Polymers ketone

Furfural—acetone resins have been used to form resin-aggregate mixtures referred to as organic concretes. Despite the reportedly excellent properties, there has been virtually no commercial use of such resins outside the former Soviet Union. The stmctures and polymerization mechanisms of these furfural—aldehyde—ketone polymers are discussed in a review (6). 

However, on a lightly cross-linked hydroxyethylmethacrylate/styrene polymer that swells in polar solvents (22, 365), or on a silica-gel support (366), catalyst performance matches that of the soluble one for the precursor amino acid substrates. A rhodium-DIOP analog has also been supported on a polymer containing pendent optically active alcohol sites [incidentally, formed via hydrosilylation and hydrolysis of a ketonic polymer component using an in situ rhodium(I)-DIOP catalyst]. The supported catalyst in alcohol again matched that of the soluble catalyst for... 

Xue, S. N. and Yin, G. P. 2006. Proton exchange membranes based on polyjvinylidene fluoride) and sulfonated polyjether ether ketone). Polymer 47 5044-5049. 

Photochemistry of Ketone Polymers in the Solid Phase A Review... 

GUILLET et AL. Thin Film Studies of Vinyl Ketone Polymers... 

Somersall, A. C., Guillet, J. E., Photochemistry of Ketone Polymers VIII, ... 

Treatment of the monomer with an acidic catalyst leads initially to polymers of low molecular weight and ultimately to crosslinked, black, insoluble, heat-resistant resin (17). Despite their reportedly excellent properties, virtually no commercial use of such resins exists outside the Soviet Union. The structure and polymerization mechanism of these furfural-ketone polymers are described in a recent study (18). An excellent combustion-resistant resin has been reported (19) from the addition of dialkylphosphites to bis(2-furfurylidene) ketone (6). Furfural condensates with other aliphatic and aromatic ketones have been reported (20,21) to provide photo-crosslinkable resins and hypergol components. 

Muramoto, A., "Dependence of Interaction Parameter on Molecular Weight and Concentration for Solutions of Poly(dimethylsiloxane) in Methyl Ethyl Ketone," Polymer, 23, 1311 (1982). 

Much work has been devoted to the photochemistry of ketone polymers despite their limited commercial application. The main reason for this is that initiation of the photodegradation of different polymers is attributed to carbonyl groups incorporated during manufacture or processing. Another reason is that the photochemistry of low molecular weight ketones is the most thoroughly studied of any class of compounds and is now comparatively well understood, so the mechanism of the photodegradation of ketone polymers can be established on a sounder base. 

Quantum yields of the Norrish reactions of both types depends on the structure of the ketone polymer in the following ways. 

A polymeric pinacol,poly[3-methyl-2-(4-vinylphenyl)-2,3-butanediol],has been prepared by radical polymerization of the styrenic diol monomer and shown to be cleanly and quantitatively converted to a non-conjugated ketone in the solid state by reaction with a photochemically-generated acid [151,348, 350]. The rearrangement reaction can be readily monitored by IR spectroscopy as the disappearance of the hydroxyl OH absorption is accompanied by appearance of a new ketone carbonyl absorption (Fig. 116). Since a polar alcohol (isopropanol) dissolves the polar diol polymer in the unexposed regions but cannot dissolve the less polar ketone polymer produced in the exposed regions, the resist functions as a negative system with alcohol as a developer. The diol polymer is stable thermally to 225 °C in the absence of acid. 

Methyl Vinyl Ketone 3-Buten-2-one A3-2 -but-enone methylene acetone acetyl ethylene 3-oxo -a -butyl-ene. C4H(0 mol wt 70.09. C 68.55%, H 8.63%, O 22.83%. CHJCOCH=CHi. Prepn by condensation of acetone and formaldehyde to 3 -keto butanol and dehydration to methyl vinyl ketone Merling Kohler, J. Soc. Chem. Ind 29> 1037 (1910) White, Haward, X Chem. Soc. 1943, 25. Prepn from vinylaoetylene Conaway, U S. pat. 1,967,225 (1934 to du Pont). For review and polymerization characteristics see 4<Vinyl Ketone Polymers in Encyclopedia of Polymer Science and Technology vol. 14 (Interscience, New York, 197]) pp 617-636. 

Amerik and J.E. Guillet, The Photochemistry of ketone polymers. IV. Photolpsis of methyl vinyl ketone copol3miers, Macromolecules 4, 375 (1971) E. Dan and J.E. Guillet, Photochemistry of ketone polymers. X. Chain scission reaction in the solid state, Macromolecules 6, 230 (1973). 

Source Reprinted with permission from J. A. Slivinskas and J. E. Guillet, Y-Radioly is of ketone polymers. Journal of Polymer Science, Polym. Chem. Ed. 11, 3053 (1973). Copyri t 1973 John Wiley Sons, Inc. 

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