SOLVAY SOLVAYSOLEXIS 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 nameHGalden 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 thebifunctional 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.comtypical 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 KellyATTACHMENT 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 thebifunctional 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 MolecularWeight

118184234300

NormalBoilingPoint(°c)

356085

Rate Constant at 25°C for Reaction with Hydroxy Radical (cm3/molecule s) Photochemical Reactivity Index (relative to Methane).37.38.75.78

OzoneDepletion 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 320 570

184 Mn: number 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 NOAEL > 5% by volume

(pure CI-W•OCF2OCHF2

element) Cardiac sensitization

(dog)

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)