Visible light‐induced RAFT polymerization of methacrylates with benzaldehyde derivatives as organophotoredox catalysts

The benzaldehyde derivatives, such as 2,4‐dimethoxy benzaldehyde (PC1) and p‐anisaldehyde (PC2), were successfully used as photoredox catalysts (PCs) in combination with typical RAFT agent 4‐cyano‐4‐(phenylcarbonothioylthio)pentanoic acid (CTP) for the controlled photoinduced electron transfer RAFT polymerization (PET‐RAFT) of methyl methacrylate (MMA) and benzyl methacrylate (BnMA) at room temperature. The kinetics of the polymerizations showed first order with respect to monomer conversions. Besides, the average number molecular weights (M_n) of the produced polymers increased linearly with the monomer conversions and kept relatively narrow polydispersity (PDI = M_w/M_n). For example, the M_n of PMMA increased from about 3400 to 17,300 g mol⁻¹ with the increasing in monomer conversion from 11% to 85%, and the PDI maintained around 1.36. The living features of polymerizations with the PC1 and PC2 as catalysts have also been further supported by chain extension and synthesis of PMMA‐b‐PBnMA diblock copolymer. As a result, the simplicity and efficiency of benzaldehyde derivatives catalyzed PET‐RAFT polymerization have been demonstrated under mild conditions. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 229–236     

Encapsulants for light‐emitting diodes from visible light‐cured epoxy monomers

During the last decade, light‐emitting diodes (LEDs) have replaced incandescent, fluorescent, and neon lamps due to their ability to produce high luminosity at low currents and voltages. LEDs are currently encapsulated by thermally curable epoxy resins. However, long periods of curing at high temperature result in high consumption of energy and require stringent process control to avoid failure of the devices. In addition, the thermal cure results in yellowing of the encapsulant, which decreases the efficiency of the LED. In recent years, photoinitiated polymerization has received much interest as it congregates a wide range of economic and ecological benefits. Cationic photoinitiators, such as diaryliodonium salts, generate Brønsted acid in situ, which initiates polymerization. The process can be triggered on demand by irradiating the mixture with light. Results from the present research reveal that cycloaliphatic epoxy monomers, photoactivated with an iodonium salt and Camphorquinone, polymerize readily under visible light irradiation (470 nm) in the absence of external heating. The partial replacement of cycloaliphatic epoxy with aromatic diglycidyl ether of bisphenol‐A (DGEBA) is an effective means of improving the refractive index of the material and consequently the efficiency of the photoemission. Visible light polymerization of DGEBA pure proceeds at a slow rate; however, it is enhanced by the increase in temperature during the polymerization of the highly reactive cycloaliphatic monomer. From results obtained in the present research, it may be concluded that visible light polymerization of epoxy monomers is a promising route for the processing of LED encapsulants. Copyright © 2013 John Wiley & Sons, Ltd.     

Visible light‐induced controlled radical polymerization of methacrylates with perfluoroalkyl iodide as the initiator in conjugation with a photoredox catalyst fac‐[Ir(ppy)]3

A new visible light‐induced controlled radical polymerization of methacrylate with perfluoro‐1‐iodohexane (CF₃(CF₂)₅I) as the initiator in the presence of a photoredox catalyst (fac‐[Ir(ppy)₃]) was developed. Mechanistically, a photoexcited fac‐[Ir(ppy)₃]* complex reacted with dormant C‐I species to generate the chain propagating radical and Ir^IVI complex, which could be reversibly reduced by the propagating radical. The molecular weight (M_n) and the corresponding distribution index (M_w/M_n = 1.4) were controlled in the polymerization of methyl methacrylate (MMA). For the polymerization of functional monomers, such as glycidyl methacrylate (GMA) and trifluoroethyl methacrylate, their monomer conversions could be up to 96 and 94%, respectively. No polymerization reaction took place without external light stimulation, indicating that the system was an ideal photo “on?off” switchable system. Furthermore, a clean diblock copolymer PMMA‐b‐PGMA was successfully synthesized with PMMA‐I as the macroinitiator. With CF₃(CF₂)₅I as the initiator, short CF₃(CF₂)₅? group tags were introduced on the produced polymer chains. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 3283–3291     

Visible light‐emitting diode‐sensitive thioxanthone derivatives used in versatile photoinitiating systems for photopolymerizations

Novel thioxanthone (TX) derivatives are used as versatile photoinitiators upon visible light‐emitting diode (LED; e.g., 405, 425, and 450 nm) exposure. The mechanisms for the photochemical generation of reactive species (i.e., cations and free radicals) produced from photoinitiating systems based on the photoinitiator and an iodonium salt, tris(trimethylsilyl)silane, or an amine, were studied by UV–vis spectroscopy, fluorescence, cyclic voltammetry, steady‐state photolysis, and electron spin resonance spin‐trapping techniques. The reactive species are particularly efficient for cationic, free radical, hybrid, and thiol‐ene photopolymerizations upon LED exposure. The optimized photoinitiating systems exhibit higher efficiency than those of reference systems (i.e., isopropyl TX‐based photoinitiating systems), especially in the visible range. According to their beneficial features, these photoinitiating systems have considerable potential in photocuring applications. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 4037–4045     

Visible light-induced synthesis of polysulfone-based graft copolymers by a grafting from approach

The synthesis of polysulfone (PSU) graft copolymers by a two-step “grafting from” approach is described. First, a chlorofunctional PSU (PSU-Cl) is formed via chloromethylation of a commercial PSU. The formed polymers are used macroinitiator for the dimanganese decacarbonyl assisted free-radical polymerization of tert-butyl acrylate, methyl methacrylate, and styrene to give the desired graft copolymers. Moreover, amphiphilic graft copolymers are also formed via posthydrolyzation of poly(tert-butyl acrylate) containing graft copolymers. The intermediates at various stages and the ultimate graft copolymers are characterized by various analysis techniques. © 2020 Wiley Periodicals, Inc. J. Polym. Sci. 2020 , 58, 412–416     

Visible and long‐wavelength photoinitiated cationic polymerization

A new system for efficiently carrying out cationic photopolymerizations with visible and long‐wavelength UV light is described. This system is based on the principle that certain onium salt cationic photoinitiators can be reduced by free radicals produced by the hydrogen abstraction reactions of photoexcited ketones. Thus, when camphorquinone, benzil, 2‐isopropylthioxanthone, and 2‐ethylanthraquinone are irradiated in the presence of a monomer that can serve as a hydrogen donor, the resulting monomer‐bound radical rapidly reduces a diaryliodonium salt or a dialkylphenacylsulfonium salt, and the resulting monomer‐centered cations initiate the polymerizations of epoxides, vinyl ethers, and heterocyclic compounds. Onium salts with high reduction potentials, such as triarylsulfonium salts, do not undergo sensitization by this new system. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 39: 343–356, 2001     

Copper and iron complexes as visible‐light‐sensitive photoinitiators of polymerization

The utilization of visible lights for the fabrication of polymeric materials is recognized as a promising and environmentally friendly approach. This process relies on the photochemical generation of reactive species (e.g., radicals, radical cations, or cations) from well‐designed photoinitiators (PIs) or photoinitiating systems (PISs) to initiate the polymerization reactions of different monomers (acrylates, methacrylates, epoxides, and vinyl ethers). In spite of the fact that metal complexes such as ruthenium‐ or iridium‐based complexes have found applications in organic and polymer synthesis, the search of other low‐cost metal‐based complexes as PISs is emerging and attracting increasing attentions. Particularly, the concept of the photoredox catalysis has appeared recently as a unique tool for polymer synthesis upon soft conditions (use of light emitting diodes and household lamp). This highlight focuses on recently designed copper and iron complexes as PI catalysts in the application of photoinduced polymerizations (radical, cationic, interpenetrated polymer networks, and thiol‐ene) or controlled radical polymerization under visible light irradiation. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 2673–2684     

Atom‐transfer radical grafting polymerization of 2‐methacryloyloxyethyl phosphorylcholine from silicon wafer surfaces

2‐Methacryloyloxyethyl phosphorylcholine (MPC), a biomimetic monomer, was grafted from silicon wafer surfaces at room temperature by combining self‐assembly of initiator and surface‐initiated atom transfer radical polymerization. Two methods were used to control the grafting process. One was to add free initiator to the reaction system; the other was to add excess deactivator. The grafting densities up to 0.3 chains/nm² were obtained. The surface thickness increased linearly with MPC conversion. The thickness depended on catalyst and monomer concentrations, as well as activator/deactivator ratio. Poly(MPC) layers of >100 nm thick were obtained by optimizing the polymerization conditions. A second block of either poly(MPC) or poly[2‐(dimethylamino)ethyl methacrylate] was also grown from the grafted poly(MPC), demonstrating the system livingness. X‐ray photoelectron spectroscopy was used to examine the surface chemical compositions showed good agreement with the theoretical values. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 2931–2942, 2004     

Living radical photopolymerization induced grafting on thiol–ene based substrates

The formation of reactive substrates with iniferter‐mediated living radical photopolymerization is a powerful technique for surface modification, which can readily be used to facilitate the incorporation of a variety of surface functionalities. In this research, the photopolymerization kinetics of novel bulk thiol–ene systems have been compared with those of typical acrylate and methacrylate systems when polymerized in the presence of the photoiniferter p‐xylene bis(N,N‐diethyl dithiocarbamate) (XDT). In the presence of XDT, the thiol–ene systems photopolymerize more quickly than the traditional acrylate and methacrylate systems by one to two orders of magnitude. Fourier transform infrared spectroscopy has been used to monitor the photografting kinetics of various monomers on dithiocarbamate‐functionalized surfaces. Furthermore, this technique has been used to evaluate surface‐initiation kinetics and to emphasize the influence of bulk substrate properties on grafting kinetics. Finally, photopatterning has been demonstrated on a dithiocarbamate‐incorporated thiol–ene substrate with conventional photolithographic techniques. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 2134–2144, 2005     

Facile synthesis of well‐defined pH‐liable Schiff‐base‐type photosensitive polymers via visible‐light‐activated ambient temperature RAFT polymerization

Inspired by the structure character and photosensitive molecular mechanism of natural rhodopsin or bacteriorhodopsin, a novel pH‐liable photosensitive polymer whose chromophores directly bind with Schiff base linkages was designed. Accordingly, 2‐((3‐phenylallylidene)amino)ethyl methacrylate (PAAEMA), 2‐((3‐(4‐fluorophenyl)allylidene)amino)ethyl methacrylate (FPAAEMA), and 2‐((3‐(4‐methoxyphenyl)allylidene)amino)ethyl methacrylate (MPAAEMA) monomers were synthesized. These monomers were polymerized upon irradiating with mild visible light at ambient temperature. The results indicate that Schiff base linkages of these monomers are stable under such mild polymerizing conditions, and the weak absorption of dithioester functionalities in the visible wave range leads to a rapid and well‐controlled RAFT polymerization. The polymerization rate slows down but initialization period significantly shortens on increasing the feed molar ratio of monomer. The pendant electron‐withdrawing‐group‐substituted chromophore improves the reactivity of monomer, but electron‐donating‐group‐substituted chromophore significantly inactivates monomer. Glycidyl methacrylate (GMA) may well incorporate in this polymer via RAFT random copolymerization of PAAEMA and GMA monomers due to the comparable reactivity ratios of this monomer pair. PolyMPAAEMA exhibits reversible fluorescence emitting or quenching upon deprotonating or protonating the Schiff base linkages. This fluorescence behavior may be of interest in the fabrication of pH‐responsive photosensors, light modulators, or actuators. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 6668–6681, 2009     

Thermally induced fixed diradical generation on solid supports for surface‐initiated polymerization

A method is presented for generation of all surface‐bound radicals on solid polymer surfaces. Thus, secondary amide group of newly synthesized crosslinking comonomer, methacryloyloxyethyl methacrylamide was determined as versatile precursor for generation fixed diradicals on solid microspheres, obtained by copolymerization with methyl methacrylate (MMA) in aqueous suspension. Nitrosoation of the secondary amide groups on the microbeads and followed thermolysis above 90 °C was demonstrated to give surface‐bound radicals, capable of initiating polymerization of vinyl monomers, such as; styrene, MMA, N‐vinyl formamide, and N‐vinyl, 2‐pyrrolidone, as evidenced by H NMR, Fourier transform infrared, thermogravimetric analysis, and differential scanning calorimeter techniques. Appreciable grafting yields (55.1%–286.1%) and low free‐homopolymer formation (7.2%–19.7%) were noted within 6 h of the grafting at 100 °C in each case. This strategy involving the use of amide functional crosslinker seemed to be generally applicable to generate surface‐bound radicals for surface‐initiated polymerization from various solid substrates. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Nitroxide decomposition: Implications toward nitroxide design for applications in living free‐radical polymerization

Nitroxides bearing an α‐hydrogen decompose upon heating in a bimolecular reaction. A new mechanism is proposed for the decomposition of t‐butylisopropylphenyl nitroxide (TIPNO) involving the formation of a head‐to‐tail dimer, single electron transfer to form an oxammonium salt, epimerization to the corresponding nitrone, and elimination to form a conjugated oxime. This mechanism may provide insights into designing new nitroxides for use in controlled polymerization. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 697–717, 2006     

A copper‐based reverse atom‐transfer radical polymerization process for the living radical polymerization of polyacrylonitrile

The reverse atom‐transfer radical polymerization (RATRP) technique using CuCl₂/2,2′‐bipyridine (bipy) complex as a catalyst was applied to the living radical polymerization of acrylonitrile (AN). A hexasubstituted ethane thermal iniferter, diethyl 2,3‐dicyano‐2,3‐diphenylsuccinate (DCDPS), was firstly used as the initiator in this copper‐based RATRP initiation system. A CuCl₂ to bipy ratio of 0.5 not only gives the best control of molecular weight and its distribution, but also provides rather rapid reaction rate. The rate of polymerization increases with increasing the polymerization temperature, and the apparent activation energy was calculated to be 57.4 kJ mol^?1. Because the polymers obtained were end‐functionalized by chlorine atoms, they were used as macroinitiators to proceed the chain extension polymerization in the presence of CuCl/bipy catalyst system via a conventional ATRP process. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 226–231, 2006     

New selenium‐based iniferter agent for living free radical polymerization of styrene under UV irradiation

P,P‐Diphenyl phosphinodiselenoic acid benzyl ester was synthesized and used as a mediator for the polymerization of styrene under UV–vis irradiation. Moderately controlled evidence was found: linear polymerization kinetics, linear evolution of molecular weight with monomer conversion, and relatively narrow molecular weight distribution (1.5–2.0). The structure of the obtained polymers was characterized using NMR and oxidative eliminaton. Based on polymerization results, an iniferter mechanism was proposed for the current polymerization system. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Well‐controlled RAFT polymerization initiated by recyclable surface‐modified Nb(OH)5 nanoparticles under visible light irradiation

A recyclable solid‐state photoinitiator based on the surface modified niobium hydroxide is prepared and successfully introduces into reversible addition–fragmentation chain transfer (RAFT) polymerization under visible light illumination. It is revealed by gel permeation chromatography analysis that well‐defined polymers with controlled molecular weight and narrow polydispersity index can be achieved when the feed ratio of photoinitiator to the RAFT agent was controlled properly. It is also found that the polymerization is highly responsive to external stimulus and when light is removed from the system polymerization stops almost immediately. In addition, the photoinitiator can be recycled and reused to initiate the polymerization for many times without significant decrease of initiation efficiency. At last, the mechanism for the light initiated polymerization is proposed to illuminate how the initiation and chain propagation proceed. This facile, green and visible light initiation methodology could attract more and more applications in polymer science with the depletion of fossil energy. A recyclable solid‐state photoinitiator based on the surface modified niobium hydroxide was prepared and successfully introduced into reversible addition–fragmentation chain transfer (RAFT) polymerization under visible light illumination. It is revealed that well‐defined polymers with controlled molecular weight and narrow polydispersity index (PDI) can be achieved when the feed ratio of photoinitiator to the RAFT agent was controlled properly. It is also found that the polymerization is highly responsive to light initiation. In addition, the photoinitiator can be recycled and reused to initiate the polymerization for many times without significant decrease of initiation efficiency. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 2715–2724     

Optimal irradiation wavelength in iniferter‐based photocontrolled radical polymerization

In iniferter‐based photocontrolled radical polymerization optimal irradiation wavelength was examined for precise molecular design of star vectors, which can function as high‐performance gene carriers. Monochromatic light in the range from 330 to 400 nm with the interval of about 10 nm was irradiated to tetrafunctional iniferter, 1,2,4,5‐tetrakis(N,N‐diethyldithiocarbamylmethyl)benzene, in the presence of N,N‐dimethyaminopropylacrylamide (DMAPAAm), as a model monomer, in toluene. In all wavelengths tetrabranched polymers were produced except for 400‐nm‐irradiation. The highest conversion reaching to about 35% was observed at the wavelength of 370 nm after only 40 min of irradiation. There was no further increase in conversion by combination with another two wavelengths. HPLC analysis and NMR spectra showed that the polymerization at the optimal wavelength of 370 nm was occurred in a living manner with the ability to control the chain length (from about 5000 to 40,000) having very narrow polydispersity (about 1.6) by changing of the irradiation time, the intensity, and the monomer concentration. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 4505–4512, 2008     

Surface‐initiated atom transfer radical polymerization grafting of poly(2,2,2‐trifluoroethyl methacrylate) from flat silicon wafer surfaces

Poly(2,2,2‐trifluoroethyl methacrylate) (PTFEMA), a partially fluorinated polymer, was directly grafted from silicon wafer surfaces by a surface‐initiated atom‐transfer radical polymerization (ATRP). The polymer layer thickness increased linearly with monomer conversion and molecular weight of free polymers in solution. The thickness was mainly determined by the experimental conditions such as activator/deactivator ratio, monomer/catalyst ratio, and monomer concentration. PTFEMA layers of more than 100‐nm thick were obtained. The grafted PTFEMA chains were “living” and allowed the extension of a second block of PMMA. X‐ray photoelectron spectroscopy study showed that the chemical compositions at the surfaces agreed well with their theoretical values. A novel surface‐attachable difunctional initiator was also synthesized and applied to the grafting of PTFEMA. The grafting density was doubled using this difunctional initiator, from 0.48 to 0.86 chains/nm². © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 1252–1262, 2006     

Synthesis of polymeric core–shell particles using surface‐initiated living free‐radical polymerization

An easy and novel approach to the synthesis of functionalized nanostructured polymeric particles is reported. The surfactant‐free emulsion polymerization of methyl methacrylate in the presence of the crosslinking reagent 2‐ethyl‐2‐(hydroxy methyl)‐1,3‐propanediol trimethacrylate was used to in situ crosslink colloid micelles to produce stable, crosslinked polymeric particles (diameter size ～ 100–300 nm). A functionalized methacrylate monomer, 2‐methacryloxyethyl‐2′‐bromoisobutyrate, containing a dormant atom transfer radical polymerization (ATRP) living free‐radical initiator, which is termed an inimer (initiator/monomer), was added to the solution during the polymerization to functionalize the surface of the particles with ATRP initiator groups. The surface‐initiated ATRP of different monomers was then carried out to produce core–shell‐type polymeric nanostructures. This versatile technique can be easily employed for the design of a wide variety of polymeric shells surrounding a crosslinked core while keeping good control over the sizes of the nanostructures. The particles were characterized with scanning electron microscopy, transmission electron microscopy, optical microscopy, dynamic light scattering, and Raman spectroscopy. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 1575–1584, 2007     

Some novel accelerating agents for nitroxide‐mediated living free‐radical polymerization

Malononitrile (MN), trifluoroacetic acid anhydride, acetylacetone, acetoacetic ester, and diethyl malonate have been identified as novel rate‐accelerating additives for nitroxide‐mediated living free‐radical polymerization. Among these additives, MN has the greatest accelerating effect. Adding MN at an MN/2,2,6,6‐tetramethylpiperidine‐oxyl (TEMPO) molar ratio of 4.0 results in a nearly 20 times higher rate of polymerization of styrene (St), and adding MN at an MN/TEMPO molar ratio of 2.5 results in a nearly 15 times higher rate of copolymerization of St and methyl methacrylate. The polymerization of St proceeds in a living fashion, as indicated by the increase in the molecular weight with time and conversion and the relatively low polydispersity. The polymerization rate of St is so quick that the conversion reaches 70% within 1 h at 125 °C when the molar ratio of MN to TEMPO is 4:1. Moreover, the reaction temperature can be reduced to 110 °C. A possible explanation for this effect is that the formation of hydrogen bonds between the MN and TEMPO moiety weakens the C? ON bond at the end of the polymer chain. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 5246–5256, 2005