Formaldehyde—continued

Fig. 9.10. Mechanism of the proton-catalyzed polymerization of monomeric formaldehyde (top), formalin (middle) and 1,3,5-trioxane (F bottom) to give polyformaldehyde ("paraformaldehyde" H), respectively. The carboxonium ions A, B, C, E etc. play a central role. They are transformed into each other through the nucleophilic reaction of a formaldehyde monomer on the respective carboxonium carbon atom. Analogously, E and formaldehyde continue to react to yield a high-molecular carboxonium ion that is intercepted by (traces of) water to furnish the final neutral product H.

Table 4-1. Facilities That Manufacture or Process Formaldehyde (continued)...

Another reason for predicting low emissions is that the small amount of residual formaldehyde that might be present in the prepared resin is diminished even farther by reactions which occur when the resin cures. Phenolic resins are cured under heat and pressure in a hot-press, usually under highly alkaline conditions. Curing temperatures are usually in the range of 130-220 C. Under these conditions, unreacted formaldehyde continues to react with phenol to form larger phenol formaldehyde polymers. Also, some formaldehyde reacts with various chemical constituents in the wood. Moreover, some formaldehyde is probably converted to methyl alcohol and formic acid by way of the Cannizzaro reaction (J ). ... 

Oxidation, (i) Dissolve 5 g. of potassium dichromate in 20 ml. of dil. H2SO4 in a 100 ml. bolt-head flask. Cool and add 1 ml. of methanol. Fit the flask with a reflux water-condenser and warm gently a vigorous reaction soon occurs and the solution turns green. The characteristic pungent odour of formaldehyde is usually detected at this stage. Continue to heat for 3 minutes and then fit the flask with a knee-tube (Fig. 59, p. 100) and distil off a few ml. Test the distillate with blue litmus-paper to show that it is definitely acid. Then apply Test 3 p. 350) for formic acid. (The reflux-distillation apparatus (Fig. 38, p. 63) can conveniently be used for this test.)... 

C. Palladium on carbon catalyst (5 per cent. Pd). Suspend 41-5 g. of nitric acid - washed activated carbon in 600 ml. of water in a 2-litre beaker and heat to 80°. Add a solution of 4 1 g. of anhydrous palladium chloride (1) in 10 ml. of concentrated hydrochloric acid and 25 ml. of water (prepared as in A), followed by 4 ml. of 37 per cent, formaldehyde solution. Stir the suspension mechanically, render it alkaUne to litmus with 30 per cent, sodium hydroxide solution and continue the stirring for a further 5 minutes. Filter off the catalyst on a Buchner funnel, wash it ten times with 125 ml. portions of water, and dry and store as in B. The yield is 46 g. 

Technological advances continue to be made, several recent patents describe advanced phenol—formaldehyde—furfuryl alcohohol biader systems (68—70). These systems are free of nitrogen compounds that can be detrimental to metal iategrity. Systems with extended bench life have also been developed (71). 

In production, anhydrous formaldehyde is continuously fed to a reactor containing well-agitated inert solvent, especially a hydrocarbon, in which monomer is sparingly soluble. Initiator, especially amine, and chain-transfer agent are also fed to the reactor (5,16,17). The reaction is quite exothermic and polymerisation temperature is maintained below 75°C (typically near 40°C) by evaporation of the solvent. Polymer is not soluble in the solvent and precipitates early in the reaction. 

The enthalpy of the copolymerization of trioxane is such that bulk polymerization is feasible. For production, molten trioxane, initiator, and comonomer are fed to the reactor a chain-transfer agent is in eluded if desired. Polymerization proceeds in bulk with precipitation of polymer and the reactor must supply enough shearing to continually break up the polymer bed, reduce particle size, and provide good heat transfer. The mixing requirements for the bulk polymerization of trioxane have been reviewed (22). Raw copolymer is obtained as fine emmb or flake containing imbibed formaldehyde and trioxane which are substantially removed in subsequent treatments which may be combined with removal of unstable end groups. 

Ma.nufa.cture. AU. manufacturers of butynediol use formaldehyde ethynylation processes. The earliest entrant was BASF, which, as successor to I. G. Farben, continued operations at Ludwigshafen, FRG, after World War II. Later BASF also set up a U.S. plant at Geismar, La. The first company to manufacture in the United States was GAF in 1956 at Calvert City, Ky., and later at Texas City, Tex., and Seadrift, Tex. The most recent U.S. manufacturer is Du Pont, which went on stream at La Porte, Tex., about 1969. Joint ventures of GAF and Hbls in Mad, Germany, and of Du Pont and Idemitsu in Chiba, Japan, are the newest producers. 

Benefits depend upon location. There is reason to beheve that the ratio of hydrocarbon emissions to NO has an influence on the degree of benefit from methanol substitution in reducing the formation of photochemical smog (69). Additionally, continued testing on methanol vehicles, particularly on vehicles which have accumulated a considerable number of miles, may show that some of the assumptions made in the Carnegie Mellon assessment are not vahd. Air quaUty benefits of methanol also depend on good catalyst performance, especially in controlling formaldehyde, over the entire useful life of the vehicle. 

Staged reactions, where only part of the initial reactants are added, either to consecutive reactors or with a time lag to the same reactor, maybe used to reduce dipentaerythritol content. This technique increases the effective formaldehyde-to-acetaldehyde mole ratio, maintaining the original stoichiometric one. It also permits easier thermal control of the reaction (66,67). Both batch and continuous reaction systems are used. The former have greater flexibiHty whereas the product of the latter has improved consistency (55,68). 

Historically, formaldehyde has been and continues to be manufactured from methanol. EoUowing World War II, however, as much as 20% of the formaldehyde produced in the United States was made by the vapor-phase, noncatalytic oxidation of propane and butanes (72). This nonselective oxidation process produces a broad spectmm of coproducts (73) which requites a complex cosdy separation system (74). Hence, the methanol process is preferred. The methanol raw material is normally produced from synthesis gas that is produced from methane. 

Trioxane and Tetraoxane. The cycHc symmetrical trimer of formaldehyde, trioxane [110-88-3] is prepared by acid-catalyzed Hquid- or vapor-phase processes (147—151). It is a colorless crystalline soHd that bods at 114.5°C and melts at 61—62°C (17,152). The heats of formation are — 176.9 kJ/mol (—42.28 kcal/mol) from monomeric formaldehyde and —88.7 kJ/mol (—21.19 kcal/mol) from 60% aqueous formaldehyde. It can be produced by continuous distillation of 60% aqueous formaldehyde containing 2—5% sulfuric acid. Trioxane is extracted from the distillate with benzene or methylene chloride and recovered by distillation (153) or crystallization (154). It is mainly used for the production of acetal resins (qv). 

An early source of glycols was from hydrogenation of sugars obtained from formaldehyde condensation (18,19). Selectivities to ethylene glycol were low with a number of other glycols and polyols produced. Biomass continues to be evaluated as a feedstock for glycol production (20). 

Novolak Resins. In a conventional novolak process, molten phenol is placed into the reactor, foHowed by a precise amount of acid catalyst. The formaldehyde solution is added at a temperature near 90°C and a formaldehyde-to-phenol molar ratio of 0.75 1 to 0.85 1. For safety reasons, slow continuous or stepwise addition of formaldehyde is preferred over adding the entire charge at once. Reaction enthalpy has been reported to be above 80 kj /mol (19 kcal/mol) (29,30). The heat of reaction is removed by refluxing the water combined with the formaldehyde or by using a small amount of a volatile solvent such as toluene. Toluene and xylene are used for azeotropic distillation. FoHowing decantation, the toluene or xylene is returned to the reactor. 

Continuous production of urea—formaldehyde resins has been described in many patents. In a typical example, urea and formaldehyde are combined and the solution pumped through a multistage unit. Temperature and pH are controlled at each stage to achieve the appropriate degree of polymerization. The product is then concentrated in a continuous evaporator to about 60—65% soflds (31). 

A melamine laminating resin used to saturate the print and overlay papers of a typical decorative laminate might contain two moles of formaldehyde for each mole of melamine. In order to inhibit crystallization of methylo1 melamines, the reaction is continued until about one-fourth of the reaction product has been converted to low molecular weight polymer. A simple deterrnination of free formaldehyde may be used to foUow the first stage of the reaction, and the build-up of polymer in the reaction mixture may be followed by cloud-point dilution or viscosity tests. 

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