Classifications

• • 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 relates to dispersant additives and processes for their preparation, and is particularly directed to an improved dispersant additive obtained via the Koch reaction and a process for preparing the same.
• 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-containing unctional group, such as a carboxylic acid or a carboxylic ester functional group.
• Koch-based dispersants include derivatives ofthe Koch reaction product.
• 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 prope ⁇ ies, and in the context ofthe invention polymers have a number average molecular weight ( M n ) of at least 500.
• Light polymer used herein refers to polymer having less than 300 molecular weight (e.g., 48 to 288). Deeper cut polymers herein refer to polymers having less than 500 molecular weight (e.g., 48 to 490).
• raw polymer is herein intended to refer to polymer as manufactured containing the above described light polymer and deeper cut polymers.
• 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.
• 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 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 fractionating (e.g., stripping) raw polymer to remove at least the light polymers or alternatively light hydrocarbon from the raw polymer prior to the reaction described above.
• the removal ofthe light polymer fraction results in a surprising reduction in the amount of heretofore unwanted by- products, such as light polymer esters formed during the Koch reaction.
• the removal ofthe deeper cut polymer fraction results in a fractionated polymer which allows a lubricating oil additive to be made of su ⁇ risingly improved dispersant properties.
• the functionalized fractionated polymer must be treated prior to the derivatization step.
• the crude ester produced in the carbonylation contains inter alia the functionalized fractionated polymer, impurities, and in the case ofthe use ofthe preferred nucleophilic trapping agent, unreacted halophenol (e.g., 2,4-dichlorophenol).
• unreacted halophenol e.g., 2,4-dichlorophenol
• the functionalized fractionated polymer is further treated to remove the unreacted halophenol.
• the distillate is collected and fractionally distilled to recover and recycle the unreacted halophenol.
• 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 ofthe 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-
• 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 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 a polymer used in the Koch reaction for making dispersant additives comprising: fractionating a polymer to remove a light hydrocarbon fraction prior to the carbonylation step.
• the present invention is also a functionalized, fractionated hydrocarbon polymer wherein the fractionated polymer backbone has M n ⁇ 500, functionalization is by groups ofthe 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, optionally, at least 50 mole % of the functional groups are attached to a tertiary carbon atom ofthe fractionated polymer backbone, the fractionated polymer prepared by fractionating a raw hydrocarbon polymer to remove a light hydrocarbon fraction from said raw hydrocarbon 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 attachment of groups ofthe 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, optionally, at least 50 mole % ofthe functional groups are attached to a tertiary carbon atom of the polymer backbone
• the present invention relates to an improved process for functionalization of fractionated hydrocarbon polymer wherein the fractionated polymer backbone has M n > 500 and light polymer (e.g., less than 300 molecular weight) has been removed prior to functionalization and the functionalization is by groups ofthe formula: -CO-Y-R 3 wherein Y is O or S, and either R 3 is (i) H, hydrocarbyl and at least 50 mole % ofthe functional groups are attached to a tertiary carbon atom ofthe polymer backbone or (ii) R 3 is aryl, substituted aryl or substituted hydrocarbyl and, optionally, at least 50 mole% ofthe functional groups are attached to a tertiary carbon atom ofthe polymer backbone.
• POLY (CR ] R2 CO-Y-R 3 ) n (I) wherein POLY is a fractionated hydrocarbon polymer backbone having a number average molecular weight of at least 500, n is a number greater than 0, R**, R 2 and R 3 may be the same or different and are each H or hydrocarbyl with the optional provisos that either (1) R ⁇ and R 2 are selected such that at least 50 mole percent ofthe -CRlR 2 groups wherein both R ⁇ and R 2 are not H, or (2) when R 3 is aryl, substituted aryl or substituted hydrocarbyl, R* and R 2 are selected such that at least 50 mole percent of the -CR-R*** groups wherein both R' and R 2 are not H.
• the present invention relates to a lubricating oil nitrogen- containing dispersant additive exhibiting improved dispersancy
• a nitrogen- containing polymeric material derived from a fractionated polymer having a M n of from about 700 to 10,000, a M w /M n , (molecular weight distribution, MWD) of from about 1.2 to 3 and containing less than about 10 mole% of polymer chains having a molecular weight of less than 500.
• the nitrogen-containing polymeric material comprises the reaction product of an amine compound and functionalized, fractionated polymer prepared by functionalizing the fractionated polymer to contain mono- or dicarboxylic acid producing groups.
• the functionalization is preferably via the Koch reaction as herein described, but can be carried out by any other methods suitable for introducing mono- or dicarboxylic acid producing groups into the fractionated polymer, such as by reacting the fractionated polymer with a carboxylic reactant selected from the group consisting of a monounsaturated monocarboxylic acid producing compound and a monounsaturated dicarboxylic acid producing compound.
• the present invention provides a process for preparing a lubricating oil nitrogen -containing dispersant exhibiting improved dispersancy properties which comprises (A) functionalizing a fractionated polymer having a M n of from about 700 to 10,000 and a MWD of from about 1.2 to 3 and containing less than about 10 mole% of polymer chains having a molecular weight of less than 500; and (B) reacting said functionalized, fractionated polymer with a nitrogen-containing compound.
• the functionalizing step preferably comprises carbonylating the fractionated polymer using a Koch reaction, but can be by any suitable method for introducing mono- or dicarboxylic acid producing groups, such as by reacting the fractionated polymer with a carboxylic reactant selected from the group consisting of a monounsaturated monocarboxylic acid producing compound and a monounsaturated dicarboxylic acid producing compound.
• the functionalization step can also be accomplished by alkyiation of a hydroxy aromatic compound (e.g., phenol) with the fractionated polymer; the resulting polymer substituted hydroxy aromatic compound can then be derivatized by reaction with am aldehyde and a reactive nitrogen- containing compound (e.g., an alkylene polyamine) to form a Mannich base dispersant.
• a hydroxy aromatic compound e.g., phenol
• a reactive nitrogen- containing compound e.g., an alkylene polyamine
• Hydrocarbon groups that is, aliphatic, (e.g., alkyl or alkenyl), alicyclic (e.g., cycloalkyl or cycloalkenyl), aromatic, aliphatic- and alicyclic- substituted aromatic, aromatic-substituted aliphatic and alicyclic radicals, and the like, as well as cyclic radicals wherein the ring is completed through another portion ofthe molecule (that is, the two indicated substituents may together form a cyclic radical).
• aliphatic e.g., alkyl or alkenyl
• alicyclic 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)
• Any hydrocarbyl radical containing aromatic is broadly referred to herein as
• Substituted hydrocarbon groups that is, radicals containing non- hydrocarbon substituents which, in the context of this invention, do not alter predominantly hydrocarbon character ofthe radical.
• substituents e.g., halo, hydroxy, alkoxy, carbalkoxy, nitro, alkylsulfoxy.
• 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 an 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.
• substituted hydrocarbyl denotes a radical having a carbon atom directly attached to the remainder ofthe molecule, wherein the character ofthe radical is not exclusively hydrocarbon due to the presence of non-hydrocarbon substituents, such as those noted above in describing "hydrocarbyl", or heteroatom groups in the radical.
• Any substituted hydrocarbyl radical containing aromatic is broadly referred to herein as “substituted aryl”
• the functionalized fractionated 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 bond via a Koch reaction to form the carboxylic acid, - 8 -
• carboxylic ester or thio acid or thio ester it is the object of this invention to remove light polymer or light hydrocarbon from the raw polymer prior to the functionalization. In another aspect, it is the object of this invention to remove deeper cut polymer from the raw polymer prior to the functionalization. While it is also possible to functionaiize the raw polymer and to then fractionate the functionalized raw polymer to remove functionalized light polymers or functionalized deeper cut polymers therefrom, this is not preferred as additional manufacturing costs will generally result.
• Koch reactions have not heretofore been applied to polymers having number average molecular weights greater than 500.
• the hydrocarbon polymer preferably has M n 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 ofthe type described in the prior art.
• the Koch reaction as applied in the process ofthe present invention, may result in good yields of functionalized polymer, even 90 mole % or greater.
• POLY in general formula I, represents a fractionated hydrocarbon polymer backbone having M n of at least 500 with the polymer less than 300 molecular weight removed, and/or light hydrocarbon of carbon number C4 to C24- M n may be determined by available techniques such as gel permeation chromatography (GPC). POLY is derived from unsaturated polymer. Such GPC methods are useful in determining the molecular weight and molecular weight distribution ofthe raw polymer, the fractionated polymer, the light polymer and the deeper cut 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 ofthe present invention.
• 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 inte ⁇ olymer) and mixtures.
• Homopolymers and inte ⁇ olymers include those derived from polymerizable olefin monomers of 2 to about 16 carbon atoms; usually 2 to about 6 carbon atoms. Particular reference is made to the alpha olefin polymers made using organo metallic coordination compounds A particularly preferred class of polymers are ethylene alpha olefin copolymers such as those disclosed in US-A-5017299.
• the polymer unsaturation can be terminal, intemal 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.
• Low molecular weight polymers also referred to herein as dispersant range molecular weight polymers, are polymers having M n 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 or GPC.
• Low molecular weight polymers are useful in forming dispersants for lubricant additives.
• low molecular weight polymers are preferably removed by fractionation (e.g., stripping or distillation) to obtain fractionated polymers having less than 10 mole% of deeper cut polymer chains, as described herein.
• Medium molecular weight polymers M n '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 M ⁇ can be determined by membrane osmometry.
• the higher molecular weight materials have M n 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.
• M n '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 ofthe ratio M w /M n referred to as molecular weight distribution (MWD) are not critical. However, a typical minimum M w /M n value of about 1.1-2.0 is preferred with typical ranges of about 1.1 up to about 4.
• the polymer material used for preparing the nitrogen- containing dispersant additives of this invention having improved dispersancy properties comprises a fractionated polymer having a M n of from about 700 to 10,000, more preferably from about 800 to 5,000, and most preferably from about 1,000 to 4,000 and a MWD of from about 1 2 to 3, most preferably from about 1 2 to 2.5, and containing less than about 10 mole% (preferaoly less than about 5 mole%, more preferably less than about 3 mole%) of polymer chains having a molecular weight of less than 500 Lub ⁇ cating oil dispersant additives prepared from such fractionated polymers have been found to exhibit su ⁇ singly improved dispersancy properties in internal combustion engine, crankcase lubricating oil applications
• polymerizable intemal olefin monomers (sometimes referred to in the patent literature as medial olefins) characterized by the presence within their structure ofthe group
• internal olefin monomers they normally will be employed with terminal olefins to produce polyalkenes which are inte ⁇ olymers
• 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) is deemed to be a terminal olefin
• 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 de ⁇ vatization reactions of this invention
• substituted hydrocarbon groups normally will not cont ⁇ bute more than about 10% by weight ofthe total weight ofthe 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
• the term "lower” when used with a chemical group such as in "lower alkyl” or “lower alkoxy” is intended to desc ⁇ be groups having up to seven carbon atoms
• the polyalkenes may include aromatic groups and cycloaliphatic groups such as would be obtained from polyme ⁇ zable cyclic olefins or cycloaliphatic substituted- polymerizable acrylic olefins
• polyalkenes free from aromatic and cycloaliphatic groups (other than the diene styrene mte ⁇ olymer exception already noted)
• polyalkenes de ⁇ ved from homopolymers and inte ⁇ olymers of terminal hydrocarbon olefins of 2 to 16 carbon atoms This further preference is qualified by the proviso that, while inte ⁇ olymers of terminal olefins are usually preferred, inte ⁇ olymers optionally containing up to about 40% of polymer units derived from intemal 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
• terminal and intemal 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.; propyl ene-tetramer; diisobutylene, isobutylene trimer; butadiene- 1,2; butadiene- 1,3; pentadiene-1,2; pentadiene-1,3, etc
• Useful polymers include alpha-olefin homopolymers and inte ⁇ olymers, and ethylene alpha-olefin copolymers and te ⁇ olymers.
• 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 te ⁇ olymers 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.
• R 4 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, l-butene, hexene-1, octene-1, etc., and mixtures thereof (e.g. mixtures of propylene and l-butene, and the like)
• Preferred polymers are copolymers of ethylene and propylene and ethylene and butene- 1 - 12 -
• the molar ethylene content ofthe 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.
• size exclusion chromatography also known as gel permeation chromatography (GPC)
• GPC gel permeation chromatography
• 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 amo ⁇ hous.
• the preferred ethylene alpha-olefin polymers are further characterized in that up to about 95% and more ofthe 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 carbon- 13 NMR.
• the preferred alpha-olefin monomers are butene- 1 and propylene and preferred alpha-olefin polymers are polypropylene, polybutene-1 and butene- 1- propylene copolymer (e.g., butene- 1 -propylene copolymers having 5 to 95 mole%, more typically 5 to 40 mole%, propylene).
• Preferred alpha-olefin polymers comprise polymer chains possessing high terminal unsaturation.
• 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 ofthe 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 den v ame 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 ⁇ 1 transition metal ("Group” refers to an identified group ofthe Periodic Table of Elements, comprehensively presented in "Advanced Inorganic Chemistry," F A Cotton, G Wilkinson, Fifth Edition, 1988, John Wiley & Sons).
• Other 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
• 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 X are present, they may be bridged.
• 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 ofthe Periodic Table of Elements
• the metallocene catalyst is represented by the formulas:
• Various forms ofthe catalyst system ofthe metallocene type may be used in the polymerization process of this invention.
• Exemplary ofthe development of metallocene catalysts in the an 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 Welbo , Jr. These publications teach the structure ofthe metallocene catalysts and include alumoxane as the cocatalyst.
• alumoxane there are a variety of methods for preparing alumoxane, one of which is described in US-A-4665208 For the pu ⁇ oses of this patent specification, 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 ofthe Periodic Table of Elements.
• the bulky transition metal compound are metallocenes, which are activated by trialkylaluminum compounds, aiumoxanes 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.
• ionizing compounds may contain an active proton, or some other cation associated with but not coordinated, or only loosely coordinated to the remaining ion ofthe ionizing ionic compound.
• 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.
• 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.
• 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 ofthe 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
• Polymers useful for dispersants in lubricant applications can comprise a mixture or distribution of molecular weights This distribution is a result ofthe processes used to make the polymers. Number average molecular weight is a useful way to represent the molecular weight dist ⁇ bution
• Light functionalized product can be formed by two routes Route one involves the introduction of light functionalized product 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 fractionating the raw polymer feed to remove light polymer and unreacted monomers such as olefins 9 /20127
• the amount of undesirable light functionalized polymer e.g., polymer esters
• the polymer thus functionalized can be reacted with a nitrogen-containing compound to prepare a derivative ofthe fractionated polymer that has improved lubricating oil dispersant properties.
• the fractionating ofthe polymer feed can be accomplished by any suitable means, such as by distillation with or without a (partial) vacuum, by stripping with an inert gas (e.g., nitrogen) with or without a (partial) vacuum, by solvent extraction, or by selective so ⁇ tion or the like.
• the fractionation can take place in a batch or continuous process.
• a short path evaporator (or wiped film evaporator) is a useful means for distilling 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 ofthe light polymer removed 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 ofthe 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 distilling. 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 ofthe light polymer removal may be improved by optional agitation ofthe polymer feed in the evaporator or by the use of inert gas stripping (e.g., nitrogen stripping) to assist in separating the light polymer from the polymer residue.
• inert gas stripping e.g., nitrogen stripping
• Carbonylation is the part ofthe 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 a halophenol such as 2,4-dichlorophenol, or, preferably 2-chloro-4-methylphenol.
• an acid catalyst preferably BF3
• a nucleophilic trapping agent conveniently a halophenol such as 2,4-dichlorophenol, or, preferably 2-chloro-4-methylphenol.
• 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 ofthe halophenol is used in the reaction and it is necessary to remove the unreacted halophenol from the crude ester produced in the reaction and recover it for reuse.
• the crude ester produced in the carbonylation reaction consists
• 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 halophenol 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. In general, this equipment compnses 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 men gas (e.g., nitrogen) passing through the liquid mass can also assist in liquid/vapor disengagement.
• Sho ⁇ path evaporators are particularly useful.
• a condenser and collector either extemal or intemal to the short path evaporator.
• components that boil lower than the functionalized polymer such as the halophenol, 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 halophenol
• some ofthe impurities especially light esters that boil close to halophenol as well as light halogenated compounds, are also inadvertently recycled.
• the recycle stream will become saturated with undesirable components. Since the evaporation is a single stage operation, an equilibrium level of undesirables will build up in the process streams. The levels of light ester will increase in the residue product, possibly adversely affecting the performance ofthe final dispersant. In order to maintain low impurity levels, the distillate might have to be frequently purged. This is very costly Thus, it is very desirable to minimize the amount of light ester present in the crude ester fed to the evaporators.
• n is generally greater than 0 and represents the functionality (F) or average number of functional groups per polymer chain, based on the polymer introduced into the Koch reaction
• functionality can be expressed as the average number of moles of functional groups per "mole of polymer" charged to the functionalization reactor
• F corresponds to n of Formula (I)
• the functionalized polymer product will generally include polymer 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 carbon- 13 NMR The optimum number of functional groups needed for desired performance will typically increase with M n of the polymer 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 polymers which are generally more stable and less 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) the polymer defined by formula (I), Y is O
• R 1 and R 2 are be the same or different and are selected from H, a hydrocarbyl group, and a polyme ⁇ c group
• Y is O or S
• R 1 and R 2 are 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 (aryl) and a substituted aromatic group (substituted aryl)
• This embodiment is generally more reactive towards de ⁇ vatization with amines and alcohol compounds especially where the R 3 substituent contains electron withdrawing species.
• a prefened 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 ofthe leaving group determines how readily the system will react with derivatizing compounds to produce de ⁇ vatized product
• R 3 is represented by the formula
• X each of which may be the same or different, is an electron withdrawing substituent, T, each of which may be the same or different, represents a non-electron withdrawing substituent (e.g. electron donating), and 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 prefened R 3 is derived from 2,4-dichlorophenol
• the composition derived from the present invention includes derivatized polymer which is the reaction product ofthe Koch functionalized polymer and a derivatizing compound.
• Prefened 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 ofthe following groups amide, i ide, oxazoline, and ester, and metal salt. The suitability for a particular end use may be improved by appropriate selection ofthe polymer. M n and functionality used in the derivatized polymer is discussed hereinafter.
• the Koch reaction permits controlled functionalization of unsaturated polymers.
• a carbon o the carbon-carbon double bond is substituted with hydrogen, it will result in an "iso" functional group, i.e. one of R ⁇ or R 2 of Formula I is H; or when a carbon ofthe double bond is fully substituted with hydrocarbyl groups it will result in an "neo" functional group, i e. both R ⁇ or R 2 of Formula I are non ⁇ hydrogen groups.
• 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 ofthe 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
• 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 ofthe 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 fractionated hydrocarbon polymer as described herein and containing ethylenic double bonds ; (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 % ofthe ethylenic double bonds; or d) wherein the nucleophilic trapping agent has a pKa of less than
• the process ofthe 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 -1 1.5.
• 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 -1 1.5.
• 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 % ofthe polymer double bonds will react to form acyl groups wherein the non-carboxyl portion of the acyl group is determined by the identity ofthe 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. 21
• Prefened 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.
• a terminally unsaturated polymer reacted via the Koch mechanism to form an acid or an ester.
• the polymer is contacted with carbon monoxide or a suitable carbon monoxide source such as formic acid in the presence of an acidic catalyst.
• the catalyst contributes a proton to the carbon-carbon double bond to form a carbenium ion This is followed by addition of CO to form an acylium ion which reacts with the nucleophilic trapping agent.
• POLY, Y, Rl, R 2 and R 3 are defined as above.
• R 2 R 2 (carbenium ion)
• R 2 R 2 (acylium ion)
• the Koch reaction is pa ⁇ icularly useful to functionalize poly(alpha olefins) and ethylene alpha olefin copolymers formed using metaliocene-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 ofthe acid catalyst is preferably balanced against detnmental side reactions which can occur when the acid is too strong
• H2SO4 as a catalyst involves control ofthe acid concentration to achieve the desired Hammett Scale Value range.
• Prefened 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 , C 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
• nucleophilic trapping agent such as an alcohol or phenolic, or thiol compound
• the use of water releases the catalyst to form an acid
• hydroxy trapping agents releases the catalyst to form an ester
• a thiol releases the catalyst to form a thio ester
• Koch product also refened to herein as functionalized polymer, typically will be derivatized as described hereinafter De ⁇ vatization reactions involving ester functionalized polymer will typically have to displace the alcohol de ⁇ ved moiety therefrom Consequently, the alcohol de ⁇ ved portion ofthe Koch functionalized polymer is sometimes refened to herein as a leaving group
• the ease with which a leaving group is displaced du ⁇ ng de ⁇ vatization will depend on its acidity, i e the higher the acidity the more easily it will be displaced
• the acidity in turn ofthe alcohol is expressed in terms of its pKa
• Prefened 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 examples: phenol, naphthol, cresol, resorcinol, catechol, the chlorophenols.
• the alcohols preferably can contain up to about 40 aliphatic carbon atoms.
• the polyhydric alcohols 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 prefened alcohols include those having the formula R*2CHOH where an R is independently hydrogen, an alkyl, aryl, hydroxyalkyl, or cycloalkyl. Specific alcohols include alkanols such as methanol, ethanol, etc.
• prefened useful alcohols include aromatic alcohols, phenolic compounds and polyhydric alcohols as well as monohydric
• 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 ofthe functionalized polymer.
• the most prefened 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 alkyiation ofthe phenol by the polymer during the Koch reaction. This further improves yield to desired ester functionalized polymer.
• the most prefened 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
• 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. More preferably X is selected from Cl, F, Br, cyano or nitro groups and m is preferably from 1 to 5, more preferably from 1 to 3, and more preferably 1 to 2
• a particularly preferred group of trapping agents encompassed by Formula (V) are the halophenols and especially the chlorophenois including monochlorophenols such as 2-chlorophenol and 4-chlorophenol, dichlorophenols such as 2,4- dichlorophenol, and chloroalkylphenols such as 2-chloro-4-methylphenoI and 4-chloro- 2-methyl phenol.
• the trapping agent is preferably selected from 2,4-dichlorophenol and 2-chloro-4-methyl phenol, and is most preferably 2-chloro-4-methylphenol.
• the relative amounts of reactants and catalyst, and the conditions controlled in a manner sufficient to functionaiize 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 prefened to use an excess of alcohol over the stoichiometric amount.
• the alcohol performs the dual role of reactant and diluent for the reaction.
• the amount ofthe 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 ofthe 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 abso ⁇ tion 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 20°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 0.75 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 Upon completion ofthe reaction, the polymer is recovered by suitable means
• a suitable means can be used to separate the polymer.
• a prefened 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 ofthe nucleophilic trapping agent as a solvent minimizes transesterification ofthe 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.
• I -C- R moiety is not added to the polymer in the sense of
• Rl and R 2 represent groups originally present on, or constituting part of, the 2 carbons bridging the double bond before functionalization. However, Rl and R 2 were included within the parenthetical so that - 27 -
• neo acyl groups could be differentiated from iso acyl groups in the formula depending on the identity of Rl and R 2
• the functionalized, fractionated polymer ofthe present invention is preferably prepared using the Koch reaction as heretofore described, it can also be prepared by any method suitable for introducing mono- or dicarboxylic acid producing groups (e.g., acid, ester, or anhydride groups) into the fractionated polymer.
• the functionalized, fractionated polymer can be prepared, for example, by reacting the fractionated polymer with a monounsaturated carboxylic reactant, which is typically a monounsaturated monocarboxylic acid producing compound or a monounsaturated dicarboxylic acid producing compound or mixtures thereof.
• monounsaturated C4 to C 10 dicarboxylic acid wherein (a) the carboxyl groups are vicinal (i.e., located on
• Exemplary monounsaturated carboxylic reactants are fumaric acid, itaconic acid, maleic acid, maleic anhydride, chloromaleic anhydride, acrylic acid, methacrylic acid, and C ⁇ to C4 alkyl esters ofthe foregoing; e.g., methyl maleate, ethyl fumarate, methyl acrylate, etc.
• Maleic anhydride is the preferred monounsaturated carboxylic reactant.
• the fractionated polymer can be functionalized by reaction with the monounsaturated carboxylic reactant using a variety of methods.
• the polymer can be first chlorinated to about 1 to 8 wt.% chlorine based on the weight of the polymer by passing chlorine through the polymer at a temperature of about 60 to 250°C for about 0.5 to 10 hours.
• the chlorinated polymer may then be reaced with sufficient monounsaturated carboxylic reactant at about 100 to 250°C for about 0.5 to 10 hours, so the product obtained will contain the desired number of moles ofthe monounsaturated carboxylic reactant per mole of chlorinated polymer.
• Processes of this general type are taught in, for example, US-A-3087436, 3172892, and 3272746. Altematively, the fractionated polymer and the monounsaturated carboxylic reactant can be mixed and heated while adding chlorine to the hot material. Processes of this type are disclosed in, for example, US-A-3215707, 3231587, 3912764,4110349 and 4234435.
• Fractionated polyisobutene e.g., having a M n of from 700 to 3,000, or more preferably from 900 to 2,500, and having a MWD of from 1.2 to 2.5
• MWD MWD of from 1.2 to 2.5
• the fractionated polymer and the monounsaturated carboxylic reactant can also be contacted at elevated temperatures to cause a thermal ene reaction to occur.
• the polymer and the carboxylic reactant will be contacted with stirring and in the absence of O2 and water (e.g., under N2) in a carboxylic reactant to polymer mole ratio of about 1: 1 to 10: 1 at a temperature of about 120 to 260°C for about 1 to 20 hours.
• Thermal ene processes are described, for example, in US-A-3361673 and US-A-3401118.
• Fractionated polyisobutene e.g., having a M n of from 700 to 3,000, or more preferably from 900 to 2,500, and having a MWD of from 1.2 to 2.5
• MWD MWD
• 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, fractionated 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 f nctionalization step can also be accomplished by alkylating a hydroxy aromatic compund (e.g., phenol) with the fractionated polymer to form a polymer substituted hydroxy aromatic compound , and wherein the resulting polymer substituted hydroxy aromatic compound is then derivatized by reaction with an aldehyde and an amine (e.g., an alkylene polyamine) to form a Mannich base dispersant, as will be discussed more fully below.
• a hydroxy aromatic compund e.g., phenol
• an amine e.g., an alkylene polyamine
• the funct ⁇ o:-i.:zec pcv- mer can be used as a dispersant multifunctional viscosity modifier ⁇ :.-. e rune:: onal group contains the requisite polar group.
• the functional group c : aiso enable the polymer to participate in a variety of chemical reactions.
• Derivar es of functionalized polymers can be formed through reaction of the functional grout These cen atized polymers may have the requisite properties for a variety of uses imt ding use as dispersants and viscosity modifiers.
• a derivatized polymer is one whirr, has beer, chemically modified to perform one or more functions in a significantly i ⁇ rroved way relative to the unfunctionalized polymer and/or the functionalized po ⁇ .er Representative of such functions, are dispersancy and/or viscosity modifiercn in lubr.cating oil compositions.
• the deriva — ng compound typically contains at least one reactive derivatizing group selected to ⁇ tzz ⁇ with :.-.e functional groups ofthe functionalized polymers by various reactions " representative of such reactions are nucleophilic substitution, transesterificatior. .alt formation, and the like.
• the derivatizing compound preferably also contains at ⁇ t ⁇ : one additional group suitable for imparting the desired properties to the derivatized rciymer. e g , polar groups.
• such derivatizing compounds typically will con :r. one or more groups including amine, hydroxy, ester, amide, imide, thio, thioamco. oxazciine, or carboxylate groups or form such groups at the completion ofthe lerivatization reaction.
• the deriv ⁇ ized polymers include the reaction product ofthe above recited functionalized po ⁇ -r.er with a nucleophilic reactant which include amines, alcohols, amino-alcohols an: mixtures thereof to form oil soluble salts, amides, oxazoline, and esters.
• a nucleophilic reactant which include amines, alcohols, amino-alcohols an: mixtures thereof to form oil soluble salts, amides, oxazoline, and esters.
• the functionalized polymer can be reacted with basic metal salts to form metal sain cf the pciymer
• Prefened metals are Ca, Mg, Cu, Zn, Mo, Na, K, Mn and the like.
• Functionaized, fractionated polymers prepared by reacting the fractionated polymer with a mr ⁇ ounsaturated carboxylic reactant which is typically a monounsaturate — onocarboxylic acid producing compound or a monounsaturated dicarboxylic acic rroducing compound or mixtures thereof, can be reacted with a amine or hydroxyamine or alcohol compound according to methods known in the art using a variety of methods
• a polymer -substituted (e.g., poiyisobutenyl- substituted) succinic anhydride or succinic acid, prepaied by reaction of a fractionated polymer (e.g., polyisobutene) of this invention with maleic anhydride can be reacted with an alkylene polyamine or hydroxy amine using the methods disclosed in U. S. Patents 4,683,624, 4, 102,798, 4, 1 16,876, 4,1 13,639, 5,266,223, (the disclosures which are
• Mannich condensation lubricating oil dispersants can be prepared by condensing about 1 mole of a high molecular weight hydrocarbyl substituted hydroxy aromatic material such as mono- or polyhydroxy benzene (wherein the high molecular weight hydrocarbyl substitutent comprises the fractionated polymer of this invention, e.g., having a number average molecular weight of 700 or greater) with about 1 to 2.5 moles of an aldehyde such as formaldehyde or paraformaldehyde and about 0.5 to 2 moles polyamine as disclosed, e.g., in U.S. Pat. Nos.
• 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.
• an MFVI will be derived from functionalized polymer having typically up to about one and at least about 0.5 functional groups, (i.e "n" of formula (I)) for each 20,000, preferably for each 10,000, most preferably for each 5,000 M n molecular weight segment in the backbone polymer.
• Dispersants typically up to about one and at least about 0.5 functional groups, (i.e "n" of formula (I)) for each 20,000, preferably for each 10,000, most preferably for each 5,000 M n molecular weight segment in the backbone polymer.
• 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 ofthe ash-producing (also known as detergents) and ashless type, the latter type being prefened.
• 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 prefened dispersants are those derived from the functionalized polymer ofthe 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. Where the functional group is a carboxylic acid, carboxylic ester or thiol ester, it reacts with the amine to form an amide.
• Prefened amines are aliphatic saturated amines.
• Useful amines include polyalkylene polyamines having about 2 to 60 (e.g., 2 to 30), preferably 2 to 40 (e.g., 3 to 20) total carbon atoms and about 1 to 12 (e.g., 2 to 9), preferably 3 to 12 nitrogen atoms in the molecule.
• Non-limiting examples of 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; polypropylene amines such as 1,2-propylene diamine, di-(l,2-propylene) triamine and di-(l,3- propylene) triamine; N,N-dimethyl-l,3-diaminopropane; N,N'-di-(2-aminoethyl) ethylene diamine, 3-dodecylpropylamine, N-dodecyl- 1,3 -propane diamine; mono-, di-, and tri-tallow amines; aminomo ⁇ holines such as N-(3-aminopropyl) mo ⁇ holine; and mixtures thereof.
• Hydroxyamines which can be used include 2-amino-l-butanol, 2-amino-2- methyl-1 -propanol, p-(beta-hydroxyethyl)-aniline, 2-amino-l -propanol, 3 -amino- 1- propanol, 2-amino-2-methyl 1,3-propane-diol, 2-amino-2-ethyl-l,3-propanediol, N- (beta— hydroxypropyl)-N'-(beta-arnino-ethyl)-piperazine, tris(hydroxymethyl) amino- methane (also known as trismethylolaminomethane), 2-amino-l-butanol, ethanolamine, beta-(beta--hydroxyethoxy)-ethvlam ⁇ ne and the like Mixtures of these or similar amines can also be employed
• 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, such as commercial mixtures of polyethylene polyamines averaging 5 to 7 nitrogen atoms per molecule available under the trade names E-100 (Dow Chemical) and HPA-X (Union Carbide)
• Useful amines also include polyoxyalkylene polyamines
• a particularly useful class of amines are the polyamido and related amines.
• the amine compound can be a heavy polyamine, which is defined herein as a mixture of higher oligomers of polyalkylene polyamines, having an average of at least about 7 nitrogen atoms per molecule
• a prefened heavy polyamine is a mixture of polyethylene polyamines containing essentially no TEPA, at most small amounts of pentaethylene hexamme, and the balance oligomers with more than 6 nitrogens, the heavy polyamine having more branching than conventional commercial polyamines mixtures, such as the E-100 and HPA-X mixtures noted in the preceding paragraph
• a useful heavy polyamine composition is commercially available from Dow Chemical under the tradename HA-2 Useful heavy polyamines are further described in USSN 273,294, filed July 1 1, 1994, herein inco ⁇ orated by reference in its entirety
• 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 prefened
• 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
• the functionalized polymer of this invention is reacted with the alcohols according to conventional esterification, or transesteriftcation 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 ofthe 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% ofthe functional groups are derivatized.
• the functionalized and/or derivatized polymers from the present invention may be post-treated.
• USSN 534,891, filed September 25, 1995 discloses processes for post treatment and is inco ⁇ orated herein by reference.
• the functionalized polymers derivatized with amine compounds can be borated by treatment with a borating agent Suitable borating agents incude boron halides (e.g., boron trifluoride, boron tribromide, boron trichloride), boron acids, and simple esters ofthe boron acids (e.g., trialkyl borates containing 1 to 8 carbon alkyl groups such as methyl, ethyl, n-octyl, 2-ethylhexyl, etc.)
• boron halides e.g., boron trifluoride, boron tribromide, boron trichloride
• boron acids e.g., boron acids
• the boration reaction is typically carried out by adding from about 0.05 to 5 wt.%, e.g. 1 to 3 wt.%), (based on the weight ofthe amine-containing polymeric material) ofthe borating agent, and heating with stirring at from about 90 to 250°C, preferably 135 to 190°C, e.g., 140 to 170°C, for from about 1 to 10 hours followed by nitrogen stripping in said temperature ranges.
• the borating agent is preferably boric acid which is most usually added as a slurry to the reaction mixture.
• a prefened low sediment process involves borating with a particulate boric acid having a particle size distribution characterized by a ⁇ value of not greater than about 450. The process is described in US-A-5430105, herein inco ⁇ orated by reference.
• the borated product contains at least about 0.01 up to about 10 wt.% boron based on the total weight of product, but preferably has 0.05 to 5 wt.%, e.g., 0.05 to 2 wt.% boron.
• the functionalized polymers of this invention 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 inco ⁇ oration into an oleaginous material such as fuels and lubricating oils.
• USSN 534,891 discloses the use ofthe additive derived from the present invention in fuels and lubricating oils and is inco ⁇ orated 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
• Example A had only 0.79 grams light ester per kg functionalized polymer whereas Example B had 2.91 grams

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• 1995
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