Study on the Copolymerization Kinetics of 8-Quinolinyl Methacrylate with Methyl Methacrylate,n-Butyl Methacrylate and Styrene

Abstract

The 8-quinolinyl methacrylate (8-QMA) monomer was prepared and characterized by the conventional methods of analysis. The 8-QMA monomer was copolymerized with methyl methacrylate (MMA), n-butyl methacrylate (BMA) and styrene under different monomer feed ratio using azobisisobutyronitrilic (AIBN) as an initiator by solution copolymerization. The polymerization reaction was allowed to proceed only upto sim; 10%. The composition of the resulting copolymers was determined by UV-visible spectrophotometry and reactivity ratio for each monomer pair was calculated. The relative reactivity of the monomers was discussed on the basis of the size of alkyl group in methacrylates and effect of resonance on the stability of the styryl radicals during the copolymerization.     

Homopolymer of 4-chloro-3-methyl Phenyl Methacrylate and its Copolymers with Butyl Methacrylate: Synthesis, Characterization, Reactivity Ratios and Antimicrobial Activity

The methacrylate monomer 4-chloro-3‐methyl phenyl methacrylate (CMPM) was synthesized by reacting 4-chloro-3‐methyl phenol with methacryloyl chloride. The homopolymer and various copolymers of CMPM with n-butyl methacrylate were synthesized by free-radical polymerization in toluene at 70°C using 2,2′-azobis(isobutyronitrile) as the initiator. The CMPM monomer was characterized by Fourier transform IR and ¹H-NMR studies. The copolymers were characterized by IR spectroscopy. The molecular weights (M _n and M _w) and the polydispersity index were obtained from gel permeation chromatography. The solubility and intrinsic viscosity of the homopolymer and the copolymers are also discussed here. The copolymer composition obtained from UV spectra led to the determination of reactivity ratios employing Fineman-Ross and Kelen-Tudos linearization methods. Thermogravimetric analyses of the homopolymer and the copolymers were carried out under a nitrogen atmosphere. The homopolymer and the copolymers prepared were tested for their antimicrobial activity against bacteria, fungi and yeasts.     

Free radical copolymerization of 4-phenylbut-1-en-3-yne with methylmethacrylate

Summary Free radical copolymerization of 4-phenylbut-1-en-3-yne (PB) with methyl methacrylate(MMA) was studied. The polymerization of MMA was inhibited by the presence of small amounts of PB, but the copolymerization yield increased with increase in the PB concentration, and PB-rich copolymers were obtained. The monomer reactivity ratios, r_MMA and r_PB, were found to be 0.096 and 2.83, respectively. The Q and e values of PB were calculated by using the values of MMA and were found to be 2.69 and 0.74, respectively. The slow polymerization and low molecular weights were attributed to the low propagating activity of PB radicals.     

Polymerization of Cyclophosphazenes with Spriocyclic Methacrylate Containing Substituents

The radical addition polymerization and copolymerization of the cyclophosphazene monomers with spirocyclic methacrylate containing substituents, spiro(2,3-dioxypropylmethacryloyl)tetrachlorocyclotriphosphazene, N₃P₃Cl₄[OCH₂CH(OC(O)=CH₂)O] (1) and spiro((2-methyl-3-oxy-2-(oxymethyl)propyl)methacryloyl)tetrachlorocyclotriphosphazene, N₃P₃Cl₄[OCH₂CMe(CH₂OC(O)=CH₂)CH₂O] (2), has been investigated. In the case of 1, homopolymerization using AIBN as the initiator yielded only cross-linked solids. Copolymerization of 1 with methyl methacrylate was accomplished using VAZO 52 under milder initiation temperature. GPC of copolymer suggested a significant amount of chain transfer. Homopolymerization of 2 gave low isolated yields of the homopolymer but copolymerization with methyl methacrylate yielded the expected copolymers. The reactive chlorine atoms in the copolymers of 2 can be replaced by trifluoroethoxide or methyl amine. Thermal properties of the copolymers were examined by DSC, TGA and pyrolysis mass spectrometry.     

Photoinitiated graft copolymerization of glycidyl methacrylate and 2-hydroxyethyl methacrylate onto polyacrylonitrile and application of the synthesized graft copolymers in penicillin–amidase immobilization

The photoinitiated graft copolymerization of hydroxyethyl methacrylate and/or glycidyl methacrylate onto polyacrylonitrile (PAN) and the applicability of the matrices synthesized in this way for penicillin–amidase immobilization are discussed. The copolymers are prepared by putting irradiated PAN fibers with preliminary adsorbed benzophenone on them into the polymerization feed that includes hydroxyethyl methacrylate and/or glycidyl methacrylate dissolved in a water–methyl ethyl ketone mixture. The degree of grafting varies between 11.7 and 46.0%, and its efficiency, between 27.8 and 78.9%. The concentration of epoxy groups in the synthesized copolymers is in the range between 210 and 2220 μmol/g. The reactivity ratios of the two comonomers are determined to be r_GM = 0.70 ± 0.15 and r_HEMA = 2.73 ± 0.14. The grafted copolymers containing HEMA units provide milder conditions for penicillin–amidase covalent binding. The optimum pH and temperature values of penicillin–amidase immobilized on these matrices are 7.5 and 45°C, respectively. © 1994 John Wiley & Sons, Inc.     

Monomer-to-water ratios as a tool in controlling emulsion copolymer composition: The methyl acrylate–indene system

A drifting copolymer composition as a function of conversion is an aspect typical of copolymerization. Reducing this so-called composition drift in batch copolymerizations will lead to a decrease in chemical heterogeneity of the copolymers formed. For monomer systems in which the more water-soluble monomer is also the more reactive one, theory predicts that composition drift in emulsion copolymerization can be reduced or even minimized by optimizing the monomer-to-water ratio. The monomer combination methyl acrylate–indene (MA–Ind) meets the requirements needed to minimize composition drift in batch emulsion copolymerization. Therefore, this monomer combination is chosen as a model monomer system in order to verify this theoretical prediction. Reactivity ratios needed for model predictions have been determined by low conversion bulk polymerization, resulting in r_MA = 0.92 ± 0.16 and r_Ind = 0.086 ± 0.025. Furthermore, emulsion copolymerization reactions at the same monomer mole fraction are performed at different monomer to water ratios. From the good agreement between experiments and theoretical predictions for MA–Ind, it was concluded that control and even minimization of composition drift in batch emulsion copolymerization for monomer systems in which the more water-soluble monomer is also the more reactive one is indeed possible by changing the initial monomer-to-water ratio of the reaction mixture provided that the reactivity ratios of both monomers are not too far from unity. © 1994 John Wiley & Sons, Inc.     

Radical Copolymerization of 2-(3′-Acryloxy)propoxythioxanthone and 1-Methyl-4-(3′-acryloxy)propoxythioxanthone with Methyl Methacrylate

Two new monomers based on thioxanthone, 2-(3′-acryloxy)propoxythioxanthone (M-2) and 1-methyl-4-(3′-acryloxy)propoxythioxanthone (M-4), were prepared and their radical copolymerization at 70°C with methyl methacrylate (MMA) was studied. By varying the conversion reached for a fixed feed composition, f_MMA=0·983, and using Jaacks method, the reactivity ratios were determined. Identical values of reactivity ratios were found for both systems, with values of r_MMA=2·46 and r_M-2=r_M-4=0·4. The homopolymerization of MMA in the presence of a model compound, 1-methyl-4-propoxythioxanthone, was also examined and confirmed that the thioxanthone chromophore does not have any influence on the free radical polymerization of MMA. © of SCI.     

Reactivity ratios and copolymer properties of 2‐(diisopropylamino)ethyl methacrylate with methyl methacrylate and styrene

Free radical copolymerization kinetics of 2‐(diisopropylamino)ethyl methacrylate (DPA) with styrene (ST) or methyl methacrylate (MMA) was investigated and the corresponding copolymers obtained were characterized. Polymerization was performed using tert‐butylperoxy‐2‐ethylhexanoate (0.01 mol dm^?3) as initiator, isothermally (70 °C) to low conversions (<10 wt%) in a wide range of copolymer compositions (10 mol% steps). The reactivity ratios of the monomers were calculated using linear Kelen–Tüd?s (KT) and nonlinear Tidwell–Mortimer (TM) methods. The reactivity ratios for MMA/DPA were found to be r₁ = 0.99 and r₂ = 1.00 (KT), r₁ = 0.99 and r₂ = 1.03 (TM); for the ST/DPA system r₁ = 2.74, r₂ = 0.54 (KT) and r₁ = 2.48, r₂ = 0.49 (TM). It can be concluded that copolymerization of MMA with DPA is ideal while copolymerization of ST with DPA has a small but noticeable tendency for block copolymer building. The probabilities for formations of dyad and triad monomer sequences dependent on monomer compositions were calculated from the obtained reactivity ratios. The molar mass distribution, thermal stability and glass transition temperatures of synthesized copolymers were determined. Hydrophobicity of copolymers depending on the composition was determined using contact angle measurements, decreasing from hydrophobic polystyrene and poly(methyl methacrylate) to hydrophilic DPA. Copolymerization reactivity ratios are crucial for the control of copolymer structural properties and conversion heterogeneity that greatly influence the applications of copolymers as rheology modifiers of lubricating oils or in drug delivery systems. © 2015 Society of Chemical Industry     

Copolymerization of methyl methacrylate with 4‐vinylpyridine initiated by a novel Ni(II)α‐Benzoinoxime complex

Copolymerizations of methyl methacrylate (MMA) with 4‐vinylpyridine (4VP) were performed from different monomer feed ratios in 1,4‐dioxan at 30°C under free radical initiation experimental conditions, using Ni(II)α‐Benzoinoxime complex as initiator. The obtained copolymers (PMMA4VP) were examined by FTIR and ¹H NMR spectroscopies. The composition of these copolymers was calculated, using ¹H NMR spectra and elemental analysis. Monomer reactivity ratios were estimated from Fineman–Ross (FR, r_m = 0.550, r_v = 1.165) and Kelen–Tudos (KT, r_m = 0.559, r_v = 1.286) linearization methods, as well as nonlinear error in variables model (EVM) method using the RREVM computer program (RREVM, r_m = 0.559, r_v = 1.264). These values suggest that MMA‐4VP pair copolymerizes randomly. ¹H NMR spectra provide information about the stereochemistry of the copolymers in terms of sequence distributions and configurations. These results showed that the age of the Ni complex has an impact not only on its activity towards polymerization reactions but also on the features of the corresponding copolymers, whereas the chemical composition was insensitive to this prominent factor. The mechanism of MMA‐4VP copolymerization is consistent with a radical process as supported by microstructure and molecular weight distribution studies. Thermal behaviours of these copolymers were investigated by differential scanning calorimetry and thermogravimetric analysis. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2008     

Synthesis and characterization of perfluorinated acrylate–methyl methacrylate copolymers

A novel perfluorinated acrylic monomer 3,5‐bis(perfluorobenzyloxy)benzyl acrylate (FM) with perfluorinated aromatic units was synthesized with 3,5‐bis(perfluorobenzyl)oxybenzyl alcohol, acryloyl chloride, and triethylamine. Copolymers of FM monomer with methyl methacrylate (MMA) were prepared via free‐radical polymerization at 80°C in toluene with 2,2′‐azobisisobutyronitrile as the initiator. The obtained copolymers were characterized by ¹H‐NMR and gel permeation chromatography. The monomer reactivity ratios for the monomer pair were calculated with the extended Kelen–Tüdos method. The reactivity ratios were found to be r₁ = 0.38 for FM, r₂ = 1.11 for MMA, and r₁r₂ < 1 for the pair FM–MMA. This shows that the system proceeded as random copolymerization. The thermal behavior of the copolymers was investigated by thermogravimetric analysis and differential scanning calorimetry (DSC). The copolymers had only one glass‐transition temperature, which changed from 46 to 78°C depending on the copolymer composition. Melting endotherms were not observed in the DSC traces; this indicated that all of the copolymers were completely amorphous. Copolymer films were prepared by spin coating, and contact angle measurements of water and ethylene glycol on the films indicated a high degree of hydrophobicity. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

A comparison of composition and sequence distribution of p(AM-MADQUAT) prepared by solution and inverse microemulsion polymerization

Acrylamide (AM)/2-(methacryloyloxy)ethyltrimethylammonium chloride (MADQUAT) copolymers were prepared by solution and inverse microemulsion polymerization using ammonium persulfate ((NH₄)₂S₂O₈)/sodium hydrosulfite (NaHSO₃) as redox initiator at 30 °C. The comonomer reactivity ratios, determined using the Kelen–Tudos (KT) method, were r _A = 0.30, r _M = 1.31 in solution and r _A = 0.63, r _M = 1.13 in the inverse microemulsion, respectively. The copolymer microstructure was deduced from the run number and the heterogeneity, based on reactivity ratios. It was found that copolymerization in the inverse microemulsion resulted in close to ideal copolymerization, giving almost random copolymers; copolymerization in solution resulted in some alternating copolymers. The copolymer compositions indicated that high-conversion samples obtained from the inverse microemulsion are much more homogeneous in composition compared with those obtained in solution. It was found that the composition distribution of the copolymer prepared by inverse microemulsion polymerization remained at approximately the feed ratio. The sequence distribution of the copolymer was predicted by first-order Markov statistical and Bernoulli statistical models, respectively. The results showed that the sequence distribution of the copolymer prepared by inverse microemulsion polymerization was almost random, which led to a wider cationic charge distribution and a microstructure that was coincident with the feed ratio.     

Controllable radical copolymerization of styrene and methyl methacrylate using 1,1,2,2‐tetraphenyl‐1,2‐bis(trimethylsilyloxy) ethane as initiator

Copolymerization of styrene (St) and methyl methacrylate (MMA) was carried out using 1,1,2,2‐tetraphenyl‐1,2‐bis (trimethylsilyloxy) ethane (TPSE) as initiator; the copolymerization proceeded via a “living” radical mechanism and the polymer molecular weight (M_w) increased with the conversion and polymerization time. The reactivity ratios for TPSE and azobisisobutyronitrile (AIBN) systems calculated by Finemann–Ross method were r_St = 0.216 ± 0.003, r_MMA= 0.403 ± 0.01 for the former and r_St= 0.52 ± 0.01, r_MMA= 0.46 ± 0.01 for the latter, respectively, and the difference between them and the effect of polymerization conditions on copolymerization are discussed. Thermal analysis proved that the copolymers obtained by TPSE system showed higher sequence regularity than that obtained by the AIBN system, and the sequence regularity increased with the content of styrene in copolymer chain segment. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 1474–1482, 2001     

Radical polymerization and copolymerization behavior of 1-cyanoethanoyl-4-acryloylthiosemicarbzide

1-Cyanoethanoyl-4-acryloylthiosemicarbazide (CEATS) was synthesized for the first time as a new chelating monomer. Its structure was confirmed by both elemental and spectral analyses. Radical polymerization and copolymerization of CEATS was been carried out in dimethylformamide (DMF) in the presence of azobisisobutyronitrile (AIBN) as an initiator. Kinetic studies for the polymerization behavior of CEATS were performed. The complex formation of the CEATS monomer and polymer (PCEATS) with Cu II cation was investigated and its stability constant determined. The rate of copolymerization of CEATS with some conventional monomers, namely vinyl acetate, methyl methacrylate and acrylonitrile, was measured as a function of the mole fraction of the monomers. The reactivity ratios (r₁, r₂) for the various copolymer systems investigated together with the Q and e values of the CEATS monomer were determined. Moreover, the thermal gravimetric analysis of the prepared polymers and their copolymers with acrylonitrile were also studied.     

Coordination copolymerization of butadiene and isoprene with rare earth chloride–alcohol–aluminum trialkyl catalytic systems

Butadiene and isoprene were copolymerized with LnCl₃–ROH–AIR₃ catalytic system. The products obtained were confirmed to be copolymers by their glass transition temperatures and characteristic pyrolytic chromatograms, etc. The equation for copolymerization rate may be expressed as R_p = K_p(M)²(cat). The rate constants of copolymerization, activation energy, and monomer reactivity ratios for catalytic systems containing various rare earth elements in III-B family and different solvents were determined. It was found that the reactivity ratio of butadiene was greater than that of isoprene and r₁r₂ near 1, and the composition and microstructure of copolymers were not much affected by variation of polymerization conditions. Both monomer repeat units in the copolymers had cis-1,4 contents above 95%, which is a distinguishing feature of coordination polymerization with the lanthanide catalyst system.     

Atom transfer radical copolymerization of methyl methacrylate with N‐cyclohexylmaleimide

Atom transfer radical polymerization has been applied to simultaneously copolymerize methyl methacrylate (MMA) and N‐cyclohexylmaleimide (NCMI). Molecular weight behaviour and kinetic study on the copolymerization with the CuBr/bipyridine(bpy) catalyst system in anisole indicate that MMA/NCMI copolymerization behaves in a ‘living’ fashion. The influence of several factors, such as temperature, solvent, initiator and monomer ratio, on the copolymerization were investigated. Copolymerization of MMA and NCMI in the presence of CuBr/bpy using cyclohexanone as a solvent instead of anisole displayed poor control. The monomer reactivity ratios were evaluated as r_NCMI = 0.26 and r_MMA=1.35. The glass transition temperature of the resulting copolymer increases with increasing NCMI concentration. The thermal stability of plexiglass could be improved through copolymerization with NCMI. © 2000 Society of Chemical Industry     

Free radical copolymerization of N,N‐dimethylaminoethyl methacrylate with styrene and methyl methacrylate: monomer reactivity ratios and glass transition temperatures

BACKGROUND: The properties of copolymers depend strongly on their composition; therefore in order to tailor some for specific applications, it is necessary to control their synthesis, and, in particular, to know the reactivity ratios of their constituent monomers. Free radical copolymerizations of N,N‐dimethylaminoethyl methacrylate (DMAEM) with styrene (ST) and methyl methacrylate (MMA) in toluene solution using 1‐di(tert‐butylperoxy)‐3,3,5‐trimethylcyclohexane as initiator at 70 °C were investigated. Monomer reactivity ratios were determined for low conversions using both linear and nonlinear methods. RESULTS: For the DMAEM/ST system the average values are r₁ = 0.43 and r₂ = 1.74; for the DMAEM/MMA system the average values are r₁ = 0.85 and r₂ = 0.86. The initial copolymerization rate, R_p, for DMAEM/ST sharply decreases as the content of ST in the monomer mixture increases up to 30 mol% and then attains a steady value. For the DMAEM/MMA copolymerization system the composition of the feed does not have a significant influence on R_p. The glass transition temperatures (T_g) of the copolymers were determined calorimetrically and calculated using Johnston's sequence length method. A linear dependence of T_g on copolymer composition for both systems is observed: T_g increases with increasing ST or MMA content. CONCLUSION: Copolymerization reactivity ratios enable the design of high‐conversion processes for the production of copolymers of well‐defined properties for particular applications, such as the improvement of rheological properties of lubricating mineral oils. Copyright © 2009 Society of Chemical Industry     

Synthesis and characterization of methyl methacrylate/styrene hyperbranched copolymers via living radical mechanism

Free‐radical copolymerizations of N,N‐diethylaminodithiocarbamoylmethylstyrene (inimer: DTCS) with a methyl methacrylate (MMA)/zinc chloride (ZnCl₂) complex were carried out under UV light irradiation. DTCS monomers play an important role in this copolymerization system as an inimer that is capable of initiating living radical polymerization of the vinyl group. The reactivity ratios (r₁ = 0.56 and r₂ = 0.52: DTCS [M₁]; MMA [M₂]) obtained for this copolymerization system were different from a corresponding model system (alternating copolymer) of a styrene and MMA/ZnCl₂ complex (r₁ = 0.25 and r₂ = 0.056). It was found that the hyperbranched copolymers produced exhibited a random branching structure. It was found that the Lewis acid ZnCl₂ formed the complex not only with MMA but also with the carbamate group of inimer. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 2490–2495, 2003     

Batch and semicontinuous emulsion copolymerization of vinylidene chloride and butyl methacrylate. I. Kinetics in VDC–BMA emulsion polymerization and surface and colloidal properties of VDC–BMA latexes

Vinylidene chloride (VDC)—butyl methacrylate (BMA) comonomer mixtures with various composition (83 : 17, 60 : 40, 33 : 67 in mol %) were polymerized at 25°C using redox catalyst by batch and seeded semicontinuous emulsion copolymerization. The reactivity ratios determined in VDC (M₁)—BMA (M₂) emulsion copolymerization system were r₁ = 0.22 and r₂ = 2.41. Seven 35% solids (83 : 17 mol %) VDC–BMA copolymer latexes were prepared: one batch (G), one seeded batch (F), and 5 seeded semicontinuous polymerizations of 5 different monomer feed rates ranging from 0.27 (A) to 1.10 wt %/min (E). The kinetic studies of seeded semicontinuous polymerizations A-E showed that the rates of polymerizations (R_p) were controlled by the monomer addition rates (R_a). The conversion versus time curves for the polymerizations of 0 : 100–100 : 0 VDC–BMA mixtures by batch polymerization showed that the rate of polymerization (R_p) was a function of the number of particles, and that the rate of polymerization in a latex particle (R_pp) increased with increasing proportions of butyl methacrylate in the monomer mixture. All of the latexes had narrow particle size distributions. The greater particle number density in VDC polymerization and the greater water solubility of VDC suggest that the homogeneous nucleation mechanism is operative in VDC–BMA copolymerizations. The latex copolymers prepared by semicontinuous polymerization had lower number-and weight-average molecular weights than those of the corresponding batch copolymers, resulting from the monomer starvation occurring during the semicontinuous polymerization. The surface characterization study of the cleaned latexes showed that for the latexes by batch process, the surface charge density derived from strong-acid groups decreased with increasing proportion of VDC in the monomer mixture. On the other hand, for the latexes prepared by semicontinuous polymerization, the surface charge density derived from strong-acid groups did not depend on the monomer composition of the copolymers.     

Synthesis of graft copolymers from a linear polyolefin through a combination of coordination polymerization and atom transfer radical polymerization

This article reports on a facile route for the preparation of methyl acrylate and methyl methacrylate graft copolymers via a combination of catalytic olefin copolymerization and atom transfer radical polymerization (ATRP). The chemistry first involved a transforming process from ethylene/allylbenzene copolymers to a polyolefin multifunctional macroinitiator with pendant sulfonyl chloride groups. The key to the success of the graft copolymerization was ascribed to a fast exchange rate between the dormant species and active radical species by optimization of the various experimental parameters. Polyolefin‐g‐poly(methyl methacrylate) and polyolefin‐g‐poly(methyl acrylate) graft copolymers with controlled architecture and various graft lengths were, thus, successfully prepared under dilute ATRP conditions. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Chiral copolymers of (R)‐N‐(1‐phenylethyl) methacrylamide and 2‐hydroxyethyl methacrylate: copolymerization characteristics and chiroptical properties

The aim of this investigation was the copolymerization of a chiral monomer, (R)‐N‐(1‐phenylethyl) methacrylamide, with an achiral monomer, 2‐hydroxyethyl methacrylate (HEMA). The copolymerization characteristics as well as the chiroptical properties (optical rotation and circular dichroism) and their variation with copolymer composition and temperature are discussed. The copolymers are statistical and enriched in HEMA. The monomer reactivity ratio of the chiral monomer (r₁) is 0.133 whereas that of HEMA (r₂) is 1.042 based on the Kelen–Tudos method. The sequence of consecutive chiral monomer units predominates for a feed composition between 0.5 and 0.9 (mole fraction). On the other hand, the sequence of HEMA is uniform and it predominates for a feed composition of around 0.5 (mole fraction). The chiroptical properties of the copolymers do not vary linearly with the content of chiral units in the copolymers. The optical rotation and circular dichroism attain optimum values above 30–40 mol% of chiral monomer units in the copolymers. However, the circular dichroism of the copolymers varies linearly with the temperature. The chiral monomer being a more bulky structure is less reactive than HEMA. The nonlinear variation of chiroptical properties of the copolymers with the content of chiral units may be due to the secondary interaction in the copolymers associated with the hydrogen bonding involving the amide linkage (CONH) present in the pendant chromophore of the chiral monomer as well as the hydroxyl pendant group of HEMA and also the aromatic π–π interaction. Copyright © 2009 Society of Chemical Industry