Synthesis, Characterization and Properties of the New Unsaturated Polyester Resins for Composite Applications

SYNTHESIS, CHARACTERIZATION AND PROPERTIES OF THE NEW UNSATURATED POLYESTER RESINS FOR COMPOSITE APPLICATIONS

by

NOORSHASHILLAWATI AZURA BINTI MOHAMMAD

Thesis submitted in fulfilment of the requirements for the degree of Master of Science

APRIL 2007

ACKNOWLEDGEMENTS

Alhamdulillah, praised to Allah The Almighty for His love, guidance and strength until I completed this Master thesis.

I would like to thank to Assoc. Prof Dr. Abdul Khalil Shawkataly, my main supervisor and Dr. Issam Ahmed Mohammed, my co-supervisor for their guidance, encouragement and support throughout my graduate study. They acted as the driving force behind this research. They provide the opportunity for each student to do his/her research, yet when asked, they are always willing to provide their knowledge and expertise to assist in understanding the problem. Their professional and personable attitude has made my stay at USM a very rewarding and memorable experience.

I would also like to thank to Dean, Professor Rozman Hj Din and all lecturers of Bio-Resource, Paper and Coating Divison (BPC), School of Industrial Technology, for their guidance and help.

Grateful thanks express to lab assistant of BPC Division, Mr. Azhar, Mr. Farim, Mr. Mat, Tuan Haji Ishak, Mrs. Hasni, Mrs. Aida, Mr. Maarof, Mr. Abu, Mr. Shamsul, Mr. Ali and Mr. Md. Hassan for their assistance and co-operation in lab works and technical support during my graduate study.

Special thanks are given to my friends, Neza, Fir, Syed Asri, Pali, Kak Wani, Kak Nida, Amzar, Husna, Rose, Zaim, Falah, Kang and all my friends for their love, support, and helpful discussions. The assistance and moral support from

ii

other colleagues and friends is also appreciated. I also would like to acknowledge Ministry of Science, Technology and Innovative (MOSTI) for financial support.

My utmost appreciation and thanks are given to my beloved mama, Halijah binti Ngah and papa Mohammad bin Ngah, for their love, prayers, support throughout my graduate career and who made me what I am today. I also thank my siblings Norazlina, Nurul Emi Nor Ain, Mohd. Alif Fakrol and Mohd. Amirul Firdaus for their love and encouragement during the most critical time, in the hour of need and frustration. Thank you for everything.

Finally, I would like to dedicate this thesis to my beloved late sister, Noor Erra Wahyu for bringing so much joy the moment she came into my life. Your love, support and patience make me strong and capable to complete this thesis. Without you I could never have accomplished our dream because you raise me up, my dear.

iii

TABLE OF CONTENTS Page ACKNOWLEDGEMENTS TABLE OF CONTENTS LIST OF TABLES LIST OF FIGURES LIST OF ABBREVIATION LIST OF PUBLICATION AND SEMINARS ABSTRAK ABSTRACT ii iv ix x xii xiii xiv xv

CHAPTER ONE: INTRODUCTION 1.0 1.1 Introduction Objectives of the Research 1 5

CHAPTER TWO: LITERATURE REVIEW 2.0 Composite Materials 7 8 9 11 13 14 15 17 21 22 27 27 28

2.0.1 Definition of Composite 2.0.2 Classification of Composite Materials 2.0.3 Fiber Reinforced Composites 2.0.4 How Does a Composite Work? 2.1 Matrix Materials

2.1.1 Thermoset 2.1.1.1 2.1.1.2 2.1.1.3 2.1.1.4 Current Interest Research of Unsaturated Polyester Classification Preparation Cross-linking Reactions Initiators Kinetic Studies on Cure Reactionsiv

2.1.1.4.1 2.1.1.4.2

2.1.1.4.3 2.1.1.5 2.1.1.5.1 2.1.1.5.2 2.1.1.5.3 2.1.1.5.4 2.1.1.5.5

Characterization of Cured Networks

31 32 32 33 34 35 37

Cured Networks and Properties Mechanical Properties Shrinkage Control during Cure Thermal and Oxidative Stability Properties Applications

2.1.2 Thermoplastic 2.2 Fiber Reinforcement Fiber Matrix Interface Lignocellulose Fiber Composite Classification of Lignocellulose Fibres Chemical Composition of Lignocellulose Fibres

38 40 44 46 46 47

2.2.1 2.3

2.3.1 2.3.2 2.3.3 2.3.4 2.3.5

Physical and Mechanical Properties of Lignocellulose Fibres 48 Oil Palm Empty Fruit Bunch Fibre and Its Composites Limitations of Lignocellulose Fibres 50 53

CHAPTER THREE: STRUCTURAL ELUCIDATION OF MONOMERS AND POLYMERS 3.0 3.1 Introduction Materials Fumaric acid 1, 6-hexanediol p-toluene Sulfonic Acid Sodium Bicarbonate Triethylaminev

58 59 59 59 59 59 60

3.1.1 3.1.2 3.1.3 3.1.4 3.1.5

3.1.6 3.1.7 3.1.8 3.1.9 3.2 3.2.1

Ethanol Tetrahydrofuran Ethylene Glycol Methylene Chloride Methods Synthesis of Unsaturated Polyester Oligomers Synthesis of Bis-(2-hydroxyethy) fumarate Synthesis of Bis-(6-hydroxyhexyl) fumarate

60 60 60 60 61 61 61 62 62 65 65 65 66 67 67 67 68 70 72 72 74 76 77

3.2.1.1 3.2.1.2 3.2.2

Preparation of the Polymers

3.3 Characterization of Monomers and Polymers 3.3.1 Fourier Transform Infrared Spectroscopy (FT-IR) 3.3.2 Nuclear Magnetic Resonance Spectroscopy (1H-NMR) 3.3.3 CHN Elemental Analyses 3.3.4 Image Analyzer(IA) 3.4 Results and Discussions

3.4.1 Characterization of Monomers 3.4.1.1 3.4.1.2 Synthesis and characterization of Monomer I Synthesis and Characterization of Monomer II

3.4.2 Characterization of Polymers 3.4.2.1 3.4.2.2 Synthesis and Characterization of Polymer I Synthesis and Characterization of Polymer II

3.4.3 CHN Analyses 3.4.4 Image Analyzer

vi

CHAPTER FOUR: THERMAL PROPERTIES OF MONOMERS AND POLYMERS

4.0 4.1 4.2

Introduction Materials Methods

79 82 82 82 83 83 83 86

4.2.1 Thermogravimetric Analysis (TGA) 4.2.2 Differential Scanning Calorimetry (DSC) 4.3 Results and Discussion 4.3.1 Thermal Stability of Monomers 4.3.2 Thermal Stability of Polymers

4.3.3 Melting and Glass Transition Temperature (Tg) of Monomers and 90 Polymers

CHAPTER FIVE: MECHANICAL PROPERTIES AND PHYSICAL PROPERTIES OF COMPOSITES 5.0 5.1 Introduction Material 95 96 96 96 96 97 97 97

5.1.1 Oil Palm Empty Fruit Bunches (OPEFB) 5.1.2 Unsaturated Polyesters Resin 5.1.3 Methyl Ethyl Ketone Peroxide (MEKP) 5.1.4 Styrene 5.2 Methods

5.2.1 Preparation of Non-Woven Oil Palm Empty Fruit Bunches (OPEFB) Fiber 5.2.2 Preparation of Unsaturated Polyester Resins 5.2.3 Composite Preparation Process

98 99

vii

5.2.4 Impregnation and Curing Process of the Composite 5.3 Characterization of Composites

100 101 101 102 104 105 106 106 106 106 108 110 112 112 114 116 119 119

5.3.1 Tensile Test (ASTM D 638-03) 5.3.2 Flexural Test (ASTM D 790-03) 5.3.3 Impact Test (ASTM D6110-05a) 5.3.4 Water Absorption of Composites (ASTM D 570) 5.4 Results and Discussion

5.4.1 Mechanical Properties 5.4.1.1 Tensile Properties Tensile Strength Tensile Modulus Elongation at Break

5.4.1.1.1 5.4.1.1.2 5.4.1.1.3 5.4.1.2

Flexural Properties Flexural Strength Flexural Modulus Impact Properties

5.4.1.2.1 5.4.1.2.2 5.4.1.2.3

5.4.2 Physical Properties 5.4.2.1 Water Absorption

CHAPTER SIX: CONCLUSION AND RECOMMENDATION FOR FUTURE WORK 6.0 6.1 Conclusion Recommendations for Future Work 122 123

BIBLIOGRAPHY

125

viii

LIST OF TABLES Page Table 2.1 Inhibitor-Accelerator Curing for Room Temperature 28

Table 2.2

Typical Values for Various Properties of Cured Polyester, Unfilled and Reinforced Some Typical Properties of Thermoset and Thermoplastic Resins

36

Table 2.3

40

Table 2.4

Chemical Composition Lignocellulose Fibers

of

Some

Common

47

Table 2.5

Mechanical and Physical Properties of Lignocellulose Fibers and Synthetic Fibers

48

Table 3.1

Yield and Elemental Analysis of Unsaturated Polyesters Thermal Stability of Monomers Thermal Stability of Polymers Thermal Properties of Monomers Thermal Properties of Polymers Solubility Results of Unsaturated Polyester

76

Table 4.1 Table 4.2 Table 4.3 Table 4.4 Table 5.1

84 87 90 92 99

ix

LIST OF FIGURES Page Figure 2.1 Anhydrides Acid, Acids, Unsaturated Anhydrides Acids and Alcohols Formed Polyester. Classifications of Fibers (Lilholt & Lawther, 2003) Bis-(2-hydroxylethyl) fumarate Bis-(6-hydroxylhexyl) fumarate Synthesis of Bis-(2-hydroxylethyl) fumarate and Its Polymer Synthesis of Bis-(6-hydroxylhexyl) fumarate and Its Polymer 22

Figure 2.2 Figure 3.1 Figure 3.2 Figure 3.3

43 61 62 63

Figure 3.4

64

Figure 3.5 Figure 3.6 Figure 3.7 Figure 3.8 Figure 3.9 Figure 3.10

FT-IR Spectrum of Monomer I1

69 70 71 72 73 74

H-NMR Spectroscopy of Monomer I

FT-IR Spectrum of Monomer II1

H-NMR Spectroscopy of Monomer II

FT-IR Spectrum of Polymer I1

H-NMR Spectroscopy of Polymer I

Figure 3.11 Figure 3.12 Figure 3.13 Figure 3.14 Figure 3.15 Figure 3.16 Figure 4.1 Figure 4.2

FT-IR Spectrum of Polymer II1

75 76 77 77 78 78 84 85

H-NMR Spectroscopy of Polymer II

Image Analysis of Monomer I Image Analysis of Monomer II Image Analysis of Polymer I Image Analysis of Polymer II Thermogravimetric Analysis of Monomer I Thermogravimetric Analysis of Monomer II

x

Figure 4.3 Figure 4.4 Figure 4.5

Thermogravimetric Analysis of Polymer I Thermogravimetric Analysis of Polymer II Differential Monomer I Differential Monomer II Scanning Calorimetry Analysis of

87 88 91

Figure 4.6

Scanning

Calorimetry

Analysis

of

91

Figure 4.7

Differential Scanning Calorimetry Analysis of Polymer I Differential Scanning Calorimetry Analysis of Polymer II Unsaturated Polyesters Resin Methyl Ethyl Ketone Peroxide (MEKP) Styrene Non-Woven Oil Palm Fiber Mat Schematic Process Diagram of Composite Preparation