Emulsifier free emulsion copolymerization

Thus in the emulsifier-free emulsion copolymerization the emulsifier (graft copolymer, etc.) is formed by copolymerization of hydrophobic with hydrophilic monomers in the aqueous phase. The ffee-emulsifier emulsion polymerization and copolymerization of hydrophilic (amphiphilic) macromonomer and hydro-phobic comonomer (such as styrene) proceeds by the homogeneous nucleation mechanism (see Scheme 1). Here the primary particles are formed by precipitation of oligomer radicals above a certain critical chain length. Such primary particles are colloidally unstable, undergoing coagulation with other primary polymer particles or, later, with premature polymer particles and polymerize very slowly. 

The emulsifier-free emulsion copolymerization of styrene and poly(meth-acrylic acid) (PMA) macromonomers... 

Emulsifier-Free Emulsion Copolymerization of Styrene with Acrylamide and Its Derivatives... 

Guillaume JL, Pichot C, Guillot J. Emulsifier-free emulsion copolymerization of styrene and butyl acrylate. II. Kinetic studies in the presence of ionogenic comonomers. J Polym Sci Part A Polym Chem 1988 26 1937-1959. 

Ganachaud F, Sauzedde F, Elaissari A, Pichot C. Emulsifier-free emulsion copolymerization of styrene with two different amino-containing cationic monomers I. Kinetic studies. J Appl Polym Sci 1997 65 2315-2330. 

The emulsion copolymerization of styrene and methacrylic acid in the presence of a new polymerizable macromonomer based on PEG as stabilizer is proposed by Hincel and Serpen [55] to obtain larger and more surface-carboxyl-charged monodisperse particles relative to those obtained by the same emulsifier-free emulsion copolymerization. 

PS/PHEM A particles in micron-size range were also obtained by applying the single-stage soapless emulsion copolymerization method [124]. But, this method provided copolymer particles with an anomalous shape with an uneven surface. PS or PHEMA particles prepared by emulsifier-free emulsion polymerization were also used as seed particles with the respective comonomer to achieve uniform PS/PHEMA or PHEMA/PS composite particles. PS/PHEMA and PHEMA/PS particles in the form of excellent spheres were successfully produced 1 iLitm in size in the same study. 

Poly(ethylene oxide) (PEO) macromonomers constitute a new class of surface active monomers which give, by emulsifier-free emulsion polymerization or copolymerization, stable polymer dispersions and comb-like materials with very interesting properties due to the exceptional properties of ethylene oxide (EO) side chains. They are a basis for a number of various applications which take advantage of the binding properties of PEO [39], its hydrophilic and amphipathic behavior [40], as well as its bio compatibility and non-absorbing character towards proteins [41]. Various types of PEO macromonomers have been proposed and among them the most popular are the acrylates and methacrylates [42]. 

Free-radical copolymerizations have been performed ia bulb (comonomers without solvent), solution (comonomers with solvent), suspension (comonomer droplets suspended ia water), and emulsion (comonomer emulsified ia water). On the other hand, most ionic and coordination copolymerizations have been carried out either ia bulb or solution, because water acts as a poison for many ionic and coordination catalysts. Similarly, few condensation copolymerizations iavolve emulsion or suspension processes. The foUowiag reactions exemplify the various copolymerization mechanisms. 

Different approaches are used to prepare polymer particles with attaching to surface-functionalized groups. In majority of the cases, they consist of step-batch or -semibatch polymerizations in dispersed media, being among them pulsion polymerization (emulsifier-free or not) the most used polymerization process (i) emulsion homopolymerization of a monomer containing the desired functional group (functionalized monomer), (ii) emulsion copolymerization of styrene (usually) with the functionalized monomer, (iii) seeded copolymerization to produce composite functionalized latexes, and (iv) surface modification of preformed latexes. 

Vinyl acetate is polymerized in aqueous emulsion and used widely in surface coating and in adhesives. Copolymerized with vinyl esters of branched carboxylic acids and small quantities of acrylic acid, it gives paint latices of excellent performance characteristics. G. C. Vegter found that a coagulum-free latex of very low residual monomer content can be produced from a mixture of an anionic and a nonionic emulsifier according to a specific operating procedure. The freeze/thaw stability of polymeric latices has been investigated by H. Naidus and R. Hanzes. 

Carboxylated polybutadiene ionomers, which are close relatives of the polyethylene ionomers described above, have an essentially polybutadiene backbone that contains some acrylonitrile and styrene to adjust its flexibility and toughness, and, in addition, up to 6% by weight of acrylic or methacrylic acid. Like the polyethylene ionomers, they are usually made by direct copolymerization with the carboxylic acid monomer using, however, emulsion methods. Typically the monomers are slurried in water with sodium dodecylbenzene sulfonate as the emulsifier and potassium persulfate as the free-radical initiator. The tendency of the carboxyhc add monomer to dissolve in the aqueous phase instead of remaining in the butadiene-rich phase is suppressed by making the aqueous phase acidic so that the monomer remains in the nonionized form. 

Our account of the aforesaid factors influencing the kinetics and mechanism of emulsion polymerization (in both presence and absence of an emulsifier) has enabled the inflnence of comonomers on the processes of formation of polymeric dispersions based on (meth)acrylates to be explained. Changes of some conditions of reaction have tnmed ont to affect the character of influence of other ones. For example, increasing the concentration of MAA at its copolymerization with MA at a relatively low initiation rate leads to a decrease in the rate and particle nnmber and to an increase in the coagnlnm amonnt. Bnt at high initiation rates, the nnmber of particles in the dispersion in the presence of MAA rises and their stability improves. The same effects were revealed for emnlsifier-free polymerization of bntylacrylate as well, when at high temperatnres its partial replacement by MAA results in better stabilization of the dispersion, an increase in the reaction rate and the nnmber of particles (whereas their decrease was observed in the presence of an emulsifier). 

Grafting a second polymer to the NR molecule in the latex stage is one of the many routes to chemically modified NR. An olefinic monomer with unsaturated double bonds such as methyl methacrylate (MMA), styrene and acrylonitrile are important monomers used for such grafting. " For example, MMA monomer is first converted into an emulsion with some suitable emulsifiers and then mixed with NR latex to copolymerize the monomer in a seeded emulsion polymerization process. It is important to ensure the seed latex particles are saturated with the monomer supplied through diffusion from the emulsified monomer droplets. An oil- or water-soluble initiator can be used to start the reaction. With proper control of the system and reaction conditions, the free radical reaction can be made to propagate within the latex particles as far as possible, so that only grafted NR occurs, without the formation of free homopolymer from the monomer. In this way only chemically modified NR... 

Apart from the fluoro monomers vinyl fluoride (VF), vinylidene fluoride (VF2), and tetrafluoroethylene (TFE), only chlorofluoroethylene has found commercial use as homopolymer. It is applied as thermoplastic resin based on its vapor-barrier properties, superior thermal stability (Tdec > 350 °C), and resistance to strong oxidizing agents [601]. Chlorofluoroethylene is homo- and copolymerized by free-radical-initiated polymerization in bulk [602], suspension, or aqueous emulsion using organic and water-soluble initiators [603,604] or ionizing radiation [605], and in solution [606]. For bulk polymerization, trichloroacetyl peroxide [607] and other fluorochloro peroxides [608,609] have been used as initiators. Redox initiator systems are described for the aqueous suspension polymerization [603,604]. The emulsion polymerization needs fluorocarbon and chlorofluorocarbon emulsifiers [610]. 

The aim of this review is to summarize and discuss the kinetic data of the emulsion polymerization and copolymeiization of vinyl chloride. The current understanding of the kinetics of free-radical polymerization of conventional monomer is briefly described and kinetic data of radical polymerization and copolymerization of vinyl chloride in the presence of hydrophobic and hydrophilic additives are summarized. Efiects of the initiator type and concentration, the reaction conditions and the type of diluent are evaluated. Variation of kinetic and molecular weight parameters in the heterogeneous polymerizations with emulsifier type and concentration are discussed. 

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