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     

Visible‐Light‐Driven CO2 Reduction by Mesoporous Carbon Nitride Modified with Polymeric Cobalt Phthalocyanine

The integration of molecular catalysts with low‐cost, solid light absorbers presents a promising strategy to construct catalysts for the generation of solar fuels. Here, we report a photocatalyst for CO₂ reduction that consists of a polymeric cobalt phthalocyanine catalyst (CoPPc) coupled with mesoporous carbon nitride (mpg‐CN_x) as the photosensitizer. This precious‐metal‐free hybrid catalyst selectively converts CO₂ to CO in organic solvents under UV/Vis light (AM 1.5G, 100 mW cm^?2, λ>300 nm) with a cobalt‐based turnover number of 90 for CO after 60 h. Notably, the photocatalyst retains 60 % CO evolution activity under visible light irradiation (λ>400 nm) and displays moderate water tolerance. The in situ polymerization of the phthalocyanine allows control of catalyst loading and is key for achieving photocatalytic CO₂ conversion.     

Photocontrolled Iodine‐Mediated Reversible‐Deactivation Radical Polymerization: Solution Polymerization of Methacrylates by Irradiation with NIR LED Light

Herein, near‐infrared (NIR) photocontrolled iodide‐mediated reversible‐deactivation radical polymerization (RDRP) of methacrylates, without an external photocatalyst, was developed using an alkyl iodide (e.g., 2‐iodo‐2‐methylpropionitrile) as the initiator at room temperature. This example is the first use of a series of special solvents containing carbonyl groups (e.g., 1,3‐dimethyl‐2‐imidazolidinone) as both solvent and catalyst for photocontrolled RDRP using long‐wavelength (λ_max=730 nm) irradiation. The polymerization system comprises monomer, alkyl iodide initiator, and solvent. Well‐defined polymers were synthesized with excellent control over the molecular weights and molecular weight distributions (M_w/M_n<1.21). The living features of this system were confirmed by polymerization kinetics, multiple controlled “on‐off” light switching cycles, and chain extension experiments. Importantly, the polymerizations proceeded successfully with various barriers (pork skin and A4 paper), demonstrating the advantage of high‐penetration NIR light.     

Cationic polymerization of n‐hexyloxyallene by using halogen‐bonding organocatalysts

The cationic polymerization of n‐hexyloxyallene was investigated by using halogen‐bonding organocatalysts ( Cat A – Cat D ). Although the neutral catalyst Cat C showed a poor polymerization activity, iodine‐carrying bidentate cationic catalyst Cat A brought about the smooth polymerization giving rise to a polymer with M_n of 2710 under [ Cat A ]:[IBVE‐HCl]:[monomer] = 10:10:500 in mM concentrations. Judging from the color change of polymerization system and electrospray ionization mass spectra of recovered catalyst, the decomposition of organocatalyst was suggested. When α‐bromodiphenylmethane was used as an initiator, the relatively controlled polymerization proceeded at the low monomer conversion likely due to the weak halogen‐bonding interaction of Cat A with the bromide anion. On the other hand, bromine‐carrying bidentate catalyst Cat D gave low‐molecular‐weight polymers (M_n < 1550) to be less suitable for polymerization. From the ¹H‐NMR spectrum, it was found that the 1,2‐polymerization unit and 2,3‐polymerization unit are included in 75:25. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 2436–2441     

Photocontrolled Iodine-Mediated Reversible-Deactivation Radical Polymerization: Solution Polymerization of Methacrylates by Irradiation with NIR LED Light

Herein, near-infrared (NIR) photocontrolled iodide-mediated reversible-deactivation radical polymerization (RDRP) of methacrylates, without an external photocatalyst, was developed using an alkyl iodide (e.g., 2-iodo-2-methylpropionitrile) as the initiator at room temperature. This example is the first use of a series of special solvents containing carbonyl groups (e.g., 1,3-dimethyl-2-imidazolidinone) as both solvent and catalyst for photocontrolled RDRP using long-wavelength (λ_max=730 nm) irradiation. The polymerization system comprises monomer, alkyl iodide initiator, and solvent. Well-defined polymers were synthesized with excellent control over the molecular weights and molecular weight distributions (M_w/M_n<1.21). The living features of this system were confirmed by polymerization kinetics, multiple controlled “on-off” light switching cycles, and chain extension experiments. Importantly, the polymerizations proceeded successfully with various barriers (pork skin and A4 paper), demonstrating the advantage of high-penetration NIR light.     

Synthesis of polyacrylonitrile mediated by manganese(III) acetylacetonate (Mn(acac)3) and 2‐cyanoprop‐2‐yl dithionaphthalenoate

2‐Cyanoprop‐2‐yl dithionaphthalenoate (CPDN) was successfully used as the chain transfer agent to prepare polyacrylonitrile in combination with manganese(III) acetylacetonate (Mn(acac)₃) as the initiator. The novel polymerization exhibited well “living”/controlled characteristics. The polymerization behavior was revealed to comply with features of reversible addition–fragmentation chain transfer polymerization process. Mn(acac)₃ played a key role as the initiator rather than the radical trapping agent in polymerization and exhibited better control performance than azo‐initiator. The narrowest molecular weight distribution was 1.31 under the condition of [AN]₀:[Mn(acac)₃]₀:[CPDN]₀ = 200:1:0.025 and AN:DMF = 1:1 (V/V). Various feed ratios of Mn(acac)₃ and CPDN were also investigated in detail. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 1305–1309     

Air‐tolerantly surface‐initiated AGET ATRP mediated by iron catalyst from silica nanoparticles

Well‐defined polymer‐nanoparticle hybrids were prepared by a newly reported method: atom transfer radical polymerization using activators generated by electron transfer (AGET ATRP) mediated by iron catalyst. The kinetics of the surface‐initiated AGET ATRP of methyl methacrylate from the silica nanoparticles, which was mediated by FeCl₃/triphenylphosphine as a catalyst complex, ascorbic acid as a reducing agent, N,N‐dimethylformamide as the solvent in the presence of a “sacrificial” (free) initiator, was studied. Both the free and grafted polymers were grown in a control manner. The chemical composition of the nanocomposites was characterized by Fourier transform infrared spectroscopy, X‐ray photoelectron spectroscopy, and ¹H nuclear magnetic resonance spectroscopy. Thermogravimetric analysis was used to estimate the content of the grafted organic compound, and transmission electron micrographs was used to observe the core‐shell structure of the hybrid nanoparticles. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 2006–2015, 2010     

Iron‐mediated AGET ATRP of methyl methacrylate using metal wire as reducing agent

Methyl methacrylate (MMA) were successfully polymerized by atom transfer radical polymerization with activator generated by electron transfer (AGET ATRP) using copper or iron wire as the reducing agent at 90°C. Well‐controlled polymerizations were demonstrated using an oxidatively stable iron(III) chloride hexahydrate (FeCl₃·6H₂O) as the catalyst, ethyl 2‐bromoisobutyrate (EBiB) as the initiator, and tetrabutylammonium bromide (TBABr) or triphenylphosphine as the ligand. The polymerization rate was fast and affected by the amount of catalyst and type of reducing agents. For example, the polymerization rate of bulk AGET ATRP with a molar ratio of [MMA]₀/[EBiB]₀/[FeCl₃·6H₂O]₀/[TBABr]₀ = 500/1/0.5/1 using iron wire (the conversion reaches up to 82.2% after 80 min) as the reducing agent was faster than that using copper wire (the conversion reaches up to 86.1% after 3 h). At the same time, the experimental M_n values of the obtained poly(methyl methacrylate) were consistent with the corresponding theoretical ones, and the M_w/M_n values were narrow (～1.3), showing the typical features of “living”/controlled radical polymerization. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Controlled ring‐opening polymerization of propylene oxide catalyzed by double metal‐cyanide complex

A double metal‐cyanide catalyst based on Zn₃[Co(CN)₆]₂ was prepared. This catalyst is very effective for the ring‐opening polymerization of propylene oxide. Polyether polyols of moderate molecular weight having low unsaturation (<0.015 meq/g) can be prepared under mild conditions. The molecular weight of polymer is entirely controlled by a reacted monomer‐to‐initiator ratio. The polymers prepared with stepwise addition of monomer exhibit a narrower molecular weight distribution as compared with those prepared with one‐step addition of monomer. Various compounds containing active hydrogen, except basic compounds and low‐carbon carboxylic acid, may be used as initiators. The reaction rate increases with increasing catalyst amount and decreases with rising initiator concentration. Polymerization involves a rapid exchange reaction between the active species and the dormant species. It was also proven that, to a certain extent, the chain termination of this catalytic system is reversible or temporary. ¹³C NMR analysis showed that the polymer has a random distribution of the configurational sequences and head‐to‐tail regiosequence. It is assumed that the polymerization proceeds via a cationic coordination mechanism. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 1142–1150, 2002     

Tetramethylguanidino‐tris(2‐aminoethyl)amine: A novel ligand for copper‐based atom transfer radical polymerization

With CuBr/tetramethylguanidino‐tris(2‐aminoethyl)amine (TMG₃‐TREN) as the catalyst, the atom transfer radical polymerization (ATRP) of methyl methacrylate, n‐butyl acrylate, styrene, and acrylonitrile was conducted. The catalyst concentration of 0.5 equiv with respect to the initiator was enough to prepare well‐defined poly(methyl methacrylate) in bulk from methyl methacrylate monomer. For ATRP of n‐butyl acrylate, the catalyst behaved in a manner similar to that reported for CuBr/tris[2‐(dimethylamino)ethyl]amine. A minimum of 0.05 equiv of the catalyst with respect to the initiator was required to synthesize the homopolymer of the desired molecular weight and low polydispersity at the ambient temperature. In the case of styrene, ATRP with this catalyst occurred only when a 1:1 catalyst/initiator ratio was used in the presence of Cu(0) in ethylene carbonate. The polymerization of acrylonitrile with CuBr/TMG₃‐TREN was conducted successfully with a catalyst concentration of 50% with respect to the initiator in ethylene carbonate. End‐group analysis for the determination of the high degree of functionality of the homopolymers synthesized by the new catalyst was determined by NMR spectroscopy. The isotactic parameter calculated for each system indicated that the homopolymers were predominantly syndiotactic, signifying that the tacticity remained the same, as already reported for ATRP. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 5906–5922, 2005     

Investigation of Mizoroki‐Heck coupling polymerization as a catalyst‐transfer condensation polymerization for synthesis of poly(p‐phenylenevinylene)

Mizoroki‐Heck coupling polymerization of 1,4‐bis[(2‐ethylhexyl)oxy]‐2‐iodo‐5‐vinylbenzene ( 1 ) and its bromo counterpart 2 with a Pd initiator for the synthesis of poly(phenylenevinylene) (PPV) was investigated to see whether the polymerization proceeds in a chain‐growth polymerization manner. The polymerization of 1 with ^tBu₃PPd(Tolyl)Br ( 10 ) proceeded even at room temperature when 5.5 equiv of Cy₂NMe (Cy = cyclohexyl) was used as a base, but the molecular weight distribution of PPV was broad. The polymerization of 2 hardly proceeded at room temperature under the same conditions. In the polymerization of 1 , PPV with H at one end and I at the other was formed until the middle stage, and the polymer end groups were converted into tolyl and H in the final stage. The number‐average molecular weight (M_n) did not increase until about 90% monomer conversion and then sharply increased after that, indicating conventional step‐growth polymerization. The occurrence of step‐growth polymerization, not catalyst‐transfer chain‐growth polymerization, may be interpreted in terms of low coordination ability of H‐Pd(II)‐X(^tBu₃P) (X = Br or I), formed in the catalytic cycle of the Mizoroki‐Heck coupling reaction, to π‐electrons of the PPV backbone; reductive elimination of H‐X from this Pd species with base would take place after diffusion into the reaction mixture. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 543–551     

RAFT made methacrylate copolymers for reversible pH‐responsive nanoparticles

In this study, we designed and investigated pH‐responsive nanoparticles based on different ratios of monomers with primary, secondary or tertiary amino groups. For this purpose, copolymers of methyl methacrylate (MMA) with different compositions of amino methacrylates (2‐(dimethylamino)ethyl methacrylate (DMAEMA), 2‐(tert‐butylamino)ethyl methacrylate (tBAEMA) and 2‐aminoethyl methacrylate hydrochloride (AEMA·HCI)) were synthesized using the reversible addition‐fragmentation chain transfer (RAFT) polymerization process. The controlled nature of the radical polymerization was demonstrated by kinetic studies. All copolymers show low dispersities (?_M < 1.2) with amino contents between 9 and 21 mol %. For the nanoparticle formation, nanoprecipitation with subsequent solvent evaporation was used. All suspensions were characterized by dynamic light scattering (DLS) and scanning electron microscopy (SEM). Different initial conditions of the formulations resulted in differently sized nanoparticles that have monomodal size distributions, relatively narrow polydispersity index (PDI) values and positive zeta potential values. The pH‐stability test results demonstrated that, depending on the structure and amount of the amino content, the obtained nanoparticles reveal a reversible pH‐response, such as dissolution at acidic pH values. The ability of the nanoparticles to encapsulate guest molecules was confirmed by pyrene fluorescence studies. The cytotoxicity assay results showed that the nanoparticles did not have any significant cytotoxic effect. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 2711–2721     

Iron(III)‐mediated AGET ATRP of styrene using tris(3,6‐dioxaheptyl)amine as a ligand

A commercially available tris(3,6‐dioxaheptyl)amine (TDA‐1) was used as a novel ligand for activator generated by electron transfer atom transfer radical polymerization (AGET ATRP) of styrene in bulk or solution mediated by iron(III) catalyst in the presence of a limited amount of air. FeCl₃ · 6H₂O and (1‐bromoethyl)benzene (PEBr) were used as the catalyst and initiator, respectively; and environmentally benign ascorbic acid (VC) was used as the reducing agent. The polymerizations show the features of “living”/controlled free‐radical polymerizations and well‐defined polystyrenes with molecular weight M_n = 2400–36,500 g/mol and narrow polydispersity (M_w/M_n = 1.11–1.29) were obtained. The “living” feature of the obtained polymer was further confirmed by a chain‐extension experiment. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 2002–2008, 2009     

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     

Novel synthesis of rod‐coil block copolymers by combination of coordination polymerization and ATRP

Combination of coordination polymerization and atom transfer radical polymerization (ATRP) was applied to a novel synthesis of rod‐coil block copolymers. The procedure included the following steps: (1) monoesterification reaction of ethylene glycol with 2‐bromoisobutyryl bromide yielded a α‐bromo, ω‐hydroxy bifunctional initiator, (2) CpTiCl₃ (bifunctional initiator) catalyst was prepared from a mixture of trichlorocyclopentadienyl titanium (CpTiCl₃) and bifunctional initiator. Coordination polymerization of n‐butyl isocyanate initiated by such catalyst provided a well‐defined macroinitiator, poly(n‐butyl isocyanate)‐Br (PBIC‐Br), and (3) ATRP method of vinyl monomers using PBIC‐Br provided rod (PBIC)‐coil block copolymers. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 4037–4042, 2007     

Controlled polymerization of epoxides: Metal‐free ring‐opening polymerization of glycidyl phenyl ether initiated by tetra‐n‐butylammonium fluoride in the presence of protic compounds

Metal‐free controlled ring‐opening polymerization of glycidyl phenyl ether (GPE) was achieved using tetra‐n‐butylammonium fluoride (Bu₄NF) as an initiator in the presence of water and ethanol as chain transfer agents (CTAs). Number‐averaged molecular weight of poly(GPE) increased with an increase of [GPE]₀/([Bu₄NF]₀ + [CTA]₀) values, showing relatively narrow molecular weight distributions. NMR spectroscopic analysis exhibited a formation of ethoxy groups as well as FCH₂ at the initiating polymer chain‐end when ethanol was used as the CTA in the polymerization. These results indicate that Bu₄NF acts as a catalyst as well as the initiator for this polymerization system. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Cyclometalated 2‐phenylpyridine complex [RuII(o‐C6H4‐py)(MeCN)4]PF6 as a tunable catalyst for living radical polymerization

The cyclometalated complex [Ru^II(o‐C₆H₄‐py)(MeCN)₄]PF₆ ( 1 ) with a σ‐Ru? C bond and four substitutionally labile acetonitrile ligands mediates radical polymerization of different vinyl monomers, viz. n‐butyl acrylate, methyl methacrylate, and styrene, initiated by three alkyl bromides: ethyl 2‐bromoisobutyrate, methyl 2‐bromopropionate, and 1‐phenylethyl bromide. The polymerization requires the presence of Al(OiPr)₃ and occurs uncontrollably as a conventional radical process. The variation of the molar ratio of the components of the reaction mixture, such as initiator, Al(OiPr)₃ and catalyst, affected the polymerization rates and the molecular weights but did not improve the control. A certain level of control has been achieved by adding 0.5 eq of SnCl₂ as a reducing agent. Tin(II) chloride decreased the rate of polymerization and simultaneously the molecular weights became conversion‐dependent and the polydispersities were also narrowed. Remarkably, the level of control was radically improved in the presence of excess of the poorly soluble catalyst ( 1 ), when the added amount of ( 1 ) was not soluble any more, i.e., under heterogeneous conditions, the system became adjustable and the living polymerization of all three monomers was finally achieved. Possible mechanisms of the ( 1 )‐catalyzed polymerization are discussed. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 4193–4204, 2008     

A bidirectional ATRP‐NMRP initiator: The effect of nitroxide size on the rate of nitroxide‐mediated polymerization

An N‐alkoxyamine macroinitiator bearing a polymeric nitroxide cap was synthesized and used to investigate the effect of nitroxide size on the rate of nitroxide‐mediated radical polymerization (NMRP). This macroinitiator was prepared from asymmetric double‐headed initiator 9 , which contains both an α‐bromoester and an N‐alkoxyamine functionality. Poly(methyl methacrylate) was grown by atom transfer radical polymerization from the α‐bromoester end of this initiator, resulting in a macroinitiator (M_n = 31,000; PDI = 1.34) bearing a nitroxide cap permanently attached to a polymer chain. The polymerization kinetics of this macroinitiator in NMRP were compared with known N‐alkoxyamine initiator 1 . It was found that the rate of polymerization was unaffected by the size of the macromolecular nitroxide cap. It was confirmed that NMRP using this macroinitiator is a “living” process. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 2015–2025, 2007     

Cationic ring‐opening polymerization of trimethylene carbonate to α,ω‐dihydroxy telechelic and star‐shaped polycarbonates catalyzed by reusable o‐benzenedisulfonimide

Cationic ring‐opening polymerization of trimethylene carbonate using o‐benzenedisulfonimide as a reusable catalyst under mild conditions was described. The polymerization proceeded homogeneously without decarboxylation and poly(trimethylene carbonates) (PTMCs) were synthesized with well‐controlled molecular weights and narrow polydispersities (M_w/M_n = 1.12–1.18). The spectra of ¹H‐NMR, SEC, and MALDI–ToF MS clearly demonstrated the incorporation of the initiator residue into the polymer chains and the controlled/living nature of the polymerizations. Furthermore, the catalyst can be easily recovered, and its efficiency was fully retained. In addition, 1,3‐propanediol, 1,1,1‐trimethylolpropane, and pentaerythritol were successfully used as initiators to produce telechelic and star‐shaped polycarbonates which were determined by intrinsic viscosity experiments. The number of arms estimated by the shrinking factors ( ) were 2.0, 2.6, and 3.5, respectively, indicating the successful syntheses of the two‐, three‐, and four‐armed PTMCs. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 729–736     

Atom transfer radical polymerization of ionic liquid 2‐(1‐butylimidazolium‐3‐yl)ethyl methacrylate tetrafluoroborate

Polymeric forms of ionic liquids may have many potential applications because of their high thermal stability and ionic nature. They are generally synthesized by conventional free‐radical polymerization. Here we report a living/controlled free‐radical polymerization of an ionic liquid monomer, 2‐(1‐butylimidazolium‐3‐yl)ethyl methacrylate tetrafluoroborate (BIMT), via atom transfer radical polymerization. Copper bromide/bromide based initiator systems polymerized BIMT very quickly with little control because of fast activation but slow deactivation. With copper chloride as the catalyst and trichloroacetate, CCl₄, or ethyl α‐chlorophenylacetate as the initiator, BIMT was polymerized at 60 °C in acetonitrile with first‐order kinetics with respect to the monomer concentration. The molecular weight was linearly dependent on the conversion. The monomer concentration strongly affected the polymerization: a low monomer concentration caused the polymerization to be incomplete, probably because of catalyst disproportionation in polar solvents. The addition of a small amount of pyridine suppressed such disproportionation, but a further increase in the amount of pyridine greatly slowed the polymerization. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 5794–5801, 2004