Preparation of phenol-formaldehyde resin

Introduction:
Phenol formaldehyde resins (PF) are synthetic polymers obtained by the reaction of phenol or substituted phenol with formaldehyde. Phenol-formaldehyde resins, as a group, are formed by a step-growth polymerization reaction that can be either acid- or base-catalysed. 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:

Novolacs are phenol-formaldehyde resins with a formaldehyde to phenol molar ratio of less than one. The polymerization is brought to completion using acid-catalysis such as oxalic acid, hydrochloric acid or sulfonate acids. The phenol units are mainly linked by methylene and/or ether groups. Novolacs are commonly used as photoresists. The molecular weights are in the low thousands, corresponding to about 10-20 phenol units. 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 Resoles. 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.

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

Structure of phenolformaldehyde resins: (a) Novolac, and (b) Resol

Bakelite

Procedure:
1- A mixture of phenol (52 g.), formalin (41 g.), and oxalic acid (0.4 g.) is refluxed in an R.B. flask for one hour. The mixture becomes viscous. 2- Water (120 ml.) is added and the flask cooled and allowed to stand for some time. 3- The supernatant liquid is decanted. The resin is obtained as a pasty mass.

Applications:
1- Phenolic resins are mainly used in the fabrication of printed circuit boards. 2- They are better known however for the production of molded products including pool balls, laboratory countertops, and as coating and adhesives.