Fluorochemical surfactants of the formula ##STR1## wherein R.sub.f is perfluoroalkyl of 4-20 carbon atoms or perfluoroalkoxyperfluoroalkyl of 4-20 carbon atoms; PA0 A is straight or branched chain alkylene of 1-10 carbon atoms which is unsubstituted or substituted by halo; PA0 n is 1 to 50; PA0 R.sub.1 is hydrogen or alkyl of 1-4 carbon atoms and R.sub.2 is hydrogen or alkyl of 1-4 carbon atoms.

The instant invention relates to novel fluorinated non-ionic surfactants of 
the general formula 
##STR2## 
wherein R.sub.f is perfluoroalkyl of 4 to 20 carbon atoms; 
A is straight or branched chain alkyl of 1-10 carbon atoms which is 
unsubstituted or is substituted by chloro or fluoro; 
n is 1-50 
R.sub.1 is hydrogen or alkyl of 1-4 carbon atoms and 
R.sub.2 is hydrogen or alkyl of 1-4 carbon atoms. 
Preferably, R.sub.f is perfluoroalkyl of 4-16 carbon atoms or said 
perfluoroalkyl substituted by perfluoroalkoxy of 2-4 carbon atoms; A is 
ethylene; n is 5-25, R.sub.1 is hydrogen and R.sub.2 is hydrogen or 
methyl. Most preferably R.sub.2 is methyl. 
Where n is less than 5, the resulting compounds have little water 
solubility. However, such compounds are useful as surfactants in 
non-aqueous systems, as mold release agents in the plastics and silicone 
industry, as well as grease and oil repellants for paper. Those compounds 
wherein R.sub.1 is predominately lower alkyl are likewise characterized by 
their limited water solubility and likewise possess utility as surfactants 
in non aqueous systems, as mold release agents and as grease and oil 
repellants for paper and the like. 
Preferred compounds are those wherein R.sub.1 is at least predominately 
hydrogen and n is 5-50. Such compounds are essentially water soluble. 
Such water soluble compounds are valuable aqueous surfactants and are 
useful industrial wetting agents. Thus, they are useful wetting agents for 
biocides, cleaning compositions and detergents, as rinse-aids for cars, 
dishes and the like, as emulsifiers, and as leveling agents in the dye and 
pigment industry. 
The compounds of the instant invention are easily prepared by any one of a 
number of routes. 
For example. The compounds can be prepared conveniently by reacting a 
alkoxylated compound of the formula 
##STR3## 
with epichlorohydrin in bulk or in a common dry and aprotic solvent, 
including ketones, such as acetone or methyl ethyl ketone; ethers, such as 
diethylether, ethylenegycol-dimethylether or tetrahydrofuran; esters such 
as ethyl acetate or methyl cellosolve acetate; and amides, such as 
dimethylformamide or N-methyl pyrrolidone. A Lewis acid catalyst, such as 
boron trifluoride (usually in the form of the diethyl ether complex 
thereof) or aluminum chloride, is used to promote the formation of the 
halohydrin intermediate. If the reaction is run in the absence of a 
solvent, it is advantageously run at a temperature above the melting point 
of the alkoxylated compound with boron trifluoride-etherate. The reaction 
is ordinarily exothermic. It is generally not necessary to isolate the 
halohydrin intermediate, and the next reaction can be carried out in the 
same reaction vessel. The halohydrin intermediate has the formula 
##STR4## 
In the second step, the perfluoroalkylene mercaptan (R--A--SH) is added to 
the halohydrin intermediate, followed by the addition of an equivalent 
amount of base as an acid acceptor. This step may advantageously be 
carried out in bulk or in the presence of aprotic or protic solvents. As 
apotic solvents, there may be used those recited above for the first step. 
Suitable protic solvents include water, and alcohols such as methanol, 
ethanol, isopropanol, tert. butyl alcohol, hexyleneglycol and 
ethyleneglycol. Suitable bases include sodium hydroxide, potassium 
hydroxide, pyridine, lutidine and triethylamine. Conveniently, a solvent 
is selected which dissolves the reactants and desired product, but not the 
by-product salt, so that the salt will precipitate out as the reaction 
proceeds and can then be removed by conventional techniques, such as 
filtration. The fluorochemical surfactant product may be left in solution 
or evaporated to remove the solvent. The reaction is preferably carried 
out between about 30.degree. and 80.degree. C., under a nitrogen 
atmosphere, with stirring. There is generally an exotherm as the base is 
added to the reaction mixture. 
Alternatively, the surfactants of the instant invention may be prepared by 
first reacting equimolar amounts of perfluoroalkylene mercaptan, R.sub.f 
--A--SH, and epichlorohydrin by placing them in a reaction vessel and 
stirring the reactants in the presence of an inert solvent, such as methyl 
cellosolve acetate. Then a stoichiometric amount of a base, such as 50% 
aqueous sodium hydroxide, is slowly added to the reaction mixture. The 
resulting reaction is exothermic and the reaction temperature is 
advantageously maintained between about 20.degree.-60.degree. C. with 
stirring for B 1-3 hours. The resulting epoxide intermediate has the 
formula 
##STR5## 
The by-product salt is removed from the epoxide intermediate and any 
residual water is removed by vacuum distillation. 
The epoxide intermediate is then reacted with an equimolar amount, or a 
slight excess, of an alkoxylated compound of the formula 
##STR6## 
This reaction is advantageously conducted under substantially anhydrous 
conditions in the presence of a catalyst, such as BF.sub.3. etherate, at a 
temperature of about 30.degree.-60.degree. C. in the presence or absence 
of an inert solvent, such as methyl cellosolve acetate. In one technique, 
the catalyst is dispersed in a mixture of the alkoxylated compound and the 
solvent, and slowly added to the epoxide intermediate with stirring. 
Preferably, this reaction is carried out under a nitrogen blanket. 
The product fluorochemical surfactant may be left in solution and used as 
such, or may be evaporated or distilled under vacuum to remove the 
solvent. 
The fluorochemical surfactants of this invention are distinguished by their 
increased surface active properties vis-a-vis their related hydrocarbon 
surfactant analogs. As a result, they improve or impart properties such as 
wetting, penetration, spreading, leveling, foam stability, flow properties 
dispersion properties and oil and water repellency.