1. New Innovations in Development of Di- and Mono- Benzoates in Coatings Applications
Marianne Conner, William D. Arendt,
and Emily L. McBride
Emerald Kalama Chemical, LLC
Kalama, Washington
NW Coatings Fest
October 8-10, 2014
Hood River, Oregon
© Copyright October 2014, Emerald Kalama Chemical, LLC. All rights reserved.

2. Presentation Outline Background Goal Evaluation Recap
Historic benzoate overview
New products
Goal
Evaluation
Initial benzoate introduction
Physical properties, volatility, and VOC’s
Interior architectural paint with higher MFFT polymers
Partitioning
Most recent developments in interior paint
Update on exterior paint performance
Recap

3. Historical Development
1938
DPG/DEG dibenzoate - 1st patent – vinyl application
1953
Patent US : polyalkylene glycol dibenzoates, and resinous compositions plasticized therewith.
1980
Introduction of isodecyl benzoate as a coalescent/viscosity modifier.
1990’s
Proprietary blend of three dibenzoates (TEG,DE,DP) brought to market as a product with improved VOC, low odor, handling.
2000’s
2-EHB introduced for coatings industry. New blends of dibenzoates introduced with improved efficiency and economics.
Today
New blends of dibenzoates introduced with improved efficiency and economics.

4. Benzoate Coalescent Development
Benzoates: non-phthalates, commercially available for decades for coatings and other applications
Recently created dibenzoate platform was presented in Waterborne 2011 conference
850S - low VOC diblend of two dibenzoates
975P - low VOC type with lower freeze point than most diblends, broader range of compatibility in polar polymers
Global products
On inventories in the US, EU, and numerous others around the world

5. New Products In 2013, commercialized:
500P - Lowest VOC of the line of dibenzoates. Proprietary blend of diethylene and dipropylene glycol dibenzoates.
Introducing new monobenzoates for coatings:
613 (3–Phenylpropyl benzoate) – Significantly lower in VOC than TMPDMIB. Listed as a flavor additive in EU.
BOB (Benzyl benzoate) – Also significantly lower in VOC than TMPDMIB. Listed as a flavor additive.

6. Goal Review previously presented information:
Interior architectural paint with harder polymer
Exterior paint
Introduce and discuss most recent results on new dibenzoate coalescents for use in coatings:
Interior architectural paint

7. Coalescent VOC’s

8. VOC Measurement
In the US, EPA 24 is the guideline on VOC measurement method
ASTM D2369 oven volatility method (110ºC for 1 hour)
2,2,4-Trimethyl-1,3-pentanediol monoisobutyrate (TMPDMIB) is 100% volatile as is the diisobutyrate (TMPDMDIB)
ASTM D6886 under revision:
A modified version of D6885
Future of ASTM D6886 use of methyl palmitate boiling point marker (b.p at standard atmospheric pressure). Compounds eluting before considered VOC.

9. Coalescents Evaluated
975P: DPG/DEG/PGDB dibenzoate triblend
850S: Second generation dibenzoate binary blend
500P: Third generation dibenzoate diblend
613: 3–Phenylpropyl benzoate
BOB: Benzyl benzoate
TEGDO: Triethylene glycol di-2-ethylhexanoate, competitive low VOC coalescent, primary control
TMPDMIB: 2,2,4-Trimethyl-1,3-pentanediol monoisobutyrate

10. Coalescent Properties
Boiling Point,
°C at 5 mm Hg [760 mm Hg])
Vapor Pressure
(mm Hg at 25°C)
Flash Point
(°C)
TMPDMIB
110 [254]
1.3 x 10-2
120
TEGDO
160 [344]
< 1 x 10-4
195
850S
180 [>330]
9.0 x 10-5
193
975P
215 [>350]
3.6 x 10-6
202
X-613
191 [337]
5.0 x 10-5
BOB
156 [320]
8 x 10-3
148
500P
236 [>350]
1.0 x 10-8
232

11. Coalescent Vapor Pressure vs. Boiling Point Curve

12. VOC, 110ºC for 1 Hour ASTM D-2369, Part of EPA 24

13. Volatility by Thermogravametric Analyzer VOC
We need to rename xBOB. Also need TGA for xBOB and TXIB as well.

14. VOC, ASTM D6886

15. Proposed Modification of ASTM D6886 GC VOC Method - Methyl Palmitate BP Marker
Boiling Point at atmospheric pressure of methyl palmitate: 417ºC, 332ºC and ºC.
In California, South Coast Air Quality Management District (SCAQMD) is considering adoption of this method to quantify VOC. TMPDMIB, TMPDDIB and many other coalescents will be 100% VOC by this definition. (Draft Method 313) if set to this marker.

16. ASTM D6886 with Methyl Palmitate Marker X-613

17. Initial Coatings Evaluation

18. First Experimental Protocol
Goal
Provide data to demonstrate the utility of the new benzoate triblend for coatings
Formulations
Three polymers
Vinyl acrylic type: MFFT = 9ºC, Tg = 12ºC
Soft acrylic for low VOC applications: MFFT = 8ºC, Tg = 7ºC
Harder acrylic copolymer: MFFT = 28ºC, Tg = 31ºC
Three paints
Flat based on vinyl acrylic: Volume solids = 34.8%, PVC = 58%, VOC = 50 g/L
Semigloss based on acrylic: Volume solids = 33%, PVC = 29.8%, VOC = 50 g/L
Gloss based on harder acrylic copolymer: Volume solids = 35%, PVC = 18%, VOC = 160 g/L

19. Total Coatings’ VOC and Calculated Contribution of Coalescents

20. Experimental Protocols: Tests
Wet paint and filming – Viscosity, rheology, heat stability, leveling, freeze/thaw, wet edge/open time, dry to touch, mud cracking
Dry paint – Adhesion, scrub resistance, blocking, wet adhesion, dry adhesion, accelerated dirt pick up, contrast ratio, reflectance, color, gloss
Not all tests run for each evaluation. Not all tests discussed.

21. Semigloss Paint Blocking Resistance

22. Gloss Paint Scrub Versus Coalescent Concentration

23. Next Step: Interior Architectural Paint Based on a Harder Polymer

24. Paint Formulation Variables
Vinyl Acrylic Flat
Polymer, 7°C MFFT, 22°C Tg
Volume Solids = 38.1%
PVC = 53 %
Coalescent level = 6 pounds/100 gallons
Control TMPDMIB
Low VOC coalescents of 850P, 975P and TEGDO
Acrylic Semigloss
Polymer, 17°C MFFT, 19°C Tg Volume solids = 34%,
PVC = 22%,
VOC = 150 g/L
Coalescent level = 12 pounds/100 gallons
Control TMPDMB with 150 g/L formula adjusted to < 50 g/L
Low VOC coalescent paints adjusted to < 20 g/L

25. Results
The following tests were equal or similar to the control, TMPDMIB, in both the flat and the semigloss:
Wet Adhesion (1 week, gloss alkyd), Viscosity, ICI, Flow & Leveling.
Hiding, Freeze / Thaw - 3 Cycles, Dry-to-Touch Time.
Block Resistance
But there were some positive performance improvements – Illustrated in the following slides
Scrub resistance
Scrub resistance versus coalescent concentration
Gloss development

26. Vinyl Acrylic Flat Paint Scrub Versus Coalescent Concentration

27. Acrylic Semigloss Scrub Versus Coalescent Concentration

28. Acrylic Semigloss Block Resistance
The general trend here shows that the blocking resistance of the Texanol formulations tended to be slightly better than the blocking of the low VOC coalescents. However, it is worth emphasizing that the Texanol formulations were at the <150 g/L or the <50 g/L VOC level, while the low VOC formulations were <20 g/L.

29. Acrylic Semigloss Gloss development

30. New Benzoates Interior Architectural Paint Based on Hard Polymer

31. Paint Formulation Variables
Vinyl Acrylic Flat
Polymer, 7°C MFFT, 22°C Tg
Volume Solids = 38.1%, PVC = 52.8
Coalescents all at 6 pounds/100 gallons
Acrylic Semigloss
Polymer, 17°C MFFT, 19°C Tg
Volume solids = 34%, PVC = 22%
Coalescents all at 12 pounds/100 gallons
Control TMPDMIB, 50 g/L formula
Low VOC paints, < 20 g/L formula

32. Total Coatings’ VOC and Calculated Contribution of Coalescent

33. Results
The following tests were equal or similar to the control, TMPDMIB in both the flat and the semigloss for 500P, 613 and BOB:
WPG, pH, Viscosity, ICI, Sag
Contrast Ratio - 3 Mils, Reflectance, Freeze / Thaw - 3 Cycles, Dry To Touch Time
But there were some positive performance improvements:
VOC reduction
Better leveling and wet edge in the flat

34. Vinyl Acrylic Flat Open-time / Wet Edge Rating

35. Vinyl Acrylic Flat Scrub Resistance

36. Semigloss Acrylic Open-time / Wet edge Rating

37. Semigloss Acrylic Scrub Resistance

38. Exterior Paint Evaluation

39. Florida Fence Data to Date

40. Exterior Paint Test Protocol
Goal
Determine the performance of commercial dibenzoate blends in exterior paint
Formulations
Polymer – Two base polymer emulsions
Low VOC acrylic type: MFFT = 8°C, Tg = 7°C
All acrylic exterior type: MFFT = 11°C, Tg = 9°C
Paint
Exterior flat - all acrylic exterior type polymer Volume solids = 38.2%
PVC = 46.0%
Coalescent at 7.7 pounds/100 gallons for each (10% excess)
Exterior semigloss - soft low VOC acrylic polymer Volume solids = 33.7%
PVC = 29.8%
Coalescent at 3.5 pounds/100 gallons for each

41. Three Year Fence Data: South and North Vertical
South Vertical, Southern Pine, Flat paints dried at 4.4°C
General appearance, mildew: TMPDMIB – 5.5, TEGDO – 6, 850S – 7.5, 975P – 6
Dirt pick up: all rated
North Vertical, Southern Pine, Flat and Semi-gloss paint dried at RT
Flats
General appearance and dirt pick up: all 8’s
Cracking/delamination: all are still rated 10
Mildew: all >8
Semigloss
All 2’s for mildew and general appearance
Dirt pick up: all 7’s

42. Fence Data: South 45° 45° South
General appearance and mildew growth fell below 8 at 18 months
Dirt pickup fell below 8 after 24 months

43. Partitioning

44. Partitioning
Factors affecting the rate of partition into the polymer particles
Water-insoluble versus water-soluble coalescent types.
Tg of the polymer, hardness.
Type of surfactant present.
Mixing and temperature during incorporation.
Protocol to determine partitioning:
Mix emulsion.
Add coalescent at level recommended.
Take MFFT at different time intervals.
Consider surfactants – effect on MFFT, particularly HLB value.

45. Minimum Film Formation Temperature
Coalescents at 3% on the polymer emulsion, or 16 #/ 100 gallons, Polymer MFFT = 16°C.

46. Partitioning with 850S in Styrenated Acrylic Emulsion
MFFT, °C

47. Recap and Conclusions
Low VOC alternates by any method of test, the new dibenzoate blends (975P, 850S and 500P) and monobenzoates (613 and BOB) function well in architectural paint versus a common low VOC plasticizer/coalescent
Specifically in paint properties
With dibenzoate blends, scrub and block resistance tests are the same as or better than the high VOC coalescent films – Tough films
Monobenzoates are listed as flavor additives and while higher in VOC than dibenzoates are still quite low
Similar in other properties
Exterior exposure data does not expose any deficiencies in the paints with the dibenzoate blends

48. Next Architectural Coating
In late began exterior exposure series in flat and semigloss in Kalama, Florida, and Southeast Asia.
Control, 975P, 500P, 613, and BOB.
Industrial Maintenance Coating
First quarter 2014 – began evaluation for DTM primer and topcoat.
Control, 975P, 850S, 500P, and 613.

49. Acknowledgements
Permission to publish by Emerald Kalama Chemical LLC, Ed Gotch, CEO
Debbie Davidson, Sarah Strother, Ian Query, Emily McBride, and Dan Marschall for data development
Emerald Kalama’s Research and Applications Lab Building.
Some of the Emerald Kalama Research Staff
in front of the lab

50. Disclaimer
The information contained herein is believed to be reliable, however is based upon laboratory work with small scale equipment and does not necessarily indicate end-product performance. Because of variations in methods, conditions and equipment used commercially in processing these materials, Emerald makes no representations, warranties or guarantees, express or implied, as to the suitability of the products for particular applications, including those disclosed, or the results to be obtained. Full-scale testing and end-product performance are the responsibility of the user. Emerald Performance Materials shall not be liable for and the customer assumes all risk and liability for use and handling of any materials beyond Emerald’s direct control. Nothing contained herein is to be considered as permission, recommendation nor as inducement to practice any patented invention without permission of the patent owner.

51. Test Methods Test Reference/Method pH ASTM E70 Stormer Viscosity
ASTM D562
ICI Viscosity
ASTM D4287
Contrast Ratio, Reflectance, and CIE Values
ASTM D2805, E97, D2244 – 3 mil wet film over a Leneta 3B chart dried for 5 days. Contrast ratio is reflectance of black over reflectance over white.
Gloss and Sheen
ASTM D2243 – 3 mil wet film on Leneta 3B chart
dried for five days.
Low Temperature Coalescence
Paint and equipment conditioned at 40°F for 2 hours. Paint drawn down on a Leneta Form HK to 6 mils wet. The films were dried horizontal for 24 hours and rated (see lab rating system below).
Thermogravametic Analysis (TGA)
TA Q-500 TGA employed. Isothermal under air with a flow rate of 160 ml/minute. 5 mg sample size
VOC, Oven method
EPA 24, D-2369, 3 ml toluene used with 0.3 g sample.
Lab Rating System
10= Excellent, 0= Very poor
VOC, GC method
ASTM D-6886, post add of 1.5% coalescent to a commercial zero VOC paint
VOC GC method
ISO
Boiling point, atmospheric or reduced pressure
Reported values as available reported for reduced pressure or atmospheric pressure. Most of atmospheric extrapolated for reduced pressure data
Flow and Leveling
ASTM D4062 – Leneta test blade used to apply paint. Dried paint rated.
Dry Adhesion
ASTM D3359B – Paint was applied to dried aged alkyd with a brush and dried for 7 days before testing by cross hatch tape adhesion.

52. Test Methods Continued
Reference/Method
Scrubbability
ASTM D2486 – Paint applied at 7 mils wet to a leneta P121-10N chart and dried at room temperature for 7 days. A 10 shim was employed with abrasive media (SC-2). Failure was a continuous thin line at the shim.
Wet adhesion
ASTM D A gloss alkyd (ICI / Devoe Devguard Medium Green) was applied by drawdown and cured for 6 to 12 weeks at room temperature on a Leneta P121-10N scrub chart. A drawdown of the test paint was made perpendicular to the gloss alkyd and allowed to dry for 24 hours. The coating was then crosshatched into squares with sufficient pressure to cut the latex paint film but not enough pressure to cut the alkyd film. The test panel was soaked for 5 minutes in water. The panel was placed in the scrub machine so that the squares were in the path of the nylon brush. The % removed after 500 cycles were reported.
Sag resistance
ASTM D-4400
Dirt pick up
3 mil of paint applied to aluminum panel and dried for 24 hours. Then it was placed in the QUV chamber for 7 days of exposure. The top half of the panel was covered up and the synthetic dirt was spread evenly over the un-covered portion. The panel was placed in a 120’ oven for 30 minutes. The panels were removed from the oven and the loose dirt was removed by tapping on the panel. The top portion of the panel was uncovered. The % Y reflectance of the tested part and the untested part were read. The % Y reflectance retained was reported. The higher the %, the better the dirt pick up resistance.
Porosity Ratio
ASTM D3793 – A 6 mil applicator was used to apply paint film to white Leneta WB charts. The ambient (dried 7-Days) and low temperature conditioned at 40ºF (dried 48 hours) were stained with 10 mils of Leneta Staining Medium for 5 minutes. The stain was washed off with mineral spirits and then air dried 3 hours. The difference in porosity of the unstained and stained was calculated for each the ambient and 40ºF conditioned panels. The ratio of the porosities of the 40ºF to the ambient was calculated.

53. Test Methods Continued
Flow and Leveling
ASTM D4062 – Leneta test blade used to apply paint. Dried paint rated.
Dry Adhesion
ASTM D3359B – Paint was applied to dried aged alkyd with a brush and dried for 7 days before testing by cross hatch tape adhesion.
Wet Edge/Open Time
Paint applied with notched drawdown bar on Leneta WB chart. At 1 minute intervals ¼ of 1” brush was dipped into the paint and brushed 10 strokes across the line. The wet edge was rated with the lab system.
Scrubbability
ASTM D2486 – Paint applied at 7 mils wet to a leneta P121-10N chart and dried at room temperature for 7 days. A 10 shim was employed with abrasive media (SC-2). Failure was a continuous thin line at the shim.
Blocking Resistance
ASTM D4946 – 3 mil wet films applied to Leneta WB chart and the films were dried for 7 days. Blocking was tested face to face at ambient and 120°F with a 1 Kg weight in place. The samples were separated and rated.
Color Acceptance
Tinted paint (with 2 ounces/gallon black) drawn down at 3 mils. After one minute the paint is rubbed up in the unsealed area. The color acceptance is then rated.
Touch Up
Touch up was tested with the paint prepared for the color acceptance. Self primed Upsom was used and applied with a Linzer 2”Bristle and polyester brush at RT and 40°F and allowed to dry overnight. The test paint was applied and rated for sheen uniformity and color difference.
Low Temperature Touch-Up
(Brush over Roll)
ASTM D7489 – Wet tinted paint was roller applied onto 1 sq.ft. Upson Board panels, all conditioned in constant temperature environmental room and dried for 24 hours. For touch up, the paint, brush, and panel conditioned at 40ºF for 4 hours, and immediately 5 strokes vertical and 5 strokes horizontal of the conditioned paint were applied as second coat onto panel. Panel replaced into 40ºF and condition for additional 24 hours. ASTM Standardized Scoring System used to rate for visual and instrumental: Rating of 1 = Poor, 3 = Good, 5 = Excellent.
Mudcracking
Paint was applied with a Leneta Antisag meter (14-60 mils) on an HK chart at ambient and 40°F. After 24 hour dry the greatest mils without cracking noted.

54. Test Methods Continued
Reference/method
Freeze/Thaw
ASTM D2243 – Frozen at 0°C and thawed at ambient. 3 cycles used.
Heat Stability
ASTM D1849 – Tested at 120°F for two weeks.Initial and final viscosities taken.
Drying Time
ASTM D1640 – 3 mil wet film applied to Leneta 3B, set to touch determined at ambient.