聚十二烷基三苯乙炔基硅烷树脂的合成与介电性能
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摘要
以十二烷基三氯硅烷和苯乙炔为原料,通过格利雅反应制备了十二烷基三苯乙炔基硅烷(DTPES)。采用傅里叶变换红外光谱(FTIR)和核磁共振波谱(~1H-NMR、~(13)C-NMR和~(29)Si-NMR)对DTPES单体结构进行了表征。借助示差扫描量热仪(DSC)确定了单体的固化工艺,并通过热聚合方法制备了聚十二烷基三苯乙炔基硅烷树脂(PDTPES),通过矢量网络分析仪和介电常数测试仪分析了树脂在不同频率下的介电性能。结果表明:树脂在不同频率下具有较低的介电常数和损耗角正切值,是一种新颖的透波材料用树脂基体。
The dodecyl(triphenylethynyl)silane(DTPES) was synthesized by Grignard reaction of dodecyltrichlorosilane and phenylacetylene. The chemical structure of DTPES was characterized by Fourier transform infrared spectroscopy(FTIR) and nuclear magnetic resonance spectroscopy(~1 H-NMR,~(13) C-NMR and ~(29) Si-NMR). The curing process of the DTPES was analyzed by Differential Scanning Calorimetry(DSC). The corresponding polydodecyl(triphenylethynyl)silane resin(PDTPES)was also prepared by thermal polymerization,and the dielectric property was discussed under different frequency by vector network analyzer and dielectric constant tester. The results showed that PDTPES exhibited lower dielectric constant and dielectric loss. It was a novel wave-transparent resin matrix.
The dodecyl(triphenylethynyl)silane(DTPES) was synthesized by Grignard reaction of dodecyltrichlorosilane and phenylacetylene. The chemical structure of DTPES was characterized by Fourier transform infrared spectroscopy(FTIR) and nuclear magnetic resonance spectroscopy(~1 H-NMR,~(13) C-NMR and ~(29) Si-NMR). The curing process of the DTPES was analyzed by Differential Scanning Calorimetry(DSC). The corresponding polydodecyl(triphenylethynyl)silane resin(PDTPES)was also prepared by thermal polymerization,and the dielectric property was discussed under different frequency by vector network analyzer and dielectric constant tester. The results showed that PDTPES exhibited lower dielectric constant and dielectric loss. It was a novel wave-transparent resin matrix.
引文
[1]Itoh M,Inoue K,Iwata K,et al.A heat-resistant silicon-based polymer[J].Adv.Mater.,1997,9(15):1187-1190.
[2]Guo K,Li P,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]Wrackmeyer B,Bayer S,Tok O,et al.Alkynylsilanes and alkynyl(vinyl)silanes.Synthesis,molecular structures and multinuclear magnetic resonance study[J].Zeitschrift Für Naturforschung B,2010,65(6):725-744.
[7]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.
[8]Tan D X,Wu X L,Wang Y L,et al.Synthesis,characterization and curing behavior of propyl-tri(phenylethynyl)silane[J].Iran Polym.J.,2016,25(8):687-695.
[9]Kim C,Jeong K,Jung I.Progress toward limiting generation of dendritic ethynylsilanes(Ph C≡C)4-nMenSi(n=0-2)[J].J.Polym.Sci.Polym.Chem.,2000,38(15):2749-2759.
[10]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.
[11]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.
[12]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.
[13]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.
[14]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.
[15]Tan D X,Wang Y L,Li Z,et al.Synthesis and cure kinetics of diphenyl(diphenylethynyl)silane monomer[J].Res.Chem.Intermed,2013,39(7):3427-3440.
[16]Tan D X,Wu X L,Wang Y L,et al.Synthesis,characterization and curing behavior of methyl-tri(phenylethynyl)silane[J].Res.Chem.Intermed,2016,42(5):4669-4681.
[17]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.
[18]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.
[19]Sastri S,Armistead J,Keller T.Cure kinetics of a multisubstituted acetylenic monomer[J].Polymer,1995,36(7):1449-1454.
[20]吴小乐.三苯乙炔基硅烷树脂的合成、固化动力学及性能分析[D].安徽理工大学,2016.
[21]徐远.芳炔基硅烷单体的制备、动力学分析及其聚合物性能研究[D].安徽理工大学,2017.
[22]刘顺华,刘军民,董星龙,等.电磁波屏蔽及吸波材料[M].北京:化学工业出版社,2013,84-85.
[2]Guo K,Li P,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]Wrackmeyer B,Bayer S,Tok O,et al.Alkynylsilanes and alkynyl(vinyl)silanes.Synthesis,molecular structures and multinuclear magnetic resonance study[J].Zeitschrift Für Naturforschung B,2010,65(6):725-744.
[7]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.
[8]Tan D X,Wu X L,Wang Y L,et al.Synthesis,characterization and curing behavior of propyl-tri(phenylethynyl)silane[J].Iran Polym.J.,2016,25(8):687-695.
[9]Kim C,Jeong K,Jung I.Progress toward limiting generation of dendritic ethynylsilanes(Ph C≡C)4-nMenSi(n=0-2)[J].J.Polym.Sci.Polym.Chem.,2000,38(15):2749-2759.
[10]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.
[11]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.
[12]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.
[13]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.
[14]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.
[15]Tan D X,Wang Y L,Li Z,et al.Synthesis and cure kinetics of diphenyl(diphenylethynyl)silane monomer[J].Res.Chem.Intermed,2013,39(7):3427-3440.
[16]Tan D X,Wu X L,Wang Y L,et al.Synthesis,characterization and curing behavior of methyl-tri(phenylethynyl)silane[J].Res.Chem.Intermed,2016,42(5):4669-4681.
[17]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.
[18]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.
[19]Sastri S,Armistead J,Keller T.Cure kinetics of a multisubstituted acetylenic monomer[J].Polymer,1995,36(7):1449-1454.
[20]吴小乐.三苯乙炔基硅烷树脂的合成、固化动力学及性能分析[D].安徽理工大学,2016.
[21]徐远.芳炔基硅烷单体的制备、动力学分析及其聚合物性能研究[D].安徽理工大学,2017.
[22]刘顺华,刘军民,董星龙,等.电磁波屏蔽及吸波材料[M].北京:化学工业出版社,2013,84-85.