Ambient temperature rapid SARA ATRP of acrylates and methacrylates in alcohol–water solutions mediated by a mixed sulfite/Cu(ii)Br2 catalytic system

Abreu, Carlos M. R.; Serra, Arménio C.; Popov, Anatoliy V.; Matyjaszewski, Krzysztof; Guliashvili, Tamaz; Coelho, Jorge F. J.

doi:10.1039/c3py00772c

Cited by 72 publications

(98 citation statements)

References 53 publications

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“…45 Due to its poor solubility in organic solvents, 61 the concentrations of S 2 O 4 2- anion and consequently the concentrations SO 2 •- resulting from dithionite anion dissociation are very small. In these solvents, an excess of Na 2 S 2 O 4 , was employed, 45,46 and the concentration of SO 2 •- species was maintained low and constant during the course of the polymerization. In aqueous media (more than 75% of water content) the Na 2 S 2 O 4 can be fully soluble, and consequently can generate a very high concentration of SO 2 •- species.…”

Section: Resultsmentioning

confidence: 99%

“…Similar results have been obtained when sulfites were used to polymerize (meth)acrylates in organic solvents. 45,46 In the absence of the ATRP initiator (Table 2, entry 4), the polymerization was much slower (~ 230 times), which indicated that the only a very few polymer chains were initiated directly from the SO 2 •- radical anions.…”

Section: Resultsmentioning

confidence: 99%

“…DMSO) 45 and in more eco-friendly solvents like ionic liquids, 49 alcohols and alcohols/water mixtures. 46-48 …”

Section: Introductionmentioning

confidence: 99%

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Aqueous SARA ATRP using inorganic sulfites

Abreu

Carmali

et al. 2017

Polym. Chem.

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Aqueous supplemental activator and reducing agent atom transfer radical polymerization (SARA ATRP) using inorganic sulfites was successfully carried out for the first time. Under optimized conditions, a well-controlled poly[oligo(ethylene oxide) methyl ether acrylate] (POEOA) was obtained with <30 ppm of soluble copper catalyst using tris(2-pyridylmethyl)amine (TPMA) ligand in the presence of an excess of halide salts (e.g. NaCl). Inorganic sulfites (e.g. Na2S2O4) were continuously fed into the reaction mixture. The mechanistic studies proved that these salts can activate alkyl halides directly and regenerate the activator complex. The effects of the feeding rate of the SARA agent (inorganic sulfites), ligand and its concentration, halide salt and its concentration, sulfite used, and copper concentration, were systematically studied to afford fast polymerizations rates while maintaining the control over polymerization. The kinetic data showed linear first-order kinetics, linear evolution of molecular weights with conversion, and polymers with narrow molecular weight distributions (Đ ~1.2) during polymerization even at relatively high monomer conversions (~80%). “One-pot” chain extension and “one-pot” block copolymerization experiments proved the high chain-end functionality. The polymerization could be directly regulated by starting or stopping the continuous feeding of the SARA agent. Under biologically relevant conditions, the aqueous SARA ATRP using inorganic sulfites was used to synthesize a well-defined protein-polymer hybrid by grafting of P(OEOA480) from BSA-O-[iBBr]30.

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

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Aqueous SARA ATRP using inorganic sulfites

Abreu

Carmali

et al. 2017

Polym. Chem.

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“…Taking into account the Matyjaszewski's researches [17,23,24] it can be stated that the SARA ATRP mechanism is correct. SARA ATRP/SET-LRP was successfully applied to relatively nonpolar monomers (e.g., styrene [25], butyl acrylate [26], methyl acrylate [14,24,26,27], 2-(diisopropylamino) ethyl methacrylate [26,28], methyl methacrylate [19,26,29]), as well as polar monomers (e.g., oligo(ethylene oxide) monomethyl ether acrylate [13], N-isopropylacrylamide [30]) for the preparation of a variety of polymeric materials with different structures and architectures, including homopolymers, and well-defined block copolymers. However, tri-block copolymers have sparked much interest and their potential has been realized in many areas.…”

Section: Introductionmentioning

confidence: 99%

PSt-b-PU-b-PSt copolymers using tetraphenylethane-urethane macroinitiator through SARA ATRP

Chmielarz¹,

Król²

2016

Express Polym. Lett.

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Abstract. The course of supplemental activator and reducing agent (SARA) atom transfer radical polymerization (ATRP) has been presented in the presence of Cu 0 . The novelty of this work is that SARA ATRP has been used for the first time to synthesize polystyrene-b-polyurethane-b-polystyrene copolymers by using tetraphenylethane-urethane macroinitiator as transitional products reacting with styrene in the presence of Cu II Br 2 /TPMA catalyst complex. The influence of copper surface area on the polymerization was examined. It was confirmed that in all cases, both the molecular weight of resulting copolymer increases linearly with increasing conversion as well as the value of ln([M] 0 /[M]) as a function of polymerization time increases linearly. A successful formation of the urethane-styrene copolymers was confirmed by NMR spectral studies.

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“…The advent of Controlled/"Living" Radical Polymerization (CLRP) brought unprecedented tools to synthesize polymers with controlled structures, chain-end functionalities, architecture and narrow molecular weight distribution [16][17][18][19]. Among the CLRP methods, Atom Transfer Radical Polymerization [20] is the most used method due to several intrinsic advantages, such as: easy procedures, commercial availability of the compounds, mild reaction conditions and, more recently, residual amounts of metal complexes [21][22][23][24][25][26][27]. In this paper, we report the use of an amphiphilic copolymer based on poly(ethylene glycol) and poly(4-vinyl pyridine) blocks (mPEG-b-P4VP) [28] for dispersing photocatalytic TiO2 nanoparticles in water, followed by its ∼ ∼ incorporation in an acrylic varnish formulation.…”

Section: Introductionmentioning

confidence: 99%

Stabilization of nano-TiO2 aqueous dispersions with poly(ethylene glycol)-b-poly(4-vinyl pyridine) block copolymer and their incorporation in photocatalytic acrylic varnishes

Monteiro

Dias

Mendes

et al. 2014

Progress in Organic Coatings

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In this work, TiO2 nanoparticles were dispersed and stabilized in water using a novel type of dispersant based on tailor-made amphiphilic block copolymers of poly(ethylene glycol)-block-poly(4-vinyl pyridine) (mPEG-b-P4VP) prepared by atom transfer radical polymerization (ATRP). The performance of this new block copolymer as dispersant was compared to a polyelectrolyte dispersant commonly used for TiO2, sodium salt of polyacrylic acid (Na-PAA). The effect of dispersion technique and type and amount of dispersant on deagglomeration and stability of the TiO2 aqueous suspensions were studied. After incorporation in a standard waterborne acrylic varnish formulation, dry film transparency, photocatalytic activity, and nanoparticle cluster size were also evaluated. The results show that mPEG-b-P4VP copolymer with appropriate block lengths can have a better performance than Na-PAA in terms of aqueous dispersion stabilization and cluster size reduction in the acrylic matrix. This translates into higher film transparency and photocatalytic performance.

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Ambient temperature rapid SARA ATRP of acrylates and methacrylates in alcohol–water solutions mediated by a mixed sulfite/Cu(ii)Br2 catalytic system

Cited by 72 publications

References 53 publications

Aqueous SARA ATRP using inorganic sulfites

Aqueous SARA ATRP using inorganic sulfites

PSt-b-PU-b-PSt copolymers using tetraphenylethane-urethane macroinitiator through SARA ATRP

Stabilization of nano-TiO2 aqueous dispersions with poly(ethylene glycol)-b-poly(4-vinyl pyridine) block copolymer and their incorporation in photocatalytic acrylic varnishes

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