Unlocking the Benefits of bio-

based Susterra® 1,3

propanediol in Industrial PUD
applications

Sean L. Gahan
Technical Service Manager
DuPont Tate & Lyle Bio Products Company, LLC

September 2, 2020

1
Agenda 2

1. Company Introduction
2. Susterra® Propanediol (bio-based 1,3-propanediol).
3. Coatings Segments
4. Polyurethane basics
5. Technical Studies – PDO-Based Waterborne 2K-
Polyurethane Dispersions.
▪ Textile Applications
▪ Direct-to-Metal Applications
6. Technical Study: PDO-Based Polyurethane Cast
Elastomers – Pipe Liners.
7. Summary
8. Question & Answer Session
 Who is DuPont Tate & Lyle?
DTL is a joint venture formed in 2004 between DuPont and Tate & Lyle to produce bio-based propanediol
from fermentation of glucose.

DuPont is a global innovation leader with Tate and Lyle is a global provider of
technology-based materials, ingredients renewable ingredients, solutions and
and solutions that help transform services to the food, beverage and
industries and everyday life. industrial customers.

3
 Our Bio-based Technology
Renewably sourced feedstocks are harvested, fermented, and refined to manufacture bio-based
Susterra® propanediol.
Harvest
Renewably sourced
feedstocks are harvested, dried
and then wet-milled to create
a range of carbohydrate rich
feedstocks such as glucose.
4
Fermentation Refining
Glucose is converted into The 1,3 propanediol is refined
1,3 propanediol using to a high purity by
a patented microorganism deactivating and removing
under exact temperatures the microorganism, water,
and conditions. and other byproducts.
DTL Product Facility
Loudon, Tennessee USA

Awards
2003 EPA Presidential Green Chemistry
Award.
2007 ACS Heroes of Chemistry Award.
2009 ACS-BIOT Industrial Biotechnology
Award.
2010 State of Tennessee Governor’s
Award for Trade Excellence.

Manufacturing
• Started November 2006, 100 million lbs.
• 2010 capacity expanded 35%.
• 2019 capacity expanded 25%
• 2019 Current Capacity, 170 million lbs.

5
6
 7

Physical and Chemical Properties Susterra® Propanediol

What is it?
CAS Number 504-63-2 • A pure, petroleum-free glycol alternative.
Molecular Formula C3H8O2 • 100% sustainably and renewably
Molecular Weight 76.1 sourced.
Molecular Structure HO OH
Melting/Freezing point, oC -27.65 How is it made?
Boiling point, oC 214.22 • Made in the USA
Refractive Index, 20oC 1.436 • Three step process: Harvest,
Lower explosion limit, %vol 2.6 Fermentation, Refining.
Vapor pressure @ 20oC, hPa (mm Hg) 0.0159 (0.0119) • USDA 100% Certified Bio-Based
Vapor pressure @ 25oC, hPa (mm Hg) 0.0267 (0.0200) Product, ASTM D6866
Vapor pressure @ 100oC, hPa 8.77
• GRAS, Halal, Kosher certified
Specific gravity @ 20oC 1.053
• Suitable for use in many different
Water solubility infinity
Coatings’ applications
log Kow -1.04
Auto-ignition temperature, oC 400
Viscosity, kinematic @ 20 oC / cSt 46
Viscosity, dynamic @ 20 oC / cP 49

7
 Susterra® Life Cycle Assessment* Comparison
From “Cradle-to-Gate,” the production of Susterra® consumes 46% less non-renewable
energy and reduces GHG emissions by more than 48% vs. petroleum-based BDO.

*Susterra® LCA data based on Loudon process design data; peer reviewed by Five Winds International. Estimates based upon
Ecoinvert models for BDO (Reppe Process), propylene oxidation method for fossil PDO and design data for Susterra
8
Coating Applications

9
 10

Polyurethane Chemistry

10
 11

Polyurethane Chemistry: Type & Reactions

1K 2K

11
 Polyurethane Production
Susterra® propanediol can be used as a chain extender or polyol.

Susterra®
propanediol

BDO Chain
TPU
Extender

AA/SA/SB PU Leather
Polyester
Polyol End User
BDO/EG/DEG
Polyether PU Adhesives
Susterra® Polyol
propanediol
Isocyanate PU Coatings

12
 Susterra® Propanediol
Structural Differences and the Odd-Even Effect

The odd even effect varies the packing of the hard block segments, and results in
unique mechanical properties of the final product (High Hardness– Shore-A 95).

1,3 PDO hard block 1,4 BDO hard block

Dipole O O O H
induces Staggered
R 1 3 R packing R 1 3 O N
bending N O O N N O R
and strain 2 gives no 2 4
H H dipole H O
O O O H
R R R O N
N O O N N O R
Long Short
H H H O
hydrogen hydrogen
O O bond O H
bond
R R R O N
N O O N N O R
H H H O

Sources:
L. Born, H. Hespe, J. Crone, K.H. Wolf, Colloid and Polymer Science, 1982, 260(9), 819-828.
13
J. Blackwell, M.R. Najarajan, T.B. Hoitink Polymer, 1981, 22, 1534-1539.
O. Bayer, Agnew. Chem., A59, 257 (1947)
 Polyol
Polyol
Hard Segment Soft Segment Hard Segment
Susterra® Propanediol as a Polyester Polyol:
Hard Segment Soft Segment Hard Segment
Hard Segment Soft Segment Hard Segment

Step 1: Step 2:
Step 1: Polyol
Polyester Step 2: Polyester Polyol
Step 1:
Step 2: Step 2: Prepolymer
Polyester
Step
Step 2: 2:Polyol
Step 2: Step 2:Polyester PolyolPolyester Polyol
Prepolymer
Polyester Polyol
Prepolymer
Polyester
Step Prepolymer
Polyol Glycol
Polyester Polyol Polyester Polyol
Step 2: 2:
Prepolymer
Prepolymer Step 2:
Prepolymer
Polyester PolyolPolyester Polyol
Dicarboxylic Acid Prepolymer
Glycol
Polyester Polyol
Step 2:
Prepolymer Dicarboxylic Acid Polyester PolyolPolyester Polyol
Prepolymer Prepolymer
Dicarboxylic Acid Glycol
Polyester Polyol
Prepolymer
p 2: Step 2: Diisocyanate Diisocyanate
ppolymer
2: Step 2: Polyester PolyolPolyester +
Polyol Diisocyanate Diisocyanate
ppolymer
2:
Prepolymer
Step 2:
Diisocyanate
Diisocyanate
Diisocyanate
Polyester PolyolPolyester +
Polyol Diisocyanate Diisocyanate
Diisocyanate Diisocyanate
Diisocyanate Diisocyanate
Polyester PolyolPolyester Polyol+
Prepolymer Diisocyanate Diisocyanate Diisocyanate
polymer Prepolymer Diisocyanate
Diisocyanate Diisocyanate Diisocyanate Diisocyanate
Diisocyanate
Diisocyanate Diisocyanate Polyester Polyol
Polyester PolyolPolyester Polyol Polyester Polyol
Polyester Polyol Urethane Polyester Polyol Urethane
Diisocyanate Diisocyanate Polyester Diisocyanate
Polyol Diisocyanate
Polyester Polyol
Urethane Urethane
Diisocyanate Urethane
Diisocyanate Urethane
Polyester
Polyester Polyol
Diisocyanate
Polyol Urethane
Group
Diisocyanate Urethane Group
Urethane
Urethane Polyester Polyol
Urethane
Urethane
Group Urethane
Group
Diisocyanate Group
Diisocyanate Urethane
Group Polyester Polyol
Diisocyanate Group
Diisocyanate Urethane
Group
Urethane
Urethane
Group
Group Urethane Urethane
Urethane
Group
Group Urethane Group
Urethane Group Urethane Group
Group
Group Group Group
Group Group
Polyester
Group Polyol Polyester Polyol Group
Step 3:
Polyester PolyolPolyester Polyol Chain Extender
Step 3: Urethane
Step 3: Urethane Step 3:
Crosslinking Urethane Chain Extender PREPOLYMER
Urethane + Chain Extender
HO—R’—OH
Step
Step 3: 3: Urethane
Step 3:
Group
Polyester
Urethane
Group
Polyol
PREPOLYMER Polyester
Crosslinking
Polyol
Step 3: PREPOLYMER ++
Urethane
Group +Urethane
Chain
Chain Extender
Group
Extender
Chain Extender
PREPOLYMER
Chain Extender
+ Chain Extender
HO—R’—OH
Crosslinking
Step
Step 3: 3:
Crosslinking
Crosslinking
Crosslinking
Urethane
Group
Step 3:
Crosslinking
PREPOLYMER
GroupPREPOLYMER
Urethane Crosslinking
PREPOLYMER ++
PREPOLYMER
Urethane
HO—R’—OH
Group Chain +Urethane
Chain Extender
Group
HO—R’—OH
Extender
HO—R’—OH
HO—R’—OH
PREPOLYMER
Chain Extender
HO—R’—OH
+ HO—R’—OH
Step 3:
Crosslinking
Crosslinking Group
Crosslinking GroupPREPOLYMER
PREPOLYMER ++
PREPOLYMER +
Chain Extender Polyester
HO—R’—OH
Group HO—R’—OH Group HO—R’—OH
Crosslinking Polyester Polyester HO—R’—OH Polyester
Polyol
p 3: Step 3: Polyester
Polyester
Polyol Polyester
Chain Extender Chain Extender Polyester
Polyol
Polyol
p 3:
osslinking Step 3:
Crosslinking
PREPOLYMER Polyester
Polyol +
Polyester
PREPOLYMERPolyol +
Polyester
Chain Extender Chain
Polyol
HO—R’—OH Extender
HO—R’—OH Polyol
p 3:
osslinking Step 3:
Crosslinking
PREPOLYMER PREPOLYMER
Polyol +
Polyester
Polyol Hard
Chain +
Segment
Extender Chain
Polyol
HO—R’—OH Extender
HO—R’—OH
Soft Segment Hard Segmen
Hard
osslinking Crosslinking Hard
Segment PREPOLYMER
Segment
Hard Segment PREPOLYMER
Soft
Soft
+
Polyol
Segment Hard
Hard
Segment
+
Segment
Soft Segment HO—R’—OH
HO—R’—OH
Segment
Hard Soft
Soft
Hard
Segment
Segment Hard Segment
Segment
Segment
Hard Segmen
Hard Segmen
Hard Segment Hard Segment
Polyester Soft Segment Soft Segment
Polyester Hard Segment Hard Segment
Hard
Hard Segment
Segment Hard Segment Soft
Soft Segment
Segment Soft Segment HardHard Segment
Segment Hard Segment
Hard Segment Polyester
Polyol Polyester
Polyol
Soft Segment Hard Segment
Polyester
Polyol Polyester
Step 1:
Polyol
Step
Hard Segment
1: Hard Step 1: Soft Segment Soft Step
Segment
Polyol Polyol 1: Polyol
Polyester
Segment
Step
Step 1:
1: Hard Step 1: Soft Step 1: Polyol Hard Segment Hard Segment
Polyester
Polyester
Hard Segment
Step 1: PolyolPolyester
Segment Polyol
Segment Soft Segment Hard Segment Hard Segment
Step 1: Hard
Polyester
Polyester
Hard Segment PolyolStep
Polyol 1: Soft
Polyester
Segment Polyol
Segment Soft Polyester
Segment Polyol Hard Segment Hard Segment
Step 1:
14Polyester
Polyester Polyol
PolyolPolyester Polyol
Polyester Polyol
ep 1: Step 1:Source: DuPont Tate & Lyle BioProducts
 Polytrimethylene ether glycol (PO3G)
Polyurethanes and Thermoplastic Polyurethanes

H [ O
C
C
C
] OH
n

Polytrimethylene ether glycol

(PTMEPOL or PO3G)
Susterra® propanediol may be polymerized
to form PO3G which may be used as 100%
bio-based polyether polyol.

PO3G or PTMEPOL is not a DuPont Tate &

Lyle product. Third parties license a DuPont
technology in order to manufacture and sell
PO3G as separate entities.

For more information on PO3G properties

please contact Allessa GmbH or SK
Chemicals.

15
Technical Studies

2K Waterborne Polyurethane Dispersions (PUDs)

Textile Applications DTM Applications PU Cast Elastomers

Wood Applications
16
 Anionic type PUD
Preparation
Step 1: NCO-terminated prepolymer is prepared by
reacting aliphatic diisocyanate with a blend of
polyol and chain extender DMPA (2,2-
dimethylolpropionic acid) to introduce the pendant
carboxylic group into the prepolymer backbone.

Step 2: The carboxylic group is neutralized with

triethylamine (TEA), forming a salt group that helps
with dispersion of NCO-prepolymer in water.

Step 3: The NCO-prepolymer is dispersed in water.

Step 4: The NCO-prepolymer is chain extended

with diamine (50% diethanolamine and 50%
ethylene diamine) to form poly(urethane-urea) water
dispersion, HFO-4.
Basic steps in preparation of anionic PUDs.

17
Effect of Hydroxyl Oligomer type (HFO-4) on amount of Isocyanate cross-linker.
1K PUD 2K PUD 2K PUD 2K PUD
PUD PDO_A PDO_A PDO_A PDO_A
2000 2000 (Type A) 2000 (Type A) 2000 (Type B)

DEA added first, DEA added first, EDA added first, Variables:
Property Only EDA
then EDA then EDA then DEA
• Order of addition
Equivalent ratio: NCO*/OH-PUD-4 - 1.5 2.0 2.0 for diamine chain
Rate of Instron speed 4 in./min. 4 in./min. 4 in./min. 4 in./min. extender.

Tensile stress @ Break, psi 5394±665 1940±392 2740±478 1975±175 • Equivalent ratio:
NCO/OH-HFO-4
Tensile strain @ Break, psi 795±93 232±39 200±40 217±22

Tensile stress @ Extension 50%, psi 442±46 708±117 945±74 893±74

Tensile stress @ Extension 100%, psi 524±50 952±187 1348±139 1124±131

Tensile stress @ Extension 200%, psi 689±76 1544±310 2343±22 1729±27

Tensile stress @ Extension 300%, psi 974±141 - - -

18 * BAYHIDUR XP 2655 (Covestro).

Formulations and properties of HFO-4 Water Dispersions.
1K PUD/ 2K-PUD/ 2K-PUD/ 2K-PUD/ 2K-PUD/ PUD/ 2K-PUD/ 2K-PUD/
PUD designation PDO-A PDO-A PDO-Sb PDO-C12 BDO-A Polycarbonate PTMG PO3G
2000 2000 2000 2000 2000 2000 2000 2000

Formulations (pbw) Polyesters PC Polyethers

Polyol 2000, g 100.00 100.00 100.00 100.00 100.00 100.00 101.95 100.00
DMPA, g 6.71 6.71 6.71 6.71 6.71 6.71 6.71 6.71
Desmodur I, g 35.01 35.01 35.01 35.01 35.01 35.01 35.01 35.01
Triethylamine, g 4.77 4.92 4.92 4.92 4.92 4.92 4.92 4.92
Dabco T-12, g 4 drops 4 drops 4 drops 4 drops 4 drops 4 drops 4 drops 4 drops
Acetone 0.00 0.00 0.00 200.00 0.00 100.00 0.00 0.00
Water, g 263.00 280.00 270.00 276.00 270.00 270.00 276.00 276.00
DEA, g 0.00 6.83 8.26 6.26 6.26 6.26 6.26 6.26
Ethylenediamine, g 3.41 1.71 1.57 1.57 1.57 1.57 1.57 1.57
Reaction time
(Step-1 synthesis), hrs. - 2.33 2.50 2.25 2.42 2.00 2.50 2.50
Properties
Stability of dispersion
(visual observation) Stable Stable Stable Stable Stable Stable Stable Unstable*
Solids, % 32.74 33.98 33.43 31.68 32.69 33.36 33.96 33.36
Viscosity (25°C), mPas 20.46 13.74 14.22 32.94 11.58 33.78 21.66 30.48
*Viscosity decrease and homogenous after heating to 700C with mixing.

19
 20

Stress-strain curves of PUD films

6000
1
PDO Based
5000 2K-PUDs
4 PDO-based 2K-PUD trends.
4000

1. Lower tensile stress (strength).

Tensile stress [psi]

3000 6 2
3
2. Higher tensile strain (elongation).
2000 5
3. Higher Tensile stress modulus.
1000

0
0 100 200 300 400 500 600 700 800 900 1000

-1000
Tensile strain (Extension) [%]
1) 1K PUD PDO ADIPATE 2000 2) 2K PUD PDO ADIPATE 2000
3) 2K PUD PDO SEBACATE 2000 4) 2K PUD BDO ADIPATE 2000
5) 2K PUD PO3G 2000 6) 2K PUD PTMG 2000

20
ASTM D2370
 21

Coating Properties
1K PUD 2K PUD 2K PUD 2K PUD 2K PUD 2K PUD 2K PUD 2K PUD
PUD PDO_A PDO_A PDO_Sb PDO_C12 BDO_A PC PTMG PO3G
2000 2000 2000 2000 2000 2000 2000 2000
2K-PUD Bio-content, % 34 25 65 60 0 0 0 65
Polyol type Polyester PC Polyether

Hardness, pencil > 9H > 9H > 9H > 9H > 9H > 9H 8H > 9H

No tear @ No tear @ No tear @ No Tear @ No tear @ No Tear @ No tear @ No tear @

Impact Resistance
max. height max. height max. height max. height max. height max. height max. height max. height

Gloss of film, GU 87±8 69±7 76±8 - 79±4 - 99±10 89±4

(cardboard bgd.)
-33.68
Glass Transition Temp.
-47.9 -48.7 -51.2 40 C / 99 C -52.63 -34.58 -80.24 -69.2
(Tg),oC
(MT)

21
 22
Tensile Stress Retention, before and after Hydrolytic Aging.

3518±1278 (break)
Tensile stress @ Break, psi 5394±665 2739±478 2844±429 3097±348* (yield)
1822±253 3244±644
106±39 (break)
Tensile strain@ Break, psi 795±93 199±39 239±48 7.4±1.4 (yield)
206±28 157±29
Hydrolytic Aging properties (50oC, 95% RH, 3 days)
Tensile stress @ Break, psi 3111±335 2131±391 2670±402 3502±545 1799±192 1944±284
Tensile strain@ Break, psi 668±69 165±33 232±27 140±20 193±18 135±14
Retention of Tensile Stress, % 57.6 77.8 93.0 - 98.7 60.0
Polyol 1K PDO-A 2K PDO-A PDO-Sb BDO-A PO3G PTMG
22 Historically: Polyether > Polyester for hydrolytic resistance (aging).
PUD Coating Properties
Abrasion Resistance of PUDs, ASTM D4060

1K PUD 2K PUD 2K PUD 2K PUD 2K PUD 2K PUD

PUD PDO_A PDO_A PDO_Sb BDO_A PO3G PTMG
2000 2000 2000 2000 2000 2000
DEA, then DEA, then DEA, then DEA, then DEA, then
Only EDA
EDA EDA EDA EDA EDA
Equivalent ratio:
- 2.0 2.0 2.0 2.0 2.0
NCO/OH-PUD-4

Taber abrasion test conditions: ASTM D4060: test wheel C-10, 1000 cycles*

Weight of test sample, g 1.490 1.178 1.330 1.301 1.121 1.543

Weight Loss, mg/1000 cycles 20 35 22 14

* PUDs were coated on Popular wood substrate (2618, Home Depot), 1/4" thickness. The PUD thickness was ~ 0.1mm (~ 4 mils)

23
 PUD Coating Properties
Solvent Resistance of PUD Coating to Isopropyl Alcohol (IPA, ASTM D5402), Rub Test

1K PUD 2K PUD 2K PUD 2K PUD 2K PUD 2K PUD 2K PUD

2K PUD
PUD PDO_A PDO_A PDO_Sb PDO_C12 BDO_A PolyCarb PO3G
PTMG 2000
2000 2000 2000 2000 2000 2000 2000

DEA, then DEA, then DEA, then DEA, then DEA, then DEA, then DEA, then
Only EDA
EDA EDA EDA EDA EDA EDA EDA

Equivalent ratio:
- 2.0 2.0 2.0 2.0 2.0 2.0 2.0
NCO/OH-PUD-4
Test Method: Double Rub Test, 200 rubs, Coated on Metal substrate
Change in Film thickness
-17.95 -13.17 +10.54 0.00 -3.70 -3.39 -17.22 -7.34
after 100 double rubs, %
Change in Film thickness
-43.97 -15.22 +8.31 -2.69 -7.24 -9.72 -17.41 -3.67
after 200 double rubs, %
Group Ranking* 5 4 2 1 2 2 3 1

Overall Ranking** 8 6 3 1 3 5 7 2

* Polyether or polyester PUDs; Lower number is better. ** All PUDs

24
Textile
Applications

25
 Testing of PUD coated fabrics
Gloss of 2K-PUDs coated on various fabrics*

1K PUD 2K PUD 2K PUD 2K PUD 2K PUD 2K PUD

PUD PDO_A PDO_A PDO_Sb BDO_A PO3G PTMG
2000 2000 2000 2000 2000 2000

Only EDA DEA, then EDA DEA, then EDA DEA, then EDA DEA, then EDA DEA, then EDA

Equivalent ratio:
- 2.0 2.0 2.0 2.0 2.0
NCO/OH-PUD-4
Gloss on
2.1±0.00 1.8±0.00 1.4±0.22 1.6±0.06 1.6±0.06 1.6±0.08
Cotton Sateen
Gloss on
- 1.8±0.06 1.6±0.00 1.7±0.00 1.7±0.00 1.6±0.00
Nylon
Gloss on
1.6±0.14 1.5±0.05 1.2±0.05 1.4±0.08 1.4±0.08 1.5±0.00
Polyester Duck

* The Gloss was measured via ETB-0686 glossmeter. PUDs were coated with Wire Coat 100 (10 mil or 70 microns) on fabrics.

26
 Testing on PUD Coated Fabrics
Stain Resistance of PUDs coated on Fabrics (cotton, nylon, and polyester)*
Stain Ink Coffee Ketchup Lotion
(cleaner) (20% bleach soln.) (Liquid dish soap) (Formula 409) (Liquid dish soap)

Group** Overall #
Fabric Cotton Nylon Polyester Cotton Nylon Polyester Cotton Nylon Polyester Cotton Nylon Polyester TOTAL
Ranking Ranking

PUD

1K PUD
3 1 1 2 1 2 1 2 1 1 1 1 17 1 2
PDO_A 2000

2K PUD
3 1 2 3 1 2 1 2 2 1 1 1 20 4 5
PDO_A 2000

2K PUD
2 2 1 2 2 1 1 3 1 1 1 1 18 2 3
PDO_Sb 2000

2K PUD
3 1 2 2 1 1 1 3 1 1 1 1 18 2 3
BDO_A 2000

2K PUD
1 2 1 3 `1 2 1 2 1 1 1 1 16 1 1
PO3G 2000

2K PUD
2 3 3 3 1 3 1 3 1 1 1 1 23 2 6
PTMG 2000

* Relative scale: 1 - Best, 5 – Worst, ** Group: Polyester and Polyether, # Ranking – All PUDs.
27
 Testing on PUD Coated Fabrics
Effect of Hydrolytic Aging (50oC, 70% RH, 7 days) on Water hold out for PUDs coated Fabrics.

Wire Coater No. 100 (non-aged fabric) 15 (aged fabric) 100 (aged fabric)
Water drop holding (min) Water drop holding (min) Water drop holding (min)

Overall **
Coated Fabric Cotton Nylon Polyester Cotton Nylon Polyester Cotton Nylon Polyester

Group *
Total #
Fabric only < 1 min < 1 min < 1 min

PUD Type

1K- PUD
> 5 min 2-3 min > 5 min > 5 min > 5 min < 30 sec > 5 min 2-3 min > 5 min 35.5 4 5
PDO-A 2000

2K- PUD
> 5 min > 5 min > 5 min > 5 min < 1 min < 2 min > 5 min > 5 min > 5 min 38.0 3 4
PDO-A 2000

2K- PUD
> 5 min > 5 min > 5 min > 5 min > 5 min > 5 min > 5 min > 5 min > 5 min 45.0 1 1
PDO-Sb 2000

2K- PUD
> 5 min 5 min> > 5 min > 5 min < 2 min 4-5 min > 5 min > 5 min > 5 min 41.5 2 2
BDO-A 2000

2K-PUD
> 5 min 1-2 min > 5 min > 5 min < 30 sec > 5 min > 5 min 1-2 min > 5 min 33.0 2 6
PO3G 2000

2K-PUD
> 5 min > 5 min 4-5 min > 5 min > 5 min < 2min > 5 min > 5 min 4-5 min 41.5 1 2
PTMG-2000
# Total, Sum of times, midpoint or maximum.
28
* Polyether or polyester PUDs ** All PUDs. Relative ranking, Lower number is better
Effect of Washing+ on Water Hold-Out of PUDs coated Fabrics.
Wire Coater 100 (non-aged) 100 (after washing, 5 cycles)
Rankings
Water drop holding (min) Water drop holding (min)

Ranking**
Fabric Cotton Nylon Polyester Cotton Nylon Polyester

Ranking*

Overall
Group
Total
Fabric only < 1 min < 1 min < 1 min

PUD Type

1K PUD
PDO_A 2000 > 5 min 2-3 min > 5 min < 1 min < 30 sec 4-5 min 18.50 4 6

2K PUD
PDO_A 2000 > 5 min > 5 min > 5 min > 5 min < 30 sec > 5 min 25.50 3 3

2K PUD
PDO_Sb 2000 > 5 min > 5 min > 5 min > 5 min < 2 min > 5 min 27.00 1 1

2K PUD
BDO_A 2000 > 5 min > 5 min > 5 min > 5 min 30 sec-1 min > 5 min 25.75 2 2

2K PUD
PO3G 2000 > 5 min 1-2 min > 5 min > 5 min < 30 sec > 5 min 22.00 2 5

2K PUD
PTMG 2000 > 5 min > 5 min 4-5 min > 5 min 30 sec-1 min > 5 min 25.25 1 4

ALL samples on All fabric sources maintained a 5A on the peel test (before/after).
+ Wash cycle: RT, 30 min, detergent/water.
* Relative Ranking Polyether or polyester PUDs. ** Relative Ranking for All PUDs. Lower number is better.
29
 Ranking of PUDs for Textile Applications*
1K PUD 2K PUD 2K PUD 2K PUD 2K PUD 2K PUD
PUD PDO_A PDO_A PDO_Sb BDO_A PO3G PTMG
2000 2000 2000 2000 2000 2000
Test Method Only EDA DEA, then EDA DEA, then EDA DEA, then EDA DEA, then EDA DEA, then EDA

Abrasion Resistance 4 6 5 3 1 2
Solvent Resistance
6 4 2 1 5 2
(Rub Test)
Solvent Resistance
6 3 5 1 1 4
(Coating, 10 drops)
Hydrolytic Aging
5 4 1 2 6 2
(Wire Coater =100)
Stain Resistance 4 5 2 2 1 6

Water Hold Out

6 3 1 2 5 4
After Washing
Total (All, Sum) 31 25 16 11 19 20

Total (Fabric only, Sum) 15 12 4 6 12 12

* Relative ranking 1 – Best, 6 – Worst.

Overall: BDO-AA > PDO-Sb > PO3G > PTMG > PDO-A > 1K-PUD PDO-AA; Sum - Lower number is better.

30 On Fabric: PDO-Sb > BDO-AA > PO3G, PDO-AA, PTMG > 1K PDO-AA
 Direct to Metal
Applications

31
 32
Effect of Hydrolytic Aging (38°C, 95%RH, 7 days) on Properties of 2K-PUDs coated on
Various Metal Substrates.
2K-PUD/ 2K-PUD/ 2K-PUD/ 2K-PUD/ 2K-PUD/ 2K- PUD/ 2K-PUD/
2K-PUD Designation PDO-A PDO-Sb PDO-C12 BDO-A Polycarbonate PTMG PO3G
2000 2000 2000 2000 2000 2000 2000
Property Substrate
Aluminum 0/2 tear 1/2 tear 0/2 tear 0/2 tear 1/2 tear 1/2 tear 0/2 tear
Adhesion – peel test Steel 0/2 tear 0/2 tear 0/2 tear 0/2 tear 2/2 tear 0/2 tear 0/2 tear
(2 specimen tested) Stainless Steel 0/2 tear 1/2 tear 0/2 tear 0/2 tear 2/2 tear 0/2 tear 0/2 tear
ASTM D2794 Aluminum 601- 7075 0/2 tear 1/2 tear 0/2 tear 0/2 tear 1/2 tear 2/2 tear 0/2 tear
Aluminum 202-2024 0/2 tear 1/2 tear 2/2 tear 0/2 tear 1/2 tear 0/2 tear 1/2 tear
Category Score Total 0 4 2 0 7 3 1
Aluminum 0/2 break 0/2 break 0/2 break 0/2 break 0/2 break 0/2 break 0/2 break
Impact strength Steel 0/2 break 0/2 break 1/2 break 0/2 break 0/2 break 0/2 break 0/2 break
(2 specimen tested) Stainless Steel 0/2 break 0/2 break 0/2 break 0/2 break 0/2 break 0/2 break 0/2 break
ASTM D3359 Aluminum 601-7075 1/2 break 0/2 break 0/2 break 0/2 break 0/2 break 0/2 break 0/2 break
Aluminum 202- 2024 0/2 break 0/2 break 0/2 break 0/2 break 0/2 break 0/2 break 0/2 break
Category Score Total 1 0 1 0 0 0 0

Blistering
(2 specimen tested)
No Blistering observed for all PUDs on all metal substrates

Signs of Rust 3/3 signs 1/3 signs 2/3 signs 2/3 signs 1/3 signs 1/3 signs 2/3 signs
(3 specimen tested) Steel
of rust of rust of rust of rust of rust of rust of rust
Category Score Total 3 1 2 2 1 1 2
Overall Score* Total 4 5 5 2 8 4 3

Category Score & Overall Score: Red = 1st, Blue = 2nd, Green = 3rd, lower numbers are better.
32
 33

Solvent Resistance of 2K-PUDs to SKYDROL® LD4 (Eastman) Fire

Resistant Hydraulic Fluid on Aluminum Substrates (2024 & 7075).

2K-PUD/ 2K-PUD/ 2K- PUD/ 2K-PUD/ 2K-PUD 2K- PUD/ 2K- PUD
2K-PUD
Designation
PDO-Adipate PDO-Sebacate PDO-C12 BDO-Adipate PC PTMG PO3G
2000 2000 2000 2000 2000 2000 2000

Substrate Polyester Polycarbonate Polyether

Aluminum alloy
1 1 2 2 3 2 4
601-7075

Aluminum alloy
1 1 2 2 3 2 3
202-2024
Notes: 10 drops solvent, 10 minutes
1- No effect , 2- non-penetrating, scratches, 3- penetrating scratches, 4-delamination

33
 34
Corrosion Resistance of Steel Coupons ( Q-panel Type CXB-12, 1 x 2 x 0.125 inches)
Coated with 2K-PUDs Immersed in 3% NaCl solution
2K-PUD/ 2K-PUD/ 2K-PUD/ 2K-PUD/ 2K-PUD/ 2K-PUD/ 2K-PUD/
2K-PUDs
PDO-A PDO-Sb PDO-C12 BDO-A PC PTMG PO3G
Designation
2000 2000 2000 2000 2000 2000 2000
2K- PUD formulation Polyester Polycarbonate Polyether
HFO-4 100.00 100.00 100.00 100.00 100.00 101.95 100.00
Isocyanate* 11.43 10.65 10.38 10.13 10.80 10.38 10.34
Dabco T-12 0.23 0.22 0.22 0.21 0.23 0.22 0.22
Asconium 142-DA 1.14 1.10 1.10 1.07 1.14 1.11 1.09
Corrosion
evaluation/grading

Rust Coverage, 2 days 3/10 2/10 1/10 3/10 2/10* 2/10 1/10
Rust Coverage, 6 days 5/10 3/10 2/10 4/10 2/10* 3/10 1/10
Rust Coverage, 8 days 6/10 4/10 2/10 4/10 3/10* 3/10 2/10

Rust Coverage, 10 days 6/10 4/10 3/10 4/10 3/10* 3/10 2/10

Corrosion Score 6 4 3 4 3 3 2
Blistering of Coating None None Severe None None Slight Slight
Notes: Relative rating: 1 – best; 10 – the worst; dark area due to corrosion taken into consideration for rating

Corrosion score ranking: Red = 1st, Blue = 2nd, Green = 3rd * BAYHIDUR XP 2655 (Covestro).
34 Corrosion score/Blistering Ranking: Blue = 1st, Green = 2nd.
 35

Ranking of PUDs for Metal Applications* .

Retention – Hydrolytic aging

Property PDO-A PDO-Sb PDO-C12 BDO-A PC PTMG PO3G

Adhesion (peel) 1 6 4 1 7 5 3

Impact Resistance 7 1 7 1 1 1 1

Signs of Rust 7 1 4 4 1 1 4
Solvent Resistance,
1 1 3 3 6 3 7
SKYDROL® LD4
Corrosion Resistance
6 2 7 2 1 5 2
& Blistering
Adhesive strength 5 2 3 3 1 6 7

Total 27 13 28 14 17 21 24

Overall Ranking* 6 1 7 2 3 4 5

* Relative ranking 1 – Best, 7 – Worst.

35 • For each metal substrate, ranked each 2K-PUD system 1-7 based on retention values.
• Overall ranking is the sum of all substrate rankings. Lowest number is best.
 Polyurethane
Cast Elastomers

36
 37
Prep- Prep-
Prepolymer Prep-PPG Prep-PTMG Prep-PO3G
PDO-Sb
Prep-PC
PPG/PO3G
Polyol, g 684.01 341.73- 680.58 340.20 340.83
Blend of 50%
Prep-PPG and
TDI, Lupranate T-80 115.99 58.27 119.42 59.8 59.17 50% Prep-PO3G TDI Prepolymer
formulations
3.58 3.48 3.45 3.55 3.52 3.52
NCO % & properties
Viscosity at 70°C, mPa·s 753 2,982 2425 6,610 47,280 1348
-53.0 -72.9, -64.6 -34.1, -36.3, -59.9
Transitions via DSC, °C
-39.4, 24.8 48.5 42.2

Cast Elastomer CE-PPG CE-PTMG CE-PO3G CE-PDO-Sb CE-PC CE-PPG/PO3G

PU-CE Bio-content 0 0 78 78 0 39
Prepolymer 55.20 55.33 55.37 55.24 55.22 55.28*
Ethacure 300 4.80 4.67 4.63 4.76 4.78 4.71
Cast Elastomers:
Reaction conditions
Gel time, s 852 525 493 661 375 65 Formulation &
Mix time, s at 2200 rpm 60 120 90 90 90 40 Curing Conditions
Isocyanate Index 1.05
Prepolymer pre-heat, °C 80
Carver Press temperature, °C 80
Approximate press pressure,
psi 20,000
Time in press, min 60
Post cure 7 days at ambient room conditions

* 27.64 g Prep-PPG and 27.64g Prep-PO3G

 Hardness of Cast Elastomer prepared with Various Polyols

74.2 84.3 82.0 75.3 86.8 90.8

100

80
Hardness

60

40 23.4 34.3 29.5 24.4 36.8 39.2

20

PPG PTMG PO3G PPG/PO3G SbPDO PC

Shore A Shore D Cast Elastomer Formulation

38
Reference: ASTM D2240
 Resilience (%) and Tear Strength (N/cm) of Cast Elastomers with Various Polyols

595 1177 1118 885 1213 1290

49.4 57.5 53.9 53.5 47.4 34.0
60 1250
Resilience, Bayshore Rebound, %

1000

Tear strength, N/cm2

40
750

500
20

250

0 0
PPG PTMG PO3G PPG/PO3G SbPDO PC PPG PTMG PO3G PPG/PO3G SbPDO PC

Cast Elastomer Formulation Cast Elastomer Formulation

Reference: ASTM D-430 Reference: ASTM D-624

39
 Abrasion resistance (mg loss/1000 cycles) of Cast Elastomers prepared
with Various Polyols

334 16 50 104 17 3

40
Reference: ASTM D1044
 Tensile strength at break and Elongation at break for Cast Elastomers of
various polyols for Initial & After Hydrolytic Aging, Retention%.
103% 96% 97% 80% 106% 89% 80% 84% 84% 75% 86% 82%
6000 1500

Initial After Hyrdrolytic Aging Initial After Hydrolytic Aging

Tensile strength at break, psi

5000 1250

Elongation at break, %
4000 1000

3000 750

2000 500

1000 250

0 0
PPG PTMG PO3G PPG/PO3G SbPDO PC PPG PTMG PO3G PPG/PO3G SbPDO PC
Cast Elastomer Formulation Cast Elastomer Formulation

41
• ASTM D412: Hydrolytic Aging conditions : 5 days, 60°C and 95% RH
• Retention %: After Hydrolytic Aging / Initial * 100
Tensile Modulus at 100% Elongation of Cast Elastomers under Different
Environmental Conditions.
RT 50°C 70°C Hydrolytic Aged
1500
Tensile strength at 100% elongation, psi

1250

1000
Tensile Modulus is a
measure of material’s
750
resistance to elastic
deformation.
500
• TM = Stress / Strain
250

PPG PTMG PO3G PPG/PO3G SbPDO PC

Cast Elastomer Formulation

ASTM D-412; Hydrolytic Aging conditions: 5 days, 60°C and 95% RH

42
Resistance of Cast Elastomers by Immersion (weigh change, %) in Various Solutions.

Oil 0.1N HCl 0.1N KOH

2

1.8

1.6

1.4
Weight Change, %

1.2

0.8

0.6

0.4

0.2

0
PPG PTMG PO3G PPG/PO3G SbPDO PC
Cast Elastomer Formulation

43
Conditions: Immersion, 3 days, RT.
 44
Ranking of Polyols for Polyurethane Cast Elastomer Applications*. 44

Property PPG PTMG PO3G PPG/PO3G PDO-Sb PC

Hardness (Shore A/D) 6 3 4 5 2 1
Resilience, Bayshore Rebound (%) 4 1 2 3 5 6
Tear strength, N/cm2 6 3 4 5 2 1
Abrasion Resistance 6 2 4 5 3 1
Hydrolytic Aging

Tensile strength at Break,

retention %
6 4 3 3 1 5
Elongation at Break,
retention %
5 2 2 6 1 4
Tensile Modulus stability per
Environmental Condition
5 1 3 6 2 4

Immersion weight gain, % 6 3 4 5 2 1

Adhesive Strength, Load at Break
(retention %)
6 5 1 3 4 2

Total 50 24 27 41 22 25
Overall Ranking* 6 2 4 5 1 3
* Relative ranking 1 – Best, 6 – Worst.
• For each category, ranked each Cast Elastomer system 1-6 based on test performance.
• Overall ranking is based on the sum of all categorical rankings. Lowest number is best.
 45

Summary: Susterra® Propanediol

• Susterra® Propanediol is a pure, petroleum-free glycol (# 2 Industrial corn, glucose to 1,3-PDO via fermentation).
• Susterra® is sustainably and renewably sourced with a favorable LCA (PG, BDO).
• Susterra® is suitable for many Coatings application where polyols are utilize for a multitude of functions.
• Susterra® can be used as a polyol (Polyester/Polyether) and/or chain extender in PUDs.
• PDO-based PUDs introduce a lower tensile stress, higher tensile strain, and higher tensile modulus vs. BDO & PTMG.
• 2K-PUD PDO-Sb 2000 offers hydrolytic aging performance ≥ 2K-PUD Polyether's (PTMG).
• 2K-PUDs based on PDO (PDO-Sb, PDO-A, PO3G) performed well on textile fabric substrates.
• 2K-PUDs based on PDO-Sb 2000 performed exceptionally well on metal substrates

• Impact strength, Corrosion resistance, SKYDROL® LD4 resistance & Adhesive strength).
• 2K-PUD based on PDO-C12 2000 Mw was identified as a good candidate for hot melt adhesives.
• PU Cast Elastomers (Pipe Liners) based on PDO-Sb performed ≥ PC and PTMG, both high performance CE systems.
• PDO offers formulators an alternative polyol to drive a unique combination: High Performance & Sustainability

Note: It is important to know your environment, identify priority performance properties, and
45 invest the time to evaluate & differentiate.
 Questions?
Sean Gahan
Technical Service Manager
198 Blair Bend Drive
Loudon, TN 37774
865.399.5472 Mobile
Sean.L.Gahan@dupont.com
www.duponttateandlyle.com

Copyright © 2018 DuPont Tate & Lyle Bio Products Company, LLC.
46 Susterra® is a registered trademark of DuPont Tate & Lyle Bio Products Company, LLC, for its brand of bio-based propanediol. All rights reserved.