|
|
- 2016
聚硼硅氮烷杂化芳炔基树脂制备及抗热氧化性能
|
Abstract:
合成带乙炔基聚硼硅氮烷(PBSZ),并与含硅芳炔树脂(PSA)进行杂化制备聚硼硅氮烷杂化芳炔基(PBSZ/PSA)树脂,以改善芳炔基树脂的抗热氧化性能。采用FTIR、NMR和凝胶渗透色谱(GPC)对合成的PBSZ进行结构表征;采用旋转流变和DSC对PBSZ/PSA树脂的工艺性能进行研究;采用TGA、SEM和EDS对PBSZ/PSA树脂固化物的热稳定性和抗热氧化性能进行了研究。结果表明:PBSZ/PSA树脂具有良好的加工性能,树脂固化放热量较低,可在210℃下固化;树脂固化物在空气气氛1000℃下的残留率为38.0%,且其氧化后表面形成了60~80 μm厚致密的保护层,可起到良好的隔绝氧气作用;改性树脂固化物1200℃烧结物展现出优异的抗热氧化性能,烧结物1200℃氧化后表面形成约10 μm厚的致密陶瓷保护层,可有效地阻止氧气对材料的侵蚀。 Polyborosilazane with ethynyl group (PBSZ) was synthesized and hybrided with poly(silicon-containing arylacetylene) (PSA) resin to improve thermal-oxidation resistance of polyarylacetylene resin. The structure of PBSZ was characterized by FTIR, NMR and gel permeation chromatography (GPC). The processing properties of PBSZ/PSA resin were investigated by rotational rheometer and DSC, and the thermostability and thermal-oxidation resistance of PBSZ/PSA resin were examined by TGA, SEM and EDS. The results show that PBSZ/PSA resin offers good processability, and could be cured at 210℃ with low exothermal heat. The cured resin residual yields up to 38.0% at 1000℃ under air, and a dense protective layer about 60-80 μm thickness is formed after being oxidized, which inhibits the materials from being oxidized by oxygen. Besides, the sinter of cured resin by 1200℃ also has thermal-oxidation resistance, and a dense ceramic protective layer about 10 μm thickness is produced after being oxidized at 1200℃ and effectively keeps the materials from being oxidized by oxygen. 国家自然科学基金(90816021)
| [1] | HUANG J X, DU W, ZHANG J, et al. Study on the copolymers of silicon-containing arylacetylene resin and acetylene-functional benzoxazine[J]. Polymer Bulletin, 2012, 62(2):127-138. |
| [2] | ZHANG J, HUANG J X, DU W, et al. Thermal stability of the copolymers of silicon-containing arylacetylene resin and acetylene-functional benzoxazine[J]. Polymer Degradation and Stability, 2011, 96(12):2276-2283. |
| [3] | 黄发荣, 杜磊, 齐会民, 等. 新型含硅芳炔树脂的设计及其开发研究[C]//中国工程院化工、冶金与材料工学部第七届学术会议论文集. 天津:化学工业出版社, 2009:1735-1739. HUANG F R, DU L, QI H M, et al. Design, development and research on novel silicon-containing arylacetylene resins[C]//The Chinese Academy of Engineering Chemical Industry, Metallurgy and Materials Engineering Division of the Seventh Conference Proceeding. Tianjin:Chemical Industry Press, 2009:1735-1739(in Chinese). |
| [4] | ITOH M, MITSUZUKA M, IWATA K, et al. Novel synthesis and extremely high thermal stability of poly[(phenykdylene)-ethynylene-1,-phenyleneethynylene] acromoleeules[J]. Journal of Materials Science, 1994, 27(26):7917-7919. |
| [5] | BUVAT P, JOUSSE F, NONY F, et al. Compositions with poly (ethynylene phenylene ethynylene silylenes):US20050065285[P]. 2005-03-24. |
| [6] | 严浩, 齐会民, 黄发荣. 新颖含硅芳基多炔树脂的合成与性能[J]. 石油化工, 2004, 33(9):880-884. YAN H, QI H M, HUANG F R. The synthesis and performance of novel aromatic quito acetylene containing silicon resin[J]. Eochemical Industry, 2004, 33(9):880-884(in Chinese). |
| [7] | WANG F, ZHANG J, HUANG J X, et al. Synthesis and characterization of poly(dimethylsilylene ethynylenephenylene-ethynylene) terminated with phenylacetylene[J]. Polymer Bulletin, 2006, 56(1):19-26. |
| [8] | 高金淼, 齐会民, 张建, 等. 新型含硅芳炔树脂及其复合材料的性能[J]. 化工新型材料, 2008, 36(12):45-46. GAO J M, QI H M, ZHANG J, et al. Properties of new siliconaryl-acetylene resin and its composite materials[J]. New Chemical Materials, 2008, 36(12):45-46(in Chinese). |
| [9] | 张玲玲, 高飞, 周围, 等. 含硅氢基团甲基芳炔树脂的合成及表征[J]. 过程工程学报, 2009, 9(3):574-579. ZHANG L L, GAO F, ZHOU W, et al. Synthesis and characterization of poly(arylacetylene)resins containing mcthylsilylone groups[J]. The Chinese Journal of Process Engineer 2009, 9(3):574-579(in Chinese). |
| [10] | 刘衍兵, 郭康康, 齐会民, 等. 聚硅烷改性含硅芳炔树脂的耐热性能研究[J]. 化工新型材料, 2010, 38(4):84-87. LIU Y B, GUO K K, QI H M, et al. Thermal stability of blends of polysilane and silicon-containing arylacetylene resin[J]. New Chemical Materials, 2010, 38(4):84-87(in Chinese). |
| [11] | ISHIKAWA J, IWATA K, INOUE K, et al. Heat-and oxidation-resistant siliconized acetylene resin compositions:JP10053708[P]. 1998-06-20. |
| [12] | ICHITANI M, YONEZAWA K, SUGIMOTO T. Silyl-carborane hybridized diethnylbenzene-silylene polymer[J].Polymer Journal, 1999, 31(11):908-912. |
| [13] | KIMURA H, OKITA K, ICHITANI M. Structure study of silyl-carborane hybrid diethnyl-benzenesilylene polymer by high-resolution solid-state11B, 13C, and 29Si NMR spectroscopy[J]. Chemisty of Material, 2003, 15(1):355-362. |
| [14] | Keller T M. High temperature copolymers from inorganic-oganic hybrid polymer and multi-ethynylbenzenes:US5552505[P]. 1996-09-03. |
| [15] | WANG C F, JIANG Y, GAO Y, et al.Carborane-incorporated poly(silylene-ethynylenephenyleneethynylene)s with different side groups[J]. Polymer Engineering & Science.2012, 52(6):1301-1308. |
