Monomer phase

Initiators of suspension polymerization are organic peroxides or azo compounds that are soluble in the monomer phase but insoluble in the water phase. The amount of initiator influences both the polymerization rate and the molecular weight of the product (95). 

When initiator is first added the reaction medium remains clear while particles 10 to 20 nm in diameter are formed. As the reaction proceeds the particle size increases, giving the reaction medium a white milky appearance. When a thermal initiator, such as AIBN or benzoyl peroxide, is used the reaction is autocatalytic. This contrasts sharply with normal homogeneous polymerizations in which the rate of polymerization decreases monotonicaHy with time. Studies show that three propagation reactions occur simultaneously to account for the anomalous auto acceleration (17). These are chain growth in the continuous monomer phase chain growth of radicals that have precipitated from solution onto the particle surface and chain growth of radicals within the polymer particles (13,18). 

Divinylbenzene copolymers with styrene are produced extensively as supports for the active sites of ion-exchange resins and in biochemical synthesis. About 1—10 wt % divinylbenzene is used, depending on the required rigidity of the cross-linked gel, and the polymerization is carried out as a suspension of the monomer-phase droplets in water, usually as a batch process. Several studies have been reported on the reaction kinetics (200,201). 

Polymerization in two phases, the Hquid monomer phase and the swollen polymer gel phase, forms the basis for kinetic descriptions of PVC polymerization (79—81). The polymerization rate is slower in the Hquid monomer phase than in the swoUen polymer gel phase on account of the greater mobiHty in Hquid monomer, which allows for greater termination efficiency. The lack of mobiHty in the polymer gel phase reduces termination and creates a higher concentration of radicals, thus creating a higher polymerization rate. Thus the polymerization rate increases with conversion to polymer. 

The most important feature of o/w suspension polymerization is the formation of an oil droplet suspension of the monomer in the water and the maintenance of the individual droplets throughout the polymerization process. Droplet formation in an oil-in-water mixture is accomplished and controlled by two major factors mechanical stirring and the volume ratio of the monomer phase to water. The stirring speed is a key factor in controlling the size of oil droplets and the final size of the polymers. The stirring speed usually needs to be over... 

Beaded polymeric supports are produced by a two-phase suspension polymerization in which microdrops of a monomer solution are directly converted to the corresponding microbeads. The size of a microdroplet is usually determined by a number of interrelated manufacturing parameters, which include the reactor design, the rate of stirring, the ratio of the monomer phase to water, the viscosity of both phases, and the type and concentration of the droplet stabilizer. 

In addition to monomers and the initiator, an inert liquid (diluent) must be added to the monomer phase to influence the pore structure and swelling behavior of the beaded resin. The monomer diluent is usually a hydrophobic liquid such as toluene, heptane, or pentanol. It is noteworthy that the namre and the percentage of the monomer diluent also influence the rate of polymerization. This may be mainly a concentration or precipitation effect, depending on whether the diluent is a solvent or precipitant for the polymer. For example, when the diluent is a good solvent such as toluene to polystyrene, the polymerizations proceed at a correspondingly slow rate, whereas with a nonsolvent such as pentanol to polystyrene the opposite is true. 

Monomer-soluble initiators are used in this polymerization technique. The monomer phase containing an initiator is dissolved in an inert solvent or solvent mixture including a steric stabilizer. The polymers or oligomer... 

Soapless seeded emulsion copolymerization has been proposed as an alternative method for the preparation of uniform copolymer microspheres in the submicron-size range [115-117]. In this process, a small part of the total monomer-comonomer mixture is added into the water phase to start the copolymerization with a lower monomer phase-water ratio relative to the conventional direct process to prevent the coagulation and monodispersity defects. The functional comonomer concentration in the monomer-comonomer mixture is also kept below 10% (by mole). The water phase including the initiator is kept at the polymerization temperature during and after the addition of initial monomer mixture. The nucleation takes place by the precipitation of copolymer macromolecules, and initially formed copolymer nuclei collide and form larger particles. After particle formation with the initial lower organic phase-water ratio, an oligomer initiated in the continuous phase is... 

The pore volume and the specific surface area of the uniform macroporous particles increased and the average pore size decreased with the increasing divinylbenzene concentration within the monomer phase. 

Polymerization until the separate monomer phase is consumed... 

Volume of Monomer and Particle Phases. Additional time dependent differential equations were written for the volumes of the particle and aqueous phases. The volume of the monomer phase was calculated from the total emulsion volume and the volumes of the aqueous and polymer phases. This procedure allowed the determination of whether monomer droplets are present (Interval II) or absent (Interval III). 

In an emulsion polymerization, the reaction mixture is initially heterogeneous due to the poor solubility of the monomer in the continuous phase. In order for a reaction to take advantage of the desirable Smith-Ewart kinetics [96], the monomer and initiator must be segregated with the initiator preferentially dissolved in the continuous phase and not the monomer phase. Because of the kinetics of an emulsion polymerization, high molecular weight polymer can be produced at high rates. The polymer which results from an emulsion polymerization exists as spherical particles typically smaller than one pm in diameter. However, due to the high solubility of most vinyl monomers in C02, emulsion polymerization in C02 probably will not be a very useful process for commercially important monomers. 

Liquid-molding resins, based on poly(dicyclopentadiene), 20 432 Liquid monomer phase, in PVC polymerization, 25 667 Liquid NaK alloy, 20 603. See also NaK entries... 

Second example was obtained from the copolymerization initiated with starch. The results were shown in Fig. 12. The copolymer isolated from the monomer phase was produced by the thermal polymerization and the composition curve was completely similar to the ordinary curve of the radical copolymerization product. The copolymer isolated from the water phase differed from the usual copolymer. The upper curve indicated that the HA formed by starch were soft, and soft MMA was much more easily incorporated than hard St. 

At CMC, micelles (aggregates of SD" with some counterions, such as Na+) are formed, and some Na+ ions are bound to these, which is also observed from conductivity data. In fact, these data analyses have shown that approximately 70% Na+ ions are bound to SD" ions in the micelle. The surface charge was estimated from conductivity measurements (Birdi, 2002). Therefore, the concentration of Na+ will be higher than SD" ions after CMC. A large number of reports are found in the literature, in which the transition from the monomer phase (before CMC) to the micellar phase (after CMC) have been analyzed. 

HRP/IL phase. The electrical conductivity of the PANI films prepared by solvent casting from the aqueous solutions showed a relatively high and similar value even after the fifth run (Fig. 12), which demonstrates the validity of our approach and the ease of recyclability and reuse of the enzyme inside the IL. For the PEDOT, the process of recovery and reuse was successfully repeated up to ten times using the same HRP/EDOT catalytic phase (Fig. 13), further confirming the success of the synthetic approach and the ease of recyclability and reuse of the enzyme inside the EDOT monomer phase. 

In the crystal structure of the polymer phase (Fig. 17a), the polymer chains are aligned along the c-axis and the distance (3.71 A) between the centres of adjacent cyclobutane and pyrazine rings corresponds to half the c-axis repeat of the unit cell. For comparison between the monomer and polymer structures, an overlay plot of these structures is shown in Fig. 17b. It is clear that the solid-state reaction is associated with only very small atomic displacements at the site of the [2-1-2] photocyclization reaction (the displacement of the carbon atoms of the C=C double bonds of monomer molecules on forming the cyclobutane ring of the polymer is only ca. 0.8 A for one pair of carbon atoms and ca. 1.6 A for the other pair). Such small displacements are completely in accord with the assignment of this solid-state reaction as a topochemical transformation [124—127] (in which the crystal structure of the reactant monomer phase imposes geometric control on the pathway of the... 

The mixture CMC is plotted as a function of monomer composition in Figure 1 for an ideal system. Equation 1 can be seen to provide an excellent description of the mixture CMC (equal to Cm for this case). Ideal solution theory as described here has been widely used for ideal surfactant systems (4.6—18). Equation 2 can be used to predict the micellar surfactant composition at any monomer surfactant composition, as illustrated in Figure 2. This relation has been experimentally confirmed (ISIS) As seen in Figure 2, for an ideal system, if the ratio XA/yA < 1 at any composition, it will be so over the entire composition range. In classical phase equilibrium thermodynamic terms, the distribution coefficient between the micellar and monomer phases is independent of composition. 

Assuming that the CMC is small, so that the activity coefficients may be neglected, the monomer phase chemical potentials are given by Equations 9-11. 

Figure 2. CMC s for 3((>Cxo/Nl E50 mixtures variation of the mixture critical micelle concentration with monomer phase composition for mixtures of decyl benzene sulfonate with a nonyl phenol ethyoxy-late having an ethylene oxide chain length of 50, at 27 °C.

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