Grafting of acrylic monomers onto the renewable feedstock starch via free radical polymerizations has been investigated for many years. Many potential applications have been studied, such as superabsorbents, flocculants, thickening agents and so forth. It is expected that size and spacing of the grafts have a large influence on the performance of such polymers. Yet, information upon the structure-property relationships is only scarcely found in literature. Moreover, there is no clear overview of how reaction variables can be used to influence the grafted structure. In this review, an assessment has been made of the relation between the architecture of the grafts and potential applications. Then, from a selection of relevant literature data it is demonstrated that reaction variables such as the relative concentrations of initiator and monomer, have a large impact on the average size and spacing of the grafts. The emergence of controlled radical polymerizations, like Atom Transfer Radical Polymerization (ATRP) and Reversible Addition-Fragmentation chain Transfer (RAFT), is discussed, both the current status and future prospects. These methods are promising in the future of starch grafting, especially for systems where homopolymer formation may be a problem. Nevertheless, higher costs and other related issues make these advanced methods more suitable in high added-value products.
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