Synthesis of new substituted lactones by "click" chemistry

Riva, Raphaël; Chafaqi, Laila; Jérôme, Robert; Lecomte, Philippe

doi:10.3998/ark.5550190.0008.a19

Cited by 19 publications

(4 citation statements)

References 27 publications

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“…CL modification can be conducted directly at the α-carbon by electrophilic substitution via formation of an anion using a strong base or by synthesizing functionalized CL using Baeyer−Villiger oxidation. Previously, CL has been modified with functional groups such as halogens (bromide, 16 chloride, 17 iodide 18 ), azide, 19 ATRP initiators, 20 methylene, 21 and hydroxyl. 22 Various approaches have been used to introduce a shape memory effect in poly(ε-caprolactone) (PCL).…”

Section: Introductionmentioning

confidence: 99%

Thermoresponsive Semicrystalline Poly(ε-caprolactone) Networks: Exploiting Cross-linking with Cinnamoyl Moieties to Design Polymers with Tunable Shape Memory

Garle

Kong

Ojha

et al. 2012

ACS Appl. Mater. Interfaces

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The overall goal of this study was to synthesize semicrystalline poly(ε-caprolactone) (PCL) copolymer networks with stimuli-responsive shape memory behavior. Herein, we investigate the influence of a cinnamoyl moiety to design shape memory polymer networks with tunable transition temperatures. The effect of various copolymer architectures (random or ABA triblock), the molecular weight of the crystalline domains, PCL diol, (M(w) 1250 or 2000 g mol(-1)) and its composition in the triblock (50 or 80 mol %) were also investigated. The polymer microstructures were confirmed by NMR, DSC, WAXS and UV-vis spectroscopic techniques. The thermal and mechanical properties and the cross-linking density of the networks were characterized by DSC, tensile testing and solvent swelling, respectively. Detailed thermomechanical investigations conducted using DMA showed that shape memory behavior was obtained only in the ABA triblock copolymers. The best shape memory fixity, R(f) of ~99% and shape recovery, R(r) of ~99% was obtained when PCL diol with M(w) 2000 g mol(-1) was incorporated in the triblock copolymer at a concentration of 50 mol %. The series of triblock copolymers with PCL at 50 mol % also showed mechanical properties with tunable shape memory transition temperatures, ranging from 54 °C to close to body temperature. Our work establishes a general design concept for inducing a shape memory effect into any semicrystalline polyester network. More specifically, it can be applied to systems which have the highest transition temperature closest to the application temperature. An advantage of our novel copolymers is their ability to be cross-linked with UV radiation without any initiator or chemical cross-linker. Possible applications are envisioned in the area of endovascular treatment of ischemic stroke and cerebrovascular aneurysms, and for femoral stents.

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Section: Introductionmentioning

confidence: 99%

Thermoresponsive Semicrystalline Poly(ε-caprolactone) Networks: Exploiting Cross-linking with Cinnamoyl Moieties to Design Polymers with Tunable Shape Memory

Garle

Kong

Ojha

et al. 2012

ACS Appl. Mater. Interfaces

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“…25 Although amino polyesters were not prepared, a number of other reports have explored the use of bromo-, chloro, and azido-functionalized lactones towards the synthesis of functional polyesters. [26][27][28][29]…”

Section: Synpacts Syn Lettmentioning

confidence: 99%

Progress towards the Synthesis of Amino Polyesters via Ring-Opening Polymerization (ROP) of Functional Lactones

Hao

Elkassih

Siegwart

2016

Synlett

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Amine-functionalized polyesters are an important class of materials for biomedical applications due to their utility in gene and drug delivery, bioconjugation reactions, hydrogels, and controlled release systems. The synthesis of amino polyesters by ring-opening polymerization (ROP) is an ongoing challenge that is being aided by advances in reaction development. For the benefit of this important research area, this article highlights the related works of synthesizing amino polyesters by ROP as well as our recent synthesis of a new library of amino polyesters from amine-functionalized lactone monomers. 1 Polymerization of Lactone Monomers with Unprotected Amine Functionalities 2 Synthesis of Amino-Functionalized Polyesters via Postpolymerization Modification of Functionalized Monomers 3 Design of Novel Amino-Functionalized Lactone Monomers and Direct Synthesis of Amino Polyesters

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“…The experimental conditions used were so mild that the grafting of PEO was also very effective onto more sensitive PLA-co-P(αN 3 εCL) copolyesters (LA stands for lactide or 3,6-dimethyl-1,4dioxane-2,5-dione) [6]. More recently, a range of novel functional ε-caprolactones were made available by the direct cycloaddition of alkynes substituted by several functional groups, e.g., esters, unprotected alcohols, acrylates, ammonium salts, onto 5-azidooxepane-2-one without any detrimental ring-opening of the lactone [12]. Until now, only few examples of cross-linking by "click" chemistry were reported [13][14][15][16][17].…”

Section: Introductionmentioning

confidence: 99%