CN108219062A - 一种光诱导电子转移-可逆加成断裂链转移聚合制备有机多孔材料的方法 - Google Patents
一种光诱导电子转移-可逆加成断裂链转移聚合制备有机多孔材料的方法 Download PDFInfo
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Abstract
本发明公开了一种光诱导电子转移‑可逆加成断裂链转移聚合（RAFT）在油包水包油（O/W/O）双乳液体系中制备有机多孔材料的方法。是将可聚合的功能单体、交联剂、链转移试剂和表面活性剂为油相，以光氧化还原催化剂的水溶液为连续相，在搅拌下将油相滴加水相，然后向水相滴加有机溶剂，继续搅拌一段时间，得到水包油型乳液（O/W）；再将上述得到的O/W型乳液滴加到含有表面活性剂的有机溶剂中，通过进一步搅拌制得O/W/O型乳液，通氮除氧。室温下光照射进行聚合反应，制得有机多孔材料。该方法制备的有机多孔材料呈规整球形结构，表面及内部具有丰富的孔道结构。
Description
技术领域
本发明属于高分子材料技术领域，具体是一种光诱导电子转移-可逆加成断裂链转移聚合制备有机多孔材料的方法。
背景技术
可逆加成断裂链转移（RAFT）聚合一种高效的制备可控聚合聚合物的方法（JohnChiefari, Y. K. (Bill) Chong, Frances Ercole, Julia Krstina, Justine Jeffery,Tam P. T. Le, Roshan T. A. Mayadunne, Gordon F. Meijs, Catherine L. Moad,Graeme Moad, Ezio Rizzardo and San H. Thang Living Free-RadicalPolymerization by Reversible Addition−Fragmentation Chain Transfer: The RAFTProcess. Macromolecules, 1998, 31(16): 5559-5562.）。RAFT在体系中加入链转移剂（CTA），可以有效的建立活性增长自由基和休眠物种之间的平衡，随着单体转化率的増加，聚合物链以一定的比例增长。这种方法被用来合成多种分子量和分子量分布可控的聚合物。最近，Boyer课题组发展了一个光引发活性自由基聚合的体系，即光诱导电子转移-可逆加成断裂链转移聚合（PET-RAFT）（S Shanmugam, J Xu, C Boyer. Light-RegulatedPolymerization under Near-Infrared/Far-Red Irradiation Catalyzed byBacteriochlorophyll a. Angewandte Chemie, 2016, 128(3): 1036-1040）。这个聚合体系适用的单体范围广，对聚合物的结构以及分散度控制的很好。光氧化还原催化剂可以通过光诱导电子转移机制来活化可逆加成断裂链转移聚合。在可见光的激发下，光氧化还原催化剂从基态激发到能量最低的三线态。硫代碳酸酯的氧化还原电势比处往激发态的光氧化还原催化剂电势高。光氧化还原催化剂可以通过光诱导电子转移的过程来还原硫代碳酸酯化合物，产生的自由基可以引发单体的RAFT聚合。光引发活性聚合可以在室温下进行。通过控制光源这个外部刺激可以实现聚合反应的＂开＂和＂关＂。
将油相和水相第一次乳化制得的水包油(O/W)乳液，将其转移到另一油相再次乳化制备的乳液就是O/W/O型乳液。O/W/O型乳液的优点是稳定好，可以用于制备有机多孔材料。利用O/W/O型乳液进行光诱导电子转移-可逆加成断裂链转移聚合制备有机多孔材料的方法尚未见报道。
发明内容
本发明的目的是利用光诱导电子转移-可逆加成断裂链转移聚合在O/W/O体系中制备有机多孔材料的方法。具体制备工艺如下：
(1) 将可聚合的功能单体、交联剂、链转移试剂和表面活性剂混合形成油相，它们的重量分别为油相总重量的30-70%、3-18%、0.1-10%和8-35%；
(2) 将光氧化还原催化剂溶解在去离子水中形成水相，光氧化还原催化剂浓度为0.001-0.005 g/L；
(3) 在搅拌下将油相逐滴加入水相中，滴加结束，再加入有机溶剂，继续搅拌，形成乳液；将形成的乳液加入到含有表面活性剂的有机溶剂中，进一步搅拌，得到O/W/O型乳液；
(4) 通氮除氧30 min，室温下开始光照8-24 h，所得产物用水和甲醇分别索氏提取24h，60℃真空干燥24 h，得到有机多孔材料；
本发明一种光诱导电子转移-可逆加成断裂链转移在Q/W/Q乳液体系中聚合制备有机多孔材料的方法，得到的聚合物结构规整，形状均一，孔道分布均匀，且制备的多孔聚合物具有良好的力学性能。使用光诱导电子转移-可逆加成断裂链转移在Q/W/Q乳液体系中聚合制备有机多孔材料的方法，不但实现了有机多孔材料的室温下快速制备，缩短制备周期，而且有机多孔材料孔道尺寸减小到微米级，可以加快传质作用。
具体实施方案：
实施例1：
将2.653 g 丙烯腈、1.13 g二乙烯基苯、0.095 g 4-氰基戊酸二硫代苯甲酸、0.9 g 聚氧乙烯月桂醚搅拌混合，得到油相。将光氧化还原催化剂TiO2 1.8 mg和28.9 g水混合得到水相。在搅拌下将油相逐滴加入水相中，完毕后继续搅拌，再加入10 ml甲苯，继续搅拌。将得到乳液加入到含有5 g 聚氧乙烯月桂醚的30 mL甲苯中，搅拌一段时间，通氮除氧。常温下，光照进行反应。反应结束后，过滤，抽提，真空干燥，得到油机多孔材料。
实施例2：
将1.976 g 甲基丙烯酸甲酯、0.84 g二乙烯基苯、0.083 g 4-氰基戊酸二硫代苯甲酸、0.85 g 聚氧乙烯月桂醚搅拌混合，得到油相。将光氧化还原催化剂曙红Y 0.05 mg和30.3g水混合得到水相。在搅拌下将油相逐滴加入水相中，完毕后继续搅拌，再加入12 ml环己烷，继续搅拌。将得到乳液加入到含有4.6 g 聚氧乙烯月桂醚的30 ml环己烷中，搅拌一段时间，通氮除氧。常温下，光照进行反应。反应结束后，过滤，抽提，真空干燥，得到油机多孔材料。
实施例3：
将1.685 g 苯乙烯、0.72 g二乙烯基苯、0.078 g 4-氰基戊酸二硫代苯甲酸、0.92 g聚氧乙烯月桂醚搅拌混合，得到油相。将光氧化还原催化剂ZnO 1.6 mg和36.3 g水混合得到水相。在搅拌下将油相逐滴加入水相中，完毕后继续搅拌，再加入8 ml正己烷，继续搅拌。将得到乳液加入到含有6.2 g 聚氧乙烯月桂醚的35 ml正己烷中，搅拌一段时间，通氮除氧。常温下，光照进行反应。反应结束后，过滤，抽提，真空干燥，得到油机多孔材料。
实施例4：
将1.42 g 丙烯酰胺、0.61 g N,N'-亚甲基双丙烯酰胺、0.088 g 4-氰基戊酸二硫代苯甲酸、0.68 g 聚氧乙烯月桂醚搅拌混合，得到油相。将光氧化还原催化剂曙红Y 0.04 mg和26.6 g水混合得到水相。在搅拌下将油相逐滴加入水相中，完毕后继续搅拌，再加入15 ml正己烷，继续搅拌。将得到乳液加入到含有8.3 g 聚氧乙烯月桂醚的40 ml正己烷中，搅拌一段时间，通氮除氧。常温下，光照进行反应。反应结束后，过滤，抽提，真空干燥，得到油机多孔材料。
Claims (8)
1.光诱导电子转移-可逆加成断裂链转移聚合制备有机多孔材料的方法，其特征在于包括以下步骤：
(1) 将可聚合的功能单体、交联剂、链转移试剂和表面活性剂混合形成油相，它们的重量分别为油相总重量的30-70%、3-18%、0.1-10%和8-35%；
(2) 将光氧化还原催化剂溶解在去离子水中形成水相，光氧化还原催化剂浓度为0.001-0.005 g/L；
(3) 在搅拌下将油相逐滴加入水相中，滴加结束，再加入有机溶剂，继续搅拌，形成乳液（O/W）；将形成的乳液加入到含有表面活性剂的有机溶剂中，进一步搅拌，得到O/W/O型乳液；
(4) 通氮除氧30 min，室温下开始光照8-24 h，所得产物用水和甲醇分别索氏提取24h，60℃真空干燥24 h，得到有机多孔材料。
2.根据权利要求1所述的光诱导电子转移-可逆加成断裂链转移聚合制备有机多孔材料的方法，其特征在于，所述步骤(1)中，所述的可聚合的功能单体为苯乙烯、甲基丙烯酸甲酯、丙烯腈、丙烯酰胺、甲基丙烯酸β-羟乙酯中的一种或者多种组成。
3.根据权利要求1所述的光诱导电子转移-可逆加成断裂链转移聚合制备有机多孔材料的方法，其特征在于，所述步骤(1)中，所述的交联剂为二乙烯基苯、N,N'-亚甲基双丙烯酰胺。
4.根据权利要求1所述的光诱导电子转移-可逆加成断裂链转移聚合制备有机多孔材料的方法，其特征在于，所述步骤(1)中，所述的链转移试剂为4-氰基戊酸二硫代苯甲酸。
5.根据权利要求1所述的光诱导电子转移-可逆加成断裂链转移聚合制备有机多孔材料的方法，其特征在于，所述步骤(1)和(3)中，所述的表面活性剂为脂肪醇聚氧乙烯醚、聚氧乙烯月桂醚。
6.根据权利要求1所述的光诱导电子转移-可逆加成断裂链转移聚合制备有机多孔材料的方法，其特征在于，所述步骤(2)中，所述的光氧化还原催化剂为叶绿素a、曙红Y、荧光素、TiO2、ZnO。
7.根据权利要求1所述的光诱导电子转移-可逆加成断裂链转移聚合制备有机多孔材料的方法，其特征在于，所述步骤(3)中，所述的有机溶剂为环己烷、甲苯、苯、对二甲苯、正己烷、正庚烷。
8.根据权利要求1所述的光诱导电子转移-可逆加成断裂链转移聚合制备有机多孔材料的方法，其特征在于，所述步骤(4)中，所述的光照射的光源为LED灯、高压汞灯。
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