Synthesis and modification of high-temperature hydrogen-containing vinyl silicone resins

Abstract

Abstract: Silicone resin is a kind of high temperature resistant material with excellent properties, and has broad application prospects in the field of heat resistance With the high-speed silicone resin thermal protection coating in national defense industry, it is difficult to meet the current needs Therefore, it is of great strategic value to improve the high temperature resistance of silicone resin. Thermally stable vinyl silicone resin containing hydrogen was successfully prepared from alkoxysilane containing silicon-hydrogen bond and silicon-ethylene bond by a simple two-step method under acidic conditions The synthesis conditions of modified silicone resin were studied by infrared spectroscopy TG, its chemical structure and thermal stability TG-IR, and its thermal decomposition mechanism The results showed that the synthesis conditions were as follows: triethoxysilane and vinyl triethoxysilane as monomer, ethanol and hydrochloric acid as organic solvent, pH 1, hydrolysis temperature 30 ℃ and hydrolysis time 3 h The remaining 97.84% of silicone resin at 800 ℃ was synthesized under the optimum conditions, and its high temperature resistance was far higher than that of ordinary silicone resin Hydrogen-containing vinyl silicone resin mainly includes two thermal decomposition stages: the first stage occurs at about 253 ℃, which is mainly the oxidative degradation of partial vinyl of side-linked branches of silicone resin; The second stage appeared at 578 ℃, which was mainly caused by the random fracture and rearrangement of SR skeleton caused by the back bite of silicone hydroxyl groups at the end of silicone resin.

References

[1]Kuo C J, Chen J. Study on the synthesis and application of silicone resin containing phenyl group[J]. Journal of Sol-Gel Science and Technology, 2015, 76(1): 66-73.
[2]Lin Y, Li Y, Lei I, et al. Enhanced reliability of LEDs encapsulated with surface-modified zirconia/silicone hybrids under thermal shock[J]. Materials Chemistry and Physics, 2018, 206: 136-143.
[3]Lei H, He D, Guo Y, et al. Synthesis and characterization of UV-absorbing fluorine-silicone acrylic resin polymer[J]. Applied surface science, 2018, 442: 71-77.
[4]Fang W, Zeng X, Lai X, et al. Investigation of the tracking and erosion resistance of cured liquid silicone rubber containing ureido-modified MQ silicone resin[J]. IEEE Transactions on Dielectrics and Electrical Insulation, 2016, 23(6): 3668-3675.
[5]Hidayah N, Mustapha M, Ismail H, et al. Linear low-density polyethylene/silicone rubber nanocomposites[J]. Journal of Elastomers & Plastics, 2018, 50(1): 36-57.
[6]Nair S, Aswathy U V, Mathew A, et al. Studies on the thermal properties of silicone polymer based thermal protection systems for space applications[J]. Journal of Thermal Analysis and Calorimetry, 2017, 128(3): 1731-1741.
[7]Liu Y, Chen Z, Qin Y, et al. Silicone Resin-Based Composite Materials for High Thermal Stability and Thermal Conductivity[J]. Journal of Electronic Materials, 2020, 49(7): 4379-4384.
[8]Wu C, Huang M, Luo D, et al. SiO2 nanoparticles enhanced silicone resin as the matrix for Fe soft magnetic composites with improved magnetic, mechanical and thermal properties[J]. Journal of Alloys and Compounds, 2018, 741: 35-43.
[9]沙艳松，张长生，罗世凯. 硅橡胶耐热性能的研究进展[J]. 有机硅材料，2012,26(2)：122-126.
[10]Chen J, Fu Z, Huang H, et al. A facile route to prepare homogeneous silicone resin doped with titanium[J]. Journal of Applied Polymer Science, 2019, 136(32): 47834.
[11]Babonneau F, Maquet J. Nuclear magnetic resonance techniques for the structural characterization of siloxane–oxide hybrid materials[J]. Polyhedron, 2000, 19(3): 315-322.
[12]翟倩倩，严岑琪，赵士贵等. 含钛杂化硅树脂的制备与耐热性能研究[J]. 功能材料，2014(21)：21025-21030，21034.
[13]Huang Y, Feng Y, Sun X, et al. Preparation of ZrO2/silicone hybrid materials for LED encapsulation via in situ sol‐gel reaction[J]. Polymers for Advanced Technologies, 2019, 30(7): 1818-1824.
[14]Guo T, Lin X, Hu X, et al. Direct synthesis of zirconium containing phenyl silicone resin for LED encapsulation[J]. International journal of polymer analysis & characterization, 2018, 23(2): 120-127.
[15]Yang L, Cao K, Huang Y, et al. Synthesis and properties of cross-linkable polysiloxane via incorporating benzocyclobutene[J]. High Performance Polymers, 2014, 26(4): 463-469.
[16]Chen X, Zhou S, You B, et al. Mechanical properties and thermal stability of ambient-cured thick polysiloxane coatings prepared by a sol–gel process of organoalkoxysilanes[J]. Progress in Organic Coatings, 2012, 74(3): 540-548.
[17]Kuo C J, Chen J. Study on the synthesis and application of silicone resin containing phenyl group[J]. Journal of Sol-Gel Science and Technology, 2015, 76(1): 66-73.
[18]Kuo C J, Chen J. Study on the synthesis and application of silicone resin containing phenyl group[J]. Journal of Sol-Gel Science and Technology, 2015, 76(1): 66-73.
[19]Tong L, Feng Y, Sun X, et al. High refractive index adamantane-based silicone resins for the encapsulation of light-emitting diodes[J]. Polymers for Advanced Technologies, 2018, 29(8): 2245-2252.
[20]Huang R, Yao J, Mu Q, et al. Study on the Synthesis and Thermal Stability of Silicone Resin Containing Trifluorovinyl Ether Groups[J]. Polymers, 2020, 12(10): 2284.
[21]Li Q, Zhong J, Li Y, et al. Study on a C-class solvent-free silicone impregnating varnish[J]. IEEE transactions on dielectrics and electrical insulation, 2010, 17(3): 785-790.
[22]Wang G, Liu X, Mi C, et al. High-temperature structural evolution and hydrolytic stability of poly(phenylborosiloxane)[J]. Pigment & Resin Technology, 2018, 47(4): 308-314.
[23]Robeyns C, Picard L, Ganachaud F. Synthesis, characterization and modification of silicone resins: An “Augmented Review”[J]. Progress in Organic Coatings, 2018, 125: 287-315.