Browse
Submit Data
Databases
API
Help

Dataset Information

14 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Polymerization of Biobased Farnesene in Miniemulsions by Nitroxide-Mediated Polymerization.

ABSTRACT: Biobased farnesene (Far) was polymerized by nitroxide-mediated polymerization in miniemulsions using two different alkoxyamine initiators, the SG1-based and succinimidyl-modified BlocBuilder (NHS-BB) and Dispolreg 007 (D7). Stable emulsions were observed after 30 h of reaction at 90 °C, where NHS-BB-initiated systems resulted in smaller particles (?300 nm) than using D7 (?400 nm). Successful chain extension of the poly(Far) macroinitiators (24,500-39,700 g mol^-1) with styrene were achieved using 15 wt % surfactant relative to monomer concentration. Compartmentalization effects were not observed in these emulsions as the polymerization rate was still much slower compared to the bulk, even though Z-averaged particle sizes were around 300-400 nm. Finally, all biobased diblock copolymers were synthesized by chain-extending poly(Far) macroinitiators with isobornyl methacrylate (iBOMA), where the D7 initiator showed more effective chain extension (less unreacted macroinitiator) than NHS-BB.

SUBMITTER: Luk SB

PROVIDER: S-EPMC7905948 | biostudies-literature | 2021 Feb

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Polymerization of Biobased Farnesene in Miniemulsions by Nitroxide-Mediated Polymerization.

Luk Sharmaine B SB Maríc Milan M

ACS omega 20210211 7

Biobased farnesene (Far) was polymerized by nitroxide-mediated polymerization in miniemulsions using two different alkoxyamine initiators, the SG1-based and succinimidyl-modified BlocBuilder (NHS-BB) and Dispolreg 007 (D7). Stable emulsions were observed after 30 h of reaction at 90 °C, where NHS-BB-initiated systems resulted in smaller particles (∼300 nm) than using D7 (∼400 nm). Successful chain extension of the poly(Far) macroinitiators (24,500-39,700 g mol<sup>-1</sup>) with styrene were ach ...[more]

PMID: 33644601

Similar Datasets

Miktoarm Star Copolymers Prepared by Transformation from Enhanced Spin Capturing Polymerization to Nitroxide-Mediated Polymerization (ESCP-Ŧ-NMP) toward Nanomaterials.

Project description:Reversible-deactivation radical polymerization (RDRP) serves as a powerful tool nowadays for the preparations of unique linear and non-linear macromolecules. In this study, enhanced spin capturing polymerizations (ESCPs) of styrene (St) and tert-butyl acrylate (tBA) monomers were, respectively, conducted in the presence of difunctional (1Z,1'Z)-1,1'-(1,4-phenylene) bis (N-tert-butylmethanimine oxide) (PBBN) nitrone. Four-arm (PSt)4 and (PtBA)4 star macroinitiators (MIs) can be afforded. By correspondingly switching the second monomer (i.e., tBA and St), miktoarm star copolymers (μ-stars) of (PSt)2-μ-(PtBA-b-PSt)2 and (PtBA)2-μ-(PSt-b-PtBA)2) were thus obtained. We further conducted hydrolysis of the PtBA segments to PAA (i.e., poly(acrylic acid)) in μ-stars to afford amphiphilic μ-stars of (PSt)2-μ-(PAA-b-PSt)2 and (PAA)2-μ-(PSt-b-PAA)2. We investigated each polymerization step and characterized the obtained two sets of "sequence-isomeric" μ-stars by FT-IR, 1H NMR, differential scanning calorimeter (DSC), and thermogravimetric analysis (TGA). Interestingly, we identified their physical property differences in the case of amphiphilic μ-stars by water contact angle (WCA) and atomic force microscopy (AFM) measurements. We thus proposed two microstructures caused by the difference of polymer chain sequences. Through this polymerization transformation (Ŧ) approach (i.e., ESCP-Ŧ-NMP), we demonstrated an interesting and facile strategy for the preparations of μ-stars with adjustable/switchable interior and exterior polymer structures toward the preparations of various nanomaterials.

| S-EPMC8467092 | biostudies-literature

Biobased Composites by Photoinduced Polymerization of Cardanol Methacrylate with Microfibrillated Cellulose.

Project description:Biobased monomers and green processes are key to producing sustainable materials. Cardanol, an aromatic compound obtained from cashew nut shells, may be conveniently functionalized, e.g., with epoxy or (meth)acrylate groups, to replace petroleum-based monomers. Photoinduced polymerization is recognized as a sustainable process, less energy intensive than thermal curing; however, cardanol-based UV-cured polymers have relatively low thermomechanical properties, making them mostly suitable as reactive diluents or in non-structural applications such as coatings. It is therefore convenient to combine them with biobased reinforcements, such as microfibrillated cellulose (MFC), to obtain composites with good mechanical properties. In this work a cardanol-based methacrylate monomer was photopolymerized in the presence of MFC to yield self-standing, flexible, and relatively transparent films with high thermal stability. The polymerization process was completed within few minutes even in the presence of filler, and the cellulosic filler was not affected by the photopolymerization process.

| S-EPMC8746221 | biostudies-literature

Controlled Synthesis of Poly(pentafluorostyrene-ran-methyl methacrylate) Copolymers by Nitroxide Mediated Polymerization and Their Use as Dielectric Layers in Organic Thin-film Transistors.

Project description:A library of statistically random pentafluorostyrene (PFS) and methyl methacrylate (MMA) copolymers with narrow molecular weight distributions was produced, using nitroxide mediated polymerization (NMP) to study the effect of polymer composition on the performance of bottom-gate top-contact organic thin-film transistors, when utilized as the dielectric medium. Contact angle measurements confirmed the ability to tune the surface properties of copolymer thin films through variation of its PFS/MMA composition, while impedance spectroscopy determined the effect of this variation on dielectric properties. Bottom-gate, top-contact copper phthalocyanine (CuPc) based organic thin-film transistors were fabricated using the random copolymers as a dielectric layer. We found that increasing the PFS content led to increased field-effect mobility, until a point after which the CuPc no longer adhered to the polymer dielectric.

| S-EPMC7361672 | biostudies-literature

Synthesis of High-Molecular-Weight Biobased Aliphatic Polyesters by Acyclic Diene Metathesis Polymerization in Ionic Liquids

Project description:Acyclic diene metathesis (ADMET) polymerization of an

| S-EPMC9948555 | biostudies-literature

A Proximal Bisnitroxide Initiator: Studies in Low-Temperature Nitroxide-Mediated Polymerizations.

Project description:Nitroxide-mediated "living" radical polymerization with bisalkoxyamine 2,5,5,8,8,11-hexamethyl-4,9-(1-phenylethoxy)-3,10-diphenyl-4,9-diazadodecane produces polymers of controlled length and narrow molecular weight distributions at temperatures ranging from 70 to 110 °C. Polymerizations were run successfully with styrene (St), tert-butyl acrylate (tBA), and dimethylacrylamide (DMA). EPR measurements of the homolysis of this bisalkoxyamine and monoalkoxyamine 2,2,5-trimethyl-3-(1-phenylethoxy)-4-phenyl-3-azahexane at temperatures ranging from 85 to 105 °C give rate constants for the bisalkoxyamine that are approximately twice as large as those for the monoalkoxyamine. (1)H NMR investigations of the decomposition of both alkoxyamines at 125 °C show enhanced decomposition for the bisalkoxyamine. EPR decomposition studies at 120 °C on the corresponding bis- and mononitroxides 2,5,5,8,8,11-hexamethyl-3,10-diphenyl-4,9-diazadodecane-4,9-bisnitroxide and 2,2,5-trimethyl-4-phenyl-3-azahexane-3-nitroxide also show accelerated bisnitroxide decomposition. Low-temperature EPR studies of the bisnitroxide reveal an unusually strong radical-radical interaction, suggesting enhanced stabilization of the intermediate mononitroxide formed during polymerization by interaction with the proximal N-alkoxyamine. The transient mononitroxide is postulated to be stabilized by delocalization of the unpaired electron density over five atoms.

| S-EPMC3090629 | biostudies-literature

Biocatalytic Synthesis and Polymerization via ROMP of New Biobased Phenolic Monomers: A Greener Process toward Sustainable Antioxidant Polymers.

Project description:Antioxidant norbornene-based monomers bearing biobased sterically hindered phenols (SHP)-NDF (norbornene dihydroferulate) and NDS (norbornene dihydrosinapate)-have been successfully prepared through biocatalysis from naturally occurring ferulic and sinapic acids, respectively, in presence of Candida antarctica Lipase B (Cal-B). The ring opening metathesis polymerization (ROMP) of these monomers was investigated according to ruthenium catalyst type (GI) vs. (HGII) and monomer to catalyst molar ratio ([M]/[C]). The co-polymerization of antioxidant functionalized monomer (NDF or NDS) and non-active norbornene (N) has also been performed in order to adjust the number of SHP groups present per weight unit and tune the antioxidant activity of the copolymers. The polydispersity of the resulting copolymers was readily improved by a simple acetone wash to provide antioxidant polymers with well-defined structures. After hydrogenation with p-toluenesulfonylhydrazine (p-TSH), the radical scavenging ability of the resulting saturated polymers was evaluated using ?,?-diphenyl-?-picrylhydrazyl (DPPH) analysis. Results demonstrated that polymers bearing sinapic acid SHP exhibited higher antiradical activity than the polymer bearing ferulic acid SHP. In addition it was also shown that only a small SHP content was needed in the copolymers to exhibit a potent antioxidant activity.

| S-EPMC5744638 | biostudies-literature

Solid-State Polymerization of Poly(ethylene furanoate) Biobased Polyester, I: Effect of Catalyst Type on Molecular Weight Increase.

Project description:In this work, we report the synthesis of poly(ethylene furanoate) (PEF), catalyzed by three different catalysts, namely, titanium (IV) isopropoxide (TIS), tetrabutyltitanate (TBT), and dibutyltin (IV) oxide (DBTO), via the two-stage melt polycondensation method. Solid-state polymerization (SSP) was conducted at different reaction times (1, 2, 3.5, and 5 h) and temperatures 190, 200, and 205 °C, under vacuum. The resultant polymers were analyzed according to their intrinsic viscosity (IV), end groups (⁻COOH), and thermal properties, via differential scanning calorimetry. DSC results showed that the post polymerization process was favorable to enhance the melting point of the prepared PEF samples. As was expected, the intrinsic viscosity and the average molecular weight of PEF increased with the SSP time and temperature, whereas the number of carboxyl end-groups was decreased. A simple kinetic model was also developed and used to predict the time evolution of polymers IV, as well as the carboxyl and hydroxyl content of PEF during the SSP. From both the experimental measurements and the theoretical simulation results it was proved that the presence of the TIS catalyst resulted in higher transesterification kinetic rate constants and higher reaction rates. The activation energies were not much affected by the presence of different catalysts. Finally, using DBTO as a catalyst, the polyesters produced have higher crystallinity, and as a consequence, higher number of inactive carboxyl and hydroxyl groups.

| S-EPMC6418636 | biostudies-literature

Synthesis of Biobased Long-Chain Polyesters by Acyclic Diene Metathesis Polymerization and Tandem Hydrogenation and Depolymerization with Ethylene.

Project description:Acyclic diene metathesis (ADMET) polymerization of biobased α,ω-dienes of bis(undec-10-enoate) with diols (1,4-butanediol, isosorbide, isomannide, and 1,4-cyclohexanedimethanol) afforded high-molecular weight unsaturated polyesters, and subsequent tandem hydrogenation (H2 1.0 MPa, 50 °C, 3 h) gave the saturated polymers upon addition of a small amount of Al2O3 (1.0-1.7 wt %). Subsequent reaction of the unsaturated polymers with ethylene afforded the oligomers (by depolymerization and degradation).

| S-EPMC7391851 | biostudies-literature

Controlled Polymer Synthesis Toward Green Chemistry: Deep Insights into Atom Transfer Radical Polymerization in Biobased Substitutes for Polar Aprotic Solvents.

Project description:Cyrene (dihydrolevoglucosenone) and its derivative Cygnet 0.0, recognized as eco-friendly alternatives to polar aprotic solvents, were utilized in atom transfer radical polymerization (ATRP) of a wide range of both hydrophobic and hydrophilic (meth)acrylates. The detailed kinetics study and electrochemical experiments of the catalytic complex in these solvents reveal the opportunities and limitations of their use in controlled radical polymerization. Both solvents produce precisely controlled polymers using supplemental activator and reducing agent (SARA) ATRP. They offer an efficient reaction medium for crafting well-defined branched architectures from naturally derived cores such as riboflavin, β-cyclodextrin, and troxerutin, thereby significantly expanding the application scope of these solvents. Notably, Cygnet 0.0 significantly reduces side reactions between the solvent and the catalyst compared to Cyrene, allowing the catalyst complex to be used at a reduced concentration down to 75 ppm. The effective mass yield values achieved in Cyrene and Cygnet 0.0 underscore a substantial advantage of these solvents over DMF in generating processes that adhere to the principles of green chemistry. Furthermore, the copper residue in the final polymers was several hundred times lower than the permissible daily exposure to orally administered copper in pharmaceuticals. As a result, the resulting polymeric materials hold immense potential for various applications, including the pharmaceutical industry.

| S-EPMC10966734 | biostudies-literature

Computation of nitroxide-nitroxide distances in spin-labeled DNA duplexes.

Project description:Nanometer distances in nucleic acids can be measured by EPR using two 1-oxyl-2,2,5,5-tetramethylpyrroline radicals, with each label attached via a methylene group to a phosphorothioate-substituted backbone position as one of two phosphorothioate diastereomers (R(P) and S(P)). Correlating the internitroxide distance to the geometry of the parent molecule requires computational analysis of the label conformers. Here, we report sixteen 4-ns MD simulations on a DNA duplex d(CTACTGCTTTAG) .d(CTAAAGCAGTAG) with label pairs at C7/C19, T5/A17, and T2/T14, respectively. For each labeled duplex, four simulations were performed with S(P)/S(P), R(P)/R(P), S(P)/R(P), and R(P)/S(P) labels, with initial all trans label conformations. Another set of four simulations was performed for the 7/19-labeled duplex using a different label starting conformation. The average internitroxide distance r(MD) was within 0.2 A for the two sets of simulations for the 7/19-labeled duplex, indicating sufficient sampling of conformational space. For all three labeled duplexes studied, r(MD) agreed with experimental values, as well as with average distances obtained from an efficient conformer search algorithm (NASNOX). The simulations also showed that the labels have conformational preferences determined by the linker chemistry and label-DNA interactions. These results establish computational algorithms that allow use of the 1-oxyl-2,2,5,5-tetramethylpyrroline label for mapping global structures of nucleic acids.

| S-EPMC2430107 | 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