Monomer diffusion

The surfactant is initially distributed through three different locations dissolved as individual molecules or ions in the aqueous phase, at the surface of the monomer drops, and as micelles. The latter category holds most of the surfactant. Likewise, the monomer is located in three places. Some monomer is present as individual molecules dissolved in the water. Some monomer diffuses into the oily interior of the micelle, where its concentration is much greater than in the aqueous phase. This process is called solubilization. The third site of monomer is in the dispersed droplets themselves. Most of the monomer is located in the latter, since these drops are much larger, although far less abundant, than the micelles. Figure 6.10 is a schematic illustration of this state of affairs during emulsion polymerization. 

Figure 9 The schematical representation of dispersion polymerization process, (a) initially homogeneous dispersion medium (b) particle formation and stabilizer adsorption onto the nucleated macroradicals (c) capturing of radicals generated in the continuous medium by the forming particles and monomer diffusion to the forming particles (d) polymerization within the monomer swollen latex particles, (e) latex particle stabilized by steric stabilizer and graft copolymer molecules (f) list of symbols.

The effect of temperature on the kinetics of the direct radiation method is quite complex. Increase in temperature increases the monomer diffusion rate but also increases transfer and termination reaction rates of the growing chains and reduces the importance of the gel effect. Solubility and radical mobility may also change as the temperature is varied [88,89]. 

For the analysis of the role of monomer diffusion during ethylene polymerization while forming a solid polymer a model of the polymer grain (see Fig. 2) has been suggested (95). This model is consistent with the results of the study of nascent morphology of the polymer and its porosity (95, 100, 103). According to this model three levels are considered in the analysis of transport phenomena. 

Fig. 2. Models of the primary particle (a) and polymer grain (b) for the analysis of the role of monomer diffusion to tbe catalyst surface, (a) 1—catalyst 2—polymer film, (b) 1—micrograin 2—macropore.

Polymerizations often give such high viscosities that laminar flow is inevitable. A t5rpical monomer diffusivity in a polymerizing mixture is 1.0 X 10 ° m/s (the diffusivity of the polymer will be much lower). A pilot-scale reactor might have a radius of 1 cm. What is the maximum value for the mean residence time before molecular diffusion becomes important What about a production-scale reactor with R= 10 cm ... 

The theory of radiation-induced grafting has received extensive treatment [21,131,132]. The typical steps involved in free-radical polymerization are also applicable to graft polymerization including initiation, propagation, and chain transfer [133]. However, the complicating role of diffusion prevents any simple correlation of individual rate constants to the overall reaction rates. Changes in temperamre, for example, increase the rate of monomer diffusion and monomer... 

First, the water soluble initiator decomposes to form free radicals in the aqueous phase. These free radicals then add to comonomers dissolved in the aqueous phase to start a free radical oligomer chain. If the monomers are present to a greater concentration than the saturation concentration, they form a separate comonomer droplet phase. This phase then acts as a reservoir to feed the polymerization which occurs in the polymer (latex) particles. Monomers diffuse into the aqueous phase, diffuse into the polymer particles, and polymerize. 

Radical Desorption Rate. It is evaluated, according to the law proposed by Nonura (36), as the result of three stages in series Chain transfer of a growing chain to monomer, diffusion of the active, low molecular weight product to the particle surface and diffusion in the aqueous phase. The resulting expression has been extended to the multlconponent case as follows ... 

Particular attention was placed on the crossover from segmental diffusion to the center of mass diffusion at Q 1/Rg and to the monomer diffusion at Q /i, respectively, by Higgins and coworkers [119,120]. While the transition at small Q is very sharp (see Fig. 43, right side), a broader transition range is observed in the regime of larger Q, where the details of the monomer structure become important (see Fig. 44). The experimental data clearly show that only in the case of PDMS does the range 2(Q) Q3 exceed Q = 0.1 A-1, whereas in the case of PS and polytetrahydrofurane (PTHF) it ends at about Q = 0.06-0.07 A-1. Thus, the experimental Q-window to study the internal dynamics of these polymers by NSE is rather limited. 

Fig. 44. Double logaritmic plot of Q(Q)/Q2 vs. Q for various dilute solutions under good solvent conditions visualize the crossover from segmental to monomer diffusion [119]. The solid lines result from fitting the theoretical predictions of Akcasu et al. [94] to the experimental data using B = 0.38 and T s and a = / as adjustable parameters. The dotted lines are the corresponding predictions for 0 conditions. (Reprinted with permission from [119]. Copyright 1981 American Chemical Society, Washington)...

The first term on the RHS of (III-8) represents mutual termination of radicals in the polymer particles (i.e. second order termination). The second term represents a first order termination of radicals in the polymer particles by monomer soluble impurities (MSI), which are present in the polymer particles due to their transfer in there with monomer during the monomer diffusion phase from monomer droplets. 

Auto-acceleration was observed in the homopolymerization of methacrylic acid solutions over limited concentration ranges in methanol and in water. Perhaps under such conditions swelling of the polymer favors monomer diffusion leading to a larger amount of pre-oriented structures III. Alternatively, a monomer-solvent complex may arise which favors a pre-oriented structure and thus, may be responsible for the onset of a matrix effect (9). 

The narrow molecular weight distributions accomplished by the supported catalysts were attributed to the absence of any organoaluminium co-catalyst dissocia-tion/reassociation processes at the heterogenized active neodymium centers. Furthermore, the order of the grafting sequence seemed to have minor implications for the catalyst performance. Control experiments have been conducted to explain the lower activity [0.9 (47) and 1.1 kg-PBD molNd h (48)] of the supported neodymium catalyst. Accordingly, an increase of the catalyst concentration (48) and use of a nonporous silica support (49) suggested that monomer diffusion and accessibility of the Nd centers are limited by the relatively small mesopores [dp = 2.4 (47) and 2.5 nm (48), after grafting]. 

Other exceptions to the first-order dependence of the polymerization rate on the monomer concentration occur when termination is not by bimolecular reaction of propagating radicals. Second-order dependence of Rp on [M] occurs for primary termination (Eq. 3-33a) and certain redox-initiated polymerizations (Sec. 3-4H-2). Less than first-order dependence of Rp on [M] has been observed for polymerizations (Sec. 9-8a-2) taking place inside a solid under conditions where monomer diffusion into the solid is slower than the normal propagation rate [Odian et al., 1980] and also in some redox polymerizations (Sec. 3-4b-2) [Mapunda-Vlckova and Barton, 1978]. 

The rate of monomer consumption by polymerization was found to be several times larger than the estimated maximum rate of monomer diffusion through the polymer deposit. Therfore, these authors believed polymerization must occur only in the outermost regions of the polymer... 

Above about —100° C [CtG] [CSG] and the second term in Eq. (1) becomes negligible. Thus, P(l, 3)/P(l, 2) reduces to k /k, i.e., the structure ratio is independent of monomer concentration. At lower temperatures, where the reaction was postulated to become monomer diffusion controlled, it was impossible to determine the effect of [M] on structure ratio predicted by the model. 

Monomer diffusion in the rubbery phase of PVC-rich reaction products is difficult, and this was demonstrated by polymerizing vinyl chloride (200 grams) at 70°C in the presence of a crude polymerizate (360 grams) containing 9% total rubber suspended in an aqueous solution of poly-(vinyl alcohol) (1.2% with respect to the polymer + monomer weight), so as to obtain a ratio of water/crude + monomer = 2.4 and by using benzoyl peroxide (0.38% with respect to the reacting monomer). 

It is accepted that the radical entry rate coefficient for miniemulsion droplets is substantially lower than for the monomer-swollen particles. This is attributed to a barrier to radical entry into monomer droplets which exists because of the formation of an interface complex of the emulsifier/coemulsifier at the surface of the monomer droplets [24]. The increased radical capture efficiency of particles over monomer droplets is attributed to weakening or elimination of the barrier to radical entry or to monomer diffusion by the presence of polymer. The polymer modifies the particle interface and influences the solubility of emulsifier and coemulsifier in the monomer/polymer phase and the close packing of emulsifier and co emulsifier at the particle surface. Under such conditions the residence time of entered radical increases as well as its propagation efficiency with monomer prior to exit. This increases the rate entry of radicals into particles. 

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