SOLVAY 

SOLVAY 

SOLEXIS 

February l0,2005 

CERTIFIED MAIL 

RETURN RECEIPTREQUESTED 

Mr. Steve Page 

Director, OAQPS 

USEPA (Mail Code 0404-04) 

Research Triangle Park, NC 27711 

RE: SOLVAY SOLEXIS, INC 

VOC DELISTING PETITION 

H-GALDEN 

Solvay Solexis, Inc hereby requests that the Office of Air Quality Planning and Standards of the 

United States Environmental Protection Agency add a novel family of hydrogen containing 

fluorinated polyethers ("Hydrofluoropolyethers, HFPEs"), also known by the trade name HGalden TM to the list of "Volatile Organic Compounds of Negligible Photochemical Reactivity that 

Should be Exempt from Regulation Under State Implementation Plans" see Fed. Reg. 35314 (July 8, 

1977). These compounds are very similar in structure to the delisted compounds noted in 40 CFR 

51.100(s)(1)ii "cyclic, branched, or linear, completely fluorinated ethers with no unsaturations. 

The compounds for which the exemption is requested will play a role in the substitution of high 

GWP compounds such as PFC's in a number of applications, particularly in the areas of heat 

transfer and fire suppression. SNAP application A9142 VID 253 was submitted to USEPA in July 

1999. The EPA approved the use of H-Galden in streaming agent applications in 68 Fed. Reg. 4004 

dated January 27, 2003. 

H-Galden vM products are a family of products having the general formula: 

HCF20(CF20)n(CF2CF20)mCF2H (1) 

that consist of random combinations of-CF20- and -CF2CF20- moieties and are characterized by 

-OCF2H chain ends. 

HFPEs are produced in an industrial process, utilizing proprietary technology of Solvay Solexis, 

comprised of a photo-initiated tetrafluoroethylene-oxygen co-polymerization process, followed by 

chemical reduction of the peroxidic precursor with hydrogen over a suitable catalyst to yield a 

distribution of substantially hi-functional products. Hydrolysis and decarboxylation of the bifunctional intermediates in the presence of the proton donors result in the final product as a 

polydispersed mixture of the components of general formula (1) with boiling point ranging from 35 

to > 200 °C. Hydrofluoropolyethers are TSCA registered, and are SNAP listed as fire extinguishing 

fluids (see Federal Register Vol. 68, No. 17, Monday, January 27, 2003, page 4004) 

HFPE fluids have been found to maintain several of the remarkable properties of perfluorinated 

fluids such as low vapor pressure, wide liquid interval, viscostaticity. HFPEs furthermore show a 

lower environmental impact in terms of atmospheric lifetime and global warming potential. A 

Solvay Solexis, Inc. 

10 Leonard Lane, Thorofare, NJ 08086 

856.853.8119 Fax: 856.853.6405 

www.solvaysolexis.com 
typical set of set of commercial HFPE grades shows boiling points ranging from 60 to 180 °C 

(properties shown in Table 1). All these grades are mixtures ofhomologues, obtained from the 

fractional distillation of the crude product. Therefore the values reported in Table 1 must be 

considered as commercial specifications, which may vary within a reasonable range depending 

upon intrinsic variability of industrial processes on polydispersed products. 

Table 1 

H Galden Properties 

ZV60 ZV75 ZT85 ZT100 ZT130 ZT150 ZT180 

Normal Boiling Point (°C) 56 75 85 T0-O "f3U 3"5"6r 77"8 

Pour Point (°C) -120 -120 -120 -114 -115 -110 -110 

Kinematic Viscosity (cSt) @ -40°C 2.03 2.18 4.53 7.32 11.30 

Kinematic Viscosity (cSt) @ 25°C 0.37 0.56 0.59 0.62 0.89 1.20 1.50 

Density (g/cm3) @ -40°C 1.74 1.74 1.78 1.80 1.83 

Density (g/cm3) @ 25°C 1.56 1.61 1.62 1.63 1.68 1.69 1.72 

Surface Tension (mN/m) @25°C 13.7 14 14.6 14.6 14.6 

Vapor Pressure (torr) @ 25°C 276 112 62.4 60.0 7.92 5.50 1.80 

Molecular Weight (a.m.u.) 230 355 360 400 500 570 650 

HFPEs have zero ODP, and show negligible photochemical reactivity. The ODP, atmospheric 

reactivities and Photochemical Reactivity Index of some of the lower boiling HFPEs are reported in 

Attachment 1. The atmospheric lifetime and GWP values are also shown in Attachment 1. The 

studies performed on the atmospheric decomposition mechanism and on the decomposition 

products have shown the HFPEs to fully mineralize, without the formation of long lived organic 

intermediates. 

The toxicity of HFPEs have been characterized and determined to be of low acute toxicity. They 

have no irritation or skin sensitization and no detectable genotoxic activity in vitro or in vivo. Unlike 

certain halogenated hydrocarbon materials, they show no cardiac sensitization potential. The rat 

inhalation NOAEL for subchronic exposure was determined to be 10057 ppm and the NOEL was 

1014 ppm HFPE showed a similarly low potential for developmental toxicity: an NOAEL value of 

10006 ppm was concluded for maternal and embryonic/fetal toxicity in rats exposed to HFPE by 

inhalation. More details are included in Attachment 1 and the references cited therein. 

In the light of the foregoing, Solvay Solexis, Inc. respectfully requests that the Agency add the 

Hydrofluoropolyethers to its list of VOC compounds exempt from mandatory regulation under 

States Implementation Plans Respecting Ozone. 

If you need further information or have any question regarding these materials or this request, 

please do contact me at (856)251-3426. 

Virginia Hubert 

VP Health, Safety and Environment 

Attachments 

cc: Mario Visca, Srini Padmanabhan, Doug Kelly 
ATTACHMENT 1 

HFPE Physicochemical and Toxicological Properties 

HFPEs have been designed as low envirorunental impact substitutes of CFCs and of high GWP 

compounds like PFCs in a number of applications, particularly in the areas of heat transfer and fire 

suppression [1,2]. They consist of a random combination of-CF20- and -CF2CF20- moieties mad 

are characterized by -OCF2H chain ends, and have the general formula: 

HCF20(CF20)n(CF2CF20)mCF2H (1) 

ttFPEs are produced in an industrial process, utilizing proprietary technology of Solvay Solexis, 

comprised of a photo-initiated tetrafluoroethylene-ox3,gen co-polymerization process, followed by 

chemical reduction of the pemxidic precursor with hydrogen over a suitable catalyst to yield a 

distribution of substantially bi-functional products. Hydrolysis and decarboxylation of the bifunctional intermediates in the presence of the proton donors result in the final product as a 

polydispersed mixture of the components of general formula (i) with boiling point ranging from 35 

to > 200 °C. 

HFPE fluids have been found to maintain several of the remarkable properties of perfluorinated 

fluids such as low vapor pressure, wide liquid interval, viscostaticity. HFPEs furthermore show a 

lower environmental impact in terms of atmospheric lifetime and global warming potential. A 

typical set of set of cormnercial HFPE grades shows boiling points ranging from 60 to 180 °C 

(properties shown in Table 1). All these grades are mixtures ofhomologues, obtained from the 

fractional distillation of the crude product. Therefore the values reported in Table 1 must be 

considered as corrunercial specifications, which may vary within a reasonable range depending 

upon intrinsic variability of industrial processes on polydispersed products. 

Table 1 

H Galden Properties 

•ROPERTY ZV60 ZV75 ZT85 ZT100 ZT130 ZT150 ZT180 

Normal Boiling Point (°C) 56 75 85 100 130 "F50 •78 

Pour Point (°C) -120 -120 -120 -114 -115 -110 -110 

Kinematic Viscosity (cSt) @ -40°C 2.03 2.18 4.53 7.32 11.30 

Kinematic Viscosity (cSt) @ 25°C 0.37 0.56 0.59 0.62 0.89 1.20 1.50 

Density (g/cm3) @ -40°C 1.74 1.74 1.78 1.80 1.83 

Density (g/cm3) @ 25°C 1.56 1.61 1.62 1.63 1.68 1.69 1.72 

Surface Tension (mN/m) @25°C 13.7 14 14.6 14.6 14.6 

Vapor Pressure (torr) @ 25°C 276 112 62.4 60.0 7.92 5.50 1.80 

Molecular Weight (a.m.u.) 230 355 360 400 500 570 650 

HFPEs have zero ODP, and show negligible photochemical reactivity. The ODP and reactivities of 

the lower boiling components of the H-Galden family are listed in Table 2, both as absolute Rate 

Constants with OH radicals and as Photochemical Reactivity Index (relative to methane) [3]. 

These elements have been selected as the ones having higher volatility. They are representative of 

the whole family, as it can be inferred from the values of the absolute rate constants being of the 

same order of magnitude independently of the molecular weight. 
Table 2 

H Galden Rate Constants and photochemical Reactivity Indexes 

Product 

HCF2OCF2H 

HCF2OCF2OCF2H 

HCF2OCF2CF2OCF2H 

HCF2OCF2OCF2CF2OCF2H 

Molecular 

Weight 

118 

184 

234 

300 

Normal 

Boiling 

Point 

(°c) 

35 

60 

85 

Rate Constant at 

25°C for Reaction 

with Hydroxy 

Radical 

(cm3/molecule s) 

Photochemical 

Reactivity 

Index (relative 

to Methane) 

.37 

.38 

.75 

.78 

Ozone 

Depletion 

Potential 

0 [4] 

0 [4] 

0 [4] 

o [4] 

The higher molecular weight fractions of the HFPEs will have higher boiling points and the 

measurement of the rate constants will become increasingly difficult due to low vapor pressure. 

Since the rate determining step for the degradation of these products is the abstraction of the 

terminal hydrogen atom, the chain length of the fluorinated backbone will have a negligible effect 

on the atmospheric lifetime. Hence it can be safely predicted that the rate constant for the reaction 

of these higher molecular weight fractions with OH is not higher than 4.9 !045 cm3/molecules. It 

follows that the Photochemical Reactivity Index for these fractions will be similar to that of the 

lower boiling fractions. 

The reaction rate constants herein reported were the basis for the calculation of the atmospheric 

lifetime and GWP values reported in Table 3 [5]. 

Table 3 

Atmospheric Lifetime and GWP values 

(from: "SCIENTIFIC ASSESSMENT OF OZONE DEPLETION: 2002") 

N3yfle 

H-Galden 1040x 

Chemical Formula 

CHF2OCF2OCF2CF2OCHF2 

Radiative 

Efficiency 

W m-2 ppb-•) 

1.37 

Atmospheric 

lifetime 

(y) 

6.3 

HFE-236cal 2 CI-W2OCF2OCI-IF2 0.66 12.1 

HFE-338pec 13 CHF2OCF2CF2OCHF2 0.87 6.2 

GWP vs. COz for given 

time horizon: 

20y 100y 500y 

5940 1840 572 

7560 2780 864 

4770 1480 459 

Studies have also been perfomaed on the atmospheric decomposition mechanism and on the 

decomposition products. The mechanisln has been evaluated (see figure 1) [6] by experimental 

determination of the decomposition products, which resulted to be only carbonyl fluoride (COF2). 

This is indicative of the complete mineralization of the product upon atmospheric degradation. 

Several HFPE fractions have been tested to evaluate their toxicity. The repeated dose toxicity and 

studies have been carried out on lower boiling rnaterial, in order to provide reproducibility in the 

high concentration range. The subacute (28 d repeated dose) and subchromc (90 d repeated dose) 

studies have been perfon-ned only by inhalation administration, due to the intrinsic volatility and to 

the projected uses and exposure routes of the material. Cardiac sensitization studies have been 

performed using both low boiling pure compotmd with boiling point of 35 °C (to guarantee the 

maximum concentration in the gas phase) and on the broad MWD product candidate for the 

application in fire suppression. 
Figure 1 [6] 

The characteristics of the low MW and of the broad MWD fractions used in the toxicological 

studies are shown in Table 4. [7] 

Table 4 

Property HFPE low HFPE broad CI-I•2OCF2OCI-IF2 

MW MWD 

Mn: number 320 570 184 average Molecular Weight (amu) 

MW Range (amu) 

Boiling point (°C) (range) 

184-336 

72.5 (35-110) 

350- 830 

154 (98-210) 35 

The results of the preliminary acute studies are reported in Table 5 [8]. The low-MW HYPE 

material has low acute toxicity, no potential for irritation or skin sensitization and no detectable 

genotoxic activity in vitro or in vivo. Unlike certain halogenated hydrocarbon materials, it has shown no 

cardiac sensitization potential. 
Table 5 

Test 

Acute oral toxicity 

4 h Acute inhalation toxicity 

LDs0 > 5000 mg/kg 

Acute eye irritation (rabbit) 

Results 

LCS0 > 26400 ppmv (maximum 

concentration) 

NOAEL for anesthetic-like effects 

13802 ppmv 

attainable vapor 

between 9500 and 

No deaths and no lung damage at aH concentrations 

Acute dermal toxicity LDso > 2000 mg/kg 

Skin sensitization (guinea pigs) Not a sensitizer 

Acute dermal irritation (rabbit) Non irritant 

Non irritant 

Cardiac sensitization (dog) NOAEL > 5% by volume (pure CI-W•OCF2OCHF2 element) 

Inhalation exposure to low-MW HFPE at high atmospheric concentrations (>18000 ppln) during 

the acute and 5- or 14-day inhalation tests, produced occasional sedative effects, comparable to the 

mild anaesthetic effects known to be caused by other volatile organic liquids (e.g.: HCFCs and 

HFCs (ECETOC, 1994)). These effects were not further observed in the subacute and subchronic 

inhalation studies, where less extreme maximum atmospheric concentrations of HFPE were 

employed. 

The rat inhalation NOAEL for subchronic low-MW HFPE exposure was determined to be 10057 

ppm and the NOEL was 1014 ppm. HFPE showed a similarly low potential for developmental 

toxicity: an NOAEL value of 10006 ppm is concluded for maternal and embryonic/foetal toxicity in 

rats exposed to low-MW HFPE by inhalation [7]. 

References 

M. Visca, G. Carignano, P. Maccone, G. Malinverno, S. Petricci, and G. Marchionni, 

Proceedings of the conference "The Earth Technology Forum", Washington, D.C. (2000) 

[2] M. Visca, P. Maccone, R. Romelaer, and G. Marchionni, Proceedings of the conference "The 

Earth Technology Forum", Washington, D.C. (2002); 

[3] Calculated as the ratio between the rate constant of each element and the rate constant for 

Methane 

[4] The product does not comain chlorine or bromine 
[5] World Meteorological Organization Global Ozone Research and Monitoring Project Report 

No. 47 "SCIENTIFIC ASSESSMENT OF OZONE DEPLETION: 2002" Chapter 1, pages 1.22 

1.33 

[6] E.C. Tuazon, Environ. Sci. Technol. 31, 1817 (1997) 

[7] G. Malinverno, I. Colombo, and M. Visca, Regulatory Toxicology and Pharmacology, Accepted 

for publication, dec. 2004 

[8] G. Marchionni, R. Silvani, G. Fontana, G. Malinvemo, and M. Visca, J. Fluorine Chem. 95, 41 

(1999)