A Facile Synthesis of Poly(Acrylanilide-Co-Acrylic Acid)
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Asian Journal of Chemistry; Vol. 25, No. 6 (2013), 3247-3251 http://dx.doi.org/10.14233/ajchem.2013.13608 A Facile Synthesis of Poly(acrylanilide-co-acrylic Acid) * XIAOMING ZHOU, BINGTAO TANG and SHUFEN ZHANG State Key Laboratory of Fine Chemicals, Dalian University of Technology, Dalian 116023, P.R. China *Corresponding author: Fax: +86 411 84986264; Tel: +86 411 84986265; E-mail: [email protected]; [email protected] (Received: 16 February 2012; Accepted: 14 December 2012) AJC-12558 A range of poly(acrylanilide-co-acrylic acid) was synthesized through a facile one-pot condensation of poly(acrylic acid) with aromatic amines. Thionyl chloride was added in a stepwise manner to N,N-dimethyl acetamide and poly(acryloyl chloride) need not be isolated during the reaction. Compared with conventional methods, the condensation of poly(acryloyl chloride) with aromatic amines could perform without the addition of other bases (such as triethylamine, pyridine, etc.). Regardless of electron-withdrawing or electron- donating groups the aromatic amines contain, the reaction was carried out smoothly. Different molar ratios of poly(acrylic acid) (acrylic acid units) to aromatic amines were investigated and moderate yields were obtained. The products were characterized by nuclear magnetic resonance spectroscopy and Fourier-transform infrared spectroscopy. Key Words: One-pot synthesis, Poly(acrylanilide-co-acrylic acid), Thionyl chloride. INTRODUCTION Recently, a synthesis of acrylanilides and anilides directly from acrylic acid and other organic acids using thionyl chloride In recent years, the aromatic amide derivatives of which is a commonly available reagent at a relatively low cost poly(acrylic acid) (PAAc) and poly(methacrylic acid) (PMAc) was investigated and a high conversion was achieved18. To our have been paid much attention because of their ease of best of knowledge, there was no report about synthesis of functionalization and processing, good performance, excellent PAAn-co-AAc directly from poly(acrylic acid) using thionyl 1 physical and chemical stability . They show potential appli- chloride. Encouraged by the formation of acryanilides using 2-7 cations in biosensors and biomedical fields , drug delivery thionyl chloride in N,N-dimethyl acetamide (DMAC) at 8,9 10-13 systems , detection and analytical chemistry fields and ambient temperature and also by the ability of N,N-dimethyl 14-16 optical materials . These poly(methacrylamides) and acetamide to dissolve both poly(acrylic acid) and aromatic poly(acrylamides) with various functional groups could be amines, it is expected that the synthesis of PAAn-co-AAc could prepared by polymerization of monomers. However, it was be achieved via a direct condensation of poly(acrylic acid) frequently failed to attempt free radical polymerization or and aromatic amines without using reactive acryloyl chloride anionic polymerization of acrylanilides or methacrylanilides and poly(acryloyl chloride), so we extended this approach monomers, only low molecular weight oligomers were towards the synthesis of PAAn-co-AAc (Scheme-I). obtained and the yields were quite low, due to the influences of steric hindrance and inhibition groups (e.g., nitro groups)14,15. EXPERIMENTAL Therefore, there is a need to develop new strategies for synthe- Acrylic acid, thionyl chloride, petroleum ether (boiling sizing poly(acrylanilide-co-acrylic acid) (PAAn-co-AAc) range 90-120 ºC) and analytical grade N,N-dimethyl acetamide polymers. Additional approaches for the synthesis of PAAn- were obtained from Tianjin Bodi Chemical Holding Co. Ltd. co-AAc via the reaction of poly(methacryloyl chloride) or Azo-bis-isobutyronitrile (AIBN) was purchased from Tianjin poly(acryloyl chloride) with aromatic amines have been Guangfu Fine Research Institute and was recrystallized from applied in some reports14,15,17. However, due to that methacryloyl ethanol before use. Isopropanol was obtained from Tianjin chloride, acryloyl chloride, poly(methacryloyl chloride) and Fuyu Fine Co., Ltd. 4-Nitroaniline was from Shanghai Kefeng poly(acryloyl chloride) are extremely moisture sensitive and Chemical Reagents Co. Ltd. and p-methoxyaniline was from readily hydrolyzed, they have to be strictly dealt with. It would Shanghai Auxiliaries Factory. 3-(N,N-Diethylamino)aniline be more satisfactory if PAAn-co-AAc could be synthesized in was obtained from the hydrolysis of N-(3-N,N-diethylamino- a one-pot condensation directly from poly(acrylic acid) without phenyl) acetamide according to literature19. Before use, N,N- the use of reactive acryloyl chloride or poly(acryloyl chloride). dimethyl acetamide was dried using 4 Å molecular sieves. 3248 Zhou et al. Asian J. Chem. NH2 i ii H H2 H H2 H H2 + C C C C C C R1 n x y R C C 2 O NH O OH O OH R1 R2 1 2 3 a R1=H R2=H b R1=H R2=NO2 c R1=H R2=OCH3 d R1=N(CH2CH3)2 R2=H Scheme-I: Synthesis of P(AAn-AAc) 3a-d. i, N,N-dimethyl acetamide, -5 ºC, SOCl2; ii, aromatic amine, 20-70 ºC 4-Nitroaniline and p-methoxaniline were recrystallized from A range of PAAn-co-AAc was synthesized and the reac- ethyl acetate and toluene mixture (1:2, v/v). All other reagents tions were carried out under the same procedure as described were used as commercially received except indicated. above, except that different molar ratios of poly(acrylic acid) Synthesis of poly(acrylic acid): Poly(acrylic acid) was and the aromatic amine to thionyl chloride were used. The prepared by precipitation polymerization in petroleum ether molar ratios of aromatic amine: poly(acrylic acid) (calculated as already reported20-22. In a 250 mL three-neck flask fitted as carboxyl groups): thionyl chloride were 1.0:4.0:4.4, with a reflux condenser, acrylic acid (15 g, 0.208 mol) was 2.0:4.0:4.4, 4.0:4.0:4.4, respectively. The functionalizations added dropwise within 0.5 h to a stirred solution of isopropanol of all samples were defined as the molar ratio of the aromatic (15 g) and azo-bis-isobutyronitrile (1 g) in 100 mL petroleum amine to the carboxyl group of the polymer. ether at 80 ºC. After the addition of acrylic acid, polymerization The reaction solutions of 3a were poured into 200 mL ice was performed with a mechanical stirrer at 80 ºC for 3.5 h. At water. After filtration, the filter cake was washed with water the completion of the reaction, the solvent was removed under until the filtrate was neutral, then vacuum dried at 30 ºC to reduced pressure at 90 ºC/5 mmHg and the products were obtain the crude products. The crudes of 3a were washed with withdrawn from the reactor and dried under vacuum at 50 ºC dichloromethane for several times until no aniline (Rf = 0.53) for 24 h. The average molecular weight (Mw) and the poly- were detected by thin-layer chromatography (TLC n-petro- dispersity index of poly(acrylic acid) were measured by gel leum ether:ethyl acetate = 1/9, v/v) then dried under vacuum at permeation chromatography(GPC) at 25 ºC using deionized 30 ºC. Final cakes of 3c were also obtained in the same way. water as the eluent at a flow rate of 1 mL/min. Narrow disperse The crude products of 3b were similarly obtained with poly(ethylene glycol) was used as calibration standards. the procedure above-mentioned for 3a. The crude products of Molecular weight (Mw) and its distribution of the polymers 3b were dissolved in 20 mL acetone and the solutions were were determined by gel permeation chromatography on an precipitated using 100 mL ethyl ether. The procedure was Agilent 1200 apparatus. And a molecular weight of 84345 repeated 5 times to remove the residual 4-nitroaniline. Then g/mol and a polydispersity index of 1.93 were obtained. the final cakes were dried under vacuum at 30 ºC. General procedure for the preparation of PAAn-co- The reaction solutions of 3d were precipitated into 200 AAc: A solution of poly(acrylic acid) (1.8 g, 0.025 mol acrylic mL acetone and washed extensively with acetone to get the acid units) and dried N,N-dimethyl acetamide (25 mL) was crude products and then vacuum dried at 30 ºC to obtain the cooled to -5 ºC in a 100 mL three-neck flask equipped with crude products. The solution pH was adjusted to 4.5 with a mechanically stirrer and a scrubber containing sodium sodium carbonate after the crudes of 3d were dissolved in hydroxide solution. After the solution was vigorously stirred 30 mL ice water. After filtration, the final cakes were washed under nitrogen atmosphere for 15 min, the desired amount with ice water until no 3-(N,N-diethylamino)aniline was of thionyl chloride was added dropwise over 10 min. The detected by TLC (Rf = 0.87, n-petroleum ether:ethyl acetate = solution was stirred under nitrogen at -5 ºC for another 0.5 h, 1/9, v/v) and then dried under vacuum at 30 ºC. then the solution was warmed up to 20 ºC and kept at this Analytical techniques: The 1H NMR spectra were temperature for 20 min, followed by the addition of aromatic recorded on a VARIAN INOVA (400 MHz) spectrometer using amines in 5 mL N,N-dimethyl acetamide over 15 min. Upon TMS as an internal standard. FT-IR spectra were determined complete addition, the solution was stirred at 20 ºC for 20 min on a Perkin-Elmer 983 infrared spectrometer using KBr pellets. and then at 70 ºC for 14 h. Nitrogen was bubbled throughout Elemental analysis of N, O and H for the polymer samples the process. was performed with a Vario-EL analyzer. The measurement Vol. 25, No. 6 (2013) A Facile Synthesis of Poly(acrylanilide-co-acrylic Acid) 3249 of average molecular weight was carried on Agilent Techno- 1665 1714 logies 1200 series GPC.