Thiol-ene vs. ADMET: a complementary approach to fatty acid-based biodegradable polymers

Türünç, Oğuz; Meier, Michael A. R.

doi:10.1039/c0gc00773k

Cited by 85 publications

(41 citation statements)

References 26 publications

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“…More widely spread and available are α,ω‐olefins, which can be polymerized through acyclic diene metathesis (ADMET) polymerization following a step‐growth pathway (i.e., polycondensation under release of ethylene) . ADMET does not have the features of a living/controlled polymerization but offers the possibility to synthesize polymers, which otherwise are not accessible, for instance, biodegradable unsaturated polymers from bio‐derived ω‐unsaturated fatty acids . Apart from that, however, ADMET polymerization was scarcely applied to produce bio‐derived polymers with heteroatoms along the main chain, e.g., polyamides from amino acids.…”

Section: Introductionmentioning

confidence: 99%

ADMET Polymerization of Amino‐Acid‐Based Diene

Führer

Schlaad

2014

Macro Chemistry & Physics

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1,4‐Di(homo)allyl‐2,5‐diketopiperazines are synthesized and polymerized via ADMET using the Hoveyda–Grubbs 2nd generation catalyst. The but‐3‐enylated diketopiperazine can be converted into unsaturated tertiary polyamide with molar mass of <3000 g mol−1, whereas the allylated diketopiperazine cannot. Double‐bond isomerization occurs regardless of whether or not benzoquinone is present. A polyesteramide with a higher molar mass of ca. 4800 g mol−1 is obtained by the alternating copolymerization (ALTMET) of 1,4‐di(but‐3‐enyl)‐2,5‐diketopiperazine and ethylene glycol diacrylate. A post‐polymerization modification of the poly(ester)amides via radical thiol‐ene chemistry, however, fails.

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Section: Introductionmentioning

confidence: 99%

ADMET Polymerization of Amino‐Acid‐Based Diene

Führer

Schlaad

2014

Macro Chemistry & Physics

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“…[1][2][3] In this context, biobased polymers obtained from vegetable oils are considered a promising sustainable alternative to fossil-derived polymeric materials and present potential biodegradability and low toxicity, allowing their application for high value added and/or biomedical purposes. [4][5][6][7] Thiol-ene polymerization is considered a type of click-chemistry reaction, because it can be carried out under mild conditions and normally provides high yields and offers high atom economy.…”

Section: Introductionmentioning

confidence: 99%

Biocompatible Polymeric Nanoparticles From Castor Oil Derivatives via Thiol‐Ene Miniemulsion Polymerization

Cardoso

Machado²,

Feuser³

et al. 2017

Euro J Lipid Sci & Tech

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Biocompatible polymeric nanoparticles are obtained via thiol-ene polymerization of a biobased monomer in miniemulsion. The α,ω-diene-diester monomer is synthesized through esterification reaction of a glycerol derivative, namely 1,3-propanediol, with 10-undecenoic acid, a long-chain diene carboxylic acid. In order to investigate how different monomeric structures behave toward thiolene polymerization in miniemulsion, two types of thiols are investigated: 1,4-butanedithiol and 2-mercaptoethyl ether. Poly(thioether-ester)s with weight average molecular weight up to 15 kDa (M n ) are obtained, depending on initiator concentration and types of surfactant and dithiol employed. Finally, biobased poly(thioether-ester) nanoparticles are submitted to cytotoxicity and hemolysis analyses. High cell viability and no significant changes in cell morphology are observed after the incubation on murine fibroblast (L929) and human cervical cancer cells (HeLa). Last, hemolysis assays revealed blood compatibility and therefore polymeric nanoparticles have been shown to be a potential alternative drug delivery vector for intravenous administration. Practical Applications: There is a great demand for polymeric systems that fulfill a number of requirements, such as biodegradability and biocompatibility, for biomedical applications. In this context, biobased polymers obtained from vegetable oils are a very attractive sustainable alternative to fossil-derived polymeric materials, presenting potential biodegradability and low toxicity. By thiol-ene reactions, polymeric materials containing ester groups in the main chain -which can undergo hydrolysis-can be prepared in miniemulsion, enabling their degradation in physiological environment and, therefore, being interesting for biomedical applications and material disposal. Such novel materials could be used in temporary implants, tissue engineering, and drug delivery systems.

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“…[2, 23-27, 30, 31] Low temperature and UV radiation have been used to introduce thiols onto vegetable oil backbones through the thiol-ene photoreaction to obtain thiol functionalized vegetable oils. [2,7,23,27] Thiol-ene chemistry with terminal functional groups under thermal conditions has been studied, [20,38] however, the mid-chain unsaturated groups are less likely to undergo the same reactions due to their much lower reactivity. [39] We proposed that the thiol-ene reaction between thiols and the mid-chain double bonds on the vegetable oils could be initiated with the aid of thermal free radical initiators, as illustrated in Scheme 1.…”

Section: Resultsmentioning

confidence: 99%

Synthesis of Soybean Oil‐Based Thiol Oligomers

Wu¹,

Fernando²,

Weerasinghe³

et al. 2011

ChemSusChem

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Industrial grade soybean oil (SBO) and thiols were reacted to generate thiol-functionalized oligomers via a thermal, free radical initiated thiol-ene reaction between the SBO double bond moieties and the thiol functional groups. The effect of the reaction conditions, including thiol concentration, catalyst loading level, reaction time, and atmosphere, on the molecular weight and the conversion to the resultant soy-thiols were examined in a combinatorial high-throughput fashion using parallel synthesis, combinatorial FTIR, and rapid gel permeation chromatography (GPC). High thiol functionality and concentration, high thermal free radical catalyst concentration, long reaction time, and the use of a nitrogen reaction atmosphere were found to favor fast consumption of the SBO, and produced high molecular weight products. The thiol conversion during the reaction was inversely affected by a high thiol concentration, but was favored by a long reaction time and an air reaction atmosphere. These experimental observations were explained by the initial low affinity of the SBO and thiol, and the improved affinity between the generated soy-thiol oligomers and unreacted SBO during the reaction. The synthesized soy-thiol oligomers can be used for renewable thiol-ene UV curable materials and high molecular solids and thiourethane thermal cure materials.

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Thiol-ene vs. ADMET: a complementary approach to fatty acid-based biodegradable polymers

Cited by 85 publications

References 26 publications

ADMET Polymerization of Amino‐Acid‐Based Diene

ADMET Polymerization of Amino‐Acid‐Based Diene

Biocompatible Polymeric Nanoparticles From Castor Oil Derivatives via Thiol‐Ene Miniemulsion Polymerization

Synthesis of Soybean Oil‐Based Thiol Oligomers

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