CN108530610A - 具有隔热性和阻燃性的共轭微孔聚合物及其制备方法 - Google Patents

具有隔热性和阻燃性的共轭微孔聚合物及其制备方法 Download PDF

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CN108530610A
CN108530610A CN201810395209.0A CN201810395209A CN108530610A CN 108530610 A CN108530610 A CN 108530610A CN 201810395209 A CN201810395209 A CN 201810395209A CN 108530610 A CN108530610 A CN 108530610A
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polymer
zcmp
benzotriazole
heat
flammability
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朱照琪
孙寒雪
李安
魏慧娟
王菲
焦芮
张政
梁卫东
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Lanzhou University of Technology
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    • C08G2261/31—Monomer units or repeat units incorporating structural elements in the main chain incorporating aromatic structural elements in the main chain
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Abstract

本发明公开一种具有隔热性和阻燃性的如式1或式2所示的苯并三唑的共轭微孔聚合物，以及制备方法。本发明的聚合物表现出在空气中的较低热导率，使

Description

具有隔热性和阻燃性的共轭微孔聚合物及其制备方法
技术领域
本发明涉及一种共轭微孔聚合物，以及这种聚合物的制备方法及用途。
背景技术
共轭微孔聚合物（Conjugated Microporous Polymers，CMPs）是多孔有机聚合物的一种，与传统的多孔材料相比，CMPs具有较高的比表面积、良好的热稳定性（分解温度超过300℃）、较高的物理化学稳定性（不溶解于所有的有机溶剂中）等优点。这使得其在很多领域都拥有较好的应用价值，比如气体的存储和转化、电极材料、光捕获、催化、超级电容器等领域。
在传统的阻燃材料中，卤系阻燃是应用最有效的阻燃剂，通过释放活性自由基（X˙）捕获参与反应的自由基（H˙和HO˙）终止燃烧反应，但卤系燃烧会释放大量浓烟，产生腐蚀性气体和有毒物质，这就限制了其应用范围。从实际应用角度出发，我们发现常用的建筑保温材料都是由一些易燃的有机物或聚合物构成，很容易引起火灾事故，造成人员伤亡和财产损失。因此，开发具有绿色、环保、高效的新型阻燃材料仍然是现代建筑领域的一大挑战。
发明内容
本发明提供一种可克服现有技术不足的、具有隔热性和阻燃性的共轭微孔聚合物，以及其制备方法和用途。
本发明所述的聚合物是如式1或式2所示的苯并三唑的共轭微孔聚合物，其中：式1
示聚合物命名为ZCMP-1，这种聚合物在空气中的热导率值0.03 W m-1 K-1，热释放速率低于11.9 W g-1。接近为0.03 W m-1 K-1，式2示聚合物命名为ZCMP-2，其空气中的热导率值接近为0.03 W m-1 K-1，热释放速率低于9.9 W g-1。
本发明所述的聚合物制备方法是将氯代苯并三唑与炔基苯简单的一锅法通过交叉偶联反应制备。
本发明所述的聚合物具体制备方法是：在制备中ZCMP-1是由5-氯-1-（4-氯苯）苯并三唑与1,3,5-三乙炔基苯或1,4-二乙炔基苯的摩尔比1-20，以甲苯和三乙胺为溶剂、Pd(0)和CuI为催化剂，在70℃下聚合72 h；ZCMP-2是由5-氯-1-（4-氯苯）苯并三唑与1,4-二乙炔基苯的摩尔比1-20，以甲苯和三乙胺为溶剂、Pd(0)和CuI为催化剂，在70℃下聚合72 h。
本发明的聚合物可在阻燃材料中的应用，也可在隔热材料中的应用，或者在建筑材料中的应用。
本发明的聚合物表现出在空气中的较低热导率，使其在阻燃、隔热或建筑材料中有极好的应用前景。特别是本发明的聚合物中含有绿色阻燃元素(无卤素元素)，受热后分解可释放出氮气，是一种低毒、无腐蚀、绿色环保的优良材料，作为保温材料或是阻燃材料使用时还具备防潮性和自清洁性，可延长其使用寿命。因此，ZCMPs在隔热领域和阻燃领域中具有很高的实用性。
附图说明
图1为本发明的两种含苯并三唑共轭微孔聚合物的分子模拟图。图2为本发明的含苯并三唑共轭微孔聚合物的隔热效果图，其中：(a) 为ZCMP-1热成像照片， (b) 为ZCMP-2的热成像照片。图3为本发明的含苯并三唑共轭微孔聚合物在燃烧实验前后的图片，其中：(a) 为ZCMP-1， (b)为 ZCMP-2；左边为燃烧前，右边为燃烧后。
具体实施方式
一、制备实施例
制备实施例1
称取5-氯-1-（4-氯苯）苯并三唑（396.2 mg），1,3,5-三乙炔基苯（150.1 mg），四（三苯基膦）钯（0）（100 mg），碘化亚铜（30 mg）置于50 mL三口瓶中，量取甲苯、三乙胺各5 mL，N2保护下加入三口瓶中，持续通N2保持40 min；脱气完毕后将油浴锅温度缓慢升至70 ℃，避光下回流反应72 h。反应结束后，将反应体系温度自然冷却至室温，得到的粗产品依次用三氯甲烷、丙酮、水、甲醇洗涤数次直至洗涤液澄清，洗涤后产品用甲醇索氏抽提72 h；将索氏抽提后得到的产品置于鼓风干燥箱在70 ℃下干燥24 h，得到如式1示结构的聚合物，命名为ZCMP-1。
制备实施例2
称取5-氯-1-（4-氯苯）苯并三唑（264.1 mg），1,4-二乙炔基苯（126.2 mg），四（三苯基膦）钯（0）（100 mg），碘化亚铜（30 mg）置于50 mL三口瓶中，量取甲苯、三乙胺各5 mL，N2保护下加入三口瓶中，持续通N2保持40 min；脱气完毕后将油浴锅温度缓慢升至70 ℃，避光下回流反应72 h。反应结束后，将反应体系温度自然冷却至室温，得到的粗产品依次用三氯甲烷、丙酮、水、甲醇洗涤数次直至洗涤液澄清，洗涤后产品用甲醇索氏抽提72 h；将索氏抽提后得到的产品置于鼓风干燥箱在70 ℃下干燥24 h，得到如式2示结构的聚合物，命名为ZCMP-2。
实施例3：ZCMPs的阻燃与隔热测试
将本发明的聚合物（ZCMP-1和ZCMP-2）置于鼓风干燥箱中，在60 ℃下干燥8 h，将其加入热导率测试的模具中，在常温常压的条件下，用导热系数测试仪检测ZCMPs在空气中的热导率值，其中ZCMP-1和ZCMP-2的导热系数分别为0.032 W m-1 k-1和0.038 W m-1 k-1。
将本发明的聚合物（ZCMP-1和ZCMP-2）置于鼓风干燥箱中，在75 ℃下干燥8 h，分别称取5.0 mg的ZCMP-1和ZCMP-2，用微试样燃烧量热仪测热释放速率（HRR）值，其中ZCMP-1和ZCMP-2的热释放速率峰值（pHRR）分别为11.9 W g-1和9.9 W g-1。
（1）将ZCMP-1和ZCMP-2进行热导率的测试，发现ZCMP-1的隔热效果最佳；
（2）通过燃烧实验发现ZCMPs表面没有明显的火焰，燃烧后ZCMPs基本保持原始形状没有被破坏，再通过微型量热测试数据表明ZCMPs能够抑制燃烧，且ZCMP-2的热释放速率峰值比ZCMP-1低了16.8%。
实施例4：将ZCMPs置于鼓风干燥箱中，在75 ℃下干燥8 h，称取5.0 mg的ZCMPs，用微试样燃烧量热仪测试ZCMPs的热释放速率（HRR），其中ZCMP-1和ZCMP-2的热释放速率峰值（pHRR）分别为11.9 W g-1和9.9 W g-1，总热释放量（THR）分别为6.7 KJ g-1和5.9 KJ g-1。
通过图2的红外热成像图片中的颜色分布，可以清晰的看出ZCMP-1和ZCMP-2表面的温度分布情况，可见1cm厚的ZCMP-1就能够形成20℃的温差（Δt/Δd=20℃/cm），1.5cm厚的ZCMP-2可形成28℃的温差（Δt/Δd=18.7℃/cm），这意味着ZCMP-1和ZCMP-2都具有优异的隔热性。
从图3可见，在燃烧实验完成后，参见右图，可以看出ZCMP-1和ZCMP-2都保留着原始形状，基本没有被损坏，这表明ZCMPs的结构没有发生坍塌，只是在其表面形成了一层炭，这层炭提供了一个强大的保护屏障，它可以隔绝氧气和热量传递到基底材料中，保护基底材料不被燃烧，起到凝聚相阻燃的作用。

Claims (7)

1.命名为ZCMP-1、如式1示的苯并三唑的共轭微孔聚合物
在空气中的热导率值接近为0.03 W m-1 K-1，热释放速率低于11.9 W g-1。
2.命名为ZCMP-2、如式2示的苯并三唑的共轭微孔聚合物
在空气中的热导率值接近为0.03 W m-1 K-1，热释放速率低于9.9 W g-1。
3.权利要求1或2所述的聚合物制备方法，其特征在于将氯代苯并三唑与炔基苯简单的一锅法通过交叉偶联反应制备。
4.根据权利要求3所述的聚合物制备方法，其特征在于制备中ZCMP-1是由5-氯-1-（4-氯苯）苯并三唑与1,3,5-三乙炔基苯的摩尔比1-20，以甲苯和三乙胺为溶剂、Pd(0)和CuI为催化剂，在70℃下聚合72 h；ZCMP-2是由5-氯-1-（4-氯苯）苯并三唑与1,4-二乙炔基苯的摩尔比1-20，以甲苯和三乙胺为溶剂、Pd(0)和CuI为催化剂，在70℃下聚合72 h。
5.权利要求1或2所述的聚合物在阻燃材料中的应用。
6.权利要求1或2所述的聚合物在隔热材料中的应用。
7.权利要求1或2所述的聚合物在建筑材料中的应用。
CN201810395209.0A 2018-04-27 2018-04-27 具有隔热性和阻燃性的共轭微孔聚合物及其制备方法 Pending CN108530610A (zh)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102492117A (zh) * 2011-12-01 2012-06-13 大连理工大学 一种有机共轭聚合物薄膜、其合成方法及应用
CN103694191A (zh) * 2013-12-10 2014-04-02 电子科技大学 一种多官能团腈基树脂单体和聚合物及其制备方法
CN107698742A (zh) * 2017-06-14 2018-02-16 中南大学 苯并二噻吩二酮基共轭微孔聚合物制备及其光催化应用
CN107814933A (zh) * 2017-11-22 2018-03-20 兰州理工大学 具有抑菌活性的共轭微孔聚合物的制备方法及用途

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102492117A (zh) * 2011-12-01 2012-06-13 大连理工大学 一种有机共轭聚合物薄膜、其合成方法及应用
CN103694191A (zh) * 2013-12-10 2014-04-02 电子科技大学 一种多官能团腈基树脂单体和聚合物及其制备方法
CN107698742A (zh) * 2017-06-14 2018-02-16 中南大学 苯并二噻吩二酮基共轭微孔聚合物制备及其光催化应用
CN107814933A (zh) * 2017-11-22 2018-03-20 兰州理工大学 具有抑菌活性的共轭微孔聚合物的制备方法及用途

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
HUIJUAN WEI ET AL: "Benzotriazole-based conjugated microporous polymers as effiffifficient flflame retardants with better thermal insulation properties*;", 《JOURNAL OF MATERIALS CHEMISTRY A：ROYAL SOCIETY OF CHEMISTRY》 *

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Application publication date: 20180914