Many condensed polymers [A1-A7] were prepared via reaction of (Ethylenediaminetetraacetic  acid = EDTA), with different prepared imide-diamines  by modification  [ modification of  amino acids and antibiotics  (B1-B7)] Imide-diamines were prepared by chlorination of  L-amino acids such as [ L-Histidine, L-Alanine, L-Valine, L-Glycine and  L-Aspargine ] or selected antibiotics such as [Cephallixine monohydrate and  Amoxilline ] with thionyl chloride at 0°C, then reacted with ammonia to obtain imide-diamines [B1-B7] . The physical properties of all prepared condensed polymers [A1-A7], new prepared diamines [B1-B7] were studied and characterized by  FT -IR spectroscope   to certify the structural formulas. The thermal analysis (TGA, DTA) were studied, and the intrinsic viscosities were measured at 30°C using Ostwald viscometer. Keywords: polymerization, thermal analysis (TGA, DTA), diamines and Viscosity Measurement

H. Al-Noor, Taghreed

H.Rashed, Haider

M.Ali, Fiyral.

English

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Advances in Life Science and Technology                                                                                                 www.iiste.org ISSN 2224-7181 (Paper) ISSN 2225-062X (Online) Vol.35, 2015  15 Polycondensation of Ethylenediaminetetraacetic Acid with Some Prepared Diamines Derived from Amino Acids or Antibiotic   Fiyral. M.Ali1            Taghreed H. Al-Noor2          Haider H.Rashed1 1, AL-Mustansiriyah University, College of Science, Baghdad -Iraq  2, Ibn -Al-Haithem College of Education for pure science, Baghdad University  Abstract Many condensed polymers [A1-A7] were prepared via reaction of (Ethylenediaminetetraacetic  acid = EDTA), with different prepared imide-diamines  by modification  [ modification of  amino acids and antibiotics  (B1-B7)] Imide-diamines were prepared by chlorination of  L-amino acids such as [ L-Histidine, L-Alanine, L-Valine, L-Glycine and  L-Aspargine ] or selected antibiotics such as [Cephallixine monohydrate and  Amoxilline ] with thionyl chloride at 0°C, then reacted with ammonia to obtain imide-diamines [B1-B7] . The physical properties of all prepared condensed polymers [A1-A7], new prepared diamines [B1-B7] were studied and characterized by  FT -IR spectroscope   to certify the structural formulas. The thermal analysis (TGA, DTA) were studied, and the intrinsic viscosities were measured at 30°C using Ostwald viscometer. Keywords: polymerization, thermal analysis (TGA, DTA), diamines and Viscosity Measurements  1. Introduction During the  condensation (polymerization   )  process, the monomers tend to form dimers (two linked monomers) and trimers (three linked monomers) first. Then, these very short chains react with each other and with monomers. The overall result is that, at the beginning of polymerization, there are many relatively short chains. It is only near the end of polymerization that very long chains are formed.  [1-4].  In organic chemistry, an imide is a function group consisting of two carbonyl groups bound to nitrogen. These compounds are structurally related to acid anhydrides .The relationship between esters and amide and between imides and anhydrides are analogous; the amine-derived groups are less reactive. In terms of commercial application, imdes are best known as components of high strength polymers. [5]. Most common imides are prepared by heating dicarboxylic acids or their anhydrides and ammonia or primary amines. The result is a condensation reaction: (RCO)2 O + R'NH2→(RCO)2N R' + H2O These reactions proceed via the intermediacy of amides. The intra-molecular reactions of carboxylic acids with amides are far faster than the intra-molecular reaction, which is rarely observed [6].The Ethylenediaminetetraacetic acid (EDTA)= (C10H16N2O8) molecule has six potential sites for bonding metal ions: the four  carboxyl groups (-COO - ) and the two amino groups (-NH2), each of the latter with unshared pair of electrons. Thus, EDTA is a hexadentate ligand  [7], See figure (1). It is used to treat acute and chronic lead poisoning by pulling toxins (including heavy metals such as lead, cadmium, and mercury) from the bloodstream. The word "chelate" comes from the Greek root chele,   which means "to claw." EDTA has a claw-like molecular structure that binds to heavy metals and other toxins.[8]              Figure 1: EDTA structure( a)   and   its cheater form (b) 2. Experimental 2.1 Materials  Most of the chemicals used were of Analytical Grade. The drug (antibiotics) were   obtained from (the state Enterprise   for the drugs Industries ,and Medical Appliances) in Samarra- Iraq (SDI)., EDTA, L-amino acids   and solvents  were purchased from (B.D.H) and Merck  and used without any further purification, dimethyIformamide and dioxan distilled before use. The FTIR spectra  were recorded in the 4000-400cm-1 range form a fourier transform Shimadzu 7R-40E spectrometer, Thermalizes of polymers were performed with TGA Curves. Ostwald viscometer was used for measured of viscosities.  Advances in Life Science and Technology                                                                                                 www.iiste.org ISSN 2224-7181 (Paper) ISSN 2225-062X (Online) Vol.35, 2015  16  Modification of  L- amino acids and antibiotics (B1-B7): A thionyl chloride (5 ml, 0.04 mol) was add gradually to a mixture of (0.04 mol) of dissolved amino acids or antibiotics in (10 ml) of DMF, the mixture was stirred using ice bath and the yellow product was collected and washed with ether. The corresponding imide derivatives were prepared using dissolved (2gm.of urea) which added to a dissolved of amino acid chlorides or antibiotic acid chlorides. After stirring for 2hrs, the solvent was evaporated; the product was recrystallized from ethanol. Table (1) shows the physical properties of prepared compounds.  Table (1) Formula and physical properties of prepared compounds [B1-B7]  Polycondensation of (EDTA) with prepared imide-diamines (A1-A7):   (1gm. 0.00342 mol ) of EDTA was dissolved in 5ml of DMF , then the (0.938 gm , 0.00342 mol ) of dissolved B1  in 6ml of Dioxan : DMF mixture (5:1 by vol.) were introduced in a single-neck round-bottom flask which was equipped with  a condenser , the mixture was refluxed and  stirred with magnetic bar  for 1hr., then the solvent was evaporated and clear polymer, was obtained , washed with diethyl ether. Finally, it was dried under vacuum oven, a constant weight was obtained. All prepared polymers (A1-A7) were obtained by the same method of condensation polymerization. See Table -2 .    Advances in Life Science and Technology                                                                                                 www.iiste.org ISSN 2224-7181 (Paper) ISSN 2225-062X (Online) Vol.35, 2015  17 Table (2) lists the physical properties of prepared polymers.      (2)Physical properties of prepared polymers of (EDTA)with prepared  imide-diamines(A1-A7) NHNHNHNHH2CH2C NNCCCCOOOOOHHOR R Viscosity Measurements [9,10]  Ostwald, capillary viscometer was used to determine viscosities of the prepared polymers in dioxane at 300C. DMF was also used as the solvent for some of the prepared polymers. Four types of viscosities of the polymers were calculated µrel, µsp, µred and µin, the last type which is the intrinsic viscosities was estimated by extra-piloting the curve in Fig. (1). the results of intrinsic viscosities are listed in Table (2). Advances in Life Science and Technology                                                                                                 www.iiste.org ISSN 2224-7181 (Paper) ISSN 2225-062X (Online) Vol.35, 2015  18  figure 2 : Carve of µin to concentration        Where   t= time of flow rate of polymer solution                      t0 =time of flow rate of the solvent only  Results and Discussion  The mechanism of modification of    L-amino acid and antibiotics (B1-B7): The modification of amino acids and antibiotics done by reacting them with thionyl chloride [11,12], at 0°C to prevent the polymerization between amino acid chlorides and then immediately adding urea to release  ammonia ( NH3). So the reaction done by two steps to prepare imide-diamine compounds as shown in scheme 1  Scheme 1 General reaction for the modification of  L-amino acids and antibiotics     C = gm/100ml Advances in Life Science and Technology                                                                                                 www.iiste.org ISSN 2224-7181 (Paper) ISSN 2225-062X (Online) Vol.35, 2015  19 The mechanism goes as shown in scheme 2: R1 CH2N OH2OS OClCl+coolingR1 CH2NOOHS OClClstrringcoolingstrringR1 CH2N OOS OCl+ HClcoolingstrringClR1 CH2N OOS OClcoolingstrringR1 CH2N OOS OClClcoolingstrringR1 CH2N ClO+ SO2 + coolingstrringR1 CH2N ClONH3Cl+R1 CH2N ClONH2H-HClR1 CH2N NH2Oheat ref luxstrringheatrefluxstrringR1C NH2ClOR1 CH2N NH2O+heatref luxstrringR1C NH2OR1 CH2N NOClH Hheatref luxstrringR1C NH2R1 CH2N NHO O Scheme 2 : General mechanism for prepared imide-diamines  Fourier Transform Infrared spectra (FT-IR) The relevant vibration bands of the free ligands and the complexes are in the region 400–4000cm−1[13]. The FT-IR spectra assignment off Modification of  L- amino acids and antibiotics (B1-B7)were  summarized in (Table 3) ,  Table (3): Selected FT-IR bands for  Modification of  L- amino acids and antibiotics (B1-B7)  Polycondensation of (EDTA) with prepared imide-diamine compounds (A1-A7): In this research the new amide polymer was prepared from condensation of prepared imide-diamines with EDTA as chelate polymer containing amino acids and antibiotics through back bone of main chain of the Advances in Life Science and Technology                                                                                                 www.iiste.org ISSN 2224-7181 (Paper) ISSN 2225-062X (Online) Vol.35, 2015  20 polymer ,the following equation is illustrated the formation of the polymer .  The mechanism of the reaction was suggested as below:  R1CCCCOOOOOHOHHOHOR2 NH2H2N1DMF:10Dioxanref lux+R1CCCCOOOOOHHOR2 NH2NHOHOH HR1CCCCOOOOHO OHR2H2NHN OHR2 NH2H2NR1CCCCOOOOOHHOR2 NH2NHOH HR2HNH2N R1CCCCOOOOOHHOR2 NHHNR2HNHN+ H2O2  Fourier Transform Infrared spectra (FT-IR) Fourier Transform Infrared spectra (FT-IR) The relevant vibration bands of the compounds   were recorded in KBr disc in the region 400–4000 cm−1. The assignment of the characteristic bands (FT-IR) spectrum of the (A3), figure (4), and (A5), Figure (5) are summarized in Table (4). FTIR- spectrum, Fig (4) of polymer (A3) exhibits the characteristic absorption bond at 1656 cm-1 due to the C=O stretching vibration of the carboxylic groups. The absorption at 1667 cm-1 was attributed to the formation ester groups.  Table (4) : Poly condensation of (EDTA) with prepared imide-diamine compounds (A1-A7) ,  The thermal stability study Fig .(6) Showed TGA and DTA of prepared polymers [A1] (B1 with EDTA) which indicate the high thermal resistance, and showed three steps of weight loss-temperature, the first is ranged at 255C° with 33.704 % weight loss % , the second at 540 C° with 41.9% weight loss % and the third at 785C° with 97.4% weight loss % . This high thermal resistance is indicating the high molecular weight of the polymer, and presence of amide and imide groups through the backbone of the polymer chain.   Advances in Life Science and Technology                                                                                                 www.iiste.org ISSN 2224-7181 (Paper) ISSN 2225-062X (Online) Vol.35, 2015  21  Figure.3 FT-IR  spectrum  for compound B4   Figure.4 FT-IR spectrum  for polymer A3   Figure.5 FT-IR spectrum   for polymer A5 Advances in Life Science and Technology                                                                                                 www.iiste.org ISSN 2224-7181 (Paper) ISSN 2225-062X (Online) Vol.35, 2015  22   Figure.6 TGA for prepared polymer A1  References  1-Odian G  Principles of polymerization, 4th Ed. Wiley, New York (2004) 2- H.R Allcock., F. Lampe, J Mark. Contemporary polymer chemistry, 3rdEd.Prentice-Hall, Englewood Cliffs (2004). 3-Elias, H. G. An introduction to polymer science. VCH, Weinheim(1997). 4-Flory, P. J. Principles of Polymer Chemistry; Cornell University Press: Ithaca,NY; (1953). 5-Ballentine, Carol."Taste of Raspberries, Taste of Death "U.S Food and Drug Administration.June. FDA Consumer Magazine. Last retrieved Dec.(2007) 6- W Walter. and Michael."Polyimides" in Ullmanns´ Encyclopedia of Industrial Chemistry, Weinheim . doi:10.1002/1436007.a21-253, (2002). 7- S, West, Holler, Crouch Fundamental of Analytical Chemistry 8th ed. (2004). 8-Shrihari JS, Roy A, Prabhakaran D, Reddy KS. Role of EDTA chelation therapy in cardiovascular diseases. Natl Med J India. 2006;19(1):24-6. 9-Mori  H., Kato  I.,Matsuyama  M., EndoT., polymerization of acrylamides containing prolineand hydroxyproline moiety: Controlled synthesis of water-soluble and thermoresponsive polymers Macromolecules, 41, P.5604-5615. (2008) 10- Khudheyer J.Kadem (Synthesis And Study Of Some Novel Polymers Containing Different Drug Substituted Groups) PhD. Thesis University of Babylon College of Science, Dept. of Chemistry (2012). 11-Firyal M.A. (Modification of acryloylchlorides polymers) Um-Salama Science Journal .Vol.2 (4)(2005). 12-John Mc Murry . Organic Chemistry.  7th ed.(2008) 13-Nakamoto K.; (1996) “Infrared spectra of Inorganic and coordination compounds “4ED th ; J. Wiely and Sons, New york, 14- Firyal M.A., Taghreed H.Al-Noor   and Saif  M. Synthesis and Characterization of Gelatin- G-Poly (Acryloyl Amide) Proflavine and Controlled Release Study  Chemical and Process Engineering Research .2015., 32: 53-61.  The IISTE is a pioneer in the Open-Access hosting service and academic event management.  The aim of the firm is Accelerating Global Knowledge Sharing.  More information about the firm can be found on the homepage:  http://www.iiste.org  CALL FOR JOURNAL PAPERS There are more than 30 peer-reviewed academic journals hosted under the hosting platform.   Prospective authors of journals can find the submission instruction on the following page: http://www.iiste.org/journals/  All the journals articles are available online to the readers all over the world without financial, legal, or technical barriers other than those inseparable from gaining access to the internet itself.  Paper version of the journals is also available upon request of readers and authors.   MORE RESOURCES Book publication information: http://www.iiste.org/book/ Academic conference: http://www.iiste.org/conference/upcoming-conferences-call-for-paper/   IISTE Knowledge Sharing Partners EBSCO, Index Copernicus, Ulrich's Periodicals Directory, JournalTOCS, PKP Open Archives Harvester, Bielefeld Academic Search Engine, Elektronische Zeitschriftenbibliothek EZB, Open J-Gate, OCLC WorldCat, Universe Digtial Library , NewJour, Google Scholar   

Polycondensation of Ethylenediaminetetraacetic Acid with Some Prepared Diamines Derived from Amino Acids or Antibiotic

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Polycondensation of Ethylenediaminetetraacetic Acid with Some Prepared Diamines Derived from Amino Acids or Antibiotic

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