Phenol Formaldehyde

• Phenol-formaldehyde resins (phenolic resins), the first

thermosetting plastics, are considered to be the first
truly synthetic commercially available plastic resins.
• Unlike celluloids, the first man-made plastic resins,
phenolic resins are made from purely synthetic
materials.
• Phenol-formaldehyde resins are formed by the chemical
reaction between phenols and formaldehyde solutions
(formalin).
 Raw Materials
• Phenol-formaldehyde resins are general-purpose thermosets
formed mainly by the polycondensation reaction between phenols
and formaldehyde solutions.
• The three major raw materials for making phenolic resins are:
(1) Phenol C,H,OH.
(2) Formaldehyde CH,O.
(3) Hexamethylene Tetramine (CH,),N,.
• Other phenols, such as cresols (monomethyl-phenols), xylenols
(dimethyl- phenols), resorcinol (m-dihydroxybenzene), and
alkylated-phenols, can be used in place of phenol, but their usage
is limited due to the availability of less expensive synthetic phenol.
PHENOL
• Phenol is primarily obtained from the fractional
distillation of coal tar and various synthetic processes.
• There are at least six known commercial synthetic
processes for making phenol, of which the four most
common are Cumene, Raschig, Dow, and Sulfonation.
• The Sulfonation process, although popular at one time,
is no longer in use.
• Cumene Process for Making Phenol
• In the cumene process, commercialized in 1952 by H. Hook,
the reaction between benzene and propylene with an
aluminum chloride catalyst yields isopropyl benzene
(cumene). Cumene oxidizes to hydroperoside, which is
broken down by acidification into phenol and acetone:
• Raschig Process
• The Raschig process passes benzene, hydrogen, and air over a
heated copper catalyst at 200 to 300°C. The intermediate product
is chlorobenzene and water in the gaseous state. The water
hydrolyses the chlorobenzene, when passed over hot silica
catalyst at 5OO°C, to phenol and HCl.
• Dow Process
• The Dow process, established in 1920, uses the direct
vigorous reaction of chlorobenzene and sodium
hydroside solution at 300°C and 4000 psi:
FORMALDEHYDE (CH₂O)
• Formaldehyde is produced by the controlled catalytic oxidation of methyl
alcohol (methanol).
• The result is the dehydrogenation of methanol to formaldehyde. In the
process, a mixture of methanol vapor and air is passed over a heated
copper oxide catalyst at 300°C to 6OO’C to produce a mixture of
formaldehyde and water.
• The product is a 37% solution formaldehyde that is subsequently enriched
to a 40% solution known as formalin:
HEXAMETHYLENE TETRAMINE (Hexamine or “HEXA”)
(CH₂)₆N₄
• HEXA is produced by passing ammonia gas into a 30%
formaldehyde solution at room temperature:
RESINIFICATION (PRODUCTION) of
PHENOL-FORMALDEHYDE RESINS
Reaction Chemistry
• It is known, however, that the reaction is initiated by the
activation of the benzene ring by the hydroxyl group such that a
methylol group (CH₂OH) joins the benzene nucleus at the ortho
and para positions.
• The reaction produces a resole if an alkaline catalyst is used and a
novolac if an acid catalyst is used.
• From the work of Baekeland and Lebacht, three basic stages are
recognized in the phenol-formaldehyde reaction:
1. A-stage or resole.
2. B-stage or resitol.
3. C-stage or resite.
• At the A-stage, the initial condensation products are mainly
alcohols. The resin at this point is thermoplastic and soluble
in inorganic solvents.
• At the B-stage, there is a higher degree of condensation and
some crosslinking, with a consequent increase in molecular
weight and viscosity, and a decrease in solubility. The resin is
not fully cured; it is soft and fusible when hot but hard and
brittle when cold.
• At the C-stage, the degree of polymerization and crosslinking
is very high, and there is almost a complete cure. The resin is
infusible and insoluble.
Polymerization Process
• Phenolics are produced by the polycondensation reaction
between phenols and formalin (40% aqueous solution of
formaldehyde).
• The trifunctional phenol reacts with the difunctional
formaldehyde, resulting in a three dimensional matrix when the
reaction is carried out beyond the gel point.
• After the gel point, further curing results in a thermoset.
• The ready-to-be-used resin is processed to just before the gel
point during the polymerization process. Based on this, there are
two main types of phenolic resins:
(1) Resoles or one-stage resins.
(2) Novolacs or two-stage resins.
 Resole Phenolic Resins
• Resole phenolic resins are produced by polymerizing (heating) a 1:
1 (or more) molar ratio of phenol and formalin in a reactor vessel
in the presence of an alkaline catalyst such as ammonia, sodium
carbonate, or sodium hydroxide at 100°C for about I hour.
• It is usual to have 1.1 to 1.5 mole of the formaldehyde for each
mole of phenol.
• Polymerization is stopped short of the gel point by cooling
(B-staging).
• The product at this point is an intermediate resole
phenol-formaldehyde resin. If a solid product is desired, the
intermediate is dried by heating under a vacuum for 3 to 4 hours
to prevent heat hardening.
Schematic of typical reactor vessel for the bulk polymerization of phenol-formaldehyde resins
• Resole phenol-formaldehyde resin is a water soluble methyl
(-CH,OH) bearing thermoplastic.
• The curing process to the final thermoset material can be initiated
by just heating the resole in a mold above its gel point.
• The resole resins formed have reactive methylol and hydroxyl
groups.
• When heated, resoles form larger molecules with methylene
crosslinks without the use or addition of a curing agent.
• The phenol-formaldehyde resin resinification reaction is a typical
polycondensation reaction since water is given off as a
by-product.
 Resinification Reaction of Resole-type Phenol-Formaldehyde Resin

• Resole phenolic resins have a short shelf life: less than 1 year (less
than 60 days in most cases). They are referred to as one-step
phenolics because they do not require curing agents, only heat.
• Casting resins, bonding resins, and resins for laminating paper
and wood are made in this way.
 Novolac Phenol-Formaldehyde Resins
• The polymerization of phenol-formaldehyde novolac resin is
carried out in the presence of an acid catalyst such as oxalic
acid, sulfuric acid, hydrochloric acid, formic acid, and
aromatic sulfuric acids.
• Sulfuric and oxalic acids are the two most commonly used.
• The gel point of the cure is deliberately delayed by using a
phenol-formaldehyde feedstock that is deficient in
formaldehyde.
• It is customary to use a phenol-formaldehyde ratio of 1:0.8 in
the first stage (prepolymerization).
• Polymerization is carried out by heating the mixture for 2 to
4 hours at reflux, with water removal at temperatures as
high as 160°C.
• The resultant low-molecular weight molten intermediate is
cooled.
• The glassy material is carefully crushed and blended with
hexamethylene tetramine (HEXA) (in powder form) to
produce a molding compound.
• The HEXA is the second part or hardener; hence, the blended
resins arc referred to as two-step resins or novolac phenolic
resins.
• Upon heating the novolac resins to about 165°C in a mold, the HEXA
decomposes to provide the formaldehyde necessary for the final curing.
• The addition of HEXA gives the resin a final working
phenol-formaldehyde molar ratio of 1: 1.5.
• Novolac phenolic resins have an infinite shelf life under normal storage
conditions.

Resinification Reaction of Novolac-type Phenol-Formaldehyde resin

 RESOL NOVOLAC
Resole phenolic resins are produced by using Novolac resins are produced via acidic catalysts
alkaline catalysts
Resole phenolic resins are produced via B-staging Novolac resins are made by prepolymerization

Resole phenolic resins are methylol-bearing resins Novolacs are non-methylol-bearing resins

Resoles typically have a shelf life of less than 1 year Novolacs have an infinite shelf life
(less than 60 days)
Resoles split off water when they cure Novolacs give off ammonia when they cure
Less dimensionally stable Novolac resins are twice more dimensionally stable
than resoles.
Resoles are typically casting and bonding resins, molding compounds are made from novolacs
Resoles are usually liquids Novolacs are solids.
 Properties
• In Phenol formaldehyde wide range of molding powders is available in which the
composition of the resin, fillers etc is varied to provide mouldings suitable for
many purposes.
• Here compression and transfer processes commonly used.
• It is very easy to mould. Phenolic resin has Retain properties at freezing
temperatures.
• The phenol formaldehyde have Improved strength and dimensional stability and
Improved impact resistance and also cast resins.
• It’s color is good normally transparent and may be colorless It is good dimensional
stability on heating up to about 300 degree F.
• Poor conductors of heat , so that handles of pans etc stay cool to touch. It can
burn only with difficulty.
• Age of phenolic resin is negligible deterioration.
• Electrical if we will verify then it is good electrical insulators, Laminated Plastics.
 Applications
• There are live major areas of phenolic resins application:
plywood, adhesive and bonding, laminates, molded
parts, and coatings.
• Plywood and laminates are part of the adhesive and
bonding market, but the large volume usage of phenolic
resins in plywood (49% of the phenolic resin market)
and laminates (6%) warrant their consideration as
distinct areas of application of phenolic resins.