28 Furan Resins

28.1

INTRODUCTION

The furan or furane resins mainly find use because of their excellent chemical and heat resistance. In the past they have mainly been used in applications peripheral to the plastics industry such as foundry resins, for chemically resistant cements and for binders. Recent developments have facilitated their use in laminates for chemical plant.

28.2

PREPARATION OF INTERMEDIATES

The two intermediates of commercial furan resins are furfural and furfuryl alcohol. Furfural occurs in the free state in many plants but is obtained commercially by degradation of hemicellulose constituents present in these plants. There are a number of cheap sources of furfural, and theoretical yields of over 20% (on a dry basis) may be obtained from both corn cobs and oat husks. In practice yields of slightly more than half these theoretical figures may be obtained. In the USA furfural is produced in large quantities by digestion of corn cobs with steam and sulphuric acid. The furfural is removed by steam distillation. Furfural is a colourless liquid which darkens in air and has a boiling point of 161.7"C at atmospheric pressure. Its principal uses are as a selective solvent used in such operations as the purification of wood resin and in the extraction of butadiene from other refinery gases. It is also used in the manufacture of phenolfurfural resins and as a raw material for the nylons. The material will resinify in the presence of acids but the product has little commercial value. Catalytic hydrogenation of furfural in the presence of copper chromite leads to furfuryl alcohol, the major intermediate of the furan resins (Figure 28.1). 810

CH-CH

cq ,y
0
CHO

II

II

[H21
Copper Chromite
Figure 28.1

Resinification

8 11

CH-CH CH
0

II

II
CH,OH

The alcohol is a mobile liquid, light in colour, with a boiling point of 170C.
It is very reactive and will resinify if exposed to high temperatures, acidity, air

or oxygen. Organic bases such as piperidine and n-butylamine are useful inhibitors.

28.3 RESINIFICATION
Comparatively little is known of the chemistry of resinification of either furfuryl alcohol or furfural. It is suggested that the reaction shown in Figure 28.2 occurs initially with furfuryl alcohol.

+
-

Furfuryl H,O

Alcohol

Figure 28.2

The liberation of small amounts of formaldehyde has been detected in the initial stage but it has been observed that this is used up during later reaction. This does not necessarily indicate that formaldehyde is essential to cross-linking, and it would appear that its absorption is due to some minor side reaction. Loss of unsaturation during cross-linking indicates that this reaction is essentially a form of double bond polymerisation, viz Figure 28.3.

Figure 28.3

812 Furan Resins This reaction, like the initial condensation, is favoured by acidic conditions and peroxides are ineffective. The polymerisation of furfural is apparently more complex and less understood. For commercial use a partially condensed furan resin is normally prepared which is in the form of a dark free-flowing liquid. Final cure is carried out in situ. The liquid resins are prepared either by batch or continuous process by treating furfuryl alcohol with acid. Initially the reaction mixture is heated but owing to the powerful exothermic an efficient cooling system is necessary if cross-linking is to be avoided. Water of condensation is removed under vacuum and the reaction stopped by adjusting the pH to the point of neutrality. Great care is necessary to prevent the reaction getting out of hand. This may involve, in addition to efficient cooling, a judicious choice of catalyst concentration, the use of a mixture of furfuryl alcohol and furfural which produces a slower reaction but gives a more brittle product and, possibly, reaction in dilute aqueous solution. The resins are hardened in situ by mixing with an acidic substance just before application. A typical curing system would be four parts of toluene-p-sulphonic acid per 100 parts resin. The curing may take place at room temperature if the resin is in a bulk form but elevated temperature cures will often be necessary when the material is being used in thin films or coatings. 28.4 PROPERTIES OF THE CURED RESINS

The resins are cross-linked and the molecular segments between the cross-links are rigid and inflexible. As a consequence the resins have an excellent heat resistance, as measured in terms of maintenance of rigidity on heating, but are rather brittle. Cured resins have excellent chemical resistance. This is probably because, although the resins have some reactive groupings, most of the reactions occurring do not result in the disintegration of the polymer molecules. Therefore, whilst surface layers of molecules may have undergone modification they effectively shield the molecules forming the mass of the resin. The resins have very good resistance to water penetration. Compared with the phenolics and polyesters the resins have better heat resistance, better chemical resistance, particularly to alkalis, greater hardness and better water resistance. In these respects they are similar to, and often slightly superior to, the epoxide resins. Unlike the epoxides they have a poor adhesion to wood and metal, this being somewhat improved by incorporating plasticisers such as poly(viny1 acetate) and poly(viny1 formal) but with a consequent reduction in chemical resistance. The cured resins are black in colour. 28.5 APPLICATIONS

The principal applications for furan resins are in chemical plant. Specific uses include the lining of tanks and vats and piping and for alkali-resistant tile cements. The property of moisture resistance is used when paper honeycomb structures are treated with furan resins and subsequently retain a good compression strength even after exposure to damp conditions.

Bibliography

8 13

Laminates have been prepared for the manufacture of chemical plant. They have better heat and chemical resistance than the polyester- epoxide- phenolic- or aminoplastic-based laminates but because of the low viscosity of the resins were not easy to handle. Because they were also somewhat brittle, furan-based laminates have been limited in their applications. This situation may be expected to change somewhat with the advent of new polymers of greater viscosity (375-475 cP) (37.5-47.5 N s/m2) and generally easier handling qualities. Whilst patents (e.g. Ger. Pat. 1927 776) describe polymeric blends of UF and furane resins as being suitable for such laminating it has been stated that the commercially available polymers (e.g. Quacorr RP100A-Quaker Oats Co.) are basically furfuryl alcohol polymers not modified by PF or UF resins. They are cured by modified acid catalysts, giving a rather more gentle cure than the earlier catalyst systems. Furane resin-chopped strand mat laminates have tensile strengths in excess of 20 000 lbf/in2 (140 MPa), a heat distortion temperature of about 218C and good fire resistance. Not only does the material have excellent resistance to burning but smoke emission values are reported to be much less than for fire-retardant polyester resin. The laminates are being increasingly used in situations where corrosion is associated with organic media, where corrosion is encountered at temperatures above 100C as in fume stacks and where both fire retardance and corrosion resistance are desired as in fume ducts. One other substantial development of the 1960s was the use of ureaformaldehyde-furfuryl alcohol materials as foundry resins, particularly for hot-box operations. The furfuryl alcohol component of the resin is usually in the range 25 -40%. Furane resins are useful in impregnation applications. Furfural alcohol resinified in situ with zinc chloride catalysts can be used to impregnate carbon (including graphite) products and be cured at 93-150C to give products of greater density and strength and which have much lower permeability to corrosive chemicals and gases. The resins are also used for coating on to moulds to give a good finish that is to be used for polyester hand-lay up operations. Development work by Russian workers had led to interesting products formed by reaction of furfuryl alcohol with acetone and with aniline hydrochloride. The resins formed in each case have been found to be useful in the manufacture of organic-mineral non-cement concretes with good petrol, water and gas resistance. They also have the advantage of requiring only a small amount of resin to act as a binder.

Bibliography
Encyclopedia of Polymer Science and Technology (2nd Edition), Vol. 7, pp. 454-73, John Wiley, New York (1987) MCDOWALL, R., and LEWIS, P., Trans. Plastics Inst., 22, 189 (1954) MORGAN, P., Glass-reinforced Plastics, Iliffe, London, 3rd Edn (1961) RADCLIFFE, A. T. (Eds. WHELAN. A , , and BRYDSON. I. A,)Chapter 5 of Developments wifh Thermosetting Plastics, Applied Science, London (1975)
GANDINI, A. FURAN RESINS,

See also various articles by Itinskii, Kamenskii, Ungureau and others in Plasticheskie Massy from 1960 onwards. (Translations published as Soviet Plastics by Rubber and Technical Press Ltd, London.)