Dielectric Relaxation of Methyl Methacrylate and Ethyl Methacrylate on Complexation with Phenols

Dielectric absorption studies of H-bonded complexes of methyl methacrylate (MMA) and ethyl methacrylate (EMA) with p-cresol, p-chlorophenol, 2,4-dichlorophenol, and p-bromophenol were studied at microwave frequency 9.37 GHz in dilute solution of carbon tetrachloride at 308 K. Different dielectric parameters like dielectric constantε′ and dielectric loss ε″ at microwave frequency, static dielectric constant ε_0 and dielectric constant ε_∞ at optical frequency were determined. The validity of the single frequency equation of Higasi et al. for multiple relaxation time τ_(1) was found to be a function of the hydrogen bonding strength of phenolic hydrogen, whereas the group rotation relaxation time τ_(2) was a function of the steric interaction of proton donor. The relaxation time was the maximum at 50∶50 (molar ratio) of methacrylates with phenols.     

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…     

Synthesis of Copolymers of Unsaturated β-Diketones with Styrene and Methyl Methacrylate

Copolymerization of styrene and methyl methacrylate with various unsaturated -diketones was studied. The influence exerted by the reaction temperature, structure of -diketone, and its content in the comonomer mixture on the kinetic parameters of copolymerization and molecular weights of the products was examined.     

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…     

Free-Radical Copolymerization of Methyl Methacrylate and α-Methacrylophenone. I. Reactivity Ratios

The free-radical copolymerization of methyl methacrylate and methacrylophenone (MAP) initiated by azobisisobutyroni-trile at 60°C has been studied in ethylbenzene solution and in bulk. The process is characterized by a competitive Diels-Alder condensation of methacrylophenone and by a very low reactivity of methacrylophenone-terminated macroradicals in propagation reactions. The experimental composition data are consistent with a terminal unit model: r_A = 1.77 ± 0.02, r_B = 0.110 ± 0.006. Copolymerization with depropagation of methacrylophenone-terminated growing chains and copolymerization affected by penultimate effects have been tested as optimized possible models to take into account the inability of MAP to undergo homopolymerization.     

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. …     

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.     

Oxidative Esterification of Methacrolein to Methyl Methacrylate over Supported Palladium Catalyst

Methyl methacrylate (MMA) is an important monomer, widely used for producing acrylic plastics, polymer dispersions for paints and coatings. Traditional acetone cyanhydrin (ACH) method involves toxic hydrogen cyanide and a large quantity of ammonium bisulf…     

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.     

Analysis and Characterization of Microwave Irradiation–Induced Graft Copolymerization of Methyl Methacrylate onto Delignified Grewia Optiva Fiber

Grafting of methyl methacrylate (MMA) onto delignified Grewia optiva fiber using ascorbic acid/H₂O₂ as an initiator was carried out under microwave irradiation. The effects of varying the microwave power, exposure time, and concentration of initiator and monomer of graft polymerization were studied to obtain maximum grafting percentage (26.54%). The experimental results showed that the optimal conditions for grafting were: exposure time, 10min; microwave power, 110 W; ascorbic acid concentration, 3.74mol/L × 10^?2; H₂O₂ concentration, 0.97mol/L × 10^?1; monomer concentration, 1.87mol/L × 10^?1. The graft copolymers were characterized by Fourier transform-infrared (FT-IR) spectroscopy, scanning electron microscopy (SEM), and thermogravimetric analysis (TGA).     

Copolymerization of 4‐Propanoylphenyl Acrylate with Methyl Methacrylate: Synthesis,Characterization and Reactivity Ratios

The new acrylic monomer 4‐propanoylphenyl acrylate (PPA) was synthesized and copolymerized with methyl methacrylate (MMA) in methyl ethyl ketone at 70±1°C using benzoyl peroxide as a free radical initiator. The copolymers were characterized by FT‐IR, ¹H‐NMR and ¹³C‐NMR spectroscopic techniques. The compositions of the copolymers were determined by ¹H‐NMR analysis. The reactivity ratios of the monomers were determined using Fineman‐Ross (r₁=0.5535 and r₂=1.5428), Kelen‐Tüdös (r₁=0.5307 and r₂=1.4482), and Ext. Kelen‐Tüdös (r₁=0.5044 and r₂=1.4614), as well as by a nonlinear error‐in‐variables model (EVM) method using a computer program, RREVM (r₁=0.5314 and r₂=1.4530). The solubility of the polymers was tested in various polar and non‐polar solvents. The elemental analysis was determined by a Perkin‐Elmer C‐H analyzer. The molecular weights (M_w and M_n) of the copolymers were determined by gel permeation chromatography. Thermogravimetric analysis of the polymers reveals that the thermal stability of the copolymers increases with an increase in the mole fraction of MMA in the copolymers. Glass transition temperatures of the copolymers were found to increase with an increase in the mole fraction of MMA in the copolymers.     

Copper Catalyzed ATRP of Methyl Methacrylate Using Aliphatic α-Bromo Ketone Initiator

The atom transfer radical polymerization (ATRP) of MMA was examined using 3-bromo-3-methyl-butanone-2 (MBB) as an initiator in the presence of CuBr as catalyst and 2,6-bis[1-(2,6-diisopropylphenylimino)ethyl]pyridine (BPIEP) as a tridentate N-donor ligand. The effect of various other N-donor ligands including a bisoxazoline ligand, namely, 2,6-bis(4,4-dimethyl-2-oxazolin-2-yl) pyridine (dmPYBOX) was studied in ATRP and reverse ATRP of MMA. The ATRP of MMA in toluene at 90 °C using MBB as initiator was relatively slow in the case of bidentate and faster in the case of tridentate N-donor ligands. The apparent rate constant, k_app, with MBB as initiator and BPIEP as ligand in toluene (50%, v/v) at 90 °C was found to be 7.15 × 10⁻⁵ s⁻¹. In addition, reverse ATRP of MMA in diphenylether at 70 °C using BPIEP/CuBr₂ as catalyst system was very effective in reducing the reaction time from several hours to 24 h for polymerization of MMA.     

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…     

Copolymerization of ω-Unsaturated Oligo(Methyl Methacrylate): New Macromonomers

Abstract

The free-radical copolymerization of ω-unsaturated oligo(methyl methacrylate) (1) with each of ethyl acrylate, styrene, methyl methacrylate, acrylonitrile, and vinyl acetate have been investigated. Incorporation of (1) into the polymer was observed in all cases although the molecular weights of the copolymers were substantially lower than those of the homopolymers obtained in the absence of (1) but under otherwise identical conditions. These experiments, together with a product study of the reactions of (1) with cyanoisopropyl radicals, have shown that the addition of free radicals to the double bond of (1) occurs readily. The sterically hindered radical so formed, however, undergoes facile β-scission, resulting in the termination of chains (chain transfer) in competition with chain propagation. The implications of these findings to the usefulness of (1) in the synthesis of graft copolymers and their relevance to the chemistry of free-radical polymerizations when methyl methacrylate is employed as a monomer or comonomer are discussed.     

Phase Behavior and Morphology of Poly(Methyl Methacrylate)/Poly(α‐Methyl Styrene‐co‐Acrylonitrile) Blends Under Quiescent and Shear Flow

The kinetics of spinodal decomposition (SD) for the binary blend poly(methyl methacrylate), PMMA, and Poly(α‐methylstyrene‐co‐acrylonitrile), PαMSAN, with 31 wt% AN content (LCST‐type phase diagram) has been thoroughly studied using a time‐resolved light scattering technique. The early stage SD was dominated by a diffusion process and can be well described within the framework of the linearized Cahn‐Hilliard theory. The spinodal temperature could be evaluated from the analysis of the early stage SD based on the Cahn theory. In addition, viscoelastic properties of this system have been systematically investigated at temperatures below and above the LCST phase diagram. The linear viscoelastic properties of the blends were found to be greatly changed by phase separation in the two‐phase regime. This change in the linear viscoelastic properties attributed to an additional contribution of concentration fluctuations to the material functions at the phase separation temperatures. The phase diagram of the blends was also estimated rheologically through the dynamic temperature ramps of G′, G″ and η*. Furthermore, the phase behavior and morphology of this system has been studied under different shear rates using simple shear apparatus and transmission electron microscopy (TEM), respectively.     

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, Characterization and Application of Benzyl-substituted Cyclopentadienyl lanthanide Complexes as Catalyst Precursors for the Syndiotactic Polymerization of Methyl Methacrylate

Benzyl-substituted cyclopentadienyl lanthanide complexes were synthesized and characterized by elemental analysis, MS and IR spectroscopy. The analytical data point out the formation of monomeric, unsolvated complexes.In conjunction with AI(Et)3 as co-catalyst, the title complexes are efficient catalysts for the syndiotactic polymerization of methyl methacrylate. For the complex (C6HsCH2C5H4)2YCl, under the optimum polymerization conditions(60℃,n(MMA):n(catalyst):n(co-catalyst)=1000:1:10),a predominantly syndiotactic (rr=66%) polymerof high molecular weight (Mη=105000) was obtained.     

Effect of Bis(6-methylpyridazinyl)-3,3′-disulfide in the Radical Polymerizations of Styrene and Methyl Methacrylate

Thermal and photo polymerizations of styrene (St) have been carried out in the presence of bis-(6-methylpyridazinyl)-3,3′-disulfide (I). I was found to initiate the photo polymerization of St but to retard the thermal polymerization of St. The chain transfer constants of I in the polymerizations of St and methyl methacrylate were determined to be 1.64 and 1.8 × 10^?2, respectively, from which the Q_tr and e_tr values were calculated to be 5.32 × 10^?2 and 3.86, respectively.     

Molecular Architecture of Non-Linear Polymers: Kinetic Modeling and Experimental Characterization of the System Methyl Methacrylate + Ethylene Glycol Dimethacrylate

A general kinetic approach allowing the prediction of the molecular architecture of non-linear polymers is applied to the study of the copolymerization of methyl methacrylate (MMA) with ethylene glycol dimethacrylate (EGDMA). Dynamic predictions of molecular weight distributions, sequence length distributions and mean square radius of gyration are possible before and after gelation. A set of experiments concerning the copolymerization of MMA and EGDMA was carried out in toluene solution at 60 °C for which classic radical kinetics is a good approximation. The time evolution of key polymer properties was followed using a SEC system with a refractive index detector coupled with MALLS allowing the determination of absolute weight average molecular weight and apparent molecular size distributions as well as z-average radius of gyration. Special focus was given to assess the influence of the initial amount of cross-linker on the dynamics of the non-linear structure build-up of these products. A kinetic scheme comprising 23 different chemical species and 76 chemical reactions was used in the modeling studies of this chemical system. Most of the kinetic parameters used in the simulations have been collected from previous studies. For experiments at low monomer conversion (up to about 0.5) a good agreement between predictions and experimental measurements is observed for molecular weights and z-average radius of gyration by fitting a small number of parameters describing gel effect (with a conversion dependent but chain length independent termination rate parameter) and the relative propagation on pendant double bonds. However, predicted values of weight-average molecular weights and z-average radius of gyration before gelation are too low at higher monomer conversions with non-linear systems. The likely cause is the presence of intramolecular reactions which should not be neglected in these circumstances.