Free radical polymerization of vinyl acetate in the presence of liquid polysulfides

The free radical polymerization of vinyl acetate in the presence of a liquid polysulfide H(SCH₂CH₂OCH₂OCH₂CH₂S)_nH (thiocol) was investigated from the point of view of reaction mechanism and characterization of the resulting copolymers. It was shown that, besides the thiol end groups that were consumed very rapidly, the disulfide groups within the thiocol chain were also involved in chain transfer processes. The chain transfer constant of the thiocol S–S groups in the polymerization reaction was estimated from their rate of consumption versus the rate of monomer consumption (C_T = 0.89). The resulting copolymers, made up of randomly distributed thiocol sequences and PVAc blocks, were characterized by ¹H NMR, GPC, DSC and TGA measurements. The copolymers displayed only one glass transition each, which decreased as the PVAc block length decreased, while their thermal stability was lower than that of both thiocol and PVAc. The molecular weight of the copolymers increased with VAc conversion as a consequence of the insertion of PVAc blocks within the thiocol chain.     

Free-radical polymerization with long-chain branching: Batch polymerizations of vinyl acetate in t-butanol

Vinyl acetate was batch polymerized at 60°C in t-butanol solution. Conversion and molecular weights were measured as functions of time for several initiator and solvent concentrations. Although the overall rate constant depends somewhat on solvent concentration, the reaction is first order in monomer concentration up to at least 60% conversion and one-half order in the concentration of initiator. Molecular weights were independent of initiator concentration, confirming that the polymerization is transfer dominated. Measurements of M?_w and M?_w versus conversion were used to establish the individual transfer constants. All are independent of solvent concentration, except C_p, the polymer transfer constant, which decreases systematically with increasing solvent concentration.     

Effect of the radical scavenger t-butanol on gas-liquid mass transfer

The alcohol t-butanol has been used as a radical scavenger in the studies of ozone reactions in water and has been found to affect the gas-liquid mass transfer rates. An understanding of the effects of t-butanol on mass transfer parameters, including bubble size, gas holdup, mass transfer coefficient and the mass transfer specific surface area, is of key importance to not only improve the knowledge of this particular system but also to gain fundamental understanding about the effects of gas/liquid surface modifiers on the contact between phases and the mass transfer rates. An experimental study has been carried out to investigate the effects of t-butanol concentrations on the physical properties of aqueous solutions, including surface tension and viscosity. It was found that t-butanol reduced both properties-by 4% for surface tension and by a surprising 30% for viscosity. These reductions in the solution physical properties were correlated to enhancement in the mass transfer coefficient, k_L. The hydrodynamic behaviour of the system used in this work was characterised by a homogeneous bubbling regime. It was also found that the gas holdup was significantly enhanced by the addition of t-butanol. An equation to predict the gas holdup from the gas flow rate and t-butanol concentration was proposed to describe the experimental data. Moreover, the addition of t-butanol was found to significantly reduce the size of gas bubbles, leading to enhancement in the volumetric mass transfer coefficient, k_La. Bubble mean diameter was predicted using an equation developed by the Radial Basis Function Neural Network architecture obtained from the literature, and the mass transfer coefficient, k_L, was predicted using an equation based on the surface coverage ratio model. The ratio was found not to depend either on t-butanol concentration or on gas flow rate. A significant increase in the volumetric mass transfer coefficient, k_La, due to an increase in both k_L and a, was obtained following the addition of t-butanol, even at low concentrations.     

Controlled chain branching free radical polymerization manipulate with trithiocarbonates

Soluble, branched (methyl) methacrylate copolymers have been prepared via facile, one‐step, batch solution free radical polymerizations taken to high conversion. Methyl methacrylate (MMA) or methacrylate has been copolymerized with the branching comonomer (BCM) using a trithiocarbonate (TTC) to inhibit gelation. The BCMs employed were tripropylene glycol diacrylate (TPGDA) and trihydroxymethylpropyl triacrylate (TMPTA). Soluble branched copolymers containing unreacted double bonds have been produced and characterized by ¹H‐NMR spectroscopy. These two brancher monomers have been shown to produce regularly branched material with the small molar mass distributions in the presence of TTC. The results of DSC and Mark–Houwink constant α analyses support the production of the branched architectures. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Free radical desorption in continuous emulsion polymerization

A mathematical model for continuous emulsion polymerization which accounts for the desorption of radicals from polymer particles is presented. The desorption factor has been incorporated into the Sato-Taniyama model and the resulting systems of equations solved iteratively. The effects of desorption on variables such as concentration of particles, polymerization rate, and average number of radicals per particle are illustrated. Fit of the model to experimental data is presented and discussed.     

Non-ideal kinetics in vinyl polymerization primary radical termination and chain transfer to solvent in benzoyl peroxide initiated polymerization of vinyl acetate in benzene

The kinetics of vinyl acetate polymerization initiated by benzoyl peroxide in benzene at 60°C have been studied. Deviation of the rate of polymerization from kinetic orders of 0.5 in initiator and 1.0 in monomer is discussed in terms of primary radical termination and chain transfer to solvent.     

Free radical oxidative copolymerization of indene with vinyl acetate and isopropenyl acetate: Synthesis and characterization

Copolyperoxides of different compositions of indene with vinyl acetate and isopropenyl acetate were synthesized by the free radical‐initiated oxidative copolymerization. The compositions of copolyperoxides obtained from ¹H‐ and ¹³C‐NMR spectra have been used to determine the reactivity ratio of the monomers. The reactivity ratios reveal that the copolyperoxides contain a larger proportion of the indene units in random placement. The NMR studies further suggest irregularities in the copolyperoxide chain possibly due to the cleavage reactions of the propagating peroxide radical. The thermal analysis by differential scanning calorimetry (DSC) supports the alternating peroxide units in the copolymer chain. The activation energy for the thermal degradation suggests that the degradation is dependent on the dissociation of the peroxide (? O? O? ) bonds in the copolyperoxide chain. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86:639–646, 2002     

Molecular weight distribution in continuous stirred tank vinyl acetate emulsion polymerization

Emulsion polymerization typically produces polymers of high molecular weight with broad distributions of molecular size. Many models have been proposed that use either a Flory type distribution, resulting in a polydispersity of two, or a distribution function to represent the breadth of the distribution. In this work, a model for the distribution of molecular weights is derived as a approximation from a detailed molecular weight model that was previously developed. The model is found to approximate the distribution of molecular weights well for several emulsifier concentrations is continuous stirred tank emulsion polymerization of vinyl acetate. An analysis is also conducted of the transformation of gel permeation chromatography data to weight and number fractional distributions of the molecular sizes.     

Controlled radical polymerization of vinyl acetate in supercritical CO2 catalyzed by CuBr/terpyridine

Poly(vinyl acetate) (PVAc) was synthesized by the atom transfer radical polymerization of vinyl acetate (VAc) in supercritical carbon dioxide using CuBr/2,2′:6′,2″-terpyridine complex as a catalyst and ethyl 2-bromoisobutyrate as an initiator. Polymerization proceeded in a controlled manner, and low to moderate conversion was achieved within a reasonable time. The effects of the monomer amount, temperature, pressure, initiator, and ligand loading on monomer conversion, molecular weight and molecular weight distribution of the polymer were examined. The reaction kinetics was also investigated. The polymerization reaction was found to be first-order with respect to the monomer concentration. The molecular weights of the resulting PVAc increased linearly with increasing VAc conversion.     

Reversible addition-fragmentation chain transfer polymerization of vinyl acetate and vinyl pivalate in supercritical carbon dioxide

Two highly supercritical CO₂-soluble, poly(vinyl acetate) (PVAc)-based macro-reversible addition-fragmentation chain transfer (RAFT) agents were synthesized. The RAFT agents were used for the first time in RAFT/macromolecular design via the interchange of xanthates (MADIX) and polymerization of vinyl acetate (VAc) and vinyl pivalate (VPi) in supercritical carbon dioxide (scCO₂). A homopolymer PVAc and a block copolymer PVAc-b-PVPi made by RAFT/MADIX polymerization were characterized, and the effects of time and RAFT agents on polymerization were examined. For the 8.4 wt% RAFT agent in VAc, the molecular mass (M _n ) of homopolymer PVAc was 26,000 g mol^?1 and PDI was 1.35. For the copolymerization of VPi using 9.8 wt% PVAc-RAFT agent in VPi for 24 h, the M _n and PDI of PVAc-b-PVPi reached 32,400 g mol^?1 and 1.42, respectively. These results suggest that the polydispersity can be controlled during the clean production of PVAc and PVPi by RAFT/MADIX polymerization in scCO₂.     

Controlled radical copolymerization of vinyl acetate and dibutyl maleate by iodine transfer radical polymerization

Iodine transfer radical homo‐ and copolymerization of vinyl acetate (VAc) with dibutyl maleate (DBM) were carried out in the presence of ethyl iodoacetate (EtIAc) and 2,2′‐azobis(isobutyronitrile) (AIBN) as chain transfer agent and initiator, respectively, at 60 °C. Molecular weight and its distribution and (co)polymer structure (i.e. copolymer composition and chain end groups) were analysed using gel permeation chromatography and ¹H NMR spectroscopy, respectively. Homo‐ and copolymerization reactions proceed via a controlled characteristic with predetermined molecular weight and relatively narrow molecular weight distribution. The presence of DBM in the reaction mixture decreases the consumption rate of EtIAc as well as the polymerization rate. This is attributed to the effect of DBM on the transfer constant to the EtIAc and probably on the iodine exchange rate constant between the growing chains. The effect of the concentration of AIBN, EtIAc and overall monomers on the conversion, molecular weight and its distribution was studied. Simultaneously high conversion and molecular weight with a relatively narrow molecular weight distribution can be achieved only when equimolar and intermediate concentration of EtIAc and AIBN is used in the reaction mixture. End‐group analysis by ¹H NMR reveals that iodinated VAc end groups in the (co)polymer chains are unstable, resulting in aldehyde end groups. Thermogravimetric analysis shows that the thermal stability of the VAc‐based polymer increases on incorporating DBM units into the copolymer chains. © 2013 Society of Chemical Industry     

Atom transfer radical polymerization and copolymerization of vinyl acetate catalyzed by copper halide/terpyridine

Copper‐mediated atom transfer radical polymerization (ATRP) is versatile for living polymerizations of a wide range of monomers, but ATRP of vinyl acetate (VAc) remains challenging due to the low homolytic cleavage activity of the carbon‐halide bond of the dormant poly(vinyl acetate) (PVAc) chains and the high reactivity of growing PVAc radicals. Therefore, all the reported highly active copper‐based catalysts are inactive in ATRP of VAc. Herein, we report the first copper‐catalyst mediated ATRP of VAc using CuBr/2,2′:6′,2″‐terpyridine (tPy) or CuCl/tPy as catalysts. The polymerization was a first order reaction with respect to the monomer concentration. The molecular weights of the resulting PVAc linearly increased with the VAc conversion. The living character was further proven by self‐chain extension of PVAc. Using polystyrene (PS) as a macroinitiator, a well‐defined diblock copolymer PS‐b‐PVAc was prepared. Hydrolysis of the PS‐b‐PVAc produced a PS‐b‐poly(vinyl alcohol) amphiphilic diblock copolymer. © 2009 American Institute of Chemical Engineers AIChE J, 2009     

Probing the reaction kinetics of vinyl acetate free radical polymerization via living free radical polymerization (MADIX)

Living free radical polymerization technology (macromolecular design via the interchange of xanthates (MADIX)) was applied to give accesses to chain length and conversion dependent termination rate coefficients of vinyl acetate (VAc) at 80 °C using the MADIX agent 2-ethoxythiocarbonylsulfanyl-propionic acid methyl ester (EPAME). The kinetic data were verified and probed by simulations using the PREDICI^® modelling package. The reversible addition-fragmentation transfer (RAFT) chain length dependent termination (CLD-T) methodology can be applied using a monomer reaction order of unity, since VAc displays significantly lower monomer reaction orders than those observed in acrylate systems (ω(VAc, 80 °C)=1.17±0.05). The observed monomer reaction order for VAc is assigned to chain length dependent termination and a low presence of transfer reactions. The α value for the chain length regime of log(i)=1.25−3.25 (in the often employed expression ) reads 0.09±0.05 at low monomer to polymer conversion (10%) and increases significantly towards larger conversions (α=0.55±0.05 at 80%). Concomitantly with a lesser amount of midchain radicals, the chain length dependence of k_t is significantly less pronounced in the VAc system than in the corresponding acrylate systems under identical reaction conditions. The RAFT(MADIX)-CLD-T technique also allows for mapping of k_t as a function of conversion at constant chain lengths. Similar to observations made earlier with methyl acrylate, the decrease of k_t with conversion is more pronounced at increased chain lengths, with a strong decrease in k_t exceeding two logarithmic units from 10 to 80% conversion at chain lengths exceeding 1800.     

Loop polymerization of vinyl acetate

The emulsion polymerization of vinyl acetate was studied using a loop reactor. The results were compared with some earlier work done in a batch reactor. A parallel was drawn with the results obtained with a tubular loop reactor and with a continuous reactor using styrene as monomer. The same phenomena of the optimum conversion peak with styrene at the laminar turbulent flow transition zone also occurred for the vinyl acetate. The peak obtained in this case was, however, broader and in the lower turbulent zone. The effect of the surfactant concentration on the broadness of the peak is discussed.     

Copolymerization of ethylene with vinyl acetate. I. Effect of polymerization temperature on degree of branching

The degree of branching of a series of ethylene–vinyl acetate copolymers was found to be strongly dependent upon polymerization temperature. The copolymers were prepared by free-radical polymerization and had low molecular weights and molar ratios of ethylene: vinyl acetate greater than 3:1. Nuclear magnetic resonance and infrared studies showed that copolymers prepared at 150°C were highly branched and had little crystallinity. Branches were mainly alkyl groups on the polymethylene backbone segments. There was no evidence of δ-acetoxyalkyl branches. Long branches originating by intermolecular H abstraction from the acetylmethyl groups were also expected but could not be detected. These results were consistent with an intramolecular “backbiting” mechanism similar to that found in ethylene homopolymerizations. There was little or no participation by the vinyl acetate moiety in the branching scheme. Copolymers prepared at about 90°C had very few long or short branches and were more crystalline. Copolymers prepared between these temperatures had intermediate degrees of branching and crystallinity.     

Controlled synthesis of poly(vinyl acetate) by traditional radical emulsion polymerization

A new redox initiation system, potassium persulfate/N,N‐dimethylethanolamine, was used to initiate traditional radical emulsion polymerization of vinyl acetate at low temperature. Polymers were characterized using gel permeation chromatography, scanning electron microscopy and dynamic light scattering. The results showed that poly(vinyl acetate) with high molar mass and small dispersity (?) was successfully synthesized. © 2016 Society of Chemical Industry     

On semicontinuous polymerization of vinyl acetate

A semicontinuous emulsion process was used to polymerize vinyl acetate. The parameters studied were the rate of addition of the various ingredients. The polymerization evolution was followed as samples were taken at regular intervals. These emulsion samples were analyzed for monomer conversion, rate of polymerization as well as for the size and the size distribution of the particles. The molecular weight and molecular weight distribution were obtained by gel permeation chromatography (GPC). Our study showed that the total surface of the particles is an important factor, that the reaction mechanism follows Krackeler's and Wessling's theory, and that the Smith-Ewart ideal case does not apply here.     

Kinetics of vinyl chloride and vinyl acetate emulsion polymerization

The kinetics of vinyl chloride and vinyl acetate emulsion polymerization are reexamined. The validity of Ugelstad's model for systems with high desorption rate is confirmed by simulating conversion histories for both systems at different initiator concentrations and particle numbers. On the basis of the model, it is shown that at ordinary initiation rates, termination reactions are unimportant with respect to molecular weight development in both systems, and as a consequence, molecular weight development is independent of number and size distribution of polymer particles and of initiator and emulsifier level. Based on this conclusion, it is shown that in accordance with experimental facts, the molecular weight distribution obtained in vinyl chloride emulsion polymerization is the most probable distribution, and it is concluded that the number of long-chain branch points per repetition unit is less than 2 × 10^?4 at high conversions. In vinyl acetate emulsion polymerization, an almost logarithmic normal distribution is obtained. The distribution is strongly broadened by branching reactions with the number of long-chain branch points increasing rapidly with monomer conversion. The increase of M_n with increasing conversion is due to terminal double-bond polymerization, while the increase in M_w is due mainly to transfer to polymer.     

The effect of radical desorption on the particle size distribution in vinyl acetate emulsion polymerization

The effect of free radical desorption is studied by using a mathematical model of particle size distribution in continuous emulsion polymerization. By comparing the theoretical prediction with experimental data, the value of D_o for the vinyl acetate (VAc) system is best chosen as 0.19 × 10^?7 cm²/h. The effect of radical desorption as well as mean residence time on the absolute particle size distribution, total concentration of polymer particles, conversion, and average number of radicals per polymer particle are analyzed by the model proposed.