氨基POSS/环氧树脂有机无机杂化材料的动态力学性能

为了提高环氧树脂(EP)的综合性能,以含氨基官能团的笼型倍半硅氧烷(POSS)作为EP的改性剂,得到有机-无机POSS改性EP杂化树脂;然后以4,4′-二氨基二苯基砜(DDS)为固化剂对杂化树脂进行固化,得到有机-无机杂化材料。重点考察了POSS含量对杂化材料动态力学性能的影响。结果表明:不同杂化材料体系均呈单相结构,POSS在EP基体中分散较均匀,说明两者间相容性良好;随着POSS含量的不断增加,杂化材料体系的玻璃化转变温度(Tg)增大,与传统杂化材料不同的是损耗峰强度随POSS含量增加而降低,但损耗峰宽度几乎不变。     

多氨基倍半硅氧烷改性环氧树脂E-51固化动力学及热性能

以氯甲基笼型倍半硅氧烷(CM-POSS)为原料,与乙二胺通过取代反应合成多氨基倍半硅氧烷(POSS-NH2),并通过红外光谱(FT-IR)对产物进行表征.采用动态差示扫描量热法(DSC)和热失重分析(TGA)研究多氨基倍半硅氧烷( POSS-NH2)/环氧树脂(E-51)/二氧基二苯基砜(DDS)和E-51体系的固化动力学和热性能.结果表明:杂化树脂的固化反应活化能较大,POSS-NH2的加入提高了固化杂化树脂的热性能.     

甲基笼型倍半硅氧烷/CE杂化复合材料的力学性能

以甲基笼型倍半硅氧烷(POSS)作为氰酸酯树脂(CE)的改性剂,制备出一种POSS/CE杂化复合材料。研究了杂化复合材料中POSS用量对CE结构及力学性能的影响,同时采用红外光谱(FT-IR)法对不同POSS/CE体系的反应性进行了研究。结果表明:POSS的加入对CE的反应性影响不大,有利于POSS/CE杂化体系固化工艺的制定;当杂化体系中w(POSS)=5%时,材料的冲击强度(9.7 kJ/m2)相对最大(提高了49%),弯曲强度(90 MPa)也相对较高,说明适量的POSS对CE具有明显的增韧、增强作用。     

新型双马来酰亚胺改性环氧树脂体系性能研究

用含二氮杂萘联苯结构的双马来酰亚胺(DHPZ-BM I)与4,4'-二氨基二苯砜(DDS)为复合固化剂固化环氧树脂(E-51)。采用示差扫描量热仪(DSC)研究了该体系的固化反应动力学,求得固化反应表观活化能Ea=63.28 kJ/mol,碰撞因子A=1.55×106s-1,反应级数n=0.89,该体系与链延长型双马来酰亚胺PPEK-BM I(DP=15)/DDS/E-51体系的固化反应动力学数据几乎相同,证明二者的固化反应过程相同。采用热失重分析仪(TGA)分析研究了上述2种固化体系的热分解动力学,前者的热分解活化能达215.04 kJ/mol,为后者的1.5倍以上,说明DHPZ-BM I/DDS/E-51是1种热稳定性能良好的耐高温环氧树脂体系。     

环氧树脂/胺化酰亚胺潜伏性固化体系的制备

为了深入了解新型环氧树脂/胺化酰亚胺潜伏性固化体系的使用条件,采用差示扫描量热（DSC）技术考察了E–51型环氧树脂/脂肪族胺化酰亚胺体系的非等温固化反应过程,研究了体系的固化条件及固化物性能。结果表明：E–51与固化剂的物质的量比为1∶0.1;体系的固化条件为固化150℃/2 h,后固化180℃/1 h。树脂试样制备工艺简单,无挥发性有机溶剂,树脂混合物贮存稳定性好。体系固化反应平稳且放热量较少,完全固化后的树脂试样具有良好的耐水性、耐热性和物理机械性能。     

EP/POSS/SiO2纳米复合材料性能研究

以自制的两种不同黏度的环氧基倍半硅氧烷(POSS)为改性剂,对双酚A型环氧树脂(EP)/4,4’–二氨基二苯砜(DDS)进行改性,制备EP/POSS杂化材料。再以纳米SiO2为填料制备了EP/POSS/SiO2纳米复合材料。结果表明,与EP相比,杂化材料和纳米复合材料的弯曲强度和弯曲弹性模量都有所提高,其中纳米复合材料(分别添加低黏度和高黏度的POSS)的弯曲弹性模量分别提高了15.03%和9.44%,添加高黏度的POSS和纳米SiO2后其杂化材料和纳米复合材料体系的弯曲强度均有所提高,杂化材料和纳米复合材料的最大分解温度和在高温时的热残留量都有所提高。     

POSS-环氧树脂纳米分子杂化材料的固化动力学分析

采用非等温DSC对胺丙基低聚倍半硅氧烷(NH2-POSS)/环氧树脂(E51)/4,4-二氨基二苯砜(DDS)体系的固化过程进行研究。利用外推法确定体系的固化工艺条件,通过Kissinger和Ozawa方程计算体系的活化能,研究了n级和自催化模型对体系的适用性。结果表明,NH2-POSS/E51/DDS体系的活化能为68.01kJ/mol,且自催化动力学模型适用于固化体系。     

超支化环氧树脂的分子模拟及其杂化树脂的性能

利用一步法合成了4种不同分子质量的低黏度液态超支化环氧树脂,并利用该树脂与双酚A型环氧树脂(E-51)杂化复合,研究其固化物的冲击性能.杂化树脂的冲击性能随超支化环氧树脂含量和/或分子质量的增加先增加后下降,具有最大值;当相对分子质量在3 400左右、质量分数为12%左右时,体系的冲击强度达到最大值,与纯E-5l相比提高了208.8%.利用FT-IR和分子模拟技术对超支化环氧树脂的性质和结构进行了表征,采用sEM对杂化树脂的断裂表面进行表征.并解释了增韧机理.     

双酚A型环氧树脂/芳香胺固化体系的固化动力学研究

分别以4,4‘-二氨基二苯甲烷（DDM）和4,4‘-二氨基二苯砜（DDS）为固化剂，采用非等温差示扫描量热法（DSC）研究了E-44和E-51两种双酚A型环氧树脂的固化反应动力学。收集与分析了在25～350℃范围内分别以5、10、15、20℃/min的升温速率进行固化的反应参数，然后采用Starink法计算得到不同环氧固化体系的表观活化能。同时，借助各固化体系的动态流变性能，分析了双酚A型环氧树脂/芳香胺固化体系的固化反应机理，并选用双参数自催化模型计算了各固化体系的反应速率方程。研究结果表明：当环氧固化体系的固化剂不同时，采用DDM作为固化剂的环氧固化体系（E-44/DDM、E-51/DDM），其表观活化能均低于添加DDS固化剂的环氧体系；选用同种固化剂（DDM或DDS）时，E-51树脂体系的表观活化能均低于E-44树脂固化体系。反应速率方程结果显示，该双参数自催化模型与实际试验结果的吻合性良好，可用于描述双酚A型环氧树脂/芳香胺固化体系的固化历程。     

聚芳醚酮增韧混合环氧树脂体系研究 Ⅰ.反应动力学及增韧机理

本文阐述了采用耐热的热塑性聚合物——聚芳醚酮(PEK—C)对4,4’—二氨基二苯基砜(DDS)固化AG—80/双酚A型环氧树脂体系的增韧作用。用DSC法研究该体系的固化反应及其动力学,用拉力机和TMA法测定固化树脂的性能,以及用DMS和SEM研究体系的相分离现象和试样的断裂面形貌。结果表明:两种环氧树脂混合后对DDS的固化反应存在某种协同作用;PEK—C的加入对其固化反应没有影响;PEK—C含量在2～10％范围内,固化产物的断裂伸长率和断裂能随PEK—C含量的增加而提高,但模量和Tg基本不变;PEK—C对AG—80/E—44的增韧效果优于AG—80/E—51体系;改性体系的动态力学性能研究显示出相分离特征。用SEM观察结果进一步证买了PEK—C的增韧作用。     

环氧基POSS/PAMAM杂合材料的制备及性能研究

以3-缩水甘油基氧丙基三甲氧基硅烷(EPTMS)为原料,合成得到了八官能团缩水甘油醚-多面体低聚倍半硅氧烷(简称POSS-EP)。采用4代树型端氨基聚酰胺-胺(PAMAM)作为POSS-EP和双酚A型环氧树脂(DGEBA)共混物的固化剂,制备了5个环氧基POSS/PAMAM杂化材料。通过动态差示扫描量热仪(DSC),研究了环氧和PAMAM的固化反应动力学。通过DSC、热重分析(TGA)、拉力和冲击测试,对环氧基POSS/PAMAM杂化材料的热性能和力学性能进行了研究。结果表明,该环氧基POSS/PAMAM杂化材料具有优良的热性能和力学性能。     

Hybrid nanocomposites based on novolac resin and octa(phenethyl) polyhedral oligomeric silsesquioxanes (POSS): miscibility, specific interactions and thermomechanical properties

Hybrid nanocomposites were prepared via solution blending of octaphenethyl POSS into novolac resin. The resulted hybrid blends were investigated by Fourier-transformed infrared spectra (FTIR), polarized optical microscopy (POM), wide X-ray diffraction and differential scanning calorimetry (DSC). FTIR results showed that there existed intermolecular hydrogen bond between the hydroxyl groups of the phenolic resin and POSS siloxane groups, which could promote POSS to disperse well in the polymer matrix up to 20 wt% POSS loading. At higher POSS loading, POSS would aggregate and lead to macrophase separation, which was demonstrated by POM, DSC and WXRD. Finally, hexamethylene tetramine was used to cure the novolac blends to form hybrid network phenolic nanocomposites. Dynamic mechanical analysis results showed that the storage modulus of the hybrid networks was improved up to 20 wt% POSS loading; the T _g was increased with increasing POSS content and higher than that of the control phenolic resin except that 5 wt% POSS loading. Thermo gravimetric analysis showed that the thermal stability of hybrid networks was also enhanced with the incorporation of POSS.     

POSS/CE杂化复合材料的制备与介电性能研究

为制备介电常数(ε)低、介电损耗因子(tanδ)小的集成电路板用树脂基体,以笼型倍半硅氧烷(POSS)对双酚A型氰酸酯(CE)树脂进行改性,制备出一种POSS/CE无机-有机杂化复合材料。着重探讨了POSS用量和后处理工艺等对POSS/CE树脂体系介电性能的影响。结果表明:当w(POSS)=2%(相对于CE单体质量而言)、后处理工艺为240℃/3 h时,改性体系的介电性能相对最好,其测试频率为60 MHz时的ε(为2.9)和tanδ(为0.004 5)分别比纯CE树脂降低了9.4%和35.7%;该改性体系的表观活化能为51.9 kJ/mol。     

Thermal conductivity and thermal properties of POSS/polytriazole organic–inorganic hybrid material

To decrease the thermal conductivity of polytriazole‐based fiber reinforced composites, an organic–inorganic POSS/polytriazole hybrid resin was obtained. The influences of various proportions of POSS on thermal conductivity and the thermal properties of hybrid materials were emphatically investigated. The results show that POSS incorporation resulted in not only decreased thermal conductivity but also increased T_g and thermal decomposition temperature. The enhancement was ascribed to the nanoscale effect of POSS structure and the fact that the POSS framework has a high heat resistance property. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41967.     

Epoxy/benzoxazinyl POSS nanocomposite resin with low dielectric constant and excellent thermal stability

Benzoxazinyl modified polyhedral oligomeric silsesquioxane (BZPOSS) is successfully synthesized and used to prepare nanocomposites with bisphenol A type epoxy resin (E51). The differential scanning calorimetry results showed the curing peak temperature of E51/BZPOSS blend decrease to 242°C, suggesting the high catalytic activity of BZPOSS to the polymerization of E51. The scanning electron microscope micrographs of poly(E51/BZPOSS)s and silicon element distribution maps given by EDS both demonstrated homogeneous dispersion of BZPOSS. Dielectric properties tests confirmed the dielectric constant can be reduced by the introduction of BZPOSS, which is attributed to the nano-pores from the cage structure of POSS. When 20 wt% BZPOSS was added, the dielectric constant decreased to 2.28 at 1 MHz. Meanwhile, DMA and TGA results indicated the thermal stability and heat resistance of poly(E51/BZPOSS)s at high temperature increased with the increase of BZPOSS, which is due to the increase of the crosslinking density and the change of crosslinking structure of copolymer.     

Synthesis of EP‐POSS mixture and the properties of EP‐POSS/epoxy,SiO2/epoxy,and SiO2/EP‐POSS/epoxy nanocomposite

The hybrid material of EP‐POSS mixture was synthesized by the hydrolysis and condensation of (γ‐glycidoxypropyl) trimethoxysilane. A series of binary systems of EP‐POSS/epoxy blends, epoxy resin modified by silica nanoparticles (SiO₂/epoxy), and ternary system of SiO₂/EP‐POSS/epoxy nanocomposite were prepared. The dispersion of SiO₂ in the matrices was evidenced by transmission electron micrograph, and the mechanical properties, that is, flexural strength, flexural modulus, and impact strength were examined for EP‐POSS/epoxy blends, SiO₂/epoxy, and SiO₂/EP‐POSS/epoxy, respectively. The fractured surface of the impact samples was observed by scanning electron micrograph. Thermogravimetry analysis were applied to investigate the different thermal stabilities of the binary system and ternary system by introducing EP‐POSS and SiO₂ to epoxy resin. The results showed that the impact strength, flexural strength, and modulus of the SiO₂/EP‐POSS/epoxy system increased around by 57.9, 14.1, and 44.0% compared with the pure epoxy resin, T_i, T_max and the residues of the ternary system were 387°C, 426°C, and 25.2%, increased remarkably by 20°C, 11°C and 101.6% in contrast to the pure epoxy resin, which was also higher than the binary systems. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 810‐819, 2013     

环氧树脂/POSS杂化材料力学性能和耐热性研究

以自行合成的环氧基倍半硅氧烷（POSS）为改性剂,分别对环氧树脂139S/六氢苯酐和环氧树脂BE 188EL/六氢苯酐进行改性,制备环氧树脂/POSS杂化材料。力学性能分析结果表明,两种杂化材料的冲击强度和弯曲强度都有明显的提高,冲击强度分别提高了57.45 %和32.26 %,弯曲强度分别提高了9.23 %和5.07 %。热性能分析结果表明,两种杂化材料在高温时的热残留量都有所提高,分别提高了50.19 %和20.16 %。两种杂化材料的热膨胀系数也得到了降低,即热稳定性得到了提高。