Synthesis of hyperbranched polycarbonate by novel polymerization of di-tert-butyl tricarbonate with 1,1,1-tris(4-hydroxyphenyl)ethane

Abstract

Hyperbranched polycarbonates (HBPCs) with M n ¼2.1-7.1Â10 3 were synthesized by A 2 +B 3 polymerization using di-tert-butyl tricarbonate as the A 2 monomer and 1,1,1-tris(4-hydroxyphenyl)ethane as the B 3 monomer. A 2 +B 3 polymerization with different feed ratios was achieved, controlling the degree of branching (DB) and the ratio of terminal functional groups. The DB of the HBPCs is 0.5-0.7. The Boc-terminated PC was prepared by either a 1-pot or a 2-pot synthesis. In contrast, PC with terminal phenol groups was prepared by deprotection of Boc-terminated PC.

Hyperbranched polymers from A2 + B3 strategy: recent advances in description and control of fine topology

“…For hyperbranched polyimides from 2,2-bis(3,4-dicarboxylphenyl) hexafluoropropane dianhydride (A 2 ) and 2,4,6-triaminopyrimidine (B 3 ), 139 the DB increased from 0.36 to 0.83 when the feed ratio of A 2 : B 3 was increased from 1 : 1 to 2 : 1. Nishikubo et al 145 observed the same phenomenon in the polycondensation reaction of di-tertbutyl tricarbonate (A 2 ) and 1,1,1-tris(4-hydroxyphenyl)ethane (B 3 ), where the DB of the hyperbranched polycarbonates increased from 0.52 to 0.78 when the feed ratio was increased from 1 : 1 to 2 : 1. Similarly, for typical hyperbranched poly (amine-ester)s from the polycondensation between diesters (A 2 ) and triethanolamine (B 3 ), catalyzed by Candida antarctica lipase B, 146 the DB of poly(amine-ester)s at a feed ratio of 2 : 1 was much higher than that at a feed ratio of 1 : 1.…”

Aliphatic Hyperbranched Polycarbonates: Synthesis, Characterization, and Solubility in Supercritical Carbon Dioxide

“…Hyperbranched polycarbonates (HBPC) have been known since the early works of Bolton and Wooley , concerning synthesis and properties of aromatic analogues of linear, commercially available bisphenol A-based polycarbonates, but there is still a limited number of such polymers reported in the literature. Recently, similar aromatic HBP’s were reported by Nishikubo et al, who synthesized HBPC according to double monomer methodology (DMM) using di- tert -butyl tricarbonate and 1,1,1-tris(4-hydroxyphenyl)ethane as A 2 and B 3 monomers . Synthesis and functionalization with methacrylic acid residues of aromatic hyperbranched polycarbonates based on bisphenol A bis(chloroformate) and 1,1,1-tris(4-hydroxyphenyl)ethane performed in the presence of pyridine in THF were reported by the same authors .…”

“…Recently, similar aromatic HBP's were reported by Nishikubo et al, who synthesized HBPC according to double monomer methodology (DMM) using di-tert-butyl tricarbonate and 1,1,1-tris(4-hydroxyphenyl)ethane as A 2 and B 3 monomers. 14 Synthesis and functionalization with methacrylic acid residues of aromatic hyperbranched polycarbonates based on bisphenol A bis(chloroformate) and 1,1,1-tris(4hydroxyphenyl)ethane performed in the presence of pyridine in THF were reported by the same authors. 15 Aliphatic starshaped polycarbonates were reported by Hult and coworkers.…”

Blended vinylogous urethane/urea vitrimers derived from aromatic alcohols

“…Nowadays, these aromatic alcohols are used for countless applications, e.g. epoxy resins [34][35][36] , phenolic resins (resorcinol) [37][38][39][40] , polyesters [41][42][43][44][45][46] , dyes (fluorescin, eosin) 47,48 , medical diagnostics 49 and other usages 50 , which make them promising candidates for the use of recyclable and reprocessable polymer networks. Moreover, we introduce 2,7-naphtalendiol and 1,1,1-tris(4-hydroxyphenyl)ethane as less toxic alternatives to the widely established toxic and carcinogenic bisphenol-A and resorcin-based polymers, which are increasingly being avoided and replaced by industry.…”