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PRESENTED TO
The Brazilian Congress of Rubber The Brazilian Congress of Rubber
TechnologyTechnologyBY
Jerry McCallTSE Industries, Inc.
28-April-2004
� PolyurethanesPolyurethanes- Classify / Define
- Building Blocks
� Millable Polyurethane RubberMillable Polyurethane Rubber- Key Properties
- Ether vs. Ester and Sulfur vs. Peroxide
- TSE Product Portfolio
� Demanding Applications for:Demanding Applications for:- Footwear
- Rolls
What is Important to Know?What is Important to Know?
SLABSTOCK
MOLDING
SEMI-RIGID
PADDING FOAM
FLEXIBLE FOAM
SLABSTOCK
BOARDS WITH
FACING
CAVITY FILLING
FOAMS
IN-SITU FOAM
RIGID FOAM
FLEXIBLE
STRUCTURAL FOAMS
RIGID STRUCTURAL
FOAMS
REINFORCED
STRUCTURAL FOAMS
STRUCTURAL FOAM
FOAMS
CAST AND SPRAY
ELASTOMERS
THERMOPLASTIC
ELASTOMERS
PU RUBBER
SOLID PU
LAQUERS, PAINTS,
AND COATINGS
TEXTILE, PAPER,
LEATHER COATINGS
ADHESIVES
BINDERS
PU FOR SURFACES
FIBERS
MICROCAPSULES
GELS
ORGANO-MINERAL
PRODUCTS
SPECIAL
NON CELLULAR
CASE
POLYURETHANES
SLABSTOCK
MOLDING
SEMI-RIGID
PADDING FOAM
FLEXIBLE FOAM
SLABSTOCK
BOARDS WITH
FACING
CAVITY FILLING
FOAMS
IN-SITU FOAM
RIGID FOAM
FLEXIBLE
STRUCTURAL FOAMS
RIGID STRUCTURAL
FOAMS
REINFORCED
STRUCTURAL FOAMS
STRUCTURAL FOAM
FOAMS
CAST AND SPRAY
ELASTOMERS
THERMOPLASTIC
ELASTOMERS
PU RUBBER
SOLID PU
LAQUERS, PAINTS,
AND COATINGS
TEXTILE, PAPER,
LEATHER COATINGS
ADHESIVES
BINDERS
PU FOR SURFACES
FIBERS
MICROCAPSULES
GELS
ORGANO-MINERAL
PRODUCTS
SPECIAL
NON CELLULAR
CASE
POLYURETHANES
FORMS OF POLYURETHANESFORMS OF POLYURETHANES
� Polyurethanes are high molecular weight polymers
based on isocyanate chemistry which feature a wide
range of properties:
• Elastomeric, plastic or thermoset
• Full density or foamed
• Very soft to very hard polymers
� Polyurethane is a very general term which is utilized for a
significant number of different polymers.
� Polyurethanes are made up from a multitude of different
building blocks:
� The two most common are polyisocyanates and polyols
Understanding PolyurethanesUnderstanding Polyurethanes
PolyolsPolyolsPolytetramethylene Ether glycol
(C4-Ethers based on polytetrahydrofuran)
Polyesteradipates(based on adipic acid and diols like ethanediol, diethylene glycol,
butanediol, methylpropanediol, hexanediol, neopentyl glycol, etc., and
blends of diols)
IsocyanatesIsocyanatesAromatic Isocyanates (MDI, TDI)
Aliphatic Isocyanates (HDI, H12 MDI, TMXDI)
Chain ExtendersChain ExtendersLow molecular weight chain extenders like Ethylene glycol, 1,4-butanediol,
hydroquinone bis-(2-hydroxyethoxy)ether, Glycerol monoallylether,
trimethylolpropane monoallylether
BUILDING BLOCKS FOR BUILDING BLOCKS FOR
POLYURETHANE RUBBERPOLYURETHANE RUBBER
RNCO
ISOCYANATE
ROH
POLYOL
RNHCOOR
URETHANE
POLYURETHANE CHEMISTRYPOLYURETHANE CHEMISTRY
Difference of Polyurethane RubberDifference of Polyurethane Rubbertoto
Other Polyurethane ElastomersOther Polyurethane Elastomers
Castable Polyurethane
Pre-Polymer System
Produced with a high
excess of diisocyanate
Thermoplastic
Polyurethane (TPU)
Produced with a slight
excess of diisocyanate
Polyurethane RubberPolyurethane RubberProduced with a Produced with a
stoichiometric deficiency stoichiometric deficiency
of diisocyanateof diisocyanate
Achievable Properties of Achievable Properties of
Millable Polyurethane RubberMillable Polyurethane Rubber
� Mechanical properties such as abrasion resistance and
tensile strength far superior to all other known natural or
synthetic rubber
� Hardness from 25 A to 90 A
� Oil and fuel resistance better than NBR or HNBR
� Gas permeation as low as butyl rubber
� Heat resistance up to 120°C
� Low temperature flexibility down to minus 55°C
POLYMER COMPARISONPOLYMER COMPARISON
Ratings: E-Excellent; G-Good; F-Fair; P-Poor
F-GEPEF-GHeat build-up
FGFG-EEAbrasion
GFF-GGF-GCompression set
FGFGETear strength
GGFGECut resistance
EPPF-GEOzone resistance
175100120120100Max service temp C
25-9030-10020-10010-9510-95Hardness range,
Shore A
FG-EFG-EETensile strength
EPDMNatural
rubber
NitrileNeopreneUrethaneProperty/Material
Property Comparison of Ether Property Comparison of Ether
and Ester Polyurethane Rubberand Ester Polyurethane RubberPROPERTY
Abrasion Resistance
Coefficient of Friction
Wet Traction
Dry Traction
Water Resistance
Oils
Fuels
Solvents
Heat Resistance
Compression Set
Low Durometer
Bonding to Metal
Rebound
ETHER
E
High
F
E
E
G
F
F
G
F-G
G
E
High
ESTER
E
Medium
G
F
G (protected)
E
G
E
G-E
G-E
E
G
Low to High
Code: E = Excellent G = Good F = Fair P = Poor
COMPARISON OF SULFUR COMPARISON OF SULFUR
AND PEROXIDE CURESAND PEROXIDE CURESPROPERTY
Tensile strength
Tear strength, Die C
Compression set
Heat aging
Reversion resistance
Flexing resistance
Lower heat build-up
Abrasion resistance
Solvent resistance
SULFUR
+
+
-
-
-
+
+
+
+
PEROXIDE
-
-
+
+
+
-
-
+
+
TSE Product PortfolioTSE Product Portfolio
Transparent, brightly
colored parts
PeroxideMillathane 97Polyether/H12MDI
High temperatureSulfur/PeroxideMillathane HTPolyester/H12MDI
Abrasion resistance, low
durometer
Sulfur/PeroxideMillathane 76Polyester TDI
Hydrolytic stabilitySulfur/PeroxideMillathane CMMillathane
E34
Polyether/TDI
High stress strain, low
temp flex
PeroxideMillathane 5004Millathane 66Polyester/MDI
FeatureCureGradeGradeType
Selection of the Right Millable Selection of the Right Millable Polyurethane RubberPolyurethane Rubber
Judgement of the properties: ++ = excellent, + = good, o = fair, - = inadequate
-++o+++++Resistance to diesel fuels
o +++++++++Oil resistance
++ o++o++oResistance to hydrolysis
++ +---oCrystal clear colorless vulcanizates
o ++o++o++Permeability resistance
++ ++++++++Low temperature performance
-+o+++oMechanical properties at low hardness
-+ooo+Mechanical properties at high hardness
-+o+++Tear resistance
+ ++++++++Elongation at break
++ ++o+++Rebound resilience
+ ++++++++Tensile strength
-++o+o++Heat resistance
o ++ooo++Compression set
+++++++++++Abrasion resistance
Millathane
97
Millathane
66
Millathane
E34
Millathane
76
Millathane
CM
Millathane
5004Product
Peroxide
Cured
Peroxide
CuredSulfur Cured
Peroxide
CuredCure System
Selection of the Right Millable Selection of the Right Millable
Polyurethane RubberPolyurethane Rubber
Judgement of the properties: ++ = excellent, + = good, 0 = fair, - = inadequate
PROCESSING PROPERTIES
+++++++++++Hot air vulcanization
--+-+-Steam vulcanization
+++++++++++Extrusion
+++++0++Injection molding
+++++++++++Transfer molding
++++++++++++Compression molding
0+0++++Preparation of low-hardness
compounds
0+++++Preparation of high-
hardness compounds
Millathane
97
Millathane
66
Millathane
E34
Millathane
76
Millathane
CM
Millathane
5004Product
Peroxide
Cured
Peroxide
CuredSulfur Cured
Peroxide
CuredCure System
Bonding PU Rubber to MetalBonding PU Rubber to Metal
List of Adhesives
Chemlok 219, TYPly BN, Chemlok 218
Water-based Chemlok 8007/8560
Thixon 715-1/720 one coat
Thixon P-11 primer
Aqueous-based Thixon 7010
Why Use Millables ?Why Use Millables ?
� Better abrasion resistance
� Improve cut and tear resistance
� Reduce shoe weight
� Improve overall performance and durability
Ingredient phr
Polyether PU 100.0 Durometer, A 70
Zinc Stearate 0.5 Tensile Strength, MPa 25.6
Stearic Acid 0.5 Elongation, % 430
Carbowax 3.0 Tear Die C kN/m 54.2
Hi-Sil 233 30.0 Akron Abrasion, g loss 0.006
TP 95 8.0
Methyl Zimate 1.0
BTS 4.0
MBT 4.0
Thanecure ZM 2.0
Sulfur 2.0
MILLABLE PU OUTSOLE MILLABLE PU OUTSOLE
FORMULATIONFORMULATIONPolyether - 1
Ingredient phr
Polyether PU 100.0 Cure @ 150C 7.0’
Stearic Acid 0.5 Durometer, A 66
Fumed Silica 20.0 Tensile, MPa 30.1
Silane A-172 0.5 Elongation, % 682
Sartomer SR 231 6.0 Tear Die C, kN/m 53.1
Ultramarine Blue 0.003
Lupersol 231 0.5
MILLABLE PU OUTSOLE MILLABLE PU OUTSOLE
FORMULATIONFORMULATION
Polyether - 2
Ingredient phr
Polyether PU 100.0 Cure @ 150C 15.0’
Stearic Acid 0.5 Durometer, A 65
Fumed Silica 20.0 Tensile, MPa 26.6
Ultramarine Blue 0.003 Elongation, % 380
Lupersol 231 0.5 Tear Die C, kN/m 26.7
MILLABLE PU OUTSOLE MILLABLE PU OUTSOLE
FORMULATIONFORMULATION
Polyether - 3
Ingredient phr
Polyether PU 100.0 Cure @ 150C 15.0’
Stearic Acid 0.25 Durometer, A 69
Fumed Silica 20.0 Tensile, MPa 26.1
Silane A-172 0.25 Elongation, % 395
Sartomer SR 231 3.0 Tear Die C, kN/m 29.7
Ultramarine Blue 0.003
Lupersol 231 0.5
MILLABLE PU OUTSOLE MILLABLE PU OUTSOLE
FORMULATIONFORMULATION
Polyether - 4
Why Use Millables ?Why Use Millables ?
� Superior abrasion resistance
� Excellent cut and tear strength
� Great resistance to ozone, fuels and oils
� High compressive strength
� Very good low temperature flexibility
Why Not Cast ?Why Not Cast ?
� MPUR offers better physicals from 40 – 70 A
� Shorter cycle times
� Higher coefficient of friction
� Low durometer is easier to repair and offers
better tear strength
Polymer Comparison for RollsPolymer Comparison for Rolls
F
F-G
G
E
F
E
G-E
E
E
F-G
Abrasion
Heat Build-Up
GFF-GGF-GCompression Set
FGFGETear Strength
FGFGECut Resistance
EPPF-GEOzone resistance
175100120120100Max Service Temperature C
25-9030-10020-10010-9510-95Hardness Range Shore A
FG-EFG-EETensile Strength
EPDMNitrileNatural
RubberNeopreneUrethaneProperty/Material
Ratings:
E=Excellent, G=Good, F=Fair, P=Poor
Performance Comparison Performance Comparison
of Elastomers in rollsof Elastomers in rolls
757099100Scaled performance index (100=best)
8579112113Performance index
21323Swell resistance in polar solvents (e.g.,
ultraviolet inks)
32334Low heat build-up at high operating
speeds
32454Tear and abrastion resistance
45555Ink pick-up
34555Swell resistance in non-polar solvents
(oils)
43555Stability of hardness in solvents
(resistance to extraction)
Property
NeopreneNitrileMillable
Urethanes
Cast
Urethanes
Relative
ImportanceElastomer type
Ingredient phr Cure time @ 160°C 15’
Millathane E34 100.0 Durometer, A 49
Zinc Stearate 0.5 Tensile, MPa 25.2
Poly AC617A 2.0 Elongation, % 610
Akrofax 758 10.0 Tear Die C, kN/m 42.7
Hi-Sil 233 10.0 Bayshore Rebound, % 56
TP 95 10.0
MBTS 4.0
MBT 2.0
Thanecure ZM 1.0
Sulfur 1.5
MILLABLE PU ROLLER FORMULATIONMILLABLE PU ROLLER FORMULATIONLow Durometer Sulfur Cure
Ingredient phr Durometer, A 89
Millathane 66 100.0 Tensile, MPa 22.7
Stearic Acid 0.5 Elongation, % 278
Poly 617A 2.0 Tear, kN/m 130
Resin Process Aid 4.0 DIN Abrasion, mm3 lost 85
Water washed Clay 60.
Trimethacrylate 12.5
DBPH 50 6.0
MILLABLE PU ROLLER FORMULATIONMILLABLE PU ROLLER FORMULATIONHigh Durometer Peroxide Cure
Ingredient phr Durometer, A 25
Millathane 76 100.0 Tensile ,MPa 22
Zinc Stearate 0.5 Elongation, % 745
Factice 11 12.0 Resistivity, Ohm CM 1.2 E +09
Struktol AW1 20.0
MBTS 4.0
MBT 2.0
Thanecure ZM 1.0
Sulfur 1.5
MILLABLE PU ROLLER FORMULATIONSMILLABLE PU ROLLER FORMULATIONSLow Durometer antistatic
MILLATHANE MILLATHANE MILLABLE POLYURETHANEMILLABLE POLYURETHANE
APPLICATIONSAPPLICATIONS
OO--RingsRings Tester PadsTester Pads
SealsSeals GasketsGaskets
HoseHose BeltingBelting
BladderBladder BushingsBushings
BearingsBearings Solid TiresSolid Tires
Pharmaceutical StoppersPharmaceutical Stoppers
Vibration DampersVibration Dampers
MILLATHANE MILLATHANE MILLABLE POLYURETHANEMILLABLE POLYURETHANE
