylen/Propylen-Polymerisate, Verfahren zu ihrer Herstellung und ihre Verwendung
US3437464A (en) 1968-03-05 1969-04-08 Sun Oil Co Gelling normally liquid volatile hydrocarbons with atactic propylene-ethylene copolymers
US3598552A (en) 1968-12-13 1971-08-10 Exxon Research Engineering Co Pour depressants for middle distillates
CH544835A (de) * 1970-10-14 1974-01-15 Ciba Geigy Ag Verwendung von Benzofuranen zum optischen Aufhellen von Textilmaterial
US3676521A (en) 1970-10-05 1972-07-11 Sun Oil Co Synthetic lubricants from low molecular weight olefins
US3832403A (en) 1971-03-01 1974-08-27 Univ Akron Method for reacting organic halides
US3850586A (en) 1972-04-13 1974-11-26 Dai Ichi Kogyo Seiyaku Co Ltd Gelled hydrocarbon composition
US3923919A (en) 1972-07-07 1975-12-02 Sun Ventures Inc Ethylene-propylene copolymer oil
CA1059111A (en) 1974-12-20 1979-07-24 Dominic A. Apikos Metal working lubricant comprising ethylene copolymers
US4137274A (en) 1975-06-18 1979-01-30 Upo Inc. Process for motor fuel production by olefin polymerization
SU732364A1 (ru) 1978-01-31 1980-05-05 Предприятие П/Я В-8952 Способ получени синтетического смазочного масла
US4231883A (en) 1979-05-04 1980-11-04 Ethyl Corporation Lubricant composition
ZA803258B (en) 1979-06-15 1981-05-27 Mobil Oil Corp Process for making synthetic lubricating oils
DE3007725A1 (de) 1980-02-29 1981-09-17 Hansjörg Prof. Dr. 2000 Hamburg Sinn Verfahren zur herstellung von polyethylen, polypropylen und copolymeren
JPS573804A (en) * 1980-06-10 1982-01-09 Mitsui Petrochem Ind Ltd Production of ethylene copolymer
DE3127133A1 (de) 1981-07-09 1983-01-27 Hoechst Ag, 6000 Frankfurt Verfahren zur herstellung von polyolefinen und deren copolymerisaten
US4377720A (en) 1981-12-14 1983-03-22 Exxon Research And Engineering Co. Preparation of linear olefin products
US4547202A (en) 1982-02-02 1985-10-15 Atlantic Richfield Company Hydrocarbon oils with improved pour points
US4463201A (en) 1982-04-12 1984-07-31 Mobil Oil Corporation Process for making synthetic lubricating oils
US4413156A (en) 1982-04-26 1983-11-01 Texaco Inc. Manufacture of synthetic lubricant additives from low molecular weight olefins using boron trifluoride catalysts
JPH0710900B2 (ja) * 1982-06-18 1995-02-08 エクソン リサーチ アンド エンヂニアリング コムパニー 中級蒸留物燃料油用流動性改良剤
US4510342A (en) 1982-12-29 1985-04-09 The Standard Oil Company High viscosity index synthetic oils and synthesis thereof
US5324800A (en) 1983-06-06 1994-06-28 Exxon Chemical Patents Inc. Process and catalyst for polyolefin density and molecular weight control
US4789714A (en) 1983-06-15 1988-12-06 Exxon Research & Engineering Co. Molecular weight distribution modification in tubular reactor
US4540753A (en) 1983-06-15 1985-09-10 Exxon Research & Engineering Co. Narrow MWD alpha-olefin copolymers
US4507515A (en) 1983-12-21 1985-03-26 Exxon Research & Engineering Co. Lubricating oil compositions containing ethylene-alpha-olefin polymers of controlled sequence distribution and molecular heterogeneity
US4621111A (en) 1983-12-28 1986-11-04 Exxon Research And Engineering Company Acid base interacting polymer solutions
DE3443087A1 (de) 1984-11-27 1986-05-28 Hoechst Ag, 6230 Frankfurt Verfahren zur herstellung von polyolefinen
US4666619A (en) 1984-12-17 1987-05-19 Exxon Research & Engineering Co. Ethylene polymer useful as a lubricating oil viscosity modifier E-25
DE3678024D1 (de) 1985-03-26 1991-04-18 Mitsui Petrochemical Ind Fluessiges statisches ethylencopolymer, verfahren zur herstellung und anwendung desselben.
US4668834B1 (en) 1985-10-16 1996-05-07 Uniroyal Chem Co Inc Low molecular weight ethylene-alphaolefin copolymer intermediates
EP0230753B1 (en) 1985-12-16 1991-10-23 Exxon Research And Engineering Company Copolymer compositions containing a narrow mwd component and process of making same
JPH086113B2 (ja) 1986-07-11 1996-01-24 三井石油化学工業株式会社 作動油
US4658078A (en) 1986-08-15 1987-04-14 Shell Oil Company Vinylidene olefin process
JPH072617B2 (ja) 1986-12-01 1995-01-18 三井石油化学工業株式会社 皮膚外用剤
US4794096A (en) 1987-04-03 1988-12-27 Fina Technology, Inc. Hafnium metallocene catalyst for the polymerization of olefins
US4804794A (en) 1987-07-13 1989-02-14 Exxon Chemical Patents Inc. Viscosity modifier polymers
US4855526A (en) 1987-12-18 1989-08-08 Mobil Oil Corporation Process for preparing ethylene-higher olefin copolymer oils with Ziegler-Natta catalyst in mixed aliphatic-aromatic solvent
DE3743320A1 (de) 1987-12-21 1989-06-29 Hoechst Ag 1-olefinstereoblockpolymerwachs und verfahren zu seiner herstellung
GB8804033D0 (en) 1988-02-22 1988-03-23 Shell Int Research Process for preparing normally liquid hydrocarbonaceous products from hydrocarbon feed
US5043515A (en) 1989-08-08 1991-08-27 Shell Oil Company Ethylene oligomerization catalyst and process
CA2000182C (en) 1988-10-27 1999-04-06 Lynn H. Slaugh Ethylene oligomerization process and catalyst
US5321107A (en) 1989-01-31 1994-06-14 Mitsui Petrochemical Industries, Ltd. Olefin polymerization catalyst and process for the polymerization of olefins
US5068476A (en) 1989-04-28 1991-11-26 Mobil Oil Corporation Lubricant oligomers of C2 -C5 olefins
US4990709A (en) 1989-04-28 1991-02-05 Mobil Oil Corporation C2-C5 olefin oligomerization by reduced chromium catalysis
US5151204A (en) 1990-02-01 1992-09-29 Exxon Chemical Patents Inc. Oleaginous compositions containing novel ethylene alpha-olefin polymer viscosity index improver additive
JPH04117414A (ja) * 1990-09-06 1992-04-17 Idemitsu Petrochem Co Ltd エチレン・α―置換スチレン系共重合体及びその製造方法
US5171919A (en) 1990-10-17 1992-12-15 Idemitsu Kosan Co., Ltd. Process for producing propylene based oligomers
US5087788A (en) 1991-03-04 1992-02-11 Ethyl Corporation Preparation of high purity vinylindene olefin
US5310490A (en) 1991-03-13 1994-05-10 Exxon Chemical Products Inc. Viscosity modifer polymers
US5276227A (en) 1992-02-03 1994-01-04 Mobil Oil Corporation C2 -C5 olefin oligomer compositions as shear stable viscosity index improvers
US5217636A (en) 1992-03-10 1993-06-08 Albright & Wilson Americas Inc. Lubricating oil viscosity index improver composition
EP0641362B1 (en) 1992-04-20 1998-11-11 Exxon Chemical Patents Inc. Ethylene/branched olefin copolymers
US5296515A (en) 1992-06-03 1994-03-22 Phillips Petroleum Company Hydrovisbreaking of hydrocarbon polymers
DE69229044T2 (de) 1992-08-31 1999-10-07 Fina Research S.A., Feluy Verfahren zur Herstellung von flüssigen statistischen Copolymerisaten des Typs Ethylen
IL107927A0 (en) * 1992-12-17 1994-04-12 Exxon Chemical Patents Inc Oil soluble ethylene/1-butene copolymers and lubricating oils containing the same
US5554310A (en) 1992-12-17 1996-09-10 Exxon Chemical Patents Inc. Trisubstituted unsaturated polymers
US5330666A (en) 1993-02-22 1994-07-19 Exxon Research And Engineering Company Lubricant composition containing alkoxylated amine salt of hydrocarbylsalicyclic acid
GB9307652D0 (en) 1993-04-14 1993-06-02 Bp Chem Int Ltd Lubricating oils
US5451630A (en) 1994-08-02 1995-09-19 Dsm Copolymer, Inc. Solid sheared polymer blends and process for their preparation
US5557023A (en) 1995-05-23 1996-09-17 The Governors Of The University Of Alberta Olefin oligomerization in the presence of novel complexes
US5721842A (en) * 1995-08-25 1998-02-24 Apex Pc Solutions, Inc. Interconnection system for viewing and controlling remotely connected computers with on-screen video overlay for controlling of the interconnection switch
DE19711339B4 (de) * 1996-03-19 2008-09-11 Denki Kagaku Kogyo K.K. Copolymer aus Ethylen und aromatischer Vinylverbindung, Verfahren zu dessen Herstellung, Formkörper daraus sowie Zusammensetzung umfassend das Copolymer
US5763556A (en) 1996-05-21 1998-06-09 Exxon Chemical Patents Inc. Copolymers of ethylene and geminally disubstituted olefins
US5811379A (en) 1996-06-17 1998-09-22 Exxon Chemical Patents Inc. Polymers derived from olefins useful as lubricant and fuel oil additives, processes for preparation of such polymers and additives and use thereof (PT-1267)
US6100354A (en) 1997-02-24 2000-08-08 Exxon Chemical Patents Inc. Olefin copolymers from bridged bis(arylamido) Group 4 catalyst compounds
US6124513A (en) * 1997-06-20 2000-09-26 Pennzoil-Quaker State Company Ethylene-alpha-olefin polymers, processes and uses
TW432094B (en) 1997-12-16 2001-05-01 Dow Chemical Co Seals produced from alpha-olefin/vinylidene aromatic and/or hindered aliphatic vinylidene/interpolymer based materials

Also Published As

Publication number Publication date
ZA200000038B (en) 2000-07-12
AR022133A1 (es) 2002-09-04
JP2001151820A (ja) 2001-06-05
NO20000194L (no) 2001-05-25
CA2292360A1 (en) 2001-05-24
AR022132A1 (es) 2002-09-04
US6586646B1 (en) 2003-07-01
HK1034982A1 (en) 2001-11-09
CA2292360C (en) 2006-10-24
NO20000194D0 (no) 2000-01-14
CN1297949A (zh) 2001-06-06
KR20010049193A (ko) 2001-06-15
EP1103568A1 (en) 2001-05-30
MY121130A (en) 2005-12-30

Similar Documents

Publication Publication Date Title
CN1122675C (zh) 含亚乙烯基的聚合物及其制备方法和用途
CN100390256C (zh) 合成润滑油和润滑油组合物
JP3583149B2 (ja) エチレン−α−オレフィン重合体、製法および使用法
CN103080146B (zh) 可官能化的合成的烃流体和用于生产所述烃流体的集成的方法
CN1291204A (zh) 用桥连的二茂铪化合物制备烯烃共聚物的聚合方法
CN101925617B (zh) 在生产茂金属催化的聚α烯烃中线性α烯烃的改进利用
JP2002518582A (ja) メタロセン触媒を使用して製造されるオリゴデセン、その製造および潤滑剤における成分としてのその使用
CN1549852A (zh) 聚α-烯烃的合成及其用途
CN1576359B (zh) 用于润滑油的粘度指数改进剂
CN102482365B (zh) 用于形成高粘度聚α-烯烃的二阶段方法和系统
KR20030097860A (ko) 윤활유로서 1-데센과 1-도데센의 공중합체
US4906799A (en) Process for the production of reduced viscosity high VI hydrocarbon lubricant
JP2006503973A (ja) 合成潤滑油組成物およびその製造方法
CN1241195A (zh) 官能化聚合物
US20230312774A1 (en) Processes For Polymerizing Alpha-Olefins, Internal Olefins And Compositions Thereof
EP0902081B1 (en) Lubricating oil or lubricating oil composition and fuel oil composition
US5068476A (en) Lubricant oligomers of C2 -C5 olefins
CN106795449A (zh) 润滑油组合物
CN109369835A (zh) 用于α-烯烃聚合的茂稀土金属催化剂组合物及其应用
CN102015798A (zh) α-烯烃/异丁烯二嵌段共聚物
AU747216B2 (en) Vinylidene-containing polymers and uses thereof
AU2002300501B2 (en) Vinylidene-containing polymers and uses thereof
JPS62177099A (ja) トラクシヨン用フル−ド
RU2804659C2 (ru) Синтетические жидкости, обладающие улучшенной биологической разлагаемостью
MXPA00001236A (en) Vinylidene-containing polymers and uses thereof

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20031001

Termination date: 20180114

CF01 Termination of patent right due to non-payment of annual fee