Stereochemical and compositional assignments of trans‐4‐methacryloyloxyazobenzene–methyl methacrylate copolymers by one‐ and two‐dimensional NMR spectroscopy

The microstructure of trans‐4‐methacryloyloxyazobenzene–methyl methacrylate copolymers prepared by solution polymerization process using AIBN as initiator is analyzed by one‐and two‐dimensional spectroscopy. Sequence distribution was calculated from the ¹³C(¹H)‐NMR spectra of the copolymers. Comonomer reactivity ratios were determined using the Kelen–Tudos and the nonlinear error‐in‐variables methods are r_A = 1.14 ± 0.08 and r_M = 0.51 ± 0.03; r_A = 1.13 ± 0.1 and r_M = 0.50 ± 0.04, respectively. The sequence distribution of A‐ and M‐centered triads determined from ¹³C(¹H)‐NMR spectra of copolymer is in good agreement with triad concentration calculated from a statistical model. The 2‐D heteronuclear single‐quantum correlation and correlated spectroscopy (TOCSY) was used to analyze the complex ¹H‐NMR spectrum. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 3016–3025, 1999     

Microstructure determination of isobornyl methacrylate-styrene copolymer by NMR spectroscopy

An investigation of the microstructure of isobornyl methacrylate - styrene (I/S) copolymers prepared by the atom transfer radical polymerization (ATRP) using methyl-2-bromopropionate as an initiator and PMDETA copper complex as catalyst under nitrogen atmosphere at 70 °C has been done by two-dimensional NMR techniques. 2D- HSQC and TOCSY have been utilized to resolve the complex ¹H NMR spectrum and to establish the compositional and configurational sequences of isobornyl methacrylate-styrene (I/S) copolymers. 2D HSQC and TOCSY spectra showed compositional and configurational sensitivity of α-methyl carbon of I unit and methine proton of S unit and are assigned up to the triad level. The methylene carbon (C₁₀) also shows triad level of compositional sensitivity in 2D HSQC spectra. Heteronuclear multiple-bond correlation (HMBC) spectroscopy has been used to study carbonyl/quaternary carbon-proton coupling. The carbonyl and quaternary carbons showed compositional and configurational sensitivity upto the triad level. The values of reactivity ratios were determined by Kelen-Tudos (KT) and nonlinear error in variable method (RREVM) using copolymer composition data that were determined by ¹H NMR spectrum. Reactivity ratios of co-monomers in I/S copolymer, determined from a linear Kelen-Tudos method (KT) and non-linear Error-in-Variable Method (EVM), are r_I?=?0.39?±?0.09, r_S?=?0.44?±?0.08 and r_I?=?0.42, r_S?=?0.47, respectively.     

Sequence determination of vinyl acetate–methyl acrylate copolymers by NMR spectroscopy

Vinyl acetate/methyl acrylate (V/M) copolymers were prepared by free-radical solution polymerization in benzene. Copolymer compositions were obtained from ¹H-NMR spectroscopy. Reactivity ratios for the copolymerization of V with M were calculated using the Kelen-Tudos (KT) and the nonlinear error in variables (EVM) methods. The reactivity ratios obtained from the KT and EV methods are r_V = 0.04 ± 0.03 and r_M = 7.28 ± 2.88 and r_v = 0.04 ± 0.01 and r_M = 7.28 ± 0.37, respectively. The microstructure was obtained in terms of the distribution of V- and M-centered triad sequences from ¹³C{¹H}-NMR spectra of copolymers. Homonuclear ¹H-2D-COSY and 2D-NOESY NMR were used to determine the most probable conformer for the V/M copolymer. The copolymerization behavior of the V/M copolymers as a function of conversion is also reported. © 1994 John Wiley & Sons, Inc.     

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).     

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).     

Sequencing of N‐vinyl‐2‐pyrrolidone/glycidyl methacrylate copolymers by one‐dimensional and two‐dimensional nuclear magnetic resonance spectroscopy

Copolymers of N‐vinyl‐2‐pyrrolidone (V) and glycidyl methacrylate (G) monomers of different compositions were prepared by free‐radical solution polymerization. The copolymer composition of these copolymers was determined with ¹H‐NMR spectra. The reactivity ratios calculated from the Kelen–Tudos and nonlinear least‐square error‐in‐variable methods were r_V = 0.03 ± 0.01 and r_G = 5.05 ± 0.84 and r_V = 0.02 and r_G = 4.72, respectively. The triad sequence distribution in terms of V and G centered triads was determined from ¹³C{¹H}‐NMR spectroscopy. The complete spectral assignment of ¹³C{¹H}‐ and ¹H‐NMR spectra was performed with the help of distortionless enhancement by polarization transfer and two‐dimensional ¹³C–¹H heteronuclear single quantum coherence. The ¹H–¹H couplings were explained with total correlation spectroscopy and nuclear Overhauser enhancement spectroscopy spectra. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 50–60, 2002; DOI 10.1002/app.10186     

Stereochemical assignments of the nuclear magnetic resonance spectra of isobornyl acrylate/methacrylonitrile copolymers

Isobornyl acrylate (B)/methacrylonitrile (N) copolymers with different compositions were synthesized by the free‐radical bulk polymerization with azobisisobutyronitrile as the initiator under a nitrogen atmosphere at 70°C. The copolymer compositions were calculated from quantitative ¹³C(¹H)NMR spectra. The reactivity ratios of the comonomers in the B/N copolymers determined from the linear Kelen–Tudos method and nonlinear error‐in‐variable method were r_B = 0.66 ± 0.11 and r_N = 1.54 ± 0.22 and r_B = 0.74 and r_N = 1.65, respectively. The complete spectral assignments of the ¹H‐NMR and ¹³C(¹H)‐NMR spectra were carried out with the help of distortionless enhancement by polarization transfer, two‐dimensional (2D) heteronuclear single quantum coherence, and 2D total correlation spectroscopy. The nitrile carbon of the N unit and the methine and OCH carbons of the B unit were assigned to triad compositional sequences, whereas the β‐methylene carbons of the B and N units were assigned to the tetrad compositional and configurational sequences. The α‐methyl carbon of the N unit was also assigned to the triad level of configurational and compositional sequences. Similarly, the nitrile and quaternary carbon resonances with the methine, methylene, and methyl protons were studied in detail with 2D heteronuclear multiple‐bond correlation spectra. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Microstructure of vinylidene chloride-ethyl acrylate copolymers by one- and two-dimensional NMR spectroscopy

Vinylidene chloride/ethyl acrylate (V/E) copolymers were prepared by photopolymerization using uranyl ion as a photosensitizer at room temperature. Copolymers were characterized by chlorine estimation, gel permeation chromatography, ¹H- and ¹³C-NMR, 2D heteronuclear single quantum correlation (HSQC), and homonuclear 1H–2D double quantum filter correlation spectroscopy (DQF-COSY). Reactivity ratios for the copolymerization of V with E were calculated using the Kelen-Tudos (KT) and the nonlinear error in variables (EVM) methods. The reactivity ratios obtained from the EVM methods are r_V = 0.80 ± 0.15 and r_E = 0.87 ± 0.04. The microstructure was calculated in terms of the distribution of V- and E-centered triad sequences from ¹³C{¹H}-NMR spectra of the copolymers. 2D HSQC was used to analyze the complex ¹H-NMR spectrum and 2D COSY shows the various bond interactions, thus inferring the possible structure of the copolymers. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 67: 417–426, 1998     

One- and two-dimensional nuclear magnetic resonance studies on the compositional sequence and the microstructure of acrylonitrile–pentyl methacrylate copolymers

The chemical microstructure of acrylonitrile–pentyl methacrylate (A–P) copolymers prepared by photopolymerization using uranyl ion as the photo sensitizer is analyzed by ¹³C{¹H} nuclear magnetic resonance spectroscopy. The composition of the copolymers were determined by elemental analysis, and comonomer reactivity ratios were determined by the Kelen–Tudos (KT) and the error in variable (EVM) methods. The terminal model reactivity ratios obtained from the EVM method are r_A = 0.20 and r_P = 2.62. The complete spectral assignment of the overlapping proton and carbon spectra of these copolymers were done with the help of distortionless enhancement by polarization transfer and two-dimensional ¹H–¹³C heteronuclear shift correlation (inverse HETCOR) spectroscopy. The assignment of the various conformational and configurational sequences in the proton spectrum were made possible by two-dimensional correlated spectroscopy and total correlation spectroscopy experiments. Monte Carlo simulation was used to study the effect of the degree of polymerization on the triad fractions. © 1998 John Wiley & Sons, Inc. J Appl Polm Sci 69: 2507–2516, 1998     

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     

Atom transfer radical homo‐ and copolymerization of styrene and methyl acrylate initiated with trichloromethyl‐ terminated poly(vinyl acetate) macroinitiator: A kinetic study

Atom transfer radical bulk copolymerization of styrene (St) and methyl acrylate (MA) initiated with trichloromethyl‐terminated poly(vinyl acetate) macroinitiator was performed in the presence of CuCl/PMDETA as a catalyst system at 90°C. Linear dependence of ln[M]₀/[M] versus time data along with narrow polydispersity of molecular weight distribution revealed that all the homo‐ and copolymerization reactions proceed according to the controlled/living characteristic. To obtain more reliable monomer reactivity ratios, the cumulative average copolymer composition at moderate to high conversion was determined by ¹H‐NMR spectroscopy. Reactivity ratios of St and MA were calculated by the extended Kelen‐Tudos (KT) and Mao‐Huglin (MH) methods to be r_St = 1.018 ± 0.060, r_MA = 0.177 ± 0.025 and r_St = 1.016 ± 0.053, r_MA = 0.179 ± 0.023, respectively, which are in a good agreement with those reported for the conventional free‐radical copolymerization of St and MA. Good agreement between the theoretical and experimental composition drifts in the comonomer mixture and copolymer as a function of the overall monomer conversion were observed, indicating that the reactivity ratios calculated by copolymer composition at the moderate to high conversion are accurate. Instantaneous copolymer composition curve and number‐average sequence length of comonomers in the copolymer indicated that the copolymerization system tends to produce a random copolymer. However, MA‐centered triad distribution results indicate that the spontaneous gradient copolymers can also be obtained when the mole fraction of MA in the initial comonomer mixture is high enough. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Atom transfer radical copolymerization of glycidyl methacrylate and methyl methacrylate

Glycidyl methacrylate (GMA) and methyl methacrylate (MMA) copolymers were synthesized by atom transfer radical polymerization (ATRP). The effect of different molar fractions of GMA, ranging from 0.28 to 1.0, on the polymer polydispersity index (weight‐average molecular weight/number‐average molecular weight) as the indicator of a controlled process was investigated at 70°C, with ethyl 2‐bromoisobutyrate as an initiator and 4,4′‐dinonyl‐2,2′‐bipyridyne (dNbpy)/CuBr as a catalyst system in anisole. The monomer reactivity ratios (r values) were obtained by the application of the conventional linearization Fineman–Ross method (r_GMA = 1.24 ± 0.02 and r_MMA = 0.85 ± 0.03) and by the Mayo–Lewis method (r_GMA = 1.19 ± 0.04 and r_MMA = 0.86 ± 0.03). The molecular weights and polydispersities of the copolymers exhibited a linear increase with GMA content. The copolymer compositions were determined by ¹H‐NMR and showed a domination of syndiotactic structures. The glass‐transition temperatures (T_g) of the copolymers analyzed by differential scanning calorimetry (DSC) decreased in the range 105–65°C with increasing GMA units. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

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     

Microstructure determination and thermal studies of n‐acryloylcarbazole/vinyl acetate copolymers

Copolymers of N‐acryloylcarbazole (A) and vinyl acetate (V) were synthesized by bulk polymerization using benzoyl peroxide (BPO) as free‐radical initiator at 65°C in different in‐feed ratios. The composition of the copolymer was determined by ¹H‐NMR spectrum. The comonomer reactivity ratios, determined by Kelen–Tudos (KT) and nonlinear error‐in‐variables (EVM) methods, were r_A= 16.75 ± 1.38, r_V = 0.015 ± 0.002, and r_A = 16.36, r_V = 0.015, 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) and total correlation spectroscopy (TOCSY). The methine and methylene carbon resonances were found to be compositional as well as configurational sensitive. The signals obtained were broad pertaining to the restricted rotation of bulky carbazole group. The thermal stability and glass‐transition temperatures (T_g) of the copolymers were found to be dependant on polymer composition and characteristic of rotational rigidity of the polymer chain. Variation in the values of T_g with the copolymer composition was found to be in good agreement with theoretical values obtained from Johnston and Barton equations. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 2720–2733, 2007     

Microstructure analysis of methyl acrylate/methyl methacrylate copolymers by two‐dimensional NMR spectroscopy

Methyl acrylate (A)/methyl methacrylate (B) copolymers of different compositions were synthesized in bulk at 50°C and the compositions were determined from ¹H NMR spectra. Reactivity ratios were optimized using the least square methodology. Compositional and configurational assignments were done using two‐dimensional (2D) Heteronuclear Single Quantum Correlation (HSQC) and Total Correlation Spectroscopy (TOCSY) experiments. Methylene proton and carbon resonances were assigned for compositional and configurational sensitivity at tetrad level. Carbon resonances of methine group of methyl acrylate were assigned for compositional sensitivity up to triad level with the help of 2D HSQC spectra. α‐Methyl group of methyl methacrylate was assigned up to triad level of compositional and configurational placements for carbon and proton resonances by 2D HSQC spectroscopy. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 1437–1445, 2006     

Investigation of microstructure of 4‐vinyl pyridine–methacylonitrile copolymers by NMR spectroscopy

4‐Vinyl pyridine–methacrylonitrile (V/M) copolymers of different composition were prepared by bulk polymerization using benzoyl peroxide as an initiator. The copolymer composition was determined from quantitative ¹³C{¹H}‐NMR spectra. The reactivity ratios for V/M copolymer obtained from a linear Kelen‐Tudos method (KT) and nonlinear error‐in‐variables method (EVM) are r_V = 0.79 ± 0.12, r_M = 0.38 ± 0.09 and r_V = 0.79 ± 0.13, r_M = 0.38 ± 0.07, respectively. The complete spectral assignment in term of compositional and configurational sequences of these copolymers were done with the help of distortionless enhancement by polarization transfer (DEPT), two‐dimensional heteronuclear single quantum coherence spectroscopy (HSQC). Total correlated spectroscopy (TOCSY) experiment was used to assign the various three‐bond ¹H‐¹H couplings in the V/M copolymer. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 3232–3238, 2003     

Microstructure determination of the acrylonitrile–styrene–methyl methacrylate terpolymers by NMR spectroscopy

Acrylonitrile–styrene–methyl methacrylate (A–S–M) terpolymers were prepared by photopolymerization using uranyl nitrate ions as photo initiators, which were analyzed by NMR spectroscopy. The terpolymer compositions were determined by Goldfinger's equation using comonomer reactivity ratios: r_as = 0.04; r_sa = 0.31; r_am = 0.17, r_ma = 1.45; r_sm = 0.52; r_ms = 0.47. The terpolymer compositions were also determined from the quantitative ¹³C(¹H)‐NMR spectroscopy. The sequence distribution of the acrylonitrile‐, styrene‐, and methyl methacrylate–centered triads were determined from the ¹³C(¹H)‐NMR spectra of the terpolymers and are in good agreement with triad concentrations calculated from the statistical model. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 3026–3032, 1999     

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

A novel acrylic monomer, 4-cyanophenyl acrylate (CPA) was synthesized by reacting 4-cyanophenol dissolved in methyl ethyl ketone with acryloyl chloride in the presence of triethylamine as a catalyst. Copolymers of CPA with methyl methacrylate (MMA) at different composition was prepared by free radical solution polymerization at 70 ± 1 °C using benzoyl peroxide as an initiator. The copolymers were characterized by FT-IR, ¹H-NMR and ¹³C-NMR spectroscopic techniques. The solubility tests were checked in various polar and non polar solvents. The molecular weight and polydispersity indices of the copolymers were estimated by using gel permeation chromatography. The glass transition temperature of the copolymers increases with increases MMA content. The thermal stability of the copolymer increases with increases in mole fraction of CPA content in the copolymer. The copolymer composition was determined by using ¹H-NMR spectra. The monomer reactivity ratios determined by the application of linearization methods such Fineman–Ross (r ₁ = 0.535, r ₂ = 0. 0.632), Kelen–Tudos (r ₁ = 0.422, r ₂ = 0.665) and extended Kelen–Tudos methods (r ₁ = 0.506, r ₂ = 0. 0.695).     

Compositional and configurational sequence determination of methacrylonitrile–vinylidene chloride copolymers by nuclear magnetic resonance spectroscopy

Methacrylonitrile–vinylidene chloride (M/V) copolymers of different composition were prepared by bulk polymerization using benzoyl peroxide as an initiator under nitrogen atmosphere in a sealed tube. The copolymer composition was determined from quantitative ¹³C[¹H] NMR spectra. The reactivity ratios for M/V copolymers obtained from a linear Kelen–Tudos method and nonlinear error‐in‐variables method are r_M = 2.47 ± 0.14, r_V = 0.40 ± 0.02, and r_M = 2.43, r_V = 0.39, respectively. The complete spectral assignment in term of compositional and conformational sequences of these copolymers were done with the help of distortionless enhancement by polarization transfer, two‐dimensional heteronuclear single‐quantum coherence spectroscopy. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 1865–1874, 2005     

Copolymerization of N‐aryl substituted itaconimide with methyl methacrylate: Effect of substituents on monomer reactivity ratio and thermal behavior

The article describes the synthesis and characterization of N‐(4‐methoxy‐3‐chlorophenyl) itaconimide (MCPI) and N‐(2‐methoxy‐5‐chlorophenyl) itaconimide (OMCPI) obtained by reacting itaconic anhydride with 4‐methoxy‐3‐chloroanisidine and 2‐methoxy‐5‐chloroanisidine, respectively. Structural and thermal characterization of MCPI and OMCPI monomers was done by using ¹H NMR, FTIR, and differential scanning calorimetry (DSC). Copolymerization of MCPI or OMCPI with methyl methacrylate (MMA) in solution was carried out at 60°C using AIBN as an initiator and THF as solvent. Feed compositions having varying mole fractions of MCPI and OMCPI ranging from 0.1 to 0.5 were taken to prepare copolymers. Copolymerizations were terminated at low percentage conversion. Structural characterization of copolymers was done by FTIR, ¹H NMR, and elemental analysis and percent nitrogen content was used to calculate the copolymer composition. The monomer reactivity ratios for MMA–MCPI copolymers were found to be r₁ (MMA) = 0.32 ± 0.03 and r₂ (MCPI) = 1.54 ± 0.05 and that for MMA–OMCPI copolymers were r₁ (MMA) = 0.15 ± 0.02 and r₂ (OMCPI) = 1.23 ± 0.18. The intrinsic viscosity [η] of the copolymers decreased with increasing mole fraction of MCPI/or OMCPI. The glass transition temperature as determined from DSC scans was found to increase with increasing amounts of OMPCI in copolymers. A significant improvement in the char yield as determined by thermogravimetry was observed upon copolymerization. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 2391–2398, 2006