Citation: Yong Guan, Jian Hu, Yong-Kang Huang, Yang You, Huan-Yao Zhang, An-Na Zheng, Xiang Xu, Da-Fu Wei. Synthesis of Cerium-containing Polymethylphenyl Silicone and Its Antioxidant Effect on Fluorosilicone Rubber[J]. Chinese Journal of Polymer Science, ;2019, 37(8): 783-789. doi: 10.1007/s10118-019-2266-4 shu

Synthesis of Cerium-containing Polymethylphenyl Silicone and Its Antioxidant Effect on Fluorosilicone Rubber

Yong Guan ^1,2 ,
Jian Hu ¹ ,
Yong-Kang Huang ¹ ,
Yang You ¹ ,
Huan-Yao Zhang ¹ ,
An-Na Zheng ¹ ,
Xiang Xu ^1,2,, ,
Da-Fu Wei ¹

a.
Key Laboratory for Ultrafine Materials of Ministry of Education, School of Materials Science and Engineering, East China University of Science and Technology, Shanghai 200237, China
b.
Key Laboratory for Specially Functional Polymeric Materials and Related Technology of the Ministry of Education, School of Materials Science and Engineering, East China University of Science and Technology, Shanghai 200237, China

Corresponding author: Xiang Xu, xiangxu@ecust.edu.cn
Received Date: 4 January 2019
Revised Date: 14 March 2019
Available Online: 10 May 2019

As an essential elastomer used in edge technologies, fluorosilicone rubber (FSR) suffers serious oxidative ageing problem when serving at high temperature. Cerium oxide is generally used as an antioxidant additive but remains unsatisfactory. In order to obtain better antioxidant effect on improving the thermal stability of FSR, a kind of cerium-containing polymethylphenyl silicone (PSI-Ce) was synthesized and the structure was verified by Fourier-transform infrared spectroscopy (FTIR) and proton nuclear magnetic resonance (¹H-NMR). Due to the homogeneous dispersion on molecular scale, PSI-Ce imposed much better antioxidant effect than the commercial CeO₂ did, no matter from isothermal degradation at 320 °C or thermal-oxidative ageing test at 230 °C. In particular, after ageing for 72 h, FSR/PSI-Ce (2 phr) maintained 82% of tensile strength and 63% of elongation at break, in comparison to the corresponding values of 48% and 42% for FSR/CeO₂ (2 phr). Moreover, 2 phr PSI-Ce was equivalent to 0.046 phr CeO₂ according to cerium element conservation.
- Polymethylphenyl silicone,
- Cerium,
- Fluorosilicone rubber,
- Thermal stability
1. [1]
  Zhang, X. K.; Poojari, Y.; Drechsler, L. E.; Kuo, C. M.; Fried, J. R.; Clarson, S. J. Pervaporation of organic liquids from binary aqueous mixtures using poly(trifluoropropylmethylsiloxane) and poly(dimethylsiloxane) dense membranes. J. Inorg. Organomet. Polym. Mater. 2007, 18, 246-252.
2. [2]
  Esmizadeh, E.; Naderi, G.; Barmar, M. Effect of organo-clay on properties and mechanical behavior of fluorosilicone rubber. Fibers Polym. 2014, 15, 2376-2385. doi: 10.1007/s12221-014-2376-0
3. [3]
  Cypryk, M.; Delczyk, B.; Juhari, A.; Koynov, K. Controlled synthesis of trifluoropropylmethylsiloxane-dimethylsiloxane gradient copolymers by anionic ROP of cyclotrisiloxanes. J. Polym. Sci., Part A: Polym. Chem. 2009, 47, 1204-1216. doi: 10.1002/pola.v47:4
4. [4]
  Gao, Y.; Jiang, W.; Guan, Y.; Yang, P.; Zheng, A. N. A novel approach for anionic bulk polymerization of 1,3,5-tris(trifluoropropylmethyl)cyclotrisiloxane. Polym. Eng. Sci. 2010, 50, 2440-2447. doi: 10.1002/pen.21690
5. [5]
  Liu, Y.; Liu, H.; Zhang, R.; Zhou, C.; Feng, S. Preparation and properties of heat curable blended methylfluorosilicone rubber. Polym. Eng. Sci. 2013, 53, 52-58. doi: 10.1002/pen.v53.1
6. [6]
  Kahlig, H.; Zollner, P.; Mayer-Helm, B. X. Characterization of degradation products of poly[(3,3,3-trifluoropropyl)methylsiloxane] by nuclear magnetic resonance spectroscopy, mass spectrometry and gas chromatography. Polym. Degrad. Stab. 2009, 94, 1254-1260. doi: 10.1016/j.polymdegradstab.2009.04.019
7. [7]
  Xu, X.; Xu, Z.; Chen, P.; Zhou, X.; Zheng, A. N; Guan, Y. Preparation of fluorosilicone random copolymers with properties superior to those of fluorosilicone/silicone polymer blends. J. Inorg. Organomet. Polym. Mater. 2015, 25, 1267-1276. doi: 10.1007/s10904-015-0236-z
8. [8]
  Dai, Y.; Ruan, X.; Bai, F.; Yu, M.; Li, H.; Zhao, Z.; He, G. High solvent resistance PTFPMS/PEI hollow fiber composite membrane for gas separation. Appl. Surf. Sci. 2016, 360, 164-173. doi: 10.1016/j.apsusc.2015.11.014
9. [9]
  Bhuvaneswari, C. M.; Dhanasekaran, R.; Chakravarthy, S. K. R.; Kale, S. S.; Gouda, G. Evaluation of fluorosicone-silicone elastomer blend for aeronautical fuel system. Prog. Rubber Plast. Recycl. Technol. 2015, 31, 207-218. doi: 10.1177/147776061503100305
10. [10]
  Smitha Alex, A.; Rajeev, R. S.; Krishnaraj, K.; Sreenivas, N.; Manu, S. K.; Gouri, C.; Sekkar, V. Thermal protection characteristics of polydimethylsiloxane-organoclay nanocomposite. Polym. Degrad. Stab. 2017, 144, 281-291. doi: 10.1016/j.polymdegradstab.2017.08.026
11. [11]
  Camino, G.; Lomakin, S. M.; Lazzari, M. Polydimethylsiloxane thermal degradation Part 1. Kinetic aspects. Polymer 2001, 42, 2395-2402. doi: 10.1016/S0032-3861(00)00652-2
12. [12]
  Camino, G.; Lomakin, S. M.; Lagerad, M. Thermal polydimethylsiloxane degradation part 2. The degradation mechanisms. Polymer 2002, 43, 2011-2015. doi: 10.1016/S0032-3861(01)00785-6
13. [13]
  Patel, M.; Skinner, A. R. Thermal ageing studies on room-temperture vulcanised polysiloxane rubbers. Polym. Degrad. Stab. 2001, 73, 399-402. doi: 10.1016/S0141-3910(01)00118-5
14. [14]
  Jovanovic, J. D.; Govedarica, M. N.; Dvornic, P. R.; Popovic, I. G. The thermogravimetric analysis of some polysiloxanes. Polym. Degrad. Stab. 1998, 61, 87-93. doi: 10.1016/S0141-3910(97)00135-3
15. [15]
  Zhang, S.; Wang, H. Thermal degradation of amino-group-modified polydimethylsiloxane. J. Therm. Anal. Calorim. 2010, 103, 711-716.
16. [16]
  Lewicki, J. P.; Liggat, J. J.; Patel, M. The thermal degradation behaviour of polydimethylsiloxane/montmorillonite nanocomposites. Polym. Degrad. Stab. 2009, 94, 1548-1557. doi: 10.1016/j.polymdegradstab.2009.04.030
17. [17]
  Liu, Y. R.; Huang, Y. D.; Liu, L. Thermal stability of POSS/methylsilicone nanocomposites. Compos. Sci. Technol. 2007, 67, 2864-2876. doi: 10.1016/j.compscitech.2007.01.023
18. [18]
  Zheng, A. N.; Huang, Y.; You, Y.; Hu, J.; Wei, D.; Xu, X.; Guan, Y. Boron particles acting as antioxidants for fluorosilicone rubber due to their radical scavenging activity. Polym. Degrad. Stab. 2018, 158, 168-175. doi: 10.1016/j.polymdegradstab.2018.09.017
19. [19]
  Guan, Y.; Yang, R.; Huang, Y.; Yu, C.; Li, X.; Wei, D.; Xu, X. Multi-walled carbon nanotubes acting as antioxidant for fluorosilicone rubber. Polym. Degrad. Stab. 2018, 156, 161-169. doi: 10.1016/j.polymdegradstab.2018.06.018
20. [20]
  Xu, X.; Liu, J.; Chen, P.; Wei, D.; Guan, Y.; Lu, X.; Xiao, H. The effect of ceria nanoparticles on improving heat resistant properties of fluorosilicone rubber. J. Appl. Polym. Sci. 2016, 133, 44117.
21. [21]
  Paul, D. R.; Mark, J. E. Fillers for polysiloxane (" silicone”) elastomers. Prog. Polym. Sci. 2010, 35, 893-901. doi: 10.1016/j.progpolymsci.2010.03.004
22. [22]
  Li, H.; Tao, S.; Huang, Y.; Su, Z.; Zheng, J. The improved thermal oxidative stability of silicone rubber by using iron oxide and carbon nanotubes as thermal resistant additives. Compos. Sci. Technol. 2013, 76, 52-60. doi: 10.1016/j.compscitech.2012.12.019
23. [23]
  Zhang, X.; Zhang, Q.; Zheng, J. Effect and mechanism of iron oxide modified carbon nanotubes on thermal oxidative stability of silicone rubber. Compos. Sci. Technol. 2014, 99, 1-7. doi: 10.1016/j.compscitech.2014.05.003
24. [24]
  Shentu, B. Q.; Gan, T. F.; Weng, Z. X. Modification of Fe2O3 and its effect on the heat-resistance of silicone rubber. J. Appl. Polym. Sci. 2009, 113, 3202-3206. doi: 10.1002/app.v113:5
25. [25]
  Gan, T. F.; Shentu, B. Q.; Weng, Z. X. Modification of CeO₂ and its effect on the heat-resistance of silicone rubber. Chinese J. Polym. Sci. 2008, 26, 489-494. doi: 10.1142/S0256767908003163
26. [26]
  Botter, W.; Ferreira Soares, R.; Galembeck, F. Interfacial reactions and self-adhesion of polydimethylsiloxanes. J. Adhes. Sci. Technol. 1992, 6, 791-805. doi: 10.1163/156856192X00449
27. [27]
  Sim, L. C.; Ramanan, S. R.; Ismail, H.; Seetharamu, K. N.; Goh, T. J. Thermal characterization of Al2O3 and ZnO reinforced silicone rubber as thermal pads for heat dissipation purposes. Thermochim. Acta. 2005, 430, 155-165. doi: 10.1016/j.tca.2004.12.024
28. [28]
  Yao, Y. Y.; Lu, G. Q.; Boroyevich, D. S.; Ngo, K. D. T. Effect of Al₂O₃ fibers on the high-temperature stability of silicone elastomer. Polymer 2014, 55, 4232-4240. doi: 10.1016/j.polymer.2014.05.044
29. [29]
  Nielsen, J. M. Oxidative stabilization of dimethyl silicone fluids with iron between 70 and 370 °C. J. Polym. Sci., Polym. Symp. 1973, 40, 189-197.
30. [30]
  Baker, H. R.; Singleterry, C. R. Stabilization of silicone lubricating fluids above 200 °C by iron, copper, cerium, and other metal compounds. J. Chem. Eng. Data 1961, 6, 146-154. doi: 10.1021/je60009a030
31. [31]
  Han, W. Q.; Wu, L. J.; Zhu, Y. M. Formation and oxidation state of CeO₂-x nanotubes. J. Am. Chem. Soc. 2005, 127, 12814-12815. doi: 10.1021/ja054533p
32. [32]
  Belyavskii, S. G.; Mingalyov, P. G.; Giulieri, F.; Combarrieau, R.; Lisichkin, G. V. Chemical modification of the surface of a carbonyl iron powder. Prot. Met. 2006, 42, 244-252. doi: 10.1134/S0033173206030064
33. [33]
  Ikaev, A. M.; Mingalyov, P. G.; Lisichkin, G. V. Chemical modification of iron oxide surface with organosilicon and organophosphorous compounds. Colloid J. 2007, 69, 741-746. doi: 10.1134/S1061933X07060105
34. [34]
  Pu, H. T.; Jiang, F. J.; Yang, Z. L. Studies on preparation and chemical stability of reduced iron particles encapsulated with polysiloxane nano-films. Mater. Lett. 2006, 60, 94-97. doi: 10.1016/j.matlet.2005.07.079
35. [35]
  Huang, R. H.; Wang, L.; Lin, Y.; Dong, Y.; You, D. Surface modification of carbonyl iron powders with silicone polymers in supercritical fluid to get higher dispersibility and higher thermal stability. Surf. Interface Anal. 2017, 49, 79-84. doi: 10.1002/sia.v49.2
36. [36]
  Li, Y. M.; Zheng, Z. M.; Xu, C. L.; Ren, C.; Zhang, Z.; Xie, Z. Synthesis of iron-containing polysilazane and its antioxidation effect on silicone oil and rubber. J. Appl. Polym. Sci. 2003, 90, 306-309. doi: 10.1002/(ISSN)1097-4628
37. [37]
  Cai, D.; Neyer, A.; Kuckuk, R.; Heise, H. M. Raman, mid-infrared, near-infrared and ultraviolet-visible spectroscopy of PDMS silicone rubber for characterization of polymer optical waveguide materials. J. Mol. Struct. 2010, 976, 274-281. doi: 10.1016/j.molstruc.2010.03.054
38. [38]
  Colthup, N. B.; Daly, L. H.; Wiberley, S. E. Introduction to infrared and Raman spectroscopy. Academic Press, San Diego, 1990, p. 355.
39. [39]
  Sopicka-Lizer, M.; Michalik, D.; Plewa, J.; Juestel, T.; Winkler, H.; Pawlik, T. The effect of Al―O substitution for Si―N on the luminescence properties of YAG:Ce phosphor. J. Eur. Ceram. Soc. 2012, 32, 1383-1387. doi: 10.1016/j.jeurceramsoc.2011.04.021
40. [40]
  Selvaraj, M.; Kim, B. H.; Lee, T. G. FTIR studies on selected mesoporous metallosilicate molecular sieves. Chem. Lett. 2005, 34, 1290-1291. doi: 10.1246/cl.2005.1290
41. [41]
  Lin, S. L.; Hwang, C. S.; Lee, J. F. Characterization of CeO₂-Al₂O₃-SiO₂ glasses by infrared and X-ray absorption near edge structure spectroscopies. J. Mater. Res. 1996, 11, 2641-2650. doi: 10.1557/JMR.1996.0332
42. [42]
  Park, S. H.; Kim, B. H.; Selvaraj, M.; Lee, T. G. Synthesis and characterization of mesoporous Ce-Mn-MCM-41 molecular sieves. J. Ind. Eng. Chem. 2007, 13(4), 637-643.
43. [43]
  Laha, S. C.; Mukherjee, P.; Sainkar, S. R.; Kumar, R. Cerium containing MCM-41-Type mesoporous materials and their acidic and redox catalytic properties. J. Catal. 2002, 207, 213-223. doi: 10.1006/jcat.2002.3516
44. [44]
  Radhakrishnan T S. New method for evaluation of kinetic parameters and mechanism of degradation from pyrolysis-GC studies: Thermal degradation of polydimethylsiloxanes. J. Appl. Polym. Sci. 1999, 73: 441-450. doi: 10.1002/(ISSN)1097-4628
45. [45]
  Korsvik, C.; Patil, S.; Seal, S.; Self, W. T. Superoxide dismutase mimetic properties exhibited by vacancy engineered ceria nanoparticles. Chem. Commun. 2007, 1056-1058.
46. [46]
  Tarnuzzer, R. W.; Colon J.; Patil S.; Seal S. Vacancy engineered ceria nanostructures for protection from nanostructures for protection from radiation-induced cellular damage. Nano Lett. 2005, 5, 2573. doi: 10.1021/nl052024f
47. [47]
  Xue, Y.; Luan, Q. F.; Yang, D.; Yao, X.; Zhou, K. B. Direct evidence for hydroxyl radical scavenging activity of cerium oxide nanoparticles. J. Phys. Chem. C 2011, 115, 4433-4438. doi: 10.1021/jp109819u
1. [1]
  Guizhi Zhu , Junrui Tan , Longfei Tan , Qiong Wu , Xiangling Ren , Changhui Fu , Zhihui Chen , Xianwei Meng . Growth of CeCo-MOF in dendritic mesoporous organosilica as highly efficient antioxidant for enhanced thermal stability of silicone rubber. Chinese Chemical Letters, 2025, 36(1): 109669-. doi: 10.1016/j.cclet.2024.109669
2. [2]
  Shunshun Jiang , Ji Zhang , Jing Wang , Shan-Tao Zhang . Excellent energy storage properties in non-stoichiometric Bi_0.5Na_0.5TiO₃-based relaxor ferroelectric ceramics. Chinese Chemical Letters, 2024, 35(7): 108955-. doi: 10.1016/j.cclet.2023.108955
3. [3]
  Bo Yang , Pu-An Lin , Tingwei Zhou , Xiaojia Zheng , Bing Cai , Wen-Hua Zhang . Facile surface regulation for highly efficient and thermally stable perovskite solar cells via chlormequat chloride. Chinese Chemical Letters, 2024, 35(10): 109425-. doi: 10.1016/j.cclet.2023.109425
4. [4]
  Yuchen Zhou , Huanmin Liu , Hongxing Li , Xinyu Song , Yonghua Tang , Peng Zhou . 设计热力学稳定的贵金属单原子光催化剂用于乙醇的高效非氧化转化形成高纯氢和增值产物乙醛. Acta Physico-Chimica Sinica, 2025, 41(6): 100067-. doi: 10.1016/j.actphy.2025.100067
5. [5]
  Xiangyu Chen , Aihao Xu , Dong Wei , Fang Huang , Junjie Ma , Huibing He , Jing Xu . Atomic cerium-doped CuO_x catalysts for efficient electrocatalytic CO₂ reduction to CH₄. Chinese Chemical Letters, 2025, 36(1): 110175-. doi: 10.1016/j.cclet.2024.110175
6. [6]
  Sixiao Liu , Tianyi Wang , Lei Zhang , Chengyin Wang , Huan Pang . Cerium-based metal-organic framework-modified natural mineral vermiculite for photocatalytic nitrogen fixation under visible-light irradiation. Chinese Chemical Letters, 2025, 36(3): 110058-. doi: 10.1016/j.cclet.2024.110058
7. [7]
  Juan Guo , Mingyuan Fang , Qingsong Liu , Xiao Ren , Yongqiang Qiao , Mingju Chao , Erjun Liang , Qilong Gao . Zero thermal expansion in Cs₂W₃O₁₀. Chinese Chemical Letters, 2024, 35(7): 108957-. doi: 10.1016/j.cclet.2023.108957
8. [8]
  Xinzhi Ding , Chong Liu , Jing Niu , Nan Chen , Shutao Xu , Yingxu Wei , Zhongmin Liu . Solid-state NMR study of the stability of MOR framework aluminum. Chinese Journal of Structural Chemistry, 2024, 43(4): 100247-100247. doi: 10.1016/j.cjsc.2024.100247
9. [9]
  Jingyuan Yang , Xinyu Tian , Liuzhong Yuan , Yu Liu , Yue Wang , Chuandong Dou . Enhancing stability of diradical polycyclic hydrocarbons via P=O-attaching. Chinese Chemical Letters, 2024, 35(8): 109745-. doi: 10.1016/j.cclet.2024.109745
10. [10]
  Ting Wang , Xin Yu , Yaqiang Xie . Unlocking stability: Preserving activity of biomimetic catalysts with covalent organic framework cladding. Chinese Chemical Letters, 2024, 35(6): 109320-. doi: 10.1016/j.cclet.2023.109320
11. [11]
  Tao LIU , Yuting TIAN , Ke GAO , Xuwei HAN , Ru'nan MIN , Wenjing ZHAO , Xueyi SUN , Caixia YIN . A photothermal agent with high photothermal conversion efficiency and high stability for tumor therapy. Chinese Journal of Inorganic Chemistry, 2024, 40(8): 1622-1632. doi: 10.11862/CJIC.20240107
12. [12]
  Zhengzhong Zhu , Shaojun Hu , Zhi Liu , Lipeng Zhou , Chongbin Tian , Qingfu Sun . A cationic radical lanthanide organic tetrahedron with remarkable coordination enhanced radical stability. Chinese Chemical Letters, 2025, 36(2): 109641-. doi: 10.1016/j.cclet.2024.109641
13. [13]
  Ruizhi Yang , Xia Li , Weiping Guo , Zixuan Chen , Hongwei Ming , Zhong-Zhen Luo , Zhigang Zou . New thermoelectric semiconductors Pb5Sb12+xBi6-xSe32 with ultralow thermal conductivity. Chinese Journal of Structural Chemistry, 2024, 43(3): 100268-100268. doi: 10.1016/j.cjsc.2024.100268
14. [14]
  Chaozheng He , Pei Shi , Donglin Pang , Zhanying Zhang , Long Lin , Yingchun Ding . First-principles study of the relationship between the formation of single atom catalysts and lattice thermal conductivity. Chinese Chemical Letters, 2024, 35(6): 109116-. doi: 10.1016/j.cclet.2023.109116
15. [15]
  Zhiqing Ge , Zuxiong Pan , Shuo Yan , Baoying Zhang , Xiangyu Shen , Mozhen Wang , Xuewu Ge . Novel high-temperature thermochromic polydiacetylene material and its application as thermal indicator. Chinese Chemical Letters, 2024, 35(11): 109850-. doi: 10.1016/j.cclet.2024.109850
16. [16]
  Shuai Liang , Wen-Jing Jiang , Ji-Xiang Hu . Achieving colossal anisotropic thermal expansion via synergism of spin crossover and rhombus deformation. Chinese Journal of Structural Chemistry, 2025, 44(2): 100430-100430. doi: 10.1016/j.cjsc.2024.100430
17. [17]
  Yi Herng Chan , Zhe Phak Chan , Serene Sow Mun Lock , Chung Loong Yiin , Shin Ying Foong , Mee Kee Wong , Muhammad Anwar Ishak , Ven Chian Quek , Shengbo Ge , Su Shiung Lam . Thermal pyrolysis conversion of methane to hydrogen (H₂): A review on process parameters, reaction kinetics and techno-economic analysis. Chinese Chemical Letters, 2024, 35(8): 109329-. doi: 10.1016/j.cclet.2023.109329
18. [18]
  Rongliang Deng , Yihang Chen , Xiaotong Fan , Guolong Chen , Shuli Wang , Changzhi Yu , Xiao Yang , Tingzhu Wu , Zhong Chen , Yue Lin . Break of thermal equilibrium between optical and acoustic phonon branches of CsPbI₃ under continuous-wave light excitation and cryogenic temperature. Chinese Chemical Letters, 2024, 35(7): 109346-. doi: 10.1016/j.cclet.2023.109346
19. [19]
  Ziyi Liu , Feifei Guo , Tingting Cao , Youxuan Sun , Xutang Tao , Zeliang Gao . High thermal conductivity in Ga2TeO6 crystals: Synergistic effects of rigid polyhedral frameworks and stereochemically inert cations. Chinese Journal of Structural Chemistry, 2025, 44(4): 100544-100544. doi: 10.1016/j.cjsc.2025.100544
20. [20]
  Hang Chen , Chengzhi Cui , Hebo Ye , Hanxun Zou , Lei You . Enhancing hydrolytic stability of dynamic imine bonds and polymers in acidic media with internal protecting groups. Chinese Chemical Letters, 2024, 35(5): 109145-. doi: 10.1016/j.cclet.2023.109145

Get Citation

PDF

XML

Metrics

PDF Downloads(0)
Abstract views(756)
HTML views(7)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142