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Synthesis and Characterization of Polymer and Polymer Complex with Some Transition Metal Ions
Synthesis and Characterization of Polymer and Polymer Complex with Some Transition Metal Ions
Journal of the Korean Chemical Society. 2010. Feb, 54(1): 43-48
Copyright © 2010, The Korean Chemical Society
  • Received : August 11, 2009
  • Accepted : January 18, 2010
  • Published : February 20, 2010
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About the Authors
S. K. Badr
drsamykh@yahoo.com
T. Y. Mohamed

Abstract
Polyamide derived from azo compound of o-amino phenol coupled with acetyl acetone, maleic anhydride acid and p-phenylene diamine were prepared. The prepared polyamide (PA) was refluxed with metal salts of transition metal ions include, Co +2 , Cr +2 , Ni +2 , Cu +2 , Zn +2 , Cd +2 and Fe +3 in dimethyl formamide (DMF) in different molar ratios. These complexes were characterized and identified by elemental and thermal analysis, IR, 1 H NMR spectra. The data showed that PA ligand coordinates with metal ions in abidentate manner through donating N=N and O-H groups. The metal ions are surrounded by coordinated water molecules and anions to establish the geometrical structure of the complexes. The thermal analysis degradation at different temperatures explained the weight loss of hydrated water and the decompositions of complexes until a constant weight loss of metal oxides is obtained.
Keywords
INTRODUCTION
In recent years much emphasis have been given to the synthesis of polymers containing chromophoric groups. For example, the aromatic azo group which can form a part of the main chain. 1 The aromatic azo group is of special interest because of the existence of cis-trans isomerism and its effect on the photochromic properties of the polymers. 2 - 4 Therefore, polymers that contain the azo group have potential use in a variety of application. 5 - 8 The chelate-forming polymeric ligands have been extensively studied by several authors. 9 , 10 Such ligands are characterized by the presence of reactive functional groups of O, N, S and P in the polymer matrix capable of coordinating to different metal ions. Moyers and Fritz 11 condensed m-phenylenediamine tartaric acid with resorcinol and formaldehyde to get a resin containing two imino-diacetic acid functional groups anchored to benzene ring and used the resin to separate Co(II) from Ni(II) in a gravity flow column.
Schiff bases having multidentate coordination sites are known to form complexes with transition metal ions readily. 12 - 17 Present in a polymeric matrix, they are expected to show affinity and selectivity towards these metal ions at an appropriate pH. This lead us to synthesize a number of phenolic Schiff bases by condensing several aliphatic and aromatic diamines with phenolic carbonyls, or conversely, dicarbonyls with aminophenols. These Schiff bases were found to undergo condensation polymerization readily with formaldehyde and furfuraldehyde. In the reaction conditions set for polycondensation, the C=N bond of the Schiff bases did not undergo hydrolytic cleavage.
The aim of the work to prepare a new chelating copolymers containing azo group units as ligating centers with different molar ratios of metal ions, the formed polymer complexes were examined by using IR, and thermal analysis and also by using the atomic absorption spectrophotometer to determine the metal ion content in the solution of the dissolved polymer complex, from these analysis the stability of complexes were identified.
- Measurements
Reagent grade chemicals were used. Elemental analysis was determined by the analytical unit of Cairo University of Egypt. Atomic absorption spectrophotometry Perkin Elmer A. Analyst 100 was used to determine the metal ion content. IR-spectra and Jasco FT/IR 46 Plus 200 - 4000 cm -1 a Perkin Elmer spectrophotometer (400 - 4000 cm -1 ). Thermal analysis Shimadzu: Thermogravimetric analyzer TGA sec. (DTA) and TGA) was carried out in the temperature rate 10 ℃/min. in the range 27 ℃ - 700 ℃. 1 H NMR spectrum of polyamide was recorded in d 6 -DMSO using TMS as internal standard by avarian Gemini spectra photometer operating at 200 MHz.
All metal-complexes were dried in Vacuo oven at 40 ℃.
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Preparation of acetyl acetone Azodye
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Polyamide Preparation
MATERIAL AND METHODS
Acetyl acetone (BDH chemicals Ltd), sodium nitrite, o-amino phenol (Fluka), maleic anhydride (Oxford Lab. Mumbai), p-phenylene diamine (Fluka), chloride salt of ferric, cadmium, chromium, cobalt, and sulphate of nickel, zinc and lead acetate are in pure grade of national companies as aldrish, sigma and Fluca and are used as it received.
- Experimental
Preparation of Azo dye . A mixture of O-amino phenol (0.02 mol) was dissolved in concentration hydrochloric acid 37% (4.8 mL) then cooled to -5 ℃. Sodium nitrite (1.8 gm, 0.022 mol) was dissolved in 20 mL distilled H 2 O and slowly added with continuous stirring over 15 min (Diazotization and coupling methods according to the general methods). 18 The diazonium salt was coupled with alkaline acetyl acetone (0.02 mol) solution and stirred in ice bath for 6 hrs. The prepared azo dye (Azo Ac) were filtered and washed several times with distilled water and dried in an vacuum oven at 60 ℃ for 4 hrs. and recrystalized from hot ethanol and then precipitated.
Preparation of polyamide. The polyamide was prepared by melt condensation of diamine p-phenylene diamine (0.1 mol) and maleic anhydride (0.05 mol) and a few drops of trimethyl amine as a basic catalysis 19 in step (I) at temperature range 140 - 160 ℃ (3 hrs). In the step (II) azo acetate (0.05 mol) was added and temperature raised gradually 160 - 200 ℃. The reaction was carried in three necked flask dipped in an oil bath (thermally controlled) provided with mechanical stirrer and deen stark trap to collect, the water produced. A pipette was inserted through a stopper down to the flask to introduce a slow stream of dry deoxygenated nitrogen gas in order to facilitate the removal of water produced. When the reaction is completed the polyamide (PA) was dissolved in DMF then precipitate into large amount of petroleum ether 40 - 60 then collected and dried in a vacuum oven at 40 ℃ for about 6 hrs.
Preparation of polyamide metal ion complexes. The polyamide (PA) complexes were synthesized 19 by refluxing a calculating amount of the polyamide (0.01 mol) and (0.01 mol) of lead acetate with (0.01 mol) of different metal ions Fe +3 , Cr +3 , Ni +2 , Cd +2 , Co +2 , Cu +2 , Zn +2 gradually in DMF for about 4 hrs. The solution is then allowed to cool and an excess distilled water acidified with HCl was added where the solid complexes were precipitated, filtered off and dried in a vacuum oven at 40 ℃ for 3 hrs.
- Measurements
- Characterization of polymer.
Determination of acid value (AV): The weighted sample of copolymer is placed in conical flask dissolved in DMF and titrated with (0.05 N) alcoholic KOH using phenolphthaline indicator till the end point and calculate AV according to the equation:
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where: N: The normality of KOH
V: The volume of KOH
Determination of hydroxyl value: 3 gm of sample is placed in Erlenmeyer flask and exactly 20 mL of acetylating mixture (1 volume of acetic anhydride 3 volume of pyridine) were refluxed for 30 min. A blank determination is carried out at the same time. The flask was cooled by cold distilled water (50 mL) and the free acetic acid titrated with 1 N NaOH then the hydroxyl value calculated by the standard methods. 20
Viscosity measurements: The viscosities were determined by Ostwald 21 viscometer at six different concentrations ranged from 0.5 to 3.0% of the copolymer in DMF at 33 ℃. The intrinsic viscosity (η) was calculated using Huggins equation [eq. (1)] 22 and Krammer equation [eq. (2)]. 23
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where C is the concentration (g/100 mL), η rel is the ratio of the viscosity of the solution (η) to the viscosity of the solvent (η o ) (η rel = η / η o ) and η sp is a function derived from η rel. The relative viscosity (η sp = η - η o / η o = η / η o -1 = (η rel )-1]. k 1 and k 2 are constants for a given polymer/solvent temperature system.
RESULTS AND DISCUSSION
- Physical properties of prepared polyamide
The physical properties of the prepared polyamide (PA) and polyamide complex with different metal ions were listed in 1 . The data indicate that the prepared polyamide (PA) yellowish and mean molecular weight (M.wt.) 6647 and degree of polymerization (N) about 13 unit. This mean that the prepared polyamide (PA) have medium molecular weight with repeating unit have functional group used to form chelating polymer with different metal ions with different ratios and repeating unit have degree of conjugation help to form stable polyamide complex. The data also indicate the measurement of density which range between 0.97 - 1.65 gm/cm 3 . From 1 the measurement of hydroxyl value (OH value) of Azo Ac and polyamide (PA) were found to be 23, 68 respectively.
Physical properties of polymer and polymer complex
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aWhere N: Degree of polymerization.
Viscometric measurements were carried out in a DMF at 33 ℃ with Ostwaled viscometer. 21 The reduced viscosity (η rel ) versus the concentration (0.5 - 3.0%) was plotted for the set of data. (η) was determined from corresponding linear plots. Equations (1) and (2) were used to determine the Huggin 22 and Krammer 23 constants, respectively. As η rel is dependent on the concentration of the polymer sample, it is necessary to extrapolate a plot of η rel against the polymer concentration (C) to the zero concentration to get [η], which is characteristic parameter of a polymer. Hence [η] is given in equations (5) and (6) as follows:
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or
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According to this relation, the plots of η SP /C and Ln η rel /C against C were linear with slops of K 1 and K 2 , respectively. The intercept on the viscosity function axis gave the [η] value in both plots. The calculated values of constants k 1 and k 2 satisfy the relation k 1 + k 2 = 0.5 favorably,31 and this indicates that the solvent used or the viscosity measurement was of good quality; [η] for the polyamide were show in 1 . The data of viscosity measurements show relative increase in polymer than monomer which related to the increase of hydrogen bond and also to use of aromatic amine.
- Elemental analysis of the complexes
By dissolving 0.1 gm of the complex in diluted HCl and completed the solution till 50 mL measuring flask by distilled water. The metal content was recorded in 2 . Also, the micro analysis of C, H, N of the complexes were recorded in 3 it was found that the amount of metals which are introduced to forming a complex was in molar ratio 2:1 metal:ligand (M:L) or 1:1:1 (M:L:M), these metals could bonded to the ligand to form a complex and the results indicated the presence of the two metals which are bonded to the center of chelation as shown in 2 .
Also, the results in 3 confirmed the composition of the complex and its molecular formula due to the presence of the two metals coordinated in the center of chelation by the chemical bonds.
IR Spectra. The bonding of the ligand to the metal has been deduced from IR spectra. The characteristic bands of the ligand and metal complexes were presented in 4 . The IR spectra of the ligand shows abroad medium bands in the 3505 - 3200 cm -1 ranges, attributed to intramolecular hydrogen bonding between OH and C=O groups in the same molecule and also NH groups 24 . 1 .
Elemental analysis of complexes by using AAS
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Elemental analysis of complexes by using AAS
C, H, N analysis of the complexes
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C, H, N analysis of the complexes
IR spectra (assignments) of azo PA and its metal complexes
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IR spectra (assignments) of azo PA and its metal complexes
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(a) IR Spectra of PA. (b) IR Spectra of PA (Pb + Fe) Complex.
The bands at 3407 - 3110 and 1605 cm -1 are assigned to secondary ν(NH), νC=O, bands at 1513 and 1326 cm -1 correspond to ν(CH=CH) AL and νC-O respectively. 25
The complexes show broad band from lattice water at 3650 - 3300 for (Pb-Ni) complex. Coordinated water appears at 3960 cm -1 . While for (Pb-Fe) complex coordinated water appears at 3589 cm -1 which for (Pb-Co) complex appeared at 3650 cm -1 .
The complexes show bands between 3060 - 2368, 2927 - 237 and 2927.4 - 2367 cm -1 which are attributed to ν (NH), 4 . Also, bands appeared at 1662, 1655 and 1660 cm -1 assigned to (Pb-Ni)-PA, (Pb-Fe)-PA, (Pb-Co)-PA complexes these bands shows a shift than the bands of the ligand only.
Also, bands appeared at 1602, 1603, 1560 cm -1 for complexes in the same order due to νN=N group, 4 , bands appeared at 1405, 1309 and 1310 for νCH=CH of the complexes, while bands appeared at 668, 758 and 667.2 cm -1 due to frequencies of M-O bond, νO-H groups appeared at the range of 850 - 833 cm -1 , due to bridging H-bonds in the molecule.
The 1 H NMR of ligand PA polymer show bands (3H-CO-CH 3 ) at δ 2.5, 1H (CH-N=N) δ 2.1, 2H (CH 2 -CO) at δ 2.5, 1H (CH-N=N) δ 3.6, 2H (CH 2 -CH-) δ 3.4, 2H (CH=CH) at δ 5.2, δ 6.6, 1H (OH-Ar) at δ 4.9, (11H) with interference aromatic protons at δ 7.4-7.7, 3H (NH) band at δ 9.8-10.4, 1H (COOH), δ 11.4.
Thermal data for the metal complexes
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Thermal data for the metal complexes
From the previous data, the suggested structure of the prepared complexes as follows:
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Thermal analysis. Thermal analysis curves DTA, TGA, show an endothermic peaks within the temperature range 27 - 190 ℃ corresponding to the complexes 26 firstly for (Pb-Fe) complex an endothermic peaks are appeared with weight loss (6 - 41%) due to the elimination of hydrated water. Also, for (Pb-Ni) complex, decomposition occurred at the range of (27 - 200 ℃) with weight loss (3.072%) due to the elimination of the hydrated water for (Pb-Co) complex the elimination at the range (27 - 180 ℃) with weight loss (6.35%) due to the hydrated water continuous decomposition at the range of (19 - 350 ℃) for (Pb-Fe) complex with weight loss (19.52%), and at the range of 200 - 300 ℃ with weight loss (14.024%) for (Pb-Ni)-PAC complex and at the range 200 - 350 with weight loss (18.39%) for Pb-Co complex, these decomposition due to the elimination of chlorine atoms and coordinated water. After that an exothermic peaks are appeared above 300 ℃ for Pb-Fe showed decomposition at the range of 305 - 400 ℃ with a weight loss of (35.78%), continuous decomposition of the complex from 550 - 700 ℃ with weight loss of (26.62%) due to the change to metal oxides of Pb or Fe oxide (Pb-Ni) complex showed exothermic peaks at the ranges of 325 - 450 with a weight loss (10.19%) corresponding to the change of metal carbonate which will decomposed at the range of (550 - 700) with weight loss of (24.57%) to metal oxides.
Pb-Co complex showed a decomposition at the same ranges of 350 - 465 with weight loss of 32.27%, due the formation of metal carbonate and decomposition to metal oxides of Pb and Co oxides occurred at the ranges of 475 - 600 with an endothermic peak of weight loss 51%, as shown in 5 .
Finally, the stability of the complexes will be obeyed the following range order:
  • [Pb-Ni] complex > [Pb-Fe] complex > [Pb-Co] complex
the stability of [Pb-Ni] complex due to its decomposition in thermal analysis till metal oxides at higher temperature ranges.
CONCLUSIONS
A new chelating copolymers containing azo group units as ligating centers with different molar ratios of metal ions were synthesized and examined by using IR, 1 H NMR spectra and also the polymer complexes were examined by thermal analysis technique. Elemental analysis were elucidated by atomic absorption spectrophotometer and IR-spectra. →→ The thermal study of these polymer complexes was used to elucidated the supposed structure of the polymer complex and explained the coordinated water in the structure, also explained that the stability of the complexes in the range order [Pb-Ni] complex > [Pb-Fe] complex > [Pb-Co] complex.
References
Bach H. C. , InMark H. F. , Gaylrod N. G. , Bikalo M. M. 1969 Encyclopedia of polymer science and technology Interscience New York Editors 671 -
Agolini F. , Gay F. P. 1970 Macromolecules 3 349 -    DOI : 10.1021/ma60015a015
David TLC , Movawetz H. H. 1976 Macomolecules 9 463 -    DOI : 10.1021/ma60051a015
Blair H. S. , Pague V. I. , Riordan J. F. 1980 Polymer 21 1195 -    DOI : 10.1016/0032-3861(80)90087-7
Morgan P. W. 1974 US Patent. 3 791 -
Balasubramannian M. , Nanjan M. J. , Santappa M. 1979 Macromol. Chem. 180 2517 -    DOI : 10.1002/macp.1979.021801028
Balasubramainnan M. , Nanjan M. J. , Santappa M. 1981 Macromol. Chem. 182 853 -    DOI : 10.1002/macp.1981.021820316
Srinivasan P. R. , Srinivasan M. , Mahadevanv J. 1982 Polym. Sci. 20 1145 -
Blasius E. , Brozio B. , Flaschka H. A. , Bamad A. J. 1967 Chelates in Analytical Chemistry 1 49 -
Kantipuly C. , Katragadda S. , Chow A. , Gesser H. D. 1990 Talanta. 37 491 -    DOI : 10.1016/0039-9140(90)80075-Q
Moyers E. M. , Fritz J. S. 1977 Anal. Chem. 49 (3) 418 -    DOI : 10.1021/ac50011a023
Ueno K. , Martell A. 1955 J. Phys. Chem. 59 998 -    DOI : 10.1021/j150532a002
Ueno K. , Martell A. E. 1956 J. Phys. Chem. 60 1270 -    DOI : 10.1021/j150543a029
Okawa H. 1985 J. Chem. Soc. 59 -
Sinn E. 1985 Inorg. Chem. 24 127 -    DOI : 10.1021/ic00196a003
Collins T. J. 1986 J. Am. Chem. Soc. 108 6593 -    DOI : 10.1021/ja00281a024
Che C. M. , Cheng W. K. 1986 J. Chem. Soc. Chem. Commun. 1443 -    DOI : 10.1039/c39860001443
Rangnekar D. W. , Parekh R. R. 1987 Dyes Pigments 8 475 -    DOI : 10.1016/0143-7208(87)85039-8
Radwan M. A. , Badr S. K. 1999 J. Appl. Sci 6 14 -
Haslam J. 1969 Introduction to the chemical analysis of plastics, English Translation Ilife Books Ltd. London
Patel J. R. , Sutaria D. H. , Patel M. N. 1995 React. Polym. 25 17 -    DOI : 10.1016/0923-1137(95)00003-2
Huggins M. L. 1942 J. Am. Chem. Soc. 74 2715 -
Kraemer E. O. 1938 Ind. Eng. Chem. 30 1200 -    DOI : 10.1021/ie50346a023
Cukurovali A. , Yilmas I. 2006 Trans Met. Chem. 31 207 -    DOI : 10.1007/s11243-005-6353-8
El-Boraey H. A. , El-Tabl A. S. 2003 Polish J. Chem. 77 1759 -
El-Tabl A. S. , Imam S. M. 1997 Trans. Met. Chem. 22 259 -    DOI : 10.1023/A:1018464508113