CN115181243A - 一种自修复可拆解的丁羟胶固化物及其复合物 - Google Patents

一种自修复可拆解的丁羟胶固化物及其复合物 Download PDF

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CN115181243A
CN115181243A CN202210613351.4A CN202210613351A CN115181243A CN 115181243 A CN115181243 A CN 115181243A CN 202210613351 A CN202210613351 A CN 202210613351A CN 115181243 A CN115181243 A CN 115181243A
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周琳
向仕鹏
陈茂
付奇岩
张魁宝
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Southwest University of Science and Technology
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Abstract

本发明提出一种自修复可拆解的丁羟胶固化物及其复合物，首先利用含动态键的二羟基化合物和二异氰酸酯化合物在氮气气氛下反应得到含动态键的二异氰酸酯前驱体，随后该前驱体和丁羟胶在一定温度下固化完全得到一种自修复可拆解的丁羟胶固化物。在前驱体和丁羟胶的固化过程中加入无机填料即可制备丁羟胶的复合物。该基于动态键的自修复可拆解丁羟胶固化物及其复合物具有良好耐溶剂性，在高温溶剂中也只溶胀不溶解，且在高温下可重塑、可修复，在特定刺激条件下可拆解，其复合物在拆解后能够实现无机填料的有效回收。

Description

一种自修复可拆解的丁羟胶固化物及其复合物
技术领域
本发明属于高分子材料领域，涉及一种自修复可拆解的丁羟胶固化物及其复合物。
背景技术
丁羟胶又称端羟基聚丁二烯，也称液体橡胶，末端有两个以上的羟基可很容易和二异氰酸酯固化反应形成三维交联网络，所得的丁羟胶固化物具有优异的力学性能、耐酸碱以及化学结构稳定等特点在航空航天、轮船汽车、涂层、防水防腐、胶粘剂和保温材料等方面得到了广泛的应用。然而丁羟胶固化物也属于热固性聚合物，内部的永久三维交联网络使其不能重复利用和再加工，故废弃的材料只能通过填埋和焚烧处理，造成了一定的环境污染和资源浪费。
将可逆动态键引入到热固性聚合物中构建适应性网络可赋予材料自修复、拆解和再加工等性能，从而使丁羟胶固化物具有修复和拆解成为可能。故将可逆动态键引入到丁羟胶固化物中既能保持其特有的优异性能也可以修复拆解，从一定程度上缓解了部分环境和资源压力。
在本文中，我们设计了一种基于动态共价键交联的丁羟胶固化物。一方面借助动态共价键的可逆动态性能，使丁羟胶固化物具有可修复、可拆解、可再加工的性能。另一方面，在得到丁羟胶固化物前驱体时加入无机填料，可得到含动态键的丁羟胶固化物复合物，该复合物可在丁羟胶固化物有效拆解后回收填料。
发明内容
一种基于动态共价键交联的丁羟胶固化物，使用二异氰酸酯和含动态键的羟基化合物反应形成含动态键的二异氰酸酯前驱体，该前驱体和丁羟胶混合均匀后固化完全得到含动态键的自修复可拆解的丁羟胶固化物。其复合物由二异氰酸酯前驱体和丁羟胶以及不同质量分数的无机填料在相同条件下固化形成。
所述的二异氰酸酯包括异佛尔酮二异氰酸酯、甲苯二异氰酸酯、六亚甲基二异氰酸酯、二苯基甲烷二异氰酸酯、二环己基甲烷二异氰酸酯，所述含动态键的二羟基化合物中动态键包括二硫键、亚胺键和苯硼酸酯键，所述无机填料为二氧化硅微粉。
附图说明
图1自修复可拆解的丁羟胶固化物及其复合物的拆解、修复机理示意图。
图2含二硫键的自修复可拆解的丁羟胶固化物拆解、修复。
图3 含二硫键的丁羟胶复合物的拆解、回收。
具体实施方式
本发明技术方案不限于下列具体实施方式，还包括各具体实施方式间的任意组合。
具体实施方式一：本发明的自修复可拆解的丁羟胶固化物及其复合物，按照二异氰酸酯（22mmol）和含动态键的羟基化合物（10mmol）及超干四氢呋喃组成混合体，并加入二月桂酸二丁基锡作为催化剂，在70℃氮气气氛下搅拌6小时，形成含动态二硫键的二异氰酸酯前驱体，该前驱体和丁羟胶（10mmol）在60℃下固化完全得到基于动态键交联的自修复可拆解丁羟胶固化物，复合物由二异氰酸酯前驱体和丁羟胶及不同质量分数（50-100wt%）的二氧化硅微粉混合均匀后在60℃下固化形成。
所述的二异氰酸酯为异佛尔酮二异氰酸酯，所述含动态键化合物为含二硫键二羟基化合物。
该基于二硫键的自修复可拆解的丁羟胶固化物及复合物具有优异的拆解性和修复性以及填料循环回收性。丁羟胶固化物的拆解、修复如图2所示，修复方式，包括划痕修复、焊接、碎片热压。复合物的拆解、回收如图3所示。
具体实施方式二：本发明的自修复可拆解的丁羟胶固化物及其复合物，按照二异氰酸酯（22mmol）和含动态键的羟基化合物（10mmol）及超干四氢呋喃组成混合体，并加入二月桂酸二丁基锡作为催化剂，在70℃氮气气氛下搅拌6小时，形成含动态键的二异氰酸酯前驱体，该前驱体和丁羟胶（10mmol）在60℃下固化完全得到基于动态键交联的自修复可拆解丁羟胶固化物，复合物由二异氰酸酯前驱体和丁羟胶及不同质量分数（50-100wt%）的二氧化硅微粉混合均匀后在60℃下固化形成。
所述的二异氰酸酯为六亚甲基二异氰酸酯，含动态键化合物为含亚胺键二羟基化合物。
该基于亚胺键的自修复可拆解的丁羟胶固化物及复合物具有优异的拆解性和修复性以及填料循环回收性，修复方式包括划痕修复、焊接、碎片热压。
具体实施方式三：本发明的自修复可拆解的丁羟胶固化物及其复合物，按照二异氰酸酯（22mmol）和含动态键的羟基化合物（10mmol）及超干四氢呋喃组成混合体，并加入二月桂酸二丁基锡作为催化剂，在70℃氮气气氛下搅拌6小时，形成含动态键的二异氰酸酯前驱体，该前驱体和丁羟胶（10mmol）在60℃下固化完全得到基于动态键交联的自修复可拆解丁羟胶固化物，复合物由二异氰酸酯前驱体和丁羟胶及不同质量分数（50-100wt%）的二氧化硅微粉混合均匀后在60℃下固化形成。
所述的二异氰酸酯为甲苯二异氰酸酯，含动态键化合物为含硼酸酯键二羟基化合物。
该基于硼酸酯的自修复可拆解的丁羟胶固化物及复合物具有优异的拆解性和修复性以及填料循环回收性，修复方式包括划痕修复、焊接、碎片热压。
具体实施方式四：本发明的自修复可拆解的丁羟胶固化物及其复合物，按照二异氰酸酯（22mmol）和含动态键的羟基化合物（10mmol）及超干四氢呋喃组成混合体，并加入二月桂酸二丁基锡作为催化剂，在70℃氮气气氛下搅拌6小时，形成含动态键的二异氰酸酯前驱体，该前驱体和丁羟胶（10mmol）在60℃下固化完全得到基于动态键交联的自修复可拆解丁羟胶固化物，复合物由二异氰酸酯前驱体和丁羟胶及不同质量分数（50-100wt%）的二氧化硅微粉混合均匀后在60℃下固化形成。
所述的二异氰酸酯为异佛尔酮二异氰酸酯，含动态键化合物为含亚胺键二羟基化合物。
该基于亚胺键的自修复可拆解的丁羟胶固化物及复合物具有优异的拆解性和修复性以及填料循环回收性，修复方式包括划痕修复、焊接、碎片热压。

Claims (1)

1.一种基于动态共价键交联的丁羟胶固化物，使用二异氰酸酯和含动态键的羟基化合物反应形成含动态键的二异氰酸酯前驱体，该前驱体和丁羟胶混合均匀后固化完全得到含动态键的自修复可拆解的丁羟胶固化物。其复合物由二异氰酸酯前驱体和丁羟胶以及不同质量分数的无机填料在相同条件下固化形成。所述的二异氰酸酯包括异佛尔酮二异氰酸酯、甲苯二异氰酸酯、六亚甲基二异氰酸酯、二苯基甲烷二异氰酸酯、二环己基甲烷二异氰酸酯。所述含动态键的二羟基化合物中动态键包括二硫键、亚胺键、和苯硼酸酯键。所述无机填料为二氧化硅微粉。
CN202210613351.4A 2022-06-01 2022-06-01 一种自修复可拆解的丁羟胶固化物及其复合物 Pending CN115181243A (zh)

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