United States

ENVIRONMENTAL PROTECTION AGENCY

Washington, DC 20460 AGENCY USE ONLY

OMB Control No.: 2060

- 0226

Expires: 8/31 /2014



### SNAP INFORMATION NOTICE

For Significant New Alternatives Date of Receipt:

Date 90 Day Review Begins:

Date Review Comple ted:

CBI Status: When completed send this form to:

Via US Postal Service: Via Overnight Delivery Service:

SNAP DOCUMENT CONTROL OFFICER SNAP DO CUMENT CONTROL OFFICER

OFFICE OF AIR AND RADIATION, 6205 J U.S. EPA

U.S. EPA 1310 L STREET NW

1200 PENNSYLVANIA AVE NW 10 th FL OOR (MC 6205J)

WASHINGTON, DC 20460 WASHINGTON, DC 20005

Enter the total number of pages in your SNAP information Notice: 54 Document Control Number

INTRODUCTION

GENERAL INSTRUCTIONS

This form may be used to sub mit information under the Significant New Alternatives Policy (SNAP) program for the review of

alternatives to class I and class II ozone

- depleting substances (ODS) under section 612 of the Clean Air Act. Submitters are

required to provide this informatio n on new substitutes to assist the Agency in assessing the acceptability of chemicals or

processes that are considered alternatives for ODSs. A separate notice must be filed for each alternative you are submitting

.

PAPER SUBMISSIONS: All paper submission s must be provided in three complete copies. If information is to be claimed as

confidential, all confidential information must be excised from one of the copies, which will be placed in the public docket; the

other two copies must include the confidentia l material. If no claims of confidentiality are made for the submission, all copies

must be identical.

CD

- ROM SUBMISSIONS: The SNAP program also accepts submissions via CD

- ROM. If information is to be claimed as

confidential, all confidential informatio n must be excised from one of the files on the CD

- ROM, which will be placed in the public

docket; the other file must include the confidential material. The file with the confidential material must include “contain s CBI” in

the file name.

STEP

- BY

- STEP IN STRUCTIONS: The Instructions for the SNAP Information Notice and TSCA/SNAP Addendum (“Instructions”)

are designed to assist applicants in completing this form. The Instructions provide step

- by

- step guidance on submitting a SNAP

notice, asserting confident iality claims, completing the notice form, sector

- specific data requirements, and submitting test data

and supplemental information.

To facilitate Agency review of alternatives, this form must be filled out as completely as possible. Please provide all i nformation

requested to the extent that it is known or reasonably ascertainable. Make reasonable estimates if actual data is unavailabl e.

TYPE OF NOTICE (Check only one box)

Select the appropriate box identifying the type of notice submitted:

Manufactu rer Submission: New alternative, Substance, or Formulation___________________________________________ X

Petition: New alternative, Substance, or Formulation__________________________________________________________ 

## 

Petition: Revision of the Existing SNAP list_________________________________________________________________

_ 

## 

Petition: Request to Grandfather Use of An Unacceptable Substitute_____________________________________________ 

## 

Form 1265

- 07 (Revised 09/2011)

OMB Control No.: 2060

- 0226

Previous editions are obsolete 1Part I

- GENERAL INFORMATION

You must provide the identity of the alternative chemical o r

processes and the identity and percentages of all

components in a blend and/or process, even if you claim the

identity as confidential. You may authorize another person

to submit the identity for you, but your submission will not be

complete and review cannot begin until EPA receives this

information.

Part II

- ALTERNATIVE

- SPECIFIC INFORMATION

Please indicate the sector(s) for which you are submitting

information on the s ubstitute by checking the appropriate

boxes:

• Refrigeration and Air Conditioning 

• Foam Blowing X

• Solvent Cleaning 

• Fire Extinguishing

and Explosion Prevention 

• Sterilization 

• Aerosol s 

• Adhesives, Coatings, and Inks 

• Tobacco Expansion 

• Pesticides 

You may need additional copies of Part II if there are several

manufacturing, processing, or use operations that you will

describe in this notice. Pl ease reproduce these sections as

needed.

If you r substitute is also subject to review under FIFRA,

provide the FIFRA Registration Number:

_____________________________ Part III

- RELEASE AND EXPOSURE DATA

Please reproduce additional copies of Part III as necessary.

Part IV

- LIST OF ATTACHMENTS

Please attach additional sheets if you do not have enough space on

the form to fully answer a question. Label each continuation sheet

with the corresponding section heading and the question. In part

IV, list these attachments and any test data, other data, or any

optional information that you include in this notice.

TEST DATA AND OTHER DATA

You are required to submit all test data in your possession or

control and to provide a description of all other data known to you if

these data are related to the health and environmental effects of

the manufacture, processing, distribution in commerce, use, or

disposal of the alternative. Standard literature citations may be

submitted if they do not appear in the open scientific literature.

Complete test data (in English), not summaries of data, must be

submitted if they do not appear in the open literature. The following

are test data and other data that might be submitted (see the

Instructions for a more complete li st of data to be submitted.)

Please indicate test data to be included in your submission notice

by checking the appropriate boxes:

• Health Effects Data X Yes  No

• Flammability Data X Yes  No

• Environmental Effects

Data X Yes  No

• Environmental Fate

Data X Yes  No

• Risk Assessments X Yes  No

1. Test Data Not in the Possession/

Control of the Submitter  Yes X No

• Other Data X Yes  No

CONFIDENTIALITY CLAIMS

Anyone submitting information must assert a claim of confidentiality at the time of submission for any data which are to be t reated as

Confidential Business Information (CBI). Substantiation of this claim must also be provided at t his time. All information claimed as

CBI will be treated in a manner consistent with 40 CFR Part 2, Subpart B. Failure to assert a claim of confidentiality at th e time of

submission may result in disclosure of information by the Agency without further no tice.

To assert a claim on this form, circle or bracket the information you claim as confidential and mark the confidential box at the bottom

of the page. Then provide substantiation of this claim on an attachment to the notice. If any information is cl aimed as confidential,

you must provide a “sanitized” version of this notice, including attachments, to EPA with y our submission. For additional information

on claiming information as confidential, please see the Instructions Manual.

Information submitte d as CBI may be accessed by companies designated as Authorized Representatives of the United States

Environmental Protection Agency (EPA) under an EPA contract for the purpose of assisting EPA in the development and

implementation of national regulations f or the protection of stratospheric ozone, including the development of the SNAP program.

These Authorized Representatives may have access to any information received by the Stratospheric Protection Division within the

EPA Office of the Atmospheric Program s for use in reviewing the need for possible control of any substance, practice, process or

activity that may reasonably be anticipated to affect stratospheric ozone. Access to such information is necessary to ensure that

these companies can complete the work required by the contract.

Authorized Representatives of the Administrator are subject to the provisions of 42 U.S.C. 7414(c) respecting confidential bu siness

information as implemented by 40 CFR 2.301(h).

Form 1265

- 07 (Revised 09/2011)

OMB Control No.: 2060

- 0226

Previous editions are obsolete 2Part I

- GENERAL INFORMATION

Section A

- SUBMITTER IDENTIFICATION

1. (a) Person Submitting Notice (in U.S.)

Chris Martin

______________________________________________________________ ______________________________________ _______ __ Name of Authorized Official Title

Holland Applied Technologies

___________________________________ _______________________________________________________ ______ ___ Company/Organization

7050 High Grove Blvd. Burr Ridge, Illinois 60527 Phone: 630

- 325

- 5130 Fax: 630

- 325

- 5161

_____________________________________________ ________________________________________________________ ______ _ Mailing Address Telephone & Fax Numbers

chris.martin@hollanda pt.com

____________________________________________________________________________________________________________

E

- mail Address

(b) Agent (if applicable)

Angelina Duggan, PhD. Se nior Managing Scientist

__________________________________________________________________________________________________ ______ _ Name of Authorized Official Title

Exponent, Inc Health Practice Center for Toxicology and Mechanistic Biology

_______________________________________________________________________________________ ___ ________ ___ _ Company/Organization

1150 Connecticut Avenue Suite 1100 Washington, DC 20036

____________________________________________________________________________________________________ ______ _ Mailing Address Telephone & Fax Numbers

aduggan@exponent.com Fax: 202

- 772

- 4979; Cell: 646

- 660

- 2677

________ ____________________________________________________________________________________________________ E

- mail Address

(c) Joint Submitter (if applicable)

_________________________________________________________________________________________________ ______ __ Name of Authorized Official Title

____________________________________________________________________________________________ ______ __ Company/ Organization

_____________________________________________________________________________________________________ ______ _ Mailing Address Telephone & Fax Numbers

___________ __________________________________________________________________________________________ E

- mail Address

2. Technical Contact (in U.S.)

Angelina Duggan, PhD. Senior Managing Scientist

____________________________________________________________________________________________________ ____ __ Name of Authorized Official Title

Exponent, Inc Health Practice Center for Toxicology and Mechanistic Biology

______________________________________________________________________________________________________ ___ Company/Organization

115 0 Connecticut Avenue Suite 1100 Washington, DC 20036

___________________________________________________________________________________________________ ____ _ Mailing Address Telephone & Fax Numbers

aduggan@exponent.com Fax: 202

- 772

- 4979; Cell: 646

- 660

- 2677

___________________________________________________________________________________________________ E

- mail Address

3. If you have had a prior communication with EPA concerning this notice, note the date and type of com munication (letter, phone,

etc.) and the EPA staff person’s name:

January 14 and 16, 2014: Margaret Sheppard Telephone Conferences to discuss general SNAP application and process questions

Mark (X) if None ________________ 

Mark (X) this box if this pag e contains CBI __________ 

Form 1265

- 07 (Revised 09/2011)

OMB Control No.: 2060

- 0226

Previous editions are obsolete 3Part I

- GENERAL INFORMATION (continued)

Section B

- ALTERNATIVE IDENTIFICATION

1. Commercial/Trade name (s) of alternative:

Methylal

2. (a) Name of chemical(s) (preferably IUPAC nomenclature ) and/or process name. For blends, provide the percent composition of each

constituent. For powdered aerosols used in fire suppression, s ee page 11 of the Instructions for additional necessary composition information.

(b) Chemical Abstracts Service (CAS) registry number and mo lecular formula.

(c) For alternative processes and technologies describe the technology and provide a diagram of the system. Also provide the information

on any chemical constituents.

(d) If you have applied for or hold a patent on the substitute, provide the patent name

, number (if available), and information on the topics

covered in the patent.

Methane, dimethoxy

- (CAS N omenclature ; CAS RN 109

- 87

- 5) is a mono constituent chemical substance that

belongs to a class of chemicals referred to as acetals. Acetals are derived from the acid c ondensation of aldeh y d es

and alcohols. As such, acetals are not chemically analogous to ethers.

Dimethoxymethane ( EINE CS 203

- 714

- 2) is the IUPAC and EU designation

. The molecular formula is C3H8O2.

Figure 1. Methylal Structure

C AS 109

- 87

- 5

The most often used common name is m ethylal and t his designation for CAS 109

- 87

- 5 will be used throughout

this SNAP application. The structure of methylal ( Methane, dimethoxy

- ) is illustrated above in Figure 1.

Other comm on names include : Formal; Formaldehyde Dimethyl E ther ; Dimethylformal ; Methylene Dimethylate;

Methylene Dimethyl Ether; Methylene Glycol Dimethyl Ether; Formaldehyde Dimethyl; Formaldehyde

Dimethylacetal; Anesthenyl ; Bis(Methoxy)Methane ; Dimethoxymethane ; Dimethyl Formal Formaldehyde;

Methyl Ketal ; Methoxymethyl Methyl Ether ; Formaldehyde Dimethoxy Acetal ; M

- 222 ; Methyl Formal ; HSDB

1820

The CAS IES Report is included as Attachment 1.

3. Generic name :

I f the name of the substitute is declared Conf idential Business Information , provide a generic name

.

None

Mark (X) this box if this page contains CBI __________ 

Form 1265

- 07 (Revised 09/2011)

OMB Control No.: 2060

- 0226

Previous editions are obsolete 44. Specific End

- Use (a) Describe each end

- use that may be reasonably anticipated for the alternative. Be sure to provide a broad description

(e.g.

, terpene

- based semi

- aqueous solvent cleaner for electronic parts, or HFC substitute refrigerant for cent rifugal chillers). For a list of end

uses, see Appendix A to the I nstructions, beginning on p. 23

. If the alternative is a refrigerant, indicate whether it is a candidate for use in

retrofits of existing equipment, for use in new equipment only, or both.

(b) Identify the ODS and the quantity of substitute needed to replace it for each end use in pounds ( i.e., the replacement ratio).

[Current and Proposed Use CBI H as Been Removed]

EPA and international regulators have mandated the replacement of ODS s ubstances such as, CFC

- 11, CFC

- 12,

CFC

- 113, CFC

- 114, HCFC

- 141b, HCFC

- 142b and HCFC

- 22 . Since m ethylal does not contain any halogen

atoms, it is therefore by definition not classified as an ozone depleting substance . As such, methylal is a suitable

replac ement for the ODS chemicals, such as HCFC

- 141b , that were previously used as blowing agents in the

preparation of polyurethane foams.

Methylal has already been approved by the United Nations Development Program (UNDP) as a potential

replacement of HCFC

- 1 41b (refer to Attachment 2 a (the summary report) and 2b (the full report and analysis ) ) :

Methylal as Blowing Agent in the Manufacture of Polyurethane Foam Systems (March 2012).

[Current and Proposed Use CBI H as Been Removed]

(b) HCFC

- 141b can be gener ally re placed by approximately 70% of m ethylal ( i.e., 100 lbs of HCFC

- 141b can be

replaced by 70 lbs of methylal). This is linked to the difference in molecular weight . But this is not a strict

percentage because it can vary from one formulation to the ot her.

Mark (X) this box if this page contains CBI __________ 

Form 1265

- 07 (Revised 09/2011)

OMB Control No.: 2060

- 0226

Previous editions are obsolete 5Part I

- GENERAL INFORMATION (continued)

Section B

- ALTERNATIVE IDENTIFICATION (Continued)

As a result of its in

- depth project assessment, U N D P (2012, Attachment 2a) c oncluded the following ; key points

have been bolded :

“ As a result of the project, it can be concluded that methylal can serve as a feasible

alternative blowing agent to replace HCFC

- 141b in PU foam applications

... The final project

report als o provided recommendations for setting up the technological process of using methylal

as a blowing agent to ensure safety and environmental considerations. The use of methylal

instead of HCFC

- 141b will have a significant positive impact on climate: methyla l’s GWP is

ne gligible compared to the GWP for 725 HCFC

- 141b (IPCC Fourth Assessment Report,

2007). The project also considered cost of conversion and found them to be similar to the use of

HCFC

- 141b. However, the costs will depend on the local economic a nd market conditions.”

Mark (X) this box if this page contains CBI __________ 

Form 1265

- 07 (Revised 09/2011)

OMB Control No.: 2060

- 0226

Previous editions are obsolete 65. Impurities

(a) Identify each impurity that may reasonably be anticipated to be present in the chemical alternative as manufactured for commercial

purposes. If there are unidentified impurities, enter “unidentified.”

(b) Provide the CAS Reg istry Number for each impurity if available.

(c) Estimate the maximum weight percentage of each impurity. If there are unidentified impurities, estimate their total weig ht

percentages.

Methylal will be manufactured at the Lambiotte & Cie S.A. pla nt at Grand ‘Rue 79 B

- 6724

, Marbehan

, Belgium

and imported into the United States.

M ethylal is generally manufactured through an acid

- ca talyzed dehydration reaction that includes two molar

equivalents of methanol and one molar equivalent of formaldehyde . Formaldehyde is produced from the

oxidation of methanol which is derived from natural gas, an abundant substance in nature. The overall r eaction

sequen ce of the production process is indicated below in Figure 2 . Unlike hydrocarbon blowing agents (e.g.

, pentane and or cy clopentane), the production of methylal does not consume non

- renewable oils.

Figure 2. Methylal Production Process



### Natural Gas Synthesis gas CH 3



### - OH

[O] Methylal

CH 2 

### O

It should also be noted that biosourced methanol , albeit more expen sive, is now also available. Theref ore

, methylal could, in the future, be prepared from biosourced methanol if the economics eventually become more

attractive.

[Manufacturing CBI H as Been Removed]

Mark (X) this box if this page contains CBI __________ 

Form 1265

- 07 (Revised 09/2011)

OMB Control No.: 2060

- 0226

Previous editions are obsolete 76.Byproducts:

(a) Describe any byproducts o r degradation products resulting from the manufacturer, processing, use or disposal of the chemical alternative

or chemicals used in the new alternative. If there are unidentified byproducts/ degradation products enter “unidentified.”

(b) Provide the CAS Registry Number for each byproduct or degradation product if available.

(c) Indicate where the byproduct/degradation product is formed (e.g. during manufacturing, during use, in case of fire, etc. ) and the amount

or rate at which it is formed.

a) There are no identified by

- products or degradation products that would result from either the

manufa cturing process or the use of methylal as a PU b lowing agent under the conditions recommended

by Lambiotte

.

b) Not applicable

c) In case of severe fire or combustion, methylal would produce non

- noxious substances, i.e., carbon

dioxide and water. Methylal is ther mally stable for 7 days at 200° (Attachment 2 b UNEP, 2012 page

17).

d) Methylal is also stable against pe roxide formation

, since there is no need to blanket the chemical with an

inert gas. Experimental results confirm t here is no formation of peroxides after 1143 days . Refer to

information in Attachment s 3 ga and 3gb.

e) [Manufacturing CBI H as Been Removed]

Mark (X) this box if this page contains CBI __________ 

Form 1265

- 07 (Revised 09/2011)

OMB Control No.: 2060

- 0226

Previous editions are obsolete 8Part II

- ALTERNATIVE

- SPECIFIC INFORMATION 1, 2 ,3

Section A

- PHYSICAL AND CHEMICAL PROPERTIES

– See Appendix B to the I nstructions to see which

properties apply to which uses

.

1. Molecul ar weight 76.09 2. Physical state at 20 o C Clear Liquid

3. Melting point at 1 atm. pressure o C

- 95.38 (EPI Suite TM calculation) 4. Boiling point at 101.3 hPa 42.3 o C

5. Specific gravity (relative density) 0.861 g/mL @20 o C 6. Odor T hreshhol d N/D mg/m 3

7. Solubility using solvent @ temperature o C g/L Miscible with alcohol, ether and oils

8. Solubility in water @ temperature 323,000 mg/L @ 16 o C (32% by

weight; solubility of water in methylal is 4% by wei ght

9. Partition coefficient Log K

ow 0

. 00 (experimental) Log K 

Log K

ow - 0.19 (calculated)

10. Vapor pressure @ 20 o C 40,000 Pa

(Also provide vapor pressure

- temperature curve for refrigerants.) 11. Critica l temperature

215.2 o C 12. Critical

Pressure

psi

13. Are spectra attached? Yes r efer to Attachment 3 14. Disassociation constant in water pKa 3.1

15. Pa rticle size distribution : N/A 16. Volatilization from soil : N/D

17. Volatilization from water : Henry’s Database (EPI Suite TM ) 0.000173

atm

- m3/mole 18. Viscosity @ 20 o C 0.325 mPa .s

19. pH@concentration : N/ D 20. Thermal conductivity (for foam blow ing

agents

See Table 3 below:



### λ (10

- 2, W/m.K) = 1.45; T ( o C) = 41.85



### λ (10

- 2, W/m.K) = 2.0390; T ( o C) = 109.85

21. Adsorption coefficient : Not Determined 22. Flammability limits (LFL, UFL) 2.2

(or 71 g/ m3)

- 19.9 % (or 630 g/ m 3 vol )

23. Flash poin t :

- 30.5 o C @101.3 hPa 24. Heat of combustion :

Δ f H°

gas = 348.2 ± 0.79 kJ/mol 3

25. Maximum pressure rise : Illustrated in Attachment 2b on page 71 /105. 26. Maximum rate of pressure rise : Illustrated in

Attachment 2b on pages 71/105

.

27. Other (sp ecify) GWP: Negligible

Not corrosive ; not oxidizing; no chemical explosive chemical groups Auto Ignition 

### : 235 o C

1 The data entered into the Part II Section A t able above are derived from the calculations and experimental data

included in the EPA public ally available model EPI Suite TM 4.1 calculations (Refer to Attachment 4 a (ultimate

degradation) and 4b (primary degradation ).

2 P hysicochemical data are included in Attachment 4 Methylal EpiSuite 4.1 Calculations and Attachment 5

Lambiotte Dimethoxymethan e Chemical Safety Assessment Report on pages 1

- 4.

3 Methylal National Institute of Standards and Technology Material Measurement Laboratory

http://webbook.nist.gov/cgi/cbook.cgi?ID=C109 875&Mask=1F

.

Mark (X) this box if this page contains CBI __________ 

Form 1265

- 07 (Revised 09/2011)

OMB Control No.: 2060

- 0226

Previous editions are obsolete 928

. Flammability: Provide any information on flammability concerns. For example, if any abatement techniques are being used

to minimize the risks associated with flammable substances or mixtures, detail those techniques below. If a substitute is

flamm able, an assessment of overall risk in each end

- use may be required. For flammable refrigerants, provide a fault tree

analysis for each end use.

For flammable foam blowing agents used in spray foam, provide a training program that addresses flammability concerns

specific to this substitute. (See Appendix B to I nstructions for sector

- specific data requirements for flammable substances).

M ethylal has been classified as a flammable liq uid Class II (highly flammable) due to its having a flash point of

-

30.5 oC and a boiling point of 42.3 oC. See Attachmen t 5: Methylal CSR (11

- 20

- 2012)

, Pages 3 and 4

.

However, w ith a boiling point of ca 42.3 oC and vapor pressure (44. 0 kPa at 20 o C and 126.3 kPa @ 50 o C ), the

physicochemical properties of methylal are al s o i deal for its intended use as a foam blowing agent. Overall,

methylal is less flammable than blowing agents such as n

- pentane, isopentane and methyl formate all of which are

flammable liquid Class I.

The s uitability of replacement blowing agents is gener ally classified according to their boiling points. Tab le 3

below compares the boiling points of various chemicals that are currently or previously used as foam blowing

agents. The values reported below are from various publically available sources.

Table 3 Comparison of Methylal Boiling Point with Other Blowing Agents

Product Structure Boiling Point o C

Cyclopentane (CH 2 ) 5 49

Met h ylal CH 3 - O

- CH 2 - OCH 3 42.3

Methylene Chloride CH 2 Cl 2 40

HFC

- 365

- mfc CF3CH2CF2CH3 40

n

- Pentane CH 3 - (CH 2 ) 3 - CH 3 36

Methyl Form ate CH 3 - O

- CH=O 31.5

HCFC

- 141b CH 3 - CCl 2 F 32

Isopentane CH 3 - CH(CH 3 )

- CH 2 - CH 3 28

HFC

- 245fa CF 3 - CH 2 - CHF 2 15

HFC

- 134a CH 2 F

- CF 3 - 26

Liquid Carbon Dioxide CO 2 Gas

Training program for use of methylal as a blowing agent:

On the basis of the acute, subc hronic repeat dose toxicology and mutagenicity testing provided in Part 3 Section A,

it can be concluded that methylal is can be used safely by workers with proper personal protective equipment and

ventilation. Thus, ensuring the safe use of methylal as a foam blowing agent is contingent on providing workers with

specific information about its flammability and most especially how to minimize the risk of fires. This information

is included in the MSDS (refer to Attachment 7) and is also reviewed in Section E Occupational Exposure at End

Use. In addition, the UNDP ( Attachment 2b, 2012 page 73/105) has provided recommendations for systems houses

that process pure grade methylal and for downstream users that process polyol and or isocyanate blends. The

UNDP’s complete assessment of methylal’s flammability is included on pages 60

- 73/105 of Attachment 2b.

.

Mark (X) this box if this page contains CBI __________ 

Form 1265

- 07 (Revised 09/2011)

OMB Control No.: 2060

- 0226

Previous editions are obsolete 10The UND P (Attachment 2b, 2012 on page 73/105) has concluded that:

“Methylal as a pure liq uid is very flammable and requires proper safeguards. The risk of

detonation or explosion is, however, remote because of its low heat of combustion....

Table 4 illustrates the comparative heats of combustion of methylal with other blowing agents and ethanol in its

capability to replace HCFC

- 141b

. UND P (2012, Attachment 2 b , page 70/105 ) also provided the following

comments regarding combustibility and its suitability to replace HCFC

- 141b

.

“ Combustability

- a blowing agent is commonly stored and processed as a liquid but turns into a

gas as part of a foam expansion, due to exothermic reaction between water and isocyanate (and to

a lesser extent polyol and isocyanate), expanding the still liquid reaction mixture and filling the

generated foam cells. Addressi ng the combustibility of a blowing agent as a liquid is equally

important as of a gas. For instance, HCFC

- 141b is not flammable as a liquid but its vapors may

still burn. As it easily generates vapors at ambient conditions, it should also be tested for ga seous

flammable properties. HCFC

- 141b is therefore frequently listed in an MSDS as “moderately”

flammable or simply “yes” 3 . Methylal is on the other side, ( is ) even as a liquid flammable (which

does not necessarily imply explosive). Its burning potential i s ve ry much like alcohol [ethanol],

i

. e

. , it burns with low energy, blue flame and its energy of combustion is very low much

- more

like HCFC

- 141b than pentanes...”

Table 4 Heat of Combustion for Methylal and Other Blowing Agents

Substance Heat of Combust ion (kcal/g) Comments

H CFC

- 141b 1

. 9

-- Methylal 6.1

--

Ethanol 7.1

-- Pentane (Commercial Mix) 11.5 Cyclopentane estimated to be 10% lower

1. Panov, GE, and Polozkov, V.T., “Flammable Substances, Encyclopedia of Occupational Health and Safety , 3 rd edit ion, Inter national

Labor Office Geneva, pages 881

- 883 (1983).

As noted above, the application of methylal in spray foams (which provide insulation on roofs and in walls)

necessitates a special training program to address flammability concerns. Lambiotte has not developed a specific

training program for the use of methylal in spray foam applications. But, it should be taken into consideration that

the risk of flammability in spray foam applications may be reduced by either increasing the amount of water (t hat

results in a decrease in the amount of methylal) or by blending methylal with HFC

- 245fa or HFC

- 365mfc/HFC

227fa.

[ Reduced Flammability CBI H as Been Removed]

Mark (X) this box if this page contains CBI __________ 

Form 1265

- 07 (Revised 09/2011)

OMB Control No.: 2060

- 0226

Previous editions are obsolete 11Highly viscous polyols (unless made less viscous in system formulations) do not provide good quality polyurethane

foams. Table 5 demonstrates that increasing the content of methylal provides a decrea se in viscocity of the methylal

polyol mixture

.

Table 5 Reduction in Polyol V iscosity by Increasing the Concentration of Methylal

The flash point depends on the viscosity and /or the nature of the polyol. P olyols of higher viscosities give h igher

flash points , but are undesirable for manufacturing polyurethane

. Blending methylal with polyols result s in both a

decrease of polyol viscosity and for the mixture high er a closed cup flash point compared to neat methylal

. Table 6

below indicates th at b lends of various polyols with methylal have a high closed cup flash point

. Polyols of higher

viscosities give higher flash points and as such

, may have a more dramatic effect in reducing the potential for

methylal flammability. However, polyols of ev en of low viscosity, that include 8% of methylal

, do not ignite in the

presence of a flame.

Table 6 Closed Cup Flash Point Reduction with Blends of Polyol and Methylal

Blend % (w/w) Flash point (closed cup) (°C) Abel IP 170 Flash Point Analyzer)

Poly ol Methylal Polyol (visco

at 22°C : 930

mPa.s) Tercarol

8092

(viscosity at

25°C: 14500

mPa.s) Terate 2033 Terate 2541 Terate 7541

100 0

99.5 0

. 5 >70.0

99 1 48

98.5 1.5 39.0 58.0 56.0 47.0

98 2.0 25.5 45.0 53.0 37.0 35.5

96 4 9.0 31 .5

Blends of polyols with very high amount s of methylal, i.e., ~ 10% which is above the quantity usually used for foam

production, show as illustrated in Table 7 below (UND P, 2012 Attachment 2b ), a low tendency for combustion. In

Europe, this point is very important for systems houses because European legislation states that, if the flash point of

a blend is between 21°C and 55°C, and the blend does n o t contribute to the combustion, the substance does not need

to be labelled as flammable. The EU ANN EX VI: General Classification and Labelling Requirements for

Dangerous Substances A nd Preparations is included as Attachment 6, refer specifically to Pages 7

- 8.

G enerally

, it is the specific polyol system formulations that will be sold to customers to use in the manufacture of

polyurethanes with specific isocyanates and not as th e unfor mulated neat methylal. As such, polyol systems

formulations will have controlled flammability and are not labeled as flammable.

Mark (X) this box if this page conta ins CBI __________  Composition % w/w Viscosity (mPa.s)

Polyol Methylal Tercarol 8092

(at 20°C) Polyol

(visco at 22°C :

930 mPa.s)

100 0 21840 930

98 2 8740 700

96 4 4566 500

94 6 3183 380

92 8 1416 300

90 10 448 235

85 15 361 140

Form 1265

- 07 (Revised 09/2011)

OMB Control No.: 2060

- 0226

Previous editions are obsolete 12However, neat methylal may also be sold to producers (in lesser quantities) of finished polyurethane products. That

is, manufacturers of polyurethane products that do not buy polyol process system formulations, but produce both the

po lyurethane process formulations and finished polyurethane in the same manufacturing facility. Methylal for these

polyurethane manufacturers will be labeled as flammable. However, neat methylal drums should be grounded to

prevent ignition from electrical sp arks.

Ta bl e 7 R eduction in Combustibility for Blends of Polyol and Methylal

Blend % (wt/wt) Combustion Description (in the presence of a flame)

Polyol Methylal

98 2 No ignition

96 4 No ignition

94 6 No ignition

92 8 No ignition

90 10 Single ignit ion of the vapors; no further ignition in the

presence of a flame

88 12 Ignition of the vapor s; can be repeated, but is self

extinguishing

86 14 Continuous burning

• Methylal is also miscible with pre

- polymer isocyanates products ( e.g., Suprasec 5025 Is ocyanate). Thus,

alternatively, in some cases, methylal may be sold mixed with isocy a nate and then reacted with a polyol.

The methylal

- isocy a nate mixtures are also not labeled as flammable. Table 8 illustrates that closed cup

flash points of blends of isocyanate with a low percentage of methylal are high with a low risk of

flammability

.

Table 8 Closed Cup Flash Points with Blends of Isocyanate and Methylal

Product Closed Cup Flash Point O C

Supra sec 5025 Isocyanate Methylal

99.5 0.5 > 70.0

99. 0 1.0 46.0

98.5 1.5 29.0

98.0 2.0 23.0

97.5 2.5 18.0

97.0 3.0 12.0

96.5 3.5 8.0

96.0 4.0 4.0

To summarize, t he above data in Tables 7 and 8 confirm that t he risk of methylal flammability can be significantly

reduced and control led for its use as a foaming agent during the reaction of polyols with isocyanate to prepare

polyurethanes.

[ Methylal Benefits CBI Has Been Removed]

Mark (X) this box if this page contains CBI __________ 

Form 1265

- 07 (Revised 09/2011)

OMB Control No.: 2060

- 0226

Previous editions are obsolete 13[ Methylal Benefits CBI H as Been Remov ed]

Mark (X) this box if this page contains CBI __________ 

Form 1265

- 07 (Revised 09/2011)

OMB Control No.: 2060

- 0226

Previous editions are obsolete 141. Ozone

- depletion potential (ODP):

(a) Provide the 100 year ODP of the alternative relative to CFC

- 11, if known. If the substitute is a blend, provide the ODPs of the

individual constituents. Reference the source for each ODP.

(b) Provide any additional data on the ODP of the alternative (e.g. atmospheric lifetime, chlorine or bromine loading potentials). Reference

the source of this information and attach any supporting documentation.

M ethylal does not contain any halogen (F, Cl, Br) atoms and therefore is not designated as either a Cl ass I or

Class II Ozone Depleting S ubstance ( ODS )

.

Mark (X) this box if thi s page contains CBI __________  Part II

- ALTERNATIVE

- SPECIFIC INFORMATION (Continued)

Section B

- ATMOSPHERIC INFORMATION

Form 1265

- 07 (Revised 09/2011)

OMB Control No.: 2060

- 0226

Previous editions are obsolete 152. Global Warming Characteristics:

(a) Provide the alternative’s atmospheric lifetime and global warming potential (GWP) relative to carbon di oxide over 100

- year time

horizon, and 20

- year or 500

- year time horizon, if known. Reference the most rece nt assessment report of the Intergovernmental Panel on

Climate Change (IPCC AR4) . Alternate sources may include the 2010 World Meteorological Organization (WMO) Scientific Assessment of

Ozone Depletion or the peer

- reviewed literature

. If the substitute i s a blend, provide the GWPs of the individual constituents and an estimate

of the blend at its nominal composition

.

(b) If known, provide the alternative’s expected impact on energy efficiency relative to the substance it is replacing (e.g. +/

- X%) and results

of any testing or modeling done (both theoretical and actual testing). Energy efficiency information is particularly useful for refrigerants and

foams.

(c) For GWP values that do not come from AR4 or WMO 2010, p rovide any available additiona l data on the atmospheric lifetime and GWP

of the alternative, including infrared absorption spectrum and infrared absorption capacity. Reference the source of this information.

Table 9 illustrates t he Global Warming Potential (GWP) for various blowing agents reported in the 2013

Intergovern mental Panel on Climate Change (IPCC) R eport

, http:/www.ipcc.ch/pdf/special

- reports/sroc/sroc0

. It is generally accepted that the GWP of methylal is comparable to n

- pentane, iso

- pentane and methy l formate.

T hus

, th e GWP for methylal should also be considered t o be negligible.

Table 9 Comparative GWP for Blowing Agents

Product 100 Year GWP

HCFC

- 141

- b 725

HFC

- 365mfc 794

n

- Pentane

-

Iso

- Pentane

- Cyclopentane 11

Methyl Formate

-

Carbon Dioxide 1

Methylal negligible

The GWP d epends on the following factors and is adversely impacted ( correlates ) with a large infrared absorption

and a long atmospheric lifetime

• The degradation of organic chemicals released in the atmosphere starts with their reaction with the

hydro xyl radical. The reaction of hydroxyl radicals with methylal is slow

. This rate is 14 times slower

than expected by calculation if meth ylal is considered to be an ether type chemical

.

• The degradation of organic chemicals released in the atmosphe re is initiated by the reaction with

hydroxyl radical . Atmospheric OH Rate Constant is expressed as OH/cm 3 /molecule

- sec. The Syracuse

University Research Corporation (SRC) database ( http://library.sy r.edu/databases/?type=11 ) reported

that Atmospheric OH Rate Constant for methyl al ( 4.6 +/

- 0.1 10

- 12 ) is in line with n

- pentane (3.94x10

- 12 ),

and iso

- pentane (3.94x10

- 12 )

.

• The atmospheric d egradation of methylal has been investigated to its decompositi on to CO2 and H2O.

The major intermediate atmospheric degrada tion products that have been identified are dimeth yl

carbonate and methoxy methylformate. The intermediate potential production of formaldehyd e is a

minor product. I f emitted into air

, m ethyla l will migrate to the upper ozone forming layer of the

atmosphere where it would only make a moderate contribution to the formation of tropospheric ozone.

M ethylal therefore has a low Photochemical Ozone Creation Potential (POCP).

Table 10 illustrates a comparison of Maximum Incremental Reactivity (MIR) data of methylal with pentanes

. Overall, the MIR reflects the potential increase in ozone formation per unit weight of a compound when added to

the atmosphere

. As noted in Table 10, methylal has a relati vely lower Maximum Incremental Reactivity (MIR),

0.94, in comparison to other pentane blowing agents which indicates a lower potential to produce ozone in the

at mosphere (: http://w ww.arb.ca.gov/consprod/regs/2012/4mirtable50411.pdf ).

Mark (X) this box if this page contains CBI __________ 

Form 1265

- 07 (Revised 09/2011)

OMB Control No.: 2060

- 0226

Previous editions are obsolete 16Table 10 Comparative Methylal MIR with Pentanes

Product MIR Percent Increase

Methylal 0.94

-

n

- Pentane 1.31 + 35%

Iso

- Pentane 1.45 + 55%

Cyclopentane 2.39 + 154 %

Part II

- ALTERNATIVE

- SPECIFIC INFORMATION (continued)

Section C

- OTHE R STATUTES AND STANDARDS

1. Describe whether and how the manufacture, use, and disposal of the alternative is regulated under other environmental regulatory statutes

such as those listed below. List any concentration

- based or other numerical standards t o which the alternative is subject under the standards

and regulations.

The following is based on internet searches and MSDS citations

T he Clean Air Act (CAA) other than Title VI: Not listed as a hazardous air pollutants or Class I or II ODP.

T he Clean Water Act (CWA): Not listed as a Hazardous Substance under the CWA.

T he Safe Drinking Water Act (SDWA) : Not listed under SDWA

.

T he Resource Conservation and Recovery Act (RCRA) : Not listed

.

T he Federal Insecticide, Fungicide, and Rodenticide Act (FI FRA): No restrictions or registrations

.

T he Toxic Su bstances Control Act (TSCA) : Included on the Inventory

.

T he Comprehensive Environmental Response, Compensa tion and Liability Act (CERCLA): Not listed ; no

ass igned RQ

.

T he Emergency Planning and Commu nity Right to Know Act (EPCRA or SARA Title III) : No assigned TPQ;

CAS # 109

- 87

- 5: immediate, fire, reactive.

S tate and local laws : Found on the following state right to know lists: California, New Jersey, Pennsylvania,

Minnesota, Massachusetts.

Other a pplicable environmental federal, state, and local laws not mentioned above:

California Prop 65: No Significant Risk Level ( not listed )

.

Not considered highly hazardous by OSHA.

Section 313: Not reportable under Section 313.

Mark (X) this box if this page contains CBI ___

____ _ 

Form 1265

- 07 (Revised 09/2011)

OMB Control No.: 2060

- 0226

Previous editions are obsolete 172. Describe whether and how occupational, consumer, or general population exposure to the alternative is regulated under

health and safety related statutory authorities, such as those implemented by the Food and Drug Administration (FDA), the

Occupatio nal Safety and Health Administration (OSHA), the Department of Transportation (DOT), and state and local laws.

List any concentration

- based or other numerical standards to which the alternative is subject under the above statutes and

regulations. Also li st any other standard

- setting organizations such as the National Fire Prevention Association (NFPA) the

American Society of Heating, Refrigerating, and Air Conditioning Engineers (ASHRAE), or Underwriters Laboratories (UL)

that will evaluate the substitut e from a health and safety perspective

.

Dimethoxymethane (Methylal) (CAS Number: 109

- 87

- 5) :

FDA : Threshold of Regulation (TOR): Food Contact Substance,

http://www.accessdata. fda.gov/scripts/fdcc/?set=TOR&id=2009

- 0 0 2

Use

Limitatio ns For use as a chain transfer agent in the polymerization of polyoxy methylene copolymers in the

manu facture of repeat use food

- contact articles, at temperatures below 250°F, and in contact with a ll food

types, except those containing more than 15% alcohol.

NLB TOXNET: http://toxnet.nlm.nih.gov/cgi

- bin/sis/search/a?dbs+hsdb:@term+@DOCNO+1820

OSHA: 8 hr Tim e

- Weighted avg: 1,000 ppm (3,100 mg/cu m)

[29 CFR 1910.1000 (7/1/90)] **PEER REVIEWED** (ToxNET)

Threshold Limit Values:

8 hr Time Weighted Avg (TWA): 1000 ppm.

[American Conference of Governmental Industrial Hygienists TLVs and BEIs. Threshold Limit Val ues for Chemical

Substances and Physical Agents and Biological Exposure Indices. Cincinnati, OH, 2008, p. 39] **QC REVIEWED**

Excursion Limit Recommendation: Excursions in worker exposure levels may exceed 3 times the TLV

- TWA for no more

than a total of 30 minutes during a work day, and under no circumstances should they exceed 5 times the TLV

- TWA,

provided that the TLV

- TWA is not exceeded.

[American Conference of Governmental Industrial Hygienists TLVs and BEIs. Threshold Limit Values for Chemical

Substa nces and Physical Agents and Biological Exposure Indices. Cincinnati, OH, 2008, p. 5] **QC REVIEWED**

NIOSH Recommendations:

10 hr Time

- Weighted avg: 1,000 ppm (3,100 mg/cu m).

[NIOSH. NIOSH Pocket Guide to Chemical Hazards. DHHS (NIOSH) Publication No. 94

- 116. Washington, D.C.: U.S.

Government Printing Office, June 1994., p. 198] **QC REVIEWED**

DOT:

Hazard Class: 3 3

UN Number: UN1234

Packing Group: II

State and Local Laws:

Found on the following state right to know lists: California, New Jersey, Pen nsylv ania, Minnesota, Massachusetts.

California Prop 65: No Significant Risk Level: not listed.

National Fire Prevention Association (NFPA): No citation found for methylal

American Society of Heating, Refrigerating : No citation found for methylal

Air Co nditioning Engineers (ASHRAE) : No citation found for methylal

Underwriters Laboratories (UL) : No citation found for methylal

Mark (X) this box if this page contains CBI __________ 

Form 1265

- 07 (Revised 09/2011)

OMB Control No.: 2060

- 0226

Previous editions are obsolete 18Part II

- ALTERNATIVE

- SPECIFIC INFORMATION (continued)

[ Section D

- COST AND AVAILABILITY OF THE ALTERNATIVE

Estimate the cost per pound for the substitute chemical. For alternative processes and technologies, describe installation c osts associated with

the alternative. Please describe the information used as the basis for this cost estimate.

[Pricing and Cost CBI H as Been Removed]

Mark (X) this box if this page contains CBI __________ 

Form 1265

- 07 (Revised 09/2011)

OMB Control No.: 2060

- 0226

Previous editions are obsolete 19More detail on the specific product improvements are included below:

[Pricing and Cost CBI H as Been Removed]

Mark (X) this box if this page contains CBI __________ 

Form 1265

- 07 (Revised 09/2011)

OMB Control No.: 2060

- 0226

Previous editions are obsolete 20[Yearly Volumes CBI H as Been Removed]

Mark (X) this box if this page contains CBI __________ 

Form 1265

- 07 (Revised 09/2011)

OMB Control No.: 2060

- 0226

Previous editions are obsolete 21[Estimated Marketing Penetration and Projections CBI H as Been Removed]

Mark (X) this box if this page contains CBI __________ 

Form 1265

- 07 (Revised 09/2011)

OMB Control No.: 2060

- 0226

Previous editions are obsolete 223. Describe any new equipment and use profiles that will be necessary in order to use the substitute . If retrofitting of existing equipment is

required, detail changes in technologies needed to use the alternative and address any materials compatibility issues. Provide information on

each end

- use and capital costs associated with the substitute or alternative process. Include cost of equipment and/or any new materi als,

equipment lifetime, c hanges in labor and energy costs

.

The 2012 UND P Report (Attachment 2a,b) : Methylal As a Blowing Agent in the Manuf a c ture of Polyurethane

Foam Systems (An Assessment For Application in MLF Projects ) provides an in depth assessment for replacing

high GWP H FCs (such as

, HCFC

- 141b ) and hydrocarbons high in investment costs with methylal . UNEP

concluded that the methylal produced by Lambiott e is commonly available and not i ncumbered by intellectual

property or patent restrictions to use in PU foam applicati ons. Additionally, the use of methylal as a blowin g

agent, and alternative to replace the high GWP HFCs (such as HCFC

- 141b)

, in PU foam applications is feasible.

UNEP considered and provided th e following in their assessment as summaries and in attachmen ts to the Report

• Health, safety and environmental considerations

• Process c a pa bility, including stability, compatibility shipping and storage

• Syst em composition information

• Overview of physical properties obtained from trials for different applications

• Ind icative conversion costs

[Estimated Marketing Penetration and Projections CBI Has Been Removed]

Mark (X) this box if this pag e contains CBI __________ 

Form 1265

- 07 (Revised 09/2011)

OMB Control No.: 2060

- 0226

Previous editions are obsolete 23Part III

- RELEASE AND EXPOSURE DATA

The following data has also been summarized and cited in the 2012 UNDP Report Methylal As a Blowing Agent

in the Manufacture of Polyurethane Foam Systems (Attachments 2a and 2b) and th e Lambiotte Methylal

Chemical Safety Report (Attachment 5 ).

The UNDP (2012, 2a) provided the following overall summary conclusions in its health, safety and environment

assessment:

• Methylal does not create incremental health concerns;

• Methylal does not pose an environmental hazard;

• Methylal shipments and storage in its pure form must c omply with its flammability status;

• While on downstream level, safety concerns may be mitigated through preblending, methylal still

requires safety measures

− In fully formul ated systems <2% methylal (polyols) or <2% methylal (isocyanates) the use of

methylal requires no special safety considerations;

− Systems containing 2

- 5 php methylal need individual consideration and above that level, compliance

with the Globally Harmonized System (GHS) category 2 or 3 is required;

− Local regulations are also to be complied with.

Section A

- TOXICITY AND HAZARD INFORMATION

For chemical alternatives and for chemicals used with alternative processes, summarize below (and attach supporting info rmation on) the

acute and chronic toxicity of the substitute and of its constituent chemicals on any organism (e.g. human and/or other mammal s, fish, wildlife,

and plants), if available. Include any data on impurities and degradation products if known. A lso include information on any permissible

exposure limits (PELs), occupational exposure limits (OELs), or Acceptable Exposure Limits (AELs) that have been set for the substitute for

use in the workplace. In addition, please attach a copy of any hazard wa rning statement, label, material safety data sheet, or other information

which will be provided to any person who is reasonably likely to be exposed. (See Pgs. 16

- 17 of the Instructions for sector

- specific

requirements for toxicity testing).

A recent Lam biotte MSDS is included as Attachment 7

.

Mark (X) this box if this page contains CBI __________ 

Form 1265

- 07 (Revised 09/2011)

OMB Control No.: 2060

- 0226

Previous editions are obsolete 24[Mammalian Toxicology CBI H as Been Removed]

Mark (X) this box if this page contains CBI __________ 

Form 1265

- 07 (Revised 09/2011)

OMB Control No.: 2060

- 0226

Previous editions are obsolete 25[Mammalian Toxicology CBI H as Been Removed]

Mark (X) this box if this page contains CBI __________ 

Form 1265

- 07 (Revised 09/2011)

OMB Control No.: 2060

- 0226

Previous editions are obsolete 26[Mammalian Toxicology CBI H as Been Removed]

Mark (X) this box if this page contains CBI

__________ 

Form 1265

- 07 (Revised 09/2011)

OMB Control No.: 2060

- 0226

Previous editions are obsolete 27[Mammalian Toxicology CBI H as Been Removed]

Mark (X) this box if this page contains CBI __________ 

Form 1265

- 07 (Revised 09/2011)

OMB Control No.: 2060

- 0226

Previous editions are obsolete 28[Mammalian Toxicology CBI H as Been Removed]

Mark (X) this box if this page contains CBI __________ 

Form 1265

- 07 (Revised 09/2011)

OMB Control No.: 2060

- 0226

Previous editions are obsolete 29[Mammalian Metabolism CBI H as Been Removed]

Mark (X) this box if this page contains CBI __________ 

Form 1265

- 07 (Revised 09/2011)

OMB Control No.: 2060

- 0226

Previous editions are obsolete 30[Mammalian Metabolism CBI H as Been Removed]

Mark (X) this box if this page contains CBI __________ 

Form 1265

- 07 (Revised 09/2011)

OMB Control No.: 2060

- 0226

Previous editions are obsolete 31[Mammalian Metabolism and Environmental Fate CBI H as Been Removed]

Mark (X ) this box if this page contains CBI __________ 

Form 1265

- 07 (Revised 09/2011)

OMB Control No.: 2060

- 0226

Previous editions are obsolete 32[ Environmental Fate CBI H as Been Removed]

Mark (X) this box if this page contains CBI __________ 

Form 1265

- 07 (Revised 09/2011)

OMB Control No.: 2060

- 0226

Previous editions are obsolete 33[ Environmental Fate CBI H as Been Removed]

Mark (X) this box if this page contains CBI __________ 

Form 1265

- 07 (Revised 09/2011)

OMB Control No.: 2060

- 0226

Previous editions are obsolete 34[ Environmental Fate and Hazard CBI H as Been Removed]

Mark (X) this box if this page contains CB I __________ 

Form 1265

- 07 (Revised 09/2011)

OMB Control No.: 2060

- 0226

Previous editions are obsolete 35[ Environmental Hazard CBI H as Been Removed]

Mark (X) this box if this page contains CBI __________ 

Form 1265

- 07 (Revised 09/2011)

OMB Control No.: 2060

- 0226

Previous editions are obsolete 36[ Environmental Hazard CBI H as Been Removed]

Mark (X) this box if this page contains CBI __________ 

Form 1265

- 07 (Revised 09/2011)

OMB Control No.: 2060

- 0226

Previous editions are obsolete 37PART III RELEASE AND EXPOSURE DATA

- Section B

- ENVIRONMENTAL RELEASE AND DISPOSAL AT MANUFACTURE

For each manufacturing site ( for manufacturing of substitutes and/or products con taining substitutes) :

(a) Identify all site locations (i.e.

, name and address) for each chemical manufacturing process.

(b) Identify all site locations for manufacturing of products using substitutes (e.g.

, refrigerators containing the substitut es).

(c) Identify the points of release and/or exposure during the manufacture of: (i) the substitute and/or (ii) products contain ing

the substitutes.

(d) Provide information on the magnitude of release if available, along with the media to which the substitute is released

(e.g.

, indoor air, outdoor air, water, land).

T his section is non

- applicable because as noted previously, methylal will be manufactured at the Lambiotte &Cie

S.A. plant at Grand ‘Rue 79 B

- 6724 Marbehan Belgium and imported into the United States in either 55 gallon

drums or Totes. Distribution and the U.S. sales, for foam blowing and other applications, are managed by Holland

Applied Technologies, 7050 High Grove Blvd. Burr Ridge, Illinois 60527

[Environmental Release and Di sposal CBI H as Been Removed]

Mark (X) this box if this page contains CBI __________ 

Form 1265

- 07 (Revised 09/2011)

OMB Control No.: 2060

- 0226

Previous editions are obsolete 38Section C

- OCCUPATIONAL EXPOSURE AT MANUFACTURE

manufacturing site (manufacturing of substitutes and/or products containing su bstitutes):

(a) Describe the activities in which workers may be exposed to chemicals at the manufacturing facility

. Answer items (b) through (g) for

each activity.

(b) Describe any protective equipment and engineering controls used to protect workers (e.g.

, goggles, gloves, chemical hoods).

(c) Indicate the physical form of chemicals at the time of handling/exposure (e.g.

, solid, liquid, gas).

(d) Estimate average and maximum numbers of workers involved in each activity.

(e) Esti mate average and maximum duration of activity for any worker, in terms of (1) hour s /day and (2) days/year.

(f) Enter the contact pathway (e.g.

, ingestion, inhalation, dermal).

(g) Estimate the average and high

- end exposure concentrations (separat ed by a /), being sure to provide units of measure.

[Occupational Exposure at Manufacture CBI H as Been Removed]

Mark (X) this box if this page contains CBI __________ 

Form 1265

- 07 (Revised 09/2011)

OMB Control No.: 2060

- 0226

Previous editions are obsolete 39Section D

- ENVIRONMENTAL RELEASE AND DISPOSAL IN END

- USE

For each end

- use of a substitute (end

- uses using the substitute in products and/or processes):

(a) Provide the estimated amount (in kg /day) of each chemical released to the environment (e.g., as a solid waste or wastewater effluent) at

the point of, or subsequent to, the end

- use at a site using the substitute (e.g., in products containing the substitute and processes using the

substitute ).

(b) Identify the media (indoor air, outdoor air, land, water) to which the chemical will be released from that release point.

(c) Describe the control technology used to limit release; estimate the amount released to the environment with the c ontrol technology in

place to limit release. If the substitute is to be disposed of, indicate the method and location of disposal.

(d) Are releases covered under RCRA? If so, identify the RCRA hazardous waste codes.

(e) Identify the approximate number of sites expected to use the substitute.

(f) Provide information on recycling of the substitute. Describe any associated costs and equipment.

[Environmental Release and Disposal in End

- Use CBI H as Been Removed]

Mark (X) this box if this page contains CBI __________ 

### 

Form 1265

- 07 (Revised 09/2011)

OMB Control No.: 2060

- 0226

Previous editions are obsolete 40[Environmental Release and Disposal in End

- Use CBI H as Been Removed]

Mark (X) this box if this page contains CBI __________ 

### 

Form 1265

- 07 (Revised 09/2011)

OMB Control No.: 2060

- 0226

Previous editions are obsolete 41[Environmental Release and Disposal in End

- Use CBI H as Been Removed]

Mark (X) this box if this page contains CBI __________ 

### 

Form 1265

- 07 (Revised 09/2011)

OMB Control No.: 2060

- 0226

Previous editions are obsolete 42Part III

- RELEASE AND EXPOSURE DATA (continued)

Section E

- OCCUPATIONAL EXPOSURE AT END

- USE

For all end

- use scenarios of the substitute (end

- uses utilizing the substitute in products and/or processes):

(a) Describe the activities in which workers may be ex posed to chemicals at the end

- use (i.e., during installation, maintenance, inspection,

servicing, or use)

. Answer items (b) through (g) for each activity.

(b) Describe any protective equipment or engineering controls used to protect workers (e.g.

, goggles, gloves, chemical hoods).

(c) Indicate the physical form of chemicals at the time of handling/exposure (e.g.

, solid, liquid, gas).

(d) Estimate average and maximum numbers of workers involved in each activity.

(e) Estimate average a nd maximum duration of activity for any worker, in terms of (1) hours/day and (2) days/year.

(f) Enter the contact pathway (e.g

, . ingestion, inhalation, dermal).

(g) Estimate the average and high

- end exposure concentrations (separated by a /), be ing sure to provide units. Personal monitoring data

may be required for some end uses (see pg s. 17

- 18 of Instructions)

____________________________

[Occupational Exposure at End

- Use CBI H as Been Removed]

Personal protection (also refer to MSDS)

• Respira tory protection : Where excessive vapor may result, wear an appropriate NIOSH and OSHA approved

mask and or respirator.

• Hand protection : In case of repeated or prolonged contact wear gloves.

• Skin protection : No special clothing/skin protection equipment is recommended under normal

• conditions of use.

• Eye protection : Goggles.

• Ingestion : When using, do not eat, drink or smoke.

• Industrial hygiene : Local exhaust and general ventilation must be adequate to meet exposure

• standards.

• TLV

- TWA [ppm] : 1000

Mark (X) this box if this page contains CBI __________ 

### 

Form 1265

- 07 (Revised 09/2011)

OMB Control No.: 2060

- 0226

Previous editions are obsolete 43The typical formulations to which methylal

– polyol formulators may be exposed are reported below in Tables 19

and 20 . The methylal

- polyol blowing agent f o r mulations are also compared to com parable/analogous HCFC 141b

blowing agent formulations. In t he methylal

– polyol blowing agent formulations methylal concentrations range

from 8% in typical rigid foam formulations to 2.74% in flexible molded formulations. Note that in each case the

amount of methylal by weight is sign ificantly lower that of HCFC

- 141b which is 14.52 and 3.65% respectively . The

UNEP Report (Attachment 2b) provides specific product application formulations that compare the percent in

formulations for both methylal and HCFC

- 141b. The maximum concentration cited is for the “Pour in Pl ace”

formulation in which the amount of methylal is listed to be 10.5% in the formulation and the amount of HCFC

- 141b

is listed to be 14.6%. The information in Table 19 highlights the reduce volume for volume use of methylal

compared to HCFC

- 141b.

Table 19

. Typical Rigid Foam Formulation

Table 20

. Typical Flexible Molded Foam Formulation

Mark (X) this box if this page contains CBI __________ 

Form 1265

- 07 (Revised 09/2011)

OMB Control No.: 2060

- 0226

Previous editions are obsolete 44[Occupational Exposure at End

- Use CBI H as Been Removed]

Questions e and g

It is likely that no more than 1 or 2 workers per site would be involved either in the transfer of methylal to prepare

pol yol

- methylal formulations (System Houses) or the transfer of methylal polyol blowing agent formulations

(Downstream End

- Users) to react with isocyanate in the manufacture of a particular rigid or flexible polyurethane

foam product. As previously noted in this SNAP the following are the current EPA worker exposure Federal

guidelines:

OSHA: 8 hr Time

- Weighted avg: 1,000 ppm (3,100 mg/cu m)

[29 CFR 1910.1000 (7/1/90)] **PEER REVIEWED** (ToxNET)

Threshold Limit Values (TLV )

8 hr Time Weighted Avg (TWA): 1000 ppm.

[American Conference of Governmental Industrial Hygienists TLVs and BEIs. Threshold Limit Values for Chemical Substances

and Physical Agents and Biological Exposure Indices. Cincinnati, OH, 2008, p. 39] **QC REVIEWED**

Excursion Limit Recommendatio n: Excursions in worker exposure levels may exceed 3 times the TLV

- TWA for no more than a

total of 30 minutes during a work day, and under no circumstances should they exceed 5 times the TLV

- TWA, provided that the

TLV

- TWA is not exceeded.

[American Confere nce of Governmental Industrial Hygienists TLVs and BEIs. Threshold Limit Values for Chemical Substances

and Physical Agents and Biological Exposure Indices. Cincinnati, OH, 2008, p. 5] **QC REVIEWED**

NIOSH Recommendations:

10 hr Time

- Weighted avg: 1,00 0 ppm (3,100 mg/cu m).

[NIOSH. NIOSH Pocket Guide to Chemical Hazards. DHHS (NIOSH) Publication No. 94

- 116. Washington, D.C.: U.S.

Government Printing Office, June 1994., p. 198] **QC REVIEWED**

Mark (X) this box if this page contains C BI __________ 

### 

Form 1265

- 07 (Revised 09/2011)

OMB Control No.: 2060

- 0226

Previous editions are obsolete 45[Occupational Exposure at End

- Use CBI H as Been Removed]

Mark (X) this box if this page contains CBI __________ 

### 

Form 1265

- 07 (Revised 09/2011)

OMB Control No.: 2060

- 0226

Previous editions are obsolete 46Section F

- CONSUMER EXPOSURE

For each end

- use of a substitute (end

- u ses where a consumer might be exposed) :

(a) Identify the potentially exposed consumer population (e.g

, . indoor residents).

(b) Identify the exposure medium (e.g.

, air).

(c) Enter the contact pathway (e.g

, . ingestion, inhalation, dermal).

(d) De s cribe the exposure point of concentration. Provide (1) average and (2) high

- end concentration estimates , including units of measure

.

[Consumer Exposure CBI H as Been Removed]

Mark (X) this box if this page contains CB I __________ 

### 

Form 1265

- 07 (Revised 09/2011)

OMB Control No.: 2060

- 0226

Previous editions are obsolete 47Part III

- RELEASE AND EXPOSURE DATA (continued)

Section G

- GENERAL POPULATION EXPOSURE (optional)

For manufacturing of substitutes and products containing substitutes:

(a) Identify and number potential general population exposure points.

(b) For each exposure point described in (a), identify the potentially exposed population (e.g.

, residents at the fenceline to the

manufacturing facility ).

(c) Identify the contact pathway (e.g.

, ingestion, inhalation, dermal).

(d) I dentify the exposure medium (e.g.

, air, water).

(e) Enter the exposure point concentration (mg/m 3 or ppb ). Provide (1) average and (2) high

- end estimates.

Refer to Section F

Mark (X) this box if this pa ge contains CBI __________ 

### 

Form 1265

- 07 (Revised 09/2011)

OMB Control No.: 2060

- 0226

Previous editions are obsolete 48Part IV

- LIST OF ATTACHMENTS

List below any attachments that complete the responses to the questions on this form or that provide additional information t hat may assist

EPA’s review of the alternative under Section 612 of th e Clean Air Act. Also, provide citation s for information already submitted to EPA as

part of past regulatory and information activities, as well as for other information that could not be included with this sub mission. If you have

attached continuation p ages, describe the Part, Section and question number being continued. Attach additional pages if necessary. Mark (X)

in the CBI box next to any attachment that contains information you claim as confidential.

Attachment Name Question # Number of

Pages CB I

#1 CAS IES Report Part 1; Sec B

(2a) 4

#2a UND P (2012 a ) Methylal As Blowing Agent in The Manufacture of

Polyurethane Foam Systems

– Report Summary

#2b UN D P (2012b) Methylal As Blowing Agent in The Manufacture

of Polyurethane Foam Systems

– Full Report and Analysis Part 1; Sec B (5) 112

[Attachment CBI H as Been Removed] Part 1; Sec B (5) 3 7 X

# 4 a Methylal EPISuite TM 4.1 Calculations

– Ultimate Fugacity

#4b Methylal EPISuite TM 4.1 Calculations

– Primary Fugacity Part 2 Section A 7

[Attachment CBI H as Been Removed] Part 2 Section A 640 X

#6) EU ANNEX VI: General Classification and Labelling

Requirements for Dangerous

Substances And Preparations Part 2 Section A

28. Flammability 21

#7) Methylal MSDS Part 3 Section A 10

[Attachment CBI H as B een Removed] Part 3 Section A 26 X

#9) Weaver FL, Hough AR, Highman B, Fairhall LT [1951]. The

toxicity of methylal. Br J Ind Med 8 :279

- 283 Part 3 Section A 6

[Attachment CBI H as Been Removed] Part 3 Section A 25 X

Mark (X) this box if this page con tains CBI __________ 

Form 1265

- 07 (Revised 09/2011)

OMB Control No.: 2060

- 0226

Previous editions are obsolete 49[Attachment CBI H as Been Removed] Part 3 Section A 22 X

[Attachment CBI H as Been Removed] Part 3 Section A 34 X

[Attachment CBI H as Been Removed] Part 3 Section A 49 1 X

[Attachment CBI H as Been Removed] Part 3 Section A 1 57 X

[Attachment CBI Has Been Removed] Part 3 Section A 36 X

[Attachment CBI Has Been Removed] Part 3 Section A 56 X

Mark (X) this box if this page contains CBI __________ 

Form 1265

- 07 (Revised 09/2011)

OMB Control No.: 2060

- 0226

Previous editions are obsolete 50[Attachment CBI Has Been Removed] Part 3 Section A 30 X

[Attachment CBI Has Been Removed] Part 3 Section A 40 X

[Attachment CBI Has Been Removed] Part 3 Section A 14 X

[Attachment CBI Has Been Removed] Part 3 Section A 9 X

[Attachment CBI Has Been Removed] Part 3 Section A 7 X

[Attachment CBI Has Been Remov ed] Part 3 Section A 8 X

[Attachment CBI Has Been Removed] Part 3 Section A 10 X

[Attachment CBI Has Been Removed] Part 3 Section A 4 X

Mark (X) this box if this page contains CBI __________ 

Form 1265

- 07 (Revised 09/2011)

OMB Control No.: 2060

- 0226

Previous editions are obsolete 51[Attachment CBI Has Been Removed] Part 3 Section A 14 X

[Attachment CBI Has Been Removed] Part 3 Section A 25 X

[Attachment CBI Has Been Removed] Part 3 Section A 68 X

[Attachment CBI Ha s Been Removed] Part 3 Section A 18 X

[Attachment CBI Has Been Removed] Part 3 Section A 8 X

[Attachment CBI Has Been Removed] Part 3 Section A 6 X

[Attachment CBI Has Been Removed] Part 3 Section A 31 X

[Attachment CBI Has Been Removed] Part 3 Section A 4 X

Mark (X) this box if this page contains CBI __________ 

Form 1265

- 07 (Revised 09/2011)

OMB Control No.: 2060

- 0226

Previous editions are obsolete 52[Attachment CBI Has Been Removed] Part 3 Section A 12 X

[Attachment CBI Has Been Removed] Part 3 Section A 19 X

[Attachment CBI Has Been Removed] Part 3 Section A 11 X

[Attachment CBI Ha s Been Removed] Part 3 Section A 19 X

#37) ECOSAR Modeling Part 3 Section A 3

[Attachment CBI Has Been Removed] Part 3 Section D 44 X

Mark (X) this box if this page contains CBI __________ 

Form 1265

- 07 (Revised 09/2011)

OMB Control No.: 2060

- 0226

Previous editions are obsolete 53