有机锡低聚倍半硅氧烷催化固化双酚A型苯并噁嗪树脂结构与性能研究
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摘要
利用八异丁基二硅烷醇与二丁基二氯化锡封端反应合成了有机锡倍半硅氧烷(DOSn-Bu),采用傅里叶红外光谱(FTIR)、核磁共振氢谱(1H-NMR)、X-射线单晶衍射等方法证实了化合物的分子结构.随后利用溶液共混法制备了系列双酚A-苯胺型苯并噁嗪(BA-a-Bz)/DOSn-Bu杂化树脂.从杂化树脂分段固化的FTIR图中可看出,噁嗪环在160～180°C发生开环. DSC结果表明:DOSn-Bu的催化作用使BA-a-Bz的起始固化温度下降了约50°C、峰值固化温度下降了约30°C,动态力学热分析(DMTA)、热失重(TGA)测试结果也表明杂化材料的储能模量和残炭率有所提高.从扫描电镜元素分布图(SEM mapping)看出,催化剂在体系中分散均一,与树脂基体相容性良好且断面SEM图像显示杂化后材料的粗糙度比纯噁嗪树脂的增加.
Polybenzoxazines(PBz) is a new type of phenolic-like resins,which have excellent properties such as good mechanical and thermal properties,no volatile release upon cure,and molecular designing flexiblility.However,their major drawbacks are the high curing temperature and similar brittleness as phenolic resins.In this study,organotin silsesquioxanes(DOSn-Bu) are synthesized via capping reaction based on disilanol-POSS and Bu_2SnCl_2.Due to the cage-type hybrid structure,the metal-based oligomeric silsesquioxane(POMSS) possesses good thermal stability and mechanical properties.The mental centers are Lewis acid that catalyze ring-opening polymerization of benzoxazine monomers.The structure of DOSn-Bu was characterized by Fourier transform infrared spectroscopy(FTIR),nuclear magnetic resonance spectroscopy(~1H-NMR) and X-ray single crystal diffraction.A series of benzoxazine/DOSn-Bu hybrid resins were prepared by ultrasonic blending.FTIR results showed that the benzoxazine began to ring-open at 160 – 180 °C.The results of DSC showed that the initial curing temperature decreased by almost 50 °C and the peak curing temperature decreased by approximately 30 °C with the addition of DOSn-Bu.The thermal and mechanical properties of the hybrid material with different DOSn-Bu incorporation were measured by dynamic mechanical thermal analysis(DMTA) and thermal gravimetric analysis(TGA).DMTA result showed that the storage modulus(E′) and glass transition temperature of the hybrid materials were improved.When 2 wt% of DOSn-Bu was added,the resins retained high storage modulus(E′ =2.1 GPa at 50 °C) and high glass transtion temperature(T_g = 228 °C).TGA study showed that the hybrid materials possessed good thermal stability.From the scanning electron microscopy(SEM) mapping,it was found that the Si and Sn elements were greatly distributed in the system,thereby indicating that the catalysts were uniformly dispersed in the system with good compatibility with the resin matrix.The fracture surface morphologies of the cured resin were investigated by SEM.The roughness of the fracture surface of the hybrid material was increased compared with that of the pure benzoxazine resin and its texture became more complicated.
Polybenzoxazines(PBz) is a new type of phenolic-like resins,which have excellent properties such as good mechanical and thermal properties,no volatile release upon cure,and molecular designing flexiblility.However,their major drawbacks are the high curing temperature and similar brittleness as phenolic resins.In this study,organotin silsesquioxanes(DOSn-Bu) are synthesized via capping reaction based on disilanol-POSS and Bu_2SnCl_2.Due to the cage-type hybrid structure,the metal-based oligomeric silsesquioxane(POMSS) possesses good thermal stability and mechanical properties.The mental centers are Lewis acid that catalyze ring-opening polymerization of benzoxazine monomers.The structure of DOSn-Bu was characterized by Fourier transform infrared spectroscopy(FTIR),nuclear magnetic resonance spectroscopy(~1H-NMR) and X-ray single crystal diffraction.A series of benzoxazine/DOSn-Bu hybrid resins were prepared by ultrasonic blending.FTIR results showed that the benzoxazine began to ring-open at 160 – 180 °C.The results of DSC showed that the initial curing temperature decreased by almost 50 °C and the peak curing temperature decreased by approximately 30 °C with the addition of DOSn-Bu.The thermal and mechanical properties of the hybrid material with different DOSn-Bu incorporation were measured by dynamic mechanical thermal analysis(DMTA) and thermal gravimetric analysis(TGA).DMTA result showed that the storage modulus(E′) and glass transition temperature of the hybrid materials were improved.When 2 wt% of DOSn-Bu was added,the resins retained high storage modulus(E′ =2.1 GPa at 50 °C) and high glass transtion temperature(T_g = 228 °C).TGA study showed that the hybrid materials possessed good thermal stability.From the scanning electron microscopy(SEM) mapping,it was found that the Si and Sn elements were greatly distributed in the system,thereby indicating that the catalysts were uniformly dispersed in the system with good compatibility with the resin matrix.The fracture surface morphologies of the cured resin were investigated by SEM.The roughness of the fracture surface of the hybrid material was increased compared with that of the pure benzoxazine resin and its texture became more complicated.
引文
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22Li Tao(李滔),Yang Wenhao(杨文灏),Zhang Yuwei(张玉卫),Niu Maoshan(牛茂善),Xu Riwei(徐日炜),Yu Dingsheng(余鼎声).Acta Polymerica Sinica(高分子学报),2014,(3):302-308
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24Sudo A,Hirayama S J,Endo T.J Polym Sci,Part A:Polym Chem,2010,48(2):479-484
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26Velez-Herrera P,Doyama K,Abe H,Ishida H.Macromolecules,2008,41(24):9704-9714
2Ye Q,Zhou H,Xu J W.Chem Asian J,2016,11(9):1322-1337
3Feher F J.J Am Chem Soc,1986,108(13):3850-3852
4Feher F J,Newman D A,Walzer J.J Am Chem Soc,1989,111(5):1741-1748
5Ouyang J,Sun H T,Liang Y L,Li D,Commisso A,Xu R W,Yu D S.Curr Org Chem,2017,21(28):2829-2848
6Duchateau R,Dijkstra T W,Severn J R,van Santen R A,Korobkov I V.Dalton Trans,2004,(17):2677-2682
7Gun’ko Y K,Nagy L,Brüser W,Lorenz V,Fischer A,Gieβmann S,Edelmann F T,Jacob K,Vértes A.Monatsh Chem,1999,130(1):45-54
8Strachota A,RodzeńK,Ribot F,TrchováM,Steinhart M,Starovoytova L,Pavlova E.Macromolecules,2014,47(13):4266-4287
9Beletskiy E V,Hou X L,Shen Z L,Gallagher J R,Miller J T,Wu Y Y,Li T H,Kung M C,Kung H H.J Am Chem Soc,2016,138(13):4294-4297
10Beletskiy E V,Shen Z L,Riofski M V,Hou X L,Gallagher J R,Miller J T,Wu Y Y,Kung H H,Kung M C.Chem Commun,2014,50(99):15699-15701
11Beletskiy E V,Wu Y Y,Kung M C,Kung H H.Organometallics,2016,35(3):301-302
12Ishida H,Allen D J.J Polym Sci,Part B:Polym Phys,1996,34(6):1019-1030
13Ishida H,Sanders D.J Polym Sci,Part B:Polym Phys,2000,38(24):3289-3301
14Holly W F,Cope A C.J Am Chem Soc,1944,66(11):1875-1879
15Sudha,Sarojadevi.High Perform Polym,2015,28(3):331-339
16Xin N,Ishida H.J Polym Sci,Part A:Polym Chem,1994,32(6):1121-1129
17Xu Y,Dai J,Ran Q C,Gu Y.Polymer,2017,123:232-239
18Hanbeyoglu B,Kiskan B,Yagci Y.Macromolecules,2013,46(21):8434-8440
19Ishida H,Rodriguez Y.J Appl Polym Sci,1995,58(10):1751-1760
20Wang Y X,Ishida H.Polymer,1999,40:4563-4570
21Ru?igaj A,Ali?B,?ebenuk U.Express Polym Lett,2015,9(7):647-657
22Li Tao(李滔),Yang Wenhao(杨文灏),Zhang Yuwei(张玉卫),Niu Maoshan(牛茂善),Xu Riwei(徐日炜),Yu Dingsheng(余鼎声).Acta Polymerica Sinica(高分子学报),2014,(3):302-308
23Sharma P,Kumar D,Roy P K.Polymer,2018,138:343-351
24Sudo A,Hirayama S J,Endo T.J Polym Sci,Part A:Polym Chem,2010,48(2):479-484
25Shan Jiajia(单家佳),Cheng Xiaojun(程晓君),Wu Yixian(吴一弦),Xu Riwei(徐日炜),Yu Dingsheng(余鼎声).Synthetic Mater Aging Appl(合成材料老化与应用),2008,37(3):11-15
26Velez-Herrera P,Doyama K,Abe H,Ishida H.Macromolecules,2008,41(24):9704-9714