A new type of base-triggered self-amplifying degradable polyurethane is reported that degrades under mild conditions, with the release of increasing amounts of amine product leading to self-amplified degradation. The polymer incorporates a base-sensitive Fmoc-derivative into every repeating unit to enable highly sensitive amine amplified degradation. A sigmoidal degradation curve for the linear polymer was observed consistent with a self-amplifying degradation mechanism. An analogous cross-linked polyurethane gel was prepared and also found to undergo amplified breakdown. In this case, a trace amount of localized base initiates the degradation, which in turn propagates through the material in an amplified manner. The results demonstrate the potential utility of these new generation polyurethanes in enhanced disposability and as stimuli responsive materials.
more »
« less
Construction from destruction using a photo-triggered self-propagating degradable polyurethane as a one-pot epoxy
We report a photo-triggered, base generating, base propagating degradable polyurethane that is triggered by 365 nm UV light irradiation. A small area of this polyurethane material can be exposed to 365 nm UV light irradiation to generate basic species that can initiate a base propagated degradation process within the bulk material leading to global degradation without the need for continous UV irradiation. The polymer was synthesized by a polycondensation polymerization of a small amount of o -nitrobenzene diol 2 , a large amount of Fmoc-based diol 3 , and hexylmethylene diisocyanate. Integrating both photosensitive and base-sensitive carbamate moieties into the polymer 1 backbone provides the UV light-triggered base propagating degradable polyurethane material. Degradation studies of polymer 1 using 1 H NMR and gel permeation chromatography (GPC) suggest that initial UV irradiation triggers the degradation of the photosensitive o -nitrobenzene carbamate linkages, releasing a primary amino group that causes a cascade of amines to form by further degrading the remaining Fmoc carbamate groups. A bulk polyurethane film was prepared using Fmoc-based triol 4 as a monomer. UV-irradiation of a small localized area of the film initiates the propagation throughout, leading to efficient bulk degradation of the entire material. The amine degradation products could be utilized to make a one-pot epoxy adhesive, showing a potential upcycling application of this self-propagating degradable polyurethane system.
more »
« less
- Award ID(s):
- 1709718
- PAR ID:
- 10252342
- Date Published:
- Journal Name:
- Polymer Chemistry
- Volume:
- 11
- Issue:
- 38
- ISSN:
- 1759-9954
- Page Range / eLocation ID:
- 6215 to 6220
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
-
Abstract Ultraviolet (UV), visible, and near‐infrared (NIR) broadband organic photodetectors are fabricated by sequential solution‐based thin film coatings of a polymer electron blocking layer (EBL) and a polymer photoactive layer. To avoid damage to a preceding polymer EBL during a subsequent solution‐based film coating of a polymer photoactive layer due to lack of solvent orthogonality, 2‐(((4‐azido‐2,3,5,6‐tetrafluorobenzoyl)oxy)methyl)−2‐ethylpropane‐1,3‐diyl bis(4‐azido‐2,3,5,6‐tetrafluorobenzoate) (FPA‐3F) is used as a novel organic cross‐linking agent activated by UV irradiation with a wavelength of 254 nm. Solution‐processed poly[N,N′‐bis(4‐butylphenyl)‐N,N′‐bis(phenyl)‐benzidine] (poly‐TPD) films, which are cross‐linked with a FPA‐3F photocrosslinker, are used for a preceding polymer EBL. A ternary blend film composed of PTB7‐Th, COi8DFIC, and PC71BM is used as a NIR‐sensitive organic photoactive layer with strong photosensitivity in multispectral (UV–visible–NIR) wavelengths of 300–1,050 nm. Poly‐TPD films are successfully cross‐linked even with a very small amount of 1 wt% FPA‐3F. Small amounts of FPA‐3F have little detrimental effect on the electrical and optoelectronic properties of the cross‐linked poly‐TPD EBL. Finally, organic NIR photodetectors with a poly‐TPD EBL cross‐linked by the small addition of FPA‐3F (1 wt%) show the detectivity values higher than 1 × 1012Jones for the entire UV–visible–NIR wavelengths from 300 nm to 1050 nm, and the maximum detectivity values of 1.41 × 1013Jones and 8.90 × 1012Jones at the NIR wavelengths of 900 and 1000 nm, respectively.more » « less
-
Photocatalytic self-cleaning coatings with a high surface area are important for a wide range of applications, including optical coatings, solar panels, mirrors, etc. Here, we designed a highly porous TiO2 coating with photoinduced self-cleaning characteristics and very high hydrophilicity. This was achieved using the swelling-assisted sequential infiltration synthesis (SIS) of a block copolymer (BCP) template, which was followed by polymer removal via oxidative thermal annealing. The quartz crystal microbalance (QCM) was employed to optimize the infiltration process by estimating the mass of material infiltrated into the polymer template as a function of the number of SIS cycles. This adopted swelling-assisted SIS approach resulted in a smooth uniform TiO2 film with an interconnected network of pores. The synthesized film exhibited good crystallinity in the anatase phase. The resulting nanoporous TiO2 coatings were tested for their functional characteristics. Exposure to UV irradiation for 1 h induced an improvement in the hydrophilicity of coatings with wetting angle reducing to unmeasurable values upon contact with water droplets. Furthermore, their self-cleaning characteristics were tested by measuring the photocatalytic degradation of methylene blue (MB). The synthesized porous TiO2 nanostructures displayed promising photocatalytic activity, demonstrating the degradation of approximately 92% of MB after 180 min under ultraviolet (UV) light irradiation. Thus, the level of performance was comparable to the photoactivity of commercial anatase TiO2 nanoparticles of the same quantity. Our results highlight a new robust approach for designing hydrophilic self-cleaning coatings with controlled porosity and composition.more » « less
-
After decades of UV disinfection practice and numerous studies on the potential for pathogens to undergo dark or photo-repair after UV exposure, recent advances in UV light emitting diode (LED) technologies prompt renewed attention to bacterial reactivation and regrowth processes after UV exposure. The aspect of photorepair conditions warrants particular attention, because even studies on conventional mercury vapor lamps have not sufficiently characterized these parameters. Wastewater encounters a wide range of environmental conditions upon discharge ( e.g. , solar irradiation and dissolved organics) which may affect repair processes and ultimately lead to overestimations of pathogen removal. Escherichia coli was used here to investigate the impacts of changing reactivation conditions after UV 254 and UV 278 irradiation. UV 254 and UV 278 doses of 13.75 ± 0.4 mJ cm −2 and 28.3 ± 0.8 mJ cm −2 were required to induce a 3.0 log inactivation of E. coli , respectively. Specifically, photoreactivation conditions were varied across dissolved organic matter (DOM) content and photoreactivation wavelengths and intensities. Photoreactivation achieved higher log recoveries than dark repair, ranging from 0.8 to 1.8 log differences, but a secondary disinfection effect occurred under UVA irradiation. During photoreactivation, humic acid inhibited the initial repair of UV 278 -dosed E. coli , but culture media enhanced recovery for both dosage wavelengths. Photoreactivation profiles under UV 395 , UV 365 , and visible light depended on both fluence and time, with more regrowth observed upon exposure to visible light and the least under 365 nm. The susceptibility of E. coli to UVA was increased by prior exposure to UVC.more » « less
-
Abstract Polymer nanocomposite coatings of solar photovoltaic cells that absorb solar ultraviolet (UV) radiation and convert it into visible and near-infrared (NIR) light can increase the operational lifetime and the energy efficiency of the cells. We report a polymer nanocomposite spectrum converting layer (SCL) made of colorless polyimide CORIN impregnated with the nanoparticles (NPs) of fluoride NaYF4doped with three-valent ions of Europium at a molar concentration of 60%. The NPs were the nanocrystals (179 ± 35 nm in size) in thermally stable hexagonal beta-phase. The visible-NIR photoluminescence quantum yield of the nano-powder was ∼69%. The SCLs were applied using the open-air multi-beam multi-target pulsed laser deposition method to silicon heterojunction (SHJ), copper-indium-gallium-selenide (CIGS), and inverted metamorphic multijunction (IMM) solar cells. The cells were exposed to UV radiation from a 365 nm light emitting diode. TheI–Vcharacteristics of the cells were measured with a solar simulator using AM0 filter. The proposed SCLs improved the UV stability of all three types of the cells: the power degradation of SHJs and IMMs cells was stopped or slightly reversed and the degradation rate of CIGSs decreased by ∼25%. The proposed SCLs have great commercial potential, especially for applications to space power.more » « less
An official website of the United States government

