Reaction epoxy-amine: Suivi du mecanisme reactionnel et de la cinetique par RMN 13C, 15N et HPLC

The curing reaction of diglycidyl ether of bisphenol A (DGEBA) with metaphenylene diamine (mPDA) was investigated with high performance liquid chromatography (HPLC) and Fourier transform nuclear magnetic resonance spectroscopy (FT NMR ¹³C and ¹⁵N). With the results obtained from a series of models a mechanism was proposed and the cure kinetics were obtained at 100°C. The major conclusion is that the cure proceeded mainly by chain extension, whereas crosslinking occurred in the reaction of hydroxyl groups with epoxides and resulted in the formation of ether linkages.     

Kinetics of the crosslinking reaction of a bisnadimide model compound in thermal and microwave cure processes

The kinetic studies of the crosslinking reaction of a nadic end-capped imide model compound, N,N′-(oxydi-3,4′-phenylene) bis(5-norbornene-2,3-dicarboximide), a bisnadimide, in thermal and microwave processes were investigated. The conversion of the endo isomer to exo isomer proceeds at a much lower temperature than the crosslinking reaction. The crosslinking reaction was monitored by the combined decrease in the infrared absorptions of the endo and exo isomers at 840 and 780 cm⁻¹, respectively. The decrease in the concentration of starting materials follows first-order kinetics in the thermal and microwave processes. At the same temperatures (230 or 280°C), the crosslinking reaction proceeds at about 10 times faster in the microwave process than in the thermal process. Solid-state ¹³C-NMR showed no significant loss in C=C double bond resonance in the cured products by comparison with the starting material. This study provides direct evidence that the microwave process may be an efficient method to cure nadic end-capped polyimides. © 1998 John Wiley & Sons, Inc. J. Polym. Sci. A Polym. Chem. 36: 2653–2665, 1998     

Comparison of electron spin resonance probe and dielectric relaxation in physically and chemically crosslinked polymers

Dielectric relaxation spectroscopy in the frequency range from 10⁻² Hz to 10⁶ Hz and electron spin resonance (ESR) experiments are employed to study the dynamics in chemically and physically crosslinked networks. As examples for physically crosslinked networks ortho- and para-cresol novolacs were investigated. Dielectrically these materials show low-temperature β- and high-temperature α-relaxation. Both relaxation regions differ for both types of novolacs. This is also reflected by the ESR measurements and is discussed in terms of different hydrogen bonds found to be stronger in para-cresol novolac. For the chemically crosslinked poly(triallyl isocyanurate) only a β-peak is found by the dielectric measurements. Also in the ESR experiment the slow motion regime is characterized up to high temperatures. This means that the segmental motion is strongly suppressed by chemical crosslinking. Nevertheless the obtained change in the formal T_50G value can be used to characterize the glass transition in highly crosslinked systems by the ESR method.     

Calorimetric investigation of polymerization reactions. IV. Curing reaction of polyester fumarate with styrene

The curing reaction of polyester fumarate with styrene was investigated with a differential scanning calorimeter (DSC) operated isothermally. The change in rate of cure was followed over the whole range of conversion. The rate of cure is accelerated by the gel effect to about ten to fifty times the rate of model copolymerization of diethyl fumarate with styrene. This autoacceleration is much enhanced for systems with higher crosslinking densities and at lower temperatures. The results confirm that both termination and propagation steps of the curing reaction are controlled by diffusion of polymeric segments and monomer molecules over almost the whole range of conversion. The final extent of conversion is short of completion for isothermal cure and even for postcure of polyester fumarate with styrene because of crosslink formation. The final conversion of isothermal cure decreases with increasing crosslinking density and shows a maximum with increasing reaction temperature. This temperature dependency of the final conversion is caused by the difference in the activation energies for two propagation rate constants k_pf and k_ps, which were evaluated to be 7–10 and 5–8 kcal/mole, respectively, for the intermediate stage of the curing reaction.     

The influence of reagent concentration on the kinetics of carbon dioxide-propylene oxide copolymerization in the presence of a cobalt complex

The effect of the concentrations of propylene oxide and the catalyst (salen)CoDNP/[PPN]Cl ((salen)CoDNP: [PPN]Cl = 1: 1, mol/mol) on the kinetics of the copolymerization of CO₂ and propylene oxide at 0.5 MPa and 20°C has been studied. The reaction proceeds at a constant rate after an induction period, and the value of this period varies with the reagent concentrations. The steady-state reaction rate increases linearly with the propylene oxide concentration in the range 5.0–14.3 mol/L. At high catalyst concentrations, such as (5.2–7.3) × 10^?3 mol/L, the reaction rate is first order in the catalyst; at concentrations below 5 × 10^?3 mol/L, the reaction rate is second order in the catalyst. Molecular mass increases in proportion to the propylene oxide conversion, that is consistent with a living polymerization process. A regioregular copolymer with 96% head-to-tail (HT) connectivity of propylene oxide has been obtained.     

Ruthenium (III) catalysed and uncatalysed oxidation of torsemide by hexacyanoferrate (III) in aqueous alkaline medium: A kinetic comparative approach

The kinetics approach of oxidation of torsemide (TOR) by hexacyanoferrate (III) [HCF (III)] has been identified spectrophotometrically at 420 ​nm in the alkaline medium in the presence and absence of catalyst ruthenium (III) at 25 ​°C, by keeping ionic strength (1 ​× ​10⁻² ​mol ​dm⁻³) constant. The reaction exhibits at the stoichiometry ratio 1:2 of TOR and HCF (III), for uncatalysed and catalysed reactions. In the absence and presence of the catalyst, the order of the reactions obtained for TOR and HCF (III) was unity. However, the rate of the reactions enhanced by the increase in the concentration of catalyst, as well as the rate increases with an increase in alkaline concentration. The activation parameters for the reaction at the slow step were identified, and the effect of temperature on the rate of the reaction was analysed. A suitable mechanism has been demonstrated by considering the obtained results. The derived rate laws are reliable with analysed experimental kinetics.     

Physical & thermal properties of model polysiloxane rubbers: impact of crosslink density and tin concentration

The influence of the tin octanoate catalyst on the physical and thermal properties of RTV 5370 polysiloxane rubbers has been studied. To assess the likely influence of crosslinking on a number of physical and thermal properties in polysiloxanes, “model siloxane networks” (representing networks of well defined composition/structure) have been formulated by the hydrosilylation of polysiloxane diols of known average molecular weight with tetraethoxysilane curing agent. It was found that linear swell and the crystallisation melting transitions of these systems were both significantly affected by changes in crosslink density. A selection of RTV5370 foamed rubbers with different tin concentrations were prepared in a similar manner to assess the influence of the tin catalyst. For these materials it was found that the area of the crystalline melting transition decreased with increasing tin concentration, an effect indicative of increased crosslinking. Samples with double the standard amount of tin (10% wt catalyst) show a shift in the crystallisation transition to higher temperature with no further effect beyond this concentration. Furthermore, the storage modulus (E') of the rubbers at room temperature appears to be independent of the tin catalyst concentration. Through correlation with the data from the model siloxanes, these results suggests that increasing the catalyst concentration appears to induce additional crosslinking interactions that are stable at low temperatures but not stable at room temperature.     

Effect of the reference chain dimension on the viscoelastic and stress–strain behavior of poly(n-butyl methacrylate) networks

The linear viscoelastic and stress-strain behavior of poly(n-butyl methacrylate) networks at a content of crosslinking agent (ethyleneglycol dimethacrylate) of c? 0–1 × 10^?4 mole/cm³ was investigated in the main transition and rubberlike region in the temperature interval from 20 to 150°C. The dependence of the unperturbed chain dimensions on temperature was determined from thermoelastic measurements in the rubberlike region; this dependence was unaffected by the content of crosslinking agent. Application of time–temperature superposition to the linear viscoelastic behavior did not give a continuous superimposed curve in the proximity of the rubberlike region; superposition within the whole time region required introducing the change of the unperturbed chain dimensions with temperature. This correction was sufficient for a sample with a higher content of the crosslinking agent. However, for loose networks (c< 0.1 × 10^?4 mole/cm³) it was insufficient, because of another relaxation mechanism in the region of high temperatures. It was found that the intensity and temperature dependence of this relaxation mechanism, which is probably due to a change of the number of entanglements with temperature, are connected with the magnitude and the temperature dependence of the C₂ constant of the Mooney-Rivlin equation.     

Curing of an epoxy resin modified with poly(methylmethacrylate) monitored by simultaneous dielectric/near infrared spectroscopies

Simultaneous dielectric and near infrared measurements have been performed in “real-time” to follow polymerisation reactions on blends of a diglycidyl ether of bisphenol-A epoxy resin with 4,4^′-diaminodiphenylmethane hardener and different amounts of poly(methylmethacrylate) as modifier. The effect of the modifier amount on the polymerisation reactions has been studied, as well as that of the curing temperature. Epoxy and amine conversions have been followed by near infrared spectroscopy (NIR), while changes in molecular mobility in the reaction mixture have been analysed by dielectric relaxation spectroscopy (DRS). Evolutions of ionic conductivity and α-relaxation have been analysed and vitrification times have been obtained. The relaxational behaviour has been analysed through curing in the frequency domain, being the change of the main relaxation indicative of the cure reaction advancement. DRS data are also presented as complex impedance Z(ω). Vitrification times, obtained by dielectrometry have been compared with those obtained by rheological measurements and gelation times obtained by NIR have been compared with those obtained by solvent extraction.     

Dynamic mechanical behavior of lightly crosslinked networks of poly(n-butyl methacrylate) and poly(n-butyl acrylate) in the rubberlike region

An investigation was made of the dynamic mechanical behavior in the rubberlike region of poly(n-butyl methacrylate) (PBuMA) and poly(n-butyl acrylate) (PBuA) networks lightly crosslinked with ethylene dimethacrylate to concentrations from 10^?6 to 10^?4 mole/cm³. The measurements were carried out by use of an apparatus for low-frequency forced vibrations working in the frequency range 2.5 × 10^?4 to 1 Hz. With parameters c₁ and c₂ of the Williams-Landel-Ferry equation, obtained from data in the main transition region, the data did not reduce in the rubberlike region for the poly(butyl methacrylate) networks; the spread of the deviations decreases with increasing concentration of the crosslinking agent. Superposition could be achieved in all cases when a shift factor was used on the vertical axis. At sufficiently low reduced frequencies and at high temperatures the storage compliance decreases in both series of polymers with increasing concentration of the crosslinking agent as expected. At higher reduced frequencies and at higher temperatures of measurement, however, anomalous behavior was observed with uncrosslinked samples having a lower compliance than those crosslinked to a very low degree. This finding was explained as due to very long relaxation times of the untrapped entanglements present in the noncrosslinked polymer, which are absent in the same polymer crosslinked already to very low degrees. The retardation spectra of both PBuMA and PBuA exhibited secondary relaxation mechanisms which were shifted by four logarithmic decades toward higher retardation times in comparison with the primary retardation maximum.     

Low molar mass polybutadiene made crosslinkable by the introduction of styrenic moieties via urethane linkage: synthesis, kinetic and crosslinking studies

The introduction of styrenic moieties was chosen for the radical crosslinking of polybutadiene bearing hydroxy functions. The modifications were carried out with 3-isopropenyl-α,α-dimethylbenzyl isocyanate (TMI) with or without catalyst (DBTL). A 2nd order kinetic fits our experimental results up to high conversion. Arrhenius parameters were calculated. Thermally catalyzed crosslinking was studied. The reaction was followed by measuring swelling (Q) in toluene as well as mechanical parameters (storage modulus E^′ at the rubbery plateau and tanδ). The influence of temperature, the nature and concentration of initiators, the number of styrenic groups per chain (n=1.2, 2, 2.4) were investigated. In the range of our experimental conditions, a “reaction master curve” was established to predict the evolution of E^′ and Q as a function of time, for any temperature, initiator concentration and value of n.     

Investigation of the kinetics of formation of 1 : 1 complex between chromium(III) with 1,3-propanediamine-N,N′-diacetate-N,N′-di-3-propionate ion in aqueous acidic media

The kinetics of formation of the 1?:?1 complex of chromium(III) with 1,3-propanediamine-N,N′-diacetate-N,N′-di-3-propionate (1,3-pddadp) were followed spectrophotometrically at λ _max?=?557?nm. The reaction was first-order in chromium(III). Increasing the 1,3-pddadp concentration from 2.2?×?10^?2 to 0.11?mol?dm^?3 accelerated the reaction rate. Increasing the hydrogen ion concentration from 1.995?×?10^?5 to 6.31?×?10^?4 mol?dm^?3 retarded the reaction rate. The reaction rate was also retarded by increasing ionic strength and dielectric constant of the reaction medium. A mechanism was suggested to account for the results obtained which involves ion-pair formation between the various reactants. Values of 22?kJ?mol^?1 and ?115?J?K^?1 mol^?1 were obtained for the energy and the entropy of activation, respectively, which indicate an associative mechanism. The logarithm of the formation constant of the 1?:?1 complex formed was 11.3.     

Hydrogenation of Styrene‐Butadiene Rubber Catalyzed by Ru(CHCHPh)Cl(CO)(PCy3)2

Summary: The hydrogenation of a copolymer of styrene and butadiene (SBR) catalyzed by Ru(CHCHPh)Cl(CO)(PCy₃)₂ was experimentally investigated within the temperature range of 120–160 °C, at Pequation/tex2gif-inf-7.gif of 300–1 200 psi, and a catalyst concentration of 10–78 × 10⁻⁶ M . Special attention was paid to minimizing the catalyst metal residue and crosslinking in the product. The results indicated that high‐quality hydrogenated SBR was achieved without crosslinking and the metal residue was less than 7 ppm without a post‐treatment.

IR spectra of the styrene–butadiene rubber before (a) and after (b) hydrogenation with the Ru(CHCHPh)Cl(CO)(PCy₃)₂ catalyst were observed as reported here. The disappearance of all characteristic absorbencies of CC (724, 910, 967, and 994 cm⁻¹) suggests nearly quantitative hydrogenation of the CC bonds.     

Stopped‐flow polymerizations of ethene and propene in the presence of the catalyst system rac‐Me2Si(2‐methyl‐4‐phenyl‐1‐indenyl)2ZrCl2/methylaluminoxane

The kinetics of ethene and propene polymerization at 20–60°C in the presence of the homogeneous catalyst system rac‐Me₂Si(2‐methyl‐4‐phenyl‐1‐indenyl)₂ZrCl₂/methylaluminoxane was investigated by means of stopped‐flow techniques. The specific rate of chain propagation, measured at the very short reaction times typical of this method, turned out to be ≈10² times higher for ethene than for propene; this suggests that diffusion limitations through the poly(ethylene) precipitating at longer reaction times may be responsible for the fact that the two monomers polymerize instead at comparable rates under “standard” conditions. It was also found that the concentration of active sites is significantly lower than the analytical Zr concentration.     

Kinetics and mechanism of water catalytic oxidation by a Ru3+(bpy)3 complex in the presence of colloidal cobalt hydroxide

Kinetics of the catalytic oxidation of water to molecular oxygen by a tris(bipyridyl) Ru(III) complex is studied in the presence of colloidal cobalt hydroxide stabilized by starch. Oxidant consumption follows the first-order rate law with respect to the oxidant concentration. The dependence of the apparent rate constant of this process on the catalyst concentration, initial oxidant concentration, and initial concentration of its reduced form was determined. The dependence of the oxygen yield on H⁺ at pH 7–11 and a catalyst concentration of 10-⁷-10-³ mol¹ is studied. An intermediate product of the reaction was found, which is probably a bridged peroxo complex of cobalt. The kinetic scheme and mechanism of the reaction is proposed, which agree with experimental observations.     

Bulk hydrosilylation reaction of poly(dimethylsiloxane) chains catalyzed by a platinum salt: Effect of the initial concentration of reactive groups on the final extent of reaction

Model silicone networks obtained by curing linear poly(dimethylsiloxane) (PDMS) chains with end‐vinyl groups, (B₂), with a polyfunctional silane‐terminated crosslinker of functionality f, (A_f), through a hydrosilylation reaction have been widely used. In these networks, the principal characteristics of their ultimate molecular structure are strongly affected by the final extent of reaction reached during the crosslinking reaction. This work analyzes the effect of the initial concentration of the reactive end groups on the maximum attainable extent of reaction under normal bulk crosslinking conditions. This was accomplished by examining the reaction between linear B₂ PDMS chains with difunctional and trifunctional silanes. The experimental results were fitted by an exponential equation to have an empirical equation able to predict the maximum extent of reaction to be obtained as a function of the initial concentration of reactive groups. Molecular parameters relevant to this study, such as the degree of polymerization, the weight‐average molecular weight for the A₂ + B₂ system, or the weight fraction of solubles for the A₃ + B₂ system, were calculated with a mean field theory (recursive approach). © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 1099–1106, 2003     

Kinetics and mechanism of the formation of poly[(1,1,3,3-tetramethyldisiloxanyl)ethylene] and poly(methyldecylsiloxane) by hydrosilylation

The kinetics of the formation of poly(carbosiloxane), as well as of alkyl-substituted poly(siloxane), by Karstedt's catalyst catalyzed hydrosilylation were investigated. Linear poly(carbosiloxane), poly[(1,1,3,3-tetramethyldisiloxanyl)ethylene], (PTMDSE), was obtained by hydrosilylation of 1,3-divinyltetramethyldisiloxane (DVTMDS) and 1,1,3,3-tetramethyldisiloxane (TMDS), while alkyl-substituted poly(siloxane), poly(methyldecylsiloxane), (PMDS), was synthesized by hydrosilylation of poly(methylhydrosiloxane) (PMHS) and 1-decene. To investigate the kinetics of PTMDSE formation, two series of experiments were performed at reaction temperatures ranging from 25 to 56 °C and with catalyst concentrations ranging from 7.0 × 10⁻⁶ to 3.1 × 10⁻⁵ mol Pt/mol CHCH₂. A series of experiments was performed at reaction temperatures ranging from 28 to 48 °C, with catalyst concentrations of 7.0 ×10⁻⁶ mol of Pt per mol of CHCH₂, when kinetics of PMDS formation was investigated. All reactions were carried out in bulk, with equimolar amounts of the reacting Si H and CHCH₂ groups. The course of the reactions was monitored by following the disappearance of the Si H bands using quantitative infrared spectroscopy. The results obtained showed typical first order kinetics for the PTMDSE formation, consistent with the proposed reaction mechanism. In the case of PMDS an induction period occurred at lower reaction temperatures, but disappeared at 44 °C and the rate of Si H conversion also started to follow the first-order kinetics. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 2246–2258, 2007     

Synthesis and thermal crosslinking reaction of polymers containing pendant carboxyl and epoxy groups

Polymers containing both pendant carboxyl and epoxy groups were synthesized by the radical copolymerization of p-vinylbenzyl glycidyl ether (VBGE) and itaconic acid monomethyl ester (IAME). The copolymerization proceeded smoothly under various conditions, and polymer soluble in 1,4-dioxane with no gel fraction was obtained. However, the carboxyl-epoxy addition reaction between VBGE and IAME was observed, when DMSO or DMF were used as polymerization solvents. The IR and ¹H-NMR spectrum of copolymers of VBGE and IAME showed the corresponding structure. The thermal crosslinking reaction of the resulting copolymers was examined under various conditions. Tetrabutylammonium bromide (TBAB) showed catalytic activity for the reaction. However, a 100% gel fraction of polymer was achieved after only 15 min without any catalyst, when the crosslinking reaction was performed at 150°C. © 1996 John Wiley & Sons, Inc.     

Investigation of oxidation and tautomerization of a recently synthesized Schiff base in micellar media using multivariate curve resolution alternative least squares and rank annihilation factor analysis methods

The oxidation of the recently synthesized Schiff base 3,6-bis((2-aminoethyl-5-Br-salicyliden)thio)pyridazine (PABST) with hydrogen peroxide was investigated using spectrophotometric studies. The reaction rate order and observed rate constant of the oxidation reaction was obtained in the mixture of N,N-dimethylformamide (DMF):water (30:70, v/v) at pH 10 using multivariate cure resolution alternative least squares (MCR-ALS) method and rank annihilation factor analysis (RAFA). The effective parameters on the oxidation rate constant such as percents of DMF, the effect of transition metals like Cu²⁺, Zn²⁺, Mn²⁺ and Hg²⁺ and the presence of surfactants were investigated. The keto-enol equilibria in DMF:water (30:70, v/v) solution at pH 7.6 was also investigated in the presence of surfactants. At concentrations above critical micelle concentration (cmc) of cationic surfactant cetyltrimethylammonium bromide (CTAB), the keto form was the predominant species, while at concentrations above cmc of anionic surfactant sodium dodecyl sulfate (SDS), the enol form was the predominant species. The kinetic reaction order and the rate constant of tautomerization in micellar medium were obtained using MCR-ALS and RAFA. The results obtained by both the methods were in a good agreement with each other. Also the effect of different volume percents of DMF on the rate constant of tautomerization was investigated. The neutral surfactant (Triton X-100) had no effect on tautomerization equilibrium.