邻苯二甲腈基联苯酚醛树脂中空微球的制备与性能研究

李芝华; 段芳芳; 华斯嘉; 刘夏清; 邹德华; 牛捷; 刘兰兰

doi:10.11777/j.issn1000-3304.2017.16174

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邻苯二甲腈基联苯酚醛树脂中空微球的制备与性能研究

研究论文 | 更新时间：2021-05-18

- 邻苯二甲腈基联苯酚醛树脂中空微球的制备与性能研究
- Preparation and Properties of Phthalonitrile Biphenyl Novolac Resin Hollow Microspheres
- 高分子学报 2017年第4期页码：596-604
- 作者机构：
  
  1.中南大学有色金属材料科学与工程教育部重点实验室长沙 410083
  2.国网湖南省电力公司带电作业中心长沙 410000
- 作者简介：
  
  李芝华, E-mail:ligfz@mail.csu.edu.cn Zhi-hua Li, E-mail:ligfz@mail.csu.edu.cn
- 基金信息：
  
  湖南省重点科技研发项目计划(2015GK3042);中南大学贵重仪器设备开放共享基金(CSUZC2014008)
- DOI：10.11777/j.issn1000-3304.2017.16174
  中图分类号：
- 纸质出版日期：2017-4，
  
  收稿日期：2016-5-20，
  
  修回日期：2016-6-16，
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李芝华, 段芳芳, 华斯嘉, 刘夏清, 邹德华, 牛捷, 刘兰兰. 邻苯二甲腈基联苯酚醛树脂中空微球的制备与性能研究[J]. 高分子学报, 2017,(4):596-604.

Zhi-hua Li, Fang-fang Duan, Si-jia Hua, Xia-qing Liu, De-hua Zou, Jie Niu, Lan-lan Liu. Preparation and Properties of Phthalonitrile Biphenyl Novolac Resin Hollow Microspheres[J]. Acta Polymerica Sinica, 2017,(4):596-604.
李芝华, 段芳芳, 华斯嘉, 刘夏清, 邹德华, 牛捷, 刘兰兰. 邻苯二甲腈基联苯酚醛树脂中空微球的制备与性能研究[J]. 高分子学报, 2017,(4):596-604. DOI： 10.11777/j.issn1000-3304.2017.16174.

Zhi-hua Li, Fang-fang Duan, Si-jia Hua, Xia-qing Liu, De-hua Zou, Jie Niu, Lan-lan Liu. Preparation and Properties of Phthalonitrile Biphenyl Novolac Resin Hollow Microspheres[J]. Acta Polymerica Sinica, 2017,(4):596-604. DOI： 10.11777/j.issn1000-3304.2017.16174.

摘要

以苯酚及4，4'-二氯甲基联苯为单体，盐酸作催化剂经Friedel-Crafts烷基化反应，合成了联苯酚醛（BN）树脂，并在此基础上通过BN树脂和4-硝基邻苯二甲腈发生亲核反应合成了邻苯二甲腈基联苯酚醛（PBN）树脂，采用高温发泡法制备了邻苯二甲腈基联苯树脂中空微球.利用红外吸收光谱（FTIR）、核磁氢谱（

H-NMR）、凝胶渗透色谱（GPC）、热失重（TG）以及扫描电子显微镜（SEM）等对制备的PBN树脂以及PBN中空微球进行了结构与性能表征.研究结果表明，采用自固化和固化剂固化的PBN树脂中空微球均已完全固化，2种固化产物中都形成了异吲哚啉和酞菁环结构，固化剂固化产物中还有三嗪环结构的形成.PBN树脂的自固化产物和固化剂固化产物固化物在1000 ℃氩气氛围残炭率分别为67%和70%，在600 ℃空气氛围残炭率分别为70%和47%.PBN树脂中空微球粒径分布范围为350~800 μm，数均粒径和体积平均粒径分别为562和583 μm，单分散指数为1.04.

Abstract

Started from phenol and 4

4-dichloro-methyl-biphenyl

biphenyl-type novolac (BN) was synthesized by Friedel-Crafts alkylation reaction. Phthalonitrile biphenyl novolac (PBN) was then synthesized through nucleophilic substitution between 4-nitro-phthalonitrile and BN. Hollow PBN microsphere was prepared by high-temperature foaming for the first time. Structure and thermal properties of PBN and its cured products were examined by Fourier transform infrared spectroscopy (FTIR)

H nuclear magnetic resonance spectroscopy (

H-NMR)

gel permeation chromatography (GPC)

thermal gravimetric analysis (TG) and laser particle measurement

respectively. Structure of the PBN microspheres was characterized by optical microscopy and scanning electron microscope (SEM). FTIR showed that nucleophilic substitution occurred for phenolic hydroxyl group and phthalonitrile was successfully grafted to BN backbone. Grafting rate of phthalonitrile was 53.63% calculated from

H-NMR analysis. GPC analysis indicated that PBN and BN had similar dispersion index

indicating that nucleophilic substitution did not alter the molecular structure of BN main chain. FTIR analysis of the cured PBN indicated that the cure mechanism was dependent on the grafting rate of phthalonitrile. PBN underwent crosslinking through phenol-mediated reaction of its nitrile groups. By self-curing without curing agents

cured PBN formed rigid structures with isoindoline and phthalocyanine rings. With curing agents

triazine ring was formed in cured PBN

in addition to isoindoline and phthalocyanine rings. TG analysis showed that char yield of cured PBN was 67% by self-curing and it was 70% with curing agents used when curing was done in argon at 1000 ℃

while those figures became 70% and 47% at 600 ℃ in air. Hollow PBN microsphere was highly spherical as seen under SEM. The number average particle diameter was 562 μm and the volume average particle diameter was 583 μm

respectively

with a polydispersity index of 1.04.

关键词

邻苯二甲腈联苯酚醛树脂中空微球热性能

Keywords

PhthalonitrileBiphenyl novolacHollow microspheresThermal performance

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