Applications of Polybutadiene-based...
Transcript of Applications of Polybutadiene-based...
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
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-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