聚(丙烯酸-co-2-丙烯酰胺基-2-甲基-1-丙烷磺酸)/凹凸棒石复合高吸水树脂的制备及溶胀动力学
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摘要
以N,N'-亚甲基双丙烯酰胺和三羟甲基丙烷三缩水甘油醚为交联剂,利用部分中和的丙烯酸、2-丙烯酰胺基-2-甲基-1-丙烷磺酸和凹凸棒石为原料制备了高吸水树脂,并采用丙三醇和硅酸钠进行表面交联及与硫酸铝和碳酸钠无机盐共混技术对高吸水树脂进行了后处理,对高吸水树脂的结构进行了表征,分析了该树脂有高的吸水速率和吸水倍数的原因,考察了溶液的pH、离子种类及离子强度对树脂溶胀动力学的影响。结果表明,溶液的pH对树脂的溶胀动力学有影响,在不同pH的NaCl溶液中都表现出supercaseΠ扩散行为。高价阳离子溶液对树脂溶胀动力学影响显著,出现了退溶胀现象,采用Díez-Pe?a的模型对退溶胀现象进行了定量分析,与实验数据吻合度较好。阴离子对树脂溶胀动力学影响不大,在不同阴离子溶液中树脂的扩散行为符合supercaseΠ扩散类型。
A fast swelling sulfonic acid macroporous superabsorbent composite was prepared by copolymerization of partially neutralized acrylic acid, 2-acryloylamino-2-methyl-1-propa-nesulfonicacid, and attapulgite using glycerine and sodium silicate as surface-crosslinker, and then the surface-crosslinked copolymer was blended with aluminum sulfate and sodium carbonate in post treatment process. The structure of superabsorbents was studied. The effects of pH values, ions and their concentrations on the swelling behavior of the samples were investigated. The results show that the swelling behavior of the samples is affected by pH value. The supercase Ⅱ diffusion is observed in all NaCl solutions with different pH values. An overshooting effect appears in all solutions containing multivalent cations. A quantitative kinetics model proposed by Díez-Pe?a was used to interpret it and the theoretical curves are in good agreement with the experimental data. For anions, it shows little effect on swelling process, and the supercase Π diffusion is observed in all solutions.
A fast swelling sulfonic acid macroporous superabsorbent composite was prepared by copolymerization of partially neutralized acrylic acid, 2-acryloylamino-2-methyl-1-propa-nesulfonicacid, and attapulgite using glycerine and sodium silicate as surface-crosslinker, and then the surface-crosslinked copolymer was blended with aluminum sulfate and sodium carbonate in post treatment process. The structure of superabsorbents was studied. The effects of pH values, ions and their concentrations on the swelling behavior of the samples were investigated. The results show that the swelling behavior of the samples is affected by pH value. The supercase Ⅱ diffusion is observed in all NaCl solutions with different pH values. An overshooting effect appears in all solutions containing multivalent cations. A quantitative kinetics model proposed by Díez-Pe?a was used to interpret it and the theoretical curves are in good agreement with the experimental data. For anions, it shows little effect on swelling process, and the supercase Π diffusion is observed in all solutions.
引文
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[6] Qi X H,Liu M Z,Chen Z B.Study on swelling behavior of poly(sodiumacrylate-co-2-acrylo-ylamino-2-methyl-1-propanesulfonic acid)/attapulgite macroporous superabsorbent composite[J].Polym.Eng.Sci.,2014,55:681-687.
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[8] Díez-Pe?a E,Quijada-Garrido I,Barrales-Rienda J M.Analysis of the swelling dynamics of cross-linked P (N-iPAAm-co-MAA) copolymers and their homopolymers under acidic medium:a kinetics interpretation of the overshooting effect[J].Macromolecules,2003,36:2475-2483.
[2] Yilmaz S S,Kul D,Erdol M,et al.Synthesis of a novel crosslinked superabsorbent copolymer with diazacyclooctadecane crown ether and its sorption capability[J].Eur.Polym.J.,2007,43:1923-1932.
[3] Dutkiewicz J K.Superabsorbent materials from shellfish waste-a review[J].J.Biomed.Mater.Res.,B,2002,63:373-381.
[4] Qi X H,Liu M Z,Zhang F,et al.Synthesis and properties of poly(sodium acrylateco-2-acryloy-lamino-2-methyl-1-propanesulfonicacid)/attapulgite as a salt-resistant superabsorbent composite[J].Polym.Eng.Sci.,2009,49:182-188.
[5] Qi X H,Liu M Z,Chen Z B,et al.Preparation and properties of macroporous superabsorbent composite[J].Polym.Adv.Technol.,2010,21:196-204.
[6] Qi X H,Liu M Z,Chen Z B.Study on swelling behavior of poly(sodiumacrylate-co-2-acrylo-ylamino-2-methyl-1-propanesulfonic acid)/attapulgite macroporous superabsorbent composite[J].Polym.Eng.Sci.,2014,55:681-687.
[7] Alfrey J T,Gurnee E F,Lloyd W G.Diffusion in glassy polymers[J].J.Polym.Sci.:Part C,l966,12:249-261.
[8] Díez-Pe?a E,Quijada-Garrido I,Barrales-Rienda J M.Analysis of the swelling dynamics of cross-linked P (N-iPAAm-co-MAA) copolymers and their homopolymers under acidic medium:a kinetics interpretation of the overshooting effect[J].Macromolecules,2003,36:2475-2483.