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Before the Environmental Protection Agency

Petition to Exempt

2-Amino-2-Methyl-1-Propanol

CAS No. 124-68-5

From Regulation As A Volatile Organic Compound

Submitted by

The Dow Chemical Company

Linda E. Troester

EH&S Product Stewardship Manager

The Dow Chemical Company

1500 E. Lake Cook Rd

Buffalo Grove, IL 60089

TEL: 847-808-3432

E-mail: LTroester@dow.com

Donald Fontaine

Toxicology and Environmental Research 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 60089
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Executive Summary

The Dow Chemical Company submits this petition requesting that EPA modify the

definition of volatile organic compound (VOC) found at 40 CFR 51.100(s) to exempt 2-Amino-2-

methyl-1-propanol (AMP) from regulation as a VOC.

AMP is used to disperse pigments in water-based coatings and has significant performance

advantages compared to available substitute materials. AMP also is used as an additive in

metalworking fluids, as an intermediate in chemical synthesis, as an additive in the production of

food contact paper, as a neutralizer in personal care products, and also into some other minor uses.

AMP meets the criteria that have been used to grant prior VOC petitions. Specifically, the

current maximum incremental reactivity (MIR) value for AMP is 0.25 grams ozone per gram of

VOC, which is below the MIR value of the benchmark chemical ethane, which is 0.28 gram ozone

per gram of VOC. Older MIR values that are no longer accepted as valid, are addressed in the

petition.

Species which scavenge radicals tend to have higher variability associated with their MIR

values. This is the case with AMP. The MIR value in fact is negative under many conditions,

meaning that the presence of AMP inhibits ozone formation under those conditions. AMP also is

a solid at ambient temperatures and has low volatility, such that less than 100 percent of emitted

AMP is available to contribute to ozone formation. Modeling that assumes 100 percent

availability tends to overstate AMP’s potential contribution to ozone formation. These points are

explained further in the petition.

AMP is not regulated as a hazardous air pollutant (HAP) under Title III of the Clean Air

Act. Nor is it listed as a toxic chemical under section 313 of the Emergency Planning and

Community Right-to-Know Act (EPCRA).

Dow Chemical respectfully urges prompt consideration and action on this petition.

Manufacturers and formulators of water-based coatings need access to AMP to meet VOC limits

on their products without impairing performance of their products. For reasons explained in the

petition, there is considerable urgency to the situation.
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Table of Contents

1. Introduction

2. What is AMP?

3. Basis for the exemption of AMP from VOC regulation

4. Other Environmental Fate Considerations

5. Reasons for 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

Abbreviated

Appendix 3: AMP Mammalian Toxicology Environmental Fate and Effects Summary

Appendix 4: AMP HPV Submission IUCLID

Appendix 5: 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) 141S.161S,

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

Aerosol Coatings

Appendix 8: Harris and Pitts (1983) Rates of Reaction of Hydroxyl Radicals with 2-

(dimethylamino)ethanol and 2-amino-2-methyl-1-propanol 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 Company submits this petition requesting that EPA exempt 2-Amino-2-

methyl-1-propanol (AMP) from regulation as a VOC. The current maximum incremental

reactivity (MIR) value for AMP is below the MIR value of the benchmark chemical ethane.

Accordingly, AMP meets the criteria for exemption from regulation as a VOC.

2-Amino-2-methyl-1-propanol (AMP) is a unique primary aminoalcohol marketed and sold by

The Dow Chemical Company. AMP is a molecule with molecular weight of 89 and boiling point

of 165 oC. The vapor pressure of pure AMP is 0.34 mm Hg @ 20 oC. The pure chemical is a gellike crystalline solid which is miscible in water. As sold, the material is typically of various

purities, and sold in aqueous solutions of different concentrations for ease of handling.

Some simple physical properties of this material are as follows:

Property

AMPREGULARTM AMP-95TM Pure AMP

Water, % by wt < 0.8 < 5.8 < 0.3

Boiling Pt, 760 mm Hg, o C 163.8 100-165 165

Melting Pt, o C 30 -2 31

Flash Pt, degrees F 172 178 172

Specific Gravity 0.93 (40/40 o C) 0.94 (25/25 o C) 0.92 (density)

pH of 0.1 M aqueous sol’n

@ 20 oC 11.3 11.3 11.3

pKa @ 25 oC 9.72

Solubility in water @ 20 oC

g/100 ml Miscible miscible miscible

Viscosity, cps @ 25 oC 102 147 solid

2. What is AMP?

2-Amino-2-methyl-1-propanol (AMP) is a primary amino alcohol with some unique properties

that are valuable for pigment dispersion and neutralization for many different applications.

Chemically this substance contains amine and alcohol functional groups, and thus provides the

physical features and chemical reactivity of both classes of compounds.

There are various grades of AMP products for different target markets, including the following:
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Basic AMP products:

AMP-REGULARTM JSCI 2-Amino-2-methyl-1-propanol

AMP-REGULAR 2-Amino-2-methyl-1-propanol

AMP-75TM 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-methyl-1-propanol

AMP Cosmetic Grade Products:

AMP-ULTRATM PC 1000, Neutralizing Amine

AMP-ULTRAPC 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 Neutralizing Amine

Within each of these groups there is an amount of water added to the product in order to reduce

the viscosity of the material for ease in handling for certain customers. Therefore, AMP-95 has

approximately 5% water, while AMP-75 has approximately 25% water. Customers can choose

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 16981-16987. Air Quality: Revision to Definition of Volatile Organic CompoundsExclusion of a Group of Four Hydrofluoropolyethers (HFPEs) and in the Federal Register Vol. 74,

No. 12 Wednesday, January 21, 2009. Rules and Regulations pages 3437-3441. 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 negligible 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 concentrations. The EPA has expressly

recognized that exempting such compounds creates an incentive for industry to use negligibly

reactive compounds in place of more highly reactive compounds that are regulated as VOCs.

(Federal Register Vol. 70, No. 176, September 13, 2005, pages 54046-54051. Interim Guidance on

Control of Volatile Organic Compounds in Ozone State Implementation Plans). The EPA lists
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compounds that it has determined to be negligibly reactive in its regulations (at 40 CFR 51.100(s))

as being excluded from the definition of VOC. Also the policy of excluding negligibly reactive

compounds from the VOC definition was first laid out in the “Recommended Policy on Control of

Volatile Organic Compounds” (U.S. EPA, 1977) and was supplemented most recently with the

“Interim Guidance on Control of Volatile Organic Compounds in Ozone State Implementation

Plans” (Interim Guidance) (U.S. EPA, 2005). The EPA uses the reactivity of ethane as the

threshold for determining whether a compound has negligible reactivity. Compounds that are less

reactive than, or equally reactive to, ethane under certain assumed conditions may be deemed

negligibly reactive and therefore suitable for exemption from the VOC definition. Compounds that

are more reactive 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 chamber experiments that underlay the 1977 policy.

The EPA’s 2005 Interim Guidance also noted that concerns have sometimes been raised about the

potential impact of a VOC exemption on environmental endpoints other than ozone

concentrations, including fine particle formation, air toxics exposures, stratospheric ozone

depletion, and climate change. The EPA has recognized, however, that there are existing

regulatory and non-regulatory programs that are specifically designed to address these issues, and

the EPA continues to believe that the impacts of VOC 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 consideration of a compound's

contribution to ozone formation (Interim Guidance 70 FR 54046 September 13, 2005, and Final

Rule 77 FR 37610 June 22, 2012).

We are 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

air quality standard (NAAQS) for ozone under Title I of the Clean Air Act (CAA). This proposed

revision would add AMP to the list of compounds excluded from the definition of VOC on the

basis that this compound makes a negligible contribution to tropospheric ozone formation.

The EPA has used three different metrics to compare the reactivity of a specific compound to that

of ethane: (i) The reaction rate constant (known as kOH) with the hydroxyl radical (OH); (ii) the

maximum incremental reactivities (MIR) of ethane and the compound 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 10-11 cm3

molecule-1 sec-1. (Table 1) The corresponding kOH for ethane is 2.4 x 10-13 cm3 molecule-1 sec-1.

The rate constant for AMP is greater than that of ethane and corresponds to an atmospheric

lifetime (1/e) of about 4 hours under the conventional assumption of a hydroxyl radical

concentration of 3 x 106 molecules / cm3. For most VOCs reaction with 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 reactive. AMP, with a larger kOH,

is more reactive than ethane, but as explained in detail in Carter 2008, AMP’s reaction primarily

terminates radicals rather than cycling them and therefore generally 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 radical that is responsible for the cycling of NOx and producing ozone.
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The nitrogen centered radical scavenges radicals, primarily NOx, and is proposed to form a

nitramine which is assumed to be inert (Harris and Pitts 1983). The effect of AMP addition in the

chamber experiments of Carter 2008 was the reduction in ozone concentration consistent with this

mechanism.

The MIR value is a measure of photochemical reactivity derived from a computer-based

photochemical model that considers the complete ozone forming activity of a compound, not

merely the first reaction step. The MIR values for ethane and AMP in units of g O3 / g VOC are

given in Table 1. The ozone forming reactivity of AMP is less than that of ethane on this mass

basis. Given the relatively low molecular weight of ethane compared to most VOCs, the use of

MIR on a mole basis results in fewer VOCs falling into the ‘‘negligibly reactive’’ class versus the

mass basis. This is the case for several exempt materials listed in Table 1 and is also the case for

AMP, where the molar MIR value is greater than that of ethane, but the mass MIR value is less

than that of ethane.

The EPA has considered the choice between a molar or mass basis for the comparison to ethane in

past rulemakings and guidance. The design of the VOC exemption policy, including the choice

between a mass and mole basis, has been critiqued in the published literature. Most recently, in

‘‘Interim Guidance on Control of Volatile Organic Compounds in Ozone State Implementation

Plans’’ published on September 13, 2005 (70 FR 54046), EPA stated:

‘‘* * * a comparison to ethane on a mass basis strikes the right balance between a

threshold that is low enough to capture compounds that significantly affect ozone

concentrations and a threshold that is high enough to exempt some compounds that may

usefully substitute for more highly reactive compounds. * * *

When reviewing compounds that have been suggested for VOC exempt status, EPA will

continue to compare them to ethane using kOH expressed on a molar basis and MIR values

expressed on a mass basis.’’

Relying on a comparison of mass MIR values consistent with this guidance, EPA can revise its

definition of VOC at 40 CFR 51.100(s) to add AMP to the list of compounds that are exempt

because it is negligibly reactive since it is equal to or less reactive than ethane on a mass basis.

Two MIR values for AMP have appeared in regulations. The initial estimate, an upper limit MIR

estimate (ULMIR), of 15.08 g O3 / g VOC appeared in the original California Aerosol coatings

Consumer Products regulation in July 18, 2001 and this value was used by the EPA in the 2009

National Aerosol Coatings Rule published in the Federal Register volume 74, p29595-29607, June

23, 2009. This ULMIR estimate was based on a procedure developed by Carter (2000), for VOCs

for which mechanisms were not derived. Such compounds were assigned MIRs based on their

atmospheric reaction rates (if known), and the MIRs of the most reactive compounds of the same

type. AMP, with a reasonably high reaction rate and an amine function, was assigned a large

ULMIR. The second and currently accepted MIR value, 0.25 g O3 / g VOC, is much lower and it

reflects the experimental results and derived mechanisms for AMP reported by Carter in 2008.

This value was adopted in the California aerosol coatings regulation in October 2010. It is the
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current MIR value for AMP in California. This current MIR value is explained further is a report

prepared by Dr. Carter, attached as Appendix 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 which reduce ozone. The relative rates of these two competing processes will

depend on the nature of the radical scavenger and the environmental conditions. Since AMP

scavenges radicals it is expected to have its estimated MIR vary depending on environmental

conditions. The MIR calculation is based upon the average of the MIRs for 39 standard city

scenarios and can be calculated for the one scenario representing the average of the 39 standard

scenarios. For AMP these MIRs were 0.25 and 0.26 g O3 / g VOC, respectively. In either case the

MIR is less than that estimated for ethane (0.28 g O3 / g VOC). Further, as described in Dr.

Carter’s report, these values likely overstate AMP’s contribution to ozone formation. To the

extent that MIR values may be used to estimate reactivity (Luecken 2007) we may conclude that,

for the conditions used to define MIR, AMP has a reactivity that is less than or equal to that of

ethane.

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

Chemical

Formula Name CAS No.

Molecular

Weight

kOH1,2

(cm3/(moleculesec))

MIR3(gm O3/gm

VOC)

MIR4(gm

O3/mol VOC) VOC Status

C2H6 Ethane 74-84-0 30.07 2.4 x 10-13 0.28 8.4 Benchmark

C4H6O3

Propylene

Carbonate 108-32-7 102.09 6.9 x 10-13

0.27 27.56 Exempt

C3H6O3 Dimethyl Carbonate 616-38-6 90.08 3.49 x 10-13

0.056 5.04 Exempt

C3H2F4

1,3,3,3-

tetrafluoropropene

or HFO-1234ze 29118-24-9 114.04 9.25 x 10-13

0.098 11.2 Exempt

C4H11NO

2-Amino-2-methyl1-propanol (AMP) 124-68-5 89.14 2.8 x 10-11

0.25 22.25

Seeking

Exemption

1

kOH value for ethane is from: R.Atkinson., D. L. Baulch, R. A. Cox, J. N. Crowley, R. F.

Hampson, Jr., R. G. Hynes, M.E. Jenkin, J. A. Kerr, M. J. Rossi and J. Troe (2004), Summary of

Evaluated Kinetic and Photochemical Data for Atmospheric Chemistry as cited in the Fed Reg

volume 74, p29595-29607, June 23, 2009

2

kOH value for AMP is reported in: Harris and Pitts EST 17 50-51 (1983) Rates of Reaction of

Hydroxyl Radicals with 2-(Dimethylamino)ethanol and 2-Amino-2-methyl-1-propanol in the Gas

Phase at 300 ± 2 K

3 All maximum incremental reactivities or MIR (g O3/g VOC) values are from: W. P. L. Carter,

‘‘Updated Maximum Incremental Reactivity Scale and Hydrocarbon Bin Reactivities for

Regulatory Application" Table A-1 Updated table of MIR values and uncertainty classifications.
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This may be found at http://www.arb.ca.gov/regact/2009/mir2009/mir10.pdf updated 1/28/2010

and http://www.arb.ca.gov/regact/2009/mir2009/mir2009.htm

4 All maximum incremental reactivities expressed on a mole basis, MIR (g O3/mole VOC), are

calculated from the MIR expressed on a gram basis and the molecular weight of the VOC.

4. Other Environmental Fate Considerations

AMP is a reasonably strong base and forms salts with acids. In many formulations AMP functions

as a neutralizer and exists in the ionic or salt form. Very little AMP will evaporate to be available

for atmospheric reactions. It is difficult to transfer even un-ionized AMP quantitatively to the air.

In Carter 2008, best fits of the chamber concentration data were obtained assuming that only 5 to

50% of injected AMP was in the vapor phase. That is, 50 to 95% of the injected AMP was not

available in the atmosphere for reaction. Because AMP is a base it will also react with acid and pH

buffers in environmental media, soil, water, and air. These reactions are certain to ensure that

something less than 100% of the AMP that might be released from a formulated product will be

available to react to form ozone in the atmosphere.

Once in soil or water AMP will be biodegraded as it has been shown to be readily biodegradable.

(ANGUS 2010) These alternative fates will reduce the amount of AMP available for reaction in

the atmosphere.

Because any AMP that does exist in the vapor phase has a relatively short lifetime, and because it

does not contain chlorine or bromine, it does not contribute to the depletion of the stratospheric

ozone layer and has an ozone depletion potential value of zero.

Again, because AMP has a relatively short atmospheric lifetime, its contribution to global

warming, typically measured on a 100 year time scale, will be insignificant. This contribution to

global warming is at most equal to that of the carbon dioxide equivalent of its carbon content

assuming 100% atmospheric availability and conversion to CO2. A consideration of the relative

amounts of CO2 from degradation of AMP to that from burning carbon suggests that even this

overestimate of AMP’s contribution to global carbon dioxide is insignificant.

Amines are known to participate in atmospheric particle formation, in part from amine salt

formation and possibly absorption onto particles. Amines such as AMP have both photochemical

and non photochemical routes to particles. Acid gases such as HNO3, H2SO4 and HCl will react

with AMP to form salts. Photochemical products such as the nitramide and peroxy species can

also form particles. Environmental chamber experiments (Carter 2008) showed that the PM

formation of AMP was lower than other amines and d-limonene but greater than most alkanes.

Currently VOCs are not regulated based on their impacts on particles, and this is not directly

relevant to the issue of whether AMP should be regulated as a VOC ozone precursor.

AMP not only meets criteria that have been used to grant prior exemptions, its environmental

effects, although smaller than those obtained by assuming that 100% of AMP 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 formulators of water-based coatings need access to AMP to meet VOC limits on their

products without impairing performance of their products.

AMP is widely used in various applications as a preferred multifunctional neutralizer to adjust pH

of the formulations. AMP is the leading additive used for neutralization 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 glycols.

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 substitution to other materials that are VOC-exempt but that have less favorable

attributes in other respects, as described further 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 achieve 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 in 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 substance (ammonia).

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 in next generation

paints and coatings. AMP has an excellent toxicity profile (see Appendices 2-6), is not listed as a

hazardous air pollutant under the CAA or a toxic chemical 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 of VOC would allow companies to either

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-propanol (AMP) has a favorable 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

Sterlington, LA, USA, or in Ibbenburen, Germany.

2-Amino-2-methyl-1-propanol is manufactured according to the reaction below:

NO2

H H

O

+

O2N

OH H2NOH

[Catalyst] [Catalyst]

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

Markets and Uses:

AMP products are highly useful materials for a wide variety of applications. The uses discussed

below are representative but should not be considered as all-inclusive.

In Coatings: AMP is utilized by manufacturers of coatings for the dispersion 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 improves stability of the viscosity. As an efficient

base, AMP will stabilize the pH of latex paints, minimize can corrosion, stabilize zinc oxide paint

formulations, and improve the properties of the dry film. The coatings manufacturer reaps the

benefit of the cost-reducing advantages of AMP, such as simplified surfactant formulation, and

more efficient utilization of thickeners. The 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 formulators are considering water-soluble coatings

systems. Studies show 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 of the

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 Fluids: AMP-95TM is an excellent primary amino alcohol for use in

metalworking-fluid formulations. The use of AMP-95 in the formulation of synthetic, semisynthetic, and soluble oil metalworking fluids can result in superior overall performance.

Evaluations of alkalinity development, emulsion stability, and foam propensity clearly support the

use of AMP-95. It is completely water-soluble, has good thermal stability, a high flash point, and

is low in odor. These properties make it easy to handle in the workplace. Typical 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 alcohols such as salts

with mineral or organic acids, amides, amide esters, oxazolines, imides and imines, oxazolidines,

diamines and amino acids. The difunctionality of amino alcohols makes them useful as raw
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materials in polymer applications. One of the unique synthetic approaches is their reaction with

carboxylic acids to form the oxazoline structure. Films of oxazoline alkyds, for example, are

characterized by better resistance to water and alkali, better gloss retention on exposure, better mar

resistance, and better salt-spray resistance than are attained with 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-Amino-2-methyl-1-propanol would be used up as a raw material or intermediate

for the production.

Personal Care and Cosmetics: AMP is also widely used in cosmetic and personal care product

formulation such as lotions and hairsprays (typical use concentrations 2-5% by weight), for

neutralization and solubilization of acid-functional polymers. The Cosmetics Ingredients Review

Expert Panel of the Personal Care Products Council [http://www.cir-safety.org/] reported in their

review of AMP in “Safety Assessment of Aminomethyl Propanol and Aminomethyl Propanediol”,

24-Sep-2007, that the uses of AMP based on reporting of their members at that time included:

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 highest concentration reported in that document was up to 7% in hair dyes

and colors, with uses at 3% concentrations or less for the other applications. For the full

information please see this copyrighted document, which can be obtained from the Personal Care

Products Council, 1101 17 St. NW Suite 412, Washington, DC 20036-4702, TEL: 202-331-

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 creams, home maintenance products such as floor

polishes and cleaners, and industrial products such as insecticide sprays and asphalt emulsions.

AMP-95TM Amino Alcohol forms particularly efficient emulsifying 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 emulsion formulations and still

obtain better clarity, less odor, and more stability than can be obtained with weaker or more

fugitive amines. The utility of amino alcohols in emulsions is not limited to anionic (amine soaps)

applications. In nonionic polyethylene emulsions, the need for caustic can be lessened or even

eliminated by AMP. The effect of water on the dry polish film is thereby lessened to a great

extent. The stability and low color of AMP itself assure the formulator that finished products will

be low in color both initially and after storage. Typical use concentrations in an emulsion

formulation would be 1-5%.

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 condensatereturn lines. Laboratory studies and field experience indicate that AMP-95 provides excellent

corrosion inhibition for metals of construction, efficient absorption of carbon dioxide, adequate

distribution ratio to assure protection in steam-line runs, and minimum amine loss in the

deaerating heater. This is a minor use in the USA today. Typical use concentrations in a steam

boiler line would be in the 30 ppm (30 mg/L) range.
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As Catalysts: The salts of the amino alcohols can be used to prepare textile-resin catalysts with

variable curing rates – catalysts useful for resins which impart dimensional stabilization,

creaseproofing, or wash-and wear characteristics to fabrics. The hydrochloride salts of the amino

alcohols are the most widely used, but other salts such as nitrates, sulfates, phosphates, or

sulfonates may also be effective catalysts. These salts may be used alone, or in combination with

magnesium chloride or zinc nitrate, to produce balanced curing action with selected resins. Such

catalysts have also been proven to be effective in the coatings industry for improving the package

stability and cure of baking enamels. Typical use concentrations in textile uses would be in the 1-

2% range; however, this is a very minor use today.

Formaldehyde Scavenging: Oxazolidines form quite readily, so readily in fact that the amino

alcohols may be used to tie up formaldehyde which otherwise might be released to the

atmosphere. This reaction is reversible, with the oxazolidine formed at a high pH. The amino

alcohols are best used when the pH of the system containing formaldehyde is >8.0. An example

of this approach is the use of AMP in metalworking fluids to effectively reduce the amount of

formaldehyde found above a triazine containing fluid. This ability of amino alcohols provides an

excellent solution to the odor and irritation problem often associated with the use of ureaformaldehyde, melamine-formaldehyde, phenol-formaldehyde, or resorcinol- formaldehyde resins.

Also, the oxazolidine itself can act as a cross linking agent and upgrade the performance of the

system in terms of improved physical properties. Typical use concentrations for formaldehyde

scavenging would be one mole of AMP for each mole of formaldehyde, i.e. about 3% or so [if we

assume free formaldehyde never exceeds 1% then roughly 3% maximum AMP would be needed

to completely scavenge it].

Other Uses: AMP has shown value as amine buffer with small amounts sold in minor quantities

in a variety of pharmaceutical, diagnostic and biochemical applications. AMP has some minor

uses in cleaning products and in gas treatment where the AMP is present at fairly low

concentrations, < 5% [generally less than 1%]. AMP also has uses as a pigment dispersant with

titanium dioxide used in the manufacture of food contact paper and cardboard (see next

paragraph).

FDA Clearances: AMP possesses the following FDA clearances for use in indirect food contact

applications (please consult the specific regulation for further information):

Section 175.105 lists AMP among substances cleared for use as components of food

packaging adhesives (AMP is designated as aminomethylpropanol in the regulations).

Sections 176.170 and 176.180 – AMP is cleared for use as an indirect food additive for use

as a pigment dispersant at levels up to 0.25% by weight of pigment. The resulting dispersion

may be used to coat paper which will contact fatty, dry, or aqueous foods in room

temperature, refrigerated, or frozen storage.

Section 175.300 lists substances cleared for use as components in resinous and polymeric

coatings intended for use in contact with food. AMP is listed as a permissible catalyst for

modification of triazine-formaldehyde resins in paragraph (b)(3)(xiii)(a) of this section. The

FDA has identified AMP by the ambiguous name “methylpropanolamine”. The resins and
Page: 14

coatings cleared under Section 175.300 have 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 dioxide 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 plants is used in the USA and the

rest sold in many countries around the world. The primary markets for AMP products by volume

are: Paint and Coatings (20%), Metalworking Fluids (10%), Intermediate Production Use (6%),

Indirect Food Contact (3%), and Personal Care products (2%). The remainder is sold into a

variety of minor uses such as cleaning products, flue gas treatment, boiler water treatment and

others.

7. Conclusion

For the reasons presented in this petition, The Dow Chemical Company respectfully requests that

EPA modify the definition of VOC at 40 CFR 51.100(s) to exempt AMP from regulation as a

VOC.

TMTrademark of The Dow Chemical Company or an affiliated company of Dow.
Page: 15

References

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DETERMINATION OF BIODEGRADABILITY ACCORDING TO OECD GUIDELINE 301F -

MANOMETRIC RESPIROMETRY”. Testing laboratory: The Dow Chemical Company,

Toxicology & Environmental Research and Consulting, unpublished data of ANGUS Chemical

Company, a subsidiary of The Dow 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

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308, May 8. Available at: http://www.cert.ucr.edu/~carter/reactdat.htm. Accessed August 10, 2012

Carter, W. P. L. (2008). “Reactivity Estimates for Selected Consumer Product Compounds,” Final

Report to California Air Resources Board Contract No. Board Contract No. 06-408, February 19.

Available at http://www.cert.ucr.edu/~carter/pubs/aminrep.pdf

Carter, W. P. L. (2010). ‘‘Updated Maximum Incremental Reactivity Scale and Hydrocarbon Bin

Reactivities for Regulatory Application". Available at

http://www.arb.ca.gov/regact/2009/mir2009/mir10.pdf

Harris and Pitts (1983). “Rates of Reaction of Hydroxyl Radicals with 2-(dimethylamino)ethanol

and 2-amino-2-methyl-1-propanol in the gas phase at 300 ± 2 K EST 17 50-51”. Document

attached as Appendix 8.

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

Aerosol Coatings” Docket ID EPA-HQ-OAR-2006-0971. Available at www.regulations.gov

US EPA Federal Register VOL.42 No 131 pages 35314-35316 July 8, 1977. “Recommended

Policy on Control of Volatile Organic Compounds”.

US EPA Federal Register VOL. 70 54046 September 13, 2005. “Interim Guidance on Control of

Volatile Compounds in Ozone State Implementation Plans”. Docket ID No. OAR 2003-0032 at

www.epa.gov/edocket