Source: http://www.google.com/patents/US5856524?ie=ISO-8859-1
Timestamp: 2014-10-01 07:10:44
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Patent US5856524 - Oil and fuel additive; modificed polyolefin - Google PatentsSearch Images Maps Play YouTube News Gmail Drive More »Sign in<nobr>Advanced Patent Search</nobr>PatentsA process for preparing compounds useful as intermediates used for preparing lubricant and fuel additives. The intermediates include the products prepared by the process and dilactones....http://www.google.com/patents/US5856524?utm_source=gb-gplus-sharePatent US5856524 - Oil and fuel additive; modificed polyolefinAdvanced Patent SearchPublication numberUS5856524 APublication typeGrantApplication numberUS 08/993,816Publication dateJan 5, 1999Filing dateDec 18, 1997Priority dateAug 22, 1995Fee statusLapsedAlso published asCA2183612A1, DE69611011D1, DE69611011T2, EP0759435A2, EP0759435A3, EP0759435B1, US5739356, US5786490Publication number08993816, 993816, US 5856524 A, US 5856524A, US-A-5856524, US5856524 A, US5856524AInventorsJeffery G. Dietz, Mark R. Baker, Paul E. AdamsOriginal AssigneeThe Lubrizol CorporationExport CitationBiBTeX, EndNote, RefManPatent Citations (14), Non-Patent Citations (16), Referenced by (15), Classifications (58), Legal Events (5) External Links: USPTO, USPTO Assignment, EspacenetOil and fuel additive; modificed polyolefinUS 5856524 AAbstract A process for preparing compounds useful as intermediates used for preparing lubricant and fuel additives. The intermediates include the products prepared by the process and dilactones.
What is claimed is: 1. A composition comprising compounds of the formula ##STR13## wherein n=0; y=0 or 1; wherein X is a divalent hydrocarbyl group selected from the group consisting of ##STR14## when y=0, and ##STR15## when y=1 wherein R1 is H or a hydrocarbon based group;each R3 is independently H or hydrocarbyl; each R4 is independently a divalent hydrocarbylene group; R5 is H or hydrocarbyl; each of R6, R7 and R8 is independently H or a hydrocarbon based group, and T is --OH. 2. The composition of claim 1 wherein each of R1 and R3 is independently H or a lower alkyl or alkenyl group.
The Catalyst The process of this invention is optionally conducted in the presence of an acidic catalyst. Acid catalysts, such as organic sulfonic acids, for example, paratoluene sulfonic acid and methane sulfonic acid, heteropolyacids, the complex acids of heavy metals (e.g., Mo, W, Sn, V, Zr, etc.) with phosphoric acids (e.g., phosphomolybdic acid), and mineral acids, for example, H2 SO4 and phosphoric acid, are useful. The amount of catalyst used is generally small, ranging from about 0.01 mole % to about 10 mole %, more often from about 0.1 mole % to about 2 mole %, based on moles of olefinic reactant.
The Compounds In another embodiment, this invention relates to a composition comprising regioisomers selected from the group consisting of compounds of the formula ##STR10## wherein y=0 or 1, n=0 or 1 and X is a divalent hydrocarbyl group selected from the group consisting of ##STR11## when y=0, and ##STR12## when y=1, and T is selected from the group consisting of --OH and R5. More often T is --OH.
EXAMPLE 1 A reactor is charged with 450 parts of polyisobutene having Mn about 1000 and 92 parts 50% aqueous glyoxylic acid. The materials are heated under N2 at 200� C. to 205� for 36 hours while collecting 35 parts distillate in a Dean-Stark trap. The materials are stripped to 180� C. at 2 nm Hg pressure for 1 hour, then are filtered at 150� C. with a diatomaceous earth filter aid. Infrared spectrum shows prominent C═O absorption. saponification No.=36. Total acid No.=5.5
EXAMPLE 2 A reactor is charged with 380 parts polyisobutene having Mn about 1000 and 75 parts glyoxylic acid monohydrate. The materials are heated under N2 at 200�-210� C. for 7 hours while collecting aqueous distillate in a Dean-Stark trap. The materials are filtered at 150�-160� C. with a diatomaceous earth filter aid.
EXAMPLE 3 A reactor is charged with 300 parts polyisobutene (CE5203, BASF) having a Mn about 1000 and containing about 49 mole % terminal vinylidene groups, 88.8 parts 50% aqueous glyoxylic acid and 1 part sulfuric acid and a few drops of silicone antifoam agent. Under N2, the materials are heated to 100� C. and held at 100� C. for 1 hour, then to 125� C. and held at 125� C. for 2 hours, then heated to 150� C. and maintained at 150� C. for 3 hours, collecting a total of 49 parts distillate in a Dean-Stark trap. The materials are filtered at 150� C. with a diatomaceous earth filter aid. Saponification No.+71.4; total acid no.=27, 7% unreacted polyisobutene determined by thin layer chromatography using a flame ionization detector (TLC-FID).
EXAMPLE 4 A reactor is charged with 1360 parts polyisobutene (Glissopal ES3250) having Mn about 1000 and containing about 87 mole percent terminal vinylidene groups, 250 parts glyoxylic acid monohydrate and 1.35 parts 70% aqueous methane sulfonic acid. The materials are heated under N2 for 4 hours at 155�-160� C. while collecting 82 parts aqueous distillate in a Dean-Stark trap. The materials are filtered at 155�-160� C. with a diatomaceous earth filter aid. Infra red spectrum: very strong lactone C═O at 1774 cm-1. Saponification No.+107; Total acid no+31.8, 9% unreacted polyisobutene (TLC-FID).
EXAMPLE 5 A reactor is charged with 500 parts of the polyisobutene of Example 3 and 148 parts 50% aqueous glyoxylic acid. The materials are heated to 150� and held at 150� for 3 hours while removing aqueous distillate. Unreacted polyisobutylene (TLC-FID)+29.2% The materials are mixed at 150� with 144 parts mineral oil diluent the solution is filtered employing a diatomaceous earth filter aid. Saponification No.=46; total acid No.=13.
EXAMPLE 6 To a reactor are charged 1000 parts of the polyisobutene of Example 4, 296 parts 50% aqueous glyoxylic acid and a few drops silicone antifoam agent. The mixture is heated to 160� and is held at 160� for 16 hours while removing aqueous distillate. The material contains by TLC-FID 22% unreacted polyisobutene. Diluent oil, 287 parts, is added, the materials are heated to 110� C. and filtered with a diatomaceous earth filter aid. Saponification No.=57, Total acid no.=11.5.
EXAMPLE 7 A reactor is charged with 300 parts polyisobutene (Glissopal ES 3252, BASF) having Mn about 2400 and containing about 70 mole percent terminal vinylidene groups and 35.8 parts 50% aqueous glyoxylic acid. The materials are heated to 160� C. and are held at 160� C. for 16 hours. Unreacted polyisobutene (TLC-FID)=24%. Mineral oil diluent, 84 parts, is added and the materials are mixed at 110� C. the filtered with a diatomaceous earth filter aid. Saponification No.=22.4,Total acid No.=6.9.
EXAMPLE 8 A reactor is charged with 500 parts of polyisobutene (Ultravis 10, BP Chemicals) having Mn about 1000 which is heated to 100� C., then 9 parts 70% aqueous methanesulfonic acid are added followed by dropwise addition of 148 parts 50% aqueous glyoxylic acid over 0.5 hour. The temperature is increased to 150� C. and the materials are held at 150� C. over 12 hours. TLC-FID analysis shows 10.6% unreacted polyisobutene. The materials are mixed with 144 parts mineral oil diluent and filtered with a diatomaceous earth filter aid. Saponification no.=44, total acid no.=17.5.
EXAMPLE 9 The procedure of Example 1 is repeated replacing the polyisobutylene with an equivalent amount, based on C═C, of C16-18 alpha olefin.
EXAMPLE 10 The procedure of Example 2 is repeated replacing the polyisobutylene with equivalent amounts (based on C═C) of C24-28 alpha olefin.
EXAMPLE 13 A reactor is charged with 3000 parts of polyisobutylene having a number average molecular weight of about 2400 (Glissopal ES 3252, BASF), 230.3 parts glyoxylic acid monohydrate, 17.5 parts 70% aqueous methane sulfonic acid and a few drops of a silicone antifoam agent. The materials are heated under N2 purge (0.3 cubic feet per hour) to 130� C. and then are heated at 130� C. for a total of 11 hours while collecting a total of 140 parts aqueous distillate. The materials are cooled to room temperature, 2093 parts mineral oil diluent are added and the solution is stirred while heating to 130� C. whereupon the solution is filtered with a diatomaceous earth filter aid. Saponification no.=20.2; Total acid no.=6.7. Unreacted polyisobutylene=11% (TLC-FID).
Patent CitationsCited PatentFiling datePublication dateApplicantTitleUS3172892 *Mar 30, 1959Mar 9, 1965 Reaction product of high molecular weight succinic acids and succinic anhydrides with an ethylene poly- amineUS3215707 *Mar 31, 1964Nov 2, 1965Lubrizol CorpLubricantUS3454607 *Feb 10, 1969Jul 8, 1969Lubrizol CorpHigh molecular weight carboxylic compositionsUS3954808 *Nov 1, 1973May 4, 1976Edwin Cooper & Company LimitedMethylene bis-phenol alkanoic acid compoundsUS4103023 *Mar 24, 1977Jul 25, 1978Imperial Chemical Industries LimitedAntiulcer, 3,3a,6,6a-tetrahydrofuro(3,4-b)furan derivativesUS4234435 *Feb 23, 1979Nov 18, 1980The Lubrizol CorporationNovel carboxylic acid acylating agents, derivatives thereof, concentrate and lubricant compositions containing the same, and processes for their preparationUS4412031 *Feb 18, 1983Oct 25, 1983Nippon Zeon Co., Ltd.Carbon blackUS4412041 *Feb 18, 1983Oct 25, 1983Nippon Zeon Co. Ltd.Process for modifying rubbers employing a compound containing a carboxyl and an aldehyde groupUS4525541 *Jun 22, 1983Jun 25, 1985Nippon Zeon Co. Ltd.Method for modifying rubbersUS4654435 *Dec 20, 1983Mar 31, 1987Nippon Zeon Co., Ltd.Process for addition reaction of unsaturated organic compoundsUS4704427 *Mar 27, 1986Nov 3, 1987Nippon Zeon Co., Ltd.Method for improving rubbersDE2103686A1 *Jan 27, 1971Aug 17, 1972 Alpha-hydroxy-gamma-lactones prepn - from alpha -oxocarboxylic acid and olefinic unsatd cpds with acid catalystsEP0624638A1 *May 12, 1994Nov 17, 1994The Lubrizol CorporationCompositions useful as additives for lubricants and liquid fuelsWO1995031488A1 *May 11, 1995Nov 23, 1995Exxon Research Engineering CoCarbonyl containing compounds and their derivatives as multi-functional fuel and lube additives* Cited by examinerNon-Patent CitationsReference1 *B.B. Jarvis et al., Synthesis, 11, 1079 (1990).2 *B.B. Snider et al., J. Org. Chem. 44,3567 (1979).3 *Chida et. al., J. Chem. Soc. Perkin Trans. 1, pp. 2667 2673, 1992.4Chida et. al., J. Chem. Soc. Perkin Trans. 1, pp. 2667-2673, 1992.5 *D. Savostianoff, C.R. Acad. Sc. Paris, 263, 605 (Aug. 22, 1966).6 *Horihaura et. al., Chem. Abstracts, vol. 92, 215174, 1980.7 *I.M. Akhmedov et al., Synthetic Communications, 24, 137 (1994).8 *K. Mikami et al., Chem. Rev. 92, 1021 (1992).9 *K. Mikami et al., Tetrahedron Letters 35, 3133 (1994).10 *M. Kerfanto et al., C.R. Acad. Sc. Paris, 264, 232 (1967).11 *M. Terada et al., J. Chem. Soc. Chem. Commun., 833 (1994).12 *M. Terada et al., Tetrahedron Letters, 35, 6693 (1994).13 *T. Mukaiyama et al., Bull. Chem. Soc. Japan, V44, pp. 161 166 (1971).14T. Mukaiyama et al., Bull. Chem. Soc. Japan, V44, pp. 161-166 (1971).15 *Villhauer et. al., J. Org. Chem., vol. 52, pp. 1186 1189, 1987.16Villhauer et. al., J. Org. Chem., vol. 52, pp. 1186-1189, 1987.* Cited by examinerReferenced byCiting PatentFiling datePublication dateApplicantTitleUS6211122 *Jul 27, 1998Apr 3, 2001The Lubrizol CorporationCarboxylic compositions and derivatives thereof and use as lubricating oil and fuel additivesUS6245721Nov 2, 1999Jun 12, 2001Peter ChunNaphthenic and paraffinic oils; chlorinated paraffin; wear, oxidation, friction resistance; internal combustion engines metal powder suspensionWO2009045979A1Sep 30, 2008Apr 9, 2009Lubrizol CorpLubricants that decrease micropitting for industrial gearsWO2011059626A1Oct 14, 2010May 19, 2011The Lubrizol CorporationLubricant system clean-up compositions and methods thereofWO2011146289A1May 11, 2011Nov 24, 2011The Lubrizol CorporationMethods and compositions that provide detergencyWO2011149799A1May 23, 2011Dec 1, 2011The Lubrizol CorporationMethod to provide power gain in an engineWO2011159742A1Jun 15, 2011Dec 22, 2011The Lubrizol CorporationMethods of removing deposits in oil and gas applicationsWO2012084906A1Dec 20, 2011Jun 28, 2012Rhodia OperationsFuel additive composition containing a dispersion of iron particles and a detergentWO2012162020A1May 15, 2012Nov 29, 2012The Lubrizol CorporationStabilized blends containing antioxidantsWO2012162027A1May 15, 2012Nov 29, 2012The Lubrizol CorporationStabilized blends containing friction modifiersWO2012162219A1May 21, 2012Nov 29, 2012The Lubrizol CorporationStabilized blends containing friction modifiersWO2012162282A1May 22, 2012Nov 29, 2012The Lubrizol CorporationStabilized blends containing friction modifiersWO2012177529A1Jun 18, 2012Dec 27, 2012The Lubrizol CorporationLubricating compositions containing salts of hydrocarbyl substituted acylating agentsWO2013043332A1Aug 29, 2012Mar 28, 2013The Lubrizol CorporationQuaternary ammonium salts in heating oilsWO2014066344A1Oct 22, 2013May 1, 2014The Lubrizol CorporationDiesel detergent without a low molecular weight penalty* Cited by examinerClassifications U.S. Classification549/283, 549/285, 549/306International ClassificationC10L10/08, C10L1/24, C07D493/04, C08L23/00, C10L1/188, C10L1/14, C10L1/18, C10L1/19, C10M129/95, C10M159/12, C08L23/26, C10L1/238, C10L1/198, C08F8/00, C10M129/93, C10L1/22Cooperative ClassificationC08F8/28, C10N2210/01, C10L1/198, C10M2207/129, C10M2207/122, C10M2207/124, C10L1/222, C10L1/231, C10L1/2475, C10M2207/289, C10L1/143, C10M2207/282, C10M2207/22, C07D493/04, C10M2207/281, C10L1/2418, C10L1/238, C10M2207/121, C10L1/1855, C10L1/2286, C10M2207/283, C10M2207/123, C10M129/93, C10L1/1881, C10M2207/286, C10M129/95, C10L1/1817, C10L1/19, C10M2207/125European ClassificationC08F8/00, C10L1/198, C10L1/185B1, C10L1/24P3, C10L1/18W, C10M129/95, C07D493/04, C10L1/14B, C10L1/238, C10M129/93Legal EventsDateCodeEventDescriptionMar 6, 2007FPExpired due to failure to pay maintenance feeEffective date: 20070105Jan 5, 2007LAPSLapse for failure to pay maintenance feesJul 26, 2006REMIMaintenance fee reminder mailedJun 14, 2002FPAYFee paymentYear of fee payment: 4Dec 18, 1997ASAssignmentOwner name: LUBRIZOL CORPORATION, THE, OHIOFree format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:DIETZ, JEFFRY G.;BAKER, MARK R.;ADAMS, PAUL E.;REEL/FRAME:008911/0581Effective date: 19951019RotateOriginal ImageGoogle Home - Sitemap - USPTO Bulk Downloads - Privacy Policy - Terms of Service - About Google Patents - Send FeedbackData provided by IFI CLAIMS Patent Services©2012 Google