碱法制备蔗渣纳米纤维素/丁苯橡胶复合材料性能

doi:10.11949/j.issn.0438-1157.20171282

摘要/Abstract

摘要：

针对目前硫酸法制备纳米纤维素高污染、高危险、高处理成本的缺点，采用环境友好、低能耗、低成本的碱法从蔗渣中制备纳米纤维素（2-BNC），补强丁苯橡胶（SBR），并与硫酸法制备的纳米纤维素（S-BNC）以及白炭黑（silica）补强SBR的性能进行对比，探究2-BNC的加入对复合材料性能的影响。结果表明，2-BNC在基体中的分散性优于silica，与SBR基体有良好的界面结合，在同等填料份数下，SBR/2-BNC硫化胶的储能模量高于SBR/silica硫化胶，损耗因子下降，耐磨耗性能更加突出，且力学性能更佳；2-BNC和S-BNC对SBR的整体补强效果相当。

关键词: 蔗渣, 纳米纤维素, 纳米材料, 丁苯橡胶, 复合材料, 二氧化硅

Abstract:

The preparation of nanometer cellulose (S-BNC) by sulfuric acid hydrolysis had the disadvantages of high pollution, high risk and high treatment cost, but alkaline hydrolysis was environmentally friendly with low energy and low cost. Nano-cellulose (2-BNC) was prepared from bagasse by alkaline hydrolysis and was used to reinforce styrene butadiene rubber (SBR). The effects of 2-BNC on the performance of SBR were investigated, and further compared with SBR/silica and SBR/S-BNC composites at the same amout of fillers. The results show that the interface between 2-BNC and SBR matrix is better than that of SBR/silica system. Under the same packing fraction, DMA test results show that the addition of 2-BNC can improve the cold resistance of SBR vulcanizate. Compared to the SBR and SBR/silica systems, the SBR/2-BNC system glass transition temperature (T_g) of move towards low temperature. At high elastic state, the modulus of SBR/2-BNC system are higher than that of SBR/silica system; SBR/BNC composites exhibited better mechanical properties and abrasion resistance compared with SBR/silica composites. At the same amount of filler, the tensile strength and elongation at break of SBR/2-BNC vulcanizate are equal to that of SBR/silica vulcanizate. The stress and tear strength of SBR/2-BNC vulcanizate are higher than that of SBR/silica vulcanizate; Scanning electron microscopy (SEM) analysis show that the 2-BNC and SBR matrix has good interfacial compatibility. Dispersity of 2-BNC is better than that of silica in the matrix. The reinforcing effect of 2-BNC on SBR has no significant difference compared with that of S-BNC.

Key words: bagasse, nanocellulose, nanometer materials, SBR, composite, silica

中图分类号:

TB332

沈佩瑶, 梁小容, 李彩新, 古菊. 碱法制备蔗渣纳米纤维素/丁苯橡胶复合材料性能[J]. 化工学报, 2018, 69(6): 2759-2766.

SHEN Peiyao, LIANG Xiaorong, LI Caixin, GU Ju. Properties of bagasse nano-cellulose by alkaline hydrolysis/styrene butadiene rubber composite[J]. CIESC Journal, 2018, 69(6): 2759-2766.

参考文献 31

[1]	刘颖,任学宏. 纳米纤维素微晶的制备、改性及其应用[J]. 材料导报, 2015, (11):133-137+143. LIU Y, REN X H. Preparation modification and application of nano-crystalline cellulose[J]. Materials Review, 2015, (11):133-137+143.
[2]	GATENHOLM P, KLEMM D. Bacterial nanocellulose as a renewable material for biomedical applications[J]. MRS Bulletin, 2010, 35(3):208-213.
[3]	DANIAL D, HABIBOLLAH M, ZAHRA E D, et al. Thermal and antimicrobial properties of chitosan-nanocellulose films for extending shelf life of ground meat[J]. Carbohydrate Polymers, 2014, 109(6):148-154.
[4]	FAZLI F A, EHSANI M R, GHANBARZADEH B, et al. Nano crystalline cellulose production and its application in novel food packaging[C]//International Proceedings of Chemical Biological & Environmental, 2012.
[5]	MAI I, OAKI Y, TANAKA Y, et al. Fabrication of nanocellulose-hydroxyapatite composites and their application as water-resistant transparent coatings[J]. Journal of Materials Chemistry B, 2015, 3(28):5858-5863.
[6]	陈红莲, 高天明, 黄茂芳, 等. 纳米纤维素晶体的制备及其在聚合物中应用的研究进展[J]. 热带作物学报, 2010,31(11):2051-2058. CHEN H L, GAO T M, HUANG M F, et al. Progress in preparation of nano cellulose crystals and their applications in polymers[J]. Proceedings of the Tropical Crop Science, 2010, 31(11):2051-2058.
[7]	宋冰, 石勇, 陆海龙, 等. 纤维素纳米纤维-丁苯胶乳复合材料的制备与表征[J]. 中华纸业, 2016, 37(10):29-32. SONG B, SHI Y, LU H L, et al. Preparation and characterization of cellulose nanofiber SBR latex[J]. Zhonghua Paper, 2016, 37(10):29-32.
[8]	NGE T T, LEE S H, ENDO T. Preparation of nanoscale cellulose materials with different morphologies by mechanical treatments and their characterization[J]. Cellulose, 2013, 20(4):1841-1852.
[9]	YE D. Preparation of nanocellulose[J]. Progress in Chemistry, 2007, 19(10):1568-1575.
[10]	吴巧妹, 陈思源, 陈燕丹. 丝瓜络纳米纤维素晶体的制备与表征[J]. 西北农林科技大学学报(自然科学报), 2014, (4):229-234. WU Q M, CHEN S Y, CHEN Y D. Preparation and characterization of nanocellulose crystals from luffa sponge[J]. Journal of Northwest A & F University (Natural Science Edition), 2014, (4):229-234.
[11]	YANG H, CHEN D, VEN T G M V D. Preparation and characterization of sterically stabilized nanocrystalline cellulose obtained by periodate oxidation of cellulose fibers[J]. Cellulose, 2015, 22(3):1743-1752.
[12]	XU Q, GAO Y, QIN M, et al. Nanocrystalline cellulose from aspen kraft pulp and its application in deinked pulp[J]. International Journal of Biological Macromolecules, 2013, 60(9):241-247.
[13]	HAMAD W Y, HU T Q. Structure-process-yield interrelations in nanocrystalline cellulose extraction[J]. Canadian Journal of Chemical Engineering, 2010, 88(3):392-402.
[14]	CHEN W S, YU H P, LIU Y X, et al. Isolation and characterization of cellulose nanofibers from four plant cellulose fibers using a chemical-ultrasonic process[J]. Cellulose, 2011, 18(2):433-442.
[15]	金浩, 黄广华. 硫酸水解法制备纳米纤维素晶体的谱学性能研究[J]. 广州化工, 2016, (20):46-48. JIN H, HUANG G H. Study on spectrum of nanocellulose crystal prepared with sulfuric acid hydrolysis[J]. Guangzhou Chemical Industry, 2016, (20):46-48.
[16]	黄思维, 周定国, 吴清林. 玉米叶纳米纤维素的提取及表征[J]. 中国造纸学报, 2015, (3):1-4. HUANG S W, ZHOU D G, WU Q L. Preparation and characterization of nanocellulose from corn leaf[J]. Transactions of China Pulp and Paper, 2015, (3):1-4.
[17]	李彩新, 梁小容, 古菊. 蔗渣纳米纤维素的制备与表征[J]. 高等学校化学学报, 2017, (7):1286-1294. LI C X, LIANG X R, GU J. Preparation and characterization of bagasse nano cellulose[J]. Chemical Journal of Chinese Universities, 2017, (7):1286-1294.
[18]	古菊, 梁小容, 李彩新. 一种蔗渣纳米纤维素的制备方法:105839440A[P]. 2016. GU J, LIANG X R, LI C X. A preparation method of bagasse nano cellulose:105839440A[P]. 2016.
[19]	汪娟. 废纸纳米微晶纤维素的制备及其替代炭黑补强天然橡胶的研究[D]. 广州:华南理工大学, 2016. WANG J. Preparation of waste paper nano microcrystalline cellulose and its substitution for carbon black reinforcing natural rubber[D]. Guangzhou:South China University of Technology, 2016.
[20]	古菊, 梁小容, 黄飞, 等. 纳米纤维素补强橡胶研究进展[J]. 华南理工大学学报(自然科学版),2016, 44(2):124-132. GU J, LIANG X R, HUANG F, et al. Progress in research on nano cellulose reinforced rubber[J]. Journal of South China University of Technology (Natural Science), 2016, 44(2):124-132.
[21]	高磊, 魏绪玲, 龚光碧, 等. 木质素补强乳聚丁苯橡胶研究进展[J]. 高分子通报, 2014, (11):116-121. GAO L, WEI X L, GONG G B, et al. Progress of study on lignin reinforced poly (styrene butadiene rubber)[J]. Proceedings of the Polymer Society, 2014, (11):116-121.
[22]	RAMIER J, CHAZEZU L, GAUTHIER C, et al. Influence of silica and its different surface treatments on the vulcanization process of silica filled SBR[J]. Rubber Chemistry & Technology, 2007, 80(1):183-193.
[23]	CHOI S S, PARK B H, SONG H. Influence of filler type and content on properties of styrene-butadiene rubber (SBR) compound reinforced with carbon black or silica[J]. Polymers for Advanced Technologies, 2010, 15(15):122-127.
[24]	THOMAS M G, ABRAHAM E, JYOTISHKUMAR P, et al. Nanocelluloses from jute fibers and their nanocomposites with natural rubber:preparation and characterization[J]. International Journal of Biological Macromolecules, 2015, 81:768-777.
[25]	ZHANG C, ZHAI T, SABO R, et al. Reinforcing natural rubber with cellulose nanofibrils extracted from bleached eucalyptus kraft pulp[J]. Journal of Biobased Materials & Bioenergy, 2014, 8(3):317-324.
[26]	章毅鹏, 朱长风, 桂红星, 等. 纳米晶纤维素补强天然橡胶的研究[J]. 热带农业科学, 2008, 28(3):16-18. ZHANG Y P, ZHU C F, GUI H X, et al. Study on reinforcing natural rubber with nano crystalline cellulose[J]. Tropical Agricultural Science, 2008, 28(3):16-18.
[27]	刘玄, 陈福林, 白二雷, 等. 改性微晶纤维素的制备及其对丁苯橡胶性能的影响[J]. 橡胶工业, 2015, 62(12):720-723. LIU X, CHEN F L, BAI E L, et al. Modified preparation of microcrystalline cellulose and its influence on the properties of styrene butadiene rubber[J]. Rubber Industry, 2015, 62(12):720-723.
[28]	GUO B C, CHEN F, LEI Y D, et al. Significantly improved performance of rubber/silica composites by addition of sorbic acid[J]. Polymer Journal, 2010, 42(4):319-326.
[29]	TABSAN N, WIRASATE S, SUCHIVA K. Abrasion behavior of layered silicate reinforced natural rubber[J]. Wear, 2010, 269(5/6):394-404.
[30]	VALENTIN J L, MORABARRANTES I, CANRETEROGONZALEZ J, et al. Novel experimental approach to evaluate filler-elastomer interactions[J]. Macromolecules, 2010, 43(1):334-346.
[31]	LI Y, HAN B, WEN S, et al. Effect of the temperature on surface modification of silica and properties of modified silica filled rubber composites[J]. Composites Part A Applied Science & Manufacturing, 2014, 62(17):52-59.