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CN101351531A - Stabilized biodiesel fuel compositions - Google Patents

Stabilized biodiesel fuel compositions Download PDF

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Publication number
CN101351531A
CN101351531A CNA2006800503485A CN200680050348A CN101351531A CN 101351531 A CN101351531 A CN 101351531A CN A2006800503485 A CNA2006800503485 A CN A2006800503485A CN 200680050348 A CN200680050348 A CN 200680050348A CN 101351531 A CN101351531 A CN 101351531A
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alkyl
phenyl
group
oxygen
butyl
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N·R·李
D·R·休斯
P·库萨蒂斯
D·奥伦斯基
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BASF Schweiz AG
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Ciba SC Holding AG
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    • 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
    • C10L1/185—Ethers; Acetals; Ketals; Aldehydes; 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
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    • C10L1/232—Organic compounds containing nitrogen containing nitrogen in a heterocyclic ring
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    • 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
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    • 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
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    • C10L1/18—Organic compounds containing oxygen
    • 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
    • C10L1/185—Ethers; Acetals; Ketals; Aldehydes; Ketones
    • C10L1/1852—Ethers; Acetals; Ketals; Orthoesters
    • C10L1/1855—Cyclic ethers, e.g. epoxides, lactides, lactones
    • 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
    • C10L1/30—Organic compounds compounds not mentioned before (complexes)
    • 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1011—Biomass
    • 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
    • C10L1/182—Organic compounds containing oxygen containing hydroxy groups; Salts thereof
    • C10L1/183—Organic compounds containing oxygen containing hydroxy groups; Salts thereof at least one hydroxy group bound to an aromatic carbon atom
    • 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
    • C10L1/182—Organic compounds containing oxygen containing hydroxy groups; Salts thereof
    • C10L1/183—Organic compounds containing oxygen containing hydroxy groups; Salts thereof at least one hydroxy group bound to an aromatic carbon atom
    • C10L1/1832—Organic compounds containing oxygen containing hydroxy groups; Salts thereof at least one hydroxy group bound to an aromatic carbon atom mono-hydroxy
    • 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
    • C10L1/19—Esters ester radical containing compounds; ester ethers; carbonic acid esters
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00—Technologies for the production of fuel of non-fossil origin
    • Y02E50/10—Biofuels, e.g. bio-diesel
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Liquid Carbonaceous Fuels (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Cosmetics (AREA)

Abstract

Disclosed are stabilized biodiesel fuel compositions, which compositions comprise a bio- diesel fuel, for example the methyl esters of the fatty acids of rapeseed or soy oil, and one or more additives selected from the group consisting of the 3-arylbenzofuranones and the hin- dered amine light stabilizers, and optionally, one or more hindered phenolic antioxidants.

Description

Stable biodiesel fuel compositions
The present invention relates to biodiesel fuel (or biofuel) composition, its heat resistanceheat resistant by effective amount of stabilizer, the deleterious effect of light and oxygen is stablized, described stablizer is selected from 3-arylbenzofuranones as stabilisers and space hindered amine as light stabilizer, 3-arylbenzofuranones as stabilisers that the stablizer that perhaps described stablizer was selected from and was selected from hindered phenol anti-oxidants is combined and space hindered amine as light stabilizer.
WO2004055141 has instructed the stabilization of fat, oil and food.Described stablizer is selected from 3-aryl benzofuranone, long-chain N, azanol, nitrone and the amine oxide of N-dialkyl group azanol, replacement.
U.S. patent No.6548580 has instructed by the space hindered amine or by N-hydroxyl or N-oxygen base (oxyl) derivative and has stablized the goods that Alathon and multipolymer manufacturing are used to store and transport biodiesel fuel.
JP2004059720 discloses the polyoxymethylene resin that contains hindered amine as light stabilizer, and it is used for the part that directly contacts with biodiesel fuel.
EP1170296 has instructed a kind of method that is used to prepare 3-aryl-benzofuranone.Fuel dope is wherein disclosed.
EP1486555, EP1484387 and EP1484388 disclose a kind of low-corrosiveness fuel composition, and it is used for the blue-flame stove of boiler or the Huang Yanlu of optimization.
Biodiesel fuel is as renewable fuel source and more and more important.It can for example act as a fuel and itself use, and perhaps can be used in combination with diesel oil fuel.
The invention discloses biodiesel fuel compositions, its deleterious effect for heat, light and oxygen is stable, and said composition comprises:
Biodiesel fuel and
Effective one or more additives of stable quantity, this additive be selected from 3-arylbenzofuranones as stabilisers and hindered amine as light stabilizer and
Choose wantonly, be selected from one or more additives of hindered phenol anti-oxidants.
A kind of stable method of deleterious effect that is used to make biodiesel fuel heat resistanceheat resistant, light and oxygen is also disclosed, this method comprises one or more additives of sneaking into effective stable quantity in biodiesel fuel, this additive is selected from 3-arylbenzofuranones as stabilisers and hindered amine as light stabilizer and optional, and one or more are selected from the additive of hindered phenol anti-oxidants.
Biodiesel fuel is a kind of renewable resources and more and more important.
Biodiesel fuel comprises the low alkyl group fatty acid ester, and for example for example methyl alcohol or alcoholic acid transesterify prepare by tri-glyceride and lower alcohol for they.A kind of typical biodiesel fuel is the fatty acid methyl ester of rapeseed oil or soybean oil.The source that is used for biodiesel fuel comprises the plant and animal source.The culinary art oil of recycling can be a source of biodiesel fuel.
Biodiesel fuel and preparation thereof for example are disclosed in, in the U.S. Patent No. 5578090,5713965,5891203,6015440,6174501 and 6398707.
Biodiesel fuel of the present invention for example comprises the lower alkyl esters derived from the mixture of the saturated and unsaturated straight chain fatty acid of 12-22 C atom of plant or oleaginous seed.Term " lower alkyl esters " expression C 1-C 5-ester class, particularly methyl ester and ethyl ester.Saturated, monounsaturated and polyunsaturated C 16-C 22The methyl ester mixture of-lipid acid is known as " biofuel " or " Semen Brassicae campestris methyl ester ".
Biodiesel fuel according to the present invention is 100% low alkyl group fatty acid ester, or the combination of low alkyl group fatty acid ester and diesel oil fuel.Described biodiesel fuel is for example about about 95 weight % fatty acid esters of 5-and about about 5 weight % diesel oil fuels of 95-.For example, biodiesel fuel is the about 90 weight % fatty acid esters of about 10-and about about 10 weight % diesel oil fuels of 90-.For example, biodiesel fuel is the about 75 weight % fatty acid esters of about 25-and about about 25 weight % diesel oil fuels of 75-.
3-aryl benzofuranone antioxidant of the present invention is for example to be disclosed in U.S. Patent No. 4325863; U.S.4388244; U.S.5175312; U.S.5252643; U.S.5216052; U.S.5369159; U.S.5488117; U.S.5356966; U.S.5367008; U.S.5428162; U.S.5428177; With among the U.S.5516920 those.
Specially suitable in the present invention 3-aryl benzofuranone is the compound of formula I:
Figure A20068005034800091
Wherein, if n is 1, then
R 1It is naphthyl, phenanthryl, anthryl, 5,6,7,8-tetrahydrochysene-2-naphthyl, 5,6,7,8-tetrahydrochysene-1-naphthyl, thienyl, benzo [b] thienyl, naphtho-[2,3-b] thienyl, thianthrenyl, dibenzofuran group, benzopyranyl, xanthenyl, fen oxathiin base, pyrryl, imidazolyl, pyrazolyl, pyrazinyl, pyrimidyl, pyridazinyl, the indolizine base, isoindolyl, indyl, indazolyl, purine radicals, quinolizinyl, isoquinolyl, quinolyl, 2, the 3-phthalazinyl, 1, the 5-phthalazinyl, quinoxalinyl, quinazolyl, the cinnolines base, pteridyl, carbazyl, the β-Ka Lin base, phenanthridinyl, acridyl, perimidinyl, the phenanthroline base, phenazinyl, isothiazolyl, phenothiazinyl isoxazolyl, the furazan base, biphenyl, terphenyl, fluorenyl or phenoxazinyl, perhaps any one substituted these carbocyclic rings or heterocyclic group, it is to use C 1-C 4Alkyl-, C 1-C 4Alkoxyl group-, C 1-C 4The alkyl sulfenyl-, hydroxyl-, halo-, amino-, C 1-C 4Alkylamino-, phenyl amino-or two (C 1-C 4Alkyl) amino replaces; Perhaps R 1It is the group of formula II
Figure A20068005034800101
And
If n is 2, then
R1 is unsubstituted or C 1-C 4Alkyl-or the hydroxyl phenylene or the naphthylidene that replace; Or-R 12-X-R 13-,
R 2, R 3, R 4And R 5Be hydrogen, chlorine, hydroxyl, C independently of one another 1-C 25Alkyl, C 7-C 9Benzene alkyl, unsubstituted or C 1-C 4The phenyl that alkyl replaces; Unsubstituted or C 1-C 4The C that alkyl replaces 5-C 8Cycloalkyl; C 1-C 18Alkoxyl group, C 1-C 18Alkylthio, C 1-C 4Alkylamino, two (C 1-C 4Alkyl) amino, C 1-C 25Alkanoyloxy, C 1-C 25Alkanoylamino, C 3-C 25Alkenoyl oxygen base, with oxygen, sulphur or
Figure A20068005034800102
The C that interrupts 3-C 25Alkanoyloxy; C 6-C 9Cycloalkyl-ketonic oxygen base, benzoyloxy or C 1-C 12The benzoyloxy that alkyl replaces; Or, as selectable, if radicals R 2With R 3Perhaps radicals R 3With R 4Perhaps radicals R 4With R 5, form the benzo ring with the C atom that they connected, so R 4Additionally be-(CH 2) p-COR 15Perhaps-(CH 2) qOH or, if R 3, R 5And R 6Be hydrogen, R so 4Additionally be the group of formula III:
Figure A20068005034800111
R wherein 1Definition is with the top definition that is used for n=1,
R 6Be the group of hydrogen or formula IV:
Figure A20068005034800112
Here R 4Not the group and the R of formula III 1Definition is with the top definition that is used for n=1, R 7, R 8, R 9, R 10And R 11Be hydrogen, halogen, hydroxyl, C independently of one another 1-C 25Alkyl, with oxygen, sulphur or
Figure A20068005034800113
The C that interrupts 2-C 25Alkyl; C 1-C 25Alkoxyl group, with oxygen, sulphur or
Figure A20068005034800114
The C that interrupts 2-C 25Alkoxyl group; C 1-C 25Alkylthio, C 3-C 25Alkenyl, C 3-C 25Alkenyloxy, C 3-C 25Alkynyl, C 3-C 25Alkynyloxy group, C 7-C 9Benzene alkyl, C 7-C 9Phenyl alkoxyl group, unsubstituted or C 1-C 4The phenyl that alkyl replaces; Unsubstituted or C 1-C 4The phenoxy group that alkyl replaces; Unsubstituted or C 1-C 4The C that alkyl replaces 5-C 8Cycloalkyl; Unsubstituted or C 1-C 4The C that alkyl replaces 5-C 8Cycloalkyloxy; C 1-C 4Alkylamino, two (C 1-C 4Alkyl) amino, C 1-C 25Alkyloyl, with oxygen, sulphur or
Figure A20068005034800115
The C that interrupts 3-C 25Alkyloyl; C 1-C 25Alkanoyloxy, with oxygen, sulphur or
Figure A20068005034800116
The C that interrupts 3-C 25Alkanoyloxy; C 1-C 25Alkanoylamino, C 3-C 25Alkenoyl, with oxygen, sulphur or
Figure A20068005034800117
The C that interrupts 3-C 25Alkenoyl; C 3-C 25Chain ene acyloxy, with oxygen, sulphur or
Figure A20068005034800118
The C that interrupts 3-C 25Chain ene acyloxy; C 6-C 9Naphthene base carbonyl, C 6-C 9Naphthene base carbonyl oxygen base, benzoyl or C 1-C 12The benzoyl that alkyl replaces; Benzoyloxy or C 1-C 12The benzoyloxy that alkyl replaces;
Figure A20068005034800121
Perhaps
Figure A20068005034800122
, perhaps, selectively, in formula II, radicals R 7And R 8Perhaps radicals R 8And R 11, form phenyl ring with the C atom that they connected,
R 12And R 13Be unsubstituted or C independently of one another 1-C 4Phenylene or naphthylidene that alkyl replaces,
R 14Be hydrogen or C 1-C 8Alkyl,
R 15Be hydroxyl,
Figure A20068005034800123
, C 1-C 18Alkoxyl group or
Figure A20068005034800124
R 16And R 17Be hydrogen, CF independently of one another 3, C 1-C 12Alkyl or phenyl, perhaps R 16And R 17, form unsubstituted or with 1-3 C with the C atom that they connected 1-C 4The C that alkyl replaces 5-C 8The ring alkylidene;
R 18And R 19Be hydrogen, C independently of one another 1-C 4Alkyl or phenyl,
R 20Be hydrogen or C 1-C 4Alkyl,
R 21Be hydrogen, unsubstituted or C 1-C 4The phenyl that alkyl replaces; C 1-C 25Alkyl, with oxygen, sulphur or
Figure A20068005034800125
The C that interrupts 2-C 25Alkyl; Unsubstituted or with 1-3 C 1-C 4The C that alkyl replaces on phenyl 7-C 9The benzene alkyl; Unsubstituted or with 1-3 C 1-C 4That alkyl replaces on phenyl and with oxygen, sulphur or
Figure A20068005034800126
The C that interrupts 7-C 25The benzene alkyl, perhaps, selectively, radicals R 20And R 21, the C atom that connects with them forms C 5-C 12Cycloalkylidene ring, this ring are unsubstituted or with 1-3 C 1-C 4Alkyl replaces;
R 22Be hydrogen or C 1-C 4Alkyl,
R 23Be hydrogen, C 1-C 25Alkyloyl, C 3-C 25Alkenoyl, with oxygen, sulphur or
Figure A20068005034800127
The C that interrupts 3-C 25Alkyloyl; With two (C 1-C 6Alkyl) C of phosphonate groups replacement 2-C 25Alkyloyl; C 6-C 9Naphthene base carbonyl, Thenoyl, furoyl base, benzoyl or C 1-C 12The benzoyl that alkyl replaces;
Figure A20068005034800131
Figure A20068005034800132
Or
R 24And R 25Be hydrogen or C independently of one another 1-C 18Alkyl,
R 26Be hydrogen or C 1-C 8Alkyl,
R 27Be direct key, C 1-C 18Alkylidene group, with oxygen, sulphur or
Figure A20068005034800134
The C that interrupts 2-C 18Alkylidene group; C 2-C 18Alkylene group, C 2-C 20Alkylidene, C 7-C 20Phenyl alkylidene, C 5-C 8Cycloalkylidene, C 7-C 8Inferior bicyclic alkyl, unsubstituted or C 1-C 4The phenylene that alkyl replaces, perhaps
Figure A20068005034800135
Or
Figure A20068005034800136
R 28Be hydroxyl,
Figure A20068005034800137
, C 1-C 18Alkoxyl group or
Figure A20068005034800138
R 29Be oxygen ,-NH-or
Figure A20068005034800139
R 30Be C 1-C 18Alkyl or phenyl,
R 31Be hydrogen or C 1-C 18Alkyl,
M is a r valency metallic cation,
X be direct key, oxygen, sulphur or-NR 31-,
N is 1 or 2,
P is 0,1 or 2,
Q is 1,2,3,4,5 or 6,
R be 1,2 or 3 and
S is 0,1 or 2.
Naphthyl, phenanthryl, anthryl, 5,6,7,8-tetrahydrochysene-2-naphthyl, 5,6,7,8-tetrahydrochysene-1-naphthyl, thienyl, benzo [b] thienyl, naphtho-[2,3-b] thienyl, thianthrenyl, dibenzofuran group, benzopyranyl, xanthenyl, fen oxathiin base, pyrryl, imidazolyl, pyrazolyl, pyrazinyl, pyrimidyl, pyridazinyl, the indolizine base, isoindolyl, indyl, indazolyl, purine radicals, quinolizinyl, isoquinolyl, quinolyl, 2, the 3-phthalazinyl, 1, the 5-phthalazinyl, quinoxalinyl, quinazolyl, the cinnolines base, pteridyl, carbazyl, the β-Ka Lin base, phenanthridinyl, acridyl, perimidinyl, the phenanthroline base, phenazinyl, isothiazolyl, phenothiazinyl isoxazolyl, the furazan base, biphenyl, terphenyl, fluorenyl or phenoxazinyl or any one substituted these carbocyclic rings or heterocyclic group, it is to use C 1-C 4Alkyl-, C 1-C 4Alkoxyl group-, C 1-C 4Alkylthio-, hydroxyl-, halo-, amino-, C 1-C 4Alkylamino-, phenyl amino-or two (C 1-C 4Alkyl) amino replaces, for example, the 1-naphthyl, the 2-naphthyl, 1-phenyl amino-4-naphthyl, 1-methyl naphthyl, 2-methyl naphthyl, 1-methoxyl group-2-naphthyl, 2-methoxyl group-1-naphthyl, 1-dimethylamino-2-naphthyl, 1,2-dimethyl-4-naphthyl, 1,2-dimethyl-6-naphthyl, 1,2-dimethyl-7-naphthyl, 1,3-dimethyl-6-naphthyl, 1,4-dimethyl-6-naphthyl, 1,5-dimethyl-2-naphthyl, 1,6-dimethyl-2-naphthyl, 1-hydroxyl-2-naphthyl, 2-hydroxyl-1-naphthyl, 1,4-dihydroxyl-2-naphthyl, 7-phenanthryl, 1-anthryl, the 2-anthryl, the 9-anthryl, 3-benzo [b] thienyl, 5-benzo [b] thienyl, 2-benzo [b] thienyl, the 4-dibenzofuran group, 4, the 7-dibenzofuran group, 4-methyl-7-dibenzofuran group, the 2-xanthenyl, 8-methyl-2-xanthenyl, 3-xanthenyl, 2-fen oxathiin base, 2,7-fen oxathiin base, 2-pyrryl, the 3-pyrryl, 5-methyl-3-pyrryl, 2-imidazolyl, 4-imidazolyl, the 5-imidazolyl, 2-methyl-4-imidazolyl, 2-ethyl-4-imidazolyl, 2-ethyl-5-imidazolyl, the 3-pyrazolyl, 1-methyl-3-pyrazolyl, 1-propyl group-4-pyrazolyl, 2-pyrazinyl, 5,6-dimethyl-2-pyrazinyl, 2-indolizine base, 2-methyl-3-isoindolyl, 2-methyl isophthalic acid-isoindolyl, 1-methyl-2-indyl, 1-methyl-3-indyl, 1,5-dimethyl-2-indyl, 1-methyl-3-indazolyl, 2,7-dimethyl-8-purine radicals, 2-methoxyl group-7-methyl-8-purine radicals, the 2-quinolizinyl, 3-isoquinolyl, 6-isoquinolyl, the 7-isoquinolyl, isoquinolyl, 3-methoxyl group-6-isoquinolyl, 2-quinolyl, the 6-quinolyl, the 7-quinolyl, 2-methoxyl group-3-quinolyl, 2-methoxyl group-6-quinolyl, 6-2, the 3-phthalazinyl, 7-2,3-phthalazinyl, 1-methoxyl group-6-2, the 3-phthalazinyl, 1,4-dimethoxy-6-2, the 3-phthalazinyl, 1,8-naphthyridine-2-base, 2-quinoxalinyl, the 6-quinoxalinyl, 2,3-dimethyl-6-quinoxalinyl, 2,3-dimethoxy-6-quinoxalinyl, the 2-quinazolyl, 7-quinazolyl, 2-dimethylamino-6-quinazolyl, 3-cinnolines base, 6-cinnolines base, 7-cinnolines base, 3-methoxyl group-7-cinnolines base, the 2-pteridyl, the 6-pteridyl, 7-pteridyl, 6,7-dimethoxy-2-pteridyl, the 2-carbazyl, 3-carbazyl, 9-methyl-2-carbazyl, 9-methyl-3-carbazyl, β-Ka Lin-3-base, 1-methyl-β-Ka Lin-3-base, 1-methyl-β-Ka Lin-6-base, the 3-phenanthridinyl, the 2-acridyl, 3-acridyl, 2-perimidinyl, 1-methyl-5-perimidinyl, 5-phenanthroline base, 6-phenanthroline base, 1-phenazinyl, the 2-phenazinyl, the 3-isothiazolyl, 4-isothiazolyl, 5-isothiazolyl, the 2-phenothiazinyl, the 3-phenothiazinyl, 10-methyl-3-phenothiazinyl, 3-isoxazolyl, the 4-isoxazolyl, the 5-isoxazolyl, 4-methyl-3-furazan base, 2-phenoxazinyl or 10-methyl-2-phenoxazinyl.
That especially preferably provide is unsubstituted or C 1-C 4Alkyl-, C 1-C 4Alkoxyl group-, C 1-C 4Alkylthio-, hydroxyl-, phenyl amino-or two (C 1-C 4Alkyl) the amino naphthyl that replaces, phenanthryl, anthryl, 5,6,7,8-tetrahydrochysene-2-naphthyl, 5,6,7,8-tetrahydrochysene-1-naphthyl, thienyl, benzo [b] thienyl, naphtho-[2,3-b] thienyl, thianthrenyl, dibenzofuran group, benzopyranyl, xanthenyl, fen oxathiin base, pyrryl, isoindolyl, indyl, phenothiazinyl, biphenyl, terphenyl, fluorenyl or phenoxazinyl, for example, the 1-naphthyl, 2-naphthyl, 1-phenyl amino-4-naphthyl, 1-methyl naphthyl, 2-methyl naphthyl, 1-methoxyl group-2-naphthyl, 2-methoxyl group-1-naphthyl, 1-dimethylamino-2-naphthyl, 1,2-dimethyl-4-naphthyl, 1,2-dimethyl-6-naphthyl, 1,2-dimethyl-7-naphthyl, 1,3-dimethyl-6-naphthyl, 1,4-dimethyl-6-naphthyl, 1,5-dimethyl-2-naphthyl, 1,6-dimethyl-2-naphthyl, 1-hydroxyl-2-naphthyl, 2-hydroxyl-1-naphthyl, 1,4-dihydroxyl-2-naphthyl, 7-phenanthryl, the 1-anthryl, 2-anthryl, 9-anthryl, 3-benzo [b] thienyl, 5-benzo [b] thienyl, 2-benzo [b] thienyl, the 4-dibenzofuran group, 4, the 7-dibenzofuran group, 4-methyl-7-dibenzofuran group, 2-xanthenyl, 8-methyl-2-xanthenyl, the 3-xanthenyl, 2-pyrryl, 3-pyrryl, the 2-phenothiazinyl, 3-phenothiazinyl, 10-methyl-3-phenothiazinyl.
Halogen (halo) for example is, chlorine, bromine or iodine.What preferably provide is chlorine.
Having the alkyloyl that is up to 25 C atoms is side chain or the group of non-side chain, for example, and formyl radical, ethanoyl; propionyl, butyryl radicals, pentanoyl, caproyl; oenanthyl, capryloyl, nonanoyl, decanoyl; undecanoyl, lauroyl, tridecanoyl; tetradecanoyl, pentadecanoyl, hexadecanoyl; heptadecane acyl group, octadecanoyl, eicosane acyl group or docosane acyl group.What preferably provide is to have 2-18, particularly 2-12, for example alkyloyl of 2-6 C atom.What especially preferably provide is ethanoyl.
With two (C 1-C 6Alkyl) C of phosphonate groups replacement 2-C 25Alkyloyl for example is, (CH 3CH 2O) 2POCH 2CO-, (CH 3O) 2POCH 2CO-, (CH 3CH 2CH 2CH 2O) 2POCH 2CO-, (CH 3CH 2O) 2POCH 2CH 2CO-, (CH 3O) 2POCH 2CH 2CO-, (CH 3CH 2CH 2CH 2O) 2POCH 2CH 2CO-, (CH 3CH 2O) 2PO (CH 2) 4CO-, (CH 3CH 2O) 2PO (CH 2) 8CO-or (CH 3CH 2O) 2PO (CH 2) 17CO-.
Have that to be up to 25 C atom alkanoyloxies be side chain or the group of non-side chain, for example, methanoyl, acetoxyl group, propionyloxy, butyryl acyloxy, penta acyloxy, hexylyloxy, heptan acyloxy, hot acyloxy, the ninth of the ten Heavenly Stems acyloxy, the last of the ten Heavenly stems acyloxy, undecane acyl-oxygen base, dodecane acyl-oxygen base, tridecane acyl-oxygen base, mnyristoyl oxygen base, pentadecane acyl-oxygen base, n-Hexadecane acyl-oxygen base, heptadecane acyl-oxygen base, octadecane acyl-oxygen base, eicosane acyloxy or docosane acyloxy.What preferably provide is to have 2-18, particularly 2-12, for example alkanoyloxy of 2-6 C atom.What especially preferably provide is acetoxyl group.
Alkenoyl with 3-25 C atom is side chain or the group of non-side chain, for example, and acryl; the 2-butylene acyl group, 3-crotonoyl, methacryloyl; positive 2; 4-pentadiene acyl group, 3-methyl-2-butene acyl group, positive 2-octene acyl group; positive 2-dodecylene acyl group; different dodecylene acyl group, oleoyl, positive 2-vaccenic acid acyl group or positive 4-vaccenic acid acyl group.What preferably provide is to have 3-18, particularly 3-12, for example alkenoyl of 3-6, especially 3-4 C atom.
With oxygen, sulphur or
Figure A20068005034800161
The C that interrupts 3-C 25Alkenoyl is, for example CH 3OCH 2CH 2CH=CHCO-or CH 3OCH 2CH 2OCH=CHCO-.
Chain ene acyloxy with 3-25 C atom is side chain or the group of non-side chain, for example, and acryloxy, the 2-butylene acyloxy, 3-butylene acyloxy, iso-butylene acyl-oxygen base, positive 2,4-pentadiene acyloxy, 3-methyl-2-butene acyloxy, positive 2-octene acyloxy, positive 2-dodecylene acyloxy, different dodecylene acyloxy, oily acyloxy, positive 2-vaccenic acid acyloxy or positive 4-vaccenic acid acyloxy.What preferably provide is to have 3-18, particularly 3-12, for example chain ene acyloxy of 3-6, especially 3-4 C atom.
With oxygen, sulphur or The C that interrupts 3-C 25Chain ene acyloxy for example is, CH 3OCH 2CH 2CH=CHCOO-or CH 3OCH 2CH 2OCH=CHCOO-.
With oxygen, sulphur or
Figure A20068005034800163
The C that interrupts 3-C 25Alkyloyl is CH for example 3-O-CH 2CO-, CH 3-S-CH 2CO-, CH 3-NH-CH 2CO-, CH 3-N (CH 3)-CH 2CO-, CH 3-O-CH 2CH 2-O-CH 2CO-, CH 3-(O-CH 2CH 2-) 2O-CH 2CO-, CH 3-(O-CH 2CH 2-) 3O-CH 2CO-or CH 3-(O-CH 2CH 2-) 4O-CH 2CO-.
With oxygen, sulphur or
Figure A20068005034800171
The C that interrupts 3-C 25Alkanoyloxy is CH for example 3-O-CH 2COO-, CH 3-S-CH 2COO-, CH 3-NH-CH 2COO-, CH 3-N (CH 3)-CH 2COO-, CH 3-O-CH 2CH 2-O-CH 2COO-, CH 3-(O-CH 2CH 2-) 2O-CH 2COO-, CH 3-(O-CH 2CH 2-) 3O-CH 2COO-or CH 3-(O-CH 2CH 2-) 4O-CH 2COO-.
C 6-C 9Naphthene base carbonyl is a cyclopentylcarbonyl for example, cyclohexyl-carbonyl, suberyl carbonyl or ring octyl group carbonyl.Cyclohexyl-carbonyl is preferred.
C 6-C 9Naphthene base carbonyl oxygen base is, for example cyclopentylcarbonyl oxygen base, cyclohexyl-carbonyl oxygen base, suberyl ketonic oxygen base or ring octyl group ketonic oxygen base.The cyclohexyl-carbonyl oxygen base is preferred.
C 1-C 12The benzoyl that alkyl replaces, it preferably has 1-3, particularly 1 or 2 alkyl group; be for example adjacent-,-or right-methyl benzoyl, 2; the 3-dimethylbenzoyl, 2, the 4-dimethylbenzoyl; 2,5-dimethylbenzoyl, 2; the 6-dimethylbenzoyl, 3, the 4-dimethylbenzoyl; 3,5-dimethylbenzoyl, 2-methyl-6-ethylamino benzonitrile acyl group; 4-tert.-butylbenzene formyl radical; 2-ethylamino benzonitrile acyl group, 2,4; the 6-trimethylbenzoyl; 2,6-dimethyl-4-tert.-butylbenzene formyl radical or 3,5-di-t-butyl benzoyl.Preferred substituted is C 1-C 8Alkyl, particularly C 1-C 4Alkyl.
C 1-C 12The benzoyloxy (it preferably has 1-3, particularly 1 or 2 alkyl group) that alkyl replaces be for example adjacent-, between-or right-toluyl oxygen base, 2,3-dimethyl benzene methanoyl, 2,4-dimethyl-benzoyloxy, 2,5-dimethyl benzene methanoyl, 2,6-dimethyl benzene methanoyl, 3,4-dimethyl benzene methanoyl, 3,5-dimethyl benzene methanoyl, 2-methyl-6-ethylamino benzonitrile acyl-oxygen base, 4-tert.-butylbenzene methanoyl, 2-ethyl-benzoyloxy, 2,4,6-Three methyl Benzene methanoyl, 2,6-dimethyl-4-tert.-butylbenzene methanoyl or 3,5-di-t-butyl-benzoyloxy.Preferred substituted is C 1-C 8Alkyl, particularly C 1-C 4Alkyl.
Having the alkyl that is up to 25 C atoms is side chain or the group of non-side chain, for example, and methyl, ethyl, propyl group, sec.-propyl, normal-butyl, sec-butyl, isobutyl-, the tertiary butyl, the 2-ethyl-butyl, n-pentyl, isopentyl, 1-methyl amyl, 1, the 3-dimethylbutyl, n-hexyl, 1-methyl hexyl, n-heptyl, different heptyl, 1,1,3,3-tetramethyl butyl, 1-methylheptyl, the 3-methylheptyl, n-octyl, 2-ethylhexyl, 1,1,3-trimethylammonium hexyl, 1,1,3,3-tetramethyl-amyl group, nonyl, decyl, undecyl, 1-methyl undecyl, dodecyl, 1,1,3,3,5,5-hexamethyl hexyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, eicosyl or docosyl.R 2And R 4A kind of preferred implication for example be, C 1-C 18Alkyl.R 4Particularly preferred implication is C 1-C 4Alkyl.
Alkenyl with 3-25 C atom is side chain or the group of non-side chain, for example, and propenyl, crotyl, 3-butenyl, isobutenyl, positive 2, the 4-pentadienyl, 3-methyl-2-butene base, positive 2-octenyl, positive 2-dodecenyl succinic, different dodecenyl succinic, oil base, positive 2-vaccenic acid base or positive 4-vaccenic acid base.What preferably provide is to have 3-18, particularly 3-12, for example alkenyl of 3-6, especially 3-4 C atom.
Alkenyloxy with 3-25 C atom is side chain or the group of non-side chain, for example, and propenyloxy group, 2-butylene oxygen base, 3-butenyloxy, iso-butylene oxygen base, positive 2,4-pentadiene oxygen base, 3-methyl-2-butene oxygen base, positive 2-octene oxygen base, positive 2-dodecylene oxygen base, different dodecylene oxygen base, oily oxygen base, positive 2-vaccenic acid oxygen base or positive 4-vaccenic acid oxygen base.What preferably provide is to have 3-18, special 3-12, for example alkenyloxy of 3-6, especially 3-4 C atom.
Alkynyl with 3-25 C atom is side chain or the group of non-side chain, for example, and proyl (CH 2-C ≡ CH), 2-butyne base, 3-butynyl, positive 2-octyne base or positive 2-dodecyne base.What preferably provide is to have 3-18, special 3-12, for example alkynyl of 3-6, especially 3-4 C atom.
Alkynyloxy group with 3-25 C atom is side chain or the group of non-side chain, for example, and the third alkynyloxy group (OCH 2-C ≡ CH), 2-butyne oxygen base, 3-fourth alkynyloxy group, the hot alkynyloxy group of positive 2-, perhaps positive 2-dodecyne oxygen base.What preferably provide is to have 3-18, special 3-12, for example alkynyloxy group of 3-6, especially 3-4 C atom.
With oxygen, sulphur or
Figure A20068005034800181
The C that interrupts 2-C 25Alkyl is CH for example 3-O-CH 2-, CH 3-S-CH 2-, CH 3-NH-CH 2-, CH 3-N (CH 3)-CH 2-, CH 3-O-CH 2CH 2-O-CH 2-, CH 3-(O-CH 2CH 2-) 2O-CH 2-, CH 3-(O-CH 2CH 2-) 3O-CH 2-or CH 3-(O-CH 2CH 2-) 4O-CH 2-.
C 7-C 9The benzene alkyl is a benzyl for example, α-Jia Jibianji, α, α-Er Jiajibianji or 2-phenyl-ethyl.Benzyl and α, α-Er Jiajibianji are preferred.
C 7-C 9(it is unsubstituted or uses 1-3 C on phenyl group the benzene alkyl 1-C 4Alkyl replaces) be benzyl for example, α-Jia Jibianji, α, α-Er Jiajibianji, 2-phenylethyl, 2-methyl-benzyl, 3-methyl-benzyl, 4-methyl-benzyl, 2,4-dimethyl benzyl, 2,6-dimethyl benzyl or 4-tertiary butyl benzyl.Benzyl is preferred.
C 7-C 25(it is unsubstituted or uses 1-3 C on phenyl group the benzene alkyl 1-C 4That alkyl replaces and with oxygen, sulphur or
Figure A20068005034800182
Interrupt) be group side chain or non-side chain, for example, phenoxymethyl, 2-methylenedioxy phenoxy ylmethyl, 3-methylenedioxy phenoxy ylmethyl, 4-methylenedioxy phenoxy ylmethyl, 2,4-dimethyl phenoxy methyl, 2,3-dimethyl phenoxy methyl, phenyl sulfenyl methyl, N-methyl-N-phenyl methyl, N-ethyl-N-phenyl methyl, 4-tertiary butyl phenoxymethyl, 4-tert.-butylbenzene oxygen base oxethyl methyl, 2,4-di-t-butyl phenoxymethyl, 2,4-di-tert-butyl oxygen base oxethyl methyl, phenoxy group ethoxy ethoxy ethoxy methyl, benzyloxymethyl, benzyloxy ethoxyl methyl, N-benzyl-N-ethyl-methyl or N-benzyl-N-isopropyl methyl.
C 7-C 9The phenyl alkoxyl group is a benzyloxy for example, Alpha-Methyl benzyloxy, α, alpha-alpha-dimethyl benzyloxy or 2-phenyl ethoxy.Benzyloxy is preferred.
C 1-C 4The phenyl (it preferably contains 1-3, special 1 or 2 alkyl group) that alkyl replaces be for example adjacent-,-or right-aminomethyl phenyl, 2, the 3-3,5-dimethylphenyl, 2, the 4-3,5-dimethylphenyl, 2,5-3,5-dimethylphenyl, 2, the 6-3,5-dimethylphenyl, 3, the 4-3,5-dimethylphenyl, 3,5-3,5-dimethylphenyl, 2-methyl-6-ethyl-phenyl, the 4-tert-butyl-phenyl, 2-ethylphenyl or 2,6-diethyl phenyl.
C 1-C 4The phenoxy group that alkyl replaces, it preferably contains 1-3, special 1 or 2 alkyl group, be for example adjacent-,-or right-methylphenoxy, 2,3-dimethyl phenoxy, 2,4-dimethyl phenoxy, 2,5-dimethyl phenoxy, 2, the 6-dimethyl phenoxy, 3, the 4-dimethyl phenoxy, 3,5-dimethyl phenoxy, 2-methyl-6-ethyl phenoxy group, 4-tertiary butyl phenoxy group, 2-ethyl phenoxy group or 2,6-diethyl phenoxy group.
Unsubstituted or C 1-C 4The C that alkyl replaces 5-C 8Cycloalkyl is a cyclopentyl for example, methylcyclopentyl, dimethylcyclopentyl, cyclohexyl, methylcyclohexyl, Dimethylcyclohexyl, trimethylammonium-cyclohexyl, tert-butylcyclohexyl, suberyl or ring octyl group.What preferably provide is cyclohexyl and tert-butylcyclohexyl.
Unsubstituted or C 1-C 4The C that alkyl replaces 5-C 8Cycloalkyloxy is a cyclopentyloxy for example, methyl cyclopentyloxy, dimethyl cyclopentyloxy, cyclohexyloxy, methyl cyclohexane oxygen base, dimethyl cyclohexyloxy, 3-methyl cyclohexanol oxygen base, tertiary butyl cyclohexyloxy, ring oxygen base in heptan or ring octyloxy.What preferably provide is cyclohexyloxy and tertiary butyl cyclohexyloxy.
Having the alkoxyl group that is up to 25 C atoms is side chain or the group of non-side chain, methoxyl group for example, oxyethyl group, propoxy-, isopropoxy, n-butoxy, isobutoxy, pentyloxy, isopentyloxy, hexyloxy, heptan the oxygen base, octyloxy, the last of the ten Heavenly stems oxygen base, tetradecyloxyaniline, n-Hexadecane oxygen base or octadecane oxygen base.What preferably provide is to have 1-12, special 1-8, for example alkoxyl group of 1-6 C atom.
With oxygen, sulphur or
Figure A20068005034800201
The C that interrupts 2-C 25Alkoxyl group is CH for example 3-O-CH 2CH 2O-, CH 3-S-CH 2CH 2O-, CH 3-NH-CH 2CH 2O-, CH 3-N (CH 3)-CH 2CH 2O-, CH 3-O-CH 2CH 2-O-CH 2CH 2O-, CH 3-(O-CH 2CH 2-) 2O-CH 2CH 2O-, CH 3-(O-CH 2CH 2-) 3O-CH 2CH 2O-or CH 3-(O-CH 2CH 2-) 4O-CH 2CH 2O-.
Having the alkylthio that is up to 25 C atoms is side chain or the group of non-side chain, for example, and methylthio group, ethylmercapto group, rosickyite base, iprotiazem base, positive butylthio, isobutyl sulfenyl, penta sulfenyl, the isoamyl sulfenyl, own sulfenyl, heptan sulfenyl, hot sulfenyl, the last of the ten Heavenly stems sulfenyl, tetradecane sulfenyl, n-Hexadecane sulfenyl or octadecane sulfenyl.What preferably provide is to have 1-12, special 1-8, for example alkylthio of 1-6 C atom.
Having the alkylamino that is up to 4 C atoms is side chain or the group of non-side chain, for example, and methylamino, ethylamino, propyl group amino, sec.-propyl amino, normal-butyl amino, isobutylamino or tertiary butyl amino.
Two (C 1-C 4Alkyl) amino also represent these two groups independent of each other be side chain or non-side chain, for example, dimethylamino, methylethyl amino, diethylamino, methyl-n-propyl amino, isopropyl methyl amino, methyl-normal-butyl amino, methyl-isobutyl amino, ethyl sec.-propyl amino, ethyl-normal-butyl amino, the ethyl isobutylamino, ethyl-tertiary butyl amino, diethylamino, diisopropylaminoethyl, sec.-propyl-normal-butyl amino, sec.-propyl isobutylamino, di-n-butyl amino or diisobutyl amino.
Having the alkanoylamino that is up to 25 C atoms is side chain or the group of non-side chain, for example, and formyl radical amino; acetylamino; propionyl amino, butyryl radicals amino, pentanoyl amino; caproyl amino; oenanthyl amino, capryloyl amino, nonanoyl amino; decanoyl amino; undecanoyl amino, lauroyl amino, tridecanoyl amino; tetradecanoyl amino; pentadecanoyl amino, hexadecanoyl amino, heptadecane acyl group amino; octadecanoyl amino, eicosane acyl amino or docosane acyl amino.What preferably provide is to have 2-18, special 2-12, for example alkanoylamino of 2-6 C atom.
C 1-C 18Alkylidene group is side chain or the group of non-side chain, for example, and methylene radical, ethylidene, propylidene, trimethylene, tetramethylene, pentamethylene, hexa-methylene, heptamethylene, eight methylene radical, decamethylene, ten dimethylenes or 18 methylene radical.That preferably provide is C 1-C 12Alkylidene group, special C 1-C 8Alkylidene group.
C 1-C 4The C that alkyl replaces 5-C 12(it preferably contains 1-3 to the cycloalkylidene ring, alkyl group group special 1 or 2 side chain or non-side chain) is cyclopentylidene for example, the methyl cyclopentylidene, dimethyl cyclopentylidene, cyclohexylidene, the methyl cyclohexylidene, the dimethyl cyclohexylidene, trimethylammonium cyclohexylidene, tertiary butyl cyclohexylidene, inferior suberyl, inferior ring octyl group or inferior ring decyl.What preferably provide is cyclohexylidene and tertiary butyl cyclohexylidene.
With oxygen, sulphur or
Figure A20068005034800211
The C that interrupts 2-C 18Alkylidene group be for example-CH 2-O-CH 2-,-CH 2-S-CH 2-,-CH 2-NH-CH 2-,-CH 2-N (CH 3)-CH 2-,-CH 2-O-CH 2CH 2-O-CH 2-,-CH 2-(O-CH 2CH 2-) 2O-CH 2-,-CH 2-(O-CH 2CH 2-) 3O-CH 2-,-CH 2-(O-CH 2CH 2-) 4O-CH 2-or-CH 2CH 2-S-CH 2CH 2-.
C 2-C 18The chain alkenylene is for example vinylidene, methyl vinylidene, octenyl ethylidene or dodecylene ethylidene.That preferably provide is C 2-C 8The chain alkenylene.
Alkylidene with 2-20 C atom is an ethidine for example, the propylidene base, fourth fork base, the pentylidene base, 4-methyl pentylidene base, heptan the fork base, the ninth of the ten Heavenly Stems fork base, tridecane fork base, nonadecane fork base, 1-methyl ethidine, 1-ethyl propylidene base or 1-ethyl pentylidene base.That preferably provide is C 2-C 8-alkylidene.
Phenyl alkylidene with 7-20 C atom is a benzal base for example, oneself fork base of 2-phenyl ethidine or 1-phenyl-2-.That preferably provide is C 7-C 9-phenyl alkylidene.
C 5-C 8Cycloalkylidene is the stable hydrocarbon group with two free valencys and at least one ring element, and it is for example cyclopentylidene, cyclohexylidene, inferior suberyl or inferior ring octyl group.What preferably provide is cyclohexylidene.C 7-C 8Inferior bicyclic alkyl is for example inferior two suberyl or inferior two ring octyl groups.
Unsubstituted or C 1-C 4Phenylene that alkyl replaces or naphthylidene are for example 1,2-, 1,3-, 1,4-phenylene, 1,2-, 1,3-, 1,4-, 1,6-, 1,7-, 2,6-or 2,7-naphthylidene.1, the 4-phenylene is preferred.
C 1-C 4The C that alkyl replaces 5-C 8(it preferably contains 1-3 to cycloalkanes fork basic ring, alkyl group particularly 1 or 2 side chain or non-side chain) group is a cyclopentylidene base for example, methyl cyclopentylidene base, dimethyl cyclopentylidene base, cyclohexylidene base, methyl cyclohexane fork base, dimethyl cyclohexylidene base, 3-methyl cyclohexanol fork base, tertiary butyl cyclohexylidene base, the hot fork base of ring fork in heptan base or ring.What preferably provide is cyclohexylidene base and tertiary butyl cyclohexylidene base.Single-, two or trivalent metal cation basic metal preferably, alkaline-earth metal or aluminium cations, for example, Na+, K+, Mg++, Ca++ or Al+++.
A kind of particularly preferred composition of the present invention contains the 3-aryl benzofuranone of at least a formula I, wherein, if n=1, R 1Be unsubstituted or at contraposition C 1-C 18Alkylthio or two (C 1-C 4Alkyl) the amino phenyl that replaces; Single-to the alkane phenyl of five-replacement, it contains maximum 18 C atoms altogether in 1-5 alkyl substituent; Naphthyl, biphenyl, terphenyl, phenanthryl, anthryl, fluorenyl, carbazyl, thienyl, pyrryl, phenothiazinyl or 5,6,7, the 8-tetralyl, its each be unsubstituted or use C 1-C 4Alkyl, C 1-C 4Alkoxyl group, C 1-C 4Alkylthio, hydroxyl or amino replace.
What preferably provide is the compound of formula I, wherein, if n is 2, then
R 1Be-R 12-X-R 13-,
R 12And R 13Be phenylene,
X be oxygen or-NR 31-and
R 31Be C 1-C 4Alkyl.
What also preferably provide is the compound of formula I, wherein, if n is 1,
R 1Be unsubstituted or C 1-C 4Alkyl-, C 1-C 4Alkoxyl group-, C 1-C 4Alkylthio-, hydroxyl-, halo-, amino-, C 1-C 4Alkylamino-or two (C 1-C 4-alkyl) the amino naphthyl that replaces, phenanthryl, thienyl, dibenzofuran group, carbazyl, the group of fluorenyl or formula II, wherein
R 7, R 8, R 9, R 10And R 11Independent of each other is hydrogen, chlorine, bromine, hydroxyl, C 1-C 18Alkyl is with the C of oxygen or sulphur interruption 2-C 18Alkyl; C 1-C 18Alkoxyl group is with the C of oxygen or sulphur interruption 2-C 18Alkoxyl group; C 1-C 18Alkylthio, C 3-C 12Alkenyloxy, C 3-C 12Alkynyloxy group, C 7-C 9The benzene alkyl, C 7-C 9The phenyl alkoxyl group, unsubstituted or C 1-C 4The phenyl that alkyl replaces; Phenoxy group, cyclohexyl, C 5-C 8Cycloalkyloxy, C 1-C 4Alkylamino, two (C 1-C 4-alkyl) amino, C 1-C 12Alkyloyl is with the C of oxygen or sulphur interruption 3-C 12Alkyloyl; C 1-C 12Alkanoyloxy is with the C of oxygen or sulphur interruption 3-C 12Alkanoyloxy; C 1-C 12Alkanoylamino, C 3-C 12Alkenoyl, C 3-C 12Chain ene acyloxy, cyclohexyl-carbonyl, cyclohexyl-carbonyl oxygen base, benzoyl or C 1-C 4The benzoyl that alkyl replaces; Benzoyloxy or C 1-C 4The benzoyloxy that alkyl replaces;
Figure A20068005034800221
Perhaps
Figure A20068005034800222
, perhaps selectable, in formula II, radicals R 7And R 8Or radicals R 8And R 11, form phenyl ring with the C atom that they connected,
R 15Be hydroxyl, C 1-C 12Alkoxyl group or
Figure A20068005034800223
R 18And R 19Be hydrogen or C independently of one another 1-C 4Alkyl,
R 20Be hydrogen,
R 21Be hydrogen, phenyl, C 1-C 18Alkyl is with the C of oxygen or sulphur interruption 2-C 18Alkyl; C 7-C 9The benzene alkyl, C 7-C 18-benzene alkyl, its unsubstituted or on phenyl group with 1-3 C 1-C 4That alkyl replaces and interrupt, perhaps selectable with oxygen or sulphur, radicals R 20And R 21, forming the cyclohexylidene ring with the C atom that they connected, this ring is unsubstituted or with 1-3 C 1-C 4Alkyl replaces,
R 22Be hydrogen or C 1-C 4Alkyl,
R 23Be hydrogen, C 1-C 18Alkyloyl, C 3-C 18Alkenoyl is with the C of oxygen or sulphur interruption 3-C 12Alkyloyl; With two (C 1-C 6-alkyl) C of phosphonate groups replacement 2-C 12Alkyloyl; C 6-C 9Naphthene base carbonyl, benzoyl,
Figure A20068005034800232
Or
Figure A20068005034800233
R 24And R 25Be hydrogen or C independently of one another 1-C 12Alkyl,
R 26Be hydrogen or C 1-C 4Alkyl,
R 27Be C 1-C 12Alkylidene group, C 2-C 8The chain alkenylene, C 2-C 8Alkylidene, C 7-C 12The phenyl alkylidene, C 5-C 8Cycloalkylidene or phenylene,
R 28Be hydroxyl, C 1-C 12Alkoxyl group or
Figure A20068005034800234
R 29Be oxygen or-NH-,
R 30Be C 1-C 18Alkyl or phenyl and
S is 1 or 2.
What equally preferably provide is the compound of formula I, wherein, if n is 1, then
R 1Be phenanthryl, thienyl, dibenzofuran group, unsubstituted or C 1-C 4The carbazyl that alkyl replaces; Or fluorenyl; Perhaps R 1Be the group of formula II, wherein
R 7, R 8, R 9, R 10And R 11Independent of each other is hydrogen, chlorine, hydroxyl, C 1-C 18Alkyl, C 1-C 18Alkoxyl group, C 1-C 18Alkylthio, C 3-C 4Alkenyloxy, C 3-C 4Alkynyloxy group, C 2-C 18Alkanoyloxy, phenyl, benzoyl, benzoyloxy or
R 20Be hydrogen,
R 21Be hydrogen, phenyl or C 1-C 18Alkyl, perhaps selectable, radicals R 20And R 21, forming the cyclohexylidene ring with the C atom that they connected, this ring is unsubstituted or with 1-3 C 1-C 4Alkyl replaces,
R 22Be hydrogen or C 1-C 4Alkyl and
R 23Be hydrogen, C 1-C 18Alkyloyl or benzoyl.
What especially preferably provide is the compound of formula I, wherein, if n is 1, then
R 7, R 8, R 9, R 10And R 11Be hydrogen, C independently of one another 1-C 4Alkylthio or phenyl.
Making us interested especially is the compound compositions that contains at least a formula I, wherein R 2, R 3, R 4And R 5Be hydrogen independently of one another, chlorine, C 1-C 18Alkyl, benzyl, phenyl, C 5-C 8Cycloalkyl, C 1-C 18Alkoxyl group, C 1-C 18Alkylthio, C 1-C 18Alkanoyloxy, C 1-C 18Alkanoylamino, C 3-C 18Chain ene acyloxy or benzoyloxy; Perhaps, selectable, radicals R 2And R 3Perhaps radicals R 3And R 4Perhaps radicals R 4And R 5, form phenyl ring with the C atom that they connected, R 4Additionally be-(CH 2) p-COR 15Perhaps-(CH 2) qOH, perhaps, if R 3, R 5And R 6Be hydrogen, R 4Additionally be the group of formula III,
R 15Be hydroxyl, C 1-C 12Alkoxyl group or
Figure A20068005034800242
R 16And R 17Be methyl group or, form C with the C atom that they connected 5-C 8Cycloalkanes fork basic ring, this ring are unsubstituted or with 1-3 C 1-C 4Alkyl replaces,
R 24And R 25Be hydrogen or C independently of one another 1-C 12Alkyl,
P be 1 or 2 and
Q is 2,3,4,5 or 6.
Equally very interesting is the compound compositions that contains at least a formula I, wherein radicals R 2, R 3, R 4And R 5In at least two be hydrogen.
Making us interested especially is the compound compositions that contains at least a formula I, wherein R 3And R 5Be hydrogen.
Making us interested extremely especially is the compound compositions that contains at least a formula I, wherein
R 2Be C 1-C 4Alkyl,
R 3Be hydrogen,
R 4Be C 1-C 4Alkyl or, if R 6Be hydrogen, R 4Additionally be the group of formula III,
R 5Be hydrogen and
R 16And R 17, form the cyclohexylidene basic ring with the C atom that they connected.
Following compound is the example of benzofuran-2-ones type, and it is particularly suitable for composition of the present invention: 3-[4-(2-acetoxyethoxy) phenyl]-5,7-di-t-butyl-benzofuran-2-ones; 5,7-di-t-butyl-3-[4-(2-octadecane acyl-oxygen base oxethyl) phenyl] benzofuran-2-ones; 3,3 '-two [5,7-di-t-butyl-3-(the 4-[2-hydroxyl-oxethyl] phenyl) benzofuran-2-ones]; 5,7-di-t-butyl-3-(4-ethoxyl phenenyl) benzofuran-2-ones; 3-(4-acetoxy-3,5-3,5-dimethylphenyl)-5,7-di-t-butyl benzo furans-2-ketone; 3-(3,5-dimethyl-4-new pentane acyloxy-phenyl)-5,7-di-t-butyl-benzofuran-2-ones; 5,7-di-t-butyl-3-phenyl benzofuran-2-ones; 5,7-di-t-butyl-3-(3, the 4-3,5-dimethylphenyl)-benzofuran-2-ones; 5,7-di-t-butyl-3-(2, the 3-3,5-dimethylphenyl) benzofuran-2-ones.
Making us interested equally especially is the compound compositions that comprises at least a formula V
Figure A20068005034800251
Wherein
R 2Be hydrogen or C 1-C 6Alkyl,
R 3Be hydrogen,
R 4Be hydrogen or C 1-C 6Alkyl,
R 5Be hydrogen,
R 7, R 8, R 9, R 10And R 11Independent of each other is hydrogen, C 1-C 4Alkyl or C 1-C 4Alkoxyl group has qualification promptly: radicals R 7, R 8, R 9, R 10Perhaps R 11In at least two be hydrogen.
What very particularly preferably provide is the compound compositions that contains at least a formula Va or Vb
Figure A20068005034800261
The perhaps mixture of two of formula Va and Vb compounds.
Described space hindered amine stabilizer comprises the formula of at least a portion:
Figure A20068005034800262
Here G 1, G 2, G 3, G 4And G 5Be the alkyl or the G of 1-8 C atom independently 1And G 2Perhaps G 3And G 4Be pentamethylene together.
Described hindered amine is disclosed in for example U.S. Patent No. 5004770,5204473,5096950,5300544,5112890,5124378,5145893,5216156,5844026,5980783,6046304,6117995,6271377,6297299,6392041,6376584 and 6472456 and disclosed U. S. application No.09/714717 (November 16 2000 applying date) and in 10/485377 (August 6 2002 applying date).
Above-cited U.S. Patent No. 6271377,6392041 and 6376584 discloses blocked hydroxyl group alkoxylamine stablizer.
Suitable hindered amine for example comprises:
1) 1-cyclohexyloxy-2,2,6,6-tetramethyl--4-octadecyl amino piperidine,
2) two (2,2,6,6-tetramethyl piperidine-4-yl) sebate,
3) two (1-acetoxyl group-2,2,6,6-tetramethyl piperidine-4-yl) sebate,
4) two (1,2,2,6,6-pentamethyl--4-yl) sebate,
5) two (1-cyclohexyloxy-2,2,6,6-tetramethyl piperidine-4-yl) sebate,
6) two (1-octyloxy-2,2,6,6-tetramethyl piperidine-4-yl) sebate;
7) two (1-acyl group-2,2,6,6-tetramethyl piperidine-4-yl) sebate,
8) two (1,2,2,6,6-pentamethyl--4-piperidyl) normal-butyl-3,5-di-tert-butyl-4-hydroxyl benzyl-malonic ester
9) 2, two [(1-cyclohexyloxy-2,2,6,6-tetramethyl piperidine-4-yl) butyl the amino]-6-of 4-(2-hydroxyl-ethylamino-s-triazine,
10) two (1-cyclohexyloxy-2,2,6,6-tetramethyl piperidine-4-yl) adipic acid ester,
11) 2, two [(1-cyclohexyloxy-2,2,6,6-piperidin-4-yl) butyl the amino]-6-chloro-s-triazines of 4-,
12) 1-(2-hydroxy-2-methyl propoxy-)-4-hydroxyl-2,2,6, the 6-tetramethyl piperidine,
13) 1-(2-hydroxy-2-methyl propoxy-)-4-oxo-2,2,6, the 6-tetramethyl piperidine,
14) 1-(2-hydroxy-2-methyl propoxy-)-4-octadecane acyl-oxygen base-2,2,6, the 6-tetramethyl piperidine,
15) two (1-(2-hydroxy-2-methyl propoxy-)-2,2,6,6-tetramethyl piperidine-4-yl) sebate,
16) two (1-(2-hydroxy-2-methyl propoxy-)-2,2,6,6-tetramethyl piperidine-4-yl) adipic acid ester,
17) 2,4-pair N-[1-(2-hydroxy-2-methyl propoxy-)-2,2,6,6-tetramethyl piperidine-4-yl]-N-butyl amino }-6-(2-hydroxyethyl amino)-s-triazine,
18) 4-benzoyl-2,2,6, the 6-tetramethyl piperidine,
19) two (1,2,2,6,6-pentamethyl-piperidin-4-yl) are to methoxyl group benzal phenyl malonic ester,
20) 4-stearoyl-oxy-2,2,6, the 6-tetramethyl piperidine,
21) two (1-octyloxy-2,2,6,6-tetramethyl-piperidyl) succinate,
22) 1,2,2,6,6-pentamethyl--4-amino piperidine,
23) 2-undecyl-7,7,9,9-tetramethyl--1-oxa--3,8-diaza-4-oxo-spiral shell [4,5] decane,
24) three (2,2,6,6-tetramethyl--4-piperidyl) nitrilotriacetate,
25) three (2-hydroxyl-3-(amino-(2,2,6,6-tetramethyl piperidine-4-yl) propyl group) nitrilotriacetate,
26) four (2,2,6,6-tetramethyl--4-piperidyl)-1,2,3,4-butane-tetracarboxylic ester,
27) four (1,2,2,6,6-pentamethyl--4-piperidyl)-1,2,3,4-butane-tetracarboxylic ester,
28) 1,1 '-(1,2-ethane two bases)-two (3,3,5,5-tetramethyl-piperazine ketone),
29) 3-n-octyl-7,7,9,9-tetramethyl--1,3,8-thriazaspiro [4.5] decane-2, the 4-diketone,
30) 8-ethanoyl-S-dodecyl-7,7,9,9-tetramethyl--1,3,8-thriazaspiro [4.5] decane-2, the 4-diketone,
31) 3-dodecyl-1-(2,2,6,6-tetramethyl--4-piperidyl) tetramethyleneimine-2, the 5-diketone,
32) 3-dodecyl-1-(1,2,2,6,6-pentamethyl--4-piperidyl) tetramethyleneimine-2, the 5-diketone,
33) N, N '-two-formyl radical-N, N '-two (2,2,6,6-tetramethyl--4-piperidyl) hexamethylene-diamine,
34) 2, two [(1-cyclohexyloxy-2,2,6,6-piperidin-4-yl) butyl amino]-6-chloro-s-triazine and the N of 4-, N '-two (3-aminopropyl) ethylene diamine) reaction product,
35) 1-(2-hydroxyethyl)-2,2,6, the condenses of 6-tetramethyl--4-hydroxy piperidine and Succinic Acid,
36) N, N '-two (2,2,6,6-tetramethyl--4-piperidyl)-hexamethylene-diamine and uncle's 4-octyl group amino-2, the linearity or the ring-shaped condensate of 6-two chloro-1,3,5-triazines,
37) N, N '-two (2,2,6,6-tetramethyl--4-piperidyl)-hexamethylene-diamine and 4-cyclohexyl amino-2, the linearity or the ring-shaped condensate of 6-two chloro-1,3,5-triazines,
38) N, N '-two-(2,2,6,6-tetramethyl--4-piperidyl) hexamethylene-diamine and 4-morpholino-2, the linearity or the ring-shaped condensate of 6-two chloro-1,3,5-triazines,
39) N, N '-two-(1,2,2,6,6-pentamethyl--4-piperidyl) hexamethylene-diamine and 4-morpholino-2, the linearity or the ring-shaped condensate of 6-two chloro-1,3,5-triazines,
40) the 2-chloro-4, two (4-normal-butyl amino-2,2,6,6-the tetramethyl-piperidyl)-1,3,5-triazines and 1 of 6-, and the condenses of two (3-amino propyl amino) ethane of 2-,
41) the 2-chloro-4,6-two (4-normal-butyl amino-1,2,2,6,6-pentamethyl-piperidyl)-1,3,5-triazines and 1, and the condenses of 2-pair-(3-amino propyl amino) ethane,
42) 7,7,9,9-tetramethyl--2-encircles undecyl-1-oxa--3, the reaction product of 8-diaza-4-oxo-spiral shell [4,5] decane and Epicholorohydrin,
43) poly-[methyl, (3-oxygen-(2,2,6,6-tetramethyl piperidine-4-yl) propyl group)] siloxanes, CAS#182635-99-0,
44) maleic anhydride-C 18-C 22-alpha-olefin copolymer and 2,2,6, the reaction product of 6-tetramethyl--4-amino piperidine,
45) oligomeric compound, it is 4,4 '-hexa-methylene two (amino-2,2,6,6-tetramethyl piperidine) with 2-chloro-4, two (the dibutylamino)-s-triazines of 6-are end capped 2,4-two chloro-6-[(2,2,6,6-tetramethyl--piperidin-4-yl) butyl amino]-condensation product of s-triazine
46) oligomeric compound, it is 4,4 '-hexa-methylene two (amino-1,2,2,6,6-pentamethyl-piperidines) with 2-chloro-4, two (dibutyl-amino)-s-triazines of 6-are end capped 2,4-two chloro-6-[(1,2,2,6,6-pentamethyl-piperidin-4-yl) butyl amino]-condensation product of s-triazine
47) oligomeric compound, it is 4,4 '-two (amino-1-propoxy--2,2 of hexa-methylene, 6, the 6-tetramethyl piperidine) with 2-chloro-4, two (the dibutylamino)-s-triazines of 6-are end capped 2,4-two chloro-6-[(1-propoxy--2,2,6,6-tetramethyl piperidine-4-yl) butyl amino]-condensation product of s-triazine
48) oligomeric compound, it is 4,4 '-two (amino-1-acyloxy-2,2 of hexa-methylene, 6, the 6-tetramethyl piperidine) with 2-chloro-4, two (the dibutylamino)-s-triazines of 6-are end capped 2,4-two chloro-6-[(1-acyloxy-2,2,6,6-tetramethyl piperidine-4-yl) butyl amino]-condensation product of s-triazine and
49) with 1, the product that two (3-aminopropyl amino) ethane of 2-and cyanuryl chloride react acquisition reacts the product of acquisition with (2,2,6,6-tetramethyl piperidine-4-yl) butylamine.
That also comprise is the space of any above mentioned compound N-H that is obstructed, N-methyl, N-methoxyl group, N-propoxy-, N-octyloxy, N-cyclohexyloxy, N-acyloxy and N-(2-hydroxy-2-methyl propoxy-) analogue.For example, replace the N-H hindered amine will use the N-methyl analogue to replace N-H with N-methyl hindered amine.
Described hindered phenol anti-oxidants for example is:
1.1. Alkylating single phenols, for example 2,6-di-t-butyl-4-sylvan, the 2-tertiary butyl-4,6-dimethyl phenol, 2,6-di-t-butyl-4-ethyl phenol, 2,6-di-t-butyl-4-normal-butyl phenol, 2,6-di-t-butyl-4-isobutyl-phenol, 2,6-two cyclopentyl-4-sylvan, 2-(Alpha-Methyl cyclohexyl)-4,6-dimethyl-phenol, 2,6-two (octadecyl)-4-sylvan, 2,4,6-thricyclohexyl phenol, 2,6-di-t-butyl-4-methoxymethyl phenol is the nonyl phenol of linearity or side chain on its side chain, for example, 2,6-dinonyl-4-sylvan, 2,4-dimethyl-6-(1-methyl undecane-1-yl) phenol, 2,4-dimethyl-6-(1-methyl heptadecane-1-yl) phenol, 2,4-dimethyl-6-(1-methyl tridecane-1-yl) phenol and their mixture.
1.2. Alkylthio methyl phenols, for example 2,4-dioctyl sulfenyl methyl-6-tert butyl phenol, 2,4-dioctyl sulfenyl methyl-6-sylvan, 2,4-dioctyl sulfenyl methyl-6-ethyl phenol, 2,6-two (dodecyl) sulfenyl methyl-4-nonyl phenol.
1.3. Hydroquinone type and alkylating hydroquinone type, for example 2,6-di-t-butyl-4-methoxyl group phenol, 2, the 5-di-tert-butyl hydroquinone, 2,5-two tert-pentyl Resorcinol, 2,6-phenylbenzene-4-octadecane oxygen base phenol, 2, the 6-di-tert-butyl hydroquinone, 2,5-di-t-butyl-4-hydroxyanisol, 3,5-di-t-butyl-4-hydroxyanisol, 3,5-di-tert-butyl-hydroxy phenyl stearate, two-(3,5-di-t-butyl-4-hydroxyphenyl) adipic acid ester.
1.4. Tocopherol, alpha-tocopherol for example, 5,8-dimethyl tocol, Gamma-Tocopherol, Delta-Tocopherol and their mixture (vitamin-E).
1.5. Hydroxylated sulfo-diphenylether, for example 2,2 '-thiobis (the 6-tertiary butyl-4-sylvan), 2,2 '-thiobis (4-octyl phenol), 4,4 '-thiobis (the 6-tertiary butyl-3-sylvan), 4,4 '-thiobis (the 6-tertiary butyl-2-sylvan), 4,4 '-thiobis-(3,6-di-sec-amyl phenol), 4,4 '-two (2,6-dimethyl-4-hydroxyl-phenyl) disulphide.
1.6. The alkylidene bisphenolsFor example 2,2 '-methylene-bis (the 6-tertiary butyl-4-sylvan), 2,2 '-methylene-bis (the 6-tertiary butyl-4-ethyl phenol), 2,2 '-methylene-bis [4-methyl-6-(Alpha-Methyl cyclohexyl)-phenol], 2,2 '-methylene-bis (4-methyl-6-cyclohexyl phenol), 2,2 '-methylene-bis (6-nonyl-4-sylvan), 2,2 '-methylene-bis (4, the 6-di-tert-butylphenol), 2,2 '-ethidine two (4,6-di-t-butyl-phenol), 2,2 '-ethidine two (the 6-tertiary butyl-4-isobutyl-phenol), 2,2 '-methylene-bis [6-(α-Jia Jibianji)-4-nonyl phenol], 2,2 '-methylene-bis [6-(α, α-Er Jiajibianji)-the 4-nonyl phenol], 4,4 '-methylene-bis (2, the 6-di-tert-butylphenol), 4,4 '-methylene-bis (the 6-tertiary butyl-2-sylvan), 1, two (5-tertiary butyl-4-hydroxy-2-aminomethyl phenyl) butane of 1-, 2, two (the 3-tertiary butyl-5-methyl-2-hydroxybenzyl)-4-sylvans of 6-, 1,1,3-three (5-tertiary butyl-4-hydroxy-2-aminomethyl phenyl) butane, 1, two (5-tertiary butyl-4-hydroxy-2-methyl-phenyl)-3-dodecyl sulfydryl butane of 1-, ethylene glycol bis [3, two (3-tert-butyl-hydroxy phenyl) butyric esters of 3-], two (3-tertiary butyl-4-hydroxy-5-methyl-phenyl) Dicyclopentadiene (DCPD), two [2-(3 '-tertiary butyl-2-hydroxy-5-methyl base benzyl)-the 6-tertiary butyl-4-aminomethyl phenyl] terephthalate, 1,1-pair-(3,5-dimethyl-2-hydroxy phenyl) butane, 2,2-two-(3, the 5-di-tert-butyl-hydroxy phenyl) propane, 2,2-pair-(5-tertiary butyl-4-hydroxy 2-aminomethyl phenyl)-4-dodecyl sulfydryl butane, 1,1,5,5-four (5-tertiary butyl-4-hydroxy-2-aminomethyl phenyl) pentane.
1.7. Benzyl compounds, for example 3,5,3 ', 5 '-tetra-tert-4,4 '-the dihydroxyl dibenzyl ether, octadecyl-4-hydroxyl-3,5-dixylyl mercaptoacetate, tridecyl-4-hydroxyl-3,5-di-t-butyl-benzyl mercaptoacetate, three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) amine, 1,3,5-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl)-2,4,6-Three methyl Benzene, two (3,5-di-t-butyl-4-acrinyl) sulphur, 3,5-di-tert-butyl-4-hydroxyl benzyl-sulfydryl-acetate isooctyl acrylate, two-(the 4-tertiary butyl-3-hydroxyl-2,6-dimethyl benzyl) two mercaptan terephthalates, 1,3,5-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) isocyanuric acid ester, 1,3,5-three (the 4-tertiary butyl-3-hydroxyl-2,6-dimethyl benzyl) isocyanuric acid ester, 3,5-di-tert-butyl-4-hydroxyl benzyl-di(2-ethylhexyl)phosphate (octadecyl) ester and 3,5-di-tert-butyl-4-hydroxyl benzyl-monoethyl phosphate, calcium salt.
1.8. The hydroxybenzyl malonic ester, two (octadecyl)-2 for example, 2-two-(3,5-di-t-butyl-2-acrinyl)-and malonic ester, two (octadecyl)-2-(3-tertiary butyl-4-hydroxy-5-methyl-benzyl)-malonic ester, two (dodecyl) mercaptoethyl-2,2-two-(3, the 5-di-tert-butyl-4-hydroxyl benzyl) malonic ester, it is two that [4-(1,1,3, the 3-tetramethyl butyl) phenyl]-2, two (3, the 5-di-tert-butyl-4-hydroxyl benzyl) malonic esters of 2-.
1.9. Aromatics acrinyl compound, for example 1,3,5-three-(3,5-di-t-butyl-4-hydroxyl-benzyl)-2,4,6-Three methyl Benzene, 1, two (3, the 5-di-tert-butyl-4-hydroxyl benzyl)-2,3,5 of 4-, 6-tetramethyl-benzene, 2,4,6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) phenol.
1.10. Triaizine compounds, for example 2, two (octyl group the sulfydryl)-6-(3,5-di-t-butyl-4-hydroxyl-anilino)-1 of 4-; 3, the 5-triazine, 2-octyl group sulfydryl-4,6-two (3; 5-di-t-butyl-4-hydroxybenzene amido)-and 1,3,5-triazines, 2-octyl group sulfydryl-4; two (3,5-di-t-butyl-4-the hydroxyphenoxy)-1,3,5-triazines of 6-; 2,4,6-three (3,5-di-t-butyl-4-hydroxyphenoxy)-1; 2,3-triazine, 1,3; 5-three-(3,5-di-t-butyl-4-acrinyl) isocyanuric acid ester, 1,3; 5-three (the 4-tertiary butyl-3-hydroxyl-2,6-dimethyl benzyl) isocyanuric acid ester, 2,4; 6-three-(3,5-di-tert-butyl-hydroxy phenyl ethyl)-1,3,5-triazines; 1,3,5-three (3,5-di-t-butyl-4-hydroxyl-phenyl propionyl)-six hydrogen-1; 3,5-triazine, 1; 3,5-three (3,5-dicyclohexyl-4-acrinyl) isocyanuric acid ester.
1.11. Benzylphosphonic acid ester classDimethyl-2 for example, 5-di-tert-butyl-4-hydroxyl benzyl phosphonic acid ester, diethyl-3,5-di-tert-butyl-4-hydroxyl benzyl phosphonic acid ester, two (octadecyls) 3,5-di-t-butyl-4-acrinyl phosphonic acid ester, two (octadecyl)-5-tertiary butyl-4-hydroxies-3-methyl-benzyl phosphonic acid ester, 3, the calcium salt of 5-di-tert-butyl-4-hydroxyl benzyl phosphonic mono ethyl ester.
1.12. The acyl amino phenols, N-4-hydroxyl-lauroyl aniline for example, N-4-hydroxyl-stearanilide, 2,4-is two-octyl group sulfydryl-6-(3,5-tertiary butyl-4-hydroxy anilino)-s-triazine and octyl group-N-(3, the 5-di-tert-butyl-hydroxy phenyl)-carbamate.
1.13. β-(3,5-di-t-butyl-4-hydroxyphenyl) propionic acid and single-or the ester of polyhydroxy-alcohol, described alcohol for example is methyl alcohol, ethanol, n-Octanol, isooctyl alcohol, Stearyl alcohol, 1,6-hexylene glycol, 1,9-nonanediol, ethylene glycol, 1,2-propylene glycol, neopentyl glycol, sulfo-glycol ether, glycol ether, triglycol, tetramethylolmethane, three (hydroxyethyl) isocyanuric acid ester, N, N '-two (hydroxyethyl) oxamide, 3-thia hendecanol, 3-thia pentadecylic alcohol, trimethylammonium hexylene glycol, TriMethylolPropane(TMP), 4-hydroxymethyl-1-phospha-2,6,7-trioxa-l-phosphabicyclo [2.2.2] octane.
1.14. β-(5-tertiary butyl-4-hydroxy-3-aminomethyl phenyl) propionic acid and single-or the ester of polyhydroxy-alcohol, described alcohol for example is methyl alcohol, ethanol, n-Octanol, isooctyl alcohol, Stearyl alcohol, 1,6-hexylene glycol, 1,9-nonanediol, ethylene glycol, 1,2-propylene glycol, neopentyl glycol, sulfo-glycol ether, glycol ether, triglycol, tetramethylolmethane, three (hydroxyethyl) isocyanuric acid ester, N, N '-two-(hydroxyethyl) oxamide, 3-thia hendecanol, 3-thia pentadecylic alcohol, trimethylammonium hexylene glycol, TriMethylolPropane(TMP), 4-hydroxymethyl-1-phospha-2,6,7-trioxa-l-phosphabicyclo [2.2.2] octane.
1.15. β-(3,5-dicyclohexyl-4-hydroxyphenyl) propionic acid and single-or the ester of polyhydroxy-alcohol, described alcohol for example is methyl alcohol, ethanol, octanol, Stearyl alcohol, 1,6-hexylene glycol, 1,9-nonanediol, ethylene glycol, 1,2-propylene glycol, neopentyl glycol, sulfo-glycol ether, glycol ether, triglycol, tetramethylolmethane, three (hydroxyethyl) isocyanuric acid ester, N, N '-two (hydroxyethyl) oxamide, 3-thia hendecanol, 3-thia pentadecylic alcohol, trimethylammonium hexylene glycol, TriMethylolPropane(TMP), 4-hydroxymethyl-1-phospha-2,6,7-trioxa-l-phosphabicyclo [2.2.2] octane.
1.16. 3,5-di-t-butyl-4-hydroxyphenyl acetate and single-or the ester of polyhydroxy-alcohol, described alcohol for example is methyl alcohol, ethanol, octanol, Stearyl alcohol, 1,6-hexylene glycol, 1,9-nonanediol, ethylene glycol, 1,2-propylene glycol, neopentyl glycol, sulfo-glycol ether, glycol ether, triglycol, tetramethylolmethane, three (hydroxyethyl) isocyanuric acid ester, N, N '-two (hydroxyethyl) oxamide, 3-thia hendecanol, 3-thia pentadecylic alcohol, trimethylammonium hexylene glycol, TriMethylolPropane(TMP), 4-hydroxymethyl-1-phospha-2,6,7-trioxa-l-phosphabicyclo [2.2.2] octane.
1.17. The acid amides of β-(3,5-di-t-butyl-4-hydroxyphenyl) propionic acid, N for example, N '-two (3; 5-di-tert-butyl-hydroxy phenyl propionyl) hexa-methylene diamide; N, N '-two (3,5-di-t-butyl-4-hydroxyl-phenyl propionyl) trimethylene diamide; N; N '-two (3,5-di-tert-butyl-hydroxy phenyl propionyl) hydrazides, N; N '-two [2-(3-[3,5-di-tert-butyl-hydroxy phenyl] propionyloxy) ethyl] oxamide (Naugard
Figure A20068005034800321
XL-1 is provided by Uniroyal).
Each described 3-aryl benzofuranone and hindered amine as light stabilizer, and the consumption of optional phenol antioxidant is based on the about 5000ppm weight of about 5ppm-of biodiesel fuel weight, for example about about 5000ppm weight of 50ppm-, for example about about 5000ppm weight of 100-.For example, each described additive is with based on the about 4000ppm weight of about 150-of biodiesel fuel weight, the about about 3000ppm weight of 200-, the perhaps about about 2500ppm weight of 250-and existing.In some example, described amount can be high to about 1 weight %, and about 2 weight % or about 3 weight % are based on biodiesel fuel weight.
Described stable biodiesel fuel shows the stability in storage of raising with respect to unstabilized sample.The degraded of the biodiesel fuel under heat, light or oxygen condition is observed by the formation of carboxylic acid, superoxide, aldehyde and alcohol.
Embodiment
The Rancimat that use grows up in foodstuffs industry tests the oxidative stability of testing soybean biological diesel oil (methyl ester of soya fatty acid).The soybean biological diesel samples of 3.0g is remained on 111.7 ℃ and be exposed in the bubbling air-flow of air (10 liters/hour).Sampling receptacle is vented to second container, and here waste gas forms bubble by the distilled water of 60ml.The volatile oxygenolysis product of this thermometrically is superoxide, alcohol, aldehyde and carboxylic acid for example.Described volatile decomposition products (mainly being formic acid) flows through sampling receptacle and is vented in second container, and here they are distilled the water collection.By using electrode to come the specific conductivity as the function of time of successive monitoring water.Specific conductivity point of inflexion on a curve (nonspecific value) is measured induction time.Should be noted that some samples had very high electricity and lead before reaching flex point, lead and other samples only have slight electricity.The increase of oxidative stability is represented in the increase of induction time.The result is in following table.The amount of additive is based on the weight percent of biofuel weight.
The Rancimat induction time
Figure A20068005034800331
Additive A is two-(1,1,2,2,6,6-pentamethyl--4-piperidyl) sebate; B is 3-(3, the 4-3,5-dimethylphenyl)-5,7-di-t-butyl-benzofuran-2-ones.It is necessary that 6 hours induction time satisfies the EN14214 standard.

Claims (10)

1. the stable biodiesel fuel compositions of harmful toxic action of a heat resistanceheat resistant, light and oxygen, said composition comprises:
Biodiesel fuel and
Effective one or more additives of stable quantity, this additive be selected from 3-arylbenzofuranones as stabilisers and hindered amine as light stabilizer and
Choose wantonly, be selected from one or more additives of hindered phenol anti-oxidants.
2. according to the composition of claim 1, it comprises the 3-arylbenzofuranones as stabilisers of one or more formulas I:
Figure A2006800503480002C1
Wherein, if n is 1, then
R 1It is naphthyl, phenanthryl, anthryl, 5,6,7,8-tetrahydrochysene-2-naphthyl, 5,6,7,8-tetrahydrochysene-1-naphthyl, thienyl, benzo [b] thienyl, naphtho-[2,3-b] thienyl, thianthrenyl, dibenzofuran group, benzopyranyl, xanthenyl, fen oxathiin base, pyrryl, imidazolyl, pyrazolyl, pyrazinyl, pyrimidyl, pyridazinyl, the indolizine base, isoindolyl, indyl, indazolyl, purine radicals, quinolizinyl, isoquinolyl, quinolyl, 2, the 3-phthalazinyl, 1, the 5-phthalazinyl, quinoxalinyl, quinazolyl, the cinnolines base, pteridyl, carbazyl, the β-Ka Lin base, phenanthridinyl, acridyl, perimidinyl, the phenanthroline base, phenazinyl, isothiazolyl, phenothiazinyl isoxazolyl, the furazan base, biphenyl, terphenyl, fluorenyl or phenoxazinyl, perhaps any one substituted these carbocyclic rings or heterocyclic group, it is to use C 1-C 4Alkyl-, C 1-C 4Alkoxyl group-, C 1-C 4The alkyl sulfenyl-, hydroxyl-, halo-, amino-, C 1-C 4Alkylamino-, phenyl amino-or two (C 1-C 4Alkyl) amino replaces; Perhaps R 1It is the group of formula II
Figure A2006800503480002C2
And
If n is 2, then
R 1Be unsubstituted or C 1-C 4Alkyl-or the hydroxyl phenylene or the naphthylidene that replace; Or-R 12-X-R 13-,
R 2, R 3, R 4And R 5Be hydrogen, chlorine, hydroxyl, C independently of one another 1-C 25Alkyl, C 7-C 9Benzene alkyl, unsubstituted or C 1-C 4The phenyl that alkyl replaces; Unsubstituted or C 1-C 4The C that alkyl replaces 5-C 8Cycloalkyl; C 1-C 18Alkoxyl group, C 1-C 18Alkylthio, C 1-C 4Alkylamino, two (C 1-C 4Alkyl) amino, C 1-C 25Alkanoyloxy, C 1-C 25Alkanoylamino, C 3-C 25Alkenoyl oxygen base, with oxygen, sulphur or The C that interrupts 3-C 25Alkanoyloxy; C 6-C 9Naphthene base carbonyl oxygen base, benzoyloxy or C 1-C 12The benzoyloxy that alkyl replaces; Or, as selectable, radicals R 2With R 3Perhaps radicals R 3With R 4Perhaps radicals R 4With R 5, form the benzo ring with the C atom that they connected, R 4Additionally be-(CH 2) p-COR 15Perhaps-(CH 2) qOH or, if R 3, R 5And R 6Be hydrogen, R so 4Additionally be the group of formula III:
Figure A2006800503480003C2
R wherein 1Definition is with the top definition for n=1,
R 6Be the group of hydrogen or formula IV:
Figure A2006800503480003C3
Here R 4Be the group and the R of other formula III 1Definition is with the top definition that is used for n=1, R 7, R 8, R 9, R 10And R 11Be hydrogen, halogen, hydroxyl, C independently of one another 1-C 25Alkyl, with oxygen, sulphur or
Figure A2006800503480003C4
The C that interrupts 2-C 25Alkyl; C 1-C 25Alkoxyl group, with oxygen, sulphur or
Figure A2006800503480004C1
The C that interrupts 2-C 25Alkoxyl group; C 1-C 25Alkylthio, C 3-C 25Alkenyl, C 3-C 25Alkenyloxy, C 3-C 25Alkynyl, C 3-C 25Alkynyloxy group, C 7-C 9Benzene alkyl, C 7-C 9Phenyl alkoxyl group, unsubstituted or C 1-C 4The phenyl that alkyl replaces; Unsubstituted or C 1-C 4The phenoxy group that alkyl replaces; Unsubstituted or C 1-C 4The C that alkyl replaces 5-C 8Cycloalkyl; Unsubstituted or C 1-C 4The C that alkyl replaces 5-C 8Cycloalkyloxy; C 1-C 4Alkylamino, two (C 1-C 4Alkyl) amino, C 1-C 25Alkyloyl, with oxygen, sulphur or
Figure A2006800503480004C2
The C that interrupts 3-C 25Alkyloyl; C 1-C 25Alkanoyloxy, with oxygen, sulphur or
Figure A2006800503480004C3
The C that interrupts 3-C 25Alkanoyloxy; C 1-C 25Alkanoylamino, C 3-C 25Alkenoyl, with oxygen, sulphur or
Figure A2006800503480004C4
The C that interrupts 3-C 25Alkenoyl; C 3-C 25Chain ene acyloxy, with oxygen, sulphur or
Figure A2006800503480004C5
The C that interrupts 3-C 25Chain ene acyloxy; C 6-C 9Naphthene base carbonyl, C 6-C 9Naphthene base carbonyl oxygen base, benzoyl or C 1-C 12The benzoyl that alkyl replaces; Benzoyloxy or C 1-C 12The benzoyloxy that alkyl replaces;
Figure A2006800503480004C6
Perhaps
Figure A2006800503480004C7
Otherwise, in formula II, radicals R 7And R 8Perhaps radicals R 8And R 11, form the benzo ring with the C atom that they connected,
R 12And R 13Be unsubstituted or C independently of one another 1-C 4Phenylene or naphthylidene that alkyl replaces,
R 14Be hydrogen or C 1-C 8Alkyl,
R 15Be hydroxyl,
Figure A2006800503480004C8
C 1-C 18Alkoxyl group or
Figure A2006800503480004C9
R 16And R 17Be hydrogen, CF independently of one another 3, C 1-C 12Alkyl or phenyl, perhaps R 16And R 17, form unsubstituted or with 1-3 C with the C atom that they connected 1-C 4The C that alkyl replaces 5-C 8The ring alkylidene;
R 18And R 19Be hydrogen, C independently of one another 1-C 4Alkyl or phenyl,
R 20Be hydrogen or C 1-C 4Alkyl,
R 21Be hydrogen, unsubstituted or C 1-C 4The phenyl that alkyl replaces; C 1-C 25Alkyl, with oxygen, sulphur or
Figure A2006800503480004C10
The C that interrupts 2-C 25Alkyl; Unsubstituted or with 1-3 C 1-C 4The C that alkyl replaces on phenyl 7-C 9The benzene alkyl; Unsubstituted or with 1-3 C 1-C 4That alkyl replaces on phenyl and with oxygen, sulphur or
Figure A2006800503480005C1
The C that interrupts 7-C 25The benzene alkyl, perhaps, selectively, radicals R 20And R 21, the C atom that connects with them forms C 5-C 12Cycloalkylidene ring, this ring are unsubstituted or with 1-3 C 1-C 4Alkyl replaces;
R 22Be hydrogen or C 1-C 4Alkyl,
R 23Be hydrogen, C 1-C 25Alkyloyl, C 3-C 25Alkenoyl, with oxygen, sulphur or
Figure A2006800503480005C2
The C that interrupts 3-C 25Alkyloyl; With two (C 1-C 6Alkyl) C of phosphonate groups replacement 2-C 25Alkyloyl; C 6-C 9Naphthene base carbonyl, Thenoyl, furoyl base, benzoyl or C 1-C 12The benzoyl that alkyl replaces;
Figure A2006800503480005C3
R 24And R 25Be hydrogen or C independently of one another 1-C 18Alkyl,
R 26Be hydrogen or C 1-C 8Alkyl,
R 27Be direct key, C 1-C 18Alkylidene group, with oxygen, sulphur or
Figure A2006800503480005C4
The C that interrupts 2-C 18Alkylidene group; C 2-C 18Alkylene group, C 2-C 20Alkylidene, C 7-C 20Phenyl alkylidene, C 5-C 8Cycloalkylidene, C 7-C 8Inferior bicyclic alkyl, unsubstituted or C 1-C 4The phenylene that alkyl replaces, perhaps
Figure A2006800503480005C5
Or
Figure A2006800503480005C6
R 28Be hydroxyl,
Figure A2006800503480005C7
C 1-C 18Alkoxyl group or
Figure A2006800503480005C8
R 29Be oxygen ,-NH-or
Figure A2006800503480005C9
R 30Be C 1-C 18Alkyl or phenyl,
R 31Be hydrogen or C 1-C 18Alkyl,
M is a r valency metallic cation,
X be direct key, oxygen, sulphur or-NR 31-,
N is 1 or 2,
P is 0,1 or 2,
Q is 1,2,3,4,5 or 6,
R be 1,2 or 3 and
S is 0,1 or 2.
3. according to the composition of claim 2, wherein said 3-aryl benzofuranone is formula I, n=1 wherein, R 1Be unsubstituted or at contraposition C 1-C 18Alkylthio or two (C 1-C 4Alkyl) the amino phenyl that replaces; Single-to the alkane phenyl of five-replacement, it contains maximum 18 C atoms altogether in 1-5 alkyl substituent; Naphthyl, biphenyl, terphenyl, phenanthryl, anthryl, fluorenyl, carbazyl, thienyl, pyrryl, phenothiazinyl or 5,6,7, the 8-tetralyl, its each be unsubstituted or use C 1-C 4Alkyl, C 1-C 4Alkoxyl group, C 1-C 4Alkylthio, hydroxyl or amino replace.
4. according to the composition of claim 2, wherein said 3-aryl benzofuranone is formula I, and wherein n is 2, R 1Be-R 12-X-R 13-, R 12And R 13Be phenylene, X be oxygen or-NR 31-, and R 31Be C 1-C 4Alkyl.
5. according to the composition of claim 2, wherein said 3-aryl benzofuranone is selected from 3-[4-(2-acetoxyethoxy) phenyl]-5,7-di-t-butyl-benzofuran-2-ones; 5,7-di-t-butyl-3-[4-(2-octadecane acyl-oxygen base oxethyl) phenyl] benzofuran-2-ones; 3,3 '-two [5,7-di-t-butyl-3-(the 4-[2-hydroxyl-oxethyl] phenyl) benzofuran-2-ones]; 5,7-di-t-butyl-3-(4-ethoxyl phenenyl) benzofuran-2-ones; 3-(4-acetoxy-3,5-3,5-dimethylphenyl)-5,7-di-t-butyl benzo furans-2-ketone; 3-(3,5-dimethyl-4-new pentane acyloxy-phenyl)-5,7-di-t-butyl-benzofuran-2-ones; 5,7-di-t-butyl-3-phenyl benzofuran-2-ones; 5,7-di-t-butyl-3-(3, the 4-3,5-dimethylphenyl)-benzofuran-2-ones and 5,7-di-t-butyl-3-(2, the 3-3,5-dimethylphenyl)-benzofuran-2-ones.
6. according to the composition of claim 1, it comprises one or more hindered amine as light stabilizer, and this stablizer contains the part of at least one following formula:
Figure A2006800503480007C1
Here G 1, G 2, G 3, G 4And G 5Be the alkyl or the G of 1-8 C atom independently 1And G 2Perhaps G 3And G 4Be pentamethylene together.
7. according to the composition of claim 6, hindered amine described here is the amine that N-H, N-methyl, N-methoxyl group, N-propoxy-, N-octyloxy, N-cyclohexyloxy, N-acyloxy or N-(2-hydroxy-2-methyl-propoxy-) replace.
8. according to the composition of claim 1, it comprises one or more hindered amine as light stabilizer and one or more hindered phenol anti-oxidants.
9. composition according to Claim 8, hindered phenol anti-oxidants described here is selected from butylated hydroxytoluene, butylated hydroxyanisol, tocopherol, phosphonic acids benzyl ester, β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid and single-or ester of polyhydroxy-alcohol, β-(5-tertiary butyl-4-hydroxy-3-aminomethyl phenyl) propionic acid and singly-or ester, the β-(3 of polyhydroxy-alcohol, 5-dicyclohexyl-4-hydroxy phenyl) propionic acid and single-or the ester and 3 of polyhydroxy-alcohol, 5-di-tert-butyl-hydroxy phenyl acetate and singly-or the ester of polyhydroxy-alcohol.
10. stable method of deleterious effect that makes biodiesel fuel to heat, light and oxygen, this method comprises one or more additives of sneaking into effective stable quantity in biodiesel fuel, this additive is selected from 3-arylbenzofuranones as stabilisers and hindered amine as light stabilizer and optional, and one or more are selected from the additive of hindered phenol anti-oxidants.
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