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Phenol Formaldehyde The phenol-formaldehyde polymers are the oldest commercial synthetic polymers, first introduced around 100

years ago. Their inventor, Leo Bakeland, had no idea what was happening in his reaction kettles, but he was able to work out conditions to produce a tough, light, rigid, chemically resistant solid from two inexpensive ingredients. Phenol formaldehyde resins (PF) are synthetic polymers obtained by the reaction of phenol or substituted phenol with formaldehyde. Phenolic resins are made by reaction of formaldehyde with phenol and substituted phenol. The main reaction is the production of methyl bridges between aromatic rings. Thermoset resins are usually prepared as prepolymer and then in the second stage they are cross-linked by the effect of catalyst, heat and pressure. Phenolic resins are thermoset type polymers. Physical Properties Phenolic resins are yellow to brown color and the coloration can be very intense. Phenolic resins which are not cross-linked are commercially available as solids or solutions. The polycondensation can be driven so far that the resins are no longer should but can only be swelled by organic solvents. The softening point of solids resins can be determined by capillary melting point.

Formation and structure


Phenol-formaldehyde resins, as a group, are formed by a step-growth polymerization reaction that can be either acid- or base-catalyzed. 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-formaldehyde resins represent an important type of adhesive employed in the production of wood based panels of superior water resistance. Novolacs
Novolacs are phenol-formaldehyde resins with 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.

Resoles Base-catalyzed phenol-formaldehyde resins are made with 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.

In a strongly acidic medium, hydroxymethyl groups are rapidly converted into methyl bridges. Therefore, the synthesis of resols can only be catalyzed by bases or salts of weak acids or bases.

Phenolic resins are polycondensation products of phenols and aldehydes, in particular phenol and formaldehyde. Amino Resins Amino resins are thermosetting resins with excellent tensile strength, hardness, and impact resistance, and they are used as molding materials. The principal attractions of amino resins and plastics are water solubility before curing, which allows easy application to and with many other materials, colorlessness, which allows unlimited colorability with dyes and pigments, excellent solvent resistance in the cured state, outstanding hardness and corrosion resistance, and good heat resistance. Limitations of these materials include release of formaldehyde during cure. Some amino resins are used as additives to modify the properties of other materials. Automobile tires are strengthened by amino resins which improve the adhesion of rubber to tire cord. A racing sailboat may have a better chance to win because the sails of Dacron (Du Pont) polyester have been treated with an amino resin (1). Amino resins can improve the strength of paper even when it is wet. Molding compounds based on amino resins are used for parts of electrical devices, bottle and jar caps, molded plastic dinnerware, and buttons. Amino resins are also often used for the cure of other resins, such as Alkyd Resins, and reactive acrylic polymers. These polymer systems may contain 550% of the amino resin and are commonly used in the flexible backings found on carpets and draperies, as well as in protective surface coatings, particularly the durable baked enamels of appliances, automobiles.

Raw Materials Most amino resins are based on the reaction of formaldehyde [50-00-0] with urea or melamine. Although formaldehyde will combine with many other amines, amides, and aminotriazines to form useful products, only a few are used and are of minor importance compared with products based on urea and melamine.