CN109535315B - 一种具有自修复及防腐蚀功能的复合壳材微胶囊及其制备方法 - Google Patents

一种具有自修复及防腐蚀功能的复合壳材微胶囊及其制备方法 Download PDF

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CN109535315B
CN109535315B CN201811440645.1A CN201811440645A CN109535315B CN 109535315 B CN109535315 B CN 109535315B CN 201811440645 A CN201811440645 A CN 201811440645A CN 109535315 B CN109535315 B CN 109535315B
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罗静
刘仁
董佳豪
陶俊杰
褚航航
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Abstract

本发明公开了一种具有自修复及防腐蚀功能的复合壳材微胶囊，所述微胶囊的壳材由聚苯胺、烯类聚合物、纳米SiO2组成；所述微胶囊的芯材为可聚合活性单体；所述微胶囊尺寸为5～100μm，所述微胶囊的壳层厚度为100nm～2μm；所述烯类聚合物的单体为单官能度烯类单体和双官能度烯类单体的混合；所述可聚合活性单体为桐油、甲苯二异氰酸酯、二苯基甲烷二异氰酸酯、六亚甲基二异氰酸酯、异氟尔酮二异氰酸酯中的一种或多种。本发明微胶囊壳材中含有具有防腐蚀功能的聚苯胺，同时内核中负载有活性单体，其聚合后既可实现涂层破损处的自修复，又能有效抑制金属的腐蚀。

Description

一种具有自修复及防腐蚀功能的复合壳材微胶囊及其制备 方法
技术领域
本发明涉及高分子材料技术领域，尤其是涉及一种具有自修复及防腐蚀功能的复合壳材微胶囊及其制备方法。
背景技术
微胶囊技术是目前最常用的功能物负载方法，优势在于它是一种有效的物质固定化技术，可以通过囊壁将分子封装而与外界环境隔离，保护囊芯性质不被影响，同时在适当条件如加压、升温或辐射下使囊壁破坏，或使囊芯物质透过囊壁向外扩散来实现可控释放。目前，制备微胶囊的方法众多，例如模板法、界面缩聚法、原位聚合法等，其中Pickering乳液模板法为微胶囊的制备提供了简便且有效的制备途径，Pickering乳液即以细微固体颗粒(比如二氧化硅、木质素、硫酸钡和高岭土)代替传统表面活性剂稳定的乳液，与传统乳液相比，Pickering乳液具有超级稳定性，而且起泡性低、无分子迁移带来的毒害性问题。
在涂层中添加具有自修复功能的微胶囊是一种有效的金属防腐蚀手段。主要通过在微胶囊中负载一些可聚合活性单体，当微胶囊随涂层破裂后，负载物释放并聚合，反应形成聚合物层，起到涂层自修复的功能。
目前已报道了多种聚合物(如聚苯乙烯，聚氨酯等)可用作壳材制备制备自修复微胶囊，但大多数壳材主要起包覆作用并提供力学支撑，但对腐蚀本身不存在抑制作用，同时微胶囊与基体相容性差也是目前一个主要的问题。因此目前急需要开发研究壳层具有多功能同时与涂层基体具有优异相容性的自修复微胶囊来满足更广泛的应用要求。
发明内容
针对现有技术存在的上述问题，本发明申请人提供了一种具有自修复及防腐蚀功能的复合壳材微胶囊及其制备方法。本发明微胶囊壳材中含有具有防腐蚀功能的聚苯胺，同时内核中负载有活性单体，其聚合后既可实现涂层破损处的自修复，又能有效抑制金属的腐蚀。
本发明的技术方案如下：
一种具有自修复及防腐蚀功能的复合壳材微胶囊，所述微胶囊的壳材由聚苯胺、烯类聚合物、纳米SiO2组成；所述微胶囊的芯材为可聚合活性单体；所述微胶囊尺寸为5～100μm，所述微胶囊的壳层厚度为100nm～2μm；
所述烯类聚合物的单体为单官能度烯类单体和双官能度烯类单体的混合；
所述可聚合活性单体为桐油、甲苯二异氰酸酯、二苯基甲烷二异氰酸酯、六亚甲基二异氰酸酯、异氟尔酮二异氰酸酯中的一种或多种。
所述单官能度烯类单体为(甲基)丙烯酸缩水甘油酯、(甲基)丙烯酸二甲氨基乙酯、(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丁酯、(甲基)丙烯酸异辛酯、(甲基)丙烯酸羟乙酯、(甲基)丙烯酸乙基己酯、(甲基)丙烯酸、(甲基)丙烯酸叔丁酯、甲氧基聚乙二醇丙烯酸酯、乙氧基乙氧基乙基丙烯酸酯、苯乙烯、N-异丙基丙烯酰胺、丙烯酰胺、2-丁烯酰胺中的一种或多种。
所述双官能度烯类单体为1,6-己二醇丙烯酸酯、1,6-己二醇二(甲基)丙烯酸酯、三缩丙二醇双丙烯酸酯、N,N-亚甲基双丙烯酰胺、二(甲基)丙烯酸乙二醇酯、二乙二醇二丙烯酸酯、新戊二醇二乙氧基丙烯酸酯、邻苯二甲酸二甘醇二丙烯酸酯、二丙二醇二丙烯酸酯、二乙烯基苯中的一种或多种。
一种所述具有自修复及防腐蚀功能的复合壳材微胶囊的制备方法，所述制备方法包括如下步骤：
(1)将纳米SiO2均匀分散于超纯水中作为水相，同时将烯类聚合物单体、苯胺、可聚合活性单体和光引发剂溶解于有机溶剂中作为油相，将油水两相混合，在乳化机作用下形成稳定水包油型乳液；
(2)将步骤(1)制备的乳液置于紫外光下光照2～5min，之后逐滴加入含苯胺引发剂的水溶液，静置状态，在0～20℃条件下反应8～24h；之后采用水和乙醇交替洗涤并干燥，得到负载可聚合活性单体的复合壳材微胶囊，即所述具有自修复及防腐蚀功能的复合壳材微胶囊。
步骤(1)中所述纳米SiO2为市售的气相纳米SiO2、溶胶-凝胶法合成的纳米SiO2、通过硅烷偶联剂疏水改性的气相纳米SiO2中的一种；所述纳米SiO2的粒径为10～100nm。
所述疏水改性用硅烷偶联剂为二苯基二甲氧基硅烷、(3-巯基丙基)三甲氧基硅烷、3-氨基丙基三乙氧基硅烷、3-缩水甘油醚氧基丙基三甲氧基硅烷、3-甲氧丙烯酰氧基丙基三甲氧基硅烷中的一种或多种；所述疏水改性的方法为：将市售气相纳米SiO2分散于乙醇中，加入占SiO2质量2～10％的硅烷偶联剂，之后氨水调节pH为8～10，在50～70℃反应8～16h，反应后用乙醇和超纯水交替洗涤、干燥，制得到硅烷偶联剂疏水改性的气相纳米SiO2。
步骤(1)中所述纳米SiO2在超纯水中的浓度为3～5wt％；所述苯胺单体用量占油相的5～20vol％；所述烯类聚合物的单体中双官能度单体与烯类单官能度单体的体积比为1:1～4，加入总量占油相的30～60vol％；所述可聚合活性单体的用量占烯类聚合物单体和苯胺的10～40wt％；所述光引发剂的用量为烯类聚合物单体的2～5wt％；所述油相与水相的体积比为1:1～4。
步骤(1)中所述有机溶剂为苯、甲苯、二甲苯、氯仿、乙醚、白油、己烷、溴丙烷、二氯乙烷、三氯甲烷、乙酸乙酯、正戊烷、正丁醇中的一种或多种；所述光引发剂为光引发剂1173、光引发剂369、光引发剂2959、光引发剂184、光引发剂907、光引发剂651、光引发剂127、光引发剂819中的一种或多种。
步骤(2)中所述苯胺引发剂为过硫酸铵、过硫酸钾或三氯化铁；所述苯胺引发剂的用量与苯胺单体的摩尔比为1:1～4。
本发明有益的技术效果在于：
本发明采用Pickering乳液模板法制备微胶囊，可通过改变颗粒乳化剂SiO2用量调节乳液滴的粒径从而控制所得微胶囊的大小，同时与传统表面活性剂相比，颗粒乳化剂用量更少，制备的乳液粒径分布更为均匀，稳定性更高，可根据需要调节其亲疏水性，以满足不同油水相极性的需要。另外Pickering乳液模板法制备微胶囊过程简单，经济环保，减少了表面活性剂过度使用造成的污染问题。
本发明微胶囊壳材中含有具有防腐蚀功能的聚苯胺，同时内核中负载有活性单体，其聚合后可实现涂层破损处的自修复，可有效抑制金属的腐蚀，通过电化学阻抗谱(EIS)表征发现添加微胶囊的涂层在NaCl饱和溶液中浸泡1个月后低频区仍具有较高的阻抗模量，证明了微胶囊的添加有效提高了涂层的防腐蚀性能。
本发明微胶囊壳材中含有烯类聚合物，可有效提高微胶囊在涂层中的相容性，同时烯类聚合物可提高微胶囊的韧性和力学强度，弥补聚苯胺刚性较大，质脆的缺点。
附图说明
图1为实施例1合成的自修复及防腐蚀功能的复合壳材微胶囊的结构示意图。
图2为实施例1合成的自修复及防腐蚀功能的复合壳材微胶囊的SEM照片。
图3为实施例1合成的自修复及防腐蚀功能的复合壳材微胶囊在环氧树脂涂层中分散情况的超景深和数码照片。
具体实施方式
下面结合附图和实施例，对本发明进行具体描述。
实施例1
一种具有自修复及防腐蚀功能的复合壳材微胶囊的制备方法，包括如下步骤：
(1)首先称取6g的纳米SiO2分散于50mL溶剂乙醇中，之后加入120mg的二苯基二甲氧基硅烷，加入氨水调节pH为10，在50℃反应8h，反应后用乙醇和超纯水交替洗涤得到改性纳米SiO2；
(2)通过超声将180mg步骤(1)制得的改性纳米SiO2均匀分散于6mL超纯水中作为水相，同时将0.3mL苯胺、0.9mL甲基丙烯酸缩水甘油酯(GMA)、0.9mL1,6-己二醇丙烯酸酯(HDDA)、36mg光引发剂369、180mg异氟尔酮二异氰酸酯(IPDI)溶解于3.9mL甲苯中作为油相，将油水两相混合，通过8000rmp的乳化机乳化2min，形成稳定水包油(O/W)型乳液；
(3)将步骤(2)制得的乳液置于紫外光下光照3min，使烯类单体聚合，光照后逐滴加入含750mg过硫酸铵、25μL HCl(1M)的2mL水溶液，使苯胺聚合，无需任何搅拌在0℃反应10h，用水和乙醇交替洗涤并干燥得到负载活性单体的复合壳材微胶囊，即所述具有自修复及防腐蚀功能的复合壳材微胶囊。
本实施例合成的具有自修复及防腐蚀功能的复合壳材微胶囊的SEM照片如图2所示，由图2可以看出，本发明微胶囊呈规整球型结构，粒径在25μm左右，同时微胶囊未发生破裂，说明壳材可对内部活性单体起到很好的保护作用。
本实施例合成的具有自修复及防腐蚀功能的复合壳材微胶囊在环氧树脂涂层中分散情况的超景深和数码照片如图3所示，在环氧树脂固化前，将占树脂质量2％的具有自修复及防腐蚀功能的复合壳材微胶囊通过搅拌分散到其中，通过辊涂的方式涂覆于金属表面，之后加热固化形成分散有具有自修复及防腐蚀功能的复合壳材微胶囊的环氧树脂涂层。图为树脂固化后的照片，可以看到微胶囊可以在涂层中均匀分散，没有明显的聚集情况。
实施例2
一种具有自修复及防腐蚀功能的复合壳材微胶囊的制备方法，包括如下步骤：
(1)首先称取6g的纳米SiO2分散于50mL溶剂乙醇中，之后加入300mg的3-甲氧丙烯酰氧基丙基三甲氧基硅烷，加入氨水调节pH到8左右，在60℃反应12h,反应后用乙醇和超纯水交替洗涤得到产物。
(2)通过超声将240mg步骤(1)制得的改性纳米SiO2均匀分散于6mL超纯水中作为水相，同时将0.3mL苯胺、0.75mL甲基丙烯酸二甲氨基乙酯(DMAEMA)、0.75mL二乙烯基苯(DVB)、450mg六亚甲基二异氰酸酯(HDI)溶解于1.2mL油相乙酸乙酯中，同时加入54mg光引发剂1173。将油水两相混合，通过10000rmp的乳化剂乳化5min形成稳定水包油(O/W)型乳液。
(3)将步骤(2)制得的乳液置于紫外光下光照4min，使烯类单体聚合，光照后逐滴加入含250mg过硫酸铵、50μL HCl(1M)的2mL水溶液，使苯胺聚合，无需任何搅拌在10℃反应16h，用水和乙醇交替洗涤并干燥得到负载活性单体的复合壳材微胶囊。
实施例3
一种具有自修复及防腐蚀功能的复合壳材微胶囊的制备方法，包括如下步骤：
(1)通过超声将300mg的市购气相SiO2均匀分散于6mL超纯水中，同时将0.3mL苯胺、0.72mL苯乙烯(St)、0.18mL二丙二醇二丙烯酸酯(DPGDA)、324mg二苯基甲烷二异氰酸酯(MDI)溶解于0.3mL油相二氯乙烷中，同时加入41mg光引发剂907。将油水两相混合，通过12500rmp的乳化剂乳化10min形成稳定水包油(O/W)型乳液。
(2)将步骤(1)制得的乳液置于紫外光下光照5min，使烯类单体聚合。光照后逐滴加入含250mg过硫酸铵、100μL HCl(1M)的2mL水溶液，使苯胺聚合，无需任何搅拌在20℃反应24h，用水和乙醇交替洗涤并干燥得到负载活性单体的复合壳材微胶囊。

Claims (9)

1.一种具有自修复及防腐蚀功能的复合壳材微胶囊，其特征在于，所述微胶囊的壳材由聚苯胺、烯类聚合物、纳米SiO2组成；所述微胶囊的芯材为可聚合活性单体；所述微胶囊尺寸为5~100μm，所述微胶囊的壳层厚度为100nm~2μm；
所述烯类聚合物的单体为单官能度烯类单体和双官能度烯类单体的混合；
所述可聚合活性单体为甲苯二异氰酸酯、二苯基甲烷二异氰酸酯、六亚甲基二异氰酸酯、异氟尔酮二异氰酸酯中的一种或多种。
2.根据权利要求1所述的复合壳材微胶囊，其特征在于，所述单官能度烯类单体为（甲基）丙烯酸缩水甘油酯、（甲基）丙烯酸二甲氨基乙酯、（甲基）丙烯酸甲酯、(甲基)丙烯酸乙酯、（甲基）丙烯酸丁酯、（甲基）丙烯酸异辛酯、（甲基）丙烯酸羟乙酯、（甲基）丙烯酸乙基己酯、（甲基）丙烯酸、（甲基）丙烯酸叔丁酯、甲氧基聚乙二醇丙烯酸酯、乙氧基乙氧基乙基丙烯酸酯、苯乙烯、N-异丙基丙烯酰胺、丙烯酰胺、2-丁烯酰胺中的一种或多种。
3.根据权利要求1所述的复合壳材微胶囊，其特征在于，所述双官能度烯类单体为1,6-己二醇二丙烯酸酯、1,6-己二醇二（甲基）丙烯酸酯、三缩丙二醇双丙烯酸酯、N,N-亚甲基双丙烯酰胺、二（甲基）丙烯酸乙二醇酯、二乙二醇二丙烯酸酯、新戊二醇二乙氧基丙烯酸酯、邻苯二甲酸二甘醇二丙烯酸酯、二丙二醇二丙烯酸酯、二乙烯基苯中的一种或多种。
4.一种权利要求1所述具有自修复及防腐蚀功能的复合壳材微胶囊的制备方法，其特征在于，所述制备方法包括如下步骤：
（1）将纳米SiO2均匀分散于超纯水中作为水相，同时将烯类聚合物单体、苯胺、可聚合活性单体和光引发剂溶解于有机溶剂中作为油相，将油水两相混合，在乳化机作用下形成稳定水包油型乳液；
（2）将步骤（1）制备的乳液置于紫外光下光照2~5 min，之后逐滴加入含苯胺引发剂的水溶液，静置状态，在0~20℃条件下反应8~24 h；之后采用水和乙醇交替洗涤并干燥，得到负载可聚合活性单体的复合壳材微胶囊，即所述具有自修复及防腐蚀功能的复合壳材微胶囊。
5.根据权利要求4所述的制备方法，其特征在于，步骤（1）中所述纳米SiO2为市售的气相纳米SiO2、溶胶-凝胶法合成的纳米SiO2、通过硅烷偶联剂疏水改性的气相纳米SiO2中的一种；所述纳米SiO2的粒径为10~100 nm。
6.根据权利要求5所述的制备方法，其特征在于，所述疏水改性用硅烷偶联剂为二苯基二甲氧基硅烷、(3-巯基丙基)三甲氧基硅烷、3-氨基丙基三乙氧基硅烷、3-缩水甘油醚氧基丙基三甲氧基硅烷、3-甲氧丙烯酰氧基丙基三甲氧基硅烷中的一种或多种；所述疏水改性的方法为：将市售气相纳米SiO2分散于乙醇中，加入占SiO2质量2~10%的硅烷偶联剂，之后氨水调节pH为8~10，在50~70℃反应8~16 h，反应后用乙醇和超纯水交替洗涤、干燥，制得到硅烷偶联剂疏水改性的气相纳米SiO2。
7.根据权利要求4所述的制备方法，其特征在于，步骤（1）中所述纳米SiO2在超纯水中的浓度为3~5wt%；所述苯胺单体用量占油相的5~20vol%；所述烯类聚合物的单体中双官能度单体与烯类单官能度单体的体积比为1:1~4，加入总量占油相的30~60 vol%；所述可聚合活性单体的用量占烯类聚合物单体和苯胺的10~40 wt%；所述光引发剂的用量为烯类聚合物单体的2~5wt%；所述油相与水相的体积比为1:1~4。
8.根据权利要求4所述的制备方法，其特征在于，步骤（1）中所述有机溶剂为苯、甲苯、二甲苯、氯仿、乙醚、白油、己烷、溴丙烷、二氯乙烷、三氯甲烷、乙酸乙酯、正戊烷、正丁醇中的一种或多种；所述光引发剂为光引发剂1173、光引发剂369、光引发剂2959、光引发剂184、光引发剂907、光引发剂651、光引发剂127、光引发剂819中的一种或多种。
9.根据权利要求4所述的制备方法，其特征在于，步骤（2）中所述苯胺引发剂为过硫酸铵、过硫酸钾或三氯化铁；所述苯胺引发剂的用量与苯胺单体的摩尔比为1:1~4。
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