Browse
Submit Data
Databases
API
Help

Dataset Information

7 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Photoinduced Iron-Catalyzed ATRP of Renewable Monomers in Low-Toxicity Solvents: A Greener Approach.

ABSTRACT: Producing polymers from renewable resources via more sustainable approaches has become increasingly important. Herein we present the polymerization of monomers obtained from biobased renewable resources, employing an environmentally friendly photoinduced iron-catalyzed atom transfer radical polymerization (ATRP) in low-toxicity solvents. We demonstrate that renewable monomers can be successfully polymerized into sustainable polymers with controlled molecular weights and narrow molar mass distributions (Đ as low as 1.17). This is in contrast to reversible addition-fragmentation chain-transfer (RAFT) polymerization, arguably the most commonly employed method to polymerize biobased monomers, which led to poorer molecular weight control and higher dispersities for these specific monomers (Đs ∼ 1.4). The versatility of our approach was further highlighted by the temporal control demonstrated through intermittent "on/off" cycles, controlled polymerizations of a variety of monomers and chain lengths, oxygen-tolerance, and high end-group fidelity exemplified by the synthesis of block copolymers. This work highlights photoinduced iron-catalyzed ATRP as a powerful tool for the synthesis of renewable polymers.

SUBMITTER: Parkatzidis K

PROVIDER: S-EPMC9301913 | biostudies-literature |

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Similar Datasets

Photoinduced iron-catalyzed C-H alkylation of polyolefins.

Project description:Chemically introducing diverse polar groups into polyolefins via carbon-hydrogen bond alkylation with polar olefins is of substantial value in the synthesis of next-generation lightweight thermoplastics, which is still underdeveloped. In this work, we report a new approach for efficient carbon-hydrogen bond alkylation in commodity polyolefins using photoinduced iron catalysis. Various polyolefins could be functionalized with broad scope. Polar groups could be incorporated in a single step. The controllable synthesis of multi-polar functional polyolefins could be achieved by a designed module-assembled process. Remarkably, even low levels of functionalization could upcycle the polyolefin materials to exhibit unusual physical properties, such as enhancement of the transparencies, strains, stresses at break of the materials, and hydrophilicity.

| S-EPMC10498505 | biostudies-literature

Renewable Fabric Surface-Initiated ATRP Polymerizations: Towards Mixed Polymer Brushes.

Project description:A totally new approach in the synthesis of mixed polymer brushes tethered on polyamide (PA) surfaces is presented herein. As a proof of concept, two types of homopolymers were synthesized in sequential surface-initiated atom transfer radical polymerization (SI-ATRP) reactions: poly(methyl methacrylate)/poly((2-dimethylamino)ethyl methacrylate) and polystyrene /poly((2-dimethylamino)ethyl methacrylate). The ATRP initiator was immobilized on the surface through PA chain-end groups in two subsequent steps, separated by homo-polymerizations. The amount of the PA chains' end groups available on the modified surface was tuned by the thermal rearrangement of the surface.

| S-EPMC7153387 | biostudies-literature

Photoinduced Metal-Free Surface Initiated ATRP from Hollow Spheres Surface.

Project description:Well-defined amphiphilic diblock copolymer poly (methyl methacrylate)-b-poly (N-isopropylacrylamide) grafted hollow spheres (HS-g-PMMA-b-PNIPAM) hybrid materials were synthesized via metal-free surface-initiated atom transfer radical polymerization (SI-ATRP). The ATRP initiators ?-Bromoisobutyryl bromide (BIBB) were attached onto hollow sphere surfaces through esterification of acyl bromide groups and hydroxyl groups. The synthetic ATRP initiators (HS-Br) were further used for the metal-free SI-ATRP of methyl methacrylate (MMA) and N-isopropyl acrylamide (NIPAM) using 10-phenylphenothiazine (PTH) as the photocatalyst. The molecular weight of the polymers, structure, morphology, and thermal stability of the hybrid materials were characterized via gel permeation chromatography (GPC), X-ray photoelectron spectroscopy (XPS), ¹H-nuclear magnetic resonance spectroscopy (¹H NMR), transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FT-IR), and thermogravimetric analysis (TGA), respectively. The results indicated that the ATRP initiator had been immobilized onto HS surfaces successfully followed by metal-free SI-ATRP of MMA and NIPAM, the Br atom had located at the end of the main PMMA polymer chain, and the polymerization process possessed the characteristic of controlled/"living" polymerization. The thermal stability of the hybrid materials was increased significantly compared to the pure PMMA and PNIPAM.

| S-EPMC6523302 | biostudies-literature

Silyl Ketene Acetals/B(C₆F₅)₃ Lewis Pair-Catalyzed Living Group Transfer Polymerization of Renewable Cyclic Acrylic Monomers.

Project description:This work reveals the silyl ketene acetal (SKA)/B(C₆F₅)₃ Lewis pair-catalyzed room-temperature group transfer polymerization (GTP) of polar acrylic monomers, including methyl linear methacrylate (MMA), and the biorenewable cyclic monomers γ-methyl-α-methylene-γ-butyrolactone (MMBL) and α-methylene-γ-butyrolactone (MBL) as well. The in situ NMR monitored reaction of SKA with B(C₆F₅)₃ indicated the formation of Frustrated Lewis Pairs (FLPs), although it is sluggish for MMA polymerization, such a FLP system exhibits highly activity and living GTP of MMBL and MBL. Detailed investigations, including the characterization of key reaction intermediates, polymerization kinetics and polymer structures have led to a polymerization mechanism, in which the polymerization is initiated with an intermolecular Michael addition of the ester enolate group of SKA to the vinyl group of B(C₆F₅)₃-activated monomer, while the silyl group is transferred to the carbonyl group of the B(C₆F₅)₃-activated monomer to generate the single-monomer-addition species or the active propagating species; the coordinated B(C₆F₅)₃ is released to the incoming monomer, followed by repeated intermolecular Michael additions in the subsequent propagation cycle. Such neutral SKA analogues are the real active species for the polymerization and are retained in the whole process as confirmed by experimental data and the chain-end analysis by matrix-assisted laser desorption/ionization time of flight mass spectroscopy (MALDI-TOF MS). Moreover, using this method, we have successfully synthesized well-defined PMMBL-b-PMBL, PMMBL-b-PMBL-b-PMMBL and random copolymers with the predicated molecular weights (Mn) and narrow molecular weight distribution (MWD).

| S-EPMC6017534 | biostudies-literature

Gelation in Photoinduced ATRP with Tuned Dispersity of the Primary Chains.

Project description:We investigated gelation in photoinduced atom transfer radical polymerization (ATRP) as a function of Cu catalyst loading and thus primary chain dispersity. Using parallel polymerizations of methyl acrylate with and without the addition of a divinyl crosslinker (1,6-hexanediol diacrylate), the approximate values of molecular weights and dispersities of the primary chains at incipient gelation were obtained. In accordance with the Flory-Stockmayer theory, experimental gelation occurred at gradually lower conversions when the dispersity of the primary chains increased while maintaining a constant monomer/initiator/crosslinker ratio. Theoretical gel points were then calculated using the measured experimental values of dispersity and initiation efficiency. An empirical modification to the Flory-Stockmayer equation for ATRP was implemented, resulting in more accurate predictions of the gel point. Increasing the dispersity of the primary chains was found not to affect the distance between the theoretical and experimental gel points and hence the extent of intramolecular cyclization. Furthermore, the mechanical properties of the networks, such as equilibrium swelling ratio and shear storage modulus showed little variation with catalyst loading and depended primarily on the crosslinking density.

| S-EPMC10018774 | biostudies-literature

Assemblies of Polyacrylonitrile-Derived Photoactive Polymers as Blue and Green Light Photo-Cocatalysts for Cu-Catalyzed ATRP in Water and Organic Solvents.

Project description:Photoluminescent nanosized quasi-spherical polymeric assemblies prepared by the hydrothermal reaction of polyacrylonitrile (PAN), ht-PLPPAN, were demonstrated to have the ability to photo-induce atom transfer radical polymerization (ATRP) catalyzed by low, parts per million concentrations of CuII complex with tris(2-pyridylmethyl)amine (TPMA). Such photo induced ATRP reactions of acrylate and methacrylate monomers were performed in water or organic solvents, using ht-PLPPAN as the photo-cocatalyst under blue or green light irradiation. Mechanistic studies indicate that ht-PLPPAN helps to sustain the polymerization by facilitating the activation of alkyl bromide species by two modes: 1) green or blue light-driven photoreduction of the CuII catalyst to the activating CuI form, and 2) direct activation of dormant alkyl bromide species which occurs only under blue light. The photoreduction of the CuII complex by ht-PLPPAN was confirmed by linear sweep voltammetry performed under illumination. Analysis of the polymerization kinetics in aqueous media indicated even though CuI complexes comprised only 1-1.4% of all Cu species at equilibrium, they exhibited high activation rate constant and activated the alkyl bromide initiators five to six orders of magnitude faster than ht-PLPPAN.

| S-EPMC8407075 | biostudies-literature

Nanorod-Shaped Basic Al2O3 Catalyzed N,N-Diformylation of Bisuracil Derivatives: A Greener "NOSE" Approach.

Project description:A feasible "NOSE" (nanoparticles-catalyzed organic synthesis enhancement) protocol has been developed for N,N-diformylation of bisuracil derivatives using nano-Al2O3 rods as an efficient, inexpensive, and recyclable catalyst under solvent-free reaction condition at 40°C. The catalyst was reused up to the 4th cycle without affecting the rate and yield of the N,N-diformylation products appreciably.

| S-EPMC3767338 | biostudies-literature

Vinyl ethers and epoxides photoinduced copolymerization with perfluoropolyalkylether monomers.

Project description:New perfluoropolyalkylether (PFPAE) monomers, chain extended with different alkyl groups and functionalized with vinyl ether or epoxide end-groups, were employed, together with trimethylolpropane trivinyl ether or trimethylolpropane triglycidyl ether, to produce fluorinated copolymers. The photoinduced cationic polymerization was investigated, and the PFPAE-based copolymer properties were thoroughly characterized. Interesting surface properties and two different values of refractive index were observed: thus, these fluorinated copolymers can be suitable materials for the manufacture of self-cleaning coatings and optical waveguides.

| S-EPMC7952294 | biostudies-literature

An Expeditious and Greener Synthesis of 2-Aminoimidazoles in Deep Eutectic Solvents.

Project description:A high-yield one-pot two-step synthesis of 2-aminoimidazoles (2-AI), exploiting an under-air heterocyclodehydration process between ?-chloroketones and guanidine derivatives, and using deep eutectic solvents (DESs) as nonconventional, "green" and "innocent" reaction media, has been accomplished successfully. The combination of either glycerol or urea with choline chloride (ChCl) proved to be effective for decreasing the reaction time to about 4-6 h in contrast to the 10-12 h usually required for the same reaction run in toxic and volatile organic solvents and under an argon atmosphere. In addition, the use of the ChCl-urea as a DES also enables the direct isolation of triaryl-substituted 2-AI derivatives by means of a simple work-up procedure consisting in filtration and crystallization, and allows the recycle of the DES mixture. A plausible mechanism highlighting the potential role played by hydrogen bonding catalysis has also been illustrated.

| S-EPMC6273198 | biostudies-literature

Fast, greener and scalable direct coupling of organolithium compounds with no additional solvents.

Project description:Although the use of catalytic rather than stoichiometric amounts of metal mediator in cross-coupling reactions between organic halides and organometallic counterparts improves significantly the atom economy and waste production, the use of solvents and stoichiometric generation of main-group byproducts (B, Sn and Zn) hamper the 'greenness' and industrial efficiency of these processes. Here we present a highly selective and green Pd-catalysed cross-coupling between organic halides and organolithium reagents proceeding without additional solvents and with short reaction times (10 min). This method bypasses a number of challenges previously encountered in Pd-catalysed cross-coupling with organolithium compounds such as strict exclusion of moisture, dilution and slow addition. Operational ease of this protocol combines the use of industrially viable catalysts loadings (down to 0.1 mol%), scalability of the process (tested up to 120 mmol) and exceptionally favourable environmental impact (E factors in several cases as low as 1).

| S-EPMC4895725 | biostudies-literature

OmicsDI is part of the ELIXIR infrastructure

OmicsDI is an Elixir interoperability service. Learn more ›

Tweets

OmicsDI Databases

PRIDE
PeptideAtlas
MassIVE
JPOST Repository
Physiome Model Repository

EGA
EVA
ENA
LINCS
PAXDB
Cell Collective

MetaboLights
Metabolomics Workbench
MetabolomeExpress
GNPS
BioModels
FAIRDOMHub

ArrayExpress
dbGaP
ExpressionAtlas
GEO
NODE

Information

Databases
Help
API
Contact us
Code on GitHub
Terms of use
Submit Data