Facile Photopolymerization Research Articles

Facile Photopolymerization of High-Molecular-Weight Polyaniline Composites Induced by g-C3N4 at Room Temperature for Trace Fe Ion Sensors

Facile Photopolymerization of High-Molecular-Weight Polyaniline Composites Induced by g-C₃N₄ at Room Temperature for Trace Fe Ion Sensors

Iridescent structural colors printing on cellulose fabrics with robust structural coloration

Structural coloration originating from colloidal particle assembly has drawn tremendous interest because of the brilliant dye-free colors in line with green and low-carbon development of the world. However, challenges like preparing structural colors with high saturation, durability, and time-efficiency in an unsmooth flexible surface such as fabrics are still remain. Here, a facile photopolymerization process is developed to construct high saturation and durable structural colors on cotton fabrics. The structural colors derive from the fast assembly of external magnetic field triggered Fe3O4@C particles. It is easy to regulate structural colors by adjusting magnetic particle sizes. In addition, by designing photo masks on transparent polyester films, the magnetic field induced assembly and photo polymerization strategy can conveniently print structural colored patterns on cotton fabric. This strategy may open a new gate in the textile printing field, as well as bring a new method by using fabrics to improve the mechanical properties of structural colors.

Rational design of high-performance continuous flow catalytic membrane reactor based on poly(4-vinylpyridine) brush-anchored Au nanoparticles

The catalytic membrane reactor (CMR) is recognized as one of the most effective strategies to treat the organic wastewater system. Yet so far, inefficiency, lack of bactericidal ability, and serious membrane fouling have limited its further application. In this study, we designed a novel polyacrylonitrile (PAN) catalytic separation membrane loaded with gold nanoparticles (Au NPs) via a facile photopolymerization method. The Au NPs on the catalytic separation membrane (PAN-Au) surface can serve as a high-performance catalyst, and the ligand of the 4-vinylpyridine (4VP) acts as an efficient protecting ligand for Au NPs to avoid leakage and agglomeration. The PAN-Au membrane was applied to CMR, which can one-step catalytic separation of nitrophenols and methylene blue efficiently in a flow-through mode (up to 97.5% over multiple cycles of reuse). Even after contamination with organic dyes, the PAN-Au membrane can still recover the catalytic separation performance by self-cleaning. Moreover, a remarkable antibacterial (with an efficiency of ≈100%) activity of the PAN-Au membrane, with a strong correlation with the small-sized and well-distributed Au NPs loaded on the membrane surface. The tremendous catalytical, self-cleaning, and antibacterial performance of the PAN-Au membrane provides new insights for the rational design of flow CMR for industrial applications.

Tough Adhesive, Antifreezing, and Antidrying Natural Globulin-Based Organohydrogels for Strain Sensors.

Hydrogels are often used to fabricate strain sensors; however, they also suffer from freezing at low temperatures and become dry during long-time storage. Encapsulation of hydrogels with elastomers is one of the methods to solve these problems although the adhesion between hydrogels and elastomers is usually low. In this work, using bovine serum protein (BSA) as the natural globulin model and glycerol/H2O as the mixture solvent, BSA/polyacrylamide organohydrogels (BSA/PAAm OHGs) were prepared by a facile photopolymerization approach. At the optimal condition, BSA/PAAm OHG demonstrated not only high toughness but also tough adhesion properties, which could strongly adhere to various substrates, such as glass, metals, rigid polymeric materials (even poly(tetrafluoroethylene), i.e., PTFE), and soft elastomers. Moreover, BSA/PAAm OHG was flexible and showed tough adhesion at -20 °C. The toughening mechanism and the adhesive mechanism were proposed. On being encapsulated by poly(dimethylsiloxane) (PDMS), it illustrated good antidrying performance. After introducing a conductive filler, the encapsulated BSA/PAAm OHG could be used as a strain sensor to detect human motions. This work provides a better understanding of the adhesive mechanism of natural protein-based organohydrogels.

Luminescent and ultrastable perovskite-acrylate based elastomers with excellent stretchability and self-healing capability for flexible backlight display

All-inorganic lead halide perovskite nanocrystals (NCs) have received considerable attention due to their exceptional optoelectronic characteristics and photovoltaic performance, but their practical applications are restricted by their poor stability. Integrating multifunctionality such as high stability, outstanding flexibility, stretchability and self-healing capability has also been highly desired for flexible full-color displays, soft optical devices, and wearable applications. Here, we developed a facile one-pot photopolymerization strategy to produce highly stable self-healing CsPbBr3-based elastomers with outstanding flexibility, scalability, and stretchability. The obtained perovskite NCs (∼10 nm; PLQY of 78%) were capped and passivated with bifunctional methacrylic acid ligands, which provided free double bonds on their surface. The CsPbBr3-based elastomers were obtained via the photo-induced copolymerization of functionalized CsPbBr3 NCs with methyl methacrylate (MMA) and n-butyl acrylate (BA) at room temperature. This yielded homogenous CsPbBr3 nanocrystals (∼10 nm) dispersed in the copolymer, which displayed a high photoluminescence quantum yield (PLQY > 70%). Versatile and specific luminescent shapes and patterns could be fabricated from the CsPbBr3-based elastomers by regulating the constituent content, reaction time, or molding process. The obtained CsPbBr3-based elastomers exhibited high air and water stability, high stretchability (∼1300% elongation), tensile recovery (∼100%), and excellent self-healing capability, which also permitted twisting or bending. This facile photopolymerization strategy greatly expands the methods for fabricating highly stable perovskite materials with excellent stretchability and self-healing properties for use in flexible optoelectronic devices.

Ion-binding ameliorates the organic solvents nanofiltration performance of poly (butyl acrylamide-co-divinylbenzene) composites

• Poly (butyl acrylamide-co-divinylbenzene) nanofiltration membrane was synthesized. • The toplayer regularly distributed oxygen and nitrogen groups to anchor metal ions. • Fe-binding treatment enhanced the permeance and dye rejection in organic solvents. • Changes of the void size and the charge density in the toplayer were disclosed. A new nanofiltration composite membrane poly (butyl acrylamide-co-divinylbenzene) (poly-TaDb) was synthesized via a facile photopolymerization on polyetherimide using the monomers of n- tert -butyl acrylamide and divinylbenzene, and evaluated the separation performance in organic solutions. The unique poly-TaDb toplayer has a feature of branch structure containing regularly distributed oxygen and nitrogen groups that work as the interacting sites with metal ions (Fe 3+ , Zn 2+ , and Cu 2+ ), as reflected by the characterizations of ATR-FTIR, XPS, AFM, etc. Without the metal ion treatment, the optimal poly-TaDb membrane shows the permeance of 31, 17, 20.4 L m −2 h −1 MPa −1 respectively for organic solutions of tetrahydrofuran (THF), methanol (MeOH) and acetonitrile (ACN), with the rejection rates higher than 90% toward EB dye (879.8 g.mol −1 ). After interacting with these metal ions, the obtained Fe-binding poly-TaDb membranes possess higher permeance, with the THF, MeOH, and ACN permeance enhanced respectively to 113, 35, and 24.2 L m −2 h −1 MPa −1 , meanwhile maintaining high dye rejection rate. While the Cu- and Zn-binding membranes show much higher permeance but lower dye rejection rate. Density functional theory (DFT) calculations disclose that the void size of the toplayer network increases in the order of: the pristine (11.40 Å) < Fe-binding (11.54 Å) < Zn-binding (11.60 Å) < Cu-binding membrane (11.63 Å). It is the suitable void size and charge density distribution in the toplayer network of Fe-binding membrane. that results in the superior nanofiltration performance. This work provides a facile route to explore new polymeric network materials for highly effective separation performance in organic solvents.

One-Component DNA Mechanoprobes for Facile Mechanosensing in Photopolymerized Hydrogels and Elastomers

DNA mechanosensors offer unique properties for mechano-adaptive and self-reporting materials, such as programmable bond strength and geometrical strain response, tunable fluorescent strain sensing, interfacing to biological systems, and the ability to store mechanical information. However, the facile incorporation of advanced DNA motifs into polymer networks and achieving robustness in application settings remain difficult. Herein, we introduce one-component DNA mechanoprobes that can be easily polymerized into polymer hydrogels and even elastomers to allow strain-induced fluorescence sensing. The all-in-one mechanoprobe contains a DNA hairpin for programmable force sensing, an internal fluorophore-quencher pair as a reporter, and methacrylamide groups on both ends for rapid and facile photopolymerization into networks based on the nontoxic water-soluble monomer methoxy triethylene glycol acrylate (mTEGA). In addition to mechanosensing hydrogels, we utilize the low Tg of p(mTEGA) to develop the first bulk elastomer materials with DNA force sensors, which show high elasticity and stronger mechanofluorescence. The system makes decisive steps forward for DNA-based mechanoprobes by overcoming the classical multicomponent design of such probes, allowing photopolymerization useful for the design of complex objects or even 3D printing and demonstrating that such motifs may even be useful in dry bulk materials.

Biodegradable hydrogel with thermo-response and hemostatic effect for photothermal enhanced anti-infective therapy

Massive bleeding and infectious complication remain the leading cause of worldwide trauma deaths. To tackle this issue, a platelet-inspired degradable antibacterial hydrogel (Gel/PP-TA-Ag) is synthesized based on gelatin methacrylate (GelMA), tannic acid (TA), polyphosphate (PolyP) and gallic acid functionalized silver nanoparticles (Ag NPs) via a facile photopolymerization process. Accompanied by the degradation of the hydrogel, the released PolyP can activate the coagulation pathway, resulting in a better hemostatic effect than commercial gauze in the mice-bleeding model. Simultaneously, benefiting from hyperthermia originated from Ag NPs and photothermal accelerated release of TA and Ag+, 97.57% of methicillin-resistant Staphylococcus aureus (MRSA) and 95.99% of E. coli are eliminated in vitro. Moreover, in vivo experiments reveal that 91.76% of MRSA in wounds is removed, and the wound healing is effectively improved with more angiogenesis and collagen deposition. The level of inflammation in the wounds is also significantly reduced. As a result, Gel/PP-TA-Ag hydrogel possesses great potential in achieving satisfactory efficacy in infected wound healing.

Systematic Modulation and Structure–Property Relationships in Photopolymerizable Thermoplastics

Thermoplastics encompass the majority of commercial plastics but are limited to manufacturing techniques that require heat and/or solvent to enable material reprocessing and reshaping. Photopolymerization offers a readily accessible in situ alternative to conventional processing techniques but has typically been restricted to cross-linked networks, thus removing the potential for recycling/reprocessing of the materials. In this work, the paradigm of photopolymerizable thermoplastics consisting of semicrystalline thiol–ene polymers with repeat units structures mimicking those of poly(ethylene terephthalate) is explored. These materials are rapidly photopolymerized (<10 s) under mild irradiation conditions by using commercially available, unpurified dithiol and diene monomers to give polymeric materials with distinctive mechanical properties. The complex relationships between monomer structure, crystallization, and material properties (optical, thermal, and mechanical) were investigated by modifying the dithiol alkyl chain length (xDT, x = 2–10). Though subtle, these monomeric structural perturbations significantly impacted both the rate (∼0.3–19 MPa min–1) and extent of crystallization as well as the corresponding material properties (e.g., Young’s modulus and elongation to break ranging from 80–280 MPa and 500–840%, respectively). To confirm the expansive applicability of this facile photopolymerization method, substitutions to the diene functionalities that participate in crystallization were explored to understand the relationship between the monomer structure, the extent of crystallinity, and the mechanical performance. The photopolymers reported herein provide a basic framework to expand access to photocurable step-growth linear polymers with well-controlled polymerization-induced crystallization for a variety of applications, including for the rapid manufacture of prototypical or sacrificial components in 3D printing.

Online high-efficient specific detection of zearalenone in rice by using high-loading aptamer affinity hydrophilic monolithic column coupled with HPLC

Via the facile photopolymerization and thiol-ene click chemistry, a hydrophilic polyhedral oligomeric silsesquioxane (POSS)-containing affinity monolithic column with a high load of aptamers and fast preparation was presented, and successfully applied to the efficient specific recognition and sensitive detection of zearalenone (ZEN) by coupling with HPLC. Optimization of polymerization reaction and polymer recipe were studied, and characteristics such as structural morphology, affinity performance and specificity to ZEN were evaluated. A highly hydrophilic POSS-based aptamer affinity monolith was rapidly prepared in 1.1 h, and a high capacity of aptamer reached 2772.61 pmol/μL that was much higher than that of the current POSS-based aptamer affinity monoliths. By this way, the hydrophilic nature and aptamer coverage indensity in POSS monoliths were well improved. The mixed-mode mechanism including aptamer affinity recognition and hydrophilic interaction were employed for the specific analysis of ZEN. Applied to the monitoring of ZEN, a good selective recognition and sensitive detection were obtained with the detection limit (LOD) of 0.02 ng/mL. The stability and reproducibility were acceptable and the intra-day, inter-day and column-to-column relative standard deviations (RSDs) of the ZEN recovery were gained in the range from 2.28% to 5.32%, respectively. Satisfactory recoveries of ZEN in rice samples were realized ad 98.6 ± 2.8%–100.8 ± 2.0%. It might provide a preferable access to online specific analysis of ZEN via the hydrophilic POSS-based affinity monolith with a large capacity of aptamers and a high preparation efficiency.

Multifunctional Highly Oleophobic and Superhydrophilic Fabric Coatings Prepared by Facile Photopolymerization

AbstractIn this work, a facile approach through UV polymerization is developed for the preparation of highly oleophobic and superhydrophilic coating on polyester fabric by using short‐fluorochain acrylate (1H,1H,2H,2H‐tridecafluoro‐n‐octyl acrylate) together with hydrophilic monomer and crosslinker. The coated fabric has an oil contact angle of ≈146° for hexadecane and &gt;150° for many other oils including cooking oil and engine oil. A water drop can completely spread on the fabric within 68 ms. As a result, oil drops on the fabric surface can be easily lifted off by immersion in water. Because of its selective wettability to water, the coated fabric can also be used for oil–water filtration or water absorption from bulk oil. It is further demonstrated that the coated fabric has good hygroscopic and antistatic properties. Fabrics with these functions may find applications including oil–water separation and especially functional clothing for which the oil repellency and easy oil removal are essential while the water repellency is less important. Antistatic properties as shown by this material, are also demanded, in areas such as work clothing for auto repair and oil industries.

Ultrahigh Molecular Weight Hydrophobic Acrylic and Styrenic Polymers through Organic-Phase Photoiniferter-Mediated Polymerization.

As many physical properties of polymers scale with molecular weight, the ability to achieve polymers of nearly inaccessibly high molecular weight provides an opportunity to probe the upper size limit of macromolecular phenomena. Yet many of the most stimulating macromolecular designs remain out of reach of current ultrahigh molecular weight (UHMW) polymer synthetic approaches. Herein, we show that UHMW polymers of diverse composition can be achieved by irradiation of thiocarbonylthio photoiniferters with long-wave ultraviolet or visible light in concentrated organic solution. This facile photopolymerization strategy is general to acrylic-, acrylamido-, methacrylic-, and styrenic-based monomers, enabling the synthesis of well-defined macromolecules with molecular weights in excess of 106 g/mol. The high chain-end fidelity afforded by photoiniferter polymerization conditions facilitated the design of UHMW amphiphilic block copolymers, which were found to self-assemble into micellar morphologies up to 200 nm in diameter.

Homogeneous Freestanding Luminescent Perovskite Organogel with Superior Water Stability.

Metal-halide perovskites have become appealing materials for optoelectronic devices. While the fast advancing stretchable/wearable devices require stability, flexibility and scalability, current perovskites suffer from ambient-environmental instability and incompatible mechanical properties. Recently perovskite-polymer composites have shown improved in-air stability with the protection of polymers. However, their stability remains unsatisfactory in water or high-humidity environment. These methods also suffer from limited processability with low yield (2D film or beads) and high fabrication cost (high temperature, air/moisture-free conditions), thereby limiting their device integration and broader applications. Herein, by combining facile photo-polymerization with room-temperature in-situ perovskite reprecipitation at low energy cost, a one-step scalable method is developed to produce freestanding highly-stable luminescent organogels, within which CH3 NH3 PbBr3 nanoparticles are homogeneously distributed. The perovskite-organogels present a record-high stability at different pH and temperatures, maintaining their high quantum yields for > 110 days immersing in water. This paradigm is universally applicable to broad choices of polymers, hence casting these emerging luminescent materials to a wide range of mechanical properties tunable from rigid to elastic. With intrinsically ultra-stretchable photoluminescent organogels, flexible phosphorous layers were demonstrated with > 950% elongation. Rigid perovskite gels, on the other hand, permitted the deployment of 3D-printing technology to fabricate arbitrary 2D/3D luminescent architectures.

A facile photo-polymerization method for reconfigurable shape memory polymers

This paper reports a facile preparation of re-configurable shape memory polymer (SMP) with photo-polymerization method. A novel SMP was successfully prepared from the photo-curable resin synthesized with hexamethylenediacrylate and 1,6-Hexanedithiol. The photo-cured polymer forms semi-crystalline reversible phase and chemically cross-linked netpoints. They show good thermal-induced shape memory effect with about 92% shape fixity and about 99% shape recovery. Moreover, the photo-cured SMPs have excellent thermal-induced shape reconfiguration properties. A new permanent shape could be reconfigured easily by heat treatment at 130 °C. It is thus proposed that the photo-curable resin could be used as “printing ink” for SMP 4D printing applications.

Fuel cell electrolyte membranes based on copolymers of protic ionic liquid [HSO3-BVIm][TfO] with MMA and hPFSVE

Polymeric ionic liquids (PILs) have recently been attracting great attention as new types of electrolytes for polymer exchange membrane fuel cells (PEMFCs), clean energy devices, due to their outstanding properties. In this work, the copolymerization of the ionic liquid (IL) 1-(4-sulphobutyl)-3-vinylimidazolium trifluoromethanesulphonate, [HSO3-BVIm][TfO], with methyl methacrylate (MMA) and perfluoro-3,6-dioxa-4-methyl-7-octene sulfonyl fluoride in its hydrolyzed form (hPFSVE), respectively, was performed for the preparation of structurally new IL copolymer membranes with enhanced conductive properties in comparison with the pristine PIL form. Membranes were synthesized through a facile photopolymerization method under UV radiation. The effect of temperature under wet and dry conditions on the ionic conductivities of the resulting membranes was analyzed. The performances of the new membranes were also assessed in a proton exchange fuel cell for power generation. Both poly([HSO3-BVIm][TfO]-co-MMA) and poly([HSO3-BVIm][TfO]-co-hPFSVE) electrolyte membranes offered high conductivity even in dry conditions (in the order 10−3 - 10−2 S cm−1). At low MMA and hPFSVE amounts (10 mol%), the ionic conductivity and power performances of the resulting membranes were enhanced in comparison with the membrane only constituted of the polymerizable IL showing the promising prospects of these ionic liquid-based copolymers as proton exchange membranes, with power outputs up to 45 mW cm−2.

Synthesis of a photocurable acrylated poly(ethylene glycol)-co-poly(xylitol sebacate) copolymers hydrogel 3D printing ink for tissue engineering.

Photocurable hydrogel scaffolds for tissue engineering must have excellent biocompatibility, tunable mechanical characteristics, and be biodegradable at a controllable rate. Hydrogels developed as ink for 3D printing require several other properties such as optimal viscosity and shorter photocrosslinking time to ensure continuous extrusion and to avoid untimely collapse of the printed structure. Here, a novel photocurable hydrogel made of acrylated poly(ethylene glycol)-co-poly(xylitol sebacate) (PEXS-A) is developed for tissue engineering and 3D printing applications. Synthesis of PEXS-A hydrogel with equilibrated water content above 90% is achieved via a quick and facile photopolymerization process. Changing the acrylation ratio of the PEXS-A hydrogel has an impact on its crosslinking density, mechanical properties and degradation rate, thus highlighting PEXS-A tunability. PEXS-A could be employed as ink as demonstrated by the 3D printing of a 30-layers cubic grid with high structural integrity. Furthermore, 3T3 fibroblast cells encapsulated into PEXS-A during photocrosslinking maintain a viability of 93.76% after seven days, which showed the good biocompatibility of this novel hydrogel. These results indicate that PEXS-A hydrogel could have multiple applications including as 3D printing ink and as tissue engineering scaffold.

High-Performance All-Solid-State Polymer Electrolyte with Controllable Conductivity Pathway Formed by Self-Assembly of Reactive Discogen and Immobilized via a Facile Photopolymerization for a Lithium-Ion Battery.

All-solid-state polymer electrolytes (SPEs) have aroused great interests as one of the most promising alternatives for liquid electrolyte in the next-generation high-safety, and flexible lithium-ion batteries. However, some disadvantages of SPEs such as inefficient ion transmission capacity and poor interface stability result in unsatisfactory cyclic performance of the assembled batteries. Especially, the solid cell is hard to be run at room temperature. Herein, a novel and flexible discotic liquid-crystal (DLC)-based cross-linked solid polymer electrolyte (DLCCSPE) with controlled ion-conducting channels is fabricated via a one-pot photopolymerization of oriented reactive discogen, poly(ethylene glycol)diacrylate, and lithium salt. The experimental results indicate that the macroscopic alignment of self-assembled columns in the DLCCSPEs is successfully obtained under annealing and effectively immobilized via the UV photopolymerization. Because of the existence of unique oriented structure in the electrolytes, the prepared DLCCSPE films exhibit higher ionic conductivities and better comprehensive electrochemical properties than the DLCCSPEs without controlled ion-conductive pathways. Especially, the assembled LiFePO4/Li cells with oriented electrolyte show an initial discharge capacity of 164 mA h g-1 at 0.1 C and average specific discharge capacities of 143, 135, and 149 mA h g-1 at the C-rates of 0.5, 1, and 0.2 C, respectively. In addition, the solid cell also shows the first discharge capacity of 124 mA h g-1 (0.2 C) at room temperature. The outstanding cell performance of the oriented DLCCSPE should be originated from the macroscopically oriented and self-assembled DLC, which can form ion-conducting channels. Thus, combining the excellent performance of DLCCSPE and the simple one-pot fabricating process of the DLC-based all-solid-state electrolyte, it is believed that the DLC-based electrolyte can be one of the most promising electrolyte materials for the next-generation high-safety solid lithium-ion batteries.

One-step synthesis of bifunctional PEGDA/TiO2 composite film by photopolymerization for the removal of Congo red

Wrinkled structures can provide enlarged surface areas for some living organisms to ingest nutrients. Imitating biological wrinkle structures offers an efficient way to enhance the adsorption surface for removing hazardous pollutants in wastewater. In this work, poly-(ethylene glycol) double acrylate (PEGDA)/TiO2 composite film with tunable surface wrinkles was synthesized. TiO2 nanoparticles were evenly immobilized in the PEGDA hydrogel simply by a facile photopolymerization method within 700 ms. Various wrinkle morphologies were obtained by precisely controlling UV exposure time. The composite film was characterized by X-ray diffraction, scanning electron microscopy, diffuse reflection spectroscopy, etc. Congo red was chosen as a model pollutant to demonstrate the adsorption and degradation capacity of the composite film. The experimental results showed that the introduction of wrinkled polymer improved the dispersibility of TiO2 nanoparticles. The removal efficiency reached 100% after 180-min adsorption in the darkness and 180-min UV irradiation. The composite film exhibited a much higher enrichment and photocatalysis capacity than the pure TiO2 powder, and could be developed as a reusable film for the removal of the organic pollutants in wastewater.

A facile photopolymerization method for fabrication of pH and light dual reversible stimuli-responsive surfaces.

Dual reversible surfaces with pH and light responsive properties were prepared via two-stage photopolymerization by grafting dimethylaminoethyl methacrylate (DMAEMA) and 2-methyl-4-phenylazo acrylate (MPA-Azo) on a substrate. The wettability of the modified surface could be reversibly controlled because of the protonation and deprotonation of DMAEMA at different pH values and the photoisomerization of MPA-Azo under UV irradiation at different wavelengths. This facile two-stage photopolymerization method has potential applications in fabrication of various external stimuli-responsive surfaces in the future.

Photopolymerization kinetics, photorheology and photoplasticity of thiol–ene–allylic sulfide networks

AbstractBACKGROUND: Thiol–ene networks are of interest due to their facile photopolymerization and their open network structure. In this work, an allylic disulphide divinyl ether monomer is reacted with tetrathiol and divinyl ether monomers, which allows the network structure to permanently change in shape if stressed while under irradiation. We also study the photo‐differential scanning calorimetry (DSC) kinetics and photorheology during cure and the dynamic mechanical properties after cure.RESULTS: The heat of polymerization is similar for the thiol–ene systems and suggests ca 80% conversion of the vinyl ether groups. An increase in the initiator concentration increases the photocure rate as expected. The activation energy for photopolymerization is 7.6 kJ mol−1. DSC and rheometry studies show that the polymerization kinetics is slowed by the addition of the allylic disulfide divinyl possibly due to the formation of less reactive radicals. However, as shown by dynamic mechanical thermal analysis, the network structure is not changed very much by addition of this monomer. If radicals are generated by irradiation of a photoinitiator in the network while a stress is being applied, the polymer will permanently deform depending on the fraction of 2‐methylenepropane‐1,3‐di(thioethyl vinyl ether) in the network, due to a bond interchange reaction.CONCLUSION: The rate of thiol–ene reaction is slowed by the addition of the allylic disulfide divinyl ether. Photoplasticity is observed in the networks containing the allylic disulfide groups. Further work is required to optimize the extent of photoplasticity in these systems. Copyright © 2007 Society of Chemical Industry