## Before the Environmental Protection Agency


# Petition to Exempt 2-Amino-2-Methyi-1-Propanol CAS No. 124-68-5 From Regulation As A Volatile Organic Compound
Submitted by The Dow Chemical Company October 3rd, 

# 2012

Linda E. Troester EH&S Produ ct Stewardship Manager The Dow Che mical Company 1500 E. Lake Cook Rd Buffalo Grove, IL 60089 TEL: 847-808-3432 E-mail: LTroester @ dow .com Donald Fontaine Toxicology and Environmental Rese arch Consultant The Dow Chemical Company 1803 Building Midland, MI 48674 Asghar Peera Associate Scientist The Dow Chemical Company 1500 E. Lake Cook Rd Buffalo Grove, IL 600 89
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## Executive Summary T he Dow Chemical Comp any submits this petition requesting that EPA modi fy the defini tion of volatile organic co mpound (VOC) found at 40 CFR 5 1

. 100( s) to exe mpt 2-A min o-2- methyl- 1-prop anol (AMP) from regu lation as a VOC. AMP is u sed to disperse pigments in water-based coatings and has s ignificant performanc e advantages compared to available substitute mate ri als. AMP a lso i s used as an additive in metalworking fluids , as an intermediate in chem ical synthesis, as an additi ve in the production of food co ntact paper, as a neutralizer in personal care products, and also into so me other min or uses. AMP meets the criteria that have been used to grant prior VOC petitions. Specifically, t he current maximum incremental reactivity (M IR) value for AMP is 0.25 grams ozone per gram of VOC , w h ich is below the MIR value of the benchmark c hem ical ethane, which is 0.28 gram ozone per gram ofVO C. Older MIR values t h at are no lo nger accepted as va lid, are addressed in the pe tition. Species whic h scavenge radicals tend to have h igher variability associated with thei r MIR values. Th is is the case with AMP. The MIR val ue in fact is negative under many conditions, me aning that the presence of AMP inhibits ozone formation under th ose condition s. AMP also is a solid at ambi ent temp era tures and has low volatility, such that less than 100 percent of e mi tted AMP is available to contribute to ozone formation. Modeling that assumes I 00 percent availability tend s to overstate AMP 's potential contribution to ozone fo rm ation. These points are explaine d further i n the petition. AMP i s n ot regulated as a hazardous air pollutant (HAP) under Title III of t he Clean Air Act. No r is it listed as a toxic chemical un de r section 3 13 of the Emergency Planning and Community Ri g h t-to-Know Act (EPCRA). Dow Chemical respectfully urges prompt consideration and action on this petition. Manufacturers and fo rmu lators of wate r-based coatings need access to AMP to meet VOC li mi ts o n t heir products without impairing performance of their prod ucts. For r eason s ex pl ai n ed in the petition , there is considerable urgency to the situation

.

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## Table of Contents

I. Introduction 2. What is AMP? 3. Basis for the exe mp tion of AMP from VOC regulation 4. Other Environmental Fate Considerations 

### 5. Reasons fo r Requesting Prompt Action on the Petition 6. Production and Use of AMP 7. Conclusion 

## Attachments Appendix 1: AMP Regulatory Status Appendix 2: AMP Mammalian Toxicology Environmental Fate and Effects Summary Data Abb reviated Appendix 

### 3: AMP Mammalian Toxicology Environmental Fate and Effects Summary Appendix 4: AMP HPV Submission IUCLID Appendix S: AMP ECHA REACh Public Dossier Appendix 

### 6: C. L. Burnett et al. ''Final Amended Report on Safety Assessment on Aminomethyl Propanol and Aminomethyl Propanediol" , International Journal of Toxicology 28(6S) 141 S.161 S, 2009 Appendix 

### 7: Luecken, D (2007) Memorandum: Review of the Technical Basis for use of the One-dimensional MIR Scale in the National Volatile Organic Compound Emission Standards for Aeroso l Coatings Appendix 8: Harris and Pitts ( 19 83) Rates of Reaction of Hydroxyl Radicals with 2- (dimethylamino)ethanol and 2-amino- 2-methyl -1-prop ano l in the gas phase at 300 ± 2 K EST 17 50-51 Appendix 9: Summary Report by Dr. William P. L. Carter (2012). Atmospheric Ozone Reactivity Estimates for 2-Amino-2-Methyl-1-Propanol

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## 1. Introduction The Dow Chemical Co mpany submits this petition requesting that EPA exempt 2-Amino-2- methyl-1-propanol (AMP) from regulation as a VOC. The current maximum incremental reactivity (MlR ) value for AMP i s below the MIR value of the benchmark chemical e thane. Accordingly, AMP meets the criteria for exemption from regu l ation as a VOC. 2-Amino-2-methyl-1-propanol (AMP) is a unique primary aminoalcohol mar keted and sold by The Dow Chem ical Company. AMP is a molecule wit h molecular weight of 89 and boiling point of 165 °C. The vapor pressure ofpure AMP is 0.34 mm Hg @ 20 °C. The pu re chemical is a gellike crystalline solid whic h is misci ble in water
. As sold, the materi a l is typically of various puri t ies, and so ld in aqueous solutions of different concentrations for ease of h andling.



# H2N~OH 2-Amino-2

- methy l -1-p ropano l (AMP) CAS: 124-68-5 Some simple physical properties of this material are as follows:AMPProperty REGULARTM AMP-95TM Water, % b y wt < 0.8 < 5.8 Boiling Pt, 760 mm Hg, ° C 163.8 1 00-165 Me lting Pt, o C 30 -2 Flash Pt , degrees F 172 178

Specific G ravity 0.93 (40/ 40 ° C) 0. 94 (25 /25 o C ) pH ofO.l M aqueous sol'n @ 20°C 11.3 1 1.3 pKa @2 5 oc 9.72 Solubility in water @ 20 °C g/1 00 ml M i scible miscible Viscosity , cps @ 25 °C 10 2 147 

## 2. What is AMP? Pure AMP < 0.3

165 31 172 0.92 (den sity) 11. 3

miscible

solid

2-Amino-2-methyl- 1-propanol (AMP) is a primary amino alcohol wi th some unique properties that are valuable for pigment dispersion and neutralizatio n for many different applications. Chemically this substance contai ns amine and alcohol functio n al groups , and thus provides t he physical features and chemical reactivit y of both classes of compounds. There are various grades of AMP produ cts for differen t target mark ets, includin g the following:

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### Basic AMP products: AMP-REGULARTM JSCI 2-Amino-2-methyl-1-p ropanol AMP-REGULAR 2-Amino-2-methyl-1-propanol AMP-7STM 2-Amino-2-methyl-1-propanol AMP-90TM 2-Amino-2-methyl-1-propanol AMP-90 Textile, 2-Amino-2-methyl-1-propanol AMP-95TM SG 2-Amino-2-methyl-1-propanol AMP-95 2-Amino-2-meth yl- 1-propanol 

### AMP Cosmetic Grade Products: AMP-ULTRATM PC 1000, Neutra lizing Amine AMP-ULTRA PC 2000, Neutralizing Amine AMP-ULTRA PC 3000, Neutralizing Amine 

### Metalworking Fluid Grades: CORRGUARDTM -75, Amino Alcohol CORRGUARD -95 Amino Alcohol CORRGUARD A, Amino Alcohol 

### Metalworking Fluid High Purity Grades: CORRGUARD LSA 6000 Neutralizing Amine CORRGUARD LSA 7000 Neutralizing Amine CORRGUARD LSA 8000 Neutralizin g Amine Within each of these groups the re is an amount of water added to the product in order to reduce the viscosity of the mate rial for ease in handling for certain customers. Therefor e, AMP-95 has approxi mat ely 5% water, while AMP-7 5 h as app roximately 25% water. Customers can c hoo se whichever works best in their systems. 

## 3. Basis for the exemption of AMP from VOC regulation AMP meets the criteria that have been used to propose and grant prior VOC exemptions. These criteria are described 

### in the Federal Register Vol. 77, No. 57 Friday, March 23, 2012. Proposed Rules pages 16 981-16987. Air Quality: Revision to Definition of V o latile Organic CompoundsExclusion of a Group of Four Hydrofluoropolyethers (HFPEs) and in the Federal Register Vol. 74 , No

. 12 Wednesday , January 2 1 ,2009. Rules and Regu l ations pages 3437

- 344 1. Air Quality: Revision to Definition of Volatile Organic Compounds- Exclusion of Propylene Carbonate and Dimethyl Carbonate. In addition, it has been the EPA's policy that organic compounds with a neg ligible level of reactivity should be excluded from the regulatory VOC definition so as to focus VOC control efforts on compounds that do significantly increase ozone concent rat ions. The EPA h as expressly recognized that exempting such compounds creates an incentive for industry to use negligibly reactive compounds in place of mo re highly reactive compounds that are regulated as VOCs. (Federal Register Vol. 70, No. 176, September 13 , 2005, pages 54046-54051. ln terim Guidance on Control ofVola tile Organic Compound s in Ozone State Implementation Plans). The EPA lists
Page: 5compounds that it has determined to be negligibly reacti ve in its regulations (at 40 CFR 5 J .lOO(s)) as being excluded from th e definition of VOC. Also the policy of excluding negligibly reac tive compounds from the VOC definition was first laid out in the "Recommended Policy on Control of Volatile Organic Compounds" (U.S. EPA, 1 977) and was supplemented most recently wit h the "Interi m Guidance on Contro l ofVolatile Organic Compounds in Ozone State Implementation Plans" (Interim Guidance) (U.S. EPA, 2005). The EPA uses the react ivity of ethane as the threshold for determining whether a compound has negligible reactivity

. Co mpounds that are less reactive than , or equally reactive to, ethane under certain assumed conditions may be deemed negligibl y reactive and t h e refore suita ble for exemption fro m the VOC definition. Compounds th at are more react ive than ethane continue to be considered VOCs for regulatory purposes and therefore subject to control requirements. The selection of ethane as the threshold compound was based on a series of smog ch amber experiments that underlay the 1 977 policy. The EPA's 2005 Interim Guidance also noted that concerns h ave sometimes been raised about the potential impact of a VOC exemption on envi ronmental endpoints othe r than ozone concentrations , including fine particle formation, air toxics exposures, stratospheric ozone depletion, and climate ch ange. The EPA has recognized, however, that there are ex isting regulatory and non-regulatory programs that are specifically designed to address these issues, and the EPA continues to believe that the impacts ofVOC exemptions on environmental endpoints other than ozone formation will be adequately addressed by these programs. Hence the EPA states that VOC exemption decisions will continue to be based solely on conside ration of a compound's contributi on to ozone formation (Interim Guida nce 70 FR 54046 September 13,2005 , and Final Rule 77 FR 376 10 June 22 , 20 12)

. We a re requesting that the EPA revise the agency's definition of volatile organic compounds (VOCs) for purposes of preparing State Implementation Plans (SIPs) to attain the national ambient ai r qua lity standa rd (NAAQS) for ozone under Title I of the Clean Ai r Act (CAA). This proposed revision would add AMP to the li st of compounds excluded from the definition ofVOC on the basis that t his compound makes a negligible contribution to tropospheric ozone formation. The EPA has used three different metrics to compare the reactivity o f a specific compound to that of ethane: (i) The rea ctio n rate constant (known as kOH) with the hydroxyl radical (OH); (ii) the maximum incremen t al reactivities (MIR) of et han e and the co mpoun d in question expressed on a reactivity per mass basis; and (iii) the MIR of ethane and the compound in question expressed on a reactivity per mole basis. AMP reacts with hydroxyl radicals with kOH 

### = 2.8 x 1 o -t t cm3 molecule- sec- •. (Table 1) The corresponding kOH fo r ethane is 2.4 x J 

## o- 13 cm 3 molecule-• sec- 1

. The rate constant for AMP is greater than that of ethane and corresponds to an atmospheric lifetime (lie) of about 4 hours under the conventional assumption of a h yd roxyl radical concentration of 3 x 106 molecules 

### I cm 3

. Fo r mo st VOCs reaction w ith hydroxyl radical is the first step in the series of reactions that cycles radicals and leads to ozone formation. If this rate is slower than that for ethane the VOC may be deemed negligibly react ive. AMP, wit h a larger kOH, is more reactive than ethane, but as explained in detail in Carter 2008, AMP's reaction primarily term inates rad i cals rath er than cycling them and theref ore genera ll y reduces ozone. The primary (80%) initial product is a nitrogen centered radical (Carter 2008). This nitrogen centered radical lacks hydrogen on an adjacent carbon and is therefore unable to react with molecular oxygen to produce the hydroperoxy radica l that is responsib le fo r the cycling ofNOx and producing ozone.
Page : 6The nitrogen centered rad ical scavenge s radicals, prim ari l y NOx, an d is proposed to form a nitramine which i s assum ed to be inert (Harri s and Pit ts 19 83). The effect of AMP addition in th e c hamb er experiments of Carter 20 08 was the reduction in ozone concentration consi ste nt with th is mech anism. T he MIR va l ue is a measure of photochemical reactivity de rived from a computer-b ased photochemical model that co n siders the complete ozone forming activity of a compo und, not merely the first react ion step. The MIR values for e th ane a nd AM P 

### in units of g 

### 0 3 

### I g VOC are given 

### in Table 1

. The ozone forming reactivity of AMP is le ss than that of ethane o n thi s mass basis. Given the rela tively low molecu lar weight of ethane compare d to most VOCs, the use of MIR on a mole basis results in fewer VOCs falling into t he " negl igi b ly reactive " class versus th e mass basis. Th is is the case for several exe mpt material s list ed in Table I a nd is also the case for AMP, w here the molar MIR value is greate r than that of ethan e, but the mass MIR value is less th an that of ethan e. The EPA has con sid ered the c hoice between a molar or mass basis fo r the comp arison to e thane in past rulemaking s and guidan ce. The de sign of the VOC exe mption pol i cy, includin g th e choic e between a mass and mole basis, has be en critiqued in the publis hed literature. Most recently, in " Interim Guidance on Control ofVolatile O rganic Compounds in Ozone State Impleme ntat ion Plans " publi s hed on September 13,2005 (7 0 FR 54046) , E P A stated : ''* 

## * * a co mpari son to ethane on a mass bas i s st rike s the righ t balance between a threshol d tha t is low enough to capture compounds that significantly affect ozone concent r ations and a thres hold that is high enough to exempt so me compounds that may usefully substitute for more h ighly reactive compounds

. 

## * * * When reviewing co mpounds that h ave been suggested for VOC exe mpt status, EPA will con tinue to compare t hem to ethane u sin g kOH exp re sse d on a molar basis and MIR values exp ressed on a mas s basis.'' Relying on a co mpari son of mass MIR values consistent with this guidance, EPA can revise its definition ofVOC at 40 CFR 51.100(s) to add AMP to the list of compounds that are exempt because it is neg ligib l y reactive since it is equal to or less reactive than e thane on a mass b as is. Two MIR values for AMP have appeared in regulation s. The init ial estimate, an upper limit MIR esti mate (ULM IR), of I 5.08 g 

### 0 3 I g VOC appeared 

### in t he original California Aerosol coatings Consu mer Products regul ation 

### in July 1 8, 200 1 and thi s value was us ed by the EPA in the 2009 National Ae roso l Coatings Rule published in the Fed e ral Register volume 74, p29595-29607, Jun e 23, 2009. Thi s U LMIR estimate was based on a p rocedure develop ed by Carter (2000), for VOC s fo r which mech anisms we re not derived. Such compounds we re as signed MIRs ba sed on their atmospheric reaction rates (if known), and t he MlRs of the most react ive com p ounds of the same type. AMP, with a r easonab l y high reaction rate and an am ine functi o n , was assigned a la rge U LMIR

. The seco nd and currently accepted MIR value, 0.25 g 

### 0 3 

### I g VOC, is mu c h lower and it reflects t he ex perimental resu lts and derived mechanisms for AMP repo rted by Carter in 2008. T h is value was adopted in the California ae rosol coatings regulatio n in October 20 1 0. It is the

Page : 7current M IR va lu e for AMP in Ca lif

ornia. This current MIR value is exp l ained furth er is a repo rt prepared by Dr. Ca rter, attached as Appen dix 9. Species which scavenge radicals will have greater variability associated with their MIR values than species which simply react slowly. The reason for this is that a species which scavenges radicals will react with NOx and NOx is both necessary for ozone formation and is capable of producing species whlch reduce ozone. Th e relative rates ofthese two comp et in g processes will depen d on the nature of the radical scavenger and the environmental conditions. Since AMP scavenges radicals it i s expected to have its esti m ated MIR vary depend i n g on environmental co nd itions. The MIR calculation is based upon the ave rage of the MIR s fo r 39 standard city scenarios and can be calculated for the one scen ario repre senting th e average of the 39 s tandard scenari os. For AM P these MIRs w ere 0.25 and 0.26 g 

### 03 I g VOC, respectivel y. 

### In ei the r case the MIR i s less than that estimated for ethane ( 0 .28 g 

### 0 3 I g VOC). Furth e r, as d escribed in D r . Carter' s report , t hese val ue s likely overstate AMP's contribution to o zone formation. To the extent that MIR values may be used to estimate reactivity (Lu ecken 2007) we may conclude that , for the condition s used to define MIR, AMP has a reactivity that is less than or equal to that of et

h ane. Table 1: Reactivities of Ethane, some Exempt Compounds and AMP

Chemical Molecular kOH'•' MIR3 (gm O.Jgm MIR4 (g m Formu l a Name CAS N o. Weight (cm 3 l(mole culesec)) VOC) O.JmoiVOC) VOC Status

C

2H6 Ethane 74-84-0 30.07 2.4x 10 · 13 0.28 8

. 4 Benchmark Propylene c.H60 3 Carbona te 108-32-7 102.09 6

. 9x 10' 13 0.27 27 .5 6 Exempt C3H60 l Dimethyl Carbonate 616
-38-6 90.08 3.49 X 10' 13 0.056 5.04 Exempt 1,3,3,3
- tetrafl uoroprop ene C

3 H 2 F 4 or HF0
- 1234ze 29118 ·24-9 114.04 9

. 25 X 10' 13 0.098 11.2 Exempt 2
- Amino-2-methyl

- Seeking C

4 H 11 NO 1
- propano l (AMP) 124-68-5 89.14 2

. 8 X 10 ' 11 0.25 22.25 Exempti on
1 kOH value fo r ethane is fro m: R.Atkinson., D. 

### L. Baulch, R. A. Cox, J. N. Crowley, R. F. Hampson, Jr. , R. G. Hyne s, M.E. J enkin, J. A. Kerr, M. J. Rossi and J. T roe (2004), S ummary of Evalua ted Kinetic an d Photo c h emi cal D ata fo r Atmospheric C hem istry as cited in th e Fed Reg volume 74 , p29595-29607 , June 23 , 2009
2 kOH value for AMP is r eported in: Harris and Pitts ES T 1 7 50-5 1 (1983) Rate s of Reaction of Hydroxyl Radicals with 2-(Di methylamino)ethanol and 2-A mino -2-methyl-1-propanol in the Gas Phase at 300 ± 2 K
3 All maximu m incrementa l reactivities o r MIR (g 

### 0 3 1g VOC) va lu es are from: W. P. 

### L. Carter, "U pdated Maximum Incremental Reactivity Scale and Hydrocarbon Bin Reactivities for Regulatory Application" Table A-I Updated table ofMIR values and uncertainty c l assifications

. Page: 8This ma y b e found at http: // www.arb.ca.gov/regact/2009 / mir2009/ mir10.pdfupdated 1128/20 10 and http: //www.arb.ca .gov / regact/2009/rnir2009/mir2009.htm 4 All m aximum incremental reac tivities expressed on a m ole basis , MIR (g

**mole** VOC) , are calculated fro m the MIR expressed on a gram basis and the molecul a r weight of the VOC. 

## 4. Other Environmental Fate Considerations AMP is a reaso na bly strong base and forms salts wit h acids. 

### In many formulations AMP function s as a neutralizer and exists in th e ionic or salt form

. Very little AMP will evaporate to be available fo r atmo sphe ri c re actions. It is difficult to transfer even un-ionized AMP quantitatively to the air

. In Carte r 2008, best fits of the chamb er concentration data were obtained assumin g th at only 5 to 50 % of injected AMP was in the vapor phase. That i s , 50 to 95% of t h e injected AMP was not avai la ble in the atmosphere for reaction. Because AMP is a base it will also react with acid and pH buffers in e n vironmental media, so il , water, and air. T h ese re actio n s are certain to ensure that so methin g less than 1 00 % of the AMP that might b e re lease d from a formulated product will b e available to react to form ozone in th e atmosp he re. Once in soi l or water AMP w ill be biodegraded as it has been shown to be readily biodegradab le. (ANGUS 20 l 0) These alternative fates will reduce the amount of AMP avai labl e for reaction in the at mo sp he re. Because any AMP that does exist in the vapor p hase b a s a relatively s h ort lifetime, and because it does not contain c hlorine or b romine, it does not contr ibute to the d e pletion of the s tratospheric ozone layer and has an ozone depletion potential val u e of zero. Again, beca u se AMP has a relatively short atmos p h eric lifetime , its contribution to global wa rm ing , typica ll y measured on a 100 year ti me scale , w ill be insigni fican t
. This cont r ibution to global warming is at m ost equ al to that of t he carbon dioxide equivalent of its carbon content assum in g I00% a tmo sp heric availability and convers i on to C0 2. A considerat ion of the relative amounts of C02 from deg ra d at ion of AMP to that from bu rning carbon suggests that eve n this ove restim ate of AMP's cont ribution to g l obal carbon dioxide is in sign ificant. Amines are known to participate in atmospheric part i cle formation , in pa rt from amine salt formation and possibly absorption onto particles. Amines such as AMP h ave both photochemica l an d non pho toche mical r ou tes to particl es. Acid gases such as HN0 3 , H 2 S04 and HCI will reac t w it h AMP to form salts. Photochemical products such as the nitrami de and p eroxy species can a lso form particles. Environmental chamber experiments (Carter 200 8 ) showed that the PM fo rm ation of AMP was lower than other ami nes and d-limonene but greater than most alkanes. Cu rrently VOCs are not regulated based on their im p acts on particles , and this is not di re ctly relevant to the iss u e of whether AMP s h ould be r egulated as a VOC ozone pr ecursor . AMP not only meets criter ia that h ave been used to gra nt prior exemptions, its environmental effects , although s ma ller than those obtained by assuming that 1 00 % of AM P reacts in the atmosphere, will be to reduce ozone and NOx.
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## 5. Reasons for Requesting Prompt Action on the Petition Dow Chemical respectfully urges prompt consideration and action on this petition. Manufacturers and formu la tors of water-based coatings need access to AMP to meet VOC limits on their products without impairing performance of their p roducts. AMP is widely used in various applications as a preferred multifunctional neutralizer to adj ust pH of the fo rmulati ons. AMP is the leading additive used for neutrali zati on and improved pigment dispersion in the paints and coatings industry. AMP provides the industry with multifunctional benefits throughout the manufacturing , application and final film properties , including the ability for formulators /companies to reduce the level of other components such as dispersants, surfactants and g lyco ls

. Paints and coatings companies seek to be environmentally responsible and are trying to create 'greener ', more ' environmentally sustainable' products. AMP's regulatory status as a VOC encourages s ub stitution to other materials that are VOC-exempt but that have less favorable attributes in oth er respects , as described furthe r below

. VOC exemption for AMP, in line with its lower MIR value compared to ethane, will allow AMP to continue to be a preferred additive. Prompt action is needed so that companies do not incur the cost of changing formulations in ways that will not ach i eve any real benefit. This potential substitution for AMP is mainly seen when companies develop new product lines and substitute AMP with neutralizing agents such as ammonia and inorganic salts (hydroxides, carbonates) that are used i n paint formulations only for pH adjustments. These alternatives only provide neutralization with no additional performance benefits or possibility of formulation optimization. 

### In addition, the alternatives do not have very favorable EH &S profile. They are either corrosive (inorganic hydroxides, ammonia), toxic (ammonia) or considered to be environmentally hazardous substa nce (ammon ia). If the Volatile Organic Compounds (VOC) exemption under the federal Clean Air Act (CAA) is granted, The Dow Chemical Company, believes that formulators in the USA will continue to use AMP as the more effective alternative and environmentally beneficial product i n next generation paints and coatings. AMP has an excellent toxicity p rofile (see Appendices 2-6), is not listed as a hazardous air poHutant under the CAA or a toxic c hemical under ECPRA (see Appendix 1 ), and has negligible contribution to the tropospheric ozone. Recognition of the lack of ozone formation from use of AMP by excluding it from the definition ofVOC would allow compa nie s to eit her maintain or develop more sustainable products that reduce the formation of ground level ozone. The Dow Chemical Company, believes that AMP would see continued use in other markets, including metalworking fluids and personal care applications. AMP would remain a preferred multifunctional neutralizer due to its reduced ozone potential and favorable toxicity profile compared to commodity amines in both these applications. Based on all the information discussed in this summary report , we believe that 2-Amino-2-methyl1-pr opanol (AMP) has a favo rab le toxicity profile and has negligible contribution to atmospheric ozone and it deserves a non VOC status.
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## 6. Production and Use of AMP: 2-Amino-2-methyl-1-propanol products are produced in manufacturing facilities either in Sterlin f:,rtOn, LA, USA, or in Ibbenburen, Germany . 2-Amino-2-methyl-1 -p ropanol is manufactured according to the reaction below:

+ [Catalyst] [Catalyst]

2 -nitropropane fonnaldehyde 2-nitro-2-methyl-1-propanol 2-amino-2-methyl
- 1-propanol (AMP) 

### Markets and Uses: AMP products ar e highly useful materials for a wide variety of appl icat ions. The uses discussed below are representative but should not be considered as all-inclusive. In Coatings: AMP is utilized by manufa cturers of coatings for the dispe rsion of pigments in water-based paints or as the amine neutralizer for solubilizing acid-functional polymers in water. AMP is a highly efficient co-dispersant which im proves stability of the v iscosity. As an efficient base, AMP will stabilize the pH of latex paints , minimize can corrosion, stabilize zinc oxide paint formulations, and improve t he properties of t he dry film. The coatings manufacturer reaps the benefit of the cost-reducing advantages of AMP, such as simplified su rfactant formulation, and more efficient u ti li zation of thickeners. Th e user prefers paints with AMP because of their low odor and superior performance. For most applications, AMP is the most efficient amine available to the formulator. 

### In order to comply with air pollution regulations and volatile organic compounds (VOC) restrictions, more and more fo rmu lators are considering water-soluble coatings systems. Studies s how that resin solutions with superior stability and rheological properties can be obtained with less co-solvent and at a lower amine level with AMP. Improved performance ofthe dry film is observed. AMP formulations yield higher gloss and greater water resistance than do formulations with other neutralizing amines. Typical uses of AMP in paints and coatings would be 0 .2-0.5% by weight in the paint formulation. In Metalworking Fluid s: AMP-95TM is an excellent primary amino alcohol for use in m

etalwor king-fluid formulations. The us e of AMP-95 in the formu l ation of synthetic , se misynthetic, and soluble oil metalworking fluids can result in superior overall performance

. Evaluations of alkalinity development, emulsion stability, and foa m propensity clearly support the use of AMP-95. It is comp letely water-soluble, h as good thermal stabi lity , a high flash point, and is low in odor. These properties make it easy to handle in the workplace. T ypical concentrations of AMP in metalworking fluid concentrates would be 1-5 % by weight, while the final use diluted fluid would typically contain< 1% by weight of AMP. For Synthesis: Many useful products can be synthesized from the amino alcohol s such as salts with mineral or organic acids, amides, amide esters, oxazolines, imides and imines, oxazo lid ines, diamines and amino acids. The difunctionality of amino alcohols makes them useful as raw
Page: 11materials in polymer applications. One of the unique synt hetic approaches is their reaction with carboxylic acids to form the oxazoline structu re. Fi lm s of oxazoline alkyds, for example, are c haracterized by better resistance to water and alkali, better g loss r etention on exposure , better m ar resistance, and better salt-spray resistance than are attained wit h films of conventional alkyds. The utility of oxazolines is not limited to polymers. Oxazoline structures have applications as surface active agents , corrosion inhibitors, antifoam compounds and lubrication additives. 

### In this application the 2-A mino -2-met hyl-l-propanol would be u se d up as a raw material or intermediate for t he production. Personal Care and Cosmetics: AMP is also widely u sed in cosmetic and personal care product formulation such as lotion s and hairsprays (typical use concentrations 2-5% by weight), for neutralization and solubilization of acid-functional polymers. The Cosmetics Ingredi ents Review Expert Pan e l of the Personal Care Products Cou ncil [ http: // www.cir-safety.org/] reported in their review of AMP in "Safety Assessment of A minomethyl Propanol and Aminometbyl Propanediol ", 24-Sep-2007, t hat the use s of AMP based on reporting of their mem bers at that ti me incl uded: hairsprays and other hair-care products, hair dyes and colors, soaps and detergents, eye makeup, fragrance products, deodorants, skin care and aftershave lotions, although this is not a fully detailed list here. The hi ghest concentration reported in that document was up to 7% in hair dy es and colors , with uses at 3% concentrations o r less for the other applications. For the full information please see this copyrig hted document, which can be obtained from the Personal Care Products Council, 1101 17 St. NW Suite 412, Washington , DC 20036-4702, TEL: 202-33 1- 0651/FAX: 202-331-0088. This document is attached as Appendix 6. In Emulsions: Amine soaps of fatty acids are widely-used emulsifying agents. They appear in personal care products such as cosmetics and c reams, home maintenance products such as floor polishes and cleaners, and industrial products such as insecticide sp rays and asphalt emulsions. AMP-95TM Amino Alcohol forms particularly efficient em ulsifying agents which are far superior to those formed with the more traditional amines. The high base strength, low neutral equivalent , and low volatility of AMP make it possible to use less amine in emul sion formulations and still obtain better clarity, less odor, and more sta bility than can be obtained with weaker or more fugitive amines

. The utility of ami no alcohols in emulsions is not limited to anionic (amine soaps) application s. In nonionic polyethylene emulsions, the need for caustic can be lessened or even elimi nated by AMP. The effect of water on the dry polish film is there by lessened to a great extent. The stability and low color of AMP itself assure the formulator that fmished products will be low in color bot h initially and after storage. Typical use conce ntrations in an emul sion formulation would be l -5%. In Boiler Water Treatment: In AMP-95-Amino Alcohol , industry has available an amino alcohol which offers a proven solution to the problem of corrosion in steam-boiler condensate

return lines. Laboratory stu dies and field experience indicate that AMP-95 provide s excellent corrosion inhibition for metals of construction , efficient absorption of carbon dioxide , adequate distribution ratio to assure protection in steam-l ine runs, and minimum amine lo ss in the deaerating heater. This i s a minor use in the USA to day. Typical use concentrations in a steam boiler line would be in the 30 ppm (30 mg/L) range.

Page: 1 2As Catalysts: The salts of the amino a l cohol s can be used to prepare textile-resin catalysts with variable curing rates

- ca tal ysts use ful for re sin s which impart dimen s ional stabilization, c rease pro ofing, or wash-and wear characteristics t o fabrics. The hydrochloride salts of the amino alcoho ls are the most widely used , bu t ot h er salts such as nitrates, sulfates, phosphates , o r s ulfonates may also be effective catalysts. These sa l ts may be used alone , or in combination with magnesium ch loride or zinc nitrate, to produ ce balanced c uring acti on with selected resins. Such catalysts have also been prove n to be effectiv e in the coatings industry for impro v in g the package sta b i lit y and cur e ofbaking ename ls

. Typi cal use concentrations in text il e uses would be in the 1

- 2% range ; however, thi s is a very minor use toda y. Formaldehyde Scavenging: Oxazolidines form quite readily, so readily in fact th at the amino alco hols m ay be used to ti e up formaldehyde which otherwise might b e released to th e atmosphe re . This reaction i s reversible, with the oxazolidine formed at a high pH

. The amino alcoho ls are best used when the pH o f the system contai ni ng formaldehyde is >8.0. An example of this app roach is the use of AMP in m etalwor k

ing flui d s to effectively reduce the amoun t of formaldehyde found above a triazine containing fluid. Th i s ability of amino alcohols provides an excell ent solutio n to the odor and irritation problem often associated with the us e of u reaformaldehyde , melamine -fo rm aldehyde , phenol-formalde hyde, or re sorci nol

- form aldehyde resins. Also, the oxazol i dine itself can act as a cross linking agent and upgrade the performance of the system in terms of imp roved physical p roperties. Typical u se concentratio n s for formaldehyde scavenging wou ld be one mole of AMP for each mole of formaldehyde , i.e. about 3% or so [if we assume free formaldehyde neve r exceeds I % then roug hl y 3% maximum AMP would be needed to co mpl e te ly scavenge it]. Other Uses: AMP h as s hown value as amine b uffer wit h sma ll am o unts sold in mino r quantities in a variety of p h armaceutical, diagno s tic and b iochemica l a pp licati ons. AMP has some minor uses in cleaning p roduc ts and in gas treatment wh ere the AMP is pr esent at fairly low co ncen trati o n s, < 5% [generally less th an I %]. AMP a lso has us es as a p ig m ent dispersant with titanium dioxide used in the manufacture of food co ntact paper and cardb oard (see next paragrap h). FDA Clearances: AM P possesses the following FDA c l earances for u se in in direct foo d contact application s (please consult the sp ec ifi c regulation for furthe r information): Section 175 .1 05 lists AM P among substances c leared fo r use as components of food packaging adhesives (AMP is de s ignated as aminomethylpropanol in the regulations). Section s 176. 1 70 and 176.180

- AMP i s cleared for use as an indirect food additive for use as a pigment dispersant at levels up to 0.25% by we ight ofpigment. The resulting dispersion may be used to coat paper w hich will contact fatty, dry, or aqueous foo d s in room temperature, refrigerat ed, or frozen storage. Section 175.300 li sts s ub stances cleared for us e as co mponen ts in r esi nou s and polymeric coatings intended fo r use in contact with food. AMP is listed as a permissible catalyst for modification of triazine-fo rmaldehyde resins in p aragraph (b)(3)(xiii)(a) ofth i s section

. The FDA has id e ntified AMP by t he ambiguous na me " methylpropanolamine ". T h e resins and
Page: 1 3coatings cleared under Section 175.300 hav e been cleared by cross reference for use as provided in the following sections: Section 175.380 Xylene-formaldehyde resins condensed with 4,4'- isopropylidenediphenolepichlorohydrin epoxy resins Section 175.390 Zinc-silicon diox i de matrix coatings Section 177.1210 Closures with sealing gaskets for food containers Section 177.2260 Filter, resin-bonded In indirect food contact in Section 176

. 170 and 176.180, AMP is cleared for use at levels up to 0.25% by weight of the pigment. Roughly 50% of the total 

### AMP produced globally in both of the plan ts i s used in the USA and the rest sol d in many co untrie s around the world. The primary markets fo r AMP products by vo lume are: Paint and Coatings (20%), Metalworking Fluids ( 10%), Intermediate Production Use (6%), Indirect Food C ontact (3%), and Personal Care pr oducts (2%). The remainder is so ld into a variety of minor uses such as cleaning products , flue gas treatment, b o iler water treatment and others. 

## 7. Conclusion
For the reasons presen ted in this petition , The Dow Chemical Company re spectfully requests that EPA modify the definition ofVOC at 40 CFR 51.100(s) to exempt AMP from regulation as a VOC.

TMTrademark ofThe Dow Chemical Compan y or an affiliated compan y of Dow.
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## References The Dow Chemical Company (201 0). "AMP (2-AM I N0-2 -METHYL- l -PROPANO L): DETERMINATION OF BIODEGRADABILITY ACCORDING TO OECD GUIDELINE 30 I FMANOMETRIC RESPIROMETRY". Testing laboratory: The Dow C hemical Company, Toxicology 

### & Environmental Re sea rch and Consulting, unpublished data of ANGUS Chemical Company, a subsidiary of The D ow Chemical Company, Midland, Michigan USA. Details in Appendix 3, page 5. Carter, W. P. L. (2000). " Documentation of the SAPRC-99 Chemical Mechanism for VOC Reactivity Assessment," Report to the California Air Resources Board, Contracts 92-329 and 95 308, May 8. Avai l ab le at: http://www.cert.ucr.edu / -carte r /reactdat.htm. Accessed August 10,2012 Carter, W. P. L. (2008). "Reactivity Estimates for Selected Consumer Product Compounds ," Final Report to Cal ifornia Air Resources Board Contract No. Board Contract No. 06-408, Feb ruary 19. Ava ilable at http: //www .cert. ucr. edu/-carter /pubs/ aminrep.pdf Carter, W. P. 

### L. (20 10). "Updated Maximum Incr emental Reactivi ty Scale and H yd rocarbon Bin Reactivities for Regulatory Application". Availab le at http: / / www.arb.ca. gov/ regact/2009/ mir2009/ mir 1 O.pdf Harri s and Pitts (1983). " Rates o f Reaction of Hydroxyl Radicals with 2-(dimethylamino)ethanol and 2-amino-2-methyl-1-propanol in the gas phase at 300 ± 2 K EST 1 7 50-51". Document attached as Appendix 8. Luecken, D

. (2007). " Memorandum: Review of the T ech nica l Basis fo r use of th e One dimensional MIR Scale in the Nati onal Volatile O rganic Compound Emission Standard s for Ae rosol Coatings" Docket ID EPA-HQ-OAR-2006-0971. Available at www.regulations.gov US EPA Federal Regi ster VOL.42 No 131 pages 353 14-35316 July 8, 1 977. "Recommended Po lic y on Control of Volatile Organic Compounds". US EPA Federal Register VO L. 70 54046 September 1 3, 2005. "Interim Guidance on Control of Volatile Compounds in Ozone State Imp lementati on Plans". Docket ID No. OAR 2003-0032 at www.epa.gov / edocket

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