CN105348553B - 一种有催化活性的纤维素薄膜制备方法 - Google Patents
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Abstract
本发明涉及一种有催化活性的纤维素薄膜制备方法，其特征在于在采用相转变法制备纤维素膜的基础上，将纤维素膜浸渍在不同浓度的多胺基硅烷偶联剂溶液中，处理7‑24h，而后在逐步升温的条件下进行非均相接枝反应，经乙醇后处理后，即得多胺基功能化的纤维素膜。本制备方法简单可行，易于操作，生产成本低，纤维素胺基化功能膜对Knoevenagel缩合反应和Henry反应均表现出了良好的催化活性，且具有环保、易于回收、可重复使用等绿色催化剂的优点。此外，本发明提供的胺基功能化纤维素薄膜具有多孔性特征，可对催化生成的产物进行负载，便于进一步的应用。
Description
技术领域
本发明属于一种纤维素薄膜的制备技术领域，具体涉及一种具有催化活性的胺基功能化的纤维素薄膜制备方法。
背景技术
纤维素膜的制备技术及其高附加值化是近年来纤维素科学与技术领域的研究重点。研究的方向主要包括以下方面：(1)开发新的膜制备技术，如纳米纤维素的水悬浮液成膜技术、传统的相转化法和荷电化修饰等技术相结合而制备的新颖纤维素膜；(2)采用共混、负载、以及吸附等物理方法以提高纤维素膜的高性能和功能化，如利用纤维素多孔结构的负载金属、金属氧化物、稀土等各种无机纳米粒子，以赋予赋予其导电、导磁、化学催化、抗菌、光学等功能；(3)利用纤维素大分子链含有的羟基，对其进行氧化、酯化、胺基化、醚化以及接枝共聚等表面改性，以实现纤维素膜的功能化；(4)分析和研究已研制出的功能化纤维素膜，以开发新的功能性，进一步拓宽其应用领域。
胺类催化剂是碱性催化剂的重要一种，除了广泛应用于Knoevenagel缩合反应、Baylis-Hillman反应以及Aldol反应外，还可用于PU合成、环氧树脂的固化以及酚醛、脲醛、三聚氰胺甲醛的聚合中。近年来，绿色化学和绿色催化剂的概念日益深入人心，胺类催化剂的研究已从传统地提高反应速率以及产率以及更温和反应条件的获得转变为解决催化剂不能重复使用，回收困难，催化剂与产物分离步骤繁琐，具有腐蚀性及废水排放造成污染等问题。各种有机胺以及新颖的催化剂如胺基修饰的生物催化剂等对环境友好的固体碱催化剂的出现，尽管达到了高效的、绿色的、可重复回收利用的目的，但仍存在反应的适应性以及生产成本较高的问题。本发明在采用相转变法制备多孔纤维素膜的基础上，以多胺基硅烷偶联剂为改性剂，进行非均相氨基接枝，经胺基修饰的多孔纤维素膜对Knoevenagel缩合反应表现出了良好的催化活性，本发明既制备了新型的胺类催化剂，又为胺基功能化的纤维素膜的应用前景指出了一条新的途径。
发明内容
本发明的目的是提供一种有催化活性的胺基功能化的纤维素薄膜制备方法。该方法制备工艺简单，生产成本低，适于工业化生产。所得胺基功能化纤维素膜对Knoevenagel缩合反应和Henry反应均表现出了良好的催化活性，且具有环保、易于回收、可重复使用等绿色催化剂的优点。
为达到上述目的，一种具催化性能的多孔结构纤维素薄膜制备方法如下：
(1)制备纤维素薄膜：采用相转变法制备多孔纤维素膜；
(2)硅烷偶联剂溶液的配置：将一定量的硅烷偶联剂溶解在溶剂中，冰醋酸调节溶液pH(3-5)；
(3)接枝纤维素薄膜：将纤维素薄膜浸渍在步骤(2)中配置好的溶液中一段时间(7-24h)后取出在烘箱中热处理，反应温度为30-150℃，反应时间时间为2-8h；
(4)将改性后的纤维素薄膜经过乙醇溶剂浸泡洗涤多次，室温下干燥，最终制成氨基功能化纤维素薄膜。
所述步骤(1)的多孔纤维素膜，是再生纤维素膜、纳米纤维素膜以及细菌纤维素膜中的一种。
所述步骤(2)中硅烷偶联剂为N-(β-氨乙基)-γ-氨丙基三甲氧基硅烷，3-氨丙基三甲氧基硅烷，N-(β-氨乙基)-γ-氨丙基三甲氧基硅烷中的一种。
所述步骤(3)中的多胺基硅烷偶联剂溶液浓度为0.5wt％-8wt％
本发明的有益效果在于：
(1)本发明提供的胺基功能化纤维素薄膜制备方法具有原料丰富、价格低廉、绿色环保，制备过程简单、便捷的特点。
(2)本发明提供的胺基功能化纤维素薄膜对Knoevenagel缩合反应和Henry反应均表现出了良好的催化活性，有较好的热稳定性和催化性能，具有高活性，副反应少，可回收，重复使用，无污染等特点，避免了传统催化剂与产物分离步骤繁琐，具有腐蚀性及废水排放造成污染等问题，符合现代绿色化学发展要求。
(3)本发明提供的胺基功能化纤维素薄膜具有多孔性特征，可对催化生成的产物进行负载，便于进一步的应用。
附图说明
图1：多胺基硅烷偶联剂接枝纤维素膜前后的红外图谱；
图2：胺基功能化前后的纤维素膜催化生成苯亚甲基丙二酸二乙酯产率的对比。
具体实施方式
实施例1
第一步，将5g棉短绒分散在100g碱性溶液中，所得纤维素悬浮液放入-20℃下的冰箱冷冻，24h以后取出，高速机械搅碎后得到粘稠的纤维素溶液，随后将纤维素溶液在离心机上离心除去气泡，条件为恒定离心机温度为5℃，转速为8000r/min，离心10min。通过这种简单方法得到的纤维素溶液在玻璃板上推制成薄层，然后浸入浓硫酸溶液凝固再生得到透明纤维素膜，纤维素膜反复去离子水水洗后备用。
第二步，将N-(β-氨乙基)-γ-氨丙基三甲氧基硅烷(1.75)溶解在体积比为4∶1的无水乙醇/水(40ml)的混合溶液中，滴加稀醋酸溶液使其混合液pH调节为3，然后将裁剪成约7cm×8cm的矩形纤维素膜浸没在上述配置好的偶联剂溶液中，24h以后取出放入烘箱热处理，前段温度为40℃，时间为3h，后段温度为80摄氏度，时间为4h。随后将偶联改性的纤维素用乙醇索氏抽提18h，室温干燥备用，接枝率为1.64％
实施例2
第一步，将经酸解得到的纳米纤维素悬浮液稀释至0，5wt％，在冰浴的情况下用300W的超声功率处理10min，以确保纳米纤维素均匀分散在水中。然后用铺有有机过滤膜的玻璃换膜过滤装置过滤上述稀释液，并用真空泵真空过滤。待纳米纤维素均匀地形成纳米纤维素膜后连同有机过滤膜一同取出，盖上一片有机过滤膜后，在室温下干燥2～3天，再移到60℃的真空干燥箱中干燥2～3天。干燥完毕后揭开即可得到透明的纳米纤维素膜。
第二步，将N-(β-氨乙基)-γ-氨丙基三甲氧基硅烷(1.51g)溶解在体积比为4∶1的丙酮/水(40ml)的混合溶液中，滴加稀醋酸溶液使其混合液pH调节为4，然后将裁剪成约7cm×8cm的矩形纤维素膜浸没在上述配置好的偶联剂溶液中，24h以后取出放入烘箱热处理，前段温度为30℃，时间为2h，后段温度为90摄氏度，时间为3h。随后将偶联改性的纤维素用乙醇索氏抽提18h，室温干燥备用，接枝率为0.97％
实施例3
第一步，将6g棉短绒分散在100g碱性溶液中，所得纤维素悬浮液放入-20℃下的冰箱冷冻，24h以后取出，高速机械搅碎后得到粘稠的纤维素溶液，随后将纤维素溶液在离心机上离心除去气泡，条件为恒定离心机温度为5℃，转速为8000r/min，离心10min。通过这种简单方法得到的纤维素溶液在玻璃板上推制成薄层，然后浸入5wt％浓硫酸溶液凝固再生得到透明纤维素膜，纤维素膜反复去离子水水洗后备用。
第二步，将3-氨丙基三甲氧基硅烷(1.25g)溶解在体积比为4∶1的无水乙醇/水(40ml)的混合溶液中，滴加稀醋酸溶液使其混合液pH调节为4.5，然后将裁剪成约7cm×8cm的矩形纤维素膜浸没在上述配置好的偶联剂溶液中，24h以后取出放入烘箱热处理，前段温度为60℃，时间为4h，后段温度为120摄氏度，时间为2h。随后将偶联改性的纤维素用乙醇索氏抽提18h，室温干燥备用，接枝率为0.73％
实施例4
第一步，室温下，将烘至绝干的细菌纤维素在100mL乙二胺溶液中浸渍处理90min，然后用大量的蒸馏水和甲醇洗涤，80℃真空烘干。在250mL三口圆底烧瓶中加入100mLDMAc，8g经150℃真空烘干的LiCl，然后搅拌，并用油浴锅对三口烧瓶进行加热。待LiCl完全溶解后，再加入经乙二胺浸渍处理后的细菌纤维素，加热搅拌3h，冷却至室温静置直到其完全溶解。上述细菌纤维素溶液在恒温热玻璃板上刮制成膜，浸入25℃凝固浴，然后自然晾干。
第二步，将N-(β-氨乙基)-γ-氨丙基三甲氧基硅烷(0.71)溶解在体积比为4∶1的丙酮/水(40ml)的混合溶液中，滴加稀醋酸溶液使其混合液pH调节为3.5，然后将裁剪成约7cm×8cm的矩形纤维素膜浸没在上述配置好的偶联剂溶液中，15h以后取出放入烘箱热处理，前段温度为40℃，时间为2h，后段温度为100摄氏度，时间为2h。随后将偶联改性的纤维素用乙醇索氏抽提18h，室温干燥备用，接枝率为0.61％
催化性能测试方法
将0.5g使用过的实施例1制备的氨基功能化的纤维素薄膜用乙醇溶液常温浸泡5h，过滤去溶液，纤维素薄膜经多次水洗，干燥得到0.49g氨基功能化的纤维素薄膜。在带有回流装置的50ml三颈烧瓶中，以甲苯(10ml)为溶剂，硝基甲烷(50mmol)和苯甲醛(5mmol)混合，加入回收处理的0.49g氨基功能化的纤维素薄膜，磁力搅拌下在110℃反应8h后，冷却，离心，取上层清液在GC9790气相色谱仪上进行分析，苯甲醛的转化率为97％。
综上，本发明所述的氨基功能化纤维素薄膜对Henry反应有高效的催化活性，而且可回收利用，回收后的纤维素薄膜仍然有较强的催化性能。
以上所述仅为本发明的具体实施例而已，并不用于限制本发明，凡在本发明的精神和原则之内，所做的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。
Claims (1)
1.一种有催化活性的纤维素薄膜制备方法，其特征在于，
第一步，将5g棉短绒分散在100g碱性溶液中，所得纤维素悬浮液放入-20℃下的冰箱冷冻，24h以后取出，高速机械搅碎后得到粘稠的纤维素溶液，随后将纤维素溶液在离心机上离心除去气泡，条件为恒定离心机温度为5℃，转速为8000r/min，离心10min；得到的纤维素溶液在玻璃板上推制成薄层，然后浸入浓硫酸溶液凝固再生得到透明纤维素膜，纤维素膜反复去离子水水洗后备用；
第二步，将N-(β-氨乙基)-γ-氨丙基三甲氧基硅烷1.75g溶解在体积比为4∶1的无水乙醇/水40ml的混合溶液中，滴加稀醋酸溶液使其混合液pH调节为3，然后将裁剪成约7cm×8cm的矩形纤维素膜浸没在上述配置好的偶联剂溶液中，24h以后取出放入烘箱热处理，前段温度为40℃，时间为3h，后段温度为80摄氏度，时间为4h；随后将偶联改性的纤维素用乙醇索氏抽提18h，室温干燥备用，接枝率为1.64％。
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