基于改性含氰基聚合物的复合纳滤膜的制备研究
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摘要
聚丙烯腈具有很好的热稳定性和化学稳定性，适合作为制备复合纳滤膜的基
膜。并且聚丙烯腈基膜上具有不饱和的－CN 基团，通过对其进行适当的改性，
可以将－CN 基团在碱性环境下水解生成－COOH，它能在对对’－二氨基二苯甲
烷（DDM）和均苯三甲酰氯（TMC）进行界面聚合反应时，与复合层形成具有
化学键连接的复合纳滤膜。这个创新工作尚未见报道。
本工作采用 L-S 相转化法，以 PAN 为原料、NMP 为溶剂、H3PO4和 PEG600
为添加剂，用不同的制膜配方制备了超滤膜作为基膜。对以一定配比制备基膜，
以一定浓度的 NaOH 溶液在不同温度下改性一定时间，再以一定浓度的 HCl 溶
液在室温下改性，得到用于制备纳滤膜的改性基膜。最后根据 P.W.Morgan 的界
面聚合原理，以经 NaOH 化学改性后的 PAN 超滤膜为基膜，以 DDM 和 TMC 为
主要单体，经界面聚合反应，制备了聚对对’－二氨基二苯甲烷酰胺复合纳滤膜。
用接触角测定仪表征了基膜和改性后基膜的表面亲水性，用 FTIR 研究了基
膜改性和界面聚合后的成份变化，用 ESEM 研究了基膜、改性后的基膜和界面
聚合后的复合膜的表面和断面的变化。并且表征了基膜、改性后的基膜和界面聚
合后的复合膜的纯水通量、基膜和改性后的基膜对 BSA 溶液的截留性能和界面
聚合后的复合膜对 MgSO4溶液的脱盐率。
本工作采用计算机直接实验设计方法对 PAN基膜的制膜配方和PAN基膜改
性配方进行优化设计，并采用 SAS 软件和 VB 软件对实验结果进行回归分析。
结果分析可以量化，大大减少实验次数，这是一项有意义的创新工作。
通过分析，得到针对基膜水通量、截留率和平均孔径的三个回归模型，可用
这三个模型计算预测得到各项性能的优化配方，选择其中三项性能俱优者。研究
了 PAN 浓度、添加剂种类和添加剂浓度、蒸发时间和溶剂选择对 PAN 基膜性能
的影响。得到基膜对 BSA 溶液的截留率达 93 %以上，水通量在 100 L/m2·h 以
上，平均孔径低于 40nm。
得到针对改性后基膜的水通量、对 BSA 溶液渗透通量、对 BSA 截留率和膜
表面的水接触角四个回归模型，可用这四个模型计算预测得到各项性能的优化配
方，选择其中四项性能俱优者。讨论了 NaOH 溶液浓度、改性温度和改性时间
对改性基膜性能的影响。改性后基膜的水通量达到 70 L/m2·h 以上，对 BSA 溶
液的截留率达到 83％以上，水接触角 40 度左右。
讨论了水相单体的选择、水相胺的浓度、酸接受剂的浓度、界面聚合时间、
沥干时间和后处理时间对复合膜性能的影响。得到结果如下：选择伯胺 DDM 为
水相单体，界面聚合时间 15s，沥干时间 60s，DDM 的浓度 0.1％，酸接受剂的
浓度 0.1%~0.2%。复合膜在 0.3－0.8MPa 下，对 1g/L MgSO4 溶液的脱盐率达
74.46%，水通量为 1－2 L/m2·h。
从 FTIR 谱图可以证明 PAN 基膜的表面确实有部分－CN 基被改性成－
COOH 基团。从 ESEM 电镜图和 FTIR 谱图证实了在改性的 PAN 基膜表面已经
界面聚合上了一层致密的复合层。
Polyacrylonitrile(PAN) with excellent thermostability and chemical stability was
suitable for preparing support membrane of composite nanofiltration(NF) membranes.
Furthermore, PAN support membrane had unsaturated nitrile group that can hydrolyze
and be transferred into carboxyl group under alkalescent condition through proper
modification. Interfacial polymerization took place on the membrane surface where
there were the nitrile groups, P P'-Diamino-diphenylmethane（DDM） and trimesoyl
chloride（TMC）. Consequently, composite NF membrane with chemical bonds would
be formed.
In this work support membrane of composite nanofiltration membrane was
prepared with PAN as polymer materials, N-methylpyrrolidone (NMP) as solvent,
Polyethylene glycol 600 (PEG600) or phosphoric acid (H3PO4) as additive by means
of L-S phase inversion method. Support membranes with a certain preparation
conditions and proportion of concentration of PAN, concentration of NMP and
concentration of H3PO4 were modified with certain concentration of sodium
hydroxide (NaOH) within certain time and with certain concentration of hydrochloric
acid (HCl) within certain time. Composite nanofiltration membrane was prepared
with DDM and TMC as monomers by means of interfacial polymerization according
to P.W.Morgan’s interfacial polymerization theory.
The hydrophilicity of support membrane and modified support membrane was studied by the
determination of contact angle of the membranes. Infrared spectrum (FTIR) was used to study the
component change of modified support membrane and composite nanofiltration membrane. The
microstructure of support membrane, modified support membrane and composite nanofiltration
membrane was observed using by environmental scanning electric microscope (ESEM). Water
flux of support membrane, modified support membrane and composite nanofiltration membrane,
rejection for bovine serum albumin (BSA) of support membrane and modified support membrane,
desalination for magnesium sulfate (MgSO4) of composite nanofiltration membrane were also
characterized in this work.
In this work Random-arranged experimental design with aid of computer was used to
optimize the preparation conditions of support membrane and modified support membrane. And
experimental data were calculated and regression analyzed with Statistical Analysis System (SAS)
software and Visual Basic (VB) software.
The models for water flux, rejection for BSA and average pore size of support membrane
were obtained to predict the character of membrane with different preparation conditions.
Additionally, the effects of concentration of PAN, the evaporation time of nascent membrane, kind
of additive and concentration of additive were studied. As a result, support membrane was
prepared with rejection for BSA over 93 %, water flux about 100 L/m2·h, average pore size about
40nm.
The models for water flux, rejection for BSA, flux of BSA and contact angle of the modified
membrane were obtained to predict the character of membrane with different modification
conditions. And the effects of concentration of NaOH, modification temperature and modification
time were discussed. In conclusion, support membrane was modified with rejection for BSA about
83%, water flux about 70 L/m2·h, contact angle of the modified membrane about 40。.
The effects of kind of monomer in water phase, concentration of DDM, concentration
of TMC, interfacial polymerization time, draining time and post-treatment time were
studied. And composite nanofiltration membrane was prepared with 0.1% of DDM,
0.2% of TMC, interfacial polymerization time 15s, draining time and post-treatment
time 60s, which showed the character of water flux 1-2 L/m2·h and rejection for MgSO4
74.46% at 0.3-0.8MPa.
The FTIR spectra for modified membrane confirmed that some nitrile group of the support
membrane had been transformed to carboxyl (-COOH). Furthermore, the composite film which
had polymerized on the modified membrane was confirmed by the FTIR spectr
膜。并且聚丙烯腈基膜上具有不饱和的－CN 基团，通过对其进行适当的改性，
可以将－CN 基团在碱性环境下水解生成－COOH，它能在对对’－二氨基二苯甲
烷（DDM）和均苯三甲酰氯（TMC）进行界面聚合反应时，与复合层形成具有
化学键连接的复合纳滤膜。这个创新工作尚未见报道。
本工作采用 L-S 相转化法，以 PAN 为原料、NMP 为溶剂、H3PO4和 PEG600
为添加剂，用不同的制膜配方制备了超滤膜作为基膜。对以一定配比制备基膜，
以一定浓度的 NaOH 溶液在不同温度下改性一定时间，再以一定浓度的 HCl 溶
液在室温下改性，得到用于制备纳滤膜的改性基膜。最后根据 P.W.Morgan 的界
面聚合原理，以经 NaOH 化学改性后的 PAN 超滤膜为基膜，以 DDM 和 TMC 为
主要单体，经界面聚合反应，制备了聚对对’－二氨基二苯甲烷酰胺复合纳滤膜。
用接触角测定仪表征了基膜和改性后基膜的表面亲水性，用 FTIR 研究了基
膜改性和界面聚合后的成份变化，用 ESEM 研究了基膜、改性后的基膜和界面
聚合后的复合膜的表面和断面的变化。并且表征了基膜、改性后的基膜和界面聚
合后的复合膜的纯水通量、基膜和改性后的基膜对 BSA 溶液的截留性能和界面
聚合后的复合膜对 MgSO4溶液的脱盐率。
本工作采用计算机直接实验设计方法对 PAN基膜的制膜配方和PAN基膜改
性配方进行优化设计，并采用 SAS 软件和 VB 软件对实验结果进行回归分析。
结果分析可以量化，大大减少实验次数，这是一项有意义的创新工作。
通过分析，得到针对基膜水通量、截留率和平均孔径的三个回归模型，可用
这三个模型计算预测得到各项性能的优化配方，选择其中三项性能俱优者。研究
了 PAN 浓度、添加剂种类和添加剂浓度、蒸发时间和溶剂选择对 PAN 基膜性能
的影响。得到基膜对 BSA 溶液的截留率达 93 %以上，水通量在 100 L/m2·h 以
上，平均孔径低于 40nm。
得到针对改性后基膜的水通量、对 BSA 溶液渗透通量、对 BSA 截留率和膜
表面的水接触角四个回归模型，可用这四个模型计算预测得到各项性能的优化配
方，选择其中四项性能俱优者。讨论了 NaOH 溶液浓度、改性温度和改性时间
对改性基膜性能的影响。改性后基膜的水通量达到 70 L/m2·h 以上，对 BSA 溶
液的截留率达到 83％以上，水接触角 40 度左右。
讨论了水相单体的选择、水相胺的浓度、酸接受剂的浓度、界面聚合时间、
沥干时间和后处理时间对复合膜性能的影响。得到结果如下：选择伯胺 DDM 为
水相单体，界面聚合时间 15s，沥干时间 60s，DDM 的浓度 0.1％，酸接受剂的
浓度 0.1%~0.2%。复合膜在 0.3－0.8MPa 下，对 1g/L MgSO4 溶液的脱盐率达
74.46%，水通量为 1－2 L/m2·h。
从 FTIR 谱图可以证明 PAN 基膜的表面确实有部分－CN 基被改性成－
COOH 基团。从 ESEM 电镜图和 FTIR 谱图证实了在改性的 PAN 基膜表面已经
界面聚合上了一层致密的复合层。
Polyacrylonitrile(PAN) with excellent thermostability and chemical stability was
suitable for preparing support membrane of composite nanofiltration(NF) membranes.
Furthermore, PAN support membrane had unsaturated nitrile group that can hydrolyze
and be transferred into carboxyl group under alkalescent condition through proper
modification. Interfacial polymerization took place on the membrane surface where
there were the nitrile groups, P P'-Diamino-diphenylmethane（DDM） and trimesoyl
chloride（TMC）. Consequently, composite NF membrane with chemical bonds would
be formed.
In this work support membrane of composite nanofiltration membrane was
prepared with PAN as polymer materials, N-methylpyrrolidone (NMP) as solvent,
Polyethylene glycol 600 (PEG600) or phosphoric acid (H3PO4) as additive by means
of L-S phase inversion method. Support membranes with a certain preparation
conditions and proportion of concentration of PAN, concentration of NMP and
concentration of H3PO4 were modified with certain concentration of sodium
hydroxide (NaOH) within certain time and with certain concentration of hydrochloric
acid (HCl) within certain time. Composite nanofiltration membrane was prepared
with DDM and TMC as monomers by means of interfacial polymerization according
to P.W.Morgan’s interfacial polymerization theory.
The hydrophilicity of support membrane and modified support membrane was studied by the
determination of contact angle of the membranes. Infrared spectrum (FTIR) was used to study the
component change of modified support membrane and composite nanofiltration membrane. The
microstructure of support membrane, modified support membrane and composite nanofiltration
membrane was observed using by environmental scanning electric microscope (ESEM). Water
flux of support membrane, modified support membrane and composite nanofiltration membrane,
rejection for bovine serum albumin (BSA) of support membrane and modified support membrane,
desalination for magnesium sulfate (MgSO4) of composite nanofiltration membrane were also
characterized in this work.
In this work Random-arranged experimental design with aid of computer was used to
optimize the preparation conditions of support membrane and modified support membrane. And
experimental data were calculated and regression analyzed with Statistical Analysis System (SAS)
software and Visual Basic (VB) software.
The models for water flux, rejection for BSA and average pore size of support membrane
were obtained to predict the character of membrane with different preparation conditions.
Additionally, the effects of concentration of PAN, the evaporation time of nascent membrane, kind
of additive and concentration of additive were studied. As a result, support membrane was
prepared with rejection for BSA over 93 %, water flux about 100 L/m2·h, average pore size about
40nm.
The models for water flux, rejection for BSA, flux of BSA and contact angle of the modified
membrane were obtained to predict the character of membrane with different modification
conditions. And the effects of concentration of NaOH, modification temperature and modification
time were discussed. In conclusion, support membrane was modified with rejection for BSA about
83%, water flux about 70 L/m2·h, contact angle of the modified membrane about 40。.
The effects of kind of monomer in water phase, concentration of DDM, concentration
of TMC, interfacial polymerization time, draining time and post-treatment time were
studied. And composite nanofiltration membrane was prepared with 0.1% of DDM,
0.2% of TMC, interfacial polymerization time 15s, draining time and post-treatment
time 60s, which showed the character of water flux 1-2 L/m2·h and rejection for MgSO4
74.46% at 0.3-0.8MPa.
The FTIR spectra for modified membrane confirmed that some nitrile group of the support
membrane had been transformed to carboxyl (-COOH). Furthermore, the composite film which
had polymerized on the modified membrane was confirmed by the FTIR spectr
引文
[1] Raman L P，Cheryan M，Rajagopalan N．Consider nanofiltration for membrane
separation．Chemical Engineering Progress ，1994 ，March：68-74．
[2] 邵刚．膜法水处理技术及工程实例．北京：化学工业出版社，2002．
[3] 夏冰，董声华，金秀龙，等．荷电纳滤膜的研制．水处理技术，1992，18(2)：75-83．
[4] 俞三传，高从堦，鲁学仁，等．磺化聚醚砜复合半渗透膜的研制．膜科学与技术，1995，
- 19 -
福州大学硕士学位论文
15(2)：31-38．
[5] 邢丹敏，张伟，孙同升，等．复合纳滤膜的性能研究．第二届全国膜与膜过程学术报
告会．杭州：1996．
[6] 刘淑秀，姚仕仁，郑大威，等．纳滤膜及其表面活性剂分离特性的研究．膜科学与技
术，1997，17(2)：20-23．
[7] 鲁学仁，高从堦，张建飞，等．PVDF 荷电膜制备与性能的研究．膜科学与技术．1994,
14(2)：22-25．
[8] 鲁学仁，高从堦，王更珍．丙烯酸-丙烯共聚物盐荷电膜的制备和性能的研究．水处理
技术，1997，23(1)：1-5．
[9] Raman L P，Cheryan M，Rajagopalan N．Consider nanofiltration for membrane
separations．Chemical Engineering Progress，1994，March：68~74．
[10] 蹇锡高，张守海，黛英，等．新型磺化聚醚砜酮复合纳滤膜．膜科学与技术．2001．21
（1）：11-14．
[11] 于品早，周冠生，陈小良．三醋酸纤维素中空纤维纳滤膜的研制．膜科学与技术．2001．21
（6）：1-4．
[12] 高田耕一．高分子论文集，1988，45（1）：47-53．
[13] 刘国良．条状 1520＃CA-CTA 低压反渗透膜，全国电渗析技术交流会论文（1980）．
[14] J-Y Lai， F-C．Lin，C-C Wang，D-M Wang．Effect of nonsolvent additives on the
porosity and morphology of asymmetric TPX membranes ． Journal of Membrane
Science．1996， 118：49–61．
[15] P．Radovanovic，S．W． Thiel，S．T． Hwang．Formation of asymmetric polysulfone
membranes by immersion precipitation．Part II．The effects of casting solution and gelation
bath compositions on membrane structure and skin formation．Journal of Membrane
Science．1992，65：231–246．
[16] I. Pinnau，W．J．Koros，Structures and gas separation properties of asymmetric polysulfone
membranes made by dry， wet and dry/wet phase inversion， J．Appl．Polym. Sci，1991，
43：1491–1502．
[17] I．Pinnau，W．J．Koros，A qualitative skin layer formation mechanism for membranes made
by dry/set phase inversion．J．Polym. Sci， Polym．Phys．1993，31：410–427．
[18] H. Kawakami，M Mikawa, S．Nagaoka，Gas permeability and selectivity through
asymmetric polyimide membranes．J． Appl．Polym. Sci．1996， 62：965–971．
[19] H．Kawakami，M．Mikawa，S．Nagaoka，Formation of surface skin layer of asymmetric
polyimide membranes and their gas transport properties．J．Membr．Sci．1997，137：
241–250．
[20] S．C．Pesek，W．J．Koros，Aqueous quenched asymmetric polysulfone membranes prepared
by dry/wet phase separation．J．Membr．Sci．1993， 81：71–88．
[21] In-Chul Kim， Kew-Ho Lee ， Tae-Moon Tak ． Preparation and characterization of
integrallyskinned uncharged polyetherimide asymmetric nanofiltration membrane[J].
- 20 -
基于改性含氰基聚合物的复合纳滤膜的制备研究
Journal of Membrane Science．2001，183：235–247．
[22] W．Richard Bowen_，Teodora A．Doneva，H.B．Yin．Polysulfone — sulfonated poly(ether
ether) ketone blend membranes systematic synthesis and characterization．Journal of
Membrane Science．2001，181：253–263．
[23] Liu，J．Teo，W．K，Chew，C．H，Gan， L.M．Nanofiltration membranes prepared by
direct microemulsion copolymerization using poly(ethylene oxide) macromonomer as a
polymerizable surfactant．Journal of Applied Polymer Science．2000，77：2785-2794．
[24] 高从堦等．荷电的反渗透膜和超滤膜．水处理技术．1987．13(5)：140-145．
[25] Miyama H，Fujii N，Kuwano A，Nagaoka S，Mori Y，Noishiki Y．J Biomed Mater Res，
1986，20：895．
[26] Miyama H，Tanaka K，Nosaka Y，Fujii N，Tanzsawa H，Nagaoka S．J Appl Polym Sci，
1988，36：925．
[27] 邵刚．膜法水处理技术及工程实例．北京：化学工业出版社．2002．
[28] J E Cadotte，R W Schaffenbery，R J Peterson，Proc．Int．Mem br Conf on the 25 th
Anniversary of Membrane Research in Canada，NRCC 1986：203．
[29] R J Peterson．Composise reverse osmosis and nanofiltration membranes．Journal of
Membrane Science．1993．83：81-150．
[30] M Kurihara， Y H im esh im a．Polymer J．1991，25(5)：513-520．
[31] K Ikeda，etal．Abstr Int Congr Membr Processes Tokyo，1987：6-17．
[32] H Ohya， Maku(Membrane)，1985，10：101．
[33] R J Peterson．Composise reverse osmosis and nanofiltration membranes．Journal of
Membrane Science．1993，83：81-150．
[34] 鲁学仁，高从堦等．膜科学与技术，1994，14(2)：22．
[35] 梁雪梅，陆晓峰，刘光全，等．界面缩聚法制备聚芳酯复合纳滤膜的研究Ⅰ基膜的制
备．华东理工大学学报，1999，25：297-301．
[36] 梁雪梅，陆晓峰，刘光全，等．界面缩聚法制备聚芳酯复合纳滤膜的研究Ⅱ界面缩聚
对复合纳滤膜的影响．华东理工大学学报，1999，25：394-397．
[37] 陆晓峰，施柳青，卞晓锴．NF 系列复合纳滤膜的制备及结构性能的研究．膜科学与
技术，2001，21：11-15．
[38] 蹇锡高，张守海，戴英等．新型磺化聚醚砜酮复合纳滤膜．膜科学与技术．2001，21：
11-14．
[39] 俞三传，金可勇，潘巧明等．聚哌嗪酰胺复合纳滤膜研制．膜科学与技术．2001，21：
1-3．
[40] NAM-WUN OH，JONGGEON JEGAL，KEW-HO LEE．Preparation and Characterization
of Nanofiltration Composite Membranes Using Polyacrylonitrile(PAN) Ⅰ preparation and
Modification of PAN Supports．Journal of Applied Polymer Science，2001，80：
1854-1862．
- 21 -
福州大学硕士学位论文
[41] NAM-WUN OH，JONGGEON JEGAL，KEW-HO LEE．Preparation and Characterization
of Nanofiltration Composite Membranes Using Polyacrylonitrile(PAN) Ⅱ preparation and
Characterization of Polyamide Composite Membrane．Journal of Applied Polymer
Science，2001，80：2729-2738．
[42] S. Bequet a，T．Abenoza a，P．Aptel a，J-M．Espenan b，J-C． Remigy a，A. R i c a
r d a．New composite membrane for water softening．Desalination．2000，131：299-305．
[43] Deepak A．Musale，Ashwani Kumar．Effects of surface crosslinking on sieving
characteristics of chitosan:poly(acrylonitrile) composite nanofiltration membranes．Separa-
tion and Purification Technology．2000，21：27–38．
[44] Jegal, Jonggeon，Oh，Nam-Wun，Park，Duck-Soon，Lee， Kew-Ho．Characteristics of
the nanofiltration composite membranes based on PVA and sodium alginate． Journal of
Applied Polymer Science．Mar 2001，79：2471-2479．
[45] Sforca，M．L．Nunes，S．P．Peinemann，K．-V．Composite nanofiltration membranes
prepared by in situ polycondensation of amines in a poly(ethylene oxide-b-amide)
layer．Journal of Membrane Science．1997，135：179-186．
[46] Raman L P，Cheryan M，Rajagopalan N．Consider nanofiltration for membrane
separations．Chemical Engineering Progress，1994，March：68-74．
[47] Winston H W S．Sirkar K K，eds．Membrane handbook．New York：Van Mostrand
Reinhold，1992．
[48] Vrijenhoek，Eric M．；Waypa，John J．Arsenic removal from drinking water by a loose
nanofiltration membrane．Desalination，2000，130：265-277．
[49] Mavrov，V．；Chmiel，H．；Belieres，E．Spent process water desalination and organic
removal by membranes for water reuse in the food industry．Desalination．2001，138：
65-74．
[50] Khalik，Agus；Praptowidodo，V．S．Nanofiltration for drinking water production from deep
well water．Desalination．2000，132：287-292．
[51] Kettunen，Riitta；Keskitalo，Pertti．Combination of membrane technology and limestone
filtration to control drinking water quality．Desalination．2000，131：271-283．
[52] Oh， J．I；Yamamoto，K．；Kitawaki， H．；Nakao， S．；Sugawara，T．；Rahman，
M．M．；Rahman，M．H．Application of low-pressure nanofiltration coupled with a bicycle
pump for the treatment of arsenic-contaminated groundwater．Desalination，2000，132：
307-314．
[53] Boussahel，R．；Bouland，S．；Moussaoui，K.M．；Montiel，A. Removal of pesticide
residues in water using the nanofiltration process．Desalination．2000．132： 205-209．
[54] Glucina，K．；Alvarez，A．；Laine，J．M．Assessment of an integrated membrane system
for surface water treatment． Desalination．2000，132：73-82．
[55] Afonso ， M.DYanez ， R.B ． Nanofiltration of wastewater from the fishmeal
industry．Desalination．2001，139：429．
- 22 -
基于改性含氰基聚合物的复合纳滤膜的制备研究
[56] Mavrov，V；Belieres，E．Reduction of water consumption and wastewater quantities in the
food industry by water recycling using membrane processes．Desalination. 2000，131：
75-86．
[57] Van der Bruggen，B De Vreese，I Vandecasteele，C．Water reclamation in the textile
industry: Nanofiltration of dye baths for wool dyeing．Industrial and Engineering Chemistry
Research．2001，40： 3973-3978．
[58] Koyuncu，I Kural，E Topacik，D Pilot scale nanofiltration membrane separation for
waste management in textile industry．Water Science and Technology．2001，43：233-240
[59] 方开泰，马长兴．正交与均匀试验设计．北京：科学出版社，2001．
[60] 方开泰．均匀设计与均匀设计表．北京：科学出版社，1994．
[61] 胡良平．现代统计学与 SAS 应用．北京：军事医学科学出版社，2002．
[62] 林维宣．试验设计方法．大连海事大学出版社．1995．
[63] 高齐圣，隋树林，孟宪德．均匀设计在橡胶配方研究中的应用．橡胶工业．1996，43：
583～586．
[64] 曾云龙．均匀设计在制备药物中的应用．桂林医学院学报．1997，10(4)：519～520．
[65] 刘杨，钱新民，高培基．应用均匀设计方法改进光合细菌类胡萝卜素生．山东大学学
报．1994，19(2)： 224～229．
[66] 张学中．计算机直接试验设计．数理统计与管理，1995，14：43-46．
[67] 宋玉军，刘福安，杨勇等．用直接实验设计方法优化聚砜超滤膜制膜工艺．纺织科学
研究，1999，3：13-17．
[68] 吴开芬，王静荣，王正军等．高通量聚丙烯腈超滤膜的研究．膜科学与技术，1999，
19(3)：48-50．
[69] 王兰娟，张才菁．聚丙烯腈超滤膜铸膜液配方的优选试验．石油大学学报（自然科学
版），1997，21：67-69．
[70] Stoiko Perov，Penka Petkova．Preparation of polyacrylonitrile ultrafiltration membranes
from polymer solutions containing glycerol．Journal of Membrane Science，1991，64：
183-187．
[71] 何昌生．聚丙烯腈超滤膜表面结构的初步探讨．水处理技术，1987，13：260-266．
[72] 张旺玺．聚丙烯腈纤维的改性．合成技术及应用，1998，15：27-31．
[73] 王保国，蒋维钧．聚丙烯腈中空纤维超滤膜．水处理技术，1995，21：11-14．
[74] DEEPAK A．MUSALE，ASHWANI KUMAR．Solvent and pH Resistance of Surface
Crosslinked Chitosan/Poly(acrylonitrile) Composite Nanofiltration Membranes．Journal of
Applied Polymer Science，2000，77：1782-1793．
[75] Deepak A．Musale，Ashwani Kumar．Effects of surface crosslinking on sieving charact-
eristics of chitosan/poly(acrylonitrile) composite nanofiltration membranes．Separation and
Purification Technology，2000，21：27–38．
[76] 董大均．SAS-统计分析软件应用指南．北京：电子工业出版社，1993．
separation．Chemical Engineering Progress ，1994 ，March：68-74．
[2] 邵刚．膜法水处理技术及工程实例．北京：化学工业出版社，2002．
[3] 夏冰，董声华，金秀龙，等．荷电纳滤膜的研制．水处理技术，1992，18(2)：75-83．
[4] 俞三传，高从堦，鲁学仁，等．磺化聚醚砜复合半渗透膜的研制．膜科学与技术，1995，
- 19 -
福州大学硕士学位论文
15(2)：31-38．
[5] 邢丹敏，张伟，孙同升，等．复合纳滤膜的性能研究．第二届全国膜与膜过程学术报
告会．杭州：1996．
[6] 刘淑秀，姚仕仁，郑大威，等．纳滤膜及其表面活性剂分离特性的研究．膜科学与技
术，1997，17(2)：20-23．
[7] 鲁学仁，高从堦，张建飞，等．PVDF 荷电膜制备与性能的研究．膜科学与技术．1994,
14(2)：22-25．
[8] 鲁学仁，高从堦，王更珍．丙烯酸-丙烯共聚物盐荷电膜的制备和性能的研究．水处理
技术，1997，23(1)：1-5．
[9] Raman L P，Cheryan M，Rajagopalan N．Consider nanofiltration for membrane
separations．Chemical Engineering Progress，1994，March：68~74．
[10] 蹇锡高，张守海，黛英，等．新型磺化聚醚砜酮复合纳滤膜．膜科学与技术．2001．21
（1）：11-14．
[11] 于品早，周冠生，陈小良．三醋酸纤维素中空纤维纳滤膜的研制．膜科学与技术．2001．21
（6）：1-4．
[12] 高田耕一．高分子论文集，1988，45（1）：47-53．
[13] 刘国良．条状 1520＃CA-CTA 低压反渗透膜，全国电渗析技术交流会论文（1980）．
[14] J-Y Lai， F-C．Lin，C-C Wang，D-M Wang．Effect of nonsolvent additives on the
porosity and morphology of asymmetric TPX membranes ． Journal of Membrane
Science．1996， 118：49–61．
[15] P．Radovanovic，S．W． Thiel，S．T． Hwang．Formation of asymmetric polysulfone
membranes by immersion precipitation．Part II．The effects of casting solution and gelation
bath compositions on membrane structure and skin formation．Journal of Membrane
Science．1992，65：231–246．
[16] I. Pinnau，W．J．Koros，Structures and gas separation properties of asymmetric polysulfone
membranes made by dry， wet and dry/wet phase inversion， J．Appl．Polym. Sci，1991，
43：1491–1502．
[17] I．Pinnau，W．J．Koros，A qualitative skin layer formation mechanism for membranes made
by dry/set phase inversion．J．Polym. Sci， Polym．Phys．1993，31：410–427．
[18] H. Kawakami，M Mikawa, S．Nagaoka，Gas permeability and selectivity through
asymmetric polyimide membranes．J． Appl．Polym. Sci．1996， 62：965–971．
[19] H．Kawakami，M．Mikawa，S．Nagaoka，Formation of surface skin layer of asymmetric
polyimide membranes and their gas transport properties．J．Membr．Sci．1997，137：
241–250．
[20] S．C．Pesek，W．J．Koros，Aqueous quenched asymmetric polysulfone membranes prepared
by dry/wet phase separation．J．Membr．Sci．1993， 81：71–88．
[21] In-Chul Kim， Kew-Ho Lee ， Tae-Moon Tak ． Preparation and characterization of
integrallyskinned uncharged polyetherimide asymmetric nanofiltration membrane[J].
- 20 -
基于改性含氰基聚合物的复合纳滤膜的制备研究
Journal of Membrane Science．2001，183：235–247．
[22] W．Richard Bowen_，Teodora A．Doneva，H.B．Yin．Polysulfone — sulfonated poly(ether
ether) ketone blend membranes systematic synthesis and characterization．Journal of
Membrane Science．2001，181：253–263．
[23] Liu，J．Teo，W．K，Chew，C．H，Gan， L.M．Nanofiltration membranes prepared by
direct microemulsion copolymerization using poly(ethylene oxide) macromonomer as a
polymerizable surfactant．Journal of Applied Polymer Science．2000，77：2785-2794．
[24] 高从堦等．荷电的反渗透膜和超滤膜．水处理技术．1987．13(5)：140-145．
[25] Miyama H，Fujii N，Kuwano A，Nagaoka S，Mori Y，Noishiki Y．J Biomed Mater Res，
1986，20：895．
[26] Miyama H，Tanaka K，Nosaka Y，Fujii N，Tanzsawa H，Nagaoka S．J Appl Polym Sci，
1988，36：925．
[27] 邵刚．膜法水处理技术及工程实例．北京：化学工业出版社．2002．
[28] J E Cadotte，R W Schaffenbery，R J Peterson，Proc．Int．Mem br Conf on the 25 th
Anniversary of Membrane Research in Canada，NRCC 1986：203．
[29] R J Peterson．Composise reverse osmosis and nanofiltration membranes．Journal of
Membrane Science．1993．83：81-150．
[30] M Kurihara， Y H im esh im a．Polymer J．1991，25(5)：513-520．
[31] K Ikeda，etal．Abstr Int Congr Membr Processes Tokyo，1987：6-17．
[32] H Ohya， Maku(Membrane)，1985，10：101．
[33] R J Peterson．Composise reverse osmosis and nanofiltration membranes．Journal of
Membrane Science．1993，83：81-150．
[34] 鲁学仁，高从堦等．膜科学与技术，1994，14(2)：22．
[35] 梁雪梅，陆晓峰，刘光全，等．界面缩聚法制备聚芳酯复合纳滤膜的研究Ⅰ基膜的制
备．华东理工大学学报，1999，25：297-301．
[36] 梁雪梅，陆晓峰，刘光全，等．界面缩聚法制备聚芳酯复合纳滤膜的研究Ⅱ界面缩聚
对复合纳滤膜的影响．华东理工大学学报，1999，25：394-397．
[37] 陆晓峰，施柳青，卞晓锴．NF 系列复合纳滤膜的制备及结构性能的研究．膜科学与
技术，2001，21：11-15．
[38] 蹇锡高，张守海，戴英等．新型磺化聚醚砜酮复合纳滤膜．膜科学与技术．2001，21：
11-14．
[39] 俞三传，金可勇，潘巧明等．聚哌嗪酰胺复合纳滤膜研制．膜科学与技术．2001，21：
1-3．
[40] NAM-WUN OH，JONGGEON JEGAL，KEW-HO LEE．Preparation and Characterization
of Nanofiltration Composite Membranes Using Polyacrylonitrile(PAN) Ⅰ preparation and
Modification of PAN Supports．Journal of Applied Polymer Science，2001，80：
1854-1862．
- 21 -
福州大学硕士学位论文
[41] NAM-WUN OH，JONGGEON JEGAL，KEW-HO LEE．Preparation and Characterization
of Nanofiltration Composite Membranes Using Polyacrylonitrile(PAN) Ⅱ preparation and
Characterization of Polyamide Composite Membrane．Journal of Applied Polymer
Science，2001，80：2729-2738．
[42] S. Bequet a，T．Abenoza a，P．Aptel a，J-M．Espenan b，J-C． Remigy a，A. R i c a
r d a．New composite membrane for water softening．Desalination．2000，131：299-305．
[43] Deepak A．Musale，Ashwani Kumar．Effects of surface crosslinking on sieving
characteristics of chitosan:poly(acrylonitrile) composite nanofiltration membranes．Separa-
tion and Purification Technology．2000，21：27–38．
[44] Jegal, Jonggeon，Oh，Nam-Wun，Park，Duck-Soon，Lee， Kew-Ho．Characteristics of
the nanofiltration composite membranes based on PVA and sodium alginate． Journal of
Applied Polymer Science．Mar 2001，79：2471-2479．
[45] Sforca，M．L．Nunes，S．P．Peinemann，K．-V．Composite nanofiltration membranes
prepared by in situ polycondensation of amines in a poly(ethylene oxide-b-amide)
layer．Journal of Membrane Science．1997，135：179-186．
[46] Raman L P，Cheryan M，Rajagopalan N．Consider nanofiltration for membrane
separations．Chemical Engineering Progress，1994，March：68-74．
[47] Winston H W S．Sirkar K K，eds．Membrane handbook．New York：Van Mostrand
Reinhold，1992．
[48] Vrijenhoek，Eric M．；Waypa，John J．Arsenic removal from drinking water by a loose
nanofiltration membrane．Desalination，2000，130：265-277．
[49] Mavrov，V．；Chmiel，H．；Belieres，E．Spent process water desalination and organic
removal by membranes for water reuse in the food industry．Desalination．2001，138：
65-74．
[50] Khalik，Agus；Praptowidodo，V．S．Nanofiltration for drinking water production from deep
well water．Desalination．2000，132：287-292．
[51] Kettunen，Riitta；Keskitalo，Pertti．Combination of membrane technology and limestone
filtration to control drinking water quality．Desalination．2000，131：271-283．
[52] Oh， J．I；Yamamoto，K．；Kitawaki， H．；Nakao， S．；Sugawara，T．；Rahman，
M．M．；Rahman，M．H．Application of low-pressure nanofiltration coupled with a bicycle
pump for the treatment of arsenic-contaminated groundwater．Desalination，2000，132：
307-314．
[53] Boussahel，R．；Bouland，S．；Moussaoui，K.M．；Montiel，A. Removal of pesticide
residues in water using the nanofiltration process．Desalination．2000．132： 205-209．
[54] Glucina，K．；Alvarez，A．；Laine，J．M．Assessment of an integrated membrane system
for surface water treatment． Desalination．2000，132：73-82．
[55] Afonso ， M.DYanez ， R.B ． Nanofiltration of wastewater from the fishmeal
industry．Desalination．2001，139：429．
- 22 -
基于改性含氰基聚合物的复合纳滤膜的制备研究
[56] Mavrov，V；Belieres，E．Reduction of water consumption and wastewater quantities in the
food industry by water recycling using membrane processes．Desalination. 2000，131：
75-86．
[57] Van der Bruggen，B De Vreese，I Vandecasteele，C．Water reclamation in the textile
industry: Nanofiltration of dye baths for wool dyeing．Industrial and Engineering Chemistry
Research．2001，40： 3973-3978．
[58] Koyuncu，I Kural，E Topacik，D Pilot scale nanofiltration membrane separation for
waste management in textile industry．Water Science and Technology．2001，43：233-240
[59] 方开泰，马长兴．正交与均匀试验设计．北京：科学出版社，2001．
[60] 方开泰．均匀设计与均匀设计表．北京：科学出版社，1994．
[61] 胡良平．现代统计学与 SAS 应用．北京：军事医学科学出版社，2002．
[62] 林维宣．试验设计方法．大连海事大学出版社．1995．
[63] 高齐圣，隋树林，孟宪德．均匀设计在橡胶配方研究中的应用．橡胶工业．1996，43：
583～586．
[64] 曾云龙．均匀设计在制备药物中的应用．桂林医学院学报．1997，10(4)：519～520．
[65] 刘杨，钱新民，高培基．应用均匀设计方法改进光合细菌类胡萝卜素生．山东大学学
报．1994，19(2)： 224～229．
[66] 张学中．计算机直接试验设计．数理统计与管理，1995，14：43-46．
[67] 宋玉军，刘福安，杨勇等．用直接实验设计方法优化聚砜超滤膜制膜工艺．纺织科学
研究，1999，3：13-17．
[68] 吴开芬，王静荣，王正军等．高通量聚丙烯腈超滤膜的研究．膜科学与技术，1999，
19(3)：48-50．
[69] 王兰娟，张才菁．聚丙烯腈超滤膜铸膜液配方的优选试验．石油大学学报（自然科学
版），1997，21：67-69．
[70] Stoiko Perov，Penka Petkova．Preparation of polyacrylonitrile ultrafiltration membranes
from polymer solutions containing glycerol．Journal of Membrane Science，1991，64：
183-187．
[71] 何昌生．聚丙烯腈超滤膜表面结构的初步探讨．水处理技术，1987，13：260-266．
[72] 张旺玺．聚丙烯腈纤维的改性．合成技术及应用，1998，15：27-31．
[73] 王保国，蒋维钧．聚丙烯腈中空纤维超滤膜．水处理技术，1995，21：11-14．
[74] DEEPAK A．MUSALE，ASHWANI KUMAR．Solvent and pH Resistance of Surface
Crosslinked Chitosan/Poly(acrylonitrile) Composite Nanofiltration Membranes．Journal of
Applied Polymer Science，2000，77：1782-1793．
[75] Deepak A．Musale，Ashwani Kumar．Effects of surface crosslinking on sieving charact-
eristics of chitosan/poly(acrylonitrile) composite nanofiltration membranes．Separation and
Purification Technology，2000，21：27–38．
[76] 董大均．SAS-统计分析软件应用指南．北京：电子工业出版社，1993．