含硅芳炔树脂/苯并噁嗪/氰酸酯三元聚合体系研究

以双酚A型氰酸酯(BADCy)和含炔丙氧基苯并噁嗪(P-appe)为改性剂,通过与含硅芳炔树脂(PSA)的溶液混合与浓缩制备了含硅芳炔树脂/氰酸酯/苯并噁嗪三元共混体系(PPB),研究了该共混体系的热固化过程、共混树脂的热稳定性和动态力学性能、弯曲性能和冲击性能.结果表明,开环后的苯并噁嗪能催化氰酸酯的环三聚反应,可降低氰酸酯的固化温度;PPB热固化中三嗪环可与噁嗪环反应形成氰酸酯与苯并噁嗪共聚;当PPB树脂中PSA树脂的质量分数为70%时,三元共混树脂浇铸体在氮气中质量损失5%的温度(Td5)高于500oC,玻璃化转变温度高于450oC;BADCy/P-appe改性PSA树脂的三元共混体系相容性好,共混树脂浇铸体PPB-5的弯曲强度较PSA树脂提高了115%,冲击强度提升了104%,断裂面出现明显的韧性断裂特征.     

三(3-乙炔基苯胺)-苯基硅烷改性含硅芳炔树脂的性能

以苯基三氯硅烷、3-氨基苯乙炔为原料,通过胺解反应合成了三(3-乙炔基苯胺)苯基硅烷(SZTA),并通过傅里叶变换红外光谱(FT-IR)和核磁共振氢谱(1 H-NMR)表征了其结构。随后通过熔融共混的方法制备了不同配比的改性含硅芳炔树脂(PSA/SZTA),借助黏度计、流变仪、差示扫描量热仪(DSC)、电子万能试验机、热重分析仪(TG)等考察了改性树脂的工艺性能、固化特性、弯曲性能、热稳定性能和热解动力学等。结果显示,引入SZTA后,改性PSA树脂的黏度降低62%;改性PSA树脂固化物的弯曲强度最高达到34.6MPa,比未改性的PSA树脂提高了约54%;且改性树脂固化物在N_2中的5%热失重温度(T_(d5))均高于500℃,保持了良好的耐热性能;PSA/SZTA-20固化物的热解表观活化能(Ea)的平均值为249kJ/mol。     

全内炔型含硅聚三唑树脂的制备与性能

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%。     

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

设计并制备了一种新型乙炔基封端聚醚酰亚胺大分子偶联剂(BDA-K),探究了其对石英纤维(QF)/含硅芳炔(PSA)复合材料界面增强增韧的效果.在常温下,加入大分子偶联剂的复合材料层间剪切强度、弯曲强度和缺口冲击强度分别提高了54.1%,59.0%和23.8%;在250℃时,层间剪切强度和弯曲强度保留率分别达到89.0%和89.6%,500℃时保留率分别达到63.3%和67.9%.傅里叶变换红外光谱和X光电子能谱分析结果表明,BDA-K参与PSA的交联固化,与QF发生有效化学键合;热重分析(TGA)结果表明,由于BDA-K的分子结构中引入耐热官能团酰亚胺环等,使其大分子偶联剂的T_(d5)达到489℃;扫描电子显微镜(SEM)结果表明,柔软的大分子层提供了适中的界面结合,使强度和韧性都得到提高.     

含噁嗪环硅烷偶联剂对石英纤维/含硅芳炔复合材料性能的影响

从石英纤维(QF)、含硅芳炔树脂(PSA)分子结构特点出发,设计并合成了一种含有噁嗪环和端炔的新型硅烷偶联剂(BCA),并以BCA改善QF/PSA复合材料的界面性能。采用差示扫描量热分析(DSC)、红外光谱分析(FT-IR)、X-射线电子能谱(XPS)及扫描电镜(SEM)等测试手段表征了BCA与QF/PSA复合材料的相互作用和界面改性效果。结果表明:BCA能够分别与PSA和QF形成良好的化学键合,改善复合材料的界面黏结;经w=2.0%的BCA处理后,QF/PSA复合材料的层间剪切强度、弯曲强度分别较未处理前提高了69.1%和68.8%。     

乙炔基封端液晶-含硅芳炔共聚树脂的固化机理

将热致性乙炔基封端液晶单体(MPBE)与含硅芳炔树脂(PSA)进行共聚,制得乙炔基封端液晶改性含硅芳炔树脂(PSA-MPBE)。采用FT-IR在线表征了PSA-MPBE树脂固化过程的结构变化,用裂解-气相色谱-质谱联用仪(Py-GC-MS)分析了其高温裂解产物,研究了其固化机理,用偏光显微镜(POM)、扫描电子显微镜(SEM)和透射电子显微镜(TEM)分析了共混树脂的相结构、断裂形貌和微观结构。结果表明:MPBE与PSA发生了共聚反应,使介晶域固定在交联网络中,形成结构均匀的以介晶相为小岛的海岛结构,PSA-MPBE树脂的断裂行为从典型的脆性断裂转变为微塑性断裂。     

含氟苯并噁嗪-含硅芳炔改性树脂的制备与性能

采用溶剂法合成了一系列带有活性基团的含氟苯并噁嗪(烯丙基含氟苯并噁嗪(BOZF-1)、苯乙炔基含氟苯并噁嗪(BOZF-2)和炔丙基含氟苯并噁嗪(BOZF-3)),并将其与含硅芳炔树脂(PSA)进行共混改性,研究不同氟苯并噁嗪(BOZF)的结构与质量分数对改性树脂性能的影响.采用差示扫描量热法(DSC)研究BOZF/PS...     

硅炔杂化树脂改性有机硅树脂及其复合材料的性能

用一种硅炔杂化树脂聚（甲基硅烷-二乙炔基苯）（PSP）改性有机硅树脂（HS）,通过FT—IR和TGA研究了树脂体系的固化反应及耐热性,并对制备的复合材料进行力学性能、耐热性能和介电性能研究。结果表明：当HS与PSP的质量比为5：5时综合性能最优,树脂体系在氮气氛围下质量损失5％时的温度（T幽）为691℃,1000℃时质量保留率为88％;HS—PSP树脂短切玻纤复合材料冲击强度为21kJ／m^2,弯曲强度为65MPa,200℃时的弯曲强度高温保留率为78％,介电常数为4．6,介电损耗因数为7．9×10,体积电阻为6．7×10^13Ω。改性后的复合材料具有优异的力学、耐热和介电性能。     

基于甲基三苯乙炔基硅烷的新型聚三唑树脂的制备与性能

首先采用格氏试剂法合成了甲基三苯乙炔基硅烷(MTPES),通过傅里叶变换红外光谱(FT-IR)、核磁共振氢谱(1 H-NMR)对其结构进行了表征。然后以MTPES和4,4’-二叠氮甲基联苯(BAMBP)为原料制备了新型聚三唑树脂(MPTA)。利用FT-IR和差示扫描量热(DSC)研究了MPTA树脂的固化行为,通过动态力学热分析(DMA)和热重分析(TG)研究了炔基与叠氮基配比对树脂热性能的影响,并通过测试凝胶时间随贮存时间的变化研究了树脂及其四氢呋喃(THF)溶液的贮存稳定性。结果表明,固化后的树脂玻璃化转变温度(Tg)达到236℃,在氮气中的5%热失重温度(T_(d5))在320℃左右。MPTA树脂在35℃和25℃下分别贮存7d和20d后,100℃下树脂的凝胶时间分别为40min和25min,MPTA树脂的THF溶液在同样条件下贮存28d后,凝胶时间分别为54min和61min,具有比现有聚三唑树脂更好的贮存稳定性。单向T700碳纤维-MPTA复合材料常温下的弯曲强度为1 660 MPa,弯曲模量为129 GPa,150℃下的弯曲强度保留率为70%。     

聚甲基二间苯二乙炔基硅烷改性二氧化双环戊二烯环氧树脂及其复合材料的性能

用聚甲基二间苯二乙炔基硅烷树脂（PSA）改性二氧化双环戊二烯（R-122环氧树脂）得到R-122/PSA树脂体系,并以该树脂为基体制备了玻璃纤维复合材料。通过FT-IR、DSC和TGA研究了R-122/PSA树脂的固化反应及其耐热性能,同时研究了R-122/PSA基复合材料的力学性能、耐热性能、介电性能和耐水性能。结果表明：改性树脂在高温下保持了良好的耐热性能,mPSA/mR-122=0.2的固化物在800°C下质量保留率比纯R-122树脂的提高了30%。所制备的复合材料常温下弯曲强度达到735 MPa,220°C下的弯曲强度达到418.4 MPa,不仅保留了良好的力学性能,而且耐热性能得到了很好的提升,同时其浸泡96 h后的吸水率仅为0.65%,耐水性能优异。     

Synthesis and properties of sulfur‐contained poly(silylene arylacetylene)s

Poly(silylene arylacetylene) (PSA) is a kind of poly(arylacetylene) silicon‐containing resins with excellent heat resistance and good mechanical performances. In this article, the sulfur atom is introduced into the main chain of the PSA molecule to obtain a sulfur‐containing poly(silylene arylacetylene), named S‐PSA. By Williamson and Sonogashira reactions, bis(4‐ethynylphenyl)sulfide and bis(4‐ethynylphenyl)sulfone were synthesized. Thereafter, through Grignard reagent way, the poly(silylene ethynylene phenylene sulfide phenylene ethynylene) (PSESE) and poly(silylene ethynylene phenylene sulfone phenylene ethynylene) (PSESO₂E) were synthesized from bis(4‐ethynylphenyl)sulfide, bis(4‐ethynylphenyl)sulfone, and methylphenyl dichlorosilane. Poly(silylene ethynylene phenylene sulfoxide phenylene ethynylene) (PSESOE) was synthesized by the oxidation of PSESE. The structures and properties of these resins were characterized and the mechanical properties of the T300 reinforced composites were tested. The results show that the novel S‐PSA resins have excellent heat resistance and good mechanical properties, and could be used as resin matrices for high‐performance composites in high‐tech fields. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 2324–2332     

Surface modification of boron nitride by bio‐inspired polydopamine and different chain length polyethylenimine co‐depositing

We established a novel, easy, and versatile method of obtaining diverse and controllable interphases between epoxy resin and fillers. The method involved the co‐deposition of polydopamine (PDA) and polyethyleneimine (PEI) with different molecular lengths on boron nitride (BN) surface. The obtained PDA/PEI‐modified BN composites showed significantly improved mechanical properties, including tensile strength, toughness, and elongation at break. For example, the tensile strength, fracture toughness, and elongation at break of EP composite increased by 51%, 132%, and 170% compared with EP when the PEI molecular weight was 10 000, respectively. These results suggested that the interphases between BN and EP matrix can be adjusted by changing the molecular lengths of grafted modifiers, thereby offering a new method for the reasonable designing and exploitation of the BN‐based composite materials.     

有机硅改性双酚A型环氧树脂研究

采用二氯二甲基硅烷 (DMS) ,或DMS与α ,ω 二氯聚二甲基硅氧烷 (DPS)的混合物来改性双酚A型环氧树脂 ,通过对固化物的冲击强度、拉伸强度、断裂伸长率和玻璃化转变温度 (Tg)的测定 ,探讨了改性方法、有机硅组成与含量等对材料性能的影响 .结果表明 ,用 5 7phr的DMS改性时 ,树脂固化物的冲击强度达2 0 2kJ m2 ,拉伸强度达 6 7 0MPa ,断裂伸长率达 11 2 9% ,Tg 达 16 8 0℃ ;分别比未改性时提高了 9 4kJ m2 ,2 1 1MPa ,5 4 %以及 32 6℃ .而用 0 7phrDMS +10phrDPS共同改性时 ,除Tg 和拉伸强度略有上升外 ,冲击强度达到了 31 6kJ m2 ,断裂伸长率达到 81 6 % ,分别比纯环氧提高了 2 0 8kJ m2 和 75 7% .     

端羟基丁腈橡胶增韧环氧树脂研究

本文研究了端羟基丁腈橡胶(HTBN)对环氧树脂的增韧作用。加入10—20phr的HTBN,环氧树脂性能可以大幅度提高,粘接碳钢剪切强度30MPa,冲击强度9×10~(-2)J/cm~2,浇注试样抗张强度61MPa,伸长10％,玻璃化温度115℃;不加HTBN的环氧树脂固化物,剪切强度24MPa,冲击强度34×10~(-2)J/cm~2,抗张强度30MPa,伸长5％,玻璃化温度124℃。 本文还通过DSC、SEM研究观察到增韧环氧树脂的两相结构。     

原位制备PEI/SiO2复合材料及其改性环氧树脂的研究

在N,N-二甲基乙酰胺/四氢呋喃(DMAc/THF)混合溶剂中,在正硅酸乙酯(TEOS)存在条件下,通过溶胶-凝胶法原位制备了聚醚酰亚胺(PEI)/SiO2复合材料.在该复合材料中,当SiO2含量低于20 wt％时,透射电镜(TEM)和扫描电镜(SEM)的观察表明,SiO2纳米粒子可以均匀分散,粒径可在80～300 n...     

Bio-based tri-functional epoxy resin (TEIA) blend cured with anhydride (MHHPA) based cross-linker: Thermal,mechanical and morphological characterization

A novel renewable resource based tri-functional epoxy resin from itaconic acid (TEIA) was blended with petroleum based epoxy resin (DGEBA) and fabricated at different ratios. Then, it was by thermally cured with methylhexahydrophthalic anhydride (MHHPA) in presence of 2-methylimidazole (2-MI) catalyst. The tensile, modulus, strength of virgin epoxy resin (41.97 MPa, 2222 MPa) increased to 47.59 MPa, 2515 MPa, respectively, with the addition of 30% of TEIA. The fracture toughness parameter, critical stress intensity factor (K_IC) revealed enhancement of toughness in the TEIA bio-based blends system. The thermomechanical properties of TEIA (tri-functional epoxy resin from itaconic acid) modified petroleum-epoxy networks were investigated by differential scanning calorimetry (DSC), thermogravimetric analysis (TGA) and dynamic mechanical analysis (DMA). The fracture morphology was also studied by the scanning electron microscopy and atomic force microscopy respectively.     

Preparation of Low-dielectric Permittivity Polyimide Resins with High Surface Activity from Chemically Bonded Hyperbranched Polysiloxane

Thermosetting resin matrix is the key component of advanced wave-transparent composites,where low dielectric constant,excellent processability,high thermal stability,as well as good bonding ability are required for resins.Herein,we prepared a series of phenylethynyl terminated polyimide(PI)resins by grafting amine-functionalized hyperbranched polysiloxane(HBPSi)to PI chains during the in situ polymerization.The effects of HBPSi on the processability of oligomers,molecular packing,thermal stability,dielectric property and bonding ability to reinforce Kevlar fibers of the cured PI/HBPSi composite resins have been examined in detail.The dielectric constants of the cured composite resins were greatly reduced from 3.29 to 2.19 without compromising its processability and thermal stability.Meanwhile,the 10 wt％HBPSi-containing PI resin demonstrated better bonding ability to reinforce fibers with the interfacial shear strength(IFSS)of 37.64 MPa,compared with that of neat PI-6 matrix(27.34 MPa),and better adhesion to metal with the lap shear strength of 10.48 MPa,50％higher than that of neat resin PI-6(6.98 MPa).These resultant PI/HBPSi composite resins exhibit excellent comprehensive properties,indicating their great potential as low-dielectric constant resin matrix in radar radome.