Polymer formation chain growth rate

Finally, we were led to the last stage of research where we treated the crystallization from the melt in multiple chain systems [22-24]. In most cases, we considered relatively short chains made of 100 beads they were designed to be mobile and slightly stiff to accelerate crystallization. We could then observe the steady-state growth of chain-folded lamellae, and we discussed the growth rate vs. crystallization temperature. We also examined the molecular trajectories at the growth front. In addition, we also studied the spontaneous formation of fiber structures from an oriented amorphous state [25]. In this chapter of the book, we review our researches, which have been performed over the last seven years. We want to emphasize the potential power of the molecular simulation in the studies of polymer crystallization. 

The overall rate of crystallization is determined by both the rate of nuclei formation and by the crystal growth rate. The maximum crystal growth rate lies at temperatures of between 170 and 190 °C [71, 72], as does the overall crystallization rate [51, 61, 75], The former is measured using hot stage optical microscopy while the latter is quantified by the half-time of crystallization. Both are influenced by the rate of nucleation on the crystal surface and the rate of diffusion of polymer chains to this surface. It has been shown that the spherulite growth rate decreases with increasing molecular weight due to the decrease in the rate of diffusion of molecules to this surface [46, 50, 55, 71, 74],... 

Let us for the moment disregard chain transfer reactions. Radical polymerization then consists of three component reactions initiation, propagation of the polymer chains, and termination of chain growth. The rate of primary radical formation, v, by decomposition of the initiator I, may be written ... 

The presence of defects caused by incomplete reaction in the particles has been found while comparing intra- and intermolecular reaction rates in polycomplexes obtained by mixing polymer solutions, and by matrix polymerization 461. In the latter case a polycomplex is formed simultaneously with the chain growth which is connected with the complementary macromolecule, the matrix. This process of polycomplex formation is closer to the equilibrium one — in any case there are considerably fewer obstacles here for forming an uninterrupted sequence of intermolecular bonds. That is why the rate and conversion of thermochemical reactions (which are connected with the presence or absence of defects — loops or tension in double-stranded chains of the polycomplex) depend on how the polycomplex have been obtained. After its destruction and reconstruction (e.g., by increasing and then decreasing of pH in the case of p.c. (PMA — PVPD)) the matrix polycomplex does not differ from the one obtained by mixing 46). 

The chemical reaction mechanism of electropolymerization can be described as follows. The first step in course of the oxidative electropolymerization is the formation of cation radicals. The further fate of this highly reactive species depends on the experimental conditions (composition of the solution, temperature, potential or the rate of the potential change, galvanostatic current density, material of the electrode, state of the electrode surface, etc.). In favorable case the next step is a dimerization reaction, and then stepwise chain growth proceeds via association of radical ions (RR-route) or that of cation radical with a neutral monomer (RS-route). There might even be parallel dimerization reactions leading to different products or to the polymer of a disordered structure. The inactive ions present in the solution may play a pivotal role in the stabilization of the radical ions. Potential cycling is usually more efficient than the potentiostatic method, i.e., at least a partial reduction... 

The degree of polymerization (DP)—i.e., the average number of monomer units per polymer molecule—is given by the number of chain propagation steps for each reaction between a pair of polymer radicals—i.e., for each formation of a dead polymer molecule. Therefore, DP is equal to the rate of chain growth divided by half the rate of chain termination ... 

Each polymer molecule/chain increases in size at a rapid rate once its growth has been started by formation of an active center. When the macromolecule stops growing (due to termination reaction) it can generally not react with more monomers (barring side reactions). 

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