Isothermal frontal polymerization: Confirmation of the isothermal nature of the process and the effect of oxygen and polymer seed molecular weight on front propagation

Isothermal frontal polymerization is a directional polymerization that utilizes the Norish‐Trommsdorff (gel) effect to produce optical gradient materials. When a solution of methyl methacrylate and thermal initiator contacts a polymer seed (a small piece of poly(methyl methacrylate), a viscous region is formed in which the polymerization rate is faster than in the bulk solution. We obtained definitive evidence of the isothermal nature of the process by placing thermocouples above the propagating front. Using the optical technique of laser line deflection (Weiner's method), we studied the front propagation to determine the induction period, and the maximum distance propagated as a function of the molecular weight of the seed. We determined that the polymer seed must have a minimum molecular weight to initiate a front. We also determined that oxygen would act as a bulk polymerization inhibitor and increase the front propagation distance, but after purging the monomer–initiator solution with oxygen for several hours, the distance was shortened. We ascribed this behavior to the formation of peroxy radicals from the slow decomposition of the initiator and subsequent reaction with oxygen. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 3601–3608, 2006     

Reversible chain reaction between <Emphasis Type="Italic">N,N</Emphasis>′-diphenyl-1,4-benzoquinonediimine and 2,5-dichlorohydroquinone: Kinetics,mechanism, and the rate constants of elementary steps

The kinetics of the reversible chain reaction between N,N′-diphenyl-1,4-benzoquinonediimine and 2,5-dichlorohydroquinone was studied in chlorobenzene at 298 and 343 K. Experiments in the presence of an initiator proved that the reaction proceeds via a chain mechanism with a chain length of ～10⁴ to 10⁵ units, depending on the reactant and initiator concentrations and temperature. The reaction rate first increases and then decreases with increasing concentrations of the reaction products (N,N′-diphenyl-1,4-phenylenediamine and 2,5-dichloroquinone) due to the pronounced reversibility of the chain termination and propagation steps involving the reaction products. The reaction orders with respect to the components were determined. The rate constants and activation energies of most of the elementary steps of the forward and backward chain reactions were determined or reliably estimated. Induction periods were observed for the first time in the reversible chain reactions in the quinoneimine + hydroquinone systems. The induction periods are due to the long time required for the establishment of the steady-state radical concentrations in the system.     

Kinetics and mechanism of group transfer polymerization of N-butyl acrylate catalyzed by Hgl2/(CH3)3Sil in toluene

The group transfer polymerization (GTP) of n-butyl acrylate (nBuA) using 1-methoxy-1-(trimethylsiloxy)-2-methyl-1-propene (MTS) as an initiator, mercuric iodide (HgI₂) as a catalyst in toluene at room temperature gives a very good control of molecular weight and narrow molecular weight distribution. (M̄_w/M̄_n < 1.2). Kinetic studies in this system reveal that this reaction is rather slow, half-lives being in the range of hours. The kinetic order of the apparent rate constant of propagation with respect to initiator and catalyst concentrations were found to be near to unity. However, the first-order time-conversion plots exhibit considerable induction periods. Upon addition of trimethylsilyl iodide (TMSI) the induction periods vanish and the rates are increased by two orders of magnitude. The reaction is first-order with respect to TMSI indicating that it takes part in the reaction by activating the catalyst. The complex from HgI₂ and TMSI acts as a nucleophilic catalyst, similar to oxyanions in the GTP of MMA in THF. It is proposed that the induction periods are due to the formation of TMSI from MTS and HgI₂.     

The Anionic Polymerization of Trimethylvinylsilane

Trimethylvinylsilane was found to polymerize anionically in cyclo-hexane much like styrene or dienes, except for the occurrence of a termination step. The propagation and initiation reactions were found to be first order with respect to trimethylvinylsilane and one-half order with respect to the initiator and chain ends initially, but first order after the initiator was consumed. Rate constants for initiation, propagation, and termination were found to increase in the presence of ethers, with the termination rate constant increasing the fastest. In the absence of ethers, the propagation rate constant is small, 1.4 mL^1/2/(mol^1/2 min) at 22°C.     

In situ chemical oxidation of aniline by persulfate with iron(Ⅱ) activation at ambient temperature

<正>The kinetics of aniline degradation by persulfate processes with iron(Ⅱ) activation at ambient temperature was investigated in this study.With iron(Ⅱ) as initiator,the oxidation reactions were found to follow a biphasic rate phenomenon:a rapid transformation followed by a slow but sustained oxidation process.In the first 30 s,the reaction mainly relies on the persulfate-Fe~(2+) reaction in which aniline is oxidized rapidly.After 30 s,the aniline was still oxidized but the rate of reaction tended to be slower and the rates were clearly linear-proportional.After the initial fast oxidation,the reactions appeared to follow a pseudo-first-order model.     

Initiated oxidation of polyenes formed in the thermal degradation of PVC

Polyenes formed in the thermal degradation of PVC are readily oxidized in the liquid phase in the presence of a radical initiator. In pure oxygen at a constant rate of initiation, different length polyenes are consumed by a first-order reaction: the rate of consumption is proportional to the polyene length and to the square root of initiator concentration. Applying the relationships given by the theory of chain reactions, we determined the ratio of the rate constant of chain propagation calculated for one double bond k₂ to the square root of the chain-termination rate constant k₄. The value obtained, which is relatively high in comparison to other unsaturated hydrocarbons, reflects very well the high reactivity of polyenes of the degraded PVC sample towards oxidation. Intramolecular chain propagation steps are also likely to play a role in the oxidation of polyenes.     

Redox control within single-site polymerization catalysts

The activity of a single-site titanium-based lactide polymerization initiator supported by a ferrocenyl-derivatized salen ligand is shown to be modulated by a chemical redox switch; a substantially higher rate of propagation is found for the neutral catalyst compared to its oxidized dicationic ferrocenium counterpart.     

Isoprene Polymerization by Butyllithium in Cyclohexane. II. Propagation Reaction

The kinetics of the propagation reaction in the polymerization of isoprene initiated by n-, sec-, or t-butyllithium, in the absence or in the presence of the three corresponding lithium butoxides, are studied in the two possible major cases. In the first case, the propagation takes place without simultaneous initiation; the reaction is then first-order versus the monomer concentration and one-sixth-order versus the polyisoprenyllithium concentration. The lithium butoxides decrease the propagation rate, but the effect is not very dependent on the nature of the butoxide. In the second case, the presence of the initiator decreases the propagation rate in a manner which depends on the concentrations of the reactants and on the nature of the initiator. The effect of the lithium butoxide is not simply additive. Depending on the relative concentrations, a synergistic effect may be observed. It is suggested that the active species are chiefly ion pairs of unassociated polyisoprenyllithium. Ion pairs from associated molecules may have limited activity.     

Tailored heterogeneity indices in anionic polymerization

Equations are derived for the differential molecular weight distribution curve and for the heterogeneity index for several types of delayed initiator addition in anionic polymerization. All the results are in closed and easily used form, and depend only upon the product of the rate constant of the propagation reaction, the total initiator concentration, and a parameter representative of the rate of initiator addition. The results are plotted versus the above-mentioned product, so that one can determine the heterogeneity index to be expected under a wide range of the variables involved.     

Elementary reactions of the emulsions polymerization of styrene with the localization of radical formation acts at the interface

The localization of radical formation acts at the interface achieved by the application of specially prepared surfactant initiators, fixation of initiating sites on the surface of seed latex particles by covalent bonds, or by redox initiating systems were experimentally studies. It is ascertained that the fixation of the initiator of polymerization at the interface of the emulsion system brings about a change of the kinetic parameters of its decomposition—an increase in the decomposition rate and decrease in the initiation efficiency. The experiments (measurements of chain propagation rate) demonstrated that the nature of emulsifying agent and initiator has no effect on the chain propagation acts. The kinetics of the chain termination depends on the properties of the emulsion system that is revealed in the dependence of chain termination constants on the type of initiator and the diameter of latex particles. These effects are supposed to be explained by influence of the colloid and chemical parameters of the reaction system on the conformation entropy of the growing macroradicals; and the low values of the chain termination constants (10²–10⁴ L mol^?1 s^?1) are due to the higher activation energy of chain termination for the emulsion polymerization.     

基团转移聚合的动力学研究

<正> 作为一种新的极性单体加聚方式的基团转移聚合(Group Transfer Polymerization,GTP),近年来发展很快。对不同引发体系和单体的基团转移聚合进行动力学研究,由此得到规律性的认识,明确聚合过程的影响因素,有利于聚合机理的完善。文献已报道了用     

Living diradical polymerization

A diradical initiator containing two thermoreversible bonds was prepared and used for the polymerization of styrene at 90°C. The monomer consumption and the variation of the molecular weight were monitored with time. The results show that the process can be considered as living and that the polymerization rate is independent of the radical initiator concentration. By elemental analysis of the chain ends it was concluded that the propagation reaction occurs at both ends.     

Caesium as counter-ion in the anionic polymerization of ethylene oxide—II: Kinetics in hmpt

Results are reported for the kinetics of the anionic polymerization of ethylene oxide in hexamethylphosphoramide using the caesium alkoxide of the monoethylether of diethylene glycol as initiator at 40·0°.The reactions were found to be first order in monomer and 0·5 in initiator; rates are depressed by adding caesium tetraphenyl boride. These results indicate that propagation takes place by free ions and ion pairs; the respective propagation rate constants are k_(?) = 22 and k_(±) = 0·2 M 'sec.     

Assessment of Microwave Effect on Polymerization Conducted under ARGET ATRP Conditions

A comprehensive kinetic model based on the method of moments is developed for understanding the kinetics of activators regenerated by electron transfer atom transfer radical polymerization (ARGET ATRP) under microwave irradiation. Both the experimental data and the simulation results show that the polymerization under microwave irradiation is much faster than the thermal polymerization. Simulation results indicate that the acceleration of polymerization can be attributed to the increase of propagation rate coefficient and the radical generation by microwave irradiation. Kinetic behaviors, such as the effect of catalyst concentration and initial initiator, are investigated in detail. Results show that the catalyst concentration has negligible influence on polymerization rate while the initiator concentration can affect both the molecular weight and the reaction rate. In conclusion, this work thoroughly investigates the kinetic mechanism of ARGET ATRP under microwave irradiation, providing both theoretic and experimental supports to improve the product property of polymer materials.     

Thermal polymerization of styrene in the presence of some ferrocene derivatives. I. Evidence of ferrocene–styrene interaction

Styrene has been polymerized thermally at 60.5°C, without added initiator, in the presence of ferrocene. An increase in the rate of polymerization was observed, but the degree of polymerization remained constant. Evidence of ferrocene–styrene interaction is presented, and a kinetic scheme involving propagation with styrene in such an interaction state is proposed to account for these findings. Various kinetic parameters defined by this scheme have been evaluated.     

Kinetic Studies of the Ring-Opening Polymerization of 1-β-Cyanoethylazetidine

The ring-opening polymerization rate of 1-β-cyanoethylazetidine (CA) with 3-hydroxy-1-propanesulfonic acid sultone (HPSS) as an initiator has been investigated in acetonitrile. The polymerization of CA with HPSS proceeded by way of a zwitterion formed by the addition reaction of CA and HPSS. The course of polymerization involved, as an early stage, slow initiation due to the low reactivity of the zwitterion. The propagation constants were obtained as were the enthalpy of activation for propagation (ΔH_p? = 12 kcal/mol) and the entropy of activation for propagation (ΔS_p? = ?31 cal/K·mol).     

Anionic polymerization of methacrylonitrile—II.: Polymerization with 1,1-diphenyl-n-hexyllithium and sec-butyllithium as initiators

The anionic polymerization of methacrylonitrile has been investigated at ?75° in toluene with 1,1-diphenyl-n-hexyllithium and sec-butyllithium as initiators. With both initiators, initiation was fast and no unreacted initiator was left. The efficiency was much higher for 1,1-diphenyl-n-hexyllithium than for sec-butyllithium probably for steric reasons. With both initiators, a second order dependence on initiator was found. To check that this is not an artifact resulting from measurements in a medium starting to gel at a point which is difficult to detect precisely, kinetic measurements were also carried out with 2-polystyryl-l,l-diphenylethyllithium as an initiator. Second order kinetics were again obtained; the propagation rate constants, taking into account the efficiencies of initiators, were the same within experimental error for all three initiators. Viscosity measurements performed on a methacrylonitrile “capped” 2-polystyryl-l,l-diphenylethyllithium initiator showed the living polymethacrylonitrile chains to be associated.     

Vinyl polymerization in the presence of copper salts

The radical polymerization of several vinyl monomers has been studied in the presence of cupric chloride. A termination reaction with Cu^II species leads to the formation of Cu^I species which can also participate significantly in termination with some, but not all, of the monomers studied. A theoretical treatment of the kinetics of such systems is presented which takes full account of initiator depletion during extended inhibition during extended inhibition periods. Specific velocity constants for reactions of polymer radicals with both Cu^II and Cu^I moieties are derived from observations on the nonstationary phase at the end of the inhibition period and from the subsequent steady state of polymerization. On the basis of the results presented here, together with the work of other authors, the patterns-of-reactivity approach gives α = ?5.4, β = 9.0 as the parameters for copper (II) chloride. The implications of the results in relation to the mechanisms of the reactions between polymer radicals and both copper(II) chloride and copper(I) chloride are discussed. The kinetic treatment also provides an improved method for the determination of the rate of initiator decomposition and the rate of initiation form studies of the inhibition period.     

Diffusion-controlled reactions in vinyl chloride suspension polymerization

The vinyl chloride suspension polymerization is kinetically modeled with a general approach for the independent calculation of diffusion effects on polymerization reactions. For the initiator decomposition, propagation and termination an apparent rate coefficient is determined, built up from two contributions: the intrinsic rate coefficient and a diffusional contribution. The diffusional contribution is calculated with the Smoluchowski model, the diffusion coefficients being determined from the free volume theory. When applying the free volume theory no adjustable parameters are used. The intrinsic rate coefficients are taken from the literature. Hence, a model without any adjustable parameters is obtained. Calculations show that the glass effect appears only at (very) high conversions. Due to the cage effect the initiator efficiency decreases strongly as soon as the monomer phase has disappeared. The gel effect always occurs in the polymer-rich phase and results in a decrease of the termination rate coefficient at the start of the third stage in the polymerization process. There is a good agreement with experimental results.