Embed Size (px)
Citation preview
Natural Rubber Materials
Volume 1: Blends and IPNs
Edited by
Sabu Thomas, Rajisha K. R., Hanna J. Maria
Mahatma Gandhi University, Kottayam, India
Email: [email protected]
Chin Han Chan
MARA University of Technology, Selangor, MalaysiaEmail: [email protected]
and
Laly A. Pothen
Bishop Moore College, Mavelikkara, India
Email: [email protected]
RSC Publishing
Contents
Chapter 1 Natural Rubber Based Blends and IPNs: State of the Art,New Challenges and Opportunities 1
Gordana Markovic, Milena Marinovic-Cincovic,
Vojislav Jovanovic, Suzana Samarzija-Jovanovic and
Jaroslava Budinski-Simendic
1.1 Introduction and History 1
1.1.1 Interpenetrating Polymer Networks 9
1.1.2 History of IPN Development 9
1.1.3 Properties of Polymer Blends and IPNs 11
1.1.4 Glass Transition and Viscoelastic Behaviour 12
1.1.5 Morphology 13
1.2 Recent Trends and Developments in Natural Rubber
Based Blends and IPNs 14
1.3 Applications and the Potential Market for IPNs 20
1.4 Environmental Impact and Recycling 22
1.5 Conclusions 23
Acknowledgements 24
References 24
Chapter 2 Natural Rubber: Biosynthesis, Structure, Properties and
Application 28
Jitladda Tangpakdee Sakdapipanich and Porntip Rojruthai
2.1 Introduction 28
2.2 Biosynthesis of NR 30
2.3 Structure and Properties of NR 33
2.3.1 Initiating Terminal of the Rubber Molecule 33
2.3.2 Terminating End of the Rubber Molecule 35
RSC Polymer Chemistry Series No. 7
Natural Rubber Materials, Volume 1: Blends and IPNs
Edited by Sabu Thomas, Chin Han Chan, Laly A. Pothen, Rajisha K. R., Hanna J. Maria
© The Royal Society of Chemistry 2014
Published by the Royal Society of Chemistry, www.rsc.org
ix
X Contents
2.3.3 Structure of Branch Points, Gel and Storage
Hardening 37
2.3.4 Properties of NR 38
2.4 Chemical Modification of NR 39
2.4.1 Hydrogenation 40
2.4.2 Epoxidation 40
2.4.3 Chlorination 41
2.4.4 Grafting Copolymerization 41
2.4.5 Oxidative Degradation 42
2.4.6 Cyclization 43
2.5 Processing of NR and its Applications 44
2.5.1 Processing of NR 44
2.5.2 Applications of NR 45
2.6 Conclusions 46
References 46
Chapter 3 Non-Rubbers and Abnormal Groups in Natural Rubber 53
Eng Aik Hwee
3.1 Non-Rubbers in Natural Rubber 53
3.1.1 Lipids 54
3.1.2 Proteins, Amino Acids and Other Nitrogenous
Compounds 57
3.1.3 Inositols and Carbohydrates 61
3.1.4 Ash 62
3.1.5 Volatile Matter 63
3.2 Abnormal Groups in Natural Rubber 63
3.2.1 rraws-Isoprene and Dimethylallyl (DMA)
Groups 64
3.2.2 Ester Groups, Fatty Acids and Phospholipids 64
3.2.3 Epoxide Groups 64
3.2.4 Aldehyde Groups 65
3.2.5 Bonded Proteins and Amino Groups 67
3.3 Future Trends 67
References 67
Chapter 4 The Production of Natural Rubber from Hevea brasiliensis
Latex: Colloidal Properties, Preservation, Purification and
Processing 73
C. C. Ho
4.1 Introduction 73
4.2 Sources of NR 74
4.3 Evolution of NR as an Industrial Elastomer 75
4.4 Colloidal Properties of NR Latex and Stability 78
Contents xi
4.5 Production of Commercial NR Latex from
Hevea 80
4.5.1 Preservation of NR Latex 81
4.5.2 Latex Purification and Concentration
Processes 82
4.5.3 Commercial Concentration Methods for NR
Latex 84
4.5.4 Specialty NR Latices 87
4.5.5 Chemically Modified Rubber Latices 90
4.5.6 Recent Advances in NR Latex Technology 93
4.6 NR Production Methods 94
4.6.1 Sheet Rubbers: USS, RSS and ADS 95
4.6.2 Crepe Rubbers: Pale Crepe, White Crepe and
Brown Crepe 97
4.6.3 Block Rubbers: Technically Specified Rubbers
and Standard Technical Rubbers 98
4.6.4 Rubber Products from Field Coagula 98
4.6.5 Skim Rubbers 100
4.6.6 Specialty Rubbers and Chemically Modified
Rubbers 100
4.7 Major Industrial Applications of NR and
NR Latex 103
References 104
Chapter 5 Natural Rubber Blends and Based IPNs: ManufacturingMethods 107
Wanvimon Arayapranee
5.1 Introduction 107
5.2 Latex Based Methods 110
5.2.1 Latex Mixing 111
5.2.2 Maturation 112
5.2.3 Latex Curing Processes 112
5.3 Solution Based Methods 114
5.3.1 Solution Manufacturing Processes 115
5.3.2 Solution Mixing 115
5.4 Solid Natural Rubber Based Methods 115
5.4.1 Two-Roll Mills 116
5.4.2 Internal Batch Mixers 118
5.4.3 Continuous Mixers 122
5.4.4 Solid Rubber Curing Processes 126
5.5 Advantages and Disadvantages of Each
Technique 128
5.6 Conclusions 130
References 130
xii Contents
Chapter 6 Filler Migration in Natural Rubber Blends During the
Mixing Process 132
Hai Hong Le, Sybill Ilisch, Gert Heinrich and
Hans-Joachim Radusch
6.1 Introduction 132
6.2 Theoretical Prediction of Filler Localization in
Rubber Blends at an Equilibrium State using the
Z-Model 133
6.3 The Wetting Concept for Experimental Determination
of Filler Localization in Rubber Blends 137
6.4 Equipment and Experimental Methods 141
6.4.1 Preparation of Blends 141
6.4.2 Characterization 142
6.5 Results and Discussion 144
6.5.1 Silica Localization in Rubber Blends 144
6.5.2 Carbon Black Localization in Rubber Blends 157
6.5.3 Carbon Nanotube (CNT) Localization in
Rubber Blends 162
6.5.4 Nanoclay Transfer in Rubber Blends 168
6.6 Conclusions 171
Acknowledgements 172
References 172
Chapter 7 NR Blends and IPNs: Miscibility and Immiscibility 177
Wiwat Pichayakom, Jirapomchai Suksaeree and
Prapaporn Boonme
7.1 Introduction 177
7.2 Definitions 178
7.3 Miscibility and Immiscibility of NR Blends and IPNs 180
7.3.1 Techniques for Preparing NR Blends 180
7.3.2 Identification Parameters for Determination of
Miscibility 181
7.3.3 NR Blends and IPNs 182
7.4 Thermodynamics of NR Blends and IPNs 185
7.5 Phase Separation and Compatibilization 186
7.5.1 Achievement of Thermodynamic Miscibility 187
7.5.2 Addition of Block or Graft Copolymers 187
7.5.3 Addition of Functional or Reactive Polymers 189
7.5.4 In Situ Graft Polymerization or Reactive
Blending 190
7.6 Techniques for Measuring Miscibility and
Immiscibility Properties 191
7.6.1 Glass Transition Temperature Studies 191
Contents xiii
7.6.2 Scattering Studies 192
7.6.3 Morphological Studies 192
7.6.4 Infrared Spectroscopy 192
7.7 Conclusions 193
References 193
Chapter 8 Natural Rubber Based Non-Polar Synthetic Rubber
Blends 195
Seiichi Kawahara
8.1 Introduction 195
8.2 Miscible NR Blends 196
8.2.1 Background 196
8.2.2 Characterization of NR-Sol and NR-Gel 198
8.2.3 LCST Phase Behaviour 199
8.3 Immiscible NR Blends 203
8.3.1 Background 203
8.3.2 Characterization of NR/SBR Blends 204
8.3.3 Tear Energy 205
8.4 Conclusions 210
References 210
Chapter 9 Natural Rubber Based Polar Synthetic Rubber Blends 213
Konstantinos G. Gatos
9.1 Introduction 213
9.2 Preparation Methods 214
9.2.1 Latex 214
9.2.2 Solution Mixing 215
9.2.3 Melt Blending 215
9.3 Blend Characteristics 217
9.3.1 Rheology 217
9.3.2 Curing 219
9.3.3 Swelling and Oil Resistance 220
9.3.4 Morphology 222
9.3.5 Mechanical and Dynamic-MechanicalBehaviour 225
9.3.6 Thermal Properties 229
9.3.7 Dielectric Properties 230
9.3.8 Infrared Absorbance 232
9.3.9 Ageing and Other Properties 235
9.4 Applications 236
9.5 Outlook 237
References 237
xiv Contents
Chapter 10 Thermoplastic Elastomers from High-Density Polyethylene/Natural Rubber/Thermoplastic Tapioca Starch: Effects of
Different Dynamic Vulcanization 242
Mohd Kahar Ab Wahab, Nadras Othman and
Hanafi Ismail
10.1 Introduction 242
10.2 Materials and Methodology 246
10.2.1 Preparation of Thermoplastic TapiocaStarch (TPS) 246
10.2.2 Dynamic Vulcanization with HVA-2 and
Sulfur Curative Agent 246
10.2.3 Tensile Properties 246
10.2.4 Gel Content 247
10.2.5 Fourier Transform Infrared Spectroscopy(FTIR) 247
10.2.6 Scanning Electron Microscopy (SEM) 248
10.2.7 Thermogravimetric Analysis (TGA) 248
10.2.8 Dynamic Mechanical Thermal Analysis
(DMTA) 248
10.2.9 Differential Scanning Calorimetry (DSC) 248
10.3 Results and Discussion 248
10.3.1 Processing Characteristics 248
10.3.2 Tensile Properties 250
10.3.3 Gel Content 253
10.3.4 Structural Analysis 254
10.3.5 Blend Morphology 255
10.3.6 Thermogravimetric Analysis 258
10.3.7 Differential Scanning Calorimetry 260
10.4 Conclusions 262
Acknowledgements 262
References 262
Chapter 11 Natural Rubber/Engineering Thermoplastic Elastomer
Blends 265
E. Purushothaman and Mehar Al Minath
11.1 Introduction 265
11.2 Recent Developments in TPEs 267
11.3 Preparation of TPEs 268
11.3.1 Mixing 268
11.3.2 Solution Casting 269
11.4 Characterization of TPEs 270
11.4.1 Rheological Studies 270
11.4.2 Morphological Studies 271
11.4.3 Scattering Analyses 273
Contents xv
11.4.4 Mechanical Properties 273
11.4.5 Thermal Analyses 276
11.4.6 Dielectric Properties 278
11.5 Applications of TPEs 279
11.6 Conclusions 280
References 280
Chapter 12 Radiation Processing of Natural Rubber with Vinyl Plastics 284
Chantara Thevy Ratnam, Zurina Mohamad and
Mohammad Khalid Siddiqui
12.1 Introduction 284
12.2 Radiation Effects on Polymers 285
12.3 Radiation Crosslinking of Polymers 285
12.4 Radiation Sensitizers used as Crosslinking Agents 286
12.5 Radiation Crosslinking of Natural Rubber (NR) 286
12.5.1 The Properties of Radiation Crosslinked NR 287
12.6 Radiation Crosslinking of Epoxidized Natural
Rubber (ENR) 288
12.7 Radiation Crosslinking of NR Based Blends 289
12.7.1 Radiation Crosslinking of PVC/ENR Blends 290
12.7.2 Radiation Crosslinking of EVA/ENR Blends 292
12.7.3 Radiation Crosslinking of PVC/NR Blends 294
12.8 Conclusions 297
Acknowledgements 297
References 297
Chapter 13 Blends and IPNs of Natural Rubber with Acrylic Plastics 300
Wiwat Pichayakorn, Jirapornchai Suksaeree and
Prapaporn Boonme
13.1 Introduction 300
13.2 The History of Natural Rubber-Acrylate Blends and
IPNs 301
13.3 Preparation Methods of Natural Rubber-Acrylate
Blends and IPNs 302
13.3.1 Natural Rubber-Acrylate Blends 302
13.3.2 Natural Rubber-Acrylate IPNs 306
13.4 Natural Rubber-Acrylate Blends and IPNs:
Properties and Characterization Techniques 307
13.4.1 Morphological Properties 307
13.4.2 Mechanical Properties 313
13.4.3 Thermal and Thermornechanical Properties 315
13.4.4 Rheological Properties 318
xvi Contents
13.5 Applications of Natural Rubber-Acrylate Blends
and IPNs 320
13.6 Conclusions 321
References 322
Chapter 14 Photoreactive Nanomatrix Structures Formed byGraft Copolymerization of 1,9-NonanedioI Dimethacrylateonto Natural Rubber 324
Oraphin Chaikumpollert, Nanthaporn Pukkate and
Seiichi Kawahara
14.1 Introduction 324
14.2 Inclusion Complex Formation ofNDMA and |3-CD 327
14.3 Graft Copolymerization of Inclusion Complex onto
DPNR Particles 330
14.4 Conclusions 334
References 334
Chapter 15 Blends and n»Ns of Natural Rubber with Thermosetting
Polymers 336
Raju Thomas, Ishak Ahmad, Sahrim Hj. Ahmad and
Shinu Koshy
15.1 Introduction 336
15.2 Elastomer-Modified Epoxy Resin Systems 337
15.3 Elastomer-Modified Unsaturated Polyester Resin
Systems 344
15.4 Conclusions 346
References 346
Chapter 16 Natural Rubber Blends with Biopolymers 349
Silvia Maria Martelli, Carol Sze Ki Lin, Zheng Sun,
Nathalie Berezina, Farayde Malta Fakhouri and
Lucia Helena Innocentini-Mei
16.1 Introduction 349
16.2 Natural Rubber/Lignin Blends 350
16.2.1 General Information 350
16.2.2 Blends and their Applications 351
16.3 Natural Rubber/Protein Blends 353
16.3.1 General Information 353
16.3.2 Blends and their Applications 356
16.4 Natural Rubber/Polysaccharide Blends 357
16.4.1 General Information 357
16.4.2 Blends and their Applications 358
Contents xvii
16.5 Natural Rubber/Polyester Blends 360
16.5.1 General Information 360
16.5.2 Blends and their Applications 361
16.6 Conclusions and Outlook 366
References 367
Chapter 17 Clay Reinforcement in Natural Rubber Based Blends:
Micro and Nano Length Scales 370
Yamuna Munusamy, Hanafi Ismail and
Chantara Thevy Ratnam
17.1 Introduction 370
17.2 Recent Developments 371
17.3 Preparation Methods 372
17.3.1 Development of Ethylene Vinyl Acetate/Natural Rubber/Organoclay Ternary Blends 374
17.4 Characterization of Nanocomposites 375
17.4.1 Morphology 375
17.4.2 Mechanical Properties 379
17.4.3 Thermal Properties 384
17.4.4 Flammability 386
17.5 Crosslinking Techniques 386
17.5.1 Chemical Crosslinking 386
17.5.2 Irradiation Crosslinking 389
17.6 Conclusions 391
References 391
Chapter 18 Rheological Behaviour of Natural Rubber Based Blends 394
Ploenpit Boochathum
18.1 Introduction 394
18.2 Rheological Behaviour 396
18.2.1 Natural Rubber-Thermoplastic Blends 396
18.2.2 Natural Rubber-Synthetic Rubber Blends 405
18.2.3 Chemically Modified Natural Rubber Blends 416
References 439
Chapter 19 Spectroscopy: Natural Rubber Based Blends and IPNs 441
SA-AD Riyajan
19.1 Introduction 441
19.2 UV-Vis Spectroscopy 442
19.2.1 Introduction to UV-Vis Spectroscopy 442
19.2.2 Sample Preparation and Typical Conditions
for UV-Vis Spectroscopy Measurement 442
19.2.3 Analysis of Polymer Blends 443
xviii Contents
19.3 Fourier Transform Infrared Spectroscopy (FTIR) 445
19.3.1 Introduction to FTIR 445
19.3.2 Sample Preparation and Typical Conditions
for FTIR 446
19.3.3 Analysis of Polymer Blends 447
19.4 Nuclear Magnetic Resonance (NMR)
Spectroscopy 460
19.4.1 Introduction to NMR Spectroscopy 460
19.4.2 Sample Preparation and Typical Conditions
for NMR 460
19.4.3 Analysis of Polymer Blends 461
19.5 Raman Spectroscopy 472
19.5.1 Introduction to Raman Spectroscopy 472
19.5.2 Sample Preparation and Typical Conditions
for Raman Spectroscopy 473
19.5.3 Analysis of Polymer Blends 473
19.6 Electron Spin Resonance (ESR) Spectroscopy 475
19.6.1 Introduction to ESR 475
19.6.2 Sample Preparation and Typical Conditions
for ESR 476
19.6.3 Analysis of Polymer Blends 476
19.7 Applications 477
19.8 Conclusions 478
Acknowledgements 478
References 478
Chapter 20 Mechanical and Viscoelastic Properties of Natural Rubber
Based Blends and IPNs 481
Wiwat Pichayakorn, Jirapornchai Suksaeree and
Prapaporn Boonme
20.1 Introduction 481
20.2 Instruments and Techniques for Mechanical and
Viscoelastic Evaluations 482
20.2.1 Mechanical Properties 482
20.2.2 Viscoelastic Properties 485
20.3 Mechanical and Viscoelastic Properties of Natural
Rubber Blends and IPNs 487
20.3.1 Natural Rubber/Thermoplastics 487
20.3.2 Natural Rubber/Thermosets 491
20.3.3 Natural Rubber/Synthetic Rubbers 494
20.3.4 Natural Rubber/Biopolymers 496
20.4 Conclusions 499
References 499
Contents xix
Chapter 21 Scattering Studies on Natural Rubber Based Blends and
IPNs 501
Valerio Causin
21.1 Introduction 501
21.2 Wide Angle X-Ray Diffraction 502
21.3 Small-Angle X-Ray Scattering 507
21.4 Small-Angle Neutron Scattering 517
21.5 Small-Angle Light Scattering 521
References 523
Chapter 22 Transport of Penetrant Molecules Through Natural Rubber
Based Blends and IPNs 530
Isaac O. Igwe
22.1 Introduction 530
22.2 Natural Rubber: Properties and Applications 533
22.3 Natural Rubber Based Blends 534
22.4 Natural Rubber Based Interpenetrating PolymerNetworks (IPNs) 535
22.5 Transport of Penetrant Molecules through Natural
Rubber Based Blends and IPNs 536
22.6 The Effects of Penetrant Absorption on the
Properties of Natural Rubber Systems 544
22.7 Conclusions 545
References 546
Chapter 23 Life Cycle Analysis, Ageing and Degradation Behaviour of
Natural Rubber Based Blends and IPNs 550
Cristina Russi Guimardes Furtado and
Mdrcia Christina Amorim Moreira Leite
23.1 Introduction 550
23.2 Life Cycle Assessment 551
23.3 Ageing and Degradation of NR Based Blends and
Interpenetrating Polymer Networks (IPNs) 553
23.3.1 Polymer Blends and IPNs 553
23.3.2 Ageing and Degradation 554
23.3.3 NR/Thermoplastic Blends and IPNs 555
23.3.4 NR/Synthetic Rubber Blends and IPNs 558
23.3.5 NR/Biopolymer Blends and IPNs 561
23.4 Conclusions 564
References 564
XX Contents
Chapter 24 Application of Natural Rubber Based Blends and IPNs in
Tyre Engineering and other Fields 569
Mir Hamid Reza Ghoreishy and Mohammad Alimardani
24.1 Introduction 569
24.1.1 Properties of Natural Rubber 569
24.1.2 Elastomer Blends 572
24.1.3 General Aspects of Compounding of NR
and Blends 572
24.2 NR and its Blends for Tyre Components 575
24.3 NR in Seismic Isolation Bearings 577
24.3.1 Why NR as Seismic Isolation? 578
24.4 Toughened Thermoplastics and IPNs of NR in the
Automotive Industry 579
24.5 Membrane Technology 585
24.5.1 Introduction 585
24.5.2 Recent Achievements in the Field of NR
Blends as Membranes 586
24.6 Miscellaneous Applications of Natural Rubber
Based Blends 595
24.6.1 Retreading of Tyres 595
24.6.2 NR as an Insulator 595
24.6.3 Use of NR for Modification of Plastic
Properties 596
References 596
Subject Index 600
