Emulsion polymerization of vinyl

Wheieas the BPO—DMA ledox system works well for curing of unsaturated polyester blends, it is not a very effective system for initiating vinyl monomer polymerizations, and therefore it generally is not used in such appHcations (34). However, combinations of amines (eg, DMA) and acyl sulfonyl peroxides (eg, ACSP) are very effective initiator systems at 0°C for high conversion suspension polymerizations of vinyl chloride (35). BPO has also been used in combination with ferrous ammonium sulfate to initiate emulsion polymerizations of vinyl monomers via a redox reaction (36). 

Many different combinations of surfactant and protective coUoid are used in emulsion polymerizations of vinyl acetate as stabilizers. The properties of the emulsion and the polymeric film depend to a large extent on the identity and quantity of the stabilizers. The choice of stabilizer affects the mean and distribution of particle size which affects the rheology and film formation. The stabilizer system also impacts the stabiUty of the emulsion to mechanical shear, temperature change, and compounding. Characteristics of the coalesced resin affected by the stabilizer include tack, smoothness, opacity, water resistance, and film strength (41,42). 

Mechanisms. Because of its considerable industrial importance as well as its intrinsic interest, emulsion polymerization of vinyl acetate in the presence of surfactants has been extensively studied (75—77). The Smith-Ewart theory, which describes emulsion polymerization of monomers such as styrene, does not apply to vinyl acetate. Reasons for this are the substantial water solubiUty of vinyl acetate monomer, and the different reactivities of the vinyl acetate and styrene radicals the chain transfer to monomer is much higher for vinyl acetate. The kinetics of the polymerization of vinyl acetate has been studied and mechanisms have been proposed (78—82). 

Emulsion polymerizations of vinyl acetate in the presence of ethylene oxide- or propylene oxide-based surfactants and protective coUoids also are characterized by the formation of graft copolymers of vinyl acetate on these materials. This was also observed in mixed systems of hydroxyethyl cellulose and nonylphenol ethoxylates. The oxyethylene chain groups supply the specific site of transfer (111). The concentration of insoluble (grafted) polymer decreases with increase in surfactant ratio, and (max) is observed at an ethoxylation degree of 8 (112). 

The kinetics of vinyl acetate emulsion polymeriza tion in the presence of alkyl phenyl ethoxylate surfactants of various chain lengths indicate that part of the emulsion polymerization occurs in the aqueous phase and part in the particles (115). A study of the emulsion polymerization of vinyl acetate in the presence of sodium lauryl sulfate reveals that a water-soluble poly(vinyl acetate)—sodium dodecyl sulfate polyelectrolyte complex forms, and that latex stabihty, polymer hydrolysis, and molecular weight are controlled by this phenomenon (116). 

MAIs may also be formed free radically when all azo sites are identical and have, therefore, the same reactivity. In this case the reaction with monomer A will be interrupted prior to the complete decomposition of all azo groups. So, Dicke and Heitz [49] partially decomposed poly(azoester)s in the presence of acrylamide. The reaction time was adjusted to a 37% decomposition of the azo groups. Surface active MAIs (M, > 10 ) consisting of hydrophobic poly(azoester) and hydrophilic poly(acrylamide) blocks were obtained (see Scheme 22) These were used for emulsion polymerization of vinyl acetate—in the polymerization they act simultaneously as emulsifiers (surface activity) and initiators (azo groups). Thus, a ternary block copolymer was synthesized fairly elegantly. 

In the emulsion polymerization of vinyl chloride (VC) initiated with type II MAI composed of PDMS, block efficiency was as high as 95-97%, and solid particles with a narrow range of particle size, 0.1-50 microns, were obtained in high yield [15]. 

The performance of secondary alkanesulfonates in applications as emulsifiers in the widespread emulsion polymerization of vinyl monomers can be assessed by their hydrophilic-lipophilic balance (HLB) numbers. The HLB numbers can... 

Capek, L Kinetics of the Free-Radical Emulsion Polymerization of Vinyl Chloride. Vol. 120, pp. 135-206. 

Litt, M.H. Chang, K.H.S. Symp. on Emulsion Polymerization of Vinyl Acetate, Lehigh University, 1980. 

El-Aasser, M.S. Vanderhofif J.W., 9%, Emulsion Polymerization of Vinyl Acetate, Applied Science Publishers, London. 

Donescu, D., Ciupitoiu, A., Gosa, K. Languri, L, 1993, Water Polymer Interaction During Emulsion Polymerization of Vinyl Acetate, Revue Roumcane de Chimie, 38(12), 1441-1448. 

Fig. 4-4 Plot of percent conversion versus time for emulsion polymerization of vinyl chloride at 50°C for monomer/water ratio of 26/74 and 0.883% surfactant. The initiator concentrations are 0.0012% (plot 1), 0.0057% (plot 2), and 0.023% (plot 3). After Vidotto et al. [1970] (by permission of Huthig and Wepf Verlag, Basel, and Wiley-VCH, Weinheim).

The final product of emulsion polymerization is an emulsion —a stable, heterogeneous mixture of fine polymer beads in an aqueous solution, sometime called a latex emulsion. Water-based paints, for example, can be formed from the emulsion polymerization of vinyl acetate. In this process, I m of water containing 3% poly(vinyl alcohol) and 1% surfactant are heated to 60°C in a reaction vessel (see Figure 3.27) The temperature rises to around 80°C over a 4 to 5 hour period as monomer and an aqueous persulfate solution are added. The rate at which heat can be removed limits the rate at which monomer can be added. 

Gamma radiation-induced mass and emulsion polymerization of vinyl monomers has been studied by the American, Metz, and the German, Hummel. 

Many different combinations of surfactant and protective colloid are used in emulsion polymerizations of vinyl acetate as stabilizers. 

The emulsion polymerization of vinyl hexanoate has been studied to determine the effect of chain transfer on the polymerization kinetics of a water-insoluble monomer. Both unseeded and seeded runs were made. For unseeded polymerizations, the dependence of particle concentration on soap is much higher than Smith-Ewart predictions, indicating multiple particle formation per radical because of chain transfer. Once the particles have formed, the kinetics are much like those of styrene. The lower water solubility of vinyl hexanoate when compared with styrene apparently negates its increased chain transfer, since the monomer radicals cannot diffuse out of the particles. 

An interesting variation on the use of azo groups-containing polymers is the use of polyacrylamide prepolymers as both initiator and emulsifying agent for the emulsion polymerization of vinyl acetate. The observed reaction kinetics were typical (see Fig. 4.7) for an emulsion polymerization and, in particular, the slope (a = 1) of the plot of lg Rp vs lg CPrep confirms the double function of these prepolymers very clearly. 

Thus these characterization results demonstrate that polymethacrylic acid does not function in the same manner as polyvinyl alcohol in the emulsion polymerization of vinyl acetate and that the adsorbed polymethacrylic acid can be separated from the bulk polymer, thus distinguishing it from grafted polymer. 

The objective of this study was to investigate the feasibility of using a tubular reactor for the seeded emulsion polymerization of vinyl acetate, and to study the effect of process variables on conversion rate and latex properties. 

This study of the continuous, tubular, seeded emulsion polymerization of vinyl acetate has led to the following conclusions ... 

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