CN112280033A - 一种聚苯胺缓蚀剂及其制备方法 - Google Patents
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Abstract
本发明公开了一种聚苯胺类缓蚀剂及其制备方法，包括：1)对苯二胺与对二溴苯、4,7‑二溴‑2,1,3‑苯并噻二唑经Buchwald‑Hartwig芳胺化反应合成含有苯并噻二唑的单元的端氨基聚苯胺；2)端氨基聚苯胺与1,2‑环氧十二烷亲核开环，制备长链烷烃封端的聚苯胺溶液作为缓蚀剂；本发明制备的长链烷烃封端的聚苯胺具有较低聚合度，并且分子规整性较低，因此水溶性良好，阻垢效率达97％，在水系统缓蚀剂中有广泛的应用前景。
Description
技术领域
本发明涉及一种有机高分子缓蚀剂，尤其涉及一种聚苯胺类缓蚀剂及其制备方法。
背景技术
在工业生产中，大多数水系统的设备或管道被腐蚀是常见问题，一方面，由于水系统中常含有大量的腐蚀离子和分子，如Cl-、SO2等等，其极易对碳钢及其他金属材质造成腐蚀；另一方面，由于系统中一些特定的操作步骤，如循环水系统中会采用酸洗的方法除垢、油田开采中有油井酸化过程，使得系统管壁与酸溶液接触，造成酸腐蚀。腐蚀不仅会引起系统老化与破损，造成环境污染，同时还会给全球带来经济、资源和能源上的损失。投加缓蚀剂防止金属腐蚀是一种操作简单方便、经济有效的防腐蚀方法，缓蚀剂分为无机盐、有机小分子、有机高分子，无机缓蚀剂如铬酸盐、磷酸盐、钼酸盐，因其对环境的破坏和人们健康的危害，已逐渐被淘汰；相比于有机小分子，高分子化合物作为缓蚀剂吸附活性中心更多，在被保护基底的吸附覆盖面积大、并容易形成单层或多层致密的保护膜，缓蚀保护能力更持久等优势，成为缓蚀剂研究领域中的趋势之一。
聚苯胺分子结构含有中含有N原子和苯环，N原子上的孤对电子与苯环形成共轭π键电子能与金属管道Fe原子的d空轨道进行配位结合，化学附着在管道壁上，形成稳定的缓蚀层。另外，聚苯胺合成容易、成本低廉、具有耐划伤和耐腐蚀性能已成为最有应用价值的聚合物材料之一，广泛应用于防腐防护领域。
但聚苯胺的高度共轭和规整的分子链结构，使其溶解性级差，常用的方法是复配或掺杂无机酸或有机酸或有机高分子羧酸以提高其水溶解性，但掺杂酸的性质会影响缓蚀剂在水体系中的稳定性。有研究表明，苯胺低聚物相比于高聚物有更好的溶解性，因为低分子量聚苯胺链间的作用力与缠绕程度相比于高分子量大大减小；但苯胺低聚体物的化学结构、导电性与聚苯胺相似，另外加入苯胺衍生物降低分子链的规整度，也有利于增加其水溶性。
发明内容
针对上述技术现状，本发明提供一种聚苯胺缓蚀剂，利用对苯二胺和对二溴苯及其衍生物的Buchwald-Hartwig芳胺化反应，缩合制备低分子量聚苯胺衍生物，另外以疏水长链烷烃封端，该聚苯胺衍生物复配盐酸后具有良好的水溶性，缓蚀效率达90％以上。
所述聚苯胺缓蚀剂，具有如下分子式：
式中，y:x＝0～(1:3)，x和y均取整数。
上述聚苯胺缓蚀剂的反应流程及制备方法如下：
把对苯二胺、催化剂、碱和溶剂放入反应釜中，开启氩气保护，温度升高至100～120℃后，开始滴加对二溴苯和4,7-二溴-2,1,3-苯并噻二唑的混合溶液，于0.5～1h滴完后保温反应10～12h，经过滤、洗涤、干燥制备聚苯胺衍生物p(ANI-co-BZTDZ)。
将聚苯胺衍生物p(ANI-co-BZTDZ)溶于盐酸溶液中，加入1,2-环氧十二烷，升温至50～60℃，搅拌1～2h结束反应，制备得到一种聚苯胺缓蚀剂溶液。
上述制备方法所述的催化剂为钯磷配合物，可以是四(三苯基膦)钯、二(三叔丁基膦)钯。
上述制备方法所述的碱可以是叔丁醇及其盐、双(三甲硅基)氨基钠。
上述制备方法所述的溶剂可以是甲苯、二氧六环。
上述制备方法所述的对苯二胺、对二溴苯、4,7-二溴-2,1,3-苯并噻二唑的投料比为2.2～2.5:1.4～2:0～0.5(摩尔量)。
上述制备方法所述的盐酸溶液为质量分数为10～30％的盐酸水溶液。
上述制备方法所述的1,2-环氧十二烷与p(ANI-co-BZTDZ)的投料质量比例为1:0.3～0.5。
本发明具有如下优点和有益效果：
(1)本发明利用Buchwald-Hartwig芳胺化反应制备聚苯胺衍生物，p(ANI-co-BZTDZ)具有较低的聚合度，4,7-二溴-2,1,3-苯并噻二唑作为第三缩合单体，降低了聚苯胺分子链的规整性，大大提高了聚苯胺的水溶性。
(2)本发明制备的p(ANI-co-BZTDZ)中的苯并噻二唑为杂环单元，进一步提高了聚苯胺分子链的吸附活性中心。
(3)本发明制备的聚苯胺缓蚀剂以长链烷烃封端，长链烷烃的疏水作用能够排斥酸性离子与金属表面的接触，进一步减低金属被酸腐的程度。
附图说明
图1为聚苯胺缓蚀剂的FT-IR图。
图2为碳钢在实施例1～3制备的p(ANI-co-BZTDZ)的1mol/L HCl溶液中浸泡2小时后的极化曲线图(25℃)。
具体实施方式
下面结合具体实施例对本发明做进一步详细说明，但实施例并不对本发明做任何形式的限定。除非特别说明，本发明采用的试剂、方法和设备为本技术领域常规试剂、方法和设备。
实施例1
准确称量10.03g(0.09mol)对苯二胺、0.04g(0.07mmol)双(二亚苄基丙酮)钯、5.15g(0.05mol)叔丁醇钠并加入反应釜中，加入100mL甲苯溶解，通入氩气，15min后注射加入3.5mL三叔丁基膦，升温至100℃开始滴加二溴苯的甲苯溶液[13.92g(0.06mol)对二溴苯和6.20g(0.02mol)4,7-二溴-2,1,3-苯并噻二唑溶于30mL甲苯]，于0.5h内滴完，保温反应10h，反应结束后抽滤，用丙酮洗涤滤饼，在50℃真空烘箱干燥24h，得到p(ANI-co-BZTDZ)。
称取2.23g p(ANI-co-BZTDZ)溶于10mL质量分数为20％的盐酸水溶液中，加入0.81g 1,2-环氧十二烷，升温至60℃，搅拌2h结束反应，制备得到一种聚苯胺缓蚀剂。
实施例2
准确称量5.12g(0.05mol)对苯二胺、0.02g(0.09mmol)醋酸钯、2.88g(0.03mol)叔丁醇钠并加入反应釜中，加入20mL溶解，通入氩气，15min后注射加入0.13g(0.5mmol)三苯基膦，升温至120℃开始滴加二溴苯的甲苯溶液[8.04g(0.03mol)对二溴苯和1.11g(3.79mmol)4,7-二溴-2,1,3-苯并噻二唑溶于20mL甲苯]，于0.5h内滴完，保温反应12h，反应结束后抽滤，用丙酮洗涤滤饼，在50℃真空烘箱干燥24h，得到p(ANI-co-BZTDZ)。
称取3.05g p(ANI-co-BZTDZ)溶于10mL质量分数为20％的盐酸水溶液中，加入1.1g 1,2-环氧十二烷，升温至50℃，搅拌2h结束反应，制备得到一种聚苯胺缓蚀剂。
实施例3
制备不含苯并噻二唑单元的聚苯胺缓蚀剂。
准确称量8.55g(0.08mol)对苯二胺、0.04g(0.07mmol)双(二亚苄基丙酮)钯、3.86g(0.04mol)叔丁醇钠并加入反应釜中，加入20mL二氧六环溶解，通入氩气，15min后注射加入3.5mL三叔丁基膦，升温至100℃开始滴加对二溴苯的甲苯溶液[16.22g(0.07mol)对二溴苯溶于30mL甲苯]，于0.5h内滴完，保温反应11h，反应结束后抽滤，用丙酮洗涤滤饼，在50℃真空烘箱干燥24h，得到p(ANI-co-BZTDZ)。
称取6.21g p(ANI-co-BZTDZ)溶于20mL质量分数为20％的盐酸水溶液中，加入2.24g 1,2-环氧十二烷，升温至50℃，搅拌2h结束反应，制备得到一种聚苯胺缓蚀剂。
实施例4
按照GB/T 18175-2014《水处理剂缓蚀性能的测定-旋转挂片法》对实施例1～3制备的聚苯胺缓蚀剂的缓蚀性能进行测试，按以下公式计算缓蚀率：
式中，W0是空白溶液中碳钢的失重量，W1是加入聚苯胺缓蚀剂溶液中碳钢的失重量。
缓蚀剂溶液的测试浓度均为0.05g/L[0.05g p(ANI-co-BZTDZ)],结果：实施例1为97.3％，实施例2为92.5％，实施例3为90.8％。
实施例5
采用实施例1制备的p(ANI-co-BZTDZ)制备不同浓度、酸度、1,2-环氧十二烷投料量的缓蚀剂溶液，并按实施例4方法测定缓蚀率，结果列于表1。
从表中可知，实施例1制备的p(ANI-co-BZTDZ)在浓度0.05g/L时，缓蚀效果最好；测试溶液的酸度对缓蚀率的影响不显著，说明复配氯离子前后，缓蚀剂的水溶性和与金属的配位能力影响不大；另外，加入1,2-环氧十二烷封端后的缓蚀剂缓蚀效率明显挺高，说明疏水链起到排斥腐蚀因子的作用。
Claims (8)
1.一种聚苯胺类缓蚀剂，其特征在于，具有如下分子结构：
式中，y:x＝0～(1:3)，x和y均取整数。
2.一种聚苯胺类缓蚀剂的制备方法，其特征在于，包括以下步骤：
把对苯二胺、催化剂、碱和溶剂放入反应釜中，开启氩气保护，温度升高至100～120℃后，开始滴加对二溴苯和4,7-二溴-2,1,3-苯并噻二唑的混合溶液，与0.5～1h滴完后保温反应10～12h，经过滤、洗涤、干燥制备聚苯胺衍生物p(ANI-co-BZTDZ)；
将聚苯胺衍生物p(ANI-co-BZTDZ)溶于盐酸溶液中，加入1,2-环氧十二烷，升温至50～60℃，搅拌1～2h结束反应，制备得到一种聚苯胺缓蚀剂溶液。
3.根据权利要求2所述的一种聚苯胺类缓蚀剂的制备方法，其特征在于，所述的催化剂为钯磷配合物，可以是四(三苯基膦)钯、二(三叔丁基膦)钯。
4.根据权利要求2所述的一种聚苯胺类缓蚀剂的制备方法，其特征在于，所述的碱可以是叔丁醇及其盐、双(三甲硅基)氨基钠。
5.根据权利要求2所述的一种聚苯胺类缓蚀剂的制备方法，其特征在于，所述的溶剂可以是甲苯、二氧六环。
6.根据权利要求2所述的一种聚苯胺类缓蚀剂的制备方法，其特征在于，所述的对苯二胺、对二溴苯、4,7-二溴-2,1,3-苯并噻二唑的投料比为2.2～2.5:1.4～2:0～0.5(摩尔量)。
7.根据权利要求2所述的一种聚苯胺类缓蚀剂的制备方法，其特征在于，所述的盐酸溶液为质量分数为10～30％的盐酸水溶液。
8.根据权利要求2所述的一种聚苯胺类缓蚀剂的制备方法，其特征在于，所述的1,2-环氧十二烷与p(ANI-co-BZTDZ)的投料质量比例为1:0.3～0.5，每1gp(ANI-co-BZTDZ)需要盐酸水溶液4～6mL。
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