Synthesis of Wholly Aromatic Polyketones Containing Optically Active Macrocycles

Abstract

ABSTRACT:Wholly aromatic polyketones 7 containing bisbinaphthyl macrocycles were synthesized via P 2 O 5 -MsOH mediated direct condensation reaction of compound 3 with chlorobenzoic acids 4, nucleophilic aromatic substitution reaction of the resulting binaphthyl (5)

Synthesis of aromatic poly(ether ketone)s bearing optically active macrocycles through Suzuki coupling polymerization

“…In addition, molecular weights of poly(ether ketone)s 12a-c in this study are much higher than those of wholly aromatic polyketones (M n : 5000-6400) synthesized through nickel complex-mediated aromatic homo-coupling polymerization, previously reported. 15 The difference between these polymerization behaviors probably depends on the length of the linkers that connect the macrocycles. The macrocycles are so large and bulky that homo-coupling polymerization with nearby neighboring macrocycles would be disadvantageous for producing the polymer.…”

“…In addition, the T g s of poly(ether ketone)s (12a-c) are much higher than those of macrocycle-bearing wholly aromatic polyketones (176-178 1C) synthesized through homo-coupling polymerization, previously reported. 15 The reasons for this variation in T g are the increase in molecular weight and the difference of the connecting positions of binaphthylene units, that is, 2,2¢-positions or 6,6¢-positions. Polymers bearing binaphthyl-2,2¢-ene groups will be more rigid than those bearing binaphthyl-6,6¢-ene groups according to the difference in steric hindrance.…”

“…Furthermore, we developed aromatic polyketones containing optically active macrocycles [9][10][11][12][13] composed of 1,1¢-binaphthyl-2,2¢-dioxy units. 14,15 These macrocycle-bearing polymers have adequate thermal and optical properties and solubility for use in engineering applications.…”

Synthesis of thermally robust benzimidazolone-based wholly aromatic polyketones

“…While some aliphatic polyketones 3 had been synthesized, wholly aromatic polyketones, [4][5][6][7][8][9][10][11][12] a new series of highperformance polymers, were reported by Yonezawa's group (see Scheme 1). There were some aliphatic substitutes such as methoxyl and triuoromethyl side groups in these polymers synthesized by either C-C coupling polycondensation or electrophilic polycondensation considering the solubility of polymer.…”

Poly(arylene ether ketone)s composed of a 1,8-diaroylenenaphthalene moiety: a non-coplanarly accumulated aromatic-ring repeating unit

“…Such modifications to the chemical structure have also afforded highmolecular-weight wholly aromatic polyketones, that is, poly(arylene ketone)s that are free from ether linkages in the main chain. We have achieved the synthesis of wholly aromatic polyketones 3 via the electrophilic aromatic aroylation polycondensation using the minute molecular design of acyl-acceptant molecules composed of 2,2 0 -dioxy-1,1 0 -biphenylylene, 4 2,2 0 -dioxy-1,1 0 -binaphthylylene, 5 and o-terphenylylene 6 moieties.…”