Determination of the activation rate constants of alkyl halide initiators for atom transfer radical polymerization

The second-order activation rate constants k_A for low-molar-mass alkyl halides catalyzed by cuprous halide complexes Cu(I)X/2L (X = Cl or Br; L = 4,4′-diheptyl-2,2′-bipyridine) were determined by the nitroxide capping method along with ¹H NMR. The k_A for 1-phenylethyl bromide, a typical initiator for atom transfer radical polymerization (ATRP), with the Cu(I)Br complex was found to be close to the known value of the k_A for a polystyryl bromide, being large enough for the initiation to be completed at an early stage of polymerization. It was also found that k_A strongly depends on the kind of halogen and the steric factor of the alkyl halide in question.     

Alkyl halide/tertiary amine as novel initiators for free radical polymerizations of methyl methacrylate,methyl acrylate and styrene

A series of combinations of alkyl halide with tertiary amine such as ethyl α-bromophenylacetate/tris[2-(dimethylamino)ethyl)]amine (αEBP/Me₆TREN), ethyl 2-bromoisobutyrate/triethylamine (EBiB/TEA), and ethyl 2-chloropropionate/N,N,N′,N′,N′′-pentamethyldiethylenetriamine (ECP/PMDETA) have been developed as novel free radical initiators and used for the polymerizations of methyl acrylate (MA), methyl methacrylate (MMA) and styrene (St). The effects of the structure of alkyl halide and tertiary amine on the polymerization of MA were investigated. Gel permeation chromatograph (GPC) and proton nuclear magnetic resonance (¹H NMR) have been utilized to analyze the end group of the obtained poly(methyl acrylate). Electron spin resonance (ESR) spectroscopy was employed to identify the structure of the radicals produced by αEBP/Me₆TREN, and the results indicated that αEBP reacted with Me₆TREN via a single electron transfer (SET) nucleophilic mechanism to produce corresponding ethyl α-phenylacetate radicals which subsequently initiated the polymerization of MA. As both alkyl halide and tertiary amine are commercially available at low cost, non-explosive, and ease of use and storage in comparison with conventional azo, peroxide or persulfate initiators, the combination of alkyl halide and tertiary amine as a free radical initiator is promising for large-scale practical applications.     

Mechanism of carbon-halogen bond reductive cleavage in activated alkyl halide initiators relevant to living radical polymerization: theoretical and experimental study

The mechanism of reductive cleavage of model alkyl halides (methyl 2-bromoisobutyrate, methyl 2-bromopropionate, and 1-bromo-1-chloroethane), used as initiators in living radical polymerization (LRP), has been investigated in acetonitrile using both experimental and computational methods. Both theoretical and experimental investigations have revealed that dissociative electron transfer to these alkyl halides proceeds exclusively via a concerted rather than stepwise manner. The reductive cleavage of all three alkyl halides requires a substantial activation barrier stemming mainly from the breaking C-X bond. The activation step during single electron transfer LRP (SET-LRP) was originally proposed to proceed via formation and decomposition of RX(?-) through an outer sphere electron transfer (OSET) process (Guliashvili, T.; Percec, V. J. Polym. Sci., Part A: Polym. Chem. 2007, 45, 1607). These radical anion intermediates were proposed to decompose via heterolytic rather than homolytic C-X bond dissociation. Here it is presented that injection of one electron into RX produces only a weakly associated charge-induced donor-acceptor type radical anion complex without any significant covalent σ type bond character between carbon-centered radical and associated anion leaving group. Therefore, neither homolytic nor heterolytic bond dissociation applies to the reductive cleavage of C-X in these alkyl halides inasmuch as a true radical anion does not form in the process. In addition, the whole mechanism of SET-LRP has to be revisited since it is based on presumed OSET involving intermediate RX(?-), which is shown here to be nonexistent.     

Diorganotin halide carboxylates,thiocarboxylates and halide haloacetates

Twenty-eight diorganotin halide acetates, thioacetates, haloacetates and carboxylates, eighteen not previously reported, have been synthesized by the reaction between the diorganotin oxides and acid halides, and by transacyloxylation reactions between diorganotin halide acetates and carboxylic acids. Infrared in the 2000—200 cm^-1 range, proton and carbon-13 NMR and tin-119m Mössbauer data are interpreted in terms of acetoxy-bridged, trigonal bipyramidal tin in the solid phase with depolymerization occurring in solution where a dynamic equilibrium between diorganotin dihalide and dicarboxylate species is rapidly established. A new infrared absorption also appears at 100–125 cm^-1 to higher frequency of the v_asym(CO₂) which disappears on heating. A dimeric structure based upon four-membered Sn₂O₂ or Sn₂OX rings in which carboxylate group oxygen atoms bridge tin atoms of a second molecule leaving the CO group free is proposed. The halide thioacetates are associated in the solid state but are monomeric in solution.     

Theoretical study on halide and mixed halide Perovskite solar cells: Effects of halide atoms on the stability and electronic properties

Increasing the stability of perovskite solar cells is one of the most important tasks in the photovoltaic industry. Thus, the structural, energetic, and electronic properties of pure CH₃NH₃PbI₃ and fully doped compounds (CH₃NH₃PbBr₃ and CH₃NH₃PbCl₃) in cubic and tetragonal phases were investigated using density functional theory calculations. We also considered the effects of mixed halide perovskites CH₃NH₃PbI₂X (where X = Br and Cl) and compared their properties with CH₃NH₃PbI₃. The DFT results indicate that the phase transformation from tetragonal to cubic phase decreases the band gap. The calculated results show that the X‐site ion plays a vital role in the geometrical stability and electronic levels. An increase in the band gap and a reduction in the lattice constants are more apparent in CH₃NH₃PbI₂X compounds (I > Br > Cl).     

Azo initiators for the preparation of hydroxyl-terminated polybutadienes

Azo compounds such as di(4-hydroxybutyl)-2,2′-azobisisobutyrate, di(3-hydroxybutyl)-2,2′-azobisisobutyrate, di(2-hydroxypropyl)-2,2′-azobisisobutyrate, and di(2-hydroxyethyl)-2,2′-azobisisobutyrate were prepared and used as initiators for the preparation of hydroxyl-terminated polybutadienes (HTPBs) of molecular weight (M?_n) ranging from 2000 to 7500 and functionality between 1.90 and 3.0. The polymers were prepared by free-radical solution polymerization in dioxane and toluene. The polymers obtained were characterized for their molecular weight, hydroxyl number, functionality, and instrinsic viscosity.     

Heterogeneous initiators for the synthesis of polymer nanocomposites

Nanocomposites are obtained by the radical polymerization of styrene and methyl methacrylate on the surface of a dispersed filler containing chemisorbed compounds of quaternary ammonium, which catalyze decomposition of cumene hydroperoxide. The heterogeneous catalysts of hydroperoxide decomposition are obtained via the adsorption of cetyltrimethyl ammonium bromide and acetylcholine chloride on sodium montmorillonite, cellulose, and chitosan. The highest rate of the polymerization of both monomers is provided by the cellulose–cetyltrimethyl ammonium bromide catalyst. For a more hydrophilic methyl methacrylate, the rate of radical initiation is significantly lower at the same concentrations of the catalyst and hydroperoxide compared with hydrophobic styrene; however, the rate of polymerization is higher than for styrene because of a higher activity of methyl methacrylate in chain-propagation reactions. Relatively high rates of radical generation upon contact of cellulose–cetyltrimethyl ammonium bromide and cellulose–acetylcholine with hydroperoxides open the possibility to create cellulose-based disinfecting and medical materials.     

Micellar free radical initiators

The effect of the nature of the surfactant, peroxide (ROOH), and medium on the rate of radical initiation in a surfactant-ROOH mixed micellar system has been studied. Cationic surfactants, as distinct from anionic and nonionic ones, have been found to catalyze ROOH decomposition to form radicals. Cationic surfactants in an organic medium exhibit higher catalytic effect than in an aqueous solution. The catalytic activity of the surfactants is strongly dependent on the counterion nature. The highest catalytic activity is shown by cetyltrimethylammonium chloride.     

Recent insights for achieving mixed halide perovskites without halide segregation

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Polymer-metal halide interactions

Zirconium tatrafluoride forms stable complexes with Nylon 6 and caprolactam entailing the amide moieties. In compositions up to 5% ZiF₄ the crystalline structure of the polyamide appears unaffected by the complexed chain segments formed during melt blending. These segments become upon solidification part of the amorphous regions of the polyamide. This molecular reinforcement results in significant increases in both yield stress and tensile modulus. The polyamide compositions are characterized by increased rates of nucleation and a stable, fine crystalline structure in the solid state.     

Tailoring of polyacrylates with combined initiators

This article summarizes possibilities of tailoring polyacrylates and polymethacrylates prepared by anionic polymerization initiated with combined (mixed) initiators especially those containing alkali metal tert-alkoxides as stabilizing additives. First part gives a short overview of side reactions in anionic polymerization of polar vinyl monomers and the ways of solving the problem. Second part is devoted to the anionic polymerization of acrylic and methacrylic esters initiated with mixed initiators. Examples of synthetic methods are given for the preparation of special polymeric products based on acrylates, and the necessity of using different polymerization conditions for individual acrylic esters is demonstrated with respect to branching of the ester alkyl group.     

Theoretical analysis of the structure and intramolecular dynamics of imidazolium halide and N-methylimidazolium halide ion pairs

A plant for the theoretical analysis of the structure and intramolecular dynamics of ion pairs of organic salts based on the combined use of the results of quantum-chemical calculations and molecular mechanics has been proposed. The potential-energy surfaces of the interionic interactions in imidazolium halide and N-methylimidazolium halide ion pairs have been investigated, and the equilibrium geometric parameters and frequencies of the interionic vibrations have been determined. It has been established that these ion pairs should be classified as stereochemically nonrigid molecules.Deceased.Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 21, No. 5, pp. 522–529, September–October, 1985.     

Hydrazone initiators for vinyl polymerizations

A series of hydrazones were prepared and tested for their ability to act as free‐radical initiators for vinyl monomers. The most active initiators were the tertiary butyl hydrazones of aromatic, aliphatic ketones. The most reactive vinyl monomers were acrylate‐type monomers, with methacrylate‐type monomers being somewhat less reactive. When the most reactive hydrazone initiators, such as compound 1 , were added to ambient‐temperature solutions of acrylate monomers, such as aqueous sodium acrylate or aqueous acrylamide, polymerizations to hard gels occured within 1 min. In some cases of vinyl polymerizations, these hydrazone initiators can act as low‐temperature alternatives to redox initiators. © 2001 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 39: 1391–1402, 2001     

Resorbable initiators for polymerizations of lactones

Numerous nontoxic (resorbable) salts were prepared from cations and anions belonging to the human metabolism, such as Na, K, Mg, Ca, Zn and Fe in combination with chloride, iodide, hydroxide, carbonate, acetate, stearate, glycolate, L‐lactate, D‐mandelate and various N‐substituted α‐amino acids. All these salts were used as initiators for polymerizations of L‐lactide in bulk at 100–180°C. Furthermore, Grignard reagents, hemin and hematin were included in this study. Zn L‐lactate was found to be the most useful initiator in terms of reactivity, maximum molecular weight of the isolated poly(L‐lactide) and its optical purity. Zn L‐lactate initiated copolymerizations of L‐lactide and glycolid or L‐lactide and ϵ‐caprolactone were also studied. Finally, first studies of the polymerization mechanism of zinc stearate and zin 2‐ethylhexanoate were performed. They suggest that zinc carboxylates combined with an alcohol as coinitiator form reactive zinc alkoxides which are the true initiators at temperatures < 150°C.     

Resorbable initiators for polymerizations of lactones

Numerous salts were prepared from cations and anions belonging to the human metabolism, such as Na, K, Mg, Ca, Zn and Fe in combination with chloride, iodide, hydroxide, carbonate, acetate, stearate, glycolate, L-lactate, D-mandelate and various N-substituted α-amiono acids. All these salts were used as initiators for polymerizations of L-lactide in bulk at 100–180°C. Furthermore, Grignard reagents, hemin and hematin were included in this study. Zn L-lactate was found to be the most useful initiator in terms of reactivity, maximum molecular weight of the isolated poly(L-lactide) and its optical purity. Zn L-lactate initiated copolymerizations of L-lactide and glycolide or ϵ-caprolactone were also studied.     

Metallo-Supramolecular initiators for the preparation of novel functional architectures

Polymeric materials containing coordinative units have become a field of increasing interest. The combination of inorganic metal-containing units and macromolecules leads to supramolecular structures with new properties. One promising approach to such systems is the application of metallo-supramolecular initiators for living and controlled polymerization methods. The utilization of bi- and terpyridine units and complexes for this purpose will be discussed in this article.