CN111704710A - 含氟酰氨基脲高性能动态聚合物及其制备方法 - Google Patents

含氟酰氨基脲高性能动态聚合物及其制备方法 Download PDF

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CN111704710A
CN111704710A CN202010645563.1A CN202010645563A CN111704710A CN 111704710 A CN111704710 A CN 111704710A CN 202010645563 A CN202010645563 A CN 202010645563A CN 111704710 A CN111704710 A CN 111704710A
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dynamic polymer
semicarbazide
fluorochemical
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夏和生
杨茂雨
王硕
王占华
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Sichuan University
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Abstract

本发明公开了含氟酰氨基脲高性能动态聚合物及其制备方法，由以下原料按照质量份数制备而成：单体10～80份，所述的单体为聚醚胺单体或者聚酯多元醇单体或者聚醚多元醇单体中的一种或几种；二异氰酸酯单体5～50份；含氟二酰肼单体5～50份；交联剂0.1～10份。本发明获得材料结构简单，易于合成制备；材料具有优异的力学性能、光学性能、耐水性能以及热稳定性同时，也展现出良好的自修复、重加工和可回收性能。

Description

含氟酰氨基脲高性能动态聚合物及其制备方法
技术领域
本发明涉及光学聚合物材料领域，尤其是含氟酰氨基脲高性能动态聚合物及其制备方法。
背景技术
常见光学材料往往可以分为无机和有机两大类。无机光学材料包括光学玻璃、微晶玻璃、 光学晶体、金属材料等，其中以光学玻璃应用最广。目前，常见和常用的有机光学材料包括 聚甲基丙烯酸甲酯(PMMA)、聚苯乙烯(PS)、聚碳酸酯(PC)、烯丙基二甘醇聚碳酸酯(CR-39)、 苯乙烯丙烯腈(SAN)、苯乙烯丙烯酸(NAS)、丁苯树脂(LH)和有机透明橡胶等，其中以PMMA、 PS、PC、CR-39、有机硅橡胶性能突出在光学零件中应用最广。其中有机光学材料相较于无 极光学材料有很多独特的优点，例如质轻、耐冲击、成本低等，但同样也存在一些缺点：热 膨胀系数大、耐候性差等。其中芳香族聚酰亚胺(PI)是一类分子链中含有酰亚胺芳杂环的聚合 物，它具有其他很多高分子材料所无法比拟的优异力学性能与耐高温、耐低温性能。另外， 聚酰亚胺抗蠕变能力强，具有良好的韧性，有一定的抗紫外辐照性能，合成及成型工艺温和， 性能改性空间大。随着环境问题的日益凸显，赋予材料自修复性能延长材料的使用周期，且 赋予材料的可回收性制备环境友好型材料，是未来材料的重要研究方向。聚酰亚胺材料由于 聚合物分子链的刚性，分子链运动困难，很难实现材料的自修复和回收，因此合成新型的动 态光学聚合物材料尤为重要。
发明内容
本发明要解决的技术问题是：为了解决目前柔性显示领域所使用的聚酰亚胺类材料(PI) 的修复和回收问题，本发明提供了一种新型的含氟聚酰氨基脲动态聚合物及其制备方法，该 该聚合物材料结构简单、原料易得且易于合成制备；材料力学性能优异，具有高的强度、模 量和韧性；材料光学性能优异(高的可见光透过)；材料耐水性能优异；材料具有良好的热稳 定性；材料具有优异的自修复和回收性能，多次重加工后，仍能保持力学性能与光学性能几 乎不变。
本发明解决其技术问题所采用的技术方案是：
一种含氟酰氨基脲高性能动态聚合物，该聚合物由以下各种原料按照重量份数制备而成：
单体10～80份，所述的单体为聚醚胺单体或者聚酯多元醇单体或者聚醚多元醇单体中的 一种或几种；
二异氰酸酯单体5～50份；
含氟二酰肼单体5～50份；
交联剂0.1～10份。
具体地，聚醚胺单体为聚醚二元胺D-230、D-400、D-2000、ED-600、ED-900、ED-2003、 polyTHF amine 350、polyTHF amine 1700中的一种或几种。
具体地，聚酯多元醇单体为聚己二酸乙二醇酯、聚己二酸乙二醇丙二醇酯、聚己二酸乙 二醇丁二醇酯、聚ε-己内酯二醇中的一种或几种。
具体地，聚醚多元醇单体为聚环氧丙烷均聚醚多醇、聚环氧乙烷均聚醚多醇、四氢呋喃 均聚醚多醇中的一种或者几种。
具体地，含氟二酰肼单体包括如下结构式的化合物中的一种或者几种，
Figure BDA0002572342240000021
具体地，二异氰酸酯单体包括如下结构式得化合物中得一种或者几种：
Figure BDA0002572342240000022
Figure BDA0002572342240000031
具体地，交联剂包括如下结构式得化合物中得一种或者几种：
Figure BDA0002572342240000032
含氟酰氨基脲高性能动态聚合物的制备方法，将含氟二酰肼单体、二异氰酸酯单体、交 联剂溶于溶剂中，在快速搅拌的同时加入聚醚胺或者聚酯二元醇或者聚醚二元醇单体，80℃ 下反应12h后，真空干燥除去溶剂即可得到含氟酰氨基脲高性能动态聚合物材料。
该聚合物材料可用于制作柔性显示透明基板，将柔性显示电子元件及材料安装在该基板 上，能够赋予显示器弯曲或卷曲成任意形状的特性，以实现柔性显示技术。此外还可以作为 有机光学玻璃应用于汽车、电子电器、建材、航空航天、光学等领域。在该类材料中添加无 机或有机填料，如石墨烯、MXene、碳纳米管、黏土、金属氧化物、金属盐、玻纤、碳纤维、 天然纤维等，但依然利用本发明所述材料功能的应该属于本专利范畴。无论使用何种加工手 段，如热压、注塑、挤出、纺丝、吹塑等，更换溶剂或者调整加料顺序，都应属于本专利范 畴。
本发明的有益效果是：本发明提供了一种含氟聚酰氨基脲动态聚合物及其制备方法，该 该聚合物材料结构简单、原料易得且易于合成制备；材料力学性能优异，具有高的强度、模 量和韧性；材料光学性能优异(高的可见光透过)；材料具有优异的耐水性能；材料具有良好 的热稳定性；材料具有优异的自修复和回收性能，多次冲加工后，仍能保持力学性能、光学 性能和耐水性能几乎不变。
附图说明
图1a是本发明的含氟酰氨基脲动态聚合物-1材料热压回收两次的应力应变曲线图；
图1b是本发明的含氟酰氨基脲动态聚合物-1材料热压回收两次的可见光透过率测试图；
图1c是本发明的含氟酰氨基脲动态聚合物-1材料热压回收两次的水接触角测试图；
图2a是本发明的含氟酰氨基脲动态聚合物-2材料热压回收两次的应力应变曲线图；
图2b是本发明的含氟酰氨基脲动态聚合物-2材料热压回收两次的可见光透过率测试图；
图2c是本发明的含氟酰氨基脲动态聚合物-2材料热压回收两次的水接触角测试图；
图3a是本发明的含氟酰氨基脲动态聚合物-3材料热压回收两次的应力应变曲线图；
图3b是本发明的含氟酰氨基脲动态聚合物-3材料热压回收两次的可见光透过率测试图；
图3c是本发明的含氟酰氨基脲动态聚合物-3材料热压回收两次的水接触角测试图；
图4a是本发明的含氟酰氨基脲动态聚合物-4材料热压回收两次的应力应变曲线图；
图4b是本发明的含氟酰氨基脲动态聚合物-4材料热压回收两次的可见光透过率测试图；
图4c是本发明的含氟酰氨基脲动态聚合物-4材料热压回收两次的水接触角测试图；
图5a是本发明的含氟酰氨基脲动态聚合物-5材料热压回收两次的应力应变曲线图；
图5b是本发明的含氟酰氨基脲动态聚合物-5材料热压回收两次的可见光透过率测试图；
图5c是本发明的含氟酰氨基脲动态聚合物-5材料热压回收两次的水接触角测试图。
具体实施方式
下面结合附图和实施例对本发明进一步说明。
实施例1
含氟酰氨基脲动态聚合物-1的制备：将4.4456g异佛尔酮二异氰酸酯(IPDI)和0.3364g 六亚甲基二异氰酸酯三聚体(Tri-HDI)溶解于30ml N,N’-二甲基甲酰胺中，并在搅拌速度为200 r/min的条件下加入3.4992g八氟己二酸二酰肼，待其完全反应溶解，溶液呈透明液体后，提 升搅拌速度为600r/min，迅速加入10g事先配制好的60wt％聚醚胺(ED600)/DMF溶液，搅 拌片刻后，将其放置在80℃烘箱中固化12h，再置于100℃下真空干燥24h，即可得到含氟 酰氨基脲动态聚合物材料。
实施例2
含氟酰氨基脲动态聚合物-1材料回收性能展示：将实施1中所值得的含氟酰氨基脲动态 聚合物-1材料剪成碎片，在140℃、15MPa下热压1h后，即可得到性能突出的材料。为充 分展示其优异的可回收性能，将热压成型后的材料再次剪成碎片进行热压。图1a到图1c分 别是热压回收前后的应力-应变曲线、透光性测试曲线和水接触角实验。
实施例3
含氟酰氨基脲动态聚合物-2的制备：将3.364g六亚甲基二异氰酸酯(HDI)和0.3364g六 亚甲基二异氰酸酯三聚体(Tri-HDI)溶解于30ml N,N’-二甲基甲酰胺中，并在搅拌速度为200 r/min的条件下加入7.6717g 2,2-双[4-(4-酰肼-2-三氟甲基苯氧基)苯基]六氟丙烷，待其完全反 应溶解，溶液呈透明液体后，提升搅拌速度为600r/min，迅速加入10g事先配制好的50wt％ (PCL500)/DMF溶液，搅拌片刻后，将其放置在80℃烘箱中固化12h，再置于100℃下真空 干燥24h，即可得到含氟酰氨基脲动态聚合物材料。
实施例4
含氟酰氨基脲动态聚合物-2材料回收性能展示：将实施3中所值得的含氟酰氨基脲动态 聚合物-2材料剪成碎片，在140℃、15MPa下热压1h后，即可得到性能突出的材料。为充 分展示其优异的可回收性能，将热压成型后的材料再次剪成碎片进行热压。图2a到图2c分 别是热压回收前后的应力-应变曲线、透光性测试曲线和水接触角实验。
实施例5
含氟酰氨基脲动态聚合物-3的制备：将5.247g4,4’-二环己基甲烷二异氰酸酯(HMDI)和 0.3364g六亚甲基二异氰酸酯三聚体(Tri-HDI)溶解于30ml N,N’-二甲基甲酰胺中，并在搅拌 速度为200r/min的条件下加入4.6648g 2,2’-双三氟甲基-4,4’-二酰肼二苯醚，待其完全反应溶 解，溶液呈透明液体后，提升搅拌速度为600r/min，迅速加入10g事先配制好的60wt％聚 丙二醇(PPG600)/DMF溶液，搅拌片刻后，将其放置在80℃烘箱中固化12h，再置于100℃ 下真空干燥24h，即可得到含氟酰氨基脲动态聚合物材料。
实施例6
含氟酰氨基脲动态聚合物-3材料回收性能展示：将实施5中所值得的含氟酰氨基脲动态 聚合物-3材料剪成碎片，在140℃、15MPa下热压1h后，即可得到性能突出的材料。为充 分展示其优异的可回收性能，将热压成型后的材料再次剪成碎片进行热压。图3a到图3c分 别是热压回收前后的应力-应变曲线、透光性测试曲线和水接触角实验。
实施例7
含氟酰氨基脲动态聚合物-4的制备：将5.0048g二苯基甲烷二异氰酸酯(MDI)和0.3364g 六亚甲基二异氰酸酯三聚体(Tri-HDI)溶解于30ml N,N’-二甲基甲酰胺中，并在搅拌速度为200 r/min的条件下加入5.1735g 2,2’-双三氟甲基-4,4’-二酰肼二苯基砜，待其完全反应溶解，溶液 呈透明液体后，提升搅拌速度为600r/min，迅速加入10g事先配制好的65wt％聚四氢呋喃 (PTMEG650)/DMF溶液，搅拌片刻后，将其放置在80℃烘箱中固化12h，再置于100℃下真 空干燥24h，即可得到含氟酰氨基脲动态聚合物材料。
实施例8
含氟酰氨基脲动态聚合物-4材料回收性能展示：将实施7中所值得的含氟酰氨基脲动态 聚合物-4材料剪成碎片，在140℃、15MPa下热压1h后，即可得到性能突出的材料。为充 分展示其优异的可回收性能，将热压成型后的材料再次剪成碎片进行热压。图4a到图4c分 别是热压回收前后的应力-应变曲线、透光性测试曲线和水接触角实验。
实施例9
含氟酰氨基脲动态聚合物-5的制备：将4.8858g1,3-双(2-异氰基-2-丙基)苯(TMXDI)和 0.3364g六亚甲基二异氰酸酯三聚体(Tri-HDI)溶解于30ml N,N’-二甲基甲酰胺(DMF)中，并在 搅拌速度为200r/min的条件下加入4.8215g 2,2’-双三氟甲基-4,4’-二酰肼二苯硫醚，待其完全 反应溶解，溶液呈透明液体后，提升搅拌速度为600r/min，迅速加入10g事先配制好的60wt％ 聚乙二醇(PEG600)/DMF溶液，搅拌片刻后，将其放置在80℃烘箱中固化12h，再置于100℃ 下真空干燥24h，即可得到含氟酰氨基脲动态聚合物材料。
实施例10
含氟酰氨基脲动态聚合物-5材料回收性能展示：将实施9中所值得的含氟酰氨基脲动态 聚合物-5材料剪成碎片，在140℃、15MPa下热压1h后，即可得到性能突出的材料。为充 分展示其优异的可回收性能，将热压成型后的材料再次剪成碎片进行热压。图5a到图5c分 别是热压回收前后的应力-应变曲线、透光性测试曲线和水接触角实验。

Claims (8)

1.一种含氟酰氨基脲高性能动态聚合物，其特征在于，由以下原料按照质量份数制备而成：
单体 10～80份，所述的单体为聚醚胺单体或者聚酯多元醇单体或者聚醚多元醇单体中的一种或几种；
二异氰酸酯单体 5～50份；
含氟二酰肼单体 5～50份；
交联剂 0.1～10份。
2.根据权利要求1所述的含氟酰氨基脲高性能动态聚合物，其特征在于：所述的聚醚胺单体为聚醚二元胺D-230、D-400、D-2000、ED-600、ED-900、ED-2003、polyTHF amine 350、polyTHF amine 1700中的一种或几种。
3.根据权利要求1所述的含氟酰氨基脲高性能动态聚合物，其特征在于：所述的聚酯多元醇单体为聚己二酸乙二醇酯、聚己二酸乙二醇丙二醇酯、聚己二酸乙二醇丁二醇酯、聚ε-己内酯二醇中的一种或几种。
4.根据权利要求1所述的含氟酰氨基脲高性能动态聚合物，其特征在于：所述的聚醚多元醇单体为聚环氧丙烷均聚醚多醇、聚环氧乙烷均聚醚多醇、四氢呋喃均聚醚多醇中的一种或者几种。
5.根据权利要求1所述的含氟酰氨基脲高性能动态聚合物，其特征在于：所述的含氟二酰肼单体包括如下结构式的化合物中的一种或者几种：
Figure FDA0002572342230000011
6.根据权利要求1所述的含氟酰氨基脲高性能动态聚合物，其特征在于：所述的二异氰酸酯单体包括如下结构式得化合物中得一种或者几种：
Figure FDA0002572342230000021
7.根据权利要求1所述的含氟酰氨基脲高性能动态聚合物，其特征在于：所述的交联剂包括如下结构式得化合物中得一种或者几种:
Figure FDA0002572342230000022
Figure FDA0002572342230000031
8.根据权利要求1-7中任一项所述的含氟酰氨基脲高性能动态聚合物的制备方法，其特征在于：将含氟二酰肼单体、二异氰酸酯单体、交联剂溶于溶剂中，在快速搅拌的同时加入所述的单体，80℃下反应12h后，真空干燥除去溶剂即可得到含氟酰氨基脲高性能动态聚合物材料。
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