聚二苯基二苯乙炔基硅烷树脂的制备与非等温热分解
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摘要
以溴乙烷、二苯基二氯硅烷、苯乙炔为原料,通过格利雅反应合成二苯基二苯乙炔基硅烷单体(DPDPES),利用FTIR和~1H-NMR对单体分子结构进行表征。采用热聚合方法制备了聚二苯基二苯乙炔基硅烷树脂(PDPDPES),借助TG-DTG技术研究了PDPDPES的非等温热分解过程,运用模型法对热分解过程进行分析,建立动力学函数,推导出热分解机理,并应用非模型法对热分解机理函数进行验证。实验结果表明,6种分析方法得到的热分解活化能E_a=245.37kJ/mol,指前因子lgA=13.78s~(-1),机理函数式:f(α)=10/23·(1-α)·[-ln(1-α)]~(-1.3);g(α)=[-ln(1-α)]~(2.3)。
Diphenyldiphenylethynylsilane monomer(DPDPES)was synthesized with ethyl bromide,diphenyldichlorosilane and phenylacetylene by Grignard reaction.The molecular structure was characterized by FTIR and ~1H-NMR spectroscopy.The polymer of polydiphenyl(diphenylethynyl)silane(PDPDPES)was also prepared by thermal polymerization.Non-isothermal thermal decomposition process of PDPDPES was studied with TG-DTG technology via model method to get thermal decomposition function and the corresponding mechanism which was further verified by model-free method.Results show that the apparent activation energy and the pre-exponential factor are about E_a =245.37kJ/mol and lgA=13.78s~(-1) obtained by six different kinetic methods,respectively.The mechanism of functions are f(α)=10/23·(1-α)·[-ln(1-α)]~(-1.3) and g(α)=[-ln(1-α)]~(2.3)。
Diphenyldiphenylethynylsilane monomer(DPDPES)was synthesized with ethyl bromide,diphenyldichlorosilane and phenylacetylene by Grignard reaction.The molecular structure was characterized by FTIR and ~1H-NMR spectroscopy.The polymer of polydiphenyl(diphenylethynyl)silane(PDPDPES)was also prepared by thermal polymerization.Non-isothermal thermal decomposition process of PDPDPES was studied with TG-DTG technology via model method to get thermal decomposition function and the corresponding mechanism which was further verified by model-free method.Results show that the apparent activation energy and the pre-exponential factor are about E_a =245.37kJ/mol and lgA=13.78s~(-1) obtained by six different kinetic methods,respectively.The mechanism of functions are f(α)=10/23·(1-α)·[-ln(1-α)]~(-1.3) and g(α)=[-ln(1-α)]~(2.3)。
引文
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[24]ZHANG S,SHI H S,HUANG S W,et al.Dehydration characteristics of struvite-K pertaining to magnesium potassium phosphate cement system in non-isothermal condition[J].Journal of Thermal Analysis and Calorimetry,2013,111(1):35-40.
[25]卢林刚,韩中凯,杨守生.新型无卤阻燃剂双酚S-二(5,5-二甲基-1,3-二氧杂己内磷酸酯)的热分解动力学研究[J].分子科学学报,2010,26(4):261-265.LU L G,HAN Z K,YANG S S.Study on thermal decomposition kinetics of novel halogen-free flame retardant from bisphenol s-bis(5,5-dimethyl-1,3-dioxaphosphorinanyl-2-oxy)[J].Journal of Molecular Science,2010,26(4):261-265.
[26]胡拥鹏,赵旭芳,赵宁宁,等.DNGTz的非等温热分解动力学及热安全性[J].含能材料,2014,22(6):767-773.HU Y P,ZHAO X F,ZHAO N N,et al.Non-isothermal thermal decomposition kinetics and thermal safety of DNGTz[J].Chinese Journal of Energetic Materials,2014,22(6):767-773.
[27]胡荣祖,高胜利,赵凤起,等.热分析动力学[M].2版.北京:科学出版社,2008.55-117.HU R Z,GAO S L,ZHAO F Q,et al.Thermal Analysis Kinetics[M].2nd ed.Beijing:Science Press,2008.55-117.
[2]ZHOU Y,HUANG F,DU L,et al.Synthesis and properties of silicon-containing arylacetylene resins with polyhedral oligomeric silsesquioxane[J].Polymer Engineering&Science,2015,55(2):316-321.
[3]SHEN Y,YUAN Q,HUANG F,et al.Effect of neutral nickel catalyst on cure process of silicon-containing polyarylacetylene[J].Thermochimica Acta,2014,590:66-72.
[4]谭德新,王艳丽,邢宏龙,等.聚苯基三苯乙炔基硅烷的制备及热分解动力学[J].固体火箭技术,2013,36(3):385-389.TAN D X,WANG Y L,XING H L,et al.Preparation and thermal decomposition kinetics of poly(phenyl(triphenylethynyl)silane)s[J].Journal of Solid Rocket Technology,2013,36(3):385-389.
[5]ZHANG J,HUANG J,YU X,et al.Preparation and properties of modified silicon-containing arylacetylene resin with bispropargyl ether[J].Bull Korean Chem Soc,2012,33(11):3706-3710.
[6]MAJI A,HAZRA A,MAITI D.Direct synthesis ofα-trifluoromethyl ketone from(hetero)arylacetylene:design,intermediate trapping,and mechanistic investigations[J].Organic Letters,2014,16(17):4524-4527.
[7]吴永胜,余若冰,朱长进,等.硅烷改性芳基乙炔固化物的耐热性能[J].上海大学学报(自然科学版),2013,19(6):562-566.WU Y S,YU R B,ZHU C J,et al.Heat resistance of cured arylacetylene modified by siloxane[J].Journal of Shanghai University(Natural Science),2013,19(6):562-566.
[8]宋宁.含硅、氮、硼元素耐高温芳基乙炔树脂及其复合材料的研究[D].上海:华东理工大学,2012.SONG N.Study on high-temperature resistant aryl-acetylene resins containing silicon,nitrogen and boron elements and their composites[D].Shanghai:East China University of Science and Technology,2012.
[9]戴泽亮,陈麒,倪礼忠.双(N-间乙炔基苯基邻苯二甲酰亚胺)醚改性甲基二苯乙炔基硅烷[J].复合材料学报,2005,22(5):89-93.DAI Z L,CHEN Q,NI L Z.Di-N-m-accetylenephenylphthalimide-ether modifying methyl-di-phenylacetylene-silane[J].Acta Materiae Compositae Sinica,2005,22(5):89-93.
[10]颜梅,江金强,施伟,等.有机硅耐烧蚀材料的研究进展[J].有机硅材料,2001,15(2):24-27.YAN M,JIANG J Q,SHI W,et al.Research advance of the silicone ablative material[J].Silicone Material,2001,15(2):24-27.
[11]刘衍兵,郭康康,齐会民,等.聚硅烷改性含硅芳炔树脂的耐热性能研究[J].化工新型材料,2010,38(4):84-88.LIU Y B,GUO K K,QI H M,et al.Thermal stability of blends of polysilane and silicon-containing arylacetylene resin[J].New Chemical Materials,2010,38(4):84-88.
[12]KOWNACKI I,ORWAT B,MARCINIEC B,et al.A new and efficient route for the synthesis of alkynyl functionalized silicon derivatives[J].Tetrahedron Letters,2014,55(2):548-550.
[13]LIU H Q,HARROD J F.Copper(I)chloride catalyzed crossdehydrocoupling reactions between silanes and ethynyl compounds a new method for the copolymerization of silanes and alkynes[J].Canadian Journal of Chemistry,1990,68(7):1100-1105.
[14]MAIENTHAL M,HELLMANN M,HABER C P,et al.The preparation of some aryl silanes1[J].Journal of the American Chemical Society,1954,76(24):6392-6393.
[15]ISHIKAWA J,ITOH M.Dehydrogenative coupling between hydrosilanes and alkynes catalyzed by alkoxides,alkylmetals,and metalamides[J].Journal of Catalysis,1999,185(2):454-461.
[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.CHEN M F,ZHOU Q,NI L Z,et al.Synthesis and fluorescence properties of conjugated monomers containing phenylacetylene[J].Polymer Materials Science&Engineering,2013,29(12):1-4.
[17]TAN D,WANG Y,LI Z,et al.Synthesis and cure kinetics of diphenyl(diphenylethynyl)silane monomer[J].Research on Chemical Intermediates,2013,39(7):3427-3440.
[18]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.WANG Y L,TAN D X,YU F,et al.The non-isothermal thermal decomposition process of poly(phenyltri(phenylethynyl)silane)s[J].Journal of Functional Materials,2014,45(21):21040-21044.
[19]SUN Y J,JIANG J C,WANG Y J,et al.Kinetic analysis of biomass and coal mono-pyrolysis as well as co-pyrolysis by CoatsRedfern[J].Chemistry&Industry of Forest Products,2014,34(5):8-14.
[20]YAO X D,FANG R N,PANG H J,et al.Preparation and nonisothermal kinetics analysis of N-[(4-bromo-3,5-difluorine)phenyl]acrylamide[J].Advanced Materials Research,2013,781:580-584.
[21]BLAINE R L,KISSINGER H E.Homer kissinger and the kissinger equation[J].Thermochimica Acta,2012,540:1-6.
[22]杭祖圣,谈玲华,居法银,等.非等温热重分析三聚氰胺热分解动力学[J].分析科学学报,2011,27(3):279-283.HANG Z S,TAN L H,JU F Y,et al.Non-isothermal kinetic studies on the thermal decomposition of melamine by thermogravimetric analysis[J].Journal of Analytical Science,2011,27(3):279-283.
[23]ZHU L,WANG X,WU L,et al.Thermal decomposition properties of cross-linked polycarbonate derived from carbon dioxide,propylene oxide and pyromellitic dianhydride[J].Materials Letters,2014,128:396-399.
[24]ZHANG S,SHI H S,HUANG S W,et al.Dehydration characteristics of struvite-K pertaining to magnesium potassium phosphate cement system in non-isothermal condition[J].Journal of Thermal Analysis and Calorimetry,2013,111(1):35-40.
[25]卢林刚,韩中凯,杨守生.新型无卤阻燃剂双酚S-二(5,5-二甲基-1,3-二氧杂己内磷酸酯)的热分解动力学研究[J].分子科学学报,2010,26(4):261-265.LU L G,HAN Z K,YANG S S.Study on thermal decomposition kinetics of novel halogen-free flame retardant from bisphenol s-bis(5,5-dimethyl-1,3-dioxaphosphorinanyl-2-oxy)[J].Journal of Molecular Science,2010,26(4):261-265.
[26]胡拥鹏,赵旭芳,赵宁宁,等.DNGTz的非等温热分解动力学及热安全性[J].含能材料,2014,22(6):767-773.HU Y P,ZHAO X F,ZHAO N N,et al.Non-isothermal thermal decomposition kinetics and thermal safety of DNGTz[J].Chinese Journal of Energetic Materials,2014,22(6):767-773.
[27]胡荣祖,高胜利,赵凤起,等.热分析动力学[M].2版.北京:科学出版社,2008.55-117.HU R Z,GAO S L,ZHAO F Q,et al.Thermal Analysis Kinetics[M].2nd ed.Beijing:Science Press,2008.55-117.