Perfluoroalkyl halides and derivatives

Novel mixtures of perfluoroalkyl halides and derivatives thereof are described. These mixtures contain some compounds with a straight perfluoroalkyl group and some with a branched perfluoroalkyl group. Methods of preparation and use are also described.

FIELD OF THE INVENTION 
This invention relates to perfluoroalkyl halides and derivatives thereof, 
and to the preparation and use of such halides and derivatives in 
imparting water and oil repellency to substrates. 
BACKGROUND OF THE INVENTION 
Fluorocarbon derivatives (sometimes called organofluorine compounds or 
fluorochemicals) are a class of substances containing portions which are 
fluorocarbon in nature, e.g. hydrophobic, oleophobic, and chemically 
inert, and portions which are organic or hydrocarbon in nature, e.g. 
chemically reactive in organic reactions. The class includes some 
substances which are familiar to the general public, such as those which 
give oil and water repellency and stain and soil resistance to textiles, 
e.g. Scotchgard.TM. carpet protector. Other substances of the class have 
various industrial uses, such as reducing the surface tension of liquids, 
reducing evaporation and flammability of volatile organic liquids, and 
improving the leveling of organic polymer coatings. Examples of industrial 
substances are the Fluorad.TM. fluorochemical surfactants described in 3M 
Company trade bulletin 98-0211-2213-4 (38.3) BPH, issued March, 1988. 
Conventional fluorochemicals can be prepared from precursors such as 
fluoroalkyl iodides, fluoroalkyl carboxylic acid fluorides, and 
fluoroalkyl sulfonyl fluorides. See for example, "Organofluorine Chemicals 
and Their Industrial Applications", R. E. Banks, Ed., Ellis Horwood, Ltd., 
Chichester, England, 1979, pp. 214-234. 
Some perfluoroalkyl iodides can be prepared by telomerization of C.sub.2 
F.sub.5 I or (CF.sub.3).sub.2 CFI with C.sub.2 F.sub.4 yielding C.sub.2 
F.sub.5 (C.sub.2 F.sub.4).sub.n I or (CF.sub.3).sub.2 CF(CF.sub.2 
CF.sub.2).sub.n I, respectively, where n is typically from 1 to 4. See R. 
E. Banks, supra. All of the perfluoroalkyl iodides obtained from 
(CF.sub.3).sub.2 CFI contain perfluoroalkyl groups with a terminal branch, 
and such branched-chain perfluoroalkyl groups will hereinafter be 
represented by "R.sub.fb ". All of the perfluoroalkyl iodides obtained 
from C.sub.2 F.sub.5 I contain straight-chain perfluoroalkyl groups 
without branches, and such straight-chain (or "linear") perfluoroalkyl 
groups will hereinafter be represented by "R.sub.fs ". For brevity, 
"R.sub.f " will hereinafter be used to represent a perfluoroalkyl group 
with either a straight or a branched-chain. Perfluoroalkyl iodides can be 
converted into other functional (or reactive) materials, for example by 
the following illustrative schemes. 
##STR1## 
The alcohol, thiol, and olefin derivatives of the above schemes can be 
further converted to a great variety of derivatives, e.g., acrylates and 
polymers thereof, sulfates and salts thereof, carboxylic acids and esters 
thereof, etc. These further derivatives retain the original structure of 
the R.sub.f group, that is, the R.sub.f group remains either straight or 
branched. 
Functional materials derived from telomer iodides will (as stated above) 
contain either 100% straight-chain (R.sub.fs) or 100% branched-chain 
(R.sub.fb) perfluoroalkyl groups. Contradictory data have been reported in 
the literature regarding the relative advantage of straight-chain versus 
branched-chain perfluoroalkyl groups. In U.S. Pat. No. 4,127,711 (Lore et 
al.) perfluoroalkyl straight-chains are said to be preferred for textile 
applications, whereas in U.S. Pat. No. 3,525,758 (Katsushima et al.) it is 
disclosed that surfactants containing 100% branched-chain perfluoroalkyl 
groups are more effective than surfactants containing straight-chain 
perfluoroalkyl groups in lowering the surface tension of aqueous 
solutions. However, it has generally been accepted that among fluorinated 
surfactants of the same carbon number, straight-chain products generally 
give lower surface tension in aqueous solutions. Banks, supra at 222-223, 
describes that, except at very low concentrations (less than 0.01% or 100 
ppm), lower surface tension is attained with straight-chain 
fluorochemicals. Additionally, an article written by Bennett and Zismann 
(J. Phys. Chem., 71, 1967, p. 2075-2082) discloses that a condensed 
monolayer of a fully fluorinated straight-chain alkanoic acid has a lower 
critical surface energy than its terminally branched analogue with the 
same chain length. 
In addition to the telomerization procedure described above, another method 
of producing many fluorochemicals or their precursors is the fluorination 
process commercialized initially in the 1950s by 3M Company, which 
comprises passing an electric current through a mixture of the organic 
starting compound and liquid anhydrous hydrogen fluoride. This 
fluorination process is commonly referred to as "electrochemical 
fluorination" or "ECF". Some early patents describing such technology 
include U.S. Pat. Nos. 2,519,983 (Simons), 2,567,011 (Diesslin et al.), 
2,666,797 (Husted et al.), 2,691,043 (Husted et al.), and 2,732,398 (Brice 
et al.); they describe the preparation of such fluorochemical compounds as 
perfluoroalkyl carbonyl fluorides, e.g. C.sub.4 F.sub.9 --COF, and 
perfluoroalkyl sulfonyl fluorides, e.g. C.sub.4 F.sub.9 --SO.sub.2 F, and 
derivatives thereof. 
When perfluoroalkyl carbonyl fluorides and perfluoroalkyl sulfonyl 
fluorides are prepared by electrochemical fluorination (ECF) of 
appropriate hydrocarbon precursors, the resulting products are mixtures of 
compounds, where some of said compounds contain a straight-chain 
perfluoroalkyl group, e.g., R.sub.fs --SO.sub.2 F, and others of said 
compounds contain a branched-chain perfluoroalkyl group, e.g., R.sub.fb 
--SO.sub.2 F. Such mixtures of compounds result even when the starting 
materials contain only compounds with straight-chain alkyl groups. Such 
mixtures of compounds, e.g. a mixture of R.sub.fs --SO.sub.2 F and 
R.sub.fb --SO.sub.2 F, can be represented, for brevity, by the formula, 
R.sub.fsb --SO2F, which formula represents a mixture of compounds. The 
"sb" subscripts indicate that the formula represents a mixture of 
compounds, that is, a mixture of R.sub.fs --SO.sub.2 F and R.sub.fb 
--SO.sub.2 F. 
ECF-derived acid fluorides can be converted into other functional 
materials, for example by the following illustrative schemes. 
##STR2## 
Each R.sub.fsb containing formula, e.g., R.sub.fsb --COF, represents ECF 
derived mixtures which contain some compounds with a straight-chain 
perfluoroalkyl group and other compounds with a branched-chain 
perfluoroalkyl group. 
U.S. Pat. No. 2,950,317 (Brown et al) describes a process for the 
preparation of fluorocarbon sulfonyl chlorides from the corresponding 
fluorocarbon sulfonyl fluorides. 
An article by Park et al. (23, J. Org. Chem, 1166-1169 (1958)) describes 
the preparation of certain fluorochemical compounds with three or less 
fully-fluorinated carbon atoms. Compounds described include n--C3F.sub.7 
--CH.sub.2 CH.sub.2 --I and n--C3F.sub.7 --CH.sub.2 --CO.sub.2 H. 
SUMMARY OF THE INVENTION 
Briefly, the present invention, in one aspect, provides novel 
fluorochemical compositions which comprise a mixture of perfluoroalkyl 
halide compounds. Some of the perfluoroalkyl halide compounds of the 
mixture contain a straight-chain group (the term "straight-chain" is used 
herein in its accepted sense to mean normal or unbranched perfluoroalkyl 
group, e.g., CF.sub.3 CF.sub.2 CF.sub.2 CF.sub.2 --), and some contain a 
branched-chain perfluoroalkyl group (e.g., (CF.sub.3).sub.2 CFCF.sub.2 
--). 
The perfluoroalkyl halide compounds comprise a perfluoroalkyl group, a 
halogen atom selected from the group consisting of Cl, Br, and I, and a 
fluorine-free alkylene linking group bonded to the perfluoroalkyl group 
and to the halogen atom. 
The alkylene linking group contains at least two catenary carbon atoms, one 
of which is bonded to the perfluoroalkyl group, and the other of which is 
bonded to the halogen atom (e.g., as in R.sub.fsb --CH.sub.2 CH.sub.2 --I, 
but not as in R.sub.fsb --CH(CH.sub.3)--I). The carbon atom of the 
alkylene linking group which is directly bonded to the perfluoroalkyl 
group will be referred to as the alpha carbon atom, and the catenary 
carbon atom of the alkylene linking group which is bonded to said alpha 
carbon atom will be referred to as the "beta carbon atom". Such .alpha. 
and .beta. carbon atoms are illustrated, for example, in the formula 
##STR3## 
In another aspect, this invention provides novel fluorochemical 
compositions which comprise a mixture of perfluoroalkyl derivative 
compounds of said perfluoroalkyl halide compounds. Some of said 
perfluoroalkyl derivative compounds of said mixture contain a 
straight-chain perfluoroalkyl group, e.g., CF.sub.3 CF.sub.2 CF.sub.2 
CF.sub.2 --, and some contain a branched-chain perfluoroalkyl group, e.g., 
(CF.sub.3).sub.2 CFCF.sub.2 --. Said derivatives are obtained from said 
halides by one or more steps, and retain from the precursor halides the 
perfluoroalkyl group and the alpha and beta carbon atoms of the linking 
group. One or both of said alpha and beta carbon atoms may be converted, 
for example, to a carbonyl (C.dbd.O) or alkenylene carbon atom (C.dbd.C), 
but they are always retained in some form in the derivative. 
In still another aspect, the present invention provides novel 
fluoropolymers having both straight chain and branched chain pendant 
perfluoroalkyl groups. These fluoropolymers may be made, for example, 
through the polymerization of monomers having both branched and straight 
chain pendant perfluoroalkyl groups, or through the copolymerization of a 
first monomeric species having straight chain pendant perfluoroalkyl 
groups with a second monomeric species having branched chain pendant 
perfluoroalkyl groups (in the latter method, the ratio of the first 
monomeric species to the second monomeric species will preferably be 
within the range of about 1.5:1 to about 9:1, and more preferably within 
the range of about 2:1 to about 6:1). The monomeric species may be 
polymerized before or after being applied to a substrate. Preferably, 
about 60 to about 90% of the pendant perfluoroalkyl groups in the polymer 
are straight chain and about 10 to about 40% of the perfluoroalkyl groups 
in the polymer are branched chain, and more preferably, about 60 to about 
90% of the pendant perfluoroalkyl groups in the polymer are straight chain 
and about 10 to about 40% of the perfluoroalkyl groups are branched chain. 
The fluoropolymers of the present invention form better emulsifications, 
and exhibit better physical properties (e.g., improved solubility, better 
oil repellency and higher spray ratings) than the corresponding polymers 
having only straight chain or only branched chain pendant perfluoroalkyl 
groups. 
DETAILED DESCRIPTION OF THE INVENTION 
Preferably, the compositions of this invention comprise a mixture of 
compounds wherein 50 to 95% of said compounds contain a straight-chain 
perfluoroalkyl group (R.sub.fs), and wherein 5 to 50% of said compounds 
contain a branched-chain perfluoroalkyl group (R.sub.fb). Most preferably, 
the compositions of this invention comprise a mixture of compounds wherein 
60 to 90% of said compounds contain a straight-chain perfluoroalkyl group 
(R.sub.fs), and wherein 10 to 40% of said compounds contain a 
branched-chain perfluoroalkyl group (R.sub.fb). 
The compositions of this invention also may contain mixtures of compounds 
such that the number of carbon atoms in the perfluoroalkyl groups are 
predominately, e.g., greater then 70%, of one length, for example where 
greater then 70% of all perfluoroalkyl groups in the mixture of compounds 
have 8 carbon atoms. 
Because of the wide variety of the fluorochemical compositions of this 
invention, they can be used in numerous applications, including those 
where conventional fluorochemicals are used. Such applications are 
described, for example, in Banks, supra, which descriptions are 
incorporated herein. The fluorochemical compositions of this invention are 
useful in improving or imparting properties to solutions and substrates 
such as wetting, penetration, spreading, leveling, foaming, foam 
stabilization, flow properties, emulsification, dispersability, and oil, 
water, and soil repellency. 
A class of the fluorochemical compositions of this invention comprises a 
mixture of perfluoroalkyl halide compounds which mixture can be 
represented by Formula I. 
EQU R.sub.fsb --CH.sub.2 CH(R.sup.1)R.sup.2 --X I. 
In Formula I, the "fsb" subscript is meant to indicate that Formula I 
represents a mixture of compounds, that is, a mixture of R.sub.fs 
--CH.sub.2 CH(R.sup.1)R.sup.2 --X and R.sub.fb --CH.sub.2 
CH(R.sup.1)R.sup.2 --X. Some of said compounds contain a straight-chain 
perfluoroalkyl group (R.sub.fs) and all others of said compounds contain a 
branched-chain perfluoroalkyl group (R.sub.fb). 
In Formula I, R.sub.fsb is a perfluoroalkyl group. Said perfluoroalkyl 
group is saturated, mono-valent, and has at least 4 fully-fluorinated 
carbon atoms. While the perfluoroalkyl group can contain a large number of 
carbon atoms, compounds where the perfluoroalkyl group is not more than 20 
carbon atoms will be adequate and preferred since larger radicals usually 
represent a less efficient utilization of the fluorine (lower fluorine 
efficiency) than is obtained with shorter chains. Perfluoroalkyl groups 
containing from about 4 to about 10 carbon atoms are most preferred. 
In Formula I, R.sup.1 is a lower alkyl group, e.g., with 1 to 4 carbon 
atoms, or an aromatic group, e.g., phenyl, or combinations thereof, e.g., 
tolyl. R.sup.1 may also contain hereto atoms, e.g., S, O, N, Si, for 
example R.sup.1 may be --CH.sub.2 --OH. 
In Formula I, R.sup.2 is a covalent bond or an alkylene group such as 
(CH.sub.2)m, where m is from 1 to 20, or --CH(R) where R is as defined for 
R.sup.1, and R.sup.2 may also contain said hereto atoms. 
In Formula I, the carbon atom bonded to the perfluoroalkyl group may be 
referred to as the alpha carbon atom and is represented in Formula I as 
the "C" in CH.sub.2. The other depicted carbon atom, which is bonded to 
the alpha carbon atom, may be referred to as the beta carbon atom and is 
represented in Formula I as the "C" in CH(R.sup.1). 
In Formula I, X is I, Cl, or Br. 
A subclass of the fluorochemical compositions of this invention comprises a 
mixture of perfluoroalkyl halide compounds which mixture can be 
represented by Formula II. 
EQU R.sub.fsb --(CH.sub.2 CH.sub.2).sub.n --X II 
In Formula II, R.sub.fsb and X are as described above for Formula I and n 
is an integer from 1 to 5. 
The perfluoroalkyl halide mixtures of this invention are reactive chemicals 
and can be converted into their reactive or functional derivatives by one 
or more steps. A class of such derivatives can be represented by the 
formula R.sub.fsb --Z where R.sub.fsb is as defined and described above 
and Z is an organic moiety or an oxygen-containing inorganic moiety that 
is a one-step or multi-step derivative of the halide compounds. Various 
functional embodiments of Z make the derivatives useful reagents for the 
introduction of the R.sub.fsb moiety into molecules. Z can be an organic 
functional moiety, i.e., one which contains one or more carbon atoms, such 
as carbonyl-containing, sulfonyl-containing, alkylene-containing, 
nitrogen-containing, and oxygen-containing moieties or Z can be an 
oxygen-containing inorganic moiety, such as sulfonyl-containing and 
sulfonyloxy-containing moieties. Representative functional Z moieties are, 
for example, polymerizable groups which will undergo electrophilic, 
nucleophilic, or free radical reaction, derivatives with such groups being 
useful to form polymers comprising polymeric chains having a plurality of 
pendant perfluroalkyl groups. Derivative compounds of this invention 
include carboxylic and sulfonic acids and their metal and ammonium salts, 
esters, including alkyl and alkenyl esters, amides, tetrahydroalcohols 
(--C.sub.2 H.sub.4 OH), esters of tetrahydro-alcohols, acrylates (and 
polyacrylates), mercaptans, alkenyl ethers, etc. Stated otherwise, Z in 
the above formulas can contain --COOH, --COOM.sub.1/v, --COONH.sub.4, 
--CH.sub.2 COOR, --CONH.sub.2, --COONR.sup.1 R.sup.2, --NR.sup.1 R.sup.2, 
--CONR.sup.1 R.sup.3 A, --CH.sub.2 OH, 
##STR4## 
--CF.sub.2 OCF(CF.sub.3)COF, --CH.sub.2 NCO, --CH.sub.2 SH, --CN, 
--SO.sub.3 H, --SO.sub.3 M.sub.1/v, --SO.sub.3 NH.sub.4, --SO.sub.2 
NR.sup.1 R.sup.2, --SO.sub.2 NR.sup.1 R.sup.3 A, --SO.sub.2 NH.sub.2, 
--SO.sub.3 R, --CH.sub.2 SH, --CH.sub.2 NR.sup.1 R.sup.2, --CH.sub.2 
OCOCR.sup.4 .dbd.CH.sub.2, CH.sub.2 OCOCF.sub.2 SF.sub.5, and the like, 
where M is a metal atom having a valence "v", such as a monovalent metal 
atom like K or Na; R is alkyl (e.g. with 1 to 14 carbon atoms), aryl (e.g. 
with 6 to 10 or 12 ring carbon atoms), or a combination thereof (e.g. 
alkaryl or aralkyl); R.sup.1 and R.sup.2 are each independently H or R; 
R.sup.3 is alkylene (e.g. with 1 to 13 carbon atoms; R.sup.4 is H or 
CH.sub.3 ; A is an aliphatic or aromatic moiety, which can contain a 
carboxy or sulfo group or an alkali metal or ammonium salt or ester 
thereof, a carboxamido, a sulfonamido, or contain 1 to 3 hydroxy groups, 1 
or more ether-oxygen or oxirane-oxygen atoms, a cyano group, a phosphono 
group, or one or more primary, secondary, or tertiary amine groups, or 
quaternized amine group, or other functional group. 
The above illustrated derivatives can be converted to other derivative 
fluorochemical compositions of this invention. For example, hydroxy 
functional derivatives can be converted to corresponding sulfate 
derivatives useful as surfactants as described, for example, in U.S. Pat. 
No. 2,803,656 (Ahlbrecht et al.) or phosphate derivatives useful as 
textile and leather treating agents as described, for example, in U.S. 
Pat. No. 3,094,547 (Heine). Hydroxy functional derivatives can also be 
reacted with isocyanates to make carbamato-containing derivatives such as 
urethanes, carbodiimides, biurets, allophanates, and quanidines useful in 
treating fibrous substrates such as textiles as described, for example, in 
U.S. Pat. Nos. 3,398,182 (Guenthner et al.), 4,024,178 (Landucci), 
4,668,406 (Chang), 4,606,737 (Stern), and 4,540,497 (Chang et al.), 
respectively. 
Amine functional derivatives can be converted to corresponding amine salts 
useful as surfactants, as described, for example, in U.S. Pat. Nos. 
2,764,602 (Ahlbrecht), 2,759,019 (Brown et al.) or amphoteric surfactants 
as described, for example, in U.S. Pat. No. 4,484,990 (Bultman et al.). 
Amine functional derivative can be successively reacted to form an 
amphoteric surfactant as described, for example, in U.S. Pat. No. 
4,359,096 (Berger) (see Table I thereof). 
The polymerizable functional derivatives of this invention can be used to 
make polymers such as polyacrylates, polyesters, polyurethanes, 
polyamides, and polyvinyl ethers. Such polymers can be made by 
conventional step-growth, chain-growth, or graft polymerization techniques 
or processes. The step-growth polymers can be made, for example, from 
those derivatives having hydroxyl, carboxyl, isocyanato, or amino 
polymerizable groups. The acrylate, methacrylate, or vinyl derivatives of 
this invention can be used to make chain-growth polymers, such as 
polyacrylates. Fluorochemical ethylenically unsaturated monomers of this 
invention can be homopolymerized to make homopolymers, or copolymerized 
with copolymerizable monomers to make random, alternating, block, and 
graft polymers. Copolymerizable monomers which can be used include 
fluorine-containing and fluorine-free (or hydrocarbon) monomers, such as 
methyl methacrylate, ethyl acrylate, butyl acrylate, 
octadecylmethacrylate, acrylate and methacrylate esters of 
poly(oxyalkylene) polyol oligomers and polymers, e.g., poly(oxyethylene) 
glycol dimethacrylate, glycidyl methacrylate, ethylene, vinyl acetate, 
vinyl chloride, vinylidene chloride, vinylidene fluoride, acrylonitrile, 
vinyl chloroacetate, isoprene, chloroprene, styrene, butadiene, 
vinylpyridine, vinyl alkyl ethers, vinyl alkyl ketones, acrylic and 
methacrylic acid, 2-hydroxyethyl acrylate, N-methylolacrylamide, 
2-(N,N,N-trimethylammonium)ethyl methacrylate and the like. 
The polymers can be applied in the form of an aqueous or non-aqueous 
solution or emulsion as a coating or finish to modify the free surface 
energy of a substrate, e.g. a non-porous substrate such as glass, metal, 
plastic, and ceramic or a fibrous or porous substrate such as textile, 
e.g., nylon carpet fiber or polyester outerwear fabrics, leather, paper, 
paperboard, and wood to impart oil and water repellency thereto, as 
described, for example, in the Banks reference supra. 
The relative amounts of various comonomers which can be used with the 
monomers of this invention generally will be selected empirically and will 
depend on the substrate to be treated, the properties desired from the 
fluorochemical treatment, e.g., the degree of oil and/or water repellency 
desired, and the mode of application to the substrate. Generally, in the 
case of copolymers, of the interpolymerized or repeating units in the 
polymer chain, 5 to 95 mole percent of such units will contain pendant 
perfluoroalkyl groups. The fluoroaliphatic polymers of this invention can 
be blended with other or known polymers, such as 
perfluoromethyl-terminated fluoroaliphatic vinyl polymers, and the blend 
used to modify surface properties, e.g. of textiles such as fabrics to 
provide them with improved properties such as oil and water repellancy. 
Fluorochemicals of this invention which are useful as surfactants generally 
are those having a polar group such as --CO.sub.2 Na, --SO.sub.2 
NHC3H.sub.6 N.sup.+ (CH.sub.3).sub.3 Cl.sup.--, --SO.sub.2 N(C.sub.2 
H.sub.5)C.sub.2 H.sub.4 O(C.sub.2 H.sub.4 O).sub.7 H, and --CONHC3H.sub.6 
N.sup.+ (CH.sub.3).sub.2 CH.sub.2 CO.sub.2 --, these moieties being 
representative of the polar groups in anionic, cationic, non-ionic, and 
amphoteric surfactants, respectively. The surfactants are useful in 
improving or imparting properties to aqueous and non-aqueous (organic) 
liquid systems such as wetting, penetration, spreading, leveling, foaming, 
foam stabilization, flow properties, emulsification, dispersability, and 
oil, water, and soil repellency. Said liquid system generally will 
comprise a liquid phase (in which the surfactant will be dissolved or 
dispersed) and one or more other phases selected from the group consisting 
of another liquid phase, a gas phase, and a phase of dispersed solids 
(e.g. polymer solids), and the system can be in the form of an emulsion, 
suspension, or foam (such as an air foam). Examples of such liquid 
systems, or application areas for said surfactants, include rinsing, 
cleaning, etching, and plating baths, floor polish emulsions, photographic 
processes, water base coatings, powder coatings, solvent based coatings, 
alkaline cleaners, fluoropolymer emulsions, soldering systems, and 
specialty inks, such as described, for example, in 3M Bulletin 
98-0211-2213-4 (38.3) BPH. 
The fluorochemicals useful as surfactants also can be incorporated into or 
mixed with other substances. For example, if sufficiently thermally 
stable, they can be incorporated into polymeric materials, such as 
polyamides, e.g. nylon, or polyolefins, e.g., polypropylene, which are 
cast, blown, extruded, or otherwise formed into shaped articles, such as 
films and fibers, the so-incorporated fluorochemicals modifying the 
properties of the shaped articles, such as the oil and water repellency of 
their surfaces. The fluorochemical surfactants of this invention can also 
be mixed with other surfactants, such as hydrocarbon surfactants and/or 
the conventional fluorochernical surfactants, e.g. those disclosed in said 
U.S. Pat. Nos. 2,567,011 and 2,732,398, and such mixed surfactants used to 
form, for example, aqueous, film-forming foams as described in U.S. Pat. 
No. 3,562,156 (Francen). 
In the following examples, it is shown that the fluorochemical compositions 
of this invention impart improved properties. As shown in the working 
examples below, some of the compositions of this invention impart improved 
oil repellency to textile substrates compared to fluorochemical 
compositions derived from ECF and containing a sulfonamido linking group. 
As also shown, some of the compositions of this invention provide lower 
surface tension to, and have better solubility in, organic or aqueous 
systems compared to fluorochemical compositions obtained from 
telomerization (compositions where all compounds have straight-chain, or 
where all compounds have branched-chain perfluoroalkyl groups). 
A convenient route to the perfluoroalkyl halide mixtures of this invention 
utilizes perfluoroalkyl sulfonyl fluorides (obtained from ECF) according 
to the following illustrative schemes. 
##STR5## 
The perfluoroalkyl halide mixtures from Schemes A, B and C are readily 
converted to various derivatives containing for example hydroxyl, thiol, 
amino, acids, acid salts, esters, etc., and adducts and derivatives 
thereof, e.g., urethanes, acrylates and polymers thereof, etc., using 
conventional synthetic procedures, many of which are described in the 
examples. Each perfluoroalkyl halide mixture can be converted to either of 
the other two perfluoroalkyl halide mixtures.

In the following examples, all of the perfluoroalkyl sulfonyl fluorides 
utilized in Examples of this invention were prepared from the hydrocarbon 
precursors by electrochemical fluorination (ECF). 
EXAMPLES 
The following procedures were used where referred to in the examples. 
Padding Application Procedure 
Polymer emulsions were applied to a 100% cotton fabric (bleached mercerized 
cotton poplin, style #407, obtained from Test Fabrics, Inc., Middlesex, 
N.J.) by immersing the fabric in the treatment bath using a padding 
technique well known to those skilled in the art. The saturated fabric was 
run through a roller to remove excess emulsion to give a wet pick-up of 
approximately 60%. After treatment, the wet cotton fabric was dried and 
cured by placing in a forced air oven set at 150.degree. C. for 10 minutes 
to give a percent solids on fabric of approximately 0.3% SOF. 
Oil Repellency Test 
The oil repellency of the treated fabric was measured using AATCC Test 
Method 118-1975, "Oil Repellency: Hydrocarbon Resistance Test" as 
described in AATCC Technical Manual, 1977, 53, 223. This test measures the 
resistance of a fibrous substrate to wetting by a series of hydrocarbon 
liquids, with a range of surface tensions. Treated fabrics are given an 
"Oil Repellency" (OR) value ranging from "0" (least repellent) to "8" 
(most repellent). 
Spray Rating Test 
The resistance of the treated fabric to wetting with water, was measured 
using AATCC Test Method 22-1977, "Water Repellency: Spray Test" as 
described in American Association of Textile Chemists and Colorists 
Technical Manual, 1977, 53, 245. Treated fabrics are given a "Spray 
Rating" (SR) value on a scale of "0" to "100", with "0" indicating 
complete wetting of the upper and lower surfaces of the substrate and with 
"100" indicating no wetting. 
Laundering Procedure 
The procedure set forth below was used to prepare treated samples 
designated in the examples below as "5.times. Laundered". 
A 230 g sample of generally square, 400 cm.sup.2 to about 900 cm.sup.2 
sheets of treated substrate is placed in a conventional washing machine 
along with a ballast sample (1.9 kg of 8 oz fabric in the form of 
generally square, hemmed, 8100 cm.sup.2 sheets). Conventional detergent 
(TIDE.TM., 46 g, available from Procter & Gamble Co., Cincinnati, Ohio) is 
added and the washer is filled to high water level with hot water 
(40.degree. C..+-.3.degree. C). The substrate and ballast load is washed 
five times using a 12-minute normal wash cycle and the substrate and 
ballast are dried together in a conventional clothes dryer set on the 
"heat" setting for about 45 minutes. The dry substrate is pressed using a 
hand iron set at the temperature recommended for the particular substrate 
fabric. 
Dry Cleaning Procedure 
Substrate samples designated in the examples below as "Dry Cleaned" were 
treated as set forth in AATCC Test Method 7-1975, note 8.1. One dry 
cleaning cycle was used in all cases. 
Example 1 
In this example, the conversion of a perfluoroalkyl sulfonyl fluoride to a 
1,1,2,2-tetrahydroperfluoroalkyl iodide, R.sub.fsb CH.sub.2 CH.sub.2 I, 
will be described. Into a three-necked 5 L flask, fitted with a reflux 
condenser, thermometer, and stirrer, were placed 585 g 1,4-dioxane, 585 g 
deionized water and 248 g sodium sulfite. Using the synthetic procedure 
outlined in U.S. Pat. No. 3,420,877, Example 2, except 700 g 
perfluorodecanesulfonyl fluoride was used instead of 
perfluorooctanesulfonyl fluoride, and 435 g iodine instead of bromine. The 
perfluorodecanesulfonyl fluoride used comprised a mixture of about 65% 
straight-chain isomer and about 35% branched-chain isomer. After the 
reaction was completed, the perfluorodecyliodide formed was steam 
distilled out of the reaction mixture to give 428 g (72%) yellow product 
boiling 94.degree. C. to 100.degree. C. The product was washed at about 
45.degree. C. with a 400 g 10% sodium sulfite solution in water. The 
product (419 g) was a colorless liquid at 45.degree. C. and a solid-liquid 
mixture at room temperature. F-NMR analysis indicated that about 65% of 
the perfluoroalkyl chains were linear, about 10% contained a 
perfluorinated isopropyl branch, --CF(CF.sub.3).sub.2 at the end of the 
carbon chain, about 0.2% contained a terminal perfluoro t-butyl group 
--C(CF.sub.3).sub.3 and the remainder contained internal branches. The 
F-NMR data were obtained by using a solution of the product in acetone D6 
and using a 94.2 MHz F-NMR instrument. 
Into a 3 L steel kettle were placed 295 g (0.45 mole) of perfluorodecyl 
iodide from above, 1.8 g di t-butylperoxide and 4.6 g catalyst. The 
catalyst was prepared by mixing 30 g alumina, 2 g anhydrous cupric 
chloride, 2 g tin tetrachloride and 8 mL 2-aminoethanol. The reactants 
formed a blue-violet powder. The reactor was degassed and a nitrogen 
atmosphere was established. 12.8 g ethylene (0.45 mole) was charged into 
the reactor in 3 equal portions. After each addition, the pressure rose to 
about 120 psi (0.83 MPa) at a temperature of 108.degree. C. In about 30 
minutes after the first addition, the pressure dropped to about 40 psi 
(0.28 MPa) and the second portion of ethylene was added. The third portion 
was added in similar fashion. After all the ethylene was charged, the 
heating was continued at 108.degree. C. until the pressure had decreased 
to 40 psi (0.28 MPa) and stabilized at this pressure, indicating all 
ethylene was consumed. The warm reaction product was drained from the 
reactor. A slightly yellow solid product (307 g) was obtained. H-NMR 
analysis indicated that the perfluorodecyl tetrahydroiodide C.sub.10 
F.sub.21 CH.sub.2 CH.sub.2 I was formed. The product was dissolved in 1000 
g acetone, and the catalyst filtered off. After solvent evaporation, a 
slightly yellow solid was obtained. F-NMR analysis indicated that the 
perfluorinated chain composition of the perfluorodecyl tetrahydroiodide 
product was essentially the same as that of the perfluoroecyliodide 
precursor. 
Examples 2-5 
Following the procedure outlined in Example 1, the products of Examples 2 
to 5 were prepared. 
TABLE 1 
______________________________________ 
Starting Material 
Ex. (% straight-chain isomer) 
End Product 
______________________________________ 
2 C.sub.4 F.sub.9 SO.sub.2 F (90%) 
C.sub.4 F.sub.9 CH.sub.2 CH.sub.2 I 
3 C.sub.6 F.sub.13 SO.sub.2 F (80%) 
C.sub.6 F.sub.13 CH.sub.2 CH.sub.2 I 
4 C.sub.8 F.sub.13 SO.sub.2 F (70%) 
C.sub.8 F.sub.17 CH.sub.2 CH.sub.2 I 
5 *C.sub.10 F.sub.21 SO.sub.2 F (about 40%) 
C.sub.10 F.sub.21 CH.sub.2 CH.sub.2 I 
______________________________________ 
*Perfluorodecanesulfonyl fluoride at room temperature was a mixture of 
liquid components and semisolid components. In Example 1, the semisolid 
C.sub.10 F.sub.21 SO.sub.2 F was used; FNMR indicated that this fraction 
contains a major portion (about 65%) of linear perfluorinated chains. In 
Example 5, the liquid components of perfluorodecanesulfonyl fluoride 
(about 40% linear, 60% branched) were used. FNMR indicated the following 
composition of the resulting perfluordecyltetrahydroiodide product of 
Example 5: about 40% linear perfluorinated chain, about 10% terminal 
perfluoroisopropyl group, about 3.0% terminal perfluoro tbutyl group and 
the remainder (about 44.5%) internally branched material, CF.sub.3 
--(CF.sub.2).sub.x --CF(CF.sub.3)--(CF.sub.2).sub.y --, where x and y are 
each greater than zero. 
F-NMR indicated that the products of Examples 2-4 comprised a mixture of 
compounds with the following approximate composition: linear chains, 
CF.sub.3 --(CF.sub.2).sub.x --, 70-90%; branched-chains 10-30% comprising 
perfluoroisopropyl branches, (CF.sub.3).sub.2 CF(CF.sub.2).sub.x, about 
10%; perfluoro t-butyl branches, (CF3).sub.3 C--(CF.sub.2).sub.x about 
0.3%; and internal branching, about 15 to 20%. 
In Examples 6-11, the conversion of perfluoroalkanesulfonyl fluorides to 
tetrahydrochlorides (Examples 6-10) and homologs and a tetrahydrobromide 
(Example 11) are described. 
Example 6 
Perfluorooctanesulfonyl chloride was prepared from the corresponding 
sulfonyl fluoride (U.S. Pat. No. 3,420,877) containing about 70% 
straight-chain and 30% branched-chain isomers. The crude reaction product 
was washed with water, dilute aqueous potassium bicarbonate, water and 
dried with anhydrous sodium sulfate. Perfluorooctanesulfonyl chloride (12 
g, 0.0232 mole) and di t-butyl peroxide (0.40 g) were added to a thick 
wall glass ampoule. The ampoule was placed in a liquid nitrogen bath, 
evacuated with a pump, then ethylene (1.28 g, 0.046 mole) was condensed 
into the ampoule. The ampoule was sealed, placed into a Hastalloy B vessel 
which had been padded with a glass wool cushion, and the vessel was 
pressurized with nitrogen gas (to balance the pressure inside the 
ampoule). The reaction vessel was heated at 115.degree. C. for 6 hours, 
cooled to room temperature; then the glass ampoule cooled in liquid 
nitrogen and opened to yield a dark brown, semi-solid product (11 g). 
GC/MS analysis showed the product to be a mixture of C.sub.8 F.sub.17 
CH.sub.2 CH.sub.2 Cl and C.sub.8 F.sub.17 (CH.sub.2 CH.sub.2).sub.2 Cl. 
NMR analysis showed a product ratio of 2:1 of the 1 to 1 and 1 to 2 
adducts. The product contained a mixture of compounds, 70% of which 
contained straight-chain and 30% of which contained branched-chain 
perfluoroalkyl group. 
Example 7 
In this example, in order to better control the product ratios, ethylene 
was added incrementally to a heated mixture of perfluorooctanesulfonyl 
chloride using di t-butyl peroxide as free radical initiator. Thus a 
mixture of C.sub.8 F.sub.17 SO.sub.2 Cl(300 g, 0.58 mole) and di t-butyl 
peroxide initiator (1.8 g) was charged into a 300 mL Monel reactor. 
Ethylene (2.6 g) was added, and the mixture was heated with shaking to 
115.degree. C. Additional ethylene charges (2.5, 4.0, 3.0, and 2.7 g) were 
incrementally added over a three hour period for a total of 14.7 g of 
ethylene. Upon cooling to room temperature a slushy product (303 g), 
mainly C.sub.8 F.sub.17 C.sub.2 H.sub.4 Cl was obtained. 
Example 8 
Similarly, C.sub.8 F.sub.17 SO.sub.2 Cl (30 g) was dissolved in isooctane 
(30 g), benzoyl peroxide (0.1 g) added and the mixture agitated at 
100.degree. C. in a glass lined Hastalloy B reactor containing excess 
ethylene gas (8 g). After an eight hour reaction time at 
100.degree.-105.degree. C., the product, mainly C.sub.8 F.sub.17 C.sub.2 
H.sub.4 Cl, was isolated as a light, cream-colored solid. 
Example 9 
A mixture of 10 g (0.024 mole) perfluorohexanesulfonyl chloride containing 
about 80% straight-chain isomer, ethylene (1.3 g, 0.046 mole), and di 
t-butyl peroxide (0.4 g) was placed in a glass ampoule. The mixture was 
heated at 100.degree. C. for 18 hours. The product was isolated as a 
dark-colored liquid. GC analysis showed a product ratio of 3:2 of 1:1 and 
1:2 adducts. Mass spectral analysis and plasma chromatography showed the 
products contained no sulfur and had the structures C.sub.6 F.sub.13 
CH.sub.2 CH.sub.2 Cl and C.sub.6 F.sub.13 (CH.sub.2 CH.sub.2).sub.2 Cl. 
Example 10 
Perfluorodecanesulfonyl chloride prepared from the corresponding sulfonyl 
fluoride (about 60% straight-chain isomer), was used to prepare the 
corresponding tetrahydrochloride product. The perfluorodecanesulfonyl 
chloride (20.0 g, 0.032 mole), ethylene (5.0 g, 0.17 mole) and 
azobisisobutyronitrile (VAZO 64) were placed in a glass-lined 180 mL 
capacity Hastalloy B reactor and the vessel shaken and heated to 
70.degree.-75.degree. C. for 16 hours. The reaction vessel was cooled, 
excess pressure released, and the product (21.3 g) isolated as a waxy 
solid. A sample was purified by vacuum sublimation to afford a white 
crystalline product. Analysis by NMR and GC/MS verified the product to be 
a mixture of predominantly 1:1 and 1:2 adducts having the structure 
C.sub.10 F.sub.21 (CH.sub.2 CH.sub.2)nCl where n is mainly 1 and 2 with a 
very small amount of (&lt;5%) product where n=3. 
Example 11 
Perfluorobutanesulfonyl bromide was prepared using the method described by 
Harzdorf in Justus Liebig's Annalen der Chemie 1973, 33-39, whereby 
perfluorobutane sulfinic acid (from C.sub.4 F.sub.9 SO.sub.2 F about 90% 
linear isomer) was brominated in acetic acid. A mixture of 
perfluorobutanesulfonyl bromide (10.0 g, 0.0226 moles), ethylene (0.046 
moles) and di t-butyl peroxide 10.4 g) was heated at 90.degree. C. for 16 
hours in a glass-lined 180 cc Hastalloy B reactor. At the end of the 
reaction, a dark liquid (6.5 g) was isolated. The acidic components in the 
reaction mixture were removed by washing the liquid phase with aqueous 
potassium bicarbonate solution followed by two water washes and drying 
with sodium sulfate. GC/MS analysis showed the presence of a low boiling 
component (C.sub.4 F.sub.9 Br) and the desired products C.sub.4 F.sub.9 
CH.sub.2 CH.sub.2 Br and C.sub.4 F.sub.9 (CH.sub.2 CH.sub.2).sub.2 Br in a 
2:3 ratio. 
Example 12 
In this example, the conversion of a perfluoroalkyltetrahydroiodide to a 
perfluoroalkyl tetrahydroalcohol will be described. 
Into a 3 L, three-necked flask, fitted with a stirrer, a reflux condenser, 
and a thermometer, were placed 574 g (1 mole) of C.sub.8 F.sub.17 CH.sub.2 
CH.sub.2 I, as prepared in Example 4, 594 g (6 moles) of 
N-methylpyrrolidone and 72 g (4 moles) of water. The mixture was heated to 
reflux (about 117.degree. C.). The reaction was continued for 40 hours to 
yield a dark brown reaction mixture, which was cooled to about 80.degree. 
C. to give a 2 phase reaction mixture. Deionized water (1 L) was added and 
the mixture heated to 70.degree. C. for 1 hour to give 2 liquid phases. 
The brown bottom phase containing the reaction product was separated and 
washed two additional times at about 70.degree. C. using 1 L of water each 
time. The bottom product phase was separated from the water layer and 
purified by steam distillation using a Dean Stark trap with 400 mL water. 
Product boiling from 94.degree. C. to 102.degree. C. was collected. Total 
yield was 475 g, about 40 g was liquid, the remaining 435 g a slushy 
solid. The liquid was identified by H-NMR and GC-MS to be the olefin, 
C.sub.8 F.sub.17 CH.dbd.CH.sub.2. The solid analyzed by gas chromatography 
was shown to be the 95% of the tetrahydroalcohol, C.sub.8 F.sub.17 
CH.sub.2 CH.sub.2 OH. The remainder was unreacted tetrahydroiodide. The 
yield of tetrahydroalcohol was 84%. F-NMR analysis indicated that the 
product mixture, contained about 74% linear chains, about 11% terminal 
perfluoroisopropyl groups, about 0.2% terminal perfluoro t-butyl groups, 
and about 14% internal branching. Upon standing at room temperature, the 
slushy solid separated into 2 physical phases: a small top liquid phase 
and a major bottom semi-solid phase. The top liquid was separated off and 
analyzed by F-NMR. The mixture of compounds of the liquid phase contained 
about 44% linear materials, about 12% terminal perfluoroisopropyl groups, 
about 0.3% terminal t-butyl groups, and about 43% internal branches. 
Examples 13, 14 
Using the procedure outlined in Example 12, the following perfluoroalkyl 
tetrahydroalcohols were made from the tetrahydroiodides of Examples 1 and 
2. 
TABLE 2 
______________________________________ 
STARTING MATERIAL 
Ex. (% straight-chain) 
END PRODUCT YIELD 
______________________________________ 
13 C.sub.4 F.sub.9 CH.sub.2 CH.sub.2 I (90%) 
C.sub.4 F.sub.9 CH.sub.2 CH.sub.2 OH 
88% 
14 C.sub.10 F.sub.21 CH.sub.2 CH.sub.2 I (65%) 
C.sub.10 F.sub.21 CH.sub.2 CH.sub.2 OH 
80% 
______________________________________ 
Example 15 
In this example, the conversion of perfluoroalkyl tetrahydroiodide to a 
perfluoroalkyl tetrahydrothiol will be described. 
Into a 3 L, three-necked flask, fitted with a stirrer, a thermometer, and a 
reflux condenser, were placed 574 g (1 mole) of perfluorooctyl 
tetrahydroiodide (prepared as described in Example 4), C.sub.8 F.sub.17 
CH.sub.2 CH.sub.2 I, 114 g (1.5 mole) of thiourea and 400 g of ethanol. 
The reaction mixture was heated at 75.degree. C. under a nitrogen 
atmosphere for 5 hours. The reaction was cooled to 50.degree. C. under 
nitrogen. Then 120 g of a 50% solution of NAOH (1.5 mole) and 200 g 
deionized water were added and heating at 50.degree. C. continued for 1 
hour. Addition of 1 L of water gave 2 liquid phases. The brown bottom 
phase containing the reaction product was washed twice with 1 L of water 
at room temperature and the product phase separated. A Dean Stark trap was 
set up, 400 g of water added, and the perfluoroalkyl tetrahydrothiol 
product steam distilled at a temperature of 94.degree. C. to 99.degree. 
C., to give 430 g of a colorless liquid product. Gas chromatographic 
analysis indicated an 84% yield of C.sub.8 F.sub.17 CH.sub.2 CH.sub.2 SH, 
and about 2% olefin, C.sub.8 F.sub.17 CH.dbd.CH.sub.2. F-NMR indicated 
that the C.sub.8 F.sub.17 CH.sub.2 CH.sub.2 SH product mixture contained 
about 77% linear chains, about 9% terminal perfluoroisopropyl groups, 
about 0.2% terminal perfluoro t-butyl groups, and about 13% internal 
branching. 
Examples 16-19 
Using the procedure outlined in Example 15, the following perfluoroalkyl 
tetrahydrothiols were made: 
TABLE 3 
______________________________________ 
STARTING MATERIAL 
Ex. (% straight-chain) 
END PRODUCT YIELD 
______________________________________ 
16 C.sub.4 F.sub.9 CH.sub.2 CH.sub.2 I (90%) 
C.sub.4 F.sub.9 CH.sub.2 CH.sub.2 SH 
75% 
17 C.sub.10 F.sub.21 CH.sub.2 CH.sub.2 I (65%) 
C.sub.10 F.sub.21 CH.sub.2 CH.sub.2 SH 
88% 
18 C.sub.10 F.sub.21 CH.sub.2 CH.sub.2 I (40%) 
C.sub.10 F.sub.21 CH.sub.2 CH.sub.2 SH 
85% 
19 C.sub.8 F.sub.17 (CH.sub.2 CH.sub.2).sub.1.3 Cl (70%) 
C.sub.8 F.sub.17 (CH.sub.2 CH.sub.2).sub.1.3 
33% 
______________________________________ 
Example 20 
In this example, the conversion of a perfluoroalkyl tetrahydroalcohol into 
the corresponding perfluoroalkyl acrylate is described. 
Into a three-necked 500 mL flask, fitted with a condenser, a stirrer, and a 
thermometer, were placed 232 g (0.5 mole) of perfluorooctyl 
tetrahydroalcohol (prepared as described in Example 12) C.sub.8 F.sub.17 
CH.sub.2 CH.sub.2 OH, and 90 g methyl ethyl ketone (MEK). Using a Dean 
Stark trap, 20 g MEK was distilled out, the reaction mixture cooled to 
room temperature under nitrogen, then 50.5 g (0.5 mole) of dry 
triethylamine and 100 ppm Irgonox 1010 antioxidant (Ciba-Geigy) were 
added. Using an addition funnel and a nitrogen purge, 45 g (0.5 mole) of 
acryloyl chloride were added over a 1 hour period. An exotherm of about 
20.degree. C. was noticed. A white slurry was obtained in the exothermic 
(about 20.degree. C. temperature rise) reaction. After the addition was 
complete, the reaction mixture was maintained at 50.degree. C. for 2 
hours. Gas chromatographic analysis indicated a conversion of 95% to 
acrylate. The reaction mixture was washed three times using 200 mL of 
water. The yield of colorless liquid product, C.sub.8 F.sub.17 CH.sub.2 
CH.sub.2 OCOCH.dbd.CH.sub.2, was 237 g (94%). 
Example 21 
Following the procedure of Example 20, C.sub.4 F.sub.9 CH.sub.2 CH.sub.2 
OCOCH.dbd.CH.sub.2, was prepared in a 90% yield as a slightly yellow 
liquid, starting from the alcohol of Example 13. 
Comparative Example 22 
In this example, the conversion of perfluoroalkyl tetrahydroiodide into a 
perfluoroalkyl olefin will be described. 
Into a 1 L, three-necked flask, fitted with a condenser, a thermometer, and 
a stirrer, were placed 57.5 g (0.1 mole) perfluorooctyl tetrahydroiodide 
as prepared in Example 4, 100 g isopropanol and 8.4 g (0.15 mole) 
potassium hydroxide. The reaction mixture was heated at reflux for 5 hours 
to give a brown reaction mixture. Gas chromatographic analysis showed a 
conversion to about 96% olefin. Deionized water (400 mL) was added and the 
reaction mixture was steam distilled using a Dean Stark trap. In a 
temperature range 94.degree.-98.degree. C., 43 g (95%) of colorless liquid 
olefin product, C.sub.8 F.sub.17 CH.dbd.CH.sub.2, was obtained in a purity 
greater than 98%. F-NMR analysis indicated that the mixture of compounds 
contained about 74% linear material, about 10% terminal 
perfluoroisopropyl, about 0.2% terminal perfluoro t-butyl, and about 13% 
internal branching. 
Example 23 
Following the procedure of Example 22, C.sub.10 F.sub.21 CH.dbd.CH.sub.2 
was prepared from the tetrahydroiodide of Example 5. This olefin product 
mixture contained about 42% linear perfluorinated chains, about 10% 
perfluoroisopropyl terminated, and about 46% internally branched material. 
Example 24 
In this example, the conversion of a perfluoroalkyl tetrahydroalcohol into 
a perfluoroalkyl dihydrocarboxylic acid is described. 
Into a 1 L, three-necked flask, fitted with a reflux condenser, a 
thermometer, and a stirrer, were placed 46.6 g (0.1 mole) of 
tetrahydroalcohol, C.sub.8 F.sub.17 CH.sub.2 CH.sub.2 OH (prepared in 
Example 6), and 450 g acetone. The solution was cooled to about 5.degree. 
C. in an ice bath and 23.7 g (0. 15 mole) of potassium permanganate added 
in small portions over a 2 hour period. The reaction was exothermic, and a 
color change from purple to brown was observed. After all the potassium 
permanganate had been added, the reaction was allowed to react for 1 hour 
at room temperature. The reaction was then slowly heated up to reflux 
temperature (about 58.degree. C.) and maintained for about 3 hours. Then 
50 g of water were added to the brown product slurry and all acetone was 
removed by distillation. The reaction was cooled to about 5.degree. C. 
using an ice bath, and 100 g of 95% sulfuric acid were added slowly over a 
2 hour period. After the acid addition, the reaction mixture was heated at 
95.degree. C. for 2 hours. After cooling to about 40.degree. C., 200 mL of 
water was added to the two-phase mixture. The brown bottom phase was 
separated from the water layer at 65.degree. C. and washed twice using 200 
mL water at 75.degree. C. The bottom phase was collected and distilled. 
The product fraction collected from 100.degree. C. to 130.degree. C. at 
about 20 torr yielded 35 g of a solid material at room temperature. GC-MS 
analysis indicated the presence of about 78% C.sub.8 F.sub.17 CH.sub.2 
COOH, about 11% C.sub.8 F.sub.17 CH.sub.2 COOCH.sub.2 CH.sub.2 C.sub.8 
F.sub.17 (ester of the starting alcohol and the formed acid) and about 10% 
C.sub.8 F.sub.17 COOH. The yield of perfluorooctyl dihydrocarboxylic acid, 
C.sub.8 F.sub.17 CH.sub.2 COOH, was about 57%. 
Example 25 
Into a 500 mL three-necked flask, fitted with a reflux condenser, a 
thermometer, and a stirrer, were placed 61.8 g (1 mole) boric acid, 232 g 
(4 moles) allyl alcohol and 120 g toluene. A Dean Stark trap was used to 
collect water during the azeotropic distillation. The initial white slurry 
present before the reaction mixture was heated became a clear solution 
after heating to reflux and forming 53 g of water in the azeotropic 
distillation. Toluene, excess allyl alcohol and triallyl borate ester 
product were distilled off. The triallyl borate (161 g, 89%) was obtained 
as a colorless, viscous liquid. Into a 500 mL three-necked flask, fitted 
with a reflux condenser, a thermometer, and a stirrer were placed 18.2 g 
(0.1 mole) of the above triallyl borate, 20 g ethyl acetate, 103.8 g (0.3 
mole) C.sub.4 F.sub.9 I, prepared following Example 1a, and 0.2 g 
azobisisobutyronitrile (AIBN). The mixture was heated at about 40.degree. 
C. and degassed using aspirator vacuum and nitrogen. The reaction mixture 
was heated to reflux, and an additional 0.2 g of AIBN were added. Heating 
at reflux was continued for 15 hours under a nitrogen atmosphere, followed 
by addition of another 0.2 g of AIBN and refluxing for an additional 5 
hours. Gas chromatographic analysis of the clear, yellow product solution 
indicated that about 2% of unreacted C.sub.4 F.sub.9 I was left unreacted 
and that the major product was C.sub.4 F.sub.9 CH.sub.2 CH(I)CH.sub.2 OH. 
After addition of 230 g of deionized water and distilling off ethyl 
acetate, the reaction mixture was heated at 95.degree. C. for 1 hour. The 
bottom yellow-brown organic layer containing the reaction product was 
washed twice with 200 g of water at 95.degree. C. 
Example 26 
To the yellow-brown liquid product from Example 25 was added at room 
temperature, 24 g (0.3 mole) of a 50% aqueous sodium hydroxide solution, 
100 g isopropanol and 30 g water. The reaction mixture was heated at 
40.degree. C. for 2 hours, then 300 g of water were added. The brown 
bottom phase of the mixture, containing the reaction product, was washed 
twice with 200 g water. Distillation at reduced pressure gave 61.7 g (74% 
yield) of epoxy 
##STR6## 
in a purity of 93% as determined by GC, and H- and F-NMR analysis. A by 
product (3%) was C.sub.4 F.sub.9 CH.dbd.CHCH.sub.2 OH. The epoxy product 
mixture contained about 74% straight-chains, about 11% terminal 
perfluoroisopropyl branches and about 14% internal branching. 
Example 27 
Following the same procedure as in Examples 25 and 26, 
##STR7## 
was prepared from C.sub.8 F.sub.17 I and triallyl borate. The intermediate 
product C.sub.8 F.sub.17 CH.sub.2 CH(I)CH.sub.2 OH was not isolated. 
The following Table shows the structures of the major products in the 
mixtures produced in Examples 1.intg.27. Table 4 also lists the weight % 
of compounds containing a straight-chain perfluoroalkyl group and the 
weight % of compounds containing a branched-chain perfluoroalkyl group in 
each product mixture. 
TABLE 4 
______________________________________ 
Percent straight and branched 
Perfluoroalkyl Groups 
Examples 
Product straight 
branched 
______________________________________ 
1 C.sub.10 F.sub.21 CH.sub.2 CH.sub.2 I 
65 35 
2 C.sub.4 F.sub.9 CH.sub.2 CH.sub.2 I 
90 10 
3 C.sub.6 F.sub.13 CH.sub.2 CH.sub.2 I 
83 17 
4 C.sub.8 F.sub.17 CH.sub.2 CH.sub.2 I 
74 26 
5 C.sub.10 F.sub.21 CH.sub.2 CH.sub.2 1 
40 60 
6 C.sub.8 F.sub.17 (CH.sub.2 CH.sub.2).sub.1.3 Cl 
70 30 
7 C.sub.8 F.sub.17 (CH.sub.2 CH.sub.2).sub.1 Cl 
70 30 
8 C.sub.8 F.sub.17 (CH.sub.2 CH.sub.2).sub.1 Cl 
70 30 
9 C.sub.6 F.sub.13 (CH.sub.2 CH.sub.2).sub.1.4 Cl 
80 20 
10 C.sub.10 F.sub.21 (CH.sub.2 CH.sub.2).sub.1.3 Cl 
60 40 
11 C.sub.4 H.sub.9 (CH.sub.2 CH.sub.2).sub.1.6 Br 
90 10 
12 C.sub.8 F.sub.17 CH.sub.2 CH.sub.2 OH* 
74 26 
C.sub.8 F.sub.17 CH.sub.2 CH.sub.2 OH** 
44 56 
13 C.sub.4 F.sub.9 CH.sub.2 CH.sub.2 OH 
91 9 
14 C.sub.10 F.sub.21 CH.sub.2 CH.sub.2 OH 
63 37 
15 C.sub.8 F.sub.17 CH.sub.2 CH.sub.2 SH 
77 23 
16 C.sub.4 F.sub.9 CH.sub.2 CH.sub.2 SH 
89 11 
17 C.sub.10 F.sub.21 CH.sub.2 CH.sub.2 SH 
65 35 
18 C.sub.10 F.sub.21 CH.sub.2 CH.sub.2 SH 
40 60 
19 C.sub.8 F.sub.17 (CH.sub.2 CH.sub.2).sub.1.3 SH 
75 25 
20 C.sub.8 F.sub.17 CH.sub.2 CH.sub.2 OCOCH=CH.sub.2 
77 23 
21 C.sub.4 F.sub.9 CH.sub.2 CH.sub.2 OCOCH=CH.sub.2 
90 10 
22 C.sub.8 F.sub.17 CH=CH.sub.2 
74 26 
23 C.sub.10 F.sub.21 CH=CH.sub.2 
42 58 
24 C.sub.8 F.sub.17 CH.sub.2 COOH 
75 25 
25 C.sub.4 F.sub.9 CH.sub.2 CH(CH.sub.2 OH)I 
90 10 
26 
##STR8## 89 11 
27 
##STR9## 74 26 
______________________________________ 
*Slushy Product 
**Liquid Phase 
Example 28 
In this example, the conversion of a perfluoroalkyl tetrahydrothiol to a 
perfluoroalkyl melamine is described. 
Into a 500 mL three-necked flask, fitted with a stirrer, a reflux 
condenser, and a thermometer, were placed 39.0 g (0.1 mole) 
hexametboxymethyl melamine (HMMM) available from American Cyanamid, as 
Aerotex 302), 192 g (0.4 mole) perfluorooctyl tetrahydrothiol, from 
Example 15 and 0.34 g p-toluene sulfonic acid. The action mixture was 
slowly heated to 80.degree. C. under nitrogen. Methanol forming in the 
reaction caused some foaming. The temperature was slowly increased over a 
2 hour period to 120.degree. C. In this period, about 10 g of methanol was 
formed and trapped in a Dean Stark trap. The foam had completely 
collapsed. The reaction mixture was heated during 30 minutes from 
120.degree. C. to 180.degree. C. under nitrogen yielding an additional 2.5 
g methanol in the Dean Stark trap. Heating of the reaction mixture was 
continued at 180.degree. C. for 5 hours under a nitrogen atmosphere. The 
condensation reaction product was a yellow-brown solid at room temperature 
and comprises a mixture of compounds of formula C.sub.3 N.sub.6 (CH.sub.2 
OCH.sub.3).sub.x (CH.sub.2 SC.sub.2 H.sub.4 C.sub.8 F.sub.17).sub.y where 
x and y have average values of about 2 and 4, respectively. 
Into a 500 mL three-necked flask, fitted with a reflux condenser, a 
thermometer, and a stirrer, were charged 180 g solids of the above 
prepared condensate (from (a)) and 270 g butyl acetate. The reaction 
mixture was heated at 65.degree. C. to yield a clear yellow-brown 
solution. 
Into a separate 1 L beaker were placed 18.0 g Marlowet.TM. 5401 emulsifier 
(Huls, Germany), 108 g ethyl Cellosolve.TM. and 720 g of deionized water 
and stirred and heated to about 65.degree. C. until a clear solution 
resulted. While stirring vigorously, the above butyl acetate solution of 
the fluorochemical melamine product was added to the aqueous solution at 
about 65.degree. C. A preemulsion resulted, which was passed through a 
preheated (at 70.degree. C.) Manton-Gaulin emulsifier at about 4000 psi 
(27.6 MPa) pressure. A yellow-brown, nearly transparent emulsion at about 
70.degree. C. resulted. The solvent was removed using a vacuum pump at 
about 1 to 10 torr and 50.degree. C. A nearly transparent, aqueous 
dispersion resulted. The solids content was about 18%. 
Example 29, Comparative Examples C1-C3 
Following the same procedure as in Example 28, Example 29 and Comparative 
Examples C1-C3 were prepared, as shown below. The Comparative Examples 
C.sub.2 and C3 contain straight-chain fluoroalkyl groups only. Comparative 
Example C1 contains a sulfonamido group directly attached to the 
perfluoroalkyl group. 
TABLE 5 
______________________________________ 
MOLAR RATIO 
FLUOROCHEMICAL HMMM/FC- 
EX. INTERMEDIATE USED INTERMEDIATE 
______________________________________ 
29 C.sub.10 F.sub.21 CH.sub.2 CH.sub.2 SH as prepared in 
1:4mple 
18 
C1 C.sub.8 F.sub.17 SO.sub.2 N(CH.sub.3)CH.sub.2 CH.sub.2 OH 
1:4 
(available from 3M) 
C2 C.sub.n F2.sub.n+1 CH.sub.2 CH.sub.2 SH with &lt;n&gt; = 10 
1:4 
(available from Ciba Geigy) 
C3 C.sub.n F2.sub.n+1 CH.sub.2 CH.sub.2 OH with &lt;n&gt; = 8 
1:4 
(available from DuPont) 
______________________________________ 
Examples 28 and 29, and Comparative Examples C1-C3 (containing R.sub.fs 
groups), were used as dispersions to treat textile fabrics. 
An aqueous treatment bath, which is usually a dispersion or emulsion, is 
prepared containing the fluorochemical compositions and other required or 
desired ingredients such as resins, catalysts, extenders, softeners, etc. 
The textile fabric is immersed in the treatment bath by a padding 
technique, which is well known to those skilled in the art. The saturated 
fabric is run through a roller to remove excess dispersion/emulsion, dried 
and cured in an oven for the desired temperature and time. The resulting 
treated fabrics are tested for oil and water repellency by test methods 
set forth below: 
______________________________________ 
Water spray (SR) test 
AATCC Test Method 22-1977 
Oil repellency (OR) test 
AATCC Test Method 118-1975 
Bundesmann test: 
Deutche Industries Norm (DIN) 
53-888 
Dry cleaning procedure: 
AATCC Test Method 7-1975 
Laundering procedure: 
A 230 g sample of 400 cm.sup.2 to about 900 cm.sup.2 of 
treated fabric is placed in a conventional washing machine along with a 
ballast sample (1.9 kg of 8 oz. fabric). Conventional detergent (46 g) 
is 
added and the washer filled to high water level with hot water 
(40 .+-. 3.degree. C.). The substrate and ballast is washed 5 times 
using 12 minute normal wash cycle and the substrate and ballast are 
dried 
together in a conventional clothes dryer for about 45 minutes. The dry 
substrate is pressed using a hand iron set at the temperature 
recommended 
for the particular fabric. 
______________________________________ 
Evaluation (using the above test methods and procedures) of fabric samples 
treated with the compositions of Examples 28 and 29 and Comparative 
Examples C1, C2, and C3 is given in Table V below. 
A polyester/cotton 50/50 blend fabric was treated at 0.3% solids by weight 
on total weight of the fabric using a treatment bath containing: a) the 
fluorochemical melamine dispersions containing approximately 18 wt. % 
solids, as described above; b) 12 g/L resin LYOFIX CHN (Chem. Fabrik 
Pfersee, Germany) 6 g/L Knittex catalyst 20 (Chem. Fabrik Pfersee) and 2 
mL/L acetic acid (60%). The treated fabrics were dried and cured at 
150.degree. C. for 5 minutes. Results are shown in Table 6. 
TABLE 6 
______________________________________ 
After 1 
Bundesman After 5 Dry 
Initial 1 5 10 Launderings 
Cleaning 
Ex. OR SR (Minutes) OR SR OR SR 
______________________________________ 
28 6 100 5 5 5 5 90 5 100 
29 5 100 5 5 5 4 80 5 90 
C1 3 100 4.5 4.5 4 2 90 2 100 
C2* 5 100 5 5 5 3 90 4 100 
C3 5 100 4.5 3.5 3 4 80 4 90 
______________________________________ 
*In the emulsification step, hexafluoroxylene was used as the organic 
solvent. 
As the results indicate (compare, for example the results for Example 28 to 
the results for Comparative Examples C1 and C3) the compositions of the 
invention impart better oil and water repellency to fabrics, and the 
treated fabrics retain repellency after laundering and dry cleaning. The 
results show that the compositions obtained from reactions using 
intermediates of the invention are, at equal carbon atom content in the 
perfluoroalkyl group, superior to compositions made using intermediates 
containing 100% straight-chain perfluoroalkyl groups (R.sub.fs), or 
compositions with a sulfonamido linking group (containing straight and 
branched-chain perfluoroalkyl groups). These intermediates of this 
invention are more effective oil and water repellency agents than those 
derived from the two other classes of intermediates. Even more surprising 
is the comparison of Example 28 and Comparative Example C2, which shows 
that the C.sub.8 thiol of this invention gives a product with equal or 
slightly better properties than the composition derived from a 
straight-chain C.sub.10 thiol, indicating a better fluorine efficiency. 
Another advantage of these intermediates and compositions of this invention 
is their superior solubility in organic solvents, which is important if 
the compositions are used as aqueous dispersions. Comparative Example C2 
could only be emulsified when hexafluoroxylene was used as a solvent, 
while the products of Examples 28 and 29 were easily soluble in a variety 
of organic solvents such as esters or ketones. The solubility of the 
product of Comparative Example C3 was also poorer than products of 
Examples 28 and 29, although better than Comparative Example C2 (perhaps 
due to its shorter average chain length). 
Example 30 
Into a 500 mL three-necked flask, fitted with a stirrer, a reflux 
condenser, and a thermometer, were placed 46.4 g (0.1 mole) of C.sub.8 
F.sub.17 CH.sub.2 CH.sub.2 OH (as prepared in Example 12) and 80 g ethyl 
acetate. A Dean Stark trap was set up and 20 g ethyl acetate distilled 
out. The reaction was cooled to about 40.degree. C. under nitrogen; then 
40.8 g (0.3 isocyanate equivalent) of PAPI (an oligomeric aromatic 
isocyanate of chemical structure: 
OCNC.sub.6 H.sub.4 CH.sub.2 C.sub.6 H3(NCO)!.sub.n CH.sub.2 C.sub.6 
H.sub.4 NCO (average of n=0.7) available from Upjohn Co.) and 3 drops of 
dibutyltin dilaurate were added. The reaction was heated to reflux (about 
78.degree. C.) under nitrogen, and heating continued for 5 hours at 
reflux. The reaction mixture was cooled to about 45.degree. C. under N2, 
then 17.4 g (0.2 mole) of 2-butanone oxime (Servo Comp., The Netherlands) 
added over about 30 minutes resulting in an immediate exotherm of about 
10.degree. C. Heating of the reaction mixture was continued for 1 hour at 
60.degree. C., after which time no isocyanate absorption by infrared 
analysis could be detected. A clear, brown solution containing a 
fluorochemical oligomeric urethane was obtained. 
Into a 500 mL three-necked flask, fitted with a stirrer, a thermometer, and 
a reflux condenser, were placed the above obtained ethyl acetate solution 
and 80 g of additional ethyl acetate. The mixture was heated to about 
60.degree. C. to yield a clear, brown solution. Into a separate 1 L beaker 
were placed 10.3 g Marlowet.TM. 5401 emulsifier (commercially available 
from Huls), 60 g ethylene glycol and 355 g deionized water. This solution 
was heated to about 60.degree. C.; then under vigorous stirring, the 
organic solution was added to the aqueous solution. The resulting 
preemulsion was passed 3 times through a preheated Manton Gaulin 
emulsifier at about 55.degree. C. and 4000 psi (27.6 MPa) pressure. The 
ethyl acetate solvent was distilled out using an aspirator vacuum to yield 
a pale brown, slightly transparent aqueous dispersion containing about 18 
wt. fluorochemical urethane oligomer. 
Comparative Examples C4, C5 
Using the same synthetic and emulsification procedure as in Example 30, 
further examples were prepared as shown in Table VI. Comparative Example 
C.sub.4 was made using N-methylperfluoroctanesulfonamido ethanol, C.sub.8 
F.sub.17 SO.sub.2 N(CH.sub.3)CH.sub.2 CH.sub.2 OH, (available from 3M 
Company) and Comparative Example C5 was made using perfluorodecyl 
tetrahydroalcohol, C1OF.sub.21 CH.sub.2 CH.sub.2 OH (available from 
Hoescht Co., Germany), double the amount of solvent had to be used during 
emulsification. 
Using the same fabric, treatment method and test procedures as described 
above for Examples 28, 29, and Comparative Examples C1-C3, the following 
test results were obtained: 
TABLE 7 
______________________________________ 
Treatment with 
Composition of 
Initial 5 Launderings 
1 Dry Cleaning 
Example OR SR OR SR OR SR 
______________________________________ 
30 4 100 3 80 2 80 
C4 2 100 0 70 0 70 
C5 3 100 2 80 2 70 
______________________________________ 
The results indicate again that the compositions of this invention are 
superior to compositions containing 100% straight-chain perfluoroalkyl 
group. The compositions of this invention are also superior to sulfonamido 
derived compositions. Again, the intermediates of this invention show 
better fluorine efficiency, better performance and better solubility. 
Example 31 
In this example, compositions of the invention were used to make an 
oligomeric fluorochemical urethane derivative. 
Into a 500 mL three-necked flask was placed 51.8 g (0. 1 mole) of the 
acrylate prepared in Example 20, 2 g (0.025 mole) of 2-mercaptoethanol, 
0.4 g AIBN initiator and 40 g ethyl acetate. The mixture was heated to 
about 40.degree. C. and degassed. The reaction mixture was then heated at 
reflux (about 78.degree. C.) for 16 hours under nitrogen. A clear, pale 
yellow solution was obtained, containing a hydroxy functionalized 
fluorochemical oligomer of average molecular weight about 2,200. Gas 
chromatography indicated that virtually all reagents had been reacted. The 
reaction mixture was cooled to about 45.degree. C. under nitrogen and 
about 60 g ethyl acetate was added. A Dean Stark trap was set up and 20 g 
ethyl acetate distilled out. The reaction mixture was cooled to about 
45.degree. C. under nitrogen; then 10.2 g (0.075 isocyanate equivalents) 
of PAPI were added together with three drops of dibutyltindilaurate. The 
reaction mixture was heated at reflux (about 78.degree. C.) under nitrogen 
for 5 hours, then cooled to about 50.degree. C. under nitrogen. After 
addition of 4.3 g 2-butanone oxime (0.05 mole), the reaction mixture was 
heated at 70.degree. C. for 1 hour. A clear, brown solution was obtained, 
which was free of isocyanate groups (infrared analysis). 
The oligomeric fluorochemical urethane product was emulsified and tested 
according to the procedures described and used for Example 30. Two 
commercially available fluorochemical agents were also evaluated. The 
fabric used was 100% cotton. The results are shown in Table 8. 
TABLE 8 
______________________________________ 
Treatment with 
Composition of 
Initial 5 Launderings 
1 Dry Cleaning 
Example OR SR OR SR OR SR 
______________________________________ 
31 6 100 5 90 5 100 
AG-310* 2 100 1 60 2 70 
Oleophobol PF** 
5 100 2 90 3 100 
______________________________________ 
*AG-310 is a fluorochemical containing commercial product available from 
Asahi Glass Co., Ltd. 
**Oleophobol PF is a fluorochemical containing product available from 
Chemische Fabrik Pfersee. 
As can be seen, Examples of the invention give excellent results, compared 
to commercially available products, even on fabrics which are known to 
those skilled in the art to be difficult to treat. 
Example 32 
In this example, a fluorochemical thiol of the invention was added across 
the triple bond of propargyl alcohol and the resulting adduct converted 
into a blocked oligomeric urethane derivative. Into a 500 mL three-necked 
flask, fitted with a reflux condenser, a thermometer, and a stirrer, were 
placed 48 g (0.1 mole) of C.sub.8 F.sub.17 CH.sub.2 CH.sub.2 SH as 
prepared in Example 15, 2.8 g (0.05 mole) of propargyl alcohol, 20 g 
methyl ethyl ketone and 0.15 g AIBN. The reaction mixture was degassed and 
heated at reflux (about 76.degree. C.) under nitrogen. After 6 hours, 
another 0.15 g AIBN was added, and the reaction continued for 15 hours at 
reflux under nitrogen to yield a clear, yellow solution. Gas 
chromatography indicated about 10% residual fluorochemical thiol. The 
reaction mixture was cooled to about 40.degree. C. under nitrogen; then 40 
g methyl ethyl ketone, 20.4 g (0.15 isocyanate equivalents) of PAPI and 
three drops of dibutyltindilaurate were added. The reaction mixture was 
heated at reflux under nitrogen for 5 hours. The reaction mixture was 
cooled again to about 50.degree. C. under nitrogen; then 8.2 (0.01 mole) 
of 2-butanone oxime was added, and the reaction mixture heated at 
70.degree. C. for 1 hour to yield a clear brown solution containing an 
oligomeric urethane derivative having blocked isocyanate groups and one 
hydroxy functionalized adduct of the fluorochemical thiols of this 
invention. The reactions are shown in the following scheme: (See U.S. Pat. 
No. 4,158,672, Ex. 1) 
##STR10## 
The product was emulsified following the procedure outlined in Example 30. 
Further compositions (Examples 33 and 34) using this procedure and 
emulsification procedure were prepared and are shown in Table 9. 
TABLE 9 
__________________________________________________________________________ 
EQUIVALENTS 
RATIO 
FC FUNCTIONAL A/B/C/2- 
INTERMEDIATE 
ALKYNE ISOCYANATE 
BUTANONE 
EX. A B C OXIME 
__________________________________________________________________________ 
33 Example 15 
2,4- TDI* 4/1/2/1 
hexadiyne 
1,6-diol 
34 Example 15 
2,4- PAPI 4/1/3/2 
hexadiyne- 
1,ol 
__________________________________________________________________________ 
*Toluene Diisocyanate 
The fluorochemical oligomeric urethane materials of Examples 33 and 34 were 
used to treat a polyester/cotton 65/35 blend fabric at 0.3% by weight of 
fluorochemical on fabric by the methods described above. Test results are 
shown in Table 10. 
TABLE 10 
______________________________________ 
Treatment with 5 1 Dry 
Composition of 
Initial Launderings 
Cleaning 
Example OR SR OR SR OR SR 
______________________________________ 
32 6 100 4 90 4 90 
33 3 90 1 50 2 70 
34 7 100 6 80 5 80 
______________________________________ 
As can be seen from the data, excellent results were obtained using the 
fluorochemical compositions of this invention. 
Example 35 
Into a carefully dried 500 mL three-necked flask, fitted with a condenser, 
stirrer, and thermometer, were placed 15.3 g (0.1 mole) of POCl13 (under 
nitrogen) and 20 g toluene. Deionized water (1.8 g, 0.1 mole) was added 
dropwise under vigorous stirring over about 15 minutes. An exotherm of 
about 25.degree. C. was observed and HCl was liberated. The reaction was 
heated to 70.degree. C. until no more HCl was liberated. Then 46.4 g (0.1 
mole) of C.sub.8 F.sub.17 CH.sub.2 CH.sub.2 OH, as prepared in Example 12, 
was added over 15 minutes. The reaction mixture was heated at 90.degree. 
C. under a gentle nitrogen flow until no more HCl was liberated (about 3 
hours). The reaction was cooled to 50.degree. C. under nitrogen; then 1.8 
g (0.1 mole) of deionized water was added. The reaction mixture was heated 
to 90.degree. C. under a gentle N.sub.2 flow until no more HCl was 
liberated (about 2 hours). Then a gentle vacuum (by aspirator) was used to 
remove the last traces of HCl. Deionized water (200 g) was then added and 
all the toluene was distilled off. The reaction mixture was neutralized to 
pH of 8 using 10% aqueous NH.sub.4 OH and then diluted to 10% solids with 
isopropanol and water. (Final ratio of water/isopropanol was 70/30.) A 
sample of the resulting clear solution was analyzed by gas chromatography 
(after reacting with diazomethane) and was shown to contain approximately 
3% unreacted alcohol, 85% monoester, 10% diester, and 2% triester. 
The materials of the invention were diluted in water to 0.05% (500 ppm) 
and/or 0.01% (100 ppm), and the surface tension of the aqueous solution 
was measured using a Du Nouy tensiometer. Foam height was measured as 
volume in a graduated cylinder. Half-life time (t 1/2) is the time for 
half the liquid present in the foam to drain from the foam. The foam was 
generated by a wire wisk in a Hobart mixer. Thus, 200 mL of surfactant 
solution to be tested is placed in a bowl of Hobart Model N-50 mixer 
equipped with a wire wisk stirrer and stirred for 3 minutes at medium 
speed (setting 2=300 rpm). The foam produced was immediately transferred 
to a 4000 mL graduated cylinder for measuring foam height and half-life 
time. 
Examples 36-39, Comparative Examples C6-C11 
Using the synthetic procedure of Example 35, further examples (36-39) and 
Comparative Examples (C6-C11) were prepared as shown in Table 11. 
TABLE 11 
______________________________________ 
Ex. Fluorochemical Alcohol Used 
______________________________________ 
36 C.sub.8 F.sub.17 CH.sub.2 CH.sub.2 OH from Example 12, containing 
44% linear 
material 
37 C.sub.4 F.sub.9 CH.sub.2 CH.sub.2 OH from Example 13 
38** C.sub.10 F.sub.21 CH.sub.2 CH.sub.2 OH from Example 14, containing 
65% linear 
material 
39 C.sub.10 F.sub.21 CH.sub.2 CH.sub.2 OH containing 40% linear 
material 
C6 C.sub.8 F.sub.17 SO.sub.2 N(C.sub.2 H)CH.sub.2 CH.sub.2 OH N-ethyl 
perfluorooctane- 
sulfonamido ethanol (available from 3M) 
C7** CnF2n+1CH.sub.2 CH.sub.2 OH &lt;n&gt; = 8 (available from DuPont) 
C8* C.sub.10 F.sub.21 CH.sub.2 CH.sub.2 OH (available from Hoechst) 
C9 Zonyl FSP (ammonium salt of a fluorochemical phosphate mixture, 
available from DuPont) 
C10 Isomers of C.sub.6 F.sub.11 --CF.sub.2 OCF(CF.sub.3)CH.sub.2 OH as 
described in EP 
314,380 
C11 CF.sub.3 (CF.sub.2).sub.3 OCF(CF.sub.3)CF.sub.2 OCF(CF.sub.3)CH.sub.2 
OH 
______________________________________ 
*The ammonium salts of the phosphate esters were insoluble in 
water/isopropanol mixtures, even at very low concentrations. 
**The reaction products had to be diluted to 5% solids in 
water/isopropanol prior to testing. 
Example 40 
Into a 500 mL three-necked flask fitted with a stirrer, a reflux condenser, 
and a thermometer, were placed 27.6 g (0.1 mole) of 
##STR11## 
(as prepared in Example 26), 26.4 g (0.1 mole) of C.sub.4 F.sub.9 CH.sub.2 
CH.sub.2 OH (as prepared in Example 13) and 60 g benzene. Using a Dean 
Stark trap, 20 g benzene was distilled out. The reaction was cooled to 
about 40.degree. C. under N.sub.2, and then 0.25 g of boron 
trifluoride-etherate complex in ether was added. An immediate exotherm was 
observed of about 10.degree. C. The reaction was heated at 75.degree. C. 
under nitrogen for 5 hours, during which time a clear brown solution was 
formed. At room temperature, two liquid phases were obtained. The benzene 
layer containing the products was removed. The reaction mixture was 
analyzed by gas chromatography and found to contain about 15% unreacted 
C.sub.4 F.sub.9 CH.sub.2 CH.sub.2 OH alcohol, about 70% monoadduct of 1 
mole alcohol reacted with 1 mole epoxide, about 10% of diadduct of 1 mole 
alcohol reacted with 2 moles epoxide and about 3% of higher homologues. 
The reaction product was converted into a mixture of phosphate esters and 
their ammonium salts following the procedure described in Example 35. 
Example 41 
Following the procedure outlined in Example 25, the reaction product of 2 
moles C.sub.4 F.sub.9 CH.sub.2 CH.sub.2 SH, as prepared in Example 16, and 
1 mole of propargylalcohol, CH.tbd.CCH.sub.2 OH, was prepared. The 
resulting adduct containing hydroxyl functionality was converted into the 
mixture of phosphate esters and their ammonium salts following the 
procedure described in Example 35. 
Example 42 
Into a 500 mL three-necked flask, fitted with a stirrer, a reflux 
condenser, and a thermometer were placed 6.7 g malic acid (0.05 mole), 
26.4 g (0.1 mole) C.sub.4 F.sub.9 CH.sub.2 CH.sub.2 OH as prepared in 
Example 13), 30 g methylisobutylketone and 0.2 g p-toluenesulfonic acid. 
The mixture was heated at reflux (about 98.degree. C.) and H2O was 
collected in a Dean Stark trap. After 6 hours of reflux, 1.7 g H.sub.2 O 
were trapped and the reaction stopped. All reaction solvent was removed. A 
diester alcohol of structure C.sub.4 F.sub.9 CH.sub.2 CH.sub.2 
OC(O)CH.sub.2 CH(OH)C(O)OCH.sub.2 CH.sub.2 C.sub.4 F.sub.9 was formed, 
which was subjected to the synthetic procedure followed in Example 35 to 
make ammonium salts of phosphate esters. 
TABLE 12 
______________________________________ 
FOAM HALF-LIFE SURFACE 
PRODUCT HEIGHT TIME TENSION 
OF (VOLUME) (SEC) (dyne/cm) 
EXAMPLE 500 ppm 500 ppm 500 ppm 
500 ppm 
______________________________________ 
35 200 &lt;30 sec. 17.5 18.1 
36 400 &lt;30 sec. 18.5 25.7 
37 400 &lt;30 sec. 33.3 44.9 
38 400 &lt;30 sec. 16.4 18.9 
39 400 &lt;30 sec. 18.7 24.3 
40 1100 1 min. 15 sec. 
21.2 29.3 
41 1000 50 sec. 21.7 36.7 
42 200 &lt;30 sec. 21.3 28.5 
C6 1600 4 min 10 sec. 
17.2 18.5 
C7 200 &lt;30 sec. 17.6 26.0 
C8 insoluble 
C9 300 &lt;30 sec. 18.0 26.6 
C10 400 &lt;30 sec. 20.4 26.8 
C11 300 &lt;30 sec. 29.5 35.8 
______________________________________ 
The data shows that the surfactants of this invention (compare, for 
example, Example 35 to Comparative Examples C6 and C7) have unexpected 
properties: low foaming and low surface tension in water. Compared to 
sulfonamido linking group containing derivatives (Comparative Example 6) 
our materials are low foaming, and compared to straight-chain derivatives 
(Comparative Example C7), the materials of this invention give lower 
surface tensions at equal perfluorinated chain lengths. The solubility of 
materials of this invention in aqueous systems is much better than their 
analogues (compare Examples 38 and 39 to Comparative Example C8. 
Compositions with 100% straight-chain materials give good properties but 
are usually poorly soluble at perfluorinated chain length of 8 carbons or 
more, and with 100% branched-chain materials (Comparative Example 10 and 
11) are very soluble even at long carbon chains, e.g. C.sub.10 or higher, 
but they are not as good for imparting lower surface tension. As Examples 
35, 36, and 38 show, the preferable compositions contain from 45% to 95% 
straight perfluoroalkyl chains (5-55% branched) and more preferably 
contain from 50% to 85% straight-chain linear materials (15%-50% 
branched). 
Example 43 
Into a carefully dried 500 mL three-necked flask, fitted with a reflux 
condenser, thermometer, and a stirrer, were placed 46.4 g (0.1 mole) of 
C.sub.8 F.sub.17 CH.sub.2 CH.sub.2 OH (as prepared in Example 12) and 20 g 
dry dioxane under nitrogen at room temperature. Then, 0.1 mole 
chlorosulfonic acid ClSO.sub.3 H (12.7 g) was added dropwise over about 30 
minutes. An exotherm and formation of HCl was observed. The reaction was 
heated at 70.degree. C. under nitrogen until no more HCl could be detected 
(about 4 hours). A vacuum was then applied by aspirator to remove all 
residual HCl, and 200 g deionized water added and dioxane stripped off. 
The reaction mixture was neutralized to PH of 8 using 10% aqueous NH.sub.4 
H and then diluted to 10% solids with 70/30 water/isopropanol. A clear 
yellow solution resulted containing the ammonium salt of the 
fluorochemical sulfate, C.sub.8 F.sub.17 CH.sub.2 CH.sub.2 OSO.sub.3 
NH.sub.4. 
Example 44, Comparative Examples C12, C13 
Using the same procedure as in Example 43, Example 44 and Comparative 
Examples C12 and C13 were made (as shown in Table 13). 
TABLE 13 
______________________________________ 
EX. FLUOROCHEMICAL ALCOHOL USED 
______________________________________ 
44 C.sub.8 F.sub.17 CH.sub.2 CH.sub.2 OH from Example 12, containing 
44% straight-chain 
material. 
C12 C.sub.8 F.sub.17 SO.sub.2 N(C.sub.2 H)CH.sub.2 CH.sub.2 OH 
(available from 3M Company) 
C13* C.sub.n F2.sub.n +1CH.sub.2 CH.sub.2 OH &lt;n&gt; = 8 (available from 
DuPont) 
______________________________________ 
*A dilution to 5% had to be made using 50/50 water/isopropanol as solvent 
mixture in order to obtain a clear solution. 
The fluorochemical ammonium sulfate salts were tested as outlined under 
Example 35. The results of testing are shown in Table 14. 
TABLE 14 
______________________________________ 
PRODUCT FOAM SURFACE TENSION 
OF HEIGHT t 1/2 sec (dyne/cm) 
EXAMPLE 500 ppm 500 ppm 500 ppm 500 ppm 
______________________________________ 
43 400 &lt;30 sec 19.5 22.8 
44 800 &lt;30 sec. 20.5 26.3 
C12 2200 6 min. 5 sec. 
17.1 18.2 
C13 400 &lt;30 sec. 23.3 29.5 
______________________________________ 
The data shows that the materials of this invention are generally low 
foaming and impart low surface tension. 
Example 45 
(See Example 1, U.S. Pat. No. 4,167,639) 
Into a 500 mL three-necked flask, fitted with a condenser, a thermometer, 
and a stirrer, were placed 52.8 g (0.2 mole) of C.sub.4 F.sub.9 CH.sub.2 
CH.sub.2 OH as prepared in Example 13, 9.8 g maleic anhydride (0.1 mole) 
and 0.2 g sulfuric acid (95%). The reaction mixture was heated under 
nitrogen to 140.degree. C. Water formed in the reaction was trapped in a 
Dean Stark collector. After about 6 hours of reaction, 1.7 mL water was 
obtained. The reaction mixture was a dark brown oil containing an 
unsaturated diester obtained from the ring opening and esterification 
reaction. The reaction mixture was cooled to room temperature, and 160 g 
deionized water, 80 g isopropanol and 19 g (0.1 mole) sodium metabisulfite 
(Na.sub.2 S.sub.2 O.sub.5) was added. The two-phase mixture was degassed, 
then heated at reflux under nitrogen for 15 hours. A clear, one-phase, 
brown solution was obtained containing the diester sulfosuccinate sodium 
salt product NMR analysis confirmed the structure to be C.sub.4 F.sub.9 
CH.sub.2 CH.sub.2 OC(O)CH.sub.2 CH(SO.sub.3 Na)C(O)OCH.sub.2 CH.sub.2 
C.sub.4 F.sub.9. The reaction mixture was diluted to 10% solids to give a 
final solvent ratio of water/isopropanol =65/35. 
Example 46, Comparative Examples C14, C15 
Example 46 and Comparative Examples C 14 and C 15 were prepared as 
described above in Example 44. The reactants are shown in Table 15. 
TABLE 15 
______________________________________ 
RATIO FC 
ALCOHOL 
TO SUL- 
FLUOROCHEMICAL MALEIC FONATING 
EX. ALCOHOL ANHYDRIDE* AGENT 
______________________________________ 
46 C.sub.8 F.sub.17 CH.sub.2 CH.sub.2 OH 
1:1 Na.sub.2 SO.sub.3 
(Example 12) 
C14 C.sub.4 F.sub.9 CH.sub.2 CH.sub.2 OH 
2:1 Na.sub.2 S.sub.2 O.sub.5 
(available from Asahi Glass, 
100% linear) 
C15 C.sub.n F2.sub.n+ 1CH.sub.2 CH.sub.2 OH &lt;n&gt; = 8 
1:1 Na.sub.2 SO.sub.3 
(available from DuPont) 
______________________________________ 
*1:1 ratios yield monoester sulfosuccinate product; 2:1 ratios yield 
diestersulfosuccinate product. 
The product of Examples 45, 46, and C14 and C15 were tested as described in 
Example 35. The results are shown in Table 16. 
TABLE 16 
______________________________________ 
SURFACE TENSION 
PRODUCT (dynes/cm) 
OF EXAMPLE 500 ppm 100 ppm 
______________________________________ 
45 17.7 24.2 
46 20.1 22.0 
C14 21.7 30.5 
C15 20.5 29.5 
Hoe S-2407* 38.8 -- 
______________________________________ 
*A sulfosuccinate diester sodium salt available from Hoechst. 
The data shows that materials of this invention impart lower surface 
tension values in water than their straight-chain analogues. 
Example 47 
Surfactants can also be made by Michael addition of R.sub.fsb -thiols of 
the invention to carbon-carbon double bonds containing an electron 
withdrawing group. Into a 500 mL three-necked flask fitted with a stirrer, 
thermometer, and reflux condenser, were placed 20.7 g (0.1 mole) of 
N-(3-sulfo-2,2-dimethylpropyl) acrylamide (AMPS), 50 g of dimethyl 
formamide (DMF) and 6.9 g (0.05 mole) of potassium carbonate. The mixture 
was stirred vigorously for 15 minutes. A clear, colorless solution 
resulted. Then 48.0 g (0.1 mole) of C.sub.8 F.sub.17 CH.sub.2 CH.sub.2 SH 
and 0.01 g KOH were added. The reaction was heated at 70.degree. C. for 8 
hours. Gas chromatography analysis indicated that virtually no starting 
R.sub.fsb -thiol was left. A clear solution was obtained at 10% dilution 
using water/isopropanol 65/35 as diluent. NMR analysis confirmed the 
structure to be C.sub.8 F.sub.17 CH.sub.2 CH.sub.2 SCH.sub.2 CH.sub.2 
C(O)NHCH.sub.2 C(CH.sub.3).sub.2 CH.sub.2 SO.sub.3 K. 
Examples 48-54, Comparative Examples C16, C17 
Example 48-54 and Comparative Examples 16 and 17 were prepared as in 
Example 47. The reactants are shown in Table 17. 
TABLE 17 
______________________________________ 
FLUOROCHEMICAL UNSATURATED 
EXAMPLE THIOL COMPOUND 
______________________________________ 
48 C.sub.8 F.sub.17 CH.sub.2 CH.sub.2 SH 
AMPS - sodium salt 
(Example 15) 
49 C.sub.8 F.sub.17 CH.sub.2 CH.sub.2 SH 
acrylic acid - sodium salt 
(Example 15) 
50 C.sub.8 F.sub.17 CH.sub.2 CH.sub.2 SH 
Carbowax .TM. 750 acrylate 
(Example 15) (CW750 is a methoxy 
polyethylene glycol available 
from Union Carbide) 
51 C.sub.10 F.sub.21 CH.sub.2 CH.sub.2 SH 
Carbowax .TM. 750 acrylate 
(Example 17) 
52 C.sub.10 F.sub.21 CH.sub.2 CH.sub.2 SH 
Carbowax .TM. 750 acrylate 
(Example 18) 
53 C.sub.8 F.sub.17 CH.sub.2 CH.sub.2 SH 
dimethylamino ethyl acrylate, 
(Example 15) quaternized with 
diethylsulfate 
54 C.sub.8 F.sub.17 CH.sub.2 CH.sub.2 SH 
dimethylamino ethyl acrylate, 
(Example 15) reacted with propane sultone 
C16 C.sub.10 F.sub.21 CH.sub.2 CH.sub.2 SH 
Carbowax .TM. 750 acrylate 
(available from Atochem) 
C17 C.sub.n F.sub.2n+1 CH.sub.2 CH.sub.2 SH* 
Carbowax .TM. 750 acrylate 
______________________________________ 
*Made from DuPont tetrahydroiodide following procedure of Example 15. 
All fluorochemical surfactant materials of Examples 48-54 and Comparative 
Examples C16-C17 were tested as described in Example 35. The results are 
shown in Table 18. 
TABLE 18 
______________________________________ 
SURFACE TENSION 
PRODUCT (dynes/cm) 
OF EXAMPLE 500 ppm 100 ppm 
______________________________________ 
47 19.0 24.0 
48 18.7 24.0 
49 17.5 21.7 
50 18.5 23.4 
51 17.0 19.5 
52 18.7 19.8 
53 18.7 19.8 
54 18.1 19.5 
C16 insoluble 
C17 20.0 26.8 
______________________________________ 
The data shows that products of the invention impart very low surface 
tensions, and have good solubility, in aqueous media up to a 
perfluorinated chain length of 10 carbons. These results also indicate 
that, for fluorochemical surfactant compositions of this invention, it is 
preferred that at least 40% of the compounds in the mixture contain 
straight-chain perfluoroalkyl group and more preferably at least 60% 
contain a straight-chain perfluoroaklyl group. 
Example 55 
In this example, the Michael addition of amines (or polyamines) to 
acrylates of this invention described. Into a 500 mL three-necked flask, 
fitted with a reflux condensor, a thermometer, and a stirrer, were placed 
10.3 g (0.05 mole) AMPS, 80 g DMF and 3.6 g (0.025 mole) of K.sub.2 
CO.sub.3. The reaction was stirred vigorously at room temperature. A clear 
solution was obtained after 15 minutes. Then 25.9 g (0.05 mole) of C.sub.8 
F.sub.17 CH.sub.2 OCOCH.dbd.CH.sub.2, as prepared in Example 20, was added 
followed by 3 g (0.03 mole) of ethylene diamine (EDA). An exotherm of 
10.degree. C. was observed. The reaction was heated at about 50.degree. C. 
for 3 hours. Gas chromatography indicated that essentially no reagents 
were left. The reaction mixture was diluted to 5% solids in 
water/isopropanol 50/50. The product mixture was tested as above in 
Example 35. NMR analysis confirmed the product structure to be C.sub.8 
F.sub.17 CH.sub.2 CH.sub.2 OC(O)CH.sub.2 CH.sub.2 NHCH.sub.2 CH.sub.2 
NHCH.sub.2 CH.sub.2 C(O)NHCH.sub.2 C(CH.sub.3).sub.2 CH.sub.2 SO.sub.3 K. 
Examples 56-65 
Examples 56-65 were prepared as in Example 55. The reactants are shown in 
Table 19. 
TABLE 19 
__________________________________________________________________________ 
FLUOROCHEMICAL COREAGE 
MOLAR 
ACRYLATE AMINE NT RATIO 
EX. A B C A/B/C 
__________________________________________________________________________ 
56 C.sub.8 F.sub.17 CH.sub.2 CH.sub.2 OCOCH=CH.sub.2 
EDA.sup.a 
AMPS-Na.sup.+ 
1/1/1 
(Example 20) 
57 C.sub.8 F.sub.17 CH.sub.2 CH.sub.2 OCOCH=CH.sub.2 
DMAPA.sup.b 
AMPS-K.sup.+ 
1/1/1 
(Example 20) 
58 C.sub.8 F.sub.17 CH.sub.2 CH.sub.2 OCOCH=CH.sub.2 
EDA CW750 1/1/1 
(Example 20) acrylate 
C59 CnF2n + 1 CH.sub.2 CH.sub.2 OCOCH=CH.sub.2 
EDA CW750 1/1/1 
&lt;n&gt; = 8 acrylate 
(available from DuPont) 
60 C.sub.8 F.sub.17 CH.sub.2 CH.sub.2 OCOCH=CH.sub.2 
EDA acrylic 
1/1/1 
(Example 20) acid K.sup.+ 
61.sup.c 
C.sub.8 F.sub.17 CH.sub.2 CH.sub.2 OCOCH=CH.sub.2 
EDA DMAEMA/ 
1/1/1 
(Example 20) DES 
62.sup.f 
C.sub.8 F.sub.17 CH.sub.2 CH.sub.2 OCOCH=CH.sub.2 
DMAPA propane 
1/1/2 
(Example 20) sultone 
63 C.sub.4 F.sub.9 CH.sub.2 CH.sub.2 OCOCH=CH.sub.2 
EDA AMPS-Na.sup.+ 
2/1/1 
(Example 21) 
64 C.sub.4 F.sub.9 CH.sub.2 CH.sub.2 OCOCH=CH.sub.2 
DETA.sup.d 
AMPS-Na.sup.+ 
3/1/1 
(Example 21) 
65 C.sub.4 F.sub.9 CH.sub.2 CH.sub.2 OCOCH=CH.sub.2 
TETA.sup.c 
AMPS-Na.sup.+ 
4/1/3 
(Example 21) 
__________________________________________________________________________ 
.sup.a EDA represents ethylene diamine 
.sup.b DMAPA represents dimethylaminopropylamine 
.sup.c DMAEMA/DES represents dimethylaminoethylacrylate, the tertiary 
nitrogen being quaternized with diethylsulfate (DES). Structure was 
confirmed by NMR to be C.sub.8 F.sub.17 CH.sub.2 CH.sub.2 OC(O)CH.sub.2 
CH.sub.2 NHCH.sub.2 CH.sub.2 NHCH.sub.2 CH.sub.2 C(O)OCH.sub.2 CH.sub.2 
N.sup.+ (CH.sub.3).sub.2 CH.sub.2 CH.sub.3 !CH.sub.3 CH.sub.2 
SO.sup.-.sub.3 
.sup.d DETA represents diethylene triamine 
.sup.e TETA represents triethylene tetramine 
.sup.f NMR confirmed structure to be 
##STR12## 
- The above materials were tested as surfactants in water as in Example 
35. The results are shown in Table 20. 
TABLE 20 
______________________________________ 
SURFACE TENSION 
PRODUCT (dynes/cm) 
OF EXAMPLE 500 ppm 100 ppm 
______________________________________ 
55 20.1 26.2 
56 20.5 26.0 
57 19.7 25.4 
58 18.4 22.6 
C59 18.8 25.6 
60 19.0 22.7 
61 19.9 21.3 
62 18.9 20.7 
63 18.7 25.8 
64 17.5 24.5 
65 22.0 29.8 
______________________________________ 
The data shown that materials of the invention give very good surfactant 
properties. 
Example 66 
Into a 500 mL three-necked flask, fitted with a stirrer, a thermometer, and 
a reflux condenser, were placed 15 g of C.sub.8 F.sub.17 CH.sub.2 CH.sub.2 
OCOCH.dbd.CH.sub.2 as prepared in Example 20, 35 g of Pluronic 44 
diacrylate (the diacrylate ester of Pluronic 44, a diol containing block 
segments of oxyethylene and oxypropylene, available from BASF), 0.3 g 
n-octylmercaptan, 0.3 g AIBN and 35 g ethyl acetate. The reaction was 
warmed to about 40.degree. C. and degassed three times using an aspirator 
vacuum. The reaction was heated at reflux (about 78.degree. C.) under 
nitrogen and continued for 15 hours. Gas chromotagraphy indicated that 
only traces of starting materials were left. Ethyl acetate was distilled 
off (aspirator vacuum) to yield a clear, viscous solution containing a 
fluorochemical nonionic surfactant of this invention. 
Example 67 
Into a 500 mL three-necked flask, fitted with a condenser, a thermometer, 
and a stirrer, was placed 20.7 g (0.1 mole) AMPS, 50 g DMF and 10.5 g (0.1 
mole) diethanolamine under vigorous stirring at room temperature. After 15 
minutes, a colorless solution was obtained. Then 9.6 g (0.02 mol) C.sub.8 
F.sub.17 CH.sub.2 CH.sub.2 SH (Example 15), was added together with 0.2 g 
AIBN. The reaction mixture was warmed to about 50.degree. C. and degassed 
using an aspirator vacuum. The reaction mixture was heated at 85.degree. 
C. under nitrogen for 15 hours. A clear yellow solution was obtained after 
filtration. NMR analysis confirmed the oligomeric product 
##STR13## 
NH.sub.2 (CH.sub.2 CH.sub.2 OH).sub.2 where n has an average value of 
about 5. 
Example 68 
Using the same procedure as in Example 67 but using C.sub.8 F.sub.17 
CH.sub.2 CH.sub.2 I (Example 4), in place of the thiol, another adduct of 
the invention was prepared, 
##STR14## 
where n has an average value of about 5. 
Example 69 
Into a 500 mL three-necked flask of 500 mL, fitted with a reflux condenser, 
a thermometer, and a stirrer, were placed 23.3 g (0.05 mole) of C.sub.8 
F.sub.17 CH.sub.2 CH.sub.2 OH as prepared in Example 12, and 50 g 
methylethylketone (MEK). Then 20 g MEK was distilled out and trapped in a 
Dean Stark trap. The mixture was cooled to room temperature under 
nitrogen; then a Dewar condenser, filled with a dry ice/acetone mixture, 
was set up and 0.2 g boron trifluoride etherate complex in ether was 
added. Then 17.6 g (0.4 mole) of ethylene oxide were bubbled through the 
reaction solution over 2 hours and the reaction mixture heated at 
35.degree. to 40.degree. C. Then the reaction was continued for 1 hour at 
40.degree. C. until no reflux of ethylene oxide was observed. The reaction 
mixture was heated at about 70.degree. C. for 2 hours to yield a clear 
yellow-brown solution, containing a nonionic surfactant, C.sub.8 F.sub.17 
C.sub.2 H.sub.4 O(C.sub.2 H.sub.4 O).sub.n H where n has an average value 
of 8, as indicated by NMR and G/C analysis. All MEK was stripped off and 
the product was dissolved in a 70/30 mixture water/isopropanol at 10% 
solids. A clear yellow-brown solution resulted. 
Example 70 
Using the same procedure as in Example 69, a non-ionic surfactant was 
prepared using C.sub.8 F.sub.17 CH.sub.2 CH.sub.2 SH (as prepared in 
Example 15) and a mixture of ethylene oxide and propylene oxide. The molar 
ratio R.sub.fsb thiol/ethylene oxide/propylene oxide was 1/12/3. NMR shows 
the product to be primarily C.sub.8 F.sub.17 CH.sub.2 CH.sub.2 S(CH.sub.2 
CH.sub.2 O).sub.12 (CH.sub.2 CH(CH.sub.3)O).sub.3 H where the repeating 
units are randomly distributed. 
Example 71 
In a 500 mL three-necked flask, fitted with a reflux condenser, a stirrer, 
and a thermometer, were placed 10.2 g (0.1 mole) of N,N dimethyl amino 
propylamine and 50 g ethanol. The mixture was warmed to 50.degree. C. and 
47.6 g (0.1 MOLE) of 
##STR15## 
(as prepared in Example 27), were added over 30 minutes. The heating was 
continued at 60.degree. C. for 2 hours. Gas chromatography indicated that 
all the fluorochemical epoxide was consumed. Then 0.2 mole (24.4 g) of 
propane sultone was added over 15 minutes. An exotherm of about 15.degree. 
C. was observed. The heating was continued for 2 hours at 90.degree. C. to 
yield a clear brown solution. The product was diluted to 10% solids using 
deionized water. The product was primarily 
##STR16## 
Example 72 
Into a 500 mL three-necked flask, fitted with a stirrer, a reflux 
condenser, and a thermometer, were placed 4.9 g (0.05 mole) maleic 
anhydride, 10 g methyl ethyl ketone and 37.5 g (0.05 mole) of dry Carbowax 
750 (a methoxypolyethylene glycol available from Union Carbide). The 
mixture was heated at 70.degree. C. for 16 hours. After this period, no 
anhydride peak in the infrared spectrum could be detected. Then 24 g (0.05 
mole) of C.sub.8 F.sub.17 CH.sub.2 CH.sub.2 SH, as prepared in Example 15, 
were added together with 0.4 g triethylamine catalyst. Heating was 
continued for 16 hours at 60.degree. C. to yield a clear yellow-brown 
reaction solution. Gas chromatography indicated that only traces of thiol 
were left. Then the MEK was stripped off and the reaction product was 
dissolved in a 70/30 mixture of water/isopropanol at 10% solids. A clear 
solution containing a mixed anionic-nonionic surfactant was prepared by 
adding 4 g (0.05 mole) of a 50% NaOH solution in water. The product was a 
mixture of C.sub.8 F.sub.17 CH.sub.2 CH.sub.2 SCH.sub.2 (CO2Na)CH.sub.2 
C(O)O(CH.sub.2 CH.sub.2 O).sub.n CH.sub.3 and C.sub.8 F.sub.17 CH.sub.2 
CH.sub.2 SCH.sub.2 (CH.sub.2 CO2Na)C(O)O(CH.sub.2 CH.sub.2 O).sub.n 
CH.sub.3, where n has an average value of about 16. 
The products of Examples 66 to 72 were tested as surfactants in water (at 
500 ppm) as in Example 35. The results are shown in Table 21. 
TABLE 21 
______________________________________ 
PRODUCT SURFACE TENSION 
OF EXAMPLE 
NATURE OF SURFACTANT 
(dynes/cm) 
______________________________________ 
66 oligomeric nonionic 
32.1 
67 oligomeric anionic 
25.7 
68 oligomeric anionic 
23.5 
69 nonionic 21.7 
70 nonionic 23.1 
71 amphoteric 17.5 
72 mixture of anionic + nonionic 
20.7 
______________________________________ 
The data shows that surfactants of this invention exhibit very good aqueous 
surface tension properties, regardless of the nature of the polar group, 
i.e. ionic or nonionic, or of molecular weight. 
Examples 73-77, Comparative Examples C60 and C61 
Using the synthetic procedure of Example 35, several perfluoroalkyl 
group-containing phosphates having various percentages of C.sub.8 
straight-chain and branched perfluoroalkyl groups were synthesized from 
their alcohols. Their surface tensions in water were measured at 500 ppm 
and 100 ppm, and their solubilities in water at 500 ppm solids were noted. 
Alcohols used in Comparative Examples C60 and C61, purchased from 
Fluorochem Ltd., England, were 100% linear (i.e., straight-chain) C.sub.8 
tetrahydro alcohol and 100% branched C.sub.9 tetrahydro alcohol, 
respectively. Thealcohol mixtures used in Examples 73, 75 and 76 were 
blends of the alcohol used in Comparative Example C60 (100% linear or 
straight chain) and the alcohol used in Example 74 or Example 77 (both 
alcohols from Example 12). 
Results are shown in Tables 22a-b. 
TABLE 22a 
______________________________________ 
Example Fluorochemical Alcohol Used 
______________________________________ 
C60 C.sub.8 F.sub.17 CH.sub.2 CH.sub.2 OH, 100% linear 
(available from Fluorochem Ltd., England) 
73 C.sub.8 F.sub.17 CH.sub.2 CH.sub.2 OH, 80% linear 
(blend of alcohols from Ex. C60 and Ex. 74) 
74 C.sub.8 F.sub.17 CH.sub.2 CH.sub.2 OH, 74% linear 
(alcohol semi-solid phase from Ex. 12) 
75 C.sub.8 F.sub.17 CH.sub.2 CH.sub.2 OH, 65% linear 
(blend of alcohols from Ex. C60 and Ex. 77) 
76 C.sub.8 F.sub.17 CH.sub.2 CH.sub.2 OH, 55% linear 
(blend of alcohols from Ex. C60 and Ex. 77) 
77 C.sub.8 F.sub.17 CH.sub.2 CH.sub.2 OH, 44% linear 
(alcohol liquid phase from Ex. 12) 
C61 (CF.sub.3).sub.2 CF(CF.sub.2).sub.6 CH.sub.2 CH.sub.2 OH, 0% 
linear 
(avail. from Fluorochem Ltd., England) 
______________________________________ 
TABLE 22b 
______________________________________ 
Product 
% Linear Water Solub. 
Surface Tension (dynes/cm) at: 
of Ex.: 
Chains (500 ppm) 500 ppm 100 ppm 
______________________________________ 
C60 100 Borderline 17.6 21.7 
73 80 Soluble 17.4 18.7 
74 74 Soluble 17.6 18.1 
75 65 Soluble 17.4 18.6 
76 55 Soluble 18.0 20.0 
77 44 Soluble 18.5 21.4 
C61 0 Low 18.8 23.5 
______________________________________ 
The data in Tables 22a-b show a synergistic lowering of surface tension 
with the blends of C.sub.8 straight-chain and branched perfluoroalkyl 
groups, with the synergism especially prominent at 100 ppm fluorochemical 
surfactant. Optimal surface tension lowering was obtained when at least 
50%, but less than 100%, of the surfactant contained straight-chain 
perfluoroalkyl groups (Examples 73-76), with particularly good results 
when the ratio of straight-chain to branched-chain materials was within 
the range of about 65:35 (approximately 3:2) to about 80:20 (4:1). Also, 
improved water solubility of the phosphates was noted with the blends vs. 
100% straight-chain or 100% branched perfluoroalkyl groups. 
Examples 78-81, Comparative Examples C62 and C63 
Using the synthetic procedure of Example 35, several perfluoroalkyl 
group-containing phosphates having various percentages of C.sub.10 
straight-chain and branched perfluoroalkyl groups were synthesized from 
their alcohols. Their surface tensions in water were measured at 500 ppm 
and 100 ppm, and their solubilities in water at 500 ppm solids were noted. 
Alcohols used in Comparative Examples C62 and C63, purchased from 
Fluorochem Ltd., England, were 100% linear (i.e., straight-chain) C.sub.10 
tetrahydro alcohol and 100% branched C.sub.11 tetrahydro alcohol 
repectively. The alcohol mixtures used in Examples 78 and 80 were blends 
of the alcohol used in Comparative Example C62 (100% linear or straight 
chain) and the alcohol used in Example 79 (the alcohol from the solid 
phase of Example 14) or Example 81. 
Results are shown in Tables 23a-b. 
TABLE 23a 
______________________________________ 
Example Fluorochemical Alcohol Used 
______________________________________ 
C62 C.sub.10 F.sub.21 CH.sub.2 CH.sub.2 OH, 100% linear 
(available from Fluorochem Ltd., England) 
78 C.sub.10 F.sub.21 CH.sub.2 CH.sub.2 OH, 75% linear 
(blend of alcohols from Ex. C62 and Ex. 79) 
79 C.sub.10 F.sub.21 CH.sub.2 CH.sub.2 OH, 63% linear 
(alcohol semi-solid phase from Ex. 14) 
80 C.sub.10 F.sub.21 CH.sub.2 CH.sub.2 OH, 55% linear 
(blend of alcohols from Ex. C62 and Ex. 81) 
81 C.sub.10 F.sub.21 CH.sub.2 CH.sub.2 OH, 40% linear 
(alcohol liquid phase from Ex. 14) 
C63 (CF.sub.3).sub.2 CF(CF.sub.2).sub.6 CH.sub.2 CH.sub.2 OH, 0% 
linear 
(avail. from Fluorochem Ltd., England) 
______________________________________ 
TABLE 23b 
______________________________________ 
Product 
% Linear Water Solub. 
Surface Tension (dynes/cm) at: 
of Ex.: 
Chains (500 ppm) 500 ppm 100 ppm 
______________________________________ 
C62 100 Low 19.2 25.7 
78 75 Soluble 16.7 18.7 
79 63 Soluble 16.6 18.1 
80 55 Soluble 17.4 18.6 
81 40 Soluble 18.5 20.0 
C63 0 Low 20.7 25.4 
______________________________________ 
The data in Tables 23a-b show that, at 500 and 100 ppm concentrations in 
water, the phosphate surfactant blends containing greater than 50% but 
less than 100% straight-chain C.sub.10 perfluoroalkyl groups (Examples 
78-80) produce lower surface tensions than does the blend containing only 
40% straight-chain perfluoroalkyl groups (Example 81), with optimal 
results achieved when the ratio of straight-chain to branched-chain 
materials was within the range of about 55:45 (approximately 1:1) to about 
75:25 (3:1). 
The C.sub.10 phosphate blends in Tables 23a-b gave lower surface tensions 
than their C.sub.8 counterparts in Tables 22a-b, showing the advantage of 
solubilizing the solubility C.sub.10 chain. 
Phosphates containing 100% of either straight-chain or branched C.sub.10-11 
perfluoroalkyl groups (Comparative Example C62 or C63 respectively) were 
too insoluble in water to be useful surfactants. 
Examples 82-84, Comparative Examples C64 and C65 
Using the synthetic procedure of Example 43, several perfluoroalkyl 
group-containing sulfates having various percentages of C.sub.8 
straight-chain and branched perfluoroalkyl groups were synthesized from 
their alcohols. Their surface tensions in water were measured at 500 ppm 
and 100 ppm, and their solubilities in water at 500 ppm solids were noted. 
Alcohols used in Comparative Examples C64 and C65, purchased from 
Fluorochem Ltd., England, were 100% linear (i.e., straight-chain) C.sub.8 
tetrahydro alcohol and 100% branched C.sub.9 tetrahydro alcohol 
respectively. The alcohol mixture used in Examples 83 was a blend of the 
alcohol used in Comparative Example C64 (100% linear or straight chain) 
and the alcohol used in Example 84 (the alcohol from Example 12). 
Results are shown in Tables 24a-b. 
TABLE 24a 
______________________________________ 
Example Fluorochemical Alcohol Used 
______________________________________ 
C64 C.sub.8 F.sub.17 CH.sub.2 CH.sub.2 OH, 100% linear 
(available from Fluorochem Ltd., England) 
82 C.sub.8 F.sub.17 CH.sub.2 CH.sub.2 OH, 74% linear 
(alcohol mixture intermediate from Ex. 12) 
83 C.sub.8 F.sub.17 CH.sub.2 CH.sub.2 OH, 60% linear 
(blend of alcohols from Ex. C64 and Ex. 84) 
84 C.sub.8 F.sub.17 CH.sub.2 CH.sub.2 OH, 44% linear 
(alcohol liquid phase from Ex. 12) 
C65 (CF.sub.3).sub.2 CF(CF.sub.2).sub.6 CH.sub.2 CH.sub.2 OH, 0% 
linear 
(avail. from Fluorochem Ltd., England) 
______________________________________ 
TABLE 24b 
______________________________________ 
Product 
% Linear Water Solub. 
Surface Tension (dynes/cm) at: 
of Ex.: 
Chains (500 ppm) 500 ppm 100 ppm 
______________________________________ 
C64 100 Borderline 22.3 25.5 
82 74 Soluble 19.2 22.8 
83 60 Soluble 20.8 23.7 
84 44 Soluble 21.9 24.5 
C65 0 Low 23.7 28.6 
______________________________________ 
The data in Tables 24a-b show that, at 500 and 100 ppm concentrations in 
water, the sulfate surfactant blends containing greater than 50% but less 
than 100% straight-chain C.sub.8 perfluoroalkyl groups (Examples 82 and 
83) produce lower surface tensions than does the blend containing only 44% 
straight-chain perfluoroalkyl groups (Example 84), with optimal results 
obtained near a ratio of 74:26 (approximately 3:1). Sulfates containing 
100% of either straight-chain C.sub.8 or branched C.sub.8-9 perfluoroalkyl 
groups (Comparative Example C64 or C65, respectively) were too insoluble 
in water to be useful surfactants. 
Examples 85 and 86, Comparative Examples C66 and C67 
Using the synthetic procedure of Example 55 to synthesize Michael adducts 
having the composition shown in Example 58, perfluoroalkyl 
group-containing acrylates having various percentages of C.sub.8 
straight-chain and branched perfluoroalkyl groups were reacted with 
ethylene diamine (EDA) and the acrylate of Carbowax.TM. 750 
(methoxy-terminated 750 molecular weight polyoxyethylene) in a 1:1:1 molar 
ratio. Their surface tensions in water were measured at 500 ppm and 100 
ppm, and their solubilities in water at 500 ppm solids were noted. 
Acrylates used in Comparative Examples C66 and C67, purchased from 
Fluorochem Ltd., England, were derived from 100% linear (i.e., 
straight-chain) C.sub.8 tetrahydro alcohol and 100% branched C.sub.9 
tetrahydro alcohol respectively. The Michael adduct used in Examples 85 
was made from the 74% straight-chain perfluoroalkyl acrylate prepared in 
Example 20 (made in turn from the alcohol mixture prepared in Example 12). 
The Michael adduct used in Example 86 was made by reacting EDA and the 
acrylate of Carbowax.TM. 750 with an perfluoroalkyl acrylate, which in 
turn was made by reacting acrylic acid with a blend of the 100% 
straight-chain C.sub.8 F.sub.17 CH.sub.2 CH.sub.2 OH alcohol available 
from Fluorochem and the 44% linear C.sub.8 F.sub.17 CH.sub.2 CH.sub.2 OH 
alcohol from the liquid phase isolated in Example 12. 
Results are shown in Tables 25a-b. 
TABLE 25a 
______________________________________ 
Example Fluorochemical Alcohol Used 
______________________________________ 
C66 C.sub.8 F.sub.17 CH.sub.2 CH.sub.2 OH, 100% linear 
(available from Fluorochem Ltd., England) 
85 C.sub.8 F.sub.17 CH.sub.2 CH.sub.2 OH, 74% linear 
(alcohol mixture intermediate from Ex. 12) 
86 C.sub.8 F.sub.17 CH.sub.2 CH.sub.2 OH, 65% linear 
(blend of alcohols from Ex. C60 and Ex. 77) 
C67 (CF.sub.3).sub.2 CF(CF.sub.2).sub.6 CH.sub.2 CH.sub.2 OH, 0% 
linear 
(avail. from Fluorochem Ltd., England) 
______________________________________ 
TABLE 25b 
______________________________________ 
Product 
% Linear Water Solub. 
Surface Tension (dynes/cm) at: 
of Ex.: 
Chains (500 ppm) 500 ppm 100 ppm 
______________________________________ 
C66 100 Borderline 18.6 25.0 
85 74 Soluble 18.4 22.1 
86 65 Soluble 18.6 23.7 
C67 0 Low 20.6 28.1 
______________________________________ 
The data in Tables 25a-b show that, at 100 ppm concentration in water, the 
Michael adduct surfactant blends containing greater than 50% but less than 
100% straight-chain C.sub.8 perfluoroalkyl groups (Examples 85 and 86) 
produce lower surface tensions than does the Michael adduct containing 
100% of straight-chain C.sub.8 perfluoroalkyl groups (Comparative Example 
C66), with optimal results occuring at ratios of straight-chain to 
branch-chain materials within the range from about 65:35 (approximately 
3:1) to about 74:26 (approximately 3:1). The Michael adduct containing 
100% of branched C9 perfluoroalkyl groups (Comparative Example C67) was 
too insoluble in water to be a useful surfactant. 
Example 87, Comparative Examples C68 and C69 
Using the synthetic procedure of Example 71 to synthesize propane sultone 
adducts, perfluoroalkyl group-containing epoxides having various 
percentages of C.sub.8 straight-chain and branched perfluoroalkyl groups 
were reacted with N,N-dimethylaminopropylamine and propane sultone at a 
1:1:2 molar ratio. Their surface tensions in water were measured at 500 
ppm and 100 ppm, and their solubilities in water at 500 ppm solids were 
noted. Epoxides used in Comparative Examples C68 and C69, purchased from 
Fluorochem Ltd., England, were derived from 100% straight-chain (i.e., 
linear) C.sub.8 tetrahydro alcohol and 100% branched C.sub.9 tetrahydro 
alcohol respectively. The propane sultone adduct used in Examples 85 was 
made from the 74% straight-chain perfluoroalkyl epoxide prepared in 
Example 27. 
Results are shown in Tables 26a-b. 
TABLE 26a 
______________________________________ 
Example Fluorochemical Epoxide Used 
______________________________________ 
C68 C.sub.8 F.sub.17 CH.sub.2 CHCH.sub.2, 100% linear 
(available from Fluorochem Ltd., England) 
87 C.sub.8 F.sub.17 CH.sub.2 CHCH.sub.2, 74% linear 
(epoxide intermediate from Ex. 27) 
C69 (CF.sub.3).sub.2 CF(CF.sub.2).sub.6 CH.sub.2 CHCH.sub.2, 0% 
linear 
(avail. from Fluorochem Ltd., England) 
______________________________________ 
TABLE 26b 
______________________________________ 
Product 
% Linear Water Solub. 
Surface Tension (dynes/cm) at: 
of Ex.: 
Chains (500 ppm) 500 ppm 100 ppm 
______________________________________ 
C68 100 Low 20.3 26.5 
87 74 Soluble 17.8 19.8 
C69 0 Low 22.8 31.2 
______________________________________ 
The data in Tables 26a-b show that the propane sultone adduct containing 
74% straight-chain C.sub.8 perfluoroalkyl groups (Example 87) shows better 
water solubility than does the propane sultone adduct containing either 
100% of straight-chain C.sub.8 perfluoroalkyl groups (Comparative Example 
C68) or 100% of branched C.sub.9 perfluoroalkyl groups (Comparative 
Example C69), with optimal results occuring near a ratio of straight-chain 
to branched-chain material of about 74:26 (approximately 3:1). The mixed 
chain adduct in Example 87 exhibits good surface tension reduction of 
water. 
Comparative Example C70 
A polyacrylate copolymer emulsion containing 100% straight-chain 
perfluoroalkyl groups was made using the following polymerization 
procedure. 
In a 250 mL bottle were charged 47.5 g of C.sub.8 F.sub.17 CH.sub.2 
CH.sub.2 OC(O)CH.dbd.CH.sub.2 (100% straight-chain perfluoroalkyl 
group-containing acrylate monomer, available from Fluorochem Ltd., 
England), 2.5 g of isobutyl methacrylate, 93.3 g of deionized water, 23 g 
of acetone, 1.25 g of Ethoquad.TM.0 18/25 surfactant (available from Akzo 
Nobel Chemicals, Chicago, Ill.), 0.12 g of Sipomer.TM. Q-6 cationic 
monomer (available from Rhone-Poulenc, North Americal Chemicals, Cranbury, 
N.J.), 0.1 g of Vazo.TM. V-50 initiator 2,2'-azobis(2-amidinopropane) 
hydrochloride! (available from Wako Chemicals USA, Inc., Richmond, Va.), 
and 0.25 g of tert-dodecyl mercaptan. The bottle and contents were 
degassed by vacuum aspiration followed by pressurization with nitrogen. 
The polymerization was run for 16 hours at 70.degree. C. under nitrogen, 
giving an emulsion with about 30% (wt) solids. 
Examples 88-91 and Comparative Example C71 
Polyacrylate copolymer emulsions containing varying percentages of 
straight-chain and branched perfluoroalkyl groups was made using the same 
polymerization procedure as described in Comparative Example C70 except 
that the following fluoroalkyl monomers were used in place of the 100% 
straight-chain perfluoroalkyl group-containing acrylate monomer: 
______________________________________ 
Example 
Perfluoroalkyl Group-Containing Acrylate Monomer 
______________________________________ 
88 C.sub.8 F.sub.17 CH.sub.2 CH.sub.2 OC(O)CH.dbd.CH.sub.2, 85% 
straight-chain R.sub.f 
(blend of acrylate monomers from Comparative 
Example C70 and Example 89) 
89 C.sub.8 F.sub.17 CH.sub.2 CH.sub.2 OC(O)CH.dbd.CH.sub.2, 77% 
straight-chain R.sub.f 
(acrylate monomer from Example 20) 
90 C.sub.8 F.sub.17 CH.sub.2 CH.sub.2 OC(O)CH.dbd.CH.sub.2, 65% 
straight-chain R.sub.f 
(blend of acrylate monomers from Example 89 and 
Example 91) 
91 C.sub.8 F.sub.17 CH.sub.2 CH.sub.2 OC(O)CH.dbd.CH.sub.2, 44% 
straight-chain R.sub.f 
(acrylate monomer made from the tetrahydro alcohol 
of Example 12, using the procedure described in 
Example 20) 
C71 (CF.sub.3).sub.2 CF(CF.sub.2).sub.6 CH.sub.2 CH.sub.2 OC(O)CH.dbd.C 
H.sub.2, 0% straight-chain 
R.sub.f (available from Fluorochem Ltd., England) 
______________________________________ 
The quality of polyacrylate copolymer emulsions made in Examples 88-91 
(microemulsions) was clearly superior to the quality of polyacrylate 
copolymer emulsions made in Comparative Examples C70-C71 (milky 
emulsions). 
Examples 92-95 and Comparative Examples C72-C73 
The acrylate copolymer emulsions made in Examples 88-91 and Comparative 
Examples C70-C71, with varying percent straight-chain perfluoroalkyl 
groups (% SC), were applied to style #407 cotton fabric using the Padding 
Application Procedure, and the treated fabrics were evaluated for 
repellency using the Spray Rating Test (SR) and the Oil Repellency Test 
(OR), initially and after five launderings or after one dry cleaning. 
Results are set forth in Table 27. 
TABLE 27 
______________________________________ 
5 .times. 
Acrylate Launder- Dry 
Polymer: Initial: ed: Cleaned: 
Ex. Ref. % SC OR SR OR SR OR SR 
______________________________________ 
C72 C70 100 4 80 2 50 3 70 
92 88 85 5 90 3 70 4 70 
93 89 77 5 90 3 70 4 70 
94 90 65 4 80 2 50 4 70 
95 91 44 3 70 2 50 3 50 
C73 C71 0 3 70 1 50 2 50 
______________________________________ 
The data in Table 27 show that acrylate copolymers made from monomers 
containing mixtures of straight-chain and branched chain perfluoroalkyl 
groups show improved oil repellency and water spray rating when compared 
to acrylate copolymers made from monomers containing 100% straight-chain 
or branched chain perfluoroalkyl groups, initially and after either 
laundering or dry cleaning. Best results were achieved when straight-chain 
perfluoroalkyl groups were incorporated at levels of at least 50%. 
Examples 96-99 and Comparative Examples C74-C75 
Various fluorochemical urethane oligomers were prepared by reacting 
OCNC.sub.6 H.sub.4 CH.sub.2 C.sub.6 H.sub.3 (NCO)!.sub.n CH.sub.2 C.sub.6 
H.sub.4 NCO polyisocyanate with 2-butanone oxime and with the 
perfluoroalkyl tetrahydroalcohols listed below, using the synthetic and 
emulsifying procedures set forth earlier in Example 30: 
______________________________________ 
Example 
Perfluoroalkyl Group-Containing Tetrahydro Alcohol 
______________________________________ 
C74 C.sub.8 F.sub.17 CH.sub.2 CH.sub.2 OH, 100% straight-chain 
R.sub.f 
(available from Fluorochem Ltd., England) 
96 C.sub.8 F.sub.17 CH.sub.2 CH.sub.2 OH, 85% straight-chain R.sub.f 
(blend of tetrahydro alcohols from Comparative Example C74 
and Example 97) 
97 C.sub.8 F.sub.17 CH.sub.2 CH.sub.2 OH, 74% straight-chain R.sub.f 
(a tetrahydro alcohol from Example 12) 
98 C.sub.8 F.sub.17 CH.sub.2 CH.sub.2 OH, 65% straight-chain R.sub.f 
(blend of tetrahydro alcohols from Example 97 
and Example 99) 
99 C.sub.8 F.sub.17 CH.sub.2 CH.sub.2 OH, 44% straight-chain R.sub.f 
(a tetrahydro alcohol from Example 12) 
C75 (CF.sub.3).sub.2 CF(CF.sub.2).sub.6 CH.sub.2 CH.sub.2 OH, 0% 
straight-chain R.sub.f 
(available from Fluorochem Ltd., England) 
______________________________________ 
The quality of the fluorochemical urethane oligomer emulsions prepared in 
Comparative Examples C74 and C75 was inferior to those emulsions made in 
Examples 96-99, probably due to a lower solubility of the urethane 
oligomers in ethyl acetate which made emulsification far more difficult. 
The fluorochemical urethane oligomer emulsions made in Examples 96-99 and 
in Comparative Examples C74-C75 were applied to style #407 cotton fabric 
using the Padding Application Procedure and were evaluated for repellency 
using the Oil Repellency Test and the Spray Rating Test, initially and 
after laundering or dry cleaning. Test results are set forth in Table 28. 
TABLE 28 
______________________________________ 
5 .times. 
Launder- Dry 
Urethane Oligomer: 
Initial: ed: Cleaned: 
Ex. % SC OR SR OR SR OR SR 
______________________________________ 
C74 100 3 100 2 70 2 70 
96 85 3 100 3 90 3 80 
97 74 3 100 3 80 2 80 
98 65 2 100 2 80 2 80 
99 44 2 100 1 70 1 70 
C75 0 2 90 1 70 1 70 
______________________________________ 
The data in Table 28 show that the urethane oligomers made from mixed 
straight-chain and branched perfluoroalkyl groups and having at least 65% 
straight-chain groups shows improved spray rating and slightly better oil 
resistance after laundering or dry cleaning. 
Example 100 
A fluorochemical carbodiimide oligomer was prepared by reacting OCNC.sub.6 
H.sub.4 CH.sub.2 C.sub.6 H.sub.3 (NCO)!.sub.n CH.sub.2 C.sub.6 H.sub.4 
NCO polyisocyanate with a perfluoroalkyl tetrahydroalcohol having 74% 
straight-chain perfluoroalkyl groups using the following procedure. 
Into a 3-necked flask equipped with a stirrer, heating mantle, condensor 
and thermometer were charged 75 g (0.3 mol) of OCNC.sub.6 H.sub.4 CH.sub.2 
C.sub.6 H.sub.3 (NCO)!.sub.n CH.sub.2 C.sub.6 H.sub.4 NCO polyisocyanate 
(average value of n=0.7, available from Upjohn Co., Kalamazoo, Mich.) and 
40 g of dry ethyl acetate. The mixture was heated to 65.degree. C. with 
mixing under a nitrogen atmosphere. Then, using an addition funnel, a 
solution consisting of 92.8 g (0.2 mol) of the perfluoroalkyl 
tetrahydroalcohol prepared in Example 12 in 50 g of dry ethyl acetate was 
added over a 3 hour period, maintaining the reaction temperature at 
65.degree. C. After a 1 hour reaction time, 1 drop (0.03 mL) of dibutyltin 
dilaurate was added, and the reaction was cooled for an additional 3 hours 
at 70.degree. C. under nitrogen. A clear solution was obtained. 
To this urethane reaction product containing unreacted isocyanate was added 
6 g of camphene phospholene oxide catalyst and the reaction temperature 
was increased to 80.degree. C. (still under nitrogen). Gentle evolution of 
carbon dioxide was observed, suggesting carbodiimide formation. The 
reaction was allowed to run for 16 hours at 80.degree. C., after which a 
clear solution resulted. Infrared analysis indicated that all residual 
isocyanate groups from the isocyanate-alcohol reaction had reacted with 
each other to form carbodiimide groups. 
The resulting carbodiimide oligomer solution in ethyl acetate was 
emulsified in water using the same procedure as described in Example 30. 
Comparative Examples C76 and C77 
The same reaction and emulsifying procedures were conducted as described in 
Example 100 except that perfluoroalkyl tetrahydroalcohol having 100% 
straight-chain perfluoroalkyl groups (available from Fluorochem Ltd.) and 
perfluoroalkyl tetrahydroalcohol having 0% straight-chain perfluoroalkyl 
groups ((CF.sub.3).sub.2 CF(CF.sub.2).sub.6 CH.sub.2 CH.sub.2 OH, 
available from Fluorochem Ltd.) were substituted for the perfluoroalkyl 
tetrahydroalcohol having 74% straight-chain perfluoroalkyl groups for 
Comparative Examples C76 and C77 respectively. In both bases, the ethyl 
acetate solutions of the urethane intermediates and the carbodimide 
oligomers were hazy, indicating poor solubility relative to the urethane 
intermediate and carbodiimide oligomer prepared in Example 100. 
The fluorochemical carbodiimide oligomer emulsions made in Example 100 and 
Comparative Examples C76-C77 were applied to style #407 cotton fabric 
using the Padding Application Procedure and were evaluated for repellency 
using the Oil Repellency Test and the Spray Rating Test, both initially 
and after laundering or dry cleaning. Test results are set forth in Table 
29. 
TABLE 29 
______________________________________ 
5 .times. 
Carbodiimide Launder- Dry 
Oligomer: Initial: ed: Cleaned: 
Ex. % SC OR SR OR SR OR SR 
______________________________________ 
C76 100 4 70 2 50 1 0 
100 74 5 80 3 70 2 50 
C77 0 3 70 1 50 0 0 
______________________________________ 
The data in Table 29 show in all cases that carbodiimide oligomers made 
from mixed straight-chain and branched perfluoroalkyl groups exhibited 
improved spray rating and better oil repellency, both initially and after 
laundering or dry cleaning. 
Example 101 
A fluorochemical ester oligomer was prepared by reacting adipic acid with a 
perfluoroalkyl tetrahydroalcohol/epichlorohydrin adduct having 74% 
straight-chain perfluoroalkyl groups. 
The precursor perfluoroalkyl tetrahydroalcohol/epichlorohydrin adduct was 
first prepared using the following procedure. Into a 500 mL 3-necked flask 
equipped with a stirrer, heating mantle, condensor and thermometer were 
charged 92.8 g (0.2 mol) of the perfluoroalkyl tetrahydroalcohol 
previously prepared in Example 12 and 20 g of toluene under a nitrogen 
blanket. The content were warmed to about 50.degree. C., then 21 g (0.22 
mol) of epichlorohydrin was added, followed by 1 g of anhydrous SnCl.sub.4 
catalyst, resulting in an exotherm. The contents were allowed to react for 
3 hours at 50.degree. C. under nitrogen. A clear brown solution resulted, 
which, when analyzed by gas chromatography, showed the reaction product to 
consist of C.sub.8 F.sub.17 CH.sub.2 CH.sub.2 OCH.sub.2 CH(CH.sub.2 
Cl)!.sub.n OH, with 28.7% of n=0 (starting alcohol), 53.5% of n=1, 10.1% 
of n=2, 3.2% of n=3 and 4.5% of n.gtoreq.4. 
The fluorochemical ester oligomer was prepared by esterifying the precursor 
perfluoroalkyl tetrahydroalcohol/epichlorohydrin adduct with adipic acid 
using the following procedure. Toluene was stripped from the 
epichlorohydrin adduct solution at 90.degree.-110.degree. C. and aspirator 
vacuum of approximately 20 torr. Then 80 g of methyl isobutyl ketone 
(MIBK), 15.6 g (0.1 mol) of adipic acid and 0.52 g of p-toluenesulfonic 
acid catalyst were added, and the reaction mixture was heated to reflux, 
removing the water of reaction via azeotropic distillation with a 
Dean-Stark trap. After 6 hours, the reaction mixture had reached 
120.degree. C. and no further water was collected, so the reaction was 
stopped. 
The resulting ester oligomer solution in MIBK was emulsified in water using 
the same procedure as described in Example 30. 
Comparative Examples C78 and C79 
The same reaction and emulsifying procedures were conducted as described in 
Example 101 except that perfluoroalkyl tetrahydroalcohol having 100% 
straight-chain perfluoroalkyl groups (available from Fluorochem Ltd.) and 
perfluoroalkyl tetrahydroalcohol having 0% straight-chain perfluoroalkyl 
groups ((CF.sub.3).sub.2 CF(CF.sub.2).sub.6 CH.sub.2 CH.sub.2 OH, 
available from Fluorochem Ltd.) were substituted for the perfluoroalkyl 
tetrahydroalcohol having 74% straight-chain perfluoroalkyl groups for 
Comparative Examples C78 and C79 respectively. 
The fluorochemical ester oligomer emulsions made in Example 101 and 
Comparative Examples C78-C79 were applied to style #407 cotton fabric 
using the Padding Application Procedure and were evaluated for repellency 
using the Oil Repellency Test and the Spray Rating Test, both initially 
and after laundering or dry cleaning. Test results are set forth in Table 
30. 
TABLE 30 
______________________________________ 
5 .times. 
Carbodiimide Launder- Dry 
Oligomer: Initial: ed: Cleaned: 
Ex. % SC OR SR OR SR OR SR 
______________________________________ 
C78 100 6 50 1 0 0 0 
101 74 7 60 2 50 1 0 
C79 0 4 0 0 0 0 0 
______________________________________ 
The data in Table 30 show that ester oligomers made from mixed 
straight-chain and branched perfluoroalkyl groups showed improved spray 
rating and oil repellency, both initially and after laundering. The ester 
oligomers containing all straight-chain or branched perfluoroalkyl groups 
showed no oil repellency after dry cleaning. 
Various modifications and variations of this invention will become apparent 
to those skilled in the art without departing from the scope and spirit of 
this invention.