Copper(0)‐Mediated Living Radical Polymerization of Methyl Methacrylate in a Non‐polar Solvent

Hornby, Ben; West, Andrew; Tom, Jessica; Waterson, Carl; Harrisson, Simon; Perrier, Sébastien

doi:10.1002/marc.201000031

Cited by 59 publications

(70 citation statements)

References 32 publications

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“…[38][39][40][41][42][43][44][45][46][47][48] In ARGET ATRP, various reducing agents (RAs) including zero valent copper, zinc, magnesium, iron, and ascorbic acid are used to reduce transition metal complex in a high oxidation state to in a low oxidation state. [49][50][51][52] SET-LRP of methyl methacrylate catalyzed by in situ prepared Cu(0) at ambient temperature using various metallic powders including Zn(0), Ni(0), Mg(0), and Fe(0) was attempted. 53 There has been no report on the application of Mg powder to obtain high tacticity PAN by SET-LRP.…”

Section: -33mentioning

confidence: 99%

“…A Waters 2414 differential refractometer was used as detector. 13 C NMR spectra were obtained on a Bruker Avance 400 NMR spectrometer using DMSO-d 6 as the solvent. The method for evaluating the tacticity of PAN was according to a previously described procedure.…”

Section: Characterizationmentioning

confidence: 99%

“…Methine (CH) signal detected by 13 C-NMR spectroscopy was used to determine the triad tacticity of PAN. As shown in Table 1, Pan was obtained with a triad tacticity mm of 34.1% by SET-LRP of AN in the presence of Mg powder, complying with the earlier reports.…”

Section: Characterizationmentioning

confidence: 99%

See 2 more Smart Citations

Synthesis of high performance polyacrylonitrile by RASA SET-LRP in the presence of Mg powder

Chen

Liang

et al. 2013

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

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Section: -33mentioning

confidence: 99%

Section: Characterizationmentioning

confidence: 99%

See 1 more Smart Citation

Synthesis of high performance polyacrylonitrile by RASA SET-LRP in the presence of Mg powder

Chen

Liang

et al. 2013

J. Polym. Sci. Part A: 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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“…[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.…”

Section: Introductionmentioning

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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Copper(0)‐Mediated Living Radical Polymerization of Methyl Methacrylate in a Non‐polar Solvent

Cited by 59 publications

References 32 publications

Synthesis of high performance polyacrylonitrile by RASA SET-LRP in the presence of Mg powder

Synthesis of high performance polyacrylonitrile by RASA SET-LRP in the presence of Mg powder

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

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

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