Methylation of poly(acrylic acid), prepared using RAFT polymerization, with trimethylsilyldiazomethane: A metamorphosis of the thiocarbonyl group to a thiol-end group

López-Pérez, Liliana; Maldonado‐Textle, Hortensia; Elizalde-Herrera, Luis Ernesto; Telles-Padilla, J. Guadalupe; Guerrero‐Santos, Ramiro; Collins, Scott; Jiménez‐Regalado, Enrique J.; Thomas, Claude St

doi:10.1016/j.polymer.2019.02.025

Cited by 7 publications

(4 citation statements)

References 62 publications

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“…The presence of this asymmetry could be essentially ascribed to the methylation process. Recently, López‐Pérez et al 50 revealed the impact of the TMSCHN 2 on the degradation of thiocarbonyl to a thiol end‐group inducing to a split of the symmetric functionalized RAFT polymers.…”

Section: Resultsmentioning

confidence: 99%

Impact of additives on the rheological properties of associating water‐soluble multiblock polyelectrolytes

Muñoz-López¹,

Thomas

Garcı́a-Cerda³

et al. 2021

J of Applied Polymer Sci

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The impact of additives on the rheological behavior of four associating water‐soluble multiblock polyelectrolytes previously synthesized via reversible addition‐fragmentation chain transfer (RAFT) polymerization was described. These polyelectrolytes contained different number of blocks ranged from 1 to 7 divided into hydrophilic and hydrophobic. The rheological analyses of polymers were performed at 25°C at a given concentration (0.1–15 wt%) in the presence of sodium chloride (NaCl) 0.1–0.5 M, sodium dodecyl sulfate (SDS) 2–10 mM or a mixture of both. Data demonstrated an increase in the viscosity of macroRAFT (ɳ = 0.002–9 Pa·s) and triblock copolymer‐TBC (ɳ = 0.003–0.04 Pa·s) versus the concentration of NaCl. Meanwhile, the viscosity of penta and heptablock copolymer exhibited a diminution whatever the (NaCl) used. Results from the rheological analyses of the associative polyelectrolytes at different (SDS) revealed that the viscosity of macroRAFT and triblock copolymer was kept constant in spite of the increment of the (SDS) while the viscosity of PBC and HBC displayed a pronounced diminution at the lower (SDS). Finally, the results from the rheological analyses of these polyelectrolytes versus a mixture of NaCl‐SDS showed a diminution in the viscosity of these solutions at any concentration of additives.

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Section: Resultsmentioning

confidence: 99%

Impact of additives on the rheological properties of associating water‐soluble multiblock polyelectrolytes

Muñoz-López¹,

Thomas

Garcı́a-Cerda³

et al. 2021

J of Applied Polymer Sci

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“…Furthermore, the block copolymer also exhibits three main maxima at the same regions, confirming the presence of poly(NVC) block. [ 67 ] Thus, the GPC trances of copolymer demonstrated the formation of the desired block copolymer which is further confirmed by its IR and UV–visible spectral analysis. Currently, we are synthesizing various block copolymers from these poly(LAMs) and exploring their applications.…”

Section: Resultsmentioning

confidence: 62%

Controlled Polymerization of N‐Vinyl Imidazole, N‐Vinyl Pyrrolidone, and N‐Vinyl Carbazole with Dithiocarbamates toward High Molar Mass Polymers

Haribabu,

Vijayakrishna

2024

Macro Chemistry & Physics

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Achieving control over the polymerization of less activated monomers (LAMs) like N‐vinyl carbazole (NVC), N‐vinyl pyrrolidone (NVP), and N‐vinyl imidazole (NVIm) to produce high molar mass polymers posing a significant challenge. To accomplish this, we synthesized eight different dithiocarbamates based RAFT (reversible addition‐fragmentation chain transfer) agents and employed them to polymerize NVIm, NVC and NVP in order to understand and establish a suitable agent for their controlled polymerization to achieve high molar mass polymers. Chain ends presence of these RAFT‐derived polymers was established through 1H NMR studies. Further, these active chain ends are used for chain extension reactions to prepare block copolymers. Synthesized RAFT agents 04, 05, 06, and 08 that are bearing primary leaving groups (methyl 2‐acetate, ethyl 2‐acetate, tert‐butyl 2‐acetate and cyanomethane) displayed moderate to good control over the polymerization of NVIm and NVC. Among these, RAFT agent‐08 with cyanomethane leaving group produced poly(NVIm) and poly(NVC) with the highest molar masses of 44,670 Da (1.52) and 53,620 Da (1.4) respectively. Interestingly, RAFT agents bearing both secondary and primary leaving groups showed good control over the NVP polymerization. Notably, RAFT agent‐02 with ethyl‐2‐propionate leaving group yielded poly(NVP) with the highest molar mass of 89,450 Da and dispersity of 1.43.This article is protected by copyright. All rights reserved

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“…A shift of the SEC trace toward higher molecular weights with the polymerization time can be observed, while there are shoulders at low molecular weight area in the products obtained after 24 h, suggesting the possible existence a small quantity of residual low‐molecular‐weight “dead” chains. In this study, trimethylsilyldiazomethane was employed as an efficient methylating agent to obtain methylated samples from the carboxylic‐acid‐containing poly( N ‐acryloyl amino acid)s. Recently, Thomas et al reported that trimethylsilyldiazomethane reacts with the thiocarbonyl group during the methylation of poly(acrylic acid) prepared by RAFT polymerization with a dithiobenzoate, a symmetric trithiocarbonate and an asymmetric trithiocarbonate 60 . They demonstrated that some of the polymer chains have a thiol end group, depending on the structures of the thiocarbonyl group and polymer main chain.…”

Section: Resultsmentioning

confidence: 99%

“…In this study, trimethylsilyldiazomethane was employed as an efficient methylating agent to obtain methylated samples from the carboxylic-acid-containing poly(N-acryloyl amino acid)s. Recently, Thomas et al reported that trimethylsilyldiazomethane reacts with the thiocarbonyl group during the methylation of poly(acrylic acid) prepared by RAFT polymerization with a dithiobenzoate, a symmetric trithiocarbonate and an asymmetric trithiocarbonate. 60 They demonstrated that some of the polymer chains have a thiol end group, depending on the structures of the thiocarbonyl group and polymer main chain. In contrast, dithiocarbamate chain-ends were reported be substantially less susceptible to nucleophilic attack when compared with most other RAFT end-groups.…”

Section: Raft Dispersion Polymerization Of St In the Presence Of Methyl Ester Forms Of Amino-acid-based Polymersmentioning

confidence: 99%

Polymerization‐induced self‐assembly of amino‐acid‐based nano‐objects by reversible addition–fragmentation chain‐transfer dispersion polymerization

Masuko

Kumano

Sugawara

et al. 2021

Journal of Polymer Science

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A series of amino-acid-based amphiphilic diblock copolymer nano-objects having different morphologies were developed by reversible additionfragmentation chain-transfer (RAFT) dispersion polymerization of styrene (St) in methanol. This was mediated by six different hydrophilic poly(Nacryloyl amino acid) macro-chain transfer agents (CTAs), including three carboxylic-acid-containing ones, poly(N-acryloyl-L-proline) (PAProOH), poly (N-acryloyl-4-trans-hydroxy-L-proline) (PAHypOH), and poly(N-acryloyl-Lthreonine) (PAThrOH) prepared by RAFT polymerization, and their methyl ester forms, PAProOMe, PAHypOMe, and PAThrOMe. The effects of polymerization conditions on RAFT dispersion polymerization of St using a dithiocarbamate-terminated PAProOH was investigated. A systematic study of the effects of monomer conversion and concentration afforded the formation of various morphologies (i.e., spheres, worms, and vesicles). The effects of hydrogen-bonding and ionic interactions of the macro-CTAs on the assembled structures of the nano-objects were evaluated using six different macro-CTAs.Transforming the products from methanol to water via dialysis produced amino-acid-based block copolymer nano-objects, exhibiting pH-responsive morphological change, in aqueous solution.

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Methylation of poly(acrylic acid), prepared using RAFT polymerization, with trimethylsilyldiazomethane: A metamorphosis of the thiocarbonyl group to a thiol-end group

Cited by 7 publications

References 62 publications

Impact of additives on the rheological properties of associating water‐soluble multiblock polyelectrolytes

Impact of additives on the rheological properties of associating water‐soluble multiblock polyelectrolytes

Controlled Polymerization of N‐Vinyl Imidazole, N‐Vinyl Pyrrolidone, and N‐Vinyl Carbazole with Dithiocarbamates toward High Molar Mass Polymers

Polymerization‐induced self‐assembly of amino‐acid‐based nano‐objects by reversible addition–fragmentation chain‐transfer dispersion polymerization

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