Vinyl Polymerization. 254.∗ Polymerization of Methyl Methacrylate by the System Cellulose-Water-Carbon Tetrachloride

Radical polymerization of methyl methacrylate initiated by the system cellulose-water-carbon tetrachloride was kinetically studied. Results obtained are: 1) The amounts of water, carbon tetrachloride, and cellulose affected the conversion. Michaelis-Menten's equation was applied to the relationship between the rate of polymerization and the amount of MMA. 2) Other methacrylates and acrylates were also polymerized by this system. 3) When methanol or ethanol was used instead of water, some weak polymerization activity was observed. 4) Initiating ability depended on the kind of cellulose used. 5) The activity of cellulose was not changed by washing with boiling water or by solvent extraction. 6) Polymerization was inhibited by the presence of air. 7) Heating in the presence of water and carbon tetrachloride markedly decreased the activity of the cellulose.     

Polymerization of Methyl Methacrylate in the Presence of N-Acetyl-ε-aminocaproic Acid Acetylamide

The effect of N-acetyl--aminocaproic acid acetylamide on radical polymerization of methyl methacrylate initiated with lauroyl peroxide was studied.     

Redox Polymerization of Methyl Methacrylate in the Fluorous Triphasic System

Fluorous-phase chemistry is currently a topic of considerable interest1-6. Since fluoroustriphasic reactions were first described by the Curran and co-workers7, this triphasicsystem has been widely used for detagging7,8 and phase-vanishing reactions9-11. …     

Studies on the Mechanism of Methyl Methacrylate Polymerization Initiated by Volatile and Nonvolatile Products of Methyl Methacrylate Plasma

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Monitor of Polymerization of Inverse Microemulsions Containing Methyl Methacrylate and Acrylic Acid

Microemulsions are isotropic, optically transparent and thermodynamically stabledispersion systems consisting of water, oil and suitable surfactants. Polymerization inmicroemulsions has been widely studied since 1980s, which can be divided intooil-in-wate…     

Polymerization of Methyl Methacrylate by Diisopropylamido bis(methylcyclopentadienyl) ytterbium Complex

Poty(methymethacryate)(PMMA)isaniInPOrtanPOlyInrwithawiderangOfusesinmateriaisandsurfaCecoatingindustrie5.lnl993,H.Yasudaetal.firstrePortedthalanhanocenehydrideandalkylcomPOundsareabletopo1ymerizemethylmethacrylateinalivingfashiontochrdtheSyndiotacticPMMAwithhighmo1ecularweightsandextremelynarrowmolecularweightdistributions[l1.Recentl}'.wehavefirstfoundthatthelanthanocenecomplexcontalningLn-Nobond(MeCp)=YbN(i-Pr)=(THF)isanotherkindofhighl'effectivecatalystfOrMMAPOtweriZationghng…     

Semibatch Emulsifier-free Emulsion Copolymerization of Methyl Methacrylate and n-Butyl Acrylate in the Presence of 2-Hydroxyethyl Methacrylate

ThemethodsofimProvingthestabilityofemulsifier-freeemulsionpolymerizationhavebeenreportedinliteraturet(a)choosingionizableinitiators,suchaspotassiumpersulfate'andazo-bis(isobutyramidinehydrochloride)';(b)copolymerizationwithhydrophiliccomonomers,whichinvolvestheionictypesuchascarboxylicmonomers',sulfoderivativesofvinylmonomers',andthenonionictypesuchasglycidylmethacrylate';(c)copolymerizationwithsurface-activemonomers,suchassulfodecylslyrylether';(d)addingorganicsolventstothesystem,suchasmethano…     

Vinyl Polymerization Initiated by Ceric Ion–Ethyl Cellosolve Redox System in Aqueous Nitric Acid

Abstract

Polymerizations of methyl methacrylate (MMA) and acrylonitrile (AN) were carried out in aqueous nitric acid at 30°C with the redox initiator system ammonium ceric nitrate-ethyl cellosolve (EC). A short induction period was observed as well as the attainment of a limiting conversion for polymerization reactions. The consumption of ceric ion was first order with respect to Ce(IV) concentration in the concentration range (0.2–0.4) × 10^?2 M, and the points at higher and lower concentrations show deviations from a linear fit. The plots of the inverse of pseudo-first-order rate constant for ceric ion consumption, (k ¹)^?1 vs [EC]^?1, gave straight lines for both the monomer systems with nonzero intercepts supporting complex formation between Ce(IV) and EC. The rate of polymerization increases regularly with [Ce(IV)] up to 0.003 M, yielding an order of 0.41, then falls to 0.0055 M and again shows a rise at 0.00645 M for MMA polymerization. For AN polymerization, R _p shows a steep rise with [Ce(IV)] up to 0.001 M, and beyond this concentration R _p shows a regular increase with [Ce(IV)], yielding an order of 0.48. In the presence of constant [NO^? ₃], MMA and AN polymerizations yield orders of 0.36 and 0.58 for [Ce(IV)] variation, respectively. The rates of polymerization increased with an increase in EC and monomer concentrations: only at a higher concentration of EC (0.5 M) was a steep fall in R _p observed for both monomer systems. The orders with respect to EC and monomer for MMA polymerization were 0.19 and 1.6, respectively. The orders with respect to EC and monomer for AN polymerization were 0.2 and 1.5, respectively. A kinetic scheme involving oxidation of EC by Ce(IV) via complex formation, whose decomposition gives rise to a primary radical, initiation, propagation, and termination of the polymeric radicals by biomolecular interaction is proposed. An oxidative termination of primary radicals by Ce(IV) is also included.     

Tb(lll) and Ca(ll) Ion Equilibria in the Presence of Glutamic Acid and Glutamine

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Synthesis of Sub-100 nm Nanoparticles by Emulsifier-free Emulsion Polymerization of α-Methylstyrene,Methyl Methacrylate and Acrylic Acid

The emulsifier-free emulsion copolymerization of α-methylstyrene (AMS) and methyl methacrylate (MMA) in the presence of functional monomer acrylic acid (AA) was carried out in batch process, giving birth to sub-100 nm nanoparticles. The kinetics of polymerization was investigated. The morphology and size of particles were monitored by TEM. The influences of the functional monomer AA concentration, initiator ammonium persulfate (APS) concentration, and polymerization temperature were studied. It was found that AMS caused a drastic decrease in both the rate of polymerization and the average degree of polymerization. The activation energy calculated from Arrhenius plot turned out to be 83.6 kJ/mol.     

Synthesis of A-B-A Type Block Copolymer of Methyl Methacrylate and Styrene by Living Free-Radical Polymerization†

Abstract

A newly synthesized iniferter, N,N′-dimethyl-N,N′-bis(phenethyl)-thiuram disulfide, has been used in the free-radical living polymerization of styrene by a photochemical method. The low molecular weight (M _w = 6000) difunctionalized polystyrene was used as a macroiniferter to photopolymerize methyl methacrylate, and was fractionated to obtain an A-B-A type block copolymer containing two poly(methyl methacrylate) units and one polystyrene unit in each block. The glass transition temperature, thermal stability, and ¹³C NMR of the block copolymer are discussed.     

Photocatalytic Activity of Tio2 Nanostructures Formed by Sol–Gel Method in the Presence of Hydrofluoric Acid in the Transformation of Carbon Oxides

Theoretical and Experimental Chemistry - The photocatalytic activity of TiO2 nanostructures in the reduction of CO2 to CH4 and oxidation of CO to CO2 was studied. It depends significantly on the...     

Oxidation of Oxalic Acid in the Ozone–Chloride–Ion Reaction System in an Aqueous Solution

Russian Journal of Physical Chemistry A - It is shown that the rate of oxidation of oxalic acid H2C2O4 during the ozonation of its solutions grows considerably if sodium chloride is added to the...     

Some Problems Concerning the Mechanism of the Isotactic Polymerization of Methyl Methacrylate Initiated by Organomagnesium Compounds in Toluene Solution—Application of Modified Dilatometer and NMR Methods

A dilatometer capable of being rapidly filled with monomer and initiator solutions mixed under carefully controlled conditions and a modification of an NMR T₁ program, adapted to store and display on recall the results of frequent sweeps at 30-s intervals of relevant proton resonances of a polymerizing mixture, are reported. These techniques have been applied to the identification of the optimum conditions for efficient, initiation of isotactic polymerization and investigation of the mechanism of propagation. It is shown that heat treatment does not remove the coordinated THF (1 molecule per RMg group) when toluene-soluble “tBuMgBr” or “PhMgBr” initiators are prepared and that the optimum THF concentration is slightly in excess of this. The nature of the solute in the toluene-soluble initiator solutions is discussed. The kinetics of the polymerization change from internal zero order to internal order of one with respect to monomer as the temperature increases from 225–275 K. This is consistent with a previously proposed mechanism in which propagation proceeds through a complex between monomer and the active center.     

N-Chlorosuccinimide(NCS):A Novel Initiator for Atom Transfer Radical Polymerization of Methyl Methacrylate

Atom transfer radical polymerization （ATRP） of methyl methacrylate （MMA） was achieved, using N-chlorosuccinimide （NCS） as an initiator together with catalytic system CuCl/PMDETA （N,N,N＇,N＇,N＂-pentamethyldiethylenetriamine）, CuCl/MA5-DETA （N,N＇,N＇,N＂-penta（methylacrylate）diethylenetriamine）, and CuCl/bipy （bipy= 2,2＇-bipyridyl） respectively. The results indicated that the polymerization possessed typical controlled/living radical polymerization characteristics. The analysis for terminal group of obtained polymer by ^1H NMR proved that NCS is an initiator for ATRP. In comparison with NBS, the polymerization rate was slower and the resulted polymer had narrower molecular weight distribution （MWD） when NCS was employed as the initiator.     

Adsorptive Stripping Voltammetric Study of the Enhancement of Copper(Ⅱ) in Phosphate and Carbonate media and in the Presence of Silicate

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Spectroscopic Study on Interaction of Lomefloxacin with Human Serum Albumin in the Presence of Copper Ion

The interaction of lomefloxacin （LMF） with human serum albumin （HSA） in the presence of copper ions in a physiological medium and its thermodynamic characteristics were investigated by multi-spectroscopy. The experimental results showed that both LMF and LMF-Cu^2＋ could quench the fluorescence of HSA with a static quenching mechanism, indicating that LMF or LMF-Cu^2＋ could react with HSA. The apparent binding constants/numbers of binding sites were estimated as 4.924± 105 Lomol 1/1.473 for LMF-HSA, 8.990± 104 L·mol^-1/1.785 for LMF- Cu^2＋-HSA, 1.10± 105 L·mol^-1/1.21 for LMF-Cu^2＋ and 7.30± 102 L·mol^-1/0.82 for HSA-Cu^2＋, respectively. AH and AS for LMF-HSA system were calculated to be --2.189 kJ·mol^-1 and 61.25 J·mol^-1·K^-1, while those for LMF-Cu^2＋-HSA system were -7.401 kJ·mol^-1 and 47.63 J·mol^-1·K^-1 Although the values of AH and AS in these two systems were different, the treads were similar, which indicated that electrostatic interactions in these two systems played a major role. According to Forster theory, the distances were given as 5.006 nm for HSA-LMF and 4.709 nm for HSA-LMF-Cu^2＋. Synchronous fluorescence and circular dichroism spectra confirmed further that the conformations of human serum albumin before and after interacting with LMF or LMF-Cu^2＋ were different. All the results revealed that copper ions promoted the interaction of lomefloxacin with human serum albumin.