Jerry L. Reddinger and Kenneth M.

Hillman
Huntsman Corporation Austin, Texas USA

1980s: Texacos Austin Research Laboratories develop polyurea

reaction-injection-molding (RIM) for automotive exterior body panel applications.

I I I I I

1989:

Texacos Austin Research Laboratories develop and introduce 100% solids polyurea spray elastomer coatings.

1990s: Numerous equipment advances by industry leaders. 1990s: Huntsman Corporation and ICI Polyurethanes co-develop and
commercialize isocyanate prepolymers for polyurea spray.

1990s: Introduction of key secondary amine chain extenders for use in

polyurea elastomer coatings.

2000:

Formation of Polyurea Development Association

POLYURETHANE
OCN NCO + R HO R' OH
Catalyst R N H

O R' O O

O N n H

Isocyanate Prepolymer

Polyol

Urethane Linkage
O O R' N H N
H

POLYUREA
OCN NCO + R H2N R' NH2
R

N
H

N n H

Isocyanate Prepolymer

Polyamine

Urea Linkage

Resin Component Main Chain Extender

POLYUREA
Polyetheramine

Class 1 Hybrid

Class 2 Hybrid

Class 3 Hybrid
Polyol

PU
Polyol

Polyetheramine Polyetheramine Polyamine (Hydroxyl Containing)

Polyamine

Polyol

Polyamine

Polyol

Catalyst Package

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.

I I I I I

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 TEMPERATURE INSENSITIVE DURING APPLICATION EXCELLENT PHYSICAL PROPERTIES HIGH THERMAL STABILITY (UP TO 175 C)

I I

I I I I I I

Tensile strength Shore Hardness Elongation Tear strength 100% Modulus 300% Modulus

up to 28 MPa (4000 psi) A30 to D80 up to 1200 % up to 127000 N/m (725 pli) up to 14 MPa (2000 psi) up to 17 MPa (2500 psi)

Aromatic-Based Systems
CH2 CH2

NCO

OCN

NCO

OCN

4,4'-MDI

2,4'-MDI

Aliphatic-Based Systems
NCO

NCO H3C CH3 IPDI CH3

H2N CH CH3

CH2 O

CH2 CH CH3

NH2 x

Product

5-6 JEFFAMINE D-400 JEFFAMINE D-2000 32-34

CH2[OCH2CH(CH3)]NH2 x HC [OCH2CH(CH3)]NH2 y CH2[OCH2CH(CH3)]NH2 z x + y + z = ~81

JEFFAMINE T-5000

H3C CH2 NH2

HN
CH3 H3C NH2 CH2

NH CH3 CH3

H3C CH2 H3C CH2

ETHACURE 100
NH2 H3C S CH3

UNILINK 4200

HN
NH2 S H3C

NH CH3 CH3

H3C CH2 H3C CH2

ETHACURE 300

CLEARLINK 1000

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

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.

ISOCYANATE COMPONENT 15.4% NCO MDI-Based Quasi-Prepolymer RESIN COMPONENT JEFFAMINE D-2000 JEFFAMINE T-5000 ETHACURE 100 UNILINK 4200 Index: 1.05 57.7% 5.3% 18.6% 18.6% 100% Hardness: Tensile Strength: Elongation: Modulus, 100%: Modulus, 300%: Tear Strength: D51 14.7 MPa (2128 psi) 529 % 7.1 MPa (1027 psi) 10.1 MPa (1471 psi) 79846 N/m (456 pli) Gel Time: Tack-Free Time: 7.0 s 12.5 s

Volume Ratio: 1:1

ISOCYANATE COMPONENT 20.4% NCO MDI-Based Quasi-Prepolymer RESIN COMPONENT JEFFAMINE D-2000 JEFFAMINE D-400 JEFFAMINE T-5000 ETHACURE 100 UNILINK 4200 Index: 1.10 22.0% 26.0% 10.0% 27.0% 15.0% 100% Gel Time: Tack-Free Time: Hardness: Tensile Strength: Elongation: Tear Strength: 2.5 s 4.0 s D70 24.3 MPa (3522 psi) 73 % 125372 N/m (716 pli)

Volume Ratio: 1:1

Isocyanate 15.4% NCO MDI-Based Resin Blend JEFFAMINE D-2000 JEFFAMINE T-5000 ETHACURE 100 UNILINK 4200 TIOXIDE TiO2 INDEX: 1.30 51.4% 10.3% 9.5% 20.6% 8.2% VOLUME A/B: 1:1 100%

WORKING TIME: ~2 min

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.

POLYUREA TRIGGERMAN SINCE 1985

CHIP EMERSON

RICHARD ROMERO