Triethylene Glycol Divinyl Ether Research Articles

UV-Cured Highly Crosslinked Polyurethane Acrylate to Serve as a Barrier against Chemical Warfare Agent Simulants.

Ultraviolet (UV) curing is an efficient and environmentally friendly curing method. In this paper, UV-cured polyurethane acrylates (PUAs) were investigated as potential military coatings to serve as barriers against chemical warfare agents (CWAs). Seven UV-cured PUA coatings were formulated utilizing hydroxyethyl methacrylate-capped hexamethylene diisocyanate trimer (HEMA-Htri) and trimethylolpropane triacrylate-capped polycarbonate prepolymer (PETA-PCDL) as the PUA monomers. Isobornyl acrylate (IBOA) and triethyleneglycol divinyl ether (DVE-3) were employed as reactive diluents. Gas chromatography was utilized to investigate the constitutive relationships between the structures of the PUA coatings and their protective properties against simulant agents for CWAs, including dimethyl methylphosphonate (DMMP), a nerve agent simulant, and 2-chloroethyl ethyl sulfide (CEES), a mustard simulant. The glass transition temperature (Tg) and crosslinking density (υe) of PUAs were found to be crucial factors affecting their ability to serve as barriers against CWAs. The incorporation of IBOA units led to enhanced Tg and barrier performance of the PUAs, resulting in a DMMP retention of less than 0.5% and nearly 0 retention of CEES. However, an excessive introduction of polycarbonate chains decreased the υe and barrier performance of the PUAs. These findings may offer valuable insights for enhancing the protection of UV-cured PU coatings against CWAs.

Additive and Interface Engineering via Crosslinked 3D Polymer Network for Efficient and Stable Perovskite Solar Cells

In this study, a facile and promising strategy is presented to enhance the performance and stability of perovskite solar cells (PeSC) by incorporating tri(ethylene glycol) divinyl ether (TEGDVE) as the additive and dopant for perovskite active layer and amine‐functionalized perylene diimide (PDIN) cathode interfacial layer, respectively. The results indicate that the electron‐donating oxygen atoms of TEGDVE can interact with undercoordinated Pb2+ via the formation of coordination bond, which synchronously passivates the defects within perovskite film and manipulates the crystallization kinetics. Additionally, the vinyl functional groups on TEGDVE can undergo thermal cross‐linking reaction and form three‐dimensional polymer network, enabling perovskite film to possess good optoelectronic properties and enhanced moisture stability. In addition, the incorporation of TEGDVE can induce n‐doping of PDIN due to its adequate electron donation capability offered by oxygen atoms. With these appealing features, the resulting device delivers not only high power conversion efficiency up to 20.90% but also satisfied ambient stability, greatly outperforming those of the PeSC without TEGDVE. This work provides a new avenue to improve the efficiency and stability of PeSC based on a facile strategy. The findings present a significant step towards the practical applications of this emerging technology.

Designing a novel polythioether/multiwall carbon nanotube nanocomposites: A complete overview of mechanical, thermal, and morphological properties

AbstractPolythioether is an elastomer with proper thermal resistance and elongation at break, which can be used in various high‐temperature and high‐pressure sealing applications. This research is aimed to determine the suitable thiol/vinyl ratio and the branching agent content to synthesize a novel polythioether and the polythioether/multiwall carbon nanotube (MWCNT) composite using two monomers, including dimercapto dioxaoctane (DMDO) and triethylene glycol divinylether. For each synthesis process, the gel permeation chromatography (GPC) was used to measure the molecular weight and the polydispersity index of the polymer chains. Fourier transforms infrared spectroscopy and Nuclear Magnetic Resonance were used to study the bond formation, while the glass transition of the polymer was evaluated by differential scanning calorimetry. Tensile and lap adhesion tests were also used to assess the mechanical properties of the samples. Field emission scanning electron microscopy was utilized to observe the dispersion of nanoparticles in polythioether/MWCNT nanocomposite. GPC results showed that the thiol/vinyl ratio of 0.5 and branching agent molar ratio of 0.2 (relative to vinyl monomer) led to the most suitable average molecular weight (2022 g/mol) which had the highest mechanical properties. The nanocomposite containing 1 wt% MWCNT, showed the highest tensile strength and elongation at break up to 2.12 MPa and 303%, respectively. A considerable increase of 30°C is obtained in maximum degradation temperature of the produced nanocomposite compared to neat polythioether.

Photodisulfidation of alkenes with linear disulfides: Reaction scope and kinetics

Thiol-ene and thiol-yne photomediated conjugations have received substantial attention in research and in practice. Herein is presented the photodisulfidation of alkenes based on the radical-mediated 1:1 reaction of a disulfide and a vinyl ether, which provides an additional route for the formation of the types of sulfides seen in thiol-ene and thiol-yne polymers. Although similar linkages are formed, this approach starting with disulfides is expected to have benefits over the thiol-ene and thiol-yne reactions including extended shelf life of disulfides compared to thiols, reduced shrinkage stress, and increased refractive index of the resulting materials. It was determined that vinyl ethers were the only alkenes capable of undergoing photodisulfidation under ambient conditions and in reasonable timescales. The reaction between vinyl ethers and disulfides performed well in a variety of solvents providing modest to excellent yields (100% for bis(1-methylacetate) disulfide (DSMA)/triethyleneglycol divinylether (TEGDVE)) for numerous disulfide substrates evaluated. It was determined that the mechanism of the photodisulfidation reaction involves an auto-propagating cycle of thiyl radicals which add into either end of a vinyl ether to form thio-ether and thio-acetal linkages in the final product. Finally, although the reaction rate is slower than that of the thiol-ene reaction, the photodisulfidation reaction proceeds relatively rapidly under the explored conditions.

Facile preparation of reprocessable and degradable phenolic resin based on dynamic acetal motifs

Phenolic resins with irreversible cross-links structure make them difficult to degrade and recycle. It is an emerging trend for phenolic resins thermoset to develop a rapid and facile closed-loop recycling approach. Herein, the degradable and reprocessable phenolic thermosets (PRTs) based on reversible acetal bonds were synthesized by tri(ethylene glycol) divinyl ether (TEGDVE) and linear phenolic resin through one-step “click” addition reaction. By employing the chain mobility induced by dynamic weak acetal motifs and linear TEGDVE in PRTs, the mechanical strengths could be rationally adjusted, and more moderate reprocessing and degradation conditions were achieved. Accordingly, the flexible structure units containing weak reversible acetal linkages were expected to accelerate the mobility of the chain segments and decrease the reprocessing temperature, while the linear phenolic structure afforded the high mechanical strength. Remarkedly, a champion degradation rate of 121.8 mg·mL−1·h−1 was achieved under acid condition by adjusting the ratio of flexible chains consisting of dynamic acetal bonds. In addition, compared with pristine PRTs, regenerative one maintained 93.41% of elongation at break. This work may shed a light for realizing degradable and reprocessable dynamic network materials with high efficiency.

Enhanced properties of well-defined polymer networks prepared by a sequential thiol-Michael - radical thiol-ene (STMRT) strategy

A sequential thiol-Michael - radical thiol-ene (STMRT) strategy was used to produce poly(ethylene glycol)-based model networks and enable establishment of a structure–property relationship from the network characteristics. Selective double thiol-Michael reactions on a series of poly(ethylene glycol) diacrylates (PEGDA), that differed in average chain length, with two molar equivalents of the trithiol trimethylolpropane tris(3-mercaptopropionate) (TMPTMP) yielded well-defined telechelic poly(ethylene glycol)-based tetrathiols. These tetrathiols were in turn used to produce model (co–)networks by photo-induced radical thiol-ene polymerization with either the same poly(ethylene glycol) diacrylates or with tri(ethyleneglycol) divinylether (TEGDVE). The properties of these networks were studied by Fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA). The STMRT-produced model networks possess storage moduli (E′) up to 4-fold larger and glass transition temperatures (Tg) of up to 10 °C lower than conventionally produced counterparts. The STMRT strategy allows the properties of the model networks to be finely tuned by manipulation of crosslink density and average polymer chain length.

Two-photon induced polymerization in a porous polymer film to create multi-layer structures.

Two-photon induced polymerization for three-dimensional (3D) printing has attracted increasing attention. Here, we report the two-photon induced polymerization of triethylene glycol divinyl ether (TEGDVE) in a porous polymer film using 4,4',4''-nitrilotribenzoic acid (NTB) as the photosensitizer and diphenyliodonium hexafluorophosphate (HIP) as the initiator, enabling the printing of multi-layer structures in the porous support.

Preparation and characterization of environmentally friendly agar/κ-carrageenan/montmorillonite nanocomposite hydrogels

In the present study, for the first time, agar/κ-carrageenan and agar/κ-carrageenan/montmorillonite hydrogel materials were prepared by the free-radical crosslinking reaction of agar and κ-carrageenan in the presence of triethylene glycol divinyl ether (TEGDE) as the crosslinker agent. Here, montmorillonite (MMT) modified with phenylalanine was used as additive agent. Agar/κ-carrageenan hydrogel materials with and without MMT were characterized by FTIR, SEM and XRD analyses. The effect of free radical initiator (ammonium persulfate, APS) concentration, crosslinking agent (TEGDE) concentration, reaction temperature, polysaccharide ratio and MMT concentration on the swelling performance and surface property of hydrogel material was investigated and optimum reaction conditions were determined. Maximum equilibrium swelling capacity of the agar/κ-carrageenan hydrogel was found to be 2523 % under the optimum conditions ([APS] = 5 × 10−4 M, [TEGDE] = 5 × 10−4 M, T = 70 °C and magar:mκ-carrageenan = 1:4). An increase of the MMT content within hyrogel matrix led to a decrease in the swelling values of hydrogels. All of the hydrogels prepared in various formulations exhibited non-Fickian swelling behavior. New hydrogel materials obtained from this study could be potential candidates for biomedical applications.

Naphthoquinone derivatives: Naturally derived molecules as blue-light-sensitive photoinitiators of photopolymerization

Two naphthoquinone derivatives, i.e. 5-hydroxy-1,4-naphthoquinone (5HNQ) and 2-hydroxy-1,4-naphthoquinone (2HNQ), combined with different additives such as diphenyliodonium hexafluorophosphate (Iod), N-vinylcarbazole (NVK), phenacyl bromide (R-Br), N-phenyl glycine (NPG) and ethyl 4-dimethylamino benzoate (EDB), are investigated as photoinitiating systems (PISs) for free radical polymerization of trimethylolpropane triacrylate (TMPTA) and cationic polymerization of triethyleneglycol divinyl ether (DVE-3). The photopolymerization of the thiol-ene system trimethylolpropane tris(3-mercaptopropionate) (Trithiol)/DVE-3 with 5HNQ or 2HNQ based PISs are also investigated. 5HNQ shows maximum absorption in visible light region (blue light) which thus has the potential to perform under the irradiation of blue LED light. For the free radical polymerization of TMPTA, 5HNQ/Iod/NPG shows the highest photoinitiating ability among all the naphthoquinone derivative-based PISs, while 2HNQ-based systems are inefficient. The addition of Trithiol to TMPTA can significantly increase the double bond conversion of TMPTA during the photopolymerization. For the cationic photopolymerization of DVE-3, 2HNQ/Iod shows the highest photoinitiating ability among all the naphthoquinone derivative-based photoinitiating systems. 5HNQ-based systems also demonstrate good photoinitiation ability for DVE-3, but with slower polymerization rate compared to 2HNQ-based systems. In thiol-ene photopolymerization, 5HNQ PISs shows better photoinitiation ability than 2HNQ PIs systems. The results illustrate that the position of hydroxyl group in 1,4-naphthoquinone molecules plays an important role on photoinitiation ability of naphthoquinone derivatives. Steady state photolysis and electron spin resonance trapping experiments are also carried out to evaluate the relevant photochemical mechanism.

Facile Functionalization of Poly(Dimethylsiloxane) Elastomer by Varying Content of Hydridosilyl Groups in a Crosslinker.

Crosslinked poly(dimethylsiloxane) (PDMS) has been widely used as a dielectric elastomer for electrically driven actuators because it exhibits high elasticity, low initial modulus, and excellent moldability in spite of low dielectric constant. However, further improvement in the characteristics of the PDMS elastomer is not easy due to its chemical non-reactivity. Here, we report a simple method for functionalizing the elastomer by varying content of hydridosilyl groups in PDMS acted as a crosslinker. We synthesized poly(dimethylsiloxane-co-methylvinylsiloxane) (VPDMS) and poly(dimethylsiloxane-co-methylsiloxane) (HPDMS). Tri(ethylene glycol) divinyl ether (TEGDE) as a polar molecule was added to the mixture of VPDMS and HPDMS. TEGDE was reacted to the hydridosilyl group in HPDMS during crosslinking between VPDMS and HPDMS in the presence of platinum as a catalyst. Permittivity of the crosslinked film increased from ca. 25 to 36 pF/m at 10 kHz without a decline in other physical properties such as transparency and elasticity (T > 85%, E ~150 kPa, ɛ ~270%). It depends on the hydridosilyl group content of HPDMS. The chemical introduction of a new molecule into the hydridosilyl group in HPDMS during crosslinking would provide a facile, effective method of modifying the PDMS elastomers.

Applicability of 1,6-Diphenylquinolin-2-one Derivatives as Fluorescent Sensors for Monitoring the Progress of Photopolymerisation Processes and as Photosensitisers for Bimolecular Photoinitiating Systems.

The applicability of new 1,6-diphenylquinolin-2-oneas derivatives as fluorescent molecular sensors for monitoring the progress of photopolymerisation processes by Fluorescence Probe Technique (FPT) has been tested. The progress of cationic, free-radical and thiol-ene photopolymerisation for commercially available monomers: triethylene glycol divinyl ether (TEGDVE), trimethylolpropane triacrylate (TMPTA) and trimethylpropane tris(3-mercaptopropropionate) (MERCAPTO) was monitored. It was found that new derivatives of 1,6-diphenylquinolin-2-one shifted their fluorescence spectra towards shorter wavelengths with the progress of polymerisation, which enabled monitoring the progress in terms of fluorescence intensity ratios as the progress indicator. Derivatives of 1,6-diphenylquinolin-2-one show sensitivity to changes in both polarity and viscosity in the surrounding microenvironment during photopolymerisation processes. Therefore, it was shown that they are good candidates to act as fluorescent sensors for monitoring the kinetics of very quick processes, such as photopolymerisation processes. Furthermore, the effect of the nature of substituents attached to the 1,6-diphenylquinolin-2-one ring on the characteristics of emission spectra was identified. Moreover, the sensitivity of fluorescent sensors was compared with commercially available model sensors, such as 7-diethylamino-4-methylcoumarin (Coumarin 1) and trans-2-(2′,5′-dimethoxyphenyl)ethenyl-2,3,4,5,6-pentafluorobenzene (25ST). Moreover, it was also proven that selected derivatives of 1,6-diphenylquinolin-2-one exhibit an accelerating effect on the progress of cationic photopolymerisation of vinyl monomers (TEGDVE). Thus, the new 1,6-diphenylquinolin-2-one derivatives can be successfully used both as molecular fluorescence sensors to monitor the progress of photopolymerisation processes and as diaryliodonium salt photosensitisers to initiate cationic photopolymerisation processes in a UV-A range of 365 nm.

Mechanism of interaction of aminocoumarins with reaction medium during cationic photopolymerization of triethylene glycol divinyl ether

Applicability of a series of coumarin derivatives as fluorescent probes for monitoring progress of cationic photopolymerization processes by Fluorescence Probe Technique (FPT) has been studied using triethylene glycol divinyl ether as a model monomer and diphenyliodonium hexafluorophospate as a cationic photoinitiator. The following coumarins were evaluated: Coumarin 1, Coumarin 6H, Coumarin 102, Coumarin 120, Coumarin 151, Coumarin 343 and Coumarin 466. It has been found that despite the presence of an amino group in their structure, at low concentrations of the order of 0.1%, the Coumarins 1, 102, 343 and 466 can be used as the fluorescent probes for the cationic photopolymerization, while Coumarin 343 exhibits the best performance. At high concentrations, the aminocoumarins slow down the photopolymerization rate and extend induction period. All of the aminocoumarins are applicable as long-wavelength sensitizers for diphenyliodonium photoinitiators, enabling photopolymerization at the irradiation wavelengths, where the photoinitiator does not absorb. At short wavelengths, where both photoinitiator and probe absorb light, and at the probe concentrations below 0.1%, Coumarin 343 and Coumarin 1 accelerate the cationic photopolymerization by supplying an additional route for the photoinitiator cleavage beside its direct cleavage upon light absorption. The direct initiation and sensitization mechanisms are proposed.

Applicability of samarium(III) complexes for the role of luminescent molecular sensors for monitoring progress of photopolymerization processes and control of the thickness of polymer coatings

Applicability of 15 trivalent samarium complexes as novel luminescent probes for monitoring progress of photopolymerization processes or thickness of polymer coatings by the Fluorescence Probe Technique (FPT) was studied. Three groups of samarium(III) complexes were evaluated in cationic photopolymerization of triethylene glycol divinyl ether monomer (TEGDVE) and free-radical photopolymerization of trimethylolpropane triacrylate (TMPTA). The complexes were the derivatives of tris(4,4,4-trifluoro-1-(2-thienyl)-1,3-butanedionate)samarium(III), tris(4,4,4-trifluoro-1-phenyl-1,3-butanedionate)samarium(III) and tris(4,4,4-trifluoro-1-(2-naphthyl)-1,3-butanedionate)samarium(III), which were further coordinated with auxiliary ligands, such as 1,10-phenanthroline, triphenylphosphine oxide, tributylphosphine oxide and trioctylphosphine oxide. It has been found that most of the complexes studied are sensitive enough to be used as luminescent probes for monitoring progress of cationic photopolymerization of vinyl ether monomers over entire range of monomer conversions. In the case of free-radical polymerization processes, the samarium(III) complexes are not sensitive enough to changes of microviscosity and/or micropolarity of the medium, so they cannot be used to monitor progress of the polymerization. However, high stability of luminescence intensity of some of these complexes under free-radical polymerization conditions makes them good candidates for application as thickness sensors for polymer coatings prepared by free-radical photopolymerization. A quantitative relationship between a coating thickness and the luminescence intensity of the samarium(III) probes has been derived and verified experimentally within a broad range of the thicknesses.

Polymeric nanocapsules via interfacial cationic photopolymerization in miniemulsion

The synthesis of polymeric nanocapsules by means of miniemulsion cationic polymerization has been investigated here. The core-shell structure was obtained by confining the reaction at the interface between continuous and dispersed phase of an oil-in-water miniemulsion. This hallmark also allows to carry out the cationic UV-activated polymerization of a vinyl monomer, namely triethylene glycol divinyl ether, in water. The study firstly focused on formulation design. Various kinds of surfactant were examined and SDS provided optimal miniemulsion stability. Moreover, several amounts of surfactant, photoinitiator and oil were tested to optimize formulation composition. Nanocapsules were successfully synthesized and their average size, dimensional distribution, surface zeta potential, stability over time, morphology and thermal behavior were explored. Then, processing conditions, namely irradiation time and sonication time, were investigated. Results highlighted the possibility to design nanocapsule dimension by acting on ultrasound exposure time and a minimum size of 200 nm was identified.

Preparation of 3DPSL-1 Type Photosensitive Resin and Study on Its Properties

3DPSL-1(3D printing stereolithography No.1) type photosensitive resin was prepared with 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate (ERL-4221), bisphenol A type epoxy diacrylate (DH-306), tripropylene glycol diacrylate (TPGDA), Diglycidyl 4,5-epoxycyclohexane-1,2-dicarboxylate(TDE-85), triethylene glycol divinyl ether (DVE-3), benzil dimethyl ketal (Irgacure651) and a mixture of triarylsulfonium hexafluoroantimonate salts (UVI-6976) as raw materials. Some properties of the photosensitive resin were investigated. The viscosity of the photosensitive resin at 30 ℃ was 355mPa.S, the glass transition temperature (Tg) of the UV-cured specimen was 52 ℃, and the weight loss of the UV-cured specimen at 200 ℃ was less than 4%. The photosensitive resin and its UV-cured specimen were also characterized by infrared (IR).

Synthesis of polymeric microcapsules by interfacial-suspension cationic photopolymerisation of divinyl ether monomer in aqueous suspension

Polymeric microcapusles have been synthesised with a markedly more hydrophillic monomer than previously reported, triethylene glycol divinyl ether, using cationic photopolymerisation in an aqueous environment.

Thiol‐Ene Step‐Growth as a Versatile Route to Functional Polymers

AbstractA new use of the thiol‐ene reaction to generate functional, redox‐tunable polymers is described. To illustrate the versatility of this approach, tailored divinyl ether monomers were polymerized with triethylene glycol dithiol to yield polymers containing either a carbonate or zwitterionic phosphocholine within the polymer backbone. Similarly, dithioerythritol was polymerized with triethylene glycol divinyl ether to yield a polymer with pendant diols and show how functional groups can be designed into either the divinyl ether or dithiol monomer. Using the thioether functional group inherent to this polymerization, all three polymers were selectively and quantitatively oxidized to either sulfoxides or sulfones by treatment with dilute hydrogen peroxide or mCPBA, respectively. With these illustrative examples, it is shown that the thiol‐ene polymerization is a broad‐reaching method to access a class of new redox‐active polymers which contain varied and dense functional‐group compositions.

Thiol-Ene Step-Growth as a Versatile Route to Functional Polymers.

A new use of the thiol-ene reaction to generate functional, redox-tunable polymers is described. To illustrate the versatility of this approach, tailored divinyl ether monomers were polymerized with triethylene glycol dithiol to yield polymers containing either a carbonate or zwitterionic phosphocholine within the polymer backbone. Similarly, dithioerythritol was polymerized with triethylene glycol divinyl ether to yield a polymer with pendant diols and show how functional groups can be designed into either the divinyl ether or dithiol monomer. Using the thioether functional group inherent to this polymerization, all three polymers were selectively and quantitatively oxidized to either sulfoxides or sulfones by treatment with dilute hydrogen peroxide or mCPBA, respectively. With these illustrative examples, it is shown that the thiol-ene polymerization is a broad-reaching method to access a class of new redox-active polymers which contain varied and dense functional-group compositions.

An in situ intercalative polymerization method for preparing UV curable clay–polymer nanocomposites

ABSTRACTA novel in situ intercalative polymerization technique was used to disperse clay mineral in a precursor resin for use in UV curing by performing an in situ ion exchange reaction during polyesterification. Unmodified montmorillonite (MMT) was added to a reaction mixture composed of monomers and methyl, tallow, bis‐2‐hydroxyethyl ammonium (MTEtOH) during the synthesis of unsaturated polyesters to create resins containing highly dispersed, organically modified MMT. UV‐curable clay–polymer nanocomposite (CPN) films were then prepared utilizing donor–acceptor chemistry through reactions of the unsaturated polyester resin with triethylene glycol divinyl ether. Functional group conversion improved up to 15% by the incorporation of clay mineral into the polymer matrix through the in situ polymerization method. The CPNs also had improved barrier, mechanical, and thermal properties over a control film containing no clay mineral. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015, 132, 42601.

Study of Ink‐Jet Printable Vinyl Ether‐Graphene UV‐Curable Formulations

AbstractThis work reports the formulation of vinyl ether containing functionalized graphene sheets in order to produce UV‐curable conductive inks. The best graphene‐surfactant ratio was found to give a stable dispersion of graphene into triethyleneglycol divinyl ether (DVE3) resin, avoiding the presence of large filler aggregates that could clog printing head during ink‐jet process. Propylene carbonate was used as solvent to adjust the viscosity of the formulation. The presence of graphene did not significantly hindered the UV‐curing process. Crosslinked nanocomposite materials show a decrease of resistivity of seven order of magnitude with respect to the pristine polymeric matrix.