POLYFLUOROALKYL ESTERS AND THEIR USE

ESTERS POLYFLUOROALCOYLES

English Abstract

ABSTRACT OF THE DISCLOSURE
Compounds, and process for preparing such compounds,
defined below are useful for treating textile materials
to impart dry soil resistance and oil and water re-
pellency properties to such materials and are useful
for treating paper to impart oil and water repellency
properties to such paper:
<IMG>
wherein
Rf is perfluoroalkyl containing 4 - 20 carbon
atoms;
R1 is optionally substituted alkyl, aryl,
aralkyl, cycloalkyl or cycloalkenyl, and
n is a number from 1 to 4.

Claims

The embodiments of the invention in which
an exclusive property or privilege is claimed are
defined as follows.
1. A compound having the formula:
<IMG>
wherein
Rf is a saturated, monovalent, non-aromatic,
fluorinated aliphatic which is straight or branched
chain or cyclic and contains at least 3 carbons;
R1 is alkyl, aryl, aralkyl or cycloalkyl;
and
n is a number from 1 to 4.
2. A compound of Claim 1 wherein Rf is a
perfluoroalkyl containing 3 to 20 carbons; and n is
2 to 4.
3. A compound of Claim 2 wherein R1 is
derived from citric, o-, m- or p-phthalic acid,
succinic, chlorendic or a benzene polycarboxylic
acid.
4. A compound having the formula:
<IMG>
wherein
Rf is a saturated, monovalent, non-aromatic,
fluorinated aliphatic which is straight or branched
chain or cyclic and contains at least 3 carbons;
- 31 -

R1 is derived from citric acid; and
n is a number from 1 to 4.
5. A compound of Claim 3 wherein R1 is
derived from o-phthalic acid.
6. A compound of Claim 3 wherein R1 is
derived from isophthalic acid.
7. A compound of Claim 3 wherein R1 is
derived from trimellitic acid.
8. A compound of Claim 3 wherein R1 is
derived from pyromellitic acid.
9. A compound according to Claim 1 wherein
Rf contains 4 to 16 carbons.
10. A compound according to Claim 2 wherein
Rf contains 4 to 16 carbons.
11. A compound according to Claim 3 wherein
Rf contains 4 to 16 carbons.
12. A compound according to Claim 4 wherein
Rf contains 4 to 16 carbons.
13. A compound according to Claim 5 wherein
Rf contains 4 to 16 carbons.
14. A compound according to Claim 6 wherein
Rf contains 4 to 16 carbons.
15. A compound according to Claim 7 wherein
Rf contains 4 to 16 carbons.
16. A compound according to Claim 8 wherein
Rf contains 4 to 16 carbons.
17. A compound according to any one of
Claims 9, 10 and 11 wherein Rf has an average value
of 6 to 8 carbons.
18. A compound according to any one of
Claims 12, 13 and 14 wherein Rf has an average value
of 6 to 8 carbons.
19. A compound according to Claim 15 or
Claim 16 wherein Rf has an average value of 6 to 8
carbons.
- 32 -

20. A process which comprises reacting
chlorine with a reactant compound having the formula:
<IMG>
so as to produce an end-product compound having the
formula:
<IMG>
wherein
Rf is a saturated, monovalent, non-aromatic
fluorinated aliphatic which is straight or branched
chain or cyclic and contains at least 3 carbons;
R1 is alkyl, aryl, alkenyl, aralkyl,
cycloalkyl, or cycloalkenyl; and
n is a number from 1 to 4;
during said reaction, said reactant compound being
in molten form or dissolved or suspended in a liquid
medium which is inert under the reaction conditions.
21. A process of Claim 20 wherein Rf is
a perfluoroalkyl containing 3 to 20 carbons; and n
is 2 to 4.
22. A process of Claim 21 wherein Rf is a
perfluoroalkyl containing 3 to 20 carbons; R1 is
derived from citric, o-, m- or p-phthalic acid,
succinic, chlorendic, or a benzene polycarboxylic
acid and n is 2 to 4.
23. A process which comprises reacting
- 33 -

chlorine with a reactant compound having the formula:
<IMG>
so as to produce an end-product compound having the
formula:
<IMG>
wherein
Rf is a saturated, monovalent, non-aromatic
fluorinated aliphatic which is straight or branched
chain or cyclic and contains at least 3 carbons;
R1 is derived from citric acid; and
n is a number from 1 to 4;
during said reaction, said reactant compound being
in molten form or dissolved or suspended in a liquid
medium which is inert under the reaction conditions.
24. A process of Claim 22 wherein R1 is
derived from o-phthalic acid.
25. A process of Claim 22 wherein R1 is
derived from isophthalic acid.
26. A process of Claim 22 wherein R1 is
derived from trimellitic acid.
27. A process of Claim 22 wherein R1 is
derived from pyromellitic acid.
28. A process of Claim 20 wherein Rf
contains 4 to 16 carbons.
29. A process of Claim 21 wherein Rf
contains 4 to 16 carbons.
- 34 -

30. A process of Claim 22 wherein Rf
contains 4 to 16 carbons.
31. A process of Claim 23 wherein Rf
contains 4 to 16 carbons.
32. A process of Claim 24 wherein Rf
contains 4 to 16 carbons.
33. A process of Claim 25 wherein Rf
contains 4 to 16 carbons.
34. A process of any one of Claims 28, 29
and 30 wherein Rf has an average value of 6 to 8
carbons.
35. A process of any one of Claims 31, 32
and 33 wherein Rf has an average value of 6 to 8
carbons.
36. A process for imparting oil- or water-
repellency, or dry soil resistance to a substrate
which comprises applying to the substrate at least
one compound of Claim l.
37. A process of Claim 36 wherein Rf is a
perfluoroalkyl containing 3 to 20 carbons; and n is
2 to 4.
38. A process of Claim 37 wherein R1 is
derived from citric, o-, m- or p-phthalic acid.
succinic, chlorendic, or a benzene polycarboxylic
acid.
39. A process for imparting oil- or water-
repellency, or dry soil resistance to a substrate
which comprises applying to the substrate at least
one compound of Claim 4.
40. A process of Claim 38 wherein R1 is
derived from o-phthalic acid.
41. A process of Claim 38 wherein R1 is
derived from isophthalic acid.
42. A process of Claim 38 wherein R1 is
derived from trimellitic acid.
- 35 -

43. A process of Claim 38 wherein R1 is
derived from pyromellitic acid.
44. A process of any of Claims 36, 37
and 38 wherein Rf contains 4 to 16 carbons.
45. A process of any of Claims 39, 40
and 41 wherein Rf contains 4 to 16 carbons.
46. A process according to Claim 42, or
Claim 43 wherein Rf contains 4 to 16 carbons.
47. A process of Claim 36 wherein Rf has
an average value of 6 to 8 carbons.
48. A substrate having at least one
compound of Claim 1 deposited thereon and exhibiting
oil- or water- repellency or dry soil resistance.
49. A substrate of Claim 48 wherein Rf is
a perfluoroalkyl containing 3 to 20 carbons; and n
is 2 to 4.
50. A substrate of Claim 49 wherein R1 is
derived from citric, o-, m- or p-phthalic acid,
succinic, chlorendic, or a benzene polycarboxylic
acid.
51. A substrate having at least one
compound of Claim 4 deposited thereon and exhibiting
oil- or water- repellency or dry soil resistance.
52. A substrate of Claim 50 wherein R1 is
derived from o-phthalic acid.
53. A substrate of Claim 50 wherein R1 is
derived from isophthalic acid.
54. A substrate of Claim 50 wherein R1 is
derived from trimellitic acid.
55. A substrate of Claim 50 wherein R1 is
derived from pyromellitic acid.
56. A substrate of any of Claims 48, 49
and 50 wherein Rf contains 4 to 16 carbons.
57. A substrate of any of Claims 51, 52
and 53 wherein Rf contains 4 to 16 carbons.
- 36 -

58. A substrate according to Claim 54 or
Claim 55 wherein Rf contains 4 to 16 carbons.
59. A substrate of Claim 55 wherein Rf has
an average value of 6 to 8 carbons.
- 37 -

Description

1 233 1 8~
TITLE
POLYFLUOROALKYL ESTERS AND THEIR USE
BA;CKGROUND OF TXE INVENTION
Field of the Invention
_ _ _
This invention r~lates to chloromethyl-substituted
polyfluoroalkyl esters of polybasic acids and their
use in treating a variety of substrates, such as tex-
tile fabrics and paper, so as to provide the sub-
strate with soil resistance as well as water and oil
repellency. It relates further to a process for pre~
paring the compounds of this invention wherein iodine-
substituted polyfluoroalkyl esters are reacted with
elemental chloxine in which the iodine-substituted
esters are in the molten state or dissolved or suspended
in an inert liquid.
Description of the Prior Art
_
In recent years, polymers and other compounds con-
taining highly_fluorinated segments have been used
widely for imparting dry soil resistance as well as oil
and water repellency to textile substrates. A degree
of resistance to dry, traffic-caused soiling in carpets
prepared from synthetic fibers (such as polyesters, poly-
amides, polyacrylics) i5 said to be provided by fluoro-
polymeric coatings, e.g. polymers of perfluoroalkyl
25 acrylates and methacrylates. Because ~uch coated
fibers may support the advance of a flame~more readily
than an uncoated fiber, highly fluorinated mono- and
polycarboxylic acid esters have been used to provide dry
soil resistance and resistance to ~urning; U.S. Patents
30 3,923,715 and 4,029,585.
U.S. Patent 3,716,401 discloses and claims a
process for rendering a vinyl surface oil resistant by
applying thereto a polymeric composition containing a
vinyl polymer dissolved in a volatile solvent and an
35 ester derived from perfluoroethanol and a mono- or poly-
carboxylic acid.
CH-1074

~ 2~3 ~ ~
U.S. Patent 3,145,222 discloses and claims com-
pounds having the formula Y(C~F2n)O wherein Y is
hydrogen, fluorine, chlorine or bromine; n is 1-20,
q is -CH2CHIO2CR; -CH2CHI(CH2)m(CH2)2CO2H;
-CH=CH(CH2)m(CH2)2cO2H; ~CM2c~2(c~2)mo( 2 2
or -CH=CI(CH2)mCO2H; R is lower alkyl; and m is 0-14.
Although the disclosure and claims do not otherwise
contemplate such a compound, that pa~ent also discloses
the compound, C3F7CH2CHICH2O2CCH3, and indicates it
may be hydrolyzed and treated with alkali to give a
polyfluoroepoxy polymer intermediate.
U.S. Patent 4,034,022 discloses isomers having
the formula:
CnF2n+l-CHCl-CH2-O-~-X
~0
C F2 l-CH-O-P;;~
CH2C 1
wherein CnF2n+l is a perfluorinated aliphatic chain, n
is an integer from 2 to 18, X and Y are the same or
different and are each a halogen atom, a hydroxyl
radical, the group OM in which M is a metallic equivalent
or an alkoxy, chloroalkoxy, hydroxypolyalkyleneoxy,
aryloxy or -NZZ' group in which Z and Z' are the same or
different and are each a hydrogen atom or an alkyl,
cycloalXyl or aryl group. It is stated the compounds are
liable to find use as emulsifying or foaming agents,
particularly when a tensioactive agent resistant to acids
and oxidants is needed, as leveling or anti-stain agents
for polishes or emulsion paints, as corrosion inhibitors,
solvent evaporation retarders or as hydrophobic and
oleophobic agents.

:~3~1~5
SUMMARY OF THE INVENTION
This invention relates to compounds having the
formula:
O
5RfCH2CHC- R
CH2Cl n
wherein
R~ is a fluorinated aliphatic containing at
least 3 carbons;
Rl is optionally substituted alkyl, aryl, alkenyl,
aralkyl, cycloalkyl, or cycloalkenyl; and
n is a number from 1 to 4, preferably 2 to 4.
It relates also to a method for preparing the compounds
of this invention, and to a process of using compounds
of this invention to treat textile materials so as to
give them dry soil resistance and oil and water re-
pellency. This in~ention relates still further to a
process or the treatment of paper so as to make it
repel water and oil.
DE~AILED DESCRI~TION OF THE INVENTION
.
Rf is a saturated, monovalent, non-aromatic, ali-
phatic radical. The chain may be straight, branched
or cyclic, and may be in~errupted by divalent oxygen
atoms or trivalent nitrogen atoms bonded only to car-
bon atoms. A fully fluorinated group is preferred, but
hydrogen or chlorine atoms may be present as sub-
stitutents in the fluorinated aliphatic radical pro-
vided that not more than one atom of either is present
3~ in the radical for every two carbon atoms, and that the
radical must at leas-t contain a terminal perfluoromethyl
group. In a preferred embodiment, the fluorinated ali-
phatic radical contains not more than 20 carbon atoms
because such a large radical results in inefficient use
of the fluorine content. In a more preferred embodi-
ment, R~ is a perfluoroalkyl containing 3 to 20 carbons.

~ ~3~
The compounds of this invention can be prepared by
the reaction se~ forth in the following equation:
LRfCH2fHC~20C~ R ~- Cl2--~~fCH2C~OC ~Rl ~ ICl
I n C~2C n
While most of the iodine will be present in the ul-
timate reaction mixture as ICl,some elemental io~ine will
be pres~nt. Mbreover some IC~ may ~e present. The iodine ~ -
stitute polyfluoroalkyl ester starting materi~ for the pEePara-
tion of the compounds of this invention can be prepared
by the reaction set forth in the following equation:
RfI + j~N2=CHC~I20C--~ R ' ~fC~12CHCH20C--]R
n I n
A wide variety of allyl esters can be used accord-
ing to~this in~ention. In a prefexred embodiment, Rl
is alkyl, aryl, aralkyl or cycloalkyl. Thus, for ex-
ample, Rl can be the residue remaining after esterifica-
tion of citric, phthalic (o, m or p isomer), benzoic,
succinic, chlorendic, benzene polycarboxylic acids,
such as trimellitic, pyromellitic and the like.
The reaction of the iodine-substi~uted polyfluoro-
alkyl ester with chlorine can be carried out by melting
the iodine-substituted polyfluoroalkyl ester and con-
tacting the molten ester with chlorine, or the iodine-
substituted polyfluoroalkyl ester can be suspended or
dissolved in a suitable liquid and reacted with
chlorine. A suitable liquid is inert under the
reaction conditions; e.q. alcohols or water should be
avoided since they would be expected to react. Pre-
ferred liquids include 1,1,2-trichloro-1,2,2-trifluoro-
ethane, 1,1,1,2-tetrachloro-2,2-difluoroethane and
tetrachloromethane~ It is possible also to use chloro-
form. All such halocarbons unction as solvents for
the iodine substituted polyfluoroalkyl ester starting
material. Although it is nok necessary that the liquid
medium be a solvent for that ester, it is pre~erred

~;~33~L~S
that the ester be at least partially soluble in the
liquid medium.
The reaction of the iodine-substituted polyfluoro-
alkyl ester with chlorine is mildly exothermic, being
somewhat more exothermic at the start of the reaction
than at a point near its completion. When a solvent
is used for the ester starting material, reflux there-
of provides effective control of the exotherm. The
temperature of the reaction with chlorine is not
critical nor is pressure. One can run the reaction
at a temperature between 0C and the melting point of
the iodine-substituted polyfluoroalkyl ester. Usually,
the reaction is run at a temperature between about 40
and 55C when a solvent is used, and between about 85
and 90C when the ester starting material is molten
during the reaction with chlorine. Although the
reaction, whether in solution or in molten rorm, is
usually run at atmospheric pressurP, elevated pressures
can be used as well. Normally, the reaction is run until
essentially all of the covalently bound iodine is dis-
placed from the este~.
Noxmally, a slight excess of chlorine, over thatrequired to satisfy the reaction given above, is used.
Introducing chlorine in excess of the amount which is
required to displace all iodine in the ester starting
material will do no harm, but such an e~cess does
nothing in aid of the reaction either. However, if the
R moiety has some tendency to rea~t with chlorine,
it may be desirable to avoid a large excess of chlorine.
3a In that way, if the Rl moiety reacts relatively
slowly wi~h chlorine, it may be possible to carry the
desired displacement of iodine to completion before
a significant amount of chlorine reacts with the ~1
moiety.
After all of the iodine has been displaced
from the ester, it is best to convert the iodine

~33~8~
chloride~s) and iodine, if any, to iodide and chloride
ions. For example, one can add water and a soluble
salt such as sodlnm bisulfite for that purpose.
The preraration of the iodine-subst:ituted poly-
5 1uoroalkyl ester is carried out in the presence of afree radical initiator at temlperatures in the range
between about 50 and 140C and at pre~sures between
about 1 and 50 atmospheres. If the polyfluoroalkyl
iodide or the allyl ester used in the reaction has a
10 boiling point below the desired reaction temperature,
a pre~sure system would be used; otherwise, the
reaction may be carried out at atmospheric pressure.
The free radical initiator may be either an azo com-
pound or a pero~y compound, e.g. ~,a'-azobis-(isobutyro-
15 nitrile); 2,2'-azobis-(~,4-dimethyl~aleronitrile);
acetyl peroxide; benzoyl peroxide; di-t-butyl peroxide
and the like.
The polyfluoroalkyl iodides can be prepared by a
variety of reactions. See for example Brace et al.,
20 JACS, 73, 4016 (1951); Krespan, J. Org. Chem., 23,
2016 (1958); Haszeldine, J. Chem. Soc., 1949, 2856; 1952,
4259; 1953, 376; Hauptschein et al., JACS, 79, 254g
(1957).
The principal use of compounds of this invention
25 involves application of solutions or aqueous dispersions
of said compounds to carpets, other woven or non-woven
textiles, or paper. The desirable character-
istics imparted by the application of said compounds
include water repellency, oil repellency, and resistance
30 to soiling. The degree to which said desirable character-
istics are achieved i5 evaluated in different ways for
the different substrates.
Fur example, in the case of carpets, dry soil
resistance provides a measure of the ability of the
35 carpet to retain its new appearance under normal traffic

3 ~33 ~ 85
cond1tions~ In addition, oil and water repellency is
required in carpets to provide resistance to staining
by spilled liquids
In most o~ the other end uses, achievement of the
5 desired effects is assayed simply by measuring oil
and/or water repellency. ~hat may be done ~y drop
tests as reported in Tables 3, 4 and 6 k,y penetration
as reported in Table 5.
Application of the novel compounds of this in-
10 vention from solution or aqueous dispersion to any of
the foregoing substrates may be carried out in any
known manner so as to deposit on the substrate from
about 0.01% to 1.0% of the novel compound, based on the
dry weight of the substrate. Preferably, application
15 of the novel compounds of this invention is made from
an aqueous dispersion. Subject to the above-defined
range of quantities of the novel compounds being de-
posited on the substrate, the aqueous dispersions of
compounds of this invention can be blended with an
20 aqueous polymeric suspension. For example, addition of
an aqueous suspension of polymethyl methacrylate, makes
a composition which can be diluted with water for ap-
plication to the various substrates contemplated by this
invention. The presence of the polymeric suspension,
25 such as an aqueous polymethylmethacrylate, improves dry
soil resistance. Such a dispersion, before dilution
with water, will normally contain from about 2% ~o about
20% of fluorinated ester of this inven~ion and between
about 2% and about 40~ of the polymer, dry basis~ pro-
30 vided by the above-mentioned suspension. For application
to textile substrates, such as carpets, the above-
described dispersion is diluted still further with water.
Application can be made by any known technique, such as
padding, exhaust spraying, and the like.
After a compound ~or compounds) of this invention,
as a solution or dispersion and optionally containing
okher components such as, for example, poly~methylmeth-

acrylate), has been applied to~the desired substrate,
it will usually be dried to remove water and~or sol-
vent. Normally, drying is efected by heating to
about 120-170C, although higher or lower temperatures
S may be used. In particular, drying at ambient tempera-
ture is frequently sufficient, although heating is
usually preferred to hasten the drying. Furthermore,
repellency effects frequently are improved by heat
treatment beyond that required for drying. It appears
that such treatment at least partially melts the com-
position of this invention so that it spreads and more
effectively coats the substrate.
The oil repellency test used herein is an adapta-
tion of AATCC Test Me~hod 118-1978. Oil rep~llency is
defined as the ability o~ a substrate to resist wetting
by oily liquids. According to the test method, drops
of standard test liquids, consisting of a selected
series of hydrocarbons with varying surface tensions,
are placed on the substrate and observed f or wetting.
~o The oil repellency rating is the highest numbered test
liquid which will not wet the surface of the substrate
within a period of 30 seconds. Wetting of the surface
of the substrate is normally evident by a darkening
thereof at the interface. On black or dark surfaces,
wetting can be detected by a loss of "sparkle" within
the drop~ The standard test liquids are set forth in
Table 1.

Table 1
Standard Test Liquids
Oil Repellency
~ C~mposition _
1 "Nujol"
2 65/35 "Nujol"/n-hexa-
decane by volume at
70F (21C~
3 n-hexadecane
4 n-tetradecane
n-dodecane
6 n-decane
7 n-octane
8 n-heptane
"Nujol" is the trademark of Plough, Inc., for a mineral
oil having a Saybolt viscosity of 360/390 at 100DF
(38C) and a specific gravity of 0.880/0.900 at 60F
(15C).
The water repellency test provides an index of
aqueous stain resistance in that, generally, the higher
the water repellency rating, the better the resistance
to staining by water~based substances. Like the oil
repellency rating, the water repellency rating is the
highest numbered test liquid which will not wet the
surface of the substrate in a specified amount of time,
in this case 10 seconds. The standard test solutions
are those of Table 2.

1 2 ~
Table 2
Standard Test Sol_ ions Flash Point
Water RepellencyComposition (TCC)
Ratin~ Numher ~ Isopropa _1* %~2** C
5 1 2 98 - -
2 5 95 50 12
3 10 90 40 104
4 20 80 28 82
~0 19 ~6
* Reagent Grade, percentage by volume
** Distilled
In accordance with the test procedure, one begins with
the lowest numbered test liquid (Water Repellency Rating
No. 1), and carefully places one drop thereof at each of
three locations on the surface of the substrate. If
after 10 seconds two of the three drops are still
visible in spherical or hemi-spherical form, drops of
the next higher numbered test liquid are placed in an
adjacent site and obser~ed for 10 seconds. The above-
described procedure is continued until at least two or
the three drops of the test liquid fail to remain
spherical or hemi-spherical 10 seconds after applica-
tion.
The following examples are given by way of illus-
tration,not by way of limitation. Unless otherwise
indicated, all parts and percentages are by weight;
temperatures are expressed in degrees Centigrade and
pressur~s in mm of Hg.
In some of the examples that follow, the term MPI
has been used as an abbreviation for Mixed Perfluoro-
alkyl Iodides of the formula, CnF2n~lI, having the
following composi~ion (average n = 8):

1 2~3 1 8~
11
n W ~ )
4 1~2
6 27-28
8 32-34
20-22
12 8-11
14 4-5
16 1-2
>16 small amounts
It is not necessary that mixed perfluoroalkyl
iodides be used in making compounds of this invention.
In addition, mixed perfluoroalkyl iodides other than the
foregoing can be used, e.g. a mixture of the above for-
mula having the composition (avPrage n = 6):
nWeight % ~Approximate~
-
4 3
6 52
8 30
11
12 3
14
In ths examples that follow, the term ABI is an
abbreviation for 2,2'-azobis-~isobutyronitrile). More-
over, in those examples, ~he term "deoxygenated" means
~5 that the material so treated was stirred overnight at
ambient temparature under a current of nitrogen or
stirred for at least one hour at about 60C under a
current of nitrogen. In the examples, "nonianic surfact-
ant" means the product of the reaction o 15 moles of
ethylene oxide with 1 mole of a mixture of n-dodecanQl-
1, n-tetradecanol-l, and n-hexadecanol-l. "Arquad" lS-
50 means a 50% solution of octadecyl trimethyl ammonium
chloride in water.

1 2 ~ 1 85
12
Example 1
Preparation of Adduct
MPI 146 g
Triallyl trimellitate 26.4 g
5 ABI 1.65 g
The MPI and the triallyl trimellitate were mixed
and deoxygenated. Then, while maintain.ing a nitrogen
atmosphere, the ABI was added portionwi~e over a
period of about 24 hours on the following time
schedule
Elapsed Time Tempera~ ABI
(Hours)ture~ddition
0 65C 0.2 g
~-1/3 64C 0.2 g
3-1/12 67C 0.2 g
5-5/6* 64-72C 0.~ g
24 raised to 0~65 g
99C
Total 1.65 g
24-3/4 reaction terminated
* The reaction mass was heated so that the
temperature was raised to 72C.
Preparation of Dispersion and Testing on Nylon Carpet
. . _ . ~
Adduct 100 g
25 MetXylisobutyl ketone 50 g
"Ar~uad" 18-50 6 g
Nonionic surfactant 3 ` g
Water about 125 g
2-Methyl-2,4-pentanediol O.S g
All components were combined at 50-80C in a
blender, agitated therein for about 10 minutes,
and then passed twice through a Manton-Gaulin**
homogenizer (2 stages, S00 and 6000 p5i). The
methyl isobutyl ketone was then distilled out, along
with some water, using a partial vacuum and temperatures
up to about 55C.
** denoted Trade Mark
12

1:23~85
A portion of the finished dispersion was diluted
with water and mixed with acetic acid and an aqueous
dispPrsion of polymethylmethacrylate (PMMA). The P~MA
in the dispersion had an inherent viscosity of about
0.7 (0.5 g of PMMA in 100 ml of acetone at 30CJ, and
was made up of particles having an average size of
about 0.06 micron. The mixed dispersion comprising
the adduct, acetic acid, PMMA and water was then
sprayed onto the face of nylon carpet so that the face
fibers of the carpet received 0.055~ of fluorine (in
covalently bound form), 0.186% of polymethylmeth-
acrylate, 0.01~ of acetic acid, and about 25% of
H2O based on the weight of the fiber. The carpet
was dried for 30 minutes in a forced air oven at
270~F. Samples of the carpet were tested for oil and
water repellency. Samples thereof were also tested
for dry soil resistance by being placed in a heavily-
travelled hallway along with untreated samples of the
same carpet, being rated for soil-resistance in com-
parison with the untreated carpet. The results oftestiny of the carpet samples are set forth in Table
3.
Another portion of the finished dispersion was
diluted with water and mixed with acetic acid. It was
then sprayed onto the face of nylon carpet so that the
face fibers thereof received 0.055% of fluorine (in
covalently bound form~, 0.01% of acetic acid and
about 25% of water. The treated carpet was then dried
and tested as described abovel giving the data set
forth in Table 4.
Example 2
Preparation of Triallyl Citrate Adduct
MPI 820 g
Triallyl citrate 161 g
35 ABI 9.5 9
Tha MPI and 47 ml of the triallyl citrate were

14
mixed and deoxygenated overnight. The next day, the
following schedule was followed:
Elapsed Tempera- ABI Addi- Triallyl
Time ture tion Citrate Ad-
(min) (:C) (g) dition (ml)
_ _ ,
0 25 (heating) 0.5
64
62 5
88 6~ 10
96 64 10
125 66 15
146 71 1.0
158 72 remainder
158-270 72-91
330 81 2.0
375 81 2.0
414 81 4.0
441 81 Shut down overnigh~ (cold time not
441-486 88-100 counted)
486 95 Reaction terminated
Dispersions of the product of this example, with
and without polymethyl methacryla~e, were prepared by
the procedures described in Example 1. Separate
5 portions thereof were applied to carpet samples and
tested as in Example 1, the results thereof being
recited in Tables 3 and 4.
Example 3
In a round-bottom flask fitted with a reflux con-
den~er main~ained at 0C were placed 320 g of the
product of Example 1 and 120 ml of 1,1,2-trichloro-
1,2~2-trifluoroethane. The mixture was stirred at
48-52C and 36 g of chlorine gas were introduced below
the surface of the liquid over a period of 75 minutes~
3 This ~ixture was left at room temp~rature overnight.
The next morning, the temperature was held in the
14

~233~
range of 43-52 while 40 ml of water and then 140 ml
of a saturated aqueous solution of sodium bisulfite
were added. The temperature was raised to 80 to
distill out the 1,1,2-trichloro-1,2,2-trifluoro-
ethane. At ~he same temperature, 100 ml of methylisobutyl ketone were added, followed by about 147 ml
of 20% aqueous sodium hydroxide ~o bring the pH to
5.4. Then, 120 ml of methyl isobutyl ketone and 60
g of MgSO4-7H2O were added, and after the latter
lQ dissolved, the lower aqueous layer was removed in a
separatory funnel. To the organic layer was added
200 ml of a hot aqueous solution of MgSO4 7H2O (sat-
urated at about 60C). After mixing well at 80C, the
lower aqueous layer was discarded. The organic layer
was washed with 200 ml of water at 80C, and the
product in methyl isobutyl ketone formed the bottom
layer. The uppex layer was discarded, and after
e~aporation of part of the methyl isobutyl ketone in
the bottom layer, 339 g of residue were obtained. A
sample thereof was dried in a vacuum oven and found to
be 67.5% non-volatile. That corresponds to 229 g of
dry product which is 83% of the theoretical yield.
The structure of the product is as follows:
~ C~2Cl
C-O~C~CH2~cnF2n+1
C~O~C~CX2-CnF2n+
O CH~Cl
c-o - c-cH2 ~CnT~n+l
() CH2Cl
wherein n is the same as given in the definition of
MPI. The structure of the product was established by
NMR spectroscopy and is supported by elemental
analysis. The latter gives the following results for
n with an average value of 8:

~ ~3~
16
Element Calc. % Found
C 2g.7 31.0
H 1.2 1.4
F 57.1 55
Cl 6.3 6.1
I 0 0.4
Preparation of Dispersion and Testing OTl Carpet
A dispersio~ was prepared as described in Example
1, using 352 g of the 67.5% solids methyl isobutyl
ketone solution described above. The other ingredients
were:
Water 100 ml
"Arquad" 18-50 18 g
Nonionic Surfactant 73 g
2-Methyl-2,4-pentanediol 0.5 g
Homogenization, removal of methyl isobutyl ketone,
application to carpet ~with and without polymethyl
methacrylate) and testing were carried out as described
in Example 1. Test results are set forth in Tables 3
and 4.
Example 4
Chlorination of the Product of Example 2
In a 500 ml round-bottom flask fitted with a re-
flux condenser maintained at 0 were placed 160 g of
the product of Example 2 and 60 ml of 1,1,2-trichloro-
1,2,2-trifluoroethane. The mixture was stirred at 48-
51 and 24 g of chlorine gas were introduced below the
surface over a period of about 75 minutes. Then, 20 ml
of water was poured down the condenser, followed by
80 ml of a saturated aqueous solution of sodium bisul-
fite added 510wly. The reflux condenser was then re-
moved and the flask was heated to 84-85 and held at
that temperature for about 15 minutes to distill out
the chlorofluorocarbon. Next, was added 90 ml of methyl
isobutyl ketone. The aqueous lower layer was removed by
16

~2~31~
means of a separatory funnel. The organic layer was
washed with 100 ml of hot, concentrated magnesium
sulfate solution. Isopropanol (50 ml) was added to
facilitate the separation of the aqueous phase. The
final wash was 100 ml of water to which 20 ml of iso-
propanol was added. The resulting solution of the
product in methyl isobutyl ketone weighed 237 g and was
56.4~ non-volatile, corresponding to 134 g of dry
produc~, 97~ of the theoretical yield.
The structure of the product, established by NMR
spectroscopy and elemental analysis, is
o CH2Cl
c~l2-c-O-c-cH2 CnF2n+1
¦ O CH2C
HO-C-C-O-C-CH2-CnF2n+
I 2
CH2 C-O-C~CH2 CnF2n+1
The average value of n in the MPI used as starting
material is 8, and therefore the average empirical for-
~ _ _ _ _
nula is C39H17F51O7C13. The dried material was analyzed:
Eleme _ Calc. % Found %
~5 C 28.0 28.95
H 1.0 102
F 57.9 55.4
Cl 6.4 6.4
I 0 0.4
The foregoing elemental analysis gives sa~isfactory
agreement with ~he theoretical, and supports the
structure set forth above.
Preparation of the Dispersion and Tes~ing on Carpet
.
The dispersion was made as described in Example
1, using 179 g of the methyl isobutyl ketone solution

18produced as described above. The other ingredients
were as described in Example 1, except that no methyl
isobutyl ketone was added per se. The dispersion was
distilled under vacuum to remove the methyl isobutyl
ketone and applied to nylon carpet as hereinbefore
described. The results of testing of the treated
carpet are set forth in Tables 3 and 4.
Example 5
C6F13I 200.7 g
10 Triallyl citrate 31.2 g
Isooctane 31.2 g
2,2'-azobis-(isobutyronitrile) 3.3 g
All of the above ingredients were combined and
deoxygena~ed. Then the mixture was stirred at 67-74
for 70 minutes, followed by 150 minutes at 70-75 and
then for 80 minutes at 79-83. During the first
twenty minutes of the period, the reaction was exo-
thermic and required cooling ~after initial heating to
bring to reaction temperature). Later, heating was
again required.
Volatile materials (87 g) were then removed on
the steam bath with aspirator vacuum, using a rotary
evaporator. The volatile materials consistea of iso-
octane (25 g) and perfluorohexyl iodide (62 g). Thus,
three mole proportions of perfluoroalkyl iodide had
been consumed per mole of triallyl citrate, indicating
that the structure of the product is:
O
1~ ~
CH2-C--O--CH2-cH-c~2 CÇF13
¦ O
"
HO--C-C-O--CH2-CH-CH2-C6Hl3
¦ O
CH2-C-O-CH2-CH-CH2-C6H13
Examination of the product by nuclear magnetic
18

1 ~33 ~ 85
19
resonance indicated that 94~ of the allyl double
bonds had been convexted to the following structural
moiety: -CF2-CH2-C~I-CH2-.
The product was dispersed in water and tested on
carpet as described in Example 1. The results are
set forth in Tables 3 and 4.
Example 6
Preparation of Adduct
MPI 154 g
10 Diallylphthalate 34 g
ABI 1.7 g
The MPI and the diallylphthalate were mixed and
deoxygenated. Then, while maintaining a nitrogen
atmosphere, the ABI was added and temperature was
lS controlled according to the following schedule:
Elapsed Time (min) Temperature ~C) ABI Addition
0 heating from 25 0.1 g
15-43 6~-68
g3 6~0.1 g
59 69.50.2 g
59-85 69-76.5
71.50.3 g
103 710.5 g
25 103-148 69.5-84
148 79~ 0.5 g
212 74.5-100
212 91 reaction terminated
Preparation of Dispersion and Testin ~
This was carried out as described in Example 1
and the results are recorded in Table 3.
Examp e 7
Preparation of Adduct
MPI 110
35 Allyl benzoate 32 g
ABI 3,55 g
19

~2331~5
The procedure was as described in Example 6,
with the following schedule for temperature and ad-
dition of ABI.
Elapsed Time Temperature ABI Ad-
5~(min) (:C) dition
0 61 0.1
54 6~ Ool
122 60 0.1 ~
198 6Q 0.4 g
10303 61 0.4
720 61 cooled
O (after r~g) 56
12 59 0 . 4 g
130 60 t~rature control reset to 71
15~4 71 0 . 4 g
439 71 0 . 4 g
840 72 cooled
O (after r~warminq) 56
56-80
20 150 80 1.05 g
150-745 80-90 griefly cooled to 5~ at 258
745 90 reaction terminated
Preparation of emulsion and testing on carpet were
carried out as described in Example 1 and the results
are recorded in Table 3.
Preparation of the adduct was carried out
essentially as described in Example 7, with the follow-
ing exceptions:
MPI was replaced by C8F17I; and
the adduct was purified by re-
crystallization from isopropanol.
Chlorination of the ~dduct
The equipment was the same as used in Example 4.
The materia~ charged were:

~ 2~3 ~ ~
21
Adduct (purified) 125 g
1,1,2-Trichloro-1,2,2- 50 ml
trifluoroethane
Chlorine gas (15 g) was introduced during two hours,
while the flask contents were maintained between 39
and 55. Thereafter, 20 ml of water were added, fol-
lowed by 80 ml of a saturated aqueous solution of
sodium bisulfite. The mixture separated into 2 layers
and was let stand for 25 days.
The layers were separated, the the lower layer
was washed with three 200-ml portions of water, to t~e
last of which was added 10 ml of isopropanol. The
chlorofluorocarbon was then evaporated in a vacuum oven
at 90-100. The product was a clear, amber, viscous
15 li~uid and weighed 102 g, representing a 94% yield of:
C8F17-CH2-CH-CH2-C
O
O=C ~
The product crystallized wlthin a day. The structure
was established by elemental analysis and NMR
spectroscopy, both proton and Carbon-l~. The
elemental analysis gave the following results:
' Calc. % Found %
C 35.0 34.9
F 52.4 51.7
~ 1.6 1.~
30 Cl 5.8 6.4
I 0.0 0.3
To a 400-ml ~stello~ C-lined bomb was added
10 g of the foregoing product, 10 ml of pyridine and
50 ml of isopropanol. The bomb was chilled to about
(-)75C and evacuated to about 3 mm pressure. Then,
the bomb was closed and heated to 160C for 4 hours.
The bomb was then cooled. The contents were a
* denotes Trade Mark 21
,

1 ~3~
homogeneous dark amber liquid. Of this liquid, 0.4 g
was taken and mixed with 100 ml of water to give a
rather turbid solution or suspension. The foregoing
solution or suspension has a surface tension of 22.4
5 dynes/cm~, measured by the ring method using a Du Nouy
tensiometer.
Example 9
In a round-bottom flask equipped with an ice-
water-cooled reflux condenser were placed 74 g of the
10 product of Example 6 and 30 ml of 1,1,2-trichloro-
1,2,2-trifluoroethane. The mixture was maintained at
51~C while 15 g of chlorine was added below the sur-
face over a period of 53 minutes. ~he~, 40 ml of a
saturated aqueous solution of sodium bisulfite were
15 added, dropwise, followed by sufficient 30% aqueous
sodium hydroxide to bring the pH to about 6 (about 35
ml). The temperature was then raised to 85 to distill
out 1,1,2 trichloro-1,2,2-trifluoroethane. The result-
ing mixture was transferred to a separatory funnel and
20 50 ml of methyl isobutyl ketone were added~ After
shaking, the lower layer was discarded and 50 ml of a
saturated aqueous solution of magnesium sulfate and
20 ml of isopropanol were added and the mixture was
shaken again. The lower layer was again discarded and
25 50 mi of hot water were added. After shaking, the solu-
tion of the product (lower layer) was drawn off.
The product solution was evaporated in vacuum
(removing methyl isobutyl ketone) until it weighed 69
grams. Fifty-seven grams of the resulting product
30 were mixed with:
"Arquad" 18-50 3 g
Nonionic surfactant 1.5 g
2-Methyl~2,4-pentanediol 0.25 g
Water approx. 60 ml5 The resulting mixture was well agitated in a blender,

3 ~
23
th~n diluted with water and mixed with acetic acid.
That mixture was sprayed onto nylon carpet so that
the face fibers received 0.055~ of fluorine (in co-
valently bound form), 0.01~ of acetic acid, and 25%
of water based on the weight of the fiber. The carpe~
was dried and tested as described in Example 1. The
test data are set for~h in Table 4.
Table 3 (With PMMA)
Ex. Dry Soil Oil Water
10 No. Resistance* Repellency Repellency
1 N_C(a) 5 5
2 C-M(a) 5
3 N-C 5 6
4 M 5-6 5-6
15 5 N-C(a) S S
6 C 5 5
7 N 0 3
Untreated - o o
C~et
* Degree of superiority over untreated carpet
E = equal
N = noticeably better
C = considerably better
M = much better
(a~ = O.11% PMMA
Table 4 (Without PMMA)
__.
Ex. Dry Soil Oil Water
No. Resistance* Repellency Repellency
,
1 N-C 5 5
2 C 5 5
30 3 S* 5 S
~ ~ 5 5
MW** 4 5
9 M 3-4 S
* S = slightly better
** MW = much worse
.
23

~ 233 ~ 8~
24
Te~c~ ve~ F.brics
The diluted dispersions tested on non-woven fab-
ric wereo
A. The product of Example 3 t dispersed in water
as described in Example 3, methyl isobutyl ketone re-
moved as described in said Example. That product was
then diluted with water to con~ain 0.035~ of fluorine.
B. The product of Example 4, treated as described
in A to contain 0.035% fluorine.
10 C. The product of Example 9, in the form of a 50
solution in methyl isobutyl ketone, was dispersed in
water as described in Example 4O After distillation
of the m~thyl isobutyl ketone, the dispersion was
diluted to contain 0.035% fluorine.
15 The non-woven fabric was a 60% polyester/40% wood
pulp fabric intended for use in o~erating-room garments.
The diluted dispersions were padded onto the non-woven
fabric to obtain a wet pick-up of 193 + 5%. They were
then dried by passing twice through a mangle heated to
325F, the heat being applied once on each side of the
fabric, with a contact time in the mangle of 75 seconds.
The treated fabrics, as well as an untreated
sample, were ~ubjected to the DART* 80.9 test, in which
a sample of the fabric is cut to the size of the disc of
a s~andard two-piece mason jar lid. A one-quart mason
jar is charged with 600 ml of water containing 0.9%
NaCl; the disc is clamped to the top of the jar and
the jar is inverted. The time for water to penetrate
the disc is recorded as set forth in Table 5.
Table 5
~ilute Dispersion Used Time for Penetration
A >60 min.
B 31 min.
C 5 min.
None instantaneous
* DisposableS Association Recommended Test
24

123318~
Tests on Kraft Paper
The treating dispersions used were the same
type as described in "Tests on Non-woven," but of
different concentration. The paper, Claremont*un-
bleached Rraft weighing 20 lbs/100 sq ft, waspadded with the dispersions as listed to give 138 + 2
wet pick-upo The paper was then dried by two
passes through a 220F mangle, once with each side
up. Contact time was 75 seconds. The treated papers
and an untreated control were given the AATCC oil
repellency test, and the results are given in Table 6.
Table 6
~ ~ Treated Paper
Synthesized Fluorine Oil
Dispersion Active Ing.edient Content Repel1ency
D Ex. 3 0.08% 4-5
E 3 0.04~ 1-2
F 4 0.08~ 5
G 4 0.044 1-2
H 9 0.08~ 5
J g 0-04% 4
Untreated paper - ~
Example 10
Chlorination of Triallyl Trimellitate Adduct
Without Solver.t
Product of Example 1 984 g
Chlorine 117~g
Saturated aqueous soaium bisulfite 290 ml
30% Aqueous sodium hydroxide 455 ml
The product of Example 1 (984 g) was charged to
a 3-liter round-bottom flask with bottom outlet,
furnished with a heating mantle and a cold-finger for
tap-water cooling. Nitrogen was passed through the
flask while the contents were heated to 85C to melt.
The conter.ts of the flask were agitated while chlorine
gas was introduced below the surface of the liquid as
detailed below.
* denotes Trade Mark

1 2 33 ~ B5
26
Elapsed Time Tempexature Action and
(mi~) (C) Remarks
_
0 82 started C12
84 14 g C12 in
83 37 g C12 in
76 61 g C12 in
145 61 117 g C12 in- C12
stopped ~ N~ ~æ~p star~
160 60 added 250 ml water
162 52 started addition of
NaHSO3 solution
162~200 52-79
(fluctuated)
200 68 stopped addition of
NaHSO3 solution
201 57 started addition of NaOH
solution
220 63 stopped addition of NaOH
solution pH = 3.7
Agitation was stopped and the mixture was allowed to
cool to room temperature and stand overnight. The
following morning, the mixture was heated to 70C and
the upper, aqueous layer was siphoned off. Water
(400 ml) and 490 ml of methyl isobutyl ketone were
added, and the mixture was hea~ed with agitation
from 55 to 68C. Agitation was stopped and the upper,
aqueous layer was siphoned off. Wa~er (400 ml,
preheated to 75-80C) was added and the mixture was
agitated for 15 minutes at 70-80C. Agitation was
stopped and the lower, organic layer was drained out.
It weighed 1245 g. A sample was dried in vacuum oven
at 90-100C for one hour and showed 64.7% non-volatiles,
corresponding to 806 g of product, a 95% yield. NMR
(proton) examination of the vacuum-dried product con-
firmed that the product of Example 3 had been
duplicated~
26

~ 2~
Example 11
Chlorination of Triallyl Citrate Adduct Without
Solvent _ _
Produot of Example 2 399.6 g
5 Chlorine 45 g
Saturated aqueous sodium bisulfite 210 ml
30~ Aqueous sodium hydroxide 105 ml
A one-liter round-bottom flask with bottom outlet
was used. A mantle (Glas-Col~ was used for heafing.
10 The product of Example 2 was charged to the flask at
room temperature and was melted under nitrogen. Then,
the contents of the flask were agitated while chlorine
gas was introduced below the liquid surface, according
to the following schedule:
Elapsed Time Temperature Action and Remarks
(min) (C)
.
0 83 C12 started
11 g C12 in
2050 83 29 g C12 in
78 83 45 g C12 in.Cl stopped~
N2 sweep star~ed
100 83 Added 200 ml H2O
101 58 reheating to 80-85
25ilO 81 started addition o~ NaHSO3
solution
125 84 finished addition of NaHSO3
solution
130 83 started addition of NaOH
solution
30160 finished addition of NaOH
solutio~
170 85 pH = 3.5
Agitation was stopped at this point and the upper,
aqueous layer was siphoned off. Then, 300 ml. water
wereadded and the mixture was reheated to 88~C with
agitation. Agitation was stopped and the molten
product (330 g) was drained off the bottom. A sample
* denotes Trade Mark
27

1~33~
28
o the product was dried at 100C in a vacuum oven and
showe~ 95% non-volatiles. That represents 91% of the
theoretical yield. Elemental analysis gave the follow-
ing results:
5ElementCalc. ~ Found
C 28.2 31~62
Cl 6.4 6.4
F 58.4 56.6
H 1.2 0.98
10 I 0.0 0.76
NMR (proton~ and elemental analysis indicate theproduct has the structure given in Example 4.
Example 12
Preparation_of MPI/Diallyl Isophthalate (DAIP) Adduct
15 MPI 8655 g
DAIP 1980 g
ABI 60 g
All of the MPI was placed in a round-bottom flask,
set in a water bath for temperature control. Of the
20 DAIP, 600 ml. were added and the mixture was de-
oxygenated. The mixture was heated to 72 ~ 3C~ and
the following schedule of additions was followed:
Elapsed Time ABI Addition(g) DAIP Addition (ml)
0 6
2558 200
89 200
118 200
120 6
30178 200
180 6
238 200
240 6
298 - remainder
35300 6
360 6
420 6
28

123~18~
29
E ~ ABI Addition(g) DAIP Addition (ml)
~80 6
5~0 6
1410 temperature raised to 76 (material
was partially frozen)
1410-1450 temperature gradually raised to 82
to melt produc~
1485 reaction terminated
Chlorination of ~dduct
__
The above-described adduct (4000 g~ and 1,1,2-tri-
chloro-1,2,2-trifluoro ethane (2775 g.) were placed in a ra~-
bottom flask with bottom outlet and reflux condenser
and heated until stirrable, approximately 40C.
Chlorine (520 g) was added below the surface of the
li~uid over a 3. 5 hour period, while the temperature
was maintained between 35 and 50C., then 1 liter of
water was added. Over a period of 2.5 hours, 2200 ml.
of a saturated aqueous sodium hisulfite solu~ion were
added at a temperature in the range between 32-50Co
While cooling so as to maintain the temperature in
the range between 30 and 50C, 30% aqueous sodium
hydroxide was added. When after 1.5 hours, the pH
reached 5.4, addition of the aqueous sodium hydroxide
was terminated, 1865 ml. thereof having been used.
During the addition of the sodium hydroxide solution,
some salts formed inside the neck of the flask. One
liter of water was used in periodically rinsing the
salts from the neck of the flask. The mixture was let
stand ~or 0.5 hour and then the top layer (aqueous)
was drawn off. Watex (2900 ml.~, 1,1,2-trichloro-
1,2,2-trifluoromethane (250 ml~, isopropanol (250 ml.)
were added and the mixture was agitated and then
allowed to stand. The product, in solution in chloro-
fluorocarbon (a pale amber solution~ was drawn off the
bottom. The product, weighing 534 g was 57.4% solids
(by drying in vacuum oven, 90-100C), corresponding to
2~

1~318S
3072 g. of product, a 83.6% yield. The product,
in solution, is a very pale amber liquid. NMR is
consistent with the following structure:
O CH2Cl
,. .
C~O-CH~CH2~c~F2n+1
I~L- c -o lcH-cH2-cnF2n~
C~2
~0