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History: Phenol Formaldehyde Resins or Phenolic Resins Are Synthetic Polymers Obtained by The Reaction

Phenol formaldehyde resins (PF resins) were the first commercial synthetic resins. They are synthesized through a reaction of phenol or substituted phenol with formaldehyde. There are two main types - novolak resins which are acid catalyzed and have a phenol to formaldehyde ratio of 1:0.5-0.8, and resole resins which are base catalyzed and have a ratio of 1:1-1.5. PF resins find major applications as wood adhesives for plywood and particleboard due to their ability to form chemical bonds with lignin in wood. They are also used to produce molded products and as coatings and adhesives.

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214 views

History: Phenol Formaldehyde Resins or Phenolic Resins Are Synthetic Polymers Obtained by The Reaction

Phenol formaldehyde resins (PF resins) were the first commercial synthetic resins. They are synthesized through a reaction of phenol or substituted phenol with formaldehyde. There are two main types - novolak resins which are acid catalyzed and have a phenol to formaldehyde ratio of 1:0.5-0.8, and resole resins which are base catalyzed and have a ratio of 1:1-1.5. PF resins find major applications as wood adhesives for plywood and particleboard due to their ability to form chemical bonds with lignin in wood. They are also used to produce molded products and as coatings and adhesives.

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IBIZA
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© © All Rights Reserved
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PHENOL FORMALDEHYDE RESINS  (PF)

HISTORY

Phenol formaldehyde resins or phenolic resins are synthetic polymers obtained by the reaction
of phenol or substituted phenol with formaldehyde. Used as the basis for Bakelite, PFs were the
first commercial synthetic resins (plastics). Many people date the beginning of the modern
plastics industry to 1907, when Leo Hendrik Baekeland, a Belgian-born American chemist,
applied for a patent on a phenol-formaldehyde thermoset that eventually became known by the
trademarked name Bakelite. Also known as phenolic resins, phenol-formaldehyde polymers were
the first completely synthetic polymers to be commercialized. Although molded products no
longer represent their most important application, through their use as adhesives they still
represent almost half of the total production of thermosetting polymers.

They have been widely used for the production of molded products including billiard balls,
laboratory countertops, and as coatings and adhesives. They were at one time the primary
material used for the production of circuit boards but have been largely replaced with epoxy
resins and fiberglass cloth, as with fire-resistant FR-4circuit board materials.

TYPES OF P-F RESIN

Two methods are used to make phenol-formaldehyde polymers.


1)Novolak resin:
acid catalyzed ; P:F RATIO IS 1: 0.5-0.8

In one, involves reacting formaldehyde with an excess of phenol using an acid catalyst to


produce prepolymers called novolacs. One reacts phenol and formaldehyde directly to produce
a thermosetting network polymer, while the other restricts the formaldehyde to produce a
prepolymer known as novolac which can be moulded and then cured with the addition of more
formaldehyde and heat. There are many variations in both production and input materials that are
used to produce a wide variety of resins for special purposes.

Novolacs resemble the polymer except that they are of much lower molecular weight and are
still thermoplastic. Curing to network polymer is accomplished by the addition of more
formaldehyde or, more commonly, of compounds that decompose to formaldehyde on heating.
2)Resole resin

base catalyzed ; P:F RATIO IS 1: 1-1.5

The other method an excess of formaldehyde is reacted with phenol in the presence of
a base catalyst in water solution to yield the resole, which is a low-molecular-weight prepolymer
with CH2OH groups attached to the phenol rings. On heating, the resole condenses further, with
loss of water and formaldehyde, to yield thermosetting network polymers.

APPLICATIONS
Phenol-formaldehyde polymers make excellent wood adhesives for plywood and particleboard
because they form chemical bonds with the phenollike lignin component of wood. Wood
adhesives, in fact, represent the largest market for these polymers. The polymers are dark in
colour as a result of side reactions during polymerization. Because their colour frequently stains
the wood, they are not suitable for interior decorative paneling.
They are the adhesive of choice for exterior plywood, however, owing to their good moisture
resistance.

Phenolic resins, invariably reinforced with fibres or flakes, are also molded into heat-resistant
objects such as electrical connectors and appliance handles.

CHEMISTRY OF SYNTHESIS

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. The polymerization of phenol
with formaldehyde involves electrophilic aromatic substitution at the ortho and parapositions of
phenol (probably somewhat randomly), followed by cross-linking of the polymeric chains.
Phenol reacts with 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


2 HOC6H4CH2OH → (HOC6H4CH2)2O + H2O

The diphenol (HOC6H4)2CH2 (sometimes called a "dimer") is called bisphenol F,


which is an important monomer in the production of epoxy resins. Bisphenol-F can
further link generating tri- and tetra-and higher phenol oligomers.

Novolaks

Novolaks (or novolacs) are phenol-formaldehyde resins with a formaldehyde to phenol molar
ratio of less than one. In place of phenol itself, they are often produced from cresols
(methylphenols). The polymerization is brought to completion using acid-catalysis such
as sulfuric acid, oxalic acid, hydrochloric acid and rarely, sulfonic acids. The phenolic units are
mainly linked by methylene and/or ether groups. The molecular weights are in the low
thousands, corresponding to about 10–20 phenol units. Obtained polymer is thermoplastic and
require a curing agent or hardener to form a thermoset.

Novolacs have multiple uses as tire tackifier, high temperature resin, binder for carbon bonded
refractories, carbon brakes, photoresists and as a curing agent for epoxy resins. See
also photolithography.
Resoles

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.

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 through the elimination of water molecules. 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. Resols are referred to as "one step" resins as they cure without a cross linker
unlike novolacs, a "two step" resin.

Resols are major polymeric resin materials widely used for gluing and bonding building
materials. Exterior plywood, oriented strand boards (OSB), engineered laminated composite
lumber (LCL) are typical applications.

CROSSLINKING

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 novolacs (F:P <1) do not harden without the addition of a crosslinking
agents, and why resols with the formula F:P >1 will

Hexamethylenetetramine is a hardener added to crosslink novolac. At a temperature greater than


90 °C, it forms methylene and dimethylene amino bridges.

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