CN117362499A - 一种聚合物基阻垢缓蚀剂的制备工艺 - Google Patents
一种聚合物基阻垢缓蚀剂的制备工艺 Download PDFInfo
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- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
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- C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
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Abstract
本发明涉及阻垢缓蚀技术领域，且公开了一种聚合物基阻垢缓蚀剂的制备工艺，本发明的技术效果：本发明的聚合物基阻垢缓蚀剂含有丰富的羧基、亚氨基和磺酸等基团，对Ca2+有很强螯合能力，可以抑制硫酸钙或碳酸钙晶体的生长，并且在20‑25mg/L的低浓度时，对硫酸钙和碳酸钙也具有很好的阻垢性能。同时聚合物基阻垢缓蚀剂的羧基、巯基、磺酸基团，可以与钢表面的铁原子发生配合螯合作用，使聚合物基阻垢缓蚀剂在钢表面形成牢固的高分子膜，抑制腐蚀介质与钢表面进行接触，避免钢等金属发生腐蚀，表现出优异的缓蚀性能，在石油化工等领域中的冷却循环水设备、加氢塔顶装置、裂化装置有很好的应用前景。
Description
技术领域
本发明涉及阻垢缓蚀技术领域，具体为一种聚合物基阻垢缓蚀剂的制备工艺。
背景技术
石油化工领域中的冷却循环水设备、加氢塔顶装置、加氢裂化装置在实际生产过程中，普遍存在结垢、腐蚀生锈的现象，会导致机械设备损坏，使用寿命降低，生产水平下降，甚至会引起安全事故。目前可以采用阻垢剂和缓蚀剂对这些设备进行阻垢和缓蚀防腐。
开发新型阻垢剂和缓蚀剂应用于石油化工领域具有重要的意义。专利CN103289745B公开了一种用于加氢装置的阻垢缓蚀剂，由咪唑啉季铵盐、疏基三唑衍生物、中和性胺类物质等复配得到，可以有效解决加氢精制、加氢裂化装置设备腐蚀的问题；但是该阻垢缓蚀剂没有表现出很好的阻垢性能。
专利CN104258735B公开了一种反渗透膜阻垢剂及其制备方法，以丙烯酰胺、磺酸盐、丙烯酸酯、马来酸酐四元共聚物为主要成分，对不同污堵物质都有很好的阻垢分散作用，但是该阻垢剂没有表现出很好的金属缓蚀防腐性能。
发明内容
本发明解决的技术问题：制备了一种高阻垢性能和缓蚀性能的聚合物基阻垢缓蚀剂。
本发明的技术方案：一种聚合物基阻垢缓蚀剂，包括如下重量份数的原料，400-700份水、200-300份乙醇或异丙醇助溶剂、100份磺酸半胱氨酸丙烯酸酯单体、0.45-0.6份偶氮二异丁腈；磺酸半胱氨酸丙烯酸酯单体的化学结构式如下：
聚合物基阻垢缓蚀剂的制备工艺如下：向水中加入助溶剂、磺酸半胱氨酸丙烯酸酯单体，搅拌溶解，氮气气氛下滴加偶氮二异丁腈，进行反应，将溶液倒入进丙酮中析出沉淀，过滤，丙酮洗涤沉淀并干燥，得到聚合物基阻垢缓蚀剂。
进一步的，反应控制温度为60-75℃，控制时间为3-5h。
进一步的，磺酸半胱氨酸丙烯酸酯单体的制备工艺如下所示：
（1）向丙酮中加入摩尔比为1:（1-1.3）的3-氯-2-羟基丙基甲基丙烯酸酯、丁二酸酐，55-65℃的温度下回流10-20h，浓缩溶剂，中间体产物加入到氯化亚砜中，70-80℃的温度下回流2-4h，浓缩溶剂，石油醚洗涤，得到中间体1。
（2）向二氯甲烷中加入3-氯-2-羟基丙烷磺酸钠和三乙胺，0-5℃下加入中间体1，搅拌均匀后加热至25-35℃，反应6-12h，浓缩溶剂，石油醚洗涤，产物在乙醇中重结晶纯化，得到中间体2。
（3）向四氢呋喃、1,4-二氧六环、乙酸乙酯任一种反应溶剂中加入半胱氨酸、中间体2和三乙胺，进行反应，滴加盐酸溶液控制溶液的pH至6，浓缩溶剂，石油醚洗涤，产物在乙醇中重结晶纯化，得到磺酸半胱氨酸丙烯酸酯单体。
进一步的，步骤（2）中3-氯-2-羟基丙烷磺酸钠、三乙胺、中间体1的摩尔比为（0.9-1.3）:（1.1-1.3）:1。
进一步的，步骤（3）中半胱氨酸、中间体2、三乙胺的摩尔比例为（1.8-2.4）:1:（2.2-2.6）。
进一步的，步骤（3）中反应控制温度为70-100℃，时间控制为12-24h。
本发明的技术效果：本发明以廉价易得的3-氯-2-羟基丙基甲基丙烯酸酯、丁二酸酐、氯化亚砜、3-氯-2-羟基丙烷磺酸钠、半胱氨酸等作为反应物，经过简单的酸酐开环、酯化、取代等反应，制备了一种含有巯基、羧基和磺酸基团的磺酸半胱氨酸丙烯酸酯单体，在醇-水溶剂体系中聚合反应得到新型的聚合物基阻垢缓蚀剂。
本发明的聚合物基阻垢缓蚀剂含有丰富的羧基、亚氨基和磺酸等基团，对Ca2+有很强螯合能力，可以抑制硫酸钙或碳酸钙晶体的生长，并且在20-25mg/L的低浓度时，对硫酸钙和碳酸钙也具有很好的阻垢性能。
本发明的聚合物基阻垢缓蚀剂中含有丰富的羧基、巯基、磺酸基团，可以与钢表面的铁原子发生配合螯合作用，使聚合物基阻垢缓蚀剂在钢表面形成牢固的高分子膜，抑制腐蚀介质与钢表面进行接触，避免钢等金属发生腐蚀，表现出优异的缓蚀性能。聚合物基阻垢缓蚀剂在石油化工等领域中的冷却循环水设备、加氢塔顶装置、裂化装置有很好的应用前景。
附图说明
图1是聚合物基阻垢缓蚀剂的红外光谱。
具体实施方式
实施例1
（1）向80mL 丙酮中加入摩尔比为50mmol 3-氯-2-羟基丙基甲基丙烯酸酯、58mmol丁二酸酐，65℃的温度下回流10h，浓缩溶剂，中间体产物加入到60mL氯化亚砜中，80℃的温度下回流2h，浓缩溶剂，石油醚洗涤，得到中间体1。
（2）向150mL二氯甲烷中加入65 mmol 3-氯-2-羟基丙烷磺酸钠和65mmol三乙胺，0℃下加入50mmol中间体1，搅拌均匀后加热至30℃，反应12h，浓缩溶剂，石油醚洗涤，产物在乙醇中重结晶纯化，得到中间体2。
（3）向100mL乙酸乙酯溶剂中加入72 mmol半胱氨酸、30mmol中间体2和78mmol三乙胺，加热至80℃反应24h，滴加盐酸溶液控制溶液的pH至6，浓缩溶剂，石油醚洗涤，产物在乙醇中重结晶纯化，得到磺酸半胱氨酸丙烯酸酯单体。反应路线如下：
（4）向100g水中加入50g乙醇助溶剂、20g磺酸半胱氨酸丙烯酸酯单体，搅拌溶解，氮气气氛下滴加0.1g偶氮二异丁腈，加热至60℃反应5h，将溶液倒入进丙酮中析出沉淀，过滤，丙酮洗涤沉淀并干燥，得到聚合物基阻垢缓蚀剂。
说明书图1的红外光谱显示，磺酸半胱氨酸丙烯酸酯单体的巯基-SH吸收峰出现在2496cm-1，酯基中C=O的吸收峰出现在1740cm-1，烯基中C=C的吸收峰出现在1669cm-1，磺酸基团中S=O的吸收峰出现在1164cm-1。
聚合物基阻垢缓蚀剂中巯基-SH吸收峰出现在2503cm-1，酯基中C=O的吸收峰出现在1735cm-1，磺酸基团中S=O的吸收峰出现在1166cm-1，1669cm-1处的烯基C=C的吸收峰消失，说明磺酸半胱氨酸丙烯酸酯单体发生聚合反应，生成了聚合物基阻垢缓蚀剂。
实施例2
（1）向100mL 丙酮中加入摩尔比为50mmol 3-氯-2-羟基丙基甲基丙烯酸酯、65mmol丁二酸酐，60℃的温度下回流12h，浓缩溶剂，中间体产物加入到80mL氯化亚砜中，80℃的温度下回流2h，浓缩溶剂，石油醚洗涤，得到中间体1。
（2）向150mL二氯甲烷中加入65 mmol 3-氯-2-羟基丙烷磺酸钠和65mmol三乙胺，5℃下加入50mmol中间体1，搅拌均匀后加热至25℃，反应12h，浓缩溶剂，石油醚洗涤，产物在乙醇中重结晶纯化，得到中间体2。
（3）向80mL 1,4-二氧六环溶剂中加入54 mmol半胱氨酸、30mmol中间体2和66mmol三乙胺，加热至100℃反应12h，滴加盐酸溶液控制溶液的pH至6，浓缩溶剂，石油醚洗涤，产物在乙醇中重结晶纯化，得到磺酸半胱氨酸丙烯酸酯单体。
（4）向80g水中加入40g异丙醇助溶剂、20g磺酸半胱氨酸丙烯酸酯单体，搅拌溶解，氮气气氛下滴加0.09g偶氮二异丁腈，加热至75℃反应3h，将溶液倒入进丙酮中析出沉淀，过滤，丙酮洗涤沉淀并干燥，得到聚合物基阻垢缓蚀剂。
实施例3
（1）向60mL 丙酮中加入摩尔比为50mmol 3-氯-2-羟基丙基甲基丙烯酸酯、50mmol丁二酸酐，55℃的温度下回流20h，浓缩溶剂，中间体产物加入到60mL氯化亚砜中，70℃的温度下回流4h，浓缩溶剂，石油醚洗涤，得到中间体1。
（2）向80mL二氯甲烷中加入45 mmol 3-氯-2-羟基丙烷磺酸钠和55mmol三乙胺，0℃下加入50mmol中间体1，搅拌均匀后加热至35℃，反应6h，浓缩溶剂，石油醚洗涤，产物在乙醇中重结晶纯化，得到中间体2。
（3）向装有冷凝回流管的反应瓶中加入100mL四氢呋喃溶剂、60 mmol半胱氨酸、30mmol中间体2和78mmol三乙胺，置于水浴锅中，水浴锅加热至70℃，回流反应24h，滴加盐酸溶液控制溶液的pH至6，浓缩溶剂，石油醚洗涤，产物在乙醇中重结晶纯化，得到磺酸半胱氨酸丙烯酸酯单体。
（4）向140g水中加入60g乙醇助溶剂、20g磺酸半胱氨酸丙烯酸酯单体，搅拌溶解，氮气气氛下滴加0.12g偶氮二异丁腈，加热至70℃反应4h，将溶液倒入进丙酮中析出沉淀，过滤，丙酮洗涤沉淀并干燥，得到聚合物基阻垢缓蚀剂。
对比例1
向100g水中加入50g乙醇助溶剂、20g 3-氯-2-羟基丙基甲基丙烯酸酯（结构式为），搅拌溶解，氮气气氛下滴加0.1g偶氮二异丁腈，加热至60℃反应5h，将溶液倒入进丙酮中析出沉淀，过滤，丙酮洗涤沉淀并干燥，得到阻垢缓蚀剂。
对比例2
向100g水中加入50g乙醇助溶剂、20g中间体1（结构式为），搅拌溶解，氮气气氛下滴加0.1g偶氮二异丁腈，加热至60℃反应5h，将溶液倒入进丙酮中析出沉淀，过滤，丙酮洗涤沉淀并干燥，得到阻垢缓蚀剂。
对比例3
向100g水中加入50g乙醇助溶剂、20g中间体2（结构式为），搅拌溶解，氮气气氛下滴加0.1g偶氮二异丁腈，加热至60℃反应5h，将溶液倒入进丙酮中析出沉淀，过滤，丙酮洗涤沉淀并干燥，得到阻垢缓蚀剂。
阻垢性能测试：将40mmol氯化钙溶解在500mL水中，配置成氯化钙溶液；将40mmol硫酸钠或碳酸氢钠溶解在500mL水中，配置成硫酸钠或碳酸氢钠溶液；分别移取500mL氯化钙溶液和500mL硫酸钠或碳酸氢钠溶液混匀，然后加入一定量的阻垢缓蚀剂并调控溶液中阻垢缓蚀剂的浓度，25℃或加热至70℃保温12h，然后通过等离子发射光谱法测定溶液中Ca2+的浓度。计算阻垢率。阻垢率=（C2-C1）/（C0-C1）×100%。
C2是加入阻垢剂，同时70℃保温12h后溶液中Ca2+离子浓度。
C1是没有加入阻垢剂，70℃保温12h后溶液中Ca2+离子浓度。
C0是没有加入阻垢剂，25℃保温12h后溶液中Ca2+离子浓度。
表1硫酸钙阻垢性能测试。
表2碳酸钙阻垢性能测试表。
各实施例以磺酸半胱氨酸丙烯酸酯单体进行聚合反应，得到聚合物基阻垢缓蚀剂，当阻垢剂的浓度为20-25mg/L时，对硫酸钙和碳酸钙的阻垢性能最好，最高达到97.3%、98.4%，这是因为聚合物基阻垢缓蚀剂中含有丰富的羧基、亚氨基和磺酸基团，对Ca2+有很强螯合能力，可以抑制硫酸钙或碳酸钙晶体的生长，起到非常好的阻垢效果。
对比例1、2制备的阻垢缓蚀剂不含有羧基、亚氨基和磺酸基团，对Ca2+螯合能力的很差，无法抑制硫酸钙或碳酸钙晶体的生长，因此阻垢效果不好。
对比例3制备的阻垢缓蚀剂不含有羧基、亚氨基，只含有磺酸基团，对Ca2+螯合能力的不佳，因此阻垢效果较差。
缓蚀性能测试：向0.5mol/L的硫酸溶液中加入阻垢缓蚀剂，并控制溶液阻垢缓蚀剂的浓度，作为测试介质溶液；以N80钢作为工作电极，并浸泡在测试介质溶液中30min，然后以铂电极作对电极，饱和甘汞电极作参比电极，采用电化学工作站测试极化曲线测试。扫描范围为-0.8V至-0.2V，扫描速率为0.01V/s。计算缓蚀率n，n=（J1-J2）/J1×100%。J1是测试介质溶液中未加入阻垢缓蚀剂的腐蚀电流。J2是测试介质溶液中加入阻垢缓蚀剂的腐蚀电流。
表3阻垢缓蚀剂的缓蚀性能测试表
经过缓蚀性能测试后，各实施例以磺酸半胱氨酸丙烯酸酯单体进行聚合反应，得到聚合物基阻垢缓蚀剂，当测试介质溶液中阻垢剂的浓度为50-60mg/L时，缓蚀率最高，达到94.3%，这是因为聚合物基阻垢缓蚀剂中含有丰富的羧基、巯基、磺酸基团，可以与钢表面的铁原子发生配合螯合作用，使阻垢缓蚀剂在钢表面形成牢固的高分子膜，抑制腐蚀介质与钢表面进行接触，避免钢等金属发生腐蚀，表现出优异的缓蚀性能。
Claims (8)
1.一种聚合物基阻垢缓蚀剂的制备工艺，其特征在于，聚合物基阻垢缓蚀剂包括如下重量份数的原料，400-700份水、200-300份助溶剂、100份磺酸半胱氨酸丙烯酸酯单体、0.45-0.6份偶氮二异丁腈；所述磺酸半胱氨酸丙烯酸酯单体的化学结构式如式（Ⅰ）所示：
（Ⅰ）
所述聚合物基阻垢缓蚀剂的制备工艺如下所示：向水中加入助溶剂、磺酸半胱氨酸丙烯酸酯单体，搅拌溶解，氮气气氛下滴加偶氮二异丁腈，进行反应，将溶液倒入进丙酮中析出沉淀，过滤，丙酮洗涤沉淀并干燥，得到聚合物基阻垢缓蚀剂。
2.根据权利要求1所述的聚合物基阻垢缓蚀剂的制备工艺，其特征在于，所述助溶剂包括乙醇或异丙醇。
3.根据权利要求1所述的聚合物基阻垢缓蚀剂的制备工艺，其特征在于，所述反应控制温度为60-75℃，控制时间为3-5h。
4.根据权利要求1所述的聚合物基阻垢缓蚀剂的制备工艺，其特征在于，所述磺酸半胱氨酸丙烯酸酯单体的制备工艺如下所示：
（1）向丙酮中加入摩尔比为1:（1-1.3）的3-氯-2-羟基丙基甲基丙烯酸酯、丁二酸酐，55-65℃的温度下回流10-20h，浓缩溶剂，中间体产物加入到氯化亚砜中，70-80℃的温度下回流2-4h，浓缩溶剂，石油醚洗涤，得到中间体1；
（2）向二氯甲烷中加入3-氯-2-羟基丙烷磺酸钠和三乙胺，0-5℃下加入中间体1，搅拌均匀后加热至25-35℃，反应6-12h，浓缩溶剂，石油醚洗涤，产物在乙醇中重结晶纯化，得到中间体2；
（3）向反应溶剂中加入半胱氨酸、中间体2和三乙胺，进行反应，滴加盐酸溶液控制溶液的pH至6，浓缩溶剂，石油醚洗涤，产物在乙醇中重结晶纯化，得到磺酸半胱氨酸丙烯酸酯单体。
5.根据权利要求4所述的聚合物基阻垢缓蚀剂的制备工艺，其特征在于，所述步骤（2）中3-氯-2-羟基丙烷磺酸钠、三乙胺、中间体1的摩尔比为（0.9-1.3）:（1.1-1.3）:1。
6.根据权利要求4所述的聚合物基阻垢缓蚀剂的制备工艺，其特征在于，所述步骤（3）中反应溶剂包括四氢呋喃、1,4-二氧六环、乙酸乙酯。
7.根据权利要求4所述的聚合物基阻垢缓蚀剂的制备工艺，其特征在于，所述步骤（3）中半胱氨酸、中间体2、三乙胺的摩尔比例为（1.8-2.4）:1:（2.2-2.6）。
8.根据权利要求4所述的聚合物基阻垢缓蚀剂的制备工艺，其特征在于，所述步骤（3）中反应控制温度为70-100℃，时间控制为12-24h。
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Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5776875A (en) * | 1996-07-16 | 1998-07-07 | Nalco Chemical Company | Use of biodegradable polymers in preventing scale build-up |
| US20070125987A1 (en) * | 2003-06-25 | 2007-06-07 | Emma Hills | Tagged scale inhibiting polymers, compositions comprised thereof and preventing or controlling scale formation therewith |
| CN101260176A (zh) * | 2006-07-21 | 2008-09-10 | 国家淀粉及化学投资控股公司 | 磺化接枝共聚物 |
| CN101358352A (zh) * | 2008-09-11 | 2009-02-04 | 河北理工大学 | 新型氨基酸衍生物酸洗缓蚀剂及其应用方法 |
| CN102417593A (zh) * | 2011-09-26 | 2012-04-18 | 河南清水源科技股份有限公司 | 一种生物可降解的水处理剂天冬酰胺基聚环氧琥珀酸及其制备方法 |
| CN106279572A (zh) * | 2016-07-26 | 2017-01-04 | 上海台界化工有限公司 | 一种含聚天冬氨酸的建筑用缓凝剂及其制备方法 |
| CN108056107A (zh) * | 2017-12-11 | 2018-05-22 | 常州中翔科技有限公司 | 一种复合型缓蚀阻垢杀菌剂及其制备方法 |
| CN111961146A (zh) * | 2020-09-09 | 2020-11-20 | 中国石油天然气集团有限公司 | 高效溶蚀、低腐蚀、抑垢及环保的酸液体系及制备方法 |
| CN112499780A (zh) * | 2020-11-25 | 2021-03-16 | 山东天庆科技发展有限公司 | 一种耐高温阻垢分散剂及其制备方法 |
-
2023
- 2023-12-05 CN CN202311649147.9A patent/CN117362499B/zh active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5776875A (en) * | 1996-07-16 | 1998-07-07 | Nalco Chemical Company | Use of biodegradable polymers in preventing scale build-up |
| US20070125987A1 (en) * | 2003-06-25 | 2007-06-07 | Emma Hills | Tagged scale inhibiting polymers, compositions comprised thereof and preventing or controlling scale formation therewith |
| CN101260176A (zh) * | 2006-07-21 | 2008-09-10 | 国家淀粉及化学投资控股公司 | 磺化接枝共聚物 |
| CN101358352A (zh) * | 2008-09-11 | 2009-02-04 | 河北理工大学 | 新型氨基酸衍生物酸洗缓蚀剂及其应用方法 |
| CN102417593A (zh) * | 2011-09-26 | 2012-04-18 | 河南清水源科技股份有限公司 | 一种生物可降解的水处理剂天冬酰胺基聚环氧琥珀酸及其制备方法 |
| CN106279572A (zh) * | 2016-07-26 | 2017-01-04 | 上海台界化工有限公司 | 一种含聚天冬氨酸的建筑用缓凝剂及其制备方法 |
| CN108056107A (zh) * | 2017-12-11 | 2018-05-22 | 常州中翔科技有限公司 | 一种复合型缓蚀阻垢杀菌剂及其制备方法 |
| CN111961146A (zh) * | 2020-09-09 | 2020-11-20 | 中国石油天然气集团有限公司 | 高效溶蚀、低腐蚀、抑垢及环保的酸液体系及制备方法 |
| CN112499780A (zh) * | 2020-11-25 | 2021-03-16 | 山东天庆科技发展有限公司 | 一种耐高温阻垢分散剂及其制备方法 |
Non-Patent Citations (1)
| Title |
|---|
| 孙耀冉等: "丁二酸单酯酰氯的合成工艺研究", 石家庄学院学报, vol. 12, no. 06, pages 21 - 24 * |
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