Polymers, formaldehyde Manufacture

In 1933, ICI purchased an interest in urea-formaldehyde manufacturer Croydon Mouldrite Limited, forerunner of ICI (Plastics) Ltd. (1938). ICI took up research into urea-formaldehyde polymers at Billingham (and phenol-formaldehyde products at its dyestuffs division). 

Some commercially important cross-linked polymers go virtually without names. These are heavily and randomly cross-linked polymers which are insoluble and infusible and therefore widely used in the manufacture of such molded items as automobile and household appliance parts. These materials are called resins and, at best, are named by specifying the monomers which go into their production. Often even this information is sketchy. Examples of this situation are provided by phenol-formaldehyde and urea-formaldehyde resins, for which typical structures are given by structures [IV] and [V], respectively ... 

Several new types of pigments have been introduced commercially which are based on polymers that do not contain formaldehyde. These pigments have some different characteristics but have the advantage of not giving off formaldehyde. Most of the primary manufacturers provide these types of pigments and more are being developed. 

Nippon Shokubai and U.K. Seung are producing a fluorescent polymer claimed to be made from a co-condensation of ben2oguanamine and formaldehyde. Fine highly thermoset particles are manufactured in solution and later dried. It is useful in a wide range of appHcations, specifically plastics, and markets where bleed is a problem. 

Isocyanates. The commodity isocyanates TDI and PMDI ate most widely used in the manufacture of urethane polymers (see also Isocyanates, organic). The former is an 80 20 mixture of 2,4- and 2,6-isomers, respectively the latter a polymeric isocyanate obtained by phosgenation of aniline—formaldehyde-derived polyamines. A coproduct in the manufacture of PMDI is 4,4 -methylenebis(phenyHsocyanate) (MDI). A 65 35 mixture of 2,4- and 2,6-TDI, pure 2,4-TDI and MDI enriched in the 2,4 -isomer are also available. The manufacture of TDI involves the dinitration of toluene, catalytic hydrogenation to the diamines, and phosgenation. Separation of the undesired 2,3-isomer is necessary because its presence interferes with polymerization (13). 

Poly(vinyl alcohol) is employed as a modifier of thermosetting resins used as adhesives in plywood and particle board manufacture (314,315). The polymer is added to urea-formaldehyde or urea—melamine—formaldehyde resins to improve initial grab, to increase viscosity, and, in general, to improve the characteristics of the board. 

Various polymers and latexes ai e used in manufacturing different articles for medical use. Safety measures in using such articles require strict control measures which provide for detecting toxic substances on hygienic standard levels or on the permissible migration level (PML) (mg/dm ). Chromatographic reaction methods ai e used to reveal formaldehyde, phenol, and epichlorhydrin. 

From the time that formaldehyde was first isolated by Butlerov in 1859 polymeric forms have been encountered by those handling the material. Nevertheless it is only since the late 1950s that polymers have been available with the requisite stability and toughness to make them useful plastics. In this period these materials (referred to by the manufacturers as acetal resins or polyacetals) have achieved rapid acceptance as engineering materials competitive not only with the nylons but also with metals and ceramics. 

In order to manufacture such polymers, it is first necessary to produce a very pure form of formaldehyde. This is typieally produced from an alkali-precipitated low molecular weight polyformaldehyde which has been carefuly washed with distilled water and dried for several hours under vacuum at about 80°C. The dried polymer is then pyrolysed by heating at 150-160°C, and the resultant formaldehyde passed through a number of cold traps (typically four) at -15°C. Some prepolymerisation occurs in these traps and removes undesirable... 

In the manufacture of pure resorcinol resins, the reaction can be violently exothermic unless controlled by the addition of alcohols. Because the alcohols perform other useful functions in the glue mix, they are left in the liquid adhesive. PRF adhesives are generally prepared firstly by reaction of phenol with formaldehyde to form a PF resol polymer, that has been proved to be in the greatest percentage, and often completely, linear [95], In the reaction step that follows the resorcinol chemical is added in excess to the PF-resol to react it with the PF-resin -CH2OH groups to form PRF polymers in which the resorcinol groups can be resorcinol chemical or any type of resorcinol-formaldehyde polymer. 

As polymer chemistry advanced in the 1930s and 1940s, stronger and more durable synthetic adhesives such as early phenol, resorcinol and urea formaldehydes began to supplant natural glues in wood aircraft manufacture. Around this time however, metal began to replace wood as the dominant material for aircraft manufacture. Aerospace adhesives research and development moved on to focus on metals, primarily aluminum, as the substrates of interest. 

Organic materials Corrosive vapours are sometimes emitted by organic materials used either in packaging or in the manufactured article, and may be troublesome in confined spaces. Some woods, particularly unseasoned oak and sweet chestnut, produce acetic acid (see Section 18.10), and certain polymers used in paints, adhesives and plastics may liberate such corrosive vapours as formic acid and hydrogen sulphide . It may be necessary to carry out exposure trials, particularly where materials capable of liberating formaldehyde or formic acid are involved. Most corrosion problems of this kind can be prevented by using desiccants, and in many cases they are confined to imperfectly cured materials. For an excellent review see Reference 9. 

Baekeland A process for making organic polymers by reacting phenols with formaldehyde. Based on an observation by A. von Bayer in 1872 and developed into an industrial process by L. H. Baekeland from 1905 to 1909. It was used to make Bakelite, one of the first commercial plastics. The first industrial manufacture began in Germany in 1910. 

In general, the acid-sorbing resins may be classified as high molecular weight polyamines or polyimines. Thus, the original Adams and Holmes material was a polymer of m-phenylenediamine. Cation Exchange materials include synthetic resins, such as sulfonated phenol-formaldehyde or polystyrene types, and sulfonated coal. Some manufacturers have a variety of sub-types which are considered superior for particular applications. 

The workhorse of the VLSI industry today is a composite novolac-diazonaphthoquinone photoresist that evolved from similar materials developed for the manufacture of photoplates used in the printing industry in the early 1900 s (23). The novolac matrix resin is a condensation polymer of a substituted phenol and formaldehyde that is rendered insoluble in aqueous base through addition of 10-20 wt% of a diazonaphthoquinone photoactive dissolution inhibitor (PAC). Upon irradiation, the PAC undergoes a Wolff rearrangement followed by hydrolysis to afford a base-soluble indene carboxylic acid. This reaction renders the exposed regions of the composite films soluble in aqueous base, and allows image formation. A schematic representation of the chemistry of this solution inhibition resist is shown in Figure 6. 

This is used in manufacture of brake linings and is a polymer based on cashew nutshell liquid admixed with formaldehyde or furfuraldehyde and other ingredients. The polymerised resin mixture is cast into 8 cm thick slabs and then ground finely to produce the friction dust. Several fires have been experienced during bulk storage of the dust, attributed to autoxidation of the still partially unsaturated resin compound. Previously, linseed oil was used in place of the nutshell liquid, but fires were then more frequent. 

Together, antifreeze, PET, and polyester polymers account for about 98% of the ethylene glycol produced in the United States. It is also used sometimes as a deicer for aircraft surfaces. The two hydroxyl groups in the EG molecule also make EG suitable for the manufacture of surfactants and in latex paints. Other applications include hydraulic brake fluid, the manufacture of alkyd resins for surface coatings, and stabilizers for water dispersions of urea-formaldehyde and melamine-formaldehyde The hygroscopic properties (absorbs moisture from the air) make EG useful as a humectant for textile fibers, paper, leather, and adhesives treatment. 

The formaldehyde process is an air oxidation of methanol, CH3OH, which has water as a by-product. Formaldehyde is a gas at room temperature, but is usually handled either as a water solution called formalin or as polymers called paraformaldehyde and trioxane. Both are readily converted back ro formaldehyde. Some uses of formaldehyde are the manufacture of polymer resins and as a germicide. 

The polymerization of phenols or aromatic amines is applied in resin manufacture and the removal of phenols from waste water. Polymers produced by HRP-catalyzed coupling of phenols in non-aqueous media are potential substitutes for phenol-formaldehyde resins [123,124], and the polymerized aromatic amines find applications as conductive polymers [112]. Phenols and their resins are pollutants in aqueous effluents derived from coal conversion, paper-making, production of semiconductor chips, and the manufacture of resins and plastics. Their transformation by peroxidase and hydrogen peroxide constitutes a convenient, mild and environmentally acceptable detoxification process [125-127]. 

Figure 17 provides an overview of the function of the diazoquinone/novolac materials. The matrix resin is a copolymer of a phenol and formaldehyde. The generic term for this class of polymers is novolac (18) meaning "new lacquer" and describes the purpose for which they were first developed. The chemical industry produces millions of tons of novolac each year where its end use is that of a thermoset resin and adhesive. Novolac is commonly used, for example, as the principle adhesive in the manufacture of plywood. 

By 1924 Bakelite had become so popular that it was featured on the cover of Time magazine as a substance that will not burn and will not melt. Bakelite jewelry, telephones, pens, radios, car parts, airplane propellers, ashtrays, billiard balls, and cameras were everywhere. Just about the only item that did not become popular was the Bakelite coffin. People would wear, cook in, and eat off plastic, but they refused to be buried in it. Bakelite s success stimulated research to improve the material even further, especially after scientists pointed out that in the manufacture of Bakelite the small phenol and formaldehyde molecules had joined together to make a giant three-dimensional lattice. In other words. Bakelite was the world s first synthetic giant molecule, the first synthetic polymer. 

Diacetoxy-2-butene. Mitsubishi commercialized a new proces, the acetoxy-lation of 1,3-butadiene, as an alternative to the Reppe (acetylene-formaldehyde) process for the production of l,4-diacetoxy-2-butene. l,4-Diacetoxy-2-butene is tranformed to 1,4-butanediol used in polymer manufacture (polyesters, polyurethanes). Additionally, 1,4-butanediol is converted to tetrahydrofuran, which is an important solvent and also used in polymer synthesis. 

Manufacture and Processing. The cyanoacrylic esters are prepared via the Knoevenagel condensation reaction, in which the corresponding alkyl cyanoacetale reacts with formaldehyde in the presence of a basic catalyst to form a low molecular weight polymer. The polymer slurry is acidified and the water is removed. Subsequently, the polymer is cracked and redistilled at a high temperature onto a suitable stabilizer combination to prevent premature repolymerization. Strong protonic or Lewis acids arc normally used in combination with small amounts of a free-radical stabilizer. 

---