Copolymers of Phenoxyethyl Methacrylate with Glycidyl Methacrylate: Synthesis,Characterization and Reactivity Ratios

The free radical copolymerization of phenoxyethyl methacrylate (POEMA) and glycidyl methacrylate (GMA) was carried out using α,α′-azobisisobutyronitrile (AIBN) in 2-butanone solution at 333 ± 1 K. The copolymers were characterized by FTIR, ¹H-NMR and ¹³C-NMR spectroscopic methods. Thermal properties of the copolymers were also studied by thermogravimetric analysis (TGA). The compositions of the copolymers were established by ¹H-NMR analysis. The monomer reactivity ratios were computed using the Fineman–Ross (F-R) and Kelen–Tüdos (K-T) methods. These parameters were also estimated using a nonlinear computational fitting procedure, known as reactivity ratios error in variable model (RREVM). The mean sequence lengths determination indicates that the copolymers obtained are random in nature. Differences in the reactivity ratios obtained by the classical methods and RREVM were observed. GMA is more reactive than POEMA and although the copolymers are random, some tendency to GMA small block formation is reported.     

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.     

Synthesis, Characterization and Reactivity Ratios of Phenylethyl Acrylate/Methacrylate Copolymers

2-Phenylethyl acrylate (PEA) and 2-Phenylethyl methacrylate (PEMA) were synthesized by reacting 2-Phenyl ethanol with acryloyl and methacryloyl chloride respectively. Homopolymers and copolymers were prepared by free radical polymerization technique using benzoylperoxide as initiator. Copolymers of PEA and PEMA with methyl acrylate (MA) and N-vinyl pyrollidone (NVP) of different compositions were prepared. The monomers and polymers were characterized by IR and NMR techniques. Thermal stability of the polymers were determined by TG analysis. The composition of the copolymer was determined using ¹H-NMR analysis. The reactivity ratios of the monomers were determined by the application of Finemann–Ross and Kelen–Tudos methods. The prepared copolymers were tested on leather for their pressure sensitive adhesive property.     

Copolymerization of 2-(4-tert-butylphenoxy)-2-oxo-ethyl Methacrylate with Methyl Methacrylate and Styrene: Synthesis, Characterization, and Monomer Reactivity Ratios

A tertierbutylphenoxy group containing methacrylate based monomer 2-(4-tert-butylphenoxy)-2-oxo-ethyl methacrylate (TBPOEMA) was synthesized by reacting 4-tertierbutylphenyl chloroacetate (TBPClAcO) with sodium methacrylate in acetonitrile. TBPClAcO was prepared by reacting tertierbutylphenol dissolved in benzene with chloroacetylchloride. The free-radical-initiated copolymerization of TBPOEMA, with methyl methacrylate (MMA) and styrene (ST) was carried out in dimethylsulphoxide (DMSO) solution at 65°C using 2,2-azobisisobutyronitrile (AIBN) as an initiator with different monomer-to-monomer ratios in the feed. The monomer TBPOEMA and copolymers were characterized by FTIR, ¹H- and ¹³C-NMR spectral studies. The copolymer composition obtained from the ¹H-NMR spectra led to the determination of reactivity ratios. The reactivity ratios of the monomers were determined by the application of Finemann–Ross and Kelen–Tüdös linear methods and the Behnken nonlinear least-squares method. The analysis of reactivity ratios revealed that MMA and ST are more reactive than TBPOEMA, and copolymers formed are statistical in nature. The molecular weights _w and _n) and polydispersity index of the polymers were determined using gel permation chromagtography. Thermogravimetric analysis of the polymers reveal that the thermal stability of the copolymers increases with an increase in the mole fraction of TBPOEMA in the copolymers. Glass transition temperatures of the copolymers were found to decrease with an increase in the mole fraction of TBPOEMA in the copolymers. The apparent thermal decomposition activation energies (E _d) were calculated by Ozawa method using the SETARAM Labsys TGA thermobalance.     

Synthesis and Characterization of Homo- and Copolymers of N-4-Azodiphenyl Maleimide with Methyl Methacrylate and Styrene

The synthesis and free radical homopolymerization of N-4-azodiphenylmaleimide (ADPMI) and copolymerization of methyl methacrylate (MMA) and styrene (ST) with ADPMI using an AIBN initiator were performed in THF solvent at 70°C. A series of copolymers, ADPMI-MMA and ADPMI-ST, were prepared using different feed ratios of comonomers. The polymer samples have been characterized by solubility tests, intrinsic viscosity measurements, FT-IR, ¹H-NMR spectral analysis, and thermo-gravimetric analysis. The values of monomer reactivity ratios r₁ and r₂ determined by Fineman-Ross and Kelen-Tudos methods are 0.16 and 0.63, and 0.26 and 0.25 in ADPMI/MMA and ADPMI/ST systems, respectively. Alfrey-Price Q-e values for ADPMI are Q = 2.27 and e = 1.92, and 0.41 and 1.949 for ADPMI/MMA and ADPMI/ST systems, respectively. It was found that the initial and final decomposition temperatures increased with the increase of ADPMI content in the copolymer samples.     

Copolymerization of 4-cyanophenyl methacrylate with methyl methacrylate: Synthesis,characterization and determination of monomer reactivity ratios

Summary A novel methacrylic monomer, 4-cyanophenyl methacrylate (CPM) was synthesized by reacting 4-cyanophenol dissolved in methyl ethyl ketone (MEK) with methacryloyl chloride in the presence of triethylamine as a catalyst. Copolymers of CPM with methyl methacrylate(MMA) at different composition was prepared by free radical solution polymerization at 70±1 °C using benzoyl peroxide as initiator. The copolymers were characterized by FT-IR, ¹H-NMR and ¹³C-NMR spectroscopic techniques. The solubility of the polymers was tested in various polar and non polar solvents. The molecular weight and polydispersity indices of the copolymers were determined using gel permeation chromatography. The glass transition temperature of the copolymers increases with increase in mole fraction of MMA content. The thermal stability of the copolymer increases with increases in mole fraction of CPM content in the copolymer. The copolymer composition was determined by using ¹H-NMR spectroscopy. The monomer reactivity ratios estimated by the application of linearization methods such as Fineman-Ross (r₁=2.524±0.038, r₂=0.502±0.015), Kelen-Tudos (r₁=2.562±0.173, r₂=0.487±0.005) and extended Kelen-Tudos methods (r₁=2.735±0.128, r₂=0.4915±0.007).     

Synthesis,Characterization, Reactivity Ratio and Photo Crosslinking Properties of the Copolymer of 4-Cinnamoyl Phenyl Methacrylate with Butyl Methacrylate

Copolymers of 4-cinnamoyl phenyl methacrylate (4-CPMA) and n-butyl methacrylate (BMA) were prepared in a methyl ethyl ketone (MEK) solution with benzoyl peroxide (BPO) as an initiator at 70°C. They were characterized with UV, IR, ¹H-NMR, ¹³C-NMR, TGA, DSC and gel permeation chromatography. Copolymers were prepared by using different feed ratio of monomers. The monomer reactivity ratios determined by the method of Kelen-Tudos (K-T) were r₁ (CPMA) = 2.32, r₂ (BMA) = 0.56. The glass transition temperature of the copolymer shows a single Tg indicating the formation of random copolymer for all of the monomer feed composition. Thermogravimetric analysis in air has shown that the initial decomposition temperature of the copolymer was above 220°C. The photocrosslinking properties of the copolymer were examined by UV irradiation with polymer film.     

Free Radical Copolymerization of Methyl Methacrylate and Styrene with N-(4-Carboxyphenyl)maleimide

The free radical copolymerization of methyl methacrylate (MMA) or styrene (St) with N-(4-carboxyphenyl)maleimide (CPMI) was carried with AIBN as an initiator in THF solvent at 80°C. A series of copolymers of MMA and St with CPMI were prepared using different feed ratios of comonomers. The values of monomer reactivity ratios (r₁, r₂) determined by Fineman-Ross and Kelen-Tudos methods are 0.26 and 2.51 in the CPMI/MMA system and 0.08 and 0.22 in the CPMI/St system. Alfrey–Price Q-e values for CPMI were calculated as Q = 1.05 and e = 0.41 in the CPMI/MMA system and Q = 1.21 and e = 0.91 in the CPMI/St system. The polymer samples have been characterized by solubility tests, intrinsic viscosity measurements, FT-IR and ¹H-NMR spectral analysis, and thermo-gravimetric analysis. It was found that the initial and final decomposition temperatures increased with increasing the amount of CPMI in the copolymer. The integral procedural decomposition temperature and energy of activation of thermal degradation have also been reported.     

Copolymerization of Methyl Methacrylate,Ethyl Acrylate,and Butyl Acrylate with N-2-Anisylmaleimide and Characterization of the Copolymers

The free radical copolymerizations of methyl methacrylate (MMA), ethyl acrylate (EA), and butyl acrylate (BA) with N-2-Anisylmaleimide (AMI), initiated by AIBN, were performed in THF solvent at 65°C. A series of copolymers of AMI-MMA, AMI-EA, and AMI-BA were prepared using different feed ratios of comonomers. The polymer samples have been characterized by solubility tests, intrinsic viscosity measurements, FT-IR, and ¹H-NMR spectral analysis, and thermo-gravimetric analysis. The values of monomer reactivity ratios r₁ and r₂ determined by Fineman-Ross and Kelen-Tudos methods are 0.43 and 0.42 in AMI/MMA, 0.72 and 0.62 in AMI/EA and 0.76 and 0.72 in AMI/BA systems. Alfrey-Price Q-e values for AMI are Q = 3.13 and e = 1.71 in AMI/MMA, Q = 1.10 and e = 1.46 in AMI/EA and Q = 1.02 and e = 1.63 in AMI/BA systems. It was found that the initial and final decomposition temperature increased with increasing the component of AMI in the copolymer.     

Copolymerization of 2-methyl-N-1,3-thiazole-2-ylacrylamide with glycidyl methacrylate: synthesis, characterization, reactivity ratios and biological activity

The free-radical copolymerization of 2-methyl-N-1,3-thiazole-2-ylacrylamide monomer (TMA) with glycidyl methacrylate (GMA) was carried out in 1,4-dioxane at 65 ± 1 °C using azobisisobutironitril (AIBN) as an initiator. The copolymers were characterized by FTIR, ¹³C-NMR and ¹H-NMR spectroscopic methods. The copolymer compositions were determined by elemental analysis. The weight-average and number-average molecular weights of the copolymers were obtained by gel permeation chromatography (GPC). The polydispersity indices of the polymers, determined with gel permeation chromatography, suggested a strong tendency for chain termination by disproportionation. Thermal properties of the polymers were also studied by thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). The monomer reactivity ratios were calculated according to the general copolymerization equation using Kelen–Tudos and Fineman–Ross linearization methods. The reactivity ratios indicated a tendency toward for alternation. The thermal decomposition activation energies of the polymers were evaluated by Ozawa method. The antibacterial and antifungal effects of the copolymers were also investigated on various bacteria and fungi. All the products showed moderate activity against different strains of bacteria and fungi.     

Synthesis and characterization of ethyl methacrylate-acrylamide copolymers

Free radical copolymerization of ethyl methacrylate (EMA) and acrylamide (AA) was carried out in the presence of 2,2′-azobisisobutyronitrile (AIBN) in dimethyl formamide (DMF) at 60°C. The percentage composition of the copolymers were established by elemental analysis. The copolymerization reactivity ratios were determined by both Fineman-Ross (F-R) and Kelen-Tudos (K-T) methods. The copolymers were characterized by IR, ¹H-NMR, thermal, and dielectric studies. Glass transition temperatures (T_g) have been determined by DSC. The solubility parameter of this copolymer was evaluated by studying the intrinsic viscosity in different solvents.     

Charge transfer copolymerization and properties of isopropyl methacrylate with acrylonitrile and methacrylonitrile

Isopropyl methacrylate (IPMA) with Acrylonitrile (AN) and Methacrylonitrile (MAN) copolymers of different copositions were prepared at 60°C and 80°C, respectively, using a mixture of n-Butylamine (nBA) and carbon tetrachloride (CCl₄) in dimethyl sulphoxide (DMSO) as a charge transfer (CT) initiator. The percentage composition of the copolymers was established by elemental analysis. The copolymerization reactivity ratios were computed by the Kelen–Tudos method. In both the systems, IPMA was found to be more reactive; the copolymers sequence was random in nature. The copolymers were characterized by IR, ¹H-NMR, ¹³C-NMR spectroscopy and intrinsic viscosity measurements in dimethyl formamide (DMF) at 30±0.1°C. The thermal behavior of the AN-IPMA copolymers was studied by thermogravimetry (TG) in air. The thermal stability increased, with increasing AN content in the copolymer chain. The solubility parameter of AN-IPMA copolymer was evaluated by studying the intrinsic viscosity in different solvents. The solubility parameter of the copolymer was found to be 9.7 (cal/cc)^1/2.     

Copolymerization of 4-biphenyl methacrylate with glycidyl methacrylate: Synthesis, Characterization, thermal properties and determination of monomer reactivity ratios

Summary The methacrylic monomer, 4-biphenylmethacrylate (BPM) was synthesized by reacting 4-biphenyl phenol dissolved in ethyl methyl ketone (EMK) with methacryloyl chloride in presence of triethylamine as a catalyst. The copolymers of BPM with glycidyl methacrylate (GMA) were synthesized by free radical polymerization in EMK solution at 70±1 °C using benzoyl peroxide as a free radical initiator. The copolymerization behaviour was studied in a wide composition interval with the mole fractions of BPM ranging from 0.15 to 0.9 in the feed. The copolymers were characterized by FT-IR, ¹H-NMR and ¹³C-NMR spectroscopic techniques. The solubility was tested in various polar and non polar solvents. The molecular weight and polydispersity indices of the polymers were determined using gel permeation chromatography. The glass transition temperature of the copolymers increases with increase in BPM content. The thermogravimetric analysis of the polymers showed that the thermal stability of the copolymer increases with BPM content. The copolymer composition was determined using ¹H-NMR spectra. The monomer reactivity ratios were determined by the application of conventional linearization methods such as Fineman-Ross (r₁=0.392 ± 0.006, r₂ = 0.358 ± 0.007, Kelen-Tudos (r₁= 0.398 ± 0.004, r₂= 0.365 ± 0.013) and extended Kelen-Tudos methods (r₁= 0.394 ± 0.004, r₂= 0.352 ± 0.006).     

Silicone/polypropylene oxide-polyethylene oxide copolymer/clay composites (i) - curing behavior,intermolecular interaction and thermomechanical properties

The copolymerization of 2-(3-mesityl-3-methylcyclobutyl)-2-ketoethyl methacrylate monomer with acrylonitrile and styrene were carried out in 1,4-dioxane solution at 60^○C using AIBN as an initiator. The copolymers were characterized by Fourier transform infrared, ¹H-NMR, and ¹³C-NMR spectroscopic techniques. Thermal properties of the polymers were also studied by thermogravimetric analysis and differential scanning calorimetry. The copolymer compositions were determined by elemental analysis and ¹H-NMR technique. The monomer reactivity ratios were calculated by the application of conventional linearization methods as a result of Fineman–Ross and Kelen–Tüdös to less than 1 for both monomers.     

Water-soluble Copolymers of N-vinylpyrrolidone and Vinyl Acetate: Synthesis, Characterization, and Monomer Reactivity at High Conversions

Homogeneous copolymers of N-vinylpyrrolidone (VP) and vinyl acetate (VA) which form clear aqueous solutions were prepared by free radical polymerization in a solution of isopropanol alcohol, using 2,2-azobisisobutyronitrile as an initiator. They were characterized by FTIR, ¹H-NMR, and element analysis studies. The reactivity ratios of the monomer were computed by the Extended Kelen–Tüdós method at high conversions, using data from both ¹H-NMR and elemental analysis studies. The reactivity ratios of VP and VA in a homogenous copolymer were observed to be very different from that of a heterogeneous copolymer. Additional information was obtained by finding out the sequence length distribution for copolymers.     

Organotin polymers. IX. Copolymerization parameters of di-(tri-n-butyltin) itaconate with styrene and methyl methacrylate

Copolymerization reactions of di-(tri-n-butyltin) itaconate with styrene and methyl methacrylate were carried out in solution at 70°C using 1 mol% azobisisobutyronitrile as a free radical initiator. The copolymer compositions were determined by chemical analysis as well as from ¹H-NMR data. The monomer reactivity ratios for copolymerizations of di-(tri-n-butyltin) itaconate with styrene and methyl methacrylate have been found to be r₁ = 0.228, r₂ = 0.677, and r₁ = 0.220, r₂ = 1.635, respectively. The sequence distribution of the triad fractions were calculated from reactivity ratios and compared with those obtained from ¹H-NMR data.     

Copolymerization of methyl methacrylate with N-(methoxyphenyl) itaconimides

This article describes the synthesis and characterization of N-(3-methoxyphenyl) itaconimide (MAI) and N-(4-methoxyphenyl) itaconimide (PAI) obtained by the reaction of itaconic anhydride with m-anisidine and p-anisidine, respectively. Structural and thermal characterization of MAI and PAI monomers was performed with Fourier transform infrared (FTIR), ¹H-NMR, differential scanning calorimetry (DSC), and thermogravimetric analysis. Copolymerization of methyl methacrylate (MMA) with various amounts of MAI or PAI ranging from 0.1 to 0.5 was performed in solution with azobisisobutyronitrile as an initiator. Structural and molecular characterization of copolymers was performed with FTIR, ¹H-NMR, elemental analysis, and gel permeation chromatography. The nitrogen percentage was used to calculate the copolymer composition. The monomer reactivity ratios for MMA–MAI copolymers were found to be 1.00 ± 0.01 for MMA and 0.99 ± 0.07 for MAI; those for MMA–PAI copolymers were 0.93 ± 0.02 for MMA and 1.11 ± 0.10 for PAI. The molecular weights of the copolymers were in the range of 0.94–9.7 × 10³ (number-average molecular weight) and 3.3–101.8 × 10³ (weight-average molecular weight), with polydispersity indices in the range of 1.5–4.1. The molecular weight decreased with the increasing molar fraction of imide in the polymer backbone. The glass-transition temperature, as determined from DSC scans, increased with increasing amounts of itaconimides in the copolymers. A significant improvement in the char yield, as determined by thermogravimetry, was observed upon copolymerization. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Synthesis of Triblock Copolymers via Photopolymerization of Styrene and Methyl Methacrylate Using Macrophotoinitiators Possessing Poly(ethylene glycol) Units

Macrophotoinitiators based on poly(ethylene glycol)s bearing benzyl tereftalmono amid moieties were synthesized by the reaction of poly(ethylene glycol) (PEG) terminated with terephtaloyl chloride and benzyl amine. The initiators possessing PEG with different molecular weights were used in the photoinduced radical polymerization of styrene (S) and methyl methacrylate (MMA) to yield poly(styrene-b-ethylene glycol-b-styrene) and poly(methyl methacrylate-ethylene glycol-b-methyl methacrylate) triblock copolymers. Characterization of macrophotoinitiators were performed by elemental anlysis, IR and ¹H-NMR spectrum. The elemental analysis results agreed with the theoretical values. The IR and ¹H-NMR spectra showed that the poly(ethylene glycol) units were reacting with the tereftloyl chloride and benzylamine. Characterization of the block copolymers was carried out by spectral measurements, GPC and fractional precipitation methods. The polydispersities of the block copolymers were observed between 1.2–2.32 for poly(methyl methacrylate-ethylene glycol-b-methyl methacrylate) and 1.25–1.90 for poly(styrene-b-ethylene glycol-b-styrene) from GPC measurements.     

Composition Regulation by Flow Copolymerization of Methyl Methacrylate and Glycidyl Methacrylate with Free Radical Method

It is important to match the feeding ratio of comonomers to the composition ratio in the resulting copolymers as closely as possible in industrial production, where the goal is often to produce more a homogeneous composition in copolymers. In this study, a flow copolymerization system with a conventionally initiated free radical method, together with randomly selected polymerization conditions is investigated. It is succeeded in achieving a closer match between the composition ratio and feeding ratio than previously reported in the copolymerization of styrene with methyl methacrylate and of glycidyl methacrylate with methyl methacrylate, which will widen the range of applications, by precisely controlling the mixing and heating in a flow polymerization apparatus. This is confirmed by the fact that the estimated values of reactivity ratios, r₁ and r₂, which are used in the reaction kinetics of copolymerization, are close to 1.     

Copolymerization of 4-methyl- and 4-methoxyphenyl acrylates with glycidyl methacrylate: Synthesis,characterization, reactivity ratios,and application as adhesives for the leather industry

Copolymers of 4-methyl- and 4-methoxyphenyl acrylates with glycidyl methacrylate having different copolymer compositions were synthesized in 1,4-dioxan using benzoyl peroxide as a radical initiator at 70 ± 0.5°C. The composition of the monomers in the copolymers were calculated using ¹H-NMR spectroscopy by comparing the integral values of well-separated aromatic and alifatic proton peaks. The reactivity ratios were calculated by Fineman-Ross, Kelen-Tudos, and extended Kelen-Tudos methods. The copolymers were characterized by ¹H-NMR and proton decoupled ¹³C-NMR spectroscopic techniques. Gel permeation chromatography was used for determining the $\overline {M_w }$ and $\overline {M_n }$ and polydispersity indexes of the copolymers. Thermal stability of the homo- and copolymers was calculated using thermogravimetric analysis, while differential scanning calorimetry was utilized in determining the glass transition temperature. Copolymers of suitable composition were chosen for curing reactions with diethanolamine in chloroform. The cured resins were tested as adhesives for leather-leather bonding at different temperatures (50, 90, 100, and 110°C). It was found that copoly(MOPA-GMA) at 50°C gave the best adhesive property over all other samples tested. © 1996 John Wiley & Sons, Inc.