Polymerization parameters, sodium

In an inverse emulsion polymerization, a hydrophilic monomer, frequently in aqueous solution, is emulsified in a continuous oil phase using a water-in-oil emulsifier and polymerized using either an oil-soluble or water-soluble initiator the products are viscous latices comprised of submicroscopic, water-swollen, hydrophilic polymer particles colloidally suspended in the continuous oil phase. The average particle sizes of these latices are as small as 0.05 microns. The technique is applicable to a wide variety of hydrophilic monomers and oil media. The inverse emulsion polymerization of sodium p-vinylbenzene sulfonate initiated by both benzoyl peroxide and potassium persulfate was compared to the persulfate-initiated polymerization in aqueous solution. Hypotheses for the mechanism and kinetics of polymerization were developed and used to calculate the various kinetic parameters of this monomer. 

During polymerization, parameters such as temperature, flow rate, and agitation speed must be controlled carefully to get the right conversion. Polymerization is normally allowed to proceed to about 60% conversion in cold polymerization and 70% in hot polymerization before it is stopped with a terminal agent that reacts rapidly with the free radicals. Common terminal agents include sodium dimethyldithiocarbamate and diethyl hydroxylamine. 

Table 9. The absolute values of k, and kt at 25 °C and their Arrhenius parameters for anionic polymerization of sodium polystyryl in various ethereal solvents...

Table IV. Polymerization Parameters for Sodium Styrenesulfonate in Water-DMSO Mixtures at 70 C...

Only fragmented data are available on polymerization of other methacrylates. Propagation constants and the respective Arrhenius parameters for the homopolymerization of various methacrylates initiated by sodium metallo-organics were reported recently +3,56) and are given in Table 2. 

A molecularly imprinted polypyrrole film coating a quartz resonator of a QCM transducer was used for determination of sodium dodecyl sulphate (SDS) [147], Preparation of this film involved galvanostatic polymerization of pyrrole, in the presence of SDS, on the platinum-film-sputtered electrode of a quartz resonator. Typically, a 1-mA current was passed for 1 min through the solution, which was 0.1 mM in pyrrole, 1 mM in SDS and 0.1 M in the TRIS buffer (pH = 9.0). A carbon rod and the Pt-film electrode was used as the cathode and anode, respectively. The SDS template was then removed by rinsing the MlP-film coated Pt electrode with water. The chemosensor response was measured in a differential flow mode, at a flow rate of 1.2 mL min-1, with the TRIS buffer (pH = 9.0) as the reference solution. This response was affected by electropolymerization parameters, such as solution pH, electropolymerization time and monomer concentration. Apparently, electropolymerization of pyrrole at pH = 9.0 resulted in an MIP film featuring high sensitivity of 283.78 Hz per log(conc.) and a very wide linear concentration range of 10 pM to 0.1 mM SDS. 

To optimize the use of the amorphous sodium titanate powders as catalyst substrates, it is important to fully characterize the ion-exchange properties of the material. Further, the solution properties of the active metal to be loaded onto the support will be an important parameter in the control of the adsorption process. For example, exposure of sodium titanate to a nickel salt solution does not guarantee that nickel will be loaded onto the sodium titanate, or that the nickel, if loaded, will be dispersed on an atomic level. Sodium titanate only behaves as a cation exchange material under certain pH conditions. The solution pH also influences the hydrolysis and speciation of dissolved nickel ions (3), which can form large polymeric clusters or colloidal particles which are not adsorbed by the sodium titanate via a simple ion-exchange process. 

The results of the simulations shown above suggest that the parameter f should be related to the temperature. Greer has studied the extent of polymerization as a function of temperature for living poly(o -methylstyrene) in THF initiated by sodium naphthalide with mole fraction of monomers x = 0.15378, and the mole ratio of initiators to monomers r = 0.0044. Based on their data, simulations were completed. The results are shown in Table 10.2. Thus we obtained the relation between f and temperature as shown in Figure 10.4. As temperature increases, the value of f increases monotonically and the extent of polymerization increases too. 

TABLE 7.2 Ion Pair Rate Constants for Anionic Polymerization of Poly(styryl)sodium in Ethereal Solvents and the Equilihrium Constant and Thermodynamic Parameters for Ion Pair Equilibrium [48]... 

The second approach for improving the processabihty of ICPs is to prepare their colloidal dispersions in water or an appropriate solvent The colloid dispersions of ICPs can be obtained by chemical or electrochemical oxidation of the monomer in the presence of a steric stabihzer [29-31].The key parameter for such synthesis is the choice of an appropriate steric stabihzer which adsorbs or grafts onto the polymer coUoidal particles to prevent their aggregation or precipitation. Several polymers such as polyfethylene oxide) [32], poly(vinyl pyrroHdone) [33,34], poly(vinyl alcohol) [35], ethyl hydroxy cellulose [36], poly(vinyl alcohol-co-acetate) [37], poly(vinyl methyl ether) [38,39] and block copolymer stabihzer [40] have been used as steric stabihzers to produce PPy coUoidal dispersions. Surfactants are also employed for the synthesis of ICP coUoidal dispersions [41,42]. Very recently, stable PPy dispersions were prepared by Lu et al. by polymerizing pyrrole in an aqueous medium containing different anionic salts such as sodium benzoate, potassium hydrogen phthalate, and sodium succinate [43]. These authors also reported that the conductivity of PPy dispersions was enhanced when sodium benzoate was used as dopant. Chemical oxidahve polymerization in the presence of PSS in aqueous medium produces coUoidal dispersions and improves processability [44]. CoUoidal dispersions... 

---