Solid anti-friction devices – materials therefor – lubricant or se – Lubricants or separants for moving solid surfaces and... – Heterocyclic ring compound; a heterocyclic ring is one...
Reexamination Certificate
2001-11-08
2003-04-15
McAvoy, Ellen M. (Department: 1764)
Solid anti-friction devices, materials therefor, lubricant or se
Lubricants or separants for moving solid surfaces and...
Heterocyclic ring compound; a heterocyclic ring is one...
C508S290000, C508S231000, C508S221000, C044S348000, C044S331000, C548S546000, C548S547000
Reexamination Certificate
active
06548458
ABSTRACT:
TECHNICAL FIELD
The present invention is directed to novel succinimide-acid compounds prepared by reaction of hydrocarbyl-substituted succinic acylating agents with amino acids, as well as derivatives thereof useful as lubricity additives, lubricant dispersants, friction modifiers, liquid hydrocarbonaceous fuel detergents, antioxidants and alkali and/or alkaline-earth metal detergents.
BACKGROUND OF THE INVENTION
Hydrocarbyl-substituted succinic anhydride derivatives are widely used as fuel and lubricant additives. The hydrocarbyl-substituted succinic anhydride derivatives are typically prepared by reacting a hydrocarbyl-substituted succinic acylating agent with a polyamine to form a succinimide.
For example, hydrocarbyl-substituted succinic anhydrides and derivatives thereof prepared by the thermal reaction of a polyolefin and maleic anhydride, are described, for example in U.S. Pat. Nos. 3,361,673 and 3,676,089. Alternatively, hydrocarbyl-substituted succinic anhydrides can be prepared by the reaction of chlorinated polyolefins with maleic anhydride, are described, for example, in U.S. Pat. No. 3,172,892. Additional examples of hydrocarbyl-substituted succinic anhydrides and derivatives thereof can be found, for example, in U.S. Pat. Nos. 4,234,435; 4,997,456; 5,393,309 and 5,620,486.
U.S. Pat. Nos. 4,218,328; 4,655,949; and 4,834,892 disclose lubricating oil additives comprising metal salts of amino-acids.
None of these patents teach the succinimide-acids, or the derivatives thereof, of the present invention.
SUMMARY OF THE INVENTION
The succinimide-acid compounds of the present invention are prepared by reacting amino acids with a hydrocarbyl-substituted succinic acylating agent. The amino moiety of the amino acid undergoes reaction with the succinic acylating agent resulting in a succinimide moiety. This succinimide contains a pendant carboxylic acid moiety. The pendant carboxylic acid moiety can be utilized by reaction with various compounds including amines, alkoxylated amines and polyols to prepare products useful as dispersants, lubricity additives, friction modifiers, fuel detergents, antioxidants and alkali and/or alkaline-earth metal detergents.
DETAILED DESCRIPTION OF THE INVENTION
The Succinimide-Acid Compound
The succinimide-acid compounds of the present invention are prepared by reacting an amino acid with a hydrocarbyl succinic acylating agent in a reaction media. Suitable reaction media include, but are not limited to, organic solvents, such as toluene, or process oil. Water is a by-product of this reaction. The use of toluene allows for azeotropic removal of water.
The hydrocarbyl-substituted succinic acylating agents include the hydrocarbyl-substituted succinic acids, the hydrocarbyl-substituted succinic anhydrides, the hydrocarbyl-substituted succinic acid halides (especially the acid fluorides and acid chlorides), and the esters of the hydrocarbyl-substituted succinic acids and lower alcohols (e.g., those containing up to 7 carbon atoms), that is, hydrocarbyl-substituted compounds which can function as carboxylic acylating agents. Of these compounds, the hydrocarbyl-substituted succinic acids and the hydrocarbyl-substituted succinic anhydrides and mixtures of such acids and anhydrides are generally preferred, the hydrocarbyl-substituted succinic anhydrides being particularly preferred.
The acylating agent for producing the hydrocarbyl substituted acylating agent is preferably made by reacting a polyolefin of appropriate molecular weight (with or without chlorine) with maleic anhydride. However, similar carboxylic reactants can be employed such as maleic acid, fumaric acid, malic acid, tartaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, mesaconic acid, ethylmaleic anhydride, dimethylmaleic anhydride, ethylmaleic acid, dimethylmaleic acid, hexylmaleic acid, and the like, including the corresponding acid halides and lower aliphatic esters.
The hydrocarbyl-substituted succinic anhydrides are typically prepared by heating a mixture of maleic anhydride and an aliphatic olefin at a temperature of about 175-275° C. The molecular weight of the olefin can vary widely depending upon the intended use of the substituted succinic anhydrides. Typically, the substituted succinic anhydrides will have a hydrocarbyl group of from 8-500 carbon atoms. Friction modifiers, lubricity additives, antioxidants and fuel detergents generally have a hydrocarbyl group of about 8-100 carbon atoms, while substituted succinic anhydrides used to make lubricating oil dispersants will typically have a hydrocarbyl group of about 40-500 carbon atoms. With the very high molecular weight substituted succinic anhydrides, it is more accurate to refer to number average molecular weight (Mn) since the olefins used to make these substituted succinic anhydrides are a mixture of different molecular weight components resulting from the polymerization of low molecular weight olefin monomers such as ethylene, propylene and isobutylene.
The low molecular weight alkyl-substituents typically contain from 8 to 100 carbon atoms, preferably from 12 to 30 carbon atoms, more preferably 16 to 26 carbon atoms. The low molecular weight alkyl substituents include alpha-olefins having single carbon number fraction between C9 and C30 or a mixture of carbon number fractions between C9 and C30. The alpha-olefins may be isomerized to produce an olefin containing an internal double bond, which may be used for alkylation of the hydroxyaromatic compound. Also useful as the low molecular weight alkyl substituents are oligomers of 1-olefins.
Examples of such compounds include tridecylsuccinic acid, pentadecylsuccinic acid, tetradecenylsuccinic acid, hexadecenylsuccinic acid, dodecylsuccinic acid, tetradecylsuccinic acid, hexadecylsuccinic acid, octadecenylsuccinic acid, tetrapropylene-substituted succinic acid, docosenylsuccinic acid and mixtures thereof. Preferred acylating agents are alkyl and/or alkenyl succinic anhydrides in which the alkyl or alkenyl group is substantially straight chain in configuration and contains 12 to 30 carbon atoms, and more preferably an average of about 16 to about 26 carbon atoms. An especially preferred acylating agent of this type is octadecenylsuccinic acid or anhydride.
Still another preferred hydrocarbyl-substituted acylating agent is an alkyl- or alkenylsuccinic acid or anhydride in which the alkyl or alkenyl group is bifurcated on the beta-carbon atom and is composed of two substantially linear chains. Preferred alkyl groups of this type may be represented by the formula
where n is an integer in the range of 2 to 10. A preferred group of such bifurcated alkenyl groups may be represented by the formula
where n is an integer in the range of 2 to 10. It will be understood and appreciated that the double bond in such alkenyl group may be isomerized to different positions from that depicted (which is the preferred position) by treating the alkenylsuccinic acid or anhydride with an isomerization catalyst such as silica gel, a trialkylborane, or the like. Such alkyl- and alkenyl substituted succinic acids and anhydrides can be formed from dimerized 1-olefins such as by dimerizing 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 4-methyl-1-pentene, 6-methyl-1-heptene, 5-ethyl-1-decene, or 3,5,5-trimethyl-1-undecene with an aluminum alkyl dimerization catalyst according to known procedures. See for example Ziegler et al, Ann. 629, 121-166 (1960) all disclosure of which is incorporated herein by reference. The resultant dimerized olefin (sometimes referred to as a vinylidene olefin) is then used to alkylate maleic anhydride or an ester of maleic acid, etc., to form the alkenyl-substituted succinic acid compound by the “ene” reaction. See in this connection Hoffman, Angew. Chem., Int. Ed. (English), 8, 556-577 (1969); Snider, J. Org. Chem., 39, 255 (1974); and Keung et al, J. Chem. Educ., 49. 97-100 (1972), all disclosures of which are incorporated herein by reference. As is well known, the “ene” reaction may be facilit
Ethyl Corporation
McAvoy Ellen M.
Rainear Dennis H.
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