摘要
本文研究了溴化丁基橡胶(BIIR)在热氧、紫外照射、溶剂浸泡和盐雾环境中的老化行为,初步推断其热氧和紫外老化机理,并选择不同评价指标预测溴化丁基橡胶在不同环境中的使用寿命。
在热氧环境中,BIIR老化后表面产生粉化与裂纹,并且温度升高将导致裂纹数目增加,宽度增大。随热氧老化时间的延长,当温度在25～60℃时,BIIR的交联密度、硬度、拉伸强度和扯断伸长率几乎不变化,当温度在70℃以上时,BIIR的硬度和交联密度逐渐增大,而拉伸强度和扯断伸长率逐渐降低,当温度达到110℃以后,BIIR的硬度仍在增大,而拉伸强度和扯断伸长率几乎丧失,交联密度也出现降低。热氧作用对BIIR的热稳定性影响较大。热氧老化使BIIR分子中的双键减少的同时,伴随有羟基和羧基等基团生成,同时BIIR结构中主链断裂氧化导致-CH2-、异丙基基团减少,热氧老化温度升高加剧上述基团变化程度。在BIIR热分解过程中,-C-Br键因键能较低而首先发生断裂,出现脱溴化氢的反应,之后-C-C-键所形成的主链断裂,断链后的低聚物后期在氧的存在作用下大量生成烃类气体分子。
在紫外照射环境中,老化使BIIR表面产生粉化与开裂,且裂纹的密度随紫外老化时间的延长而逐渐增大。随紫外老化时间延长,BIIR的交联密度和硬度逐渐增大,而拉伸强度和扯断伸长率则逐渐降低,且拉伸强度在初始老化2天时间内有所增大。紫外照射环境对BIIR的热稳定性影响不大。紫外老化过程中氧的参与作用导致羟基和羧基等基团的增多,继而使BIIR分子中的主链断裂而导致-CH2-基团和异丙基基团的减少。BIIR中,-C-Br键键能较低,紫外光照射下首先发生断裂生成气体逸出,之后与双键相连的a位的甲基氢处形成过氧化反应中心,引致之后链断裂。
50℃环境下,在93#汽油中,BIIR10天后质量溶胀率超过100%且表面出现发粘,其耐油性较差；在环己烷非极性溶剂中,7天后质量溶胀率达96.2%且未出现表面发粘现象；在乙醇极性溶剂中,6天后质量溶胀率仅0.45%,几乎不能溶解或溶胀。
在35℃盐雾环境中,随着老化时间延长,BIIR表面产生凹凸不平和空洞,并有微裂纹产生；质量变化率逐渐增大；硬度增大,而拉伸强度和扯断伸长率则逐渐降低,随老化时间延长,变化趋势逐渐平缓。
50℃条件下,在热氧环境中,当选用交联密度、硬度、拉伸强度和扯断伸长率作为评价指标时,BIIR的使用寿命分别为68天、107天、63天和54天；在紫外环境中,当选用交联密度、硬度、拉伸强度和扯断伸长率作为评价指标时,BIIR的使用寿命分别为47天、540天、41天和34天；在溶剂环境中,当选用质量溶胀率作为评价指标时,BIIR在93#汽油和环己烷中的使用寿命均为1天,而在乙醇中的使用寿命则较长；在盐雾环境中,当选用质量变化率、硬度和扯断伸长率作为评价指标时,BIIR的使用寿命分别为24195天、4359天和622天,以拉伸强度作为评价指标时,其使用寿命则较长。
Aging behavior of brominated butyl rubber(BIIR) were studied in thermal-oxidative,UV irradiation,solvent immersion and salt spray environments,and the mechanism in the environment of thermal-oxidative and UV irradiation were predicted.Different Evaluating indicators were adopted to predict the service life of BIIR in various environments.
In thermal-oxidative environment, crack and powder were produced on the surface of BIIR after aging.The higher the temperature and the wider the crack.When the temperature were during 25～60℃,the crosslink denstiy,hardness,tensile strength and elongation at break rarely changed with aging.The hardness and crosslink density increased,while the tensile strength and elongation at break decreased at 70℃and above with the elongation of aging time.When the temperature reached 110℃,the hardness increased,while the tensile strength and elongation at break were almost lost,and crosslink density began lower.The thermal-oxidative stability was deteriorated after aging in this environment.From the results of ATR-FTIR spectroscopy it can be concluded that the increasing strength of the peak of carboxy groups and hydroxyl groups of BIIR,but the decreasing of double bonds, isopropyl groups and methylene groups of its with the increasing temperatures. The bond energy of -C-Br is low and first fractured in the process of BIIR thermal decomposition,the reaction of hydrogen bromide off happened. Then, the main strand broke and formed -C-C-bond.In the late period,the oligomers at the presence of oxygen generated hydrocarbon gas molecules.
In the UV irradiation environment,crack and powder appeared on the surface and the crack density increased gradually with aging.The hardness and crosslink density tended to increase while the tensile strength and elongation at break decreased.The thermal-oxidative stability was not deteriorated upon exposure to UV. The spectroscopy of ATR-FTIR illustrated oxygen took part in the aging and the increasing strength of the peak of carboxy groups and hydroxyl groups,but the decreasing of methylene groups and isopropyl groups of BIIR with aging-C-Br bond in BIIR is low and the bond was broken first to generate gas under UV irradiation. After that peroxide reaction center formed in the position of a of methyl hydrogen connected with double bond resulting in strand breaks later.
Under 50℃, the swelling rate of the brominated butyl rubber reached more than 100% after 10 days in 93# gas, and the surface was sticky. It indicated the oil resistance of BIIR was poor.Under the same temperature in cyclohexane as the non-polar solvent, swelling rate was 96.2% after 7 days and the surface did not appear sticky,while in polar solvents ethanol, the swelling rate of BIIR was 0.45% after 6 days almost insoluble or swelling.
In the environment of salt spray at 35℃, with increasing of aging time, the surface of BIIR became uneven and cavity, and micro-cracks. Rate of quality change increased.The hardness gradually increased, while the tensile strength and elongation at break decreased gradually.With the elongation of time,these change gradually flattened.
In thermal-oxidative environment,the service life of BIIR is 68d,107d,63d and 54d when crosslink density,hardness,tensile strength and elongation at break are used as evaluating indicators,respectively.In UV irradiation environment,its service life is 47d,540d,41d and 34d when crosslink density,hardness,tensile strength and elongation at break are used as evaluating indicators,respectively. In the solvent environment, selected the rate of quality change as evaluating indicator, its service life in the 93# gasoline and in cyclohexane is 1d respectively, while in ethanol is longer. In the salt spray environment, the service life of BIIR is 24195d,4359d and 622d when rate of quality change,hardness and elongation at break are used as evaluating indicators respectively,and its service life is longer when tensile strength as evalutating indicator.
引文
[1]甘复兴,林安.开展西部环境中高分子材料快速老化失效问题的研究[J].中国科学基金,2005,6：331-333
[2]化学工业部合成材料老化研究所.高分子材料老化与防老化[M].北京：化学工业出版社,1979
[3]陈经盛.橡胶老化防护与监测(一)[J].化工标准化与质量监督,1996,(1)：30-32
[4]R P Brown, G Soulagnet. Microhardness profiles on aged rubber compounds[J].Polymer Testing,2001(20):295-303
[5]Garance Lopitaux,Xavier Coqueret,Frederic Boursereau,et al. Immediate and long-term effects of electron beam irradiation on nitrile-butadiene rubber[J].Nucl. Instr. and Meth. in Phys. Res. B,2003,208:500-504
[6]雷卫华,王建华,田野.MVQ-EPDM并用胶及泡沫的热老化性能研究[J].特种橡胶制品,2005,26(3)：16-18
[7]李德军.关于奥地轿车橡胶配件耐臭氧老化龟裂的研究[J].特种橡胶制品,1992,(3)：57-59
[8]Marcia M Rippel, Carlos A P Leite, Lay-Theng Lee, et al...Formation of calcium crystallites in dry natural rubber particles[J].Journal of Colloid and Interface Science,288(2):449-456
[9]崔燕,赵铱民,邵龙泉.臭氧老化作用对SY—1硅橡胶机械性能的影响[J].实用口腔医学杂志,2002,18(3)：268-269
[10]李旭日,梁悦,孙影,等.轮胎胎面胶老化交联密度与机械性能研究[J].河南化工,2008,25(2)：24-26
[11]Mogon Patel, Anthony R Skinner, Robert S. Maxwell. Sensitivity of condensation cured polysiloxane rubbers to sealed and open-to air thermal ageing regimes [J].Polymer Testing,2005,24(5):663-668
[12]Mitra S,Ghanbari-Siahkali A,Kingshott P,et al.Chemical degradation of crosslinked ethylene-propylene-diene rubber in an acidic environment. Part Ⅱ. Effect of peroxide crosslinking in the presence of a coagent[J]. Polymer Degradation and Stability,2006(91):81-93
[13]Kenneth T Gillen, Robert Bernstein,Dora K Derzon.Evidence of non-Arrhenius behaviour from laboratory aging and 24-year field aging of polychloroprene rubber materials[J].Polymer Degradation and Stability,2005,87(1):57-67
[14]苏正涛,朱华,吴涛,等.氟硅橡胶硫化胶的老化性能[J].有机硅材料,2007,21(5)：284-286
[15]M.Garbarczyk et al.Characterization of aged nitrile rubber elastomers by NMR spectroscopy and microimaging[J].Polymer,2002(43):3169-3172
[16]Sirirat Jitkarnka,,Boonrudee Chusaksr,Pitt Supaphol, et al..Influences of thermal aging on properties and pyrolysis products of tire tread compound[J].Journal of Analytical and Applied Pyrolysis,2007,80(1):269-276
[17]李庆峰,宿志一.高压直流复合绝缘子5000 h人工加速老化试验[J].电网技术,2006,30(12)：64-68
[18]周红萍,李敬明,何强,等.MVQ海绵老化性能的研究[J].橡胶工业,2007,54(1)：14-16
[19]Y T Wei, L Nasdala, H Rothert, et al.. Experimental investigations on the dynamic mechanical properties of aged rubbers[J]. Polymer Testing,2004,23(4):447-453
[20]Gwaily SE,Badawy MM,Hassan HH,et al..Influence of thermal aging on crosslinking density of boron carbide/natural rubber composites [J].Polymer Testing,2003,22(1):3-7
[21]Dong Myung Park,Won Hi Hong,Sang Goo Kim, et al.. Heat generation of filled rubber vulcanizates and its relationship with vulcanizate network structures [J]. European Polymer Journal,2000,36(11):2429-2436
[22]Mogon Patel,Anthony R Skinner,Amiya Chaudhry,et al.Impact of thermal ageing on the tin catalyst species in room temperature vulcanised polysiloxane rubbers[J].Polymer Degradation and Stability,2004,83(1):157-161
[23]M. Di et al. Radiation effect of 150 keV protons on methyl silicone rubber reinforced with MQ silicone resin [J].Nucl. Instr. and Meth. in Phys. Res. B,2006,248(1):31-36
[24]Ranimol Stephen et al. Thermal stability and ageing properties of sulphur and gamma radiation vulcanized natural rubber (NR) and carboxylated styrene butadiene rubber (XSBR) latices and their blends[J].Polymer Degradation and Stability,2006,91(8):1717-1725
[25]罗权焜,郭建华.几种合成橡胶的共混、硫化特性与性能的研究[J].特种橡胶制品,2007,28(2)：5-13
[26]耿新玲,苏正涛,钱黄海,等.镀银镍粉填充型导电硅橡胶的性能研究[J].橡胶工业,2006,53(7)：417-419
[27]A I Eatah, A A Ghani, A A Hashem.Thermal ageing dependence of electrical conductivity for butyl rubber (IIR) loaded with HAF carbon black[J].Polymer Degradation and Stability, 1989,26(2):145-150
[28]S.E.Gwaily, M M Badawy,H H Hassan,et al.Natural rubber composites as thermal neutron radiation shields 1. B4C/NR composites[J]. Polymer Testing,2002,21(2):513-517
[29]Yangyang Sun,Shijian Luo,Ken Watkinsc,er al..Electrical approach to monitor the thermal oxidation aging of carbon black filled ethylene propylene rubber[J].Polymer Degradation and Stability,2004,86(2):209-215
[30]范刚.车用橡胶制品老化问题研究[J].汽车科技,2003：16,17,27.
[31]朱绪飞,文威,贾红兵,等.电容器密封橡胶及其老化机理[J].弹性体,2002,12(1)：58-62
[32]金冰,胡小锋,魏伯荣,等.天然橡胶的热氧老化研究[J].广州化工,2006,34(6)：32-33
[33]张凯,范敬辉,马艳,等.ZN-1阻尼橡胶材料老化性能及其老化机理[G].中国工程物理研究院科技年报,2006,(1)：474-475
[34]Naba K Dutta, D K Tripathy.The influence of curing systems on the properties of bromobutyl rubber:Part 2-Effect of concentration of curing resin on the dynamic mechanical properties[J].Polymer Degradation and Stability,1990,30(2):231-256
[35]高晓敏,何舟,杨雪海.部分高分子材料老化研究进展[J].合成材料老化与应用,2005,34(1)：39-42
[36]钱红莲,王平粤,陈鹰.老化对环氧化天然橡胶分子结构及性能的影响[J].应用化学,2005,22(10)：1145-1147
[37]余和平,许逵.环氧化天然橡胶的热老化性能[J].应用化学,2004,21(1)：76
[38]张北龙,陈美,刘惠伦.硫化环氧化天然橡胶的热分析[J].应用化学,2001,18(4)：332-334
[39]杨春亮,黎涛,黎志平.热处理对环氧化天然橡胶性能的影响[J]._橡胶工业,2002,49(7)：400-402
[40]钱红莲,王平粤,杨春亮.用橡胶加工分析仪研究环氧化天然橡胶的性能[J].特种橡胶制品,2004,25(3)：51-53
[41]李思东,余和平,彭政,等.用FTIR研究环氧化天然橡胶的热老化[J].应用化学,1999,16(2)：111-112
[42]F Sundardi, S Kadariah. Radiation grafting of methyl methacrylate monomer on natural rubber latex[J].Journal of Applied Polymer Science,1984,29(5):1515-1521
[43]刘洪涛,张华,向明,等.ENR、MG塑炼胶的热氧老化性能研究[J].合成材料老化与应用,2007,36(1)：5-7
[44]张北龙,刘惠伦.环氧化天然橡胶／PVC共混物的热氧降解[J].橡胶工业,2001,48(6)：330-333
[45]付秋兰,吴向荣,温茂添.缩合型室温硫化硅橡胶耐热性的研究进展[J].有机硅材料,2003,17(1)：28-31
[46]谢择民,李其山,王金亭.改进硅橡胶耐热性的研究[J].特种橡胶制品,1981(2)：1
[47]Radhak rishnan T S.New method for evaluation of kinetic parameters and mechanism of degradation from pyrolysis-GC studies:Thermal degradation of polydimethylsilOxanes[J].J Appl Polym Sci,1999,73(3):441
[48]Grassie N,Macfarlane I G.The thermal degradation of polysiloxanes(I):Poly(dimethyl siloxane) [J].Eur Polym J,1978,14(11):875
[49]Grassie N,Macfarlane I G,Francey K F. The thermal degradation of polysiloxanes(Ⅱ): Poly(methyl henyisiloxane) [J].Eur Polym J,1979,15(5):415
[50]Deshpande G,Rezac M E.The effect of phenyl content on the degradation of poly(dimethyldiphenyl)siloxane copolymers [J].Polym Degrad Stab,2001,74(2):363
[51]张凯,范敬辉,吴菊英,等.硅橡胶泡沫材料的热氧老化机理研究[J].合成材料老化与应用,2007,36(3)：18-21
[52]程买增,胡新嵩,莫万奎.室温硫化硅橡胶耐热性的研究进展[J].有机硅材料,2006,20(1)：38-41
[53]M Patel,A R Skinner.Thermal ageing studies on room-temperature vulcanised polysiloxane rubbers[J]. Polymer Degradation and Stability,2001,73(3):399-402
[54]M Abdul Kader, Anil K Bhowmick.Thermal ageing, degradation and swelling of acrylate rubber,fluororubber and their blends containing polyfunctional acrylates[J].Polymer Degradation and Stability,2003,79(2):283-295
[55]N O Goga,D E Demco,J.Kolz,et al..Surface UV ageing of elastomers investigated with microscopic resolution by single-sided NMR[J].Journal of Magnetic Resonance,2008,192(1):1-7
[56]Virgili L,Giantomassi F,Pugnaloni A,et al.. FT-IR and biological evaluations of native and artificially aged rubber mixes[J].Polymer Degradation and Stability,2005,87(1):143-151
[57]齐藤孝臣.各种橡胶的老化机理[J].橡胶参考资制,1996,26(6)：9-20
[58]陈舜娥.橡胶的大气老化[J].合成材料老化与应用,2003,(1)：34-49
[59]王作龄编译.防老剂应用技术[J].世界橡胶工业,2001,28(1)：55-59
[60]江畹兰编译.周期性形变及臭氧对橡胶寿命的影响[J].世界橡胶工业,1999,26(4)：33-34
[61]C.K. Radhakrishnan, Rosamma Alex, G. Unnikrishnan.Thermal, ozone and gamma ageing of styrene butadiene rubber and poly(ethylene-co-vinyl acetate) blends[J].Polymer Degradation and Stability,2006,91(4):902-910
[62]陈经盛.橡胶老化防护与监测(二)[J].化工标准化与质量监督,1996,(2)：23-26
[63]张友南,杨军,陈忠海.天然橡胶制品抗疲劳性能的因素简析[J].世界橡胶工业,2002,29(6)：35-39
[64]王梦蛟等.橡胶工业手册第二分册第2版[M].化学工业出版社,1989：172
[65]Visser S A,Hewitt C,Binga T D.Stability of filled poly(diphenylsiloxane-co-dimethylsilOxane)elastomers to cyclic stress at elevated temperatu re[J].J Polym Sci(Part B):Polym Phys,1996,34(9):1679
[66]李青山,王新伟,殷永传.硅橡胶氟橡胶及其共混物阻燃热稳定和耐热油性的研究[J].世界橡胶工业,2005,32(2)：40-44
[67]Mohammadreza Mofidi, Elisabet Kassfeldt, Braham Prakash.Tribological behaviour of an elastomer aged in differentoils[J].Tribology International,2008,41(9-10),:860-866
[68]Van der Waal G. The relationship between the chemical structure of ester base fluids and their influence on elastomer seals, and wear characteristics[J].J Synth Lubr,1984,(1-4):35-47
[69]Torbacke M, Johansson A.Seal material and base fluid compatibility:an overview[J]. J Synth Lubr,2005,22(2):123-42
[70]刘新民,吴霞.SBS基热塑性弹性体的老化性能研究[J].弹性体,2003,13(5)：16-20
[71]肖琰,魏伯荣,杜茂平.橡胶加速老化试验及贮存期推算方法[J].合成材料老化与应用,2007,36(1)：40-43
[72]李永清,晏欣,郑淑贞.硫化橡胶防老化涂层的研制[J].合成材料老化与应用,2004,33(4)：31-35
[73]R P Brown,G Soulagnet. Microhardness profiles on aged rubber compounds[J].Polymer Testing,2001,20:295-303
[74]P R Morrell,M Patel,A R Skinner.Accelerated thermal ageing studies on nitrile rubber O-rings[J]. Polymer Testing,2003,22:651-656
[75]David R Bauer, John M Baldwin, Kevin R Ellwood-Rubber aging in tires. Part 2:Accelerated oven aging tests [J].Polymer Degradation and Stability,2007,92(1):110-117
[76]Deng Huang, Bart J LaCount, Jose M Castro, et al..Development of a service-simulating, accelerated aging test method for exterior tire rubber compounds[J].Polymer Degradation and Stability,2001 (74):353-362
[77]Bart J LaCount,Jose M Castro,Frederick Ignatz-Hoover.Development of a service-simulating, accelerated aging test methodfor exterior tire rubber compounds II.Design and development of an accelerated outdoor aging simulator[J].Polymer Degradation and Stability,2002,75(2):213-227
[78]Kenneth T Gillen,Mathew Celina,Robert Bernstein. Validation of improved methods for predicting long-term elastomeric seal lifetimes from compression stress-relaxation and oxygen consumption techniques[J].Polymer Degradation and Stability,2003,82 (1):25-35
[79]刘振海.热分析导论[M].北京：化学工业出版社,1991
[80]Yu H P,Li S D,Zhong J P,et al..Studies of thermooxidative degradation process of chlorinated natural rubber from latex[J].Thermochimica Aeta,2004,410(1):119-124
[81]Mathew A P, Packirisamy S, Thomas S. Studies on the thermal stability of natural rubber/ polystyrene interpenetrating polymer networks: thermogravimetric analysis[J].Polymer Degradation and Stability,2001,72(3):423-439
[82]Kader M A, Bhowmick A K. Thermal aging, degradation and swelling of acrylate rubber, fluororubber and their blends containing polyfunctional acrylates[J].Polymer Degradation and Stability.2003,79(2):283-295
[83]黄华明,陈美,曾宗强,等.用TG、DTA研究不同品系天然橡胶热降解[J].热带农业工程,2006,(2)：35-37
[84]侯婷婷,李程鹏,钟杰平,等.氯化钙凝固天然橡胶的热分析研究[J].广东化工,2006,33(163)：26-28
[85]Sirait K T,Suwarno S.Evaluation of surface degradation of silicone rubber under natural tropical aging using thermogravimetric and thermomechanical analysis[A].Proceedings of the IEEE International Conference on Properties and Applications of Dielectric Materlals[C].Xi'an:Institute of Electrical and Electronics Engineers Inc.,2000:645-648
[86]Wei Y T,Nasdala L,Rothert H,et al..Experimental investigations on the dynamic mechanical properties of aged rubbers [J].Polymer Testing,2004,23(4):447-453
[87]Xie Z M,Wi Y T,Liu Y Y,el al..Dynamic mechanical properties of aged filled rubbers [J]. Journal of Macromolecular Science-Physics,2004,43 (4) 805 817
[88]Wei Y T,Nasdala L,Rothert H,et al..Experimental investigations on the dynamic mechanical properties of aged rubbers [J].Polymer Testing,2004,23(4):447-453
[89]Patel M,Morrell PR,Evans J.Load bearing property testing of a silica filled room temperature vulcanised polysiloxane rubber[J].Polymer Testing,2004,23(5):605-611
[90]张苹,兰慧萍,唐学明.1,2-聚丁二烯硫化胶的热氧老化性能及其防护体系的研究[J].高分子材料科学与工程,1989,5(6)：55-60
[91]Denardin E I G,Janissek P R,Samios D.Time-temperature dependence of the thermo-oxidative aging of polychloroprene rubber[J].Thermochimica Acta,2003,395(2):159-167
[92]赵霞,张雪芹,黄铃,等.同步热分析法研究聚丁二烯橡胶热降解过程[J].橡胶工业,2006,53(6)：370-372
[93]A E Somers,T J Bastow,M I Burgar,et al..Quantifying rubber degradation using NMR[J].Polymer Degradation and Stability 2000,70(1):31-37
[94]Parker D D, KoerIig J L.Solid-state 13C-NMR studies of changes in crosslinked carbon structure of natural rubber during heating under air and nitrogen environments[J]. Journal of Applied Polymer Science,1998,70(7):1371-1383
[95]Manfred Knorgcn,Uwe Heuert,Horst Schneider,et al..Spatially resolved and integral NMR investigation of the aging process of carbon black filled natural rubber[J].Polymer Bulletin,1997,38(1):101-108
[96]J Y Buzare,G Silly,J Emery,et al.. Aging effects on vulcanized natural rubber studied by high resolution solid state 13C-NMR [J].European Polymer Journal,2001,37(1):85-91
[97]Maciej Garbarczyk, Winfried Kuhn, Jacek Klinowski,et al..Characterization of aged nitrile rubber elastomers by NMR spectroscopy and microimaging[J].Polymer,2002,43(11):3169-3172
[98]N O Goga,D E Demco,J Kolz,et al..Surface UV aging of elastomers investigated with microscopic resolution by single-sided NMR[J]. Journal of Magnetic Resonance, 2008,192(1):1-7
[99]Resendes R,Hopkins W,Niziolek T,et al..Cost-effective modifiers for the preparation of BIIR based tire tread formulations [J].Rubber World,2003,228(6):46-51
[100]Kumar A,Commereuc S,Verney V.Aging of elastomers:a molecular approach based on rheological chamcterization[J].Polymer Degradation and Stability,2004,85(2):751-757
[101]李思东,彭政,余和平,等.用红外差谱表征橡胶的热老化[J].橡胶工业,1998,45(8)：494-498
[102]张静芳,译.增塑溴化丁基橡胶撕裂断裂及拉伸断裂的扫描电镜观察[J].橡胶译丛,1992,(4)：71-76
[103]N Dadvand,R S Lehrle,I W Parsons,et al..Use of pyrolysis-GC-MS to assess the thermal degradation behaviour of polymers containing chlorine II. Thermal stability characteristics of Neoprene/chlorobutyl rubber composites, before and after artificial ageing[J].Polymer Degradation and Stability,2000,67(3):407-419
[104]F Delor-Jestin,J Lacoste,N Barrois-Oudin,et al..Photo-,thermal and natural ageing of ethylene-propylene-diene monomer (EPDM) rubber used in automotive applications.Influence of carbon black, crosslinking and stabilizing agents [J].Polymer Degradation and Stability,2000,67(3):469-477
[105]魏小琴,余淑华,许明,等.用X射线光电子能谱法研究氟硅橡胶的热氧老化机理[J].橡胶工业,2008,55(7)：441-443
[106]Mpatel.Aging and characterization of polysiloxane rubbers[J].Aging Studies and Lifetime Extension of Materials,1999,36(1):97-101
[107]A N Chaudhry,N. C Billingham.Characterisation and oxidative degradation of a room-temperature vulcanized poly(dimethylsiloxane) rubber[J]. Polymer Degradation and Stability,2001,73(3):505-510
[108]Tuyet-Trinh Do,Mathew Celina,Peter M Fredericks. Attenuated total reflectance infrared microspectroscopy of aged carbon-filled rubbers [J].Polymer Degradation and Stability,2002,77(3):417-422
[109]Zhu Y,Otsubo M,Honda C,et al..Loss and recovery in hydrophobicity of silicone rubber exposed to corona discharge[J].Polymer Degradation and Stability,2006,91 (7):1448-1454
[110]Nsouli B,Roumie M,Zahraman K,et al..PIXE, micro-PIXE and RBS analysis of thermal aged rubber material:On the additives behaviour versus aging time[J].Nucl. Instr. and Meth. in Phys. Res. B,2002,198(3-4):201-207
[111]W.Stephen Fulton, Graham C Smith, Keith J. Titchener.Interfacial microanalysis of rubber-tyre-cord adhesion and the influence of cobalt[J].Applied Surface Science 2004,221(1-4):69-86
[112]周大纲,谢颌成.塑料老化与防老化技术[M],北京：中国轻工业出版社,1998：12
[113]Gillen K T.New method for predicting lifetime of seals from compression stress relaxation experiments[R].Albuquerque:Sanfia National Laboratories,1998
[114]叶苑殉.聚合物防老化实用手册[M].北京化学工业出版社,1999
[115]张凯,黄渝鸿,马艳,等.橡胶材料加速老化试验及其寿命预测方法.化学推进剂与高分子材料,2004,2(6)：44-48
[116]李咏今.硫化橡胶热氧老化时物理机械性能变质规律的研究[J].特种橡胶制品,1997,18(1)：42-57
[117]朱华,张洪燕,杨希仁,等.计算机辅助航空橡胶和密封剂老化寿命预测.材料工程,2001,7：45-47
[118]袁立明,顾伯勤,陈哗.应用老化损伤因子评估纤维增强橡胶基密封材料的寿命[J].合成材料老化与应用,2003,32(2)：27-31
[119]曹翠微,蔡体敏.橡胶老化性能的神经网络研究方法[J].固体火箭技术,2005,28(2)：142-1448
[120]梁星宇.丁基橡胶应用技术[M].北京：化学工业出版社,2004,5：254-310
[121]Naba K Dutta,D K Tripathy. Influence of curing systems on the properties of bromobutyl rubber:Part Ⅲ—Effect of different types of curing systems on the cure characteristics, physical properties and thermo-oxidative degradation characteristics[J].Polymer Degradation and Stability,1992,36,(1):73-80
[122]W Hopkins,W von Hellens.Reinforcement of BIIR with silica[J].Rubber World,2002,226(1):37-41
[123]钱寒东.溴化丁基橡胶性能研究[J].世界橡胶工业,2004,31(2)：6-11
[124]谭志海,任文坛,张勇,等.白炭黑补强溴化丁基橡胶的性能及特点[J].特种橡胶制,2006,27(1)：10-13
[125]马文石,汪军,邓卫星,等.补强剂对酚醛树脂硫化BIIR性能的影响[J].橡胶工业,2006,53(8)：467468
[126]黄祖长译.卤化丁基橡胶内衬层对轮胎工作性能的影响[J].橡胶参考资料,2007,39(3)：23-27
[127]王怀宇译.充气压力保持率对轮胎老化和耐久性的影响[J].橡胶参考资料,2008,38(1)：20-24
[128]Quanlin Zhao, Xiaogang Li, Jin Gao. Aging of ethyleneepropyleneediene monomer (EPDM) in artificial weathering environment[J]. Polymer Degradation and Stability, 2007,9(10):1841-1846
[129]李咏今.橡胶老化文献数据的再处理[J].橡胶工业,1996,43(9)：515-516
[130]茆诗松,王玲玲.加速寿命试验[M].北京：科学出版社,2000
[131]伍一波,李树新,郭文莉.溴化丁基橡胶的制备与结构表征[J].合成橡胶工业,2006 5,29(4)：267-270
[132]董炎明.高分子材料实用剖析技术[M].北京：中国石化出版社,1997
[133]姚允斌,解涛,高英敏.物理化学手册[M].上海：上海科学技术出版社,1985：114-118.
[134]橡胶工业手册(第八分册)[M].北京：化学工业出版社,1992
[135]T. Ha-Anh,T. Vu-Khanh. Prediction of mechanical properties of polychloroprene during thermo-oxidative aging[J].Polymer Testing,2005,24(6):775-780
[136]E V Bystritskaya,A L Pomerantsev,O Ye Rodionova.Evolutionary design of experiment for accelerated aging tests[J].Polymer Testing,2000,19(2):221-229
[137]MM.Badawy.Effect of HAF-carbon black on the elastic behavior of butyl rubber vulcanizates[J].Polymer Testing,2000,19(3):341-348
[138]赵泉林,李晓刚,高瑾.三元乙丙橡胶的人工气候老化[J].北京科技大学学报,2008,30(12)：1422-1427
[139]Milena Ginic-Markovic,Namita Roy Choudhury,Maria Dimopoulos,et al..Weatherability of coated EPDM rubber compound by controlled UV irradiation[J].Polymer Degradation and Stability,2000,69(2):157-168
[140]Zhao Quanlin,Li Xiaogang,Gao Jin.Aging behavior and mechanism of ethylene-propylene-diene monomer (EPDM) rubber in fluorescent UV/condensation weathering environment[J].Polymer Degradation and Stability,2009,94(3):339-343
[141]刘宏敏,杨其,冯彦龙,等.炭黑对丁苯橡胶耐热氧和紫外老化性能的影响[J].合成橡胶工业,2009,32(1)：53-57
[142]Anil K Bhowmick, J Heslop, J R White.Effect of stabilizers in photodegradation of thermoplastic elastomeric rubber-polyethylene blends-a preliminary study[J].Polymer Degradation and Stability,2001,74(3):513-521
[143]R P Singh, R Chandra.Ageing of butyl rubber against UV irradiation[J].Polymer Photochemistry,1982,2(4):257-267
[144]Mingwei Di,Shiyu He,Ruiqi Li,et al.. Radiation effect of 150 keV protons on methyl silicone rubber reinforced with MQ silicone resin[J].Nuclear Instruments and Methods in Physics Research Section B:Beam Interactions with Materials and Atoms,2006,248(1):31-36
[145]张凯,黄渝鸿,马艳,等.丁基橡胶密封材料贮存寿命的预测[J].四川化工,2004,7(1)：4-6