Polymerization Rate Considerations for High Molecular Weight Polyisoprene-b -Polystyrene-b -Poly(N ,N -dimethylacrylamide) Triblock Polymers Synthesized Via Sequential Reversible Addition-Fragmentation Chain Transfer (RAFT) Reactions

2015 ◽  
Vol 216 (17) ◽  
pp. 1831-1840 ◽  
Author(s):  
Ryan A. Mulvenna ◽  
Rafael A. Prato ◽  
William A. Phillip ◽  
Bryan W. Boudouris
Keyword(s):  
Molecular Weight ◽  
High Molecular Weight ◽  
Chain Transfer ◽  
Polymerization Rate ◽  
Reversible Addition ◽  
Triblock Polymers

Synthesis and characterization of high molecular weight and low dispersity polystyrene homopolymers by RAFT polymerization

e-Polymers ◽  
2012 ◽  
Vol 12 (1) ◽  
Author(s):  
Cheng Jin ◽  
Chun Liu ◽  
Bo Jiang ◽  
Qin-jian in
Keyword(s):  
Molecular Weight ◽  
High Molecular Weight ◽  
Chain Transfer ◽  
Raft Polymerization ◽  
Polymerization Temperature ◽  
Polymer Molecular Weight ◽  
Mild Conditions ◽  
Reversible Addition ◽  
Polymerization Method

AbstractHigh molecular weight polystyrene homopolymers with low dispersity were synthesized by a reversible addition-fragmentation chain transfer (RAFT) polymerization method using 0.03 and 0.3 wt% of cumyl dithiobenzoate (CDB) vs. styrene (St) and the azobis(isobutyronitrile) initiator, at the polymerization temperature of 60 or 70 °C. The optimal high molecular weight polystyrene via this synthetic scheme shows Mw = 46.5×104, Mn = 33.3×104, and a dispersity of 1.40. The polystyrene chain contains a dithiobenzoate C=S moiety and thus can be used as a macro-chain-transfer agent for the polymerization of other monomers and for the synthesis of diversified block copolymers under mild conditions. The changes of the polystyrene molecular weight and dispersity were studied by the influences of the initial concentration ratio of CDB to styrene ([CDB]0/[St]0), the polymerization temperature, and the polymerization time. The PS molecular weight is inversely proportional to the [CDB]0/[St]0 ratio. Decreasing CDB from 0.3 to 0.03 wt%, a high MW PS was obtained, while the dispersity was observed to increase from 1.10 to 1.40. The PS molecular weight increases with the increase of the reaction time, while the dispersity of PS varies little from 1.12 to 1.23. The molecular weight and dispersity increase with the increase of the polymerization temperature. As the temperature arises from 60°C to 70°C, the conversion increases considerably from 25.8% to 39.9%, and the dispersity increases slightly from 1.15 to 1.17. As the temperature reaches 80°C, the conversion increases considerably to 64.7%, and the dispersity increases to 1.53. The polymer molecular weight of the polystyrene prepared by the RAFT method is suitable for the applications of engineering materials.

scholarly journals Nano-Assemblies from Amphiphilic PnBA-b-POEGA Copolymers as Drug Nanocarriers

Polymers ◽  
2021 ◽  
Vol 13 (7) ◽  
pp. 1164
Author(s):  
Angeliki Chroni ◽  
Thomas Mavromoustakos ◽  
Stergios Pispas
Keyword(s):  
Molecular Weight ◽  
Chain Transfer ◽  
Raft Polymerization ◽  
Polymeric Nanocarriers ◽  
Reversible Addition ◽  
2D Noesy ◽  
Drug Nanocarriers ◽  
Glycol Methyl Ether ◽  
Different Molecular Weight

The focus of this study is the development of highly stable losartan potassium (LSR) polymeric nanocarriers. Two novel amphiphilic poly(n-butyl acrylate)-block-poly(oligo(ethylene glycol) methyl ether acrylate) (PnBA-b-POEGA) copolymers with different molecular weight (Mw) of PnBA are synthesized via reversible addition fragmentation chain transfer (RAFT) polymerization, followed by the encapsulation of LSR into both PnBA-b-POEGA micelles. Based on dynamic light scattering (DLS), the PnBA30-b-POEGA70 and PnBA27-b-POEGA73 (where the subscripts denote wt.% composition of the components) copolymers formed micelles of 10 nm and 24 nm in water. The LSR-loaded PnBA-b-POEGA nanocarriers presented increased size and greater mass nanostructures compared to empty micelles, implying the successful loading of LSR into the inner hydrophobic domains. A thorough NMR (nuclear magnetic resonance) characterization of the LSR-loaded PnBA-b-POEGA nanocarriers was conducted. Strong intermolecular interactions between the biphenyl ring and the butyl chain of LSR with the methylene signals of PnBA were evidenced by 2D-NOESY experiments. The highest hydrophobicity of the PnBA27-b-POEGA73 micelles contributed to an efficient encapsulation of LSR into the micelles exhibiting a greater value of %EE compared to PnBA30-b-POEGA70 + 50% LSR nanocarriers. Ultrasound release profiles of LSR signified that a great amount of the encapsulated LSR is strongly attached to both PnBA30-b-POEGA70 and PnBA27-b-POEGA73 micelles.

scholarly journals Study on MMA and BA Emulsion Copolymerization Using 2,4-Diphenyl-4-methyl-1-pentene as the Irreversible Addition–Fragmentation Chain Transfer Agent

Polymers ◽  
2020 ◽  
Vol 12 (1) ◽  
pp. 80
Author(s):  
Zuxin Zhang ◽  
Daihui Zhang ◽  
Gaowei Fu ◽  
Chunpeng Wang ◽  
Fuxiang Chu ◽  
...  
Keyword(s):  
Molecular Weight ◽  
Tensile Properties ◽  
Chain Transfer ◽  
Monomer Conversion ◽  
Degree Of Polymerization ◽  
Polymerization Rate ◽  
Chain Transfer Agent ◽  
Regulation Mechanism ◽  
Transfer Coefficients ◽  
Emulsion Copolymerization

As a chain transfer agent, 2,4-diphenyl-4-methyl-1-pentene (αMSD) was first introduced in the emulsion binary copolymerization of methyl methacrylate (MMA) and butyl acrylate (BA) based on an irreversible addition–fragmentation chain transfer (AFCT) mechanism. The effects of αMSD on molecular weight and its distribution, the degree of polymerization, polymerization rate, monomer conversion, particle size, and tensile properties of the formed latexes were systematically investigated. Its potential chain transfer mechanism was also explored according to the 1H NMR analysis. The results showed that the increase in the content of αMSD could lead to a decline in molecular weight, its distribution, and the degree of polymerization. The mass percentage of MMA in the synthesized polymers was also improved as the amounts of αMSD increased. The chain transfer coefficients of αMSD for MMA and BA were 0.62 and 0.47, respectively. The regulation mechanism of αMSD in the emulsion polymerization of acrylates was found to be consistent with Yasummasa’s theory. Additionally, monomer conversion decreased greatly to 47.3% when the concentration of αMSD was higher than 1 wt% due to the extremely low polymerization rate. Moreover, the polymerization rate was also decreased probably due to the desorption and lower reactivity of the regenerative radicals from αMSD. Finally, the tensile properties of the resulting polyacrylate films were significantly affected due to the presence of αMSD.

Effect of silica nanoparticle loading and surface modification on the kinetics of RAFT polymerization

2012 ◽  
Vol 32 (1) ◽  
Author(s):  
Mehdi Salami-Kalajahi ◽  
Vahid Haddadi-Asl ◽  
Farid Behboodi-Sadabad ◽  
Saeid Rahimi-Razin ◽  
Hossein Roghani-Mamaqani
Keyword(s):  
Molecular Weight ◽  
Surface Modification ◽  
Chain Transfer ◽  
Raft Polymerization ◽  
Silica Nanoparticle ◽  
Maximum Level ◽  
Silica Content ◽  
Considerable Change ◽  
Polymerization Rate ◽  
Raft Agent

Abstract S-(thiobenzoyl)thioglycolic acid was used to synthesize poly(methyl methacrylate) via reversible addition-fragmentation chain transfer (RAFT) polymerization. To study the polymerization kinetics, in situ polymerization reactions were performed with different loading of nanoparticles. To investigate the effect of surface modification on the poly­merization kinetics, similar reactions were performed with 3-methacryloxypropyldimethylchlorosilane-modified nanoparticles. Conversion, reaction rate, molecular weight and polydispersity index (PDI) were monitored during poly­merization. According to results, pseudo-first order kinetics is achieved, but the rate constant of chain transfer reaction to the RAFT agent (Ctr) has a very small value. Adding nanoparticles causes no considerable change in the kinetic curves, while there is an optimum value for nanoparticles loading in which the polymerization rate reaches its maximum level. A similar trend is observed for molecular weight; however, increasing silica content results in an increase in PDI values. In comparison with pristine silica nanoparticles, the polymerization rate increases slowly in the case of modified particles. Also, molecular weight and PDI for free and graft chains are studied separately. The molecular weight of free chains increases with increasing nanoparticles loading up to 7 wt% and then decreases, while PDI values increase continually by adding nanoparticles. However, for graft chains, molecular weight and PDI values increase with increasing nanoparticle content.

Synthesis of Polystyrene-B-Poly(Ethylene Oxide)monomethyl Ethermethacrylate Block Copolymers and its Self-Assembly in Aqueous Solution

2011 ◽  
Vol 284-286 ◽  
pp. 769-772
Author(s):  
Qian Qian You ◽  
Pu Yu Zhang
Keyword(s):  
Aqueous Solution ◽  
Molecular Weight ◽  
Block Copolymers ◽  
Self Assembly ◽  
Chain Transfer ◽  
Functional Group ◽  
Transmission Electron ◽  
Reversible Addition ◽  
Ft Ir ◽  
A Chain

The block copolymer of PSt-b-POEOMA with the end of -COOH functional group has been synthesized by reversible addition fragmentation chain-transfer (RAFT) using S,S′-Bis(α,α′-dimethyl-α′′-acetic acid)-trithiocarbonate (BDATC) as a chain transfer agent. The architectures of the copolymers were confirmed by FT-IR and 1HNMR spectra. GPC analysis was used to estimate the molecular weight and the molecular weight distribution of the copolymers. Meanwhile, The nanostructures of the block copolymers PSt-b-POEOMA micelles formed in aqueous solution were observed by transmission electron microscopy (TEM) and dynamic light scattering (DLS).

scholarly journals Synthesis and characterization of triphenylamine and Bbis(indolyl)methane center-functionalized polymer via reversible addition-fragmentation chain transfer polymerization

e-Polymers ◽  
2008 ◽  
Vol 8 (1) ◽  
Author(s):  
Jie Xu ◽  
Wei Shang ◽  
Jian Zhu ◽  
Zhenping Cheng ◽  
Nianchen Zhou ◽  
...  
Keyword(s):  
Molecular Weight ◽  
Chain Transfer ◽  
Raft Polymerization ◽  
Chloroform Solution ◽  
Monomer Conversion ◽  
Benzyl Ester ◽  
Chain Extension ◽  
Reversible Addition ◽  
Raft Agent ◽  
Cyclic Voltammetry Method

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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