Sizing Solution polymerization

Other than fuel, the largest volume appHcation for hexane is in extraction of oil from seeds, eg, soybeans, cottonseed, safflower seed, peanuts, rapeseed, etc. Hexane has been found ideal for these appHcations because of its high solvency for oil, low boiling point, and low cost. Its narrow boiling range minimises losses, and its low benzene content minimises toxicity. These same properties also make hexane a desirable solvent and reaction medium in the manufacture of polyolefins, synthetic mbbers, and some pharmaceuticals. The solvent serves as catalyst carrier and, in some systems, assists in molecular weight regulation by precipitation of the polymer as it reaches a certain molecular size. However, most solution polymerization processes are fairly old it is likely that those processes will be replaced by more efficient nonsolvent processes in time. 

Since microgels are intramolecularly crosslinked macromolecules of colloidal dimensions, it is necessary for their synthesis to control the size of the growing crosslinked molecules. This can be achieved by carrying out polymerization and crosslinking in a restricted volume, i.e. that of a micelle or of a polymer coil. Thus, two general methods of microgel synthesis are available (1) emulsion polymerization, and (2) solution polymerization. 

Sander et al. [63] investigated the effect of microparticulate silica pore size on the properties of solution-polymerized Cig stationary phases and observed both an increase in bonding density and shape recognition for wider pore (>120 A) silica. A size-exclusion mechanism was proposed, in which the reaction of the silane polymer on the surface is enhanced for wide pores and reduced for narrow pores. Polymeric Ci8 phases prepared on substrates with narrow pores exhibited monomeric-like chromatographic properties. This effect may be the result of an increase in competitive surface linkage with the less sterically hindered monomers that coexist with the bulkier oligomers that have polymerized in the reaction solution (Figure 5.13). 

Figure 2. Percentage conversion (%) and particle size (A) as a function of time for a dispersion polymerization and percentage conversion as a function of time for an equivalent solution polymerization...

Emulsion polymerization is usually carried out isothermally in batch or continuous stirred-tank reactors. Temperature control is much easier than for bulk or solution polymerization because the small ( 0.5 fim) polymer particles, which are the locus of the reaction, are suspended in a continuous aqueous medium. This complex, multiphase reactor also shows multiple steady states under isothermal conditions. In industrial practice, such a reactor often shows sustained oscillations. Solid-catalyzed olefin polymerization in a slurry batch reactor is a classic example of a slurry reactor where the solid particles change size and characteristics with time during the reaction process. 

Vinyl solution resins are usually made via suspension or solution polymerization techniques. Plastisols are defined as suspensions of homopolymers or copolymers in nonaqueous liquids. The liquids, which are normally vinyl plasticizers, are selected so that they do not solvate the polymer to any extent at room temperature. The suspension is maintained by residual emulsifier left on the particle, and the very small particle size of the polymer itself (all pass through a 200-mesh screen). A finite quantity of plasticizer must be present in order to form the plastisol or "paste" no plasticizer, no plastisol. As with all vinyl systems, consideration may have to be given to plasticization, heat and light stabilization, pigmentation, etc. 

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