Emulsion polymerization particle size distribution

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. 

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. 

ABS compositions with bimodal particle size distributions of the grafted rubber can be prepared by emulsion graft polymerization techniques. The preparation of ABS types by emulsion polymerization consists in brief of (13) ... 

The emulsion free-radical polymerization carried out in different steps ensures a precise control of the particle size and particle size distribution. The particle diameter can be adjusted between 100 nm and 1000 nm, with a low polydispersity (generally less than 1.1) (Chapter 8). Rubber particles with sizes lower than 100 nm are ineffective for toughening purposes (Sec. 13.3.2b). 

In 1952 W. J. Priest, in an important paper, laid out all of the basic qualitative features of the theory of homogeneous nucleation in emulsion polymerization as it is known today (12). This was based upon his studies of particle size distributions in vinyl acetate polymerization initiated by potassium persulfate (K2S20g) in the presence of varying amounts of different stabilizers and inhibitors at several temperatures. Priest proposed that (1) "polymerization in solution is the initial process" ... 

This work has shown that by monitoring conversion curves by a computer, emulsifier metering can be varied to produce a desired particle size distribution of smalls in a seeded PVC emulsion polymerization. 

For example, the particle size distribution in emulsion, suspension, and precipitation polymerization can be a crucial product specification. One of the greatest difficulties in achieving quality control of the polymer product is that the actual customer specifications may be in terms of non-molecular parameters such as tensile strength, crack resistance, temperature stability, color or clarity, absorption capacity for plasticizer, etc. 

Synthesis. A series of latexes was prepared by semicontinuous emulsion polymerization of methyl methacrylate. A dialkyl ester of sodium sulfosuccinic acid surfactant yielded the narrow particle size distribution required. An ammonium persulfate/sodium metabisulfate/ferrous sulfate initiator system was used. The initiator was fed over the polymerization time, allowing better control of the polymerization rate. For the smaller size latexes (200 to 450 nm), a seed latex was prepared in situ by polymerizing 10% of the monomer in the presence of the ammonium persulfate. Particle size was adjusted by varying the level of surfactant during the heel reaction. As the exotherm of this reaction subsided, the monomer and the sodium metabisulfate/ferrous sulfate feeds were started and continued over approximately one hour. The... 

Poehlein and Degraff [336] extended the derivation of Gershberg and Long-field [330] to the calculation of both molecular weight and particle size distribution in the continuous emulsion polymerization of St in a CSTR. On the other hand, Nomura et al. [163] carried out the continuous emulsion polymerization of St in a cascade of two CSTRs and developed a novel model for the system by incorporating their batch model [ 14], which introduced the concept that the radical capture efficiency of a micelle relative to a polymer particle was much lower than that predicted by the diffusion entry model (pocd -°). The assumptions employed were almost the same as those of Smith and Ewart (Sect. 3.3), except that the model did not assume a constant value of p. The elementary reactions and their rate expressions employed in the first stage are as follows ... 

One of the methods for preparing monodispersed latices, i.e. latices of uniform particle size distribution, is to use mixed surfactants as the emulsifier in the emulsion polymerization process. The term mixed surfactants, in general, refers to mixtures of ionic and nonionic surfactants. 

Besides giving latices of narrow particle size distribution, mixed surfactant systems have shown several other interesting characteristics which lighten some aspects concerning the mechanism of particle nucleation in emulsion polymerization process. 

From mixed surfactant systems of emulsion polymerization, monodispersed latices were usually obtained at fairly low conversions with rather wide variations in emulsifier compositions (j ). Therefore, samples for the determination of the particle size distribution in this system should be taken at relatively low conversions, otherwise, monodispersed latices will be obtained due to competitive growth from all samples regardless of the surfactant ratios in the recipe of polymerization. These particles will be different in size, but not in size distribution. 

We hav shown that with the use of a mixed surfactant system in styrene emulsion polymerization, the composition of the mixed surfactant has an effect on the rate of polymerization, the number of particles formed and the particle size distribution. We have also shown that a change in the ratio, r of the two surfactants in the mixture results in a considerable change in the micellar weight of the resultant mixed micelles. We have thus proposed and proven that the efficiency of nucleation of particles (even when the same number of micelles is used in the experiment) is dependent on the size of the mixed micelle, and that there is an optimum size at which the polymerization rate is the fastest and the particle size distribution is the narrowest. 

Particle Size Distribution (Ratio of Volume to Number Average) for Polyvinyl Chloride Latices Produced by Radiation Induced Emulsion Polymerization... 

The data on particle size distributions for both PVA and PMMA emulsions suggest that small particles could be quite important in the kinetic scheme, and that the larger particles probably grow by internal polymerization and by flocculation with smaller particles. The experiments with the tubular reactor installed upstream of the CSTR demonstrate a practical way to eliminate uncontrolled transients with continuous systems. We believe that the particles generated in the tube prevent CSTR oscillations by avoiding the unstable particle formation reactions in the CSTR. Berrens (8 ) accomplished the same results by using a particle seed in the feed stream to a CSTR with PVC emulsion polymerizations. 

Polystyrene can be easily prepared by emulsion or suspension techniques. Harkins (1 ), Smith and Ewart(2) and Garden ( ) have described the mechanisms of emulsTon polymerization in batch reactors, and the results have been extended to a series of continuous stirred tank reactors (CSTR)( o Much information on continuous emulsion reactors Ts documented in the patent literature, with such innovations as use of a seed latex (5), use of pulsatile flow to reduce plugging of the tube ( ), and turbulent flow to reduce plugging (7 ). Feldon (8) discusses the tubular polymerization of SBR rubber wTth laminar flow (at Reynolds numbers of 660). There have been recent studies on continuous stirred tank reactors utilizing Smith-Ewart kinetics in a single CSTR ( ) as well as predictions of particle size distribution (10). Continuous tubular reactors have been examined for non-polymeric reactions (1 1 ) and polymeric reactions (12.1 31 The objective of this study was to develop a model for the continuous emulsion polymerization of styrene in a tubular reactor, and to verify the model with experimental data. 

Emulsion polymerizations normally produce polymer particles with diameters ofO.I-l pm(l pm= I micron= 10 cm), although much larger particles can be made by special techniques mentioned in Chapter 8. Tlie polymer particles made by suspension reactions have diameters in the range of 50-500 pm. Recall that free-radical initiation in suspension reactions is in the monomer phase, whereas the aqueous phase is the initiation site in emulsion polymerizations. The two processes often dilTer also in the types of stabilizers that are used. Microsuspension polymerization is an alternative technique which can yield particles in the same size range as emulsion processes. This method uses a monomer-soluble initiator and anionic emulsifiers similar in nature and concentration to those used in emulsion polymerizations. A microdispersion of the mixture of the reaction ingredients is first produced mechanically and is then polymerized to provide polymer with essentially the initial fine particle size distribution. 

Emulsion polymerization reactors are made of stainless steel and are normally equipped with top-entry stirrers and ports for addition of reactants. Control of the reaction exotherm and particle size distribution of the polymer latex is achieved most readily by semibatch (also called semicontinuous) processes, in which some or all of the reactants are fed into the reactor during the course of the polymerization. Examples are given in Chapter 8. In vinyl acetate copolymerizations, a convenient monomer addition rate is such that keeps the vinyl acetate/water azeotrope retluxing. at about 70°C. 

The technique of emulsion polymerization is characterized by the formation of the polymer in the form of a latex. The particle size distribution (PSD) of the latex and the molecular weight distribution (MWD) of the contained polymer are two important measurable parameters of the latex. Not only do they influence the end-use behavior of the product, but they also reflect the growth history of the emulsion polymerization process. In what follows, we review the theories that have been developed to describe the PSD and MWD-of emulsion polymers. 

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