### Solvay	Fluorides,	LLC

SNAP	APPLICATION	SUMMARY: Solkane® 365/227 1


### The	purpose	of	this	document	is	to	summarize	and	organize	the	information	submitted	to the	U.S.	Environmental	Protection	Agency	(“EPA”)	by	Solvay	Fluorides,	LLC	(hereinafter, “Solvay”)	in	furtherance	of	Sol v ay ’ s	application	to	list its Solkane 365/227 liquid hydrofluorocarbon (“HFC”) blend as	an	alternative	to	HCFC

- 141b	in	all	foam

- blowing	end

uses. The	Agency	notified	Solvay	in	a	February	10,	2012	letter,	that	this	SNAP	application was	complete	as	of	January	3 1,	2012. Solkane	365/227

Composition: Blowing agent blend containing from 7 to 13 % HFC

- 227ea and the remainder HFC

365mfc: CAS No. Formula Amount HFC

- 365mfc: 1,1,1,3,3

- pentafluorobutane 406

- 58

- 6 C 4 

### H 5 

### F 5 

### 93

– 87% HFC

- 227 ea : 1,1,1,2,3,3,3

- heptafl uoropropane 431

- 89

- 0 C 3 

### HF 7 

### 7

– 13% See EPA

- HQ

- OAR

- 2003

- 0118

- 0278 ; Letter from Dr. Marc A. Feldman to Mel i s sa Fiffer, EPA (Jan. 30, 2012)

End

- Uses : Replacement for HCFC

- 141b in the following end

- uses:

• Rigid Polyurethane: Appliance

• Rigid Polyurethane: Spr ay, Commercial Refrigeration, and Sandwich Panels

• Rigid Polyurethane: Slabstock and Other

• Rigid Polyurethane & Polyisocyanurate Laminated Boardstock

• Flexible Polyurethane

• Integral Skin Polyurethane

• Polystyrene: Extruded Sheet

• Polystyrene: Extruded Boardsto ck & Billet

• Polyolefin

• Phenolic Insulation Board & Bunstock

Atmospheric Performance: HFC

- 365mfc has been determined by EPA to be “less harmful to the ozone layer” and is approved as an alternative to HCFC

- 141b in foam blowing applications. See EPA

- HQ

OAR

- 2003

- 0118

- 0235 Risk Screen for HFC

- 365mfc in Foam Blowing

. Similarly, HFC

- 227ea does not deplete the ozone layer

. EPA has approved HFC

- 227ea as an ODS alternative for us e in chillers, and as a substitute to H alon 1 3 01 in total flooding and certain streami ng fire suppression systems

. See generally, Protection of Stratospheric Ozone , 59 Fed . Reg. 13,044 (March 18, 1994). See also EPA

- HQ

- OAR

- 2003

- 0118

- 0004 , Risk Screen on The Use of Substitutes For Class I Ozone

- Depleting Substances: Fire Suppression And E xplosion Protection (Halon Substitutes)

. The agency also has listed HFC

- 227ea as acceptable for use in metered dose inhalers because it meets a specialized application in metered dose inhalers where other substitutes do not provide acceptable performance. See Protection of Stratospheric Ozone, 63 Fed. Reg. 28,251 (May 22, 1998). The GWP s of HFC

- 365mfc and

- 227ea, individually and as a blend , are comparable to

1 Solkane® is a registered trademark of Solvay Corporation S.A.

### Solvay	Fluorides,	LLC

Solkane	365/227 other alternatives approved by EPA for foam blowing applications:
ODP GWP

- 100 * ALT VOC CFC

- 11 1 4,750 45 No HCFC

- 141b 0.11 725 9.3 No Formacel Z

- 6 0 370

– 1 , 290 + ?? No HFC

- 245fa 0 1,030 7.6 No HFC

- 365mfc 0 79 0 8.6 No HFC

- 365/245fa 2 0 865

- 960 ** 8.6/7.6 N o HFC

- 227ea 0 3,220 40 No S o lkane 365/227 0 959

- 1,105 ‡ 8.6/40 No

* All GWP

- 100 values are from the ¶ 2.10.2, IPCC Fourth Assessment Report: Climate Change 2007 available at http://www.ipcc.ch/publications_and_data/ar4/wg1/en/ch2s2

- 10

- 2.html , except where expres sly indicated.

+ Protection of Stratospheric Ozone: Determination 27 for Significant New Alternatives Policy Program , 77 Fed. Reg. 47,768, 47,472 (August 10, 2012)

** Protection of Stratospheric Ozone: Notice 24 for Significant New Alternatives Policy Pro gram , 74 Fed. Reg. 50,129, 50,133 (September 30, 2009) ‡ Calculated



### Flammability Neat HFC

- 365mfc is flammable , but the addition of HFC

- 227 ea, which notably has been approved for use as a flame suppressant, renders the blend non

- flammable

. See generally Attachment A1

– Solkane ® 365 Foaming Agents ; Note that some jurisdictions, such as Japan, do not regulate HFC

- 365mfc as flammable

. So long as there is at least 5% by weight HFC

- 2 27ea , Solkane 365/227 will not be flammable. Thus , it is expected that in

- us e concentrations of the blend will contain at least 7% HF C

- 227ea to account for the non

- azeotropic characteristics of HFC

- 227ea. The flammability limits in air of Solkane 365/227 are nearly the same as for HFC

- 365mfc (3.6

– 13.3 % by volume ), but have been demonstrated not to present an issue during spray foam application. See Attachment A 2

– Blowing Agent Emissions During Spraying

Toxicity As a general matter, EPA has previously evaluated the toxicity of both HFC

- 365mfc and HFC

- 227ea under the SNAP prog ram. With regard to HFC

- 365mfc, EPA has determined that it has low toxicity with a recommendation th at long

- term exposures not exceed 1,000 ppm as an 8

- hour time weighted average. Consumer exposures to low levels of HFC

365mfc over time do not pose a sig nificant toxicity risk, as the exposures would be very small compared to AEL values developed for occupational exposures. In addition, c hronic exposures to the substitute are not expected for the general population. See EPA

- HQ

- OAR

- 2003

- 0118

- 0235 Risk Scre en for HFC

- 365mfc in Foam Blowing ; see also Protection of Stratospheric Ozone: Notice 14 for Significant New Alternatives Policy Program , 65 Fed. Reg. 78,977 (Dec. 18, 2000) With regards to HFC

- 227ea, Solvay provided toxicity and degradation information on this substance in its September 2, 2011 letter to Monica Shimamura, EPA Stratospheric Protection Branch. In addition, EPA has previously evaluated the toxicity of HFC

- 227a in prior SNAP submissions, albeit, not involving foam end uses. See EPA

- HQ

- OAR

- 20 03

- 0118

- 0004 , Risk Screen on The Use of Substitutes For Class I Ozone

- Depleting Substances:

2 The total global warming potential (GWP) of these mixture was calculated as a weighted average, derived from the sum of the weight fractions of the individual substances multiplied by their GWP. See e.g., Regulation (EC) No 842/2006 on certain fluorinate d greenhouse gases , Annex I, Pt.2.

### Solvay	Fluorides,	LLC

Solkane	365/227 Fire Suppression And Explosion Protection (Halon Substitutes) ; Protection of Stratospheric Ozone , 59 Fed. Reg. 13,044 (March 18, 19 94) ; and Protection of Stratosphe ric Ozone, 63 Fed. Reg. 28,251 (May 22, 1998). Solvay also provided degradation information on Solkane 365/227 blends in its January 30, 2012 letter addressed to Melissa Fiffer :

“ In both product blends it was shown, that there is no temperature influence up to 200 C. During production of Polyurethane Foams, in general, a process of carbonization starts at 170 o 

### C. So, temperatures higher than this will always be avoided. Due to this temperature limitation, So l kane® 365mfc and Solkane 227ea will not decompos e. Solkane® 365/227 has been used in the industry (outside the U.S.) for approximately seven (7) years and there have been no reports of any decomposition. Our experience with cell gas analysis shows no byproducts inside the foam with a detection limit of 200 ppm. ” See Letter from Dr. Marc A. Feldman to Melis sa Fiffer, EPA (Jan. 30, 2012) ; Letter from Dr. Marc A. Feldman to Margaret Sheppard, EPA (Sept. 19, 2011)

Cost, Use and Performance Information on the cost, ease of use and performance of Solkane 365/ 227 was provided in Solvay’s initial TSCA/SNAP addendum and in response to various Agency inquiries :

“ Solkane 365mfc will be sold for approximately $5/lb at the time it is first introduced commercially into the U.S. for the f oam blowing applications identi fied herein. This is in range of the current global world price for Solkane 365mfc currently being used in these applications. ” With the exception of new hoses and fittings, “ i t is not anticipated that the use of Solkane 365/227 will require new equipment, retrofitting of existing equipment, or changes in current foam blowing technologies. ” See EPA

- HQ

- OAR

- 2003

- 0118

- 0278 , TSCA/SNAP Addendum for Solkane® 365/227 ; Letter from Dr. Marc A. Feldman to Melissa Fiffer, EPA (Jan. 30, 2012); Letter from Dr. Marc A. Feldman to Margaret Sheppard, EPA (Sept. 19, 2011)

. The spray foam industry is very familiar with transitions to alternative fluorocarbons especially with products that are currently used in other global markets. Solkane 365/227 has been used in Europe si nce January 2004, and has provided Solvay with extensive, successful in situ experience in spray foam applications. The blend also has been used in Canad a for the past year and a half and total user experience has been extremely positive from a handling a nd energy performance standpoint. It is Solvay’s experience in these global markets that less of the Solkane 365/227 blend will be needed than HCFC

- 141b as spray foam formulations have evolved to use less blowing agents

. In addition, Solkane 365/227 provi des other advantage when compared to other blowing agents :

• Storage and Handling : Solkane 365/227 can be used in spray foam equipment currently in use for other HFC blowing agents without major modifications. No additional training should be needed , but as with other blowing agents, users should follow all requirements and recommendations specified in the MSDS and other

### Solvay	Fluorides,	LLC

Solkane	365/227 safety precautions and requirements generally applicable to foam blowing operations , such as the Spray Polyurethane Foam Equipment Guidelin es

. See http://www.sprayfoam.org/downloads/pdf/AY%20137.pdf

.

• Energy Performance : HFC

- 365mfc has the best insulation performance (lowe st specific gas thermal conductivity “ λ or k value”) of all commercially available OD S alternatives (HFC and hydrocarbons). Foams blown with Solkane 365/227 also obtain this energy performance benefit as the following applications indicate:

o Insulation of Liquefied Natural Gas (“LNG”) Tankers

– Solkane 365/2 27 is the preferred blowing agent in this insulating application critical to maintaining LNG at approximately

- 260 °F

. See Attachment B 1

– Solkane® 365: LNG Storage Tank Insulation

o Insulation of Solar Water Heate r s

– Solar water heaters are widely used in Asia as an efficient means of heating water. Once heate d, it is critical to provide appropriate insulation to limit heat loss. Solkane 365 /227 is the preferred blowing agent for solar water heater applications because of its efficient insulation to dens ity ratio. See Attachment B 2

– Solkane® 365: Solar Water Heater Production

. o Insulation of Reefer

- Containers

– Because its “heat loss factor” is the lowest of any third generation blowing agent, Solkane 365/227 is the preferred system in Europe for insula ting foams that are needed to keep perishable food at

- 4 °F. See Attachment B 3

– Solkane® 365: Reefer Container Production

.

• Physical Performance and Other Characteristics : Foams blown with Solkane 365/227 also can benefit from improved physical characte ristics, including:

o Low weight and a high

- grade surface finish that provided automotive parts with an unblemished appearance, without streaks or air bubbles “ virtually impossible to obtain with other blowing agents.” See Attachment B4

– Bayer Polymers, Bay flex® 20/30 Foamed With Solkane® 365/227

. o These foams also were found to o ffer much better abrasion resistance , v ery high tear strength , and energy absorbing capacity

. Id.

• Compatibility : Solkane 365/227 is chemically stable allowing for long storage tim es of fully formulated systems

. See generally Attachment A1 :

o Its relatively high boiling point (real liquid up to ~70 °F) provides advantages during handling and transportation of fully formulated systems, including lower drum pressure

. o Solkane 365/227 is fully compatible with all raw materials commonly in use today , providing for energy and other performance improvements without market upheavals

.

# ATTACHMENT A 1

Solkane 365 Foaming Agents

# Solvay Special Chemicals SOLKANE ® 

# 365 Foaming Agents 

# Insulation2 Solvay Special Chemicals 

## SOLKANE ® 

## 365 – A Multi-Facted Blowing Agent for Plastic Foams Product description and handling
SOLKANE ® 365mfc is a hydrofluorocarbon of the latest generation. It has no ozone depleting potential and with its boiling point of 40 °C it can be handeled as a true liquid at room temperature. It is a colourless, compound with a faintly ethereal odour, used for a wide range of applications within PU foams, solvents or heat transfer fluids. The chemical stability of SOLKANE ® 365mfc is even better when com

pared to HFC 141b. Therefor no stabilizer is needed if SOLKANE ® 365mfc is stored under appropriate conditions (for details please refer to our SDS).
Top team SOLKANE ® 365mfc is a perfect team player. It is miscible with a wide range of other organic foam blowing agents like other HFCs or even hydrocarbons. The choices are up to you and almost unlimited. Blending of i.e. cyclopentane with SOLKANE ® 365mfc strongly improves the lambda value while reducing the density of the resulting PU foam. That means, running SOLKANE ® 365mfc in your system minimizes raw material costs while improving insulation performance. That is what we call a win win situation!Solvay Special Chemicals 3 Strong protection
SOLKANE ® 365mfc is your first choice when fire safety is demanded. Fire classifiactions and fire performance tests are of increased importance for modern PU products especially in the building industry. Combined with the Solvay's IXOL ® range of reactive flame retardant polyols, SOLKANE ® 365mfc blown PU foams reach the highest possible classifica

tions for organic insulation materials. Pole position For high performance PUR at competitive prices its tough to beat SOLKANE ® 365mfc. SOLKANE ® 365mfc gives you the best lambda values of any ODP zero foaming agent. Ask for our latest eco-efficiency studies which impressively demonstrate how SOLKANE ® 365mfc brings out the best in your PUR/PIR products – economically and ecologically!

Best choice Solvay's own range of SOLKANE ® 365/227 blends are approved solutions for a wide number of applications – utilising all of SOLKANE ® 365mfc ben

efits in a non-flammable blend. Ask for our expertise.4 Solvay Special Chemicals 

## Physical Data Stability and Storage Compared to HFC 141b the thermal and chemical stability of SOLKANE ® 365mfc is excellent. It should not be exposed to strong alka

line compounds or alkali metals. Under high temperatures or / and pres

sure hazardous reactions are possible with reactive metals e.g. Zinc, Aluminium and its alloys, Magnesium as well as with air. In pre-formulated PU-foam systems SOLKANE ® 365mfc has been observed to be stable, so no stabiliser is needed. SOLKANE ® 365mfc should be stored in a cool and well ventilated area. The contact to heat sources, open flames or sparks should be avoided. For additional information please refer to our SDS or ask our specialist.


## Quality

Packaging

The following table showes the physical properties of SOLKANE ® 365mfc based blowing agents provided by Solvay.

■ Purity of SOLKANE ® 365mfc 99.5 % min.
■ Water 100 ppm max. ■ Acid 1 ppm max. ■ Non volatile residue 100 ppm max.

SOLKANE ® 365mfc is available in:

Non returnable drums (240 kg) ISO-tank container (20 mt) Roadtanker (20 mt) Other quantities on request

Chemical name Blend of 1,1,1,3,3-Pentafluorobutane 1,1,1,3,3-Pentafluorobutane and 1,1,1,2,3,3,3-Heptafluoropropane
Formula CF 3 -CH 2 -CF 2 -CH 3 CF 3 -CH 2 -CF 2 -CH 3 and CF 3 -CHF-CF 3 Ratio [mass-%] 100 93/7 87/13 Molecular weight average [g/mol] 148.09 149.6 150.9 Boiling point [°C at 1.013 bar] 40.2 30 24
Flammable yes no no Vapour pressure at 20 °C [kPa] 47 70 93 Density of liquid at 20 °C [kg/dm 3 ] 1.27 1.28 1.29 Density of vapour at 20 °C (Air = 1) 5.7 6.4 6.5 Thermal conductivity of vapour at 25 °C [mW/m.K] 10.6 10.7 10.9 Viscosity of liquid at 20 °C [μPa.s] 452 447 432 Log P o/w (pure SOLKANE ® 365mfc) 1.6 Solubility in water at 23 °C [g/kg] 0.84 0.84Solvay Special Chemicals 5 SOLKANE ® 365 / 227 versus Temperature

SOLKANE ® 365 / 227 versus Temperature 

## Liquid Density

SOLKANE ® 365 / 227 versus Temperature 

## Viscosity Vapour Pressure6 Solvay Special Chemicals The polyol solubility* is lower than known from SOLKANE ® 141b and is higher than hydrocarbons in most cases.

* Solubility in g per 100 g Polyol

** no changes expected for SOLKANE ® 365/227 blends solubility behavior. SOLKANE ® 365/227 blends are practically identical to pure SOLKANE ® 365. SOLKANE ® 365mfc is a material friendly compound. It is compatible with a wide range of sealing materials as shown in table below.

Thermoplastics Percent change of weight

PVC -0.02

PE-HD 0.4

PMMA 57 Polycarbonate 0.3

PP 0.2 Nylon 66 - 0.3
PS 0.2
Elastomers Neoprene 1.0
Viton A 90.5

EPDM 1.6
Natural rubber 7.2
Nitril rubber 2.5
Silicone 16.1
Change in % by weight after 7 days immersion.

Polyol SOLKANE ® SOLKANE ® n-pentane c-pentane 141b 365mfc **
Caradol ® 585 100 32 5 11
Castor Oil 100 18 47 100 Ethyleneglycol 4 3 1 1
IXOL ® M125 37 5 2 5 Stepanpol ® 3152 33 30 6 7
TCPP 100 100 10 100
Tercarol ® A 350 100 100 36 100
Tercarol ® RF 55 100 100 4 18
Voranol ® RA 640 100 100 20 100 

## Materials Compatibility for SOLKANE ® 

## 365

Solubility in PolyolsSolvay Special Chemicals 7 

## Miscibility As mentioned before SOLKANE ® 365mfc is miscible with a wide range of organic compounds. It forms azeotropes even with some popular co-blowing agents.



## Toxicity Long term evaluation of SOLKANE ® 365mfc has been finished and showed no toxicity concern, even less effect than HCFC 141b. Based on these good results, the registration of the product has been done in Europe. SOLKANE ® 365mfc is registered in ELINCS under the number 430-250-1. The average exposure limit will probably be set to 500 or 1000ppm which is comparable to HCFC 141b (500 ppm). All results available up to date indicate the product to be safe for a broad range of industrial applications when the recommended standard hygiene practices and safety rules are observed. SOLKANE ® 365mfc / 227ea blends offered by Solvay have no flash point (ISO 1516 / 1523) and are not subject to flammable liquid regulation. Being non azeotropic blends, the composition can change during han

dling. Below a concentration of 5 mass % of SOLKANE ® 227ea the liquid becomes flammable. Straight SOLKANE ® 365mfc has a flash point below –27 °C (DIN 51755, Teil 2) but is difficult to ignite. The minimum ignition energy is around 50 times higher than of n-pentane and is 10.4 mJ (25 °C, 8 Vol % in air at 1 bar). The explosion limits at standard conditions in dry air are:
■ Lower explosion limit (LEL) 3.6 % by volume in air
■ Upper explosion limit (UEL) 13.3 % by volume in air For more information please read our brochure about flammability charac

teristics and handling.

Compound Composition Boiling Point [pbw SOLKANE ® 365mfc] [°C]
Methanol 94 37.5
Ethanol 97.5 39.5
n-Pentane 58 27
Iso-Pentane 46 22.5 Cyclo-Pentane 72 32 1,2-trans-Dichloroethylene 70 36
Galden HT 55 65 36
Galden HT 70 66 37 

## Flammability35/232/05.11/007/250

Disclaimer: The use of SOLKANE ® 36 5 mfc and of blends containing SOLKANE ® 36 5 mfc might fall within the scope of U.S. patent no. 5,496,866. The following must be noted regarding the USA (until March 5, 2013): (1) SOLKANE ® 36 5 mfc cannot be used in the USA, by itself or in a blend, as a blowing agent to foam a plastic based on an isocyanate to form plastic foam compositions; (2) SOLKANE ® 36 5 mfc and blends containing SOLKANE ® 36 5 mfc must not be made, used, offered for sale, or sold in the USA, or imported into the USA, for such blowing uses; and (3) closed cell plastic foam compositions prepared by foaming a plastic material based on isocyanate in the presence of a propellant comprising SOLKANE ® 36 5 mfc and/or a blend contain

- ing SOLKANE ® 36 5 mfc, cannot be made, used, offered for sale, or sold, within the USA, or imported into the USA. To do so can result in a claim of patent infringement under U.S. patent no. 5,496,866. Solvay will not sell SOLKANE ® 36 5 mfc or blends containing SOLKANE ® 36 5 mfc to any purchaser intending to use the product accordingly. For technical or sales information please refer to Solvay Fluor GmbH Postfach 220 30002 Hannover Germany Phone +49 511 857-2444 Fax +49 511 817338 foaming.agents@solvay.com www.solvay-fluor.com Solvay (Shanghai) Co. Ltd. Zhang Jiang Hi-Tech Park Building 7, No.899, Zu Chong Zhi Rd Shanghai 201203, P.R. China Phone +86 21 50805080 Fax +86 21 50807501 Solvay Fluorides LLC 3333 Richmond Avenue Houston, Texas 77098 USA Phone +1 713 525-6000 Fax +1 713 525-7805

# ATTACHMENT A 2

Blowing Agent Emissions During Spraying

# ATTACHMENT B 1

Solkane® 365: LNG Storage Tank InsulationLNG, a liquefied natural gas, is becoming more and more important as a fossil fuel to compete with crude oil all over the world. Gathered in warmer regions like Qatar it has to be transported over greater distances by sea. The natural gas (cooled for transport to –162°C) is shipped in so called LNG tankers, which are specifically equipped for this kind of overseas transport. The standards for insulation at cryogenic temperatures are demanding. The highest priority is given to keeping low storage temperatures and to minimizing expensive losses during transport. LNG storage tanks are insulated with polyurethane foam (PUF) and cargo containments are often insulated with glass fiber reinforced polyurethane foams (R-PUF). In the beginning CFC 11 was used as a blowing agent, followed by HCFC-141 b, which in turn has been substituted by Solkane ®

.

Blowing Gas CFC 11 HCFC 141b Solkane ® 365/227 93:7 Carbon Dioxide

Formula CCl 3 F CCl 2 FCH 3 CF 3 CH 2 CF 2 CH 3 CO 2 Mol. Wt. 128 117 148 44 Boiling Point [30°C] 23.8 32.1 40.2 subt. –78.5 Heat Conductivity of Vapor [mW/m.K, 25°C] 8.8 9.5 10.7 16.6

ODP 1 0.11 0 0
GWP 4750 725 964 [2] 1 [1] GWP (ITH 100 y), Source IPCC 4th Assessment Report issued in 2007 (International Panel on Climate Change) [2] Based on weighted average (1,1,1, 3,3-pentafluorobutane: 93 %, 1,1,1,2,3,3,3-heptafluoropropane 7 %) Table 1: Properties of various blowing agents Large temperature differences of up to 190°C (between –160°C and +30°C) cause high strain due to the LNG’s static pressure, sloshing etc. Different PU densities are required to fulfill the dimensional and compressive stability requirements; table 2 shows the very similar mechanical data when HCFC 141b is compared to 3 rd generation Solkane ® 365/227.

Unit [MPa] Solkane ® 365/227 HCFC 141b Water

A E I R-PUF A E I R-PUF Density (dev.) [kg/m 3 ] Mea 41.5 (0.16) 82.7 (0.15) 110.0 (0.31) 125.38 (0.77) 42.0 (0.50) 84.0 (0.72) 118.0 (2.32) 123.47 (0.58) Req ≤ 46.0 85.0 2 118.0 130.0 46.0 85.0 118.0 130.0 Comp. strength (dev.) z-dir. Amb. 0.34 (0.018) 0.84 (0.005) 1.33 (0.003) 1.26 (0.027) 0.27 (0.023) 0.77 (0.010) 1.28 (0.095) 1.31 (0.046) Req ≤ 0.17 0.53 0.87 1.2 0.17 0.53 0.87 1.2 Cryo. 0.84 1.13 1.95 1.43 0.53 1.69 2.52 1.45 Req ≥ 0.22 0.69 1.23 * 0.22 0.69 1.23 * 

### Mechanical Properties of PUFs and R-PUF

Table 2: Mechanical properties in comparison Notes: Mea. = measured value; Amb. = ambient temperature (23°C) Cryo. = cryogenic temperature; Req. = required value 

# Solvay Special Chemicals SOLKANE ® 365 LNG Storage Tank Insulation35/240/05.12/007/pdf

It is evident from table 2 that the compressive strength at both ambient and cryogenic tempera

tures shows no remarkable differences between Solkane ® 365/227 and HCFC 141b foam systems. This is also valid for the tensile and shear strengths, which can be reviewed in the proceedings [1]

. The initial thermal conductivity of PUFs did not show any significant differences between Solkane ® 365/227 and HCFC 141b systems. All results for PUFs and R-PUF discussed in this paper show good thermal stabilities at cryogenic temperatures. Based on these test results it is possible to substitute HCFC 141b with Solkane ® HFC 365/227 as a blowing agent in the LNG industry. Besides, R-PUF blown with Solkane ® HFC 365/227 seems to be a better selection as a new insulator for LNG cargo containment than R-PUF blown with water in the current situations. 

### Fresh/initial Thermal Conductivity of PUFs and R-PUF

Table 3: Thermal conductivities

Unit [MPa] Solkane ® 365/227 HCFC 141b Water

A E I R-PUF A E I R-PUF

Fresh/initial λ -value [W/m/K] Amb. (23°C) 0.021 0.0225 0.0244 0.0261 0.0208 0.0222 0.0238 0.0374

Req ≤ 0.0213 0.0229 0.0251

- 0.0213 0.0229 0.0251

-



### Conclusion Another main criterion to achieve the expected and required properties, besides mechanical strength, is high performance insulation. As shown in table 3, the λ -value of Solkane ® 365/227 is almost as good as that of HCFC 141b.

[1] Proceedings of 5 th (2005) International Offshore and Polar Engineering Conference, Seoul, Korea, June 19–24 (477– 481) Notes: Amb. = ambient temperature; Req. = required value

Disclaimer: The use of SOLKANE ® 36 5 mfc and of blends containing SOLKANE ® 36 5 mfc might fall within the scope of U.S. patent no. 5,496,866. The following must be noted regarding the USA (until March 5, 2013): (1) SOLKANE ® 36 5 mfc cannot be used in the USA, by itself or in a blend, as a blowing agent to foam a plastic based on an isocyanate to form plastic foam composi

tions; (2) SOLKANE ® 36 5 mfc and blends containing SOLKANE ® 36 5 mfc must not be made, used, offered for sale, or sold in the USA, or imported into the USA, for such blowing uses; and (3) closed cell plastic foam compositions prepared by foaming a plastic material based on isocyanate in the presence of a propellant comprising SOLKANE ® 36 5 mfc and/or a blend contain

ing SOLKANE ® 36 5 mfc, cannot be made, used, offered for sale, or sold, within the USA, or imported into the USA. To do so can result in a claim of patent infringement under U.S. patent no. 5,496,866. Solvay will not sell SOLKANE ® 36 5 mfc or blends containing SOLKANE ® 36 5 mfc to any purchaser intending to use the product accordingly. For technical or sales information please refer to Solvay Fluor GmbH Postfach 220 30002 Hannover Germany Phone +49 511 857-2444 Fax +49 511 817338 foaming.agents@solvay.com www.solvay-fluor.com Solvay (Shanghai) Co. Ltd. Zhang Jiang Hi-Tech Park Building 7, No.899, Zu Chong Zhi Rd Shanghai 201203, P.R. China Phone +86 21 50805080 Fax +86 21 50807501 Solvay Fluorides LLC 3333 Richmond Avenue Houston, Texas 77098 USA Phone +1 713 525-6000 Fax +1 713 525-7805

# ATTACHMENT B 2

Solkane® 365: Solar Water Heater ProductionSangle: Wang Bin, Ding Haicheng Dongda: Liu Jun, Wang Xinli, Wang Chao Solvay: Liu Hongci, Wang Luzhen 

## The Chinese solar water heater industry and HCFC 141b phase-out The Chinese solar water heater industry is currently using HCFC141b as a blowing agent to produce rigid foam for water tank insulation. According to the new schedule of the Montreal Protocol, the HCFCs phase-out in developing countries will hap

pen 10 years earlier. In view of its 30 % growth rate and its scale, which represents 80 % of the global output, the Chinese environmental protection department has included solar water heaters as one of the priorities for HCFC 141b phase-out within the PU foam industry. Therefore, solar water heater manufac

turers are trying different new blowing agents to develop their own technology to prepare for the conversion. 

## Sangle – its alternative selection Having compared different blowing agents, Sangle believes that SOLKANE ® 365/ 227 should be very suitable for solar water heater applications due to its advantages, such as 0 ODP, high boiling point for easy processing, low thermal conductiv

ity, outstanding compressive strength and no requirement for equipment modification. In the second half of 2009, Sangle together with Dongda and Solvay started trials for the use of SOLKANE ® 365/227 in solar water heater production to find an effective way for the replacement of HCFC 141b within the industry. 

## Dongda – 365/227 based PO development With respect to the technical requirements of Sangle, Dongda developed a SOLKANE ® 365/ 227 based Polyol system and tested it several times at Sangle’s production line for optimization. 1. Experiment conditions 2. Experimental formulation



## Results analysis 1. PO structure & bonding performance During the foaming process on water tanks, foam should have good adhesion to colored steel sheet. Separation of the two parts would be disastrous for the product quality. It was discov

ered in these trials that blending polyols of different structures cannot only reduce effectively the brittleness of the foam sur

face, but also improve both the bonding strength and the com

pressive strength of foam. Results are as follows:
Comment:

Polyether A, B (OH: 380 ± 10mg KOH / g) Polyether C (OH: 110 ± 10mg KOH / g) Polyether D (OH: 160 ± 10mg KOH / g)

Material pbw Polyether 100
Foam stabilizer 2.0 – 2.5 Catalyst 1.0 – 3.0

Water 1.8 – 2.2
HFC-365/227 15 – 20 Isocyanate Index 1.05– 1.10

Equipment Standard Parameter Blowing machine OMS high pressure flux: 600 g/s injection pressure: 120 – 130 MPa Mat. Temp. (P/I): 21±3°C/ 21 ±3°C Water tank 1800 mm x 20 tubes Filling pressure: 0.24 MPa

Cold storage –40°C Polyether Ratio Density kg/m 3 Compressive strength kPa Foam Perfor mance

A/D 80/ 20 34.1 140 debonding, seri

ous shrinkage

A/C 90/10 33.5 170 slight debonding, no shrinkage

B/C 90/10 33.1 175 slight debonding, no shrinkage

A/B/C 75/15/ 10 34.5 169 strong adhesion, no shrinkage 

# SOLKANE ® 365 Solar Water Heater Production



# Solvay Special Chemicals35/238/05.12/007/pdf 2. Additives selection In Polyol systems, foam stabilizers and catalysts are of criti

cal importance for the foam quality and foaming process. For SOLKANE ® 365/ 227 foaming, it was found during the experiments that the use of mixed catalysts DC13/DC12/DC17 and B8538 stabilizer can improve the product quality and foam

ing process. 3.Foam properties

The above figures show that with 14.5 % density reduction, SOLKANE ® 365/227 based foam can provide the same com

pressive strength as the HCFC 141b system and a lower thermal conductivity than the cyclo-pentane version. 4. Low temperature resistance performance The SOLKANE ® 365/ 227 based water tank was placed in a cold storage room to test breaking, shrinkage and debonding of the foam. It was proved that after 72 hours of storage at –5 °C – 25 °C, its dimensional stability was good at low tem

perature, and that the product meets the requirements for use in winter time. 

## Conclusion
SOLKANE ® 365/227 based foam can satisfy the requirements of the solar water heater industry in terms of its product quality and production process with the following benefits:

n Foam density 15 % reduction compared with HCFC 141b

10 % reduction compared with pentane
n Lambda 10 % lower than Cp Based on the above-mentioned results and rough estimates of replacement cost (replacing HCFC 141b with SOLKANE ® 365/227, the cost increase can be minimized to RMB 14 per unit), Sangle has considered using SOLKANE ® 365/227 for a batch of scale production for the purpose of process optimization. Three parties believe that HFC 365/227 as Blowing Agent used in solar WH has its unique advantages for the technolo

gy conversion within the solar water heater industry. For the HCFC 141b phase-out target, HFC 365/227 can ease the tran

sition with no safety concerns or investment burdens for manufac

turers, leaving room for their fur

ther development in future. Blowing Agent 141b 365/227 CP Overall density kg /m 3 55 47 52 Core density kg /m 3 42 38 37
λ at 23°C mw/m.k 19.1 20.5 22.8 Compressive strength KPa 168 171 161

Solar heater made by Sangle in China.

Disclaimer: The use of SOLKANE ® 36 5 mfc and of blends containing SOLKANE ® 36 5 mfc might fall within the scope of U.S. patent no. 5,496,866. The following must be noted regarding the USA (until March 5, 2013): (1) SOLKANE ® 36 5 mfc cannot be used in the USA, by itself or in a blend, as a blowing agent to foam a plastic based on an isocyanate to form plastic foam compositions; (2) SOLKANE ® 36 5 mfc and blends containing SOLKANE ® 36 5 mfc must not be made, used, offered for sale, or sold in the USA, or imported into the USA, for such blowing uses; and (3) closed cell plastic foam compositions prepared by foaming a plastic material based on isocyanate in the presence of a propellant comprising SOLKANE ® 36 5 mfc and/or a blend containing SOLKANE ® 36 5 mfc, cannot be made, used, offered for sale, or sold, within the USA, or imported into the USA. To do so can result in a claim of patent infringement under U.S. patent no. 5,496,866. Solvay will not sell SOLKANE ® 36 5 mfc or blends containing SOLKANE ® 36 5 mfc to any purchaser intending to use the product accordingly. For technical or sales information please refer to Solvay Fluor GmbH Postfach 220 30002 Hannover Germany Phone +49 511 857-2444 Fax +49 511 817338 foaming.agents@solvay.com www.solvay-fluor.com Solvay (Shanghai) Co. Ltd. Zhang Jiang Hi-Tech Park Building 7, No.899, Zu Chong Zhi Rd Shanghai 201203, P.R. China Phone +86 21 50805080 Fax +86 21 50807501 Solvay Fluorides LLC 3333 Richmond Avenue Houston, Texas 77098 USA Phone +1 713 525-6000 Fax +1 713 525-7805

# ATTACHMENT B 3

Solkane® 365: Reefer Cont ainer ProductionReefer containers – insulated with polyurethane foam – are considered first choice for oversea transports of temperature sensitive products. The preferred blowing agent for this application in recent years has been HCFC141b. When the European Parliament decided to ban the use of HCFC in the European countries, this regulation also has an impact on imports of finished products. In terms of reefer containers the requirement is HCFC-free PU insulation. The company Yangzhou Tonglee Reefer Equipment Co Ltd (Tonglee) has been a well-known producer of reefer containers in China since 1994. Prompted by the strong interest in the export business Tonglee started to look into ODP zero blowing agents in order to be prepared to meet the requirements of the Montreal Protocol. The following table compares alternatives to HCFC 141b:

A decision was taken in favour of Solkane ® 365/227 93:7 when comparing alternative blowing agent technologies. The fact that there is practically no need for equipment investment when switching from HCFC141b to Solkane ® 365/227 was one of the major eco

nomic arguments. Both products are non-flammable, and their physical prop

erties, such as the boiling points, are in the same range. From a technical point of view the change to the zero odp alternative could be arranged smoothly. The material costs of Solkane ® 365/227 93:7 and HCFC141b are different. In close cooperation with Huntsman Polyurethanes (China) Ltd. a new polyu

rethane system was developed. The consumption of HFC 365/227 has been reduced by > 20 % versus an equimolar replacement of the blowing agent, without a negative impact on the processing and foam properties. Although this means a higher MDI consumption when using less blowing agent, the increase in MDI consumption is still in an acceptable range. Molecular Weight [kg/kmol] Boiling Point [°C] Therm. Conductivity [mW/m.K; 25°C] HCFC 141b 116.95 32 9.5 HFC 245fa 134.05 15 12.2 HFC 365mfc 148.08 40 10.6 Solkane ® 365/227 93:7 149.43 30 10.7 cyclo-Pentane 70.15 49 12.0



# SOLKANE ® 365 Reefer Container Production



# Solvay Special Chemicals35/237/05.12/007/1.pdf 

## Cost Analysis for Blowing Agent Technologies Assuming an FEU – 40-ft Container – uses 550 kg of PU material

When changing production parameters to replace HCFC141b, close attention is paid to maintaining insulation efficiency and high mechanical strength, both properties being seen as key issues by the shipping lines and leasing companies, who are the final consumers of reefer containers. Meeting customer requirements while considering both economic terms and environmental regulations is the objective and requires the combined efforts of all parties, including blowing agent manufacturers, polyurethane material reefer containers and end users.

Blowing Agent (B.A.) Boiling Point [°C] Mixing ratio Polyol:B.A.:MDI Average Foam density [kg/m3] B.A. price* B.A. costs* per FEU MDI/ Polyol price* MDI/ Polyol Cost* per FEU Total cost per FEU (US $) HCFC 141b 32 100 : 25 : 130 42 1** 1** 1** 1** 1,167 HFC 365mfc/227ea 93:7 30 Reference system 100 : 24 : 130 42 5.5 5.3 1 1 1,496

HFC 365mfc/227ea 93:7 30 Huntsman system 100 : 19 : 132 42 5.5 4.2 1 1.03 1,450

* raw material prices are generalized and subject to market fluctuations

** price indications for HCFC141b, MDI and polyols are fixed as 1

Disclaimer: The use of SOLKANE ® 36 5 mfc and of blends containing SOLKANE ® 36 5 mfc might fall within the scope of U.S. patent no. 5,496,866. The following must be noted regarding the USA (until March 5, 2013): (1) SOLKANE ® 36 5 mfc cannot be used in the USA, by itself or in a blend, as a blowing agent to foam a plastic based on an isocyanate to form plastic foam compositions; (2) SOLKANE ® 36 5 mfc and blends containing SOLKANE ® 36 5 mfc must not be made, used, offered for sale, or sold in the USA, or imported into the USA, for such blowing uses; and (3) closed cell plastic foam compositions prepared by foaming a plastic material based on isocyanate in the presence of a propellant comprising SOLKANE ® 36 5 mfc and/or a blend containing SOLKANE ® 36 5 mfc, cannot be made, used, offered for sale, or sold, within the USA, or imported into the USA. To do so can result in a claim of patent infringement under U.S. patent no. 5,496,866. Solvay will not sell SOLKANE ® 36 5 mfc or blends containing SOLKANE ® 36 5 mfc to any purchaser intending to use the product accordingly. For technical or sales information please refer to Solvay Fluor GmbH Postfach 220 30002 Hannover Germany Phone +49 511 857-2444 Fax +49 511 817338 foaming.agents@solvay.com www.solvay-fluor.com Solvay (Shanghai) Co. Ltd. Zhang Jiang Hi-Tech Park Building 7, No.899, Zu Chong Zhi Rd Shanghai 201203, P.R. China Phone +86 21 50805080 Fax +86 21 50807501 Solvay Fluorides LLC 3333 Richmond Avenue Houston, Texas 77098 USA Phone +1 713 525-6000 Fax +1 713 525-7805

# ATTACHMENT B 4

Bayer Polymers, Bayflex® 20/30 Foamed With Solkane® 365/227

## T he effect of chlorofluorocarbons (CFCs) on the ozone layer in the stratosphere is a generally known fact. The position of the United Nations on substances that damage the ozone layer was defined in the Montreal Protocol of 1987 and subsequent amendments. The European Union and a few other countries will halt the production of CFCs even before the deadline set by the United Nations.

With arm rests and steering wheels it is difficultto achieve a balanced relationship between hardness, weight and surface finish, but this can be achieved with integral skin foam systems blown with Solkane ® 365/227. These systems also offer much better abrasion resistance than systems containing blowing agents such as water or Solkane ® 134a.
The transport segment also includes, of course, two-wheeled vehicles. Bicycles and motorcycles need a saddle that is not onlylight and comfortable, but also weatherproofed. Thanks to the specific properties described above, the Bayflex ® 20/30 integralfoam systems currently offer the only practicable solution for such applications.
In the furniture industry, properties similar to those specified by the automotive segmentare needed, although the mechanical stresses to which different products are subjected vary considerably.
Bayflex ® 20/30 with Solkane ® 365/227 hasa very high tear strength and energy absorbing capacity. Here are a few examples from the multitude of possible applications for this system: impact-absorbing shoulder andelbow protectors for motorcycle suits, hydrolOne use of CFCs is as a blowing agent in the production of rigid and flexible polyurethane integral skin foams. The integral skin foamsused in the furniture and automotive industries in particular have to meet particularly strict specifications and quality standards. The ban on the use of blowing agents with an Ozone Depletion Potential (ODP) presents producers of these foams with major problems.
In order to comply with the legal requirements, Bayer has introduced a Bayflex ® 20/30 integral skin foam system blown with Solkane ® 365/227, which offers users the full range of properties required for the production of vehicle and furniture parts.

Solkane ® 365/227 is a hydrofluorocarbon (HFC).

What applications are involved, and what advantages does Solkane ® 365/227 have over other approved blowing agents?
In the automotive segment, the Solkane ® 365/227-blown Bayflex ® 20/30integral skin foam system offers manufacturers of head restraints, for example, the advantage of low weight in combination with a high-grade surface finish. This permits the production of parts with an unblemished appearance, without streaks or air bubbles, which is virtually impossible to obtain with other blowing agents. ysis-resistant head and arm rests for bathtubs, weather-resistant equipment for children's playgrounds (e.g. seats for swings and impact-absorbing parts for kiddies' rides), and flexible seats, benches and wheels for gym equipment.
Bayflex ® 20/30 delivers all the specified physical and mechanical properties, such as hardness, density, abrasion resistance and weather resistance.
Our expert for Bayflex ® 20/30 is Dr. Hoffmann, who can be contacted at andreas.hoffmann@bayerpolymers.com. Cross section through Bayflex ® 20/30 

# Bayflex ® 

# 20/30 foamed with Solkane ® 

# 365/227 A flexible integral skin foam and its applications in the furniture and automotive industries P OLYURETHANE G LOSSARY

Bayer AG Bayer Polymers 51368 Leverkusen, Germany www.bayerpolymers.com
This information and our technical advice – whether verbal‚ in writing or by way of trials – are given in good faith but without warranty‚ and this also applies where proprietary rights of third parties are involved. Our advice does not release you from the obligation to verify the information currently provided – especially that contained in our safety data and technicalinformation sheets – and to test our products as to their suitability for the intended processes and uses. The application‚use and processing of our products and the products manufactured by you on the basis of our technical advice are beyond our control and‚ therefore‚ entirely your own responsibility. Our products are sold in accordance with the current version of our General Conditions of Sale and Delivery.

Printed in Germany For further information, comments and suggestions contact: Clive A. Jennings, Bayer plc Newbury Tel.: +44 1635 56 32 62; Fax: +44 1635 56 32 72 E-mail: clive.jennings.cj1@bayer.co.uk Bayer AG Bayer Polymers 51368 Leverkusen, Germany www.bayerpolymers.com
This information and our technical advice – whether verbal‚ in writing or by way of trials – are given in good faith but without warranty‚ and this also applies where proprietary rights of third parties are involved. Our advice does not release you from the obligation to verify the information currently provided – especially that contained in our safety data and technicalinformation sheets – and to test our products as to their suitability for the intended processes and uses. The application‚use and processing of our products and the products manufactured by you on the basis of our technical advice are beyond our control and‚ therefore‚ entirely your own responsibility. Our products are sold in accordance with the current version of our General Conditions of Sale and Delivery.

Printed in Germany For further information, comments and suggestions contact: Monika Brandt Tel.: +49 214 30 33013; Fax: +49 214 30 55352 E-mail: monika.brandt@bayerpolymers.com

Order no.: PU 6446384 Order no.: PU 6446384 

# In

Baydur ® 

## /Bayflex ® 

## – Polyurethanes for Design and Functionality 

# Form Issue 2/2003