Classifications

• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
  • C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
  • C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
  • C10G2/33—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used
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  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
  • C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
  • C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
  • C10G2/33—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used
  • C10G2/331—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals
• • 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
  • C10L1/16—Hydrocarbons
  • C10L1/1616—Hydrocarbons fractions, e.g. lubricants, solvents, naphta, bitumen, tars, terpentine
• • 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
  • C10L1/16—Hydrocarbons
  • C10L1/1625—Hydrocarbons macromolecular compounds
  • C10L1/1633—Hydrocarbons macromolecular compounds homo- or copolymers obtained by reactions only involving carbon-to carbon unsaturated bonds
  • C10L1/1641—Hydrocarbons macromolecular compounds homo- or copolymers obtained by reactions only involving carbon-to carbon unsaturated bonds from compounds containing aliphatic monomers
• • 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
  • C10L1/16—Hydrocarbons
  • C10L1/1625—Hydrocarbons macromolecular compounds
  • C10L1/1633—Hydrocarbons macromolecular compounds homo- or copolymers obtained by reactions only involving carbon-to carbon unsaturated bonds
  • C10L1/1658—Hydrocarbons macromolecular compounds homo- or copolymers obtained by reactions only involving carbon-to carbon unsaturated bonds from compounds containing conjugated dienes
• • 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
  • C10L1/16—Hydrocarbons
  • C10L1/1691—Hydrocarbons petroleum waxes, mineral waxes; paraffines; alkylation products; Friedel-Crafts condensation products; petroleum resins; modified waxes (oxidised)
• • 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
  • C10L1/195—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
  • C10L1/196—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and a carboxyl group or salts, anhydrides or esters thereof homo- or copolymers of compounds having one or more unsaturated aliphatic radicals each having one carbon bond to carbon double bond, and at least one being terminated by a carboxyl radical or of salts, anhydrides or esters thereof
  • C10L1/1963—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and a carboxyl group or salts, anhydrides or esters thereof homo- or copolymers of compounds having one or more unsaturated aliphatic radicals each having one carbon bond to carbon double bond, and at least one being terminated by a carboxyl radical or of salts, anhydrides or esters thereof mono-carboxylic
• • 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
  • C10L1/195—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
  • C10L1/197—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and an acyloxy group of a saturated carboxylic or carbonic acid
  • C10L1/1973—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and an acyloxy group of a saturated carboxylic or carbonic acid mono-carboxylic
• • 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
  • 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
  • C10L1/1985—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 polyethers, e.g. di- polygylcols and derivatives; ethers - esters
• • 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
  • C10L1/22—Organic compounds containing nitrogen
  • C10L1/222—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond
• • 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
  • C10L1/22—Organic compounds containing nitrogen
  • C10L1/222—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond
  • C10L1/224—Amides; Imides carboxylic acid amides, imides
• • 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
  • C10L1/22—Organic compounds containing nitrogen
  • C10L1/234—Macromolecular compounds
  • C10L1/238—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, 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
  • C10L1/22—Organic compounds containing nitrogen
  • C10L1/234—Macromolecular compounds
  • C10L1/238—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
  • C10L1/2383—Polyamines or polyimines, or derivatives thereof (poly)amines and imines; derivatives thereof (substituted by a macromolecular group containing 30C)

Definitions

• This invention concerns a fuel additive.
• this invention concerns a fuel additive suitable for lowering low temperature operability below the cloud point of a fuel oil.
• Fuel additives are known for reducing the low temperature operability of fuel oils. However, known fuel additives are often ineffective in lowering the low temperature operability of fuel oils having a cloud point of less than or equal to -25°C.
• CFPP cold filter plugging point test- see J. Inst. Pet. vol. 52 (510), June 1966, pp 173-285) is a test that is widely used in Europe to determine cold flow operability of fuels. In North America this test is replaced by LTFT (low temperature filterability test, ASTM D 4539).
• the aim of the present invention is to provide an improved fuel additive for lowering the low temperature operability of fuel oils.
• a further aim of the present invention is to provide a cold flow additive for fuel oils having a cloud point of less than or equal to -20°C.
• a further aim of the present invention is to provide a fuel additive that can be used to replace, in part or in full, the use of kerosene in fuel oils, preferably diesel fuel oils, having a cloud point of less than or equal to -20°C.
• a fuel additive comprising
• the fuel additive preferably comprises:
• the fuel additive also preferably comprises:
• the fuel additive also preferably comprises:
• the fuel additive also preferably comprises:
• a fuel oil composition comprising the fuel additive defined above and fuel oil.
• a method for reducing the cloud point of a fuel oil comprising the step of adding the fuel additive defined above to the fuel oil.
• the fuel additive of the present invention is particularly effective in fuel oils having a cloud point of less than or equal to -15°C, preferably less than or equal to -20°C, and even more preferably less than or equal to -25°C.
• a fuel additive concentrate comprising the fuel additive defined above in admixture with a compatible solvent.
• Waxes have conventionally been defined by reference to their gross physical characteristics in view of the large and varied number of hydrocarbon components that they contain and the difficulties in separating such closely homologous hydrocarbon molecules.
• 'Industrial Waxes' by H. Bennett published in 1975 describes the different types of petroleum wax and indicates that the characteristics of melting point and refractive index have proved useful in classifying the variety of waxes available from different sources.
• the wax needs to have a melting point of less than 40°C.
• the wax has a melting point of between 10 and 40°C. More preferably the wax has a melting point of between 15 and 35°C.
• the melting point is determined using DSC, i.e. differential scanning calorimetry, at heating/cooling rates of 2-5°C per minute. Further details of the DSC test are provided in the Examples.
• the wax needs to have a refractive index of greater than 1.4550 at 70°C.
• the wax has a refractive index of greater than 1.4600, more preferably greater than 1.4650.
• the wax preferably has a refractive index of less than 1.475.
• the refractive index is determined in accordance with the standard test method ASTM D1747-94, in which the temperature at the point of measurement has been set to 70°C.
• the wax is preferably a non-normal paraffinic wax.
• the term 'non-normal paraffinic wax' is used to mean a wax that comprises less than 40% of n-alkanes by weight, based on the total weight of the wax.
• the non-normal paraffinic wax contains less than 35%, more preferably less than 30%, and even more preferably less than 20%, of n-alkanes by weight.
• the non-normal paraffinic wax contains less than 10% of n-alkanes by weight.
• the wax is typically obtained by appropriate separation and fractionation of waxcontaining distillate fractions, and is available from wax suppliers.
• a single wax having the required refractive index and melting point may be used in the fuel additive.
• a mixture of one or more waxes, at least one of which having the required refractive index and melting point, may also be used.
• the wax is preferably present in the fuel oil in an amount ranging from 10 to 10,000 ppm, preferably from 50 to 5,000 ppm and most preferably from 100 to 1,000 ppm.
• the growth arrestor is also known as a growth inhibitor.
• the growth arrestor is preferably a copolymer of ethylene and an unsaturated ester.
• a copolymer of ethylene and an unsaturated ester has a polymethylene backbone divided into segments by hydrocarbyl side chains interrupted by one or more oxygen atoms and/or carbonyl groups.
• the copolymer may comprise an ethylene copolymer having, in addition to units derived from ethylene, units of the formula -CR 1 R 2 -CHR 3 - wherein R 2 represents hydrogen or a methyl group; R 1 represents a -OOCR 4 or -COOR 4 group wherein R 4 represents hydrogen or a C 1 to C 28 , preferably a C 1 to C 16 , more preferably a C 1 to C 9 , straight or branched chain alkyl group; and R 3 represents hydrogen or a -COOR 4 or -OOCR 4 group.
• the growth arrestor may comprise a copolymer of ethylene with an ethylenically unsaturated ester, or a derivative thereof.
• An example is a copolymer of ethylene with an ester of an unsaturated carboxylic acid such as ethylene-acrylate (e.g. ethylene-2-ethylhexylacrylate), but the ester is preferably one of an unsaturated alcohol with a saturated carboxylic acid such as described in GB-A-1,263,152.
• An ethylene-vinyl ester copolymer is preferably selected from: an ethylene-vinyl acetate, an ethylene vinyl propionate, an ethylene-vinyl hexanoate, an ethylene-vinyl 2-ethylhexanoate, or an ethylene-vinyl octanoate copolymer.
• Neo acid vinyl esters are also useful.
• the copolymers contain from 1 to 25, preferably 5 to 20, mole % of vinyl ester, more preferably from 5 to 18 mole % of vinyl ester. They may also be in the form of mixtures of two copolymers such as those described in US-A-3,961,916 and EP-A-113,581.
• number average molecular weight, as measured by vapour phase osmometry, of the copolymer is 1,000 to 10,000, more preferably 1,000 to 5,000.
• the copolymers may be derived from additional comonomers, e.g. they may be terpolymers or tetrapolymers or higher polymers, for example where the additional comonomer is isobutylene or diisobutylene or another ester giving rise to different units of the above formula and wherein the above-mentioned mole %'s of ester relate to total ester.
• the copolymers may additionally include small proportions of chain transfer agents and/or molecular weight modifiers (e.g. acetaldehyde or propionaldehyde) that may be used in the polymerisation process to make the copolymer.
• chain transfer agents e.g. acetaldehyde or propionaldehyde
• molecular weight modifiers e.g. acetaldehyde or propionaldehyde
• the copolymers may be made by direct polymerisation of comonomers. Such copolymers may also be made by transesterification, or by hydrolysis and reesterification, of an ethylene unsaturated ester copolymer to give a different ethylene unsaturated ester copolymer.
• ethylene-vinyl hexanoate and ethylene-vinyl octanoate copolymers may be made in this way, e.g. from an ethylene vinyl acetate copolymer.
• Preferred copolymers are ethylene-vinyl acetate or ethylene-vinyl propionate copolymers, or ethylene-vinyl 2-ethylhexanoate or ethylene-vinyl octanoate co- or terpolymers, such as ethylene-vinyl acetate-vinyl 2-ethylhexanoate terpolymers.
• the copolymers may, for example, have 15 or fewer, preferably 10 or fewer, more preferably 6 or fewer, most preferably 2 to 5, methyl terminating side branches per 100 methylene groups, as measured by nuclear magnetic resonance spectroscopy, other than methyl groups on a comonomer ester and other than terminal methyl groups.
• the copolymers may have a polydispersity of 1 to 6, preferably 2 to 4; polydispersity being the ratio of weight average molecular weight to number average molecular weight both as measured by Gel Permeation Chromatography using polystyrene standards.
• the growth arrestor may also be a copolymer of ethylene and 1-alkenes having a carbon chain length of 3 to 8; or a hydrogenated polybutadiene.
• the growth arrestor is preferably present in the fuel oil in an amount ranging from 5 to 5,000 ppm, preferably from 10 to 1,000 ppm and most preferably from 20 to 500 ppm.
• the polar nitrogen compound is also known as a wax anti-settling additive ('WASA').
• Polar nitrogen compounds include an oil-soluble polar nitrogen compound carrying one or more, preferably two or more, hydrocarbyl substituted amino or imino substituents, the hydrocarbyl group being monovalent and containing 8 to 40 carbon atoms, and the substituents optionally being in the form of a cation derived therefrom.
• the oil-soluble polar nitrogen compound is either ionic or non-ionic and is capable of acting as a wax crystal growth modifier in fuel oils.
• the hydrocarbyl group is linear or slightly linear, i.e. it may have one short length (1-4 carbon atoms) hydrocarbyl branch. When the substituent is amino, it may carry more than one said hydrocarbyl group, which may be the same or different.
• hydrocarbyl refers to a group having a carbon atom directly attached to the rest of the molecule and having a hydrocarbon or predominantly hydrocarbon character.
• hydrocarbon groups including aliphatic (e.g. alkyl or alkenyl), alicyclic (e.g. cycloalkyl or cycloalkenyl), aromatic, alicyclic-substituted aromatic, aromatic-substituted aliphatic and alicyclic groups.
• Aliphatic groups are advantageously saturated. These groups may contain non-hydrocarbon substituents provided their presence does not alter the predominantly hydrocarbon character of the group. Examples include keto, halo, hydroxy, nitro, cyano, alkoxy and acyl. If the hydrocarbyl group is substituted, a single (mono) substituent is preferred.
• substituted hydrocarbyl groups examples include 2-hydroxyethyl, 3-hydroxypropyl, 4-hydroxybutyl, 2-ketopropyl, ethoxyethyl, and propoxypropyl.
• the groups may also or alternatively contain atoms other than carbon in a chain or ring otherwise composed of carbon atoms. Suitable hetero atoms include, for example, nitrogen, sulphur, and, preferably, oxygen.
• the or each amino or imino substituent is bonded to a moiety via an intermediate linking group such as -CO-, -CO 2 (-) , -SO 3 (-) or hydrocarbylene.
• an intermediate linking group such as -CO-, -CO 2 (-) , -SO 3 (-) or hydrocarbylene.
• the substituent is part of a cationic group, as in an amine salt group.
• the linking groups for each substituent may be the same or different.
• Suitable amino substituents are long chain C 12 -C 40 , preferably C 12 -C 24 , alkyl primary, secondary, tertiary or quaternary amino substituents.
• the amino substituent is a dialkylamino substituent, which, as indicated above, may be in the form of an amine salt thereof; tertiary and quaternary amines can form only amine salts.
• Said alkyl groups may be the same or different.
• amino substituents include dodecylamino, tetradecylamino, cocoamino, and hydrogenated tallow amino.
• secondary amino substituents include dioctadecylamino and methylbehenylamino. Mixtures of amino substituents may be present such as those derived from naturally occurring amines.
• a preferred amino substituent is the secondary hydrogenated tallow amino substituent, the alkyl groups of which are derived from hydrogenated tallow fat and are typically composed of approximately 4% C 14 , 31% C 16 and 59% C 18 n-alkyl groups by weight.
• Suitable imino substituents are long chain C 12 -C 40 , preferably C 12 -C 24 , alkyl substituents.
• the moiety may be monomeric (cyclic or non-cyclic) or polymeric.
• non-cyclic it may be obtained from a cyclic precursor such as an anhydride or a spirobislactone.
• the cyclic ring system may include homocyclic, heterocyclic, or fused polycyclic assemblies, or a system where two or more such cyclic assemblies are joined to one another and in which the cyclic assemblies may be the same or different. Where there are two or more such cyclic assemblies, the substituents may be on the same or different assemblies, preferably on the same assembly.
• the or each cyclic assembly is aromatic, more preferably a benzene ring.
• the cyclic ring system is a single benzene ring when it is preferred that the substituents are in the ortho or meta positions, which benzene ring may be optionally further substituted.
• the ring atoms in the cyclic assembly or assemblies are preferably carbon atoms but may for example include one or more ring N, S or O atom, in which case or cases the compound is a heterocyclic compound.
• polycyclic assemblies examples include polycyclic aromatics, rings joined "end-on” such as diphenyl, heterocylics or alicyclics.
• an amine salt and/or amide of a mono- or poly-carboxylic acid e.g. having 1 to 4 carboxylic acid groups. It may be made, for example, by reacting at least one molar proportion of a hydrocarbyl substituted amine with a molar proportion of the acid or its anhydride.
• the linking group When an amide is formed, the linking group is -CO-, and when an amine salt is formed, the linking group is -CO 2 (-) .
• the moiety may be cyclic or non-cyclic.
• cyclic moieties are those where the acid is cyclohexane 1,2-dicarboxylic acid; cyclohexane 1,2-dicarboxylic acid; cyclopentane 1,2-dicarboxylic acid; and naphthalene dicarboxylic acid.
• such acids have 5 to 13 carbon atoms in the cyclic moiety.
• Preferred such cyclic acids are benzene dicarboxylic acids such as phthalic acid, isophthalic acid, and terephthalic acid, and benzene tetracarboxylic acids such as pyromelletic acid, phthalic acid being particularly preferred.
• US-A-4,211,534 and EP-A-272,889 describes polar nitrogen compounds containing such moieties.
• non-cyclic moieties are those when the acid is a long chain alkyl or alkylene substituted dicarboxylic acid such as a succinic acid, as described in US-A-4,147,520 for example.
• non-cyclic moieties are those where the acid is a nitrogen-containing acid such as ethylene diamine tetracetic acid and nitrilotriacetic acid.
• B represents an aromatic system
• A represents a hydrocarbyl group
• R 1 and R 2 are the same or are different and each independently is an aliphatic hydrocarbyl group containing 10-40 carbon atoms provided that one of R 1 and R 2 may represent a hydrogen atom
• z is at least 1 and wherein the aromatic system carries at least one substituent group which is an activating group for the ring system or a derivative of an activating group.
• hydrocarbyl in this specification is meant an organic moiety that is composed of hydrogen and carbon, which is bonded to the rest of the molecule by a carbon atom or atoms and which, unless the context states otherwise, may be aliphatic, including alicyclic, aromatic or a combination thereof. It may be substituted or unsubstituted, alkyl, aryl or alkaryl and may optionally contain unsaturation or heteroatoms such as O, N or S, provided that such heteroatoms are insufficient to alter the essentially hydrocarbyl nature of the group. It is preferred that A is an aliphatic hydrocarbyl group and more preferably that A is a methylene group.
• aromatic system is meant to include aromatic homocyclic, heterocyclic or fused polycyclic assemblies, or a system where two or more such cyclic assemblies are joined to one another and in which the cyclic assemblies may be the same or different. Where there are two or more cyclic assemblies and Z is 2 or more the -(A-NR 1 R 2 ) groups present may be in the same or different assemblies. It is preferred that the aromatic system is a ring system based on benzene rings.
• the ring atoms in the aromatic system are preferably carbon atoms but may, for example, include one or more heteroatoms such as N, S, or O in the system in which case the compound is a heterocyclic compound.
• polycyclic assemblies examples include
• activating group is meant any group, other than a substituent aliphatic hydrocarbyl group which activates the aromatic system to substitution reactions such as electrophilic substitution, nucleophilic substitution or to the Mannich reaction.
• the activating group may be a non-substituent group such as functionality that is within the aromatic system as in, for example, heterocyclic compounds such as indole.
• the activating group is located at least within or on each of the rings of the aromatic system which are substituted with an -(A-NR 1 R 2 ) group. It is preferred that the activating group is a group that is on the ring system as opposed to being within the aromatic system.
• the activating group or groups activate the aromatic system to electrophilic substitution or to the Mannich reaction, most preferably to the Mannich reaction. It is preferred that the activating group activates the aromatic system in the ortho or para position relative to itself.
• the preferred activating group is a hydroxyl group.
• the preferred activated aromatic system is a hydroxy aromatic system.
• derivative of an activating group is meant any group that can be produced by the reaction of the activating group. For example, when the activating group is a hydroxyl group one derivative would be an -O-C(O)-CH 3 group produced by reaction of the hydroxyl group with, for example, acetic anhydride.
• activating group or a derivative of an activating group on or in the aromatic system; they may be in or on the same or different rings. There may also be other substituents present that are in or on the aromatic system and are not activating groups or derivatives of activating groups.
• Each aliphatic hydrocarbyl group constituting R 1 and R 2 in the invention may, for example, be an alkyl or alkylene group or a mono or polyalkoxyalkyl group or aliphatic hydrocarbyl group that contains heteroatoms such as O, N or S.
• each aliphatic hydrocarbyl group is a straight chain alkyl group.
• the number of carbon atoms in each aliphatic hydrocarbyl group is preferably 12-24, most preferably 16 to 22.
• the additional substituent of general formula II may also be present in the aromatic system when z is 2 or more. When there is no additional substituent of general formula II present in the ring system it is preferred that z is 2 or more.
• D represents a hydroxyl group or a derivative of a hydroxyl group.
• D is a derivative of a hydroxyl group it is preferably a -O-C(O)-CH 3 group.
• the C 10 -C 40 aliphatic hydrocarbyl groups may be linear or branched chains. It is preferred that the chains are linear.
• the benzene ring may be part of a larger ring system such as a fused polycyclic ring system or may be a heterocyclic ring or an aromatic ring other than benzene.
• R 3 , R 4 , R 7 and R 8 are hydrogen.
• the aliphatic hydrocarbyl groups R 1 and R 2 may be the same or different and are preferably independently C 10 -C 40 alkyl groups. Desirably the alkyl groups are independently C 12 -C 24 alkyl groups and most preferably C 16 -C 22 alkyl groups. When there is more than one R 1 or R 2 group present they may be the same or different aliphatic hydrocarbyl groups. Preferred combinations of alkyl groups are those wherein R 1 /R 2 are either C 16 /C 18 , C 20 /C 22 , C 18 /C 18 or C 22 /C 22 .
• the aliphatic hydrocarbyl groups may also contain hetero atoms such as O, N or S. It is preferred that no hetero atoms are present in the aliphatic hydrocarbyl groups and that the groups are linear or those which have low levels of branching.
• the divalent group Y may be a substituted or unsubstituted aliphatic group such as for example methylene, -C(CH 3 ) 2 -, -CH(Ph)-, a group of formula V or similar groups, or groups such as -C(O)-, S(O)-, S(O) 2 -, -O-, -S-, -C(O)-O- and -C(O)-O-R 11 -O-C(O)- wherein R 11 is a hydrocarbyl group as hereinbefore defined.
• R 11 is a hydrocarbyl group as hereinbefore defined.
• the divalent group Y may also be an aromatic group.
• the divalent group Y may also contain activated cyclic rings which have the substituent group -(A-NR 1 R 2 ) present in the cyclic ring.
• the compounds of general formula III may also be substituted with non-hydrocarbyl groups such as for example NO 2 or CN groups.
• the activating group is preferably a hydroxyl group.
• the hydroxyl-aromatic system is hereinafter referred to as an activated compound.
• the compound is prepared by reacting under Mannich condensation conditions a formaldehyde or an aldehyde and a secondary amine which comprises independently C 10 -C 40 aliphatic hydrocarbyl groups.
• the reactants may be used in equimolar or substantially equimolar proportions.
• the mole ratio of the activated compound to secondary amine may be less than equimolar for example 1:2, 1:3 or 1:4 or more. It is preferred that the mole ratio of activated compound to secondary amine is 1:2 or substantially 1:2 and that there is sufficient formaldehyde present to enable this mole ratio to be achieved in the final product.
• the reaction may be carried out in a solvent for example toluene or without a solvent and at a temperature in the range of 80°C to 120°C.
• the aldehyde may be any aldehyde that reacts with an activated compound and a C 10 -C 40 aliphatic hydrocarbyl secondary amine under Mannich condensation conditions. It is preferred that formaldehyde is used in the method.
• the formaldehyde may be employed in any of its conventional forms; it may be used in the form of an aqueous solution such as formalin, as paraformaldehyde or as trioxane.
• Suitable hydroxyaromatic compounds include for example: substituted phenols such as 2-, 3-, or 4-hydroxybenzophenone, 2-, 3-, or 4-hydroxybenzoic acid and 1 or 2-naphthol; dihydroxy compounds such as resorcinol, catechol, hydroquinone, 2,2'- biphenol, 4,4'biphenol, fluorescein, 2,2-bis(p-hydroxy phenyl)propane, dihydroxybenzophenones, 4,4'-thiodiphenol, or dihydroxy benzoic acids such as 2,4-, or 3,5-dihydroxybenzoic acid; or trisphenolic compounds such as 1,1,1-tris-(4-hydroxy phenyl)ethane.
• substituted phenols such as 2-, 3-, or 4-hydroxybenzophenone, 2-, 3-, or 4-hydroxybenzoic acid and 1 or 2-naphthol
• dihydroxy compounds such as resorcinol, catechol, hydroquinone, 2,2'- biphenol, 4,4'bi
• the hydroxy aromatic compounds may be substituted, for example, with one or more of the following substituents: no-hydrocarbyl groups such as -NO 2 or CN; or hydrocarbyl groups such as -CHO, -COOR, -COR, -COOR; or aliphatic hydrocarbyl groups such as alkyl groups.
• the substituent or substituents may be in the ortho, para or meta or any combination of these positions in relation to the hydroxyl group or groups.
• the hydroxyaromatic compound is a substituted phenol it is preferred that the substitution is in the ortho or para position.
• Phenols which have certain para substituents have been found to produce bisdialkylaminomethyl Mannich reaction products, derived from secondary amines with aliphatic hydrocarbyl groups of C 10 to C 40 , under milder reaction conditions and with greater ease than when using unsubstituted phenol. In some cases substitution in the ortho position also allows easier reaction under milder conditions, though some such substituents are not beneficial, such as those substituents which are able to hydrogen bond with the hydroxyl group.
• a suitable ortho substituent is a cyano group. It will be understood that with dihydroxy compounds such as catechol where two or more hydroxy groups are present in the same ring, that any one substituent may be ortho with respect to one of these hydroxy groups and meta in relation to the other.
• the amine may be any secondary amine that contains linear and/or branched chain aliphatic hydrocarbyl groups of C 10 -C 40 , and preferably C 12 -C 24 and most preferably C 16 -C 22 .
• Preferred secondary amines are linear or those that have low levels of branching.
• suitable secondary amines include the simple secondary amines such as N,N-dihexadecylamine, N,N-dioctadecylamine, N,N-dieicosylamine, N,N-didocosylamine, N,N-dicetylamine, N,N-distearylamine, N,N-diarachidylamine, N,N-dibehenylamine, N,N-di hydrogenated tallow amine and mixed secondary amines which comprise a mixture of any two of the following functionality: hexadecyl, octadecyl, eicosyl, docosyl, cetyl, stearyl, arachidyl, behenyl or hydrogenated tallow or that derived from the fatty acids of coconut oil.
• Additional substituents of general formula II may be formed on the aromatic system during the above reaction by reacting activated compounds which have a carboxylic acid group present, with the corresponding amount of amine to take part in the above reaction and also to neutralise the carboxylic acid groups present.
• the carboxylic acid groups may be neutralised after the reaction by adding the required amount of amine, which may be the same or a different amine to that used in the reaction, to neutralise the carboxylic acid groups.
• polymers such as described in GB-A-2,121,807, FR-A-2,592,387 and DE-A-3,941,561; and also esters of telomer acid and alkanoloamines such as described in US-A-4,639,256; and the reaction product of an amine containing a branched carboxylic acid ester, an epoxide and a mono-carboxylic acid polyester such as described in US-A-4,631,071.
• EP 0,283,292 describes amide containing polymers and EP 0,343,981 describes amine-salt containing polymers.
• polar nitrogen compounds may contain other functionality such as ester functionality.
• the polar nitrogen compound is preferably present in the fuel oil in an amount ranging from 5 to 5,000 ppm, preferably from 10 to 1,000 ppm and most preferably from 20 to 500 ppm.
• the nucleator is preferably a polyoxyalkylene compound.
• examples include polyoxyalkylene esters, ethers, ester/ethers and mixtures thereof, particularly those containing at least one, preferably at least two, C 10 to C 30 linear alkyl groups and one or more polyoxyalkylene glycol group of molecular weight up to 5,000, preferably 200 to 5,000, the alkylene group in said polyoxyalkylene glycol containing from 1 to 4 carbon atoms, as described in EP-A-61 895 and in U.S. Patent No. 4,491,455.
• Preferred glycols are substantially linear polyethylene glycols (PEG) and polypropylene glycols (PPG) having a molecular weight of about 100 to 5,000, preferably about 200 to 2,000.
• Esters are also preferred and fatty acids containing from 10 to 30 carbon atoms are useful for reacting with the glycols to form the ester additives, it being preferred to use C 18 to C 24 fatty acid, especially stearic and behenic acids.
• the esters may also be prepared by esterifying polyethoxylated fatty acids, polyethoxylated alcohols or polyols.
• Polyoxyalkylene diesters, diethers, ether/esters and mixtures thereof are suitable as additives, when minor amounts of monoethers and monoesters (which are often formed in the manufacturing process) may also be present.
• stearic or behenic diesters of polyethylene glycol, polypropylene glycol or polyethylene/polypropylene glycol mixtures are preferred.
• Examples of other compounds in this general category are those described in Japanese Patent Publication Nos. 2-51477 and 3-34790, and EP-A-117,108 and EP-A-326,356, and cyclic esterified ethoxylates such as described EP-A-356,256.
• esters are those obtainable by the reaction of:
• an alkoxylated aliphatic monohydric alcohol in which the alcohol has greater than 18 carbon atoms prior to alkoxylation and in which the degree of alkoxylation is 5 to 30 moles of alkylene oxide per mole of alcohol.
• the ester may be formed from a single acid reactant (i) and single alcohol reactant (ii), or from mixtures of acids (i) or alcohols (ii) or both. In the latter cases, a mixture of ester products will be formed which may be used without separation if desired, or separated to give discrete products before use.
• These materials may also be prepared by alkoxylation of a fatty acid ester of a polyol (e.g. ethoxylated sorbitan tristearate having the trade name TWEEN 65, which is available from Uniqema, owned by ICI).
• a polyol e.g. ethoxylated sorbitan tristearate having the trade name TWEEN 65, which is available from Uniqema, owned by ICI.
• the degree of alkoxylation of the aliphatic monohydric alcohol is preferably 10 to 25 moles of alkylene oxide per mole of alcohol, more preferably 15 to 25 moles.
• the alkoxylation is preferably ethoxylation, although propoxylation or butoxylation can also be used successfully.
• Mixed alkoxylation for example a mixture of ethylene and propylene oxide units, may also be used.
• the acid reactant (i) preferably has 18 to 30 carbon atoms, more preferably 16 to 24 carbon atoms such as 18 or 22 carbon atoms.
• the acid is preferably a saturated aliphatic acid, more preferably an alkanoic acid.
• Alkanoic acids of 16 to 30 carbon atoms are particularly useful.
• n-Alkanoic acids are preferred.
• Such acids include behenic acid and arachidic acid, with behenic acid being preferred.
• the alcohol reactant (ii) is preferably derived from an aliphatic monohydric alcohol having no more than 28 carbon atoms, and more preferably no more than 26 (or better, 24) carbon atoms, prior to alkoxylation.
• the range of 18 to 22 is particularly advantageous for obtaining good wax crystal modification.
• the aliphatic alcohol is preferably a saturated aliphatic alcohol, especially an alkanol (i.e. alkyl alcohol).
• Alkanols having 16 to 28 carbon atoms, and particularly 18 to 26, such as 18 to 22 carbon atoms are preferred.
• n-Alkanols are most preferred, particularly those having 16 to 24 carbon atoms, and preferably 18 to 22 carbon atoms.
• the alcohol reactant (ii) is a mixture of alcohols
• this mixture may comprise a single aliphatic alcohol alkoxylated to varying degrees, or a mixture of aliphatic alcohols alkoxylated to either the same or varying degrees.
• the average carbon number prior to alkoxylation should be above 16 and preferably within the preferred ranges recited above.
• the individual alcohols in the mixture should not differ by more than 4 carbon atoms.
• esterification can be conducted by normal techniques known in the art.
• one mole equivalent of the alkoxylated alcohol is esterified by one mole equivalent of acid by azeotroping in toluene at 110-120°C in the presence of 1 weight percent of p-toluene sulphonic acid catalyst until esterification is complete, as judged by Infra-Red Spectroscopy and/or reduction of the hydroxyl and acid numbers.
• the alkoxylation of the aliphatic alcohol is also conducted by well-known techniques.
• a suitable alcohol is (where necessary) melted at about 70°C and 1 wt % of potassium ethoxide in ethanol added, the mixture thereafter being stirred and heated to 100°C under a nitrogen sparge until ethanol ceases to be distilled off, the mixture subsequently being heated to 150°C to complete formation of the potassium salt.
• the reactor is then pressurised with alkylene oxide until the mass increases by the desired weight of alkylene oxide (calculated from the desired degree of alkoxylation).
• the product is finally cooled to 90°C and the potassium neutralised (e.g. by adding an equivalent of lactic acid).
• the acid (i) is an alkanoic acid and the alkoxylated alcohol (ii) is formed from one mole of a C 18 to C 22 alkanol and 15 to 25 moles of ethylene oxide have been found to be particularly effective as low temperature flow and filterability improvers, giving excellent wax crystal modification.
• the acid (i) is preferably an n-alkanoic acid having 18 to 22 carbon atoms and the alkanol preferably has 16 to 22, more preferably 18 to 22 carbon atoms.
• Such a combination of structural features has been found to be particularly advantageous in providing improved wax crystal modification.
• the nucleator is preferably present in the fuel oil in an amount ranging from 5 to 1,000 ppm, preferably from 10 to 500 ppm and most preferably from 10 to 200 ppm.
• Comb polymers are discussed in "Comb-Like Polymers. Structure and Properties", N. A. Platé and V. P. Shibaev, J. Poly. Sci. Macromolecular Revs., 8, p 117 to 253 (1974).
• comb polymers consist of molecules in which long chain branches such as hydrocarbyl branches, optionally interrupted with one or more oxygen atoms and/or carbonyl groups, having from 6 to 30 such as 10 to 30, carbon atoms, are pendant from a polymer backbone, said branches being bonded directly or indirectly to the backbone.
• long chain branches such as hydrocarbyl branches, optionally interrupted with one or more oxygen atoms and/or carbonyl groups, having from 6 to 30 such as 10 to 30, carbon atoms
• indirect bonding include bonding via interposed atoms or groups, which bonding can include covalent and/or electrovalent bonding such as in a salt.
• comb polymers are distinguished by having a minimum molar proportion of units containing such long chain branches.
• the comb polymer is a homopolymer or a copolymer having at least 25 and preferably at least 40, more preferably at least 50, molar per cent of units having side chains containing at least 6, such as at least 8, and preferably at least 10, atoms, selected from, for example, carbon, nitrogen and oxygen, in a linear chain or a chain containing a small amount of branching such as a single methyl branch.
• the comb polymer may contain units derived from other monomers if desired or required, examples being CO, vinyl acetate and ethylene. It is within the scope of the invention to include two or more different comb copolymers.
• the comb polymers may, for example, be copolymers of maleic anhydride or fumaric acid and another ethylenically unsaturated monomer, e.g. an ⁇ -olefin or an unsaturated ester, for example, vinyl acetate as described in EP-A-214,786. It is preferred but not essential that equimolar amounts of the comonomers be used although molar proportions in the range of 2 to 1 and 1 to 2 are suitable. Examples of olefins that may be copolymerized with e.g.
• maleic anhydride include 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and styrene.
• Other examples of comb polymers include methacrylates and acrylates.
• the copolymer may be esterified by any suitable technique and although preferred it is not essential that the maleic anhydride or fumaric acid be at least 50% esterified.
• alcohols that may be used include n-decan-1-ol, n-dodecan-1-ol, n-tetradecan-1-ol, n-hexadecan-1-ol, and n-octadecan-1-ol.
• the alcohols may also include up to one methyl branch per chain, for example, 1-methylpentadecan-1-ol, 2-methyltridecan-1-ol as described in EP-A-213,879.
• the alcohol may be a mixture of normal and single methyl branched alcohols.
• the number of carbon atoms in the alkyl group is taken to be the average number of carbon atoms in the alkyl groups of the alcohol mixture; if alcohols that contain a branch at the 1 or 2 positions are used, the number of carbon atoms in the alkyl group is taken to be the number in the straight chain backbone segment of the alkyl group of the alcohol.
• the copolymer may also be reacted with a primary and/or secondary amine, for example, a mono- or di-hydrogenated tallow amine.
• the comb polymers may especially be fumarate or itaconate polymers and copolymers such as for example those described in European Patent Applications 153 176, 153 177, 156 577 and 225 688, and WO 91/16407.
• Particularly preferred fumarate comb polymers are copolymers of alkyl fumarates and vinyl acetate, in which the alkyl groups have from 12 to 20 carbon atoms, more especially polymers in which the alkyl groups have 14 carbon atoms or in which the alkyl groups are a mixture of C 12 /C 14 alkyl groups, made, for example, by solution copolymerizing an equimolar mixture of fumaric acid and vinyl acetate and reacting the resulting copolymer with the alcohol or mixture of alcohols, which are preferably straight chain alcohols.
• the mixture it is advantageously a 1:1 by weight mixture of normal C 12 and C 14 alcohols.
• mixtures of the C 12 ester with the mixed C 12 /C 14 ester may advantageously be used.
• the ratio of C 12 to C 12 /C 14 is advantageously in the range of from 1:1 to 4:1, preferably 2:1 to 7:2, and most preferably about 3:1, by weight.
• the particularly preferred fumarate comb polymers may, for example, have a number average molecular weight in the range of 1,000 to 100,000, preferably 1,000 to 50,000, as measured by Vapour Phase Osmometry (VPO).
• comb polymers are the polymers and copolymers of ⁇ -olefins and esterified copolymers of styrene and maleic anhydride, and esterified copolymers of styrene and fumaric acid as described in EP-A-282,342; mixtures of two or more comb polymers may be used in accordance with the invention and, as indicated above, such use may be advantageous.
• comb polymers are hydrocarbon polymers such as copolymers of ethylene and at least one ⁇ -olefin, preferably the ⁇ -olefin having at most 20 carbon atoms, examples being n-octene-1, iso octene-1, n-decene-1 and n-dodecene-1, n-tetradecene-1 and n-hexadecene-1 (for example, as described in WO 93/19106).
• the number average molecular weight measured by Gel Permeation Chromatography against polystyrene standards of such a copolymer is, for example, up to 30,000 or up to 40,000.
• the hydrocarbon copolymers may be prepared by methods known in the art, for example using a Ziegler type catalyst. Such hydrocarbon polymers may for example have an isotacticity of 75% or greater.
• the comb polymer may be present in the fuel oil in an amount ranging from 5 to 5,000 ppm, preferably from 10 to 1,000 ppm and most preferably from 20 to 500 ppm.
• Suitable alkyl phenol formaldehyde condensates are disclosed in EP 0 311 452 and EP 0 851 776.
• the alkyl phenol formaldehyde condensate may be obtainable by the condensation reaction between:
• the alkyl phenol formaldehyde condensate may be present in the fuel oil in an amount ranging from 5 to 5,000 ppm, preferably 10 to 1,000 ppm and most preferably from 20 to 500 ppm.
• the fuel additive may comprise one or more other conventional co-additives known in the art, such as: detergents, antioxidants, corrosion inhibitors, de-hazers, demulsifiers, metal deactivators, antifoaming agents, cetane improvers, co-solvents, package compatibilizers, lubricity additives and antistatic additives.
• detergents such as: detergents, antioxidants, corrosion inhibitors, de-hazers, demulsifiers, metal deactivators, antifoaming agents, cetane improvers, co-solvents, package compatibilizers, lubricity additives and antistatic additives.
• the fuel oil may be a hydrocarbon fuel oil such as a petroleum-based fuel oil, for example kerosene or distillate fuel oil, or a middle distillate fuel oil, i.e. a fuel oil obtained in refining crude oil as the fraction between the lighter kerosene and jet fuels fraction and the heavier fuel oil fraction.
• a hydrocarbon fuel oil such as a petroleum-based fuel oil, for example kerosene or distillate fuel oil, or a middle distillate fuel oil, i.e. a fuel oil obtained in refining crude oil as the fraction between the lighter kerosene and jet fuels fraction and the heavier fuel oil fraction.
• Such distillate fuel oils generally boil within the range of about 100°C to about 500°C, such as 150°C to about 400°C, for example, those having a relatively high final boiling point of above 360°C.
• ASTM-D86 Middle distillates contain a spread of hydrocarbons boiling over a temperature range. They are also characterised by pour point, cloud point and CFPP,
• the fuel oil can comprise atmospheric distillate or vacuum distillate, or cracked gas oil or a blend in any proportion of straight run and thermally and/or catalytically cracked distillates.
• the most common petroleum distillate fuels are kerosene, jet fuels, diesel fuels, heating oils and heavy fuel oils, diesel fuels and heating oils being preferred.
• the diesel fuel or heating oil may be a straight atmospheric distillate, or may contain minor amounts, e.g. up to 35 wt %, of vacuum gas oil or cracked gas oils or both.
• Heating oils may be made of a blend of virgin distillate, e.g. gas oil, naphtha, etc. and cracked distillates, e.g. catalytic cycle stock.
• a representative specification for a diesel fuel includes a minimum flash point of 38°C and a 90% distillation point between 282 and 380°C (see ASTM Designations D-396 and D-975).
• the fuel oil may be an animal or vegetable oil (i.e. a 'biofuel'), or a mineral oil as described above in combination with one or more animal or vegetable oils.
• oils examples include rapeseed oil, coriander oil, soyabean oil, cottonseed oil, sunflower oil, castor oil, olive oil, peanut oil, maize oil, almond oil, palm kernel oil, coconut oil, mustard seed oil, beef tallow and fish oils.
• Rapeseed oil which is a mixture of fatty acids esterified with glycerol, is preferred as it is available in large quantities and can be obtained in a simple way by pressing from rapeseed.
• esters such as methyl esters, of fatty acids of the vegetable or animal oils.
• esters can be made by transesterification.
• lower alkyl esters of fatty acids consideration may be given to the following, for example, as commercial mixtures: the ethyl, propyl, butyl and especially methyl esters of fatty acids with 12 to 22 carbon atoms, for example, of lauric acid, palmitic acid, stearic acid, oleic acid, ricinoleic acid and linoleic acid.
• the fuel additive is particularly effective as a cold flow improver in fuel oils, preferably diesel fuel oils, having a cloud point of less than or equal to -15°C, preferably less than or equal to -20°C, and even more preferably less than or equal to -25°C.
• the fuel additive is also particularly effective in fuel oils having a final boiling point of less than 360°C.
• the concentration of the fuel additive in the fuel oil may, for example, be in the range of 1 to 10,000 ppm of fuel additive (active ingredient) by weight per weight of fuel oil, for example, 10 to 5,000 ppm, such as 25 to 2,500 ppm (active ingredient) by weight per weight of fuel oil, preferably 50 to 1,500 ppm, more preferably 200 to 1,200 ppm.
• the fuel additive concentrate comprises the fuel additive defined above in admixture with a compatible solvent.
• the fuel additive composition may take the form of a concentrate.
• Concentrates comprising the fuel additive in admixture with a carrier liquid (e.g. as a solution or a dispersion) are convenient as a means for incorporating the additive into bulk oil such as distillate fuel, which incorporation may be done by methods known in the art.
• the concentrates may also contain other additives as required and preferably contain from 3 to 90 wt %, more preferably 10 to 80 wt %, most preferably 20 to 75 wt % of the additives preferably in solution in oil.
• carrier liquids are organic solvents including hydrocarbon solvents, for example petroleum fractions such as naphtha, kerosene, diesel and heater oil; aromatic hydrocarbons such as aromatic fractions, e.g.
• the carrier liquid must, of course, be selected having regard to its compatibility with the fuel additive and with the fuel oil.
• the fuel additives of the invention may be incorporated into bulk oil by other methods such as those known in the art. If co-additives are required, they may be incorporated into the bulk oil at the same time as the additives of the invention or at a different time.
• the DSC method measures the amount of heat (i.e. heat flow) needed to maintain a sample at the same temperature as a reference sample (i.e. an empty container) that is similarly cooled and heated.
• the DSC test method involves heating a sample of wax (3-15mg) in a small, sealed, aluminium container in a differential scanning calorimeter to a temperature above its melting point. The wax is then cooled at 5°C/min to a temperature well below its melting point. Finally the wax sample is then heated again at 5°C/min back to a temperature above its melting point.
• a plot of temperature versus heat flow is prepared. Any phase changes, such as melting or freezing points, can be readily identified as more rapid changes in heat flow. Some waxes, depending on their composition, do not have sharp melting points so the end of melting can be difficult to pinpoint. In such cases, it is useful to draw a tangent from the steep part of the curve and to mark the point where it crosses the extended baseline, and denote this as the melting point.
• Blend B comprises 75% of blend A and 25% of an aromatic solvent (Solvesso 150).
• Wax Blend B Pour Point (°C) Appearance of Blend B at test temperature after 1 week ID Melting Point (°C) by DSC Refractive Index at 70°C 20°C 40°C 50°C A1 23 1.4699 9 Hazy fluid clear fluid, ⁇ 5% settled clear fluid A2 22 1.4714 9 Hazy fluid clear fluid clear fluid B1 34 1.4611 15 clear fluid clear fluid clear fluid C 38 1.4472 30 gel clear fluid clear fluid D 77 1.4639 >50 gel gel gel gel E 50 1.4546 38 gel gel fluid F 53 1.4518 42 gel gel fluid, 40% settled G 55 1.4628 42 gel semi-gel clear fluid H 63 1.4698 >40 gel semi-gel clear fluid 58 1.4354 45 gel gel fluid J 36 1.4403 15 50% settled clear fluid clear fluid K 37 1.4454 24 gel clear fluid, 10% settled clear fluid
• waxes that have low melting points give additive blends that have low pour points and are fluid at ambient temperature.
• Waxes having melting points above 36°C produce additive blends that are gelled at ambient temperature.
• Component Code Polar nitrogen compound the product of the reaction of 2 moles dihydrogenated tallow amine with 1 mole phthalic anhydride
• WASA Growth arrestor Ethylene-Vinyl Acetate copolymer, having an Mn of 3,500 and containing 16 mole% vinyl acetate
• EVA Test wax A1 - microfiltrate
• Wax Ethoxylated Sorbitan Tristearate Tween 65 Alkyl Phenol Formaldehyde Condensate APFC
• Nucleators PEG 400 Distearate PEGS PEG 400 Dibehenate PEGB
• Additive Blend A containing Wax A1 (the microfiltrate), was also tested in other fuels and compared to existing, commercial LTFT additives. The results are shown in Table 7. Fuel Description Additive Treat Rate (ppm ai) Lowest LTFT Pass (°C) Comments Canada 1 None 0 -31 Canada 1 Blend A using wax A1 700 -35 Canada 1 Blend A using Wax A1 875 -38 Additive of the invention at 875 ppm enables half of the kerosene in Canada 2 to be diverted to other uses Canada 1 R541 800 -32 Other, commercial LTFT additives are not effective in this type of fuel Canada 1 R533 900 -32 Canada 2 None 0 -37 Shows that fuel Canada 1 requires an equal volume of kerosene for a -37°C LTFT, without additive Canada 3 None 0 -31 Canada 3 Blend A using wax A1 700 -36 Canada 3 Blend A using wax A1 860 -37 Canada 3 R541 1350 Fail -36
• R541 is a blend of EVA (a combination of EVA nucleator and EVA arrestor) with the WASA (see Table 6).
• R533 is a blend of EVA, a hydrogenated polybutadiene MDFI and WASA (see Table 6).
• R541 and R533 contain neither an ethoxylate di-ester nor a wax.
• Canada 2 is a blend of Canada 1 and kerosene in a ratio of 46:54. Canada 3 is from a different refinery than Canada 1.

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• 2002
  • 2002-11-05 EP EP02257660A patent/EP1314771A3/de not_active Withdrawn

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