高交联密度硅橡胶的制备与性能研究
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摘要
通过液面悬浮法和阶梯升温法,采用四甲基四乙烯基环四硅氧烷和四甲基四氢环四硅氧烷在铂催化剂作用下发生硅氢加成反应制得高交联密度硬质硅橡胶。利用差示扫描量热仪、傅里叶红外光谱仪、原子力显微镜、邵氏硬度计和热重分析仪对高交联密度硅橡胶的固化过程、表面形貌、硬度和热稳定性进行分析,并利用平衡溶胀法计算其交联密度。结果表明:阶梯升温法能有效控制交联反应;高交联密度硅橡胶具有极低的粗糙度,均方根粗糙度Rq为1. 74 nm,平均粗糙度Ra为1. 39 nm,邵尔D型硬度为78度,交联密度为2. 87×10~(-3)mol·cm~(-3);当高交联密度硅橡胶的质量损失率为5%时,对应温度为602. 1℃,其最终残余质量占分解前质量的83. 57%。
The highly crosslinked and hard silicone rubber was obtained by hydrosilylation reaction of tetramethyltetravinylcyclotetrasiloxane and tetramethyltetrahydrocyclotetrasiloxane under the action of platinum catalyst by liquid suspension method and multi-step heating method. The curing process,surface morphology,hardness and thermal stability of the highly crosslinked silicone rubber were analyzed by differential scanning calorimeter,Fourier infrared spectrometer,atomic force microscope,Shore hardness tester and thermogravimetric analyzer,and the crosslink density was calculated by equilibrium swelling method. The results showed that,multi-step heating method could effectively control the crosslinking reaction. The surface of the highly crosslinked silicone rubber had a very low roughness,the root mean square roughness Rq was 1. 74 nm,and the average roughness Ra was 1. 39 nm. The Shore D hardness reached 78,and the crosslinking density was 2. 87×10~(-3) mol·cm~(-3). The TG testing results showed that the temperature was 602. 1 ℃ when the mass loss rate of highly crosslinked silicone rubber reached 5%,and the final residual mass accounted for 83. 57% of the mass before decomposition.
The highly crosslinked and hard silicone rubber was obtained by hydrosilylation reaction of tetramethyltetravinylcyclotetrasiloxane and tetramethyltetrahydrocyclotetrasiloxane under the action of platinum catalyst by liquid suspension method and multi-step heating method. The curing process,surface morphology,hardness and thermal stability of the highly crosslinked silicone rubber were analyzed by differential scanning calorimeter,Fourier infrared spectrometer,atomic force microscope,Shore hardness tester and thermogravimetric analyzer,and the crosslink density was calculated by equilibrium swelling method. The results showed that,multi-step heating method could effectively control the crosslinking reaction. The surface of the highly crosslinked silicone rubber had a very low roughness,the root mean square roughness Rq was 1. 74 nm,and the average roughness Ra was 1. 39 nm. The Shore D hardness reached 78,and the crosslinking density was 2. 87×10~(-3) mol·cm~(-3). The TG testing results showed that the temperature was 602. 1 ℃ when the mass loss rate of highly crosslinked silicone rubber reached 5%,and the final residual mass accounted for 83. 57% of the mass before decomposition.
引文
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[3]MichalczykMJ,FarnethWE,VegaVJ. High–temperature StabilizationofCross–linkedSiloxanesGlasses[J]. Chemicalof Materials,1993,5(12):1687-1689.
[4]Vieyres A,Albouy P A,Sanseau O. Sulfur–cured Natural Rubber ElastomerNetworks:CorrelatingCross-linkDensity,Chain Orientation,and Mechanical Response by Combined Techniques[J].Macromolecules,2013,46(3):889-899.
[5]Flory P J,Paul J,Rehner J. Effect of Deformation on the Swelling Capacity of Rubber[J]. Journal of Chemical Physics,1944,12(10):412-414.
[6]HongIK,LeeS. CureKineticsandModelingtheReactionof Silicone Rubber[J]. Journal of Industrial and Engineering Chemistry,2013,19(1):42-47.
[7]Shi Y H,Huang G S,Liu Y F,et al. Synthesis and Thermal Properties of Novel Room Temperature Vulcanized(RTV)Silicone Rubber ContainingPOSSUnitsinPolysioxaneMainChains[J]. Journalof Polymer Research,2013,20(9):1-11.
[8]Fang W Z,Zeng X R,Lai X J,et al. Thermal Degradation Mechanism of Addition–cureLiquidSiliconeRubberwithUrea–containing Silane[J]. Thermochimica Acta,2015,605:28-36.
[9]Xu Q,Pang M L,Zhu L X,et al. Mechanical Properties of Silicone RubberComposedofDiverseVinylContentSiliconeGums Blending[J]. Materials and Design,2010,31(9):4083-4087.
[10]Yin YL,ChenX T,LuJ,etal. InfluencesofBranched Vinyl Silicone Oil on Highly Ultraviolet Transparent Silicone Rubber[J].Journal of Rubber Research,2014,17(23):161-169.
[11]Clarizio S C,Tatara R A. Tensile Strength,Elongation,Hardness, and TensileandFlexuralModuliofPLAFilledwithGlycerol–plasticized DDGS[J]. Journal of Polymers and the Environment,2012,30(3):638-646.
[12]BaenaL,JaramilloF,CalderonJ A. Aggressivenessofa20%Bioethanol80%GasolineMixtureon Autoparts:Behaviorof Polymeric Materials[J]. Fuel,2012,95:312-319.
[13]Luyt AS,MessoriM,FabbriP. PolycarbonateReinforcedwith Silica Nanoparticles[J]. Polymer Bulletin,2011,66(7):991-1004.