Recent Trends in Terpolymer Preparation and

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Terpolymer Preparation

Recent Trends in Terpolymer Preparation and Characterization – An Overview S. S. Syed Abuthahir,[a,e]* P.Shanthy,[b] N.Vijaya,[c] R.Joseph Rathish,[d] S.Santhana Prabha,[d] A. Jamal Abdul Nasser, [a] and S. Rajendran[e]

A new polymer made from the combination of three different monomers is known as terpolymer, which has high molecular weight. Terpolymerization is the joint polymerization of three or more monomer species. It is carried out to vary the properties of polymer such as hardness, strength, rigidity, heat resistance etc., It is used in high performance elastomers with excellent high temperature, oil and chemical resistance available as conventional copolymers and terpolymers. Special terpolymer can be designed for improving mechanical properties in moulding and extrusion applications. High viscosity terpolymer that provides excellent balance of physical properties for moulded products. Very high viscosity terpolymer for superior mechanical and composition set resistance provides improved adhesion to substrate. Terpolymer resin is used in ion exchange process to recover certain metal ions from waste solutions and for the purpose of waste water solution and removal of iron from boiler water. It is used in energy storage capacitors as high dielectric constant terpolymer. The terpolymeric ligand and its polychelates are used against certain pathogenic bacterias. Generally the terpolymer is synthesized by solution condensation, melt condensation or emulsion polymerization in an acid medium, base medium or catalyst. The recent trends in preparation and characterization of terpolymer and its chelates are discussed Keywords: Terpolymer, synthesis and characterization, polymer metal complex, polymer review.

*Corresponding Authors [a] Post Graduate & Research Department of Chemistry, Jamal Mohamed College, Tiruchirappalli 620 020, India. Email : [email protected], [email protected] [b] Department of Chemistry,Kunthavai Naachiar Govt. Arts College, Thanjavur, India. [c] Department of Chemistry,Vellalar College for Women, Thindal, Erode, India. [d] PSNA College of Engineering and Technology, Dindigul, India. [e] Department of Chemistry, RVS School of Engineering and Technology, Dindigul-624 005, India. Email : [email protected].

1. INTRODUCTION The term terpolymerization refers to the simultaneous polymerization of three monomers together. This review presents an account of the synthesis and characterization of terpolymer metal complexes. Examination of the early literature reveals that terpolymerization was initiated when polymer science was in its infancy. It continued to grow to become a subject of major importance and evoked the interest of both academics and industrialists alike. The terpolymerization is readily achieved through the application of the concept and techniques already developed for multicomponent polymerization. It allows the gathering of information about the reactivity of certain classes of monomers otherwise not available. It is proposed to develop the many effects such as heat resistance, elasticity, tensile strength, transparency, solvent resistance and dimensational stability which were obtained through the proper choice of the two monomers and special effects such as vulcanization, modified flow properties, antiseptic properties and drying ability which were obtained by the incorporation of a third monomer. The polymer metal complex is a metal complex containing a polymer ligand presenting a remarkably specific structure in which central metal ions are surrounded by an enormous polymer chain [1]. Based on this polymeric ligand, the polymer metal complex shows interesting and important characteristics, especially catalytic activities which are different from the corresponding ordinary metal complexes of low molecular weight [2]. In recent years polymer metal complex has been of interest to many chemists, because they have come to understand that these compounds could lead to highly efficient catalysts and chemically modified electrodes [3]. Coordination polymers acquired a renewed research interest in the recent past because of their interesting properties such as ability to bind toxic metal ions, thermal stability, exhibition of catalyst, Int. J. Nano. Corr. Sci. Engg. 1(1) (2014)

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photoluminescence properties [4-8]. The biochemical applications of these types of polychelates have further motivated the researchers for the new synthesis of new coordination polymers. Transition metal chelated thiourea-formaldehyde resin was synthesized and reported for its good antimicrobial activity and high thermal stability [9]. Terpolymers involving anthranilic acid and thiourea with formaldehyde resin was synthesized and reported [10]. An eco-friendly technique was employed for the synthesis of a terpolymer where the metal ion binding properties of the prepared polymer are also reported [11]. 8-hydroxyquinoline-5-sulphonic acid and oxamide with formaldehyde terpolymer was proved to be an excellent metal binding polymer for selective metal ions [12]. A survey of the literature reveals that the polymer complexes derived from low molecular weight polymer and transition metals draw the attention of synthetic chemist due to their varied biological activities [13]. Terpolymer chelates possess attractive applications for environment pollution control, bioinorganic catalysts, hydrometallurgy, semiconducting devices and metal recovery from dilute solutions [14-18]. Salicylaldehyde oligomer-metal complexes demonstrated high stability against thermo-oxidative degradation and the half degradation temperature of Zn(II) and Co(II) complexes which are higher than that of the ligand [19]. Polymermetal complexes of copper (II) and Nickel (II) derived from poly(2-hydroxy-4-(meth)acryloxy acetophenone oxime found to have good thermal stability and poor conductivity [20]. Ion exchange process is a powerful and eco-friendly extraction technique for the separation of metal ions and recovery of toxic heavy metal ions etc., from the industrial wastes, tannery effluent and sewages [21-22]. In the recent past, there are several incidents of metal ion toxicity to human being through the contamination of ecosystems, increasing environmental concerns that have led us to use organic ligands anchored to solid supports in order to remove and recover important as well as toxic metal ions from aqueous solutions. Ion exchange resin plays a vital role in these types of environmental issues. Chelation ion exchange behavior of a terpolymer was reported for its good sorption capacity for Cu(II), Ni(II) and Fe(III) metal ions among the other metal ions under study [23]. Terpolymer involving O-nitrophenol-thiourea-paraformladehyde resin were synthesized and reported for its excellent ionexchange capacity [10 & 17]. Terpolymer resin derived from salicylic acid and formaldehyde with resorcinol was reported for its capacity to separate two synthetic mixtures such as Pb(II)-Cd(II) and Ni(II)-Cu(II)-Zn(II) at optimum conditions of Kd values and also used to analyze the constituents of brass [24]. The heavy metal ion toxicity has increased substantially because of the use of metal ions as catalyst in various industries. Many methods such as electro deposition, co precipitation, and solid-liquid extraction have been developed for pre concentration and removal of metal ions. However the metal ion removed by chelating ion exchange resin using batch equilibrium method has gained rapid acceptance because of its wide variety of sorbent phases, high degree of selectivity, high loading capacity and enhanced hydrophilicity [25-27]. Interest in supra molecular chemistry has triggered in particular, attempts to synthesize metal containing conjugated polymer systems and to study their electrical, electrochemical and photo physical properties [28-29]. Extensive research on transition metal complexes have displayed a broad spectrum of interesting properties from metal centered or ligand centered behavior to these in which strong metal-ligand interaction leads to charge transfer between two units [30-32]. The synthesis of new anti-microbial polymers with reactive functional group has evoked considerable interest in recent years. The functional group containing oxygen, nitrogen, phosphorous and sulphur present in the polymer matrix is capable of coordinating with different metal ions and to form polymer metal complexes with wide spread applications in nuclear chemistry, pre-concentration, recovery of trace metal ions, pollution control, hydrometallurgy, polymer drug drafts and waste water treatement [33-37].

1.1. Polymer Metal Complexes Synthesis and Characterization Polychelates of few transition metals were prepared using the terpolymer ligand formed from the polymerization of anthranilic acid and thiosemicarbazide with formaldehyde. The ligand and the polychelates are characterized by elemental analysis, FTIR, electronic absorption and NMR spectroscopy. The metal to ligand ratio in all the polychelates was found to be 1:2. The chemical composition and structure are proposed based on various spectroscopic techniques. The thermal stability of the ligand and polychelates was studied by Thermo Gravimetric Analysis, in addition to that the activation energy for the formation of both the terpolymer ligand and its polychelates were calculated using the TGA and freeman-caroll method. Thermal stability of the ligand and its polychelates can be determined using thermogravimetric analyzer at a heating rate of 10 o c/min. in a static nitrogen atmosphere and the degradation pattern is also proposed. The electron delocalization along a conjugated system is having the two stages of degradation. The activation energy for the synthesis of ligand and the formation of polychelates is calculated using the following freeman-caroll method ‘[38]. ∆

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Where, dw/dt – is the rate of change of weight with time Wr = Wc-W, Wc – is the weight loss at the completion of reaction or at definite time W – is the total weight loss up to time t n-is the order of the reaction T and R are the temperature and gas constant respectively.

Hence, a plot of ∆ slope is equal to

versus

give an intercept on the Y axis equal to n and the

.

The electronic spectra give clear evidence to confirm the electronic structure of the polychelates. The band appearing in the range of 250-300 nm is assigned as π π* transition of the terpolymer ligand,where the band at 450-490 nm is assigned to polychelates, which clearly establishes the metal ion coordination takes place through the nitrogen of NH2 group of Ar-NH2 and the nitrogen atom in the thiomicarbazide moiety. The ligand and its polychelates have good inhibition against the growth of pathogenic bacterial strains [39]. Terpolymer ligand was synthesized from 8-hydroxyquinoline and anthranilic acid with formaldehyde by solution condensation in an acid medium. Polychelates of Cu(II), Ni(II), Zn(II) and Pb(II) were prepared using the terpolymer as ligand . The Ligand and its polychelates possess antimicrobial activity for certain bacteria such as staphylococcus aureus, Escherichia Coli, Fungi Aspergillus niger and candida albicans. The viscosity-average molecular weight of the terpolymeric ligand is determind using a brooke viscometer in DMSO solvent by selecting the appropriate spindle and adjusting the spindle speed, the viscosity –average molecular weight of the terpolymer .The electrical conductivity of this ligand and its polychelates is also measured using a Yokogawa 7651 instrument with a Nickel sheet as a blank substrate and the polymer in DMSO solvent by the pour point method at a current rate of 5amperes per second. The electrical properties were measured at various concentration such as 0.05, 0.2, 0.4 and 0.6M and the temperature ranging from 50 to 100 oC.This study was reported by Riswan Ahamed et.al.,[40]. A chelating terpolymer resin was synthesized from 8-hydroxyquinoline and salicylic acid with formaldehyde by solution condensation technique in acid medium. It is characterized by elemental analysis, infra red and nuclear magnetic resonance spectroscopy. The average molecular weight and the polydispersity index for the terpolymer is calculated using gel permeation chromatography.A batch equilibrium method is employed to study the selectivity and sorption capacity of the terpolymer resin towards certain divalent metal ions such as Pb2+ ,Zn2+,Cu2+,Ni2+,Ba2+,Co2+ and Mn2+ in various electrolyte concentrations wide pH ranges and different time intervals and the distribution of metal ion at different pH level by using the following equation . The distribution of metal ion is designated as Kp.

Kp

=

Weight of metal ions taken up by 1 g of the resin sample Weight of metal ions present in 1 ml of the solution

The rate of metal ion uptake is also calculated by using the following equation Metal ion uptake =

Amount of metal ion adsorbed Amount of metal ion adsorbed at equilibrium

x 100

The amount of metal ion uptake of terploymer resin depends on the nature and concentrations of the electrolyte used for chelation studies. This terpolymer resin can also be reused after repeated washing with water [41]. The terpolymer resin involving phthalic acid and urea with formaldehyde is synthesized by condensation polymerization in glacial acetic acid medium and proved to be selective chelation ion-exchange terpolymer for certain metals. The resin was characterized by FTIR and NMR spectroscopy. The average molecular weight and morphology of the terpolymer resin can be used to recover certain metal ions from waste water and removal of Int. J. Nano. Corr. Sci. Engg. 1(1) (2014)

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iron from boiler water .This terpolymer resin is soluble in solvents like Dimethyl formamide, Tetrahydrofuran, Dimethy Sulphoxide, aqueous sodium and potassium hydroxide and insoluble in alcohol, chloroform and carbon tetra chloride. The physicochemical parameters such as moisture content , solid percentage , void volume fraction , true density and sodium exchange capacity of the terpolymer are studied and reported [42]. 4-hydroxybenzoic acid-thiourea-formaldehyde terpolymer is prepared by polycondensation technique in 2:3:5 mole ratio using 2M H2SO4 as a catalyst. The characterization and the structural elucidation of the prepared terpolymer is confirmed by elemental analysis, FTIR and NMR spectral studies. The gelpermeation chromatography is used to determine the average molecular weight of the terpolymer resin. The cation-exchange properties of the terpolymer is determined by batch equilibrium method, this terpolymer is found to be an excellent cation-exchanger for selective metal ions. The method involves ion-exchange behavior of the terpolymer with specific cations like Cd2+, Mg2+, Fe3+, Cu2+ and Mo2+ in various electrolytes, wide pH range and at different time intervals[43]. Anthranilic acid–thiourea-formaldehyde terpolymer resin is synthesized by eco-friendly techniques using dimethyl formamide as a reaction medium. The terpolymer resin is characterized by FTIR, nuclear magnetic resonance, thermal analysis and viscosity-average molecular weight and the physicochemical parameter is also determined. The kinetic parameters such as energy of activation and the order of the reaction are also evaluated on the basis of the thermogravimetric data using freeman-caroll method .The transition state between crystalline and amorphous is established .The colour of the terpolymer is confirmed by optical microscopy, the electrical property of the terploymer is confirmed by optical microscopy , the electrical property of the terpolymer showed an appreciable change in its conductivity at various concentrations and temperature. One of the important applications of these types of polymer is their capacity to act as chelating ion-exchangers. The electrical conductivity of the terpolymer is measured by doping carbon fibre with the polymer using DMSO solvent by pour point method at a current rate of 5A/S. The electrical property of the terploymer resin is measured at various concentrations such as 0.05, 0.2, 0.6 and 0.8mM and temperatures ranging from 50 to 120 oC with nickel sheet as a substrate using gans instrument are reported [44]. The terpolymer was synthesized by condensation of 2-hydroxy-4-ethoxyacetophenone with 1,4- butane diol in the presence of polyphosphoric acid as a catalyst at 145 oC for 10 hours .The synthesized resin is used to synthesize its polychelates with 4f-block elements. The resin and its polychelates were characterized on the basis of elemental analysis, electronic spectra, magnetic susceptibilities, FTIR, NMR and thermo gravimetric analysis, number average molecular weight is measured by vapour pressure osmometry. Adsorption studies at different electrolyte concentration pH and rates have been carried out for 4f-block elements in the resin. It is observed that the resin can be used as efficient adsorption agent. The number average molecular weight of the polymeric ligand sample was estimated by vapour pressure osmometry (VPO). Dilute solutions of the polymer samples of 2.21, 4.42, 6.63 and 8.84g.mol-1 were prepared in DMF, the vapour pressure osmometry was carried out for each concentration and the corresponding bridge output reading on milivolts was 30.00, 54.00, 80.00 and 102.00 respectively .The plot of milivolts versus concentration was drawn with the help of the slope and the VPO constant K were reported [45]. 2-hydroxy-4-acryloyloxy acetophenone formaldehyde macromonomer containing polymerizable vinyl group prepared by condensing 3-hydroxy-4-acetyl phenylacrylate with formaldehyde in the presence of oxalic acid is polymerized in methyl ethyl ketone at 70oC using benzoyl peroxide as intiator. Polychelates are obtained when the DMF solution of this polymeric resin containg a few drops of ammonia is treated with the aqueous solution of Cu(II), Ni(II). Elements analysis of the polychelates indicates a metal –ligand ratio of 1:2.the IR spectral data of polychelates indicate that the metals are coordinated through the oxygen of the keto group and oxygen of the phenolic OH group .The diffuse reflectance spectra and magnetic moment of polychelates indicate an octahedral and square planer geometry respectively [46]. Novel tetradentate salicyclic acid-formaldehyde ligand containing piperazine moiety is synthesized by condensation of salicyclic acid, formaldehyde and piperazine in presence of base catalyst which is subjected for the preparation of coordination polymers with metal ions like Mn(II), Cu(II), Co(II), Ni(II) and Zn(II). All the synthesized polymeric compounds are characterized by elemental analysis, IR, NMR and electronic spectral studies. Electronic spectral data and magnetic moment values revealed that polymer metal complexes of Mn(II), Co(II), and Ni(II) showed an octahedral geometry and tetrahedral geometry respectively. The antimicrobial screening of the ligand and coordination polymers was done by using ager well diffusion method against various bacteria and fungi are reported [47].

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Semicarbazazide-formaldehyde resin is prepared by the condensation of semicarbazide with formaldehyde in an acidic medium and its polymer metal complexes were prepared with transition metal ions. All the synthesized polymers were characterized by elemental analysis, FTIR, NMR, electronic spectroscopy, magnetic moment measurements and thermogravimetric analysis. The percentage of metal in all the polymer metal complexes is found to be consistent with 2:1 stoichiometry. The magnetic susceptibility measurement and electronic spectra of all the terploymer metal complexes confirmed the geometry of the complexes .The entire polymer metal complexes showed excellent antimicrobial activity and low toxicity when compared to their parental polymeric resin [48]. Terpolymer of N-isopropyl acrylamide(NIPAAM) with poly (ethyleneglycol) methacrylate several terpolymer samples were prepared by taking varying amount of monomers, NIPAAM and PEGMA in the initial feed using hydrophilic (IRGA-CURE-2959) and hydrophobic (DURACURE-1173) photo initiator. In order to investigate the effect of reaction conditions, terpolymers are prepared below or above the lower critical solution temperature using water or water: ethanol (50:50) as solvent and by varying the amount of cross linker hydrogels prepared under varying conditions were characterized for its swelling behavior using optical microscope, phase transition temperature using DSC and morphology using SEM. Terpolymer films having an optimum combination of swelling and performance properties are evaluated as switchable cell culture membrane. Hepatic cancer cell lines are used to study the cell growth and detachment. Cell viability is found comparable to trypsin which alsi supports application of these films as cell membrane [49]. A new generation of segmented thermoplastic poly(urethane-thiourea imides) & (PUTIs) is synthesized via reaction of polyethylene glycol and thiourea based terpolymer with dianhydride as chain extenders. NCO terminated polymer is synthesized from a new di isocyanate,3,3-[(4-isocyanatophenyl) carbonyl) thioureido ] phenyl-4-isocyanatophenyl carbamate as a hard segment and PEG forming soft segment. The starting materials and polymers are characterized by conventional methods and physical properties such as solubility, solution viscosity, molecular weight, thermal stability and thermal behavior are studied. PUTIs show partially crystalline structure. Investigation of the results authenticated the approach of introducing thiourea and imide structure in polyurethane for the improvement of thermal stability [50]. Terpolymer resin is prepared by the condensation of resorcinol, thiourea and formaldehyde in presence of 2M HCl as catalyst at 1400C. The synthesized terpolymer resin is characterized by FTIR, NMR and gelpermeation chromatographic techniques. To establish the thermal stability of the resin, TGA analysis is performed. The Doyle, HOROwitz & Metzger, Broido and Dharwakdar & Kharkhanavala are used to calculate the thermodynamic parameters which include enthalpy of activation, entropy of activation, free energy of activation and kinetic parameters like energy of activation and pre exponential factor for various steps of thermal decomposition of PTFI, chelation and ionexchange property of the terpolymer is studied for Fe 3+, Co2+, Cu2+, Zn2+, Pb2+ and Cd2+ ions [51]. Terpolymer resin is synthesized by the condensation of p-Cresol and Oxamide with formaldehyde in the presence of aid catalyst. It is proved to be selective chelation ion-exchange terpolymer for certain metals. The chelating ion-exchange properties of these terpolymer were studied for Fe(III), Cu(II), Ni(II), Co(II), Zn(II), Cd(II) and Pb(II) ions in the form of their metal nitrate solutions. A batch equilibrium method is employed in the study of selectivity of metal ion uptake involving the measurements of the distribution of a given metal ion between the terpolymer sample and a metal containing the metal ion. The study is carried out over a wide pH range shaking time and in media of various ionic strengths of different electrolyte the terpolymer showed a higher selectivity for Fe(III), Cu(II) and Ni(II) ions than Co(II), Zn(II), Cd(II) and Pb(II) ions. Distributions ratio of metal ions are found to be increased by increasing pH of solutions. The ion-exchange capacity of metal ions has also been determined experimentally and compared with other commercial resins. The terpolymer resin is characterized by viscometric measurements in dimethyl sulphoxide and nuclear magnetic resonance spectra. The physic-chemical and spectral methods are used to elucidate the structure of terpolymer resins. The morphology of the terpolymer is studied by scanning electron microscope, which shows amorphous nature of the resin. Therefore it can be used as a selective ion-exchanger for certain metal ions [52].

1.2. Determination of metal uptake in the presence of various electrolyte and different concentration: Generally the terpolymer sample is suspended in an electrolyte solution of known concentrations. The pH of the suspension is adjusted to the required value using either 0.1M HNO 3 or 0.1M NaOH. The suspension is stirred for 24 hours at 300 C, and 2ml of 0.1M solution of the metal ion is added. The pH is adjusted to the required value and the mixture is stirred again at 300C for 24 hours. The polymer is then filtered off and washed Int. J. Nano. Corr. Sci. Engg. 1(1) (2014)

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with distilled water. The filtrate and the washing are collected and then amount of metal ion is estimated by titrating against standard EDTA at the same pH (Experimental reading). The same titrations have been carried out without polymer (Blank reading). The amount of metal ion uptake of the polymer is calculated from the difference between a blank experiment without polymer and the reading in the actual experiment is repeated in presence of several electrolytes. The metal ion uptake can be determined as: Metal ion adsorbed (uptake) by resin = (X-Y)Z mmol/g Where Z(ml) is the difference between actual experiment reading and blank reading; X (mg) is the metal ion in 2ml 0.1M metal nitrate solution before uptake; and Y (mg) is metal ion 2ml 0.1ml metal nitrate solution after uptake. By using this equation the uptake of various metal ions by resin can be calculated and expressed in terms of millimols per gram of the terpolymer.

1.3. Evaluation of the Distribution of metal Ions at Different pH solutions The distribution of each of the seven metal ions i.e., Cu(II), Ni(II), Co(II), Zn(II), Cd(II),

Pb(II) and Fe(III) between the polymer phase and the aqueous phase was determined at 300C and in the presence of 1M NaNO3 solution. The experiments were carried out as described above at different pH values. The distribution ratio D is defined by the following relationship.

Amount of metal ion on resin

×

volume of solution (mL)

D= Amount of metal ion in solution

weight of resin (g)

Metal ion adsorbed by the resin = [ZX\Y] 2/0.025 Where Z is the difference between actual experimental reading and blank reading, C(g) is the amount of metal nitrate solution, and Y(g) is the amount of metal ion in 2mL of metal nitrate solution after uptake.

1.4. Viscometric Study Viscometric measurements were carried out in DMSO solutions at 30 0C using Tuan-Fuoss viscometer fabricated in research laboratory at different concentration ranging from 1.00 to 0.031%. Intrinsic viscosity (η) was calculated from relevant plots of Huggin’s eqn (1) and Kraemer eqn (2). ηsp/C = [η] + K1 [η] .C -------------- (1) In: ηr/C = [η]-K2 [η]2.C

--------------- (2)

Where C is concentration in g/100 mL; is the ratio between viscosity of solution [η] and the viscosity of the solvent [η0] that is known as relative viscosity, ηr = η/ η0; ηsp has been derived from relative viscosity and given by ηsp = (η- η0)/ η0 = η/ η0-1; [η] is intrinsic viscosity obtained by extra plotting of a plot of η sp/C or ln ηr/C against concentration; and [η] is lim C 0 (ηsp/C). The intrinsic viscosity is one of the characteristics of a polymer according to the above relations. The plots of ηsp/C and ln ηr/C against concentration are linear with slopes K1 and K2 respectively. Intercepts on the viscosity function axis given [η] value in both plots [52]. A terpolymer is synthesized by condensation of 4-hydroxybenzaldehyde oxime –formaldehyde and chloro, bromo. Methoxy or methyl substituted acetophenone at 100-120oC. The terpolymer is characterized by FTIR, 1H NMR, electronic spectroscopy and molecular weight. Polydispersity is determined by gelpermeation chromatography. Molecular weight is observed in the range 2966-4370 and the polydispersity index range is 1040-1.45. Thermal stability of the polymer is investigated by using thermal gravimetric analysis and differential scanning colorimetry. The synthesized polymer shows excellent antimicrobial activities as compared to the standard ciprofloxacin and amphotericin –II drugs [53].

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Terpolymer (8-hyroxyquinoline- guanidine- formaldehyde) is synthesized using monomers 8hyroxyquinoline, guanidine and formaldehyde in 1:1:2 molar proportions, the structure of 8-HQGF is elucidated on the basis of elemental analysis, various physicochemical techniques i.e. UV-Visible, FTIR and 1H NMR spectroscopy. Detailed thermal degradation study of the terpolymer is carried out to ascertain its thermal stability. Sharp-wentworth and Freeman-caroll methods are used to calculate activation energy and thermnal stability. The activation energy is calculated by using sharp-wentworth which is found to be good agreement with that calculated Freeman-caroll methods. Thermodynamic parameters such as free energy change, entropy change, apparent entropy change and frequency factor are also evaluated on the basis of the data of Freeman-caroll methods [55]. Log (dc/dt)/1-C = log (A/β) – Ea/2.303 × 1/T Where dc/dt is the fraction of mass with time t, β - dT/dt, A= pre-exponential factor of frequency and C= Concentration of mole fraction or amount of reactants. A series of anhydride-co-imide terpolymer based on trimellitylimido-L-tyrosine (TMA-Tyr)sebacic acid (SA), 1.3-bis (carboxyphenoxy)propane (CPP) is synthesized by melt condensation polymerization. It is desirable to incorporate tyrosine into the backbone of the polymer system due to its inherent ability to enhance the immune response to vaccine antigents. CPP and SA were copolymerized with the tyrosine derivative, TMATyr in order to develop a polymer with suitable material properties for drug delivery (e.g. high molecular weight amorphous and good solubility in low-boiling organic solvents) as well as to provide a series of polymer capable of a wide range of degradation and antigen release properties. To our knowledge their review represents the report of the synthesis and characterization of terpolyanhydrides designed specifically to deliver drugs such as vaccine antigens. A systematic series of study is performed to evaluate and optimize the influence of monomer ratio, reaction time and temperature, reaction catalysis and catalyst concentration on polymer molecular weight, percent TMA-Tyr incorporation and crystalinity. Terpolymer is synthesized with weight, average molecular weight in excess of 80,000 by using heterogenic catalyst and highly purified monomers with low degree of oligomerization. In addition the terpolymer has no crystalline, the only exception being polymers with >60% SA in their backbone. Monomers and polymers were characterized by 1H NMR, IR spectroscopy, elemental analysis, thermal transition temperature analysis and gelpermeation chromatography. The stability of these polymers in the solid state and in chloroform at various temperatures is also reported [56]. Poly(€-caprolactone-Co-1,2-butylene carbonate (PBCCL) is synthesized via terpolymerization of carbon dioxide, 1,2-butylene oxide (BO) and €-caprolactone (CC). A polymer supported bimetallic complex (PBM) is used as catalyst. The influence of various reaction conditions such as reaction content, reaction time and reaction temperature on properties of terpolymer was investigated. When CC content is increased, the viscosity average molecular weight, glass transition temperature and decomposition temperature of PBCCL improved relative to those of poly(1,2-butylene carbonate) (PBC). Prolonging the reaction time resulted in increase viscosity average molecular weight and glass transition temperature. As reaction temperature increased the molar fraction increased obviously. When the reaction temperature went beyond 80 0C the resulting terpolymers tended to be crystalline. Thermal properties and degradation behavior of PBCCL were investigated by differential scanning colorimetry and therogravimetric analysis. The apparent activation energy and thermal degradation of mode of PBCCL was estimated by means of ozawa-flynn-wall method and Phadnis-Deshpande method respectively. The results showed that glass transition temperature and decomposition temperature of polymer PBCCL were much higher than those of PBC. The thermal degradation behavior of PBCCL was evidenced by one step thermal degradation profile. The average apparent activation energy was calculated as 77.06 KJ/mol [57]. Condensation of bis-(salicylaldehyde) metal (II) (metal = Be, Zn and Cd) an diamines (1,4-diaminobenzene or 4,4-diaminodophenyl) yield polymeric complexes which are investigated for their characteristics, composition, structure, thermal stability and polymeric nature. The stable powdery solids are obtained by refluxing 1:1 bis (salicylaldehyde) metal. Chelate (in DMF) and diamine (ethanoic) have the composition and are insoluble in common solvents. IR study indicates that the salicylaldehyde molecule is bonded to the metal ion through the oxygen atom of phenolic and aldehydic group in bis-(salicylaldehyde) metal chelates. On introduction with diamines, the polymeric complexes are formed. The nitrogen atoms of the amino groups replace the aldehydic oxygens. The terminal nitrogens of the diamines and the polymeric chain grow in a similar manner. The complexes obtained from 4-41 diaminophenyl are thermally more stable than those from 1,4-diaminobenzene [58].

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Terpolymer MAF is synthesized by the polycondensation of melamine (M) and aniline (A) with formaldehyde (F) in the presence of an acid catalyst in 1:13 molar proportions of the reacting monomers. Polychelates were prepared by using metal acetate, metal salts and MAF ligand in dimethylformamide medium. The prepared terpolymer and its metal chelates were characterized by using elemental analysis, magnetic studies and spectral analysis. The electrical properties of the terpolymer and its polychelates were studied over a wide range of temperature and in the order of MAF < Mn(II) < Fe(II) and Co(II). On the basis of electrical conductivity measurements of terpolymer and its polychelates found that a higher temperature conductivity increases linearly showing semiconducting behavior and hence useful in electronic industry [59]. Terpolymer (p-COF-II) is synthesized by the condensation of p-cresol(p-C) and oxamide (O) with formaldehyde (F) in the presence of acid catalyst and using 2:13 molar proportions of the reacting monomers. The synthesized terpolymer resin is characterized by elemental analysis and spectral studies like IR, NMR and XRD. The morphology of synthesized terpolymer is studied by scanning electron microscopy. The electrical property is measured over a wide range of temperature (313-403K). The chelating ion-exchange study is carried out over a wide pH range, shaking time and in media of various ionic strengths for seven metal ions Fe(III), Cu(II), Ni(II), Co(II), Zn(II), Cd(II) and Pb(II) in the form of their metal nitrate solutions. The terpolymer shows a higher selectivity for Fe(III), Cu(II) and Ni(II) ions. Thermal study of the resin is carried out to determine its mode of decomposition and thermal stability. Using data of thermogravimetry, various kinetic parameters like frequency factor (Z), entropy change (ΔS), free energy change (ΔF) and apparent entropy change (S*) have been determined using Freeman-carroll method [60]. Terpolymer resin (4-HABF) is synthesized by the condensation of 4-hydroxyacetophenone and biuret with formaldehyde in the presence of acid catalyst and using varied molar ratios of reacting monomers. Terpolymer resin compositions have been determined on the basis of their elemental analysis and number average molecular weight of this resin is determined by conductometric titration in non-aqueous medium. Viscometric measurements in dimethylformamide have been carried out with a view to ascertaining the characteristic functions and constant. UV-Visible, IR and NMR spectra are studied to elucidate the structure. Chelation ionexchange a property of this resin is also studied employing batch equilibrium method. It is employed to study selectivity of metal ion uptake over a wide pH range and in media of various ionic strengths [61]. A synthetic route for the preparation of a novel solution terpolymer derived from styrene, methyl styrene, and polyaniline (PANI) and its organoclay nanocomposite are prepared. Soluble PANI was synthesized by the incorporation of brominated poly(styrene-co-methyl styrene) onto the emeraldine form of PANI. Styrene-comethyl styrene copolymer was synthesized via nitroxide-mediated living radical polymerization by 2,2,6,6tetramethylpiperidinyloxy iniferter and then was brominated with N-bromosuccinimide. The solution terpolymer derived from styrene, methyl styrene, and PANI was synthesized through the N-grafting reaction of deprotonated PANI and brominated terpolymer. Nanocomposites of the terpolymer with modified montmorillonite were prepared with a solution intercalation method. The conductivity of the terpolymer was measured by the fourpoint probe method. The structures of the intermediate, terpolymer, and nanocomposite were investigated by Fourier transform infrared spectroscopy, 1H-NMR, and X-ray diffraction techniques. The molecular weight of the terpolymer was determined by gel permeation chromatography. Their thermal behavior was examined by differential scanning calorimetry and thermogravimetric analysis [62]. pH- and thermo‐sensitive polyethersulfone (PES) hollow fiber membranes were prepared by blending a terpolymer of poly(N-isopropylacrylamide-co-methacrylic acid-co-methyl methacrylate) (P(NIPAAm-MAAMMA)) via dry–wet spinning technique based on a liquid–liquid phase separation. The terpolymer was synthesized via free radical solution polymerization. Scanning electron microscopy (SEM) results showed that the membrane morphology had been altered after the introduction of the terpolymer. The modified PES hollow fiber membranes showed pH-sensitivity, and the pH-valve effect was observed at the pH value between 7.0 and 10.0; the modified PES membranes also showed thermo-sensitivity, the hydrodynamic permeability changed slightly while the pore sizes changed significantly when the temperature increased, which indicated that the modified membranes could be used for thermo-sensitivity separation, but not suitable for thermo-sensitivity hydrodynamic permeability control. The membranes also showed excellent pH- and thermo-reversibilities [63]. A monomer, vanillin oxime (VO), has been synthesized from vanillin and hydroxylamine hydrochloride, and its terpolymer resin VO-formaldehyde-p- hydroxyacetophenone (VOFHA) has also been synthesized by condensation polymerisation of VO, formaldehyde, and p-hydroxyacetophenone (HA) in 1:2:1 M proportion in the presence of hydrochloric acid. The structures of monomer and terpolymer have been investigated by FT-IR and 1H NMR techniques. The number-average molecular weight and polydispersity index of the terpolymer were found to be 5337.6 g/mol and 1.33, respectively, by gel permeation chromatography. Terpolymer (VOFHA) has Int. J. Nano. Corr. Sci. Engg. 1(1) (2014)

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shown highest zone of inhibition as compare to other terpolymer and standard drugs. This novel bio-responsive antimicrobial terpolymer shows promise for use in the control of medical devices associated infections [64].

FUTURE SCOPE This paper attempts to present the overview of synthesis and characterization of terpolymer metal complexes. It has endeavored to cover the growing synthetic potential of terpolymer synthesis from its beginning until now. The evolution of new polymerizing techniques has enabled the organic polymer chemist to overcome many of the inherent limitations of this class of polymers. In future high thermal stability of nanocomposites can be prepared using this method. Terpolymer ligands which contain hetero atoms show antimicrobial activities that can act medicine against some disease. High load bearing, high temperature withstanding and high electrical conductivity polymer can be prepared by using the terpolymerization. Toxic metals present in water can be removed. Good adhesion properties of polymer can be prepared.

ACKNOWLEDGEMENTS The authors are thankful to their management of Jamal Mohamed College, Tiruchirappalli,Tamilnadu, India. S.S.Syed Abuthahir and Dr.S.Rajendran are thankful to Dr.R.Saravanan, Director, B.Kothandaraman, CEO, Mr.K.Senthi Gasesh. Managing Trustee and Dr.K.V.Kuppusamy, Chairman of RVS Educational Trust’s Group of Institutions, Dindigul-05, Tamilnadu, India.

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Received: (30-09-2014) Accepted: (07-11-2014)

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