Applications of Polybutadiene-based TPU s

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

Liquid polymer : Ricon, Krasol, Poly Bd Functionalities: R R x y z m Molecular weight (< 10,000g/mol) Vinyl / styrene content Wide range of Tg and viscosity Hydrogenation ( partial/ complete) Hydroxyl Epoxy Maleic anhydride Methacrylate Acid Tailor made

HCR Wingtack, Norsolene Composition spectrum A wide range of polarity CH3 P AMS Indene CH3 Styrene CH3 Vinyl toluene CH3 Aliph. 1 H (%) 100 90 80 70 60 50 40 Wingtack 98 Wingtack Extra Wingtack ET Wingtack 86 Norsolene A (PIP) Norsolene M (TERP) Norsolene S Norsolene W Wingtack STS

Metallic Monomers Dymalink (TM) Zinc Diacrylate, Dimethacrylate, Monomethacrylate (ZDA, ZDMA, ZMMA) Calcium Diacrylate (CaDA) free-flowing powders Very reactive with free radicals Zn C a zinc diacrylate Dymalink 705 calcium diacrylate Dymalink 636 Zn Zn H zinc dimethacrylate Dymalink 708 zinc monomethacrylate (ZMMA) Dymalink 709

TPU formation Polybutadiene TPU is done from Krasol BH 2000 which has 65% vinyl = Polyol = diisocyanate = chain extender polymerization soft segment hard segment n phase separation effective hard block domains (H-bonding) 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 Typical properties Type Soft segment Hard segment Poly Bd 2035 TPU TPU Polybutadiene Polyurethane Poly Bd 7840 TPU TPU Polybutadiene Polyurethane Shore A Hardness Tensile Strength (MPa) Elongation (%) 100% Modulus (MPa) Glass Transition Temp( C) Softening Point ( C) Compatibility with SBR, BR, THF, Ethyl acetate 82 25.0 510 8.7-35 90 No 81 27.2 540 8.1-34 88 Yes

Advantages of Polybutadiene based TPU

Characteristics - 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

Chemical Resistance 90 80 Share A Hardness 70 60 50 40 30 20 Poly bd 7840 TPU Polyether TPU 10 0 reference 10% CH3CH 60% H2S4 40% HN3 50% NaH EtH 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

Electrical Resistivity Poly bd 7840 TPU Polyether TPU Volume resistivity (Ωm) 1.03 x 10 14 5.48 x 10 9 Surface resistivity (Ω) 1.54 x 10 16 1.03 x 10 13 Diene-based TPUs demonstrate much higher electrical resistivity compared to Polyether TPUs Potential for wire & cable applications

Crosslinkable Material 45 PPA Curve 180 C : Peroxide Vulcanisation of TPU2035 S' ; dnm 40 35 30 25 20 15 10 1phr Luperox F40P 3phr Luperox F40P 6 phr Luperox F40P Formulation : TPU 2035 100 Ricon 130 20 Silica 20 Increase of the torque answer as a network is being built. 5 0 0 5 10 15 20 25 30 Time; min Co-reticulation with diene elastomers possible (Sulfur and peroxides)

Applications in Rubber Systems 13 Presentation Title

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 16 Presentation Title

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 bjective: to demonstrate adhesion to both sulfur-cured diene compound and polyurethane, effectively forming a tie-layer polyurethane Poly bd 7840 TPU rubber Rubber Compound Ingredient phr Non-Productive BR or PI 100.0 Carbon Black (N330) 50.0 Process il (paraffinic) 10.0 Antioxidant (TMQ) 1.0 Zinc xide 5.0 Stearic Acid 2.0 Productive Sulfur 2.5 Accelerator (TBBS) 0.7 in-situ curing of laminate to t 90 of rubber formulation

Qualitative Results Thermoplastic Materials to Rubber Compound Substrate B Substrate A Thermoplastic Materials to other Thermoplastics Component A Component B Failure Rubber compound Poly Bd 7840 TPU cohesive Rubber compound Polyether TPU adhesive Rubber compound Polyester TPU adhesive Rubber compound SBS cohesive Rubber compound SIS cohesive Rubber compound SEBS adhesive Component A Component B Failure Poly Bd 7840 TPU Polyether TPU cohesive Poly Bd 7840 TPU Polyester TPU cohesive SBS TPE Polyether TPU adhesive SBS TPE Polyester TPU adhesive nly diene-containing thermoplastic materials adhered to cured rubber compound nly Poly bd 7840 TPU consistently adhered to PU components The diene-urethane segmental structure of Poly bd 7840 TPU can successfully mate rubber components to urethane components

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 20 Presentation Title

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 Ingredient phr Model formulation: Non-Productive ESBR (1502) a 100.0 Carbon Black (N330) 60.0 Process il (aromatic) 20.0 Antioxidant (IPPD) b 2.0 Antioxidant (TMQ) c 1.0 Zinc xide 3.0 Stearic Acid 2.0 Thermoplastic Elastomer 0, 5.0, 10.0, 25.0 Productive Sulfur 2.0 Accelerator (CBS) d 1.4 a emulsion styrene-butadiene rubber, 23.5% styrene b N-isopropyl-N'-phenyl-p-phenylenediamine c 2,2,4-trimethyl-1,2-hydroquinoline d N-cyclohexylbenzothiazole-2-sulfenamide

Uncured Properties Uncured shear modulus gives an indication of processing characteristics @ T < T soft, G increases with loading: green strength Poly bd 7840 TPU improves processing at elevated temps (lower T soft ) Poly bd 7840 TPU G, 8.33 Hz, 15% strain Normalized Value 140 130 120 110 100 90 80 70 60 50 Shear Modulus (G') 0 5 10 25 Poly bd 7840 phr 100 C 60 C

Cured Properties Normalized Value 150 140 130 120 110 100 90 80 70 60 50 Tensile Properties 0 5 10 25 Tensile Strength % Elongation 100% Modulus 300% Modulus Tear Strength Poly bd 7840 TPU (phr) As a function of Poly bd 7840 TPU loading: 100% modulus maintained, 300% increased (M300/M100 increased) tensile strength and tear increased

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 0.9 0.9 0.8 0.8 0.7 0.7 Tangent Delta 0.6 0.5 0.4 0.3 control 5 phr 10 phr 25 phr Tangent Delta 0.6 0.5 0.4 0.3 control 5 phr 10 phr 25 phr 0.2 0.1 0-125 -100-75 -50-25 0 25 50 75 100 125 0.2 0.1 0-125 -100-75 -50-25 0 25 50 75 100 125 Temperature (C) Temperature (C) 11 Hz, 0.1% strain

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 25 25 crack width (mm) 20 15 10 5 10 phr (modulus~ 2.0 MPa) 25 phr (modulus~2.4 MPa) crack width (mm) 20 15 10 5 0 0 5000 10000 15000 20000 25000 30000 35000 cycles 0 0 5000 10000 15000 20000 25000 30000 35000 cycles control SBS Poly bd 7840 TPU Polyether TPU

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 Adhesion Results Tangent Delta 1.0 0.9 0.8 0.7 0.6 0.5 0.4 0.3 0.2 0 phr 5 phr 15 phr 25 phr Adhesive Force (lb/in) 25 20 15 10 5 phase separated 0.1 0.0-150 -100-50 0 50 100 150 0 0 5 15 25 Temperature (C) Poly bd 7840 TPU (phr) 11 Hz, 0.1% strain adhesive force correlates to phase separation ARDL peel adhesion test results

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