Emulsion compositions, continuous

Compositional control for other than azeotropic compositions can be achieved with both batch and semibatch emulsion processes. Continuous addition of the faster reacting monomer, styrene, can be practiced for batch systems, with the feed rate adjusted by computer through gas chromatographic monitoring during the course of the reaction (54). A calorimetric method to control the monomer feed rate has also been described (8). For semibatch processes, adding the monomers at a rate that is slower than copolymerization can achieve equilibrium. It has been found that constant composition in the emulsion can be achieved after ca 20% of the monomers have been charged (55). 

The nudeation stage constitutes the so-called Interval I in an emulsion polymerization, the initial perind in which the particle number is changing. In Intervals II and III the paftide number is believed to he essentially constant. Nudeation of new particles may in some cases also take place during Intervals II and III. This phenomenon is often referred to as secondary nudeation and may be encountered in systems with poor stability (coagulation) or with changing composition (continuous and semi-continuous polymerizations). The present chapter will attempt to treat all mechanisms that may lead to formation of polymer partides, in whatever stage of the polymerization they take place. 

The emulsifying effect of a copolymer can be characterized by determining the type of emulsion (DMF in hexane or hexane in DMF), its stability, its viscosity, and the particle size of the dispersed phase. These characteristics of oil-in-oil emulsions obtained with PS-PI block copolymers were studied as functions of solvent volume ratio, molecular weight, composition, and structure of the copolymer (5). Although Bancroft s rule was established for conventional oil-water emulsions, it appears to apply also to oil-in-oil emulsions—the continuous phase of the emulsion is preferentially formed by the solvent having the best solubility for the emulsifier (6, 7). Thus, block or graft copolymers can be prepared giving hexane/DMF, DMF/hexane, or both types of emulsions. 

The Function of Poly(acrylic acid) Thickeners in Emulsion Compositions. Poly(acrylic acid) thickeners are used in many commercial emulsion formulations. In general, the poly(acrylic acid) thickeners are not adsorbed at the oil-water interface and, therefore, cannot, by themselves, prevent coalescence of the emulsion droplets. Primary emulsifiers are required for emulsification and stabilization of the emulsion droplets against coalescence. Poly(acrylic acid) thickeners are now used principally to modify the rheology of the continuous water phase and to confer viscosity and yield value on that phase. As a consequence, emulsion droplets are effectively suspended, and creaming of the emulsion is prevented. 

Much preliminary work was needed to determine quantities and coiqiosl-tlons of emulsions to be used and the hydrodynamics df the membrane system, and to develop an assay for toluene and heptane In the various streams. This series of experiments is detailed by Murrer (17). Based on his work, the emulsion compositions listed In Table I were chosen for the continuous feasibility study. Inlet and outlet... 

There are two common types of continuous reactors continuous stirred tank reactors (CSTRs) (53), and plug flow reactors (PFRs). CSTRs are simply large tanks that are ideally well-mixed (such that the emulsion composition is uniform throughout the entire reactor volume) in which the polymerisation takes place. CSTRs are operated at a constant overall conversion. CSTRs are often used in series or trains to build up conversion incrementally. Styrene-butadiene rubber has been produced in this manner. Not all latex particles spend the same amount of time polymerising in a CSTR. Some particles exit sooner than others, producing a distribution of particle residence times, diameters and compositions. 

An issue relevant for potential antifoam behavior for compositions within the coexistence curve concerns the physical state of the two conjugate solutions. Essentially they form an emulsion, the continuous phase of which is in part determined by the relative amounts of each phase. Consider then the tie line shown in Figure 4.33 joining compositions Ti and it2. The relative amounts of each phase L( iti) and at the overall composition xj/j on the tie line is then given by the lever rule so that... 

The batch-suspension process does not compensate for composition drift, whereas constant-composition processes have been designed for emulsion or suspension reactions. It is more difficult to design controUed-composition processes by suspension methods. In one approach (155), the less reactive component is removed continuously from the reaction to keep the unreacted monomer composition constant. This method has been used effectively in VT)C-VC copolymerization, where the slower reacting component is a volatile and can be released during the reaction to maintain constant pressure. In many other cases, no practical way is known for removing the slower reacting component. 

This paper presents the physical mechanism and the structure of a comprehensive dynamic Emulsion Polymerization Model (EPM). EPM combines the theory of coagulative nucleation of homogeneously nucleated precursors with detailed species material and energy balances to calculate the time evolution of the concentration, size, and colloidal characteristics of latex particles, the monomer conversions, the copolymer composition, and molecular weight in an emulsion system. The capabilities of EPM are demonstrated by comparisons of its predictions with experimental data from the literature covering styrene and styrene/methyl methacrylate polymerizations. EPM can successfully simulate continuous and batch reactors over a wide range of initiator and added surfactant concentrations. 

In the production of crude oil, the greatest part of the crude oil occurs as a water-in-oil emulsion. The composition of the continuous phase depends on the water/oil ratio, the natural emulsifier systems contained in the oil, and the origin of the emulsion. The natural emulsifiers contained in crude oils have a complex chemical structure, so that, to overcome their effect, petroleum-emulsion demulsifiers must be selectively developed. As new oil fields are developed, and as the production conditions change at older fields, there is a constant need for demulsifiers that lead to a rapid separation into water and oil, as well as minimal-residual water and salt mixtures. 

One way that contaminants are retained in the subsurface is in the form of a dissolved fraction in the subsurface aqueous solution. As described in Chapter 1, the subsurface aqueous phase includes retained water, near the solid surface, and free water. If the retained water has an apparently static character, the subsurface free water is in a continuous feedback system with any incoming source of water. The amount and composition of incoming water are controlled by natural or human-induced factors. Contaminants may reach the subsurface liquid phase directly from a polluted gaseous phase, from point and nonpoint contamination sources on the land surface, from already polluted groundwater, or from the release of toxic compounds adsorbed on suspended particles. Moreover, disposal of an aqueous liquid that contains an amount of contaminant greater than its solubility in water may lead to the formation of a type of emulsion containing very small droplets. Under such conditions, one must deal with apparent solubility, which is greater than handbook contaminant solubility values. 

The model system used by Mabille et al. [149, 150] was a set of monodisperse dilute (2.5 wt% of dispersed oil) emulsions of identical composition, whose mean size ranged from 4 p.m to 11 p.m. A sudden shear of 500 s was applied by means of a strain-controlled rheometer for durations ranging from 1 to 1500 s. All the resulting emulsions were also monodisperse. At such low oil droplet fraction, the emulsion viscosity was mainly determined by that of the continuous phase (it was checked that the droplet size had no effect on the emulsion viscosity). The viscosity ratio p = t]a/t]c = 0.4 and the interfacial tension yi t = 6 mN/m remained constant. 

Artificial control of the monomer concentrations is possible by changing the monomer feed methods, which includes multishot, stage feed (19), and continuous feed. A multishot emulsion polymerization is expected to form multilayered particles if the monomers are chosen properly. When the layers are sufficiently thin, the particles exhibit unique thermal and mechanical properties. The stage feed system is shown in Figure 11.1.6. It makes it possible to produce particles having gradient composition of different monomer units. 

If both continuous and dispersed phases of highly concentrated emulsions contain monomeric species, it is possible to obtain hydrophilic/hydrophobic polymer composite materials. Polyacrylamide/polystyrene composites have been prepared in this manner [180], from both w/o and o/w HIPEs containing aqueous acrylamide and a solution of styrene in an organic solvent. 

The unusual sensitivity of some composite-modified double-phase propellants before curing has justified intensive effort to exploit a nonmechanical mixing process. First introduced in about 1959 as the quick-mix process by Rocketdyne Division of North American Aviation (5, 10), the inert diluent process has been developed at the Naval Ordnance Station, Indian Head, Md. for application to a variety of propellant compositions. Separate streams of solids, slurried in heptane, and an emulsion of plasticizers in heptane, are combined in a non-mechanical mixing chamber. The complete propellant slurry is allowed to settle, and the heptane is separated and recycled in a continuous operation. Figure 1... 

Gulf Canada Limited (20, 2T). The process developed by Gulf consists of a pumping system wfnch continuously delivers measured volumes of sulfur and asphalt to a mixing device which disperses the molten sulfur in the liquid asphalt. The composition of the emulsion is typically in the range 25-60 parts sulfur to 75-40 parts asphalt. The temperatures of the sulfur, asphalt and S/A emulsion are maintained in the ranges 121-154 C, 121-177 C, and 121-154 C, respectively. 

Heterogeneous Copolymerization. When copolymer is prepared in a homogeneous solution, kineiic expressions can be used to predict copolymer composition Bulk and dispersion polymerization are somewhat different since the reaction medium is heterogeneous and polymeri/aiion occurs simultaneously in separate loci. In bulk polymerization, for example, the monomer swollen polymer particles support polymerization within the particle core us well as on the particle surface, lit aqueous dispersion or emulsion polymeri/aiion the monomer is actually dispersed in two or three distinct phases a continuous aqueous phase, a monomer droplet phase, and a phase consisting of polymer particles swollen at Ihe surface with monomer. This affect the ultimate polymer composition because llie monomers are partitioned such that the monomer mixture in the aqueous phase is richer in the more water-soluble monomers than the two organic phases. 

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