CN103635242A - 嵌入分子笼型化合物的薄膜复合膜 - Google Patents
嵌入分子笼型化合物的薄膜复合膜 Download PDFInfo
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- CN103635242A CN103635242A CN201280033055.1A CN201280033055A CN103635242A CN 103635242 A CN103635242 A CN 103635242A CN 201280033055 A CN201280033055 A CN 201280033055A CN 103635242 A CN103635242 A CN 103635242A
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Images
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Abstract
载体上的聚合物膜,其中聚合物膜包含共价结合于分子笼型化合物上的交联聚合物。还公开了制备聚合物膜的界面聚合方法。
Description
技术领域
本公开内容涉及包含化学结合的分子笼型化合物的聚合物膜。该膜可用于例如过滤应用中,或者应用于另一膜上以在其上形成性能增强层。
背景技术
膜技术如微滤(MF)、超滤(UF)、纳米过滤(NF)和反渗透(RO)广泛用于水净化,因为它们是能量有效、有成本效益的且操作简单。基于反渗透(RO)的膜过滤是海水或含盐水脱盐的最有希望方法之一,包含在多孔载体上的超薄活性层的薄膜复合物(TFC)或薄膜纳米复合物(TFNC)膜广泛用于该应用。在TFC膜中,活性层在控制水和盐传输性能中起重要作用,同时载体层提供足够的机械强度以容忍高操作压力。通过间苯二胺(MPD)和均苯三甲酰氯(trimesoyl chloride,TMC)的界面聚合而制备的交联芳族聚酰胺在商业脱盐膜中用作活性层。
通过膜的增强的水通量贡献于降低膜过滤方法期间的总操作能。尽管一些芳族聚酰胺TFC膜具有非常高的脱盐率(≥99%),开发新的活性层以改善水通量,同时保持该高脱盐率。例如,在经交联的多胺膜中嵌入物理地并入聚合物基质中的纳米颗粒如沸石或二氧化硅。
发明概述
物理并入的纳米颗粒在膜过滤方法期间会从膜活性层中沥出。在本公开内容中,在界面聚合期间可化学结合在芳族聚酰胺上的官能化纳米材料形成具有增强的RO性能的更耐久的纳米复合物活性层。一般而言,本发明涉及具有并入化学结合的分子笼型化合物的活性层的薄膜。合适的分子笼型化合物包含当薄膜使用界面聚合方法形成时可与酰基卤反应物反应的反应性官能。
例如,如果化学结合在活性层上的分子笼型化合物具有比水分子直径更大的内部空穴,则通过活性层的水渗透速度可提高,这可增强通过活性层的水通量。通过控制结合在活性层上的分子笼型化合物的量,可基本保持活性层的表面密度以保持层的有利脱盐性能。
在一个实施方案中,本发明涉及载体上的聚合物膜,其中聚合物膜包含交联聚合物,且其中交联聚合物共价结合在分子笼型化合物上。
在另一实施方案中,本发明涉及一种方法,所述方法包括:
a)将载体膜浸入水溶液中,其中水溶液包含胺化合物和官能化笼型化合物,其中笼型化合物选自POSS、环糊精、杯芳烃及其组合;
b)将载体膜从水溶液中取出;和
c)将载体膜浸入包含酰基卤化合物的有机溶液中,其中有机溶液与水不溶混。
本发明一个或多个实施方案的细节描述于附图和以下说明中。本发明的其它特征、目的和优点会从说明书和图以及权利要求书中获悉。
附图简述
图1为TFC过滤膜的一个实施方案的截面层示意图。
图2为可用于生产本公开内容所述聚酰胺TFC膜的界面聚合程序的一个实施方案的示意图。
图3为参比聚酰胺(REF)和含POSS聚酰胺膜的水通量(左)和脱盐率(右)数据的图。POSS0.3和POSS0.5分别表示间苯二胺水溶液内0.3%(w/v)和0.5%(w/v)A-POSS载荷。
图4为参比聚酰胺和包含0.01%(w/v)和0.05%(w/v)A-POSS的纳米复合物聚酰胺膜的水通量(左)和脱盐率(右)数据的图。
图5为用于本申请的工作实施例中的官能化POSS化合物的示意图。
图中类似的符号表示类似的要素。
发明详述
图1阐述包含载体12的TFC膜10。提供膜结构的结构完整性的载体12可包含多种多孔层,且不限于图1所示排列。
在图1所示实施方案中,载体12包含如果需要的话性质上可以为纤维状的挠性多孔有机聚合物材料的载体网14。纤维支持或载体材料14为具有微米范围内的直径的纺粘聚合物(例如聚酯)纤维的纸状网。
多孔载体膜16居于载体14上。多孔载体膜16可取决于TFC膜10的意欲应用宽泛地变化。在一个实施方案中,多孔载体膜16为可用于支撑用界面聚合方法制备的RO/NF膜的超滤膜。多孔载体膜可以为挠性或刚性的,并可包含有机材料、无机材料、金属材料或前述材料的组合。用于多孔载体膜的典型有机材料包括乙酸纤维素、硝酸纤维素、再生纤维素、聚砜、聚醚砜、聚哌嗪酰胺(例如以商品名FILMTEC由Dow Chemical,Midland,MI得到的那些)、聚丙烯腈和共聚物、径迹蚀刻聚酯(例如以商品名CYCLOPORE由Whatman Ltd出售的那些)、聚碳酸酯(例如以商品名NUCLEPORE由Whatman Ltd出售的那些)、聚(偏二氟乙烯)、聚丙烯、尼龙6,6、聚(四氟乙烯)(例如以商品名PORO-TEX和PARA-TEL由DeWAL Industries出售的那些)及前述材料的组合。用于多孔载体膜的典型无机材料包括纳米孔氧化铝(Al2O3)(例如以商品名ANOPORE由Whatman Ltd.出售的那些)、氧化铍(BeO)、二氧化钛(TiO2)、氧化锆(ZrO2)、二氧化硅(SiO2)、氧化镁(MgO)、氧化钙(CaO)、三氧化二钇(Y2O3)、氧化锶(SrO)、氧化镧(La2O3)、二氧化铪(HfO2)、铁氧化物、氧化锰(MnO)、碳化物、氮化物、硅化物及前述材料的组合。用于多孔载体膜的典型金属包括例如镍、镍合金和不锈钢。
多孔载体膜16优选具有约1至约1000nm、约1-100nm(0.1μm)、约1-10nm、约2至约8nm,甚至更优选约3至约6nm的平均孔径。在该申请中,术语“孔”指从多孔载体膜的一面延伸至相对面的规则和不规则空隙和/或通道。微滤(MF)载体膜具有约0.1μm的平均孔尺寸和约500,000道尔顿的截留分子量。超滤(UF)载体膜具有约0.01至约0.1μm的平均孔尺寸和约1,000-500,000道尔顿的截留分子量。纳米过滤(NF)载体膜具有约0.001至约0.01μm的平均孔尺寸和约100道尔顿至约1000道尔顿的截留分子量。反渗透(RO)载体膜具有约0.001μm或更小的平均孔尺寸和小于约100道尔顿的截留分子量。以下实施例中所用聚(砜)(PSF)超滤载体膜的孔径大小为约1至约10nm。
多孔载体膜16可具有1μm-10mm,更特别地1-100μm,更特别地1-80μm,甚至更特别地1-50μm的厚度。
再次参考图1,活性层20居于载体12上。图2为可用于形成TFC膜10的活性层20的界面聚合(IP)反应顺序的示意图。然而,图2仅显示一个实例,且本发明不限于该具体程序或操作顺序。
在图2所示实施方案中,TFC膜10的活性层20衍生自载体层16(图1)上水性化学混合物(A)与有机化学混合物(B)之间的界面聚合(IP)反应。水性化学混合物(A)和有机化学混合物(B)是不溶混的。当混合物(A)和(B)接触时,不溶混意指(A)与(B)之间存在界面。化学混合物(A)和(B)可独立地为溶液、分散体或其组合。优选(A)和(B)都为溶液,并在以下讨论中称为溶液。
水性化学混合物(A)包含式1所示单体多胺反应物22:
R(NH2)z 式1
其中式1中的R表示选自脂族、脂环族、芳族、杂环基团及其组合的有机基团,且z表示2或更大、2-20或2-8的整数。在该申请中,通过端点列举数字范围包括该范围内所包含的所有数字(例如1-5包括1、1.5、2、2.75、3、3.80、4、5等)。在式1化合物的一些实施方案中,R包括芳族基团,更优选由一个或多个芳族基团组成。
在一些实施方案中,式1单体多胺反应物中的R表示具有2-30个碳原子,或2-20个碳原子,或6-20个碳原子的有机基团。例如R可包括选自苯环、萘环、环己烷环、金刚烷(admanthane)环、降冰片烷环及其组合的芳族有机基团。在一些实施方案中,式1中的R为苯环,且z等于2。
再次参考图2,水性化学混合物(A)进一步包含至少一种官能化分子笼型化合物30。分子笼型化合物包含笼和笼状结构,其具有结合的原子或分子排列以产生完全或基本受限空间,其在本文中称为内部空穴。具有基本受限空间的结构包括例如具有一个或多个开口端的圆柱形结构。内部空穴的尺寸可取决于活性层的所需性能广泛地变化,并可选择以增强活性层的孔隙率。例如,为增强通过膜的水通量,可使用内径比水分子的直径(约0.28nm)更大的内部空穴。在并入分子笼型化合物以后,预期通过活性层的水渗透速度高于缺乏分子笼型化合物的传统交联聚酰胺层的水通量。通过控制活性层中分子笼型化合物的载量,可使活性层的顶面足够致密以保持高脱盐率。
合适的分子笼型化合物显示于下表1中,包括但不限于环糊精、杯芳烃和POSS化合物。表1进一步包括这些官能化笼型化合物类型的成员的内部空穴的典型近似内径。表1所列官能化分子笼型化合物为基本水溶性的,且在其顶部包含能够与有机化学混合物(B)中的酰基卤反应物24反应以将分子笼型化合物化学结合在交联活性层20(图2)上的官能团R。
表1
在表1所述化合物中,R独立地选自含胺和含醇结构部分。R优选独立地选自(L)n-OH、(L)n-NH2或(L)n-NH2HX,且其中L为连接基团,例如亚烷基、亚芳基、甲硅烷氧基、醚键或其组合,n为0-10的整数,优选0-6的整数,且X为卤素。
例如,可合成具有笼状结构的POSS化合物以包含在其笼顶的多种连接基团和/或官能团(在本文中通常称为官能团)。POSS化合物上的连接基团和/或官能团可包含适于使POSS单体聚合或接枝在聚合物链上的反应性官能,以及连接在官能团上和/或增强例如POSS化合物与特定聚合物体系的溶解度和相容性的非反应性官能。连接基团和/或官能团可用于使POSS化合物与多种共聚单体聚合。
在本申请中,术语POSS化合物指具有以下结构(I)、(II)或(III)的树脂,其中:
由式T8 R表示,其中T表示RSiO3/2;
由式T10 R表示,其中T表示RSiO3/2;
由式T12 R表示,其中T表示RSiO3/2。
在以上结构(I)-(III)中的每一个中,R独立地选自含胺和含醇结构部分。R优选独立地选自(L)n-OH、(L)n-NH2或(L)n-NH2HX,且其中L为连接基团,例如亚烷基、亚芳基、甲硅烷氧基、醚键或其组合,n为0-10的整数,优选0-6,且X为卤素。
以上结构(I)-(III)中的官能化POSS化合物可由通式Tm R表示,其中m等于8、10或12。当m=8时,化合物的常用名为八(N)硅倍半氧烷,其中N为R基团的名称。
在一些实施方案中,用于制备本发明薄膜的配制剂可包含具有不同R基团的T8 R POSS化合物的混合物、具有不同R基团的T10 R POSS化合物的混合物、和/或具有不同R基团的T12 R POSS化合物的混合物。在一些实施方案中,本发明组合物可包含T8 R、T10 R和T12 R POSS化合物的混合物。
表1的分子笼型化合物上的官能团和上述POSS化合物上的官能团R可独立地选自可与图2的有机化学混合物(B)中的酰基卤反应的任何官能团。合适的实例包括但不限于含胺结构部分和含醇结构部分。例如,发现含胺结构部分如(CH2)3NH2特别适于与制备过滤膜的界面聚合方法中常用的酰基卤反应。
特别优选的POSS化合物包括以上结构式(III)的化合物,其中官能团包含含胺结构部分。合适的实例显示于图5中,其中官能团为含胺结构部分,例如(CH2)3NH2和(CH2)3NH2HCl。合适的官能化POSS化合物可由Hybrid Plastics Co.,Hattiesburg,MS得到。
溶液(A)中笼型化合物的量可取决于活性层的所需性能而宽泛地变化,但通常为约0.01-0.5%w/v(官能化笼型化合物的重量比水溶液(A)的体积,以g/ml为单位测量),优选约0.01至约0.3%,更优选约0.01至约0.05%。
可任选将碱加入水溶液(A)中以改善单体多胺反应物的溶解度和清除界面聚合期间产生的计划外酸性反应。水溶液(A)中所用碱可宽泛地变化,并可包括有机碱、无机碱及其组合。例如,溶液(A)中的碱可包括无机氢氧化物、有机氢氧化物、碳酸盐、碳酸氢盐、硫化物、胺及其组合。合适的碱包括但不限于NaOH、KOH、Ca(OH)2、Na2CO3、K2CO3、CaCO3、NaHCO3、KHCO3、三乙胺、吡啶、氢氧化四甲铵及其组合。
图2的界面聚合方法中的有机化学混合物(B)包含式2表示的单体多官能酰基卤反应物:
其中式2中的R1表示选自脂族、脂环族、芳族、杂环基团及其组合的有机基团,X为选自氟、氯、溴和碘的卤素,且p表示2或更大、2-20或2-8的整数。
在一些实施方案中,式2的多官能酰基卤反应物中的R1表示具有1-30个碳原子,或1-20个碳原子,或1-15个碳原子的有机基团。在一些实施方案中,在式2的多官能酰基卤反应物中,R1可包含选自苯环、萘环、环己烷环、金刚烷环、降冰片烷及其组合的有机基团。
在一些实施方案中,式2的多官能酰基卤反应物中的R1表示式3所示有机基团:
其中W表示选自CH2、O、S、C=O、SO2、C(CH3)2、C(CF3)2及其组合的有机基团,s表示0或1的整数,且一价COX化学键合在苯环上,其中X独立地选自氟、氯、溴和碘。
在一些实施方案中,溶液(B)中的单体多官能酰基卤反应物包含至少一种式4所示二价有机化合物或式5所示三价有机化合物:
其中R23、R24、R25、R26和R27各自独立地选自一价COX,其中X独立地选自氟、氯、溴和碘。
在其它实施方案中,溶液(B)中的单体多官能酰基卤反应物包含至少一种选自式6所示三价有机化合物或式7所示二价有机化合物的化合物:
其中R28、R29、R30、R31和R32各自独立地选自一价COX,且X独立地选自氟、氯、溴和碘,其中W表示选自CH2、O、S、C=O、SO2、C(CH3)2、C(CF3)2及其组合的有机基团,且其中s表示0或1的整数。
在其它实施方案中,溶液(B)中的单体多官能酰基卤反应物包含选自式37-61中的任何化合物及其组合的化合物:
有机溶液(B)中所用有机溶剂可宽泛地变化,并可包括具有1-20个碳原子,或1-16个碳原子,或1-12个碳原子的有机化合物。合适的有机溶剂包括但不限于正己烷、正庚烷、正辛烷、正癸烷、正十二烷、四氯化碳、氯仿、二氯甲烷、氯苯、二甲苯、甲苯、苯及其组合。
任选地,可将相转移催化剂或表面活性剂或其它添加剂加入溶液(A)和/或(B)中以增强反应性或改善膜性能。
水溶液(A)中单体多胺反应物或有机溶液(B)中酰基卤反应物的浓度可宽泛地变化。例如,水溶液(A)中的单体多胺反应物浓度可以为0.01-20%(w/v),或0.5-10%(w/v),或1-5%。类似地,有机溶液(B)中的酰基卤反应物浓度可以为0.01-10%(w/v),或0.05-5%(w/v),或0.1-2%。
选择单体胺反应物和酰基卤反应物上的官能团以提供聚合的聚合反应产物,其在下文通常称为交联多胺。例如,二胺单体总是通过与酰基氯如均苯三甲酰氯(TMC)反应而制备交联多胺。在界面聚合以后,形成交联芳族聚酰胺,其交联密度可任选通过与交联试剂或分子量提高试剂如甲烷磺酰卤、表卤代醇、三甲胺三氧化硫配合物、甲醛、乙二醛等后聚合反应而进一步提高。
另一方面,本发明为聚合薄膜反应产物,其包含具有化学结合其上的分子笼型化合物的交联聚合物。在一个优选实施方案中,薄膜反应产物包含具有共价结合其上的分子笼型化合物的交联多胺。分子笼型化合物化学结合并形成嵌入交联聚合物基质中的分散相。优选共价结合于交联聚合物上的分子笼型化合物衍生自官能化笼型化合物如环糊精、杯芳烃或POSS。官能化笼型化合物包含在胺反应物与酰基卤反应物之间的界面反应形成交联多胺基质期间能够与酰基卤反应的官能团,使得笼型化合物变得共价结合并嵌入基质中。特别优选衍生自官能化POSS化合物的分子笼型化合物。
为控制薄膜反应产物的厚度,可任选使用与可聚合混合物(A)和(B)的所有组分溶混的稀释剂。优选的稀释剂包括但不限于乙醇、乙醇与水的混合物或异丙醇。
在另一实施方案中,本发明为制备包含载体上载的活性层的TFC复合膜。再次参考图2所示实例方法,更详细地讨论制备多层活性层的一个实施方案,其不意欲为限制性的。在该实施方案中,将经预处理的载体膜16放入水溶液(A)中几分钟,通常约1至约5分钟。尽管图2的方法包括将载体膜16放入水溶液(A)中,作为选择,该方法可通过将载体膜16放入水溶液(B)中引发。
将过量溶液(A)从载体膜16的浸涂表面排去(或将过量溶液通过用橡胶辊辊压而除去)并任选将经涂覆载体膜16在空气中在室温下干燥约1至约10分钟。
然后将二胺饱和载体膜16浸入溶液(B)中,在反应约1分钟以后,在载体16上形成交联活性膜层20。
然后可任选将TFC膜10(图1)干燥。干燥条件可宽泛地变化,但在一些实施方案中,将膜10在空气中在室温下干燥约1分钟至约5分钟,或者任选在保持在约30至约70℃的温度下的烘箱中干燥约1分钟至约5分钟。
可任选将TFC膜10用例如0.2%(w/w)碳酸钠溶液冲洗约5分钟并在膜试验以前储存在水中。
TFC膜10的活性层20优选具有小于约1μm的厚度,在一些实施方案中,可具有小于约500nm的厚度。
在将载体膜16引入溶液(A)中以前,可任选使用化学或物理处理(等离子体或UV-臭氧)以提高载体膜16表面的亲水性。尽管不愿受任何理论束缚,目前有效的证据表明聚砜载体的等离子体和/或UV-臭氧处理产生更亲水的表面(完全被水润湿),所以它可增强聚酰胺单体在载体层上的覆盖密度。
另外的结构完整性可任选通过将载体膜16层压在第二载体膜或层14上而提供给TFC膜。第二载体膜或层14优选为如果需要的话性质上可以为纤维状的挠性多孔有机聚合物材料。纤维状支持或载体材料的实例为具有微米范围内的直径的纺粘聚合物(例如聚乙烯)纤维的纸状网。
使用本文所述膜的平片型(例如螺旋绕制型)水净化或选择性渗透组件用于各种应用,例如海水脱盐、含盐水脱盐、乳清浓缩、电镀化学回收、市政或家庭用途的硬水软化、锅炉给水处理和涉及溶质或污染物脱除的其它水处理。
现在参考以下非限定性实施例进一步描述本发明。
实施例
间苯二胺(MPD片,>99%)和均苯三甲酰氯(TMC,98%)购自Sigma-Aldrich,并在使用以前将TMC蒸馏。氯化钠(NaCl)和碳酸钠(Na2CO3)购自J.T.Baker。己烷购自OmniSolv。去离子水用于所有实验。
胺官能化POSS(以上A-POSS结构(III),R=(CH2)3NH2·HCl)由HybridPlastics Inc.,Hattiesburg,MS得到,并将四个R基团用氢氧化钠中和以得到所需化合物,其在本文中称为A-POSS(图5,R=(CH2)3NH2·HCl(50%)且R=(CH2)3NH2(50%))。
聚砜(PSF)超滤(UF)膜购自Sepro Membranes,Inc。
实施例1:参比聚酰胺膜的生产
将经预处理的PSF UF膜放入2%(w/v)MPD的水溶液中2分钟,并将膜用橡胶辊辊压以除去过量溶液。然后将MPD饱和的PSF膜浸入0.1%(w/v)TMC的己烷溶液中。在反应1分钟以后,将TMC溶液倒出,并将所得膜用0.2%(w/v)碳酸钠的水溶液冲洗并储存在纯水中。
实施例2:包含胺官能化POSS(A-POSS)的纳米复合物聚酰胺膜的生产
将经预处理的PSF UF膜放入包含少量A-POSS的2%(w/v)MPD水溶液中2分钟,并将膜用橡胶辊辊压以除去过量溶液。然后将PSF膜浸入0.1%(w/v)TMC的己烷溶液中。在反应1分钟以后,将TMC溶液倒出,并将所得膜用0.2%(w/v)碳酸钠的水溶液冲洗并储存在纯水中。
A-POSS的载量为0.01-0.5%(w/v)。
表2显示通过X射线光电子光谱分析的含POSS聚酰胺膜的Si浓度。通过将水溶液中的A-POSS载荷从0.01%提高至0.10%,所得交联多胺膜中总硅(Si)的浓度和硅与碳(Si/C)的原子比实际上提高,表示A-POSS分子有效地化学并入芳族聚酰胺基质中。
表2
A-POSS载荷 | Si | Si/C |
A-POSS0.00% | 0.013 | 0.0002 |
A-POSS0.01% | 0.033 | 0.0005 |
A-POSS0.05% | 0.057 | 0.0008 |
A-POSS0.10% | 0.077 | 0.0011 |
实施例3:包含POSS的纳米复合物聚酰胺膜的评估
使用交叉流过滤系统评估膜性能。纯水通量在将膜在200psi下压缩3.5小时以后在室温下测量。然后在相同的压力下用2000ppm NaCl水溶液测量脱盐率。用TFC聚酰胺膜得到的水通量和脱盐率值汇总于图3和图4中。
如图3所示,含POSS聚酰胺RO膜在用2000ppm NaCl进料溶液测试的实验室规模交叉流过滤条件下评估。图3显示用包含0.3%(w/v)和0.5%(w/v)A-POSS的聚酰胺膜得到的水通量(左)和脱盐率(右)值。还评估以上在实施例1中描述为参比聚酰胺膜的不具有A-POSS载荷的交联芳族聚酰胺膜用于数据对比。
水通量通过将POSS并入聚酰胺活性层中而显著增强;然而,脱盐率同时降低。该结果表示0.3%(w/v)和0.5%(w/v)A-POSS载荷在交联多胺活性层中产生太多自由体积,这产生比实施例1的参比聚酰胺膜中观察到的更高的盐通过。
为保持高脱盐率,同时改进水通量,降低活性层中A-POSS载荷的量。图4显示用由0.01%(w/v)、0.05%(w/v)和0.1%(w/v)A-POSS载荷制备的含POSS聚酰胺膜观察到的水通量(左)和脱盐率(右)值。在低A-POSS载荷下,含POSS聚酰胺膜显示比实施例1的参比聚酰胺膜更高的水通量,同时还保持类似或稍微更高的脱盐率。
如图4所示,基于含POSS聚酰胺膜的通量和脱盐率数据,在该实施例中得到水通量和脱盐率的最好组合的A-POSS载荷的最佳量为约0.05%(w/v)。
已描述了本发明的各个实施方案。这些和其它实施方案在以下权利要求书的范围内。
Claims (20)
1.载体上的聚合物膜,其中聚合物膜包含交联聚合物,且其中交联聚合物共价结合于分子笼型化合物上。
2.根据权利要求1的膜,其中分子笼型化合物选自POSS、环糊精、杯芳烃及其组合。
3.根据权利要求1的膜,其中分子笼型化合物为POSS。
4.根据权利要求1的膜,其中分子笼型化合物具有至少一个能与单体反应形成交联聚合物的官能团。
5.根据权利要求4的膜,其中分子笼型化合物衍生自官能化POSS化合物。
6.根据权利要求5的膜,其中POSS化合物包含选自含醇结构部分和含胺结构部分的官能团。
8.根据权利要求7的膜,其中至少一个R基团为含胺结构部分。
9.根据权利要求7的膜,其中至少一个R基团为(CH2)3NH2。
10.一种方法,其包括通过界面聚合形成权利要求1的膜。
11.一种方法,其包括:
a)将载体膜浸入水溶液中,其中水溶液包含胺化合物和官能化笼型化合物,其中笼型化合物为选自POSS、环糊精、杯芳烃及其组合的官能化化合物;
b)将载体膜从水溶液中取出;和
c)将载体膜浸入包含酰基卤化合物的有机溶液中,其中有机溶液在水中不溶混。
12.根据权利要求11的方法,其中水溶液包含0.01-0.5重量%笼型化合物每单位体积水溶液。
13.根据权利要求11的方法,其中水溶液包含0.01-0.1重量%笼型化合物每单位体积水溶液。
14.根据权利要求11的方法,其中水溶液包含0.01-0.05重量%笼型化合物每单位体积水溶液。
16.根据权利要求15的方法,其中至少一个R基团为(CH2)3NH2。
17.根据权利要求16的方法,其中水溶液包含0.01-0.05重量%POSS衍生物每单位体积水溶液。
18.根据权利要求11的方法,其进一步包括在步骤(c)以后将膜用碱性水溶液冲洗。
19.根据权利要求11的方法,其进一步包括在步骤(b)以后将水从载体膜除去。
20.根据权利要求11的方法,其中胺化合物为间苯二胺且酰基卤化合物为均苯三甲酰氯。
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WO2013006288A1 (en) | 2013-01-10 |
US20130001153A1 (en) | 2013-01-03 |
US20150021262A1 (en) | 2015-01-22 |
CN103635242B (zh) | 2016-06-15 |
US8895104B2 (en) | 2014-11-25 |
US9333465B2 (en) | 2016-05-10 |
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