Molecular weight resists

A basic theme throughout this book is that the long-chain character of polymers is what makes them different from their low molecular weight counterparts. Although this notion was implied in several aspects of the discussion of the shear dependence of viscosity, it never emerged explicitly as a variable to be investi-tated. It makes sense to us intuitively that longer chains should experience higher resistance to flow. Our next task is to examine this expectation quantitatively, first from an empirical viewpoint and then in terms of a model for molecular motion. 

Note that the diffusion coefficient for a polymer through an environment of low molecular weight molecules is typically on the order of magnitude of 10"" m" sec". If the first subscript indicates the diffusing species, and the second the surrounding molecules, and P stands for polymer and S for small molecules, we see that the order of diffusion coefficients is Ds g > Dp g > Dp P sequence which makes sense in terms of relative frictional resistance. 

Furfural reacts with ketones to form strong, crosslinked resins of technical interest in the former Soviet Union the U.S. Air Force has also shown some interest (42,43). The so-called furfurylidene acetone monomer, a mixture of 2-furfurylidene methyl ketone [623-15-4] (1 )> bis-(2-furfurylidene) ketone [886-77-1] (14), mesityl oxide, and other oligomers, is obtained by condensation of furfural and acetone under basic conditions (44,45). Treatment of the "monomer" with an acidic catalyst leads initially to polymer of low molecular weight and ultimately to cross-linked, black, insoluble, heat-resistant resin (46). 

Positive-Tone Photoresists based on Dissolution Inhibition by Diazonaphthoquinones. The intrinsic limitations of bis-azide—cycHzed mbber resist systems led the semiconductor industry to shift to a class of imaging materials based on diazonaphthoquinone (DNQ) photosensitizers. Both the chemistry and the imaging mechanism of these resists (Fig. 10) differ in fundamental ways from those described thus far (23). The DNQ acts as a dissolution inhibitor for the matrix resin, a low molecular weight condensation product of formaldehyde and cresol isomers known as novolac (24). The phenoHc stmcture renders the novolac polymer weakly acidic, and readily soluble in aqueous alkaline solutions. In admixture with an appropriate DNQ the polymer s dissolution rate is sharply decreased. Photolysis causes the DNQ to undergo a multistep reaction sequence, ultimately forming a base-soluble carboxyHc acid which does not inhibit film dissolution. Immersion of a pattemwise-exposed film of the resist in an aqueous solution of hydroxide ion leads to rapid dissolution of the exposed areas and only very slow dissolution of unexposed regions. In contrast with crosslinking resists, the film solubiHty is controUed by chemical and polarity differences rather than molecular size. 

The polymers dissolve in l,l,l,3,3,3-hexafluoro-2-propanol [920-66-1/, hot phenols, and /V, /V- dim ethyl form am i de [68-12-2] near its boiling point. The excellent solvent resistance notwithstanding, solvents suitable for measurement of intrinsic viscosity, useflil for estimation of molecular weight, are known (13,15). 

The polymeric products can be made to vary widely in physical properties through controlled variation in the ratios of monomers employed in thek preparation, cross-linking, and control of molecular weight. They share common quaHties of high resistance to chemical and environmental attack, excellent clarity, and attractive strength properties (see Acrylic ester polymers). In addition to acryHc acid itself, methyl, ethyl, butyl, isobutyl, and 2-ethylhexyl acrylates are manufactured on a large scale and are available in better than 98—99% purity (4). They usually contain 10—200 ppm of hydroquinone monomethyl ether as polymerization inhibitor. 

Many challenging industrial and military applications utilize polychlorotriduoroethylene [9002-83-9] (PCTFE) where, ia addition to thermal and chemical resistance, other unique properties are requited ia a thermoplastic polymer. Such has been the destiny of the polymer siace PCTFE was initially synthesized and disclosed ia 1937 (1). The synthesis and characterization of this high molecular weight thermoplastic were researched and utilized duting the Manhattan Project (2). The unique comhination of chemical iaertness, radiation resistance, low vapor permeabiUty, electrical iasulation properties, and thermal stabiUty of this polymer filled an urgent need for a thermoplastic material for use ia the gaseous UF diffusion process for the separation of uranium isotopes (see Diffusion separation methods). 

Vinyl organosol coatings, which incorporate a high molecular weight thermoplastic PVC organosol dispersion resin, are extremely flexible. Soluble thermosetting resins, including epoxy, phenoHc, and polyesters, are added to enhance the film s product resistance and adhesion. 

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