Photografting reactions

Similar results were obtained in the photografting reaction of N-methyloyloxethyl-N-methyl-p-toluidine... 

MMA and DMAPMA poly(MMA-co-DMAPMA) 23, obtained by radical copolymerization, can produce a photografting reaction with acrylonitrile (AN) using BP as the initiator [61]. The formation of a graft copolymer, poly[(MMA -c<7-DMAPMA)- -AN] was confirmed by FT-IR spectrophotometry. Based on ESR studies and end group analysis, the mechanism of grafting reaction is proposed as follows ... 

It further appears that sensitized photografting reactions are more attractive, since longer wavelengths of excitation may be used, thus increasing the possibility of a potentially valuable... 

SCHEME 13.23 Mechanism of photografting reaction unable-to-be-irradiated surfaces. 

Grafting reactions on a polymer substrate, i.e. on the surface of a polymer film, can be carried out via radical generation processes. For example, hydrophobic hydrocarbon surfaces can be made more hydrophilic by a photografting reaction with acrylic acid. The photografting of a UV screen-type stabilizer would be highly desirable. 

When the source of initiation is altered from ionising radiation to UV, analogous additive effects to those previously discussed have been found. For reasonable rates of reaction, sensitisers such as benzoin ethyl ether (B) are required in these UV processes. Thus inclusion of mineral acid or lithium perchlorate in the monomer solution leads to enhancement in the photografting of styrene in methanol to polyethylene or cellulose (Table V). Lithium nitrate is almost as effective as lithium perchlorate as salt additive in these reactions (Table VI), hence the salt additive effect is independent of the anion in this instance. When TMPTA is included with mineral acid in the monomer solution, synergistic effects with the photografting of styrene in methanol to polyethylene are observed (Table VII) consistent with the analogous ionising radiation system. 

Choice of sensitizer is related to the base polymer properties. Besides triplet sensitizers, dyes(4, 5), metal salts(11, 12), and radical initiators(7, 11, 12) have been used in photografting. These sensitizers other than triplet sensitizers are, however, not capable of initiating surface photografting onto polyolefins. Although benzoin isopropyl ether has been used for photografting of polypropylene, the reaction conditions seem to be in favor of deep grafting(12). 

Apart from the chemical effects of solvent as hydrogen donor, being heterogeneous systems, an important role of solvent is to provide appropriate reaction sites on the balance of solvent interactions with base polymer and growing graft chain. For the study of solvent effects, AM is not an adequate monomer since it is scarcely soluble in non-polar solvents. Instead, acrylic acid(AA) was employed and photografting was conducted as shown in Figure 8. 

Table Base Solvents (S) 4. Summary of Solvent Film 0PP, Monomer AM, S - 0PP BP 3 + S interaction reaction Effects on Surface Photografting. Sensitizer BP, Irradiation at 366nm. Surface Rate of Proposed structure concentration grafting of grafted 0PP film of polyAM ...

The fact that many anthraquinone dyes, when adsorbed on cellulose, undergo a photochemical reaction with the polymer was used by Geacintov, Stannett, Abramson and Hermans 17> as a means photografting upon cellulose. 

The photoinitiator may be loaded on the membrane surface by adsorption or may be dissolved in the monomer solution. For example, PET nucleopore membranes were modified using BP dissolved in the monomer solution following UV irradiation of the solution and the immersed membrane (Yang and Yang 2003). It was shown that photografting occurred mainly on the top membrane surface rather than in the membrane pores. This approach is relatively simple however, its main drawback is a low local concentration of BP on the membrane surface because BP moves to the membrane surface only by diffusion. This results in a low grafting efficiency. High bulk BP concentration may cause a side reaction, such as homopolymerization. In addition, the use of monomers that do not have a common solvent with BP is limited BP is almost insoluble in water. 

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