Historical Formaldehyde

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. 

Einbrodt et al. (1976) exposed students to 0.26-0.92 ppm formaldehyde vapors for 3 hours, with urine samples collected immediately after exposure and 21 hours after exposure. Urine formaldehyde and urine formic acid (formate) concentrations were found to be higher immediately after exposure compared to 21 hours later however, no baseline sample was obtained prior to exposure. If historic formaldehyde and formic acid baseline levels were assumed, then a closer examination of these data indicates that more formaldehyde (and metabolite) was excreted in the urine than could have possibly been absorbed by inhalation, indicating another route of exposure (perhaps dermal), or co-exposure to another chemical that also has formate as a metabolite (e.g., methanol), or higher personal exposures than were actually measured. There was also no indication that the urine formate levels were adjusted to compensate for urine specific gravity using urine creatinine levels, which may have markedly influenced the test results. 

Rhoda.mines, Rhodamines are commercially the most important arninoxanthenes. If phthalic anhydride is used in place of formaldehyde in the above condensation reaction with y -dialkylarninophenol, a triphenyknethane analogue, 9-phenylxanthene, is produced. Historically, these have been called rhodamines. Rhodamine B (Basic Violet 10, Cl45170) (17) is usually manufactured by the condensation of two moles of y -diethylaminophenol with phthahc anhydride (24). An alternative route is the reaction of diethylamine with fluorescein dichloride [630-88-6] (3,6-dichlorofluoran) (18) under pressure. 

Process parameters can be varied to change the MDA isomer distribution and oligomeric content of PMDA products. Generally, aniline to formaldehyde molar ratios of 2 to 5 are used. To increase the MDA content, higher ratios of aniline to formaldehyde are employed. Increasing the acid to aniline ratio also increases the 4,4 -MDA content of the diamine fraction. Historically, the polyurethane industry consumes as much of the 4,4 -MDI isomer as possible. Recently, however, there has been an increasing demand for higher 2,4 -MDI and 2,4 -PMDI products to be used as replacements for... 

Historical. PE was first isolated by Tollens who was examining the effect of heat and reagents on formaldehyde. Apparently the crude formaldehyde he was working with contained a small % of acetaldehyde, which accounts for the PE formed. Although Tollens isolated it in 1882, it was not identified as PE until 1888 (Ref 2). Further details of the prepn and props of PE appeared in 1891 (Ref 3). The prepn is essentially a condensation betw 3 moles of formaldehyde and 1 of acetaldehyde to give an intermediate tris(hydroxymethyl)-acetaldehyde which is not isolated. An Intermolecular oxidn/redn then takes place betw this intermediate, and a 4th mole of formaldehyde, giving PE and formic ac (Ref 13, p 2). This type reaction is discussed under Cannizzaro Reaction in the Encycl (Vol 2, C25)... 

Thermosets differ molecularly from thermoplastics in that their individual chains are anchored to one another through crosslinks. The resulting network creates cohesive materials that demonstrate better thermal stability, rigidity, and dimensional stability than thermoplastics. Some examples of traditional thermosets are melamine-formaldehyde resins, which are used to treat fabrics to make them wrinkle-free, and Bakelite (a phenol-formaldehyde resin), a historically important polymer used in many applications, such as costume jewelry, electrical switches, and radio casings. 

The scope of the present article comprises syntheses of sugar-type compounds containing four or more carbon atoms, an aldehyde or a ketone group, and a minimum of two hydroxyl groups (or their equivalents, such as amino or thiol groups) at least one of them being bound to a center of chirality. The subject of aldol-type reactions of formaldehyde and two- or three-carbon atom hydroxy aldehydes and hydroxy ketones has been omitted a comprehensive discussion of this topic, including a historical survey, has appeared in this Series.5... 

It should be noted that although these potential substitutes avoid the use of NTA, the process of synthesis using amine, formaldehyde, and cyanide also leads to trace amounts of NTA being formed that have to be removed for some applications. With NTA reclassification in Europe now official, the use of these new variants in applications where historically NTA has been used is accelerating. 

Commercially, formaldehyde is sold as u. IKt aquruus so lulion Good reactivity, low price, and important end-use markets have combined lo give formaldehyde its growth mi pcliiv Formaldehyde is produced by vnpor-pha.se oAidulnm or by dehydration of methanol Its mam muricis are in production ot phenolic and urea resins The price of formaldehyde has historically been coupled closely to the price of methanol... 

Some report that over 50 percent of the urea-formaldehyde resins consumed went into particleboard. This is brought out because there may be a shift away from urea resin for certain types of oriented particleboard used in structural plywood constructions. Historically, particleboard has been used for inner plies as previously mentioned in some hardwood plywood. There is now one plant in production in Idaho which produces mechanically oriented strand particleboard for use specifically as core for softwood plywood production. It is anticipated that this trend to some degree will increase in the future, and phenolic resins appear to be the mechanism with which this particleboard will be bonded. 

Some of the chemical strategies used in weatherproofing have been applied to the preservation of cellulosics for indoor storage and display. The historical Wasa sails of 1628 were preserved by copolymerizing acrylates and styrene onto this material (36). Antimicrobial treatment of cotton goods by polymerization in situ of a urea-mercury compound with formaldehyde or immersion in a quaternary ammonium salt solution protected the fabric for up to three years storage provided it did not need to be laundered (37). 

From Formaldehyde.—Historically and physiologically, the most important synthesis of hexose mono-saccharoses is from formaldehyde. In 1861 Butlerow found that dioxymethylene (tri-oxymethylene), produced by polymerizing formaldehyde, yielded with hot lime water a sweet substance to which he gave the name of methylenitan. The substance reduced Fehling s solution, but was optically inactive and non-fermentable with yeast zymase. Later, Loew obtained a sweet, non-fermentable syrup by the direct action of lime-water on formaldehyde. This substance he called formose. He afterward obtained what he considered another sugar by the action of magnesium hydroxide upon formaldehyde. This substance was fermentable by yeast and to it he gave the name of methose. In 1887, Fischer and Tafel... 

Neither a historical review nor a complete story of this field of polymer making is presented here. Rather, this is a series of views of the chemistry and procedures, from which one may obtain some idea of the potential as well as of the limitations of the methods. The discussion includes only reactions which yield essentially linear polymers, bypassing polyurethane foams and phenol-formaldehyde condensates. 

Historically, the reaction of phenol with formaldehyde was of vital importance to the polymer industry, being one of the first totally synthetic commercial polymer resin systems developed. In 1907, Leo H. Baekeland commercialized, under the tradename Bakelite , a range of cured phenol-formaldehyde resins, which were useful in producing heat-resistant molded products . Since this early work, phenol-formaldehyde resins have been used in many applications, including refractory compounds, adhesives, thermal insulation and electrical industries ". ... 

Despite this practical progress, great uncertainty still exists as to the precise mechanism by which formaldehyde is held within a board and slowly released as a gas to the atmosphere. Historically, many have considered the emission potential of a board to be governed, particularly in a board s early life, by the board s so-called free formaldehyde content (9). 

Stewart (USA) 1986 Comparison of historical exposures, current exposures, and job titles to develop a final exposure estimate Formaldehyde Cumulative exposure (ppm)... 

J. (1986). Estimating historical exposures to formaldehyde in a retrospective mortality study. Appl Ind Hyg 1, 34 1. 

In naming aldehydes, acids, and esters the roots for one and two carbons are usually form- and acet-, as in formaldehyde and acetic acid, these historical names being more commonly used than the strict lUPAC methanal and ethanoic acid. Departures from lUPAC nomenclature often... 

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