Synthesis and Solution Self-Assembly of Poly(1,3-dioxolane)

Abstract

Poly(1,3-dioxolane) (PDO) is widely used as a pH-and temperaturesensitive water-soluble polymer applied in functional hydrogels and nanoparticles. In this contribution, we report a series of highly efficient rare-earth triflate catalysts for a Brønsted-acid-free ring-opening polymerization of DO. The repeat unit of PDO comprises perfectly alternating hydrophilic ethylene glycol and hydrophobic methyl aldehyde units leading to hydrogen-bonding-controlled self-assembly in aqueous solution. Spherical aggregates are observed in transmission electron microscopy images whose sizes can be tuned by concentration and temperature, further confirming that the hydrate is derived from "blocked" water molecules through hydrogen bonding. The size and morphology of the aggregates can be modulated not only by the annealing process owing to the realignment of semicrystalline regions but also by metal salts generating rodlike, wormlike, or spherical structures. In this case, PDO is able to act as both a surfactant and as a reductant on account of the acidolysis of acetal moieties, which form a core−shell Cudecorated hybrid material in situ in one step, thus providing a promising future template for the generation of metal nanoparticles.

Self‐Enhancing Gel Polymer Electrolyte by In Situ Construction for Enabling Safe Lithium Metal Battery

“…The results of 1 H NMR and 13 C NMR spectra were accordant with the theory and related literature, indicating the successful polymerization of DOL. [ 13 , 19 ] Furthermore, no obvious peaks related to the crystallization or melting behavior were observed in the differential scanning calorimetry curves (−20–60 °C) (Figure S5b , Supporting Information), which meant that the polymer electrolyte was almost amorphous due to the plasticizing effects of LiTFSI, favoring the Li + conductivity. [ 20 ]…”

Janus Polymerization: A One‐Shot Approach towards Amphiphilic Multiblock Poly(ester‐acetal)s Directly from 1,3‐Dioxolane with ε‐Caprolactone

“…A melting temperature at 53°C and strong X‐ray diffractions at 2 θ of 21.5° and 23.8° are detected, which contribute to homo‐PCL of Janus copolymers (Sample 6 in Table 1, Figures 2A and 2B). [ 18 ] The signals at around 34°C and 48°C indicate the relatively intact poly(1,3‐dioxolane) (PDO, Figure S12) because DO is consumed more than CL in CROP [ 31 ] and CL is mostly consumed in AROP. Since no melting signal is found in DSC analyses (Figures 1A and S13), amorphous copolymers are synthesized either by RE(OTf) 3 (RE = Y, Nd, Gd and Lu) catalyst or in the absence of an epoxy initiator.…”

“…[ 30 ] Thus, DO is a prospective monomer for the construction of polyacetals with good wettability because of the modest hydrophilic backbone and good mechanical performances. [ 31 ] The catalysts for the polymerizations of DO have been studied over the past years, for instance, triflic anhydride, [ 32 ] boron trifluoride, [ 33 ] maghnite‐H [ 34 ] and halomethyl ether with indium(III) bromide. [ 30 ] Copolymers of DO with CL, to the best of our knowledge, are not available due to the greatly different reactivities of the two monomers in CROPs, [ 35 ] while the incorporation of CL as comonomers improves not only the mechanical properties but also the biocompatibility of the product.…”

Functionalization and metathesis polymerization induced self-assembly of an alternating copolymer into giant vesicles

“…Ordered structured homopolymers reported are more prone to assemble into micelles and vesicles. [19][20][21][22] Not surprisingly, PDI functionalized P1 (Fig. 3a) showed uniform vesicles morphology with an average size of 50 nm, and FL inserted P2 (Fig.…”