Polyurethanes from vegetable oils
Published on: Mar 4, 2016
Transcripts - Polyurethanes from vegetable oils
Polyurethanes from Vegetable OilsPolyurethanes from Vegetable Oils
• Polyurethane (PUR and PU) is a polymerPolyurethane (PUR and PU) is a polymer composed of a chain of organiccomposed of a chain of organic units joinedunits joined
by carbamate (urethane) links.by carbamate (urethane) links.
Mechanical properties eg- high tensile strength & elongation.Mechanical properties eg- high tensile strength & elongation.
Thermal properties:- 40-80Thermal properties:- 40-8000
c ( both long & short term application).c ( both long & short term application).
Hydrolytic stability:- highest resistanceHydrolytic stability:- highest resistance
to water at elevated temperature .to water at elevated temperature .
Oil,grease and solvent resistanceOil,grease and solvent resistance
The major application of polyurethanes are
Adhesives & sealants
characteristics of polyurethane materialscharacteristics of polyurethane materials
Why vegetable oil based polymer ?Why vegetable oil based polymer ?
Vegetable oils are excellent but very heterogeneous renewable raw
materials for polyurethanes
It gaining popularity due to some attractive properties related to the
specific structure of oils
It concerns about the environment and sustainability.
Inherent bio degradability
Some oils like tung (wood) oil have conjugated double bonds, which
tend to polymerize easily when exposed to air.
Its composition and price.
Price wise, soybean oil, palm oil, and rapeseed oil are the most
attractive for large-scale industrial products.
Polyurethanes are based on:Polyurethanes are based on:
Castor oilCastor oil
Soybean oilSoybean oil
Fatty Acid Polyols.
Polyfunctional Vegetable Oil-based Polyols.
Fatty Acid Polyester.
Sun flower, canola,corn,etc
Urethane polymer from soybean oilUrethane polymer from soybean oil
Oils and fats are triacylglycerols (triglycerides) i.e., esters of glycerin
and different fatty acids.
Soy fatty acids are useful for modification of polyurethanes.Soy fatty acids are useful for modification of polyurethanes.
Fatty acids can easily be converted to reactive multifunctionalFatty acids can easily be converted to reactive multifunctional
This modification is achieved by base catalysis of oil withThis modification is achieved by base catalysis of oil with
diethanolamine to give dialkanol soyamides.diethanolamine to give dialkanol soyamides.
Heat resistant Pu foams are obtained from epoxidized soybeanHeat resistant Pu foams are obtained from epoxidized soybean
oil ,diethylene glycol,MDI & polyethylene glycol.oil ,diethylene glycol,MDI & polyethylene glycol.
Fire resistant & dimensionally stable Pu’s are epoxidized oil,Fire resistant & dimensionally stable Pu’s are epoxidized oil,
halogenated bis phenol, TDI & phenolic resins.halogenated bis phenol, TDI & phenolic resins.
Castor Oil-based Polyurethanes.
Glass transition of castor oil/pure MDI may vary with the hydroxyl
number. it is around 5o
when the isocyanate index ([NCO]100/[OH]) was increased to 120, Tg
Properties of polyurethane networks could be modified by
copolymerizing with different monomers to obtain interpenetrating
carbodiimide modified MDI gives Tg with castor oil of around 8o
Particularly active in the field of interpenetrating networks with
castor oil polyurethanes was the Sperling group.
Casting electro-insulating compounds based on crude MDI and filled
castor oil have been used in the electrical industry for encapsulating
Polyurethanes from Fatty Acid Polyols.
It isIt is prepared either from fatty acids by transesterification of the
polyols with glycols and removing glycerin.
Such polyols may have lower viscosity but also lower functionality.
Properties of a polyurethane from MDI and a polyol obtained by
epoxidation and ring opening with methanol having an OH number of
173 with those made by transesterification of polyol with ethylene
If one breaks up the triglyceride structure by transesterification with
methanol and removes the glycerin.
Primary hydroxyls give more thermally stable urethane bonds but in
the case of EG-fatty acid polyurethane, the break up and evaporation
of ethylene glycol may have taken place catalyzed by the residual tin-
based esterification catalyst.
Segmented PUs from Polyfunctional
Vegetable Oil-based Polyols
Addition of glycerin Increasing Tg and the rigidity of the vegetable oil-
based polyurethane networks.
Glass transition of the soft phase (soy-based matrix) was found to
decrease with increasing soft segment concentration (SSC).
Linear Segmented Polyurethane Elastomers from Fatty Acid
Polyester Soft Segments:
Thermoplastic polyurethane elastomers are block copolymers
consisting of alternating soft and hard segments.
Hard segments consisted of mixed esters of terephthalic acid and/or
dimeric acid with dimerol and ethylene glycol or butane diol.
Soft segments were polytetramethylene oxide diols of a MW weight
Effect of the polyol OH number on Tg of PUs from
Properties of Vegetable Oil-based PUs
Vegetable oils are fairly non-polar compounds and as such
could be used as a substitute for petrochemical
Electrical and mechanical properties of castor oil and soy-
based polyurethanes showed excellent properties, While
castor oil gave rubbery polyurethanes, soy-based
compounds were glassy.
Castor oil casting compounds displayed higher permittivity.
Thermal Stability :
It is not high primarily due to the presence of labile
Standard petrochemical polyurethanes based on propylene
oxide are very unstable in the oxidative atmosphere.
Polyurethanes from polyols with primary hydroxyls are
more stable than those with secondary OH
Crosslinking density increases thermal stability
Ethylene glycol extended polyurethanes from fatty acid
polyols are the least stable
The thermal stability of polyurethanes decreased with
Vegetable oils have three ester bonds susceptible to
The urethane bonds also may hydrolyze when exposed to
high humidity to give an amine and carbon dioxide
R-NH-COOR’ + HOH -> RNHCOOH + R’OH
R-NH-COOH -> RNH2 + CO2
polyurethane foams and cast polyurethanes are
It is desirable for packaging materials and materials
intended for short useful life.
It is undesirable in engineering materials with long service
Polyurethane prepared from polyols from soybean oil,
triolein, and linseed oil by the epoxidation route and
hydroformylation using respirometry, measures the
evolution of CO2 as a result of bacterial activity on the
exposed powdered material in soil.
Vegetable oils offer a variety of new structures in polyols
depending on the method of synthesis, resulting in PUs
with new properties, suitable for a range of applications.
Currently, vegetable oil polyols must be used in conjunction
with petrochemical polyols in flexible foams, but they could
be used as sole polyols in other applications.
New structures are continually being developed and
properties are being improved.
With time we can expect a dramatic increase in the use of
vegetable oil-based polyols in the polyurethane field.
Live for better tomorrowLive for better tomorrow
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“Characterization of triacylglycerol &diacylglycerol
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Pryde, E. H.; Gast, L. E.; Frankel, E. N.; Carlson, K. D.
“Vegetable oils and animal fats as renewable resources for
plastics and coatings applications”, Polym.-Plast. Technol.
Eng. 1976, 7, 1–26.
D.L.KAPLAN(ED.)”Biopolymers from Renewable