Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
  • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
  • C08F290/04—Polymers provided for in subclasses C08C or C08F
  • C08F290/042—Polymers of hydrocarbons as defined in group C08F10/00
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
  • C08F222/04—Anhydrides, e.g. cyclic anhydrides
  • C08F222/06—Maleic anhydride
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F8/00—Chemical modification by after-treatment
  • C08F8/02—Alkylation
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F8/00—Chemical modification by after-treatment
  • C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
  • C08F8/32—Introducing nitrogen atoms or nitrogen-containing groups by reaction with amines
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F8/00—Chemical modification by after-treatment
  • C08F8/48—Isomerisation; Cyclisation
• • 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
  • C10M145/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • C10M145/10—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate
  • C10M145/16—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate polycarboxylic
• • 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
  • C10M149/00—Lubricating compositions characterised by the additive being a macromolecular compound containing nitrogen
  • C10M149/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • C10M149/10—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a nitrogen-containing hetero ring
• • 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
  • C10M149/00—Lubricating compositions characterised by the additive being a macromolecular compound containing nitrogen
  • C10M149/12—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2800/00—Copolymer characterised by the proportions of the comonomers expressed
  • C08F2800/10—Copolymer characterised by the proportions of the comonomers expressed as molar percentages
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2810/00—Chemical modification of a polymer
  • C08F2810/30—Chemical modification of a polymer leading to the formation or introduction of aliphatic or alicyclic unsaturated groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2810/00—Chemical modification of a polymer
  • C08F2810/40—Chemical modification of a polymer taking place solely at one end or both ends of the polymer backbone, i.e. not in the side or lateral chains
• • 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
  • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
  • C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
• • 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
  • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
  • C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
  • C10M2205/028—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms
• • 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
  • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions
  • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
  • C10M2215/04—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms
• • 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
  • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions
  • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
  • C10M2215/04—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms
  • C10M2215/042—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Alkoxylated derivatives thereof
• • 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
  • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions
  • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
  • C10M2215/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
  • C10M2215/066—Arylene diamines
• • 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
  • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions
  • C10M2215/086—Imides [having hydrocarbon substituents containing less than thirty carbon atoms]
• • 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
  • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions
  • C10M2215/24—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions having hydrocarbon substituents containing thirty or more carbon atoms, e.g. nitrogen derivatives of substituted succinic acid
  • C10M2215/28—Amides; Imides
• • 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
  • C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
  • C10M2217/06—Macromolecular compounds obtained by functionalisation op polymers with a nitrogen containing compound
• • 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
  • C10N2030/04—Detergent property or dispersant property
  • C10N2030/041—Soot induced viscosity control
• • 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
  • C10N2040/25—Internal-combustion engines

Definitions

• the disclosed subject matter relates to copolymers made using polyolef ⁇ ns and unsaturated acidic reagents, dispersants using same, and methods of making same.
• Copolymers of polyolefins and unsaturated acidic reagents, and dispersants made from same are useful components in lubricants, fuels, and other applications.
• polyisobutylene (PIB) succinic anhydride (SA) copolymers commonly referred to as "polyPIBSA”
• SA polyisobutylene
• polyPIBSA succinic anhydride
• the polyPIBSA is then reacted with a polyamine to form polysuccinimides, or otherwise derivitized, for use in different compositions.
• U.S. Patent Nos. 5,112,507, 5,175,225, 5,616,668, 6,451,920, and 6,906,011 see, e.g., U.S. Patent Nos. 5,112,507, 5,175,225, 5,616,668, 6,451,920, and 6,906,011 , the entire contents of each of which are hereby incorporated herein by reference.
• polyPIBSA made using conventional methods does not necessarily have appropriate properties to be useful in a variety of climates.
• conventional polyPIBSA, and/or dispersants made from same may have a Cold Cranking Simulator (CCS) viscosity and/or kinematic viscosity (kv) that is too high at relatively low temperatures (e.g. , below O 0 C) to enable the use of that polyPIBSA in lubricants intended for harsh winter climates.
• CCS Cold Cranking Simulator
• kv kinematic viscosity
• copolymers made by copolymerizing an allyl-terminated polyolefin with an unsaturated acidic reagent, dispersants made using such copolymers, and methods of making same.
• a copolymer of an unsaturated acidic reactant and a high molecular weight polyolefin, wherein the polyolefin includes an allyl-terminated polymeric product is provided.
• the allyl-terminated polymeric product is prepared by:
• step (b) reacting the carbocation terminated polyolefin from step (a) with an allylsilane compound in the presence of a Lewis acid, and
• step (c) terminating step (b) to form the allyl-terminated polymeric product.
• a copolymer of an unsaturated acidic reactant and a high molecular weight polyolefin, wherein the polyolefin includes an allyl-terminated quasi-living polymeric product is provided.
• the allyl-terminated quasi-living polymeric product is prepared by (a) forming a quasi-living tert-halide terminated polyolefin under suitable quasi- living conditions in the presence of a Lewis acid, and (b) reacting the quasi- living tert-halide terminated polyolefin with an allylsilane compound, and (c) terminating the reaction of step (b) to form the allyl terminated quasi-living polymeric product.
• the copolymer can be formed by contacting the polyolefin with the unsaturated acidic reactant in the presence of a free radical initiator, such as a peroxide.
• the high molecular weight polyolefin has a number average molecular weight between about 500 and about 10,000, e.g., between about 900 and about 5,000, e.g., between about 900 and about 2,500, or, e.g., between about 2,000 and about 4,000.
• the copolymer has a succinic ratio of between about 1 and about 2, or between about 1.0 and about 1.5,.
• the polyolefin has an allylic end-group content of at least about 75%, or at least about 90%, or at least about 91%, or at least about 92%, or at least about 93%, or at least about 94%, or at least about 95%, or at least about 96%, or at least about 97%, or at least about 98%, or at least about 99%, or about 100%.
• the polyolefin has a dispersion index of less than about 2.0, or less than about 1 A, or less than about 1.3, or less than about 1.2, or less than about 1.1 , or about 1.0.
• the high molecular weight polyolefin is polyisobutylene. In some embodiments, the high molecular weight polyolefin has sufficient molecular weight and chain length to lend solubility in lubricating oil to its reaction products. In some embodiments, the reaction products can dissolve in aliphatic and/or aromatic hydrocarbons such as lubricating oils and fuels in substantially all proportions.
• the unsaturated acidic reactant can be of the formula:
• the copolymer has the formula:
• Ri, R 2 , R 3 , and R 4 are hydrogen and the other is high molecular weight polyalkyl; wherein each of x, y, and n is, independently, 1 or greater, wherein the ratio of x:y is about 2: 1 to about 1 : 1 , or about 1.5:1 to about 1 :1. In some embodiments, n is between 1 and 40, or between 1 and 20, or between 1 and 10, or 2 or greater.
• the high molecular weight polyalkyl can include a polyisobutyl group having at least 30 carbon atoms, or at least 50 carbon atoms.
• the copolymer of this invention has a degree of oligomerization of between 1 and 40, or between 1 and 20, or between 1 and 10, or 2 or greater, and the % actives is greater than about 60%, or greater than about 70%, or greater than about 75%, or greater than about 80%, or greater than about 85%, or greater than about 90%, or greater than about 95%.
• % actives refers to the amount of copolymer in the product of the reaction of the unsaturated acidic reactant and high molecular weight polyolefin.
• a polysuccinimide prepared by reacting: a) a copolymer of an unsaturated acidic reactant and a high molecular weight polyolefin, wherein the polyolefin includes an allyl-terminated polymeric product, with b) an amine, a polyamine having at least two basic nitrogen atoms, or mixtures thereof, is provided.
• a lubricating oil composition including a major amount of an oil of lubricating viscosity and a minor amount of the above-mentioned polysuccinimide is provided.
• a method of making a copolymer includes (a) forming a high molecular weight, allyl-terminated polyolefin; and (b) contacting the polyolefin with an unsaturated acidic reactant in the presence of a free radical initiator (such as a peroxide) to form a copolymer.
• a free radical initiator such as a peroxide
• forming the polyolefin includes forming a tert-halide terminated polyolefin, and contacting the tert-halide terminated polyolefin with an allylsilane compound and a Lewis acid.
• allyl refers to the following structure:
• alkyl refers to a carbon chain or group containing from 1 to 20 carbons, or 1 to 16 carbons. Such chains or groups may be straight or branched. Exemplary alkyl groups herein include, but are not limited to, methyl, ethyl, propyl, isopropyl, isobutyl, n-butyl, sec-butyl, tert-butyl, iospentyl, neopentyl, tert-pentyl, or isohexyl. As used herein, “lower alkyl” refers to carbon chains or groups having from 1 carbon atom to about 6 carbon atoms.
• alkenyl refers to a carbon chain or group containing from 2 to 20 carbons, or 2 to 16 carbons, wherein the chain contains one or more double bonds.
• An example includes, but is not limited to, an allyl group.
• the double bond of an alkenyl carbon chain or group may be conjugated to another unsaturated group.
• An alkenyl carbon chain or group may be substituted with one or more heteroatoms.
• An alkenyl carbon chain or group may contain one or more triple bonds.
• alkynyl refers to a carbon chain or group containing from 2 to 20 carbons, or 2 to 16 carbons, wherein the chain contains one or more triple bonds.
• An example includes, but is not limited to, a propargyl group.
• the triple bond of an alkynyl carbon chain or group may be conjugated to another unsaturated group.
• An alkynyl carbon chain or group may be substituted with one or more heteroatoms.
• An alkynyl carbon chain or group may contain one or more double bonds.
• aryl refers to a monocyclic or multicyclic aromatic group containing from about 6 to about 30 carbon atoms.
• Aryl groups include, but are not limited to, fluorenyl, phenyl, or naphthyl.
• alkaryl refers to an aryl group substituted with at least one alkyl, alkenyl, or alkynyl group.
• aralkyl refers to an akyl, alkenyl, or alkynyl group substituted with at least one aryl group.
• amide refers to a compound of formula:
• Rj-R 3 are each, independently, hydrogen or hydrocarbyl.
• amine refers to a compound of formula:
• Ri-R 3 are each, independently, hydrogen or hydrocarbyl.
• carbocation terminated polyolefin refers to a polyolefin containing at least one carbocation end group. Examples include, but are not limited to, compounds of the formula:
• chain end concentration refers to the sum of the concentrations of olefin end groups, tert-halide end groups, and carbenium ions.
• the chain end concentration is approximately equal to the initiator concentration.
• the functionality of the initiator equals x
• the chain end concentration is approximately equal to x times the initiator concentration.
• chain transfer agent refers to a compound which interchanges its halide ion with a carbenium ion to form a new carbenium ion.
• common ion salt refers to an ionic salt that is optionally added to a reaction performed under quasiliving carbocationic polymerization conditions to prevent dissociation of the propagating carbenium ion and counter-ion pairs.
• common ion salt precursor refers to an ionic salt that is optionally added to a reaction performed under quasiliving carbocationic polymerization conditions, which generates counter-anions that are identical to those of the propagating chain ends, via in situ reaction with a Lewis acid.
• diluting agent refers to a liquid diluting agent or compound. Diluents may be a single or a mixture of two or more compounds. Diluents may completely dissolve or partially dissolve the reaction components. Examples include, but are not limited to, hexane or methyl chloride, or mixtures thereof.
• dispersion index refers to the ratio of the weight average molecular weight of a polymer to the number average molecular weight of the polymer, and is reflective of the distribution of molecular masses in a polymer.
• a dispersion index of 1 indicates that the polymer is monodisperse.
• a dispersion index of greater than 1 indicates that there is a distribution of molecular masses of polymer chains in the polymer.
• electron donor refers to a molecule that is capable of donating a pair of electrons to another molecule. Examples include, but are not limited to, molecules capable of complexing with Lewis acids. Further examples include, but are not limited to, bases and/or nucleophiles. Further examples include, but are not limited to, molecules capable of abstracting or removing a proton.
• free radical initiator refers to a material that decomposes at elevated temperatures to form free radicals which react with an unsaturated acidic reagent and a polyolefin to form a copolymer.
• halide refers to F, Cl, Br, or I.
• hydrocarbyl refers to a monovalent linear, branched or cyclic group which contains only carbon and hydrogen atoms.
• inifer refers to a compound that acts as both an initiator and a chain transfer agent.
• initiator refers to a compound that provides a carbocation for a quasi living or inifer polymerization. Examples include, but are not limited to, compounds or polyolefins with one or more tertiary end groups.
• An initiator may be mono-functional or multi-functional.
• mono-functional initiator refers to an initiator that provides approximately one stoichiometric equivalent of carbocation relative to initiator.
• multi-functional initiator refers to an initiator that provides approximately x stoichiometric equivalents of carbocation relative to initiator, wherein x represents the functionality of the initiator.
• the chain end concentration is approximately equal to the initiator concentration.
• the functionality of the initiator equals x, then the chain end concentration equals x times the initiator concentration.
• ionized polyolefin refers to a polyolefin containing at least one carbenium ion.
• An example includes, but is not limited to, a tert-halide terminated polyolefin that has been ionized into a carbocation terminated polyolefin.
• a further example includes, but is not limited to, a quasiliving carbocation terminated polyolefin.
• a further example includes, but is not limited to, a vinylidene terminated polyolefin that has been ionized into an ionized polyolefin or quasiliving carbocation terminated polyolefin.
• a further example includes, but is not limited to, a polyolefin containing an olefin that has been ionized into a quasi-living carbocation terminated polyolefin or an ionized polyolefin.
• a further example includes, but is not limited to, an ionized polyolefin derived from an inifer.
• Lewis acid refers to a chemical entity that is capable of accepting a pair of electrons.
• “monomer” refers to an olefin that is capable of combining with a carbocation to form another carbocation.
• pyridine derivative refers to a compound of the formula:
• Ri, R 2 , R 3 , R 4 , and R 5 are each, independently, hydrogen or hydrocarbyl; or Ri and R 2 , or R 2 and R 3 , or R 3 and R 4 , or R 4 and R 5 independently form a fused aliphatic ring of about 4 to about 7 carbon atoms or a fused aromatic ring of about 5 to about 7 carbon atoms.
• quadsiliving carbocationic polymerization conditions refers to quasiliving polymerization conditions that allow for the formation of quasiliving carbocationic polyolefins.
• quadsiliving carbocationic polyolefin refers to a carbocationic polyolefin that has been formed under quasiliving polymerization conditions.
• quadsiliving polymerization refers to polymerizations that proceed in the absence of irreversible chain-breaking events. Quasiliving polymerizations proceed by initiation and is followed by propagation, wherein propagating (living) species are in equilibrium with non-propagating (non-living) polymer chains.
• quadsiliving polymerization conditions refers to reaction conditions that allow quasiliving polymerization to occur.
• termination or “terminating” refers to the chemical reaction that terminates a polymerization process by destruction of a Lewis acid.
• tert-halide terminated polyolefin refers to a polyolefin that contains at least one tertiary halide end group.
• An example includes, but is not limited to, a compound of formula:
• vinylidene refers to a compound of the formula:
• R is hydrocarbyl, e.g., methyl or ethyl.
• R is methyl
• the vinylidene is methylvinylidene.
• methods of forming copolymers such as those described herein include the steps of (1) providing a high molecular weight polyolefin, which is an allyl-terminated polymeric product, and (2) reacting the polyolefin with an unsaturated acidic reagent in the presence of a free radical initiator, to form the copolymer.
• the polyolefin is a polyolefin having an allyl-terminated chain end
• the free radical initiator is a peroxide
• the unsaturated acidic reagent is maleic anhydride.
• the resulting copolymer is of the formula:
• , R 2 , R 3 , and R 4 are hydrogen and the other is high molecular weight polyalkyl; wherein each of JC, y, and n is, independently, 1 or greater.
• the ratio of x:y is from about 2: 1 to about 1 :1, or about 1.5:1 to about 1 : 1, and /i is between 1 and 40, or between 1 and 20, or between 1 and 10, or 2 or greater.
• Rj, R 2 , and R 3 are hydrogen
• R 4 is a high molecular weight polyisobutylene chain.
• Such a copolymer is referred to as polyallyl polyisobutylene succinic anhydride, or polyallyl PIBSA.
• the polyolefin is allyl-terminated PIB of the formula:
• allylic end groups e.g., at least about 75%, or at least about 90%, or at least about 91%, or at least about 92%, or at least about 93%, or at least about 94%, or at least about 95%, or at least about 96%, or at least about 97%, or at least about 98%, or at least about 99%, or about 100%.
• allylic end groups e.g., at least about 75%, or at least about 90%, or at least about 91%, or at least about 92%, or at least about 93%, or at least about 94%, or at least about 95%, or at least about 96%, or at least about 97%, or at least about 98%, or at least about 99%, or about 100%.
• allylic end groups also has a DI of less than about 2.0, or less than about 1.4, or less than about 1.3, or less than about 1.2, or less than about 1.1 , or about 1.0.
• the allyl-terminated PIB is contacted with the free radical initiator, e.g., a peroxide such as di-tert-amyl peroxide, and with the unsaturated acidic reactant maleic anhydride, to form polyallyl PIBSA.
• the free radical initiator e.g., a peroxide such as di-tert-amyl peroxide
• maleic anhydride unsaturated acidic reactant maleic anhydride
• conventional PIB it is meant PIB that has a relatively low percent of methylvinylidene end groups, e.g., less than about 80%, and has a high dispersion index (DI), e.g., greater than 1.4.
• DI dispersion index
• Such conventional PIB is sometimes referred to as “high methylvinylidene PIB,” or “highly reactive PIB.”
• the use of allyl-terminated PIB in the formation of polyallyl PIBSA provides a polymeric product having a degree of oligomerization of between 1 and 40, or between 1 and 20, or between 1 and 10, or 2 or greater; and the % actives is greater than about 60%, or greater than about 70%, or greater than about 75%, or greater than about 80%, or greater than about 85%, or greater than about 90%, or greater than about 95%.
• the copolymer has a succinic ratio of between about 1 and about 2, or between about 1.0 and about 1.5.
• the polyolefin has an allylic end- group content of at least about 75%, or at least about 90%, or at least about 91%, or at least about 92%, or at least about 93%, or at least about 94%, or at least about 95%, or at least about 96%, or at least about 97%, or at least about 98%, or at least about 99%, or about 100%.
• the polyolefin has a dispersion index of less than about 2.0, or less than about 1.4, or less than about 1.3, or less than about 1.2, or less than about 1.1 , or about 1.0.
• the relatively high degree of oligomerization of polyallylPIBSA is believed to be due to the fact that allyl terminated PIB has fewer allylic protons compared to conventional PIB resulting in less efficient chain transfer and a higher degree of oligomerization (higher molecular weight).
• allyl terminated polyolefins are prepared by first ionizing a polyolefin to form a carbocation terminated polyolefin, followed by reaction of the carbocation terminated polyolefin with an allyl silane compound to form the allyl terminated polyolefin.
• Carbocation terminated polyolefins may be made by any suitable method known to those of skill in the art. Examples include, but are not limited to, ionizing a tert-halide with a Lewis acid; ionizing a preformed polyolefin with a proton source; polymerizing an olefin monomer under quasiliving carbocationic polymerization conditions; or performing the "inifer" method.
• the carbocation terminated polyolefin contains one or more carbocation end groups. In some embodiments, the carbocation terminated polyolefin contains one carbocation end group. In some embodiments, the carbocation terminated polyolefin contains two carbocation end groups. In some embodiments, the carbocation terminated polyolefin contains three carbocation end groups. In some embodiments, the carbocation terminated polyolefin is a polyisobutylene with a cationic end group. In some embodiments, the carbocation terminated polyolefin is a compound of the following formula:
• the carbocation terminated polyolefin is derived from a tert-halide terminated polyolefin. In some embodiments, the carbocation terminated polyolefin is derived form a tert-chloride terminated polyolefin, tert-bromide terminated polyolefin, or tert-iodide terminated polyolefin. In some embodiments, the carbocation terminated polyolefin is derived from a tert-chloride terminated polyolefin or tert-bromide terminated polyolefin. In some embodiments, the carbocation terminated polyolefin is derived from tert-chloride terminated polyisobutylene of the following formula:
• Tert-halide terminated polyolefins may be made by any method known to those of skill in the art.
• the carbocation terminated polyolefin is generated by contacting a tert-halide terminated polyolefin with a Lewis acid. In some embodiments, the carbocation terminated polyolefin is generated by contacting a tert-chloride terminated polyolefin, tert-bromide terminated polyolefin, or tert-iodide terminated polyolefin with a Lewis acid. In some embodiments, the carbocation terminated polyolefin is generated by contacting a tert-chloride terminated polyolefin with a Lewis acid.
• the tert-halide is derived from an inifer.
• the carbocation terminated polyolefin is derived from a preformed polyolefin.
• such preformed polyolefin contains one or more double bonds.
• such preformed polyolefin contains one double bond.
• such preformed polyolefin is a polyisobutylene derivative.
• such preformed polyolefin contains one or more endo olefins.
• the carbocation terminated polyolefin is generated by contacting a proton source with a preformed polyolefin in the presence of a Lewis acid. In some embodiments, the carbocation terminated polyolefin is generated by contacting a preformed polyolefin containing one or more double bonds with a proton source in the presence of a Lewis acid. In some embodiments, the carbocation terminated polyolefin is generated by contacting a preformed polyolefin containing one double bond with a proton source in the presence of a Lewis acid.
• the carbocation terminated polyolefin is generated by contacting a polyisobutylene derivative with a proton source in the presence of a Lewis acid. In some embodiments, the carbocation terminated polyolefin is generated by contacting a preformed polyolefin containing one or more endo olefins with a proton source in the presence of a Lewis acid. (c) Carbocation terminated polyolefins from the inifer method
• the carbocation terminated polyolefin is derived from an inifer using methods known to those of skill in the art. Non-limiting examples of such methods are described in U.S. Pat Nos. 4,276,394 and 4,568,732, each of which is incorporated by reference herein.
• a monomer is reacted with an inifer carrying at least two tertiary halogens under cationic polymerization conditions.
• the inifer is a binifer or a trinifer.
• the inifer is tricumyl chloride, paradicumyl chloride, or tricumyl bromide.
• the carbocation terminated polyolefin is derived from olefinic monomers under quasi-living carbocationic conditions. Under such conditions, a quasi-living carbocationic polyolefin is generated. Such conditions may be achieved by any quasiliving method known to those of skill in the art.
• a monomer, an initiator, and a Lewis acid are used. Non-limiting examples of such methods are described in EP 206756 Bl and WO 2006/1 10647 Al , both of which are incorporated by reference herein.
• the carbocation terminated polyolefin is a quasi-living carbocationic polyisobutylene of the following formula:
• the initiator is a compound or polyolefin with one, or more than one, end group capable of initiating a cationic olefin polymerization.
• the initiator can be a compound of formula (X'-CR a R b ) n R c wherein R a and Rb are, independently, hydrogen, alkyl, aryl, alkaryl, or aralkyl, provided that at least one of R 8 or R b is not hydrogen; and R 0 has a valence of n, and n is an integer of one to 4.
• X 1 is an acetate, etherate, hydroxyl group, or a halogen.
• R 3 , R b and Rc are hydrocarbon groups containing one carbon atom to about 20 carbon atoms. In a preferred embodiment, R 3 , Rb and R c are hydrocarbon groups containing one carbon atom to about 8 carbon atoms.
• X' is a halogen. In a preferred embodiment, X 1 is chloride.
• the structure of R 3 , R b and R 0 mimics the growing species or monomer. In some embodiments, such structure is a l-halo,l-phenylethane initiator for polystyrene or a 2,4,4-trimethyl pentyl halide initiator for polyisobutylene.
• R 3 , Rb and R 0 are each hydrocarbon groups containing one carbon atom to about 8 carbon atoms for the initiation of an isobutylene polymerization.
• the initiator is a cumyl, dicumyl or tri cumyl halide.
• Some exemplary initiators include 2-chloro-2-phenylpropane, i.e., cumyl chloride; l,4-di(2-chloro-2-propyl)benzene, i.e., di(cumylchloride); l,3,5-tri(2-chloro-2- propyl)benzene, i.e., tri(cumyl chloride); 2,4,4-trimethyl-2-chloropentane; 2-acetyl-2- phenylpropane, i.e., cumyl acetate; 2-propionyl-2-phenyl propane, i.e., cumyl propionate; 2-methoxy-2-phenylpropane, i.e., cumylmethyl ether; l,4-di(2-methoxy-2-propyl)benzene, i.e., di(cumylmethyl ether); l,3,5-tri(2-methoxy-2-propy
• the initiator can be mono-functional, bi-functional, or multi-functional.
• mono-functional initators include 2-chloro-2- phenylpropane, 2-acetyl-2-phenylpropane, 2-propionyl-2-phenylpropane, 2-methoxy-2- phenylpropane, 2-ethoxy-2-phenylpropane, 2-chloro-2,4,4-trimethylpentane, 2-acetyl-2,4,4,- trimethylpentane, 2-propionyl-2,4,4-trimethylpentane, 2-methoxy-2,4,4-trimethylpentane, 2- ethoxy-2,4,4-trimethylpentane, and 2-chloro-2,4,4-trimethylpentane.
• bi- functional initiators include l,3-di(2-chloro-2-propyl)benzene, l,3-di(2-methoxy-2- propyl)benzene, l,4-di(2-chloro-2-propyl)benzene, l,4-di(2-methoxy-2-propyl)benzene, and 5-tert-butyl-l ,3,-di(2-chloro-2-propyl) benzene.
• multi-functional initiators include l,3,5-tri(2-chloro-2-propyl)benzene and l,3,5-tri(2-methoxy-2-propyl)benzene.
• the monomer is a hydrocarbon monomer, i.e., a compound containing only hydrogen and carbon atoms, including but not limited to, olefins and diolefins, and those having from about 2 to about 20 carbon atoms, e.g., from about 4 to about 8 carbon atoms.
• Some exemplary monomers include isobutylene, styrene, beta pinene, isoprene, butadiene, 2-methyl-l-butene, 3 -methyl- 1-butene, and 4-methyl-l-pentene. Mixtures of monomers can also be used.
• the monomers are polymerized to produce polymers of different, but substantially uniform molecular weights.
• the molecular weight of the polymer is from about 300 to in excess of a million g/mol.
• such polymers are low molecular weight liquid or viscous polymers having a molecular weight of from about 200 to 10,000 g/mol, or solid waxy to plastic, or elastomeric materials having molecular weights of from about 100,000 to 1,000,000 g/mol, or more.
• the Lewis acid is a non- protic acid, e.g., a metal halide or non-metal halide.
• metal halide Lewis acids include a titanium (IV) halide, a zinc
• halide e.g., titanium tetrabromide, titanium tetrachloride, zinc chloride, AlBr 3 , and alkyl aluminum halides such as ethyl aluminum dichloride and methyl aluminum bromide.
• non-metal halide Lewis Acids include an antimony (VI) halide, a gallium (III) halide, or a boron (III) halide, e.g., boron trichloride, or a trialkyl aluminum compound such as trimethyl aluminum.
• Mixtures of two, or more than two, Lewis acids can also used.
• a mixture of an aluminum (III) halide and a trialkyl aluminum compound is used.
• the stoichiometric ratio of aluminum (III) halide to trialkyl aluminum is greater than 1 , while in other embodiments, the stoichiometric ratio of aluminum (III) halide to trialkyl aluminum is less than 1.
• (III) halide to trialkyl aluminum compound a stoichiometric ratio of 2:1 aluminum (III) halide to trialkyl aluminum compound; or a stoichiometric ratio of 1 :2 aluminum (III) halide to trialkyl aluminum can be used.
• a mixture of aluminum tribromide and trimethyl aluminum is used.
• the Lewis acid can be added in a suitable number of aliquots, e.g., in one aliquot or more than one aliquot, e.g., two aliquots.
• some electron donors are capable of converting traditional polymerization systems into quasiliving polymerization systems.
• the methods described herein are performed in the presence of an electron donor.
• the electron donor is capable of complexing with Lewis acids.
• the electron donor is a base and/or nucleophile.
• the electron donor is capable of abstracting or removing a proton.
• the electron donor is an organic base.
• the electron donor is an amide.
• the electron donor is N,N-dimethylformamide, N,N-dimethylacetamide, or N,N-diethylacetamide.
• the electron donor is a sulfoxide.
• the electron donor is dimethyl sulfoxide.
• the electron donor is an ester.
• the electron donor is methyl acetate or ethyl acetate. In some embodiments, the electron donor is a phosphate compound. In some embodiments, the electron donor is trimethyl phosphate, tributyl phosphate, or triamide hexamethylphosphate. In some embodiments, the electron donor is an oxygen-containing metal compound. In some embodiments, the electron donor is tetraisopropyl titanate.
• the electron donor is pyridine or a pyridine derivative. In some embodiments, the electron donor is a compound of formula:
• Ri, R 2 , R 3 , R 4 , and R 5 are each, independently, hydrogen or hydrocarbyl; or Ri and R 2 , or R 2 and R 3 , or R 3 and R 4 , or R 4 and R 5 independently form a fused aliphatic ring of about 3 to about 7 carbon atoms or a fused aromatic ring of about 5 to about 7 carbon atoms.
• Ri and R 5 are each, independently, hydrocarbyl
• R 2 -R 4 are hydrogen.
• the electron donor is 2,6-di-f ⁇ rt-butylpyridine, 2,6-lutidine, 2,4-dimethylpryidine, 2,4,6-trimethylpyridine, 2-methylpyridine, or pyridine.
• the electron donor is N,N-dimethylaniline or N,N-dimethyltoluidine. In some embodiments, the electron donor is 2,6-lutidine.
• common ion salts or salt precursors may be optionally added to the reaction mixture in addition to or in replacement of the electron donor. In some embodiments, such salts may be used to increase the ionic strength, suppress free ions, and interact with ligand exchange.
• the common ion salt precursor is tetra- n-butylammonium chloride. In some embodiments, the common ion salt precursor is tetra-n- butylammonium iodide In some embodiments, the concentration of the common ion salts or salt precursors in the total reaction mixture may be in the range from about 0.0005 moles per liter to about 0.05 moles per liter.
• the concentration of the common ion salts or salt precursors is in the range from about 0.0005 moles per liter to about 0.025 moles per liter. In some embodiments, the concentration of the common ion salt or salt precursors is in the range from about 0.001 moles per liter to about 0.007 moles per liter.
• a carbocation terminated polyolefin Once a carbocation terminated polyolefin has been generated, it is then reacted with an allylsilane compound to form an allyl-terminated polyolefin.
• the allylsilane compound used in the preparation of the allyl-terminated polyolefins has the following structure:
• R 5 , R 6 , and R 7 are alkyl, aryl, alkaryl, or aralkyl.
• R 5 , R 6 , R 7 can be, independently, methyl, ethyl, propyl, or phenyl.
• the allylsilane compounds is allyltrimethylsilane.
• a carbocationic polyolefin chain end is reacted with allytrimethylsilane in the presence of a Lewis acid, as illustrated below: Polyolefin- --- ⁇ ⁇ — CH2
• the Lewis acid can be one of the Lewis acids listed above in Section IA(d)(iii), or can be another suitable Lewis acid.
• the Lewis acid is TiCl 4 .
• the carbocationic polyolefin chain end is derived from a quasi-living polymerization and the reaction of the quasi-living carbocationic chain end with the allylsilane compound is conducted in situ.
• the following references the entire contents of each of which are incorporated by reference herein: "One-pot synthesis of allyl-terminated linear and tri-arm star polyisobutylenes, and epoxy- and hydroxyl-telechelics therefrom," Ivan et al., J. Poly. Sci., Part A 28, No. 1, pp.
• the allyl-terminated polyolefin is copolymerized with an unsaturated acidic reactant.
• the copolymerization is performed in the presence of a free radical initiator.
• the product of the copolymerization is polyallyl PIBSA.
• saturated acidic reactant refers to maleic or fumaric reactants of the general formula:
• X and X' are each independently selected from the group consisting of -OH, -Cl, - O-lower alkyl, and when taken together, X and X' are -O-.
• X and X' are such that both carboxylic functions can enter into acylation reactions.
• Maleic anhydride is one example of a useful unsaturated acidic reagent.
• the use of maleic anhydride in copolymers such as those described herein is particularly useful because the resulting succinic anhydride groups throughout the copolymer can subsequently be modified, e.g., as described in greater detail below, in order to further modify the characteristics of the copolymer.
• a variety of free radical initiators are suitable for use in initiating the copolymerization of the allyl-terminated polyolefin and the unsaturated acidic reagent.
• the copolymerization can be initiated by any suitable free radical initiator.
• suitable free radical initiators are well known in the art.
• Peroxide-type polymerization initiators, azo-type polymerization initiators, and radiation are examples of useful free initiators for copolymerization reactions such as those described herein.
• the peroxide-type free radical initiator can be organic or inorganic, in some embodiments the organic having the formula R 3 OOR 3 wherein R 3 is any organic radical and R 3 is selected from the group consisting of hydrogen and any organic radical.
• R 3 and R 3 ' can be organic radicals, e.g., hydrocarbon, aryl and acyl radicals, optionally carrying substituents such as halogens.
• useful peroxides include di- tert-amyl peroxide, di-tert-butyl peroxide, tert-butyl peroxybenzoate, dicumyl peroxide, benzoyl peroxide, lauroyl peroxide, other tertiary butyl peroxides, 2,4-dichloro-benzoyl peroxide, tertiary-butyl hydroperoxide, acetyl hydroperoxide, diethylperoxycarbonate, tertiary butyl perbenzoate, and the like.
• the azo-type compounds are also well known free radical promoting materials.
• Other suitable azo compounds include, but are not limited to, p-bromo benzenediazonium fluoroborate, p- topydiazoaminobenzene, p-bromobenzenediazonium hydroxide, azomethane, and phenyldiazonium halides.
• the copolymerization reaction can be conducted neat, that is, the quasi-living allyl-terminated polyolefin, the unsaturated acidic reactant, and the free radical initiator can be combined in the proper ratio and then stirred at the reaction temperature.
• the unsaturated acidic reactant can be added over time, or all at once.
• the reaction can be conducted in a diluent.
• the reactants can be combined in a solvent.
• the diluent can be a single compound or a mixture of two or more compounds, that completely, nearly completely, or partially dissolves the reaction components. After the reaction is complete, volatile components can be stripped off.
• the amounts of the different reactants and the temperature of reaction are selected to provide the resulting copolymer (e.g., allyl polyPIBSA) with the desired characteristics.
• the amount of free radical initiator to employ, exclusive of radiation depends to a large extent on the particular free radical initiator chosen, the olefin used, and the reaction conditions.
• the free radical initiator is soluble in the reaction medium.
• Exemplary concentrations of free radical initator are between 0.001 :1 and 0.20: 1 moles of free radical initiator per mole of acidic reactant, e.g., between 0.005: 1 and 0.10: 1.
• the polymerization temperature is sufficiently high to break down the initiator to produce the desired free-radicals and to maintain the reactants in a liquid phase at the reaction pressure (e.g. , atmospheric pressure).
• the reaction time is sufficient to result in the substantially complete conversion of the acidic reactant and quasi-living allyl-terminated polyolefin to copolymer.
• Example reaction times are between one and 24 hours, e.g., between two and 10 hours.
• the subject reaction occurs in liquid phase.
• the quasi-living allyl-terminated polyolefin, unsaturated acidic reactant, and free radical initiator can be brought together in any suitable manner, e.g. , such that the quasi-living allyl-terminated polyolefin and unsaturated acidic reactant are brought into intimate contact in the presence of free radicals generated by the free radical initiator.
• the reaction can be conducted in a batch system where the quasi-living allyl-terminated polyolefin is added all initially to a mixture of unsaturated acidic reactant, and free radical initiator; alternately, the quasi-living polyolefin can be added intermittently or continuously to the reaction pot.
• the reactants can also be added in other orders.
• the initiator and unsaturated acidic reactant can be added to a reaction pot containing the quasi-living allyl-terminated polyolefin.
• the components in the reaction mixture are added continuously to a stirred reactor with continuous removal of a portion of the product to a recovery train or to other reactors in series.
• the reaction can also suitably take place in a coil-type reactor where the components are added at one or more points along the coil.
• residual unsaturated acidic reactant can optionally be removed using conventional techniques, e.g., by reducing the pressure over the copolymer to substantially strip off the reactant.
• Copolymers made with allyl-terminated polyolefins and unsaturated acidic reactants can be reacted with various reactants in order to provide a desired functionality and/or to adjust other characteristics of the copolymers.
• the resulting polyallyl PIBSA derivatives can then be used in various compositions, such as lubricating oils, fuels, and concentrates.
• a polysuccinimide can be prepared by reacting a copolymer made as described herein, e.g., polyallyl PIBSA made with allyl-terminated PIB and maleic anhydride, with either an amine or a polyamine, under reactive conditions.
• a copolymer made as described herein e.g., polyallyl PIBSA made with allyl-terminated PIB and maleic anhydride
• the amine or polyamine is employed in amounts such that there are 0.1 to 1.5 equivalents of amine or polyamine per equivalent of acidic groups in the polyallyl PIBS A/acid-catalyzed thermal allyl PIBSA mixture.
• a polyamine is used having at least two nitrogen atoms and 4 to 20 carbon atoms.
• the reaction may be desirable to conduct the reaction in an inert organic solvent.
• Useful solvents will vary and can be determined from literature sources or routine experiments.
• the reaction is conducted at temperatures in the range of from about 6O 0 C to 18O 0 C, e.g., 15O 0 C to 17O 0 C, for from about 1 to 10 hours, e.g., from about 2 to 6 hours.
• the reaction is conducted at about atmospheric pressure; however, higher or lower pressures can also be used depending on the reaction temperature desired and the boiling point of the reactants or solvent.
• Water, present in the system or generated by this reaction, can be removed from the reaction system during the course of the reaction via azeotroping or distillation. After reaction completion, the system can be stripped at elevated temperatures (typically 100 0 C to 25O 0 C) and reduced pressures to remove any volatile components that may be present in the product.
• An amine or a polyamine is used, e.g., a polyamine with at least one or more amine nitrogen atoms per molecule, e.g., 4 to 12 amine nitrogens per molecule.
• Polyamines having from about 6 to 10 nitrogen atoms per molecule can also be used.
• Some useful polyalkene polyamines also contain from about 4 to 20 carbon atoms, e.g., from 2 to 3 carbon atoms per alkylene unit, and in some embodiments have a carbon-to-nitrogen ratio of from 1 : 1 to 10: 1.
• Such polyamines encompass isomers, such as branched-chain polyamines, and substituted polyamines, including hydrocarbyl- substituted polyamines.
• HPA-X heavy polyamine contains an average of approximately 6.5 amine nitrogen atoms per molecule.
• polyether diamines such as Jeffamine® ED-900 and the like, available from Huntsman Chemical Company, may be used.
• aromatic amines such as N-phenyl- 1 ,4-phenylenediamine (NPPDA) and the like may be used.
• NPPDA N-phenyl- 1 ,4-phenylenediamine
• mixtures of amines, polyamines, polyether diamines, and aromatic amines may be used.
• the polyamine reactant can be a single compound or a mixture of compounds reflecting commercial polyamines.
• commercial polyamines are a mixture in which one or several compounds predominate with the average composition indicated.
• tetraethylene pentamine prepared by the polymerization of aziridine or the reaction of dichloroethylene and ammonia typically includes both lower and higher amine members, e.g. , triethylene tetramine, substituted piperazines and pentaethylene hexamine, but the composition is largely tetraethylene pentamine and the empirical formula of the total amine composition closely approximates that of tetraethylene pentamine.
• Suitable polyamines include admixtures of amines of various molecular weights. Included are mixtures of diethylene triamine and heavy polyamine. One exemplary polyamine admixture is a mixture containing 20% by weight diethylene triamine and 80% by weight heavy polyamine.
• the amine is a primary amine, secondary amine, or mixture thereof, and can have at least 10 carbon atoms, e.g. , between 12 and 18 carbon atoms.
• Aromatic, aliphatic, saturated, and unsaturated amines may be employed.
• Useful amines include aliphatic primary amines. Examples of suitable amines include, but are not limited to, octadecylamine and dodecylamine.
• An example of a suitable mixture of amines is tallowamine (a partially saturated mixture of amines including mainly C ⁇ $ amines).
• Mixtures of monoamines and polyamines can be used. Also, polyoxyalkylene polyamines (for example, materials supplied under the trade name Jeffamine®) and aminoalcohols can also be suitably used.
• Polyesters can be prepared by reacting a copolymer made as described herein, e.g., polyallyl PIBSA made with quasi-living allyl-terminated PIB and maleic anhydride, with a polyol, under reactive conditions.
• the polyols have the formula R"(OH) X where R" is a hydrocarbon radical and x is an integer representing the number of hydroxy radicals and has a value of from 2 to about 10.
• the polyols contain less than 30 carbon atoms, and have from 2 to about 10, e.g. , 3 to 6, hydroxy radicals.
• alkylene glycols and poly(oxyalkylene) glycols such as ethylene glycol, di(ethylene glycol), tri(ethylene glycol), di(propylene glycol), tri(butylene glycol), penta(ethylene glycol), and other poly(oxyalkylene) glycols formed by the condensation of two or more moles of ethylene glycol, propylene glycol, octylene glycol, or a like glycol having up to 12 carbon atoms in the alkylene radical.
• polyhydric alcohols include glycerol, pentaerythritol, 2,4-hexanediol, pinacol, erythritol, arabitol, sorbitol, mannitol, 1,2- cyclohexanediol, xylylene glycol, and 1 ,3,5-cyclohexanetriol.
• Other useful polyols are disclosed in U.S. Pat. No. 4,034,038, issued JuI. 5, 1977 to Vogel, which is incorporated by reference in its entirety.
• Esterification can be effected, for example, at a temperature of about 100 0 C to about 18O 0 C, e.g., about 15O 0 C. to about 16O 0 C.
• the reaction is carried out at substantially atmospheric pressure, although pressures above atmospheric can be employed, e.g., with more volatile reactants. In some emboidments, stoichiometric amounts of reactants are employed.
• the reaction can be run in the absence of a catalyst, or in the presence of an acid-type catalyst such as mineral acids, sulfonic acids, Lewis type acids and the like. Suitable reaction conditions and catalysts are disclosed in U.S. Pat. No. 3,155,686, issued Nov. 3, 1964 to Prill et al., which is incorporated by reference in its entirety.
• polysuccinimides made as described above e.g. , polysuccinimides made using polyallyl PIBSA made with quasi-living allyl- terminated PIB and maleic anhydride, can be further modified by reaction with a cyclic carbonate.
• the resulting post-treated product has one or more nitrogens of the polyamino moiety substituted with a hydroxy hydrocarbyl oxycarbonyl, a hydroxy poly(oxyalkylene) oxycarbonyl, a hydroxyalkylene, hydroxyalkylenepoly(oxyalkylene), or mixture thereof.
• the cyclic carbonate post-treatment is conducted under conditions sufficient to cause reaction of the cyclic carbonate with secondary amino groups of the polyamino substituents.
• the reaction is conducted at temperatures of about O 0 C to 25O 0 C, e.g., from 100 0 C to 200 0 C, e.g., from about 150 0 C to 18O 0 C.
• the reaction can be conducted neat, and optionally is conducted in the presence of a catalyst (such as an acidic, basic or Lewis acid catalyst). Depending on the viscosity of the reactants, it may be useful to conduct the reaction using an inert organic solvent or diluent, e.g., toluene or xylene.
• a catalyst such as an acidic, basic or Lewis acid catalyst.
• an inert organic solvent or diluent e.g., toluene or xylene.
• suitable catalysts include phosphoric acid, boron trifluoride, alkyl or aryl sulfonic acid, and alkali or alkaline earth carbonate.
• the molar charge of cyclic carbonate employed in the post-treatment reaction is, in some embodiments, based upon the theoretical number of basic nitrogen atoms contained in the polyamino substitutent of the succinimide.
• a molar charge ratio of 2 would theoretically require that two moles of cyclic carbonate be added for each basic nitrogen, or in this case 6 moles of cyclic carbonate for each mole equivalent of succinimide.
• Mole ratios of the cyclic carbonate to the basic amine nitrogen are typically in the range of from about 1 : 1 to about 4: 1 ; preferably from about 2:1 to about 3:1.
• polysuccinimides made as described above can be further modified by reaction with boric acid or a similar boron compound to form borated dispersants.
• boric acid examples include boron oxides, boron halides and esters of boric acid. In some embodiments, from about 0.1 equivalent to about 1 equivalent of boron compound per equivalent of basic nitrogen or hydroxyl in the compositions of this invention may be employed.
• Polysuccinimides based on polyallyl PIBSA made with quasi-living allyl- terminated PIB and maleic anhydride, such as those described above, are useful as detergent and dispersant additives in lubricating oils.
• such polysuccinimides can, for example, be used in amounts of about 1 to about 10 percent by weight (on an actives basis) of the total composition, e.g., less than about 5 percent by weight (on an actives basis). Actives basis indicates that only the active ingredients of the polysuccinimides are considered when determining the amount of the additive relative to the remainder of a composition. Diluents and any other inactives, such as unreacted polyolefin, are excluded. Unless otherwise indicated, in describing the lubricating oil and final compositions or concentrates, active ingredient contents are intended with respect to the polysuccinimides.
• the lubricating oil used with the polysuccinimides may be mineral or synthetic oils of lubricating viscosity and preferably suitable for use in the crankcase of an internal combustion engine.
• Crankcase lubricating oils typically have a viscosity of about 1300 cSt at O 0 F (-17.8 0 C) to 22.7 cSt at 210 0 F (99 0 C).
• Useful mineral oils include paraffinic, naphthenic and other oils that are suitable for use in lubricating oil compositions.
• Synthetic oils include both hydrocarbon synthetic oils and synthetic esters.
• Useful synthetic hydrocarbon oils include polymers of alpha olefins having suitable viscosity, e.g., the hydrogenated liquid oligomers of C 6 to Ci 2 alpha olefins, such as 1-decene trimer. Likewise, alkyl benzenes of proper viscosity such as didodecyl benzene can be used.
• Useful synthetic esters include the esters of both monocarboxylic acids and polycarboxylic acids as well as monohydroxy alkanols and polyols.
• Examples are didodecyl adipate, pentaerythritol tetracaproate, di-2- ethylhexyl adipate, dilaurylsebacate and the like.
• Complex esters prepared from mixtures of mono and dicarboxylic acid and mono and dihydroxy alkanols can also be used.
• Blends of hydrocarbon oils and synthetic oils are also useful. For example, blends of 10 to 25 weight percent hydrogenated 1-decene trimer with 75 to 90 weight percent 150 SUS (100 0 F) mineral oil gives an excellent lubricating oil base.
• Other additives which may be present in the formulation include detergents (overbased and non-overbased), rust inhibitors, foam inhibitors, metal deactivators, pour point depressants, antioxidants, wear inhibitors, zinc dithiophosphates and a variety of other well known additives.
• polysuccinimides prepared as described above can be employed as dispersants and detergents in hydraulic fluids, marine crankcase lubricants and the like.
• the polysuccinimide is added at from 0.1 to 5 percent by weight (on an active polysuccinimide basis) to the fluid, and preferably at from 0.5 to 5 weight percent (on an active polysuccinimide basis).
• Polysuccinimides can also be used in additive concentrates, which in some embodiments include from 90 to 10 percent, e.g., 20 to 60 weight percent, of an organic liquid diluent and from 10 to 90 weight percent, e.g., 80 to 40 weight percent, (on a dry basis) of the polysuccinimide.
• the concentrates contain sufficient diluent to make them easy to handle during shipping and storage.
• Suitable diluents for the concentrates include any inert diluent, preferably an oil of lubricating viscosity, so that the concentrate may be readily mixed with lubricating oils to prepare lubricating oil compositions.
• Suitable lubricating oils which can be used as diluents typically have viscosities in the range from about 1300 cSt at O 0 F (-17.8 0 C) to 22.7 cSt at 21O 0 F (99°C), although an oil of lubricating viscosity can be used.
• polysuccinimides prepared as described above When used in fuels, useful concentrations of polysuccinimides prepared as described above, to obtain the desired detergency, is dependent upon a variety of factors including the type of fuel used, the presence of other detergents or dispersants or other additives, etc.
• the range of concentration of the polysuccinimide in the base fuel is 10 to 10,000 weight parts per million, e.g. , from 30 to 5,000 parts per million. If other detergents are present, a lesser amount of the polysuccinimide may be used.
• the polysuccinimides can also be formulated as a fuel concentrate, using an inert stable oleophilic solvent boiling in the range of about 150-400 0 F (65.6-204.4 0 C).
• an aliphatic or an aromatic hydrocarbon solvent such as a benzene, toluene, xylene or higher-boiling aromatics or aromatic thinners.
• Aliphatic alcohols of about 3 to 8 carbon atoms, such as isopropanol, isobutylcarbinol, n-butanol and the like in combination with hydrocarbon solvents are also suitable for use with the polysuccinimide.
• the amount of the polysuccinimide will, in some embodiments, be at least 5 percent by weight and not more 70 percent by weight, e.g. , from 5 to 50, e.g., from 10 to 25 weight percent.
• a four-neck 3000 milliliter round-bottom flask was equipped with an overhead mechanical stirrer and platinum resistance thermometer. This assembly was immersed into a heptane bath at -70°C under dry nitrogen gas in a substantially inert atmosphere glove box. The flask was then charged with the following reactants:
• the solution was removed from the glove box and volatile components (e.g. methyl chloride) were evaporated under ambient conditions.
• volatile components e.g. methyl chloride
• the organic phase was extracted with a 5% HCl aqueous solution followed by extraction with deionized water.
• the purified organic phase was then dried with MgSO 4 , filtered, and solvents vacuum stripped to yield 31Og allyl-terminated PIB.
• NMR characterization indicated the PIB contained greater than 98 mole percent allyl chain ends.
• a number average molecular weight of 1050 g/mol and DI of 1.1 was determined using gel permeation chromatography equipped with a multi angle laser light scattering detector and a refractive index detector.
• the allyl PIB was heated to 15O 0 C and to this was added 1.66 g of di-tert-amyl peroxide (0.01 mol) via one syringe pump at a rate of 0.017 mL/min and 16.2 g of molten maleic anhydride (0.165 mol) via a heated (8O 0 C) syringe pump at a rate of 0.104 niL/min. The total time of addition was 2 h. The mixture was then heated at 150° C for an additional 4 h. The mixture was then heated to 180°C and the unreacted maleic anhydride was removed in vacuo.
• the product had a SAP number (saponification number as determined by ASTM D94) of 98.4 mg KOH/g, an actives content (weight percent of product containing anhydride groups) of 86.5 wt%, and a succinic ratio of 1.2.
• the number average molecular weight of the product was 1940 and the dispersion index was 2.84.
• the succinic ratio refers to the ratio calculated in accordance with the procedure and mathematical equation set forth in columns 5 and 6 of U.S. Patent No. 5,334,321, the entire contents of which are incorporated by reference herein. Normally, the succinic ratio refers to the number of succinic groups per polybutene tail. In the context of this application, the succinic ratio refers to the ratio of succinic anhydride to polybutene tails that are present in the polyallyl PIBSA polymer.
• Both syringe needles were positioned below the surface of the liquid so that the tips of the needles were just touching each other.
• the reaction was heated for an additional 2 h.
• the excess maleic anhydride was removed by distillation at reduced pressure at 18O 0 C over a 2 h period.
• the polyPIBSA had a SAP number (saponification number as determined by ASTM D94) of 123.7mg KOH/g and contained 81.6 wt % actives.
• the succinic ratio was 1.6.
• the number average molecular weight of the product (determined using gel permeation chromatography with Universal Calibration) was 1310 and the dispersion index was 2.59.
• Comparative example A was repeated except that maleic anhydride (14.34g, 0.146 mol), di-tert-amyl peroxide (1.4g, 0.0096 mol) were used, 25g tetrachloroethylene was used as a solvent, and the temperature was 140°C instead of 15O 0 C. The solvent was removed in vacuo to give a product that had a SAP number of 96.4 mg KOH/g sample and contained 61.2% actives.
• the succinic ratio was 1.7.
• the number average molecular weight of the product (determined using gel permeation chromatography with Universal Calibration) was 1130 and the dispersion index was 2.59.
• Comparative example B was repeated except that high methylvinylidene PIB (102.Sg 0.098 mol), maleic anhydride (14.7g 0.150 mol), t-butylperoctanoate (2.25g, 0.0098 mol) was used, and the temperature was 90°C instead of 14O 0 C.
• the solvent was removed in vacuo to give a product that had a SAP number of 47.6 mg KOH/g sample and contained 52% actives.
• the succinic ratio was 0.9.
• the number average molecular weight of the product (determined using gel permeation chromatography with Universal Calibration) was 1560 and the dispersion index was 5.34.
• Example 2 The copolymer characteristics of Example 2 and Comparative Examples A through C are shown in Table 1. Table 1
• Multigrade oils meet the SAE 1 OW viscosity limit at low temperature and the SAE 30 viscosity limit at high temperature.
• Example of ways to meet the desired viscosity targets are to use: 1 ) blends of different viscosity base oils (for example 100 neutral plus 600 neutral oils), 2) unconventional base oils with high viscosity index (YI), 3) a detergent/inhibitor additive package with a lower Cold Crank Simulator (CCS) thickening and 4) viscosity index improvers (VI improvers) which improve the viscosity index of formulated oils.
• the use of the right combination of these four variables can produce formulated oils with high kinematic viscosity (kv) at 100 0 C and low CCS viscosity at for example -2O 0 C.
• a dispersant may have both a low CCS viscosity and a low kv. This can be determined by measuring the CCS and the kv for a dispersant dissolved in a diluent oil. A dispersant with a lower CCS and kv may have the best performance.
• PCMO passenger car motor oil
• the dispersant Under other conditions, it is sometimes desirable for the dispersant to have a high kv and a low CCS viscosity so that less VI improver is needed to meet the desired viscosity grade This can be determined by plotting the CCS versus kv and measuring the slope. The dispersant with the lowest slope has the best performance.
• the data in Table 3 shows that the polymeric dispersant of Example 3 made from allyl polyPIBSA had lower CCS and lower kv than the polymeric dispersant of Comparative Example D made from high methylvinylidene polyPIBSA even though the allyl polyPIBSA had a higher M n than the high methylvinylidene polyPIBSA. This may be desirable, for example, for use in a high fuel economy passenger car motor oil (PCMO) formulation.
• the polymeric dispersant of Example 3 had about the same CCS/kv slope as the polymeric dispersant of Comparative Example D even though the polymeric dispersant of Example 3 had a higher M n than the polymeric dispersant of Comparative Example D. This may be desirable in cases where less VI improver is needed to meet the desired viscosity grade.
• Soot dispersancy tests were also carried out on the polysuccinimide of Example 3 at different dosages in the soot thickening bench test. The details of this test are described in U.S. Patent No. 5,716,912, the entire contents of which are incorporated by reference herein.
• the soot thickening bench test the kinematic viscosity of an oil is measured with and without carbon black. Since carbon black is known to agglomerate, this normally causes an increase in the kinematic viscosity of the oil. Consequently, a dispersant that gives a lower viscosity increase in the presence of carbon black is expected to perform better than a dispersant that gives a higher viscosity increase in the presence of carbon black. That is because a dispersant that has better performance prevents the agglomeration of carbon black.
• Table 4 The results of the soot thickening bench test are presented in Table 4.

Landscapes

• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Organic Chemistry (AREA)
• General Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
• Macromonomer-Based Addition Polymer (AREA)
• Lubricants (AREA)

Priority Applications (4)

Applications Claiming Priority (2)

Publications (2)

Family

ID=41530811

Family Applications (1)

Country Status (6)

Cited By (1)

Families Citing this family (5)

Citations (15)

Family Cites Families (17)

• 2008
  • 2008-07-18 US US12/176,292 patent/US20100016191A1/en not_active Abandoned
• 2009
  • 2009-07-17 EP EP09798796.0A patent/EP2303939B1/en active Active
  • 2009-07-17 WO PCT/US2009/050965 patent/WO2010009379A2/en not_active Ceased
  • 2009-07-17 CA CA2730127A patent/CA2730127C/en active Active
  • 2009-07-17 JP JP2011518929A patent/JP5806614B2/ja active Active
  • 2009-07-17 CN CN2009801278717A patent/CN102099389B/zh active Active
• 2015
  • 2015-10-14 US US14/883,519 patent/US20160032041A1/en not_active Abandoned

Patent Citations (15)

Non-Patent Citations (3)

Also Published As

Similar Documents

Legal Events