ALKYD RESINS

Nishad Vaidya
PraveenKumar M
Introduction
• Alkyd resins form the largest group of the synthetic resins available
to the paint industries and consumption is greater than that of the
any other resin for wide variety of application due to their low cost
and versatility.
• Alkyd resins are easy to pigment and are compatible with most
substance used in surface coating industries and have they can be
easily modified for special application.
• Alkyd resins are formed as a result from the polycondensation of
polyols with polyacids (a part of the polyacids will comprise a fatty
acid or oil).
Raw materials
Dibasic acids
• Most commonly dibasic acids
used is Phthalic anhydride as it
reacts at low temperature as
compare to other anhydrides.
• When improved film hardness
and chemical resistance are
required, isophthalic acid and
terphthalic acid are also
employed in alkyd resin
manufacture.
• Trimellitic anhydride has been
increasable used in water soluble
or water dispersible alkyds
Raw materials
Polyols
• The most widely used polyhydric alcohols are glycerol
and Pentaerythritol but in some specific areas of
application trimethylol propane and sorbitol are also
employed.
• Glycerol contain two primary and one secondary
hydroxyl group and it reacts at same rate with fatty
acids. With dibasic acids the primary alcholos reacts
more readily than secondary.
• Pentaerythritol contains four primary hydroxyl groups
and thus from relatively complex resin than glycerol with
better performance properties like fast drying greater
hardness , better gloss etc.
• The higher functionality of Pentaerythritol limits its used
in short and medium oil types of alkyds as it gel rapidly
but widely used for long and medium long oil alkyds.
• Trimethylol propane has three primary alcohol but the
reactivity is slow because of sterically hindered
structure. It has low molecular weight and viscosity than
glycerol alkyds
Raw materials
Oils and Fatty acids
• Saponification: When oil is
heated in presence of alkali,
followed by acidification,
they give glycerol and fatty
acids.
• Oils are divided into three
types depends on amount
of unsaturation as : drying,
semidrying and non-drying
• Oleic , Linoleic , Linolenic ,
liconic acid are most
commonly used
Oil
• Properties such as drying time, hardness, color and moisture sensitivity all
depend on the drying oil, its type and the degree of unsaturation.
• Soya bean oil has been shown to give good drying rates and good color
retention.
• Castor and coconut oils have good color retentive properties and are used
as plasticizing resins because of their nonoxidizing characteristics
• Linseed oils generally dry faster but darken on exposure to light.
Soya Bean Oil

Linseed Oil
Manufacture of alkyd resins
Monoglyceride process
• When oil is used , it is necessary to carry out synthesis in two
stages.
– Alcoholysis of the oil by a part of the polyol used.
– Esterification by a polyacid and the remainder of the polyol
Manufacture of alkyd resins
Fatty acid process :
• Fatty acids derived from oils are used.
• Since fatty acids contain carboxylic group, they easily react with polyol and so there is no need to carry out
alcoholysis or acidolysis of oil.
• Thus fatty acid, polyol and dibasic acid are together charged directly and polycondensation is carried out
to produce alkyd resin.
• Fatty acids are expensive as compare to oils but they facilitate shorter process time and better products.
To make it cost effective generally a mixture of fatty acids and oil is frequently used.

POLYCONDENSATION OF FATTY ACID AND ALCOHOL

Manufacture of alkyd resins
Acidolysis process :
• In this technique oil is first reacted with acid. This technique is normally used only where there are
problems of reactivity or solubility of dibasic acids encountered.
• The intermediate reaction occurs at a temperature around 270°C – 290°C until perfect compatibility is
attained. The reaction mixture obtained is then cooled and polyol is added.
• The polycondensation reaction is then carried out as for the previous processes.
Types of Alkyds
• Alkyds are classified
– Depends on oil length as
» Long oil alkyds (contains >55% of drying oil)
» Medium oil alkyds (contains 45-55% of drying oil)
» Short oil alkyds (contains <45% of drying oil)
– Depends on nature of oil as
» Oxidizing alkyds
» Non oxidizing alkyds
Curing of alkyd resins
The mechanism of curing of alkyd resins is given by :

CURING OF ALKYDS WITH CONJUGATED DOUBLE BONDS

CURING OF ALKYDS WITHOUT CONJUGATED DOUBLE BONDS

 Curing of alkyd resins

Reaction with methylol groups Reaction with etherified amino/ Phenolic resins Reaction with alkyd carboxyl group

Self condensation of methylol groups Reaction with Phenolic resins

Catalysis of curing
• The rates at which uncatalyzed non conjugated drying oils dry are slow. So
the metal salts are added to catalyze drying.
• The most widely used driers are oil soluble cobalt, manganese, lead,
zirconium, and calcium salts of 2-ethylhexanoic acid or naphthenic acids.
• Cobalt and manganese salts, called top driers or surface driers, primarily
catalyze drying at the film surface.
• Lead and zirconium salts catalyze drying throughout the film and are
called through driers.
Waterborne alkyds
Mechanism of waterborne solvents
• Alkyd Resins
 In this technique, alkyds are produced with residual acidity (pendent carboxylic acid
groups) and further neutralized with volatile amines to get a temporary water-
soluble amine salt.
 Modification of alkyds with water loving polyether polyols such as di or tri ethylene
glycol also makes them water soluble.
 Higher molecular weight polymers can be produced by a two-step reaction which
involves the initial polymerization of an alkyd with a hydroxyl value higher than normal
hydroxyl value, and then reaction of the produced material with additional anhydride to
give the carboxylated polymer
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