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CN106632961B - 利用4,4′-联苯二酚扩链制备形状记忆聚氨酯的方法 - Google Patents

利用4,4′-联苯二酚扩链制备形状记忆聚氨酯的方法 Download PDF

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CN106632961B
CN106632961B CN201610925825.3A CN201610925825A CN106632961B CN 106632961 B CN106632961 B CN 106632961B CN 201610925825 A CN201610925825 A CN 201610925825A CN 106632961 B CN106632961 B CN 106632961B
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shape memory
memory polyurethane
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biphenyl diphenol
nitrogen atmosphere
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CN106632961A (zh
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李裕琪
徐旭
陆绍荣
韦春
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Guilin University of Technology
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6633—Compounds of group C08G18/42
    • C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/664—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3203—Polyhydroxy compounds
    • C08G18/3215—Polyhydroxy compounds containing aromatic groups or benzoquinone groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
    • C08G18/4269—Lactones
    • C08G18/4277—Caprolactone and/or substituted caprolactone
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    • C08G2280/00—Compositions for creating shape memory

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Abstract

本发明公开了一种利用4,4′‑联苯二酚扩链制备形状记忆聚氨酯的方法。将2.0g重均分子量为1000的聚己内酯二元醇放入圆底烧瓶中，在氮气氛下加热至80℃并磁力搅拌直至融化，然后加入20ml N,N‑二甲基甲酰胺和0.1 ml二月桂酸二丁基锡，将混合物加热至105℃保温15min除水，再降温至80℃，加入0.67ml六亚甲基二异氰酸酯，于80℃下反应3~5h，制得含有端异氰酸酯聚氨酯预聚体的混合液，再加入0.38g 4,4′‑联苯二酚，在氮气氛中于80℃下搅拌反应12h，然后一起倒入50~80℃下预热过的模具中，在70~90℃下加热固化6~8h，即制得利用4,4′‑联苯二酚扩链的形状记忆聚氨酯。本发明方法操作简单，且所制得的形状记忆聚氨酯材料具有优异的力学、热学和形状记忆性能。

Description

利用4,4′-联苯二酚扩链制备形状记忆聚氨酯的方法
技术领域
本发明属于智能高分子材料技术领域，特别涉及一种利用4,4′-联苯二酚扩链制备形状记忆聚氨酯的方法。
背景技术
形状记忆材料在生物医用领域，结构件领域，纺织领域具有重要的应用价值，是近年来学术界和工业界的研究热点和重点。尤其是形状记忆高分子（Shape Memory Polymer，简称SMP）材料具有易加工、易成型、质轻等优点，具有十分巨大的潜在应用价值，从80年代开始，世界各国的研究人员加大了对SMP的投入和研究，使得SMP的研究得到了快速的发展，成为当前一种重要的功能材料。
作为最早开始被用于研发SMP的材料之一，形状记忆聚氨酯（Shape MemoryPolyurethane，简称SMPU）自80年代由日本三菱重工工业开发成功后得到了广泛的关注。聚氨酯是由多异氰酸酯和聚醚多元醇或者聚酯多元醇及小分子多元醇、多元胺等作为扩链剂等原料制备的一种聚合物。该聚合物中，异氰酸酯基和扩链剂的链刚性表现为硬段，硬段间的氢键以及其他链缠绕作用能在SMP中起到物理交联的作用，而聚酯或者聚醚二元醇是软段，则可以起到分子开关的作用。所以，软硬段的结构设计和比例调节是制备高性能SMPU的关键所在。
聚己内酯（polycaprolactone，简称PCL）是由ε-己内酯开环聚合得到的半结晶聚酯高分子，常用于SMPU的制备。由于PCL具有端基可反应性，可以通过选择不同的引发剂制备得到星状、枝状等不同结构的PCL，从而制得不同结构的SMPU，这使得PCL在SMP材料研究中占有重要一席。但PCL的机械性能较差，限制了SMP的应用。
4,4′-联苯二酚（4,4’-Biphenol，简称BP）由于其耐热性能极佳，是合成高聚物的重要中间体原料，例如用作聚酯、聚氨酯、聚碳酸酯、聚砜及环氧树脂的改性单体，用以制造优良的工程塑料和复合材料。
本发明通过分子设计，利用BP进行扩链，结合PCL通过交联改性机制制备出综合性能良好的SMPU。本思路目前未见文献报道。
发明内容
本发明的目的是提供一种利用4,4′-联苯二酚扩链制备形状记忆聚氨酯的方法。
具体步骤为：
(1)将2.0g重均分子量为1000的聚己内酯二元醇放入圆底烧瓶中，在氮气氛下加热至80℃并磁力搅拌直至融化，然后加入20ml N,N-二甲基甲酰胺（DMF）和0.1 ml二月桂酸二丁基锡（DBTDL），将混合物加热至105℃保温15min除水，再降温至80℃，加入0.67ml六亚甲基二异氰酸酯（HDI），于80℃下反应3~5h，制得含有端异氰酸酯聚氨酯预聚体的混合液。
(2)将0.38g 4,4′-联苯二酚加入到步骤(1)制得的含有端异氰酸酯聚氨酯预聚体的混合液中，在氮气氛中于80℃下搅拌反应12h，然后一起倒入50~80℃下预热过的模具中，在70~90℃下加热固化6~8h，即制得利用4,4′-联苯二酚扩链的形状记忆聚氨酯。
本发明方法操作简单，且所制得的形状记忆聚氨酯材料具有优异的力学、热学和形状记忆性能。其主要性能指标如下：断裂伸长率达到近600%；拉伸强度达到35MPa左右；3%的热失重温度≥275℃；二次循环形状固定率为80%~100%；二次循环形状回复率为90%~100%。
具体实施方式
实施例：
(1)将2.0g重均分子量为1000的聚己内酯二元醇放入圆底烧瓶中，在氮气氛下加热至80℃并磁力搅拌直至融化，然后加入20ml N,N-二甲基甲酰胺（DMF）和0.1 ml二月桂酸二丁基锡（DBTDL），将混合物加热至105℃保温15min除水，再降温至80℃，加入0.67ml六亚甲基二异氰酸酯（HDI），于80℃下反应4h，制得含有端异氰酸酯聚氨酯预聚体的混合液。
(2)将0.38g 4,4′-联苯二酚加入到步骤(1)制得的含有端异氰酸酯聚氨酯预聚体的混合液中，在氮气氛中于80℃下搅拌反应12h，然后一起倒入60℃下预热过的模具中，在80℃下加热固化7h，即制得利用4,4′-联苯二酚扩链的形状记忆聚氨酯。
将本实施例制得的形状记忆聚氨酯进行测试，其断裂伸长率为599.5%，拉伸强度为34.67MPa；二次循环形状固定率为83.24%，二次循环形状回复率为93.78%；3%热失重温度为277℃，最大分解温度为336℃，550℃的残碳率为4.438%，综合性能较为优异。

Claims (1)

1.一种利用4,4′-联苯二酚扩链制备形状记忆聚氨酯的方法，其特征在于具体步骤为：
(1)将2.0g重均分子量为1000的聚己内酯二元醇放入圆底烧瓶中，在氮气氛下加热至80℃并磁力搅拌直至融化，然后加入20ml N,N-二甲基甲酰胺和0.1 ml二月桂酸二丁基锡，将混合物加热至105℃保温15min除水，再降温至80℃，加入0.67ml六亚甲基二异氰酸酯，于80℃下反应3~5h，制得含有端异氰酸酯聚氨酯预聚体的混合液；
(2)将0.38g 4,4′-联苯二酚加入到步骤(1)制得的含有端异氰酸酯聚氨酯预聚体的混合液中，在氮气氛中于80℃下搅拌反应12h，然后一起倒入50~80℃下预热过的模具中，在70~90℃下加热固化6~8h，即制得利用4,4′-联苯二酚扩链的形状记忆聚氨酯。
CN201610925825.3A 2016-10-31 2016-10-31 利用4,4′-联苯二酚扩链制备形状记忆聚氨酯的方法 Active CN106632961B (zh)

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CN109912773B (zh) * 2019-03-29 2021-10-26 中国科学院宁波材料技术与工程研究所 一种形状记忆聚氨酯及其制备方法
CN109880054A (zh) * 2019-03-29 2019-06-14 中国科学院宁波材料技术与工程研究所 具有形状记忆功能的聚氨酯及其制备方法
CN110437402A (zh) * 2019-08-09 2019-11-12 中国科学院兰州化学物理研究所 一种具有形状记忆性能的互穿网络聚合物的制备方法
CN112094397B (zh) * 2020-09-23 2022-09-02 广东石油化工学院 一种剑麻基形状记忆聚氨酯泡沫的制备方法
CN114478981A (zh) * 2022-01-21 2022-05-13 中国科学院武汉岩土力学研究所 一种垃圾填埋场柔性闭气材料及其制备方法、使用方法

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