Thiol‐ene photopolymerization for efficient curing of vinyl esters

Monomers for radical photopolymerization based on vinyl esters (VEs) have recently been identified as suitable alternatives to (meth)acrylates on account of their low irritancy and cytotoxicity. The drawback of most VEs with abstractable hydrogens is their relatively low reactivity compared with (meth)acrylates. Within this article, we proved by photo‐differential scanning calorimetry measurements and real‐time Fourier transform infrared spectroscopy that the thiol‐ene concept is able to improve the photoreactivity of these VEs to a large extent to a level between those of acrylates and methacrylates. Other VEs have now a reactivity of at least the level of similar acrylates. Mechanical properties as determined by Dynamic Mechanical Analysis and Charpy impact tests showed significant toughening of these materials. Furthermore, we were able to confirm low toxicity of all components by osteoblast cell culture experiments. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013     

Biomaterials based on low cytotoxic vinyl esters for bone replacement application

In recent days, additive manufacturing technologies (AMT) based on photopolymerization have also found application in tissue engineering. Although acrylates and methacrylates have excellent photoreactivity and afford photopolymers with good mechanical properties, their cytotoxicity and degradation products disqualify them from medical use. Within this work, (meth)acrylate‐based monomers were replaced by vinyl esters with exceptional low cytotoxicity. The main focus of this paper lies on the determination of the photoreactivity and investigations concerning mechanical properties and degradation behavior of the new materials. Tested monomers provide sufficient photoreactivity for processing by AMT. Mechanical properties similar to natural bone could be obtained by adding suitable fillers like hydroxylapatite (HA). The right ratio of hydrophobic and hydrophilic monomers allows the tuning of the degradation behavior. Finally, with the optimum formulation, cellular 3D structures were built using digital light processing. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011.     

Synthesis and photopolymerization of novel multifunctional vinyl esters

Novel mono‐ and multifunctional vinyl ester monomers containing thioether groups were synthesized via an amine‐catalyzed Michael addition reaction between vinyl acrylate and multifunctional thiols. Using photo‐differential scanning calorimetry and real‐time Fourier transform infrared (RTIR) spectroscopy, the polymerization kinetics and oxygen inhibition of the homopolymerizations of the vinyl ester monomers were investigated. The effect of the vinyl ester and thioether group on acrylate/vinyl ester and thiol/vinyl ester copolymerizations was determined using real‐time IR spectroscopy to monitor polymerization rates of acrylate, vinyl, and thiol groups simultaneously. Polymerization of the vinyl esters used was found to be relatively insensitive to oxygen inhibition. We propose that the thioether group is responsible for reducing oxygen inhibition by a series of chain transfer/oxygen‐scavenging reactions. In polymerization of a acrylate/vinyl ester mixture both in nitrogen and in air, the vinyl ester monomer significantly enhances the polymerization rates and the conversion of the acrylate double bonds via plasticization of the crosslinked matrix and reduction of inhibition by oxygen. Ultimately, the vinyl ester monomer is incorporated into the polymer network. Thiol/vinyl ester free‐radical copolymerization is much faster than either thiol/allylether copolymerization or vinyl ester homopolymerization. The electron‐rich vinyl ester double bonds ensure rapid copolymerization with thiol. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 4424–4436, 2004     

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     

Photopolymerization of biocompatible phosphorus‐containing vinyl esters and vinyl carbamates

Phosphorus‐containing vinyl esters and vinyl carbamates were synthesized as new biocompatible and degradable photopolymers. Reactivity of the monomers with one, two, and three polymerizable double bonds was evaluated by photo‐differential scanning calorimetry. With respect to their potential application in the biomedical field, studies on cytotoxicity, mechanical stability, and hydrolytic erosion behavior of the poly(vinyl alcohol)‐based derivatives were performed. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 2916–2924, 2010     

Silicon‐based mercaptans: High‐performance monomers for thiol‐ene photopolymerization

Ester‐free silane and siloxane‐based thiol monomers were successfully synthesized and evaluated for application in thiol‐ene resins. Polymerization reaction rates, conversion, network properties as well as degradation experiments of those thiol monomers in combination with triallyl‐1,3,5‐triazine‐2,4,6(1H,3H,5H)‐trione (TATT) as ene component were performed and compared with formulations containing the commercially available mercaptopropionic ester‐based thiol pentaerythritol tetra‐3‐mercaptopropionate. Kinetic analysis revealed appropriate reaction rates and conversions reaching 90% and higher. Importantly, storage stability tests of those formulations clearly indicate the superiority of the synthesized mercaptans compared with pentaerythritol tetra‐3‐mercaptopropionate/TATT resins. Moreover, photocured samples containing silane‐based mercaptans provide higher glass transition temperatures and withstand water storage without a significant loss in their network properties. This behavior together with the observed excellent degradation resistance of photocured silane‐based thiol/TATT formulations make these multifunctional mercaptans interesting candidates for high‐performance applications, such as dental restoratives and automotive resins. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 418–424     

Functional off‐stoichiometry thiol‐ene‐epoxy thermosets featuring temporally controlled curing stages via an UV/UV dual cure process

We present a facile two‐stage UV/UV activation method for the polymerization of off‐stoichiometry thiol‐ene‐epoxy, OSTE+, networks. We show that the handling and processing of these epoxy‐based resins is made easier by introducing a material with a controlled curing technique based on two steps, where the first step offers excellent processing capabilities, and the second step yields a polymer with suitable end‐properties. We investigate the sequential thiol‐ene and thiol‐epoxy reactions during these steps by studying the mechanical properties, functional group conversion, water absorption, hydrolytic stability, and thermal stability in several different thiol‐ene‐epoxy formulations. Finally, we conclude that the curing stages can be separated for up to 24 h, which is promising for the usefulness of this technique in industrial applications. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 2604‐2615     

Toughness enhancers for bone scaffold materials based on biocompatible photopolymers

Providing access to the benefits of additive manufacturing technologies in tissue engineering, vinyl esters recently came into view as appropriate replacements for (meth)acrylates as precursors for photopolymers. Their low cytotoxicity and good biocompatibility as well as favorable degradation behavior are their main assets. Suffering from rather poor mechanical properties, particularly in terms of toughness, several improvements have been made over the last years. Especially, thiol–ene chemistry has been investigated to overcome those shortcomings. In this study, we focused on additional means to further improve the toughness of an already established biocompatible vinyl ester‐thiol formulation, eligible for digital light processing‐based stereolithography. All molecules were based on poly(ε‐caprolactone) as building block and the formulations were tested regarding their reactivity and the resulting mechanical properties. They all performed well as toughness enhancer, ultimately doubling the impact resistance of the reference system. © 2018 The Authors. Journal of Polymer Science Part A: Polymer Chemistry published by Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 110–119     

Application of thiol‐ene click chemistry to preparation of functional polyethylene with high molecular weight and high polar group content: Influence of thiol structure and vinyl type on reactivity

A series of functional polyethylenes have been simply and efficiently synthesized via the combination of regioselective ethylene/5‐vinyl‐2‐norbornene (VNB) copolymerization using [PhNC(CF₃)CHCO(Ph)]₂TiCl₂ catalyst and following ultraviolet light initiated thiol‐ene click reaction. On treatment of ethylene/VNB copolymer with different thiols including mercaptoethanol, 1‐thioglycerol, methyl mercaptoacetate, methyl mercaptopropionate, 2‐mercaptoethylamine, mercaptoacetic acid, and mercaptopropanoic acid, various polar groups have been successfully introduced into the polyethylene. Except 2‐mercaptoethylamine, the functionalizations are quite efficient with the degree of functionalization higher than 94%, which is independent of thiol structure and double bond content. The content of polar group in functional polyethylene can be tuned in a wide range of 0–30 mol %. Gel permeation chromatography profiles indicate all functional polyethylenes that have very high molecular weights (160–336 kg/mol) with homogeneous formation. Besides, systematic investigation of the influence of vinyl type and thiol structure on reactivity has been also carried out. By treatment of mercaptoethanol with different copolymers (ethylene/VNB, ethylene/5‐ethylidene‐2‐norbornene, and ethylene/dicyclopentadiene copolymer), the order of vinyl reactivity can be summarized as terminal > internal > cyclic double bond. For different thiols, the reactivity has the sequence of SHCH₂COOH > SHCH₂COOCH₃ > SHCH₂CH₂COOH > SHCH₂CH₂COOCH₃ > SHCH₂CH(OH)CH₂OH > SHCH₂CH₂OH > SHCH₂CH₂NH₂, which is depended on the solubility and the electron‐withdrawing inductive effect of polar group. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Vinyl esters: Low cytotoxicity monomers for the fabrication of biocompatible 3D scaffolds by lithography based additive manufacturing

Lithography based additive manufacturing technologies (AMT) like stereolithography or digital light processing have become appealing methods for the fabrication of 3D cellular scaffolds for tissue engineering and regenerative medicine. To circumvent the use of (meth)acrylate‐based photopolymers, that suffer from skin irritation and sometimes cytotoxicity, new monomers based on vinyl esters were prepared. In vitro cytotoxicity studies with osteoblast‐like cells proofed that monomers based on vinyl esters are significantly less cytotoxic than (meth)acrylates. Photoreactivity was followed by photo‐differential scanning calorimetry and the mechanical properties of the photocured materials were screened by nanoindentation. Conversion rates and indentation moduli between those of acrylate and methacrylate references could be observed. Furthermore, osteoblast‐like cells were successfully seeded onto polymer specimens. Finally, we were able to print a 3D test structure out of a vinyl ester‐based formulation by μ‐SLA with a layer thickness of 50 μm. For in vivo testing of vinyl esters these 3D scaffolds were implanted into surgical defects of the distal femoral bone of adult New Zealand white rabbits. The obtained histological results approved the excellent biocompatibility of vinyl esters. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2009     

N‐vinylcaprolactam‐based microgels for biomedical applications

Three types of poly(N‐vinylcaprolactam)‐based temperature‐sensitive microgel particles were synthesized by emulsion polymerization. The uptake of a model drug (calcein) into the particles was analyzed in terms of the amount of calcein absorbed and equilibrium–swelling degree. By incubating the microgels with primary neuronal cell cultures of embrionary rats, cell viability and biocompatibility tests were carried out. The results show that the driving force for the model drug to penetrate into the microgel particles is H‐bonding associations. On the other hand, cell death was microgel concentration and incubation period dependent. Microgels can be stored in a dried state and resuspended in water when necessary without changing their swelling–deswelling ability. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 1173–1181, 2010     

Enzyme-catalyzed transesterification of vinyl esters on cellulose solids

Enzyme-catalyzed transesterification of several cellulose solids in organic media have been investigated. Several protease enzymes were made soluble in organic media through ion-paired enzyme–surfactant complexes. Subtilisin Carsberg was found to be catalytically active in the transesterification of cellulose with vinyl propionate and vinyl acrylate in anhydrous pyridine. The ester carbonyl groups in acylated cellulose derivatives were confirmed by Fourier transform infrared spectroscopy. The surfaces of these cellulose derivatives became hydrophobic as demonstrated by increased water-contact angles. The enzyme-catalyzed transesterification was confirmed to regioselectively target the primary hydroxyl group of cellulose by reactions on specifically substituted cellulose. The cellulose esters from enzyme-catalyzed transesterification could be hydrolyzed partially by the same enzyme in aqueous media, and were thus biodegradable. Surface grafting of cellulose acrylate was demonstrated using azobisisobutyronitrile-initiated polymerization of acrylonitrile in dimethylformamide. Polyacrylonitrile (PAN)-g-cellulose shows a different thermal behavior from cellulose, homopolymer PAN, and PAN/cellulose blends. The grafted PAN on PAN-g-cellulose at a 16% grafting add-on is incapable of cyclization. © 2001 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 39: 1931–1939, 2001     

Mechanical properties of polymer composites based on commercial epoxy vinyl ester resin and glass fiber

The effect of the addition of methyl ethyl ketone peroxide (MEKP) and cobalt naphthenate (CoNaph) on the mechanical behavior of epoxy vinyl ester resin (EVER) laminates has been investigated by using a factorial experimental design, in which the MEKP and NaphCo contents were varied. Previous results showed that there is an interaction effect between the process variables analysed on the mechanical properties evaluated. It was also observed that the MEKP/CoNaph ratio affected the tensile behavior of the EVER/glass fiber composites.     

Vinylcarbonates and vinylcarbamates: Biocompatible monomers for radical photopolymerization

The last decade has seen a remarkable interest in the use of biocompatible and biodegradable polymers as scaffolds for tissue engineering. The fabrication of 3D scaffolds by lithography‐based additive manufacturing technology (AMT) represents an appealing approach. As poly(lactic acid), the state of the art biocompatible and biodegradable material, cannot be processed by these photopolymerization‐based techniques, it has so far been necessary to use selected (meth)acrylates. By developing new photopolymers based on vinyl carbonates and vinyl carbamates as a reactive group we have been able to avoid most of the disadvantages of classical (meth)acrylate‐based photopolymers. The new generation of biocompatible monomers show low cytotoxicity, have good storage stability, and are sufficiently photoreactive to be structured by lithography based AMT. The mechanical properties and rates of degradation of the polymers can be easily tuned over a broad range. Degradation results in the formation of nonacidic and nontoxic degradation products of low molecular weight that can be easily transported within the human body. Initial in vivo tests showed significant osseointegration of the 3D cellular scaffolds and no signs of implant rejection. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Comparative studies of polymer‐dispersed liquid crystal films via a thiol‐ene click reaction

In this work, the thiol‐ene click reaction is employed to fabricate polymer‐dispersed liquid crystal (PDLC) films by photoinitiated polymerization. The PDLC films are prepared by systematic variation of key conditions: variety and content of ‐ene monomer, liquid crystal (LC) content, curing time, and curing light intensity. We find that both the morphologies and electro‐optic properties of these films are adjustable. When increasing the length of alkyl main chain of ‐ene monomers, the driving voltages reduce, but in turn, the contrast ratio decreases. Increasing ‐ene monomer content raises the driving voltages as well as the response time, and the increase of LC content lowers the driving voltages but has a negative effect on the contrast ratio. The changes to the curing conditions (both curing time and UV light intensity) can be used to modify the driving voltages, response time, and contrast ratios of PDLC films. These comparative studies will elucidate new insights in commercial applications of intelligent PDLC films.     

Interpenetrating polymer networks of polyurethane and graft vinyl ester resin–polyurethane formed with diphenylmethane diisocyanate

For enhancing the compatibility and/or the interpenetration of the simultaneous interpenetrating networks (SINs) composed of polyurethane (PU) formed with uretonimine modified 4,4′‐diphenylmethane diisocyanate and vinyl ester resin (VER), a series of graft VERs consisting of different lengths of side chains were synthesized and characterized. It was found that there exists some limited short‐range order due to the strong hydrogen bonding in the graft VER network composed of butanol side chains (BO‐g‐VER). The graft VER network composed of poly(oxypropylene) (PPO) side chains (M_n: 200, 200‐g‐VER) showed compatible system, while the VER network consisting of longer PPO grafts (M_n: 390, 390‐g‐VER) exhibited microphase separated morphology. Based upon the DSC and FTIR measurements as well as the SEM and TEM observation, the lengths of side chains existing in graft VER network have great effect on the morphologies of PU/graft VER SINs. For PU/BO‐g‐VER SINs, there has been some interpenetration between the two networks because of the miscibility between the BO‐g‐VER network and the hard segments existing in the PU network. For PU/200‐g‐VER SINs, the good compatibility and/or the interpenetration between the two phases was observed, since the long‐range ordered structure of hard segments in PU phase was greatly suppressed, resulting from the excellent miscibility between the urethane groups as well as the PPO side chains existing in the 200‐g‐VER network and those in the PU network, respectively. Thus, the strong reinforcement effect of these two graft networks on the PU network and the excellent mechanical properties of the SIN systems were observed. However, the PU/390‐g‐VER SINs showed the complicated morphologies because of existing microphase‐ separated morphology of 390‐g‐VER network in itself. In this case, the enhancement effect of such a graft VER network on the PU network is limited. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 136–144, 2000     

Physically crosslinked poly(vinyl alcohol)-hydroxyethyl starch blend hydrogel membranes: Synthesis and characterization for biomedical applications

Poly(vinyl alcohol), PVA is a polymer of great importance because of its many appealing characteristics specifically for various pharmaceutical and biomedical applications. Physically crosslinked hydrogel membranes composed of different amounts of hydroxyethyl starch (HES) in (PVA) and ampicillin were prepared by applying freeze–thawing method. This freezing–thawing cycle was repeated for three consecutive cycles. Physicochemical properties of PVA–HES membrane gel such as gel fraction, swelling, morphology, elongation, tensile strength, and protein adsorption were investigated. Introducing HES into freeze–thawed PVA structure affected crystal size distribution of PVA; and hence physicochemical properties and morphological structure have been affected. Increased HES concentration decreased the gel fraction %, maximum strength and break elongation. Indeed it resulted into a significant incrementing of the swelling ability, amount of protein adsorption, broader pore size, and pore distribution of membrane morphological structure. Furthermore, an increase in HES concentration resulted in better and still lower thermal stability compared to virgin PVA and freeze–thawed PVA. The maximum weight loss of PVA–HES hydrogel membranes ranged between 18% and 60% according to HES content, after two days of degradation in phosphate buffer saline (PBS), which indicates they are biodegradable. Thus, PVA–HES hydrogel membranes containing ampicillin could be a novel approach for biomedical application e.g. wound dressing purposes.     

The influence of vinyl activating groups on β‐allyl sulfone‐based chain transfer agents for tough methacrylate networks

In radical polymerization of monofunctional monomers, addition fragmentation chain transfer (AFCT) agents are well known to regulate polymerization and yield polymers with lower molecular weights and narrower molecular weight distributions. Papers concerning bulk photopolymerization of monomer mixtures with AFCT agents are rarely found in literature. In this article, AFCT reagents based on β‐allyl sulfones with different vinyl activating groups were synthesized and compared. The compounds were tested in mono‐ and difunctional monomer systems providing information about the influence on photoreactivity, molecular weight, as well as thermal and mechanical properties of the resultant polymers. Where more potent activating groups (‐Ph, ‐CN) markedly influenced polymerization at lower concentrations, the AFCT reagent with an ester activating group reacted at a similar rate to the methacrylate monomer (C_T ≈ 1) and provided the best overall performance. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 1417‐1427     

Thiourethane‐based thiol‐ene high Tg networks: Preparation,thermal, mechanical,and physical properties

Thiourethane‐based thiol‐ene (TUTE) films were prepared from diisocyanates, tetrafunctional thiols and trienes. The incorporation of thiourethane linkages into the thiol‐ene networks results in TUTE films with high glass transition temperatures. Increases of T_g were achieved by aging at room temperature and annealing the UV cured films at 85 °C. The aged/annealed film with thiol prepared from isophorone diisocyanate and cured with a 10,080‐mJ/cm² radiant exposure had the highest DMA‐based glass transition temperature (108 °C) and a tan δ peak with a full width at half maximum (FWHM) of 22 °C, indicating a very uniform matrix structure. All of the initially prepared TUTE films exhibited good physical and mechanical properties based on pencil hardness, pendulum hardness, impact, and bending tests. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 5103–5111, 2007     

Simultaneous study of cure kinetics and rheology of montmorillonite/vinyl ester resin nanocomposites

In this work, the effect of quaternary ammonium salt containing nanoclay content (1–5 wt%) on phase morphology, rheology, cure kinetics, and mechanical properties of the vinyl ester resin (VER)‐based nanocomposites was studied. The morphological characterization including d‐spacing measurement, microscopy observation and phase‐height image processing were performed on the prepared nanocomposites using small angel X‐ray scattering (SAXS), transmission electron microscopy (TEM) and atomic force microscopy (AFM). According to the results obtained from these techniques, it was concluded that an intercalated morphology existed for all the nanocomposites. The kinetic analyses of the isothermal curing followed by storage modulus obtained from the rheometry experiments are shown to be an affective rheological characteristic to investigate the cure behavior of VER/clay nanocomposites. In addition, the most important finding regarding the effect of nanoclay on the cross‐linking behavior of VER systems lays on the chemisorption and physisorption of the reacting monomers and initiator molecules on the nanoclay platelets surface which is found to be responsible for the retardation of the cure reaction caused by organoclay. Eventually, the mechanical characterizations were performed through the tensile, flexural and impact analysis tests. In this case, a considerable improvement of the bulk mechanical responses such as tensile and flexural strengths and also the corresponding moduli were observed for the nanocomposites. Copyright © 2011 John Wiley & Sons, Ltd.