USH1799H - Star polymer viscosity index improver for oil compositions - Google Patents
Star polymer viscosity index improver for oil compositions Download PDFInfo
- Publication number
- USH1799H USH1799H US08/164,733 US16473393A USH1799H US H1799 H USH1799 H US H1799H US 16473393 A US16473393 A US 16473393A US H1799 H USH1799 H US H1799H
- Authority
- US
- United States
- Prior art keywords
- polyisoprene
- star
- star polymer
- molecular weight
- polystyrene
- 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.)
- Abandoned
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- 229920000642 polymer Polymers 0.000 title claims abstract description 84
- 239000000203 mixture Substances 0.000 title claims abstract description 26
- 229920001195 polyisoprene Polymers 0.000 claims abstract description 32
- 239000004793 Polystyrene Substances 0.000 claims abstract description 30
- 229920002223 polystyrene Polymers 0.000 claims abstract description 30
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 30
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims description 29
- 229920001400 block copolymer Polymers 0.000 claims description 24
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 18
- 239000007822 coupling agent Substances 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 6
- 239000010707 multi-grade lubricating oil Substances 0.000 claims description 5
- 230000000379 polymerizing effect Effects 0.000 claims description 5
- 239000002199 base oil Substances 0.000 claims 3
- 238000002156 mixing Methods 0.000 claims 1
- 229920001577 copolymer Polymers 0.000 abstract description 2
- 239000003921 oil Substances 0.000 description 16
- 125000003118 aryl group Chemical group 0.000 description 14
- 239000010687 lubricating oil Substances 0.000 description 9
- 239000000155 melt Substances 0.000 description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 7
- WGOPGODQLGJZGL-UHFFFAOYSA-N lithium;butane Chemical compound [Li+].CC[CH-]C WGOPGODQLGJZGL-UHFFFAOYSA-N 0.000 description 7
- 238000005984 hydrogenation reaction Methods 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- 239000000654 additive Substances 0.000 description 5
- 238000005227 gel permeation chromatography Methods 0.000 description 5
- 238000005859 coupling reaction Methods 0.000 description 4
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- PERLSLNQWLZSLS-UHFFFAOYSA-N ethyl hexanoate;nickel Chemical compound [Ni].CCCCCC(=O)OCC PERLSLNQWLZSLS-UHFFFAOYSA-N 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 239000010705 motor oil Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 2
- ROGIWVXWXZRRMZ-UHFFFAOYSA-N 2-methylbuta-1,3-diene;styrene Chemical compound CC(=C)C=C.C=CC1=CC=CC=C1 ROGIWVXWXZRRMZ-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 239000010734 process oil Substances 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 238000001374 small-angle light scattering Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- 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
- 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
-
- 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
- C08F297/02—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 anionic type
-
- 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
- C08F297/02—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 anionic type
- C08F297/04—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 anionic type polymerising vinyl aromatic monomers and conjugated dienes
- C08F297/044—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 anionic type polymerising vinyl aromatic monomers and conjugated dienes using a coupling agent
-
- 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
- C08F297/02—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 anionic type
- C08F297/04—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 anionic type polymerising vinyl aromatic monomers and conjugated dienes
- C08F297/046—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 anionic type polymerising vinyl aromatic monomers and conjugated dienes polymerising vinyl aromatic monomers and isoprene, optionally with other conjugated dienes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
- C08G81/02—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers at least one of the polymers being obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C08G81/021—Block or graft polymers containing only sequences of polymers of C08C or C08F
-
- 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
- C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
- C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
- C10M2203/108—Residual fractions, e.g. bright stocks
-
- 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
- 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
- C10N2040/255—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
Definitions
- This invention relates to star polymers of hydrogenated isoprene and styrene, and to oil compositions containing the star polymers.
- oils are identified by a viscosity index which is a function of the oil viscosity at a given lower temperature and a given higher temperature.
- the given lower temperature and the given higher temperature have varied over the years but are fixed at any given time in an ASTM test procedure (ASTM D2270).
- ASTM test procedure ASTM D2270.
- the lower temperature specified in the test is 40° C. and the higher temperature specified in the test is 100° C.
- asymmetric star-shaped polymers are both solid polymers and effective VI improvers for lubricating oil compositions as disclosed in U.S. Pat. No. 4,849,481.
- the patent describes asymmetric star polymers of conjugated diolefin blocks, such as polyisoprene, and monoalkenyl aromatic blocks, such as polystyrene.
- the star polymers contain a substanial amount of the monoalkenyl aromatic blocks and produce oil compositions having reduced high temperature, high shear rate (HTHSR) viscosities.
- HTHSR high temperature, high shear rate
- the asymmetric star polymers have sufficient amounts of the monoalkenyl aromatic blocks to be cyclone finishable as a polymer crumb.
- HTHSR viscosities Although reduced HTHSR viscosities likely indicate good fuel efficiency, increased HTHSR viscosities are needed for high performance engines which operate at higher temperatures and rpms, or for engines having marginally designed journal bearings. Minimum HTHSR viscosities have been proposed as an industry standard. Star polymers having a sufficiently low amount of the monoalkenyl aromatic blocks to have a high HTHSR viscosity were expected to not have a sufficient amount of the monoalkenyl aromatic blocks to be cyclone finishable as a polymer crumb or were expected to cause gelation.
- FIG. 1 of the patent does suggest that oil compositions such as multigrade SAE 10W-40 (graded according to the SAE J300 standard of the SAE Engine Oil Viscosity Classification System) can be produced with the asymmetric star polymers having a low monoalkenyl aromatic block content.
- the patent does not suggest that the star polymers having low amounts of the monoalkenyl aromatic blocks would be both cyclone finishable and useful in preparing oil compositions having higher HTHSR viscosities.
- the present invention includes star polymers which can be used as viscosity index improvers in oil compositions formulated for high performance engines.
- the star polymers have specific block copolymer arms of hydrogenated polyisoprene and polystyrene.
- the star polymers contain a sufficient amount of hydrogenated polyisoprene for good viscosity index improving properties and a sufficient amount of polystyrene to be cyclone finishable as a polymer crumb.
- the star polymer viscosity index (VI) improvers of the present invention are produced by coupling living block copolymer molecules having specific structures.
- the living molecules consist essentially of a polystyrene block connected to a living block of polyisoprene, wherein the polyisoprene block has a number average molecular weight (MW I ) between 30,000 and 70,000 and the styrene block has a number average molecular weight (MW S ) from 4,000-MW I /30 to 3,000+MW I /30.
- the living polymer molecules are coupled with a polyalkenyl coupling agent such as divinylbenzene wherein the ratio of moles of divinylbenzene to living polymer molecules is at least 2.5:1.
- the star polymer is then selectively hydrogenated to saturate at least 95% by weight of the isoprene units and less than 15% by weight of the styrene units.
- star polymers of the present invention are readily produced by the processes described in Canadian Patent No. 716,645 and U.S. Pat. No. Re 27,145 which process descriptions are incorporated by reference herein. However, the star polymers of the present invention have molecular weights not taught by the references.
- each polyisoprene block When the number average molecular weight of each polyisoprene block is at least about 75,000, the star polymers are cyclone finishable as a solid crumb in the absence of blocks of polystyrene. However, the longer hydrogenated polyisoprene blocks are prone to shearing when used as a VI improver. On the other hand, star polymers having polyisoprene blocks with number average molecular weights less than 30,000 may require excessively large polystyrene blocks to be cyclone finishable and do not provide a suitable low temperature oil viscosity. All number average molecular weights recited herein are determined from a conventional gel permeation chromatography (GPC) curve unless stated otherwise.
- GPC gel permeation chromatography
- the present invention includes the suprising discovery that cylcone finishable star polymers having high HTHSR viscosities and good low temperature performance can be prepared by limiting the size of the polystyrene blocks.
- the star polymers of this invention which are useful as VI improvers are prepared by anionically polymerizing polystyrene in the presence of sec-butyllithium, adding isoprene to the living polystyrene molecules to making living block copolymer molecules, coupling the living block copolymer molecules with a polyalkenyl coupling agent to form a star polymer, and selectively hydrogenating the polyisoprene blocks.
- the star polymers of the present invention may be characterized prior to hydrogenation as having a dense center or nucleus of crosslinked poly(polyalkenyl coupling agent) and a number of block copolymer arms extending outwardly therefrom.
- the number of arms may vary considerably but typically range from about 6 to about 13.
- the actual number of arms is unknown since GPC-Low Angle Laser Light Scattering indicates a substantially greater number of arms than conventional GPC techniques.
- the star-shaped polymers of this invention may be represented by the general formula (A-B) n -X wherein A-B is a block copolymer comprising a single block A of polystyrene and a single block B of hydrogenated polyisoprene, n is the number of block copolymer arms in the star polymer, and X is the poly(polyalkenyl coupling agent) nucleus.
- the star polymers may be hydrogenated using any of the techniques known in the prior art to be suitable for selective hydrogenation of olefinic unsaturation over aromatic unsaturation.
- the hydrogenation conditions must be sufficient to hydrogenate at least 95% of the original olefinic unsaturation.
- Hydrogenation of aromatic unsaturation must be less than 15% to avoid reduction of the amount of polystyrene needed to finish the star polymers.
- hydrogenation involves the use of a suitable catalyst as described in U.S. Pat. No. Re 27,145 which is herein incorporated by reference.
- a mixture of nickel ethylhexanoate and triethylaluminum having from 2 to 3 moles of aluminum per mole of nickel is preferred.
- the hydrogenated star polymers of this invention may be added to a variety of lubricating oils to improve viscosity index characteristics.
- the selectively hydrogenated star polymers may be added to fuel oils such as middle distillate fuels, synthetic and natural lubricating oils, crude oils and industrial oils.
- any amount of the selectively hydrogenated star polymers may be blended into the oils, with amounts from about 0.05 to about 10 wt % being most common. Amounts within the range from about 0.5 to about 2.5 wt % are preferred.
- Lubricating oil compositions prepared with the selectively hydrogenated star polymers of this invention may also contain other additives such as anti-corrosive additives, antioxidants, detergents, pour point depressants, one or more additional VI improvers and the like.
- additives which are useful in the lubricating oil composition of this invention and their description will be found in U.S. Pat. Nos. 3,772,196 and 3,835,083, the disclosure of which patents are herein incorporated by reference.
- a star polymer is produced by anionically polymerizing styrene and then isoprene to produce living polystyrene-polyisoprene-Li molecules.
- the polyisoprene blocks preferably have a number average molecular weight between 30,000 and 60,000 and the polystyrene blocks preferably have a number average molecular weight from 3,000 to 4,000.
- the living block copolymer molecules are coupled with divinylbenzene using 3 moles of divinylbenzene per mole of copolymer molecules.
- the coupled polymers are selectively hydrogenated with a solution of nickel ethylhexanoate and triethylaluminum having a Al/Ni ratio of about 2.5:1 to saturate at least 98% of the isoprene units and less than 10% of the styrene units.
- Such star polymers are cyclone finishable as a polymer crumb and produce oil compositions having a good balance of high and low temperature viscosities suitable for high performance engines.
- a star polymer consisting essentially of arms of a block copolymer containing a single block of polystyrene and a single block of hydrogenated polyisoprene was prepared.
- living molecules of polystyrene were prepared by anionically polymerizing styrene in cyclohexene.
- the polymerization of styrene was initiated by adding sec-butyllithium.
- the polymerization of the styrene was completed to produce living polystyrene molecules having a number average molecular weight of 3,100.
- Polyisoprene blocks were then formed by adding isoprene to the solution of living polystyrene molecules.
- the polymerization of isoprene was completed to produce polyisoprene blocks having a number average molecular weight of 53,400.
- the living block copolymer arms were then coupled with divinylbenzene using 3 moles of divinylbenzene per mole of the living block copolymer molecules.
- the coupling reaction was allowed to proceed to completion after which the lithium sites remaining in the star polymer were deactivated by adding an alcohol.
- the star polymer was next hydrogenated so as to saturate greater than 98% of the olefinic unsaturation originally contained in the isoprene blocks and less than 15% of the aromatic unsaturation using a catalyst prepared by combining nickel ethylhexanoate and triethylaluminum (2.3 moles of aluminum per mole of nickel).
- the melt viscosity of the star polymer was sufficiently high to permit finishing as a solid polymer crumb.
- the melt viscosity of the star polymer was 38.2 megapoise at 250° F. The data and results are summarized in Table 1.
- a star polymer consisting essentially of arms of a styrene/isoprene block copolymer was prepared using the procedure summarized in Example 1 except that the number average molecular weight of the polystyrene blocks was 3,720 and the number average molecular weight of the polyisoprene blocks was 46,300.
- the melt viscosity of the star polymer was 36.2 megapoise at 250° F. The data and results are summarized in Table 1.
- a star polymer consisting essentially of arms of a styrene/isoprene block copolymer was prepared using the procedure summarized in Example 1 except that the number average molecular weight of the polystyrene blocks was 4,610 and the number average molecular weight of the polyisoprene blocks was 51,200.
- the melt viscosity of the star polymer was 48.5 megapoise at 250° F. The data and results are summarized in Table 1.
- a star polymer consisting essentially of arms of a styrene/isoprene block copolymer was prepared using the procedure summarized in Example 1 except that the number average molecular weight of the polystyrene blocks was 2,200 and the number average molecular weight of the polyisoprene blocks was 41,500.
- the melt viscosity of the star polymer was 5.0 megapoise at 250° F. The data and results are summarized in Table 1.
- a star polymer consisting essentially of arms of a styrene/isoprene block copolymer was prepared using the procedure summarized in Example 1 except that the number average molecular weight of the polystyrene blocks was 2,200 and the number average molecular weight of the polyisoprene blocks was 48,100.
- the melt viscosity of the star polymer was 12.3 megapoise at 250° F. The data and results are summarized in Table 1.
- a star polymer consisting essentially of arms of a styrene/isoprene block copolymer was prepared using the procedure summarized in Example 1 except that the number average molecular weight of the polystyrene blocks was 5,750 and the number average molecular weight of the polyisoprene blocks was 54,000.
- the melt viscosity of the star polymer was 69.4 megapoise at 250° F. The data and results are summarized in Table 1.
- a hydrogenated asymmetric star polymer comprising arms of a block copolymer containing a single block of polystyrene and a single block of hydrogenated polyisoprene and arms of hydrogenated polyisoprene was prepared.
- living molecules of polystyrene were prepared by anionically polymerizing styrene in cyclohexene.
- the polymerization of the styrene was initiated by adding sec-butyllithium.
- the polymerization of the styrene was completed to produce living polystyrene molecules having a number average molecular weight of 7,800.
- Polyisoprene blocks and living polyisoprene molecules were then formed by adding additional sec-butyllithium and isoprene to the solution of living polystyrene molecules.
- the ratio of the second amount of sec-butyllithium to the first amount of sec-butyllithium was about 11:5.
- the polymerization of isoprene was then completed to produce polyisoprene blocks and living polyisoprene molecules having a number average molecular weight of 46,400.
- the indicated ratio of sec-butyllithium prepares a mixture of about 30% living block copolymer molecules and 70% living polyisoprene molecules.
- the living polymer molecules were then coupled with divinylbenzene using 3 moles of divinylbenzene per mole of the polymer molecules.
- the coupling reaction was allowed to proceed to completion after which the lithium sites remaining in the star polymer were deactivated by adding methanol.
- the star polymer was next hydrogenated so as to saturate greater than 98% of the olefinic unsaturation originally contained in the polyisoprene and less than 15% of the aromatic unsaturation using the catalyst of Example 1 (2.8:1 Al/Ni).
- the ratio of block copolymer arms to homopolymer arms is believed to be the same as the ratio of these components in the initial blend of block copolymer molecules and homopolymer molecules used to prepare the star-shaped polymer; i.e. 5 to 11 or about 30% block copolymer arms.
- the melt viscosity of the asymmetric star polymer was 35.0 megapoise at 250° F. The data and results are summarized in Table 1.
- the star polymers produced in Examples 1-3 were used as VI improvers in a SAE 10W-40 multigrade lubricating oil composition.
- the base stock used in the preparation of the multigrade lubricating oil composition was a blend of an HVI 10ON oil and an HVI 250N oil.
- the amount of each VI improver was varied so as to provide a lubricating oil composition having a kinematic viscosity of 14 centistokes (cst) at 100° C.
- the multigrade lubricating oil compositions prepared in these examples contained 31.0% by weight of HVI 250N (DP), 7.75 wt % of a commercially available additive package (Lubrizol 7573A), and 0.3 wt % Acryloid 160.
- the viscosity index (VI), the cold cranking simulator (CCS) viscosity at -20° C., the engine oil pumpability (TP1) at -25° C. using the mini-rotary viscometer (ASTM D4684), and the high temperature high shear rate (HTHSR) viscosity at 150° C. at 1 ⁇ 10 6 seconds -1 using the tapered bearing simulator (TBS) (ASTM D4683) were determined for each lubricating oil composition.
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Inorganic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Lubricants (AREA)
- Graft Or Block Polymers (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US08/164,733 USH1799H (en) | 1991-11-08 | 1993-12-07 | Star polymer viscosity index improver for oil compositions |
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US79061091A | 1991-11-08 | 1991-11-08 | |
US8385793A | 1993-06-25 | 1993-06-25 | |
US08/164,733 USH1799H (en) | 1991-11-08 | 1993-12-07 | Star polymer viscosity index improver for oil compositions |
Related Parent Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US8385793A Division | 1991-11-08 | 1993-06-25 |
Publications (1)
Publication Number | Publication Date |
---|---|
USH1799H true USH1799H (en) | 1999-08-03 |
Family
ID=25151229
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US08/164,733 Abandoned USH1799H (en) | 1991-11-08 | 1993-12-07 | Star polymer viscosity index improver for oil compositions |
Country Status (7)
Country | Link |
---|---|
US (1) | USH1799H (pt) |
EP (1) | EP0541180A3 (pt) |
JP (1) | JPH05222114A (pt) |
KR (1) | KR930010066A (pt) |
AU (1) | AU656434B2 (pt) |
BR (1) | BR9204322A (pt) |
CA (1) | CA2082331A1 (pt) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6034042A (en) * | 1998-02-19 | 2000-03-07 | Shell Oil Company | Star polymer viscosity index improver for oil compositions |
CN112708085A (zh) * | 2019-10-24 | 2021-04-27 | 中国石油化工股份有限公司 | 氢化异戊二烯/苯乙烯嵌段偶合聚合物光缆油膏胶凝剂及其制备方法和在光缆油膏中的应用 |
Families Citing this family (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
TW274086B (pt) * | 1992-06-04 | 1996-04-11 | Shell Internat Res Schappej Bv | |
US5458796A (en) * | 1994-03-31 | 1995-10-17 | Shell Oil Company | Synthesis of polyisobutylene star-branched polymers via living carbocationic polymerization |
CA2342788C (en) * | 1998-08-20 | 2008-10-14 | Kaneka Corporation | Resin composition, polymer and process for producing polymer |
AU7446200A (en) * | 1999-09-28 | 2001-04-30 | Bayer Aktiengesellschaft | Optical material comprising star-shaped hydrogenated polystyrene block copolymer, process for producing the same, and substrate for optical disk |
US20030170564A1 (en) * | 2000-04-26 | 2003-09-11 | Nobuaki Kido | Optical recording medium and substrate for use therein |
US7001956B2 (en) | 2002-06-04 | 2006-02-21 | Kraton Polymers U.S. Llc | Articles prepared from hydrogenated block copolymers |
EA007296B1 (ru) | 2002-06-04 | 2006-08-25 | Кратон Полимерз Рисёч Б.В. | Композиция, содержащая сопряженный блок-сополимер, и способ ее получения |
KR100807917B1 (ko) * | 2004-03-03 | 2008-02-27 | 크레이튼 폴리머즈 리서치 비.브이. | 높은 유동성의 블록공중합체를 함유하는 엘라스토머성이성분섬유 |
US8999905B2 (en) | 2010-10-25 | 2015-04-07 | Afton Chemical Corporation | Lubricant additive |
CN110499206B (zh) * | 2019-08-14 | 2020-10-16 | 深圳昆油石化技术有限公司 | 含有星型sep共聚物润滑油粘度指数改性剂及其制备方法 |
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US4849481A (en) * | 1987-07-10 | 1989-07-18 | Shell Oil Company | Star shaped asymmetric block copolymer of monoalkenyl aromatic hydrocarbon and conjugated diene |
US5070131A (en) * | 1990-09-28 | 1991-12-03 | Shell Oil Company | Gear oil viscosity index improvers |
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US4391949A (en) * | 1981-11-12 | 1983-07-05 | Shell Oil Company | Asymmetric block copolymers and corresponding adhesive formulations |
US4900875A (en) * | 1987-07-10 | 1990-02-13 | Shell Oil Company | Polymeric viscosity index additive and oil composition comprising the same |
US4788361A (en) * | 1987-10-30 | 1988-11-29 | Shell Oil Company | Polymeric viscosity index improver and oil composition comprising the same |
-
1992
- 1992-11-05 EP EP19920203401 patent/EP0541180A3/en not_active Withdrawn
- 1992-11-05 KR KR1019920020678A patent/KR930010066A/ko not_active Application Discontinuation
- 1992-11-06 AU AU28201/92A patent/AU656434B2/en not_active Ceased
- 1992-11-06 JP JP4297155A patent/JPH05222114A/ja active Pending
- 1992-11-06 BR BR929204322A patent/BR9204322A/pt not_active Application Discontinuation
- 1992-11-06 CA CA002082331A patent/CA2082331A1/en not_active Abandoned
-
1993
- 1993-12-07 US US08/164,733 patent/USH1799H/en not_active Abandoned
Patent Citations (10)
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US27145A (en) * | 1860-02-14 | Mortising-machine | ||
CA716645A (en) * | 1965-08-24 | Shell Oil Company | Block polymers and process for preparing them | |
USRE27145E (en) | 1969-05-20 | 1971-06-22 | Side-chain | |
US3985830A (en) * | 1974-07-15 | 1976-10-12 | The University Of Akron | Star polymers and process for the preparation thereof |
US3985830B1 (en) * | 1974-07-15 | 1998-03-03 | Univ Akron | Star polymers and process for the preparation thereof |
US4116917A (en) * | 1976-02-10 | 1978-09-26 | Shell Oil Company | Hydrogenated star-shaped polymer |
US4156673A (en) * | 1976-02-10 | 1979-05-29 | Shell Oil Company | Hydrogenated star-shaped polymer |
US4780367A (en) * | 1983-06-27 | 1988-10-25 | Minnesota Mining And Manufacturing Company | Tackified star block copolymer pressure-sensitive adhesive composition and the sheet materials coated therewith |
US4849481A (en) * | 1987-07-10 | 1989-07-18 | Shell Oil Company | Star shaped asymmetric block copolymer of monoalkenyl aromatic hydrocarbon and conjugated diene |
US5070131A (en) * | 1990-09-28 | 1991-12-03 | Shell Oil Company | Gear oil viscosity index improvers |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6034042A (en) * | 1998-02-19 | 2000-03-07 | Shell Oil Company | Star polymer viscosity index improver for oil compositions |
CN112708085A (zh) * | 2019-10-24 | 2021-04-27 | 中国石油化工股份有限公司 | 氢化异戊二烯/苯乙烯嵌段偶合聚合物光缆油膏胶凝剂及其制备方法和在光缆油膏中的应用 |
Also Published As
Publication number | Publication date |
---|---|
BR9204322A (pt) | 1993-05-11 |
CA2082331A1 (en) | 1993-05-09 |
AU2820192A (en) | 1993-05-13 |
AU656434B2 (en) | 1995-02-02 |
EP0541180A3 (en) | 1993-11-18 |
EP0541180A2 (en) | 1993-05-12 |
JPH05222114A (ja) | 1993-08-31 |
KR930010066A (ko) | 1993-06-22 |
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Legal Events
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Owner name: SHELL OIL COMPANY, TEXAS Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:RHODES, ROBERT B.;ATWOOD, HARVEY E.;GORMAN, JOHN E.;REEL/FRAME:009552/0148;SIGNING DATES FROM 19911218 TO 19911219 |
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STCF | Information on status: patent grant |
Free format text: PATENTED CASE |