含磺酸基团的环氧琥珀酸类共聚物的合成及性能比较
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摘要
选用烯丙基磺酸钠(SAS)、苯乙烯磺酸钠(SS)、2-丙烯酰胺基-2-甲基丙磺酸(AMPS)和衣康酸(IA)为单体,与环氧琥珀酸(ESA)分别合成了ESA/SAS、ESA/SS、ESA/AMPS和ESA/IA/AMPS四种含磺酸基团的环氧琥珀酸类共聚物,利用FTIR对共聚物的结构进行了表征,利用SEM对使用不同共聚物时生成的碳酸钙晶型进行了观察。对各种共聚物的阻垢分散性能进行了研究,并与聚环氧琥珀酸(PESA)进行了比较。实验结果表明,4种共聚物中,ESA/IA/AMPS具有全面的水处理性能,在高硬度和高碱度水质条件下表现出优异的阻碳酸钙垢和阻磷酸钙垢性能。当其加药量为40mg/L时,对CaCO_3的阻垢率为82.7%,比PESA提高了10.4%。当加药量为30mg/L时,对Ca_3(PO_4)_2的阻垢率可达100%。同时,ESA/IA/AMPS易于生物降解,14天后可以降解72.7%。电镜分析结果表明,加入共聚物后,垢样中出现了球霰石型碳酸钙,这说明共聚物可以使不稳定相稳定存在,增加了碳酸钙在水中的溶解性和分散性。
Four ESA-polymers containing sulfonic acid groups were synthesized by copolymerization of monomers of epoxysuccinic acid(ESA)and sodium allyl sulfonate(SAS),sodium styrene sulfonate(SS),2-acrylamido-2-methylpropanesulfonic acid(AMPS)and itaconic acid(IA). Their molecule structures were characterized by FTIR spectrum,and the crystalline shapes of the CaCO_3 formed from different polymers were observed by SEM. The scale inhibition and dispersion performances of the polymers were studied and compared with those of PESA. The results showed that the polymer of ESA/IA/AMPS had comprehensive water treatment performances,which showed excellent scale inhibition performances to CaCO_3 and Ca_3(PO_4)_2 in the water of high hardness and alkalinity. When the dosage was 40mg/L,the inhibition rate to CaCO_3 scales was 82.7%,10.4% higher than that of PESA. When the dosage was 30mg/L,the scale inhibition rate to Ca_3(PO_4)_2 reached 100%. Moreover,ESA/IA/AMPS was easy to be biodegraded,and its biodegradation percentage reached 72.7% after 14d.The results of SEM showed that there were vaterite type CaCO_3 in the scales formed in the water samples with the addition of the polymers.This indicated that the polymers could stabilize the unstable phase,and thus enhance the solubility and dispersion of CaCO_3 in water.
Four ESA-polymers containing sulfonic acid groups were synthesized by copolymerization of monomers of epoxysuccinic acid(ESA)and sodium allyl sulfonate(SAS),sodium styrene sulfonate(SS),2-acrylamido-2-methylpropanesulfonic acid(AMPS)and itaconic acid(IA). Their molecule structures were characterized by FTIR spectrum,and the crystalline shapes of the CaCO_3 formed from different polymers were observed by SEM. The scale inhibition and dispersion performances of the polymers were studied and compared with those of PESA. The results showed that the polymer of ESA/IA/AMPS had comprehensive water treatment performances,which showed excellent scale inhibition performances to CaCO_3 and Ca_3(PO_4)_2 in the water of high hardness and alkalinity. When the dosage was 40mg/L,the inhibition rate to CaCO_3 scales was 82.7%,10.4% higher than that of PESA. When the dosage was 30mg/L,the scale inhibition rate to Ca_3(PO_4)_2 reached 100%. Moreover,ESA/IA/AMPS was easy to be biodegraded,and its biodegradation percentage reached 72.7% after 14d.The results of SEM showed that there were vaterite type CaCO_3 in the scales formed in the water samples with the addition of the polymers.This indicated that the polymers could stabilize the unstable phase,and thus enhance the solubility and dispersion of CaCO_3 in water.
引文
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[19]白雪,李海花,张利辉,等.ESA/AMPS共聚物阻垢性能与机理研究[J].水处理技术,2016,42(4):51-54.BAI X,LI H H,ZHANG L H,et al.Study on scale inhibition performance and mechanism of ESA/AMPS copolymer[J].Technology of Water Treatment,2016,42(4):51-54.
[20]李猛,谢风龙.聚环氧琥珀酸合成方法的改性及其阻垢性能研究[J].内蒙古科技与经济,2012,8(16):106-108.LI M,XIE F L.Improvement of synthesis method and its scale inhibition performance of polyeoxysuccinic acid[J].Inner Mongolia Science Technology&Economy,2012,8(16):106-108.
[21]中华人民共和国国家质量监督检验检疫总局,中国国家标准化管理委员会.水处理剂阻垢性能的测定碳酸钙沉淀法:GB/T 16632—2008[S].北京:中国标准出版社,2008.General Administration of Quality Supervision,Inspection and Quarantine of the People's Republic of China,Standardization Administration of the People's Republic of China.Determination of scale inhibition performance of water treatment agents-Calcium carbonate precipitation method:GB/T 16632—2008[S].Beijing:Standards Press of China,2008.
[22]中华人民共和国国家质量监督检验检疫总局,中国国家标准化管理委员会.水处理剂阻垢性能的测定磷酸钙沉积法:GB/T22626—2008[S].北京:中国标准出版社,2008.General Administration of Quality Supervision,Inspection and Quarantine of the People's Republic of China,Standardization Administration of the People's Republic of China.Determination of scale inhibition performance of water treatment agents-Calcium phosphate precipitation method:GB/T 22626—2008[S].Beijing:Standards Press of China,2008.
[23]中华人民共和国国家质量监督检验检疫总局,中国国家标准化管理委员会.锅炉用水和冷却水分析方法磷酸盐的测定:GB/T6913—2008[S].北京:中国标准出版社,2008.General Administration of Quality Supervision,Inspection and Quarantine of the People's Republic of China,Standardization Administration of the People's Republic of China.Analysis of water used in boiler and cooling system——determination of phosphorus:GB/T 6913—2008[S].Beijing:Standards Press of China,2008.
[24]喻献国.含磺酸基聚合物阻垢剂的合成及其性能研究[D].长沙:湖南大学,2002.YU X G.Study on synthesis and properties of sulfonic acid based polymers as scale inhibitors[D].Changsha:Hunan University,2002.
[25]魏刚,许亚男,熊蓉春.阻垢剂的可生物降解性研究[J].北京化工大学学报,2001,28(1):59-62.WEI G,XU Y N,XIONG R C.A study on biodegradability of scale inhibitors[J].Journal of Beijing University of Chemical Technology,2001,28(1):59-62.
[2]ZAFERANI S H,SHARIFI M,ZAAREI D,et al.Application of eco-friendly products as corrosion inhibitors for metals in acidpickling processes-A review[J].Journal of Environmental Chemical Engineering,2013,1(4):652-657.
[3]KETSETZI A,STATHOULOPOULOU A,DEMADIS K D.Being"green"in chemical water treatment technologies:issues,challenges and developments[J].Desalination,2008,223(1/2/3):487-493.
[4]熊蓉春,董雪玲,魏刚.水处理剂发展趋向绿色化[J].中国环保产业,2003,6:46-47.XIONG R C,DONG X L,WEI G.Water treatment agents develop to green[J].China Environmental Protection Industry,2003,6:46-47.
[5]陈燕敏,孙彩霞,吴晋英,等.一种环保型阻垢缓蚀剂的性能[J].化工进展,2014,33(1):204-208.CHEN Y M,SUN C X,WU J Y,et al.Performance of an environmentally friendly scale and corrosion inhibitor[J].Chemical Industry and Engineering Progress,2014,33(1):204-208.
[6]张丽华,郑成松,张严,等.环境友好聚环氧琥珀酸的研究进展[J].工业水处理,2010,30(5):5-8.ZHANG L H,ZHENG C S,ZHANG Y,et al.Development of environmental friendly polymer PESA[J].Industrial Water Treatment,2010,30(5):5-8.
[7]LIU D,DONG W,LI F,et al.Comparative performance of polyepoxysuccinic acid and polyaspartic acid on scaling inhibition by static and rapid controlled precipitation methods[J].Desalination,2012,304(42):1-10.
[8]李风亭,张冰如,李璐,等.聚天冬氨酸的合成及应用研究进展[J].工业水处理,2007,27(7):5-7.LI F T,ZHANG B R,LI L,et al.Research progress in the synthesis and application of polyaspartic acid[J].Industrial Water Treatment,2007,27(7):5-7.
[9]何永智,张冰如,李风亭,等.聚环氧琥珀酸用于高炉煤气洗涤水的阻垢分散[J].化工进展,2007,26(4):590-593.HE Y Z,ZHANG B Y,LI F T,et al.Research on performance of polyspoxysuccinic acid used in washing water of blast furnace gas[J].Chemical Industry and Engineering Progress,2007,26(4):590-593.
[10]雷武,王风云,夏明珠,等.绿色阻垢剂聚环氧琥珀酸的合成与阻垢机理初探[J].化工学报,2006,57(9):2207-2213.LEI W,WANG F Y,XIA M Z,et al.Synthesis and its scale inhibition effect of green scale inhibitor polyepoxysuccinic acid[J].Journal of Chemical Industry and Engineering(China),2006,57(9):2207-2213.
[11]王骁,潘明,王书海,等.聚环氧琥珀酸的合成及其阻垢性能[J].精细石油化工,2012,29(2):37-40.WANG X,PANG M,WANG S H,et al.Synthesis and scale inhibiting property of polyepoxysuccinic acid[J].Speciality Petrochemicals,2012,29(2):37-40.
[12]闫岩,杨校领.含磺酸盐共聚物作为阻垢分散剂的技术现状[J].工业水处理,1993,13(4):7-11.YAN Y,YANG X L.[J].Technology status of the containing sulfonate copolymers as scale inhibitors and dispersants[J].Industrial Water Treatment,1993,13(4):7-11.
[13]张跃华,张其平,雷武,等.含荧光基团的AA-SAS共聚物的合成及性能研究[J].工业水处理,2010,30(2):53-56.ZHANG Y H,ZHANG Q P,LEI W,et al.Research on the preparation of acrylic acid/sodium acrysulfonate copolymer containing flurescent groups and its performance[J].Industrial Water Treatment,2010,30(2):53-56.
[14]袁鹰,刘明源.AA/MA/AMPS共聚物阻垢剂的合成及缓蚀性研究[J].应用化工,2013,42(3):578-582.YAN Y,LIU M Y.Study on anticorrosive property and synthesis of AA/MA/AMPS copolymer scale inhibitor[J].Applied Chemical Industry,2013,42(3):578-582.
[15]魏晓飞,王明刚.MOPBG-AMPS共聚物阻垢剂的合成及硫酸钡阻垢性能评价[J].化工进展,2012,31(9):2049-2052.WEI X F,WANG M G.Synthesis of MOPBG-AMPS copolymer and evaluation of inhibition of barium sulfate scale[J].Chemical Industry and Engineering Progress,2012,31(9):2049-2052.
[16]邢卫国,冯泽峰,魏晓飞,等.含磺酸基聚羧酸阻垢分散剂的合成与性能评价[J].工业水处理,2012,32(3):48-51.XING W G,FENG Z F,WEI X F,et al.Synthesis and capacity of the scale inhibitor and dispersant,sulfonic radical-containing polycarboxylic acid[J].Industrial Water Treatment,2012,32(3):48-51.
[17]邢卫国.含磺酸基的聚羧酸阻垢分散剂的合成与性能研究[D].济南:山东大学,2011.XING W G.Synthesis and properties evaluation of polycarboxylic acids containing sulfonic group used as scale inhibitor and dispersant[D].Jinan:Shandong University,2011.
[18]宋娜.新型绿色阻垢剂ESA-HAPS共聚物合成工艺及性能[D].呼和浩特:内蒙古工业大学,2013.SONG N.Synthesis and performance of a new environmental friendly scale inhibitor ESA-HAPS copolymer[D].Hohhot:Inner Mongolia University of Technology,2013.
[19]白雪,李海花,张利辉,等.ESA/AMPS共聚物阻垢性能与机理研究[J].水处理技术,2016,42(4):51-54.BAI X,LI H H,ZHANG L H,et al.Study on scale inhibition performance and mechanism of ESA/AMPS copolymer[J].Technology of Water Treatment,2016,42(4):51-54.
[20]李猛,谢风龙.聚环氧琥珀酸合成方法的改性及其阻垢性能研究[J].内蒙古科技与经济,2012,8(16):106-108.LI M,XIE F L.Improvement of synthesis method and its scale inhibition performance of polyeoxysuccinic acid[J].Inner Mongolia Science Technology&Economy,2012,8(16):106-108.
[21]中华人民共和国国家质量监督检验检疫总局,中国国家标准化管理委员会.水处理剂阻垢性能的测定碳酸钙沉淀法:GB/T 16632—2008[S].北京:中国标准出版社,2008.General Administration of Quality Supervision,Inspection and Quarantine of the People's Republic of China,Standardization Administration of the People's Republic of China.Determination of scale inhibition performance of water treatment agents-Calcium carbonate precipitation method:GB/T 16632—2008[S].Beijing:Standards Press of China,2008.
[22]中华人民共和国国家质量监督检验检疫总局,中国国家标准化管理委员会.水处理剂阻垢性能的测定磷酸钙沉积法:GB/T22626—2008[S].北京:中国标准出版社,2008.General Administration of Quality Supervision,Inspection and Quarantine of the People's Republic of China,Standardization Administration of the People's Republic of China.Determination of scale inhibition performance of water treatment agents-Calcium phosphate precipitation method:GB/T 22626—2008[S].Beijing:Standards Press of China,2008.
[23]中华人民共和国国家质量监督检验检疫总局,中国国家标准化管理委员会.锅炉用水和冷却水分析方法磷酸盐的测定:GB/T6913—2008[S].北京:中国标准出版社,2008.General Administration of Quality Supervision,Inspection and Quarantine of the People's Republic of China,Standardization Administration of the People's Republic of China.Analysis of water used in boiler and cooling system——determination of phosphorus:GB/T 6913—2008[S].Beijing:Standards Press of China,2008.
[24]喻献国.含磺酸基聚合物阻垢剂的合成及其性能研究[D].长沙:湖南大学,2002.YU X G.Study on synthesis and properties of sulfonic acid based polymers as scale inhibitors[D].Changsha:Hunan University,2002.
[25]魏刚,许亚男,熊蓉春.阻垢剂的可生物降解性研究[J].北京化工大学学报,2001,28(1):59-62.WEI G,XU Y N,XIONG R C.A study on biodegradability of scale inhibitors[J].Journal of Beijing University of Chemical Technology,2001,28(1):59-62.