ABSTRACT Electrochemically mediated atom transfer radical polymerizations (ATRPs) provide well‐defined polymers with designed dispersity as well as under external temporal and spatial control. In this study, 1‐cyano‐1‐methylethyl diethyldithiocarbamate, typically used as chain‐transfer agent (CTA) in reversible addition–fragmentation chain transfer (RAFT) polymerization, was electrochemically activated by the ATRP catalyst CuI/2,2′‐bipyridine (bpy) to control the polymerization of methyl methacrylate. Mechanistic study showed that this polymerization was mainly controlled by the ATRP equilibrium. The effect of applied potential, catalyst counterion, catalyst concentration, and targeted degree of polymerization were investigated. The chain‐end functionality was preserved as demonstrated by chain extension of poly(methyl methacrylate) withn‐butyl methacrylate and styrene. This electrochemical ATRP procedure confirms that RAFT CTAs can be activated by an electrochemical stimulus. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem.2019,57, 376–381
more »
« less
Transformation of gels via catalyst-free selective RAFT photoactivation
This work explores the concept of structurally tailored and engineered macromolecular (STEM) networks by proposing a novel metal-free approach to prepare the networks. STEM networks are composed of polymer networks with latent initiator sites affording post-synthesis modification. The proposed approach relies on selectively activating the fragmentation of trithiocarbonate RAFT agent by relying on visible light RAFT iniferter photolysis coupled with RAFT addition–fragmentation process. The two-step synthesis explored in this work generates networks that are compositionally and mechanically differentiated than their pristine network. In addition, by careful selection of crosslinkers, conventional poly(ethylene glycol) dimethacrylate ( M n = 750) or trithiocarbonate dimethacrylate crosslinker (bis[(2-propionate)ethyl methacrylate] trithiocarbonate (bisPEMAT)), and varying concentrations of RAFT inimer (2-(2-( n -butyltrithiocarbonate)-propionate)ethyl methacrylate (BTPEMA)), three different types of primary (STEM-0) poly(methyl methacrylate) (PMMA) networks were generated under green light irradiation. These networks were then modified with methyl acrylate (MA) or N , N -dimethylacrylamide (DMA), under blue light irradiation to yield STEM-1 gels that are either stiffer or softer with different responses to polarity (hydrophilicity/hydrophobicity).
more »
« less
- Award ID(s):
- 1726525
- PAR ID:
- 10128307
- Date Published:
- Journal Name:
- Polymer Chemistry
- Volume:
- 10
- Issue:
- 19
- ISSN:
- 1759-9954
- Page Range / eLocation ID:
- 2477 to 2483
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
-
The direct-growth technique was used to synthesize several macromonomers (MMs) employing reversible addition–fragmentation chain transfer (RAFT) polymerization by growing directly from a norbornene-functionalized chain transfer agent (CTA). We aimed to investigate the formation of bisnorbornenyl species resulting from radical termination by combination ( i.e. , coupling) during RAFT polymerization at different monomer conversion values in four types of monomers: styrene, tert -butyl acrylate, methyl methacrylate and N -acryloyl morpholine. Ring-opening metathesis polymerization (ROMP) of these MMs using Grubbs' 3rd generation catalyst (G3) at an MM : G3 ratio of 100 : 1 resulted in the formation of bottlebrush polymers. Analysis by size-exclusion chromatography (SEC) revealed high molar mass shoulders of varying intensities attributed to the incorporation of these bisnorbornenyl species to generate dimeric or higher-order bottlebrush polymer oligomers. The monomer type in the RAFT step heavily influenced the amount of these bottlebrush polymer dimers and oligomers, as did the monomer conversion value in the RAFT step: We found that the ROMP of polystyrene MMs with a target backbone degree of polymerization of 100 produced detectable coupling at ≥20% monomer conversion in the RAFT step, while it took ≥80% monomer conversion to observe coupling in the poly( tert -butyl acrylate) MMs. We did not detect coupling in the poly(methyl methacrylate) MMs, but broadening of the SEC peaks and an increase in dispersity occurred, suggesting the presence of metathesis-active alkene-containing chain ends created by disproportionation. Finally, poly( N -acryloyl morpholine) MMs, even when reaching 90% monomer conversion in the RAFT step, showed no detectable coupling in the bottlebrush polymers. These results highlight the importance of monomer choice and RAFT polymerization conditions in making MMs for ROMP grafting-through to make well-defined bottlebrush polymers.more » « less
-
null (Ed.)A one pot synthesis is applied to control the chain structure and architecture of multiply dynamic polymers, enabling fine tuning of materials properties by choice of polymer chain length or crosslink density. Macromolecules containing both non-covalent linkers based on quadruple hydrogen-bonded 2-(((6-(3-(6-methyl-4-oxo-1,4-dihydropyrimidin-2-yl)ureido)hexyl)carbamoyl)oxy)ethyl methacrylate (UPyMA), and thermoresponsive dynamic covalent furan–maleimide based Diels–Alder linkers are explored. The primary polymer's architecture was controlled by reversible addition-fragmentation chain transfer (RAFT) polymerization, with the dynamic non-covalent (UPyMA) and dynamic covalent furfuryl methacrylate (FMA) units incorporated into the same backbone. The materials are crosslinked, taking advantage of the “click” chemistry properties of the furan–maleimide reaction. The polymer materials showed stimulus-responsive thermomechanical properties with a decrosslinking temperature increasing with the polymer's primary chain length and crosslink density. The polymers had good thermally promoted self-healing properties due to the dynamic covalent Diels–Alder bonds. Besides, the materials had excellent stress relaxation characteristics induced by the exchange of the hydrogen bonds in UPyMA units.more » « less
-
Abstract Photomediated reversible addition fragmentation chain transfer (RAFT) step‐growth polymerization is performed using a trithiocarbonate‐based chain transfer agent (CTA) and acrylate‐based monomers both with and without a photocatalyst. The versatility of photo‐mediated RAFT step‐growth is demonstrated by one‐pot synthesis of a graft copolymer via sequential monomer addition. Furthermore, oxygen‐tolerant photo‐mediated RAFT step‐growth is demonstrated, facilitated by the appropriate selection of photocatalyst and solvent pair (zinc tetraphenyl porphyrin [ZnTPP] and dimethyl sulfoxide [DMSO]), enabling ultralow volume polymerization under open‐air conditions.more » « less
-
Photomediated RAFT step-growth polymerization was performed with and without the presence of a photocatalyst using a trithiocarbonate-based CTA and a maleimide monomer. Under catalyst-free conditions, the polymerization proceeded with an appreciable rate under irradiation with blue and green light, which was extended to red light in the presence of ZnTPP.more » « less
An official website of the United States government

