Polyurea Spray Elastomers an Overview of Current Technology
Transcript of Polyurea Spray Elastomers an Overview of Current Technology
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Jerry L. Reddinger and Kenneth M. HillmanHuntsman Corporation
Austin, Texas USA
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■ 1980’s: Texaco’s Austin Research Laboratories develop polyurea reaction-injection-molding (RIM) for automotive exterior body panel applications.
■ 1989: Texaco’s Austin Research Laboratories develop and introduce 100% solids polyurea spray elastomer coatings.
■ 1990’s: Numerous equipment advances by industry leaders.
■ 1990’s: Huntsman Corporation and ICI Polyurethanes co-develop and commercialize isocyanate prepolymers for polyurea spray.
■ 1990’s: Introduction of key secondary amine chain extenders for use in polyurea elastomer coatings.
■ 2000: Formation of Polyurea Development Association
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UreaLinkage
UrethaneLinkage
NR
H
O
O
R'O N
O
Hn
R'HO OH
ROCN NCO +
Catalyst
IsocyanatePrepolymer
Polyol
POLYURETHANEPOLYURETHANE
NR
H
N
O
R'N N
O
HH HnR'
H2N NH2R
OCN NCO +
IsocyanatePrepolymer
Polyamine
POLYUREAPOLYUREA
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ResinComponent
POLYUREA Class 1Hybrid
Class 2Hybrid
Class 3Hybrid
PU
MMaaiinn Polyetheramine Polyetheramine Polyetheramine Polyol Polyol
CChhaaiinnEExxtteennddeerr Polyamine
Polyamine(Hydroxyl
Containing)Polyol Polyamine Polyol
CCaattaallyyssttPPaacckkaaggee NONE NONE YES YES YES
NOTE: A myriad of other additives can be incorporated into any of these systems. Examples include pigments, adhesion promoters, UV-absorbers, anti-oxidants, and texturing agents.
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■ SPRAYABLE COATING APPLICATIONS
■ TWO COMPONENT, 100% SOLIDS SYSTEMS
■ 1:1 VOLUME MIX RATIO, WIDE FORMULATION LATITUDE
■ FAST REACTIVITY AND CURE WITHOUT A CATALYST
■ RELATIVELY MOISTURE AND TEMPERATUREINSENSITIVE DURING APPLICATION
■ EXCELLENT PHYSICAL PROPERTIES
■ HIGH THERMAL STABILITY (UP TO 175° C)
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■ Tensile strength up to 28 MPa (4000 psi)
■ Shore Hardness A30 to D80
■ Elongation up to 1200 %
■ Tear strength up to 127000 N/m (725 pli)
■ 100% Modulus up to 14 MPa (2000 psi)
■ 300% Modulus up to 17 MPa (2500 psi)
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CH2
OCN NCO
4,4'-MDI
CH2
OCN
NCO
2,4'-MDI
Aromatic-Based Systems
Aliphatic-Based Systems
H3CCH3 CH3
NCO
NCO
IPDI
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CHH2N CH2
CH3
OCH2
CHNH2
CH3
x
x
y
z
x + y + z = ~81
HC
CH2[OCH2CH(CH3)]NH2
CH2[OCH2CH(CH3)]NH2
[OCH2CH(CH3)]NH2
JEFFAMINE® T-5000
Product x
JEFFAMINE D-400 5-6 JEFFAMINE D-2000 32-34
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NH2
NH2
CH2
CH3
CH2
H3C
H3C
ETHACURE® 100
NHHN
H3CCH3 CH2
CH3CH2
H3C
UNILINK ® 4200
NH2
NH2
S
SH3C
CH3
H3C
ETHACURE® 300CLEARLINK ® 1000
NH
H3C CH2
CH3
HN
CH3CH2
H3C
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SYSTEM TYPE: aromatic or aliphatic
UREA DENSITY INDEX (UDI): directly related to %NCO value of prepolymer
PREPOLYMER TYPE: isocyanate type, isomer distribution, and polyol (polyetheramine) composition can greatly affect overall elastomer properties
INDEX: can be used to help overcome brittleness and extend working time
CROSSLINK DENSITY: can affect brittleness, permeability, and chemical resistance
SECONDARY AMINE CONTENT: modulates system speed
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■ Component Viscosity: <2000 cps (at RT) If too high: pump cavitation may occur
If mismatched: large pressure differential may exist
along with poor mixing
■ Operating Pressure: >138 bar (2000 psi) If too low: poor mixing and loss of spray
pattern may occur.
■ System Temperature: 60-80C (150-170F) If too low: poor mixing and loss of spray
pattern may occur.
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ISOCYANATE COMPONENTISOCYANATE COMPONENTISOCYANATE COMPONENTISOCYANATE COMPONENT
15.4% NCO MDI-Based
Quasi-Prepolymer 100%
RESIN COMPONENTRESIN COMPONENTRESIN COMPONENTRESIN COMPONENT
JEFFAMINE® D-2000 57.7%
JEFFAMINE® T-5000 5.3%
ETHACURE® 100 18.6%
UNILINK ® 4200 18.6%
Index: 1.05 Volume Ratio: 1:1
Gel Time: 7.0 sTack-Free Time: 12.5 s
Hardness: D51Tensile Strength: 14.7 MPa
(2128 psi)Elongation: 529 %Modulus, 100%: 7.1 MPa
(1027 psi)Modulus, 300%: 10.1 MPa
(1471 psi)Tear Strength: 79846 N/m
(456 pli)
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ISOCYANATE COMPONENTISOCYANATE COMPONENTISOCYANATE COMPONENTISOCYANATE COMPONENT
20.4% NCO MDI-Based
Quasi-Prepolymer 100%
RESIN COMPONENTRESIN COMPONENTRESIN COMPONENTRESIN COMPONENT
JEFFAMINE® D-2000 22.0%
JEFFAMINE® D-400 26.0%
JEFFAMINE® T-5000 10.0%
ETHACURE® 100 27.0%
UNILINK ® 4200 15.0%
Index: 1.10 Volume Ratio: 1:1
Gel Time: 2.5 sTack-Free Time: 4.0 s
Hardness: D70Tensile Strength: 24.3 MPa
(3522 psi)Elongation: 73 %Tear Strength: 125372 N/m
(716 pli)
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IsocyanateIsocyanateIsocyanateIsocyanate
15.4% NCO MDI-Based 100%
Resin BlendResin BlendResin BlendResin Blend
JEFFAMINE® D-2000 51.4%
JEFFAMINE® T-5000 10.3%
ETHACURE® 100 9.5%
UNILINK ® 4200 20.6%
TIOXIDE ® TiO2 8.2%
INDEX: 1.30 VOLUME A/B: 1:1
WORKING TIME: ~2 min
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POLYUREA IS NOT A MIRACLE COATING!!!
■ The appropriate polyurea elastomer system must be selected for the given application.
■ Even the best suited elastomer system will fail without proper substrate preparation.
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POLYUREA TRIGGERMANSINCE 1985
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CHIP EMERSONCHIP EMERSON RICHARD ROMERORICHARD ROMERO
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