Heterogeneous polymerization initiation

Reactive radical ions, cations and anions are frequent intermediates in organic electrode reactions and they can serve as polymerization initiators, e.g. for vinylic polymerization. The idea of electrochemically induced polymerization of monomers has been occasionally pursued and the principle has in fact been demonstrated for a number of polymers But it appears that apart from special cases with anionic initiation the heterogeneous initiation is unfavorable and thus not competitive for the production of bulk polymers A further adverse effect is the coating of electrodes... 

Ionic polymerizations, especially cationic polymerizations, are not as well understood as radical polymerizations because of experimental difficulties involved in their study. The nature of the reaction media in ionic polymerizations is often not clear since heterogeneous inorganic initiators are often involved. Further, it is extremely difficult in most instances to obtain reproducible kinetic data because ionic polymerizations proceed at very rapid rates and are extremely sensitive to the presence of small concentrations of impurities and other adventitious materials. The rates of ionic polymerizations are usually greater than those of radical polymerizations. These comments generally apply more to cationic than anionic polymerizations. Anionic systems are more reproducible because the reaction components are better defined and more easily purified. 

Another consideration in the application of the various kinetic expressions is the uncertainty in some reaction systems as to whether the initiator-coinitiator complex is soluble. Failure of the usual kinetic expressions to describe a cationic polymerization may indicate that the reaction system is actually heterogeneous. The method of handling the kinetics of heterogeneous polymerizations is described in Sec. 8-4c. 

Electron-transfer initiation also occurs in heterogeneous polymerizations involving dispersions of an alkali metal in monomer. Initiation involves electron transfer from the metal to monomer followed by dimerization of the monomer radical-anion to form the propagating... 

Lactam polymerizations (nonassisted as well as assisted) are usually complicated by heterogeneity, usually when polymerization is carried out below the melting point of the polymer [Fries et al., 1987 Karger-Kocsis and Kiss, 1979 Malkin et al., 1982 Roda et al., 1979]. (This is probably the main reason why there are so few reliable kinetic studies of lactam polymerizations.) An initially homogeneous reaction system quickly becomes heterogeneous at low conversion, for example, 10-20% conversion (attained at a reaction time of no more than 1 min) for 2-pyrrolidinone polymerization initiated by potassium t-butoxide and A-benzoyl-2-pyrrolidinone. The (partially) crystalline polymer starts precipitating from solution (which may be molten monomer), and subsequent polymerization occurs at a lower rate as a result of decreased mobility of /V-acyl lactam propagating species. 

The work described here was undertaken on the premise that measurements of the number of particles, total particle surface, and concentration of trapped radicals are needed in conjunction with rate measurements over a wide range of initiation rate and monomer concentration to understand more thoroughly the important factors in this type of heterogeneous polymerization. However, as will become apparent from the results reported here, variations in particle number and total surface are small and have little effect on the polymerization rate. Under our conditions trapped radicals were present in too low a concentration to be detected and cannot account for the peculiar features of the reaction kinetics. 

The rate of polymerization in the constant rate period is shown in Figure 5 as a function of AIBN concentration, both on logarithmic scales. At low concentrations of initiator (I) the rate varies as I0 89, but the slope drops as low as 0.33 at high rates of initiation. Similar results have been reported by Chapiro and Sebban-Danon (12) for polymerizations initiated by ionizing radiation at 19 °C. Initiator exponents significantly higher than the normal value of 0.5 have been reported by many workers (6, 10, 17, 25, 30, 31) for the polymerization of acrylonitrile under heterogeneous conditions. 

The preceding discussion has led us to the conclusion that the surface is the only locus of polymerization which needs to be considered in the heterogeneous polymerization of acrylonitrile. Radicals arrive at the surface at a rate determined by the decomposition of the initiator and efficiency of initiation. Propagation occurs on the surface at a rate determined by the activity of monomer at the surface. By analogy with emulsion polymerization, where monomer diffuses into the particles rapidly enough to maintain near equilibrium activity (14), we assume that the activity of the monomer adsorbed on the particle surface is approximately equal to the mole fraction in solution. The propagation rate constant is presumably influenced somewhat by the presence of the solid surface. 

The various latexes were characterized with respect to particle size and size distribution, surface charge and functional group density, and electrophoretic mobility behavior. As observed by transmission electron microscopy all latexes were found highly monodisperse with a uniformity ratio between 1.001 and 1.010, a property due to the short duration of the nucleation period involved in the various radical-initiated heterogeneous polymerization processes. The surface charge density was determined by a colorimetric titration method reported elsewhere [13]. 

Heterogeneous polymerizations proceed in two or more phases. Heterogeneity may be caused by the presence of a solid or of a gaseous phase or else the liquid monomer may be dispersed in another liquid with which it does not dissolve. Very important are the systems (a) with a solid initiator and (b) of two practically immiscible liquids. The former is useful for producing stereospecific polymers which are usually formed by a coordination mechanism. The latter makes possible an elegant and efficient removal of the heat of polymerization and it is applied technically with radical polymerizations in suspension or emulsion. 

The peroxy initiators bis(perfluoro-2-Ar-propoxypropionyl) peroxide (BPPP) and diethyl peroxydicarbonate (DEPDC) have had the greatest application in the heterogeneous polymerization of fluoroolefins in CO2. 

The observed increase of the yields cannot be explained only by an increase of the initiation rate. If all the energy dissipated into the solid is quantitatively used for the initiation process through a solid-gas transfer phenomenon, and if the heterogeneous polymerization mechanism is the same as the homogeneous one, the G pp cannot exceed largely the Ghom. 

Another aqueous heterogeneous polymerization was recently reported for the precipitation polymerization of MMA and styrene complexed with methylated /3-cyclodextrin.256 The polymerization was carried out in water with 1-21 (X = Br)/CuBr/L-4 to give polymers with controlled molecular weights and relatively narrow MWDs (MJMn = 1.3—1.8). Initially, the reaction mixture was homogeneous with the hydrophilic cyclodextrin-complexed MMA, but sooner or later it became heterogeneous due to the formation of water-insoluble polymers. 

The classic Ziegler-Natta heterogeneous catalysts initiate polymerization at diverse, somewhat randomly scattered active sites on modified TiCls crystals, with the result that polymer chain length is variable even though essentially complete isotacticity can be achieved. Furthermore, these catalysts offer little opportunity to manipulate the degree of stereoregularity and hence the mechanical properties of the product—the Ziegler-Natta polypropylenes are exclusively isotactic. 

A well-defined monodisperse penta(L-alanine)- -butylamide H-[Ala]5-NHBu was synthesized by an activated ester method " and other natural abundant polypeptides, [Ala]n-5, [Leu]n-1 and [Leu]n-2, were synthesized by the N-carboxy a-amino-acid anhydride (NCA) method.Fully N-labelled homopolypeptides, [Ala ]n (99 at.% of N purity MASSTRACE, Inc.) and [Leu ]n (99 at.% of N purity MASSTRACE, Inc.), which show characteristic differences in conformation such as the a-helix and /3-sheet forms, were prepared by the heterogeneous polymerization of the corresponding NCAs in acetonitrile with -butylamine as an initiator. Conformational characterization of these samples was made on the basis of the conformation-dependent C and chemical shifts determined from the CP-MAS NMR method and from the characteristic bands in the IR and far-IR spectra. Figs. 38 and 39 show the 75.5 MHz C and 30.4 MHz N CP-MAS NMR spectra respectively of these fully N-labelled (99 at.% purity of N) homopolypeptides adopting the a-helical and /3-sheet forms (A) [Ala ]n-2 (a-helix), (B) [Ala ]n-1 (/3-sheet), (C) [Leu ]n-2 (a-helix), (D) [Leu ]n-1 (/3-sheet) in the solid state. Synthetic conditions and conformational characteristics of these samples are summarized... 

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