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PDA Europe 2011 Annual Conference –The Hague, 14-16 November 1
New UV/Color Stable Spray
Aliphatic Polyurea Coating
Technology
Albemarle Corporation
PDA Europe 2011 Annual Conference –The Hague, 14-16 November 2
Company Overview – Who We Are
Albemarle provides innovative development, manufacturing and marketing of complex
chemistry solutions and services that create exceptional customer value while maximizing
shareholder wealth.
Diversified mix of solution-based products and custom services sold to a wide range of customers and end markets.
• Over 3400 customers, 100 countries
• Operate 45 facilities, encompassing production, research & development facilities, and administrative offices in North and South America, Europe, the Middle East and Asia
• Over 4000 employees around the world
2010 Net Sales
38% 38% 24%
Catalysts Polymer Solutions Fine Chemistry
PDA Europe 2011 Annual Conference –The Hague, 14-16 November
Scale and Scope
3
Weifang City, China
Beijing, China
Magnolia, AR, USA
Tyrone, PA, USA
Baton Rouge, LA, USA
Orangeburg, SC, USA
Pasadena, TX, USA
Twinsburg, OH, USA
South Haven, MI, USA
Bayport, TX, USA
Santa Cruz, Brazil
Avonmouth, UK
Amsterdam,
The Netherlands
Safi, Jordan
Niihama, Japan
St. Jakob/Breitenau, Austria
Shanghai, China
Seoul, Korea
Louvain-la-Neuve, Belgium
Singapore
Tokyo, Japan
Osaka, Japan,
Zhejiang Province, China
Nanjing, China
Ningbo, China
Moscow, Russia
Doncaster East VIC, Australia
Al-Jubail, Saudi Arabia
Bergheim, Germany
2010 Net Sales
42% 34% 24%
Americas Europe Asia
Regional/Sales Office
Manufacturing
R&D
Corporate Headquarters (Baton Rouge, LA, USA)
Houston, TX, USA
Budapest, Hungary
Dubabi, UAE
Joint Venture
PDA Europe 2011 Annual Conference –The Hague, 14-16 November
$0
$100
$200
$300
$400
$500
$600
$700
2000 2001 2002 2003 2004 2005 2006 2007 2008 2009 2010
New
Pro
du
cts
Sale
s
4
Differentiated by Our Innovation
Research and process development expertise that allow us to bring innovative technologies to the market more quickly and at a lower capital cost than our competitors.
We provide innovative development, production and service for the application of complex
chemistry to create exceptional customer value.
PDA Europe 2011 Annual Conference –The Hague, 14-16 November 5
Polyurea Spray Coatings
• Two component solventless coatings (zero VOC) – A Side: Isocyanate prepolymer
– B Side: Resin blend containing • Amine Curative hard segment
• Polyetheramine soft segment
• Systems are fast reacting – Quick return to service
– Need to moderate reactivity for cure rate control and smooth surface
• Most systems are aromatic (MDI and Ethacure 100) and thus lack UV/color stability.
PDA Europe 2011 Annual Conference –The Hague, 14-16 November 6
Ethacure® 90
• New aliphatic amine curative commercialized in 2011 (TSCA registration in US in February).
• Chemical structure designed to provide moderate cure speed.
• Allows formulation of robust fully aliphatic spray polyurea systems.
• Global registration underway.
NH
HN
PDA Europe 2011 Annual Conference –The Hague, 14-16 November 7
Aliphatic Polyurea Coatings
• The aliphatic polyurea coating system in this presentation is based on an HDI polyisocyanurate.
• Screening of formulations involved: – Mixing resin side components in a Speedmixer
– Providing a 1:1 volume ratio with a dual cartridge syringe
– Mixing iso and resin through a static mixer equipped with an air spray nozzle.
• Gel times were obtained by measuring time until the material no longer flowed when sprayed on a vertical surface
PDA Europe 2011 Annual Conference –The Hague, 14-16 November 8
Ethacure 90 gives significantly longer gel times
with HDI than other aliphatic secondary amines.
PDA Europe 2011 Annual Conference –The Hague, 14-16 November 9
Addition of PEA D-400 Provides Allows Cure Rate
Control as well as Increasing Elongation
20
14
6
25
16
28
88
0
5
10
15
20
25
0 30.7 41.1 49.6
Level of PEA D-400
Ge
l T
im
e (se
c)
0
10
20
30
40
50
60
70
80
90
100
% E
lo
ng
atio
n
Formulation Flexibility
PDA Europe 2011 Annual Conference –The Hague, 14-16 November 10
Base Formulations and Coating Properties
Iso-side wt% Formula 1 Formula 2
HDI 19.4% NCO 100 100
Resin-Side, wt %
E90 47.6 43.9
PEA D-400 17.6 23.4
PEA D-2000 23.3 21.2
IPDA 6.5 6.5
TiO2 5 5
Index 1.10 1.10
Gel time, sec 8 <6
Physical Properties
Thickness, mils 69 105
Hardness Shore A 94 95
Tensile Strength, psi 1920 2260
Elongation, % 68 90
Tear Strength, pli 520 460
PDA Europe 2011 Annual Conference –The Hague, 14-16 November 11
1. Aliphatic System: HDI-based spray aliphatic
coating cured with Ethacure 90
2. Aromatic System: MDI-based spray aromatic
coating
3. Aromatic/Topcoat System: MDI-based spray
aromatic coating with aliphatic (polyaspartic)
topcoat
Comparison of Aliphatic vs. Aromatic
Spray Polyurea Coating Systems
PDA Europe 2011 Annual Conference –The Hague, 14-16 November
12
New E90-based One Coat All Aliphatic
• Taber Abrasion and QUV (Weathering) Testing
1-Coat: E90-
based All
Aliphatic
2-Coat: Aromatic
with Polyaspartic
Topcoat
1-Coat: All
Aromatic
In 2-coat system,
topcoat was abraded
off allowing coating
discoloration.
Yellowing
throughout in all
aromatic system.
No yellowing in
E90-based all
aliphatic system.
PDA Europe 2011 Annual Conference –The Hague, 14-16 November
13
WVTR (Water Vapor Transmission Rate)
following ASTM E 96-05
New aliphatic coating has 2-2.5 X lower moisture transmission rate than aromatic systems.
y = 12.79x-0.84
R2 = 0.95 y = 33.87x
-0.91
R2 = 0.90
y = 32.25x-0.84
R2 = 0.98
0.0
0.5
1.0
1.5
2.0
0 20 40 60 80 100 120 140 160
THICKNESS (MIL)
WA
TE
R V
AP
OR
TR
AN
SM
ISS
ION
RA
TE
(P
ER
MS
)
ALIPHATIC
AROMATIC WITH TOPCOAT
AROMATIC
PDA Europe 2011 Annual Conference –The Hague, 14-16 November 14
New aliphatic technology provides same moisture
barrier protection at much lower coating thickness.
Required Coating Thickness for low MVT Rate (0.55 Perms)
0
20
40
60
80
100
120
140
ALIPHATIC AROMATIC WITH TOPCOAT AROMATIC
CO
AT
ING
TH
ICK
NE
SS
(M
IL)
RE
QU
IRE
D
PDA Europe 2011 Annual Conference –The Hague, 14-16 November 15
2011 Applications
• New Ethacure 90-HDI based polyurea coating on the
concrete below an amusement park ride.
PDA Europe 2011 Annual Conference –The Hague, 14-16 November 16
Discovery Channel’s Storm Chaser vehicle
The tough, new aliphatic spray coating protected the Discovery Channel’s
Storm Chaser vehicle from the severe tornado season of spring 2011.
PDA Europe 2011 Annual Conference –The Hague, 14-16 November 17
Decorative Coatings
• Aliphatic system allows the colorful coating on this
amusement park ride.
PDA Europe 2011 Annual Conference –The Hague, 14-16 November 18
Conclusions
• The commercialization of Ethacure 90 in 2011 provides a new slow aliphatic diamine for formulators, allowing the formulation of robust fully aliphatic spray polyurea systems.
• The cure rate is slow enough to allow one to formulate with faster primary amines like PEA D-400 and IPDA.
• The WVTR of the aliphatic polyurea is less than half of that of the aromatic polyurea systems.
• The improved moisture barrier performance allows application of a thinner aliphatic polyurea coating, significantly improving the system economics.
• Global rollout and registrations in 2011-2012.
PDA Europe 2011 Annual Conference –The Hague, 14-16 November 19 19
For more information regarding Albemarle’s curatives,
please visit www.curatives.com
Special thanks to co-authors: Paul Wiggins (Albemarle), Terry Pe (Line-X
Performance Coatings), Thalan Burris (Albemarle), and Dustin Le (HORN)