Applications of Polybutadiene-based TPU’s

AGENDA

Introduction TPU synthesis Advantages of polybutadiene based TPU Use of TPU as a tie layer Use of TPU as an additive

Molecular weight (< 10,000g/mol)

Vinyl / styrene content

Wide range of Tg and viscosity

Hydrogenation ( partial/ complete)

Liquid polymer : Ricon, Krasol, Poly Bd

Functionalities:

Hydroxyl

Epoxy

Maleic anhydride

Methacrylate

Acid

Tailor made…

R R

x y z m

HCR – Wingtack, Norsolene

Composition spectrum – A wide range of polarity

Aliph. 1H (%)

100 40 50 60 90 70

Norsolene S

Norsolene W

Norsolene A (PIP)

Norsolene M (TERP)

Wingtack Extra

Wingtack ET

Wingtack STS

Wingtack 86

Wingtack 98

80

CH3

CH3CH3

CH3

Vinyl toluene

Styrene

AMS Indene

P

Metallic Monomers – Dymalink (TM)

Zinc Diacrylate, Dimethacrylate, Monomethacrylate (ZDA, ZDMA, ZMMA)

Calcium Diacrylate (CaDA)

• free-flowing powders

• Very reactive with free radicals

zinc diacrylate Dymalink 705

zinc dimethacrylate Dymalink 708

OZn

O

O O

OZn

O

O Ozinc monomethacrylate (ZMMA)

Dymalink 709

OZn

OH

O

O C a

O

O O calcium diacrylate Dymalink 636

TPU formation

= diisocyanate = chain extender = Polyol polymerization

effective hard block domains (H-bonding)

soft segment

hard segment

n phase separation

Polybutadiene TPU is done from Krasol BH 2000 which has 65% vinyl

TPU2035 is matured PU under granulate form Linear structure provides thermoplastic properties :

Mold material Possibility to blend with other elastomer ( polar and non-polar)

Typical Properties

Yes NoCompatibility with SBR, BR, THF, Ethyl acetate…

8127.25408.1-3488

8225.05108.7-3590

Shore A HardnessTensile Strength (MPa)Elongation (%)100% Modulus (MPa)Glass Transition Temp(°C)Softening Point (°C)

TPUPolybutadienePolyurethane

TPUPolybutadienePolyurethane

TypeSoft segmentHard segment

Poly Bd 7840 TPUPoly Bd 2035 TPUTypical properties

Yes NoCompatibility with SBR, BR, THF, Ethyl acetate…

8127.25408.1-3488

8225.05108.7-3590

Shore A HardnessTensile Strength (MPa)Elongation (%)100% Modulus (MPa)Glass Transition Temp(°C)Softening Point (°C)

TPUPolybutadienePolyurethane

TPUPolybutadienePolyurethane

TypeSoft segmentHard segment

Poly Bd 7840 TPUPoly Bd 2035 TPUTypical properties

Advantages of Polybutadiene based TPU

- Lower density

- polybutadiene based TPU: 0.95 to 1.10

- Polyether & polyester based TPU: 1.10 to 1.30

- Lower Moisture Vapour Transmission Rate due to the higher hydrophobicity of the polybutadiene backbone

TPU 7840 Poly Bd Estane range

MVTR (g/m2 per 24h) 0.5 - 1 > 300

Characteristics

Chemical Resistance

By adding diene character, Poly bd 7840 TPU exceeds the acid and base resistance of common Polyether TPUs

Diene-based TPUs are soluble in certain hydrocarbon solvents, and can be applied from solution to create a thin film

0102030405060708090

reference 10%CH3COOH

60%H2SO4

40% HNO3

50% NaOH

EtOH

Shar

e A

Hard

ness Poly bd 7840 TPU

Polyether TPU

Electrical Resistivity

Diene-based TPUs demonstrate much higher electrical resistivity compared to Polyether TPUs

Potential for wire & cable applications

Poly bd 7840 TPU Polyether TPU

Volume resistivity (Ωm) 1.03 x 1014 5.48 x 109

Surface resistivity (Ω) 1.54 x 1016 1.03 x 1013

Increase of the torque answer as a network is being built.

Crosslinkable Material

Co-reticulation with diene elastomers possible (Sulfur and peroxides)

PPA Curve 180°C : Peroxide Vulcanisation of TPU2035

0

5

10

15

20

25

30

35

40

45

0 5 10 15 20 25 30

Time; min

S' ;

dNm

1phr Luperox F40P3phr Luperox F40P6 phr Luperox F40P

Formulation :TPU 2035 100Ricon 130 20Silica 20

Applications in Rubber Systems

Presentation Title 13

Potential

The application of urethanes (traditional PUs and TPUs) has been limited due to poor compatibility with rubber systems

• poor thermodynamics of mixing – pre-crosslinked PU / polarity

• incompatible with sulfur cure

• no adhesion between dissimilar adjoining components

Diene-based TPUs overcome these issues by incorporating a polybutadiene soft segment

• commercial production only recently possible: development of Krasol linear polybutadiene diols, and prepolymers derived thereof

• expanded thermodynamic and cure compatibility

• demonstrates adhesion to both rubber and PU substrates

Applications

1. “Tie-Layer” adhering a Urethane component to a Rubber Compound substrate

• Diene-segments interpenetrate and co-cure with rubber compound

• Urethane segments bond to similar structure in PU

2. Additive to a traditional Rubber Compound

• varied loading increases impact on physical properties

• impart modulus while minimizing hysteresis (vs. TPE)

• realize advantages from phase structure at higher loadings

1. Adhesive Tie-Layer

Presentation Title 16

Adhesive Tie-Layer

Structural novelty creates opportunities to compatibilize dissimilar elastomeric materials

• Diene segment ⇒ interacts with diene-based compound

• Urethane segment ⇒ interacts with PU material

Objective: to demonstrate adhesion to both sulfur-cured diene compound and polyurethane, effectively forming a “tie-layer”

polyurethane

Poly bd 7840 TPU

rubber in-situ curing of laminate to t90 of rubber formulation

Rubber Compound Ingredient phr

Non-Productive BR or PI 100.0 Carbon Black (N330) 50.0 Process Oil (paraffinic) 10.0 Antioxidant (TMQ) 1.0 Zinc Oxide 5.0 Stearic Acid 2.0

Productive Sulfur 2.5 Accelerator (TBBS) 0.7

Qualitative Results

Only diene-containing thermoplastic materials adhered to cured rubber compound

Only Poly bd 7840 TPU consistently adhered to PU components

Thermoplastic Materials to Rubber Compound

Thermoplastic Materials to other Thermoplastics

The diene-urethane segmental structure of Poly bd 7840 TPU can successfully mate rubber components to urethane components

Substrate B

Substrate A

Component A Component B FailureRubber compound Poly Bd 7840 TPU cohesiveRubber compound Polyether TPU adhesiveRubber compound Polyester TPU adhesiveRubber compound SBS cohesiveRubber compound SIS cohesiveRubber compound SEBS adhesive

Component A Component B FailurePoly Bd 7840 TPU Polyether TPU cohesivePoly Bd 7840 TPU Polyester TPU cohesive

SBS TPE Polyether TPU adhesiveSBS TPE Polyester TPU adhesive

Potential Adhesion Applications

Dissimilar Polymers • between polar and non-polar elastomeric compounds

• between compounds with incompatible cure systems

Elastomeric Compound to Polyurethanes • adhering elastomeric compounds to thermoset or thermoplastic urethanes

Elastomeric Compounds to Fabrics/Cord • treatment of fabric with soluble Poly bd 7840 TPU

2. TPU as a Rubber Additive

Presentation Title 20

TPU as an Additive

Thermoplastic materials were added to a model tire carcass formulation

• Tensile, viscoelastic, and flex fatigue properties were evaluated as a function of loading

• Model formulation:

Ingredient phr

Non-Productive ESBR (1502)a 100.0Carbon Black (N330) 60.0Process Oil (aromatic) 20.0Antioxidant (IPPD)b 2.0Antioxidant (TMQ)c 1.0Zinc Oxide 3.0Stearic Acid 2.0Thermoplastic Elastomer 0, 5.0, 10.0, 25.0

Productive Sulfur 2.0Accelerator (CBS)d 1.4

aemulsion styrene-butadiene rubber, 23.5% styrenebN-isopropyl-N'-phenyl-p-phenylenediaminec2,2,4-trimethyl-1,2-hydroquinolinedN-cyclohexylbenzothiazole-2-sulfenamide

Uncured Properties

Uncured shear modulus gives an indication of processing characteristics

• @ T < Tsoft, G’ increases with loading: green strength

• Poly bd 7840 TPU improves processing at elevated temps (lower Tsoft)

Poly bd 7840 TPU

G’, 8.33 Hz, 15% strain

Shear Modulus (G')

50

60

70

80

90

100

110

120

130

140

0 5 10 25Poly bd 7840 phr

Nor

mal

ized

Val

ue

100 C

60 C

Cured Properties

As a function of Poly bd 7840 TPU loading:

• 100% modulus maintained, 300% increased (M300/M100 increased)

• tensile strength and tear increased

Tensile Properties

5060708090

100110120130140150

0 5 10 25Poly bd 7840 TPU (phr)

Norm

aliz

ed V

alue

Tensile Strength

% Elongation

100% Modulus

300% Modulus

Tear Strength

Compatibility

The compatibility of the diene-based thermoplastic elastomers in the model formulation was evaluated (DMA)

• SBS was compatible at all loadings

• Poly bd 7840 TPU became incompatible at 25 phr

SBS TPE Poly bd 7840 TPU

11 Hz, 0.1% strain

0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

-125 -100 -75 -50 -25 0 25 50 75 100 125

Temperature (C)

Tang

ent D

elta control

5 phr

10 phr

25 phr

0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

-125 -100 -75 -50 -25 0 25 50 75 100 125

Temperature (C)

Tang

ent D

elta control

5 phr

10 phr

25 phr

Flex Fatigue

Phase structure required to impart improved crack growth resistance

• Demattia samples tested at similar modulus (given below)

• @ 10 phr, no differentiation in performance

• @ 25 phr, TPUs phase separate and improve flex fatigue

10 phr (modulus~ 2.0 MPa) 25 phr (modulus~2.4 MPa)

control Poly bd 7840 TPU SBS Polyether TPU

0

5

10

15

20

25

0 5000 10000 15000 20000 25000 30000 35000

cycles

crac

k w

idth

(mm

)

0

5

10

15

20

25

0 5000 10000 15000 20000 25000 30000 35000

cycles

crac

k w

idth

(mm

)

Additive for Adhesion

Alternatively, Poly bd 7840 TPU was used as an additive to promote adhesion between a cis-PI compound and a polyurethane

• 100 phr PI (GY Natsyn) / 60 phr CB / sulfur cured • 0, 5, 15, 25 phr TPU resin – adhesion to poly(ether) polyurethane

DMA Results

11 Hz, 0.1% strain

Adhesion Results

ARDL peel adhesion test results

adhesive force correlates to phase separation

0.00.10.20.30.40.50.60.70.80.91.0

-150 -100 -50 0 50 100 150

Temperature (C)

Tang

ent D

elta

0 phr

5 phr

15 phr

25 phr

0

5

10

15

20

25

0 5 15 25

Poly bd 7840 TPU (phr)

Adhe

sive

For

ce (l

b/in

) phase separated

Summary

Diene-based TPUs have a unique structure incorporating both soft, hydrophobic diene and hard urethane segments

The resultant physical properties of the novel material reflect the somewhat amphiphilic nature of its structure

Diene-based Poly bd 7840 TPU can expand the use of thermoplastic urethanes into applications otherwise closed to traditional TPUs, including the rubber market