Electron‐beam curing of hydrogenated acrylonitrile–butadiene rubber

The electron‐beam‐induced crosslinking of hydrogenated acrylonitrile–butadiene rubber (HNBR) was investigated. HNBR sheets were exposed to electron‐beam irradiation in air at a room temperature of 25 ± 2°C over a dose range of 0–20 Mrad. An attempt was made to correlate the structure of the irradiated rubber with the properties. The ratio of chain scission to crosslinking and the gelation dose were determined by a method proposed elsewhere. The gel content and dynamic storage modulus increased with the radiation dose. Fourier transform infrared studies revealed the formation of double bonds and carbonyl and ether groups. These observations were further supported by a thermogravimetric analysis of the carbonaceous residue of irradiated HNBR. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 648–651, 2005     

Exothermic effect in the process of electron‐beam curing of epoxy resins

Temperature measurements have been performed in the process of electron‐beam curing of EB‐I and EB‐II epoxy resin systems. The influence of initiator content, resin type, and dose rate on the temperature of the systems was studied. Transverse and longitudinal temperatures of samples in the glass vessel were also analyzed. The nature of temperature curves varied with the different epoxy resin systems in the steel mold, but did not change with different contents of the initiator. At the same time, the heat had no effect on the gel fraction of epoxy resin systems. The temperature curve was greatly affected by the dose rate, and its peak value, peak width, and plateau value also increased with it. The transverse temperature of EB‐II glass vessel samples increased as the radiation dose increased and, in the same sample, the temperature reduced as the distance between the radiation center and the test point increased. The longitudinal temperature of EB‐I and EB‐II resin systems in a glass vessel decreased as the radiation depth increased. As the radiation dose increased, the temperature of the EB‐I resin system increased simultaneously, while that of the EB‐II resin system initially increased and then kept constant when the dose reached a certain value. The temperatures of these two resin systems decreased rapidly when the radiation process stopped. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 2217–2222, 2004     

Lifetime prediction of the epoxy system DGEBA (n = 0)/1,2‐DCH modified with an epoxy reactive diluent by thermogravimetric analysis

Thermogravimetric analysis was used to predict the lifetime of two three‐component systems of diglycidyl ether of bisphenol A (n = 0)/1,2‐diamine cyclohexane [DGEBA (n = 0)/1,2‐DCH] modified with different concentrations of an epoxy reactive diluent, vinylcyclohexene dioxide (VCHD). Experimental results were treated using two methods. The first method was independent of the degradation mechanism, and the second was based on the thermodegradation kinetic mechanism. The activation energies of the reaction were determined using the Flynn–Wall–Ozawa method. These values were compared with those obtained using Kissinger's method. From experimental results it was found that the optimum temperature of service for these materials were different, so one or the other must be selected, depending on the application temperature considered. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 3835–3839, 2003     

Characterization of UV‐curable reactive diluent containing quaternary ammonium salts for antistatic coating

Reactive diluent with quaternary ammonium salts (RDQ) for UV‐curable antistatic coating was synthesized by reacting glycidyl methacrylate (GMA) and piperazin with dropping the methansulfonic acid. In order to compare the curing behavior of RDQ with commercial monomers, the photopolymerization of RDQ, 1,6‐hexandiol diacrylate (HDDA) and 1,6‐hexandiol dimethacrylate (HDDMA) were studied by using real‐time IR spectroscopy. Surface properties such as surface resistance, pencil hardness, and solvent resistance of the cured films containing RDQ were investigated. When used as a reactive diluent in the UV‐curable coating formulation, the RDQ imparted excellent antistatic properties to the final material. The results of an Fourier transform infrared/attenuated total reflectance (FTIR/ATR) depth profile analysis show that RDQ molecules are more concentrated near the surface within a micrometer‐thick layer, indicating that existence of the ionic components in the surface layer is responsible for antistatic property. Film cured from the formulation containing 12 wt % of RDQ showed the best mechanical properties with reasonable surface properties. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 132–137, 2002; DOI 10.1002/app.10273     

The curing of UF resins studied by low‐resolution 1H‐NMR

A series of UF resins and one MUF resin were studied by low‐resolution ¹H‐NMR. The mobility of the resin during curing could be followed by measuring the spin‐spin relaxation time (T₂) with curing time. The relative curing behavior was similar to that found by traditional gel time measurements. In addition, extra features in the T₂ plots with curing time showed at what point the bulk of the condensation reactions took place. The speed of cure was also related to the chemical groups in the liquid resin, and it was found that the linear methylol groups were mainly responsible for the curing speed of the resins. By studying the curing with different hardener levels and glue concentrations it was found that a UF resin is more sensitive to the glue mix concentration than an MUF resin. A cured resin was also studied after curing to investigate postcuring effects. Water seemed to play the biggest role in the postcure, with substantial amounts present immediately after cure, which decreased with curing time and aging. For the low mol ratio resins studied here further curing reactions did not seem to play a major role in the post curing phenomenon. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 754–765, 2000     

Influence of a long‐side‐chain‐containing reactive diluent on the structure and mechanical properties of UV‐cured films

The dimethacrylate reactive diluent (HEMA‐DDSA), a long‐side‐chain‐containing reactive diluent, was prepared by reacting 2‐dodecen‐1‐ylsuccinic anhydride with two equivalents of hydroxyethyl methacrylate. Its structure was characterized by IR and ¹H NMR spectroscopy. This new diluent was added into the formulation of UV‐curable epoxy acrylate networks. Results show that the formulation with the addition of HEMA‐DDSA has massively reduced viscosity and shows several attractive properties of epoxy acrylate oligomers. The mechanical resistance of the films is dramatically enhanced with the incorporation of long alkyl groups derived from HEMA‐DDSA, the plastic deformation zone expands, thus decreasing the inner stress of the polymer structure. Moreover, the cured coatings have a higher glass transition temperature as the percentage of HEMA‐DDSA is increased up to 5 wt%. Due to the excellent integrated performance of the polymeric films, HEMA‐DDSA proved to be an effective reactive diluent, which is of potential interest for applications in high performance materials. © 2016 Society of Chemical Industry     

Dynamic mechanical analysis study of the curing of phenol‐formaldehyde novolac resins

The curing reaction of typical commercial phenol‐formaldehyde novolac resins with hexamethylentetraamine (HMTA) was followed by dynamic mechanical analysis. The evolution of the rheological parameters, such as storage modulus G′, loss modulus G″, and tanδ (G″/G′), as a function of time, for samples of the phenolic resins on cloth, was recorded. The curing reaction, leading to the formation of a crosslinked structure, is described by a third‐order phenomenological equation. This equation takes into account a self‐acceleration effect, as a consequence not only of the chemical reaction of crosslinking after the gel point but of phase segregation as well. This rheokinetic model of the curing of phenolic novolac resins permits the determination of the numerical values of the kinetic equation constants. The influence of the composition, structure, and physical treatment on the curing kinetics of the novolac resins is evaluated. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 1902–1913, 2001     

Cationic electron‐beam curing of a high‐functionality epoxy: effect of post‐curing on glass transition and conversion

This paper reports on the cationic electron‐beam curing of a high‐functionality SU8 epoxy resin, which is extensively used as a UV‐curing negative photoresist for micro‐electronics machine systems (MEMS) applications. Results show that elevated post‐curing treatment significantly increased both the conversion and the glass transition. The degree of conversion and the glass transition temperature were measured by using Fourier‐transform infrared (FTIR) spectroscopy and modulated differential scanning calorimetry (MDSC^®), respectively. The glass transition temperature (T_g), which has been observed to be dependent on the degree of conversion, reaches a maximum of 162 °C at 50 Mrad and post‐curing at 90 °C. The degradation pattern of the cured resin does not show much variation for exposure at 5 Mrad, but does show significant variation for 50 Mrad exposure at various post‐curing temperatures. A degree of conversion of more than 0.8 was achieved at a dosage of 30 Mrad with post curing at 80 °C, for the epoxy resin with an average functionality of 8 a feature simply not achievable when using UV‐curing. Copyright © 2004 Society of Chemical Industry     

Thermal and dielectric properties of bismaleimide‐triazine resins containing octa(maleimidophenyl)silsesquioxane

Octa(maleimidophenyl)silsesquioxane (OMPS) was synthesized, characterized, and employed to modify the BT resin which composed of 4,4′‐bismaleimidodiphenylmethane (BMI) and 2,2′‐bis(4‐cyanatophenyl)propane (BCE). The curing reaction between OMPS and BT resin was first investigated. It was found that OMPS accelerate the curing reaction of BCE, and the onset temperature of the cyclotrimerization was reduced up to 95.5°C (by DSC). As demonstrated by DSC and FTIR, there was no evidence that indicated the coreaction between maleimide and cyanate ester. 2,2′‐diallyl bisphenol A (DBA) and diglycidyl ether of bisphenol A (E‐51) (Wuxi Resin Factory, Jiangsu Province, China) were also used to enhance the toughness of BT resin, and the formulated BTA (containing DBA) and BTE (containing E‐51) resins were obtained. The thermal properties of BT, BTA, and BTE resins incorporated with OMPS were then investigated. The results of DMA and TG showed that the BT, BTA, and BTE resins containing 1 wt % of OMPS exhibit enhanced thermal properties in comparison with their pristine resins respectively, while more contents of OMPS may impair the thermal properties of the polymer matrix, though the effect of OMPS was slight. Finally, the dielectric constant of these hybrid materials were detected, and their dielectric constant were distinctly reduced by the incorporation of OMPS, while overmuch contents of OMPS were disadvantageous for dielectric constant because of the aggregation of OMPS. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci 2008     

A new method to improve the stability,tensile strength,and heat resistant properties of shape‐memory epoxy resins: Two‐stages curing

In this article, we design a new thermal curing method: two‐stage curing. The purpose of using this approach is to maintain the excellent shape‐memory property of epoxy resin system after first stage curing, and the material can be folded in small size to storage or transportation and recovery its original shape commodiously by heating temperature. Then, after second stage curing, the stability, glass transition temperature(T_g), and tensile strength of material can be improved effectively. For this aim, a series of mixtures have been prepared. Differential scanning calorimetry (DSC), Fourier transform infrared spectroscopy (FTIR), tensile test, scanning electron microscope (SEM), dynamic mechanical analysis (DMA), and fold‐deploy shape‐memory test have been used to characterize the feasibility of two‐stage curing process, curing degree, tensile strength, morphology, thermodynamic properties, and shape‐memory performance of these polymers. DSC results show that two independent curing stages can be achieved successfully. Tensile tests and DMA results suggest that tensile strength and heat resistance have been improved after the second curing stage. SEM results reveal that the addition of latent curing agent do not change the fracture mechanism. Furthermore, the fold‐deploy shape‐memory tests prove that the composites after first stage curing possess eximious shape‐memory property. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39882.     

Electron beam curing of aliphatic unsaturated polyesters. I. Mechanistic study on converting to pressure‐sensitive adhesives

Aliphatic unsaturated polyesters (UPEs) mixed with N, N‐diethylaminoethyl methacrylate (DEAEMA) were convertible by electron beam irradiation to soft solids of high peeling strength. Double bond conversions, gel contents, molecular weight distributions, and crosslinking densities of the irradiated mixtures were studied in comparison with those of UPE–vinyl acetate mixtures, which gave very low peel strength on irradiation. The latter system started gel formation even at earlier stages of irradiation and had higher cross‐linking densities as a result of copolymerization between polyester and monomer double bonds. In contrast, the UPE–DEAEMA system exhibited slow gel formation with predominant conversion of monomer double bonds, indicating formation of graft copolymers. This system also had lower crosslinking densities than the other system. Therefore, it was concluded that the pressure‐sensitive adhesive nature of the electron‐beam‐cured UPE–DEAEMA mixtures could be attributed to the formation of flexible graft polymers entangled in a loosely crosslinked network. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 1854–1857, 2003     

Electron‐beam processing of nylon 6 and HNBR blends. Part II: development of high strength,heat‐ and oil‐resistant thermoplastic elastomers

The effects of electron‐beam irradiation on morphology, mechanical properties and on the heat and hot oil resistance of the thermoplastic elastomeric blend of 30:70 and 70:30, nylon 6 and hydrogenated nitrile rubber (HNBR) were investigated over the dose range 0–8 Mrad. The insoluble content of blends increased with increase in the radiation dose. The morphology of the blend was studied in scanning electron microscopy, with special reference to the effect of radiation prior to processing via injection molding. Irradiated pellets showed better mechanical properties after injection molding compared with irradiated sheets at low radiation dose. The observed differences in mechanical properties are explained on the basis of morphology of the blend. The blend properties were also found to have a strong dependence on nylon content. It was found that the blends rich in nylon had superior mechanical properties, hot oil and solvent resistance, whereas blends with higher HNBR content had better set and heat resistance. The effect of radiation on interaction in these blends was also evaluated and was found to induce possible inter‐chain crosslinking in the blends. Copyright © 2006 Society of Chemical Industry     

Influence of an epoxy reactive diluent on the thermal degradation process of the system DGEBA n = 0/1,2 DCH

The thermal degradation of two epoxy systems diglycidyl ether of bisphenol A (DGEBA n = 0)/1,2‐diamine cyclohexane (DCH) containing different concentrations of an epoxy reactive diluent, vinylcyclohexene dioxide (VCHD), was studied by thermogravimetric analysis to determine the reaction mechanism of the degradation process for these two systems. Values of the activation energy, necessary for this study, were calculated by using various integral and differential methods. Values obtained by using the different methods were compared to the value obtained by Kissinger's method, which does not require a knowledge of the reaction mechanism. All the experimental results were compared to master curves in the range of Doyle's approximation (20–35% of conversion). Analysis of the results suggests that the two reaction mechanisms are R_n and F_n deceleratory type in contrast with the sigmoidal A₂ type of the system with filler and the sigmoidal A₄ type of the system without additives. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 1199–1207, 2004     

含氟活性稀释剂对环氧树脂流变性能的影响

为解决环氧树脂的高粘度给成型带来的困难,用NXS-11A型旋转粘度计研究了含氟活性稀释剂对环氧树脂体系的流变性能的影响。研究结果表明,含氟活性稀释剂/环氧树脂体系在常温(35℃)时为牛顿型流体;常温下,环氧树脂体系粘度随含氟活性稀释剂添加量的增加下降显著,当氟活性稀释剂添加6%时,其粘度约可下降50%;但温度较高时,粘度随含氟活性稀释剂添加量的增加下降缓慢。随着含氟活性稀释剂的增加,环氧树脂体系的流动活化能明显下降。     

Electron‐beam‐induced crosslinking of natural rubber/acrylonitrile–butadiene rubber latex blends in the presence of ethoxylated pentaerythritol tetraacrylate used as a crosslinking promoter

A natural rubber latex, an acrylonitrile–butadiene rubber latex, and their 50: 50 blends were exposed to an electron beam in air. A polyfunctional monomer, ethoxylated pentaerythritol tetraacrylate, was used as a crosslinking promoter. Cast films from the irradiated systems were characterized for their gel contents, swelling properties, and tensile strength. An increase in the radiation dose from 0 to 500 kGy resulted in increased crosslinking, as measured by an increase in the gel content and better swelling resistance. The effect of the polyfunctional monomer, ethoxylated pentaerythritol tetraacrylate, as a crosslinking promoter was studied with infrared spectros copy. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1206–1214, 2007     

电子束固化水性聚氨酯丙烯酸酯的制备及性能

研究了一种制备水性聚氨酯丙烯酸酯的新方法,通过在扩链剂分子结构中组装离子基团来改善亲水性,解决了聚氨酯丙烯酸酯与水难相溶的问题。采用这种方法制备了一种聚氨酯丙烯酸酯产物,使用FTIR和1H NMR对产物结构进行了表征。对产物与水的储存稳定性、黏度、电子束固化行为及固化后性能进行了研究。结果表明,分散乳液储存稳定性好,经电子束固化后性能(如硬度、附着力、光泽度、柔韧性、热稳定性)优良。     

Studies of fluorine‐containing bismaleimide resins part I: Synthesis and characteristics of model compounds

A series of fluorine‐containing bismaleimide (FBMI) monomers are synthesized by a 3‐step reaction for using as the applications of low‐k materials. The synthesized FBMI monomers are characterized by the ¹H, ¹³C, ¹⁹F nuclear magnetic resonance (NMR) spectroscopy and element analysis. These FBMI monomers react with free radical initiator or self‐cure to prepare FBMI‐polymers. All the self‐curing FBMI resins have the glass transition temperatures (T_g) in the range of 128–141°C and show the 5% weight loss temperatures (T_5%) of 235–293°C in nitrogen atmosphere. The higher heat resistance of self‐curing FBMI resin relative to FBMI‐homopolymer is due to its higher crosslinking density. The FBMI resins exhibit improved dielectric properties as compared with commercial bismaleimide (BMI) resins with the dielectric constants (D_k) lower than 2.49, which is related to the low polarizability of the C? F bond and the large free volume of CF₃ groups in the polymers. Besides, the flame retardancy of all these FBMI resins could be enhanced via the introduction of Br‐atom. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Studies of phosphonate‐containing bismaleimide resins. I. Synthesis and characteristics of model compounds and polyaspartimides

Two phosphonate‐containing bismaleimide (BMI) [(4,4′‐bismaleimidophenyl)phosphonate] monomers with different melting temperatures and similar curing temperatures were synthesized by reacting N‐hydroxyphenylmaleimide with two kinds of dichloride‐terminated phosphonic monomers. The BMI monomers synthesized were identified with ¹H‐, ¹³C‐, and ³¹P‐nuclear magnetic resonance (NMR) spectroscopy and elemental analysis. The phosphonate‐containing BMI monomers react with a free‐radical initiator to prepare phosphonate‐containing BMI polymers and also with various aromatic diamines to prepare a series of polyaspartimides as reactive flame retardants. The polymerization degrees of polyaspartimides depend on the alkalinity and nucleophility of diamines as chain extenders. Differential scanning calorimetry (DSC) and thermogravimetry analysis (TGA) were used to study the thermal properties of the phosphonate‐containing BMI resins such as the melting temperature, curing temperature, glass transition temperature (T_g), and thermal resistance. All the phosphonate‐containing BMI resins, except the BMI polymers, have a T_g in the range of 210–256°C and show 5% weight loss temperatures (T_5%) of 329–434 and 310–388°C in air and nitrogen atmospheres, respectively. The higher heat resistance of cured BMI resin relative to the BMI polymer is due to its higher crosslinking density. Since the recrosslinking reactions of BMI polymers and polyaspartimides occur more easily in an oxidation environment, their thermal stabilities in air are higher than are those in nitrogen gas. In addition, the thermal decomposition properties of polyaspartimides depend on the structures and compositions of both the diamine segments and the BMI segments. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 1919–1933, 2002     

TTT and CHT curing diagrams of water‐borne polycondensation resins on lignocellulosic substrates

Lignocellulosic substrates such as wood were found to have a marked modifying influence on both lower temperature and higher temperature zones of TTT and CHT diagrams during hardening of phenol–resorcinol–formaldehyde (PRF) and melamime–urea–formaldehyde (MUF) polycondensates. Although the modifying influence of the substrate on the higher temperature zone of CHT diagrams presented the same trend of what was already reported for phenol–formaldehyde (PF) and urea–formaldehyde (UF) polycondensates, marked differences from what reported in the literature were recorded for TTT diagrams of all these polycondensates as well for the lower temperature zones of the CHT diagrams on lignocellulosic substrates, both of which had not been investigated previously. The chemical and physical mechanisms of the interactions of the resins, the substrate, and the water carrier causing such marked variations are presented and discussed. Although in the higher temperature zones both substrate and water carrier play an important role, in the lower temperature zone the presence of water appears to be the dominant factor causing the observed variations. The generalized modified CHT and TTT diagrams characteristic of the behavior of these water‐borne polycondensates on lignocellulosic substrates can be used to describe the behavior and complex changes of phase the formaldehyde‐based polycondensation resins undergo when used as wood adhesives during their curing directly in the wood joint. The results also show that diagrams obtained with pure resin cannot be used to predict the behavior of the polycondensate when this is markedly modified by the presence of interacting solvents and substrates. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 2128–2139, 2001     

Influence of accelerated ageing on methacrylate‐based denture resins heterogeneity as viewed by ESR‐spin‐probe method

The electron‐spin‐resonance (ESR) spin‐probe method, was used to study the heterogeneity of denture resins based on poly(methyl methacrylate). Results for three resins processed by microwave energy, conventional curing and cold curing (depending on the curing procedure and exposed to ageing in various environmental conditions) were compared. All three cured resins were stored over the same time (1200 h) in distilled water at ambient temperature and in artificial saliva at 348 K. The temperature‐dependent ESR spectra of a spin probe dispersed in the denture resins are analyzed in terms of line‐shapes and line‐widths. The appearance of two spectral components was taken as an indication of resin heterogeneity. The results reveal that the cold‐cured resin has a lower local density in comparison with microwave and conventionally cured resin. The amount of residual monomer also contributes to the local motion of polymer segments. The change of denture resins exposed to ageing is influenced both by the structure of the original resin and the ageing conditions. Restricted motion of a spin probe incorporated into the acrylic resins exposed to accelerated ageing suggests additional crosslinking of polymer chains. The differences are observed for all the investigated resins, but the highest change is observed with the cold‐cured resin. The ESR results are accompanied by T_g and T_m measurements. Copyright © 2005 Society of Chemical Industry