Heterogeneous-Type Grafts

This and the following subsection will compare heterogeneous and homogeneous synthetic methods, with emphasis on cellulosics. Fibrous cellulosic graft copolymers, prepared by radiation-induced free-radical copolymerization reactions of vinyl monomers with cellulose, retain some 

As noted above, the fine structure of cotton fibers is similar to that of the wood tracheid cells discussed in Section 9.8. Thus, grafting can occur on the outer and inner surfaces, as well as in the amorphous portions of the fiber. 

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Different approaches have been used in the preparation of heterogeneous Sharpless-type catalytic systems for the asymmetric epoxidation of allylic alcohols, although in most cases the chiral induction was modest (50-60%). Li and coworkers described the preparation of an organic-inorganic hybrid chiral catalyst grafted onto the surface of silica and in mesopores of MCM-41, and its successful application in asymmetric epoxidation . Enantiomeric excesses were higher than 80% with conversions in the range 22-76%. 

Dispersion polymerization differs from emulsion polymerization in that the reaction mixture, consisting of monomer, initiator, and solvent (aqueous or nonaque-ous), is usually homogeneous. As polymerization proceeds, polymer separates out and the reaction continues in a heterogeneous manner. A polymeric surfactant of the block or graft type (referred to as protective colloid ) is added to stabilize the particles once formed. 

The structural complexity of synthetic polymers can be described using the concept of molecular heterogeneity (see Fig. 1) meaning the different aspects of molar mass distribution (MMD), distribution in chemical composition (CCD), functionality type distribution (FTD) and molecular architecture distribution (MAD). They can be superimposed one on another, i.e. bifunctional molecules can be linear or branched, linear molecules can be mono- or bifunctional, copolymers can be block or graft copolymers, etc. In order to characterize complex polymers it is necessary to know the molar mass distribution within each type of heterogeneity. 

The time course of fibrinogen adsorption onto the two types of poly-(HEMA) is depicted in Figure 3 which also includes representative points for poly (HEMA) grafted onto Silastic. The slow rise to the final adsorption level seen for both types of poly (HEMA) is very similar to the kinetics observed for grafted poly (HEMA), as is the actual amount of adsorption. The slight disparity between the poly (HEMA) types is probably related to the more open and thus rougher surface of the heterogeneous poly (HEMA). 

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