Polymerization, dispersion solvent effects

These block copolymers can act as effective steric stabilizers for the dispersion polymerization in solvents with ultralow cohesion energy density. This was shown with some polymerization experiments in Freon 113 as a model solvent. The dispersion particles are effectively stabilized by our amphi-philes. However, these experiments can only model the technically relevant case of polymerization or precipitation processes in supercritical C02 and further experiments related to stabilization behavior in this sytem are certainly required. 

The elementary reactions of carbocationic polymerizations can be separated into three types. Deactivation of carbenium ions with anions and transfer to counteranion are ion-ion reactions, propagation and transfer to monomer are ion-dipole reactions, and ionization is a dipole-dipole reaction [274]. Ion-ion and dipole-dipole reactions with polar transition states experience the strongest solvent effects. Carbocationic propagation is an ion-dipole reaction in which a growing carbenium ion adds electro-philically to an alkene it should be weakly accelerated in less polar solvents because the charge is more dispersed in the transition state than in the ground state [276]. However, a model addition reaction of bis(p-methoxyphenyl)carbenium ions to 2-methyl- 1-pentene is two times faster in nitroethane (e = 28) than in methylene chloride (e = 9) at - 30° C [193]. However, this is a minor effect which corresponds to only ddG = 2 kJ morit may also be influenced by specific solvation, polarizability, etc. [276,277]. 

A consistent theme from paint manufacturers is to produce water-based blacks with equal jetness, and hue, to solvent-based paints. The highest jetness blacks have extremely high surface areas (300-550 m /g) and are extremely difficult to stabilize effectively. A series of high surface area blacks with different surface chemistries has been evaluated with a range of polymeric dispersants to study optimum jetness. 

Shim, S.E. Oh, S. Chang, Y.H. Jin, M.J. Choe, S. Solvent effect on TEMPO-mediated living free radical dispersion polymerization of styrene. Polymer 2004, 45 (14), 4731-4739. 

Also referred to as polyelectrolytes, ionic polymeric dispersants consist of chain segments that carry ionized groups and are therefore effective in aqueous solvents. On dissociation, the ionized groups in the chain segment can produce negatively charged species (anionic polymers) or positively charged species (ca-... 

The main purpose of pesticide formulation is to manufacture a product that has optimum biological efficiency, is convenient to use, and minimizes environmental impacts. The active ingredients are mixed with solvents, adjuvants (boosters), and fillers as necessary to achieve the desired formulation. The types of formulations include wettable powders, soluble concentrates, emulsion concentrates, oil-in-water emulsions, suspension concentrates, suspoemulsions, water-dispersible granules, dry granules, and controlled release, in which the active ingredient is released into the environment from a polymeric carrier, binder, absorbent, or encapsulant at a slow and effective rate. The formulation steps may generate air emissions, liquid effluents, and solid wastes. 

Paine et al. [85] extensively studied the effect of solvent in the dispersion polymerization of styrene in the polar media. In their study, the dispersion polymerization of styrene was carried out by changing the dispersion medium. They used hydroxypropyl cellulose (HPC) as the stabilizer and its concentration was fixed to 1.5% within a series of -alcohols tried as the dispersion media. The particle size increased from only 2.0 /itm in methanol to about 8.3 /itm in pentanol, and then decreased back to 1 ixm in octadecanol. The particle size values plotted against the Hansen solubility parameters... 

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 ... 

The dispersion polymerization system is composed of monomer, solvent, initiator, and stabilizer. The combination of monomer, solvent, and stabilizer is essential for particle preparation. That is to say, the stabilizer is chosen to meet the demand of the monomer and solvent. In any system, the stabilizer has affinity or cohesive strength for both the medium and the polymer particles. In a dispersion polymerization, the medium and polymer particles both are organic compounds. Therefore, it is not rational to rely on dispersion stabilization, which comes from the electrostatic repulsion force between particles. The stabilizer for dispersion polymerization that makes interfacial energy low must have affinity for particles due to the same quality and solvation at the surface of particles. It is desired that the stabilizer be a polymer that indicates a steric stabilization effect on the surface (5). 

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