Poly , photooxidation

Photooxidation of poly(styrene) has been a subject of considerable interest over the past 25 years (14,15). However, the surface photooxidation of poly(styrene), the aspects of which are most pertinent to the proposed photooxidative scheme, has only been examined recently (16,17). Free radical intermediates have been proposed to account for the formation of oxidized groups upon 254 nm irradiation of poly(styrene). 

A photooxidative scheme has been developed to pattern sub half-micron images in single layer resist schemes by photochemical generation of hydrophilic sites in hydrophobic polymers such as poly(styrene) and chlorinated poly(styrene) and by selective functionalization of these hydrophilic sites with TiCU followed by O2 RIE development. Sub half-micron features were resolved in 1-2 pm thick chlorinated poly(styrene) films with exposures at 248 nm on a KrF excimer laser stepper. The polymers are much more sensitive to 193 nm (sensitivity 3-32 mJ/cm2) than to 248 nm radiation (sensitivity -200 mJ/cm2) because of then-intense absorption at 193 nm. 

An example of the application of IR spectroscopy is in the photooxidation of poly(propylene) (1.3). During the early stages of oxidation absorption due to aldehydes... 

Figure 8. Thermally stimulated current in photooxidized poly- S-vinylcarbazole film. Films are (i) not illuminated (ii) illuminated for 60 min (Hi) illuminated for 2 min with the 330-nm UV light in air at room temperature. In all cases, these photo-oxidized films were cleaned by heating to 100°C prior to the measurement, cooled to —1S0°C, and illuminated with the total light of the Hg lamp for 20 min in vacuo.

Poly(pyrido[3,4- ]pyrazine vinylene) 693 has been synthesized via condensation of 3,4-diamino-2,5-dibtomopyridine 691 with l,2-bis[3-(2 -ethylhexyloxy)phenyl]-ethane-l,2-dione 692 followed by coupling with l,2-bis(tri- -butyl-stannyl)ethylene in DMF at 110°C in the presence of tetrakis(triphenylphosphine)palladium. The vinylene polymer 693 showed improved stability toward photooxidation compared with similar polymers with purely aliphatic side chains and also had smaller band gaps (Equation 58) <2002SM(131)53>. 

Nickel complexes are of considerable importance as stabilizers and antioxidants for polymers of various kinds. The nickel(II) complex of the benzoic acid derivative (12) (see Section 66.4) acts as a stabilizer against oxidation of polybutadiene,46 but is less effective in this respect than the manganese and cobalt complexes. Complex (20) is effective in decreasing the rate of photooxidation of two-phase poly(vinyl chloride)-polybutadiene rubbers 74... 

To understand these reactions, the so-called Bolland and Gee reaction scheme17-18 and its subsequent developments has been applied to explain the chain reaction characteristics of both thermal and photooxidation of polyolefins. The scheme (Scheme 2.1) has been found to be a useful model for many other polymers comprising significant aliphatic character, such as aliphatic polyamides and polyesters and certain polyvinyls including poly(vinyl chloride) (PVC). 

The effect of ultraviolet irradiation in air on the wettability of thin films of amorphous polymers has been studied. With poly(vinyl chloride), poly(methyl methacrylate), poly(n-butyl methacrylate), poly (ethylene terephthalate), and polystyrene the changes in contact angles for various liquids with irradiation time are a function of the nature of the polymer. A detailed study of polystyrene by this technique and attenuated total reflectance spectra, both of which are sensitive to changes in the surface layers, indicates that the contact angle method is one of the most sensitive tools for the study of polymer photooxidation in its early stages. The method is useful in following specific processes and in indicating solvents to be used in the separation and isolation of photooxidation products. 

That photooxidation is indeed responsible for the observed changes is indicated by a comparison with the results obtained with films irradiated in vacuum. Both polystyrene and poly(n-butyl methacrylate) irradiated in vacuum showed no changes in contact angles after exposures up to 120 min. with poly (ethylene terephthalate), contact angles for all of the liquids tended to increase slightly. 

The Ni and Pt complexes can also be incorporated into polymer films of quaternized poly(vinylpyridine) (PVP) and deposited onto the transparent electrode (84). Photocurrents are enhanced to microamps (pA), an increase that may be attributed to either the effect of immobilization of the complexes near the electrode surface or an increase of the excited-state lifetimes in the polymer matrix. However, the effective concentrations of the complexes in this study were much greater than for the acetonitrile solutions in their earlier work. The polymer films are not stable to continuous photolysis, and voltammograms of the films are quite sensitive to anions used in the supporting electrolyte. The system can be stabilized by using a polymer blend of PVP and a copolymer containing quaternary ammonium ion and including [Fe(CN)6]4- in the electrolyte solution (85). Upon irradiation of the visible MLCT bands of [M(mnt)2]2 (M = Ni, Pt), photocurrents are produced. The mechanism (Scheme 4) is believed to involve photooxidation of the metal bis(dithiolene) triplet state by the Sn02 electrode, followed by [Fe(CN)6]4 reduction of the monoanion, with completion of the ET cycle as ferricyanide, Fe(CN)6 3, diffuses to the other electrode and is reduced. 

Fabris F, Benaglia M, Danelli T, Sperandio D, Pozzi G (2002) Poly(ethylene glycol)-supported tetrahydroxyphenyl porphyrin a convenient, recyclable catalyst for photooxidation reactions. Org Lett 4 4229 -242... 

After the examination of the PS photooxidation mechanism, a comparison of the photochemical behavior of PS with that of some of its copolymers and blends is reported in this chapter. The copolymers studied include styrene-stat-acrylo-nitrile (SAN) and acrylonitrile-butadiene-styrene (ABS). The blends studied are AES (acrylonitrile-EPDM-styrene) (EPDM = ethylene-propylene-diene-monomer) and a blend of poly(vinyl methyl ether) (PVME) and PS (PVME-PS). The components of the copolymers are chemically bonded. In the case of the blends, PS and one or more polymers are mixed. The copolymers or the blends can be homogeneous (miscible components) or phase separated. The potential interactions occurring during the photodegradation of the various components may be different if they are chemically bonded or not, homogeneously dispersed or spatially separated. Another important aspect is the nature, the proportions and the behavior towards the photooxidation of the components added to PS. How will a component which is less or more photodegradable than PS influence the degradation of the copolymer or the blend We show in this chapter how the... 

PHOTOOXIDATION OF BLENDS OF POLYSTYRENE AND POLY(VINYL METHYL ETHER) (PVME-PS)... 

The materials analyzed were blends of polystyrene (PS) and poly(vinyl methyl ether) (PVME) in various ratios. The two components are miscible in all proportions at ambient temperature. The photooxidation mechanisms of the homo-polymers PS and PVME have been studied previously [4,7,8]. PVME has been shown to be much more sensitive to oxidation than PS and the rate of photooxidation of PVME was found to be approximately 10 times higher than that of PS. The photoproducts formed were identified by spectroscopy combined with chemical and physical treatments. The rate of oxidation of each component in the blend has been compared with the oxidation rate of the homopolymers studied separately. Because photooxidative aging induces modifications of the surface aspect of the material, the spectroscopic analysis of the photochemical behavior of the blend has been completed by an analysis of the surface of the samples by atomic force microscopy (AFM). A tentative correlation between the evolution of the roughness measured by AFM and the chemical changes occurring in the PVME-PS samples throughout irradiation is presented. 

In contrast to the relative stability of as-polymerized poly-DSP crystals in the air, amorphous poly-DSP is rapidly photooxidized in the air upon exposure to sunlight and produces nitrile derivatives together with products containing carbonyl and hydroxy... 

As already described, amorphous poly-DSP is readily photooxidized upon exposure to the sunlight in the air69) however, the same sample is thermally depolymerized to the monomer in an oxygen-free atmosphere more rapidly than the crystalline polymer65). 

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