Abstract
For the copolymerization of non-conjugated olefins and maleimides, it is known that under certain conditions periodic ABA monomer sequences are formed. In this work, such a copolymerization is used to create polymers which have defined (periodic) monomer sequences and can be functionalized after polymerization. The copolymerization of pentafluorophenol (PFP) active esters of 4-pentenoic acid and perillic acid with N-phenyl maleimide (PhMI) was studied in 1,2-dichloroethane (DCE) and 1,1,1,3,3,3-hexafluoro-2-phenyl-2-propanol (HFPP). In DCE and for the copolymerization of the PFP ester of 4-pentenoic acid and PhMI in HFPP, polymers were formed where the active esters were separated by at least one PhMI unit. The average number of separating PhMI units can be controlled by varying the feed ratio of the monomers. For the copolymerization of the PFP ester of perillic acid in HFPP, a preference for the formation of periodic copolymers was observed, where active esters were preferably separated from each other by a maximum of two PhMI moieties. Therefore, the copolymerization of said active ester containing monomers with PhMI provides a platform to create polymers in which reactive moieties are distributed along the polymer chain in different fashions. The active esters in the non-conjugated vinyl monomers could be used in a post-polymerization functionalization step to create functionalized polymers with defined monomer sequences in a modular way.
Highlights
It is well known that the structure of macromolecules strongly relates to their properties [1,2,3,4,5].Structural features such as the architecture, molecular weight, tacticity and monomer sequence all play a role
Besides alternating copolymers, which can be prepared with relative ease, e.g., by choosing a pair of monomers that are electron-rich and -deficient, respectively [12,13,14,15], hardly any sequence-defined polymers are known for chain-growth polymerizations
Similar to other monomers with non-conjugated vinyl groups [19,20,21,22], these monomers are expected to copolymerize with maleimides though, and for some of these other monomers, periodic ABA
Summary
It is well known that the structure of macromolecules strongly relates to their properties [1,2,3,4,5] Structural features such as the architecture, molecular weight (or distribution thereof), tacticity and monomer sequence all play a role. Whereas significant progress has been made to control the architecture and molecular weight of synthetic polymers (notably using controlled free-radical techniques [6,7,8,9]) as well as the tacticity (e.g., using metal-catalyzed polymerization [10], and in radical polymerizations [11]), the monomer sequence is still difficult to control. Besides alternating copolymers, which can be prepared with relative ease, e.g., by choosing a pair of monomers that are electron-rich and -deficient, respectively [12,13,14,15], hardly any sequence-defined polymers are known for chain-growth polymerizations. Periodic ABA copolymers, the second simplest sequence imaginable, have e.g., only been described a few times in the literature
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