Phenohcs

Picrates of aromatic ethers. Most phenohc ethers react with picric acid in chloroform or alcoholic solution to yield crystalUne picrates (compare At oTnatic Hydrocarbons, Section IV,9,1). 

Dissolve 0 01 mol of the phenohc ether in 10 ml. of warm chloroform, and also (separately) 0 01 mol of picric acid plus 5 per cent, excess (0 -241 g.) in 10 ml. of chloroform. Stir the picric acid solution and pour in the solution of the phenohc ether. Set the mixture aside in a 100 mb beaker and ahow it to crystallise. Recrystahise the picrate from the minimum volume of chloroform. In most cases equahy satisfactory results may be obtained by conducting the preparation in rectified spirit (95 per cent. CjHgOH). The m.p. should be determined immediately after recrystallisation. It must be pointed out, however, that the picrates of aromatic ethers suflFer from the disadvantage of being comparatively unstable and may undergo decomposition during recrystaUisation. 

Furfural is a resin former under the influence of strong acid. It will self-resinify as well as form copolymer resins with furfuryl alcohol, phenoHc compounds, or convertible resins of these. Conditions of polymerization, whether aqueous or anhydrous, inert or oxygen atmosphere, all affect the composition of the polymer. Numerous patents have issued relating to polymerization and to appHcations. Although the resins exhibit a degree of britdeness, they have many outstanding properties a number of appHcations are discussed under "Uses."... 

Under acidic conditions, furfuryl alcohol polymerizes to black polymers, which eventually become crosslinked and insoluble in the reaction medium. The reaction can be very violent and extreme care must be taken when furfuryl alcohol is mixed with any strong Lewis acid or Brn nstad acid. Copolymer resins are formed with phenoHc compounds, formaldehyde and/or other aldehydes. In dilute aqueous acid, the predominant reaction is a ring opening hydrolysis to form levulinic acid [123-76-2] (52). In acidic alcohoHc media, levulinic esters are formed. The mechanism for this unusual reaction in which the hydroxymethyl group of furfuryl alcohol is converted to the terminal methyl group of levulinic acid has recendy been elucidated (53). 

Furfuryl alcohol is shipped in bulk or dmms. Although not corrosive to metals, it is a powerful solvent and penetrant containers, tanks, lines, and valves need to be in good condition to avoid potential leakage. Furfuryl alcohol can be stored in containers lined with baked phenoHc resin coatings however, it should not be put in containers that are coated with lacquers, varnishes, or epoxy resins because it is an excellent solvent for many such coatings. 

Uses. Furfuryl alcohol is widely used as a monomer in manufacturing furfuryl alcohol resins, and as a reactive solvent in a variety of synthetic resins and appHcations. Resins derived from furfuryl alcohol are the most important appHcation for furfuryl alcohol in both utihty and volume. The final cross-linked products display outstanding chemical, thermal, and mechanical properties. They are also heat-stable and remarkably resistant to acids, alkaUes, and solvents. Many commercial resins of various compositions and properties have been prepared by polymerization of furfuryl alcohol and other co-reactants such as furfural, formaldehyde, glyoxal, resorcinol, phenoHc compounds and urea. In 1992, domestic furfuryl alcohol consumption was estimated at 47 million pounds (38). 

Furfuryl alcohol alone, or in combination with other cross-linkable binders such as phenoHc reins, chemical by-products and pitch, catalyzed with acid, gives carbon yields of 35—56%. Furfural together with cyclohexanone, pitch, or phenoHc resins gives, under acid catalysis, yields of 35—55% carbon under basic catalysis yields of 5—50% are achieved. FurfuryHdeneacetone resins (13 and 14), catalyzed by acid or base, give carbon yields of 48—56 and... 

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. 

I ovolac Synthesis and Properties. Novolac resins used in DNQ-based photoresists are the most complex, the best-studied, the most highly engineered, and the most widely used polymers in microlithography. Novolacs are condensation products of phenoHc monomers (typically cresols or other alkylated phenols) and formaldehyde, formed under acid catalysis. Figure 13 shows the polymerization chemistry and polymer stmcture formed in the step growth polymerization (31) of novolac resins. 

Fig. 21. Representative nonionic photoacid generators. A variety of photochemical mechanisms for acid production ate represented. In each case a sulfonic acid derivative is produced (25,56,58—60). (a) PAG that generates acid via 0-nitrobenzyl rearrangement (b) PAG that generates acid via electron transfer with phenohc matrix (c) PAG that is active at long wavelengths via electron-transfer sensitization (d) PAG that generates both carboxylic acid and...

Acid-C t lyzed Chemistry. Acid-catalyzed reactions form the basis for essentially all chemically amplified resist systems for microlithography appHcations (61). These reactions can be generally classified as either cross-linking (photopolymerization) or deprotection reactions. The latter are used to unmask acidic functionality such as phenohc or pendent carboxyhc acid groups, and thus lend themselves to positive tone resist apphcations. Acid-catalyzed polymer cross-linking and photopolymerization reactions, on the other hand, find appHcation in negative tone resist systems. Representative examples of each type of chemistry are Hsted below. 

Testing—includes test specimen preparation, bond durabiHty tests, and stmctural performance tests. It should be noted that formaldehyde emission tests of phenoHc bonded products such as stmctural plywood are not required because emissions are normally about 0.02—.03 pl/L (ppm), weU below the previously noted safe level of 0.10 p.L/L (ppm). 

Eig. 6. Decomposition of polymers as a function of temperature during heating. A, polymethylene B, polytetrafluoroethylene C, silicone D, phenoHc resin ... 

Cork [61789-98-8] is an effective low cost charring ablator. In order to reduce moisture absorption and related poor performance, cork particles are often blended in a silicone or phenoHc resin. The result is a uniform ablative material in a sheet form that is easy to apply. 

Bond Type. Most bonded abrasive products are produced with either a vitreous (glass or ceramic) or a resinoid (usually phenoHc resin) bond. Bonding agents such as mbber, shellac, sodium siHcate, magnesium oxychloride, or metal are used for special appHcations. 

Shipment, Storage, and Price. Butynediol, 35% solution, is available in tank cars, tank trailers, and dmms. Stainless steel, nickel, aluminum, glass, and various plastic and epoxy or phenoHc liners have ak been found satisfactory. Rubber hose is suitable for transferring. The solution is nonflammable and freezes at about —5°C. 

Shipment, Stora.ge, ndPrice. Tank cars and tank trailers, selected to prevent color formation, are of aluminum or stainless steel, or lined with epoxy or phenoHc resins dmms are lined with phenoHc resins. Flexible stainless steel hose is used for transfer. Because of butanediol s high freezing point (about 20°C) tank car coil heaters are provided. The U.S. Hst price for bulk quantities in 1991 was about 2.18/kg, but heavy discounting was prevalent for large contracts. 

Shipment, Stora.ge, ndPrice. Butyrolactone is shipped in unlined steel tank cars and plain steel dmms. Plain steel, stainless steel, aluminum, and nickel are suitable for storage and handling mbber, phenoHcs, and epoxy resins are not suitable. Butyrolactone is hygroscopic and should be protected from moisture. Because of its low free2ing point (—44° C), no provision for heating storage vessels is needed. 

Shipment, Stora.ge, ndPrices. Methyl vinyl ether is available in tank cars or cylinders, while the other vinyl ethers are available in tank cars, tank wagons, or dmms. Mild steel, stainless steel, and phenoHc-coated steel are suitable for shipment and storage. If protected from air, moisture, and acidic contamination, vinyl ethers are stable for years. United States bulk prices in 1991 for methyl vinyl ether, ethyl vinyl ether, and butyl vinyl ether were listed as about 5.78/kg, 6.28/kg, and 6.08/kg, respectively. 

Aqueous solutions of 50% acrylamide should be kept between 15.5 and 38°C with a maximum of 49°C. Below 14.5°C acrylamide crystallizes from solution and separates from the inhibitor. Above 50°C the rate of polymer buildup becomes significant. Suitable materials of constmction for containers include stainless steel (304 and 316) and steel lined with plastic resin (polypropylene, phenoHc, or epoxy). Avoid contact with copper, aluminum, their alloys, or ordinary iron and steel. 

The effectiveness of phenoHc inhibitors is dependent on the presence of oxygen and the monomers must be stored under air rather than an inert atmosphere. Temperatures must be kept low to minimise formation of peroxides and other products. Moisture may cause mst-initiated polymerization. 

Phenolic Resins. Phenohc resins (qv) are formed by the reaction of phenol [108-95-2] C H O, and formaldehyde [50-00-0] CH2O. If basic conditions and an excess of formaldehyde are used, the result is a resole phenohc resin, which will cure by itself Hberating water. If an acid catalyst and an excess of phenol are used, the result is a novolac phenohc resin, which is not self-curing. Novolac phenohc resins are typically formulated to contain a curing agent which is most often a material known as hexamethylenetetraamine [100-97-0] C H22N4. Phenohc resin adhesives are found in film or solution... 

---