石墨烯改性白炭黑填料对天然橡胶性能的影响

doi:10.3976/j.issn.1002-4026.20230074

摘要/Abstract

摘要：

白炭黑(主要成分为纳米SiO₂,nano-SiO₂)由于易于制取、绿色环保等优点,现被广泛用于橡胶补强中,但是白炭黑因为结构上的特点,导致其在橡胶中的分散性和补强能力比炭黑差。利用硅烷偶联剂改善白炭黑在橡胶中的分散性,并研究改性白炭黑和石墨烯(GE)的协同补强作用对天然橡胶(NR)的影响。使用助分散剂单宁酸(TA)修饰的石墨烯与使用硅烷偶联剂KH570改性的白炭黑通过迈克尔加成反应得到杂化填料(KS-TGE),与天然橡胶充分混合制得KS-TGE/NR复合材料。经过测试,白炭黑经过改性后不仅改善了其在橡胶中的分散性,并且其和石墨烯制得的杂化填料与天然橡胶共混后,天然橡胶的力学性能得到提升。与未改性的nano-SiO₂/NR相比,改性后的复合材料拉伸强度最高提升36.3%,断裂伸长率最高提升79.5%,此外KS-TGE/NR仍能保持优异的弹性和动态力学性能。

关键词: 白炭黑, 石墨烯, 天然橡胶, 硅烷偶联剂, 杂化填料, 力学性能

Abstract:

Silica (mainly comprising nano-SiO₂) is widely used in rubber reinforcement owing to its advantages of easy preparation and environmental protection. However, owing to its structural characteristics, silica has poorer dispersion and reinforcement ability than carbon black. The purpose of this paper is to present a proposal to improve the dispersion of silica in rubber using a silane coupling agent and to study the effect of synergistic reinforcement of modified silica and graphene on natural rubber. The hybrid filler KS-TGE was obtained through a Michael addition reaction between graphene modified by dispersant tannic acid and silica (KS) modified by the silane coupling agent KH570. Subsequently, the KS-TGE/NR composites were prepared by mixing KS-TGE with natural rubber. Test results showed that the modified silica improves the dispersion in rubber and the mechanical properties of natural rubber after blending with the hybrid filler prepared using graphene and natural rubber. Compared with unmodified nano-SiO₂/NR, the tensile strength of the modified composites increased by 36.3% and the elongation at break increased by 79.5%. In addition, KS-TGE/NR can maintain excellent elastic and dynamic mechanical properties.

Key words: silica, graphene, natural rubber, silane coupling agent, hybrid filler, mechanical properties

中图分类号:

TQ332.5

郭竞泽, 谭双美, 李昱彤, 刘致华, 李嵩, 辛振祥, 赵帅, 李琳. 石墨烯改性白炭黑填料对天然橡胶性能的影响[J]. 山东科学, 2024, 37(1): 69-79.

GUO Jingze, TAN Shuangmei, LI Yutong, LIU Zhihua, LI Song, XIN Zhenxiang, ZHAO Shuai, LI Lin. Effect of graphene-modified silica filler on the properties of natural rubber[J]. Shandong Science, 2024, 37(1): 69-79.

图/表 10

图1

表1

表2

图2

图3

表3

图4

表4

图5

图6

参考文献 37

[1]	KHAN A H, GHOSH S, PRADHAN B, et al. Two-dimensional (2D) nanomaterials towards electrochemical nanoarchitectonics in energy-related applications[J]. Bulletin of the Chemical Society of Japan, 2017, 90(6): 627-648. DOI: 10.1246/bcsj.20170043.
[2]	IDA S. Development of light energy conversion materials using two-dimensional inorganic nanosheets[J]. Bulletin of the Chemical Society of Japan, 2015, 88(12): 1619-1628. DOI: 10.1246/bcsj.20150183.
[3]	GEORGAKILAS V, TIWARI J N, KEMP K C, et al. Noncovalent functionalization of graphene and graphene oxide for energy materials, biosensing, catalytic, and biomedical applications[J]. Chemical Reviews, 2016, 116(9): 5464-5519. DOI: 10.1021/acs.chemrev.5b00620. pmid: 27033639
[4]	HIGGINS D, ZAMANI P, YU A P, et al. The application of graphene and its composites in oxygen reduction electrocatalysis: a perspective and review of recent progress[J]. Energy & Environmental Science, 2016, 9(2): 357-390. DOI: 10.1039/C5EE02474A.
[5]	JOSHI R K, ALWARAPPAN S, YOSHIMURA M, et al. Graphene oxide: the new membrane material[J]. Applied Materials Today, 2015, 1(1): 1-12. DOI: 10.1016/j.apmt.2015.06.002.
[6]	MBAYACHI V B, NDAYIRAGIJE E, SAMMANI T, et al. Graphene synthesis, characterization and its applications: a review[J]. Results in Chemistry, 2021, 3: 100163. DOI: 10.1016/j.rechem.2021.100163.
[7]	BERGER C, SONG Z M, LI T B, et al. Ultrathin epitaxial graphite: 2D electron gas properties and a route toward graphene-based nanoelectronics[J]. The Journal of Physical Chemistry B, 2004, 108(52): 19912-19916. DOI: 10.1021/jp040650f.
[8]	ZHANG Y, ZHANG L Y, ZHOU C W. Review of chemical vapor deposition of graphene and related applications[J]. Accounts of Chemical Research, 2013, 46(10): 2329-2339. DOI: 10.1021/ar300203n. pmid: 23480816
[9]	STANKOVICH S, PINER R D, CHEN X Q, et al. Stable aqueous dispersions of graphitic nanoplatelets via the reduction of exfoliated graphite oxide in the presence of poly(sodium 4-styrenesulfonate)[J]. Journal of Materials Chemistry, 2006, 16(2): 155-158. DOI: 10.1039/B512799H.
[10]	PAREDES J I, VILLAR-RODIL S, SOLÍS-FERNÁNDEZ P, et al. Preparation, characterization and fundamental studies on graphenes by liquid-phase processing of graphite[J]. Journal of Alloys and Compounds, 2012, 536: S450-S455. DOI: 10.1016/j.jallcom.2011.10.025.
[11]	DEAN C R, YOUNG A F, MERIC I, et al. Boron nitride substrates for high-quality graphene electronics[J]. Nature Nanotechnology, 2010, 5(10): 722-726. DOI: 10.1038/nnano.2010.172. pmid: 20729834
[12]	MAYOROV A S, GORBACHEV R V, MOROZOV S V, et al. Micrometer-scale ballistic transport in encapsulated graphene at room temperature[J]. Nano Letters, 2011, 11(6): 2396-2399. DOI: 10.1021/nl200758b. pmid: 21574627
[13]	NAIR R R, BLAKE P, GRIGORENKO A N, et al. Fine structure constant defines visual transparency of graphene[J]. Science, 2008, 320(5881): 1308. DOI: 10.1126/science.1156965. pmid: 18388259
[14]	BISWAS C, LEE Y H. Graphene versus carbon nanotubes in electronic devices[J]. Advanced Functional Materials, 2011, 21(20): 3806-3826. DOI: 10.1002/adfm.201101241.
[15]	LIU H T, LIU Y Q, ZHU D B. Chemical doping of graphene[J]. Journal of Materials Chemistry, 2011, 21(10): 3335-3345. DOI: 10.1039/C0JM02922J.
[16]	DREYER D R, PARK S, BIELAWSKI C W, et al. The chemistry of graphene oxide[J]. Chemical Society Reviews, 2010, 39(1): 228-240. DOI: 10.1039/B917103G. pmid: 20023850
[17]	LI Y, HAN B Y, WEN S P, 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 and Manufacturing, 2014, 62: 52-59. DOI: 10.1016/j.compositesa.2014.03.007.
[18]	YANG G W, LIAO Z F, YANG Z J, et al. Effects of substitution for carbon black with graphene oxide or graphene on the morphology and performance of natural rubber/carbon black composites[J]. Journal of Applied Polymer Science, 2015, 132(15):41832. DOI: 10.1002/app.41832.
[19]	XU T W, JIA Z X, LUO Y F, et al. Interfacial interaction between the epoxidized natural rubber and silica in natural rubber/silica composites[J]. Applied Surface Science, 2015, 328: 306-313. DOI: 10.1016/j.apsusc.2014.12.029.
[20]	CHEN X, GUG J, SOBKOWICZ M J. Role of polymer/filler interactions in the linear viscoelasticity of poly(butylene succinate)/fumed silica nanocomposite[J]. Composites Science and Technology, 2014, 95: 8-15. DOI: 10.1016/j.compscitech.2014.01.025.
[21]	CHOI S S, NAH C, JO B W. Properties of natural rubber composites reinforced with silica or carbon black: influence of cure accelerator content and filler dispersion[J]. Polymer International, 2003, 52(8): 1382-1389. DOI: 10.1002/pi.1232.
[22]	徐惠, 史建新, 翟钧, 等. 纳米TiO₂表面接枝甲基丙烯酸甲酯的聚合反应[J]. 高分子材料科学与工程, 2008, 24(2): 27-30. DOI: 10.16865/j.cnki.1000-7555.2008.02.007.
[23]	NATARAJAN B, NEELY T, RUNGTA A, et al. Thermomechanical properties of bimodal brush modified nanoparticle composites[J]. Macromolecules, 2013, 46(12): 4909-4918. DOI: 10.1021/ma400553c.
[24]	TUNLERT A, PRASASSARAKICH P, POOMPRADUB S. Effect of modified silica particles with phenyltriethoxysilane on mechanical and thermal properties of natural rubber composites[J]. Macromolecular Symposia, 2015, 354(1): 62-68. DOI: 10.1002/masy.201400105.
[25]	WANG L L, JIANG X Y, WANG C L, et al. Titanium dioxide grafted with silane coupling agents and its use in blue light curing ink[J]. Coloration Technology, 2020, 136(1): 15-22. DOI: 10.1111/cote.12434.
[26]	RASHID M H, YUAN Y X. Convergence properties of a restricted Newton-type method for generalized equations with metrically regular mappings[J]. Applicable Analysis, 2022, 101(1): 14-34. DOI: 10.1080/00036811.2017.1392018.
[27]	AHMED N, FAN H, DUBOIS P, et al. Nano-engineering and micromolecular science of polysilsesquioxane materials and their emerging applications[J]. Journal of Materials Chemistry A, 2019, 7(38): 21577-21604. DOI: 10.1039/C9TA04575A.
[28]	全国橡胶与橡胶制品标准化技术委员会. 橡胶中炭黑和炭黑/二氧化硅分散的评估快速比较法: GB/T 6030—2006[S]. 北京: 中国标准出版社, 2007.
[29]	全国橡胶与橡胶制品标准化技术委员会. 硫化橡胶或热塑性橡胶拉伸应力应变性能的测定: GB/T 528—2009[S]. 北京: 中国标准出版社, 2009.
[30]	全国橡标委橡胶物理和化学试验方法标准化分技术委员会. 硫化橡胶回弹性的测定: GB/T 1681—2009[S]. 北京: 中国标准出版社, 2009.
[31]	全国橡胶与橡胶制品标准化技术委员会通用试验方法分技术委员会. 硫化橡胶耐磨性能的测定: GB/T 1689—2014[S]. 北京: 中国标准出版社, 2015.
[32]	全国纤维增强塑料标准化技术委员会. 聚合物基复合材料玻璃化转变温度试验方法动态力学分析法: GB/T 40396—2021[S]. 北京: 中国标准出版社, 2021.
[33]	张云浩, 翟兰兰, 王彦, 等. 硅烷偶联剂KH-570表面改性纳米SiO₂[J]. 材料科学与工程学报, 2012, 30(5): 752-756. DOI: 10.14136/j.cnki.issn1673-2812.2012.05.030.
[34]	AHN B, KIM D, KIM K, et al. Effect of the functional group of silanes on the modification of silica surface and the physical properties of solution styrene-butadiene rubber/silica composites[J]. Composite Interfaces, 2019, 26(7): 585-596. DOI: 10.1080/09276440.2018.1514145.
[35]	高瑞丰. 氧化石墨烯天然橡胶复合材料的制备与摩擦磨损性能研究[D]. 北京: 北京化工大学, 2021.
[36]	XUE C, GAO H Y, HU G. Viscoelastic and fatigue properties of graphene and carbon black hybrid structure filled natural rubber composites under alternating loading[J]. Construction and Building Materials, 2020, 265: 120299. DOI: 10.1016/j.conbuildmat.2020.120299.
[37]	WU W L, WANG J. Effect of KH550 on the preparation and compatibility of carbon fibers reinforced silicone rubber composites[J]. Silicon, 2018, 10(5): 1903-1910. DOI: 10.1007/s12633-017-9700-4.

试样	拉伸强度/ MPa	100%定伸应力/MPa	300%定伸应力/MPa	500%定伸应力/MPa	断裂伸长率/%	力最大值/N	回弹/%
KS-TGE/NR-0-1	21.20	1.40	4.70	15.30	585.78	209.20	79.70
KS-TGE/NR-1-1	22.40	1.50	5.70	17.50	570.37	183.50	79.40
KS-TGE/NR-2-1	27.20	1.70	5.60	16.60	630.49	222.70	76.40
KS-TGE/NR-3-1	27.80	1.70	6.80	19.40	590.37	220.00	77.90
KS-TGE/NR-0-0.4	26.80	1.40	4.40	15.00	621.81	220.10	80.30
KS-TGE/NR-1-0.4	28.90	1.40	4.60	14.80	627.97	234.70	80.00
KS-TGE/NR-2-0.4	27.20	1.40	4.90	14.30	665.33	220.10	79.40
KS-TGE/NR-3-0.4	27.70	1.40	5.10	15.80	634.01	223.10	79.40

试样	平均聚集体尺寸/μm	分散度/%
KS-TGE/NR-0-1	9.3	95.5
KS-TGE/NR-1-1	8.5	92.0
KS-TGE/NR-2-1	9.4	93.9
KS-TGE/NR-3-1	10.0	90.9
KS-TGE/NR-0-0.4	10.6	95.6
KS-TGE/NR-1-0.4	11.3	96.9
KS-TGE/NR-2-0.4	11.4	92.9
KS-TGE/NR-3-0.4	10.7	93.1
nano-SiO₂/NR	13.6	96.9

试样	t_g/℃	0 ℃时的tan δ	60 ℃时的tan δ
nano-SiO₂/NR	-41.14	0.148	0.029
KS-TGE/NR-0-1	-40.61	0.177	0.032
KS-TGE/NR-1-1	-41.10	0.148	0.033
KS-TGE/NR-2-1	-42.01	0.147	0.035
KS-TGE/NR-3-1	-41.20	0.156	0.040
KS-TGE/NR-0-0.4	-41.76	0.144	0.032
KS-TGE/NR-1-0.4	-42.24	0.142	0.036
KS-TGE/NR-2-0.4	-40.94	0.168	0.038
KS-TGE/NR-3-0.4	-42.36	0.137	—