Update and Overview of Polyurea
Spray Technology and New Amine
Chain Extenders Useful inPolyurethane Systems
Mark L. Posey
Huntsman LLC : Austin Research Labs
2005 Polyurethane Manufacturers Association Annual Meeting
Rancho Mirage, CA April 17-19, 2005
1

The History and Background ofPolyurea Spray Elastomers

2Key Developments Along thePolyurea Spray Elastomer Timeline
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 andintroduce 100% solids polyurea spray elastomer coatings.
1990’s: Numerous equipment advances by industry leaders.
1990’s: Huntsman Corporation and ICI Polyurethanes co-develop andcommercialize 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
inlate 1990s. Allows first “roll-on” polyureas.

3

Key Developments Along thePolyurea Spray Elastomer Timeline-cont.
2000: Formation of the Polyurea Development Association
2002: Huntsman commercializes JEFFLINK® 754 chain extender forpolyurea and other polymer markets.

2002: UOP suddenly exits chain extender market in December.
2003: UOP sells rights to UNILINK® 4200 and CLEARLINK® 1000chain extenders to Dorf Ketal in India.

2004: Nissan is first company to offer OEM truck-bed liner.
2005: Huntsman commercializes Secondary Polyetheramines.

4THE POLYUREA SPRAY ELASTOMERMARKET AT AGLANCE*ESTIMATED 2001 SYSTEM SOLD:

20-25MM LBS

ESTIMATED MARKET VALUE:$60-75MMGEOGRAPHIC BREAKDOWN:NORTHAMERICAAPAC
EUROPE
SOUTH AMERICA

85%
10%
4%
1%

*-2001 Industry Report Conducted by the Polyurea Development Association5POLYUREA SPRAY ELASTOMERAPPLICATION AREAS*
5%10%10%

15%60%
ConcreteBedliners

SteelRoofing

Other*-2001 Industry Report Conducted by the Polyurea Development Association6CHEMICAL REACTIONS:POLYURETHANE AND POLYUREA
O
OCN

NCO
R+Isocyanate

HOOH
R'=O

R

R'
N

OONHn

H

PolyolUrethane
OOCN

NCO
R

Isocyanate+HR"NNR"HR'Polyamine=O

R

R'N

N

H

R"

NHNH
nUrea

7

THE POLYUREA/POLYURETHANE
ELASTOMER SPECTRUM

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.
8BENEFITS OFPOLYUREA SPRAY ELASTOMERS••••••••

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.

9

TYPICAL PHYSICAL PROPERTIESFOR POLYUREA ELASTOMERS••••••

Tensile Strength
Shore Hardness
Elongation
Tear Strength
100% Modulus(Stress@100%)
300% Modulus(Stress@300%)

up to 28 MPa (4000 psi)
A30 to D75
up to 1200 %up to 127000 N/m (725 pli)
up to 14 MPa (2000 psi)
up to 17 MPa (2500 psi)

10Common Raw Materials for
Polyurea Spray Elastomers“New” Amines for Possible
Use in Polyurethanes

11

ISOCYANATE SYSTEMS FORPOLYUREA ELASTOMER COATINGS
Aromatic-Based Systems
CH2CH2NCO

OCN

NCOOCN

4,4'-MDI

2,4'-MDI

Aliphatic-Based Systems

NCO

OOCN---6(H 2C)
NCO

H3C

CH3CH3OCN

IPDI

NNCO
NCO

H12MDI(CH2)6 ---NCO

CCNO(CH2)6 -----NCO

HDI Trimer
12

ISOCYANATE PREPOLYMERSFOR ELASTOMER COATINGS
Aromatic-Based Systems
O

CH3OCN

ONH

O

O
O
~32

CH3NH
NCO

O

MDI-PPG-2000 Prepolymer
Aliphatic-Based Systems
H3C

CH3

H3C
O

H3C
OCN

CH3H3C
O

NH

NH

CH3HN

NH
O
~32

CH3NCOO

IPDI - D-2000 Prepolymer
13

AROMATIC CHAIN EXTENDERS FORPOLYUREA ELASTOMER COATINGSNH2H3C
CH2S

H3C

CH3NH2NH2CH3H3C

CH2S
H3C

NH2ETHACURE® 100 curing agent

ETHACURE® 300 curing agent

HNNH

H3C
CH2CH3H3C

CH2CH3UNILINK® 4200 chain extender
ETHACURE is a trademark of Albemarle. UNILINK is a trademark of Dorf Ketal.

14

CYCLOALIPHATICCHAIN EXTENDERSNHJEFFLINK® 754 curing agent
NH

CLEARLINK® 1000 curing agent
HN

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.

NH15

Secondary Aspartic Ester Amines
OONHONHOOOOODESMOPHEN® NH1420 curing agent

DESMOPHEN is a trademark of Bayer.

16

JEFFAMINE® POLYETHERAMINESFOR POLYUREA ELASTOMER COATINGS
H2N

CH2 CH2 NH2 CH OCHx
CH3CH3Product
JEFFAMINE® D-400 amine
JEFFAMINE® D-2000 aminex5-632-34

NH 2Ox
OR

CH 2n

NH 2y
NH 2OzJEFFAMINE(R) T-403 amine
x + y + z = ~ 5.3
R = C2 H5 n = 1JEFFAMINE(R) T-3000 amine
x + y + z = ~ 50
R = H n =0
JEFFAMINE(R) T-5000 amine
x + y + z = ~ 85
R = H n =0
JEFFAMINE is a trademark of Huntsman LLC or an affiliate thereof in one or more, but not all countries.

17

New Secondary Polyetheramines•

Proprietary Huntsman catalyst technology allows high secondaryamine formation with little primary or tertiary.
ORO
NHRy NH

NHnORRONHO
NHxRz• Intrinsic reactivity drops roughly a factor of 20 for secondary compared toprimary amines.
- Steric hindrance plays an additional role• Cure speed (gel time) of a formulation is dependent on concentrations andintrinsic reactivity.
• Products are stable, so there is no off-gassing of reversible blocking agents.
18

Huntsman’s New SecondaryPolyetheramines
Product NameXTJ-584

XTJ-585

XTJ-576

XTJ-586

Secondary Version ofD-230

D-400

D-2000T-403

222

30.885

0.921

0.978

0.923

718

209

46

Total Amine,meq/gram

5.3-6.3

3.5-4.0

0.9-1.0

4.5-5.5

Target Equivalent weight,grams/eq

172

270

1042

204

Approximate Functionality
Density, 25°C, g/cm3
Kinematic Viscosity, 25°C,cSt

19

OTHER FORMULATION ADDITIVESCOMMON ADDITIVES:• Pigment, such as TiO2
• Adhesion Promoter• UV-Stabilizers/Antioxidants• Thixotrope• “Defoamer”/”Dispersant”• Solvent• Plasticizer• “Filler”
20Processing Polyurea Spray Elastomers

21Static-Mix Dispensing
Equipment

22

Gusmer H-2000
Proportioning Unit

23

HIGH TEMPERATURE/ HIGH PRESSURE
IMPINGEMENT-MIX SPRAY APPLICATION

24

STANDARD SPRAYPROCESSING PARAMETERS• 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 spraypattern may occur.

• System Temperature: 60-80C (150-170F)––

If too low: poor mixing and loss of spraypattern may occur.
25

Formulating Polyurea
Spray Elastomers

26

KEY FORMULATION PARAMETERS
AFFECTING ELASTOMER PROPERTIESSYSTEM TYPE: aromatic or aliphatic (cost vs. UV-color stability)
PREPOLYMER TYPE: isocyanate type, isomer distribution, and polyol(polyetheramine) composition can greatly affectelastomer 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, andchemical resistance
SECONDARY AMINE CONTENT: modulates system speed

27

THE EFFECT OF %NCO VALUE
ON ELASTOMER HARDNESS
80Hardness (Shore D)

7060
50403020101520

NCO Value (%)
28

FINDING THE OPTIMAL SYSTEM INDEX
3000Tensile Strength, psi

2500

2000
1500
1000

500
00.90.95

11.051.11.15

Isocyanate/Amine Index

29THE DECELERATING EFFECTS
OF SECONDARY AMINES
605040Gel Time
Tack-Free TimeTime (s) 30
201000%

8.1%

18.6%

29.9%

Secondary Amine Content (% Resin Side)30

THE TYPICAL POLYUREA SPRAY
ELASTOMER FORMULATION PROFILEVOLUME RATIO: 1:1
ISOCYANATE COMPONENT
Adduct, Prepolymer, orQuasi-Prepolymer

100%RESIN COMPONENTPolyetheramine

40-70%

Chain Extender

10-50%

Additives

0-10%
31

STARTING-POINT FORMULATION FOR
AN AROMATIC POLYUREA COATINGISOCYANATE COMPONENTGel Time:
Tack-Free Time:

15.4% NCO MDI-BasedQuasi-Prepolymer

7.0 s
12.5 s100%
Hardness: D51

RESIN COMPONENT

Tensile Strength:2128 psiElongation:

529 %JEFFAMINE® D-2000 amine

57.7%

Modulus, 100%:JEFFAMINE® T-5000 amine

1027 psi

5.3%

Modulus, 300%:

1471 psi

Tear Strength:456 pli

ETHACURE® 100 curing agent 18.6%
UNILINK® 4200 curing agent
Index: 1.05

18.6%

Volume Ratio: 1:132

STARTING-POINT FORMULATION FOR
AN ALIPHATIC POLYUREA COATINGISOCYANATE COMPONENTIPDI / D-2000 or PPG-2000
Pre-polymer: 16.8% NCO

100%

Lot Number:

8276-59

Gel Time:
Tack-Free Time:

5.0 s
22.0 sHardness: D55

RESIN COMPONENT

Tensile Strength:2670 psi

JEFFAMINE® D-2000 amine

39.0%

Elongation:

875 %JEFFAMINE® T-5000 amine

10.0%

Modulus, 100%:

1003 psi

JEFFLINK® 754 curing agent

44.0%

Modulus, 300%:

1120 psi

TiO2

7.0%

Tear Strength:

526 pliIndex: 1.06

Volume Ratio: 1:1
33

Application Examples ofPolyurea Spray Elastomers

34

Polyurea Applications
Steel coating - automotive, bridges, tanks, etc.
• Concrete coating - roads, parking structures,water-proofing, explosion mitigation, etc.
• Naval vessels - corrosion protection, nonskid, anti-fouling, explosion mitigation.
• Water/waste-water tanks and piping• Other substrates - polystyrene, plastic, ….
•35

SLOW-SET POLYUREA ELASTOMERTANK LININGS

36

POLYUREA ELASTOMERSAS PROTECTIVE COATINGS

37

Truck Bed Liner38

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 toPU 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.
39

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

40

Conclusions• The lines between polyurethane and polyurea arebecoming blurred.
• There are many new amines available, especiallysecondaries, that can be used in PU formulations.
• The ability to use both polyols and amines greatly
increases formulating flexibility.
• Formulators and applicators with knowledge ofboth chemistries will increase their breadth ofprojects and profits.
41

More Information•

http://www.huntsman.com/performance_products/index.cfm?PageID=2136•

JEFFAMINE.com••

Huntsmanchainextenders.com
Polyurea Development Association (PDA)•

www.pda-online.org
mark_posey@huntsman.com
Disclaimer

All information contained herein is provided "as is" without any warranties, express or implied, and under no circumstances shall the authors or Huntsman beliable for any damages of any nature whatsoever resulting from the use or reliance upon such information. Nothing contain in this presentation should beconstrued as a license under any intellectual property right of any entity, or as a suggestion, recommendation, or authorization to take any action that wouldinfringe 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.

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