Phenol formaldehyde resin

Phenol formaldehyde resins (PF) include synthetic thermosetting resins such as obtained by the reaction of phenols with formaldehyde. Sometimes the precursors include other aldehydes or other phenol. Phenolic resins are mainly used in the production of circuit boards. They are better known however for the production of molded products including pool balls, laboratory countertops, and as coatings and adhesives. In the form of Bakelite, they are the earliest commercial synthetic resin.^[1][2]

Formation and structure

Phenol-formaldehyde resins, as a group, are formed by a step-growth polymerization reaction that can be either acid- or base-catalysed. Since formaldehyde exists predominantly in solution as a dynamic equilibrium of methylene glycol oligomers, the concentration of the reactive form of formaldehyde depends on temperature and pH.

Phenol is reactive towards formaldehyde at the ortho and para sites (sites 2, 4 and 6) allowing up to 3 units of formaldehyde to attach to the ring. The initial reaction in all cases involves the formation of a hydroxymethyl phenol:

HOC₆H₅ + CH₂O → HOC₆H₄CH₂OH

The hydroxymethyl group is capable of reacting with either another free ortho or para site, or with another hydroxymethyl group. The first reaction gives a methylene bridge, and the second forms an ether bridge:

HOC₆H₄CH₂OH + HOC₆H₅ → (HOC₆H₄)₂CH₂ + H₂O

The diphenol (HOC₆H₄)₂CH₂ (sometimes called a "dimer") is called bisphenol F, which is itself an important monomer in the production of epoxy resins. Bisphenol-F can further link generating tri- and tetra-and higher phenol oligomers.

2 HOC₆H₄CH₂OH → (HOC₆H₄CH₂)₂O + H₂O

Novolac

Novolacs (originally Novolak, the name given by Leo Baekeland),are phenol-formaldehyde resins made where the molar ratio of formaldehyde to phenol of less than one. The polymerization is brought to completion using acid-catalysis. The phenol units are mainly linked by methylene groups. Novolacs are commonly used as photoresists. See also photolithography. The molecular weights are in the low thousands, corresponding to about 10-20 phenol units.

Hexamethylene tetramine or "hexamine" is a hardener that is added to crosslink novolac. At ≥180 °C, the hexamine forms crosslinks to form methylene and dimethylene amino bridges.

Resols

Base-catalysed phenol-formaldehyde resins are made with a formaldehyde to phenol ratio of greater than one (usually around 1.5). These resins are called resols. Phenol, formaldehyde, water and catalyst are mixed in the desired amount, depending on the resin to be formed, and are then heated. The first part of the reaction, at around 70 °C, forms a thick reddish-brown tacky material, which is rich in hydroxymethyl and benzylic ether groups.

The rate of the base-catalysed reaction initially increases with pH, and reaches a maximum at about pH = 10. The reactive species is the phenoxide anion (C₆H₅O^-) formed by deprotonation of phenol. The negative charge is delocalised over the aromatic ring, activating sites 2, 4 and 6, which then react with the formaldehyde.

Being thermosets, hydroxymethyl phenols will crosslink on heating to around 120 °C to form methylene and methyl ether bridges. At this point the resin is a 3-dimensional network, which is typical of polymerised phenolic resins. The high crosslinking gives this type of phenolic resin its hardness, good thermal stability, and chemical imperviousness.

Crosslinking and the phenol/formaldehyde ratio

When the molar ratio of formaldehyde:phenol reaches one, in theory every phenol is linked together via methylene bridges, generating one single molecule, and the system is entirely crosslinked. This is why bakelites (F:P <1) don't harden without the addition of a crosslinking agent, and why resins with the formula F:P >1 will.

Applications

Phenolic resins are found in myriad industrial products. Phenolic laminates are made by impregnating one or more layers of a base material such as paper, fiberglass or cotton with phenolic resin and laminating the resin-saturated base material under heat and pressure. The resin fully polymerizes (cures) during this process. The base material choice depends on the intended application of the finished product. Paper phenolics are used in manufacturing electrical components such as punch-through boards and household laminates. Glass phenolics are particularly well suited for use in the high speed bearing market. Phenolic micro-balloons are used for density control. Snooker balls as well as balls from many table-based ball games are also made from Phenol formaldehyde resin.

The Dutch forger Han van Meegeren mixed phenol formaldehyde with his oil paints before baking the finished canvas in order to fake the drying out of the paint over the centuries.

Trade names

• Bakelaque is a rigid laminate or tube made from phenolic resin on a substrate cotton fabric, paper or glass.^[3]
• Bakelite is made from Phenol resin and wood flour.
• Novotext is cotton fibre-reinforced phenolic, using randomly oriented fibres.
• Oasis is "[a]n open-celled phenolic foam that readily absorbs water and is used as a base for flower arrangements."^[4]
• Paxolin Paperstone]^[5] and Richlite are made from phenolic resin and paper.
• Trymer Green is a rigid cellular phenolic thermal insulation.
• Tufnol is made from phenolic resin and woven cotton or linen fabric.^[6]

See also

• Urea-formaldehyde

References

1. ^ A. Gardziella, L.A. Pilato, A. Knop, Phenolic Resins: Chemistry, Applications, Standardization, Safety and Ecology, 2nd edition, Springer, 2000
2. ^ Wolfgang Hesse "Phenolic Resins" in Ullmann's Encyclopedia of Industrial Chemistry, 2002, Wiley-VCH, Weinheim. doi:10.1002/14356007.a19_371.
3. ^ "Attwater Group Industrial Laminates". Attwater Group. http://www.attwater.com/products/laminate.asp. 
4. ^ "Smithers Oasis Resource Center". Web.archive.org. Archived from the original on 2008-04-07. http://web.archive.org/web/20080407213030/http://www.smithersoasis.com/res_techfacts.php. Retrieved 2010-10-21. 
5. ^ "PaperStone | The Countertop With a Conscience". Paperstoneproducts.com. http://www.paperstoneproducts.com/. Retrieved 2010-10-21. 
6. ^ "TUFNOL Fabric laminates". Tufnol. http://www.tufnol.com/tufnol/default.asp?id=21. 

External links

• Safety data for phenol-formaldehyde resin