<=>/30< 87 9-56 835 ?3=2 <90.3-5 ;010;07.0 =8 37=0;0<==0;313.-=387 2@KHOHL -ACRJ 4HEJH - =GDPHP <RAKHQQDC EMO QGD /DFODD ME 9G/ @Q QGD >LHSDOPHQV ME <Q" -LCODTP %*)% 1RJJ KDQ@C@Q@ EMO QGHP HQDK HP @S@HJ@AJD HL ;DPD@OBG,<Q-LCODTP+1RJJ=DUQ @Q+ GQQN+##ODPD@OBG!ODNMPHQMOV"PQ!@LCODTP"@B"RI# 9JD@PD RPD QGHP HCDLQHEHDO QM BHQD MO JHLI QM QGHP HQDK+ GQQN+##GCJ"G@LCJD"LDQ#%$$&’#&*(% =GHP HQDK HP NOMQDBQDC AV MOHFHL@J BMNVOHFGQ STUDIES ON PALM OIL WITH SPECIAL REFERENCE TO INTERESTERIFICATION being a Thesis presented by HAlv1IRIN ABDUL KIFLI, M.Sc. to the UNIVERSITY OF ST. ANDREWS in application for THE DEGREE OF DOCTOR OF.PHILOSOPHY February 1981 SUMMARY Interesterification which can be considered as the removal of fatty acids at random from glyceride molecules, the shuffli.ng of these acids and their replacement of the glyceride m.olecules, has been investigated for palrn oil, palrn oil fractions and palm oil mixed with other vegetable o11s. The reaction 'has been 0 effected at 90 C in the presence o£ sodium. methoxide as a catalyst. Pancreatic lipolysis has been ernployed to check the completene s s of the reacti.on. On cOluplete :candornisation, the fatty acid composition. of the 2-position is the sarne as that of the whole fat either before 014 after interestel'ification. The changes in the glyceride cO:tYlposition resulting fron'1 interesterification have been exarnined by various standard technique s. Silver ion thin layer chron'1atography which separates glycerides according to their degree of unsaturation has been used extensively. Using luethyl heptadecanoate as an internal standard various com.ponent glyc,erides have been ", " ~ ··;.{Y' quantified. . GLG of glycerides has als~,l1!s~nused to study the . ''''?;'~ changes in glyceride composition of fats cont£'tning a wide ". range of fatty acid cOluposHion. The application of thin layer chromatography, usi.ng methy_l heptadecanoate as an interncll standard, ha.s aiso been extended to deterrnine the esters for.r-ned during interesterification when sodiur:n. methoxide is used as a catalyst. The changes in physical properti.es which resuE from interestel'ification have been determined by NMR (solids .fat content) and DSC (thermal behaviour). Attempts to prepare a mixture of fats and oils containing palm oil and / or palm oil fraction s which simulate s vanaspati have been made. Many rnixtul'es have been subjected to interesterification and the physical properties of the products have been investigated using NMR for all the mixtures and DSC of selected mixtures. The SFC curve of each rnixture has been compared with that of vana spati. Some potentially useful mixtures are recognised. Stereospecific glyceride analysis of various types of palm oils has also been carried out using Brockerhoff1 s method. This involves partial deacylation of the triacylglyce!'ols, i.solation of the a,l3-diacylglycerols, conversion of these diacylglycerols to phospholipid derivatives and finally stereospecific hydrolysis by Phospholipase A from fmake Z venom, The possible component glycerides have then been z- computed as suming a i-random, random, 3.:. random distribution of the fatty acids found in each of these positions. The results have been discussed in tenus of double bond nUluber and of carbon nunlber: The latter has been compared with results obtained by gas chromatography of the whole oil. To Atasha and Siti Anabaena DEC LARA TICYN I hereby declare that this thesi-s is a record of the results of my own experirnentG, that it is my own composi.tion, and that it has not previously been presented ill application for a higher degree. The research was carried out in the Chemistry Research Department of the University of St. Andrews under the direction of Professor F.D. Gunstone, D.Sc. ,F.R.I.C. C ERTIFIC P.T.E I hereby certify that Mr. Hamil'in Abdul Kifli has spent twelve terms at reseaJ:ch work under my supervision, has fulfilled the conditions of the Resolution of the University Court No.1 (1967) and that he is qualified to subm.it the accompanying thesis in application for the degree of Doctor of Philo s oph y. Re search Supervi sor LECTURE "The Compo sition and Physical Behaviour of Fats Before and After Interesterificz"Ltion With Special Reference to Palm Oilll B.A. Kifli and F.D. Gunstone, presented to the ISF/AOCS Congress, New York,April 28th, 1980. ACKNOWLEDGEMENTS I wish to express xny sincere grc(titude to Professor F.D. Gunstone for his continued supervisi.on, guidance and assistance throughout this research and writing of this thesis. I wish also to record my sincere thanks and appreciation to Dr. Charlie Scrimgeour for much practical advice and discussion atthebencli., toMr. OhChuanHo and Mr. K.G. Berger of Pall"n Oil Research Institute of Malaysia and also to Dr. F.B. Padley of Unilever Research, Colworth House, Bedford, England; for their assistance in NMR and DSC analyses. Thanks must also be expressed to Pepe (E. Ba(3cetta) for his help and good company, to Andrew Watson for his help in photographic work and to Mr s. VV ilma Pogorzelec for typing this thesis. I must also express my deepest thanks and appreciation to rny wife, Atasha, for hel' artistic talent and for sacrificing many long hours in drawing all graphs and histograms of this the si s. Finally, I must convey my gratitude to the Director General of the Palm Oil Research lnst,i.tute of Malaysia for the study grant and full pay study leave. CONTENTS A bbreviations and Footnote 8 i Sumrnary ii CHAPTER ONE - General Introduction of Palm Oil 1 CHAPTER TWO - Interesterification Studies 8 General Introduction 8 Interesterification 8 Directed Interesterification 10 Randorn Intere sterification 12 Application of Random Interesterification 14 Nutriti.onal Evaluation of Interesterified Fats and Oils 16 Results and Discussion Method s of Follo\ving the Proce S8 and Examining the Products 17 Mechanism of Intere8terification U sing Sodium Methoxide as a Catalyst 23 Changes in Glyceride Composition DuX'ing Interesterification 25 + Ag TLC 25 Lipolysis 34 GLC of Triglycerides 37 Formation of Methyl Esters During Interesterification 46 Physical Properties of Int,eresteri£i.ed Fats and Oils 49 Thermal Properties by DSC Analysis 55 CHAPTER THREE - Atternpts to Prepare a Mixture of Fats and Oils Containing Palm Oil and/or Palm Oil-Derived Fraction which Simulates Vanaspati. 63 Introduction 63