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| - Radical Polymerization Initiated from a Solid Substrate. 1. TheoreticalBackground
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| - From a survey of the literature on grafting free radical polymerization from solid surfaceswe suggest kinetic schemes for the process. The system of differential equations in partial derivativesincluding the diffusion equation based on the classical theory of free radical polymerization and theassumption that surface-bonded free radicals terminate by (1) reactions with bulk free radicals and (2)chain transfer to solvent or monomer are introduced. Computer simulations performed using the equationshave shown good agreement with the characteristic features of the grafting process. The rate of graftingis linearly proportional to the surface concentration of the initiator and decreases as the initiation ratein the bulk increases. It follows from the concentration profiles of the bulk free radicals that free radicalconcentration in the vicinity of the surface can be several times larger than that in the bulk. Theconcentration profile depends on the distance between two surfaces. For distances less than a criticaldistance of about 2 μm, the concentration profile of the bulk free radicals is homogeneous.
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