N,N'-二-(4,6-二氯-[1,3,5]-三嗪基)-2,6-二氨基己酸的合成与鞣制性能
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摘要
在水为介质的条件下,以三聚氯氰(TCT)与赖氨酸(Lys)为原料,经缩合反应制备N,N?-二-(4,6-二氯-[1,3,5]-三嗪基)-2,6-二氨基己酸(简称DTDHA),利用FTIR和1HNMR对其结构进行了表征。通过正交实验考察了原料物质的量之比、缚酸剂种类、反应时间对产物收率的影响,得出较适宜的反应条件为:n(三聚氯氰)∶n(赖氨酸)=3.0∶1.0,KOH做缚酸剂,反应时间6 h,在该条件下DTDHA产率为91%。并将产物应用于生皮鞣制,以鞣制坯革的收缩温度为考察指标,采用单因素实验对鞣制工艺条件进行了优化。得到适宜的鞣制工艺条件为:鞣剂用量20%(以灰皮质量为基准,下同),温度从25℃开始每隔2 h阶梯上升15℃,最终达到55℃,鞣制总时间8h,在该条件下,坯革的收缩温度为85.6℃。该鞣制工艺下合成产物具有良好的鞣制效应,是一种新型的有机合成鞣剂。
N,N'-Bis-(4,6-dichloro-[1,3,5]-triazin-2-yl)-2,6-diaminohexanic acid(DTDHA) was synthesized by condensation reaction of cyanuric chloride(TCT) and lysine(Lys) in the presence of water,and was characterized by FTIR and 1 HNMR.The effects of molar ratio of raw material,type of acid-binding agent and reaction time on the yield of product were investigated by orthogonal experiment.The suitable reaction conditions were obtained as followed:the molar ratio of cyanuric chloride to lysine was 3.0∶1.0,potassium hydroxide was used as acid binding agent,and the reaction time was 6 h.Under these optimized conditions,the yield of product was 91%.The product was then applied to the tanning of raw hides.The single factor test method was used to optimize the technical conditions of the tanning process by using the shrinkage temperature of tanned leather as an inspection index.The results showed that the optimum tanning process conditions were that tanning agent dosage 20%(based on the mass of raw hide,the same below),temperature rising from 25 ℃,stepwise control rising by 15 ℃ every 2 hours,finally reaching to 55 ℃,total tanning time 8 hours.Under the above-mentioned conditions,the shrinkage temperature of crust leather was 85.6 ℃.The synthetic product has a good tanning effect and belongs to a new type of organic synthesis tanning agent.
N,N'-Bis-(4,6-dichloro-[1,3,5]-triazin-2-yl)-2,6-diaminohexanic acid(DTDHA) was synthesized by condensation reaction of cyanuric chloride(TCT) and lysine(Lys) in the presence of water,and was characterized by FTIR and 1 HNMR.The effects of molar ratio of raw material,type of acid-binding agent and reaction time on the yield of product were investigated by orthogonal experiment.The suitable reaction conditions were obtained as followed:the molar ratio of cyanuric chloride to lysine was 3.0∶1.0,potassium hydroxide was used as acid binding agent,and the reaction time was 6 h.Under these optimized conditions,the yield of product was 91%.The product was then applied to the tanning of raw hides.The single factor test method was used to optimize the technical conditions of the tanning process by using the shrinkage temperature of tanned leather as an inspection index.The results showed that the optimum tanning process conditions were that tanning agent dosage 20%(based on the mass of raw hide,the same below),temperature rising from 25 ℃,stepwise control rising by 15 ℃ every 2 hours,finally reaching to 55 ℃,total tanning time 8 hours.Under the above-mentioned conditions,the shrinkage temperature of crust leather was 85.6 ℃.The synthetic product has a good tanning effect and belongs to a new type of organic synthesis tanning agent.
引文
[1]Chen Wuyong(陈武勇),Li Guoying(李国英).Tanning chemistry[M].Beijing(北京):China Light Industry Press(中国轻工业出版社),2011:2.
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[9]Cui Lu(崔璐),Qiang Xihuai(强西怀),Chen Miaomiao(陈苗苗),et al.Chemical composition and application technology of TANFORTMSeries tanning agents[J].China Leather(中国皮革),2017,46(7):8-15.
[10]Li Jing(李靖),Shi Bi(石碧),Zhang Jing(张净),et al.Study on environmental performance of non-pickling chrome-free tanning agent TWT[J].Western Leather(西部皮革),2014,35(2):20-23.
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[12]Wei Shilin(魏世林).Tanning technology[M].Beijing(北京):China Light Industry Press(中国轻工业出版社),2012:129-147.
[13]Published by the National Development and Reform Commission of the People's Republic of China(中华人民共和国发展和改革委员会).Leather physical and mechanical testing-Determination of shrinkage temperature:QB/T 2713-2005[S].Beijing(北京):China Light Industry Press(中国轻工业出版社),2005.
[14]Yang Guibao(杨贵宝).Study on the reaction between aliphatic polyamines and cyanuric chloride and synthesis of multi-arm dendritic initial cores[D].Suzhou(苏州):Suzhou University(苏州大学),2009.
[15]Published by the National Development and Reform Commission of the People's Republic of China(中华人民共和国发展和改革委员会).Leather physical and mechanical testing-Determination of shrinkage temperature:QB/T 1873-2010[S].Beijing(北京):China Light Industry Press(中国轻工业出版社),2010.
[2]Sundarapandiyan S,Brutto P E,Siddhartha G,et al.Enhancement of chromium uptake in tanning using oxazolidine[J].Journal of Hazardous Materials,2011,190(1/2/3):802-809.
[3]Fabiani C,Ruscio F,Spadoni M,et al.Chromium(Ⅲ)salts recovery process from tannery wastewaters[J].Desalination,1997,108(1):183-191.
[4]Rao J R,Kanthimathi M,Thanikaivelan P,et al.Pickle-free chrome tanning using a polymeric synthetic tanning agent for cleaner leather processing[J].Clean Technologies and Environmental Policy,2004,6(4):243-249.
[5]Yu Congzheng(俞从正),Sun Genxing(孙根行),Guo Shengwei(郭生伟).A preliminary study on the origin of hexavalent chromium in leather[J].China Leather(中国皮革),2002,31(3):25-29.
[6]Ma Jianzhong(马建中).Synthetic principles and application technology of leather chemicals[M].Beijing(北京):China Light Industry Press(中国轻工业出版社),2009:100-204.
[7]Cao Yong(曹勇),Deng Yu(邓宇),Jia Jia(贾佳),et al.Leather tanning preparation and application method thereof:CN102127605B[P].2011-07-20.
[8]Xu Jiali(徐佳丽),Tang Jie(汤杰),Zheng Rulan(郑如兰),et al.Study on tanning properties of several chromium-free tanning agents[J].China Leather(中国皮革),2015,44(16):9-15.
[9]Cui Lu(崔璐),Qiang Xihuai(强西怀),Chen Miaomiao(陈苗苗),et al.Chemical composition and application technology of TANFORTMSeries tanning agents[J].China Leather(中国皮革),2017,46(7):8-15.
[10]Li Jing(李靖),Shi Bi(石碧),Zhang Jing(张净),et al.Study on environmental performance of non-pickling chrome-free tanning agent TWT[J].Western Leather(西部皮革),2014,35(2):20-23.
[11]Renekin C,Gamalino R,Temmark L,et al.Non-metallic tanning methods:CN102933725B[P].2013-02-13.
[12]Wei Shilin(魏世林).Tanning technology[M].Beijing(北京):China Light Industry Press(中国轻工业出版社),2012:129-147.
[13]Published by the National Development and Reform Commission of the People's Republic of China(中华人民共和国发展和改革委员会).Leather physical and mechanical testing-Determination of shrinkage temperature:QB/T 2713-2005[S].Beijing(北京):China Light Industry Press(中国轻工业出版社),2005.
[14]Yang Guibao(杨贵宝).Study on the reaction between aliphatic polyamines and cyanuric chloride and synthesis of multi-arm dendritic initial cores[D].Suzhou(苏州):Suzhou University(苏州大学),2009.
[15]Published by the National Development and Reform Commission of the People's Republic of China(中华人民共和国发展和改革委员会).Leather physical and mechanical testing-Determination of shrinkage temperature:QB/T 1873-2010[S].Beijing(北京):China Light Industry Press(中国轻工业出版社),2010.