Source: https://patents.google.com/patent/US6020500?oq=6272333
Timestamp: 2018-03-22 03:14:45
Document Index: 305021550

Matched Legal Cases: ['arts 70', 'arts 50', 'arts 50', 'arts 50', 'arts 50', 'arts 50', 'arts 50', 'arts 70']

US6020500A - Hydroxy-substituted monolactones useful as intermediates for preparing lubricating oil and fuel additives - Google Patents
Hydroxy-substituted monolactones useful as intermediates for preparing lubricating oil and fuel additives Download PDF
US6020500A
US6020500A US08518069 US51806995A US6020500A US 6020500 A US6020500 A US 6020500A US 08518069 US08518069 US 08518069 US 51806995 A US51806995 A US 51806995A US 6020500 A US6020500 A US 6020500A
US08518069
In one preferred embodiment, at least one R is derived from polybutene, that is, polymers of C4 olefins, including 1-butene, 2-butene and isobutylene. Those derived from isobutylene, i.e., polyisobutylenes, are especially preferred. In another preferred embodiment, R is derived from polypropylene. In another preferred embodiment, R is derived from ethylene-alpha olefin polymers, particularly ethylene-propylene-diene polymers. Molecular weights of such polymers may vary over a wide range, but especially preferred are those having number average molecular weights (Mn) ranging from about 300 to about 20,000, preferably 700 to about 5000. In one preferred embodiment, the olefin is an ethylene-propylene-diene copolymer having Mn ranging from about 900 to about 2500. An example of such materials are the Trilene® polymers marketed by the Uniroyal Company, Middlebury, Conn., U.S.A.
The process of this invention is conducted at temperatures ranging from ambient up to the lowest decomposition temperature of any of the reactants, usually from about 60° C. to about 220° C., more often from about 120° C. to about 180° C., preferably up to about 160° C. The process employs from about 0.6 moles (B) per mole of (A) to 1.5 moles (B) per equivalent of (A), more often from about 0.8 moles (B) per mole of (A) to about 1.2 moles (B) per equivalenet of (A), even more often from about 0.95 moles (B) per mole of (A) to about 1.05 moles (B) per equivalent of (A).
A reactor is charged with 3000 parts of a polyisobutene having a number average molecular weight of about 1000 and which contains about 80 mole % terminal vinylidene groups and 6 parts 70% aqueous methansulfonic acid. The materials are heated to 160° C. under N2 followed by addition of 577.2 parts 50% aqueous glyoxylic acid over 4 hours while maintaining 155-160° C. Water is removed and is collected in a Dean-Stark trap. The reaction is held at 160° C. for 5 hours, cooled to 140° C. and filtered with a diatomaceous earth filter aid. The filtrate has total acid no. (ASTM Procedure D-974)=34.7 and saponification no. (ASTM Procedure D-74)=53.2Mn (Gel permeation chromatography (GPC))=1476 and MW (GPC)=3067; unreacted polyisobutene (Thin layer chromatography-Flame ionization detector (TLC-FID))=8.6%.
A reactor is charged with 300 parts of polyisobutene having a number average molecular weight of about 1000 and containing about 70 mole % of terminal vinylidene groups, 44 parts 50% aqueous glyoxylic acid and 100 parts cyclohexane. The materials are heated to reflux (75° C.) under N2 and the water is azeotropically removed, collecting 22 parts water. The reactor is equipped for vacuum distillation and is stripped to 120° C. at 10 mm Hg. Infrared analysis of residue shows vilylidene olefin remains. To the reactor are charged 22 parts additional 50% aqueous glyoxylic acid and 100 parts cyclohexane, heated to reflux (75° C.) while azeotropically removing 11 parts water. The materials are stripped to 120° C. at 10 mm Hg and filtered using a diatomaceous earth filter aid. The filtrate shows 18% unreacted polyisobutene (TLC-FID) and saponification No.=61.7.
One mole (based on total C═C content) of C18-24 alpha olefin and 1.2 moles glyoxylic acid monohydrate are reacted in the presence of 2 mole % 70% aqueous methane sulfonic acid under a N2 blanket at 120° C. for four hours, removing water. The reaction product is dried by heating to 130° C. for 1 hour, aqueous distillate being collected in a Dean-Stark trap. The residue is filtered employing a diatomaceous earth filter aid.
A reactor equipped with a stirrer, thermowell, Dean-Stark trap with condenser and sub-surface N2 inlet is charged with 500 parts polyisobutylene having a number average molecular weight of about 1000 and containing about 70 mole % of terminal vinylidene groups and 80 parts 50% aqueous glyoxylic acid. The materials are heated to 160° C. and are held at 160° C. for 6 hours while removing H2 O maintaining a slow N2 purge. The materials are diluted with 143 parts of mineral oil, reheated to 100° C. and filtered through a diatomaceous earth filter aid.
A reactor equipped as in Example 4 is charged with 400 parts polyisobutylene having a number average molecular weight of about 1000 and containing less than 10 mole % of terminal vinylidene groups, 100 parts cyclohexane, and 4 parts methane sulfonic acid. The materials are heated to reflux and 27 parts 50% aqueous glyoxylic acid are added over 0.5 hour. The materials are held at reflux for 1 hour while azeotropically removing water. An additional 27 parts 50% aqueous glyoxylic acid are added over 0.5 hour. The materials are held at reflux for 4 hours while azeotropically removing water. The materials are then heated to 150° C. by removing distillate and the materials are held at 150° C. for 1 hour. At this point the materials contain by analysis (TLC-FID) 19% unreacted polyisobutylene. The materials are filtered through a diatomaceous earth filter aid. The filtrate has saponification no.=50.1.
A reactor equipped as in Example 4 is charged with 1000 parts polyisobutylene having a number average molecular weight of about 1000, 207.2 parts 50% aqueous glyoxylic acid, 5 parts 70% aqueous methane sulfonic acid, 0.1 parts silicone antifoam agent and 300 parts cyclohexane. The reaction is heated to 105° C. under N2 and is held there for 6 hours, under N2, collecting water. The temperature is increased to 110° C. and held for 4 hours, collecting water. Cyclohexane is removed by heating at 110° C. for 2 hours. Strip to 120° C. at 25 mm Hg for 2 hours then filter with a diatomaceous earth filter aid. Filtrate shows 15.3% unreacted polyisobutylene (TLC-FID). Saponification no.=58.4.
1. A composition comprising a compound of the formula ##STR12## wherein y=1; wherein X is a divalent hydrocarbyl group
wherein each of R1 and R2 is H or a hydrocarbon based group;
2. The composition of claim 1 wherein each of R1, R2 and R3 is H.
19. A composition comprising a compound of the formula ##STR13## wherein n=0 or 1; y=0 or 1; wherein X is a divalent hydrocarbyl group selected from the group consisting of ##STR14## wherein each of R1 and R2 is H or a hydrocarbon based group; R3 is H or hydrocarbyl;
wherein R6 is an aliphatic group containing from 30 to about 100 carbon atoms and is derived from a polymer selected from the group consisting of homopolymerized and interpolymerized C2-10 olefins, and each of R7 and R8 is independently H or a hydrocarbon based group.
20. The composition of claim 19 wherein each of R1, R2 and R3 is independently H or a lower alkyl or alkenyl group.
27. A composition comprising a compound of the formula wherein n=0 or 1; y=0 or 1;
wherein X is a divalent hydrocarbyl group selected from the group consisting of ##STR16## wherein each of R1 and R2 is H or a hydrocarbon based group; R3 is H or hydrocarbyl;
R6 is H or a hydrocarbon based group;
wherein at least one of R7 and R8 is an aliphatic group containing from about 30 to about 100 carbon atoms and is derived from a polymer selected from the group consisting of homopolymerized and interpolymerized C2-10 olefins.
28. The composition of claim 27 wherein each of R1, R2 and R3 is independently H or a lower alkyl or alkenyl group.
36. The composition prepared by the process comprising reacting, in the presence of an acidic catalyst selected from the group consisting of organic sulfonic acids, heteropolyacids, and mineral acids, (A) at least one olefinic compound of the general formula
(R.sup.1)(R.sup.2)C═C(R.sup.6)(CH(R.sup.7)(R.sup.8))
wherein each of R1 and R2 is, independently, hydrogen or a hydrocarbon based group and each of R6, R7 and R8 is, independently, hydrogen or a hydrocarbon based group provided that at least one is hydrocarbon based group containing at least 7 carbon atoms; and
R.sup.3 C(O)(R.sup.4).sub.m C(O)OR.sup.5                   (IV)
and compounds of the formula ##STR18## wherein each of R3, R5 and R9 is independently H or a hydrocarbyl group, R4 is a divalent hydrocarbylene group, and n is 0 or 1 in amounts ranging from 0.6 moles (B) per mole of (A) to 1.5 moles (B) per equivalent of (A).
37. The composition of claim 36 wherein the at least one reactant (B) is glyoxylic acid.
40. The composition of claim 39 wherein the olefinic compound is a polyolefin comprising a mixture of isomers, at least about 50% by weight of the mixture comprising isomers of the formula
41. The composition of claim 40 wherein the polyolefin is polyisobutylene.
US08518069 1995-08-22 1995-08-22 Hydroxy-substituted monolactones useful as intermediates for preparing lubricating oil and fuel additives Expired - Fee Related US6020500A (en)
US08518069 US6020500A (en) 1995-08-22 1995-08-22 Hydroxy-substituted monolactones useful as intermediates for preparing lubricating oil and fuel additives
JP21581896A JPH09132789A (en) 1995-08-22 1996-08-15 Hydroxy-substituted monolactone useful as intermediate for preparing lubricating oil additive and fuel additive
CA 2183610 CA2183610A1 (en) 1995-08-22 1996-08-19 Hydroxy-substituted monolactones useful as intermediates for preparing lubricating oil and fuel additives
DE1996618109 DE69618109T2 (en) 1995-08-22 1996-08-20 Hydroxy substituted lactones as intermediates for preparing lubricating oil and fuel additives
ES96306063T ES2170207T3 (en) 1995-08-22 1996-08-20 Lactones of hydroxy substitution useful as intermediates for preparing lubricating oil additives and fuel.
DE1996618109 DE69618109D1 (en) 1995-08-22 1996-08-20 Hydroxy substituted lactones as intermediates for preparing lubricating oil and fuel additives
EP19960306063 EP0759443B1 (en) 1995-08-22 1996-08-20 Hydroxy-substituted monolactones useful as intermediates for preparing lubricating oil and fuel additives
US09232975 US6114547A (en) 1995-08-22 1999-01-19 Hydroxy-substituted monolactones and use thereof as intermediates for preparing lubricating oil and fuel additives
US09232975 Division US6114547A (en) 1995-08-22 1999-01-19 Hydroxy-substituted monolactones and use thereof as intermediates for preparing lubricating oil and fuel additives
US6020500A true US6020500A (en) 2000-02-01
ID=24062415
US08518069 Expired - Fee Related US6020500A (en) 1995-08-22 1995-08-22 Hydroxy-substituted monolactones useful as intermediates for preparing lubricating oil and fuel additives
US09232975 Expired - Fee Related US6114547A (en) 1995-08-22 1999-01-19 Hydroxy-substituted monolactones and use thereof as intermediates for preparing lubricating oil and fuel additives
US (2) US6020500A (en)
EP (1) EP0759443B1 (en)
JP (1) JPH09132789A (en)
CA (1) CA2183610A1 (en)
DE (2) DE69618109T2 (en)
ES (1) ES2170207T3 (en)
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EP0759443A3 (en) 1998-01-07 application
JPH09132789A (en) 1997-05-20 application
US6114547A (en) 2000-09-05 grant
EP0759443A2 (en) 1997-02-26 application
DE69618109T2 (en) 2002-06-20 grant
ES2170207T3 (en) 2002-08-01 grant
CA2183610A1 (en) 1997-02-23 application
DE69618109D1 (en) 2002-01-31 grant
EP0759443B1 (en) 2001-12-19 grant
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:BAKER, MARK R.;ADAMS, PAUL E.;DIETZ, JEFFRY G.;REEL/FRAME:007889/0353;SIGNING DATES FROM 19951107 TO 19951114