Effect of Guest Compounds on Template Polymerization of Multivinyl Monomer of Cyclodextrins

Abstract

Copper-mediated atom transfer radical polymerization of the following three methacryloyl type multivinyl monomers was carried out with many guest compounds; the effect of the guest on degree of polymerization [DP] of methacryloyl group was investigated. The multivinyl monomers were α-MVM with 17.4 methacryloyl groups prepared from α-cyclodextrin [a-CD], β-MVM1 with 11.6 methacryloyl groups prepared from β-cyclodextrin [β-CD], and β-MVM2 with 20.4 methacryloyl groups prepared from β-CD. The arrangement of the methacryloyl groups in the multivinyl monomer by inclusion of the guest compound was simulated by MM2 and measured by 2D-NMR. Methacrylic acid oligomers [PMAA] were obtained by hydrolysis of the polymerized products. The DP of PMAA was determined by GPC measurements calibrated with MALDI-TOF-mass measurement. Molecular weight and molecular weight distribution of PMAA were varied by the guest compound. A long alkyl group in the guest enhanced the ordering of methacryloyl groups in the multivinyl monomer, and PMAA with DP = 6 and 7 with narrow molecular weight was obtained for multivinyl monomers with α-CD and βCD, respectively. A phenyl group in the guest disturbed the arrangement of the methacryloyl groups and resulted in the intermolecular polymerization.