scholarly journals Design of Waterborne Asymmetric Block Copolymers as Thermoresponsive Materials

Polymers ◽  
2020 ◽  
Vol 12 (6) ◽  
pp. 1253
Author(s):  
Gordana Siljanovska Petreska ◽  
Christof van Sluijs ◽  
Clemens Auschra ◽  
Maria Paulis
Keyword(s):  
Mechanical Properties ◽  
Block Copolymers ◽  
Film Formation ◽  
Miniemulsion Polymerization ◽  
Two Phase ◽  
Dsc Measurements ◽  
Reversible Addition ◽  
Raft Agent ◽  
Different Temperatures ◽  
Morphological Differences

AB diblock waterborne copolymers made of styrene (St) and 2-ethylhexyl acrylate (2EHA) were synthesized by means of two-step reversible addition fragmentation chain transfer (RAFT) (mini)emulsion polymerization. Monofunctional asymmetric RAFT agent was used to initiate the polymerization. The hard polystyrene “A” block was synthesized via miniemulsion polymerization followed by 2EHA pre-emulsion feeding to form the soft “B” block. Polymerization kinetics and the evolution of the molecular weight distribution were followed during synthesis of both initial and final block copolymers. DSC measurements of the block copolymers revealed the existence of two glass transition temperatures (Tgs) and thus the occurrence of two-phase systems. Microscopic techniques (atomic force microscopy (AFM) and transmission electron microscopy (TEM)) were used to study the phase separation within the particles in the latex form, after film formation at room temperature cast directly from the latex and after different post-treatments well above the Tg of the hard-polystyrene domains, when complete particle coalescence had occurred. The morphological differences observed after different annealing temperatures were correlated with the mechanical properties analyzed by DMTA measurements. Finally, the differences found in the mechanical properties of the block copolymers annealed at different temperatures were correlated to their heat seal application results.

scholarly journals Mechanical and Morphological Properties of Waterborne ABA Hard-Soft-Hard Block Copolymers Synthesized by Means of RAFT Miniemulsion Polymerization

Polymers ◽  
2019 ◽  
Vol 11 (8) ◽  
pp. 1259 ◽  
Author(s):  
Gordana Siljanovska Petreska ◽  
Arantxa Arbe ◽  
Clemens Auschra ◽  
Maria Paulis
Keyword(s):  
Molecular Weight ◽  
Block Copolymers ◽  
Film Formation ◽  
Miniemulsion Polymerization ◽  
Morphological Properties ◽  
Phase System ◽  
Two Phase ◽  
Raft Agent ◽  
Different Temperatures ◽  
Equilibrium Morphology

High molecular weight waterborne ABA block copolymers of styrene (St) and 2-ethylhexyl acrylate (2EHA) containing hard and soft domains were synthesized by means of RAFT (mini)emulsion polymerization using a bifunctional symmetric S,S-dibenzyl trithiocarbonate (DBTTC) RAFT agent. Miniemulsion polymerization was initially used for the synthesis of the A-block, which forms hard domains, followed by 2EHA pre-emulsion feeding to build the B-block soft domains. Polymerization kinetics and the evolution of the Molecular Weight Distribution (MWD) were followed during the synthesis of different ABA block copolymers. The thermal properties of the final symmetric block copolymers were studied on dried films by means of DSC. It was found that the block copolymers have two glass transitions, which indicates the presence of a two-phase system. Phase separation was investigated by means of microscopic techniques (AFM and TEM) and SAXS, both of the particles in the latex form, as well as after film formation at room temperature and after different post-treatments. Films were annealed at temperatures well above the glass transition temperature (Tg) of the hard phase to study the bulk morphology of the films after complete particle coalescence. Moreover, for comparison purposes, the films were re-dissolved in THF, and films were again cast directly from the homogeneous THF solutions. As THF is a good solvent for both blocks, such films serve as a reference for the equilibrium morphology. Finally, DMTA studies of the films annealed at different temperatures were performed to correlate the morphology changes with the mechanical properties of the block copolymers.

scholarly journals Synthesis of Poly(lactic acid)-block-poly(N,N-dimethylaminoethyl methacrylate) Copolymers with Controllable Block Structures via Reversible Addition Fragmentation Polymerization from Aminolyzed Poly(lactic acid)

2018 ◽  
Vol 2018 ◽  
pp. 1-9
Author(s):  
Wenwen Yu ◽  
Lijing Zhu ◽  
Jiangao Shi ◽  
Cunting Zhao
Keyword(s):  
Lactic Acid ◽  
Block Copolymers ◽  
Raft Polymerization ◽  
Poly Lactic Acid ◽  
Pseudo First Order Reaction ◽  
Oh Groups ◽  
Dimethylaminoethyl Methacrylate ◽  
Reversible Addition ◽  
Raft Agent ◽  
Different Temperatures

Poly(lactic acid)-block-poly(N,N-dimethylaminoethyl methacrylate) (PLA-PDMAEMA) copolymers were synthesized from aminolyzed PLA via reversible addition fragmentation (RAFT) polymerization. PLA undergoes aminolytic degradation with ethylenediamine (EDA). The kinetics of the aminolysis reaction of PLA at different temperatures and EDA concentrations was investigated in detail. The molar masses of products rapidly decreased in the initial stage at low aminolytic degree. Meanwhile, reactive –NH2 and –OH groups were introduced to the end of shorter PLA chains and used as sites to further immobilize the RAFT agent. PLA-PDMAEMA block copolymers were synthesized. A pseudo-first-order reaction kinetics was observed for the RAFT polymerization of PDMAEMA at a low conversion. By controlling the aminolysis reaction of PLA and RAFT polymerization degree of DMAEMA, the length distributions of the PLA and PDMAEMA blocks can be controlled. This method can be extended to more systems to obtain block copolymers with controllable block structure.

Synthesis and Characterization of Polystyrene-Graphite Nanocomposites via Surface Raft-Mediated Polymerization

2012 ◽  
Vol 463-464 ◽  
pp. 527-532
Author(s):  
Hussein M. Etmimi ◽  
Ronald D. Sanderson
Keyword(s):  
Mechanical Properties ◽  
Miniemulsion Polymerization ◽  
X Ray Diffraction ◽  
X Ray ◽  
Transmission Electron ◽  
Reversible Addition ◽  
Raft Agent ◽  
Polymerization Method ◽  
Better Than

The synthesis of polystyrene/GO (PS-GO) nanocomposites using the reversible addition-fragmentation chain transfer (RAFT) mediated polymerization method is described. The GO was synthesized and immobilized with a RAFT agent to afford RAFT-functionalized GO nanosheets. The RAFT-immobilized GO was used for the synthesis of PS nanocomposites in a controlled manner using miniemulsion polymerization. The moelcular weight and dispersity of the PS in the nanocomposites depended on the amount of RAFT-grafted GO in the system, in accordance with the features of the RAFT-mediated polymerization. X-ray diffraction and transmission electron microscopy analyses revealed that the nanocomposites had exfoliated morphology, even at relatively high GO content. The thermal stability and mechanical properties of the PS-GO nanocomposites were better than those of the neat PS polymer. Furthermore, the mechanical properties of the nanocomposites were dependent on the RAFT grafted GO content.

scholarly journals Photo-Responsive Polymersomes as Drug Delivery System for Potential Medical Applications

Molecules ◽  
2020 ◽  
Vol 25 (21) ◽  
pp. 5147
Author(s):  
Wanting Hou ◽  
Ruiqi Liu ◽  
Siwei Bi ◽  
Qian He ◽  
Haibo Wang ◽  
...  
Keyword(s):  
Drug Delivery ◽  
Block Copolymers ◽  
Drug Delivery System ◽  
Delivery System ◽  
Raft Polymerization ◽  
Amphiphilic Block Copolymers ◽  
Medical Applications ◽  
Drug Molecules ◽  
Reversible Addition ◽  
Raft Agent

Due to a strong retardation effect of o-nitrobenzyl ester on polymerization, it is still a great challenge to prepare amphiphilic block copolymers for polymersomes with a o-nitrobenzyl ester-based hydrophobic block. Herein, we present one such solution to prepare amphiphilic block copolymers with pure poly (o-nitrobenzyl acrylate) (PNBA) as the hydrophobic block and poly (N,N’-dimethylacrylamide) (PDMA) as the hydrophilic block using bulk reversible addition-fragmentation chain transfer (RAFT) polymerization of o-nitrobenzyl acrylate using a PDMA macro-RAFT agent. The developed amphiphilic block copolymers have a suitable hydrophobic/hydrophilic ratio and can self-assemble into photoresponsive polymersomes for co-loading hydrophobic and hydrophilic cargos into hydrophobic membranes and aqueous compartments of the polymersomes. The polymersomes demonstrate a clear photo-responsive characteristic. Exposure to light irradiation at 365 nm can trigger a photocleavage reaction of o-nitrobenzyl groups, which results in dissociation of the polymersomes with simultaneous co-release of hydrophilic and hydrophobic cargoes on demand. Therefore, these polymersomes have great potential as a smart drug delivery nanocarrier for controllable loading and releasing of hydrophilic and hydrophobic drug molecules. Moreover, taking advantage of the conditional releasing of hydrophilic and hydrophobic drugs, the drug delivery system has potential use in medical applications such as cancer therapy.

Fluorinated amphiphilic block copolymers via RAFT polymerization and their application as surf-RAFT agent in miniemulsion polymerization

RSC Advances ◽  
2015 ◽  
Vol 5 (20) ◽  
pp. 15461-15468 ◽  
Author(s):  
Bishnu P. Koiry ◽  
Arindam Chakrabarty ◽  
Nikhil K. Singha
Keyword(s):  
Block Copolymer ◽  
Block Copolymers ◽  
Ethylene Glycol ◽  
Raft Polymerization ◽  
Miniemulsion Polymerization ◽  
Amphiphilic Block Copolymers ◽  
Poly Ethylene Glycol ◽  
Raft Agent ◽  
Poly Ethylene ◽  
Glycol Methyl Ether

Preparation of an amphiphilic block copolymer (Am-BCP) based on poly(ethylene glycol) methyl ether methacrylate (PEGMA) and heptafluorobutyl acrylate (HFBA) via RAFT polymerization and application of this Am-BCP as surf-RAFT agent for polymerization of styrene.

RAFT Polymerization of Monomers with Highly Disparate Reactivities: Use of a Single RAFT Agent and the Synthesis of Poly(styrene-block-vinyl acetate)

2013 ◽  
Vol 66 (12) ◽  
pp. 1564 ◽  
Author(s):  
Lily A. Dayter ◽  
Kate A. Murphy ◽  
Devon A. Shipp
Keyword(s):  
Block Copolymers ◽  
Vinyl Acetate ◽  
Chain Transfer ◽  
Raft Polymerization ◽  
Good Control ◽  
Scanning Calorimetry ◽  
Styrene Polymerization ◽  
Reversible Addition ◽  
Raft Agent ◽  
End Group

A single reversible addition–fragmentation chain transfer (RAFT) agent, malonate N,N-diphenyldithiocarbamate (MDP-DTC) is shown to successfully mediate the polymerization of several monomers with greatly differing reactivities in radical/RAFT polymerizations, including both vinyl acetate and styrene. The chain transfer constants (Ctr) for MDP-DTC for both these monomers were evaluated; these were found to be ~2.7 in styrene and ~26 in vinyl acetate, indicating moderate control over styrene polymerization and good control of vinyl acetate polymerization. In particular, the MDP-DTC RAFT agent allowed for the synthesis of block copolymers of these two monomers without the need for protonation/deprotonation switching, as has been previously developed with N-(4-pyridinyl)-N-methyldithiocarbamate RAFT agents, or other end-group transformations. The thermal properties of the block copolymers were studied using differential scanning calorimetry, and those with sufficiently high molecular weight and styrene composition appear to undergo phase separation. Thus, MDP-DTC may be useful for the production of other block copolymers consisting of monomers with highly dissimilar reactivities.

Reversible Addition–Fragmentation Chain Transfer (RAFT) Polymerization in Miniemulsion Based on In Situ Surfactant Generation

2011 ◽  
Vol 64 (8) ◽  
pp. 1033 ◽  
Author(s):  
S. R. Simon Ting ◽  
Eun Hee Min ◽  
Per B. Zetterlund
Keyword(s):  
Potassium Hydroxide ◽  
Colloidal Stability ◽  
Chain Transfer ◽  
Raft Polymerization ◽  
Miniemulsion Polymerization ◽  
High Energy ◽  
Reversible Addition ◽  
Raft Agent ◽  
Surface Active

Reversible addition–fragmentation chain transfer (RAFT) polymerization of styrene has been implemented in aqueous miniemulsion based on the in situ surfactant generation approach using oleic acid and potassium hydroxide in the absence of high energy mixing. The best results were obtained using the RAFT agent 3-benzylsulfanyl thiocarbonyl sufanylpropionic acid (BSPAC), most likely as a result of the presence of a carboxylic acid functionality in the RAFT agent that renders it surface active and thus imparts increased colloidal stability. Stable final miniemulsions were obtained with no coagulum with particle diameters less than 200 nm. The results demonstrate that the RAFT miniemulsion polymerization of styrene employing the low energy in situ surfactant method is challenging, but that a system that proceeds predominantly by a miniemulsion mechanism can be achieved under carefully selected conditions.

scholarly journals Amphiphilic Block Copolymers with Vinyl Caprolactam as Kinetic Gas Hydrate Inhibitors

Energies ◽  
2021 ◽  
Vol 14 (2) ◽  
pp. 341
Author(s):  
Faraz Rajput ◽  
Milan Maric ◽  
Phillip Servio
Keyword(s):  
Block Copolymers ◽  
Formation Rate ◽  
Water System ◽  
Water Soluble ◽  
Chain Extension ◽  
Methane Formation ◽  
Initial Growth ◽  
Reversible Addition ◽  
Pure Methane ◽  
Raft Agent

Macrosurfactants consisting of water-soluble poly(vinylcaprolactam) (PVCap) or poly(vinylpyrrolidone) (PVP) segments with comparatively shorter hydrophobic poly(styrene) (PS) or poly(2,3,4,5,6-pentafluorostyrene) (PPFS) segments were used as kinetic hydrate inhibitors (KHIs). These were synthesized with 2-cyanopropan-2-yl N-methyl-N-(pyridin-4-yl)dithiocarbamate switchable reversible addition–fragmentation chain transfer (RAFT) agent at 60 °C or 90 °C for 1-P(S/PFS) or 1-PVCap, respectively, followed by chain extension at 90 °C or 70 °C with PVCap or PVP, respectively. The addition of PVCap to the pure methane-water system resulted in a 53% reduction of methane consumption (comparable to PVP with 51% inhibition) during the initial growth phase. A PS-PVCap block copolymer comprised of 10 mol% PS and 90 mol% PVCap improved inhibition to 56% compared to the pure methane-water system with no KHIs. Substituting PS with a more hydrophobic PPFS segment further improved inhibition to 73%. By increasing the ratio of the hydrophobic PS- to PVCap- groups in the polymer, an increase of its inhibition potential was measured. For PPFS-PVCap, an increase of PPFS ratio from 5% to 10% decreased the methane formation rate by 6%. However, PPFS-PVCap block copolymers with more than 20 mol% PPFS were unable to dissolve in water due to increase in hydrophobicity and the attendant low critical micelle concentration (CMC).

scholarly journals Mechanical Properties of Powder Metallugry (Ti-6Al-4V) with Hot Isostatic Pressing

2020 ◽  
Vol 10 (3) ◽  
pp. 5637-5642
Author(s):  
M. A. Elfghi ◽  
M. Gunay
Keyword(s):  
Mechanical Properties ◽  
Titanium Alloys ◽  
Performance Optimization ◽  
High Performance ◽  
Hot Isostatic Pressing ◽  
Two Phase ◽  
Manufacturing Defects ◽  
Isostatic Pressing ◽  
Different Temperatures ◽  
The Impact

Titanium alloys are widely used due to their high performance and low density in comparison with iron-based alloys. Their applications extend to aerospace and military in order to utilize their high resistance for corrosion. Understanding the mechanical properties and microstructure of titanium alloys is critical for performance optimization, as well as their implications on strength, plasticity, and fatigue. Ti-6Al-4V is an α+β two-phase alloy and is considered one of the most commonly used titanium alloys for weight reduction and high-performance. To avoid manufacturing defects, such as porosity and composition segregation, Hot Isostatic Pressing (HIP) is used to consolidate alloy powder. The HIP method is also used to facilitate the manufacturing of complex structures that cannot be made with forging and casting. In the current research, Ti-6Al-4V alloys were manufactured with HIP and the impact on heat treatment under different temperatures and sintering durations on the performance and microstructure of the alloy was studied. The results show changes in mechanical properties and microstructure with the increase of temperature and duration.

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