明胶接枝共聚制备高吸水性树脂的研究
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摘要
本文以丙烯酸(钾)、丙烯酰胺、丙烯酸铵其中的一种或两种单体与明胶接枝共聚合成可生物降解性高吸水性树脂，明胶为可完全生物降解的天然高分子材料，其与各种单体聚合后所得的树脂经降解性能测试可知产物具有可生物降解性。
本文采用水溶液聚合法，以过硫酸钾为引发剂，N，N′-亚甲基双丙烯酰胺为交联剂，分别以氢氧化钾部分中和的丙烯酸单体、氢氧化钾部分中和的丙烯酸和丙烯酰胺、氨水中和的丙烯酸和丙烯酰胺三种不同类型的单体接枝到明胶上，试验结果表明接枝共聚产物的吸(盐)水倍率、吸水速率、保水能力等各项性能均较好，并且在吸液性能上存在如下规律：明胶／丙烯酸(钾)接枝共聚物远小于明胶／丙烯酸(钾)／丙烯酰胺接枝共聚物和明胶／丙烯酸铵／丙烯酰胺接枝共聚物，而明胶／丙烯酸(钾)／丙烯酰胺接枝共聚物略小于明胶／丙烯酸铵／丙烯酰胺接枝共聚物。
高吸水性树脂的吸液性能是衡量高吸水性树脂性能的最主要指标，为了提高吸液倍率，进行了各种不同条件的研究，通过考察引发剂、交联剂、明胶的用量及丙烯酸中和度(或氨化度)、单体质量分数、单体之间的不同配比等各因素对产物吸(盐)水倍率的影响，从而得出聚合反应的最佳试验条件：明胶／丙烯酸(钾)接枝共聚高吸水性树脂的较佳试验条件为：引发剂用量为1％，交联剂用量为0.1％，明胶用量为10％～15％，丙烯酸中和度为75％，单体质量分数为20％；明胶／丙烯酸(钾)／丙烯酰胺接枝共聚高吸水性树脂的较佳试验条件为：引发剂用量为1％，交联剂用量为0.01％，明胶用量为4％，丙烯酸：丙烯酰胺的质量比为1.5：1，丙烯酸中和度为75％，单体质量分数为20％；明胶／丙烯酸铵／丙烯酰胺接枝共聚高吸水性树脂的较佳试验条件为：引发剂用量为1％，交联剂用量为0.05％，明胶用量为2％，丙烯酸：丙烯酰胺的质量比为1.5：1，丙烯酰胺的氨化度为120％，单体质量分数为15％。
本文还对高吸水性树脂的其它性能进行了表征，如在不同温度或压力下的保水性、接枝率、吸水速率、不同盐分下的吸液比较、吸水凝胶对盐水的应答性等，结果表明所制得的高吸水性树脂具有较好的保水性，接枝率较高，吸水速率较快。为了检验所得产物是否已发生了接枝共聚反应，本文通过傅立叶红外光谱仪分析了其结构。IR分析表明，高吸水性树脂乃是明胶与单体的接枝共聚物，为一种均一性聚合物，并非简单的加合。
生物降解性能的探索性研究讨论了活性污泥法对高吸水性树脂的降解效果，通过几组试验的对比可得出：天然高分子明胶10d左右即可降解完，随后合成系聚合物高分子聚丙烯酸、聚丙烯酰胺也能降解一部分。结果表明，本文所研究的三种类型的高吸水性树脂的都具有一定的生物降解性，属于环境友好材料。而且由于氢氧化钾或氨水参加了聚合反应，其中的钾和氮元素以及明胶中的氮元素等对于农业上的施肥性具有较大的好处，故初步认为此类树脂具有较好的应用前景，特别是在农业上的应用。
With one or two of potassium acrylate, acrylamide, ammonium acrylate as raw material, biodegradable SAP was prepared by grafting copolymerizing with gelatin. The resin prepared by copolymerized with several monomers and gelatin, which is natural polymer material and can biodegrade completely, had the performance of biodegradability by testing. Three types of high water absorbent resin were prepared by grafting acrylic acid partly neutralized by potassium hydroxide, acrylamide and acrylic acid partly neutralized by potassium hydroxide, acrylamide and acrylic acid neutralized by ammonia onto gelatin with potassium persulfate as initiator, N,N' -methylene-bis-acylamide as cross-linker, by means of water solution copolymerization. The result of these experimentation showed that the grafting copolymers had good performance of every item, for instance, water absorbency, saline water absorbency, water-absorption velocity, water-holding power, etc., and the performance of liquid absorption had such rule as following: the liquid absorption of the grafting copolymer of potassium acrylate, acrylamide and gelatin far more than the grafting copolymer of potassium acrylate and gelatin, but less than the grafting copolymer of ammonium acrylate, acrylamide and gelatin.
The capability of absorbing water is the uppermost index to judge the resin. To improve the capability of liquid absorption of the resin, the synthesis under a series of process conditions was done. The factors of amount of initiator, cross-linker and gelatin, degree of neutralization of acrylic acid, concentration of monomer, the ratio of two monomers influencing on the capability of pure water-absorption or brine-absorption of the resins were investigated, and the optimal experimental condition was educed according to these factors. The optimal condition of synthesis of the SAP grafted copolymerization of gelatin and acrylic acid was: initiator amount 1%, cross-linker amount 0.1%, gelatin amount 10%～15%, neutralization degree 7.5%, and monomer concentration 20%; the optimal condition of synthesis of the SAP grafted copolymerization of gelatin, acrylic acid and acrylamide was: initiator amount 1%, cross-linker amount 0.01%, gelatin amount 4%, ratio of acrylic acid and acrylamide 1.5:1, neutralization degree 75%, and monomer concentration 20%; the optimal condition of synthesis of the SAP grafted copolymerization of gelatin, ammonium acrylate and acrylamide was: initiator amount 1%, cross-linker amount 0.05%, gelatin amount 2%, ratio of acrylic acid and acrylamide 1.5:1, neutralization degree 120%, and monomer concentration 15%.
In addition, other performances of the resins were also studied, including the water-holding power under different temperature and different pressure, the grafting efficiency, the water-absorption velocity, the compare of liquid-absorption in different electrolytical solutions, the respondent performance, and so on. The result of the experimentation showed that the SAP had good water-holding power, high grafting efficiency, and rapid water-absorption velocity. The structure property of the SAP was tested by Fourier Transform Infrared (FTIR) Spectroscopy so as to check up whether the grafting copolymerizing reaction had occurred in the experimentation. IR analysis indicated that SAP was the grafting copolymer of the gelatin and monomer, homogeneous but not mixture.
The biodegradability of SAP was studied with the active mud method, and the effect of the biodegradability was tested. From the contrast of several experimentations, it showed that the biodegradability of nature polymer, gelatin could biodegraded completely in about 10 days, then the polymers based on synthesized macromolecule, poly (acrylic acid), poly (acrylamide), could biodegrade in a measure. So it made sure that the three types of SAP researched in this thesis had excellent property of biodegradability, and was friendly to the environment. Furthermore nitrogen, which came from gelatin and ammonia as raw material in the copolymerization action, and potassium, which hailed from potassium hydroxide, are good for fertilizing at agriculture, so the SAP prepared in this thesis is considered good-future for application, especially practice at agriculture.
本文采用水溶液聚合法，以过硫酸钾为引发剂，N，N′-亚甲基双丙烯酰胺为交联剂，分别以氢氧化钾部分中和的丙烯酸单体、氢氧化钾部分中和的丙烯酸和丙烯酰胺、氨水中和的丙烯酸和丙烯酰胺三种不同类型的单体接枝到明胶上，试验结果表明接枝共聚产物的吸(盐)水倍率、吸水速率、保水能力等各项性能均较好，并且在吸液性能上存在如下规律：明胶／丙烯酸(钾)接枝共聚物远小于明胶／丙烯酸(钾)／丙烯酰胺接枝共聚物和明胶／丙烯酸铵／丙烯酰胺接枝共聚物，而明胶／丙烯酸(钾)／丙烯酰胺接枝共聚物略小于明胶／丙烯酸铵／丙烯酰胺接枝共聚物。
高吸水性树脂的吸液性能是衡量高吸水性树脂性能的最主要指标，为了提高吸液倍率，进行了各种不同条件的研究，通过考察引发剂、交联剂、明胶的用量及丙烯酸中和度(或氨化度)、单体质量分数、单体之间的不同配比等各因素对产物吸(盐)水倍率的影响，从而得出聚合反应的最佳试验条件：明胶／丙烯酸(钾)接枝共聚高吸水性树脂的较佳试验条件为：引发剂用量为1％，交联剂用量为0.1％，明胶用量为10％～15％，丙烯酸中和度为75％，单体质量分数为20％；明胶／丙烯酸(钾)／丙烯酰胺接枝共聚高吸水性树脂的较佳试验条件为：引发剂用量为1％，交联剂用量为0.01％，明胶用量为4％，丙烯酸：丙烯酰胺的质量比为1.5：1，丙烯酸中和度为75％，单体质量分数为20％；明胶／丙烯酸铵／丙烯酰胺接枝共聚高吸水性树脂的较佳试验条件为：引发剂用量为1％，交联剂用量为0.05％，明胶用量为2％，丙烯酸：丙烯酰胺的质量比为1.5：1，丙烯酰胺的氨化度为120％，单体质量分数为15％。
本文还对高吸水性树脂的其它性能进行了表征，如在不同温度或压力下的保水性、接枝率、吸水速率、不同盐分下的吸液比较、吸水凝胶对盐水的应答性等，结果表明所制得的高吸水性树脂具有较好的保水性，接枝率较高，吸水速率较快。为了检验所得产物是否已发生了接枝共聚反应，本文通过傅立叶红外光谱仪分析了其结构。IR分析表明，高吸水性树脂乃是明胶与单体的接枝共聚物，为一种均一性聚合物，并非简单的加合。
生物降解性能的探索性研究讨论了活性污泥法对高吸水性树脂的降解效果，通过几组试验的对比可得出：天然高分子明胶10d左右即可降解完，随后合成系聚合物高分子聚丙烯酸、聚丙烯酰胺也能降解一部分。结果表明，本文所研究的三种类型的高吸水性树脂的都具有一定的生物降解性，属于环境友好材料。而且由于氢氧化钾或氨水参加了聚合反应，其中的钾和氮元素以及明胶中的氮元素等对于农业上的施肥性具有较大的好处，故初步认为此类树脂具有较好的应用前景，特别是在农业上的应用。
With one or two of potassium acrylate, acrylamide, ammonium acrylate as raw material, biodegradable SAP was prepared by grafting copolymerizing with gelatin. The resin prepared by copolymerized with several monomers and gelatin, which is natural polymer material and can biodegrade completely, had the performance of biodegradability by testing. Three types of high water absorbent resin were prepared by grafting acrylic acid partly neutralized by potassium hydroxide, acrylamide and acrylic acid partly neutralized by potassium hydroxide, acrylamide and acrylic acid neutralized by ammonia onto gelatin with potassium persulfate as initiator, N,N' -methylene-bis-acylamide as cross-linker, by means of water solution copolymerization. The result of these experimentation showed that the grafting copolymers had good performance of every item, for instance, water absorbency, saline water absorbency, water-absorption velocity, water-holding power, etc., and the performance of liquid absorption had such rule as following: the liquid absorption of the grafting copolymer of potassium acrylate, acrylamide and gelatin far more than the grafting copolymer of potassium acrylate and gelatin, but less than the grafting copolymer of ammonium acrylate, acrylamide and gelatin.
The capability of absorbing water is the uppermost index to judge the resin. To improve the capability of liquid absorption of the resin, the synthesis under a series of process conditions was done. The factors of amount of initiator, cross-linker and gelatin, degree of neutralization of acrylic acid, concentration of monomer, the ratio of two monomers influencing on the capability of pure water-absorption or brine-absorption of the resins were investigated, and the optimal experimental condition was educed according to these factors. The optimal condition of synthesis of the SAP grafted copolymerization of gelatin and acrylic acid was: initiator amount 1%, cross-linker amount 0.1%, gelatin amount 10%～15%, neutralization degree 7.5%, and monomer concentration 20%; the optimal condition of synthesis of the SAP grafted copolymerization of gelatin, acrylic acid and acrylamide was: initiator amount 1%, cross-linker amount 0.01%, gelatin amount 4%, ratio of acrylic acid and acrylamide 1.5:1, neutralization degree 75%, and monomer concentration 20%; the optimal condition of synthesis of the SAP grafted copolymerization of gelatin, ammonium acrylate and acrylamide was: initiator amount 1%, cross-linker amount 0.05%, gelatin amount 2%, ratio of acrylic acid and acrylamide 1.5:1, neutralization degree 120%, and monomer concentration 15%.
In addition, other performances of the resins were also studied, including the water-holding power under different temperature and different pressure, the grafting efficiency, the water-absorption velocity, the compare of liquid-absorption in different electrolytical solutions, the respondent performance, and so on. The result of the experimentation showed that the SAP had good water-holding power, high grafting efficiency, and rapid water-absorption velocity. The structure property of the SAP was tested by Fourier Transform Infrared (FTIR) Spectroscopy so as to check up whether the grafting copolymerizing reaction had occurred in the experimentation. IR analysis indicated that SAP was the grafting copolymer of the gelatin and monomer, homogeneous but not mixture.
The biodegradability of SAP was studied with the active mud method, and the effect of the biodegradability was tested. From the contrast of several experimentations, it showed that the biodegradability of nature polymer, gelatin could biodegraded completely in about 10 days, then the polymers based on synthesized macromolecule, poly (acrylic acid), poly (acrylamide), could biodegrade in a measure. So it made sure that the three types of SAP researched in this thesis had excellent property of biodegradability, and was friendly to the environment. Furthermore nitrogen, which came from gelatin and ammonia as raw material in the copolymerization action, and potassium, which hailed from potassium hydroxide, are good for fertilizing at agriculture, so the SAP prepared in this thesis is considered good-future for application, especially practice at agriculture.
引文
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