Ibrahim Erol

Synthesis and characterization of two new cyclobutyl and aryl hydroxyethyl methacrylate monomers and their polymers

Two new hydroxyethyl methacrylates having aryl and cyclobutane rings were synthesized by addition to 1-(epoxyethyl)-3-aryl-3-methylcyclobutane to methacrylic acid. The monomers prepared are 2-(3-methyl-3-phenylcyclobutyl)-2-hydroxyethyl methacrylate (PCHEMA) and 2-(3-methyl-3-mesitylcyclobutyl)-2-hydroxyethyl methacrylate (MCHEMA). Both monomers were polymerized at 60°C in 1,4-dioxane solution using benzoyl peroxide as initiator. Poly(PCHEMA) and poly(MCHEMA) and their monomers were characterized by FT-IR and 1H- and 13C-NMR techniques. Weight average molecular weights of the polymers were determined for poly(PCHEMA) poly(MCHEMA) by gel permation chromatography. Thermal stabilities of the polymers were essentially the same. Glass transition temperatures for poly(PCHEMA) and poly(MCHEMA) were determined as 105 and 137°C, respectively. No changes of the polymers by irradiation with UV light at 254 nm were observed.

SYNTHESIS, CHARACTERIZATION, AND POLYMERIZATION OF NEW METHACRYLATE ESTERS HAVING PENDANT AMIDE MOIETIES

ABSTRACT In this paper, the synthesis of a number of new methacrylate esters containing amide group are described. The monomers produced from the reaction of corresponding α-chloro-N-aryl or -N-alkyl acetamides with sodium methacrylate were polymerized with AIBN as initiator. The monomers and their polymers were characterized by IR, 1H- and 13C-NMR spectroscopy. The glass transition temperature and thermal decomposition temperature of the polymers were investigated by DSC-50 and TGA-50 thermobalance, respectively. The photocrosslinking properties of the polymers were also discussed.

Copolymerization and monomer reactivity ratios of 2-(3-mesityl-3-methylcyclobutyl)-2-hydroxyethyl methacrylate with acrylonitrile

Abstract The free radical copolymerization of 2-3-(mesityl-3-methylcyclobutyl)-2-hydroxyethyl methacrylate (MCHEMA) with acrylonitrile (AN) has been carried out in 1,4-dioxane at 60°C. The copolymers were characterized by infrared, 13C and 1H NMR spectroscopic methods. The copolymer compositions were established by elemental analysis. The reactivity ratios of copolymerization were computed by using the Fineman–Ross and Kelen–Tudős methods, and were found to be r1=0.29±0.002, r2=0.98±0.003 and r1=0.21±0.009, r2=0.75±0.003, respectively (r2 is reactivity ratios of MCHEMA). The glass transition temperature and thermal decomposition temperature were investigated by DSC-50 and TGA-50 thermobalance, respectively. The solubility parameters and densities of all the copolymers were determined.

COPOLYMERIZATION OF METHYL METHACRYLATE WITH 2-METHYLBENZYL METHACRYLATE AND 4-METHYLBENZYL METHACRYLATE: SYNTHESIS, CHARACTERIZATION, AND MONOMER REACTIVITY RATIOS

ABSTRACT Two types of copolymers based on 2-methylbenzyl methacrylate and 4-methylbenzyl methacrylate with methyl methacrylate were synthesized. Several copolymers of 2-methylbenzyl methacrylate (2-MBZMA) and 4-methylbenzyl methacrylate (4-MBZMA) with methyl methacrylate (MMA) having different copolymer compositions were performed in 1,4-dioxane using 2,2′-azobisisobutyronitrile (AIBN) as a free radical initiator at 60±1°C. The copolymers were characterized by FT-IR, 1H- and 13C-NMR spectroscopic techniques. The composition of monomeric units in the copolymer system was calculated using 1H-NMR spectroscopy by comparing the integral values of well separated aromatic and aliphatic proton peaks. The reactivity ratios were calculated by employing Fineman-Ross and Kelen-Tüdös methods. The values of r1 and r2 obtained by the Fineman-Ross and Kelen-Tüdös methods appear to be in close agreement with each other, i.e., r1(2-MBZMA):1.03±0.039 and r2(MMA): 0.77±0.012 for the copoly(2-MBZMA-MMA) system, r1(4-MBZMA): 0.97±0.040 and r2(MMA):0.77±0.050 for the copoly(4-MBZMA-MMA) system. Thermal stabilities of the homo- and co-polymers were investigated using thermogravimetric analysis, while differential scanning calorimetry was used to determine the glass transition temperature.

Synthesis and Characterization of Novel Methacrylates Derived from Morpholine and Pyrrolidine: The Determination of Kinetic Parameters with Thermogravimetric Analysis

Abstract The synthesis of two new methacrylate esters containing morpholine and pyrrolidine group are described. The monomers produced from the reaction of corresponding morpholino chloroacetamide and pyrrolidino chloroacetamide with sodium methacrylate were polymerized in DMSO solution at 65°C using AIBN as an initiator. The monomers and their polymers were characterized by Fourier transform infrared (FTIR), 1H‐ and 13C‐NMR spectroscopy. The glass transition temperature of the polymers were investigated by DSC and thermal decomposition activation energies were calculated by the Ozawa method using the SETARAM Labsys thermogravimetric analysis (TGA) thermobalance, respectively. By using gel permeation chromatography, weight average (M¯w) and number average (M¯n) molecular weights and polidispersity indices of the polymers were determined.

A STUDY OF COPOLYMERIZATION WITH 4-BROMOBENZYL METHACRYLATE AND ETHYL METHACRYLATE

ABSTRACT 4-Bromobenzyl methacrylate [BrBMA] monomer was synthesized from a reaction of sodium methacrylate with 4-bromobenzylbromide. The copolymerization of this monomer with ethyl methacrylate (EMA) and its homopolymerization were carried out in a 1,4-dioxane solution at 60°C using 2,2′-azobisisobutyronitrile [AIBN] as initiator. The monomer and the polymers were characterized by IR, 1H and 13C-NMR techniques. The composition of monomeric units in the copolymer system was calculated using 1H-NMR spectroscopy by comparing the integral values of well separated aromatic and aliphatic proton peaks. The monomer reactivity ratios of copolymerization were determined by using the Kelen-Tüdös (K-T), Inverted Fineman-Ross (IFR) and Yezrielev-Brokhina-Roskin (YBR) methods, and were found to be r1=0.44, r2=0.63 and r1=0.24, r2=0.47 and r1=0.37, r2=0.64, respectively (r1 is the monomer reactivity ratio of BrBMA). Based on the experimental data of the K-T method, triad analysis was performed. It is concluded that this copolymerization results in statistical-type macromolecules. The solubility parameters and the glass transition temperature of the copolymers were determined as a function of copolymer composition.

Synthesis and Characterization of Novel Methacrylate Monomers Having Pendant Oxime Esters and Their Copolymerization with Styrene

New methacrylate monomers, 2‐{[(diphenylmethylene)amino]oxy}‐2‐oxoethyl methacrylate (DPOMA) and 2‐{[(1‐phenylethylidene)ami no]oxy}‐2‐oxoethyl methacrylate (MMOMA) were prepared by reaction of sodium methacrylate with diphenylmethanone O‐(2‐chloroacetyl) oxime and 1‐phenylethanone O‐(2‐chloroacetyl) oxime, respectively. They were obtained from a reaction of chloroacetyl chloride with benzophenone oxime or acetophenone oxime. The free‐radical‐initiated copolymerization of (DPOMA) and (MMOMA) with styrene (St) were carried out in 1,4‐dioxane solution at 65°C using 2,2‐azobisisobutyronitrile (AIBN) as an initiator with different monomer‐to‐monomer ratios in the feed. The monomers and copolymers were characterized by FTIR, 1H‐ and 13C‐NMR spectral studies. The copolymer compositions were evaluated by nitrogen content in polymers. The reactivity ratios of the monomers were determined by the application of Fineman–Ross and Kelen–Tüdös methods. The molecular weights (M¯w and M¯n) and polydispersity index of the polymers were determined by using 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 St in the copolymers. The activation energies of the thermal degradation of the polymers were calculated with the MHRK method. Glass transition temperatures of the copolymers were found to decrease with an increase in the mole fraction of DPOMA or MMOMA in the copolymers. The antibacterial and antifungal effects of the monomers and polymers were also investigated on various bacteria and fungi. The photochemical properties of the polymers were investigated by UV and FTIR spectra.

Synthesis and Evaluation of Thermal Properties of Fluorinated Poly(aryl ether) Dendritic Structures Based on Calix[4]arenes

By using a convergence approach two new poly(aryl ether) dendritic structures carrying 4-fluorobenzyl bromide on the surface and calix[4]arenes as a core with G1 were synthesized for the first time. Fluorinated dendritic structures are connected through ether bonds on the lower rim of the calix[4]arene unit. Its structure was determined by 1H-NMR and elemental analysis. The thermal stabilities of fluorinated dendritic structures, based on calix[4]arenes, were investigated using thermogravimetric analysis. The activation energies and thermal degradation of the structures were calculated with the Ozawa Method.

Synthesis, Characterization, Thermal and Biological Properties of a New Methacrylate Polymer and Its Derivatives

A new type of methacrylate monomer, 2-(4-acetylphenoxy)-2-oxoethyl-2-methylacrylate(AOEMA), was synthesized. The radical homopolymerization of AOEMA was performed at 65 °C in a 1,4-dioxane solution with benzoyl peroxide as an initiator. The oxime, and thiosemicarbazone derivatives of poly[2-(4-acetylphenoxy)-2-oxoethyl-2-methylacrylate] (AOEMA) were prepared with hydroxylamine hydrochloride, and thiosemicarbazone hydrochloride, respectively. The monomer and its homopolymer were characterized with Fourier transform infrared and NMR techniques. The thermal stabilities of poly(AOEMA) and its derivatives were investigated using thermogravimetric analysis and differential scanning calorimetry. The ultraviolet stability of the polymers were compared. The antibacterial and antifungal effects of the monomer and the polymer and its derivatives were also investigated on various bacteria and fungi. The activation energies of the thermal degradation of the polymers were calculated with the Ozawa method.

Copolymers of 2‐(3‐(6‐tetralino)‐3‐methyl‐1‐cyclobutyl)‐2‐Hydroxyethyl Methacrylate with Acrylonitrile and 4‐Vinylpyridine: Synthesis, Characterization, and Monomer Reactivity Ratios

The copolymerization of 2‐(3‐(6‐tetralino)‐3‐methyl‐1‐cyclobutyl)‐2‐hydroxyethyl methacrylate (TCHEMA), monomer with acrylonitrile and 4‐vinylpyridine were carried out in 1,4‐dioxane solution at 65°C using AIBN as an initiator. The copolymers were characterized by FTIR, 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. The monomer reactivity ratios were calculated by the Fineman‐Ross and Kelen‐Tüdös method. Also, the apparent thermal decomposition activation energies were calculated by the Ozawa method with a Shimadzu TGA 50 thermogravimetric analysis thermobalance.