腐植酸基高吸水性树脂的制备及其性能
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摘要
以风化煤中提取的腐植酸(HA)和丙烯酸(AA)为原料,利用水溶液聚合法合成腐植酸基高吸水性树脂(HA-PAA),分析过硫酸铵(APS)、N,N′-亚甲基双丙烯酰胺(MBA)、腐植酸(HA)用量及NaOH中和度对合成树脂吸水倍率的影响;通过红外光谱仪和扫描电镜对吸水性树脂进行分析,测试其耐盐、耐酸碱、耐温和保水性能。结果表明,水溶液聚合法合成HA-PAA最佳条件为HA质量分数6%,NaOH中和度50%,MBA质量分数0.04%,APS质量分数2.1%。该条件下制备的HA-PAA,吸纯水倍率最高可达1 403 g·g~(-1),吸盐水倍率最高可达214.5 g·g~(-1),可反复使用多次。通过表征结果可证实HA和PAA发生充分聚合反应,HA-PAA生成后表面更加粗糙,疏松多孔且呈现分层现象,合成树脂的吸水性大幅提升。
The humic acid and acrylic acid extracted from the weathered coal were taken as the raw material. The effects of factors such as the ammonium sulphate(APS) dosage, the amount of N, N′-methylenebisacrylamide(MBA), the amount of HA and the neutralization degree of NaOH on the water absorption capacity were discussed to determine the best synthetic conditions. FTIR and SEM were adopted to characterize and analyze the resin. Experiments were carried out to test its properties of salt-resistance, pH-resistance, temperature-resistance and water retention. The results show that the optimum reaction conditions of HA-PAA by aqueous solution are as follows: the neutralization degree of NaOH is 50%, and the mass ratio of the HA, MBA, APS, is 6%, 0.04%, 2.1% respectively. HA-PAA that has good performance can be used repeatedly. The absorbency in distilled water can reach 1 403 g·g~(-1) and the absorbency in saline water can reach 214.5 g·g~(-1) under the optimums conditions. The polyreaction occurs between the humic acid and acrylic acid. The resin′s surface is found to be rough,loose and layered,and the porosity increases, which can enhance the water absorbency of the resin.
The humic acid and acrylic acid extracted from the weathered coal were taken as the raw material. The effects of factors such as the ammonium sulphate(APS) dosage, the amount of N, N′-methylenebisacrylamide(MBA), the amount of HA and the neutralization degree of NaOH on the water absorption capacity were discussed to determine the best synthetic conditions. FTIR and SEM were adopted to characterize and analyze the resin. Experiments were carried out to test its properties of salt-resistance, pH-resistance, temperature-resistance and water retention. The results show that the optimum reaction conditions of HA-PAA by aqueous solution are as follows: the neutralization degree of NaOH is 50%, and the mass ratio of the HA, MBA, APS, is 6%, 0.04%, 2.1% respectively. HA-PAA that has good performance can be used repeatedly. The absorbency in distilled water can reach 1 403 g·g~(-1) and the absorbency in saline water can reach 214.5 g·g~(-1) under the optimums conditions. The polyreaction occurs between the humic acid and acrylic acid. The resin′s surface is found to be rough,loose and layered,and the porosity increases, which can enhance the water absorbency of the resin.
引文
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[10] 李本刚,范玉曼,张严丹,等.聚丙烯酸钠/纳米纤维素晶体-g-聚丙烯酰胺复合高吸水性树脂的制备与表征[J].高分子材料科学与工程,2018,34(7):156-161. LI B G,FAN Y M,ZHANG Y D,et al.Preparation and characterization of sodium polyacrylate/(nanocrysatlline cellulose)-g-polyacrylamide superabsorbent composites[J].Polymer Materials Science & Engineering,2018,34(7):156-161.(in Chinese)
[11] JIANG T,WEI S Q,FLANAGAN D C,et al.Effect of abiotic factors on the mercury reduction process by humic acids in aqueous systems[J].Pedosphere,2014,24(1):125-136.
[12] 谢华飞,张翠荣,贾振宇,等.原位聚合法制备壳聚糖-g-聚丙烯酸/高岭土复合树脂[J].化工新型材料,2012,40(2):49-52. XIE H F,ZHANG C R,JIA Z Y,et al.Study on the preparation of superabsorbent composite of chitosan-g-poly(acrylic acid)/kaolin by in-situ polymerization[J].New Chemical Materials,2012,40(2):49-52.(in Chinese)
[13] ZHONG K,LIN Z T,ZHENG X L,et al.Starch derivative-based superabsorbent with integration of water-retaining and controlled-release fertilizers[J].Carbohydrate Polymers,2013,92:1367-1376.
[14] 马畅柠,郭雅妮,惠璠,等.陕西黄陵风化煤中腐殖酸的提取工艺[J].西安工程大学学报,2016,30(5):583-588. MA C N,GUO Y N,HUI F,et al.The humic acid extraction process of Huangling weathered coal in Shaanxi province[J].Journal of Xi′an Polytechnic University,2016,30(5):583-588.(in Chinese)
[15] 牛育华,赵冬冬,魏恩志,等.PEG/PVA/PAA 复合高吸水性树脂的制备及其保水性能[J].精细化工,2016,33(6):628-634. NIU Y H,ZHAO D D,WEI E Z,et al.Preparation and water retention of PEG/PVA/PAA superabsorbent resin[J].Fine Chemicals,2016,33(6):628-634.(in Chinese)
[16] 何新健,谢建军.PAAAM高吸水树脂吸液及保水性能研究[J].精细石油化工进展,2013,14(3):51-54. HE X J,XIE J J.Absorbency capacities and water retention properties of PAAAM superabsorbent resin[J].Advances in Fine Petrochemicals,2013,14(3):51-54.(in Chinese)
[2] 李铭杰,李仲谨,诸晓峰,等.天然高分子改性制备高吸水性树脂研究进展[J].化工进展,2010,29(3):573-578. LI M J,LI Z J,ZHU X F,et al.Research progress in super absorbent resin prepared from modification of natural polymers[J].Chemical Industry and Engineering Progress,2010,29(3):573-578.(in Chinese)
[3] TELI M D,WAGHMARE N G.Synthesis of superabsorbents from amaranthus starch[J].Carbohydrate Polymers,2010,81(3):695-699.
[4] 宋学锋,张雅倩.改性聚丙烯酰胺吸水性树脂的吸水性能及抗碎化性能[J].材料导报,2016,30(3):56-60. SONG X F,ZHANG Y Q.Water absorption and fragmentation resistance of modified polyacrylamide absorbent resin[J].Materials Review,2016,30(3):56-60.(in Chinese)
[5] 赵林,蔡雅红,何荷苗,等.高吸水性树脂的制备工艺及应用研究进展[J].工程塑料应用,2018,46(8):143-148. ZHAO L,CAI Y H,HE H M,et al.Research progress on preparation method and application of super absorbent resins[J].Engineering Plastics Application,2018,46(8):143-148.(in Chinese)
[6] 张小磊.高吸水性树脂的制备及表面交联的研究[D].广州:华南理工大学,2014:18-20. ZHANG X L.Study on preparation and surface crosslinking of super absorbent polymer[D].Guangzhou:South China University of Technology,2014:18-20.(in Chinese)
[7] 牛育华,骆筱,廉玉起,等.KGM/HA/AA复合高吸水性树脂的制备及其性能[J].现代化工,2017,37(3):125-128. NIU Y H,LUO X,LIAN Y Q,et al.Preparation and properties of KGM/HA/AA superabsorbent resin[J].Modern Chemical Industry,2017,37(3):125-128.(in Chinese)
[8] 张景迅,魏雨,韩枚江,等.改性聚烯酸类吸水性树脂性能比较及在植物种植中的应用研究[J].化工新型材料,2017,45(12):205-208. ZHANG J X,WEI Y,HAN M J,et al.Performance comparison of modified polyacrylic absorbent resin and its application in plant[J].New Chemical Materials,2017,45(12):205-208.(in Chinese)
[9] 刘丽君,张含,张雪莹,等.聚丙烯酸类互穿聚合物网络高吸水性树脂的合成[J].天津科技大学学报,2018,33(2):43-48. LIU L J,ZHANG H,ZHANG X Y,et al.Synthesis of interpenetrating polymer network superabsorbent resin based on polyacrylate[J].Journal of Tianjin University of Science & Technology,2018,33(2):43-48.(in Chinese)
[10] 李本刚,范玉曼,张严丹,等.聚丙烯酸钠/纳米纤维素晶体-g-聚丙烯酰胺复合高吸水性树脂的制备与表征[J].高分子材料科学与工程,2018,34(7):156-161. LI B G,FAN Y M,ZHANG Y D,et al.Preparation and characterization of sodium polyacrylate/(nanocrysatlline cellulose)-g-polyacrylamide superabsorbent composites[J].Polymer Materials Science & Engineering,2018,34(7):156-161.(in Chinese)
[11] JIANG T,WEI S Q,FLANAGAN D C,et al.Effect of abiotic factors on the mercury reduction process by humic acids in aqueous systems[J].Pedosphere,2014,24(1):125-136.
[12] 谢华飞,张翠荣,贾振宇,等.原位聚合法制备壳聚糖-g-聚丙烯酸/高岭土复合树脂[J].化工新型材料,2012,40(2):49-52. XIE H F,ZHANG C R,JIA Z Y,et al.Study on the preparation of superabsorbent composite of chitosan-g-poly(acrylic acid)/kaolin by in-situ polymerization[J].New Chemical Materials,2012,40(2):49-52.(in Chinese)
[13] ZHONG K,LIN Z T,ZHENG X L,et al.Starch derivative-based superabsorbent with integration of water-retaining and controlled-release fertilizers[J].Carbohydrate Polymers,2013,92:1367-1376.
[14] 马畅柠,郭雅妮,惠璠,等.陕西黄陵风化煤中腐殖酸的提取工艺[J].西安工程大学学报,2016,30(5):583-588. MA C N,GUO Y N,HUI F,et al.The humic acid extraction process of Huangling weathered coal in Shaanxi province[J].Journal of Xi′an Polytechnic University,2016,30(5):583-588.(in Chinese)
[15] 牛育华,赵冬冬,魏恩志,等.PEG/PVA/PAA 复合高吸水性树脂的制备及其保水性能[J].精细化工,2016,33(6):628-634. NIU Y H,ZHAO D D,WEI E Z,et al.Preparation and water retention of PEG/PVA/PAA superabsorbent resin[J].Fine Chemicals,2016,33(6):628-634.(in Chinese)
[16] 何新健,谢建军.PAAAM高吸水树脂吸液及保水性能研究[J].精细石油化工进展,2013,14(3):51-54. HE X J,XIE J J.Absorbency capacities and water retention properties of PAAAM superabsorbent resin[J].Advances in Fine Petrochemicals,2013,14(3):51-54.(in Chinese)