KR100288120B1 - Reactive blue dyes containing monochlorotriazine and acetoxyethyl sulfone groups - Google Patents
Reactive blue dyes containing monochlorotriazine and acetoxyethyl sulfone groups Download PDFInfo
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- KR100288120B1 KR100288120B1 KR1019990004295A KR19990004295A KR100288120B1 KR 100288120 B1 KR100288120 B1 KR 100288120B1 KR 1019990004295 A KR1019990004295 A KR 1019990004295A KR 19990004295 A KR19990004295 A KR 19990004295A KR 100288120 B1 KR100288120 B1 KR 100288120B1
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- ORLGPUVJERIKLW-UHFFFAOYSA-N 5-chlorotriazine Chemical compound ClC1=CN=NN=C1 ORLGPUVJERIKLW-UHFFFAOYSA-N 0.000 title abstract description 7
- ZNEZVLKEOCTFHJ-UHFFFAOYSA-N 2-(2-acetyloxyethylsulfonyl)ethyl acetate Chemical group CC(=O)OCCS(=O)(=O)CCOC(C)=O ZNEZVLKEOCTFHJ-UHFFFAOYSA-N 0.000 title 1
- 239000001045 blue dye Substances 0.000 title 1
- 239000000985 reactive dye Substances 0.000 claims abstract description 32
- YLKCIGNYHDIGOF-UHFFFAOYSA-N [2-(2-acetyloxy-2-amino-2-phenylethyl)sulfonyl-1-amino-1-phenylethyl] acetate Chemical compound C=1C=CC=CC=1C(N)(OC(=O)C)CS(=O)(=O)CC(N)(OC(C)=O)C1=CC=CC=C1 YLKCIGNYHDIGOF-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 6
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims description 40
- 238000005859 coupling reaction Methods 0.000 claims description 22
- APRRQJCCBSJQOQ-UHFFFAOYSA-N 4-amino-5-hydroxynaphthalene-2,7-disulfonic acid Chemical compound OS(=O)(=O)C1=CC(O)=C2C(N)=CC(S(O)(=O)=O)=CC2=C1 APRRQJCCBSJQOQ-UHFFFAOYSA-N 0.000 claims description 17
- 150000001875 compounds Chemical class 0.000 claims description 13
- 238000006482 condensation reaction Methods 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 11
- MGNCLNQXLYJVJD-UHFFFAOYSA-N cyanuric chloride Chemical compound ClC1=NC(Cl)=NC(Cl)=N1 MGNCLNQXLYJVJD-UHFFFAOYSA-N 0.000 claims description 8
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 claims description 4
- 230000003472 neutralizing effect Effects 0.000 claims description 3
- 239000000975 dye Substances 0.000 abstract description 43
- 238000000034 method Methods 0.000 abstract description 40
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 35
- 238000004043 dyeing Methods 0.000 abstract description 24
- 150000003839 salts Chemical class 0.000 abstract description 18
- 239000002351 wastewater Substances 0.000 abstract description 8
- 238000009938 salting Methods 0.000 abstract description 7
- AFOSIXZFDONLBT-UHFFFAOYSA-N divinyl sulfone Chemical group C=CS(=O)(=O)C=C AFOSIXZFDONLBT-UHFFFAOYSA-N 0.000 abstract description 6
- 239000000706 filtrate Substances 0.000 abstract description 4
- 238000001914 filtration Methods 0.000 abstract description 4
- 238000004065 wastewater treatment Methods 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 49
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 33
- 239000007864 aqueous solution Substances 0.000 description 23
- 238000003756 stirring Methods 0.000 description 23
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 17
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 15
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 15
- 238000006193 diazotization reaction Methods 0.000 description 12
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 11
- 238000006386 neutralization reaction Methods 0.000 description 11
- -1 polyoxyethylene nonylphenyl ether Polymers 0.000 description 11
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 10
- MAFGFYFHPXKEJJ-UHFFFAOYSA-N [2-[2-acetyloxy-2-(4-aminophenyl)ethyl]sulfonyl-1-(4-aminophenyl)ethyl] acetate Chemical compound C=1C=C(N)C=CC=1C(OC(=O)C)CS(=O)(=O)CC(OC(C)=O)C1=CC=C(N)C=C1 MAFGFYFHPXKEJJ-UHFFFAOYSA-N 0.000 description 10
- 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 10
- JVMSQRAXNZPDHF-UHFFFAOYSA-N 2,4-diaminobenzenesulfonic acid Chemical compound NC1=CC=C(S(O)(=O)=O)C(N)=C1 JVMSQRAXNZPDHF-UHFFFAOYSA-N 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 239000011734 sodium Substances 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 239000002270 dispersing agent Substances 0.000 description 6
- 229910052708 sodium Inorganic materials 0.000 description 6
- 238000005160 1H NMR spectroscopy Methods 0.000 description 5
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000009833 condensation Methods 0.000 description 5
- 230000005494 condensation Effects 0.000 description 5
- 230000008878 coupling Effects 0.000 description 5
- 238000010168 coupling process Methods 0.000 description 5
- 239000000376 reactant Substances 0.000 description 5
- 239000011541 reaction mixture Substances 0.000 description 5
- 239000011780 sodium chloride Substances 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 238000005185 salting out Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 229920000742 Cotton Polymers 0.000 description 2
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- JFKMCWAQZYLKJP-UHFFFAOYSA-N [2-[2-acetyloxy-2-(3-aminophenyl)ethyl]sulfonyl-1-(3-aminophenyl)ethyl] acetate hydrochloride Chemical compound CC(=O)OC(CS(=O)(=O)CC(C1=CC(=CC=C1)N)OC(=O)C)C2=CC(=CC=C2)N.Cl JFKMCWAQZYLKJP-UHFFFAOYSA-N 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229940092714 benzenesulfonic acid Drugs 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 238000009967 direct dyeing Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- QJQOQCWGYQJWBV-UHFFFAOYSA-N n-[4-[2-[2-(4-acetamidophenyl)-2-hydroxyethyl]sulfonyl-1-hydroxyethyl]phenyl]acetamide Chemical compound C1=CC(NC(=O)C)=CC=C1C(O)CS(=O)(=O)CC(O)C1=CC=C(NC(C)=O)C=C1 QJQOQCWGYQJWBV-UHFFFAOYSA-N 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 125000000542 sulfonic acid group Chemical group 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- MBDUIEKYVPVZJH-UHFFFAOYSA-N 1-ethylsulfonylethane Chemical compound CCS(=O)(=O)CC MBDUIEKYVPVZJH-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 1
- 150000008041 alkali metal carbonates Chemical class 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000011033 desalting Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 210000004243 sweat Anatomy 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- 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
- C09B62/00—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves
- C09B62/02—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group directly attached to a heterocyclic ring
- C09B62/04—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group directly attached to a heterocyclic ring to a triazine ring
- C09B62/08—Azo dyes
- C09B62/082—Azo dyes dyes containing in the molecule at least one azo group and at least one other chromophore group
-
- 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
- C09B29/0007—Monoazo dyes prepared by diazotising and coupling from diazotized anilines containing acid groups, e.g. CO2H, SO3H, PO3H2, OSO3H, OPO2H2; Salts thereof
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Coloring (AREA)
Abstract
본 발명은 삼반응기형 청색 반응성염료에 관한 것으로서, 더욱 상세하게는 한 염료 분자 내에 모노클로로트리아진과 두 개의 비닐설폰기가 반응기로 도입되어 있어 염착률이 월등히 높아 염색 폐수가 거의 발생하지 않고, 뿐만 아니라 염료 분자내에 적어도 한 개의 아미노페닐-β-아세톡시에틸설폰 반응기가 도입되어 있어 물에 대한 용해도가 낮아 염석공정시에 소량의 염을 사용하게 되므로 폐수처리 비용을 크게 절감시킬 수 있고, 염석 후 여과시 여액으로 빠져 나가는 염료의 손실량을 최대한 줄일 수 있는 효과를 가지는 다음 화학식 1로 표시되는 삼반응기형 청색 반응성염료에 관한 것이다.The present invention relates to a three-reactor type blue reactive dye, and more particularly, monochlorotriazine and two vinyl sulfone groups are introduced into a reactor in a dye molecule, so that the dyeing rate is extremely high, so that almost no dyeing wastewater is generated. At least one aminophenyl-β-acetoxyethylsulfone reactor is introduced in the dye molecule, so that the solubility in water is low, so that a small amount of salt is used in the salting process, thereby greatly reducing the cost of wastewater treatment and filtering after salting. It relates to a tri-reactor type blue reactive dye represented by the following formula (1) having the effect of reducing the loss of the dye going out into the filtrate as much as possible.
상기 화학식 1에서 : Z 및 Z'는 서로 같거나 다른 것으로서 OSO3M 또는 OCOCH3를 나타내며, Z 및 Z'중 적어도 하나는 OCOCH3이고,n은 0, 1 혹은 2를 나타내며, M은 알칼리금속원자를 나타낸다.In Formula 1, Z and Z 'are the same as or different from each other and represent OSO 3 M or OCOCH 3 , at least one of Z and Z' is OCOCH 3 , n represents 0, 1 or 2, and M is an alkali metal. Represents an atom.
Description
본 발명은 삼반응기형 청색 반응성염료에 관한 것으로서, 더욱 상세하게는 한 염료 분자 내에 모노클로로트리아진과 두 개의 비닐설폰기가 반응기로 도입되어 있어 염착률이 월등히 높아 염색 폐수가 거의 발생하지 않고, 뿐만 아니라 염료 분자내에 적어도 한 개의 아미노페닐-β-아세톡시에틸설폰 반응기가 도입되어 있어 물에 대한 용해도가 낮아 염석공정시에 소량의 염을 사용하게 되므로 폐수처리 비용을 크게 절감시킬 수 있고, 염석 후 여과시 여액으로 빠져 나가는 염료의 손실량을 최대한 줄일 수 있는 효과를 가지는 다음 화학식 1로 표시되는 삼반응기형 청색 반응성염료에 관한 것이다.The present invention relates to a three-reactor type blue reactive dye, and more particularly, monochlorotriazine and two vinyl sulfone groups are introduced into a reactor in a dye molecule, so that the dyeing rate is extremely high, so that almost no dyeing wastewater is generated. At least one aminophenyl-β-acetoxyethylsulfone reactor is introduced in the dye molecule, so that the solubility in water is low, so that a small amount of salt is used in the salting process, thereby greatly reducing the cost of wastewater treatment and filtering after salting. It relates to a tri-reactor type blue reactive dye represented by the following formula (1) having the effect of reducing the loss of the dye going out into the filtrate as much as possible.
화학식 1Formula 1
상기 화학식 1에서 : Z 및 Z'는 서로 같거나 다른 것으로서 OSO3M 또는 OCOCH3를 나타내며, Z 및 Z'중 적어도 하나는 OCOCH3이고,n은 0, 1 혹은 2를 나타내며, M은 알칼리금속원자를 나타낸다.In Formula 1, Z and Z 'are the same as or different from each other and represent OSO 3 M or OCOCH 3 , at least one of Z and Z' is OCOCH 3 , n represents 0, 1 or 2, and M is an alkali metal. Represents an atom.
반응성염료를 합성한 후에 반응 혼합물로부터 염료를 분리회수하는 방법으로서 일반적으로는 염석(saliting out)을 수행하고 있다. 그러나, 다음 화학식 2a로 표시되는 아미노페닐-β-설페이토에틸설폰을 중간체로 사용하여 비닐설폰계 반응성염료를 제조하는 경우, 염료의 물에 대한 용해도가 대단히 높기 때문에 염석(salting-out)을 실시하는 대신에 주로 다량의 염을 사용하거나 분사건조시켜 반응혼합물로부터 염료를 분리회수 하고 있다. 그러나, 이러한 분사건조 또는 다량의 염(salt)을 이용한 염료 분리방법은 염료 및 염 농도가 높은 폐수를 발생시켜 환경 오염의 주범이 될 수 있으며 잔류 염료의 농도가 높기 때문에 폐수 처리에 많은 비용이 소요되는 문제가 있다.As a method of separating and recovering the dye from the reaction mixture after synthesizing the reactive dye, salting out is generally performed. However, when preparing a vinyl sulfone-based reactive dye using aminophenyl-β-sulfatoethylsulfone represented by the following formula (2a) as a intermediate, salting-out is produced because the solubility of the dye in water is very high. Instead of carrying out, a large amount of salt is used or spray-dried to separate and recover the dye from the reaction mixture. However, this method of spray drying or dye separation using a large amount of salt may cause wastewater with high dye and salt concentrations, which may be a major cause of environmental pollution. There is a problem.
최근, 유럽 및 미국 등 선진국에서는 염색 폐수의 염 농도도 환경 규제의 대상이 되고 있어서 소량의 염을 포함하는 저염 염료를 만들려는 연구가 계속되고 있고, 이런 염료들이 현재 출시되고 있다. 또한 작업자의 건강 및 최근의 염색공정 자동화에 따른 정확한 계량을 위해 액화염료를 사용하려는 경향이 점차 증가되고 있는 추세에 있는 바, 안정한 액화염료를 만들기 위해서는 염이 제거된 고농도의 염료를 사용해야 한다.Recently, in developed countries such as Europe and the United States, salt concentrations of dyeing wastewater are also subject to environmental regulation, and researches are being made to make low salt dyes containing a small amount of salts, and these dyes are currently on the market. In addition, the tendency to use liquefied dye for accurate weighing according to the health of workers and the recent automation of the dyeing process is gradually increasing, and to make a stable liquefied dye, it is necessary to use a high concentration of dye from which the salt is removed.
따라서, 상기 화학식 2a로 표시되는 아미노페닐-β-설페이토에틸설폰 만을 사용하여 합성된 염료에 비하여 물에 대한 용해도가 상대적으로 낮은 다음 화학식 3으로 표시되는 아미노페닐-β-아세톡시에틸설폰을 반응기로 사용하여 염료를 합성하면 보다 염석이 용이해질 수 있다.Accordingly, the aminophenyl-β-acetoxyethylsulfone represented by the following Chemical Formula 3 has a relatively low solubility in water compared to the dye synthesized using only the aminophenyl-β-sulfatoethylsulfone represented by the above Chemical Formula 2a. Synthesis of dyes using the reactor can make salting easier.
실제로 상기 화학식 2b로 표시되는 아미노페닐-β-아세톡시에틸설폰을 반응기로 포함하는 반응성염료의 합성과정에서 수행하는 염석공정의 경우, 기존의 염료 합성공정에서 보다 소금의 사용량을 줄일 수 있어 폐수의 염 농도를 낮출 수 있었다. 또한, 제조된 염료의 용해도가 낮아 여과시 여액으로 빠져나가는 염료의 양이 적기 때문에 기존의 염료 제조방법에서 보다 폐수내 염료의 농도를 낮출 수 있어서 폐수 처리 비용을 절감할 수 있었다. 또한, 이런 방법으로 얻어진 염료는 보다 적은 양의 염을 포함하는 고순도의 염료를 얻을 수 있어서 염색 폐수의 염 농도를 줄일 수 있으며, 액화염료를 만들기 위한 탈염 과정도 보다 용이해지는 장점이 있다.Actually, in the salting process performed in the synthesis process of the reactive dye comprising aminophenyl-β-acetoxyethylsulfone represented by the above formula (2b) as a reactor, it is possible to reduce the amount of salt used in the conventional dye synthesis process to reduce waste water. The salt concentration could be lowered. In addition, since the solubility of the produced dye is low because the amount of the dye is released into the filtrate during filtration, the concentration of the dye in the waste water can be lowered than in the conventional dye production method can reduce the waste water treatment cost. In addition, the dye obtained in this way can obtain a high-purity dye containing a smaller amount of salt to reduce the salt concentration of the dyeing waste water, there is an advantage that the desalting process for making a liquefied dye is also easier.
한편, 상기 화학식 2a로 표시되는 아미노페닐-β-설페이토에틸설폰과 상기 화학식 2b로 표시되는 4-아미노페닐-β-아세톡시에틸설폰은 이미 공지된 화합물로서 이의 제조방법 역시 몇몇 문헌에 개시되어 있다. 이들 화합물의 대표적인 합성예[일본특허공개 소81-22354호, 독일특허 제2,929,107호]는 다음 반응식 1에 나타내었다.Meanwhile, aminophenyl-β-sulfatoethylsulfone represented by Formula 2a and 4-aminophenyl-β-acetoxyethylsulfone represented by Formula 2b are already known compounds, and methods for preparing the same are also disclosed in some literatures. It is. Representative synthesis examples of these compounds [Japanese Patent Laid-Open No. 81-22354, German Patent No. 2,929,107] are shown in Scheme 1 below.
상기 반응식 1에 의하면, 4-아세트아미노페닐-β-하이드록시에틸설폰과 98% 황산을 반응시켜 상기 화학식 2a로 표시되는 화합물과 상기 화학식 2b로 표시되는 화합물이 최고 30 : 70 비율로 혼합되어 있는 혼합물을 얻을 수 있으며, 이 혼합물을 사용하여 합성된 염료는 좋은 염색 특성을 나타낸다고 보고한 바 있다. 그러나, 상기 반응식 1에 의해 얻은 혼합물을 이용하여 염료를 합성하게 되면, 4-아미노페닐-β-설페이토에틸설폰 존재로 인한 높은 수용해도로 인하여 직접성이 떨어지는 문제가 있다.According to Scheme 1, 4-acetaminophenyl-β-hydroxyethylsulfone and 98% sulfuric acid are reacted to mix the compound represented by Chemical Formula 2a with the compound represented by Chemical Formula 2b in a maximum ratio of 30:70. Mixtures can be obtained, and dyes synthesized using this mixture have been reported to exhibit good dyeing properties. However, when the dye is synthesized using the mixture obtained by the reaction scheme 1, there is a problem that the directivity is poor due to high water solubility due to the presence of 4-aminophenyl-β-sulfatoethylsulfone.
이상에서 설명한 바와 같이, 반응성염료의 큰 문제점 중의 하나가 낮은 염착률로 인해 염료의 낭비가 많아 경제적 손실이 크고, 염색 폐수에 미고착 염료가 많이 남아 있어 환경오염을 유발함은 물론 폐수 처리에 많은 비용이 소요된다는 것이다. 이러한 문제를 해결하기 위해, 한 염료 분자내에 두 개의 반응기를 도입하여 염착률을 높인 이반응기형 반응성염료들이 많이 연구 개발되어 출시되고는 있으나, 흡족할 만한 염착률을 보여 주지 못하고 있다. 한편, 염착률 개선을 위하여 한 염료 분자내에 세 개 이상의 반응기를 도입시킨 삼반응기형 반응성염료가 개발된 바도 있으나, 빨리 포화되어 빌드업성이 저조해지는 또다른 문제점이 제시되었다.As described above, one of the major problems of reactive dyes is a large waste of dye due to low dyeing rate, resulting in high economic loss, and many unfixed dyes remain in the dyeing wastewater, causing environmental pollution, It is costly. In order to solve this problem, many reactor-type reactive dyes, which have increased dyeing rates by introducing two reactors in one dye molecule, have been researched and released, but have not shown satisfactory dyeing rates. On the other hand, a tri-reactor type reactive dye in which three or more reactors are introduced in one dye molecule to improve the dyeing rate has been developed, but another problem of poor saturation and poor buildup has been proposed.
한편, 본 출원인은 아미노페닐-β-아세톡시에틸설폰과 모노클로로트리아진을 반응기로 도입하여 염료 제조시 오염원을 줄이고, 색상이 선명하고, 낮은 수용해도를 가지며 직접성이 좋아 염착률이 높은 이반응기형 청색 반응성 염료를 이미 특허출원한 바도 있다[대한민국특허출원 제98-10609호].On the other hand, the present applicant introduces aminophenyl-β-acetoxyethylsulfone and monochlorotriazine into the reactor to reduce the source of contamination during dye production, the color is clear, has a low water solubility and has a high degree of direct dyeing reaction There has also been a patent application for a malformed blue reactive dye (Korean Patent Application No. 98-10609).
이에, 본 발명자들은 상기 연구결과에 만족하지 않고 염착률이 매우 높은 청색 반응성염료를 고수율 및 고순도로 제조할 수 있는 방법에 대하여 지속적으로 연구 노력하였다. 그 결과 염료 분자내에 모노클로로트리아진과 두 개의 비닐설폰기를 반응기로 도입되어 있고, 적어도 한 개의 아미노페닐-β-아세톡시에틸설폰 반응기가 도입되어 있는 신규 삼반응기형 청색 반응성염료를 합성함으로써 본 발명을 완성하였다.Accordingly, the present inventors have continuously studied how to produce a blue reactive dye having a high dyeing rate and not being satisfied with the above research results with high yield and high purity. As a result, the present invention was prepared by synthesizing a novel trireactor type blue reactive dye in which a monochlorotriazine and two vinylsulfone groups were introduced into the reactor and at least one aminophenyl-β-acetoxyethylsulfone reactor was introduced into the dye molecule. Completed.
따라서, 본 발명은 염료 제조시 오염원을 줄이고, 색상이 선명하고, 낮은 수용해도를 가지며 직접성이 좋아 염착률이 매우 높은 삼반응기형 청색 반응성염료를 제공하는데 그 목적이 있다.Accordingly, an object of the present invention is to provide a tri-reactor type blue reactive dye which reduces the source of contamination during dye production, has a clear color, has a low water solubility, and has a high direct dyeing rate.
본 발명은 다음 화학식 1로 표시되는 삼반응기형 청색 반응성염료에 관한 것이다.The present invention relates to a trireactive blue reactive dye represented by the following formula (1).
화학식 1Formula 1
상기 화학식 1에서 : Z 및 Z'는 서로 같거나 다른 것으로서 OSO3M 또는 OCOCH3를 나타내며, Z 및 Z'중 적어도 하나는 OCOCH3이고,n은 0, 1 혹은 2를 나타내며, M은 알칼리금속원자를 나타낸다.In Formula 1, Z and Z 'are the same as or different from each other and represent OSO 3 M or OCOCH 3 , at least one of Z and Z' is OCOCH 3 , n represents 0, 1 or 2, and M is an alkali metal. Represents an atom.
또한, 본 발명은In addition, the present invention
a) 다음 화학식 2로 표시되는 화합물을 디아조화하고 1-나프톨-8-아미노-3,6-디설폰산 중화액과 커플링 반응시키는 과정;a) diazotizing the compound represented by the following Chemical Formula 2 and coupling-reacting with 1-naphthol-8-amino-3,6-disulfonic acid neutralizing solution;
b) 이와는 별도로 0∼5℃ 조건에서 페닐렌디아민 설폰산 중화액과 시아누릭 클로라이드(Cyanuric chloride)를 축합반응시키는 과정;b) separately condensing the phenylenediamine sulfonic acid neutralized solution with cyanuric chloride at 0 ° C. to 5 ° C .;
c) 상기 b) 축합물을 디아조화한 후, 0∼5℃ 조건에서 a) 반응액에 일시에 투입하고 pH 7 이하로 유지시켜 커플링 반응시키는 과정; 그리고c) diazotizing the condensate b) and then subjecting a) to the reaction solution at a time of 0 to 5 ° C. and maintaining the pH at 7 or less; And
d) 상기 c)커플링 반응액에 35∼45℃ 조건에서 아미노페닐-β-아세톡시에틸설폰 혹은 아미노페닐-β-설페이토에틸설폰 화합물을 첨가하여 축합반응시키는 다음 화학식 1로 표시되는 삼반응기형 청색 반응성염료의 제조방법을 포함한다.d) Condensation reaction of c) coupling reaction solution by addition of aminophenyl-β-acetoxyethylsulfone or aminophenyl-β-sulfatoethylsulfone compound at 35-45 ° C. It includes a method for producing a reactive blue reactive dye.
화학식 1Formula 1
상기 화학식 1에서 : Z 및 Z'는 서로 같거나 다른 것으로서 OSO3M 또는 OCOCH3를 나타내며, Z 및 Z'중 적어도 하나는 OCOCH3이고,n은 0, 1 혹은 2를 나타내며, M은 알칼리금속원자를 나타낸다.In Formula 1, Z and Z 'are the same as or different from each other and represent OSO 3 M or OCOCH 3 , at least one of Z and Z' is OCOCH 3 , n represents 0, 1 or 2, and M is an alkali metal. Represents an atom.
본 발명에 따른 상기 화학식 1로 표시되는 삼반응기형 청색 반응성염료의 제조과정을 보다 상세히 설명하면 다음과 같다.Hereinafter, a process of preparing the trireactive type blue reactive dye represented by Chemical Formula 1 according to the present invention will be described in detail.
첫 번째 과정은 상기 화학식 2로 표시되는 화합물을 통상의 방법대로 디아조화한 후, 이를 1-나프톨-8-아미노-3,6-디설폰산 중화액과 커플링 반응시키는 과정이다. 이때 디아조화 방법은 통상의 방법으로서 예컨대 0∼5℃의 온도에서 상기 화학식 2로 표시되는 화합물을 물에 분산시킨 후 진한 염산 혹은 황산과 NaNO2를 첨가하여 디아조화 반응을 수행한다.The first process is to diazotize the compound represented by Chemical Formula 2 according to a conventional method, and then perform a coupling reaction with a 1-naphthol-8-amino-3,6-disulfonic acid neutralization solution. At this time, the diazotization method is a conventional method, for example, by dispersing the compound represented by the formula (2) in water at a temperature of 0 ~ 5 ℃ and then conducts the diazotization reaction by adding concentrated hydrochloric acid or sulfuric acid and NaNO 2 .
한편, 1-나프톨-8-아미노-3,6-디설폰산 중화액은 1-나프톨-8-아미노-3,6-디설폰산에 염기를 투입하여 화합물에 존재하는 설폰산기(-SO3H)를 설폰산 금속염(-SO3M)으로 전환시킨 용액이다. 이때 사용되는 염기로는 알칼리금속 수산화물, 알칼리금속 탄산염 등 통상적인 것으로서, 바람직하기로는 NaOH, LiOH, Na2CO3, Li2CO3를 사용한다. 염기의 사용량은 1-나프톨-8-아미노-3,6-디설폰산에 대하여 당량비로 투입한다. 그리고, 0∼5℃의 온도를 유지하면서 상기 디아조액에 1-나프톨-8-아미노-3,6-디설폰산 중화액을 일시에 첨가하여 커플링 반응시킨다.Meanwhile, the 1-naphthol-8-amino-3,6-disulfonic acid neutralizing solution is a sulfonic acid group (-SO 3 H) present in the compound by adding a base to 1-naphthol-8-amino-3,6-disulfonic acid. To a sulfonic acid metal salt (-SO 3 M). The base used at this time is a conventional one such as alkali metal hydroxide, alkali metal carbonate, and preferably NaOH, LiOH, Na 2 CO 3 , Li 2 CO 3 is used. The base is used in an equivalent ratio with respect to 1-naphthol-8-amino-3,6-disulfonic acid. Then, 1-naphthol-8-amino-3,6-disulfonic acid neutralization solution is added to the diazo solution at a time while maintaining the temperature at 0 to 5 ° C. for coupling reaction.
두 번째 반응은 별도의 반응용기에서 페닐렌디아민 설폰산 중화액과 시아누릭 클로라이드(Cyanuric chloride)를 축합반응시키는 과정이다. 페닐렌디아민 설폰산 중화액은 상기 첫 번째 반응에서 예시한 염기를 사용하여 화합물에 존재하는 설폰산기(-SO3H)를 설폰산 금속염(-SO3M)으로 전환시킨 용액이다. 그리고, 온도 0∼5℃ 조건하에서 축합반응을 수행하여 부산물의 생성을 최대한 억제토록 한다.The second reaction is a condensation reaction between phenylenediamine sulfonic acid neutralization solution and cyanuric chloride in a separate reaction vessel. The phenylenediamine sulfonic acid neutralization solution is a solution obtained by converting a sulfonic acid group (-SO 3 H) present in the compound into a sulfonic acid metal salt (-SO 3 M) using the base illustrated in the first reaction. The condensation reaction is carried out under a temperature of 0 to 5 ° C. to minimize the formation of by-products.
세 번째 반응은 상기 첫 번째 및 두 번째 반응에서 제조한 반응액을 혼합하여 커플링 반응시키는 과정이다. 커플링 반응을 수행함에 앞서서, 상기 두 번째 과정에서 얻은 축합물은 통상의 방법에 의해 디아조화한다. 커플링 반응은 pH 7 이하 및 0∼5℃ 조건하에서 수행하는 것이 바람직하다.The third reaction is a process of mixing and reacting the reaction liquids prepared in the first and second reactions. Prior to carrying out the coupling reaction, the condensate obtained in the second step is diazotized by conventional methods. The coupling reaction is preferably carried out at pH 7 or below and under 0 to 5 ° C.
네 번째 반응은 상기 세 번째 과정의 반응 혼합물에 상기 화학식 2로 표시되는 화합물을 첨가하여 축합반응시켜 본 발명이 목적으로 하는 상기 화학식 1로 표시되는 삼반응기형 청색 반응성염료를 제조하는 과정이다. 이때 축합반응은 35∼45℃ 온도범위내에서 수행하며 축합반응이 완료되면 염석(salting-out)하여 목적물을 얻는다.The fourth reaction is a process of preparing a trireactive type blue reactive dye represented by Chemical Formula 1 by condensation reaction by adding the compound represented by Chemical Formula 2 to the reaction mixture of the third process. At this time, the condensation reaction is carried out in the temperature range of 35 ~ 45 ℃ and when the condensation reaction is completed by salting out to obtain the target product.
상기한 바와 같은 본 발명의 제조방법에서는 상기 화학식 2로 표시되는 화합물을 맨 마지막으로 도입하는 바, 본 발명자들의 실험결과에 따르면 아미노페닐-β-아세톡시에틸설폰 혹은 아미노페닐-β-설페이토에틸설폰을 미리 도입하게 되면 부반응 생성물이 많이 생기는 문제가 있기 때문이다.In the preparation method of the present invention as described above, the compound represented by the formula (2) is finally introduced. According to the experimental results of the present inventors, aminophenyl-β-acetoxyethylsulfone or aminophenyl-β-sulfato This is because when the ethyl sulfone is introduced in advance, there is a problem that many side reaction products are generated.
이상의 제조방법에 의해 제조된 상기 화학식 1로 표시되는 청색 반응성염료는 모노클로로트리아진과 두 개의 비닐설폰기가 반응성기로 도입되어 있는 삼반응기형 염료로서, 낮은 수용해도로 인하여 염석이 매우 용이하며, 염석에 의한 분리방법으로 적은 양의 염을 포함하는 고농도 염료 및 반응부산물이 거의 포함되지 않은 순수한 염료를 얻게 되므로 염료로부터의 염의 제거가 용이하여 작업자의 건강 및 최근의 염색공정 자동화에 따른 정확한 계량을 위한 액화염료를 만드는데 특히 유리하며, 여액에는 보다 적은 염료 및 염을 포함하고 있어 폐수처리면에서도 경제적이다.The blue reactive dye represented by Chemical Formula 1 prepared by the above manufacturing method is a trireactive dye in which monochlorotriazine and two vinyl sulfone groups are introduced into a reactive group, and are easily salted due to low water solubility. As a result of the separation method, a high concentration of dye containing a small amount of salt and a pure dye containing little reaction by-product are obtained, so it is easy to remove salts from the dye and liquefy for accurate weighing according to worker's health and recent automation of dyeing process. It is particularly advantageous for making dyes, and because the filtrate contains less dyes and salts, it is also economical in terms of wastewater treatment.
또한, 본 발명의 삼반응기형 청색 반응성염료를 면섬유에 염색하면 종래의 청색 반응성염료로 염색된 천에 비하여 색수율, 염착률이 매우 높다.In addition, when the tri-reactive type blue reactive dye of the present invention is dyed to cotton fibers, the color yield and dyeing rate are very high as compared to the cloth dyed with conventional blue reactive dyes.
이와 같은 본 발명을 실시예에 의거하여 상세하게 설명하겠는 바, 본 발명이 실시예에 한정되는 것은 아니다.Although this invention is demonstrated in detail based on an Example, this invention is not limited to an Example.
제조예 : 4-아미노페닐-β-아세톡시에틸설폰의 제조Preparation Example: Preparation of 4-aminophenyl-β-acetoxyethylsulfone
100 ㎖ 반응기에 고무풍선을 단 컨덴서를 부착시킨 다음, 여기에 아세트산 60 g(1 mol)과 물 1.8 g(0.1 mol)을 넣고 반응용액의 온도를 15℃로 유지하면서 염화수소기체 5.5 g(0.15 mol)을 2 시간에 걸쳐서 서서히 반응용액에 주입하였다. 4-아세트아미노페닐-β-하이드록시에틸설폰 24.3 g(0.1 mol)을 넣고 1시간에 걸쳐서 70℃ 내지 75℃로 서서히 가열한 후 9시간 동안 교반하였다.Attach a condenser with a rubber balloon to a 100 ml reactor, add 60 g (1 mol) of acetic acid and 1.8 g (0.1 mol) of water, and keep 5.5 g (0.15 mol) of hydrogen chloride gas while maintaining the temperature of the reaction solution at 15 ° C. ) Was slowly injected into the reaction solution over 2 hours. 24.3 g (0.1 mol) of 4-acetaminophenyl-β-hydroxyethylsulfone was added thereto, and the mixture was slowly heated to 70 to 75 ° C. over 1 hour, followed by stirring for 9 hours.
천천히 교반하면서 반응물을 실온으로 냉각시킨 후 여과하고 아세트산(5 ㎖)으로 2회 세척하였다. 여과된 고체를 60℃에서 진공 건조시킨 후, 얼음(10 g)과 물(25 ㎖)에 분산시킨 다음, 용액이 중성이 되도록 15% 탄산나트륨 수용액으로 중화시켜 결정을 여과하였다. 물(5 ㎖)로 3회 세척한 후 건조하여 고체 형태인 백색의 순수한 4-아미노페닐-β-아세톡시에틸설폰 20.6 g(수율: 84.8%, 순도: 97.5%)을 얻었다.The reaction was cooled to room temperature with slow stirring, filtered and washed twice with acetic acid (5 mL). The filtered solid was dried in vacuo at 60 ° C., then dispersed in ice (10 g) and water (25 mL), and then the crystals were filtered by neutralization with 15% aqueous sodium carbonate solution to make the solution neutral. After washing three times with water (5 mL) and dried to give 20.6 g (yield: 84.8%, purity: 97.5%) of pure, white 4-aminophenyl-β-acetoxyethylsulfone in solid form.
녹는점 : 92∼93℃Melting Point: 92 ~ 93 ℃
실시예 1Example 1
a) 과정a) process
4-아미노페닐-β-아세톡시에틸설폰 13.17 g(97%, 0.0525 mol)을 물 100 ㎖와 얼음 20 g에 분산시킨 후 NaNO217.9 ㎖(3N, 0.0537 mol)를 가하였다. 반응물의 온도를 0℃ 내지 5℃로 유지시킨 후 반응물에 얼음 20 g을 넣은 다음, 35% HCl 11.4 ㎖(0.131 mol)를 첨가하였다. 1시간 동안 교반하여 디아조화 반응을 완결시킨 후 소량의 설파믹산을 가하여 과량의 HNO2를 제거하였다.13.17 g (97%, 0.0525 mol) of 4-aminophenyl-β-acetoxyethylsulfone was dispersed in 100 ml of water and 20 g of ice, followed by addition of 17.9 ml (3N, 0.0537 mol) of NaNO 2 . The temperature of the reaction was maintained at 0 ° C. to 5 ° C., 20 g of ice was added to the reaction, and then 11.4 mL (0.131 mol) of 35% HCl was added thereto. After stirring for 1 hour to complete the diazotization reaction, a small amount of sulfamic acid was added to remove excess HNO 2 .
별도의 반응용기에서 1-나프톨-8-아미노-3,6-디설폰산 20.79 g(82.1%, 0.05 mol)을 물 120 ㎖에 넣고 4N NaOH 수용액 12.5 ㎖로 중화시켜 녹였다. 위에서 얻은 디아조액에 얼음 25 g을 넣은 후 1-나프톨-8-아미노-3,6-디설폰산 중화액을 일시에 첨가하고 2시간 교반하여 커플링 반응을 완결시켰다.In a separate reaction vessel, 20.79 g (82.1%, 0.05 mol) of 1-naphthol-8-amino-3,6-disulfonic acid was added to 120 ml of water and neutralized with 12.5 ml of 4N NaOH aqueous solution. 25 g of ice was added to the diazo solution obtained above, and then 1-naphthol-8-amino-3,6-disulfonic acid neutralization solution was added at a time and stirred for 2 hours to complete the coupling reaction.
b) 과정b) process
m-페닐렌디아민-4-설폰산 10.56 g(98%, 0.055 mol)을 물 70 ㎖에 분산시킨 후 4N NaOH 수용액 13.5 ㎖를 가해 중화시켜 녹였다.10.56 g (98%, 0.055 mol) of m-phenylenediamine-4-sulfonic acid was dispersed in 70 ml of water, and 13.5 ml of 4N NaOH aqueous solution was added to neutralize and dissolved.
별도의 반응용기에서 시아누릭 클로라이드 10.99 g(99%, 0.06 mol)에 물 120 ㎖와 얼음 10 g, 분산제로서 폴리옥시에틸렌 노닐페닐 에테르(KONION NP-9) 10% 수용액 0.6 g을 넣고 분산시킨 분산액을 0℃ 내지 5℃로 유지시켰다. 여기에 얼음 10 g을 넣은 후, 위에서 녹인 m-페닐렌디아민-4-설폰산 중화액을 적하 깔때기로 1시간 동안 서서히 첨가한 후 30분간 더 교반하여 축합반응을 완결시켰다.In a separate reaction vessel, 10.99 g (99%, 0.06 mol) of cyanuric chloride was dispersed in 120 ml of water and 10 g of ice and 0.6 g of a 10% aqueous solution of polyoxyethylene nonylphenyl ether (KONION NP-9) as a dispersant. Was maintained at 0 ° C to 5 ° C. After 10 g of ice was added thereto, m-phenylenediamine-4-sulfonic acid neutralized solution dissolved above was slowly added to the dropping funnel for 1 hour, followed by further stirring for 30 minutes to complete the condensation reaction.
C) 과정C) process
상기 b) 과정에서 얻은 축합 용액에 35% HCl 11.5 ㎖(0.132 mol)를 가하고, 반응물의 온도를 0℃ 내지 5℃로 유지시킨 후 얼음 10 g을 넣은 다음, NaNO218.3 ㎖(3N, 0.055 mol)를 첨가하였다. 1시간 동안 교반하여 디아조화 반응을 완결시킨 후 소량의 설파믹산을 가하여 과량의 HNO2를 제거하였다.11.5 ml (0.132 mol) of 35% HCl was added to the condensation solution obtained in step b), and the temperature of the reactant was maintained at 0 ° C. to 5 ° C., followed by 10 g of ice, followed by 18.3 ml of NaNO 2 (3N, 0.055 mol). ) Was added. After stirring for 1 hour to complete the diazotization reaction, a small amount of sulfamic acid was added to remove excess HNO 2 .
그리고 상기 a) 과정에서 얻은 모노아조 화합물 용액의 온도를 0℃ 내지 5℃로 유지시킨 후 얼음 30 g을 넣은 다음, 상기 디아조액을 일시에 가하였다. 15% Na2CO3수용액 65 ㎖를 적하 깔때기를 이용하여 pH가 6.5∼7.0이 넘지 않도록 30분 동안 천천히 적가한 후 1.5시간 더 교반하여 2차 커플링 반응을 완결시켰다.Then, the temperature of the monoazo compound solution obtained in step a) was maintained at 0 ° C to 5 ° C, 30 g of ice was added thereto, and the diazo solution was added at a time. 65 ml of 15% Na 2 CO 3 aqueous solution was slowly added dropwise for 30 minutes using a dropping funnel so as not to exceed pH 6.5 to 7.0, followed by further stirring for 1.5 hours to complete the second coupling reaction.
d) 과정d) process
상기 c) 과정에서 얻은 2차 커플링 용액에 2N HCl 수용액 9 ㎖를 가하여 pH를 5∼5.5로 조정한 후 4-아미노페닐-β-아세톡시에틸설폰 13.17 g(97%, 0.0525 mol)을 가하고 1시간에 걸쳐 40℃ 내지 45℃로 서서히 승온하였다. pH를 4∼5로 조정하면서 2시간 더 교반하여 반응이 완결되면 NaOAc를 가하여 pH를 6∼6.5로 조정하였다. 50℃ 내지 55℃로 승온하고 NaCl을 가하여 염석한 후 여과하고 건조하여 상기 구조식을 가진 청색 반응성염료를 얻었다.9 ml of 2N HCl aqueous solution was added to the secondary coupling solution obtained in step c) to adjust the pH to 5 to 5.5, and then 13.17 g (97%, 0.0525 mol) of 4-aminophenyl-β-acetoxyethylsulfone was added thereto. It heated up gradually to 40-45 degreeC over 1 hour. The mixture was stirred for 2 hours while adjusting the pH to 4 to 5, and when the reaction was completed, NaOAc was added to adjust the pH to 6 to 6.5. The reaction mixture was heated to 50 ° C to 55 ° C, salted with NaCl, filtered, and dried to obtain a blue reactive dye having the above structural formula.
1H-NMR(300 MHz, DMSO-d6) : δ 1.76(3H, s), 1.79(3H, s), 3.71(2H, t), 3.79(2H, t), 4.28∼4.32(4H, m), 7.08(1H, d), 7.51(2H, d), 7.67(1H, d), 7.85(2H, d), 8.02(2H, d), 8.25(2H, d), 8.27(1H, s), 8.30(1H, s), 9.22(1H, s), 10.52(1H, s), 10.68(2H, s), 11.53(1H, s), 16.28(1H, s) 1 H-NMR (300 MHz, DMSO-d 6 ): δ 1.76 (3H, s), 1.79 (3H, s), 3.71 (2H, t), 3.79 (2H, t), 4.28-4.32 (4H, m ), 7.08 (1H, d), 7.51 (2H, d), 7.67 (1H, d), 7.85 (2H, d), 8.02 (2H, d), 8.25 (2H, d), 8.27 (1H, s) , 8.30 (1H, s), 9.22 (1H, s), 10.52 (1H, s), 10.68 (2H, s), 11.53 (1H, s), 16.28 (1H, s)
실시예 2Example 2
a) 과정a) process
3-아미노페닐-β-아세톡시에틸설폰 염산염 2.96 g(99%, 0.0105 mol)을 물 25 ㎖와 얼음 10 g에 녹인 후 35% HCl 1.83 ㎖(0.021 mol)를 가하였다. 반응물의 온도를 0℃ 내지 5℃로 유지시킨 후 반응물에 얼음 10 g을 넣은 다음, NaNO23.5 ㎖(3N, 0.0105 mol)를 첨가하였다. 1시간 동안 교반하여 디아조화 반응을 완결시킨 후 소량의 설파믹산을 가하여 과량의 HNO2를 제거하였다.2.96 g (99%, 0.0105 mol) of 3-aminophenyl-β-acetoxyethylsulfone hydrochloride was dissolved in 25 ml of water and 10 g of ice, followed by addition of 1.83 ml (0.021 mol) of 35% HCl. The temperature of the reaction was maintained at 0 ° C. to 5 ° C., 10 g of ice was added to the reaction, and 3.5 mL of NaNO 2 (3N, 0.0105 mol) was added thereto. After stirring for 1 hour to complete the diazotization reaction, a small amount of sulfamic acid was added to remove excess HNO 2 .
별도의 반응용기에서 1-나프톨-8-아미노-3,6-디설폰산 4.16 g(82.1%, 0.01 mol)에 물 25 ㎖를 넣고 4N NaOH 수용액 2.5 ㎖로 중화시켜 녹였다. 위에서 얻은 디아조액에 얼음 20 g을 넣고 1-나프톨-8-아미노-3,6-디설폰산 중화액을 일시에 가한 다음 2시간 교반하여 커플링 반응을 완결시켰다.In a separate reaction vessel, 25 ml of water was added to 4.16 g (82.1%, 0.01 mol) of 1-naphthol-8-amino-3,6-disulfonic acid and neutralized with 2.5 ml of 4N NaOH aqueous solution to dissolve it. 20 g of ice was added to the diazo solution obtained above, 1-naphthol-8-amino-3,6-disulfonic acid neutralization solution was added at once, followed by stirring for 2 hours to complete the coupling reaction.
b) 과정b) process
m-페닐렌디아민-4-설폰산 2.11 g(98%, 0.011 mol)을 물 20 ㎖에 분산시킨 후 4N NaOH 수용액 2.75 ㎖를 가해 중화시켜 녹였다.2.11 g (98%, 0.011 mol) of m-phenylenediamine-4-sulfonic acid was dispersed in 20 ml of water, and then neutralized by dissolving 2.75 ml of 4N NaOH aqueous solution.
별도의 반응용기에서 시아누릭 클로라이드 2.20 g(99%, 0.012 mol)에 물 25 ㎖와 얼음 10 g, 분산제로서 폴리옥시에틸렌 노닐페닐 에테르(KONION NP-9) 10% 수용액 0.6 g을 넣고 분산시킨 분산액을 0℃ 내지 5℃로 유지시켰다. 여기에 얼음 10 g을 넣은 후, 위에서 녹인 m-페닐렌디아민-4-설폰산 중화액을 적하 깔때기로 약 1시간 동안 서서히 첨가한 후 30분간 더 교반하여 축합반응을 완결시켰다.In a separate reaction vessel, 2.20 g (99%, 0.012 mol) of cyanuric chloride was dispersed in 25 ml of water, 10 g of ice, and 0.6 g of a 10% aqueous solution of polyoxyethylene nonylphenyl ether (KONION NP-9) as a dispersant. Was maintained at 0 ° C to 5 ° C. After 10 g of ice was added thereto, m-phenylenediamine-4-sulfonic acid neutralized solution dissolved in the above was slowly added to the dropping funnel for about 1 hour, followed by further stirring for 30 minutes to complete the condensation reaction.
C) 과정C) process
b) 과정에서 얻은 축합 용액에 35% HCl 2.29 ㎖(0.0264 mol)를 가하고, 반응물의 온도를 0℃ 내지 5℃로 유지시킨 후 반응물에 얼음 10 g을 넣은 다음, NaNO23.67 ㎖(3N, 0.011 mol)를 첨가하였다. 1시간 동안 교반하여 디아조화 반응을 완결시킨 후 소량의 설파믹산을 가하여 과량의 HNO2를 제거하였다.b) To the condensation solution obtained in the process, 2.29 ml (0.0264 mol) of 35% HCl was added and the temperature of the reactant was maintained at 0 ° C to 5 ° C. 10 g of ice was added to the reactant, and 3.67 ml of NaNO 2 (3N, 0.011) was added. mol) was added. After stirring for 1 hour to complete the diazotization reaction, a small amount of sulfamic acid was added to remove excess HNO 2 .
그리고 상기 a) 과정에서 얻은 모노아조 화합물 용액의 온도를 0℃ 내지 5℃로 유지시킨 후, 얼음 10 g을 넣은 다음, 상기 디아조액을 일시에 가하였다. 15% Na2CO3수용액 16 ㎖를 적하 깔때기를 이용하여 pH가 6.5∼7.0이 넘지 않도록 천천히 적가한 후 2시간 더 교반하여 2차 커플링 반응을 완결시켰다.After maintaining the temperature of the monoazo compound solution obtained in step a) at 0 ° C to 5 ° C, 10 g of ice was added, and the diazo solution was added at a time. 16 ml of 15% Na 2 CO 3 aqueous solution was slowly added dropwise using a dropping funnel so as not to exceed pH 6.5 to 7.0, followed by further stirring for 2 hours to complete the secondary coupling reaction.
d) 과정d) process
c) 과정에서 얻은 2차 커플링 용액에 3-아미노페닐-β-아세톡시에틸설폰 염산염 2.98 g(99%, 0.0106 mol)을 가하고 15% Na2CO3수용액을 사용하여 pH를 4.5∼5.5로 유지하면서 1시간에 걸쳐 35℃ 내지 40℃로 서서히 승온하였다. 1시간 더 교반하여 반응이 완결되면 NaOAc를 가하여 pH를 6∼6.5로 조정하였다. 35℃ 내지 40℃에서 NaCl을 가하여 염석한 후 여과하고 건조하여 상기 구조식을 가진 청색 반응성염료를 얻었다.c) To the secondary coupling solution obtained in the process, 2.98 g (99%, 0.0106 mol) of 3-aminophenyl-β-acetoxyethylsulfone hydrochloride was added and the pH was adjusted to 4.5-5.5 using 15% Na 2 CO 3 aqueous solution. It heated up gradually to 35 degreeC-40 degreeC over 1 hour, maintaining. After further stirring for 1 hour to complete the reaction, the pH was adjusted to 6-6.5 by adding NaOAc. NaCl was added at 35 ° C. to 40 ° C. for salting, followed by filtration and drying to obtain a blue reactive dye having the above structural formula.
1H-NMR(300 MHz, DMSO-d6) : δ 1.76(3H, s), 1.79(3H, s), 3.81(4H, t), 4.30∼4.35(4H, m), 7.07(1H, d), 7.49(2H, d), 7.57∼7.67(3H, m), 7.79(1H, t), 7.91(1H, d), 8.34(1H, d), 8.37(1H, d), 8.62(2H, s), 9.23(1H, s), 10.47(1H, s), 10.58(2H, br. s), 11.51(1H, s), 16.27(1H, s) 1 H-NMR (300 MHz, DMSO-d 6 ): δ 1.76 (3H, s), 1.79 (3H, s), 3.81 (4H, t), 4.30-4.35 (4H, m), 7.07 (1H, d ), 7.49 (2H, d), 7.57 to 7.57 (3H, m), 7.79 (1H, t), 7.91 (1H, d), 8.34 (1H, d), 8.37 (1H, d), 8.62 (2H, s), 9.23 (1H, s), 10.47 (1H, s), 10.58 (2H, br.s), 11.51 (1H, s), 16.27 (1H, s)
실시예 3Example 3
a) 과정a) process
4-아미노페닐-β-아세톡시에틸설폰 7.74 g(99%, 0.0315 mol)을 물 100 ㎖에 분산시킨 후 NaNO210.5 ㎖(3N, 0.0315 mol)를 가하였다. 반응물의 온도를 0℃ 내지 5℃로 유지시킨 후 반응물에 얼음 50 g을 넣은 다음, 35% HCl 6.8 ㎖(0.0782 mol)를 첨가하였다. 1시간 동안 교반하여 디아조화 반응을 완결시킨 후 소량의 설파믹산을 가하여 과량의 HNO2를 제거하였다.7.74 g (99%, 0.0315 mol) of 4-aminophenyl-β-acetoxyethylsulfone was dispersed in 100 ml of water, followed by addition of 10.5 ml (3N, 0.0315 mol) of NaNO 2 . The temperature of the reaction was maintained at 0 ° C to 5 ° C, 50 g of ice was added to the reaction, and then 6.8 ml (0.0782 mol) of 35% HCl was added. After stirring for 1 hour to complete the diazotization reaction, a small amount of sulfamic acid was added to remove excess HNO 2 .
별도의 반응용기에서 1-나프톨-8-아미노-3,6-디설폰산 12.47 g(82.1%, 0.03 mol)을 물 60 ㎖에 넣고 4N NaOH 수용액 7.5 ㎖로 중화시켜 녹였다. 위에서 얻은 디아조액에 얼음 50 g을 넣은 후 1-나프톨-8-아미노-3,6-디설폰산 중화액을 일시에 첨가하고 2.5시간 교반하여 커플링 반응을 완결시켰다.In a separate reaction vessel, 12.47 g (82.1%, 0.03 mol) of 1-naphthol-8-amino-3,6-disulfonic acid was added to 60 ml of water and neutralized with 7.5 ml of 4N NaOH aqueous solution. 50 g of ice was added to the diazo solution obtained above, and then 1-naphthol-8-amino-3,6-disulfonic acid neutralization solution was added at a time and stirred for 2.5 hours to complete the coupling reaction.
b) 과정b) process
m-페닐렌디아민-4-설폰산 6.34 g(98%, 0.033 mol)을 물 50 ㎖에 분산시킨 후 4N NaOH 수용액 8.2 ㎖를 가해 중화시켜 녹였다.6.34 g (98%, 0.033 mol) of m-phenylenediamine-4-sulfonic acid was dispersed in 50 ml of water, and then neutralized by dissolving 8.2 ml of 4N NaOH aqueous solution.
별도의 반응용기에서 시아누릭 클로라이드 6.6 g(99%, 0.036 mol)에 물 50 ㎖와 얼음 25 g, 분산제로서 폴리옥시에틸렌 노닐페닐 에테르(KONION NP-9) 10% 수용액 0.6 g을 넣고 분산시킨 분산액을 0℃ 내지 5℃로 유지시켰다. 여기에 얼음 20 g을 넣은 후, 위에서 녹인 m-페닐렌디아민-4-설폰산 중화액을 적하 깔때기로 1시간 동안 서서히 첨가한 후 30분간 더 교반하여 축합반응을 완결시켰다.In a separate reaction vessel, 6.6 g of cyanuric chloride (99%, 0.036 mol) was dispersed in 50 ml of water and 25 g of ice, and 0.6 g of 10% aqueous polyoxyethylene nonylphenyl ether (KONION NP-9) as a dispersant was dispersed. Was maintained at 0 ° C to 5 ° C. After 20 g of ice was added thereto, m-phenylenediamine-4-sulfonic acid neutralized solution dissolved in the above was slowly added to the dropping funnel for 1 hour, followed by further stirring for 30 minutes to complete the condensation reaction.
C) 과정C) process
b)에서 얻은 축합 용액에 35% HCl 6.9 ㎖(0.079 mol)를 가하고, 반응물의 온도를 0℃ 내지 5℃로 유지시킨 후 얼음 30 g을 넣은 다음, NaNO211 ㎖(3N, 0.033 mol)를 첨가하였다. 1시간 동안 교반하여 디아조화 반응을 완결시킨 후 소량의 설파믹산을 가하여 과량의 HNO2를 제거하였다.6.9 ml (0.079 mol) of 35% HCl was added to the condensation solution obtained in b), and the temperature of the reaction was maintained at 0 ° C. to 5 ° C., followed by 30 g of ice, followed by 11 ml of NaNO 2 (3N, 0.033 mol). Added. After stirring for 1 hour to complete the diazotization reaction, a small amount of sulfamic acid was added to remove excess HNO 2 .
그리고 a)에서 얻은 모노아조 화합물 용액의 온도를 0℃ 내지 5℃로 유지시킨 후 얼음 15 g을 넣은 다음, 상기 디아조액을 일시에 가하였다. 15% Na2CO3수용액 50 ㎖를 적하 깔때기를 이용하여 pH가 6.5∼7.0이 넘지 않도록 30분 동안 천천히 적가한 후 물 90 ㎖를 첨가하고 1.5시간 더 교반하여 2차 커플링 반응을 완결시켰다.Then, the temperature of the monoazo compound solution obtained in a) was maintained at 0 ° C to 5 ° C, 15 g of ice was added thereto, and the diazo solution was added at a time. 50 ml of 15% Na 2 CO 3 aqueous solution was slowly added dropwise for 30 minutes using a dropping funnel so as not to exceed pH 6.5-7.0, and then 90 ml of water was added and stirred for an additional 1.5 hours to complete the second coupling reaction.
d) 과정d) process
상기 c) 과정에서 얻은 2차 커플링 용액에 4-아미노페닐-β-설페이토에틸설폰 9.67 g(96%, 0.033 mol)을 가하고 1시간에 걸쳐 40℃ 내지 45℃로 서서히 승온하였다. pH를 5∼5.5로 조정하면서 2.5∼3시간 더 교반하여 반응이 완결되면 NaOAc를 가하여 pH를 6∼6.5로 조정하였다. 50℃ 내지 55℃로 승온하고 NaCl을 가하여 염석한 후 여과하고 건조하여 상기 구조식을 가진 청색 반응성염료를 얻었다.9.67 g (96%, 0.033 mol) of 4-aminophenyl-β-sulfatoethylsulfone was added to the secondary coupling solution obtained in step c), and the temperature was gradually raised from 40 ° C to 45 ° C over 1 hour. The mixture was stirred for 2.5 to 3 hours while adjusting the pH to 5 to 5.5, and when the reaction was completed, NaOAc was added to adjust the pH to 6 to 6.5. The reaction mixture was heated to 50 ° C to 55 ° C, salted with NaCl, filtered, and dried to obtain a blue reactive dye having the above structural formula.
1H-NMR(300 MHz, DMSO-d6) : δ 1.76(3H, s), 3.62(2H, t), 3.78(2H, t), 3.98(2H, t), 4.29(2H, t), 7.08(1H, d), 7.50(2H, d), 7.65(1H, d), 7.85(2H, d), 8.01(2H, d), 8.25(2H, d), 8.27(1H, s), 8.30(1H, s), 9.20(1H, s), 10.50(1H,s), 10.67(2H, s), 11.51(1H, s), 16.27(1H, s) 1 H-NMR (300 MHz, DMSO-d 6 ): δ 1.76 (3H, s), 3.62 (2H, t), 3.78 (2H, t), 3.98 (2H, t), 4.29 (2H, t), 7.08 (1H, d), 7.50 (2H, d), 7.65 (1H, d), 7.85 (2H, d), 8.01 (2H, d), 8.25 (2H, d), 8.27 (1H, s), 8.30 (1H, s), 9.20 (1H, s), 10.50 (1H, s), 10.67 (2H, s), 11.51 (1H, s), 16.27 (1H, s)
실시예 4Example 4
a) 과정a) process
4-아미노페닐-β-설페이토에틸설폰 9.23 g(96%, 0.0315 mol)을 물 100 ㎖에 넣은 후 35% HCl 6.8 ㎖(0.0782 mol)를 첨가하고 분산제로서 폴리옥시에틸렌 노닐페닐 에테르(KONION NP-9) 10% 수용액 0.6 g을 가하여 30분 동안 분산시켰다. 반응물의 온도를 0℃ 내지 5℃로 유지시킨 후 반응물에 얼음 50 g을 넣은 다음, NaNO211.0 ㎖(3N, 0.033 mol)를 첨가하였다. 1시간 동안 교반하여 디아조화 반응을 완결시킨 후 소량의 설파믹산을 가하여 과량의 HNO2를 제거하였다.9.23 g (96%, 0.0315 mol) of 4-aminophenyl-β-sulfatoethylsulfone were added to 100 ml of water, followed by addition of 6.8 ml (0.0782 mol) of 35% HCl and polyoxyethylene nonylphenyl ether (KONION) as a dispersant. NP-9) 0.6 g of a 10% aqueous solution was added and dispersed for 30 minutes. The temperature of the reaction was maintained at 0 ° C to 5 ° C, 50 g of ice was added to the reaction, and then 11.0 mL (3N, 0.033 mol) of NaNO 2 was added. After stirring for 1 hour to complete the diazotization reaction, a small amount of sulfamic acid was added to remove excess HNO 2 .
별도의 반응용기에서 1-나프톨-8-아미노-3,6-디설폰산 12.47 g(82.1%, 0.03 mol)을 물 60 ㎖에 넣고 4N NaOH 수용액 7.5 ㎖로 중화시켜 녹였다. 위에서 얻은 디아조액에 얼음 50 g을 넣은 후 1-나프톨-8-아미노-3,6-디설폰산 중화액을 일시에 첨가하고 2.5시간 교반하여 커플링 반응을 완결시켰다.In a separate reaction vessel, 12.47 g (82.1%, 0.03 mol) of 1-naphthol-8-amino-3,6-disulfonic acid was added to 60 ml of water and neutralized with 7.5 ml of 4N NaOH aqueous solution. 50 g of ice was added to the diazo solution obtained above, and then 1-naphthol-8-amino-3,6-disulfonic acid neutralization solution was added at a time and stirred for 2.5 hours to complete the coupling reaction.
b) 과정b) process
m-페닐렌디아민-4-설폰산 6.34 g(98%, 0.033 mol)을 물 50 ㎖에 분산시킨 후 4N NaOH 수용액 8.2 ㎖를 가해 중화시켜 녹였다.6.34 g (98%, 0.033 mol) of m-phenylenediamine-4-sulfonic acid was dispersed in 50 ml of water, and then neutralized by dissolving 8.2 ml of 4N NaOH aqueous solution.
별도의 반응용기에서 시아누릭 클로라이드 6.6 g(99%, 0.036 mol)에 물 50 ㎖와 얼음 25 g, 분산제로서 폴리옥시에틸렌 노닐페닐 에테르(KONION NP-9) 10% 수용액 0.6 g을 넣고 분산시킨 분산액을 0℃ 내지 5℃로 유지시켰다. 여기에 얼음 20 g을 넣은 후, 위에서 녹인 m-페닐렌디아민-4-설폰산 중화액을 적하 깔때기로 1시간 동안 서서히 첨가한 후 30분간 더 교반하여 축합반응을 완결시켰다.In a separate reaction vessel, 6.6 g of cyanuric chloride (99%, 0.036 mol) was dispersed in 50 ml of water and 25 g of ice, and 0.6 g of 10% aqueous polyoxyethylene nonylphenyl ether (KONION NP-9) as a dispersant was dispersed. Was maintained at 0 ° C to 5 ° C. After 20 g of ice was added thereto, m-phenylenediamine-4-sulfonic acid neutralized solution dissolved in the above was slowly added to the dropping funnel for 1 hour, followed by further stirring for 30 minutes to complete the condensation reaction.
C) 과정C) process
상기 b) 과정에서 얻은 축합 용액에 35% HCl 6.9 ㎖(0.079 mol)를 가하고, 반응물의 온도를 0℃ 내지 5℃로 유지시킨 후 얼음 30 g을 넣은 다음, NaNO211 ㎖(3N, 0.033 mol)를 첨가하였다. 1시간 동안 교반하여 디아조화 반응을 완결시킨 후 소량의 설파믹산을 가하여 과량의 HNO2를 제거하였다.6.9 ml (0.079 mol) of 35% HCl was added to the condensation solution obtained in step b), and the temperature of the reactant was maintained at 0 ° C. to 5 ° C., followed by 30 g of ice, followed by 11 ml of NaNO 2 (3N, 0.033 mol). ) Was added. After stirring for 1 hour to complete the diazotization reaction, a small amount of sulfamic acid was added to remove excess HNO 2 .
그리고 상기 a) 과정에서 얻은 모노아조 화합물 용액의 온도를 0℃ 내지 5℃로 유지시킨 후 얼음 20 g을 넣은 다음, 상기 디아조액을 일시에 가하였다. 15% Na2CO3수용액 60 ㎖를 적하 깔때기를 이용하여 pH가 6.5∼7.0이 넘지 않도록 30분 동안 천천히 적가한 후 2.5시간 더 교반하여 2차 커플링 반응을 완결시켰다.Then, the temperature of the monoazo compound solution obtained in step a) was maintained at 0 ° C to 5 ° C, 20 g of ice was added thereto, and the diazo solution was added at a time. 60 ml of 15% Na 2 CO 3 aqueous solution was slowly added dropwise for 30 minutes using a dropping funnel so as not to exceed pH 6.5 to 7.0, followed by further stirring for 2.5 hours to complete the secondary coupling reaction.
d) 과정d) process
상기 c) 과정에서 얻은 2차 커플링 용액에 5N HCl 수용액 5 ㎖를 가하여 pH를 5.0 정도로 조정한 후 4-아미노페닐-β-아세톡시에틸설폰 8.11 g(99%, 0.033 mol)을 가하고 1시간에 걸쳐 40℃ 내지 45℃로 서서히 승온하였다. pH를 4∼5로 조정하면서 2.5시간 더 교반하여 반응이 완결되면 NaOAc를 가하여 pH를 6∼6.5로 조정하였다. 45℃ 내지 50℃로 승온하고 NaCl을 가하여 염석한 후 여과하고 건조하여 상기 구조식을 가진 청색 반응성염료를 얻었다.5 ml of 5N HCl aqueous solution was added to the secondary coupling solution obtained in step c) to adjust the pH to about 5.0, and then 8.11 g (99%, 0.033 mol) of 4-aminophenyl-β-acetoxyethylsulfone was added for 1 hour. It heated up gradually to 40-45 degreeC over the time. The mixture was stirred for 2.5 hours while adjusting the pH to 4 to 5, and when the reaction was completed, NaOAc was added to adjust the pH to 6 to 6.5. The temperature was raised to 45 ℃ to 50 ℃, NaCl was added to the salted out, filtered and dried to obtain a blue reactive dye having the above structural formula.
1H-NMR(300 MHz, DMSO-d6) : δ 1.78(3H, s), 3.69(4H, t), 4.00(2H, t), 4.27(2H, t), 7.06(1H, d), 7.48(2H, d), 7.65(1H, d), 7.84(2H, d), 8.01(2H, d), 8.23(2H, d), 8.25(1H, s), 8.29(1H, s), 9.20(1H, s), 10.50(1H, s), 10.67(2H, s), 11.55(1H, s), 16.25(1H, s) 1 H-NMR (300 MHz, DMSO-d 6 ): δ 1.78 (3H, s), 3.69 (4H, t), 4.00 (2H, t), 4.27 (2H, t), 7.06 (1H, d), 7.48 (2H, d), 7.65 (1H, d), 7.84 (2H, d), 8.01 (2H, d), 8.23 (2H, d), 8.25 (1H, s), 8.29 (1H, s), 9.20 (1H, s), 10.50 (1H, s), 10.67 (2H, s), 11.55 (1H, s), 16.25 (1H, s)
실시예 5Example 5
a) 과정a) process
4-아미노페닐-β-아세톡시에틸설폰 2.63 g(97%, 0.0105 mol)을 물 30 ㎖와 얼음 10 g에 분산시킨 후 NaNO23.5 ㎖(3N, 0.0105 mol)를 가하였다. 반응물의 온도를 0℃ 내지 5℃로 유지시킨 후 반응물에 얼음 10 g을 넣은 다음, 35% HCl 2.28 ㎖(0.0262 mol)를 첨가하였다. 1시간 동안 교반하여 디아조화 반응을 완결시킨 후 소량의 설파믹산을 가하여 과량의 HNO2를 제거하였다.2.63 g (97%, 0.0105 mol) of 4-aminophenyl-β-acetoxyethylsulfone was dispersed in 30 ml of water and 10 g of ice, followed by addition of 3.5 ml (3N, 0.0105 mol) of NaNO 2 . The temperature of the reaction was maintained at 0 ° C. to 5 ° C., 10 g of ice was added to the reaction, and then 2.28 ml (0.0262 mol) of 35% HCl was added thereto. After stirring for 1 hour to complete the diazotization reaction, a small amount of sulfamic acid was added to remove excess HNO 2 .
별도의 반응용기에서 1-나프톨-8-아미노-3,6-디설폰산 4.16 g(82.1%, 0.01 mol)을 물 25 ㎖에 넣고, 4N NaOH수용액 2.5 ㎖로 중화시켜 녹였다. 위에서 얻은 디아조액에 얼음 10 g을 넣은 후 1-나프톨-8-아미노-3,6-디설폰산 중화액을 일시에 첨가하고 2.5시간 교반하여 커플링 반응을 완결시켰다.In a separate reaction vessel, 4.16 g (82.1%, 0.01 mol) of 1-naphthol-8-amino-3,6-disulfonic acid was added to 25 ml of water, neutralized with 2.5 ml of 4N NaOH aqueous solution, and dissolved. 10 g of ice was added to the diazo solution obtained above, and then 1-naphthol-8-amino-3,6-disulfonic acid neutralization solution was added at a time and stirred for 2.5 hours to complete the coupling reaction.
b) 과정b) process
4,6-디아미노-1,3-벤젠설폰산 3.48 g(85%, 0.011 mol)을 물 20 ㎖에 분산시킨 후 4N NaOH 수용액 5.5 ㎖를 가해 중화시킨 후(용해되지 않음) 5N HCl 4.4 ㎖를 넣어 분산시켰다.3.48 g (85%, 0.011 mol) of 4,6-diamino-1,3-benzenesulfonic acid was dispersed in 20 ml of water, followed by neutralization by adding 5.5 ml of 4N NaOH aqueous solution (not dissolved), 4.4 ml of 5N HCl. To disperse.
별도의 반응용기에서 시아누릭 클로라이드 2.20 g(99%, 0.012 mol)에 물 25 ㎖와 얼음 10 g, 분산제로서 폴리옥시에틸렌 노닐페닐 에테르(KONION NP-9) 10% 수용액 0.6 g을 넣고 분산시킨 분산액을 0℃ 내지 5℃로 유지시켰다. 여기에 얼음 10 g을 넣은 후, 위의 4,6-디아미노-1,3-벤젠설폰산 분산액을 서서히 첨가한 후 4시간 더 교반하여 축합반응을 완결시켰다.In a separate reaction vessel, 2.20 g (99%, 0.012 mol) of cyanuric chloride was dispersed in 25 ml of water, 10 g of ice, and 0.6 g of a 10% aqueous solution of polyoxyethylene nonylphenyl ether (KONION NP-9) as a dispersant. Was maintained at 0 ° C to 5 ° C. After 10 g of ice was added thereto, the above 4,6-diamino-1,3-benzenesulfonic acid dispersion was slowly added, followed by further stirring for 4 hours to complete the condensation reaction.
C) 과정C) process
상기 b) 과정에서 얻은 축합 용액에 35% HCl 2.39 ㎖(0.0275 mol)를 가하고, 반응물의 온도를 0℃ 내지 5℃로 유지시킨 후 얼음 10 g을 넣은 다음, NaNO23.67 ㎖(3N, 0.011 mol)를 첨가하였다. 1시간 동안 교반하여 디아조화 반응을 완결시킨 후 소량의 설파믹산을 가하여 과량의 HNO2를 제거하였다.2.39 ml (0.0275 mol) of 35% HCl was added to the condensation solution obtained in step b), and the temperature of the reactant was maintained at 0 ° C. to 5 ° C., followed by 10 g of ice, followed by 3.67 ml of NaNO 2 (3N, 0.011 mol). ) Was added. After stirring for 1 hour to complete the diazotization reaction, a small amount of sulfamic acid was added to remove excess HNO 2 .
그리고 상기 a) 과정에서 얻은 모노아조 화합물 용액의 온도를 0℃ 내지 5℃로 유지시킨 후 얼음 10 g을 넣은 다음, 상기 디아조액을 일시에 가하였다. 15% Na2CO3수용액 14 ㎖를 적하 깔때기를 이용하여 pH가 6.5∼7.0이 넘지 않도록 천천히 적가한 후 1.5시간 더 교반하여 2차 커플링 반응을 완결시켰다.And the temperature of the monoazo compound solution obtained in step a) was maintained at 0 ° C to 5 ° C and 10 g of ice was added, and then the diazo solution was added at a time. 14 ml of 15% Na 2 CO 3 aqueous solution was slowly added dropwise using a dropping funnel so as not to exceed 6.5 to 7.0, followed by further stirring for 1.5 hours to complete the secondary coupling reaction.
d) 과정d) process
상기 c) 과정에서 얻은 2차 커플링 용액에 5N HCl 수용액을 가하여 pH를 5.0 정도로 조정한 후 4-아미노페닐-β-아세톡시에틸설폰 2.58 g(99%, 0.0105 mol)을 가하고 1시간에 걸쳐 40℃ 내지 45℃로 서서히 승온하였다. pH를 4∼5로 조정하면서 1시간 더 교반하여 반응이 완결되면 NaOAc를 가하여 pH를 6∼6.5로 조정하였다. NaCl을 가하여 염석한 후 여과하고 건조하여 상기 구조식을 가진 청색 반응성염료를 얻었다.5N HCl aqueous solution was added to the secondary coupling solution obtained in step c) to adjust the pH to about 5.0, and then 2.58 g (99%, 0.0105 mol) of 4-aminophenyl-β-acetoxyethylsulfone was added over 1 hour. It heated up gradually to 40-45 degreeC. The mixture was stirred for 1 hour while adjusting the pH to 4 to 5, and when the reaction was completed, NaOAc was added to adjust the pH to 6 to 6.5. NaCl was added, salted, filtered and dried to obtain a blue reactive dye having the above structural formula.
1H-NMR(300 MHz, DMSO-d6) : δ 1.74(3H, s), 1.77(3H, s), 3.66(2H, t), 3.76(2H, t), 4.25∼4.29(4H, m), 7.48(2H, d), 7.83(2H, d), 7.99(2H, d), 8.15(1H, S), 8.23(1H, s), 8.24(2H, d), 8.26(1H, s), 9.22(1H, s), 10.65(2H, br. s), 10.74(1H, s), 11.55(1H, s), 16.22(1H, s) 1 H-NMR (300 MHz, DMSO-d 6 ): δ 1.74 (3H, s), 1.77 (3H, s), 3.66 (2H, t), 3.76 (2H, t), 4.25 to 4.29 (4H, m ), 7.48 (2H, d), 7.83 (2H, d), 7.99 (2H, d), 8.15 (1H, S), 8.23 (1H, s), 8.24 (2H, d), 8.26 (1H, s) , 9.22 (1H, s), 10.65 (2H, br.s), 10.74 (1H, s), 11.55 (1H, s), 16.22 (1H, s)
비교예Comparative example
상기 실시예 3과 동일한 방법으로 하되, 4-아미노페닐-β-아세톡시에틸설폰 대신에 p-설파닐산을 사용하여 청색 반응성염료를 얻었다.In the same manner as in Example 3, except for 4-aminophenyl-β-acetoxyethylsulfone, p-sulfanic acid was used to obtain a blue reactive dye.
실험예Experimental Example
상기 실시예 1∼5 및 비교예에서 합성한 청색 반응성염료를 면에 침염 염색을 실시한 후, 염착률을 측정하였다. 염착률은 다음 수학식 1에 의해 측정하였다.After dyeing the cotton with the blue reactive dyes synthesized in Examples 1 to 5 and Comparative Examples, the dyeing rate was measured. Dyeing rate was measured by the following equation (1).
상기 수학식 1에서: A0는 염색 전 염욕의 흡광도를 나타낸 것이고, A는 염색과 수세 후 잔욕의 흡광도의 합을 나타낸다.In Equation 1: A 0 represents the absorbance of the dye bath before dyeing, A represents the sum of the absorbances of the remaining bath after dyeing and washing with water.
상기 표 1에 나타낸 바와 같이, 본 발명의 삼반응기형 청색 반응성염료(실시예 1∼5)를 이용하여 얻어진 염색물은 종래의 이반응기형 반응성염료(비교예)와 비교하여 월등히 높은 염착률을 보여 주었다. 일광견뢰도는 대체로 3% o.w.f.인 경우 약간 떨어지지만 세탁견뢰도(KS K 030 A-4), 땀(산성, 알칼리성)견뢰도(AATCC Method 14) 및 염소견뢰도(JIS-0884-1983)는 모두 5등급으로서 뛰어 났고, 균염성 및 재현성도 우수하였다.As shown in Table 1, the dyeings obtained by using the tri-reactive type blue reactive dyes (Examples 1 to 5) of the present invention have a much higher dyeing rate compared to conventional di-reactive type dyes (comparative examples). Showed. Daylight fastness is slightly lower at 3% owf, but washing fastness (KS K 030 A-4), sweat (acid, alkaline) fastness (AATCC Method 14) and chlorine fastness (JIS-0884-1983) are all 5 grades. It was excellent and had excellent leveling and reproducibility.
상술한 바와 같이, 분자 구조내에 모노클로로트리아진과 두 개의 비닐설폰기를 반응성기가 도입된 본 발명의 삼반응기형 청색 반응성염료는 제조시 오염원을 줄일 수 있고, 색상이 선명하고, 낮은 수용해도를 가지며 직접성이 좋아 염착률이 높음을 알 수 있다.As described above, the tri-reactor type blue reactive dye of the present invention, in which a monochlorotriazine and two vinyl sulfone groups are introduced into a molecular structure, can reduce pollution during preparation, have a clear color, low water solubility and directness. This good dyeing rate is understood to be high.
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