Spherical Glycopolymer Architectures using RAFT: From Stars with a ?-Cyclodextrin Core to Thermoresponsive Core–Shell Particles

2009 ◽  
Vol 62 (8) ◽  
pp. 813 ◽  
Author(s):  
Ling Zhang ◽  
Martina H. Stenzel

Glycopolymers with a seven-arm star architectures based on a β-cyclodextrin core (β-CD-RAFT) were successfully prepared using reversible addition–fragmentation chain transfer (RAFT) polymerization. A bimodal molecular weight distribution was observed in the early stages of the polymerization. At monomer conversions of N-acryloyl glucose (AGA) above 10% the polymerization proceeded according to a living behaviour and molecular weights of more than 200000 g mol–1 were obtained. However, the resulting star polymers did not undergo well-controlled chain extension with N-isopropyl acrylamide (NIPAAm) and the formation of block structures in each arm was prevented. Alternatively, the arm-first technique was employed. Block copolymers based on AGA and PNIPAAm were self-assembled into micelles at a solution temperature above the lower critical solution temperature. Subsequent core-crosslinking with hexan-1,6-diol diacrylate resulted in unimolecular micelles with thermoresponsive properties. Dynamic light scattering studies, surface tensiometry, and transmission electron microscopy confirmed the formation of core–shell particles.


2021 ◽  
Vol 0 (0) ◽  
Author(s):  
Nasrullah Shah ◽  
Zubair Ullah Khan ◽  
Manzoor Hussain ◽  
Touseef Rehan ◽  
Abbas Khan

Abstract The study and application of reversible addition-fragmentation chain transfer (RAFT) polymerization have been widely reported in the literature because of its high compatibility with numerous monomers, reaction conditions, and low polydispersity index. The effect of RAFT agents on the characteristics of the final product is greatly needed to be explored. Our present study aimed to compare the influence of two different types of RAFT agents on the characteristics of the water-soluble polymer (2-acrylamido-2-methylpropane sulfonic acid) (polyAMPS) and their polyAMPS@butyl methacrylate (BMA) core-shell particles. Different analytical techniques including scanning electron microscopy (SEM), fourier transform infrared spectroscopy (FTIR), energy dispersive X-ray analysis (EDX), X-ray diffraction (XRD), and thermogravimetric analysis (TGA) were used to ascertain the final morphological, structural, and thermal properties of the resultant products. It was found that RAFT agents have shown a clear influence on the final properties of the resultant polyAMPS and their core-shell particles such as particle size, shape, size distribution, and thermal behavior. This study confirms that RAFT agents can control the final properties of the polymers and their core-shell particles.



2011 ◽  
Vol 89 (3) ◽  
pp. 317-325 ◽  
Author(s):  
Binxin Li ◽  
Daniel Majonis ◽  
Peng Liu ◽  
Mitchell A. Winnik

We describe the synthesis of an end-functionalized copolymer of N-(2-hydroxypropyl)methacrylamide (HPMA) and N-hydroxysuccinimide methacrylate (NMS) by reversible addition–fragmentation chain transfer (RAFT) polymerization. To control the polymer composition, the faster reacting monomer (NMS) was added slowly to the reaction mixture beginning 30 min after initating the polymerization (ca. 16% HPMA conversion). One RAFT agent, based on azocyanopentanoic acid, introduced a –COOH group to the chain at one end. Use of a different RAFT agent containing a 4-amino-1,8-naphthalimide dye introduced a UV–vis absorbing and fluorescent group at this chain end. The polymers obtained had molecular weights of 30 000 and 20 000, respectively, and contained about 30 mol% NMS active ester groups.



2011 ◽  
Vol 306-307 ◽  
pp. 410-415
Author(s):  
Li Sun ◽  
Fu Tian Liu ◽  
Qi Hui Jiang ◽  
Xiu Xiu Chen ◽  
Ping Yang

Core/shell type nanoparticles with an average diameter of 20nm were synthesized by chemical precipitation method. Firstly, Monodisperse Fe3O4 nanoparticles were synthesized by solvethermal method. FeSO4ž7H2O and NaBH4 were respectively dissolved in distilled water, then moderated Fe3O4 particles and surfactant(PVP) were ultrasonic dispersed into the FeSO4ž7H2O solution. The resulting solution was stirred 2 h at room temperature. Fe could be deposited on the surface of monodispersed Fe3O4 nanoparticles to form core-shell particles. The particles were characterized by using various experimental techniques, such as transmission electron microscopy (TEM), X-ray diffraction (XRD), AGM and DTA. The results suggest that the saturation magnetization of the nanocomposites is 100 emu/g. The composition of the samples show monodisperse and the sides of the core/shell nanoparticles are 20-30nm. It is noted that the formation of Fe3O4/Fe nanocomposites magnetite nanoparticles possess superparamagnetic property.



2014 ◽  
Vol 1033-1034 ◽  
pp. 996-1001
Author(s):  
Shao Jin Jia ◽  
Zhen Qi Zhang ◽  
Zhen Gang Ding ◽  
Xiao Tian Hou ◽  
Ping Kai Jiang

A core-shell composite polymer was produced by the method of high internal phase emulsion polymerization. The continuous phase of emulsion contained styrene(St), butyl methacrylate(BMA), octamethylcylotetrasiloxane(D4), and azobisisobutyronitrile (AIBN) which worked as an initiator. The block copolymers with St, BMA, D4 units are particularly promising for surface modification and hydrophobicity. The core-shell structure is proved by the use of Transmission electron microscopy (TEM). In addition, the water contact angle increased with the increasing weight ratio of D4. The results show that the concentrated emulsion system has good stability and the water resistance of the polymer has been improved greatly.



RSC Advances ◽  
2016 ◽  
Vol 6 (42) ◽  
pp. 35621-35627 ◽  
Author(s):  
Ren He ◽  
Xiaoli Zhan ◽  
Qinghua Zhang ◽  
Fengqiu Chen

Reactive core–shell particles for epoxy toughening were synthesized via reversible addition–fragmentation chain transfer emulsion polymerization mediated by an amphiphilic macro-RAFT agent followed by core-crosslinking to increase stability.



2005 ◽  
Vol 13 (7) ◽  
pp. 721-726
Author(s):  
Shunsheng Cao ◽  
Xiaobo Deng ◽  
Bailing Liu

Core-shell microspheres ranging in average diameter from 12.829 to 15.039 μm, with a poly butyl methacrylate (BMA) core, and a poly 3-(methacryloxypropyl)-trimethoxysilane (MATS) shell, were prepared with methanol as the dispersion medium, by a successive seeding method under kinetically controlled conditions. To date, although some of particles (PSi/PA) have been prepared by seeded emulsion polymerisation, only a few core/shell (PA/PSi) microspheres have been reported the literatures. To prepare core/shell (PA/PSi), the core was first synthesized by dispersion polymerisation and to form seeds; addition of MATS monomer was started after 90~95% conversion of the BMA. The reaction was prolonged for another 12 h to achieve complete consumption of MATS monomer. Microspheres; containing hydrophilic PBMA as the core and hydrophobic PMATS as the shell, were successfully formed through the free radical of surface in the core. The particles morphology and size distribution were examined using a Transmission electron microscope and a Malvern Master Sizer/E particle size analyser, respectively.



2019 ◽  
Vol 72 (7) ◽  
pp. 479 ◽  
Author(s):  
Amin Reyhani ◽  
Thomas G. McKenzie ◽  
Qiang Fu ◽  
Greg G. Qiao

Reversible addition–fragmentation chain transfer (RAFT) polymerization initiated by a radical-forming redox reaction between a reducing and an oxidizing agent (i.e. ‘redox RAFT’) represents a simple, versatile, and highly useful platform for controlled polymer synthesis. Herein, the potency of a wide range of redox initiation systems including enzyme-mediated redox reactions, the Fenton reaction, peroxide-based reactions, and metal-catalyzed redox reactions, and their application in initiating RAFT polymerization, are reviewed. These redox-RAFT polymerization methods have been widely studied for synthesizing a broad range of homo- and co-polymers with tailored molecular weights, compositions, and (macro)molecular structures. It has been demonstrated that redox-RAFT polymerization holds particular promise due to its excellent performance under mild conditions, typically operating at room temperature. Redox-RAFT polymerization is therefore an important and core part of the RAFT methodology handbook and may be of particular importance going forward for the fabrication of polymeric biomaterials under biologically relevant conditions or in biological systems, in which naturally occurring redox reactions are prevalent.



2014 ◽  
Vol 6 (24) ◽  
pp. 21954-21960 ◽  
Author(s):  
Qinran Li ◽  
Kaiguang Yang ◽  
Yu Liang ◽  
Bo Jiang ◽  
Jianxi Liu ◽  
...  


2006 ◽  
Vol 2006 ◽  
pp. 1-10 ◽  
Author(s):  
Bérangère Bailly ◽  
Anne-Carole Donnenwirth ◽  
Christèle Bartholome ◽  
Emmanuel Beyou ◽  
Elodie Bourgeat-Lami

Polystyrene (PS) chains with molecular weights comprised between 8000 and 64000g⋅mol-1and narrow polydispersities were grown from the surface of silica nanoparticles (Aerosil A200 fumed silica and Stöber silica, resp.) through nitroxide-mediated polymerization (NMP). Alkoxyamine initiators based on N-tert-butyl-1-diethylphosphono-2,2-dimethylpropyl nitroxide (DEPN) and carrying a terminal functional group have been synthesized in situ and grafted to the silica surface. The resulting grafted alkoxyamines have been employed to initiate the growth of polystyrene chains from the inorganic surface. The maximum grafting density of the surface-tethered PS chains was estimated and seemed to be limited by initiator confinement at the interface. Then, the PS-grafted Stöber silica nanoparticles were entrapped inside latex particles via miniemulsion polymerization. Transmission electron microscopy indicated the successful formation of silica-polystyrene core-shell particles.



e-Polymers ◽  
2008 ◽  
Vol 8 (1) ◽  
Author(s):  
Jie Xu ◽  
Wei Shang ◽  
Jian Zhu ◽  
Zhenping Cheng ◽  
Nianchen Zhou ◽  
...  

AbstractA novel bis-functional reversible addition-fragmentation chain transfer (RAFT) agent bearing triphenylamine (TPA) and bis(indolyl)methane (BIM) groups, {4-[bis(1-carbodithioic acid benzyl ester-indol-3-yl)methyl]phenyl}diphenylamine (BCIMPDPA), was synthesized and successfully used as the RAFT agent to mediate the polymerization of styrene (St). The polymerization results showed that reversible addition-fragmentation chain transfer (RAFT) polymerization of St could be well controlled. The kinetic plot showed it was of first order and the numberaverage molecular weight (Mn(GPC)) of the polymer measured by GPC increased linearly with monomer conversion, simultaneously, the molecular weight distribution of the polymer was also relatively narrow. In addition, the existence of the TPA and BIM groups in the middle of polymer chain was confirmed by chain extension reaction and 1H NMR spectrum. The optical properties of the functionalized polystyrene (PS) in chloroform solution were also investigated. Furthermore, the redox process of the RAFT agent and the functionalized PS were studied by cyclic voltammetry method.



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