天然橡胶与其环氧化物并用胶基复合材料的黏弹阻尼性能
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摘要
为改善天然橡胶(NR)的阻尼性能,在密炼机中以质量比20∶80混合不同环氧度环氧化天然橡胶(ENR)与天然橡胶制备ENR-NR并用橡胶基体,在橡胶基体的混炼与开炼过程加入其他填充组分(硫磺、促进剂2,2′-二硫代二苯并噻唑(DM)、促进剂N-环己基-2-苯并噻唑次磺酰胺(CZ)、ZnO、硬脂酸、炭黑)得到了宽温域阻尼ENR-NR基复合材料。采用橡胶加工分析仪和动态力学热分析仪,研究了ENR-NR混炼胶和硫化胶的动态力学和阻尼性能。结果表明:NR环氧化增强了分子链局部刚性,改善了胶体与填料的黏结性,但ENR吸附较多炭黑后不易均匀分散于连续相NR中。因此,ENR-NR并用混炼胶的黏度和储能模量随ENR环氧度增大而增加;在NR中加入ENR可改善硫化胶的弹性和阻尼性能。ENR-NR并用胶的有效阻尼温度范围拓宽到较高温度,环氧度为25的ENR与NR并用后,有效阻尼温度范围为-57~1℃,明显宽于NR的-57~-20℃,但高环氧度并用胶则出现阻尼失效区。加入少量ENR对NR的硬度、模量和断裂伸长率影响不大。
In order to improve the damping performance of natural rubber(NR),it was blended in mass ratio of20∶80 with epoxidized natural rubber(ENR)of different epoxidation degrees in a mixer to obtain blend rubber matrix of ENR-NR.The ENR-NR matrix was further filled in mixing and smelting process with other components(sulfur,accelerator 2,2′-dibenzothiazole disulfde(DM),promoter N-cyclohexylbenzothiazde-2-sulphenamide(CZ),ZnO,stearic acid,carbon black)to prepare a wide temperature-range damping ENR-NR matrix composites.The dynamic mechanical properties and the damping characteristics of the plasticized ENR-NR mixtures and their vulcanized rubbers were tested by rubber processing analyzer(RPA)and DMA.The results show that epoxidation of NR enhances the rigidity local molecular chain and improves the adhesion between the matrix and the fillers while ENR adsorbing more carbon black is inhomogeneously dispersed in the continuous phase NR.ENR and its blend rubber with NR exhibit higher viscosity and storage modulus for ENR with higher epoxied degree.The combination of ENRinto NR can obtain materials with better elastic and damping performances for vulcanizates when damping range is widened to higher temperature for ENR-NR compound rubber.The effective range is-57-1℃for ENR-NR with epoxidation degree 25 in comparison with-57--20℃for NR although there is ineffective damping zone for composite rubber when natural rubber being epoxidized to higher degree.However,the addition of a small amount of ENR has little effect on the hardness,modulus and elongation at break of NR matrix composite.
In order to improve the damping performance of natural rubber(NR),it was blended in mass ratio of20∶80 with epoxidized natural rubber(ENR)of different epoxidation degrees in a mixer to obtain blend rubber matrix of ENR-NR.The ENR-NR matrix was further filled in mixing and smelting process with other components(sulfur,accelerator 2,2′-dibenzothiazole disulfde(DM),promoter N-cyclohexylbenzothiazde-2-sulphenamide(CZ),ZnO,stearic acid,carbon black)to prepare a wide temperature-range damping ENR-NR matrix composites.The dynamic mechanical properties and the damping characteristics of the plasticized ENR-NR mixtures and their vulcanized rubbers were tested by rubber processing analyzer(RPA)and DMA.The results show that epoxidation of NR enhances the rigidity local molecular chain and improves the adhesion between the matrix and the fillers while ENR adsorbing more carbon black is inhomogeneously dispersed in the continuous phase NR.ENR and its blend rubber with NR exhibit higher viscosity and storage modulus for ENR with higher epoxied degree.The combination of ENRinto NR can obtain materials with better elastic and damping performances for vulcanizates when damping range is widened to higher temperature for ENR-NR compound rubber.The effective range is-57-1℃for ENR-NR with epoxidation degree 25 in comparison with-57--20℃for NR although there is ineffective damping zone for composite rubber when natural rubber being epoxidized to higher degree.However,the addition of a small amount of ENR has little effect on the hardness,modulus and elongation at break of NR matrix composite.
引文
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[23]殷俊,张玉红,张伟丽,等.氧化石墨烯/天然橡胶-丁睛橡胶复合材料的制备与性能[J].复合材料学报,2016,33(9):1879-1885.YIN J,ZHANG Y H,ZHANG W L,et al.Manulaciure and properties olgraphite oxide/natural rubber-nitrile-butadiene rubber[J].Acta Materiale Compositae Sinica,2016,33(9):1879-1885(in Chinese).
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[25]KENJI U,TAKASHI M,TOSHIKAZU T,et al.Damping elastomer based on model irregular networks of end-linked poly(dimethylsiloxane)[J].Chemistry of Materials,2015,16(1):173-178.
[2]王丽,任昆,丁新静.聚合物基复合材料阻尼研究进展[J].纤维复合材料,2015,32(4):24-27.WANG L,REN K,DING X J.Research progress on damping technology for polymer composites[J].Fiber Composites,2015,32(4):24-27(in Chinese).
[3]ZHAO X,YANG J,ZHAO D,et al.Natural rubber/nitrile butadiene rubber/hindered phenol composites with highdamping properties[J].International Journal of Smart and Nano Materials,2016,6(4):239-250.
[4]WU C,WEI C,GUO W,et al.Dynamic mechanical properties of acrylic rubber blended with phenolic resin[J].Journal of Applied Polymer Science,2008,109(4):2065-2070.
[5]JIAMJITSIRIPONG K,PATTAMAPROM C.Effects of epoxidized natural rubber on gas barrier and mechanical properties of NR/BIIR composites[J].Journal of Elastomers and Plastics,2011,43(4):341-355.
[6]BAKER C S L,GELLING I R.Epoxidized natural rubber[J].Rubber Chemistry&Technology,1987,58(1):67-85.
[7]LU X,LI X,TIAN M.Preparation of high damping elastomer with broad temperature and frequency ranges based on ternary rubber blends[J].Polymers for Advanced Technologies,2014,25(1):21-28.
[8]余和平,李思东,彭政.环氧化天然橡胶玻璃化转变温度与环氧化程度的关系[J].弹性体,1999,9(3):21-23.YU H P,LI S D,PENG Z.The relation between Tgand B of epoxidized natural rubber[J].China Elastomerics,1999,9(3):21-23(in Chinese).
[9]LU X,LI X.Broad temperature and frequency range damping materials based on epoxidized natural rubber[J].Journal of Elastomers&Plastics,2014,46(1):84-95.
[10]TANRATTANAKUL V,KAEWPRAKOB T.Effect of different curing systems on heat shrinkability and mechanical properties of ethylene vinyl acetate/epoxidized natural rubber blends[J].Journal of Applied Polymer Science,2010,119(1):38-46.
[11]PICHAIYUT S,NAKASON C,KUMMERLWE C,et al.Thermoplastic elastomer based on epoxidized natural rubber/thermoplastic polyurethane blends:Influence of blending technique[J].Polymers for Advanced Technologies,2012,23(6):1011-1019.
[12]SENGLOYLUAN K,SAHAKARO K,DIERKES W K,et al.Silica-reinforced tire tread compounds compatibilized by using epoxidized natural rubber[J].European Polymer Journal,2014,51:69-79.
[13]许体文,贾志欣,罗远芳,等.环氧化天然橡胶对天然橡胶/炭黑复合材料的改性作用[J].橡胶工业,2014,61(4):202-207.XU T W,JIA Z X,LUO Y F,et al.Properties of NR/carbon black composites modified by ENR[J].China Rubber Industry,2014,61(4):202-207(in Chinese).
[14]POH B T,TE C S.Cure index and activation energy of vulcanization of natural rubber and epoxidized natural rubber vulcanized in the presence of antioxidants[J].Journal of Applied Polymer Science,2000,77(14):3234-3238.
[15]HE C,WANG Y,LUO Y,et al.Thermal degradation kinetics and mechanism of epoxidized natural rubber[J].Journal of Polymer Engineering,2013,33(4):331-335.
[16]XU K,HE C Z,WANG Y Q,et al.Preparation and characterization of epoxidized natural rubber[J].Advanced Materials Research,2011,396-398:478-481.
[17]汪月琼,彭政,许逵,等.NR/ENR/SiO2复合材料的阻尼性能研究[J].热带作物学报,2014,35(9):1848-1852.WANG Y Q,PENG Z,XU K,et al.Damping properties of NR/ENR/SiO2composites[J].Chinese Journal of Tropical Crops,2014,35(9):1848-1852(in Chinese).
[18]中国国家标准化管理委员会.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.Standardization Administration of the People’s Republic of China.Rubber,vulcanized or thermoplastic-Determination of tensile stress-strain properties:GB/T 528—2009[S].Beijing:China Standards Press,2009(in Chinese).
[19]中国国家标准化管理委员会.硫化橡胶或热塑性橡胶撕裂强度的测定(裤形、直角形和新月形试样):GB/T 529—2008[S].北京:中国标准出版社,2008.Standardization Administration of the People’s Republic of China.Rubber vulcanized or thermoplastic-Determination of tear strength(Trouser,angle and crescent test pieces):GB/T 529—2008[S].Beijing:China Standards Press(in Chinese).
[20]中国国家标准化管理委员会.硫化橡胶或热塑性橡胶压入硬度试验方法第1部分:邵氏硬度计法(邵尔硬度):GB/T531.1—2008[S].北京:中国标准出版社,2008.Standardization Administration of the People’s Republic of China.Rubber,vulcanized or thermoplastic.Determination of indentation hardness-Part 1:Duromerer method(Shore hardness):GB/T 531.1—2008[S].Beijing:China Standards Press,2008(in Chinese).
[21]WANG L,XIANG P Y,ZHANG L Q,et al.Effect of epoxidized natural rubber on the properties of rectorite/carbon black/natural rubber nanocomposites[J].Journal of Applied Polymer Science,2013,128(4):2578-2584.
[22]MOHAMAD N,YAAKUB J,ABD R J,et al.Effects of epoxidized natural rubber(ENR-50)and processing parameters on the properties of NR/EPDM blends using response surface methodology[J].Journal of Applied Polymer Science,2014,131(17):8777-8784.
[23]殷俊,张玉红,张伟丽,等.氧化石墨烯/天然橡胶-丁睛橡胶复合材料的制备与性能[J].复合材料学报,2016,33(9):1879-1885.YIN J,ZHANG Y H,ZHANG W L,et al.Manulaciure and properties olgraphite oxide/natural rubber-nitrile-butadiene rubber[J].Acta Materiale Compositae Sinica,2016,33(9):1879-1885(in Chinese).
[24]方庆红,宋博,高雨,等.纳米石墨/天然橡胶复合材料的应力软化与动态性能[J].复合材料学报,2014,31(6):1446-1451.FANG Q,SONG B,GAO Y,et al.Stress softening and dynamic properties of nano-graphite/natural rubber composites[J].Acta Materiae Compositae Sinica,2014,31(6):1446-1451(in Chinese).
[25]KENJI U,TAKASHI M,TOSHIKAZU T,et al.Damping elastomer based on model irregular networks of end-linked poly(dimethylsiloxane)[J].Chemistry of Materials,2015,16(1):173-178.