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
  • C10M159/20—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products
  • C10M159/22—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products containing phenol radicals
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D17/00—Separation of liquids, not provided for elsewhere, e.g. by thermal diffusion
  • B01D17/02—Separation of non-miscible liquids
  • B01D17/04—Breaking emulsions
  • B01D17/045—Breaking emulsions with coalescers
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D17/00—Separation of liquids, not provided for elsewhere, e.g. by thermal diffusion
  • B01D17/02—Separation of non-miscible liquids
  • B01D17/04—Breaking emulsions
  • B01D17/047—Breaking emulsions with separation aids
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C65/00—Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
  • C07C65/01—Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups containing hydroxy or O-metal groups
  • C07C65/17—Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups containing hydroxy or O-metal groups containing rings other than six-membered aromatic rings
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
  • C07C69/76—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring
  • C07C69/94—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring of polycyclic hydroxy carboxylic acids, the hydroxy groups and the carboxyl groups of which are bound to carbon atoms of six-membered aromatic rings
• • 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, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/143—Organic compounds mixtures of organic macromolecular compounds with organic non-macromolecular 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, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • 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
  • C10L1/1981—Condensation polymers of aldehydes or ketones
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M145/00—Lubricating compositions characterised by the additive being a macromolecular compound containing oxygen
  • C10M145/18—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
  • C10M145/20—Condensation polymers of aldehydes or ketones
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2603/00—Systems containing at least three condensed rings
  • C07C2603/92—Systems containing at least three condensed rings with a condensed ring system consisting of at least two mutually uncondensed aromatic ring systems, linked by an annular structure formed by carbon chains on non-adjacent positions of the aromatic system, e.g. cyclophanes
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
  • C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
  • C10M2209/101—Condensation polymers of aldehydes or ketones and phenols, e.g. Also polyoxyalkylene ether derivatives thereof
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2227/00—Organic non-macromolecular compounds containing atoms of elements not provided for in groups C10M2203/00, C10M2207/00, C10M2211/00, C10M2215/00, C10M2219/00 or C10M2223/00 as ingredients in lubricant compositions
  • C10M2227/09—Complexes with metals
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2010/00—Metal present as such or in compounds
  • C10N2010/02—Groups 1 or 11
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2040/00—Specified use or application for which the lubricating composition is intended
  • C10N2040/25—Internal-combustion engines
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2040/00—Specified use or application for which the lubricating composition is intended
  • C10N2040/25—Internal-combustion engines
  • C10N2040/251—Alcohol-fuelled engines
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2040/00—Specified use or application for which the lubricating composition is intended
  • C10N2040/25—Internal-combustion engines
  • C10N2040/252—Diesel engines
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2040/00—Specified use or application for which the lubricating composition is intended
  • C10N2040/25—Internal-combustion engines
  • C10N2040/252—Diesel engines
  • C10N2040/253—Small diesel engines
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2040/00—Specified use or application for which the lubricating composition is intended
  • C10N2040/25—Internal-combustion engines
  • C10N2040/255—Gasoline engines
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2040/00—Specified use or application for which the lubricating composition is intended
  • C10N2040/25—Internal-combustion engines
  • C10N2040/255—Gasoline engines
  • C10N2040/28—Rotary engines

Definitions

• the present invention relates to cyclic calixarene compounds containing within the calixarene ring at least one unit of salicylic acid or salt thereof.
• the compounds of the invention are particularly suitable as thermal stabilising additives in fuel and for use in lubricating oil compositions for medium or low speed diesel engines, especially four stroke engines.
• the invention also relates to fuel compositions and to lubricating oil compositions comprising said compounds, e.g. aviation fuel compositions.
• the liquid fuel is combusted to produce power, but also is circulated in the aircraft as a heat exchange fluid to remove the excess heat generated at such speeds e.g. in lubricating oils.
• the fuel is thus maintained for long periods at high temperatures, which results in discoloration and decomposition to produce soluble coloured products and insoluble products such as gums, sediments and granular material; insoluble products can form deposits that reduce the heat exchange capacity and can block filters potentially causing loss of power.
• Soluble coloured by-products are unsightly and an indication of some decomposition.
• the cause of discoloration etc. may be from phenols, naphthenates and sulphur compounds and/or metals which are often present in the fuels.
• kerosine oil fuel is passed down a narrow metal feed pipe to the combustion chamber where it is burnt.
• Parts of the pipe are sufficiently near the hot chamber for them to be heated to significant temperatures, resulting in the risk of thermal degradation of the fuel in the pipe, especially with slow feed rates and high residence times in the pipe. This degradation can form solid deposits which reduce the flow and ultimately stop it, causing the combustion to stop.
• manufacturers of such devices have for many years recommended to their users that at least once each 6 months such pipe parts are cleaned of solid deposits of coke or other materials.
• USP5478367 describes the addition to diesel or jet fuel of a substituted unsaturated polyamine derivative dispersant to reduce particulate emissions on combustion and to reduce fouling i.e. deposition of insoluble deposits.
• Canadian Patent Publ. 2067907 describes the addition to distillate jet fuels of hydroxylamines to stabilise them against degradation at elevated temperatures.
• USP5468262 describes addition to jet fuels of thermal stability additives which are prepared by reacting a polyamine, aldehyde and phenol to form a condensate which is then reacted with a succinic anhydride containing a polyolefin derived unsaturated group.
• the additives are effective at 0.2% by weight.
• EP-A-678568 describes addition to jet engine fuels of anti deposition agents which are derivatives of (thio)phosphonic acids.
• the present invention provides a cyclic compound comprising m units of the formula la.
• Y is a divalent bridging group which may be the same or different in each unit;
• R° is H or (Ci-Ce) alkyl or is a metal or ammonium cation, (so the group C0 R° is a carboxylic salt);
• R 5 is H or (C ⁇ -C 6 o) alkyl; and
• j is 1 or 2;
• R is hydrogen, a hydrocarbyl or a hetero-substituted hydrocarbyl group; each of R 1 , R 2 and R 4 , which may be the same or different, is hydroxyl, hydrogen, hydrocarbyl or hetero-substituted hydrocarbyl, with the proviso that at least one of R 1 , R 2 , R 4 is hydroxyl, and m + n is 4 to 20, m is 1-8 and n is at least 3 and preferably either R 1 is hydroxyl and R 2 and R 4 are independently either hydrogen, hydrocarbyl or hetero- substituted hydrocarbyl, or R 2 and R 4 are hydroxyl and R 1 is either hydrogen, hydrocarbyl or hetero-substituted hydrocarbyl; and m + n is from 4 to 20, m is from 1 to 8 and n is at least 3 and with the proviso that at least one of the following features (a) to (e) is met namely the cyclic compound comprises at least one of (a) at least one formula
• the cyclic compound has at least 2 of (a) (b) (c) (d) and (e) preferably 3, most preferably 4 and especially all 5 in particular (a) and (c), or (b) and (c), and especially (d).
• the invention provides a cyclic compound wherein m is 2, n is 6, and both the units of formula (la) are in the form of a potassium carboxylate salt, and the cyclic compound comprises the substantial absence of linear species comprising formula (la) and (lb) units and the substantial absence of unreacted formula (la) and (lb) units.
• the cyclic compound is preferably a compound of the formula (I) with a ring structure.
• Y 1 and Y 2 are divalent bridging groups, which may be the same or different;
• R 3 is hydrogen, a hydrocarbyl or a hetero-substituted hydrocarbyl group; each of R 1 , R 2 and R 4 , which may be the same or different, is hydroxyl hydrogen, hydrocarbyl or hetero- substituted hydrocarbyl, with the proviso that at least one of R 1 , R 2 , R 4 is hydroxyl, and m + n is 4 to 20, m is 1-8 and n is at least 3 and wherein the compound of formula I comprises at least one of (a) at least one COOH grouping in the form of a carboxylate anion (b) at least one COOH grouping is in the form of an alkaline earth or alkali metal salt, preferably a potassium or sodium salt, especially a potassium salt (c) at least 2 e.g.
• the cyclic compound has at least 2 of (a) (b) (c) (d) and (e) preferably 3, most preferably 4 and especially all 5 in particular (a) and (c), or (b) and (c), especially (d).
• the invention provides a cyclic compound wherein m is 2, n is 6, and both carboxyl groups are in the form of potassium carboxylate salt and the cyclic compound is in the substantial absence of linear species comprising salicylate or salicylic acid units and phenol units and the substantial absence of unreactived salicylate or salicylic acid units and phenol units.
• Y 1 and Y 2 may each independently be a hydrocarbyl bridging group or be a hetero- substituted hydrocarbyl group or up to 50% mole of the totality of Y 1 and Y 2 group may be a hetero atom.
• the hydrocarbyl bridging group is preferably aliphatic and has a chain of 1-4 carbon atoms; preferably the group is of formula (CR 7 R 8 )d e.g. (CHR 8 ) d where each of R 7 and R 8 , which may be the same or different, represents hydrogen or hydrocarbyl e.g. of 1-6 carbons, such as methyl or ethyl and d is an integer of 1-4 preferably 2 or especially 1; advantageously the group is of formula (CHR 6 ) or (CHR 8 ) d where R 8 is as defined above preferably methyl or especially hydrogen.
• Y 1 and/or Y 2 may also represent a hetero-substituted hydrocarbyl group with a hetero atom, e.g. O, S or NH interrupting a chain of carbon atoms e.g. 2-4 carbon atoms, such as in CH OCH 2 , CH 2 SCH 2 or CH 2 NHCH 2 .
• a hetero atom e.g. O, S or NH interrupting a chain of carbon atoms e.g. 2-4 carbon atoms, such as in CH OCH 2 , CH 2 SCH 2 or CH 2 NHCH 2 .
• Up to 50 mole% of the totality of Y 1 and Y 2 groups may be a hetero atom e.g. O or NH or especially 5, e.g. 1-50 mole% especially 8-20 mole% of said groups.
• Y 1 and Y 2 are hydrocarbyl groups, and the compound of formula I is sulphur free.
• Each of R 1 , R 2 and R 4 represents hydroxyl, hydrogen, hydrocarbyl or hetero- substituted hydrocarbyl with the proviso that at least one of R 1 , R 2 and R 4 represents hydroxyl.
• all three may represent hydroxyl as in a phloroglucinol derivative, or two as in a resorcinol derivative (i.e. the compound of formula I contains a resorcinarene group), or one as in a phenol derivative.
• R 1 is hydroxyl and R 2 and R 4 are independently either hydrogen (which is preferred), hydrocarbyl or hetero-substituted hydrocarbyl, or R 2 and R 4 are hydroxyl and R 1 is either hydrogen, hydrocarbyl or hetero- substituted hydrocarbyl.
• hydrocarbyl includes (Ci-C ⁇ o) alkyl such as t-butyl, t-amyl, s-butyl, isopropyl, octyl, nonyl, dodecyl and octadecyl.
• the hydrocarbyl group may be derived from a polyolefin, for example polyethylene, polypropylene, polybutylene or a polyolefin copolymer, for example an ethylene/propylene copolymer, preferably derived from a polyisobutene.
• a polyolefin for example polyethylene, polypropylene, polybutylene or a polyolefin copolymer, for example an ethylene/propylene copolymer, preferably derived from a polyisobutene.
• Alternatives include isoprene-butadiene, styrene-isoprene or styrene-butadiene block copolymers such as those disclosed in WO 96/40846, or ethylene-propylene and ethylene-butene-1 copolymers having molecular weights from 1500 to 2500 or 7500, as disclosed in US 5567344 and US 5578237. Mixtures of all the above may also be
• Each of R ! -R 5 may otherwise be as described for R 3 below.
• the hydrocarbyl group for R 1 , R 2 or R 4 usually has 1-14 e.g. 1-6 carbons and is preferably saturated, especially an alkyl group e.g. methyl, ethyl, propyl, butyl or hexyl group.
• the hetero-substituted hydrocarbyl group has at least one e.g. 1-3 especially 1 hetero atom e.g.
• R 3 is hydrogen, hydrocarbyl or a hetero-substituted hydrocarbyl group.
• R 3 is hydrocarbyl or a hetero-substituted hydrocarbyl in at least R 3 group in the compound of formula I, especially with n such groups in the molecule.
• the hydrocarbyl group may be alkyl, alkenyl, cycloalkyl, aryl, aralkyl and contains at least 1 especially at least 4 or at least 8 carbon atoms e.g. 4-40 carbons in particular with 8-20 carbons in a chain.
• 8-24 or 8-20 carbons such as decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, lauryl, myristyl, stearyl, palmityl, propylene tetramer or alkenyl e.g. of 6-24 carbons such as oleyl, or cycloalkyl e.g. of 5-8 carbons such as cyclohexyl, aryl e.g. of 6-24 carbons such as phenyl, tolyl and alkylphenyl with 6- 16 carbons in the alkyl e.g. dodecylphenyl and aralkyl e.g.
• R 3 may also represent a polymeric hydrocarbyl group e.g. from a polyolefin group, especially from one or more olefins of 2-6 carbons such as ethylene, propylene, butene, isobutene; the polymeric groups may be from polyethylene, polypropylene, polybutene, an ethylene propylene copolymer or polyiso butene (which is preferred).
• Molecular weights of polymeric R 3 groups may be 300-6000 e.g. 500-2000. In the compound of formula I, there may be different R 3 groups in the same molecule.
• m is from 1 to 8 e.g. 1-4 especially 2 or in particular 1, while n is at least 3 e.g. 3-10, in particular 5-9 especially 6-8.
• the sum of m + n is 4- 20, preferably 5-10 in particular 7-9, e.g. 6 or 8, or a mixture of compounds with m + n having the value of 6 and 8.
• m is 1 or 2 and m + n is 5-10 e.g. 8.
• Y 1 or Y 2 is CH ;
• R 1 is hydroxyl;
• R 2 and R 4 are independently either hydrogen, hydrocarbyl or hetero-substituted hydrocarbyl;
• R 3 is either hydrocarbyl or hetero-substituted hydrocarbyl;
• R° is H or is substituted by an alkali metal ion, in particular a potassium ion;
• R 5 is hydrogen or an alkyl group of 6 to 50 carbon atoms, preferably 4 to 40 carbon atoms, more preferably of 6 to 25 carbon atoms;
• j is 2 or preferably 1;
• m + n has a value of at least 5, preferably at least 6, typically at least 8, where m is 1 or 2, preferably 1.
• R 2 and R 4 are hydrogen; R' is hydrocarbyl, preferably alkyl of 10 greater than 4, preferably greater than 9 carbon atoms; R is hydrogen; and m + n is from 6 to 12 e.g. 8; m is 1 or 2.
• R 2 and R 4 are hydrogen, m is 1 or 2, n is 5, 6 or 7, m + n is 6 and/or 8, R 1 is hydroxyl, R 3 is alkyl of 8-20 carbons e.g. dodecyl or octadecyl, or polyisobutenyl.
• the metal in the salt form may be an alkali metal e.g. Li, Na, K, Rb or Cs, or an alkaline earth metal e.g. Mg or Ca, or ammonium or a quatenary ammonium salt e.g. of formula R'R ⁇ R 4 wherein R'-R 4 are as defined above, especially with at least 3 and in particular 4 of them of less than 10 carbons.
• alkali metal e.g. Li, Na, K, Rb or Cs
• an alkaline earth metal e.g. Mg or Ca
• ammonium or a quatenary ammonium salt e.g. of formula R'R ⁇ R 4 wherein R'-R 4 are as defined above, especially with at least 3 and in particular 4 of them of less than 10 carbons.
• salixarenes For convenience the cyclic compounds are herein referred to as "salixarenes”.
• Calixarenes having a substituent hydroxyl group or groups include homocalixarenes, oxacalixarenes, homooxacalixarenes and heterocalixarenes.
• Salixarenes of the present invention may be made by reacting together appropriate amounts of the optionally substituted salicylic acid (or carboxylic ester), an optionally substituted phenol, and a carbonyl compound which is preferably an aldehyde e.g. formaldehyde, or acetaldehyde, in the presence of a base and optionally a catalyst.
• the reaction may be performed in the presence of sulphur if the compound of formula I is to contain combined sulphur.
• the salixarenes may be made by a process comprising reacting together, in the presence of a basic catalyst, compounds of the formulas (Ila) and (lib)
• Preferred basic catalysts are alkali metal hydroxides such as sodium hydroxide, potassium hydroxide and lithium hydroxide
• a proportion of the product may comprise linear molecules.
• Linear molecules are also composed of units having formulas (la) and (lb) except that instead of the ends of the molecule being joined to form a ring, each end has a terminal group which is independently one of the following
• the cyclic form comprises at least 40 %, more preferably at least 60 % and most preferably at least 80 % by weight of the reaction product.
• the process may be performed with an amount of base which is 0.01-0.2 equivalents per mole of the salicylic acid, with the base being effectively in catalytic amount.
• the process may be performed in a melt or in the presence of water or a solution or suspension.
• the water may be added with the base e.g. aqueous sodium or potassium hydroxide solution, and/or a possible solvent for the formaldehyde (e.g. 10-30% formaldehyde solution), the amount of added water being usually 1-20% of the total S weight of the reactant e.g. 5-15%.
• the process is performed with the water present initially, and then once reaction has started, then any water present as well as water produced as by product is removed e.g. by evaporation or distillation, whether under reduced pressure, and/or heating at above 110°C.
• the process may also be performed in the presence of an inert organic liquid which may be a solvent for at least one of the reactants, e.g. the phenol and/or salicylic acid and/or a solvent or non solvent for at least one of the phenolic products, especially a salixarene e.g. of formula I and/or a linear phenolic species.
• the liquid is usually a hydrocarbon of atmospheric boiling point 100-160°C, such as toluene or a xylene or methylbenzene.
• the amount of liquid may be 10-90% of the total weight of solvent and reactants, especially 50-90%o.
• the liquid is immiscible with water and can entrain water in its distillation and/or reflux, e.g. a Dean and Stark apparatus.
• the solvent if any may be evaporated to leave a crude product, or the reaction product (optionally with solvent) treated or used as such.
• the direct product of the process to make the salixarenes may be used as such (i.e. without purification from other phenolic compounds) or may be converted from one salt form to another e.g. via ion exchange or by way of acidification to form the free acids, and then if desired formation of a salt by neutralisation.
• the direct product is purified to increase its content of cyclic and/or carboxylic species.
• the direct product may be distributed between a substantially water immiscible organic solvent e.g. an aliphatic liquid hydrocarbon, such as kerosene or hexane or an aromatic hydrocarbon such as toluene or xylene, and an aqueous medium.
• the medium may be basic e.g.
• the aqueous medium can extract the carboxylic species, while the non carboxylic species remains in the organic phase; the phases are then separated and then carboxylic salt recovered from the aqueous phase, or acidified to free carboxylic acid and recovered from an organic phase.
• the direct product may also be purified, when dissolved in organic solvent, by addition of a compound capable of producing a salt insoluble in the solvent e.g. addition of a barium salt (as such or in organic or aqueous solution) can cause precipitation of an insoluble barium carboxylate salt, which may be separated from the non carboxylic compounds. Acidification of the barium salt enables the free carboxylic acid to be recovered.
• the direct product in organic solution is e.g. an aliphatic or aromatic hydrocarbon such as one described above, may be contacted with an anion exchange resin, so that the carboxylic compound(s) are bound to the resin, while the non carboxylic compounds are not.
• the treated resin may then be separated and treated with alkali metal hydroxide or alkoxide solution to regenerate the resin for reuse and to liberate the alkali metal salt of the carboxylic acid.
• the process may be batch wise or continuous (with a pair of resins in parallel, one for separation while the other is being regenerated).
• the resin is preferably a macroreticular one, and usually has quaternary ammonium cationic substituents; an example of such a resin is that sold under the Trade Mark Amberlyst 15.
• the direct product may also be purified by shape selective separation by contact of the direct product (in acid or salt form) in organic solution with an inorganic porous solid, whose pores are insufficiently large to allow the salixarene to enter, but allow the linear products to enter.
• Preferred maximum diameter for pores are 100 A, especially ⁇ 70 or ⁇ 50 A and especially above 20 A.
• porous solids are silica, alumina and silica/alumina as well as ceramic membranes, e.g. made of alumina or zirconia.
• the contact may be batch wise, e.g.
• the separation is continuous e.g. in a cross flow made and/or with a tube of ceramic membrane, through the walls of which the non cyclics pass while the cyclics pass down the tube and are concentrated.
• the amount of base is at least 0.2 equivalents per mole of the salicylic acid, in particular 0.2-10, such as 0.9-5 especially 2-5 or about 1.
• the base chosen is usually the one which provides the cations required in the product, e.g. sodium or potassium hydroxide or carbonate to provide sodium or potassium salixarene salt.
• the base for the reaction may be different, and then the reaction product salt may be converted into the desired salt e.g. via ion exchange.
• an alkali metal base can be used in the reaction and the salt converted to for example quaternary ammonium or calcium, salt form.
• a preformed salt thereof may be used, e.g. sodium or potassium salicylate, in the form for example of a solid or in aqueous solution.
• the process preferably involves reaction of the salicylic acid and the phenol in a molar percentage of at least 20% salicylic acid units based on the total of salicylic and phenol e.g. 20-90%, such as 20- 40%).
• the amount of base present is 0.2-8 equivalents, based on the equivalents of carboxyl groups in the salicylic acid e.g. 2-5 equivalents.
• the process usually involves the presence of a base with a cation of appropriate size, the larger the cation the larger the ring.
• a spread of salixarene ring sizes is obtained, the average is lower for Li e.g. 5-7, than Na e.g. 6-8, than K 7-9 and Cs 9-11.
• the fuel or lubricating composition e.g. jet fuel composition may also contain a non ring i.e. linear form of the compound of formula la/lb I, i.e. with structural units as shown in the Formulae I but terminated usually by the phenol and/or salicylic acid units.
• the present invention also provides the use of at least one of these "salixarenes" to reduce the discoloration on heating of fuel compositions e.g. jet fuel and fuel compositions comprising kerosine.
• the preferred additive is dodecyl-salicylic calix[8]arene, which is a Salix[8]arene comprising 7 dodecyl substituted phenolic units and one salicylic acid unit joined by methylene bridges.
• Another preferred compound is the corresponding salixarene with 2 salicylic groups and 6 dodecylphenol units preferably at least partially as an alkali metal salt e.g. potassium salt and especially in the form of the dipotassium salt.
• the additive may be present in the composition in amount of at least 1, at least Sppm, such as 1-1000, 5-1000 e.g. 5-500 especially 5-200 or 10-lOOppm based on the weight of the composition e.g. the jet fuel composition.
• the additive may be mixed with the jet or other fuel composition in the form of a concentrate in solution, e.g. in an aliphatic aromatic hydrocarbon in 20-80% w/w solution, or it may be added as such to give a solution in the fuel.
• More than one of the salixarenes may be present e.g. 2-4, especially differing only in the values of at least one of m and n, especially n.
• the composition can comprise jet fuel.
• the composition can comprise kerosine, in particular in jet fuel.
• the main component of the jet fuel itself is usually a middle boiling distillate boiling point in the range 150-250°C at atmospheric pressure and the fuel is usually kerosine which may be mixed with gasoline and optionally light petroleum distillate as in mixtures of gasoline and kerosene.
• the jet fuel may comprise mixtures of gasoline and light petroleum distillate, e.g. in weight amounts of 20-80:80-20 such as 50- 75:50-25 which weight amounts may also be used for mixtures of gasoline and kerosene.
• the jet fuels for military use are designated JP4 to 8 e.g. JP4 as 65% gasoline/35%) light petroleum distillate (according to US Mil. Spec.
• Jet fuel for civilian use is usually a kerosene type fuel and designated Jet A or Jet Al.
• the jet fuel may have a boiling point of 66-343°C or 66-316°C (150-650°F e.g. 150 - 600°F), initial boiling point of 149-221°C, e.g. 204°C (300-430°F, e.g.
• Jet fuel for turbojet use may boil at 93-260°C (200-500°F) (ASTM D1655-59T). Further details on aviation fuels may be obtained from "Handbook of Aviation Fuel Properties", Coordinating Research Council Inc., CRC Report No. 530 (Society of Automotive Engineers Inc., Warrendale, PA, USA, 1983) and on US military 25 fuels, from "Military Specification for Aviation Turbine Fuels", MIL-T-5624P.
• the jet fuel may be the straight run kerosene optionally with added gasoline, but preferably has been purified to reduce its content of components contributing to or encouraging formation of coloured products and/or precipitates.
• components include aromatics and olefins and mercaptans.
• the fuels may be purified to reduce their mercaptan content e.g. Merox fuels and copper sweetened fuels or to reduce their sulphur content e.g. hydrofined fuels or Merifined fuels.
• Merox fuels are made by oxidation of the mercaptans and have a low mercaptan S content (e.g.
• Hydrofined jet fuels are ones in which the original fuel has been hydrogenated to remove at least some of sulphur compounds e.g. thiols and under severe conditions to saturate the aromatics and olefins; hydrofined jet fuels have very low sulphur contents (e.g. less than 0.01% S by weight).
• Merifined fuels are fuels that have been extracted with an organic extractant to reduce or remove their contents of sulphur compounds and/or phenols.
• the jet fuel may also contain metals, either following contact with metal pipes or carried over from the crude oil; examples of such metals are copper, nickel, iron and chromium usually in amounts of less than 1 ppm e.g. each in 10-150 ppb amounts.
• Merox and hydrofined fuels are preferred and may be used in JP 4-8 jet fuels.
• the fuel comprising kerosine may also be a fuel for combustion especially for non motive purposes, e.g. power generation, steam generation, and heating, especially for use 15 in buildings and for cooking, e.g. as described above.
• the fuel is particularly suitable for the devices e.g. boilers and slow cookers as described above in which there is localised preheating of the fuel before it is combusted.
• Such fuels are known as burning kerosine and may have the same physical properties as the kerosine based jet fuels described above, e.g. straight run kerosine, or kerosine modified to reduce its content of at least one of aromatics, olefins and sulphur compounds, as described above.
• the fuel may also contain metals as described above.
• the fuel compositions of the invention contains the cyclic compound of formula la/lb or I and may also contain at least one conventional additive e.g. for jet fuels or burning fuels such as an antioxidant, corrosion inhibitor, dispersant/detergent, (in particular in the case of hydroxy carboxylic acids (see below)), especially in amounts each of 1-lOOOppm, e.g. 20-200ppm.
• the "salixarene" additives of formula I may be present in the composition especially with a dispersant; the dispersant is in particular one for solids known for use in fuels e.g. automotive burning or aviation fuels.
• Such dispersants usually have a polymeric carbon backbone with pendant groups containing nitrogen, which may be primary, secondary or tertiary, in cyclic or acyclic systems, and especially in amine, amide or imide groupings, in particular cyclic imide groups.
• the dispersants may also contain 1-5 polymer chains which are bridged by the nitrogen containing groups. Examples of such dispersants are the reaction products of polyisobutene succiic anhydride (PIBSA) and polyamines.
• PIBSA polyisobutene succiic anhydride
• Such dispersants are known compounds for dispersing particles of in non aqueous systems e.g. hydrocarbon systems.
• the weight ratio of "salixarene" to dispersant may be 99: 1 to 10:90, especially 30:70 to 70:30.
• the additives and the fuel composition are preferably substantially ashless. Burning kerosine is usually substantially free of the above additives apart from that of formula I or la/l
• the fuel compositions of the invention containing the compounds of formula I, la, lb have an improved thermal stability as shown by a reduced tendency to discolour and/or produce solids on heating compared to the fuel alone (in the isothermal corrosion and oxidation test (ICOT based on ASTM D487 1)).
• the combination of the compounds of formula I and certain other hydroxy carboxylic acid derivatives imparts to some fuels further improved stability still, better than either additive alone. This synergistic behaviour is found with combinations of the compound of formula I, la, lb and the hydroxycarboxylic acid in Merox fuels.
• the invention also provides a blend comprising at least one compound of formula I, la, lb and at least one hydroxy carboxylic acid
• the invention also provides a fuel composition comprising said blend and a fuel comprising kerosine and/or a jet fuel which is a Merox fuel, especially one which has a mean deposit forming tendency in the ICOT test according to ASTM D4871 of 80-120mg deposit per litre of fuel, in particular 80-105mg/l.
• the weight ratio of the compound (c) of formula I, la, lb to hydroxycarboxylic acid is usually 10-90:90-1, in particular 30-85:70-15 and especially 35-65:65-35.
• the amount of the blend in the fuel is usually 10-lOOOppm e.g. 30-200ppm.
• the hydroxycarboxylic acid contains in total at least 1 hydroxyl group e.g. 1-4 such as 2 or 3 but preferably 1 hydroxyl group.
• hydroxy acid usually contains a hydroxyl group on a carbon atom alpha, beta or gamma to the carbon atom to which the carboxylic acid group is bonded and may optionally have 1 or more hydroxyl groups elsewhere in the molecule: preferably the only hydroxyl group in the molecule is in the alpha, beta or gamma especially the beta position.
• the hydroxy acid may be of formula,
• each of R 10 , R 1 and R 14 which may be the same or different, represents hydrogen or an organic group, bonded via carbon or a heteroatom, which is O, N or S, with the proviso that at least one, and preferably only one of R 10 -R 14 represents an organic group containing a carbon chain of at least 8 carbon atoms.
• the organic groups, bonded via carbon are alkyl, cycloalkyl, alkenyl, aralkyl or aryl, e.g.
• the organic group bonded via nitrogen are amino groups with long chain hydrocarbyl group e.g. 8-24 carbons, or amido or imido groups from long chain carboxylic acids with 8-3000 carbons, e.g. 8-24 carbons such as fatty acids e.g. stearic and palmitic acids, or 50-3000 carbons e.g.
• R 1 preferably represents hydroxyl/or hydrogen
• R 10 represents hydrogen or a long chain hydrocarbyl group of at least 8 carbons, especially 8-24 or 50-3000 carbons
• R 12 represents hydrogen or alkyl of 1-6 carbons e.g. methyl or ethyl
• R 13 represents hydroxyl or hydrogen
• R 14 represents hydrogen or a amino, amido or imido group with a long chain aliphatic group or long chain mono or di acyl group, in particular a long chain succiic imide e.g. PIBSA.
• R 10 or R 14 contains a long chain aliphatic group but not both.
• hydroxy carboxylic acid are N(long chain acyl) derivatives of beta hydroxy amino acids e.g. seine and threonine and long chain hydrocarbyl alpha hydroxy acids e.g. 1 -hydroxy dodecanoic, 1-hydroxypalmitic and 1-hydroxystearic acids, 1- hydroxyl polyiso butenyl-1 -carboxylic acid (from PIB aldehyde).
• the invention also provides a fuel composition comprising liquid hydrocarbons, 30 at least a majority of which boil at atmospheric pressure at 251-350°C (according to ASTM D86).
• the hydrocarbon fuel may be diesel oil (e.g.
• gas oil e.g. as defined in its European Standard the dislcosure of which is herein incorporated by reference
• the gas oil is a hydrocarbon fraction boiling between kero sine and light lubricating oil.
• the gas oil may be straight run gas oil, from direct distillation of crude oil under atmospheric pressure, cracked gas oil, which has the above boiling range and is made by distillation of the product of cracking high boiling or other oils either thermally or catalytically, or vacuum gas oil, with the above boiling range made by vacuum distillation of a residue, e.g.
• liquid hydrocarbon in the fuel composition may also be a product of hydrotreating or hydrofining a gas oil as described above; more information on these is provided below.
• the fuel composition can thus contain at least a majority of a gas oil e.g. 51-100%> (of the liquid hydrocarbons) e.g. at least 70% such as 70-90%>, with usually up to 30% by weight (of total liquid hydrocarbons) of liquid hydrocarbons boiling above or below the gas oil, e.g. kerosine bp 150-250°C and heavy gas oils of Final Boiling Point 350- 410°C.
• kerosine bp 150-250°C e.g. kerosine bp 150-250°C
• heavy gas oils of Final Boiling Point 350- 410°C.
• Blends comprising a majority of gas oil with a minority of kerosene, or a majority of gas oil with a minority in total of kerosine and the heavy gas oil are preferred.
• the fuel composition may contain one or more of the types of gas oil discussed above, preferably with straight run gas oil and at least one other gas oil, especially with at least 50% or at least 70% of the straight run gas oil and up to 30%) in total of one or more other gas oils e.g. cracked gas oil.
• the fuel of the invention may comprise diesel fuel itself e.g. for use in diesel engines for motive use such as automobiles, trucks and buses, rather than the cruder gas oil, which contains diesel and a wide range of liquid hydrocarbons of boiling point alone 25 and below diesel.
• the gas oil is preferred for non motive uses.
• the fuel may also comprise biofuel from vegetable and/or animal sources, such as rapeseed oil esters e.g. the methyl ester, especially in weight ratios to liquid hydrocarbons of bp 251-350°C of 5- 30:95-70.
• the liquid hydrocarbons in the fuel of the invention may have at least one of and 30 preferably all of the following distillation properties 220-250°C an initial bp (IBP) of 140-220°C, a 10% distillation point of 190-250°C, 50% distillation point of 220-250°C, 90% distillation point of 280-380°C (e.g. 300-350°C) 95% distillation point of 320- 380°C (e.g.340-360°C) and a Final Boiling Point of 290-385°C (such as 330-360°C).
• IBP initial bp
• the hydrocarbons may have Conradson Carbon contents (by weight) of 0.01-1 e.g. 0.01-0.1 or 0.1-1. They may have aniline points of 40-80°C e.g. 60-75°C (as in gas oils) or 10-40 e.g. 15-30 (as in diesel oil). They may have a Specific Gravity of 0.80-0.90, e.g. 0.82-0.88 or 0.82-0.86, and a minimum Flash Point of at least 38°C (Closed, Abel.) or at least 55°C such as 75-95°C (Closed Pensky Martens). The cetane Number may be at least 40, 45, 49 or 51 such as 40-55, e.g.
• the S chemical analysis may be less than 0.5% sulphur compounds (expressed as elemental sulphur) such as 0.0001-0.5%), preferably less than 0.2% or 0.05% or 0.01%S, such as 0.05-0.2%S.
• the aromatic contents of the liquid hydrocarbons is usually less than 40%> total aromatics e.g. 20-40% but especially less than 20%) such as 5-15% total aromatics.
• the liquid hydrocarbons e.g. gas oil or diesel preferably have been purified to reduce their content of components contributing to or encouraging formation of coloured products and/or precipitates or sulphur oxides on combustion.
• aromatics and olefins and sulphur compounds are aromatics and olefins and sulphur compounds.
• the fuels may be purified to reduce their sulphur content e.g. hydrofined fuels or Merifined fuels.
• Hydrofined fuels are ones in which the original fuel has been hydrogenated to remove at least some of sulphur compounds e.g. thiols and under severe conditions to saturate the aromatics and olefins; hydrofined fuels have very low sulphur contents (e.g. less than 0.01%) S by weight).
• Merifined fuels are fuels that have been extracted with an organic extractant to reduce or remove their contents of sulphur compounds and/or phenols.
• the fuel of the invention may also contain metals, either following contact with metal pipes or carried over from the crude oil; examples of such metals are copper, nickel, iron and chromium usually in amounts of less than 1 ppm e.g. each in 10-150 ppb amounts. Hydrofined fuels are preferred.
• the fuel compositions of the invention include the cyclic compound of formula la/lb or I and may also contain at least one conventional additive for automotive, heating or burner fuels e.g. an antioxidant, corrosion inhibitor, stabilisers, pour depressant, demulsiflers, antifoams, cetane improvers, lubricity additives, anti-static additives, dehazers, lubricity additives package compatibilisers and dispersant/detergent, (in particular in the case of hydroxy carboxylic acids (see below)), especially in amounts each of 1-lOOOppm, e.g. 20-200ppm.
• at least one conventional additive for automotive, heating or burner fuels e.g. an antioxidant, corrosion inhibitor, stabilisers, pour depressant, demulsiflers, antifoams, cetane improvers, lubricity additives, anti-static additives, dehazers, lubricity additives package compatibilisers and dispersant/detergent, (in particular in the case of
• the "salixarene" additives of formula I may be present in the composition especially with a dispersant; the dispersant is in particular one for solids known for use in fuels e.g. heating or burner fuels.
• a dispersant usually have a polymeric carbon backbone with pendant groups containing nitrogen, which may be primary, secondary or tertiary, in cyclic or acyclic systems, and especially in amine, amide or imide groupings, in particular cyclic imide groups.
• the dispersants may also contain 1-5 polymer chains which are bridged by the nitrogen containing groups. Examples of such dispersants are the reaction products of polyisobutene succiic anhydride (PIBSA) and polyamines.
• PIBSA polyisobutene succiic anhydride
• Such dispersants are known compounds for dispersing particles of in non aqueous systems e.g. hydrocarbon systems.
• the weight ratio of "salixarene" to dispersant may be 99: 1 to 10:90, especially 30:70 to 70:30.
• the additives and the fuel composition are preferably substantially ashless.
• the fuel compositions of the invention containing the compounds of formula I, la, lb have an improved thermal stability as shown by a reduced tendency to discolour and/or produce solids on heating compared to the fuel alone.
• the combination of the compounds of formula I and certain other hydroxy carboxylic acid derivatives imparts to some fuels further improved stability still, better than either additive alone in particular with Merox fuels.
• the fuel composition may also include at least one hydroxy carboxylic acid 20 (different from said compound) with at least one chain of at least 8 carbon atoms.
• the fuels of the invention may be used in combustion apparatus for motive use or in particular for non motive use in which the fuel is subjected to heating to a temperature e.g. of 100-400°C such as 200-300°C before combustion e.g. by proximity to the combustion chamber or otherwise (which may be at 500-700°C).
• the feed pipes to the combustion chamber are usually made of metal e.g. copper or steel such as stainless steel, which may become corroded resulting in metal leaching into the oil encouraging degradation.
• the oil may be emitted into the chamber via a nozzle which becomes hot.
• the combustion may be in a vaporising burner in which metal in the burner chamber is heated by the flame and in turn vaporises the fuel; examples of such burners are vaporising and pot burners.
• the combustion is preferably in an atomising burner in which the fuel is atomised either directly, as in pressure jet burners (of low, medium or high pressure) (including simple and wide range burners) and blast burners, or indirectly as in rotary cup burners in which a sheet of fuel is made first and then atomised by contact with air.
• the atomising burners usually have a hot nozzle on and in which degradation deposits can form.
• the combustion apparatus may be used to produce heat directly as in industrial furnaces, e.g.
• the apparatus is used for raising power as in gas turbines for electrical power generation.
• the invention also provides lubricating oil compositions suitable for 'medium- or low-speed diesel engines, typically the four-stroke trunk-piston engine comprising said cyclic compound. Details of suitable lubricating oils and their other additives in addition to the cyclic compound are described in WO 9925677, the disclosure of which is hereby incorporated by reference.
• a reaction apparatus was then set up incorporating the 5L flange flask, a flange lid and clip, overhead stirrer with paddle and PTFE stirrer gland, and double surface condenser and distillate collector.
• the reactor contents were heated by an electric mantle/thermocouple/Endotherm temperature controller system.
• the glassware from just above the mantle to just below the condenser was lagged with wool.
• reaction mixture was rapidly heated to 90°C, and the temperature then further increased very slowly at a rate of approximately 1°C every 10 minutes.
• Water (77ml) was collected over period of 7 hours, at the end of which the temperature had reached 140°C.
• the mixture was then allowed to cool overnight before being heated at about 140°C for a further 2 5 hours
• JFTOT Jet Fuel Thermal Oxidation Tests
• EP- A-660077 the disclosure of which is herein incorporated by reference
• the fuel contacts a heated standard aluminium tube under limited oxygen to produce deposits on the tube surface, the thickness of the deposits being determined either by colour (according to ASTM 3241) or ellipsometry according to EP- A-660077
• the tubes were heated at 335°C for 5hr, and the deposit volume found from the thickness profile by ellipsometry
• Fractions 2-5 are non carboxylic fractions of high or low molecular weight and of S poor activity, compared to Fraction 1.

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