Emulsion systems, particle size

Microemulsion Polymerization. Polyacrylamide microemulsions are low viscosity, non settling, clear, thermodynamically stable water-in-od emulsions with particle sizes less than about 100 nm (98—100). They were developed to try to overcome the inherent settling problems of the larger particle size, conventional inverse emulsion polyacrylamides. To achieve the smaller microemulsion particle size, increased surfactant levels are required, making this system more expensive than inverse emulsions. Acrylamide microemulsions form spontaneously when the correct combinations and types of oils, surfactants, and aqueous monomer solutions are combined. Consequendy, no homogenization is required. Polymerization of acrylamide microemulsions is conducted similarly to conventional acrylamide inverse emulsions. To date, polyacrylamide microemulsions have not been commercialized, although work has continued in an effort to exploit the unique features of this technology (100). 

In such a system, the rate of oxidation is influenced by the emulsion composition (relative concentrations of substrate and emulsifier) and especially, by the partition of the emulsifier between the interface and the water phases. Other factors influencing lipid oxidation in emulsions are particle size of the oil droplets, the ratio of oxidizable to non-oxidizable compounds in the emulsion droplets, and the packing properties of the surface-active molecules. In addition, the amount and composition of the oil phase in an emulsion are important factors that influence oxidative stability, formation of volatiles, and partition of the decomposition products, between the oil and water phase. 

There are three keys to the use of particulate solids as emulsion stabilizers particle size, the state of stabilizer particle dispersion, and the relative wettability of the particles by each liquid component of the emulsion system. The stabilizer particles must be small compared to the emulsion droplet and in a state of incipient flocculation that is, the particle dispersion must be near the limit of stability so that their location at the interface will result in some attractive particle-particle interaction to give strength to the system. 

Monomer compositional drifts may also occur due to preferential solution of the styrene in the mbber phase or solution of the acrylonitrile in the aqueous phase (72). In emulsion systems, mbber particle size may also influence graft stmcture so that the number of graft chains per unit of mbber particle surface area tends to remain constant (73). Factors affecting the distribution (eg, core-sheU vs "wart-like" morphologies) of the grafted copolymer on the mbber particle surface have been studied in emulsion systems (74). Effects due to preferential solvation of the initiator by the polybutadiene have been described (75,76). 

In addition to graft copolymer attached to the mbber particle surface, the formation of styrene—acrylonitrile copolymer occluded within the mbber particle may occur. The mechanism and extent of occluded polymer formation depends on the manufacturing process. The factors affecting occlusion formation in bulk (77) and emulsion processes (78) have been described. The use of block copolymers of styrene and butadiene in bulk systems can control particle size and give rise to unusual particle morphologies (eg, coil, rod, capsule, cellular) (77). 

There are two principal PVC resins for producing vinyl foams suspension resin and dispersion resin. The suspension resin is prepared by suspension polymerization with a relatively large particle size in the 30—250 p.m range and the dispersion resin is prepared by emulsion polymerization with a fine particle size in the 0.2—2 p.m range (245). The latter is used in the manufacture of vinyl plastisols which can be fused without the appHcation of pressure. In addition, plastisol blending resins, which are fine particle size suspension resins, can be used as a partial replacement for the dispersion resin in a plastisol system to reduce the resin costs. 

Preparation of Emulsions. An emulsion is a system ia which one Hquid is coUoidaHy dispersed ia another (see Emulsions). The general method for preparing an oil-ia-water emulsion is to combine the oil with a compatible fatty acid, such as an oleic, stearic, or rosia acid, and separately mix a proportionate quantity of an alkah, such as potassium hydroxide, with the water. The alkah solution should then be rapidly stirred to develop as much shear as possible while the oil phase is added. Use of a homogenizer to force the resulting emulsion through a fine orifice under pressure further reduces its oil particle size. Liquid oleic acid is a convenient fatty acid to use ia emulsions, as it is readily miscible with most oils. 

Copolymers with butadiene, ie, those containing at least 60 wt % butadiene, are an important family of mbbers. In addition to synthetic mbber, these compositions have extensive uses as paper coatings, water-based paints, and carpet backing. Because of unfavorable reaction kinetics in a mass system, these copolymers are made in an emulsion polymerization system, which favors chain propagation but not termination (199). The result is economically acceptable rates with desirable chain lengths. Usually such processes are mn batchwise in order to achieve satisfactory particle size distribution. 

Phenomena at Liquid Interfaces. The area of contact between two phases is called the interface three phases can have only aline of contact, and only a point of mutual contact is possible between four or more phases. Combinations of phases encountered in surfactant systems are L—G, L—L—G, L—S—G, L—S—S—G, L—L, L—L—L, L—S—S, L—L—S—S—G, L—S, L—L—S, and L—L—S—G, where G = gas, L = liquid, and S = solid. An example of an L—L—S—G system is an aqueous surfactant solution containing an emulsified oil, suspended soHd, and entrained air (see Emulsions Foams). This embodies several conditions common to practical surfactant systems. First, because the surface area of a phase iacreases as particle size decreases, the emulsion, suspension, and entrained gas each have large areas of contact with the surfactant solution. Next, because iaterfaces can only exist between two phases, analysis of phenomena ia the L—L—S—G system breaks down iato a series of analyses, ie, surfactant solution to the emulsion, soHd, and gas. It is also apparent that the surfactant must be stabilizing the system by preventing contact between the emulsified oil and dispersed soHd. FiaaHy, the dispersed phases are ia equiUbrium with each other through their common equiUbrium with the surfactant solution. 

Many different combinations of surfactant and protective coUoid are used in emulsion polymerizations of vinyl acetate as stabilizers. The properties of the emulsion and the polymeric film depend to a large extent on the identity and quantity of the stabilizers. The choice of stabilizer affects the mean and distribution of particle size which affects the rheology and film formation. The stabilizer system also impacts the stabiUty of the emulsion to mechanical shear, temperature change, and compounding. Characteristics of the coalesced resin affected by the stabilizer include tack, smoothness, opacity, water resistance, and film strength (41,42). 

An example of liquid/liquid mixing is emulsion polymerization, where droplet size can be the most important parameter influencing product quality. Particle size is determined by impeller tip speed. If coalescence is prevented and the system stability is satisfactory, this will determine the ultimate particle size. However, if the dispersion being produced in the mixer is used as an intermediate step to carry out a liquid/liquid extraction and the emulsion must be settled out again, a dynamic dispersion is produced. Maximum shear stress by the impeller then determines the average shear rate and the overall average particle size in the mixer. 

Many emulsion polymerizations can be described by so-called zero-one kinetics. These systems are characterized by particle sizes that are sufficiently small dial entry of a radical into a particle already containing a propagating radical always causes instantaneous termination. Thus, a particle may contain either zero or one propagating radical. The value of n will usually be less than 0.4. In these systems, radical-radical termination is by definition not rate determining. Rates of polymerization are determined by the rates or particle entry and exit rather than by rates of initiation and termination. The main mechanism for exit is thought to be chain transfer to monomer. It follows that radical-radical termination, when it occurs in the particle phase, will usually be between a short species (one that lias just entered) and a long species. 

Sulfosuccinamates like DTSM or TTSM are used in emulsion polymerization [92-94]. TTSM imparts small particle sizes ( 0.02-0.06 pm) in many systems except vinyl acetate. It can be used in all monomer systems including... 

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. 

The defined size ranges and limits are somewhat arbitrary since there are no specific boundaries between the categories. The transition of size ranges, either from molecular dispersions to colloids or from colloids to coarse dispersions, is very gradual. For example, an emulsion may exhibit colloidal properties, and yet the average droplet size may be larger than 1 pm. This is due to the fact that most disperse systems are heterogeneous with respect to their particle size [1-2]. 

Research on the modelling, optimization and control of emulsion polymerization (latex) reactors and processes has been expanding rapidly as the chemistry and physics of these systems become better understood, and as the demand for new and improved latex products increases. The objectives are usually to optimize production rates and/or to control product quality variables such as polymer particle size distribution (PSD), particle morphology, copolymer composition, molecular weights (MW s), long chain branching (LCB), crosslinking frequency and gel content. 

Models for emulsion polymerization reactors vary greatly in their complexity. The level of sophistication needed depends upon the intended use of the model. One could distinguish between two levels of complexity. The first type of model simply involves reactor material and energy balances, and is used to predict the temperature, pressure and monomer concentrations in the reactor. Second level models cannot only predict the above quantities but also polymer properties such as particle size, molecular weight distribution (MWD) and branching frequency. In latex reactor systems, the level one balances are strongly coupled with the particle population balances, thereby making approximate level one models of limited value (1). 

Particle Size Distribution Determination. To consider the full PSD, a population balance or age distribution analysis on particles must be employed. Table II gives a summary of recent work concerning the determination of PSD s in emulsion systems, using both the "monodispersed" approximation and the population balance approach. More details can be found in the literature sources cited in the Table. 

Deriving an expression for f(t) a considerable simplification occurs if one takes all polymer particles to be nucleated at the same size dp(t,t). The generation of new polymer particles in an emulsion system is basically due to two mechanisms micellar and homogeneous particle production. Then, the rate of particle nucleation, fit), can be expressed as (12) ... 

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