CHEMISTRY pdf

DEGRADABILITY OF POLYMER COMPOSITES FROM RENEWABLE RESOURCES A Thesis submitted to the UNIVERISTY OF PUNE for the degree of DOCTOR OF PHILOSOPHY in CHEMISTRY by JITENDRA KUMAR PANDEY Polymer Chemistry Division National Chemical Laboratory Pune – 411008 India December 2004 DEDICATED TO AMMA, BAPPA & PROF. RAM GOPAL YADAV CERTIFICATE This is to certify that the work incorporated in this thesis entitled “Degradability of Polymer Composites from Renewable Resources” submitted by Mr. Jitendra Kumar Pandey was carried out by the candidate under my supervision at the National Chemical Laboratory. Such material has been obtained from other sources has been duly acknowledged. Date: (R.P.Singh) Research guide Acknowledgements I got the opportunity to associate myself with Dr. Raj Pal Singh, senior scientist, Polymer Chemistry Division, National Chemical Laboratory Pune, as my supervisor. As an outstanding scientist and teacher he has given me the benefit of his guidance throughout the course work. I am grateful to him for showing me all the angles of research life. I also take this opportunity to thank, Head of Polymer Chemistry Division and all scientific staff, my seniors and colleague from this laboratory, for their unparalleled company and valuable support. On this special occasion of my life, I also remember and express my gratitude to Dr. S.P. Tripathi, Sri Subhash Tiwari, Sri Bhola Singh and all the friends of my father who always called and encouraged me during difficult time. I am thankful to my all family members for their courageous assistance during my research. It’s my privilege to thank the Director, NCL for giving me this opportunity and providing all necessary infrastructure and facilities. Financial assistance from CSIR, New Delhi is greatly acknowledged. (Jitendra Kumar Pandey) ABBREVIATIONS ASTM American Society for Testing and Materials AESO Acrylated Epoxidized Soybean Oil CMC Carboxymethylcellulose CA Cellulose Acetate CFRP Carbon fiber reinforced composites CEN Comite Europeen de Normalisation DMSO Dimethyl sulfoxide DSC Differential Scanning Calorimetry DIN Deutsches Institut für Normung Ev DS Degree of Substitution CDA-g-PLAs Cellulose diacetate-graft-poly(lactic acid)s CDA Cellulose Diacetate DD Degree of Deacetylation DMA Dynamic Mechanical Analyzer DFC Direct Fiber Composite DP Degree of Polymerization EVSEM Environmental Scanning Electron Microscopy EP Ethylene -Propylene Co-polymer EPMA Ethylene-Propylene-Maleic Anhydride co-polymer EVA Ethylene vinyl aetate copolymer ESO Epoxidised soybean oil EVAc Co-polymers of ethylene with vinyl acetate EVAl Ethylene- vinylalcohol co-polymer EVAMA EVAc modified with maleic anhydride ESR Electron Spin Resonance ESCA Electron Scanning Chemical Analysis ELO Epoxidized linseed oil GPTMS 3-glycidoxypropyltrimethoxysilane GFC Graft Fiber Composite GC Gas Chromatography GPC Gel Permission Chromatography [Size Exclusion Chromatography] GC- MS Gas Chromatography – Mass Spectroscopy HTA Hydrogenated tallow alkyl ISO International Organization for Standardization LDPE Low Density Polyethylene LC Liquid Chromatography LSC Liquid Scintillation Counting MC Methyl Cellulose MMT Montmorillite MAH Maleic anhydride MALDI-TOF Matrix Assisted Laser Desorption Ionization Time-of-flight Mass Spectrometry MW Molecular Weight MBS Methyl Methacrylate -Butadiene-Styrene co-polymer Na+-MMT Sodium Montmorillite O-PCL Oligomeric polycaprolactone OMMT Orgonically modified montmorillite PCL Poly (ε-caprolactone) PP-g-MA Polypropylene grafted maleic anhydride PS Polystyrene PLA Poly actiacid PE Polyethylene PHB Poly (hydroxybutyrate) PHA Polyhydroxyalkanoates PBS Poly (butylenes succinate) PALF Pineapple Leaf Fibre PCA Plasticized Cellulose Acetate PS Polystyrene PHBV Poly(3-hydroxybutyrate-co-3-hydroxyvalerate) PVOH Polyvinylalcohol PVA Polyvinylacetate PP-MAH Polymer functionalized with maleic anhydride. RH Relative Humidity SMA Styrene-Maleic Anhydride co-polymer SEM Scanning Electron Microscopy TPS Thermo Plastic Starch TPP Tripolyphosphate TEM Tunneling Electron Microscopy TGA Thermal Gravimetric Analysis UV Ultra violet VATM Vacuum Assisted Transfer Molding WVA Water vapor Absorption WG Waste Gelatin XRD X-Ray Diffraction WAXD Wide Angle X-Ray Diffraction ABSTRACT ABBREVIATIONS CHAPTER I: POLYMER COMPOSITES FROM RENEWABLE RESOURCES 1.1. Introduction 1 1.2. Renewable resources 2 1.3. Importance of renewable resources 2 1.4. Polymers from renewable resources 2 1.5.Degradation of polymeric materials 4 1.5.1. Photodegradation 4 1.5.2. Thermal Degradation 5 1.5.3. Biodegradation 5 1.5.3.1. Degradable Plastic 5 1.5.3.2. Biodegradable Plastic 5 1.6. Miscellaneous 6 1.7. Evaluation methods for degradability. 6 1.8. Polymer composites from renewable resources. 10 1.8.1. Biofiber composite 10 1.8.1.2. Degradability of biofibres 11 1.8.1.3. Composites from cellulose 11 1.8.2. Starch composites 15 1.8.2.1. Composites of starch with synthetic polymers 16 1.8.2.2. Composites of starch with natural polymers 18 1.8.2.3. Composites of starch after chemical modification 19 1.8.2.4. Nanocomposites of starch 20 1.8.2.5. Commercial biodegradable products of starch 21 1.8.3. Composites of PLA 23 1.8.3.1. Composites with natural polymers 23 1.8.3.2. Nanocomposites of PLA 24 1.8.3.3. Commercial degradable products from PLA 25 1.8.4. Poly ( hydroxy alkanoates) 25 1.8.5. Composites from Natural oils 27 1.8.6. Composites from Pectin 28 1.8.7. Composites from Gelatin 29 1.8.8. Composites from Chitosan 30 1.8.9. Soy Plastics 31 1.8.10. Miscellaneous 32 1.9. Conclusions and future trends 34 1.10. References 35 CHAPTER II: OBJECTIVES AND APPROACHES OF PRESENT INVESTIGATION 2.1 Objective of the Present work 46 2.2. Approaches 47 2.3. References 48 CHAPTER III: DEGRADABILITY OF PE, PP AND EP COPOLYMERS UNDER BIOTIC AND ABIOTIC ENVIRONMENTS 3.1. Introduction 49 3.2. Experimental 49 3.2.1. Materials 49 3.2.2 Preparation of films 50 3.2.3. UV irradiation 50 3.2.4. Viscosity Measurement 50 3.2.5. Incubation in compost 50 3.2.6. Incubation in culture 51 3.2.7. FT-IR Spectroscopy 52 3.2.8. Scanning Electron Microscopy 52 3.3 Results and Discussion 52 3.3.1 Incubation in Compost 52 3.3.2. Variation in viscosity 54 3.3.3. FT-IR Spectroscopy 55 3.3.4 Incubation in culture 60 3.3.5. Morphological aspects 61 3.4. Conclusions 63 3.5. References 64 CHAPTER IV: DEGRADABILITY OF BIOCOMPOSITES PREPARED FROM CELLULOSE AND PE, PP , EP COPOLYMERS 4.1 Introduction 66 4.2. Experimental Part 67 4.2.1. Material 67 4.2.2. Preparation of composites 67 4.2.3. Characterization and performance evaluation 68 4.3. Results and discussion 68 4.3.1. Compatibility of fiber and polymer matrix 68 4.3.2. Photodegradation 71 4.3.3. Biodegradation 74 4.3.3.1.Composting 74 4.3.3.2. Culture testing 79 4.3.4 Morphological aspects 81 A. PCL–granular starch blends 85 B. Hydrophobic coating of starch granules and melt blending with PCL 87 C. Synthesis of PCL-grafted dextran copolymers and use as compatibilizer in PCL–granular starch blends 88 D. In situ PCL grafting onto starch granules and melt blending with PCL. 92 4.4. Conclusions 94 4.5. References 95 CHAPTER V: DEGRADABILITY OF POLYMER COMPOSITES PREPARED FROM LAYERED SILICATE 5.1. Introduction 98 5.2. Experimental 99 5.2.1. Materials 99 5.2.2. Preparation of nanocomposites and characterization 99 5.2.3. Durability evaluation 100 5.3. Results and discussion 101 5.3.1. Structure of composites 101 [...]... advantage, particularly, as a solution to the plastic waste generated problems in the environment One of the exciting directions for this field is the growing interface between molecular biology and polymer chemistry This interface combines powerful control over polymer structure with the functional attributes of polymers, leading to new and useful applications for these types of biopolymers However, overtime . OF PUNE for the degree of DOCTOR OF PHILOSOPHY in CHEMISTRY by JITENDRA KUMAR PANDEY Polymer Chemistry Division National Chemical Laboratory Pune – 411008 India. I got the opportunity to associate myself with Dr. Raj Pal Singh, senior scientist, Polymer Chemistry Division, National Chemical Laboratory Pune, as my supervisor. As an outstanding scientist. showing me all the angles of research life. I also take this opportunity to thank, Head of Polymer Chemistry Division and all scientific staff, my seniors and colleague from this laboratory, for