Biodegradable polymers and plastics

M. Vert, J. Feijen, A. Albertsson, G. Scott, Emo Chiellini0851862071, 9780851862071

During the past 50 years polymers have totally changed human life and the plastics industry has developed durable materials increasingly adapted to specific uses. In response to demands for temporary applications, scientists are now working on polymeric systems that can serve as materials and undergo degradation at controlled and predetermined rates after task completion. This interdisciplinary text presents the latest international research in the field, covers both practical and theoretical aspects of the subject, and also includes mathematical modelling for biodegradation. It explores most of the basic problems relevant to polymer degradation and gives special emphasis to biodegradable applications. The book should be beneficial to research scientists involved in agricultural chemistry, biotechnology, cell and molecular biology, toxicology, environmental chemistry, materials sciences, polymer science, and medicinal and pharmaceutical chemistry.

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Table of contents :
Handbook of Biodegradable Polymers……Page 1
REFERENCES……Page 7
PREFACE……Page 9
CONTRIBUTORS……Page 10
CONTENTS……Page 5
Contents……Page 0
Section1: Synthetic Absorbable Polymers……Page 15
INTRODUCTION……Page 16
Poly ( L-lactide)……Page 18
Acquisition, Characterization, and Qualification of Glycolide and Lactide Monomers……Page 19
Small-scale Polymerization of Glycolide, L-lactide, and DL-lactide……Page 20
Molecular Weight and Molecular-Weight Distribution……Page 21
PROCESSING……Page 22
DEGRADATION……Page 23
Biocompatibility of PL……Page 27
PG and PGL Copolymers……Page 29
PL Homopolymers……Page 30
SRPL……Page 31
Melt-processed PL……Page 32
CONCLUSION……Page 33
REFERENCES……Page 34
APPENDIX……Page 40
INTRODUCTION……Page 41
SYNTHESIS OF p-DIOXANONE MONOMER……Page 43
SYNTHESIS OF POLY(p-DIOXANONE)……Page 45
Polymer Extrusion……Page 46
Breaking Strength Retention In Vivo (BSR)……Page 48
In Vivo Absorption/Tissue Reaction……Page 49
POLY(p-DIOXANONE-CO-L (-) LACTIDE) SEGMENTED COPOLYMERS……Page 51
RESULTS AND DISCUSSION……Page 53
POLY(P-DIOMONE-CO-GLYCOLIDE) SEGMENTED COPOLYMERS……Page 55
RESULTS AND DISCUSSION……Page 58
POLY(p-DIOWONE-CO-GLYCOLIDE) BLOCK COPOLYMERS……Page 59
POLY(p-DIOXANONE-CO-e-CAPROLACTONE) COPOLYMERS……Page 61
POLY(p-DIOaVONE-CO-GLYCOLIDE-CO-MCTIDE) TERPOLYMERS……Page 63
POLY(p-DIOMONE-CO-KmENE OXIDE) COPOLYMERS……Page 64
Poly (p-DIOXANONE-CO-CARBONATE) COPOLYMERS……Page 65
POLY(p-DIOWONE-GLYCOLIDE-MCTIDE) RANDOM TEFWOLWERS……Page 66
RESULTS AND DISCUSSION……Page 67
RADIATION STERILIZABLE ABSORBABLE PDO COPOLYMERS……Page 68
SUMMARY……Page 71
REFERENCES……Page 72
POLYMERIZATION OF POLYMERS AND COPOLYMERS OF POLY (E-CAPROLACTONE)……Page 74
Acquisition and Characterization of 6-Caprolactone Monomer……Page 75
Small-scale Polymerization of e-Caprolactone……Page 76
Pilot-scale Polymerization of 6-Caprolactone……Page 77
Caprolactone Comonomer Ratio……Page 78
PROCESSING……Page 79
PCL HOMOPOLYMER DEGRADATION……Page 80
Drug Delivery Applications……Page 81
Sutures……Page 83
REFERENCES……Page 84
APPENDIX……Page 88
Biosynthesis of Polyhydroxyalkanoates……Page 89
Physical Properties of Polyhydroxyalkanoates……Page 91
Biodegradation of Polyhydroxyalkanoates……Page 93
REFERENCES……Page 95
SYNTHESIS……Page 97
CHARACTERIZATION……Page 103
ORTHOPAEDIC APPLICATIONS……Page 105
REFERENCES……Page 106
Polymer Hydrolysis……Page 108
Poly(0rtho Ester) II……Page 109
Preparation of 3,9-bis (ethylidene)-2,4,8,10-tetraoxaspim[5,5]undecant……Page 112
Preparation of Linear Polymers……Page 113
Characterization……Page 114
Control of PolymerHydrolysis Rate……Page 115
(b) Short Term Delivery……Page 118
(c) Long Term Delivery……Page 119
Poly(0rtho Ester) Ill……Page 120
Typical Experimental Procedure……Page 121
Applications……Page 122
1,4-Cyclohexanedimethanol monoacetate…….Page 123
4-Acetoxymethyl-l,l-cyclohexanedimethanol…….Page 124
Preparation of Polymer……Page 125
REFERENCES……Page 126
Poly ( ether-esters )……Page 128
Synthesis of l,5-dioxepan-2-one(DX0) polymers (Mathisen, 1989;Lofgren, 1994)……Page 129
Poly(ester-ether) networks……Page 131
Poly(ester amides) (PEA) and Functionalized Polyesters……Page 133
3M poly (ester-amides)……Page 134
Synthesis of Poly (ester-amides) ContainingDegradable Blocks……Page 135
Synthesis of Morpholine 2,s-dione and Derivatives……Page 136
Poly (ester-urethane) Elastomeric Networks……Page 138
Polyphosphate Esters……Page 139
REFERENCES……Page 140
ABBREVIATIONS……Page 142
SYNTHESIS……Page 144
Unsaturated Polymers……Page 146
Amino Acid Based Polymers……Page 149
Soluble Aromatic Copolymers……Page 150
Poly ( ester-anhydrides )……Page 151
Fatty Acid Based Polyanhydrides……Page 152
Composition by-H NMR……Page 153
Crystallinity……Page 154
Infra Red and Raman Analysis……Page 155
STABILITY……Page 156
INNITRO DEGRADATION AND DRUG RELEASE……Page 158
BIOCOMPATIBILITY AND ELIMINATION……Page 161
APPLICATIONS……Page 163
REFERENCES……Page 164
ABBREVIATIONS……Page 167
GENERAL INTRODUCTION……Page 169
Ring-opening Polymerization……Page 170
Polymerization Method by Hornbaker and Li……Page 172
Amino Acid Derivatives……Page 173
Hydrophilic Polyphosphazenes……Page 180
Other Biodegradable Polyphosphazenes……Page 181
BIOMEDICAL APPLICATIONS OF POLY[ (ORGANO) PHOSPHAZENES]……Page 182
BIOCOMPATIBILITY OF POLY[ (ORGAVO) PHOSPHAZENES]……Page 185
REFERENCES……Page 187
SYNTHESIS AND PURIFICATION OF CYANOACRYLATE MONOMERS……Page 191
SYNTHESIS OF THE POLYMER AND MECHANISM OF POLYMERIZATION……Page 192
Spectroscopic Analysis……Page 193
Molecular Weight……Page 194
Adhesive Properties……Page 195
Polymer Degradability……Page 196
APPLICATIONS OF CYANOACRYLATES IN THE DESIGN OF DRUG PARTICULATE CARRIERS……Page 198
Degradation of Poly(alkylcyanoacrylates) Nanoparticles……Page 199
Experimental Cancers……Page 200
Controlled Delivery of Peptides and Proteins……Page 202
Controlled Delivery of Antisense Oligonucleotides……Page 203
CONCLUSION……Page 204
REFERENCES……Page 205
ABBREVIATIONS……Page 209
INTRODUCTION……Page 211
Chemical Gels……Page 212
Physical Gels……Page 213
TYPE OF DEGRADATION……Page 214
MECHANISMS OF DEGRADATION IN BIODEGRADABLE HYDROGELS……Page 218
APPLICATIONS OF DEGRADABLE HYDROGELS……Page 221
REFERENCES……Page 233
Synthesis……Page 239
Nomenclature……Page 240
Chemical and Physical Properties……Page 241
Gellation of the Poloxamers in Solution……Page 242
Toxicology of Poloxamer 188……Page 244
Toxicology of Poloxamer 407……Page 245
Treatment of Tissue Ischemia and Reperfusion Injury……Page 246
Reduction of Blood Viscosity……Page 247
USE OF POLOXAMER 407 FOR PREVENTION OF POSTS!RGICAL ADHESIONS……Page 248
Effect of Poloxarner 407 on Peritoneal Adhesions……Page 249
Site Specific Drug Delivery……Page 250
Drug-like Properties of the Poloxamers……Page 251
REFERENCES……Page 252
APPENDIX……Page 256
Amino Acid Derived Polymers with Modilied Backbones……Page 258
Pseudo-Poly (amino acids)……Page 259
Monomer Design and Synthesis……Page 260
Polycarbonate Design and Synthesis……Page 262
Polyiminocarbonate Design and Synthesis……Page 264
Tyrosine-Derived Polycarbonates……Page 267
Tyrosine-Derived Polyarylates……Page 269
Tyrosine-Derived Polyminocarbonates……Page 271
Tyrosine-Derived Polycarbonates……Page 272
Tyrosine-Derived Polyiminocarbonates……Page 274
SUMMARY……Page 275
REFERENCES……Page 276
SECTION 2: NATURAL, SEMI-SYNTHETIC AND BIOSYNTHETIC POLYMERS……Page 280
INTRODUCTION……Page 281
CHEMICAL MODIFICATIONS……Page 284
POLYSACCHARIDES ANALYSIS……Page 285
PROPERTIES AND APPLICATIONS……Page 286
Alginate……Page 287
Chitin and Chilosan……Page 288
Dextran……Page 290
Hyaluronic Acid……Page 291
Starch……Page 292
REFERENCES……Page 293
INTRODUCTION……Page 296
HISTORY OF DE’ELOPMENT……Page 297
NITROGEN DIOXIDE OXIDATION……Page 298
Johnson &Johnson Process – Liquid Phase Oxidation……Page 300
Mechanism of Oxidation……Page 301
Structural Considerations……Page 304
BIODEGRADATION……Page 305
BIOABSORITION……Page 306
Topical Absorbable Hemostatic Agent……Page 307
Drug Delivery Matrix……Page 308
REFERENCES……Page 309
CHEMICAL COMPOSITION AND STRUCTURE……Page 312
PHYSICAL AND CHEMICAL PROPERTIES……Page 313
Solubility……Page 314
Colloid and Emuisifying Properties……Page 315
MANUFACTURE AND PROCESSING……Page 316
ECONOMIC ASPECTS……Page 317
Food Products……Page 318
Derivatized Gelatin……Page 319
REFERENCES……Page 320
INTRODUCTION……Page 323
PREPARATION OF INSOLUBLE COLLAGEN……Page 324
PREPARATION OF SOLLBLE COLLAGEN……Page 325
COLLAGEN CHARACTERIZATION……Page 326
COLLAGEN PROCESSING INTO DEVICES……Page 330
DEVICE PACKAGING AND STERILIZATION……Page 332
2. Sensitization Test……Page 333
5 . Pyrogenicity Test……Page 334
Immunogenicity of Collagen……Page 335
Bovine Spongiform Encephalopathy ( BSE )……Page 336
Drug Delivery……Page 337
Collagen Fiber, Fabrics and Tubes……Page 339
Collagen Films, Membranes and Matrices……Page 340
Cell Culture on Collagen (Tissue Engineering)……Page 342
Acknowledgements……Page 343
REFERENCES……Page 344
INTRODUCTION……Page 351
METHODS OF ISOLATION……Page 353
CHARACTERIZATION OF FIBRINOGEN……Page 354
FIBRIN POLYMERIZATION AND CHARACTERIZATION OF THE CLOT……Page 356
FIBRINOLYSIS……Page 361
Examples……Page 362
Safety Issues……Page 363
REFERENCES……Page 364
INTRODUCTION……Page 370
Synthetic Gene Constructions and Ex@ression in E. coli……Page 371
Examples of Concatemerized Genes, i.e., Series of Achieved Chain Lengths……Page 373
Purification……Page 374
Inverse Temperature Transitional Properties……Page 375
Elastic Modulus of Cross-LinkedMatrices……Page 378
Inlrafiktoneal Implantation of the Elastic State Containing Chemical Clocks……Page 379
Biocompatibility (Toxicity) of Representative States……Page 380
Synthetic Polypeptides as Antigens……Page 381
Screening Assays……Page 382
Drug Delivery……Page 383
The Principle of Tensepiiy……Page 385
Consideration of Urological Prostheses……Page 386
REFERENCES……Page 388
DESIGN, SYNTHESIS AND PURIFICATION OF BIOLOGICALLY PRODUCED PROTEIN POLYMERS……Page 390
Biological Production Methods……Page 392
Polymer Gene Construction……Page 393
Crystalline BetaSilk Protein Polymers……Page 394
Prolastin Polymers……Page 395
ProNectin Protein Polymers……Page 396
Collagenlike Protein (CLP) Polymers……Page 398
Chemical Characterization Of Protein Polymers……Page 400
Protein Polymer Solutions……Page 401
Protein Polymer Fibers……Page 402
ProLastin Fibrous Meshes……Page 403
Coatings……Page 404
Surface Modification By Co-Injection Molding……Page 405
In-Vivo Resorption……Page 406
ProLastin films……Page 408
ProLastin sponges……Page 410
Biocompatibility……Page 411
Immunogenicity……Page 412
REFERENCES……Page 413
SECTION 3: GENERAL PROPERTIES OF POLYMERS……Page 418
INTRODUCTION……Page 419
X-ray Photoelectron Spectroscopy (xps)……Page 420
Static Secondary Ion Mass Spectrometry (SSIMS)……Page 424
Scamming Probe Microscopes……Page 427
Poly (esters)……Page 430
Poly (ortho esters)……Page 434
Poly (anhydrides)……Page 436
Poly (ester) copolymers……Page 438
Poly (anhydride) copotymers……Page 441
AFM CHARACTERIZATION OF BIOERODIBLE POLYMERS……Page 443
CONCLUDING REMARKS……Page 449
REFERENCES……Page 450
INTRODUCTION……Page 453
The Definition of a Degradable Polymer……Page 454
The Type of Chemical Bond……Page 455
Crystallinity and Molecular Weight……Page 457
pH……Page 458
Enzymatic Degradation……Page 459
Homogenous and Heterogeneous Erosion……Page 460
Morphological Changes……Page 461
The Release of Monomers and Drugs from DegradabIe Polymers During Erosion……Page 463
A Brief Summary on Potential Erosion Mechanisms……Page 464
POLYMER ELIMINATION……Page 465
APPROACHES TO POLYMER EROSION MODELING……Page 466
SUMMARY……Page 469
REFERENCES……Page 470
INTRODUCTION……Page 474
DEFINITIONS FOR ENVIRONMENTALLY DEGRADABLE POLYMERS……Page 476
POTENTIAL USES FOR ENVIRONMENTALLY DEGRADABLE POLYMERS……Page 477
TEST PROTOCOLS FOR ENVIRONMENTALLY DEGRADABLE POLYMERS……Page 479
Test Protocols for Photodegradable / Oxidatively Degradable Plastics……Page 480
Test Protocols for Biodegradable Polymers……Page 481
Anaerobic Emironment……Page 482
Photodegradable and Oxidative Degradable Polymers……Page 484
Biodegradable Polymers……Page 488
CONCLUSIONS……Page 505
REFERENCES……Page 506