聚离子液体修饰碳纳米管及其对环氧树脂力学性能的影响

为改善多壁碳纳米管(MWCNTs)在环氧树脂(EP)中的分散性和界面性质,以1-乙烯基-3-丁基咪唑六氟磷酸盐([VBIM]PF6)为单体合成聚离子液体(PIL),用于MWCNTs的表面改性.用热重分析(TG),拉曼光谱(Raman)和扫描电镜(SEM)对改性碳纳米管(PIL-CNTs)进行了表征.结果表明,PIL可吸附在MWCNTs表面且不改变MWCNTs的电子结构.与原始MWCNTs相比,PIL-CNTs在丙酮中的分散性更好.在EP中加入0.5 wt%的PIL-CNTs,以4,4'-二氨基二苯甲烷(DDM)为固化剂制备环氧树脂固化物.动态力学(DMA)研究表明,PIL-CNTs提高了EP的储能模量,玻璃化温度比纯EP和MWCNTs/EP分别提高了5.6℃和3.3℃;PILCNTs/EP的拉伸强度,弯曲强度和冲击强度较纯EP分别提高了35.2%,26.4%和45.0%.拉伸断面的SEM可看出PIL-CNTs在复合材料中的分散性和与环氧树脂基体的界面结合力均优于原始MWCNTs.     

Mechanical and Thermal Properties and Morphology of Epoxy Resins Modified by a Silicon Compound

A silicon compound (GAPSO) was synthesized to modify the diglycidyl ether of bisphenol-A (DGEBA). The chemical structure of GAPSO was confirmed using FT-IR, ²⁹Si NMR and GPC. The mechanical and thermal properties and morphologies of the cured epoxy resins were investigated by impact testing, tensile testing, differential scanning calorimetry and environmental scanning electron microscopy. The impact strength and tensile strength were both increased by introducing GAPSO, meanwhile the glass transition temperature (T_g ) was not decreased and the morphologies of the fracture surfaces show that the compatibility of GAPSO with epoxy resin was very good and the toughening follows the pinning and crack tip bifurcation mechanism. The high functional groups in GAPSO can react during the curing process, and chemically participate in the crosslinking network. GAPSO is thus expected to improve the toughness of epoxy resin, meanwhile maintain the glass transition temperature.     

化学结构变化对刚棒状环氧树脂相行为和热力学性能的影响

用线性酚醛树脂(PN)和4-氨基苯基氨基砜(SAA)作为固化剂, 与刚性棒状环氧树脂联苯环氧(DGEBP)、四甲基联苯环氧(DGETMBP)和传统双酚A环氧树脂(DGEBA)分别进行固化. 研究了固化剂和环氧树脂化学结构的改变对热固网络相行为和热力学性能的影响. 结果表明, 刚性环氧网络比传统的DGEBA具有更好的热力学性能. DGEBP可形成不同类型的取向网络, 而取向态的类型也直接影响了热固网络的热力学性能. 用扫描电镜(SEM)观察不同网络体系的断裂面结构, 发现取向的刚性棒状环氧网络的断裂面呈韧性断裂, 而其它无定形环氧网络则呈典型的脆性断裂.     

含氟嵌段聚合物改性环氧树脂性能研究

用AGET ATRP法制备含环氧基的含氟嵌段聚合物聚甲基丙烯酸六氟丁酯-b-聚甲基丙烯酸缩水甘油酯(PHFMA-b-PGMA),将其用于双酚A型环氧树脂改性.表面性能测试表明,PHFMA-b-PGMA改性环氧涂膜的表面疏水疏油性优于纯环氧,且经长时间水浸泡、丁酮浸泡或高温热处理后,其表面稳定性仍表现优良.热性能测试表明,PHFMA-b-PGMA改性环氧的热稳定性优于纯环氧.机械性能测试结果表明,用PHFMA-bPGMA改性环氧有助于韧性提高,与断裂面SEM测试结果相吻合.     

聚醚接枝聚硅氧烷共聚物改进环氧树脂表面性能的研究

共混改性;形态;聚醚接枝聚硅氧烷共聚物改进环氧树脂表面性能的研究     

咪唑盐聚合物与环氧树脂复合的研究

用红外光谱和X射线光电子能谱研究了咪唑与金属铜的反应,证明反应生成了咪唑铜盐聚合物,此聚合物能在铜表面形成极薄的保护层,并能引发环氧树脂开环聚合固化,用DSC对咪唑铜盐聚合物引发苯基缩水甘油醚的动力学进行了初步研究,同时测定了界面复合的剪切强度。     

Characterization in the Toughening Process of CTBN Modified Epoxy Resins Induced by Electron Beam Radiation

Epoxy resins are widely utilized as high performance thermosetting resins for many industrial applications but characterized by a relatively low toughness. Electron beam (EB) curing of polymer resins has a number of advantages over conventional thermal curing, such as shorter curing time, low energy consumption, low cure temperature, dimensional stability, reduced manufacturing cost. In the present work liquid carboxyl-terminated butadiene acrylonitrile (CTBN) copolymers containing 8% acrylonitrile is added at different contents to improve the toughness of diglycidyl ether of bisphenol A (DGEBA) epoxy resins using triarylsulfonium hexafluoroanimonate as a photointiator. The EB irradiation was conducted 5 kGy to 250 kGy in nitrogen. The physics properties of CTBN modified epoxy resins were examined by determine gel content, DMA (dynamic mechanical analysis), UTM (Instron model 4443), SEM (scanning electron microscopy).     

Synthesis and Property of Flame Retardant Epoxy Resins Modified with 2-（Diphenylphosphinyl）-l,4-benzenediol

2-（Diphenylphosphinyl）-1,4-benzenediol（DPO-HQ） was synthesized by the reaction of diphenylphos- phine oxide（DPO） with 1,4-benzoquinone（BQ）, and characterized by Fourier transform infrared（FTIR）, and nuclear magnetic resonance（1H NMR, 13C NMR, 31p NMR） spectrometries. The thermal stability of DPO-HQ was investi- gated by thermogravimetric analysis（TGA）. Flame retardant epoxy resin was synthesized based on DPO-HQ. The thermal properties and burning performance of cured epoxy resins were measured by differential scanning calorime- try（DSC）, thermogravimetric analysis（TGA）, limited oxygen index（LOI） and vertical burning test（UL-94V）. The morphologies of cured epoxy resins after combustion were investigated by scanning electron microscopy（SEM） and electron probe microanalysis（EPMA）. Moreover, the thermal stability（both in air and in N2） of DPO-HQ and its cured epoxy resin was compared with that of 10-（2,5-dihydroxyphenyl）-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10- oxide（DOPO-HQ） and its cured epoxy resin. The thermal stability of DPO-HQ is comparable with that of DOPO-HQ, while the thermal stability of cured epoxy resin based on DPO-HQ is better than that based on DOPO-HQ.     

丁腈羟增韧环氧树脂形态与力学性能

研究了丁腈羟增韧环氧树脂的力学性能和形态结构，丁腈羟的用量、丁腈羟中丙烯腈的含量、固化条件对所形成的微区尺寸都有较大影响，并进一步影响固化物的力学性能。     

高性能可回收环氧树脂及其复合材料的制备与性能研究

采用戊二酸酐为固化剂,乙酰丙酮锌为催化剂制备了一种综合性能优异的高性能可回收环氧树脂.系统研究了固化剂及催化剂含量对树脂结构、热学及动态性能的影响,实现了树脂组成的优化设计.基于酯交换反应的热可逆性,制备的vitrimer树脂通过物理热压方法可实现良好回收,力学强度保持率可达80%.采用RTM工艺制备的碳纤维织物增强vitrimer树脂复合材料表现出与传统热固性树脂基复合材料相当的力学性能,并且通过醇类溶剂热降解树脂的方法,可实现复合材料中碳纤维的高效无损回收,回收率近100%.     

松香改性酚醛环氧树脂的合成与表征

以松香,环氧氯丙烷,甲醛及苯酚等为主要原料,合成了一种新型的环氧树脂。通过正交实验法确定了环氧化反应的最佳实验条件,即环氧化温度90℃,碱用量13 g,催化剂为cat 1,其最佳用量为0.018 mol,环氧氯丙烷的用量为50 g,碱浓度为30%(以上数值均以松香用量为70 g时计)。在最佳实验条件下合成得到了松香改性酚醛环氧树脂(简称RAPE),并用HPLC、FT-IR、NMR对其进行结构表征。结果表明,得到的RAPE其环氧值为0.28 mol/100g,平均聚合度约为3.4,酚羟基和树脂酸上的羧基基本反应完全,得到一种新型的缩水甘油醚型和缩水甘油酯型的环氧树脂。     

环氧/粘土纳米复合材料的形成机理与性能

粘土／聚合物纳米复合材料由于具有优良的物理力学性能和特殊功能而倍受关注。实验证明,粘土也很容易被环氧树脂插层,并在固化过程中剥离,得到纳米复合材料。本文重点综述了粘土／环氧纳米复合材料的形成机理,结构形态和力学性能,并对该类材料的应用前景进行了展望。     

碳纤维三向织物/环氧树脂复合材料的制备与力学性能

选择不同纱线间距[即二经(纬)纱之间的中心距]尺寸的碳纤维三向织物,采用热压成型技术制备了碳纤维三向织物/环氧树脂复合材料.研究了纱线间距及样品裁剪角度等对力学性能的影响,并与碳纤维二向织物/环氧树脂复合材料的力学性能进行对比.结果表明,随着纱线间距尺寸从2 mm增加到6 mm,0°方向断裂强度从221. 7 MPa下降到148. 1 MPa,撕裂强力从1000 N下降到600 N; 90°方向断裂强度从50. 0MPa下降到22. 1 MPa,撕裂强力从330 N下降到100 N;顶破强力从424 N下降到216 N.这些力学性能的逐渐降低是单位面积的碳纤维增强体含量减少和织物的孔洞增大共同作用的结果.纱线间距为2 mm的碳纤维三向织物复合材料在0°(以纬纱为基准),30°,45°,60°和90°方向的断裂强度分别为221. 7,48. 5,44. 3,227. 7和50. 0 MPa,即断裂强度在0°和60°方向大于在30°,45°及90°方向.由三向织物的编织原理可知,0°与60°方向完全相同,因此其断裂强度相似,且样品中有一组纱线与外加载荷平行,对形变破坏具有一定的约束作用,而...     

聚醚链段长度对氨基聚醚-环氧树脂力学性能的影响

以柔性端氨基聚醚(BATPE)和双酚A环氧树脂(DGEBA)为原料, 制备了无微相分离结构的无定型AB交联热固性树脂. 测试了3种不同聚乙二醇(PEG)链段长度(M_PE)的BATPE-DGEBA环氧树脂固化产物的应力-应变曲线、动态力学温度谱和冲击断面形貌. 结果表明, 在环氧树脂交联网络中引入两端与DGEBA化学连接的PEG链段能避免微相分离结构的生成, 有利于提高DGEBA链段的应变松弛速率. 增加M_PE, 一方面能降低环氧树脂固化产物的玻璃化转变温度和室温下的刚度和拉伸强度, 增加韧性(包括冲击强度和拉伸韧性)、断裂应变和模量损耗因子; 另一方面也能提高固化产物在低温下的储存模量. 优化M_PE可制备出在中低温下同时具有优异的拉伸强度、模量、断裂应变和冲击性能的BATPE-DGEBA环氧树脂.     

Synthesis and Properties of Silphenylene-containing Epoxy Resins with High UV-stability

Two novel silphenylene-containing cycloaliphatic epoxy resins, 1,4-di [2-(3, 4-epoxycyclohexylethyl) dimethylsilyl] benzene (DEDSB) and 1,3,5-tri [2-(3, 4-epoxycyclohexylethyl) dimethylsilyl] benzene (TEDSB) were synthesized through in situ Grignard reaction and hydrosilylation, and characterized by FT-IR and ¹H-NMR. They were colorless transparent viscous liquids. Methyhexahydrophthalic anhydride (MeHHPA) was used to cure the epoxy resins to give glassy solids with high optical clarity. Differential scanning calorimetry (DSC) results indicated that DEDSB and TEDSB showed similar curing reactivity. The cured TEDSB had a higher glass transition temperature, a higher storage modulus and a lower coefficient of linear thermal expansion than the cured DEDSB due to a higher crosslink density. The cured silphenylene-containing epoxy resins exhibited a much higher resistance to discoloration under UV irradiation than the commonly used epoxy resins diglycidyl ether of bisphenol-A (DGEBA). XPS analysis revealed that they were much less susceptible to photo-oxidation than DGEBA.     

橡胶活性官能团对增韧环氧树脂动态力学性能的影响

用动态扭摆法测试聚丙烯酸丁酯橡胶增韧环氧树脂的动态力学行为,研究在环氧树脂低固化度和高固化度时,橡胶活性官能团种类(环氧基官能团与羧基官能团)和数量(官能度)对其影响。研究体系中橡胶玻璃化转变温度(Tg)的移动大小,与橡胶和基体树脂健合程度之间的关系。     

中空多壳层TiO2填充对环氧树脂复合材料力学性能的影响

为改善环氧树脂(EP)材料的力学性能, 采用次序模板法合成了TiO₂中空多壳层结构(HoMS)材料, 利用偶联剂对获得的TiO₂ HoMSs进行接枝改性后填充到EP中, 制备了TiO₂ HoMSs/EP复合材料; 并与单壳层TiO₂中空结构进行比较, 研究了壳层数和偶联剂改性对复合材料力学性能的影响规律. 结果表明, 随着壳层数的增加, 复合材料的力学性能增强, 并且偶联剂改性的TiO₂ HoMSs可进一步提高复合材料的力学性能. 在该体系中, 经硅烷偶联剂KH-560改性后的三壳层TiO₂ HoMSs(3S-TiO₂ HoMSs)/EP复合材料的拉伸强度、 断裂伸长率和冲击强度可分别达到71.66 MPa, 7.4%和35.81 kJ/m². 扫描电子显微镜(SEM)断面形貌表征结果显示, 相较于纯EP材料, TiO₂ HoMSs/EP复合材料的断面更加粗糙, 说明TiO₂ HoMSs材料起到了吸收外界应力和阻碍裂纹扩展的作用, 提高了复合材料的韧性, 提升了复合材料的冲击性能.     

有机在同聚物改性环氧树脂的方法与机理

综述了有机硅高聚物改性环氧树脂的各种改性方法、反应机理以及改性机理的研究进展。     

温度效应对氟链封端聚醚酰亚胺改性环氧树脂相分离的影响

用差示扫描量热仪(DSC)、扫描电镜(SEM)和时间分辨光散射(TRLS)比较了全氟碳链封端和苯环封端聚醚酰亚胺改性环氧树脂在不同温度下的相分离.结果表明,与P-blend相比,F-blend的固化速度和相分离速度较慢,诱导期和相结构固定时间推迟,相间距较小.升高温度,相间距因相分离速度加快而增大,同时由于全氟碳链端基引起的差异减小.因此,通过改变固化温度和聚醚酰亚胺的端基来降低聚醚酰亚胺的表面能,可以在一定程度上调控反应诱导相分离体系的相结构,并获得相间距较小的双连续结构.