不同引发剂用量下三元共聚物的制备及其性能表征
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摘要
以水溶液聚合法合成新型三元共聚物阻垢剂,以马来酸酐(MA)、对苯乙烯磺酸钠(SSS)和甲基丙烯酸羟乙酯(HEMA)为单体,合成反应的引发剂、分子调节剂分别采用过硫酸铵和叔丁醇。将引发剂过硫酸铵(APS)的用量分别设计为5%、10%和15%3档,制备出共聚物MA/SSS/HEMA(APS 5%、10%和15%)。通过对3个共聚物进行红外光谱及凝胶色谱分析,表明均有多种官能团进行协同作用,且主要区别在于随着引发剂用量的增加,共聚物相对分子质量逐渐减小,相对分子质量分布逐渐变宽。碳酸钙与硫酸钙的阻垢试验结果表明:共聚物MA/SSS/HEMA(APS 5%、10%和15%)均有较好的阻垢性能,均优于市面常用阻垢剂,且随着引发剂用量增加,共聚物相对分子质量减小,阻垢性能明显提升,共聚物MA/SSS/HEMA(APS 15%)的阻垢性能明显优于共聚物MA/SSS/HEMA(APS 5%和10%)。
A novel terpolymer was synthesized by aqueous solution polymerization with maleic anhydride(MA), sodium p-styrenesulfonate(SSS) and hydroxyethyl methacrylate(HEMA) as monomers. The initiator and the molecular regulator of the polymerization reaction were ammonium persulfate and t-butanol. Terpolymer MA/SSS/HEMA(with APS 5%,10%,15%) were prepared with different dosage levels of APS(5%,10%,15%). IR spectra analysis and gel chromatography were performed and results show there is synergistic effect among varieties of functional groups,and the main difference is that the terpolymer molecular weight decreases with the increase of dosage of initiator, while the molecular weight distribution becomes widen gradually. Calcium carbonate and calcium sulfate scale inhibition test results show that the terpolymer MA/SSS/HEMA 5%, 10%, 15%(APS) all have better scale inhibition performance than the commonly used scale inhibitors in the market. With the increase of dosage of initiator, the terpolymer molecular weight decreases, and scale inhibition performance is improved significantly. The scale inhibition performance of terpolymer MA/SSS/HEMA(APS 15%) is superior to that of the terpolymer MA/SSS/HEMA(APS 5%, 10%).
A novel terpolymer was synthesized by aqueous solution polymerization with maleic anhydride(MA), sodium p-styrenesulfonate(SSS) and hydroxyethyl methacrylate(HEMA) as monomers. The initiator and the molecular regulator of the polymerization reaction were ammonium persulfate and t-butanol. Terpolymer MA/SSS/HEMA(with APS 5%,10%,15%) were prepared with different dosage levels of APS(5%,10%,15%). IR spectra analysis and gel chromatography were performed and results show there is synergistic effect among varieties of functional groups,and the main difference is that the terpolymer molecular weight decreases with the increase of dosage of initiator, while the molecular weight distribution becomes widen gradually. Calcium carbonate and calcium sulfate scale inhibition test results show that the terpolymer MA/SSS/HEMA 5%, 10%, 15%(APS) all have better scale inhibition performance than the commonly used scale inhibitors in the market. With the increase of dosage of initiator, the terpolymer molecular weight decreases, and scale inhibition performance is improved significantly. The scale inhibition performance of terpolymer MA/SSS/HEMA(APS 15%) is superior to that of the terpolymer MA/SSS/HEMA(APS 5%, 10%).
引文
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[14] 韩志超, 李萍, 赵杉林, 等. IA/MA/AMPS三元共聚物阻垢剂的合成研究[J]. 应用化工, 2015, 44(2): 268-272Han Zhichao, Li Ping, Zhao Shanlin, et al. Research on the synthesis of IA/MA/AMPS terpolymer scale inhibitor[J]. Applied Chemical Industry, 2015, 44(2): 268-272 (in Chinese)
[15] 徐广通,袁洪福,陆婉珍. 现代近红外光谱技术及应用进展[J]. 光谱学与光谱分析, 2000, 20(2): 134-142Xu Guangtong, Yuan Hongfu, Lu Wanzhen. Advances in modern near infrared spectroscopy and its application[J]. Spectroscopy and Spectral Analysis, 2000, 20(2): 134-142 (in Chinese)
[16] 朱胜利. 生物可降解的马来酸酐三元共聚物阻垢剂的合成及性能研究[D]. 上海: 华东理工大学, 2014Zhu Shengli. Synthesis and properties of biodegradable maleic anhydride terpolymer scale inhibitor[D]. Shanghai: East China University of Science and Technology, 2014 (in Chinese)
[17] Gu X, Qiu F. Preparation and application of polymers as inhibitors for calcium carbonate and calcium phosphate scales[J]. International Journal of Polymeric Materials and Polymeric Biomaterials, 2013, 62(6): 323-329
[18] Li J, Zhou Y. Preparation and evaluation of a polyether-based polycarboxylate as a kind of inhibitor for water systems[J]. Industrial & Engineering Chemistry Research, 2017, 56(10):2 624-2 633
[19] 张治宏, 王彩花, 王晓昌. 阻垢剂的合成与性能研究[J]. 西安工业学院学报, 2005, 25(5): 455-459Zhang Zhihong, Wang Caihua, Wang Xiaochang. Study on synthesis and properties of scale inhibitor[J]. Journal of Xi’an Institute of Technology, 2005, 25(5): 455-459(in Chinese)
[2] 张欣,刘智安,赵巨东,等. 强制对流换热器表面CaCO3附着垢方解石及文石晶体质量分数变化分析[J]. 环境工程学报, 2016, 10 (7): 3 560-3 564Zhang Xin, Liu Zhian, Zhao Judong, et al. Analysis on mass fraction change of calcite and aragonite crystals in CaCO3 adherent scale on surface of forced convection heat exchanger[J]. Chinese Journal of Environmental Engineering, 2016, 10(7): 3 560-3 564 (in Chinese)
[3] 李凡修, 辛焰, 陈武. 共聚物类阻垢剂的研制进展[J]. 工业水处理, 2000, 20(3):7-10Li Fanxiu, Xin Yan, Chen Wu. The development in the study of copolymer scale inhibitors[J]. Industrial Water Treatment, 2000, 20(3):7-10 (in Chinese)
[4] 徐诚, 唐华东.自由基聚合引发剂的研究进展[J]. 浙江化工, 2015, 46(6): 34-37Xu Cheng, Tang Huadong. Research progress of free radical polymerization initiator[J]. Zhejiang Chemical Industry, 2015, 46(6): 34-37 (in Chinese)
[5] 王文燕, 郑昌仁. 水溶性功能高聚物的相对分子质量对阻垢性能的影响[J]. 工业水处理, 1992, 12(3): 3-6Wang Wenyan, Zheng Changren. Effect of molecular weight of water-soluble functional polymer on scale inhibition performance [J].Industrial Water Treatment, 1992, 12(3): 3-6 (in Chinese)
[6] 潘祖仁. 高分子化学[M]. 5版. 北京: 化学工业出版社, 2011Pan Zuren. High polymer chemistry[M]. 5th Ed. Beijing: Chemical Industry Press, 2011 (in Chinese)
[7] 李强, 张丽芬, 柏良久, 等. 原子转移自由基聚合的最新研究进展[J]. 化学进展, 2010, 22(11): 2 079-2 088Li Qiang, Zhang Lifen, Bai Liangjiu, et al. Atom transfer radical polymerization[J]. Progress in Chemistry, 2010, 22(11): 2 079-2 088 (in Chinese)
[8] 牟静, 李小瑞, 费贵强, 等. MA/AA/AM/AMPS四元共聚物的合成及其对硫酸钙和碳酸钙的阻垢性能[J]. 功能材料, 2013, 2(44): 182-186Mou Jing, Li Xiaorui, Fei Guiqiang, et al. Synthesis of MA/AA/AM/AMPS quaternary copolymer and its scale inhibition performance for calcium sulfate and calcium carbonate[J]. Journal of Functional Materials, 2013, 2(44): 182-186 (in Chinese)
[9] 杨迪. 凝胶色谱测定聚合物分子量及其分布[J]. 现代塑料加工应用, 2005, 17(6): 36-39Yang Di. Determination of relative molecular weight and distribution of polymers by gel chromatography[J]. Modern Plasticsprocessing and Applications, 2005, 17(6): 36-39 (in Chinese)
[10] 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积法: GB/T 16632-2008[S]. 北京: 中国标准出版社, 2008General 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 (in Chinese)
[11] 蒋守红, 徐杰武. 有机膦酸阻碳酸钙垢性能研究[J]. 化学世界, 2013,5: 273-275Jiang Shouhong, Xu Jiewu. Inhibition performance of organic phosphonic acid on calcium carbonate scale[J]. Chemical World, 2013, 5: 273-275 (in Chinese)
[12] Shriner R, Hermann C, Morrill T, et al. The systematic identification of organic compounds[M]. 8th Ed. Beijing: Chemical Industry Press, 2007
[13] 陈香萌, 程亮, 冯乐乐, 等. MA/AA/SSS三元共聚物的制备及其阻垢性能研究[J]. 现代化工, 2016, 36(2): 98-103Chen Xiangmeng, Cheng Liang, Feng Lele, et al. Synthesis of MA/AA/SSS terpolymer and its scale inhibition performance[J]. Modern Chemical Industry, 2016, 36(2): 98-103 (in Chinese)
[14] 韩志超, 李萍, 赵杉林, 等. IA/MA/AMPS三元共聚物阻垢剂的合成研究[J]. 应用化工, 2015, 44(2): 268-272Han Zhichao, Li Ping, Zhao Shanlin, et al. Research on the synthesis of IA/MA/AMPS terpolymer scale inhibitor[J]. Applied Chemical Industry, 2015, 44(2): 268-272 (in Chinese)
[15] 徐广通,袁洪福,陆婉珍. 现代近红外光谱技术及应用进展[J]. 光谱学与光谱分析, 2000, 20(2): 134-142Xu Guangtong, Yuan Hongfu, Lu Wanzhen. Advances in modern near infrared spectroscopy and its application[J]. Spectroscopy and Spectral Analysis, 2000, 20(2): 134-142 (in Chinese)
[16] 朱胜利. 生物可降解的马来酸酐三元共聚物阻垢剂的合成及性能研究[D]. 上海: 华东理工大学, 2014Zhu Shengli. Synthesis and properties of biodegradable maleic anhydride terpolymer scale inhibitor[D]. Shanghai: East China University of Science and Technology, 2014 (in Chinese)
[17] Gu X, Qiu F. Preparation and application of polymers as inhibitors for calcium carbonate and calcium phosphate scales[J]. International Journal of Polymeric Materials and Polymeric Biomaterials, 2013, 62(6): 323-329
[18] Li J, Zhou Y. Preparation and evaluation of a polyether-based polycarboxylate as a kind of inhibitor for water systems[J]. Industrial & Engineering Chemistry Research, 2017, 56(10):2 624-2 633
[19] 张治宏, 王彩花, 王晓昌. 阻垢剂的合成与性能研究[J]. 西安工业学院学报, 2005, 25(5): 455-459Zhang Zhihong, Wang Caihua, Wang Xiaochang. Study on synthesis and properties of scale inhibitor[J]. Journal of Xi’an Institute of Technology, 2005, 25(5): 455-459(in Chinese)