加成型液体氟硅橡胶等温固化的分析与模拟
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摘要
通过旋转流变仪对环状含氢氟硅油(D_F~H)和四甲基四乙烯基环四硅氧烷(D_4~(Vi))发生硅氢加成反应得到的加成型液体氟硅橡胶的固化过程流变学进行了研究。研究了不同等温固化温度对该体系固化反应过程的影响,并得到了体系固化反应的凝胶点为α=0.63。讨论了体系的固化反应模型,确定了Kamal自催化模型适用于体系的固化反应,得到了相关的模型参数及Kamal自催化模型方程。Kamal自催化模型方程对加成型液体氟硅橡胶的固化过程有重要的指导意义。
In this paper, the rheology of curing process for the additive liquid fluorosilicone rubber, which was synthesized by the hydrosilylation reaction of cyclic hydrofluorosiliconoil(D_F~H) and 1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane(D_4~(Vi)) was studied. The effects of different isothermal curing temperatures on the curing process of the system were investigated, the gel point(α=0.63) of the curing reaction was obtained. The curing reaction model of the system was discussed, and the Kamal autocatalytic model applied to the curing reaction of the system was determined. The related model parameters and the Kamal autocatalytic model equation were acquired. The Kamal autocatalytic model equation is of great guiding significance for the curing process of the additive liquid fluorosilicone rubber.
In this paper, the rheology of curing process for the additive liquid fluorosilicone rubber, which was synthesized by the hydrosilylation reaction of cyclic hydrofluorosiliconoil(D_F~H) and 1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane(D_4~(Vi)) was studied. The effects of different isothermal curing temperatures on the curing process of the system were investigated, the gel point(α=0.63) of the curing reaction was obtained. The curing reaction model of the system was discussed, and the Kamal autocatalytic model applied to the curing reaction of the system was determined. The related model parameters and the Kamal autocatalytic model equation were acquired. The Kamal autocatalytic model equation is of great guiding significance for the curing process of the additive liquid fluorosilicone rubber.
引文
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[8] Boey F Y C, Song X L, Yue C Y, et al. Modeling the curing kinetics for a modified bismaleimide resin[J]. J. Polym. Sci. Part A: Polym. Chem., 2015, 38: 907-913.
[9] Fan M, Li X, Zhang J, et al. Curing kinetics and shape-memory behavior of an intrinsically toughened epoxy resin system[J]. J. Therm. Anal. Calorim., 2015, 119: 1-10.
[10] Martin J S, Laza J M, Morrás M L, et al. Study of the curing process of a vinyl ester resin by means of TSR and DMTA[J]. Polymer, 2000, 41: 4203-4211.
[11] 代晓青, 肖加余, 曾竟成,等. 等温DSC法研究RFI用环氧树脂固化动力学[J]. 复合材料学报, 2008, 25(4): 18-23.Dai X Q, Xiao J Y, Zeng J C, et al. Curing kinetics of epoxy resin for RFI process using isothermal DSC[J]. Acta Materiae Compositae Sinica, 2008, 25(4): 18-32.
[12] Lei Z, Xiao H. A variable reaction order model for prediction of curing kinetics of thermosetting polymers[J]. Polymer, 2007, 48: 6125-6133.
[13] Stauffer D. Gelation in concentrated critically branched polymer solutions. Percolation scaling theory of intramolecular bond cycles[J]. J. Chem. Soc. Faraday Trans., 1976, 72: 1354-1364.
[14] Atarsia A, Boukhili R. Relationship between isothermal and dynamic cure of thermosets via the isoconversion representation[J]. Polym. Eng. Sci., 2000, 40: 607-620.
[15] Kamal M R. Thermoset characterization for moldability analysis[J]. Polym. Eng. Sci., 2010, 14: 231-239.
[16] Xu X, Zhou Q, Song N, et al. Kinetic analysis of isothermal curing of unsaturated polyester resin catalyzed with tert-butyl peroxybenzoate and cobalt octoate by differential scanning calorimetry[J]. J. Therm. Anal. Calorim., 2017, 129: 843-850.
[2] 吕志勇, 李静, 孙筱萌,等. MQ树脂增强硅橡胶及其透紫外影响因素分析[J]. 高分子材料科学与工程, 2016, 32(2): 90-94. Lü Z Y, Li J, Sun X M, et al. MQ resin reinforced silicone rubber and analysis of influencing factors of ultraviolet-transparent[J]. Polymer Materials Science & Engineering, 2016, 32(2): 90-94.
[3] Shi Y, Huang G, Liu Y, et al. Synthesis and thermal properties of novel room temperature vulcanized (RTV) silicone rubber containing POSS units in polysioxane main chains[J]. J. Polym. Res., 2013, 20: 245.
[4] Owen M J. Why silicones behave funny[J]. Chemtech, 2005, 11:288-292.
[5] Dhara M G, Banerjee S. Fluorinated high-performance polymers: poly(arylene ether)s and aromatic polyimides containing trifluoromethyl groups[J]. Prog. Polym. Sci., 2010, 35: 1022-1077.
[6] Yin Y, Chen X, Lu J, et al. Influence of molar ratio of Si-H to Si-CH=CH2 on mechanical and optical properties of silicone rubber[J]. J. Elastomers Plast., 2016, 48: 1-11.
[7] Flitney B. Extending the application of fluorosilicone elastomers[J]. Seal. Technol., 2005, 2005: 6-11.
[8] Boey F Y C, Song X L, Yue C Y, et al. Modeling the curing kinetics for a modified bismaleimide resin[J]. J. Polym. Sci. Part A: Polym. Chem., 2015, 38: 907-913.
[9] Fan M, Li X, Zhang J, et al. Curing kinetics and shape-memory behavior of an intrinsically toughened epoxy resin system[J]. J. Therm. Anal. Calorim., 2015, 119: 1-10.
[10] Martin J S, Laza J M, Morrás M L, et al. Study of the curing process of a vinyl ester resin by means of TSR and DMTA[J]. Polymer, 2000, 41: 4203-4211.
[11] 代晓青, 肖加余, 曾竟成,等. 等温DSC法研究RFI用环氧树脂固化动力学[J]. 复合材料学报, 2008, 25(4): 18-23.Dai X Q, Xiao J Y, Zeng J C, et al. Curing kinetics of epoxy resin for RFI process using isothermal DSC[J]. Acta Materiae Compositae Sinica, 2008, 25(4): 18-32.
[12] Lei Z, Xiao H. A variable reaction order model for prediction of curing kinetics of thermosetting polymers[J]. Polymer, 2007, 48: 6125-6133.
[13] Stauffer D. Gelation in concentrated critically branched polymer solutions. Percolation scaling theory of intramolecular bond cycles[J]. J. Chem. Soc. Faraday Trans., 1976, 72: 1354-1364.
[14] Atarsia A, Boukhili R. Relationship between isothermal and dynamic cure of thermosets via the isoconversion representation[J]. Polym. Eng. Sci., 2000, 40: 607-620.
[15] Kamal M R. Thermoset characterization for moldability analysis[J]. Polym. Eng. Sci., 2010, 14: 231-239.
[16] Xu X, Zhou Q, Song N, et al. Kinetic analysis of isothermal curing of unsaturated polyester resin catalyzed with tert-butyl peroxybenzoate and cobalt octoate by differential scanning calorimetry[J]. J. Therm. Anal. Calorim., 2017, 129: 843-850.