Fineman-Ross Research Articles

Novel Methacrylamide Polymers Based on Thiazole and Styrene: A Study on Synthesis, Characterization, and Determination of Monomer Reactivity Ratios

In this study, firstly, a thiazole methacrylamide (TMAAm) monomer was synthesized from methacryloyl chloride with 2-aminothiazole. Later on, a series of copolymers of 2-thiazole methacrylamide (TMAAm) with styrene (St) using strange compositions in the feed has been prepared in solution via radical at 70 oC with AIBN as initiator. The structure of the copolymers was elucidated by FT-IR, 1H-NMR, and 13C-NMR spectroscopy methods. The compositions of the copolymers were determined from the nitrogen (N) difference according to the elemental analysis results. Monomer reactivity ratios; The rTMAAm and rSt, Fineman-Ross (FR), Kelen-Tüdös (KT) linear methods, and the error method model in non-linear variables were calculated with the computer program RREVM. The molecular weights and heterogeneity indices of the copolymers were determined by the GPC method. The thermal stability of the copolymers was investigated by thermogravimetry (TG) measurements.

Synthesis, Characterization and Antimicrobial studies of N-tert-amyl acrylamide (NTA) and 7-methacryloyloxy-4- methylcoumarin (MACU) Copolymers

Copolymers of N-tert-amylacrylamide (NTA) and 7-methacryloyloxy-4-methylcoumarin (MACU) were prepared by free radical polymerization in DMF at 600C using AIBN as an initiator. The copolymer compositions were determined by 1H-NMR analysis. The reactivity ratios of monomers were determined by Fineman-Ross (FR) (r1 = 1.33 and r2 = 0.60), KelenTudos (KT) (r1 = 1.33and r2 = 0.59). The r1.r2 = 0.798 indicated the formation of random copolymers.Tg found to increasing feed content of MACU. The antimicrobial studies showed that the copolymers are active against both Bacteria and Fungi.

Synthesis, Characterization and Antibacterial Application of Copolymers Based on N,N-Dimethyl Acrylamide and Acrylic Acid.

Hydrogel copolymers based on N,N-dimethyl acrylamide (DMA) and acrylic acid (AAc) were synthesized using a solution polymerization technique with different monomer ratios and ammonium persulfate as an initiator. This paper investigates the thermal stability, physical and chemical properties of the hydrogel copolymer. Testing includes Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), scanning electron microscopy (SEM) and elemental analysis (CHNS). The copolymer composition was determined by elemental analysis, and the reactivity ratios of monomers were calculated through linearization methods such as Fineman–Ross (FR), inverted Fineman–Ross (IFR), Kelen–Tudos (KT) and Mayo–Lewis (ML). Good agreement was observed between the results of all four methods. The ratio of r1 and r2 were 0.38 (r1) and 1.45 (r2) (FR), 0.38 (r1) and 1.46 (r2) (IFR), 0.38 (r1) and 1.43 (r2) (KT), and 0.38 (r1) and 1.45 (r2) (ML). Hydrogel copolymers exhibited good thermal stability, and SEM showed three-dimensional porous structures. Antibiotic-free and antibiotic-loaded hydrogels demonstrated antimicrobial properties against both Gram-positive and Gram-negative bacteria. As the ratio of DMA in hydrogel copolymer increased, the activity of copolymer against bacteria enhanced. The results indicated that these hydrogels have the potential to be used as antibacterial materials.

Spectroscopic characterization of glycidyl methacrylate with acrylonitrile copolymers and monomer reactivity ratios.

We report herein that copolymers containing glycidyl methacrylate (GMA) with acrylonitrile (AN) units were synthesized by free radical solution polymerization technique using benzoyl peroxide as a free radical initiator and 1,4-dioxane as a solvent at 70°C. The copolymerization behavior was studied in different composition with the mole fractions of GMA ranging from 0.20 to 0.80 in the feed and under 10% copolymer conversion. The copolymers were characterized by Fourier transform infrared spectroscopy, gel permeation chromatography, and scanning electron microscopy techniques. The thermogravimetric analysis of the copolymers suggest an overall decrease in the thermal stability of the copolymer with decreasing content of GMA in the copolymers. Thermal decomposition activation energies are calculated by the Ozawa method. The copolymer composition was determined by the application of elemental analysis method. The monomer reactivity ratios were estimated by the application of conventional linearization methods, such as Kelen-Tudos (K-T), Fineman-Ross (F-R) methods, and a nonlinear error in variable model (RREVM) method using a computer program, and all results were discussed and compared with the literature.

Investigation of mercaptan/ε-caprolactam initiated bulk copolymerization of methyl methacrylate with vinyl monomers

The bulk copolymerization of methyl methacrylate (MMA) with vinyl monomers initiated by e-caprolactam (CL) and n-dodecyl mercaptan (RSH) was investigated. Acrylonitrile (AN) and vinyl acetate (VAc) were used to copolymerize with MMA at 90 °C in the presence of CL and RSH, respectively. As evidenced by first-order kinetics of polymerization, linear increase of molecular weights with monomer conversions, and relatively low PDI values within a range of 1.3 to 1.6, both the copolymerization reactions exhibited living characteristics. Dependences of the copolymerization on the monomer feed ratio was also studied. An increase in the feed ratio of MMA induced an increased rate of copolymerization. In contrast, an increase in the initial loading of vinyl monomer leaded to the decrease in rate of copolymerization. The reactivity ratios of each pair of comonomers were also assessed using Fineman-Ross (FR) method. The results showed that the CL has an important influence on the kinetics of copolymerization, which caused the copolymerization parameters different from the most previously reported values.

Semibatch RAFT copolymerization of acrylonitrile and N-isopropylacrylamide: Effect of comonomer distribution on cyclization and thermal stability

Utilizing reversible addition-fragmentation chain transfer (RAFT) polymerization, the composition profile of PAN-based copolymers becomes a tunable parameter in preparing carbon fiber precursors. In this work, poly(acrylonitrile-co-N-isopropylacrylamide) copolymers were prepared via a semibatch process mediated by 2-cyano-2-propyl dodecyl trithiocarbonate (CPDT). The monomer reactivity ratios were determined by the Fineman-Ross (FR), Kelen-Tüdos (KT), and non-linear least squares (NLLS) models. The number average sequence length of acrylonitrile (AN) was found to be highly dependent on the content of N-isopropylacrylamide (NIPAM). NIPAM was introduced at controlled rates into a reaction vessel in attempt to facilitate its distribution in the polymer backbone. These semibatch copolymers were evaluated based on their ring-closing cyclization efficiency, which was characterized by differential scanning calorimetry (DSC), fourier transform infrared spectroscopy (FTIR), and thermogravimetric analysis (TGA). Significantly, DSC exotherms were reduced and cyclization occurred much faster reaching a greater thermal stability when NIPAM was introduced at slow feed rates.

나프탈이미도프로필 아크릴레이트와 GMA 공중합체의 합성과 물성

이 논문은 napthalimidopropylacrylate(NIPA)와 glycidylmethacrylate(GMA) 공중합체의 합성과 물성에 관한 연구로서 공중합체의 조성, 단량체 반응성비, 공명효과(Q)와 극성효과(e), 나프탈렌발색단을 가진 물질의 형광특성 등을 조사하였다. Azobisisobutyronitronitryl(AIBN) 개시제와 dimethylformamide(DMF) 용매를 <TEX>$60^{\circ}C$</TEX>에서 공중합하였다. 단량체의 반응성비는 Fineman-Ross(F-R), Kelen-<TEX>$T{\ddot{u}}d{\ddot{o}}s$</TEX>(K-T) 법으로 단량체 반응성비를 구한바, <TEX>$r_1$</TEX>은 <TEX>$r_2$</TEX>보다 크게 나타났다. NIPA이 GMA보다 공중합의 형성이 더 많음을 알 수 있다. 단량체 반응성비의 곱(<TEX>$r_1{\cdot}r_2$</TEX>)이 1보다 적어서 불규칙한 교대공중합체가 형성되었고 다른 단량체끼리 결합하게 된 교호공중합체를 형성된 것으로 간주된다. 380 nm에서 약한 분자 형광띠와 460 nm에서 강한 중합체 엑시머 형광띠가 나타났다. NIPA 단량체의 형광수명은 실온에서 UV 355 nm 파장에서 형광붕괴커브를 나타냈으며 <TEX>$5.1449{\times}10^{-7}s$</TEX>로 나타났다. GMA 공단량체를 아크릴계에 공중합시켜 우수한 내열성 열경화성 접착제나 코팅제에 응용될 것으로 사료된다. This work, which was about the synthesis of naphthalimidopropyl acrylate and GMA copolymers and their physical properties, investigated the compositions of the copolymer, the reactivity ratios of the monomer, resonance effect (Q), polar effect (e) and fluorescence of naphthalene. Azobisisobutyronitronitryl (AIBN) as an initiator was employed at <TEX>$60^{\circ}C$</TEX> with dimethylformamide (DMF) of solvent for the copolymerization of NIPA. <TEX>$r_1$</TEX> was found to be higher than <TEX>$r_2$</TEX> from the reactivity ratios of the monomer obtained from Fineman-Ross (F-R), Kelen-<TEX>$T{\ddot{u}}d{\ddot{o}}s$</TEX>(K-T) methods. NIPA was found to be more copolymerized than GMA. <TEX>$r_1{\cdot}r_2$</TEX> product was lower than 1, copolymerization was maked random-alternating type. The fluorescence spectrum of these polymers showed a weak monomer fluorescence band at 380 nm and a strong excimer fluorescence band at about 460 nm. Fluorescence life time of NIPA monomer showed fluorescence cover with UV 355 nm at room temperature, and life time showed <TEX>$5.1449{\times}10^{-7}s$</TEX>.

Synthesis, Antimicrobial Activity and Semi-conducting Properties of Novel 2-(4-Chloro-1-Naphtyloxy)-2-Oxoethyl Methacrylate with 2-(Diethylamino)Ethyl Methacrylate Copolymers

The free-radical initiated copolymerization of 2-(4-chloro-1-naphtyloxy)-2-oxoethyl methacrylate (ClNOEMA) with 2-(diethylamino) ethyl methacrylate (DEAEMA) was carried out in 1,4-dioxane solution at 70 ± 1°C using 2,2′-azobisisobutyronitrile (AIBN) as an initiator with different monomer-to-monomer ratios (ranging from 0.15 to 0.85) in the feed. The copolymer composition obtained by elemental analysis led to the determination of reactivity ratios employing Fineman-Ross (F-R) and Kelen-Tüdös (KT) linearization methods. These parameters were also estimated using a non-linear computational fitting procedure, known as reactivity ratios error in variable model (RREVM). The prepared homo and copolymers were tested for their antimicrobial activity against bacteria and yeast. These copolymers have been converted into novel salts by reaction with the iodemethane (CH3I). The copolymers and the corresponding salts have been characterized fully by a range of spectroscopic analysis techniques. The electrical conductivity dependence of temperature of the polymers were measured and the polymers exhibit the semi-conducting behavior, confirming that the electrical conductivity increases with increasing temperature. The poly(CINOEMA-co-DEAEMA) polymer doped by CH3I for 15 min shows the highest conductivity. The optical band gap, activation energy and room temperature conductivity values of these polymers were obtained. These electronic parameters suggest that the poly(CINOEMA-co-DEAEMA)s doped by CH3I for 15 min is an organic semiconductor with the thermally activated conduction mechanism.

Reactivity Ratios of the Copolymerization Styrene/ Methyl Methacrylate Using FT-IR Spectroscopy with Comparing to Mathematically Method

Free Radical Copolymerization of Styrene/ Methyl Methacrylate were prepared chemically under Nitrogen ,which was investigated, in the present of Benzoyl Peroxide as Initiator at concentration of 2 × 10-3 molar at 70 °C, which was carried out in Benzene as solvent to a certain low conversion . FT-IR spectra were used for determining of the monomer reactivity ratios ,which was obtained by employing the conventional linearization method of Fineman-Ross (F-R) and Kelen-Tüdos (K- T). The experimental results showed the average value for the Styrene r1 / Methyl Methacrylate r2 system, Sty r1 = 0.45 , MMA r2 = 0.38 in the (F–R) Method and r1 = 0.49 , r2 = 0.35 in the (K–T) Method, The Results of this indicated show the random distribution of monomers in the copolymer.Likewise The monomer reactivity ratios were evaluated Mathematically in comparison in the (F–R) Method with the data STY r1 = 0.61 , MMA r2 = 0.47 , and r1 = 0.45 , r2 =0.38 in the (K–T) Method. And were used the values r1 ,r2 for STY / MMA Copolymers in computing integral curves for the instantaneous Copolymer composition throughout the whole range of conversion.

Reactivity Ratios of the Copolymerization Styrene/ Methyl Methacrylate Using FT-IR Spectroscopy with Comparing to Mathematically Method

Free Radical Copolymerization of Styrene/ Methyl Methacrylate were prepared chemically under Nitrogen ,which was investigated, in the present of Benzoyl Peroxide as Initiator at concentration of 2 × 10-3 molar at 70 °C, which was carried out in Benzene as solvent to a certain low conversion . FT-IR spectra were used for determining of the monomer reactivity ratios ,which was obtained by employing the conventional linearization method of Fineman-Ross (F-R) and Kelen-Tüdos (K- T). The experimental results showed the average value for the Styrene r1 / Methyl Methacrylate r2 system, Sty r1 = 0.45 , MMA r2 = 0.38 in the (F–R) Method and r1 = 0.49 , r2 = 0.35 in the (K–T) Method, The Results of this indicated show the random distribution of monomers in the copolymer.Likewise The monomer reactivity ratios were evaluated Mathematically in comparison in the (F–R) Method with the data STY r1 = 0.61 , MMA r2 = 0.47 , and r1 = 0.45 , r2 =0.38 in the (K–T) Method. And were used the values r1 ,r2 for STY / MMA Copolymers in computing integral curves for the instantaneous Copolymer composition throughout the whole range of conversion.

Copolymers of glycidyl methacrylate and octadecyl acrylate: synthesis, characterization, swelling properties, and reactivity ratios

The free radical copolymerization of glycidyl methacrylate (GMA) and octadecyl acrylate (ODA) was carried out at 70 °C in solution using toluene as solvent and 2,2′-azobisisobutyronitrile (AIBN) as initiator. The copolymer compositions were determined using 1H NMR spectroscopy. The monomer reactivity ratios were computed using five linear methods at low conversions, i.e. Mayo–Lewis (ML), Fineman–Ross (FR), inverted Fineman-Ross (IFR), Ezrielev–Brokhina– Roskin (EBR) and Kelen–Tudos (KT). The reactivity ratios resulted from different methods are in agreement with each other and showed higher reactivity for GMA monomer in comparison with ODA monomer (FR: r G = 1.29 and r O = 0.68). Crosslinked GMA–ODA copolymers were also prepared using ethylene glycol dimethacrylate as a crosslinker. Thermal properties and swelling behaviors of crosslinked copolymers in different polar and nonpolar solvents were evaluated. GMA incorporation in the crosslinked copolymers improved T g values, while decreased T m quantities and swelling in nonpolar solvents. The swelling values are in the acceptable range and the prepared functional crosslinked copolymers can be used for nonpolar solvents absorbency applications.

Synthesis and characterization of poly[(1-vinyl-1,2,4-triazole)-co -(monomer with carboxylic acid group(s))] and determination of monomer reactivity ratios: I. Acrylic acid

Copolymers of 1-vinyl-1,2,4-triazole (VTAz) and acrylic acid (AA) having different mole ratios were synthesized using free radical-initiated solution polymerization in dimethylformamide at 70 °C with α,α′-azobisisobutyronitrile as initiator in nitrogen atmosphere. The compositions of the synthesized copolymers for a wide range of monomer feeds were determined using Fourier transform infrared (FTIR) spectroscopy through recorded absorption bands for VTAz (1510 cm−1, CN (triazole ring) stretching mode) and AA (1710 cm−1, CO stretching mode) units. The structures of the copolymers were characterized using FTIR and 1H NMR spectroscopy. The copolymer compositions were also determined from 1H NMR analysis following proton signals of carboxyl group at 11.8–12.5 ppm of AA and of triazole ring at 7.5–8.1 ppm of VTAz. Monomer reactivity ratios for the VTAz-AA pair were estimated using linear methods, i.e. Fineman–Ross (FR) and Kelen–Tüdös (KT). From FTIR evaluation, monomer reactivity ratios were calculated as r1 = 0.404 and r2 = 1.496 using the FR method and r1 = 0.418 and r2 = 1.559 using the KT method. These values were found to be very close to those obtained from NMR evaluation. The two cases r1r2 < 1 and r1 < r2 indicated the random distribution of the monomers in the final copolymers and the presence of a greater amount of AA units in the copolymer than in the feed, respectively. The observed relatively high activity of complexed growing radical-AA• … VTAz was explained by the effect of complex formation between carbonyl groups and triazole fragments in chain growth reactions. Thermal behaviours of copolymers with various compositions were investigated using thermogravimetric and differential scanning calorimetric analyses. It was observed that thermal stabilities and glass transition temperatures of the copolymers increased resulting from complex formation between acid and triazole units. © 2012 Society of Chemical Industry

Polymers Based on Methacrylate Bearing Coumarin Side Group: Synthesis via Free Radical Polymerization, Monomer Reactivity Ratios, Dielectric Behavior, and Thermal Stabilities

Copolymerization and homopolymerization of 7-methacryloyloxy coumarin (MAOC) and its copolymers with benzyl methacrylate (BMA), methyl methacrylate (MMA), ethyl methacrylate (EMA), and isobuthyl methacrylate (IBMA) were performed by the free radical polymerization method (FRP) at low conversions (&lt;15%). The resulting polymers were characterized by FTIR, 1H NMR, GPC, DSC, and TGA. The monomer reactivity ratios of MAOC and BMA were computed using Kelen-Tüdös (K-T) and Fineman-Ross (F-R) methods and were found to be r1=0.45, r2=1.29; r1=0.46; r2=1.33, respectively (r1 is monomer reactivity ratio of MAOC). Blends of poly(MAOC) and poly(BMA) obtained via FRP method were prepared by casting films from dichloromethane solution and were characterized by DTA and TGA techniques. Dielectric measurements for MAOC homopolymer and its copolymers with EMA, MMA, and IBMA were carried out by means of an impedance analyzer as a function of temperature and frequence. Dielectric properties of polymer samples prepared in a plate form were measured at room temperature over the frequency range 0.1 kHz–2 MHz and given as compared with each other.

Synthesis and Characterization of Organotin Containing Copolymers: Reactivity Ratio Studies

Organotin monomers containing dibutyltin groups – dibutyltin citraconate (DBTC) as a new monomer and dibutyltin maleate (DBTM) – were synthesized. Free radical copolymerizations of the organotin monomers with styrene (ST) and butyl acrylate (BA) were performed. The overall conversion was kept low (≤15% wt/wt) for all studied samples and the copolymers composition was determined from tin analysis using the Gillman and Rosenberg method. The reactivity ratios were calculated from the copolymer composition using the Fineman-Ross (FR) method. The synthesized monomers were characterized by elemental analysis, 1H-, 13C-NMR and FTIR spectroscopy.

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

Phenoxyethyl methacrylate (POEMA) and butyl methacrylate (BMA) were copolymerized by free-radical copolymerization using α,α′-azobisisobutyronitrile (AIBN) in 2-butanone solution at 333±1 K. Copolymers were characterized by FTIR, 1H-NMR and 13C-NMR spectroscopic methods and by comparison of the spectra with the corresponding homopolymers. Thermogravimetric analysis of the copolymers was carried out in order to know their thermal stability. Copolymer composition was established by 1H-NMR analysis. Monomer reactivity ratios (MRR) were computed using the classical Fineman – Ross (FR) and Kelen – Tüdos (KT) procedures. MRR were also estimated using a nonlinear computational fitting procedure, known as reactivity ratios error in variable model (RREVM). The mean sequence lengths of the copolymers were estimated and suggest that random copolymers were obtained.

Novel Copolymers of 4-Chloronaphthyl Methacrylate with Acrylonitrile: Determination of Monomer Reactivity Ratios and Antimicrobial Activity

Methacrylate based monomer, 4-chloronaphthyl methacrylate (4-CNMA) was synthesized by reacting 4-chloro naphthol with methacryloyl chloride in the presence of triethylamine (NR3) at 0–5°C. The free-radical initiated copolymerization of (4-CNMA), with acrylonitrile (AN) was carried out in 1,4-dioxane-dimethyl sulfoxide mixture (8:2) solution at 70 ± 1°C using 2,2′-azobisisobutyronitrile (AIBN) as an initiator with different monomer-to-monomer ratios in the feed. The monomer 4-CNMA, poly(4-CNMA) and copolymers were characterized by FT-IR and 1H-and 13C-NMR spectral studies. The copolymer composition obtained by elemental analysis led to the determination of reactivity ratios employing Fineman-Ross (F-R), Kelen-Tüdös (KT) and Extended Kelen-Tüdös (EKT) linearization methods. These parameters were also estimated using a non-linear computational fitting procedure, known as reactivity ratios error in variable model (RREVM). The solubility of the polymers was tested in various polar and non-polar solvents. Gel permeation chromatography was employed to determine the molecular weights (Mw and Mn) and polydispersity index of polymers. Thermogravimetric analysis of the polymers reveals that the thermal stability of the copolymers increases with increase in the mole fraction of 4-CNMA in the copolymers. The prepared homo and copolymers were tested for their antimicrobial activity against bacteria, fungi and yeast.

ANTIMICROBIAL ACTIVITY OF COPOLYMERS OF 2,4-DICHLOROPHENYL ACRYLATE WITH STYRENE: SYNTHESIS, CHARACTERIZATION AND REACTIVITY RATIOS

Some copolymers of 2,4-dichlorophenyl acrylate (2,4-DCPA) with styrene (St) of different feed compositions were prepared by free radical polymerization technique using 2,2′-azobisisobutyronitrile (AIBN) as an initiator, and the copolymers were characterized by IR spectroscopy. The copolymer composition obtained by UV-spectra led to determination of reactivity ratio by employing Fineman-Ross (F-R) and Kelen-Tudos (K-T) methods. Average molecular weight, as well as intrinsic viscosity, was obtained by vapor pressure osmometry (VPO) and Ubbleholde viscometer. Thermo gravimetric analysis (TGA) and differential thermal analysis (DTA) of copolymers were carried out under nitrogen atmosphere. Antimicrobial effects of the homo and copolymers were also investigated against various microorganisms such as bacteria, fungi and yeasts.

N-vinylpyrrolidone and 4-vinyl Benzylchloride Copolymers: Synthesis, Characterization and Reactivity Ratios

The copolymers prepared in this study by free radical copolymerization of N-vinylpyrrolidone (M 2) with 4-vinylbenzylchloride (M 1) using 2,2′-azobisisobutyronotrile (AIBN) initiator in 1,4-dioxane solvent at 70°C were characterized by FTIR, 1H-NMR and 13C-NMR techniques. Polymer solubility was tested in both polar and nonpolar solvents. The thermal properties were studied by thermogravimetric analysis (TGA) and differential scanning calorimeter (DSC). Copolymer compositions were established by H1-NMR spectra, while reactivity ratios of the monomers were computed using the linearization methods viz., Fineman-Ross (FR) (r 1 = 1.67 and r 2 = 0.67), Kelen-Tudos (KT) (r 1 = 1.77 and r 2 = 0.65) and extended Kelen-Tudos (EK-T) (r 1 = 1.72 and r 2 = 0.63) methods at lower conversion. Furthermore, reactivity ratios in nonlinear error-in-variables method (RREVM) also compute the reactivity ratios (r 1 = 1.76 and r 2 = 0.66); these are found to be in good agreement with each other. The distribution of monomer sequence along the copolymer chain was calculated using a statistical method based on the calculated reactivity ratios.

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.

Copolymerization of N‐(4‐bromophenyl)‐2‐methacrylamide with n‐butyl methacrylate: Synthesis, characterization and monomer reactivity ratios

AbstractThe monomer, N‐(4‐bromophenyl)‐2‐methacrylamide (BrPMAAm) has been synthesized by reacting 4‐bromoaniline with methacryloyl chloride in the presence of triethylamine (NR3) at 0−5°C. Copolymerization of BrPMAAm with n‐butyl methacrylate (n‐BMA) has been carried out in 1,4‐dioxane by free radical solution polymerization at (70 ± 0.1)°C utilizing 2,2′‐azobisisobutyronitrile (AIBN) as an initiator in different in‐feed ratios. The composition of the copolymer was determined by the elemental analysis. The comonomer reactivity ratios determined by Fineman‐Ross (FR), Kelen‐Tüdös (KT), and extended Kelen‐Tüdös (EKT) methods. The copolymers were characterized by FTIR, 1H‐, and 13C NMR spectroscopic technique. Gel permeation chromatography was employed for estimating the weight–average (Mw) and number–average (Mn) molecular weights and polydispersity index (PDI) of the copolymers. Glass transition temperatures (Tg) were determined by differential scanning calorimetry and found to be characteristic of copolymer composition. As the N‐(4‐bromophenyl)‐2‐methacrylamide content increases, the Tg increases from 339 to 437 K. Thermal stabilities of the homo‐ and copolymers were calculated using thermogravimetric analysis. Thermally stable copolymers were obtained by the incorporation of BrPMAAm units as the initial decomposition temperature of the copolymers increased with the increase in concentration of BrPMAAm units. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008