Construction of membrane reactors coupled with conjugated network hollow microspheres for cascade production of block copolymers

Abstract

We present a design for cascade polymer production by exploiting the construction of membrane reactors coupling with conjugated network hollow microspheres as suspended catalysts to combine aqueous photopolymerization and membrane separation process.

Structure and Morphology Engineering of Hollow Conjugated Microporous Photocatalysts to Boost Photo-Controlled Polymerization at Near-Infrared Wavelengths

“…The deconvoluted N 1s core-level spectrum of the S- h PorIPN MSs comprised three peak components with BEs at 397.8 eV for the combined cyano nitrogen ((C) N ) and imine nitrogen ((C) N −) species, 399.7 eV for the amine nitrogen (− N −), and 402.0 eV for the partially quaternized ammonium (− N + ) from the porphyrin rings and IPN linkages, respectively (Figure f′). These results were in good accordance with the previously reported porphyrinic CMPs. , Based on the results obtained from the elemental analysis (3.05 wt % sulfur) and the hypothesis that all the iodide atoms have been consumed in the Sonogashira–Hagihara polycondensation, the amount of sulfonic acid groups and porphyrin catalytic units in the S- h PorIPN MSs was determined to be 2.36 × 10 –6 and 0.84 × 10 –6 mol•mg –1 , respectively. Generally, the hollow structures will shorten the diffusion pathway and enhance the accessibility of reagents to the reactive sites of h PorIPN MSs, yielding a higher addition of sulfonic acids to the S- h PorIPN MSs.…”

“…The h PorIPN MSs showed two major peaks centered at 0.55 and 0.93 nm, whereas the S- h PorIPN MSs displayed two major peaks centered at 0.61 and 1.08 nm (Figure S4). Powder X-ray diffraction (XRD) measurements revealed the typical amorphous characteristics of h PorIPN and S- h PorIPN MSs, which were consistent with previous reports of amorphous analogues produced by Sonogashira–Hagihara cross-coupling (Figure c). − Additionally, the UV–visible spectrum of S- h PorIPN MSs displayed a red-shift in optical absorption over a broad Q -band range from 650 to 780 nm (Figure d). The authors ascribed the bathochromic shift as the incorporation of electron-withdrawing cyano and sulfonic acid groups to the fully π-conjugated organic frameworks .…”

“…By the procedure given in our previous publication, the SiO 2 @PorIPN core–shell MSs were obtained by changing the IB to 3,6-diiodophthalonitrile (IPN) in the template-assisted synthesis (Scheme ). − The SiO 2 @PorIPN core–shell MSs appeared as solid SiO 2 cores surrounding by uniform and coarse polymeric coronas, as determined by field emission scanning electron microscopy (FESEM) and transmission electron microscopy (TEM) (Figure a,d). The average diameter of SiO 2 @PorIPN MSs was measured to be 261.5 ± 10.7 nm (Figure S3a).…”

“…These results were in good accordance with the previously reported porphyrinic CMPs. 44,45 Based on the results obtained from the elemental analysis (3.05 wt % sulfur) and the hypothesis that all the iodide atoms have been consumed in the Sonogashira− Hagihara polycondensation, the amount of sulfonic acid groups and porphyrin catalytic units in the S-hPorIPN MSs was determined to be 2.36 × 10 −6 and 0.84 × 10 −6 mol•mg −1 , respectively. Generally, the hollow structures will shorten the diffusion pathway and enhance the accessibility of reagents to the reactive sites of hPorIPN MSs, yielding a higher addition of sulfonic acids to the S-hPorIPN MSs.…”

“…In this study, metal-free hollow CMPs (S- h PorIPN MSs) were exploited as a heterogeneous PC to induce aqueous PET–RAFT polymerization of various monomers under the irradiation of a 740 nm NIR light. The S- h PorIPN microspheres (MSs) were obtained by Sonogashira–Hagihara polycondensation, followed by the removal of silica templates and sulfonation of the conjugated shell. − Employing triethanolamine (TEOA) as a reductant reinforced the oxygen tolerance of this system and allowed the preparation of well-structured polymers with narrow dispersity at faster polymerization rates without prior deoxygenation. The enhanced penetration of NIR light allowed the photopolymerizations to be conducted through synthetic or biological barriers.…”