[go: up one dir, main page]

WO1996017041A1 - Melanges polymeres contenant des copolymeres d'olefines et des polymeres ramifies en etoile - Google Patents

Melanges polymeres contenant des copolymeres d'olefines et des polymeres ramifies en etoile Download PDF

Info

Publication number
WO1996017041A1
WO1996017041A1 PCT/US1995/015707 US9515707W WO9617041A1 WO 1996017041 A1 WO1996017041 A1 WO 1996017041A1 US 9515707 W US9515707 W US 9515707W WO 9617041 A1 WO9617041 A1 WO 9617041A1
Authority
WO
WIPO (PCT)
Prior art keywords
polymer
olefin copolymer
composition
star
crystalline
Prior art date
Application number
PCT/US1995/015707
Other languages
English (en)
Inventor
Alfred Karl Jung
Maria Magdalena Kapuscinski
James W. Moore
Robert T. Biggs
Original Assignee
Ethyl Additives Corporation
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 Ethyl Additives Corporation filed Critical Ethyl Additives Corporation
Priority to AU45072/96A priority Critical patent/AU4507296A/en
Priority to EP95943653A priority patent/EP0794995A1/fr
Publication of WO1996017041A1 publication Critical patent/WO1996017041A1/fr

Links

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
    • C10M157/00—Lubricating compositions characterised by the additive being a mixture of two or more macromolecular compounds covered by more than one of the main groups C10M143/00 - C10M155/00, each of these compounds being essential
    • C10M157/04—Lubricating compositions characterised by the additive being a mixture of two or more macromolecular compounds covered by more than one of the main groups C10M143/00 - C10M155/00, each of these compounds being essential at least one of them being a nitrogen-containing compound
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/16—Ethene-propene or ethene-propene-diene copolymers
    • 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
    • C10M143/00—Lubricating compositions characterised by the additive being a macromolecular hydrocarbon or such hydrocarbon modified by oxidation
    • C10M143/02—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
    • 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
    • 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
    • C10M143/12—Lubricating compositions characterised by the additive being a macromolecular hydrocarbon or such hydrocarbon modified by oxidation containing conjugated diene
    • 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
    • C10M143/14—Lubricating compositions characterised by the additive being a macromolecular hydrocarbon or such hydrocarbon modified by oxidation containing non-conjugated diene
    • 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
    • C10M149/00—Lubricating compositions characterised by the additive being a macromolecular compound containing nitrogen
    • C10M149/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M149/06—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an amido or imido group
    • 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
    • C10M149/00—Lubricating compositions characterised by the additive being a macromolecular compound containing nitrogen
    • C10M149/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M149/10—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a nitrogen-containing hetero 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
    • C10M157/00—Lubricating compositions characterised by the additive being a mixture of two or more macromolecular compounds covered by more than one of the main groups C10M143/00 - C10M155/00, each of these compounds being essential
    • 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
    • C10M2205/022—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
    • C10M2205/04—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
    • C10M2205/06—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing conjugated dienes
    • 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
    • C10M2205/08—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing non-conjugated dienes
    • 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
    • C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2217/02—Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2217/024—Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an amido or imido group
    • 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
    • C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2217/02—Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2217/028—Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a nitrogen-containing hetero 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
    • C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2217/06—Macromolecular compounds obtained by functionalisation op polymers with a nitrogen containing compound
    • 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
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • 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
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • C10N2040/251—Alcohol-fuelled engines
    • 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
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • C10N2040/252—Diesel engines
    • 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
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • C10N2040/252—Diesel engines
    • C10N2040/253—Small diesel engines
    • 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
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • C10N2040/255—Gasoline engines
    • 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
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • C10N2040/255—Gasoline engines
    • C10N2040/28—Rotary engines
    • 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
    • C10N2070/00—Specific manufacturing methods for lubricant compositions
    • C10N2070/02—Concentrating of additives

Definitions

  • This invention relates to additive compositions. Specifically, the present invention relates to additives which are blends of either crystalline olefin copolymers and star branched polymers or amorphous olefin copolymers and star branched polymers or blends of crystalline and amorphous olefin copolymers with star branched polymers.
  • Lubricating oil compositions which use ethylene- propylene copolymer (EPM) or ethylene-propylene diene terpolymer (EPDM) as viscosity index improvers are known in the art. It is also known that such polymers can be amorphous or partly crystalline based on their ethylene/propylene content. Typically, random EPMs or EPDMs containing 40-70 mole % ethylene are amorphous, while copolymers or terpolymers containing over 70 mole % ethylene are partly crystalline. The crystallinity increases with the amount of ethylene.
  • EPM ethylene- propylene copolymer
  • EPDM ethylene-propylene diene terpolymer
  • Linear amorphous polymers can flow under ambient conditions while the crystalline materials have excellent dimensional stability.
  • solutions of partially crystalline olefin copolymers (OCPs) behave differently from amorphous OCPs as they can form ordered aggregates which tend to reduce viscosity.
  • Lubricating oils containing neat, partially crystalline OCPs show improvement over conventional amorphous OCPs in low temperature cranking or pumbability performance, but their pour points are not satisfactory.
  • VI improvers by contrast to amorphous OCP polymer VI improvers, the VI improvers based on partially crystalline OCPs require elevated temperatures for handling and storage as well as special blending conditions to achieve satisfactory performance.
  • compositions comprising blends of at least one olefin copolymer and at least one star polymer. Additionally, the instant invention encompasses lubricating oil compositions comprising a mixture of base oil and the present polymer blends.
  • compositions falling within the scope of the present invention can be dimensionally stable, and enhance the low temperature properties of a lubricating oil composition to which they have been added, and improve the viscosity index of lubricating oil.
  • the present invention comprises lubricating oil composition containing a major portion of a lubricating oil (base oil) and minor amounts of a lubricant additive composition comprising crystalline olefin copolymers and star polymers or amorphous olefin copolymers and star polymers or a mixture of crystalline and amorphous olefin copolymers with star polymers.
  • base oil a lubricating oil
  • a lubricant additive composition comprising crystalline olefin copolymers and star polymers or amorphous olefin copolymers and star polymers or a mixture of crystalline and amorphous olefin copolymers with star polymers.
  • the present invention relates to dimensionally stable blends of linear crystalline OCPs with star polymers or dimensionally stable crystalline and amorphous OCPs with star polymers or amorphous OCPs with star polymers which are useful for VI improver applications in lubricant oil compositions.
  • These polymeric blends exhibit the desirable properties of their individual components but reduce or eliminate their undesirable properties.
  • Blends of crystalline OCPs and star polymers as well as blends of crystalline and amorphous OCPs with star polymers exhibit dimensional stability and also provide lubricating oil compositions which have a high degree of shear stability and exhibit enhanced low temperature properties.
  • the blend of amorphous OCPs and star polymers can be used in lubricant oil compositions to provide lubricant oil compositions with desirable properties such as good shear stability and enhanced low temperature property.
  • the novel polymer blend may comprise an oil- soluble composition comprising a star polymer and an amorphous copolymer (random EPM or EPDM) wherein the copolymer or terpolymer has an ethylene content from 40 to 70 mole %, and a partially crystalline copolymer or terpolymer having an ethylene content from above 70 to 85 mole%. It may also comprise a star polymer and a partially crystalline olefin copolymer or terpolymer having an ethylene content from above 70 to 85% mole and a star polymer.
  • an oil- soluble composition comprising a star polymer and an amorphous copolymer (random EPM or EPDM) wherein the copolymer or terpolymer has an ethylene content from 40 to 70 mole %, and a partially crystalline copolymer or terpolymer having an ethylene content from above 70 to 85 mole%. It may also comprise a star polymer and a partially crystalline o
  • the amorphous and crystalline copolymer and terpolymers may be prepared using known Ziegler-Natta polymerization methods. Ethylene-propylene copolymers (EPM) and ethylene-propylene-diene terpolymers (EPDM) with and without polar groups attached to the main polymeric chain are preferred for the purpose of this invention.
  • EPM Ethylene-propylene copolymers
  • EPDM ethylene-propylene-diene terpolymers
  • the unsaturated monomers (third monomers) used for the preparation of terpolymers are preferably linear, but may be branched. The amount of the third monomer contained in the terpolymer may range from 0.01 to about 10 weight %.
  • polymeric additive compositions also comprise blends analogous to those mentioned hereinabove in which amorphous EPM or EPDM with attached polar functional groups are employed.
  • EPM and EPDM with attached polar groups include but are not limited to all known dispersant olefin copolymers (DOCP) or dispersant antioxidant olefin copolymers (DAOCP) .
  • DOCP and DAOCP are known to workers in the field as exemplified in De Rosa et al U.S. Patents 5,013,469 and 5,112,508 and Kapuscinski et al. U.S. Patent 5,094,766 herein incorporated by reference.
  • the DAOCP and DOCP polymers may be part of or the only OCP used in the lubricant additive mixture of this invention.
  • blends of DOCP with other OCP's or blends of DAOCP with other OCP's may be used.
  • Preferred blends are about 10 to 70% amorphous OCPs and about 90 to 30% DOCP or about 90 to 30% DAOCP.
  • Most preferred blends are about 30 to 60% of OCPs and about 70 to 40% DOCP or about 70 to 40% DAOCP.
  • Star polymers are known and can be prepared by anionic polymerization methods as exemplified by Rhodes et al. U.S. Patent 5,035,820 and Echert, U.S. Patent 4,358,565, which are herein incorporated by reference. These polymers generally produced by the process comprising the following reaction steps:
  • the star polymer may be hydrogenated.
  • the living polymers obtained by reaction step (a), which are linear unsaturated living polymers, are prepared from one or more conjugated dienes, e.g., C 4 to C, j conjugated dienes and, optionally, one or more 1 monoalkenyl arene compounds.
  • conjugated dienes include butadiene (1,3-butadiene) ; isoprene, 1,3- pentadiene (piperylene) ; 2,3-dimethyl-1,3-butadiene; 3- butyl-1,3-octadiene, 1-phenyl-l,3-butadiene; 1,3- hexadiene; and 4-ethyl-1,3-hexadiene with butadiene and/or isoprene being preferred.
  • the living polymers may also be partly derived from one or more monoalkenyl arene compounds.
  • Preferred monoalkenyl arene compounds are the monovinyl aromatic compounds such as styrene, monovinylnapthalene as well as the alkylated derivatives thereof such as o-, m- and p-methylstyrene, alpha-methylstyrene and tertiary- butylstyrene.
  • Styrene is the preferred monoalkenyl arene compound.
  • the living polymers produced in reaction step (a) are then reacted, in reaction step (b) , with a polyalkenyl compounding agent.
  • Polyalkyl compounding agents capable of forming star-shaped polymers are known. See generally, Fetters et al., U.S. Pat. No. 3,985,830; Milovich, Canadian Pat. No. 716,645; and British Pat. No. 1,025,295. They are usually compounds having at least two non-conjugated alkenyl groups. Such groups are usually attached to the same or different electron withdrawing groups, e.g., an aromatic nucleus. Such compounds have the property that at least two of the alkenyl groups are capable of independent reaction with different living polymers.
  • star polymers are star branched hydrogenated isoprenes.
  • Hydrogenated star branched isoprene are commercially available.
  • Examples of commercially available hydrogenated star branched isoprenes polymers that can be used in the instant compositions include, but are not limited to, the SHELLVIS 200 series, such as SHELLVIS 250, SHELLVIS 200, and SHELLVIS 260.
  • Solid polymer blends comprising shear stable and/or non shear stable partially crystalline linear olefin copolymers with star polymers have been found to give good dimensional stability, excellent shear stability and satisfactory solubility in mineral oils.
  • the present polymer additive blends are viscosity index improvers and provide improved low temperature properties to motor oils and do not show adverse reactivity with other components.
  • the aforementioned additive polymer compositions may be added to a major portion of lubricating oil (base oil) resulting in a composition comprising a major portion of lubricating oil (base oil) and a minor portion of lubricant additive composition. With respect to the present invention a major portion is considered to be 80- 90 wt % while a minor portion is 1-20 wt %.
  • One embodiment of this invention relates to polymeric additive compositions comprising a mixture of at least one crystalline ethylene-propylene copolymer (EPM) or ethylene-propylene-diene terpolymer (EPDM) with at least one star polymer which are useful for preparing shear stable VI improvers.
  • EPM crystalline ethylene-propylene copolymer
  • EPDM ethylene-propylene-diene terpolymer
  • star polymer which are useful for preparing shear stable VI improvers.
  • the instant blends show good dimensional stability when they preferably contain at least about 10 wt % of a crystalline OCP component.
  • Preferred blends of crystalline OCPs and star polymers comprise from about 10 to 70 wt% crystalline OCP and from about 90 to 30 wt% star polymers, most preferred are about 20 to 60 wt% crystalline OCPs and about 80 to 40 wt% star polymers, most preferable are about 30 to 50 wt% crystalline OCPs and about 70 to 50 % star polymers.
  • Yet another embodiment of this invention relates to a lubricant additive composition, comprising a mixture of at least one amorphous and at least one crystalline olefin copolymers with at least one star polymer.
  • Preferred blends comprise about 30 % crystalline OCP, about 50 % amorphous OCP and 20 % star polymers. More preferably about 20 to 60% crystalline OCP, about 30 to 70% amorphous OCP and 10 to 50% star polymers and most preferred is 30 to 50% OCP 20 to 40% amorphous OCP and 10 to 30 star polymers.
  • the instant lubricant additive blends which include a crystalline olefin are easily shippable as solids and retain their dimensional stability.
  • compositions comprising amorphous EPM or EPDM with star polymers.
  • Preferred blends comprises about 10 to 90wt% amorphous OCPs and 90 to 10wt% star polymers. Most preferred is about 20 to 60wt% amorphous OCPs and about 80 to 40 wt% star" polymer. Most preferable is about 30 to 50 wt% amorphous OCPs and 70 to 50wt% star polymer. Compared to neat amorphous OCP, these blends provide enhanced low temperature properties in motor oils.
  • the blends can be prepared by various conventional methods such as by devolatilization of blended polymer solutions or by blending of the solid rubbers in the mastificator, Brabender mixer or extruder.
  • One method is to mix solutions of the polymers and then to devolatilize the mixed solutions to produce a solid polymer blend.
  • Another method is to mix solid polymers, referred to as rubbers, in a masticator, the Brabender Mixer, or an extruder. In the solution/devolatilization procedure, the solvent from the solution of the copolymer rubbers is removed by evaporation.
  • Oil concentrates of the dimensionally stable polymer blend are prepared as follows:
  • a base oil or a mineral lubricating oil or synthetic oil is heated to 80-300°F in a vessel equipped with a mechanical stirrer and a heating jacket.
  • Pieces of the polymer blend are charged gradually to the oil forming a mixture.
  • the mixture is stirred at 80-300°F until the rubber is completely dissolved, which may require from 1-24 hours.
  • the polymer content may be adjusted to a required viscosity level.
  • Lubricating oils in which the multifunctional additives of this invention may find use may include automotive, aircraft, marine, railway, etc., oils; oils used in spark ignition or compression ignition; summer or winter oils, etc.
  • the lubricating oils may be characterized by a b.p. of about 570 ⁇ F. to about 660°F., preferably 610°F., an e.p. of about 750°F. to about 1200°F., preferably 1020 ⁇ F.; an API gravity of about 25 to about 31, preferably about 29.
  • a typical lubricating oil in which the polymer of this invention may be present may be automotive or diesel engine oil.
  • the polymer blends of the invention show good dimensional stability and the performance of these blends provide enhanced low temperature (cold cranking) performance in motor oils, good pour points, and satisfactory cold storage properties.
  • Pieces of various polymers ( ⁇ i n cubes) are charged gradually to a mixer fitted with a reflux condenser and containing a low boiling hydrocarbon solvent, typically n-hexane, cyclohexane or n-heptane.
  • a low boiling hydrocarbon solvent typically n-hexane, cyclohexane or n-heptane.
  • the mixture is stirred at 60 to 80 C until the rubbers are completely dissolved (approx. 8 hours)
  • the solvent is removed by evaporation under vacuum.
  • the polymer blend residue is tested for dimensional stability and the solution properties in oil are examined.
  • the equipment and dissolution procedure typically used for the manufacture of OCP VI improvers from solid rubber is used for the preparation of the VI improvers from polymer blends:
  • Base oil is heated to 80 - 300 F in a mixer equipped with a mechanical stirrer and heating jacket.
  • Pieces of polymer blend ( ⁇ #" cubes) are charged gradually to the mixer.
  • the mixture is stirred to 80 to 300 F until the rubber is completely dissolved (approx. 1 - 24 hours) .
  • the polymer content is adjusted to the required viscosity level. It can vary with molecular weight of the polymer and blend composition.
  • the resulting concentrated solution is used "as is” for further testing.
  • Polymers are dissolved in n-heptane at 60 C for 8 hours at a temperature of 150 F in a mixer equipped with a mechanical stirrer, reflux condenser and heating jacket. Following complete dissolution of the polymers, the heptane is removed by evaporation under vacuum. A 1" cube is formed from the polymer blend residue and cooled to room temperature.
  • a l" cube of solid rubber is placed between two 3" x C aluminum plates at ambient temperature.
  • the change in the dimensions of the polymer with time is observed and described as follows: excellent - no change good - slight change fair - significant change poor - flows
  • Standard Texaco or ASTM test methods were used for the evaluation of the physical properties of the VI improvers.
  • SSI Shear Stability Index
  • Vbs - Vas x l00% TP Vbs - Vas x l00% TP
  • TP is the thickening power measured by the difference between Vbs and solvent viscosity.
  • Vbs - Vas x 100% is viscosity loss determined VBS according to the ASTM Method D-3945 (Proc. A) .
  • Bench Dispersancv
  • sample VI improver is blended into a formulated oil, which does not contain a dispersant, to make a 10 wt% VI improver solution.
  • the blend is then tested for dispersancy in the Bench VE Test.
  • the evaluation of the cold storage behavior of VI improvers and motor oils containing them was made by utilizing the Ultra Low Temperature Environmental Chamber (Thermotron S-8C) . This piece of equipment allows the determination of the stability of materials under cold temperature conditions. Such conditions were simulated by programming temperatures between -60 and 4 deg. F using an 18 hour time cycle. The samples were examined at 10 degrees Fahrenheit after 8 weeks of storage under these conditions.
  • Thermotron S-8C Ultra Low Temperature Environmental Chamber
  • Polymer blends were prepared using different ratios of a partially crystalline ethylene copolymer, amorphous ethylene copolymer and star isoprenes, SHELLVIS 250 or SHELLVIS 200. The components used and their properties are listed in Table I.
  • Polymer A is a blend consisting of 40 wt% of partially crystalline ethylene-propylene-diene terpolymer containing approximately 77-80 mole % ethylene, about 0.1- 1.0 weight percent diene monomer, with the balance being propylene, and 60 wt% of amorphous ethylene-propylene diene terpolymer containing 56-62 mole % ethylene, about 0.1-0.5 weight percent diene monomer and the balance propylene.
  • Polvmer B is a commercial polymer, SHELLVIS 250, having a star branch structure with polyisoprene branches attached to a central core.
  • Polvmer C is a commercial polymer, SHELLVIS 200, having a star branch structure with polyisoprene branches attached to a central core. The molecular weight of this polymer is lower than that of Polvmer B.
  • Polymer D is a partially crystalline ethylene- propylene-diene terpolymer containing approximately 77-80 mole % ethylene, about 0.1-1.0 weight percent diene monomer, and the balance propylene.
  • Polymer E is an amorphous ethylene-propylene- diene terpolymer containing 56-62 mole % ethylene, about 0.1-1.0 weight percent piece monomer, and the balance propylene.
  • Polymer F is a blend consisting of 20 wt% of partially crystalline ethylene-propylene-diene terpolymer containing approximately 77-80 mole % ethylene, about 0.1- 1.0 weight percent diene monomer, and the balance propylene, and of 80 wt% dispersant amorphous ethylene- propylene-diene terpolymer containing 56-62 mole % ethylene, and about 2 wt% of pendant units derivatized from N-vinylpyrrolidone.
  • a number average molecular weight as measured by GPC is approximately 70,000, a molecular weight distributions of approximately 2.01, and a crystallinity of about 3%.
  • Polvmer G is a dispersant amorphous ethylene- propylene-diene terpolymer containing 56-62 mole % ethylene, about 0.1-1.0 weight percent diene monomer, and about 2 wt% of pendant units derivatized from N- vinylpyrrolidone.
  • a number average molecular weight as measured by GPC is approximately 70,000, a molecular weight distribution of approximately 2.1.
  • Polymer H is a dispersant/antioxidant amorphous ethylene-propylene copolymer containing 56-62 mole % ethylene, and about 1 wt% of pendant units derivatized from maleic anhydride and N-phenyl-p-phenylenediamine.
  • Polymer blends were prepared using different ratios of a partially crystalline ethylene copolymer blend, designated Polvmer A, and of star polymer (SHELLVIS 250) designated Polymer B. The resulting blends were tested for dimensional stability in the Dimensional Stability Test and for shear stability in the Shear Stability test. The results were compared to the individual polymers: Polymer A and Polvmer B (Table II)
  • Polymer blends were prepared using different ratios of a partially crystalline ethylene copolymer blend, designated Polymer A, and of star polymer (SHELLVIS 200) designated Polymer C. The resulting blends were tested for dimensional stability in the Dimensional Stability Test and shear stability in the Shear Stability test. The results were compared to the individual polymers: Polymer A and Polymer C (Table III)
  • Polymer blends were prepared using 60 wt% of a partially crystalline ethylene copolymer, designated Polymer D, and 40 wt% of star polymer (SHELLVIS 250) designated Polymer B. The resulting blends were tested for dimensional stability in the Dimensional Stability Test. The Shear Stability Index was calculated from the blend components. The results were compared to the individual polymers: Polymer D and Polymer B (Table IV) Tftble IV, SAMPLES OF EXAMPLE III
  • Polymer blends were prepared using 60 wt% of a amorphous OCP designated Polymer E, and 40 wt% of star polymer (SHELLVIS 250) designated Polymer B. The resulting blends were tested for dimensional stability in the Dimensional Stability Test. The Shear Stability Index was calculated from the blend components. The results were compared to the individual polymers: Polymer E and Polymer B (Table V)
  • Polymer blends were prepared using 80 and 90 wt% of a dispersant crystalline OCP blend, designated Polymer F, and the balance of star polymer (SHELLVIS 250) designated Polymer B. The resulting blends were tested for dimensional stability in the Dimensional Stability Test. The shear stability was calculated from the blend components. The results were compared to the individual polymers: Polymer F and Polymer B (Table VI) Table VI. SAMPLES OF EXAMPLE V
  • Polymer blends were prepared using 80 wt% of a dispersant amorphous OCP, designated Polymer G, and 20 wt% of star polymer (SHELLVIS 250) designated Polymer B. The resulting blends were tested for dimensional stability in the Dimensional Stability Test. The shear stability was calculated from the blend components. The results were compared to the individual polymers: Polymer G and Polymer B (Table VII)
  • Polymer blends were prepared using 80 wt% of a dispersant/antioxidant amorphous OCP, designated Polymer H, and 20 wt% of star polymer (SHELLVIS 250) designated Polymer B. The resulting blends were tested for dimensional stability in the Dimensional Stability Test. The shear stability was calculated from the blend components. The results were compared to the individual polymers: Polymer H and Polymer B (Table VIII) Table VIII. SAMPLES OF EXAMPLE VII
  • the blends containing star polyisoprene give products with significantly better pour points and Brookfield Viscosities.
  • the appearance during the extended cold storage is satisfactory for both neat VI improvers and fully formulated oils containing them.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Lubricants (AREA)

Abstract

Cette invention concerne de nouveaux mélanges polymères utilisés comme additifs et qui améliorent l'indice de viscosité d'huiles de lubrification. En particulier, les compositions additives polymères comprennent des copolymères d'oléfines partiellement cristallins (CPO) tels que EPM (copolymère d'éthylène-propylène) ou EPDM (terpolymère éthylène-propylène diène) et de polymères de styrène isoprène en étoile et des copolymères d'oléfine amorphes tels que EPM ou EPDM et des polymères à base de styrène/isoprène en étoile ou des copolymères d'oléfine cristallins et amorphes avec des polymères à base de styrène/isoprène en étoile. Les compositions additives de l'invention sont particulièrement utiles pour la préparation de polymères solides ayant une excellente stabilité dimensionnelle. Ces mélanges polymères, lorsqu'ils sont dissous dans des huiles minérales, comprennent des additifs lubrifiants qui améliorent l'indice de viscosité et les propriétés à basse température des compositions d'huile lubrifiante. Des mélanges d'EPM ou EPDM cristallins et amorphes avec des groupes fonctionnels polaires rattachés et des polymères en étoile sont également utiles en tant qu'additif. Ces produits ont des propriétés de performances multifonctionnelles et sont considérés comme des copolymères d'oléfines dispersants ou dispersants/antioxydants.
PCT/US1995/015707 1994-12-02 1995-12-04 Melanges polymeres contenant des copolymeres d'olefines et des polymeres ramifies en etoile WO1996017041A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
AU45072/96A AU4507296A (en) 1994-12-02 1995-12-04 Polymer blends containing olefin copolymers and star branched polymers
EP95943653A EP0794995A1 (fr) 1994-12-02 1995-12-04 Melanges polymeres contenant des copolymeres d'olefines et des polymeres ramifies en etoile

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US34845594A 1994-12-02 1994-12-02
US08/348,455 1994-12-02

Publications (1)

Publication Number Publication Date
WO1996017041A1 true WO1996017041A1 (fr) 1996-06-06

Family

ID=23368123

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1995/015707 WO1996017041A1 (fr) 1994-12-02 1995-12-04 Melanges polymeres contenant des copolymeres d'olefines et des polymeres ramifies en etoile

Country Status (3)

Country Link
EP (1) EP0794995A1 (fr)
AU (1) AU4507296A (fr)
WO (1) WO1996017041A1 (fr)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002010276A3 (en) * 2000-07-31 2002-04-25 Lubrizol Corp Polymeric mixture useful as viscosity improver for lubricating oils
EP1632504A3 (fr) * 2004-08-27 2006-06-07 Polimeri Europa S.p.A. Copolymères à base d'éthylène et propylène ayant une stabilité de forme améliorée et utilisables pour modifier des huiles lubrifiantes et procédé de préparation de ceux-ci
WO2007093446A1 (fr) * 2006-02-16 2007-08-23 Polimeri Europa S.P.A. Copolymères éthylène-propylène adaptés à la modification d'huiles lubrifiantes et procédé de synthèse desdits copolymères
EP1925657A3 (fr) * 2006-10-10 2010-03-31 Infineum International Limited Compositions d'huile lubrifiante
US7776804B2 (en) 2005-03-16 2010-08-17 The Lubrizol Corporation Viscosity improver compositions providing improved low temperature characteristics to lubricating oil
WO2011029580A1 (fr) 2009-09-08 2011-03-17 Unilever Plc Utilisation de copolymères ramifiés dans des mélanges de polymères
US8188021B2 (en) 2005-11-04 2012-05-29 Infineum International Limited Lubricating oil compositions
CN105273816A (zh) * 2015-10-16 2016-01-27 大连创达技术交易市场有限公司 一种具有抗高温蒸发的合成发动机润滑油

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1337475A (en) * 1970-06-02 1973-11-14 Exxon Research Engineering Co Lubricant containing ethylene/alphaolefin copolymers
FR2391268A2 (fr) * 1977-05-19 1978-12-15 Orobis Ltd Composition a base d'un copolymere sequence et d'un autre copolymere, destinee a ameliorer l'indice de viscosite d'une huile lubrifiante, et composition lubrifiante formulee comportant cet additif
US4833194A (en) * 1987-11-13 1989-05-23 R.J.F. International Corporation Elastomeric thermoplastic compositions
EP0452813A2 (fr) * 1990-04-12 1991-10-23 UNION CARBIDE CHEMICALS AND PLASTICS COMPANY INC. (a New York corporation) Procédé pour le moulage à froid de copolymères de propylène
EP0555930A2 (fr) * 1992-02-13 1993-08-18 Shell Internationale Researchmaatschappij B.V. Formulations de revêtement de sol et de mur

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1337475A (en) * 1970-06-02 1973-11-14 Exxon Research Engineering Co Lubricant containing ethylene/alphaolefin copolymers
FR2391268A2 (fr) * 1977-05-19 1978-12-15 Orobis Ltd Composition a base d'un copolymere sequence et d'un autre copolymere, destinee a ameliorer l'indice de viscosite d'une huile lubrifiante, et composition lubrifiante formulee comportant cet additif
US4833194A (en) * 1987-11-13 1989-05-23 R.J.F. International Corporation Elastomeric thermoplastic compositions
EP0452813A2 (fr) * 1990-04-12 1991-10-23 UNION CARBIDE CHEMICALS AND PLASTICS COMPANY INC. (a New York corporation) Procédé pour le moulage à froid de copolymères de propylène
EP0555930A2 (fr) * 1992-02-13 1993-08-18 Shell Internationale Researchmaatschappij B.V. Formulations de revêtement de sol et de mur

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002010276A3 (en) * 2000-07-31 2002-04-25 Lubrizol Corp Polymeric mixture useful as viscosity improver for lubricating oils
US8524645B2 (en) 2003-03-28 2013-09-03 The Lubrizol Corporation Viscosity improver compositions providing improved low temperature characteristics to lubricating oil
EP1632504A3 (fr) * 2004-08-27 2006-06-07 Polimeri Europa S.p.A. Copolymères à base d'éthylène et propylène ayant une stabilité de forme améliorée et utilisables pour modifier des huiles lubrifiantes et procédé de préparation de ceux-ci
US7208543B2 (en) 2004-08-27 2007-04-24 Polimeri Europa S.P.A. Ethylene-propylene copolymers with an improved shape stability suitable for modifying lubricating oils and process for the preparation thereof
US7776804B2 (en) 2005-03-16 2010-08-17 The Lubrizol Corporation Viscosity improver compositions providing improved low temperature characteristics to lubricating oil
US8188021B2 (en) 2005-11-04 2012-05-29 Infineum International Limited Lubricating oil compositions
WO2007093446A1 (fr) * 2006-02-16 2007-08-23 Polimeri Europa S.P.A. Copolymères éthylène-propylène adaptés à la modification d'huiles lubrifiantes et procédé de synthèse desdits copolymères
RU2430962C2 (ru) * 2006-02-16 2011-10-10 Полимери Эуропа С.П.А. Сополимеры этилена и пропилена, пригодные для модифицирования смазочных масел, и способ их получения
US8193135B2 (en) 2006-02-16 2012-06-05 Polimeri Europa S.P.A. Ethylene-propylene copolymers suitable for the modification of lubricating oils and process for the preparation thereof
EP1925657A3 (fr) * 2006-10-10 2010-03-31 Infineum International Limited Compositions d'huile lubrifiante
WO2011029580A1 (fr) 2009-09-08 2011-03-17 Unilever Plc Utilisation de copolymères ramifiés dans des mélanges de polymères
CN105273816A (zh) * 2015-10-16 2016-01-27 大连创达技术交易市场有限公司 一种具有抗高温蒸发的合成发动机润滑油

Also Published As

Publication number Publication date
AU4507296A (en) 1996-06-19
EP0794995A1 (fr) 1997-09-17

Similar Documents

Publication Publication Date Title
US5070131A (en) Gear oil viscosity index improvers
EP0498549B1 (fr) Polyoléfines abaissant le point d'écoulement
CA1255029A (fr) Produit pouvant servir d'additif pour huile lubrifiante, sa preparation et huile qui le renferme
CA2127918A1 (fr) Melange de polymere solide de taille fixe et composition d'huile lubrifiante en contenant
US3630905A (en) Oil-extended vi improvers
JPH0586114A (ja) 粘度指数向上剤
EP0700942B1 (fr) Polymère en étoile en tant qu'agent améliorant l'indice de viscosité pour compositions des huiles lubrifiantes
US4970009A (en) Modified VI improvers
EP0344836B1 (fr) Agent améliorant l'indice de viscosité et composition contenant celui-ci
WO1996017041A1 (fr) Melanges polymeres contenant des copolymeres d'olefines et des polymeres ramifies en etoile
USH1799H (en) Star polymer viscosity index improver for oil compositions
EP0425027B1 (fr) Polymère en étaile, sa préparation et les compositions lubrifiantes contenant celui-ci
KR20170068392A (ko) 점도 지수 개선제 농축물
EP0711790A2 (fr) Additif dispersant améliorant l'indice de viscosité pour huiles lubrifiantes
EP0497411B1 (fr) Polymère améliorant l'indice de viscosité
EP0498489B1 (fr) Compositions d'huile contenant des polymères fonctionnalisés
US4081390A (en) Viscosity index improver composition
EP0647703B1 (fr) Compositions de polymères à compatibilité améliorée dans une huile
JPH04218568A (ja) ポリマー変性ビチューメンおよびその製造方法
EP0458415B1 (fr) Compositions d'huile contenant des polymères fonctionnalisés
JPH02263848A (ja) スルホン化コポリマー及びターポリマー組成物

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AL AM AT AU BB BG BR BY CA CH CN CZ DE DK EE ES FI GB GE HU IS JP KE KG KP KR KZ LK LR LS LT LU LV MD MG MK MN MW MX NO NZ PL PT RO RU SD SE SG SI SK TJ TM TT UA UG US UZ VN

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): KE LS MW SD SZ UG AT BE CH DE DK ES FR GB GR IE IT LU MC NL PT SE BF BJ CF CG CI CM GA GN ML MR NE SN TD TG

CFP Corrected version of a pamphlet front page
CR1 Correction of entry in section i
WD Withdrawal of designations after international publication

Free format text: US

DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
121 Ep: the epo has been informed by wipo that ep was designated in this application
WWE Wipo information: entry into national phase

Ref document number: 1995943653

Country of ref document: EP

WWP Wipo information: published in national office

Ref document number: 1995943653

Country of ref document: EP

REG Reference to national code

Ref country code: DE

Ref legal event code: 8642

WWW Wipo information: withdrawn in national office

Ref document number: 1995943653

Country of ref document: EP