Emulsion polymerization 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). 

Even though the chemical reactions are the same (i.e. combination, disproportionation), the effects of compartmentalization are such that, in emulsion polymerization, particle phase termination rates can be substantially different to those observed in corresponding solution or bulk polymerizations. A critical parameter is n, the average number of propagating species per particle. The value of h depends on the particle size and the rates of entry and exit. 

The effect of surfactant structures and properties on emulsion polymerization have been investigated by numerous authors [82-89]. Efforts were made to study the effects of surfactants with different molecular weights on the rate of polymerization [82], swelling and solubilization effects [83], effects of alkyl chain length of homologous series on the rate of polymerization, particle size... 

Using the so-called two-step process [15, 16], polymer nanoparticles are first synthesized via emulsion polymerization. The size of the resulting nanoparticles can be tuned by a simple process parameter and covers a range of about 30-400 nm. In a second step these nanoparticles are used to coat microbubbles in a controlled bubble formation process. The nanoparticles migrate to the surface of the bubbles (this is related to the interface activity of hydrophobic nanoparticles in general) and build a monolayer around the bubbles. Consequently, the size of the nanoparticles determines the shell thickness of the final microcapsules. Additionally, a carefully chosen nanoparticle concentration regime results in a certain microcapsule size distribution. In principle, particle sizes in the range of 0.5-10 jum can be adjusted and the microcapsule size distributions are ex-... 

Although the well-defined water-resistant metal-alkylidene complexes do not dissolve in water, they can be used in emulsion polymerizations. Small size polymer particles and polymer latex can be prepared with this method in aqueous media in the presence of cationic surfactants (e.g., Dode cyltrimethylammonium bromide (DTAB)). Water-soluble, biologically active glycopolymers have been also synthesized with ruthenium-alkylidene complexes in... 

The production of organic polymeric particles in tire size range of 30-300 nm by emulsion polymerization has become an important teclmological application of surfactants and micelles. Emulsion polymerization is very well and extensively reviewed in many monographs and texts [67, 68], but we want to briefly illustrated tire role of micelles in tliis important process. 

Figure 6.10 Schematic representation of the distribution of surfactant in an emulsion polymerization. Note the relative sizes of suspended particles. [From J. W. Vanderhoff, E. B. Bradford, H. L. Tarkowski, J. B. Shaffer, and R. M. Wiley,Chem. 34 32(1962).]...

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. 

Emulsion Polymerization. When the U.S. supply of natural mbber from the Far East was cut off in World War II, the emulsion polymerization process was developed to produce synthetic mbber. In this complex process, the organic monomer is emulsified with soap in an aqueous continuous phase. Because of the much smaller (<0.1 jira) dispersed particles than in suspension polymerization and the stabilizing action of the soap, a proper emulsion is stable, so agitation is not as critical. In classical emulsion polymerization, a water-soluble initiator is used. This, together with the small particle size, gives rise to very different kinetics (6,21—23). 

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. 

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. 

Monosized polystyrene particles in the size range of 2-10 /am have been obtained by dispersion polymerization of styrene in polar solvents such as ethyl alcohol or mixtures of alcohol with water in the presence of a suitable steric stabilizer (59-62). Dispersion polymerization may be looked upon as a special type of precipitation polymerization and was originally meant to be an alternative to emulsion polymerization. The components of a dispersion polymerization include monomers, initiator, steric stabilizer, and the dispersion medium... 

A new process, from Norway, has filled the size gap between emulsion and suspension polymerization techniques [7,8]. This novel polymerization method, the so-called swollen emulsion polymerization has been developed by Ugelstad for producing uniform polymeric particles in the size range of 2-100 /nm. This process comprises successive swelling steps and repolymerizations for increasing the particle size of seed polymer particles by keeping the monodispersity of the seed latex. 

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