A 13C nuclear magnetic resonance study of the microstructure of poly(vinyl alcohol)

Vercauteren, F.F.; Donners, W. A. B.

doi:10.1016/0032-3861(86)90062-5

Cited by 19 publications

(10 citation statements)

References 21 publications

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“…One of the main reasons for the broadening is most probably the accumulation of the less reactive primary C-SC(S)OR 0 terminal originating from the head-to-head addition, which is inherent in the VAc radical polymerization. [44][45][46][47][48] These results suggest that Mn 2 (CO) 10 induces the controlled/living radical polymerization of VAc even in conjunction with a xanthate via the reversible activation of the C-SC(S)OR terminal.…”

Section: Measurementsmentioning

confidence: 79%

Mn2(CO)10-Induced RAFT Polymerization of Vinyl Acetate, Methyl Acrylate, and Styrene

2009

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A dinuclear manganese complex [Mn 2 (CO) 10 ] induced the controlled/living radical polymerization of various conjugated and unconjugated vinyl monomers including vinyl acetate, methyl acrylate, and styrene in conjunction with dithiocarbonyl compounds [R-SC(S)Z] under weak visible light at 40 C. The obtained polymers had controlled molecular weights, narrow molecular weight distributions, and well-defined chain-end groups originating from R-SC(S)Z, as indicated by SEC, 1 H NMR, and MALDI-TOF-MS analyses. The polymerization most probably proceeds via the reversible activation of the C-SC(S)Z bond by Á Mn(CO) 5 via the metal-catalyzed process and/or by the carbon-centered radical species via the additionfragmentation chain transfer (RAFT) process.KEY WORDS: Vinyl Acetate / Acrylate / Styrene / Living Radical Polymerization / RAFT Polymerization / Manganese Complex / Various aspects of the controlled/living radical polymerization have been significantly developed in this decade, including a variety of initiating systems, controllable monomers, polymer structures, fusion with other substances, and applications to functional materials. Among the numerous initiating systems, there are now three representatives in terms of wide applicability and good controllability; i.e., the nitroxide-mediated radical polymerization (NMP), 1,2 metal-catalyzed living radical polymerization or atom transfer radical polymerization (ATRP), [3][4][5][6][7][8][9][10][11][12][13][14][15][16][17] and reversible addition-fragmentation chain transfer (RAFT) 18 polymerization or macromolecular design via interchange of xanthate (MADIX). 19 Although the components and the mechanisms are different, they are all based on the reversible transient activation of the dormant covalent species into the growing radical species. However, each system has its own characteristics or features due to the differences, which suggests that the choice of initiating systems is important depending on the monomers, conditions, purposes, etc.The metal-catalyzed living radical polymerization or ATRP is one of the best methods in terms of the well-defined architecture of the polymers from a variety of conjugated monomers, such as methacrylates, acrylates, acrylamides, acrylonitrile, and styrenes. This polymerization is generally initiated by the carbon radical generated from the alkyl halide upon the activation of the carbon-halogen bond by the transition metal catalyst, and then proceeds via the metalcatalyzed reversible activation of the carbon-halogen terminal into the growing radical species. One growing polymer chain end is thus generated from one carbon-halogen bond, which can permit the well-defined polymer synthesis. Although various transition metals, such as ruthenium, 3 20 The choice of the metal complexes including metals and ligands as well as the halides is important for the precise control of the polymerizations depending on the monomers.In contrast, the RAFT/MADIX system with the dithiocarbonyl compounds [R-SC(S)Z] is one of the most widely applica...

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Section: Measurementsmentioning

confidence: 79%

Mn2(CO)10-Induced RAFT Polymerization of Vinyl Acetate, Methyl Acrylate, and Styrene

2009

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“…The minor peaks at 14.1ppm, 21.1ppm, 30.0ppm, 60.3ppm, 177.3 ppm from initiator EBiB were also well resolved in the spectrum. Based on Levy and Nelson' method49, 50 the minor peaks at 24.6 ppm and 27.1 ppm were attributed to the tail‐to‐tail structure (Scheme ), which was about 5.7% of the total repeating units. The signal of the head‐to‐head structure (carbon m, n) at about 75–77 ppm and the ω‐terminal methine carbon with a C‐Br bond (carbon i, ∼76 ppm) were unfortunately overlapped in the solvent CDCl 3 peaks.…”

Section: Resultsmentioning

confidence: 99%

Microsatellite instability and expression of MLH1 and MSH2 in carcinomas of the small intestine

Schulmann

Hahn

Brasch

et al. 2003

Cancer

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Copper‐mediated atom transfer radical polymerization (ATRP) is versatile for living polymerizations of a wide range of monomers, but ATRP of vinyl acetate (VAc) remains challenging due to the low homolytic cleavage activity of the carbon‐halide bond of the dormant poly(vinyl acetate) (PVAc) chains and the high reactivity of growing PVAc radicals. Therefore, all the reported highly active copper‐based catalysts are inactive in ATRP of VAc. Herein, we report the first copper‐catalyst mediated ATRP of VAc using CuBr/2,2′:6′,2″‐terpyridine (tPy) or CuCl/tPy as catalysts. The polymerization was a first order reaction with respect to the monomer concentration. The molecular weights of the resulting PVAc linearly increased with the VAc conversion. The living character was further proven by self‐chain extension of PVAc. Using polystyrene (PS) as a macroinitiator, a well‐defined diblock copolymer PS‐b‐PVAc was prepared. Hydrolysis of the PS‐b‐PVAc produced a PS‐b‐poly(vinyl alcohol) amphiphilic diblock copolymer. © 2009 American Institute of Chemical Engineers AIChE J, 2009

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“…47,48 The minor peaks at 14.1ppm, 21.1ppm, 30.0ppm, 60.3ppm, 177.3 ppm from initiator EBiB were also well resolved in the spectrum. Based on Levy and Nelson' method 49,50 the minor peaks at 24.6 ppm and 27.1 ppm were attributed to the tail-to-tail structure (Scheme 2), which was about 5.7% of the total repeating units. The signal of the head-to-head structure (carbon m, n) at about 75-77 ppm and the x-terminal methine carbon with a C-Br bond (carbon i, $76 ppm) were unfortunately overlapped in the solvent CDCl 3 peaks.…”

Section: Nmr Study On the Microstructure Of Pvacmentioning

confidence: 99%

Atom transfer radical polymerization and copolymerization of vinyl acetate catalyzed by copper halide/terpyridine

2009

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in Wiley InterScience (www.interscience.wiley.com).Copper-mediated atom transfer radical polymerization (ATRP) is versatile for living polymerizations of a wide range of monomers, but ATRP of vinyl acetate (VAc) remains challenging due to the low homolytic cleavage activity of the carbon-halide bond of the dormant poly(vinyl acetate) (PVAc) chains and the high reactivity of growing PVAc radicals. Therefore, all the reported highly active copper-based catalysts are inactive in ATRP of VAc. Herein, we report the first copper-catalyst mediated ATRP of VAc using CuBr/2,2 0 :6 0 ,2 00 -terpyridine (tPy) or CuCl/tPy as catalysts. The polymerization was a first order reaction with respect to the monomer concentration. The molecular weights of the resulting PVAc linearly increased with the VAc conversion. The living character was further proven by self-chain extension of PVAc. Using polystyrene (PS) as a macroinitiator, a well-defined diblock copolymer PS-b-PVAc was prepared. Hydrolysis of the PS-b-PVAc produced a PS-b-poly(vinyl alcohol) amphiphilic diblock copolymer.

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A 13C nuclear magnetic resonance study of the microstructure of poly(vinyl alcohol)

Cited by 19 publications

References 21 publications

Mn2(CO)10-Induced RAFT Polymerization of Vinyl Acetate, Methyl Acrylate, and Styrene

Mn2(CO)10-Induced RAFT Polymerization of Vinyl Acetate, Methyl Acrylate, and Styrene

Microsatellite instability and expression of MLH1 and MSH2 in carcinomas of the small intestine

Atom transfer radical polymerization and copolymerization of vinyl acetate catalyzed by copper halide/terpyridine

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