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Methyl Acrylate (methyl + acrylate)
Selected AbstractsPolymerization of Methyl Acrylate by a 2,6-Bis(2-benzimidazyl)pyridine Zirconium Dichloride/MAO Catalyst SystemMACROMOLECULAR CHEMISTRY AND PHYSICS, Issue 21 2006Hyun Yong Cho Abstract Summary: A novel non-metallocene Zr(IV) complex bearing a bianionic form of the ligand 2,6-bis(2-benzimidazolyl)pyridine is synthesized. This Zr complex is an active catalyst for the polymerization of MA via coordination polymerization in the presence of methylaluminoxane MAO. The activity and MWD are increased as the polymerization temperature increases. The maximum activity is observed at Al/Zr molar ratio of 100 and the deactivation is shown above 100, resulting from an inactive bimetallic complex between catalyst and free TMA presented in MAO. Decrease in MWD is observed with higher MAO concentration due to its role in chain transfer during the chain propagation. The reaction of the ligand and catalyst synthesis. [source] ChemInform Abstract: Lewis Acid Mediated Reactions of 1-Cyclopropyl-2-arylethanone Derivatives with Allenic Ester, Ethyl Acetoacetate, and Methyl Acrylate.CHEMINFORM, Issue 49 2008Min Shi Abstract ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a "Full Text" option. The original article is trackable via the "References" option. [source] Highly Diastereo- and Enantioselective Copper-Catalyzed Domino Reduction/Aldol Reaction of Ketones with Methyl Acrylate.CHEMINFORM, Issue 24 2006Julia Deschamp Abstract ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract, please click on HTML or PDF. [source] Baylis,Hillman Reactions of N-Arylidenediphenylphosphinamides with Methyl Vinyl Ketone, Methyl Acrylate, and Acrylonitrile.CHEMINFORM, Issue 39 2002Min Shi Abstract For Abstract see ChemInform Abstract in Full Text. [source] Synthesis and Reactivity of Oxametallacyclic Niobium Compounds by Using ,,,-Unsaturated Carbonyl Ligands,EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 14 2008Rocío A. Arteaga-Müller Abstract Reduction of mono(cyclopentadienyl)niobium complexes [NbCpRCl4] [CpR = C5Me4H (1), C5H4SiMe2Cl (2), C5H4SiMe3 (3)] with Na/Hg in the presence of methyl methacrylate [MMA, CH2=C(Me)C(O)OMe (a)], methyl acrylate [MA, CH2=CHC(O)OMe (b)] and mesityl oxide [MO, CMe2=CHC(O)Me (c)] afforded the corresponding derivatives [NbCpRCl2(LL)] [CpR = C5Me4H, LL = MMA (1a); CpR = C5H4SiMe2Cl, LL = MMA (2a), MA (2b), MO (2c); CpR = C5H4SiMe3, LL = MMA (3a), MA (3b)] in variable yields depending on both the cyclopentadienyl and the ,,,-unsaturated carbonyl compounds. The reactivity of these complexes was studied toward protic and Lewis acids. Addition of triflic acid TfOH (Tf = CF3SO2) to 3b gave the triflate complex [NbCpRCl2{(CH2)2C(O)OMe}(OTf)] [CpR = C5H4SiMe3 (4)]. The Lewis acids E(C6F5)3 (E = B, Al) reacted with complexes 2b and 3b to give the three-membered metallacyclic (or ,2 -enone) compounds [NbCpRCl2{,2 -CH2=CHC(OMe){O·E(C6F5)3}}] [CpR = C5H4SiMe2Cl, E = B (5), Al (6); CpR = C5H4SiMe3, E = B (7), Al (8)], which decomposed to the corresponding adducts MA·E(C6F5)3. The same reaction with the 2a and 3a derivatives only allowed the observation of the corresponding adducts MMA·E(C6F5)3. Complexes 2a,b and 3a,b reacted with CO with elimination of the acrylate compounds, MA and MMA, respectively, to give the carbonylniobium(III) compounds [NbCpRCl2(CO)2]2 [CpR = C5H4SiMe2Cl (9), C5H4SiMe3 (10)]. Analogous reactions with CNAr showed the elimination of the free MA and MMA compounds. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008) [source] Photochemical Reactivity of 2-Azido-1,3-thiazole and 2-Azido-1,3-benzothiazole: A Procedure for the Aziridination of Enol EthersEUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 6 2009Maurizio D'Auria Abstract Direct irradiation of a mixture of the azido,tetrazole tautomers of 2-azido-1,3-thiazole and 2-azido-1,3-benzothiazole in toluene solution gives products arising from the intermediate nitrene, which in turn undergoes ring opening in the case of 2-azido-1,3-thiazole to give a polymer, and dimerization in the case of 2-azido-1,3-benzothiazole to give [1,3]benzothiazolo[2,,3,:3,4][1,2,4,5]tetraazino[6,1b][1,3]benzothiazolein low yields. When irradiation is performed in the presence of methyl acrylate or various enol ethers, aziridination of the double bond is observed, with good yields in the case of enol ethers. Among these, 1-(6-methyl-3,4-dihydro-2H -pyran-2-yl)ethanone undergoes aziridination with complete diastereoselectivity to give the (1RS,3RS,6SR) diastereomer.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009) [source] Lewis Acid Induced [2+2] Cycloadditions of Silyl Enol Ethers with ,,,-Unsaturated Esters: A DFT AnalysisEUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 18 2005Manuel Arnó Abstract The Lewis acid (LA) induced cycloaddition of trimethysilyl vinyl ether with methyl acrylate has been studied by DFT methods at the B3LYP/6-31G* level. In the absence of an LA, a [4+2] cycloaddition between the silyl enol ether and methyl acrylate in the s-cis conformation takes place through an asynchronous, concerted bond-formation process. This cycloaddition presents a large activation enthalpy of 21.1 kcal,mol,1. Coordination of the LA AlCl3 to the carbonyl oxygen atom of methyl acrylate yields a change of molecular mechanism from a concerted to a two-step mechanism and produces a drastic reduction of the activation energy. This stepwise mechanism is initialized by the nucleophilic attack of the enol ether at the ,-position of methyl acrylate in a Michael-type addition. The very low activation energy (7.1 kcal,mol,1)associated with this nucleophilic attack can be related to the increase of the electrophilicity of the LA-coordinated ,,,-unsaturated ester, which favors the cycloaddition through a polar process. The subsequent ring-closure allows the formation of the corresponding [2+2] and [4+2] cycloadducts. While the [4+2] cycloadduct is formed by kinetic control, the [2+2] cycloadducts are formed by thermodynamic control. The energetic results provide an explanation for the conversion of [4+2] cycloadducts into the thermodynamically more stable [2+2] ones. The cis/trans ratio found for the catalytic [2+2] process is in agreement with the experimental outcome. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005) [source] A Versatile Solvent-Free "One-Pot" Route to Polymer Nanocomposites and the in situ Formation of Calcium Phosphate/Layered Silicate Hybrid NanoparticlesADVANCED FUNCTIONAL MATERIALS, Issue 11 2010Hans Weickmann Abstract Poly(methyl methacrylate) (PMMA), polystyrene (PS), and polyurethane (PU) nanocomposites containing well-dispersed calcium phosphate/layered silicate hybrid nanoparticles were prepared in a versatile solvent-free "one-pot" process without requiring separate steps, such as organophilic modification, purification, drying, dispersing, and compounding, typical for many conventional organoclay nanocomposites. In this "one-pot" process, alkyl ammonium phosphates were added as swelling agents to a suspension of calcium/layered silicate in styrene, methyl methacrylate, or polyols prior to polymerization. Alkyl ammonium phosphates were prepared in situ by reacting phosphoric acid with an equivalent amount of alkyl amines such as stearyl amine (SA) or the corresponding ester- and methacrylate-functionalized tertiary alkyl amines, obtained via Michael Addition of SA with methyl acrylate or ethylene 2-methacryloxyethyl acrylate. Upon contact with the calcium bentonite suspension, the cation exchange of Ca2+ in the silicate interlayers for alkyl ammonium cations rendered the bentonite organophilic and enabled effective swelling in the monomer accompanied by intercalation and in situ precipitation of calcium phosphates. According to energy dispersive X-ray analysis, the calcium phosphate precipitated exclusively onto the surfaces of the bentonite nanoplatelets, thus forming easy-to-disperse calcium phosphate/layered silicate hybrid nanoparticles. Incorporation of 5,15,wt% of such hybrid nanoparticles into PMMA, PS, and PU afforded improved stiffness/toughness balances of the polymer nanocomposites. Functionalized alkyl ammonium phosphate addition enabled polymer attachment to the nanoparticle surfaces. Transmission electron microscopy (TEM) analyses of PU and PU-foam nanocomposites, prepared by dispersing hybrid nanoparticles in the polyols prior to isocyanate cure, revealed the formation of fully exfoliated hybrid nanoparticles. [source] High-Strain Shape-Memory PolymersADVANCED FUNCTIONAL MATERIALS, Issue 1 2010Walter Voit Abstract Shape-memory polymers (SMPs) are self-adjusting, smart materials in which shape changes can be accurately controlled at specific, tailored temperatures. In this study, the glass transition temperature (Tg) is adjusted between 28 and 55,°C through synthesis of copolymers of methyl acrylate (MA), methyl methacrylate (MMA), and isobornyl acrylate (IBoA). Acrylate compositions with both crosslinker densities and photoinitiator concentrations optimized at fractions of a mole percent demonstrate fully recoverable strains at 807% for a Tg of 28,°C, at 663% for a Tg of 37,°C, and at 553% for a Tg of 55,°C. A new compound, 4,4,-di(acryloyloxy)benzil (referred to hereafter as Xini) in which both polymerizable and initiating functionalities are incorporated in the same molecule, was synthesized and polymerized into acrylate shape-memory polymers, which were thermomechanically characterized yielding fully recoverable strains above 500%. The materials synthesized in this work were compared to an industry standard thermoplastic SMP, Mitsubishi's MM5510, which showed failure strains of similar magnitude, but without full shape recovery: residual strain after a single shape-memory cycle caused large-scale disfiguration. The materials in this study are intended to enable future applications where both recoverable high-strain capacity and the ability to accurately and independently position Tg are required. [source] Fabrication of Reversibly Crosslinkable, 3-Dimensionally Conformal Polymeric Microstructures,ADVANCED FUNCTIONAL MATERIALS, Issue 20 2008Luke A. Connal Abstract Multifaceted porous materials were prepared through careful design of star polymer functionality and properties. Functionalized core crosslinked star (CCS) polymers with a low glass transition temperature (Tg) based on poly(methyl acrylate) were prepared having a multitude of hydroxyl groups at the chain ends. Modification of these chain ends with 9-anthracene carbonyl chloride introduces the ability to reversibly photocrosslink these systems after the star polymers were self-assembled by the breath figure technique to create porous, micro-structured films. The properties of the low Tg CCS polymer allow for the formation of porous films on non-planar substrates without cracking and photo-crosslinking allows the creation of stabilized honeycomb films while also permitting a secondary level of patterning on the film, using photo-lithographic techniques. These multifaceted porous polymer films represent a new generation of well-defined, 3D microstructures. [source] Siloxane Copolymers for Nanoimprint Lithography,ADVANCED FUNCTIONAL MATERIALS, Issue 1 2007P. Choi Abstract Presented here is the novel use of thermoplastic siloxane copolymers as nanoimprint lithography (NIL) resists for 60,nm features. Two of the most critical steps of NIL are mold release and pattern transfer through dry etching. These require that the NIL resist have low surface energy and excellent dry-etching resistance. Homopolymers traditionally used in NIL, such as polystyrene (PS) or poly(methyl methacrylate) (PMMA), generally cannot satisfy all these requirements as they exhibit polymer fracture and delamination during mold release and have poor etch resistance. A number of siloxane copolymers have been investigated for use as NIL resists, including poly(dimethylsiloxane)- block -polystyrene (PDMS- b -PS), poly(dimethylsiloxane)- graft -poly(methyl acrylate)- co -poly(isobornyl acrylate) (PDMS- g -PMA- co -PIA), and PDMS- g -PMMA. The presence of PDMS imparts the materials with many properties that are favorable for NIL, including low surface energy for easy mold release and high silicon content for chemical-etch resistance,in particular, extremely low etch rates (comparable to PDMS) in oxygen plasma, to which organic polymers are quite susceptible. These properties give improved NIL results. [source] Cover Picture: Synthesis of Gadolinium-Labeled Shell-Crosslinked Nanoparticles for Magnetic Resonance Imaging Applications (Adv. Funct.ADVANCED FUNCTIONAL MATERIALS, Issue 8 2005Mater. Abstract Robust, amphiphilic core,shell nanoparticles that are selectively labeled with gadolinium in the hydrophilic and water-swollen shell layer are depicted in the cover picture. These well-defined nanostructured materials exhibit high relaxivity, a large loading capacity, and are based upon a biocompatible platform for ultimate function in magnetic resonance imaging (MRI) applications, as reported by Wooley and co-workers on p.,1248. Shell-crosslinked knedel-like nanoparticles (SCKs; "knedel" is a Polish term for dumplings) were derivatized with gadolinium chelates and studied as robust magnetic-resonance-imaging-active structures with hydrodynamic diameters of 40,±,3,nm. SCKs possessing an amphiphilic core,shell morphology were produced from the aqueous assembly of diblock copolymers of poly-(acrylic acid) (PAA) and poly(methyl acrylate) (PMA), PAA52,b,PMA128, and subsequent covalent crosslinking by amidation upon reaction with 2,2,-(ethylenedioxy)bis(ethylamine) throughout the shell layer. The properties of these materials, including non-toxicity towards mammalian cells, non-immunogenicity within mice, and capability for polyvalent targeting, make them ideal candidates for utilization within biological systems. The synthesis of SCKs derivatized with GdIII and designed for potential use as a unique nanometer-scale contrast agent for MRI applications is described herein. Utilization of an amino-functionalized diethylenetriaminepentaacetic acid,Gd analogue allowed for direct covalent conjugation throughout the hydrophilic shell layer of the SCKs and served to increase the rotational correlation lifetime of the Gd. In addition, the highly hydrated nature of the shell layer in which the Gd was located allowed for rapid water exchange; thus, the resulting material demonstrated large ionic relaxivities (39,s,1,mM,1) in an applied magnetic field of 0.47,T at 40,°C and, as a result of the large loading capacity of the material, also demonstrated high molecular relaxivities (20,000,s,1,mM,1). [source] A General Approach to the Synthesis of ,2 -Amino Acid Derivatives via Highly Efficient Catalytic Asymmetric Hydrogenation of ,-AminomethylacrylatesADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 9 2010Yujuan Guo Abstract A new strategy was developed for the synthesis of a valuable class of ,-aminomethylacrylates via the Baylis,Hillman reaction of different aldehydes with methyl acrylate followed by acetylation of the resulting allylic alcohols and SN2,-type amination of the allylic acetates. Asymmetric hydrogenation of these diverse olefinic precursors using rhodium(Et-Duphos) catalysts provided the corresponding ,2 -amino acid derivatives with excellent enantioselectivities and exceedingly high reactivities (up to >99.5% ee and S/C=10,000). The first hydrogenation of (Z)-configurated substrates was studied for the synthesis of ,2 -amino acid derivatives. The high influence of the substrate geometry and steric hindrance on the reactivity and enantioselectivity was also disclosed for this reaction. This protocol provides a highly practical, facile and scalable method for the preparation of optically pure ,2 -amino acids and their derivatives under mild reaction conditions. [source] Nanogels of poly(acrylic acid): Uptake and release behavior with fluorescent oligothiophene-labeled bovine serum albuminJOURNAL OF APPLIED POLYMER SCIENCE, Issue 5 2010Simona Argentiere Abstract Nanometer-sized poly(acrylic acid) (PAA) hydrogels were synthesized by emulsion polymerization of methyl acrylate and subsequent acidic hydrolysis. The nanohydrogel was characterized by spectroscopic methods (FTIR and 1H-NMR) and scanning probe techniques, and their pH-dependent swelling behavior was studied by dynamic light scattering. To determine the suitability of PAA nanogels as pH-sensitive carriers for biomedical applications, uptake and release of an oligothiophene fluorophore and its albumin conjugated from PAA nanogels were investigated as a function of pH by absorption and photoluminescence measurements. It was observed that uptake and release processes of both the oligothiophene and its conjugate could be controlled by changing the pH of the external solution. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010 [source] Polymer electrolyte membranes having sulfoalkyl grafts into ETFE film prepared by radiation-induced copolymerization of methyl acrylate and methyl methacrylateJOURNAL OF APPLIED POLYMER SCIENCE, Issue 1 2009Truong Thi Hanh Abstract Polymer electrolyte membranes (PEMs) containing alkylsulfonic acid grafts can be prepared by radiation-induced graft copolymerization of methyl acrylate (MA) and methyl methacrylate (MMA) into a poly(ethylene- co -tetrafluoroethylene) film followed by sulfonation of the MA units in the copolymer grafts using an equimolar complex of chlorosulfonic acid and 1,4-dioxane (ClSO3H-Complex). PEMs with MA/MMA copolymer grafts that are 33%,79% MA units were prepared by preirradiation with a dose of 20 kGy and grafting in bulk comonomers at 60°C. The grafted films are treated with ClSO3H-Complex to obtain PEMs with ion exchange capacity of 0.36-0.81 mmol/g (sulfonation degrees of 20%,40%) and proton conductivity of 0.04-0.065 S/cm. These values can be controlled by changing the MA content the sulfonation occurring at an ,-carbonyl carbon. The PEMs with higher MMA content showed higher durability in water (80°C) and under oxidative conditions (3% H2O2) at 60°C. This is because the PMMA grafts in the PEMs have no proton at an ,-carbonyl carbon, which is considered to be a trigger of the degradation of grafting polymers. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009 [source] Kinetics and mechanism of the radical copolymerization of 4-vinyl pyridine with methyl acrylate initiated by p -acetylbenzylidene triphenylarsonium ylideJOURNAL OF APPLIED POLYMER SCIENCE, Issue 5 2009S. P. Tiwari Abstract The free-radical copolymerization of 4-vinyl pyridine (4-VP) with methyl acrylate (MA) initiated by p -acetylbenzylidene triphenylarsonium ylide at 60 ± 0.1°C with dioxane as an inert solvent yielded random copolymers. The kinetic equation was Rp , [Ylide]0.83[4-VP]0.33 [MA]0.40 (where Rp is the rate of polymerization); in other words, the system followed nonideal kinetics. The values of the energy of activation and kp2/kt (where kp is the rate constant of propagation and kt is the rate constant of termination) were 23.21 kJ/mol and 1.212 × 10,5 mol L,1 s,1, respectively. The reactivity ratios calculated with the Kelen,Tüdos method were 0.14 ± 0.0075 for 4-VP and 0.56 ± 0.0078 for MA. The copolymers were characterized with Fourier transform infrared, proton nuclear magnetic resonance, differential scanning calorimetry, and electron spin resonance methods. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009 [source] Properties of poly(AAc- co -HPMA- cl -EGDMA) hydrogel-bound lipase of Pseudomonas aeruginosa MTCC-4713 and its use in synthesis of methyl acrylateJOURNAL OF APPLIED POLYMER SCIENCE, Issue 1 2007Shamsher Singh Kanwar Abstract Microbial lipases (E.C. 3.1.1.3) are preferred biocatalysts for the synthesis of esters in organic solvents. Various extracellular thermoalkaliphilic lipases have been reported from Pseudomonas sp. In the present study, a purified alkaline thermoalkalophilic extracellular lipase of Pseudomonas aeruginosa MTCC-4713 was efficiently immobilized onto a synthetic poly(AAc- co -HPMA- cl -EGDMA) hydrogel by adsorption and the bound lipase was evaluated for its hydrolytic potential towards various p -nitrophenyl acyl esters varying in their C-chain lengths. The bound lipase showed optimal hydrolytic activity towards p -nitrophenyl palmitate (p -NPP) at pH 8.5 and temperature 45°C. The hydrolytic activity of the hydrogel-bound lipase was markedly enhanced by the presence of Hg2+, Fe3+, and NH salt ions in that order. The hydrogel-immobilized lipase (25 mg) was used to perform esterification in various n -alkane(s) that resulted in , 84.9 mM of methyl acrylate at 45°C in n -heptane under shaking (120 rpm) after 6 h, when methanol and acrylic acid were used in a ratio of 100 mM:100 mM, respectively. Addition of a molecular sieve (3Å × 1.5 mm) to the reaction system at a concentration of 100 mg/reaction vol (1 mL) resulted in a moderate enhancement in conversion of reactants into methyl acrylate (85.6 mM). During the repetitive esterification under optimum conditions, the hydrogel-bound lipase produced 71.3 mM of ester after 10th cycle of reuse. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 183,191, 2007 [source] Kinetics of graft copolymerization of poly(hexanedioic acid ethylene glycol) and methyl acrylate initiated by potassium diperiodatocuprate(III)JOURNAL OF APPLIED POLYMER SCIENCE, Issue 4 2007Libin Bai Abstract A redox system, potassium diperiodatocuprate(III) [DPC]/poly(hexanedioic acid ethylene glycol) (PEA) system, was employed to initiate graft copolymers of methyl acrylate (MA) and PEA in alkaline medium. The results indicate that the equation of the polymerization rate (Rp) is as follows: Rp = k [MA]1.62[Cu(III)]0.69, and that the overall activation energy of graft polymerization is 42.5 kJ/mol. The total conversion at different conditions (concentration of reactants, temperature, concentration of the DPC, and reaction time) was also investigated. The infrared spectra proved that the graft copolymers were synthesized successfully. Some basic properties of the graft copolymer were studied by instrumental analyses, including thermogravimetry and scanning electron microscope. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 2376,2381, 2007 [source] Synthesis of 4H- indeno[1,2- b]thiophenes, 8H -indeno[2,1- b]-thiophenes and 8H -indeno[2,1- b]furans having acrylic acid unitJOURNAL OF HETEROCYCLIC CHEMISTRY, Issue 2 2008Ki Joon Jeon Treatment of methyl propiolate and 2-(thiophen-2-yl)benzaldehyde, 2-(thiophen-3-yl)benzaldehyde or 2-(furan-3-yl)benzaldehyde with tetrabutylammonium iodide/zirconium (IV) chloride or treatment of methyl acrylate and the same aldehydes with 1,4-diazabicyclo[2,2,2]octane and triethanolamine induce an aldol-type reaction to furnish Baylis-Hillman adducts ,-iodo-,-(hydroxymethyl)acrylates or ,-(hydroxy-methyl)acrylates, respectively. These can be used for the preparation of indenothiophenes and indenofurans having acrylic acid unit by intramolecular Friedel-Crafts reaction with sulfuric acid in tetrachloromethane. [source] Investigations on regio- and stereoselectivities in cycloadditions involving ,- (3-pyridyl)- N -phenylnitrone: Development of an efficient route to novel nicotine analogsJOURNAL OF HETEROCYCLIC CHEMISTRY, Issue 6 2005Gurpinder Singh Thermal reactions of hitherto ,-(3-pyridyl)- N -phenylnitrone (1) with mono-substituted electron-rich and electron-neutral dipolarophiles are regio-, and stereo-selective (exo -selective), controlled by LUMO - dipole - HOMO- dipolarophile interaction, and furnish syn -5-substituted-3-(3-pyridyl)-isoxazolidines (5) in high yields. With electron deficient dipolarophiles such as acrylonitrile there is observed a loss of regioselectivity as well as stereoselectivity and the regioselectivity is reversed in reactions with methyl vinyl ketone and methyl acrylate, due to intervention of HOMO-dipole - LUMO-dipolarophile interaction, affording 4-substi-tuted-3-(3-pyridyl)-isoxazolidines (7) as major products. Reactions of nitrone (1) with disubstituted dipolarophiles such as methyl methacrylate and ethyl coronate furnish methyl syn -5-methy-3-pyridyl-1-phenyl-isoxazolidine-5-carboxylate (8) and ethyl anti -5-methy-3-pyridyl-1-phenyl-isoxazolidine-4-carboxylate (10), respectively, in high yields. Reaction with N -Phenylmaleimide affords novel isoxazolidino-pyrro-lidinediones bearing a 3-pyridyl moiety (11, 12). A mechanistic rationalization of the obtained results in terms of electronic, steric and secondary interactions is proffered. [source] The influence of solution-state conditions and stirring rate on the assembly of poly(acrylic acid)-containing amphiphilic triblock copolymers with multi-aminesJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 20 2010Jennifer L. Sorrells Abstract In the effort towards making nanoscale objects and assemblies feasible for use as functional materials, it is imperative to obtain control over the fundamental architectures and essential to understand what experimental conditions cause the manifestation of specific morphologies. A number of factors are known to influence the shape during the self-assembly of amphiphilic block copolymers in solution, including solvent composition, polymer length, hydrophobicity versus hydrophilicity, as well as the addition of additives that can interact with segments of the block copolymers. This research, focused on developing an understanding of the micellar architectures accessed by the amphiphilic triblock copolymer of acrylic acid, methyl acrylate, and styrene, PAA85 - b -PMA40 - b -PS35, as a function of the stirring rate, together with other factors, when undergoing coassembly with ethylenediamine or diethylenetriamine in water/tetrahydrofuran solutions. The work demonstrates that the rate at which the polymer solution was stirred impacts the shape of the solution-state assemblies formed by the triblock copolymer. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010 [source] Free radical and nitroxide mediated polymerization of hydroxy,functional acrylates prepared via lipase,catalyzed transacylation reactionsJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 12 2010Dragos Popescu Abstract 3-Hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 2-methyl-3-hydroxypropyl acrylate, 2-hydroxypropyl acrylate, neopentyl glycol acrylate, glyceryl acrylate, and dihydroxyhexyl acrylate were prepared via transacylation reaction of methyl acrylate with diols and triols catalyzed by Candida antarctica lipase B. After removal of the enzyme by filtration and the methyl acrylate by distillation, the monomers were polymerized via free radical polymerization (FRP) with azobisisobutyronitrile as initiator and nitroxide mediated polymerization (NMP) employing BlocbuilderÔ alkoxyamine initiator and SG-1 free nitroxide resulting in hydroxy functional poly(acrylates). The NMP kinetics are discussed in detail. In addition, the polymers obtained by FRP and NMP are compared and the results are related to the amount of bisacrylates that are present in the initial monomer mixtures resulting from the transacylation reactions. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 2610,2621, 2010 [source] Room-temperature RAFT copolymerization of 2-chloroallyl azide with methyl acrylate and versatile applications of the azide copolymersJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 6 2010Guang Li Abstract A new vinyl azide monomer, 2-chlorallyl azide (CAA), has been synthesized from commercially available reagent in one step. The reversible addition fragmentation chain transfer (RAFT) copolymerization of CAA with methyl acrylate (MA) was carried out at room temperature using a redox initiator, benzoyl peroxide (BPO)/N,N -dimethylaniline (DMA), in the presence of benzyl 1H -imidazole-1-carbodithioate (BICDT). The polymerization results showed that the process bears the characteristics of controlled/living radical polymerizations, such as the molecular weight increasing linearly with the monomer conversion, the molecular weight distribution being narrow, and a linear relationship existing between ln([M]0/[M]) and the polymerization time. Chain extension polymerization was performed successfully to prepare block copolymer. Furthermore, the azide copolymers were functionalized by CuI -catalyzed "click" reaction with alkyne-containing poly(ethylene glycol) (PEG) to yield graft copolymers with hydrophilic PEG side chains. Surface modification of the glass sheet was successfully achieved via the crosslinking reaction of the azide copolymer under UV irradiation at ambient temperature. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 1348,1356, 2010 [source] Synthesis of dendritic macromolecules through divergent iterative thio-bromo "Click" chemistry and SET-LRPJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 15 2009Brad M. Rosen Abstract The development of a novel nucleophilic thio-bromo "Click" reaction, specifically base-mediated thioetherification of thioglycerol with ,-bromoesters was reported in an earlier article. The combination of this thio-bromo click reaction with subsequent acylation with 2-bromopropionyl bromide provides an iterative two-step divergent growth approach to the synthesis of a new class of poly(thioglycerol-2- propionate) (PTP) dendrimers. In this article, the addition of a third step, the single-electron transfer living radical polymerization (SET-LRP) of methyl acrylate (MA), was shown to provides access to a three-step "branch" and "grow" divergent approach to dendritic macromolecules wherein poly(methyl acrylate) (PMA) connects the branching subunits. This facile methodology can provide a diversity of dendritic macromolecular topologies and will ultimately provide the means to the development of self-organizable dendritic macromolecules. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 3940,3948, 2009 [source] Solid acid clay mediated copolymerization of methyl acrylate and 1-octene: 2D NMR substantiation of predominant alternating comonomer sequenceJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 8 2009Sukhdeep Kaur Abstract Montmorillionite K10 powder presence during radically initiated copolymerization of methyl acrylate (M) and 1-octene (O) gave copolymers with higher incorporation of alkene unit. Highly viscous and transparent copolymers showed alternation irrespective of the copolymer composition. Increasing the amount of K10 powder increased the total percentage conversion, as well as 1-octene incorporation. The monomodal curves obtained in gel permeation chromatography (GPC) substantiated that true copolymers were formed. The alternation in the copolymers was authenticated through Heteronuclear Multiple Quantum Correlation (HMQC) experiments in conjugation with Total Correlated Spectroscopy (TOCSY). © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 2156,2162, 2009 [source] Bimolecular radical termination: New perspectives and insightsJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 10 2008Geoffrey Johnston-Hall Abstract The reversible addition-fragmentation chain transfer-chain length dependent termination (RAFT-CLD-T) method has allowed us to answer a number of fundamental questions regarding the mechanism of diffusion-controlled bimolecular termination in free-radical polymerization (FRP). We carried out RAFT-mediated polymerizations of methyl acrylate (MA) in the presence of a star matrix to develop an understanding of the effect of polymer matrix architecture on the termination of linear polyMA radicals and compared this to polystyrene, polymethyl methacrylate, and polyvinyl acetate systems. It was found that the matrix architecture had little or no influence on termination in the dilute regime. However, due to the smaller hydrodynamic volumes of the stars in solution compared to linear polymer of the same molecular weight, the gel onset point occurred at greater conversions, and supported the postulate that chain overlap (or c*) is the main cause for the observed autoacceleration observed in FRP. Other theories based on "short,long" termination or free-volume should be disregarded. Additionally, since our systems are well below the entanglement molecular weight, entanglements should also be disregarded as the cause of the gel onset. The semidilute regime occurs over a small conversion range and is difficult to quantify. However, we obtain accurate dependencies for termination in the concentrated regime, and observed that the star polymers (through the tethering of the arms) provided constriction points in the matrix that significantly slow the diffusion of linear polymeric radicals. Although, this could at first sight be postulated to be due to reptation, the dependencies showed that reptation could be considered only at very high conversions (close to the glass transition regime). In general, we find from our data that the polymer matrix is much more mobile than what is expected if reptation were to dominate. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 3155,3173, 2008 [source] Ultrafast SET-LRP of methyl acrylate at 25 °C in alcoholsJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 8 2008Gerard Lligadas Abstract 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 ,,,-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 [source] Synthesis of perfectly bifunctional polyacrylates by single-electron-transfer living radical polymerizationJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 20 2007Gerard Lligadas Abstract Poly(methyl acrylate)s, poly(ethyl acrylate)s, and poly(butyl acrylate)s with ,,,-di(bromo) chain ends and Mn 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 [source] Preparation, characterization, and chiral recognition of optically active polymers containing pendent chiral units via reversible addition-fragmentation chain transfer polymerizationJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 16 2007Jian Wang Abstract Optically active polymers bearing chiral units at the side chain were prepared via reversible addition-fragmentation chain transfer (RAFT) polymerization in the presence of 2,2,-azobisisobutyronitrile (AIBN)/benzyl dithiobenzoate (BDB), using a synthesized 6- O - p -vinylbenzyl-1,2:3,4-Di- O -isopropylidene- D -galactopyranose (VBPG) as the monomer. The experimental results suggested that the polymerization of the monomer proceeded in a living fashion, providing chiral group polymers with narrow molecular weight distributions. The optically active nature of the obtained poly (6- O - p -vinylbenzyl-1,2:3,4-Di- O -isopropylidene- D -galactopyranose) (PVBPG) was studied by investigating the dependence of specific rotation on the molecular weight of PVBPG and the concentration of PVBPG in tetrahydrofuran (THF). The results showed the specific rotation of PVBPG increased greatly with the decrease of the concentration of the PVBPG homopolymer. In addition, the effect of block copolymers of PVBPG on the optically active nature was also investigated by preparing a series of diblock copolymers of poly(methyl methacrylate) (PMMA)- b -PVBPG, polystyrene (PS)- b -PVBPG, and poly(methyl acrylate) (PMA)- b -PVBPG. It was found that both the homopolymer and the diblock copolymers possessed specific rotations. Finally, the ability of chiral recognition of the PVBPG homopolymer was investigated via an enantiomer-selective adsorption experiment. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 3788,3797, 2007 [source] Synthesis of diblock copolymers by combining stable free radical polymerization and atom transfer radical polymerizationJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 8 2006Yan Shi Abstract A stable nitroxyl radical functionalized with an initiating group for atom transfer radical polymerization (ATRP), 4-(2-bromo-2-methylpropionyloxy)-2,2,6,6-tetramethyl-1-piperidinyloxy (Br-TEMPO), was synthesized by the reaction of 4-hydroxyl-2,2,6,6-tetramethyl-1-piperidinyloxy with 2-bromo-2-methylpropionyl bromide. Stable free radical polymerization of styrene was then carried out using a conventional thermal initiator, dibenzoyl peroxide, along with Br-TEMPO. The obtained polystyrene had an active bromine atom for ATRP at the ,-end of the chain and was used as the macroinitiator for ATRP of methyl acrylate and ethyl acrylate to prepare block copolymers. The molecular weights of the resulting block copolymers at different monomer conversions shifted to higher molecular weights and increased with monomer conversion. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 2468,2475, 2006 [source] | |||||||||||||