Rapid Bonding/Debonding on Demand: Reversibly Cross-Linked Functional Polymers via Diels−Alder Chemistry

Inglis, Andrew J.; Nebhani, Leena; Altintas, Ozcan; Schmidt, Friedrich Georg; Barner‐Kowollik, Christopher

doi:10.1021/ma100945b

Cited by 134 publications

(101 citation statements)

References 28 publications

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“…[268,546,613,614] In recent work the process has been developed as a route to block copolymers, [268,296,297,548,615] graft, star, and network polymers, [309,614] and modified surfaces. [295,547,613] The method is also used in synthetic organic chemistry.…”

Section: Click Reactionsmentioning

confidence: 99%

“…[297] The reaction is thermally reversible [309,548,617] prompting a proposal that it might be used as a thermally stimulated colour switch [548,617] or be applied in reversible block [298] or network formation. [309] The Thiocarbonyl 1,3-Dipolar Cycloaddition Reaction It has been found that diazomethane undergoes a facile 1,3-dipolar cycloaddition with dithiobenzoate RAFT agents and with dithiobenzoate end-groups of polymers formed by reversible addition-fragmentation chain transfer (RAFT) polymerization. [181] Thus, 2-cyanoprop-2-yl dithiobenzoate (12), on treatment with diazomethane at room temperature, provided stereoisomeric 1,3-dithiolanes in near quantitative (.95 %) yield.…”

Section: Click Reactionsmentioning

confidence: 99%

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Living Radical Polymerization by the RAFT Process – A Third Update

2012

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This paper provides a third update to the review of reversible deactivation radical polymerization (RDRP) achieved with thiocarbonylthio compounds (ZC(¼S)SR) by a mechanism of reversible addition-fragmentation chain transfer ( Chem. 2009Chem. , 62, 1402. This review cites over 700 publications that appeared during the period mid 2009 to early 2012 covering various aspects of RAFT polymerization which include reagent synthesis and properties, kinetics and mechanism of polymerization, novel polymer syntheses, and a diverse range of applications. This period has witnessed further significant developments, particularly in the areas of novel RAFT agents, techniques for end-group transformation, the production of micro/nanoparticles and modified surfaces, and biopolymer conjugates both for therapeutic and diagnostic applications.

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Section: Click Reactionsmentioning

confidence: 99%

Section: Click Reactionsmentioning

confidence: 99%

Living Radical Polymerization by the RAFT Process – A Third Update

2012

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“…Retro-DA reaction occurs at an elevated temperature, producing the original diene and dienophile. 46, 47 …”

Section: Synthetic Strategiesmentioning

confidence: 99%

Modular and orthogonal synthesis of hybrid polymers and networks

2015

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Biomaterials scientists strive to develop polymeric materials with distinct chemical make-up, complex molecular architectures, robust mechanical properties and defined biological functions by drawing inspirations from biological systems. Salient features of biological designs include (1) repetitive presentation of basic motifs; and (2) efficient integration of diverse building blocks. Thus, an appealing approach to biomaterials synthesis is to combine synthetic and natural building blocks in a modular fashion employing novel chemical methods. Over the past decade, orthogonal chemistries have become powerful enabling tools for the modular synthesis of advanced biomaterials. These reactions require building blocks with complementary functionalities, occur under mild conditions in the presence of biological molecules and living cells and proceed with high yield and exceptional selectivity. These chemistries have facilitated the construction of complex polymers and networks in a step-growth fashion, allowing facile modulation of materials properties by simple variations of the building blocks. In this review, we first summarize features of several types of orthogonal chemistries. We then discuss recent progress in the synthesis of step growth linear polymers, dendrimers and networks that find application in drug delivery, 3D cell culture and tissue engineering. Overall, orthogonal reactions and modulular synthesis have not only minimized the steps needed for the desired chemical transformations but also maximized the diversity and functionality of the final products. The modular nature of the design, combined with the potential synergistic effect of the hybrid system, will likely result in novel hydrogel matrices with robust structures and defined functions.

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“…However, only PE containing polymers precipitate during the cooling of the toluene solution to ambient temperature so that only trace amounts of PiBoAc should be left in the material recovered by filtration. In addition, BarnerKowollik and coworkers [22] reported that the retro DielsAlder reaction can occur at temperatures of close to 80 8C, regenerating the starting Cp and dithioformate containing reactants. In the present study, the SEC analyses are performed at 150 8C to solubilize the PE-based materials.…”

Section: Synthesis Of Poly(ethylene)-block-poly(isobornyl Acrylate) (mentioning

confidence: 99%

Synthesis of Cyclopentadienyl Capped Polyethylene and Subsequent Block Copolymer Formation Via Hetero Diels‐Alder (HDA) Chemistry

Espinosa¹,

Glaßner²,

Boisson³

et al. 2011

Macromol. Rapid Commun.

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In the current contribution it is demonstrated - for the first time - that poly(ethylene) (M(n) = 1,400 as well as 2,800 g · mol(-1) , PDI = 1.2) can be readily equipped with highly reactive cyclopentadienyl (Cp) end groups. The Cp terminal poly(ethylene) can subsequently be reacted in an efficient hetero Diels-Alder (HDA) reaction with macromolecules (poly(isobornyl acrylate) (M(n) = 4,600 g · mol(-1) , PDI = 1.10) and poly(styrene) (M(n) = 6,300 g · mol(-1) , PDI = 1.13) featuring strongly electron withdrawing thiocarbonyl thio end groups, prepared via reversible addition fragmentation chain transfer (RAFT) polymerization employing benzylpyridin-2-yldithioformate (BPDF) as transfer agent. The resulting block copolymers have been analyzed via high-temperature size exclusion chromatography (SEC) as well as nuclear magnetic resonance (NMR) spectroscopy. The current system allows for the removal of the excess of the non-poly(ethylene) containing segment via filtration of the poly(ethylene)-containing block copolymer. However, the reaction temperatures need to be judiciously selected. Characterization of the generated block copolymers at elevated temperatures can lead - depending on the block copolymer type - to the occurrence of retro Diels-Alder processes. The present study thus demonstrates that RAFT-HDA ligation can be effectively employed for the generation of block copolymers containing poly(ethylene) segments.

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Rapid Bonding/Debonding on Demand: Reversibly Cross-Linked Functional Polymers via Diels−Alder Chemistry

Cited by 134 publications

References 28 publications

Living Radical Polymerization by the RAFT Process – A Third Update

Living Radical Polymerization by the RAFT Process – A Third Update

Modular and orthogonal synthesis of hybrid polymers and networks

Synthesis of Cyclopentadienyl Capped Polyethylene and Subsequent Block Copolymer Formation Via Hetero Diels‐Alder (HDA) Chemistry

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