Abstract
The impacts of hydrogen bonding on polymerization behavior has been of interest for a long time; however, universality and in-depth understanding are still lacking. For the first time, the effect of hydrogen bonding on the classical alternating-type copolymerization of styrene and maleimide was explored. N-phenylmaleimide (N-PMI)/styrene was chosen as a model monomer pair in the presence of hydrogen bonding donor solvent 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP), which interacted with N-PMI via hydrogen bonding. Reversible addition-fragmentation chain transfer polymerization (RAFT) technique was used to guarantee the “living” polymerization and thus the homogeneity of chain compositions. In comparison with the polymerization in non-hydrogen bonding donor solvent (toluene), the copolymerization in HFIP exhibited a high rate and a slight deviation from alternating copolymerization tendency. The reactivity ratios of N-PMI and St were revealed to be 0.078 and 0.068, respectively, while the reactivity ratios in toluene were 0.026 and 0.050. These interesting results were reasonably explained by using computer simulations, wherein the steric repulsion and electron induction by the hydrogen bonding between HFIP and N-PMI were revealed. This work first elucidated the hydrogen bonding interaction in the classical alternating-type copolymerization, which will enrich the research on hydrogen bonding-induced polymerizations.
Highlights
The highly polar solvent fluoroalcohol interacts with monomers via hydrogen bonding and has been frequently utilized in polymerization to facilitate polymerization and to regulate polymer microstructures [1,2,3,4,5]
To elucidate the hydrogen bonding effects on the polymerization, reversible addition-fragmentation chain transfer (RAFT) polymerizations under different molar ratios of N-PMI to St were implemented in HFIP and toluene, respectively
RAFT copolymerization of N-PMI and St was implemented in the hydrogen bonding donor solvent HFIP
Summary
The highly polar solvent fluoroalcohol interacts with monomers via hydrogen bonding and has been frequently utilized in polymerization to facilitate polymerization and to regulate polymer microstructures [1,2,3,4,5]. Takahara et al cleverly used fluoroalcohol as a hydrogen bonding donor solvent to synthesize well-defined poly(sulfobetaine) brushes via surface-initiated atom transfer radical polymerization [6]. The polymerization system was judiciously selected by using styrene (St)/maleimide as comonomer pair It is well-known that maleimide has a high cross-propagation tendency with St to form a typical alternating copolymer, which can serve as the reference standard for investigating the effects of polymerization environments on polymerization behavior and the resultant polymers. This study will offer helpful results for understanding the effects of hydrogen bonding on polymerization, and might eventually direct the synthesis of novel biocompatible polymeric materials
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