聚十二烷基三苯乙炔基硅烷树脂的制备与热性能
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摘要
以镁条、溴乙烷、苯乙炔和十二烷基三氯硅烷为原料,通过Grignard反应制得十二烷基三苯乙炔基硅烷单体(DTPES)。采用傅里叶变换红外光谱(FTIR)和核磁共振波谱(~1HNMR、~(13)CNMR和~(29)Si NMR)对DTPES结构进行了表征;利用差示扫描量热法(DSC)确定了DTPES的最佳固化工艺。通过热聚合法制得聚十二烷基三苯乙炔基硅烷树脂(PDTPES),利用TG-DTG分析了PDTPES树脂的热稳定性,并采用6种方法(Kissinger、Ozawa、Achar、Cosat-Redfern、Friedman和Vyazonvkin-Weight法)对树脂的热分解行为进行了探究。结果表明,升温速率为10℃/min时,PDTPES树脂质量损失5%的温度(T_(d5))为440℃,800℃下残炭率为48.1%。动力学分析显示,不同分析方法下,PDTPES树脂的热分解活化能(E_a)分别为182.76、181.53、179.48、179.45、187.53和178.33 kJ/mol,指前因子(A)分别为1.05×10~(12)、3.40×10~(10)、3.79×10~(12)、1.88×10~(11)、5.73×10~(11)和1.52×10~(11)s~(–1),并求得热分解动力学方程。
Dodecyltris(2-phenylethynyl)silane(DTPES)was synthesized via Grignard reaction of dodecyl trichlorosilane and phenyl acetylene in the presence of magnesium and ethyl bromide.Its chemical structure was characterized by Fourier transform infrared spectroscopy(FTIR)and nuclear magnetic resonance spectroscopy(~1HNMR,~(13)CNMR,~(29)Si NMR).Its curing process was obtained by differential scanning calorimetry(DSC).Subsequently,polydodecyl(triphenylethynyl)silane(PDTPES)was synthesized by thermal polymerization of DTPES monomer.The thermal decomposition behavior was analyzed by TG and DTG and the corresponding kinetics parameters and thermal decomposition characteristics were discussed by six kinetics methods,i.e.,Kissinger,Ozawa,Achar,Coast-Redfern,Friedman and Vyazonvkin-Weight methods.The results showed that the decomposition temperature at 5%weight loss(T_(d5))of the resin was440℃and the char yield was 48.1%at 800℃under a heating rate of 10℃/min.The activation energy E_(a )and the pre-exponential factor A were 182.76,181.53,179.48,179.45,187.53 and 178.33 kJ/mol,and1.05×10~(12),3.40×10~(10),3.79×10~(12),1.88×10~(11),5.73×10~(11) and 1.52×10~(11 )s~(–1),respectively,by the above methods.The thermal decomposition kinetics equation was also proposed.
Dodecyltris(2-phenylethynyl)silane(DTPES)was synthesized via Grignard reaction of dodecyl trichlorosilane and phenyl acetylene in the presence of magnesium and ethyl bromide.Its chemical structure was characterized by Fourier transform infrared spectroscopy(FTIR)and nuclear magnetic resonance spectroscopy(~1HNMR,~(13)CNMR,~(29)Si NMR).Its curing process was obtained by differential scanning calorimetry(DSC).Subsequently,polydodecyl(triphenylethynyl)silane(PDTPES)was synthesized by thermal polymerization of DTPES monomer.The thermal decomposition behavior was analyzed by TG and DTG and the corresponding kinetics parameters and thermal decomposition characteristics were discussed by six kinetics methods,i.e.,Kissinger,Ozawa,Achar,Coast-Redfern,Friedman and Vyazonvkin-Weight methods.The results showed that the decomposition temperature at 5%weight loss(T_(d5))of the resin was440℃and the char yield was 48.1%at 800℃under a heating rate of 10℃/min.The activation energy E_(a )and the pre-exponential factor A were 182.76,181.53,179.48,179.45,187.53 and 178.33 kJ/mol,and1.05×10~(12),3.40×10~(10),3.79×10~(12),1.88×10~(11),5.73×10~(11) and 1.52×10~(11 )s~(–1),respectively,by the above methods.The thermal decomposition kinetics equation was also proposed.
引文
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[26]Tan D, Shi T, Li Z. Synthesis, characterization and non-isothermal curing kinetics of two silicon-containing arylacetylenicmonomers[J].Res Chem Intermed, 2011, 37(8):831-845.
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[31]Ren Y, Cheng B, Zhang J, et al. Thermal degradation kinetics of N,N'-di(diethoxythiophosph-oryl)-1,4-phenylenediamine[J].Chem Res Chinese U, 2008, 24(5):628-631.
[32]Vyazovkin S, Wight C. Model-free and model-fitting approaches to kineticanalysisofisothermalandnonisothermaldata[J].Thermochim Acta, 1999, 340/341:53-68.
[33]Díaz-CelorioE,FrancoL,MárquezY,etal.Thermaldegradation studiesonhomopolymersandcopolymersbasedontrimethylene carbonateandglycolideunits[J].ThermochimicaActa,2012,528:23-31.
[34]GaoJ,TangQ,ChenX.Decompositionkineticsandprocess experiments on dolomite[J]. Journal of Functional Materials, 2012,43(23):3194-3196.
[35]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.
[36]Vyazovkin E. Evaluation of activation energy of thermally stimulated solid-statereactionsunderarbitraryvariationoftemperature[J].J Comput Chem, 1997, 18:393-402.
[37]Zhang Laying(张腊莹), Zhu Xinhua(朱欣华), Qing Hui(卿辉), et al. Thermal behavior and non-isothermal decomposition kinetics of3, 4-bis(3', 5'-dinitrophenyl-1'-yl)furoxan[J]. Journalof Solid Rocket Technology(固体火箭技术), 2011, 34(5):623-627.
[2]ChenM,LiuC,LinJ.Correlationofcross-linkedstructuresand properties in the characterization of dimethyl-diphenylethynyl-silane usingDSC,TGAandPy-GC/MSanalysis[J].PolymDegradStab,2015, 112:35-42.
[3]HanM,GuoK,WangF,etal.Synthesis,characterization,and propertiesofthermosetsbasedonthecocuringofanacetyleneterminatedliquid-crystalandsilicon-containingarylacetylene oligomer[J]. J Appl Polym Sci, 2017, 134(33):45141-45151.
[4]ItohM,InoueK,IwataK,etal.Aheat-resistantsilicon-based polymer[J]. Adv Mater, 1997, 9(15):1187-1190.
[5]ChenH,XinH,LuJ,etal.Synthesisandpropertiesofpoly(dimethylsilylene-ethynylene-phenoxyphenoxyphenylene-ethynylene)[J]. High Perform Polym, 2016, 29(5):1-7.
[6]Bu X, Zhou Y, Huang F. The strengthening and toughening effects of anovelocta(propargylpropylsulfide)POSS(OPPSP)on silicon-containingarylacetylene(PSA)resin[J].MaterLett,2016,174:21-23.
[7]GuYuanbo(顾渊博),HuYanhong(扈艳红),DuLei(杜磊),etal.Reinforcement and tougheness of quartz fiber/siliconcontainingarylacetylene with heatresistantpolyetherimidemacromolecularcoupling agent[J].Chem J Chin U(高等学校化学学报), 2017, 38(9):1670-1677.
[8]Wrackmeyer B, Bayer S, Tok O, et al. Alkynylsilanes and alkynyl(vinyl)silanes.Synthesis,molecularstructuresandmultinuclear magnetic resonance study[J]. Zeitschrift Für Naturforschung B, 2010,65(6):725-744.
[9]ChenQi(陈麒),LiYang(李扬),DaiZeliang(戴泽亮),etal.Synthesisandcharacterizationofmethyl-di(phenylethynyl)silane and its network polymer[J]. Acta Chimica Sinica(化学学报), 2005,63(3):254-258.
[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]KimC,JeongK,JungI.Progresstowardlimitinggenerationof dendriticethynylsilanes(Ph C≡C)4-nMenSi(n=0~2)[J].JPolymSci Polym Chem, 2000, 38(15):2749-2759.
[12]ZhouQ,FengX,NiL,etal.Novelheatresistantmethyl-tri(phenylethynyl)silane resin:synthesis, characterization and thermal properties[J]. J Appl Polym Sci, 2006, 102(3):2488-2492.
[13]LiuH,HarrodJ.Copper(I)chloride-catalyzedcrossdehydrocouplingreactions 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 forthesynthesisofalkynylfunctionalizedsiliconderivatives[J].Tetrahedron Lett, 2014, 55(2):548-550.
[15]IwasakiT,ShimizuR,ImanishiR,etal.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]Chen Mingfeng(陈明锋), Zhou Quan(周权), Ni Lizhong(倪礼忠),et al. Synthesis and fluorescence properties of conjugated monomers containingphenylacetylene[J].PolymerMaterialsScienceand Engineering(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)silanemonomer[J].ResChemIntermed,2013,39(7):3427-3440.
[18]Tan D, Wu X, Wang Y, 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)silaneresin[J].JApplPolymSci,2007,103(1):605-610.
[20]Hu Rongzu(胡荣祖), Gao Shengli(高胜利), Zhao Fengqi(赵凤起).Thermal analysis kinetics[M]. Beijing:Beijing Science Press(北京科学出版社), 2008:151-159.
[21]Guo K, Li Y, Zhu Y, et al. Thermal curing and degradation behavior ofsilicon-containingarylacetyleneresins[J].PolymDegradStab,2016, 131:98-105.
[22]RatioJ,DynesP,HammereshC.Thesynthesisandthermal polymerization of 4, 4′-diethynylphenylether[J]. J Polym Sci Polym Chem, 1980, 18(3):1035-1046.
[23]WuXiaole(吴小乐).Synthesis,curekineticsandpropertiesof triphenylthynylsilane[D].Huainan:Anhui University of Science and Technology(安徽理工大学), 2016.
[24]Xu Yuan(徐远). Synthesis,kinetics and property of arylalkynylsilane resin[D]. Huainan:Anhui University of Science and Technology(安徽理工大学), 2017.
[25]TanDexin(谭德新).Preparations,structuresandpropertiesof triphenylethynylsilaneresinsandtheirSiC/C(TiN/C)composite woodceramics[D]. Hefei:Hefei University of Technology(合肥工业大学), 2011.
[26]Tan D, Shi T, Li Z. Synthesis, characterization and non-isothermal curing kinetics of two silicon-containing arylacetylenicmonomers[J].Res Chem Intermed, 2011, 37(8):831-845.
[27]NaktiyokJ,BayrakcekenH,?zerA,etal.Kineticsofthermal decompositionofphospholipidsobtainedfromphosphaterock[J].Fuel Process Technol, 2013, 116(4):158-164.
[28]KissingerH.Reactionkineticsindifferentialthermalanalysis[J].Analytical Chemistry, 1957, 29(11):1702-1706.
[29]OzawaT.Anewmethodofanalyzingthermogravimetricdata[J].Bull Chem Soc Jpn, 1965, 38:1881-1886.
[30]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.
[31]Ren Y, Cheng B, Zhang J, et al. Thermal degradation kinetics of N,N'-di(diethoxythiophosph-oryl)-1,4-phenylenediamine[J].Chem Res Chinese U, 2008, 24(5):628-631.
[32]Vyazovkin S, Wight C. Model-free and model-fitting approaches to kineticanalysisofisothermalandnonisothermaldata[J].Thermochim Acta, 1999, 340/341:53-68.
[33]Díaz-CelorioE,FrancoL,MárquezY,etal.Thermaldegradation studiesonhomopolymersandcopolymersbasedontrimethylene carbonateandglycolideunits[J].ThermochimicaActa,2012,528:23-31.
[34]GaoJ,TangQ,ChenX.Decompositionkineticsandprocess experiments on dolomite[J]. Journal of Functional Materials, 2012,43(23):3194-3196.
[35]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.
[36]Vyazovkin E. Evaluation of activation energy of thermally stimulated solid-statereactionsunderarbitraryvariationoftemperature[J].J Comput Chem, 1997, 18:393-402.
[37]Zhang Laying(张腊莹), Zhu Xinhua(朱欣华), Qing Hui(卿辉), et al. Thermal behavior and non-isothermal decomposition kinetics of3, 4-bis(3', 5'-dinitrophenyl-1'-yl)furoxan[J]. Journalof Solid Rocket Technology(固体火箭技术), 2011, 34(5):623-627.