静电纺丝法制备超吸水纤维的研究
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摘要
静电纺丝是通过在聚合物溶液或熔体中施加电场来制造聚合物纤维的纺丝技术，其纤维直径在μm和nm之间。本课题采用溶液聚合法制备了可纺性的超吸水成纤共聚物溶液，研究静电纺丝法制备超吸水纤维，主要做了以下几个方面的工作。
首先，研究了超吸水成纤共聚物溶液的性质，例如密度、粘度、表面张力等与溶液浓度的关系。
其次，在合成超吸水成纤共聚物溶液的基础上，开展了静电纺丝工艺的研究。具体考察了不同的纺丝工艺条件例如溶液浓度、纺丝电压、收集距离、喷头孔径等对纤维的直径及其形态结构的影响。实验发现：随着聚合物溶液浓度的增加，纤维的直径增大；纤维的直径随着纺丝电压的增大而减小；收集距离的增大使得纤维的直径先减小后增大；纤维的直径随着喷头孔径的增大而增大。
扫描电子显微镜(SEM)的照片给出了不同纺丝工艺条件下超吸水纤维形态结构的变化。可以发现，随着聚合物溶液浓度的增大，连珠状纤维的密度减小，纺丝电压升高，接收距离增大都相应地使连珠状纤维的密度减小，纤维间的彼此粘连现象减弱。
最后，对静电纺超吸水纤维的吸水性能进行了测试。随着纤维纤度的降低，静电纺超吸水纤维的吸水倍率有显著的提高，热交联处理温度的升高使得纤维的吸水倍率先增大后减小，以180℃热交联所得纤维的吸水倍率最高，热交联处理时间对纤维吸水倍率有相同的影响，以20min热交联所得纤维的吸水倍率最高。
Electrospinning is a process that produces continuous polymer fibers with diameters in the range of nanometer to micrometer through the action of an external electric field imposed on a polymer solution or melt. The superabsorbent polymer solution was made by solution polymerization, the study on electrospinning of superabsorbent fibers included three main aspects of work as follows:
Firstly, the properties of the solution such as viscosity, surface tension were studied.
Secondly, the electrospinning process of the superabsorbent polymer solution was studied. In this work, we evaluated systematically the effects of the processing parameters such as solution concentration, spinning voltage, the distance of collection and the diameter of the sprayer, on the diameter and the morphology of the fibers formed. We found that the diameter of the electrospun super absorbent fibers increased with the increase of solution concentration. Increasing electrospinning voltage decreased the diameter of the fibers. Increasing the distance of collection made the diameter of the fibers decrease and then increase. Increasing the diameter of the sprayer increased the diameter of the fibers.
Scanning electron microscope (SEM) photos showed the change of the morphology of the electrospun superabsorbent fibers according to the different processing parameters. Higher concentration favored formation of fibers without beads, higher spinning voltage, larger distance of collection also favored the formation of fibers without beads.
Lastly, the water absorbing power of the electrospun fibers was measured. The results showed that the water absorbing power increased when the linear density of the fiber decreased; whereas increasing the temperature of the heat treatment, the water absorbing power increased and then decreased; the same result was observed when increasing the time of the heat treatment.
首先，研究了超吸水成纤共聚物溶液的性质，例如密度、粘度、表面张力等与溶液浓度的关系。
其次，在合成超吸水成纤共聚物溶液的基础上，开展了静电纺丝工艺的研究。具体考察了不同的纺丝工艺条件例如溶液浓度、纺丝电压、收集距离、喷头孔径等对纤维的直径及其形态结构的影响。实验发现：随着聚合物溶液浓度的增加，纤维的直径增大；纤维的直径随着纺丝电压的增大而减小；收集距离的增大使得纤维的直径先减小后增大；纤维的直径随着喷头孔径的增大而增大。
扫描电子显微镜(SEM)的照片给出了不同纺丝工艺条件下超吸水纤维形态结构的变化。可以发现，随着聚合物溶液浓度的增大，连珠状纤维的密度减小，纺丝电压升高，接收距离增大都相应地使连珠状纤维的密度减小，纤维间的彼此粘连现象减弱。
最后，对静电纺超吸水纤维的吸水性能进行了测试。随着纤维纤度的降低，静电纺超吸水纤维的吸水倍率有显著的提高，热交联处理温度的升高使得纤维的吸水倍率先增大后减小，以180℃热交联所得纤维的吸水倍率最高，热交联处理时间对纤维吸水倍率有相同的影响，以20min热交联所得纤维的吸水倍率最高。
Electrospinning is a process that produces continuous polymer fibers with diameters in the range of nanometer to micrometer through the action of an external electric field imposed on a polymer solution or melt. The superabsorbent polymer solution was made by solution polymerization, the study on electrospinning of superabsorbent fibers included three main aspects of work as follows:
Firstly, the properties of the solution such as viscosity, surface tension were studied.
Secondly, the electrospinning process of the superabsorbent polymer solution was studied. In this work, we evaluated systematically the effects of the processing parameters such as solution concentration, spinning voltage, the distance of collection and the diameter of the sprayer, on the diameter and the morphology of the fibers formed. We found that the diameter of the electrospun super absorbent fibers increased with the increase of solution concentration. Increasing electrospinning voltage decreased the diameter of the fibers. Increasing the distance of collection made the diameter of the fibers decrease and then increase. Increasing the diameter of the sprayer increased the diameter of the fibers.
Scanning electron microscope (SEM) photos showed the change of the morphology of the electrospun superabsorbent fibers according to the different processing parameters. Higher concentration favored formation of fibers without beads, higher spinning voltage, larger distance of collection also favored the formation of fibers without beads.
Lastly, the water absorbing power of the electrospun fibers was measured. The results showed that the water absorbing power increased when the linear density of the fiber decreased; whereas increasing the temperature of the heat treatment, the water absorbing power increased and then decreased; the same result was observed when increasing the time of the heat treatment.
引文
[1] 马光辉，苏志国主编，新型高分子材料，化学工业出版社，2002
[2] 方锡江，文勇奋，功能性纺织品及纳米技术的开发与应用，纺织科学研究，2002，(3)：1
[3] 纪明辉，魏平原，孟庆飞，纳米纤维的制备及性能高科技纤维与应用，2002，27：11
[4] 安林红，王跃，纳米纤维技术的开发及应用，当代石油化工，2002，10：41
[5] 张立德编，纳米材料，化学工业出版社，北京，2002
[6] USP4892533, Ultrahigh water-absorbing fiber-forming composition, Le-Khac, January 9,1990
[7] USP5154165, Polymer compositions and absorbent fibers produced therefrom, Le-Khac, September 29,1992
[8] 罗益锋，高吸水性树脂与纤维，高科技纤维与应用，1999，24(4)：32
[9] 祝志峰，周永远，张文赓，高吸水材料及其在纺织工业中的应用前景，中国纺织大学学报，1994，20(4)：80
[10] AFomhals. US patent, No.1,975,504 (1934)
[11] Lei Huang, R.Andrew McMillon, Robert PApkarian,etc. Generation of synthetic elastin-mimetic small diameter fibers and fiber networks. Macromolecules, 2000, 33: 2989
[12] R Jaeger, H.Schonherr, G.J.Vancso, Chain Packing in Electrospun Poly(ethyleneoxide) Visualized by Atomic force. Macromolecules 1996,29:7634
[13] Raimund Jaeger, Michel M Bergshoef, Cristina Martin I Batlle,etc. Electrospinning of Ultra-thin Polymer Fibers. Macromol Symp, 1998,127:141
[14] J. M. Deitzel, J. D. Kleinmeyer, J.K. Hirvonen, etc. Controlled deposition of elecrospun poly(ethylene oxide)fibers. Polymer ,2001,42: 8163
[15] Chrestopher J.Buchko, Loui C.Chen, Yu Shen, etc. Processing and microstructural characterization of porous biocompatible protein polymer thin films. Polymer 1999,40: 7397
[16] H.Fong ,I.Chun ,D.H.Reneker. Beaded nanofibers formed during electrospinning.
Polymer, 1999, 40:4585.
[17] Jong-Sang Kim, Darrell H Reneker. Polybenzimidazole nanofiber produced by electrospinning. Polymer Engineering and Science 1999,39:849
[18] Hao Fong, Darrell H Reneker, Journal of Polymer Science, Part B: Polymer Physics, 1999,37: 3488
[19] J.M.Deitzel, J.Kleinmeyer, D.Harris, etal. The effect of processing variables on the morphology of electrospun nanofibers and textiles. Polymer, 2001, 42:261.
[20] Jong-Sang Kim, Dai Soo Lee. Thermal Properties of Electrospun Polyesters. Polymer Journal, 2000,32:616
[21] M.M.Demir, I.Yilgor, E.Yilgor. Electrospinning of polyurethane fibers. Polymer, 2002, 43: 3303.
[22] A.Buer, S.C.Ugbolue, S.B.Wamer. Electrospirming and properties of some nanofibers. Textile Res J, 2001, 71 (4):323.
[23] Y M Shin, M M Hohman, M P Brenner, etc. Experimental characterization of electrospinning: the electrically forced jet and instabilities. Polymer 2001,42:9955
[24] Y M Shin, M M Hohman, M P Brenner, etc. Electrospinning: A whipping fluid jet generates submicron polymer fibers. Applied Physics Letters, 2001,78(8): 1149
[25] A.E.Zachariades, R.S.Porter. High modulus polymers. Polymer news, 1995,20: 206
[26] 张锡玮，夏禾，徐纪刚，静电纺丝法纺制纳米级聚丙烯腈纤维毡，塑料，2000，29(2)：16．
[27] 肖长发，电子纺丝成形及纤维形态结构研究，高科技纤维与应用，2003，28(1)：10
[28] EI-Refaie Kenawy, Gary L.Bowlin, Kevin Mansfield. Release of tetracycline hydrochloride from electrospun poly(ethylene-co-vinylacetate),poly(lactic acid),and a blend. Journal of controlled release ,2002,81: 57
[29] Sureepom Koombhongse, Wenxia Liu, Darrell H.Reneker. Flat polymer ribbons and other shapes by electrospinning. Joumal of Polymer Science, Part B:
Polymer Physics,2001,39:2598
[30] K.J.Pawlowski, H.L.Belvin, D.L.Raney. Electrospinning of a micro-air vehicle wing skin. Polymer,2003,44:1309
[31] Darrell H Reneker, Iksoo Chun. Nanometre diameter fibers of polymer, produced by electrospinning. Nanotechnology, 1996,7:216
[32] K.H.Lee, H.Y.Kim, M.S.Khil. Characterization off nano-structured poly(ε-caprolactone) nonwoven mats. Polymer,2003,44: 1287
[33] J.M.Deitzel, W.Kosik, S.H.McKmight, etal. Electrospinning of polymer nanofibers with specific surface chemistry. Polymer,2002,43:1025.
[34] Ian D.Norris, Manal M.Shaker, Frank K.Ko. Electrostatic fabrication of ultrafine conducting fibers: polyaniline/polyethylene oxide blends. Synthetic metals,2000,114:109
[35] J.S.Stephens, S.F.Risk, S.Megelski. "Real Time" Raman studies of electrospun fibers. Applied spectroscopy,2001,55(10): 1287
[36] Mikhail Bognitzki, Thomas Frese, Martin Steinhart, Preparation of fibers with nanoscaled morphologies: electrospinning of polymer blends.Polymer Engineering and Science,2001,41:982
[37] X.Fang, D.H.Reneker. DNA fibers by electrospinning. J.Macromol.Sci.Phys. 1997, 836 (2): 169
[38] Jxyesh Doshi, Darrell H.Reneker. Electrospinning process and applications of electrospun fibers. Journal of electrostatics, 1995,35:151
[39] D.H.,Reneker, W.Kataphinan, A.Theron. Nanofiber garlands of polycaprolactone by electrospinning. Polymer,2002,43:6785
[40] Xinhua Zong, Kwangsok Kim, Dufei Fang, etal. Structure and process relationship of electrospun bioabsorbable nanofiber membranes. Polymer,2002,43:4403.
[41] Haiqing Liu, You-Lo Hsieh. Ultrafine fibrous cellulose membranes from electrospinning of cellulose acetate. Journal of Polymer Science: Part B: Polymer Physics, 2002, 40:2119.
[42] 董纪震，罗鸿烈等编，合成纤维生产工艺学(第二版)，中国纺织出版社，1996
[43] 赵胜利，黄勇，高压静电场纺丝的研究与进展，纤维素科学与技术，2002，10(3)：53
[44] Darrell H.Reneker, Alexander L.Yarin, Hao Fong. Bending instability of electrically charged liquid jets of polymer solutions in electrospinning. Journal of Applied Physics,2000,87 (9): 4531
[45] L.Larrondo, R.ST.Johm Manley. Electrostatic fiber spinning from polymer melts. Ⅰ. Experimental observations on fiber formation and properties. Journal of Polymer Science, Polymer Physics Edition, 1981,19:909
[46] L.Larrondo, R.ST.Johm Manley. Electrostatic fiber spinning from polymer melts. Ⅱ. Experimental observations on fiber formation and properties. Journal of Polymer Science, Polymer Physics Edition,1981,19:921
[47] L.Larrondo, R.ST.Johm Manley. Electrostatic fiber spinning from polymer melts. Ⅲ. Experimental observations on fiber formation and properties. Journal of Polymer Science, Polymer Physics Edition, 1981,19:933
[48] A.L.Yarin, S.Koombhongse, D.H.Reneker. Taylor cone and jetting from liquid droplets in electrospinning of nanofibers. Journal of applied physics, 2001,90 (9): 4836
[49] A.L.Yarin, S.Koombhongse, D.H.Reneker. Bending instability in electrospinning of nanofibers. Journal of Applied Physics,2001,89 (5):3018
[50] Moses M.Hohman, Midhael Shin, Gregory Rutledge. Electrospinning and electrically forced jets. Ⅰ. Stability theory. Physics of fluids,2001,13(8):2201
[51] Moses M.Hohman, Midhael Shin, Gregory Rutledge. Electrospinning and electrically forced jets. Ⅱ. Stability theory. Physics of fluids,2001,13(8):2221
[52] 吕砚山，常见电工电子技术手册，化学工业出版社，北京，1995
[53] 《化工百科全书》编辑委员会编，树脂与塑料，化学工业出版社
[54] K.J.Pawlowski, H.L.Belvin, D.L.Raney. Electrospinning of a micro-air vehicle wing skin. Polymer,2003,44:1309
[55] 吴大诚，杜仲良，高绪珊编著，纳米纤维，化学工业出版社，北京，2003
[56] 郭卫红，汪济奎编著，现代功能材料及其应用，化学工业出版社，北京，2002
[57] 王国建，王公善编，功能高分子，同济大学出版社，1996
[2] 方锡江，文勇奋，功能性纺织品及纳米技术的开发与应用，纺织科学研究，2002，(3)：1
[3] 纪明辉，魏平原，孟庆飞，纳米纤维的制备及性能高科技纤维与应用，2002，27：11
[4] 安林红，王跃，纳米纤维技术的开发及应用，当代石油化工，2002，10：41
[5] 张立德编，纳米材料，化学工业出版社，北京，2002
[6] USP4892533, Ultrahigh water-absorbing fiber-forming composition, Le-Khac, January 9,1990
[7] USP5154165, Polymer compositions and absorbent fibers produced therefrom, Le-Khac, September 29,1992
[8] 罗益锋，高吸水性树脂与纤维，高科技纤维与应用，1999，24(4)：32
[9] 祝志峰，周永远，张文赓，高吸水材料及其在纺织工业中的应用前景，中国纺织大学学报，1994，20(4)：80
[10] AFomhals. US patent, No.1,975,504 (1934)
[11] Lei Huang, R.Andrew McMillon, Robert PApkarian,etc. Generation of synthetic elastin-mimetic small diameter fibers and fiber networks. Macromolecules, 2000, 33: 2989
[12] R Jaeger, H.Schonherr, G.J.Vancso, Chain Packing in Electrospun Poly(ethyleneoxide) Visualized by Atomic force. Macromolecules 1996,29:7634
[13] Raimund Jaeger, Michel M Bergshoef, Cristina Martin I Batlle,etc. Electrospinning of Ultra-thin Polymer Fibers. Macromol Symp, 1998,127:141
[14] J. M. Deitzel, J. D. Kleinmeyer, J.K. Hirvonen, etc. Controlled deposition of elecrospun poly(ethylene oxide)fibers. Polymer ,2001,42: 8163
[15] Chrestopher J.Buchko, Loui C.Chen, Yu Shen, etc. Processing and microstructural characterization of porous biocompatible protein polymer thin films. Polymer 1999,40: 7397
[16] H.Fong ,I.Chun ,D.H.Reneker. Beaded nanofibers formed during electrospinning.
Polymer, 1999, 40:4585.
[17] Jong-Sang Kim, Darrell H Reneker. Polybenzimidazole nanofiber produced by electrospinning. Polymer Engineering and Science 1999,39:849
[18] Hao Fong, Darrell H Reneker, Journal of Polymer Science, Part B: Polymer Physics, 1999,37: 3488
[19] J.M.Deitzel, J.Kleinmeyer, D.Harris, etal. The effect of processing variables on the morphology of electrospun nanofibers and textiles. Polymer, 2001, 42:261.
[20] Jong-Sang Kim, Dai Soo Lee. Thermal Properties of Electrospun Polyesters. Polymer Journal, 2000,32:616
[21] M.M.Demir, I.Yilgor, E.Yilgor. Electrospinning of polyurethane fibers. Polymer, 2002, 43: 3303.
[22] A.Buer, S.C.Ugbolue, S.B.Wamer. Electrospirming and properties of some nanofibers. Textile Res J, 2001, 71 (4):323.
[23] Y M Shin, M M Hohman, M P Brenner, etc. Experimental characterization of electrospinning: the electrically forced jet and instabilities. Polymer 2001,42:9955
[24] Y M Shin, M M Hohman, M P Brenner, etc. Electrospinning: A whipping fluid jet generates submicron polymer fibers. Applied Physics Letters, 2001,78(8): 1149
[25] A.E.Zachariades, R.S.Porter. High modulus polymers. Polymer news, 1995,20: 206
[26] 张锡玮，夏禾，徐纪刚，静电纺丝法纺制纳米级聚丙烯腈纤维毡，塑料，2000，29(2)：16．
[27] 肖长发，电子纺丝成形及纤维形态结构研究，高科技纤维与应用，2003，28(1)：10
[28] EI-Refaie Kenawy, Gary L.Bowlin, Kevin Mansfield. Release of tetracycline hydrochloride from electrospun poly(ethylene-co-vinylacetate),poly(lactic acid),and a blend. Journal of controlled release ,2002,81: 57
[29] Sureepom Koombhongse, Wenxia Liu, Darrell H.Reneker. Flat polymer ribbons and other shapes by electrospinning. Joumal of Polymer Science, Part B:
Polymer Physics,2001,39:2598
[30] K.J.Pawlowski, H.L.Belvin, D.L.Raney. Electrospinning of a micro-air vehicle wing skin. Polymer,2003,44:1309
[31] Darrell H Reneker, Iksoo Chun. Nanometre diameter fibers of polymer, produced by electrospinning. Nanotechnology, 1996,7:216
[32] K.H.Lee, H.Y.Kim, M.S.Khil. Characterization off nano-structured poly(ε-caprolactone) nonwoven mats. Polymer,2003,44: 1287
[33] J.M.Deitzel, W.Kosik, S.H.McKmight, etal. Electrospinning of polymer nanofibers with specific surface chemistry. Polymer,2002,43:1025.
[34] Ian D.Norris, Manal M.Shaker, Frank K.Ko. Electrostatic fabrication of ultrafine conducting fibers: polyaniline/polyethylene oxide blends. Synthetic metals,2000,114:109
[35] J.S.Stephens, S.F.Risk, S.Megelski. "Real Time" Raman studies of electrospun fibers. Applied spectroscopy,2001,55(10): 1287
[36] Mikhail Bognitzki, Thomas Frese, Martin Steinhart, Preparation of fibers with nanoscaled morphologies: electrospinning of polymer blends.Polymer Engineering and Science,2001,41:982
[37] X.Fang, D.H.Reneker. DNA fibers by electrospinning. J.Macromol.Sci.Phys. 1997, 836 (2): 169
[38] Jxyesh Doshi, Darrell H.Reneker. Electrospinning process and applications of electrospun fibers. Journal of electrostatics, 1995,35:151
[39] D.H.,Reneker, W.Kataphinan, A.Theron. Nanofiber garlands of polycaprolactone by electrospinning. Polymer,2002,43:6785
[40] Xinhua Zong, Kwangsok Kim, Dufei Fang, etal. Structure and process relationship of electrospun bioabsorbable nanofiber membranes. Polymer,2002,43:4403.
[41] Haiqing Liu, You-Lo Hsieh. Ultrafine fibrous cellulose membranes from electrospinning of cellulose acetate. Journal of Polymer Science: Part B: Polymer Physics, 2002, 40:2119.
[42] 董纪震，罗鸿烈等编，合成纤维生产工艺学(第二版)，中国纺织出版社，1996
[43] 赵胜利，黄勇，高压静电场纺丝的研究与进展，纤维素科学与技术，2002，10(3)：53
[44] Darrell H.Reneker, Alexander L.Yarin, Hao Fong. Bending instability of electrically charged liquid jets of polymer solutions in electrospinning. Journal of Applied Physics,2000,87 (9): 4531
[45] L.Larrondo, R.ST.Johm Manley. Electrostatic fiber spinning from polymer melts. Ⅰ. Experimental observations on fiber formation and properties. Journal of Polymer Science, Polymer Physics Edition, 1981,19:909
[46] L.Larrondo, R.ST.Johm Manley. Electrostatic fiber spinning from polymer melts. Ⅱ. Experimental observations on fiber formation and properties. Journal of Polymer Science, Polymer Physics Edition,1981,19:921
[47] L.Larrondo, R.ST.Johm Manley. Electrostatic fiber spinning from polymer melts. Ⅲ. Experimental observations on fiber formation and properties. Journal of Polymer Science, Polymer Physics Edition, 1981,19:933
[48] A.L.Yarin, S.Koombhongse, D.H.Reneker. Taylor cone and jetting from liquid droplets in electrospinning of nanofibers. Journal of applied physics, 2001,90 (9): 4836
[49] A.L.Yarin, S.Koombhongse, D.H.Reneker. Bending instability in electrospinning of nanofibers. Journal of Applied Physics,2001,89 (5):3018
[50] Moses M.Hohman, Midhael Shin, Gregory Rutledge. Electrospinning and electrically forced jets. Ⅰ. Stability theory. Physics of fluids,2001,13(8):2201
[51] Moses M.Hohman, Midhael Shin, Gregory Rutledge. Electrospinning and electrically forced jets. Ⅱ. Stability theory. Physics of fluids,2001,13(8):2221
[52] 吕砚山，常见电工电子技术手册，化学工业出版社，北京，1995
[53] 《化工百科全书》编辑委员会编，树脂与塑料，化学工业出版社
[54] K.J.Pawlowski, H.L.Belvin, D.L.Raney. Electrospinning of a micro-air vehicle wing skin. Polymer,2003,44:1309
[55] 吴大诚，杜仲良，高绪珊编著，纳米纤维，化学工业出版社，北京，2003
[56] 郭卫红，汪济奎编著，现代功能材料及其应用，化学工业出版社，北京，2002
[57] 王国建，王公善编，功能高分子，同济大学出版社，1996