高级检索

  • ISSN 1008-9357
  • CN 31-1633/O6

留言板

尊敬的读者、作者、审稿人, 关于本刊的投稿、审稿、编辑和出版的任何问题, 您可以本页添加留言。我们将尽快给您答复。谢谢您的支持!

姓名
邮箱
手机号码
标题
留言内容
验证码

生物基苯并噁嗪作为环氧树脂潜伏性固化剂的研究

王汉武 贾瑞敏 冉起超

王汉武, 贾瑞敏, 冉起超. 生物基苯并噁嗪作为环氧树脂潜伏性固化剂的研究[J]. 功能高分子学报,2022,35(3):1-8 doi: 10.14133/j.cnki.1008-9357.20210730001
引用本文: 王汉武, 贾瑞敏, 冉起超. 生物基苯并噁嗪作为环氧树脂潜伏性固化剂的研究[J]. 功能高分子学报,2022,35(3):1-8 doi: 10.14133/j.cnki.1008-9357. 20210730001
WANG Hanwu, JIA Ruimin, RAN Qichao. Study on Latent Curing Agent of Epoxy Resin Based on Bio-Benzoxazine[J]. Journal of Functional Polymers. doi: 10.14133/j.cnki.1008-9357.20210730001
Citation: WANG Hanwu, JIA Ruimin, RAN Qichao. Study on Latent Curing Agent of Epoxy Resin Based on Bio-Benzoxazine[J]. Journal of Functional Polymers. doi: 10.14133/j.cnki.1008-9357. 20210730001

生物基苯并噁嗪作为环氧树脂潜伏性固化剂的研究

doi: 10.14133/j.cnki.1008-9357. 20210730001
基金项目: 国家自然科学基金(52073188)
详细信息
    作者简介:

    王汉武(1998—),男,山西阳泉人,硕士生,研究方向为耐热高分子材料

    通讯作者:

    冉起超,E-mail:ranqichao@scu.edu.cn

  • 中图分类号: TB35

Study on Latent Curing Agent of Epoxy Resin Based on Bio-Benzoxazine

  • 摘要: 以糠胺、香草醛、多聚甲醛为原料合成了一种生物基苯并噁嗪(V-fa)。选择双环戊二烯-苯酚型环氧树脂(DCPD-ER)为研究对象,将V-fa作为固化剂按不同比例加入到DCPD-ER中,同时以二氨基二苯甲烷(DDM)为固化剂进行对比研究。通过傅里叶红外光谱(FT-IR)、核磁共振氢谱(1H-NMR)对V-fa的化学结构进行了表征,确认了其结构。采用差示扫描量热(DSC)、FT-IR系统研究了树脂体系的固化反应。此外,使用动态热机械分析(DMA)、热失重分析(TGA)考察了固化物的热性能。研究表明,与DCPD-ER/DDM相比,DCPD-ER/V-fa的起始固化反应温度和固化反应活化能较高。DCPD-ER/V-fa固化物的玻璃化转变温度(Tg)、初始分解温度和800 ℃氮气下的残炭率均高于DCPD-ER/DDM的相应值,其Tg最高可达192 ℃。同时,V-fa的加入能够改善树脂体系的阻燃性能。

     

  • 图  1  V-fa的合成反应式

    Figure  1.  Synthesis route of V-fa

    图  2  V-fa的(a)FT-IR谱图和(b)1H-NMR谱图

    Figure  2.  (a) FT-IR and (b) 1H-NMR spectra of V-fa

    图  3  V-fa、DCPD-ER/V-fa与DCPD-ER/DDM共混物的DSC曲线

    Figure  3.  DSC curves of V-fa、DCPD-ER/V-fa and DCPD-ER/DDM blends

    图  4  (a) D/V-3与 (b) DCPD-ER/DDM在不同固化阶段时的DSC曲线

    Figure  4.  DSC curves of (a) D/V-3 and (b) DCPD-ER/DDM at different curing stages

    图  5  (a) D/V-3与(b) DCPD-ER/DDM在不同固化阶段下的FT-IR谱图

    Figure  5.  FT-IR spectra of (a) D/V-3 and (b) DCPD-ER/DDM at different curing stages

    图  6  DCPD-ER/V-fa的固化反应

    Figure  6.  Curing reaction of DCPD-ER/V-fa

    图  7  (a) D/V-3与(b) DCPD-ER/DDM在不同升温速率下的DSC曲线;(c)基于Kissinger方程和Ozawa方程的拟合曲线

    Figure  7.  DSC curves of (a) D/V-3 and (b) DCPD-ER/DDM at different heating rates; (c) Fitting curves based on Kissinger equation and Ozawa equation

    图  8  DCPD-ER/V-fa与DCPD-ER/DDM固化物的DMA曲线

    Figure  8.  DMA curves of cured DCPD-ER/V-fa and DCPD-ER/DDM

    图  9  DCPD-ER/V-fa与DCPD-ER/DDM固化物在氮气中的TGA曲线

    Figure  9.  TGA curves of cured DCPD-ER/V-fa and DCPD-ER/DDM under a nitrogen atmosphere

    表  1  V-fa、DCPD-ER/V-fa与DCPD-ER/DDM共混物的DSC数据

    Table  1.   DSC data of V-fa、DCPD-ER/V-fa and DCPD-ER/DDM blends

    SampleT0/℃Tp/℃ΔH/(J·g−1
    DCPD-ER/DDM100159155
    D/V-217020395
    D/V-3171206194
    D/V-4173209248
    D/V-5179216283
    V-fa163203266
    下载: 导出CSV

    表  2  DCPD-ER/V-fa与DCPD-ER/DDM固化物的DMA与TGA数据

    Table  2.   DMA and TGA data of cured DCPD-ER/V-fa and DCPD-ER/DDM

    SampleE′/GPaTg/℃$T_{{ d}_5} $ /℃Yc/%LOI
    DCPD-ER/DDM1.6168311619.9
    D/V-22.41723392326.7
    D/V-32.21813292828.7
    D/V-41.91873253330.7
    D/V-51.71923164435.1
    下载: 导出CSV
  • [1] GHOLIPOUR-MAHMOUDALILOU M, ROGHANI-MAMAQANI H, AZIMI R, ABDOLLAHIET A. Preparation of hyperbranched poly (amidoamine)-grafted graphene nanolayers as a composite and curing agent for epoxy resin [J]. Applied Surface Science,2018,428:1061-1069. doi: 10.1016/j.apsusc.2017.09.237
    [2] LI C, ZUO C, FAN H, YU M X, LI B G. Novel silicone aliphatic amine curing agent for epoxy resin: 1, 3-Bis(2-aminoethylaminomethyl) tetramethyldisiloxane 1. Non-isothermal cure and thermal decomposition property [J]. Thermochimica Acta,2012,545:75-81. doi: 10.1016/j.tca.2012.06.031
    [3] PUCHOT L, VERGE P, PERALTA S, HABIBI Y, VANCAEYZEELE Ce, VIDAL F. Elaboration of bio-epoxy/benzoxazine interpenetrating polymer networks: A composition-to-morphology mapping [J]. Polymer Chemistry,2018,9(4):472-481. doi: 10.1039/C7PY01755C
    [4] SU W C, TSAI F C, HUANG C F, DAI L Z, KUO S W. Flexible epoxy resins formed by blending with the diblock copolymer PEO-b-PCL and using a hydrogen-bonding benzoxazine as the curing agent [J]. Polymers, 2019, 11(2): 201.
    [5] WAN J, BU Z Y, XU C J, LI B G, FAN H. Preparation, curing kinetics, and properties of a novel low-volatile starlike aliphatic-polyamine curing agent for epoxy resins [J]. Chemical Engineering Journal,2011,171(1):357-367. doi: 10.1016/j.cej.2011.04.004
    [6] MAITY T, SAMANTA B C, DALAI S, BANTHIA A K. Curing study of epoxy resin by new aromatic amine functional curing agents along with mechanical and thermal evaluation [J]. Materials Science and Engineering:A,2007,464(1-2):38-46. doi: 10.1016/j.msea.2007.01.128
    [7] HAO B, YANG R, ZHANG K. A naringenin-based benzoxazine with an intramolecular hydrogen bond as both a thermal latent polymerization additive and property modifier for epoxy resins [J]. RSC Advances,2020,10(43):25629-25638. doi: 10.1039/D0RA04702C
    [8] PATIL D M, PHALAK G A, MHASKE S T. Enhancement of anti-corrosive performances of cardanol based amine functional benzoxazine resin by copolymerizing with epoxy resins [J]. Progress in Organic Coatings,2017,105:18-28. doi: 10.1016/j.porgcoat.2016.10.027
    [9] 廖凌元, 彭忠泉, 章明秋, 阮文红. 高频印制电路板用低介电高分子材料的研究进展[J]. 功能高分子学报, 2020, 34(4): 320-335.

    LIAO L Y, PENG Z Q, ZHANG M Q, RUAN W H. Research progress of low dielectric polymers for high-frequency printed circuit boards [J]. Journal of Functional Polymers, 2020, 34(3): 320-335.
    [10] REN S T, ZHANG S Y, ZHAO W B, WANG W, MIAO X Y, SONG W Q. Synthesis and curing of amino-containing benzoxazine as a novel hardener for diglycidyl ether of bisphenol-A [J]. Polymers for Advanced Technologies,2019,30(6):1394-1402. doi: 10.1002/pat.4572
    [11] ZHANG L, WANG M, WU J. Study on an amine-containing benzoxazine: Homo- and copolymerization with epoxy resin [J]. Express Polymer Letters,2016,10(7):617-626. doi: 10.3144/expresspolymlett.2016.56
    [12] 张鸿翔, 王帆, 朱亚平, 齐会民. 含氟苯并噁嗪-含硅芳炔改性树脂的制备与性能[J]. 功能高分子学报, 2020, 34(3): 284-292.

    ZHANG H X, WANG F, ZHU Y P, QI H M. Preparation and properties of fluorinated benzoxazine modified Si-containing arylacetylene resin [J]. Journal of Functional Polymers, 2020, 34(3): 284-292.
    [13] 吕钧炜, 王斌, 李辉. 基于环氧树脂/双酚A型苯并噁嗪树脂IPN体系的力学性能及固化动力学研究 [J]. 玻璃钢/复合材料,2018(11):31-36.

    LV J W, WANG B, LI H. Study of mechanical properties and curing kinetics of IPN system based on epoxy resin/bisphenol A-based benzoxazine resin [J]. Composites Science and Engineering,2018(11):31-36.
    [14] WANG H, ZHAO P, LING H, RAN Q C, GU Y. The effect of curing cycles on curing reactions and properties of a ternary system based on benzoxazine, epoxy resin, and imidazole [J]. Journal of Applied Polymer Science,2013,127(3):2169-2175. doi: 10.1002/app.37778
    [15] 郝瑞, 李江, 杨坡, 朱蓉琪, 何岳山, 顾宜. 苯并噁嗪/环氧树脂/酸酐三元体系固化反应研究 [J]. 热固性树脂,2016(3):1-6.

    HAO R, LI J, YANG P, ZHU R Q, HE Y S, GU Y. Study on curing mechanism in ternary system of benzoxazine/epoxy/anhydride [J]. Thermosetting Resin,2016(3):1-6.
    [16] 刘富双, 凌鸿, 张华, 刘向阳, 顾宜. 双酚A型苯并噁嗪与酚醛型环氧树脂共混体系的固化反应与热性能 [J]. 高分子材料科学与工程,2009,25(10):84-86.

    LIU F S, LING H, ZHANG H, LIU X Y, GU Y. The curing reaction and thermal properties of the blends of benzoxazine and epoxy [J]. Polymer Materials Science & Engineering,2009,25(10):84-86.
    [17] CAMPANER P, D'AMICO D, LONGO L, STIFANI C, TARZIA A . Cardanol-based novolac resins as curing agents of epoxy resins [J]. Journal of Applied Polymer Science,2009,114(6):3585-3591. doi: 10.1002/app.30979
    [18] CAL E, MAFFEZZOLI A, MELE G, MARTINA F, MAZZETTO S E, TARZIAC A, STIFANIC C. Synthesis of a novel cardanol-based benzoxazine monomer and environmentally sustainable production of polymers and bio-composites [J]. Green Chemistry,2007,9(7):754-759. doi: 10.1039/b617180j
    [19] 张鸿翔, 王帆, 朱亚平, 齐会民. 含氟苯并噁嗪-含硅芳炔改性树脂的制备与性能 [J]. 功能高分子学报,2021,34(3):284-292.

    ZHANG H X, WANG F, ZHU Y P, QI H M. Preparation and Properties of Fluorinated Benzoxazine Modified Si-Containing Arylacetylene Resin [J]. Journal of Functional Polymers,2021,34(3):284-292.
    [20] ZHANG K, HAN M C, LIU Y Q, FROIMOWICZ P . Design and synthesis of bio-based high-performance trioxazine benzoxazine resin via natural renewable resources [J]. ACS Sustainable Chemistry & Engineering,2019,7(10):9399-9407.
    [21] SINI N K, BIJWE J, VARMA I K. Renewable benzoxazine monomer from Vanillin: Synthesis, characterization, and studies on curing behavior [J]. Journal of Polymer Science Part A:Polymer Chemistry,2014,52(1):7-11. doi: 10.1002/pola.26981
    [22] PENG Y, DAI J, LIU Y, CAO L J, ZHU J, LIU X Q. Bio-based polybenzoxazine modified melamine sponges for selective absorption of organic solvent in water [J]. Advanced Sustainable Systems, 2019, 3(3): 1800126.
    [23] YANG R, HAN M, HAO B, ZHANG K. Biobased high-performance tri-furan functional bis-benzoxazine resin derived from renewable guaiacol, furfural and furfurylamine [J]. European Polymer Journal,2020,131. doi: 10.1016/j.eurpolymj.2020.109706
    [24] 苗香艳, 赵颖, 宋万强, 任士通. 全生物基苯并噁嗪树脂的合成及聚合研究 [J]. 中国胶粘剂,2019,28(1):17-19.

    MIAO X Y, ZHAO Y, SONG W Q, REN S T. Synthesis and polymerization of fully bio-based benzoxazine resin [J]. China Adhesives,2019,28(1):17-19.
    [25] RAN Q, LI P, ZHANG C, GU Y. Chemorheology and curing kinetics of a new RTM benzoxazine resin [J]. Journal of Macromolecular Science Part A,2009,46(7):674-681. doi: 10.1080/10601320902939598
    [26] ZHANG K, YU X, WANG Y, LIU Y . Thermally activated structural changes of a norbornene-benzoxazine-phthalonitrile thermosetting system: Simple synthesis, self-catalyzed polymerization, and outstanding flame retardancy [J]. ACS Applied Polymer Materials,2019,1(10):2713-2722. doi: 10.1021/acsapm.9b00668
  • 加载中
图(9) / 表(2)
计量
  • 文章访问数:  132
  • HTML全文浏览量:  87
  • PDF下载量:  176
  • 被引次数: 0
出版历程
  • 收稿日期:  2021-07-30
  • 网络出版日期:  2021-11-08

目录

    /

    返回文章
    返回