Título presentación
Institute of Chemical and Environmental Technology
Chemical Engineering Department
University of Castilla La Mancha
Ciudad Real, Spain
RIGID POLYURETHANE FOAM FROM
GRAPE SEED OIL
Antonio Díaz-Medino
Manuel Carmona
Ángel Pérez
J.F. Rodríguez
RIGID POLYURETHANE FOAM FROM GRAPE SEED OIL
Título presentación
Ref: CTQ2008-06350
BES-2009-015202
RIGID POLYURETHANE FOAM FROM GRAPE SEED OIL
Título presentación Título presentación
INTRODUCTION • Basic chemistry of polyurethane
• Renewable polyols
• Why using grape seed oil as a raw material?
SCOPE
• Epoxidation of Grape Seed Oil
• Epoxide ring opening and formation of the vegetable polyol
• Synthesis of polyurethane foam
RIGID POLYURETHANE FOAM FROM GRAPE SEED OIL
Título presentación Título presentación
1. Introduction
1.1. Basic chemistry of polyurethane
n HO-R-OH + n O=C=N-R´-N=C=O [ -CO-NH-R´-NH-CO-O-R-O- ]n
Polyol Isocianate Uretane
RIGID POLYURETHANE FOAM FROM GRAPE SEED OIL
Biopoliol
?
Título presentación Título presentación
1. Introduction
1.1. Basic chemistry of polyurethane
Formation of the initial alcoholate
Propagation
RIGID POLYURETHANE FOAM FROM GRAPE SEED OIL
Título presentación Título presentación
1.2. Renewable polyol
Biomass
Waste
Vegetable oils
Starch
Terpenes
...
Polimers
Cosmetics
Drugs
...
Biodegradation
Assimilation Extraction
Recycling
Processing Utilization
RIGID POLYURETHANE FOAM FROM GRAPE SEED OIL
Título presentación Título presentación
1. Introduction
1.2. Renewable polyol
RIGID POLYURETHANE FOAM FROM GRAPE SEED OIL
Triglycerides
Vegetable
polyol
Título presentación Título presentación
1. Introduction
1.3. Why using grape seed oil as a raw material?
RIGID POLYURETHANE FOAM FROM GRAPE SEED OIL
Biopolyol production from grape seed oil
constitutes an economic
alternative for valuation of by-product
obtained from the wine
manufacture in the region of Castilla-La
Mancha (Spain)
Fatty acids Composition % weight
Lauric C12:0 0.0
Myristic C14:0 0.1
Palmitic C16:0 6.9
Palmitoleic C16:1 0.1
Estearic C18:0 4.0
Oleic C18:1 19.0
Linoleic C18:2 69.1
Linolenic C18:3 0.3
Arachidic C20:0 0.3
Gadoleic C20:1 0.0
Behenic C22:0 0.0
Erucic C22:1 0.0
Lignoceric C24:0 0.0
Nervonic C24:1 0.0
Título presentación Título presentación
2. Epoxidation of grape seed oil
2.1. Mechanism reaction
RIGID POLYURETHANE FOAM FROM GRAPE SEED OIL
Prileschajew’s Reaction Experimental conditions:
-Temperature: 60ºC
-Molar ratios: 0.5 and 2 between
acetic acid and hydrogen
peroxide respect to the
unsaturation content
-Catalyst: 2 % by weight of
sulphuric acid.
Título presentación Título presentación
2. Epoxidation of grape seed oil
2.2. Experimental equipment and analytical techniques
RIGID POLYURETHANE FOAM FROM GRAPE SEED OIL
Experimental Equipment
•UNE 53985-2 •UNE-EN 14111
•AOCS Official Method Cd 9-57
•AOCS Official Method Tx 1a-66
Determination of Hydroxyl
Index
Determination of Oxirane
Oxigen
Determination Acid Value
Determination of Iodine Index
Standards for the characterization of the products:
Analytical methods:
Gel permeation chromatography (GPC) Infrared Spectroscopy (FTIR)
Título presentación
2. Epoxidation of grape seed oil
2.3. Results
Temperature effect
RIGID POLYURETHANE FOAM FROM GRAPE SEED OIL
T (ºC) Iodine Value
(g I2/100g) Conversion % Oxirane oxygen
Hydroxyl Value
(mg KOH/ g) ŋ
50 23.38 83.1 5.75 25.4 65.15
60 9.85 92.9 5.87 31.98 66.51
70 5.21 96.2 5.65 47.02 64.02
80 4.69 96.6 3.97 100.58 44.98
50 60 70 80
0,0
0,1
0,2
0,3
0,4
0,5
0,6
0,7
0,8
Mol of double bond trasformed
Mol of epoxidized double bond
Mol of hydroxylated double bond
Mol of dimerized double bond
Mol
/ 10
0g
T (ºC)
Título presentación
2. Epoxidation of grape seed oil
2.3. Results
Temperature effect
RIGID POLYURETHANE FOAM FROM GRAPE SEED OIL
10 11 12 13 14 15 16 17
Retention Volume (ml)
50ºC
60ºC
70ºC
80ºC
T (ºC) Mw (g/mol)
50 1010
60 1152
70 1281
80 1599
10 11 12 13 14 15 16 17
Grape Seed Oil
Retention Volume (ml)
Dimers
Trimers
Título presentación
2. Epoxidation of grape seed oil
2.3. Results
Purification Process
RIGID POLYURETHANE FOAM FROM GRAPE SEED OIL
Purification by
successive
washes
•Acid Value: 10
mg KOH/g
Ion Exchange
Amberlite IRA 402
0.7 g de resin /g
product
•Acid Value 0.06 mg
KOH/g
Título presentación
2. Epoxidation of grape seed oil
2.3. Results
Kinetic model
RIGID POLYURETHANE FOAM FROM GRAPE SEED OIL
4000 3500 3000 2500 2000 1500 1000 500
20
40
60
80
100
120
Grape Seed Oil
Tra
nsm
itta
nce
(%
)
Wave Number (cm-1)
4000 3500 3000 2500 2000 1500 1000 500
0
50
100
0
50
100
0
50
100
0
50
100
0
50
100
Tra
nsm
ittan
ce (
%)
Wave number (cm-1)
240 min
Tra
nsm
ittan
ce (
%) 180min
Tra
nsm
ittan
ce (
%) 120min
Tra
nsm
ittan
ce (
%) 60min
Tra
nsm
ittan
ce (
%) 30min
Double
Bond
Double
Bond
Hydroxyl
Epoxide
Título presentación
2. Epoxidation of grape seed oil
2.3. Results
Kinetic model
RIGID POLYURETHANE FOAM FROM GRAPE SEED OIL
1) A+B↔C+D
2) C+E→F+A
3) F+D→G
4) F+G→H
5) F+H→I
A: Acetic acid
B:Hydrogen
Peroxide
C: Peracetic Acid
D: Water
E: Double Bond
F: Epoxide
G:Hydroxyl
H: Dimers
I: Trimers
Título presentación
2. Epoxidation of grape seed oil
2.3. Results
Kinetic model
RIGID POLYURETHANE FOAM FROM GRAPE SEED OIL
0 50 100 150 200 250
0.0
0.5
1.0
1.5
2.0
2.5
3.0
3.5
[ ]
(m
ol/
l)
Time (min)
[Epoxide]exp
[Double Bond]exp
[Hydroxyl]exp
[Dimer]exp
[Epoxide]mod
[Double Bond]mod
[Hydroxyl]mod
[Dimer]mod
Kinetic Constants l·mol-1·min-1
K0 7.30E-03
K0´ 2.58E-02
K1 1.18E-01
K2 7.17E-05
K3 7.49E-01
K4 1.00E-12
Título presentación Título presentación
3. Epoxide ring opening and formation of the vegetable polyol
3.1. Experimental equipment and analytical techniques
RIGID POLYURETHANE FOAM FROM GRAPE SEED OIL
Experimental Equipment
GPC
FT-IR
AOCS Official Method Cd 9-57 AOCS Official Method Tx 1a-
66
Standards for the characterization of the products:
Título presentación Título presentación
3. Epoxide ring opening and formation of the vegetable polyol
3.2. Mechanism reaction
RIGID POLYURETHANE FOAM FROM GRAPE SEED OIL
Experimental conditions:
-Temperature: 80ºC
-Pressure: 50 Bar
-Molar ratios: 1.1 between Glycerol
and the Oxirane concentration.
-Catalyst: 10 mg of DMC Catalyst
(Cobalt-Zinc Double Metal Cyanide
Complex).
-Time: 2h
Epoxidized
oil + Glycerol = Vegetable
Polyol
Epoxidized
oil
Glycerol Vegetable
Polyol
+ =
Título presentación Título presentación
3. Epoxide ring opening and formation of the vegetable polyol
3.3. Results
RIGID POLYURETHANE FOAM FROM GRAPE SEED OIL
10 11 12 13 14 15 16 17
Retention Volume (ml)
Epoxidized Oil
Vegetable Polyol
4000 3500 3000 2500 2000 1500 1000 500
0
50
100
0
50
100
0
50
100
Tra
nsm
itta
nce
(%
)
Wave Number (cm-1)
Vegetable Polyol
Tra
nsm
itta
nce
(%
) Epoxidized Oil
Tra
nsm
itta
nce
(%
) Grape Seed Oil% Oxirane
Oxygen
Hydroxyl Value
(mg KOH/ g) Mw (g/mol)
Epoxidised oil 5.87 31.98 1151.75
% Oxirane
Oxygen
Hydroxyl Value
(mg KOH/ g)
Mw
(g/mol)
Vegetable
Polyol 1.06 80.84 1800.94
Hydroxyl
Título presentación Título presentación
4. Sinthesis of Polyurethane Foam
4.1. Results
RIGID POLYURETHANE FOAM FROM GRAPE SEED OIL
Polyol 100
Water 2,5
Tegostab 1,5
Tegoamin BDE 2,5
MDI (Methylene Diphenyl
Diisocyanate ) 100
Scanning Electron
Microscopy (SEM)
Rigid polyurethane foam
from grape seed oil.
Título presentación RIGID POLYURETHANE FOAM FROM GRAPE SEED OIL
5. Conclusions
1. Epoxidation and subsequent ring opening allowed the functionalization of
vegetable oils for the production of polyols having different molecular weight and
functionality.
2. The epoxidation reaction of vegetable oil exhibited the highest selectivity towards
epoxide functional groups. Nevertheless, this selectivity was dependent on
temperature.
3. The ion exchange technology by using Amberlite IRA-402 allowed to get the total
removal of residual sulphuric acid and acetic acid from the epoxidized oil.
4. A polyol having a maximum acid value of 0.07 mg KOH/, a hydroxyl number 81 mg
KOH/g and a molecular weight of 1800 g/mol, proper to produce RPU foams was
synthesized.
5. A rigid polyurethane foam exhibiting good mechanical and physical properties
was synthesized from the natural grape seed oil.
Título presentación Título presentación
Institute of Chemical and Environmental Technology
Chemical Engineering Department
University of Castilla La Mancha
Ciudad Real, Spain
Thank you for your attention
Antonio Díaz-Medino
Manuel Carmona
Ángel Pérez
J.F. Rodríguez
RIGID POLYURETHANE FOAM FROM GRAPE SEED OIL