Combining Enzymatic Transacylation And Controlled Radical Polymerization In One-pot To Prepare Functional Polymers

In the past two decades, controlled radical polymerization(CRP) has become one of the hottest research topics in polymer chemistry.Although CRP exhibited huge advantages in preparing well-defined polymers, it has not been widely used in industry due to its intrinsic drawbacks such as slow polymerization rate, the use of metal catalysts in ATRP or the color/odor issue in RAFT polymerization. How to make fully use of the advantages of CRP and overcome its drawbacks is very important for the future development of CRP towards industrial application. In this thesis, based on the controlled features of CRP, lipase-catalyzed transacylation was associated with CRP to fabricate a one-pot tandem method for facile polymer synthesis. Such one-pot process integrated simultaneous enzymatic monomer transformation and CRP process, avoided laborious purification operations inconventional monomer synthesis, which would thus greatly improve efficiency in polymer synthesis and provide synthetic chemists with more ability to prepare polymers with various compositions and functionalities. The thesis included contents as follows: 1) Monomer transformation via enzymatic transesterification between activated vinyl ester and alcohols was combined with ATRP to develop a one-pot novel and facile polymerization methodology. The mutual compatibility of enzymatic transesterification and ATRP was investigated systematically. 2) Highly efficient enzymatic resolution of racemic secondary alcohols was further combined with ATRP to prepare optical active polymer in one-step. 3) RAFT polymerization was also used as polymerization platform. Controlled enzymatic monomer transformation was coupled with RAFT polymerization in one-pot to prepare polymers with gradient monomer sequence. 4) Multifunctional polymer possessing reactive groups was facilely produced in one-step through the concurrent enzymatic transacylation of multiple functional alcohols with acyl donor monomer and RAFT polymerization. The thus-prepared polymer was conjugated with doxorubicin and glucosamine to develop a theranostic material with multi-functionalities such as MRI, targeting, anti-cancer, pH responsiveness. The self-assembly behavior and antitumor effect of the polymer-drug conjugate was investigated.