壳聚糖改性疏水缔合聚丙烯酰胺的制备及表征
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摘要
为了改善疏水缔合聚丙烯酰胺的溶解性以及溶液稳定性,本文采用巯基壳聚糖对疏水缔合聚丙烯酰胺进行改性,红外表征结果说明巯基壳聚糖连接到了聚丙烯酰胺分子链上。对影响壳聚糖改性实验的因素进行分析,实验结果说明,壳聚糖中巯基含量增大、壳聚糖加入量增大以及改性反应温度升高都会造成聚合物分子量降低,当改性反应的反应温度不高于35℃、添加壳聚糖质量不高于单体质量的3%时,得到的改性聚合物分子量满足现场使用要求。对改性聚合物的溶解性及溶液稳定性进行了评价,结果表明,壳聚糖中巯基含量增大及壳聚糖加入量增大对聚合物溶解性及溶液稳定性有明显的改善,聚合物的溶解时间由改性前的150min最多缩短至20min,聚合物溶液黏度保留率由改性前的60%最多提高到90%以上,壳聚糖改性有望弥补疏水缔合聚合物现场使用中的一些不足。
In order to improve the solubility and solution stability of hydrophobic associated polyacrylamide, the hydrophobic associated polyacrylamide was modified by the thiolated chitosan. The FTIR spectra showed that thiolated chitosan has connected to the molecular of the hydrophobic associated polyacryamide. The factors affecting the modification of chitosan were analyzed. The result showed that the modified polymers` molecular weight decreased with the increase of the concentration of thiol group in chitosan, the quality of adding chitosan and the modified reaction temperature, and the modified polymers` molecular weight met the requirement of oilfield, when the modified reaction temperature is not higher than 35℃ and the quality of adding chitosan is not higher than 3% of the quality of monomer. The solubility and solution stability of modified polymers were evaluated. The result showed that the increase of the concentration of thiol group in chitosan and the quality of adding chitosan effectively improved the performance of the hydrophobic associated polyacrylamide. The dissolution time of the polymer was shortened from 150 minutes before modification to 20 minutes, and the retention rate of the viscosity of the polymer solution was increased from 60% to more than 90%. The chitosan modification is expected to make up for some deficiencies in the hydrophobic associated polyacrylamide.
In order to improve the solubility and solution stability of hydrophobic associated polyacrylamide, the hydrophobic associated polyacrylamide was modified by the thiolated chitosan. The FTIR spectra showed that thiolated chitosan has connected to the molecular of the hydrophobic associated polyacryamide. The factors affecting the modification of chitosan were analyzed. The result showed that the modified polymers` molecular weight decreased with the increase of the concentration of thiol group in chitosan, the quality of adding chitosan and the modified reaction temperature, and the modified polymers` molecular weight met the requirement of oilfield, when the modified reaction temperature is not higher than 35℃ and the quality of adding chitosan is not higher than 3% of the quality of monomer. The solubility and solution stability of modified polymers were evaluated. The result showed that the increase of the concentration of thiol group in chitosan and the quality of adding chitosan effectively improved the performance of the hydrophobic associated polyacrylamide. The dissolution time of the polymer was shortened from 150 minutes before modification to 20 minutes, and the retention rate of the viscosity of the polymer solution was increased from 60% to more than 90%. The chitosan modification is expected to make up for some deficiencies in the hydrophobic associated polyacrylamide.
引文
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[14]花蓉蓉,周恭明,曹大伟.壳聚糖的絮凝性能研究进展[J].化工进展,2008, 27(3):335-339.HUA R R, ZHOU G M, CAO D W. Research advances in flocculation properties of chitosan[J]. Chemical Industry and Engineering Progress,2008, 27(3):335-339.
[2]韩丽娟.油气开采用疏水缔合聚合物的研究[D].成都:西南石油学院, 2004.HAN L J. Study on hydrophobic association polymer for oil and gas exploitation[D]. Chendu:Southwest Petroleum Institute, 2004.
[3]郭金龙.驱油用疏水缔合型聚合物性能评价研究[D].长春:吉林大学, 2011.GUO J L. Evaluation of hydrophobic association polymer for oil displacement[D]. Changchun:Jilin University, 2011.
[4]张锋三,沈一丁,吴金桥,等.水包水疏水缔合聚丙烯酰胺增稠剂的合成及在压裂中的应用[J].化工进展, 2017, 36(8):3058-3065.ZHANG F S, SHEN Y D, WU J Q, et al. Synthesis of water-in-water hydrophobically associating polyacryamide and its application in fracturing[J]. Chemical Industry and Engineering Progress, 2017, 36(8):3058-3065.
[5]薛新生,郭拥军,冯茹森,等.渤海SZ36-1油田油藏条件下缔合聚合物溶液黏度老化影响因素[J].石油钻采工艺, 2007, 29(5):58-61.XUE X Sh, GUO Y J, FENG R S, et al. Factors influencing viscosity aging of associated polymer solution under reservoir conditions of SZ36-1 oilfield in Bohai sea[J]. Oil Drilling&Production Technology,2007, 29(5):58-61.
[6]王成胜,黄波,易飞,等.渤海SZ36-1油田缔合聚合物黏度损失研究[J].石油钻采工艺, 2010, 32(5):82-85.WANG C S, HUANG B, YI F, et al. Study on viscosity loss of associated polymer in oil field of SZ36-1 oilfield in Bohai sea[J]. Oil Drilling&Production Technology, 2010, 32(5):82-85.
[7]陈斌,吴彬彬,陈士佳,等.水质对疏水缔合聚合物AP-P4溶解影响[J].辽宁石油化工大学学报, 2017, 37(4):1-5.CHEN B, WU B B, CHEN S J, et al. Influencing factors of hydrophobically associating polymer AP-P4 dissolution by water quality[J]. Journal of Liaoning Shihua University, 2017, 37(4):1-5.
[8]许汇,夏燕敏,苏智青,等.二价阳离子对疏水缔合聚合物溶液性能的影响[J].石油化工, 2016, 45(9):1075-1080.XU H, XIA Y M, SU Z Q, et al. Influence of divalent cation on hydrophobically associating polyacrylamide[J]. Petrochemical Technology, 2016, 45(9):1075-1080.
[9]施晓文,邓红兵,杜予民.甲壳素/壳聚糖材料及应用[M].北京:化学工业出版社, 2015:68.SHI X W, DENG H B, DU Y M. Chitin/Chitosan materials and applications[M]. Beijing:Chemical Industry Press, 2015:68.
[10] KRAULAND A H, HOFFER M H, BERNKOP-SCHNURCH A.Viscoelastic properties of a new in situ gelling thiolated chitosan conjugate[J]. Drug Development and Industrial Pharmacy, 2005, 31:885-893.
[11]中华人民共和国石油和化学工业协会.水处理剂-丙烯酰胺:GB17514—2008[S].北京:国家质量监督检验检疫总局, 2008.Association of Petroleum and Chemical Industries of the People's Republic of China. Water treatment agent-acrylamide:GB 17514—2008[S]. Beijing:General Administration of Quality Supervision,Inspection and Quarantine of the People’s Republic of China, 2008.
[12]潘祖仁.高分子化学[M]. 4版北京:化学工业出版社, 2009:49.PAN Z R. Polymer chemistry[M]. 4th ed. Beijing:Chemical Industry Press, 2009:49.
[13]陈士佳,黄波,朱洪庆,等.疏水缔合聚合物溶液稳黏药剂评价研究[J].石油钻采工艺, 2010, 32(6):89-92.CHEN S J, HUANG B, ZHU H Q, et al. Evaluation of hydrophobic association polymer solution adhesives[J]. Oil Drilling&Production Technology, 2010, 32(6):89-92.
[14]花蓉蓉,周恭明,曹大伟.壳聚糖的絮凝性能研究进展[J].化工进展,2008, 27(3):335-339.HUA R R, ZHOU G M, CAO D W. Research advances in flocculation properties of chitosan[J]. Chemical Industry and Engineering Progress,2008, 27(3):335-339.