Semicontinuous seeded emulsion copolymerization of vinyl acetate and methyl acrylate

The semicontinuous seeded emulsion copolymerization of vinyl acetate and methyl acrylate was investigated. The effect of type of process (starved process versus semi-starved process), type of feed (neat monomer addition versus monomer emulsion addition), amount of seed initially charged in the reactor, and feed rate on the time evolution of the overall conversion, copolymer composition, and polymer particle size was analyzed. It was found that, in the case of the starved process, both monomers, but mainly vinyl acetate, accumulated in the reactor. The preferential accumulation of vinyle acetate resulted in a drift of the copolymer composition. Both monomers accumulation and copolymer composition drift were reduced by increasing the amount of seed initially charged in the reactor and by decreasing the feed rate. For the semi-starved process, it was found that a vinyl aceatate rich copolymer was formed when a low methyl acrylate feed was used, whereas a methyl acrylate rich copolymer was obtained at high methyl acrylate feed rates. For both starved process and semi-starved process, the total number of polymer particles, after an initial increase, reached a plateau value which was the same in all of the experiments carried out. These results were analyzed by means of a mathematical model developed for this system.     

Kinetics of vinyl acetate emulsion polymerization

The emulsion polymerization of vinyl acetate has generally been considered a special type of reaction that is not covered by the Smith-Ewart theory. Although the number of particles depends on coalescence rates and can not be predicted by this theory, the polymerization rate data are consistent with the general concepts of Smith and Ewart, including reaction primarily inside swollen polymer particles, escape of radicals from particles, and termination of chains inside the particles. Allowing for rapid exchange of radicals following chain transfer leads to a simple equation which fits much of the published data for cases of both very low and very high values of n , the average number of radicals per particle.      

Synthesis of high oil‐absorption resins of poly(methyl methacrylate‐butyl methacrylate) by suspended emulsion polymerization

The synthesis of high oil‐absorption resins by suspended emulsion polymerization process for the first time with butyl methacrylate (BMA) and short‐chain methyl methacrylate (MMA) as the monomers was studied. And the effects of different polymerization technological parameters, such as the comonomer, initiator, crosslinker, emulsifier, dispersant agent, and the agitation rate, on the oil absorbency of high oil‐absorption resins were discussed in detail. The optimum polymerization conditions were obtained. With the increasing contents of these factors, the oil absorbency increased first, and then decreased. The highest oil absorbency to toluene was 17.6 g/g. The particle morphology of the high oil‐absorption resins was observed by scanning electron microscopy (SEM). The resins were determined by FTIR spectrometry. Compared with the high oil‐absorption resins prepared by suspension polymerization process and emulsion polymerization process, the high oil‐absorption resins prepared by suspended emulsion polymerization process had the higher oil absorbency, faster oil‐adsorbing rate, better oil‐retention, and regeneration property. Copyright © 2010 John Wiley & Sons, Ltd.     

New poly(phenylenevinylene)‐methyl methacrylate‐based photonic crystals

Monodisperse colloids have been prepared efficiently by copolymerization of methyl methacrylate and fluorescent first‐ and second‐generation poly(phenylenevinylene) dendrons under surfactant‐free emulsion polymerization conditions. The copolymers were characterized by UV–vis and fluorescence spectroscopy and size exclusion chromatography. Transmission electron microscopy revealed that the copolymers were microspheres with smooth surfaces and narrow dispersity. The bead diameter could be varied by changing the monomer/water ratio. The materials could be crystallized to give polymer opal photonic crystals. The emission was not affected by the periodic structure because of the large spectral distance between the emission and the pseudogap position. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 2659–2665, 2010     

Kinetic analysis of seeded emulsion polymerization of vinyl acetate

Particle number and size data from a series of seeded, emulsifier-free, vinyl acetate emulsion polymerization experiments have been analyzed with the aid of polymerization and particle growth models. A secondary population of particles, with a significantly greater number concentration than the seed, was nucleated in all experiments. The two populations (seed and new) had rather narrow size distributions and large diameters. Hence the reactions were in the area normally associated with Smith–Ewart Case III kinetics. Water-phase termination reactions can be important in this reaction region but radical desorption from such large particles does not significantly influence the kinetics. The results of the analysis were used to evaluate the magnitude of water-phase termination; to estimate radical capture coefficients; and to evaluate competitive particle growth.     

Mechanical characterization of vinyl acetate based emulsion polymer blends

Emulsion blends comprise an important commercial area of polymer blend utility. Surprisingly, the fundamental study of emulsion blends is rarely noted in the literature. This study investigates emulsion blends of poly(vinyl acetate) (PVAc) and vinyl acetate‐ethylene copolymers (VAE), where both components employ poly(vinyl alcohol) (PVOH) as the protective colloid. PVOH comprises the continuous phase in the emulsion cast films for both the individual components and the blends. This provides an example whereby excellent adhesion can be expected between the particles comprising the blend. The combination of low T_g/high T_g emulsion blends has been noted to be of interest, and the PVAc/VAE emulsion blends noted here offer an excellent model to study. The PVAc/VAE blends protected with PVOH exhibit poor mechanical compatibility even though there is good adhesion. Conventional theory based on polymer/filler combinations predicts a rapid loss in elongation as filler content increases if excellent adhesion is observed. The PVAc/VAE blends (where PVAc is the filler) also exhibit similar behavior. This result implies excellent adhesion may not be desired where a compliance mismatch occurs for emulsion blends. The polymer/filler theories do not properly predict PVAc/VAE blend tensile strength results. A newer approach termed the equivalent box model (EBM) employing percolation theory agrees well with experimental results. Melt mixing of the low/high compliance PVAc/VAE emulsion blends yields a significant improvement in mechanical compatibility. This indicates that a heterogeneous mixture of the same components yields better mechanical results than an array of particles with excellent adhesion between the particles.     

Toughening effect of ethylene‐vinyl acetate rubber on nylon 1010 compatibilized by maleated ethylene‐vinyl acetate copolymers

The toughening effect of ethylene‐vinyl acetate rubbers (EVM) with maleated ethylene‐vinyl acetate copolymers (EVA‐g‐MAH) on the nylon 1010 was investigated. The addition of 5 phr (per hundred nylon 1010) EVM increased the elongation at break of nylon 1010 to a great extent. The notched Izod impact strength of nylon/EVM blends increased with increasing EVM content. Scanning electron microscope showed that the EVM particle size was around 0.5 μm when the EVM content was 5 phr and increased with increasing EVM content. After the addition of EVA‐g‐MAH to nylon/EVM (100/20) blend, the average diameter of EVM particles decreased from more than 1 μm to 0.5–0.6 μm. EVA‐g‐MAH could improve the adhesion between nylon 1010 and EVM. A sharp brittle‐ductile transition (BDT) was observed when the interparticle distance was about 0.2 μm, independent of the addition of EVA‐g‐MAH. The notched Izod impact strength of nylon/EVM blends at low temperatures was measured and the BDT shifted toward low temperatures with increasing EVM or EVA‐g‐MAH content. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 434–444, 2009     

Development of an advanced on‐line position‐specific stable carbon isotope system and application to methyl tert‐butyl ether

We present an advanced system for on‐line position‐specific carbon isotope analysis. The main limitation of on‐line intramolecular isotope ratio measurements has been that optimal pyrolytic fragments are obtained mostly at temperatures where the analyte has not completely reacted. As a result of undetermined isotopic fractionation, the isotopic signatures of the pyrolysis products are not strictly equal to these of the equivalent moieties in the parent molecule. We designed a pyrolytic unit in which both temperature and reaction time are variable parameters, enabling determination of the enrichment factor of the pyrolysis at optimal temperature by construction of a Rayleigh plot. In the case of methyl tert‐butyl ether (MTBE) presented here, a ‘pre‐pyrolysis’ fractionation of MTBE leading to a depletion of 0.9‰ was discovered and the enrichment factor of the optimal pyrolysis reaction was determined at −1.7‰. Absolute δ¹³C values of two functional groups of MTBE – the methoxy group and the 2‐methylpropane group – could be determined with 95% confidence intervals of 0.4‰ and 0.5‰, respectively. Copyright © 2009 John Wiley & Sons, Ltd.     

Additive manufacturing of fire‐retardant ethylene‐vinyl acetate

Thermocompression (with also extrusion and injection molding) is a classical polymer shaping manufacturing, but it does not easily allow designing sophisticated shapes without using a complex mold, on the contrary to 3D printing (or polymer additive manufacturing), which is a very flexible technique. Among all 3D printing techniques, fused deposition modeling is of high potential for product manufacturing, with the capability to compete with conventional polymer processing techniques. This is a quite low cost 3D printing technique, but the range of filaments commercially available is limited. However, in some specific 3D printing processes, no filaments are necessary. Polymers pellets feed directly the printing nozzle allowing to investigate many polymeric matrices with no commercial limitation. This is of high interest for the design of flame‐retarded materials, but literature is scarce in that field. In this paper, a comparison between thermocompression and 3D printing processes was performed on both neat ethylene‐vinyl acetate (EVA) copolymer and EVA flame retarded with aluminum triHydroxyde (ATH) containing different loadings (30 or 65 wt%) and with expandable graphite (EG), ie, EVA/ATH (30 wt%), EVA/ATH (65 wt%), and EVA/EG (10 wt%), respectively. Morphological comparisons, using microscopic and electronic microprobe analyses, revealed that 3D printed plates have lower apparent density and higher porosity than thermocompressed plate. The fire‐retardant properties of thermocompressed and 3D printed plates were then evaluated using mass loss calorimeter test at 50 kW/m². Results highlight that 3D printing can be used to produce flame‐retardant systems. This work is a pioneer study exploring the feasibility of using polymer additive manufacturing technology for designing efficient flame‐retarded materials.     

Synthesis of statistical glycidyl methacrylate‐n‐vinyl pyrrolidone copolymers and their reaction with naproxen

Free‐radical copolymerization of glycidyl methacrylate (GMA) with N‐vinylpyrrolidone (VPD) was carried out at 50 °C using 3.0 mol · L^?1 of N,N′‐dimethylformamide solution and 9.0 · 10^?3 mol · L^?1 of 2,2′‐azobisisobutyronitrile as an initiator. The modification reaction of GMA‐VPD copolymers with a model bioactive carboxylic acid, 6‐methoxy‐α‐methyl‐2‐naphthaleneacetic acid (naproxen), was studied in the homogeneous phase using basic catalysts. The influence of the type of catalyst and the GMA content was evaluated. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 1192–1199, 2002     

Interaction of water in polymers: Poly(ethylene‐co‐vinyl acetate) and poly(vinyl acetate)

We studied the interaction of water in poly(ethylene‐co‐vinyl acetate) of various vinyl acetate compositions and poly(vinyl acetate), on the basis of the infrared spectrum of the water dissolved therein. The spectrum shows a very sharp and distinct band at about 3690 cm^?1 (named as A), and less‐sharp two bands around 3640 (B) and 3550 cm^?1 (C), the A band being outstanding especially at a low vinyl acetate composition. As the vinyl acetate composition increases, the A band decreases in intensity relative to the C band, whereas the B band increases contrarily. Analysis of the spectral change has elucidated that one‐bonded water (of which one OH is hydrogen‐bonded to the C?O of an ester group and the other OH is free) and two‐bonded water (each OH of which is hydrogen‐bonded to one C?O) coexist in the copolymer and that two‐bonded water increases in relative population with increasing vinyl acetate composition. Dissolved water is entirely two‐bonded in poly(vinyl acetate), in which C?O groups are densely distributed in the matrix. We proved that dissolved water in polymers is hydrogen‐bonded through one or two OH groups to the possessed functional groups but does not cluster. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 777–785, 2005     

Mode of termination in the copolymerization of vinyl acetate–isobutyl methacrylate and methyl methacrylate–methyl acrylate at 60°C

The mode of termination in the vinyl acetate–isobutyl methacrylate (VA–IBMA) and methyl methacrylate–methyl acrylate (MMA–MA) copolymerization systems has been investigated at 60°C. by using the dye-interaction technique for functional endgroup estimation. The results show that pairs of poly(vinyl acetate) radicals interact almost exclusively through a disproportionation mechanism. In the homopolymerization of methyl methacrylate and methyl acrylate, about 1.16 and 1.22 carboxyl-containing endgroups per polymer molecule have been estimated, which shows the predominance of disproportionation over combination in these termination reactions. In poly(isobutyl methacrylate) about 1.55 tagged initiator fragments per chain indicate that 29% of the total radicals terminate through the disproportionation mechanism. Cross termination in the (VA–IBMA) copolymerization system occurs almost entirely through combination for monomer feeds richer in isobutyl methacrylate content while for the MMA–MA system, combination is more important at intermediate monomer feed ratios. These results have been discussed in the light of different explanations for the reaction mechanism.     

High solids content emulsion terpolymerization of vinyl acetate,methyl methacrylate,and butyl acrylate. I. Kinetics

The kinetics of the high solids content emulsion terpolymerization of vinyl acetate, methyl methacrylate, and butyl acrylate were investigated. The effect of feed flow rate, total amount of emulsifier, distribution of emulsifier between the initial charge and the feed, concentration of initiator, and solids content on the time evolution of the conversion, terpolymer composition, and total number of polymer particles were investigated. The experimental results were analyzed by means of a mathematical model that incorporated the main features of the system. © 1994 John Wiley & Sons, Inc.     

RAFT-mediated emulsion polymerization of vinyl acetate: a challenge towards producing high molecular weight poly(vinyl acetate)

The preparation of poly(vinyl acetate) with well-controlled structure has received a great deal of interest in recent years because of a large number of developments in living radical polymerization techniques. Among these techniques, the use of reversible addition–fragmentation chain transfer (RAFT)-mediated polymerization has been employed for the controlled polymerization of vinyl acetate due to the high susceptibility of this monomer towards chain transfer reactions. Here, a novel water-soluble N,N-dialkyl dithiocarbamate RAFT agent has been prepared and employed in the emulsion polymerization of vinyl acetate. The kinetic results reveal that the polymerization nucleation mechanism changes from homogeneous to micellar and RAFT-generated radicals can change the kinetic behavior from conventional emulsion polymerization to living radical polymerization. At higher concentrations of the modified RAFT agent, as a result of an aqueous phase reaction between RAFT and sulfate radicals, relatively more hydrophobic radicals are generated, which favors entry and propagation into micelles swollen with monomer. This observation was determined from the investigation of the polymerization rate and measurements of the average particle diameter and the number of particles per liter of the aqueous phase. Molecular weight analysis also demonstrated the participation of the RAFT agent in the polymerization in such a way as to restrict chain transfer reactions. This was determined by examining the evolution of polymer chain length and attaining higher molecular weights, even up to 50?% greater than the samples obtained from the conventional emulsion polymerization of vinyl acetate in the absence of the synthesized modified RAFT agent.     

Poly(acrylonitrile‐co‐methyl methacrylate‐co‐methyl acrylate): Synthesis and stereosequence distribution analysis by 2D NMR

Terpolymers of acrylonitrile (A), methyl methacrylate (B), and methyl acrylate (M) were synthesized under optimized atom transfer radical polymerization conditions using 2‐bromopropionitrile as an initiator and CuBr/dinonyl bipyridine as a catalyst. Variation of the feed composition led to terpolymers with different compositions. Composition of synthesized terpolymers were calculated from quantitative ¹³C{¹H} NMR spectra. Number average molecular weight and polydispersity index were determined by gel permeation chromatography. The overlapping and broad signals of the terpolymers were assigned completely to various compositional and configurational sequences by correlation of one‐dimensional ¹H, ¹³C{¹H}, and distortionless enhancement by polarization transfer and two‐dimensional heteronuclear single quantum coherence (HSQC) and total correlation spectroscopy (TOCSY). 2D HSQC NMR study shows one to one correlation between carbon and proton signals, while 2D TOCSY spectra were used to confirm 1, 2 bond geminal couplings between nonequivalent protons of same methylene group. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 25–37, 2009     

A high-field C-NMR study of the aqueous copolymerisation of acrylonitrile and vinyl acetate. Microstructural observations

A detailed examination has been undertaken of the high field ¹³C-NMR spectrum of various acrylonitrile/vinyl acetate copolymers prepared by radical initiation in a heterogeneous aqueous batch reaction (taken to low conversion). It has been possible to establish the triad, tetrad and pentad sequences for copolymers employing sequence patterns and peak fractions as an aid to peak assignments. These results indicate that the copolymer cotacticity is virtually independent of the comonomer feed ratio.