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1995 | Buch

Polymer Photodegradation

Mechanisms and experimental methods

verfasst von: Jan. F. Rabek

Verlag: Springer Netherlands

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Über dieses Buch

During the last two decades, the production of polymers and plastics has been increasing rapidly. In spite of developing new polymers and polymeric materials, only 40~60 are used commercially on a large scale. It has been estimated that half of the annual production of polymers is employed outdoors. The photochemical instability of most polymers limits their outdoor application as they are photodegraded quickly over periods from months to a few years. To the despair of technologists and consumers alike, photodegradation and environmental ageing of polymers occur much faster than can be expected from knowledge collected in laboratories. In order to improve polymer photostability there has been a very big effort during the last 30 years to understand the mechanisms involved in photodegradation and environmental ageing. This book represents the author's attempt, based on his 25 years' experience in research on photodegradation and photo stabilization, to collect and generalize a number of available data on the photodegradation of polymers. The space limitation and the tremendous number of publications in the past two decades have made a detailed presentation of all important results and data difficult. The author apologizes to those whose work has not been quoted or widely presented in this book. Because many published results are very often contradictory, it has been difficult to present a fully critical review of collected knowledge, without antagonizing authors. For that reason, all available theories, mechanisms and different suggestions have been presented together, and only practice can evaluate which of them are valid.

Inhaltsverzeichnis

Frontmatter
Chapter 1. Physical aspects of the photodegradation of polymers
Abstract
Photodegradation (chain scission and/or crosslinking) occurs by the activation of the polymer macromolecule provided by absorption of a photon of light by the polymer. In the case of photoinitiated degradation light is absorbed by photoinitiators, which are photocleaved into free radicals, which further initiate degradation (in non-photochemical processes) of the polymer macro-molecules. In photo-thermal degradation both photodegradation and thermal degradation processes occur simultaneously and one of these can accelerate another. Photoageing is usually initiated by solar UV radiation, air and pollutants, whereas water, organic solvents, temperature and mechanical stresses enhance these processes. The general aspects of photodegradation such as absorption of light, photophysical processes and photochemical reactions, kinetics, formation of oxidized groups, etc. have been discussed in a number of review articles [45, 57, 145, 146, 292, 374, 390, 604, 699, 752, 753, 857, 858, 861, 864, 871, 910, 960, 1212, 1219, 1316, 1321, 1383–1385, 1418, 1780, 1809, 1811, 1813, 1917, 1926, 1973] and books [742, 830, 902, 1075, 1076, 1083, 1446, 1556, 1639, 1697, 1766, 1768, 1804, 1863, 1928, 1974, 2189, 2298].
Jan. F. Rabek
Chapter 2. Photochemical aspects of degradation of polymers
Abstract
Photochemical reactions occur as a result of activation of a molecule (polymer macromolecule) by light to its excited singlet (S*) and/or triplet (T*) states (cf. section 1.2). Pure degradation (chain scission and/or crosslinking) occurs only in an inert (vacuum, nitrogen or argon) atmosphere. When air (oxygen) is present, photo-oxidative degradation occurs. In the photo-oxidative degradation of almost all polymers the following steps can be considered:
1.
Initiation step: formation of free radicals.
 
2.
Propagation step: reaction of free polymer radicals with oxygen, production of polymer oxy- and peroxy-radicals and secondary polymer radicals, resulting in chain scission.
 
3.
Termination step: reaction of different free radicals with each other, resulting in crosslinking.
 
Jan. F. Rabek
Chapter 3. Photodegradation and photo-oxidative degradation of homochain polymers
Abstract
The photodegradation and photo-oxidative degradation of different polyolefins have been subjects of many publications (Table 3.1) and reviews [570, 853, 856, 866, 1999, 2268].
Jan. F. Rabek
Chapter 4. Photodegradation and photo-oxidative degradation of heterochain polymers
Abstract
The polyoxymethylene (4.1) contains only C—C and C—O bonds and is therefore not expected to absorb light of wavelength longer than 190–220 nm. However, this polymer is not resistant to light and photo-oxidative degradation [826, 1026, 1597].
Jan. F. Rabek
Chapter 5. Role of metal compounds in the photodegradation of polymers
Abstract
Titanium dioxide (TiO2) exists in two morphological crystalline forms, which exhibit different photoactivities when incorporated into a polymer matrix:
1.
Anatase (TiO2), which is photochemically active and sensitizes (or catalyses) polymer photodegradation.
 
2.
Rutile (TiO2), which is photochemically relative inactive.
 
Jan. F. Rabek
Chapter 6. Degradation of polymers initiated by radicals formed from photolysis of different compounds
Abstract
Hydrogen peroxide (H2O2) is easily photolysed in the 200–300 nm region, where its continuous absorption (Fig. 6.1) to form hydroxyl radicals (HO·) is observed [202, 1029, 1303, 2191]:
$$ {H_2}{O_2}\xrightarrow{{hv}}2H{O^{\bullet }} $$
(6.1)
The quantum yield of the disappearance of H2O2 is 1.7 ± 0.4. In the secondary reaction 6.2, hydroperoxy (\( {H_2}O_2^{\bullet } \)) radical is formed:
$$ {H_2}{O_2} + H{O^{\bullet }} \to HO_2^{\bullet } + {H_2}O $$
(6.2)
The main products of H2O2 photolysis are water and oxygen, which are formed in the termination reactions:
$$ 2H{O^{\bullet }} \to {H_2}O + \frac{1}{2}{O_2} $$
(6.3)
$$ H{O^{\bullet }} + HO_2^{\bullet } \to {H_2}O + {O_2} $$
(6.4)
However, the termination reactions of HO· and \( {H_2}O_2^{\bullet } \) radicals again produce hydrogen peroxide:
$$ 2H{O^{\bullet }} \to {H_2}{O_2} $$
(6.5)
$$ 2HO_2^{\bullet } \to {H_2}{O_2} + {O_2} $$
(6.6)
Oxygen does not react with hydroxyl (HO·) and hydroperoxy (\( {H_2}O_2^{\bullet } \) ) radicals [201].
Jan. F. Rabek
Chapter 7. Degradation of polymers by oxygen reactive species formed from photoreactions of oxygen
Abstract
Being an endothermic allotrope of oxygen, ozone (O3) may serve as a precursor for reactive oxygen species such as atomic oxygen (\( {}^1{O_2} \)) and singlet oxygen (l02). The absorption of light by ozone consists of three bands: 200–320 nm (Hartley band), 300–360 nm (Huggins band) and 440–850 nm (Chappuis band) [352]. The primary photochemical processes differ considerably in each of these bands. The quantum yield of ozone photolysis at 254 nm is almost unity (\( \phi = 0.9\pm 0.2 \)). The main photoproducts are atomic oxygen (O) and singlet oxygen \( {}^1{O_2}({}^1{\Delta_g}) \), according to the reaction [704,990,1628]:
$$ {O_3}\xrightarrow{{hv}}O({}^1D) + {}^1{O_2}(1{\Delta_g}) $$
(7.1)
$$ O({}^1D) + {O_3} \to 2O + {O_2} $$
(7.2)
$$ {}^1{O_2}({}^1{\Delta_g}) + {O_3} \to O + 2{O_2} $$
(7.3)
The quantum yield of ozone decomposition at 334 is \( \phi = 4 \), indicating that one of the products must be excited species capable of decomposing O3 further. The primary process of O3 photolysis at 334 nm occurs according to the reactions [1628]:
$$ {O_3}\xrightarrow{{hv}}O({}^3P) + {}^1{O_2}({}^1{\Delta_g}or{}^3\sum\nolimits_g^{ + } {} ) $$
(7.4)
$$ O({}^3P) + {O_3} \to {O_2} + {O_2} $$
(7.5)
$$ {}^1{O_2}({}^1{\Delta_g}or{}^3\sum\nolimits_g^{ + } {} ) + {O_3}\xrightarrow{{hv}}O({}^3P) + 2{O_2} $$
(7.6)
From this mechanism, the overall quantum yield of O3 decomposition is \( \phi = 4 \).
Jan. F. Rabek
Chapter 8. Photodegradable polymers
Abstract
Photodegradable polymers (plastics) are especially designed in order to control their degradability when exposed to sunlight in the environment. Their main applications are in the solution of the following problems:
1.
Plastic waste disposal problems (cf. sections 8.2 and 8.3).
 
2.
Photodegradation of plastic contamination in the marine environment (cf. section 8.4).
 
3.
Production of photodegradable mulch films with carefully controlled lifetimes (cf. section 8.5).
 
Jan. F. Rabek
Chapter 9. Photodegradation of polymers in extreme conditions
Abstract
Pulsed ultraviolet laser radiation can lead to clean and precise removal of material at the irradiated site on a polymer surface (Fig. 9.1). This phenomenon was discovered in early 1980s using an excimer laser; it was termed ablative photodecomposition and was investigated for several polymers (Table 9.1) [1167,2029, 2045, 2046]. It was also widely reviewed [160, 1296, 1297, 2028, 2030, 2031, 2035, 2036, 2044].
Jan. F. Rabek
Chapter 10. Experimental methods in polymer degradation
Abstract
UV/VIS lamps used in laboratories differ significantly, depending upon the manufacturers of lamps. The main differences are:
1.
emission spectra (which are different for low, medium and high pressure lamps);
 
2.
intensity of emitted radiation;
 
3.
working temperature;
 
4.
lifetime;
 
5.
size and construction.
 
Jan. F. Rabek
Backmatter
Metadaten
Titel
Polymer Photodegradation
verfasst von
Jan. F. Rabek
Copyright-Jahr
1995
Verlag
Springer Netherlands
Electronic ISBN
978-94-011-1274-1
Print ISBN
978-94-010-4556-8
DOI
https://doi.org/10.1007/978-94-011-1274-1