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     

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     

Microstructure analysis of N‐vinyl‐2‐pyrrolidone/vinyl acetate copolymers by NMR spectroscopy

N‐Vinyl‐2‐pyrrolidone (V) and vinyl acetate (A) copolymers of different compositions were synthesized by free radical bulk polymerization. The copolymer composition of these copolymers was determined using quantitative ¹³C{¹H} NMR spectra. The reactivity ratios for these comonomers were determined using the Kelen–Tudos (KT) and non‐linear least‐square error‐in‐variable (EVM) methods. The reactivity ratios calculated from the KT and EVM methods are r_V = 2.86 ± 0.16, r_A = 0.36 ± 0.09 and r_V = 2.56, r_A = 0.33, respectively. ¹H, ¹³C{¹H} and ¹H–¹³C heteronuclear shift correlation spectroscopy (HSQC) and ¹H–¹H homonuclear total correlation spectroscopy (TOCSY) were used for the compositional and configurational assignments of V/A copolymers. The ¹³C distortionless enhancement by polarization transfer (DEPT) technique was used to resolve the methine, methylene and methyl resonance signals in the V/A copolymers. © 2002 Society of Chemical Industry     

NMR studies of poly(2-hydroxy ethyl methacrylate-co-2-vinyl pyridine)

Copolymers of 2-hydroxy ethyl methacrylate-2-vinyl pyridine (H/V) of different composition were synthesized by free radical bulk polymerization using azobisisobutyronitrile (AIBN) as an initiator under nitrogen atmosphere. The copolymer compositions were calculated from ¹H NMR spectra. The reactivity ratios for H/V copolymers obtained from a linear Kelen-Tudos method (KT) and nonlinear error-in-variables method (EVM) are r_H = 0.50 ± 0.10, r_V = 1.04 ± 0.08 and r_H = 0.55, r_V = 1.06 respectively. The complete spectral assignment of methine, methylene, methyl, carbonyl, and aromatic carbon regions in term of compositional and configurational sequences of H/V copolymers were done with the help of ¹³C{¹H} NMR, distortionless enhancement by polarization transfer (DEPT), two-dimensional heteronuclear single quantum coherence (HSQC) along with total correlated spectroscopy (TOCSY). © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

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     

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     

Synthesis and characterization of well‐defined random and block copolymers of ε‐caprolactone with l‐lactide as an additive for toughening polylactide: Influence of the molecular architecture

Well‐defined multiarmed star random and block copolymers of ε‐caprolactone with l ‐lactide with controlled molecular weights, low polydispersities, and precise numbers of arms were synthesized by the ring‐opening polymerization of respective cyclic ester monomers. The polymers were characterized by ¹H‐NMR and ¹³C‐NMR to determine their chemical composition, molecular structure, degree of randomness, and proof of block copolymer formation. Gel permeation chromatography was used to establish the degree of branching. Star‐branched random copolymers exhibited lower glass‐transition temperatures (T_g's) compared to a linear random copolymer. When the star random copolymers were melt‐blended with poly(l ‐lactic acid) (PLA), we observed that the elongation of the blend increased with the number of arms of the copolymer. Six‐armed block copolymers, which exhibited higher T_g's, caused the maximum improvement in elongation. In all cases, improvements in the elongation were achieved with no loss of stiffness in the PLA blends. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43267.     

Synthesis,characterization, reactivity ratios by nuclear magnetic resonance spectroscopy,and application of (2,5‐Dichlorophenyl acrylate‐co‐glycidyl methacrylate) polymers as adhesives for the leather industry

2,5‐ Dichlorophenyl acrylate (DPA)‐co‐glycidyl methacrylate (GMA) polymers having five different compositions were synthesized in 1,4‐dioxane using benzoyl peroxide as a free‐radical initiator at 70 ± 0.5°C. Using ¹H‐NMR spectroscopy, the composition of the two monomers in the copolymers was calculated by comparing the integral values of the aromatic and aliphatic proton peaks. The reactivity ratios were calculated by Fineman–Ross (r₁ = 0.31 and r₂ = 1.08), Kelen–Tudos (r₁ = 0.40 and r₂ = 1.15), and extended Kelen–Tudos (r₁ = 0.39 and r₂ = 1.16) methods. The nonlinear error‐in‐variables model was used to compare the reactivity ratios. The copolymers were characterized by ¹H and proton decoupled ¹³C‐NMR spectroscopes. Gel permeation chromatography was performed for estimating the M_w and M_n and M_w/M_n of the poly(DPA) and copolymers (DPA‐co‐GMA: 09 : 91 and 50 : 50). Thermal stability of the homo‐ and copolymers was estimated using TGA [poly(DPA) > DPA‐co‐GMA (50 : 50) > DPA‐co‐GMA (09:91)], while DSC was utilized for determining the glass transition temperature. T_g increased with increased DPA content in the copolymer. The 50 : 50 mol % copolymer was chosen for curing with diethanolamine in chloroform. The cured resins were tested for the adhesive properties on leather at different temperatures (50, 90, 100, and 110°C). The resin cured at 50 °C exhibited a maximum peel strength of 1.6 N/mm, revealing a good adhesive behavior. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 1167–1174, 2006     

Binary copolymerization of 4‐methyl‐1,3‐pentadiene with styrene,butadiene and isoprene catalysed by a titanium [OSSO]‐type catalyst

Binary copolymerization of 4‐methyl‐1,3‐pentadiene (4MPD) with styrene, butadiene and isoprene promoted by the titanium complex dichloro{1,4‐dithiabutanediyl‐2,2′‐bis[4,6‐bis(2‐phenyl‐2‐propyl)phenoxy]}titanium activated by methylaluminoxane is reported. All the copolymers are obtained in a wide range of composition and the molecular weight distributions obtained from gel permeation chromatographic analysis of the copolymers are coherent with the materials being copolymeric in nature. The copolymer microstructure was fully elucidated by means of ¹H NMR and ¹³C NMR spectroscopy. Differential scanning calorimetry shows an increase of glass transition temperature (T_g) with the amount of 4MPD in the copolymers with butadiene and isoprene, while in the copolymers with styrene T_g is increased on increasing the amount of styrene. © 2016 Society of Chemical Industry     

Metal ion interaction of water‐soluble copolymers containing carboxylic acid groups in aqueous phase by membrane filtration technique

This article reports the synthesis of poly(N‐maleoylglycine‐co‐itaconic acid) by radical copolymerization under different feed mole ratios and its properties to remove various metal ions, such as Cu(II), Cr(III), Co(II), Zn(II), Ni(II), Pb(II), Cd(II), and Fe(III), in aqueous phase with the liquid‐phase polymer‐based retention(LPR) technique. The interactions of inorganic ions with the hydrophilic water‐soluble polymer were determined as a function of pH and filtration factor. Metal ion retention was found to strongly depend on the pH. Metal ion retention increased as pH and MG content units in the macromolecular backbone increased. The copolymers were characterized by elemental analysis, FTIR, ¹H‐NMR, and ¹³C‐NMR spectroscopy. Additionally, intrinsic viscosity, molecular weight, and polydispersity have been determined for the copolymers. Copolymer and polymer–metal complex thermal behavior was studied using differential scanning calorimetry (DSC) and thermogravimetry (TG) techniques under nitrogen atmosphere. The thermal decomposition temperatures (TDT) were influenced by the copolymer composition. The copolymers present lower TDT than the polymer–metal complex with the same copolymer composition. All copolymers present a single T_g, indicating the formation of random copolymers. A slight deviation of the T_g for the copolymers and its complexes can be observed. The copolymer T_g is higher than the T_g value for the polymer–metal complexes. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

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     

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     

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     

Synthesis,characterization, and reactivity ratios of copolymers derived from 4‐nitrophenyl acrylate and n‐butyl methacrylate

Free‐radical copolymerization of 4‐nitrophenyl acrylate (NPA) with n‐butyl methacrylate (BMA) was carried out using benzoyl peroxide as an initiator. Seven different mole ratios of NPA and BMA were chosen for this study. The copolymers were characterized by IR, ¹H‐NMR, and ¹³C‐NMR spectral studies. The molecular weights of the copolymers were determined by gel permeation chromatography and the weight‐average (M _w) and the number‐average (M _n) molecular weights of these systems lie in the range of 4.3–5.3 × 10⁴ and 2.6–3.0 × 10⁴, respectively. The reactivity ratios of the monomers in the copolymer were evaluated by Fineman–Ross, Kelen–Tudos, and extended Kelen–Tudos methods. The product of r₁, r₂ lies in the range of 0.734–0.800, which suggests a random arrangement of monomers in the copolymer chain. Thermal decomposition of the polymers occurred in two stages in the temperature range of 165–505°C and the glass transition temperature (T_g) of one of the systems was 97.2°C. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 1817–1824, 2003     

Random copolymerization of 2,2‐dimethyltri methylene carbonate and ε‐caprolactone using a rare‐earth tris(4‐tert‐butylphenolate)s as a single‐component initiator

Highly random copolymers of 2,2‐dimethyltrimethylene carbonate (DTC) and ε‐caprolactone (CL) were synthesized by single component rare‐earth tris(4‐tert‐butylphenolate)s [Ln(OTBP)₃] for the first time. The influences of reaction conditions on the copolymerization initiated by La(OTBP)₃ have been examined in detail. The monomer reactivity ratios of DTC and CL determined by the Fineman–Ross method are 4.0 for r_DTC and 0.27 for r_CL. The microstructure of the copolymer was determined by the analyses of the diads DTC–DTC, DTC–CL, CL–DTC and CL–CL of the ¹H NMR spectra. The high degree of randomness of the chain structure was further confirmed by the ¹³C NMR spectra and differential scanning calorimetry. The thermal properties of the copolymers as a function of composition are reported. The mechanism investigated by ¹H NMR data indicates that the rare‐earth tris(4‐tert‐butylphenolate)s initiate the ring‐opening copolymerization of DTC and CL with acyl‐oxygen bond cleavages of the monomers. Copyright © 2004 Society of Chemical Industry     

Preparation and characterization of acrylonitrile‐ethyl methacrylate copolymers and the effect of LiClO4 salt on electrical properties of copolymer films

Copolymers of poly(acrylonitrile‐co‐ethyl methacrylate), P(AN‐EMA), with three different EMA content and parent homopolymers were synthesized by emulsion polymerization. The chemical composition of copolymers were identified by FTIR, ¹H‐NMR and ¹³C‐NMR spectroscopy. The thermal properties of copolymers were modified by changing the EMA content in copolymer compositions. Various amounts of LiClO₄ salt loaded (PAN‐co‐PEMA) copolymer films were prepared by solution casting. The dielectric properties of these films at different temperatures and frequencies were investigated. It was found that the dielectric constant and ac‐conductivity of copolymer films were strongly influenced by the salt amounts and EMA content in copolymers. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Novel network polymer electrolytes containing fluorine and sulfonic acid lithium prepared by ultraviolet polymerization

Poly(vinyl alcohol) (PVAL) and vinyl acetate‐vinyl alcohol copolymers (VAVAL) were esterified with 3,5‐dinitrobenzoyl chloride using the cycled urea N,N′‐dimethylpropyleneurea (1,3‐dimethyl‐3,4,5,6‐tetrahydro‐2(1H)‐pyrimidinone) (DMPU) as the solvent. Vinyl alcohol‐vinyl‐3,5‐dinitrobenzoate copolymers (VALVDNB) and vinyl acetate‐vinyl‐3,5‐dinitrobenzoate copolymers (VAVDNB) were obtained. High degrees of esterification were obtained when PVAL was esterified (86%). The degree of transformation was determined by ¹H‐NMR as well as by chemical analysis, and the structure of the resulting polymers by means of IR spectroscopy and ¹H‐ and ¹³C‐NMR. The microstructure of PVA, PVAL, VAVAL copolymers and VALVDNB copolymers were determined from ¹H‐ and ¹³C‐NMR techniques. The sequence distributions for VAVAL copolymers prepared by base‐catalyzed transesterification of PVA were blocky, while the distributions were close to random for VALVDNB copolymers obtained by esterification of PVAL. Thermal properties were studied by DSC. The T_g values of VAVAL, VALVDNB, and VAVDNB copolymers as a function of copolymer compositions were determined. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Copolymerization of methyl methacrylate with 4‐vinylpyridine initiated by a novel Ni(II)α‐Benzoinoxime complex

Copolymerizations of methyl methacrylate (MMA) with 4‐vinylpyridine (4VP) were performed from different monomer feed ratios in 1,4‐dioxan at 30°C under free radical initiation experimental conditions, using Ni(II)α‐Benzoinoxime complex as initiator. The obtained copolymers (PMMA4VP) were examined by FTIR and ¹H NMR spectroscopies. The composition of these copolymers was calculated, using ¹H NMR spectra and elemental analysis. Monomer reactivity ratios were estimated from Fineman–Ross (FR, r_m = 0.550, r_v = 1.165) and Kelen–Tudos (KT, r_m = 0.559, r_v = 1.286) linearization methods, as well as nonlinear error in variables model (EVM) method using the RREVM computer program (RREVM, r_m = 0.559, r_v = 1.264). These values suggest that MMA‐4VP pair copolymerizes randomly. ¹H NMR spectra provide information about the stereochemistry of the copolymers in terms of sequence distributions and configurations. These results showed that the age of the Ni complex has an impact not only on its activity towards polymerization reactions but also on the features of the corresponding copolymers, whereas the chemical composition was insensitive to this prominent factor. The mechanism of MMA‐4VP copolymerization is consistent with a radical process as supported by microstructure and molecular weight distribution studies. Thermal behaviours of these copolymers were investigated by differential scanning calorimetry and thermogravimetric analysis. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2008     

Tailoring the swelling and glass‐transition temperature of acrylonitrile/hydroxyethyl acrylate copolymers

Novel polyacrylonitrile (PAN)‐co‐poly(hydroxyethyl acrylate) (PHEA) copolymers at three different compositions (8, 12, and 16 mol % PHEA) and their homopolymers were synthesized systematically by emulsion polymerization. Their chemical structures and compositions were elucidated by Fourier transform infrared, ¹H‐NMR, and ¹³C‐NMR spectroscopy. Intrinsic viscosity measurements revealed that the molecular weights of the copolymers were quite enough to form ductile films. The influence of the molar fraction of hydroxyethyl acrylate on the glass‐transition temperature (T_g) and mechanical properties was demonstrated by differential scanning calorimetry and tensile test results, respectively. Additionally, thermogravimetric analysis of copolymers was performed to investigate the degradation mechanism. The swelling behaviors and densities of the free‐standing copolymer films were also evaluated. This study showed that one can tailor the hydrogel properties, mechanical properties, and T_g's of copolymers by changing the monomer feed ratios. On the basis of our findings, PAN‐co‐PHEA copolymer films could be useful for various biomaterial applications requiring good mechanical properties, such as ophthalmic and tissue engineering and also drug and hormone delivery. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Dielectric properties of lithium‐perchlorate‐filled acrylonitrile–hexyl methacrylate copolymer films

A series of poly(acrylonitrile‐co‐hexyl methacrylate), PAN‐co‐PHMA, copolymers with various hexyl methacrylate (HMA) contents were synthesized by emulsion technique. The incorporation of HMA units into the copolymers was confirmed by Fourier transform infrared and proton nuclear magnetic resonance (¹H‐NMR) spectroscopy. Glass transition temperatures (T _g) and thermal decomposition temperatures of copolymers were determined by differential scanning calorimetry and thermogravimetric analysis. The T _g of copolymers were lowered monotonically by increasing HMA content, while thermal stabilities of copolymers were enhanced. The frequency dependence of dielectric properties of three different amounts of LiClO₄ salt doped copolymer films was investigated. The influence of molar fraction of HMA on dielectric constant and ac‐conductivity of copolymer films was examined. Samples with higher HMA contents showed better stability and conductivity, as a result of increase in free volume and the mobility of the dipoles. The ac conductivity of copolymers was also improved by increasing LiClO₄ salt which was due to the existence of more charge carriers. PAN(88)‐co‐PHMA(12) copolymer with 1.5 mol% of lithium salt exhibited ionic conductivity of the 7.8 × 10⁻⁴ S/cm at 298 K. POLYM. COMPOS., 38:1792–1799, 2017. © 2015 Society of Plastics Engineers