Review of Regulatory Efforts Regarding
VOCs for Coatings and the use of
Alkanolamines to Achieve VOC
Reductions
Mike Hakos 4/26/2012
Who Am I?
• NA Market Manager (~1 year)
• Account Manager with Taminco (2 years)
• Sr. Account Representative with Eastman (8 years)
• Customer Service with Hercules Adhesives (5 years)
• EMBA St Joseph’s University (2009)
• BS Chemistry Grove City College (1997)
Who is Taminco? THE AMINE COMPANY
• Activity leading supplier of alkylamines and
derivatives
• Turnover € 800 million (2011)
• Personnel 800 people in 16 countries
• Production 7 sites
• Europe: Gent-Belgium, Leuna-Germany
• Asia-Pacific: Yixing, Fengxian, and Nanjing (J/V)
• Americas: Pace, FL & St Gabriel, LA-USA
• Installed Production
Capacity 1 million tonnes per annum
• Sales Offices 17 (5 Americas, 6 Europe, 6 Asia)
2003
•Methylamines EU
•Methylamine
Derivatives (NMP,
DMF, DMAPA, etc)
•Methylamines NA
•Basic Higher Amines
(MIPA, Ethyls, n-Butyls,
etc)
•Specialty Higher
Amines
•Methylamine
Derivatives (DMAE,
MDEA, etc)
2006
Products Offered:
2007
41 55 80
Total Annual Sales: € 185 € 353 € 800
Genesis and Growth of Taminco
Agenda
• Review of Regulatory Efforts Regarding VOC for
Coatings
• Using Alkanolamines to achieve VOC Reductions
Who are the Players in VOC Regulations?
• SCAQMD - South Coast Air Quality Management District
• Smog control agency for all or portions of Los Angeles, Orange, Riverside and San Bernardino Counties
• 10,750 square miles and is the second most populated area in the United States
• CARB – California Air Resource Board
• OTC - Ozone Transport Commission
• Responsible for advising EPA on transport issues and for
developing and implementing regional solutions to the ground-
level ozone problem in the Northeast and Mid-Atlantic regions
• EPA – Environmental Protection Agency
Typical Regulation Path
• SCAQMD tends to be national leader in legislation
reducing of VOC emissions
• In the past, it has been observed that SCAQMD
pioneers legislation and limits, which is then later
adopted by CARB, OTC, and EPA
• This makes SCAQMD activities very interesting to
industry
• Open SCAMD meetings have very diverse attendance:
paint companies, additive makers, contractors, etc.
Update on SCAQMD
• Key legislation governing Coatings VOC emissions is Rule 1113
• Adopted in 1977
• http://www.aqmd.gov/rules/reg/reg11/r1113.pdf
• One key piece removed from this was the adoption of a GC method of determining VOC
• They are currently discussing forming a VOC subcommittee in Q2 2012 to look at method’s of VOC determination
Determining VOC in Architectural Paint
• Currently determined by EPA Method 24
• Lack of precision in low VOC systems
• ASTM-D6886
• GC Methodology of VOC analysis of paint using
methyl palmitate (~330 C BP) as a cutoff
• Designed by Cal Poly
• SCAQMD Method 313
• Similar to D6886 but utilizes marker compounds
• Other industries are using Thermogravemetric Analysis
(MWF)
Key Issues on a GC Methodology
• Methyl Palmitate as a cutoff marker is very ambitious;
most if not all commonly used paint additives would be
ruled a VOC
• Column choice and carrier gas can significantly impact
results
• Although GC is an excellent method of determining
composition of a paint, it does not represent the
volatility of the paint!
• Does not account for compounds that are “Partial”
VOC’s
Our Conclusions
• Volatility is difficult to predict, as the relative volatility of
different compounds changes with temperature!
• We can see inversions in the volatile nature of
compounds as they are heated
• It is our belief that thermal methods of analysis at
temperatures as close as possible to application
temperatures give the truest understanding of the
volatility of compounds
Our Conclusions
• Are alternative test methods appropriate?
• A test like Thermogravimetric Analysis run at 81oC
would be one idea
• Chamber testing at ambient temperatures would be
another solution
What is Taminco Doing?
• We have been doing extensive studies in trying to
understand volatility in conjunction with Cal Poly
• We have prepared a paper on this issue, if you would
be interested in reading this, please get a card from me
and send me an e-mail. We are happy to share this
work
• We have presented our work to ACA, ASTM, and the
SCAQMD
Using Alkanolamines in Paint Formulas
• As you know, Amines or Ammonia are typically used
for neutralization in paint formulations as pH modifiers
• Although small portions of the overall coating
formulation, your choice of neutralizing amine can
bring some distinct benefits
• Taminco offers Advantex® and Vantex®-T as
neutralizing amines that provide interesting, more
environmentally friendly options
Advantex®
• Secondary amine
• Low Odor
• 100% VOC
• Can help significantly in formula optimization
• Can help with tint strength
• Has benefits in flash rust inhibition
• Although this product is a 100% VOC, the
multifunctional nature may allow you to reduce or
replace other VOC producing materials
Sample Formula Optimization with Advantex®
Quantities in
Pounds/100 gallons I II III IV V VI VII VIII
Water 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0
Tamol 731A 7.5 7.5 7.5 7.5 7.5 7.5 3.8 3.8
BYK 348 1.0 1.0 1.0 1.0 1.0 1.0 0.5 0.5
Tego Foamex 810 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5
Kathon LX 1.5% 1.6 1.6 1.6 1.6 1.6 1.6 1.6 1.6
Propylene Glycol 12.9 6.5 0 30.1 15.1 0 12.9 6.5
TIOXIDE TR 93 225.0 225.0 225.0 225.0 225.0 225.0 225.0 225.0
Grind
Water 101.9 101.9 101.9 101.9 101.9 101.9 126.5 126.5
Rhoplex VSR 2015 524.2 524.2 524.2 524.2 524.2 524.2 524.2 524.2
Advantex 3.5 3.5 3.5 3.5 3.5
Ammonia, 28% 6.0 6.0 6.0
BYK 348 1.0 1.0 1.0 1.0 1.0 1.0 0.5 0.5
Tego Foamex 810 2.0 2.0 2.0 2.0 2.0 2.0 1.0 1.0
RM 2020NPR 30.5 30.5 30.5 30.5 30.5 30.5 30.5 30.5
RM 8W 3.0 3.0 3.0 2.0 2.0 2.0 2.0 2.0
Water 19.2 25.7 31.7 15.1 29.2 6.5
TOTAL 1033.8 1033.9 1033.4 1033.3 1033.4 1032.4 1032.5 1032.6
PVC - 19.6%, VS - 34.5%, VOC < 50 g/l
Sample Formula Optimization with Advantex®
Quantities in
Pounds / 100 Gal I II III IV V VI VII VIII
Amine Advantex Advantex Advantex 28%
NH3(aq)
28%
NH3(aq)
28%
NH3(aq) Advantex Advantex
Amine Level 3.5 3.5 3.5 6.0 6.0 6.0 3.5 3.5
Propylene Glycol 12.9 6.5 0.0 30.1 15.1 0.0 12.9 6.5
Surfactant 2.0 2.0 2.0 2.0 2.0 2.0 1.0 1.0
Defoamer 2.5 2.5 2.5 2.5 2.5 2.5 1.5 1.5
Dispersant 7.5 7.5 7.5 7.5 7.5 7.5 3.8 3.8
Viscosity, KU 94 94 94 96 98 101 103 103
Viscosity, ICI 0.9 0.9 0.8 0.9 0.9 0.8 0.9 0.9
F/T, 3 Cycles
Final Viscosity, KU 102 104 Fail-3rd 108 Fail-1st Fail-1st 112 114
Viscosity Difference 8 10 12 9 11
Leveling
ASTM D4062 10 10 10 10 10 10 10
Low Temperature Film Formation, 6 Mils, 40 oF
Sealed 10 10 10 10 10 10 10
Unsealed 10 10 10 10 10 10 10
What did we do in this formulation by using Advantex®?
• Remove NH3 and reduce odor
• Reduce Propylene Glycol by 75%
• Reduce surfactant by 50%
• Reduce defoamer by 40%
• Optimize dispersant levels
What did we do in this formulation by using Advantex®?
• Although more expensive than NH3 up front, by
optimizing your formulations with Advantex® you
can pull out other expensive raw materials and
maintain performance!
• Pulling out all of the above can have a significant
impact on your VOC content, Advantex® can bring a
lot of flexibility to your formulations
Flash Rust Inhibition
Flat Enamel
A B C D
Amine 28% NH3 (aq.) 28% NH3 (aq.) Advantex® Advantex®
Level / 100 Gallons 8.5 8.5 4.0 4.0
Sodium Nitrite 0.0 9.0 0.0 9.0
pH 8.61 8.48 8.59 8.43
Viscosity, KU 106 108 108 105
Contrast Ratio, 3 Mils 0.974 0.978 0.976 0.978
Reflectance 92.4 92.1 92.0 92.0
Gloss, 85 Degrees 3.4 3.4 3.5 3.5
Adhesion, Cold Rolled Steel
7 Days Dry 4B 3B 4B 4B
Flash Rust (10=No Rust, 0=Heavy Rust)
24 Hours Dry, 75°F, 50%RH 6 10 10 10
Water Resistance Benefits
A B
Water 34.33 34.33
Propylene Glycol 34.55 34.55
BYK 1650 1.00 1.00
AMP-95 4.00 0.00
Advantex® 0.00 4.00
BYK 156 6.00 6.00
Triton CF-10 2.00 2.00
Ti-Pure R-900 253.50 253.50
Mincx 4 24.94 24.94
UCAR 481 562.35 562.35
Texanol 15.75 15.75
Popylene Glycol 8.64 8.64
BYK 1650 1.00 1.00
Acrysol RM-8 35.95 35.95
Water 83.33 83.33
Total 1067.34 1067.34
Water Resistance of Dried Paint Film (24 hours)
While both films still contain a fair amount of un-evaporated
alkanolamine, Advantex®, with its ideal balanced HLB value of 10,
provides for excellent water resistance at intermediate dry times.
Vantex®-T
• Tertiary Amine
• 283o C boiling point
• Very low non-amine odor, does not add to VOC load of paint
• Partial coalescent – can replace solvent and anti-freeze (both VOC’s)
• Excellent for colloid stability
• Syneresis Control
• Enabling paint makers to formulate highly functional zero-VOC paints
T#20 Formulation - Semigloss
A B C D E F
(lbs./100 gals.) (lbs./100 gals.) (lbs./100 gals.) (lbs./100 gals.) (lbs./100 gals.) (lbs./100 gals.)
Water 100.0 100.0 100.0 100.0 100.0 100.0
Natrosol Plus 330 0.5 0.5 0.5 0.5 0.5 0.5
Vantex®-T 0.0 2.0 4.0 6.0 8.0 10.0
Tamol 731A 5.0 5.0 5.0 5.0 5.0 5.0
Drewplus L-493 2.5 2.5 2.5 2.5 2.5 2.5
Carbowet DC 01 2.0 2.0 2.0 2.0 2.0 2.0
Proxel DB-20 3.0 3.0 3.0 3.0 3.0 3.0
TiPure R-706 250.0 250.0 250.0 250.0 250.0 250.0
Mixex 10 25.0 25.0 25.0 25.0 25.0 25.0
Attagel 50 3.0 3.0 3.0 3.0 3.0 3.0
Grind
Water 88.3 88.3 88.3 88.3 88.3 88.3
Optive 130 525.0 525.0 525.0 525.0 525.0 525.0
Drewplus L-493 3.0 3.0 3.0 3.0 3.0 3.0
Acrysol RM 2020 NPR 26.1 26.1 26.1 26.1 26.1 26.1
Acrysol RM 8W 17.0 17.0 17.0 17.0 17.0 17.0
Rhodoline FT-100 7.5 7.5 7.5 7.5 7.5 7.5
Water 10.0 8.0 6.0 4.0 2.0 0.0
Total 1067.9 1067.9 1067.9 1067.9 1067.9 1067.9
PVC - 24.6%, VS- 34.5%, Calculated VOC <5 g/l
Measured VOC Content under Method 24
T#21 Formulation - Flat Enamel
A B C D E F
(lbs./100 gals.) (lbs./100 gals.) (lbs./100 gals.) (lbs./100 gals.) (lbs./100 gals.) (lbs./100 gals.)
Water 275.5 275.5 275.5 275.5 275.5 275.5
Natrosol Plus 330 2.5 2.5 2.5 2.5 2.5 2.5
Vantex®-T 0.0 2.0 4.0 6.0 8.0 10.0
Acticide BW 20 1.1 1.1 1.1 1.1 1.1 1.1
FoamStar A-38 1.5 1.5 1.5 1.5 1.5 1.5
Tamol 1124 7.0 7.0 7.0 7.0 7.0 7.0
Carbowet DC 01 2.0 2.0 2.0 2.0 2.0 2.0
Tronox CR 826 235.0 235.0 235.0 235.0 235.0 235.0
#10 White 35.0 35.0 35.0 35.0 35.0 35.0
Mixex 4 35.0 35.0 35.0 35.0 35.0 35.0
Optiwhite MX 150.0 150.0 150.0 150.0 150.0 150.0
Grind
Water 45.7 45.7 45.7 45.7 45.7 45.7
EcoVAE 350.0 350.0 350.0 350.0 350.0 350.0
Polyphobe TR 116 9.0 9.0 9.0 9.0 9.0 9.0
FoamStar 1.5 1.5 1.5 1.5 1.5 1.5
Water 10.0 8.0 6.0 4.0 2.0 0.0
Total 1160.8 1160.8 1160.8 1160.8 1160.8 1160.8
PVC - 47.5%%, VS- 38.8%
Measured VOC Content under Method 24
T20 Semigloss
Sample Solids % Volatiles % Water % VOC (g/L)
T20A 53.27 46.73 44.73 26.28
T20B 52.99 47.01 45.15 24.50
T20C 52.99 47.01 46.61 5.26
T20D 53.32 46.68 46.43 3.28
T20E 53.38 46.62 45.84 10.21
T20F 53.29 46.71 46.51 2.67
T21 Flat Enamel
Sample Solids % Volatiles % Water % VOC (g/L)
T21A 57.34 42.66 41.33 28.15
T21B 57.02 42.98 43.51 -7.43
T21C 57.47 42.53 43.49 -13.28
T21D 57.50 42.50 43.95 -20.13
T21E 57.48 42.52 43.99 -20.00
T21F 57.78 42.22 43.91 -23.27
Increasing amounts of Vantex® – T do not contribute
VOC to the finished paint!
Measured VOC Content under Method 24
Syneresis Control
A B C
Water 208.6 208.6 208.6
Natrosol Plus 330 1.5 1.5 1.5
AMP 95 12.0 - -
Vantex®-T - 12.0 -
NH3 - - 12.0
Nuosept 95 1.5 1.5 1.5
Tamol 731 12.0 12.0 12.0
Carbowet DC 01 2.0 2.0 2.0
Drewplus T4507 2.0 2.0 2.0
Ti-Pure R-706 230.0 230.0 230.0
Atomite 30.0 30.0 30.0
Attagel 50 5.0 5.0 5.0
Grind
Airflex EF-833 (55.0%) 453.9 453.9 453.9
RM 2020NPR 15.0 15.0 15.0
RM 825 7.0 7.0 7.0
Drewplus T4507 2.0 2.0 2.0
Water 80.4 80.4 80.4
Total 1,062.9 1,062.9 1,062.9
Syneresis after 1 week at Room Temperature
The lower liquid/liquid interfacial tensions exhibited by aqueous
solutions of Vantex®-T lead to better pigment dispersion, emulsion
stability, and syneresis control in paints!
Why would you use Alkanolamines?
• Lower Odor
• These products have virtually no odor which is a
marked improvement for manufacturing and
application
• Flexibility in Formulation
• Vantex®– T is a zero VOC under EPA Method 24
• A new tool in the toolbox!
Future Work
• Chamber Testing
• Where should we focus our efforts?
• We need your feedback
If you would like further information..
• Mike Hakos
• Our Midwest and East Coast distribution partner,
TH Hilson
• Online at :
• www.specialtyamines.com
• www.aminestoanend.com