辐照法淀粉接枝聚丙烯酸合成高吸水性树脂
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摘要
高吸水性树脂是一种具有超强吸水和保水能力的新型高分子材料，世界各国竞相进行研究开发。目前高吸水性树脂的合成工艺存在反应时间长、能耗大、有废液污染等问题。本文利用辐射技术高效、无需引发剂、无污染等特点，开发了辐射淀粉接枝共聚合成高吸水性树脂的绿色新工艺。
通过对丙烯酸(AA)与木薯淀粉(St)接枝反应的研究，得出不同反应条件对接枝反应的影响规律。在最佳条件下(丙烯酸／淀粉=3.2ml／g，辐照剂量1332Gy)，合成的高吸水性树脂吸水倍率最高达388g／g，吸盐水倍率达53g／g。通过红外谱图和电镜扫描确定了接枝共聚产物的存在。最佳条件下的接枝率为83.98％，侧链粘均相对分子质量M_η为1.11×10~5。
为提高吸水率，在反应物中加入NaOH，制得淀粉与聚丙烯酸钠接枝共聚物。并就辐射剂量、丙烯酸与木薯淀粉配比、中和度对吸水率的影响进行了讨论。通过正交试验，得到优化条件。在优化条件下(丙烯酸／淀粉=2.6中和度为80％，辐照剂量为4.1kGy)，得到吸水和保水性能俱佳的高吸水性树脂。合成的树脂吸水率为1357g／g，吸0.9％NaCl率为153g／g．高吸水性树脂的红外光谱证明淀粉接枝上了丙烯酸钠。
广西大学硕士论文《辐照法淀粉接枝合成高吸水性树脂》
}
本文还对高吸水性树脂的吸水机理进行了讨论，从热力学角度解
释了吸水本质，通过「lory公式解释了实验中的一些现象。为进一步
建立树脂吸水的数学模型提供参考。
Super absorbent resin is a kind of novel polymer material, which has the super-performance of absorbing and retaining water. Many countries have been conducting in its research and development. At present its synthetic technology has such problems as long reaction time, high energy-consuming, and wastewater. In this paper, the irradiation technology was utilized which has many advantages such as high efficiency, without Initiator and pollution in the reaction. And a green novel technology has been developed for synthesizing super absorbent resin, based on the starch graft copolymerization under irradiation.
By the research of tapioca starch and acrylic acid graft copolymerization, influencing rules of reaction conditions were discussed. Under the optimal conditions (the proportion of acrylic acid with starch is
3.2: 1, radiation dose 1332Gy), water-absorption power of super
absorbent resin is 388g/g, salt-water absorption power is 53g/g. IR
spectrum of resin and SEM photograph of resin shows that acrylic acid has been grafted to starch. The graft percentage of optimal conditions is
83.98%. The molecular weight is 1.11 105.
In order to improve water absorbency, NaOH was added into reacting matter. Starch grafted sodium polyacrylate was make. Effects of Monomer concentration, neutralization degree and irradiation dose on water absorbency were discussed. By orthogonal experiment, optimizing condition was gotten. Under the optimizing condition (the proportion of acrylic acid with starch is 2.6: 1, neutralization degree of acrylic acid is 80%, radiation dose 4.1kGy), water absorbency and water retention performance of super absorbent resin is excellent, water-absorption power of super absorbent resin is 1357g/g, salt-water absorption power is 153g/g. IR spectrum of resin proves that sodium acrylate has been grafted to starch.
Water absorbing mechanism of resin has been discussed. The essence of water absorbing is explained from the thermodynamics. Some phenomena in experiments are explained by Flory equation. It can be the reference for further setting the mathematic model of water absorbing.
通过对丙烯酸(AA)与木薯淀粉(St)接枝反应的研究，得出不同反应条件对接枝反应的影响规律。在最佳条件下(丙烯酸／淀粉=3.2ml／g，辐照剂量1332Gy)，合成的高吸水性树脂吸水倍率最高达388g／g，吸盐水倍率达53g／g。通过红外谱图和电镜扫描确定了接枝共聚产物的存在。最佳条件下的接枝率为83.98％，侧链粘均相对分子质量M_η为1.11×10~5。
为提高吸水率，在反应物中加入NaOH，制得淀粉与聚丙烯酸钠接枝共聚物。并就辐射剂量、丙烯酸与木薯淀粉配比、中和度对吸水率的影响进行了讨论。通过正交试验，得到优化条件。在优化条件下(丙烯酸／淀粉=2.6中和度为80％，辐照剂量为4.1kGy)，得到吸水和保水性能俱佳的高吸水性树脂。合成的树脂吸水率为1357g／g，吸0.9％NaCl率为153g／g．高吸水性树脂的红外光谱证明淀粉接枝上了丙烯酸钠。
广西大学硕士论文《辐照法淀粉接枝合成高吸水性树脂》
}
本文还对高吸水性树脂的吸水机理进行了讨论，从热力学角度解
释了吸水本质，通过「lory公式解释了实验中的一些现象。为进一步
建立树脂吸水的数学模型提供参考。
Super absorbent resin is a kind of novel polymer material, which has the super-performance of absorbing and retaining water. Many countries have been conducting in its research and development. At present its synthetic technology has such problems as long reaction time, high energy-consuming, and wastewater. In this paper, the irradiation technology was utilized which has many advantages such as high efficiency, without Initiator and pollution in the reaction. And a green novel technology has been developed for synthesizing super absorbent resin, based on the starch graft copolymerization under irradiation.
By the research of tapioca starch and acrylic acid graft copolymerization, influencing rules of reaction conditions were discussed. Under the optimal conditions (the proportion of acrylic acid with starch is
3.2: 1, radiation dose 1332Gy), water-absorption power of super
absorbent resin is 388g/g, salt-water absorption power is 53g/g. IR
spectrum of resin and SEM photograph of resin shows that acrylic acid has been grafted to starch. The graft percentage of optimal conditions is
83.98%. The molecular weight is 1.11 105.
In order to improve water absorbency, NaOH was added into reacting matter. Starch grafted sodium polyacrylate was make. Effects of Monomer concentration, neutralization degree and irradiation dose on water absorbency were discussed. By orthogonal experiment, optimizing condition was gotten. Under the optimizing condition (the proportion of acrylic acid with starch is 2.6: 1, neutralization degree of acrylic acid is 80%, radiation dose 4.1kGy), water absorbency and water retention performance of super absorbent resin is excellent, water-absorption power of super absorbent resin is 1357g/g, salt-water absorption power is 153g/g. IR spectrum of resin proves that sodium acrylate has been grafted to starch.
Water absorbing mechanism of resin has been discussed. The essence of water absorbing is explained from the thermodynamics. Some phenomena in experiments are explained by Flory equation. It can be the reference for further setting the mathematic model of water absorbing.
引文
[1]蒋先明，曾宪家．引发淀粉接枝共聚的氧化还原体系[J]．淀粉与淀粉糖，1993，3：45～51
[2]葛学武等．淀粉接枝丙烯酰胺制备絮凝剂的研究方法[J]．高分子材料科学与工程，1998，15(4)：130～132
[3]G.F.Fanta, M.O.Weaver, WM Doane. Chemtech, 1974, 9:675
[4]G.Mino, S.Kaizerman.J.Polym.Sci , 1958, 31:242
[5]L.A.Gugliemelli, M.O.Weaver, C.R.Russel. J.Appl.Polym. Sci ,1969, 13:2007
[6]L.A.Gugliemelli, M.O.Weaver, C.R.Russel. USPatent 3425971(1969).
[7]C.E.Brockway. et al.J .Polym. Sci., 1964, 3733.
[8]化学工业时报(5823)．4，1993-06-05
[9]石油化学新报(6617)．3，1995-05-16
[10]江其清，袁国政．新型化工材料—高吸水性树脂，现代化工．1986(3)：28—33
[11]I.Ogawa, H.Yamano, K.Miyagama. J.Appl.Polym.Sci., 1993, 47:217.
[12]王芬盛等．高吸水性树脂的进展．精细石油化工．1988(1)：42
[13]CN85103771[P], 1986.
[14]CN1068339[P], 1993.
[15]路建美，朱秀林．高分子材料科学与工程[J]，1992，8(1)：35-39．
[16]SA—型吸水树脂鉴定材料．1987．7
[17]杜仕国．高吸水性树脂的研究进展．精细石油化工 1995(1)：57-60
[18]邹新禧．超强吸水剂．北京：化学工业出版社，1998：2-261
[19]F. L. Buchholz. Keeping Dry with Superabsorbent Polymers. Chemtech, 1994, 24(9): 38—43
[20]罗雁彬，郑小霞，陈泽芳等．丙烯酸与淀粉微波固相接枝共聚反应研究．化学研究与应用，1999，11(6)：687—690
[21]VD. Ahawale, S.C. Rathi. Syntheses and Characterization Of Starch —Poly(methacrylicacld) Graft Copolymers. J. Appl. Polym. Sci, 1997, 66: 1399—1403
[22]张志成高分子辐射化学 2-3(1983)
[23]G. F. Fanta. etal, U. S. P. 955, 828
[24]M. I. Khalil. et al. Journal of Polymer Science: Polymer Chemistry Edition, 21, 715-724 1983
[25]张志成，吴国忠，徐湘凌，张曼维高分子材料科学与工程 No．6 16-21．(1992)
[26]F. L. Buchholz. Keeping Dry with Superabsorbent Polymers. Chemtech, 1994, 24(9): 38—43
[27]王直刚．高吸水性树脂的合成及应用．石油化工 1996，25(9)：667-672
[28]翟羽伸．高吸水性树脂．石油化工 1985，14(10)：625-631
[29]刘廷栋，张立广，刘京．聚丙烯酸钠盐高吸水性树脂．合成树脂及塑料。1993，10(2)：68-72
[30]柳明珠，吴靖嘉，巨育红．吸水性高分子材料的研究(Ⅱ)——交联聚丙烯酸钠的合成及其性能研究．兰州大学学报(自然科学版)．1991，27(3)：74—79
[31]郑邦乾，朱清泉，徐僖．高吸水性HPMA的制备和性能．高分子材料科学与工程．1987(2)：68-73
[32]刘廷栋，刘京高吸水性树脂在日用化学工业中的应用[J]．日用化学工业，1995，(1)：22—24
[33]Chem Abstr,1992,116:42832; USP5,055,503
[34]朱秀林等．高分子材料科学与工程，1992，8(1)：35．
[35]喻发金等．高分子材料科学与工程，1998，14(1)：31．
[36]Chemical Week, 98, August/5:34.
[37]W.Robert. USP 57 19201(1998).
[38]S.George. DE 19621323(1997).
[39]K.Ishita.J P 09253 129(1997).
[40]C.Christian.WO9743331(1997).
[41]T.Namba, et al.In Advances in Superabsobent Polymers, ACS, 1994.
[42]H.Sekimoto, M.Fukami, O.Kishimoto, et al.Netti Nogyo, 1995, 39(4):236.
[43]H.Kobayaohi, K.Okamura, Y.Sano, et al.WO 8810, 001(1988).
[44]J.J.Sheu. USP atent 5163115(1992).
[45]万明球等．功能高分子学报，1995，8(3)：271
[46]M.Hiroshi. JP09206513(1997)
[47]张燕萍 变性淀粉制造与应用 2000(1)：329-331．
[48]温品谦二．超强吸水剂的研究[J]．有机合成化学，1980，38(6)：546～554．
[49]W.Y.Lee, R.J.Wu. J.Appl.Polym.Sci., 1996, 62:1009.
[50]P.Lepoutre, S.H.Hui , A.A.Robertson. J.Appl.Polym.Sci., 1973, 17:3143.
[51]Kimura, T.Hatsuda.EP 450924 1991
[52]功能高分子学报 1999，2(12)：214
[53]K.J.Buchanan, B.Hird.Polym Bull, 1986, 15:325.
[54]路建美，朱秀林，胡逢吉等．乌头酸与丙烯酸钠的微波辐射共聚制高吸水性树脂．石油化工，1999，28(1)：36-37
[55]东华大学学报(自然科学版)，2000，28(5)：52-54
[56]高允彦编．正交及回归试验设计方法．北京：冶金工业出版社．1988
[57]中国现场统计研究会三次设计组，全国总工会电教中心编著．正交法和三次设计．北京：科学出版社．1985
[58]北京大学数学力学系概率统计组编。正交设计。人民教育出版社 1976
[59]Adtler Research Laboratories, INC. The Sadtler Standard Spectra: Commercial Spectra IR Grating, Monomers & Polymers. 1973
[60]George Odianprinciples of Polymerization, 2nd Ed. John Wiley&Sons, 1981
[61]潼迟章，化学工业(日)，1976，27，618
[62]刘廷栋，刘京等．高分子通报，1994(3)：181
[63]Iogawa, et. al. Rate of Swelling of Sodium Polyacrylate. J. Appl. Polym.Sci 1993, 17: 217, 222
[64]P. J.Flory. Principles of Polymer Chemistry. Comell University Press. New York.1953
[65]于善普，李旭东，影响吸水聚合物的吸水能力的因素及表征．青岛化工学院学报。1997，18(2)：147-151
[66]M. Manabeet. al. Volumetric and Thermal Behaviors of Water Uptaken in Superabsorbentpolymer. Bull. Chem. Soc. Jpn. 1992, 65.. 2319—2322
[2]葛学武等．淀粉接枝丙烯酰胺制备絮凝剂的研究方法[J]．高分子材料科学与工程，1998，15(4)：130～132
[3]G.F.Fanta, M.O.Weaver, WM Doane. Chemtech, 1974, 9:675
[4]G.Mino, S.Kaizerman.J.Polym.Sci , 1958, 31:242
[5]L.A.Gugliemelli, M.O.Weaver, C.R.Russel. J.Appl.Polym. Sci ,1969, 13:2007
[6]L.A.Gugliemelli, M.O.Weaver, C.R.Russel. USPatent 3425971(1969).
[7]C.E.Brockway. et al.J .Polym. Sci., 1964, 3733.
[8]化学工业时报(5823)．4，1993-06-05
[9]石油化学新报(6617)．3，1995-05-16
[10]江其清，袁国政．新型化工材料—高吸水性树脂，现代化工．1986(3)：28—33
[11]I.Ogawa, H.Yamano, K.Miyagama. J.Appl.Polym.Sci., 1993, 47:217.
[12]王芬盛等．高吸水性树脂的进展．精细石油化工．1988(1)：42
[13]CN85103771[P], 1986.
[14]CN1068339[P], 1993.
[15]路建美，朱秀林．高分子材料科学与工程[J]，1992，8(1)：35-39．
[16]SA—型吸水树脂鉴定材料．1987．7
[17]杜仕国．高吸水性树脂的研究进展．精细石油化工 1995(1)：57-60
[18]邹新禧．超强吸水剂．北京：化学工业出版社，1998：2-261
[19]F. L. Buchholz. Keeping Dry with Superabsorbent Polymers. Chemtech, 1994, 24(9): 38—43
[20]罗雁彬，郑小霞，陈泽芳等．丙烯酸与淀粉微波固相接枝共聚反应研究．化学研究与应用，1999，11(6)：687—690
[21]VD. Ahawale, S.C. Rathi. Syntheses and Characterization Of Starch —Poly(methacrylicacld) Graft Copolymers. J. Appl. Polym. Sci, 1997, 66: 1399—1403
[22]张志成高分子辐射化学 2-3(1983)
[23]G. F. Fanta. etal, U. S. P. 955, 828
[24]M. I. Khalil. et al. Journal of Polymer Science: Polymer Chemistry Edition, 21, 715-724 1983
[25]张志成，吴国忠，徐湘凌，张曼维高分子材料科学与工程 No．6 16-21．(1992)
[26]F. L. Buchholz. Keeping Dry with Superabsorbent Polymers. Chemtech, 1994, 24(9): 38—43
[27]王直刚．高吸水性树脂的合成及应用．石油化工 1996，25(9)：667-672
[28]翟羽伸．高吸水性树脂．石油化工 1985，14(10)：625-631
[29]刘廷栋，张立广，刘京．聚丙烯酸钠盐高吸水性树脂．合成树脂及塑料。1993，10(2)：68-72
[30]柳明珠，吴靖嘉，巨育红．吸水性高分子材料的研究(Ⅱ)——交联聚丙烯酸钠的合成及其性能研究．兰州大学学报(自然科学版)．1991，27(3)：74—79
[31]郑邦乾，朱清泉，徐僖．高吸水性HPMA的制备和性能．高分子材料科学与工程．1987(2)：68-73
[32]刘廷栋，刘京高吸水性树脂在日用化学工业中的应用[J]．日用化学工业，1995，(1)：22—24
[33]Chem Abstr,1992,116:42832; USP5,055,503
[34]朱秀林等．高分子材料科学与工程，1992，8(1)：35．
[35]喻发金等．高分子材料科学与工程，1998，14(1)：31．
[36]Chemical Week, 98, August/5:34.
[37]W.Robert. USP 57 19201(1998).
[38]S.George. DE 19621323(1997).
[39]K.Ishita.J P 09253 129(1997).
[40]C.Christian.WO9743331(1997).
[41]T.Namba, et al.In Advances in Superabsobent Polymers, ACS, 1994.
[42]H.Sekimoto, M.Fukami, O.Kishimoto, et al.Netti Nogyo, 1995, 39(4):236.
[43]H.Kobayaohi, K.Okamura, Y.Sano, et al.WO 8810, 001(1988).
[44]J.J.Sheu. USP atent 5163115(1992).
[45]万明球等．功能高分子学报，1995，8(3)：271
[46]M.Hiroshi. JP09206513(1997)
[47]张燕萍 变性淀粉制造与应用 2000(1)：329-331．
[48]温品谦二．超强吸水剂的研究[J]．有机合成化学，1980，38(6)：546～554．
[49]W.Y.Lee, R.J.Wu. J.Appl.Polym.Sci., 1996, 62:1009.
[50]P.Lepoutre, S.H.Hui , A.A.Robertson. J.Appl.Polym.Sci., 1973, 17:3143.
[51]Kimura, T.Hatsuda.EP 450924 1991
[52]功能高分子学报 1999，2(12)：214
[53]K.J.Buchanan, B.Hird.Polym Bull, 1986, 15:325.
[54]路建美，朱秀林，胡逢吉等．乌头酸与丙烯酸钠的微波辐射共聚制高吸水性树脂．石油化工，1999，28(1)：36-37
[55]东华大学学报(自然科学版)，2000，28(5)：52-54
[56]高允彦编．正交及回归试验设计方法．北京：冶金工业出版社．1988
[57]中国现场统计研究会三次设计组，全国总工会电教中心编著．正交法和三次设计．北京：科学出版社．1985
[58]北京大学数学力学系概率统计组编。正交设计。人民教育出版社 1976
[59]Adtler Research Laboratories, INC. The Sadtler Standard Spectra: Commercial Spectra IR Grating, Monomers & Polymers. 1973
[60]George Odianprinciples of Polymerization, 2nd Ed. John Wiley&Sons, 1981
[61]潼迟章，化学工业(日)，1976，27，618
[62]刘廷栋，刘京等．高分子通报，1994(3)：181
[63]Iogawa, et. al. Rate of Swelling of Sodium Polyacrylate. J. Appl. Polym.Sci 1993, 17: 217, 222
[64]P. J.Flory. Principles of Polymer Chemistry. Comell University Press. New York.1953
[65]于善普，李旭东，影响吸水聚合物的吸水能力的因素及表征．青岛化工学院学报。1997，18(2)：147-151
[66]M. Manabeet. al. Volumetric and Thermal Behaviors of Water Uptaken in Superabsorbentpolymer. Bull. Chem. Soc. Jpn. 1992, 65.. 2319—2322