1. T-Butyl Acetate (TBAC): A Versatile Substitute for Toluene Daniel B. Pourreau, Ph.D. LyondellBasell FISI-ANAFAPYT Conference September 27, 2016 Mexico City, Mexico DF

2. lyb.com Tert-Butyl Acetate (CAS 540-88-5) Unusually stable and versatile Ester solvent Evaporation rate = 2.8 x faster than n-butyl acetate Minimal solubility in water (0.8 wt%) Resistant to hydrolysis, aminolysis, and oxidation Low acute and chronic toxicity Negligible environmental impact Properties and solvency similar to toluene Principal Uses: –Coatings & inks –Adhesives & sealants –Industrial cleaners and degreasers –Process solvent 2 TBAC is a versatile solvent with negligible environmental impacts

3. lyb.com TBAC Toxicology and Metabolism TBAC exposures will occur primarily by inhalation TBAC has a strong camphor-like odor (detection threshold = 8ppb) 1 TBAC vapors are irritating to the eyes (threshold = 177 ppm) 1 Inhaled TBAC metabolizes rapidly to TBA and acetic acid Blood levels of TBA increase after TBAC exposure Unlike toluene, TBAC and TBA have low solubility in lipids –Less likely to cross blood-brain barrier –Less likely to cause chronic central nervous system damage Elevated TBA blood levels cause symptoms similar to alcohol intoxication OSHA Permissible Exposure Limit (8hr PEL) is 200 ppm Humans unlikely to tolerate >50ppm TBAC for more than a few minutes 3 1 Cain and Schmidt, Atmospheric Environment, 43 (2009) 2591–2601

4. lyb.com Solvent Odor, Pungency, and Irritation Thresholds 4 TBAC and esters are much more irritating than toluene Less irritating More irritating 1 Cain and Schmidt, Atmospheric Environment, 43 (2009) 2591–2601

5. lyb.com 5 TBAC Pharmacokinetics 35 and 350 ppm TBAc in air for 6 hours urine Expired air < 1% in rat after 48 hours 35ppm 350ppm 89%67% 5%27% TBAC is rapidly metabolized and excreted Huntingdon Life Sciences METABOLISM AND PHARMACOKINETIC STUDY IN THE RAT AFTER INHALATION 2000

6. lyb.com 6 TBAC Metabolism 35 and 350 ppm TBAc in air for 6 hours t-butanol metabolites 35ppm350ppm 71%81% 26%17% TBAc metabolites unidentified metabolites 3%2% n Acetic acid is part of citric acid cycle n Acute and chronic effects of TBAc similar to t-butanol Hydrolysis to tert-butanol is rapid in the blood Huntingdon Life Sciences METABOLISM AND PHARMACOKINETIC STUDY IN THE RAT AFTER INHALATION 2000

7. lyb.com Relative Lipophilicity of Solvents and CTE Risk Blood to brain transfer rate and potential to induce chronic toxic encephalopathy (CTE) is strongly correlated to a solvent’s lipophilicity 1 7 J. van der Hoek; M. M. Verberk; G. Hageman "Criteria for solvent-induced chronic toxic encephalopathy: a systematic review". International Archive of Occupational and Environmental Health. 2000 73: 362–368."Criteria for solvent-induced chronic toxic encephalopathy: a systematic review" Lower Risk Greater Risk

8. lyb.com Implications for Inhalation Abuse and CTE Risk TBAC’s significantly higher nasal pungency and irritation potential makes it a less likely candidate for abuse than toluene TBAC’s rapid metabolism to TBA and low lipophilicity reduces the potential chronic risk to the brain and central nervous system vs. toluene HOWEVER, –The TBA metabolite also has acute CNS effects comparable to alcohol intoxication and metabolism is 4x slower than ethanol Solvent substitution SHOULD NOT be the only (or primary) precaution to mitigate inhalation risk or abuse Additional risk mitigation steps include: –Prohibit sale and prevent theft of solvent-based products to minors –Educate parents and minors on solvent hazards 8 Overexposure to All Solvents Should be Avoided

9. lyb.com Toluene’s Indirect Health Impacts Toluene is a potent precursor to ground level ozone and particulate matter (PM2.5 and PM10) 9 Toluene emissions contribute greatly to air pollution W. P. L. Carter, "Development of a database for chemical mechanism assignments for volatile organic emissions," J. Air & Waste Management Association, Volume 65, Issue 10, pages 1171-1184, 2015 http://www.engr.ucr.edu/~carter/emitdb/

10. lyb.com Volatile Organic Compounds (VOCs) are Precursors to Smog (ozone and PM) 10 VOCs + sunlight + NOx Ozone + PM2.5 + PM10 (SMOG) Carter, W. P. L. and G. Heo, “ Development of Revised SAPRC Aromatic Mechanisms,” Atmos. Eviron., 77, 404-414, 2013.Atmos. Eviron., 77, 404-414, 2013 http://www.cert.ucr.edu/~ carter/SAPRC/pmchrpt.pdf

11. lyb.com Toluene is Greatest Contributor to Ozone in CDMX “Toluene is the most emitted VOC pollutant in the city and represents 25% of all toxic VOC emissions.” (SEMARNAT 2010) “Clean air actions aiming to control tropospheric O3 in the MCMA should focus on controlling toluene sources” (J.P. Garzón et. al. 2015) 1 Company Confidential 11 1 Garzón et. al. Atmospheric Environment 119 (2015) 415-429 http://www.aire.df.gob.mx/

12. lyb.com VOC Regulations in North America Many countries limit VOC emissions from factories and VOC contents in industrial and consumer products The US and Canada have exempted TBAC and many other substances from VOC regulations based on their negligible photochemical reactivity (ozone forming potential) –This has promoted substitution of highly reactive compounds like toluene with negligibly reactive ones like TBAC and acetone Mexico also regulates VOC emissions in Federal and local rules: –NOM-121-SEMARNAT-1997 –NOM-122-SEMARNAT-1998 –NOM-123-SEMARNAT-1998 SEMARNAT also exempts compounds that are negligibly reactive such as acetone, but has outdated lists of exempt compounds. 12 SEMARNAT should update its lists of exempt compounds

13. lyb.com Toluene Also Regulated as a Toxic in the US EPA Clean Air Act Section 112(b) Hazardous Air Pollutants (HAP) list EPA SARA Title III Section 313 (Toxic Release Inventory) In 2008, Garlock Sealing Technologies of Palmyra, NY, earned an EPA Clean Air Excellence Award for replacing toluene with TBAC in their sheet gasket manufacturing process: –During the five-year, $3 million project, many solvent substitutes were investigated and a non-VOC/HAP solvent was found, tried, and proved, resulting in the development of a new manufacturing process. –The project included high-efficiency recovery systems to capture and reuse the new non-VOC solvent. The system has realized an average efficiency of 95 percent year-to-date. –In November 2007, Garlock’s Palmyra, New York facility made its last VOC/HAP based sheet gasket, resulting in the production of a better product with significantly lower environmental impact. 13 Regulations are effective for reducing toluene emissions

14. lyb.com Garlock: From Worst to Best in NY State Company Confidential 14 Garlock eliminated its TRI releases with TBAC

15. lyb.com Solvent Substitution Case Study: Garlock Gasket Manufacturing, Palmyra NY 1.TBAC added to rubber to make paste 2.Paste pressed into a sheet 3.Air in press area sent to carbon beds for purification 4.TBAC steam desorbed, decanted, and recycled Observations from solvent change: –Workers initially complained of strong TBAC odor –Ventilation and solvent recovery had to be improved –Same carbon bed solvent recovery system was used –TBAC stable to steam desorption and separation from water –95% of TBAC is now recovered and recycled –Eliminated 100% of HAP, TRI, and VOC emissions Company Confidential 15 Worker exposure to solvent also greatly reduced

16. lyb.com Other Examples of Toluene Replacement with TBAC Solvent based coatings Flexographic and Gravure printing inks Contact cements Construction sealants Single-ply roofing membrane adhesives Acrylic lacquers for concrete decking Nitrocellulose lacquers for wood finishing Automotive refinish urethane coatings Industrial maintenance coatings (epoxy and urethane) Hand-wipe solvents for aircraft surface preparation Industrial degreasers Paint thinners 16

17. lyb.com Summary TBAC is a versatile and safer alternative to toluene TBAC is VOC-exempt in the United States and Canada Regulating toluene as a VOC and toxic air contaminant has spurred it replacement in the US and Canada TBAC should be added to the lists of VOC exempt solvents in Mexico’s regulations Updating NOM-121/2/3-SEMARNAT-1997/8 VOC regulations would reduce the use of toluene and ozone-producing solvents Regulating toluene as a toxic air contaminant would also provide incentives to replace it with safer alternatives like TBAC 17 Replacing toluene would improve air quality and health

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