Preparation of nano zinc oxide/silica hybrid and its effect on properties of natural rubber composites

doi:10.16085/j.issn.1000-6613.2020-0409

Abstract

Abstract:

SiO₂ particles were cyano-functionalized by 3-cyanopropyltriethoxysilane (CTOS), and ZnO/SiO₂ hybrids (ZnO@SiO₂) were produced by deposition of the ZnO nanoparticles on cyano-functionalized SiO₂ (SiO₂-CN) surface via a facile solvothermal method. The hybrid structures were analyzed by X-ray diffractometer, Fourier transform infrared spectrometer and scanning electron microscope. ZnO@SiO₂ was used as a filler to prepare NR/ZnO@SiO₂ composites, and the interface relationship between ZnO@SiO₂ and rubber was studied. In addition, the influence of ZnO@SiO₂ on the vulcanization characteristics and mechanical properties of rubber composites was analyzed. As a result, ZnO nanoparticles was successfully deposited on the surface of SiO₂-CN, and NR/ZnO@SiO₂ composites exhibited excellent mechanical properties and vulcanization characteristics. Compared with natural rubber, the tensile strength, stress at 100% strain, and stress at 300% strain of NR/ZnO@SiO₂ composites with 5 phr hybrids were superlatively increased by 150.2%, 86.2% and 65.5%, respectively, and the curing time was reduced by 38.5%.

Key words: zinc oxide nanoparticles, silica modification, hybrid structure, rubber composites

摘要：

采用3-氰基丙基三乙氧基硅烷（CTOS）对二氧化硅（SiO₂）进行了氰基化改性，并采用热溶剂法将纳米ZnO沉积于氰基官能化SiO₂（SiO₂-CN）表面，制备出纳米氧化锌/二氧化硅杂化体（ZnO@SiO₂），并使用X射线衍射仪、傅里叶变换红外光谱仪、扫描电镜等对杂化结构进行表征。将ZnO@SiO₂作为填料添加入天然橡胶中制备复合材料（NR/ZnO@SiO₂），然后对ZnO@SiO₂与橡胶的界面关系进行了分析，并研究了ZnO@SiO₂对橡胶复合材料的硫化特性、力学性能的影响。结果表明，纳米ZnO成功沉积在SiO₂-CN表面，并且NR/ZnO@SiO₂复合材料表现出优异的机械性能和硫化特性。与天然橡胶相比，仅添加5份杂化体的NR/ZnO@SiO₂复合材料的拉伸强度、100%定伸及300%定伸强度分别增加了150.2%、86.2%和65.5%，并且正硫化时间缩短了38.5%。

关键词: 纳米氧化锌, 二氧化硅改性, 杂化结构, 橡胶复合材料

CLC Number:

TB332

Yihang LI, Yuzhu XIONG, Qingpo ZHANG, Jiangbing WU. Preparation of nano zinc oxide/silica hybrid and its effect on properties of natural rubber composites[J]. Chemical Industry and Engineering Progress, 2020, 39(8): 3213-3220.

李宜航, 熊玉竹, 张清坡, 吴江兵. 纳米氧化锌/二氧化硅杂化体的制备及其对天然橡胶复合材料性能的影响[J]. 化工进展, 2020, 39(8): 3213-3220.

References

1	MORTON M. Rubber technology[M]. SUBRAMANIAM A. Natural Rubber. New York: Van Nostrand Reinhold Co., 1999: 179-208.
2	彭政, 钟杰平, 廖双泉. 天然橡胶改性研究进展[J]. 高分子通报, 2014, 12(5): 41-48.
2	PENG Zheng, ZHONG Jieping, LIAO Shuangquan. Development of modification of natural rubber[J]. Polymer Bulletin, 2014, 12(5): 41-48.
3	RAJAN V V, DIERKES W, JOSEPH R, et al. Science and technology of rubber reclamation with special attention to NR-based waste latex products[J]. Progress in Polymer Science, 2006, 31(9): 811-834.
4	DAS A, STOCKELHUBER K W, JURK R, et al. Modified and unmodified multiwalled carbon nanotubes in high performance solution-styrene-butadiene and butadiene rubber blends[J]. Polymer, 2008, 49(24): 5276-5283.
5	XU Jun, LI Shuangxin, LI Yu, et al. Preparation, morphology and properties of natural rubber/carbon black/multi-walled carbon nanotubes conductive composites[J]. Journal of Materials Science: Materials in Electronics, 2016, 27(9): 9531-9540.
6	CUI Jian, ZHANG Ling, WU Wangchao, et al. Zinc oxide with dominant (100) facets boosts vulcanization activity[J]. European Polymer Journal, 2019, 113: 148-154.
7	MEIER J G, FRITZSCHE J, GUY L, et al. Relaxation dynamics of hydration water at activated silica interfaces in high-performance elastomer composites[J]. Macromolecules, 2009, 42(6): 2127-2134.
8	PANAMPILLY B, THOMAS S. Nano ZnO as cure activator and reinforcing filler in natural rubber[J]. Polymer Engineering and Science, 2013, 53(6): 1337-1346.
9	CHEN Yongfen, KIM M, LIAN Guoda, et al. Side reactions in controlling the quality, yield, and stability of high quality colloidal nanocrystals[J]. Journal of the American Chemical Society, 2005, 127(38): 13331-13337.
10	THOMAS S P, MATHEW E J, MARYKUTTY C V. Synthesis and effect of surface modified nano ZnO in natural rubber vulcanization[J]. Journal of Applied Polymer Science, 2012, 124(4): 3099-3107.
11	张立群, 吴友平, 王益庆. 橡胶的纳米增强及纳米复合技术[J]. 合成橡胶工业, 2000, 23(2): 71-77.
11	ZHANG Liqun, WU Youping, WANG Yiqing. The nano-reinforcing and nano-compounding technique of rubber[J]. China Synthetic Rubber Industry, 2000, 23(2): 71-77.
12	WANG Mengjiao, WOLFF S, DONNET J B. Silica surface energies and interactions with model compounds[J]. Rubber Chemistry and Technology, 1991, 64(4): 559-561.
13	WANG P, ZAKEERUDDIN S M, COMTE P, et al. Gelation of ionic liquid-based electrolytes with silica nanoparticles for quasi-solid-state dye-sensitized solar cells[J]. Journal of the American Chemical Society, 2003, 125(5): 1166-1167.
14	ZHANG Chengfeng, TANG Zhenghai, GUO Baochun, et al. Significantly improved rubber-silica interface via subtly controlling surface chemistry of silica[J]. Composites Science and Technology, 2017, 156: 70-77.
15	ZHONG Bangcha, JIA Zhixin, HU Dechao, et al. Enhancing interfacial interaction and mechanical properties of styrene-butadiene rubber composites via silica-supported vulcanization accelerator[J]. Composites Part A: Applied Science and Manufacturing, 2017, 96: 129-136.
16	LI Yihang, WU Jiangbing, ZHANG Qingpo, et al. Novel architecture of ZnO nanobundles grown on porous silica as high performance vulcanization accelerators that reinforce rubber composites[J]. Industrial & Engineering Chemistry Research, 2020, 59(10): 4493-4503.
17	WANG Lude, MA Zhao, LIU Shaogang, et al. In situ growth mechanism and the thermodynamic functions of zinc oxide nano-arrays and hierarchical structure[J]. Journal of Thermal Analysis & Calorimetry, 2014, 115(1): 201-208.
18	DU Haiyan, ZHOU Tao, ZHANG Junhua, et al. Moving-window two-dimensional correlation infrared spectroscopy study on structural variations of partially hydrolyzed poly(vinyl alcohol)[J]. Analytical and Bioanalytical Chemistry, 2010, 397(7): 3127-3132.
19	JIANG Qi, WU Zhengying, WANG Yimeng, et al. Fabrication of photoluminescent ZnO/SBA-15 through directly dispersing zinc nitrate into the as-prepared mesoporous silica occluded with template[J]. Journal of Materials Chemistry, 2006, 16(16): 1536-1542.
20	ELAZAZY M S, ISSA A A, Al-MASHREKY M, et al. Application of fractional factorial design for green synthesis of cyano-modified silica nanoparticles: chemometrics and multifarious response optimization[J]. Advanced Powder Technology, 2018, 29(5): 1204-1215.
21	BONCHER W L, LIN T C, CORDES N L, et al. Sequestration of cerium(Ⅲ) bromide into mesoporous silica[J]. Microporous and Mesoporous Materials, 2015, 211: 158-161.
22	XUE Bai, DENG Jianguo, ZHANG Junhua. Multiporous open-cell poly(vinyl formal) foams for sound absorption[J]. RSC Advances, 2016, 6(9): 7653-7660.
23	DONG F P, GUO W P, PARK S K, et al. Controlled synthesis of novel cyanopropyl polysilsesquioxane hollow spheres loaded with highly dispersed Au nanoparticles for catalytic applications[J]. Chemical Communications, 2012, 48(8): 1108-1110.
24	BAKHSHAEI S, KAMBOH M A, MOHAMAD S, et al. A novel cyano functionalized silica-titania oxide sol-gel based ionic liquid for the extraction of hazardous chlorophenols from aqueous environments[J]. RSC Advances, 2016, 6(55): 49358-49369.
25	TIAN Chenchen, CHU Guangyu, FENG Yuxing, et al. Quantitatively identify and understand the interphase of SiO₂/rubber nanocomposites by using nanomechanical mapping technique of AFM[J]. Composites Science and Technology, 2019, 170: 1-6.
26	KRIPOTOU S, PISSIS P, SAVELYEV Y V, et al. Polymer dynamics in polyurethane/clay nanocomposites studied by dielectric and thermal techniques[J]. Journal of Macromolecular Science, Part B: Physics, 2010, 49(1): 86-110.
27	FRAGIADAKIS D, PISSIS P, BOKOBZA L. Glass transition and molecular dynamics in poly(dimethylsiloxane)/silica nanocomposites[J]. Polymer, 2005, 46(16): 6001-6008.
28	RUGGERONE R, GEISER V, DALLE VACCHE S, et al. Immobilized polymer fraction in hyperbranched polymer/silica nanocomposite suspensions[J]. Macromolecules, 2010, 43(24): 10490-10497.
29	LIN Yong, ZENG Zhikai, ZHU Jiarong, et al. Graphene nanosheets decorated with ZnO nanoparticles: facile synthesis and promising application for enhancing the mechanical and gas barrier properties of rubber nanocomposites[J]. RSC Advances, 2015, 5(71): 57771-57780.
30	LIN Yong, LIU Shuqi, PENG Jian, et al. The filler-rubber interface and reinforcement in styrene butadiene rubber composites with graphene/silica hybrids: a quantitative correlation with the constrained region[J]. Composites Part A: Applied Science and Manufacturing, 2016, 86: 19-30.
31	LOO C T. High temperature vulcanization of elastomers: 2. Network structures in conventional sulphenamide-sulphur natural rubber vulcanizates[J]. Polymer, 1974, 15(6): 357-365.