Synthesis of novel macromonomers and telechelics of poly(2‐alkyl‐2‐oxazoline)s

Abstract

Novel macromonomers and telechelics of poly(2‐alkyl‐2‐oxazoline) (PROZO) were syn‐thesized by utilizing termination of propagating species (2‐oxazolinium ions) in the living polymerization of 2‐alkyl‐2‐oxazoline (ROZO) with suitable nucleophiles. Two types of p‐vinylbenzyl–type macromonomers were obtained by terminating living PROZO with sodium p‐vinylbenzyl alkoxide or with sodium p‐vinylbenzyl mercaptide. The synthesis of telechelics having a functional group (SH, COOH) on both ends of PROZO was achieved by using a bis(2‐oxazolinium salt) initiator. The PROZO dithiol was synthesized by two methods: (1) termination of the living species on both ends with NaSH, and (2) aminolysis of PROZO bis(O‐ethyldithiocarbonate) given by treatment of the living PROZO with potassium O‐ethyldithiocarbonate. Termination of the living PROZO with the sodium salt of di‐t‐butyl malonate yielded a PROZO with di‐t‐butyl malonate moieties on both polymer ends, from which the PROZO dicarboxylic acid was derived via free tetracarboxylic acid. © 1995 John Wiley & Sons, Inc.

Polymerization of cyclic imino ethers: From its discovery to the present state of the art

“…The production of PROZO telechelics has been achieved with a bis(2‐oxazolinium salt), N,N ′‐dimethyl‐2,2′‐tetramethylene bis(oxazolinium tosylate), as a bifunctional initiator 36, 41. The termination of both living ends of PROZO with water, ammonia, or alkylamine affords the corresponding telechelics of PROZO as glycols and diamines in good yields (Scheme ).…”

Poly(2‐oxazoline)s as Polymer Therapeutics

“…[23], [86] Mono- and difunctional initiators yield linear symmetric or asymmetric telechelic polymers. [15], [87] while higher plurifunctional initiators give tri-, tetra- etc. arm star polymers, [88] , bow-tie multi-arm stars [35] and ultimately, macroinitiators result in comb copolymers or at high grafting densities in molecular brushes (Figure 5).…”

Defined High Molar Mass Poly(2‐Oxazoline)s

“…[9] Theh igh tunability of the PAOx polymer structure in combination with its high biocompatibility and non-fouling behaviour have raised significant interest in the use of PAOx for biomedical applications.For acomprehensive overview of recent developments,t he reader is referred to an excellent review by Luxenhofer et al [10] Theu se of PAOx for biomedical applications has been established beyond proof-of-concept research as the first in human studies (Phase 1a clinical trials) were successfully finished by Serina Therapeutics for aP AOx-drug conjugate. This,i nc ombination with the ease of end-group functionalization has led to multiresponsive PAOx, [12][13][14] as well as intricate thermoresponsive colour changing solutions. This,i nc ombination with the ease of end-group functionalization has led to multiresponsive PAOx, [12][13][14] as well as intricate thermoresponsive colour changing solutions.…”