【作者】 王欢；

【导师】 王芳辉； 刘德新； 朱红；

【作者基本信息】 北京化工大学 ， 化学工程（专业学位）， 2022， 硕士

【摘要】 橡胶作为新世纪人类社会发展所必需的重要弹性材料,在日常生活、航空和国防等多个领域得到广泛应用。近年来,随着科技发展,对高性能橡胶材料的需求越来越迫切。补强填料可大幅提高橡胶基体的力学性能。白炭黑（Si O₂）有较细的粒子、多孔、比表面积大的特点,且不依赖化石能源,使白炭黑在橡胶补强中得到日益广泛的应用。但Si O₂表面有很多羟基,易团聚在橡胶基体中,从而影响橡胶性能。因此提高白炭黑在橡胶中的分散性显得尤为重要。本论文以白炭黑为主体补强填料,氢化丁腈橡胶（HNBR）为橡胶基体,通过不同结构聚苯胺（PANI）和聚苯胺-碳纳米管（PANI-CNTs）对Si O₂改性得到复合填料,复合填料补强氢化丁腈橡胶得到橡胶复合材料,对复合填料和橡胶复合材料进行表征测试及性能分析。主要研究内容如下:1.通过化学聚合法制备纤维状PANI,在其表面生长Si O₂,得到Si O₂-PANI复合填料,将复合填料Si O₂-PANI混炼到HNBR中得到Si O₂-PANI/HNBR复合材料。研究了Si O₂-PANI中的PANI质量分数对Si O₂-PANI/HNBR填料网络的影响,Si O₂-PANI复合填料对HNBR力学性能的影响;分析复合填料的补强作用机制。当PANI:Si O₂=2%,填料填充量为30 phr时,Si O₂-PANI/HNBR拉伸强度达到为30.31 MPa,撕裂强度为26.7k N/m,是相同份数下纯Si O₂补强填料的129.4%,邵氏A硬度和断裂伸长率均有所上升。2.采用原位聚合法在Si O₂表面生长PANI。制备不同质量比例的Si O₂@PANI复合填料,研究不同苯胺（ANI）质量比例的Si O₂@PANI填料对HNBR力学性能的影响。ANI吸附在Si O₂表面,消耗其表面羟基,减小其亲水性,增大Si O₂与橡胶的相容性,进而提高了HNBR力学性能,当Si O₂:ANI=50:2时,复合材料有最优异力学性能,Si O₂@PANI/HNBR拉伸强度为28.33 MPa,撕裂强度由相同份数下纯Si O₂补强填料的21.4k N/m提升到30.7 k N/m,断裂伸长率与邵氏A硬度均有小幅提高。3.采用的原位聚合法制备聚苯胺包覆碳纳米管材料（CNTs@PANI）,通过静电自组装在CNTs@PANI上生长Si O₂,制备CNTs@PANI不同质量分数的Si O₂-CNTs@PANI三相填料。PANI的包覆有效减轻了CNTs的自身缠结,CNTs@PANI可以降低Si O₂团聚,提高其在HNBR中的分散性,橡胶填料网络减弱。当ANI:CNTs=1:1,CNTs@PANI质量分数为1%,Si O₂-CNTs@PANI填料份数为30 phr时,Si O₂-CNTs@PANI/HNBR拉伸强度达31 MPa,与Si O₂/HNBR相比提升了92%,且Si O₂-CNTs@PANI/HNBR的拉断永久变形降低到8.96%。更多还原

【Abstract】 As an important elastic material necessary for the development of human society in the new century,rubber has been widely used in daily life,aviation,national defense and other fields.In recent years,with the development of science and technology,the demand for high performance rubber materials is becoming more and more urgent.The mechanical properties of rubber matrix can be greatly improved by reinforcing filler.White carbon black has the characteristics of fine particles,porous,large specific surface area,and does not depend on fossil energy,so white carbon black is increasingly widely used in rubber reinforcement.However,there are many hydroxyl groups on the surface of Si O₂,which are easy to condense in the rubber matrix,thus affecting the performance of rubber.Therefore,it is particularly important to improve the dispersity of silica in rubber.In this paper with white carbon black as the main body reinforcing filler,hydrogenated nitrile rubber（HNBR）as the rubber matrix,through the different structure of polyaniline（PANI）and polyaniline-modified carbon nanotubes（PANI-CNTs）on Si O₂ composite filler,reinforcing composite filler hydrogenated NBR rubber composites,the composite filler and rubber composites were characterized test and performance analysis.The main research contents are as follows:1.Fibrous PANI was prepared by chemical polymerization,Si O₂ was grown on its surface to obtain Si O₂-PANI composite filler,and Si O₂-PANI/HNBR composite material was obtained by mixing Si O₂-PANI into HNBR.The influence of PANI mass fraction in Si O₂-PANI on Si O₂-PANI/HNBR packing network and the influence of Si O₂-PANI composite packing on mechanical properties of HNBR were studied.The reinforcing mechanism of composite filler was analyzed.When PANI:Si O₂=2%and filling amount is 30 phr,Si O₂-PANI/HNBR tensile strength is 30.31 MPa and tear strength is 26.7 k N/m,which is 129.4%of that of pure Si O₂ reinforcement filler under the same number.The Hardness and elongation at break of Shaw A are both increased.2.PANI was grown on Si O₂ surface by in-situ polymerization.The effects of Si O₂@PANI packing with different mass ratios of Aniline（ANI）on mechanical properties of HNBR were studied.When Si O₂:ANI=50:2,the composite material has the best mechanical properties.The tensile strength of Si O₂@PANI/HNBR is 28.33 MPa.The tearing strength increased from 21.4k N/m to 30.7 k N/m,and the elongation at break and Shore hardness A increased slightly.3.Polyaniline-coated carbon nanotubes（CNTs@PANI）were prepared by in-situ polymerization.Si O₂ was grown on CNTs@PANI by electrostatic self-assembly to prepare Si O₂-CNTs@PANI three-phase packing with different mass fractions.PANI coating effectively reduced the self-entanglement of CNTs,CNTs@PANI could reduce Si O₂ agglomeration and improve its dispersion in HNBR,and the rubber filler network was weakened.When the mass ratio of ANI:CNTs=1:1,the mass fraction of CNTs@PANI is 1%,and the filler fraction of Si O₂-CNTs@PANI is 30 phr,the tensile strength of Si O₂-CNTs@PANI/HNBR reaches 31 MPa,which is increased by 92%compared with Si O₂/HNBR.And the permanent tensile deformation of Si O₂-CNTs@PANI/HNBR is reduced to 8.96%.更多还原