CN113398775A - 一种功能性离子液体-明胶复合膜及其制备方法 - Google Patents
一种功能性离子液体-明胶复合膜及其制备方法 Download PDFInfo
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Abstract
本发明制备了一种新的离子液体‑明胶复合膜。首次将离子液体环糊精包合物、明胶溶液和致孔剂通过简单的物理方式共混制备铸膜液，进而自然延流并经真空干燥成膜。该膜具有较为理想的均质性、透过性、稳定性及机械强度，同时结合了离子液体原有的催化、分离及明胶多孔层滤过功能。本技术丰富了功能膜材质种类，拓展了现有的离子液体固定化工艺及其应用形式；成型工艺便捷、有效，且膜易于放大制备及循环使用。
Description
技术领域
本发明涉及了一种功能性离子液体-明胶复合膜的制备方法，具体涉及将明胶基质、致孔剂及离子液体的β-环糊精包合物通过物理方式共混制备铸膜液，进而自然延流并经真空干燥成膜。该膜结合了离子液体原有的催化、分离及明胶多孔层滤过功能，属于功能性膜材料领域。
背景技术
明胶作为天然可再生大分子物质之一，来源广泛，价格低廉，具有很好的成膜性及可生物降解性。明胶结构中具有的氨基、羟基、羧基等官能团会产生分子间的范德华力、静电吸引和氢键，反应活性较高，有利于实现其功能化(杨斯乔,李海朝.甲壳素-明胶复合膜性能研究[J].食品研究与开发,2019,18:44-51.)。但明胶基材料的机械强度和阻水性差，很难满足实际应用的要求。因此，对明胶膜的性能进行改性进而制备复合型功能材料是当前的研究热点。
将离子液体(IL)固定到多孔无机载体或聚合物材料中，可以得到固定化离子液体(SIL)，使其兼具离子液体和载体材料的优势；用于分离及催化过程时有利于提高处理能力乃至选择性。SIL通过离子液体与其它介质之间的复合，增加了比表面积和稳定性，从而提升了离子液体的利用效率；用量显著减少的同时在规模化应用方面较自由态离子液体更具优势，更易实现有效回收和重复使用，因而具有良好的应用前景(贾巧焕,刘冉,郭盼香.固载离子液体催化酯化反应研究[J].现代化工,2019,39(9):152-156.)。现有的SIL报道中IL和载体的类型都比较丰富，前者几乎涵盖了所有类型的离子液体，后者常包括硅胶、纤维素、石墨烯、碳纳米管、磁性纳米材料、壳聚糖、环糊精以及某些生物大分子材料。常用的离子液体固定化方式有多种，如溶胶-凝胶法、化学接枝法、物理浸渍法、聚合法等。但很多已报道的制备方法不易推广和规模化采用，步骤繁琐，工艺参数复杂，成本相对较高。SIL的应用主要集中在有机合成与分离纯化领域，既保留了自由态离子液体作为催化和分离介质的原有作用，又能提供不同于传统溶剂环境的条件及机制，还能使相关过程更加绿色。已经报道过SIL在氢化、酯化、烷基化、生物催化、氧化及Heck反应中的应用；其既能通过所连基团提供酸性环境、促进酸催化的反应发生，还可结合含有过渡金属的催化剂以提高催化效果及反应稳定性(方东,刘祖亮,周新利.功能化离子液体室温催化合成乙酸苄酯[J].应用化学,2007,24(1):85-89.)。SIL的另一个应用方向是分离纯化领域，可用于苯类芳香族化合物、重金属、染料、天然活性成分、生物大分子乃至气体分子的分离，相较传统介质更有利于提高分离效率，改善分离度，增强吸附量以及选择性(Zhang W,Feng XT,Yohannes A,etal.Bionic multi-tentacled ionic liquid-modified silica gel for adsorption andseparation of polyphenols from green tea(Camellia sinensis)leaves[J].FoodChemistry,2017:637-648.)。
膜分离技术可根据对象化学结构及分子量水平的差异而选择具有不同截留特性的膜对某些部位进行富集和纯化。一般以压力驱动，具有操作简单、易于放大等优势。目前已成功应用于分离多种天然活性成分(如：多糖、蛋白、环烯醚萜、生物碱、氮苷、黄酮和花青素等)(CisséM,Vaillant F,Pallet D,et al.Selecting ultrafiltration andnanofiltration membranes to concentrate anthocyanins from roselle extract(hibiscus sabdariffa l.).Food Research International,2011,44(9),2607-2614.)及移除有机反应中生成的副产物水(Li Y,Han S,Zhang L,et al.Fabrication andmodeling of catalytic membrane for removing water in esterification[J].Journal of Membrane Science,2019,579:120-130.)和一些酸性气体(如：CO2、SO2和H2S等)(张正敏,吴林波,朱世平,等.固定化离子液体的制备及其在气体分离中的应用研究[J].科技通报,2009(03):55-60.)。一般可采用物理浸渍、结构改性、表面修饰、分子印迹等技术对膜材料进行改进以提高其选择性和处理能力。膜催化技术则是将催化剂覆盖在膜表面或分散在膜内，使膜成为反应区。根据膜材质的不同一般分为两类：有机催化膜的典型代表是酶固定化膜，而无机膜典型代表是钯膜和各种陶瓷、玻璃膜；两者已被广泛应用于脱氢、氧化、酯化、生化及污水处理等多个领域(张昊,马晓华,许振良.催化与分离双功能膜及膜反应器[J].膜科学与技术,2019,39(01):120-128.)。除此以外，具有双功能的催化分离膜也是膜材料领域的研究热点；此双功能膜基于一定方式将多功能介质负载于膜上实现“反应+分离”一体化，既可以消除内扩散和强化传质，还可以有效解决吸附剂、催化剂回收困难的问题。但目前经广泛检索未见适用分离或催化或两者合一的双功能离子液体-明胶复合膜材料的报道及实际应用。
发明内容
本发明提供了一种功能性离子液体-明胶复合膜及其制备方法，该法以离子液体为功能单体，以明胶为主要基质，以先包合、后混合进而成膜为关键操作步骤；通过改变离子液体的种类对功能组分进行调整以实现不同的应用目的。本发明提供了该复合膜的配方、制法以及主要技术路线：
(1)将有机尼龙微孔滤膜用少量的去离子水润湿后，置于清洁干燥的陶瓷布氏漏斗中，通过抽吸除去空气和水并使其紧贴于漏斗内侧表面，待用。
(2)为了加强离子液体在明胶膜中的固载效果，同时改善复合膜的整体性状，用超纯水为溶剂将目标离子液体与β-环糊精以1:1或1:2的摩尔比混合后，通过饱和水溶液法进行包合得到β-环糊精对目标离子液体的稳定包合物。
(3)将质量分数为4～12％的明胶水溶液、质量分数为1～7％的致孔剂(包括：聚丙烯酰胺，或氯化钠，或聚乙烯吡咯烷酮)水溶液及离子液体-β-环糊精的包合物，以不同的质量比混合后在40℃下充分搅拌1h。冷却至室温后取铸膜液0.5～2.5mL倒入已有尼龙滤膜的漏斗中自然延流成圆形薄膜，常温下真空干燥过夜，取出备用。
(4)使用时以一定的压力差(真空度0～0.8MPa)驱动被分离物或反应物缓慢地通过此功能性复合膜，完成其分离、催化、滤过过程。
上述制备方法步骤(2)中制备离子液体和β-环糊精的包合物中所用的离子液体包括表1所示结构，主要由具有不同链长取代基团和阴离子的咪唑类离子液体所组成。同时不限于这些离子液体，其它具有催化或分离功能的水溶性离子液体亦可。
表1本发明专利所包括的离子液体结构
上述制备方法步骤(2)中所述通过饱和水溶液法制备离子液体和β-环糊精的包合物，具体方法是：以超纯水配制浓度均为0.05mol/L、0.10mol/L、0.25mol/L的离子液体及环糊精水溶液，或浓度为0.05mol/L、0.10mol/L、0.25mol/L的离子液体水溶液和0.10mol/L、0.20mol/L、0.50mol/L的环糊精水溶液；在40℃下将等体积的两者混合后充分搅拌1h；然后冷却至室温过滤，将滤饼置于真空50℃下干燥，得到不同化学计量比的包合物。
上述制备方法步骤(3)中所述的不同配方的复合膜制备方法，具体方法是，将质量分数为4～12％的明胶水溶液和质量分数为1～7％的致孔剂水溶液(包括：聚丙烯酰胺，或氯化钠，或聚乙烯吡咯烷酮)以9/1～6/4的质量比分别在40℃下充分搅拌1h。冷却至室温后取铸膜液0.5～2.5mL倒入已吸有尼龙滤膜的布氏漏斗中延流成膜，常温下真空干燥过夜。进而根据应用所需，向该明胶/致孔剂体系中加入不同的离子液体和β-环糊精的包合物，得到功能性离子液体-明胶复合膜。
上述制备方法步骤(3)中制备的功能性离子液体-明胶复合膜，干燥条件是：常温下真空干燥过夜，干燥后的膜厚度为0.1～0.2mm，平均孔径为0.73μm。
以L-脯氨酸[L-pro]为阴离子、阳离子为3个亚甲基连接而成的2个N-乙烯基咪唑双阳离子液体([VIm]2C3[L-pro]2)为例。采用扫描式电子显微镜(SEM)、傅里叶红外光谱仪(FT-IR)、热重分析(TG)对该离子液体-明胶复合膜进行表征，结果如下：
(1)外观和SEM分析
如图1A所示，自然光下可见该复合膜表面光洁、平滑致密，外观厚度薄且均匀透明，便于观察使用时的传质状态；进而采用SEM观察复合膜切片微观形貌(如图1B所示)，可见无明显裂隙、沟槽或气泡存在，体现了其内部微结构的匀质性；此外分布其间的微孔道有利于液体或气体分子的传输。
(2)FT-IR表征
由图2可以看出，纯明胶在3456.96cm-1处有强峰吸收，其归属于N-H伸缩振动；1500～1650cm-1处的吸收峰可归属于羰基C＝O的伸缩振动和胺基N-H弯曲振动。纯聚丙烯酰胺(致孔剂)在3455.50cm-1处有一个较强的N-H伸缩振动吸收峰，1500～1680cm-1处的吸收峰归属于羰基C＝O伸缩振动、C＝C伸缩振动，1384.51cm-1处的吸收峰归属为C-N伸缩振动和N-H弯曲振动吸收混合峰，以及619.10cm-1处的O＝C-N的弯曲振动吸收。离子液体[VIm]2C3[L-pro]2红外图谱的特征峰如：3445.33cm-1处的N-H伸缩振动、1633.54cm-1处的C＝C双键伸缩振动、1384cm-1处的C-H弯曲振动。β-环糊精(β-CD)的IR谱图中的主要特征峰如3392.40cm-1处的O-H伸缩振动、2926.15cm-1处的-CH2-不对称伸缩振动、1157.84cm-1处的C-O-C伸缩振动以及1030.09cm-1处的环的变形振动。离子液体-明胶复合膜的红外特征峰吸收与纯明胶非常相似，这个也符合此膜以明胶为主要基质的事实。同时因膜配方中的明胶、聚丙烯酰胺、离子液体和β-环糊精形成分子间氢键而导致部分特征峰向低波数移动。
(3)TG分析
TG条件：温度范围30～800℃，升温条件：10℃/min，N2保护。将包合物的TG分析图与纯的β-环糊精(β-CD)和离子液体TG图进行比较，结果如图3所示。从纯β-CD的TG分析图可知，TG曲线主要出现三个平台，一个是30～100℃之间，此阶段质量损失14.20％，对应β-CD中存在的水分。第二个阶段是260～360℃，此阶段重量迅速损失66.59％，故β-CD的分解温度约260℃左右。当温度大于360℃质量损失出现第三个阶段，直至680℃时质量损失趋于平衡，损失12.20％，此阶段碳骨架彻底崩塌。从离子液体[VIm]2C3[L-pro]2的TG分析结果可知，TG曲线一共有四个平台，30～150℃出现第一个平台，质量损失20.70％，此阶段对应离子液体中未除去的水分。150～270℃出现第二个平台，这个阶段重量迅速损失54.58％，故离子液体的分解温度在150℃左右，第三个台阶在大于150℃到345℃之前，失重约16.32％，350～500℃之间出现第四个台阶，当温度大540℃失重达到平衡。从包合物β-CD-[VIm]2C3[L-pro]2的TG分析图可知，包合物β-CD-IL的TG曲线有四个主要台阶，30～130℃之间出现第一个失重台阶，失重约9.10％，此损失为包合物中未彻底干燥除去的水分，当温度大于150℃时，包合物的质量损失加速，故此包合物的分解温度约150℃左右，同时当温度大于670℃时，质量损失趋于平衡。对比三种物质的TG曲线，可见包合对离子液体明显存在稳定化作用。
与现有膜材料相比，本发明的优点在于：以廉价且易降解的明胶这种天然高分子为主要原料，通过加入少量以环糊精包合的功能型离子液体，结合致孔剂和基底支撑物，通过简单的物理方式迅速成膜。此研究拓展了离子液体固定化技术和应用形式，丰富了功能性膜材质及其制备手段，提供了不同于传统催化和分离介质的操作条件及作用机制。
附图说明
图1直径为50mm的复合膜外观(A)及其切片SEM照片(B)
图2复合膜各组分及成膜的红外图谱表征结果(KBr压片)
图3离子液体[VIm]2C3[L-pro]2、β-环糊精及两者包合物的TG分析结果比较
具体实施方式
此处所描述的具体实例仅用于解释和说明本专利，不能理解为对本发明保护范围的限制。
实施实例1：具有滤过功能的明胶/致孔剂体系的制备
将质量分数为4～12％的明胶水溶液、质量分数为1～7％的致孔剂水溶液(致孔剂包括：聚丙烯酰胺，或氯化钠，或聚乙烯吡咯烷酮)，以一定的配比(m明胶/m致孔剂＝9/1、8/2、7/3、6/4)在40℃下充分搅拌1h，冷却至室温；取铸膜液0.5～2.5mL倒入吸有尼龙滤膜(直径为50mm)的布氏漏斗中延流成膜，常温下真空干燥过夜。使用前用去离子水溶胀30min，之后倾去去离子水，并用水洗膜3次，最后用滤纸吸干膜表面的水分备用。在一定压力差(真空度≤0.8MPa)下对该膜透过性进行测试。包括明胶溶液的浓度、致孔剂种类、致孔剂的浓度以及明胶溶液与致孔剂溶液的质量比(m明胶/m致孔剂)在内的主要因素对成膜性及膜透过性的影响如表2所示。
表2不同膜配方的成膜性及透过性
实施实例2：离子液体[C4mim][BF4]@明胶复合膜的制备
将质量分数为8％的明胶水溶液、质量分数为5％的聚丙烯酰胺水溶液及离子液体和β-环糊精的包合物(nILs：nβ-CD＝1:1)，以配比为m明胶：m致孔剂：mβ-CD-IL＝8:2:0.3在40℃下充分搅拌1h，取铸膜液1mL倒入吸有尼龙滤膜(直径为50mm)的布氏漏斗中延流成膜，常温下真空干燥过夜。得到膜的平均厚度为0.1mm。
实施实例3：离子液体[C4mim][NTf2]@明胶复合膜的制备
将质量分数为8％的明胶水溶液、质量分数为5％的聚丙烯酰胺水溶液及离子液体和β-环糊精的包合物(nILs：nβ-CD＝1:1)，以配比为m明胶：m致孔剂：mβ-CD-IL＝8:2:1在40℃下充分搅拌1h，冷却至室温，取铸膜液1mL倒在吸有尼龙滤膜(直径为50mm)的布氏漏斗上延流，常温下真空干燥过夜。得到膜的平均厚度为0.2mm。
实施实例4：离子液体[C4mim][HSO4]@明胶复合膜的制备
将质量分数为8％的明胶水溶液、质量分数为5％的聚丙烯酰胺水溶液及离子液体和β-环糊精的包合物(nILs：nβ-CD＝1:1)，以配比为m明胶：m致孔剂：mβ-CD-IL＝8:2:0.3在40℃下充分搅拌1h，冷却至室温，取铸膜液1mL倒在吸有尼龙滤膜(直径为50mm)的布氏漏斗上延流，常温下真空干燥过夜。得到膜的平均厚度为0.1mm。
实施实例5：离子液体[VIm]2C3[L-pro]@明胶复合膜的制备及分离茶多酚的应用
将质量分数为8％的明胶水溶液、质量分数为5％的聚丙烯酰胺水溶液及离子液体和β-环糊精的包合物(nILs：nβ-CD＝1:1)，以配比为m明胶：m致孔剂：mβ-CD-IL＝8:2:0.3在40℃下充分搅拌1h，常温下真空干燥过夜，取铸膜液1mL倒入已有尼龙滤膜(直径为50mm)的布氏漏斗中延流成膜，室温干燥过夜；优选后的膜厚度为0.1mm。吸附前用去离子水溶胀30min，之后倾去去离子水，并用水洗膜3次，最后用滤纸吸干膜表面的水分，待用。
将干燥的绿茶用碾钵粉碎后过筛，称量60目茶叶粉末1g放置在锥形瓶中，用10mL的50％的乙醇-水(V/V)溶液进行超声提取。提取结束后，将除去溶剂后得到的浸膏重新溶解在25mL蒸馏水中。以一定的压力差(真空度0.6～0.8MPa)驱动提取液缓慢地通过此复合膜。对吸附后溶液进行定性及定量分析发现，此复合膜对粗提液中的茶多酚具有选择性吸附作用，吸附率可达90％以上。
实施实例6：离子液体[PSmim][HSO4]@明胶复合膜的制备及催化酯化反应的应用
将质量分数为8％的明胶水溶液、质量分数为5％的聚丙烯酰胺水溶液及离子液体和β-环糊精的包合物(nILs：nβ-CD＝1:1)，以配比为m明胶：m致孔剂：mβ-CD-IL＝8:2:0.3在40℃下充分搅拌1h，冷却至室温，取铸膜液1mL倒在吸有尼龙滤膜(直径为50mm)的布氏漏斗中上延流，常温下真空干燥过夜；优选后的膜厚度为0.1mm。
将干燥后的膜固定在上下玻璃室中间，上室装载有按摩尔比为n(苯甲醇)：n(冰乙酸)＝1:1～1:2混合均匀的反应混合物。在反应过程开始后，控制上下室间的压力差(真空度0～0.6MPa)，使得不断生成的副产物通过明胶-离子液体复合膜被缓慢移除，从而抑制酯化反应达到反应平衡，推动反应一直向正方向进行。反应效率得到明显提高，产物乙酸苄酯的产率最高可达98％。
Claims (3)
1.一种功能性离子液体-明胶复合膜，其特征在于，该复合膜由离子液体-β-环糊精包合物、明胶和致孔剂共同组成；此膜平均厚度为0.15mm，平均孔径为0.73μm。
2.如权利要求1所述的离子液体-明胶复合膜，其特征在于，固载的离子液体可以根据需求调整种类，主要由具有不同链长取代基团和阴离子的咪唑类离子液体所组成；普遍适用于由常见阴、阳离子所构成的亲水性离子液体，能够与明胶和致孔剂溶液共混形成均一铸膜液。
3.一种离子液体-明胶复合膜的制备方法，其特征在于，按以下步骤进行：
(1)以超纯水为溶剂，将目标离子液体与β-环糊精以1:1～1:2的摩尔比混合，通过饱和水溶液法进行包合，得到β-环糊精对目标离子液体的稳定包合物；
(2)将质量分数为4～12％的明胶水溶液、质量分数为1～7％的致孔剂(包括：聚丙烯酰胺，或氯化钠，或聚乙烯吡咯烷酮)水溶液及离子液体-β-环糊精的包合物，以不同的质量比混合后在40℃下充分搅拌1h，冷却至室温后取铸膜液0.5～2.5mL在预先备好的漏斗中自然延流成薄膜，常温下真空干燥过夜，取出待用；
(3)使用时以一定的压力差(真空度0～0.8MPa)驱动被分离物或反应物缓慢地通过此功能性复合膜，完成其分离、催化、滤过过程。
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