High resolution solid‐state 13C‐NMR study of as‐cured and irradiated epoxy resins

This article presents the effects of strong ionizing radiations on the physico‐chemical modifications of aliphatic or aromatic amine‐cured epoxy resins based on diglycidyl ether of bisphenol A (DGEBA). Such epoxy resins have a considerable number of applications in the nuclear industrial field and are known to be very stable under moderate irradiation conditions. Using extensively high resolution solid‐state ¹³C‐NMR spectroscopy we show that the aliphatic amine‐cured resin (DGEBA‐TETA) appears much more sensitive to gamma rays than the aromatic amine‐cured one (DGEBA‐DDM). On the one hand, qualitative analyses of the high resolution solid‐state ¹³C‐NMR spectra of both epoxy resins, irradiated under similar conditions (8.5 MGy), reveal almost no change in the aromatic amine‐cured resin whereas new resonances are observed for the aliphatic amine‐cured resin. These new peaks were interpreted as the formation of new functional groups such as amides, acids and/or esters and to alkene groups probably formed in the aliphatic amine skeleton. On the other hand, molecular dynamics of these polymers are investigated by measuring the relaxation times, T_CH, T_1ρH and T_1C , before and after irradiation. The study of relaxation data shows the formation, under irradiation, of a more rigid network, especially for the aliphatic amine‐cured system and confirms that aromatic amine‐cured resin [DGEBA‐4,4′‐diaminodiphenylmethane(DDM)] is much less affected by ionizing radiations than the aliphatic amine‐cured resin [DGEBA‐triethylenetetramine(TETA)]. Moreover, it has been shown that the molecular modifications generated by irradiation on the powder of the aliphatic‐amine‐cured resin appear to be homogeneously distributed inside the polymers as no phase separations can be deduced from the above analyses. Copyright © 2001 John Wiley & Sons, Ltd.     

Organic/inorganic hybrid epoxy nanocomposites based on octa(aminophenyl)silsesquioxane

Octa(aminophenyl)silsesquioxane (OAPS) was used as the curing agent of diglycidyl ether of bisphenol-A (DGEBA) epoxy resin. A study on comparison of DGEBA/OAPS with DGEBA/4,4′-diaminodiphenyl sulfone (DDS) epoxy resins was achieved. Differential scanning calorimetry was used to investigate the curing reaction and its kinetics, and the glass transition of DGEBA/OAPS. Thermogravimetric analysis was used to investigate thermal decomposition of the two kinds of epoxy resins. The reactions between amino groups and epoxy groups were investigated using Fourier transform infrared spectroscopy. Scanning electron microscopy was used to observe morphology of the two epoxy resins. The results indicated that OAPS had very good compatibility with DGEBA in molecular level, and could form a transparent DGEBA/OAPS resin. The curing reaction of the DGEBA/OAPS prepolymer could occur under low temperatures compared with DGEBA/DDS. The DGEBA/OAPS resin didn’t exhibit glass transition, but the DGEBA/DDS did, which meant that the large cage structure of OAPS limited the motion of chains between the cross-linking points. Measurements of the contact angle indicated that the DGEBA/OAPS showed larger angles with water than the DGEBA/DDS resin. Thermogravimetric analysis indicated that the incorporation of OAPS into epoxy system resulted in low mass loss rate and high char yield, but its initial decomposition temperature seemed to be lowered.     

环氧树脂／酚酞聚醚醚砜共混物的相行为

酚酞聚醚醚砜(PES-c)同未交联的双酚A二缩水甘油醚(DGEBA)环氧树脂的共混物呈单一的玻璃化转变温度,其相容性主要归因于混合熵的贡献。PES-C同交联的环氧树脂之间的相容性与所用的固化剂有关。以胺类作DGEBA的固化剂时,共混物不发生相分离;以酸酐作固化剂时,共混物发生相分离。     

Studies on the curing behaviour of bismaleimides and epoxy-resin blends

This paper describes the effect of diglycidyl ether of bisphenol A (DGEBA) on the curing behaviour of a chain-extended bismaleimide resin. 4,4'-Bismaleimidophenyl sulfone (BS) resin was treated with 4,4'-diaminodiphenyl ether or 4,4'-diaminodiphenyl methane to yield BS-M and BS-E resins which were then solution-blended with DGEBA containing stoichiometric amounts of amine as hardener. A decrease in the curing temperature of BS-M or BS-E was observed on blending with DGEBA. The thermal stability of the cured resin was reduced on blending.     

Kinetics and thermal properties of epoxy resins based on bisphenol fluorene structure

The fluorene-containing epoxy, diglycidyl ether of 9,9-bis(4-hydroxyphenyl) fluorene (DGEBF) was synthesized by a two-step reaction procedure. In order to investigate the relationship between fluorene structure and material properties, DGEBF and a commonly used diglycidyl ether of bisphenol A (DGEBA) were cured with 4,4-diaminodiphenyl methane (DDM) and 4,4-(9-fluorenylidene)-dianiline (FDA). The curing kinetics, thermal properties and decomposition kinetics of these four systems (DGEBA/DDM, DGEBF/DDM, DGEBA/FDA, and DGEBF/FDA) were studied in detail. The curing reactivity of fluorene epoxy resins was lower, but the thermal stability was higher than bisphenol A resins. The onset decomposition temperature of cured epoxy resins was not significantly affected by fluorene structure, but the char yield and T_g value were increased with that of fluorene content. Our results indicated that the addition of fluorene structure to epoxy resin is an effective method to improve the thermal properties of resins, but excess fluorene ring in the chain backbone can depress the curing efficiency of the resin.     

A systematic study of the microwave and thermal cure kinetics of the DGEBA/DDS and DGEBA/DDM epoxy‐amine resin systems

The microwave and thermal cure processes for the epoxy-amine systems (epoxy resin diglycidyl ether of bisphenol A, DGEBA) with 4,4′-diaminodiphenyl sulphone (DDS) and 4,4′-diaminodiphenyl methane (DDM) have been investigated for 1 : 1 stoichiometries by using fiber-optic FT-NIR spectroscopy. The DGEBA used was in the form of Ciba-Geigy GY260 resin. The DDM system was studied at a single cure temperature of 373 K and a single stoichiometry of 20.94 wt% and the DDS system was studied at a stoichiometry of 24.9 wt% and a range of temperatures between 393 and 443 K. The best values of the kinetic rate parameters for the consumption of amines have been determined by a least squares curve fit to a model for epoxy/amine cure. The activation energies for the polymerization of the DGEBA/DDS system were determined for both cure processes and found to be 66 and 69 kJ mol⁻¹ for the microwave and thermal cure processes, respectively. No evidence was found for any specific effect of the microwave radiation on the rate parameters, and the systems were both found to be characterized by a negative substitution effect. Copyright © 2002 John Wiley & Sons, Ltd.     

Nonaqueous synthesis of nanosilica in epoxy resin matrix and thermal properties of their cured nanocomposites

Nonaqueous synthesis of nanosilica in diglycidyl ether of bisphenol‐A epoxy (DGEBA) resin has been successfully achieved in this study by reacting tetraethoxysilane (TEOS) directly with DGEBA epoxy matrix, at 80 °C for 4 h under the catalysis of boron trifluoride monoethylamine (BF₃MEA). BF₃MEA was proved to be an effective catalyst for the formation of nanosilica in DGEBA epoxy under thermal heating process. FTIR and ²⁹Si NMR spectra have been used to characterize the structures of nanosilica obtained from this direct thermal synthetic process. The morphology of the nanosilica synthesized in epoxy matrix has also been analyzed by TEM and SEM studies. The effects of both the concentration of BF₃MEA catalyst and amount of TEOS on the diameters of nanosilica in the DGEBA epoxy resin have been discussed in this study. From the DSC analysis, it was found that the nanosilica containing epoxy exhibited the same curing profile as pure epoxy resin, during the curing reaction with 4,4′‐diaminodiphenysulfone (DDS). The thermal‐cured epoxy–nanosilica composites from 40% of TEOS exhibited high glass transition temperature of 221 °C, which was almost 50 °C higher than that of pure DGEBA–DDS–BF₃MEA‐cured resin network. Almost 60 °C increase in thermal degradation temperature has been observed during the TGA of the DDS‐cured epoxy–nanosilica composites containing 40% of TEOS. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 757–768, 2006     

Correlation between chain segment and ion mobility in an epoxy resin system. A free volume analysis

Steady shear viscosity and ionic conductivity have been measured for nine commercial diglycidyl ether of bisphenol-A (DGEBA) epoxy resins with molecular weights ranging from 340 to 14,200. The temperature dependence of viscosity and ionic conductivity was modeled using free volume viscosity and ionic conductivity relationships, which correlate the fractional free volume required for polymer chain segment motion (B) and the fractional free volume required for ion motion (B′) with polymer structure. The fractional free volume required for polymer chain segment mobility was observed to increase systematically with the molecular weight of the resins. The fractional free volume required for ion mobility did not vary for the resin series. A stoichiometric mixture of a low molecular weight DGEBA resin and a 4,4′-diaminodiphenyl sulfone cross-linker was partially polymerized to extents of reaction ranging from 0% to 49%. The fractional free volume required for polymer segment mobility for these partially polymerized samples was consistent with results for the neat resins. © 1993 John Wiley & Sons, Inc.     

含亚胺结构新型磷-氮协效阻燃化合物的合成及对环氧树脂的阻燃作用

采用醛胺缩合反应,以4-(5,5-二甲基-1,3-二氧杂环己内磷酰基)苯甲醛(PCHO)分别与对苯二胺、乙二胺反应合成两种磷酸酯-亚胺双官能化合物阻燃剂(FR:N¹,N⁴-二[4-(5,5-二甲基-1,3-二氧杂环己内磷酰氧基)苯基亚甲基]-1,4-苯二胺(PNB)和N¹,N²-二[4-(5,5-二甲基-1,3-二氧杂环己内磷酰氧基)苯基亚甲基]-1,2-乙二胺(PNE)),研究了FR对4,4'-二氨基二苯砜(DDS)固化双酚A二缩水甘油醚型环氧树脂(DGEBA)体系的阻燃作用及阻燃机理。 研究发现FR的引入显著提高了DGEBA/DDS在700 ℃时的残炭率(R_c),同时提升了材料的阻燃性能,其中以乙二胺合成的PNE阻燃性能显著优于以苯二胺合成的PNB。 当磷添加质量分数为1.5%时,PNE-1.5/DGEBA/DDS在N₂气下的R_c为35.1%,在空气下的R_c为14.4%,极限氧指数(LOI)为33.2%,并可达阻燃等级UL-94最高阻燃级别V-0级。 同时,PNE-1.5/DGEBA/DDS相较于DGEBA/DDS保持了弯曲强度和76%以上的冲击强度,机械性能显著优于PNB-1.5/DGEBA/DDS。 通过阻燃机理分析FR在DGEBA/DDS体系中具有凝聚相、气相及磷-氮协效共同作用的阻燃特点。 磷酸酯-亚胺双官能团化合物FR对环氧树脂体系具有良好的阻燃作用,其中PNE阻燃效率高、机械性能负面影响小,具有潜在应用价值。     

Influence of curing conditions on the morphology and physical properties of epoxy resins modified with a liquid polyamine

A diglycidyl ether of bisphenol-A (DGEBA) epoxy resin has been stoichiometrically cured with cycloaliphatic amine 4,4′-diamino-3,3′-dimethylcyclohexylmethane (3DCM) and modified with an amine terminated oligomer polyoxypropylenetriamine (POPTA) at a concentration of 15 wt %. Mixtures, postcured at the same temperature, have been precured at different temperatures. Phase separation takes place before gelation at all precure temperatures used. The variation in the glass transition region of the mixtures has been analyzed by dynamic mechanical measurements. Mechanical properties and fracture toughness of the modified mixtures have been related to their microstructural spherical features. Results are compared to those for the unmodified mixtures cured with different precure temperatures. © 1997 John Wiley & Sons, Inc.     

Curing kinetics and thermal stability of diglycidyl ether of bisphenol

Curing kinetics of diglycidyl ether of bisphenol-A (DGEBA) in the presence of varying molar ratios of aromatic imide-amines and 4,4′-diaminodiphenylsulfone (DDS) were investigated by the dynamic differential scanning calorimetry. The imide-amines were prepared by reacting 1 mole of benzophenone 3,3′,4,4′-tetracarboxylic acid dianhydride (B) with 2.5 moles of 4,4′-diaminodiphenyl ether (E)/ or 4,4′-diaminodiphenyl methane (M)/ or 4,4′-diaminodiphenylsulfone (S) and designated as BE/ or BM/ or BS. The mixture of imide-amines and DDS at ratio of 0:1, 0.25:0.75, 0.5:0.5, 0.75:0.25 and 1:0 were used to investigate the curing behaviour of DGEBA. The multiple heating rate method (5, 10, 15 and 20°C min⁻¹) was used to study the curing kinetics of epoxy resins. The peak exotherm temperature was found to be dependent on the heating rate, structure of imide-amines as well as on the ratio of imide-amine: DDS used. A broad exotherm was observed in the temperature range of 180–230°C on curing with mixture of imide-amines and DDS. Curing of DGEBA with mixture of imide-amines and/or DDS resulted in a decrease in characteristic curing temperatures. Activation energy of curing reaction as determined in accordance to the Ozawa’s method was found to be dependent on the structure of amine. The thermal stability of the isothermally cured resins was also evaluated using dynamic thermogravimetry in a nitrogen atmosphere. The char yield was highest in case of resins cured using mixture of DDS: BS (0.25:0.75; EBS-3), DDS: BM (0.5: 0.5; EBM-2) and DDS: BE (0.5: 0.5; EBE-2).     

A Well-Defined Cyclotriphosphazene-Based Epoxy Monomer and Its Application as A Novel Epoxy Resin: Synthesis,Curing Behaviors,and Flame Retardancy

Abstract

A novel cyclotriphosphazene-based epoxy monomer, hexa-[4-(glycidyloxycarbonyl) phenoxy]cyclotriphosphazene (HGCP), was synthesized via a four-step synthetic route, and fully characterized by ¹H, ¹³C, and ³¹P NMR spectroscopy, high-resolution mass spectrometry, and elemental analysis. Thermosetting systems based on HGCP with three curing agents, for example, 4,4′-diaminodiphenylsulfone (DDS), 4,4′-diaminodiphenylmethane (DDM), and dicyandiamide (DICY), were used for making a comparison of their thermal curing behaviors. The curing behaviors were measured by differential scanning calorimetry. Moreover, flame retardancy of HGCP thermosetting systems was estimated by Limiting Oxygen Index (LOI) and Vertical Burning Test (UL-94). The resulting HGCP thermosetting systems exhibited better flame retardancy than the common epoxy resins diglycidyl ether of bisphenol A (DGEBA) and the regular brominated bisphenol A epoxy resin (TBBA) cured by DDS, respectively. When HGCP was cured by DDS, its thermosetting system gave the most char residues, met the UL-94 V-0 classification, and had a limiting oxygen index value greater than 35.     

Curing and thermal behaviour of epoxy resin in the presence of a mixture of imide-amines

The curing behaviour of diglycidyl ether of bisphenol-A (DGEBA) was investigated by the dynamic differential scanning calorimetry using varying molar ratios of aromatic imide-amines and 4,4′-diaminodiphenylsulfone (DDS). The imide-amines were prepared by reacting 1 mole of naphthalene 1,4,5,8-tetracarboxylic dianhydride (N) and 4,4′-oxodiphthalic anhydride (O) with 2.5 moles of 4,4′-diaminodiphenyl ether (E) or 4,4′-diaminodiphenyl methane (M) or 4,4′-diaminodiphenylsulfone (S) and designated as NE/OE or NM/OM or NS/OS. The mixture of the imide-amines and DDS at ratio of 0:1, 0.25:0.75, 0.5:0.5, 0.75:0.25 and 1:0 were used to investigate the curing behaviour of DGEBA. A single exotherm was observed on curing with mixture of imide-amines and DDS. This clearly shows that the two amines act as co-curing agents. Curing temperatures were higher with imide-amines having sulfone linkage irrespective of anhydride. Curing of DGEBA with mixture of imide-amines and or DDS resulted in a decrease in characteristic curing temperatures. The thermal stability of the isothermally cured resins was also evaluated using dynamic thermogravimetry in a nitrogen atmosphere. The char yield was higher in case of resins cured imide-amines based on N and E. The activation energy of decomposition and integral procedural decomposition temperature were also calculated from the TG data.     

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.     

2－乙基－4－甲基咪唑固化环氧树脂的固化反应机理、动力学及其反应活性

本文应用ＤＳＣ和ＦＴＩＲ对２－乙基－４－甲基咪唑固化双酚Ａ二缩水甘油醚型环氧树脂体系的固化反应机理和２－乙基－４－甲基咪唑固化双酚Ａ二缩水甘油醚型、缩水甘油酯与脂环型环氧树脂体系的固化反应特征、动力学及其反应活性进行了研究．结果表明，双酚Ａ二缩水甘油醚型环氧树脂／咪唑体系的固化反应是分两步独立进行的，第一步是加成反应，第二步是催化聚合反应．缩水甘油酯与脂环型环氧树脂（ＴＤＥ－８５）／咪唑体系的固化反应过程也分两步进行，第一阶段反应主要是缩水甘油酯型环氧基进行的加成反应和催化聚合反应，第二阶段主要是脂环型环氧基进行的加成反应．各体系第一阶段的表现反应活化能均低于第二阶段活化能．当ＴＤＥ－８５型环氧树脂中引入缩水甘油醚型环氧树脂后，固化反应速率均较ＴＤＥ－８５环氧树脂单独固化时快．     

Curing kinetics of bio-based epoxy resin-toughened DGEBA epoxy resin blend

In the present study, TEIA bioresin was blended with the diglycidyl ether bisphenol A (DGEBA) epoxy resin in different ratios (i.e. 10, 20, 30, 40 mass%), cured with methylhexahydrophthalic anhydride curing agent in the presence of 2-methylimidazole catalyst. The optimized composition of DGEBA and TEIA bioresin blends system was employed as an adhesive strength. The adhesive strength of the TEIA-modified DGEBA epoxy resin blend system was increased from 4.14 to 6.31 MPa on an aluminium substrate compared to the DGEBA epoxy resin. The curing kinetics of non-isothermal, DGEBA epoxy resin and its bio-based blend systems were investigated employing differential scanning calorimetry. An increase in the peak temperature and reduction in a heat of curing as well as activation energy in DGEBA epoxy resin were observed with the addition of TEIA bioresin content. The activation energy (E_a) of the DGEBA resin and their bio-based blend system were obtained from Kissinger and Flynn–Wall–Ozawa methods.

     

一种液晶环氧增韧环氧树脂的研究

环氧树脂具有优异的机械性能 ,耐高温以及良好的加工工艺性 .被广泛用于机械、航天、船舶等领域 .由于环氧树脂固化后断裂延伸率小 ,脆性大 ,使其应用受到了一定的限制 .为此 ,国内外学者对环氧树脂进行了大量的改性研究工作 .用含有“柔性链段”的固化剂固化环氧 ,在交联网络中引入柔性链段[1] ;在环氧基体中加入橡胶弹性体[2 ] 、热塑性树脂[3 ,4] 、液晶聚合物[5,6] 等分散相或用热固性树脂连续贯穿于环氧树脂网络中形成互穿、半互穿网络结构[7] ,以改善环氧树脂的韧性 .本文采用液晶环氧化合物原位复合增韧环氧树脂 ,考察了液晶环氧对环…     

Mechanical properties and inhomogeneous nanostructures of dicyandiamide-cured epoxy resins

Dicyandiamide (DICY)-cured epoxy resins are important materials for structural adhesives and matrix resins for fiber reinforced prepregs. The objective of this study was to examine the mechanical and physical properties as well as the gel structures of the cured resins and discuss the relationships among them. Diglycidyl ether of bisphenol-A (DGEBA) oligomers were chosen as the common chemical structure of the epoxy resins. Four kinds of resin mixtures were formulated using the seven types of DGEBA oligomers having different molecular weight distributions. Three resin formulations having bimodal-type molecular weight distributions were designed to have almost identical rubbery plateau values of the storage modulus in dynamic mechanical analyses after curing, means that they had almost equivalent average crosslink density and basic chemical structure. However, the toughness, ductility, and environmental (heat and solvent) resistance of these three formulations were different. Atomic force microscopy revealed the existence of inhomogeneous nanoscale gel structures in these cured resins. The morphological differences in the gel structures in terms of their size, the connectivity, and the relative magnitude of the heterogeneity would cause the difference in several properties of the DICY-cured epoxy resins. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 1425–1434, 2007     

Facile synthesis of bio-based phosphorus-containing epoxy resins with excellent flame resistance

The development of high-performance biomass-derived epoxy thermosets with excellent flame resistance is vital to various applications (i.e., composites, coatings and adhesives). Herein, a difunctional epoxy monomer bis(2-methoxy-4-(oxiran-2-ylmethyl)phenyl) phenyl phosphate (BEU-EP) was synthesized from abundant and biobased eugenol. In addition, BEU-EP was cured by 4,4′-diaminodiphenyl methane (DDM) and the cured resin diglycidyl ether of bisphenol A (DGEBA)/DDM was used as a reference. Results indicated that BEU-EP/DDM not only showed a 58.1%, 28.8% and 35.1% increase in residual char (at 700 °C), flexural and storage modulus (at 30 °C) compared with DGEBA/DDM, but also exhibited excellent flame resistance and smoke suppression. BEU-EP/DDM passed V-0 rating (in UL-94 testing) with limiting oxygen index (LOI) of 38.4% and greatly decreased the peak heat release rate (pHRR) and total smoke production (TSP) by 84.9% and 80.5%, respectively. The mechanism analysis confirmed that the phosphorus-containing group and aromatic structure from BEU-EP contributed both the gas and condensed-phase flame retardation of BEU-EP/DDM network. This work provides an efficient and scalable route for synthesizing biobased epoxy thermosets with high integrated performance and superior flame resistance.     

Synthesis and thermal characterization of phosphorus containing siliconized epoxy resins

Siliconized epoxy matrix resin was developed by reacting diglycidyl ethers of bisphenol A (DGEBA) type epoxy resin with hydroxyl terminated polydimethylsiloxane (silicone) modifier, using γ-aminopropyltriethoxysilane crosslinker and dibutyltindilaurate catalyst. The siliconized epoxy resin was cured with 4, 4-diaminodiphenylmethane (DDM), 1,6-hexanediamine (HDA), and bis (4-aminophenyl) phenylphosphate (BAPP). The BAPP cured epoxy and siliconized epoxy resins exhibit better flame-retardant behaviour than DDM and HDA cured resins. The thermal stability and flame-retardant property of the cured epoxy resins were studied by thermal gravimetric analysis (TGA) and limiting oxygen index (LOI). The glass transition temperatures (T_g) were measured by differential scanning calorimetry (DSC) and the surface morphology was studied by scanning electron microscopy (SEM). The heat deflection temperature (HDT) and moisture absorption studies were carried out as per standard testing procedure. The thermal stability and flame-retardant properties of the cured epoxy resins were improved by the incorporation of both silicone and phosphorus moieties. The synergistic effect of silicone and phosphorus enhanced the limiting oxygen index values, which was observed for siliconized epoxy resins cured with phosphorus containing diamine compound.