One-pot preparation of BAB triblock copolymer nano-objects through bifunctional macromolecular RAFT agent mediated dispersion polymerization

2016 ◽  
Vol 7 (10) ◽  
pp. 1953-1962 ◽  
Author(s):  
Yaqing Qu ◽  
Shuang Wang ◽  
Habib Khan ◽  
Chengqiang Gao ◽  
Heng Zhou ◽  
...  
Keyword(s):  
Triblock Copolymer ◽  
Dispersion Polymerization ◽  
Raft Polymerization ◽  
One Pot ◽  
Raft Agent ◽  
Macromolecular Raft Agent

Nano-assemblies of a BAB triblock copolymer containing a solvophilic A block and two solvophobic B blocks were prepared through dispersion RAFT polymerization.

One-Pot Endgroup-Modification of Hydrophobic RAFT Polymers with Cyclodextrin by Thiol-ene Chemistry and the Subsequent Formation of Dynamic Core–Shell Nanoparticles Using Supramolecular Host–Guest Chemistry

2012 ◽  
Vol 65 (8) ◽  
pp. 1095 ◽  
Author(s):  
Firdaus Yhaya ◽  
Sandra Binauld ◽  
Manuela Callari ◽  
Martina H. Stenzel
Keyword(s):  
Raft Polymerization ◽  
Particle Surface ◽  
Terminal Group ◽  
Solid Particles ◽  
Core Shell ◽  
Shell Nanoparticles ◽  
One Pot ◽  
Subsequent Formation ◽  
Raft Agent ◽  
Core Shell Nanoparticles

Poly(methyl methacrylate) PMMA, synthesized using reversible addition fragmentation chain transfer (RAFT) polymerization, was heated in a solvent at 100°C for 24 h leading to the loss of the RAFT endfunctionality and the complete conversion into a vinyl group. Mono(6-deoxy-6-mercapto)-β-cyclodextrin (β-CD-SH) was subsequently clicked onto the polymer by a thiol-ene reaction leading to PMMA with one β-CD as a terminal group (PMMA70–β-CD). Meanwhile, a RAFT agent with an adamantyl group has been prepared for the polymerization of 2-hydroxyethyl acrylate (HEA) leading to PHEA95–Ada. Two processes were employed to generate core–shell nanoparticles from these two polymers: a one-step approach that employs a solution of both polymers at stoichiometric amounts in DMF, followed by the addition of water, and a two step process that uses PMMA solid particles with surface enriched with β-CD in water, which have a strong tendency to aggregate, followed by the addition of PHEA95–Ada in water. Both pathways led to stable core–shell nanoparticles of ~150 nm in size. Addition of free β-CD competed with the polymer bound β-CD releasing the PHEA hairs from the particle surface. As a result, the PMMA particles started agglomerating resulting in a cloudy solution. A similar effect was observed when heating the solution. Since the equilibrium constant between β-CD and adamantane decreases with increasing temperature, the stabilizing PHEA chains cleaved from the surface and the solution turned cloudy due to the aggregation of the naked PMMA spheres. This process was reversible and with decreasing temperature the core–shell nanoparticles formed again leading to a clear solution.

Thermoresponsive diblock copolymer micellar macro-RAFT agent-mediated dispersion RAFT polymerization and synthesis of temperature-sensitive ABC triblock copolymer nanoparticles

2014 ◽  
Vol 52 (15) ◽  
pp. 2155-2165 ◽  
Author(s):  
Chengqiang Gao ◽  
Quanlong Li ◽  
Yongliang Cui ◽  
Fei Huo ◽  
Shentong Li ◽  
...  
Keyword(s):  
Diblock Copolymer ◽  
Triblock Copolymer ◽  
Raft Polymerization ◽  
Temperature Sensitive ◽  
Raft Agent ◽  
Abc Triblock Copolymer

Macro-RAFT agent mediated dispersion polymerization: the monomer concentration effect on the morphology of the in situ synthesized block copolymer nano-objects

2015 ◽  
Vol 6 (46) ◽  
pp. 8003-8011 ◽  
Author(s):  
Zhonglin Ding ◽  
Chengqiang Gao ◽  
Shuang Wang ◽  
Hui Liu ◽  
Wangqing Zhang
Keyword(s):  
Block Copolymer ◽  
Dispersion Polymerization ◽  
Raft Polymerization ◽  
Monomer Concentration ◽  
Concentration Effect ◽  
Raft Agent

The great effect of the monomer concentration on the block copolymer morphology under dispersion RAFT polymerization is found and demonstrated.

One-pot polymer brush synthesis via simultaneous isocyanate coupling chemistry and “grafting from” RAFT polymerization

2014 ◽  
Vol 5 (8) ◽  
pp. 2816-2823 ◽  
Author(s):  
S. P. Le-Masurier ◽  
G. Gody ◽  
S. Perrier ◽  
A. M. Granville
Keyword(s):  
Chain Transfer ◽  
Raft Polymerization ◽  
Polymer Brush ◽  
One Pot ◽  
Reversible Addition ◽  
Raft Agent ◽  
Grafting From

One-pot ‘grafting from’ of polystyrene on polydopamine particles was investigated using a newly developed carbonyl-azide reversible addition–fragmentation chain transfer (RAFT) agent.

One-Pot Synthetic Strategy to Core Cross-Linked Micelles with pH-Sensitive Cross-Linked Cores and Temperature-Sensitive Shells through RAFT Polymerization

2006 ◽  
Vol 59 (10) ◽  
pp. 733 ◽  
Author(s):  
Li-Ping Yang ◽  
Cai-Yuan Pan
Keyword(s):  
Acrylic Acid ◽  
Ethylene Glycol ◽  
Raft Polymerization ◽  
Ph Sensitive ◽  
Temperature Sensitive ◽  
One Pot ◽  
Glycol Diacrylate ◽  
Synthetic Strategy ◽  
Raft Agent ◽  
Poly Acrylic Acid

Functional micelles with a poly(N-isopropylacrylamide) (PNIPAM) shell and a cross-linked poly((acrylic acid)-co-(ethylene glycol diacrylate)) core have been successfully prepared in one pot by the reversible addition–fragmentation chain transfer (RAFT) copolymerization of acrylic acid and ethylene glycol diacrylate in selective solvent using PNIPAM-SC(S)Ph as a RAFT agent. Since PNIPAM and poly(acrylic acid) are temperature- and pH-sensitive polymers, respectively, the micelles obtained should display double environmental sensitivity to temperature and pH in water.

Synergistic Interaction Between ATRP and RAFT: Taking the Best of Each World

2009 ◽  
Vol 62 (11) ◽  
pp. 1384 ◽  
Author(s):  
Yungwan Kwak ◽  
Renaud Nicolaÿ ◽  
Krzysztof Matyjaszewski
Keyword(s):  
Chain Transfer ◽  
Raft Polymerization ◽  
Atom Transfer ◽  
Step Method ◽  
One Pot ◽  
Reversible Addition ◽  
Raft Agent ◽  
Recent Developments ◽  
One Step ◽  
Leaving Groups

This review covers recent developments on the combination of atom transfer radical polymerization (ATRP) and reversible addition–fragmentation chain transfer (RAFT) polymerization to produce well controlled (co)polymers. This review discusses the relative reactivity of the R group in ATRP and RAFT, provides a comparison of dithiocarbamate (DC), trithiocarbonate (TTC), dithioester (DTE), and xanthate versus bromine or chlorine, and an optimization of catalyst/ligand selection. The level of control in iniferter polymerization with DC was greatly improved by the addition of a copper complex. New TTC inifers with bromopropionate and bromoisobutyrate groups have been prepared to conduct, concurrently or sequentially, ATRP from Br-end groups, ATRP from the TTC moiety, and RAFT polymerization from the TTC moiety, depending on the combination of monomer and catalyst employed in the reaction. The use of concurrent ATRP/RAFT (or copper-catalyzed RAFT polymerization or ATRP with dithioester leaving groups), resulted in improved control over the synthesis of homo- and block (co)polymers and allowed preparation of well-defined high-molecular-weight polymers exceeding 1 million. Block copolymers that could not be prepared previously have been synthesized by sequential ATRP and RAFT polymerization using a bromoxanthate inifer. A simple, versatile, and one-step method involving atom-transfer radical addition–fragmentation (ATRAF) for the preparation of various chain transfer agents (including DC, DTE, and xanthate) in high purity is discussed and a one-pot, two-step polymerization starting with a RAFT agent synthesized by ATRAF, followed by polymerization, is demonstrated.

Preparation of PMAM-B-PNVP and its Hydrolysate by RAFT Polymerization: Structure Characterization and its CO2 Permeation Performance

2013 ◽  
Vol 652-654 ◽  
pp. 386-397 ◽  
Author(s):  
Jiang Nan Shen ◽  
Juan Li ◽  
Ting Ting Jiang ◽  
Hui Min Ruan
Keyword(s):  
Chain Transfer ◽  
Raft Polymerization ◽  
Composite Membranes ◽  
Permeation Rate ◽  
Structure Characterization ◽  
Polydispersity Index ◽  
Relative Molecular Mass ◽  
Raft Agent ◽  
Macromolecular Raft Agent ◽  
Transfer Agents

Macromolecules chain transfer agents (MCTA) were synthesized through the reversible addition fragmentation chain transfer polymerization (RAFT) by using S-l-Dodecyl-S′-(α, α′-dimethyl-α-acetic acid) trithiocarbonate(MTTCD), S, S′-bis (2-hydroxyethyl-2′-dimethylacrylate) trihiocarbonate (BDATC), 2-cyanoprop-2-yl dithiobenzoate (CPDB) as the chain transfer agents, methacrylamide (MAM) as the first polymerization monomer. The results showed that the structures of the end-group of dithiocarbamates had significant effects on the activity of dithiocarbamates for the polymerization of PMAM. The derived block copolymer (PMAM-b-PNVP) was prepared by using the above mentioned polymer as macromolecular RAFT agent and NVP as the second polymerization monomer. N-vinyl-γ-sodium aminobutyrate-sodium methacrylate copolymer (VSA-MSA) containing -NH2 and -COOH as the CO2 facilitated carrier, a kind of new fixed carrier membrane material for CO2 separation, was synthesized by hydrolysis of the resulted PMAM-b-PNVP. The chemical composition and structure of PMAM-CTA, PMAM-b-PNVP, MSA-VSA were analyzed by FTIR, 1HNMR and DSC, the molecular weight and polydispersity index were analyzed by GPC. The Relative molecular mass of polymer was controllable. The polydispersity index (1.2~1.3) of the obtained polymer was narrow via using MTTCD and BDATC. The VSA-MSA/PS composite membranes were prepared. The CO2 and N2 permeation performance were tested at different pressure. The results showed that the resulted composited membrane had a CO2 permeation rate of 1.2×10-4 cm3 (STP) cm-2s-1cmHg-1 and a N2 permeation rate of 8.57×10-7 cm3 (STP) cm-2s-1cmHg-1 and an ideal CO2/ N2 selectivity of 140.02 at a feed gas pressure of 7.6 cmHg and 30 °C.

scholarly journals “One-pot” aminolysis/thia-Michael addition preparation of well-defined amphiphilic PVDF-b-PEG-b-PVDF triblock copolymers: self-assembly behaviour in mixed solvents

2020 ◽  
Vol 11 (2) ◽  
pp. 401-410 ◽  
Author(s):  
Enrique Folgado ◽  
Marc Guerre ◽  
Antonio Da Costa ◽  
Anthony Ferri ◽  
Ahmed Addad ◽  
...  
Keyword(s):  
Michael Addition ◽  
Self Assembly ◽  
Triblock Copolymer ◽  
Triblock Copolymers ◽  
Raft Polymerization ◽  
Mixed Solvents ◽  
One Pot ◽  
Crystalline Structures

Novel amphiphilic PVDF-based triblock copolymer (PVDF50-b-PEG136-b-PVDF50) is synthesized using RAFT polymerization and a one-pot thia-Michael addition. Self-assembly of this ABA copolymer resulted in formation of original crystalline structures.

Facile 'One-Pot' Preparation of Reversible, Disulfide-Containing Shell Cross-Linked Micelles from a RAFT-Synthesized, pH-Responsive Triblock Copolymer in Water at Room Temperature

2009 ◽  
Vol 62 (11) ◽  
pp. 1520 ◽  
Author(s):  
Xuewei Xu ◽  
Adam E. Smith ◽  
Charles L. McCormick
Keyword(s):  
Triblock Copolymer ◽  
Room Temperature ◽  
Raft Polymerization ◽  
Hydrodynamic Diameter ◽  
Ph Responsive ◽  
Solution Ph ◽  
One Pot ◽  
Simultaneous Formation ◽  
Bioactive Agents ◽  
The One

A pH-responsive triblock copolymer, α-methoxy poly(ethylene oxide)-b-poly(N-(3-aminopropyl) methacrylamide)-β-poly(2-(diisopropylamino)ethyl methacrylate) (mPEO-PAPMA-PDPAEMA), was synthesized via aqueous RAFT polymerization. This triblock copolymer dissolves in aqueous solution at low pH (<5.0) due to protonation of primary amine residues on the PAPMA block and tertiary amine residues on the PDPAEMA block. Above pH 6.0, the copolymer unimers self-assemble into micelles consisting of PDPAEMA cores, PAPMA shells, and mPEO coronas. Dynamic light scattering studies indicated a hydrodynamic diameter of 92 nm at pH 9.0. A bifunctional, reversible cross-linker, dimethyl 3,3′-dithiobispropionimidate (DTBP), was used to cross-link the micelles. The ‘one-pot’ formation of shell cross-linked (SCL) micelles was accomplished at room temperature in water by mixing the triblock copolymers and DTBP at pH 3.0, and slowly increasing the solution pH to 9.0 leading to the simultaneous formation of micelles and cross-linking. These SCL micelles are readily cleaved by the addition of the reducing agent, dithiothreitol, and can be re-cross-linked simply by exposure to air. Such SCL micelles have potential as nanocarriers for controlled release of therapeutic and diagnostic agents because the in situ cleavage of the disulfide linkages would not only allow release of bioactive agents, but also permit renal clearance of the resulting unimeric components.

Sign in / Sign up

Export Citation Format

Share Document