Classifications

• • 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
  • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
  • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
  • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
  • C08G63/16—Dicarboxylic acids and dihydroxy compounds
  • C08G63/20—Polyesters having been prepared in the presence of compounds having one reactive group or more than two reactive groups
• • 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
  • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
  • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
  • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
• • 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
  • C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
  • C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
  • C10M129/68—Esters
  • C10M129/78—Complex esters, i.e. compounds containing at least three esterified carboxyl groups and derived from the combination of at least three different types of the following five types of compound: monohydroxy compounds, polyhydroxy compounds, monocarboxylic acids, polycarboxylic acids, hydroxy carboxylic acids
• • 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
  • C10M145/00—Lubricating compositions characterised by the additive being a macromolecular compound containing oxygen
  • C10M145/18—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
  • C10M145/22—Polyesters
• • 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
  • C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
  • C10M169/04—Mixtures of base-materials and additives
• • 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
  • C10M2203/102—Aliphatic fractions
  • C10M2203/1025—Aliphatic fractions used as base material
• • 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
  • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
  • C10M2207/28—Esters
  • C10M2207/30—Complex esters, i.e. compounds containing at leasst three esterified carboxyl groups and derived from the combination of at least three different types of the following five types of compounds: monohydroxyl compounds, polyhydroxy xompounds, monocarboxylic acids, polycarboxylic acids or hydroxy carboxylic acids
• • 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
  • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
  • C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
  • C10M2209/102—Polyesters
• • 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
  • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
  • C10N2020/01—Physico-chemical properties
  • C10N2020/04—Molecular weight; Molecular weight distribution
• • 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
  • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
  • C10N2030/02—Pour-point; Viscosity index
• • 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
  • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
  • C10N2030/70—Soluble oils
• • 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
  • C10N2040/20—Metal working
• • 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
  • C10N2040/20—Metal working
  • C10N2040/22—Metal working with essential removal of material, e.g. cutting, grinding or drilling
• • 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
  • C10N2040/20—Metal working
  • C10N2040/24—Metal working without essential removal of material, e.g. forming, gorging, drawing, pressing, stamping, rolling or extruding; Punching metal
• • 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
  • C10N2070/00—Specific manufacturing methods for lubricant compositions

Definitions

• TITLE POLYMERIC POLYOL ESTERS FROM TRIHYDRIC POLYOLS FOR USE IN METALWORKING WITH IMPROVED SOLUBILITY
• polymeric polyol ester additives having compatibility with paraffinic mineral oil basestocks (hydrotreated) and usefulness in metalworking applications are described. While these polymeric polyol ester molecules are generally free of phosphorus, sulfur, and other heteroatoms (other than oxygen, carbon, and hydrogen) they can be part of an additive package that includes sulfurized hydrocarbons and phosphorus containing an ti wear or extreme pressure additives.
• Metalworking operations include for example, rolling, forging, hot-pressing, blanking, bending, stamping, drawing, cutting, punching, spinning and the like and generally employ a lubricant to facilitate the same.
• Lubricants generally improve these operations in that they can provide films of controlled friction or slip between interacting metal surfaces and thereby reduce the overall power required for the operations, and prevent sticking and decrease wear of dies, cutting bits and the like.
• the lubricant is expected to help transfer heat away from a particular metalworking contact point.
• the metal working fluid may provide a residual film on the metal part thereby adding a corrosion inhibiting property to the metal being processed.
• Metal working fluids often comprise a earner fluid and a multitude of specialty additives.
• the carrier fluid imparts some general lubricity to the metal surface and carries/delivers the specialty additives to the metal surfaces.
• the specialty additives can impart a variety of properties including friction reduction beyond hydrodynamic film lubrication, metal corrosion protection, extreme pressure or antiwear effects, etc.
• Carrier fluids include various petroleum distillates include American Petroleum Institute Group I-N basestocks and/or water.
• Group I basestocks are primarily direct fractional distillation products of petroleum.
• Group II and III basestocks are further refined petroleum products such as hydrotreated distillation products that have reduced amounts of unsaturation (e.g. less than 1 wt.%) and cyclic distillation products.
• the specialty additives can exist within the carrier fluid in a variety of forms including as dissolved, dispersed in, and partially soluble materials. Some of the metal working fluid is lost to or deposited on the metal surface during the working process; some is lost to the environment as spillage, sprays, etc; and some is recyclable if the carrier fluid and additives haven't degraded significantly during use. Due to entry of a percentage of the metal working fluid into process goods and industrial process streams, it is desirable if the components to the metal working fluid are eventually fully biodegradable and pose little risk of bioaccumulation.
• Polymeric polyol esters exhibit compatibility with and some solubility with both hydrocarbon oils and water carrier fluids, depending on molecular structure, molecular weight etc. They are biodegradable and if they don't contain other heteroatoms pose little risk of bioaccumulation. Polymeric polyol esters from pentaerythritol are known as additives for metalworking but suffer from compatibility problems at some temperatures with some lubricant basestocks materials.
• Polymeric polyol esters with improved solubility characteristics and lower acid numbers can be prepared using a portion of a trihydric alcohol like trimethylolpropane to replace a portion or all of the of pentaerythritol in a polymeric polyol ester used as a lubricant additive for metalworking. It might have been anticipated that a polyol ester including trimethylolpropane would have less short chain branching and thus reduced solubility in solvents or Group II and III basestocks, but experimental data confirms that in many instances incorporation of trimethylolpropane as a partial or complete replacement for pentaerythritol results in enhanced solubility.
• Another benefit of partial or complete replacement of pentaerythritol is that lower acid numbers are obtained in these particular polymer formulations when trimethylolpropane is part or all of the total polyol charge.
• the acid numbers are about 20 mgKOH/g of additive.
• trimethylolpropane replaces about 50 mole percent of the pentaerythritol under the same reaction conditions, the acid number can readily be reduced to less than 8 mgKOH/g and more desirably less than 5 mgKOH/g.
• the acid number can go below 5 mgKOH/g and more desirably less than 3 mgKOH/g. Higher acid numbers are undesirable to the extent that they promote coupling of polymer chains, which can significantly reduce the solubility of polymeric polyol esters in hydrocarbon oils.
• the polymeric polyol ester of this disclosure is made from the following components.
• the first is a generally linear monocarboxylic acid where R is an alk(en)yl group of 11 to 19 carbon atoms.
• the second is an alkanedioic acid such as adipic acid shown below.
• the third is an alk(en)yl substituted succinic acid or its anhydride where Ri has from 15 to 20 carbon atoms.
• the fourth is a trihydric alcohol and in the preferred embodiment is trimethylolpropane as shown below.
• the fifth component in embodiment A is not present in any substantial amount in embodiment B.
• the fifth component when present is pentaerythritol as shown below.
• the polymeric polyol ester is manufactured from four or five different components depending on whether one is making embodiment A including about 50-60 percent trihydric alcohol based on the polyhydric alcohol components or embodiment B including about 90-100 percent trihydric alcohol based on the
• the first component in the polymeric polyol ester is a substantially linear monocarboxylic acid having form about 12 to about 20 carbon atoms.
• these acids are coco fatty acid and tall oil fatty acid. These acids have some
• these (repeating units derived from monocarboxylic acids) are present in amounts from about 40 to 70 wt.%, more desirably from about 40 to 60 wt.%, and preferably from about 50-55 wt.% based on the weight of all the components in the polymeric polyol ester.
• repeating unit will be used to describe the acid, diacid, or polyol component to a repeating unit, while a more academic approach might require a repeating unit to include both an acid component and an alcohol component.
• This will be used interchangeably with wt.% of the repeating units from the particular acid, diacid, or polyol of the polyol ester since the difference in weights of the precursors and the fragment derived therefrom in the repeating units will be insubstantial.
• the amounts of linear monocarboxylic acids will be from about 10 to 90 and more preferably from about 30 to 60 wt.%.
• the second component is an alkanedioic acid having from 4 to 6 carbon atoms.
• a preferred alkanedioic acid is adipic acid.
• This component is primarily a chain extender for the formation of the polyol ester.
• the alkanedioic acid is desirably present in embodiment A in an amount from about 5 to 30 wt.%, more desirably from about 10 to 20 wt.%, and preferably from about 12 to 15 wt.% based on all of the repeating units in the polymeric polyol ester.
• the alkanedioic acid is desirably present in embodiment B in an amount from about 5 to 30 wt.% and more desirably from about 10 to 15 wt.% based on all of the repeating units in the polymeric polyol ester.
• the third component is an alk(en)yl substituted succinic acid or its anhydride.
• Alk(en)yl is shorthand for the term alkyl or alkenyl with alkenyl varying from alkyl by the inclusion of one or more carbon to carbon double bonds in the molecule fragment.
• alk(en)yl substituted succinic acid or its anhydride While unsaturation is not particularly desirable in the alk(en)yl substituted succinic acid or its anhydride, it is understood that some unsaturation may be presence due to the chemical reactions used to form the alk(en)yl substituted succinic acid reactant.
• the alk(en)yl group desirably has from about 15-20 carbon atoms so the entire molecule has about 19-24 carbon atoms along with the respective amount of hydrogen and oxygen atoms.
• a preferred alk(en)yl group would include one with one or more aliphatic branches and a desirable example would be isooctadecyl group resulting in isooctadecyl succinic anhydride.
• the alk(en)yl succinic acid or its anhydride is present in embodiment A as repeating units in the polymeric polyol ester as from about 10 to 20 wt.%, more desirably from about 12 to 16 wt.%, and preferably from about 14 to 15 wt.% based on all of the repeating units therein.
• the alk(en)yl succinic acid or its anhydride is present in embodiment B as repeating units in the polymeric polyol ester as from about 1 to 50 wt.%, more desirably from about 5 to 30 wt.%, and preferably from about 10 to 20 wt.%.
• the fourth component is the trihydric polyol. While a variety of trihydric alcohols could be used having from about 4 to 10 carbon atoms, trimethylolpropane is preferred due to the chemical stability of polyol esters made from trimethylolpropane relative to other trihydic alcohols. Desirably in embodiment A the trihydric alcohol is present from about 8 to 20 wt.% , more desirably from about 9 to 13 wt.% in the repeating units, and preferably from about 11 to 12 wt.% based on all of the repeating units. Desirably in embodiment B the trihydric alcohol is present from about 5 or 10 to 30 wt.% in the repeating units and more desirably from about 10 to 20 wt.% based on all of the repeating units.
• pentaerythritol is only present in embodiment A and not present intentionally in embodiment B.
• Pentaerythritol has the structure already shown. It is preferred over other tetrahydric alcohols because the particular structure with the (central) beta carbon from all the oxygen atoms of the hydroxyl groups lacks any attached hydrogen atoms. This helps prevent some chemical reactions that occur when the beta carbon from a hydroxyl group has a hydrogen atom(s) that can be abstracted.
• pentaerythritol is generally defined by the formula given, it is well known that commercial sources of pentaerythritol generally include trace amounts of dimer, trimer and higher oligomers from coupling pentaerythritol.
• pentaerythritol will include the generally commercially acceptable forms thereof that include some dimer, trimer, etc.
• Pentaerythritol is desirably present in embodiment A in an amount from about 5 to 15 wt.%, more desirably about 7 to 10 wt.% and preferably about 8 to 9 wt.%.
• the polymeric polyol ester can be present in a metal working from trace amounts to large amounts depending upon the application. In most conventional applications the use rate would be about 0.05 to about 50 wt.% and more desirably from about 0.1 to about 25 wt.% of this polymeric polyol ester in a hydrocarbon diluent oil.
• This particular polymeric polyol ester can be used with a wide variety of natural and synthetic oils that might be useful in metal working applications.
• This particular polymeric polyol ester has a lower pour point than polymeric polyol esters from pentaerythritol alone and similar acids and thus is more easily handled and measured at lower temperatures (requires no heating or less heating to achieve pumpable neat viscosities).
• the molecular weight of this polymeric polyol can be adjusted to achieve optimal solubility and compatibility with other components in the metal working fluid (e.g. the diluent oil).
• the number average molecular can vary from about 10,000 to about 1,000,000 for most applications and more desirably from about 20,000 to about 500,000.
• polymeric polyol esters often have number molecular weights controlled to 20,000 to 100,000.
• Acid number and hydroxyl number of the polymeric polyol ester are influenced by the molecular weight. In this application neither a large excess of residual hydroxyl nor acid groups is desirable.
• the stoicheometry of the acid groups and hydroxyl groups is near equivalent and might be expected to vary by 1, 2, or 3 mole percent up to 10 mole percent.
• Acid numbers of less than 20 and more desirably less than 10, 8, 5 or 3 mg KOH g polymer are preferred by the industry but higher acid numbers would not necessarily preclude use as a metal working additive.
• polymeric polyol esters can be made with a variety of processes well known in the art. Since it is a condensation polymerization it is desirable to purge water out of the reactants to push the condensation reaction towards completion. A diluent may be used. A suggested procedure used to make these includes mixing the reactants in a stirred reactor under an inert gas such as nitrogen and at a temperature of about 240-255 C until the acid number is acceptable (e.g. normally the reaction was stopped at an acid number between 3-8 mgKOH/g of polymer). This typically was 6-8 hours using the reactants of embodiment A.
• the polymeric polyol ester need not be the only additive in a metal working fluid. These additives work well with phosphorus and/or sulfur containing extreme pressure (EP) additives.
• EP extreme pressure
• the polymeric polyol esters can function as a partial EP replacement for chloroparaffin EP additives when used with a sulfur and/or phosphorus EP additives.
• the polymeric polyol esters work well with the organic phosphorus compounds listed in US Patent 5,798,322 as additives for metal working in combination with the polymeric polyol ester additives in that patent.
• US 5,798,322 is hereby incorporated by reference for its teachings on metal working formulation in general and its teachings on additives/variations on formulations using polymeric polyol ester additives.

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• Oil, Petroleum & Natural Gas (AREA)
• Health & Medical Sciences (AREA)
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• Polyesters Or Polycarbonates (AREA)

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• 2003
  • 2003-03-13 EP EP03716675.8A patent/EP1487945B1/en not_active Expired - Lifetime
  • 2003-03-13 US US10/508,275 patent/US7534748B2/en not_active Expired - Lifetime
  • 2003-03-13 WO PCT/US2003/008244 patent/WO2003080772A1/en not_active Ceased
  • 2003-03-13 AU AU2003220375A patent/AU2003220375A1/en not_active Abandoned
  • 2003-03-13 JP JP2003578503A patent/JP2005520919A/ja active Pending
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