Role of amine activators on the curing parameters,properties and toxicity of acrylic bone cements

A review about the accelerating effect of tertiary aromatic amines used as activator in the benzoyl peroxide/amine system for the curing of acrylic resins is presented. The kinetics, mechanism and activation energy of the reaction are considered, together with some toxicity, residuals and leaching data concerned with biomedical applications of this system, e.g. denture resins or acrylic bone cements. Furthermore, some results relating the effect of the temperature of the surroundings on the curing parameters of the cements prepared with three amines (N,N-dimethyl-4-toluidine, N,N-dimethylbenzyl alcohol and N,N-dimethylbenzyl methacrylate) are shown. The results indicate that the temperature has a significant effect on the curing parameters, and must be considered in the evaluation of new activators. The relevance of these results lies with the importance of thermal trauma generally associated with the implantation of acrylic bone cements. © 1998 SCI.     

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     

Dynamic cure kinetics of epoxy resins using an amine‐containing borate as a latent hardener

An amine‐containing borate (labeled NBD) was obtained by a one‐step esterification using neopentyl glycol, boric acid and N,N‐dimethylethanolamine (DMEA) as reactants, and nuclear magnetic resonance as well as Fourier transform infrared (FTIR) measurements were used to characterize its chemical structure. The thermally latent curing properties of NBD were confirmed by differential scanning calorimetry (DSC), FTIR and gelation time results. The cure processes of bisphenol A diglycidyl ether epoxy resins (E51) using NBD as a latent hardener in comparison with a common hardener, DMEA, were studied by DSC measurements. The Avrami and Arrhenius methods as well as the Horowitz‐Metzger method were used to calculate kinetic parameters. These methods also revealed a transition at which the cure reaction mechanism showed a marked change and provided the apparent activation energy E_a associated with the cure reaction at different reaction stages. Copyright © 2012 Society of Chemical Industry     

N-phenyl piprazine-polyester derivative as curing activator of unsaturated resins

An oligomeric compound (Pol-2A) has been synthesized by a Michael-type addition of N-phenyl piperazine to double bonds of the maleic units of a polyester resin. This compound was used as activator (with benzoyl peroxide) in the curing of unsaturated polyester resins and compared in its efficiency with N,N-dimethylaniline (DMA). Pol-2A showed actiator characteristics comparable to those of DMA, with a wider range of gel times, and similar mechanical properties of the end products, with the advantage of a severe lowering of diffusibility and related environmental toxicity.     

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     

Time–temperature–transformation cure diagrams of phenol–formaldehyde and lignin–phenol–formaldehyde novolac resins

In this study, the time–temperature– transformation (TTT) cure diagrams of the curing processes of several novolac resins were determined. Each diagram corresponded to a mixture of commercial phenol–formaldehyde novolac, lignin–phenol–formaldehyde novolac, and methylolated lignin–phenol–formaldehyde novolac resins with hexamethylenetetramine as a curing agent. Thermomechanical analysis and differential scanning calorimetry techniques were applied to study the resin gelation and the kinetics of the curing process to obtain the isoconversional curves. The temperature at which the material gelled and vitrified [the glass‐transition temperature at the gel point (_gelT_g)], the glass‐transition temperature of the uncured material (without crosslinking; T_g0), and the glass‐transition temperature with full crosslinking were also obtained. On the basis of the measured of conversion degree at gelation, the approximate glass‐transition temperature/conversion relationship, and the thermokinetic results of the curing process of the resins, TTT cure diagrams of the novolac samples were constructed. The TTT diagrams showed that the lignin–novolac and methylolated lignin–novolac resins presented lower T_g0 and _gelT_g values than the commercial resin. The TTT diagram is a suitable tool for understanding novolac resin behavior during the isothermal curing process. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

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     

Effect of isomerization on thermal behaviour of bisitaconimides

The effect of isomerization of N,N′‐bisitaconimido‐4,4′‐diphenyl ether to the corresponding biscitraconimide on the curing characteristics and thermal stability of cured resins is described. Resins having bisitaconimide:biscitraconimide ratios of 23:77–93:7 were prepared by reacting 4,4′‐diaminodiphenyl ether with itaconic anhydride in solvents of different polarities and under different reaction conditions. Resins containing a higher proportion of citraconimide had a lower melting point (191 vs 208 °C). The curing exotherm was observed immediately after melting in all the resins and exothermic peak temperature reduced with increase in citraconimide content. Resins having a higher proportion of citraconimide on isothermal curing (200 °C, 2 h) and subsequent heating in nitrogen atmosphere degraded at a slightly lower temperature. However, the char yield at 800 °C did not show any systematic dependence on citraconimide content. © 2002 Society of Chemical Industry     

One‐pot curing system of epoxy resin imines initiated with water

The curing and adhesive properties of one‐component epoxy resins containing Epikote 828 and diimines, derived from N,N′‐di(1‐ethylpropylidene)‐m‐xylylenediamine, N,N′‐di(1‐ethylpropylidene)‐1,3‐diaminomethylcyclohexane (2), and N,N′‐di(1,3‐dimethylbutylidene)‐m‐xylylenediamine, which were used as water‐initiated hardeners, were examined. Diethyl ketone‐based imines with a lower electron density on the C?N carbon were efficiently hydrolyzed and showed curing activity. 2, a novel diethyl ketone‐based diimine, served as an efficient latent hardener of the epoxy resin. A paste of the epoxy resin with 2 showed good storage stability at room temperature and good adhesive properties. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 878–882, 2003     

Toughening of cyanate ester resin by N‐phenylmaleimide–N‐(p‐hydroxy)phenyl‐maleimide–styrene terpolymers and their hybrid modifiers

N‐Phenylmaleimide–N‐(p‐hydroxy)phenylmaleimide–styrene terpolymer (HPMS), carrying reactive p‐hydroxyphenyl groups, was prepared and used to improve the toughness of cyanate ester resins. Hybrid modifiers composed of N‐phenylmaleimide–styrene copolymer (PMS) and HPMS were also examined for further improvement in toughness. Balanced properties of the modified resins were obtained by using the hybrid modifiers. The morphology of the modified resins depends on HPMS structure, molecular weight and content, and hybrid modifier compositions. The most effective modification of the cyanate ester resin was attained because of the co‐continuous phase structure of the modified resin. Inclusion of the modifier composed of 10 wt% PMS (M_w 136 000 g mol^?1) and 2.5 wt% HPMS (hydroxyphenyl unit 3 mol%, M_w 15 500 g mol^?1) led to 135% increase in the fracture toughness (K_IC) for the modified resin with a slight loss of flexural strength and retention of flexural modulus and glass transition temperature, compared with the values for the unmodified resin. Furthermore, the effect of the curing conditions on the mechanical and thermal properties of the modified resins was examined. The toughening mechanism is discussed in terms of the morphological and dynamic viscoelastic behaviour of the modified cyanate ester resin system. © 2001 Society of Chemical Industry     

Synthesis,characterization and curing of m-diethylaminophenol-formaldehyde resin

Polycondensation of m-diethylaminophenol with formaldehyde has been studied under various reaction conditions. The resins formed are fusible and soluble in common organic solvents. All the resin samples have been characterized by spectral studies, measurement of solution viscosity, estimation of M?ⁿ and by t.g.a. The curing of selected resin samples by hexamine has been studied both by measuring percentage of cured material as a function of time at different temperatures and by differential scanning calorimetry. The d.s.c. data have been analyzed by various methods to evaluate the gross kinetic parameters of the curing reactions.     

Continuous UV cure monitoring and dielectric properties of photocross-linked epoxy–acrylate resins

The changes in viscosity of epoxy–acrylate resins during the photocross-linking process have been monitored continuously. The curing show change of shape and a distinct peak especially at high intensities. The intensity dependence of gel time follows a superlinear power law of the type t_pαI^?1.6 rather than the ½ power law. The dielectric relaxation studies on these photocross-linked films having different compositions of epoxy and n-butyl methacrylate reveal a particular composition range in which various dielectric parameters pass through critical values. These various findings have been explained on the basis of phase separation taking place during the UV curing process but at a submicron level leading to a very small domain size. © 1994 John Wiley & Sons, Inc.     

Chemical Structure and Curing Behavior of Phenol–Urea–Formaldehyde Cocondensed Resins of High Urea Content

Phenol–urea–formaldehyde cocondensed (PUF) resins of high urea content were prepared by adding different forms of urea to the reaction system. The structure, curing behavior, and water resistance of the PUF resins were investigated, and their relations were also discussed by liquid ¹³C nuclear magnetic resonance (NMR) and different scanning calorimetry (DSC). The liquid ¹³C-NMR analysis showed that urea added in the form of methylolureas was well incorporated into the cocondensed resins by reacting with phenolic methylols to form cocondensed methylene bridges, and that the PUF resins had no free formaldehyde with any form. Unreacted urea and low molecule monosubstituted urea of PUF resins play a dominant role in the curing behavior and water resistance of resins. The peak temperature, curing time, and curing enthalpy (ΔH) value correspondingly increased, however, the water resistance of PUF resins decreased when urea content in PUF resins increased. The PUF cocondensed resin with up to 89.4 % (W _U/W _P) urea has relatively low cost, and moreover can pass the requirements of China Industry Standard for the exterior grade of structural plywood after 4-h cyclic boiling test.     

Preparation and Characterization of Cured Epoxy Resin with Hexachloro-Cyclo-Triphosphazene

Epoxy resins can exhibit some excellent properties. The basic principle of curing epoxy resins with a curing agent containing multiple amino groups is the crosslinking reaction between active hydrogen atoms from the curing agent and the oxirane groups in the epoxy resin structure. This study deals with the synthesis of derivative of hexachloro-cyclo-triphosphazene (HCCTP) using curing of epoxy resins. The study of our interest is nucleophilic substitution of HCCTP using N-[3-(trimethoxysilyl)propyl]ethylene diamine. The prepared derivative offers two potential advantages over conventional curing systems, namely improving properties during burning.     

Preparation and characterization of soluble bismaleimide‐triazine resins based on asymmetric bismaleimide

A series of bismaleimide‐triazine resins (EBT) were prepared from 2‐(4′‐maleimido)phenyl‐2‐(4′‐maleimidophenoxyl)phenylbutane (EBA‐BMI) and 2,2‐bis(4‐cyanatophenyl)propane (BADCy). The resins show attractive processability with good solubility in low boiling point solvents and wide processing temperature windows. Introduction of diallylbisphenol A (DBA) can decrease the curing temperature of EBT resins that the curing exothermic peak temperature shifted from 291 to 237 °C as the content of DBA increased from 0 to 20%. The curing condition influenced the thermal properties of the cured EBT resins. The glass transition temperature increased as the curing temperature and curing time increased. The cured EBT resins show high glass transition temperature up to 352 °C, high thermal stability with 5% weight loss temperature over 405 °C, low coefficient of thermal expansion about 45 to 52 ppm/°C, and high storage modulus up to 2.6 GPa at 250 °C. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44519.     

Low‐viscosity and soluble phthalonitrile resin with improved thermostability for organic wave‐transparent composites

High processing viscosity and poor solubility limit the application of heterocyclic polymers for fabricating organic wave‐transparent composites for aerospace applications. In this paper, a novel resin, poly(phthalazinone ether bisphenol fluorene) encapped with phthalonitrile (PPEBF‐Ph), was synthesized and used as the matrix. Biphenol‐based phthalonitrile monomer BP‐Ph was also synthesized and blended with PPEBF‐Ph to further lower the processing viscosity. Solubility tests showed that the resin was soluble in dimethylformamide, N,N‐dimethyl acetamide, N‐methylpyrrolidone, dimethyl sulfoxide, chloroform, and other solvents. Differential scanning calorimetry and rheological studies revealed that the mixed resins exhibited low processing viscosity and a wide processing window below the gel temperature. Thermogravimetric analysis indicated that the cured resins were stable below 510–530 °C under nitrogen atmosphere after 6 h of curing (decreased by 40–60% compared with previous reports on phthalonitrile resin). In air, the char yields of the resins reached 20–30% when heated at 800 °C. The composites were reinforced by a quartz fiber cloth and exhibited a dielectric constant of 2.94–3.27 in an electromagnetic field with frequency ranging from 8 to 18 GHz. Retention of the bending modulus exceeded 70% at 400 °C according to dynamic mechanical analysis, indicating excellent mechanical stability was obtained. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45976.     

Engineering biomass into formaldehyde‐free phenolic resin for composite materials

The use of formaldehyde to prepare phenol‐formaldehyde (PF) resins is one of the primary challenges for the world‐wide PF industry with respect to both sustainability and human health. This study reports a novel one‐pot synthesis process for phenol‐5‐hydroxymethylfurfural (PHMF) resin as a formaldehyde‐free phenolic resin using phenol and glucose, and the curing of the phenolic resin with a green curing agent organosolv lignin (OL) or Kraft lignin (KL). Evidenced by ¹³C NMR, the curing mechanism involves alkylation reaction between the hydoxyalkyl groups of lignin and the ortho‐ and para‐carbon of PHMF phenolic hydroxyl group. The curing kinetics was studied using differential scanning calorimetry and the kinetic parameters were obtained. The OL/KL cured PHMF resins were tested in terms of thermal stability, and mechanical properties for their applications in fiberglass reinforced composite materials. The results obtained demonstrated that OL/KL can be promising curing agents for the PHMF resins. © 2015 American Institute of Chemical Engineers AIChE J, 61: 1275–1283, 2015     

Influence of the synthesis conditions on the curing behavior of phenol–urea–formaldehyde resol resins

The curing behavior of synthesized phenol–urea–formaldehyde (PUF) resol resins with various formaldehyde/urea/phenol ratios was studied with differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA). The results indicated that the synthesis parameters, including the urea content, formaldehyde/phenol ratio, and pH value, had a combined effect on the curing behavior. The pH value played an important role in affecting the shape of the DSC curing curves, the activation energy, and the reaction rate constant. Depending on the pH value, one or two peaks could appear in the DSC curve. The activation energy was lower when pH was below 11. The reaction rate constant increased with an increase in the pH value at both low and high temperatures. The urea content and formaldehyde/phenol ratio had no significant influence on the activation energy and rate constant. DMA showed that both the gel point and tan δ peak temperature (T_tanδ) had the lowest values in the mid‐pH range for the PUF resins. A different trend was observed for the phenol–formaldehyde resin without the urea component. Instead, the gel point and T_tanδ decreased monotonically with an increase in the pH value. For the PUF resins, a high urea content or a low formaldehyde/phenol ratio resulted in a high gel point. The effect of the urea content on T_tanδ was bigger than that on the gel point because of the reversible reaction associated with the urea component. Too much formaldehyde could lead to more reversible reactions and a higher T_tanδ value. The effects of the synthesis conditions on the rigidity of the cured network were complex for the PUF resins. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 95: 1368–1375, 2005     

Influence of chemical composition on the rheological behavior of condensation reaction resins

In this paper, the chemorheological and dynamic mechanical behavior of melamine‐formaldehyde (MF) resins of four different formaldehyde/melamine (F/M) molar ratios (1.25, 1.5 1.75 and 2.00) are investigated. MF resins polymerize via a polycondensation reaction involving formation of up to 10 wt% of H₂O on cure. This typically results in rapid and extensive foaming of the resin when it is cured under atmospheric pressure. Experimental adaptation for the foaming behavior of MF resins is used to gather rheological information concerning the curing kinetics and the mechanical response of neat MF resins of different molar ratios. Likewise, the procedures developed allow curing of the resins under atmospheric pressure, hence allowing volatile evacuation as occurs during venting procedures (commonly used during compression molding of MF molding compounds) or as a result of absorption by hydrophilic fillers or substrates. The results show that increased moisture content in the B‐stage leads to faster reaction rates and greater foaming. Gelation and vitrification times are identified for each molar ratio, and are found to increase with decreasing molar ratio. The dynamic mechanical behavior of carefully molded neat MF samples of different molar ratios is studied using DMTA. T_g is found to be 200°C for the resin with the lowest formaldehyde content (F/M = 1.25), and around 230°C for the other resins. The storage shear modulus above T_g is studied, and the results show that the crosslink density increases with increasing molar ratio.     

Chemorheological time‐temperature‐transformation‐viscosity diagram: Foamed EPDM rubber compound

Thermal analysis, rheometry, and kinetic modeling are used to generate a comprehensive processability diagram for thermosetting and elastomeric resins. A chemorheological “time‐temperature‐transformation‐viscosity” diagram is proposed to fully characterize curing reactions toward process' on‐line control, optimization, and material design. Differential scanning calorimetry and thermogravimetric techniques are used to measure total reaction heat, degree of vulcanization, and cure kinetics. The viscosity, as a function of temperature and cure degree, is obtained from parallel plate rheometry. The auto‐catalytic Kamal–Sourour model, including a diffusion‐control mechanism, is used to model cure kinetics, while the Castro–Macosko model serves to model the rheological behavior. Non‐linear least‐squares regression and numerical integration are used to find models' parameters and to construct the chemorheological diagram. The usefulness of the proposed methodology is illustrated in the context of an industrial‐like Ethylene Propylene Diene Termononer rubber compound that includes a chemical blowing agent. Even though the rubber formulation contains crosslinking agents, primary and secondary accelerators, promoters, activators, and processing aids, the chemorheological diagram is obtained consistently, validating the proposed methodology to any thermosetting or elastomeric resin. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43966.