降冰片烯与乙炔基官能化苯并恶嗪单体研究
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摘要
采用溶剂法合成了含有降冰片烯和乙炔基团的苯并恶嗪单体(oHPNI-ac)。通过核磁共振氢谱(~1H-NMR)和傅里叶变换红外光谱(FT-IR)证实了其分子结构,并以示差扫描量热分析(DSC)和原位红外图谱(in situ FT-IR)揭示了其固化行为。结果表明,oHPNI-ac的起始固化温度为205℃,固化峰值温度为224℃。oHPNI-ac中降冰片烯的碳碳双键与乙炔基的碳碳三键可在恶嗪环开环聚合过程中交联,从而降低了降冰片烯双键的固化温度。通过Kissinger方法和Ozawa方法计算得到该苯并恶嗪活化能分别为94.6,97.1 kJ/mol,且推测得到该单体的固化反应动力学方程。
The benzoxazine monomer containing norbornene and acetylene groups(oHPNI-ac)was synthesized by solution method.The chemical structure of synthesized monomer was confirmed by ~1H-NMR and FT-IR. The curing behaviors were monitored by DSC and in situ FT-IR. The results showed that the starting polymerization temperature was 205 ℃ and the curing peak temperature was 224 ℃.The carbon-carbon double bond of norbornene in oHPNI-ac and the carbon-carbon triple bond of ethynyl group could cross-link during the ring-opening polymerization of oxazine ring,thereby reducing the curing temperature of the norbornene double bond. The activation energy of the benzoxazine calculated by Kissinger method and Ozawa method was 94.6 and 97.1 kJ/mol,respectively,and the curing kinetic equation of the monomer was presumed.
The benzoxazine monomer containing norbornene and acetylene groups(oHPNI-ac)was synthesized by solution method.The chemical structure of synthesized monomer was confirmed by ~1H-NMR and FT-IR. The curing behaviors were monitored by DSC and in situ FT-IR. The results showed that the starting polymerization temperature was 205 ℃ and the curing peak temperature was 224 ℃.The carbon-carbon double bond of norbornene in oHPNI-ac and the carbon-carbon triple bond of ethynyl group could cross-link during the ring-opening polymerization of oxazine ring,thereby reducing the curing temperature of the norbornene double bond. The activation energy of the benzoxazine calculated by Kissinger method and Ozawa method was 94.6 and 97.1 kJ/mol,respectively,and the curing kinetic equation of the monomer was presumed.
引文
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[2] Meador M A B,Johnston J C,Cavano P J. Elucidation of the crosslink structure of nadic-end-capped polyimides using NMR of 13Clabeled polymers[J]. Tuberculosis,1997,30(3):515-519.
[3] Zhang K,Liu J,Ohashi S,et al. Synthesis of high thermal stability polybenzoxazoles via ortho-imide-functional benzoxazine monomers[J]. Journal of Polymer Science Part A Polymer Chemistry,2015,53(11):1330-1338.
[4] 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.
[5] Zhang K,Liu J,Ishida H. An ultrahigh performance cross-linked polybenzoxazole via thermal conversion from poly(benzoxazine amic acid)based on smart o-benzoxazine chemistry[J]. Macromolecules,2014,47(24):8674-8681.
[6] And H I,Hong Y L. A study on the volumetric expansion of benzoxazine-based phenolic resin[J]. Macromolecules,1997,30(4):1099-1106.
[7] Shyan Bob Shen,Hatsuo Ishida. Development and characterization of high-performance polybenzoxazine composites[J]. Polymer Composites,2010,17(5):710-719.
[8] Wu J,Xi Y,Mccandless G T,et al. Synthesis and characterization of partially fluorinated polybenzoxazine resins utilizing octafluorocyclopentene as a versatile building block[J]. Macromolecules,2015,48(17):6087-6095.
[9] Ishida H,Ohba S. Synthesis and characterization of maleimide and norbornene functionalized benzoxazines[J]. Polymer,2005,46(15):5588-5595.
[10]袁伟,史铁钧,钱莹,等.降冰片烯酰亚胺型双苯并嗪的合成及性能[J].化工学报,2016,67(11):4899-4905.
[11] Kan Z,Ishida H. Thermally stable polybenzoxazines via ortho-norbornene functional benzoxazine monomers:Unique advantages in monomer synthesis,processing and polymer properties[J]. Polymer,2015,66:240-248.
[12] Zhang K,Qiu J,Li S,et al. Remarkable improvement of thermal stability of main-chain benzoxazine oligomer by incorporating ortho-norbornene as terminal functionality[J]. Journal of Applied Polymer Science,2017,134(41):45408.
[13] Kissinger H E. Reaction kinetics in differential thermal analysis[J].Analytical Chemistry,1957,29(11):1702-1706.
[14] Ozawa T. Kinetic analysis of derivative curves in thermal analysis[J]. Journal of Thermal Analysis,1970,2(3):301-324.
[15] Jubsilp C,Damrongsakkul S,Takeichi T,et al. Curing kinetics of arylamine-based polyfunctional benzoxazine resins by dynamic differential scanning calorimetry[J]. Thermochimica Acta,2006,447(2):131-140.
[16] Lei Z,Xiao H. Autocatalytic curing kinetics of thermosetting polymers:A new model based on temperature dependent reaction orders[J]. Polymer,2010,51(16):3814-3820.
[17] Friedman H L. Kinetics of thermal degradation of char-forming plastics from thermogravimetry application to a phenolic plastic[J]. Journal of Polymer Science Polymer Symposia,2010,6(1):183-195.
[18] Jubsilp C,Punson K,Takeichi T,et al. Curing kinetics of Benzoxazine-epoxy copolymer investigated by non-isothermal differential scanning calorimetry[J]. Polymer Degradation&Stability,2010,95(6):918-924.