Two in one: use of azide functionality for controlled photo-crosslinking and click-modification of polymer microspheres

Albuszis, Marco; Roth, Peter J.; Pauer, Werner; Moritz, Hans‐Ulrich

doi:10.1039/c6py00937a

Cited by 35 publications

(27 citation statements)

References 59 publications

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“…Azide-functional polymers are used as energetic materials − but are also receiving increasing interest as versatile precursors for postpolymerization modification , through a variety of reactions including Cu-catalyzed azide–alkyne cycloaddition (CuAAC), azide–thioacid amidation, and thermal or photochemical cross-linking reactions. , Para-substituted tetrafluorophenyl azides (R–C 6 F 4 –N 3 ) constitute a unique class of organic azides. With the strong electron-withdrawing effect of the fluorinated aromatic, these azides undergo a variety of reactions that are not available to the more common alkyl azides such as the formation of stable iminophosphoranes , via the Staudinger reaction with phosphines, the three-component azide–aldehyde–amine reaction, or the rapid formation of anilides with thioacids .…”

Section: Introductionmentioning

confidence: 99%

Perfluorophenyl Azides: Photo, Staudinger, and Multicomponent Postpolymerization Reactions on Homopolymers and PISA-Made Nanoparticles

Busatto

Roth

2021

Macromolecules

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A novel monomer, 4-azido-2,3,5,6-tetrafluorobenzyl methacrylate (ABMA), enabled the selective and efficient postpolymerization modification of reversible addition–fragmentation chain transfer(RAFT)-made homopolymers and diblock copolymer nanoparticles prepared through polymerization-induced self-assembly (PISA). Poly(ABMA) homopolymers were modified postpolymerization in (near-)quantitative conversions with phosphines to give stable iminophosphoranes and in a multicomponent reaction with phenylacetaldehyde and morpholine, piperidine, or the cross-linker N,N′-dimethylethylene diamine to give the corresponding amidine derivatives in one step. Product polymers were characterized by nuclear magnetic resonance and Fourier-transform infrared spectroscopy, size-exclusion chromatography, and differential scanning calorimetry. Unlike its monomer, poly(ABMA) was insoluble in ethanol and enabled the preparation of well-defined spherical, worm-shaped, and vesicular nanoparticles with azide-functional cores through RAFT dispersion polymerization with concurrent PISA. The worm-shaped particles formed physical gels that underwent a thermally reversible degelation. Multicomponent modification of spherical nanoparticles with phenyl acetaldehyde and morpholine or piperidine led to (near-)quantitative core modification and for morpholine, a significant increase in its sphere diameter. UV irradiation of nanoparticles led to cross-linking through the formation of reactive nitrene intermediates, which prevented the disassembly of nanoparticles in nonselective solvents, representing a simple and reagent-free cross-linking strategy and expanding the scope of azide-based polymer chemistry.

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Section: Introductionmentioning

confidence: 99%

Perfluorophenyl Azides: Photo, Staudinger, and Multicomponent Postpolymerization Reactions on Homopolymers and PISA-Made Nanoparticles

Busatto

Roth

2021

Macromolecules

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“…It was observed that AZPES‐1 exhibited an intense exothermic peak with a peak maximum at 252 °C during the first heating scan. The peak is attributed to the decomposition of azide moiety into highly reactive nitrene intermediates with concomitant occurrence of crosslinking reactions involving formation of intra‐ and intermolecular bonds with neighboring polymer backbone resulting into a network structure …”

Section: Resultsmentioning

confidence: 99%

A new cardo bisphenol monomer containing pendant azido group and the resulting aromatic polyesters

Maher

Nagane

Jadhav

et al. 2019

J. Polym. Sci. Part A: Polym. Chem.

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Expanding on our strategy to synthesize aromatic stepgrowth polymers containing pendant clickable azido groups via functional monomer approach, we have now designed and synthesized a new cardo bisphenol, viz., 2-(2-azidoethyl)-3, 3-bis(4-hydroxyphenyl) isoindolin-1-one (PPH-N 3 ). PPH-N 3 was conveniently synthesized starting from commercially available phenolphthalein by a three-step route in an overall yield of 65% using simple organic transformations. Aromatic (co)polyesters bearing pendant azido groups were synthesized by low-temperature solution polycondensation of PPH-N 3 or different molar ratios of PPH-N 3 and bisphenol-A (BPA) with aromatic diacid chlorides in dry dichloromethane in the presence of triethylamine (TEA) as a base. The formation of medium to reasonably high-molecular-weight (co)polyesters was evidenced from intrinsic viscosity and number-average molecular-weight measurements that were in the range 0.52-0.85 dL/g and 16,700-28,200, respectively. Tough, transparent, and flexible films could be cast from chloroform solutions of these (co)polyesters. (Co)polyesters were characterized using FTIR, 1 H NMR, 13 C NMR spectroscopy, XRD, and TGA. The thermal curing reaction of (co)polyesters involving decomposition of azido groups was studied by DSC analysis. The chemical modification of a representative copolyester containing pendant azido groups was carried out quantitatively using catalyst-free azide-maleimide cycloaddition reaction with two maleimides, namely, Nmethylmaleimide and N-hexylmaleimide.Additional supporting information may be found in the online version of this article.

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“…Bis-FB-N 3 , which is a photocrosslinker molecule and a phenylazide derivative, contains a ligand with a photosensitive moiety, which can be connected to the receptor site of relatively inert polymer moieties (e.g., alkyl chains) . Upon activation by UV light, the azide group of bis-FB-N 3 sheds a molecule of nitrogen and forms a highly reactive nitrene group that can undergo several addition and C–H insertion reactions with nearby molecules, forming covalent cross-links between different polymer backbones. , These reactions have high reaction efficiencies, excellent stability, and simple preparation. As a result, the crosslinked organic layer not only possesses a strong resistance to counter common organic solvents but also allows us to fabricate patterned structures such as a negative photoresist under UV light.…”

Section: Resultsmentioning

confidence: 99%

Two-in-One Device with Versatile Compatible Electrical Switching or Data Storage Functions Controlled by the Ferroelectricity of P(VDF-TrFE) via Photocrosslinking

Hwang

Jang

Kang

et al. 2019

ACS Appl. Mater. Interfaces

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Organic electronics demand new platforms that can make integrated circuits and undergo mass production while maintaining diverse functions with high performance. The field-effect transistor has great potential to be a multifunctional device capable of sensing, data processing, data storage, and display. Currently, transistor-based devices cannot be considered intrinsic multifunctional devices because all installed functions are mutually coupled. Such incompatibilities are a crucial barrier to developing an all-in-one multifunctional device capable of driving each function individually. In this study, we focus on the decoupling of electric switching and data storage functions in an organic ferroelectric memory transistor. To overcome the incompatibility of each function, the high permittivity needed for electrical switching and the ferroelectricity needed for data storage become compatible by restricting the motion of poly(vinylidene fluoride-trifluoroethylene) via photocrosslinking with bis-perfluorobenzoazide. The two-in-one device consisting of a photocrosslinked ferroelectric layer exhibits reversible and individual dual-functional operation as a typical transistor with nonvolatile memory. Moreover, a p-MOS depletion load inverter composed of the two transistors with different threshold voltages is also demonstrated by simply changing only one of the threshold voltages by polarization switching. We believe that the two-in-one device will be considered a potential component of integrated organic logic circuits, including memory, in the future.

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Two in one: use of azide functionality for controlled photo-crosslinking and click-modification of polymer microspheres

Abstract: UV-Irradiation of azide-functional microspheres for several minutes is shown to result in efficient crosslinking based on nitrene chemistry and to spare a controllable amount of azide functionality which is amenable to click-modification through CuAAC.

Cited by 35 publications

References 59 publications

Perfluorophenyl Azides: Photo, Staudinger, and Multicomponent Postpolymerization Reactions on Homopolymers and PISA-Made Nanoparticles

Perfluorophenyl Azides: Photo, Staudinger, and Multicomponent Postpolymerization Reactions on Homopolymers and PISA-Made Nanoparticles

A new cardo bisphenol monomer containing pendant azido group and the resulting aromatic polyesters

Two-in-One Device with Versatile Compatible Electrical Switching or Data Storage Functions Controlled by the Ferroelectricity of P(VDF-TrFE) via Photocrosslinking

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