WO1999033884A1 - Polymeres reactifs fonctionnalises par des esters - Google Patents

Polymeres reactifs fonctionnalises par des esters Download PDF

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Publication number
WO1999033884A1
WO1999033884A1 PCT/US1998/027348 US9827348W WO9933884A1 WO 1999033884 A1 WO1999033884 A1 WO 1999033884A1 US 9827348 W US9827348 W US 9827348W WO 9933884 A1 WO9933884 A1 WO 9933884A1
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ester
polymer
functionalized
group
formula
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PCT/US1998/027348
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English (en)
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Jacob Emert
David C. Dankworth
Antonio Gutierrez
Jon E. Stanat
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Exxon Chemical Patents Inc.
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Publication of WO1999033884A1 publication Critical patent/WO1999033884A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/14—Esterification

Definitions

  • the invention relates to an improved ester-functionalized polymer and a process for making the polymer via the Koch reaction.
  • the invention also relates to derivatives of the ester-functionalized polymer (e.g., amine derivatives) and fuel and lubricating oil compositions containing the ester-functionalized polymer or its derivatives.
  • 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 (“M n ”) of at least about 200.
  • hydrocarbon compound is used herein to refer to non-polymeric compounds comprising hydrogen and carbon having uniform properties such as molecular weight. However, the term “hydrocarbon” does not exclude mixtures of such compounds which individu ly are characterized by such uniform properties.
  • Carboxyl groups have the general formula -CO-OR" , where R can be H, a hydrocarbyl group, or a substituted hydrocarbyl group.
  • R can be H, a hydrocarbyl group, or a substituted hydrocarbyl group.
  • the synthesis of carboxyl group-containing compounds from olefinic hydrocarbon compounds, carbon monoxide, and water or alcohol in the presence of metal carboxyls has been disclosed, as, for example, inN. Bahrmann, Chapter 5, Koch Reactions, "New Synthesis With Carbon Monoxide", J. Falbe: Springer- Veriag, New York, 1980. Hydrocarbon compounds having olefinic double bonds react in two steps to form carboxylic acid-containing compounds.
  • the olefin compound reacts with .an acid catalyst and carbon monoxide.
  • This is followed by a second step in which the intermediate formed during the first step undergoes hydrolysis or alcoholysis to form a carboxylic acid or ester.
  • An advantage of the Koch reaction is that it can occur at moderate temperatures of -20°C to 80°C, and pressures up to 10,000 kPa (100 bar).
  • the Koch reaction can occur at double bonds where at least one carbon atom in the double bond is di-substituted to form a "neo" acid or ester, such as can be represented by formula:
  • R and R y are the same or different hydrocarbyl groups and R z is H or hydrocarbyl.
  • the Koch reaction can also occur when both carbons are mono- substituted or one is mono-substituted .and one is unsubstituted to form an "iso" acid or ester; e.g., -R ⁇ C-COOR 2 .
  • 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.
  • US-A-5629434 discloses the reaction of polymers having a number average molecular weight of at least 500 and having at least one ethylenic double bond via a Koch mechanism to form functionalized polymers containing (thio)carboxylic acid or ester groups.
  • US '434 further discloses that the functionalized polymers can contain neo substituted acid or ester functional groups, and further discloses derivatizing the functionalized polymers by reaction with nucleophilic reactant compounds including .amines, alcohols, aminoalcohols, metal reactant compounds and mixtures thereof.
  • Hydrocarbon polymers functionalized to contain a substantial proportion of neo substituted (thio)carboxylic acid or ester groups tend to be chemically stable and difficult to react with nucleophilic compounds in comparison to similar or analogous functionalized polymers having little or no neo function ⁇ group content (e.g., polyolefin substituted mono-and dicarboxylic acids such as polyisobutenyl succinic acids or anhydrides and polyisobutenyl propionic acids). This chemical stability is believed to be due at least in part to steric factors.
  • the present invention is directed to neo ester-functionalized polymers which are more reactive than the neo ester-functionalized polymers previously disclosed in the art.
  • the neo ester polymers of the present invention react more easily with amines, especially polyamines, achieving high yields of amine-derivatized product.
  • the reactive ester polymers of the present invention are characterized by having a higher proportion of less hindered ester functional groups than heretofore achieved.
  • the present invention is an ester-functionalized hydrocarbon polymer comprising -CH 2 CH 2 - units, -CH 2 CHR- units, and at least one carboxylic ester- containing unit of formula:
  • R is Ci to C ⁇ 8 line.ar alkyl, C 3 to Cig branched alkyl, or C ⁇ to C 1 aryl; R' is substituted alkyl, aryl, or substituted .aryl; and wherein:
  • the present invention is an ester-functionalized hydrocarbon polymer comprising -CH 2 CH 2 - units (dimethylene units), -CH 2 CHR- units (alkylethylene units and/or arylethylene units), and at least one carboxylic ester- containing unit of formula (I) as defined above, wherein:
  • ester-fiinctionalized polymer of the invention set forth in the preceding paragraph can alternatively be defined in terms of the following structural configurations A, B, C and D:
  • the present invention is an ester-functionalized hydrocarbon polymer comprising -CH 2 CH 2 - units (dimethylene units), -CH 2 CHR- units (alkylethylene units and/or arylethylene units), and at least one carboxylic cster- containing unit of formula (I) as defined above, and wherein
  • R in any of the ester- function.alized polymers defined above is preferably selected from linear alkyl groups of from 1 to 8 carbon atoms and branched alkyl groups of from 3 to 8 carbon atoms, is more preferably an alkyl group of from 1 to 2 carbon atoms (i.e., R is selected from the group consisting of methyl .and ethyl), and is most preferabyl is ethyl.
  • the present invention also includes derivatized polymers formed by reacting the ester-function-alized polymer as just described with a nucleophilic reactant compound selected from the group consisting of amines, amino alcohols, alcohols, reactive metals, and reactive metal compounds.
  • the present invention further includes post-treated derivatized polymers formed by treating the derivatized polymers with post-treating agents such as borating agents and acylating agents.
  • the present invention relates to a functionalized hydrocarbon polymer wherein the polymer backbone is derived from a hydrocarbon polymer having a number average molecular weight of at least about 200 and functionalization is by ester groups of formula:
  • R' is substituted .alkyl, aryl, or substituted aryl and the functional groups are attached to a tertiary carbon atom of the polymer (i.e., the functional groups .are "neo" groups).
  • R' is preferably substituted aryl.
  • the functionalized polymer can be derived from a hydrocarbon polymer comprising a 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 ester.
  • a polymer having at least one ethylenic double bond is contacted with an acid catalyst and carbon monoxide in the presence of an alcohol, which acts as a nucleophilic trapping agent.
  • an alcohol which acts as a nucleophilic trapping agent.
  • the polymers which are useful in the present invention are hydrocarbon polymers containing at least one carbon-carbon double bond (olefinic or ethylenic) unsaturation and also characterized by having aliphatic hydrocarbyl branches or aryl branches along the polymer backbone.
  • the maximum number of functional groups per polymer chain is limited by the number of double bonds per drain.
  • a polymer having one double bond per polymer chain when reacted in accordance with the Koch process as described in detail below, will form a monofunctionalized polymer.
  • the polymer typically has an average of about one to less than about 50 branches per 100 backbone carbon atoms.
  • Polymers which are useful for prep-aring the ester-fiinctionalized polymers of the invention include unsaturated ethylene ⁇ -olefin ( ⁇ AO") polymers comprising ethylene and at least one ⁇ -olefin represented by the formula:
  • R is a Ci to Cig linear alkyl group, a C 3 to C ⁇ 8 branched alkyl group, or a C ⁇ to C 1 4 aryl group.
  • R in the above formula is a linear alkyl group of from 1 to 8 carbon atoms or a branched alkyl group of from 3 to 8 carbon atoms. More preferably R is an alkyl group of from 1 to 2 carbon atoms, and is most preferably ethyl.
  • ⁇ -olefin monomers suitable for polymerization with ethylene include propylene, butene-1, pentene-1, 3-methylbutene-l, hexene-1, 4-methylpentene-l, heptene-1, octene-1, nonene-1, decene-1, dodecene-1, tridecene-1, tetradecene-1, pentadecene-1, hexadecene-1, heptadecene-1, octadecene-1, nonadecene-1, eicosene-1 and mixtures thereof (e.g., mixtures of propylene .and pentene-1, propylene and pentene-1 and hexene-1, and so forth).
  • Preferred ⁇ -olefin monomers for use with ethylene include propylene, butene-1, pentene-1, 3-methylbutene-l, hexene-1, 4-methylpentene-l, heptene-1, octene-1 and mixtures thereof. More preferred ⁇ -olefin monomers are propylene, butene-1 and a mixture of propylene and butene-1.
  • the more preferred EAO polymers are ethylene-propylene polymer, ethylene-butene-1 polymer, and ethylene-propylene-butene-1 polymer.
  • the most preferred ⁇ -olefin monomer is butene-1, and, accordingly, the most preferred EAO polymer is ethylene-butene-1 polymer.
  • R in Formula (HI) CM also be C 6 to C 14 aryl, by which is me ⁇ mt C 6 to C M unsubstituted (e.g., phenyl and naphthyl) or alkyl-substituted aromatic groups (e.g., tolyl and xylyl).
  • suitable ⁇ -olefin monomers include styrene, methylstyrenes such as 2- and 4-methylstyrene, ethylstyrenes such as 4-ethylstyrene, dimethylstyrenes such as 2,4-dimethylstyrene, ethylstyrene, allylbenzene, and naphthylethylene.
  • exemplary polymers incorporating these ⁇ -olefins are ethylene-styrene polymer, ethylene-4-methylstyrene polymer, ethylene-propylene-styrene polymer, and ethylene- butene-1 -styrene polymer.
  • the mol.ar ethylene content of the EAO polymers (i.e., the mole percent of units in the copolymer derived from ethylene) is suitably at least about 5 mole% (e.g., from about 5 to about 95 mole%) and is typically in the range of from about 15 to about 90 mole%, more typically from about 20 to about 80 mole%, and preferably from about 30 to about 65 mole%.
  • the molar ethylene content of the polymers can be determined by ⁇ -NMR or 13 C-NMR.
  • EAO polymers suitable for use in preparing the ester-fiinctionalized polymers of the invention include polymers comprising ethylene, at least one ⁇ -olefin of formula (HI), and at least one non-conjugated diene such as dicyclopentadiene, 1,4-hexadiene, and ethylidene norbornene, and other such dienes known in the art.
  • HI ⁇ -olefin of formula
  • the non- conjugated diene content of the polymer is generally less than about 15 mole% (e.g., from about 0.1 to about 15 mole%), typically less than about 10 mole% (e.g., from about 0.1 to about 10 mole%), and is especially from about 0.1 to about 5 mole%.
  • suitable EAO polymers include ethylene ⁇ -olefin diene polymers comprising from about 15 to about 90 mole% of units derived from ethylene, from about 10 to about 85 mole% of units derived from .an ⁇ -olefin of formula (HI), and from about 0.1 to about 15 mole% of units derived from a non-conjugated diene. Diene content of the polymers can be determined by 1H-NMR or 13 C-NMR The EAO polymer Iras a number average molecular weight of from about 200 to about 20,000.
  • the EAO polymers have a M n of from about 500 to about 20,000 (e.g., from about 700 to about 20,000 or from about 1,000 to about 20,000), typically from about 700 to about 15,000 (e.g., from about 1,000 to about 15,000), and more typically from about 1,000 to about 10,000 (e.g., from about 1,500 to about 10,000 or from about 2,000 to about 8,000).
  • M n of from about 500 to about 20,000 (e.g., from about 700 to about 20,000 or from about 1,000 to about 20,000), typically from about 700 to about 15,000 (e.g., from about 1,000 to about 15,000), and more typically from about 1,000 to about 10,000 (e.g., from about 1,500 to about 10,000 or from about 2,000 to about 8,000).
  • These polymers are especially useful for preparing esrter-functionalized polymers of the invention (and derivatives thereof) which are effective as dispersant additives in lubricating oils, and, accordingly, may also be referred to herein as dispersant range molecular weight polymers.
  • EAO polymers having a M n in the range of from about 900 to about 7,000 (e.g., from about 1,000 to about 6,000) are especially suitable for preparing ester- function.alized polymers of the invention (.and derivatives thereof) that are useful as lubricating oil dispersant additives.
  • the EAO polymers particularly polymers having number average molecular weights of from about 200 to about 3,000 (e.g., about 200 to about 1,500), are useful in forming ester-functionalized polymers of the invention (and derivatives thereof) that have utility as detergent and/or dispersant additives in fuels.
  • EAO polymers having number average molecular weights of from about 200 to about 1000, preferably from about 200 to about 500, are suitable for preparing ester-functionalized polymers of the invention (and derivatives thereof) that are useful as detergent additives in two-cycle engine oils.
  • M n 's of the EAO polymers can be determined by vapor phase osmometry ("VPO”; see, e.g., ASTM No. D3592) or by gel permeation chromatography ("GPC”).
  • VPO vapor phase osmometry
  • GPC gel permeation chromatography
  • the value of the ratio MJM n referred to as molecular weight distribution ("MWD"), for the EAO polymers is not critical. However, a minimum MJM n value of from about 1.1 to about 2.0 is especially suitable, and a typical range is from about 1.1 to about 5 (e.g., from about 1.1 to about 3).
  • the EAO polymer is unsaturated and has 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 about 30% (e.g., from about 30 to about 100%), typically at least about 50% (e.g., from about 50 to about 99%), preferably at least about 60% (e.g., from about 60 to about 99%), and more preferably at least about 75% (e.g., from about 75 to about 98%) of the unsaturation in the EAO polymer is terminal vinylidene (also referred to in the art as terminal ethenylidene unsaturation).
  • terminal vinylidene also referred to in the art as terminal ethenylidene unsaturation.
  • the types and percentages of unsaturation in the polymer can be determined via FTIR spectroscopic analysis, 1H-NMR, or 13 C-NMR.
  • the EAO polymers are characterized by having aliphatic hydrocarbyl branches or aryl branches along the backbone, wherein the alkyl branches are typically linear or branched Ci to C 18 alkyl groups and mixtures thereof. More particularly, the EAO polymers have an average of at least about 1 to less than about 50 branches per 100 backbone carbon atoms. The polymers typically have an average of from about 5 to less than about 50, more typically from about 10 to about 40, and preferably from about 15 to about 35 branches per 100 backbone carbon atoms. The type and amount of branching in the EAO polymers can be controlled to a large extent by the choice of ⁇ -olefin monomer(s) and the degree of incorporation of the chosen monomer(s) into the polymer.
  • the EAO polymers are prepared by polymerization of ethylene and the selected co-monomer(s) in the presence of a transition metal coordination catalyst which will generally result in a "normal" polymerization; i.e., the usual unit in the polymer derived from ethylene will be -CH2CH2- and the usual unit derived from an ⁇ -olefin of formula (DDL) will be - CH 2 CHR- wherein R is a branch on the carbon-carbon backbone.
  • DDL ⁇ -olefin of formula
  • Other units with different branching may be present due, for example, to "defective" monomer insertion during the polymerization, but such units are generally present only in negligible amounts.
  • an ethylene-propylene polymer containing 50 mole% units derived from ethylene will have an average of about 25 branches per 100 backbone carbon atoms (which is equivalent in this case to an average of about 20 branches per 100 total carbon atoms in the polymer), wherein substantially all of the branches are methyl groups.
  • the average branching in the EAO polymer can be determined by 1H-NMR or 13 C-NMR.
  • Such substituents contribute suitably not more than about 10 wt.%, typically not more than about 5 wt.%, and preferably not more than about 1 wt.%, of the total weight of the EAO polymer.
  • the EAO polymers can be prepared by polymerizing monomer mixtures comprising ethylene and the corresponding ⁇ -olefin monomers (optionally also containing non-conjugated diene(s)) 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 ethylene content can be controlled through selection of the metallocene catalyst component and by controlling the relative amounts of the monomers.
  • polymers suitable for use in the present invention are the polyolefins of ethylene, acyclic olefins (e.g., propylene, 1-butene, 2-butene, 1-pentene, 1-hexene, 1-octene, 1-tetradecene) and/or cyclic olefins (e.g., norbornene and cyclopentene) described in WO-A-96/23010.
  • these polyolefins are not "normal" polymers, and thus the branching in the resulting polyolefins typically differs from the branching in the monomer(s) from which they .are derived.
  • polymers such as polyethylenes .and polypropylenes
  • branching as characterized by the number of branches per 1000 methylene groups in the polyolefin and in the number of ethyl, propyl, butyl, amyl and hexyl or greater branches per 100 methyl branches.
  • WO '010 also describes methods for preparing these polyolefins by polymerization of the corresponding monomers in the presence of selected transition metal compounds (e.g., a transition metal complex of a bidentate ligand) and sometimes co-catalysts.
  • transition metal compounds e.g., a transition metal complex of a bidentate ligand
  • the ester-functionalized polymer of the present invention is a hydrocarbon polymer as described above which has been functionalized to contain -C0 2 R' ester groups, wherein the ester groups .are attached to a tertiary carbon atom of the polymer backbone.
  • the ester groups are neo ester groups.
  • the polymer can contain a small proportion of ester groups which are not neo substituted; i.e., up to about 25% (e.g., from about 1 to about 20%) of the ester groups can be non-neo substituents.
  • the ester-functionalized polymer of the present invention can be described as a reactive neo-ester substituted polymer, because it is more reactive with nucleophilic reactant compounds (e.g., amines, especially polyamines) tlran are neo ester- functionalized polymers heretofore known in the art.
  • the ester-functionalized polymer of the invention is characterized by having a greater proportion of less sterically hindered neo-substituted ester groups than are found in heretofore known neo-ester- functionalized polymers, and is thus more chemically reactive.
  • the ester-function ized polymer of the present invention CM be depicted in general terms by the formula: R 1
  • POLY is a backbone derived from a hydrocarbon polymer having a number average molecular weight of at least about 200; n is a number greater than 0; R 1 and R 2 are independently the .same or different and are each H, hydrocarbyl, or polymeric hydrocarbyl with the proviso that R 1 and R 2 are selected such that in at least about 75%, preferably at least about 90% (e.g., from about 95 to about 100%), of the - CR X R 2 - groups both R 1 and R 2 are not H (i.e., at least about 75% of the -C0 2 R' groups are "neo" groups); and R' is as defined in formula (I).
  • polymeric hydrocarbyl refers to a radical derived from the hydrocarbon polymer which can contain non-hydrocarbon substituents provided the radical is predominantly hydrocarbon in character.
  • n in Formula (IV) represents the functionality of the ester- function-alized hydrocarbon polymer, i.e., n is the average number of function ⁇ groups per polymer drain. Alternatively expressed, n is the average number of moles of functional groups per "mole of polymer", wherein "mole of polymer” refers to the moles of starting hydrocarbon polymer used in the functionalization reaction and therefore includes both functionalized and unfunctionalized polymer. Accordingly, the ester-fi ction ized hydrocarbon polymer product can include molecules having no functional groups, n can be determined by 13 C-NMR Specific preferred embodiments of n include l > n > 0; 2 > n >l; and n>2. For the ester-function.alized hydrocarbon polymer prepared using Koch chemistry as described below, the maximum value of n will be determined by the average number of double bonds per polymer chain in the polymer prior to functionalization.
  • R is Ci to C ⁇ 8 linear .alkyl, C 3 to Ci* branched alkyl, or C 6 to C 14 aryl; R' is substituted .alkyl, aryl, or substituted aryl; wherein at least about 80%, preferably at least about 85% and more preferably at least about 90% of the monomer units to which the neo-carboxylic ester functional groups are attached te ⁇ ninate one end of an ester-function.alized polymer chain with a -C*H 3 group (i.e., configuration A when C is attached to a unit derived from ethylene, .and configuration B when C is attached to a unit derived from ⁇ -olefin), have each of C* and C attached to a unit derived from ethylene (configuration C), or have one of C and C* attached to a unit derived from ethylene and the other of C and C* attached to a unit derived from ⁇ -o
  • R is preferably selected from line.ar alkyl groups of from 1 to 8 carbon atoms and branched alkyl groups of from 3 to 8 carbon atoms. More preferably R is an alkyl group of from 1 to 2 carbon atoms; i.e., R is more preferably selected from the group consisting of methyl and ethyl. R is most preferably ethyl.
  • R' in the ester-fiinctionalized polymers set forth above is selected from the group consisting of substituted .alkyls, aryls, and substituted aryls.
  • a substituted alkyl is a linear or branched alkyl group containing at least one electron withdrawing substituent, .and preferably at least two electron withdrawing substituents.
  • the .alkyl is preferably C 2 to Cio -alkyl, more preferably C 2 to Cg alkyl, and most preferably C 2 to C 4 alkyl.
  • the substituted .alkyl can contain electron withdrawing substituents on any one of the carbon atoms of the alkyl group, or on all of the carbon atoms, or any combination thereof, provided that the corresponding alcohol, R'OH, is chemically stable under conditions suitable for preparing the ester-functionalized polymer of the invention via the Koch reaction (described below), and under conditions suitable for derivatizing the ester- function.alized polymer of the invention (described below).
  • the substituted alkyl represents an alkyl group containing at least one primary or secondary carbon atom in a position beta to the ester moiety, wherein the beta carbon atom has at least one electron withdrawing substituent group (e.g., fluorine).
  • the substituted alkyl contains at least one electron withdrawing substituent on a carbon atom once removed from the ester moiety. More preferably, the primary or secondary beta carbon atom contains more than one electron withdrawing substituent.
  • the substituted alkyl contains two or more primary or secondary beta carbon atoms
  • at least one of the beta carbon atoms contains at least one, and preferably more than one, electron withdrawing substituent.
  • each of the beta carbon atoms contains at least one, and preferably more than one, electron withdrawing substituent.
  • each beta carbon atom present in the substituted .alkyl group is fully substituted with electron withdrawing groups.
  • the preferred substituted alkyl groups are haloalkyl groups, especially polyhaloalkyl groups (e.g., polychloroalkyl and polyfluoroalkyl groups), and most especially polyfluoroalkyl groups.
  • Particularly preferred polyhaloalkyl groups are those having at least one, and preferably more than one, halogen substituent on the beta carbon atom (or atoms) in the alkyl group.
  • Suitable polyhaloalkyl groups include, but are not limited to, 2,2-difluoroethyl, 2-2-2-trifluoroethyl, 2,2-dichloroethyl, 2,2,2- trichloroethyl, 1,1,1-trifluoroisopropyl, 1,1,1,3,3,3-hexafluoroisopropyl (often more simply referred to as hexafluoroisopropyl), 2,2,3,3,3-pentafluoropropyl, 2- methylhexafluoro-2-propyl and 2-trifluoromethylhexafluoro-2-propyl.
  • a particularly preferred polyhaloalkyl group is hexafluoroisopropyl.
  • a particularly preferred polyhaloalkyl ester functional group is hexafluoroisopropyl ester.
  • R' CM be aryl, which herein refers to an unsubstituted aromatic which will generally contain from 6 to 10 carbon atoms (e.g., phenyl, naphthyl) or to an alkyl substituted aromatic group, which suitably contains from 7 to 20 carbon atoms, and more typically contains from 7 to 12 carbon atoms (e.g., tolyl, m-ethylphenyl, o- ethyltolyl, and m-hexyltolyl).
  • R' CM be aryl, which herein refers to an unsubstituted aromatic which will generally contain from 6 to 10 carbon atoms (e.g., phenyl, naphthyl) or to an alkyl substituted aromatic group, which suitably contains from 7 to 20 carbon atoms, and more typically contains from 7 to 12 carbon atoms (e.g., tolyl, m-ethylphenyl, o- ethyltoly
  • R' can also be substituted aryl, which is an aryl group as defined in the preceding paragraph that also contains at least one electron withdrawing substituent.
  • R' has the formula:
  • X each of which is the same or different, is an electron withdrawing group; T, each of which is the same or different, is a non-electron withdrawing group (e.g., electron donating); m is an integer of from 1 to 5, and p is an integer of from 0 to 5. Preferably, m is from 1 to 3. Preferably, p is from 0 to 2, and more preferably 0 to 1.
  • X is preferably selected from halogen (especially F or Cl), CF3, CH 2 CF 3 , CN, and NO2.
  • T is preferably alkyl, especially C ⁇ to Cg alkyl, and most espedally methyl or ethyl.
  • suitable R' groups represented by formula (V) are halophenyls, such as chlorophenyl, fluorophenyl, difluorophenyl, dichlorophenyl, .and alkylchlorophenyl (e.g., methylchlorophenyl), and the like.
  • 2,4-Dichlorophenyl and 2- chloro-4-methylphenyl are preferred, and 2-chloro-4-methylphenyl is most preferred.
  • suitable substituted aryl ester functional groups include chlorophenyl ester, fluorophenyl ester, difluorophenyl ester, dichlorophenyl ester, .and methylchlorophenyl ester.
  • 2,4-dichlorophenyl ester and 2-chloro-4-methylphenyl ester are preferred substituted aryl ester functional groups, and 2-chloro-4-methylphenyl ester is most preferred.
  • the -OR' moiety of the -C0 2 R' neo-carboxylic ester functional group has a corresponding acidic species HOR' which, as described below, can be employed as a trapping agent in a Koch reaction for preparing the ester-functionalized hydrocarbon polymer of the invention.
  • the -OR' moiety is also a "leaving" group in certain of the derivatization reactions (e.g., .amidation and trans-esterification) of the ester- functionalized hydrocarbon polymer, thereby forming HOR' as a by-product.
  • -OR' has a pK a of less than or equal to about 12, preferably less than about 10, and more preferably less than about 8.
  • the pK a is determined from the corresponding acidic species HOR' in water at 25°C. This embodiment has been found to be more reactive towards derivatization with amines, especially polyamines.
  • the ester-fiinctionalized polymer of the invention CM also be characterized by its equivalent weight, which is defined as the weight in grams of ester-functionalized polymer product per equivalent of ester groups.
  • polymer product means the mixture of ester-functionalized polymer Md unfunctionalized polymer (if My) resulting from the Koch reaction following separation Md/or removal of the catalyst, solvent (if any), Md other reactMts d reagents.
  • the equivalent weight of the ester-functionalized polymer is suitably in the range of from about 300 to about 20,000.
  • Ester-functionalized polymers which are suitable per se as additives for lubricating oils Md also suitable as intermediates for the preparation of derivatives (e.g., amine derivatives) that are useful as additives (e.g., dispersMt additives) in lubricating oils typically have M equivalent weight in the range of from about 500 to about 20,000, preferably from about 600 to about 20,000, Md more preferably from about 1,000 to about 10,000 (e.g., from about 1,000 to about 7,500).
  • Ester-functionalized polymers which are suitable per se as additives for fuels Md also suitable as intermediates for the preparation of derivatives (e.g., amine derivatives) that are useful as additives in fuels typically have M equivalent weight in the range of from about 300 to about 3,500 (e.g., from about 300 to about 2,500).
  • Ester-fiinctionalized polymers having M equivalent weight of from about 300 to about 700 (e.g., from about 350 to about 600) are suitable per se as detergent additives in two-cycle engine oils Md as intermediates for the preparation of derivatives useful as detergents in two- cycle oils.
  • the ester-functionalized hydrocarbon polymers of the invention CM be prepared using the Koch reaction.
  • the Koch process involves carbonylating at least a portion of the double bond sites in a hydrocarbon polymer (especially MEAO polymer) containing at least one carbon-carbon double bond by contacting the polymer with carbon monoxide, M addic catalyst comprising BF3, d a nucleophilic trapping agent selected from .alcohols of formula R'OH Md mixtures thereof, wherein R' is substituted .alkyl, aryl, or substituted .aryl as heretofore defined.
  • the Koch reaction is conducted in a manner and under conditions to form the ester- function-alized polymer.
  • ester functional group occurs via formation of an acylium cation at the site of a carbenium ion formed by addition of a proton from the acidic catalyft to the carbon-carbon double bond, wherein the acylium cation subsequently reacts with the nucleophilic trapping agent.
  • Preferred trapping agents correspond to the acidic species HOR' of the preferred -OR' groups as described above. Referring to formula (IV), the functional group is represented by the parenthetical expression — (CR*R 2 -CO-OR'), which expression contains the acyl group -CO-OR'.
  • R 1 Md R 2 represent groups originally present on, or constituting part of, the two carbon atoms bridging the double bond before functionalization.
  • the relative amounts of reactMts Md catalyst Md the reaction conditions are controlled in a manner effective to produce an ester-fiinctionalized hydrocarbon polymer containing a substMtial proportion of less hindered neo-substituted ester groups. While not -wishing to be bound by My particular theory, it is believed that the carbenium ion that forms at the site of a carbon-carbon double bond " during the Koch reaction CM rearrange to a more or to a less sterically hindered position in the polymer before reaction occurs with CO (to form the acylium cation) and then the nucleophilic trapping agent.
  • the reactant Md catalyst amounts Md reaction conditions set forth below have been found to be effective in controlling this re>arrangement, such that a less hindered, more reactive ester-fUnction.alized polymer CM be obt ned.
  • the reactMt and catalyst amounts Md reaction conditions are also effective in functionalizing typically at least about 40, preferably at least about 80, more preferably at least about 90, Md most preferably at least about 95% of the carbon-carbon double bonds present in the starting polymer.
  • the catalyst is selected from BF 3 Md catalyst complexes of BF 3 with R'OH.
  • Preferred catalyst complexes are those prepared from R'OH corresponding to the preferred -OR' groups described above.
  • Complexes of BF 3 with substituted .aryl alcohol trapping agents are preferred, the more preferred being complexes with 2,4- dichlorophenol Md with 2-chloro-4-methylphenol, Md the most preferred being complexes with 2-chloro-4-methylphenol.
  • the catalyst or catalyst complex suitably has a Hammett Scale Value acidity ("H o ") of less thM about -7, Md typically from about -8.0 to about -11.5, in order to be sufficiently active.
  • the catalyst CM be employed by preforming a catalyst complex with the R'OH nucleophilic trapping agent or by adding the catalyst Md trapping agent separately to the reaction mixture. The latter embodiment has the advantage of eliminating the separate step of making the catalyst complex.
  • the BF 3 to CO mole ratio employed in the Koch reaction is from about 0.6 to about 1.5, preferably from about 0.7 to about 1.3, Md more preferably from about 0.8 to 1.2 (e.g., from about 0.9 to about 1.0).
  • the amount of alcohol i.e., R'OH
  • R'OH is typically at least the stoichiometric .amount required to react with the acylium cations. Accordingly, for example, the mole ratio of alcohol to a monounsaturated polymer is typically at least about 1:1.
  • an excess amount of the alcohol is used over the stoichiometric .amount (e.g., M alcohol:monounsaturated polymer mole ratio of from about 1.1:1 to about 2: 1), since the alcohol CM perform the dual role of reactMt Md diluent for the reaction.
  • M alcohol:monounsaturated polymer mole ratio of from about 1.1:1 to about 2: 1
  • the BF 3 to alcohol mole ratio is suitably in the range of from about 0.3 to less than about 2, typically from about 0.8 to about 1.9, Md preferably from about 0.9 to about 1.4.
  • the reactMts and catalyst CM be charged to the reactor concurrently or sequentially in My order.
  • the polymer CM be added to the reactMt system in a neat liquid phase, or dissolved in M inert solvent.
  • the alcohol can be mixed with the polymer Md the polymer-alcohol mixture charged to the reactor, with concurrent or subsequent charging of BF 3 Md CO, each of which is typically introduced into the reactor as a gas.
  • the BF 3 CM be pre-reacted with the alcohol to form a catalyst complex, which is then digged to the reactor separately from the polymer d CO.
  • the reaction temperature is suitably in a range of from about 0°C to about 100°C, typically from about 15°C to about 65°C, Md preferably from about 20°C to about 55°C.
  • Temperature CM be controlled by heating Md cooling meMS applied to the reactor. Since the reaction is exothermic, a cooling meMS might be required.
  • one or more of the liquid-phase reactMts (i.e., the polymer and the alcohol trapping agent) CM first be cooled to a pre-selected temperature below the desired reaction temperature, Md then charged to M adiabatic reactor where they are warmed by the heat of reaction alone (i.e., no external heating) to the maximum desired reaction temperature.
  • the liquid-phase reactor contents are typically stirred or otherwise mixed throughout the reaction to assure a uniform reaction medium.
  • System operating pressure is suitably up to about 138,000 kPa (up to about 20,000 psig)
  • Md is typically at least about 2,070 kPa (at least about 300 psig), preferably at least about 5,520 kPa (at least about 800 psig), Md most preferably at least about 6,900 kPa (at least about 1,000 psig).
  • System pressure is suitably in the range of from about 3,450 to about 34,500 kPa (from about 500 to about 5,000 psig), typically from about 4,485 to about 20,700 kPa (from about 650 to about 3,000 psig), preferably from about 4,485 to about 13,800 kPa (from about 650 to about 2,000 psig).
  • the reaction time is suitably up to about 5 hours, typically from about 0.5 to 4 hours, Md preferably from about 0.5 to 2 hours.
  • the reactor is depressurized, the contents are typically discharged, Md the ester- functionalized polymer product is separated from the catalyst Md unconsumed reactMts. Nitrogen can be used to flush the reactor Md any vessel used to receive the polymer product. Unreacted CO CM be vented off. The BF 3 is typically also released when the reartor is depressurized. A flash CM be performed at the conclusion of the reaction to allow most of the BF 3 catalyst Md unreacted CO to be released for re-use.
  • the ester-function.alized polymer-containing reaction mixture CM be a single phase, a combination of partitionable polymer Md acid phases, or M emulsion with either the polymer phase or the acid phase being the continuous phase.
  • partitionable polymer Md acid phases or M emulsion with either the polymer phase or the acid phase being the continuous phase.
  • a suitable means can be used to separate the polymer product, which means is preferably the use of fluoride salts, such as sodium or ammonium fluoride in combination with M alcohol such as butMol or metlranol to neutralize the catalyst Md phase separate the reaction complex.
  • fluoride salts such as sodium or ammonium fluoride
  • M alcohol such as butMol or metlranol
  • the fluoride ion helps trap the BF 3 complexed to the ester-functionalized polymer Md helps break emulsions generated when the crude product is washed with water.
  • Alcohols such as metlranol Md butanol Md commercial demulsifiers also help to break emulsions, especially in combination with fluoride ions.
  • the nucleophilic trapping agent is combined with the fluoride salt, when alcohols are used to separate polymers.
  • the presence of the nucleophilic trapping agent as a solvent n ⁇ nimizes trans-esterification of the ester-function-alized product.
  • the ester-function.alized polymer CM be separated from the unconsumed nucleophilic trapping agent Md BF 3 catalyst by depressurization and distillation. It has been found that the BF 3 catalyst releases more easily from reaction mixtures contmning nucleophilic trapping agents with relatively low pK,'s.
  • the reaction yield CM be determined upon completion of the reaction by separating the polar ester-functionalized polymer from the non-polar unfunction-alized polymer, using stMdard techniques such as chromatography.
  • the conversion of carbon-carbon double bonds can be determined using 13 C-NMR.
  • the Koch process as heretofore described can be operated in batch, semi- continuous, or continuous mode.
  • the batch Koch carbonylation process as generally described in US-A-5646332 is a preferred process for preparing ester-function ized polymer of the present invention, wherein the relative reactMt d catalyst amounts d reaction conditions set forth above are employed.
  • the polymer Md alcohol (R'OH) . are charged to a charge vessel which is purged with CO by bringing the vessel to M elevated pressure with CO gas.
  • BF 3 gas is charged to M empty reactor equipped with a mixer d CO gas is then charged.
  • the reactor is heated Md the mixer turned on while the contents of the charge vessel are rapidly fed into the reactor, driven by the higher pressure of CO gas in the clrarge vessel.
  • Additional CO is then fed to the reactor to reach the desired total system pressure Md desired relative reactMt Miounts (e.g., BF 3 to CO mole ratio of from about 0.6 to about 1.5).
  • ester-fiinctionalized polymer is recovered by the means heretofore described.
  • the continuous carbonylation process as generally described in US-A-5650536 is a preferred process for preparing ester-functionalized polymer of the present invention, wherein the relative reactMt Md catalyst amounts Md reaction conditions set forth above are employed.
  • reactMts are fed to the reaction system by pumps or compressors d mixed together just before or just after entering the reactor, which is either a continuous stirred tank reactor
  • CSTR CSTR
  • BF 3 Md CO gaseous reagents
  • a flash is performed at the reactor exit to allow most of the BF 3 catalyst and unconsumed CO to be released from the liquid phase Md recycled.
  • Second stage separations may be used to remove and recycle excess nucleophilic trapping agent (R'OH).
  • liquid- Md vapor-phase reartMts are fed to the single stage reactor equipped with a mechanical agitator to promote liquid/gas contact Md provide uniform concentrations throughout the reactor.
  • the CSTR configuration of the invention may use more than one reactor vessel/stage in series although a single stage is simpler Md less expensive. Multiple stages may be used to reduce total volume Md residence time.
  • in-line mixers Me spaced at intervals to promote liquid/vapor contact in a minimal total volume configuration with no mechanical seals.
  • the in-line mixers may be either static or mechanical (including those with external driven impellers).
  • the mixers are effectively positioned at residence time intervals rMging from .about 0.25 to about 5 minutes, conveniently from about 0.25 to about 3 minutes, Md especially from about 0.5 to about 1.5 minutes, between mixers.
  • the interval between mixers increases from the inlet to the exit of the reactor.
  • Each mixer provides homogeneous blending of the liquid Md disperses gas bubbles ranging in size from about 0.01 to about 3 mm, conveniently from about 0.1 to about 2 mm, Md especi.ally from about 0.1 to about 1 mm.
  • Mixer intensity may be relaxed toward the reactor exit as high gas/liquid contacting is primarily required in the front part of the reactor (although homogeneous blending is needed at the exit). Therefore, gas dispersing mixers are preferred in the front of the tubular reactor Md blending mixers are preferred in the back end of the reactor.
  • the Sulzer SMV static mixer is a suitable mixer for gas/liquid contact.
  • Mkers CM be designed to optimize bubble size Md distribution in a reactor. Larger equipment requires larger mixers.
  • a preferred continuous process of the invention includes a laminar flow process where the Reynolds Number is very low, preferably less ttran about 10, Md uses static mixers to disperse gas into liquid Md promote reaction. The mixers Me followed by open pipe to provide residence time for reaction.
  • the tubular reactor process is also advMtageous because it eliminates the need for liquid level control, Iras simple controls Md operation, has a short reaction time, provides high yields, maximizes inherent safety; Md permits use of a wide range of polymer viscosities.
  • the continuous process of the invention also provides a very clean, white product compared to batch preparations, especially where exposure to air d oxygen are avoided.
  • a particul-arly preferred continuous carbonylation process Md reactor configuration for preparing ester-functionalized polymer of the present invention is described in copending USSN (Docket No. 97L213), filed , Md entitled "Process for the Continuous Production of Functionalized Polymers”.
  • One particularly preferred reactor configuration for preparing the ester-function.alized polymer consists of (1) a dispersing zone which is series of closely spaced static mixers at the front end of the reactor operated in laminar flow to provide high intensity mixing of liquid Md gas under function-alization conditions to form a stable gas-liquid dispersion, followed by (2) a blending zone which is a zone operated in laminar flow into which the gas-liquid dispersion is passed Md mixed at low intensity under functionalization conditions to provide additional blending of the gas Md liquid with further dissolution of the gas, and then by (3) a soaking zone operated under function-alization conditions with little or no agitation of the reaction mixture to achieve a maximum reaction yield.
  • the sequence of mixers in the dispersing zone is configured -with varying diameter mixer sections, progressing from larger diameters at the feed location to smaller diameters at the highest intensity location.
  • the variation in mixer diameters is provided to allow for progressive bre.akdown of the gas into smaller bubbles in each stage while avoiding formation of large gas slugs in the reactor.
  • the variation in ammeter also improves the .ability of the reactor to operate over a wide range of polymer viscosities, .allowing greater flexibility in selection of reaction temperature for higher molecul.ar weight polymers.
  • the residence time in the front dispersing zone of the reactor is typically no more than about 20 minutes (e.g., from about 1 to about 10 minutes).
  • the blending zone typically consists of static mixers.
  • the soaking zone is an open pipe or is a pipe packed with static mixer elements or other highly porous packing to promote a plug flow residence time distribution.
  • Residence times in the blending Md soaking zones are typically no more thM about 40 minutes d no more than about 120 minutes respectively.
  • the present invention includes derivatized polymers obtained by reacting the ester-functionalized polymers of the invention with nucleophilic reactMt compounds including, but not limited to, amines, amino alcohols, alcohols, reactive metals, Md reactive metal compounds.
  • nucleophilic reactMt compounds including, but not limited to, amines, amino alcohols, alcohols, reactive metals, Md reactive metal compounds.
  • Useful amine compounds for derivatizing the functionalized polymers contain at least one amino group which CM react with the ester functional groups in the functionalized polymer to form amide groups.
  • the amine compounds preferably contain at least one primary amino group.
  • Suitable amines include mono- Md polyamines containing from about 2 to about 60, preferably about 2 to about 40 (e.g. about 3 to about 20) total carbon atoms Md from about 1 to about 12, preferably about 2 to about 12 (e.g., about 3 to about 9) nitrogen atoms in the molecule.
  • the amines may be hydrocarbyl amines or hydrocarbyl amines including other groups (e.g., hydroxy groups, .alkoxy groups, .amide groups, nitriles, imidazoline groups, and the like), provided these other groups do not substMti ly interfere with the reaction of the amino groups with the ester groups in the functionalized polymer of the invention.
  • These amines include aliphatic, cycloaliphatic, Md aromatic mono- Md polyamines.
  • the monoamines are primary or secondary monoamines, preferably primary amines.
  • Suitable aliphatic monoamines include mono- and dialkylamines, mono- Md dialkenylamines, Md mono-alkylmonoalkenylamines, typically having a total of no more thM about 20 carbon atoms.
  • Exemplary aliphatic monoamines are ethylamine, diethyhmine, n-butyl.amine, di-n-butyl.amine, laurylamine, dodecyl-amine Md the like.
  • Suitable cycloaliphatic amines include cycloalkylamines, cycloalkenylamines, Md dicycloalkylamines, Md the like, such as cyclohexylamine, cyclopentyl-amine, the cyclohexenyl-amines, dicyclohexylamine, Md so forth.
  • Suitable aromatic monoamines include aniline, naphthylamine, p-dodecylaniline, Md p-ethoxyMiline.
  • the preferred amine compounds are polyamines.
  • the polyamines are aliphatic, cycloaliphatic Md aromatic polyamines having at least two amino groups, at least one of which is a primary or secondary amino group.
  • Preferred polyamines are those having at least one primary amino group.
  • the polyamines can optionally contain one or more tertiary amino groups in addition to one or more primary andlor secondary amino groups.
  • alkylene polyamines especially ethylene polyamines Md propylene polyamines having from about 2 to about 12 (e.g., about 2 to about 9), typically from about 3 to about 12 (e.g., about 3 to about 9 or about 3 to about 10) nitrogen atoms per molecule, or mixtures of such alkylene polyamines having an average number of nitrogen atoms per molecule corresponding to the foregoing ranges.
  • Particularly useful alkylene polyamines are those having 2 to 3 carbon atoms between primary amino groups Md neighboring amino groups.
  • Exemplary alkylene polyamines include tetraethylene pentamine (“TEPA”), pentaethylene hexamine (“PEHA”), N-(2-aminoethyl)piperazine, di-(l,2- propylene)triamine, Md di-(l,3-propylenetriamine).
  • TEPA tetraethylene pentamine
  • PEHA pentaethylene hexamine
  • N-(2-aminoethyl)piperazine di-(l,2- propylene)triamine
  • Md di-(l,3-propylenetriamine Md di-(l,3-propylenetriamine.
  • the alkylene polyamine is a heavy alkylene polyamine which is defined herein as an alkylene polyamine having at least about 7 nitrogen atoms per molecule or mixtures of alkylene polyamines (e.g., a mixture of higher oligomers of alkylene polyamines) having M average of at least about 7 nitrogen atoms per molecule.
  • exemplary heavy alkylene polyamines include the linear Md branched isomers of hexaethylene heptamine, heptaethylene octamine, Md hexa-(l,2- propylene)heptamine.
  • a preferred heavy polyamine is a mixture of ethylene polyamines containing essentially no TEPA, at most s ⁇ rall amounts of PEHA, Md the balMce oligomers with more thM 6 nitrogens Md more branching thM conventional commercial polyamine mixtures such as the E-100 Md HPA-X mixtures noted in the preceding paragraph.
  • a useful heavy alkylene polyamine composition is commercially available from Dow Chemical under the tradename HA-2.
  • HA-2 is a mixture of higher boiling ethylene polyamine oligomers Md is prepared by distilling out all the lower boiling ethylene polyamine oligomers (light ends) up to Md including TEPA.
  • the TEPA content is less than 1 wt.%. Only a small amount of PEHA, less thM 25 wt.%, usually 5-15 wt.%, remains in the mixture.
  • the balMce is higher nitrogen-content oligomers with a great degree of brMching.
  • the heavy polyamine preferably contains essentially no oxygen.
  • Typical Malysis of HA-2 gives primary nitrogen values of 7.8 milliequivalents (meq) (e.g., 1.1 to 7.8) of primary amine per gram of polyamine. This calculates to be about M equivalent weight (EW) of 128 grams per equivalent (g eq). The total nitrogen content is from about 32 to about 33 wt.%.
  • EW equivalent weight
  • conventional commercial polyamine mixtures such as E-100 Md HPA-X typically have from about 8.7 to about 8.9 meq of primary amine per gram Md a nitrogen content of from about 33 to about 34 wt.%.
  • Another suitable polyamine is a one-armed amine, which is defined herein as an amine containing M average of one primary amino group Md one or more secondary or tertiary amino groups per molecule.
  • the one-armed amine preferably contains one primary amino group Md 1 to 10 secondary or tertiary amino groups. Mixtures of such one-.armed amines are also suitable.
  • Exemplary one-armed amines are dimethylamino-propylaminopropylamine Md polypropylene tetramine with one end substituted with a tallow group Md having approximately one primary amine per molecule. Suitable one-armed amines are further described in USSN 261534 (filed June 17, 1994).
  • polystyrene resin examples include polyoxyalkylene polyamines such as those described in US-A-5229022; amidoamines Md thioamidoamines as described in US-A-4857217 Md US-A-4956107; d MiinocyclohexMe derivatives as described in US-A-5296560 Md US-A-5213698.
  • Heterocyclic mono- Md polyMiines CM also be used to m.ake derivatives of the copolymer of the invention, including morpholines Md aminomorpholines (e.g., N-(3- aminopropylmorpholine), piperazines, N-aminoalkylpiperazines, piperidines, Md Miinoalkyl piperidines.
  • morpholines Md aminomorpholines e.g., N-(3- aminopropylmorpholine
  • piperazines N-aminoalkylpiperazines
  • piperidines Md Miinoalkyl piperidines.
  • Amine-derivatized polymers can be prepared by reacting the amine compound with the ester-functionalized polymer of the invention, optionally dissolved or diluted in M inert orgMic liquid (e.g., mineral oils) to a concentration of about 5 to about 95 wt.%, under conditions effective to amidate at least a portion of the ester functional groups.
  • the reaction may be carried out at any temperature up to the decomposition of the reactMts Md produds, but is typically conducted at temperatures of from about 50 to about 250°C (e.g., from about 100 to about 250°C), and preferably from about 175 to about 250°C.
  • reaction time can vary widely depending upon the choice and amount of the amine d polymer ester to be reacted, the desired degree of conversion, reaction temperature, d the like. Reaction times are typically in the range of from about 1 to about 48 hours (e.g., from about 8 to about 32 hours).
  • the amine compound may be employed in My Miount under the selected reaction time Md conditions sufficient to Miidate at least a portion of the ester functional groups.
  • the .amine is typically employed in M amount sufficient to convert a major portion (i.e., at least about 50 mole%), preferably at least about 80 mole%, (e.g., from about 80 to about 90 mole%), more preferably at least about 90 mole% (e.g., from about 90 to about 95 mole%), Md most preferably substMtially all (i.e., from about 95 to about 100 mole%) of the ester functional groups. Accordingly, the amine is typically employed in an amount of at least about one equivalent of reactive amino groups per equiv ent of ester functional groups.
  • the .amine can be used in an excess amount (e.g., from about 1.1 to about 5 or from about 1.2 to about 4 equivalents of reactive amino groups per equivalent of ester functional groups) in order to achieve substantial conversion Md to reduce reaction time.
  • an excess amount e.g., from about 1.1 to about 5 or from about 1.2 to about 4 equivalents of reactive amino groups per equivalent of ester functional groups
  • the amine When the amine contains a primary amino group (or groups) or both a primary amino group (or groups) Md a secondary amino group (or groups), the amine is preferably used in M Miount of at least about one equivalent of primary amino groups per equivalent of ester functional groups, wherein, because the primary amino groups are normally more reactive thM the secondary amino groups, the amidation reartion will occur substMtially between the ester groups Md the primary amino groups.
  • reaction progress Md degree of conversion CM be determined by measuring the disappearance of the infrared absorption peaks due to the ester group Md/or appearance of the IR peaks due to the amide groups.
  • the ester-functionalized polymers of the invention CM be reacted with alcohols to form different ester functional groups therein by trans-esterification.
  • the alcohols may be monohydric alcohols, polyhydric alcohols, aromatic hydroxy compounds, unsaturated .alcohols, or ether alcohols.
  • the .alcohols may contain other polar or reactive groups, provided they do not interfere with the reaction of the alcohols with the ester groups in the functionalized polymer of the invention.
  • the polyhydric alcohols typically contain from about 2 to about 10 hydroxy radicals per molecule.
  • Suit ⁇ le polyhydric .alcohols include ethylene glycol, diethylene glycol, triethylene glycol, glycerol, pentaerythritol, etc. Md mixtures thereof.
  • the functionalized polymers of the invention CM be reacted with the alcohols according to conventional esterification techniques. This normally involves heating the functionalized polymer with the alcohol, optionally in the presence of a normally liquid, substantially inert, org.anic liquid solvent. Temperatures from at least about 50°C up to the temperature at which one or more of the reactMts decompose are used. The temperature is usually within the range of .about 100 up to about 300°C, Md typically from about 140 to about 250°C.
  • the esterification may optionally be conduded in the presence of M addic or basic esterification catalyst (e.g., sulfuric acid, p-toluene sulfonic acid, Md the like).
  • the ester-fimctionalized polymers CM also be reacted with amino alcohols (i.e., compounds containing one or more hydroxy groups Md one or more primary or secondary amino groups) to form derivatives containing esters Md/or N-containing groups.
  • amino alcohols i.e., compounds containing one or more hydroxy groups Md one or more primary or secondary amino groups
  • suitable amino alcohols include ethMolamine, diethanolamine, N-hydroxyethyl piperazine, 3-hydroxybutyl.amine, Md N, N, N'-tris- (2-hydroxyethyl)ethylenediamine, tris-(hydroxymethyl)aminomethMe ("THAM'), Md the like.
  • THAM' tris-(hydroxymethyl)aminomethMe
  • the ester-functionalized polymers of the invention CM be reacted with amino alcohols in amounts Md under conditions substantially as set forth above for reacting amines and for reacting alcohols.
  • the ester-functionalized polymers of the invention can be reacted with reactive metals or reartive metal compounds to form metal salts or metal-containing complexes.
  • Metal salts are formed by reaction of the ester groups in the funrtionalized polymer with the reactive metal or metal compounds.
  • Metal complexes are typically achieved by reacting the ester-functionalized polymers with amines, alcohols, Md/or .amino alcohols as discussed above Md also with complex forming reactive metal compounds either during or subsequent to amination Md/or trans-esterification.
  • the compounds of alkali metals, alkaline earth metals, Md the transition metals are useful for forming the metal salts Md complexes.
  • Suitable compounds include oxides, alkoxides, hydroxides, phenoxides, alkylates (e.g., methylates), nitrates, nitrites, halides, carboxylates, phosphates, phosphites, sulfates, sulfites, carbonates Md borates.
  • Reactive metal compounds useful in preparing salts from the functionalized polymer and/or M Miine derivatized polymer as described above include the oxides, hydroxides, carbonates, halides, alkylates (e.g., methylates), Md phenoxides of the alkali metals, alkaline earth metals, zinc, cadmium, lead, cobalt and nickel. Further disclosure directed to these reactive metal compounds Md of processes for preparing the function.alized polymer salts therefrom CM be found in US Reissue 26433.
  • ester-functionalized polymer CM be reacted with My individual amine, alcohol, amino alcohol, reactive metal, reactive metal compound or My combination of two or more of My of these. Furthermore, the ester-f inctionalized polymer CM be reacted with the .amines, alcohols, amino alcohols, reactive metals, reactive metal compounds, or their mixtures simultMeously (concurrently) or sequenti.ally in y order.
  • Another aspect of the present invention involves the post-treatment of the derivatized polymers, especially the nitrogen-containing derivatized polymers.
  • the processes used for post-treating are Malogous to the post-treating processes used for conventional dispersMts. Accordingly, with suitable adjustment, the reaction conditions, ratios of reactMts Md the like disclosed for post-treating conventional dispersants CM be employed with derivatized polymers of the present invention.
  • the amine-derivatized polymer CM be post-treated with such reagents as urea, thiourea, carbon disulfide, aldehydes, inorganic acids, carboxylic acids, dicarboxylic acid anhydrides, hydrocarbyl substituted succinic anhydrides, nitriles, epoxides, boron compounds, phosphorus compounds Md the like.
  • reagents as urea, thiourea, carbon disulfide, aldehydes, inorganic acids, carboxylic acids, dicarboxylic acid anhydrides, hydrocarbyl substituted succinic anhydrides, nitriles, epoxides, boron compounds, phosphorus compounds Md the like.
  • the amine-derivatized polymer CM be borated by post- treating the product with a borating agent to obtain a borated product containing at least about 0.1 weight percent of boron based on the total weight of the borated product.
  • the borated product can suitably contain up to about 10 wt.% boron (e.g., from about 3 to about 10 wt.%) but preferably has from about 0.05 to about 2 wt.% (e.g., from about 0.05 to about 0J wt.%) boron.
  • Suitable borating agents include boron halides, (e.g.
  • boron trifluoride boron tribromide, boron trichloride
  • boron acids Md simple esters of the boron acids (e.g., trialkyl borates containing 1 to 8 carbon alkyl groups such as methyl, ethyl, n-octyl, 2-ethylhexyl, etc.).
  • the boration reaction is typically carried out by adding from about 0.05 to about 5 wt.% (e.g., from about 1 to about 3 wt.%) of the borating agent based on the weight of the amine-derivatized polymer product, d heating with stirring at from about 90 to about 250°C, preferably from about 135 to about 190°C (e.g., from about 140 to about 170°C), for from about 1 to about 10 hrs., followed by nitrogen stripping in said temperature rMges.
  • the borating agent is preferably boric acid which is usually added as a slurry to the reaction mixture.
  • a suitable low sediment process involves borating with a particulate boric acid >. having a particle size distribution characterized by a ⁇ value of not greater thM about 450. The process is described in US-A-5430105.
  • boration processes employing a protic agent (e.g., water, alcohols, phenols, or the like) in addition to the borating agent.
  • a protic agent e.g., water, alcohols, phenols, or the like
  • Such a process is described in US-A-4925983.
  • the amine-derivatized polymer can be post-treated by reaction with a phosphorus-containing agent to introduce phosphorus or phosphorus- containing moieties into the product.
  • Suitable phosphorus-containing agents include phosphorus acids, phosphorus oxides, phosphorus sulfides, phosphorus esters Md the like.
  • Suitable inorganic phosphorus compounds include phosphoric acid, phosphorus acid, phosphorus pentoxide, Md phosphorus pentasulfide.
  • Suitable organic phosphorus compounds include mono-, di- Md trihydrocarbyl phosphates, the hydrocarbylpyrophosphates, Md their partial or total sulfur analogs wherein the hydrocarbyl group(s) contain up to about 30 carbon atoms each.
  • Illustrative post- treatments employing phosphorus compounds are described in US-A-3184411, 3342735, 3403102, 3502677, 3511780, 3513093, 4615826, and 4648980, and in GB- A-l 153161 and 2140811.
  • the amine-derivatized polymer CM be post-treated by reaction with a low molecular weight dicarboxylic acid»acylating agent such as maleic anhydride, maleic acid, fumaric acid, succinic acid, alkenyl or alkyl substituted succinic acids or anhydrides (in which the alkyl or alkenyl substituent has from 1 to about 24 carbon atoms), and the like.
  • acylating agent is typically reacted with the amine-derivatized polymer at temperatures in the range of from about 80 to about 180°C for a time rMging from about 0.1 to about 10 hours, optionally in the presence of an inert solvent.
  • the amine-derivatized polymer CM also be post-treated with a high molecul-ar weight dicarboxylic acylating agent including hydrocarbyl substituted dicarboxylic anhydrides Md acids, such as succinic anhydrides or acids, having from about 25 to about 500, preferably about 50 to about 400, carbon atoms in the hydrocarbyl substituent.
  • Md acids such as succinic anhydrides or acids
  • the hydrocarbyl groups are typically aliphatic Md include polyalkyl Md polyalkenyl groups, which CM be derived from a polymer of a C 2 to C 5 monolefin, the polymer having M n of from about 300 to about 6000, preferably from about 600 to about 5000.
  • a particularly preferred high molecular weight dicarboxylic acylating agent is polyisobutenyl succinic anhydride in which the polyisobutenyl substituent has M n of from about 700 to about 3000.
  • Suitable acylating agents for post-treating the amine-derivatized polymers also include long chain monocarboxylic acids of formula R q COOH wherein R q is a hydrocarbyl group having from about 12 to about 400 carbon atoms.
  • Suitable hydrocarbyl groups include those described just above with respect to dicarboxylic acylating agents.
  • the derivatized polymers can be post-treated by reaction with a strong inorganic acid, such as with a mineral acid selected from sulfuric, nitric Md hydrochloric acid at a temperature of from about 93 to about 204°C, as described in US-A-4889646.
  • a strong inorganic acid such as with a mineral acid selected from sulfuric, nitric Md hydrochloric acid at a temperature of from about 93 to about 204°C, as described in US-A-4889646.
  • the derivatized polymers of the present invention can also be treated with lactones (e.g., ⁇ -caprolactone) as described in US-A-5629434, Md with cyclic carbonates as described in US-A-4585566.
  • the ester-function-alized polymers Md deriv.atized polymers (including post- treated amine-derivatized polymers) of the invention possess properties (e.g., dispersancy Md/or detergency) which make them useful as additives in fuels Md in lubricating oils.
  • the additives of the invention are used by incorporation into the lubricating oils Md fuels. Incorporation may be done in any convenient way Md typically involves dissolution or dispersion of the additives into the oil or fuel in M .amount effective for their intended function. The blending into the fuel or oil can occur at room or elevated temperature.
  • the additives CM be blended with a suitable oil-soluble solvent/diluent (such as benzene, xylene, toluene, lubricating base oils Md petroleum distillates, including the various normally liquid petroleum fuels noted below) to form a concentrate, Md then the concentrate CM be blended with a lubricating oil or fuel to obtain the final formulation.
  • a suitable oil-soluble solvent/diluent such as benzene, xylene, toluene, lubricating base oils Md petroleum distillates, including the various normally liquid petroleum fuels noted below
  • Such additive concentrates will suitably contain on M active ingredient ("AT') basis from about 5 to about 95 weight percent, typically from 10 to about 80 weight percent, more typically from about 20 to about 60 wt.%, Md preferably from about 40 to about 50 wt.% additive, based on the total weight of the concentrate.
  • AT' M active ingredient
  • Fuel compositions of this invention can contain other conventional additives in addition to the additive of the invention. These CM include Mti-knock agents, cetane improvers, metal deactivators, deposit modifiers/preventors, Md Mti-oxidMts.
  • the additives of the present invention find their primary utility in lubricating oil compositions which employ a base oil in which the additives are dissolved or dispersed therein.
  • base oils may be natural or synthetic.
  • Base oils suitable for use in preparing the lubricating oil compositions of the present invention include those conventionally employed as crankcase lubricating oils for spark-ignited d compression-ignited internal combustion engines, such as automobile Md truck engines, marine d railroad diesel engines, Md the like.
  • AdvMtageous results are also achieved by employing the additives of the present invention in base oils conventionally employed in Md/or adapted for use as power trMsmitting fluids, universal tractor fluids Md hydraulic fluids, heavy duty hydraulic fluids, power steering fluids and the like.
  • Natural oils include animal oils Md vegetable oils, liquid petroleum oils Md hydrorefined, solvent-treated or acid-treated mineral lubricating oils of the paraffinic, naphthenic Md mixed paraffinic-naphthenic types. Oils of lubricating viscosity derived from coal or shale are also useful base oils.
  • Synthetic lubricating oils include hydrocarbon oils Md halosubstituted hydrocarbon oils such as polymerized Md interpolymerized olefins (e.g., polybutylenes, polypropylenes, propylene-isobutylene copolymers, Md chlorinated polybutylenes).
  • hydrocarbon oils Md halosubstituted hydrocarbon oils such as polymerized Md interpolymerized olefins (e.g., polybutylenes, polypropylenes, propylene-isobutylene copolymers, Md chlorinated polybutylenes).
  • suitable synthetic oils include alkylene oxide polymers, interpolymers Md derivatives thereof where the terminal hydroxyl groups have been modified by esterification, etherification, Md the like; esters of dicarboxylic acids; esters made from C 5 to C 12 monocarboxylic acids Md polyols and polyol ethers such as neopentyl glycol; Md silicon-based oils such as the polyalkyl-, polyaryl-, polyalkoxy-, or polyaryloxysiloxMe oils Md silicate oils.
  • the additives of the invention are typically employed as detergents Md/or dispersMts.
  • the additives of the invention are used in amounts effective to perform their intended function (e.g., in M Miount effective for a dispersMt Md/or detergent function).
  • the additives of the present invention may be mixed with other types of conventional additives, each selected to perform at least one desired function.
  • other additives which may be employed in the lubricating oil formulation are viscosity index ("VI") improvers, metal-containing detergent/inhibitors Md Mti-wear agents.
  • VI improvers include hydrocarbon polymers (e.g., ethylene propylene polymers) Md polyesters, these materials having M n 's of from 10 3 to 10 6 , d option.ally derivatized to impart dispersMcy or some other property.
  • the metal detergent/inhibitors are generally basic or overbased alkali or alkaline earth metal salts or mixtures thereof (e.g.
  • Mti-wear agents are typically oil-soluble zinc dihydrocarbyl dithiophosphates.
  • Other additives which may be employed in the formulation are MtioxidMts, corrosion inhibitors, pour depressMts, friction modifiers, foMi inhibitors, demulsifiers, flow improvers, Md seal swell control agents.
  • additives of the present invention are typically blended into the base oil in amounts which are effective to provide their normal attendant function. Whether used alone or in combination with these other additives, the additives of the present invention are generally employed in an amount of from about 0.01 to about 20 wt.%, and preferably from about 0.1 to about 10 wt.% (e.g., from about 0.1 to about 6 wt.%), based upon the total weight of the composition.
  • Additive concentrates comprising concentrated solutions of the additives of this invention together with one or more of these other additives CM be prepared by mixing the additives into the base oil, wherein the subject additives of this invention can be added in the form of a concentrate as described above.
  • the collective amounts of the subject additive together with other additives is typically from about 10 to about 90 wt.% (e.g., from about 10 to about 80 wt.%), preferably from about 15 to about 75 wt.%, and most preferably from about 25 to about 60 wt.% additives with base oil as the balMce.
  • the concentrate will typically be formulated to contain the additives in the amounts necessary to provide the desired concentration in the final formulation when the concentrate is combined with a predetermined .amount of base lubricMt. Unless otherwise indicated, all of the weight percents expressed herein are based on the active ingredient content of the additive.
  • the active ingredient contents expressed herein reflect the Al content of the additives added to (i.e., incorporated into) the foregoing compositions Md concentrates.
  • This value CM differ from the actual amount of additive present in the compositions Md concentrates as a result of additive interactions Md/or environmental exposures (e.g., to air) during blending, storage Md/or use.
  • the 13 C-NMR spectra were acquired on a JEOL Delta 400 NMR spectrometer with a 9.4 Tesla field strength (corresponding to a carbon Larmor frequency of 100 MHz).
  • the samples were dissolved in deuterochloroform at a concentration of about 30 wt.%
  • the sample solutions were doped with chromium acetylacetonate — a relaxation agent — at a level of about 20 mg/ml.
  • the spectra were acquired quantitatively with inverse-gated decoupling Md a 3.4 second relaxation delay between scans.
  • the sample temperature was maintained at 50°C during acquisition. Approximately 15,000 SCMS were acquired for polymeric samples Md typically about 500 scans for the model compounds.
  • a free induction decay of 32K complex data points in the time domain was collected and Fourier trMsformed into a spectrum of 32K complex points, with 0.5 Hz LorentziM line broadening.
  • the spectrum was phased, baseline corrected, Md referenced relative to M internal tetramethylsilMe standard at 0.0 ppm.
  • model carboxylic acid Md ester compounds so prepared are shown in the following table, along with the structural features they mimic Md the corresponding pertinent chemical shifts: Model compound Configuration 1 Chemical shift (ppm): quaternary carbon carbonyl carbon
  • Configuration A acid or ester group is attached at the end of a chain having a penultimate unit derived from ethylene monomer.
  • Configuration B acid or ester group is attached at the end of a chain having a penultimate unit derived from butene monomer.
  • Configuration C C* and C atoms are both attached to units derived from ethylene.
  • Configuration D C* is attached to a unit derived from ethylene Md C is attached to a unit derived from butene or vice versa.
  • Configuration E C* and C are both attached to units derived from butene.
  • the percentage of polymer with configurations A and B was determined by summing the resonMce integrals from 46.0 to 47.0, d then dividing by the total quaternary carbon integral from 46.0 to 50.2.
  • the percentage of polymer with configurations A, B Md C was determined by summing the integrals of the carbonyl resonMces from 174.6 to 175.2, Md then dividing by the total carbonyl integral from 174.6 to 175.6.
  • the specific peak positions given above for the model carboxylic compounds and the EB polymeric ester can vary slightly depending on the temperature Md solvent used for sample acquisition, the pH of the solution, the concentration of the doping agent used, d the frequency resolution of the spectrum, which in turn depends upon the field strength, the number of points in the Fourier transform, Md the homogeneity of the magnetic field. Accordingly, the peak positions are meant to be illustrative. Shifts in the peak positions will not affect the validity of the procedure outlined above. It is merely necessary that the peaks be sufficiently resolved to perform the integrations described above.
  • CM be applied to other EB polymer esters by suitable esterification of the foregoing model acids, followed by interpretation Md Malysis of the 13 C-NMR spectra of the resulting model ester compounds Md of their ester function ized EB polymer counterpart.
  • a continuous process was carried out in a pipe reactor consisting of four closely spaced SMX-type static mixers in a dispersing section, which ranged in size from a 5.08 cm (2 inch) diameter- 16 element mixer to a 1.27 cm (0.5 inch) diameter-6 element mixer.
  • the dispersing section was followed by a blending section with a type SMXL mixer of 3.8 cm (1.5 inches) in diameter Md 1.52 m (5 feet) in length, Md a soaking section consisting of two SMX mixers, each 10.2 cm (4 inches) in diameter and 2.74 m (9 feet) in length. Additional small mixers, each 2.54 cm (1 inch) in diameter with 12 elements, were located at the feed to each SMX mixer in the scaking section.
  • Ethylene-butene-1 polymer (M n of about 2000, 25 wt.% ethylene content) was fed to the reactor at a flow rate of about 40 kg/hour.
  • 2-chloro-4-methylphenol (“CMP") was separately fed to the reactor in M amount equivalent to 7.5 wt.%, based on the total weight of polymer Md CMP.
  • the feed temperature was about 40°C.
  • Mixed BF 3 Md CO were fed through a recycle compressor at a BF 3 to CO mole ratio of 0.19.
  • the BF 3 to CMP mole ratio was 0.34.
  • the viscosity of the liquid pirase was initially about 9.0 Pa • s (9000 cP) Md thereafter decreased to a level of about 1 Pa • s (1000 cP).
  • the shear rates in the four static mixers in the dispersing section were respectively about 11 s "1 , about 32 s "1 , about 120 s '1 , Md about 800 s *1 .
  • Shear rate in the blending section was between about 1 to about 2 s "1 , and in the soaking section between about 0.25 to about 0.5 s "1 .
  • the reactor residence time was 49 minutes Md the maximum temperature during the reaction was 51°C.
  • the residence time in the dispersing sedion was 2.5 minutes, Md the time interv s between mixers in the dispersing section were between 1 and 10 seconds.
  • Initial system pressure was about 12,420 kPa (1800 psig).
  • BF 3 Md unconsumed CO were removed from the polymer product by flashing Md recycled to the reactor inlet. Unconsumed CMP was separated by evaporation Md also recycled. Steady state operation provided a product having 86 wt.% active ingredient (i.e., weight percent of functionalized polymer relative to the weight of both function ized Md unfunction.alized EB polymer in the product), as dete ⁇ nined by chromatography.
  • the adive portion of the produrt was essentially 100% neo 2-chloro-4-methylphenyl ester functionalized EB polymer, as determined by 13 C-NMR
  • the ester product was found to consist of 48% ester of configurations A Md B, 54% ester of configurations A, B, Md C, Md 74% ester of configurations A, B, C d D.
  • Examples 2-4 A series of 2-chloro-4-methylphenyl ester functionalized EB polymer products were prepared via a continuous carbonylation process similar to that described in Example 1.
  • Example 7 400 g of the CMP ester functionalized polymer product of Example 3
  • Example 8 400 g of the CMP ester functionalized polymer product of Example 4

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  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

L'invention concerne un polymère fonctionnalisé par un néo-ester présentant un encombrement stérique relativement bas et une réactivité chimique élevée. Dans un aspect, le polymère fonctionnalisé par un ester est un polymère α-oléfine d'éthylène ayant été fonctionnalisé de manière à contenir des groupes d'esters -CO2R', les groupes d'esters étant fixés à des atomes de carbone tertiaires du squelette du polymère et R' représentant un alkyle substitué, un aryle ou un aryle substitué. L'invention concerne également un procédé de préparation des polymères fonctionnalisés par des esters, le polymère α-oléfine d'éthylène étant mis en réaction avec un monoxyde de carbone et un alcool en présence de BF3, avec un rapport molaire BF3/CO compris entre 0,6 et 1,5 environ. L'invention concerne enfin des dérivés du polymère fonctionnalisé par un ester obtenus par mise en réaction avec des composés réactifs nucléophiles (par exemple des amines).
PCT/US1998/027348 1997-12-30 1998-12-23 Polymeres reactifs fonctionnalises par des esters WO1999033884A1 (fr)

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US09/000,995 1997-12-30

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3539654A (en) * 1967-05-16 1970-11-10 Auxiliare De L Inst Francais D Method of modifying natural rubber with carbon monoxide and coreactant
WO1994013709A2 (fr) * 1992-12-17 1994-06-23 Exxon Chemical Patents Inc Polymeres fonctionnalises par la reaction de koch et leurs derives
WO1995021904A1 (fr) * 1994-02-15 1995-08-17 Basf Aktiengesellschaft Utilisation d'esters d'acide carboxylique comme additifs de carburants ou de lubrifiants et leur procede de preparation
WO1995035324A1 (fr) * 1994-06-17 1995-12-28 Exxon Chemical Patents Inc. Procede de carbonylation par reaction de koch discontinue
WO1995035328A1 (fr) * 1994-06-17 1995-12-28 Exxon Chemical Patents Inc. Dispersants pour huiles lubrifiantes derives de polyamine lourde

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3539654A (en) * 1967-05-16 1970-11-10 Auxiliare De L Inst Francais D Method of modifying natural rubber with carbon monoxide and coreactant
WO1994013709A2 (fr) * 1992-12-17 1994-06-23 Exxon Chemical Patents Inc Polymeres fonctionnalises par la reaction de koch et leurs derives
WO1995021904A1 (fr) * 1994-02-15 1995-08-17 Basf Aktiengesellschaft Utilisation d'esters d'acide carboxylique comme additifs de carburants ou de lubrifiants et leur procede de preparation
WO1995035324A1 (fr) * 1994-06-17 1995-12-28 Exxon Chemical Patents Inc. Procede de carbonylation par reaction de koch discontinue
WO1995035328A1 (fr) * 1994-06-17 1995-12-28 Exxon Chemical Patents Inc. Dispersants pour huiles lubrifiantes derives de polyamine lourde

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