Emulsion technique

Copolymerization is effected by suspension or emulsion techniques under such conditions that tetrafluoroethylene, but not ethylene, may homopolymerize. Bulk polymerization is not commercially feasible, because of heat-transfer limitations and explosion hazard of the comonomer mixture. Polymerizations typically take place below 100°C and 5 MPa (50 atm). Initiators include peroxides, redox systems (10), free-radical sources (11), and ionizing radiation (12). 

Polymerization Processes. Vinyl acetate has been polymerized industrially by bulk, solution, suspension, and emulsion processes (34). Perhaps 90% of the material identified as poly(vinyl acetate) or copolymers that are predominantly vinyl acetate are made by emulsion techniques. Detailed information is in patent and scientific Hterature and in procedures available in the brochures from monomer producing companies (15,34). 

In the late 1940s, the demand for styrene homopolymers (PS) and styrene-acrylonitrile copolymers (SAN) was drastically reduced due to their inherent brittleness. Thus, the interest was shifted to multiphase high-impact polystyrene (HIPS) and rubber-modified SAN (ABS). In principle, both HIPS and ABS can be manufactured by either bulk or emulsion techniques. However, in actual practice, HIPS is made only by the bulk process, whereas ABS is produced by both methods [132,133]. 

The multiple emulsion technique includes three steps 1) preparation of a primary oil-in-water emulsion in which the oil dispersed phase is constituted of CH2CI2 and the aqueous continuous phase is a mixture of 2% v/v acetic acid solution methanol (4/1, v/v) containing chitosan (1.6%) and Tween (1.6, w/v) 2) multiple emulsion formation with mineral oil (oily outer phase) containing Span 20 (2%, w/v) 3) evaporation of aqueous solvents under reduced pressure. Details can be found in various publications [208,209]. Chemical cross-linking is an option of this method enzymatic cross-linking can also be performed [210]. Physical cross-linking may take place to a certain extent if chitosan is exposed to high temperature. 

The emulsion technique is convenient when the drug is particularly sensitive to certain parameters connected to the spray-drying. The emulsion technique may be associated to cross-Unking or other treatments of the microspheres. The following examples are self-explanatory. 

Fig. 10 Release of cromolyn sodium (sodium cromoglycate) from human serum albumin microspheres prepared using a water-oil emulsion technique with 5% glutaraldehyde as cross-linking agent. Dissolution medium pH 7 phosphate buffer. (From Ref. 98.)... 

Vinyl monomers can be polymerized using solution, bulk, suspension, and emulsion techniques. Each has its own characteristic strengths and weaknesses. 

Suspension and emulsion techniques provide additional means for modifying the properties of the resulting polymers, for example ... 

Polymerization reactions in aqueous medium can be carried out in homogeneous solution if the monomers and the polymers are soluble in water as in the case of acrylamide or methacrylic acid (see Examples 3-5,3-9, and 3-35). Since most of the monomers are only sparingly soluble in water, suspension or emulsion techniques have to be applied in these cases. 

Figure 16.2 Preparation of starch acetate microparticles by water-in-oil-in-water double emulsion technique.

Microspheres are particles ranging between 1 and 100 pm. They are typically formed from degradable polymeric materials such as albumin, polysaccharides, or poly(a-hydroxy acids) by precipitation or phase-separation emulsion techniques [6, 332]. The relatively large diameters of microspheres make their extravasation into the tumor mass difficult and the uptake of microspheres by the RES is very rapid. 

From the point of view of the organic chemist, the suspension and emulsion techniques are perhaps the best methods for preparing reasonable quantities of many homo- and copolymers. The apparatus and manipulations resemble those of familiar laboratory operations. 

Meng FT, Ma GH, Qiu W, Su ZG. W/O/W double emulsion technique using ethyl acetate as organic solvent effects of its diffusion rate on the characteristics of microparticles. J Control Release 2003 91(3) 407-416. 

POLYVINYLIDENE CHLORIDE. [CAS 9002-86-2J. A stereoregular, thermoplastic polymer is produced by the free-radical chain polymerization of vinylidene chloride (H>C=CCIi) using suspension or emulsion techniques. The monomer lias a bp of 31.6°C and was first synthesized in 1838 by Regnault. who dehydrochlorinated 1,1.2-trichloroethane which he obtained by the chlorination of ethylene. The copolymer product has been produced under various names, including Saran. As shown by the following equation, the product, in production since the late 1930s, is produced by a reaction similar to that used by Regnault nearly a century earlier ... 

The polyazophenylene units are formed from the polyrecombination of the decomposition products from bis(nitrosoacetyl)benzidine. Chain termination can occur by disproportionation of the polymer radicals and by recombination with acetoxy radicals. Despite the rate constant for the recombination of the phenyl and azophenyl radicals being much larger than that of the initiation reaction for isoprene, it is possible to synthesise copolymers from these materials by a careful choice of the various reaction parameters. However, block copolymers could only be obtained using emulsion techniques (see Table 4.11) and not in bulk or in solution. 

Similar grafting experiments by the emulsion technique were described (34) in the system vinyl chloride/copolymer butyl methacrylate-methacrylic acid and in the reverse system, and also in the system styrene/polyvinyl chloride. In this last case again as in homogenous medium, the inverse process failed (vinyl chloride on polystyrene). Grafted acrylonitrile copolymers were also prepared in order to improve their dyeability, by polymerizing acrylonitrile in emulsion in the presence of many different polymers as polyvinyl alcohol, polymethacrylamide and polyvinylpyrrolidone (119, 120, 121), polyvinyl acetate and polyacrylic acid (115), wool (224,225), proteins (136), etc. 

Hart and de Pauw 98) used this emulsion technique on the system vinyl acetate-acrylic acid. It is well known that the copolymerization parameters rx and r2 are unfavorable in this system therefore the relative solubility of the two monomers exerces only a small influence on the composition of both sequences. The degree of homogeneity of the sequences has been evaluated, after alkaline hydrolysis, by measuring the tendency to lactonization in acid medium. While 72% of the acetate groups could be lactonized in the case of a random copolymer containing 37% vinyl acetate, only 14% are transformed in a block copolymer with the same initial composition. 

The same principle can be applied using diisopropyl benzene dihydroperoxide (5, 181, 182). The synthesis of polymeric hydroperoxides in which the hydroperoxide groups occupy terminal positions in the polymer chain, was carried out in emulsion, using the system w-diisopropyl-benzene dihydroperoxide/ferrous ion/pyrophosphate the residual hydroperoxide groups on the polymer are protected from further reaction by the emulsion technique, the residence time in the aqueous phase being sufficiently short. 

Microbial biomethylation, antimony, 12, 644 Microbial dealkylation, examples, 12, 610 Microbial demethylation, examples, 12, 610 Micro-emulsion techniques, for molecular precursor transformations, 12, 46 Microencapsulation... 

When emulsion techniques are used for microsphere preparation, a number of processing factors influences the final structure of the microspheres, e.g., the choice of solvents and surfactants, phase viscosity, the ratio of the dispersed to the continuous phase, mixing speed, processing temperature, and time. Micro-... 

Many polymerizations are performed by the emulsion technique to prepare a polymeric substance. The latex obtained is then coagulated, and the polymer is isolated. A paint latex, however, is used as such in the paint formulation, which leads to some special requirements for its stability, such as storage, mechanical, electrolyte, and freeze/thaw stability. 

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