CN106133120A - 用于燃料和润滑油的腐蚀抑制剂 - Google Patents

用于燃料和润滑油的腐蚀抑制剂 Download PDF

Info

Publication number
CN106133120A
CN106133120A CN201580017192.XA CN201580017192A CN106133120A CN 106133120 A CN106133120 A CN 106133120A CN 201580017192 A CN201580017192 A CN 201580017192A CN 106133120 A CN106133120 A CN 106133120A
Authority
CN
China
Prior art keywords
polymer
fuel
acid
additive
purposes
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201580017192.XA
Other languages
English (en)
Other versions
CN106133120B (zh
Inventor
J·梅茨杰
M·佩雷托钦
A·弗洛雷斯-菲格罗亚
M·汉施
L·沃克尔
I·加西亚卡斯特罗
K·穆尔巴赫
H·波恩科
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from PCT/EP2014/076622 external-priority patent/WO2015113681A1/de
Application filed by BASF SE filed Critical BASF SE
Publication of CN106133120A publication Critical patent/CN106133120A/zh
Application granted granted Critical
Publication of CN106133120B publication Critical patent/CN106133120B/zh
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS 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
    • C10L10/00Use of additives to fuels or fires for particular purposes
    • C10L10/04Use of additives to fuels or fires for particular purposes for minimising corrosion or incrustation
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/14Monomers containing five or more carbon atoms
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00Copolymers 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 a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/04Anhydrides, e.g. cyclic anhydrides
    • C08F222/06Maleic anhydride
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS 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
    • C10L1/00Liquid carbonaceous fuels
    • C10L1/10Liquid carbonaceous fuels containing additives
    • C10L1/14Organic compounds
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS 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
    • C10L1/00Liquid carbonaceous fuels
    • C10L1/10Liquid carbonaceous fuels containing additives
    • C10L1/14Organic compounds
    • C10L1/146Macromolecular compounds according to different macromolecular groups, mixtures thereof
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS 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
    • C10L1/00Liquid carbonaceous fuels
    • C10L1/10Liquid carbonaceous fuels containing additives
    • C10L1/14Organic compounds
    • C10L1/16Hydrocarbons
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS 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
    • C10L1/00Liquid carbonaceous fuels
    • C10L1/10Liquid carbonaceous fuels containing additives
    • C10L1/14Organic compounds
    • C10L1/16Hydrocarbons
    • C10L1/1625Hydrocarbons macromolecular compounds
    • C10L1/1633Hydrocarbons macromolecular compounds homo- or copolymers obtained by reactions only involving carbon-to carbon unsaturated bonds
    • C10L1/1641Hydrocarbons macromolecular compounds homo- or copolymers obtained by reactions only involving carbon-to carbon unsaturated bonds from compounds containing aliphatic monomers
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS 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
    • C10L1/00Liquid carbonaceous fuels
    • C10L1/10Liquid carbonaceous fuels containing additives
    • C10L1/14Organic compounds
    • C10L1/18Organic compounds containing oxygen
    • C10L1/188Carboxylic acids; metal salts thereof
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS 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
    • C10L1/00Liquid carbonaceous fuels
    • C10L1/10Liquid carbonaceous fuels containing additives
    • C10L1/14Organic compounds
    • C10L1/18Organic compounds containing oxygen
    • C10L1/188Carboxylic acids; metal salts thereof
    • C10L1/1881Carboxylic acids; metal salts thereof carboxylic group attached to an aliphatic carbon atom
    • C10L1/1883Carboxylic acids; metal salts thereof carboxylic group attached to an aliphatic carbon atom polycarboxylic acid
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS 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
    • C10L1/00Liquid carbonaceous fuels
    • C10L1/10Liquid carbonaceous fuels containing additives
    • C10L1/14Organic compounds
    • C10L1/18Organic compounds containing oxygen
    • C10L1/192Macromolecular compounds
    • C10L1/195Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C10L1/196Macromolecular 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
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS 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
    • C10L1/00Liquid carbonaceous fuels
    • C10L1/10Liquid carbonaceous fuels containing additives
    • C10L1/14Organic compounds
    • C10L1/18Organic compounds containing oxygen
    • C10L1/192Macromolecular compounds
    • C10L1/195Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C10L1/196Macromolecular 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
    • C10L1/1963Macromolecular 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
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS 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
    • C10L1/00Liquid carbonaceous fuels
    • C10L1/10Liquid carbonaceous fuels containing additives
    • C10L1/14Organic compounds
    • C10L1/18Organic compounds containing oxygen
    • C10L1/192Macromolecular compounds
    • C10L1/195Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C10L1/196Macromolecular 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
    • C10L1/1966Macromolecular 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 poly-carboxylic
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS 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
    • C10L1/00Liquid carbonaceous fuels
    • C10L1/10Liquid carbonaceous fuels containing additives
    • C10L1/14Organic compounds
    • C10L1/18Organic compounds containing oxygen
    • C10L1/192Macromolecular compounds
    • C10L1/195Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C10L1/197Macromolecular 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
    • C10L1/1973Macromolecular 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
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS 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
    • C10L1/00Liquid carbonaceous fuels
    • C10L1/10Liquid carbonaceous fuels containing additives
    • C10L1/14Organic compounds
    • C10L1/18Organic compounds containing oxygen
    • C10L1/192Macromolecular compounds
    • C10L1/195Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C10L1/197Macromolecular 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
    • C10L1/1976Macromolecular 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 poly-carboxylic
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS 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
    • C10L10/00Use of additives to fuels or fires for particular purposes
    • C10L10/06Use of additives to fuels or fires for particular purposes for facilitating soot removal
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS 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
    • C10L10/00Use of additives to fuels or fires for particular purposes
    • C10L10/18Use of additives to fuels or fires for particular purposes use of detergents or dispersants for purposes not provided for in groups C10L10/02 - C10L10/16
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M129/00Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
    • C10M129/02Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
    • C10M129/26Carboxylic acids; Salts thereof
    • C10M129/28Carboxylic acids; Salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M129/30Carboxylic acids; Salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having 7 or less carbon atoms
    • C10M129/34Carboxylic acids; Salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having 7 or less carbon atoms polycarboxylic
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M129/00Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
    • C10M129/02Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
    • C10M129/68Esters
    • C10M129/72Esters of polycarboxylic acids
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M129/00Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
    • C10M129/86Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of 30 or more atoms
    • C10M129/92Carboxylic acids
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M145/00Lubricating compositions characterised by the additive being a macromolecular compound containing oxygen
    • C10M145/02Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M145/10Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate
    • C10M145/12Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate monocarboxylic
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M145/00Lubricating compositions characterised by the additive being a macromolecular compound containing oxygen
    • C10M145/02Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M145/10Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate
    • C10M145/16Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate polycarboxylic
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M159/00Lubricating compositions characterised by the additive being of unknown or incompletely defined constitution
    • C10M159/005Macromolecular compounds, e.g. macromolecular compounds composed of alternatively specified monomers not covered by the same main group
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M171/00Lubricating compositions characterised by purely physical criteria, e.g. containing as base-material, thickener or additive, ingredients which are characterised exclusively by their numerically specified physical properties, i.e. containing ingredients which are physically well-defined but for which the chemical nature is either unspecified or only very vaguely indicated
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS 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
    • C10L1/00Liquid carbonaceous fuels
    • C10L1/10Liquid carbonaceous fuels containing additives
    • C10L1/14Organic compounds
    • C10L1/22Organic compounds containing nitrogen
    • C10L1/234Macromolecular compounds
    • C10L1/236Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derivatives thereof
    • C10L1/2362Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derivatives thereof homo- or copolymers derived from unsaturated compounds containing nitrile groups
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS 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
    • C10L1/00Liquid carbonaceous fuels
    • C10L1/10Liquid carbonaceous fuels containing additives
    • C10L1/14Organic compounds
    • C10L1/22Organic compounds containing nitrogen
    • C10L1/234Macromolecular compounds
    • C10L1/236Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derivatives thereof
    • C10L1/2364Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derivatives thereof homo- or copolymers derived from unsaturated compounds containing amide and/or imide groups
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS 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
    • C10L1/00Liquid carbonaceous fuels
    • C10L1/10Liquid carbonaceous fuels containing additives
    • C10L1/14Organic compounds
    • C10L1/22Organic compounds containing nitrogen
    • C10L1/234Macromolecular compounds
    • C10L1/236Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derivatives thereof
    • C10L1/2366Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derivatives thereof homo- or copolymers derived from unsaturated compounds containing amine groups
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS 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
    • C10L1/00Liquid carbonaceous fuels
    • C10L1/10Liquid carbonaceous fuels containing additives
    • C10L1/14Organic compounds
    • C10L1/22Organic compounds containing nitrogen
    • C10L1/234Macromolecular compounds
    • C10L1/236Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derivatives thereof
    • C10L1/2368Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derivatives thereof homo- or copolymers derived from unsaturated compounds containing heterocyclic compounds containing nitrogen in the ring
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS 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
    • C10L2230/00Function and purpose of a components of a fuel or the composition as a whole
    • C10L2230/22Function and purpose of a components of a fuel or the composition as a whole for improving fuel economy or fuel efficiency
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS 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
    • C10L2270/00Specifically adapted fuels
    • C10L2270/02Specifically adapted fuels for internal combustion engines
    • C10L2270/023Specifically adapted fuels for internal combustion engines for gasoline engines
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS 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
    • C10L2270/00Specifically adapted fuels
    • C10L2270/02Specifically adapted fuels for internal combustion engines
    • C10L2270/026Specifically adapted fuels for internal combustion engines for diesel engines, e.g. automobiles, stationary, marine
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2205/00Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/02Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
    • C10M2205/028Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10Carboxylix acids; Neutral salts thereof
    • C10M2207/12Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2207/121Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of seven or less carbon atoms
    • C10M2207/123Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of seven or less carbon atoms polycarboxylic
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2209/00Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/02Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/08Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type
    • C10M2209/084Acrylate; Methacrylate
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2209/00Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/02Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/08Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type
    • C10M2209/086Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type polycarboxylic, e.g. maleic acid
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2217/00Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2217/02Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2217/022Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an amino group
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2217/00Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2217/02Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2217/024Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an amido or imido group
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2217/00Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2217/02Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2217/026Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a nitrile group
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2217/00Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2217/02Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2217/028Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a nitrogen-containing hetero ring
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/04Detergent property or dispersant property
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/12Inhibition of corrosion, e.g. anti-rust agents or anti-corrosives
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/54Fuel economy
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00Specified use or application for which the lubricating composition is intended
    • C10N2040/25Internal-combustion engines
    • C10N2040/252Diesel engines
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00Specified use or application for which the lubricating composition is intended
    • C10N2040/25Internal-combustion engines
    • C10N2040/252Diesel engines
    • C10N2040/253Small diesel engines
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00Specified use or application for which the lubricating composition is intended
    • C10N2040/25Internal-combustion engines
    • C10N2040/255Gasoline engines
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2060/00Chemical after-treatment of the constituents of the lubricating composition

Landscapes

  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Combustion & Propulsion (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Liquid Carbonaceous Fuels (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Solid Fuels And Fuel-Associated Substances (AREA)
  • Lubricants (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)
  • Fuel-Injection Apparatus (AREA)

Abstract

本发明涉及腐蚀抑制剂在燃料和润滑油中的用途。

Description

用于燃料和润滑油的腐蚀抑制剂
本发明涉及腐蚀抑制剂在燃料和润滑油中的新颖用途。
腐蚀抑制剂是燃料和润滑油中的标准添加剂,其通常基于含有酸基团的结构,如二聚体脂肪酸。
这些腐蚀抑制剂的缺点在于其具有沉淀倾向(尤其在钙离子的存在下),这导致其腐蚀抑制作用降低。另外,因该沉淀而形成的沉积物可妨碍发动机、发动机组件或燃料系统部件的工作,尤其是喷射系统,具体而言是喷射泵或喷嘴。
“喷射系统”应理解为意指机动车辆燃料系统自燃料泵向上并包括喷射器出口的部分。“燃料系统”应理解为意指与特定燃料接触的机动车辆的组件,优选自油箱向上并包括喷射器出口的区域。
在本发明的一个实施方案中,本发明的化合物不仅减少喷射系统中的沉积物,而且还减少燃料系统的其余部分中的沉积物,在本说明书中,尤其是燃料过滤器和燃料泵中的沉积物。
因此,所要解决的问题是提供这样的腐蚀抑制剂,其展现出提高的与钙离子的兼容性和在燃料添加剂包(fuel additive packages)中的良好的稳定性,并同时保持其作为腐蚀抑制剂的作用。
所述问题通过根据权利要求所述的用途来解决。
US 3382056教导了使用包含共聚形式的烯烃和琥珀酸及其衍生物的低分子量共聚物作为精制的燃料组合物中的防锈添加剂。
JP 55-085679教导了使用由具有20至60个碳原子的α-烯烃和马来酸酐所形成的摩尔质量Mw为2000至30000的水解打开共聚物作为矿物油或润滑油中的油溶性防锈剂。
US 5080686和EP 299120公开了烷基琥珀酸和烯基琥珀酸及其衍生物以及包含共聚形式的烯烃和琥珀酸及其衍生物的共聚物在含氧燃料系统中用作腐蚀抑制剂。
从这些文献中的任何一篇均不会得出本发明的腐蚀抑制剂具有提高的与钙离子的兼容性。
因此,本发明提供具有以下统计平均数的聚合物作为燃料或润滑油、优选燃料、更优选具有至少0.1重量ppm的碱金属和/或碱土金属和/或锌含量的燃料中的腐蚀抑制剂的用途:
-每个聚合物链至少4个酸基团,
-每个酸基团的碳原子比率为7至35以及
-80mg KOH/g至320mg KOH/g的酸值,通过在0.5摩尔的氢氧化钾乙醇溶液中加热3小时后用0.5摩尔的盐酸水溶液进行图形电位滴定(potentiographic titration)而测定。
本发明的聚合物可为均聚物或共聚物,优选共聚物。
所述聚合物可通过任何所需方法获得,优选通过加聚或缩聚,优选通过加聚。优选地,所述加聚可通过自由基方式或离子方式进行,优选自由基方式。
发现所述聚合物在燃料和润滑油中是特别有利的,特别是在碱金属和/或碱土金属和/或锌的含量为至少0.1重量ppm,更优选至少0.2重量ppm,甚至更优选至少0.3重量ppm且尤其为至少0.5重量ppm的燃料中。
所述聚合物的一个优势在于,在碱金属和/或碱土金属和/或锌存在下、还优选在碱土金属存在下,其也显示其腐蚀抑制作用。燃料中的碱金属和/或碱土金属包含物,例如,是因为例如在燃料泵中与含有碱金属和/或碱土金属的润滑油混合而导致的。此外,碱金属和/或碱土金属可能源自未脱盐或未充分脱盐的燃料添加剂,例如载体油。碱金属和/或碱土金属夹带到燃料中可能造成上述不利情况。锌源的一个实例为抗磨损添加剂。
碱金属特别包括钠和钾,尤其是钠。
碱土金属特别包括镁和钙,尤其是钙。
锌也应该被强调。
特别有利地,即使在钙的存在下,所述聚合物仍然起作用并且不呈现任何沉淀。
碱金属和/或碱土金属和/或锌的所述量各涉及单个金属物种。
聚合物的描述
用于本发明的用途的聚合物是具有以下统计平均数的规则、无规或嵌段共聚物:
-每个聚合物链至少4个酸基团,
-每个酸基团的碳原子比率为7至35以及
-80mg KOH/g至320mg KOH/g的酸值,通过在0.5摩尔的氢氧化钾乙醇溶液中加热3小时后用0.5摩尔的盐酸水溶液进行图形电位滴定而测定。
已发现这种聚合物是在燃料中具有良好溶解度的有效的腐蚀抑制剂。
优选地,在20℃下,本发明的聚合物在甲苯中的溶解度为至少0.5g/100mL,更优选至少1g/100mL,甚至更优选至少2g/100mL,特别为至少3g/100mL且尤其为至少5g/100mL。
在均聚物的情况下,所述聚合物具有多于4个、优选多于5个、更优选多于8个且最优选多于10个的母单体的重复单元,而在共聚物的情况下,具有多于2个的各母单体的重复单元,优选多于3个,更优选多于4个且最优选多于5个。
所述酸基团,例如,为羧基、磺酸基或膦酸基,优选羧基。
在统计平均上,每个聚合物链的酸基团的数目优选为至少5个,更优选每个聚合物链至少6个,甚至更优选至少7个且尤其为至少8个酸基团。
在统计平均上,每个聚合物链的酸基团的数目的上限为优选50个,更优选每个聚合物链40个、甚至更优选30个且尤其为26个酸基团。
除烃单元和酸基团以外,所述聚合物可具有其他官能团,例如含氧官能团,优选碳酸酯基团、醚基或酯基,或含氮官能团,优选脲基、氨基甲酸乙酯基、氨基或酰胺基。
在本说明书中,含氧官能团是指除氧原子外不包含其他杂原子的官能团。
在本说明书中,含氮官能团是指除氮原子和任选的氧原子外不包含其他杂原子的官能团。
优选地,所述聚合物每个聚合物链包含不多于5个、更优选不多于4个、甚至更优选不多于3个、特别地不多于2个且尤其地不多于1个除含氧官能团和含氮官能团以外的官能团。
优选地,所述聚合物每个聚合物链除氨基、脲基、氨基甲酸乙酯基或酰胺基外包含不多于5个、更优选不多于4个、甚至更优选不多于3个、特别地不多于2个且尤其地不多于1个含氮官能团。
在一个特别优选的实施方案中,所述聚合物每个聚合物链包含不多于2个氨基,甚至更优选不多于1个氨基且尤其为零个氨基。
在另一特别优选的实施方案中,所述聚合物每个聚合物链包含不多于10个、甚至更优选不多于8个、特别地不多于6个且尤其地不多于4个脲基、氨基甲酸乙酯基或酰胺基。
优选地,所述聚合物每个聚合物链除碳酸酯基团、醚基或酯基外包含不多于4个、更优选不多于3个、甚至更优选不多于2个、特别地不多于1个且尤其地不包含含氧官能团。
根据本发明,每个聚合物链的碳酸酯基团、醚基和/或酯基的数目,特别是每个聚合物链的酯基的数目不太相关,只要是同时符合所要求的每个酸基团的碳原子的比率。
在一个优选实施方案中,所述聚合物每个聚合物链包含不多于20个、更优选不多于15个、尤其优选不多于10个且特别地不多于5个醚基。
在另一优选实施方案中,所述聚合物每个聚合物链包含不多于50个、更优选不多于40个、尤其优选不多于30个且特别地不多于26个碳酸酯基团或酯基。
在另一同样优选的实施方案中,所述聚合物每个聚合物链包含不多于4个、更优选不多于3个、尤其优选不多于2个、特别地不多于1个且尤其为零个碳酸酯基团和酯基。
聚合物中每个酸基团的碳原子的比率定义为统计平均上的每个聚合物链的碳原子的总数除以每个聚合物链的酸基团的总数。两参数均可由所用的单体和通过凝胶渗透色谱法(用四氢呋喃和作为标准物的聚苯乙烯)确定的分子量,以及由用于聚合的单体来确定。
聚合物中每个酸基团的碳原子的比率的下限优选为至少8、更优选至少9、甚至更优选至少10、特别为至少11且尤其为至少12。
聚合物中每个酸基团的碳原子的比率的上限优选为最高达33、更优选最高达31、甚至更优选最高达29、特别地最高达27且尤其最高达25。
聚合物中每个酸基团的碳原子的特定比率首先导致在燃料中的良好的溶解性,其次有足够可用的用于腐蚀抑制的羧基。
另外,所述聚合物的酸值为80mg KOH/g至320mg KOH/g,优选90mg KOH/g至300mgKOH/g且更优选95mg KOH/g至290mg KOH/g,通过在0.5摩尔的氢氧化钾乙醇溶液中加热3小时后用0.5摩尔的盐酸水溶液进行图形电位滴定而测定。
所述聚合物通常具有0.5kDa至20kDa的重均分子量Mw,优选0.6kDa至15kDa,更优选0.7kDa至7kDa,甚至更优选1kDa至7kDa且特别为1.5kDa至5kDa(通过凝胶渗透色谱法以四氢呋喃和作为标准物的聚苯乙烯测定)。
数均分子量Mn通常为0.5kDa至10kDa,优选0.6kDa至5kDa,更优选0.7kDa至4kDa,甚至更优选0.8kDa至3kDa且尤其为1kDa至2kDa(通过凝胶渗透色谱法以四氢呋喃和作为标准物的聚苯乙烯测定)。
在一个优选实施方案中,所述聚合物包含高比例的邻接的羧酸基团——其通过测量邻接度(adjacency)来确定。为此目的,在两个聚四氟乙烯膜之间在290℃的温度下将聚合物样品加热处理30分钟时间,并在无气泡位点记录FTIR光谱。从获得的谱图中扣除聚四氟乙烯的IR光谱,测定层厚度并确定环状酸酐的含量。
在一个优选实施方案中,邻接度为至少10%,优选至少15%,更优选至少20%,甚至更优选至少25%且尤其至少30%。
用途
本发明的用途涉及抑制铁、钢和/或非铁金属表面的腐蚀。
在所述非铁金属中,优选的是铜及其合金。
更优选地,抑制钢表面的腐蚀。
将所述聚合物加入到具有上述含量的碱金属和/或碱土金属和/或锌的燃料中,通常加入量为1重量ppm至60重量ppm,且优选10重量ppm至40重量ppm。
通常,所述聚合物以燃料添加剂混合物的形式与以下常规的添加剂一起使用:
在柴油燃料的情况下,其主要是常规的清洁剂添加剂、载体油、冷流改进剂、润滑改进剂、除所述聚合物以外的腐蚀抑制剂、破乳剂、去雾剂、消泡剂、十六烷值改进剂、助燃剂、抗氧化剂或稳定剂、抗静电剂、金属茂合物、金属钝化剂、染料和/或溶剂。
因此,本发明还提供具有以下统计平均数的聚合物在下述添加剂包中用于在具有至少0.1ppm的碱金属和/或碱土金属和/或锌含量的柴油燃料中降低腐蚀的用途:
-每个聚合物链至少4个酸基团,
-每个酸基团的碳原子比率为7至35以及
-80mg KOH/g至320mg KOH/g的酸值,通过在0.5摩尔的氢氧化钾乙醇溶液中加热3小时后用0.5摩尔的盐酸水溶液进行图形电位滴定而测定,
所述添加剂包包含至少一种选自清洁剂添加剂、载体油、冷流改进剂、润滑改进剂、除所述聚合物以外的腐蚀抑制剂、破乳剂、去雾剂、消泡剂、十六烷值改进剂、助燃剂、抗氧化剂、稳定剂、抗静电剂、金属茂合物、金属钝化剂、染料和溶剂的添加剂。
在汽油燃料的情况下,其特别为润滑改进剂(摩擦改进剂)、除所述聚合物以外的腐蚀抑制剂、破乳剂、去雾剂、消泡剂、助燃剂、抗氧化剂或稳定剂、抗静电剂、金属茂合物、金属钝化剂、染料和/或溶剂。
因此,本发明还提供具有以下统计平均数的聚合物在下述添加剂包中用于在具有至少0.1ppm的碱金属和/或碱土金属和/或锌含量的汽油燃料中降低腐蚀的用途:
-每个聚合物链至少4个酸基团,
-每个酸基团的碳原子比率为7至35以及
-80mg KOH/g至320mg KOH/g的酸值,通过在0.5摩尔的氢氧化钾乙醇溶液中加热3小时后用0.5摩尔的盐酸水溶液进行图形电位滴定而测定,
所述添加剂包包含至少一种选自润滑改进剂(摩擦改进剂)、除所述聚合物以外的腐蚀抑制剂、破乳剂、去雾剂、消泡剂、助燃剂、抗氧化剂、稳定剂、抗静电剂、金属茂合物、金属钝化剂、染料和溶剂的添加剂。
合适的共添加剂的典型实例列于以下部分:
B1)清洁剂添加剂
常规的清洁剂添加剂优选为两性物质,其具有至少一个85至20 000的数均分子量(Mn)的疏水烃基和至少一个选自以下的极性部分:
(Da)具有最高达6个氮原子的单氨基或多氨基,其中至少一个氮原子具有碱性;
(Db)硝基,任选地与羟基结合;
(Dc)与单氨基或多氨基结合的羟基,其中单氨基或多氨基的至少一个氮原子具有碱性;
(Dd)羧基或者其碱金属或碱土金属盐;
(De)磺酸基或者其碱金属或碱土金属盐;
(Df)以羟基、单氨基或多氨基(其中至少一个氮原子具有碱性)或以氨基甲酸酯基封端的聚氧-C2-至C4-亚烷基部分;
(Dg)羧酸酯基团;
(Dh)衍生自琥珀酸酐并具有羟基和/或氨基和/或酰胺基和/或酰亚胺基的部分;和/或
(Di)通过取代酚与醛和单胺或多胺的曼尼希反应(Mannich reaction)而获得的部分。
上述清洁剂添加剂中的疏水烃基(其确保了在燃料中足够的溶解性)的数均分子量(Mn)为85至20 000,优选113至10 000,更优选300至5000,甚至更优选300至3000,甚至更尤其优选500至2500且尤其为700至2500,特别为800至1500。作为典型的疏水烃基,特别是与极性部分连接的疏水烃基,尤其考虑数均分子量Mn优选在每种情况下为300至5000、更优选300至3000、甚至更优选500至2500、甚至更尤其优选700至2500且尤其为800至1500的聚丙烯基、聚丁烯基和聚异丁烯基。
上组清洁剂添加剂的实例包括以下:
包含单氨基或多氨基(Da)的添加剂优选为基于Mn=300至5000、更优选500至2500且尤其为700至2500的聚丙烯或者高反应性(即主要具有末端双键)或常规(即主要具有内部双键)聚丁烯或聚异丁烯的聚亚烷基单胺或聚亚烷基多胺。此类基于高反应性聚异丁烯的添加剂——其可由可包含最高达20重量%的正丁烯单元的聚异丁烯通过氢甲醛化并用氨水、单胺或多胺(如二甲基氨基丙胺、乙二胺、二亚乙基三胺、三亚乙基四胺或四亚乙基五胺)还原胺化而制备——尤其由EP-A 244 616已知。当将主要具有内部双键(通常在β位和γ位)的聚丁烯或聚异丁烯在添加剂的制备中用作起始材料时,可能的制备路线是通过氯化并随后胺化,或者通过用空气或臭氧将双键氧化成羰基化合物或羧基化合物并随后在还原(氢化)条件下胺化。在本说明书中,用于胺化的胺,例如,可为氨水、单胺或上述多胺。基于聚丙烯的相应的添加剂更加具体记载在WO-A 94/24231中。
包含单氨基(Da)的其他特别的添加剂为平均聚合度P=5至100的聚异丁烯与氮氧化物或氮氧化物和氧的混合物的反应产物的氢化产物,如在WO-A 97/03946中更加具体地记载。
包含单氨基(Da)的其他特别的添加剂为可由聚异丁烯环氧化物通过与胺进行反应并随后使氨基醇脱氢并还原而获得的化合物,如在DE-A 196 20 262中更加具体地记载。
包含硝基(Db)(任选地与羟基结合)的添加剂优选为平均聚合度P=5-100或10-100的聚异丁烯与氮氧化物或氮氧化物和氧的混合物的反应产物,如在WO-A 96/03367和WO-A 96/03479中更加具体地记载。这些反应产物通常为纯硝基聚异丁烯(如α,β-二硝基聚异丁烯)与混合羟基硝基聚异丁烯(如α-硝基-β-羟基聚异丁烯)的混合物。
包含与单氨基或多氨基结合的羟基(Dc)的添加剂尤其为聚异丁烯环氧化物与氨水或单胺或多胺的反应产物,如在EP-A 476 485中更具体地记载,所述聚异丁烯环氧化物可由优选主要具有末端双键且Mn=300至5000的聚异丁烯获得。
包含羧基或其碱金属或碱土金属盐(Dd)的添加剂优选为C2-至C40-烯烃与马来酸酐的总摩尔质量为500至20 000的共聚物,并且其中部分或全部羧基已经转化成碱金属或碱土金属盐且任何剩余羧基均已经与醇或胺反应。此类添加剂更加具体公开在EP-A 307815中。此类添加剂主要用于防止阀座磨损并且,如在WO-A 87/01126中记载的,可有利地与常规的燃料清洁剂(如聚(异)丁烯胺或聚醚胺)结合使用。
包含磺酸基或其碱金属或碱土金属盐(De)的添加剂优选为磺基琥珀酸烷基酯的碱金属或碱土金属盐,如在EP-A 639 632中更加具体地记载。此类添加剂主要用于防止阀座磨损并且可有利地与常规的燃料清洁剂(如聚(异)丁烯胺或聚醚胺)结合使用。
包含聚氧-C2-至C4-亚烷基部分(Df)的添加剂优选为聚醚或聚醚胺,其可通过C2-至C60-烷醇、C6-至C30-烷二醇、单或双-C2-至C30-烷基胺、C1-至C30-烷基环己醇或C1-至C30-烷基酚以每个羟基或氨基(在聚醚胺的情况下)与1mol至30mol的环氧乙烷和/或环氧丙烷和/或环氧丁烷进行反应,随后用氨水、单胺或多胺进行还原胺化而获得。此类产物更加具体记载在EP-A 310 875、EP-A 356 725、EP-A 700 985和US-A 4 877 416中。在聚醚的情况下,此类产物还具有载体油的特性。其典型实例为十三烷醇丁氧基化物或异十三烷醇丁氧基化物、异壬基酚丁氧基化物以及聚异丁烯醇丁氧基化物和丙氧基化物、以及相应的与氨水的反应产物。
包含羧酸酯基团(Dg)的添加剂优选为一元羧酸、二元羧酸或三元羧酸与长链烷醇或多元醇的酯,尤其是在100℃下具有2mm2/s的最小粘度的那些,如在DE-A 38 38 918中所更加具体地记载。所用的一元羧酸、二元羧酸或三元羧酸可以是脂族酸或芳族酸,且特别合适的酯醇或酯多元醇为具有例如6至24个碳原子的长链代表物。所述酯的典型代表物为异辛醇、异壬醇、异癸醇和异十三烷醇的己二酸酯,邻苯二甲酸酯,间苯二甲酸酯,对苯二甲酸酯以及偏苯三酸酯。此类产物也满足载体油的特性。
包含衍生自琥珀酸酐并具有羟基和/或氨基和/或酰胺基和/或特别是酰亚胺基的部分(Dh)的添加剂优选为烷基-或烯基-取代的琥珀酸酐的相应的衍生物,且尤其为聚异丁烯基琥珀酸酐的相应衍生物,所述聚异丁烯基琥珀酸酐可通过使优选Mn=300至5000、更优选300至3000、甚至更优选500至2500、甚至更尤其优选700至2500且尤其是800至1500的常规的或高反应性的聚异丁烯与马来酸酐经由热途径在烯反应中进行反应或通过氯化的聚异丁烯而获得。具有羟基和/或氨基和/或酰胺基和/或酰亚胺基的部分,例如,为羧基、单胺的酸酰胺、除酰胺官能团外还具有游离胺基团的二胺或多胺的酸酰胺、具有酸官能团和酰胺官能团的琥珀酸衍生物、与单胺的羧酰亚胺、除酰亚胺官能团外还具有游离胺基团的与二胺或多胺的羧酰亚胺、或通过二胺或多胺与两个琥珀酸衍生物的反应而形成的二酰亚胺。此类燃料添加剂是公知的并记载在,例如,文献(1)和(2)中。其优选为烷基-或烯基-取代的琥珀酸或其衍生物与胺的反应产物,且更优选聚异丁烯基-取代的琥珀酸或其衍生物与胺的反应产物。在本上下文中,特别引人关注的是与脂族多胺(聚亚烷基亚胺)例如,更具体而言为亚乙基二胺、二亚乙基三胺、三亚乙基四胺、四亚乙基五胺、五亚乙基六胺和六亚乙基七胺的反应产物,其具有酰亚胺结构。
包含通过取代酚与醛和单胺或多胺的曼尼希反应而获得的部分(Di)的添加剂优选为聚异丁烯-取代的酚与甲醛和单胺或多胺(如亚乙基二胺、二亚乙基三胺、三亚乙基四胺、四亚乙基五胺或二甲基氨基丙基胺)的反应产物。所述聚异丁烯-取代的酚可源自Mn=300至5000的常规的或高反应性的聚异丁烯。此类“聚异丁烯曼尼希碱”更加具体地记载在EP-A 831 141中。
所述一种或更多种清洁剂添加剂可以以这样的量加入到燃料中,这些清洁剂添加剂的剂量优选为25至2500重量ppm,尤其为75至1500重量ppm,特别为150至1000重量ppm。
B2)载体油
另外使用的载体油可以是矿物属性或合成属性。合适的矿物载体油为在原油加工中获得的馏分,如具有SN 500–2000级的粘度的光亮油(brightstock)或基础油;以及芳族烃、石蜡族烃和烷氧基烷醇。同样有用的是在矿物油精制中获得并且称为“氢化裂化油”(沸程为约360℃至500℃的真空蒸馏馏份,可由已在高压下催化氢化并异构化和脱蜡的天然矿物油获得)的部分。同样合适的是上述矿物载体油的混合物。
合适的合成载体油的实例为聚烯烃(聚α烯烃或聚内烯烃)、(聚)酯、(聚)烷氧基化物、聚醚、脂族聚醚胺、烷基酚起始的聚醚、烷基酚起始的聚醚胺和以及链烷醇的羧酸酯。
合适的聚烯烃的实例为Mn=400至1800的烯烃聚合物,特别地基于聚丁烯或聚异丁烯(氢化或未氢化)。
合适的聚醚或聚醚胺的实例优选为包含聚氧-C2-至C4-亚烷基部分的化合物,其可通过使C2-至C60-烷醇、C6-至C30-烷二醇、单或双-C2-至C30-烷基胺、C1-至C30-烷基环己醇或C1-至C30-烷基酚以每个羟基或氨基(在聚醚胺的情况下)与1mol至30mol的环氧乙烷和/或环氧丙烷和/或环氧丁烷进行反应,随后用氨水、单胺或多胺进行还原胺化而获得。此类产物更加具体地记载在EP-A 310 875、EP-A 356 725、EP-A 700 985和US-A 4 877 416中。例如,所用的聚醚胺可以是聚-C2-至C6-环氧烷胺或其功能性衍生物。其典型实例为十三烷醇丁氧基化物或异十三烷醇丁氧基化物、异壬基酚丁氧基化物和聚异丁烯醇丁氧基化物和丙氧基化物、以及相应的与氨水的反应产物。
更特别地,长链烷醇的羧酸酯的实例为一元羧酸、二元羧酸或三元羧酸与长链烷醇或多元醇的酯,如在DE-A 38 38 918中更加具体地记载。所用的一元羧酸、二元羧酸或三元羧酸可以是脂族酸或芳族酸;特别合适的醇酯或酯多元醇为具有例如6至24个碳原子的长链代表物。所述酯的典型代表物为异辛醇、异壬醇、异癸醇和异十三烷醇的己二酸酯、邻苯二甲酸酯、间苯二甲酸酯、对苯二甲酸酯及偏苯三酸酯,例如双(正-或异十三烷基)邻苯二甲酸酯。
其他合适的载体油体系,例如,记载在DE-A 38 26 608、DE-A 41 42 241、DE-A 4309 074、EP-A 452 328和EP-A 548 617中。
特别合适的合成载体油的实例为每个醇分子具有约5至35个、优选约5至30个、更优选10至30个且尤其为15至30个C3-至C6-环氧烷单元(如环氧丙烷、环氧正丁烷和环氧异丁烷、或其混合物)的醇起始的聚醚。合适的起始醇的非限定性实例是被长链烷基取代的长链烷醇或长链酚,其中所述长链烷基尤其为直链或支链的C6-至C18-烷基。特别的实例包括十三烷醇和壬基酚。特别优选的醇起始的聚醚是一元脂族C6-至C18-醇与C3-至C6-环氧烷的反应产物(聚醚化产物)。一元脂族C6-至C18-醇的实例为己醇、庚醇、辛醇、2-乙基己醇、壬醇、癸醇、3-丙基庚醇、十一烷醇、十二烷醇、十三烷醇、十四烷醇、十五烷醇、十六烷醇、十八烷醇及其构造异构体和位置异构体。所述醇可以以纯异构体的形式或以工业级混合物的形式使用。特别优选的醇是十三烷醇。C3-至C6-环氧烷的实例为环氧丙烷(如1,2-环氧丙烷)、环氧丁烷(如1,2-环氧丁烷、2,3-环氧丁烷、环氧异丁烷或四氢呋喃)、环氧戊烷和环氧己烷。其中特别优选的是C3-至C4-环氧烷,即环氧丙烷(如1,2-环氧丙烷)和环氧丁烷(如1,2-环氧丁烷、2,3-环氧丁烷、环氧异丁烷)。尤其使用环氧丁烷。
其他合适的合成载体油是烷氧基化的烷基酚,如在DE-A 10 102 913中所记载。
特别的载体油是合成载体油,特别优选的是上述的醇起始的聚醚。
将载体油或不同载体油的混合物以优选1重量ppm至1000重量ppm、更优选10重量ppm至500重量ppm且特别为20重量ppm至100重量ppm的量加入到燃料中。
B3)冷流改进剂
原则上,合适的冷流改进剂为能够改进中间馏份燃料或柴油燃料在寒冷条件下的流动性能的所有有机化合物。为此预期目的,其必须具有足够的油溶性。更特别地,为此目的的有用的冷流改进剂为通常用于化石源的中间馏份的情况(即常规的矿物柴油燃料的情况)中的冷流改进剂(中间馏份流动改进剂,MDFI)。但是,当用于常规的柴油燃料时,也可使用部分或主要具有蜡抗沉降添加剂(WASA)特性的有机化合物。其还可以部分或主要起成核剂的作用。也可使用起MDFI作用和/或起WASA作用和/或起成核剂作用的有机化合物的混合物。
所述冷流改进剂通常选自:
(K1)C2-至C40-烯烃与至少一种其他烯键式不饱和单体的共聚物;
(K2)梳形聚合物;
(K3)聚氧亚烷基类;
(K4)极性的氮化合物;
(K5)磺基羧酸或磺酸或其衍生物;以及
(K6)聚(甲基)丙烯酸酯。
可使用来自特定类(K1)至(K6)中的一类的不同代表物的混合物或来自不同类(K1)至(K6)的代表物的混合物。
用于(K1)类共聚物的合适的C2-至C40-烯烃单体,例如,为具有2个至20个且尤其为2个至10个碳原子,并具有1个至3个且优选1个或2个碳-碳双键、尤其是具有1个碳-碳双键的烯烃单体。在后一情况下,所述碳-碳双键可排列在末端(α-烯烃)或排列在内部。但是,优选的是α-烯烃,特别优选具有2个至6个碳原子的α-烯烃,例如丙烯、1-丁烯、1-戊烯、1-己烯且特别为乙烯。
在(K1)类共聚物中,所述至少一种其他烯键式不饱和单体优选选自羧酸烯基酯、(甲基)丙烯酸酯和其他烯烃。
当其他烯烃也共聚合时,其优选比上述C2-至C40-烯烃类单体具有更高的分子量。例如,当所用的烯烃类单体为乙烯或丙烯时,合适的其他烯烃尤其为C10-至C40-α-烯烃。当还使用具有羧酸酯官能团的单体时,在大多数情况下其他烯烃仅额外地共聚合。
合适的(甲基)丙烯酸酯,例如,为(甲基)丙烯酸与以下物质的酯:C1-至C20-烷醇、尤其是C1-至C10-烷醇,特别地是与甲醇、乙醇、丙醇、异丙醇、正丁醇、仲丁醇、异丁醇、叔丁醇、戊醇、己醇、庚醇、辛醇、2-乙基己醇、壬醇和癸醇、及其结构异构体。
合适的羧酸烯基酯,例如,为具有2个至21个碳原子的羧酸(其烃基可为直链或支链的)的C2-至C14-烯基酯,例如乙烯基酯和丙烯基酯。其中,优选的是乙烯基酯。在具有支链烃基的羧酸中,优选的是其支链在羧基的α位且α-碳原子更优选为叔碳原子的羧酸,即所述羧酸为所谓的新羧酸。但是,羧酸的烃基优选为直链的。
合适的羧酸烯基酯的实例为乙酸乙烯酯、丙酸乙烯酯、丁酸乙烯酯、2-乙基己酸乙烯酯、新戊酸乙烯酯、己酸乙烯酯、新壬酸乙烯酯和新癸酸乙烯酯及相应的丙烯基酯,优选的是乙烯基酯。特别优选的羧酸烯基酯为乙酸乙烯酯;由其得到的(K1)类的典型共聚物为乙烯-乙酸乙烯酯共聚物(“EVA”),这是一些最常使用的。
特别有利的可用的乙烯-乙酸乙烯酯共聚物及其制备被记载在WO 99/29748中。
合适的(K1)类共聚物还为包含共聚形式的两种或更多种不同羧酸烯基酯的共聚物,所述羧酸烯基酯在烯基官能团和/或在羧酸基团方面不同。除羧酸烯基酯以外,同样合适的是包含共聚形式的至少一种烯烃和/或至少一种(甲基)丙烯酸酯的共聚物。
C2-至C40-α-烯烃、具有3个至15个碳原子的烯键式不饱和一元羧酸的C1-至C20-烷基酯、和具有2个至21个碳原子的饱和一元羧酸的C2-至C14-烯基酯的三元共聚物也适合作为(K1)类的共聚物。该类三元共聚物记载在WO 2005/054314中。典型的该类型的三元共聚物由乙烯、丙烯酸2-乙基己酯和乙酸乙烯酯形成。
该至少一种或其他烯键式不饱和单体是以优选1-50重量%、尤其10-45重量%且特别地20-40重量%的量共聚合到(K1)类共聚物中,基于整个共聚物计。因此,就(K1)类共聚物中的单体单元的重量而言,主要比例通常来源于C2-至C40类烯烃。
(K1)类共聚物的数均分子量Mn优选为1000-20 000、更优选1000-10 000且特别为1000-8000。
典型的组分(K2)的梳形聚合物,例如,可通过以下获得:使马来酸酐或富马酸与另一烯键式不饱和单体(例如与α-烯烃或不饱和酯,如乙酸乙烯酯)共聚合,随后用具有至少10个碳原子的醇将酸酐或酸官能团酯化。其他合适的梳形聚合物为α-烯烃和酯化的共聚单体的共聚物,例如苯乙烯和马来酸酐的酯化共聚物或者苯乙烯与富马酸的酯化共聚物。合适的梳形聚合物也可为聚富马酸酯或聚马来酸酯。乙烯基醚的均聚物和共聚物也是合适的梳形聚合物。适合作为(K2)类组分的梳形聚合物,例如,还有在WO 2004/035715和“Comb-Like Polymers,Structure and Properties”,N.A.Platéand V.P.Shibaev,J.Poly.Sci.Macromolecular Revs.8,117-253页(1974)中记载的聚合物。梳形聚合物的混合物也是合适的。
适合作为(K3)类组分的聚氧亚烷基类,例如,为聚氧亚烷基酯、聚氧亚烷基醚、混合的聚氧亚烷基酯/聚氧亚烷基醚、及其混合物。这些聚氧亚烷基化合物优选包含至少一个直链烷基、优选至少两个直链烷基(各自均具有10个至30个碳原子)以及包含数均分子量最高达5000的聚氧亚烷基基团。这样的聚氧亚烷基化合物,例如,记载在EP-A 061 895以及US4 491 455中。特别的聚氧亚烷基化合物是基于数均分子量为100-5000的聚乙二醇和聚丙二醇。其他合适的为具有10个至30个碳原子的脂肪酸(如硬脂酸或二十二烷酸)的聚氧亚烷基单酯和二酯。
适合作为(K4)类组分的极性的氮化合物可为离子的或非离子的且优选具有至少一个、尤其至少两个通式为>NR7的叔氮原子形式的取代基,在所述通式>NR7中,R7为C8-至C40-烃基。所述氮取代基也可以是季铵化的,即为阳离子形式。该氮化合物的实例为铵盐和/或酰胺,所述铵盐和/或酰胺可通过被至少一种烃基取代的至少一种胺与具有1个至4个羧基的羧酸或其合适的衍生物的反应而获得。所述胺优选包含至少一个直链C8-至C40烷基。适于制备所述极性的氮化合物的伯胺,例如,为辛胺、壬胺、癸胺、十一烷基胺、十二烷基胺、十四烷基胺以及更高级的直链同系物;适于该目的的仲胺,例如,为双十八烷基胺和甲基二十二烷基胺。同样适于该目的的是胺混合物,尤其可在工业规模获得的胺混合物,如脂肪胺或氢化牛油胺(hydrogenated tallamines),如在,例如,Ullmann’s Encyclopedia ofIndustrial Chemistry,第6版,“Amines,aliphatic”章节中记载的。适于反应的酸,例如,为长链烃基取代的环己烷-1,2-二羧酸、环己烯-1,2-二羧酸、环戊烷-1,2-二羧酸、萘二甲酸、邻苯二甲酸、间苯二甲酸、对苯二甲酸、和琥珀酸。
更特别地,(K4)类的组分为具有至少一个叔氨基的聚(C2-至C20-羧酸)与伯胺或仲胺的油溶性反应产物。具有至少一个叔氨基并形成该反应产物的基础的所述聚(C2-至-C20-羧酸)优选包含至少3个羧基,尤其是3个至12个羧基且特别为3个至5个羧基。聚羧酸中的羧酸单元优选具有2个至10个碳原子,且其尤其为乙酸单元。所述羧酸单元通常通过一个或更多个碳原子和/或氮原子而合适地键合至所述聚羧酸。其优选连接至叔氮原子,在多个氮原子的情况下,所述叔氮原子通过烃链键合。
(K4)类的组分优选为基于聚(C2-至C20-羧酸)的油溶性反应产物,所述聚(C2-至C20-羧酸)具有至少一个叔氨基且通式为IIa或IIb
其中变量A为直链或支链的C2-至C6-亚烷基或式III的部分
且变量B为C1-至C19-亚烷基。通式IIa和IIb的化合物尤其具有WASA特性。
此外,优选的组分(K4)的油溶性反应产物,特别是通式IIa或IIb的油溶性反应产物为其中无羧酸基团、一个或更多个羧酸基团已被转化成酰胺基的酰胺、酰胺-铵盐或铵盐。
变量A的直链或支链的C2-至C6-亚烷基,例如,为1,1-亚乙基、1,2-亚丙基、1,3-亚丙基、1,2-亚丁基、1,3-亚丁基、1,4-亚丁基、2-甲基-1,3-亚丙基、1,5-亚戊基、2-甲基-1,4-亚丁基、2,2-二甲基-1,3-亚丙基、1,6-亚己基(六亚甲基)且尤其为1,2-亚乙基。变量A优选包含2个至4个且尤其是2个或3个碳原子。
变量B的C1-至C19-亚烷基,例如,为1,2-亚乙基、1,3-亚丙基、1,4-亚丁基、六亚甲基、八亚甲基、十亚甲基、十二亚甲基、十四亚甲基、十六亚甲基、十八亚甲基、十九亚甲基且尤其为亚甲基。变量B优选包含1个至10个且尤其是1至4个碳原子。
作为用于形成组分(K4)的聚羧酸的反应配对物的伯胺和仲胺通常为单胺,尤其脂族单胺。这些伯胺和仲胺可选自带有可任选彼此键合的烃基的多种胺。
组分(K4)的油溶性反应产物的这些母体胺通常为仲胺并具有通式HN(R8)2,其中两个变量R8各自独立地为直链或支链的C10-至C30烷基,尤其是C14-至C24烷基。这些相对较长链的烷基优选为直链的或仅略微支化。一般而言,所述仲胺(就其相对较长链的烷基而言)衍生自天然生成的脂肪酸及其衍生物。优选地,两个R8基是相同的。
所述仲胺可以以酰胺结构的方式或者以铵盐的形式键合至聚羧酸;也可以仅部分以酰胺结构存在而另外的部分以铵盐存在。如果有的话,优选仅存在很少的游离的酸基团。组分(K4)的油溶性反应产物优选完全以酰胺结构的形式存在。
该组分(K4)的典型实例为,次氮基三乙酸、乙二胺四乙酸、或丙烯-1,2-二胺四乙酸与在每种情况下每羧基0.5-1.5mol、尤其是每羧基0.8-1.2mol的二油胺(dioleylamine)、二棕榈胺(dipalmitamine)、二椰油胺(dicocoamine)、二硬脂胺或双二十二烷基胺或尤其是二牛油胺的反应产物。特别优选的组分(K4)为1mol的乙二胺四乙酸与4mol的氢化二牛油胺的反应产物。
组分(K4)的其他典型实例包括2-N’,N’-二烷基酰胺基苯甲酸酯的N,N-二烷基铵盐,例如1mol的邻苯二甲酸酐与2mol的二牛油胺(后者是氢化或未氢化的)的反应产物,以及1mol的烯基螺双内酯与2mol的二烷基胺如二牛油胺和/或牛油胺(后两者是氢化或未氢化的)的反应产物。
用于(K4)类组分的其他典型结构类型为具有叔氨基的环状化合物或者长链伯胺或仲胺与含羧酸的聚合物的缩合物,如在WO 93/18115中所记载的。
适合作为(K5)类组分的冷流改进剂的磺基羧酸、磺酸、或其衍生物,例如,为邻磺基苯甲酸(ortho-sulfobenzoic acid)的油溶性羧酰胺和羧酸酯,其中磺酸官能团是作为具有烷基取代的铵阳离子的磺酸盐存在,如在EP-A 261 957中所记载的。
适合作为(K6)类组分的冷流改进剂的聚(甲基)丙烯酸酯为丙烯酸酯和甲基丙烯酸酯的均聚物或共聚物。优选的是在酯化醇方面不同的至少两种不同的(甲基)丙烯酸酯的共聚物。任选地,所述共聚物包含共聚形式的另一不同的烯属不饱和单体。聚合物的重均分子量优选为50 000-500 000。特别优选的聚合物为甲基丙烯酸与饱和C14-和C15-醇的甲基丙烯酸酯的共聚物,所述酸基团已被氢化牛油胺中和。合适的聚(甲基)丙烯酸酯,例如,记载在WO 00/44857中。
将冷流改进剂或不同冷流改进剂的混合物以优选10重量ppm至5000重量ppm、更优选20重量ppm至2000重量ppm、甚至更优选50重量ppm至1000重量ppm且尤其是100重量ppm至700重量ppm(例如200重量ppm至500重量ppm)的总量加入到中间馏份燃料或柴油燃料中。
B4)润滑改进剂
合适的润滑改进剂或摩擦改进剂通常基于脂肪酸或脂肪酸酯。典型实例为妥尔油脂肪酸(如在,例如,WO 98/004656中所记载的)和单油酸甘油酯。天然油或合成油(如甘油三酸酯)与链烷醇胺的反应产物(记载在US 6 743 266 B2中)也适合作为该润滑改进剂。
B5)除所述共聚物以外的腐蚀抑制剂
合适的腐蚀抑制剂,例如,为琥珀酸酯(特别是与多元醇的酯),脂肪酸衍生物,如油酸酯、低聚脂肪酸、取代的乙醇胺、和以商标名RC 4801(Rhein Chemie Mannheim,Germany)、L12(BASF SE)或HiTEC 536(Ethyl Corporation)出售的产品。
B6)破乳剂
合适的破乳剂,例如,为烷基-取代的酚-和萘磺酸酯的碱金属或碱土金属盐以及脂肪酸的碱金属或碱土金属盐、以及中性化合物(如醇烷氧基化物(如醇乙氧基化物)、酚烷氧基化物(如叔丁基酚乙氧基化物或叔戊基酚乙氧基化物))、脂肪酸、烷基酚、环氧乙烷(EO)与环氧丙烷(PO)的缩合产物(例如包括EO/PO嵌段共聚物的形式)、聚乙烯亚胺或聚硅氧烷。
B7)去雾剂
合适的去雾剂,例如,为烷氧基化酚-甲醛缩合物,例如可以以商标名NALCO 7D07(Nalco)和TOLAD 2683(Petrolite)获得的产品。
B8)消泡剂
合适的消泡剂,例如,为聚醚改性的聚硅氧烷,如可以以商标名TEGOPREN 5851(Goldschmidt)、Q 25907(Dow Corning)和RHODOSIL(Rhone Poulenc)获得的产品。
B9)十六烷值改进剂
合适的十六烷值改进剂,例如,为脂族硝酸酯,如硝酸2-乙基己酯和硝酸环己酯以及过氧化物(如二叔丁基过氧化物)。
B10)抗氧化剂
合适的抗氧化剂,例如,为取代的酚(如2,6-二叔丁基酚和6-二叔丁基-3-甲基酚)、以及苯二胺(如N,N'-二仲丁基-对苯二胺)。
B11)金属钝化剂
合适的金属钝化剂,例如,为水杨酸衍生物,如N,N'-二亚水杨基-1,2-丙二胺。
B12)溶剂
合适的溶剂,例如,为非极性有机溶剂,例如芳族和脂族烃,如甲苯、二甲苯、石油溶剂(white spirit)和以商标名SHELLSOL(Royal Dutch/Shell Group)和EXXSOL(ExxonMobil)出售的产品;以及极性有机溶剂,例如,醇,如2-乙基己醇、癸醇和异十三烷醇。所述溶剂通常与前述添加剂和共添加剂一起加入到柴油燃料中,所述添加剂和共添加剂旨在被溶解或稀释以便更好地处理。
C)燃料
原则上,本发明的用途涉及任何燃料,优选柴油燃料和汽油燃料。
中间馏份燃料(如柴油燃料或加热油)优选为沸程通常为100℃至400℃的矿物油提余油。其通常为具有95%点最高达360℃或甚至更高的馏分。其也可为所谓的“超低硫柴油”或“城市柴油”,其特征在于,例如,95%点不超过345℃且硫含量不超过0.005重量%,或者,95%点为例如285℃且硫含量不超过0.001重量%。除可通过精制而获得的矿物中间馏份燃料或柴油燃料以外,可通过煤的气化或天然气的液化[“天然气制油”(GTL)燃料]或通过生物质液化[“生物质制油”(BTL)燃料]获得的那些也是合适的。同样合适的是前述中间馏份燃料或柴油燃料与可再生燃料(如生物柴油或生物乙醇)的混合物。
所述加热油和柴油燃料的特质详细记载在,例如,DIN 51603和EN 590中(另外参见Ullmann’s Encyclopedia of Industrial Chemistry,第5版,卷A12,617页及以后)。
在化石源、植物源或动物源的中间馏份燃料(它们基本为烃的混合物)中的本发明的用途还涉及该中间馏份与生物燃料油(生物柴油)的混合物。这类混合物被术语“中间馏份燃料”涵盖。其为市售可得的且通常包含少量的生物燃料油,通常为1-30重量%、尤其3-10重量%的量,基于化石源、植物源或动物源的中间馏份与生物燃料油的总量计。
生物燃料油通常基于脂肪酸酯,优选基本上基于源自植物油和/或动物油和/或脂肪的脂肪酸的烷基酯。烷基酯通常理解为意指低级烷基酯,尤其是C1-至C4-烷基酯,其可通过用低级醇(如乙醇或特别地甲醇(“FAME”))对植物油和/或动物油和/或脂肪中产生的甘油酯、尤其甘油三酸酯进行酯交换而获得。基于植物油和/或动物油和/或脂肪(其用作生物燃料油或其组分)的典型的低级烷基酯,例如,为向日葵甲酯(sunflower methyl ester)、棕榈油甲酯(“PME”)、大豆油甲酯(“SME”)以及尤其是菜子油甲酯(“RME”)。
更优选地,所述中间馏份燃料或柴油燃料为具有低的硫含量的那些,即硫含量小于0.05重量%、优选小于0.02重量%、更特别地小于0.005重量%且尤其小于0.001重量%的那些。
有用的汽油燃料包括所有市售的汽油燃料组合物。本说明书中应提及的一种典型的代表物是EN 228的Eurosuper类燃料,其在市场上是常见的。此外,根据WO 00/47698的说明书的汽油燃料组合物也是本发明可能的应用领域。
以下实施例旨在说明本发明,并非对其进行限制。
实施例
GPC分析
除非另有说明,否则聚合物的质均分子量Mw和数均分子量Mn通过凝胶渗透色谱法(GPC)来测定。GPC分离通过两根PLge Mixed B柱(Agilent)在四氢呋喃中在35℃下进行。通过具有162-50 400Da的分子量的窄分布的聚苯乙烯标准物(来自PSS,Germany)进行校准。将己基苯用作低分子量标记物。
酸值的测定
效能值(efficacy value)的测定
在配有空气冷却器的150mL的COD管中,将50mL的0.5摩尔的KOH乙醇溶液加热至95℃,保持3个小时。用30mL的乙醇清洗所述空气冷却器,然后用0.5摩尔盐酸(HCl)水溶液对所述溶液进行图形电位滴定。
样品的测定
将约1g的样品称重到150mL的COD管中并溶解在50mL的0.5摩尔的KOH乙醇溶液中。使COD管配有空气冷却器并放置到预热至95℃的搅动的块恒温器(block thermostat)中。3个小时以后,将COD管由加热块中移出并用30mL的乙醇冲洗,用0.5摩尔盐酸(HCl)水溶液对所述溶液进行图形电位滴定。
制备实施例
一般方法
首先,在具有锚式搅拌器的反应器中装入含溶剂或不含溶剂(作为本体聚合)的烯烃或烯烃混合物。在氮气流下将混合物加热至规定温度,同时进行搅拌。向其中加入规定的自由基引发剂(任选地在相同的溶剂中稀释)和熔融的马来酸酐(1当量,基于烯烃单体计)。在相同的温度下将反应混合物搅拌规定的反应时间,然后冷却。随后,加入水(除非另有说明,否则为0.9当量,基于马来酸酐计)并将混合物在95℃下搅拌10h-14h或在压力下在110℃下搅拌3h。
合成实施例1
首先,在具有锚式搅拌器的2L的玻璃反应器中装入C20-C24烯烃(363.2g,平均摩尔质量296g/mol)与Solvesso 150(231.5g,DHC Solvent Chemie GmbH,Speldorf)的混合物。在氮气流中将混合物加热至160℃,同时进行搅拌。在5h内,向其中加入二叔丁基过氧化物(29.6g,购自Akzo Nobel)于Solvesso 150(260.5g)中的溶液和熔融的马来酸酐(120.3g)。在160℃下将反应混合物搅拌1h,然后冷却至95℃。在该温度下,在3h内加入水(19.9g),然后继续搅拌11h。
GPC(在THF中)给出共聚物的Mn=1210g/mol,Mw=2330g/mol,其对应于1.9的多分散性。
共聚物的每个酸基团的碳原子比率为13;通过上述方法测得的酸值为210.8mgKOH/g。
合成实施例2
首先,在具有锚式搅拌器的6L的金属反应器中装入C20-C24烯烃(1743g,平均摩尔质量296g/mol)与Solvesso 150(1297g,DHC Solvent Chemie GmbH,Speldorf)的混合物。在氮气流中将混合物加热至150℃,同时进行搅拌。在5h内,向其中加入二叔丁基过氧化物(118.4g,购自Akzo Nobel)于Solvesso 150(1041g)中的溶液和熔融的马来酸酐(577g)。在150℃下将反应混合物搅拌1h,然后冷却至110℃。在该温度下,随压力增加,加入水(95g),然后继续搅拌3h。
GPC(在THF中)给出共聚物的Mn=1420g/mol,Mw=2500g/mol,其对应于1.8的多分散性。
共聚物的每个酸基团的碳原子比率为13;通过上述方法测得的酸值为210.8mgKOH/g。
合成实施例3
首先,在具有锚式搅拌器的6L的金属反应器中装入C20-C24烯烃(1743g,平均摩尔质量296g/mol)与Solvesso 150(1297g,DHC Solvent Chemie GmbH,Speldorf)的混合物。在氮气流中将混合物加热至150℃,同时进行搅拌。在5h内,向其中加入二叔丁基过氧化物(23.7g,购自Akzo Nobel)于Solvesso 150(912g)中的溶液和熔融的马来酸酐(577g)。在150℃下将反应混合物搅拌1h,然后冷却至110℃。在该温度下,随压力增加,加入水(95g),然后继续搅拌3h。
GPC(在THF中)给出共聚物的Mn=1500g/mol,Mw=3200g/mol,其对应于2.1的多分散性。
共聚物的每个酸基团的碳原子比率为13;通过上述方法测得的酸值为210.8mgKOH/g。
用途实施例
通过与聚异丁烯胺(摩尔质量1000)、作为载体油的聚丙二醇、和溶剂及去雾剂进行混合,由上述合成实施例制备表2中规定的添加剂制剂,并应用于用途实施例中(以重量份计的组合物)。
1)钙兼容性试验;
在烧杯中将100mL的马达油(motor oil)(Shell图1,最左侧烧杯,具有1500ppm的Ca含量、1100ppm的Mg含量、和1300ppm的Zn含量)加热至70℃,然后加入1mL的腐蚀抑制剂。如果溶液仍清澈,则再加入1mL抑制剂。如果溶液变混浊,那么认为试验已经失败(例如,图1,右手边的烧杯)。图1示出向其中加入了合成实施例1的共聚物的油(50%,于溶剂石脑油中),其保持清澈(位于中间的)。在右手边的烧杯中,使用了二聚体脂肪酸(二聚油酸;CAS:61788-89-4,20%,于溶剂石脑油中)。出现明显可见的混浊。
2)根据ASTM D 665B的钢腐蚀试验
a)所用燃料是来自Haltermann的常规的95辛烷值E0汽油燃料,其添加有由聚异丁烯胺和载体油组成的添加剂包。将下表中规定的腐蚀抑制剂加入到制剂中,根据ASTM D665B对所述制剂进行腐蚀试验。
二聚体脂肪酸(二聚油酸;CAS:61788-89-4,作为腐蚀抑制剂,20%,于溶剂石脑油中)用作对比。
评价如下进行:
A 100%不锈
B++ 总表面积的0.1%或更少生了锈
B+ 总表面积的0.1%至5%生了锈
B 总表面积的5%至25%生了锈
C 总表面积的25%至50%生了锈
D 总表面积的50%至75%生了锈
E 总表面积的75%至100%生了锈
b)与a)类似地进行另一实验,但利用E0汽油燃料KS-0001829 CEC DF-12-09。
结果如下:
c)与a)类似地进行另一实验,但利用汽油燃料KS-0001858 MIRO 95辛烷值E10。
结果如下:
d)试验根据标准ASTM D665 A(修正的)利用蒸馏水以及根据ASTM D665 B(修正的)利用合成海水在与根据EN590 B7的柴油基燃料的混合物中进行,无性能添加剂。修正之处在于温度为60℃且试验的持续时间为4小时。
e)根据ASTM D 665 B进行另一实验,其中利用常规的95辛烷值E0汽油燃料,并添加有由聚异丁烯胺和载体油组成的添加剂包。将聚异丁烯琥珀酸(基于摩尔质量1000的聚异丁烯)和二聚体脂肪酸(二聚油酸;CAS:61788-89-4)加入到制剂中作为对比,并根据ASTMD 665 B进行腐蚀试验。
*两次试验
f)根据ASTM D 665 B进行另一实验,其中利用常规的95辛烷值E0汽油燃料,并添加有由聚异丁烯胺(基于摩尔质量1000的聚异丁烯)、去雾剂和载体油组成的添加剂包。将十二碳烯基琥珀酸(酸值392mg KOH/g)和二聚体脂肪酸(二聚油酸;CAS:61788-89-4)加入到制剂中作为对比,并根据ASTM D 665 B进行腐蚀试验。
剂量[mg/kg] NACE等级*
基值E0 RON 95 D
二聚体脂肪酸 2 A/B+
十二碳烯基琥珀酸 3.2 A/B++
十二碳烯基琥珀酸 2.75 B++/B++
*两次试验
在室温下储存时,含十二碳烯基琥珀酸的添加剂包表现出相分离,这表明十二碳烯基琥珀酸在添加剂包中不具有足够的溶解度。
3)铜腐蚀
a)在汽油中
用具有合适的抛光刷的抛光机对铜样片(尺寸49×25×1.5mm,中间打孔)进行仔细抛光,不在两侧和所有的边上面紧压。带着橡胶手套使用清洁布用二甲苯和丙酮将抛光的样片擦拭数次。将200mL的燃料引入到250mL的带螺旋盖的玻璃瓶里。用线系紧样片并使其悬浮在燃料瓶中。通过将线捆在螺纹中而使其固定。
在室温(23℃)下进行储存。第一储存期(7天)过去后,取一份样品(20-30mL),再次使玻璃瓶封闭并且通过原子吸收光谱测定金属含量。继续储存。在重复取样和液位下降以后,要确保铜样片完全被燃料覆盖。
结果列于表1中。
由表1的结果显见,在相同的剂量下,本发明所用的化合物比用作对比的二聚体脂肪酸更少倾向于在燃料中从润湿表面溶浸铜。
b)在柴油燃料中
为研究来自合成实施例1的样品关于非铁金属的腐蚀特性,用锌线和铜线进行试验。
将80mL的Aral B7 EN590燃料分别分配到四个瓶中,其中的两个已经加入来自合成实施例1的140ppm的样品。将长20cm且直径1mm的去除油污的铜线放置在一个瓶中,而另一个瓶中则不放置该样品。类似地,将长20cm且直径1mm的去除油污的锌线放置在一个瓶中,而另一个瓶中则不放置该样品。
在40℃下储存6周以后,通过原子发射光谱(ICP/OES)测定原始燃料中的铜或锌含量。
可见,本发明的化合物对非铁金属、尤其是铜具有腐蚀抑制效果。
4)PFI发动机试验DC M111E
根据CEC F-020-98用MIRO 95辛烷值E10燃料进行超过60个小时的发动机试验,测定内阀沉积物(IVD)和总腔室沉积物(TCD值)。
在保持清洁模式中,发现无腐蚀抑制剂的含添加剂的燃料的TCD值为4122mg,而有腐蚀抑制剂的含添加剂的燃料(制剂10)的TCD值为3940mg。
另外,发现无添加剂的燃料的IVD值为116mg/阀,以及在保持清洁模式中,无腐蚀抑制剂的含添加剂的燃料的IVD值为2mg/阀,而有腐蚀抑制剂的含添加剂的燃料(制剂10)的IVD值为1mg/阀。
5)在汽油直喷发动机(DISI)中的保持清洁试验
用来自MIRO的E10汽油燃料(7体积%的含氧组分)使市售可得的DISI(直喷火花喷射)发动机(气缸容量1.6升)以4000rpm的速度运转50个小时。
在第一次运转中,燃料不包含任何添加剂。FR值在0与-1之间波动。
在第二次运转中,燃料包含520mg/kg的制剂10。FR值在-2与-3之间波动。
在两次运转中,均对FR值进行测定。FR是发动机控制系统根据燃料向燃烧室的喷射而产生的参数。沉积物的形成通过在运转期间升高的FR值来显示。其增长的越多,就形成了越多的沉积物。如果FR值保持恒定或降低,那么喷射器喷嘴也保持清洁。两次运转中FR值都不升高,这表面要求保护的共聚物对喷射器清洁没有任何不利影响。
表1
表2

Claims (15)

1.具有以下统计平均数的聚合物作为燃料或润滑油、优选燃料、更优选具有至少0.1重量ppm的碱金属和/或碱土金属和/或锌含量的燃料中的腐蚀抑制剂的用途:
-每个聚合物链至少4个酸基团,
-每个酸基团的碳原子比率为7至35以及
-80mg KOH/g至320mg KOH/g的酸值,通过在0.5摩尔的氢氧化钾乙醇溶液中加热3小时后用0.5摩尔的盐酸水溶液进行图形电位滴定而测定。
2.根据权利要求1所述的用途,其中所述碱金属和/或碱土金属和/或锌选自钠、锌、镁和钙。
3.根据权利要求1或2所述的用途,其中所述酸基团为羧基。
4.根据前述权利要求任一项所述的用途,其中所述聚合物每个聚合物链带有最高达50个酸基团。
5.根据前述权利要求任一项所述的用途,其中所述聚合物每个聚合物链带有不多于5个除含氧官能团和含氮官能团以外的官能团。
6.根据前述权利要求任一项所述的用途,其中所述聚合物每个聚合物链除碳酸酯基团、醚基或酯基外带有不多于3个含氧官能团。
7.根据前述权利要求任一项所述的用途,其中所述聚合物每个聚合物链带有不多于20个醚基。
8.根据前述权利要求任一项所述的用途,其中所述聚合物每个聚合物链带有不多于50个碳酸酯基团或酯基。
9.根据前述权利要求任一项所述的用途,其中所述聚合物具有0.5kDa至20kDa的重均分子量(通过凝胶渗透色谱法以四氢呋喃和作为标准物的聚苯乙烯测定)和1至10的多分散性。
10.根据前述权利要求任一项所述的用途,其用于抑制铁、钢和/或非铁金属表面的腐蚀。
11.根据权利要求1至9中任一项所述的用途,其用于抑制铜和含铜合金的腐蚀。
12.根据前述权利要求任一项所述的用途,其中所述燃料为柴油燃料或汽油燃料。
13.根据前述权利要求任一项所述的用途,其中在20℃下,所述聚合物在甲苯中具有至少0.5g/100mL的溶解度。
14.具有以下统计平均数的聚合物在下述添加剂包中用于在具有至少0.1ppm的碱金属和/或碱土金属和/或锌含量的柴油燃料中降低腐蚀的用途:
-每个聚合物链至少4个酸基团,
-每个酸基团的碳原子比率为7至35以及
-80mg KOH/g至320mg KOH/g的酸值,通过在0.5摩尔的氢氧化钾乙醇溶液中加热3小时后用0.5摩尔的盐酸水溶液进行图形电位滴定而测定,
所述添加剂包包含至少一种选自清洁剂添加剂、载体油、冷流改进剂、润滑改进剂、除所述聚合物以外的腐蚀抑制剂、破乳剂、去雾剂、消泡剂、十六烷值改进剂、助燃剂、抗氧化剂、稳定剂、抗静电剂、金属茂合物、金属钝化剂、染料和溶剂的添加剂。
15.具有以下统计平均数的聚合物在下述添加剂包中用于在具有至少0.1ppm的碱金属和/或碱土金属和/或锌含量的汽油燃料中降低腐蚀的用途:
-每个聚合物链至少4个酸基团,
-每个酸基团的碳原子比率为7至35以及
-80mg KOH/g至320mg KOH/g的酸值,通过在0.5摩尔的氢氧化钾乙醇溶液中加热3小时后用0.5摩尔的盐酸水溶液进行图形电位滴定而测定,
所述添加剂包包含至少一种选自润滑改进剂(摩擦改进剂)、除所述聚合物以外的腐蚀抑制剂、破乳剂、去雾剂、消泡剂、助燃剂、抗氧化剂、稳定剂、抗静电剂、金属茂合物、金属钝化剂、染料和溶剂的添加剂。
CN201580017192.XA 2014-01-29 2015-01-29 用于燃料和润滑油的腐蚀抑制剂 Active CN106133120B (zh)

Applications Claiming Priority (7)

Application Number Priority Date Filing Date Title
EP14152991 2014-01-29
EP14152991.7 2014-01-29
EPPCT/EP2014/076622 2014-12-04
PCT/EP2014/076622 WO2015113681A1 (de) 2014-01-29 2014-12-04 Polycarbonsäure-basierte additive für kraft und schmierstoffe
EP14198266.0 2014-12-16
EP14198266 2014-12-16
PCT/EP2015/051825 WO2015114053A1 (de) 2014-01-29 2015-01-29 Korrosionsinhibitoren für kraft- und schmierstoffe

Publications (2)

Publication Number Publication Date
CN106133120A true CN106133120A (zh) 2016-11-16
CN106133120B CN106133120B (zh) 2019-12-13

Family

ID=53756246

Family Applications (3)

Application Number Title Priority Date Filing Date
CN201580012804.6A Active CN106459811B (zh) 2014-01-29 2015-01-29 用于燃料和润滑剂的缓蚀剂
CN201580017192.XA Active CN106133120B (zh) 2014-01-29 2015-01-29 用于燃料和润滑油的腐蚀抑制剂
CN201580006480.5A Active CN106062154B (zh) 2014-01-29 2015-01-29 聚合物作为燃料和润滑剂的添加剂

Family Applications Before (1)

Application Number Title Priority Date Filing Date
CN201580012804.6A Active CN106459811B (zh) 2014-01-29 2015-01-29 用于燃料和润滑剂的缓蚀剂

Family Applications After (1)

Application Number Title Priority Date Filing Date
CN201580006480.5A Active CN106062154B (zh) 2014-01-29 2015-01-29 聚合物作为燃料和润滑剂的添加剂

Country Status (13)

Country Link
US (3) US10377958B2 (zh)
EP (3) EP3099767A1 (zh)
KR (3) KR20160114161A (zh)
CN (3) CN106459811B (zh)
AU (2) AU2015212854B2 (zh)
BR (2) BR112016017414A2 (zh)
CA (2) CA2938220A1 (zh)
ES (1) ES2756578T3 (zh)
PL (1) PL3099768T3 (zh)
RU (3) RU2685271C2 (zh)
SG (2) SG11201605508UA (zh)
WO (3) WO2015114029A1 (zh)
ZA (1) ZA201605889B (zh)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111849588A (zh) * 2020-08-18 2020-10-30 上海金兆节能科技有限公司 抗磨润滑脂及其制备方法
CN111925857A (zh) * 2020-08-18 2020-11-13 上海金兆节能科技有限公司 抗磨微量润滑油及制备方法

Families Citing this family (25)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
PL3099720T3 (pl) 2014-01-29 2018-12-31 Basf Se Zastosowanie dodatków opartych na kwasach polikarboksylowych do paliw silnikowych
US10377958B2 (en) 2014-01-29 2019-08-13 Basf Se Corrosion inhibitors for fuels and lubricants
WO2017009305A1 (de) 2015-07-16 2017-01-19 Basf Se Copolymere als additive für kraft- und schmierstoffe
ES2762999T3 (es) * 2015-07-16 2020-05-26 Basf Se Inhibidores de la corrosión para combustibles
US9873848B2 (en) 2015-12-04 2018-01-23 Afton Chemical Corporation Fuel additives for treating internal deposits of fuel injectors
US10920001B2 (en) 2016-01-25 2021-02-16 Basf Se Process for obtaining a cationic polymer with an at least bimodal molecular weight distribution
WO2017144378A1 (de) * 2016-02-23 2017-08-31 Basf Se HYDROPHOBE POLYCARBONSÄUREN ALS REIBVERSCHLEIß-VERMINDERNDER ZUSATZ ZU KRAFTSTOFFEN
PT3481920T (pt) 2016-07-05 2021-11-10 Basf Se Utilização de inibidores de corrosão para combustíveis e lubrificantes
ES2858088T3 (es) 2016-07-05 2021-09-29 Basf Se Inhibidores de la corrosión para carburantes y lubricantes
WO2018007445A1 (de) 2016-07-07 2018-01-11 Basf Se Korrosionsinhibitoren für kraft- und schmierstoffe
US10527714B2 (en) * 2016-11-17 2020-01-07 Rohde & Schwarz Gmbh & Co. Kg Calibration device and calibration method for calibrating antenna arrays
CN110088253B (zh) 2016-12-15 2022-03-18 巴斯夫欧洲公司 作为燃料添加剂的聚合物
EP3555242B1 (de) * 2016-12-19 2020-11-25 Basf Se Additive zur verbesserung der thermischen stabilität von kraftstoffen
RU2019122807A (ru) 2016-12-20 2021-01-22 Басф Се Применение смеси комплексного сложного эфира с монокарбоновой кислотой для уменьшения трения
AU2018253240A1 (en) 2017-04-11 2019-10-17 Basf Se Alkoxylated amines as fuel additives
EP3609990B1 (de) * 2017-04-13 2021-10-27 Basf Se Polymere als additive für kraft- und schmierstoffe
US11002730B2 (en) 2018-05-23 2021-05-11 International Business Machines Corporation Molecular design to suppress desorption of self-assembled monolayers
PL3940043T3 (pl) 2020-07-14 2024-02-19 Basf Se Inhibitory korozji do paliw silnikowych i smarów
EP4247921A1 (en) 2020-11-20 2023-09-27 Basf Se Mixtures for improving or boosting the separation of water from fuels
CN116568782A (zh) 2020-12-16 2023-08-08 巴斯夫欧洲公司 用于改进添加剂包的稳定性的新的混合物
GB202118103D0 (en) 2021-12-14 2022-01-26 Innospec Ltd Fuel compositions
WO2024061760A1 (de) 2022-09-23 2024-03-28 Basf Se Verminderung der kristallisation von paraffinen in kraftstoffen
DE102022131356A1 (de) 2022-11-28 2023-01-12 Basf Se Formamidine als Kraftstoffadditive
DE102022131890A1 (de) 2022-12-01 2023-01-26 Basf Se Guanidinderivate als Kraftstoffadditive
DE102022132342A1 (de) 2022-12-06 2023-01-26 Basf Se Guanidiniumsalze als Kraftstoffadditive

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5080686A (en) * 1982-10-20 1992-01-14 Petrolite Corporation Alkyl or alkenyl succinic acids as corrosion inhibitors for oxygenated fuels
US5358651A (en) * 1985-10-25 1994-10-25 The Lubrizol Corporation Compositions, concentrates, lubricant compositions, fuel composition and methods for improving fuel economy of internal combustion engines
US20020026028A1 (en) * 2000-07-11 2002-02-28 Ulrich Epple Low molar mass aliphatic polyester polyols, their preparation and use in high performance coating compositions
US20050126070A1 (en) * 2003-12-11 2005-06-16 Clariant Gmbh Fuel oils composed of middle distillates and oils of vegetable or animal origin and having improved cold flow properties

Family Cites Families (60)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB802589A (en) * 1955-03-22 1958-10-08 California Research Corp Compounded hydrocarbon fuels
US3382056A (en) * 1966-06-03 1968-05-07 Chevron Res Maleic anhydride copolymers as rust inhibitors
US4171959A (en) 1977-12-14 1979-10-23 Texaco Inc. Fuel composition containing quaternary ammonium salts of succinimides
JPS5922791B2 (ja) * 1978-12-25 1984-05-29 三菱化学株式会社 防錆剤
SU857240A1 (ru) * 1979-02-06 1981-08-23 Предприятие П/Я А-1785 Полимерна присадка к парафинистым нефт м
US4248719A (en) 1979-08-24 1981-02-03 Texaco Inc. Quaternary ammonium salts and lubricating oil containing said salts as dispersants
US4464182A (en) 1981-03-31 1984-08-07 Exxon Research & Engineering Co. Glycol ester flow improver additive for distillate fuels
JPS58138791A (ja) 1982-02-10 1983-08-17 Nippon Oil & Fats Co Ltd 燃料油用流動性向上剤
FR2572410B1 (fr) * 1984-10-25 1987-09-04 Elf Aquitaine Copolymeres d'ethylene greffes utilisables notamment comme additifs pour l'inhibition du depot de paraffines dans les huiles brutes et compositions renfermant les huiles et lesdits additifs
US4690687A (en) 1985-08-16 1987-09-01 The Lubrizol Corporation Fuel products comprising a lead scavenger
DE3611230A1 (de) 1986-04-04 1987-10-08 Basf Ag Polybutyl- und polyisobutylamine, verfahren zu deren herstellung und diese enthaltende kraft- und schmierstoffzusammensetzungen
IN184481B (zh) 1986-09-24 2000-08-26 Exxon Chemical Patents Inc
EP0299120A1 (en) 1987-07-14 1989-01-18 Petrolite Corporation Alkyl or alkenyl succinic acids as corrosion inhibitors for oxygenated fuels
ES2032318T3 (es) 1987-09-15 1993-02-01 Basf Aktiengesellschaft Carburantes para motores otto.
DE3732908A1 (de) 1987-09-30 1989-04-13 Basf Ag Polyetheramine enthaltende kraftstoffe fuer ottomotoren
US4877416A (en) 1987-11-18 1989-10-31 Chevron Research Company Synergistic fuel compositions
DE3826608A1 (de) 1988-08-05 1990-02-08 Basf Ag Polyetheramine oder polyetheraminderivate enthaltende kraftstoffe fuer ottomotoren
DE3838918A1 (de) 1988-11-17 1990-05-23 Basf Ag Kraftstoffe fuer verbrennungsmaschinen
DE4030164A1 (de) 1990-09-24 1992-03-26 Basf Ag Kraftstoffe fuer verbrennungsmotoren und schmierstoffe enthaltende hochmolekulare aminoalkohole
DE4142241A1 (de) 1991-12-20 1993-06-24 Basf Ag Kraftstoffe fuer ottomotoren
GB9204709D0 (en) 1992-03-03 1992-04-15 Exxon Chemical Patents Inc Additives for oils
DE4309074A1 (de) 1993-03-20 1994-09-22 Basf Ag Als Kraftstoffadditiv geeignete Mischungen
DE4313088A1 (de) 1993-04-22 1994-10-27 Basf Ag Poly-1-n-alkenamine und diese enthaltende Kraft- und Schmierstoffzusammensetzungen
AT400149B (de) 1993-08-17 1995-10-25 Oemv Ag Additiv für unverbleite ottokraftstoffe sowie dieses enthaltender kraftstoff
DE4425835A1 (de) 1994-07-21 1996-01-25 Basf Ag Verwendung von Umsetzungsprodukten aus Polyolefinen und Stickoxiden oder Gemischen aus Stickoxiden und Sauerstoff als Additive für Kraftstoffe
DE4425834A1 (de) 1994-07-21 1996-01-25 Basf Ag Umsetzungsprodukte aus Polyisobutenen und Stickoxiden oder Gemischen aus Stickoxiden und Sauerstoff und ihre Verwendung als Kraft- und Schmierstoffadditive
DE4432038A1 (de) 1994-09-09 1996-03-14 Basf Ag Polyetheramine enthaltende Kraftstoffe für Ottomotoren
DE19525938A1 (de) 1995-07-17 1997-01-23 Basf Ag Verfahren zur Herstellung von organischen Stickstoffverbindungen, spezielle organische Stickstoffverbindungen und Mischungen aus solchen Verbindungen sowie deren Verwendung als Kraft- und Schmierstoffadditive
DE19620262A1 (de) 1996-05-20 1997-11-27 Basf Ag Verfahren zur Herstellung von Polyalkenaminen
FR2751982B1 (fr) 1996-07-31 2000-03-03 Elf Antar France Additif d'onctuosite pour carburant moteurs et composition de carburants
GB9618546D0 (en) 1996-09-05 1996-10-16 Bp Chemicals Additives Dispersants/detergents for hydrocarbons fuels
DE19754039A1 (de) 1997-12-05 1999-06-24 Basf Ag Verfahren zur Herstellung von Ethylencopolymeren in segmentierten Rohrreaktoren und Verwendung der Copolymere als Fließverbesserer
RU2137813C1 (ru) * 1998-01-06 1999-09-20 Соколов Борис Геннадиевич Депрессорная присадка для нефти и нефтепродуктов
GB9827366D0 (en) 1998-12-11 1999-02-03 Exxon Chemical Patents Inc Macromolecular materials
DE19905211A1 (de) 1999-02-09 2000-08-10 Basf Ag Kraftstoffzusammensetzung
AU2001248679A1 (en) 2000-03-31 2001-10-08 Texaco Development Corporation Fuel additive composition for improving delivery of friction modifier
DE10102913A1 (de) 2001-01-23 2002-07-25 Basf Ag Alkoxylierte Alkyphenole und deren Verwendung in Kraft- und Schmierstoffen
DE10123553A1 (de) * 2001-05-15 2002-11-21 Basf Ag Verfahren zur Herstellung von Polyalkenylsuccinimidprodukten, neue Polyalkenylsuccinimidprodukte mit verbesserten Eigenschaften, Zwischenprodukte und Verwendungen
FR2827608B1 (fr) * 2001-07-17 2004-01-16 Elf Antar France Polymeres a base d'olefine et d'alkylate d'alkenyle et leur utilisation comme additif multifonctionnel dans les carburants et les combustiles
DE10247795A1 (de) 2002-10-14 2004-04-22 Basf Ag Verwendung von Hydrocarbylvinyletherhomopolymeren zur Verbesserung der Wirkung von Kaltfliessverbesserern
DE10316871A1 (de) 2003-04-11 2004-10-21 Basf Ag Kraftstoffzusammensetzung
DE10356595A1 (de) 2003-12-04 2005-06-30 Basf Ag Brennstoffölzusammensetzungen mit verbesserten Kaltfließeigenschaften
MX2007000844A (es) * 2004-08-06 2007-04-17 Basf Ag Aditivos de poliamina para combustibles y lubricantes.
KR101314378B1 (ko) 2005-06-16 2013-10-15 더루우브리졸코오포레이션 연료용 4차 암모늄염 청정제
US20080113890A1 (en) 2006-11-09 2008-05-15 The Lubrizol Corporation Quaternary Ammonium Salt of a Polyalkene-Substituted Amine Compound
US20080182767A1 (en) * 2007-01-29 2008-07-31 Loper John T Compounds and Lubricating Compositions Containing the Compounds
EP2033945A1 (en) 2007-09-06 2009-03-11 Infineum International Limited Quaternary ammonium salts
DK2430131T3 (en) 2009-05-15 2017-12-04 Lubrizol Corp QUATERNARY AMMONIUM AMIDS SALTS
GB201001920D0 (en) 2010-02-05 2010-03-24 Innospec Ltd Fuel compostions
GB201003973D0 (en) 2010-03-10 2010-04-21 Innospec Ltd Fuel compositions
CN105542884B (zh) 2010-05-18 2018-01-23 路博润公司 提供去污力的方法和组合物
JP2013531097A (ja) * 2010-06-25 2013-08-01 ビーエーエスエフ ソシエタス・ヨーロピア 四級化コポリマー
EP2808350B1 (de) 2010-07-06 2017-10-25 Basf Se Säurefreie quaternisierte Stickstoffverbindungen und deren Verwendung als Additive in Kraft- und Schmierstoffen
US20130133243A1 (en) * 2011-06-28 2013-05-30 Basf Se Quaternized nitrogen compounds and use thereof as additives in fuels and lubricants
CA2789907A1 (en) 2011-11-11 2013-05-11 Afton Chemical Corporation Fuel additive for improved performance of direct fuel injected engines
US9574149B2 (en) 2011-11-11 2017-02-21 Afton Chemical Corporation Fuel additive for improved performance of direct fuel injected engines
US10131859B2 (en) 2011-12-30 2018-11-20 Butamax Advanced Biofuels Llc Corrosion inhibitor compositions for oxygenated gasolines
MY186439A (en) 2013-06-07 2021-07-22 Basf Se Use of nitrogen compounds quaternised with alkylene oxide and hydrocarbyl-substituted polycarboxylic acid as additives in fuels and lubricants
PL3099720T3 (pl) * 2014-01-29 2018-12-31 Basf Se Zastosowanie dodatków opartych na kwasach polikarboksylowych do paliw silnikowych
US10377958B2 (en) 2014-01-29 2019-08-13 Basf Se Corrosion inhibitors for fuels and lubricants

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5080686A (en) * 1982-10-20 1992-01-14 Petrolite Corporation Alkyl or alkenyl succinic acids as corrosion inhibitors for oxygenated fuels
US5358651A (en) * 1985-10-25 1994-10-25 The Lubrizol Corporation Compositions, concentrates, lubricant compositions, fuel composition and methods for improving fuel economy of internal combustion engines
US20020026028A1 (en) * 2000-07-11 2002-02-28 Ulrich Epple Low molar mass aliphatic polyester polyols, their preparation and use in high performance coating compositions
US20050126070A1 (en) * 2003-12-11 2005-06-16 Clariant Gmbh Fuel oils composed of middle distillates and oils of vegetable or animal origin and having improved cold flow properties

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111849588A (zh) * 2020-08-18 2020-10-30 上海金兆节能科技有限公司 抗磨润滑脂及其制备方法
CN111925857A (zh) * 2020-08-18 2020-11-13 上海金兆节能科技有限公司 抗磨微量润滑油及制备方法

Also Published As

Publication number Publication date
KR20160114161A (ko) 2016-10-04
RU2016134922A3 (zh) 2018-09-25
US20170183590A1 (en) 2017-06-29
US10377958B2 (en) 2019-08-13
CN106062154A (zh) 2016-10-26
US10240100B2 (en) 2019-03-26
BR112016017418A8 (pt) 2020-06-16
RU2016134921A3 (zh) 2018-09-24
AU2015212878A1 (en) 2016-08-25
KR20160114159A (ko) 2016-10-04
CN106062154B (zh) 2019-12-13
EP3099767A1 (de) 2016-12-07
US10150927B2 (en) 2018-12-11
EP3099769A1 (de) 2016-12-07
SG11201605508UA (en) 2016-08-30
ZA201605889B (en) 2017-11-29
RU2016134920A3 (zh) 2018-09-24
RU2689799C2 (ru) 2019-05-29
US20170066986A1 (en) 2017-03-09
WO2015114029A1 (de) 2015-08-06
KR20160114145A (ko) 2016-10-04
RU2684323C2 (ru) 2019-04-08
US20170037336A1 (en) 2017-02-09
SG11201606143VA (en) 2016-08-30
EP3099768A1 (de) 2016-12-07
CA2938220A1 (en) 2015-08-06
AU2015212878B2 (en) 2018-03-29
AU2015212854B2 (en) 2018-03-29
ES2756578T3 (es) 2020-04-27
CN106459811B (zh) 2020-02-18
WO2015114051A1 (de) 2015-08-06
CA2938218A1 (en) 2015-08-06
RU2685271C2 (ru) 2019-04-17
EP3099768B1 (de) 2019-08-21
AU2015212854A1 (en) 2016-08-18
WO2015114053A1 (de) 2015-08-06
BR112016017414A2 (pt) 2017-08-08
RU2016134920A (ru) 2018-03-05
BR112016017418A2 (pt) 2017-08-08
KR102378650B1 (ko) 2022-03-24
RU2016134922A (ru) 2018-03-05
CN106459811A (zh) 2017-02-22
CN106133120B (zh) 2019-12-13
RU2016134921A (ru) 2018-03-05
PL3099768T3 (pl) 2020-02-28

Similar Documents

Publication Publication Date Title
CN106133120A (zh) 用于燃料和润滑油的腐蚀抑制剂
CN104884585B (zh) 烃基环氧化物的季铵化铵盐及其作为燃料和润滑剂中的添加剂的用途
CN104114682B (zh) 季铵化烷基胺作为燃料和润滑剂中的添加剂的用途
CN103764806B (zh) 季铵化氮化合物及其在燃料和润滑剂中作为添加剂的用途
CN105849238B (zh) 用环氧烷烃和烃基取代的多羧酸季铵化的氮化合物作为燃料和润滑剂中的添加剂的用途
KR101092726B1 (ko) 저온 흐름 개선제의 효과를 증가시키기 위한 히드로카르빌비닐 에테르 단독중합체의 용도
CN101473018B (zh) 作为燃料的石蜡分散剂的极性油溶性氮化合物与酰胺的混合物
RU2377278C2 (ru) Депрессантные присадки для композиций масел
CN107001535B (zh) 共聚物及其用于降低燃料中的链烷烃晶体结晶的用途
CN107849478A (zh) 用于燃料和润滑油的腐蚀抑制剂
CN109312242A (zh) 作为用于燃料和润滑剂的添加剂的共聚物
EA025254B1 (ru) Модифицированные алкилфенолальдегидные смолы, их применение в качестве добавок для улучшения свойств жидких углеводородных топлив в холодных условиях
CN105324468A (zh) 作为燃料的添加剂的甜菜碱化合物
CN102858811B (zh) 季铵化三元共聚物
CN110088253A (zh) 作为燃料添加剂的聚合物
JP2001192681A (ja) 組成物
KR20160075699A (ko) 연료 첨가제로서의 알콕실화 폴리테트라히드로푸란의 용도
CN107849471A (zh) 作为用于燃料和润滑剂的添加剂的共聚物
JP3657611B2 (ja) 油添加剤、組成物及びそれに使用するためのポリマー
CA3066844A1 (en) Winterized pour point depressants
DE212016000150U1 (de) Korrosionsinhibitoren für Kraft- und Schmierstoffe
DE212015000271U1 (de) Korrosionsinhibitoren für Kraft- und Schmierstoffe
WO2019002167A1 (en) SPRAY DRAWERS SUITABLE FOR WINTER

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
REG Reference to a national code

Ref country code: HK

Ref legal event code: DE

Ref document number: 1227919

Country of ref document: HK

GR01 Patent grant
GR01 Patent grant
REG Reference to a national code

Ref country code: HK

Ref legal event code: WD

Ref document number: 1227919

Country of ref document: HK