Accelerated living cationic ring-opening polymerization of a methyl ester functionalized 2-oxazoline monomer

Bouten, Petra J. M.; Hertsen, Dietmar; Vergaelen, Maarten; Monnery, Bryn D.; Boerman, Marcel A.; Goossens, Hannelore; Çatak, Şaron; Hest, Jan C. M. van; Speybroeck, Véronique Van; Hoogenboom, Richard

doi:10.1039/c4py01373e

Cited by 64 publications

(114 citation statements)

References 36 publications

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“…Series of homopolymers and copolymers of EtOx and nPropOx with MestOx and C3MestOx were prepared [37,38] with varying feed ratios of 10, 20, 30, 50, and 70 mol % MestOx or C3MestOx and a constant monomer to initiator ratio of [M]/[I] = 100, yielding four sets of copolymers. All polymers were terminated with piperidine instead of the widely used methanolic sodium hydroxide /cm at 5 mg¨mL´1 and were stirred at room temperature until all polymer was dissolved.…”

Section: Resultsmentioning

confidence: 99%

“…Dry solvents were obtained from a solvent purification system from J.C. Meyer, with aluminum oxide drying system and a nitrogen flow. MestOx [37], C3MestOx [38], and nPropOx [48] were prepared according to literature procedures. In this paper we describe the synthesis and thermal properties of methyl ester-containing PAOx.…”

Section: Methodsmentioning

confidence: 99%

“…Polymerizations were carried out under microwave irradiation at 140˝C for 20 min aiming for full conversion [37,38]. After cooling to room temperature, the polymerizations were quenched by the addition of piperidine.…”

Section: Polymer Synthesismentioning

confidence: 99%

“…Functional groups, often protected, can be introduced into PAOx by making use of a functional monomer or initiator during the living cationic ring opening polymerisation (CROP, Scheme 1) of 2-oxazoline monomers or by using a functional terminating agent, yielding well-defined PAOx with control over number and type of functionalities [15,[29][30][31][32][33][34][35][36][37][38]. Methyl esters are especially interesting, because they can undergo a direct amidation with a variety of amines to easily introduce other functional groups such as alcohols, hydrazide and amines [39][40][41][42].…”

Section: Introductionmentioning

confidence: 99%

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Thermal Properties of Methyl Ester-Containing Poly(2-oxazoline)s

et al. 2015

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This paper describes the synthesis and thermal properties in solution and bulk of poly(2-alkyl-oxazoline)s (PAOx) containing a methyl ester side chain.Homopolymers of 2-methoxycarbonylethyl-2-oxazoline (MestOx) and 2-methoxycarbonylpropyl-2-oxazoline (C3MestOx), as well as copolymers with 2-ethyl-2-oxazoline (EtOx) and 2-n-propyl-2-oxazoline (nPropOx), with systematic variations in composition were prepared. The investigation of the solution properties of these polymers revealed that the cloud point temperatures (T CP s) could be tuned in between 24˝C and 108˝C by variation of the PAOx composition. To the best of our knowledge, the T CP s of PMestOx and PC3MestOx are reported for the first time and they closely resemble the T CP s of PEtOx and PnPropOx, respectively, indicating similar hydrophilicity of the methyl ester and alkyl side chains. Furthermore, the thermal transitions and thermal stability of these polymers were investigated by DSC and TGA measurements, respectively, revealing amorphous polymers with glass transition temperatures between´1˝C and 54˝C that are thermally stable up to >300˝C.

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Section: Resultsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Section: Polymer Synthesismentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Thermal Properties of Methyl Ester-Containing Poly(2-oxazoline)s

et al. 2015

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“…and star-shaped structure 16 . Furthermore the properties of PAOx are highly tunable by variation 14 of the side-chain R group as well as by copolymerization of different monomers.…”

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Functional Poly(2-oxazoline)s by Direct Amidation of Methyl Ester Side Chains

Mees

Hoogenboom

2015

Macromolecules

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Poly(2-alkyl/aryl-2-oxazoline)s (PAOx) are biocompatible pseudopolypeptides that have received significant interest for biomedical applications in recent years. The growing popularity of PAOx in recent years is driven by its much higher chemical versatility compared with the gold standard in this field, poly(ethylene glycol) (PEG), while having similar beneficial properties, such as stealth behavior and biocompatibility. We further expand the PAOx chemical toolbox by demonstrating a novel straightforward and highly versatile postpolymerization modification platform for the introduction of side-chain functionalities. PAOx having side chain methyl ester functionalities is demonstrated to undergo facile uncatalyzed amidation reactions with a wide range of amines, yielding the corresponding PAOx with side-chain secondary amide groups containing short aliphatic linkers as well as a range of side-chain functionalities including acid, amine, alcohol, hydrazide, and propargyl groups. The PAOx with side-chain methyl ester groups can be prepared by either partial hydrolysis of a PAOx followed by the introduction of the methyl ester via modification of the secondary amine groups with methyl succinyl chloride or by the direct copolymerization of a nonfunctional 2-oxazoline monomer with a 2-methoxycarbonylethyl-2-oxazoline. Thus, this novel synthetic platform enables direct access to a wide range of side-chain functionalities from the same methyl-esterfunctionalized poly(2-oxazoline) scaffold.

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The Chemistry of Poly(2‐oxazoline)s

Verbraeken

Monnery

Lava

et al. 2018

Encyclopedia of Polymer Science and Technology

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Research in the field of poly(2‐alkyl/aryl‐2‐oxazoline)s (PAOx) is rapidly expanding as this polymer class combines high synthetic versatility with good biocompatibility, opening up the way to highly functional (bio)materials. PAOx are prepared by living cationic ring‐opening polymerization (CROP) of 2‐oxazolines. The variety of 2‐oxazoline monomers that are readily available or can easily be synthesized allows for tuning of polymer properties and introduction of diverse functionalities. Moreover, thanks to the living nature of the CROP, well‐defined polymers with narrow molar mass distribution and high end‐group fidelity can be obtained. This article covers all aspects of PAOx ranging from the synthesis of 2‐oxazoline monomers, via an in‐depth discussion of the CROP mechanism to the synthesis and properties of functional PAOx (co)polymers. The presented research demonstrates that due to their structural adaptability and so‐called “stealth” behavior, PAOx are well‐suited for a range of biomedical applications, including polymer therapeutics, scaffolds for three‐dimensional cell culture, surface modification, matrix excipient for solid dispersions, and antimicrobial agents.The goal of this article is not to review all applications of PAOx, but to highlight key examples illustrating the numerous possibilities, broad application range and the general state‐of‐art use.

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Accelerated living cationic ring-opening polymerization of a methyl ester functionalized 2-oxazoline monomer

Cited by 64 publications

References 36 publications

Thermal Properties of Methyl Ester-Containing Poly(2-oxazoline)s

Thermal Properties of Methyl Ester-Containing Poly(2-oxazoline)s

Functional Poly(2-oxazoline)s by Direct Amidation of Methyl Ester Side Chains

The Chemistry of Poly(2‐oxazoline)s

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