聚十四烷基三苯乙炔基硅烷树脂的制备与热分解
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摘要
以镁条、溴乙烷、苯乙炔和十四烷基三氯硅烷为原料,通过格利雅反应制备了十四烷基三苯乙炔基硅烷(TTPES),采用红外和核磁共振光谱(~1H-NMR、~(13)C-NMR和~(29)Si-NMR)对其结构进行了表征。根据示差扫描量热法(DSC)确定了TTPES单体的固化工艺,由热聚合法制备了聚十四烷基三苯乙炔基硅烷树脂(PTTPES),利用TGDTG分析研究了PTTPES树脂的热分解行为,并采用Kissinger、Ozawa等6种方法研究了树脂的热分解动力学。结果表明,树脂的Td5为437℃,800℃残炭率高于43%。PTTPES树脂的热分解Ea为188.53 kJ/mol,指前因子A为1.27×10~(13)/s,得到了热分解动力学方程:(dα)/(dT)=(1.27×10~(13))/βexp ((-188.53)/(RT))·2/3α~(-1/2)。
The tetradecyl(triphenylethynyl)silane(TTPES)was synthesized via Grignard reaction of tetradecyl trichlorosilane and phenyl acetylene in the presence of magnesium and ethyl bromide. Its chemical structure was characterized by Fourier transform infrared spectroscopy(FT-IR)and nuclear magnetic resonance spectroscopy(~1H-NMR ~(13)C-NMR,and ~(29)Si-NMR). Its curing process was obtained by differential scanning calorimetry(DSC)and the corresponding polytetradecyl(triphenylethynyl)silane resin(PTTPES)was synthesized by thermal polymerization. The thermal decomposition behavior was analyzed by TG and DTG, and the thermal decomposition kinetics was studied by six well-known kinetic methods,i.e.,Kissinger,Ozawa. The results showed that resin′ s Td5 decomposition temperature was 437 ℃ and the char yield was over 43 % at 800 ℃. The activation energy Eaand the pre-exponential factor A was 188.53 kJ/mol and 1.27 ×1013/s respectively. The thermal decomposition kinetic equation was as follows (1.27×10~(13))/βexp ((-188.53)/(RT))·2/3α~(-1/2).
The tetradecyl(triphenylethynyl)silane(TTPES)was synthesized via Grignard reaction of tetradecyl trichlorosilane and phenyl acetylene in the presence of magnesium and ethyl bromide. Its chemical structure was characterized by Fourier transform infrared spectroscopy(FT-IR)and nuclear magnetic resonance spectroscopy(~1H-NMR ~(13)C-NMR,and ~(29)Si-NMR). Its curing process was obtained by differential scanning calorimetry(DSC)and the corresponding polytetradecyl(triphenylethynyl)silane resin(PTTPES)was synthesized by thermal polymerization. The thermal decomposition behavior was analyzed by TG and DTG, and the thermal decomposition kinetics was studied by six well-known kinetic methods,i.e.,Kissinger,Ozawa. The results showed that resin′ s Td5 decomposition temperature was 437 ℃ and the char yield was over 43 % at 800 ℃. The activation energy Eaand the pre-exponential factor A was 188.53 kJ/mol and 1.27 ×1013/s respectively. The thermal decomposition kinetic equation was as follows (1.27×10~(13))/βexp ((-188.53)/(RT))·2/3α~(-1/2).
引文
[1] Itoh M,Inoue K,I wata K,et al. A heat-resistant silicon-based polymer[J]. Adv. Mater.,1997,9(15):1187-1190.
[2] 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.
[3] Chen H,Xin H,Lu J,et al. Synthesis and properties of poly(dimethylsilylene-ethynylene-phenoxyphenoxyphenylene-ethynylene)[J]. High Perform. Polym.,2016,29(5):1-7.
[4] Bu X,Zhou Y,Huang F. The strengthening and toughening effects of a novel octa(propargylpropylsulfide)POSS(OPPSP)on siliconcontaining arylacetylene(PSA)resin[J]. Mater. lett.,2016,174:21-23.
[5]顾渊博,扈艳红,杜磊,等.聚醚酰亚胺耐热大分子偶联剂增强增韧石英纤维/含硅芳炔复合材料[J].高等学校化学学报,2017,38(9):1670-1677.
[6] Sastri S B,Armistead J P,Keller T M. Cure kinetics of a multisubstituted acetylenic monomer[J]. Polymer,1995,36(7):1449-1454.
[7] Chen M,Liu C,Lin J. Correlation of cross-linked structures and properties in the characterization of dimethyl-diphenylethynylsilane using DSC,TGA and Py-GC/MS analysis[J]. Polym. Degrad.Stab.,2015,112:35-42.
[8] Han Mengna,Guo Kangkang,Wang Fan,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.
[9] Wrackmeyer B,Khan E,Bayer S,et al. Alkynylsilanes and alkynyl(vinyl)silanes. synthesis,molecular structures and multinuclear magnetic resonance study[J]. Z Naturforsch B,2010,65(6):725-744.
[10] Tan D,Wu X,Wang Y,et al. Synthesis,characterization and curing behavior of propyl-tri(phenylethynyl)silane[J]. Iran. Polym. J.,2016,25(8):687-695.
[11] Kim C,Jeong K,Jung I. Progress toward limiting generation of dendritic ethynylsilanes(PhC≡C)4-n MenSi(n=0-2)[J]. J. Polym.Sci. Polym. Chem.,2000,38(15):2749-2759.
[12] Zhou Q,Feng X,Ni L,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.
[13] Liu H Q,Harrod J F. 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.
[14] 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.
[15] 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.
[16]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.
[17] Tan D,Wang Y,Li Z,et al. Synthesis and cure kinetics of diphenyl(diphenylethynyl)silane monomer[J]. Res. Chem. Intermed.,2013,39(7):3427-3440.
[18] Tan De Xin,Wu Xiao Le,Wang Yan Li,et al. Synthesis,characterization and curing behavior of methyl-tri(phenylethynyl)silane[J]. Res. Chem. Intermed.,2016,42(5):4669-4681.
[19] Zhou Q,Feng X,Ni L,et al. Thermal characteristics and pyrolysis of methyl-di(phenylethynyl)silane resin[J]. J. Appl. Polym. Sci.,2007,103(1):605-610.
[20]谭德新,王艳丽,唐玲,等.聚乙烯基三苯乙炔基硅烷的热分解动力学[J].材料科学与工艺,2015,23(4):81-86.
[21]王艳丽,谭德新,于峰,等.聚苯基三苯乙炔基硅烷树脂的非等温热分解过程研究[J].功能材料,2014,45(21):21040-21044.
[22]谭德新,徐远,王艳丽,等.聚二苯基二苯乙炔基硅烷树脂的制备与非等温热分解[J].材料工程,2017,45(7):77-83.
[23] Ratio J J,Dynes P J,Hammeresh C L. The synthesis and thermal polymerization of 4,4′-diethynylphenyl ether[J]. J. Polym. Sci.Polym. Chem.,1980,18(3):1035-1046.
[24]谭德新.三苯乙炔基硅烷树脂及其SiC/C(TiN/C)复合木陶瓷的制备、结构和性能研究[D].合肥:合肥工业大学,2011.
[25] Tan De Xin,Shi Tie Jun,Li Zhong. Synthesis,Characterization and non-isothermal curing kinetics of two silicon-containing arylacetylenic monomers[J]. Res. Chem. Intermed.,2011,37(8):831-845.
[26] Vlase T,Vlase G,Birta N,et al. Comparative results of kinetic data obtained with different methods for complex decomposition steps[J].J. Therm. Anal. Calorim.,2007,88(3):631-635.
[27] Ren Y L,Cheng B W,Zhang J S,et al. Thermal degradation kinetics of N,N′-di(diethoxythiophosph-oryl)-1,4-phenylenediamine[J]. Chem. Res. Chinese U.,2008,24(5):628-631.
[28] Vyazovkin S,Wight C A. Model-free and model-fitting approaches to kinetic analysis of isothermal and nonisothermal data[J]. Thermochim.,Acta.,1999,340/341:53-68.
[29]胡荣祖,高胜利,赵凤起.热分析动力学(第2版)[M].北京:科学出版社,2008.
[2] 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.
[3] Chen H,Xin H,Lu J,et al. Synthesis and properties of poly(dimethylsilylene-ethynylene-phenoxyphenoxyphenylene-ethynylene)[J]. High Perform. Polym.,2016,29(5):1-7.
[4] Bu X,Zhou Y,Huang F. The strengthening and toughening effects of a novel octa(propargylpropylsulfide)POSS(OPPSP)on siliconcontaining arylacetylene(PSA)resin[J]. Mater. lett.,2016,174:21-23.
[5]顾渊博,扈艳红,杜磊,等.聚醚酰亚胺耐热大分子偶联剂增强增韧石英纤维/含硅芳炔复合材料[J].高等学校化学学报,2017,38(9):1670-1677.
[6] Sastri S B,Armistead J P,Keller T M. Cure kinetics of a multisubstituted acetylenic monomer[J]. Polymer,1995,36(7):1449-1454.
[7] Chen M,Liu C,Lin J. Correlation of cross-linked structures and properties in the characterization of dimethyl-diphenylethynylsilane using DSC,TGA and Py-GC/MS analysis[J]. Polym. Degrad.Stab.,2015,112:35-42.
[8] Han Mengna,Guo Kangkang,Wang Fan,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.
[9] Wrackmeyer B,Khan E,Bayer S,et al. Alkynylsilanes and alkynyl(vinyl)silanes. synthesis,molecular structures and multinuclear magnetic resonance study[J]. Z Naturforsch B,2010,65(6):725-744.
[10] Tan D,Wu X,Wang Y,et al. Synthesis,characterization and curing behavior of propyl-tri(phenylethynyl)silane[J]. Iran. Polym. J.,2016,25(8):687-695.
[11] Kim C,Jeong K,Jung I. Progress toward limiting generation of dendritic ethynylsilanes(PhC≡C)4-n MenSi(n=0-2)[J]. J. Polym.Sci. Polym. Chem.,2000,38(15):2749-2759.
[12] Zhou Q,Feng X,Ni L,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.
[13] Liu H Q,Harrod J F. 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.
[14] 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.
[15] 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.
[16]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.
[17] Tan D,Wang Y,Li Z,et al. Synthesis and cure kinetics of diphenyl(diphenylethynyl)silane monomer[J]. Res. Chem. Intermed.,2013,39(7):3427-3440.
[18] Tan De Xin,Wu Xiao Le,Wang Yan Li,et al. Synthesis,characterization and curing behavior of methyl-tri(phenylethynyl)silane[J]. Res. Chem. Intermed.,2016,42(5):4669-4681.
[19] Zhou Q,Feng X,Ni L,et al. Thermal characteristics and pyrolysis of methyl-di(phenylethynyl)silane resin[J]. J. Appl. Polym. Sci.,2007,103(1):605-610.
[20]谭德新,王艳丽,唐玲,等.聚乙烯基三苯乙炔基硅烷的热分解动力学[J].材料科学与工艺,2015,23(4):81-86.
[21]王艳丽,谭德新,于峰,等.聚苯基三苯乙炔基硅烷树脂的非等温热分解过程研究[J].功能材料,2014,45(21):21040-21044.
[22]谭德新,徐远,王艳丽,等.聚二苯基二苯乙炔基硅烷树脂的制备与非等温热分解[J].材料工程,2017,45(7):77-83.
[23] Ratio J J,Dynes P J,Hammeresh C L. The synthesis and thermal polymerization of 4,4′-diethynylphenyl ether[J]. J. Polym. Sci.Polym. Chem.,1980,18(3):1035-1046.
[24]谭德新.三苯乙炔基硅烷树脂及其SiC/C(TiN/C)复合木陶瓷的制备、结构和性能研究[D].合肥:合肥工业大学,2011.
[25] Tan De Xin,Shi Tie Jun,Li Zhong. Synthesis,Characterization and non-isothermal curing kinetics of two silicon-containing arylacetylenic monomers[J]. Res. Chem. Intermed.,2011,37(8):831-845.
[26] Vlase T,Vlase G,Birta N,et al. Comparative results of kinetic data obtained with different methods for complex decomposition steps[J].J. Therm. Anal. Calorim.,2007,88(3):631-635.
[27] Ren Y L,Cheng B W,Zhang J S,et al. Thermal degradation kinetics of N,N′-di(diethoxythiophosph-oryl)-1,4-phenylenediamine[J]. Chem. Res. Chinese U.,2008,24(5):628-631.
[28] Vyazovkin S,Wight C A. Model-free and model-fitting approaches to kinetic analysis of isothermal and nonisothermal data[J]. Thermochim.,Acta.,1999,340/341:53-68.
[29]胡荣祖,高胜利,赵凤起.热分析动力学(第2版)[M].北京:科学出版社,2008.