The application of copper(II) deactivator on the single‐electron transfer living radical polymerization of tert‐butyl acrylate

We demonstrate the living radical polymerization of tert‐butyl acrylate (tBA) applying the SET mechanism, employing methyl 2‐bromopropionate (MBP) as initiator in dimethyl sulfoxide (DMSO) at ambient temperature. It is observed that introducing copper bromide into the catalyst system is necessary for controlling on the SET‐LRP polymerization of tBA. In this work, we make major investigation for the effect of the different stoichiometry quantity of copper bromide on the polymerization. Experiments show that the polymerization achieves better control with increasing the stoichiometry quantity of copper(II) deactivator. The structural analysis of the resulting polymers by ¹H NMR demonstrates the successful synthesis of poly(tBA)s by SET‐LRP in DMSO. Moreover, this work is helpful to the SET‐LRP of other monomers and is expected to expand the application of SET‐LRP. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 2793–2797, 2010     

Copolymerization of methacrylic acid with methyl methacrylate by SET‐LRP

Single‐electron transfer living radical polymerization (SET‐LRP) has developed as a reliable, robust and straight forward method for the construction well‐defined polymers. To span an even larger variety of functional monomers, we investigated the copolymerization of methyl methacrylate with methacrylic acid by SET‐LRP. Copolymerizations were catalyzed by Cu(0)/Me₆‐TREN and performed in MeOH/H₂O mixtures at 50 °C. The SET‐LRP copolymerizations of varying methacrylic acid content were evaluated by kinetic experiments. At low (2.5%) and moderate (10%) MAA loadings, the copolymerizations obeyed perfect first order kinetics (k_p^app = 0.008 min^?1 and k_p^app = 0.006 min^?1) and exhibited a linear increase in molecular weights with conversion providing narrow molecular weight distributions. The SET‐LRP of MMA/25%‐MAA was found to be significantly slower (k_p^app = 0.0035 min^?1). However, a reasonable first‐order kinetics in monomer consumption was maintained, and the control of the polymerization process was preserved since the molecular weight increased linearly with conversion and could therefore be adjusted. This work demonstrates that the copolymerization of methacrylic acid by SET‐LRP is feasible and the design of well‐defined macromolecules comprising acidic functionality can be achieved. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010     

Alkyl chloride initiators for SET‐LRP of methyl acrylate

Single‐electron transfer living radical polymerization (SET‐LRP) proceeds by an outer‐sphere single‐electron transfer mechanism that induces a heterolytic bond cleavage of the initiating and propagating R‐X (where X = Cl, Br, and I) species. Therefore, unlike the homolytic bond cleavage mechanism claimed for ATRP, SET‐LRP is expected to show a small dependence of the nature of the halide group on the apparent rate constant of activation. This means the R‐X with X = Cl, Br, and I must all be efficient initiators for SET‐LRP and no chain transfer must be observed in the case of initiators with X = Br and I. Here, we report the SET‐LRP of methyl acrylate initiated with the alkyl chlorides methyl‐2‐chloropropionate (MCP) and chloroform (CHCl₃) and catalyzed by Cu(0)/Me₆‐TREN/CuCl₂ in DMSO at 25 °C. A combination of kinetic and structural analysis was used to elucidate the MCP and CHCl₃ initiating behavior under SET‐LRP conditions, and to demonstrate the very small dependence of the SET‐LRP apparent rate constant of propagation on X while providing polymers with well defined architecture. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 4917–4926, 2008     

SET‐LRP of methyl methacrylate initiated with sulfonyl halides

Single electron transfer‐living radical polymerization (SET‐LRP) represents a robust and versatile method for the rapid synthesis of macromolecules with defined architecture. The present article describes the polymerization of methyl methacrylate by SET‐LRP in protic solvent mixtures. Herein, the polymerization process was catalyzed by a straightforward Cu(0)wire/Me₆‐TREN catalyst while initiation was obtained by toluenesulfonyl chloride. All experiments were conducted at 50 °C and the living polymerization was demonstrated by kinetic evaluation of the SET‐LRP. The process follows first order kinetic until all monomer is consumed which was typically achieved within 4 h. The molecular weight increased linearly with conversion and the molecular weight distributions were very narrow with M_w/M_n ～ 1.1. Detailed investigations of the polymer samples by MALDI‐TOF confirmed that no termination took place and that the chain end functionality is retained throughout the polymerization process. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 2236–2242, 2010     

Functionally terminated poly(methyl acrylate) by SET‐LRP initiated with CHBr3 and CHI3

The single‐electron transfer living radical polymerization (SET‐LRP) of methyl acrylate initiated with bromoform (CHBr₃) and iodoform (CHI₃) and catalyzed by Cu(0)/Me₆‐TREN in DMSO at 25 °C provides a reliable method to prepare poly (methyl acrylate) (PMA) with active chain ends and controlled structure that can undergo subsequent functionalization to provide strategies for the synthesis of different block copolymers and other complex architectures. A detailed kinetic and structural analysis was used to assess the scope and the limitations of CHBr₃ and CHI₃ as initiators under SET‐LRP conditions. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 278–288, 2008     

Ultrafast SET‐LRP of methyl acrylate at 25 °C in alcohols

Alcohols are known to promote the disproportionation of Cu(I)X species into nascent Cu(0) and Cu(II)X. Therefore, alcohols are expected to be excellent solvents that facilitate the single‐electron transfer mediated living radical polymerization (SET‐LRP) mediated by nascent Cu(0) species. This publication demonstrates the ultrafast SET‐LRP of methyl acrylate initiated with bis(2‐bromopropionyloxy)ethane and catalyzed by Cu(0)/Me₆‐TREN in methanol, ethanol, 1‐propanol, and tert‐butanol and in their mixture with water at 25 °C. The structural analysis of the resulting polymers by a combination of ¹H NMR and MALDI‐TOF MS demonstrates the synthesis of perfectly bifunctional α,ω‐dibromo poly(methyl acrylate)s by SET‐LRP in alcohols. Moreover, this work provides an expansion of the list of solvents available for SET‐LRP. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 2745–2754, 2008     

TREN versus Me6‐TREN as ligands in SET‐LRP of methyl acrylate

The commercially available tris(2‐aminoethyl)amine (TREN) was used as ligand to mediate the single‐electron transfer‐living radical polymerization (SET‐LRP) of methyl acrylate in dimethyl sulfoxide initiated with the bifunctional initiator bis(2‐bromopropionyl)ethane and catalyzed by both nonactivated and activated Cu(0) wire. A comparative study between TREN and tris(2‐dimethylaminoethyl)amine (Me₆‐TREN) ligand, that is more commonly used in SET‐LRP, demonstrated that TREN provided a slower polymerization but the chain‐ends functionality of the resulting bifunctional poly(methyl acrylate) was near quantitative and comparable to that obtained when Me₆‐TREN was used as a ligand. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012.     

SET‐LRP of methyl methacrylate initiated with CCl4 in the presence and absence of air

Single electron transfer‐living radical polymerization (SET‐LRP) represents a robust and versatile method for the rapid synthesis of macromolecules with defined architecture. The synthesis of poly(methyl methacrylate) via SET‐LRP in dimethyl sulfoxide (DMSO) by using CCl₄ as initiator is demonstrated in this work. Resorting to a rather simple Cu(0)/Me₆‐TREN catalyst a method was established that allowed for the straightforward design of well‐defined poly(methyl methacrylate). The reactions were performed at various temperatures (25, 50, 60, and 80 °C) and complete monomer conversion could be achieved. The polymerizations obeyed first order kinetic, the molecular weights increased linearly with conversion and the polymers exhibited narrow molecular weight distributions all indicating the livingness of the process. By providing a small amount of hydrazine to the reaction mixture the polymerization could be conducted in presence of air omitting the need for any elaborated deoxygenation procedures. This methodology offers an elegant way to synthesize functionalized poly(methyl methacrylate) with perfect control over the polymerization process as well as molecular architecture. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 2243–2250, 2010     

Synthesis of perfectly bifunctional polyacrylates by single‐electron‐transfer living radical polymerization

Poly(methyl acrylate)s, poly(ethyl acrylate)s, and poly(butyl acrylate)s with α,ω‐di(bromo) chain ends and M_n from 8500 to 35,000 were synthesized by single‐electron‐transfer living radical polymerization (SET‐LRP). The analysis of their chain ends by a combination of ¹H and 2D‐NMR, GPC, MALDI‐TOF MS, chain end functionalization, chain extension, and halogen exchange experiments demonstrated the synthesis of perfectly bifunctional polyacrylates by SET‐LRP. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 4684–4695, 2007     

Immortal SET–LRP mediated by Cu(0) wire

Cu(0)‐wire/Me₆‐TREN is a well established catalyst for living radical polymerization via SET–LRP. Here, it is demonstrated that this polymerization is not just living, but it is in fact the first example of immortal living radical polymerization. The immortality of SET–LRP mediated with Cu(0) wire was demonstrated by attempting, in an unsuccessful way, to irreversible interrupt multiple times the polymerization via exposure to O₂ from air. SET–LRP indeed stopped each time when the reaction mixture was exposed to air. However, the SET–LRP reaction, was restarted each time after resealing the reaction vessel and reestablishing the catalytic cycle with the same Cu(0) wire, to produce the same conversion as in the conventional uninterrupted SET–LRP process. Despite the interruption by O₂, the reactivated SET–LRP had a good control of molecular weight, molecular weight evolution, and molecular weight distribution, with perfect retention of chain‐end fidelity. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 2716–2721, 2010     

New efficient reaction media for SET‐LRP produced from binary mixtures of organic solvents and H2O

SET‐LRP is mediated by a combination of solvent and ligand that promotes disproportionation of Cu(I)X into Cu(0) and Cu(II)X₂. Therefore, the diversity of solvents suitable for SET‐LRP is limited. SET‐LRP of MA in a library of solvents with different equilibrium constants for disproportionation of Cu(I)X such as DMSO, DMF, DMAC, EC, PC, EtOH, MeOH, methoxyethanol, NMP, acetone and in their binary mixtures with H₂O was examined. H₂O exhibits the highest equilibrium constant for disproportionation of Cu(I)X. The apparent rate constant of the polymerization exhibits a linear increase with the addition of H₂O. This is consistent with higher equilibrium constants for disproportionation generated by addition of H₂O to organic solvents. Furthermore, with the exception of alcohols and carbonates, the rate constant of polymerization in binary mixtures could be correlated with the Dimroth‐Reichardt solvent polarity parameter. This is consistent with the single‐electron transfer mechanism proposed for SET‐LRP that involves a polar transition state. These experiments demonstrate that the use of binary mixtures of solvents with H₂O provides a new, simple and efficient method for the elaboration of a large diversity of reaction media that are suitable for SET‐LRP even when one of the two solvents does not mediate disproportionation of Cu(I)X. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 5577–5590, 2009     

Dramatic acceleration of SET‐LRP of methyl acrylate during catalysis with activated Cu(0) wire

A simple method for the activation of the Cu(0) wire used as catalyst in single‐electron transfer living radical polymerization (SET‐LRP) is reported. The surface of Cu(0) stored in air is coated with a layer of Cu₂O. It is well established that Cu₂O is a less reactive catalyst for SET‐LRP than Cu(0). We report here the activation of the Cu(0) wire under nitrogen by the reduction of Cu₂O from its surface to Cu(0) by treatment with hydrazine hydrate. The kinetics of SET‐LRP of methyl acrylate (MA) catalyzed with activated Cu(0) wire in dimethyl sulfoxide (DMSO) at 25 °C demonstrated a dramatic acceleration of the polymerization and the absence of the induction period observed during SET‐LRP catalyzed with nonactivated Cu(0) in several laboratories. Exposure of the activated Cu(0) wire to air results in a lower apparent rate constant of propagation because of gradual oxidation of Cu(0) to Cu₂O. This dramatic acceleration of SET‐LRP is similar to that observed with commercial Cu(0) nanopowder except that the polymerization provides excellent molecular weight evolution, very narrow molecular weight distribution and high polymer chain‐end functionality. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010     

Synthesis of well‐defined photoresist materials by SET‐LRP

Single electron transfer‐living radical polymerization (SET‐LRP) provides an excellent tool for the straightforward synthesis of well‐defined macromolecules. Heterogeneous Cu(0)‐ catalysis is employed to synthesize a novel photoresist material with high control over the molecular architecture. Poly(γ‐butyrolactone methacrylate)‐co‐(methyladamantly methacrylate) was synthesized. Kinetic experiments were conducted demonstrating that both monomers, γ‐butyrolactone methacrylate (GBLMA) and methyl adamantly methacrylate (MAMA), are successfully homopolymerized. In both cases polymerization kinetic is of first order and the molecular weights increase linearly with conversion. The choice of a proper solvent was decisive for the SET‐LRP process and organic solvent mixtures were found to be most suitable. Also, the kinetic of the copolymerization of GBLMA and MAMA was investigated. Following first order kinetics in overall monomer consumption and exhibiting a linear relationship between molecular weights and conversion a “living” process was established. This allowed for the straightforward synthesis of well‐defined photoresist polymers. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 2251–2255, 2010     

SET‐LRP of acrylonitrile in ionic liquids without any ligand

Use of ionic liquids as reaction media was investigated in the design of an environmentally friendly single electron transfer‐living radical polymerization (SET‐LRP) for acrylonitrile (AN) without any ligand by using Fe(0) wire as catalyst and 2‐bromopropionitrile as initiator. 1‐Methylimidazolium acetate ([mim][AT]), 1‐methylimidazolium propionate ([mim][PT]), and 1‐methylimidazolium valerate ([mim][VT]) were applied in this study. First‐order kinetics of polymerization with respect to the monomer concentration, linear increase of the molecular weight, and narrow polydispersity with monomer conversion showed the controlled/living radical polymerization characters. The sequence of the apparent polymerization rate constant of SET‐LRP of AN was k_app ([mim][AT]) > k_app ([mim][PT]) > k_app ([mim][VT]). The living feature of the polymerization was also confirmed by chain extensions of polyacrylonitrile with methyl methacrylate. All three ionic liquids were recycled and reused and had no obvious effect on the controlled/living nature of SET‐LRP of AN. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Single electron transfer‐living radical polymerization of methyl methacrylate in fluoroalcohol: Dual control over molecular weight and tacticity

The Cu(0)‐mediated single electron transfer‐living radical polymerization (SET‐LRP) of methyl methacrylate (MMA) using ethyl 2‐bromoisobutyrate (EBiB) as an initiator with Cu(0)/N,N,N′,N′′,N′′‐pentamethyldiethylenetriamine as a catalyst system in 1,1,1,3,3,3‐hexafluoro‐2‐propanol (HFIP) was studied. The polymerization showed some living features: the measured number‐average molecular weight (M_n,GPC) increased with monomer conversion and produced polymers with relatively low polydispersities. The increase of HFIP concentration improved the controllability over the polymerization with increased initiation efficiency and lowered polydispersity values. ¹H NMR, MALDI‐TOF‐MS spectra, and chain extension reaction confirmed that the resultant polymer was end‐capped by EBiB species, and the polymer can be reactivated for chain extension. In contrast, in the cases of dimethyl sulfoxide or N,N‐dimethylformamide as reaction solvent, the polymerizations were uncontrolled. The different effects of the solvents on the polymerization indicated that the mechanism of SET‐LRP differed from that of atom transfer radical polymerization. Moreover, HFIP also facilitated the polymerization with control over stereoregularity of the polymers. Higher concentration of HFIP and lower reaction temperature produced higher syndiotactic ratio. The syndiotactic ratio can be reached to about 0.77 at 1/1.5 (v/v) of MMA/HFIP at ?18 °C. In conclusion, using HFIP as SET‐LRP solvent, the dual control over the molecular weight and tacticity of PMMA was realized. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 6316–6327, 2009     

A comparative analysis of SET‐LRP of MA in solvents mediating different degrees of disproportionation of Cu(I)Br

Cu(I)Br/Me₆‐TREN species are unstable and disproportionate into metallic Cu(0) and Cu(II)Br₂/Me₆‐TREN in DMSO, whereas in toluene are stable and do not undergo disproportionation, at least at 25 °C. To estimate the role of the disproportionating solvent in single electron‐transfer living radical polymerization (SET‐LRP) a comparative analysis of Cu(0)/Me₆‐TREN‐catalyzed polymerization of MA initiated with methyl 2‐bromopropionate at 25 °C was performed in DMSO and toluene. A combination of kinetic experiments and chain end analysis by 500‐MHz ¹H NMR spectroscopy was used to demonstrate that disproportionation represents the crucial requirement for a successful SET‐LRP of MA at 25 °C. In DMSO a perfect SET‐LRP occurs and yields close to 100% conversion in 45 min. A first order polymerization in growing species up to 100% conversion and a PMA with perfectly functional chain ends are obtained. However, in toluene within 17 h only about 60% conversion is obtained, the polymerization does not show first order in growing species and therefore is not a living polymerization. Moreover, at 60% conversion the resulting PMA has only 80% active chain ends. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 6880–6895, 2008     

Preparation of polyacrylonitrile via SET‐LRP catalyzed by lanthanum powder in the presence of VC

A novel catalyst system based on La(0)/hexamethylenetetramine (HMTA) complexes is used for single electron transfer‐living radical polymerization (SET‐LRP) of acrylonitrile (AN) in the presence of ascorbic acid (VC) with carbon tetrachloride (CCl₄) as a initiator and N,N‐dimethylformamide (DMF) as a solvent. Compared with SET‐LRP of AN in the absence of VC, monomer conversion is markedly increased. SET‐LRP of AN in the presence of VC is also conducted in the presence of air. The kinetic studies show that the polymerizations both in the absence of oxygen and in the presence of air proceed in a well‐controlled manner. With the respect to the polymerization in the absence of oxygen, the polymerization in the presence of air provides slower reaction rate and broader polydispersity. Effects of amount of VC, La, CCl₄, and are investigated in detail. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013 , 51, 4088–4094     

SET‐LRP of methyl acrylate catalyzed with activated Cu(0) wire in methanol in the presence of air

Single electron transfer‐living radical polymerization (SET‐LRP) of methyl acrylate (MA) in methanol, catalyzed with nonactivated and activated Cu(0) wires, was performed in the presence of nondeoxygenated reagents and was investigated under a simple blanket of nitrogen. The addition of a small amount of hydrazine hydrate mediates the deoxygenation of the reaction mixture by the consumption of oxygen through its use to oxidize Cu(0) to Cu₂O, followed by the reduction of Cu₂O with hydrazine back to the active Cu(0) catalyst. SET‐LRP of MA in methanol in the presence of air requires a smaller dimension of Cu(0) wire, compared to the nonactivated Cu(0) wire counterpart. Activation of Cu(0) wire allowed the polymerization in air to proceed with no induction period, linear first‐order kinetics, linear correlation between the molecular weight evolution with conversion, and narrow molecular weight distribution. The retention of chain‐end functionality of α,ω‐di(bromo) poly(methyl acrylate) (PMA) prepared by SET‐LRP was demonstrated by a combination of experiments including ¹H NMR spectroscopy and matrix‐assisted laser desorption ionization–time of flight mass spectrometry after thioetherification of α,ω‐di(bromo) PMA with thiophenol. In SET‐LRP of MA in the presence of limited air, bimolecular termination is observed only above 85% conversion. However, for bifunctional initiators, the small amount of bimolecular termination observed at high conversion maintains a perfectly bifunctional polymer. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Copper(0)‐mediated living radical polymerization of acrylonitrile: SET‐LRP or AGET‐ATRP

Cu(0)‐mediated living radical polymerization was first extended to acrylonitrile (AN) to synthesize polyacrylonitrile with a high molecular weight and a low polydispersity index. This was achieved by using Cu(0)/hexamethylated tris(2‐aminoethyl)amine (Me₆‐TREN) as the catalyst, 2‐bromopropionitrile as the initiator, and dimethyl sulfoxide (DMSO) as the solvent. The reaction was performed under mild reaction conditions at ambient temperature and thus biradical termination reaction was low. The rapid and extensive disproportionation of Cu(I)Br/Me₆‐TREN in DMSO/AN supports a mechanism consistent with a single electron transfer‐living radical polymerization (SET‐LRP) rather than activators generated by electron transfer atom transfer radical polymerization (AGET ATRP). ¹H NMR analysis and chain extension experiment confirm the high chain‐end functionality of the resultant polymer. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010