Step-growth Diels–Alder (DA) networks using furan and maleimide groups are particularly useful in forming thermally remendable crosslinked polymers, due to the dramatic shift in equilibrium over a relatively low temperature range as compared with other diene-dienophile pairs. However, the efficient healing observed in these materials at high temperature is directly tied to their ability to depolymerize and flow, and thermal treatment often results in deformation of the original shape. To overcome this limitation, a hybrid network material is developed, which consists of orthogonal Diels–Alder and polyurethane networks. Both step-growth networks form simultaneously at elevated temperature without the presence of a catalyst. At high temperatures, the Diels–Alder network depolymerizes and flows into fractures through capillary action, while the polyurethane serves as a scaffold to maintain the overall shape of the sample. The DA network then repolymerizes at lower temperatures, creating a crosslinked, scar-like “patch” throughout the crack. This healing process is repeatable without concern of monomer depletion. During heating through the glass transition, a shape memory “assist” is observed, which reverses some of the localized damage by bringing broken edges closer together. Samples are repeatedly damaged and then healed through temperature cycling, as evidenced through tensile fracture tests and electrochemical conductivity tests.

Synthetic polymer approaches generally lack the ability to control the primary sequence, with sequence control referred to as the holy grail. Two click chemistry reactions were now combined to form nucleobase-containing sequence-controlled polymers in simple polymerization reactions. Two distinct approaches are used to form these click nucleic acid (CNA) polymers. These approaches employ thiol–ene and thiol-Michael reactions to form homopolymers of a single nucleobase (e.g., poly(A)_n) or homopolymers of specific repeating nucleobase sequences (e.g., poly(ATC)_n). Furthermore, the incorporation of monofunctional thiol-terminated polymers into the polymerization system enables the preparation of multiblock copolymers in a single reaction vessel; the length of the diblock copolymer can be tuned by the stoichiometric ratio and/or the monomer functionality. These polymers are also used for organogel formation where complementary CNA-based polymers form reversible crosslinks.

Synthetic polymer approaches generally lack the ability to control the primary sequence, with sequence control referred to as the holy grail. Two click chemistry reactions were now combined to form nucleobase-containing sequence-controlled polymers in simple polymerization reactions. Two distinct approaches are used to form these click nucleic acid (CNA) polymers. These approaches employ thiol–ene and thiol-Michael reactions to form homopolymers of a single nucleobase (e.g., poly(A)_n) or homopolymers of specific repeating nucleobase sequences (e.g., poly(ATC)_n). Furthermore, the incorporation of monofunctional thiol-terminated polymers into the polymerization system enables the preparation of multiblock copolymers in a single reaction vessel; the length of the diblock copolymer can be tuned by the stoichiometric ratio and/or the monomer functionality. These polymers are also used for organogel formation where complementary CNA-based polymers form reversible crosslinks.

Despite originating only a little more than a decade ago, click chemistry has become one of the most powerful paradigms in materials science, synthesis, and modification. By developing and implementing simple, robust chemistries that do not require difficult separations or harsh conditions, the ability to form, modify, and control the structure of materials on various length scales has become more broadly available to those in the materials science community. As such, click chemistry has seen broad implementation in polymer functionalization, surface modification, block copolymer and dendrimer synthesis, biomaterials fabrication, biofunctionalization, and in many other areas of materials science. Here, the basic reactions, approaches, and applications of click chemistry in materials science are highlighted, and a brief look is taken into the future enabling developments in this field.

The effects of the addition of small amounts of multifunctional monomers that contain functional groups capable of undergoing addition-fragmentation during radical polymerizations are investigated. Specifically, up to 6 wt % of phenyl trithiocarbonate (TTC)-containing diacrylate was added to conventional thiol-multiacrylate photopolymerizations where its addition led to up to 60% reduction in polymerization-induced shrinkage stress. The higher levels of TTC achieve the lowest stress though they also significantly depress the polymerization rate. Using up to 0.5 wt % phenyl TTC successfully reduces the stress by nearly 20%, demonstrating the effectiveness of the phenyl TTC, while minimizing the influence that the RAFT activity of the TTC unit has on the polymerization rate. When the polymerization rates of the TTC-containing resins are increased by changing the incident light intensity, complete acrylate conversion is achieved and the stress remains up to 40% lower in the TTC-containing resins. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014, 52, 1315–1321

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

There are distinct advantages to designing polymer systems that afford two distinct sets of material properties– an intermediate polymer that would enable optimum handling and processing of the material, while maintaining the ability to tune in different, final polymer properties that enable the optimal functioning of the material. In this study, by designing a series of non-stoichiometric thiol-acrylate systems, a polymer network is initially formed via a base catalyzed Michael addition reaction that proceeds stoichiometrically via the thiol-acrylate “click” reaction. This self-limiting reaction results in a polymer with excess acrylic functional groups within the network. At a later point in time, the photoinitiated, free radical polymerization of the excess acrylic functional groups results in a highly crosslinked, robust material system. These two stage reactive thiol-acrylate networks that have intermediate stage rubbery moduli and glass transition temperatures that range from 0.5 MPa and -10 °C to 22 MPa and 22 °C, respectively, are formulated and characterized. The same polymer networks can then attain glass transition temperatures that range from 5 °C to 195 °C and rubbery moduli of up to 200 MPa after the subsequent photocuring stage. The two stage reactive networks formed by varying the stoichiometric ratios of the thiol and acrylate monomers were shown to perform as substrates for three specific applications: shape memory polymers, impression materials, and as optical materials for writing refractive index patterns.

3D structures are written and developed in a crosslinked polymer initially formed by a Diels–Alder reaction. Unlike conventional liquid resists, small features cannot sediment, as the reversible crosslinks function as a support, and the modulus of the material is in the MPa range at room temperature. The support structure, however, can be easily removed by heating the material, and depolymerizing the polymer into a mixture of low-viscosity monomers. Complex shapes are written into the polymer network using two-photon techniques to spatially control the photoinitiation and subsequent thiol–ene reaction to selectively convert the Diels–Alder adducts into irreversible crosslinks.

The trithiocarbonate 1a reduces the volumetric shrinkage stress in crosslinked multi(meth)acrylate networks by promoting a reversible, free-radical-mediated network rearrangement that enables network adaptation and stress relaxation. Addition of 1a or 1b into a dimethacrylate system is examined by FT-IR. The polymerization rate is reduced in samples containing 1a, indicating a changed polymerization mechanism. The volumetric shrinkage stress is reduced by more than 50% compared to a pure dimethacrylate system with the addition of as little as 2 wt% of 1a, while maintaining the favorable mechanical properties of the methacrylate-crosslinked networks. No synthetic modification of the methacrylate monomer units is needed, allowing for adaptation to almost any radically polymerized system.

Three types of linear thiol-functionalized siloxane oligomers and three types of ene-functionalized oligomers were synthesized and subsequently photopolymerized. Within each type of thiol-functionalized oligomer, the ratio of mercaptan repeat units to nonreactive phenyl repeat units was varied to manipulate both the crosslink density and the degree of secondary interactions through π–π stacking. Similarly, the repeat units of the three ene-functionalized oligomers are composed of allyl-functional monomers, benzene-functional monomers, and octyl-functional monomers in varying ratios of benzene:octyl but with a constant fraction of allyl moieties. The structural composition of the siloxane oligomers plays a pivotal role in the observed material properties of networks formed through thiol–ene photopolymerization. Networks with a high concentration of thiol functionalities exhibit higher rubbery moduli, ultimate strengths, and Young's moduli than networks with lower thiol concentrations. Moreover, the concentration of functionalities capable of participating in secondary interactions via hydrogen bonding or π–π stacking directly impacts the network glass transition temperature and elasticity. The combination of low crosslink density and high secondary interactions produces networks with the greatest toughness. Finally, the fraction of octyl repeats correlates with the hydrophobic nature of the network. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012

Following Sharpless′ visionary characterization of several idealized reactions as click reactions, the materials science and synthetic chemistry communities have pursued numerous routes toward the identification and implementation of these click reactions. Herein, we review the radical-mediated thiol–ene reaction as one such click reaction. This reaction has all the desirable features of a click reaction, being highly efficient, simple to execute with no side products and proceeding rapidly to high yield. Further, the thiol–ene reaction is most frequently photoinitiated, particularly for photopolymerizations resulting in highly uniform polymer networks, promoting unique capabilities related to spatial and temporal control of the click reaction. The reaction mechanism and its implementation in various synthetic methodologies, biofunctionalization, surface and polymer modification, and polymerization are all reviewed.

Nach Sharpless’ visionärer Charakterisierung verschiedener idealisierter Reaktionen als Klick-Reaktionen hat man innerhalb der Materialwissenschaften und Synthesechemie große Anstrengungen unternommen, um solche Reaktionen zu finden und zu implementieren. In diesem Aufsatz diskutieren wir die radikalvermittelte Thiol-En-Reaktion, die über all die Merkmale einer Klick-Reaktion verfügt: hohe Effizienz, einfache Durchführung, keine Nebenprodukte, hohe Reaktionsgeschwindigkeiten, hohe Ausbeuten. Darüber hinaus besteht die Möglichkeit, die Thiol-En-Reaktion photoinitiiert auszuführen, was insbesondere für Photopolymerisationen zur Synthese extrem einheitlicher Polymernetzwerke genutzt wird. Der Reaktionsmechanismus wird nach dem aktuellen Kenntnisstand erläutert, und zentrale Anwendungen der Thiol-En-Reaktion in der Material- und Molekülsynthese, der Biofunktionalisierung, der Polymersynthese und der Oberflächen- und Polymermodifizierung werden zusammengefasst.

Thiol-isocyanate-acrylate ternary networks were formed by the combination of thiol-isocyanate coupling, thiol-acrylate Michael addition, and acrylate homopolymerization. This hybrid polymerization reaction sequence was preferentially controlled by using phosphine catalyst systems in combination with photolysis. The reaction kinetics of the phosphine/acrylate thiol-isocyanate coupling reactions were systematically investigated by evaluating model, small molecule reactions. The thiol-isocyanate reaction was completed within 1 min while the thiol-acrylate Michael addition reaction required ∼10 min. Both thiol-isocyanate coupling and thiol-acrylate Michael addition reactions involving two-step anionic processes were found to be both quantitative and efficient. However, the thiol-isocyanate coupling reaction was much more rapid than the thiol-acrylate Michael addition, promoting initial selectivity of the thiol-isocyanate reaction in a medium containing thiol, isocyanate, and acrylate functional groups. Films were prepared from thiol-isocyanate-acrylate ternary mixtures using 2-acryloyloxyethylisocyanate and di-, tri-, and tetra-functional thiols. The sequential thiol-isocyanate, thiol-acrylate, and acrylate homopolymerization reactions were monitored by infrared spectroscopy during film formation, whereas thermal and mechanical properties of the films were evaluated as a function of the chemical composition following polymerization. The results indicate that the network structures and material properties are tunable over a wide range of properties (T_g ∼ 14–100 °C, FWHM ∼ 8–46 °C), while maintaining nearly quantitative reactions, simply by controlling the component compositions. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 3255–3264, 2010

In this study, vinyl ester monomers were synthesized by an amine catalyzed Michael addition reaction between a multifunctional thiol and the acrylate double bond of vinyl acrylate. The copolymerization behavior of both methacrylate/vinyl ester and acrylate/vinyl ester systems was studied with near-infrared spectroscopy. In acrylate/vinyl ester systems, the acrylate groups polymerize faster than the vinyl ester groups resulting in an overall conversion of 80% for acrylate double bonds in the acrylate/vinyl ester system relative to only 50% in the bulk acrylate system. In the methacrylate/vinyl ester systems, the difference in reactivity is even more pronounced resulting in two distinguishable polymerization regimes, one dominated by methacrylate polymerization and a second dominated by vinyl ester polymerization. A faster polymerization rate and higher overall conversion of the methacrylate double bonds is thus achieved relative to polymerization of the pure methacrylate system. The methacrylate conversion in the methacrylate/vinyl ester system is near 100% compared to only ∼60% in the pure methacrylate system. Utilizing hydrophilic vinyl ester and hydrophobic methacrylate monomers, polymerization-induced phase separation is observed. The phase separated domain size is in the order of ∼1 μm under the polymerization conditions. The phase separated domains become larger and more distinct with slower polymerization and correspondingly increased time for diffusion. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 2509–2517, 2009

A visible light photoinitiator, eosin, in combination with a tertiary amine coinitiator is found to initiate polymerization despite the presence of at least 1000-fold excess dissolved oxygen, which functions as an inhibitor of radical polymerizations. Additionally, 0.4 μM eosin is able to overcome 100-fold excess (40 μM) 2,2,6,6-Tetramethyl-1-piperidinyloxy (TEMPO) inhibitor, initiating polymerization after only a 2 min inhibition period. In contrast, 40 μM Irgacure-2959, a standard cleavage-type initiator, is unable to overcome even an equivalent amount of inhibitor (40 μM TEMPO). Through additional comparisons of these two initiation systems, a reaction mechanism is developed which is consistent with the kinetic data and provides an explanation for eosin's relative insensitivity to oxygen, TEMPO, and other inhibitors. A cyclic mechanism is proposed in which semireduced eosin radicals react by disproportionation with radical inhibitors and radical intermediates in the inhibition process to regenerate eosin and effectively consume inhibitor. In behavior similar to that of eosin, rose bengal, fluorescein, and riboflavin are also found to initiate polymerization despite the presence of excess TEMPO, indicating that cyclic regeneration likely enhances the photoinitiation kinetics of many dye photosensitizers. Selection of such dye initiation systems constitutes a valuable strategy for alleviating inhibitory effects in radical polymerizations. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 6083–6094, 2009

This study investigates the formation of linear polymer grafts using thiol-acrylate conjugate addition reactions on nanoparticle surfaces. Silica nanoparticles were first modified with an amine functionality, followed by the attachment of a photocleavable acrylate. Dithiol-diacrylate films were attached to the particles through the surface acrylate groups at various stoichiometric ratios of thiol to acrylate by conducting amine-catalyzed conjugate addition polymerizations. The particles were then exposed to UV light to release the grafted polymer by photocleavage. The cleaved, grafted polymers were analyzed using infrared spectroscopy and gel permeation chromatography and compared to polymers formed in the bulk, which remained unattached to the particles. The measured number and weight average molecular weights were similar for both polymer types within experimental error and increased from 2000 to 5000 g/mol and 4000 to 10,000 g/mol, respectively, as the ratio of limiting to excess functionality increased from 0.8 to 1. Both number and weight average molecular weights followed the trend of step growth polymers with the highest molecular weight achieved for stoichiometric monomeric mixtures. Surface coverage of the nanoparticles was estimated using the molecular weight and thermogravimetric data and was found to be uniform (∼0.15 chains/nm²) irrespective of the stoichiometry of the reacting monomers. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 6896–6906, 2008