熔纺—拉伸致孔法聚氨酯/聚丙烯腈共混中空纤维膜的研究
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摘要
本文对拉伸相界面分离成孔机理，PAN／PU共混体系，PAN／PU中空纤维膜的熔融纺丝-拉伸致孔工艺及PAN／PU共混膜的结构和性能作了研究和探讨。
首先对相界面分离成孔机理作了探讨。结果表明对于“海—岛结构”非相容性共混高聚物中空纤维，经拉伸后，能形成相界面分离孔。其中共混高聚物的相界面，共混组分的泊松比，分散相的平均粒径和粒径分布，分散相的浓度和均一性等因素影响相界面分离孔的数目和网络化程度。
研究了PAN／PU共混体系。结果表明PAN／PU为热力学不相容体系，当PAN含量在0％—30％之间，PAN／PU为“海—岛结构”两相体系，其中PAN为分散相，粒径范围在0.5—4μm之间。随着PAN含量的增加，PAN／PU共混体系的流动性迅速变差。
研究了PAN／PU共混物的熔融纺丝工艺。结果表明纺丝温度在190—200℃之间，螺杆转速＜70r／min时，能够顺利纺制PAN／PU中空纤维。随着PAN含量的增加，PAN／PU中空纤维的断裂强度和断裂伸长率下降。PAN／PU具有较好的弹性回复率。
研究表明通过拉伸相界面分离致孔技术可以制得PAN／PU中空纤维膜。PAN／PU中空纤维膜的的水通量随着拉伸倍数的增大而增大，随着PAN含量的增大而增大。
本文还研究PAN／PU中空纤维膜具有压力记忆效应和温度记忆效应。结果表明水通量的记忆效应与相界面微孔密切相关。
In this paper, exhaustive studies on the mechanism of draw-interfacial phase separate micro-void, PAN/PU blending system, melt spinning technology of PAN/PU hollow fiber membrane, and the structure-property of PAN/PU hollow fiber membrane were fulfilled.
The study on the mechanism of draw-interfacial phase separate micro-void was carried out. The results showed that it is impossible for "Island-Sea" structure non-compatible blend polymer to form interfacial phase separated micro-void after being drawn. The phase interface of blending polymer, the Poisson's ratio of blending component, the average particle diameter of disperse phase, the average particle size distribution of disperse phase, the concentration of disperse phase and the homogeneity of disperse phase affect the numbers and crosslinkage of interfacial phase separated micro-void
The properties of PAN/PU blending polymer was also studied. The results showed that the PAN/PU blend system was not a thermodynamics compatibility one. The compatibility of PAN/PU blending polymer was very bad. The PAN/PU blending polymer is a "Island-Sea" structure system, and PAN content is disperse phase, and the particle diameter is from 0.5-4 u m when the concentration of PAN is from 0%-30%. The flowability of PAN/PU blending system become bad with the increase of the concentration of PAN.
The melt-spinning technology of PAN/PU blending polymer was also studied. The PAN/PU hollow fibers were successfully fabricated when the spinning temperature was controlled from 190癈 to 200癈 and the rotate speed of screw less than 70r/min. The break strength and the extension at break of PAN/PU hollow fiber decreased with the increase of the concentration of PAN. PAN/PU hollow fibers possess excellent elastic recovery percentage.
The study showed that the PAN/PU hollow fiber membranes were successfully fabricated the technic of draw-interfacial phase separate micro-void. The water flux of
PAN/PU hollow fiber membranes increased with the increase of draw ratio and concentration of PAN.
The pressure memory effect and the temperature memory effect was also studied. The study showed that the memory effect of water flux of PAN/PU hollow fiber membranes was tightly related to interfacial phase micro-void.
首先对相界面分离成孔机理作了探讨。结果表明对于“海—岛结构”非相容性共混高聚物中空纤维，经拉伸后，能形成相界面分离孔。其中共混高聚物的相界面，共混组分的泊松比，分散相的平均粒径和粒径分布，分散相的浓度和均一性等因素影响相界面分离孔的数目和网络化程度。
研究了PAN／PU共混体系。结果表明PAN／PU为热力学不相容体系，当PAN含量在0％—30％之间，PAN／PU为“海—岛结构”两相体系，其中PAN为分散相，粒径范围在0.5—4μm之间。随着PAN含量的增加，PAN／PU共混体系的流动性迅速变差。
研究了PAN／PU共混物的熔融纺丝工艺。结果表明纺丝温度在190—200℃之间，螺杆转速＜70r／min时，能够顺利纺制PAN／PU中空纤维。随着PAN含量的增加，PAN／PU中空纤维的断裂强度和断裂伸长率下降。PAN／PU具有较好的弹性回复率。
研究表明通过拉伸相界面分离致孔技术可以制得PAN／PU中空纤维膜。PAN／PU中空纤维膜的的水通量随着拉伸倍数的增大而增大，随着PAN含量的增大而增大。
本文还研究PAN／PU中空纤维膜具有压力记忆效应和温度记忆效应。结果表明水通量的记忆效应与相界面微孔密切相关。
In this paper, exhaustive studies on the mechanism of draw-interfacial phase separate micro-void, PAN/PU blending system, melt spinning technology of PAN/PU hollow fiber membrane, and the structure-property of PAN/PU hollow fiber membrane were fulfilled.
The study on the mechanism of draw-interfacial phase separate micro-void was carried out. The results showed that it is impossible for "Island-Sea" structure non-compatible blend polymer to form interfacial phase separated micro-void after being drawn. The phase interface of blending polymer, the Poisson's ratio of blending component, the average particle diameter of disperse phase, the average particle size distribution of disperse phase, the concentration of disperse phase and the homogeneity of disperse phase affect the numbers and crosslinkage of interfacial phase separated micro-void
The properties of PAN/PU blending polymer was also studied. The results showed that the PAN/PU blend system was not a thermodynamics compatibility one. The compatibility of PAN/PU blending polymer was very bad. The PAN/PU blending polymer is a "Island-Sea" structure system, and PAN content is disperse phase, and the particle diameter is from 0.5-4 u m when the concentration of PAN is from 0%-30%. The flowability of PAN/PU blending system become bad with the increase of the concentration of PAN.
The melt-spinning technology of PAN/PU blending polymer was also studied. The PAN/PU hollow fibers were successfully fabricated when the spinning temperature was controlled from 190癈 to 200癈 and the rotate speed of screw less than 70r/min. The break strength and the extension at break of PAN/PU hollow fiber decreased with the increase of the concentration of PAN. PAN/PU hollow fibers possess excellent elastic recovery percentage.
The study showed that the PAN/PU hollow fiber membranes were successfully fabricated the technic of draw-interfacial phase separate micro-void. The water flux of
PAN/PU hollow fiber membranes increased with the increase of draw ratio and concentration of PAN.
The pressure memory effect and the temperature memory effect was also studied. The study showed that the memory effect of water flux of PAN/PU hollow fiber membranes was tightly related to interfacial phase micro-void.
引文
[01]刘茉娥等．新型分离技术基础．浙江大学出版社，1993：36
[02]高以烜等．膜分离技术基础．科学出版社，1989
[03]邵刚．膜法水处理技术及工程实例．化学工业出版社，2002：1
[04]刘国信等．膜法分离技术及其应用．中国环境科学出版社，1991：6
[05]张树钧等．改性纤维与特种纤维．中国石化出版社，1995：231
[06]Th. Hazella. Biochem. Z. 194(1928): 128
[07]R.A.De Well. U.S.Pat.2972349(1961)
[08]刘茉娥等．膜分离技术．化学工艺出版社，1998：21
[09]余三传、高从锴等．膜科学与技术．1999，19(6)：45—47
[10]丁马太等，水处理技术，1991，17(4)：211
[11]殷景华等．功能材料概论．哈尔滨工业大学出版社，1999
[12]Authowy RC. Ultrafiltration membranes and applications.New York and London. Plenum Press, 1980
[13]凯斯延(美)著、王学松译．合成聚合物膜．化学工业出版社，1992：280-281
[14]James J LoweryNeil、D Plotkin. Method for preparing a uniform polyolefinic microporous hollow fiber[P].US pat: 4514981:1985-09-17
[15]Xiao Chang-fa、Liu Zhao-feng. J. of Applied Polymer Sci. 1990,Vol.41: 439
[16]候养全等．氨纶熔纺可行性探讨．合成纤维工业，1999，Vol22(4)：17
[17]N.S.Scheneider et al. J. Macromol Sci.Phys.. B3,1969:626
[18]K.D.Zeigel. J.Macromol Sci. Phys. B5(1),1971:11
[19]Shih-Hsing Chen et al. J. Membr. Sci.. 2000.173:99
[20]蜂须贺·久雄等．公开特许公报．特开平10-24223
[21]吴培熙、张留城．聚合物共混改性．中国轻工业出版社，1996
[22]封朴．聚合物合金．同济大学出版社，1997
[23]何曼君．高分子物理．复旦大学出版社，1990
[24]吴人洁等．高聚物表面与界面．科学出版社，1998
[25]刘决康．合成纤维．1990，3：38—42
[26]A. Vrij. Polymer Science A—2. 1968, 7:1919
[27]A. Vrij and M. W.J. Van Den Esker. J. of Polymer Science. 1975, 13:727
[28]R. J. Roe. J. Chem. Phys.. 1974, 60:4192
[29]J. Nose.. Polymer J.. 1976, 8:96
[30]吴秋林等．水处理技术．1993，19(4)：201
[31]叶凌碧等．微孔膜的截留作用机理和膜的选用，净水技术，1984，(2)：6-10
[32]王保国、蒋维钧．水处理技术．1995，21(1)：12
[33]陈洪钫、刘家淇．化工分离过程．化学工业出版社，1995
[34]林刚、周津等．膜科学与技术．1997，17(3)：50
[35]仲蕾兰、戚慰光等．合成纤维．1990，19(4)：13
[36]A. K. Fritzsche A. R. Arevalo and M. D. Moore. J. of Membrane Science. 1993, 81:199—201
[37]孙秀珍等．水处理技术．1987，13(2)：106
[38]叶凌碧等．膜分离科学与技术．1983，3(1)：54
[39]冯健、陈平．膜科学与技术．1994，14(1)：54
[40]金日光、华幼卿．高分子物理．化学工业出版社，1997：113
[41]邓本诚、李俊山．橡胶塑料共混改性．中国石化出版社，1996：15-64，235
[42]David D J. Analytical Chem. of Polyurethane,Newyork,Wiley-Interscience, 1969
[43]刘英俊、刘伯元．塑料填充改性．中国轻工业出版社，1998：106-107
[44]Einstein A. Physik. 1906.19289;1914.34,591
[45]Guth E.and SimnaR. Kolloidzschr.1936, 74. 266
[46]傅明源等．聚氨酯弹性体及其应用．化学工业出版社，1999：24
[47]董纪震等．合成纤维生产工艺学．纺织工业出版社，1993：30
[48]Houtz R C Textile Res J. 1950,20:786
[49]Olive G H and Olive S.Adv Polymer Sci 1979,32:123
[50]封严．聚氨酯系共混膜及分离性能的研究．天津工业大学硕士论文，2000：34
[02]高以烜等．膜分离技术基础．科学出版社，1989
[03]邵刚．膜法水处理技术及工程实例．化学工业出版社，2002：1
[04]刘国信等．膜法分离技术及其应用．中国环境科学出版社，1991：6
[05]张树钧等．改性纤维与特种纤维．中国石化出版社，1995：231
[06]Th. Hazella. Biochem. Z. 194(1928): 128
[07]R.A.De Well. U.S.Pat.2972349(1961)
[08]刘茉娥等．膜分离技术．化学工艺出版社，1998：21
[09]余三传、高从锴等．膜科学与技术．1999，19(6)：45—47
[10]丁马太等，水处理技术，1991，17(4)：211
[11]殷景华等．功能材料概论．哈尔滨工业大学出版社，1999
[12]Authowy RC. Ultrafiltration membranes and applications.New York and London. Plenum Press, 1980
[13]凯斯延(美)著、王学松译．合成聚合物膜．化学工业出版社，1992：280-281
[14]James J LoweryNeil、D Plotkin. Method for preparing a uniform polyolefinic microporous hollow fiber[P].US pat: 4514981:1985-09-17
[15]Xiao Chang-fa、Liu Zhao-feng. J. of Applied Polymer Sci. 1990,Vol.41: 439
[16]候养全等．氨纶熔纺可行性探讨．合成纤维工业，1999，Vol22(4)：17
[17]N.S.Scheneider et al. J. Macromol Sci.Phys.. B3,1969:626
[18]K.D.Zeigel. J.Macromol Sci. Phys. B5(1),1971:11
[19]Shih-Hsing Chen et al. J. Membr. Sci.. 2000.173:99
[20]蜂须贺·久雄等．公开特许公报．特开平10-24223
[21]吴培熙、张留城．聚合物共混改性．中国轻工业出版社，1996
[22]封朴．聚合物合金．同济大学出版社，1997
[23]何曼君．高分子物理．复旦大学出版社，1990
[24]吴人洁等．高聚物表面与界面．科学出版社，1998
[25]刘决康．合成纤维．1990，3：38—42
[26]A. Vrij. Polymer Science A—2. 1968, 7:1919
[27]A. Vrij and M. W.J. Van Den Esker. J. of Polymer Science. 1975, 13:727
[28]R. J. Roe. J. Chem. Phys.. 1974, 60:4192
[29]J. Nose.. Polymer J.. 1976, 8:96
[30]吴秋林等．水处理技术．1993，19(4)：201
[31]叶凌碧等．微孔膜的截留作用机理和膜的选用，净水技术，1984，(2)：6-10
[32]王保国、蒋维钧．水处理技术．1995，21(1)：12
[33]陈洪钫、刘家淇．化工分离过程．化学工业出版社，1995
[34]林刚、周津等．膜科学与技术．1997，17(3)：50
[35]仲蕾兰、戚慰光等．合成纤维．1990，19(4)：13
[36]A. K. Fritzsche A. R. Arevalo and M. D. Moore. J. of Membrane Science. 1993, 81:199—201
[37]孙秀珍等．水处理技术．1987，13(2)：106
[38]叶凌碧等．膜分离科学与技术．1983，3(1)：54
[39]冯健、陈平．膜科学与技术．1994，14(1)：54
[40]金日光、华幼卿．高分子物理．化学工业出版社，1997：113
[41]邓本诚、李俊山．橡胶塑料共混改性．中国石化出版社，1996：15-64，235
[42]David D J. Analytical Chem. of Polyurethane,Newyork,Wiley-Interscience, 1969
[43]刘英俊、刘伯元．塑料填充改性．中国轻工业出版社，1998：106-107
[44]Einstein A. Physik. 1906.19289;1914.34,591
[45]Guth E.and SimnaR. Kolloidzschr.1936, 74. 266
[46]傅明源等．聚氨酯弹性体及其应用．化学工业出版社，1999：24
[47]董纪震等．合成纤维生产工艺学．纺织工业出版社，1993：30
[48]Houtz R C Textile Res J. 1950,20:786
[49]Olive G H and Olive S.Adv Polymer Sci 1979,32:123
[50]封严．聚氨酯系共混膜及分离性能的研究．天津工业大学硕士论文，2000：34