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DuPont Tate & Lyle BioProducts Confidential 1
Bio-Based PDO
Susterra®
(1,3 Propanediol)
Understanding the Landscape of
Coatings Applications
South Asia ContactGowri S. NagarajanBusiness Development [email protected]+91-9810336798
Presentation AuthorDoug HopekMarketing ManagerDuPont Tate & LyleUSA
Bio-Based PDO (1,3 Propanediol)
What is it?• A pure, petroleum-free derived diol
• 100% sustainably and renewably sourced
• Used in a range of industrial applications including polymers, functional fluids, and polyurethanes
• Used globally in coatings, inks, and resin applications
How is it made?• Made by a fermentation process derived from glucose
• Produced in the USA (DuPont Tate & Lyle) and in China (Other)
• USA Production: USDA 100% Certified Bio-Based Product
Source: DuPont Tate & Lyle BioProducts2
1,3 Propanediol (PDO) is an alternative to wide range of glycols used in industrial applications.
Common Ingredient CAS # Formula Structure Mol. Wt. Bp, oC Mp, oC Density
EG 1,2-Ethanediol 107-21-1 C2H6O2 62.1 197.6 -12.7 1.116
PG 1,2-Propanediol 57-55-6 C3H8O2 76.1 187.3 -60 1.038
PDO 1,3-Propanediol 504-63-2 C3H8O2 76.1 214 -24 1.053
MPDiol 2-Methyl-1,3-Propanediol 2163-42-0 C4H10O2 90.1 221 -91 1.015
1,4 BDO 1,4-Butanediol 110-63-4 C4H10O2 90.1 230 16 1.017
Neopentyl Glycol 2,2-Dimethyl-1,3-Propanediol 126-30-7 C5H12O2 104.1 208 127 ~1.05
DEG Diethylene Glycol 111-46-6 C4H10O3 106.1 245 -10 1.118
Hexylene Glycol 2-Methyl-2,4-Pentanediol 107-41-5 C6H14O2 118.2 197 -40 0.925
DPG Dipropylene Glycol 25265-71-8 C6H14O3 134.17 231 1.023
HO
OH
OHHO
HO OH
HO
OH
HO
O
OH
OHOH
OHHO
3Source: DuPont Tate & Lyle BioProducts
Bio-Based PDO (1,3 Propanediol) Commercial Applications
Deicing & Functional Fluids Coatings
Laundry & Home Care Fibers
Cosmetics & Personal Care
4
Polymers
Source: DuPont Tate & Lyle BioProducts
Enabling a Renewable Economy...
The source is renewable
Oil Refining Chemistry
Crops Biomass Feedstock Metabolic Engineering
The source is not renewable
From:
To:
Coatings, Inks, Resins
Molded Parts
Fibers
Source: DuPont Tate & Lyle BioProducts5
GlucoseStarch
Fermentation Process Refine to 99.7% Pure
Process to Bio-Based PDO (1,3 Propanediol)
Bio-based 1,3 Propanediol
bioprocess
Source: DuPont Tate & Lyle BioProducts6
LCA is the only standardized method to evaluate the environmental footprint of a whole supply chain. Energy consumption and Green House Gas (CO2) emissions are key factors in determining environmental footprint.
Life Cycle Analysis (LCA) Approach
Cradle-to-gate
Cradle-to-graveCO2
Biodegradation of
product results in no net
CO2 increase
Manufacturing
Transportation TransportationUse/Reuse/
Maintenance
Recycle
Waste Management
AirEmissions
WaterborneWastes
Solid WastesCo-products
EnergyRaw Materials
Raw MaterialAcquisition
7Source: DuPont Tate & Lyle BioProducts
Bio-Based PDO Life Cycle Assessment* Comparison
*LCA data based on Loudon process design data; peer reviewed by Five Winds International, Source: DuPont Tate & Lyle BioProducts
From “Cradle-to-Gate,” the production of Bio-PDO consumes 40% less energy and reduces GHG emissions by more than 40% vs. petroleum-based 1,3 propanediol and propylene glycol.
8
Landscape of Bio-Based PDO Applications
Wood Coatings
UPR
UV Coatings
Inks
Water Based
Coatings
Powder Coatings
Polyurethane Coatings
9Source: DuPont Tate & Lyle BioProducts
Landscape of Bio-Based PDO Applications
Wood Coatings
UPR
UV Coatings
Inks
Water Based
Coatings
Powder Coatings
Polyurethane Coatings
10Source: DuPont Tate & Lyle BioProducts
Bio-Based PDO as a Polyurethanes Raw Material
Source: DuPont Tate & Lyle BioProducts11
Polyurethane Coatings/Films
1,3 Propanediol Applications:
Industrial Markets• Polyurethane coatings
• Thin film, High gloss finish • Weathering performance
Artificial Leather• Adhesion • Leather body• Surface treatment
PU Film• Functional layer• Waterproof/breathable coating applications
Source: DuPont Tate & Lyle BioProducts, Nam Liong12
Landscape of Bio-Based PDO Applications
Wood Coatings
UPR
UV Coatings
Inks
Water Based
Coatings
Powder Coatings
Polyurethane Coatings
13Source: DuPont Tate & Lyle BioProducts
Powder Coatings Based on 1,3 PDO
HYDROXYL POLYESTER(PDO, NPG, and 80/20 TPA/IPA)
POLYESTER/TGIC POWDER(PDO, NPG, and 76/24 TPA/IPA)
POLYESTER/EPOXY(PDO, NPG, and 80/20 TPA/IPA)
• Improved flexibility when NPG was replaced by PDO
• Comparable properties included: hardness, adhesion, water/salt spray corrosion and QUV resistances
• Improved resistance and flexibility
• Comparable properties included hardness, adhesion, and chemical resistances are retained over a broad range of PDO concentrations
• Viscosity of the polyester decreased as the level of PDO increased
• Improved impact resistance and flexibility
• Comparable properties included hardness, adhesion, and chemical resistances are retained over a broad range of PDO concentrations
• Viscosity of the polyester decreased as the level of PDO increased
Applications: Polyesters prepared from 1,3-propanediol (PDO), neopentyl glycol (NPG), and an terephthalic/isophthalic acid combinations
Learnings:
Sources: University of Southern Mississippi, Shell Co.14
Landscape of Bio-Based PDO Applications
Wood Coatings
UPR
UV Coatings
Inks
Water Based
Coatings
Powder Coatings
Polyurethane Coatings
15Source: DuPont Tate & Lyle BioProducts
Water Based CoatingsArchitectural Semi-Gloss Coatings
1,3 Propanediol:
• Fully miscible with water
• Clear/Colorless
• Low toxicity
1,3 Propanediol Functionality:
• Comparable low temperature freeze protection and stability vs. PG
• No adverse effect on optical properties of paints
• Adds Bio-Content
Replacement for:
• Propylene Glycol (PG)
Source: DuPont Tate & Lyle BioProducts16
• Learnings: • Properties were comparable•1,3 PDO increased the tinting strength in conventional latex formulations
3
6
Std. Dev.
1.7
1.7
2.6
1
Std. Dev.
72
40
mean
99
101
103
103
Susterra®
(mean)
2
4
Std. Dev
73
41
mean
100
100
100
100
PG
(standard)
Acrylic SG-30-2 Vinyl Acrylic SG-FT-3
71
40
mean
111
101
102
101
Susterra®
(mean)
8877Gloss 60
151648Gloss 20
Std. Dev.
Std. Dev
mean
8118SSU
0.7100S m2/gm
0.7100BO Tint Strength
0.7100DD Tint Strength
Std. Dev.
PG
(standard)
3
6
Std. Dev.
1.7
1.7
2.6
1
Std. Dev.
72
40
mean
99
101
103
103
Susterra®
(mean)
2
4
Std. Dev
73
41
mean
100
100
100
100
PG
(standard)
Acrylic SG-30-2 Vinyl Acrylic SG-FT-3
71
40
mean
111
101
102
101
Susterra®
(mean)
8877Gloss 60
151648Gloss 20
Std. Dev.
Std. Dev
mean
8118SSU
0.7100S m2/gm
0.7100BO Tint Strength
0.7100DD Tint Strength
Std. Dev.
PG
(standard)
Architectural Semi-Gloss Coating Evaluation: Tint Strength
Source: DuPont Tate & Lyle BioProducts
1,3 PDO 1,3 PDO
• Vinyl Acrylic SG-FT-3• PG vs. 1,3 PDO at 5.00%
• Acrylic SG-30-2• PG vs. 1,3 PDO at 3.26%
17
Evaluation: Open Time or Wet Edge
• 1,3 PDO has 15-20% better open time � Improves film formation
– Improve paint application– Reduce roller application time
• Replacing PG by 1,3 PDO has no adverse effect on optical properties of paints
• 1,3 PDO may show good impact on flow and leveling in lower PVC (25-30%) paints
• 1,3 PDO in machine colorants can slow in-can drying � reducing scale formation
Source: DuPont Tate & Lyle BioProducts18
Landscape of Bio-Based PDO Applications
Wood Coatings
UPR
UV Coatings
Inks
Water Based
Coatings
Powder Coatings
Polyurethane Coatings
19Source: DuPont Tate & Lyle BioProducts
Wood Coatings: Weathering Research
Research Scope• Acrylate dispersion• Acrylate dispersion blended with
1,3-propanediol based PUD• Acrylate dispersion blended with
1,6-hexanediol based PUD
Learnings:• PUD may prolong the durability of
exterior varnishes due to a higher initial elasticity and keeping it high during the exposure
• 1,3-PDO based PUD seems to be a bit more sensitive to aging by weathering influence
Source: Fraunhofer-Wilhelm-Klauditz-Institute for Wood Research20
Landscape of Bio-Based PDO Applications
Wood Coatings
UPR
UV Coatings
Inks
Water Based
Coatings
Powder Coatings
Polyurethane Coatings
21Source: DuPont Tate & Lyle BioProducts
UV Curing Coatings: Application Research
Learnings:
• UV-PU-acrylates exhibit an excellent grain enhancement
• High gloss
• Low solvent requirement
Source: Fraunhofer-Wilhelm-Klauditz-Institute for Wood Research
Characteristics:
22
Landscape of Bio-Based PDO Applications
Wood Coatings
UPR
UV Coatings
Inks
Water Based
Coatings
Powder Coatings
Polyurethane Coatings
23Source: DuPont Tate & Lyle BioProducts
Inks
PDO:
• Fully miscible with water
• Clear/Colorless
• Low toxicity
• 100% Bio-Based Material
PDO Functionality:
• Humectant
• Tonner binder
• Bio-content
• Dry performance
Replacement for:
• Humectants – PG, Glycerin
• Resins- Diol Replacement in Polyols
Source: DuPont Tate & Lyle BioProducts24
Landscape of Bio-Based PDO Applications
Wood Coatings
UPR
UV Coatings
Inks
Water Based
Coatings
Powder Coatings
Polyurethane Coatings
25Source: DuPont Tate & Lyle BioProducts
UPR Chemistry with 1,3 Propanediol
O OO
O OO
OH OH
O O
O O
O
OO
O O
O
O
O
+ +
maleicanhydride(MA)
phthalicanhydride(PA)
1,3-propanediol(1,3-PDO)
fumaricfragment(FA)
O O
O O
O
OO
O O
O
O
O
O
O
O
O
O
O
OO
OO O
O
O
fumaricfragment(FA)
styrene(STY)
+
crosslink
promotor
initiator
Step 1: UPR Synthesis
Step 2: UPR Crosslinking
During the production of UPR’s two types of reactions occur. Next to thepolycondensation, isomerization of maleic to fumaric groups takes place, renderingthe UPR reactive towards the vinylic crosslinker (styrene).
Source: DuPont Tate & Lyle Bio Products26
UPRs contain three types of building blocks.
Diols
• 1,2 Propanediol• 1,3 Propanediol• DEG• NPG• MPDiol
Unsaturated Diacids
• Maleic anhydride
Bio-Based PDO Fumeric Building Block
Saturated Diacids
• Ortho-phthalic acid• Iso-phthalic acid
Biobased Content
Material Final UPR
Bio- Based PDO (1,3 Propanediol) 100 wt% 10 - 25 wt%
Significant contribution to bio-based content
27Source: DuPont Tate & Lyle Bio Products
Formulations Studied
Monomer UPR Description in Monomer Amount [mole equivalent]
UPR-1,2-PG UPR-1,3-PDO UPR-80/20 mix
Ortho-PA 1.2 1.2 1.0
MA 0.8 0.8 1.0
Bio-Based 1,3-PDO 0 2.2 1.76
1,2-PG 2.2 0 0.44
• Formulation Range:
• Reactive resin (high MA): <~70% 1,3-PDO on total diol
• Less reactive resin (PA/MA ~ 1): <~80% 1,3-PDO on total diol
• Even less reactive resin (low MA): up to 100% 1,3-PDO on total diol
28
Processing Learnings: 1,3-PDO vs. 1,2-PG• UPR cook production aspects
• The higher boiling point of 1,3-PDO allows for shorter batch times or less loss of glycol.
• 1,3-PDO slows down the viscosity build of the UPR polymer during synthesis.
• 1,3-PDO decreases the isomerization rate of maleic units in the UPR.
– This effect is amended by additives or procedural optimizations.
– Thus, negative impact on end-use properties (e.g.; hydrolytic stability) is prevented.
• 1,3-PDO lowers the glass transition Tg of the non-crosslinked UPR below room temperature
– Rendering it sticky, rather than glassy.
• No differences in viscosity observed between UPR’s based on 1,3-PDO or 1,2-PG at 60 wt% in methylcellosolve or styrene.
• UPR / styrene crosslinking (reactivity)
• 1,3-PDO slightly reduces the SPI gel and cure times and increases the peak exotherm.
Conclusions based on recipes PA/MA/diol = 1.5/1.0/2.2 Source: DuPont Tate & Lyle Bio Products
29
End-use properties: Bio-Based PDO vs. PG
• Physical Properties
• Bio-PDO gives crosslinked UPR casts that are colorless and clear
• Mechanical Properties
• Similar glass transition temperatures were observed
• No statistical differences in the barcol hardness were observed
• Bio-PDO lowers the heat deflection temperature (HDT) of a UPR thermoset
• Bio-PDO lowers the compressive strength of a UPR material
• Bio-PDO lowers the modulus (tensile and flex), of UPR thermosets, while highervalues for strength and elongation are obtained
• Summary
Bio-Based PDO (1,3-Propanediol) based UPR thermosets are less stiff and more flexible without being detrimental to strength or hardness.
Conclusions based on recipes PA/MA/diol = 1.5/1.0/2.2 30Source: DuPont Tate & Lyle Bio Products
Landscape of Bio-Based PDO Applications
Wood Coatings
UPR
UV Coatings
Inks
Water Based
Coatings
Powder Coatings
Polyurethane Coatings
31Source: DuPont Tate & Lyle BioProducts
Landscape of Bio-Based PDO ApplicationsSummary
32
Application Function
Powder PU Coatings NPG Replacement for Performance
PU Coatings Glycol Choice for Polyol or Curative
Water-Based Coatings PG Replacement for Freeze Protection
Inks Humectant, Polyester Binder
UV Coatings Grain Enhancement, Reduce Solvents
Wood Coatings Weathering Resistance Performance
UPR Glycol Choice for Performance & Bio
Wood Coatin
gs
UPR
UV Coatin
gs
Inks
Water Based Coatin
gs
Powder
Coatings
Polyurethane Coatin
gs
Source: DuPont Tate & Lyle BioProducts