Polyurethanes based on hydrogenated

castor oil
V. D. Athawale
P. S. Pillay
S. L. Kolekar
One component polyurethanes based on Isophorone diisocyanate (IPDI), 4,4 di-phenyl
methane diisocyanate (MDI) and polyester polyol were prepared. The synthesized
polyurethanes were studied for their coating properties viz., hardness, gloss, adhesion,
impact resistance, flexibility, water repellency, moisture permeability and chemical
resistance. The IPDI based polyurethane showed better hardness, gloss, impact
resistance than that of MDI based polyurethane. However, MDI based polyurethane
showed relatively good moisture permeability.
Polyurethane coatings have been used for many years, but they are still a relatively new type
of surface coating medium. Despite the relatively high cost, their excellent durability,
resistance to corrosion, abrasion, water and chemicals, vegetables, mineral oils and many
solvents, make them suitable candidates for many high performance applications [1]. These
properties render the urethane coating system suitable for a wide variety of purposes on
practically any substrate including metal, wood, rubber, synthetic elastomers and fabrics of
various types [25].
Castor oil being the only commercially important oil containing large amounts of unsaturation
and hydroxyl functional groups is used to make new polymeric materials to meet ever
increasing expectations of the polymer industry. The hydroxyl functionality of castor oil has
been widely utilised to synthesise polyurethanes. Castor oil based polyurethanes have been
widely studied by many authors [612]. However, scanty information is available on the
synthesis of hydrogenated castor oil based polyurethanes [1314] and their utilisation in
polymer and fabrics industries have not been explored.
Hence our laboratory has undertaken a detailed research program for carrying out the
synthesis of low cost polyurethane coatings using hydrogenated castor oil. The present paper
deals with coating properties of polyurethanes and it also describes the applications of this
newly synthesised polyurethane for fabric coating.
Experimental
Materials
British standard specification (BSS) grade hydrogenated castor oil [acid value, 2.0 mg
KOH/g, hydroxyl value 162 mg KOH/g, iodine value (wij method) 25 and melting point 82
86 C] was procured from M/s Jayant oil mill (India), isophorone diisocyanate (IPDI), 4,4di
phenyl methane diisocyanate (MDI), trimethylol propane were obtained from Fluka
(Switzerland). e-Caprolactum and sebacic acid were obtained from Merck (Switzerland) and
Acros (India) respectively. All other reagents were of analytical grade and have been used
without further purification.
Synthesis of low cost
PUR coating
Polyol
A resin kettle equipped with thermometer, water condenser, stirrer and nitrogen inlet was
charged with hydrogenated castor oil, sebacic acid and trimethylol propane in a ration of 1:1:1
gram equivalent along with dibutyl tin laurate (DBTL) catalyst (0.05% w/w based on
hydrogenated castor oil). This reaction mixture was heated and maintained between 180200
C in an atmosphere of nitrogen. The reaction was continued until acid value <2mg KOH/g of
polyester polyol was obtained [15]. Water formed during the course of the reaction was
removed as an azeotropic mixture with toluene from the kettle with the aid of Dean-stark
apparatus.
Blocked polyurethane
A prepolymer (NCO/OH=2) was prepared by reacting one equivalent of polyester polyol and
two equivalents of diisocyanate and DBTL catalyst (0.01% w/w based on isocyanate) were
taken in a reaction kettle equipped with stirrer and water condenser in a thermostated water
bath. The reaction was carried out at 40 C with constant stirring until theoretical (5%wt
based on the polyurethane) isocyanate content (determined by di-n-butylamine method [16]
was reached.
The free isocyanate present in the polyurethane was treated with e-caprolactum in a
stoichiometric ratio to obtain !-caprolactum blocked polyurethane (Figure 1). The reaction
was carried out at 40 C and continued till NCO value reduced to 0%. The completion of the
reaction was confirmed by the absence of NCO band at 2270 cm
-1
in the infrared (IR)
spectrum of the newly synthesized polyurethane.
Preparation of sample
The samples were prepared as follows: 50% w/w toluene solution of blocked polyurethane
was applied on one side of the mild steel (MS)/glass panel using sheen-make bar coater (50
film thickness) and kept for deblocking and curing at 130 C for 15 mins.
Monitoring coatings properties
Infrared (IR) spectra of the polyurethanes based on IPDI and MDI were obtained on a
Shimadzu FTIR 4200 series spectrophotometer (Japan) using KB4 pellets.
For Pencil hardness testing [17] a series of lead pencils of the same brand with
hardness from 6B to 6H was assembled. The wood of the pencils was stripped to about 1/4
inch without nicking the lead. Then, the exposed leads were squared by a gentle rotary motion
against NO 400 carbide. On the sample coated (50 film thickness) mild steel panels, the
pencil in a writing position at about 45 to the plane of panel was pushed against the film
using pressure, short of breaking the lead. After each test a new edge is available by turning
the pencils. Any marring of the surface, visible at an oblique angle, shows the film is softer
than the pencil. The hardness is expressed as the pencil hardness of the next softer pencil.
Gloss is influenced by the smoothness or texture of a surface and it is the measurement
of how well, a surface functions as a mirror [18]. Gloss characteristics of coated glass panel
film were measured using sheen gloss meter at an angel of 60.
For Adhesion mild steel panels coated with the sample were examined to measure the
adhesion property by using cross-cut adhesion method [17]. The test is carried out as follows:
the sample coated on mild steel panel is cut into squares of 1 mm x 1 mm using the cross
hatch tester (Sheen-make). An adhesive tape applied to the crosscut area, was removed to
check adhesion. The number of intact squares gives a measure of the adhesion of the sample.
Cross-cut adhesion test was carried out on the mild steel panels after the samples were
matured for a week.
Impact resistance [19] was measured using a falling weight type impact tester (Komal
Scientific, Mumbai, India). In this method a hemispherical indenter of known weight is
dropped down onto coated (50 film thickness) panel, which is fixed at the base of the
instrument. An opening opposite to the indenter in the base support, on which the panel rests,
permits deformation of the panel. The indenter is dropped from increasing heights until the
film cracks (The indenter weighing about 6.25 lbs was released at a maximum height of the
24 inches). If the indenter hits directly to the film, then the test is called direct impact test and
if it hits on the back of the coated panel, then the test is called a reverse impact test.
Flexibility [20]: Sample coated tin plates were allowed to dry for a week before
checking the flexibility on conical mandrel.
Water repellency [21]: The test specimen (cut approximately 7 by 7 in.) was mounted
securely on the metal hoop and placed it facing uppermost on the base stand of the apparatus
so that the flow of the water down the specimen will coincide with its warpwise direction. 250
ml of distilled water was poured into the funnel and allowed it to spray on the fabric for
approximately 25 to 30 sec. Further on completion of the spraying period, the hoop was
grasped at one edge against a solid object, with the fabric facing the object during tapping.
Then the hoop was turned by 180, grasped at the opposite edge, and tapped at the point
previously held. Finally the wet or spotted pattern was determined according to the ASTM
D58358.
The moisture permeability of the polyurethane was determined by evaporation
methods (BS 7209:1990), where the samples were sealed over a vessel containing water
maintained at a constant temperature. The amount of water vapor passed through the samples
in a controlled atmosphere was measured over a period of time. The water vapor permeability
of the polyurethane coated nylon fabric was calculated as follows:
Moisture permebility in g m
-2
day
-1
=
Where,M = weight decrease during the test assembly in grams over a test period
t = time between successive weighting of the test assembly in hours.
A = area of the exposed test fabric, in square meters.
Chemical resistance tests [22] were carried out by immersing coated (50 film
thickness) glass panels into water, acid and alkali baths. The ends of the glass panels were
coated with wax in order to prevent migration under the film from the open ends. The panels
were then dipped into water, 3% (w/w) sulphuric acid solution and 1% sodium hydroxide
solution and were examined for the change in appearance after 24 hours.
PUR cured by deblocking the
!-caprolactum
As a result of the reaction taking place between the NCO group present in the isocyanate and
the OH groups present in the polyester polyol the polyurethane are cured by deblocking the
!-caprolactum at 130 C (Figure 2).
IR showed all the bands corresponding to urethane network
IR spectra of urethane prepolymer showed the characteristic absorption bands at 1740 cm1
and 3400 cm-1 that corresponded to urethane and amide II (-NH stretching), respectively. As
the prepolymer was isocyanate blocked, the band at the 2270 cm-1 due to NCO was not
observed. IR spectra of the polyurethanes showed all the bands corresponding to urethane
network and did not show any additional bands, thereby ruling out the possibility of
any chemical interaction between the components.!
IPDI based polyurethane
showed better hardness than
the MDI based
It can be observed from Table 1 that, the IPDI based polyurethane, showed better hardness
than the MDI based polyurethane. It may be because of high degree of branching in the IPDI
based polyurethane which increases crosslinking density making the film harder. Whereas, in
the case of MDI based polyurethane the NCO groups are much more distant, as compared to
IPDI based polyurethane hence, the crosslinking density of MDI based polyurethane is low.
Improved gloss
Gloss depends on the amount of the light reflected by the coated material. It is known that
more light is reflected from a high gloss resin. Thus, IPDI based polyurethane gives better
gloss as compared to MDI based polyurethane, which might be, because of the excellent light
stability of the former.
"00% adhesion
Both the polyurethanes based on MDI and IPDI showed 100% adhesion. It may be attributed
to the polar nature of the polyurethanes which facilitates strong affinity towards the metal
surface.
High impact resistance by optimum hardness and flexibility
In direct impact test, both of the polyurethanes showed an excellent impact resistance. It may
be ascribed to optimum hardness and flexibility of both the polyurethanes. But, in reverse
impact test, IPDI based polyurethane showed greater impact resistance than that of MDI
based polyurethane. This is because in case of MDI based polyurethane, the presence of
aromatic ring in MDI imparts rigidity to the polyurethane.
Excellent flexibility due to the soft segment of the polyol
Table 1 revealed that both the polyurethanes based on IPDI and MDI have passed the (all
inches) bend test showing excellent flexibility. The excellent flexibility of both the
polyurethanes might be, due to the soft segment of the polyester polyol, present in the
polyurethanes.
50% water repellency
Polyurethanes based on IPDI and MDI showed 50% water repellency. This was because of
the wetting of surface of both the polyurethanes on coming in contact with water and the
presence of hydrophobic chain segments of hydrogenated castor oil based polyester polyol
and hydrophilic chain segments of group trimethylol propane.
Hydrophilic chain of hydrogenated castor oil polyester polyol in PUR restricts the
swelling
Table 1 showed that MDI based polyurethane has better moisture permeability as compared
to IPDI based polyurethane. It may due to the presence of effective length of the crosslinks
network within the polymeric chain of the polyurethane which, affects the moisture
permeability as compared to IPDI based polyurethane. The moisture permeability of both the
polyurethanes may also be attributed to the presence of hydrophilic segment trimethylol
propane. But the presence of hydrophilic chain of hydrogenated castor oil polyester polyol in
polyurethane restricts the swelling and complete disolution of polyurethane in water.
High crosslinking density prevents the penetration of the solvents into the polymer
matrix
Glass panels coated with polyurethane based on IPDI and MDI were immersed in water, acid
and alkali baths for testing their chemical resistance. It did not exhibit any change in the
polyurethane film even after 24 hrs. It may be because of high crosslinking density of both the
polyurethanes, which prevent the penetration of the solvents into the polymer matrix.
Results at a glance
Based on the comparison of IPDI and MDI based polyurethanes it can be noted that both of
the polyurethanes showed good coating properties. The IPDI based polyurethane had a good
impact resistance as compared to MDI based polyurethane, where as the MDI based
polyurethane showed better moisture permeability as compared to IPDI based polyurethane.
Moreover, good water repellency of both the polyurethanes offers them as good candidates
for fabric coating.
LIFELINE
Dr. V. D. Athawale is Senior Reader in the Department of Chemistry, University of Mumbai,
India. He has participated widely in programs for the development of scientific and
technological education. The authors special research interest includes the study of coating
blends, grafting, interpenetrating polymer networks (IPNs) and chemoenzyamatic synthesis of
polymers.
S. L. Kolekar is Research Scholar in the Department of Chemistry, University of Mumbai,
India. He is working in the fields of polymer coatings, interpenetrating polymer networks
(IPNs) and has contributed to many research papers in international polymer journals of
repute.
P. S. Pillay is Research Scholar in the Department of Chemistry, University of Mumbai,
India. She is working in the fields of polymer coatings and interpenetrating polymer networks
(IPNs).
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