update and overview of polyurea spray technology and new
TRANSCRIPT
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Mark L. Posey Huntsman LLC : Austin Research Labs
2005 Polyurethane Manufacturers Association Annual Meeting Rancho Mirage, CA April 17-19, 2005
Update and Overview of Polyurea Spray Technology and New Amine
Chain Extenders Useful in Polyurethane Systems
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The History and Background of Polyurea Spray Elastomers
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1980’s: Texaco Chemical’s Austin Research Laboratories develop polyurea reaction-injection-molding (RIM) for automotive exterior body panel applications.
1989: Texaco Chemical’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. 1995: UOP introduces key aliphatic secondary amine chain
extender for use in polyurea elastomer coatings. 1990’s: Bayer introduces slower aspartic ester secondary amine products in late 1990s. Allows first “roll-on” polyureas.
Key Developments Along the Polyurea Spray Elastomer Timeline
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2000: Formation of the Polyurea Development Association 2002: Huntsman commercializes JEFFLINK® 754 chain extender for
polyurea and other polymer markets. 2002: UOP suddenly exits chain extender market in December. 2003: UOP sells rights to UNILINK® 4200 and CLEARLINK® 1000
chain extenders to Dorf Ketal in India. 2004: Nissan is first company to offer OEM truck-bed liner. 2005: Huntsman commercializes Secondary Polyetheramines.
Key Developments Along the Polyurea Spray Elastomer Timeline-cont.
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ESTIMATED 2001 SYSTEM SOLD: 20-25MM LBS ESTIMATED MARKET VALUE: $60-75MM GEOGRAPHIC BREAKDOWN:
NORTH AMERICA 85% APAC 10% EUROPE 4% SOUTH AMERICA 1%
*-2001 Industry Report Conducted by the Polyurea Development Association
THE POLYUREA SPRAY ELASTOMER MARKET AT A GLANCE*
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Concrete Bedliners Steel Roofing Other
60%
10%
15%
5%
*-2001 Industry Report Conducted by the Polyurea Development Association
10%
POLYUREA SPRAY ELASTOMER APPLICATION AREAS*
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CHEMICAL REACTIONS: POLYURETHANE AND POLYUREA
ROCN NCO
R'HO OH
NR
OR'
O NH
O O
H
+
Isocyanate Polyol
Urethane
=
n
ROCN NCO
R'HR"N NR"H
NR
NR'
NH NH
O O
H R"
+
Isocyanate Polyamine
Urea
=n
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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.
THE POLYUREA/POLYURETHANE ELASTOMER SPECTRUM
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• Sprayable coating application. • Two component, 100% solids systems, Zero VOC. • 1:1 volume mix ratio, wide formulation latitude. • Fast reactivity and cure without a catalyst, lack of catalyst
leads to better long term stability. • Relatively moisture and temperature insensitive during
application. • Excellent physical properties. • High thermal stability (up to 175° C). • Excellent abrasion resistance.
BENEFITS OF POLYUREA SPRAY ELASTOMERS
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• Tensile Strength up to 28 MPa (4000 psi) • Shore Hardness A30 to D75 • Elongation up to 1200 % • Tear Strength up to 127000 N/m (725 pli) • 100% Modulus up to 14 MPa (2000 psi) (Stress@100%) • 300% Modulus up to 17 MPa (2500 psi) (Stress@300%)
TYPICAL PHYSICAL PROPERTIES FOR POLYUREA ELASTOMERS
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Common Raw Materials for Polyurea Spray Elastomers
“New” Amines for Possible Use in Polyurethanes
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CH2
OCN NCO
4,4'-MDI
CH2
OCN
NCO
2,4'-MDI
Aromatic-Based Systems
Aliphatic-Based Systems
HDI Trimer
ISOCYANATE SYSTEMS FOR POLYUREA ELASTOMER COATINGS
IPDI
H3CCH3 CH3
NCO
NCO
N
CN
C
NC (CH2)6 ---NCOOCN---
6(H2C)
(CH2)6 -----NCO
O
OO
OCN NCO
H12MDI
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Aromatic-Based Systems
Aliphatic-Based Systems
ISOCYANATE PREPOLYMERS FOR ELASTOMER COATINGS
NH
CH3
OO
CH3
O
NH
O~32
CH3H3C
H3C
NHOCN
CH3H3C
H3C
NCOHN
IPDI - D-2000 Prepolymer
O
CH3
OO
CH3
O
O NH
O NCO~32NH
OCN
MDI-PPG-2000 Prepolymer
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NH2
NH2
CH2CH3
CH2H3C
H3C
ETHACURE® 100 curing agent
NHHN
H3CCH3 CH2CH3
CH2H3C
UNILINK® 4200 chain extender
NH2
NH2
S
SH3C
CH3H3C
ETHACURE® 300 curing agent
AROMATIC CHAIN EXTENDERS FOR POLYUREA ELASTOMER COATINGS
ETHACURE is a trademark of Albemarle. UNILINK is a trademark of Dorf Ketal.
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JEFFLINK® 754 curing agent
CYCLOALIPHATIC CHAIN EXTENDERS
CLEARLINK® 1000 curing agent HN NH
NH
NH
CLEARLINK is a trademark of Dorf Ketal. JEFFLINK is a trademark of Huntsman LLC or an affiliate thereof in one or more, but not all countries.
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Secondary Aspartic Ester Amines
NH NHO
O
O
O
O
O O
O
DESMOPHEN® NH1420 curing agent
DESMOPHEN is a trademark of Bayer.
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CHH2N CH2
CH3
OCH2
CHNH2
CH3x
JEFFAMINE® POLYETHERAMINES FOR POLYUREA ELASTOMER COATINGS
O
O
CH2
NH2
O NH2
NH2
R
x
y
z
n
JEFFAMINE(R) T-3000 amine x + y + z = ~ 50
JEFFAMINE(R) T-5000 amine x + y + z = ~ 85
JEFFAMINE(R) T-403 amine x + y + z = ~ 5.3R = C2H5 n = 1
R = H n = 0
R = H n = 0
JEFFAMINE is a trademark of Huntsman LLC or an affiliate thereof in one or more, but not all countries.
Product xJEFFAMINE® D-400 amine 5-6JEFFAMINE® D-2000 amine 32-34
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New Secondary Polyetheramines • Proprietary Huntsman catalyst technology allows high secondary amine
formation with little primary or tertiary.
• Intrinsic reactivity drops roughly a factor of 20 for secondary compared to primary amines.
- Steric hindrance plays an additional role • Cure speed (gel time) of a formulation is dependent on concentrations and
intrinsic reactivity. • Products are stable, so there is no off-gassing of reversible blocking agents.
NHO
ONH
RR
nx
y
z
O
ONH
ONH NH
R
RR
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Product Name XTJ-584 XTJ-585 XTJ-576 XTJ-586Secondary Version of D-230 D-400 D-2000 T-403Approximate Functionality 2 2 2 3Density, 25°C, g/cm3 0.885 0.921 0.978 0.923Kinematic Viscosity, 25°C, cSt 7 18 209 46Total Amine, meq/gram 5.3-6.3 3.5-4.0 0.9-1.0 4.5-5.5Target Equivalent weight, grams/eq 172 270 1042 204
Huntsman’s New Secondary Polyetheramines
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• Pigment, such as TiO2 • Adhesion Promoter • UV-Stabilizers/Antioxidants • Thixotrope • “Defoamer”/”Dispersant” • Solvent • Plasticizer • “Filler”
COMMON ADDITIVES:
OTHER FORMULATION ADDITIVES
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Processing Polyurea Spray Elastomers
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Static-Mix Dispensing Equipment
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Gusmer H-2000 Proportioning Unit
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HIGH TEMPERATURE/ HIGH PRESSURE IMPINGEMENT-MIX SPRAY APPLICATION
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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.
STANDARD SPRAY PROCESSING PARAMETERS
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Formulating Polyurea Spray Elastomers
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SYSTEM TYPE: aromatic or aliphatic (cost vs. UV-color stability) PREPOLYMER TYPE: isocyanate type, isomer distribution, and polyol
(polyetheramine) composition can greatly affect elastomer properties
INDEX: can be used to help overcome brittleness and extend working time (INDEX = Free Eq’s Isocyanate/ Free Eq’s Amine) CROSSLINK DENSITY: can affect brittleness/flexibility, permeability, and
chemical resistance SECONDARY AMINE CONTENT: modulates system speed
KEY FORMULATION PARAMETERS AFFECTING ELASTOMER PROPERTIES
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20
30
40
50
60
70
80
10 15 20
NCO Value (%)
Har
dnes
s (Sh
ore
D)
THE EFFECT OF %NCO VALUE ON ELASTOMER HARDNESS
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FINDING THE OPTIMAL SYSTEM INDEX
0
500
1000
1500
2000
2500
3000
0.9 0.95 1 1.05 1.1 1.15
Isocyanate/Amine Index
Tens
ile S
tren
gth,
psi
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0
10
20
30
40
50
60
Secondary Amine Content (% Resin Side)
Time (s)
0% 8.1% 18.6% 29.9%
Gel Time Tack-Free Time
THE DECELERATING EFFECTS OF SECONDARY AMINES
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ISOCYANATE COMPONENT
Adduct, Prepolymer, or
Quasi-Prepolymer 100%
RESIN COMPONENT
Polyetheramine 40-70%
Chain Extender 10-50%
Additives 0-10%
VOLUME RATIO: 1:1
THE TYPICAL POLYUREA SPRAY ELASTOMER FORMULATION PROFILE
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ISOCYANATE COMPONENT
15.4% NCO MDI-Based
Quasi-Prepolymer 100%
RESIN COMPONENT
JEFFAMINE® D-2000 amine 57.7%
JEFFAMINE® T-5000 amine 5.3%
ETHACURE® 100 curing agent 18.6%
UNILINK® 4200 curing agent 18.6%
Index: 1.05 Volume Ratio: 1:1
Gel Time: 7.0 s Tack-Free Time: 12.5 s Hardness: D51
Tensile Strength: 2128 psi
Elongation: 529 %
Modulus, 100%: 1027 psi
Modulus, 300%: 1471 psi
Tear Strength: 456 pli
STARTING-POINT FORMULATION FOR AN AROMATIC POLYUREA COATING
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ISOCYANATE COMPONENT
IPDI / D-2000 or PPG-2000
Pre-polymer: 16.8% NCO 100%
RESIN COMPONENT
JEFFAMINE® D-2000 amine 39.0%
JEFFAMINE® T-5000 amine 10.0%
JEFFLINK® 754 curing agent 44.0%
TiO2 7.0%
Index: 1.06 Volume Ratio: 1:1
Lot Number: 8276-59 Gel Time: 5.0 s Tack-Free Time: 22.0 s Hardness: D55
Tensile Strength: 2670 psi
Elongation: 875 %
Modulus, 100%: 1003 psi
Modulus, 300%: 1120 psi
Tear Strength: 526 pli
STARTING-POINT FORMULATION FOR AN ALIPHATIC POLYUREA COATING
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Application Examples of Polyurea Spray Elastomers
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Polyurea Applications
• Steel coating - automotive, bridges, tanks, etc.
• Concrete coating - roads, parking structures, water-proofing, explosion mitigation, etc.
• Naval vessels - corrosion protection, non-skid, anti-fouling, explosion mitigation.
• Water/waste-water tanks and piping • Other substrates - polystyrene, plastic, ….
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SLOW-SET POLYUREA ELASTOMER TANK LININGS
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POLYUREA ELASTOMERS AS PROTECTIVE COATINGS
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Truck Bed Liner
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Forms of Polyurea and Hybrids
• Caulk for concrete joints (low strength, high elongation) • Adhesive for a variety of substrates. • Polyurea Spray Foam. • Polyetheramines and amine chain extenders can be added
to PU foam formulations to make hybrid PU foams. • Reaction-Injection Molding (RIM) and other molded
polyurea parts. • Roll-on polyurea with hours of work time • Sprayed-on elastomers with seconds to hours dry time.
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Polyurethane Uses of Amines
• Isocyanate Prepolymers • Chain extenders for quicker viscosity build • Cast Polyurea parts • Polyurethane Dispersions • 1K coatings (especially secondary amines) • Polyurethane/Polyurea Hybrids
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Conclusions
• The lines between polyurethane and polyurea are becoming blurred.
• There are many new amines available, especially secondaries, that can be used in PU formulations.
• The ability to use both polyols and amines greatly increases formulating flexibility.
• Formulators and applicators with knowledge of both chemistries will increase their breadth of projects and profits.
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More Information
• http://www.huntsman.com/performance_products/index.cfm?PageID=2136
• JEFFAMINE.com • Huntsmanchainextenders.com • Polyurea Development Association (PDA)
www.pda-online.org • [email protected]
All information contained herein is provided "as is" without any warranties, express or implied, and under no circumstances shall the authors or Huntsman be liable for any damages of any nature whatsoever resulting from the use or reliance upon such information. Nothing contain in this presentation should be construed as a license under any intellectual property right of any entity, or as a suggestion, recommendation, or authorization to take any action that would infringe any patent. The term "Huntsman" is used herein for convenience only, and refers to Huntsman LLC, its direct and indirect affiliates, and their employees, officers, and directors.
Disclaimer