The Use of e-Caprolactone as a Polymerizable Solvent for the Atom Transfer Radical Polymerization of MMA at Low Temperature

Wang, Wenxin; Yin, Zhihui; Detrembleur, Christophe; Lecomte, Philippe; Lou, Xudong; Jérôme, Robert

doi:10.1002/1521-3935(20020401)203:7<968::aid-macp968>3.0.co;2-x

Cited by 22 publications

(18 citation statements)

References 13 publications

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“…The use of -CL as the solvent for ATRP reactions has been reported previously in conventional solvents. 16 In addition, we have demonstrated that -CL exhibits interesting characteristics as a cosolvent for ATRP in scCO 2 . The presence of -CL leads to better controlled living polymerization because the -CL/ scCO 2 solubilizes the propagating chain.…”

Section: Resultsmentioning

confidence: 82%

Synthesis of Graft Copolymers by the Combination of ATRP and Enzymatic ROP in scCO₂

et al. 2006

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A simple strategy is reported for the synthesis of well-defined graft copolymers of poly(methyl methacrylate-co-2-hydroxyethyl methacrylate) P(MMA-co-HEMA) with poly( -caprolactone) (PCL) grafted chains. Using scCO 2 as the only solvent, a one-step synthetic approach is adopted to prepare copolymer backbones via atom transfer radical polymerization (ATRP), and grafted chains are added via enzymatic ring-opening polymerization (eROP). Exhaustive study of the enzymatic grafting efficiency showed that only the hydroxyl groups in the backbone initiated the polymerization of -CL, resulting in an exceptional polymer architecture which is not accessible by conventional chemical polymerization methodology. The lower grafting density obtained (ca. 30-40%) with the enzymatic polymerization of -CL indicates that the system is likely limited by steric hindrance.

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Section: Resultsmentioning

confidence: 82%

Synthesis of Graft Copolymers by the Combination of ATRP and Enzymatic ROP in scCO₂

et al. 2006

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“…This concept of dual or heterofunctional initiators has successfully been applied to the combination of numerous polymerization techniques 1. Examples include ring‐opening polymerization (ROP)/nitroxide‐mediated polymerization (NMP),2–4 ROP/ATRP,5–12 and many more. In some cases, it is even possible to conduct both polymerizations in one pot without intermediate precipitation or purification step provided that there is no mutual interference between the combined polymerization techniques.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of poly(benzyl glutamate‐b‐styrene) rod‐coil block copolymers by dual initiation in one pot

Knoop¹,

Habraken²,

Gogibus³

et al. 2008

J. Polym. Sci. A Polym. Chem.

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We have developed a metal free synthetic pathway to homopolypeptide rod-coil block copolymers. The concept was proven for the synthesis of poly(benzyl-Lglutamate-b-styrene). A dual initiator containing a primary amine and a nitroxide group was used in a macroinitiation approach with high initiation efficiency. Good control over the molecular weight in the ring opening polymerization of benzyl-L-glutamate N-carboxyanhydride was obtained in DMF at 0 8C yielding poly(benzyl-L-glutamates) with low polydispersities around 1.1. The almost quantitative incorporation of the dual initiator was confirmed by MALDI-ToF analysis. Macroinitiation of styrene by nitroxide-mediated controlled radical polymerization yielded the block copolymer with high structural control. The diblock structure was confirmed by molecular weight increase upon macroinitiation by size exclusion chromatography and retention time comparison with homopolymers using gradient polymer elution chromatography. Both polymerizations were also successfully conducted in one pot without intermediate isolation owing to the high compatibility of both polymerization techniques.

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“…This was ascribed to the solvation of the metal center resulting in a more active catalyst. Wang et al17 found that the controlled polymerization of MMA could be performed with CuBr/2,2′‐bipyridine (bipy) in butanone at 25 °C with an 80% conversion after 72 h. Relatively narrowly dispersed high‐molecular‐weight poly(methyl methacrylate) (PMMA) was synthesized with CuBr/ N , N , N ′ N ′, N ″‐pentamethyldiethylenetriamine (PMDETA) in anisole at 30 °C with minimal side reactions 18. Also reported was ATRP of MMA with an optically active binol ester‐based initiator in anisole at 30 °C 19.…”

Section: Introductionmentioning

confidence: 99%

Ambient‐temperature copper‐catalyzed atom transfer radical polymerization of methacrylates in ethylene glycol solvents

Kimani

Moratti

2005

J. Polym. Sci. A Polym. Chem.

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The use of ethylene glycol solvents in the room‐temperature atom transfer radical polymerization (ATRP) of various hydrophobic and hydrophilic methacrylates is demonstrated. Unlike many of the very polar solvents described in the literature for room‐temperature ATRP, these solvents have good solvency for a wide range of polymers and monomers and are cheap and relatively nontoxic. Ethylene glycols with one hydroxyl and one methoxy group, such as tri(ethylene glycol) monomethyl ether (TEGMME), provide optimal results. The polymerization of methyl methacrylate in TEGMME with CuBr/N,N,N′N′,N″‐pentamethyldiethylenetriamine as the catalyst requires the addition of CuCl2 at the beginning of the reaction to produce well‐controlled polymerizations. This leads to polymers with predictable molecular weights and relatively narrow polydispersities. Polymerization in solvents that are fully methoxy‐capped terminate prematurely because of catalyst precipitation. The electrochemical behavior of copper complexes in selected solvents is examined to determine why these solvents provide good rates at room temperature. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 1588–1598, 2005

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The Use of e-Caprolactone as a Polymerizable Solvent for the Atom Transfer Radical Polymerization of MMA at Low Temperature

Cited by 22 publications

References 13 publications

Synthesis of Graft Copolymers by the Combination of ATRP and Enzymatic ROP in scCO₂

Synthesis of Graft Copolymers by the Combination of ATRP and Enzymatic ROP in scCO₂

Synthesis of poly(benzyl glutamate‐b‐styrene) rod‐coil block copolymers by dual initiation in one pot

Ambient‐temperature copper‐catalyzed atom transfer radical polymerization of methacrylates in ethylene glycol solvents

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The Use of e-Caprolactone as a Polymerizable Solvent for the Atom Transfer Radical Polymerization of MMA at Low Temperature

Cited by 22 publications

References 13 publications

Synthesis of Graft Copolymers by the Combination of ATRP and Enzymatic ROP in scCO2

Synthesis of Graft Copolymers by the Combination of ATRP and Enzymatic ROP in scCO2

Synthesis of poly(benzyl glutamate‐b‐styrene) rod‐coil block copolymers by dual initiation in one pot

Ambient‐temperature copper‐catalyzed atom transfer radical polymerization of methacrylates in ethylene glycol solvents

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Synthesis of Graft Copolymers by the Combination of ATRP and Enzymatic ROP in scCO₂

Synthesis of Graft Copolymers by the Combination of ATRP and Enzymatic ROP in scCO₂