Preparation of Epoxy Functionalized Hybrid Nickel Oxide Composite Polymer Particles

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1 Americn Journl of Polymer Science 2013, 3(5): DOI: /j.jps Preprtion of Epoxy Functionlized Hyrid Nickel Oxide Composite Polymer Prticles Mohmmmd S. Hossn, Mohmmd A. Rhmn, Mohmmd R. Krim, Mohmmd A. J. Mih, Hsn Ahmd * Deprtment of Chemistry, Rjshhi University, Rjshhi 6205, Bngldesh Astrct Preprtion of inorgnic orgnic hyrid mterils is ttrcting much interest s such elortion produces remrkle improvement in properties nd verstility in ppliction potentil. In this investigtion, nnosized nickel oxide (NiO) prticles were first prepred y clcintion of nickel hydroxide precursor otined y simple liquid-phse process. The produced NiO prticles were functionlized with oleic cid followed y silne coupling gent. Finlly ttempt ws mde to prepre epoxy functionl hyrid NiO/poly(methyl methcrylte-glycidyl methcrylte) revited s NiO/P(MMA-GMA) composite polymer prticles y seeded copolymeriztion in ethnol medi. The composite prticles were colloidlly stle, nd the otined prticles were chrcterized y Fourier trnsform infrred, scnning electron microscopy, X-ry diffrction, nd thermogrvimetric nlyses. Electron microscopy showed tht the composite prticles re doped with nnosized NiO. Keywords Inorgnic-orgnic Composite, Epoxy Functionlity, Seeded Copolymeriztion, NiO, Doping 1. Introduction Hyrid polymer composites re clss of mterils tht comine the properties of inorgnic mterils with the esy processility, flexiility, elsticity, lighter weight nd improved colloidl stility of orgnic polymer prticles. The friction of hyrid inorgnic/orgnic polymer composites offers dvntges especilly when those pplictions depend on mechnicl nd surfce properties. Now dy reserchers re showing much interest on the preprtion of hyrid polymer prticles ecuse one cn enhnce or even incorporte novel properties (e.g. mechnicl, electricl, ctlytic, rheologicl, mgnetic nd opticl) y independently ltering the composition, dimension nd structure. These inorgnic-orgnic hyrid polymer prticles find wide ppliction potentils in ctlysis, electricl, opticl nd electronic or photonic devices, iomterils, flme-retrdnt nd cotings[1-9]. There is n incresing interest in the synthesis of nnosized metl oxides ecuse of their lrge surfce re unusul dsorptive properties, surfce defects, fst diffusivities nd quntum size effects which re different from those of ulk mterils[10-15]. Metl (oxide) nno prticles smller thn out 20 nm hve received widespred interest recently ecuse of their envisioned pplictions in * Corresponding uthor: smrhss@yhoo.com (Hsn Ahmd) Pulished online t Copyright 2013 Scientific & Acdemic Pulishing. All Rights Reserved electronics, optics, nd mgnetic storge devices. Among the vrious oxide mterils, nickel oxide (NiO) is very importnt semiconducting oxide mteril extensively used in ctlysis, ttery cthodes, gs sensors, electrochromic films, nd mgnetic mterils[16 25]. NiO ctlyst exhiits good low temperture ctlytic performnce for oxidtive dehydrogention of ethne to ethylene rection[26]. In ddition NiO hs received considerle interest for its ctlytic properties in decomposition of mmonium perchlorte,[27] hydrocrcking rections, reforming of hydrocrons, nd methne for production of synthesis gs, the removl of tr followed y the djustment of the gs composition in iomss pyrolysis/gsifiction, in cellulose pyrolysis, nd so forth[28]. These mechnicl nd physicl properties s well s ppliction potentils cn e further improved y reducing the size nd size distriution in the nno-rnge[29]. Despite the wide ppliction potentil of hyrid NiO composite polymer prticles in different industries only few reports re ville on the designing of such polymer prticles. López et l. reported the preprtion of poly(methyl methcrylte) (PMMA)/NiO nnocomposites y in situ ulk polymeriztion[30]. Prior to this, they treted the NiO prticles with silne coupling gent. In nother reserch, polyniline/nio/sodium dodecylenzenesulfonte composite microspheres were synthesized in micelles y using mmonium peroxydisulfte inititor[31]. In n erly work the uthor studied the fesiility of seeded emulsion polymeriztion to encpsulte NiO nno prticles within PMMA shell lyer using different NiO/MMA rtio

2 84 Mohmmmd S. Hossn et l.: Preprtion of Epoxy Functionlized Hyrid Nickel Oxide Composite Polymer Prticles (w/w)[32]. However, this results in some free NiO prticles though the encpsultion efficiency ws pretty good. In the present investigtion ttempt ws mde to prepre hyrid epoxy functionl NiO/poly(MMA-glycidyl methcrylte (GMA)) composite polymer prticles vi seeded polymeriztion in presence of silne coupled functionlized NiO prticles. The introduction of esily trnsformle epoxy group would give rective strting mteril for the design of whole rnge of compounds with vrious functionl groups. These groups cn e employed directly or vi modifiction using ctionic, nionic, chelte-forming, or fluorescent routes for immoiliztion of iopolymers, dyes nd other sensitive compounds[33-36]. Additionlly PMMA hs some interesting properties like exceptionl opticl trnsprency, good mechnicl properties, good wetherility, cceptle therml stility, moldility nd esy shping[30,37]. The preprtion scheme of NiO/P(MMA-GMA) composite polymer prticles re depicted in figure Experimentl 2.1. Mterils MMA nd GMA of monomer grde purchsed from Fluk, Chemik, Switzerlnd were distilled under reduced pressure to remove inhiitors. Oil solule inititor 2,2'-zois(isoou tyronirile) (AIBN) from LOBA Chem., Indi ws recrystlized from methnol, vcuum dried t 5 C nd preserved in the refrigertor efore use. Poly(vinyl pyrrolidone) (PVP) of moleculr weight 3.6 x 10 5 gmol -1 from Fluk, Chemik, Switzerlnd were used s steric stilizer. 3-(Methcryloyloxy)propyltriethoxysilne (MPS) from Alf Aesr, UK, ws used s coupling gent. Ethnol ws dehydrted nd distilled efore use. Other chemicls Ni 2+ (q) + OH - Precipittion N 2, 70 º C such s oleic cid, Ni(NO 3 ) 2.6H 2 O, NH 4 OH were of nlyticl grde. Deionized wter ws distilled using glss (Pyrex) distilltion pprtus Instruments Scnning electron microscope or SEM (LEO Electron Microscopy Ltd, Cmridge, UK) ws used to see the morphology nd prticle size distriution. IR spectrophotometer (Perkin Elmer, FTIR-100, UK), proton NMR (JEOL spectrometer, 400 MHz, JNM-LA400, Jpn) nd tle top high speed centrifuge mchine (TG 16-WS, Chin) were used in this study. The X-ry diffrction (XRD) ptterns of the powder smples were tken on Scnning X-ry Diffrctometer (D8 Bruker AXS) using Cu K-αrdition ( nm) in prllel geometry (not focused). The intensities were mesured t 2-thet vlues from 4.5Â to 100Â t continuous scn rte of 10Â /min with position sensitive detector perture t 3Â (equivlent to 0.5Â /min with scintilltor counter). Therml nlysis ws crried out using thermogrvimetry nlyser (TGA) from TGA Iris, TG 209 F1, Netzsch (Sel, Germny) Preprtion of Nnosized NiO Prticles Aqueous solution (0.6 M) of Ni(NO 3 ) 2.6H 2 O ws heted t 80 C, nd the temperture ws grdully incresed to 100 C over 2 h under mgnetic stirring. NH 4 OH ws dded slowly into the solution until ph 7 ws reched. A green colloid solution ws otined, which ws filtered nd wshed severl times with deionized distilled wter. The residul prt ws then dried t 100 C for 10 h to otin the sprepred precursor, Ni(OH) 2 powder. The powder ws clcined in pltinum crucile t 400 C for 3 h to otin the nnosized NiO prticles. Clcintion Muffle furnce MPS, EtOH, NH 4 OH Functionliztion P(MMA-GMA) Polymeriztion MMA+GMA Ni(OH) 2 gel Clcined NiO Figure 1. Schemtic representtion for the preprtion of NiO/P(MMA-GMA) composite polymer prticles

3 Americn Journl of Polymer Science 2013, 3(5): Functionliztion of NiO Prticles In order to improve the dispersiility, oleic cid stilized NiO prticles were prepred. First clculted mounts of NiO nno prticles were dispersed in deionized distilled wter y soniction for 1 h. Then 13 ml of oleic cid per unit mss of nno prticles were dded dropwise into the NiO nno prticles dispersion t 80 C over the course of 2 h under vigorous mgnetic stirring. The oleic cid stilized NiO prticles were wshed repetedly y serum replcement using wter followed y ethnol to remove the excess oleic cid. 1.5 g of MPS per unit mss of oleic cid stilized NiO prticles ws finlly dded nd the dispersion ws mgneticlly stirred t mient temperture for 48 h under nitrogen tmosphere. The MPS functionlized NiO prticles were wshed repetedly y serum replcement using ethnol through repeted centrifugtion Preprtion of NiO/P(MMA-GMA) Composite Prticles y Seeded Copolymeriztion 0.5 g of functionlized NiO prticles dispersed in 50 g ethnol ws tken in three necked round ottomed flsk dipped in thermostt wter th mintined t 70 C g of MMA nd 0.75 g of GMA were dded into the flsk nd 0.1 g of PVP ws used s steric stilizer. Polymeriztion ws strted y dding oil solule AIBN (0.05 g) s inititor under nitrogen tmosphere while the rection ws continued for 12 h. The produced composite prticles were wshed three times y serum replcement to remove ny unrected monomer nd inititor frgments Thermogrvimetric Anlysis (TGA) Therml properties of the dried powder were mesured y heting smples under flowing nitrogen tmosphere from 20 C to 800 C t heting rte of 5 C/min nd the weight loss ws recorded. 3. Results nd Discussion SEM imges of NiO, functionlized NiO nd NiO/P (MMA-GMA) composite polymer prticles re illustrted in figure 2. The verge dimeters of re NiO prticles re in the rnge of nm nd the verge size of MPS modified NiO prticles visily incresed to lmost nm. The increse in size is ttriuted to the functionliztion of NiO prticles y oleic cid nd MPS. SEM imge of NiO/P(MMA-GMA) composite polymer prticles clerly shows deposition of smller NiO prticles on the surfce of severl micron-sized P(MMA-GMA) copolymer prticles. From the imge it is not cler whether some NiO prticles re encpsulted within the polymer shell lyer during seeded copolymeriztion though it ws expected tht presence of vinyl group in the silne coupling gent would fvour copolymeriztion of MMA nd GMA on the surfce of functionlized NiO prticles. The mechnism of formtion of NiO doped composite prticles is not yet cler. However, during seeded copolymeriztion in ethnol medium the prior formtion of P(MMA-GMA) primry prticles from secondry nucletion cn t e ruled out due to comprtively fster copolymeriztion rection etween MMA nd GMA. As the concentrtion of MMA nd GMA decresed towrds the end of the copolymeriztion functionlized NiO prticles prticipted in rection through vinyl groups, resulted in NiO doped composite prticles. It is lso evident tht NiO/ P(MMA-GMA) composite prticles re it polydispersed rnging from four to severl microns. Some smll clusters of free NiO prticles not prticipted in seeded copolymeriztion re lso visile. ) c) 0.6 μm 2 μm Figure 2. SEM photogrphs of NiO prticles ), functionlized NiO prticles ), nd NiO/P(MMA-GMA) composite polymer prticles c) FTIR is n estlished tool to detect the surfce properties of polymer prticles[38,39]. Figure 3 shows the FTIR spectr of functionlized NiO nd NiO/P(MMA-GMA) composite polymer prticles. These spectr were recorded for wshed smples in KBr pellets. The FTIR spectrum of functionl NiO shows sorption signl in the region cm -1 which indictes the formtion of metl-oxygen ond (Ni-O). Additionlly the rod nd diffuse nds ppered t round 3383 cm -1 nd 1630 cm -1 represent the existence of wter in NiO. The identifiction of Ni-O ond in the FTIR spectrum confirmed the structure of NiO. The smll sorption signl t 2912 cm -1 nd represents the liphtic C-H stretching virtion derived from oleic cid nd MPS. The spectrum of NiO doped composite polymer prticles shows strong sorption signls t 1724 cm -1 nd 1142 cm -1 due to chrcteristic C=O nd C-O stretching virtion of ester derived from MMA nd GMA comonomers. The wek sorption nds t round 960 cm -1 nd 833 cm -1 represent the presence of epoxy group from GMA. The signl intensity of liphtic C-H stretching virtion ppered t cm -1 incresed fter the copolymeriztion rection. Additionlly the oservnce of comprtively wek nd signl in the region cm -1 due to metl-oxygen ond in NiO indictes the formtion of ) 0.6 μm

4 86 Mohmmmd S. Hossn et l.: Preprtion of Epoxy Functionlized Hyrid Nickel Oxide Composite Polymer Prticles NiO doped composite polymer prticles. The chnge in chemicl environment slightly shifted this sorption signl. The presence of free NiO prticles not removed despite repeted wshing my lso contriute prtilly to this signl. NMR is etter instrumentl tool to check the composition of polymer. 1 H NMR spectrum of NiO/P(MMA-GMA) composite polymer recorded in CDCl 3 is shown in figure 4 fter removing the sedimented insolule NiO. The signls t 0.81 nd 1.78 ppm represent the C-CH 3 nd C-CH 2 -C proton signls of MPS, MMA nd GMA. The CH 3 -O-CO- proton signl of MMA nd the CH 2 -O-COproton signl of GMA ppered t 3.56 nd 4.25 ppm respectively. The chemicl shifts ppered t 3.16 nd 2.80 ppm indicted the presence of epoxy protons from GMA. Both signls re shifted to upfield due to shielding of protons s the exct conformtion of the solule polymer is unknown. It is known tht the chemicl shifts re vrile depend not only on the chemicl environment ut lso on concentrtion, temperture nd solvent. Figure 3. FTIR spectr of functionlized NiO prticles ) nd NiO/P(MMA-GMA) composite polymer prticles ) recorded in KBr pellets f g e d c CDCl 3 Figure 4. 1 H NMR spectr of NiO/P(MMA-GMA) composite polymer prticles tken in CDCl 3

5 Americn Journl of Polymer Science 2013, 3(5): The NiO prticles used to prepre functionl hyrid composite polymer prticles re pprecily crystlline in chrcter s shown even for MPS modified NiO prticles. The XRD spectrum of functionlized NiO prticles presented in figure 5 clerly shows the chrcteristic peks of cuic crystls locted t 37.5, 43.5, 62.8, 75.5 nd 79.8 corresponding to the (111), (200), (220), (311) nd (222) plnes[30,40]. The structure of polymer mtrix cn e est explined y considering the spectr otined t low ngle region tht gives ide out the morphous property. In functionlized NiO wek ut rod signl tht ppered t indicted the presence of MPS nd oleic cid lyer nd the intensity of this pek further incresed with the incorportion of P(MMA-GMA) component. This ehviour suggests tht morphous chrcter increses due to the formtion of hyrid inorgnic/orgnic polymer composites. Additionlly the strong chrcteristic signl of crystlline NiO supports the doping of NiO on the surfce of composite polymer prticles s visily oserved from SEM imge. It is to e dded tht signls ppered t 65 nd (represented y cross sign) in functionl NiO nd NiO/P(MMA-GMA) composite prticles respectively re rtefcts due to prolems with the detector. in the mesured temperture rnge, the percentge of residul inorgnic NiO content in NiO/P(MMA-GMA) composite polymer prticles is clculted to e roughly 34%. This numericl percentge is pretty high nd some free NiO not removed during wshing my lso contriute to this higher vlue. c Figure 6. TGA thermogrms of unmodified NiO prticles (reference mteril) ), functionlized NiO prticles ), nd NiO/P(MMA-GMA) composite polymer prticles Figure 5. X ry diffrction ptterns (XRD) of functionlized NiO prticles ) nd NiO/P(MMA-GMA) composite polymer prticles TGA ws used to confirm the incorportion of orgnic polymer in hyrid composite prticles. It is expected tht s the composite prticles re heted from mient temperture to 800 C the orgnic prt would e urned off nd the remining prt fter clcintion would represent the percentge of inorgnic mss i.e. NiO content. TGA curves re illustrted in figure 6. Compred to re NiO prticles (reference mteril) shrp ut smll trnsition is oserved t round 470 C in functionl NiO nd the weight loss is incresed y round 3.29%. This weight loss represents the inclusion of oleic cid nd orgnic frction of MPS in NiO. It is lso evident tht reltive to functionlized NiO seeded copolymeriztion of MMA nd GMA produced ig shrp trnsition in NiO/P(MMA-GMA) composite polymer prticles t round 287 C. Considering the complete decomposition of orgnic prt 4. Conclusions A simple three step process ws ttempted to prepre epoxy functionl NiO hyrid composite polymer prticles. The prticles were nmed s NiO/P(MMA-GMA) composite prticles. Nnosized NiO prticles were first prepred y liquid-phse process. NiO prticles were then functionlized with silne coupling gent nd finlly seeded copolymeriztion of MMA nd GMA ws crried out in ethnol medi. NiO doped epoxy functionl composite prticles were otined s confirmed y electron microgrphs, FTIR, NMR, XRD nd TGA nlyses. REFERENCES [1] J.W. Kim, J.W. Shim, J.H. Be, S.H. Hn, H.K. Kim, I.S. Chng, H.H. Kng, K.D. Suh, 2002, Titnium dioxide/poly (methyl methcrylte) composite microspheres prepred y in situ suspension polymeriztion nd their ility to protect gins UV rys. Colloid Polym. Sci., 280(6): [2] F. Cruso, 2001, Nno engineering of prticle surfces. Adv. Mter., 13(1): [3] N. Mnohrn, M.T. Elsesser, D.J. Pine, 2003, Dense pcking nd symmetry in smll clusters of microspheres. Science,

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