Development of cross-linked membranes via thiol-ene click reaction using thiol-terminated sulfonated poly(arylene ether sulfone) for proton exchange membrane

조경화,김기현,김정환,한주성,이현희,김혜진,이종찬 한국공업화학회 2019 한국공업화학회 연구논문 초록집 Vol.2019 No.1

Thiol-terminated sulfonated poly(arylene ether sulfone) (SH-SPAES) are synthesized to fabricate end-group cross-linked structure proton exchange membrane. Acrylo-polyhedral oligomeric silsesquioxane (A-POSS) is used as a multifunctional cross-linker via thiol-ene click reaction. SH-SPAES is prepared by stepwise reactions between phenoxide- terminated SPAES and end capping reagents such as decafluorobiphenyl and thiobisbenzenethiol. The cross-linked membranes exhibit improved physicochemical properties compared with linear SPAES having degree of sulfonation for 70 mol%. Under 90 oC, 100%RH condition, the power density values at 0.5 V of MEAs for C-SPAES-10 and -20 are 1.22 and 1.09 A cm^-2, respectively.

End-group cross-linked sulfonated poly(arylene ether sulfone) <i>via</i> thiol-ene click reaction for high-performance proton exchange membrane

Kim, Kihyun,Heo, Pilwon,Han, Jusung,Kim, Junghwan,Lee, Jong-Chan Elsevier 2018 Journal of Power Sources Vol.401 No.-

<P><B>Abstract</B></P> <P>End-group cross-linked sulfonated poly (arylene ether sulfone) (C-SPAES) membranes with varying degree of cross-linking density are prepared by <I>in-situ</I> casting and heating of thiol-terminated SPAES (SH-SPAES) solutions containing different amounts of multifunctional cross-linker such as acrylo-polyhedral oligomeric silsesquioxane (A-POSS) <I>via</I> thiol-ene click reaction. SH-SPAES is prepared by stepwise substitution reactions between phenoxide-terminated SPAES and end capping reagents such as decafluorobiphenyl followed by thiobisbenzethiol. The C-SPAES membranes exhibit vastly improved chemical and physical stability and mechanical strength compared with linear SPAES membrane due to effective cross-linked structure, and their proton conductivity values are higher than Nafion-212 in relative humidity range of 50–95% (at 90 °C) due to high degree of sulfonation (70 mol%) and ion exchange capacity (2.48 mequiv. g<SUP>−1</SUP>) of SH-SPAES. Under various operating conditions of proton exchange membrane fuel cell including intermediate temperature and low humidity conditions, membrane electrode assemblies employing the C-SPAES membranes with optimized cross-linker contents show outstanding cell performances (e.g., 1.08 W cm<SUP>-2</SUP> at 0.5 V under 90 °C and 50% RH with 150 kPa).</P> <P><B>Highlights</B></P> <P> <UL> <LI> Thiol terminated sulfonated poly (arylene ether sulfone) (SH-SPAES) is synthesized. </LI> <LI> SH-SPAES has high degree of sulfonation and ion exchange capacity. </LI> <LI> End-group cross-linked SPAES membranes are prepared by thiol-ene click reaction. </LI> <LI> Excellent physicochemical stability of cross-linked SPAES membranes. </LI> <LI> Outstanding cell performances of MEAs prepared with cross-linked SPAES membranes. </LI> </UL> </P> <P><B>Graphical abstract</B></P> <P>[DISPLAY OMISSION]</P>

Fabrication of schizophyllan hydrogel via orthogonal thiol-ene photopolymerization

Lee, S.,Tae, H.,Ki, C.S. Applied Science Publishers ; Elsevier Science Ltd 2017 Carbohydrate Polymers Vol.167 No.-

Schizophyllan (SPG) is a water soluble β-glucan, which is obtained from Schizophyllum commune. SPG has been widely explored with its unique properties such as triple helical structure, immune-modulation, and anti-tumoral activity. In this study, we tried to fabricate SPG hydrogel via thiol-ene photopolymerization. SPG-norbornene and SPG-thiol were synthesized from ultrasonicated SPG. Two types of SPG hydrogels (SPG and PEG/SPG hybrid) were formed via thiol-ene photo-click reaction. By controlling the SPG content and stoichiometric balance of norbornene and thiol groups, swelling ratio and shear elastic modulus of SPG hydrogel could be controlled in the range of 20-60 and 0.5-10kPa, respectively. For PEG/SPG hybrid hydrogel, we found that the triple-helical structure of SPG played a role in physical network formation with thiol-ene cross-linking. The degradability of SPG hydrogel could be also modulated by varying formulation. Therefore, such highly tunable SPG hydrogels would be utilized for various applications.

Preparation of the Water-Soluble Fluorene-Containing Fluorescent Polymer by One-Pot Method

Yuan Wang,Hongchi Zhao,Haijian Tan,Xiaomeng Li,Yunxia Qian,Libin Bai,Yonggang Wu,Shufang Lv 한국고분자학회 2015 Macromolecular Research Vol.23 No.10

A water-soluble fluorescent polymer, 2,7-di{4'-[3''-(S-poly(acryloyl ethylene diamine hydrochloride)-2'''- methyl propionic acid)propionyloxy hexyloxy]phenyl}-9,9-di(n-octyl)fluorene (P3) with regular and ordered structure, was designed and synthesized with high conversion using click reaction between thiols and carbon-carbon double bonds. Because the S-H bond is relatively weak, thiol groups are subject to rapid oxidation during purification and storage and thereby result in the low conversion in the following click reaction. To circumvent this limitation, the synthesis of thiol groups and click reaction were simultaneously performed in one system (one-pot method). The intermediate products P1 (S-1-dodecyl-S'-[poly(N-Boc-acryloyl ethylene diamine)-2'-methyl propionic acid]trithiocarbonate) and M2 (2,7-di[4-(acryloyloxy hexyloxy)phenyl]-9,9-di(n-octyl)fluorene) were prepared via reversible addition fragmentation chain transfer (RAFT) polymerization and Williamson synthesis, respectively. Then, 2,7- di{4'-[3''-(S-poly(N-Boc-acryloyl ethylene diamine)-2'''-methyl propionic acid)propionyloxy hexyloxy]phenyl}- 9,9-di(n-octyl)fluorene (P2) was synthesized with high conversion (83%) by employing a click reaction with P1 and M2 as starting materials. Finally, water-soluble fluorescent polymer P3 was obtained after the deprotection of P2. M2, P1, P2 and P3 were characterized by Fourier transform infrared (FTIR) spectrum, nuclear magnetic resonance (NMR), high-resolution mass spectroscopy (MS), gel permeation chromatograph (GPC), UV-Visible (UV-Vis) spectrum, and fluorescence, respectively. The results revealed that P3 displayed good solubility in water and not only exhibited a blue fluorescence emission band in water but also had a similar photoluminescent spectra to those of M2 and P2 in dichloromethane. The fluorescence quantum yield of P3 in aqueous solution could reach 0.10. In addition, the result of cell cytotoxicity indicates that P3 has low cytotoxicity and exhibits potential for biomedical applications. This work provides a new insight into the study of water-soluble fluorescent polymer.

Thiol-ene click reaction을 이용한 다공성 구조체 제조 및 그 응용

윤요한,안진혁,조국영 한국공업화학회 2022 한국공업화학회 연구논문 초록집 Vol.2022 No.-

Phytochemicals from Echinacea and Hypericum: A Direct Synthesis of Isoligularone

Kraus, George A.,Bae, Jaehoon,Kim, Junwon Taylor Francis 2007 Synthetic communications Vol.37 No.8

<P> Reaction of trienes with α,&bgr;-unsaturated aldehydes produces bicyclic products via a tandem Diels-Alder/ene reaction. The adduct from tiglic aldehyde was converted into isoligularone by conversion to a furan followed by benzylic oxidation.</P>

A facile and green functionalization of single-walled carbon nanotubes by polyampholytic polymers for drug delivery application

( Quoc Thang Phan ),박한솔,박찬,홍성수,임권택 한국공업화학회 2019 한국공업화학회 연구논문 초록집 Vol.2019 No.1

A novel process for the green chemistry approach of drug nanocarriers using sustainable conditions, and chemical methods involving one-pot synthesis of polymers and surface modification of SWCNTs is reported. Firstly, the polyampholytic alternating polymers were prepared with functional monomers by using thiol-ene chemistry in sustainable conditions. Then, the obtained polymers were applied for a direct functionalization onto the surface of SWCNTs in aqueous media with ultrasonication support through Diels-Alder click reaction. The synthesized hybrid was characterized by TGA, FT-IR, UV-vis, Raman spectroscopy and TEM. These hybrids were used as drug-nanocarriers to improve the drug loading capacity up to 150%. Finally, the in-vitro drug release profiles showed that there was a burst release of DOX at pH 5.5 when compare with the lower release rate at pH 7.4 in the physiological condition.

Synthesis and phase transition behavior of well-defined Poly(arylene ether sulfone)s by chain growth condensation polymerization in organic media

Lee, Jinhee,Lee, Byungyong,Park, Jeyoung,Oh, Jaehoon,Kim, Taehyoung,Seo, Myungeun,Kim, Sang Youl Elsevier 2018 Polymer Vol.153 No.-

<P><B>Abstract</B></P> <P>A series of well-defined poly(arylene ether sulfone)s (PESs) as a rod-type block was synthesized by chain-growth condensation polymerization from a diphenyl sulfone-type initiator containing a fluorine leaving group and an allyl moiety. Interestingly, these oligomeric PESs exhibited lower critical solution temperature (LCST)-type phase transition behavior in organic solvents, i.e., 1,2-dimethoxyethane (DME) and chloroform. The clouding point temperature was affected by the molecular weight and concentration of the polymers. The cloud temperature decreased as the molecular weight polymers and the concentration of polymer solution increased. And also two series of rod-coil type poly(arylene ether sulfone)-<I>b</I>-polylactides were synthesized by controlled ring-opening esterification polymerization of <SMALL>DL</SMALL>-lactide with a PES-derived macroinitiator in which the allyl group was transformed into an aliphatic hydroxyl group by a thiol-ene click reaction. These diblock copolymers also exhibited LCST behavior in DME, and the nanoscale size of the aggregates increased upon heating.</P> <P><B>Highlights</B></P> <P> <UL> <LI> Well-controlled rod-type poly(ethersulfone)s were synthesized. </LI> <LI> The poly(ethersulfone)s exhibited thermos-responsive properties in organic solvents. </LI> <LI> This phase transition behavior was also observed with diblock copolymers. </LI> <LI> Their cloud points were affected by the molecular weight and the concentration. </LI> </UL> </P> <P><B>Graphical abstract</B></P> <P>[DISPLAY OMISSION]</P>

Preparation of functionalized vegetable oil based polyol through thiol-ene click reaction for thermoplastic polyurethanes

최예진,( Prakash Alagi ),홍성철 한국공업화학회 2015 한국공업화학회 연구논문 초록집 Vol.2015 No.0

In this study, controlled preparation of polyols with primary hydroxyl and ethylene oxide functionalities are attempted through thiol-ene click coupling reaction between vegetable oil (VO) and different kinds of thiol-containing compounds. Experimental parameters, such as concentrations of chemicals, reactions time, and reaction temperature, were carefully optimized to improve reaction efficiency and to control the structural characteristics of the polyols. 1H-NMR, GPC, MALDI-TOF, and titration methods were employed to investigate the structures and functionalities of the polyols. The resulting VO-based polyols were successfully introduced into thermoplastic polyurethanes (TPUs). Thermal, mechanical, shape memory, and cytotoxicity evaluation of the TPUs were performed.

Thiol-ene click reaction for the preparation of functionalized vegetable oil polyols for thermoplastic polyurethanes

홍성철,( Prakash Alagi ),최예진 한국공업화학회 2015 한국공업화학회 연구논문 초록집 Vol.2015 No.1

In this study, controlled preparations of polyols with pre-determined -OH and ethylene oxide functionalities are attempted through thiol-ene click coupling reaction between vegetable oils and various thiol-containing compounds. The resulting polyols are investigated by 1H-NMR, GPC, MALDI-TOF and titration methods to determine their structures and functionalities. A series of thermoplastic polyurethanes (TPUs) are carefully prepared from the modified soybean oil based polyols and their polymerization characteristics are investigated. Thermal and mechanical properties of the soybean oil based TPUs are at least comparable to those prepared from petroleum resources, which ensure new applications of the eco-friendly materials in high value added technologies.