CN106589735B - 一种利用raft聚合制备自修复杂化膜的方法 - Google Patents

一种利用raft聚合制备自修复杂化膜的方法 Download PDF

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CN106589735B
CN106589735B CN201611143940.1A CN201611143940A CN106589735B CN 106589735 B CN106589735 B CN 106589735B CN 201611143940 A CN201611143940 A CN 201611143940A CN 106589735 B CN106589735 B CN 106589735B
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王文香
李玉琦
柏良久
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Ludong University
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Abstract

本发明公开了一种具有自修复性能杂化膜的合成方法，其中聚合按质量比，为丙烯酸丁酯:2‑(3‑(6‑甲基‑4‑羰基‑1,4‑二氢嘧啶基)脲基)甲基丙烯酸乙酯：二氧化硅/聚二乙烯基苯Janus纳米颗粒：二硫代萘甲酸异丁腈酯：偶氮二异丁腈=1~100：1~10：10~200：0.2~3：0.1~2，成膜后12小时修复效果较好。

Description

一种利用RAFT聚合制备自修复杂化膜的方法
技术领域
本发明涉及一种通过可逆加成—断裂链转移（RAFT）聚合制备自修复杂化膜的制备方法，属于功能高分子材料领域。
背景技术
高分子材料在其成型加工和使用过程中不可避免地会产生局部损伤和微裂纹，进而引发宏观裂缝而发生破坏，影响相关产品的正常使用和缩短使用寿命，而往往这些微损伤在开始的时候难以发现，或者即使被发现也因产品形状等限制无法得到及时修复。因此，如果能够赋予高分子材料自修复功能，即可解决上述问题，显著提高产的安全性，延长其使用寿命。至今，根据自修复机理和材料制备特点大致可分两大类:外植型和本征型自修复材料。外植型自修复高分子材料含有预先埋置的修复剂，通常修复剂装载在胶囊、空心玻璃纤维等微容器中，当材料中产生微裂纹时，分布在裂纹扩展路径上的微容器也随之破裂，释放出液态修复剂，基于毛细原理迅速抵达裂纹处，通过化学或物理作用将断面重新接合起来。本征型自修复高分子材料不需要添加修复剂，在一定的外场刺激下，依靠大分子的断链-结合可逆反应能力，即可自行修复损伤;此外,这类材料由于不存在修复剂消耗的问题，因而较易进行损伤的多次修复。
1998年Rizzardo等人第一次提出了可逆加成断裂链转移聚合，这是一种可以得到明确结构和预定分子量的共聚物的好方法。随之RAFT聚合便引起了高分子界的热议。RAFT聚合不仅有较好的满足对分子的设计，还有很多单体都可应用于RAFT聚合。
Janus是罗马神话中双面神的名字，神话中他有两副面孔，一副朝向过去，一副朝向未来。1991年，Pierre-Gilles de Gennes在他的Nobel演讲中首次用“Janus”来描述那些具有双重性质的微粒。这种Janus胶体颗粒能够同时拥有两种不同、甚至截然相反的化学性质：从形貌上看，结构的不对称性赋予Janus材料特殊的空间位阻效应，可以用来研究自组装及靶向识别等；从组成上看，Janus材料可兼具两种不同甚至相反的性质，如亲水/亲油、极性/非极性、正电荷/负电荷和磁性/非磁性等，从而赋予材料多功能性。因此，Janus材料可以根据使用环境调节材料的功能性以满足复杂环境中的使用要求。基于此特殊性质，Janus 颗粒为人们进一步设计新型颗粒乳化剂、多相催化剂、自驱动纳米马达、以及作为构筑单元组装形成超结构等都提供了理想的科研平台，在物理、化学、生物等领域有着广泛的应用前景，对促进新材料的发展起着至关重要的作用。
本发明专利基于RAFT聚合在制备功能性聚合物等方面的优势，对氢键型单体、丙烯酸丁酯和Janus纳米粒子，制备了具有自修复性能的复合膜功能材料，研究了自修复效果。
发明内容
本发明目的是提供一种具有自修复性能杂化膜的制备方法。
本发明提供了一种具有自修复性能复合膜的制备方法，包括如下步骤:
为达到上述目的，本发明具体技术方案是，利用RAFT聚合制备具有自修复性能复合膜,聚合体系包括：丙烯酸丁酯（nBA）、氢键单体（2-(3-(6-甲基-4-羰基-1,4-二氢嘧啶基)脲基)甲基丙烯酸乙酯）、Janus纳米粒子（二氧化硅/聚二乙烯基苯Janus颗粒）、RAFT试剂、自由基引发剂，其中，按质量比，丙烯酸丁酯（nBA）:单体（S3）：Janus纳米粒子：RAFT试剂：引发剂= 1~100：1~10：10~200：0.2~3：0.1~2；
所述的RAFT试剂为二硫代萘甲酸异丁腈酯；
所述自由基引发剂为：2,2'-偶氮二异丁腈（AIBN）；
所述Janus纳米粒子：二氧化硅/聚二乙烯基苯Janus颗粒；
所述复合膜制备包括：在得到的共聚物中加入四氢呋喃溶解，将溶解好的样品倒入模具中，放置在电热恒温干燥箱待溶剂挥发后得到复合膜。
应用上述RAFT聚合体系合成具有自修复性能杂化膜的方法，包括以下步骤：
(1)按照权利要求1所述配方配制聚合体系；
(2)制备复合膜及自修复性能考察。
上述技术方案中，可以通过调整反应中纳米粒子的用量，通过调整共聚单体的比例改善自修复性能。
上述技术方案中，所得由于上述技术方案运用，本发明与现有技术相比具有下列优点：本发明加入了Janus纳米粒子，提高了复合膜的强度；本发明为可控性好、自修复性能好的功能性自修复材料的设计、合成提供理论依据。
具体实施方式
实施例一：称取4.0 g的 2-氨基-4-羟基-6-甲基嘧啶和50 ml 的二甲基亚砜 于150 ml 的三口烧瓶中，反应在150摄氏度下进行，等到烧瓶里的固体全部溶解，出现淡黄色透明液体时，停止加热，冷却溶液至室温，然后迅速加入5.5 g的甲基丙烯酸异氰基乙酯，搅拌两个小时后出现白色固体，然后停止搅拌，将反应物倒入丙酮里，最后进行减压抽滤并将所得产物放入电热真空干燥箱进行干燥处理得到2-(3-(6-甲基-4-羰基-1,4-二氢嘧啶基)脲基)甲基丙烯酸乙酯。
实施例二：将100毫克单体(2-(3-(6-甲基-4-羰基-1,4-二氢嘧啶基)脲基)甲基丙烯酸乙酯)、20毫克Janus纳米粒子（二氧化硅/聚二乙烯基苯Janus颗粒），2.0毫克偶氮二异丁腈，3.0毫克二硫代萘甲酸异丁腈酯，2.0毫升丙烯酸丁酯，加入到装有1.0毫升N,N-二甲基甲酰胺的安瓿瓶中，搅拌均匀，置于65摄氏度条件下反应4小时，得到产物加入四氢呋喃，完全溶解得到原液。
实施例三：将原液倒入底部为圆形的模具中，用保鲜膜包裹防止灰尘落入，放在50摄氏度的电热恒温干燥箱中，烘干12小时，得到复合膜。
实施例四：将所得到的复合膜用剪刀剪开，拼接在一起使其接触，放在通风橱中修复，不断观察，十二小时后轻微的愈合，二十四小时愈合程度较高但还可以看出裂缝，三十六小时后完全修复，无裂纹。自修复效果显著。

Claims (1)

1.一种利用RAFT聚合制备自修复杂化膜的方法，其特征在于：RAFT聚合体系包括：Janus纳米粒子、丙烯酸丁酯、2-(3-(6-甲基-4-羰基-1,4-二氢嘧啶基)脲基)甲基丙烯酸乙酯、RAFT试剂、自由基引发剂，其中，按质量比，丙烯酸丁酯：2-(3-(6-甲基-4-羰基-1,4-二氢嘧啶基)脲基)甲基丙烯酸乙酯：Janus纳米粒子：RAFT试剂：自由基引发剂 = 1~100：1~10：10~200：0.2~3：0.1~2；
所述的Janus纳米粒子为：二氧化硅/聚二乙烯基苯Janus颗粒；
所述的RAFT试剂为：二硫代萘甲酸异丁腈酯；
所述自由基引发剂为：2,2'-偶氮二异丁腈；
复合膜制备包括：在得到的共聚物中加入四氢呋喃溶解，将溶解好的样品倒入模具中，放置在电热恒温干燥箱待溶剂挥发后得到复合膜。
CN201611143940.1A 2016-12-13 2016-12-13 一种利用raft聚合制备自修复杂化膜的方法 Expired - Fee Related CN106589735B (zh)

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