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淀粉基UV固化速降解型高吸水材料的制备及性能

Preparation and Properties of Starch-based UV-curable and Rapid Degradation Superabsorbent Material

【作者】 贺倩

【导师】 郭文迅;

【作者基本信息】 湖南大学 , 材料学, 2011, 硕士

【摘要】 本文采用熔融缩聚法制备了交联剂不饱和聚酯酰胺脲,同时以溶液聚合法合成玉米淀粉接枝丙烯酸共聚物。不饱和聚酯酰胺脲与淀粉接枝丙烯酸共聚物在紫外光照射作用下交联固化成型,制得一种具有较好吸水性能和降解性能的膜状高吸水性材料。该材料在成型过程中不添加任何光引发剂,具有无毒副作用、无残留小分子、降解速度快等特点。本文研究了制备条件对高吸水材料性能的影响,并用红外、TG-DSC和SEM分析仪对聚合物进行了表征。研究结果表明,淀粉与水的糊化比为1:10,引发剂硝酸铈铵用量为丙烯酸单体质量的0.1 %,丙烯酸与玉米淀粉反应时间3 h,反应温度60℃,丙烯酸与淀粉质量比为6,丙烯酸中和度90 %,玉米淀粉接枝丙烯酸聚合物与交联剂不饱和聚酯酰胺脲质量比为200,UV固化时间15 min时,高吸水性材料具有较好的吸水能力,常温条件下,对蒸馏水、自来水、0.9 % KCl和0.9 % NaCl水溶液的吸收能力分别可达920.58 g/g,410.73 g/g,128.70 g/g,99.13 g/g;高吸水性材料吸水速率较快,10 min内对蒸馏水的吸收倍率可达230倍;高吸水性材料保水能力较好,常温条件下,吸蒸馏水、自来水、0.9 % NaCl溶液及0.9 % KCl溶液达饱和状态后,保水率分别可达91.17 %、83.83 %、70.71 %及79.93 %。对高吸水性材料的红外分析证实淀粉接枝丙烯酸共聚物与交联剂不饱和聚酯酰胺脲发生了交联反应。TG-DSC分析证明膜状高吸水性材料具有较好的热稳定性。高吸水性材料降解性能较好,有望应用于一次性生理卫生用品领域,减少环境污染。常温条件下,在蒸馏水、1 mol/L NaOH溶液、0.9 % NaCl溶液中降解7 d后的失重率分别为85.25 %、64.73 %和36.82 %;SEM表明高吸水性材料降解前表现出一种深层中空的立体交联网络结构,表面粗糙多孔,在不同溶液中降解后,交联网络结构逐渐消失,表面粗糙程度增加并伴随有较大的裂痕,表明高吸水性材料在降解过程中先是长链断裂成短链,然后逐渐变为细小颗粒。

【Abstract】 Unsaturated polyester-urea amide which was used as cross-linking agent was prepared by melt-polycondensation in this paper, and corn starch grafted acrylic acid copolymer was prepared by aqueous solution polymerization. A membranous material with high water absorption and easy degradation was prepared, when unsaturated polyester-urea amide and corn starch grafted acrylic acid copolymer were UV-curing and cross-linking under UV irradiation. In the progress of modeling, we didn’t add any photo-initiators in it, and the material has the advantages of non-toxic side effects, no residual small molecules and can be fast degradable and so on. In this paper, the effects of preparation conditions on the properties of super absoebent were studied. The polymer was characterized by IR, TG-DSC and SEM.The research results show that in the conditions of gelatinization ratio of starch and water 1:10 , w(CAN)=0.1 % (based on acrylic acid quality), reaction time of corn starch grafting acrylic acid 3 h , reaction temperature 60℃, mass ratio of acrylic acid and corn starch 6, neutralization degree of acrylic acid 90 %, mass ratio of corn starch grafting acrylic acid polymer and unsaturated polyester-urea amide 200 , UV curing time of 15 min , the superabsorbent material has fairly good water absorption capacity, water absorbency of this material in distilled water, tap water, 0.9 % KCl and 0.9 % NaCl solutions can reach to 920.58 g/g,410.73 g/g,128.70 g/g,99.13 g/g respectively in normal temperature; the superabsorbent material also has good water retention capacity, when the material immersed in distilled water, tap water, 0.9 % KCl and 0.9 % NaCl solutions to water saturation state, 24 h water retaining rate are up to 91.17 % , 83.83 % , 70.71 % and 79.93 % separately. IR confirmed that crosslinking reaction has occurred between corn starch grafted acrylic acid copolymer and unsaturated polyester-urea amide, and TG-DSC confirmed that the membranous material with high water absorption has good thermal stability.The super absorbent material has better performance in degradation than others, and it can be used in the area of disposable physiological health articles to reduce environmental pollution. In normal temperature, the weight loss rate of it can be 85.25 % , 64.73 % and 36.82 % after being immersed in distilled water, 1 mol/L NaOH solution and 0.9% NaCl solutions respectively for 7 d . The super absorbent material shows a deep hollow and three-dimensional cross-linked network structure before degradation, and it has rough and porous surface. When degradation in different solutions, cross-linked network structure has gradually disappeared, meanwhile, roughness degree increase and accompany with large cracks in the surface. It shows that, in degradation process, long chains breaking into short chains and then change into small particles gradually.

  • 【网络出版投稿人】 湖南大学
  • 【网络出版年期】2012年 08期
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