IBRAHIM SENDIJAREVIC

Troy Polymers

STEPHEN HURFF

DuPont Tate & Lyle Bio Products Co., LLC

Advances in the use of bio-based components in aqueous polyurethane dispersions for coatings and film applications

Abstract

• This study investigates how 100% biobased 1,3-Propanediol (PDO) can be used to make waterborne urethane dispersions (PUDs) with properties suitable for coatings and films in various industries such as wood, metal, textile, leather, footwear, inks, etc.

• Biobased PDO is widely used in a variety of consumer and industrial applications as an inert ingredient as well as both a monomer and chain extender.

• To obtain PUDs with good performance, the effects of varying the block components must be understood. The introduction of dimethyol propanoic acid (DMPA) pendant ionic groups into hard segment blocks facilitates the formation of stable PUDs of acceptable solids loading by increasing hydrogen bond interactions.

• The use of lower molecular weight bio-based polyester/polyether soft segments based on 1,3-PDO with increased hard segment blocks builds on the understanding of structural relationships of the properties of coatings and adhesives.

• The bio-based coatings and films prepared in this investigation provide an extended useful thermal range compared to reference commercial petroleum based PUDs as well as equivalent toughness and flexibility for these one-component waterborne polyurethanes.

• Commercial industrial references were used to compare the properties of the PUDs based on PDO.

2

Acknowledgements

We would like to thank:

• Aisa Sendijarevic, Troy Polymers – Troy, Michigan

• Michael Shen, DuPont Tate & Lyle Bio Products Co., LLC – Shanghai, China

3

Specialty Products Division of

DowDuPont is a global innovation leader

with technology-based materials,

ingredients and solutions that help

transform industries and everyday life.

2017 proforma revenues were $21 billion.

Tate and Lyle is a global provider of

renewable ingredients, solutions and

services to the food, beverage and

industrial customers. Revenues

were $3.8 billion for Fiscal Year

ending March 31, 2018.

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.

4

Value-in-Use

5

6

Our Bio-based Technology

Harvest

Renewably sourced

feedstocks are harvested, dried

and then wet-milled to create

a range of carbohydrate rich

feedstocks such as glucose.

Fermentation

Glucose is converted into

1,3 propanediol using

a patented microorganism

under exact temperatures

and conditions.

Refining

The 1,3 propanediol is refined

to a high purity by

deactivating and removing

the microorganism, water,

and other byproducts.

Renewably sourced feedstocks are harvested, fermented, and refined to manufacture bio-based Susterra® propanediol.

7

Our Product Facility

Production

• Started November 2006

• 2010 capacity expanded 35%

• 2018 Current Capacity = 135 million lb

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

Biotechnology enables our global headquarters and production in Loudon, Tennessee to produce a stable supply of renewably sourced 1,3 propanediol

8

Life Cycle Analysis (LCA) ApproachLCA 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.

Cradle-to-gate

Cradle-to-graveCO2

Biodegradation of

product results in no net

CO2 increase

Manufacturing

Transportation Transportation

Use/Reuse/Maintenance

Recycle

Waste Management

Air Emissions Waterborne Wastes Solid WastesCo-products

EnergyRaw Materials

Raw Material

Acquisition

9

Susterra® Life Cycle Assessment* Comparison

2.18

5.0

4.5

63.9

111.0

94.6

0

20

40

60

80

100

120

0

1

2

3

4

5

6

Susterra® Propanediol(PO route)

BDO Susterra® Propanediol(PO route)

BDO

No

n R

en

ew

ab

le E

ne

rgy (M

J/k

g)G

HG

Em

iss

ion

s (

kg

CO

2e

qu

iv /

kg

) GHG Emission Non Renewable Energy

Green House Gas Emissions- 56% less than Propanediol- 52% less than BDO

Non Renewable Energy Use- 42% less than Propanediol - 32% less than 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

From “Cradle-to-Gate,” the production of Susterra® consumes 32% less energy and reduces GHG emissions by more than 52% vs. petroleum-based BDO.

10

Who is Troy Polymers?Polyurethanes Research & Development Laboratory

Since 2001, Troy Polymers supports Innovative, Sustainable and Environmentally responsible Polyurethane Technologies through all phases of commercialization from early stage R&D through Technical Sales/Marketing to Manufacturing.

11

Raw Materials Design Technical Support & MarketingPolyurethane Formulation

Applications Development

RENEWABLE & PETROCHEMICAL SOURCES

Model Systems

Evaluation

Structure Property

Correlations

FOAMS

TPU/ELASTOMERS

COATINGS

NEW LOCATION: 16,000 sq.. facility

in Madison Heights, MI (6/18)

Equipped for development, evaluation, and testing:

1. Polyurethane Raw Materials

2. Flexible & Rigid Foams, TPU, Elastomers, Microcellular Elastomers

3. Prepolymer and PUD Syntheses

Abstract

• This study investigates how 100% biobased 1,3-Propanediol (PDO) can be used to make waterborne urethane dispersions (PUDs) with properties suitable for coatings and films in various industries such as wood, metal, textile, leather, footwear, inks, etc.

• Biobased PDO is widely used in a variety of consumer and industrial applications as an inert ingredient as well as both a monomer and chain extender.

• To obtain PUDs with good performance, the effects of varying the block components must be understood. The introduction of dimethyol propanoic acid (DMPA) pendant ionic groups into hard segment blocks facilitates the formation of stable PUDs of acceptable solids loading by increasing hydrogen bond interactions.

• The use of lower molecular weight bio-based polyester/polyether soft segments based on 1,3-PDO with increased hard segment blocks builds on the understanding of structural relationships of the properties of coatings and adhesives.

• The bio-based coatings and films prepared in this investigation provide an extended useful thermal range compared to reference commercial petroleum based PUDs as well as equivalent toughness and flexibility for these one-component waterborne polyurethanes.

• Commercial industrial references were used to compare the properties of the PUDs based on PDO.

12

Polyols Studied and their Properties

13

* Indicates commercial reference polyol for property and performance comparisons

Polyols PDO adipate

1000 MW

PDO sebacate

1000 MW

*BDO adipate

1000 MW

*Poly-

caprolactone

1000 MW

PO3G

1000 MW

*Poly(oxytetra-

methylene)glycol

1000 MW

Polyol TradenamePoly S 1000

PAR

Piothane 1000

PDO-SBAPoly S 1000 BA Capa 2100 Velvetol H 1000 Terathane 1000

Source ITWCSpecialty

ResinsITWC Perstorp Allessa Invista

Polyol abbreviation PA PSb BA PCL PO3G PTMG

Properties

OH Value, mg KOH/g 108.21 110.35 105.15 111.29 106.67 113.25

Acid Value, mg KOH/g 0.38 0.19 0.27 0.04 0.05 0

Tg, DSC (°C) -68.86 ND ND -71.9 -77.41 ND

Melt transition, DSC (°C) 24.07 53.78 47.94 38.28 18.18 24.42

DSC used to confirm Polyol Tg and Melt Transition Temperatures

While the DSC results for all polyols were as expected, it is important to point out the following:

− PSb, BA and the PTMG there are no Tg temperatures detected (Fig A for PSB polyol as example)

− PA, PCL and PO3G did reveal both Tg and melt transitions (Fig B for PO3G polyether as example)

− Tc (crystallization temperature) of PO3G is -36 ˚C which is unique for polyether polyol

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Fig. A: DSC for PSB Polyol Fig. B: DSC for PO3G Polyether

Tc point is unique for a polyether polyol

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

or the acetone process can be used to avoid gelling

caused by high hard segment concentrations

yielding high viscosity pre-polymer. The acetone

process was used in this study.

Step 4: The NCO-prepolymer is chain extended

with diamine to form poly(urethane-urea) water

dispersion.

15

Preparation and Testing of PUD Dispersions, Films & Coatings

* Adhesive bonding strength of PUDs to an aluminum substrate was measured according to ASTM D1002 (Lap-shear test).

16

PUD liquid dispersions PUD-based films PUD-based coatings:

See previous slide for anionic PUD

Preparation scheme.

Films were prepared by coating PUD

dispersions onto polypropylene substrate.

The films were left to dry for 24 hours at

room temperature and conditioned for

additional two days.

Coatings were prepared using a Dr. Blade at

30 mil thickness to coat steel panels (Type S-

46, Q-Lab Corporation). The coated panels

were left to dry for 24 hours at room

temperature and conditioned for an

additional two days.

Viscosity of water polyurethane dispersions (25

°C, ASTM D 4878 (Brookfield viscometer))

Tensile strength, modulus and elongation at

break (flexibility) ASTM D2370 (ten specimens) Hardness, Pencil hardness, ASTM D3363

Stability of dispersion over time (visual

observation) Gloss (Gloss-meter) Impact resistance, ASTM D2794

pH

Thermal properties (Glass transition

temperature, Tg), DSC analysis Adhesion, Tape test, ASTM D3359

Solid content, % (4 hrs x 105 °C weight loss) FTIR analysis

Hardness and adhesion measured after 3

days in moisture chamber at 38 °C and 95%

relative humidity per ASTM D 2247.

Density, g/ml

Stress-strain measured in a moisture chamber

at 95% relative humidity, 50 °C for 3 days

Solvent rub test, ASTM D5402 (25 double

rubs)

Solvent Resistance: spreading of various

liquids (water, alkaline and acid water solution,

toluene and MEK) on film surface

PUD Formulation and Properties via the Acetone Process

The acetone loading was reduced from 200 g to 100 g in order to obtain the desired viscosity at 50% hard segment.

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PUD Designation PUD/PA_1 PUD/PA_2 PUD/PSb PUD/BA PUD/PCL PUD/PO3G PUD/ PTMG

FormulationPoly S 1000 PAR, g 100 100 - - - - -

Piothane 1000 PDO-SBA, g - - 100 - - - -

Poly S 1000 BA, g - - - 100 - - -

Capa 2100, g - - - - 100 - -

Velvetol H 1000, g - - - - - 100 -

Terathane 1000, g - - - - - - 100

DMPA, g 13.41 13.41 13.41 13.41 13.41 13.41 13.41

Desmodur I – IPDI, g 70.02 70.02 70.02 70.02 70.02 70.02 70.02

Triethylamine, g 10.12 10.01 9.61 9.61 9.72 9.46 9.61

Dabco T-12, g 0.0345 0.069 0.069 0.0345 0.069 0.0345 0.069

Reaction time, (Step-I, Scheme 1), hrs 1:30 2:00 3:15 3:00 2:50 4:00 2:30

Acetone, g 200 100 100 100 100 100 200

H2O, g 298 450 400 348 440 *430 400

Ethylenediamine, g 5.33 7.26 6.88 7.21 6.99 7.07 6.81

Hard segment, % 49.7 50.2 50.0 50.1 50.0 50.0 50.0

Properties of dispersionspH 8.0 8.5 8.5 8.5 9.0 9.0 9.0

Dispersion Stability (visual) Stable Stable Stable Stable Stable Stable Stable

Solids, % 28.20 29.86 30.60 34.50 28.78 29.40 31.30

Viscosity (25°C), cps 734 23 27 59 25 43 38

Density, g/ml 1.04 1.06 1.05 1.06 1.05 1.04 1.04

Complete Reaction Confirmed via FTIR

• FTIR was used to determine the extent of reaction.

• Below are examples of spectra for PUD/PA in Figure A and PUD/PO3G in Figure B.

• It is clear that there is no absorption in the 2230 cm-1 as indicated at the RED arrow.

• The disappearance of the peak at 2230 cm-1 corresponding to -NCO stretching vibration confirms the PUD-film was successfully synthesized and the reaction was complete as designed. This means the data from these PUD films are valuable and relevant for our evaluation and comparisons.

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Figure A. FTIR spectra of film based on PUD/PA dispersion

No absorption

Figure B. FTIR spectra of film based on PUD/POG dispersion

No absorption

PUD Film Properties

• Mechanical properties indicated that the PDO-based systems were on par with the referent systems except the PUD/PO3G films demonstrated exceptional toughness (see figure on mechanical properties to right).

• All films were transparent and clear as desired indicating a lack of soft segment crystallinity.

• Gloss values ranged from 77 to 100 and were considered acceptable (see table to the right).

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PUD FilmsFilm Clarity and Gloss

PDO films are showing the clarity and toughness needed to compete with industrial incumbent coatings systems produced from BDO Adipate, PTMG and PCL based systems.

Gloss* 77 100 90 81 91 96

*The films were placed on card-board, Gloss 2.

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Adhesion Properties on Aluminum

• PUDs as one component adhesives have many applications in textiles, footwear and automotive industries.

• The adhesive strength of PUDs based on PDO sebacate 1000 and BDO adipate 1000 were similar and higher than that of other PUDs, including that based on PDO adipate 1000.

• PUDs based on polyether polyols PO3G 1000 and PTMG 1000 exhibited similar adhesive strength, 568 psi and 589 psi, respectively.

• All PUDs exhibited “cohesive” bonding.

• Adhesion properties were measured per ASTM D1002 (apparent shear strength of Single-Lap-Joint adhesively bonded metal specimens by tension loading).

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Higher

Similar adhesive

strength

Adhesive strength and properties of the PUDs

Properties PUD/ PA PUD/PSb PUD/BA PUD/ PCL PUD/ PO3G PUD/ PTMG

Load at failure, psi 444 918 952 378 568 589

Strain at Break, % 6.05 6.15 6.26 5.68 6.79 8.13

Area under curve, (J) 0.38 ± 0.11 0.68 ± 0.17 0.73 ± 0.17 0.25 ± 0.05 0.50 ± 0.13 0.54 ± 0.17

Adhesive vs. cohesive10/10

cohesive

10/10

cohesive

10/10

cohesive

10/10

cohesive

10/10

cohesive

10/10

cohesive

Hardness, Adhesion and Impact Properties on Metal Substrate

• The PDO based systems performed equally to the reference commercial systems for hardness, tape adhesion and Impact resistance.

• No rupture was experienced from the maximum height with any of the PUD systems tested.

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Properties PUD/ PA PUD/PSb PUD/BA PUD/ PCL PUD/ PO3G PUD/ PTMG

Pencil hardness

(ASTM D3363)4H 4H 4H 4H 4H 4H

Adhesion Tape test

(ASTM D3359)5A 5A 5A 5A 5A 5A

Impact resistance

(ASTM D2794)

No rupture

from

maximum

height

No rupture

from

maximum

height

No rupture

from

maximum

height

No rupture

from

maximum

height

No rupture

from

maximum

height

No rupture

from

maximum

height

Hydrolytic Aging Test Results

• Toughness (psi) was measured before and after hydrolytic aging for 3 days at 50°C and 95% relative humidity.

• The tensile strength of all PUD-based films changed somewhat upon hydrolytic aging, which is expected due to water absorption and temperature.

• PUD/PO3G had the highest toughness after hydrolytic aging.

• The toughness of PUD films based on PTMG 1000 and PDO Sebacate 1000 slightly increased upon hydrolytic aging which could be due to annealing process.

• The PUD based on PDO sebacate 1000 performed better in hydrolytic aging testing than other types of polyester polyols based PUDs, which is due to hydrophobicity of Sebacic acid (C-10).

• PUD-based coatings performed very well in the hydrolytic aging testing. There was negligible change in hardness and adhesion in coatings after aging (refer to Table 12 in corresponding CPI paper).

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The effect of hydrolytic aging on properties of PUD-based films

Differential Scanning Calorimetry for PUD/PA film

Flexible segment transition, Tg,°C

Hard segment transition, °C

Differential Scanning Calorimetry for PUD/PO3G film

Flexible segment transition, Tg,°C

Hard segment transition, °C

Thermal Transitions of PUD Films

• Most of the polyols used in the PUD synthesis exhibited melt transition in the temperature range from ~18oC to 50oC (DSC), depending on the type of polyol.

• However, PUD-based films did not show polyol melt transitions (see two DSC examples of films to the right).

• The glass transition temperature (Tg) of PUD films was found to depend on the polyol type (see table below).

• The absence of soft segment crystallinity is important for clarity of coatings. All coatings and films based on PUDs were transparent and clear.

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Film Thermal Transitions PUD/ PA PUD/PSb PUD/BA PUD/PCL PUD/PO3G PUD/PTMG

Flexible segment, Tg ,°C (34.21) (43.46) (38.37) (59.68) (60.00) (59.68)

Hard segment transition, °C 175.09 186.87 172.03 188.02 182.38 188.02

The effect of various solvents on PUD films

Diameter of a liquid spot15 minutes after 1 drop of solvent applied.

Solvent Resistance of PUD based Films and Coatings on Metal

• Double-Rub Test (ASTM D 5402): There was no change of coating hardness after 25 double rubs with IPA and toluene as a solvent. There was slight change of coating thickness for most of coatings. The PUD based on polycaprolactone 1000 polyols exhibited significant change in thickness when exposed to IPA.

• Drop Test: In another solvent resistance test, a drop of various liquids (water, water acid solution, water alkaline solution, MEK and toluene) was applied on PUD-based films. The diameter of the liquid drop was measured 15 minutes after application. The diameter of the liquid spot varied slightly, depending on their composition and type of solvent. Overall, films based on polyether polyols PO3G and PTMG 1000 performed somewhat better than films based on polyester polyols, which was expected. PUD films based on PDO sebacate 1000 and BDO adipate 1000 were similar in this test and performed slightly better in contact with some solvents than films based on PDO adipate 1000 and polycaprolactone 1000 polyol.

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Conclusions

• Six types of waterborne PUDs were successfully synthesized from a range of different polyol chemistries by using DMPA (dimethylolpropionic acid) neutralized with triethylamine (TEA) as the ionic hydrophilic segment incorporated in the polymer backbone.

• The effects of different soft segments on the stability of waterborne PUDs, as well as the physical, mechanical, thermal and chemical resistance properties of the resultant PUDs as coatings and films were investigated.

• All coatings and films prepared were transparent and clear with relatively high gloss values which is important in industrial applications.

• Overall, a good combination of properties including high hardness combined with good toughness and impact resistance was observed. There was no change in hardness and adhesion in coatings aged for three days at 50oC and 95% relative humidity. The solvent resistance and hydrolytic aging test performance demonstrated that the PUD coatings from PDO-based polyols performed very well.

• DSC results indicated that films based on polyether PUDs had better flexibility and cold resistance than polyester-based films from PA, BA and PSb based polyol.

• Mechanical testing showed that PUD films based on PDO adipate 1000 were comparable to referent films based on BDO adipate 1000 and polycaprolactone 1000 and demonstrated higher performance than films based on PDO sebacate 1000.

• Toughness measurements illustrated that PUD/PO3G films have the best elastic behavior with good strength when compared to PUD/PTMG films and all other polyester-based PUD films studied. This finding is attributed to the odd number of carbon atoms and higher density of ether groups in the repeating unit of the PO3G soft-segment.

• The adhesive strength of polyester PUDs using PDO sebacate 1000 and BDO adipate 1000 were similar and higher than the other PUDs, including PDO adipate 1000. PUDs based on polyether polyols exhibited similar adhesive strength.

• In summary, this investigation demonstrates PDO-based polyester PUDs as well as PO3G-based polyether PUDs can be considered for use in industrial coatings and films across the a wide range of industrial applications previously mentioned.

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Thank you.

Copyright © 2016 DuPont Tate & Lyle Bio Products Company, LLC.

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

27

Stephen J. Hurff

Vice President – Marketing & Sales

DuPont Tate & Lyle Bio Products Company, LLC.

200 Powder Mill Road

Wilmington, DE 19803

stephen.j.hurff@dupont.com

www.duponttateandlyle.com

Ibrahim Sendijarevic

Business Development Director

Troy Polymers, Inc.

900 E. Mandoline Ave.

Madison Heights, MI 48071

sendijarevic@troypolymers.com

www.troypolymers.com