EP0765346A1 - Polymere a pre-extraction utilise pour ameliorer les additifs dispersants obtenus par reaction de koch - Google Patents

Polymere a pre-extraction utilise pour ameliorer les additifs dispersants obtenus par reaction de koch

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Publication number
EP0765346A1
EP0765346A1 EP95923927A EP95923927A EP0765346A1 EP 0765346 A1 EP0765346 A1 EP 0765346A1 EP 95923927 A EP95923927 A EP 95923927A EP 95923927 A EP95923927 A EP 95923927A EP 0765346 A1 EP0765346 A1 EP 0765346A1
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EP
European Patent Office
Prior art keywords
polymer
hydrocarbon
functionalized
catalyst
polymers
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Application number
EP95923927A
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German (de)
English (en)
Inventor
William Daniel Diana
Joseph Victor Cusumano
Keith Raymond Gorda
Jacob Isaac Emert
William Bernard Eckstrom
David Charles Dankworth
Jon Edmond Stanat
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Infineum USA LP
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Exxon Chemical Patents Inc
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Application filed by Exxon Chemical Patents Inc filed Critical Exxon Chemical Patents Inc
Publication of EP0765346A1 publication Critical patent/EP0765346A1/fr
Withdrawn legal-status Critical Current

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    • 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
    • C10M159/00—Lubricating compositions characterised by the additive being of unknown or incompletely defined constitution
    • C10M159/12—Reaction products
    • C10M159/16—Reaction products obtained by Mannich reactions
    • 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
    • C08F6/00—Post-polymerisation treatments
    • C08F6/04—Fractionation
    • 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
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/192—Macromolecular compounds
    • C10L1/198—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds homo- or 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 an acyloxy radical of a saturated carboxylic acid, of carbonic acid
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/22—Organic compounds containing nitrogen
    • C10L1/234—Macromolecular compounds
    • C10L1/238—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/24—Organic compounds containing sulfur, selenium and/or tellurium
    • C10L1/2462—Organic compounds containing sulfur, selenium and/or tellurium macromolecular compounds
    • C10L1/2475—Organic compounds containing sulfur, selenium and/or tellurium macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon to carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/30—Organic compounds compounds not mentioned before (complexes)
    • C10L1/301—Organic compounds compounds not mentioned before (complexes) derived from metals
    • C10L1/303—Organic compounds compounds not mentioned before (complexes) derived from metals boron compounds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/30—Organic compounds compounds not mentioned before (complexes)
    • C10L1/305—Organic compounds compounds not mentioned before (complexes) organo-metallic compounds (containing a metal to carbon bond)
    • 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
    • C10M133/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen
    • C10M133/52—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of 30 or more atoms
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

Definitions

  • the present invention is directed to an improved polymer functionalization process for the Koch reaction.
  • the Koch reaction relates to reacting at least one carbon-carbon double bond with carbon monoxide in the presence of an acidic catalyst and a nucleophilic trapping agent to form a carbonyl or thiocarbonyl functional group, and derivatives thereof.
  • polymer is used herein to refer to materials comprising large molecules built up by the repetition of small, simple chemical units. In a hydrocarbon polymer those units are predominantly formed of hydrogen and carbon. Polymers are defined by average properties, and in the context of the invention polymers have a number average molecular weight (Mn) of at least 500. Light polymer used herein refers to polymer having less than 300 molecular weight (e.g., 48 to 288).
  • hydrocarbon is used herein to refer to non polymeric compounds comprising hydrogen and carbon having uniform properties such as molecular weight. However, the term “hydrocarbon” is not intended to exclude mixtures of such compounds which individually are characterized by such uniform properties.
  • Light hydrocarbon as used herein refers to compounds having a carbon number between C4 and C24, inclusive.
  • USSN 261507 Amidation of Ester Functionalized Polymers
  • USSN 261559 Batch Koch Carbonylation Process
  • USSN 261534 Derivatives of Polyamines With One Primary Amine and Secondary or Tertiary Amines
  • USSN 261560 Continuous Process for Production of Functionalized Olefins
  • USSN 26155 Lubricating Oil Dispersants Derived from Heavy Polyamines
  • USSN 261,558 Functionalized Additives Useful In Two-Cycle Engines, all filed June 17, 1994, all contain related subject matter as indicated by their titles and are hereby incorporated by reference in their entirety for all purposes.
  • U.S. Serial No. 992,403 which is incorporated by reference herein discloses reactions of a polymer having at least one ethylenic double bond reacted via a Koch mechanism to form carbonyl or thio carbonyl group-containing compounds which may subsequently be derivatized.
  • the polymers react with carbon monoxide in the presence of an acid catalyst or a catalyst preferably complexed with the nucleophilic trapping agent.
  • a preferred catalyst is BF3 and preferred catalyst complexes include BF3»H2 ⁇ and BF3 complexed with 2,4-dichlorophenol.
  • the starting polymer reacts with carbon monoxide at point of unsaturation to form either iso- or neo- acyl groups with the nucleophilic trapping agent, e.g., with water, alcohol (preferably a substituted phenol) or thiol to form respectively a carboxylic acid, carboxylic ester group, or thio ester.
  • the functionalized polymer can be subsequently derivatized with inter alia an amine, alcohol, amino alcohol, etc. to form a dispersant additive for lubricant applications.
  • the present invention relates to stripping (e.g., removal) of light polymer (e.g., lower molecular weight fractions) on alternatively light hydrocarbon from the polymer prior to the reaction described above.
  • light polymer e.g., lower molecular weight fractions
  • the removal of the light polymer results in a surprising reduction in the amount of heretofor unwanted by-products, such as light polymer esters formed during the Koch reaction.
  • the functionalized polymer must be treated prior to the derivatization step.
  • the crude ester produced in the carbonylation contains inter alia the functionalized polymer, impurities, and in the case of the use of the preferred nucleophilic trapping agent, unreacted 2,4- dichlorophenol (DCP).
  • DCP 2,4- dichlorophenol
  • the functionalized polymer is treated to remove the unreacted DCP.
  • the distillate is collected and fractionally distilled to recover and recycle the unreacted DCP.
  • some of the impurities, especially the light polymer esters that boil close to DCP as well as light chlorinated compounds are also inadvertently recycled.
  • the recycle stream of desired unreacted DCP will be quickly saturated with the undesirable components, such as the light esters.
  • Carboxyl groups have the general formula -CO-OR, where R can be H, a hydrocarbyl group, or a substituted hydrocarbyl group.
  • the Koch reaction can occur at double bonds where at least one carbon of the 15 double bond is di-substituted to form a "neo" acid or ester
  • the Koch reaction can also occur when both carbons are mono-substituted or one is monosubstituted and one is unsubstituted to form an "iso" acid (i.e. -R ⁇ C- 25 COOR).
  • Bahrmann et al.. discloses isobutylene converted to isobutyric acid via a Koch-type reaction.
  • US-A-2831877 discloses a multi-phase, acid catalyzed, two-step process for the carboxylation of olefins with carbon monoxide.
  • EP-A-0148592 relates to the production of carboxylic acid esters and/or carboxylic acids by catalyzed reaction of a polymer having carbon-carbon double 35 bonds, carbon monoxide and either water or an alcohol, optionally in the presence of oxygen.
  • the catalysts are metals such as palladium, rhodium, ruthenium, iridium, and cobalt in combination with a copper compound, in the presence of a protonic acid such as hydrochloric acid.
  • a preferred polymer is polyisobutene, which may have at least 80% of its carbon-carbon double bonds in the form of terminal double bonds. Liquid polyisobutene having a number average molecular weight in the range of from 200 to 2,500, preferably up to 1,000 are described.
  • US-A-4927892 relates to reacting a polymer or copolymer of a conjugated diene, at least part of which is formed by 1,2 polymerization, with carbon monoxide and water and/or alcohol in the presence of a catalyst prepared by combining a palladium compound, certain ligands and/or acid except hydrohalogenic acids having a pKa of less than 2.
  • Useful Lewis acids include BF3.
  • the present invention is a process for improving the polymer used in the Koch process for making dispersant additives comprising: removing light hydrocarbon fractions from said polymer prior to the carbonylation step.
  • the present invention is also a functionalized hydrocarbon polymer wherein the polymer backbone has M n > 500, functionalization is by groups of the formula -CO-Y-R ⁇ wherein Y is O or S, and R is H, hydrocarbyl, substituted hydrocarbyl, aryl, or substituted aryl, and wherein at least 50 mole % of the functional groups are attached to a tertiary carbon atom of the polymer backbone, prepared by a process comprising: removing light hydrocarbon from said polymer prior to functionalization.
  • the present invention is also a functionalized hydrocarbon polymer wherein the polymer backbone has M n > 500, the polymer backbone prior to functionalization containing less than about 1 weight percent hydrocarbon of carbon number C24 and below, functionalization is by groups of the formula -CO-Y-R 3 wherein Y is O or S, and R 3 is H, hydrocarbyl, substituted hydrocarbyl, aryl, or substituted aryl, and wherein at least 50 mole % of the functional groups are attached to a tertiary carbon atom of the polymer backbone.
  • the present invention relates to an improved process for functionalization of hydrocarbon polymer wherein the polymer backbone has Mn > 500 and light polymer (e.g., less than 300 molecular weight) has been removed prior to functionalization and the functionalization is by groups of the formula: -CO-Y-R 3 wherein Y is O or S, and either R 3 is H, hydrocarbyl and at least 50 mole % of the functional groups are attached to a tertiary carbon atom of the polymer backbone or R 3 is aryl, substituted aryl or substituted hydrocarbyl.
  • the functionalized polymer may be depicted by the formula: POLY (CR ⁇ R 2 CO-Y-R 3 ) n (I) wherein POLY is a hydrocarbon polymer backbone having a number average molecular weight of at least 500, n is a number greater than 0, Rl, R2 and R 3 may be the same or different and are each H, hydrocarbyl with the proviso that either Rl and R2 are selected such that at least 50 mole percent of the -CR ⁇ R 2 groups wherein both Rl and R 2 are not H, or R 3 is aryl substituted aryl or substituted hydrocarbyl.
  • hydrocarbyl denotes a group having a carbon atom directly attached to the remainder of the molecule and having predominantly hydrocarbon character within the context of this invention and includes polymeric hydrocarbyl radicals.
  • radicals include the following: (1) Hydrocarbon groups; that is, aliphatic, (e.g., alkyl or alkenyl), alicyclic
  • cycloalkyl or cycloalkenyl e.g., cycloalkyl or cycloalkenyl
  • radicals are known to those skilled in the art; examples include methyl, ethyl, butyl, hexyl, octyl, decyl, dodecyl, tetradecyl, octadecyl, eicosyl, cyclohexyl, phenyl and naphthyl (all isomers being included).
  • Substituted hydrocarbon groups that is, radicals containing non- hydrocarbon substituents which, in the context of this invention, do not alter predominantly hydrocarbon character of the radical.
  • substituents e.g., halo, hydroxy, alkoxy, carbalkoxy, nitro, alkyl sulfoxy.
  • Hetero groups that is, radicals which, while predominantly hydrocarbon in character within the context of this invention, contain atoms other than carbon present in a chain or ring otherwise composed of carbon atoms.
  • Suitable hetero atoms will be apparent to those skilled in the art and include, for example, nitrogen particularly non- basic nitrogen which would deactivate the Koch catalyst, oxygen and sulfur.
  • no more than about three substituents or hetero atoms, and preferably no more than one, will be present for each 10 carbon atoms in the hydrocarbon-based radical.
  • Polymeric hydrocarbyl radicals are those derived from hydrocarbon polymers, which may be substituted and/or contain hetero atoms provided that they remain predominantly hydrocarbon in character.
  • the functionalized polymer may be derived from a hydrocarbon polymer comprising non-aromatic carbon-carbon double bond, also referred to as an olefinically unsaturated bond, or an ethylenic double bond.
  • the polymer is functionalized at that double via a Koch reaction to form the carboxylic acid, carboxylic ester or thio acid or thio ester. It is the object of this invention to remove light polymer or light hydrocarbon from the polymer prior to the functionalization. Koch reactions have not heretofore been applied to polymers having number average molecular weights greater than 500.
  • the hydrocarbon polymer preferably has Mn greater than 1,000.
  • a polymer having at least one ethylenic double bond is contacted with an acid catalyst and carbon monoxide in the presence of a nucleophilic trapping agent such as water or alcohol.
  • the catalyst is preferably a classical Broensted acid or Lewis acid catalyst. These catalysts are distinguishable from the transition metal catalysts of the type described in the prior art.
  • the Koch reaction as applied in the process of the present invention, may result in good yields of functionalized polymer, even 90 mole % or greater.
  • POLY in general formula I, represents a hydrocarbon polymer backbone having Mn of at least 500 with the polymer less than 300 molecular weight removed, and/or light hydrocarbon of carbon number C4 to C24. Mn may be determined by available techniques such as gel permeation chromatography (GPC). POLY is derived from unsaturated polymer.
  • the polymers which are useful in the Koch reaction are polymers containing at least one carbon-carbon double bond (olefinic or ethylenic) unsaturation. Thus, the maximum number of functional groups per polymer chain is limited by the number of double bonds per chain.
  • Such polymers have been found to be receptive to Koch mechanisms to form carboxylic acids or derivatives thereof, using the catalysts and nucleophilic trapping agents of the present invention. It is known that polymers useful in the Koch process include polymers containing a distribution of molecular weights (MWD).
  • Useful polymers in the Koch reaction include polyalkenes including homopolymer, copolymer (used interchangeably with interpolymer) and mixtures.
  • Homopolymers and interpolymers include those derived from polymerizable olefin monomers of 2 to about 16 carbon atoms; usually 2 to about 6 carbon atoms.
  • alpha olefin polymers made using organo metallic coordination compounds are ethylene alpha olefin copolymers such as those disclosed in US-A-5017299.
  • the polymer unsaturation can be terminal, internal or both.
  • Preferred polymers have terminal unsaturation, preferably a high degree of terminal unsaturation. Terminal unsaturation is the unsaturation provided by the last monomer unit located in the polymer. The unsaturation can be located anywhere in this terminal monomer unit.
  • At least one of R a and R ⁇ is a polymeric group of the present invention, and the remaining R D , R c and R ⁇ are hydrocarbon groups as defined with respect to R, Rl, R2, and R 3 above.
  • Low molecular weight polymers also referred to herein as dispersant range molecular weight polymers, are polymers having Mn less than 20,000, preferably 500 to 20,000 (e.g. 1,000 to 20,000), more preferably 1,500 to 10,000 (e.g. 2,000 to 8,000) and most preferably from 1,500 to 5,000. The number average molecular weights are measured by vapor phase osmometry. Low molecular weight polymers are useful in forming dispersants for lubricant additives.
  • Mn's ranging from 20,000 to 200,000, preferably 25,000 to 100,000; and more preferably, from 25,000 to 80,000 are useful for viscosity index improvers for lubricating oil compositions, adhesive coatings, tackifiers and sealants.
  • the medium Mn can be determined by membrane osmometry.
  • the higher molecular weight materials have Mn of greater than about 200,000 and can range to 15,000,000 with specific embodiments of 300,000 to 10,000,000 and more specifically 500,000 to 2,000,000. These polymers are useful in polymeric compositions and blends including elastomeric compositions.
  • Higher molecular weight materials having Mn's of from 20,000 to 15,000,000 can be measured by gel permeation chromatography with universal calibration, or by light scattering.
  • the values of the ratio Mw/Mn, referred to as molecular weight distribution, (MWD) are not critical. However, a typical minimum Mw/Mn value of about 1.1-2.0 is preferred with typical ranges of about 1.1 up to about 4.
  • medial olefins (sometimes referred to in the patent literature as medial olefins) characterized by the presence within their structure of the group:
  • internal olefin monomers When internal olefin monomers are employed, they normally will be employed with terminal olefins to produce polyalkenes which are interpolymers.
  • terminal olefins For this invention, a particular polymerized olefin monomer which can be classified as both a terminal olefin and an internal olefin, will be deemed a terminal olefin.
  • pentadiene-1,3 i.e., piperylene
  • polyalkenes generally are hydrocarbon polyalkenes, they can contain substituted hydrocarbon groups such as lower alkoxy, lower alkyl mercapto, hydroxy, mercapto, and carbonyl, provided the non-hydrocarbon moieties do not substantially interfere with the functionalization or derivatization reactions of this invention. When present, such substituted hydrocarbon groups normally will not contribute more than about 10% by weight of the total weight of the polyalkenes. Since the polyalkene can contain such non-hydrocarbon substituent, it is apparent that the olefin monomers from which the polyalkenes are made can also contain such substituents. As used herein, the term "lower” when used with a chemical group such as in "lower alkyl” or “lower alkoxy” is intended to describe groups having up to seven carbon atoms.
  • the polyalkenes may include aromatic groups and cycloaliphatic groups such as would be obtained from polymerizable cyclic olefins or cycloaliphatic substituted- polymerizable acrylic olefins.
  • aromatic groups and cycloaliphatic groups such as would be obtained from polymerizable cyclic olefins or cycloaliphatic substituted- polymerizable acrylic olefins.
  • polyalkenes free from aromatic and cycloaliphatic groups (other than the diene styrene interpolymer exception already noted).
  • polyalkenes derived from homopolymers and interpolymers of terminal hydrocarbon olefins of 2 to 16 carbon atoms There is a further preference for polyalkenes derived from homopolymers and interpolymers of terminal hydrocarbon olefins of 2 to 16 carbon atoms.
  • interpolymers of terminal olefins are usually preferred, interpolymers optionally containing up to about 40% of polymer units derived from internal olefins of up to about 16 carbon atoms are also within a preferred group.
  • a more preferred class of polyalkenes are those selected from the group consisting of homopolymers and interpolymers of terminal olefins of 2 to 6 carbon atoms, more preferably 2 to 4 carbon atoms.
  • another preferred class of polyalkenes are the latter, more preferred polyalkenes optionally containing up to about 25% of polymer units derived from internal olefins of up to about 6 carbon atoms.
  • terminal and internal olefin monomers which can be used to prepare the polyalkenes according to conventional, well-known polymerization techniques include ethylene; propylene; butene-1; butene-2; isobutene; pentene-1; etc.; propylene-tetramer; diisobutylene; isobutylene trimer; butadiene- 1,2; butadiene- 1,3; pentadiene-1,2; pentadiene-1,3; etc.
  • Useful polymers include alpha-olefin homopolymers and interpolymers, and ethylene alpha-olefin copolymers and terpolymers.
  • Specific examples of polyalkenes include polypropylenes, polybutenes, ethylene-propylene copolymers, ethylene-butene copolymers, propylene-butene copolymers, styrene-isobutene copolymers, isobutene- butadiene-1,3 copolymers, etc., and terpolymers of isobutene, styrene and piperylene and copolymer of 80% of ethylene and 20% of propylene.
  • a useful source of polyalkenes are the poly(isobutene)s obtained by polymerization of C4 refinery stream having a butene content of about 35 to about 75% by wt., and an isobutene content of about 30 to about 60% by wt., in the presence of a Lewis acid catalyst such as aluminum trichloride or boron trifluoride.
  • a Lewis acid catalyst such as aluminum trichloride or boron trifluoride.
  • a preferred source of monomer for making poly-n-butenes is petroleum feedstreams such as Raffinate II. These feedstocks are disclosed in the art such as in US-A-4952739.
  • Preferred polymers are polymers of ethylene and at least one alpha-olefin having the formula is straight chain or branched chain alkyl radical comprising 1 to 18 carbon atoms and wherein the polymer contains a high degree of terminal ethenylidene unsaturation.
  • R ⁇ in the above formula is alkyl of from 1 to 8 carbon atoms and more preferably is alkyl of from 1 to 2 carbon atoms. Therefore, useful comonomers with ethylene in this invention include propylene, 1-butene, hexene-1, octene-1, etc., and mixtures thereof (e.g. mixtures of propylene and 1 -butene, and the like).
  • Preferred polymers are copolymers of ethylene and propylene and ethylene and butene- 1.
  • the molar ethylene content of the polymers employed is preferably in the range of between about 20 and about 80%, and more preferably between about 30 and about 70%.
  • the ethylene content of such copolymer is most preferably between about 20 and about 45 wt %, although higher or lower ethylene contents may be present.
  • the most preferred ethylene- butene-1 copolymers are disclosed in USSN 992192, filed December 17, 1992.
  • the preferred method for making low molecular weight ethylene/ ⁇ -olefin copolymer is described in USSN 992690, filed December 17, 1992.
  • Preferred ranges of number average molecular weights of polymer for use as precursors for dispersants are from 500 to 10,000, preferably from 1,000 to 8,000, most preferably from 2,500 to 6,000.
  • a convenient method for such determination is by size exclusion chromatography (also known as gel permeation chromatography (GPC)) which additionally provides molecular weight distribution information.
  • Such polymers generally possess an intrinsic viscosity (as measured in tetralin at 135°C) of between 0.025 and 0.6 dl/g, preferably between 0.05 and 0.5 dl/g, most preferably between 0.075 and 0.4 dl/g. These polymers preferably exhibit a degree of crystallinity such that, when grafted, they are essentially amorphous.
  • the preferred ethylene alpha-olefin polymers are further characterized in that up to about 95% and more of the polymer chains possess terminal vinylidene-type unsaturation.
  • the preferred ethylene alpha-olefin polymer comprises polymer chains, at least about 30% of which possess terminal vinylidene unsaturation. Preferably at least about 50%, more preferably at least about 60%, and most preferably at least about 75% (e.g. 75 to 98%), of such polymer chains exhibit terminal vinylidene unsaturation.
  • the percentage of polymer chains exhibiting terminal vinylidene unsaturation may be determined by FTIR spectroscopic analysis, titration, HNMR, or Ci 3NMR.
  • the polymers can be prepared by polymerizing monomer mixtures comprising ethylene with other monomers such as alpha-olefins, preferably from 3 to 4 carbon atoms in the presence of a metallocene catalyst system comprising at least one metallocene (e.g., a cyclopentadienyl-transition metal compound) and an activator, e.g. alumoxane compound.
  • a metallocene catalyst system comprising at least one metallocene (e.g., a cyclopentadienyl-transition metal compound) and an activator, e.g. alumoxane compound.
  • the comonomer content can be controlled through selection of the metallocene catalyst component and by controlling partial pressure of the monomers.
  • the catalyst is preferably a bulky ligand transition metal compound.
  • the bulky ligand may contain a multiplicity of bonded atoms, preferably carbon atoms, forming a group which may be cyclic with one or more optional heteroatoms.
  • the bulky ligand may be a cyclopentadienyl derivative which can be mono- or polynuclear.
  • One or more bulky ligands may be bonded to the transition metal atom.
  • the transition metal atom may be a Group IV, V or VI transition metal ("Group” refers to an identified group of the Periodic Table of Elements, comprehensively presented in "Advanced Inorganic Chemistry," F.A. Cotton, G. Wilkinson, Fifth Edition, 1988, John Wiley & Sons).
  • ligands may be bonded to the transition metal, preferably detachable by a cocatalyst such as a hydrocarbyl or halogen leaving group.
  • the catalyst is derivable from a compound of the formula [L] m M[X] n wherein L is the bulky ligand, X is the leaving group, M is the transition metal and m and n are such that the total ligand valency corresponds to the transition metal valency.
  • the catalyst is four coordinate such that the compound is ionizable to a 1 + valency state.
  • the ligands L and X may be bridged to each other and if two ligands L and/or
  • the metallocenes may be full-sandwich compounds having two ligands L which are cyclopentadienyl groups or half-sandwich compounds having one ligand L only which is a cyclopentadienyl group.
  • the term "metallocene” is defined to contain one or more cyclopentadienyl moiety in combination with a transition metal of the Periodic Table of Elements.
  • the metallocene catalyst is represented by the formulas:
  • Various forms of the catalyst system of the metallocene type may be used in the polymerization process of this invention.
  • Exemplary of the development of metallocene catalysts in the art for the polymerization of ethylene is the disclosure of US-A-4871705 to Hoel, US-A-4937299 to Ewen, et al. and EP-A-0129368 published July 26, 1989, and US-A-5017714 and US-A-5120867 to Welborn, Jr.
  • These publications teach the structure of the metallocene catalysts and include alumoxane as the cocatalyst. There are a variety of methods for preparing alumoxane, one of which is described in US-A-4665208.
  • the terms "cocatalysts or activators” are used interchangeably and are defined to be any compound or component which can activate a bulky ligand transition metal compound.
  • the activators generally contain a metal of Group II and III of the Periodic Table of Elements.
  • the bulky transition metal compound are metallocenes, which are activated by trialkylaluminum compounds, alumoxanes both linear and cyclic, or ionizing ionic activators or compounds such as tri (n-butyl) ammonium tetra (pentafluorophenyl) boron, which ionize the neutral metallocene compound.
  • Such ionizing compounds may contain an active proton, or some other cation associated with but not coordinated, or only loosely coordinated to the remaining ion of the ionizing ionic compound.
  • Such compounds are described in EP- A-0520 732, EP-A-0 277 003 and EP-A-0 277 004 published August 3, 1988, and US-A-5153157; 5198401 and 5241025.
  • the metallocene catalyst component can be a monocyclopentadienyl heteroatom containing compound. This heteroatom is activated by either an alumoxane or an ionic activator to form an active polymerization catalyst system to produce polymers useful in this invention.
  • catalyst systems are described in, for example, PCT International Publication WO 92/00333 published January 9, 1992, US-A-5057475; 5096867; 5055438 and 5227440 and EP-A-0 420 436, WO 91/04257.
  • the metallocene catalysts useful in this invention can include non-cyclopentadienyl catalyst components, or ancillary ligands such as boroles or carbollides in combination with a transition metal.
  • the catalysts and catalyst systems may be those described in US-A-5064802 and PCT publications WO 93/08221 and WO 93/08199 published April 29, 1993.
  • All the catalyst systems of the invention may be, optionally, prepolymerized or used in conjunction with an additive or scavenging component to enhance catalytic productivity.
  • the polymer for use in the Koch reaction can include block and tapered copolymers derived from monomers comprising at least one conjugated diene with at least monovinyl aromatic monomer, preferably styrene. Such polymers should not be completely hydrogenated so that the polymeric composition contains olefinic double bonds, preferably at least one bond per molecule.
  • the Koch reaction can also include star polymers as disclosed in patents such as U.S. Patent Nos. 5,070,131; 4,108,945; 3,711,406; and 5,049,294.
  • Polymer Stripping Polymers useful for dispersants in lubricant applications can comprise a mixture or distribution of molecular weights. This distribution is a result of the processes used to make the polymers. Number average molecular weight is a useful way to represent the molecular weight distribution.
  • Light ester can be formed by two routes. Route one involves the introduction of light ester precursors such as C4 to C24 olefins which are impurities in the polymer feed. Route two may involve the generation of breakdown products during the carbonylation reaction.
  • This invention relates to "route one". It has been found that by stripping (e.g., removing light polymer and unreacted monomers such as olefins) from the polymer feed prior to the carbonylation step the amount of undesirable light polymer esters that is generated is reduced.
  • the stripping of the polymer feed can be accomplished by any suitable means.
  • the stripping can take place in a batch or continuous process.
  • the process equipment utilized is not critical providing that the necessary conditions of temperature and negative pressure (e.g., vacuum) can be met.
  • a short path evaporator is a useful means for stripping the polymers and is known in the art.
  • a typical short path evaporator comprises a vessel with product feed, and residue discharge means, a heating means and a distillate overhead with a condenser, a collector and vacuum pump.
  • the evaporator should be equipped with a condenser and collector means for recovery and disposal of the light polymer stripped from the polymer feed.
  • the evaporator should have sufficient volume to handle useful quantities of polymer feed (e.g., 50 kilograms per hour for a pilot unit and more for a commercial facility).
  • the evaporator should be capable of heating the polymer feed to temperature high enough for efficient evaporation of the light polymer. Suitable temperatures are in the range of 180 to 300°C, preferably 200 to 240°C, most preferably 220 to 230°C.
  • the evaporator may operate at atmospheric pressure but it is preferable to operate under negative pressure (e.g., vacuum) for more efficient stripping.
  • Suitable vacuum is in the range of 0.5 to 50 mm Hg, preferably 1.0 to 30 mm Hg, more preferably 1.5 to 20 mm Hg.
  • the efficiency of the light polymer stripping may be improved by optional agitation of the polymer feed in the evaporator or the use of inert gases (e.g., nitrogen) to assisting in separating the light polymer from the polymer residue. Techniques such as these are known in the art.
  • Carbonylation is the part of the functionalization process wherein the unsaturated polymer is reacted with carbon monoxide in the presence of an acid catalyst, preferably BF3, and a nucleophilic trapping agent, conveniently 2,4- dichlorophenol.
  • the resultant product is an ester with an attendant leaving group.
  • This functionalized product can be subsequently derivatized with an amine to form the useful dispersant for lubricant additive applications.
  • An excess over the stoichiometric amount of 2,4-dichlorophenol (DCP) is used in the reaction and it is necessary to remove the unreacted DCP from the crude ester produced in the reaction and recover it for reuse.
  • DCP 2,4-dichlorophenol
  • the crude ester produced in the carbonylation reaction consists essentially of unreacted DCP, impurities and the functionalized polymer.
  • the functionalized polymer includes lower molecular weight polymer and unreacted olefin monomers which range in carbon number from C4 to C24 which have been esterified.
  • the unreacted DCP can be removed from the crude polymer ester in a process of evaporation, stripping, or distillation.
  • Processes of this type are known in the art and can be run in equipment such as flash drums, falling film evaporators, forced film or wiped film evaporators, or short path evaporators or the like.
  • this equipment comprises a vessel or pipe wherein a liquid mass is heated to a temperature at which volatile material evaporates from the liquid mass.
  • the process can be run at atmospheric pressure or under negative pressure (e.g., vacuum). Negative pressure is preferable.
  • Agitation can be beneficial to assist in liquid/vapor disengagement.
  • Use of an inert gas (e.g., nitrogen) passing through the liquid mass can also assist in liquid/vapor disengagement.
  • Short path evaporators are particularly useful.
  • Short path evaporators are particularly useful.
  • the unreacted DCP is removed from the crude polymer ester it is desired to condense and collect it for subsequent reuse. This can be achieved by use of a condenser and collector either external or internal to the short path evaporator.
  • components that boil lower than the functionalized polymer such as the DCP, light esters and chlorinated mixtures are removed overhead to the distillate stream.
  • the bottom product of functionalized polymer is subsequently derivatized in an amination reactor. The distillate is collected and then fractionally distilled to recover and recycle the unreacted DCP.
  • n is generally greater than 0 and represents the functionality (F) or average number of functional groups per polymer chain.
  • functionality can be expressed as the average number of moles of functional groups per "mole of polymer".
  • mole of polymer includes both functionalized and unfunctionalized polymer, so that F corresponds to n of Formula (I).
  • the functionalized polymer will include molecules having no functional groups. Specific preferred embodiments of n include l > n > 0; 2 > n > l; and n >2. n can be determined by C ⁇ 3 NMR. The optimum number of functional groups needed for desired performance will typically increase with Mn of the polymer.
  • n The maximum value of n will be determined by the number of double bonds per polymer chain in the unfunctionalized polymer.
  • the "leaving group" (-YR 3 ) has a pKa of less than or equal to 12, preferably less than 10, and more preferably less than 8. The pKa is determined from the corresponding acidic species HY-R 3 in water at room temperature.
  • the functionalized polymer is very stable especially as the % neo substitution increases.
  • the Koch reaction is especially useful to make "neo" functionalized polymer which are generally more stable and labile than iso structures.
  • the polymer can be at least 60, more preferably at least 80 mole percent neofunctionalized.
  • the polymer can be greater than 90, or 99 and even about 100 mole percent neo.
  • the polymer defined by formula (I) Y is O (oxygen)
  • Rl and R 2 can be the same or different and are selected from H, a 5 hydrocarbyl group, and a polymeric group.
  • Y is O or S
  • R* and R 2 can be the same or different and are selected from H, a hydrocarbyl group a substituted hydrocarbyl group and a polymeric group
  • R 3 is selected from a substituted hydrocarbyl group, an aromatic group and a substituted aromatic group.
  • This embodiment is generally more 10 reactive towards derivatization with amines and alcohol compounds especially where the R 3 substituent contains electron withdrawing species.
  • a preferred leaving group, HYR 3 has a pKa of less than 12, preferably less than 10 and more preferably 8 or less. pKa values can range typically from 5 to 12, preferably from 6 to 10, and most preferably from 6 to 8. The pKa of the leaving 15 group determines how readily the system will react with derivatizing compounds to produce derivatized product.
  • R 3 is represented by the formula:
  • X which may be the same or different, is an electron withdrawing substituent
  • T which may be the same or different, represents a non-electron withdrawing substituent (e.g. electron donating)
  • m and p are from 0 to 5 with the sum of m and p being from 0 to 5. More preferably, m is from 1 to 5 and preferably 1 to 3.
  • a preferred R 3 is derived from 2,4- dichlorophenol.
  • composition derived from the present invention includes derivatized polymer which is the reaction product of the Koch functionalized polymer and a
  • Preferred derivatizing compounds include nucleophilic reactant compounds including amines, alcohols, amino-alcohols, metal reactant compounds and mixtures thereof.
  • Derivatized polymer will typically contain at least one of the following groups: amide, imide, oxazoline, and ester, and metal salt. The suitability for a particular end use may be improved by appropriate selection of the
  • Polymers produced by processes which result in a terminally unsaturated polymer chain can be functionalized to a relatively high yield in accordance with the process of the present invention. It has been found that the neo acid functionalized polymer can be derivatized to a relatively high yield.
  • the Koch process also makes use of relatively inexpensive materials i.e., carbon monoxide at relatively low temperatures and pressures. Also the leaving group -YR 3 can be removed and recycled upon derivatizing the Koch functionalized polymer with amines or alcohols.
  • the functionalized or derivatized polymers of the present invention are useful as lubricant additives such as dispersants, viscosity improvers and multifunctional viscosity improvers.
  • the composition derived from the present invention includes oleaginous compositions comprising the above functionalized, and/or derivatized polymer. Such compositions include lubricating oil compositions and concentrates.
  • the Koch reaction also provides a process which comprises the step of catalytically reacting in admixture: (a) at least one hydrocarbon polymer having a number average molecular weight of at least about 500, and an average of at least one ethylenic double bond per polymer chain; (b) carbon monoxide, (c) at least one acid catalyst, and (d) a nucleophilic trapping agent selected from the group consisting of water, hydroxy- containing compounds and thiol-containing compounds, the reaction being conducted a) in the absence of reliance on transition metal as a catalyst; or b) with at least one acid catalyst having a Hammett acidity of less than -7; or c) wherein functional groups are formed at least 40 mole % of the ethylenic double bonds; or d) wherein the
  • the process of the present invention relates to a polymer having at least one ethylenic double bond reacted via a Koch mechanism to form carbonyl or thio carbonyl group-containing compounds, which may subsequently be derivatized.
  • the polymers react with carbon monoxide in the presence of an acid catalyst or a catalyst preferably complexed with the nucleophilic trapping agent.
  • a preferred catalyst is BF3 and preferred catalyst complexes include BF3.H2O and BF3 complexed with 2,4- dichlorophenol.
  • the starting polymer reacts with carbon monoxide at points of unsaturation to form either iso- or neo- acyl groups with the nucleophilic trapping agent, e.g. with water, alcohol (preferably a substituted phenol) or thiol to form respectively a carboxylic acid, carboxylic ester group, or thio ester.
  • At least one polymer having at least one carbon-carbon double bond is contacted with an acid catalyst or catalyst complex having a Hammett Scale acidity value of less than -7, preferably from -8.0 to -11.5 and most preferably from -10 to -11.5.
  • an acid catalyst or catalyst complex having a Hammett Scale acidity value of less than -7, preferably from -8.0 to -11.5 and most preferably from -10 to -11.5.
  • a carbenium ion may form at the site of one of carbon-carbon double bonds.
  • the carbenium ion may then react with carbon monoxide to form an acylium cation.
  • the acylium cation may react with at least one nucleophilic trapping agent as defined herein.
  • At least 40 mole %, preferably at least 50 mole %, more preferably at least 80 mole %, and most preferably 90 mole % of the polymer double bonds will react to form acyl groups wherein the non-carboxyl portion of the acyl group is determined by the identity of the nucleophilic trapping agent, i.e. water forms acid, alcohol forms acid ester and thiol forms thio ester.
  • the polymer functionalized by the recited process of the present invention can be isolated using fluoride salts.
  • the fluoride salt can be selected from the group consisting of ammonium fluoride, and sodium fluoride.
  • Preferred nucleophilic trapping agents are selected from the group consisting of water, monohydric alcohols, polyhydric alcohols hydroxyl-containing aromatic compounds and hetero substituted phenolic compounds.
  • the catalyst and nucleophilic trapping agent can be added separately or combined to form a catalytic complex.
  • R2 R2 (carbenium ion)
  • the Koch reaction is particularly useful to functionalize poly(alpha olefins) and ethylene alpha olefin copolymers formed using metallocene-type catalysts. These polymers contain terminal vinylidene groups. There is a tendency for such terminal groups to predominate and result in neo-type (tertiary) carbenium ions.
  • the acid catalyst is preferably relatively strong. However, the strength of the acid catalyst is preferably balanced against detrimental side reactions which can occur when the acid is too strong.
  • the Koch catalyst can be employed by preforming a catalyst complex with the proposed nucleophilic trapping agent or by adding the catalyst and trapping agent separately to the reaction mixture. This later embodiment has been found to be a particular advantage since it eliminates the step of making the catalyst complex.
  • BF3.2H2O is ineffective at functionalizing polymer through a Koch mechanism ion with polymers.
  • BF3.H2O resulted in high yields of carboxylic acid for the same reaction.
  • the use of H2SO4 as a catalyst involves control of the acid concentration to achieve the desired Hammett Scale Value range.
  • Preferred catalysts are H2SO4 and BF3 catalyst systems.
  • Suitable BF3 catalyst complexes for use in the present invention can be represented by the formula:
  • R can represent hydrogen, hydrocarbyl (as defined below in connection with R') -CO-R', -SO2 - R ⁇ -PO-(OH)2, and mixtures thereof wherein R' is hydrocarbyl, typically alkyl, e.g., C ⁇ to C20 alkyl, and, e.g., Cg to C14 aryl, aralkyl, and alkaryl, and x is less than 2.
  • reaction mixture is further reacted with water or another nucleophilic trapping agent such as an alcohol or phenolic, or thiol compound.
  • water releases the catalyst to form an acid.
  • hydroxy trapping agents releases the catalyst to form an ester, the use of a thiol releases the catalyst to form a thio ester.
  • Koch product also referred to herein as functionalized polymer
  • derivatization reactions involving ester functionalized polymer will typically have to displace the alcohol derived moiety therefrom. Consequently, the alcohol derived portion of the Koch functionalized polymer is sometimes referred to herein as a leaving group.
  • the ease with which a leaving group is displaced during derivatization will depend on its acidity, i.e. the higher the acidity the more easily it will be displaced.
  • the acidity in turn of the alcohol is expressed in terms of its pKa.
  • Preferred nucleophilic trapping agents include water and hydroxy group containing compounds.
  • Useful hydroxy trapping agents include aliphatic compounds such as monohydric and polyhydric alcohols or aromatic compounds such as phenols and naphthols.
  • the aromatic hydroxy compounds from which the esters of this invention may be derived are illustrated by the following specific example: phenol, - naphthol, cresol, resorcinol, catechol, 2-chlorophenol. Particularly preferred is 2,4- dichlorophenol.
  • the alcohols preferably can contain up to about 40 aliphatic carbon atoms. They may be monohydric alcohols such as methanols, ethanol, benzyl alcohol, 2- methylcyclohexanol, beta-chloroethanol, monomethyl ether of ethylene glycol, etc.
  • the polyhydric alcohols preferably contain from 2 to about 5 hydroxy radicals; e.g., ethylene glycol, diethylene glycol.
  • Other useful polyhydric alcohols include glycerol, monomethyl ether of glycerol, and pentaerythritol.
  • Useful unsaturated alcohols include allyl alcohol, and propargyl alcohol.
  • Particularly preferred alcohols include those having the formula R 2 HOH where an R is independently hydrogen, an alkyl, aryl, hydroxyalkyl, or cycloalkyl.
  • Specific alcohols include alkanols such as methanol, ethanol, etc.
  • Also preferred useful alcohols include aromatic alcohols, phenolic compounds and polyhydric alcohols as well as monohydric alcohols such as 1,4- butanediol.
  • neo-acid ester functionalized polymer is extremely stable due, it is believed, to stearic hindrance. Consequently, the yield of derivatized polymer obtainable therefrom will vary depending on the ease with which a derivatizing compound can displace the leaving group of the functionalized polymer.
  • the most preferred alcohol trapping agents may be obtained by substituting a phenol with at least one electron withdrawing substituent such that the substituted phenol possesses a pKa within the above described preferred pKa ranges.
  • phenol may also be substituted with at least one non-electron withdrawing substituent (e.g., electron donating), preferably at positions meta to the electron withdrawing substituent to block undesired alkylation of the phenol by the polymer during the Koch reaction. This further improves yield to desired ester functionalized polymer.
  • the most preferred trapping agents are phenolic and substituted phenolic compounds represented by the formula:
  • X which may be the same or different, is an electron withdrawing substituent, and T which may be the same or different is a non-electron withdrawing group; m and p are from 0 to 5 with the sum of m and p being from 0 to 5, and m is preferably from 1 to 5, and more preferably, m is 1 or 2.
  • X is preferably a group selected from halogen, cyano, and nitro, preferably located at the 2- and/or 4- position, and T is a group selected from hydrocarbyl, and hydroxy groups and p is 1 or 2 with T preferably being located at the 4 and/or 6 position.
  • X is selected from CI, F, Br, cyano or nitro groups and m is preferably from 1 to 5, more preferably from 1 to 3, yet more preferably 1 to 2, and most preferably 2 located at the 2 and 4 locations relative to -OH.
  • the relative amounts of reactants and catalyst, and the conditions controlled in a manner sufficient to functionalize typically at least about 40, preferably at least about 80, more preferably at least about 90 and most preferably at least about 95 mole % of the carbon-carbon double bonds initially present in the unfunctionalized polymer.
  • the amount of H2O, alcohol, or thiol used is preferably at least the stoichiometric amount required to react with the acylium cations. It is preferred to use an excess of alcohol over the stoichiometric amount.
  • the alcohol performs the dual role of reactant and diluent for the reaction. However, the amount of the alcohol or water used should be sufficient to provide the desired yield yet at the same time not dilute the acid catalyst so as to adversely affect the Hammett Scale Value acidity.
  • the polymer added to the reactant system can be in a liquid phase.
  • the polymer can be dissolved in an inert solvent.
  • the yield can be determined upon completion of the reaction by separating polymer molecules which contain acyl groups which are polar and hence can easily be separated from unreacted non-polar compounds. Separation can be performed using absorption techniques which are known in the art. The amount of initial carbon-carbon double bonds and carbon- carbon double bonds remaining after the reaction can be determined by Cl 3 NMR techniques.
  • the polymer is heated to a desired temperature range which is typically between -20°C to 200°C, preferably from 0°C to 80°C and more preferably from 40°C to 65°C. Temperature can be controlled by heating and cooling means applied to the reactor. Since the reaction is exothermic usually cooling means are required. Mixing is conducted throughout the reaction to assure a uniform reaction medium.
  • the catalyst (and nucleophilic trapping agent) can be prereacted to form a catalyst complex or are charged separately in one step to the reactor to form the catalyst complex in situ at a desired temperature and pressure, preferably under nitrogen.
  • the nucleophilic trapping agent is a substituted phenol used in combination with BF3.
  • the reactor contents are continuously mixed and then rapidly brought to a desired operating pressure using a high pressure carbon monoxide source.
  • Useful pressures can be up to 138,000 kPa (20,000 psig), and typically will be at least 2070 kPa (300 psig), preferably at least 5,520 kPa (800 psig), and most preferably at least 6,900 kPa (1,000 psig), and typically will range from 3450 to 34,500 kPa (500 to 5,000 psig) preferably from 4485 to 20,700 kPa (650 to 3,000 psig) and most preferably from 4485 to 13,800 kPa (650 to 2000 psig).
  • the carbon monoxide pressure may be reduced by adding a catalyst such as a copper compound.
  • the catalyst to polymer volume ratio can range from 0.25 to 4, preferably 0.5 to 2 and most preferably .75 to 1.3.
  • the polymer, catalyst, nucleophilic trapping agent and CO are fed to the reactor in a single step.
  • the reactor contents are then held for a desired amount of time under the pressure of the carbon monoxide.
  • the reaction time can range up to 5 hours and typically 0.5 to 4 and more typically from 1 to 2 hours.
  • the reactor contents can then be discharged and the product which is a Koch functionalized polymer comprising either a carboxylic acid or carboxylic ester or thiol ester functional groups separated. Upon discharge, any unreacted CO can be vented off. Nitrogen can be used to flush the reactor and the vessel to receive the polymer.
  • the functionalized polymer containing reaction mixture may be a single phase, a combination of a partitionable polymer and acid phase or an emulsion with either the polymer phase or acid phase being the continuous phase.
  • the polymer is recovered by suitable means.
  • a suitable means can be used to separate the polymer.
  • a preferred means is the use of fluoride salts, such as sodium or ammonium fluoride in combination with an alcohol such as butanol or methanol to neutralize the catalyst and phase separate the reaction complex.
  • the fluoride ion helps trap the BF3 complexed to the functionalized polymer and helps break emulsions generated when the crude product is washed with water.
  • Alcohols such as methanol and butanol and commercial demulsifiers also help to break emulsions especially in combination with fluoride ions.
  • nucleophilic trapping agent is combined with the fluoride salt and alcohols when used to separate polymers. The presence of the nucleophilic trapping agent as a solvent minimizes transesterification of the functionalized polymer.
  • the functionalized polymer can be separated from the nucleophilic trapping agent and catalyst by depressurization and distillation. It has been found that where the nucleophilic trapping agent has lower pKa's, the catalyst, i.e. BF3 releases more easily from the reaction mixture.
  • a functionalized polymer comprises molecules which have been chemically modified by at least one functional group so that the functionalized polymer is (a) capable of undergoing further chemical reaction (e.g. derivatization) or (b) has desirable properties, not otherwise possessed by the polymer alone, absent such chemical modification. It will be observed from the discussion of formula I that the functional group is characterized as being represented by the parenthetical expression
  • R.2 moiety is not added to the polymer in the sense of
  • Rl and R represent groups originally present on, or constituting part of, the 2 carbons bridging the double bond before functionalization.
  • R and R2 were included within the parenthetical so that neo acyl groups could be differentiated from iso acyl groups in the formula depending on the identity of Rl and R .
  • the polymer will possess dispersant range molecular weights (Mn) as defined hereinafter and the functionality will typically be significantly lower than for polymer intended for making derivatized multifunctional V.I. improvers, where the polymer will possess viscosity modifier range molecular weights (Mn) as defined hereinafter.
  • any effective functionality can be imparted to functionalized polymer intended for subsequent derivatization, it is contemplated that such functionalities, expressed as F, for dispersant end uses, are typically not greater than about 3, preferably not greater than about 2, and typically can range from about 0.5 to about 3, preferably from 0.8 to about 2.0 (e.g. 0.8 to 1).
  • effective functionalities F for viscosity modifier end uses of derivatized polymer are contemplated to be typically greater than about 3, preferably greater than about 5, and typically will range from 5 to about 10.
  • end uses involving very high molecular weight polymers contemplate functionalities which can range typically greater than about 20, preferably greater than about 30, and most preferably greater than about 40, and typically can range from 20 to 60, preferably from 25 to 55 and most preferably from 30 to 50.
  • the functionalized polymer can be used as a dispersant/multifunctional viscosity modifier if the functional group contains the requisite polar group.
  • the functional group can also enable the polymer to participate in a variety of chemical reactions.
  • Derivatives of functionalized polymers can be formed through reaction of the functional group.
  • These derivatized polymers may have the requisite properties for a variety of uses including use as dispersants and viscosity modifiers.
  • a derivatized polymer is one which has been chemically modified to perform one or more functions in a significantly improved way relative to the unfunctionalized polymer and/or the functionalized polymer. Representative of such functions, are dispersancy and/or viscosity modification in lubricating oil compositions.
  • the derivatizing compound typically contains at least one reactive derivatizing group selected to react with the functional groups of the functionalized polymers by various reactions. Representative of such reactions are nucleophilic substitution, transesterification, salt formation, and the like.
  • the derivatizing compound preferably also contains at least one additional group suitable for imparting the desired properties to the derivatized polymer, e.g., polar groups.
  • such derivatizing compounds typically will contain one or more groups including amine, hydroxy, ester, amide, imide, thio, thioamido, oxazoline, or carboxylate groups or form such groups at the completion of the derivatization reaction.
  • the derivatized polymers include the reaction product of the above recited functionalized polymer with a nucleophilic reactant which include amines, alcohols, amino-alcohols and mixtures thereof to form oil soluble salts, amides, oxazoline, and esters.
  • a nucleophilic reactant which include amines, alcohols, amino-alcohols and mixtures thereof to form oil soluble salts, amides, oxazoline, and esters.
  • the functionalized polymer can be reacted with basic metal salts to form metal salts of the polymer.
  • Preferred metals are Ca, Mg, Cu, Zn, Mo, and the like.
  • Suitable properties sought to be imparted to the derivatized polymer include one or more of dispersancy, multifunctional viscosity modification, antioxidancy, friction modification, antiwear, antirust, seal swell, and the like.
  • the preferred properties sought to be imparted to the derivatized polymer include dispersancy (both mono- and multifunctional) and viscosity modification primarily with attendant secondary dispersant properties.
  • a multifunctional dispersant typically will function primarily as a dispersant with attendant secondary viscosity modification.
  • MFVI multifunctional viscosity index improvers
  • Dispersants maintain oil insolubles, resulting from oil use, in suspension in the fluid thus preventing sludge flocculation and precipitation.
  • Suitable dispersants include, for example, dispersants of the ash-producing (also known as detergents) and ashless type, the latter type being preferred.
  • the derivatized polymer compositions of the present invention can be used as ashless dispersants and multifunctional viscosity index improvers in lubricant and fuel compositions.
  • At least one functionalized polymer is mixed with at least one of amine, alcohol, including polyol, aminoalcohol, etc., to form the dispersant additives.
  • One class of particularly preferred dispersants are those derived from the functionalized polymer of the present invention reacted with (i) hydroxy compound, e.g., a polyhydric alcohol or polyhydroxy-substituted aliphatic primary amine such as pentaerythritol or trismethylolaminomethane (ii) polyoxyalkylene polyamine, e.g. polyoxypropylene diamine, and/or (iii) polyalkylene polyamine, e.g., polyethylene polyamine such as tetraethylene pentamine referred to herein as TEPA.
  • hydroxy compound e.g., a polyhydric alcohol or polyhydroxy-substituted aliphatic primary amine such as pentaerythritol or trismethylolaminomethane
  • Useful amine compounds for derivatizing functionalized polymers comprise at least one amine and can comprise one or more additional amine or other reactive or polar groups.
  • the functional group is a carboxylic acid, carboxylic ester or thiol ester, it reacts with the amine to form an amide.
  • Preferred amines are aliphatic saturated amines.
  • suitable amine compounds include: 1,2- diaminoethane; 1,3-diaminopropane; 1,4-diaminobutane; 1,6-diaminohexane; polyethylene amines such as diethylene triamine; triethylene tetramine; tetraethylene pentamine; etc.
  • Useful amine compounds include: alicyclic diamines such as 1,4- di(aminomethyl) cyclohexane, and heterocyclic nitrogen compounds such as imidazolines. Mixtures of amine compounds may advantageously be used. Useful amines also include polyoxyalkylene polyamines. A particularly useful class of amines are the polyamido and related amines.
  • the functionalized polymers of the present invention can be reacted with alcohols, e.g. to form esters.
  • the alcohols may be aliphatic compounds such as monohydric and polyhydric alcohols or aromatic compounds such as phenols and naphthols.
  • the aromatic hydroxy compounds from which the esters may be derived are illustrated by the following specific examples: phenol, beta-naphthol, alpha- naphthol, cresol, resorcinol, catechol, etc. Phenol and alkylated phenols having up to three alkyl substituents are preferred.
  • the alcohols from which the esters may be derived preferably contain up to about 40 aliphatic carbon atoms.
  • They may be monohydric alcohols such as methanols, ethanol, isooctanol, etc.
  • a useful class of polyhydric alcohols are those having at least three hydroxy radicals, some of which have been esterified with a monocarboxylic acid having from about 8 to about 30 carbon atoms, such as octanoic acid, oleic acid, stearic acid, linoleic acid, dodecanoic acid, or tall oil acid.
  • the esters may also be derived from unsaturated alcohols such as allyl alcohol, cinnamyl alcohol, propargyl alcohol.
  • Still another class of the alcohols capable of yielding the esters of this invention comprise the ether-alcohols and amino-alcohols including, for example, the oxyalkylene-, oxyarylene-, amino-alkylene-, and amino- arylene-substituted alcohols having one or more oxyalkylene, amino-alkylene or amino-arylene oxyarylene radicals. They are exemplified by Cellosolve, carbitol, phenoxyethanol, etc.
  • the functionalized polymer of this invention is reacted with the alcohols according to conventional esterification, or transesterification techniques. This normally involves heating the functionalized polymer with the alcohol, optionally in the presence of a normally liquid, substantially inert, organic liquid solvent/diluent and/or in the presence of esterification catalyst.
  • Useful reactive metals or reactive metal compounds are those which will form metal salts of the functionalized polymer or metal-containing complexes with the functionalized polymer.
  • Metal complexes are typically achieved by reacting the functionalized polymers with amines and/or alcohols as discussed above and also with complex forming reactants either during or subsequent to amination.
  • Complex- forming metal reactants include the nitrates, nitrites, halides, carboxylates, etc.
  • the appropriate functionalized polymer of this invention can be reacted with any individual derivatizing compound such as amine, alcohol, reactive metal, reactive metal compound or any combination of two or more of any of these; that is, for example, one or more amines, one or more alcohols, one or more reactive metals or reactive metal compounds, or a mixture of any of these.
  • Substantially inert organic liquid diluents may be used to facilitate mixing, temperature control, and handling of the reaction mixture.
  • reaction products produced by reacting functionalized polymer of this invention with derivatizing compounds such as alcohols, nitrogen-containing reactants, metal reactants, and the like will, in fact, be mixtures of various reaction products.
  • the functionalized polymers themselves can be mixtures of materials. While the functionalized polymers themselves possess some dispersant characteristics and can be used as dispersant additives in lubricants and fuels, best results are achieved when at least about 30, preferably, at least about 50, most preferably 100% of the functional groups are derivatized.
  • the functionalized and/or derivatized polymers from the present invention may be post-treated.
  • USSN 992,403 discloses processes for post treatment and is incorporated herein by reference.
  • the Koch functionalized polymer in addition to acting as intermediates for dispersant and MFVI manufacture, can be used as molding release agents, molding agents, metal working lubricants, point thickeners and the like.
  • the additives of the invention may be used by incorporation into an oleaginous material such as fuels and lubricating oils.
  • USSN 992,403 discloses the use of the additive derived from the present invention in fuels and lubricating oils and is incorporated herein by reference.
  • Example 1 a polymer feed was prestripped in a short path evaporator to eliminate light polymer (light ester precursors). The distillate was discarded. This prestripped polymer was fed into the carbonylation reaction (Example A) and reacted under conditions substantially similar to polymer which was not prestripped (Example B).
  • Example A and B a short path evaporator was used to strip unreacted dichlorophenol (DCP) and other impurities from crude ester produced in a carbonylation reaction. The distillate from the evaporations of Examples A and B was compared.
  • DCP dichlorophenol
  • Example 1 The data in Table 1 show that substantially less distillate was collected from the stripped polymer, 15.3 wt. % (Example A) than the unstripped polymer, 21.2 wt. % (Example B).
  • Example A had only 0.03 kg (mostly C4 and C5 esters) in 8.1 kg total distillate whereas the C4- C24 light esters of Example B amounted to about 0.1 kg (mostly C4-C6 esters) of 11.1 kg total distillate, as determined by mass balance data.
  • This near order of magnitude difference would have a dramatic economical effect on a commercial scale operation, requiring disposal and expensive handling of a much higher amount of light ester.
  • the light ester otherwise rapidly builds up in and deteriorates the production process unless removed by more expensive means.
  • Example A had only 0.79 grams light ester per kg functionalized polymer whereas Example B had 2.91 grams Table 2

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Emergency Medicine (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

L'invention se rapporte à un processus de pré-extraction appliqué à un polymère préalablement à son utilisation dans la réaction de Koch destinée à la production d'additifs dispersants. Il a été démontré que la pré-extraction ou l'extraction des hydrocarbures légers et d'un monomère n'ayant pas réagi du polymère, avant l'étape de carbonylation de la réaction de Koch, permet de minimiser le niveau d'impuretés à base d'esters légers générées. Les esters légers sont des sous-produits indésirables qui altèrent le recyclage du catalyseur provenant de l'étape de fonctionnalisation de la réaction de Koch.
EP95923927A 1994-06-17 1995-06-16 Polymere a pre-extraction utilise pour ameliorer les additifs dispersants obtenus par reaction de koch Withdrawn EP0765346A1 (fr)

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US26155794A 1994-06-17 1994-06-17
US261557 1994-06-17
PCT/US1995/007674 WO1995035326A1 (fr) 1994-06-17 1995-06-16 Polymere a pre-extraction utilise pour ameliorer les additifs dispersants obtenus par reaction de koch

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US5936041A (en) * 1994-06-17 1999-08-10 Exxon Chemical Patents Inc Dispersant additives and process
CN114195913B (zh) * 2021-12-23 2023-08-18 广东鲁众华新材料有限公司 一种提高碳五石油树脂闪蒸效果的方法

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US3539654A (en) * 1967-05-16 1970-11-10 Auxiliare De L Inst Francais D Method of modifying natural rubber with carbon monoxide and coreactant
GB8333031D0 (en) * 1983-12-10 1984-01-18 British Petroleum Co Plc Carboxylic acid esters/carboxylic acids
GB8724108D0 (en) * 1987-10-14 1987-11-18 Shell Int Research Preparation of functionalized polymers
IL107810A0 (en) * 1992-12-17 1994-02-27 Exxon Chemical Patents Inc Functionalized polymers and processes for the preparation thereof

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