Aqueous dispersion polymerization

POLYMERIC AQUEOUS DISPERSION VULCANISING AGENTS FOR GENERAL-PURPOSE LATICES AND RUBBERS... 

In mass polymerization bulk monomer is converted to polymers. In solution polymerization the reaction is completed in the presence of a solvent. In suspension, dispersed mass, pearl or granular polymerization the monomer, containing dissolved initiator, is polymerized while dispersed in the form of fine droplets in a second non-reactive liquid (usually water). In emulsion polymerization an aqueous emulsion of the monomer in the presence of a water-soluble initiator Is converted to a polymer latex (colloidal dispersion of polymer in water). 

Emulsion polymerization also has the advantages of good heat transfer and low viscosity, which follow from the presence of the aqueous phase. The resulting aqueous dispersion of polymer is called a latex. The polymer can be subsequently separated from the aqueous portion of the latex or the latter can be used directly in eventual appUcations. For example, in coatings applications-such as paints, paper coatings, floor pohshes-soft polymer particles coalesce into a continuous film with the evaporation of water after the latex has been applied to the substrate. 

Emulsion Polymerization. Emulsion polymerization is the most important industrial method for the preparation of acryhc polymers. The principal markets for aqueous dispersion polymers made by emulsion polymerization of acryhc esters are the paint, paper, adhesives, textile, floor pohsh, and leather industries, where they are used principally as coatings or binders. Copolymers of either ethyl acrylate or butyl acrylate with methyl methacrylate are most common. 

Acrylonitrile and its comonomers can be polymerized by any of the weU-known free-radical methods. Bulk polymerization is the most fundamental of these, but its commercial use is limited by its autocatalytic nature. Aqueous dispersion polymerization is the most common commercial method, whereas solution polymerization is used ia cases where the spinning dope can be prepared directly from the polymerization reaction product. Emulsion polymerization is used primarily for modacryhc compositions where a high level of a water-iasoluble monomer is used or where the monomer mixture is relatively slow reacting. 

Since polymer swelling is poor and the aqueous solubiUty of acrylonitrile is relatively high, the tendency for radical capture is limited. Consequentiy, the rate of particle nucleation is high throughout the course of the polymerization, and particle growth occurs predominantiy by a process of agglomeration of primary particles. Unlike emulsion particles of a readily swollen polymer, such as polystyrene, the acrylonitrile aqueous dispersion polymer particles are massive agglomerates of primary particles which are approximately 100 nm in diameter. 

Fig. 3. An aqueous dispersion polymerization process used in the manufacture of acrylic and modacrylic fibers.

Aqueous Dispersions. The dispersion is made by the polymerization process used to produce fine powders of different average particle sizes (58). The most common dispersion has an average particle size of about 0.2 p.m, probably the optimum particle size for most appHcations. The raw dispersion is stabilized with a nonionic or anionic surfactant and concentrated to 60—65 wt % soHds by electrodecantation, evaporation, or thermal concentration (59). The concentrated dispersion can be modified further with chemical additives. The fabrication characteristics of these dispersions depend on polymerization conditions and additives. 

The polymerization iavolves the reaction of sodium polysulftde with ethylene dichloride ia aqueous media at 70°C for 2—6 h, yielding an aqueous dispersion (latex) of the polysulftde mbber. 

Only particles of linear or very slightly cross-linked <0.6%) polymers may be produced by dispersion polymerization. Obviously, dispersion polymerization may be used for the production of monosized seed particles, which, after transfer to aqueous conditions, are used for the production of different cross-linked and macroporous particles by the activated swelling and polymerization method. 

Heterogeneous polymerization processes (emulsion, miniemulsion, non-aqueous dispersion) offer another possibility for reducing the rate of termination through what are known as compartmcntalization effects. In emulsion polymerization, it is believed that the mechanism for chain stoppage within the particles is not radical-radical termination but transfer to monomer (Section 5.2.1.5). These possibilities have provided impetus for the development ofliving heterogeneous polymerization (Sections 9.3.6.6, 9.4.3.2, 9.5.3.6). 

Free-radical polymerization of alkenes has been carried out in aqueous conditions.115 Aqueous emulsion and suspension polymerization is carried out today on a large scale by free-radical routes. Polymer latexes can be obtained as products (i.e., stable aqueous dispersions... 

The question whether the intramolecularly crosslinked microparticles of non-aqueous polymer dispersions are really microgels is also justified, considering non-aqueous dispersions prepared from acrylic copolymers and melamine/formaldehyde crosslinker with particle sizes of about 300 nm. [45, 343]. In any case, these crosslinked polymeric microparticles are useful constituents of high-solids coatings, imparting a yield stress to those solutions which probably involves attractive forces between the microparticles. 

Aqueous corrosion resistance, 13 513 Aqueous dispersion polymerization, 18 291 of acrylonitrile, 11 197-200 Aqueous dispersions, 13 292. See also Aqueous polytetrafluoroethylene dispersions... 

Personal exposure limit (PEL), for nickel compounds, 17 120. See also Permissible exposure limits (PEL) Personal hazard protection, 21 838 Personnel. See also People commitment of, 15 474 health and safety of, 21 826-827 selection and training of, 21 857 training requirements for, 24 345-347 Persulfate redox initiation, in aqueous dispersion polymerization, 11 197-198,199 Persulfates, 18 408 26 189-190 Persulfate salts, 18 409 Persulfuric acid, 18 407—408 Perturbation... 

Redox initiation, in aqueous dispersion polymerization, 11 197—198 Redox neutral atmosphere, 14 84 Redox potentials, of plutonium in acid,... 

The self-assembling character of bilayer membranes is demonstrated by the formation of free-standing cast films from aqueous dispersions of synthetic bilayer membranes. The tendencies for association are sufficiently strong to allow the addition of guest molecules (nanoparticles, proteins, and various small molecules) to these films where the connective forces are secondary in nature and not primary. Synthetic polymer chemists have made use of these self-assembling tendencies to synthesize monolayer films. In particular, a monomer that contains both reactive groups and hydrophobic and hydrophilic areas is cast onto an appropriate template that self-assembles the monomer, holding it for subsequent polymerization. Thus, a bilayer structure is formed by... 

Emulsion polymerization a sufficient amount of dispersing agent and mild agitation is employed. This produces small colloidal particles dispersed in the aqueous reaction medium. In this procedure, called aqueous dispersion polymerization, precipitation of the resin particles is avoided. The coagulated dispersion produced by emulsion polymerization is often called a fine-powder or PTFE dispersion. 

Encapsulated fluoropolymers can be made by polymerizing the encapsulating polymer in the presence of the fluoropolymer, for example in an aqueous dispersion. TSAN may provide significant advantages over PTFE, in that TSAN may be more readily dispersed in the composition. A suitable TSAN may is composed from 50% PTFE and 50% SAN (29). 

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