SET‐LRP of methyl acrylate to complete conversion with zero termination

Nguyen, Nga H.; Levere, Martin E.; Percéc, Virgil

doi:10.1002/pola.25838

Cited by 123 publications

(139 citation statements)

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“…48 Extending further it has been shown that in general, copper(0) mediated polymerization has excellent end group fidelity in comparison to other atom transfer processes. [49][50][51][52] Again, the current model would predict that under conditions of fast deactivation, such is the case in these polymerizations, termination and transfer events, which are typically long time scale, should be reduced with respect to propagation, thus allowing for the ultra high molecular weight polymers with near to 0 mol% termination that have been seen already. Although for acrylates this may be explained simply by the large k p /k t ratio, for vinyl chloride it has been shown that the molecular weight can exceed that of free radical polymerization 45 which can only be the case when molecular weight limiting reactions such as chain transfer to monomer and termination are reduced in comparison to propagation.…”

Section: Resultsmentioning

confidence: 99%

Impact of Competitive Processes on Controlled Radical Polymerization

et al. 2014

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The kinetics of radical polymerization have been systematically studied for nearly a century and in general are well understood. However, in the light of recent developments in controlled radical polymerization many kinetic anomalies have arisen. These unexpected results have been largely considered separate and various, as yet inconclusive, debates as to the cause of these anomalies 1 are ongoing. Herein we present a new theory on the cause of changes in kinetics under controlled radical polymerization conditions. We show that where the fast, intermittent deactivation of radical species takes place, changes in the relative rates of the competitive reactions that exist in radical polymerization can occur. To highlight the applicability of the model we demonstrate that the model explains well the reduction in branching in acrylic polymers in RAFT polymerization.We further show that such a theory may explain various phenomena in controlled radical polymerization and may be exploited to design precise macromolecular architectures.

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Section: Resultsmentioning

confidence: 99%

Impact of Competitive Processes on Controlled Radical Polymerization

et al. 2014

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“…In the presence of metallic copper, a so-called supplementary activator and reducing agent (SARA) ATRP or single electron transfer living radical polymerization (SET-LRP) can also be obtained depending on comproportionation or disproportionation being the dominant side reaction path for the involved catalytic species. [58][59][60] In particular for methyl acrylate, Chan et al [61] and Kwak et al [57] have recently successfully combined ARGET ATRP and the use of a copper wire reducing significantly the residual catalyst amount up to 10 ppm for a TCL of ca. 100.…”

Section: Introductionmentioning

confidence: 99%

“…[56][57][58][62][63][64] Such information is crucial for a comparison of these techniques to evaluate their potential industrial application, since the ultimate goal of a CRP technique is to produce a wide range of average chain lengths at acceptable polymerization rates while preserving control over PDI and EGF. In this work, such detailed kinetic modeling study is presented for the bulk ICAR ATRP of nBuA using the commercially available N,N,N 0 ,N 00 ,N 00 -pentamethyldiethylenetriamine (PMDETA)…”

Section: Introductionmentioning

confidence: 99%

Computer‐Aided Optimization of Conditions for Fast and Controlled ICAR ATRP of n‐Butyl Acrylate

Porras

D’hooge

Reyniers

et al. 2013

Macro Theory & Simulations

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The potential of initiators for continuous activator regeneration atom transfer radical polymerization (ICAR ATRP) for the synthesis of well‐defined poly(n‐butyl acrylate) is analyzed by means of simulations. The kinetic model accounts for reactivity differences between secondary and tertiary macrospecies and considers the possible influence of diffusional limitations. CuBr2 is used as transition metal salt and the commercially available N,N,N′,N″,N″‐pentamethyldiethylenetriamine as ligand. For targeted chain lengths (TCLs) up to 1000, the ICAR ATRP can be performed relatively quickly, and with ppm levels of ATRP catalyst. For moderate TCLs, slightly higher ppm levels are required if excellent control over chain length is also desired. In all cases, limited loss of end‐group functionality (EGF) results. magnified image

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“…[1][2][3][4][5][6][7][8][9] The simple and highly versatile SET-LRP process based on the catalysis by Cu(0) powder or wire is remarkably effective for synthesis of polyacrylate. [10][11][12][13][14][15][16][17] As we all know, the LRP is the significant and useful procedure to synthesize polymers with controlled molecular weight and narrow molecular weight distribution.…”

mentioning

confidence: 99%

Single electron transfer-living radical polymerization of acrylonitrile catalyzed by lanthanum powder

Zhang

Hao

Chen

2013

J. Polym. Sci. Part A: Polym. Chem.

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INTRODUCTIONIn recent years, single electron transfer-living radical polymerization (SET-LRP) has received great attention for its distinct advantages, including low temperature, ultrafast polymerization, and high molecular weight polymers with narrow molecular weight distribution. [1][2][3][4][5][6][7][8][9] The simple and highly versatile SET-LRP process based on the catalysis by Cu(0) powder or wire is remarkably effective for synthesis of polyacrylate. [10][11][12][13][14][15][16][17] As we all know, the LRP is the significant and useful procedure to synthesize polymers with controlled molecular weight and narrow molecular weight distribution. However, it has been accomplished only for activated monomers. [18][19][20][21][22][23] The defective has been perfected by SET-LRP for its polymerization of nonactivated vinyl chloride. [24][25][26] From the mechanism of SET-LRP, activation of initiator and dormant halide chain ends is catalyzed by the out-sphere electron transfer (OSET). 27 Compared to the inner-sphere electron transfer (ISET) of atom transfer radical polymerization (ATRP), SET-LRP has lower activation energy. The SET process occurs in the presence of solvents and ligands that facilitate the disproportionation of Cu(I) species to Cu(0) and Cu(II). [28][29][30][31] To establish the proper equilibrium between active and inactive chains, suitable solvents and ligands that enhance the disproportionation of Cu(I) complexes must be used. For this purpose, solvents like dimethyl sulfoxide (DMSO), 32,33 trifluoroethanol, 34 alcohol, 35-37 water, 38-42 ionic liquid, 43,44 and the combination of organic solvent mixture, 45,46 and ligands such as tris(2-(dimethylamino)ethyl)amine, 47,48 tris(2-aminoethyl)amine, 49-51 and polyetherimide 52 have been successfully applied. Effects of ligand on the apparent rate constant of propagation of SET-LRP of methyl acrylate (MA) in DMSO have been reported. 46,53 However, SET-LRP process is mainly catalyzed by Cu or Fe, few studies on other metals or metallic derivatives have been attempted. [54][55][56][57] In this study, SET-LRP of AN catalyzed by La(0) powder in N,N-dimethylformamide (DMF) with carbon tetrachloride (CCl 4 ) as initiator, and hexamethylenetetramine (HMTA) as ligand was investigated. Polyacrylonitrile (PAN) with well-defined molecular weight is successfully obtained. EXPERIMENTAL MaterialsAnalytical reagent grade AN (98%, Tianjin FuChen Chemical Reagents, Tianjin, China) was distilled under normal pressure and stored at 5 C. CCl 4 (>99.5%), methanol (CH 3 OH) (>99.5%), and DMF (>99.5%) were purchased from Tianjin Chemical Reagents and used as received. HMTA and La(0) powder were purchased from Aladdin Chemistry and used without further purification.UV-Vis Spectroscopic Analysis of LaCl 2 /HMTA and LaCl 3 / HMTA in AN/DMF The typical example is as follows: LaCl 2 (77.76 mg, 0.380 mmol) or LaCl 3 (93.20 mg, 0.380 mmol) was added into a dry two-neck round-bottom flask, followed by 0.2662 g of HMTA (1.90 mmol), 10 mL of AN, and 10 mL of DMF. Then the flask was ...

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SET‐LRP of methyl acrylate to complete conversion with zero termination

Cited by 123 publications

References 47 publications

Impact of Competitive Processes on Controlled Radical Polymerization

Impact of Competitive Processes on Controlled Radical Polymerization

Computer‐Aided Optimization of Conditions for Fast and Controlled ICAR ATRP of n‐Butyl Acrylate

Single electron transfer-living radical polymerization of acrylonitrile catalyzed by lanthanum powder

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