Unsaturated hydroxycarboxylic compounds useful as intermediates for preparing lubricant and fuel additives

Abstract: Compositions comprising unsaturated hydroxycarboxylic compounds, a process for reacting olefinic compounds with carboxylic reagents and products prepared by the process. The compositions containing the hydroxycarboxylic compounds and the products of the process are useful as intermediates for preparing addrives for lubricants and fuels.

Description: FIELD OF THE INVENTION This invention relates to unsaturated hydroxycarboxylic compounds which are useful particularly, but not exclusively as, intermediates for the preparation of low chlorine containing additives for lubricating oils and normally liquid fuels and to a process for preparing the compounds. BACKGROUND OF THE INVENTION Numerous types of additives are used to improve lubricating oil and fuel compositions. Such additives include, but are certainly not limited to dispersants and detergents of the ashless and ash-containing variety, oxidation inhibitors, anti-wear additives, friction modifiers, and the like. Such materials are well known in the art and are described in many publications, for example, Smalheer, et al, "Lubricant Additives", Lezius-Hiles Co., Cleveland, OH, USA (1967); M.W. Ranney, Ed., "Lubricant Additives", Noyes Data Corp., Park Ridge, NJ, USA (1973); M.J. Satriana, Ed., "Synthetic Oils and Lubricant Additives, Advances since 1979, Noyes Data Corp., Park Ridge NJ, USA (1982), W.C. Gergel, "Lubricant Additive Chemistry", Publication 694-320-65R1 of the Lubrizol Corp. , Wickliffe, OH, USA (1994); and W.C. Gergel et al, "Lubrication Theory and Practice" Publication 794-320-59R3 of the Lubrizol Corp., Wickliffe, OH, USA (1994); and in numerous United States patents, for example Chamberlin, II, US 4,326,972, Schroeck et al, US 4,904,401, and Ripple et al, US 4,981,602. Many such additives are frequently derived from carboxylic reactants, for example, acids, esters, anhydrides, lactones, and others. Specific examples of commonly used carboxylic compounds used as intermediates for preparing lubricating oil additives include alkyl-and alkenyl substituted succinic acids and anhydrides, polyolefin substituted carboxylic acids, aromatic acids, such as salicylic acids, and others. Illustrative carboxylic compounds are described in Meinhardt, et al, US 4,234,435; Norman et al, US 3,172,892, LeSuer et al, US 3,454,607 and Rense, US 3,215,707. Many carboxylic intermediates used in the preparation of lubricating oil additives contain chlorine. While the amount of chlorine present is often only a very small amount of the total weight of the intermediate, the chlorine frequently is carried over into the carboxylic derivative which is desired as an additive. For a variety of reasons, including environmental reasons, the industry has been making efforts to reduce or to eliminate chlorine from additives designed for use as lubricant or fuel additives. Accordingly, it is desirable to provide low chlorine or chlorine free intermediates which can be used to prepare low chlorine or chlorine free derivatives for use in lubricants and fuels. The present invention provides unsaturated hydroxycarboxylic compounds which meet this requirement. B.B. Snider and J.W. van Straten, J. Org. Chem., 44, 3567-3571 (1979) describe certain products prepared by the reaction of methyl glyoxylate with several butenes and cyclohexenes. K. Mikami and M. Shimizu, Chem. Rev., 92, 1021-1050 (1992) describe carbonyl-ene reactions, including glyoxylate-ene reactions. D. Savostianov (communicated by P. Pascal), C.R Acad. Sc. Paris, 263, (605-7) (1966) relates to preparation of some α-hydroxylactones via the action of glyoxylic acid on olefins. M. Kerfanto et. al., C.R. Acad. Sc. Paris, 264, (232-5) (1967) relates to condensation reactions of α-α-di-(N-morpholino)-acetic acid and glyoxylic acid with olefins. Klotman et al, DE 2,103,686 disclose the preparation of alpha-hydroxy-gammalactones by reacting olefins with alpha-oxy(hydroxy) carboxylic acids. Adams et al, EP-A-0,624,683 relates to a compound which may be formed by the reaction of phenolic compounds with carboxylic reactants and subsequently an amine. Ohta et al, EP-A-0,603,889 relates to a process for preparing a polyhydroxycarboxylic acid comprising dehydrating polycondensation of lactic acid containing impurities. Kitahara et al, US 4,654,435 describes a process for the addition reaction of an unsaturated organic compound, except a rubber, having at least one carbon-carbon double bond in a molecule, which comprises reacting the unsaturated organic compound with an organic compound having a carboxyl group and an aldehyde group in the presence of a Lewis acid. Kitahara et al, US 4,525,541 describes a method for modifying a rubber having an unsaturated carbon bond which comprises reacting the rubber with an organic compound represented by the general formula wherein -R represents a hydrocarbon group, and -X is -H,-CN or in which -Y represents an organic atomic grouping, in the presence of a Lewis acid to introduce an ester group. Optionally, the ester group introduced is converted into a carboxyl group by chemically treating the reaction product. SUMMARY OF THE INVENTION According to one aspect, the present invention provides a compound of the general formula wherein each of R 1 and R 2 is independently H or a hydrocarbon based group, R 3 is H or hydrocarbyl; R 4 is a divalent hydrocarbylene group; n = 0 or 1; y is an integer ranging from 1 to 200; R 5 is H or hydrocarbyl; and X is a group of the formula wherein each of R 6 , R 7 and R 8 is independently H or a hydrocarbon based group, provided that at least one of R 6 , R 7 and R 8 is a hydrocarbon based group containing from 30 to 100 carbon atoms. In another aspect of this invention, there is provided a process for preparing the compounds of the present invention comprising reacting, optionally in the presence of an acidic catalyst, (A) at least one olefinic compound of the general formula (R 1 )(R 2 ) C=C(R 6 )(CH(R 7 )(R 8 )) wherein each of R 1 and R 2 is, independently, hydrogen or a hydrocarbon based group and each of R 6 , R 7 and R 8 is, independently, hydrogen or a hydrocarbon based group provided that at least one is a hydrocarbon based group containing from 30 to 100 carbon atoms; with (B) at least one carboxylic reactant selected from a compound of the general formula R 3 C(O)(R 4 ) n C(O)OR 5 and a compound of the general formula wherein each of R 3 , R 5 and R 9 is independently H or a hydrocarbyl group, R 4 is a divalent hydrocarbylene group, and n is 0 or 1, wherein the ratio of reactants ranges from about 0.6 moles (B) per equivalent of (A), to about 1.5 moles (B) per equivalent of (A) wherein equivalents of (A) are defined hereinafter provided that when an organic sulfonic acid or mineral acid is used, the maximum reaction temperature is about 150°C. According to a further aspect, the present invention provides products prepared by this process . DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Various preferred features and embodiments of the present invention will now be described by way of non-limited example. As used herein, the terms "hydrocarbon", "hydrocarbyl" or "hydrocarbon based" mean that the group being described has predominantly hydrocarbon character within the context of this invention. These include groups that are purely hydrocarbon in nature, that is, they contain only carbon and hydrogen. They may also include groups containing substituents or atoms which do not alter the predominantly hydrocarbon character of the group. Such substituents may include halo-, alkoxy-, nitro-, etc. These groups also may contain hetero atoms. Suitable hetero atoms will be apparent to those skilled in the art and include, for example, sulfur, nitrogen and oxygen. Therefore, while remaining predominantly hydrocarbon in character within the context of this invention, these groups may contain atoms other than carbon present in a chain or ring otherwise composed of carbon atoms. In general, no more than about three non-hydrocarbon substituents or hetero atoms, and preferably no more than one, will be present for every 10 carbon atoms in the hydrocarbon, hydrocarbyl or hydrocarbon based groups. Most preferably, the groups are purely hydrocarbon in nature, that is they are essentially free of atoms other than carbon and hydrogen. Throughout the specification and claims the expression oil soluble or dispersible is used. By oil soluble or dispersible is meant that an amount needed to provide the desired level of activity or performance can be incorporated by being dissolved, dispersed or suspended in an oil of lubricating viscosity. Usually, this means that at least about 0.001% by weight of the material can be incorporated in a lubricating oil. For a further discussion of the terms oil soluble and dispersible, particularly "stably dispersible", see US Patent 4,320,019. As noted hereinabove, provided by this invention are certain unsaturated hydroxycarboxylic compounds and a process for preparing low chlorine or chlorine free compositions useful as intermediates for preparing low chlorine or chlorine free additives for lubricating oil and fuel compositions. The Compounds This invention provides a compound of the general formula Each of R 1 and R 2 is independently H or a hydrocarbon based group. In one preferred embodiment, each of R 1 and R 2 is independently H or a lower alkyl group provided that at least one is lower alkyl. In another preferred embodiment, one of R 1 and R 2 is H and the other is a lower alkyl group. As used herein, the expression "lower alkyl" refers to alkyl groups containing from 1 to 7 carbon atoms. Examples include methyl, ethyl and the various isomers of propyl, butyl, pentyl, hexyl and heptyl. In one especially preferred embodiment, each of R 1 and R 2 is H. R 3 is H or hydrocarbyl. These hydrocarbyl groups are usually aliphatic, preferably alkyl, more preferably, lower alkyl. Especially preferred is where R 3 is H or methyl, most preferably, H. R 4 is a divalent hydrocarbylene group. This group may be aliphatic or aromatic, but is preferably aliphatic. Preferably, R 4 is an alkylene group containing from 1 to 10 carbon atoms, more preferably from 1 to 3 carbon atoms. The 'n' is 0 or 1; that is, in one embodiment, R 4 is present and in another embodiment, R 4 is absent. More preferably, R 4 is absent. The 'y' is an integer ranging from 1 to 200, more preferably from 1 to 50 and even more preferably from 1 to 20. Preferably y is 1. The group X has the formula wherein each of R 6 , R 7 and R 8 is independently H or a hydrocarbon based group, provided that at least one of R 6 , R 7 and R 8 is a hydrocarbon based group containing from 30 to 100 carbon atoms. When at least one of R 6 , R 7 and R 8 is a hydrocarbyl group, it is preferably an aliphatic group. In one preferred embodiment R 6 may be derived from homopolymerized and interpolymerized C 2-18 olefins. In a further preferred embodiment, at least one of R 7 and R 8 is an aliphatic group containing from 10 to 300 carbon atoms. Preferably, at least one of R 7 and R 8 may be derived from homopolymerized and interpolymerized C 2-18 olefins. The polymerized olefins are preferably 1-olefins, preferably ethylene, propylene, butenes, isobutenes, and mixtures thereof. Polymerized olefins are often referred to herein as polyolefins. In yet another preferred embodiment at least one of R 7 and R 8 is an aliphatic group containing from 30 to 50 carbon atoms. Within this embodiment, preferably one of R 7 and R 8 is H and the other is the aliphatic group. R 5 is H or hydrocarbyl. When R 5 is hydrocarbyl, it is usually an aliphatic group, preferably a group containing from 1 to 30 carbon atoms, more preferably from 8 to 18 carbon atoms. In another preferred embodiment, R 5 is lower alkyl, wherein "lower alkyl" is defined hereinabove. Preferably, R 5 is H or lower alkyl. In one preferred embodiment, each of R 1 , R 2 and R 3 is independently hydrogen or a lower alkyl or alkenyl group. In one especially preferred embodiment, each of R 1 , R 2 and R 3 is hydrogen and n = 0. In another preferred embodiment, R 6 is an aliphatic group containing from 8 to 150 carbon atoms, R 5 is H, n is 0 and R 3 is H. The Process The present invention also provides a process comprising reacting, optionally in the presence of an acidic catalyst, (A) at least one olefinic compound with (B) at least one carboxylic reactant wherein (A) and (B) are defined in greater detail hereinbelow. The Catalyst The process of this invention may be conducted in the presence of an acidic catalyst; however, no catalyst is required and it is often easier to prepare and isolate the monomeric product when no catalyst is employed. However, when catalysts are used, yields are sometimes enhanced. Acid catalysts, such as organic sulfonic acids, for example, paratoluene sulfonic acid, methane sulfonic acid, heteropolylacids, the complex acids of heavy metals (e.g., Mo, W, Sn, V, Zr, etc.) with phosphoric acids (e.g., phosphomolybdic acid), and mineral acids, such as sulfuric acid and phosphoric acid, tend to lead to oligomeric products, especially when higher temperatures are also used. Lewis acids, e.g., BF 3 , AlCl 3 and FeCl 3 , are useful for promoting "ene" reactions, tend to promote formation of monomeric products, and usually do not hydrolyze esters. When they are used, catalysts are preferably used in amounts ranging from 0.01 mole % to 10 mole %, more preferably from 0.1 mole % to 2 mole %, based on moles of olefinic reactant. (A) The Olefinic Compound The olefinic compound employed as a reactant in the process of this invention has the general formula (R 1 )(R 2 ) C=C(R 6 )(CH(R 7 )(R 8 )) wherein each of R 1 and R 2 is, independently, hydrogen or a hydrocarbon based group and each of R 6 , R 7 and R 8 is, independently, hydrogen or a hydrocarbon based group provided that at least one is a hydrocarbon based group containing from 30 to 100 carbon atoms. These olefinic compounds are diverse in nature. Virtually any compound containing an olefinic bond may be used provided it meets the general requirements set forth hereinabove for (III) and does not contain any functional groups (e.g., primary or secondary amines) that would interfere with the reaction with the carboxylic reactant (B). Useful olefinic compounds may be terminal olefins, i.e., olefins having a H 2 C=C group, or internal olefins. Useful olefinic compounds may have more than one olefinic bond, i.e., they may be dienes, trienes, etc. Most often, they are mono-olefinic. Examples include linear α-olefins, cis- or trans- disubstituted olefins, trisubstituted and tetrasubstituted olefins. When (A) is a mono-olefin, one mole of (A) contains one equivalent of C=C; when (A) is a di-olefin, one mole of (A) contains 2 equivalents of C=C bonds; when (A) is a tri-olefin, one mole of (A) contains 3 equivalents of C=C bonds, and so forth. Aromatic double bonds are not considered to be olefinic double bonds within the context of this invention. As used herein, the expression "polyolefin" defines a polymer derived from olefins. The expression "polyolefinic" refers to a compound containing more than one C=C bond. Among useful preferred compounds are those that are purely hydrocarbon, i.e., those substantially free of non-hydrocarbon groups, or they may contain one or more non-hydrocarbon groups as discussed in greater detail herein. In one preferred embodiment, the olefinic compounds are substantially hydrocarbon, that is, each R group in (III) is H or contains essentially carbon and hydrogen. In one preferred aspect within this embodiment, each of R 1 , R 2 , R 7 and R 8 is hydrogen and R 6 is a hydrocarbyl group containing from 30 up to 100 carbon atoms, more preferably from 50 up to 100 carbon atoms. In another preferred aspect of this embodiment, each of R 1 and R 2 is hydrogen, R 6 is H or a lower alkyl group and the group (CH(R 7 )(R 8 )) is a hydrocarbyl group containing up to 200 carbon atoms, more preferably from 50 up to 100 carbon atoms. In another preferred embodiment, one or more of the R groups present in (III) is an organic radical which is not purely hydrocarbon. Such groups may contain or may be groups such as carboxylic acid, ester, amide, salt, including ammonium, amine and metal salts, cyano, hydroxy, thiol, tertiary amino, nitro, alkali metal mercapto and the like. Preferably, the hydrocarbyl groups are aliphatic groups. In one preferred embodiment, when an R group is an aliphatic group containing a total of from 30 to 100 carbon atoms, the olefinic compound may be derived from homopolymerized and interpolymerized C 2-18 mono- and di-olefins, preferably 1-olefins, especially those containing from 2 to 5 carbon atoms, preferably 3 or 4 carbon atoms. Examples of such olefins are ethylene, propylene, butene-1, isobutylene, butadiene, isoprene, 1-hexene, 1-octene, etc. R groups can, however, be derived from other sources, such as monomeric high molecular weight alkenes (e.g., 1-tetracontene), aliphatic petroleum fractions, particularly paraffin waxes and cracked analogs thereof, white oils, synthetic alkenes such as those produced by the Ziegler-Natta process (e.g., poly-(ethylene) greases) and other sources known to those skilled in the art. Any unsaturation in the R groups may be reduced by hydrogenation according to procedures known in the art, provided at least one olefinic group remains, as described for (III). In one preferred embodiment, at least one R is derived from polybutene, that is, polymers of C 4 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 ethylenepropylene polymers and ethylene-alpha olefin-diene, preferably ethylene-propylene - diene polymers. Molecular weights of such polymers may vary over a wide range but especially those having number average molecular weights (M n ) ranging from 300 to 20,000, preferably 700 to 5000. In one preferred embodiment the olefin is an ethylene-propylene-diene copolymer having M n ranging from about 900 to about 2500. An example of such materials are the Trilene® polymers marketed by the Uniroyal Company, Middlebury, CT, USA. A preferred source of hydrocarbyl groups R are polybutenes obtained by polymerization of a C4 refinery stream having a butene content of 35 to 75 weight percent and isobutylene content of 15 to 60 weight percent in the presence of a Lewis acid catalyst such as aluminum trichloride or boron trifluoride. These polybutenes contain predominantly (greater than 80% of total repeating units) isobutylene repeating units of the configuration These polybutenes are typically monoolefinic, that is, they contain but one olefinic bond per molecule. The olefinic compound may be a polyolefin comprising a mixture of isomers wherein from 50 percent to 65 percent are tri-substituted olefins wherein one substituent contains from 2 to 500 carbon atoms, preferably from 30 to 200 carbon atoms, more preferably from 50 to 100 carbon atoms, preferably aliphatic carbon atoms, and the other two substituents are lower alkyl. When the olefin is a tri-substituted olefin, it preferably comprises a mixture of cis- and trans-1-lower alkyl, 1-(aliphatic hydrocarbyl containing from 30 to about 100 carbon atoms), 2-lower alkyl ethylene and 1,1-di-lower alkyl, 2-(aliphatic hydrocarbyl containing from 30 to 100 carbon atoms) ethylene. In one preferred embodiment, the monoolefinic groups are vinylidene groups, i.e., groups of the formula CH 2 = C although the polybutenes may also comprise other olefinic configurations. In one preferred embodiment the polybutene is substantially monoolefinic, comprising at least 30 mole %, preferably at least 50 mole % vinylidene groups, more often at least 70 mole % vinylidene groups. Such materials and methods for preparing them are described in U.S. Patents 5,286,823 and 5,408,018. They are commercially available, for example under the tradenames Ultravis® (RTM) (BP Chemicals) and Glissopal®(RTM) (BASF). As is apparent from the foregoing, olefins of a wide variety of type and molecular weight are useful for preparing the compositions of this invention. Preferred olefins are substantially hydrocarbon and have number average molecular weight ( M n) up to 70,000, preferably up to to 7,000, more preferrably from 1,300 to 5,000 and even more preferably up to 3,000. Specific characterization of olefin reactants (A) used in the processes of this invention can be accomplished by using techniques known to those skilled in the art. These techniques include general qualitative analysis by infrared and determinations of average molecular weight, e.g., M n, number average molecular weight, etc., employing vapor phase osmometry (VPO) and gel permeation chromatography (GPC). Structural details can be elucidated employing proton and carbon 13 (C 13 ) nuclear magnetic resonance (NMR) techniques. NMR is useful for determining substitution characteristics about olefinic bonds, and provides some details regarding the nature of the substituents. More specific details regarding substituents about the olefinic bonds can be obtained by cleaving the substituents from the olefin by, for example, ozonolysis, then analyzing the cleaved products, also by NMR, GPC, VPO, and by infra-red analysis and other techniques known to the skilled person. (B) The Carboxylic Reactant The carboxylic reactant is at least one member selected from a compound of the general formula R 3 C(O)(R 4 ) n C(O)OR 5 and a compound of the general formula wherein each of R 3 , R 5 and R 9 is independently H or a hydrocarbyl group, R 4 is a divalent hydrocarbylene group, and n is 0 or 1. Preferred embodiments of the groups R 3 and R 5 are set forth hereinabove where corresponding groups in the compound (I) are described. R 9 is preferably H or lower alkyl. Examples of carboxylic reactants (B) are glyoxylic acid, carboxy aromatic aldehydes, such as 4-carboxybenzaldehyde, and other omega-oxoalkanoic acids, keto alkanoic acids such as pyruvic acid, levulinic acid, ketovaleric acids, ketobutyric acids and numerous others. The skilled worker, having the disclosure before him, will readily recognize the appropriate compound of formula (V) to employ as a reactant to generate a given intermediate. Preferred compounds of formula (V) are those that will lead to preferred compounds of formula (I). Reactant (B) may be a compound of the formula wherein each of R 3 and R 5 is independently H or hydrocarbyl preferably H or alkyl. Such compounds arise when the carboxylic reactant is hydrated. Glyoxylic acid monohydrate is a representative example. From the foregoing, it is apparent that the various 'R' groups in the product (I) correspond to the same groups in the olefinic and carboxylic reactants. The process of this invention is conducted at temperatures up to 150°C, preferably up to 120°C, even more preferably from 120°C up to 130°C. The process employs from 0.6 moles of reactant (B) per mole of olefinic compound (A), to 1.5 moles (B) per equivalent of (A), more preferably from about 0.8 moles (B) per mole of (A) to 1.2 moles (B) per equivalent of (A), even more preferably from about 0.95 moles (B) per mole of (A) to about 1.05 moles (B) per equivalent of (A). In order to maximize yield of product of this invention, it is generally desirable to conduct the reaction at as low a temperature as possible. As noted herein, many reactants contain water which may be removed. Removal of water at moderate temperatures is attainable employing reduced pressure, a solvent that aids in azeotropic distillation of water, or by purging with an inert gas such as N 2 . The progress of the reaction can be followed by observing the infra-red spectrum. The absorption for -COOH carbonyl of the products appears at about 1710 cm -1 . The total acid number as measured using essentially the procedure in ASTM D-664 (Potentiometric Method) or ASTM D-974 (Color Indicator Method) is useful together with the infrared, keeping in mind that non-acidic products (e.g., polyester products), those derived from non-acidic reactants and condensation products such as lactones will not display significant acid numbers. These procedures appear in the Annual Book of ASTM Standards, Volume 05.01, ASTM, 1916 Race Street, Philadelphia, PA, USA. The following examples are intended to illustrate several compositions of this invention as well as means for preparing same. Unless indicated otherwise, all parts are parts by weight. It is to be understood that these examples are intended to illustrate several compositions and procedures of the invention and are not intended to limit the scope of the invention. Example 1 A reactor equipped with a stirrer, thermowell, Dean-Stark trap with condenser and sub-surface N 2 inlet is charged with 300 parts polyisobutylene having a number average molecular weight of about 1000 and containing about 50% by weight of terminal vinylidene groups, 44 parts 50% aqueous glyoxylic acid and 1 part sulfuric acid. The materials are heated to 100°C and are held at 100°C for 1.5 hours while removing water under a slow N 2 purge. The materials are then heated to 125°C and held at 125°C for 2.5 hours then heated to 150°C and held at 150°C for 3 hours while continuing to remove water under a slow N 2 purge. The strong acid (neutralization number, bromphenol blue indicator) is neutralized by sodium hydroxide. At this point the materials contain by analysis (TLC-FID) 34.9% unreacted polyisobutylene. The materials are reheated to 110°C and filtered through a diatomaceous earth filter aid. The filtrate has saponification no. = 40 and total acid no. = 12.0. Example 2 A reactor equipped as in Example 1 is charged with 300 parts polyisobutylene 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 1 part sulfuric acid. The materials are heated to 100°C and are held at 100°C for 1.5 hours while removing water under a slow N 2 purge. The materials are then heated to 125°C and held at 125°C for 2.5 hours, then heated to 150°C and held at 150°C for 3 hours while continuing to remove water under a slow N 2 purge. At this point the materials contain by analysis (TLC-FID) 27.2% unreacted polyisobutylene. The materials are reheated to 110°C and filtered through a diatomaceous earth filter aid. The filtrate has saponification no. = 35.7 and total acid no. = 16.2. Example 3 A reactor equipped as in Example 1 is charged with 300 parts polyisobutylene having a number average molecular weight of about 1000 and containing about 50 mole % of terminal vinylidene groups and 44 parts 50% aqueous glyoxylic acid. The materials are heated to 100°C and are held at 100°C for 1.5 hours while removing water under a slow N 2 purge. The materials are then heated to 125°C and held at 125°C for 2.5 hours, then to 150°C and held at 150°C for 3 hours while continuing to remove water under a slow N 2 purge. At this point the materials contain by analysis (TLC-FID) 35.7% unreacted polyisobutylene. The materials are reheated to 110°C and filtered through a diatomaceous earth filter aid. The filtrate has saponification no. = 48 and total acid no. = 14.2. Example 4 The process of Example 3 is repeated employing 0.2 mole % BF 3 catalyst. While the invention has been explained in relation to its preferred embodiments, it is to be understood that various modifications thereof will become apparent to those skilled in the art upon reading the specification. Therefore, it is to be understood that the invention disclosed herein is intended to cover such modifications that fall within the scope of the appended claims.

Claims: A compound of the general formula wherein each of R 1 and R 2 is independently H or a hydrocarbon based group, R 3 is H or hydrocarbyl; R 4 is a divalent hydrocarbylene group; n = 0 or 1; y is an integer ranging from 1 to 200; R 5 is H or hydrocarbyl; and X is a group of the formula wherein each of R 6 , R 7 and R 8 is independently H or a hydrocarbon based group, provided that at least one of R 6 , R 7 and R 8 is a hydrocarbon based group containing from 30 to 100 carbon atoms. The compound of claim 1 wherein each of R 1 , R 2 and R 3 is independently hydrogen or a lower alkyl or alkenyl group, and wherein R 4 is an alkylene group containing from 1 to 10 carbon atoms. The compound of claim 1 or claim 2 wherein each of R 1 , R 2 and R 3 is hydrogen and n = zero, y = 1, and R 5 is H or lower alkyl. The compound of any preceding claim wherein R 6 contains from 30 to 100 carbon atoms and is derived from homopolymerized and interpolymerized C 2-10 olefins. The compound of any preceding claim wherein at least one of R 7 and R 8 contains from 30 to 100 carbon atoms and is derived from homopolymerized and interpolymerized C 2-10 olefins. The compound of claim 4 or 5 wherein the olefins are 1-olefins selected from ethylene, propylene, butenes, isobutylene and mixtures thereof. A process for preparing a compound of claim 1 comprising reacting, optionally in the presence of an acidic catalyst selected from organic sulfonic acids, mineral acids and Lewis acids, (A) at least one olefinic compound of the general formula (R 1 )(R 2 ) C=C(R 6 )(CH(R 7 )(R 8 )) wherein each of R 1 and R 2 is, independently, hydrogen or a hydrocarbon based group and each of R 6 , R 7 and R 8 is, independently, hydrogen or a hydrocarbon based group provided that at least one is a hydrocarbon based group containing from 30 to 100 carbon atoms; with (B) at least one carboxylic reactant selected from a compound of the general formula R 3 C(O)(R 4 ) n C(O)OR 5 and a compound of the general formula wherein each of R 3 , R 5 and R 9 is independently H or a hydrocarbyl group, R 4 is a divalent hydrocarbylene group, and n is 0 or 1, wherein the ratio of reactants ranges from 0.6 moles (B) per mole of (A) to 1.5 moles (B) per equivalent of (A) provided that when an organic sulfonic acid or mineral acid is used, the maximum reaction temperature is 150°C. The process of claim 7 wherein reactant (B) is selected from glyoxylic acid and a compound of the general formula wherein each of R 3 and R 5 is independently H or a lower alkyl group and n = 0. The process of claim 7 or claim 8 wherein each of R 1 , R 2 , R 7 and R 8 is hydrogen. The process of any one of claims 7 to 9 wherein each of R 1 and R 2 is hydrogen and R 6 is H or a lower alkyl group. The process of any one of claims 7 to 10 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 H 2 C = C(R 6 )(CH(R 7 )(R 8 )) wherein R 6 is H or lower alkyl, the group (CH(R 7 )(R 8 )) is an aliphatic group containing from 30 to 200 carbon atoms and the olefinic compound is derived from homopolymerized and interpolymerized C 2-10 olefins. The process of any one of claims 7 to 11 wherein the olefinic compound is a polyolefin comprising a mixture of isomers wherein from 50% to 65% are tri-substituted olefins wherein one substituent contains from 30 to 100 carbon atoms and the other two substituents are lower alkyl. The process of any one of claims 7 to 12 wherein R 6 is an aliphatic group, R 4 is an alkylene group containing from 1 to 10 carbon atoms, and (A) is derived from homopolymerized and interpolymerized C 2-10 olefins. The process of any one of claims 7-13 wherein the olefinic compound is a polyolefin wherein at least 75% of the polyolefins are terminal olefins. The process of any one of claims 7 to 13 wherein the olefinic compound is a monoolefin wherein at least 70% of the olefinic groups are terminal vinylidene groups.

Inventors: ADAMS PAUL E, BAKER MARK R, DIETZ JEFFRY G, ADAMS, PAUL E., BAKER, MARK R., DIETZ, JEFFRY G.
Applicants: LUBRIZOL CORP, THE LUBRIZOL CORPORATION
Application year: 1996
Main classification: C08F8
IPC codes: C08F299, C10M145, C07C59, C10L1, C07C51, C08F8, C07C69