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      Sequence-definition from controlled polymerization: the next generation of materials

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          Abstract

          An overview is given on the state-of-the-art in synthesis of sequence-controlled and sequence-defined oligomers and polymers.

          Abstract

          An overview is given on the state-of-the-art in synthesis of sequence-controlled and sequence-defined oligomers and polymers. These materials constitute chains in which chemical information is encoded along the backbone either as multiblock copolymers (controlled) or as monodisperse sequences of single monomers (defined). Focus is placed on reversible-deactivation radical polymerization techniques as these give access to a broad variety of chemical functionalities and allow for simple and fast synthesis procedures. Sequence-controlled and -defined materials have the ability to re-shape materials chemistry due to their close resemblance to biopolymers regarding structural uniformity. The field is at the edge of being able to start exploring the distinct properties that such synthetic macromolecules may have.

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          From precision polymers to complex materials and systems

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            Rapid and quantitative one-pot synthesis of sequence-controlled polymers by radical polymerization.

            A long-standing challenge in polymer chemistry has been to prepare synthetic polymers with not only well-defined molecular weight, but also precisely controlled microstructure in terms of the distribution of monomeric units along the chain. Here we describe a simple and scalable method that enables the synthesis of sequence-controlled multiblock copolymers with precisely defined high-order structures, covering a wide range of functional groups. We develop a one-pot, multistep sequential polymerization process with yields >99%, giving access to a wide range of such multifunctional multiblock copolymers. To illustrate the enormous potential of this approach, we describe the synthesis of a dodecablock copolymer, a functional hexablock copolymer and an icosablock (20 blocks) copolymer, which represents the largest number of blocks seen to date, all of very narrow molecular weight distribution for such complex structures. We believe this approach paves the way to the design and synthesis of a new generation of synthetic polymers.
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              High-order multiblock copolymers via iterative Cu(0)-mediated radical polymerizations (SET-LRP): toward biological precision.

              We report a new approach for the facile synthesis of high-order multiblock copolymers comprising very short blocks. The approach entails sequential addition of different monomers via an iterative single electron transfer-living radical polymerization technique, allowing nearly perfect control of the copolymer microstructure. It is possible to synthesize high-order multiblock copolymers with unprecedented control, i.e., A-B-C-D-E-etc., without any need for purification between iterative 24 h block formation steps. To illustrate this concept, we report the synthesis of model P(MA-b-MA...) homopolymer and P(MA-b-nBuA-b-EA-b-2EHA-b-EA-b-nBuA) copolymer in extremely high yield. Finally, the halide end-group can be modified via "click chemistry", including thiol-bromide click chemistry, sodium methanethiosulfonate nucleophilic substitution, and atom transfer radical nitroxide coupling reaction, to yield functional, structurally complex macromolecules.
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                Author and article information

                Journal
                PCOHC2
                Polymer Chemistry
                Polym. Chem.
                Royal Society of Chemistry (RSC)
                1759-9954
                1759-9962
                2018
                2018
                : 9
                : 38
                : 4692-4705
                Affiliations
                [1 ]Polymer Reaction Design Group
                [2 ]School of Chemistry
                [3 ]Monash University
                [4 ]Clayton VIC 3800
                [5 ]Australia
                [6 ]Institute for Materials Research
                [7 ]Hasselt University
                [8 ]3500 Hasselt
                [9 ]Belgium
                Article
                10.1039/C8PY01190G
                12d23e00-af75-451b-9cc4-49ff188860da
                © 2018

                http://rsc.li/journals-terms-of-use

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