Thiol-ene Polymerization Research Articles

Self-Immolative Polymers Derived from Renewable Resources via Thiol-Ene Chemistry.

The development of polymers from renewable resources is a promising approach to reduce reliance on petrochemicals. In addition, depolymerization is attracting significant attention for the breakdown of polymers at their end-of-life or to achieve specific stimuli-responsive functions. However, the design of polymers incorporating both of these features remains a challenge. Herein, we report a new class of self-immolative polymers based on lignin-derived aldehydes via a simple thiol-ene polymerization. These self-immolative polymers undergo cascade degradation in response to specific stimuli through alternating 1,6-elimination and cyclization reactions. The two methoxy substituents on the syringaldehyde monomer accelerated the desired depolymerization reaction, while enhancing stability against undesired backbone hydrolysis. Moreover, diverse responsive end-caps could be introduced through post-polymerization functionalization from a single polymer precursor.

Photo-crosslinked Diels-Alder and thiol-ene polymer networks.

Compositions of ethylene glycol dicyclopentenyl ether methacrylate (EGDEMA), a vegetable oil based alkyl methacrylate (C13MA), and furfuryl methacrylate (FMA) were terpolymerized for dual-crosslinked networks with tailored mechanical and thermal properties. Specifically, initiators for continuous activator regeneration (ICAR) atom transfer radical polymerization (ATRP) afforded materials with tailored glass transition temperature (T g) and incorporation of furan and norbornene functionalities within a single chain. The terpolymer with high furan and norbornene functionality (Ter2: F FMA = 0.42, F EGDEMA = 0.46, F C13MA = 0.12) is crosslinked to form single-crosslinked reversible networks with 1,1'-(methylenedi-4,1-phenylene)bismaleimide (BM) via Diels-Alder (DA) chemistry and dual-crosslinked networks incorporating additional non-reversible thiol-ene crosslinks. The reactions were photo-initiated using 254 nm UV light with BM : FMA molar ratios of 0.1 and 0.2 for both systems. FTIR analyses for crosslinked Ter2 samples confirmed the successful formation of DA and thiol-ene adducts, while DSC confirmed the reversibility of the DA reaction. A terpolymer with higher C13MA composition (Ter3: F C13MA = 0.75, F FMA = 0.17, F EGDEMA = 0.08) was similarly crosslinked in single and dual crosslinked networks with BM : FMA of 0.1 and 0.2. Crosslinking efficiency was evaluated for both single and dual crosslinked networks with a BM : FMA = 0.1 by comparing thermal and UV curing methods, with UV curing proving more effective for dual-crosslinked systems, leading to increased gel content (71% with UV compared to 61% thermally) and improved material properties. FTIR and DSC results confirmed the formation of the DA adducts and the reversibility of the DA reaction. The terpolymers were further analyzed for adhesive applications through rheological testing. These studies demonstrated that the incorporation of thiol-ene crosslinking alongside Diels-Alder crosslinking offers a balanced combination of reversible and permanent bonds, resulting in materials with enhanced mechanical strength, thermal stability, and functional versatility that are suitable for applications such as recyclable adhesives.

Selective binding of rare-earth ions in polymerizable cages.

We assembled metal-organic cages by combining rare-earth metals with an alkene-terminated ligand (L), allowing for subsequent thiol-ene polymerization of the cages to yield rare-earth-binding polymer networks. Mixed-metal self-assembly experiments with ligand L show that the size ratio of the respective rare-earth metals dictates the metal composition of the cages.

Off-Stoichiometry Thiol-Ene Surface Functionalization: Example with Gold Nanoparticles.

Surface modification is essential in microfluidic applications due to the inherent hydrophobicity of polymers, which can lead to biofouling and reagent denaturation. Despite the development, challenges such as hydrophobic molecule absorption and limitations in scaling are still present. Off-stoichiometry thiol-ene (OSTE) materials have emerged as a promising alternative, offering advantages like rapid prototyping, minimal hydrophobic absorption, and customizable surface chemistries. While the thiol-ene polymerization mechanism is well understood, the fundamental understanding of thiol group binding on OSTE surfaces remains limited. Existing techniques to analyze surface groups lack the capability to confirm the stable presence of thiol groups on the surface. In our study, using Raman and X-ray photoelectron spectroscopy techniques, we investigated a potential method for enhancing the surface properties of OSTE polymer-the attachment of novel linkers to the surface. We have demonstrated our synthesized compound efficiency by binding gold nanoparticles to the OSTE surface. Our findings indicate that chemical reactions involving double bonds with the material surface hold the most potential for effective surface modification for gold binding.

Plasmon-enhanced quantum efficiency of CdSe/ZnS luminescent solar concentrators through Au nanoparticle integration

Luminescent solar concentrators (LSCs) are effective large-area sunlight collectors that use solar cells to convert focused sunlight into electricity based on the emissive fluorophores. However, the development of high-performance LSCs still remains a challenge. In this work, LSCs are fabricated by incorporating CdSe/ZnS core-shell quantum dots (QDs) and Au nanoparticles (NPs) into the off-stoichiometric thiol-ene (OSTE) polymer. The light absorption efficiency and photoluminescence (PL) intensity of CdSe/ZnS QDs are significantly enhanced by the localized surface plasmon resonance (LSPR) effect of Au NPs. When the concentration of Au NPs is 2 ppm, the maximal internal quantum efficiency (ηint) and external quantum efficiency (ηext) of CdSe/ZnS LSCs are measured to be 9.90% and 3.85%, respectively. Compared to the control devices, the increases of 1.78-fold in ηint and 2.97-fold in ηext are achieved. In addition, the power conversion efficiency (PCE) and optical efficiency (ηopt) of CdSe/ZnS LSCs show increases of 0.49 times and 0.35 times, respectively. Furthermore, the LSC with 2 ppm Au NPs possesses excellent aesthetic parameters with a color rendering index (CRI) of 92.11 and an average visible transmission (AVT) of 75.02%. Therefore, the optimal concentration of Au NPs will shed light on high-efficiency LSCs with superior aesthetic parameters to meet the demands of practical applications.

Development of Functional Biointerface Using Mixed Zwitterionic Silatranes.

Strategies to design multifunctional interfaces for biosensors have been extensively investigated to acquire optimal sensitivity, specificity, and accuracy. However, heterogeneous ingredients in clinical samples inevitably generate background signals, exposing challenges in biosensor performance. Polymer coating has been recognized as a crucial method to functionalize biointerfaces by providing tailored properties that are essential for interacting with biological systems. Herein, we introduce for the first time two oligomeric silatranes, MPS-MPCn and MPS-PEGMACOOHm, which were copolymerized from mercaptopropylsilatrane (MPS) with either zwitterionic monomer 2-methacryloyloxyethyl phosphorylcholine (MPC) or carboxylated poly(ethylene glycol) methacrylate (PEGMACOOH) through thiol-ene polymerization. These oligomeric silatranes were prepared individually and in combinations in acidic and nonacid solvents for deposition on silicon wafers. Afterward, coating properties, including wettability, thickness, and elemental composition, were characterized by contact angle meter, ellipsometer, and X-ray photoelectron spectroscopy (XPS), respectively. Importantly, MPS-MPCn polymers were found to form thin films with high hydrophilicity and superior fouling repulsion to bacteria and protein, while mixed coating involving 70% MPS-PEGMACOOH2.5 and 30% MPS-MPC2.5 exhibited thinnest coating with best wettability among COOH-terminated coatings. Furthermore, the functional COOH group in the coated surfaces was exploited for postmodification with biological molecules via intermediated N-hydroxysuccinimide (NHS) ester group by amine coupling chemistry. Once again, the combination of 70% MPS-PEGMACOOH2.5 and 30% MPS-MPC2.5 provided an ultimate reduction in nonspecific adsorption (NSA) and established a finest signal discrimination through enzyme-linked immunosorbent assay. Consequently, these novel mixed oligomeric silatranes offer a promising approach for the construction of biosensor interfaces with dual functions in both nonspecific binding prevention and conjugation of biomolecules.

Photocurable Thiol-Ene/Nanocellulose Elastomeric Composites for Bioinspired and Fluorine-Free Superhydrophobic Surfaces.

Artificially prepared superhydrophobic surfaces toward a self-cleaning "lotus effect" and anticontamination performance have become critically important in the past few years. However, most approaches to create the required topology with a hierarchical roughness comprise several manufacturing steps of varying practicality. Moreover, the desired low surface energy is in most cases achieved with fluorinated moieties that are currently criticized due to biological and environmental hazards. In this work, rapidly photocuring but weak thiol-ene resins were reinforced with cellulose nanofibrils (CNFs) to replicate lotus leaves via one-step UV nanoimprint lithography. The CNFs were surface-modified using countercation exchange of carboxyl groups and grafting of thiol and methacrylate functionalities. The formulation methodology resulted in free-flowing, shear-thinning composite resins without surfactants or dispersants. The rheological and photo-cross-linking behavior of the resins, the thermal stability, the mechanical performance, and the hydrophobicity of the cured composites were characterized. Notably, the surface modifications increased the as received fibril diameter (1.9 ± 0.6 nm) by 1.6-2.3 nm and raised the fibril-resin compatibility. The resins underwent rapid polymerization and the high thermal stability of thiol-enes was retained. The methacrylated nanofibrils (10 vol %) significantly strengthened the rubbery network, outperforming the neat thiol-ene polymer in terms of hardness (3.4×), reduced modulus (5.8×), and wear resistance (>100×). Moreover, the surface of lotus-texturized composites was superhydrophobic with a water contact angle of 155°, higher than that of the neat polymer (147°), and was self-cleaning. These CNF composite resins are compatible with fast-cure processes such as 3D printing and roll-to-roll processing, are exempt of fluorine or any other hydrophobization treatment, and are extremely wear-resistant.

Construction and Regulation on Thiol–Acrylate Networks through Binary Polymerization of Thiol–Ene Polymerization and Free Radical Polymerization

Construction and Regulation on Thiol–Acrylate Networks through Binary Polymerization of Thiol–Ene Polymerization and Free Radical Polymerization

(Invited) Silicon Nanocrystals and Electrum Nanoclusters with High Quantum Yield for Light Converting Applications

While QDs are typically made of semiconductors, metals at low dimensions also turn to discrete electronic structure. The characteristic transition size from bulk to nanodot is lower, because Fermi level position is at the band middle, while discretization of levels starts from the band edge. Therefore, only for sizes of a metal entity ~ 1 nm a QD-like behavior manifests.Here we show that metal nanoclusters Au16Ag7 of an electrum alloy (gold-silver) with adamantanethiolate ligands possess PL quantum yield of ~ 70% in a thiol-ene polymer matrix [1]. PL is in NIR range with a large Stokes shift. Due to parity-forbidden transition the PL lifetime is in microseconds. These characteristics are similar to silicon QDs, where optical transition is also partly forbidden. Luminescence from Si QDs (5-10 nm size) may also feature high quantum efficiency when a defect-free core with good surface passivation is prepared. We have demonstrated a new synthesis method, which can reduce precursor cost by an order of magnitude from the established HSQ-based technique [2]. Si QDs prepared in this way have near-unity internal and > 50% external (quantum yield) efficiency with a large Stokes shift. In both nanomaterials the re-absorption is suppressed, which is of value for several applications.One such application is a semi-transparent photovoltaics for glazing in building-integration. It is based on a luminescent solar concentrator concept, where high efficiency and a large Stokes shift are necessary requirements for nanophosphors. In this configuration absorbed solar light is re-emitted and a large fraction of it is guided by total internal reflection to the edges for collection by standard solar cells. As a proof-of-concept we fabricated 20x20 cm2 prototypes, where Si QD-doped polymer layer is sandwiched between glass plates in a triplex geometry. Such “solar windows” feature high transparency (>80%), low haze (<3%), high color rendering index (~ 88) and, at the same time, deliver up to 0.6 W of electrical peak power under one sun [3]. Original measurement techniques were developed to characterize large-area devices [4,5].

Improving the removal rate of bisphenol A and Cu2+ from water using P/N coexisting β-cyclodextrin-based adsorbents by enhancing adsorbents-pollutants interactions

Improving the removal rate of bisphenol A and Cu2+ from water using P/N coexisting β-cyclodextrin-based adsorbents by enhancing adsorbents-pollutants interactions

Quercetin allylation and thiol–ene click photopolymerization to produce biobased polymer thermosets with robust thermomechanical properties

AbstractThe development of biobased and functionalized monomers along with eco‐friendly photopolymerization processes represent promising methods for the development of renewable and more environmentally friendly thermosets. Thiol–ene ‘click’ photopolymerization is particularly advantageous in this regard; however, the materials derived from this method often exhibit low glass transition temperatures (Tg) and unsuitable thermomechanical properties for applications at room temperature. Herein, we report the synthesis of biobased allyl derivatives from quercetin, a renewable flavonoid compound widely available in fruits, vegetables and plants. We demonstrated the isolation of tetra‐ and penta‐allylated quercetin (Q1 and Q2, respectively) and their subsequent photoactivated thiol–ene polymerization. By introducing a biobased thiol curing agent (PTTMP) derived from glycerol and mercaptopropionic acid, we produced fully biobased crosslinked thermosets with high content of aromatic moieties provided by the framework of the monomers. Real‐time infrared spectroscopy showed the effective thiol–ene photopolymerization of Q1 and Q2 and PTTMP with conversions of 60% and 75%, respectively, after 15 min of UV irradiation. Due to the modulated crosslinking degree from the allyl group functionalization in the monomers, the biobased crosslinked networks showed storage moduli from 420 to 739 MPa, thermal stability from 220 to 257 °C and Tg values ranging from 75 to 90 °C. This work outlines straightforward strategies for creating biobased thermosets that overcome the limited thermomechanical properties of thiol–ene networks and offer potential antimicrobial and antioxidant properties. © 2024 Society of Chemical Industry.

Thiol-based, Thermally-Conductive Adhesives for High Power Electronics

High power electronics, such as those enabling the next generation of so-called ‘5G’ devices, evolve significant amounts of heat and require improved mechanisms to dissipate that heat. As an alternative to sintered copper-based nanomaterial composites, recent work in silver nanoparticle pastes has shown great promise to provide high thermal conductivities (278.5 W/mK)[1] approaching that of neat silver (429 W/mK); however, pastes, in general, are not functional as adhesives for chip attachment under repeated thermal cycling without requisite mechanical reinforcement and interfacial stress mitigation. Work at UT Dallas, and Adaptive3D, on thermally conductive systems explores thiol-based resins composites as adhesives with excellent adhesion to metal substrates, interfaces and fillers, with tunable electrical and thermal conductivities. Voit, Lund, et al. have demonstrated thiol-ene polymer systems for flexible electronics and semiconductor packaging with excellent adhesion to metal substrates (due to the thiol-metal interaction) and excellent survivability to thermal cycling despite significant interfacial coefficient of thermal expansion (CTE) mismatch. This advantage is due to the thermoset nature of the polymer matrix, the ability to accommodate strains at the interface between CTE-mismatched materials and the lack of stress concentrators that evolve during polymerization due to the thiol-mediated chain transfer mechanisms during curing [2]. We demonstrate the ability to deposit plasma-enhanced chemical vapor deposited Silicon Nitride (CTE &lt;3) on thiol-based polymers (CTE ~70) and survive thermal cycling to 270°C without interfacial delamination. The same polymerization phenomena that enable this behavior are conducive for loading organic and inorganic filler into thiol-based systems to optimize electrical and thermal conductivity in die attach adhesives, molding compounds and unique semiconductor packaging materials. Aliev, Baughman, et al. have previously utilized multiwalled carbon nanotubes and graphene-based structures to tune thermal conductivities and properties of organic-inorganic composites [3]. Herein we will present a multi-materials approach to enhance both thermal and electrical conductivity through control of phononic resonances in semiconductor packaging adhesives and discuss the impacts of modifying metallic (silver) and carbonaceous (nanotube and graphene) fillers imbedded within a thiol-based polymer matrix. We present early work on the effects of thiol-mediated chain transfer mechanisms during polymerization on the percolation threshold of fillers and resulting electrical and thermal conductivity.

Xylose- and Nucleoside-Based Polymers via Thiol-ene Polymerization toward Sugar-Derived Solid Polymer Electrolytes.

A series of copolymers have been prepared via thiol-ene polymerization of bioderived α,ω-unsaturated diene monomers with dithiols toward application as solid polymer electrolytes (SPEs) for Li+-ion conduction. Amorphous polyesters and polyethers with low Tg's (-31 to -11 °C) were first prepared from xylose-based monomers (with varying lengths of fatty acid moiety) and 2,2'-(ethylenedioxy)diethanethiol (EDT). Cross-linking by incorporation of a trifunctional monomer also produced a series of SPEs with ionic conductivities up to 2.2 × 10-5 S cm-1 at 60 °C and electrochemical stability up to 5.08 V, a significant improvement over previous xylose-derived materials. Furthermore, a series of copolymers bearing nucleoside moieties were prepared to exploit the complementary base-pairing interaction of nucleobases. Flexible, transparent, and reprocessable SPE films were thus prepared with improved ionic conductivity (up to 1.5 × 10-4 S cm-1 at 60 °C), hydrolytic degradability, and potential self-healing capabilities.

Impact of Interfaces on the CO2 Permeability of Photopatterned Two-Stage Thiolene Polymer Films

Impact of Interfaces on the CO₂ Permeability of Photopatterned Two-Stage Thiolene Polymer Films

Enlarging the Stokes shift of CuInS2 quantum dots using thiol–ene polymers for efficient large-area luminescent solar concentrators

A thiol–ene polymer is employed to enlarge the Stokes shift of CuInS2/ZnS quantum dots for application in luminescent solar concentrators (LSCs), and a certified record power conversion efficiency of 1.36% (area of 29 × 29 cm2) was achieved.

Extending the shelf life of HLM chips through freeze-drying of human liver microsomes immobilized onto thiol-ene micropillar arrays.

Microfluidic flow reactors functionalized with immobilized human liver microsomes (HLM chips) represent a powerful tool for drug discovery and development by enabling mechanism-based enzyme inhibition studies under flow-through conditions. Additionally, HLM chips may be exploited in streamlined production of human drug metabolites for subsequent microfluidic in vitro organ models or as metabolite standards for drug safety assessment. However, the limited shelf life of the biofunctionalized microreactors generally poses a major barrier to their commercial adaptation in terms of both storage and shipping. The shelf life of the HLM chips in the wetted state is ca. 2-3 weeks only and requires cold storage at 4 °C. In this study, we developed a freeze-drying method for lyophilization of HLMs that are readily immobilized inside microfluidic pillar arrays made from off-stoichiometric thiol-ene polymer. The success of lyophilization was evaluated by monitoring the cytochrome P450 and UDP-glucuronosyltransferase enzyme activities of rehydrated HLMs for several months post-freeze-drying. By adapting the freeze-drying protocol, the HLM chips could be stored at room temperature (protected from light and moisture) for at least 9 months (n = 2 independent batches) and up to 16 months at best, with recovered enzyme activities within 60-120% of the non-freeze-dried control chips. This is a major improvement over the cold-storage requirement and the limited shelf life of the non-freeze-dried HLM chips, which can significantly ease the design of experiments, decrease energy consumption during storage, and reduce the shipping costs with a view to commercial adaptation.

Biobased Transparent Thiol–Ene Polymer Networks from Levoglucosan

Biobased Transparent Thiol–Ene Polymer Networks from Levoglucosan

Non-isocyanate polyurethanes synthesized from terpenes using thiourea organocatalysis and thiol-ene-chemistry

The depletion of fossil resources as well as environmental concerns contribute to an increasing focus on finding more sustainable approaches for the synthesis of polymeric materials. In this work, a synthesis route towards non-isocyanate polyurethanes (NIPUs) using renewable starting materials is presented. Based on the terpenes limonene and carvone as renewable resources, five-membered cyclic carbonates are synthesized and ring-opened with allylamine, using thiourea compounds as benign and efficient organocatalysts. Thus, five renewable AA monomers are obtained, bearing one or two urethane units. Taking advantage of the terminal double bonds of these AA monomers, step-growth thiol-ene polymerization is performed using different dithiols, to yield NIPUs with molecular weights of above 10 kDa under mild conditions. Variation of the dithiol and amine leads to polymers with different properties, with Mn of up to 31 kDa and Tg’s ranging from 1 to 29 °C.

Multifaceted Shape Memory Polymer Technology for Biomedical Application: Combining Self-Softening and Stretchability Properties.

Thiol-ene polymers are a promising class of biomaterials with a wide range of potential applications, including organs-on-a-chip, microfluidics, drug delivery, and wound healing. These polymers offer flexibility, softening, and shape memory properties. However, they often lack the inherent stretchability required for wearable or implantable devices. This study investigated the incorporation of di-acrylate chain extenders to improve the stretchability and conformability of those flexible thiol-ene polymers. Thiol-ene/acrylate polymers were synthesized using 1,3,5-triallyl-1,3,5-triazine-2,4,6(1H,3H,5H)-trione (TATATO), Trimethylolpropanetris (3-mercaptopropionate) (TMTMP), and Polyethylene Glycol Diacrylate (PEGDA) with different molecular weights (Mn 250 and Mn 575). Fourier Transform Infrared (FTIR) spectroscopy confirmed the complete reaction among the monomers. Uniaxial tensile testing demonstrated the softening and stretching capability of the polymers. The Young's Modulus dropped from 1.12 GPa to 260 MPa upon adding 5 wt% PEGDA 575, indicating that the polymer softened. The Young's Modulus was further reduced to 15 MPa under physiologic conditions. The fracture strain, a measure of stretchability, increased from 55% to 92% with the addition of 5 wt% PEGDA 575. A thermomechanical analysis further confirmed that PEGDA could be used to tune the polymer's glass transition temperature (Tg). Moreover, our polymer exhibited shape memory properties. Our results suggested that thiol-ene/acrylate polymers are a promising new class of materials for biomedical applications requiring flexibility, stretchability, and shape memory properties.

Synthesis and Crystallization of Waterborne Thiol-ene Polymers: Toward Innovative Oxygen Barrier Coatings.

The synthesis of waterborne thiol-ene polymer dispersions is challenging due to the high reactivity of thiol monomers and the premature thiol-ene polymerization that leads to high irreproducibility. By turning this challenge into an advantage, a synthesis approach of high solid content film-forming waterborne poly(thioether) prepolymers is reported based on initiator-free step growth sonopolymerization. Copolymerization of bifunctional thiol and ene monomers diallyl terephthalate, glycol dimercaptoacetate, glycol dimercaptopropionate, and 2,2-(ethylenedioxy)diethanethiol gave rise to linear poly(thioether) functional chains with molar mass ranging between 7 and 23 kDa when synthesized at 30% solid content and between 1 and 9 kDa at increased solid content of 50%. To further increase the polymers' molar mass, an additional photopolymerization step was performed in the presence of a water-soluble photoinitiator, i.e., lithium phenyl-2,4,6-trimethylbenzoylphosphinate, leading to high molar mass chains of up to 200 kDa, the highest reported so far for step grown poly(thioethers). The polymer dispersions presented good film-forming ability at room temperature, yielding semicrystalline films with a high potential for barrier coating applications. Nevertheless, affected by the polymer chemical repeating structure, which includes an aromatic ring, these thiol-ene chains can only crystallize very slowly from the molten state. Herein, for the first time, we present the successful implementation of a self-nucleation (SN) procedure for these types of poly(thioethers), which effectively accelerates their crystallization kinetics.