Synthesis of High-Ortho Novolak Resins from Liquefied Products of Walnut Shell
LU Yuhan, HUANG Yuanbo, YANG Xiaoqin, XU Kaimeng, LIU Can, ZHANG Quan, WANG Jida, ZHENG Zhifeng
Yunnan Provincial International Joint Research Center for Bioenergy, Yunnan Provincial Engineering Laboratory for Highly-Efficient Utilization of Biomass, Yunnan Provincial University Key Laboratory for Biomass Chemical Refinery & Synthesis,School of Materials Science & Engineering, Southwest Forestry University, Kunming 650224
Abstract: Walnut shell bio-based high-ortho novolak resins were synthesized by using liquefied products of walnut shell as raw material and zinc hydroxide as catalyst, their structure and thermal property were characterized by nuclear magnetic resonance spectroscopy (NMR), fourier transforming infrared spectrum (FT-IR), gel permeation chromatography (GPC), thermogravimetric analysis (TGA) and organic elements analysis (OEA). Results demonstrated that walnut shell bio-based high-ortho novolak resins can be synthesized by two-step addition of formaldehyde method, their long chain structure was consisted of phenol rings which linked with methylene by ortho-ortho connection (o-o), ortho-para connection (o-p), and para-para connection (p-p), in particular, structures of phenol rings with methylene by o-o and o-p were dominant, and the ratio of phenol rings with methylene by o-o to p-p were 1.22. Their number-average molecular weight was 4 499 g/mol, polydispersity index was 1.417. And their heat loss process included two stages which the maximum weight loss temperature was 375 ℃ with weight loss rate of 50%. According to OEA, their theoretical formula was C6H6O1.2.
1 Zhou J, Hu L H, Zhou Y H, et al. Liquefied degradation of enzymatic hydrolysis lignin for preparing phenolic compound used to synthesize phenolic resin[J].Engineering Plastics Application,2014(2):101(in Chinese). 周静,胡立红,周永红,等.酶解木质素液化降解制备酚醛树脂用酚类化合物的研究[J].工程塑料应用,2014(2):101. 2 Yi X L, Feng A N, Shao W Y, et al. Synthesis of boron modified phenolic resin and the mechanic performance of its molding plastics[J].Materials Review B: Research Papers,2015,29(8):52(in Chinese). 易新龙,冯安妮,邵文尧,等.硼改性酚醛树脂的合成及其模塑料力学性能研究[J].材料导报:研究篇,2015,29(8):52. 3 Li T, Liu J J, Yang X J, et al. Research on properties of a ablative modified phenolic resin[J].Fiber Reinforced Plastics/Composites,2015(7):18(in Chinese). 李婷,刘建军,杨学军,等.一种RTM用耐烧蚀改性酚醛树脂性能研究[J].玻璃钢/复合材料,2015(7):18. 4 Fu J, Wei C, Huan S J, et al. Effects of modification on the mechanical and frictional properties of PF/GO composites[J].Plastics Science and Technology,2014,42(3):43(in Chinese). 付俊,韦春,黄绍军,等.表面改性对酚醛树脂/氧化石墨烯复合材料的力学性能与摩擦性能的影响[J].塑料科技,2014,42(3):43. 5 Ma X L, Ao Y H, Xiao L H, et al. Effect of surface modification of carbon fiber on friction properties of carbon fiber/phenolic resin matrix composite[J].Cailiao Yanjiu Xuebao/Chinese Journal of Mate-rials Research,2015,29(2):101(in Chinese). 马小龙,敖玉辉,肖凌寒,等.表面改性对碳纤维/酚醛树脂基复合材料摩擦性能的影响[J].材料研究学报,2015,29(2):101. 6 Tang W L, Tian C R, Jia X R, et al. High-temperature insulation properties of Al2(SiO3)3 fiber/phenolic resine composite material[J].Packaging Engineering,2016(3):30(in Chinese). 唐文龙,田春蓉,贾晓蓉,等.硅酸铝纤维/酚醛树脂复合材料高温隔热性能研究[J].包装工程,2016(3):30. 7 Li H J. Synthesis of phenolic resin under different conditions and its time-of-flight mass spectrometry [D].Shanghai: East China Normal University,2010(in Chinese). 李红娟.不同条件下酚醛树脂的合成及其飞行时间质谱研究[D].上海:华东师范大学,2010. 8 Yu X D, Zhang X S, Yang J G, et al. Study on influence factors of char yield for thermoplastic PF[J].China Adhesives,2013(10):16(in Chinese). 俞晓东,张雪松,杨建国,等.热塑性酚醛树脂残炭率的影响因素研究[J].中国胶粘剂,2013(10):16. 9 Dai Y, Tan W H, Hu L H, et al. Investigation on thermal decomposition behaviors of Cashew nut shell liquid modified thermoplastic phenolic resin by TG-DSC-MS coupling techniques at different atmospheres[J].Journal of Instrumental Analysis,2014,33(4):387(in Chinese). 戴燕,谭卫红,胡立红,等.TG-DSC-MS联用研究不同气氛下腰果壳油改性热塑性酚醛树脂的热裂解特性[J].分析测试学报,2014,33(4):387. 10 Miroslav Huskic, Alojz Anzlovar, Majda Zigon. Montmoril-lonite-phenolic resin nanocomposites prepared by one-step-in-situ intercalative polymerization[J].Applied Clay Science,2014:484. 11 Ruan S J, Zuo X H, Zhang S L, et al. Preparation of modified thermoplastic phenol-formaldehyde resin and influence factors of residual carbon[J].China Adhesives,2012,21(12):33(in Chinese). 阮胜军,左小华,张世磊,等.改性热塑性酚醛树脂的制备及残炭率的影响因素[J].中国胶粘剂,2012,21(12):33. 12 Masahiro Nomoto, Yukio Fujikawa, Tadashi Komoto. Structure and curing mechanism of high-ortho and random novolac resins as studied by NMR[J].Journal of Molecular Structure,2010,976:419. 13 Artmann A, Bianchi O, Soares M R, et al. Rheokinetic investigations on the thermal cure of phenol-formaldehyde novolac resins[J].Materials Science & Engineering C,2010,30(8):1245. 14 Li D M, Peng Y L, Liu G M, et al.Study on chemical constituents from green husk of Juglans sigillata[J].Chinese Traditional and Herbal Drugs,2015,46(7):962(in Chinese). 李冬梅,彭友伦,刘光明.漾濞泡核桃青皮化学成分的研究[J].中草药,2015,46(7):962. 15 Foyer G, Chanfi B H, Boutevin B, et al. New method for the synthesis of formaldehyde-free phenolic resins from lignin-based aldehyde precursors[J].European Polymer Journal,2016,74:296. 16 Zheng Z F, Zou J C, Zhang H J, et al. Study on liquefaction of walnut shell in phenol and application of its resinification product as wood adhesives[J].Chemistry & Industry of Forest Products,2007,27(4):31(in Chinese). 郑志锋,邹局春,张宏健,等.核桃壳苯酚液化及其产物树脂化制备木材胶黏剂的研究[J].林产化学与工业,2007,27(4):31. 17 Yao Z, Liu W, Xiang Y S, et al. Effect of phenolic resin binder on expansion/shrinkage process and microstructure of cold ramming paste for aluminum electrolysis[J].Carbon Techniques,2015,34(1):51(in Chinese). 姚桢,刘卫,向宇姝,等.酚醛树脂黏结剂对铝用冷捣糊膨胀/收缩过程和微观结构的影响[J].炭素技术,2015,34(1):51. 18 Yin Y G, Ren R, Liu C L, et al. Synthesis and curing performance of the high-ortho thermoplastic phenolic resin[J].Polymer Materials Science and Engineering,2012,28(4):9(in Chinese). 殷勇刚,任蕊,刘春玲,等.高邻位热塑性酚醛树脂的合成及固化性能[J].高分子材料科学与工程,2012,28(4):9. 19 Zhang S J, Huang R H. The method for determination of free phenol content in waste water during thermal plastic phenol-formaldehyde resin synthesis process[J].Foundry,2013,62(1):41(in Chinese). 张苏静,黄仁和.热塑性酚醛树脂合成中废水游离酚含量的测定方法[J].铸造,2013,62(1):41.
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2018, Vol. 32 
