4‐chloro‐3‐methylphenyl methacrylate copolymers with 2,4‐dichlorophenyl methacrylate: Synthesis,characterization, and antimicrobial activity

4‐Chloro‐3‐methylphenyl methacrylate (CMPM) and 2,4‐dichlorophenyl methacrylate (2,4‐DMA) were synthesized by reacting methacryloyl chloride with 4‐chloro‐3‐methylphenol (CMP) and 2,4‐dichlorophenol (2,4‐DP), respectively. Homo and copolymers of CMPM and 2,4‐DMA were obtained from different monomer feed ratios, using 2,2′‐azobisisobutyronitrile as initiator in toluene at 70°C. IR‐spectroscopy was employed to characterize the resulting homo and copolymers. Copolymer compositions were determined by ultraviolet (UV) spectroscopy. Fineman–Ross method was used to calculate the reactivity ratios of the monomers. Average molecular weight and polydispersity index were obtained by gel permeation chromatography (GPC). Thermogravimetric analyses (TGA) and differential thermal analysis (DTA) of copolymers were carried out under a nitrogen atmosphere. Antimicrobial effects of the homo and copolymers were also investigated for various microorganisms such as bacteria, fungi, and yeast. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100:439–448, 2006     

Synthesis and characterization of N‐acryloylcarbazole/methyl methacrylate copolymers

Copolymers of N‐acryloylcarbazole (A) and methyl methacrylate (M) were synthesized in different in‐feed ratios. The composition of the copolymer was determined by the help of ¹H NMR spectrum. The comonomer reactivity ratios determined by Kelen‐Tudos (KT) and nonlinear error‐in‐variables methods were r_A = 1.12 ± 0.16, r_M = 0.94 ± 0.14, and r_A = 1.05, r_M = 0.90, respectively. Complete spectral assignments of the ¹H and ¹³C ¹H NMR spectra of the copolymers were done by the help of distortionless enhancement by polarization transfer (DEPT) and two‐dimensional NMR techniques, such as heteronuclear single quantum coherence (HSQC), total correlation spectroscopy (TOCSY), and heteronuclear multiple bond correlation (HMBC). The methine, α‐methyl, and carbonyl carbon resonances were found to be sequence sensitive. The signals obtained were broad because of the restricted rotation of bulky carbazole group and the quadrupolar effect of nitrogen present in carbazole moiety. Glass transition temperatures (T_g) were determined by differential scanning calorimetry and were found to be characteristic of copolymer composition. As the N‐acryloylcarbazole content increases, the T_g increases from 378.3 K for poly(methyl methacrylate) to 430.4 K for poly(N‐acryloylcarbazole). Variation in T_g with the copolymer composition were found to be in good agreement with theoretical values obtained from Johnston and Barton equations. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2667–2676, 2006     

Synthesis and characterization of hydrophilic copolymers of maleimide derivatives with 2‐hydroxyethyl methacrylate: electrochemical and thermal behavior

BACKGROUND: The high‐technology industries have been the driving force in the development of new synthetic polymers that combine thermal stability with specific functional properties. In this study p‐chlorophenylmaleimide, p‐hydroxyphenylmaleimide and p‐nitrophenylmaleimide (R‐PhMI) with 2‐hydroxyethyl methacrylate (HEMA) were synthesized by free radical polymerization to obtain hydrophilic polymers, in order to study the effect of the p‐chloroaryl, p‐hydroxyaryl or p‐nitroaryl group on the copolymer composition, electrochemical behavior and thermal properties. RESULTS: The thermal behavior was correlated with the copolymer composition and functional groups, maleimide derivatives, on the copolymers. Thermal decomposition temperature (TDT) and glass transition temperature (T_g) were influenced by the functional groups of R‐PhMI moiety on the copolymer. The polymers showed an electrochemically irreversible reduction process under the conditions tested. CONCLUSION: Poly[(p‐chloromaleimide)‐co‐(2‐hydroxyethyl methacrylate)] copolymer shows a higher TDT than poly[(p‐hydroxymaleimide)‐co‐(2‐hydroxyethyl methacrylate)] or poly[(p‐nitromaleimide)‐co‐(2‐hydroxyethyl methacrylate)] (NPHE). T_g decreases in going from nitro to hydroxyl to chloro groups. The NPHE copolymer shows a lower stability, losing weight at 200 °C. The NPHE copolymer shows a well‐defined reduction wave which is similar to those of the other copolymers and it also shows an additional quasi‐reversible reduction wave corresponding to the nitrobenzene group. Copyright © 2009 Society of Chemical Industry     

COPOLYMERS OF 2,4-DICHLOROPHENYL METHACRYLATE WITH BUTYL METHACRYLATE AND THEIR APPLICATION AS BIOCIDES

Copolymers of 2,4-dichlorophenyl methacrylate and butyl methacrylate were synthesized with different monomer concentrations using toluene as a solvent and 2,2′-azobisisobutyronitrile (AIBN) as an initiator at 70°C. The copolymers were characterized by IR-spectroscopy. Copolymer compositions were determined by UV-spectroscopy. The reactivity ratios for monomer pairs were determined by Fineman-Ross method. Gel permeation chromatography was employed for determining the average molecular weights and the polydispersity index. The intrinsic viscosities of polymers were also discussed. Thermogravimetric analyses of polymers were carried out in nitrogen atmosphere. The homo- and copolymers were tested for their effect on the growth of various microorganisms.     

Synthesis and characterization of novel fluorine‐containing methacrylate copolymers: Reactivity ratios,thermal properties,and antimicrobial activity

The free‐radical‐initiated copolymerization of 2‐(4‐acetylphenoxy)‐2‐oxoethyl‐2‐methylacrylate (AOEMA) and 2‐(4‐benzoylphenoxy)‐2‐oxoethyl‐2‐methylacrylate (BOEMA) with 2‐[(4‐fluorophenyoxy]‐2‐oxoethyl‐2‐methylacrylate (FPEMA) were carried out in 1,4‐dioxane solution at 65°C using 2,2′‐azobisisobutyronitrile as an initiator with different monomer‐to‐monomer ratios in the feed. The monomers and copolymers were characterized by FTIR and ¹H‐ and ¹³C‐NMR spectral studies. ¹H‐NMR analysis was used to determine the molar fractions of AOEMA, BOEMA, and FPEMA in the copolymers. The reactivity ratios of the monomers were determined by the application of Fineman‐Ross and Kelen‐Tudos methods. The analysis of reactivity ratios revealed that BOEMA and AOEMA are less reactive than FPEMA, and copolymers formed are statistically in nature. The molecular weights (M _w and M _n) and polydispersity index of the polymers were determined 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 FPEMA in the copolymers. Glass transition temperatures of the copolymers were found to decrease with an increase in the mole fraction of FPEMA in the copolymers. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

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     

4‐Acetamidophenyl acrylate copolymers with acrylonitrile and N‐vinyl‐2‐pyrrolidone: Synthesis,characterization, and reactivity ratios

4‐Acetamidophenyl acrylate (APA) was synthesized and characterized by IR, ¹H and ¹³C NMR spectroscopies. Homo‐ and copolymers of APA with acrylonitrile (AN) and N‐vinyl‐2‐pyrrolidone (NVP) were prepared by a free radical polymerization. All the copolymer compositions have been determined by ¹H NMR technique, and the reactivity ratios of the monomer pairs have been evaluated using the linearization methods Fineman–Ross, Kelen–Tudos, and extended Kelen–Tudos. Nonlinear error‐in‐variable model (EVM) method was used to compare the reactivity ratios. The reactivity ratios for copoly(APA–AN) system were APA(r₁) = 0.70 and AN(r₂) = 0.333, and for copoly(APA–NVP) system the values were APA(r₁) = 4.99 and NVP(r₂) = 0.019. Thermal stability and molecular weights of the copolymers are reported. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 1919–1927, 2006     

Photocrosslinkable copolymers based on 4‐acryloyloxyphenyl‐3′‐chlorostyryl ketone and methyl methacrylate: synthesis,comonomer reactivity ratios and UV photosensitivity

A new photosensitive acrylate monomer having a pendant chlorocinnamoyl moiety (APCSK) was copolymerized with methyl methacrylate (MMA) in different feed compositions in ethyl acetate solution at 70°C using benzoyl peroxide as a free‐radical initiator. The newly synthesized copolymers were characterized by FTIR, ¹H and ¹³C nuclear magnetic resonance (NMR) spectral techniques, as well as by size‐exclusion chromatography. Their thermal behaviour was assessed by thermogravimetric analysis in air and differential scanning calorimetry under nitrogen atmosphere. The copolymers exhibit no phase separation since there is only one glass transition temperature (T_g) value in the region of copolymer composition studied. The reactivity ratios of the comonomers were calculated by adopting linearization methods such as the Fineman–Ross (F‐R), Kelen–Tudos (K‐T) and extended Kelen–Tudos (ExtK‐T) methods, and by a non‐linear error‐in‐variables model method (EVM) using a computer program (RREVM). The results suggest that MMA is more reactive than APCSK and that their copolymerization leads to the formation of random copolymers. The photosensitivity of the copolymer samples was studied in solution as well as in thin films through UV irradiation. The influence of different factors, including solvent nature, concentration, temperature, photosensitizer and copolymer composition, on the rate of photocrosslinking of the photoreactive copolymers was investigated for effective industrial application of these polymers as negative photoresists. Copyright © 2004 Society of Chemical Industry     

Phenyl methacrylate-glycidyl methacrylate copolymers: synthesis, characterization and reactivity ratios by spectroscopic methods

The free-radical polymerization of phenyl methacrylate and glycidyl methacrylate was carried out at 70°C in the presence of benzoyl peroxide using 2-butanone as the solvent. The copolymer compositions of seven copolymer samples with different feed compositions as well as the tacticities were determined by ¹H nuclear magnetic resonance spectroscopy. The results were used to calculate the reactivity ratios by the Kelen-Tudos method, which were found to be r₁ = 1.57 ± 0.56 and r₂ = 0.84 ± 0.51. The homo- and copolymers were also characterized by Fourier-transform infra-red and ¹³C nuclear magnetic resonance spectroscopic methods. , and polydispersity indices of the copolymers were determined using gel permeation chromatography.