Pd-initiated controlled polymerization of diazoacetates with a bulky substituent: synthesis of well-defined homopolymers and block copolymers with narrow molecular weight distribution from cyclophosphazene-containing diazoacetates

Abstract

Pd-initiated polymerization of cyclophosphazene-containing diazoacetates proceeded in a controlled manner.

Pd‐initiated polymerization of diazo compounds bearing dialkoxyphosphinyl group and hydrolysis of the resulting polymers and oligomers to afford phosphonic acid‐containing products

“…Interesting to note is that the Rh‐diene initiated polymerization by Hetterscheid et al proceeds in a highly stereoselective manner, affording high molecular weight stereospecific polymers from alkyl diazoacetates . Although the polymers obtained by our Pd‐based initiators are basically atactic, monomers with a variety of ester substituents can be polymerized by the initiators . These results demonstrate the potential of the transition metal‐initiated polymerization of diazoacetates as a highly versatile method for the CC main chain polymer synthesis.…”

Poly(pentafluorobenzyl 2‐ylidene‐acetate): Polymerization and Postpolymerization Modification

“…[ 2 b] To the best of our knowledge, other functional groups that have been introduced into C1 polymers so far are epoxide, [ 4 ] alkene, [ 5 ] benzyl, [ 6 ] ethylene glycol, [ 7 ] phosphonic acid, [ 8 ] long alkyl chains, [ 9 ] mesogens, [ 10 ] polycyclic aromatic hydrocarbons, [ 11 ] and substituted cyclophosphazenes. [ 12 ]…”

“…[2b] To the best of our knowledge, other functional groups that have been introduced into C1 polymers so far are epoxide, [4] alkene, [5] benzyl, [6] ethylene glycol, [7] phosphonic acid, [8] long alkyl chains, [9] mesogens, [10] polycyclic aromatic hydrocarbons, [11] and substituted cyclophosphazenes. [12] Postpolymerization modification is a versatile synthetic tool that introduces chemical functionalities to macromolecules, which cannot be prepared by direct polymerization from its corresponding monomers. For a functional group to be utilized for the postpolymerization modification, the following conditions must be met: i) be stable during the polymerization process; ii) allow for selective and highly efficient chemical modification under mild reaction conditions.…”

Poly(carbyne)s via reductive C1 polymerization

“…Diazo compounds, 1,5-7 ylides, 5,6,8,9 isocyanides 1,10 and geminal dihalides 11 are typically used as monomers in C1 polymerizations because they are capable of generating carbenoid-like intermediates that can condense in a repeating fashion (Scheme 1(a)). Catalysts are often required to activate the monomer and some offer controlled 12 or living characteristics. [13][14][15][16][17] A relatively less studied class of C1 polymers are the poly(carbyne)s. Carbyne additions can result in different polymer architectures that depend on the bonding configuration of the repeating unit (Scheme 1(b)).…”

“…Diazo compounds, 1,5–7 ylides, 5,6,8,9 isocyanides 1,10 and geminal dihalides 11 are typically used as monomers in C1 polymerizations because they are capable of generating carbenoid‐like intermediates that can condense in a repeating fashion (Scheme 1(a)). Catalysts are often required to activate the monomer and some offer controlled 12 or living characteristics 13–17 …”