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See detailCombination of ring-opening polymerization and "click chemistry": Toward functionalization and grafting of poly(epsilon-caprolactone)
Riva, Raphaël ULg; Schmeits, Stéphanie; Jérôme, Christine ULg et al

in Macromolecules (2007), 40(4), 796-803

A straightforward strategy is proposed for the derivatization of poly(epsilon-caprolactone) (PCL). First, statistical copolymerization of alpha-chloro-epsilon-caprolactone (alpha-Cl-epsilon-CL) with ... [more ▼]

A straightforward strategy is proposed for the derivatization of poly(epsilon-caprolactone) (PCL). First, statistical copolymerization of alpha-chloro-epsilon-caprolactone (alpha-Cl-epsilon-CL) with epsilon-caprolactone (epsilon-CL) was initiated by 2,2-dibutyl-2-stanna-1,3-dioxepane (DSDOP). In a second step, pendent chlorides were converted into azides by reaction with sodium azide. Finally, duly substituted terminal alkynes were reacted with pendent azides by copper-catalyzed Huisgen's 1,3-dipolar cycloaddition, thus a "click" reaction. According to this strategy, pendent hydroxyl and acrylate groups and atom transfer radical polymerization (ATRP) initiators were successfully attached to PCL. Similarly, amphiphilic graft copolymers were prepared by cycloaddition of an alkyne end-capped poly(ethylene oxide) (PEO) onto the azide substituents of the copolyester. The dependence of the grafting yield on the experimental conditions of the "click" reaction, i.e., temperature, solvent, and catalyst, was investigated. This strategy is very versatile because a large variety of aliphatic polyesters can be easily synthesized from a single precursor, easily prepared from commercially available compounds, merely by changing the alkyne involved in the Huisgen's 1,3-dipolar cycloaddition. Last but not least, PCL subsituted by azide groups does not have to be isolated after substitution of chlorides by sodium azide, and the "click" reaction can be carried out in a "one-pot" process. [less ▲]

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See detailCombination of ring-opening polymerization and "click" chemistry for the synthesis of an amphiphilic tadpole-shaped poly(epsilon-caprolactone) grafted by PEO
Li, Haiying; Riva, Raphaël ULg; Jérôme, Robert ULg et al

in Macromolecules (2007), 40(4), 824-831

A tadpole shaped poly(epsilon-caprolactone) (PCL; Mn = 24 500) was made amphiphilic by grafting the two PCL tails with PEO. In the first step, a macrocyclic PCL was synthesized by ring-opening ... [more ▼]

A tadpole shaped poly(epsilon-caprolactone) (PCL; Mn = 24 500) was made amphiphilic by grafting the two PCL tails with PEO. In the first step, a macrocyclic PCL was synthesized by ring-opening polymerization of epsilon-caprolactone (epsilon-CL) initiated by a cyclic tin(IV) dialkoxide and stabilized by local intramolecular photo-cross-linking. In the second step, the polymerization of a mixture of epsilon CL and alpha-chloro-epsilon-caprolactone (alpha Cl epsilon CL) was resumed with formation of two activated chloride containing PCL tails. In the third step, the chlorides were converted into azides onto which alkynyl end-capped PEO was grafted by the copper-mediated Huisgen's cycloaddition [3 + 2], thus giving a "click" reaction. The thermal properties of the final copolymer and the precursors were analyzed by differential scanning calorimetry. The amphiphilicity of the final copolymer was confirmed by micellization in water. [less ▲]

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See detailSynthesis of tadpole-shaped copolyesters based on living macrocyclic poly(epsilon-caprolactone)
Li, H. Y.; Jérôme, Robert ULg; Lecomte, Philippe ULg

in Polymer (2006), 47(26), 8406-8413

Synthesis of an asymmetric tadpole-shaped aliphatic copolyester consisting of a poly(epsilon-caprolactone) ring and two poly(L-lactide) tails was reported for the first time. First, a high molecular ... [more ▼]

Synthesis of an asymmetric tadpole-shaped aliphatic copolyester consisting of a poly(epsilon-caprolactone) ring and two poly(L-lactide) tails was reported for the first time. First, a high molecular weight cyclic PCL macroinitiator (Mn = 31,000) was prepared by intramolecular photocross-linking of "living" chains. Polymerization of L-lactide was resumed by the tin dialkoxide containing macrocycles, thus making the targeted tadpole-shaped copolyester available. A preliminary investigation of the crystallization of these copolyesters was carried out by differential scanning calorimetry and polarized optical microscopy. [less ▲]

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See detailHeterograft copolymers of poly(epsilon-caprolactone) prepared by combination of ATRA "grafting onto" and ATRP "grafting from" processes
Riva, Raphaël ULg; Rieger, Jutta ULg; Jérôme, Robert ULg et al

in Journal of Polymer Science. Part A, Polymer Chemistry (2006), 44(20), 6015-6024

This paper aims at reporting on the synthesis of a heterograft copolymer by combining the "grafting onto" process based on atom transfer radical addition (ATRA) and the "grafting from" process by atom ... [more ▼]

This paper aims at reporting on the synthesis of a heterograft copolymer by combining the "grafting onto" process based on atom transfer radical addition (ATRA) and the "grafting from" process by atom transfer radical polymerization (ATRP). The statistical copolymerization of epsilon-caprolactone (epsilon-CL) and alpha-chloro-epsilon-caprolactone (alpha-Cl-epsilon-CL) was initiated by 2,2-dibutyl-2-stanna-1,3-dioxepane (DSDOP), followed by ATRA of parts of the chlorinated units of poly(alpha-Cl-epsilon-CL-co-epsilon CL) on the terminal double bond of alpha-MeO,omega-CH2=CH-CH2-CO2-poly(ethylene oxide) (PEO). The amphiphilic poly(epsilon CL-g-EO) graft copolymer collected at this stage forms micelles as supported by dynamic light scattering (DLS) and transmission electron microscopy (TEM). The unreacted pendant chloro groups of poly(epsilon-CL-g-EO) were used to initiate the ATRP of styrene with formation of copolymer with two populations of randomly distributed grafts, that is PEO and polystyrene [less ▲]

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See detailMacromolecular engineering of cyclic aliphatic polyesters by ring-opening polymerization
Lecomte, Philippe ULg; Riva, Raphaël ULg; Li, Haiying et al

Conference (2006, September 24)

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See detailRecent developments in the macromolecular engineering of aliphatic polyesters
Lecomte, Philippe ULg

Scientific conference (2006, September 06)

This oral communication was presented by Philippe Lecomte

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See detailNew prospects for the grafting of functional groups onto aliphatic polyesters. Ring-opening polymerization of alpha- or gamma-substituted epsilon-caprolactone followed by chemical derivatization of the substituents
Lecomte, Philippe ULg; Riva, Raphaël ULg; Schmeits, Stephanie ULg et al

in Macromolecular Symposia (2006), 240

Recent progress in the synthesis of aliphatic polyesters, substituted by pendent functional groups, has been reviewed. Two main strategies have to be distinguished. The first route consists of the ring ... [more ▼]

Recent progress in the synthesis of aliphatic polyesters, substituted by pendent functional groups, has been reviewed. Two main strategies have to be distinguished. The first route consists of the ring-opening polymerization of F,caprolactone substituted by various functional groups, protected if needed, in alpha- or gamma-position. In a second strategy, the functional groups are grafted onto preformed polyesters chains in alpha-position of the carbonyl groups. alpha-chloro-epsilon-caprolactone is quite an interesting monomer because, after polymerization, the activated chloride can be easily derivatized by atom transfer radical addition and "click" chemistry, respectively. Similarly, gamma-acrylic-epsilon-caprolactone is precursor of (co)polyesters wellsuited to derivatization of the pendent double bonds by Michael addition. [less ▲]

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See detailSynthesis of macrocyclic poly(epsilon-caprolactone) by intramolecular cross-linking of unsaturated end groups of chains precyclic by the initiation
Li, Haiying; Debuigne, Antoine ULg; Jérôme, Robert ULg et al

in Angewandte Chemie (International ed. in English) (2006), 45(14), 2264-2267

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See detailCombination of ring-opening polymerization and "click" chemistry towards functionalization of aliphatic polyesters
Riva, Raphaël ULg; Schmeits, Stephanie ULg; Stoffelbach, François et al

in Chemical Communications (2005), (42), 5334-5336

Azide pendent groups of aliphatic polyesters have been derivatized into tertiary amines, ammonium salts and poly(ethylene oxide) grafts. The experimental conditions have been optimized (organic solvent ... [more ▼]

Azide pendent groups of aliphatic polyesters have been derivatized into tertiary amines, ammonium salts and poly(ethylene oxide) grafts. The experimental conditions have been optimized (organic solvent, 35 degrees C), such that the aliphatic polyesters are not degraded, including even poly(lactide) which is very sensitive to attack by weak nucleophiles. [less ▲]

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See detailFunctionalization of poly(epsilon-caprolactone) by pendant hydroxyl, carboxylic acid and epoxide groups by atom transfer radical addition
Riva, Raphaël ULg; Lenoir, Sandrine ULg; Jérôme, Robert ULg et al

in Polymer (2005), 46(19), 8511-8518

A straightforward strategy is proposed for grafting hydroxyl, carboxylic acid and epoxide groups along poly (epsilon-caprolactone) chains. Statistical copolymerization of epsilon-caprolactone (epsilon-CL ... [more ▼]

A straightforward strategy is proposed for grafting hydroxyl, carboxylic acid and epoxide groups along poly (epsilon-caprolactone) chains. Statistical copolymerization of epsilon-caprolactone (epsilon-CL) with alpha-chloro-epsilon-caprolactone (alpha-Cl-epsilon-CL) has been initiated by 2,2-dibutyl-2-stanna-1,3-dioxepane (DSDOP), followed by the atom transfer radical addition (ATRA) of but-3-en-1-ol, vinylacetic acid and 1,2-epoxyhex-5-ene, respectively, onto the alpha-chloro units of a poly(alpha-Cl-epsilon-CL-co-epsilon-CL) copolymer. alpha-Cl-epsilon-CL is easily prepared by the Baeyer-Villiger oxidation of 2-chlorocyclohexanone. The influence of the experimental conditions, i.e. temperature, solvent, catalyst, on the grafting yield has been discussed. Because ATRA is tolerant of the investigated functional groups, no protection/deprotection reaction is required, which is a major advantage of the method. [less ▲]

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See detailBiodegradable polymers for biomedical applications
Lecomte, Philippe ULg; Jérôme, Robert ULg

Scientific conference (2005, July 06)

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See detailSynthesis of new substituted poly(ε-caprolactone)s by comination of ring-opening polymerization, atom transfer radical addition and click reaction
Lecomte, Philippe ULg; Riva, Raphaël ULg; Schmeits, Stephanie ULg et al

Poster (2005, May 19)

During the last few years, a great research effort has been devoted to the synthesis of aliphatic polyesters, e.g. poly(ε-caprolactone) and polylactides. Indeed, their remarkable properties of ... [more ▼]

During the last few years, a great research effort has been devoted to the synthesis of aliphatic polyesters, e.g. poly(ε-caprolactone) and polylactides. Indeed, their remarkable properties of biodegradability and biocompatibility pave the way to many new applications in the biomedical field and as substitutes for non degradable polymers. In order to tailor the polyester properties, the grafting of functional groups along the polymer backbone is highly desirable. For the last few years, CERM has reported on the synthesis and the (co)polymerization of novel ε-caprolactones γ-substituted by various functional groups, e.g., ketal, ketone, olefin, protected alcohol and carboxylic acid. Nevertheless, the grafting of a specific functional group onto the aliphatic polyester backbone requires the synthesis of the parent substituted ε-caprolactone. There is accordingly a need for a strategy that would use a unique substituted ε-caprolactone, followed by derivatization by well-established reactions, so making available a wide range of pendent functional groups, polymeric or not. The derivatization reactions have however to be quantitative under mild conditions to prevent the aliphatic polyester from degrading. Moreover, these reactions must be compatible with the functional groups of interest, e.g., hydroxyl and carboxylic acid, in order to avoid the use of cumbersome protection/deprotection reactions. This communication aims at reporting that a-chloro-e caprolactone (αCLεCL) can be easily copolymerized with εCL into poly(αCLεCL-co-εCL) copolymers, which are precursors for various aliphatic polyesters, by using either Atom Transfer Radical Addition (ATRA) or Click reactions. The number of steps is limited whatever the "Click" or the "ATRA" strategy under consideration. In both cases, mild conditions have been found, such that degradation is minimized. Pendent hydroxyl, carboxylic acid and epoxide groups have been attached without using any protection/deprotection reaction. This strategy has been implemented for the synthesis of amphiphilic poly(εCL-g-ethylene oxide) graft copolymers, that have been used to prepare poly(D,L-lactide) nanoparticles for drug delivery applications. [less ▲]

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See detailNew developments in the synthesis of aliphatic polyesters by ring-opening polymerisation
Jérôme, Robert ULg; Lecomte, Philippe ULg

in Smith, R. (Ed.) Biodegradable polymers for polymer industrial applications (2005)

Detailed reference viewed: 50 (7 ULg)