Final—October 10, 2014 

### 1 

# Significant New Alternatives Policy Program Foam-Blowing Sector
Risk Screen on Substitutes in Rigid Polyu rethane Appliance Foam; Rigid Polyurethane and Polyisocyanurate Laminated Boards tock; Rigid Polyurethane Commercial Refrigeration and Sandwich Panels; Rigid Poly urethane Slabstock and Other; Flexible Polyurethane; Integral Skin Polyurethane; an d Phenolic Insulation Board and Bunstock
Substitute: HFO-1336mzz( Z) (Formacel® 1100)

This risk screen does not contain Clean Air Act (CAA) Confidential Business Information (CBI) and, therefore, may be disclosed to the public.



### 1. INTRODUCTION
Ozone-depleting substances (ODS) are being phased out of production in response to a series of diplomatic and legislative efforts that have taken place over the past two decades, including the Montreal Protocol and the Clean Air Act Amendments of 1990 (CAAA). The U.S. Environmental Protection Agency (EPA), as authorized by Section 612 of th e CAAA, administers the Significant New Alternatives Policy (SNAP) Program, which identifies acceptable and unacceptable substitutes for ODS in specific end-uses based on assessment of their health and environmental impacts. EPA’s decision on the acceptability of a substitute is based on the findings of a screening assessment of potential human health and environmental risks posed by the substitute in specific applications. EPA has already screened a large number of substitutes in ma ny end-uses within all of the major ODS-using sectors, including refrigeration and air conditioning, solvent cleaning, foam blowing, aerosols, fire suppression, adhesives, coatings and inks, and sterili zation. The results of these risk screens are presented in a series of Background Documents that are available in EPA's docket. The purpose of this risk screen is to supplement EPA’s Background Document on the foam blowing sector (EPA 1994) (hereinafter referred to as the Ba ckground Document). This risk screen evaluates the potential use of HFO-1336mzz(Z) (also known as 2-Bute ne, 1,1,1,4,4,4-hexafluoro-,(2Z-) and hereinafter referred to as Formacel® 1100) as a substitute in rigid polyurethane appliance foam; rigid polyurethane and polyisocyanurate laminated boardstock; rigid polyurethane commercial refrigeration and sandwich panels; rigid polyurethane slabstock and other; flex ible polyurethane; integral skin polyurethane; and phenolic insulation board a nd bunstock. Table 1 presents informat ion on the proposed substitute.Final—October 10, 2014 

### 2 Table 1. Composition of Formacel® 1100

Constituent Chemical Formula CAS Number Percent of Total (by weight) 2-Butene, 1,1,1,4,4,4-hexafluoro-,(2Z-) (HFO-1336mzz(Z)) CF 3 CHCHCF 3 692-49-9
Potential Impurities (maximum concentration)

The potential risks associated with use of foam blow ing agents have been examined at length in the Background Document. The reader is referred to this reference for a detailed discussion of the methodologies used to conduct this risk screen. This risk screen addresses fl ammability risk and assesses the impact of potential releases of Formacel® 1100 on the atmosphere, climate and other environmental impacts. Occupational exposure was modeled to ensu re that manufacture and application of the proposed substitute in the proposed foam blowing end-uses do es not pose unacceptable risk to workers. Lastly, general population exposure modeling w as performed to ensure that the proposed substitute would not pose an unacceptable risk to th e population at large.

Section 2 of this report summarizes the results of the risk screen for the proposed substitute. The remainder of the report is organized into the following sections:

 Section 3: Atmospheric Assessment

 Section 4: Volatile Organic Compound Assessment

 Section 5: Potential Health Effects

 Section 6: Flammability Assessment

 Section 7: Occupationa l Exposure Assessment

 Section 8: General Population Assessment

 Section 9: Aquatic and Ecosystem Impact Assessment

 Section 10: References



### 2. SUMMARY OF RESULTS Formacel® 1100 is recommended for SNAP approval as a foam-blowing agent in the following end-uses: rigid polyurethane appliance foam; rigid polyurethan e and polyisocyanurate laminated boardstock; rigid polyurethane spray, commercial refrigeration, and san dwich panels; rigid pol yurethane slabstock and other; flexible polyurethane; integral skin polyur ethane; and phenolic insula tion board and bunstock.Final—October 10, 2014 

### 3 EPA's risk screen indicates that th e use of the proposed substitute will be less harmful to the atmosphere than the continued use of CFC-11, CFC-113, HCFC-141b, and HCFC-22, as well as other commonly used blowing agents. Given that appropriate pers onal protective equipment (PPE) (e.g., respiratory protection, goggles, impervious gloves, chemical -resistant clothing and boots) consistent with Occupational Safety & Health Administration (OSH A) guidelines will be used during manufacture; and proper procedures according to the MSDS (including provisions of engineering controls [e.g., exhaust ventilation, vapor-in-air detection systems]) will be used during manufacturing and application activities, no significant toxicity risks to workers or the gene ral population are expected. In addition, based on the non-flammable nature of the proposed substitute, Form acel® 1100 is not expected to present a significant flammability concern during manufacture or end-use (see Section 6).



### 3. ATMOSPHERIC ASSESSMENT This section presents an assessment of the potential ri sks to atmospheric integrity posed by the use of Formacel® 1100 in the foam blowing sector. The ozone depletion potential (ODP), global warming potential (GWP), and atmospheric lifetime (ALT) of th e proposed substitute are presented in Table 2. As compared to CFC-11 and HCFC-141b, CFC-113, an d HCFC-22, Formacel® 1100 is substantially less harmful to the ozone layer, has less climate impact , and a shorter atmospheric lifetime. Formacel® 1100 has a non-zero GWP, but at 8.9, this value is very small when considering continued use of HCFC-141b or HCFC-22. Further, Formacel® 1100 has a lower climate impact and a shorter atmospheric lifetime than those predicted for other substitutes examin ed in the Background Document. Thus, EPA believes that use of Formacel® 1100 would result in substantially less harm to the climate and ozone layer than the continued use of ODS.

Table 2. Atmospheric Impacts of Formacel® 1100 Compared to Other Foam-Blowing Agents Refrigerant ODP a GWP b ALT (years) b Formacel® 1100 0 c 8.9 c 22 days c CFC-11 1.0 4,750 45 CFC-113 0.85 6,130 85 HCFC-141b 0.12 725 9.3

HCFC-22 0.04 1,810 12 HFC-134a 0 1,430 14 HFC-245fa 0 1,030 7.6 HFC-365mfc 0 794 8.6

a WMO (2011)

b IPCC 4 th Assessment Report (Forster et al. 2007)

c DuPont (2011c)



### 4. VOLATILE ORGANIC COMPOUND ASSESSMENT Formacel® 1100 is regulated as a volatile organi c compound (VOC) under the CAA (40 CFR 51.000). Through regulations and st andard industry practices, emissions of Formacel® 1100 should be controlled. The submitter has indicated that a petition will be su bmitted to exempt this compound from the definition of VOC for purposes of regulations in state impl ementation plans for local air quality; however, Formacel® 1100 continues to be regulated as a VOC for that purpose unless and until EPA issues a final rule exempting it.

An assessment was performed to compare the annual VOC emissions from use of Formacel® 1100 in the foam blowing end-uses in one year to other an thropogenic sources of VOC emissions. Assuming the submitter’s maximum anticipated annual production of Formacel® 1100 for all proposed foam blowing end-uses is entirely released (in the absence of cont rols), approximately [] of VOCs would be emitted.Final—October 10, 2014 

### 4 This is approximately equal to [] percent of all anthropogenic VOC emissions from 2013 in the U.S.; 1 however, the release of total production for all foam blowing end-uses is extremely unlikely to occur. Thus, an additional analysis was performed to determine likely annual VOC emissions from use of Formacel® 1100 in the foam blowing sector. Table 3 su mmarizes leak estimates and market penetrations from the Vintaging Model for the proposed foam blowing end-uses.

Table 3. Foam Release Rates and Market Penetrations by End-Use

Foam End-Use Annual Leak Rate First Year Loss a Disposal Loss Lifetime (yrs) Average Annual Release Rate b Market Share PU Rigid – Commercial Refrigeration 0.25% 6% 90.25% 15 6% 1%
PU Rigid – Slabstock 0.75% 37.5% 51.25% 15 6% 1% PU Rigid – Appliance 0.25% 3.75% 39.88% 14 3% 13% PU Rigid – Sandwich Panels 0.50% 5.5% 69.5% 50 2% 3%
PU and PIR Rigid – Boardstock 1% 6% 44% 50 1% 78%

Flexible PU - Slabstock 0% 100% 0% 1 100% 1% Flexible PU - Integral Skin 2.5% 95% 0% 2 49% 0%

Phenolic Insulation Board and Bunstock 0.875% 23% 49% 32 2% 3%
Source: Vintaging Model (v4.4_7.29.14).

a First year losses include losses at manufacture and other production steps that occur prior to end-use.

b Calculated as (Leak Rate + First Year Loss + Disposal Loss)/Lifetime

Assuming the average annual release rates for each pr oposed foam blowing end-use, and that use of Formacel® 1100 is distributed according to existing market share for each proposed foam end-use, 2 approximately 304 MT of VOCs would be expected to be released into the atmosphere annually. This amount is approximately 1.89 x 10 -3 percent of all anthropogenic VOC emissions. In addition, the enduses with the greatest annual release rate (e.g., integr al skin and flexible polyurethane slabstock) are reasonably expected to occur indoors in a manuf acturing or disposal facility, which would have engineering controls in place (e.g., carbon adsorption systems or scrubbers) such that actual quantities of Formacel® 1100 emissions would be less than th e quantity calculated in this assessment.

Thus, use of Formacel® 1100 would not result in greater impacts on local air quality than other available options. In addition, Formacel® 1100 has a lower Maximum Incremental Reactivity (MIR) (i.e., 0.04) relative to other commonly used blowing agents (i.e ., isopentane [MIR = 0.93], n-pentane [MIR = 1.31], and cyclopentane [MIR = 2.39]) (DuPont 2012a). Thus, Formacel® 1100 has a lower potential to produce ozone in the atmosphere compared to other comm only used blowing agents. As the calculated annual releases of Formacel® 1100 from these analyses are seve ral orders of magnitude smaller than other anthropogenic sources of VOC emissions, EPA believ es that through the use of standard industry practices, the environmental impacts of these VOCs are not considered a significant concern.

1 Based on the 2013 annual total VOC emissions for the U.S. (i.e., approximately 16.1x10 6 MT) as reported in the National Emissions Inventory (EPA 2014).

2 The distribution of proposed foam end-uses is based on EPA’s Vintaging Model and may not necessarily represent the submitter’s intended market share for production of Formacel® 1100

.Final—October 10, 2014 

### 5 5. POTENTIAL HEALTH EFFECTS To assess potential health risks from exposure to this proposed substitute, DuPont developed an acceptable exposure limit (AEL) of [] for Formacel ® 1100 (DuPont 2014). The AEL represents the maximum 8-hour time weighted average (TWA) at wh ich a worker can be exposed regularly without adverse effects. In addition, the Occupational A lliance for Risk Science (OARS) proposed a workplace environmental exposure level (WEEL) of 500 ppm as an 8-hour time weighted average.

According to the MSDS, exposure to Formacel® 1100 ma y be harmful by ocular or dermal absorption, inhalation, or ingestion. Regardless of the route of exposure, the MSDS recommends that a physician be contacted in the case of any exposure. Specifically, in case of ocular exposure, the MSDS for Formacel® 1100 recommends that person(s) should immediately fl ush the eyes with water for at least 15 minutes. Exposures of Formacel® 1100 to the skin should also immediately be flushed with water for at least 15 minutes; should frostbite occur, it should be treated by gently warming the affected area. All contaminated clothing should be removed and washed before re-use. Inhalation may cause cardiac effects such as irregular heartbeat accompanied by atypical chest sensations, heart thumping, apprehension, fainting, dizziness, or weakness. In addition, Fo rmacel® 1100 vapors are heavier than air and in high concentrations cause suffocation and asphyxiation by reducing oxygen available for breathing. If Formacel® 1100 is inhaled, person(s) should be imme diately moved to fresh air. The MSDS further recommends that person(s) be kept lying and warm, a nd provided oxygen and/or artificial respiration if necessary. In situations of emergency life support, physicians should use catecholamine drugs with particular caution because of possible cardiac rhythm disturbances. In case of ingestion, the MSDS recommends having the person(s) drink one to two cups of water, if fully conscious. If the person vomits while lying on his/her back, the person should be repositioned. Do not induce vomiting without medical advice. EPA’s review of the human h ealth impacts of this proposed s ubstitute is contained in the public docket for this decision. These risks and procedures after exposure are similar for other common blowing agents.

The potential health effects of Formacel® 1100 are unlikely to occur when following good industrial hygiene practices and the PPE and engineering control (e.g., ventilation) recommendations outlined in the MSDS for Formacel® 1100 and Sections 7 and 8 of this risk screen.



### 6. FLAMMABILITY ASSESSMENT Formacel® 1100 is not flammable []; thus, the pro posed substitute is not considered to pose a flammability risk.



### 7. OCCUPATIONAL EXPOSURE ASSESSMENT This section presents an assessment of potential o ccupational exposures to Formacel® 1100, which is anticipated to occur during manufacture of blown foam. Based on this assessment, Formacel® 1100 was found not to present a significant risk to workers.

Limited data are available regarding employee exposur es to blowing agents for the proposed foam types at manufacture. The submitter, however, was able to provide results of a laboratory test to measure the worst-case occupational exposures resulting from th e manufacture of refrigerator cabinets. The monitoring results indicated that instantaneous c oncentrations did not exceed [], and 8-hour timeweighted average concentrations were [], which is si gnificantly lower than the [] AEL. In addition, the submitter indicated that the testing performed w as designed to measure the worst-case occupational exposure to industrial foam blowing manufacture of Formacel® 1100. The testing was conducted in a small room with normal air exchange rates in cont rast to commercial manufacturing facilities which areFinal—October 10, 2014 

### 6 large with local exhaust ventilation.

Although exposure data were not available for the ma nufacture of the remaining foam blowing end-uses, such as integral skin foam and slabstock foam, whic h are estimated to have the greatest first year losses (see Table 3), the majority of losses are anticipated to occur after manufacture, during processing (Jeffs 2012). For slabstock foam and flexible polyurethane fo am, this would include cutting of the foam, and for integral skin, this would include removing the foam from its molds. However, the resulting occupational exposure during these activities is not anticipated to present a significant concern (Jeffs 2012). Further, since the monitoring data indicates that the 8-hour time-weighted average exposure concentration [] during appliance foam manufacturing under a conser vative scenario are significantly lower than the 8- hour AEL for Formacel® 1100 [], it is unlikely that exposure during manufacture and processing of the other proposed foam end-uses would result in co ncentrations beyond the acceptable occupational exposure limit.

During manufacture and use of Formacel® 1100, engineer ing controls should be in place, such as vaporin air detection systems. Adequate ventilation shoul d always be established during any use, handling, or storage of Formacel® 1100. In addition, an eye wash and safety shower should be near the manufacturing facility and ready for use. In general, use of PPE is recommended, such as NIOSH-approved respiratory protection, chemical splash goggles or face shield, impervious gloves, and chemical-resistant boots and clothing consistent with OSHA guidelines (DuPont 2011c, OSHA 1994).

EPA believes that because proper handling guidelines are followed in accordance with good industrial hygiene and manufacturing practices and the MSDS for Formacel® 1100, as described above, manufacture of Formacel® 1100 foam does not present a significant risk to workers.



### 8. GENERAL POPULATION EXPOSURE ASSESSMENT This section screens potential risks to the genera l population from chronic exposure to releases of Formacel® 1100 during the lifetime of the foam, becau se these agents can slowly leak from the foam over time.

As a result, in locations where persons are regul arly present for extended periods, such as a home or apartment, the persons could be exposed to very low levels of Formacel® 1100 over time. Based on the foam blowing end-uses proposed for Formacel® 1100 , the maximum annual operating leak rate of Formacel® 1100 during the lifetime of the foam (i.e ., after manufacture and before disposal) is anticipated to be 2.5% (see Table 3), resulting in very minimal exposure concentrations well below the AEL[]. Due to the low toxicity of Formacel® 1100 and minimal expected release, EPA believes that such exposures do not pose a significant toxicity risk, a nd thus, Formacel® 1100 is not expected to cause a significant impact on human health in the general pop ulation when used as a foam blowing agent in the proposed end-uses.



### 9. AQUATIC AND ECOSYSTEM IMPACT ASSESSMENT To assess potential environmental risks from releases of the proposed substitute to water and aquatic life, EPA reviewed studies evaluating the ecotoxity of Formacel® 1100. Notably, the studies indicated that the chemical has high volatility and would very likely not remain in surface water at concentrations high enough to be considered toxic to the environment. One study, Mitsubishi (2011), indicated that Formacel® 1100 could be toxic to fish. However, the study authors had to continually replenish the Formacel® 1100 in the samples in order to try to maintain the test concentrations of 100 mg/L and observe these effects. The submitter has indicated th at releases of the proposed substitute to surface waterFinal—October 10, 2014 

### 7 are expected to be [] in accordance with facility permit limits. Because releases are expected to be minimal and highly volatile, toxic concentrations of Formacel® 1100 are not likely to occur under normal manufacture and use of the proposed substitute. B ased on these considerations, EPA believes that Formacel® 1100 will not pose significant environmenta l risks through contact with aquatic life.Final—October 10, 2014 

### 8 10. REFERENCES
DuPont Chemicals and Fluoroproducts. 2014. Letter fro m Toxicology Excellence for Risk Assessment on the Workplace Environmental Exposure Level (WEEL) de veloped by the Occupational Alliance for Risk Science for Formacel® 1100. September 10, 2014

DuPont Chemicals and Fluoroproducts. 2012a. Pe rformance Update on Formacel® 1100– a Zero ODP and Low GWP Foam Expansion Agent. May 8-9, 2012. Available at:

< http://www2.dupont.com/Formacel/e n_US/assets/downloads/20120508_FEA1100_Performance_Update_charts.pdf>

DuPont Chemicals and Fluoroproducts. 2012b. Response to Incomplete SNAP Submission for Formacel® 1100. September 5, 2012.

DuPont Chemicals and Fluoroproducts. 2011a. Formacel ® 1100 Foam Stability Testing. September 9, 2011.

DuPont Chemicals and Fluoroproducts. 2011b. Response to Incomplete SNAP Submission for Formacel® 1100. August 15, 2011.

DuPont Chemicals and Fluoroproducts. 2011c. SNAP S ubmission to EPA for Formacel® 1100. August 3, 2011.

EPA. 1994. Significant New Alternatives Policy Techni cal Background Document: Risk Screen on the Use of Substitutes for Class I Ozone-depleting Subs tances: Foam Blowing Agents. Stratospheric Protection Division. March, 1994.

EPA. 2011. National Emissions Inventory Air Pollutant Emissions Trends Data. Accessed 23 December 2011. Updated October 2011. Ava ilable at: <http://www.epa.gov/ttn/chief/trends/index.html#tables>

Forster, P., V. Ramaswamy, P. Artaxo, T. Berntsen , R. Betts, D.W. Fahey, J. Haywood, J. Lean, D.C. Lowe, G. Myhre, J. Nganga, R. Prinn, G. Raga, M. Schulz and R. Van Dorland. 2007. Changes in Atmospheric Constituents and in Radiative Forcing. In: Climate Change 2007:The Physical Science Basis. Contribution of Working Group I to the Fourth Assessment Report of the Intergovernmental Panel on Climate Change [Solomon, S., D. Qin, M. Manning, Z. Chen, M. Marquis, K.B. Averyt, M.Tignor and H.L. Miller (eds.)]. Cambridge University Press, Cambridge, United Kingdom and New York, NY, USA. Jeffs, Mike. Personal communication between ICF Inte rnational and Mike Jeffs. April 24-26, 2012.

OSHA. 1994. General description and discussion of the levels of protection and protective gear. 1910.120 App B. Last updated August 22, 1994. Available at: http://www.osha.gov/pls/oshaweb/owadisp.s how_document?p_table= STANDARDS&p_id=9767

Mitsubishi Chemical Medience Corporation. 2011. Ac ute Toxicity Test of 1100 with Medaka (Oryzias latipes). Study Number A100566. Su bmitted to DuPont-Mitsui Fluoroch emicals, Co., Ltd. August 26, 2011.

WMO (World Meteorological Organization), 2011. Sc ientific Assessment of Ozone Depletion: 2010, Global Ozone Research and Monitoring Project—Rep ort No. 52, 516 pp., Geneva, Switzerland, 2011.