笼型倍半硅氧烷(POSS)/环氧杂化树脂体系固化反应动力学及性能研究

为了提高环氧树脂的耐热性,采用笼型倍半硅氧烷(POSS)改性双酚A型环氧树脂E51,得到有机无机杂化树脂。采用Ozawa和Kissinger两种方法研究了杂化树脂/4,4′-二氨基苯砜(DDS)体系的固化反应动力学。TGA分析表明,POSS的加入提高了E51/DDS固化树脂体系的热性能。     

POSS改性环氧树脂的耐热性研究进展

回顾并总结了近年来以笼型倍半硅氧烷(POSS)提高环氧树脂耐热性的研究成果。POSS具有独特的纳米尺寸效应,及其他纳米材料所没有的交联效应,因而能够有效地限制聚合物分子链的活动能力,提高聚合物的玻璃化转变温度和热残余量;此外,POSS的Si-O-Si内核不仅键能高,而且在受热氧作用后能够形成SiO2阻隔保护层,可进一步提高环氧树脂复合材料的耐热性。POSS是一种非常有前途的纳米杂化材料,在降低成本后将能够在环氧树脂耐热性提高方面发挥更大作用。     

蓝星开发无铅环氧树脂制品

<正>蓝星新材料无锡树脂厂正在积极开发无铅化环氧树脂制品,以替代传统含铅产品。目前小试已取得很大进展,实现了阶段性研发目标。印刷电路板焊锡无铅化对环氧树脂的耐热性提出了更高的标准,通用型的环氧树脂已难以达到这一要求。为此,该厂精细化工研究所从今年年初开始研发适应这种要求的双酚A酚醛树脂、双酚A酚醛环氧树脂。目前科研人员已利用双酚A和甲醛成功合成出双酚A型酚醛树脂,利用双酚A型酚醛树脂和环氧氯丙烷成功合成出双酚A型酚醛环氧树脂,用户试用后肯定了     

用相转移催化剂合成双酚—S型环氧树脂的研究

双酚—A型环氧树脂有良好的物理及化学性能,广泛被用作胶粘剂和涂料。但由于它还存在着耐热性差等缺点,因而在尖端科学上应用受到了一定限制。如何提高环氧树脂的耐热性和胶接强度是环氧树脂改性的方向之一,我们认为用双酚—S代替双酚—A会起到这种作用。     

双酚A型环氧树脂的合成与应用研究进展

双酚A型环氧树脂由于具有优异的物理和机械性能,化学稳定性,耐化学性,耐热性和粘合性而应用广泛。到目前为止,关于双酚A型环氧树脂的合成方法有很多种,本文总结了双酚A环氧树脂不同的合成研究方法及其在不同领域的常见应用方式。     

磷溴阻燃环氧树脂的制备及应用

以双酚A型环氧树脂(E-51)、四溴双酚A、9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物(DOPO)或10-(2,5-二羟基苯基)-10-氢-9-氧杂-10-磷杂菲-10-氧化物(DOPO-HQ)为原料,合成了2种磷溴阻燃环氧树脂(简称PB-1016、PBHQ-1016),然后与双酚A型酚醛树脂固化反应制备了覆铜板,采用红外光谱,凝胶渗透色谱,热重分析及阻燃性测试对磷溴阻燃环氧树脂和覆铜板进行了结构表征与性能研究。结果表明,磷溴阻燃环氧树脂具有明显的协同阻燃效应,并可提升含溴阻燃覆铜板的耐热性和相比漏电起痕指数(CTI)。PBHQ-1016具有良好的热稳定性,以其制备的覆铜板的阻燃性、耐热性、粘接性和CTI等性能表现较优,综合性能最佳。     

高沸醇木质素环氧树脂的合成与性能研究

利用高沸醇木质素的化学活性,直接与环氧氯丙烷反应,生成木质素环氧树脂和木质素改性双酚A型环氧树脂,用环氧值、红外光谱、TGA和DSC等对树脂进行表征,并与未改性的双酚A型环氧树脂进行对比。结果表明,高沸醇木质素很容易合成木质素环氧树脂,其最佳合成条件是:n(ECH)∶n(-OH)=8,温度55～60℃,碱浓度为5%;高沸醇木质素环氧树脂能显著提高环氧树脂的耐溶剂性和耐热性。     

蓝星开发无铅环氧树脂制品

<正>近日,从蓝星新材料无锡树脂厂传出消息,该厂正在积极开发无铅化环氧树脂制品,以替代传统含铅产品。目前小试已取得很大进展,实现了阶段性研发目标。印刷电路板焊锡无铅化对环氧树脂的耐热性提出了更高的标准,通用型的环氧树脂已难以达到这一要求。为此,该厂精细化工研究所从今年年初开始研发适应这种要求的双酚A酚醛树脂、双酚A酚醛环氧树脂。目前科研人员已利用双酚A和甲醛     

二步法合成高分子量双酚A型环氧树脂的新型催化剂

<正>双酚A型环氧树脂是世界上应用最广泛、最普遍的一种环氧树脂.它可与胺、酸、酐类化合物固化成不熔不溶的热固性聚合物.利用这一反应可以制成涂料、粘合剂、层压材料、灌铸料和密封材料等,固化物具有良好的耐热性、耐化学性和机械强度.双酚A型环氧树脂是由双酚A与环氧氯丙烷缩合而成.这种环氧树脂可制成不同分子量的缩合物,成为液体、半固体、固体的树脂产品.     

2,6-萘二羧酸改性双酚A环氧树脂的性能

用2,6-萘二羧酸(NDCA)对双酚A环氧树脂进行改性,研究了NDCA加入量对双酚A环氧树脂黏度、耐热性和力学性能的影响。结果表明,NDCA能提高环氧树脂的储能模量和玻璃化转变温度,玻璃化转变温度最高达到113℃。NDCA的质量分数小于0.5%时,改性环氧树脂的断裂伸长率随着NDCA加入量的增加逐渐提高,最高达12%。结合傅立叶变换红外光谱测试,提出了NDCA改性双酚A环氧树脂的机理,并对改性环氧树脂性能增强的机理进行了探讨。     

含三聚氰胺有机硅杂化物的环氧树脂性能研究

利用羟甲基化三聚氰胺和γ-环氧丙氧基三甲氧基硅烷反应制备了三聚氰胺有机硅杂化物,并用FTIR、29S iNMR对其结构进行了表征。然后将其与环氧树脂共混固化,对固化物热性能、阻燃性、力学性能进行了分析。结果表明,该三聚氰胺有机硅杂化环氧树脂固化物不仅保持纯环氧树脂玻璃化转变温度,而且在空气和氮气中的热失重分析显示,高温区域的热稳定性及残碳率比纯环氧树脂高;三聚氰胺有机硅杂化环氧树脂固化物的极限氧指数达到30.2,与纯环氧树脂相比,该固化物的极限氧指数提高了43%左右,抗冲击强度有较大幅度的提高,当三聚氰胺有机硅杂化物的添加量为环氧树脂质量的5%时,环氧树脂固化物的抗冲击强度达到20.3 kJ/mol;扫描电子显微镜照片显示三聚氰胺有机硅杂化环氧树脂的韧性较纯环氧树脂有很大提高。     

硅磷杂化物/环氧树脂固化物的性能研究

以γ-环氧丙氧基三甲氧基硅烷(KH-560)与磷酸反应合成了一种含磷硅烷偶联剂,将这种含磷硅烷偶联剂与硅溶胶按一定配比进行水解缩聚反应,得到一种硅磷杂化物,将该硅磷杂化物引入到双酚A环氧树脂(E-51),以4,4′-二氨基二苯基甲烷为固化剂,制备了硅磷杂化物/环氧树脂固化物。对该固化物的玻璃化转变温度、热失重、拉伸强度、极限氧指数(LOI)进行了测试。结果表明,该固化物玻璃化转变温度,700℃残炭量以及LOI均比纯环氧树脂固化物高,拉伸强度却下降较少。当硅磷杂化物的添加量占环氧树脂质量的50%时,该固化物的玻璃化转变温度可以达到178℃,极限氧指数可以达到28.2,与纯环氧树脂固化物相比,分别提高了18℃和25%。与纯环氧树脂固化物相比,该硅磷杂化物/环氧树脂固化物具有较好的阻燃性及热稳定性。     

Study on the modification of epoxy resin by a phosphorus‐ and silica‐containing hybrid

A novel phosphorus‐ and silica‐containing hybrid (DPS) was synthesized by the reaction between diethyl phosphate (DEP) and polyhedral oligomeric siloxanes (POS) formed by hydrolysis condensation of 3‐glycidoxypropyltrimethoxysilane (GPTMS). The novel phosphorus‐ and silica‐containing hybrid was characterized by the flourier transform infrared spectroscope (FT‐IR), silicon nuclear magnetic resonance, and gel permeation chromatography (GPC). Then, the determination of the activation of the reaction between epoxy resin and phosphorus‐, and silica‐containing hybrids was studied by differential scanning calorimeter (DSC). In the presence of catalyst, the activation energies of the curing reaction were 63.3 and 66.7 kJ/mol calculated by Kissinger model and Ozawa model respectively. The thermal and flame retardant properties of the cured epoxy modified by DPS were determined by differential scanning calorimeter (DSC), thermal gravimetric analysis (TGA), and limited oxygen index (LOI). The results revealed that those properties were improved in comparison with unmodified epoxy resin. In addition, scanning electron microscopy (SEM) was used to investigate the morphology of the cured epoxy resin modified by DPS. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Synthesis,thermal properties,and flame retardance of the epoxy‐silsesquioxane hybrid resins

Epoxy/silsesquioxane‐OH (EP‐SDOH, ED) hybrid resins were prepared from cyclohexyl‐disilanol silsesquioxane (SDOH) and diglycidyl ether of bisphenol A via the reaction between silanol and the oxirane group, with the cobalt naphthanate as a catalyst. It was found that incorporation of SDOH allows the reaction between oxirane ring and Si? OH, and the silsesquioxane cage structure can be the main chain or as the side chain of the hybrid resin. The EP‐SDOH hybrid resins with various SDOH contents were cured by 4,4′‐diaminodiphenylsulphone, and the curing reaction was investigated by differential scanning calorimetry. The curing characteristics of EP‐SDOH hybrids had been observed to be influenced by the content of SDOH in the hybrid. The differential scanning calorimetry thermograms indicated that the EP‐SDOH hybrid exhibited a higher initial temperature, peak temperature, as well as final temperature than those of the pure epoxy resin when cured by the same curing agent 4,4′‐diaminodiphenylsulphone. The curing kinetic parameters were calculated by using the Ozawa method and the results indicated that EP‐SDOH hybrids possess the same curing mechanism as the pure epoxy resin. The properties of the cured EP‐SDOH hybrid resins such as the glass transition temperature (T_g), dynamic mechanical analysis, thermal stability, as well as the flame retardance were also investigated, and the results showed that introducing silsesquioxane‐OH unit into epoxy resin successfully modified the local structure, made the chain stiffness, restrict the chain mobility, and eventually improved thermal stability and flame retardance of epoxy resin. POLYM. ENG. SCI., 47:225–234, 2007. © 2007 Society of Plastics Engineers.     

脂肪族环氧化合物的合成及其共混树脂的研究

以聚丙二醇和环氧氯丙烷为原料合成出了低黏度的脂肪族环氧树脂。使用上述环氧树脂与双酚A型环氧树脂按不同的比例混合后,再加入大分子胺类固化剂,由此构筑出环氧树脂固化体系并对其黏度、凝胶时间和固化物的力学性能进行了表征。结果显示,该环氧树脂固化体系在常温下具有很低的黏度与较长的凝胶时间,其固化物的拉伸与弯曲性能较好,且冲击韧性有了明显的改善。     

Synthesis and curing kinetics of colored epoxy resin containing azo moiety

Colored epoxy resin containing azo moiety was synthesized by reaction between epichlorohydrin and bis-azodiol, which was synthesized by coupling bisphenol-A with aromatic amine. Colored epoxy resin was characterized by epoxy equivalent weight, IR spectra, Viscosity and UV visible spectroscopy. The curing of colored epoxy resin and DGEBA were characterized by differential scanning calorimetry (DSC). The thermal stability of cured products was characterized by thermogr avimetric analysis (TGA). The cured products have good thermal stability. Several glass fiber epoxy composites were fabricated and their mechanical properties, electrical properties and chemical resistance were studied.     

Laboratory investigation of the properties of asphalt modified with epoxy resin

Epoxy asphalts were prepared by mixing styrene–butadiene–styrene (SBS) modified asphalt with epoxy resin. The curing process and morphology of epoxy asphalts were characterized by infrared spectroscopy and fluorescent microscope, respectively. The effects of epoxy resin contents, ratio of curing agent to epoxy resin and curing temperature on properties of epoxy asphalt were investigated. Results indicated that epoxy resin and epoxy asphalt showed similar curing efficiency. Epoxy asphalts can be cured at 120 or 60°C and its viscosity at 120°C can meet the demands of asphalt mixture mixing and paving. The chemical reaction of epoxy resin in epoxy asphalt is slow and reaction occurs not only with the curing agent but also carboxylic acid in epoxy asphalt. The microstructure of epoxy asphalt transforms from the dispersed structure to networks structure with epoxy resin content increasing and phase transition starts when 30 wt % epoxy resin present in asphalt. The softening point and tensile strength of epoxy asphalt increased with epoxy resin contents increasing. The softening point and tensile strength of epoxy asphalt were markedly improved when epoxy resin content was more than 30 wt %, which is attributed to formation of continuous structure of epoxy resin. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

几种胺类固化剂对环氧树脂固化行为及固化物性能的影响

固化剂结构对环氧树脂的固化行为和固化物性能具有重要影响,本文研究了聚醚胺(D-230)、异佛尔酮二胺(IPDA)和3,3'-二甲基-4,4'-二氨基-二环己基甲烷(DMDC) 3种胺类固化剂与实验室自制的低翻度环氧树脂A进行固化反应.通过薪度分析、红外(FTIR)光谱分析、DSC分析等手段研究了环氧树脂与固化剂反应程度...     

Hybridization of aqueous PU/epoxy resin via a dual self‐curing process

Amino‐terminated and carboxyl‐containing polyurethane (PU) is prepared by an isocyanate‐terminated PU prepolymer process. Carboxyl‐containing epoxy resin is obtained from a half‐esterification of epoxy resin with maleic anhydride. These two aqueous resins are obtained after neutralization with triethylamine and dispersion into water phase, respectively. A latent curing agent (TMPTA‐AZ) is prepared by a Michael addition of aziridine with trimethylolpropane triacrylate (TMPTA). A self‐curing system of PU/epoxy hybrid is obtained from a blending of these two aqueous resins with latent curing agent. PU/epoxy hybrid is derived from two self‐curing reactions on drying. The first curing for hybridization between PU amino groups with oxirane groups of epoxy resin is via a ring‐opening reaction and the secondary curing takes place on carboxyl groups of PU/epoxy hybrid with aziridine of TMPTA‐AZ. The final properties of these dual self‐cured PU/epoxy hybrids are reported. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

New thermosetting resin from poly(p‐vinylphenol) based benzoxazine and epoxy resin

Poly(p‐vinylphenol) (VP) based benzoxazine was prepared from VP, formaline, and aniline. The curing behavior of the benzoxazine with the epoxy resin and the properties of the cured resin were investigated. Consequently, the curing reaction did not proceed at low temperatures, but it proceeded rapidly at higher temperatures without a curing accelerator. The reaction induction time or cure time of the molten mixture from VP based benzoxazine and epoxy resin was found to decrease, compared with those from conventional bisphenol A based benzoxazine and epoxy resin. The curing reaction rate of VP based benzoxazine and epoxy resin increased more than that of conventional bisphenol A based benzoxazine and epoxy resin. The properties of the cured resin from neat resins and from reinforced resins with fused silica were evaluated. The cured resins from VP based benzoxazine and epoxy resin showed good heat resistance, mechanical properties, electrical insulation, and water resistance compared to the cured resin from VP and epoxy resin using imidazole as the catalyst. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 555–565, 2001