Polyurea Spray Elastomers an Overview of Current Technology

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Jerry L. Reddinger and Kenneth M. HillmanHuntsman Corporation

Austin, Texas USA

■ 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

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

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.

■ 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)

■ 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)

CH2

OCN NCO

4,4'-MDI

CH2

OCN

NCO

2,4'-MDI

Aromatic-Based Systems

Aliphatic-Based Systems

H3CCH3 CH3

NCO

NCO

IPDI

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

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

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 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)

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)

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

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 TRIGGERMANSINCE 1985

CHIP EMERSONCHIP EMERSON RICHARD ROMERORICHARD ROMERO