纳米SiO2-木质素基酚醛泡沫的热稳定性及韧性表征

doi:10.16085/j.issn.1000-6613.2017-1538

化工进展 ›› 2017, Vol. 36 ›› Issue (12): 4569-4574.DOI: 10.16085/j.issn.1000-6613.2017-1538

纳米SiO₂-木质素基酚醛泡沫的热稳定性及韧性表征

郭亚军, 胡立红, 张娜, 周永红

中国林业科学研究院林产化学工业研究所, 国家林业局林产化学工程重点开放性实验室, 江苏南京 210042

收稿日期:2017-07-24 修回日期:2017-08-28 出版日期:2017-12-05 发布日期:2017-12-05
通讯作者: 胡立红,博士,副研究员,主要从事生物质高分子材料的应用研究。
作者简介:郭亚军(1992-),男,硕士研究生。E-mail:ggguoyajun@163.com。
基金资助:
国家十三五重点研发计划（2017YFD0601000）、国家自然科学基金面上项目（31470613）及林化所创新工程项目（LHSXKQ11）。

Characterization of thermal stability and toughness of nanoSiO₂-lignin based phenolic foam

GUO Yajun, HU Lihong, ZHANG Na, ZHOU Yonghong

Institute of Chemical Industry of Forest Products Chinese Academy of Forestry(CAF), Key and Open Laboratory of Forest Chemical Engineering, Nanjing 210042, Jiangsu, China

Received:2017-07-24 Revised:2017-08-28 Online:2017-12-05 Published:2017-12-05

摘要/Abstract

摘要： 采用溶胶-凝胶法制备的纳米SiO₂和氧化降解的木质素磺酸钙共同改性酚醛泡沫。并采用热重分析仪、电子万能试验机、扫描电镜等方法对泡沫材料进行了表征。测试结果表明，改性泡沫的热稳定性和韧性得到了提高，其中质量分数为0.5%的纳米SiO₂-木质素酚醛泡沫（LPF-0.5）性能最佳。热重分析泡沫LPF-0.5的最大速率降解温度为330℃，残炭率为54%，比纯泡沫（PPF）的145℃和49%，分别提高185℃和10%。力学性能测试表明泡沫LPF-0.5的压缩强度（0.33MPa）、弯曲强度（0.53MPa）和弯曲模量（16.01MPa）比PPF（0.27MPa、0.31MPa、10.54MPa）分别提高了23%、71%、52%。易碎性能表征泡沫LPF-0.5的粉化率降低了34%，韧性明显提高。同时扫描电镜显示泡沫LPF-0.5具有最优的泡体规整度和泡孔均匀度。

关键词: 纳米二氧化碳, 木质素, 酚醛泡沫, 热稳定性, 韧性, 粉化率

Abstract: A series of phenolic foams were prepared by nanoSiO₂ rooting in sol-gel process and calcium lignosulfonate after oxidative degradation. The properties of foam materials were characterized by thermogravimetric analyzer,electronic universal testing machine,and scanning electron microscope. Results showed that the improvements of thermal stability and toughness of modified foam varied,among which LPF-0.5,with 0.5% mass fraction of nanoSiO₂-lignin phenolic foam,had the optimum performance. TG analysis results indicated the maximum rate of degradation of LPF-0.5 was 330℃ and the char content was 53.7%,which was 185℃ and 9% higher than that of pure foam (PPF)at 145℃ and 49.3%,respectively. Mechanical properties test showed the compression strength,bending strength and bending modulus of foam LPF-0.5 were 0.33MPa,0.53MPa and 16.01MPa,respectively,while those of PPF were 0.27MPa,0.31MPa and 10.54MPa,which was increased by 23%,71% and 52%,respectively. Compared to the pure foam,the pulverization rate of LPF-0.5 decreased by 34%. Scanning electron microscopy indicated that the foam LPF-0.5 had the best bubble regularity and bubble uniformity.

Key words: nanoSiO₂, lignin, phenolic foam, thermal stability, toughness, pulverization ratio

中图分类号:

TQ322.4

郭亚军, 胡立红, 张娜, 周永红. 纳米SiO₂-木质素基酚醛泡沫的热稳定性及韧性表征[J]. 化工进展, 2017, 36(12): 4569-4574.

GUO Yajun, HU Lihong, ZHANG Na, ZHOU Yonghong. Characterization of thermal stability and toughness of nanoSiO₂-lignin based phenolic foam[J]. Chemical Industry and Engineering Progress, 2017, 36(12): 4569-4574.

参考文献

[1] LI Haiyan,ZHANG Zhisheng,MA Xiaofei,et al. Synthesis and characterization of epoxy resin modified with nano-SiO₂ and γ-glycidoxypropyltrimethoxy silane[J]. Surface and Coatings Technology,2007,201:5269-5272.
[2] LI Shan,CHEN Fenghua,ZHANG Boxing,et al. Structure and improved thermal stability of phenolic resin containing silicon and boron elements[J]. Polymer Degradation and Stability,2016,133:321-329.
[3] SONG S A,YONG S C,KIM S S. The mechanical and thermal characteristics of phenolic foams reinforced with carbon nanoparticles[J]. Composites Science and Technology,2014,103:85-93.
[4] SAZOROZCO B D,ALONSO M V,OLIET M,et al. Lignin particle-and wood flour-reinforced phenolic foams:friability,thermal stability and effect of hygrothermal aging on mechanical properties and morphology[J]. Composites Part B:Engineering,2015,80:154-161.
[5] 胡立红,周永红,李书龙. 低游离酚热塑性酚醛树脂的合成[J]. 热固性树脂,2008,23(3):29-31. HU Lihong,ZHOU Yonghong,LI Shulong. Synthesis of novolac phenolic foam with low free phenol[J]. Thermosetting Resin,2008,23(3):29-31.
[6] LIN C T,LEE H T,CHEN J K. Preparation and properties of bisphenol-F based boron-phenolic resin/modified silicon nitride composites and their usage as binders for grinding wheels[J]. Applied Surface Science,2015,330:1-9.
[7] HERNANDEZPADRON G,ROJAS F,CASTANO V. Development and testing of anticorrosive SiO₂/phenolic-formaldehydic resin coatings[J]. Surface and Coatings Technology,2006,201(3):1207-1214.
[8] XU Peijun,JING Xinli. High carbon yield thermoset resin based on phenolic resin,hyperbranched polyborate,and paraformaldehyde[J]. Polymer Advanced Technologies,2011,22(12):2592-2595.
[9] 胡立红,薄采颖,周静,等. 响应面法优化木质素氧化降解工艺及反应活性研究[J]. 工程塑料应用,2015,43(11):95-98. HU Lihong,BO Caiying,ZHOU Jing,et al. Optimization of lignin oxidation degradation technology by response surface methodology and its reactive activity[J]. Engineering Plastics Application,2015,43(11):95-98.
[10] 潘奇,陈介南,张新民,等. 纤维乙醇发酵残渣中酶解木质素的提取与表征[J]. 化工进展,2015,34(1):86-90. PAN Qi,CHEN Jienan,ZHANG Xinmin,et al. Extraction and characterization of enzymatic hydrolysis lignin from cellulosic ethanol fermentation residue[J]. Chemical Industry and Engineering Progress,2015,34(1):86-90.
[11] 平清伟,王春,潘梦丽,等. 木质纤维生物质精炼中木质素的分离及高值化利用[J]. 化工进展,2016,35(1):294-301. PING Qingwei,WANG Chun,PAN Mengli,et al. Separation and high-value utilization of lignin from lignocellulose biomass refining[J]. Chemical Industry and Engineering Progress,2016,35(1):294-301.
[12] 马灼明,李淑君,杨冬梅. 酶解木质素的活化及用于酚醛树脂的制备[J]. 森林工程,2017,33(2):64-67. MA Zhuoming,LI Shujun,YANG Dongmei. Activation of enzymatic hydrolysis lignin and used for preparation of phenol-formaldehyde resin[J]. Forest Engineering,2017,33(2):64-67.
[13] SHI Hongwei,LIU Fuchun,YANG Lihong,et al. Characterization of protective performance of epoxy reinforced with nanometer-sized TiO₂ and SiO₂[J]. Progress in Organic Coating,2008,62(4):359-368.
[14] GAO Xiaoyan,ZHU Yanchao,ZHAO Xu,et al. Synthesis and characterization of polyurethane/SiO₂ nanocomposites[J]. Applied Surface Science,2011,257(10):4719-4724.
[15] 张均成,王婷,邱志明,等. 纳米SiO₂/Fe₃O₄磁性流体的制备及其性能表征[J]. 东北电力大学学报,2015,35(4):40-46. ZHANG Juncheng,WANG Ting,QIU Zhiming,et al. Preparation and characterization of SiO₂/Fe₃O₄ magnetic fluid[J]. Journal of Northeast Dianli University,2015,35(4):40-46.
[16] 刘明伟,刘芳. 二氧化硅含量对污泥底泥制备陶粒性能的影响研究[J]. 东北电力大学学报,2016,36(3):86-90. LIU Mingwei,LIU Fang. Effect of SiO₂ on the characteristics of lightweight aggregate made from sewage sludge and river sediment[J]. Journal of Northeast Dianli University,2016,36(3):86-90.
[17] WANG M C,LEITCH M,XU C B. Synthesis of phenol-formaldehyde resol resins using organosolv pine lignins[J]. European Polymer Journal,2009,45(12):3380-3388.
[18] ZHANG Yan,SHEN Shihong,LIU Yujian. The effect of titanium incorporation on the thermal stability of phenol-formaldehyde resin and its carbonization microstructure[J]. Polymer Degradation Stability,2013,98(2):514-518.
[19] IBRAHIM M N M,ZAKARIA N,SIPAUT C S,et al. Chemical and thermal properties of lignins from oil palm biomass as a substitute for phenol in a phenol formaldehyde resin production[J]. Carbohydrate Polymers,2011,86(1):112-119.
[20] YUAN Junjie,ZHANG Yunbao,WANG Zhengzhou. Phenolic foams toughened with crosslinked poly(n-butyl acrylate)/silica core-shell nanocomposite particles[J]. Journal of Applied Polymer Science,2015,132(40):42592.
[21] JOSEPH R,ZHANG S,FORD W T. Structure and dynamics of a colloidal silica-poly(methyl methacrylate) composite by ¹³C and ²⁹Si MAS[J]. Macromolecules,1996,29(4):1305-1312.
[22] LEI Shiwen,GUO Quangui,ZHANG Dongqing,et al. Preparation and properties of the phenolic foams with controllable nanometer pore structure[J]. Journal of Applied Polymer Science,2010,117(6):3545-3550.
[23] HERNANDEZ P G,ROJAS F,GARCIAG G M,et al. Development of hybrid materials consisting of SiO₂ microparticles embedded in phenolic-formaldehydic resin polymer matrices[J]. Materials Science and Engineering A,2003,355(1):338-347.
[24] LI Qiulong,CHEN Lin,ZHANG Jinjin,et al. Enhanced mechanical properties,thermal stability of phenolic-formaldehyde foam/silica nanocomposites via in situ polymerization[J]. Polymer Engineering and Science,2016,55(12):2783-2793.
[25] KIM J,SONG T H. Vacuum insulation properties of glass wool and opacified fumed silica under variable pressing load and vacuum level[J]. International Journal of Heat and Mass Transfer,2013,64:783-791.
[26] 张华林,吕小改,李志浩,等. 带环氧基团纳米二氧化硅改性酚醛树脂的合成及热性能[J]. 化学研究,2014,25(6):563-565. ZHANG Hualin,LV Xiaozheng,LI Zhihao,et al. Preparation and themral properties of phenolic resin modified with nano-silica containing epoxy group[J]. Chemical Research,2014,25(6):563-565.
[27] 贾谊,朱春江,秦争,等. 低聚端羟基聚硅氧烷接枝增韧酚醛树脂的制备及性能[J]. 应用化学,2014,31(5):566-569. JIA Yi,ZHU Chunjiang,QIN Zheng,et al. Preparation and performance of hydroxyl-terminated oligomeric polysiloxane grafted toughneed phenolic resin[J]. Chinese Journal of Applied Chemistry,2014,31(5):566-569.

纳米SiO₂-木质素基酚醛泡沫的热稳定性及韧性表征

Characterization of thermal stability and toughness of nanoSiO₂-lignin based phenolic foam

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

参考文献

相关文章 15

编辑推荐

Metrics

本文评价

[1]	戴欢涛, 曹苓玉, 游新秀, 徐浩亮, 汪涛, 项玮, 张学杨. 木质素浸渍柚子皮生物炭吸附CO₂特性[J]. 化工进展, 2023, 42(S1): 356-363.
[2]	关红玲, 杨辉, 井红权, 刘玉琼, 谷守玉, 王好斌, 侯翠红. 木质素基控释材料及其在药物输送和肥料控释中的应用[J]. 化工进展, 2023, 42(7): 3695-3707.
[3]	于丁一, 李圆圆, 王晨钰, 纪永升. pH响应性木质素水凝胶的制备及药物控释[J]. 化工进展, 2023, 42(6): 3138-3146.
[4]	任建鹏, 吴彩文, 刘慧君, 吴文娟. 木质素-聚苯胺复合材料的制备及对刚果红的吸附[J]. 化工进展, 2023, 42(6): 3087-3096.
[5]	李云闯, 谢方明, 席亚男, 万新月, 孙玉虎, 赵永峰, 李根, 刘宏海, 高雄厚, 刘洪涛. 高水热稳定性介孔分子筛的低成本合成研究进展[J]. 化工进展, 2023, 42(4): 1877-1884.
[6]	张晨光, 封硕, 邢玉烨, 沈伯雄, 苏立超. 柴油车用NH₃-SCR铜基分子筛催化剂孤立态Cu²⁺研究进展[J]. 化工进展, 2023, 42(3): 1321-1331.
[7]	杨程瑞雪, 黄琪媛, 冉建速, 崔耘通, 王健健. 磷酸修饰二氧化硅负载钯催化剂用于木质素衍生物高效水相低温加氢脱氧[J]. 化工进展, 2023, 42(10): 5179-5190.
[8]	张鹏, 王绍庆, 李志合, 张安东, 高亮, 万震, 宋宁. 赤泥/木质素共热解制备复合吸附材料及其性能[J]. 化工进展, 2022, 41(S1): 407-414.
[9]	蒲福龙, 伍尚炜, 郑映玲, 郑玉意, 侯雪丹. 基于乳酸的深度共熔溶剂提取秸秆木质素对纤维素酶水解效率的影响[J]. 化工进展, 2022, 41(9): 4937-4945.
[10]	龙垠荧, 杨健, 管敏, 杨怡洛, 程正柏, 曹海兵, 刘洪斌, 安兴业. 木质素基材料在混合型超级电容器电极材料中的研究进展[J]. 化工进展, 2022, 41(9): 4855-4865.
[11]	汪兴, 赵子龙, 张小山, 王宏杰, 董文艺, 陈慧慧. 制备条件对生物炭载铁催化剂催化破络Ni-EDTA性能及活性组分浸出的影响[J]. 化工进展, 2022, 41(9): 4831-4839.
[12]	张丽珠, 王欢, 李琼, 杨东杰. 木质素衍生吸附材料及其在废水处理中的应用研究进展[J]. 化工进展, 2022, 41(7): 3731-3744.
[13]	张伟, 安兴业, 刘利琴, 龙垠荧, 张昊, 程正柏, 曹海兵, 刘洪斌. 木质素纳米颗粒/天然纤维基活性碳纤维材料的制备及其电化学性能[J]. 化工进展, 2022, 41(7): 3770-3783.
[14]	娄瑞, 刘钰, 田杰, 张亚男. 纳米木质素基多孔炭的制备及其电化学性能[J]. 化工进展, 2022, 41(6): 3170-3177.
[15]	申琪, 薛雨源, 杨涛伟, 张妍, 李胜任. 木质素荧光研究进展[J]. 化工进展, 2022, 41(5): 2672-2685.