Dispersed phase polymerizations

In addition to acting as impact modifiers a number of polymeric additives may be considered as processing aids. These have similar chemical constitutions to the impact modifiers and include ABS, MBS, chlorinated polyethylene, acrylate-methacrylate copolymers and EVA-PVC grafts. Such materials are more compatible with the PVC and are primarily included to ensure more uniform flow and hence improve surface finish. They may also increase gelation rates. In the case of the compatible MBS polymers they have the special function already mentioned of balancing the refractive indices of the continuous and disperse phases of impact-modified compound. 

The principal production methods for acrylamide polymers are polymerization in aqueous solutions, mixed solvent solutions, and various dispersed phases. 

An overview of the various dispersed-phase polymerizations is given in... 

Protective colloids or polymeric materials can be adsorbed onto the surface of the dispersed phase. Polymer adsorption can be accomplished simply by... 

The controlled flocculation method may be used in conjunction with the addition of a polymeric material to form a structured vehicle. After the formation of the floes, an aqueous solution of polymeric material, usually negatively charged, such as carboxy-methylcellulose or carbopol, is added. The concentration employed depends on the consistency desired for the suspension, which also relates to the size and density of the dispersed phase. Care must be taken to ensure the absence of any incompatibility between the flocculating agent and the polymer used for the formation of the structured vehicle. 

An aqueous colloidal polymeric dispersion by definition is a two-phase system comprised of a disperse phase and a dispersion medium. The disperse phase consists of spherical polymer particles, usually with an average diameter of 200-300 nm. According to their method of preparation, aqueous colloidal polymer dispersions can be divided into two categories (true) latices and pseudolatices. True latices are prepared by controlled polymerization of emulsified monomer droplets in aqueous solutions, whereas pseudolatices are prepared starting from already polymerized macromolecules using different emulsification techniques. 

In interfacial polymerization, monomers react at the interface of two immiscible liquid phases to produce a film that encapsulates the dispersed phase. The process involves an initial emulsification step in which an aqueous phase, containing a reactive monomer and a core material, is dispersed in a nonaqueous continuous phase. This is then followed by the addition of a second monomer to the continuous phase. Monomers in the two phases then diffuse and polymerize at the interface to form a thin film. The degree of polymerization depends on the concentration of monomers, the temperature of the system, and the composition of the liquid phases. 

A high internal phase liquid-liquid emulsion (HIPE) is one where the internal or dispersed phase droplets occupy >74% of the total volume of the emulsion. At this point the droplets contact each other and beyond this volume % the droplets are forced into distorted polyhedra. If for example styrene and divinylbenzene are employed as the continuous phase and water droplets dispersed in this oil phase using a suitable surfactant to form a HIPE, the comonomers can be polymerized to form a poly(styrene-divinylbenzene) polyHIPE. Typically the water droplets are... 

In contrast to the highly interconnected pores mentioned previously, closed pores can also be obtained by microemulsion polymerization if the initial volume fraction of the dispersed phase is kept lower than 30%. Recently two systems have been reported where the polymerization of the continuous phase and the subsequent removal of the Hquid dispersed phase resulted in the formation... 

Manson (72,) expanded the concept to the solid state by observing that the strength of composite materials also depended upon the acid-base interaction between continuous and dispersed phases. More directly, Vanderhoff et al. (21) addressed the issue of adhesion of polymeric materials to corroded steel. They synthesized eight corrosion products of iron, and used the interaction scheme developed by Fowkes and Manson first to characterize the iron corrosion products as Lewis acids or bases and then to select polymer vehicles for practical coating systems. Such results were employed to enhance the adhesion of epoxy systems to substrates which were predominantly iron oxide in nature. A good overview of these Issues was presented by Fowkes in 1983 (74). ... 

The monodisperse fragmentation process can be extended to produce monodis-perse solid particles [156], The general strategy consists of performing the emulsification in conditions such that the dispersed phase is in the liquid state, and to solidify the drops either by a temperature quench or through polymerization. The microscopic image in Fig. 1.29 illustrates this possibility. It corresponds to solid paraffin oil dispersed in water at room temperature. The emulsification was performed in the liquid state, at a temperature above the melting point of the... 

Relationship Between Nodular and Rejecting Layers. Nodular formation was conceived by Maler and Scheuerman (14) and was shown to exist in the skin structure of anisotropic cellulose acetate membranes by Schultz and Asunmaa ( ), who ion etched the skin to discover an assembly of close-packed, 188 A in diameter spheres. Resting (15) has identified this kind of micellar structure in dry cellulose ester reverse osmosis membranes, and Panar, et al. (16) has identified their existence in the polyamide derivatives. Our work has shown that nodules exist in most polymeric membranes cast into a nonsolvent bath, where gelation at the interface is caused by initial depletion of solvent, as shown in Case B, which follows restricted Inward contraction of the interfacial zone. This leads to a dispersed phase of micelles within a continuous phase (designated as "polymer-poor phase") composed of a mixture of solvents, coagulant, and a dissolved fraction of the polymer. The formation of such a skin is delineated in the scheme shown in Figure 11. 

It is the intent of this doeument to define the terms most commonly encountered in the field of polymer blends and eomposites. The scope has been limited to mixtures in which the eomponents differ in ehemical composition or molar mass or both and in which the continuous phase is polymeric. Many of the materials described by the term multiphase are two-phase systems that may show a multitude of finely dispersed phase domains. Hence, incidental thermodynamic descriptions are mainly limited to binary mixtures, although they can be and, in the scientific literature, have been generalized to multicomponent mixtures. Crystalline polymers and liquid-crystal polymers have been considered in other documents [1,2] and are not discussed here. 

Sol in which the dispersed phase consists of particles having a polymeric structure. 

Styrene as matrix and polybutadiene as dispersed phase. During this phase inversion the above-mentioned graft copolymers act as polymeric emulsifiers and determine, inter alia, the particle size and particle size distribution of the dispersed polybutadiene phase. This morphology is fixed through another chemical reaction, that is the crosslinking of the polybutadiene phase. Therefore, the reaction mixture at the end of the prepolymerization period (at 30% conversion) does scarcely alter its morphology when it is polymerized to complete conversion, which is done without stirring mostly in bulk in a separate vessel. 

It is also possible to generate microcapsules through interfacial polymerization using only one monomer to form the shell. In this class of encapsulations, polymerization must be performed with a surface-active catalyst, a temperature increase, or some other surface chemistry. Herbert Scher of Zeneca Ag Products (formerly Stauffer Chemical Company) developed an excellent example of the latter class of shell formation (Scher 1981 Scher et al. 1998). He used monomers featuring isocyanate groups, like poly(methylene)-poly(phenylisocyanate) (PMPPI), where the isocyanate reacts with water to reveal a free primary amine. Dissolved in the oil-dispersed phase of an oil-in-water emulsion, this monomer contacts water only at the phase boundary. The primary amine can then react with isocyanates to form a polyurea shell. Scher used this technique to encapsulate pesticides, which in their free state would be too volatile or toxic, and to control the rate of pesticide release. 

When chloro-octadecane was found to give the same result as a so-called cosurfactant, an argument arose in terms of the real role of this highly hydrophobic compound because it is not surface active and has no cooperation with surfactant. Taking account of these systems, the definition of miniemulsion polymerization will be revised to the polymerization in which a water-insoluble compound in the dispersed phase retards or inhibits diffusion degradation of the emulsion. ... 

The dispersed phase of high internal phase emulsions may also be used to prepare polymeric materials in this case, conversion of monomer dispersed droplets to polymer results in latexes or particulates. 

---