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UNIVERSITI PUTRA MALAYSIA
DEVELOPMENT OF PALM METHYL ESTER MICROEMULSIONS AS AEROSOL INSECTICIDES
ROHANA OTHMAN
FS 2015 53
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DEVELOPMENT OF PALM METHYL ESTER MICROEMULSIONS
AS AEROSOL INSECTICIDES
By
ROHANA BINTI OTHMAN
Thesis Submitted to the School of Graduate Studies, Universiti Putra Malaysia,
in Fulfilment of the Requirements for the Degree of Master of Science
October 2015
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COPYRIGHT
All material contained within the thesis, including without limitation text, logos, icons,
photographs and all other artwork, is copyright material of Universiti Putra Malaysia
unless otherwise stated. Use may be made of any material contained within the thesis for
non-commercial purposes from the copyright holder. Commercial use of material may
only be made with the express, prior, written permission of Universiti Putra Malaysia.
Copyright © Universiti Putra Malaysia
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Abstract of thesis presented to the Senate of Universiti Putra Malaysia in fulfillment of
the requirement for the Degree of Master of Science
DEVELOPMENT OF PALM METHYL ESTER MICROEMULSIONS
AS AEROSOL INSECTICIDES
By
ROHANA BINTI OTHMAN
October 2015
Chairman : Prof. Mahiran Basri, PhD
Faculty : Science
Palm methyl ester microemulsions are used as a basis for preparing aerosol insecticides
against domestic insect pests due to their favourable characteristic such as renewable
resources, biodegradable, non-flammable, and less or non-toxic to end users. The study
focuses on the development of microemulsion-insecticides using palm-based materials
as the oil phases, emulsifiers and/co-emulsifier, and apply them as a basis for preparing
aerosol insecticides for household uses. The work includes utilization of palm-based
materials containing mixed Tween 80 and Dehydol LS2 (Tween 80:DLS2) at ratios of
70:30, palm methyl esters (PME), deionized water (DH2O), and 1-propanol as a co-
surfactant (Tween 80:DLS2/PME/DH2O/1-propanol) for preparing water in oil (W/O)
and oil in water (O/W) microemulsion (µE) solutions. It involves screening process,
ternary phase diagram study, physico-chemical characterizations of microemulsions,
formulating and preparing microemulsion-insecticides as aerosol-insecticides, and
bioefficacy test of the formulated products on insect pests. The optimum compositions
and concentrations for both W/O-µE and O/W-µE solutions showed very clear
appearance and thermodynamically stable at ambient and high temperatures (45ºC) as
well as low in viscosity and very small particles with nano size. Ternary phase diagrams
systems containing mixed Tween 80:DLS2/PME/DH2O/1-propanol showed large
isotropic regions. The optimum compositions for W/O-µE solution were at the range of
20% mixed Tween 80:DLS2 (70:30); 20%-25% PME; 47.5%-40% DH2O; 12.5%-15%
1-propanol while for O/W-µE solutions, the optimum compositions were at the range of
7.5%-12.5% mixed Tween 80:DLS2 (70:30); 5%-7.5% PME; 77.5%-70% DH2O; 10%
1-propanol. Both systems were used to formulate W/O-µE and O/W-µE aerosol
insecticides to control flying insects such as Aedes Aegypti mosquitoes and crawling
insects such as Periplaneta Americana cockroaches respectively. The physical stability
and the mist behaviour of the palm methyl esters aerosol insecticides were studied.
There were very fine mist (30-50 microns) suspended longer in the air (6-8 seconds)
observed with no water droplet released and no foam formation. These properties made
them very suitable to be applied as flying insect killer (FIK) and crawling insect killer
(CIK) aerosol-spray products. The bioefficacy test on both products showed good
performance in knocking down insects by 100%, 24 hours of mortality rate as compared
to the Malaysian Standard Aerosol. In conclusion, this system consisting mixed non-
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ionics surfactants, PME, and non-toxic co-surfactant has great potential to be used in
preparing palm methyl esters aerosol insecticides which are more environmental and
end-users friendly.
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Abstrak tesis yang dikemukakan kepada Senat Universiti Putra Malaysia sebagai
memenuhi keperluan untuk Ijazah Master Sains
PENGHASILAN MIKROEMULSI METIL ESTER KELAPA SAWIT
SEBAGAI RACUN SERANGGA AEROSOL
Oleh
ROHANA BINTI OTHMAN
Oktober 2015
Pengerusi : Profesor Mahiran Basri, PhD
Fakulti : Sains
Mikroemulsi metil ester kelapa sawit digunakan sebagai asas untuk menyediakan racun
serangga aerosol bagi mengawal serangga perosak domestik disebabkan ciri-cirinya
yang bagus seperti sumber yang boleh diperbaharui, mesra alam, tidak mudah terbakar,
dan kurang atau tidak berbahaya kepada pengguna. Kajian ini menekankan penghasilan
mikroemulsi-racun serangga menggunakan bahan berasaskan kelapa sawit sebagai
minyak, pengemulsi dan/pengemulsi bersama dan digunakan sebagai asas untuk
menghasilkan racun serangga aerosol untuk digunakan di rumah. Kajian ini termasuklah
penggunaan bahan berasaskan kelapa sawit yang mengandungi campuran Tween 80 dan
Dehydol LS2 pada nisbah 70:30 (Tween 80:DLS2), metil ester kelapa sawit (PME), air
ternyahion (DH2O), dan 1-propanol sebagai surfaktan bersama (campuran Tween
80:DLS2/PME/DH2O/1-propanol)untuk menyediakan larutan mikroemulsi (μE) air
dalam minyak (W/O) dan larutan mikroemulsi (μE) minyak dalam air (O/W). Ia
melibatkan proses saringan, kajian gambarajah tiga fasa, pencirian sifat kimia fizik
mikroemulsi, memformulasi dan menghasilkan mikroemulsi-racun serangga sebagai
racun serangga aerosol, dan ujian bioefikasi produk yang diformulasi terhadap serangga
perosak. Komposisi dan kepekatan optimum untuk kedua-dua larutan W/O-μE dan
O/W-μE menunjukkan larutan yang sangat jelas dan stabil secara termodinamik iaitu
stabil pada suhu biasa dan suhu yang tinggi (45ºC) dan juga rendah kelikatan serta zarah
yang sangat kecil dengan saiz nano. Sistem gambar rajah tiga fasa yang mengandungi
campuran Tween 80:DLS2/PME/DH2O/1-propanol menunjukkan kawasan isotropik
yang besar. Komposisi optimum untuk larutan W/O mikroemulsi (μE) berada pada julat
20% campuran Tween 80:DLS2 (70:30); 20%-25% PME; 47.5%-40% DH2O; 12.5%-
15% 1-propanol manakala bagi larutan O/W mikroemulsi (μE), komposisi optimum
berada pada julat 7.5%-12.5% campuran Tween 80:DLS2 (70:30); 5%-7.5% PME;
77.5%-70% DH2O; 10% 1-propanol. Kedua-dua sistem ini telah digunakan untuk
memformulasi W/O-μE dan O/W-μE racun serangga aerosol masing-masing untuk
mengawal serangga jenis terbang seperti nyamuk Aedes Aegypti dan serangga jenis
merayap seperti lipas Periplaneta Americana. Kestabilan dan sifat fizikal kabus racun
serangga aerosol berasaskan metil ester kelapa sawit telah dikaji. Kabus yang sangat
kecil (30-50 microns) dilihat stabil di udara (selama 6-8 saat) tanpa sebarang titisan air
dibebaskan dan tiada pembentukan buih. Ciri ini menjadikan larutan ini sangat sesuai
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untuk digunakan bagi membunuh serangga terbang (FIK) dan membunuh serangga
merangkak (CIK) (produk semburan aerosol). Ujian bioefikasi pada kedua-dua produk
menunjukkan prestasi yang baik dengan membunuh serangga pada kadar kematian
100% dalam masa 24 jam berbanding dengan Aerosol Standard Malaysia.
Kesimpulannya, sistem ini yang terdiri daripada campuran surfaktan bukan ionik, PME,
dan surfaktan bersama yang tidak berbahaya mempunyai potensi yang besar untuk
digunakan dalam penyediaan racun serangga aerosol berasaskan metil ester kelapa sawit
yang lebih mesra pengguna dan alam sekitar.
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ACKNOWLEDGEMENTS
Firstly of all, in the name of Allah, The Most Merciful and The Most Gracious, I am so
thankful for giving me the strength and patience to complete my laboratory work and
preparation of this thesis. Here, I would like to express my profound gratitude and
deepest appreciation to my supervisor, Prof. Dr. Mahiran Basri for her guidance,
invaluable advices, and constructive comments which kept me on a right track.
Besides that, I would like to express my appreciation to my co-supervisor, Dr. Ismail
Ab. Raman from Malaysian Palm Oil Board (MPOB) for his continuous guidance,
constant support, and constructive encouragement throughout this project. I would also
like to thank Advanced Oleochemical Technology Division (AOTD) for providing the
financial support and other facilities under the MPOB Graduate Students Assistantship
Scheme (MPOB GSAS).
I am also grateful to the staff of AOTD, Mrs. Zuraini, Mrs. Rosmah and Mr. Shamsual,
also to the staff of Institute Bioscience (IBS), UPM, Mrs. Norhayati Yusuf who guided
and helped me to complete the requirement for this project and their kindness for
providing the facility of the various analyses of my samples.
Special thanks to my colleagues, Nor Farhana Nazarudin, Lim Rui Rui, Wong Siew Pui,
Loo Chew Hung, and many others for their continuous encouragement, inspirations,
cooperation and support whenever I need.
Last but not least, to my husband, Mohammad Zhafran Zainal, my daughter, Zahratun
Nisa’, and my family for their encouragement, endlessly supporting, love, and prayers
throughout my study at Universiti Putra Malaysia. Your patience is greatly appreciated.
Thank you so much.
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The thesis was submitted to the Senate of Universiti Putra Malaysia and has been
accepted as fulfilment of the requirements for the degree of Master of Science. The
members of the Supervisory Committee were as follows:
Mahiran Basri, PhD
Professor
Faculty of Science
Universiti Putra Malaysia
(Chairman)
Siti Salwa Abd. Gani, PhD
Senior Lecturer
Faculy of Science
Universiti Putra Malaysia
(Member)
Ismail Ab. Raman, PhD
Principal Research Officer
Advanced Oleochemical Technology Division
Malaysian Palm Oil Board
(Member)
BUJANG KIM HUAT, PhD
Professor and Dean
School of Graduate Studies
Universiti Putra Malaysia
Date:
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Declaration by graduate student
I hereby confirm that:
this thesis is my original work;
quotations, illustrations and citations have been duly referenced;
this thesis has not been submitted previously or concurrently for any other degree at
any other institutions;
intellectual property from the thesis and copyright of thesis are fully-owned by
Universiti Putra Malaysia, as according to the Universiti Putra Malaysia (Research)
Rules 2012;
written permission must be obtained from supervisor and the office of Deputy Vice-
Chancellor (Research and Innovation) before thesis is published (in the form of
written, printed or in electronic form) including books, journals, modules,
proceedings, popular writings, seminar papers, manuscripts, posters, reports, lecture
notes, learning modules or any other materials as stated in the Universiti Putra
Malaysia (Research) Rules 2012;
there is no plagiarism or data falsification/fabrication in the thesis, and scholarly
integrity is upheld as according to the Universiti Putra Malaysia (Graduate Studies)
Rules 2003 (Revision 2012-2013) and the Universiti Putra Malaysia (Research)
Rules 2012. The thesis has undergone plagiarism detection software.
Signature: _____________________ Date: __________________
Name and Matric No.: Rohana Binti Othman, GS29326
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Declaration by Members of Supervisory Committee
This is to confirm that:
the research conducted and the writing of this thesis was under our supervision;
supervision responsibilities as stated in the Universiti Putra Malaysia (Graduate
Studies) Rules 2003 (Revision 2012-2013) were adhered to.
Signature:
Name of Chairman
of Supervisory
Committee:
Professor Dr. Mahiran Basri
Signature:
Name of Member
of Supervisory
Committee:
Dr. Siti Salwa Abd. Gani
Signature:
Name of Member
of Supervisory
Committee:
Dr. Ismail Ab. Raman
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TABLE OF CONTENTS
Page
ABSTRACT i
ABSTRAK iii
ACKNOWLEDGEMENTS v
APPROVAL vi
DECLARATION viii
LIST OF TABLES xiii
LIST OF FIGURES xv
LIST OF ABBREVIATIONS xvii
CHAPTER
1 INTRODUCTION 1
1.1 Background of Research 1
1.2 Statement of Problems 3
1.3 Scope of Study 3
1.4 Objectives 4
2 LITERATURE REVIEW 6
2.1 Surfactants and Their Properties 6
2.1.1 General Classification of Surfactants 6
2.1.1.1 Anionic Surfactants 7
2.1.1.2 Nonionic Surfactants 7
2.1.1.3 Cationic Surfactants 8
2.1.1.4 Zwitterionic Surfactants 8
2.1.2 Properties of Surfactants in Aqueous Solutions 8
2.2 Micelle Formation 9
2.3 Microemulsions versus Nanoemulsions 10
2.4 Microemulsions 12
2.4.1 Formation of Microemulsions 12
2.4.2 Phase Behaviour of Microemulsions 13
2.4.3 Applications of Microemulsions 13
2.4.3.1 Microemulsion in Detergency 14
2.4.3.2 Microemulsion in Cosmetics and
Pharmaceuticals
14
2.4.3.3 Microemulsion in Agrochemicals 15
2.5 Microemulsion as Aerosol Insecticides 15
2.5.1 Advantages of Microemulsions as Aerosol Insecticides 16
2.6 The Insecticide Aerosol 16
2.6.1 Types of Formulations 17
2.6.2 Chemical Components 18
2.6.2.1 Active Ingredients 18
2.6.2.2 Solvents 21
2.6.2.3 Liquid Propellants 22
2.6.3 Types of Aerosols 22
2.6.3.1 Oil-based Aerosols 22
2.6.3.2 Water-based Aerosols 23
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3 EXPERIMENTAL 24
3.1 Materials 24
3.2 Methods 24
3.2.1 Screening Process 24
3.2.1.1 Effect of Surfactant Ratio for W/O
Microemulsions System
(PME/Surfactant/Water Systems)
24
3.2.1.2 Effect of Surfactant Ratio for O/W
Microemulsions System
(PME/Surfactant/Water/Co-S Systems)
25
3.2.2 Phase Behaviour Study 25
3.2.2.1 Construction of Ternary Phase Diagram for
W/O Microemulsions Systems
(PME/S1:S2/Water Systems)
25
3.2.2.2 Construction of Ternary Phase Diagram for
O/W Microemulsions Systems
(PME/S1:S2/Water/Co-S Systems)
26
3.2.3 Physicochemical Characterization of Microemulsions 27
3.2.3.1 Conductivity Measurement 27
3.2.3.2 Viscosity Measurement 28
3.2.3.3 pH Measurement 28
3.2.3.4 Particle Size Analysis 28
3.2.4 Formulation and Preparation of Microemulsion-
Insecticides As Aerosol insecticides
28
3.2.4.1 Selection of the System for Microemulsion-
Insecticides Formulation
28
3.2.4.2 Preparation of Microemulsions as a Base for
Aerosol Insecticides
28
3.2.4.3 Physichochemical Characterisation of Palm
Methyl Esters Microemulsion-Insecticides
29
3.2.4.4 Formulation of Microemulsion-Insecticides as
Aerosol Insecticides
29
3.2.4.5 Physical Stability and Mist Behaviour of Palm
Methyl Esters Aerosol Insecticides
30
3.2.5 Biological Efficacy Study 31
3.2.5.1 Chemical Analysis 31
3.2.5.2 Stability Test Method 31
3.2.5.3 Bioefficacy Test Method 31
4 RESULTS AND DISCUSSION 33
4.1 Screening Process 33
4.1.1 Effect of Surfactant Ratio for W/O Microemulsions
System (PME/Surfactant/Water Systems)
33
4.1.2 Effect of Surfactant Ratio for O/W Microemulsions
System (PME/ S1:S2/Water/ Co-S Systems)
36
4.2 Phase Behaviour Study 39
4.2.1 Phase Behaviour of PME/AOT:DLS2/Water Systems 39
4.2.2 Phase Behaviour of PME/AOT:1-butanol/Water
Systems
41
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4.2.3 Phase Behaviour of PME/Tween 80:DLS2/1-
propanol/Water Systems
43
4.3 Physicochemical Characterization of Microemulsions 45
4.4 Formulation and Preparation of Microemulsion-Insecticides as
Aerosol insecticides
46
4.4.1 Selection of the System for Microemulsion-Insecticides
Formulation
46
4.4.2 Preparation of Microemulsions as a Base for Aerosol
Insecticides
47
4.4.3 Formulation of Palm Methyl Esters µE-Insecticides 47
4.4.4 Physicochemical Characterisation of Palm Methyl
Esters Microemulsion-Insecticides
48
4.4.4.1 Particle Size Analysis 49
4.4.5 Formulation of Microemulsion-Insecticides as Aerosol
Insecticides
54
4.4.6 Physical Stability and Mist Behaviour of Palm Methyl
Esters Aerosol Insecticides
54
4.5 Biological Efficacy Study 56
5 CONCLUSIONS 59
5.1 Recommendation for Future Research 60
REFERENCES 61
APPENDICES 65
BIODATA OF STUDENT 91
LIST OF PUBLICATIONS 92
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LIST OF TABLES
Table Page
3.1 Methods for microemulsions preparation 29
3.2 Methods for palm methyl esters microemulsion-insectides
preparation
29
3.3 Ratio of propellant to finished product for aerosol insectides
formulation
30
4.1 Visual observation of PME/AOT:DLS2/water system at RT (25°C)
and 45°C (day 1 – day 30) under polarised light sheet
34
4.2 Visual observation of PME/AOT:hexanol/water system at RT (25°C)
and 45°C (day 1 – day 30) under polarised light sheet
34
4.3 Visual observation of PME/AOT:1-butanol/water system at RT
(25°C) and 45°C (day 1 – day 30) under polarised light sheet
35
4.4 Visual observation of PME/AOT:1-propanol/water system at RT
(25°C) and 45°C (day 1 – day 30) under polarised light sheet
35
4.5 Visual observation of PME/FAE 10EO:DLS2/1-propanol/water
systems at 65:35 ratio of mixed S1:S2 and 25:75 ratio of oil to water
36
4.6 Visual observation of PME/FAE 20EO:DLS2/1-propanol/water
systems at 50:50 ratio of mixed S1:S2 and 25:75 ratio of oil to water
37
4.7 Visual observation of PME/Tween 80:DLS2/1-propanol/water
systems at 70:30 ratio of mixed S1:S2 and 25:75 ratio of oil to water
38
4.8 Physicochemical characterization of microemulsions 46
4.9 Composition of the selected microemulsion formulations 47
4.10 Visual observation of the microemulsions formulations 47
4.11 Weight of active ingredient in palm methyl esters W/O µE-
insecticides
48
4.12 Weight of active ingredient in palm methyl esters O/W µE-
insecticides
48
4.13 Physicochemical characterisation of palm methyl esters µE-
insecticides
49
4.14 Physical Stability and Mist Behaviour of Palm Methyl Esters
Aerosol Insecticides
55
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4.15 Percentage of active ingredient in FIK aerosol 56
4.16 Percentage of active ingredient in CIK aerosol 56
4.17 Discharge rate (gm/sec) and dosage used for FIK aerosol samples
against Aedes aegypti mosquitoes using the Peet Grady Chamber
method.
57
4.18 Time-response values (KT50 and KT95) of aerosol samples against
sucrose Aedes aegypti mosquitoes.
57
4.19 Discharge rate and dosage used for CIK aerosol samples against
male Periplaneta Americana cockroaches using the Glass Cylinder
method.
57
4.20 Time-response values (KT50 and KT95) of CIK aerosol samples
against Periplaneta Americana cockroaches
58
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LIST OF FIGURES
Figure Page
1.1 The Malaysian Household Insecticides Market (2005 to 2008) in
RM Millions
3
2.1 Schematic diagram of surface-active molecule 6
2.2 Schematic illustration of the various types of surfactants 7
2.3 Schematic representation of the concentration dependence of some
physical properties for solutions of a micelle-forming surfactant
9
2.4 An illustration of a spherical micelle (for dodecyl sulfate)
emphasizing the liquid-like character with a disordered
hydrocarbon core and rough surface.
10
2.5 Schematic diagram of the free energy of microemulsion and
nanoemulsion systems compared to the phase separated state
11
2.6 An aerosol insecticide consists of a receptacle (normally a can)
containing an insecticide solution and a propellant material
17
2.7 Aedes Aegypti mosquito 17
2.8 Periplaneta Americana cockroach 18
2.9 Mechanism of action of pyrethroid 19
2.10 Structure of Prallethrin 20
2.11 Structure of d-phenothrin 20
2.12 Structure of Imiprothrin 21
2.13 Structure of Cyphenothrin 21
3.1 A schematic triangular diagram for the ternary phase behaviour
study. Oil, W, and S are types of oil, water, and surfactant used
respectively
26
3.2 A schematic triangular diagram for the effects of co-surfactant (Co-
S) on the ternary phase behaviour study. Co-S, S, and O:W are the
co-surfactant, surfactant, and ratio of oil to water respectively
27
3.3 Transparent aerosol can 30
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4.1 Samples that show (a) clear or transparent; (b) cloudy and 2 phases;
(c) 3 phases or multilayers; (d) liquid crystal or birefringent when
observed through the polarized light
38
4.2 Ternary phase diagrams of PME/AOT:DLS2/water system at (a)
RT (25°C), (b) Day 1 (45°C), (c) Day 7 (45°C), and (d) Day 14
(45°C). Indicators: = Isotropic liquid region, L1, = Liquid
crystalline region, Lc, and = Multilayer region, M
40
4.3 Ternary phase diagrams of PME/AOT:1-butanol/water system at
(a) RT (25°C), (b) Day 1 (45°C), (c) Day 7 (45°C), and (d) Day 14
(45°C). Indicators: = Isotropic liquid region, L1, = Liquid
crystalline region, Lc, and = Multilayer region, M
42
4.4 Ternary phase diagrams of PME/Tween 80:DLS2/1-propanol/water
system at (a) RT (25°C), (b) Day 1 (45°C), (c) Day 7 (45°C), and
(d) Day 14 (45°C). Indicators: = Isotropic liquid region, L1, =
Liquid crystalline region, Lc, and = Multilayer region, M
44
4.5 Palm methyl esters µE-insecticides 48
4.6 Size distribution for (a) sample F1 (20:20:12.5), and (b) sample F2
(20:25:15) at 25°C
52
4.7 Size distribution for (a) sample F3 (7.5:5:10), and (b) sample F4
(12.5:7.5:10) at 25°C
54
4.8 Palm methyl esters µE as aerosol insecticides 55
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LIST OF ABBREVIATIONS
PME Palm methyl esters
W/O Water-in-Oil
O/W Oil-in-Water
µE Microemulsions
DH2O Deionized water
FIK Flying insect killer
CIK Crawling insect killer
AOT Aerosol OT (Sodium diethylhexyl sulfosuccinate)
S1 Primary surfactant
S2 Secondary surfactant
Co-S Co-surfactant
HLB Hydrophilic-lipophilic balance
EO Ethylene oxide
LC
Wt %
w/w
L1
Lc
M
EC
EW
MEW
CPO
PKO
PKC
Liquid crystal
Weight percent
Weight per weight
Isotropic liquid region
Liquid crystalline region
Multilayer region
Emulsifiable concentrates
Water-based emulsion
Water-based microemulsion
Crude palm oil
Palm kernel oil
Palm kernel cake
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PFAME
PK-MCT
GNI
Palm fatty acid methyl esters
Palm kernel-medium chain triglycerides
Gross national income
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CHAPTER 1
INTRODUCTION
1.1 Background of Research
The palm oil industry has brought great economic benefits to Malaysia. The current
production of 19 million metric tons (Mmtons) of crude palm oil (CPO) adds 8% to the
country’s gross national income (GNI) (Zwart, 2013). In addition, Malaysia is one of the
main producers and exporters of palm oil in the world, in which about 90% of the oil is
used for foods and 10% for oleochemicals or non-food applications (Ismail, 2006). The
Malaysian palm oil industry has flourished with a favourable growth in export demand
due to the limited supply of world oils and fats. The high demand due to depleting world
stock levels results in higher prices of oils and fats as well as palm oil products (Basri et
al., 2013).
Zwart (2013) reported that oil palm plantations in Malaysia cover close to 5 million
hectares (Mha) and with the plantations in Indonesia and other parts of the world, the
total oil palm acreage reached more than 16 Mha in 2011. The plantations yield crude
palm oil (CPO), palm kernel oil (PKO) and palm kernel cake (PKC) as the products that
have been of prime interest. These are traditional ingredients for a wide variety of food,
feed and non-food products. In Malaysia, CPO production in 2011 reached 18.91
Mmtons, 2.39 Mmtons for PKC and 2.15 Mmtons for PKO. A consistent and predictable
supply of palm kernel oil and palm oil has led to the development of the oleochemical
industry in the country (MPOB, 2014).
Most oleochemicals produced in Malaysia are basic oleochemicals such as fatty acids,
fatty alcohols, soap noodles, methyl esters, and glycerines. For 2014, exports of
oleochemical products rose by 2.3% to 2.22 million tonnes. The statistics for the major
oleochemical products exported were fatty acids (0.82 million tonnes or 36.7% of total
oleochemical exports), followed by fatty alcohols (0.46 million tonnes or 20.7%), soap
noodles (0.41 million tonnes or 18.5%), methyl esters (0.29 million tonnes or 13.0%)
and glycerines (0.23 million tonnes or 10.4%). The Malaysian Palm Oil Board (MPOB)
through Advanced Oleochemical Technology Division (AOTD) has been actively
carrying out research and development activities in downstream products to develop
palm-based products (MPOB, 2014).
Oleochemicals are derived from natural oils such as palm and palm kernel oils. These
oils and their derivatives have many advantages over petrochemicals (which are derived
from petroleum) in that they are renewable, biodegradable, non-flammable and usually
less irritant to eyes and skins of end users. Thus, palm oil and its derivatives such as
palm fatty acid methyl esters (PFAME), also called as palm oil methyl esters (POME)
and palm kernel-medium chain triglycerides (PK-MCT) have potential to be utilised as
the oil phases in the study of microemulsion formulations for practical applications
(Ismail, 2006). In this work, the development of microemulsion system using palm-
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based materials as the oil phases, emulsifiers and/co-emulsifier for aerosol insecticides
formulations was studied.
Microemulsions are transparent optically isotropic (clear) and thermodynamically stable
solutions, whereby the droplets size is very small (≤100nm) and have low viscosity
(Tadros, 2005). These properties have attracted many researchers, formulators,
manufacturers, and end-users to study and apply this system for producing high value-
added products. Palm methyl esters microemulsions are used as a basis for preparing
aerosol insecticides against domestic insect pests due to their favourable characteristic
such as renewable resources, biodegradable, non-flammable, and less or non-toxic to
end users.
The global specialty or non-agricultural insecticide market is estimated at more than
$3.0 billion at the formulated product marketer level in 2003 (Kline & Company, Inc
(2004). The leading companies are Bayer, Aventis, Dow, FMC, Syngenta, S.C. Johnson,
Scotts, and Sumitomo. While the United States is the largest market segment, accounting
for an estimated 60% of the total, Pacific Rim and selected Latin American countries
have shown growth when their economies have supported it. These areas continue to
offer growth opportunities as per capita incomes rise and human health issues are
accorded more importance.
Basic insecticide producers have come to rely on the specialty segment for profitable
growth at a time when the two largest crop segments, corn and cotton, have become
depressed (or soon will be) due to the introduction of insect resistant seeds. In this
environment, specialty non-agricultural insecticide markets are perceived to offer a more
stable, profitable outlet for a small but increasing percentage of active ingredient
volume. In Malaysia, the sales of household insecticides reflected increasing affluence
of the Malaysian society at large as shown in Figure 1.1 (Lee Nai Pin, 2009). With the
outbreak of dengue fever and the desire of the citizens to control mosquitoes particularly
Aedes, the sales of aerosols and mosquito coils increased particularly in the Klang
Valley. Mosquitoes are vectors of many life threatening diseases in humans.
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Figure 1.1: The Malaysian Household Insecticides Market (2005 to 2008) in RM
Millions (Source: Lee Nai Pin, 2009)
1.2 Statement of Problems
Insecticides comprise about 20% (w/w) of the total pesticides marketed in Malaysia in
which more than 55% of the insecticides are in the form of solvent-based formulations
or emulsifiable concentrates (EC). The conventional aerosol insecticides consist of
100% solvents derived from petroleum resources, such as xylene, kerosene, toluene and
other petroleum-based solvents. (MCPA, 2002). The formulations tend to cause medical
problems (e.g., skin and eye irritations) to the end-users or operators, and they are highly
flammable and non-biodegradable. In addition, petroleum products are known to be
depleting in resources and the prices increased significantly over the years. Therefore,
there is increasing demand for safer and more convenient pesticide formulations such as
water-based emulsion (EW) or microemulsion (MEW) instead of EC-aerosol insecticide
formulations (Ismail, 2007). In recent years, most of Agrochemical companies attempt
to formulate products in forms that can be applied globally. Furthermore, there has been
dramatic shift from solvent-based to water-based aerosol insecticides due to increasing
requirement for safe and more convenient pesticide formulations to ensure easy
application and its effectiveness in killing the insect pests.
1.3 Scope of Study
Palm methyl esters microemulsions are used as a basis for preparing aerosol insecticides
against domestic insect pests due to their favourable characteristic such as renewable
resources, biodegradable, non-flammable, and less or non-toxic to end users. The studies
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emphasized the development of microemulsion-insecticides using palm-based materials
as the oil phases, emulsifiers, and/or co-emulsifier, and apply them as a basis for
preparing aerosol insecticides for household uses. The work include utilization of palm-
based materials containing anionic or mixed non-ionic surfactants, palm methyl esters
(PME), deionized water (DH2O), and 1-alkanol as a co-surfactant for preparing water in
oil (W/O) and oil in water (O/W) microemulsion (µE) solutions. It involves screening
process, ternary phase diagram study, physico-chemical characterizations of
microemulsions, formulating and preparing microemulsion-insecticides as aerosol-
insecticides, and bioefficacy test of the formulated products on insect pests.
The optimum compositions and concentrations for both W/O-µE and O/W-µE systems
were determined. Ternary phase diagrams systems were carried out to determine suitable
surfactant or mixed surfactants and/or co-surfactants for W/O-µE and O/W-µE systems
as a base for palm methyl esters aerosol insecticides formulations. The physical stability
at ambient and high temperatures, particles size, viscosity and the mist behaviour of the
palm methyl esters aerosol insecticides were studied. Both systems were used to
formulate W/O-µE aerosol insecticides to be applied as Flying Insect Killer (FIK)
aerosol-spray product to control flying insects such as mosquitoes and houseflies while
O/W-µE aerosol insecticides was applied as Crawling Insect Killer (CIK) aerosol-spray
product to control crawling insects such as cockroaches and ants respectively. Other than
that, the bioefficacy tests on both products were also determined. The invension of this
system consisting mixed surfactants, PME, and non-toxic co-surfactant has great
potential to be used in preparing palm methyl esters aerosol insecticides which are more
environmental and end-users friendly.
Novelty of palm methyl esters aerosol-insecticides:
Palm methyl esters microemulsions (μE), a nanotechnology system (< 100 nm
of particles size) was used instead of solvent-based or macroemulsion (>500
nm particles size).
The bases are formulated using palm methyl esters, which are renewable,
biodegradable and environmentally friendly.
The inerts (palm methyl esters microemulsions) are also less hazardous to end-
users and aquatic organisms.
An innovative (μE) aerosol-insecticides technology using green palm-based
materials.
Contains propellant which has an ozone depleting potential (ODP) of zero.
1.4 Objectives
To formulate microemulsion-insecticides using palm oil-based materials as the
oil phases, emulsifiers and/or co-emulsifier.
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To formulate aerosol insecticides formed with palm-based microemulsions
against insect pests for public used.
To characterize the physicochemical properties of microemulsion (µE) such as
their conductivity, viscosity, pH, and particle size.
To evaluate the bioefficacy of household insecticides.
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LIST OF PUBLICATIONS
1. Paper
Ismail Raman, Rohana Othman, Mahiran Basri, and Hazimah, Abu Hassan (2012) Palm-
Based Aerosol Insecticides. MPOB TOT Seminar, June 2012. MPOB TT No.
520, MIS No. 607
Ismail Raman, Rohana Othman, Mahiran Basri, and Hazimah, Abu Hassan (2012) Palm-
Based Microemulsions as Aerosol Insecticides. Patent No. PI2012700975, 21st
November 2012.
2. Seminars/Conferences
Ismail Raman, Rohana Othman, Mahiran Basri, and Hazimah, Abu Hassan. Palm-Based
Aerosol Insecticides. MPOB TOT Seminar. 14th June 2012. MPOB Bandar
Baru Bangi, Kajang, Selangor, Malaysia.
Ismail Raman, Rohana Othman, Mahiran Basri, and Hazimah, Abu Hassan. Palm-Based
Microemulsions as Aerosol Insecticides. Oils and Fats International Congress
(OFIC). 11-14th September 2012. KLCC Kuala Lumpur.
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UNIVERSITI PUTRA MALAYSIA
STATUS CONFIRMATION FOR THESIS / PROJECT REPORT AND COPYRIGHT
ACADEMIC SESSION:
TITLE OF THESIS / PROJECT REPORT: DEVELOPMENT OF PALM METHYL ESTER MICROEMULSIONS AS AEROSOL INSECTICIDES
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