环氧树脂水基化化学改性的研究

用对氨基苯甲酸改性环氧树脂 ,使其成为具有亲水性的树脂。测定了改性树脂的溶解性 ,发现改性后树脂在有机溶剂中的溶解性能变差 ,但在碱性溶剂中溶解性增强。对改性树脂进行了红外光谱表征 ,并根据环氧基特征峰的吸收对环氧基转化率进行了定量分析。测定了改性产物的DSC曲线 ,发现随着反应物中对氨基苯甲酸比例的提高 ,改性产物的玻璃化转变温度升高。涂膜的性能测试表明 ,对氨基苯甲酸改性环氧树脂水基涂料的机械力学性能和耐化学试剂性能比溶剂型纯环氧树脂要优越。     

环氧树脂复合水分散乳液的制备及其性能研究

通过溶液聚合法制备了丙烯酸单体改性的高相对分子量的环氧树脂复合水分散乳液.利用傅立叶变换红外光谱仪测试了改性聚合物的结构,用ZETA电位分析仪测定了水分散液的粒径及其分布,用透射电子显微镜观察了乳液粒子形态.实验结果表明,改性树脂在水等极性溶剂中有较好的溶解性;随着改性树脂中羧基中和程度的加大,水分散液粒径减小,并成为形状规则的单分散乳液.作者同时进行了改性树脂稀释行为的研究.     

化学改性环氧树脂水基涂料的研究——涂膜性能

用对氨基苯甲酸改性环氧树脂 ,使其具有亲水亲油两亲性质 ,测定了改性产物和纯环氧树脂共混物的玻璃化转变温度 ,结果显示两者能够相容 ,并以改性产物及其与纯环氧树脂的混合物制备水基涂料 ,测定了涂膜的物理和化学性能。结果表明 ,涂膜性能优良 ,保持了溶剂型环氧涂料的抗冲击强度、光泽度和硬度等方面的优点 ,而附着力提高 ,同时柔韧性大为改善 ,涂膜耐水性和耐化学药品性能优良。     

水性环氧复合乳化剂的合成及性能

以环氧树脂E-44、2-氨基-5-磺酸基苯甲酸、乙二醇丁醚和正丁醇为原料,合成一种新型阴离子环氧乳化剂EP-D;同时,E-44和聚乙二醇(PEG6000)以摩尔比2∶1反应,合成端环氧基非离子环氧乳化剂EP-PEG;将EP-D与EP-PEG按不同质量比复配获得不同配比的EP-D/EP-PEG水性环氧复合乳化剂。 分别研究了EP-D/EP-PEG及EP-PEG在环氧树脂中加入质量分数为6%~12%时的乳化性能及形成乳液的表面张力、电导率和胶粒的Zeta电位、粒径。 结果表明,当EP-D和EP-PEG以质量比3∶5复配,总加入质量分数为9%时,制备的环氧乳液性能最佳。 与EP-PEG形成的环氧乳液相比,复配环氧乳化剂用量少,乳液铺展性好、稳定性高,且乳液在相反转时的固含量提高了10%以上。 复配环氧树脂乳液中胶粒的Zeta电位为-41.9 mV、粒径为342 nm、表面张力为25.5 mN/m、粘度为14 mPa·s。 这表明利用乳化剂EP-D与EP-PEG复配新合成的EP-D/EP-PEG水性环氧复合乳化剂可制备稳定性好,固含量高的乳液。     

新型水性环氧树脂的合成研究

以2-丙烯酰胺基-2-甲基丙磺酸(AMPS)为改性剂,过氧化苯甲酰(BPO)为引发剂,通过溶液聚合,使环氧树脂获得水分散性。以改性环氧树脂的收率、粒径分布、反应体系酸值随时间的变化为指标,对反应历程进行了推断,并对改性产物的结构进行了红外光谱分析。结果表明,在整个反应中,AMPS与环氧树脂主链接枝反应和与环氧树脂的环氧基团的开环反应同时进行。高聚物收率可达76.72%,体系中的环氧基团约70%被保留下来。改性环氧树脂体系不需中和即可分散于水中。     

新型环氧丙烯酸树脂增韧剂的合成

用马来酸酐和聚乙二醇1000合成具有反应活性端基的聚乙二醇,用红外与核磁共振进行了表征,并用其对环氧丙烯酸树脂进行改性;研究反应温度、反应时间对反应及产物性能的影响;用红外对反应性聚乙二醇和环氧丙烯酸树脂的固化物进行分析.结果表明,反应性聚乙二醇参与了环氧丙烯酸树脂的固化反应,可在交联网络中构成不同长度的柔性链段,显著地提高了环氧丙烯酸树脂的冲击强度.     

硅烷化学改性环氧涂层的耐蚀性能

利用"活性"与"非活性"硅烷化学改性环氧涂层以提高其耐蚀性."活性"硅烷指含有可以与环氧树脂的环氧端基发生开环反应官能团的硅烷,通常为氨基硅烷;"非活性"硅烷指不与环氧端基发生反应,但在有机锡催化剂存在下可与环氧树脂骨架上的羟基发生缩合反应的硅烷.红外光谱显示,两类硅烷均可成功接枝在环氧树脂上.电化学阻抗谱(EIS)和加速腐蚀试验(Machu试验)测试表明,经硅烷化学改性后的环氧涂层均能提高其耐蚀性能.     

新型光固化环氧丙烯酸酯乳液的制备及其防腐性能研究

将环氧树脂和非离子型表面活性剂在一定温度下与丙烯酸反应合成出改性环氧丙烯酸酯树脂,再利用相反转乳化法制备得到光固化水性环氧乳液。对该反应的原料种类、反应条件、以及乳化工艺进行了优化研究,并对不同条件下得到的乳液进行了综合性能评价。着重考察了环氧树脂的种类以及光引发剂的种类对乳液粒径、清漆膜电化学防腐性能和耐盐雾性能的影响。结果表明:选取环氧树脂E20,光引发剂IRGACURE651,酯化反应温度为105℃,反应时间3h,乳化温度为25℃~30℃,搅拌速度为800r/min时,制得的乳液稳定性和漆膜性能(包括漆膜的力学性能、电化学防腐性能和耐盐雾性能)最佳。     

新型耐腐蚀含氟环氧乙烯基酯树脂的合成与性能

以含氟环氧树脂（F-EP）、丙烯酸（AA）和甲基丙烯酸（MAA）为单体,用顺丁烯二酸（MA）进行改性,合成了含氟环氧乙烯基酯树脂（F-EVER）。用傅里叶红外光谱、热重分析、力学性能分析等手段对产物进行表征,研究了树脂的耐腐蚀性能。结果表明：当以N,N-二甲基甲酰胺（DMF）为催化剂,羧基与环氧基摩尔比为0.9,MA与...     

含不同季铵盐结构的新型水显影感光树脂

通过不同的三乙胺盐及丙烯酸对环氧酚醛树脂的开环反应,合成了含不同季铵盐及丙烯酸酯基的新型水显影感光树脂。研究了环氧基在不同三乙胺盐开环时的转化率,产物溶解性,感光性及热稳定性等。     

Synthesis and characterization of epoxy resins containing imine group and their curing processes with aromatic diamine

The epoxy resins containing imine bonding were prepared from hydroxyl substituted Schiff base monomers in two steps. At the first step, hydroxyl substituted Schiff base monomers were synthesized via condensation reaction. At the second step, epoxy resins were synthesized from the reaction between Schiff base monomers and epichlorohydrine (EPC). Then curing processes of epoxy resins were achieved by p-phenylenediamine compound. The structures of resulting compounds were confirmed by FT-IR, UV-Vis and ¹H-NMR. TG-DTA and DSC measurements were performed for thermal characterizations of the compounds. Chemical resistances of the cured epoxy-amine systems were determined for coating applications in acidic, alkaline and organic solvents. HCl (10%, aqueous solution), NaOH (10%, aqueous solution), DMSO, DMF, N-methylpyrrolidone, ethanol, THF and acetone were used for corrosion tests. Chemical resistance data of the synthesized epoxy resins demonstrated that they have good chemical resistance against various acid, alkaline and common organic solvents. Surface morphologies of epoxy resin and the cured epoxy resin were determined with scanning electron microscopy (SEM) measurements. Also, optical band gap (E_g) values of Schiff base monomers and epoxy resins were calculated from UV-Vis measurements.     

Studies on thermal and morphological properties of 1,1-bis(3-methyl-4-cyanatophenyl)cyclohexane-epoxy-bismaleimide matrices

A new cyanate ester monomer, 1,1-bis(3-methyl-4-cyanatophenyl)cyclohexane has been synthesized and characterized. Epoxy modified with 4, 8 and 12% (by weight) of cyanate ester were made using epoxy resin and 1,1-bis(3-methyl-4-cyanatophenyl)cyclohexane and cured by using diaminodiphenylmethane. The cyanate ester modified epoxy matrix systems were further modified with 4, 8 and 12% (by weight) of bismaleimide (N,N′-bismaleimido-4,4′-diphenylmethane). The formation of oxazolidinone and isocyanurate during cure reaction of epoxy and cyanate ester blend was confirmed by IR spectral studies. Bismaleimide-cyanate ester-epoxy matrices were characterized using differential scanning calorimetry (DSC), thermogravimetric analysis (TGA) and heat deflection temperature (HDT) analysis. Thermal studies indicate that the introduction of cyanate ester into epoxy resin improves the thermal degradation studies at the expense of glass transition temperature. Whereas the incorporation of bismaleimide into epoxy resin enhances the thermal properties according to its percentage content. However, the introduction of both cyanate ester and bismaleimide influences the thermal properties according to their percentage content. DSC thermogram of cyanate ester modified epoxy and bismaleimide modified epoxy show unimodel reaction exotherms. The thermal degradation temperature and heat distortion temperature of the cured bismaleimide modified epoxy and cyanate ester-epoxy systems increased with increasing bismaleimide content. The morphology of the bismaleimide modified epoxy and cyanate ester-epoxy systems were also studied by scanning electron microscopy. Copyright © 2003 John Wiley & Sons, Ltd.     

咪唑固化不同类型环氧树脂的固化特征、固化动力学及其反应活性

以咪唑为固化剂,对缩水甘油醚型、缩水甘油酯型环氧树脂(简称链型环氧树脂)及脂环环氧树脂的固化特征、固化动力学及反应活性进行了研究.DSC实验结果表明,固化过程均分两阶段进行,链型环氧树脂固化反应表观活化能低于脂环环氧树脂.各树脂第一阶段的表观反应活化能均低于第二阶段活化能.当脂环环氧树脂中混入不同比例的链型环氧树脂后,固化反应速率均较脂环环氧树脂单独固化时快,当链型环氧树脂量大于50％时,更为明显.     

Adhesives and coatings based on phenolic/epoxy resins

Low molecular weight epoxy resin based on bis (4‐hydroxy phenyl) 1,1 cyclohexane was prepared and modified with various types of the prepared phenolic resins. Phenol–, cresol–, resorcinol–and salicylic acid–formaldehyde resins were used. The optimum conditions of formulation and curing process were studied to obtain modified wood adhesives characterized by high tensile shear strength values. This study indicated that the more suitable conditions are 1:2 weight ratio of phenol–or cresol–formaldehyde to epoxy resin in the presence of phthalic anhydride (20 wt%) of the resin content as a curing agent at 150°C for 80 min. Resorcinol–or salicylic acid–formaldehyde/epoxy resins formulated at 1:2 weight ratio were cured in the presence of paraformaldehyde (20 wt%) at 150°C for 60 min. The effect of the structure of phenolic resins on the tensile shear strength values of formulated resin samples, when mixed with the epoxy resins and cured under the previously mentioned optimum conditions for different times, was investigated. Metallic and glass coatings from the previous resins were also prepared and evaluated as varnishes or paints. Copyright © 1999 John Wiley & Sons, Ltd.     

Oligo-fluoropolymer Modified Cycloaliphatic Epoxy Resins with Excellent Compatibility,Waterproof and Mechanical Properties for LED Encapsulation

An oligo-fluoropolymer(PFM) with functional cycloaliphatic epoxy and fluorinated groups was obtained via free radical polymerization and applied to the modification of cycloaliphatic epoxy resins(CE). The chemical structure of PFM was characterized by Fourier transform infrared(FTIR) spectroscopy, gel permeation chromatography(GPC) and nuclear magnetic resonance(NMR) spectroscopy, and the effects of different PFM concentrations(0.5%—6%, mass fraction) on the thermal resistance, mechanical properties, surface dewettability, light transmission, refractive index and various cured polymer properties were studied in detail. The DSC and TGA results demonstrate that the modified epoxy resins possess a higher thermal resistance than the neat epoxy resin. The improvements in the surface dewettability and water resistance are caused by the high crosslinking density and the enrichment of the oligo-fluorinated random copolymers dispersed in the matrix. The fracture surface morphologies of the thermosets were investigated by scanning electron microscopy(SEM) and transmission electron microscopy(TEM). It was observed that the optical transmittance of the composites was maintained even though microphase separation occurred during the curing process. With respect to the corresponding properties of the neat epoxy resins, the 2 phr(parts per hundreds of resin) PFM thermoset exhibited relatively better comprehensive properties, making the cured material a good candidate for light-emitting diode(LED) encapsulation.     

基于可逆动态共价化学的新型可修复、可回收、可加工环氧树脂

利用生物来源的二聚脂肪酸为原料,合成了二聚酸酰肼和二聚酸酰腙两种衍生物,并进一步以其作为环氧E-44树脂固化剂,得到了新型的含动态共价连接的热固性环氧树脂。采用傅里叶红外光谱(FT-IR)、差式扫描量热(DSC)、扫描电子显微镜(SEM)、热重(TG)和动态力学分析(DMA)等多种测试手段对环氧树脂固化过程以及固化后材料的结构与性能关系进行了详细表征,特别研究了动态亚胺键对热固性环氧树脂性能的独特影响。结果表明:与传统环氧树脂相比,改性后的环氧树脂有更好的韧性,且其玻璃化转变温度及热稳定性没有明显下降。在升温和加压的条件下,酸可催化亚胺键的动态交换反应,赋予传统环氧树脂以全新的可修复、可回收与可多次加工性能。     

环氧树脂水基分散体系的相反转乳化

以聚乙二醇－邻苯二甲酸酐－环氧树脂Ｅ－４４多元嵌段共聚体为乳化剂,将环氧树脂Ｅ－４乳化成水包油的稳定水基乳液。用乳液体系电导率和粘度的变化表征了相反转乳化过程。研究了乳化剂浓度、三元多嵌段共聚体中亲水嵌段分子量和乳化温度对相反转乳化过程的影响。实验结果表明,体系在较高乳化剂浓度（９．１％）下为完全相反转,在低乳化剂浓度（４．１％）下为不完全相反转。相反转时水与环氧树脂Ｅ－４４的重量比值随乳化剂浓度     

Crosslinking of epoxy resins at interfaces. IV. Anhydride-cured resins at carbon and graphite surfaces

Dispersions of carbon blacks and chopped carbon fibers in epoxy resins may be characterized by infrared internal reflection spectroscopy (IR–IRS). The high surface areas of the carbons (often ≥ 100 m²/g) ensure a high degree of interfacial contact between the carbon surface and the polymer. The crosslinking kinetics and final crosslinked state of an anhydride-cured epoxy resin are shown to be affected strongly by the carbons through adsorption of the tertiary amine catalyst at oxidation sites on the carbon surface. Oxidative treatments of the carbons (nitric acid oxidation, air oxidation) increase the effect on the crosslinking chemistry. Carbon dioxide treatment of the carbons, which produces a basic surface, reduces the effect on the crosslinking. The effects on the crosslinking kinetics were confirmed by differential scanning calorimetry (DSC). The relevance of these results to the characterization of the interphase in carbon fiber/epoxy composites is discussed.