Synthesis of polymethacrylate‐bearing benzocyclobutene structure and extension to networked polymer based on thermal isomerization

Abstract

1‐Benzocyclobutenyl methacrylate‐bearing methacrylate (BCBMA) backbone has been synthesized, and radical polymerization of the monomer was performed by utilizing 2, 2′‐azobisisobutyronitrile (AIBN) as initiator to result poly‐BCBMA. Differential scanning calorimetry (DSC) measurement of the derived poly‐BCBMA revealed the lowering of thermal isomerization temperature from that of nonsubstituted benzocyclobutene. The thermal decomposition temperature of BCBMA before and after thermal treatment was confirmed by thermogravimetric analysis (TGA). The results of the TGA observation did not show significant difference in both 5% and 10% weight loss temperature (Td5 and Td10). This result suggests that the thermal conversion of the poly‐BCBMA to the networked polymer take place without thermal decomposition of the main chain based on the methacrylate framework. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 2175–2180

Bivalent monomer bearing styryl and five‐membered cyclic dithiocarbonate moieties for orthogonal radical and cationic ring‐opening polymerizations

“…The FTIR spectrum of 1 showed the characteristic absorption of thiocarbonyl group (CS) at 1186 cm −1 , whereas the absorption of CS was completely eliminated and the absorption due to carbonyl group (CO) appeared at 1637 cm −1 in the FTIR spectrum of 1b . This result indicated that the ring‐opening polymerization of 1 successfully proceeded and afforded 1b having the isomerized dithiocarbonate structure in the main chain 24 . On the other hand, the peak due to the CC absorption at 1628 cm −1 disappeared in the FTIR spectrum of 1a .…”

“…This result indicated that the ring-opening polymerization of 1 successfully proceeded and afforded 1b having the isomerized dithiocarbonate structure in the main chain. 24 On the other hand, the peak due to the C C absorption at 1628 cm À1 disappeared in the FTIR spectrum of 1a. Additionally, the absorption of C S was observed at 1186 cm À1 in the FTIR spectrum of 1a, indicating the structure of 1a having a cyclic dithiocarbonate moiety in the side chain.…”

“…On the other hand, bifunctional monomers having two different polymerizable functional groups are known as orthogonal monomers 13–23 . The two functional groups of the orthogonal monomer are polymerized by different mechanisms, resulting in networked polymers consisting two different polymer chains 15–24 . Therefore, polymers synthesized from orthogonal monomers are expected to exhibit unique functionality compared to polymers synthesized from typical bifunctional monomers.…”

“…[13][14][15][16][17][18][19][20][21][22][23] The two functional groups of the orthogonal monomer are polymerized by different mechanisms, resulting in networked polymers consisting two different polymer chains. [15][16][17][18][19][20][21][22][23][24] Therefore, polymers synthesized from orthogonal monomers are expected to exhibit unique functionality compared to polymers synthesized from typical bifunctional monomers. Recently, we achieved synthesis and cationic ring-opening polymerization of five-membered cyclic dithiocarbonate (CDTC) bearing a dibenzyl amine moiety.…”