CN105859626B - 一种二硫氰基双咪唑啉杀菌缓蚀剂及其制备方法与应用 - Google Patents

一种二硫氰基双咪唑啉杀菌缓蚀剂及其制备方法与应用 Download PDF

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CN105859626B
CN105859626B CN201610211500.9A CN201610211500A CN105859626B CN 105859626 B CN105859626 B CN 105859626B CN 201610211500 A CN201610211500 A CN 201610211500A CN 105859626 B CN105859626 B CN 105859626B
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袁斌
陈宇文
吕松
区韵莹
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Abstract

本发明公开了一种二硫氰基双咪唑啉杀菌缓蚀剂及其制备方法与应用，属于精细有机化工领域。本发明将双(羟乙基)双咪唑啉衍生物和亚硫酰氯按摩尔比1:2～3混合，低温搅拌1～1.5小时后回流反应30min，蒸馏，得到二(氯乙基)双咪唑啉衍生物；将二(氯乙基)双咪唑啉衍生物与硫氰酸钠按摩尔比1:2.1～2.3混合，加入去离子水，室温搅拌下反应30min后升温至60℃，继续反应30min，冷却，分离出有机相，洗涤后干燥，得到二硫氰基双咪唑啉衍生物杀菌缓蚀剂。在咪唑啉分子中引入硫氰基以后，增加了分子中可与金属配位的N和S原子的数量，提高了药剂的缓蚀性能，同时又增加了杀菌性能，是一种杀菌缓蚀剂。

Description

一种二硫氰基双咪唑啉杀菌缓蚀剂及其制备方法与应用
技术领域
本发明属于精细有机化工技术领域，具体涉及一种二硫氰基双咪唑啉杀菌缓蚀剂及其制备方法与应用。
背景技术
咪唑啉类缓蚀剂在油田管道防腐中已得到了广泛应用。众所周知，二硫氰基甲烷是一种高效杀藻杀菌剂。将硫氰基引入到咪唑啉分子结构中可形成的一类含氮、含硫的新型杀菌缓蚀剂。由于该物质分子中增加了可与金属配位的N及S原子数量，使药剂在金属表面可形成更好的吸附膜，从而对金属具有更好的保护效果，同时，硫氰基在咪唑啉分子中的引入，增加了该类化合物的杀菌性能，该类药剂是一种新型的多功能水处理剂。
发明内容
本发明的首要目的在于提供一种二硫氰基双咪唑啉杀菌缓蚀剂。该类药剂通过在咪唑啉分子结构中引入二个硫氰基，增加了分子中可与金属配位的N、S原子的数量，增加了与金属表面的配位能力，从而形成更紧密而牢固的吸附膜，减小了金属腐蚀速率，达到金属防腐的目的，同时，二硫氰基化合物还可作为水中的藻类和细菌的杀菌剂，缓蚀和杀菌协同增效的作用，减少了药剂的使用量，降低处理费用。
本发明的另一目的在于提供所述的二硫氰基双咪唑啉杀菌缓蚀剂的制备方法。
本发明的再一目的在于提供所述的二硫氰基双咪唑啉杀菌缓蚀剂的应用。
本发明的目的通过下述技术方案实现：一种二硫氰基双咪唑啉杀菌缓蚀剂，其分子结构通式如下：
其中：Z＝-(CH2)n-,n＝4或8。
所述的二硫氰基双咪唑啉杀菌缓蚀剂的制备方法，包括如下步骤：
将双(羟乙基)双咪唑啉衍生物和亚硫酰氯按摩尔比1:2～3混合，0-5℃搅拌1～1.5小时后回流反应30min，蒸馏，得到二(氯乙基)双咪唑啉衍生物；将所述的二(氯乙基)双咪唑啉衍生物、硫氰酸钠与去离子水按摩尔比1:2.1～2.3:20～30混合，室温搅拌下反应30min后升温至60℃，继续反应30min，冷却，分离出有机相，洗涤后真空干燥，得到二硫氰基双咪唑啉衍生物杀菌缓蚀剂。
所述的双(羟乙基)双咪唑啉衍生物优选为1,4-二[1′-(β-羟乙基)-2′-咪唑啉基]苯、1,8-二[1′-(β-羟乙基)-2′-咪唑啉基]辛烷、1,4-二[1′-(β-羟乙基)-2′-咪唑啉基]丁烷或2,6-二[1′-(β-羟乙基)-2′-咪唑啉基]吡啶。
所述的分离优选在分液漏斗中进行。
所述的洗涤优选采用除盐水洗涤一次。
所述的二硫氰基双咪唑啉衍生物杀菌缓蚀剂可以应用于抑制碳钢金属的腐蚀、大肠杆菌和氧化亚铁硫杆菌。
所述的二硫氰基双咪唑啉衍生物杀菌缓蚀剂在酸性水介质中可以有效抑制碳钢金属的腐蚀。
所述的酸性水介质优选为5％HCl溶液。
所述的二硫氰基双咪唑啉衍生物杀菌缓蚀剂在水介质中可以有效抑制大肠杆菌和氧化亚铁硫杆菌。
本发明所涉及的反应方程式为：
其中：Z＝-(CH2)n-,n＝4或8。
本发明相对于现有技术具有如下的优点及效果：本发明基于硫氰酸盐和咪唑啉类化合物对碳钢的良好缓蚀性能，将二个硫氰基和咪唑啉的分子片段衔接在一个分子中。在咪唑啉分子中引入硫氰基以后，既增加了分子中可与金属配位的N和S原子的数量，增强了与金属表面的配位络合能力，从而提高对金属的保护性能，提高了药剂的缓蚀性能；同时又增加了药剂的杀菌性能，是一种杀菌缓蚀剂，为该类药剂提供了广泛的应用前景。
具体实施方式
下面结合实施例对本发明作进一步详细的描述，但本发明的实施方式不限于此。
实施例1
在配有温度计、冷凝管和搅拌装置的三口烧瓶中，加入30.2g(0.1mol)1,4-二[1′-(β-羟乙基)-2′-咪唑啉基]苯，缓慢搅拌下，滴加35.7g(0.3mol)氯化亚砜，室温下搅拌反应1h后，回流反应30min，减压回收过量的氯化亚砜，得到1,4-二[1′-(β-氯乙基)-2′-咪唑啉基]苯中间体；
在上述反应器中加入3mol去离子水，35-40℃搅拌使有机物充分溶解，滴加20ml溶有17.9g(0.22mol)硫氰酸钠水溶液，室温搅拌下反应30min，升温至60℃，继续反应30min，冷却，用分液漏斗分离出有机相，再用除盐水洗涤一次，分出有机相真空干燥，得到1,4-二[1′-(β-硫氰基乙基)-2′-咪唑啉基]苯杀菌缓蚀剂，重33.6g，收率87.3％。
实施例2
按实施例1所述方法，用2,6-二[1′-(β-羟乙基)-2′-咪唑啉基]吡啶替代1,4-二[1′-(β-羟乙基)-2′-咪唑啉基]苯，获得2,6-二[1′-(β-硫氰基乙基)-2′-咪唑啉基]吡啶杀菌缓蚀剂，产物重31.5g，收率81.7％。
实施例3
按实施例1所述方法，用1,8-二[1′-(β-羟乙基)-2′-咪唑啉基]辛烷替代1,4-二[1′-(β-羟乙基)-2′-咪唑啉基]苯，获得1,8-二[1′-(β-硫氰基乙基)-2′-咪唑啉基]辛烷杀菌缓蚀剂，产物重33.14g，收率78.9％。
实施例4
按实施例1所述方法，用1,4-二[1′-(β-羟乙基)-2′-咪唑啉基]丁烷替代1,4-二[1′-(β-羟乙基)-2′-咪唑啉基]苯，获得1,4-二[1′-(β-硫氰基乙基)-2′-咪唑啉基]丁烷杀菌缓蚀剂，产物重31.0g，收率85.1％。
本发明所得的二硫氰基双咪唑啉衍生物可在金属表面形成良好的吸附膜，有利于金属的腐蚀防护，同时，还具有对大肠杆菌和氧化亚铁硫杆菌杀灭作用。下面只是考虑油田管道防腐和锅炉酸洗防腐进行了缓蚀试验。由于油田管道主要是N80钢材，锅炉酸洗系统主要金属材质是Q235碳钢，故采用不同的金属材料来模拟实验，检验二硫氰基双咪唑啉衍生物的缓蚀性能。用实施例1制得的1,4-二[1′-(β-硫氰基乙基)-2′-咪唑啉基]苯和实施例3制得的1,8-二[1′-(β-硫氰基乙基)-2′-咪唑啉基]辛烷做缓蚀剂。向1000ml 5％HCl溶液中分别加入0.3％二硫氰基双咪唑啉衍生物缓蚀剂，分别将Q235碳钢片和N80钢片悬挂在盐酸溶液中，恒温水浴65℃，放置6h后，测量加入缓蚀剂和未加入缓蚀剂时，钢片的质量变化计算出缓蚀率，其实验结果如下表1所示：
表1药剂缓蚀性能实验结果
采用逐级稀释和平皿活菌计数法评定了药剂对大肠杆菌的杀菌性能。采用《GBT14643.6-2009工业循环冷却水中菌藻的测定方法第6部分：铁细菌的测定MPN法》评定药剂的对氧化亚铁硫杆菌的杀菌能力。实验结果见下表2所示：
表2药剂杀菌实验结果
上述实施例为本发明较佳的实施方式，但本发明的实施方式并不受上述实施例的限制，其他的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化，均应为等效的置换方式，都包含在本发明的保护范围之内。

Claims (7)

1.一种二硫氰基双咪唑啉杀菌缓蚀剂，其特征在于，其分子结构通式如下：
其中：Z＝-(CH2)n-,n＝4或8。
2.权利要求1所述的二硫氰基双咪唑啉杀菌缓蚀剂的制备方法，其特征在于，包括如下步骤：将双(羟乙基)双咪唑啉衍生物和亚硫酰氯按摩尔比1:2～3混合，0-5℃搅拌1～1.5小时后回流反应30min，蒸馏，得到二(氯乙基)双咪唑啉衍生物；将所述的二(氯乙基)双咪唑啉衍生物、硫氰酸钠与去离子水按摩尔比1:2.1～2.3:20～30混合，室温搅拌下反应30min后升温至60℃，继续反应30min，冷却，分离出有机相，洗涤后真空干燥，得到二硫氰基双咪唑啉衍生物杀菌缓蚀剂；
其中，所述的双(羟乙基)双咪唑啉衍生物其结构式如下：
其中，所述的二(氯乙基)双咪唑啉衍生物其结构式如下：
其中：Z＝-(CH2)n-,n＝4或8。
3.根据权利要求2所述的二硫氰基双咪唑啉杀菌缓蚀剂的制备方法，其特征在于，所述的分离在分液漏斗中进行。
4.根据权利要求2所述的二硫氰基双咪唑啉杀菌缓蚀剂的制备方法，其特征在于，所述的洗涤采用除盐水洗涤一次。
5.权利要求1所述的二硫氰基双咪唑啉衍生物杀菌缓蚀剂应用于抑制碳钢金属的腐蚀、大肠杆菌和氧化亚铁硫杆菌。
6.根据权利要求5所述的二硫氰基双咪唑啉衍生物杀菌缓蚀剂的应用，其特征在于，所述的二硫氰基双咪唑啉衍生物杀菌缓蚀剂在酸性水介质中抑制碳钢金属的腐蚀。
7.根据权利要求5所述的二硫氰基双咪唑啉衍生物杀菌缓蚀剂的应用，其特征在于，所述的二硫氰基双咪唑啉衍生物杀菌缓蚀剂在水介质中抑制大肠杆菌和氧化亚铁硫杆菌。
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