聚(间二乙炔基苯-甲基氢硅烷)/含乙炔基苯并噁嗪树脂共混体系固化行为及其耐热性能研究
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摘要
聚(间二乙炔基苯-甲基氢硅烷)(PSA)和含乙炔基苯并噁嗪树脂(A-PBZ)在热作用下均能够聚合形成交联网状结构。研究了PSA/A-PBZ共混树脂(SB)的固化行为。通过红外光谱(FT-IR)、旋转流变仪和差示扫描量热仪(DSC)研究了PSA/A-PBZ质量比为5∶2时共混树脂(SB-2)的固化特性,利用动态DSC分析,根据Kissinger方法和Ozawa方法计算得出SB-2共混树脂固化反应的表观活化能分别为108.4 kJ/mol、111.1 kJ/mol,反应级数分别为0.93和0.95,固化反应遵循一级反应机理。同时还对SB共混树脂体系的耐热性能进行了探究,热重分析(TGA)结果表明:在氮气和空气氛围下,SB共混树脂固化物失重5%的温度(T_(d5))和1 000℃时的质量保留率均随着A-PBZ树脂加入量的增加而减小,但SB共混树脂仍然表现出优异的耐热性能。
Poly(m-diethynylbenzene-methylsilane)(PSA) and acetylene-functionalized benzoxazine resin(A-PBZ) have been thermally co-polymerized to form a cross-linked structure. The curing behavior of the PSA/A-PBZ blended resins(SB) was studied. The curing properties of the SB-2 blending resins were studied by FT-IR, rheological analysis and DSC. Dynamic DSC analysis gave a value of the apparent activation energy for the curing reaction of the SB-2 blending resin of about 108 kJ/mol(using the Kissinger method) and 111 kJ/mol(using the Ozawa method) and the calculated reaction orders were 0.93 and 0.95, respectively. The curing reaction follows first-order kinetics. The heat resistance of the SB blended resin was also studied. TGA in nitrogen and air showed that the temperature for 5% mass loss(T_(d5)) and the residual mass at 1 000 ℃ decreased with increasing content of A-PBZ resin, but the SB blended resin still exhibited excellent heat resistance.
Poly(m-diethynylbenzene-methylsilane)(PSA) and acetylene-functionalized benzoxazine resin(A-PBZ) have been thermally co-polymerized to form a cross-linked structure. The curing behavior of the PSA/A-PBZ blended resins(SB) was studied. The curing properties of the SB-2 blending resins were studied by FT-IR, rheological analysis and DSC. Dynamic DSC analysis gave a value of the apparent activation energy for the curing reaction of the SB-2 blending resin of about 108 kJ/mol(using the Kissinger method) and 111 kJ/mol(using the Ozawa method) and the calculated reaction orders were 0.93 and 0.95, respectively. The curing reaction follows first-order kinetics. The heat resistance of the SB blended resin was also studied. TGA in nitrogen and air showed that the temperature for 5% mass loss(T_(d5)) and the residual mass at 1 000 ℃ decreased with increasing content of A-PBZ resin, but the SB blended resin still exhibited excellent heat resistance.
引文
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[2] ITOH M,IWATA K,ISHIKAWA J I,et al.Various silicon-containing polymers with Si(H)—CC units[J].Journal of Polymer Science:Part A:Polymer Chemistry,2001,39(15):2658- 2669.
[3] CHEN M F,XIONG P L,ZHOU Q,et al.Synthesis,curing behavior and thermal properties of silicon-containing hybrid polymers with Si—CC units [J].Polymer International,2014,63(8):1531- 1536.
[4] ITOH M,INOUE K,HIRAYAMA N,et al.Fiber reinforced plastics using a new heat-resistant silicon based polymer [J].Journal of Materials Science,2002,37(17):3795- 3801.
[5] 葛娟,赛力克·达尼拜,周权,等.耐高温聚(间二乙炔基苯- 甲基氢硅烷- 苯基硅烷)树脂的合成及性能[J].材料工程,2018,46(10):149- 155.GE J,SALIKE D,ZHOU Q,et al.Synthesis and properties of high temperature resistant of poly (m-diethylenebenzene-methylsilane-phenylsilane) resin[J].Journal of Materials Engineering,2018,46(10):149- 155.(in Chinese)
[6] 冯子健,曾鸣,刘程,等.苯并噁嗪功能材料的研究进展[J].高分子材料科学与工程,2018,34(1):184- 190.FENG Z J,ZENG M,LIU C,et al.Preparation and applications of functionalized benzoxazine-based materials[J].Polymer Materials Science and Engineering,2018,34(1):184- 190.(in Chinese)
[7] ISHIDA H,AGAG T.Handbook of benzoxazine resins[M].Amsterdam:Elsevier,2011:3- 8.
[8] YAGCI Y,KISKAN B,GHOSH N N.Recent advancement on polybenzoxazine—a newly developed high performance thermoset[J].Journal of Polymer Science:Part A:Polymer Chemistry,2009,47(21):5565- 5576.
[9] KUROKI S,OKITA K,KAKIGANO T,et al.Thermosetting mechanism study of poly[(phenylsilylene)ethynylene-1,3-phenyleneethynylene] by solid-state NMR spectroscopy and computational chemistry[J].Macromolecules,1998,31(9):2804- 2808.
[10] JANG J,SHIN S.Cure studies of a benzoxazine-based phenolic resin by isothermal experiment[J].Polymer Journal,1995,27(6):601- 606.
[11] ITOH M,MITSUZUKA M,IWATA K,et al.A novel synthesis and extremely high thermal stability of poly[(phenylsilylene)ethynylene-1,3-phenyleneethynylene][J].Macromolecules,1994,27(26):7917- 7919.
[12] KIM H J,BRUNOVSKA Z,ISHIDA H.Synthesis and thermal characterization of polybenzoxazines based on acetylene-functional monomers[J].Polymer,1999,40(23):6565- 6573.
[13] JIANG D Y,ZHOU Q,FAN Q,et al.Curing behavior and thermal performance of cyanate ester resin modified by poly(methyl-benzene diethynylbenzene)siliane[J].Polymer Bulletin,2015,72(9):2201- 2214.
[14] 田巧,向海,凌鸿,等.含乙炔基苯并噁嗪的固化反应的研究[C]//2005年全国高分子学术论文报告.北京,2005:147.TIAN Q,XIANG H,LING H,et al.Study on cure reaction of acetylene-functional benzoxazine [C]//Report on Polymer Academic Papers of China.Beijing,2005:147.(in Chinese)
[15] 于伯龄,姜胶东.实用热分析[M].北京:纺织工业出版社,1990:79- 112.YU B L,JIANG J D.Application of thermal analysis[M].Beijing:China Textile & Apparel Press,1990:79- 112.(in Chinese)
[16] KISSINGER H E.Reaction kinetic in differential thermal analysis[J].Analytical Chemistry,1957,29(11):1702- 1706.
[17] FLYNN J H,WALL L A.Initial kinetic parameters from thermogravimetric rate and conversion data[J].Journal of Polymer Science:Part B:Polymer Letters,1967,5(2):191- 196.
[18] CRANE L W,DYNES P J,KAELBLE D H.Analysis of curing kinetic in polymer composites[J].Polymer Science,1973,11(8):533- 540.