TWI535839B - 液體烴及其他燃料與油之二苯基苄基醚標記物化合物 - Google Patents
液體烴及其他燃料與油之二苯基苄基醚標記物化合物 Download PDFInfo
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- 239000000446 fuel Substances 0.000 title claims description 37
- 150000001875 compounds Chemical class 0.000 title claims description 35
- 239000003550 marker Substances 0.000 title description 22
- 229930195733 hydrocarbon Natural products 0.000 title description 17
- 150000002430 hydrocarbons Chemical class 0.000 title description 17
- 239000003921 oil Substances 0.000 title description 7
- 239000007788 liquid Substances 0.000 title description 5
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 title description 4
- 235000010290 biphenyl Nutrition 0.000 title description 2
- 239000004305 biphenyl Substances 0.000 title description 2
- MHDVGSVTJDSBDK-UHFFFAOYSA-N dibenzyl ether Chemical compound C=1C=CC=CC=1COCC1=CC=CC=C1 MHDVGSVTJDSBDK-UHFFFAOYSA-N 0.000 title description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 42
- 239000003225 biodiesel Substances 0.000 claims description 19
- 125000001424 substituent group Chemical group 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 15
- 239000003209 petroleum derivative Substances 0.000 claims description 13
- 125000004642 (C1-C12) alkoxy group Chemical group 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 2
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 239000003208 petroleum Substances 0.000 description 11
- 239000000047 product Substances 0.000 description 9
- 239000000203 mixture Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 235000019198 oils Nutrition 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000002283 diesel fuel Substances 0.000 description 5
- 239000008096 xylene Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000003502 gasoline Substances 0.000 description 4
- 238000004949 mass spectrometry Methods 0.000 description 4
- 238000001953 recrystallisation Methods 0.000 description 4
- RRIQMCAOWUZVJZ-UHFFFAOYSA-N 1-methyl-4-[[4-[4-[(4-methylphenoxy)methyl]phenyl]phenyl]methoxy]benzene Chemical group C1=CC(C)=CC=C1OCC1=CC=C(C=2C=CC(COC=3C=CC(C)=CC=3)=CC=2)C=C1 RRIQMCAOWUZVJZ-UHFFFAOYSA-N 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
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- 239000003599 detergent Substances 0.000 description 3
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 150000002989 phenols Chemical class 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 125000004400 (C1-C12) alkyl group Chemical group 0.000 description 2
- INZDTEICWPZYJM-UHFFFAOYSA-N 1-(chloromethyl)-4-[4-(chloromethyl)phenyl]benzene Chemical group C1=CC(CCl)=CC=C1C1=CC=C(CCl)C=C1 INZDTEICWPZYJM-UHFFFAOYSA-N 0.000 description 2
- XYLMFSTYADTPPE-UHFFFAOYSA-N 1-(phenoxymethyl)-4-[4-(phenoxymethyl)phenyl]benzene Chemical group C=1C=C(C=2C=CC(COC=3C=CC=CC=3)=CC=2)C=CC=1COC1=CC=CC=C1 XYLMFSTYADTPPE-UHFFFAOYSA-N 0.000 description 2
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- NTWQMWCXCURRBB-UHFFFAOYSA-N 1-methyl-2-[[4-[4-[(2-methylphenoxy)methyl]phenyl]phenyl]methoxy]benzene Chemical group CC1=CC=CC=C1OCC1=CC=C(C=2C=CC(COC=3C(=CC=CC=3)C)=CC=2)C=C1 NTWQMWCXCURRBB-UHFFFAOYSA-N 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- 238000004847 absorption spectroscopy Methods 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
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- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- YYGNTYWPHWGJRM-UHFFFAOYSA-N (6E,10E,14E,18E)-2,6,10,15,19,23-hexamethyltetracosa-2,6,10,14,18,22-hexaene Chemical compound CC(C)=CCCC(C)=CCCC(C)=CCCC=C(C)CCC=C(C)CCC=C(C)C YYGNTYWPHWGJRM-UHFFFAOYSA-N 0.000 description 1
- DIIIISSCIXVANO-UHFFFAOYSA-N 1,2-Dimethylhydrazine Chemical compound CNNC DIIIISSCIXVANO-UHFFFAOYSA-N 0.000 description 1
- QECFHPLCGSKJGY-UHFFFAOYSA-N 1-methyl-3-[[4-[4-[(3-methylphenoxy)methyl]phenyl]phenyl]methoxy]benzene Chemical group CC1=CC=CC(OCC=2C=CC(=CC=2)C=2C=CC(COC=3C=C(C)C=CC=3)=CC=2)=C1 QECFHPLCGSKJGY-UHFFFAOYSA-N 0.000 description 1
- YDFVUEQCMLJLRB-UHFFFAOYSA-N 1-tert-butyl-4-[[4-[4-[(4-tert-butylphenoxy)methyl]phenyl]phenyl]methoxy]benzene Chemical group C1=CC(C(C)(C)C)=CC=C1OCC1=CC=C(C=2C=CC(COC=3C=CC(=CC=3)C(C)(C)C)=CC=2)C=C1 YDFVUEQCMLJLRB-UHFFFAOYSA-N 0.000 description 1
- VFYFMNCKPJDAPV-UHFFFAOYSA-N 2,2'-(5-oxo-1,3-dioxolan-4,4-diyl)diessigs Chemical compound C1N(C2)CN3CN1CN2C3.OC(=O)CC1(CC(O)=O)OCOC1=O VFYFMNCKPJDAPV-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical class CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- QHPQWRBYOIRBIT-UHFFFAOYSA-N 4-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C=C1 QHPQWRBYOIRBIT-UHFFFAOYSA-N 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- BHEOSNUKNHRBNM-UHFFFAOYSA-N Tetramethylsqualene Natural products CC(=C)C(C)CCC(=C)C(C)CCC(C)=CCCC=C(C)CCC(C)C(=C)CCC(C)C(C)=C BHEOSNUKNHRBNM-UHFFFAOYSA-N 0.000 description 1
- 238000005377 adsorption chromatography Methods 0.000 description 1
- 238000001042 affinity chromatography Methods 0.000 description 1
- 239000007866 anti-wear additive Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000005251 capillar electrophoresis Methods 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- PRAKJMSDJKAYCZ-UHFFFAOYSA-N dodecahydrosqualene Natural products CC(C)CCCC(C)CCCC(C)CCCCC(C)CCCC(C)CCCC(C)C PRAKJMSDJKAYCZ-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002270 exclusion chromatography Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000010720 hydraulic oil Substances 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 230000000155 isotopic effect Effects 0.000 description 1
- 238000002372 labelling Methods 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000004816 paper chromatography Methods 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 229940031439 squalene Drugs 0.000 description 1
- TUHBEKDERLKLEC-UHFFFAOYSA-N squalene Natural products CC(=CCCC(=CCCC(=CCCC=C(/C)CCC=C(/C)CC=C(C)C)C)C)C TUHBEKDERLKLEC-UHFFFAOYSA-N 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000012085 test solution Substances 0.000 description 1
- 238000004809 thin layer chromatography Methods 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 238000003828 vacuum filtration Methods 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 238000011179 visual inspection Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C43/00—Ethers; Compounds having groups, groups or groups
- C07C43/02—Ethers
- C07C43/03—Ethers having all ether-oxygen atoms bound to acyclic carbon atoms
- C07C43/14—Unsaturated ethers
- C07C43/164—Unsaturated ethers containing six-membered aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/003—Marking, e.g. coloration by addition of pigments
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/02—Preparation of ethers from oxiranes
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C43/00—Ethers; Compounds having groups, groups or groups
- C07C43/02—Ethers
- C07C43/20—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring
- C07C43/205—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring the aromatic ring being a non-condensed ring
- C07C43/2055—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring the aromatic ring being a non-condensed ring containing more than one ether bond
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C43/00—Ethers; Compounds having groups, groups or groups
- C07C43/02—Ethers
- C07C43/257—Ethers having an ether-oxygen atom bound to carbon atoms both belonging to six-membered aromatic rings
- C07C43/263—Ethers having an ether-oxygen atom bound to carbon atoms both belonging to six-membered aromatic rings the aromatic rings being non-condensed
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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
- C10L1/1852—Ethers; Acetals; Ketals; Orthoesters
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M171/00—Lubricating 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
- C10M171/007—Coloured or dyes-containing lubricant compositions
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/04—Ethers; Acetals; Ortho-esters; Ortho-carbonates
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/42—Flashing oils or marking oils
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Description
本發明係關於有用於作為液體烴及其他燃料與油之化學標記物之化合物。
以各種化學標記物對石油烴及其他燃料與油進行標記係於本領域中周知。各種化合物以及大量用於偵檢該等標記物之技術已用於此目的，該等技術係例如：吸收光譜法及質譜法。例如：美國申請案公開第2007/0184555號揭露使用各種用於標記液態烴及其他燃料與油之有機化合物。然而，對於用於此等產品之額外的標記物化合物一直有所需求。標記物的組合可用作數位標記系統，而以該等標記物之用量比例構成經標記產品之代碼。有用於作為燃料及潤滑劑標記物之額外化合物係所欲者，以最大化可用代碼。本發明欲解決之問題為尋找有用於標記液體烴及其他燃料與油之額外標記物。
本發明係提供一種具有式(I)之化合物，
其中，G表示至少一個選自C1-C12烷基和C1-C12烷氧基所組成群組之取代基。
本發明進一步提供一種用於標記石油烴、生質柴油燃料或乙醇燃料之方法，該方法包含將至少一種具有式(I)之化合物加入該石油烴、生質柴油燃料或乙醇燃料中，其中，G表示氫、C1-C12烷基或C1-C12烷氧基。
除非另外說明，否則百分比為重量百分比(wt%)且溫度為℃。濃度係以重量/重量為基準或以重量/容量(毫克(mg)/公升(L))為基準所計算之每百萬份之份數(ppm)來表示；較佳以重量/容量為基準。術語"石油烴"係指具有烴(即碳氫化合物)組成為主之產品，然而其可含有少量氧、氮、硫或磷；石油烴包含原油類以及從石油精煉過程衍生之產品；其包括，舉例而言，原油、潤滑油、液壓油、煞車油、汽油、柴油燃料、煤油、噴射機燃料及熱燃油(heating oil)。可將本發明之標記物化合物加入石油烴、生質柴油燃料、乙醇燃料、或其混合物中。生質柴油燃料為從生物衍生之含有脂肪酸烷酯(特別係甲酯)之混合物之燃料。生質柴油燃料係典型地藉由將初榨(virgin)或回收(recycled)植物油進行轉酯反應而產生，雖然亦可使用動物脂肪。乙醇燃料為含有純形式之乙醇或與石油烴混合之乙醇(如"酒精汽油(gasohol)")之任何燃料。"烷基"為具有一個至二十二個呈直鏈或分支鏈排列之碳原子之經取代或未經取代之烴基(hydrocarbyl)。較佳地，本發明之化合物係含有以其天然之同位素比例存在的元素。
於本發明之化合物中，G表示至少一個選自C1-C12烷基和C1-C12烷氧基所組成群組之取代基，亦即，式(I)中載有"G"取代基之各芳香環具有至少一個選自C1-C12烷基和C1-C12烷氧基所組成群組之取代基。較佳地，G表示在各芳香環上之一個至三個可為相同或不同的取代基，較佳為兩個或三個取代基，較佳為兩個或三個相同的取代基。然而，"G"所表示之一個或多個取代基在經G取代之兩個芳香環上係相同，亦即，該化合物以在中央聯苯部分(moiety)之苯環之間的對稱平面呈對稱。較佳地，G表示至少一個選自C1-C6烷基和C1-C6烷氧基(較佳為C2-C6烷基和C1-C6烷氧基，較佳為C1-C4烷基和C1-C4烷氧基，較佳為C2-C4烷基和C1-C4烷氧基，較佳為C1-C4烷基，較佳為C2-C4烷基)所組成群組之取代基。較佳地，G取代基係位於苯氧環的第2-位置及/或第4-位置。較佳地，G表示兩個或三個選自C1-C6烷基，較佳為C1-C4烷基，較佳為甲基和乙基之取代基，亦即，各苯氧基具有兩個或三個選自該等指定基團之取代基。
於本發明之方法中，較佳每種標記物之最小量為至少0.01 ppm，較佳為至少0.05 ppm，較佳為至少0.1 ppm，較佳為至少0.2 ppm。較佳地，每種標記物之最大量為50 ppm，較佳為20 ppm，較佳為15 ppm，較佳為10 ppm，較佳為5 ppm，較佳為2 ppm，較佳為1 ppm，較佳為0.5 ppm。較佳地，於經標記之石油烴、生質柴油燃料或乙醇燃料中，標記物化合物無法經由目視方法偵檢，亦即不可能經由肉眼目視觀察顏色或其他特徵而決定該石油烴、生質柴油燃料或乙醇燃料含有標記物化合物。較佳地，標記物化合物為一種通常不以作為石油烴、生質柴油燃料或乙醇燃料本身之成分，或作為用於該石油烴、生質柴油燃料或乙醇燃料之添加劑之方式存在於將添加該標記物化合物之石油烴、生質柴油燃料或乙醇燃料中之標記物化合物。
較佳地，該標記物化合物係具有至少3之log P值，其中，P為1-辛醇/水分配係數(partition coefficient)。較佳地，該標記物化合物具有至少4、較佳為至少5之log P值。未曾以實驗方式測定且未於文獻中發表之log P值可使用Meylan,W. M. & Howard,P. H.,J. Pharm Sci.,vol. 84,pp. 83-92(1995)中揭露之方法進行估計。較佳地，該石油烴、生質柴油燃料或乙醇燃料為石油烴或生質柴油燃料；較佳為石油烴；較佳為原油、汽油、柴油燃料、煤油、噴射機燃料或熱燃油；較佳為汽油。
於本發明之一具體實施例中，此等標記物化合物係經由使用層析技術(例如：氣相層析法、液相層析法、薄層層析法、紙層析法、吸附層析法、親和層析法、毛細管電泳、離子交換及分子排除層析法)將其從石油烴、生質柴油燃料或乙醇燃料之構成分中至少部分分離而予以偵檢。層析法後接著進行下列至少一者：(i)質譜分析，及(ii)傅立葉轉換紅外光譜分析(FTIR)。較佳係經由質譜分析測定標記物化合物之身份(identity)。較佳地，質譜分析係用以偵檢石油烴、生質柴油燃料或乙醇燃料中之標記物化合物，而無須進行任何分離。或者，標記物化合物可於分析前濃縮，例如：經由蒸餾除去石油烴或乙醇之某些較具揮發性之成分。
較佳地，存在超過一種標記物化合物。多重標記物化合物之使用促進將可用於識別石油烴、生質柴油燃料或乙醇燃料之來源與其他特徵之經編碼資訊併入石油烴、生質柴油燃料或乙醇燃料中。此代碼包含標記物化合物之身份與相對量，例如：標記物化合物之固定整數比。一種、二種、三種或更多種標記物化合物可用於形成該代碼。本發明之標記物化合物可與其他類型之標記物組合，其他類型之標記物例如，可由吸收光譜法偵檢之標記物，包括美國專利案第6,811,575號；美國專利申請案公開第2004/0250469號及歐洲申請案公開第1,479,749號中揭露之標記物。標記物化合物係直接置於石油烴、生質柴油燃料或乙醇燃料中，或置於含有其他化合物之添加劑包裝(例如，潤滑劑用抗磨損添加劑、汽油用清潔劑等等)中，再將該添加劑包裝添加到石油烴、生質柴油燃料或乙醇燃料中。
本發明之化合物可藉由本領域中已知的方法製備。例如，可使4,4’-雙氯甲基-1,1’-聯苯與經取代之酚根據下述反應式進行反應：
一個或多個取代基G可存在於酚之任何位置，例如包括，第2-、3-、4-、2,4-、2,6-、2,4,6-、3-、5-、3,5-、3,4-、2,3-等等位置。較佳地，經取代之酚僅在第2-及/或4-位置具有取代基。未經取代之酚可用於製備G=H之化合物。
將氫氧化鉀(KOH)小粒(7.26g，0.11mol基於85%活性)、二甲亞碸(DMSO)(100mL)和間甲酚(12.0g，0.11mol)裝料於已裝備加熱包、機械攪拌器且以氮氣覆蓋之250mL三頸瓶中。攪拌下，使混合物升溫至100℃維持兩小時，其間氫氧化鉀小粒會溶解且溶液變深褐色。將固體4,4’-雙氯甲基-1,1’-聯苯(12.6g，0.05mol)以五分鐘之週期加入溶液中。添加期間，移除加熱包以促進空氣冷卻且添加之限制速率以使反應之放熱不會造成內部之溫度超過115℃。反應混合物迅速地變成稠漿。使反應物料在100℃保持額外4小時後，在室溫攪拌混合物過夜，其間，混合物由漿體變為較液體。將反應物料注入含有300mL快速攪拌之水之燒杯，導致產物立即沉澱和氯化鉀(KCl)副產物溶解。藉由真空過濾且用水充分清洗以收集固體產物。將淺棕色糊狀物置於70℃之熱風式烘箱(forced air oven)乾燥維持數小時，提供19.2g(97.5%)粗產物。藉由紫外光(UV)偵檢器分析產物之GPC，證實純度非常高(>99%)。若有需要，產物可由甲苯(250mL)再結晶，產生18.0g(91.4%產率)之細晶體。1H和13C-NMR、IR、GC/MS都已確認產物之身分和純度。MP=151℃。
依據相同之程序，以甲酚之對位和鄰位異構物取代間位異構物。於各種情形下，1H、13C-NMR、IR、GC/MS與產物之身分和純度一致，也可經由對第三丁基酚製備苄基醚。
4,4’-雙(4-甲基苯氧基甲基)-1,1’-聯苯(對位異構物)；MP=206℃，二甲苯再結晶後之產率為93.9%。
4,4’-雙(2-甲基苯氧基甲基)-1,1’-聯苯(鄰位異構物)；MP=209℃，甲苯再結晶後之產率為93.5%。
4,4’-雙(4-第三丁基苯氧基甲基)-1,1’-聯苯；MP=218℃，甲苯再結晶後之產率為93.5%。
4,4’-雙(苯氧基甲基)-1,1’-聯苯；MP=176℃，甲苯再結晶後之產物。
以0.2ppm之濃度，將4,4’-雙(4-甲基苯氧基甲基)-1,1’-聯苯加入自地方Marathon加油站購買之商用柴油燃料中。藉由使用Agilent DB-35ms管柱(15公尺×0.25mm ID×0.25μm)之GC/MS分析經標記之燃料。使用下述溫度程式(program)分析該等樣本：起始於100℃，以20℃/分鐘之升溫速度升至280℃，於280℃保持10分鐘，之後以20℃/分鐘之升溫速度升至340℃，於340℃保持6分鐘，隨後以20℃/分鐘之升溫速度最終升至360℃，於360℃保持1分鐘。使用SIM：394輕易地偵檢出4,4’-雙(4-甲基苯氧基甲基)-1,1’-聯苯。重複分析(n=10)證實有少於6%之相對標準差(RSD)。重複此實驗，以0.2ppm之濃度，將4,4’-雙(2-甲基苯氧基甲基)-1,1’-聯苯之標記物加入燃料中，經由10次重複分析也證實有少於6%之相對標準差(RSD)。
使用含有100至1000ppm之標記物以及等量之鯊烯內參考標準品的二甲苯溶液，以下述方法(protocol)施行標記物的安定性及可萃取性：
洗滌：
將95份經標記之二甲苯與5份洗滌劑於100mL小瓶中混合。使用磁力攪拌棒溫和混合8小時。停止攪拌，取二甲苯溶液之等分分裝物。藉由GC分析，並比較標記物相對於參考(未洗滌)樣本之反應。
洗滌劑：
1)5%硫酸
2)98%硫酸
3)5% NaOH溶液
4)50% NaOH溶液
為了測試金屬吸附性，將100mL經標記之二甲苯測試溶液於室溫以5公克金屬切屑(shaving)處理8小時。再度使用GC分析，以測定任何流失至金屬表面之標記物。
Claims (6)
- 一種具有式(I)之化合物，
- 一種用於標記石油烴、生質柴油燃料或乙醇燃料之方法，該方法包含將至少一種具有式(I)之化合物加入該石油烴、生質柴油燃料或乙醇燃料中：
- 如申請專利範圍第2項所述之方法，其中，每種式(I)化合物係以0.05ppm至20ppm之濃度存在。
- 如申請專利範圍第3項所述之方法，其中，G表示氫或至少一個選自C1-C6烷基或C1-C6烷氧基所組成群組之取代基。
- 如申請專利範圍第4項所述之方法，其中，G表示兩個或三個選自C1-C4烷基所組成群組之取代基。
- 如申請專利範圍第5項所述之方法，其中，G表示兩個 或三個甲基或兩個或三個乙基。
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