Stereocontrol in radical polymerization of acrylic monomers

A clear effect of Lewis acids, such. as scandium trifluoromethanesulfonate [Sc(OTf)₃], on stereocontrol during the radical polymerization of a designed monomer, benzyl α-(methoxymethyl)acrylate was found. This Lewis acid also influenced the stereochemistry in the radical polymerization of methyl methacrylate giving a less syndiotactic and more isotactic polymer, although many Lewis acids were not effective. A catalytic amount of Lewis acids, such as Y(OTf)₃ and Yb(OTf)₃, also significantly enhanced isotactic-specificity during the radical polymerization of acrylamide and its derivatives, N-isopropylacrylamide (NIPAM) and N,N-dimethylacrylamide. Obvious solvent and temperature effects on tacticity were observed in these polymerizations, and poly(NIPAM) with >80% triad isotactic content has been obtained in the presence of Lewis acids.     

Synthesis and characterization of polymers from itaconic acid derivatives

Some itaconic acid derivatives were prepared and polymerized, in which itaconic acid (IA), β-monoalkyl itaconates (mRI), dialkyl itaconates (DRI), N-substituted itaconamates (IAE), itaconamides (IAm), itaconic anhydride (IAn), N-alkylitaconimides (RII), and N-(alkyl-substituted phenyl)itaconimides (RPhII) are included. The polymerization reactivity was examined, and discussed in relation to the structure of the monomers. The structure and some properties of the resulting polymers were investigated. Some citraconic acid (CA) and mesaconic acid (MA) derivatives were also polymerized, and their reactivities were compared with the corresponding IA derivatives.     

Cu-mediated selective bromination of aniline derivatives and preliminary mechanism study

A simple and efficient bromination of aniline, aniline derivatives, and analogs have been developed. Forty three examples were given and the highest yield reached was 98%. Different substrates including substituted aniline, pyridin-amine, N-substituted aniline, N,N-disubstituted aniline, N-phenyl-amide, N-phenyl-sulfonamide, and nitrogen-containing heterocycles were all reactive and selectively generated desired bromo-products. The method can be applied to synthesize drug intermediate and quinoxaline derivatives.     

Synthesis of substituted polymethylenes by radical polymerization of alkyl N,N-dialkylfumaramates and maleamates: Relative reactivity of the isomers

Bulk polymerization of alkyl N,N-dialkylfumaramates (FAE) and maleamates (MAE) was performed in the presence of a radical initiator. It has been found that FAE is more reactive than MAE when the reactivity of the two geometrical isomers was compared for their homo- and copolymerizations. From investigation on the effect of ester and N-substituents of these monomers, it has been found that the isopropyl ester shows a higher reactivity than the methyl ester and that N-ethyl and n-butyl substitution gives polymers with high molecular weight of more than several thousands. The resulting substituted polymethylenes from FAE and MAE were characterized and compared with each other. The isomerization of MAE to FAE with morpholine as an isomerization catalyst and monomer-isomerization radical polymerization were also investigated.     

The effect of the N‐substituent s‐trans to the carbonyl group of N‐methylacrylamide derivatives on the stereospecificity of radical polymerizations

Radical polymerization of N‐methylacrylamide (NMAAm), N,N‐dimethylacrylamide (DMAAm), and N‐methyl‐N‐phenylacrylamide (MPhAAm) was investigated in toluene at low temperatures. Atactic, isotactic, and syndiotactic polymers were obtained by the polymerization of NMAAm, DMAAm, and MPhAAm, respectively, indicating that the stereospecificity of the radical polymerization of acrylamide derivatives depended on the N‐substituents of the monomer used. From the viewpoint of monomer structure, the origin of the stereospecificity of radical polymerization of NMAAm derivatives is discussed. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 6534–6539, 2009     

High regioselectivity in electrochemical α-methoxylation of N-protected cyclic amines

N-Protecting groups of α-substituted cyclic amines strongly affected the regioselectivity in electrochemical methoxylation of these compounds. Namely, N-acyl derivatives were transformed into α′-methoxylated compounds, while N-cyano derivatives changed into α-methoxylated derivatives. Furthermore, Lewis acid catalyzed nucleophilic substitution of the α-methoxylated compounds protected with cyano group afforded α,α-disubstituted cyclic amines.     

Photopolymerization of 1,6‐hexanedioldiacrylate initiated by three‐component systems based on N‐arylphthalimides

Three‐component photoinitiators comprised of an N‐arylphthalimide, a diarylketone, and a tertiary amine were investigated for their initiation efficiency of acrylate polymerization. The use of an electron‐deficient N‐arylphthalimide resulted in a greater acrylate polymerization rate than an electron‐rich N‐arylphthalimide. Triplet energies of each N‐arylphthalimide, determined from their phosphorescence spectra, and the respective rate constants for triplet quenching by the N‐arylphthalimide derivatives (acquired via laser flash photolysis) indicated that an electron–proton transfer from an intermediate radical species to the N‐arylphthalimide (not energy transfer from triplet sensitization) is responsible for generating the initiating radicals under the conditions and species concentrations used for polymerization. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 4009–4015, 2004     

Hydrogen-transfer polymerization of methyl-substituted acrylamides

Base-catalyzed hydrogen-transfer polymerization and copolymerization of acrylamide and its methyl-substituted derivatives were studied in pyridine at 110°C. n-Butyllithium was used as an initiator. The observed rates of these homopolymerizations were found to decrease in the following order: acrylamide > crotonamide > methacrylamide > N-methylacrylamide > N-methylcrotonamide > tiglinamide > N-methylmethacrylamide ? α-chlorocrotonamide ? α-cyanocrotonamide = 0. Acrylamide gave the polymer with the highest degree of polymerization among the monomers examined. It was found that the number and the position of the methyl substituent in acrylamide affected significantly both the rate of polymerization and the molecular weight of the polymer. Although all polymers obtained, except the N-methyl derivatives, contained both methanol-soluble and methanol-insoluble fractions, a polyamide structure with unsaturated terminal monomer unit was confirmed by both infrared and NMR determinations. From the NMR determination of the saturated and terminal unsaturated units, the degree of polymerization of the resulting polyamides were also obtained. The monomers were also found to copolymerize by a hydrogen-transfer mechanism. However, the main chain of the resulting copolymers was composed of the more reactive monomer unit, and the less reactive monomer was incorporated only as a terminal unit when a less reactive monomer was copolymerized with a more reactive one. From these results, it was concluded that these polymerizations proceeded via an intermolecular hydrogen-transfer mechanism (i.e., stepwise mechanism).     

Michael addition reactions of cyclanones with acrylamides: Producing 2-carbamoylethyl derivatives or ene-lactams

The electron-withdrawing groups (EWGs) in the electrophilic alkenes employed in the Michael addition reaction are almost only CO2R, CN, COR, NO2, and SO2Ph. Although amides (CONR1R2) are also typical electron-withdrawing groups and are of great importance in organic synthesis, they are scarcely em-ployed as the EWGs of the electrophilic alkenes in the Michael addition reaction. In this work, the Mi-chael reactions of acrylamide and its derivatives with cyclanones were successfully carried out in the presence of enough radical inhibitors. The amide groups play a key role in producing the preferred products. The N-substituted acrylamides, including N-monosubstituted and N,N-disubstituted acryla-mides could react with cyclohexanone (CHn) to give the expected 2-carbamoylethyl derivatives; how-ever, acrylamide reacting with cyclohexanone only produced ene-lactam. Cyclanones also have effects on the products, while the ring size of cyclanones influences the reaction yield and the α-substituent decides the ratio of resulting isomeric ene-lactams.     

The Silyl Method for the Synthesis of 1[-2(Phenoxy)ethyl]uracils

A modification of the method for the synthesis of N₍₁₎-substituted derivatives of uracil is proposed using the Gilbert-Johnson reaction, which consists of the alkylation of 5-substituted 2,4-bis(trimethylsiloxy)pyrimidines with 1-bromo-2-(phenoxy)ethanes of low reactivity at 180-185° without solvent. The corresponding 1-[2-(phenoxy)ethyl]uracils, which were obtained in 55-74% yield, contained no impurities of the N₍₁₎, N₍₃₎-disubstituted compounds. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, 1071–1075, July, 2005. cf E. Ya. Lukevics and A. E. Zablotskaya. The Silyl Method for the Synthesis of Nucleosides [in Russian], Zinatne, Riga, 1985, 440 p. (Editor's note).     

Synthesis of α-(aminomethylene)-9H-purine-6-acetic acid derivatives

α-(Aminornethylene)-9H-purine-6-acetamide ( 3a ) and the corresponding ethyl acetate 9 have been synthesized by catalytic hydrogenation of 6-cyanomethylenepurine derivatives 2 and 7 which were obtained by the substitution of 6-chloropurine derivatives with α-cyanoacetamide and ethyl cyanoacetate, respectively. Substitution of α-(aminomethylene)-9-(tetrahydrofuran)-9H-purine-6-acetamide ( 3b ) with amines gave the corresponding N-alkyl- and N-arylamines 5 , which were treated with acid to give N-substituted α-(aminomethylene)-9H-purine-6-acetamides 6 . Substitution of 9 with amines gave the corresponding N-alkyl- and N-aryl substituted amines 10 .     

Synthesis of poly(tert‐butyl acrylate‐block‐vinyl acetate) copolymers by combining ATRP and RAFT polymerizations

The synthesis of poly(tert‐butyl acrylate‐block‐vinyl acetate) copolymers using a combination of two living radical polymerization techniques, atom transfer radical polymerization (ATRP) and reversible addition‐fragmentation chain transfer (RAFT) polymerization, is reported. The use of two methods is due to the disparity in reactivity of the two monomers, viz. vinyl acetate is difficult to polymerize via ATRP, and a suitable RAFT agent that can control the polymerization of vinyl acetate is typically unable to control the polymerization of tert‐butyl acrylate. Thus, ATRP was performed to make poly(tert‐butyl acrylate) containing a bromine end group. This end group was subsequently substituted with a xanthate moiety. Various spectroscopic methods were used to confirm the substitution. The poly(tert‐butyl acrylate) macro‐RAFT agent was then used to produce (tert‐butyl acrylate‐block‐vinyl acetate). © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 7200–7206, 2008     

Electrochemical and chemical polymerization of acrylamide

The electrochemical and chemical polymerization of acrylamide (AA) has been studied. The electrolysis of the monomer in N,N-dimethylformamide (DMF) containing (C₄H₉)₄NClO₄ as the supporting electrolyte leads to polymer formation in both anode and cathode compartments. The cathodic polymer dissolves in the reaction mixture and the anodic polymer precipitates during the course of polymerization. A plausible mechanism for the anodic and cathodic initiation reaction has been given. The chemical polymerization of acrylamide that has been initiated by HClO₄ is analogous to its anodic polymerization. The polymer yield increases with an increase in concentration of the monomer and HClO₄. Raising the reaction temperature also enhances the polymerization rate. The overall apparent activation energy of the polymerization was determined to be ca. 19 kcal/mole. The copolymerization of acrylamide was carried out with methyl methacrylate (MMA) in a solution of HClO₄ in DMF. The reactivity ratios are r₁ (AA) = 0.25 and r₂ = 2.50. The polymerization with HClO₄ appears to be by a free radical mechanism. When the polymerization of acrylamide is carried out with HClO₄ in H₂O, a crosslinked water-insoluble gel formation takes place.     

Kinetics of radical polymerization-XXXVI: Investigation of molecule-inhibitors in the radical polymerization of methyl acrylate

A study was made on the effect of novel molecule-inhibitors (nitroso-benzene and N-substituted p-nitroso-aniline derivatives, as well as phenothiazine) on the radical polymerization of methyl acrylate initiated by AIBN at 50°. The investigated compounds are strong inhibitors, in contrast to the “traditional” molecule-inhibitors, which only retard the polymerization of MA. The relative reactivities of the inhibitors and the stoichiometric coefficients of the inhibition reactions were determined. Phenothiazine is even more reactive than the nitroso-compounds, but the inhibition is accompanied by some chain-regeneration.     

Copper-Mediated monochlorination of anilines and nitrogen-containing heterocycles

A simple and selective copper(II) chloride-mediated monochlorination of anilines and nitrogen-containing heterocycles has been developed. Stirring a mixture of aniline, copper(II) chloride, lithium chloride in EtOH under reflux condition produced 4-chloroaniline with high yield. Eighteen substrates including substituted anilines, N-substituted anilines, N,N-disubstituted anilines, 5-nitroindole and carbazole were all reactive and afforded desired products in moderate to excellent yields (52%–98%).     

Emulsion copolymerization of vinyl acetate and butyl acrylate in the presence of fluorescent dyes

This article describes our first experiments for preparing dye‐labeled latex particles by the emulsion copolymerization of a 4/1 (w/w) mixture of vinyl acetate‐butylacrylate (VAc‐BA). We discuss the synthesis of acrylate derivatives of phenanthrene, anthracene, and pyrene [9‐acryloxymethyl phenanthrene ( 7 ), 9‐acryloxymethyl‐10‐methyl anthracene ( 8 ), and 1‐acryloxymethyl pyrene ( 10 )] and an allyl ether derivative of anthracene [9‐allyoxymethyl‐10‐methyl anthracene ( 9 )]. Although the phenanthrene derivative 7 gave latex particles with high monomer conversion and good dye incorporation, the pyrene acrylate and both anthracene comonomers strongly inhibited the free‐radical reaction. To assist our search for a dye that would serve as a useful energy acceptor for phenanthrene and without suppressing VAc‐BA polymerization, we also examined batch emulsion polymerization in the presence of a variety of dye derivatives—substituted anthracenes, acridines, a coumarin, and two benzophenone derivatives. All of the anthracene derivatives, as well as acridine, strongly inhibited monomer polymerization. The coumarin dye 7‐hydroxy‐4‐methyl coumarin ( 22 ) that had only limited solubility allowed more than 90% monomer conversion. Most promising were 2‐hydroxy‐5‐methyl benzophenone ( 23 ) and 4‐N,N‐dimethylamino benzophenone ( 24 ) that at 1 mol % in the monomer mixture permitted virtually quantitative monomer conversion to latex. 4′‐Dimethylamino‐2‐acryloxy‐5‐methyl benzophenone ( 25 ) copolymerized well with the VAc‐BA mixture, yielding latex particles in high yield and with a narrow size distribution. These dyes appear to be useful acceptor dyes for energy‐transfer experiments with phenanthrene. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 1594–1607, 2002     

Polymerization and copolymerization of an isocyanate blocking agent. N-(1,1′-dimethyl-3-oxobutyl) acrylamide oxime. Mechanical and thermal properties

The bulk polymerization and copolymerization of N-(1,1′-dimethyl-3-oxobutyl) acrylamide oxime have been studied. Polymerization of diacetone acrylamide oxime was carried out with different initiating systems. The rate of polymerization of diacetone acrylamide oxime with azoisobutyronitrile as the initiating system was much higher than with peroxides. However, in the case of perester initiating systems (t-butyl perbenzoate and t-butyl per ethyl-2-hexanoate), cobalt salt promoted the polymerization rate markedly. Diacetone acrylamide oxime readily formed copolymers with a variety of comonomers (crosslinking agents and reactive diluents). Gel permeation chromatography has shown a higher reactivity of diacetone acrylamide oxime with trimethylol propane trimethacrylate as crosslinking agent and N-vinyl-pyrrolidone as reactive diluent. Therefore, the dynamic mechanical analyses presented an increase in T_g with trimethylolpropane trimethacrylate and N-vinyl-pyrrolidone as comonomers. The terpolymer formed with diacetone acrylamide oxime, trinethylolpropane trimethacrylate, and N-vinyl-pyrrolidone exhibited interesting mechanical properties and high temperature behavior.     

Atom transfer radical polymerization of hexyl acrylate and preparation of its “all‐acrylate” block copolymers

This investigation reports the polymerization of hexyl acrylate (HA) using atom transfer radical polymerization technique and subsequently the preparation of its di‐ and triblock copolymers with methyl methacrylate. Atom transfer radical polymerization of HA was investigated using different initiators and CuBr or CuCl as catalyst in combination with varying ligands, e.g., 2,2′‐bipyridine and N,N,N′,N″,N″‐pentamethyl diethylenetriamine. Reaction parameters were adjusted to successfully polymerize HA with well‐defined molecular weights and narrow polydispersity indices. The polymerization was better controlled by the addition of polar solvents, which created a homogeneous catalytic system. UV–vis analysis showed that the polar solvent, acetone coordinated with copper (I), changes the nature of the copper catalyst, thereby influencing the dynamic equilibrium of activation–deactivation cycle. This resulted in improved control over polymerization as well as in lowering the polydispersity indices, but at the cost of polymerization rate compared with the bulk process. The presence of ? Br end group in the polymer chains was confirmed by ¹H NMR as well as MALDI‐TOF mass analysis. In addition, poly(hexyl acrylate) was used as macroinitiator to prepare various “all‐acrylate” block (diblock, triblock) copolymers that were characterized by GPC and ¹H NMR. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 3499–3511, 2008     

A Chaperonin as Protein Nanoreactor for Atom‐Transfer Radical Polymerization

The group II chaperonin thermosome (THS) from the archaea Thermoplasma acidophilum is reported as nanoreactor for atom‐transfer radical polymerization (ATRP). A copper catalyst was entrapped into the THS to confine the polymerization into this protein cage. THS possesses pores that are wide enough to release polymers into solution. The nanoreactor favorably influenced the polymerization of N‐isopropyl acrylamide and poly(ethylene glycol)methylether acrylate. Narrowly dispersed polymers with polydispersity indices (PDIs) down to 1.06 were obtained in the protein nanoreactor, while control reactions with a globular protein–catalyst conjugate only yielded polymers with PDIs above 1.84.     

Kinetic study of in situ normal and AGET atom transfer radical copolymerization of n–butyl acrylate and styrene: Effect of nanoclay loading and catalyst concentration

The effect of clay nanolayers and catalyst concentration on the kinetics of atom transfer radical copolymerization of styrene and butyl acrylate initiated by activators generated by electron transfer (AGET initiation system) or an alkyl halide (normal initiation system) was studied. Monomer conversion was studied by attenuated total reflection–Fourier transform infrared spectroscopy, and also proton nuclear magnetic resonance (¹H NMR) spectroscopy was utilized to evaluate the heterogeneity in the composition of poly(styrene‐co‐butyl acrylate) chains. A decrease in the copolymerization rate of styrene and butyl acrylate in the presence of clay platelets was observed since clay layers confine the accessibility of monomer and growing radical chains. Considering the linear first‐order kinetics of the polymerization, successful AGET and normal atom transfer radical polymerization (ATRP) in the presence of clay nanolayers were carried out. Consequently, poly(styrene‐co‐butyl acrylate) chains with narrow molecular weight distribution and low polydispersity indices (1.13–1.15) were obtained. The linearity of ln([M]₀/[M]) versus time and molecular weight distribution against conversion plots indicates that the proportion of propagating radicals is almost constant during the polymerization, which is the result of insignificant contribution of termination and transfer reactions. Controlled synthesis of poly(styrene‐co‐butyl acrylate)/clay is implemented with the diminishing catalyst concentration of copper(I) bromide/N,N,N′,N′′,N′′‐pentamethyl diethylene triamine without affecting the copolymerization rate of normal ATRP. © 2012 Wiley Periodicals, Inc. Int J Chem Kinet 44: 789–799, 2012