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RIGID AND FLEXIBLE POLYURETHANE FOAMS

PRODUCTION FROM PALM OIL-BASED POLYOL

A THESIS SUBMITTED TO THE

FACULTY OF SCIENCE

UNIVERSITY OF MALAYA

IN FULFILLMENT OF THE REQUIREMENTS

FOR THE DEGREE OF

DOCTOR OF PHILOSOPHY

BY

LEE CHOY SIN

KUALA LUMPUR

MALAYSIA

2008

ii

ACKNOWLEDGEMENT

Firstly, I would like to express my heartfelt gratitude and deepest appreciation to my

supervisor, Professor Dr Chuah Cheng Hock, for his guidance throughout the course of this

study. I am equally indebted to Dr Ooi Tian Lye, consultant of this project, for his kind

supervision and guidance during the course of my research work at Advanced

Oleochemical Technology Division (AOTD), Malaysian Palm Oil Board (MPOB).

I would like to acknowledge with thanks for the financial support from Malaysian Palm

Oil Board Graduate Students' Assistantship Scheme (MPOB-GSAS), in form of graduate

assistantship. I would express my sincere thanks to staffs of Chemistry Department,

University Malaya and AOTD for their assistances.

Last but not least, I am also greatly indebted to my parents, Lee Choon Seng and Lock Lai

Khuan; husband, Lee Song Cang; sister, Lee Choy Yan; brother, Lee Kok Kuen; and

friends, for their relentless encouragement and support that have contributed towards the

accomplishment of this project.

iii

ABSTRACT

Polyurethane foams are amongst the most important class of specialty polymers. It can be

divided into three major classes, namely rigid, semi-rigid and flexible polyurethane foams.

According to M.L. Kerman (2005), the global polyurethane market in 2004 showed that

flexible polyurethane foams contributed 47% of the market share, followed by 26% of

rigid foams, and 27% of other applications in coatings, adhesives, sealants and elastomers

(CASE), binders, foundry and machinery. Rigid polyurethane foams are particularly useful

in the construction industries as they are used as components such as polymeric concretes,

insulating materials and sealants. In addition, flexible polyurethane foams are as cushion in

the furniture, bedding and automotive industries. Conventionally, polyol is mainly derived

from petrochemicals. They play an important role in the polyurethane industry. However,

in view of the environmental and sustainability issues, the use of vegetable oil-derived

polyol can serve as a substitute in the polyurethane industry. Malaysia is one of the major

producers of palm oils. Therefore, the utilization of palm oils in the synthesis of polyols

for both rigid and flexible polyurethane foams was initiated in this study.

In this study, epoxidized diethanolamides was produced as a new type of polyol by

reacting diethanolamine (DEA) with various ratio of Epoxidized Palm Olein (EPOo) to

Refined Bleached Deodorized Palm Kernel Olein (RBDPKOo). The products were further

reacted with diisocyanate and catalyzed by AlCl3-THF to produce rigid polyurethane.

Concurrent with the production of rigid polyurethane, two minor important side-products

oxazolidones and isocyanurates were produced to give significantly a better quality of rigid

polyurethane. This is due to epoxidized diethanolamides with higher oxirane oxygen

iv

contents (OOC) that produced rigid polyurethane foams of higher compression strength

(338.8 kPa), close cell contents (97.95%) and lower thermal conductivity (0.0288 w/m.K).

In this work, only epoxides in diethanolamide polyol was reacted with isocyanate that

resulted in the formation of hard segments oxazolidone and isocyanurate in the rigid

polyurethane and this improved the compression strength and close cell contents of the

foam. In addition, higher OOC in diethanolamides also gave better dimensional stability to

the rigid foam that was conditioned at 70 °C and -25 °C. Apart from mechanical

improvements, epoxides that were retained in diethanolamide structure also improved the

thermal stability of the rigid foam. Thermogravimetric Analysis (TGA) was recorded with

higher decomposition temperature for foam produced with higher OOC diethanolamides.

Formation of oxazolidones in the urethane backbones and isocyanurates exhibited good-

heat resistance that significantly enhanced the thermal stability of the foams. Index 1.40

was determined to be the most suitable isocyanate index when the polyurethane foam were

altered by isocyanate index from 0.90 to 1.10. It produced non-brittle rigid foam with the

lowest thermal conductivity (0.0288 w/m.K) and the highest close cell contents (97.95%)

while maintaining moderate compression strength (338.8 KPa).

One type of polyester polyol is synthesized by ring opening of synthetic epoxidized resins

with dicarboxylic acids. Conventionally, the epoxides that used in the preparation of

polyester polyol were ethylene oxide, propylene oxide, phenylglycidyl ether (PGE),

diglycidyl ether of bisphenol A (DGEBA) and 3-phenoxy-1,2-epoxypropane. The versatile

polyols were used mainly as fat-based non-ionic detergent, surface active agent,

thermoplastic, paper coating resin and material for radiation shielding materials, curable

printing ink and as coating. Therefore, in the second part of this study polyester polyol was

prepared by using EPOo as the starting material instead of the synthetic epoxy resin. The

v

polyester polyol was synthesized by reacting EPOo with different carbon chain length of

aliphatic dicarboxylic acids ranging from C6 to C12. This produced a new type of polyol.

The new polyol was mixed thoroughly with 50% of commercial polyol and they were

reacted with toluene diisocyanate (TDI) to produce flexible polyurethane foam. The

flexibility of the polyurethane foam was due mainly to the high average molecular weight

and hydroxyl functional groups that were attached to the carbon chain of the polyols.

Longer carbon chain in dicarboxylic acid was found to be more reactive than the shorter

chain, which resulted in lower OOC (0.42%) of polyol mixture with bigger average

molecular weight (Mw= 10526 g/mol). However, it also produced polyester polyol with

higher hydroxyl value (103.6 mg KOH/g sample), viscosity (9755.21 cP at 25 °C, 4222.41

cP at 40°C), cloud point (20.04 °C) and pour point (12.00 °C) when compared to shorter

carbon chain of dicarboxylic acid. Longer carbon chain of dicarboxylic acid used to

produce polyester polyol resulted in the improvement of the foam properties such as

hysteresis (22.76%), elongation at break (181.1 %) and thermal stability. The temperature

of the decomposition peak (Tdec) of polyurethane as shown in DSC analysis and the

decomposition temperatures of 10%, 50% and 90% of foam weight loss in TG analysis

were increased. But, polyol synthesized from shorter carbon chain of dicarboxylic acid

produced foam with better tensile stress and tear resistant ability. Isocyanate index 1.00

was selected as the optimal index as it produced flexible foam with the lowest hysteresis

(23.64%), highest tensile stress (138.0%) and the best tear resistant ability (0.2382 N/mm).

Flexible foam produced from higher isocyanate index was determined to be more stable

thermally. However, alteration of isocyanate index did not produce foam with significant

changes in terms of cellular structure, but the open cell contents of the foams prepared with

different isocyanate index and polyester polyol were in a satisfactory range of 95-97%.

Based on physical evaluation, 2 g of water content was the most suitable amount to be used

vi

in the production of flexible foams in comparison to 3 g and 4 g of water contents. This

was mainly because 2 g of water content produced foam with the lowest hysteresis, highest

elongation at break and better tear resistance ability. Nevertheless, increment of water

content increased the foams’ open cell contents from 95% to 98% due to the emission of

carbon dioxide generated from the reaction of isocyanate with water to form hard segment

urea. Therefore, foam with higher content of urea that produced by higher water content as

blowing agent were determined to be more stable thermally. Optical microscope also

recorded open cells in various pentagon sizes that produced cells of bigger sizes in higher

water content produced foam whereas lower water content produced foams with smaller

cells in size and also more uniform in structure.

vii

ABSTRAK

Busa poliuretana merupakan salah satu jenis polimer yang penting dan boleh turut

dibahagikan kepada tiga kelas utama, iaitu, busa keras, semi-keras dan fleksibel. Menurut

kepada M.L. Kerman (2005), pasaran poliuretana dunia pada 2004 menunjukkan bahawa

poliuretane fleksibel menyumbang 47%, diikuti oleh 26% busa keras dan 27% aplikasi lain.

Busa keras sangat berguna dalam industri pembinaan iaitu sebagai bahan konkrit, penebat

haba dan sebagainya. Di samping, poliuretana fleksibel iaitu kusyen digunakan dalam

industri perabot. Kebanyakan poliol yang memainkan peranan utama dalam industri

poliuretana adalah dihasilkan dari bahan kimia petrol. Memandangkan isu pemuliharaan

dan persekitaran yang mustahak, penggunaan poliol yang berasaskan minyak sayur amat

dipentingkan. Malaysia merupakan salah sebuah negara penghasilan minyak kelapa sawit

yang utama, oleh demikian, kerja penyelidik ini menggunakan minyak kelapa sawit untuk

mensintesiskan dua jenis poliol yang boleh digunakan dalam pembuatan busa keras dan

busa fleksibel.

Poliol dietanolamida dengan kumpulan epoksi telah dihasilkan sebagai sejenis poliol baru

di mana dietanolamina ditindakbalaskan dengan pelbagai nisbah Epoxidized Palm Olein

(EPOo) dan Refined Bleached Deodorized Palm Kernel Olein (RBDPKOo). Poliol ini

kemudiannya ditindakbalaskan dengan diisosianat dan dengan kehadiran katalis AlCl3-

THF untuk menghasilkan poliuretana keras. Dua jenis hasil sampingan, iaitu

“oxazolidone” dan isosianurat telah dihasilkan dan telah memperbaiki mutu busa keras. Ini

adalah kerana dietanolamida yang mempunyai kumpulan epoksi telah menghasilkan

poliuretana keras yang lebih bermutu dari segi mekanik dan kestabilan haba. Busa tersebut

viii

adalah stabil apabila disimpan pada suhu 70 °C dan -25 °C. Analisa termagravimetrik

(TGA) menunjukkan bahawa suhu penguraiaan busa adalah lebih tinggi apabila

dietanolamida yang mengandungi epoksi yang lebih tinggi digunakan dalam tindakbalas

penghasilan busa. Indeks isosianat 1.40 telah dipilih sebagai indeks optima disebabkan

penghasilan busa yang tidak rapuh serta berkekonduksian haba(0.0288 w/m.K) yang lebih

rendah, berkekuatan ketegangan (338.8 kPa) dan berkandungan sel tertutup (97.95%) yang

tertinggi.

Poliester poliol juga disintesiskan dengan pembukaan kumpulan epoksi dari EPOo dengan

asid dikarboksilik yang berantai C6 ke C12. Poliester poliol ini dicampur separuh dengan

poliol polieter komersial dan seterusnya ditindakbalaskan dengan toluena diisosianat dalam

penyediaan busa fleksibel. Asid dikarboksilik yang berantai lebih panjang didapati adalah

lebih reaktif dengan menghasilkan poliol yang bernilai hidroksi yang lebih tinggi (103.6

mg KOH/g sample). Busa yang dihasilkan juga mempunyai nilai “hysteresis” yang lebih

rendah, nilai pemanjangan sehingga putus yang lebih tinggi serta kestabilan haba yang

lebih baik.

Suhu penguraian yang dikaji dengan analisa TGA dan “Differential Scanning Calorimeter”

(DSC) bagi busa yang dihasilkan oleh poliester poliol berantai panjang didapati adalah

lebih tinggi. Akan tetapi, busa yang dihasilkan oleh poliol berantai pendek mempunyai

nilai kekuatan ketegangan dan ketahanan dikoyak yang lebih tinggi. Indeks isosianat 1.00

dan kandungan air 2 g yang digunakan sebagai agen peniup dalam formula penghasilan

busa fleksibel telah dipilih sebagai indeks dan kandungan air yang optima. Mikroskop

optik menunjukkan sel-sel terbuka dalam busa adalah berbentuk pentagon dan mempunyai

ix

saiz-saiz yang tidak seragam bergantung kepada kandungan air yang digunakan semasa

penghasilan busa.

x

TABLE OF CONTENTS Page

Acknowledgements ii

Abstract iii

Abstrak vii

Table of Contents x

List of Schemes xvi

List of Tables xviii

List of Figures xxii

Abbreviations xxix

CHAPTER ONE: LITERATURE REVIEW

1.1 INTRODUCTION 1

1.1.1 Types of Polyols 2

1.1.2 Types of Isocyanates 4

1.1.3 Reactivity of Isocyanates 7

1.1.4 Types of Polyurethanes 8

1.2 NATURAL OIL-BASED POLYOLS 8

1.2.1 PU from Seed Oils 9

1.2.2 Polyol from Soybean Oils 11

1.2.3 Polyol from Palm Oils 13

1.2.4 Polyol from Other Natural Oils 14

1.2.5 Alkanolamide as Polyol 17

xi

1.3 POLYESTER AND POLYESTER POLYOL 19

1.3.1 Polyester Polyol from Epoxy-Carboxy Reaction 22

1.4 MODIFIED RIGID POLYURETHANE 25

1.4.1 Polyisocyanurate-Polyurethane Foam 25

1.4.2 Allophanate-Polyurethane Foam 29

1.4.3 Imide-Polyurethane 30

1.4.4 Phosphazene-Polyurethane 32

1.4.5 Oxazolidone Polyurethane 33

1.5 FLEXIBLE POLYURETHANE FOAM 36

1.5.1 The Effect of Additives on Flexible Polyurethane 37

1.5.2 The Effect of Blowing Agent on Flexible Polyurethane 39

1.5.3 The Effect of Isocyanate Index on Flexible Polyurethane 40

1.5.4 Flexible Foam Analysis Method 41

1.5.5 Ignition and Thermal Character of Flexible Foam 44

1.6 OBJECTIVE OF PRESENT STUDY 46

CHAPTER TWO: MODIFIED PALM-OIL BASED

RIGID POLYURETHANE FOAM

2.1 BACKGROUND OF THE STUDY 48

2.2 SYNTHESIS OF DIETHANOLAMIDES 48

2.2.1 Optimization of Reactions 53

2.2.1.1 Amine Values 53

2.2.1.2 Oxirane Oxygen Contents 54

2.2.2 Variation of Ratios of Starting Materials 57


2.2.2.2 Amine Values 60

2.2.2.3 Molecular Weight Determination 62

2.2.2.4 Hydroxyl Values 63

xii

2.2.2.5 Viscosity 66

2.2.2.6 Pour Point, Cloud Point and Physical Appearance 68

2.2.3 Characterization of Diethanolamides 69

2.2.3.1 Fourier Transform InfraRed Spectroscopy (FTIR) 70

2.2.3.2 High Performance Liquid Chromatography (HPLC) 72

2.2.3.3 Liquid Chromatography- Mass Spectrometry (LC-MS) 76

2.2.3.4 Gas Chromatography (GC) 80

2.2.3.5 Gas Chromatography-Mass Spectrometry (GC-MS) 88

2.3 RIGID POLYURETHANE FOAM PRODUCTION 95

2.3.1 Formulation of the Rigid Polyurethane Foam 96

2.3.2 The Effect of Isocyanate Index on Rigid Polyurethane Foam 98

2.3.2.1 Compression Strength and Density of Polyurethane 99

2.3.2.2 Close Cell Contents and Thermal Conductivity 103

of Polyurethane

2.3.3 The Effect of Oxirane Oxygen Contents (OOC) in 105

Diethanolamides on Rigid Polyurethane Foam

2.3.3.1 Thermal Stability 105

2.3.3.2 Compression Strength and Density of Polyurethane 109

2.3.3.3 Close Cell Contents and Thermal Conductivity 112

of Polyurethane

2.3.3.4 Dimensional Stability of Polyurethane Foam 114


2.4 SUMMARY 119

CHAPTER THREE: FLEXIBLE POLYURETHANE FOAM

3.1 BACKGROUND OF STUDY 122

3.2 SYNTHESIS OF POLYESTER POLYOL 123



3.2.1.2 Acid Values 133


xiii

3.2.2 Different Carbon Chain Length of Dicarboxylic Acids 137





3.2.2.5 Cloud Point, Pour Point and Physical Appearance 145

3.2.3 Characterization of Polyester Polyols 147


3.2.3.2 Nuclear Magnetic Resonance Spectroscopy (13

CNMR) 155

3.2.3.3 Nuclear Magnetic Resonance Spectroscopy (13

CNMR) 160

3.2.3.4 Gel Permeation Chromatography (GPC) 165

3.3 FLEXIBLE POLYURETHANE FOAM PRODUCTION 173

3.3.1 Formulation of the Flexible Polyurethane Foam 173

3.3.2 The Effect of Isocyanate Index on Flexible Polyurethane Foam 174

3.3.2.1 Density, Hysteresis and Compression Stress 175

3.3.2.2 Tensile Stress, Elongation at Break and Tear Resistance 178

3.3.2.3 Open Cell Contents and Microphotograph 182

3.3.2.4 Differential Scanning Calorimetry (DSC) 184

and Thermogravimetric Analysis (TGA)

3.3.3 The Effect of Water Content on Flexible Polyurethane Foam 187

3.3.3.1 Density, Hysteresis and Compression Stress 188





3.3.4 The Effect of Different Carbon Chain Length of Dicarboxylic 201

Acids in the Synthesis of Polyester Polyol for Flexible

Polyurethane Foam Production

3.3.41 Density, Hysteresis and Compression Stress 202





3.4 SUMMARY 215

xiv

CHAPTER FOUR: EXPERIMENTAL

4.1 SYNTHESIS OF DIETHANOLAMIDES 218

4.1.1 Materials and Reagents 218

4.1.2 Equipment and Instrumentation 219

4.1.3 Preparation of Diethanolamides 220


4.1.4.1 Total Amine Value of Fatty Amines, Indicator Method 221


4.1.5 Variation of Ratios of Starting Materials 222



4.1.5.3 Cloud Point Measurement 224

4.1.5.4 Pour Point Measurement 225

4.1.6 Characterization of Diethanolamides 226


4.1.6.2 High Performance Liquid Chromatography (HPLC) 226

4.1.6.3 Liquid-Chromatography-Mass Spectrometry (LC-MS) 227

4.1.6.4 Gas Chromatography (GC) 227

4.1.6.5 Gas Chromatography-Mass Spectrometry (GC-MS) 228

4.2 RIGID POLYURETHANE FOAM PRODUCTION 229

4.2.1 Isocyanate Index Determination 230

4.2.2 Density Measurement 233

4.2.3 Compression Strength Measurement 233

4.2.4 Percentage of Close Cell Contents 233

4.2.5 Thermal Conductivity Measurement 234

4.2.6 Thermogravimetric Analysis (TGA) 234

4.2.7 Fourier Transform InfraRed Spectroscopy (FTIR) 234

4.2.8 Dimensional Stability Test 235

4.2.9 Microphotograph of the Foam Cell 236

4.3 SYNTHESIS OF POLYESTER POLYOL 237

xv

4.3.1 Materials and Reagents 237

4.3.2 Equipment and Instrumentation 237

4.3.3 Preparation of Polyester Polyol 237

4.3.4 Otimization of Reactions 238



4.3.5 Analysis of the Reaction 238



4.3.5.3 Cloud Point Measurement 239

4.3.5.4 Pour Point Measurement 239

4.3.5.5 Fourier Transform InfraRed Spectral (FTIR) 240

Spectroscopy

4.3.5.6 Gel Permeation Chromatography (GPC) 240

4.3.5.7 1HNuclear Magnetic Resonance (NMR) Spectrometry 240

4.3.5.8 13

CNuclear Magnetic Resonance (NMR) Spectrometry 241

4.4 FLEXIBLE POLYURETHANE FOAM PRODUCTIION 241

4.4.1 Isocyanate Index Determination 242

4.4.2 Density Measurement 246

4.4.3 Percentage of Open and Close Cell Contents 246

4.4.4 Compression Stress and Hysteresis Measurement 247

4.4.5 Tensile Stress and Elongation at Break Measurement 247

4.4.6 Tear Resistance Test 247

4.4.7 Thermogravimetric Analysis (TGA) 248

4.4.8 Microphotograph of the Foams’ Cells 248

CHAPTER FIVE: CONCLUSION

5.1 CONCLUSION 249

5.2 SUGGESTIONS FOR FUTURE WORKS 250

References 252

Appendix

List of Publications 267

xvi

LIST OF SCHEMES

Page

Scheme 2.1: Amide formation 49

Scheme 2.2: Mechanism of the synthesis of diethanolamides 51

Scheme 2.3: Synthesis of diethanolamides 51

Scheme 2.4: Synthesis of epoxidized diethanolamide polyols 52

Scheme 2.5: Mechanism of epoxide reacts with isocyanate to form 97

oxazolidone in the presence of AlCl3 Lewis acid

Scheme 2.6: Trimerization reaction of isocyanates to yield isocyanurate 102

Scheme 2.7: Formation of biuret from the reaction of isocyanate with urea 102

Scheme 2.8: Formation of allophanate from the reaction of isocyanate 102

with urethane

Scheme 2.9: Reaction scheme in the formation of poly-2-oxazolidone 108

in the foam

Scheme 2.10: Reaction scheme in the formation of isocyanurate in the foam 108

Scheme 2.11: Reaction scheme for poly (isocyanurate-oxazolidone) 112

Scheme 3.1: Reaction of long chain carboxylic acid and ethylene oxide 122

Scheme 3.2: Esterification process of a carboxylic acid and an epoxy 123

Scheme 3.3: Side reactions of the esterification process between 124

carboxylic acid and epoxy compounds

Scheme 3.4: Formation of zwitterions by base catalysis 125

Scheme 3.5: Polymerization of diepoxide and dicarboxylic acid 126

Scheme 3.6: Mechanism of the non-catalyzed carboxy-epoxide reaction 128

Scheme 3.7: Formation of polyester polyol from the reaction of 129

diepoxides of epoxidized palm olein with dicarboxylic acid

Scheme 3.8: Formation of diester polyol from the reaction of 130

monoepoxide of epoxidized palm olein with dicarboxylic acid

xvii

Scheme 3.9: The emission of carbon dioxide and formation of urea 188

by the reaction of isocyanate with water

Scheme 3.10: The formation of biuret from the reaction of urea 191

and isocyanate

Scheme 3.11: Reaction scheme of isocyanate with carboxylic acid 206

xviii

LIST OF TABLES

Page

Table 2.1: The effect of temperatures on amine values in 54

the synthesis of diethanolamides

Table 2.2: The effect of reaction temperature on oxirane 55

oxygen contents

Table 2.3: Percentage of oxirane oxygen contents retained 57

in epoxidized diethanolamides after 7 h of reaction time

Table 2.4: The effect of different percentages of EPOo used 58

as starting material on oxirane oxygen contents

Table 2.5: The effect of various percentages of EPOo used as 60

starting material on amine values

Table 2.6: The weight average molecular weight (Mw), 63

number average molecular weight (Mn)

and polydispersity index (PDI) of the diethanolamides

Table 2.7: Functionality of the diethanolamides 65

Table 2.8: Cloud point, pour point and physical appearance 69

of the polyols

Table 2.9: Components of the diethanolamides and retention time 75

Table 2.10: Selected LC-MS fragment ions of the diethanolamides 76

Table 2.11: Composition of trimethylsilyl derivatives of adiethanolamides 83

and retention time


and retention time


and retention time

Table 2.14: Total composition in the reaction mixture 88

Table 2.15: Selected GC-MS fragment ions of trimethylsilyl derivatives 94

of diethanolamide polyola

Table 2.16: Standard formulation for rigid polyurethane foam 98

Table 2.17: The effect of isocyanate index on compression strength 100

xix

and density of the rigid polyurethane foama

Table 2.18: The effect of isocyanate index on the percentage of 103

close cell contents and thermal conductivity

of the rigid polyurethane foama

Table 2.19: The effect of OOC in diethanolamides on 106

thermal characters of rigid polyurethane foam

Table 2.20: The effect of oxirane oxygen contents on the compression 110

strength and the density of polyurethane foam

Table 2.21: The effect of oxirane oxygen contents on close cell 113

contents and thermal conductivity of polyurethane foam

Table 2.22: The effect of oxirane oxygen contents in diethanolamides 115

on the linear changes of the foam

Table 3.1: Formula and structure of dicarboxylic acids 127

used in the reaction

Table 3.2: Effect of temperature on hydroxyl value in the synthesis 132

of polyester polyol

Table 3.3: Effect of temperature on acid value in the synthesis 134

of polyester polyol

Table 3.4: Effect of temperature on oxirane oxygen contents 136

in the synthesis of polyester polyol

Table 3.5: Effect of different dicarboxylic acids on acid values 140


Table 3.6: Effect of different dicarboxylic acids on OOC 142


Table 3.7: Cloud point, pour point and physical appearance 146

of the reaction products

Table 3.8: Characteristics of FTIR peaks of epoxidized palm olein, EPOo 149

Table 3.9: Characteristics of FTIR peaks of polyester polyol B1 150

after 4 h of reaction at 180 ºC

Table 3.10: 1HNMR of EPOo 157

Table 3.11: 1HNMR of polyester polyol B1 159

Table 3.12: 13

CNMR of EPO 162

xx

Table 3.13: 13

CNMR of polyester polyol B1 164

Table 3.14: The GPC results of reaction P4 168

Table 3.15: The effects of reaction temperature on GPC results 170

Table 3.16: The GPC results of polymers B1 to B5 171

Table 3.17: Standard formulation for flexible polyurethane foam 173

Table 3.18: The effect of isocyanate index on density and hysteresis 175

of the flexible polyurethane foama

Table 3.19: The effect of isocyanate index on tensile stress and 179

elongation at break of the flexible polyurethane foama

Table 3.20: The effect of isocyanate index on open cell contents 182

of the flexible polyurethane foama

Table 3.21: The effect of isocyanate index on thermal characters 184

of flexible polyurethane foam

Table 3.22: The effect of water content on density, hysteresis and 189

compression stress of flexible foam

Table 3.23: The effect of water content on tensile stress, elongation 193

at break and tear resistance of flexible foam

Table 3.24: The effect of water content on open cell contents 195

of flexible foam

Table 3.25: The effect of water contents on thermal characters of 197

flexible polyurethane foam

Table 3.26: The effect of different polyols on density, hysteresis 203

and compression stress of flexible foam

Table 3.27: The effect of different polyols on tensile stress, tear resistance 207

and elongation at break of flexible foam

Table 3.28: The effect of different polyols on open cell contents of 210

flexible polyurethane foam

Table 3.29: The effect of different polyols on thermal characters 212

of flexible polyurethane foam

Table 4.1: Reaction compositions 220

xxi

Table 4.2: Standard formulation for rigid polyurethane foam 230

Table 4.3: Amount of MDI based on different isocyanate index 233

Table 4.4: Standard formulation for flexible polyurethane foam 242

Table 4.5: Amount of TDI based on different isocyanate index 246

xxii

LIST OF FIGURES

Page

Figure 1.1: Synthesis of polyurethane 1

Figure 1.2: Anionic mechanism to form polyether polyol 2

Figure 1.3: Synthesis of polyether polyol 3

Figure 1.4: Synthesis of polyester polyol 3

Figure 1.5: Synthesis of polycarbonate 4

Figure 1.6: Structures of TDI and MDI 5

Figure 1.7: Resonance of isocyanate 7

Figure 1.8: Isocyanate attacking by hydrogen active compounds 7

Figure 1.9: Hydroxymethylated polyol esters 9

Figure 1.10: Polyol prepared from triethanolamine and epoxidized rapeseed oil 10

Figure 1.11: Soybean polyol for rigid polyurethane production 11

Figure 1.12: Polyurethane from cardanol 15

Figure 1.13: Cardanol formaldehyde resin 16

Figure 1.14: Synthesis of hydroxymethylated diethanolamides 18

Figure 1.15: Synthesis of carboxylated diethanolamides 18

Figure 1.16: Synthesis of biodegradable aliphatic copolyester 20

Figure 1.17: Saturated and unsaturated polyester-diols 22

Figure 1.18: Side reactions that may take place during the formation of 25

epoxy-carboxy network

Figure 1.19: Structure of urethane-modified polyisocyanurate 28

Figure 1.20: Synthesis of allophanate from diurethane 30

Figure 1.21: Synthesis of poly(urethane-imide) 31

Figure 1.22: Synthesis of phosphazene crosslinking agent 32

xxiii

Figure 1.23: Ring opening of epoxide by halide anion 33

Figure 1.24: Synthesis of poly (urethane-oxazolidone) 35

Figure 1.25: Stress-strain curve for foams 37

Figure 1.26: Structure of a standard silicone surfactant 38

Figure 1.27: Deformation mechanism of voided sample 43

Figure 2.1: Oxirane oxygen contents at different logarithmic of reaction 56

temperature

Figure 2.2: Oxirane oxygen contents of reactions carried out 59

at 110°C for 5 h

Figure 2.3: Amine values of reactions carried out at 110°C for 5 h 61

Figure 2.4: Hydroxyl values of the reaction products 64

Figure 2.5: Viscosity tested at 25°C and 40°C 67

Figure 2.6: FTIR analysis on sample S0 70



Figure 2.9: HPLC chromatogram of sample S0 73



Figure 2.12: LC-MS mass spectrum of decanoic acid 77

bis-(2-hydroxy-ethyl)-amide/ C10:0 diethanolamide

Figure 2.13: LC-MS mass spectrum of dodecanoic acid 78


Figure 2.14: LC-MS mass spectrum of tetradecanoic acid 78


Figure 2.15: LC-MS mass spectrum of hexadecanoic acid 79


Figure 2.16: LC-MS mass spectrum of 79

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octadec-9-enoicacid-bis-(2-hydroxy-ethyl)-amide/

C18:1 diethanolamide

Figure 2.17: LC-MS mass spectrum of octadecanoic acid 80


Figure 2.18: Typical gas chromatogram of trimethylsilyl-diethanolamide 82

derivatives


derivatives


derivatives

Figure 2.21: GCMS mass spectrum of 89

N, N-bis (2-(trimethylsilyloxy) ethyl) hexanamide/

trimethylsilyl-derivatized C6:0 diethanolamide


N, N-bis (2-(trimethylsilyloxy) ethyl) octanamide/



N, N-bis (2-(trimethylsilyloxy) ethyl) decanamide/



N, N-bis (2-(trimethylsilyloxy) ethyl) dodecanamide/



N, N-bis (2-(trimethylsilyloxy) ethyl) tetradecanamide/



N, N-bis (2-(trimethylsilyloxy) ethyl) palmitamide/



N, N-bis (2-(trimethylsilyloxy) ethyl) octadec 9-enamide/



N, N-bis (2-(trimethylsilyloxy) ethyl) stearamide/



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8-(3-octyl-oxiran-2-yl)-N, N-bis (2-(trimethylsilyloxy)ethyl)

octanamide/ trimethylsilyl-derivatized epoxidized

C18:1 diethanolamide


8-(3-((3-pentyloxiran-2-yl)methyl)oxiran-2-yl)-N,N-bis(2-

(trimethylsilyloxy)ethyl) octanamide/

trimethylsilyl-derivatized epoxidized C18:2 diethanolamide

Figure 2.31: Structure of 8-(3-octyl-oxiranyl)-octanoic acid 95

bis-(2-trimethylsilanyloxyl-ethyl)-amide

Figure 2.32: 8-[3-(3-Pentyl-oxiranylmethyl)-oxiranyl]- 95

octanoic acid bis-(2-trimethylsilanyloxyl-ethyl)-amide

Figure 2.33: Effect of isocyanate index on the compression strength 101

and density of the foam

Figure 2.34: Effect of isocyanate index on percentage of close cell 104

contents and thermal conductivity of the foam

Figure 2.35: TGA curves of the polyurethane foam 107

Figure 2.36: The effect of oxirane oxygen contents in 111

diethanolamides on the compression strength

and the density of the polyurethane foam

Figure 2.37: The effect of oxirane oxygen contents in diethanolamides on 114

close cell contents and thermal conductivity of polyurethane foam

Figure 2.38: The effect of oxirane oxygen contents in diethanolamides 116

on the linear changes of the foam

Figure 2.39: FTIR spectra analysis of the polyurethane foam 118

Figure 3.1: Hydroxyl values at different logarithmic of reaction 133

temperatures

Figure 3.2: Acid values at different logarithmic of reaction temperatures 135

Figure 3.3: Oxirane oxygen contents at different logarithmic of reaction 137

temperatures

Figure 3.4: Hydroxyl values of the reaction products 139

Figure 3.5: Acid values of reaction mixture reacted by different 141

dicarboxylic acids with EPOo at 180 °C for 4 h

Figure 3.6: Oxirane oxygen contents of reaction mixture reacted by 143

different dicarboxylic acids with EPOo at 180 °C for 4 h

xxvi

Figure 3.7: Viscosity tested at 25 °C and 40 °C 144

Figure 3.8: Hydrogen bonds between carboxyl and hydroxyl groups 145

in the polyester polyol

Figure 3.9: Cloud point and pour point of the reaction products 146

Figure 3.10: FTIR spectrum of epoxidized palm olein, EPOo 148

Figure 3.11: FTIR spectrum of polyester polyol B1 after 4 h of reaction 149

at 180 ºC

Figure 3.12: FTIR analysis on sample B1 to monitor the formation of OH 150

band and the disappearance of C-O stretch of epoxides

Figure 3.13: FTIR analysis on sample B2 to monitor the formation of 151

OH band and the disappearance of C-O stretch of epoxides







Figure 3.17: 1HNMR spectrum of EPOo in CDCl3 156

Figure 3.18: 1HNMR spectrum of polyester polyol B1 in CDCl3 158

Figure 3.19: 13

CNMR spectrum of EPOo in CDCl3 161

Figure 3.20: 13

CNMR spectrum of polyester polyol B1 in CDCl3 163

Figure 3.21: GPC chromatograms and results of EPOo 166

Figure 3.22: GPC chromatograms and results of B1 167

Figure 3.23: The effects of reaction time on average molecular weight 169

of polyester polyol

Figure 3.24: Comparison of the average molecular weight of 170

polyester polyol, P1-P4, obtained from different temperature

Figure 3.25: Comparison of the average molecular weight of 172

polyester polyol, B1-B5, at 180 °C for 4 h

xxvii

Figure 3.26: Effect of isocyanate index on density and hysteresis of the foam 176

Figure 3.27: Effect of isocyanate index on compression stress of the foam 177

Figure 3.28: Effect of isocyanate index on tensile stress and elongation 180

at break of the foam

Figure 3.29: Effect of isocyanate index on tear resistance of the foam 181

Figure 3.30: Microphotographs of open cell flexible polyurethane foam 183

prepared with isocyanate index in the range of

0.90-1.10 at x 40 magnification

Figure 3.31: DSC curves of the polyurethane foam 185


Figure 3.33: Effect of water content on density and hysteresis of the foam 190

Figure 3.34: Effect of water content on compression stress of the foam 192

Figure 3.35: Effect of water content on tensile stress and elongation 195

at break of the foam

Figure 3.36: Effect of water content on tensile stress and tear resistance 194

of the foam


prepared from 2, 3 and 4 g of water content at x40 magnification





Figure 3.42: Effect of different polyols on density and hysteresis of the foam 204

Figure 3.43: Effect of different polyols on compression stress of the foam 205

Figure 3.44: Effect of different polyols on tensile stress and 208

tear resistance of the foam

Figure 3.45: Effect of different polyols on elongation at break 209

of the foam

Figure 3.46: Representation of the ideal structure of polyurethane 210

xxviii


prepared from different polyols and 2 g of water

at x40 magnification



Figure 4.1: Reaction setup 219

Figure 4.2: Illustration of the dimensional stability test sample 236

Figure 4.3: Tear resistance test specimens 248

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ABBREVIATIONS

AFM Atomic Force Microscopy

AOCS American Oil Chemist’s Society

AOTD Advanced Oleochemical Technology Division

ASTM American Society for Testing and Materials

ATR-FTIR Attenuated Total Reflection- Fourier Transform InfraRed

BSA N, O-bis (trimethylsilyl) acetamide

BSTFA N,O-bis(trimethylsilyl)-trifluoroacetamide

CASE Coating, Adhesives, Sealants, Elastomers

CDCl3 Deuterated chloroform

CFCs Chlorofluorocarbons

CNSL Cashew Nut Shell Liquid

DAT Diamino toluene

DEA Diethanolamine

DGEBA 2, 2-bis [4- (2, 3-epoxypropoxy) phenyl] propane/ diglycidyl ether

of bisphenol A

DMA Dynamic Mechanical Analysis

DMPA Dimethylol propionic acid

DSC Differential Scanning Calorimeter

EFB Empty Fruit Bunch

EPOo Epoxidized Palm Olein

fnOH Number average functionality

FTIR Fourier Transform InfraRed

GC Gas Chromatography

GC-MS Gas Chromatography-Mass Spectrometry

xxx

GPC Gel Permeation Chromatography

H12MDI 4, 4’ di(isocyanatocyclohexyl)methane

HDI Hexane-1, 6-diol diisocyanate

HPLC High Performance Liquid Chromatography

HTPB Hydroxyl terminated polybutadiene

IPA Isopropyl alcohol

IPDI Isophorone diisocyanate

IPDI Isophorone diisocyanate

KBr Potassium bromide

LC-MS Liquid Chromatography-Mass Spectrometry

LOI Limiting Oxygen Index

MALDI-TOF Matrix Assisted Laser Desorption /Ionization- Time Of Flight

MDI Diphenylmethane diisocyanate

Mn Number average molecular weight

MPOB Malaysian Palm Oil Board

MRI Magnetic Resonance Imaging

Mw Weight average molecular weight

NMR Nuclear Magnetic Resonance

OMO Modal aryl-alkyl diurethane

OOC Oxirane Oxygen Contents

PDI Polydispersity index

PDMS Polydimethylsiloxane

PEO-PPO Polyethylene oxide-co-propylene oxide

PGE Phenylglycidyl ether

PKO Palm Kernel Oil

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PKOo Palm Kernel Olein

PPG Polypropylene glycol

Pph Parts per hundred

PTMO Poly (oxytetramethylene) diol

PU Polyurethane

PUDs Polyurethane dispersions

Quadrol N,N,n’,N’-tetrakis[2-hydroxypropyl]ethylenediamine

RBD Refined Bleached Deodorized

RHR Rate of heat release

SAXS Small Angle X-ray Scattering

SEC Size Exclusion Chromatography

TDI Toluene diisocyanate

TEA Triethanolamine

TEBAC Triethylbenzyl ammoniumchloride

TEDA Triethylene diamine

TEM Transmission Electron Microscopy

Tg Glass transition temperature

TGA Thermogravimetric analysis

THF Tetrahydrofuran

Tdec Decomposition peak temperature

VEM Video-Enhanced Optical Microscopy

WAXS Wide-Angle X-ray Diffraction

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