Browse
Submit Data
Databases
API
Help

Dataset Information

24 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

N-Heterocyclic Olefins as Organocatalysts for Polymerization: Preparation of Well-Defined Poly(propylene oxide).

ABSTRACT: The metal-free polymerization of propylene oxide (PO) using a special class of alkene—N-heterocyclic olefins (NHOs)—as catalysts is described. Manipulation of the chemical structure of the NHO organocatalyst allows for the preparation of the poly(propylene oxide) in high yields with high turnover (TON>2000), which renders this the most active metal-free system for the polymerization of PO reported to date. The resulting polyether displays predictable end groups, molar mass, and a low dispersity (?(M)<1.09). NHOs with an unsaturated backbone are essential for polymerization to occur, while substitution at the exocyclic carbon atom has an impact on the reaction pathway and ensures the suppression of side reactions.

SUBMITTER: Naumann S

PROVIDER: S-EPMC4539597 | biostudies-literature | 2015 Aug

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

N-Heterocyclic Olefins as Organocatalysts for Polymerization: Preparation of Well-Defined Poly(propylene oxide).

Naumann Stefan S Thomas Anthony W AW Dove Andrew P AP

Angewandte Chemie (International ed. in English) 20150701 33

The metal-free polymerization of propylene oxide (PO) using a special class of alkene—N-heterocyclic olefins (NHOs)—as catalysts is described. Manipulation of the chemical structure of the NHO organocatalyst allows for the preparation of the poly(propylene oxide) in high yields with high turnover (TON>2000), which renders this the most active metal-free system for the polymerization of PO reported to date. The resulting polyether displays predictable end groups, molar mass, and a low dispersity ...[more]

PMID: 26136456

Similar Datasets

The synthesis of well-defined poly(vinylbenzyl chloride)-grafted nanoparticles via RAFT polymerization.

Project description:We describe the use of one of the most advanced radical polymerization techniques, the reversible addition fragmentation chain transfer (RAFT) process, to produce highly functional core-shell particles based on a silica core and a shell made of functional polymeric chains with very well controlled structure. The versatility of RAFT polymerization is illustrated by the control of the polymerization of vinylbenzyl chloride (VBC), a highly functional monomer, with the aim of designing silica core-poly(VBC) shell nanoparticles. Optimal conditions for the control of VBC polymerization by RAFT are first established, followed by the use of the "grafting from" method to yield polymeric brushes that form a well-defined shell surrounding the silica core. We obtain particles that are monodisperse in size, and we demonstrate that the exceptional control over their dimensions is achieved by careful tailoring the conditions of the radical polymerization.

| S-EPMC3701384 | biostudies-literature

Acid-Labile Surfactants Based on Poly(ethylene glycol), Carbon Dioxide and Propylene Oxide: Miniemulsion Polymerization and Degradation Studies.

Project description:Partially degradable, nonionic AB and ABA type di- and triblock copolymers based on poly(propylene carbonate) and poly(ethylene glycol) blocks were synthesized via immortal copolymerization of carbon dioxide and propylene oxide, using mPEG or PEG as a macroinitiator, and (R,R)-(salcy)-CoOBzF₅ as a catalyst in a solvent-free one-pot procedure. The amphiphilic surfactants were prepared with molecular weights (Mn) between 2800 and 10,000 g·mol-¹ with narrow molecular weight distributions (1.03⁻1.09). The copolymers were characterized using ¹H-, 13C- and DOSY-NMR spectroscopy and size exclusion chromatography (SEC). Surface-active properties were determined by surface tension measurements (critical micelle concentration, CMC; CMC range: 1⁻14 mg·mL-¹). Degradation of the acid-labile polycarbonate blocks was investigated in aqueous solution using online ¹H-NMR spectroscopy and SEC. The amphiphilic polymers were used as surfactants in a direct miniemulsion polymerization for poly(styrene) (PS) nanoparticles with mean diameter of 270 to 940 nm. The usage of an acid-triggered precipitation of the emulsion simplified the separation of the particles from the surfactant and purification of the nanoparticles.

| S-EPMC6419001 | biostudies-literature

Structurally Diverse Nitric Oxide-Releasing Poly(propylene Imine) Dendrimers.

Project description:Structurally diverse secondary amine-functionalized poly(propylene imine) (PPI) dendrimers capable of tunable nitric oxide (NO) release were synthesized in a straightforward, one-step manner using ring-opening or conjugate-addition reactions with propylene oxide (PO), styrene oxide (SO), acrylonitrile (ACN), poly(ethylene glycol) methyl ether acrylate (average Mn = 480) (PEG) or 1,2-epoxy-9-decene (ED). N-Diazeniumdiolate nitric oxide donors were formed on the resulting secondary amine-functionalized G2-G5 PPI dendrimers by reaction with NO gas in basic solution. The NO storage and release kinetics for the resulting dendritic scaffolds were diverse (0.9-3.8 ?mol NO/mg totals and 0.3 to 4.9 h half lives), illustrating the importance of the exterior chemical modification (e.g., steric environments, hydrophobicity, etc.) on diazeniumdiolate stability/decomposition. Tunable NO release was demonstrated by combining two donor systems on the exterior of one macromolecular scaffold. Additionally, a mathematical model was developed that allows for the simulation of dual NO release kinetics using the NO release data from the two single NO donor systems. The approaches described herein extend the range and scope of NO-releasing macromolecular scaffolds by unlocking a series of materials for use as dopants in biomedical polymers or stand-alone therapeutics depending on the exterior modification.

| S-EPMC3204868 | biostudies-literature

The Lewis Pair Polymerization of Lactones Using Metal Halides and N-Heterocyclic Olefins: Theoretical Insights.

Project description:Lewis pair polymerization employing N-Heterocyclic olefins (NHOs) and simple metal halides as co-catalysts has emerged as a useful tool to polymerize diverse lactones. To elucidate some of the mechanistic aspects that remain unclear to date and to better understand the impact of the metal species, computational methods have been applied. Several key aspects have been considered: (1) the formation of NHO-metal halide adducts has been evaluated for eight different NHOs and three different Lewis acids, (2) the coordination of four lactones to MgCl? was studied and (3) the deprotonation of an initiator (butanol) was investigated in the presence and absence of metal halide for one specific Lewis pair. It was found that the propensity for adduct formation can be influenced, perhaps even designed, by varying both organic and metallic components. Apart from the NHO backbone, the substituents on the exocyclic, olefinic carbon have emerged as interesting tuning site. The tendency to form adducts is ZnCl? > MgCl? > LiCl. If lactones coordinate to MgCl?, the most likely binding mode is via the carbonyl oxygen. A chelating coordination cannot be ruled out and seems to gain importance upon increasing ring-size of the lactone. For a representative NHO, it is demonstrated that in a metal-free setting an initiating alcohol cannot be deprotonated, while in the presence of MgCl? the same process is exothermic with a low barrier.

| S-EPMC6017504 | biostudies-literature

A Green Platform for Preparation of the Well-Defined Polyacrylonitrile: 60Co ?-ray Irradiation-Initiated RAFT Polymerization at Room Temperature.

Project description:60Co ?-ray irradiation-initiated reversible addition?fragmentation chain transfer (RAFT) polymerization at room temperature with 2-cyanoprop-2-yl 1-dithionaphthalate (CPDN) as the chain transfer agent was first applied to acrylonitrile (AN) polymerization, providing a "green" platform for preparing polyacrylonitrile (PAN)-based carbon fibers using an environment-friendly energy source. Various effects of dose rate, molar ratio of the monomer to the chain transfer agent, monomer concentration and reaction time on the AN polymerization behaviors were performed to improve the controllability of molecular the weight and molecular weight distribution of the obtained PAN. The feature of the controlled polymerization was proven by the first-order kinetics, linear increase of the molecular weight with the monomer conversion and a successful chain-extension experiment. The molecular weight and molecular weight distribution of PAN were characterized by size exclusion chromatography (SEC). ¹H NMR and Matrix assisted laser desorption ionization/time of flight mass spectra (MALDI-TOF-MS) confirmed the chain-end functionality of PAN, which also was supported by the successful chain-extension experiments of original PANs with acrylonitrile and styrene as the second monomers respectively.

| S-EPMC6432107 | biostudies-literature

Preparation and Laser Marking Properties of Poly(propylene)/Molybdenum Sulfide Composite Materials.

Project description:In this study, using molybdenum sulfide (MoS2) as laser-sensitive particles and poly(propylene) (PP) as the matrix resin, laser-markable PP/MoS2 composite materials with different MoS2 contents ranging from 0.005 to 0.2% were prepared by melt-blending. A comprehensive analysis of the laser marking performance of PP/MoS2 composites was carried out by controlling the content of laser additives, laser current intensity, and the scanning speed of laser marking. The color difference test shows that the best laser marking performance of the composite can be obtained at the MoS2 content of 0.02 wt %. The surface morphology of the PP/MoS2 composite material was observed after laser marking using a metallographic microscope, an optical microscope, and a scanning electron microscope (SEM). During the laser marking process, the laser energy was absorbed and converted into heat energy to cause high-temperature melting, pyrolysis, and carbonization of PP on the surface of the PP/MoS2 composite material. The black marking from carbonized materials was formed in contrast to the white matrix. Using X-ray diffraction (XRD), Fourier transform infrared (FT-IR) spectroscopy, and Raman spectroscopy, the composite materials before and after laser marking were tested and characterized. The PP/MoS2 composite material was pyrolyzed to form amorphous carbonized materials. The effect of the laser-sensitive MoS2 additive on the mechanical properties of composite materials was investigated. The results show that the PP/MoS2 composite has the best laser marking property when the MoS2 loading content is 0.02 wt %, the laser marking current intensity is 11 A, and the laser marking speed is 800 mm/s, leading to a clear and high-contrast marking pattern.

| S-EPMC8028170 | biostudies-literature

Preparation and properties of propylene oxide and octenylsuccinic anhydride modified potato starches.

Project description:Starch was dually chemically modified for developing food-grade ingredients of lower digestibility and their properties were compared to those of single modified and native starches. Hydroxypropylation with propylene oxide (HP) followed by esterification with octenylsuccinic anhydride (OSA) of potato starch (P-native) produced derivatives with lower digestibility than esterification solely with OSA. The dextrose equivalent, maltose and glucose contents, which were used as the main indicators for in vitro digestion, were lower for modified starches. P-HP0.2-OSA0.0200 derivative was the least digestible; the glucose and maltose contents were lowered by 28.3 and 42.1% compared to P-native. The aggregation behavior of enzymatically hydrolyzed starch derivatives was studied in aqueous solution by employing the fluorescence probe and dynamic light scattering techniques. The critical aggregation concentration for OSA modified and dually modified starches varied from 1.2 to 3 g/L and from 0.125 to 0.48 g/L, respectively, depending on the degree of OSA substitution. The study showed that above a critical concentration the hydrolyzates of modified starches tend to form the aggregates with different properties depending both on the degree of OSA substitution and chemical structure.

| S-EPMC5223253 | biostudies-literature

Influence of the Headgroup on the Interaction of Poly(ethylene oxide)-Poly(propylene oxide) Block Copolymers with Lipid Bilayers.

Project description:The lipid headgroup plays an important role in the association of polymers with lipid bilayer membranes. Herein, we report how a glycerol headgroup versus a choline headgroup affects the interaction of poly(ethylene oxide)-b-poly(propylene oxide) (PEO-PPO) block copolymers with lipid bilayer vesicles. Unilamellar vesicles composed of phosphatidylcholine and phosphatidylglycerol at various molar ratios were used as model membranes. The interactions between the block copolymers and lipid bilayers were quantified by pulsed-field gradient nuclear magnetic resonance (PFG-NMR) based on the distinctly different mobilities of free and bound polymers. All the investigated polymer species showed significantly higher binding with 1-palmitoyl-2-oleoyl-sn-glycero-3-phospho-(1'-rac-glycerol) sodium salt (POPG) liposomes than with 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine (POPC) liposomes, indicating stronger association with the glycerol headgroup compared to the choline headgroup. This effect did not become significant until the composition of mixed POPC/POPG liposomes contained more than 20 mol % POPG. A plausible explanation for the enhanced polymer binding with POPG invokes the role of hydrogen bonding between the glycerol headgroup and the ether moieties of the polymers.

| S-EPMC7302449 | biostudies-literature

Well-defined Poly(lactic acid)s Containing Poly(ethylene glycol) Side-chains.

Project description:Poly(ethylene glycol) (PEG) side-chain functionalized lactide analogues have been synthesized in four steps from commercially available L-lactide. The key step in the synthesis is the 1,3-dipolar cycloaddition between PEG-azides and a highly strained spirolactide-heptene monomer, which proceeds in high conversions. The PEG-grafted lactides analogues were polymerized via ring-opening polymerization using triazacyclodecene as organocatalyst to give well-defined tri- and hepta-(ethylene glycol)-poly(lactide)s (PLA) with molecular weights above 10 kDa and polydispersity indices between 1.6 and 2.1. PEG-poly(lactide) (PLA) with PEG chain M(n) 2000 was also prepared but GPC analysis showed a bimodal profile indicating the presence of starting macromonomer. Cell adhesion assays were performed using MC3T3 E-1 osteoblast-like cells demonstrating that PEG-containing PLA reduces cell adhesion significantly when compared to unfunctionalized PLA.

| S-EPMC3263433 | biostudies-literature

Stable Mesoionic N-Heterocyclic Olefins (mNHOs).

Project description:We report a new class of stable mesoionic N-heterocyclic olefins, featuring a highly polarized (strongly ylidic) double bond. The ground-state structure cannot be described through an uncharged mesomeric Lewis-structure, thereby structurally distinguishing them from traditional N-heterocyclic olefins (NHOs). mNHOs can easily be obtained through deprotonation of the corresponding methylated N,N'-diaryl-1,2,3-triazolium and N,N'-diaryl-imidazolium salts, respectively. In their reactivity, they represent strong ?-donor ligands as shown by their coordination complexes of rhodium and boron. Their calculated proton affinities, their experimentally derived basicities (competition experiments), as well as donor abilities (Tolman electronic parameter; TEP) exceed the so far reported class of NHOs.

| S-EPMC7154647 | biostudies-literature

OmicsDI is part of the ELIXIR infrastructure

OmicsDI is an Elixir interoperability service. Learn more ›

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