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

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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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Act 1972).

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OPEN ACCESS I agree that my thesis/project report to be published

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PATENT Embargo from_____________ until ______________ (date) (date)

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