Citation: Guang-zhao Zhang. Hybrid Copolymerization[J]. Acta Polymerica Sinica, ;2018, 0(6): 668-673. doi: 10.11777/j.issn1000-3304.2018.18074 shu

Hybrid Copolymerization

  • Corresponding author: Guang-zhao Zhang, msgzzhang@scut.edu.cn
  • Received Date: 7 March 2018
    Revised Date: 27 March 2018
    Available Online: 13 April 2018

  • Hybrid copolymerization is the process where two or more unlike monomers with different polymerizable groups polymerize together. It is revolutionary to the conventional copolymerization where the monomers have the same polymerizable groups. Hybrid copolymerization provides new routes for synthesis of polymers and gives great possibility to produce polymers with novel properties. However, because the unlike monomers follow different polymerization mechanisms and their reactivities are quite different, hybrid copolymerization has long been a challenge. Fortunately, some breakthroughs have been made in vinyl addition and ring-opening hybrid copolymerization since 1980’s. Bailey et al. first reported the radical ring-opening hybrid copolymerization of 2-methylene-1,3-dioxepane (MDO) with vinyl monomers such as styrene (St) and methyl methacrylate (MMA) in 1982. Such a copolymerization can yield relatively high molecular weight polymers (104 − 10 5), but the cyclic monomers are only limited to cyclic ketene acetals. Zwitteronic hybrid copolymerization was reported later but it only produces oligomers. With the development of organocatalysis, anionic and cationic hybrid copolymerizations were studied in recent years. Cationic hybrid copolymerization or the so-called concurrent cationic copolymerization of isobutylene oxide and vinyl ether was reported in 2013. The copolymerization is also applicable to other cyclic monomers with epoxides, but it produces polymers with a relatively low molecular weight (103 − 10 4). In 2012, anionic hybrid copolymerization of ε-caprolactone (CL) and methyl methacrylate (MMA) was reported by our laboratory for the first time. Such a copolymerization is applicable to many common monomers including cyclic ester or cyclic ether and vinyl esters. The polymer synthesized by anionic hybrid copolymerization has a high molecular weight (104 − 10 5) so that it can be used in different materials. Actually, clickable or hybranched biodegradable polymers were already prepared via the copolymerization. Particularly, it was used to develop high performance biodegradable polymers for marine anti-biofouling. The work describes the progress in hybrid copolymerization.
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