Carbon dioxide-based functional polycarbonates: Metal catalyzed copolymerization of CO2 and epoxides

Aliphatic polycarbonates synthesized from carbon dioxide (CO2) and epoxides are resource‐saving, highly biocompatible and biodegradable polymers. Since the discovery of the copolymerization of epoxides and CO2 in 1969 by Inoue et al., this has become an important and useful technology for the large‐scale utilization of CO2 in chemical synthesis, employing mainly propylene oxide, and cyclohexene oxide (CHO). Only in recent years, functionalized polycarbonates have become an emerging topic with a broad scope of potential applications. This review summarizes synthetic routes and properties of numerous functionalized polycarbonates synthesized from CO2 and functional epoxide monomers. Implications for new materials and possible applications, for instance for pharmaceutical purposes and membranes are reviewed. Besides polycarbonates based on oxirane and CHO derivatives, particular emphasis is placed on the manifold synthetic approaches and postpolymerization modifications of glycidyl ether based polycarbonates. Not only functionalized linear polycarbonates are presented but also a variety of novel polycarbonate architectures, e.g., star and hyperbranched polymers.

Functional Polycarbonates from Carbon Dioxide and Tailored Epoxide Monomers: Degradable Materials and Their Application Potential

Lignin Fractionation Methods: Can Lignin Fractions Be Separated in a True Industrial Process?

Analytical methods for obtaining binding parameters of drug-protein interactions: A review.

Hyperbranched, multifunctional polycarbonate polyols based on CO2, cyclohexene oxide (CHO), and the “inimer” (initiator–monomer) (4-hydroxymethyl)cyclohexene oxide (HCHO) were prepared in one-pot syntheses. The related linear poly(hydroxymethyl cyclohexene carbonate) structures based on protected HCHO and postpolymerization deprotection were also synthesized as model compounds. The content of hydroxyl functionalities was adjustable for both linear and hyperbranched terpolymer systems. All CO2/epoxide polymerizations were catalyzed by the (R,R)-(salcy)-Co(III)Cl complex. The polycarbonates obtained were comprehensively investigated using various 1D and 2D NMR techniques, SEC, FT-IR, UV–vis spectroscopy, and contact angle measurements. Rigid polyols with molecular weights between 3600 and 9200 g mol–1 and moderate dispersity between 1.18 and 1.64 (Mw/Mn) were obtained. In addition, the materials were examined with respect to their thermal properties, intrinsic viscosity, and their three-dimensional structur...

Rigid Hyperbranched Polycarbonate Polyols from CO2 and Cyclohexene-Based Epoxides

Polymeric stationary phases for size exclusion chromatography: A review.

The morphology of surfaces critically influences their interaction with the surrounding phase. Herein, we report a modular approach for the synthesis of organic-inorganic raspberry-, strawberry-, and seedpod-like particles to template the porosity of superficially porous particles. Divinylbenzene (DVB) microspheres were employed as core particles, which were modified with polar and nonpolar polymer shells. Subsequently, silica nanoparticle templates were covalently tethered to said particles. Further grafting of polymer shells and subsequent template removal yielded superficially porous core-shell particles. In addition, we introduce a facile procedure for the synthesis of superficially porous particles without distinguishable core-shell morphology. Organic seedpod-like particles were prepared from DVB and silica templates, yielding superficially porous particles after template removal. The surface morphology of the templated particles was investigated via scanning electron microscopy (SEM), transmission electron microscopy (TEM), and atomic force microscopy (AFM). X-ray photoelectron spectroscopy (XPS) was performed to prove the chemical modification of the particle surfaces.

Two Grapes Short of a Fruit Salad:Raspberry-, Strawberry-, and Seedpod-Like Organic Microspheres via Colloidal Nanotemplating

Multiarm star copolymers, consisting of hyperbranched poly(ethylene oxide) (hbPEO) or poly(butylene oxide) (hbPBO) polyether copolymers with glycerol branching points as a core, and linear aliphatic polycarbonate arms generated from carbon dioxide (CO2) and epoxide monomers, were synthesized via a “core-first” approach in two steps. First, hyperbranched polyether polyols were prepared by anionic copolymerization of ethylene oxide or 1,2-butylene oxide with 8–35% glycidol with molecular weights between 800 and 389,000 g·mol–1. Second, multiple arms were grown via immortal copolymerization of CO2 with propylene oxide or 1,2-butylene oxide using the polyether polyols as macroinitiators and (R,R)-(salcy)-CoCl as a catalyst in a solvent-free procedure. Molecular weights up to 812,000 g·mol–1 were obtained for the resulting multiarm polycarbonates, determined by online viscometry with universal calibration and 1H NMR. Comparing the synthesis of different multiarm star polycarbonates, a combination of a highly r...

Multiarm Polycarbonate Star Polymers with a Hyperbranched Polyether Core from CO2 and Common Epoxides

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Polymeric stationary phases for size exclusion chromatography: A review.

Two Grapes Short of a Fruit Salad:Raspberry-, Strawberry-, and Seedpod-Like Organic Microspheres via Colloidal Nanotemplating

Multiarm Polycarbonate Star Polymers with a Hyperbranched Polyether Core from CO2 and Common Epoxides