全内炔型含硅聚三唑树脂的制备与性能
|
摘要
采用格氏试剂法制备了苯乙炔封端型含硅芳炔(PTPSA),并采用傅里叶转换红外光谱(FT-IR)、核磁共振氢谱(~1 H-NMR)和差示扫描量热法(DSC)表征了其结构。以PTPSA和1,3,5-三叠氮甲基-2,4,6-三甲基苯(TAMIMB)为原料,制备了新型全内炔型含硅聚三唑树脂(P-PTA3)。利用FT-IR、DSC、动态力学分析(DMA)和热重分析(TGA)研究了树脂的固化行为及热性能,通过测试凝胶时间随贮存时间的变化研究了树脂溶液的贮存稳定性。结果表明:树脂固化物的玻璃化转变温度(Tg)可达304℃,失重率5%时的温度(Td5)达330℃以上。P-PTA3树脂溶液在35℃和25℃下贮存时间分别超过20d和40d。单向碳纤维T700/P-PTA3复合材料常温下的弯曲强度为1 875MPa,弯曲模量为135.5GPa,180℃下弯曲强度保留率为75%。
Silicon-containing arylacetylene terminated by phenylacetylene(PTPSA)was synthesized by Grignard reaction,and the molecular structure was characterized and confirmed by Fourier transforminfrared spectroscopy(FT-IR),nuclear magnetic resonance spectroscopy(1 H-NMR)and differential scanning calorimeter(DSC).A novel polytriazole(P-PTA3)resin was further synthesized through 1,3-dipolar cycloaddition reaction between PTPSA and 1,3,5-tris(azidomethyl)-2,4,6-trimethylbenzene(TAMTMB).The unidirectional T700 carbon fiber reinforced P-PTA3 resin composite(T700/P-PTA3)was prepared by compression molding.The curing behaviors of the resin were monitored by FT-IR and DSC.The effects of molar ratio of monomers on the thermal properties of P-PTA3 resin were studied by dynamic thermos mechanical analysis(DMA)and thermogravimetric(TG)analysis.The storage stability of the resin and its tetrahydrofuran(THF)solution were evaluated by measuring the variation of the gel time against storage time.The gel time was measured under 90 ℃.The results show that the glass transition temperature(Tg)of the cured P-PTA3 resin is 304℃and 5% weight loss temperature(Td5)is341℃as tested in nitrogen atmosphere(the molar ratio of the alkynyl and triazo is 1.1∶1.0),and Td5 of the samples with different molar ratios of the cured P-PTA3 resins is higher than 330 ℃.The P-PTA3 resin and its THF solution can be stored for more than 20 dand 40 dat 35 ℃ and 25 ℃,respectively.Correspondingly,the gel time of the resins at 90℃is 24 min and 42 min,respectively,which presents a better storage stability than the currently existing polytriazole resin solution at the same storage temperature.The flexural strength and flexural modulus of T700/P-PTA3 composite at room temperature was 1 875 MPa,and 135.5 GPa,respectively,while the retention rate of bending strength was 75%under180℃.
Silicon-containing arylacetylene terminated by phenylacetylene(PTPSA)was synthesized by Grignard reaction,and the molecular structure was characterized and confirmed by Fourier transforminfrared spectroscopy(FT-IR),nuclear magnetic resonance spectroscopy(1 H-NMR)and differential scanning calorimeter(DSC).A novel polytriazole(P-PTA3)resin was further synthesized through 1,3-dipolar cycloaddition reaction between PTPSA and 1,3,5-tris(azidomethyl)-2,4,6-trimethylbenzene(TAMTMB).The unidirectional T700 carbon fiber reinforced P-PTA3 resin composite(T700/P-PTA3)was prepared by compression molding.The curing behaviors of the resin were monitored by FT-IR and DSC.The effects of molar ratio of monomers on the thermal properties of P-PTA3 resin were studied by dynamic thermos mechanical analysis(DMA)and thermogravimetric(TG)analysis.The storage stability of the resin and its tetrahydrofuran(THF)solution were evaluated by measuring the variation of the gel time against storage time.The gel time was measured under 90 ℃.The results show that the glass transition temperature(Tg)of the cured P-PTA3 resin is 304℃and 5% weight loss temperature(Td5)is341℃as tested in nitrogen atmosphere(the molar ratio of the alkynyl and triazo is 1.1∶1.0),and Td5 of the samples with different molar ratios of the cured P-PTA3 resins is higher than 330 ℃.The P-PTA3 resin and its THF solution can be stored for more than 20 dand 40 dat 35 ℃ and 25 ℃,respectively.Correspondingly,the gel time of the resins at 90℃is 24 min and 42 min,respectively,which presents a better storage stability than the currently existing polytriazole resin solution at the same storage temperature.The flexural strength and flexural modulus of T700/P-PTA3 composite at room temperature was 1 875 MPa,and 135.5 GPa,respectively,while the retention rate of bending strength was 75%under180℃.
引文
[1] HUISGEN R.1,3-Dipolar cycloadditions:Past and future[J].Angewandte Chemie International Edition,1963,2(10):565-598.
[2] HUISGEN R.Kinetics and mechanism of 1,3-dipolar cycloaddition[J].Angewandte Chemie International Edition,1963,2(11):633-645.
[3] KATRITZKY A R,MEHER N,CIARAMITAR D,et al.Preparation and characterization of 1,2,3-triazole-cured polymers from endcapped azides and alkynes[J].Journal of Polymer Science Part A:Polymer Chemistry,2008,46(1):238-256.
[4] SONG S M,CHO K,PARK C E,et al.Synthesis and characterization of water-soluble polymeric adhesion promoter for epoxy resin/copper joints[J].Journal of Applied Polymer Science,2002,85(10):2202-2210.
[5] HUYNH N,BOTTLE S E,SCHWEINSBERG D P,et al.Studies on alkyl esters of carboxybenzotriazole as inhibitors for copper corrosion[J].Corrosion Science,2002,44(6):1257-1276.
[6] ACCURSO A A,DELANEY M,O’BRIEN J,et al.Improved metal-adhesive polymers from copper(Ⅰ)-catalyzed azide-alkyne cycloaddition[J].Chemistry:A European Journal,2014,20:10710-10719.
[7] HELMS B,MYANR J,L HAWEKER C J,et al.Dendronized linear polymers via“click chemistry”[J].Journal of American Chemical Society,2004,126(46):15020-15021.
[8] LEE J W,KIM J H,KIM B K,et al.Convergent synthesis of PAMAM dendrimers using click chemistry of azidefunctionalized PAMAM dendrons[J].Tetrahedron,2006,62(39):9193-9200.
[9] DKAZ D D,PUNNA S,HOLZER P,et al.Click chemistry in materials synthesis:1.Adhesive polymers from coppercatalyzed azide-alkyne cycloaddition[J].Journal of Polymer Science Part A:Polymer Chemistry,2004,42(17):4392-4403.
[10] YANG Y W,HENTSCHEL J,CHEN Y C,et al.“Clicked”fluoropolymer elastomers as robust materials for potential microfluidic device applications[J].Journal of Materials Chemistry,2012,22(3):1100-1106.
[11] XU Z Y,WAN L Q,DU L,et al.Synthesis and characterization of a novel thermostable polyether-based elastomeric polytriazole via click reaction[J].Soft Materials,2013,11(3):245-260.
[12] TIAN J J,WAN L Q,HUANG J Z,et al.Synthesis and characterization of a novel polytriazole resin with lowtemperature curing character[J].Polymers for Advanced Technologies,2007,18(7):556-561.
[13] E Y P,WAN L Q,HUANG F R,et al.New heat-resistant polytriazole adhesives:Investigation of adhesion of polytriazole resins to metal[J].Journal of Adhesion Science and Technology,2013,27(16):1767-1777.
[14]吴长伟,杜磊,唐磊,等.新型共聚聚三唑树脂体系的研究[J].绝缘材料,2013,46(4):1-4.
[15]韩冬菁,万里强,汪洋洋,等.含联炔多炔丙基化合物的合成及聚三唑树脂的制备[J].高分子材料科学与工程,2017,33(1):28-33.
[16]叶绿原,万里强,马明明,等.基于酚醛结构的聚三唑树脂及其复合材料[J].复合材料学报,2018,35(3):1-7.
[17]许建文.聚三唑树脂聚合过程的研究[D].上海:华东理工大学,2014:27-33.
[18]罗永红,扈艳红,万里强,等.N,N,N′N′-四炔丙基-4,4′-二氨基-二苯甲烷与4,4′-联苯二苄叠氮固化动力学研究[J].高等学校化学学报,2006,27(1):170-173.
[19] LIU R P,WAN L Q,HUANG F R,et al.Kinetic study of the thermal polymerization reactions between diazide and internal diyne[J].Internal Journal of Chemical Kinetics,2015,47(2):124-132.
[20]黎迎春,万里强,等.基于甲基三苯乙炔基硅烷新型聚三唑树脂的制备与性能[J].功能高分子学报,2017,30(2):233-239.
[2] HUISGEN R.Kinetics and mechanism of 1,3-dipolar cycloaddition[J].Angewandte Chemie International Edition,1963,2(11):633-645.
[3] KATRITZKY A R,MEHER N,CIARAMITAR D,et al.Preparation and characterization of 1,2,3-triazole-cured polymers from endcapped azides and alkynes[J].Journal of Polymer Science Part A:Polymer Chemistry,2008,46(1):238-256.
[4] SONG S M,CHO K,PARK C E,et al.Synthesis and characterization of water-soluble polymeric adhesion promoter for epoxy resin/copper joints[J].Journal of Applied Polymer Science,2002,85(10):2202-2210.
[5] HUYNH N,BOTTLE S E,SCHWEINSBERG D P,et al.Studies on alkyl esters of carboxybenzotriazole as inhibitors for copper corrosion[J].Corrosion Science,2002,44(6):1257-1276.
[6] ACCURSO A A,DELANEY M,O’BRIEN J,et al.Improved metal-adhesive polymers from copper(Ⅰ)-catalyzed azide-alkyne cycloaddition[J].Chemistry:A European Journal,2014,20:10710-10719.
[7] HELMS B,MYANR J,L HAWEKER C J,et al.Dendronized linear polymers via“click chemistry”[J].Journal of American Chemical Society,2004,126(46):15020-15021.
[8] LEE J W,KIM J H,KIM B K,et al.Convergent synthesis of PAMAM dendrimers using click chemistry of azidefunctionalized PAMAM dendrons[J].Tetrahedron,2006,62(39):9193-9200.
[9] DKAZ D D,PUNNA S,HOLZER P,et al.Click chemistry in materials synthesis:1.Adhesive polymers from coppercatalyzed azide-alkyne cycloaddition[J].Journal of Polymer Science Part A:Polymer Chemistry,2004,42(17):4392-4403.
[10] YANG Y W,HENTSCHEL J,CHEN Y C,et al.“Clicked”fluoropolymer elastomers as robust materials for potential microfluidic device applications[J].Journal of Materials Chemistry,2012,22(3):1100-1106.
[11] XU Z Y,WAN L Q,DU L,et al.Synthesis and characterization of a novel thermostable polyether-based elastomeric polytriazole via click reaction[J].Soft Materials,2013,11(3):245-260.
[12] TIAN J J,WAN L Q,HUANG J Z,et al.Synthesis and characterization of a novel polytriazole resin with lowtemperature curing character[J].Polymers for Advanced Technologies,2007,18(7):556-561.
[13] E Y P,WAN L Q,HUANG F R,et al.New heat-resistant polytriazole adhesives:Investigation of adhesion of polytriazole resins to metal[J].Journal of Adhesion Science and Technology,2013,27(16):1767-1777.
[14]吴长伟,杜磊,唐磊,等.新型共聚聚三唑树脂体系的研究[J].绝缘材料,2013,46(4):1-4.
[15]韩冬菁,万里强,汪洋洋,等.含联炔多炔丙基化合物的合成及聚三唑树脂的制备[J].高分子材料科学与工程,2017,33(1):28-33.
[16]叶绿原,万里强,马明明,等.基于酚醛结构的聚三唑树脂及其复合材料[J].复合材料学报,2018,35(3):1-7.
[17]许建文.聚三唑树脂聚合过程的研究[D].上海:华东理工大学,2014:27-33.
[18]罗永红,扈艳红,万里强,等.N,N,N′N′-四炔丙基-4,4′-二氨基-二苯甲烷与4,4′-联苯二苄叠氮固化动力学研究[J].高等学校化学学报,2006,27(1):170-173.
[19] LIU R P,WAN L Q,HUANG F R,et al.Kinetic study of the thermal polymerization reactions between diazide and internal diyne[J].Internal Journal of Chemical Kinetics,2015,47(2):124-132.
[20]黎迎春,万里强,等.基于甲基三苯乙炔基硅烷新型聚三唑树脂的制备与性能[J].功能高分子学报,2017,30(2):233-239.