Effect of solvent on radical polymerization of vinyl benzoate

Absolute rate constants of the vinyl benzoate polymerization have been measured by use of the intermittent illumination method in various aromatic solvents and ethyl acetate at 30°C. The determination of absolute rate constants showed that effects of solvent on the polymerization rate of vinyl benzoate were mainly ascribed to the variation of k_p values with solvents rather than that of k_t values. The k_p values for solvents used increased in the order: benzonitrile < ethyl benzoate < anisole < chlorobenzene < benzene < fluorobenzene < ethyl acetate. There was an eightfold difference between the largest and the smallest values The large variation among k_p values was explained neither by the copolymerization through solvents nor the chain transfer to solvents, but by a reversible complex formation between the propagating radical and aromatic solvents. This explanation was supported by a correlation between k_p values and calculated delocalization stabilizations for the complexes.     

Solvent effect on radical polymerization of butyl acrylate

The propagation and termination rate constants k_p and k_t for the radical polymerization of butyl acrylate initiated by biacetyl have been measured by using the rotating-sector method, in various solvents at 30°C. The value of k_p and initiation rate R_i varied with solvents, while the value of k_t did not change with solvents except for benzonitrile. The variation of k_p with aromatic solvents has a trend against Hammett σ_p of the solvent substituents similar to that for methyl methacrylate or phenyl methacrylate except for the value in benzonitrile, when it is larger than the variation for methyl methacrylate or phenyl methacrylate. The larger variation of k_p for butyl acrylate is compatible with the view that the origin of the solvent effect lies in complex formation between the propagating radical and aromatic solvent molecules. The exceptional decrease in k_p and k_t in benzonitrile is explained by a contraction of the poly(butyl acrylate) chain in the poor solvent.     

Solvent effect on the radical polymerization of di-n-butyl itaconate

Solvent effect on the polymerization of di-n-butyl itaconate (DBI) with dimethyl azobisisobutyrate (MAIB) was investigated at 50 and 61°C. The solvents used were found to affect significantly the polymerization. The polymerization rate (R_p) and the molecular weight of the resulting polymer are lower in more polar solvents. The initiation rate (R_i) by MAIB, however, shows a trend of being rather higher in polar solvents. The stationary state concentration of propagating poly(DBI) radical was determined by ESR in seven solvents. The rate constants of propagation (k_p) and termination (k_t) were evaluated by using R_p, R_i, and the polymer radical concentration observed. The k_p value decreases fairly with increasing polarity of the solvent used, whereas k_t is not so influenced by the solvents. The solvent effect on k_p is explained in terms of a difference in the environment around the terminal radical center of the growing chain. Copolymerization of DBI with styrene (St) was also examined in three solvents with different physical properties. The poly(DBI) radical shows a lower reactivity toward St in a more polar solvent.     

ESR study on radical polymerization and its application to microemulsion systems

Well-resolved electron spin resonance (ESR) spectra of propagating radicals of vinyl and diene compounds were observed in a single scan by a conventional CW-ESR spectrometry without the aid of computer accumulation and the specially designed cavity and cells. Although solvents which could be used for ESR measurements were restricted to nonpolar solvents, such as benzene, toluene, and hexane, new information on dynamic behavior and reactivity of the propagating radicals in the radical polymerization of vinyl and diene compounds were obtained. Thus, values of propagation rate constants (k_p) for vinyl and diene compounds were determined by an ESR method. Some of the k_p values were in a fair agreement with those obtained by a pulsed laser polymerization (PLP) method. Furthermore, polymer chain effect on apparent k_p was clearly observed in the radical polymerization of macromonomers and in the microemulsion polymerization. In ESR measurement on inclusion polymerization system, important information on the origin of the 9-line spectrum observed in the radical polymerization of methacrylate propagating radicals was obtained.     

Polymerization and reaction rate studies on substituted phenylmethylbis(dimethylamino)silanes

The synthesis of seven para- or meta-substituted phenylmethylbis(dimethylamino)-silane monomers has been carried out. These silanes were polymerized with 1,4-bis(hydroxydimethylsilyl)benzene in tetrahydrofuran at 30°C, and the polymerization kinetics were followed by monitoring dimethylamine evolution for 200 min. The polymers were quenched by precipitation in methanol and molecular weight data were obtained. The polymerizations followed second-order kinetics in every case as evidenced by the linear plots of 1/(a ? x) versus time. The molecular weight data generally correlated with the specific reaction rate constant k₂ to show an increasing polymer molecular weight with increasing polymerization rate, although the range of k₂ values obtained for the substituted aminosilanes was relatively small (2.50 × 10^?5–6.67 × 10^?5 l./mole-sec). The value of k₂ increased in the following order: p-OCH₃, p-F, m-CH₃, H, m-OCH₃, p-CF₃, 3,5-di(CF₃). The logarithms of the rate constants correlated with the σ constants for the substituents, with a reaction constant, ρ of 0.391. The displacement at silicon in these reactions is discussed in terms of bimolecular mechanisms in which a four-center transition state may participate.     

Photoinitiation. IV. The effect of lewis acid on the vinyl monomer polymerization photoinitiated by aromatic hydrocarbons

Polymerization of acrylonitrile photoinitiated by naphthalene, anthracene, phenanthrene, and pyrene is accelerated by an admixture of zinc (II) chloride, acetate, or nitrate. The effect of zinc (II) salts on the rate of pyrene-photoinitiated polymerization of acrylonitrile leads to an increase in this rate in the order Zn/OCOCH_3/2 < ZnCl₂ < Zn/NO_3/2. The maximum polymerization rate is achieved at the molar ratio [ZnCl₂]/([ZnCl₂] + [pyrene]) approximately 0.7. In contrast to the photoinitiated polymerization of acrylonitrile, the methyl methacrylate admixture of zinc (II) chloride exerts a smaller effect on the polymerization rate. In the pyrene-photoinitiated polymerization of styrene an admixture of zinc (II) chloride retards the polymerization rate. Fluorescence of aromatic hydrocarbon in the system acrylonitrile–aromatic hydrocarbon is efficiently quenched by zinc (II) chloride. Stern–Volmer constants determined for pyrene (80 dm³ mole^?1), phenanthrene (66 dm³ mole^?1), and naphthalene (49 dm³ mole^?1) are higher by about 2–3 orders of the Stern–Volmer constants for fluorescence quenching of aromatic hydrocarbons by acrylonitrile in the absence of ZnCl₂. The fluorescence of anthracene in acrylonitrile is not quenched by ZnCl₂. The acceleration effect of Zn (II) salts on the polymerization of acrylonitrile photoinitiated by aromatic hydrocarbons depends on two factors: an increase in the ratio of the rate constant of the growth and termination reactions, k_p/k_t, and an increase in the quenching constant of fluorescence of aromatic hydrocarbon, k_q, by the complex {acrylonitrile…ZnCl₂}. ZnCl₂ thus influences both the growth and initiation reactions of the polymerization process.     

Solvent effects on radical homo- and copolymerizations of methacryloyl fluroride

The effect of solvent in homo- and copolymerizations of methacryloyl fluoride (MAF) was investigated in various aromatic solvents. In these solvents, there is a significant effect on the rate of polymerization, on the tacticity of the resulting poly(methacryloyl fluoride), and on the copolymerization of MAF with methyl methacrylate (MMA). The equilibrium constants between MAF and aromatic solvents were determined from NMR spectroscopic measurements. These results indicated that the solvent effect on the MAF polymerization stems from changes in reactivity of MAF induced by the strong MAF–solvent interaction as well as stabilization of the MAF radical by solvents. Copolymerization of MAF with both p-methoxystyrene (MSt) and p-nitrostyrene (NSt) was also studied.     

Comments on the determination of absolute rate constants in anionic polymerization

Claims have recently been made that absolute rate constants for chain propagation of the unassociated active centers can be made in systems where a high degree of association is present. Anionic polymerization of styrene in nonpolar solvents with lithium as counterion is a typical case. The conditions required to obtain these constants (and the associated aggregate dissociation constants) are described using data from styrene polymerization with lithium and potassium as counterions and data from o-methoxystyrene polymerization. The conclusion reached must be that the k_p and K_ds values obtained for styrene with counterion lithium cannot be obtained from existing literature data and are simply artifacts of the computer analysis. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 1065–1068, 1998     

Kinetics of retarded polymerization: Investigation of the retardation of V5+–thiourea initiated polymerization of methyl acrylate by phenol

The kinetics and mechanism of the retarding action of phenol on the V⁵⁺–thiourea initiated polymerization of methyl acrylate (MA) have been studied within the temperature range of 30–50°C. The effects of retarder (phenol), metal ion (V⁵⁺), monomer (MA), sulfuric acid, some organic solvents and inorganic salts on the percentage and rate of polymerization have been studied. The remarkable observation of the present study is the positive intercept obtained from the plot of [M]/R_p vs. 1/[M]. This type of observation is significantly different from previous studies on retarded polymerization. The values of composite rate constants k₀k_t/k_ik_pkK have been calculated from plots of [M]/R_p vs. 1/[M]. On the basis of experimental findings a reaction mechanism has been suggested, and a suitable rate expression has been proposed and explained.     

Kinetics and mechanism of the cationic polymerization of trioxane. II. Consideration of hydride transfer

The occurrence of hydride-transfer reactions during the cationic polymerization of trioxane was demonstrated, and rate constants were obtained. The donor of hydride ions in the transfer reactions was the monomer. The hydride-transfer reaction was a first-order reaction with respect to the concentration of the monomer, and it was governed, just as polymerization and depolymerization were (Shieh, Y. T.; Chen. S. A. J. Polym. Sci. Part A: Polym. Chem. 1999, 37, 483–492) by morphological changes. The hydride-transfer rate constants were 5 orders of magnitude smaller than those for polymerizations and depolymerizations. The rate constants for the reactions, including the polymerizations, depolymerizations, and hydride transfers, were smaller for the active centers on the solid surface than for those in solution, that is, k^′_p was less than k_p, k^′_d was less than k_d, and k^′_ht was less than k_ht. As a reaction medium, benzene had special effects on the kinetics of the cationic polymerization of trioxane. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 4198–4204, 1999     

Effect of amines on the ceric ion-initiated polymerization of vinyl monomers. II. Polymerization of acrylonitrile by ceric ion in presence of various substituted amines

The effect of various substituted amines on the polymerization of acrylonitrile initiated by ceric ammonium sulfate has been studied in aqueous solution at 30°C. It was found that the secondary and tertiary amines considerably increased the rate of polymerization, whereas the primary amines seemed to have no effect at all. From the kinetic studies it was found that the overall polymerization rate R_p is independent of ceric ion concentration and can be expressed by the equation: R_p = k₁ [amine] [monomer] + k₂[monomer]², where k₁ and k₂ are constants (involving different rate constants). The accelerating effect of the amines was attributed to a redox reaction between the ceric ion and the amine involving a single electron transfer, the relative activity of the different amines being thus dependent on the relative electron-donating tendency of the substituents present in the amine. The mechanism of the polymerization is discussed on the basis of these results, and various kinetic constants are evaluated.     

Polymerization of acrylonitrile. Kinetics of the reaction initiated by the Ce(IV)/thioacetamide redox system

Vinyl polymerization of acrylonitrile initiated by the Ce(IV)/thioacetamide redox system has been investigated in aqueous sulfuric acid in the temperature range of 10–20°C. The rate of polymerization (R_p) and the rate of Ce(IV) disappearance (?R_Ce) were measured. The effect of certain water-soluble organic solvents, added electrolytes, and aromatic and heterocyclic organic nitrogen compounds on the rate of polymerization has been investigated. Depending on the experimental results, we have suggested a suitable reaction scheme for the system which involves the production of initiating radicals from the oxidation of thioacetamide (TAm) by ceric ion and the termination of the polymer chain by metal ions.     

Reaction of chlorine dioxide with phenol

The kinetics of phenol oxidation with chlorine dioxide in different solvents (2-methylpropan-1-ol, ethanol, 1,4-dioxane, acetone, acetonitrile, ethyl acetate, dichloromethane, heptane, tetrachloromethane, water) was studied by spectrophotometry. In all solvents indicated, the reaction rate is described by an equation of the second order w = k[PhOH]·[ClO₂]. The rate constants were measured (at 10—60 °C), and the activation parameters of oxidation were determined. The reaction rate constant depends on the solvent nature. The oxidation products are a mixture of p-benzoquinone, 2-chloro-p-benzoquinone, and diphenoquinone.     

The effect of solvent on the homo-propagation rate coefficients of styrene and methyl methacrylate

The free radical propagation rate coefficients of both Methyl Methacrylate (MMA) and Styrene (STY) have been measured using Pulsed-Laser Polymerization. The effect of solvents on the propagation rate coefficient, k_p, is reported for several solvents, namely, bromobenzene, chlorobenzene, dimethyl sulphoxide, diethyl malonate, diethyl phthalate, benzonitrile, and benzyl alcohol, at 26.5°C. This preliminary data indicated that benzyl alcohol (BzA) had a large effect on the MMA propagation reaction. As earlier work indicated that N-methyl pyrrolidinone (NMP) would also have a large effect on the k_p of MMA, Arrhenius parameters were evaluated for both MMA and STY at two different concentrations of monomer in BzA and NMP. BzA had a significant effect (at 95% confidence) increasing both the activation energy (E_a) and the preexponential factor (A) for MMA and STY. In NMP, a similar trend is observed for MMA polymerization; however, while a solvent effect on STY was observed, the effect on E_a and A was too small to discern with confidence. A series of additional experiments was performed to evaluate the influence of camphorsulfonic acid (CSA) as an additive in STY polymerization. There was no effect of CSA on k_p, confirming that the strong effect CSA has on “living” radical polymerization of styrene does not originate from complexation leading to an accelerated propagation step but rather by altering the ratio of active-to-dormant chains in the reaction. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35 : 2311–2321, 1997     

Retardation of radical polymerization by phenylacetylene and its p-substituted derivatives

Radical polymerizations of styrene and methyl methacrylate in the presence of phenylacetylene and five of its p-substituted derivatives were carried out with the use of 2,2′-azobisisobutyronitrile as the initiator at 60°C. The initial overall rates of the polymerizations of styrene and methyl methacrylate in the presence of phenylacetylene were not proportional to the square root of the initiator concentration under the experimental conditions employed. The relationship between the overall polymerization rate and the concentration of the phenylacetylenes could be expressed by the Kice equation for the rate of a radical polymerization in the presence of a terminator. From this relationship the rate constant (k_s) of the reaction of a growing polymer radical with the phenylacetylenes and the constant C_s = (k_s/k_p), where k_p is the propagation rate constant of vinyl monomers, were determined. The C_s value thus obtained agree well with that derived from the relationship between the number-average degree of polymerization and the molar ratio of the phenylacetylenes to the vinyl monomer. Therefore the mechanism of the reaction may be considered as being one in which the growing radical reacts with the ethynyl group of the phenylacetylenes to yield a comparatively stable radical which terminates mainly by reaction with the growing radical, and so apparently the phenylacetylenes retard the vinyl polymerization. The substituent effects on the reaction were discussed on the basis of the following modified Hammett equation proposed by Yamamoto and Otsu: log [C_s(p-sub. PA)/C_s(PA)] = ρσ + γE_R where PA represents phenylacetylene, σ and E_R are the Hammett polar substituent constant and resonance substituent constant, respectively, and both ρ and γ are reaction constants. The γ value for the polymerization of both styrene and methyl methacrylate was 1.7. The ρ value was 1.0 for the polymerization of styrene and approximately zero for that of methyl methacrylate. These results demonstrate that the reactivity of the phenylacetylenes with the growing chain is influenced by both polar and resonance effects of their p-substituents in the degradative copolymerization of styrene and only by the resonance effect in that of methyl methacrylate.     

Determination of absolute rate constants for free radical polymerization of ethyl α-fluoroacrylate and characterization of the polymer

The absolute rate constants for propagation (k_p) and for termination (k_t) of ethyl α-fluoroacrylate (EFA) were determined by means of the rotating sector method; k_p = 1120 and k_t = 4.8 × 10⁸ L/mol.s at 30°C. The monomer reactivity ratios for the copolymerizations with various monomers were obtained. By combining the k_p values for EFA from the present study and those for common monomers with the monomer reactivity ratios, the absolute values of the rate constants for cross-propagations were also evaluated. Reactivities of EFA and poly(EFA) radical, being compared with those of methyl acrylate and its polymer radical, were found to be little affected by the α-fluoro substitution. Poly(EFA) prepared with the radical initiator was characterized by differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). Although the glass transition temperature obtained by DSC for poly(EFA) resembled that of poly(ethyl α-chloroacrylate), its TGA thermogram showed fast chain de polymerization to EFA that was distinct from complicated degradation of poly(ethyl α-chloroacrylate).     

Chromocene-based catalysts for ethylene polymerization: Kinetic parameters

The chromocene catalyst for ethylene polymerization shows a high response to hydrogen which leads directly to highly saturated polyethylenes containing methyl groups as the major terminal functionality in the polymers. At a polymerization temperature of 90°C the ratio of termination rate constants for hydrogen (k_H) and ethylene (k_M) is k_H/k_M = 3.60 × 10³. The ratio of k_H to the chain propagation constant (k_p) is k_H/k_p = 4.65 × 10^?1 A simple relation that can be derived from polymerization kinetics and the Quackenbos equation exists between melt index and hydrogen–ethylene ratio. A deuterium isotope effect (k_H/k_D) = 1.2 was calculated for the termination reaction. The overall polymerization process has an apparent activation energy of 10.1 kcal/mole. Oxygen addition studies show catalyst activity is proportional to initial divalent chromium content.     

Electrophoretic flow of interacting polymer chains: Effects of temperature,polymer concentration,and porosity

Using a Monte Carlo simulation in three dimensions, we studied the variation of the root-meansquare (rms) displacement (R_rms) of polymer chains with time and the rates of their mass transfer (j) as a function of biased field (B), polymer concentration (p), chain length (L_c), porosity (p_s), and temperature (T). In homogeneous/annealed system, the rms displacement of the chains shows a drift-like behavior, R_rms ∼ t, in the asymptotic time regime preceded by a subdiffusive power-law (R_rms ∼ t^k, with k < 1/2) at high p. The subdiffusive regime expands on increasing L_c and p but reduces on increasing T or B. In quenched porous media, the drift-like behavior of R_rms persists at low barrier concentration (p_b) and high T. However, at high p_b and/or low T, chains relax into a subdrift and/or subdiffusive behavior especially with high p or long L_c. Flow of chains is measured via an effective permeability (σ) using a linear response assumption. In annealed system, σ increases monotonically with B at high T and low p but varies nonmonotonically at low T, high p and high L_c. We find that σ decays with L_c, σ ∼ L, where α depends on B, p and T with a typical value a α ∼ 0.43−0.64 for p = 0.1-0.3 at B = 0.5. Further, σ decays with p, σ ∼ − Cp with a decay rate C sensitive to T and B. In quenched porous media, even at low pb and high T, σ varies nonmonotonically with bias, i.e., the increase of σ is followed by decay on increasing the bias beyond a characteristic value (B_c). This characteristic bias seems to decrease logarithmically with barrier concentration, B_c ∼ −klnp_b. The prefactor k depends on the chain length, k ≈ 0.35 for shorter chains (L_c = 20, 40) and ≈ 0.15 for longer chains (L_c = 60). Scaling dependence of σ on L_c similar to that in annealed system is also observed in porous media with different values of exponent α. The current density shows a nonlinear power-law response, j ∼ B^σ, with a nonuniversal exponent δ ≈ 1.10−1.39 at high temperatures and low barrier concentrations.     

Ionic Liquids - New Solvents in the Free Radical Polymerization

Summary: The analysis of the influence of ionic liquids (ILs) in polymer synthesis as an alternative for common organic solvents is still an active field of research. 1 Using ILs as solvents for free radical polymerizations implies a significant increase in polymerization rates and molecular weights which can be observed. In this work we examined the copolymerization behaviour of styrene (S) and methyl methacrylate (MMA), glycidyl methacrylate (GMA) and 2-hydroxypropyl methacrylate (HPMA) with acrylonitrile (AN) in 1-etyhl-3-methylimidazolium ethylsulfate ([EMIM]EtSO₄). ILs are liquids with comparable high polarities and viscosities. These two characteristic properties are strongly correlated with the rate coefficients of propagation k_p and termination k_t. 2 - 4 The rate constant of termination k_t decreases when the IL concentration and therefore the viscosity of the reaction mixture is increased, whereas the propagation rate coefficient k_p increases with increasing IL content. The viscosity of the IL can be varied by either working with mixtures of IL with conventional organic solvents – here the IL [EMIM]EtSO₄ was mixed with DMF – or by variation of the temperature. The influence of the viscosity of the IL ([EMIM]EtSO₄) on polymerization kinetics of methyl methacrylate (MMA) and styrene/acrylonitrile (S/AN) was investigated.