Polymerization radical dispersion

Presented in this paper is a specific example of a semi-batch, free radical, dispersion polymerization. In this example, SimuSolv is used to quantify a Icinetic model derived from free radical polymerization principles and then used to define a new finishing process to reduce residual monomer to an acceptable level. Finally, experimental results are compared with those predicted by the computer simulation. 

The peroxide-initiated, free radical, dispersion polymerization of the single monomer is assumed to progress according to the simultaneous reactions of initiator decomposition, initiation, propagation and termination with appropriate reaction orders described elsewhere.(2-6)... 

Electron-transfer initiation also occurs in heterogeneous polymerizations involving dispersions of an alkali metal in monomer. Initiation involves electron transfer from the metal to monomer followed by dimerization of the monomer radical-anion to form the propagating... 

We begin by describing the current understanding of the kinetics of polymerization of classical unsaturated monomers and macromonomers in the disperse systems. In particular, we note the importance of diffusion-controlled reactions of such monomers at high conversions, the nucleation mechanism of particle formation, and the kinetics and kinetic models for radical polymerization in disperse systems. 

The radical polymerization in disperse systems may be divided into several types according to the nature of continuous phase and the polymerization loci the dispersion, emulsion, miniemulsion, microemulsion, suspension, etc. 

Stabilization in Nonaqueous Radical Dispersion Polymerization with AB Block Copolymers of Polystyrene and Poly(dimethyl siloxane)... 

Various patents on the homopolymerization of BD in the presence of styrene are available [581-590]. According to these patents, St is used as a solvent in which BD is selectively polymerized by the application of NdV/DIBAH/EASC. At the end of the polymerization a solution of BR in St is obtained. In subsequent reaction steps the unreacted styrene monomer is either polymerized radically, or acrylonitrile is added prior to radical initiation. During the subsequent radical polymerization styrene or styrene/acrylonitrile, respectively, are polymerized and ris-l,4-BR is grafted and partially crosslinked. In this way BR modified (or impact modified) thermoplast blends are obtained. In these blends BR particles are dispersed either in poly(styrene) (yielding HIPS = high impact poly(styrene) or in styrene-acrylonitrile-copolymers (yielding ABS = acrylonitrile/butadiene/ styrene-terpolymers). In comparison with the classical bulk processes for HIPS and ABS, this new technology allows for considerable cost reductions... 

There are four main types of liquid-phase heterogeneous free-radical polymerization microemulsion polymerization, emulsion polymerization, miniemulsion polymerization and dispersion polymerization, all of which can produce nano- to micron-sized polymeric particles. Emulsion polymerization is sometimes called macroemulsion polymerization. In recent years, these heterophase polymerization reactions have become more and more important... 

A review article by Qiu et al. [212] and references herein [217-226] covers NMCRP in miniemulsions up to 2001. Cunningham wrote a related review in 2002, also covering controlled radical polymerization in dispersed phase systems [227]. Here, the main results reported in the Qiu review will be summarized, and new developments in the field since then will be reviewed. 

Living radical dispersion polymerization is a promising way to expand the design and scope of functional polymer colloids to a wider range of other monomers. The 2,2,6,6-tetramethyl-l-piperidinyloxy (TEMPO)-mediated living radical dispersion polymerization of styrene has been carried out in presence of PS-h-P(PP-aZt-E) in decane at 135 °C [95] or PVP in alcohol-water at 130 °C [96] in order to produce microspheres with a very broad size distribution, consisting of relatively low molecular weight polystyrene (M =10 ) with M /Mn=l.l. 

Barton J, Capek I (1994) Radical Polymerization in Disperse Systems, E. Horwood, Chichester and Veda, Bratislava... 

This paper focuses on heterophase free radical polymerizations. It is limited to processes where multiple phases, distinguished by the insolubility of reagents, exists at the onset of the reaction. It therefore does not consider precipitation polymerization [1], which occurs when the polymer is insoluble in the monomer and precipitates out from an initially homogeneous solution. It also does not address emulsifier-free polymerization or dispersion polymerization. This rather general nomenclature is now accepted as applying to specific systems where the heterophase nature is produced at the onset of the reaction by homogeneous nucleation of oligomers or polymer chains which have exceeded their solubility limit [2]. 

Vinyl acetate is polymerized in dispersion form using various initiators. Exanples of ionic initiators commonly used for free-radical emulsion polymerizations are ammonium, sodium or potassium persulfate. Topical nonionic hydrophobic initiators include 2,2 -azobis(isobutyronitrile) (AIBN) and benzoyl peroxide. Water-soluble nonionic initiators such as tertiary-butyl hydroperoxide are also employed. The initiator 4,4 -azobis(4-cyanovaleric acid) in its acid state is oil soluble, while neutralization causes it to become water soluble providing for further diversity in initiators. 

J. Barton and 1. Capek, Radical Polymerization in Disperse Systems. Ellis Horwood, Chichester, 1994 (Slovak edition VEDA, Bratislava. 1991)... 

Shim, S.E. Oh, S. Chang, Y.H. Jin, M.J. Choe, S. Solvent effect on TEMPO-mediated living free radical dispersion polymerization of styrene. Polymer 2004, 45 (14), 4731-4739. 

Barton, J. and I. Capek (1994). Radical Polymerization in Disperse Systems. New York, Elhs Horwood. 

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