Ab. Rahman, Mohamad Zaki

Ahmad @ Ayob, Mansor

Haron, Md. Jelas

Silong, Sidik

Wan Badhi, Wan Ahmad

Wan Yunus, Wan Md. Zin

Universiti Putra Malaysia Institutional Repository

Chemical SciencesGraft Copolymerization of Vinyl Monomers onto Sago StarchWMZ Wan YunU5, M6 Ahmad, MZA Rahman, WA 6adhi, MJ Haron and S SilongFacultyof ScienceandEnvironmentalStudiesUniversitiPutraMalaysia43400 UPM,Serdang,SelangorMalaysiaE-mail ofCorrespondingAuthor:wanzin@fsas.upm.edu.myKey words: sago starch, graft copolymerization, vinyl monomer, characterisation.IntroductionGraft copolymerization of vinylmonomers onto a starch is an excellentmethod for preparing composites of. I 1·3 Dstarch with synthetic po ymers . e-pending on the type of monomers usedin the copolymerization reaction theproducts may be used as thickners,absorbents, sizes, adhesives, floccu-lants, resins and plastics. Althoughvarious monomers, such as methylacrylate, acrylic acid, hydroxyethylmethacrylate, acrylamide etc., havebeen successfully grafted onto starchfrom various sources (for example comand potatoes) there apparently no studyin this area has been done on sagostarch. Sago starch is one of our com-modities and is currently mainly usedfor food and food related products.Alteration starch properties by graftcopolymerization widens the scope ofits utilizations which consequentlyincrease its economic important. Theobjective of this study is to synthesizeand characterize of several graft co-polymers prepared from several vinylmonomers and sago starch.Materials and MethodsAll the monomers are purified bypassing them through activated alu-mina columns. Graft copolymerizationof these monomers onto sago starch iscarried out by a batch method using a250 mL three neck flask equipped witha mechanical stirrer, reflux condenserand thermostated water bath. Initiationprocess for the copol~erization. iscarried out using chemical techniques.To optimize the reaction conditions,effect of initiator concentration, reac-tion period, reaction temperature,monomer concentration and preswel-ling on the percentage of grafting andgrafting efficiency are investigated.Removal of homopolymer from thegrafted product is carried out by sol-vent extraction. The presence of func-tional groups on the polymer samplesis analyzed by FfIR spectroscopy.Thermal behavior of the polymers isexamined by TGA and DSC. Themorphology of the polymer surface isobserved by the scanning electron mi-croscope. Conversions of poly(methylacrylate)- and polytacrylonitrile)-grafted sago starches intopoly(hydroxamic acid) andpoly(amidoxime) chelating ion ex-change resins are carried out by treat-ing these starting polymers with hy-droxylamine solutions.Results and DiscussionOptimum conditions for grafting acry-lonitrile onto sago starch are as fol-lows: concentration of eerie ammo-nium nitrate, 9.52 x 10.3 moIL·I; con-centration of acrylonitrile, 0.50 moll.";reaction temperature, 50°C and reac-tion period, 90 min. FfIR spectrum ofpoly acrylonitrile grafted starch clearlyshows a sharp absorption peak at2244cm·1 which indicates the presenceof nitrile group in the copolymer sug-gesting that polyacrylonitrile is suc-cessfully grafted onto the starch. Thisconclusion is also supported by TGAand DSC data. The percentage ofgrafting and grafting efficiency underthe optimum conditions are 82 and96% respectively.Higher maximum percentage of graft-ing is obtained when methyl acrylate isgrafted onto sago starch. It is 130%,which is about 50% higher comparedwith the percentage for the polyacrylo-nitrile-sago starch system. The ex-perimental conditions to obtain themaximum percentage of grafting ofmethyl acrylate are as follows: con-centration of eerie ammonium nitrate,8.77 x 10.3moll,", concentration of themonomer, 0.80 moIL·I; reaction tem-perature, 50°C and reaction period, 60min. FfIR study of the purified co-polymer clearly indicates the presenceof carbonyl group suggesting thatpolymethyl acrylate is sucessfullygrafted on the backbone polymer ascarbonyl group is only originated fromthe monomer. The different thermalbehaviour of the original polymer andthe graft copolymer, observed fromDSC and TO thermograms, also sup-ports that the grafting reaction is sue-cesfully carried out. The grafting effi-ciency for grafting methyl acrylate ontosago starch under the optimum reactionconditions is 82%.Although polystyrene can be alsografted onto this starch, its percentageof grafting is only 54%, which is lowerthan the percentages for grafting poly-acrylonitrile and polymethyl acrylate.The optimum conditions for obtainingthe above percentage of grafting are:concentration of eerie ammonium ni-trate, 8.00 x 10.3 moIL·I; concentrationof styrene, 1.75 moll,", reaction tem-perature, 50°C and reaction period, 120min. The presence of the styrene com-ponent on the grafted product is verydifficult to detect directly from itsFfIR spectrum, probably due to theinsufficient amount of the styrene to bedetected. The FfIR spectrum of thehydrolysed (to remove the starch com-ponent from the copolymer) product isidentical to the pure polystyrene spec-trum. This indicates that the styrene issuccessfully grafted onto the sagostarch. The grafting efficiency of thiscopolymerization is 73%.Studies on the preparation of 2-hydroxyethyl methacrylate(HEMA)grafted sago starch are conducted usingeerie ammonium nitrate(CAN) andpotassium persulphate(PPS) as the freeradical initiators under a nitrogen at-mosphere. The optimum conditions forHEMA grafting onto sago starch usingCAN as an initiator are as follows:reaction period, 3h; reaction tempera-ture, 40oC; HEMA amount, 0.17 mol;CAN amount, 1.00 mmol. Meanwhilethe conditions for the copolymer prepa-ration using PPS an initiator are asfollows: reaction period, 2h; reactiontemperature, 40oC; amount of PPS,243UPM Research Report 1997-2000, Section 2-Extended Abstracts5.00 mmol and amount of HEMA, 0.05mol. The percentage of grafting andgrafting efficiency under optimumconditions for CAN initiation are 200%and 46% whereas for PPS initiation are406% and 63% respectively.Acrylic acid and methyl acrylate arealso grafted onto sago starch using PPSas the initiator. The graft yields forboth copolymerisations were reactionconditions dependent. Optimum condi-tions are: reaction temperature, 40°C;reaction period, 1.5h; amount of ini-tiator, IOmmol and amount monomer,0.02 mol for poly(acrlic acid)graftedsago starch and reaction temperature,50°C; reaction period, 1.5h; amount ofthe monomer, 0.09 mol and amount ofPPS, 8.33mmol for poly(methyl ac-rylate) grafted sago starch. TGA stud-ies show that the grafted sago starchesexhibit different thermal behavior ascompared to gelatinised sago starch.SEM micrographs indicate that bothacrylic acid and methyl acrylate arehomogenously grafted onto the starch.Poly(hydroxamic acid) andpoly(amidoxime) chelating ion-exchange resins are successfully pre-pared from poly(methyl acrylate)- andpolytacrylonitrile)- grafted sagostarches. Both resins show high bind-ing metal ion capacities and rapid rateof metal 'ion extraction. The sorption ofthese resins towards metals ions werepH dependent and together with theirhigh capacity and good kinetics ofextraction, this could be used for metalion extractions and separations. Thewater absorbency study ofpoly(hydroxamic acid) resin indicatesthat its water absorption capacity ispoly(methyl acrylate) content depend-ent. The water absorbency of I92g1g isobtained at 69% of poly(methyl ac-rylate).ConclusionsAcrylonitrile, methyl acrylate, HEMA,acrylic acid and styrene are success-fully grafted onto sago starch by freeradical copolymerizations. Experi-mental conditions (temperature, reac-tion period and concentrations of themonomers, the backbone polymer andthe initiator) are important parametersto determine the percentage of graftingand grafting efficiency. Poly(methylacrylate)- and poly(acrylonitrle)-grafted sago starches were successfullyconverted into poly(hydroxamic acid)and poly(amidoxime) chelating ion-exchange resins.244Benefits from the studyPolyacrynitrile, polymethyl acrylate,poly(HEMA), poly(acrylic acid) andploy(styrene) grafted sago starches arenew materials produced from sagostarch. These copolymers are potentialraw materials for many industriallyimportant applications. This study alsoindicates that poly(methyl acrylate)-and polytacrylonitrlej-grafted sagostarches can be used to prepare che-lating ion exchange resins and hydro-gels.Literature cited in the textNone.Project Publications inRefereed JournalsLutfor, M.R. Sidik, S., Wan Md. Zin, W.Y.,Mohd. Zaki, A.R. Mansor, A. and Md.Jelas, H. 2000. Metal ions binding bychelating ligands from new polymerbearing amidoxime fuctional groups. J.Chem. Research (S). 52-53.Lutfor, M.R., Sidik S., Wan Md. Zin, W.Y.,Md. Jelas, H. Mohd. Zaki A.R. andManser, A. 2000, Modification of sagostarch by graft copolymerization: Effectof reaction condition on graftingparameter. International Journal ofPolymeric Materials. 1-13.Lutfor, M.R., Sidik S., Wan Md. Zin, W.Y.,Mohd. Zaki, A.R., Manser, A. and Md.Jelas, H. 200 I. Kinetics of graftcopolymerization of acrylonitrile ontosago starch using free radicals initiated by. eerie ammonium nitrate. DesignMonomers and Polymers. 4(3): 253-260.Lutfor, M.R., Sidik S., Wan Md. Zin, W.Y.,Mohd. Zaki, A.R., Mansor, A. and Md.Jelas, H. 200 I. Synthesis andcharacterization of poly(hydroxamic acid)chelating resin from poly(methyl acrylate)grafted sago starch. Journal of AppliedPolymer Science. 79: 1256-1264.Lutfor, M.R., Sidik S., Wan Md. Zin, W.Y.,Mohd. Zaki, A.R., Mansor, A. and Md.Jelas, H. 2000. New polymer bearinghydroxamic acid chelating resin forbinding of heavy metal ions. Journal ofChemical Research (S). 552-553.Lutfor, M.R., Sidik, S., Wan Md. Zin, W.Y.,Mohd. Zaki A.R., Mansor A. andMd.Jelas, H. 1999. Kinetics andmechanism of free radical grafting ofmethyl acrylate onto sago starch. Journalof Applied Polymer Science. 77(6): 784-791.Lutfor, M.R., Sidik, S., Wan Md. Zin, W.Y.,Mohd. Zaki A.R., Mansor A. andMd.Jelas, H. 2001. Preparation andswelling of a polymeric absorbentcontaining hydroxamic acid group frompolymer grafted sago starch.Carbohydrate Polymers. 45: 95-100.Lutfor, M.R., Sidik, S., Wan Md. Zin, W.Y.,Mohd. Zaki A.R., Mansor A. andMd.Jelas, H. 2000. Preparation andcharacterization of poly(amidoxime)chelating resin from poly(acrylonitrile)grafted sago starch. European PolymerJournal. 36: 2105-21"13.Lutfor, M.R., Sidik, S., Wan Md. Zin, W.Y.,Mohd. Zaki, A.R., Manser, A. and Md.Jelas, H. 1999. Graft copolymerization ofmethyl acrylate onto sago starch usingeerie ammonium nitrate as an initiator.Journal of Applied Polymer Science.761(4): 516-523.Mohd. Zaki A.R., Lutfor, M.R., Wan Md.Zin, W.Y., Mansor, A. and Md. Jelas, H.2000. Separation of copper, iron, cobaltand cadmium using poly(hydroxamicacid) chelating resin. Oriental Journal ofChemistry. 16(1): 47-52.Mostafa, KM.1995. Graft polymerization of acrylic acidonto starch using potassium permanganateacid (redox system) J. Polym.Sci.56: 263-269.Najjar, A.M.K., Wan Md. Zin, W.Y.,Mansor, A. and Mohd. Zaki, A.R. 2000.Preparation and characterization ofpoly(2-acrylamido-z-methyl propane-sulforic grafted chitosan using potassi umpersulfate as redox initiator. Journal ofApplied Polymer Science. 77(10): 2314-2318 .Project Publications inConference ProceedingsAb Rahman, M.Z, Lutfor, M.R., Haron,M.J., Silong, S.,.Wan Yunus, W.M.Z. andAhmad. M.B. 2000. Sago starch basedpoly(hydroxamic acid) resin for extractionof lanthanide group elements fromaqueous media Abstr: 13"' MalaysianAnalytical Chemistry Symposium, PortDickson, Negeri Sembilan, 6-7 September2000.Ab Rahman, M.Z.M., Lutfor, R, Silong, S.,Wan Yunus, W.M.Z., Ahmad, M. andHaron, MJ. 1999. Sago starch-graftedpolyacrylonitrile in the preparation ofresins for metal ions extraction.Proceeding: Malaysian Science &Technology Congress 99, Kuching,Sarawak, 8-10 November 1999.Abduel Majid K. Najjar, Wan Md. Zin WanYunus, Mansor B. Ahmad and MohamadZaki Ab. Rahman. Preparation ofhydrogels by Graft Copolymerization ofChemical SciencesMethyl-2-Acrylamido-2-MethoxyacetqteOnto Sago Starch. Simposium PolimerKebangsaan 200 I. Inst. Keselamatan danKesibatan Pekerjaan Negara, Bangi, 2-3Oktober 2001.Haron, M.J .• H.A. Hamid. Ahmad. M.•WanYunus, W.M.Z. and Ab. Rahman M.Z.1998. Preparation of polybydroxamic acidion exchanger from polyacryl amidestarch copolymer. Industrial ChemistrySeminar VI. October 13. UPM.Janarthanan, P.•Wan Yunus, W.M.Z .•Ahmad. M .• Rahman. M.B.A .• Haron,M.J. and Silong. S. 1998. Sorptionbehaviour of styrene grafted sago starchin various solvents. Inter. Sci. Conf. May7-9.1998. UPM.Lutfor Rahman. Sidik Silong, Wan Md ZinWan Yunus, M. Zaki Ab Rahman.Mansor Ahmad and Jelas Haron. 1998Synthesis and Application ofPoly(bydroxamic acid) Resin fromPoly(methyl acrylate) Grafted SagoStarch. Proceeding: International Sci.Conf. Kuala Lumpur. 7-9 May 1998.M.Z. Ab. Rahman. F.A. Abu Iiaiwi, M.Ahmad. and W.M.Z. Wan Yunus (1998).Preparation and characterization ofpolyacrylonitrile and polymethacrylategrafted sago starch. Malaysian AnalyticalChemistry Symposium-XI. Nov. 4-5.UTM.Johor.Mohammad Zaki Ab. Rahman. Isam Y.M.Qudsieh. Wan Md. Zin Wan Yunus,Mansor Ahmad dan Sidik Silong. 1999.Pengkopolimeran cangkukanpoli(metakrilat) ke atas kanji sagumenggunakan sistem bahan pemulakalium persulfat dan cerik ammoniumnitrat. Abstr, Simposium Kimia AnalisisMalaysia Ke-12. 7-8 September 1999.Kuala Terengganu. pp. 98.Rafeadah Rusli, Wan Md Zin Wan Yunus,Mansor Ahmad dan Mohd ZakiAb.Rahman. 1998. PengkopolimeranCangkuk 2-Hidroksietil Metakrilat keAtas Kanji Sago. Proceeding: 111hMalaysian Analytical ChemistrySymposium. Universiti TeknologiMalaysia. Skudai, Johor, 4-5 Nov. 1998Rafeadah Rusli. Wan Md. Zin Wan Yunus,Mansor Ahmad and Mohd. Zaki AbdulRahman. 1999. Pengkopolimerancangkuk 2-hidroksietil metakrilat ke ataskanji sagu. Abstr. Simposium KimiaAnalisis Malaysia Ke-12. 7-8 September1999. Kuala Terengganu. Pp. 63.Rafeadah Rusli, Wan Md. Zin Wan Yunus,Mansor Ahmad and Mohd. Zaki AbdulRahman. 1999. Preparation andcharacterization of sago starch-graft-poly(2-hydroxyethyl methacrylate).Abstr. Malaysian Science and TechnologyCongress'99, 25-27 October 1999. KualaLumpur.Wan Md. Zin Wan Yunus, Yiam ChongBin. Md. Jelas Haron and Sidik Silong.Sintesis Berenzim Resin Penukar IonPoli(Asid Hidroksamik) Dari KopolimerKanji-Poli(Metil Akrilat). Seminar KimiaAnalisis Malaysia Ke-14. CenturyMahkota Melaka, 11-13 Sept. 200 1.Wan Yunus, W.M.Z. 2000. Penyediaan danPencirian Beberapa Kopolimer CangkukKanji Sagu-Vinil Monomer. Proceeding:13th Malaysian Analytical ChemistrySymposium. Port Dickson. NegeriSembilan, 6-7 September 2000.Wan Yunus, W.M.Z .•Rahman. M.L .•Rahman. M.Z.A .• Ahmad. M.• Silong, S.•Kassim, A. and Wan Badhi. W.A.I997.Graft copolymerization of methacylateonto sago starch. Abstract of ResearchSeminar. UPM.Wan Zin Wan Yunus, Fazliana Abd. Hamidand Mohd. Nazri Saidin. Preparation andCharacterization of Composite Material.Seminar Kimia Industri Ke-VIII. UPMSerdang, 19 Sept. 200 I.Yiam Chong Bin. Wait Mq. Zin WanYunus, Md. Jelas Haron and SidekSilong. 1999. Pengkopolimeran cangkukmetil akrilat ke atas kanji sagu denganmenggunakan kalium persulfat sebagaipemula. Abstr. Simposium Kimia AnalisisMalaysia Ke-l Z, 7-8 September 1999.Kuala Terengganu, pp. 53.Yiam Chong Bin. Wan Md. Zin WanYunus, Md. Jelas Haron and SidekSilong. 1999. Graft copolymerization ofacrylic acid onto sago starch usingpotassium persulphate as an initiator.Abstr. Malaysian Science and TechnologyCongress'Ps, 25-27 October 1999. KualaLumpur.Graduate ResearchAbdul Majid K. Najjar. (Ongoing). PolymerThesis write-up. Chemistry [Ph.D.J.Universiti Putra Malaysia.Rafaedah Rusli. 2000. Polymer Chemistry[M.S.I. Universiti Putra Malaysia.Yiam Chong Beng. 2000. PolymerChemistry [M.S.I. Universiti PutraMalaysia.Isam Yassin Mahmood Qudsieh. 1999.Polymer Chemistry [M.S.I. UniversitiPutra Malaysia.Lutfor Ab. Rahman. 1999. PolymerChemistry [Ph.D.I. Universiti PutraMalaysia.Pushparnalar alp Jonarthanan. 1999.Polymer Chemistry [M.S.I. UniversitiPutra Malaysia.245

Graft copolymerization of vinyl monomers onto sago starch

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Graft copolymerization of vinyl monomers onto sago starch

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