以苯乙炔、镁条、氯丙基三氯硅烷和溴乙烷为原料,通过Grignard反应成功制备氯丙基三苯乙炔基硅烷(CPTPES)单体。利用傅里叶变换红外光谱仪和核磁共振波谱仪(1H-NMR、13C-NMR)对单体进行结构表征;通过差示扫描量热仪(DSC)确定单体的固化工艺,采用Kissinger法、Ozawa法、Flynn-Wall-Ozawa法和Friedman法探究单体的固化特性,并预测固化反应机理。实验结果表明:CPTPES的熔点为75℃,反应活化能Ea为146.75kJ/mol,指前因子lnA为26.33,反应级数m为0.47,n为1.61,固化机理与自催化反应机理相符。
Chloropropyl(triphenylethynyl)silane (CPTPES) monomer was synthesized via Grignard reaction of phenylacetylene,magnesium,chloropropyltrichlorosilane and ethylbromide.Its chemical structure was characterized by Fourier transform infrared spectroscopy (FT-IR) and nuclear magnetic resonance spectroscopy (1H-NMR,13C-NMR).Its curing process was obtained by differential scanning calorimetry (DSC) and the curing kinetic parameters were discussed by four well-known kinetic methods,i.e.,Kissinger,Ozawa,Flynn-Wall-Ozawa and Friedman methods.Results shown that the melting was 75℃,the reaction activation energy Ea was 146.75kJ/mol,the pre-exponential factor lnA was 26.33 and the reaction order m and n were 0.47 and 1.61 respectively.The curing mechanism was in accordance with autocatalytic reaction.
[1] Sastri S,Armistead J,Keller T.Cure kinetics of a multisubstituted acetylenic monomer[J].Polymer,1995,36(7):1449-1454.
[2] Itoh M,Inoue K,Iwata K,et al.A heat-resistant silicon-based polymer[J].Adv Mater,1997,9(15):1187-1190.
[3] Bu X,Zhou Y,Huang F.The strengthening and toughening effects of a novel octa(propargylpropylsulfide) POSS (OPPSP) on silicon-containing arylacetylene (PSA) resin[J].Mater Lett,2016,174:21-23.
[4] Han M,Guo K,Wang F,et al.Synthesis,characterization,and properties of thermosets based on the cocuring of an acetylene-terminated liquid-crystal and silicon-containing arylacetylene oligomer[J].J Appl Polym Sci,2017,134(33):45141-45151.
[5] 陈麒,李扬,戴泽亮,等.甲基二苯乙炔基硅烷及其网络聚合物的合成与表征[J].化学学报,2005,63(3):254-258.
[6] Tan Dexin,Wu Xiaole,Wang Yanli,et al.Synthesis,characterization and curing behavior of propyl-tri(phenylethynyl) silane[J].Iran Polym J,2016,25(8):687-695.
[7] Kim C,Jeong K,Jung I.Progress toward limiting generation of dendritic ethynylsilanes (PhC≡C)4-nMenSi(n=0-2)[J].J Polym Sci Polym Chem,2000,38(15):2749-2759.
[8] Zhou Quan,Feng Xia,Ni Lizhong,et al.Novel heat resistant methyl-tri (phenylethynyl) silane resin:synthesis,characterization and thermal properties[J].J Appl Polym Sci,2006,102(3):2488-2492.
[9] Liu H,Harrod J.Copper (I) chloride-catalyzed cross-dehydrocoupling reactions between silanes and ethynyl compounds:a new method for the copolymerization of silanes and alkynes[J].Can J Chem,1990,68(7):1100-1104.
[10] Kownacki I,Orwat B,Marciniec B,et al.A new and efficient route for the synthesis of alkynyl functionalized silicon derivatives[J].Tetrahedron Lett,2014,55(2):548-550.
[11] Iwasaki T,Shimizu R,Imanishi R,et al.Copper-catalyzed regioselective hydroalkylation of 1,3-dienes with alkyl fluorides and grignard reagents[J].Angew Chem Int Ed,2015,54(34):9347-9350.
[12] 陈明锋,周权,倪礼忠,等.含苯乙炔基共轭单体的合成及荧光性能[J].高分子材料科学与工程,2013,29(12):1-4.
[13] Tan Dexin,Wang Yanli,Li Zi,et al.Synthesis and cure kinetics of diphenyl(diphenylethynyl)silane monomer[J].Research on Chemical Intermediat,2013,39(7):3427-3440.
[14] Tan Dexin,Wu Xxiaole,Wang Yanli,et al.Synthesis,characterization and curing behavior of methyl-tri(phenylethynyl)silane[J].Research on Chemical Intermediat,2016,42(5):4669-4681.
[15] Zhou Quan,Feng Xia,Ni Lizhong,et al.Thermal characteristics and pyrolysis of methyl-di(phenylethynyl) silane resin[J].J Appl Polym Sci,2007,103(1):605-610.
[16] Guo K,Li Y,Zhu Y,et al.Thermal curing and degradation behavior of silicon-containing arylacetylene resins[J].Polym Degrad Stab,2016,131:98-105.
[17] Ratio J,Dynes P,Hammeresh C.The synthesis and thermal polymerization of 4,4′-diethynylphenylether[J].J Polym Sci Polym Chem,1980,18(3):1035-1046.
[18] 胡荣祖,高胜利,赵凤起.热分析动力学[M].第2版.北京:科学出版社,2008:151-159.
[19] Jubsilp C,Punson K,Takeichi T,et al.Curing kinetics of benzoxazine-epoxy copolymer investigated by non-isothermal differential scanning calorimetry[J].Polym Degrad Stab,2010,95(6):918-924.
[20] Friedman H.Kinetics of thermal degradation of char-forming plastics from thermogravimetry[J].J Polym Sci Part C:Polym Symp,1964,6(1):183-195.
[21] Hatsuo Ishida,Tarek Agag.Handbook of benzoxazine resins[M].Amsterdam:Elsevier,2011:167-168.
[22] 周权,耐高温苯乙炔硅烷及苯乙炔封端聚(甲基硅烷碳硼烷)的合成、表征及性能研究[D].上海:华东理工大学,2006.
