Photodegradation, photo-oxidation and photostabilization of polymers: principles and applications . .
Saved in:
| Main Authors: | , |
|---|---|
| Format: | Book |
| Language: | English |
| Published: |
London
Wiley
1975
|
| Series: | A Wiley -Interscience Publ.
|
| Subjects: | |
| Online Access: | Inhaltsverzeichnis |
| Physical Description: | XV, 573 S. graph. Darst. |
| ISBN: | 0471707880 |
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Record in the Search Index
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|---|---|
| adam_text | Photodegradation,
Photo-oxidation and
Photostabilization
of Polymers
Principles and Applications
Professor of Polymer Technology
Qw»
J F Rabek
Assistant Professor of Polymer Technology
Department of Polymer Technology
The Royal Institute of Technology
Teknikringed, Stockholm, Sweden
A Wiley-Interscience Publication
JOHN WILEY amp; SONS
London • New York • Sydney • Toronto
Contents
1 FUNDAMENTAL PRINCIPLES OF PHOTOCHEMISTRY 1
1 1 Light and its energy 1
1 2 Absorption of radiation 3
1 3 Photochemical reactions 6
1 4 Quantum yield 6
1 5 Electronically excited states 7
151 Radiative processes 9
152 Radiationless processes 10
153 Lifetime of electronically excited states 12
154 Determination of the intersystem crossing rate constant 13
155 Information obtained from the spectral data 15
1551 Absorption spectra 15
1552 Emission spectra: fluorescence and phosphorescence 18
1553 Data calculated from spectra 19
156 Deactivation of excitation states 21
157 Non radiative energy transfer processes 27
1571 Resonance excitation transfer 27
1572 Exchange energy transfer 29
1573 The energy transfer in collisions 30
158 Radiative energy transfer 32
159 Delayed luminescence 32
1 6 Photochemical kinetics 34
161 Elements of photochemical kinetics 34
1611 Kinetics of photochemical reaction in monochromatic 34
radiation 35
1612 Kinetics of photochemical reaction in polychromatic
radiation 40
2 GENERAL MECHANISM OF POLYMER DEGRADATION 42
2 1 Primary reactions following bond dissociation in polymers 42
2 2 Primary reactions following the excitation of carbonyl groups in
polymers 48
2 3 Electron spin resonance studies of free radicals formed during the
degradation process 50
231 Introduction to esr spectroscopy 50
232 Electron spin resonance spectrometers 58
233 Electron spin resonance studies of polyolefin degradation 59
2331 The structure of free radicals 60
IX
X
23311Esr spectra of free radicals from polyethylene 60
23312Esr spectra of polypropylene radicals 65
23313 The structure of peroxy free radicals 67
2322 Decay of macroradicals in polymers 69
2323 Photoinduced radical conversion 71
2 4 Reaction kinetics of the photodegradation and crosslinking of
polymers 76
241 Introduction to the kinetics of degradation 76
242 Kinetics of photodegradation and photocrosslinking 80
243 Introduction to kinetics of photodepolymerization 83
244 Quantum yield of photodegradation 83
3 THE GENERAL MECHANISM OF OXIDATIVE DEGRADA
TION OF POLYMERS 97
3 1 Physical nature of molecular oxygen 97
3 2 Mechanism of polymer photo-oxidation 97
321 The initiation reaction 98
322 Formation of polymer hydroperoxides 98
323 Decomposition of polymer hydroperoxides 98
324 Intramolecular propagation of peroxy radicals 99
325 Formation of hydroxyl groups 99
326 Formation of carbonyl and aldehyde groups 100
327 The termination reaction 101
3 3 Physical aspects of the oxidation of polymers 102
3 4 Introduction to the kinetics of polymer photo-oxidation 106
3 5 Experimental methods in kinetic measurements 108
351 The measuring of oxygen uptake 108
352 The determination of the rate constants Ill
3 6 Chemiluminescence reactions 115
3 7 The role of metal ions and metal oxides in the oxidation of polymers 117
4 PHOTODEGRADATION AND PHOTO-OXIDATION OF
PARTICULAR POLYMERS 120
4 1 Homochain polymers 121
411 Polyolefins 121
4111 Polyethylene 121
4112 Polypropylene 128
4113 Polyisobutylene 141
412 Polyketones 143
4121 Ethylene-carbon monoxide copolymers 143
4122 Polyketones on the basis of polyesters 146
4123 Poly(methylvinyl ketone) 147
4124 Copolymer of methylvinyl ketone and methyl metha
crylate 147
4125 Poly(methyl isopropenyl ketone) 148
XI
4126 PolyCvinyl phenyl ketone) 149
4127 Copolymer of phenyl vinyl ketone and styrene 150
4128 Poly(vinylbenzophenone) 151
413 Polyacrylates and polymethacrylates 152
4131 Poly(acrylic acid) and poly(methacrylic acid) 152
4132 Poly(methyl acrylate) and poly(ethyl acrylate) 154
4133 Poly(methyl metacrylate) and poly(ethyl methacrylate) 156
4134 Other poly(acrylate esters) and poly(methacrylate esters) 161
41341 Poly(t-butyl acrylate) 161
41342 Poly(n-butyl methacrylate) 161
41343 Poly(N-dimethyl-/?-amino ethyl methacrylate) 163
414 Poly(vinyl carbamate) 164
415 Polystyrenes 165
4151 Polystyrene 165
4152 Poly(a-methylstyrene) 184
4153 Poly(p-methylstyrene) 189
416 Polyacrylonitrile 190
417 Poly(vinyl chloride) 192
4171 Other halogenated polymers and copolymers 195
418 Poly(vinyl alcohol) and poly(vinyl acetate) 196
419 Poly (vinyl pyrrolidone) 198
4 1 10 Polydienes 199
4 1 10 1 cis- 1,4-poly butadiene 199
4 1 10 2 Polypentamers 201
4 1 10 3 1,2-Polybutadiene 201
4 1 10 4 cis-1,4-Polyisoprene 203
4 1 10 5 Polypiperylene 205
4 1 10 6 3,4-Polyisoprene 206
4 1 10 7 Photo-oxidation of polydienes 206
4 1 10 8 Acrylonitrile-butadiene-styrene copolymer (ABS) 210
4 1 10 9 Chlorinated rubber 210
4 2 Heterochain polymers 210
421 Polyethers 210
4211 Polyoxymethylene 210
4212 Polyoxetanes 212
4213 Poly(2,6-dimethyl-1,4-phenylene oxide) (PPO) 215
4214 Phenoxy resins 217
422 Polysulphides and polysulphones 223
4221 Polysulphides 223
4222 Polysulphones 223
423 Polcarbonates 227
424 Polyesters 230
4241 Unsaturated polyesters 230
4242 Polyethylene terephthalate) 231
4243 Other polyesters 236
xii
425 Polyamides 236
4251 Aliphatic polyamides (nylons) 236
4252 Thermally resistant polyamides 238
4253 Photoreversible depolymerization in poly(hexamethy-
lene-a-truxillamide) 239
426 Polyimides and polyamido-imides 241
427 Polyurethanes 241
428 Polysiloxanes 243
429 Natural polymers 245
4291 Cellulose and its esters 245
42911 Cellulose 245
42912 Cllulose acetate 247
42913 Cellulose nitrate 251
4292 Wool 251
4 2 10 High-intensity light irradiation of polymers 253
5 SINGLET OXYGEN MECHANISM OF POLYMER PHOTO
OXIDATION 254
5 1 Physical nature of singlet oxygen 254
5 2 Preparation methods for singlet oxygen 257
521 Physical methods 257
522 Chemical methods 259
523 Photosensitizing methods 260
5 3 Chemical reaction of singlet oxygen 262
5 4 Elements of kinetics of singlet oxygen processes 265
541 Kinetics of singlet oxygen oxidation reaction 265
542 Method for the determination of ß-value in sensitized photo- 266
oxidation reactions
543 The determination of rate constants for the quenching of 267
singlet oxygen 271
544 The lifetime of singlet oxygen 102(1Ag) 272
5 5 Mechanism of singlet oxygen oxidation and degradation of polymers
6 PHOTOSENSITIZED REACTIONS OF POLYMERS 276
6 1 Photochemical processes of polymers in solution 276
611 Photochemistry of solvents 276
6111 Alcohols 276
6112 Ketones 277
6113 Hydrocarbons 277
6114 Tetrahydrofurane 282
6115 Organic halides 285
612 Influence of solvents on the photochemical processes of
dissolved polymers 286
xiii
6 2 Sensitized photoreactions of polymers in solution and solid state 289
621 Fundamental photochemistry of sensitizers and their role in
the photosensitized degradation and photo-oxidation of
polymers 290
6211 Photosensitizing effect of inorganic metal oxides and
metal salts 290
6212 Carbonyl compounds 292
62121 Ketones 292
62122 Diketones 302
6213 Quinones 303
6214 Peroxides 306
6215 Nitrogen chromophore compounds 307
62151 Azo-compounds 307
62152 Nitroso compounds 307
62153 DPPH as sensitizer 308
6216 Polycyclic hydrocarbons 310
622 Dye sensitized photodegradation of polymers 315
6221 Photochemistry of dyes 315
6222 The role of dyes in photosensitized degradation and
oxidation of polymers 324
623 Sensitized photocrosslinking of polymers 326
7 ENERGY TRANSFER IN POLYMERS 333
7 1 Intermolecular energy transfer in polymers 335
7 2 Intramolecular energy transfer in polymers 343
7 3 Energy transfer due to chemiluminescent reactions in polymers 350
8 PHOTOCHEMISTRY OF POLYMERS IN REACTIVE GASES 351
8 1 Formation of singlet oxygen in the atmosphere 351
8 2 Reaction of ozone with polymers 353
8 3 Reaction of atomic oxygen with polymers 354
8 4 The role of S02 and N02 in photo-ageing of polymers 357
8 5 Photochlorination of polymers 358
9 THE ROLE OF PHOTODEGRADABLE POLYMERS IN THE
PACKAGING INDUSTRY 359
10 STABILIZATION OF POLYMERS TO ULTRAVIOLET LIGHT 362
10 1 Introduction to the mechanism of ultraviolet stabilization 362
10 2 Stabilizers for commercial polymers 363
10 2 1 Pigments 363
10 211 Inorganic and organic pigments 363
10 212 Carbon Black 364
10 213 Fluorescent compounds 365
XIV
10 2 2 Absorbers with carbonyl oxygen acceptors 369
10 221 Phenyl esters of benzoic acid 369
10 222 Hydroxy-benzophenones 372
10 2 3 Absorbers with nitrogen acceptors 374
10 131 Benzotriazoles 374
10 232 S-triazines 376
10 233 Other compounds with nitrogen acceptor 377
10 2 4 Various other organic compounds as photostabilizers 378
10 2 5 Metal organic compounds as absorbers 379
10 251 Ferrocene derivatives 379
10 252 Metal chelates 379
10 2 6 Photostabilizers as quenchers of excited states of polymer 381
10 2 7 Photochromic absorbers 383
10 2 8 Polymeric ultraviolet absorbers 384
10 2 9 Stable polymers as stabilizers 387
10 3 Protective efficiency of ultraviolet stabilizers 390
10 4 Technical and commercial problems of photostabilizers 392
10 5 New trends in the synthesis and application of ultraviolet stabilizers 406
11 THE MECHANISM OF THE INHIBITION OF THE OXIDA
TION OF POLYMERS 412
11 1 Introduction to the mechanism of inhibition of oxidation 412
11 2 The role of antioxidants for the inhibition of photodegradation 418
11 3 The role of synergism in the process of oxidation and photo
oxidation 418
12 PRACTICAL METHODS IN PHOTOCHEMISTRY OF
POLYMERS 423
12 1 Introduction 423
12 2 Light sources for photochemical investigations 423
12 2 1 Sunlight 424
12 2 2 Incandescent arc lamps 425
12 221 Low pressure mercury lamps 425
12 222 Medium pressure mercury lamps 426
12 223 High pressure mercury lamps 426
12 224 Thallium-or indium-mercury lamps 435
12 225 Xenon lamps 435
12 226 Sodium lamps 438
12 227 Lamps with luminescence radiation 438
12 228 Tungsten lamps 439
12 229 Carbon arc light source 439
12 2 2 10 Vacuum ultraviolet sources 440
12 2 3 Laser sources 440
12 3 Photochemical methods and equipment 443
12 3 1 Mirrors for ultraviolet radiation 443
XV
12 3 2 Fibre optic bundle 444
12 3 3 Application of filters in photochemistry 445
12 331 Glass filters 445
12 3311 Solid transmission filters 446
12 3312 Monochromatic filters 446
12 332 Chemical filters 450
12 3321 Liquid transmission filters 450
12 3322 Liquid band-pass filters 450
12 333 Plastic filters 454
12 334 Fluorescence filters 455
12 3 4 Application of monochromators 455
12 3 5 Photochemical reactors and cells 457
12 3 6 Viscometers for photochemical studies 464
12 4 Dosimetry in photochemistry 467
12 5 Measurements of light 469
12 6 Determination of quantum yield 471
12 6 1 Potassium ferri-oxalate actinometer 472
12 6 2 Uranyl oxalate actinometer 474
12 6 3 Reinecke’s salt actinometer 475
12 6 4 MGL actinometer 475
12 6 5 Nitrobenzaldehyde actinometer 476
12 6 6 Benzophenone-benzhydryl actinometer 477
12 6 7 Butyrophenone actinometer 477
12 6 8 Gaseous actinometers for the vacuum U V region 478
12 7 Measurement of luminescence 478
12 7 1 Measurements of fluorescence spectra 478
12 7 2 The standardization of methods of recording fluorescence
emission spectra 483
12 7 3 The measurements of fluorescence lifetime 484
12 7 4 Measurements of phosphorescence spectra and lifetime 485
12 7 5 Measurement of chemiluminescence 486
12 8 Flash photolysis 487
12 9 Additional equipment in a photochemical laboratory 492
13 WEATHERABILITY OF PLASTICS MATERIALS 493
13 1 Outdoor methods for testing the weathering of polymers 493
13 2 Laboratory methods for artificial ageing and weathering of
polymers 495
13 3 Interpretation of weathering results 498
REFERENCES 501
INDEX 555
|
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| indexdate | 2024-07-09T16:40:11Z |
| institution | BVB |
| isbn | 0471707880 |
| language | English |
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| spelling | Rånby, Bengt G. 1920- Verfasser (DE-588)108785513 aut Photodegradation, photo-oxidation and photostabilization of polymers principles and applications . . B. Ranby ; J. F. Rabek London Wiley 1975 XV, 573 S. graph. Darst. txt rdacontent n rdamedia nc rdacarrier A Wiley -Interscience Publ. Photochemistry Polymers Polymere (DE-588)4046699-1 gnd rswk-swf Fotochemie (DE-588)4045873-8 gnd rswk-swf Polymere (DE-588)4046699-1 s Fotochemie (DE-588)4045873-8 s DE-604 Rabek, Jan F. Verfasser aut HEBIS Datenaustausch application/pdf http://bvbr.bib-bvb.de:8991/F?func=service&doc_library=BVB01&local_base=BVB01&doc_number=003848605&sequence=000001&line_number=0001&func_code=DB_RECORDS&service_type=MEDIA Inhaltsverzeichnis |
| spellingShingle | Rånby, Bengt G. 1920- Rabek, Jan F. Photodegradation, photo-oxidation and photostabilization of polymers principles and applications . . Photochemistry Polymers Polymere (DE-588)4046699-1 gnd Fotochemie (DE-588)4045873-8 gnd |
| subject_GND | (DE-588)4046699-1 (DE-588)4045873-8 |
| title | Photodegradation, photo-oxidation and photostabilization of polymers principles and applications . . |
| title_auth | Photodegradation, photo-oxidation and photostabilization of polymers principles and applications . . |
| title_exact_search | Photodegradation, photo-oxidation and photostabilization of polymers principles and applications . . |
| title_full | Photodegradation, photo-oxidation and photostabilization of polymers principles and applications . . B. Ranby ; J. F. Rabek |
| title_fullStr | Photodegradation, photo-oxidation and photostabilization of polymers principles and applications . . B. Ranby ; J. F. Rabek |
| title_full_unstemmed | Photodegradation, photo-oxidation and photostabilization of polymers principles and applications . . B. Ranby ; J. F. Rabek |
| title_short | Photodegradation, photo-oxidation and photostabilization of polymers |
| title_sort | photodegradation photo oxidation and photostabilization of polymers principles and applications |
| title_sub | principles and applications . . |
| topic | Photochemistry Polymers Polymere (DE-588)4046699-1 gnd Fotochemie (DE-588)4045873-8 gnd |
| topic_facet | Photochemistry Polymers Polymere Fotochemie |
| url | http://bvbr.bib-bvb.de:8991/F?func=service&doc_library=BVB01&local_base=BVB01&doc_number=003848605&sequence=000001&line_number=0001&func_code=DB_RECORDS&service_type=MEDIA |
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