Polyrethanes Based on Hydroformylated Soyabean Oil
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02/24/2003 Polyurethanes Based on Hydroformylated Soybean Oil Andrew Guo Dima Demydov Wei Zhang Zoran Petrovic Kansas Polymer Research Center Pittsburg State University 1501 S. Joplin Street Pittsburg, KS 66762
Transcript of Polyrethanes Based on Hydroformylated Soyabean Oil
02/24/2003
Polyurethanes Based on Hydroformylated
Soybean Oil
Andrew Guo Dima DemydovWei Zhang Zoran Petrovic
Kansas Polymer Research CenterPittsburg State University
1501 S. Joplin StreetPittsburg, KS 66762
02/24/2003
Functionalization of Soybean Oil
Epoxidized Soybean Oil
Soybean Polyaldehyde Primary Polyol
Polycarboxylic Acid Polyamines
Soybean Oil
Secondary Polyol
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Hydroformylation of Soybean OilO
O
OO
O
O
CH=O
CH=O
CH=O
CH=OHydroformylation
OO
OO
O
O
CO/H2, Cat.
OO
OO
O
O
CH2OH
CH2OH
CH2OH
CH2OHHydrogenation
Raney Ni/H2
Benefit: Energy efficient (100% atom economy)
Environmentally benign (0% waste)
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Catalyst Systems
Rh System
• Soybean oil
• Rh/PPh3
• H2 /CO (1:1)
• Ni/H2
Co System
• Soybean oil
• Co2(CO)8
• H2 /CO (1:1)
• Co/H2
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Catalyst Comparison
Rh System• higher yield• milder conditions
(pressure 2,000 psi, temp. 90-100°C)
• require a second metal (Ni) for hydrogenation
• Rh more costly ($1,000/Oz.)
Co System• lower yield• harsher conditions
(pressure 4,000 psi, temp. 120-180°C)
• no need of a second metal for hydrogenation
• Co cheaper ($15/lb.)
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Chemical and Physical Propertiesof the Soy Polyols
SoyPolyol
Conversion(%)
Hydroxylnumber
(mgKOH/g)
Functionality
PhysicalState
Rhodiumprocess
95% 230 4.1 viscousliquid
Cobaltprocess
67% 160 2.7 viscousliquid
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GPC Traces of Hydrof. Soy Polyols
0
10
20
30
9 10 11 12 13 14
Retention Time (min)
Det
ecto
r Sig
nal
Polyol-HF-Co
Soybean oil
Polyol-HF-Rh
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DSC Profiles of the Soy Polyols
-25
-20
-15
-10
-5
-80 -60 -40 -20 0 20 40 60 80 100Temperature (°C)
Hea
t Flo
w (m
W)
Soybean oil
Rh Polyol
Co Polyol
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Soy-based Polyurethanes
OC(O) Heat or catalyst
Oil-based polyol Isocyanate
+ OCN NCO
OH
OH
OH OH
OC(O)
OC(O)
OC(O)
OC(O)
OC(O)
Crosslinked polyurethane
OH
OH
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Glass Transition Temperaturesof the Soy Polyurethanes
Polyurethane DSCTg (°C)
TMATg (°C)
DMTATg (°C)
Rhodiumprocess
48 52 57
Cobaltprocess
20 21 22
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Stress-Strain Curves
0
10
20
30
40
50
0 20 40 60 80 100
Percent Strain (%)
Stre
ss (M
Pa)
Cobalt process
Rhodium process
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Tensile Propertiesof the Soy Polyurethanes
Polyurethane Tensilestrength
(MPa)
Young’sModulus
(MPa)
Elongationat break
(%)Rhodiumprocess
38 362 17
Cobaltprocess
11 13 93
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Property Improvement - Effect of Crosslinker
• Glass transition temperature• Tensile strength• Flexural strength• Impact Strength
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0
20
40
60
80
100
120
0 5 10 15 20 25 30
Amount of Glycerine (pph)
Tg (°
C)
Effect on Tg (by DSC)
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0
20
40
60
80
0 5 10 15 20 25 30
Amount of Glycerine (pph)
Tens
ile S
tren
gth
(MPa
)
Effect on Tensile Strength
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0
1000
2000
3000
0 5 10 15 20 25 30
Amount of Glycerine (pph)
Flex
ural
Mod
ulus
(MPa
)
Effect on Flexural Modulus
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Effect on Impact Strength
0
10
20
30
40
0 5 10 15 20 25 30
Amount of Glycerine (pph)
Impa
ct R
esis
tanc
e (J
/m)
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SUMMARY
• Rh-catalyzed Hydroformylation – Rigid plastic PU
• Co-catalyzed Hydroformylation– Hard rubber PU
• Addition of Glycerine – improves properties
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ACKNOWLEDGEMENT
U.S. Department of EnergyU.S. Department of Agriculture
United Soybean BoardKansas Soybean Commission
Pittsburg State UniversityNoveon, Inc.
Dow ADM
