Polymerization particle producing type

Our final goal in the present paper is to devise an optimal type of the first stage reactor and its operation method which will maximize the number of polymer particles produced in continuous emulsion polymerization. For this purpose, we need a mathematical reaction model which explains particle formation and other kinetic behavior of continuous emulsion polymerization of styrene. 

There are four main types of liquid-phase heterogeneous free-radical polymerization microemulsion polymerization, emulsion polymerization, miniemulsion polymerization and dispersion polymerization, all of which can produce nano- to micron-sized polymeric particles. Emulsion polymerization is sometimes called macroemulsion polymerization. In recent years, these heterophase polymerization reactions have become more and more important... 

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. 

In emulsion polymerization, monomers are polymerized in the form of emulsions and polymerization in most cases involve free-radical reactions. Like suspension polymerization, the emulsion process uses water as the medium. Polymerization is much easier to control in both these processes than in bulk systems because stirring of the reactor charge is easier due to lower viscosity and removal of the exothermic heat of polymerization is greatly facilitated with water acting as the heat sink. Emulsion polymerization, however, differs from suspension polymerization in the nature and size of particles in which polymerization occurs, in the type of substances used as initiators, and also in mechanism and reaction characteristics. Emulsion polymerization normally produces polymer particles with diameters of 0.1-3//. Polymer nanoparticles of sizes 20-30 nm are produced by microemulsion polymerization (Antonietti et al., 1999 Ytldiz et al., 2003). 

The final section Part IV is concerned with physical properties of polymeric nanocomposites (PNCs). Two types of nanoparticles, leading to two different characters and applicabilities of PNC, are discussed layered silicates (with natural or synthetic clays), used in structural-type PNCs and the others used in functional PNCs. Sender et al. in Chapter 13 describe the performance of PNCs with acicular ferroelectric particles producing PNCs with good electroactive (dc conductivity) and mechanical properties. In Chapter 15, Nicolais and Carotenuto focus on metal clusters in polymeric matrices, which combine optical transparency with magnetism, luminescence. Ultraviolet-visible absorption, thermochromism, and so on. 

Most commercial processes use this type of polymerization to produce small uniform capsules in the range of 20-30 micron diameter however, the process can be tuned to produce large microcapsules. The size of these microcapsules and the properties of the wall material/polymer matrix can be altered by using different monomers, utilizing additives, and adjusting reaction conditions. The encapsulation occurs by wall formation around the dispersed core material via the rapid polymerization of monomers at the surface of the droplets or particles. The solution of a multifunctional monomer in the core material is dispersed in an aqueous phase. The polymerization is commenced at the surfaces of the core droplets forming the capsule walls, by adding a reactant to the monomer dispersed in the aqueous phase. 

In contrast to these oil-in-water emulsions, it is possible that the emulsion polymerization can also be carried out with inverse emulsions. Inverse (water-in-oil) emulsion polymerization in which an aqueous solution of a water miscible hydrophilic monomer such as acrylamide, acrylic add, or methacrylic acid is dispersed in a continuous hydrophobic oil phase with the aid of a water-in-oil emulsifier such as sorbitan mono-oleate or -stearate. The emulsifier is ordinarily above the CMC. Polymerization can be initiated with either oil-soluble or water-soluble initiators. If an oil-soluble initiator is used, the system is an almost exact mirror-image of a conventional emulsion polymerization system. The final latex is a colloidal dispersion of submicroscopic, water-swollen particles in oil. This type of emulsion pol3unerization enables the preparation of high molecular weights water-soluble polymers at rapid reaction rates. It is also possible that the water-swollen polymer particles produced by this emulsion pol)nnerization transfer to aqueous phase rapidly by inversion of the latex. 

Definitive data on nucleation of colloidal silica particles in brine solutions at pH 4.5-5.5 and 95°C have been obtained by Makrides and associates in a study related to the deposition of silica from hot geothermal waters (106d). Their work showed conclusively that a solution of monosilicic acid requires an induction period for the formation of nuclei that strongly depends on the degree of supersaturation. Under these conditions appreciable time is required for the early stages of polymerization to produce three-dimensional polymer particles of the type that can function as nuclei. With a supersaturation ratio of 2-3. the nucleation time ranged from a few minutes to several hours. 

Figure 4.3 shows several types of morphologies of the particles produced. The incompatibility of the seed polymer with the newly formed polymer results in phase separation and cluster formation. The size of the clusters increases by both polymerization and cluster aggregation. In addition, the clusters tend to reach an equilibrium morphology, which minimizes the interfacial energy of the system and depends on the polymer-polymer and polymer-water interfacial tensions [40-44]. 

Activation and functionalisation of polymeric particles can be carried out to produce liquid chromatography adsorbents with a range of functionalities. The type of chemistries employed will depend upon the chemical nature of the polymer and the required final product functionalities. Covalent attachment may be carried out, as is required for core shell grafts or coatings applied which may or may not be further derivatised. In all cases it is essential that the derivative is stable to the chromatographic conditions employed and any clean up procedures used. 

Processes for HDPE with Broad MWD. Synthesis of HDPE with a relatively high molecular weight and a very broad MWD (broader than that of HDPE prepared with chromium oxide catalysts) can be achieved by two separate approaches. The first is to use mixed catalysts containing two types of active centers with widely different properties (50—55) the second is to employ two or more polymerization reactors in a series. In the second approach, polymerization conditions in each reactor are set drastically differendy in order to produce, within each polymer particle, an essential mixture of macromolecules with vasdy different molecular weights. Special plants, both slurry and gas-phase, can produce such resins (74,91—94). 

A typical recipe for batch emulsion polymerization is shown in Table 13. A reaction time of 7—8 h at 30°C is requited for 95—98% conversion. A latex is produced with an average particle diameter of 100—150 nm. Other modifying ingredients may be present, eg, other colloidal protective agents such as gelatin or carboxymethylcellulose, initiator activators such as redox types, chelates, plasticizers, stabilizers, and chain-transfer agents. 

Several components of the organic phase contribute greatly to the character of the final product. The pore size of the gel is chiefly determined by the amount and type of the nonsolvent used. Dodecane, dodecanol, isoamyl alcohol, and odorless paint thinner have all been used successfully as nonsolvents for the polymerization of a GPC/SEC gel. Surfactants are also very important because they balance the surface tension and interfacial tension of the monomer droplets. They allow the initiator molecules to diffuse in and out of the droplets. For this reason a small amount of surfactant is crucial. Normally the amount of surfactant in the formula should be from 0.1 to 1.0 weight percent of the monomers, as large amounts tend to emulsify and produce particles less than 1 yam in size. 

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