Dimethyl Carbonate (DMC), VOC Exempt

Ever wondered what are the chemical properties of a number of VOC Exempt Solvents – Dimethyl Carbonate, Acetone, PCBTF, TBAc, vs. other common solvents such as MEK, MIBK, IP Acetate and n-Butyl Acetate (not VOC Exempt solvents)? The case of Dimethyl Carbonate (DMC).

1. Dimethyl Carbonate (DMC) The New VOC Exempt Solvent

2. Dimethyl Carbonate (DMC) History 1997 - Manufacturing Process changes from Phosgenation to Esterification greatly reducing costs 2002 – DMC is characterized as generally safe in Europe and is named “Green Product” by Chinese equivalent to EPA 2004 – Initial Application is made to EPA for VOC Exemption 2009 – Jan. 13 th - DMC and Propylene Carbonate are characterized as VOC exempt

3. PRODUCT INTRODUCTION

4. Chemical Structure and Formula CAS: 616-38-6 Formula: C3 H6 O3

5. Dimethyl Carbonate Solvent Comparison Chart for Common Solvents Chemical Properties Dimethyl Carbonate Acetone PCBTF Tert Butyl Acetate Toluene Xylene MEK MIBK Isopropyl Acetate n-Butyl Acetate Total Hansen Solubility Parameter   10.4 9.76 8.64 8.11 8.9 8.7 9.13 8.3 8.61 8.49 Relative Evaporation rate 3.22 6.32 0.9 2.8 1.9 0.7 3.9 1.6 3 1 Flashpoint 'F 63 (-) 4 109 40 45 86 24 60 42 81 Specific Gravity @ 20'C 1.072 0.791 1.342 0.865 0.872 0.863 0.804 0.802 0.872 0.882 Boiling Point 'F 195'F 132'F 282 208 231 280 175 240 188 250 Lbs/gal 8.93 6.59 11.24 7.22 7.26 7.24 6.71 6.67 7.27 7.35 MIR value 0.06 0.43 0.11 0.22 3.97 7.37 1.49 4.31 1.12 0.89 VOC by EPA No No No No Yes yes yes yes yes yes HAPS No No No No Yes yes no yes no no

6. PRODUCT CHARACTERISTICS

7. Other VOC Exempt Solvents In the United States today there are few VOC exempt solvents that are not HAPS (or ODS) and even fewer that can be purchased for less than $2.00/lb to allow formulators an option for low cost formulations for the coating, cleaning & adhesive markets. DMC is consistently one of the least expensive options: VOC Exempt Solvents: Acetone Dimethyl Carbonate Methyl acetate P- Chlorobenzotrifluoride (PCBTF) Tertiary Butyl Acetate ( tBAc )

8. PRODUCT CHARACTERISTICS Relative Evaporation Rate for Common Solvents Chemical Properties Dimethyl Carbonate Acetone PCBTF Tert Butyl Acetate Toluene Xylene MEK MIBK Isopropyl Acetate n-Butyl Acetate Relative Evaporation Rate 3.22 6.32 0.9 2.8 1.9 0.7 3.9 1.6 3 1 VOC by EPA No No No No Yes yes yes yes yes yes HAPS No No No No Yes yes no yes no no Fast to moderate evaporation rate of 3.22 –3.4 with Butyl Acetate = 1.0. This makes it similar to TBAC at 2.8 and Isopropyl acetate at 3.0 Much slower than Acetone at 7.2 it can be used as slightly slower evaporating replacement for MEK at 3.8 or Ethyl Acetate at 4.1. It is not as slow as PCBTF at 0.9, IPA (1.7), MPK (2.3), Ethanol (1.8) and MIBK (1.6) But is faster than IPA (1.7), MPK (2.3), Ethanol (1.8) and MIBK (1.6) Evaporation Rate

9. DMC’s Odor Profile

10. PRODUCT CHARACTERISTICS Flashpoint Comparison Chart for Common Solvents Chemical Properties Dimethyl Carbonate Acetone PCBTF Tert Butyl Acetate Toluene Xylene MEK MIBK Isopropyl Acetate n-Butyl Acetate Flashpoint 'F 63 (-) 4 109 40 45 86 24 60 42 81 VOC by EPA No No No No Yes yes yes yes yes yes HAPS No No No No Yes yes no yes no no

11. California OEHHA Assessment ASSESSMENT: In 2009, California's O ffice of E nvironmental H ealth H azard A ssessment issued a toxicity assessment of DMC that used the toxicity of its primary metabolite methanol and existing DMC studies to issue a toxicological assessment of DMC They reported that there were no concerns that DMC (like methanol) would be carcinogenic CONCLUSION: The OEHHA report concluded that the levels of DMC that the general public will likely be exposed to via the inhalation in the environment appears to have “ relatively minor” environmental health concerns The report established an interim acute and chronic REL, where the acute REL is identical to MEK’s and the chronic REL similar to Isopropanol’s .

12. MIR Value DMC has the lowest MIR value of any liquid chemical in commercial use based on studies conducted by Dr. William Carter at Exxon Mobile. This ultra-low MIR value is leading to fast approval of DMC by various states due to its very favorable ozone reduction potential. MIR Value Comparison for Common Solvents Chemical Properties Dimethyl Carbonate Acetone PCBTF Tert Butyl Acetate Toluene Xylene MEK MIBK Isopropyl Acetate n-Butyl Acetate MIR value 0.06 0.43 0.11 0.22 3.97 7.37 1.49 4.31 1.12 0.89 VOC by EPA No No No No Yes yes yes yes yes yes HAPS No No No No Yes yes no yes no no

13. PRODUCT CHARACTERISTICS Solubility Comparison Chart for Common Solvents Chemical Properties Dimethyl Carbonate Acetone PCBTF Tert Butyl Acetate Toluene Xylene MEK MIBK Isopropyl Acetate n-Butyl Acetate Total Hansen Solubility Parameter  10.4 9.76 8.64 8.11 8.9 8.7 9.13 8.3 8.61 8.49

14. DMC in Waterborne Systems Being an ester, DMC can hydrolyze in acidic and basic conditions to methanol and carbon dioxide and can be stable in neutral conditions with suitable buffers (formulators may need to take precautions to prevent CO2 accumulation) DMC’s primary use should be in solvent borne systems where residual water does not normally cause any hydrolysis issues.

15. EPA Statement According to the final ruling released January 13 th of 2009, the EPA will revise its definition of volatile organic compounds (VOC) deleting DMC and Propylene Carbonate which the agency has said contribute minimally to ground level ozone formation. The final ruling, which appears in the subsequent edition of the Federal Register after the January 13 th ruling, will take effect 30 days after publication. The rule effectively and definitively removes Dimethyl Carbonate and Propylene Carbonate from the definitions of controlled volatile organic compounds at 40 C.F.R. 51.100(s).

16. DMC for Architectural, Aerosol & Automotive Coatings Each state must still exempt DMC & PC for stationary source VOC rules. As of March 2011, 45 states have exempted DMC and by the end of 2011 all states aside from California (which must have each district separately exempt DMC) will have exempted DMC. California must have each of their Air Districts separately exempt DMC for coatings, Inks and adhesives. This is currently happening (see California VOC Exemption map) For Architectural Coatings, DMC is VOC exempt in all states today except parts of California & Mass. Due to its ultra low MIR value, DMC can be used in aerosol coatings in California and is soon to be approved in every state for us in aerosol coatings.

17. DMC - VOC Exempt States Washington Oregon California Each AMD must exempt Nevada Idaho Utah Arizona Montana Texas New Mexico Colorado Wyoming Nebraska Oklahoma Kansas North Dakota South Dakota Wisconsin Minnesota Iowa Missouri Arkansas Dec. 2012 Louisiana Indiana Illinois Ohio Kentucky Mississippi Alabama Florida Georgia South Carolina North Carolina Virginia West Virginia Maryland Delaware Pennsylvania Maine Vermont Rhode Island New York New Jersey Massachusetts Connecticut New Hampshire Michigan Alaska Hawaii Tennessee VOC Exempt States = Blue

18. DMC Exemption Status in Calif. Most county AMD’s plan to exempt or have no VOC rules (functionally exempt) Shasta, Glenn & Tehema AMD’s may already exempt DMC depending on application Santa Barbara users must file for a permit Bay Area AQMD (San Francisco area) looking at when they can begin rulemaking for exempting DMC in 2011 SCAQMD (L.A. area) has deferred rule making indefinitely. SCAQMD may need to look at certain coatings applications such as car refinishing and in plant coatings to exempt first.

19. California CARB Consumer items CARB regulates consumer product applications Coatings are covered by each AQMD separately Paint thinners are in their “multi-purpose solvent” classification Some local Calif. AMD’s debate that CARB can regulate paint thinners over them)

20. Paint and Coatings

21. Biodiesel Additive

22. Household, Institutional & Industrial

23. Inks

24. Resin Manufacturing

25. Benefits & Advantages

26. DMC Cost & Supply DMC pricing is well below $ 1.00/lb, making it price competitive with most oxygenated solvents except possibly acetone. Drums and bulk isotanks readily available from our factories in China. DMC is used in very large volumes in China for coatings primarily because of its low cost. Totes can be filled from isotanks or shipped from location. All packages come neatly labeled on new pallets, shrink-wrapped with all necessary shipping documents and labels. Long term a bulk tank opportunities in USA is possible

27. Sampling Process Samples are readily available and have already been sent to over 350 prospective customers. To request a sample, please contact your CCC representative or visit us at www.ccc-group.com

28. Propylene Carbonate - Propylene Carbonate has a low viscocity 2.4 cps, and a high flashpoint of 253 º F. -PC is a very slow evaporating solvent (evaporation rate <.005, BuAc =1) which restricts its solvent use. -Its Practically non-toxic by oral, dermal or Inhalation, and is classified as a slight skin and eye irritant. - It’s manufactured by the same factories that manufacture our Dimethyl Carbonate. -PC has a very low toxicity profile which allows it’s use in cosmetic products. -Readily biodegradable -Safe for all consumer items -Useful as a co solvent, wetting agent or tailing solvent. - PC can also be used in binary & tertiary solvent systems to replace other common solvents like trichlorethane and toluene. Other VOC Exempt Products to Consider: