Sequential interpenetrating poly(ethylene glycol) hydrogels prepared by UV‐initiated thiol–ene coupling chemistry

Poly(ethylene glycol) (PEG)‐diallyls, ranging from 2 to 8 kDa, were successfully reacted with a trifunctional thiol crosslinker via thiol–ene coupling reaction to construct four different primary PEG hydrogels. These systems were used as scaffolds for the preparation of a library of sequential interpenetrating networks (SeqIPNs). The solid content of the secondary networks varied between 21 and 34% and was dependent on the length of the absorbing PEGs. The gel fractions for the IPNs were above 85%. Additionally, the lowest degree of swelling was found for the IPN based on 2‐kDa PEG (315%), whereas the 8‐kDa PEG IPN exhibited a value of 810%. The SeqIPN strategy facilitated hydrogel systems that cover a larger domain of tensile modulus (192–889 kPa) when compared with single hydrogel networks (175–555 kPa). © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013     

The power of thiol‐ene chemistry

As a tribute to Professor Charlie Hoyle, we take the opportunity to review the impact of thiol‐ene chemistry on polymer and materials science over the past 5 years. During this time, a renaissance in thiol‐ene chemistry has occurred with recent progress demonstrating its unique advantages when compared with traditional coupling and functionalization strategies. Additionally, the robust nature of thiol‐ene chemistry allows for the preparation of well‐defined materials with few structural limitations and synthetic requirements. To illustrate these features, the utility of thiol‐ene reactions for network formation, polymer functionalization, dendrimer synthesis, and the decoration of three‐dimensional objects is discussed. Also, the development of the closely related thiol‐yne chemistry is described. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 743–750, 2010     

Antibacterial poly(ethylene glycol) hydrogels from combined epoxy‐amine and thiol‐ene click reaction

Antibacterial hydrogels containing quaternary ammonium (QA) groups were prepared via a facile thiol‐ene “click” reaction using multifunctional poly(ethylene glycol) (PEG). The multifunctional PEG polymers were prepared by an epoxy‐amine ring opening reaction. The chemical and physical properties of the hydrogels could be tuned with different crosslinking structures and crosslinking densities. The antibacterial hydrogel structures prepared from PEG Pendant QA were less well‐defined than those from PEG Chain‐End QA. Furthermore, functionalization of the PEG‐type hydrogels with QA groups produced strong antibacterial abilities against Staphylococcus aureus, and therefore has the potential to be used as an anti‐infective material for biomedical devices. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 656–667     

Sequential thiol‐ene/thiol‐ene and thiol‐ene/thiol‐yne reactions as a route to well‐defined mono and bis end‐functionalized poly(N‐isopropylacrylamide)

Sequential thiol‐ene/thiol‐ene and thiol‐ene/thiol‐yne reactions have been used as a facile and quantitative method for modifying end‐groups on an N‐isopropylacrylamide (NIPAm) homopolymer. A well‐defined precursor of polyNIPAm (PNIPAm) was prepared via reversible addition‐fragmentation chain transfer (RAFT) polymerization in DMF at 70 °C using the 1‐cyano‐1‐methylethyl dithiobenzoate/2,2′‐azobis(2‐methylpropionitrile) chain transfer agent/initiator combination yielding a homopolymer with an absolute molecular weight of 5880 and polydispersity index of 1.18. The dithiobenzoate end‐groups were modified in a one‐pot process via primary amine cleavage followed by phosphine‐mediated nucleophilic thiol‐ene click reactions with either allyl methacrylate or propargyl acrylate yielding ene and yne terminal PNIPAm homopolymers quantitatively. The ene and yne groups were then modified, quantitatively as determined by ¹H NMR spectroscopy, via radical thiol‐ene and radical thiol‐yne reactions with three representative commercially available thiols yielding the mono and bis end functional NIPAm homopolymers. This is the first time such sequential thiol‐ene/thiol‐ene and thiol‐ene/thiol‐yne reactions have been used in polymer synthesis/end‐group modification. The lower critical solution temperatures (LCST) were then determined for all PNIPAm homopolymers using a combination of optical measurements and dynamic light scattering. It is shown that the LCST varies depending on the chemical nature of the end‐groups with measured values lying in the range 26–35 °C. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 3544–3557, 2009     

High‐molecular‐weight polyisobutylenes (PIBs) and PIB networks from liquid PIBs by thiol‐ene clicking

We report the synthesis of high‐molecular‐weight linear polyisobutylenes (PIBs) and PIB networks from low‐molecular‐weight PIB by thiol‐ene click chemistry. Thus, liquid allyl‐telechelic PIB was reacted with small di‐ and tri‐thiols, and the thiolated intermediates chain‐extended by UV‐ or thermally induced free radical initiation to linear and crosslinked products. PIB networks were also prepared by crosslinking SH‐telechelic PIB with a small triallyl compound. Linear products were characterized by ¹H NMR spectroscopy and GPC, and networks by FTIR spectroscopy, extractables, swelling, and permanent set. The effect of reaction conditions (nature of thiol chain extender, concentration of photo‐ and thermal initiators, UV radiation time, and reagent concentrations) on chain extension and crosslinking was investigated. Under well‐defined conditions high‐molecular‐weight PIBs and tight PIB networks were prepared. Thiol‐ene click chemistry provides novel thiolated PIB derivatives and is a useful strategy for the convenient preparation of high‐molecular‐weight rubbery PIBs and tight PIB networks from low‐molecular‐weight PIB precursors. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019     

Silica/poly (N‐vinylimidazolium) nanospheres by combined RAFT polymerization and thiol‐ene click chemistry

We report a facile method that combined sol–gel reaction, reversible addition–fragmentation chain transfer (RAFT)/macromolecular design via interchange of the xanthates process and thiol‐ene click reaction to prepare monodisperse silica core‐poly(N‐vinylimidazole) (PVim) shell microspheres of 200 nm in average diameters. First, silica with C = C double bonds was prepared by the sol–gel reaction of 3‐(trimethoxysilyl)propyl methacrylates (MPS) with tetraethoxysilane in ethanol; SiO₂@PVim were subsequently prepared by grafting PVim chain (Mn = 9800 g/mol, polydispersity index = 1.22) to MPS‐SiO₂ via the thiol‐ene click chemisty. The obtained SiO₂@PVim microspheres show higher catalytic activity toward the hydrolysis of p‐nitrophenyl acetate compared with the PVim homopolymers. The as‐prepared composites have been characterized by scanning electron microscopy, transmission electron microscopy, thermal gravimetric analysis and Fourier transform infrared spectrometry analysis. Copyright © 2014 John Wiley & Sons, Ltd.     

Antimicrobial equipment of poly(isoprene) applying thiol‐ene chemistry

The functionalization of anionically polymerized isoprene with cysteamine applying the thiol‐ene reaction is reported. Antimicrobial activity is implemented by quaternization of the amino functionality by either alkylation or by protonation. The resulting polymers were tested against Gram‐positive as well as Gram‐negative bacteria strains according to the Japanese Industrial Standard Z2801:2000 protocol, partly revealing excellent biocidal performance. Thermal stability up to 200°C allows extrusion processing of the functionalized poly(isoprene)s. The best performing polymer, that is, bearing butylated ammonium‐groups, was compounded with the commodity material poly(propylene). The compound bearing 5 wt % of the biocidal polymer exhibited satisfactory biocidal properties. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Tunable poly(hydroxyl urethane) from CO2‐Based intermediates using thiol‐ene chemistry

CO₂‐based, crosslinked poly(hydroxyl urethane)s (PHUs) are accessed via a set of efficient reactions based on the addition chemistry of thiol‐ene and amines‐cyclic carbonates. This strategy to utilize 5‐membered cyclic carbonates produced from CO₂ is robust, facile, modular, and atomically efficient in nature. The thiol‐ene reaction was utilized to access bis(cyclic carbonate), tris(cyclic carbonate), and tetrakis(cyclic carbonate) in quantitative yield from 4‐vinyl‐1,3‐dioxolan‐2‐one and thiols. Multi‐functional cyclic carbonates were simply mixed with diethylenetriamine and/or 1,6‐diaminohexane to generate crosslinked PHUs from 25 to 80 °C. These materials are easy to scale‐up and are potential candidates in many applications such as coatings, binders, and resins. The resulting polymers have glass transition temperatures between ?1 and 16 °C and thermal decomposition temperatures from 190 to 230 °C. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Evaluation of thiol‐ene click chemistry in functionalized polysiloxanes

Polysiloxanes are commonly used in a myriad of applications, and the “click” nature of the thiol‐ene reaction is well suited for introducing alternative functionalities or for crosslinking these ubiquitous polymers. As such, understanding of the thiol‐ene reaction in the presence of silicones is valuable and would lead to enhanced methodologies for modification and crosslinking. Here, the thiol‐ene reaction kinetics were investigated in functionalized oligosiloxanes having varying degrees of thiol functionalization (SH), π–π interactions (from diphenyls, DP), and ene types (C?C). In the ene‐functionalized oligomers, π–π interactions were controlled through the use of dioctyl repeats (DO). The polymerization rate and rate‐limiting steps were determined for all systems containing an allyl‐functionalized oligomer, and rates ranging from 0.10 to 0.54 mol L^?1 min^?1 were seen. The rate‐limiting step varied with the oligomer composition; examples of rate‐limited propagation (5:3:2 C?C:DP:DO/1:1 SH:DP) or chain transfer (5:3:2 C?C:DP:DO/3:1 SH:DP) were found in addition to cases with similar reaction rate constants (5:2:3 C?C:DP:DO/1:1 SH:DP). None of the siloxanes were found to exhibit autoacceleration despite their relatively high viscosities. Instead, the allyl‐, vinyl‐, and acrylate‐functionalized siloxanes were all found to undergo unimolecular termination based on their high α scaling values (0.98, 0.95, and 0.82, respectively) in the relation R_p ∝ R_i^α. © 2013 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013     

Crosslinked poly(ethylene oxide) containing siloxanes fabricated through thiol‐ene photochemistry

Homogenous amphiphilic crosslinked polymer films comprising of poly(ethylene oxide) and polysiloxane were synthesized utilizing thiol‐ene “ click ” photochemistry. A systematic variation in polymer composition was Carried out to obtain high quality films with varied amount of siloxane and poly(ethylene oxide). These films showed improved gas separation performance with high gas permeabilities with good CO₂/N₂ selectivity. Furthermore, the resulting films were also tested for its biocompatibility, as a carrier media which allow human adult mesenchymal stem cells to retain their capacity for osteoblastic differentiation after transplantation. The obtained crosslinked films were characterized using differential scanning calorimetry, dynamic mechanical analysis, thermogravimetric analysis, FTIR, Raman‐IR , and small angle X‐ray scattering. The synthesis ease and commercial availability of the starting materials suggests that these new crosslinked polymer networks could find applications in wide range of applications. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 1548–1557     

Synthesis of well‐defined poly(dimethylsiloxane) telechelics having nitrobenzoxadiazole fluorescent chain‐ends via thiol‐ene coupling

Well‐defined PDMS telechelics having nitrobenzoxadiazole (NBD) fluorescent probes covalently attached at both chain‐ends were prepared in two steps and a series of fractionation procedures starting from commercially available divinyl‐terminated PDMS having a broad molar mass dispersity. First, thiol‐ene coupling between 6‐mercapto‐1‐hexanol and vinyl chain‐ends allowed the formation of dihydroxy‐terminated PDMS telechelics through the formation of a thioether linkage. The resulting material was then sequentially fractionated using dichloromethane/methanol mixtures to afford several well‐defined dihydroxy‐terminated PDMS fractions having sharp distributions of molar masses (M_n = 99.5–158 kDa and ? < 1.2). The NBD fluorescent probes were then attached at both chain‐ends by N,N′‐dicyclohexylcarbodiimide/4‐(dimethylamino)pyridine esterification coupling between the hydroxyl groups and 6‐(7‐nitrobenzofurazan‐4‐ylamino)hexanoic acid. The resulting fluorescent PDMS telechelics were characterized by SEC, ¹H NMR, UV–visible, and fluorescence spectroscopies. These materials are suitable probes to investigate the dynamics of polymer chains in bulk or at interfaces by the fringe pattern fluorescent recovery after photobleaching technique. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Versatile functionalization of aromatic polysulfones via thiol‐ene click chemistry

A facile, efficient approach for preparation of functionalized aromatic polysulfones by postpolymerization modification with thiol‐ene click chemistry is described. The key synthetic strategy is to incorporate a pendant vinyl ether group into polysulfones as a reactive precursor with controlled degrees of functionalization. Synthetic utility of the pendant alkenyl group is demonstrated by generating diverse polymer derivatives using thiol‐ene functionalization including glycosylated polysulfone. The highly reactive alkene platform in the polymer affords convenient, metal‐free, and azide‐free click transformations to create diverse ranges of new functionalized polysulfones that could be applied in various applications. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 3237–3243     

Dendrimers in thiol‐ene crosslinked networks and the effect of subsequent generations on thermoset properties

A series of well‐defined allyl‐ether functionalized polyester dendrimers has been synthesized via the divergent approach using traditional esterification reactions. Two commercially available trifunctional thiols, trimethylolpropane tri(3‐mercaptopropanoate) (TRIS) and ethoxylated trimethylolpropane tri(3‐mercaptopropanoate) (ETTMP), were incorporated with the dendrimers into the thiol‐ene polymer networks. The thiol‐ene reactions were conducted at room temperature and cured by UV light without the addition of photoinitiatior. Highly crosslinked films were obtained and characterized with respect to mechanical (DMA) and thermal (DSC and TGA) properties. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 589–601, 2009     

Thiol‐ene click derived structurally well‐defined per(3,5‐dimethyl)phenylcarbamoylated cationic cyclodextrin separation material for achiral and chiral chromatography

In this work, a novel single sulfoether‐bridged cationic per(3,5‐dimethyl)phenylcarbamoylated‐β‐cyclodextrin separation material was prepared by thiol‐ene click chemistry and characterized by using FTIR spectroscopy, solid‐state ¹³C NMR spectroscopy and elemental analysis, which confirmed the correct structure. The separation material exhibited a good achiral separation performance for benzene homologues and phenylamine analogs, especially o‐xylene and m‐xylene, and m‐phenylenediamine and o‐phenylenediamine can be discriminated by the (3,5‐dimethyl)phenylcarbamoyl cyclodextrins. The chiral resolving ability of the separation material was evaluated by discriminating various isoxazolines, flavonoids, and β‐blockers in reversed‐phase high‐performance liquid chromatography. For isoxazolines, the material showed the best chiral discrimination toward 3‐aryl‐5‐(2‐oxopyrrolidin‐1‐yl)‐isoxazolines, where the resolution for 3ClPh‐OPr  reached 6.03. For flavonoids, it exhibited more efficient separation to the ones with more hydrophobic substituents, with a resolution of 5.93 for 6‐hydroxyflavanone. β‐Blockers were also enantioseparated satisfactorily on the material. The as‐prepared separation material is a good member of the thiol‐ene click derived cyclodextrin stationary phase family.     

One‐pot preparation of an organic polymer monolith by thiol‐ene click chemistry for capillary electrochromatography

A novel organic monolith was successfully fabricated by a one‐pot thiol‐ene click reaction of triallyl isocyanurate with pentaerythritol tetrakis‐(2‐mercaptoacetate) and mercaptopropionic acid in the presence of porogens. We investigated the effects of the ratio of monomer and cross‐linking agent, the type and ratio of porogen, and click reaction temperature on the permeability and morphology of the prepared poly triallyl isocyanurate‐co‐pentaerythritol tetrakis (2‐mercaptoacetate) monoliths. The monolith was also characterized by scanning electron microscopy and Fourier transform infrared spectroscopy. The results indicated that the monoliths had continuous porous framework, good permeability, and high mechanical stability. A series of analytes with different properties such as alkylbenzenes, polycyclic aromatic hydrocarbons, anilines, and phenols were used to evaluate the electrochromatographic performance of the prepared monoliths in pressurized capillary electrochromatography. The prepared polymer monolith showed typical reversed‐phase electrochromatographic behavior for hydrophobic substances. Moreover, the prepared monolith showed a mix of reversed‐phase and cation exchange interaction modes for basic aniline compounds. The minimum plate height of the monolith was 8.76 μm (132 100 plates/m) for propylbenzene. These results demonstrated that one‐pot thiol‐ene click chemistry can provide a simple and reliable method for the preparation of organic monoliths.     

Photopolymerization of thiol‐ene systems based on oligomeric thiols

Thiol oligomers were copolymerized with a triallyl ether by a photoinduced polymerization process. These oligomeric thiol‐ene systems comprise the same components as a photopolymerized thiol‐ene‐acrylate ternary system, yet the photopolymerized networks have much lower glass transition temperatures. An investigation into the effect of oligomeric thiol design on network formation was conducted by analyzing the reaction kinetics and thermal/mechanical properties of the thiol‐ene networks. Real‐time FTIR analysis shows that total conversion is >90% for all thiols investigated. Photo‐DSC analysis shows that the maximum exotherm rate is roughly equivalent for all of the thiols when the equivalent weight of the thiol is taken into account. As would be expected, the glass transition temperature and tensile strength increase with thiol functionality and lower thiol equivalent weight for thiols with functionality from 2 to 4. Films made using the oligomeric thiols have essentially the same glass transition temperatures and tensile modulus values regardless of thiol design. These results distinguish the method for generation of networks consisting of an initial Michael reaction of thiols and acrylates followed by a photoinitiated copolymerization with a multifunctional ene from the traditional photolysis of the corresponding thiol‐ene‐acrylate ternary systems with no Michael reaction. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 14–24, 2009