Atom transfer radical homo‐ and copolymerization of styrene and methyl acrylate initiated with trichloromethyl‐ terminated poly(vinyl acetate) macroinitiator: A kinetic study

Atom transfer radical bulk copolymerization of styrene (St) and methyl acrylate (MA) initiated with trichloromethyl‐terminated poly(vinyl acetate) macroinitiator was performed in the presence of CuCl/PMDETA as a catalyst system at 90°C. Linear dependence of ln[M]₀/[M] versus time data along with narrow polydispersity of molecular weight distribution revealed that all the homo‐ and copolymerization reactions proceed according to the controlled/living characteristic. To obtain more reliable monomer reactivity ratios, the cumulative average copolymer composition at moderate to high conversion was determined by ¹H‐NMR spectroscopy. Reactivity ratios of St and MA were calculated by the extended Kelen‐Tudos (KT) and Mao‐Huglin (MH) methods to be r_St = 1.018 ± 0.060, r_MA = 0.177 ± 0.025 and r_St = 1.016 ± 0.053, r_MA = 0.179 ± 0.023, respectively, which are in a good agreement with those reported for the conventional free‐radical copolymerization of St and MA. Good agreement between the theoretical and experimental composition drifts in the comonomer mixture and copolymer as a function of the overall monomer conversion were observed, indicating that the reactivity ratios calculated by copolymer composition at the moderate to high conversion are accurate. Instantaneous copolymer composition curve and number‐average sequence length of comonomers in the copolymer indicated that the copolymerization system tends to produce a random copolymer. However, MA‐centered triad distribution results indicate that the spontaneous gradient copolymers can also be obtained when the mole fraction of MA in the initial comonomer mixture is high enough. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Kinetics of the metal exchange reaction of a Cu(II)-poly(vinyl alcohol) complex with Zn(II)-ethylenediamine-N,N,N′,N′-tetraacetic acid in aqueous solution

The kinetics of the metal exchange reaction between Cu(II)-poly(vinyl alcohol) [Cu(II)-PVA] and Zn(II)-ethylenediamine-N,N,N′,N′-tetraacetic acid [Zn(II)-EDTA] has been studied by mixing both solutions in a spectrophotometer at pH 10.0 to 11.0, ionic strength μ=0.10(KNO₃), and 15 to 35°C. The reaction is initiated by the formation of unstable Cu(II)-H-PVA through attack of H⁺ ion on the Cu(II)-PVA complex, and both reactions, ligand exchange and metal exchange, proceed simultaneously. The metal exchange step may be rate determining. The rate equation and rate constants of this reaction were determined as follows: ?d[Cu(II)-PVA]/dt=k _0(H)[PVA^?][Cu(II)-PVA] [Zn(II)-EDTA], wherek _0(H)=k ₁+(k′₂+k′₃)[H⁺],k ₁=5.98±1.64M ^?1 s^?1, andk ₂+k ₃=k′₂ K _Cu(II)-H-PVA ^?H +k′₃ K _Zn(II)-EDTA ^H =(5.91±0.89)×10⁷ M ^?2 s^?1.     

A new simple procedure to calculate monomer reactivity ratios by using on-line 1H NMR kinetic experiments: Copolymerization system with greater difference between the monomer reactivity ratios

Free radical copolymerization reaction of vinyl acetate (VA) and methyl acrylate (MA) in solution of benzene-d₆ using benzoyl peroxide (BPO) as the initiator was studied with on-line ¹H NMR kinetic experiments at 60 °C. It was observed that composition drifts in the comonomer mixture with reaction progress is significant. Hence, the monomer reactivity ratios of VA/MA system could be calculated by the data collected only from one sample via on-line following the comonomer mixture and copolymer compositions at different reaction time intervals up to medium overall monomer conversions. The results were in good agreement with the literature data reported for this system. The good fitting between theoretical and experimental changes in the comonomer mixture compositions as a function of reaction progress was observed, indicating the accuracy of the monomer reactivity ratios calculated by the new procedure presented here.     

Kinetic study of radical polymerization. VII. Investigation into the solution copolymerization of acrylonitrile and itaconic acid by real‐time 1H NMR spectroscopy

Free radical solution copolymerization of acrylonitrile (AN) and itaconic acid (IA) was performed with DMSO‐d₆ as the solvent and 2,2′‐azobisisobutyronitrile (AIBN) as the initiator. Weight ratio of the monomers to solvent and molar ratio of initiator to monomers were constant in all experiments. The initial comonomer composition was the only variable in this study. On‐line ¹H NMR spectroscopy was applied to follow individual monomer conversion. Mole fraction of AN and IA in the reaction mixture (f) and in the copolymer chain (F) were measured with progress of the copolymerization reaction. Overall monomer conversion versus time and also compositions of monomer mixture and copolymer as a function of overall monomer conversion were calculated from the data of individual monomer conversion versus time. Total rate constant for the copolymerization reaction was calculated by using the overall monomer conversion versus time data and then k_p/k_t^0.5 was estimated. The dependency of k_p/k_t^0.5 on IA concentration was studied and it was found that this ratio decreases by increasing the mole fraction of IA in the initial feed. The variation of comonomer and copolymer compositions as a function of overall monomer conversion was calculated theoretically by the terminal model equations and compared with the experimental data. Instantaneous copolymer composition curve showed the formation of alternating copolymer chain during copolymerization reaction. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 3253–3260, 2007     

The effect of two β-alanine dosing strategies on 30-minute rowing performance: a randomized,controlled trial

Background

β-alanine (βA) supplementation has been shown to increase intramuscular carnosine content and subsequent high-intensity performance in events lasting <?4?minutes (min), which may be dependent on total, as opposed to daily, dose. The ergogenic effect of βA has also been demonstrated for 2000-m rowing performance prompting interest in whether βA may be beneficial for sustained aerobic exercise. This study therefore investigated the effect of two βA dosing strategies on 30-min rowing and subsequent sprint performance.

Methods

Following University Ethics approval, twenty-seven healthy, male rowers (age: 24?±?2?years; body-height: 1.81?±?0.02?m; body-mass: 82.3?±?2.5?kg; body-fat: 14.2?±?1.0%) were randomised in a double-blind manner to 4?weeks of: i) βA (2.4?g·d^??1, βA1); ii) matched total βA (4.8?g on alternate days, βA2); or iii) cornflour placebo (2.4?g·d^??1, PL). Participants completed a laboratory 30-min rowing time-trial, followed by 3x30-seconds (s) maximal sprint efforts at days 0, 14 and 28 (T1-T3). Total distance (m), average power (W), relative average power (W·kg^??1), cardio-respiratory measures and perceived exertion were assessed for each 10-min split. Blood lactate ([La-]_b mmol·L^??1) was monitored pre-post time-trial and following maximal sprint efforts. A 3-way repeated measures ANOVA was employed for main analyses, with Bonferonni post-hoc assessment (P?≤?0.05).

Results

Total 30-min time-trial distance significantly increased from T1-T3 within βA1 only (7397?±?195?m to 7580?±?171?m, P?=?0.002, ?p²?=?0.196), including absolute average power (194.8?±?18.3?W to 204.2?±?15.5?W, P?=?0.04, ?p²?=?0.115) and relative average power output (2.28?±?0.15?W·kg^??1 to 2.41?±?0.12?W·kg^??1, P?=?0.031, ?p²?=?0.122). These findings were potentially explained by within-group significance for the same variables for the first 10?min split (P?≤?0.01), and for distance covered (P?=?0.01) in the second 10-min split. However, no condition x time interactions were observed. No significant effects were found for sprint variables (P?>?0.05) with comparable values at T3 for mean distance (βA1: 163.9?±?3.8?m; βA2: 161.2?±?3.5?m; PL: 162.7?±?3.6?m), average power (βA1: 352.7?±?14.5?W; βA2: 342.2?±?13.5?W; PL: 348.2?±?13.9?W) and lactate (βA1: 10.0?±?0.9?mmol·L^??1; βA2: 9.2?±?1.1?mmol·L^??1; PL: 8.7?±?0.9?mmol·L^??1).

Conclusions

Whilst daily βA may confer individual benefits, these results demonstrate limited impact of βA (irrespective of dosing strategy) on 30-min rowing or subsequent sprint performance. Further investigation of βA dosage >?2.4?g·d^??1 and/or chronic intervention periods (>?4–8?weeks) may be warranted based on within-group observations.

     

Kinetic study of atom transfer radical homo- and copolymerization of styrene and methyl methacrylate initiated with trichloromethyl-terminated poly(vinyl acetate) macroinitiator

Atom transfer radical bulk copolymerization of styrene (St) and methyl methacrylate (MMA) was performed in the presence of CuCl/PMDETA as a catalyst system and trichloromethyl-terminated poly(vinyl acetate) telomer as a macroinitiator at 90 °C. The overall monomer conversion was followed gravimetrically and the cumulative average copolymer composition at moderate to high conversion was determined by ¹H NMR spectroscopy. Reactivity ratios of St and MMA were calculated by the extended Kelen–Tudos (KT) and Mao–Huglin (MH) methods to be r_St = 0.605 ± 0.058, r_MMA = 0.429 ± 0.042 and r_St = 0.602 ± 0.043, r_MMA = 0.430 ± 0.032, respectively, which are in good agreement with those reported for the conventional free-radical copolymerization of St and MMA. The 95% joint confidence limit was used to evaluate accuracy of the estimated reactivity ratios. Results showed that in the controlled/living radical polymerization systems such as ATRP, more reliable reactivity ratios are obtained when copolymer composition at moderate to high conversion is used. Good agreement between the theoretical and experimental composition drifts in the comonomer mixture and copolymer as a function of the overall monomer conversion was observed, indicating the accuracy of reactivity ratios calculated by copolymer composition at the moderate to high conversion. Instantaneous copolymer composition curve and number-average sequence length of comonomers in the copolymer indicated that the copolymerization system tends to produce a random copolymer.     

Calculation of reactivity ratios of methacrylic acid-ethyl acrylate copolymer by on-line quantitative 1H NMR spectroscopy

The solution copolymerization of methacrylic acid (MAA) and ethyl acrylate (EA) was studied by online proton nuclear magnetic resonance spectroscopy (¹H NMR) using 2,2′–azobisisobutyronitrile as an initiator in deuterated dimethyl sulfoxide at 60 °C. The chemical compositions of the copolymer and the comonomer concentrations were determined from the conversion of comonomers to copolymer by quantitative in situ NMR monitoring to estimate the reactivity ratios of the comonomers at low conversion. This is a new and easy methodology to analyze radical copolymerization. In this research, it is shown that monomer reactivity ratios can be calculated by data collected only from one initial comonomer mixture composition via online monitoring progress of the copolymerization reaction. The reactivity ratios of MAA and EA are equal to 2.360 and 0.414, respectively. This approach is used to compute the monomer reactivity ratios in a nonlinear integrated form of the copolymerization equation which is described by Mayo and Lewis terminal model. The fairly good agreement between the results and the literature data reported for the emulsion system represent the accuracy of the reactivity ratios calculated by this new approach. The calculated reactivity ratios for emulsion copolymerization are r _MAA = 2.040 and r _EA = 0.470, and the previous literature data are r _MAA = 2.580 and r _EA = 0.157.     

Acceleration of the redox kinetics of VO2+/VO2 + and V3+/V2+ couples on carbon paper

The redox kinetics of VO²⁺/VO₂ ⁺ and V³⁺/V²⁺ couples on a carbon paper (CP, HCP030 N, Shanghai Hesen, Ltd., China) electrode were investigated in terms of their standard rate constant (k ₀) and reaction mechanism. The values determined for k ₀ for VO²⁺ ?? VO₂ ⁺ and V³⁺ ?? V²⁺ using the CP electrode are 1.0 × 10^?3 and 1.1 × 10^?3 cm s^?1, respectively. The value of k ₀ increases by one or two order(s) of magnitude compared with values obtained using electrodes composed of pyrolytic graphite and glassy carbon. The acceleration of the redox kinetics of vanadium ions is a result of the large surface area of the CP electrode. An inner-sphere mechanism for the reaction on the surface of the electrode is proposed. The kinetic features of vanadium redox reactions on the CP electrode reveal that CP is suitable for use as the electrodes in vanadium redox-flow batteries.     

Polyelectrolytes with various charge densities: Synthesis and characterization of diallyldimethylammonium chloride-acrylamide copolymers

The synthesis of defined polyelectrolyte models by radical copolymerization of diallyldimethylammonium chloride (DADMAC, M₁) and acrylamide (AAM, M₂) in aqueous solution is impeded by a large difference of the reactivity ratios (r₁ ? r₂) leading to a strong conversion dependence of the copolymer composition. For the synthesis of normally distributed polyelectrolytes of the same molecular weight with various charge densities, a general algorithm based on a feeded polymerization with dosage of the more reactive monomer was therefore developed. Various copolymer compositions predictable by the Mayo-Lewis equation and determined by chloride potentiometry were obtained. The sequence lengths distributions investigated by ¹³C NMR spectroscopy followed a Markov statistic of first order. The ¹³C NMR spectroscopy is shown as alternative method to gravimetry in determining reactivity ratios. The partial specific volumes and the refractive index increments of the copolymers correspond to the additivity principle. Further molecular and dynamic parameters are determined by membrane osmometry, static and dynamic light scattering, analytical ultracentrifugation, gel permeation chromatography, and viscometry. Monomodal molecular weight distributions, small polydispersities only for copolymers with high content of DADMAC are obtained at given comonomer and initiator concentration. The number-average molecular weight is almost constant for a broad copolymer composition range. R_g-M and [η]-M relations could be established for practical use at high ionic strength, despite the various chemical compositions. Some indications for a higher stiffness of copolymers with high contents of DADMAC despite the shielding of the electrostatic interactions are, however, given. At low ionic strength the electrostatic interactions prevail. Their influence with increasing charge density is stronger on the Huggins constants (intermolecular interactions) than their effect on the intrinsic viscosities (intramolecular interactions).     

Synthesis and conformation studies of copolypeptides composed of γ-methyl-l-glutamate and ε-N-carbobenzyloxy-l-lysine

Copolypeptides (PMGCL) composed of γ-methyl-l-glutamate(MLG) and $\text{?-N-}\text{carbobenzyloxy-}\text{l}\text{-lysine(CBL)}$ covering the whole range of copolymer composition were synthesized by the N-carboxyanhydride (NCA) method. The experimentally obtained monomer reactivity ratios were r₁(MLG)=2·0±0·4 and r₂(CBL)=0·5±0·1, from which the fractions of monomer dyads and triads in copolymer were plotted against the initial comonomer composition. From experimental results on thermally induced coil-to-helix transition of the copolypeptides in dichloroacetic acid/1,2-dichloroethane (DCA-DCE) systems, it has been found that these copolypeptides can exist in the α-helix conformation in the same manner as homopolypeptides PMLG and PCBL. The van't Hoff heat of transition ΔH showed a minimum against the initial monomer composition. The enthalpy ΔH_res of formation of intramolecular hydrogen bonds per peptide bond also showed a minimum against copolymer composition. Such behaviour on ΔH and ΔH_res was also found for copolypeptide (PBGCL) composed of γ-benzyl-l-glutamate(BLG) and $\text{?-N-}\text{carbobenzyloxy-}\text{l}\text{-lysine(CBL)}$ in DCA-DCE systems reported in a previous paper. The presence of a minimum in these relationships may be attributed to specific interactions between the side chain of one comonomer and that of the other comonomer in a two component copolymer. It is also pointed out that these copolymer molecules can exist in the α-helix conformation in the solid state.     

Synthesis and Surface Active Properties of a Novel Linear Dodecyl Diphenyl Ether Sulfonate Gemini Surfactant

The linear dodecyl diphenyl ether sulfonate gemini surfactant (C₁₂-DLADS) has been synthesized by a new route from lauric acid according to a five-step reaction sequence consisting of acidification, Friedel?CCrafts acylation, Clemmensen reduction, sulfonation and a neutralization reaction. The surfactant and intermediates were characterized by ¹H-NMR, HPLC/MS and elemental analysis. The properties have been studied by surface tension (?? _CMC) and conductivity measurements. The thermodynamic parameters of micellization were calculated. The test results show that C₁₂-DLADS has lower critical micelle concentration (CMC) and better capability for lowering the ?? _CMC. The ?? _CMC and CMC are 36.04?mN/m and 6.03?×?10^?4?mol/L respectively at 45?°C. Moreover, with the increase in temperature, the conductivity of C₁₂-DLADS increased, while the counterion binding K ₀ decreased. The thermodynamic data show that the micellization process for the surfactant C₁₂-DLADS is entropy driven.     

Reactivity ratios during radiation‐induced grafting of comonomer mixtures onto polyester fabrics

Radiation‐induced grafting of binary mixtures of acrylonitrile (AN)/styrene (S) and acrylamide (AAm)/styrene (S) onto polyester fabric (PET) has been investigated. Synergism during radiation grafting was investigated by determining the graft yield fraction for each monomer in the final graft copolymer. Moreover, by knowing the mole fraction of each monomer in the grafting solution, the reactivity ratio of the individual monomers in the comonomer mixture during graft copolymerization could be determined: in the case of AN/S comonomer mixture, the calculated reactivity ratios for AN and S are 0.04 and 0.05, respectively; the calculated reactivity ratios of AAm and S in their comonomer mixture are 1.82 and 0.41, respectively. © 2001 Society of Chemical Industry     

Kinetics measurements on a stationary disk electrode in a uniformly rotating fluid (SDERF). II. The electron transfer reaction in the Fe(CN)4−6/Fe(CN)3−6-system

The operation of the SDERF-cell in the study of the electron transfer kinetics of the Fe(CN)^4?₆/Fe(CN)^3?₆-system in 1 M KCl and 1 M KNO₃-solutions at a stationary Pt-disk electrode is reported. The experimental current—overpotential curves are recorded by linear sweep voltammetry and analysed by two different methods using the theoretical relationship derived for a stationary disk electrode placed in a free rotating fluid. Both methods give the same value for the experimental rate constant k*. The effects of the temperature (0° to 40°C) and of the ratio of the rotor radius (r_r) to the electrode radius (r_e)(r_r/r_e = 0.50 to 0.81) have been studied. The activation energy for the redox process in 1 M KCl and 1 M KNO₃ are: E_a = 3.4 ± 0.6 kcal/mol and E_a = 3.7 ± 0.7 kcal/mol respectively, while the k*-values at 25°C are: k* = (5.67 ± 0.41) × 10^?3 cm.s^?1 and k* = (4.53 ± 0.29) × 10^?3 cm.s^?1 respectively. The difference from the standard rate constant k₀ ? 0.100 cm.s^?1 is explained by the effect of the cell-geometry characterized by the G-factor, so that k° = Gk*, where G ? 19 for our cell.     

Synthesis and Physicochemical Investigation of Novel Quaternary Ammonium Salt Cationic Gemini Surfactant Derived from Cyanuric Chloride

Three novel quaternary ammonium salt cationic gemini surfactants (QAS C _n ?C2?CC _n where n represents the hydrocarbon chain lengths of aliphatic amine, i.e., 6, 8, 12) were synthesized from 2,4,6?Ctrichloro?C1,3,5?Ctriazine, ethylenediamine, N,N?Cdimethylpropane?C1, 3?Cdiamine and benzyl chloride. ¹H-NMR, ¹³C-NMR, ESI?CMS spectra and elemental analysis were used to confirm the chemical structures of the prepared compounds. Their critical micelle concentrations (CMC) in the aqueous solutions were determined by surface?Ctension, electrical conductivity and steady?Cstate fluorescence methods respectively. With the increasing length of the hydrophobic chain, the values of their CMC decreased. The values of CMC, ?? _CMC, pC ₂₀, ??_max, and A _min were derived from surface tension measurements, while the thermodynamic parameters of micellization (?G _mic ^° and ?G _ads ^° ) were determined by electrical conductivity. These properties are significantly influenced by the hydrophobic chain length.     

Swelling and dye sorption studies of AAm/SA hydrogels crosslinked by glutaraldehyde and divinylbenzene

Highly swollen acrylamide (AAm)/sodium acrylate (SA) hydrogels were prepared by free radical solution polymerization in aqueous solution of AAm with SA as comonomer and two multifunctional crosslinkers such as glutaraldehyde (GL) and divinylbenzene (DVB). Water absorption and percentage swelling were determined gravimetrically. The influence of SA content in hydrogels was examined. Percentage swelling ratio of AAm/SA hydrogels was increased up to 2946–12,533%, while AAm hydrogels swelled up to 1326–1618%. The values of equilibrium water content of the hydrogels are between 0.9297–0.9921. Diffusion behavior was investigated. Water diffusion into hydrogels was found to be non‐Fickian in character. Adsorption properties of AAm/SA hydrogels in aqueous thionin solution have been investigated. Finally, the amount of sorbed thionin per gram of dry hydrogel (q_e) was calculated to be 4.81 × 10^?6?11.69 × 10^?6 mol thionin per gram for hydrogels. Removal efficiency (RE%) of the AAm/SA hydrogels was changed range 37.03–68.82%. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Ceric(IV) ion‐induced graft copolymerization of acrylamide and ethyl acrylate onto cellulose

Graft copolymerization of acrylamide (AAm) and ethyl acrylate (EA) onto cellulose has been carried out from their binary mixtures using ceric ammonium nitrate (CAN) as an initiator in the presence of nitric acid at 25 ± 1 °C. The extent of acrylamide grafting increased in the presence of the EA comonomer. The composition of the grafted chains (F_AAm = 0.52) was found to be constant during the feed molarity variation from 7.5 × 10^?2 to 60.0 × 10^?2 mol L^?1, whereas the composition of the grafted chains (F_AAm) was found to be dependent on feed composition (f_AAm) and reaction temperature. The effects of ceric(IV ) ion concentration, reaction time and temperature on the grafting parameters have been studied. The grafting parameters showed an increasing trend up to 6.0 × 10^?3 mol L^?1 concentration of CAN at a feed molarity of 30.0 × 10^?2 mol L^?1 and showed a decreasing trend on further increasing the concentration of CAN (>6.0 × 10^?3 mol L^?1) at a constant concentration of nitric acid (5.0 × 10^?2 mol L^?1). The composition of the grafted chains (F_AAm) was determined by IR spectroscopy and nitrogen content and the data obtained then used to determine the reactivity ratios of the acrylamide (r₁) and ethyl acrylate (r₂) comonomers by using a Mayo and Lewis plot. The reactivity ratios of acrylamide and ethyl acrylate were found to be r₁ = 0.54 and r₂ = 1.10, respectively, and hence the sequence lengths of acrylamide (m?M₁) and ethyl acrylate (m?M₂) in the grafted chains are arranged in an alternating form, as the product of the reactivity ratios of acrylamide and ethyl acrylate (r₁ × r₂) is less than unity. The rate of graft copolymerization of the comonomers onto cellulose was found to be dependant on the ‘squares’ of the concentrations of the comonomers and on the ‘square root’ of the concentration of ceric ammonium nitrate. The energy of activation (ΔE_a) of graft copolymerzation was found to be 5.57 kJ mol^?1 within the temperature range from 15 to 50 °C. On the basis of the results, suitable reaction steps have been proposed for the graft copolymerzation of acrylamide and ethyl acrylate comonomers from their mixtures. Copyright © 2005 Society of Chemical Industry     

Formation and relative reactivity of comonomer H-complexes in the radical copolymerization of acrylic acid with 1-vinyl-2-pyrrolidone

The dimerization constant (K_g) of acrylic acid and the association constant of the comonomer complex between acrylic acid and 1-vinyl-2-pyrrolidone (K₁) have been determined in chloroform by means of IR and ¹H NMR spectroscopy: K_d=(2.0±0.2) × 10³litre mol^?1 and K₁=68.5±0.5 litre mol^?1. A detailed equation for the copolymer composition considering the participation of the intermolecular complexes in the chain propagation has been derived with the help of a specific regular three addition states Markov chain. Applying a numerical procedure for fitting the experimental curve for the comonomer composition, this equation has been used in the estimation of the dimer and the comonomer complex relative reactivities. The considerably higher reactivities of the two complexes compared with that of the monomers are accounted for by the π-electrons' greater delocalization in the transition states involving the complexes species.     

Kinetics of Estrone Ozone/Hydrogen Peroxide Advanced Oxidation Treatment

Ozone/hydrogen peroxide batch treatment was utilized to study the degradation of the steroidal hormone estrone (E1). The competition kinetics method was used to determine the rate constants of reaction for direct ozone and E1, and for hydroxyl radicals and E1 at three pH levels (4, 7, and 8.5), three different molar O₃/H₂O₂ ratios (1:2, 2:1, and 4:1) and a temperature about 20°C. The average second-order rate constants for direct ozone-E1 reaction were determined as 6.2?×?10³?±?3.2?×?10³ M^?1s^?1, 9.4?×?10⁵?±?2.7?×?10⁵ M^?1s^?1, and 2.1?×?10⁷?±?3.1?×?10⁶ M^?1s^?1 at pH 4, 7, and 8.5, respectively. It was found that pH had the greatest influence on the reaction rate, whereas O₃/H₂O₂ ratio was found to be slightly statistically significant. For the hydroxyl radical-E1 reaction, apparent rate constants ranged from 1.1?×?10¹⁰ M^?1s^?1 to 7.0?×?10¹⁰ M^?1s^?1 with an average value of 2.6?×?10¹⁰ M^?1s^?1. Overall, O₃/H₂O₂ is shown to be an effective treatment for E1.     

Mild-thermal fabrication and phase conformation of chopped glass fiber-reinforced low-density unsaturated polyester resin with NH<Subscript>4</Subscript>HCO<Subscript>3</Subscript>

Chopped glass fiber-reinforced low-density unsaturated polyester resin product (CFR-LDUPRP) was fabricated utilizing chopped glass fiber and ammonium bicarbonate through an innovative mild-thermal process featuring an ideal phase conformation. Based on the mild-thermal mechanism and preliminary experiments, an orthogonal experiment was conducted to obtain the optimal conditions of CFR-LDUPRP fabrication. The optimal fabrication temperature of 76.0 °C, 20.00 phr of 3 mm chopped glass fiber, 2.50 phr of NH₄HCO₃ and 1.50 phr of tert-butylperoxy benzoate (TBPB) comprised the optimal conditions for CFR-LDUPRP fabrication. Under this condition, the density (ρ), compressive strength (P), and specific compressive strength (P_s) of CFR-LDUPRP specimen were 0.63?±?0.02 g cm^??3, 24.29?±?0.73 MPa, and 38.56?±?1.02 MPa g^??1 cm³, in the given order. The analyses of nonisothermal DSC and semi-quantitative FTIR revealed that NH₄HCO₃ neutralized the residual acid in the resin, leading to an early polymerization of resin and a prolonged curing process of UPR. The endothermic decomposition of NH₄HCO₃ and the vaporization of water enabled a mild-thermal mechanism, which was beneficial for the growth of bubbles and for the distribution of chopped glass fiber in the resin. Proper phase conformation of the resin, bubbles, chopped glass fiber together with cracks and microvoids in the resin matrix, characterized by SEM and ¹H NMR, facilitated the polymerization of UPR and improved properties of CFR-LDUPRP. Bubbles diameter ranged from 0.27 to 0.61 mm without linking or destroyed bubbles.     

Free‐radical homo‐ and copolymerization of vinyl acetate and n‐butyl acrylate: Kinetic studies by online 1H NMR kinetic experiments

Free‐radical homo‐ and copolymerization of vinyl acetate (VAc) and n‐butyl acrylate (BA) in benzene‐d₆ were performed by using benzoyl peroxide as an initiator at 70°C. Polymerization kinetic was followed by online ¹H NMR kinetic experiments. Significant drift in the comonomer mixture composition with reaction progress was observed. Reactivity ratios of VAc and BA were calculated by terminal unit model (TUM) as well as by simplified penultimate unit model (PUM) with r_VAc = 0. It was found that copolymer composition can be described well by the TUM. “Lumped” kinetic parameter ( $ k_p .k_t^{ - 0.5} $ ) was estimated from experimental data. A good fitting between the theoretical and experimental drifts in the comonomer mixture and copolymer compositions with reaction progress was observed. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011