Poly(2,3-Dihydrofuran): A Strong, Biorenewable, and Degradable Thermoplastic Synthesized via Room Temperature Cationic Polymerization

Abstract

Creation of strong and tough plastics from sustainable and biorenewable resources is a significant challenge in polymer science. This challenge is further complicated when attempting to make these materials using an economically viable process, which is often hindered by the production and availability of chemical feedstocks and the efficiency of the monomer synthesis. Herein, we report the synthesis and characterization of a strong thermoplastic made from 2,3-dihydrofuran (DHF), a monomer made in one step from 1,4-butanediol, a bioalcohol already produced on the plant scale. We developed a green, metal-free cationic polymerization to enable the production of poly(2,3-dihydrofuran) (PDHF) with molecular weights of up to 256 kg/mol at room temperature. Characterization of these polymers showed that PDHF possesses high tensile strength and toughness (70 and 14 MPa, respectively) comparable to commercial polycarbonate, high optical clarity, and good barrier properties to oxygen, carbon dioxide, and water. These properties make this material amenable to a variety of applications, from food packaging to high strength windows. Importantly, we have also developed a facile oxidative degradation process of PDHF, providing an end-oflife solution for PDHF materials.

Scalable, Green Chain Transfer Agent for Cationic RAFT Polymerizations

“…In addition, THF is susceptible to ring opening under acidic conditions and for the same reason this also removes 2‐methyl‐THF as an option in most cases. However, based on reports of similar solubility properties to THF, we recently identified cyclopentyl methyl ether (CPME) as an effective green solvent for the acid‐initiated cationic polymerization of dihydrofuran (DHF), [ 16 ] suggesting that CPME may also represent a promising green solvent for cationic RAFT polymerizations.…”

“…as a monomer, we hypothesized that incorporation of DHF in place of isobutyl vinyl ether (IBVE) would increase the melting point of our most commonly used cationic RAFT CTA (CTA‐1). [ 16 ] Concurrently, we reasoned that changing the diethyl amine to cyclic pyrrolidine should have the same effect without significantly changing the electronic properties of the dithiocarbamate.…”

Asymmetric Ion-Pairing in Stereoselective Vinyl Polymerization

“…AIP catalysis has been most successful for cationic polymerization in terms of its application to a variety of monomer substrates. Despite this success, there are limited reports of the stereoselective polymerization of 1,2-disubstituted alkenes, for example, propenyl ethers, to generate a ditactic polymer. , Given these polymers typically have high glass transition temperatures and are proposed as more sustainable alternatives to current glassy thermoplastics, control of their stereochemistry would enable a larger diversity of properties from these readily available and underexplored monomers. − A complementary goal is a continued pursuit of methods that provide stereoselective polymerization under living conditions, which would provide access to stereoblock materials or complex polymer architectures that could alter crystallization and thermomechanical and optical properties.…”

Visible Light Induced Degradation of Poly(methyl methacrylate‐co‐methyl α‐chloro acrylate) Copolymer at Ambient Temperature

“…Recent advances and studies on depolymerization and degradation methods enable researchers to reach higher efficiency through the process, involving either slightly modifying the polymer chain or either direct depolymerization or degradation using catalysts. [16][17][18][19][20][21][22][23][24][25][26][27][28][29][30][31][32][33][34][35] Initially in 2019, Ouchi and co-workers successfully depolymerized and degraded PMMA and chlorinated PMMA derivatives in the presence of a ruthenium catalyst. [35,36] In another promising report from Matyjaszewski's group, poly(butyl methacrylate) is depolymerized by using (CuCl 2 /tris(2-pyridylmethyl)-amine).…”