SiO_2中空微球改性含硅芳炔树脂及其复合材料的结构与性能
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摘要
采用SiO_2中空微球对含硅芳炔树脂(PSAC)进行改性,制备了SiO_2/PSAC复合材料,以改善PSAC固化后质脆的缺点,提高PSAC基复合材料的力学性能,拓展PSAC在航空航天领域的应用。对SiO_2/PSAC复合材料和石英纤维布增强SiO_2/PSAC(QF-SiO_2/PSAC)复合材料的结构与性能进行了研究,采用SEM分析SiO_2/PSAC树脂浇铸体和QF-SiO_2/PSAC复合材料断面微观结构,并分析SiO_2的增韧机制。采用DMA和TGA分析了SiO_2/PSAC复合材料耐热性能和热稳定性,虽然SiO_2会导致树脂耐热性能略有下降,但其中空结构使树脂具有优异介电性能。当SiO_2的添加量达2wt%时,SiO_2/PSAC树脂浇铸体弯曲强度达22.3 MPa,失重5%温度为551℃,1 000℃残留率为86.5%;QF-2SiO_2/PSAC复合材料的弯曲强度为298.3MPa,弯曲模量达31.0GPa,分别提高了27.5%、59.0%;当SiO_2添加量为5wt%时,QF-5SiO_2/PSAC复合材料的剪切强度提高了16.0%。
SiO_2 hollow microspheres modified Si-containing arylacetylene resin(SiO_2/PSAC)casting was prepared to ameliorate the brittleness of cured Si-containing arylacetylene resin and to improve the mechanical properties of the SiO_2/PSAC resin casting and to meet the need of the application in the field of aeronautics and astronautics.The structure and properties of the SiO_2/PSAC resin casting and quartz fiber reinforced SiO_2/PSAC(QF-SiO_2/PSAC)composites were investigated.The microstructure of SiO_2/PSAC resin castings and QF-SiO_2/PSAC composites were observed by SEM,and the toughening mechanism of SiO_2 was analyzed.The heat resistance and thermal stability of SiO_2/PSAC composites were studied by DMA and TGA.The heat resistance of the resin decreased slightly,but the porous structure made the resin excellent in dielectric properties.Meanwhile,when the content of SiO_2 is added to 2 wt%,the flexural strength of SiO_2/PSAC resin casting is 22.3 MPa.The temperature of decomposition(Td5)is 551℃ and the char yield at 1 000℃ is 86.5%;the flexural strength of QF-2 SiO_2/PSAC composite is298.3 MPa,and the modulus reaches 31.0 GPa,which increases by 27.5% and 59.0%,respectively;When the content of SiO_2 is 5 wt%,the shear strength of QF-5 SiO_2/PSAC composite increases by 16.0%.
SiO_2 hollow microspheres modified Si-containing arylacetylene resin(SiO_2/PSAC)casting was prepared to ameliorate the brittleness of cured Si-containing arylacetylene resin and to improve the mechanical properties of the SiO_2/PSAC resin casting and to meet the need of the application in the field of aeronautics and astronautics.The structure and properties of the SiO_2/PSAC resin casting and quartz fiber reinforced SiO_2/PSAC(QF-SiO_2/PSAC)composites were investigated.The microstructure of SiO_2/PSAC resin castings and QF-SiO_2/PSAC composites were observed by SEM,and the toughening mechanism of SiO_2 was analyzed.The heat resistance and thermal stability of SiO_2/PSAC composites were studied by DMA and TGA.The heat resistance of the resin decreased slightly,but the porous structure made the resin excellent in dielectric properties.Meanwhile,when the content of SiO_2 is added to 2 wt%,the flexural strength of SiO_2/PSAC resin casting is 22.3 MPa.The temperature of decomposition(Td5)is 551℃ and the char yield at 1 000℃ is 86.5%;the flexural strength of QF-2 SiO_2/PSAC composite is298.3 MPa,and the modulus reaches 31.0 GPa,which increases by 27.5% and 59.0%,respectively;When the content of SiO_2 is 5 wt%,the shear strength of QF-5 SiO_2/PSAC composite increases by 16.0%.
引文
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[21]黄赤,汪波,秦岩,等.空心玻璃微球含量对环氧复合泡沫塑料性能的影响[J].复合材料学报,2016,33(8):1630-1637.HUANG C,WANG B,QIN Y,et al.Effects of hollow glass microsphere content on properties of epoxy syntactic foams[J].Acta Materiae Compositae Sinica,2016,33(8):1630-1637(in Chinese).
[22]吕婕,姜丽,吴金剑,等.聚氨酯预聚体改性双酚A型氰酸酯树脂的研究[J].材料导报,2015,29(24):36-39.LV J,JIANG L,WU J J,et al.Study of polyurethane prepolymer modified bisphenol A cyanate ester resins[J].Mterials Review,2015,29(24):36-39(in Chinese).
[23]吴金剑,谢佳武,王志娟,等.F-48环氧树脂改性双酚A型氰酸酯树脂的研究[J].材料导报,2014,28(14):91-94.WU J J,XIE J W,WANG Z J,et al.Study of F-48epoxy resin modified bisphenol A cyanate ester resins[J].Materials Review,2014,28(14):91-94(in Chinese).
[24]袁慧五,饶秋华.无机填料对低粘度高性能环氧树脂性能的影响[J].热固性树脂,2007,22(6):33-35.YUAN H W,RAO Q H.The influence of inorganic filler on the performances of high property and low viscosity epoxy resin[J].Thermosetting Resin,2007,22(6):33-35(in Chinese).
[25]赵彦生,王华,党在清,等.无机纳米粒子增韧聚丙烯及其机理研究[J].现代塑料加工应用,2006,18(6):36-38.ZHAO Y S,WANG H,DANG Z Q,et al.The research of polypropylene toughened by inorganic nanoparticles and toughening mechanisms[J].Modern Plastics Processing and Applications,2006,18(6):36-38(in Chinese).
[26]高峰,矫桂琼,宁荣昌,等.层间颗粒增韧复合材料层压板的损伤阻抗特性[J].复合材料学报,2005,22(2):116-120.GAO F,JIAO G Q,NING R C,et al.Damage resistance of the composite laminates with interlayer thermoplastic particles[J].Acta Materiae Compositae Sinica,2005,22(2):116-120(in Chinese).
[27]武光顺.碳纤维表面纳米结构修饰及其MPSR复合材料性能研究[D].哈尔滨:哈尔滨工业大学,2016.WU G S.Study on the nanostructure based on the surface of carbon fiber and the properties of CF/MPSR composites[D].Harbin:Harbin Institute of Technology,2016(in Chinese).
[28]赵春宝,张楠楠.氰酸酯/环氧树脂/苯基三硅羟基倍半硅氧烷复合材料研究[J].化工新型材料,2012,40(11):40-42.ZHAO C B,ZHANG N N.Study on cyanate ester/epoxy resin/trisilanolphenyl polyhedral oligomeric silsesquioxane(POSS)composites[J].New Chemical Materials,2012,40(11):40-42(in Chinese).
[2]AND S K,OKITA K,KAKIGANO T,et al.Thermosetting mechanism study of poly[(phenylsilylene)ethynylene-1,3-phenylenee-thynylene]by solid-state NMR spectroscopy and computational chemistry[J].Macromolecules,1998,31(9):2804-2808.
[3]BOURY B,CORRIU R J P,MURAMATSU H.Organisation and reactivity of silicon-based hybrid materials with various cross-linking levels[J].New Journal of Chemistry,2002,26(8):981-988.
[4]WANG F,ZHANG J,HUANG J,et al.Synthesis and characterization of poly(dimethylsilyleneet-hynylenephenyleneethynylene)terminated with phenylacetylene[J].Polymer Bulletin,2006,56(1):19-26.
[5]ZHANG J,HUANG J,ZHOU W,et al.Fiber reinforced silicon-containing arylacetylene resin composites[J].eXPRESS Polymer Letters,2007,1(12):831-836.
[6]张玲玲,高飞,周围,等.含硅氢基团甲基芳炔树脂的合成及表征[J].过程工程学报,2009,9(3):574-579.ZHANG L L,GAO F,ZHOU W,et al.Synthesis and characterization of poly(arylacetylene)resins containing methylsilylene groups[J].The Chinese Journal of Process Engineer2009,9(3):574-579(in Chinese).
[7]OGASAWARA T,ISHIKAWA T,ITOH M,et al.Carbon fiber reinforced composites with newly developed silicon containing polymer MSP[J].Advanced Composite Materials,2001,10(4):319-327.
[8]YIN G,ZHANG J,WANG C,et al.Synthesis and characterization of new disilane-containing arylacetylene resin[J].Polymers,2008,8(1):771-777.
[9]LEVASSORT C,JOUSSE F,DELNAUD L,et al.Poly(ethynylene phenylene ethynylene polysiloxene(silylene))and methods for preparing same:United States,6872795[P].2005-3-29.
[10]王沪东,郭康康,周晖,等.聚硼硅氮烷杂化芳炔基树脂制备及抗热氧化性能[J].复合材料学报,2016,33(5):962-969.WANG H D,GUO K K,ZHOU H,et al.Preparation and thermal-oxidation resistance of polyborosilazane hybrid polyarylacetylene resin[J].Acta Materiae Compositae Sinica,2016,33(5):962-969(in Chinese).
[11]GUO K K,LI P,ZHU Y P,et al.Thermal curing and degradation behaviour of silicon-containing arylacetylene resins[J].Polymer Degradation and Stability,2016,131:98-105.
[12]齐会民,王光后,张健,等.含硅芳炔树脂的改性及其性能研究[C]//第十五届全国复合材料学术会议论文集.哈尔滨:中国力学学会,2009:335-339.QI H M,WANG G H,ZHANG J,et al.The performance of modified silicon-containing acetylene resin[C]//15th National Conference on Composite Materials.Harbin:Chinese Society of Theoretical and Applied Mechanics,2008:335-339(in Chinese).
[13]李晓燕,任圆,甘文君.热固性树脂的增韧进展[J].热固性树脂,2010,25(5):41-46.LI X Y,REN Y,GAN W J.Progress in toughening thermosetting resins[J].Thermosetting Resin,2010,25(5):41-46(in Chinese).
[14]汤乐旻,周燕,田鑫,等.改性含硅芳炔树脂及其复合材料性能研究[J].玻璃钢/复合材料,2012(6):41-46.TANG L Y,ZHOU Y,TIAN X,et al.Properties of siliconarylacetylene resin and its composite materials[J].Fiber Reinforced Plastics/Composites,2012(6):41-46(in Chinese).
[15]高金淼,齐会民,张建,等.新型含硅芳炔树脂及其复合材料的性能[J].化工新型材料,2008,36(12):45-46.GAO J M,QI H M,ZHANG J,et al.Properties of new siliconaryl-acetylene resin and its composite materials[J].New Chemical Materials.2008,36(12):45-46(in Chinese).
[16]韩梦娜,郭康康,王帆,等.乙炔基封端液晶-含硅芳炔共聚树脂的固化机理[J].功能高分子学报,2017,30(3):279-289.HAN M N,GUO K K,WANG F,et al.Curing mechanism of acetylene terminated liquid crystal and silicon-containing arylacetylene copolymer resin[J].Journal of Functional Polymers,2017,30(3):279-289(in Chinese).
[17]李孟宇,马雅婷,赵蕾,等.纳米SiO2改性环氧树脂复合材料的热稳定性及使用寿命[J].复合材料学报,2017,34(11):2421-2427.LI M Y,MA Y T,ZHAO L,et al.Thermal stability and service life of nano-SiO2 modified epoxy composites[J].Acta Materiae Compositae Sinica,2017,34(11):2421-2427(in Chinese).
[18]郑艳红,蔡楚江,沈志刚,等.微纳米SiO2/PP复合材料增强增韧的实验研究[J].复合材料学报,2007,24(6):19-25.ZHENG Y H,CAI C J,SHEN Z G,et al.Toughening and strengthening of micro-and nano-SiO2/PP composites[J].Acta Materiae Compositae Sinica,2007,24(6):19-25(in Chinese).
[19]吴聪,陈南春,吴志能,等.改性介孔硅-ESO/聚丙烯三元体系复合材料增强增韧机制[J].复合材料学报,2017,34(4):723-729.WU C,CHEN N C,WU Z N,et al.Reinforcing and toughening mechanisms of modified diatomite-epoxy soybean oil/polypropylene composites[J].Acta Materiae Compositae Sinica,2017,34(4):723-729(in Chinese).
[20]曾宏,张安强.催化异氰酸酯基与羟基反应选择性的研究进展[J].聚氨酯工业,2017,32(5):1-4.ZENG H,ZHANG A Q.The selectivity of catalysts for the reaction of isocyanate and hydroxyl groups[J].Polyurethane Industry,2017,32(5):1-4(in Chinese).
[21]黄赤,汪波,秦岩,等.空心玻璃微球含量对环氧复合泡沫塑料性能的影响[J].复合材料学报,2016,33(8):1630-1637.HUANG C,WANG B,QIN Y,et al.Effects of hollow glass microsphere content on properties of epoxy syntactic foams[J].Acta Materiae Compositae Sinica,2016,33(8):1630-1637(in Chinese).
[22]吕婕,姜丽,吴金剑,等.聚氨酯预聚体改性双酚A型氰酸酯树脂的研究[J].材料导报,2015,29(24):36-39.LV J,JIANG L,WU J J,et al.Study of polyurethane prepolymer modified bisphenol A cyanate ester resins[J].Mterials Review,2015,29(24):36-39(in Chinese).
[23]吴金剑,谢佳武,王志娟,等.F-48环氧树脂改性双酚A型氰酸酯树脂的研究[J].材料导报,2014,28(14):91-94.WU J J,XIE J W,WANG Z J,et al.Study of F-48epoxy resin modified bisphenol A cyanate ester resins[J].Materials Review,2014,28(14):91-94(in Chinese).
[24]袁慧五,饶秋华.无机填料对低粘度高性能环氧树脂性能的影响[J].热固性树脂,2007,22(6):33-35.YUAN H W,RAO Q H.The influence of inorganic filler on the performances of high property and low viscosity epoxy resin[J].Thermosetting Resin,2007,22(6):33-35(in Chinese).
[25]赵彦生,王华,党在清,等.无机纳米粒子增韧聚丙烯及其机理研究[J].现代塑料加工应用,2006,18(6):36-38.ZHAO Y S,WANG H,DANG Z Q,et al.The research of polypropylene toughened by inorganic nanoparticles and toughening mechanisms[J].Modern Plastics Processing and Applications,2006,18(6):36-38(in Chinese).
[26]高峰,矫桂琼,宁荣昌,等.层间颗粒增韧复合材料层压板的损伤阻抗特性[J].复合材料学报,2005,22(2):116-120.GAO F,JIAO G Q,NING R C,et al.Damage resistance of the composite laminates with interlayer thermoplastic particles[J].Acta Materiae Compositae Sinica,2005,22(2):116-120(in Chinese).
[27]武光顺.碳纤维表面纳米结构修饰及其MPSR复合材料性能研究[D].哈尔滨:哈尔滨工业大学,2016.WU G S.Study on the nanostructure based on the surface of carbon fiber and the properties of CF/MPSR composites[D].Harbin:Harbin Institute of Technology,2016(in Chinese).
[28]赵春宝,张楠楠.氰酸酯/环氧树脂/苯基三硅羟基倍半硅氧烷复合材料研究[J].化工新型材料,2012,40(11):40-42.ZHAO C B,ZHANG N N.Study on cyanate ester/epoxy resin/trisilanolphenyl polyhedral oligomeric silsesquioxane(POSS)composites[J].New Chemical Materials,2012,40(11):40-42(in Chinese).