Vinyl acetate, dispersion polymerization

Transfer agents equivalent to macromonomer, i.e., thiol-ended polyoxyethylene, are also able to stabilize dispersion polymerization of styrene with a limited amount of material [113]. Recently, it has been shown that it was possible to stabilize vinyl acetate dispersion polymerization in supercritical CO2 using perfluoroalkyl polymerizable surfactant [114]. 

Ballantine (4) observed that the y-induced emulsion polymerization of styrene is about 100 times faster and yields higher molecular weights (up to 2 X 10 ) than the y-induced bulk polymerization. He explains the large difference in reaction rates by the high radical yield (G/ value) of water, as compared with the G/j value of styrene. An over-all activation energy of 3.7 kcal. per mole was calculated from the temperature dependence of the reaction. Allen et al. (1) prepared and grafted polystyrene and poly (vinyl acetate) dispersions under the influence of y-radiation. Mezhirova et al. (28) found a temperature-independent reaction rate of the y-induced emulsion polymerization of styrene. 

Suspension polymerization is designed to combine the advantages of both the bulk and solution polymerization techniques. It is one of the extensively employed techniques in the mass production of vinyl and related polymers. Suspension polymerization (also referred to as bead or pearl polymerization) is carried out by suspending the monomer as droplets by efficient agitation in a large mass (continuous phase) of nonsolvent, commonly referred to as the dispersion or. suspension medium. Water is invariably used as the suspension medium for all water insoluble monomers because of the many advantages that go with it. Styrene, methyl methacrylate, vinyl chloride, and vinyl acetate are polymerized by the suspension... 

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. 

Uses Emulsifier, surfactant in emulsion polymerization of vinyl chloride and vinyl acetate, suspension polymerization of vinyl chloride dispersant for resins, pigments, polymers, and dyes in org. systems pigment dispersant in printing inks mst preventive food-pi, adhesives, paper/paperboard emulsifier in mfg. of food-contact artides... 

Texapon K-12 PA 15 surfactant, polymerization PVC Colonial 1240 Slurry Colonial 1250 Slurry Colonial 1260 Slurry surfactant, polymerization SBR Colonial 1240 Slurry Colonial 1250 Slurry Colonial 1260 Slurry surfactant, polymerization vinyl acetate dispersions Disponii OSS 50 KE surfactant, polymerization vinyl acetate emulsions Igepal CO-970 Igepal CO-977 Igepal CO-997... 

Almost all synthetic binders are prepared by an emulsion polymerization process and are suppHed as latexes which consist of 48—52 wt % polymer dispersed in water (101). The largest-volume binder is styrene—butadiene copolymer [9003-55-8] (SBR) latex. Most SBRlatexes are carboxylated, ie, they contain copolymerized acidic monomers. Other latex binders are based on poly(vinyl acetate) [9003-20-7] and on polymers of acrylate esters. Poly(vinyl alcohol) is a water-soluble, synthetic biader which is prepared by the hydrolysis of poly(viayl acetate) (see Latex technology Vinyl polymers). 

Suspension Polymerization. At very low levels of stabilizer, eg, 0.1 wt %, the polymer does not form a creamy dispersion that stays indefinitely suspended in the aqueous phase but forms small beads that setde and may be easily separated by filtration (qv) (69). This suspension or pearl polymerization process has been used to prepare polymers for adhesive and coating appHcations and for conversion to poly(vinyl alcohol). Products in bead form are available from several commercial suppHers of PVAc resins. Suspension polymerizations are carried out with monomer-soluble initiators predominantly, with low levels of stabilizers. Suspension copolymerization processes for the production of vinyl acetate—ethylene bead products have been described and the properties of the copolymers determined (70). Continuous tubular polymerization of vinyl acetate in suspension (71,72) yields stable dispersions of beads with narrow particle size distributions at high yields. 

Suspension polymerization produces beads of plastic for styrene, methyl methacrviaie. viny l chloride, and vinyl acetate production. The monomer, in which the catalyst must be soluble, is maintained in droplet fonn suspended in water by agitation in the presence of a stabilizer such as gelatin each droplet of monomer undergoes bulk polymerization. In emulsion polymerization, ihe monomer is dispersed in water by means of a surfactant to form tiny particles held in suspension I micellcsK The monomer enters the hydrocarbon part of the micelles for polymerization by a... 

Almog et al. [80] studied the dispersion polymerization of styrene in different alcohols as the continuous medium by using AIBN and vinyl alcohol-vinyl acetate copolymer as the initiator and the stabilizer, respectively. Their results showed that the final particle size decreased with the alcohol type according to the following order ... 

In a very recent development, Debuigne et at. of vinyl acetate at 30 °C mediated by Co"(acac)2 (121). They obtained predictable molecular weights up to Mn 100000 and dispersities < 1.3 and proposed a polymerization mechanism analogous to that shown in Scheme 9.27. The complex... 

For example, the parameters g = 0.77, h = 0.94, p = 1.4, and C = 0.158 measured for a polymer sample and compared with the plots in Figures 7.11 through 7.13 were most consistent with athree-arm star monodisperse polymer a poly disperse three-arm star would have g= 1.12,/ = 1.05,p= 1.6, and C close to 0.2. °° The second example was poly(vinyl acetate) (PVAc) prepared by emulsion polymerization. Since no data for linear equivalent were available, g and h were not calculated. At lower conversion/MW p= 1.84 was found, only slightly higher than the theoretically expected p = 1.73 for a randomly branched architecture, p slightly decreased with increasing M, indicating... 

Polymerizations conducted in nonaqueous media in which the polymer is insoluble also display the characteristics of emulsion polymerization. When either vinyl acetate or methyl methacrylate is polymerized in a poor solvent for the polymer, for example, the rate accelerates as the polymerization progresses. This acceleration, which has been called the gel effect,probably is associated with the precipitation of minute droplets of polymer highly swollen with monomer. These droplets may provide polymerization loci in which a single chain radical may be isolated from all others. A similar heterophase polymerization is observed even in the polymerization of the pure monomer in those cases in which the polymer is insoluble in its own monomer. Vinyl chloride, vinylidene chloride, acrylonitrile, and methacryloni-trile polymerize with precipitation of the polymer in a finely divided dispersion as rapidly as it is formed. The reaction rate increases as these polymer particles are generated. In the case of vinyl chloride ... 

Much work on the preparation of nonaqueous polymer dispersions has involved the radical polymerization of acrylic monomers in the presence of copolymers having the A block the same as the acrylic polymer in the particle core 2). The preparation of polymer dispersions other than polystyrene in the presence of a PS-PDMS diblock copolymer is of interest because effective anchoring of the copolymer may be influenced by the degree of compatibility between the PS anchor block and the polymer molecules in the particle core. The present paper describes the interpretation of experimental studies performed with the aim of determining the mode of anchoring of PS blocks to polystyrene, poly(methyl methacrylate), and poly(vinyl acetate) (PVA) particles. 

PVA Particles. Dispersions were prepared in order to examine stabilization for a core polymer having a glass transition temperature below the dispersion polymerization temperature. PVA particles prepared with a block copolymer having M PS) x 10000 showed a tendency to flocculate at ambient temperature during redispersion cycles to remove excess block copolymer, particularly if the dispersion polymerization had not proceeded to 100 conversion of monomer. It is well documented that on mixing solutions of polystyrene and poly(vinyl acetate) homopolymers phase separation tends to occur (10,11), and solubility studies (12) of PS in n-heptane suggest that PS blocks with Mn(PS) 10000 will be close to dissolution when dispersion polymerizations are performed at 3 +3 K. Consequently, we may postulate that for soft polymer particles the block copolymer is rejected from the particle because of an incompatibility effect and is adsorbed at the particle surface. If the block copolymer desorbs from the particle surface, then particle agglomeration will occur unless rapid adsorption of other copolymer molecules occurs from a reservoir of excess block copolymer. 

Suspension Polymerization. The suspension or pearl polymerization process has been used to prepare polymers for adhesive and coaling applications and for conversion to poly(vinyl alcohol). Suspension polymerization are carried out with monomer-soiubie initiators predominantly, with low levels of stabilizers Continuous tubular polymerization of vinyl acetate in suspension yields stable dispersions of beads with narrow particle size distributions at high yields. 

Most dispersion polymerizations in C02, including the monomers methyl methacrylate, styrene, and vinyl acetate, have been summarized elsewhere (Canelas and DeSimone, 1997b Kendall et al., 1999) and will not be covered in this chapter. In a dispersion polymerization, the insoluble polymer is sterically stabilized as colloidal polymer particles by the surfactant that is adsorbed or chemically grafted to the particles. Effective surfactants in the dispersion polymerizations include C02-soluble homopolymers, block and random copolymers, and reactive macromonomers. Polymeric surfactants for C02 have been designed by combining C02-soluble (C02-philic) polymers, such as polydimethylsiloxane (PDMS) or PFOA, with C02-insoluble (C02-phobic) polymers, such as hydrophilic or lipophilic polymers (Betts et al., 1996, 1998 Guan and DeSimone, 1994). Several advances in C02-based dispersion polymerizations will be reviewed in the following section. 

Canelas, D. A. Betts, D. E. DeSimone, J. M. Yates, M. Z. Johnston, K. P. Poly(vinyl acetate) and Poly(vinyl acetate-co-ethylene) Latexes via Dispersion Polymerizations in Carbon Dioxide. Macromolecules 1998, 31, 6794-6805. 

While vinyl acetate is normally polymerized in batch or continuous stirred tank reactors, continuous reactors offer the possibility of better heat transfer and more uniform quality. Tubular reactors have been used to produce polystyrene by a mass process (1, 2), and to produce emulsion polymers from styrene and styrene-butadiene (3 -6). The use of mixed emulsifiers to produce mono-disperse latexes has been applied to polyvinyl toluene (5). Dunn and Taylor have proposed that nucleation in seeded vinyl acetate emulsion is prevented by entrapment of oligomeric radicals by the seed particles (6j. Because of the solubility of vinyl acetate in water, Smith -Ewart kinetics (case 2) does not seem to apply, but the kinetic models developed by Ugelstad (7J and Friis (8 ) seem to be more appropriate. 

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