KR20120114663A - Nonaqueous fluid marker having n-benzyl-n-ethylaniline and preparing method thereof - Google Patents
Nonaqueous fluid marker having n-benzyl-n-ethylaniline and preparing method thereof Download PDFInfo
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- KR20120114663A KR20120114663A KR1020110032329A KR20110032329A KR20120114663A KR 20120114663 A KR20120114663 A KR 20120114663A KR 1020110032329 A KR1020110032329 A KR 1020110032329A KR 20110032329 A KR20110032329 A KR 20110032329A KR 20120114663 A KR20120114663 A KR 20120114663A
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- ethylaniline
- benzyl
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- 239000012530 fluid Substances 0.000 title claims abstract description 35
- 238000000034 method Methods 0.000 title claims description 13
- 239000003550 marker Substances 0.000 title abstract 5
- XNDVYXSTYJNTBL-UHFFFAOYSA-N n-benzyl-n-ethylaniline Chemical compound C=1C=CC=CC=1N(C[CH2])CC1=CC=CC=C1 XNDVYXSTYJNTBL-UHFFFAOYSA-N 0.000 title 1
- HSZCJVZRHXPCIA-UHFFFAOYSA-N n-benzyl-n-ethylaniline Chemical compound C=1C=CC=CC=1N(CC)CC1=CC=CC=C1 HSZCJVZRHXPCIA-UHFFFAOYSA-N 0.000 claims abstract description 27
- 150000001448 anilines Chemical class 0.000 claims abstract description 13
- 125000005843 halogen group Chemical group 0.000 claims abstract description 7
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims abstract description 6
- 125000004642 (C1-C12) alkoxy group Chemical group 0.000 claims abstract 2
- -1 n -dodecyl group Chemical group 0.000 claims description 34
- 239000002253 acid Substances 0.000 claims description 20
- 239000003795 chemical substances by application Substances 0.000 claims description 18
- 239000003086 colorant Substances 0.000 claims description 17
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- 125000003545 alkoxy group Chemical group 0.000 claims description 9
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical group CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 claims description 7
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 7
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 claims description 7
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims description 7
- 239000008096 xylene Substances 0.000 claims description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 125000005037 alkyl phenyl group Chemical group 0.000 claims description 6
- 125000005036 alkoxyphenyl group Chemical group 0.000 claims description 5
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 239000003502 gasoline Substances 0.000 claims description 3
- 239000003225 biodiesel Substances 0.000 claims description 2
- 239000003350 kerosene Substances 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- 239000010687 lubricating oil Substances 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 13
- 238000002360 preparation method Methods 0.000 abstract description 4
- 125000006539 C12 alkyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 abstract 1
- 238000004090 dissolution Methods 0.000 abstract 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 35
- 239000000243 solution Substances 0.000 description 21
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 18
- 239000000975 dye Substances 0.000 description 16
- 239000006185 dispersion Substances 0.000 description 14
- 229960000583 acetic acid Drugs 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 238000010521 absorption reaction Methods 0.000 description 9
- 235000019260 propionic acid Nutrition 0.000 description 9
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 9
- 239000011259 mixed solution Substances 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- 239000000987 azo dye Substances 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- 230000008033 biological extinction Effects 0.000 description 3
- 238000006193 diazotization reaction Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000003209 petroleum derivative Substances 0.000 description 3
- LDMOEFOXLIZJOW-UHFFFAOYSA-N 1-dodecanesulfonic acid Chemical compound CCCCCCCCCCCCS(O)(=O)=O LDMOEFOXLIZJOW-UHFFFAOYSA-N 0.000 description 2
- FKPXGNGUVSHWQQ-UHFFFAOYSA-N 5-methyl-1,2-oxazol-3-amine Chemical compound CC1=CC(N)=NO1 FKPXGNGUVSHWQQ-UHFFFAOYSA-N 0.000 description 2
- KZHGPDSVHSDCMX-UHFFFAOYSA-N 6-methoxy-1,3-benzothiazol-2-amine Chemical compound COC1=CC=C2N=C(N)SC2=C1 KZHGPDSVHSDCMX-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000000986 disperse dye Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 2
- 229940093915 gynecological organic acid Drugs 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- 239000000976 ink Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 235000005985 organic acids Nutrition 0.000 description 2
- 238000003908 quality control method Methods 0.000 description 2
- 239000001632 sodium acetate Substances 0.000 description 2
- 235000017281 sodium acetate Nutrition 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- OGIQUQKNJJTLSZ-UHFFFAOYSA-N 4-butylaniline Chemical compound CCCCC1=CC=C(N)C=C1 OGIQUQKNJJTLSZ-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- CSCPPACGZOOCGX-WFGJKAKNSA-N acetone d6 Chemical compound [2H]C([2H])([2H])C(=O)C([2H])([2H])[2H] CSCPPACGZOOCGX-WFGJKAKNSA-N 0.000 description 1
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 150000008049 diazo compounds Chemical class 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- YRIUSKIDOIARQF-UHFFFAOYSA-N dodecyl benzenesulfonate Chemical compound CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 YRIUSKIDOIARQF-UHFFFAOYSA-N 0.000 description 1
- 229940071161 dodecylbenzenesulfonate Drugs 0.000 description 1
- 125000006232 ethoxy propyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 description 1
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000003935 n-pentoxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000003506 n-propoxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 238000001392 ultraviolet--visible--near infrared spectroscopy Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N31/00—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods
- G01N31/22—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods using chemical indicators
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B29/00—Monoazo dyes prepared by diazotising and coupling
- C09B29/0025—Monoazo dyes prepared by diazotising and coupling from diazotized amino heterocyclic compounds
- C09B29/0074—Monoazo dyes prepared by diazotising and coupling from diazotized amino heterocyclic compounds the heterocyclic ring containing nitrogen and sulfur as heteroatoms
- C09B29/0077—Monoazo dyes prepared by diazotising and coupling from diazotized amino heterocyclic compounds the heterocyclic ring containing nitrogen and sulfur as heteroatoms containing a five-membered heterocyclic ring with one nitrogen and one sulfur as heteroatoms
- C09B29/0085—Thiazoles or condensed thiazoles
- C09B29/0088—Benzothiazoles
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C245/00—Compounds containing chains of at least two nitrogen atoms with at least one nitrogen-to-nitrogen multiple bond
- C07C245/02—Azo compounds, i.e. compounds having the free valencies of —N=N— groups attached to different atoms, e.g. diazohydroxides
- C07C245/06—Azo compounds, i.e. compounds having the free valencies of —N=N— groups attached to different atoms, e.g. diazohydroxides with nitrogen atoms of azo groups bound to carbon atoms of six-membered aromatic rings
- C07C245/08—Azo compounds, i.e. compounds having the free valencies of —N=N— groups attached to different atoms, e.g. diazohydroxides with nitrogen atoms of azo groups bound to carbon atoms of six-membered aromatic rings with the two nitrogen atoms of azo groups bound to carbon atoms of six-membered aromatic rings, e.g. azobenzene
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B29/00—Monoazo dyes prepared by diazotising and coupling
- C09B29/0003—Monoazo dyes prepared by diazotising and coupling from diazotized anilines
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B29/00—Monoazo dyes prepared by diazotising and coupling
- C09B29/06—Monoazo dyes prepared by diazotising and coupling from coupling components containing amino as the only directing group
- C09B29/08—Amino benzenes
- C09B29/0805—Amino benzenes free of acid groups
- C09B29/0807—Amino benzenes free of acid groups characterised by the amino group
- C09B29/0809—Amino benzenes free of acid groups characterised by the amino group substituted amino group
- C09B29/081—Amino benzenes free of acid groups characterised by the amino group substituted amino group unsubstituted alkylamino, alkenylamino, alkynylamino, cycloalkylamino, aralkylamino or arylamino
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- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/0071—Process features in the making of dyestuff preparations; Dehydrating agents; Dispersing agents; Dustfree compositions
- C09B67/0083—Solutions of dyes
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- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
- G01N21/77—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator
- G01N21/78—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator producing a change of colour
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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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Abstract
Description
본 발명은 비수용성 유체 제품 식별제로 사용 가능한, 하기 화학식 1로 표시되는 아조 염료 및 이의 제조방법에 관한 것이다.The present invention relates to an azo dye represented by the following formula (1) and a method for preparing the same, which can be used as a non-aqueous fluid product identifier.
[화학식 1][Formula 1]
아조기(-N=N-)를 발색단으로 하는 염료를 아조 염료라고 하며, 아조 염료는 현재 상용화된 염료 중 50 % 이상을 차지하고 있다. 근래에는 염료에 기능성을 부여하여 다양한 용도에 적합한 신규 아조염료를 개발하고자 하는 연구가 꾸준하게 진행되고 있다.Azo dyes (-N = N-) as a chromophore are called azo dyes, and azo dyes currently account for more than 50% of commercial dyes. In recent years, research has been continuously conducted to develop novel azo dyes suitable for various applications by providing functionalities to dyes.
최근 발표된 연구(M. R. Yazdanbakhsh. et. al., J. Mol. Liquid. 151 : 107-112(2010))에 따르면 N-벤질-N-에틸아닐린을 커플러로 사용한 헤테로 아조 분산염료가 용매화 발색 현상을 나타내는 것으로 발표하였다.According to a recently published study (MR Yazdanbakhsh. Et. Al., J. Mol. Liquid. 151: 107-112 (2010)), heteroazo disperse dyes using N -benzyl- N -ethylaniline as a coupler are solvated. It was announced to indicate a phenomenon.
예를 들면, 하기 화학식 2로 표시되는 화합물의 최대흡수파장(λmax)이 클로로포름 용매에서는 503 nm 이나, 빙초산 용매에서는 614 nm로 111 nm 장파장 이동하는 것으로 보고하였다.For example, it has been reported that the maximum absorption wavelength (λ max ) of the compound represented by Chemical Formula 2 is 111 nm long wavelength shifted to 503 nm in chloroform solvent and 614 nm in glacial acetic acid solvent.
[화학식 2][Formula 2]
현재 비수용성 유체 제품들의 식별방법으로는 비수용성 유체 제품에 식별제를 가해준 다음 발색제로 산 또는 염기를 가하여 색을 발현시키는 방법, 근적외선 영역의 빛을 흡수하는 염료를 사용하여 정량하는 방법 등이 사용되고 있으나 시간경과에 따른 식별제의 효능이 약화되어 발색제의 색상이 사라지거나, 발색제가 쉽게 분해되어 취급이 어렵거나, 물 또는 유기 용매에서 식별제의 성분이 서서히 분해되어 정량 측정이 어려운 문제점이 있다.Current methods for identifying non-aqueous fluid products include adding an identifier to a non-aqueous fluid product and then adding an acid or a base as a colorant to express color, or quantifying it using a dye that absorbs light in the near infrared region. Although it is being used, the color of the colorant disappears due to the weakening of the efficacy of the colorant over time, the colorant is easily decomposed, and the handling of the colorant is difficult. .
취급이 용이하며, 보관 안정성이 높은 다양한 아조 염료들이 유기산 또는 무기산과 반응하여 석유제품을 표지하기 위한 식별제로 사용 가능함을 미국특허 6,514,917, 미국특허 5,737,871, 미국특허 5,490,872, WO 1995-017483 및 WO 1999-067346에서 보여주고 있다. 특히, 미국특허 6,514,917에서는 발색제로 석유제품과 혼화성인 유기인산 또는 술폰산 화합물을 사용하여 석유제품으로부터 수성 상으로 추출 없이 정량화 할 수 있는 방법을 보고하였다.US Pat. No. 6,514,917, US Pat. No. 5,737,871, US Pat. No. 5,490,872, WO 1995-017483, and WO 1999-. It is shown at 067346. In particular, US Pat. No. 6,514,917 reported a method that can be quantified without extraction from an petroleum product into an aqueous phase using an organophosphoric or sulfonic acid compound that is miscible with the petroleum product as a colorant.
비수용성 유체 제품의 식별제로 유용한 물질로는 적용하는 대상 제품에 높은 용해도를 보이며, 보관 안정성이 우수하고, 미량으로 검출이 가능하며, 검출 방법이 편리하고, 다양한 비수용성 유체 제품에 사용 가능할 것이 요구되고 있다. 그러나, 기존의 아조 염료들은 석유제품, 용제류, 잉크류, 윤활유 등과 같은 비수용성 유체 제품 중 일부 제품에 대한 용해도, 발색도 면에서 식별제로 적용하기 어렵다는 문제가 있었다.
Useful materials for the identification of non-aqueous fluid products include high solubility in the target product, excellent storage stability, traceable detection, convenient detection methods, and use in a variety of non-aqueous fluid products. It is becoming. However, the existing azo dyes have a problem that it is difficult to apply as an identification agent in terms of solubility and color development of some of the non-aqueous fluid products, such as petroleum products, solvents, inks, lubricants.
이에 본 발명자들은 비수용성 유체 제품에 뚜렷한 발색을 나타내며 수성 상으로 추출 없이 정량화 할 수 있는 용이한 화합물을 개발하고자 연구 노력한 결과, N-벤질-N-에틸아닐린을 함유하는 황색 아조 분산염료를 수 종 합성하고, 이들이 비수용성 유체 제품의 식별제로 유용하게 사용될 수 있음을 확인함으로써 본 발명을 완성하게 되었다. 따라서, 본 발명은 신규한 비수용성 유체 제품 식별용 황색 아조 분산염료 및 이의 제조방법의 제공에 그 목적이 있다.
Therefore, the present inventors have tried to develop an easy compound that can be quantified without extracting into an aqueous phase and having a clear color in a water-insoluble fluid product. As a result, several species of yellow azo dispersion dyes containing N -benzyl- N -ethylaniline are selected. The present invention has been accomplished by synthesizing and confirming that they can be usefully used as identification agents for non-aqueous fluid products. Accordingly, an object of the present invention is to provide a novel yellow azo dispersion dye for identifying a water-insoluble fluid product and a method for producing the same.
본 발명은 하기 화학식 1로 표시되는 N-벤질-N-에틸아닐린을 함유하는 비수용성 유체 식별제를 그 특징으로 한다.The present invention is characterized by a water-insoluble fluid identification agent containing N -benzyl- N -ethylaniline represented by the following formula (1).
[화학식 1][Formula 1]
상기 화학식 1에서, R은 C1 ~ C12의 알킬기, C1 ~ C12의 알콕시기, C1 ~ C12의 히드록시알킬기, C1 ~ C12의 히드록시알콕시알킬기, C1 ~ C12의 알킬페닐기, C1 ~ C12의 알콕시페닐기, 니트로기, 시안기 또는 할로겐 원자이다.
In
또한 본 발명은Also,
하기 화학식 3으로 표시되는 아닐린 유도체를 디아조화 하는 단계; 및Diazotizing an aniline derivative represented by Formula 3 below; And
상기 디아조화된 아닐린 유도체와 하기 화학식 4로 표시되는 N-벤질-N-에틸아닐린을 반응시키는 단계;Reacting the diazotized aniline derivative with N -benzyl- N -ethylaniline represented by Formula 4;
를 포함하는 하기 화학식 1로 표시되는 N-벤질-N-에틸아닐린을 함유하는 비수용성 유체 식별제의 제조방법을 그 특징으로 한다.Characterized in that the method for producing a water-insoluble fluid identification agent containing N -benzyl- N -ethylaniline represented by the following formula (1) comprising a.
상기 화학식 1 및 3에서, R은 상기에서 정의한 바와 같다.
In
또한 본 발명은 상기 화학식 1로 표시되는 N-벤질-N-에틸아닐린을 함유하는 비수용성 유체 식별제를 대상 제품에 용해시키고, 산 발색제로 제품을 발색시켜 비수용성 유체 제품을 식별하는 방법을 그 특징으로 한다.
The present invention also provides a method for identifying a non-aqueous fluid product by dissolving a non-aqueous fluid identification agent containing N -benzyl- N -ethylaniline represented by the formula (1) in a target product and developing the product with an acid colorant. It features.
본 발명의 N-벤질-N-에틸아닐린을 함유하는 식별제는 비수용성 유체 제품에 높은 용해도를 보이며, 보관 안정성이 우수하고, 미량으로 검출이 가능하며, 비수용성 유체 제품 내에서 도데실벤젠 설폰산 등의 유기산, 그리고 황산, 인산 등의 무기산과 반응하여 뚜렷한 발색을 나타낸다. 따라서, 자사 제품에 이러한 식별제를 첨가할 경우, 식별제가 첨가되지 않은 타사 제품 내지는 유사 휘발유와 같은 불법유통 제품과의 구별이 용이하므로, 유통과정에서 자사제품의 품질관리를 손쉽게 할 수 있다.
The identification agent containing N -benzyl- N -ethylaniline of the present invention exhibits high solubility in water-insoluble fluid products, excellent storage stability, detectable in trace amounts, and dodecylbenzene sulfonate in water-insoluble fluid products. Reacts vividly with organic acids such as phonic acid and inorganic acids such as sulfuric acid and phosphoric acid. Therefore, when such an identification agent is added to the company's product, it is easy to distinguish it from illegally distributed products such as other companies' products or similar gasoline without the identification agent, thereby facilitating quality control of the company's product in the distribution process.
도 1은 실시예 1의 아조 분산염료를 함유한 식별제 용액에 산 발색제가 첨가되기 전과 후의 UV-VIS 흡수스펙트럼 변화를 나타낸 그래프로서, 최대 흡수파장의 변화를 나타낸다.1 is a graph showing the change in the absorption spectrum of UV-VIS before and after the addition of the acid colorant to the identification solution containing the azo dispersion dye of Example 1, showing the change in the maximum absorption wavelength.
이하에서는 본 발명을 더욱 자세하게 설명하겠다.Hereinafter, the present invention will be described in more detail.
본 발명은 하기 화학식 1로 표시되는 N-벤질-N-에틸아닐린을 함유하는 비수용성 유체 식별제에 관한 것이다.The present invention relates to a water-insoluble fluid identification agent containing N -benzyl- N -ethylaniline represented by the following formula (1).
[화학식 1][Formula 1]
상기 화학식 1에서, R은 C1 ~ C12의 알킬기, C1 ~ C12의 알콕시기, C1 ~ C12의 히드록시알킬기, C1 ~ C12의 히드록시알콕시알킬기, C1 ~ C12의 알킬페닐기, C1 ~ C12의 알콕시페닐기, 니트로기, 시안기 또는 할로겐 원자이다.In
치환기에 대해 구체적으로 설명하면 다음과 같다.The substituent is specifically described as follows.
'알킬기'는 1개에서 12개까지의 탄소원자를 가지는 직쇄상 또는 분쇄상의 지방족 포화 탄화수소기를 의미하며, 구체적으로는 메틸기, 에틸기, n-프로필기, i-프로필기, n-부틸기, i-부틸기, t-부틸기, n-펜틸기, i-펜틸기, n-헥실기, i-헥실기, n-헵틸기, i-헵틸기, n-옥틸기, i-옥틸기, n-노닐기, i-노닐기, n-도데실기, i-도데실기 등이 포함될 수 있다."Alkyl group" means a straight or pulverized aliphatic saturated hydrocarbon group having 1 to 12 carbon atoms, specifically, methyl group, ethyl group, n -propyl group, i -propyl group, n -butyl group, i- Butyl group, t -butyl group, n -pentyl group, i -pentyl group, n -hexyl group, i -hexyl group, n -heptyl group, i -heptyl group, n -octyl group, i -octyl group, n − Nonyl group, i -nonyl group, n -dodecyl group, i -dodecyl group and the like can be included.
'알콕시기'는 1개에서 12개까지의 탄소원자를 가지는 직쇄상 또는 분쇄상의 지방족 알콕시기를 의미하며, 구체적으로는 메톡시기, 에톡시기, n-프로피옥시기, i-프로피옥시기, n-부톡시기, i-부톡시기, t-부톡시기, n-펜톡시기, i-펜톡시기 등이 포함될 수 있다."Alkoxy group" means a straight or pulverized aliphatic alkoxy group having 1 to 12 carbon atoms, specifically, a methoxy group, an ethoxy group, n -propoxy group, i -propoxy group, n -butok A time period, i -butoxy group, t -butoxy group, n -pentoxy group, i -pentoxy group, etc. may be contained.
'히드록시알킬기'는 상기에서 정의된 알킬기에 히드록시기가 결합된 OH-알킬을 의미하며, 구체적으로는 히드록시메틸기, 히드록시에틸기, 히드록시n-프로필기, 히드록시n-부틸기, 히드록시i-부틸기, 히드록시n-펜틸기, 히드록시i-펜틸기, 히드록시n-헥실기, 히드록시i-헥실기 등이 포함될 수 있다.'Hydroxyalkyl group' means OH-alkyl in which a hydroxy group is bonded to the alkyl group defined above, and specifically, hydroxymethyl group, hydroxyethyl group, hydroxy n -propyl group, hydroxy n -butyl group, hydroxy i -butyl group, hydroxy n -pentyl group, hydroxy i -pentyl group, hydroxy n -hexyl group, hydroxy i -hexyl group and the like can be included.
'히드록시알콕시알킬기'는 히드록시알킬기에 알콕시기가 결합된 히드록시알킬-O-알킬을 의미하며, 구체적으로는 히드록시에톡시메틸기, 히드록시에톡시에틸기, 히드록시메톡시프로필기, 히드록시에톡시프로필기, 히드록시에톡시부틸기, 히드록시에톡시펜틸기, 히드록시에톡시헥실기 등이 포함할 수 있다."Hydroxyalkoxyalkyl group" means hydroxyalkyl-O-alkyl in which an alkoxy group is bonded to a hydroxyalkyl group, and specifically, hydroxyethoxymethyl group, hydroxyethoxyethyl group, hydroxymethoxypropyl group, hydroxy An ethoxy propyl group, a hydroxy ethoxy butyl group, a hydroxy ethoxy pentyl group, a hydroxy ethoxy hexyl group, etc. can be included.
'알킬페닐기'는 메틸페닐기, 에틸페닐기, n-프로필페닐기, n-부틸페닐기 등이 포함될 수 있다.The 'alkylphenyl group' may include methylphenyl group, ethylphenyl group, n -propylphenyl group, n -butylphenyl group and the like.
'알콕시페닐기'는 메톡시페닐기, 에톡시페닐기, n-프로피옥시페닐기, n-부톡시페닐기 등이 포함될 수 있다."Alkoxy group" are methoxy group, ethoxy group, n in the - might include butoxyphenyl-propynyl oxy group, a n.
'할로겐 원자'는 불소 원자, 염소 원자, 브롬 원자 또는 요오드 원자이다.'Halogen atom' is a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.
본 발명에 따른 유류 식별제에서 특히 바람직 한 화합물은 화학식 1에서 R이 C1 ~ C12의 알킬기, C1 ~ C12의 알콕시기인 것이다.
A particularly preferred oil in the identification of the compounds of the invention R 1 in
또한, 본 발명은 상기 화학식 1로 표시되는 N-벤질-N-에틸아닐린을 함유하는 비수용성 유체 식별제의 제조방법에 관한 것으로, 이러한 비수용성 유체 식별제는 하기 화학식 3으로 표시되는 아닐린 유도체를 디아조화 한 다음, 이를 하기 화학식 4로 표시되는 N-벤질-N-에틸아닐린과 반응시켜 제조할 수 있다.In addition, the present invention relates to a method for preparing a water-insoluble fluid identifier containing N -benzyl- N -ethylaniline represented by the formula (1), the non-aqueous fluid identifier is aniline derivative represented by the formula After diazotization, it may be prepared by reacting with N -benzyl- N -ethylaniline represented by the following formula (4).
상기 화학식 1 및 3에서, R은 상기에서 정의한 바와 같다.In
보다 자세하게 설명하면, 먼저 상기 화학식 3으로 표시되는 아닐린 유도체를 디아조화하는 단계에서, 디아조화 방법은 0 ~ 10℃에서 아닐린 유도체를 물, 초산, 또는 초산과 프로피온산의 혼합용액에 분산시킨 후, 진한 염산과 NaNO2 또는 HO3SONO를 첨가하고 반응시킴으로써 수행한다. 이때, 혼합용액은 초산과 프로피온산이 5 : 1 의 부피비로 혼합된 것이 좋다.In more detail, in the first step of diazoalizing the aniline derivative represented by Formula 3, the diazoation method is a dispersion of aniline derivative in water, acetic acid, or a mixed solution of acetic acid and propionic acid at 0 ~ 10 ℃, and then concentrated This is done by adding hydrochloric acid and NaNO 2 or HO 3 SONO and reacting. At this time, the mixed solution is preferably mixed with acetic acid and propionic acid in a volume ratio of 5: 1.
이후, 디아조화된 아닐린 유도체를 상기 화학식 4로 표시되는 N-벤질-N-에틸아닐린과 반응시키면, 화학식 1로 표시되는 황색 아조 분산염료를 얻을 수 있다. N-벤질-N-에틸아닐린을 별도의 용기에서 초산, 또는 초산과 프로피온산의 혼합용액에 용해시키고 0 ~ 10℃로 유지시켜 놓은 다음, 이러한 N-벤질-N-에틸아닐린 용액을 상기 디아조화된 아닐린 유도체 용액에 첨가하고 0 ~ 10℃에서 반응을 수행하는 것이 좋다. 이때 상기 초산과 프로피온산의 혼합용액은 초산과 프로피온산의 부피비가 5 : 1 인 것이 좋다.
Thereafter, when the diazotized aniline derivative is reacted with N -benzyl- N -ethylaniline represented by Chemical Formula 4, a yellow azo dispersion dye represented by Chemical Formula 1 may be obtained. N -benzyl- N -ethylaniline is dissolved in acetic acid, or a mixture of acetic acid and propionic acid, in a separate container and kept at 0 to 10 ° C., and then the N -benzyl- N -ethylaniline solution is diazotized. It is preferable to add to the aniline derivative solution and to carry out the reaction at 0 to 10 ° C. In this case, the mixed solution of acetic acid and propionic acid may have a volume ratio of acetic acid and propionic acid 5: 1.
또한, 본 발명은 상기 화학식 1로 표시되는 N-벤질-N-에틸아닐린을 함유하는 비수용성 유체 식별제로 대상 제품을 식별하는 방법에 관한 것이다.In addition, the present invention relates to a method for identifying a subject product by a non-aqueous fluid identification agent containing N -benzyl- N -ethylaniline represented by the formula (1).
본 발명의 상기 화학식 1로 표시되는 N-벤질-N-에틸아닐린을 함유하는 비수용성 유체 식별제는 대상 제품에 용해 시, 산 발색제와 반응하여 보라색의 발색을 나타낸다. 즉, 비수용성 유체 제품에서 본 발명의 식별제와 산 발색제가 반응하면 제품의 최대흡수파장이 410 nm 에서 장파장인 560 nm 로 이동하므로 제품의 색이 고유의 색(예. 노란색)에서 보라색으로 변한다. 따라서, 본 발명의 식별제를 함유한 비수용성 유체 제품과 식별제를 함유하지 않는 제품과의 구별이 가능하다. 즉, 비수용성 유체 제조사에서 본 발명의 식별제를 제품에 용해시킬 경우, 산 발색제를 사용하여 자사 제품을 타사 제품과 손쉽게 구별할 수 있어 유통과정에서의 자사 제품의 품질관리가 가능하다. 식별가능한 제품으로는 비수용성 유체라면 그 종류를 특별히 한정하지 않으며, 예를 들면 가솔린, 경유, 등유, 바이오디젤, 바이오에탄올, 크실렌, 잉크, 비수용성 윤활유, 용제류 등을 들 수 있으며, 이들 중 2종 이상의 혼합물에도 적용할 수 있다. 또한, 상기 산 발색제로는 도데실 설폰산 등의 유기산, 그리고 황산, 인산 등의 무기산을 들 수 있다. 바람직하기로는 도데실 설폰산을 산 발색제로 사용하는 것이 좋다.
The non-aqueous fluid identification agent containing N -benzyl- N -ethylaniline represented by
이하, 본 발명을 실시예에 의거하여 더욱 상세히 설명하겠는바 본 발명이 다음 실시예에 의해 한정되는 것은 아니다.Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited by the following Examples.
[실시예][Example]
실시예 1Example 1
디아조체로 4-부틸아닐린 5.37 g(0.036 mol)을 산 혼합용액(초산 : 프로피온산 = 5 : 1 부피비) 70 ml에 넣고 실온에서 20분 정도 교반 후, 35% 염산 7.7 ml(0.089 mol)을 가해주고 반응물을 5 ~ 10℃로 유지하였다. 그런 다음 3N NaNO2 13 ml(0.039 mol)을 반응온도가 승온되지 않도록 주의하면서 천천히 가해주고 5 ~ 10℃에서 1.5 시간 교반하여 디아조화를 완료하고 소량의 설파믹산을 가하여 과량의 아질산을 제거하였다.5.37 g (0.036 mol) of 4-butylaniline was added to 70 ml of an acid mixed solution (acetic acid: propionic acid = 5: 1 by volume), and stirred at room temperature for about 20 minutes. Then, 7.7 ml (0.089 mol) of 35% hydrochloric acid was added thereto. And the reaction was kept at 5-10 ° C. Then, 13 ml (0.039 mol) of 3 N NaNO 2 was slowly added while being careful not to raise the reaction temperature and stirred at 5 to 10 ° C. for 1.5 hours to complete diazotization, and a small amount of sulfamic acid was added to remove excess nitrite. .
한편, 커플러로 N-벤질-N-에틸아닐린 7.6 g(0.036 mol)을 산 혼합용액(초산 : 프로피온산 = 5 : 1 부피비) 20 ml에 용해하고 이를 5 ~ 10℃로 유지한 다음, 상기에서 얻은 디아조액에 천천히 첨가하고 5 ~ 10℃에서 3.5 시간 동안 교반하였다. 반응용액에 아세트산나트륨(NaOAc) 25 g을 넣고 실온에서 30 분 동안 교반 후, 반응용액을 얼음물 250 g에 더하고 1 시간 교반한 다음 생성된 고체를 여과하였다. 생성물을 정제하기 위하여 이소프로필알콜 100 ml 에 분산 시키고 실온에서 30분 교반 후 여과하고 건조하여 하기 화학식 5로 표시되는 황색의 고체 아조 분산염료인, 본 발명의 식별제를 얻었다.Meanwhile, 7.6 g (0.036 mol) of N -benzyl- N -ethylaniline was dissolved in 20 ml of an acid mixed solution (acetic acid: propionic acid = 5: 1 by volume) using a coupler, and maintained at 5 to 10 ° C., which was obtained above. The diazo solution was slowly added and stirred at 5-10 ° C. for 3.5 hours. 25 g of sodium acetate (NaOAc) was added to the reaction solution and stirred at room temperature for 30 minutes. Then, the reaction solution was added to 250 g of ice water, stirred for 1 hour, and the resulting solid was filtered. To purify the product, it was dispersed in 100 ml of isopropyl alcohol, stirred for 30 minutes at room temperature, filtered, and dried to obtain a yellow solid azo dispersion dye represented by the following formula (5).
[화학식 5][Chemical Formula 5]
실시예 2 ~ 5Examples 2 to 5
상기 실시예 1과 동일한 방법으로 실시하되, 하기 표 1에 나타낸 바와 같은 아닐린 유도체를 사용하여 황색의 고체 아조 분산염료인, 본 발명의 N-벤질-N-에틸아닐린을 함유하는 비수용성 유체 식별제를 얻었다.
A non-aqueous fluid identification agent containing N -benzyl- N -ethylaniline of the present invention, which is carried out in the same manner as in Example 1, but using aniline derivatives as shown in Table 1, which is a yellow solid azo dispersion dye. Got.
하기 표 1에는 상기 실시예 1 내지 5의 상기 화학식 3으로 표시되는 아닐린 유도체, 아닐린 유도체 사용량 및 합성 수율을 기재하였다.Table 1 below describes the amount of aniline derivatives represented by Formula 3, aniline derivatives used in Examples 1 to 5, and synthetic yields.
비교예 1Comparative Example 1
디아조체로 2-아미노-6-메톡시벤조티아졸 0.9 g(0.005 mol)을 산 혼합용액(초산 : 프로피온산 = 5 : 1 부피비) 10 ml에 넣고 실온에서 20분 정도 교반 후 반응물을 0 ~ 5℃로 유지하였다. 그런 다음 40% HO3SONO 1.05 ml(0.0053 mol)을 반응온도가 승온되지 않도록 주의하면서 천천히 가해주고, 반응물을 5 ~ 10℃에서 1.5 시간 동안 교반하여 디아조화를 완료하고 소량의 우레아를 가하여 과량의 아질산을 제거하였다.0.9 g (0.005 mol) of 2-amino-6-methoxybenzothiazole was added to the diazo body in 10 ml of an acid mixed solution (acetic acid: propionic acid = 5: 1 by volume) and stirred at room temperature for about 20 minutes. Maintained at ° C. Then, 1.05 ml (0.0053 mol) of 40% HO 3 SONO was slowly added while being careful not to raise the reaction temperature, and the reaction was stirred at 5 to 10 ° C. for 1.5 hours to complete diazotization, and a small amount of urea was added. Nitrous acid was removed.
한편, 커플러로 N-벤질-N-에틸아닐린 1.05 g(0.005 mol)을 산 혼합용액(초산 : 프로피온산 = 5 : 1 부피비) 10 ml에 용해하고 이를 0 ~ 5℃로 유지한 다음 상기에서 얻은 디아조액에 천천히 첨가하고 0 ~ 5℃에서 2 시간 동안 교반하였다. 반응용액에 아세트산나트륨(NaOAc) 2.5 g을 넣고 실온에서 30 분 동안 교반 후, 반응물을 얼음물 50 g에 더하고 1 시간 교반한 다음 생성된 고체를 여과하였다. 생성물을 정제하기 위하여 이소프로필알콜 20 ml에 분산 시키고 실온에서 30분 교반 후 여과하고 건조하여 하기 화학식 2로 표시되는 붉은색의 고체 아조 분산염료 1.78 g(수율 = 88.6 %)를 얻었다. Meanwhile, 1.05 g (0.005 mol) of N -benzyl- N -ethylaniline was dissolved in 10 ml of an acid mixed solution (acetic acid: propionic acid = 5: 1 by volume) using a coupler, and maintained at 0 to 5 ° C., followed by dia Slowly added to the crude liquid and stirred for 2 hours at 0 ~ 5 ℃. 2.5 g of sodium acetate (NaOAc) was added to the reaction solution, followed by stirring at room temperature for 30 minutes. The reaction was added to 50 g of ice water, stirred for 1 hour, and the resulting solid was filtered. To purify the product, it was dispersed in 20 ml of isopropyl alcohol, stirred for 30 minutes at room temperature, filtered, and dried to obtain 1.78 g (yield = 88.6%) of red solid azo dispersion dye represented by the following
[화학식 2][Formula 2]
비교예 2Comparative Example 2
상기 비교예 1과 동일하게 실시하되, 디아조체로 3-아미노-5-메틸이속사졸 0.49 g(0.005 mol)을 사용하여 하기 화학식 6으로 표시되는 황색의 고체 아조 분산염료 1.20 g(수율 = 75 %)를 얻었다.1.20 g (yield = 75) of a yellow solid azo dispersion dye represented by the following Chemical Formula 6, using 0.49 g (0.005 mol) of 3-amino-5-methylisoxazole as a diazo compound. %) Was obtained.
[화학식 6][Formula 6]
하기 표 2에는 실시예 1 ~ 5 및 비교예 1 ~ 2에서 제조한 각각의 N-벤질-N-에틸아닐린을 함유하는 아조 분산염료의 구조를 확인하기 위한 질량 스펙트럼(m/e) 및 1H NMR 스펙트럼 데이터를 정리하여 나타내었다.Table 2 below shows the mass spectra ( m / e ) and 1 H for confirming the structures of the azo dispersion dyes containing N -benzyl- N -ethylaniline prepared in Examples 1 to 5 and Comparative Examples 1 to 2. The NMR spectral data are shown collectively.
실험예Experimental Example : 황색 : yellow 아조AZO 분산염료의 산 반응특성 확인 실험 Acid Reaction Characteristic Test of Disperse Dyes
1) 식별제 용액 제조1) Preparation of identification solution
실시예 1 ~ 5 및 비교예 1 ~ 2에서 제조된 아조 분산염료를 적정량 취하여 크실렌으로 25 ml 용량 플라스크에 묽히고, 이중 1 ml을 취하여 크실렌으로 10 ml 용량 플라스크에 묽혀 식별제 용액을 제조하였다. 식별제 용액의 농도는 하기 표 3과 같다.
An appropriate amount of the azo dispersion dyes prepared in Examples 1 to 5 and Comparative Examples 1 to 2 was taken and diluted in a 25 ml volumetric flask with xylene, and 1 ml of the diluted solution was diluted with a 10 ml volumetric flask with xylene to prepare an identification solution. The concentration of the identification solution is shown in Table 3 below.
2) 산 발색제 용액 제조2) Acid Coloring Agent Solution Preparation
도데실벤젠 설폰산 7 g에 크실렌 3 g을 가하여 발색제 용액을 제조하였다.
3 g of xylene was added to 7 g of dodecylbenzene sulfonic acid to prepare a color developer solution.
3) UV-VIS 흡수 분광강도 및 최대흡수 파장 측정3) UV-VIS Absorption Spectral Intensity and Maximum Absorption Wavelength Measurement
상기 1)에서 준비한 시료의 UV-VIS 몰 흡광계수(ε) 및 최대 흡수파장(λmax)을 측정한 다음, 여기에 상기 2)에서 제조한 산 발색제 용액 10 ㎕를 가해주고 1분 동안 교반한 후, 시료의 UV-VIS 몰 흡광계수(ε) 및 최대 흡수파장(λmax)을 측정하여 색상의 변화를 관찰하였다. UV-VIS 몰 흡광계수 및 최대흡수파장은 UV-VIS-NIR 분광광도계(시마즈 社, UV-3101 PC)를 이용하여 측정하였다. 측정결과는 하기 표 3 및 도 1과 같다.The UV-VIS molar extinction coefficient (ε) and the maximum absorption wavelength (λ max ) of the sample prepared in 1) were measured, and then 10 μl of the acid colorant solution prepared in 2) was added thereto, followed by stirring for 1 minute. Thereafter, the UV-VIS molar extinction coefficient (ε) and the maximum absorption wavelength (λ max ) of the sample were measured to observe the change in color. The UV-VIS molar extinction coefficient and the maximum absorption wavelength were measured using a UV-VIS-NIR spectrophotometer (UV-3101 PC, Shimadzu Corporation). The measurement results are shown in Table 3 and FIG. 1.
(mg /L)Concentration
(mg / L)
(nm)Wavelength change
(nm)
Lmol-1cm-1 ε max /
Lmol -1 cm -1
Lmol-1cm-1 ε max /
Lmol -1 cm -1
알킬기가 치환된 아조 황색 분산염료인 실시예 1 ~ 4의 경우, 식별제 용액에 도데실벤젠 설폰산을 용액을 가해 주었을 때 뚜렷한 보라색의 발색과 함께 최대흡수파장이 150 nm 이상 장파장 이동함을 보여주었다.In Examples 1 to 4, in which the alkyl group was substituted with an azo yellow dispersion dye, when dodecylbenzene sulfonic acid was added to the identifier solution, the maximum absorption wavelength was shifted by 150 nm or more with distinct purple color development. gave.
메톡시기가 치환된 아조 황색 분산염료인 실시예 5의 경우, 도데실벤젠 설폰산을 용액을 가해 주었을 때, 상기 표 3과 같이 476 nm에서의 흡광도가 565 nm에서 보다 높았으며, 따라서 용액의 색상 변화는 관찰 할 수 있었으나 색상이 뚜렷하게 발현되지 않았다.In Example 5, in which the methoxy group was substituted with azo yellow dispersion dye, when dodecylbenzene sulfonic acid was added to the solution, the absorbance at 476 nm was higher at 565 nm as shown in Table 3, and thus the color of the solution. The change could be observed but the color was not apparent.
2-아미노-6-메톡시벤조티아졸을 디아조체로 사용한 비교예 1의 경우, 도데실벤젠 설폰산을 용액을 가해 주었을 때 23 nm 장파장 이동하여 용액의 색상 변화 정도가 적었으며, 또한 비교예 1의 화학식 2의 화합물은 크실렌 용매에서 발색되지 않았을 때 붉은색의 가시적인 색상을 부여하므로 식별제로 사용하기에 적합하지 않았다.In Comparative Example 1 using 2-amino-6-methoxybenzothiazole as a diazo, when the solution was added to dodecylbenzene sulfonic acid, the wavelength shifted by 23 nm was small, and the degree of color change of the solution was small. The compound of
디아조체로 3-아미노-5-메틸이속사졸을 사용한 비교예 2의 경우, 도데실벤젠 설폰산을 용액을 가해 주었을 때 43 nm 장파장 이동하여 용액의 색상 변화 정도가 적었으며, 산 발색제를 가해 준 후에도 진한 노란색의 가시적인 색상을 나타내어 식별제로 적합하지 않았다.In Comparative Example 2 using 3-amino-5-methylisoxazole as a diazo, when dodecylbenzene sulfonic acid was added to the solution, the wavelength shifted by 43 nm was small and the color change of the solution was small. Even after giving a dark yellow visible color was not suitable for identification.
따라서, 산 발색제인 도데실벤젠 설폰산의 첨가에 의하여 뚜렷한 색상을 발현하는 실시예 1 ~ 4의 알킬기가 치환된 아조 황색 분산염료가 산 반응성 식별제로 더 유용하게 사용 가능할 것으로 생각된다.Therefore, it is thought that the azo yellow dispersion dye substituted with the alkyl group of Examples 1 to 4 expressing a distinct color by the addition of dodecylbenzene sulfonic acid as an acid coloring agent may be more usefully used as an acid reactivity identifier.
Claims (6)
[화학식 1]
상기 화학식 1에서, R은 C1 ~ C12의 알킬기, C1 ~ C12의 알콕시기, C1 ~ C12의 히드록시알킬기, C1 ~ C12의 히드록시알콕시알킬기, C1 ~ C12의 알킬페닐기, C1 ~ C12의 알콕시페닐기, 니트로기, 시안기 또는 할로겐 원자이다.
A non-aqueous fluid identifier containing N -benzyl- N -ethylaniline represented by Formula 1:
[Formula 1]
In Formula 1, R is C 1 An alkyl group of C 12 , C 1 Alkoxy group of C 12 , C 1 C 12 hydroxyalkyl group, C 1 C 12 hydroxyalkoxyalkyl group, C 1 An alkylphenyl group of C 12 , C 1 C12 is an alkoxyphenyl group, nitro group, cyan group or halogen atom.
The non-aqueous fluid discriminating agent containing N -benzyl- N -ethylaniline according to claim 1, wherein R is a methyl group, n -butyl group, t -butyl group, n -dodecyl group or methoxy group.
상기 디아조화된 아닐린 유도체와 하기 화학식 4로 표시되는 N-벤질-N-에틸아닐린을 반응시키는 단계;
를 포함하는 하기 화학식 1로 표시되는 N-벤질-N-에틸아닐린을 함유하는 비수용성 유체 식별제의 제조방법:
상기 화학식 1 및 화학식 3에서, R은 C1 ~ C12의 알킬기, C1 ~ C12의 알콕시기, C1 ~ C12의 히드록시알킬기, C1 ~ C12의 히드록시알콕시알킬기, C1 ~ C12의 알킬페닐기, C1 ~ C12의 알콕시페닐기, 니트로기, 시안기 또는 할로겐 원자이다.
Diazotizing an aniline derivative represented by Formula 3 below; And
Reacting the diazotized aniline derivative with N -benzyl- N -ethylaniline represented by Formula 4;
Method for preparing a non-aqueous fluid identification agent containing N -benzyl- N -ethylaniline represented by the following formula (1) comprising:
In Formula 1 and Formula 3, R is C 1 An alkyl group of C 12 , C 1 C 12 alkoxy group, C 1 to C 12 hydroxyalkyl group, C 1 C 12 hydroxyalkoxyalkyl group, C 1 An alkylphenyl group of C 12 , C 1 C12 is an alkoxyphenyl group, nitro group, cyan group or halogen atom.
[화학식 1]
상기 화학식 1에서, R은 C1 ~ C12의 알킬기, C1 ~ C12의 알콕시기, C1 ~ C12의 히드록시알킬기, C1 ~ C12의 히드록시알콕시알킬기, C1 ~ C12의 알킬페닐기, C1 ~ C12의 알콕시페닐기, 니트로기, 시안기 또는 할로겐 원자이다.
A method of identifying a non-aqueous fluid product by dissolving a non-aqueous fluid identifier containing N -benzyl- N -ethylaniline represented by Formula 1 in a target product and developing the product with an acid colorant:
[Formula 1]
In Formula 1, R is C 1 An alkyl group of C 12 , C 1 Alkoxy group of C 12 , C 1 C 12 hydroxyalkyl group, C 1 C 12 hydroxyalkoxyalkyl group, C 1 An alkylphenyl group of C 12 , C 1 C12 is an alkoxyphenyl group, nitro group, cyan group or halogen atom.
The method of claim 4, wherein the subject product is at least one selected from gasoline, diesel, kerosene, biodiesel, bioethanol, xylene, ink, and non-aqueous lubricating oil.
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| KR1020110032329A KR101300673B1 (en) | 2011-04-07 | 2011-04-07 | Nonaqueous fluid marker having N-benzyl-N-ethylaniline and Preparing method thereof |
| PCT/KR2012/000990 WO2012138049A1 (en) | 2011-04-07 | 2012-02-10 | Non-aqueous fluid marker containing n-benzyl-n-ethylaniline and method for preparing the same |
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| KR1020110032329A KR101300673B1 (en) | 2011-04-07 | 2011-04-07 | Nonaqueous fluid marker having N-benzyl-N-ethylaniline and Preparing method thereof |
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| CN105859576A (en) * | 2016-05-05 | 2016-08-17 | 成都中恒华铁科技有限公司 | Method for synthesizing phenylbutazone drug intermediate azobenzene |
| CN107421899A (en) * | 2017-06-28 | 2017-12-01 | 重庆市宇驰检测技术有限公司 | Determine the detection method of water quality aniline, formaldehyde simultaneously based on ultraviolet-visible absorption spectroscopy |
| CN112051224B (en) * | 2020-08-12 | 2021-08-06 | 昆明理工大学 | Method for detecting blending ratio of biodiesel blending fuel based on ultraviolet-visible spectrophotometry |
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