Emulsion processes

The emulsion process can be used to synthesize inorganic and metallic nanoparticles with controlled particle size and morphology [99, lOOj. An emulsion is defined as a colloidal suspension of a hquid within another liquid. Emulsions can be divided into two categories (i) oil-in-water, where the oil droplets are suspended homogeneously in water (the droplets are referred to as micelles) and (ii) water-in-oil, where water droplets are suspended homogeneously in oil, known as reverse micelles. 

a surface-active agent or surfactant may be added to stabilize an emulsion the role of a surface-active agent is to reduce the difference in surface tension between the water and oil such that they form a stable phase in one another. The emulsion process depends heavily on the type of surfactant used, their concentration, and the aqueous-to-organic phase ratio in the hquid medium. 

The commercial production of acryloritrile-butadiene-styrene (ABS) formulations is accomplished by a number of different methods based on free radical polymerization. The two main methods are based on emulsion or solution polymerization techniques. The solution polymerization is mostly called mass or bulk polymerization because only a low amount of solvent is used. Most of the ABS ( 85%) is made using the emulsion process. Both techniques have been used in combination (emulsion/mass). Other combinations are with suspension polymerization as final step (mass/suspension and emulsion/suspen-sion) [1]. 

Although the emulsion process is commercially the most important, the mass process cannot be neglected because it has a number of advantages that will become clear from the more detailed description of both processes. 

Modem Styrenic Polymers Polystyrene and Styrenic Copolymers. Edited by J. Scheirs and D. B. Priddy ( 2003 John Wiley Sons Ltd 

The next step is the polymerization of styrene and acrylonitrile in the presence of the rubber latex. Part of the polymerized styrene-acrylontrile is grafted on to the rubber. This grafted rubber concentrate is then either mixed with additional emulsion-prepared styrene-co-acrylonitrile (SAN) copolymer and then coagulated or first isolated and then compounded with SAN. 

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The fourth and most interesting of the polymerization techniques we shall consider is called emulsion polymerization. It is important to distinguish between suspension and emulsion polymerization, since there is a superficial resemblance between the two and their terminology has potential for confusion A suspension of oil drops in water is called an emulsion. Water-insoluble monomers are used in the emulsion process also, and the polymerization is carried out in the presence of water however, the following significant differences also exist ... 

Inverse emulsion process Inverse soaps Invert molasses Invert sugar... 

Emulsion Process. The emulsion polymerization process utilizes water as a continuous phase with the reactants suspended as microscopic particles. This low viscosity system allows facile mixing and heat transfer for control purposes. An emulsifier is generally employed to stabilize the water insoluble monomers and other reactants, and to prevent reactor fouling. With SAN the system is composed of water, monomers, chain-transfer agents for molecular weight control, emulsifiers, and initiators. Both batch and semibatch processes are employed. Copolymerization is normally carried out at 60 to 100°C to conversions of - 97%. Lower temperature polymerization can be achieved with redox-initiator systems (51). 

Figure 2 shows a typical batch or semibatch emulsion process (52). A typical semibatch emulsion recipe is shown in Table 3 (53). 

The emulsion process can be modified for the continuous production of latex. One such process (68) uses two stirred-tank reactors in series, followed by insulated hold-tanks. During continuous operation, 60% of the monomers are continuously charged to the first reactor with the remainder going into the second reactor. Surfactant is added only to the first reactor. The residence time is 2.5 h for the first reactor where the temperature is maintained at 65°C for 92% conversion. The second reactor is held at 68°C for a residence time of 2 h and conversion of 95%. 

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). 

Emulsion Process. The emulsion (79,80) ABS process involves two steps, production of a mbber latex and subsequent polymerization of styrene and acrylonitrile in the presence of the mbber latex to produce an ABS latex. This latex is then processed to isolate the ABS resin (81,82). 

If a linear mbber is used as a feedstock for the mass process (85), the mbber becomes insoluble in the mixture of monomers and SAN polymer which is formed in the reactors, and discrete mbber particles are formed. This is referred to as phase inversion since the continuous phase shifts from mbber to SAN. Grafting of some of the SAN onto the mbber particles occurs as in the emulsion process. Typically, the mass-produced mbber particles are larger (0.5 to 5 llm) than those of emulsion-based ABS (0.1 to 1 llm) and contain much larger internal occlusions of SAN polymer. The reaction recipe can include polymerization initiators, chain-transfer agents, and other additives. Diluents are sometimes used to reduce the viscosity of the monomer and polymer mixture to faciUtate processing at high conversion. The product from the reactor system is devolatilized to remove the unreacted monomers and is then pelletized. Equipment used for devolatilization includes single- and twin-screw extmders, and flash and thin film evaporators. Unreacted monomers are recovered for recycle to the reactors to improve the process yield. 

Fig. 1. Transmission electron micrograph of ABS produced by an emulsion process. Staining of the mbber bonds with osmium tetroxide provides contrast...

MBS polymers are prepared by grafting methyl methacrylate and styrene onto a styrene—butadiene mbber in an emulsion process. The product is a two-phase polymer useful as an impact modifier for rigid poly(vinyl chloride). 

There are two problems in the manufacture of PS removal of the heat of polymeriza tion (ca 700 kj /kg (300 Btu/lb)) of styrene polymerized and the simultaneous handling of a partially converted polymer symp with a viscosity of ca 10 mPa(=cP). The latter problem strongly aggravates the former. A wide variety of solutions to these problems have been reported for the four mechanisms described earlier, ie, free radical, anionic, cationic, and Ziegler, several processes can be used. Table 6 summarizes the processes which have been used to implement each mechanism for Hquid-phase systems. Free-radical polymerization of styrenic systems, primarily in solution, is of principal commercial interest. Details of suspension processes, which are declining in importance, are available (208,209), as are descriptions of emulsion processes (210) and summaries of the historical development of styrene polymerization processes (208,211,212). 

Polymerization Processes. Vinyl acetate has been polymerized industrially by bulk, solution, suspension, and emulsion processes (34). Perhaps 90% of the material identified as poly(vinyl acetate) or copolymers that are predominantly vinyl acetate are made by emulsion techniques. Detailed information is in patent and scientific Hterature and in procedures available in the brochures from monomer producing companies (15,34). 

Mini-emulsion processes have been developed where the monomer is emulsified under high energy with either a long-chain alcohol or a polymer producing very small droplets. The long-chain alcohol retards the diffusion of the monomer out of the droplets (65). Polymerization takes place primarily... 

Chain transfer to monomer and to other small molecules leads to lower molecular weight products, but when polymerisation occurs ia the relative absence of monomer and other transfer agents, such as solvents, chain transfer to polymer becomes more important. As a result, toward the end of batch-suspension or batch-emulsion polymerisation reactions, branched polymer chains tend to form. In suspension and emulsion processes where monomer is fed continuously, the products tend to be more branched than when polymerisations are carried out ia the presence of a plentiful supply of monomer. 

The low vinyl acetate ethylene—vinyl acetate copolymers, ie, those containing 10—40 wt % vinyl acetate, are made by processes similar to those used to make low density polyethylene for which pressures are usually > 103 MPa (15,000 psi). A medium, ie, 45 wt % vinyl acetate copolymer with mbber-like properties is made by solution polymerisation in /-butyl alcohol at 34.5 MPa (5000 psi). The 70—95 wt % vinyl acetate emulsion copolymers are made in emulsion processes under ethylene pressures of 2.07—10.4 MPa (300—1500 psi). 

FIG. 23-23 Batch and continuous polymerizations, (a) Polyethylene in a tiihiilar flow reactor, up to 2 km long hy 6,4 cm ID, (h) Batch process for polystyrene, (c) Batch-continuous process for polystyrene, (d) Suspension (head) process for polyvinylchloride, (e) Emulsion process for polyvinylchloride, (Ray and Laurence, in Lapidus and Amundson, eds, Chemical Reactor Theory Review, Frentice-Hall, 1977. )... 

Emulsions Emulsions have particles of 0.05 to 5.0 [Lm diameter. The product is a stable latex, rather than a filterable suspension. Some latexes are usable directly, as in paints, or they may be coagulated by various means to produce massive polymers. Figures 23-23d and 23-23 show bead and emulsion processes for vinyl chloride. Continuous emulsion polymerization of outadiene-styrene rubber is done in a CSTR battery with a residence time of 8 to 12 h. Batch treating of emulsions also is widely used. 

To produce the Type 2 polymers, styrene and acrylonitrile are added to polybutadiene latex and the mixture warmed to about 50°C to allow absorption of the monomers. A water-soluble initiator such as potassium persulphate is then added to polymerise the styrene and acrylonitrile. The resultant materials will be a mixture of polybutadiene, polybutadiene grafted with acrylonitrile and styrene, and styrene-acrylonitrile copolymer. The presence of graft polymer is essential since straightforwsird mixtures of polybutadiene and styrene-acrylonitrile copolymers are weak. In addition to emulsion processes such as those described above, mass and mass/suspension processes are also of importance. 

According to the other kinetic model proposed for the soapless emulsion process, the growing macroradicals may also form micelle structures at earlier polymerization times since they have both a hydrophilic end coming from the initiator and a hydrophobic chain [74]. 

The advantages of continuous tubular reactors are well known. They include the elimination of batch to batch variations, a large heat transfer area and minimal handling of chemical products. Despite these advantages there are no reported commercial instances of emulsion polymerizations done in a tubular reactor instead the continuous emulsion process has been realized in series-connected stirred tank reactors (1, . ... 

In the production of polyvinyl chloride by the emulsion process, the percentages of catalyst, wetting agent, initiator, and solvent all affect the properties of the resultant polymer. They must be carefully metered into the reaction vessel. The vinyl chloride used must also be very pure. Either the scope must specify that the purchased raw material shall meet certain specifications, or some purification equipment must be installed so that the required quality can be obtained. 

Fluorescent silica nanoparticles, called FloDots, were created by Yao et al. (2006) by two synthetic routes. Hydrophilic particles were produced using a reverse micro-emulsion process, wherein detergent micelles formed in a water-in-oil system form discrete nanodroplets in which the silica particles are formed. The addition of water-soluble fluorescent dyes resulted in the entrapment of dye molecules in the silica nanoparticle. In an alternative method, dye molecules were entrapped in silica using the Stober process, which typically results in hydrophobic particles. Either process resulted in luminescent particles that then can be surface modified with... 

Liu et al. prepared palladium nanoparticles in water-dispersible poly(acrylic acid) (PAA)-lined channels of diblock copolymer microspheres [47]. The diblock microspheres (mean diameter 0.5 pm) were prepared using an oil-in-water emulsion process. The diblock used was poly(t-butylacrylate)-Wock-poly(2-cinna-moyloxyethyl) methacrylate (PtBA-b-PCEMA). Synthesis of the nanoparticles inside the PAA-lined channels of the microspheres was achieved using hydrazine for the reduction of PdCl2, and the nanoparticle formation was confirmed from TEM analysis and electron diffraction study (Fig. 9.1). The Pd-loaded microspheres catalyzed the hydrogenation of methylacrylate to methyl-propionate. The catalytic reactions were carried out in methanol as solvent under dihydro-... 

The emulsion process, however, competed strongly in the initial phase with the continuous mass polymerization process, one reason being the easier heat removal but the main reason being that high molecular weights were obtained in a simple manner. The process first appeared in the patent literature (19, 20) in 1927 and was further improved by H. Fikentscher (21), finding wide application in the whole field of polymer chemistry. 

First industrial-scale manufacture of SAN polymers in Ludwigshafen (emulsion process). 

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