New degradable thermosets obtained by cationic copolymerization of DGEBA with an s(γ-butyrolactone)

Diglycidylether of bisphenol A (DGEBA) was cured with different proportions of 1,6-dioxaspiro[4.4]nonane-2,7-dione (s(γ-BL)) with ytterbium triflate as initiator. The curing was studied with differential scanning calorimetry (DSC) and Fourier transform infrared in the attenuated total reflection mode (FTIR/ATR). FTIR/ATR was used to monitor the competitive reactive processes and to quantify the conversion of the epoxide, lactone and intermediate spiroorthoester (SOE) groups. The shrinkage undergone during curing was monitored by means of thermomechanical analysis (TMA). By combining the results obtained by FTIR/ATR and TMA, the processes that were and were not responsible for shrinkage were identified. The thermal and dynamic mechanical properties of the cured materials were determined by DSC and by dynamic mechanical thermal analysis (DMTA), respectively. The kinetic triplet associated with calorimetric curing was determined by means of isoconversional analysis. An increase in the proportion of lactone results in an increased curing rate, a decrease in shrinkage after gelation and a decrease in the glass transition temperature (T_g). Finally, as a preliminary measure, we examined the potential of the systems studied as reworkable materials by means of hydrolytic and thermal degradation. An increase in the ester units in the network results in materials that are less thermally stable and whose controlled degradability is greater.     

A new strategy for controlling shrinkage of DGEBA resins cured by cationic copolymerization with hydroxyl‐terminated hyperbranched polymers and ytterbium triflate as an initiator

We report a novel strategy for preparing epoxy thermosetting systems with low shrinkage and improved flexibility and degradability. Diglycidyl ether of bisphenol A (DGEBA) resin was cured with different proportions of hydroxyl‐terminated hyperbranched polymer (HBP), using ytterbium triflate as a cationic initiator. The curing process was studied using differential scanning calorimetry and thermomechanical analysis. Characterization of the resulting materials was evaluated using DSC, thermogravimetric analysis, and dynamic mechanical thermal analysis, and the fracture surface was studied using scanning electron microscopy (SEM). When DGEBA is modified with HBP, it shows a homogeneous morphology and the HBP is incorporated chemically into the network, because hydroxyl groups can react with epoxides under cationic conditions. Higher proportions of HBP reduce the glass transition temperature (T_g) and thermal stability and increase the flexibility. When the proportion of HBP in the curing mixture is increased, the degree of shrinkage is reduced significantly and expansion can be observed. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

New thermosets obtained by cationic copolymerization of DGEBA with γ‐caprolactone with improvement in the shrinkage. II. Time–temperature–transformation (TTT) cure diagram

Mixtures of diglycidylether of bisphenol A (DGEBA) with different proportions of γ‐caprolactone (γ‐CL) were cured with ytterbium triflate as initiator. The curing was studied with differential scanning calorimetry (DSC) and thermo mechanical analysis (TMA). The results are presented in the form of a time–temperature–transformation diagram. The kinetic analysis was performed by means of the isoconversional integral procedure and the kinetic model was also determined using the Coats–Redfern method. Gelation was determined by means of combined experiences of DSC and TMA. The relationship between the glass transition temperature (T_g) and the degree of conversion α was determined by DSC. Using the isoconversional lines and the T_g‐α relationship, the vitrificacion curve was obtained. The methodology developed makes it possible to obtain the TTT diagram using only no‐isothermal experiments with equivalent results to those using classical isothermal procedures. The addition of γ‐CL accelerates the curing and reduces the shrinkage after gelation and consequently the internal stresses in the material. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Cationic copolymerization of DGEBA with two bicyclic bis(γ-lactone) derivatives using rare earth metal triflates as initiators

The thermal cationic curing of mixtures in different proportions of diglycidylether of bisphenol A (DGEBA) with two differently substituted condensed bis(γ-lactone)s (BisMe and BisPhe) initiated by scandium, ytterbium and lanthanum triflates or a conventional BF₃·MEA initiator was investigated. Non-isothermal differential scanning calorimetry (DSC) experiments at a controlled heating rate were used to evaluate the evolution of the reactive systems. BF₃·MEA and rare earth metal triflates initiated curing systems follow a different evolution. Among rare earth metal triflates tested, the scandium was the most active initiator. The phenomenological changes that take place during curing were studied and represented in time-temperature-transformation (TTT) diagrams. The improvement in the reworkable character of the materials prepared was confirmed by thermogravimetry. The thermomechanical characteristics were also evaluated.     

Kinetic study by FTIR,TMA, and DSC of the curing of a mixture of DGEBA resin and γ‐butyrolactone catalyzed by ytterbium triflate

A mixture of diglycidylether of bisphenol A (DGEBA) and γ‐butyrolactone (γ‐BL) was cured in the presence of ytterbium triflate as a catalyst. The kinetics of the various elemental processes that occur in the curing process were studied by means of isothermal curing in the FTIR spectrometer. The kinetics of the contraction during the curing was also evaluated by TMA. In both cases, the kinetics was analyzed by means of isoconversional procedure and the kinetic model was determined with the so‐called compensation effect (isokinetic relationship). The isothermal kinetic analysis was compared with that obtained by dynamic curing in DSC. We found that all the reactive processes and the contraction follow a surface‐controlled reaction type of kinetic mechanism, R₃. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 381–393, 2004     

Kinetic study of the curing of mixtures of DGEBA and five‐membered cyclic carbonates with lanthanum triflate as cationic initiator

Mixtures of diglycidylether of bisphenol A (DGEBA) with 1,3‐benzodioxolane‐2‐one (CC) or 4‐phenoxymethyl‐1,3‐dioxolane‐2‐one (PGEC) were cured in the presence of lanthanum triflate. FTIR/ATR was used to study the evolution of carbonate and epoxide groups to follow the reactive processes that take place during curing. DSC was applied to study the thermal characteristics of the curing process and to determine the glass‐transition temperatures of the cured materials. The kinetics of the curing was studied isothermally by means of FTIR and the kinetic model was selected through the isokinetic relationships. DSC experiments were used to study the kinetics in nonisothermal conditions by means of isoconversional procedures and the Coats–Redfern and Criado methodologies. By TMA we could monitor the evolution of the shrinkage during isothermal curing. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 2875–2884, 2007     

Anionic copolymerization of DGEBA with two bicyclic bis(γ-lactone) derivatives using tertiary amines as initiators

The anionic copolymerization, to form thermosets, of diglycidylether of bisphenol A (DGEBA) with two condensed bis(γ-lactone)s (bisMe and bisPhe) using 4-(N,N-dimethylamino)pyridine (DMAP), 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), and 1-methylimidazole (1MI) as initiators was studied by differential scanning calorimetry (DSC). The kinetics was evaluated by isoconversional procedures. The evolution of the typical functional groups that form or disappear during curing was followed by Fourier transform infrared in the attenuated-total-reflection mode (FTIR/ATR) to clarify the reactive processes that takes place. Unexpected processes, which lead to the formation of five-membered lactones, were detected when non-stoichiometric proportions of monomers were used. The stoichiometric DGEBA/bislactone ratio produces the expected alternate poly(ester-ketone) network. The thermal degradability of the materials obtained was evaluated by TGA, and their reworkable character was confirmed. Materials obtained from stoichiometric mixtures were completely soluble in ethanolic KOH.     

Polylactic acid/ethylene glycol triblock copolymer as novel crosslinker for epoxidized natural rubber

Polylactic acid/ethylene glycol triblock copolymer (LLA₄₆EG₄₆LLA₄₆) was prepared and used in a crosslink process of epoxidized natural rubber (ENR) by employing a ring‐opening reaction using Sn(Oct)₂ as a catalyst. The OH‐capped copolymer acts as a macromolecular crosslinking agent in the formation of ENR networks, leading to drastic enhancement in tensile properties. Crosslink efficiency and chemical structures of the cured materials are examined by solvent fractionation, swelling experiments, XRD, ¹H‐NMR, and ATR‐FTIR spectroscopy. The efficiency of the curing process is dependent on the ENR/copolymer feed ratios. The degree of property improvement and gas permeability/selectivity behaviors of the cured materials are strongly dependent on the copolymer content and the efficiency of the curing process. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

New chemically reworkable epoxy coatings obtained by the addition of polyesters with star topologies to diglycidyl ether of bisphenol A resins

A new multiarm star with hyperbranched aromatic–aliphatic polyester core and poly(?-caprolactone) arms (HBPCL) was synthesized and characterized. Mixtures of diglycidyl ether of bisphenol A (DGEBA) resin and different proportions of this star type modifier were cured using a thermal cationic curing agent, Yb(OTf)₃. The HBPCL prepared has hydroxyl groups as chain ends, which are capable of chemically incorporating to the epoxy matrix by means of the monomer activated mechanism. This, together with the chemical structure of the modifier, allowed the preparation of new homogeneous thermosets for coating applications. The curing mixtures were investigated by differential scanning calorimetry (DSC) to study the curing process and evaluate the kinetic parameters of the formulations. These studies demonstrated that HBPCL decreased the curing rate and affected the gelation process. The thermosets obtained showed an improvement in impact strength with a discrete reduction of the T_g. The modified coatings showed an increased reworkability in alkaline solution with the maintenance of thermal stability.     

Catalyzed crosslinking of highly functional biobased epoxy resins

Crosslinking reactions involving epoxy homopolymerization of 100% biobased epoxidized sucrose esters (ESEs) were studied and the resulting coatings properties were compared against epoxidized soybean oil (ESO) and petrochemical-based soybean fatty acid ester resins. The low viscosity of ESE resins allowed for formulations to be developed with minimal volatile organic content. ESEs were found to have superior coatings properties, compared to ESO and the petrochemical-based soybean esters, attributable to a higher glass transition temperature (T _g) and a higher modulus. The rigid sucrose core on ESEs provided an increase in coating performance when compared to coatings from epoxidized resins synthesized with tripentaeryithritol as a core. The degree of conversion and optimization of the curing conditions were studied using differential scanning calorimetry (DSC). Thermal analysis of cured coatings was performed using DSC, dynamic mechanical analysis, and thermogravimetric analysis. In order to further enhance the coatings properties, small amounts of bisphenol A epoxy resin were added which resulted in higher moduli and T _gs.     

Curing kinetics and thermal properties of vinyl ester resins

The curing kinetics of dimethacrylate-based vinyl ester resins were studied by scanning and isothermal DSC, gel time studies, and by DMTA. The rate of polymerization was raised by increased methyl ethyl ketone peroxide (MEKP) concentration but the cocatalyst, cobalt octoate, retarded the reaction rate, except at very low concentrations. By contrast, the gel time was reduced for all increases in either peroxide or cobalt concentration. This contradictory behavior was explained by a kinetic scheme in which the cobalt species play a dual role of catalyzing the formation of radicals from MEKP and of destroying the primary and polymeric radicals. The scanning DSC curves exhibited multiple peaks as observed by other workers, but in the present work, these peaks were attributed to the individual influence of temperature on each of fundamental reaction steps in the free radical polymerization. Physical aging appeared to occur during the isothermal polymerization of samples cured below the “fully cured” glass transition temperature (T_g). For these undercured materials, the difference between the DSC T_g and the isothermal curing temperature was approximately 11°C. Dynamic mechanical analysis of a partially cured sample exhibited anomalous behavior caused by the reinitiation of cure of the sample during the DMTA experiment. For partially cured resins, the DSC T_g increased monotonically with the degree of cure, and this dependence was fitted to an equation related to the Couchman and DiBenedetto equations. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 64: 769–781, 1997     

Application of electrochemical techniques to study the effect on the anticorrosive properties of the addition of ytterbium and erbium triflates as catalysts on a powder epoxy network

New low curing temperature epoxy powder coatings cured with o-tolylbiguanide and catalyzed by the use of erbium(III) and ytterbium(III) trifluoromethanesulfonates have been formulated. Their curing kinetics and anticorrosive properties have been studied and compared with a system commonly used in industry (o-tolylbiguanide/epoxy resin). Three different tests for measuring anticorrosive properties (EIS, AC/DC/AC, and salt fog spray) have been used together with an adherence test, in order to establish the ideal system. Results show that a system using 1 phr of ytterbium triflate presents good anticorrosive properties. The technique AC/DC/AC has shown its ability to evaluate properly and much faster than other techniques the anticorrosive properties of powder coatings with similar results.     

Amorphous polyamide coating resins from sugar-derived monomers

In this article, the synthesis of bio-based polyamides for powder coating applications and their evaluation in a solventborne coating system are reported. The M _n values of the resins were between 3000 and 4000 g mol^?1 and the resins displayed T _g values from 60 to 80°C. Both amine and carboxylic acid functionalities (total ~0.6 mmol g^?1) were introduced for curing purposes. The resins were cured with triglycidyl isocyanurate (TGIC) or N,N,N′,N′-tetrakis(2-hydroxyethyl)adipamide (Primid XL-552). The curing reaction was followed using rheology which indicated that TGIC achieved higher reaction rates and higher gel contents. The DSC analysis of the cured disks showed that all cured samples were amorphous as is desired for the targeted coating application. The resins required a curing temperature higher than 150°C. Aluminum panels were coated using a solventborne approach and the coatings were cured at 180°C during 1 h. Dewetting was observed on all panels. Network formation was adequate for an amine-functional resin cured with TGIC as indicated by solvent resistance testing. In conclusion, the developed bio-based polyamide resins are promising materials to be used as binder resins in powder coating applications.     

端脂肪氨基聚醚/环氧树脂胶粘剂的固化工艺研究

以端脂肪氨基聚醚(AATPE)作为环氧树脂(EP)的固化剂,制备出一种高强度、高韧性的EP胶粘剂。采用动态差示扫描量热(DSC)法和凝胶化理论模型研究了AATPE/EP胶粘剂体系的固化反应特点,并对其固化工艺进行了优化。结果表明:AATPE/EP体系的最佳固化工艺条件为"50℃/6 h→100℃/2 h";在最佳固化工艺条件下制备的固化产物,其固化度为97.14%,并且其力学性能优异。     

Synthesis and characterization of a novel heat resistant epoxy resin based on N,N′-bis(5-hydroxy-1-naphthyl)pyromellitic diimide

A novel epoxy resin containing imide and naphthyl groups was synthesized, and characterized using NMR, NMR, FT-IR spectra and elemental analyses. The curing behavior was investigated with differential scanning calorimetry (DSC) using 4,4′-diaminodiphenylsulfone (DDS) as curing agent. The physical properties of the cured polymer were evaluated with dynamic thermal mechanical analysis (DMTA) and thermogravimetric analysis (TGA). The results showed that the cured polymer exhibited higher glass transition temperature (T_g) and better thermal stability compared with those commercial available heat resistant epoxy resins.     

咪唑促进双氰胺固化环氧树脂体系固化动力学

采用差示扫描量热(DSC)法研究了2-乙基-4-甲基咪唑(2E4MI)的含量对双氰胺(DICY)固化环氧树脂体系固化动力学的影响。非等温DSC测试结果表明,2E4MI能大幅度降低DICY固化环氧树脂所需要的温度和活化能,从而加快反应的进行。当2E4MI用量为0.2份时,活化能最低为84.2 kJ/mol且整体活化能随固化度的变化较小、固化更均匀。在2E4MI最佳用量(0.2份)下对固化体系进行等温DSC以及潜伏性测试,结果表明,该体系在160℃下20 min内可完成固化,室温储存15 d的固化度仅为0.146,说明其适合用作快速固化环氧树脂储存体系。     

DGEBA thermosets modified with an amphiphilic star polymer. Study on the effect of the initiator on the curing process and morphology

We have studied the preparation of a new class of epoxy thermosets from diglycidyl ether of bisphenol A (DGEBA) modified with an amphiphilic star polymer (SP), initiated either by 1-methyl imidazole or ytterbium triflate, anionic and cationic initiators, respectively. The curing process has been characterized by means of DSC, FTIR and rheology. The last technique allowed us to monitor the shrinkage during curing. DMTA provided valuable information about the transitions of the materials, as well as their modulus in the rubbery state. Cationic systems produce monomodal tan δ relaxations, whereas anionics presented a shoulder in this peak. By means of electron microscopy we could observe phase separation in the case of cationically initiated systems while in the anionic initiated materials zones with different electronic densities were appreciated. Finally, Young’s modulus and hardness of the materials were determined by nanoinentation.     

Curing and characterization of oxazolidone-isocyanurate-ether networks

Oxazolidone-isocyanurate-ether networks were prepared by copolymerization of mixtures of DGEBA and toluene-2,4-diisocyanate (TDI) in presence of benzyldimethylamine (BDMA) as catalyst. Changes during curing and final properties of the cured materials were investigated by using DSC, FTIR/ATR, TMA, DMTA, TGA, and densitometry. The influence of the molar ratio of isocyanate to epoxide groups on the properties and curing were studied. The kinetics of curing was analyzed by means of an integral isoconversional nonisothermal procedure. The fractions of oxazolidone, isocyanurate, and ether groups present in the final network were evaluated and were found to be dependent on the initial isocyanate/epoxy ratio and curing conditions. By increasing the initial proportion of isocyanate the glass transition temperature, the thermal stability, the shrinkage, and the amount of isocyanurate rings increase, whereas the fraction of ether linkages and oxazolidones decreases. It was observed that the gelation is controlled by the formation of isocyanurate rings at the beginning of the curing. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Curing behavior and thermal properties of multifunctional epoxy resin with methylhexahydrophthalic anhydride

The curing behavior and thermal properties of bisphenol A type novolac epoxy resin (bisANER) with methylhexahydrophthalic anhydride (MHHPA) at an anhydride/epoxy group ratio of 0.85 was studied with Fourier‐transform infrared (FTIR) spectroscopy, differential scanning calorimetry (DSC), and thermogravimetry. The results showed that the FTIR absorption intensity of anhydride and epoxide decreased during the curing reaction, and the absorption peak of ester appeared. The dynamic curing energies were determined as 48.5 and 54.1 kJ/mol with Kissinger and Flynn–Wall–Ozawa methods, respectively. DSC measurements showed that as higher is the curing temperature, higher is the glass transition. The thermal degradation of the cured bisANER/MHHPA network was identified as two steps: the breaking or detaching of ? OH, ? CH₂? , ? CH₃, OC? O and C? O? C, etc., taking place between 300 and 450°C; and the carbonizing or oxidating of aromatic rings occurring above 450°C. The kinetics of the degradation reaction was studied with Coats–Redfern method showing a first‐order process. In addition, vinyl cyclohexene dioxide (VCD) was employed as a reactive diluent for bisANER (VCD/bisANER = 1 : 2 w/w) and cured with MHHPA, and the obtained network had a higher T_g and a slight lower degradation temperature than the undiluted system. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 2041–2048, 2007