# Patent

## Title
Process for preparation of peroxides

## Abstract

wherein R.sub.f is a perfluoroalkyl, R.sub.1 is alkylene or alkyleneoxy or aminoalkylene, T is alkylene, and Z is hydrogen; hydroxy; NR.sub.3 R.sub.4, where R.sub.3 and R.sub.4 each is alkyl or together with nitrogen form a heterocyclic ring; N.sup.+ R.sub.3 R.sub.4 (R.sub.5)X.sub.z.sup.-y, where R.sub.5 is hydrogen, oxide, alkyl, or substituted alkyl, X is an anion, and y is 1 or 2; z is 0 or 1 or is --OCH.sub.2 CH.sub.2 SR.sub.1 R.sub.f ; can be prepared directly by free-radical catalyzed addition of a perfluoroalkylthiol to a vinyl ether or subsequent reaction. These compounds are useful as surfactants and oil spill collecting agents.

## Background
The novel perfluoroalkylthioethyl ether compounds of this invention are of the formula

wherein atoms or said perfluoroalkyl substituted by perfluoroalkoxy of 2 to 6 atoms; alkylenethioalkylene of 2 to 12 carbon atoms; alkylenethioalkylene of 2 to 12 carbon atoms; or alkyleneiminoalkylene of 2 to 12 carbon atoms where the imino nitrogen atom contains as a third substituent hydrogen or alkyl of 1 to 6 carbon atoms; --OCH.sub.2 CH.sub.2 SR.sub.1 R.sub.f ; --OR.sub.2, where R.sub.2 is hydrogen, alkyl of 1 to 25 carbon atoms, or acyl where said acyl is an aliphatic or aromatic carbonyl or carbamyl group of up to 25 carbon atoms. Thus, R.sub.2 can be hydrogen alkyl of 1 to 24 carbon atoms, alkanoyl of 2 to 24 carbon atoms, alkenoyl of 3 to 24 carbon atoms, benzoyl or benzoyl substituted by 1 to 3 of chloro, bromo, alkyl of 1 to 18 carbon atoms, C.sub.2 -C.sub.24 alkyl carbonate or C.sub.2 -C.sub.24 alkyenylcarbamate; --NR.sub.3 R.sub.4, where of 1 to 22 carbon atoms; or R.sub.3 and R.sub.4, together with the nitrogen to which they are bonded, form a piperazine, piperidine, morpholine or pyrrolidine ring; and --NR.sub.3 R.sub.4 (R.sub.5).sub.y X.sub.z.sup.-y where carbon atoms which is unsubstituted or substituted with; 1 or 2 hydroxyl groups, a carboxylic acid group, or an anionic function selected from sulfonate, sulfate, or carboxylate; or R.sub.3, R.sub.4 and R.sub.5 together with the nitrogen to which they are attached, represent pyridyl; lower alkanoate, lower alkylsulfonate, phenylsulfonate, tolysulfonate phosphate, sulfate, or lower alkylsulfate; must be oxygen or said alkyl substituted by an anionic function; if z is 1, R.sub.5 may not be oxygen.

Preferred compounds are those where substituted by perfluoroalkoxy of 2 to 6 carbon atoms; alkylenethioalkylene of 2 to 8 carbon atoms, alkylenethioalkylene of 2 to 8 carbon atoms, alkyleneoxyalkylene of 2 to 8 carbon atoms or alkyleneiminoalkylene of 2 to 8 carbon atoms where the imino nitrogen atom contains hydrogen or methyl as a third substituent; is an aliphatic hydrocarbon or aromatic hydrocarbon carbonyl or carbamyl group up to 18 carbon atoms, --NR.sub.3 R.sub.4, where of 1 to 6 carbon atoms; or R.sub.3 and R.sub.4, together with the nitrogen to which they are bonded, form a piperazine, piperidine, morpholine or pyrrolidine ring: --NR.sub.3 R.sub.4 (R.sub.5).sub.y X.sub.z.sup.-y, where carbon atoms which is substituted with: 1 or 2 hydroxyl groups, carboxylic acid group, or an anionic function selected from sulfonate, sulfate, or carboxylate; acetate, phosphate, sulfate, methosulfate or ethosulfate;

Particularly preferred are those compounds where where carbon atoms; --N.sup.+ R.sub.3 R.sub.4 (R.sub.5).sub.y X.sub.z.sup.-y where unsubstituted substituted by --COOH, or an anionic function selected from sulfonate, sulfate or carboxylate; methosulfate and ethosulfate;

By sulfonate, sulfate and carboxylate is meant the --SO.sub.3.sup.- and --OSO,.sub.3.sup.-, and --COO.sup.- radicals, respectively.

The novel R.sub.f -surfactants described herein can be obtained either; formula --NR.sub.3 R.sub.4 with such quaternizing agents as alkyl halides, dialkyl sulfates and the like to yield cationic surfactants or with inorganic acids or organic acids to form salts, or by reaction with such alkylation reagents as chloroacetic acid, sodium chloroacetate, propane sultone, propiolactone and the like, to yield amphoteric surfactants, Amine oxide derivatives wherein R.sub.5 is oxygen are prepared by treatment with hydrogen peroxide at about 0.degree. to 60.degree. C. --OH with anhydrides or acid halides to form esters or with isocyanates to form urethanes.

One group of preferred compounds has the formula

where especially where

Another group of preferred compounds have the formula (CH.sub.3).sub.2 and the corresponding ammonium derivatives (CH.sub.3).sub.2 C.sub.2 H.sub.5 C.sub.2 H.sub.5 SO.sub.4.sup.- and N(CH.sub.3).sub.2 N.sup.+ (CH.sub.3).sub.2 CH.sub.2 CO.sub.2.sup.- where R.sub.f is as described above.

In one embodiment the vinyl ether has the formula CH.sub.2 .dbd.CHO--T--OH where T is a straight chain alkylene of 2 to 4 carbon atoms.

In another embodiment the vinyl ether has the formula CH.sub.2 .dbd.CHO--T--NR.sub.3 R.sub.4 where T is a straght chain alkylene of 2 to 3 carbon atoms, and R.sub.3 and R.sub.4 are each independently straight chain alkyl of 1 to 3 carbon atoms; or R.sub.3 and R.sub.4 are both methyl or ethyl groups.

The vinyl ethers which are generally available and are particularly useful for this invention include:

Perfluoroalkyl thiols useful herein are well documented in the prior art. For example, thiols of the formula R.sub.f R'--SH have been described in a number of U.S. Patents including U.S. Pat. Nos. 2,894,991; 2,961,470; 2,965,677; 3,088,849; 3,172,190; 3,544,663; and 3,655,732.

Thus, U.S. Pat. No. 3,655,732 discloses mercaptans of formula

where R' is alkylene of 1 to 16 carbon atoms and R.sub.f is perfluoroalkyl and teaches that halides of formula R.sub.f --R'hal are well known. Reaction R.sub.f I with ethylene under free-radical conditions gives R.sub.f (CH.sub.2 CH.sub.2).sub.a I as is further taught in U.S. Pat. Nos. 3,088,849; 3,145,222; 2,965,659 and 2,972,638.

U.S. Pat. No. 3,655,732 further discloses compounds of formula R.sub.f --R'--X--R"--SH where R' and R" are alkylene of 1 to 16 carbon atoms, with the sum of carbon atoms of R' and R" being no greater than 25; R.sub.f is perfluoroalkyl of 4 through 14 carbon atoms and X is --S-- or --NR'" where R"' is hydrogen or alkyl of 1 through 4 carbon atoms.

U.S. Pat. No. 3,544,663 teaches that the mercaptan R.sub.f C.sub.2 CH.sub.2 SH where R.sub.f is perfluoroalkyl of 5 to 13 carbon atoms, can be prepared by reacting the perfluoroalkylalkylene iodine with thiourea or by adding H.sub.2 S to a perfluoroalkyl substituted ethylene (R.sub.f --CH.dbd.CH.sub.2), which in turn can be prepared by dehydrohalogenation of the halide R.sub.f --CH.sub.2 CH.sub.2 --hal.

The reaction of the iodide R.sub.f --R'--I with thiourea followed by hydrolysis to obtain the mercaptan R.sub.f --R'--SH is the preferred synthetic route. The reaction is applicable to both linear and branched chain iodides. U.S. Pat. No. 3,514,487 described perfluoroalkoxyalkyl iodides of general formula

where m is 1-3.

Particularly preferred herein are the thiols of formula R.sub.f CH.sub.2 CH.sub.2 SH where R.sub.f is perfluoroalkyl of 6 to 12 carbon atoms. These R.sub.f -thiols can be prepared from R.sub.f CH.sub.2 CH.sub.2 I and thiourea in very high yields.

For the addition of a perfluoroalkylthiol of formula R.sub.f R.sub.1 SH to a vinyl ether it is necessary to use an azo-type free-radical catalyst.

The reaction temperature and choice of azo-type free-radical catalyst are considered to be mutually dependent. The temperature range of 40.degree. C. to 100.degree. C. is one wherein the formation of undesirable by-products is minimized and wherein the reaction products are stable. In order to achieve a reasonable reaction rate of these temperatures, it is desirable to use an azo-type catalyst that is reactive to a reasonable extent in this temperature range. It is, therefore, preferred to use an azo-type free-radical catalyst having a 1-hour half-life temperature of 40.degree. to about 100.degree. C.

Suitable solvents are such in which the reactants are soluble at reaction temperatures and include aliphatic or aromatic hydrocarbons such as heptane, benzene, toluene, etc; chlorinated or fluorinated aliphatic or aromatic hydrocarbons such as methylene chloride, chloroform, methyl chloroform, carbon tetrachloride, trichloroethylene, perchloroethylene, Freon's such as 1,1,2-trifluoro-1.2.2-trichloroethane, etc., chlorobenzene, benzotrifluoride or hexafluoroxylene, ketones, esters and ethers such as acetone, methyl isobutyl ketone, ethyl acetate and higher homologs, dialkyl ethers, tetrahydrofuran, ethylene glycol monomethyl or monoethyl ether, ethylene glycol dimethyl or diethyl ether, and acetonitrile.

If possible it is preferred to carry out the addition reaction in bulk.

Vinyl ethers are described in "Acetylene--Its Properties, Manufacture and Uses," Vol. 2, E. Bern Ltd, London and in brochures of the GAF Corporation.

The novel surfactants of this invention are useful to improve or impart properties such as: emulsification, dispersion, and oil and water repellency. Based on these unique properties are numerous applications, some of which follow. Although applications are suggested for a particular use area, the general applicability of each concept is inferred for other applications. polymers. surfaces including natural and synthetic rubbers, resins, plastics detection. hydrocarbons the pigments are rendered non-reactive and bacteriostats encapsulated materials regulators, parasiticides, insecticides, germicides, bactericides, nematocides, microbiocides, defolients and fertilizers desalination and foaming. May improve soil suspension and decrease redeposition resistance) based. coatings.

The following examples are presented to illustrate the preparation of the novel compounds of this invention and to demonstrate their valuable surface properties and utility as oil spill collecting agents.

2-(1,1,2,2-Tetrahydroperfluorodecanethio)ethyl hydroxyethyl ether

1,1,2,2-Tetrahydroperfluorodecanethiol (4.82 g, 0.0100 mole), 2-hydroxyethyl vinyl ether (0.93 g, 0.0105 mole), and 2,2'-azobis(2-methylpropionitrile) (0.03 g) were reacted in methanol (3.5 g) at 60.degree. C. overnight. The product was distilled at 121.degree. C. under diffusion vacuum pump to yield 5.23 g product (92.1% of theory) as a white solid which was 100% pure by GLC. NMR showed proton resonances at 1.80, 1 proton, OH 2.00-2.60, 2 protons, CF.sub.2 CH.sub.2 CH.sub.2 S; 2.80, 4 protons, CF.sub.2 CH.sub.2 CH.sub.2 SCH.sub.2 CH.sub.2 O; and 3.70, 6 protons, SCH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OH. Analysis for C.sub.14 H.sub.13 F.sub.17 O.sub.2 S: Calc.: C, 29.59; H, 2.31; F, 56.83. Found: C, 29.35; H, 2.28 F, 56.19.

2-(1,1,2,2-Tetrahydroperfluorododecanethio)ethyl hydroxyethyl ether OH

1,1,2,2-Tetrahydroperfluorododecanthiol (11.60 g., 0.02 mole), 2-hydroxyethyl vinyl ether (1.76 g., 0.02 mole), and 2,2'-azobis(2-methylpropionitrile) (0.05 g.) were reacted in methanol (10 ml) at 60.degree. C. overnight. The product was distilled at 135.degree. C. under diffusion vacuum pump to yield 12.1 g (90.5% of theory) as a waxy white solid which was 96.0% pure by GLC. The melting point range was 93.0.degree. to 96.0.degree..

Analysis for C.sub.16 H.sub.13 F.sub.21 O.sub.2 S: Calc.: C, 28.76; H, 1.96; F, 59.70. Found: C, 28.60; H, 1.88 F, 59.09.

2-(1,1,2,2-Tetrahydroperfluorodecanethio)ethyl 4-hydroxybutyl ether CH.sub.2 CH.sub.2 OH

1,1,2,2-Tetrahydroperfluorodecanethiol (4.82 g, 0.0100 mole), 4-hydroxybutyl vinyl ether (1.22 g, 0.0105 mole), and 2,2'-azobis(2-methylpropionitrile) (0.03 g) were reacted in methanol (3.5 g) at 60.degree. C. overnight. The product was distilled at 132.degree. C. under diffusion vacuum pump to yield 4.19 g product (70.3% of theory) as a white solid which was 100% pure by GLC. NMR showed proton resonances at .delta.1.65, 4 protons, OCH.sub.2 CH.sub.2 CH.sub.2 OH.

Analysis for C.sub.16 H.sub.17 F.sub.17 O.sub.2 S: Calc.: C, 32.22; H, 2.87; F, 54.16. Found: C, 32.18; H, 2.87; F, 54.03.

2-(1,1,2,2-Tetrahydroperfluorodecanethio)ethyl 4-hydroxybutyl ether CH.sub.2 CH.sub.2 OH

1,1,2,2-Tetrahydroperfluorodecanethiol (11.60 g., 0.02 mole), 4-hydroxybutyl vinyl ether (2.32 g., 0.02 mole) and 2,2'-azobis-(2-methylpropionitrile) (0.05 g.) were reacted in methanol (10 ml) at 60.degree. C. overnight. The product was crystallized from methanol and distilled at 147.degree. C. under diffusion vacuum pump to yield 5.65 g. (40.6% of theory) as a waxy white solid which was 97.2% pure by GLC. The melting point range was 86.0.degree. to 87.2.degree. C.

Analysis for C.sub.18 H.sub.17 F.sub.21 O.sub.2 S: Calc.: C, 31.05; H, 2.46; F, 57.29. Found: C, 30.88; H, 2.62; F, 56.44.

2-(1,1,2,2-Tetrahydroperfluorodecanethio)ethyl 4-hydroxybutyl ether CH.sub.2 OH

1,1,2,2-Tetrahydroperfluorodecanethiol (10.00 g, 0.0229 mole), 4-hydroxybutyl vinyl ether (2.55 g, 0.0250 mole), and 2,2'-azobis-(2-methylpropionitrile) (0.05 g) were reacted at 60.degree. C. overnight. The resultant mixture was stripped of all non-product volatiles to yield 11.2 g product as a water white liquid (92.4% of theory) which was 98.9% pure by GLC. NMR showed proton resonances at .delta.1.02, 4 protons, OCH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 OH: .delta.2.00-2.60, 2 protons, CH.sub.2 CH.sub.2 CH.sub.2 ; .delta.2.23, 1 proton; CH.sub.2 OH; .delta.2.76-2.83, 4 protons, CH.sub.2 SCH.sub.2 ; .delta.3.54-3.67, 6 protons, CH.sub.2 OCH.sub.2 CH.sub.2 CH.sub.2 OH.

2-Dimethylaminoethyl 2'-(1,1,2,2-tetrahydroperfluorodecanethio) ethyl ether N(CH.sub.3).sub.2

1,1,2,2-Tetrahydroperfluorodecanethiol (15.00 g, 0.031 mole), dimethylaminoethyl vinyl ether (3.78 g, 0.033 mole), and 2,2'-azobis-(2-methylpropionitrile) (0.10 g) were reacted at 70.degree. C. for 5 hours. The resultant mixture was stripped of volatiles and distilled at 110.degree. C./0.02 mm Hg to yield 15.95 g of light yellow liquid (85.9% of theory) which was 99.6% pure by GLC. NMR showed proton resonances at .delta.2.16, 6 protons, 2.times.CH.sub.2 NCH.sub.3 ; .delta.2.20-2.84, 8 protons, CH.sub.2 CH.sub.2 CH.sub.2 SCH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 N(CH.sub.3).sub.2 ; .delta.3.40-3.74, 4 protons, 2.times.0 CH.sub.2.

Analysis for C.sub.16 H.sub.18 F.sub.17 NOS: Calc.: C, 32.28; H, 3.05; F, 54.25; N, 2.35. Found: C, 32.16; H, 2.83; F, 54.26; N, 2.17.

2-(1,1,2,2-Tetrahydroperfluorodecanethioethoxy)ethyltrimethylammonium iodide N.sup.+ (CH.sub.3).sub.3  .sup.- I

2-Dimethylaminoethyl 2'(1,1,2,2-tetrahydroperfluorodecanethio) ethyl ether (4.76 g, 0.008 mole), iodomethane (2.27 g, 0.016 mole), and methanol (3 g) were reacted overnight at room temperature. The product was crystallized twice from methanol to yield 4.15 g of white powder (70.3% of theory). NMR showed proton resonances at .delta.2.58, 2 protons, C.sub.8 F.sub.17 CH.sub.2 ; .delta.2.82, 4 protons, CH.sub.2 SCH.sub.2 ; .delta.3.15, 9 protons, 3.times.N.sup.+ CH.sub.3 ; .delta.3.60-3.67, 4 protons, SCH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 N.sup.+ ; .delta.3.89, 2 protons, OCH.sub.2 CH.sub.2.sup.+ N.

Analysis for C.sub.17 H.sub.21 F.sub.17 NOS: Calc.: C, 27.69; H, 2.87; F, 43.80; I, 17.21; N, 1.90. Found: C, 27.57; H, 2.67; F, 44.56; I, 16.92; N, 1.93.

2-(1,1,2,2-Tetrahydroperfluorodecanethioethoxy)ethyldimethylammonium ethyl sulfate N.sup.+ (CH.sub.3).sub.2 CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.2 SO.sub.4 -

2-Dimethylaminoethyl 2'(1,1,2,2-tetrahydroperfluorodecanethio) ethyl ether (2.02 g, 0.0034 mole), and diethyl sulfate (0.54 g, 0.0035 mole) were reacted in methanol (4.00 g) overnight at 40.degree. C. All volatiles were stripped off under high vacuum to give 2.05 g product (80.4% of theory) as a yellow gel NMR showed proton resonances at .delta.1.20, 6 protons, NCH.sub.2 CH.sub.3 and CH.sub.3 CH.sub.2 SO.sub.4 ; .delta.2.21, 4 protons, CH.sub.2 SCH.sub.2 ; .delta.2.50, 2 protons, C.sub.8 F.sub.17 CH.sub.2 ; .delta.3.06-3.40, 6 protons, CH.sub.3 NCH.sub.3, .delta.3.26-3.98, 8 protons, CH.sub.2 OCH.sub.2 and CH.sub.2 NCH.sub.2.

Analysis for C.sub.20 H.sub.28 F.sub.17 NO.sub.5 S.sub.2 : Calc.: C, 32.05; H, 3.77; F, 43.09; N, 1.87. Found: C, 29.47; H, 3.36; F, 44.46; N, 1.81.

2-Dimethylaminoethyl 2'-(1,1,2,2-tetrahydroperfluoroalkylthio) ethyl ether N(CH.sub.3).sub.2

1,1,2,2-Tetrahydroperfluoroalkenethiol (14.00 g, 0.032 mole), dimethylaminoethyl vinyl ether (3.78 g, 0.033 mole), and 2,2'-, azobis(2-methylpropionitrile) (0.10 g) were reacted under nitrogen at 70.degree. C. for 5 hours. The resultant amber colored liquid was 98.3% pure by GLC.

2-(1,1,2,2-Tetrahydroperfluoroalkylthioethoxy)ethyltrimethylammonium iodide (CH.sub.3).sub.3   .sup.- I

2-Dimethylaminoethyl 2'-(1,1,2,2-tetrahydroperfluoroalkylthio) ethyl ether (500 g 0.009 mole), iodomethane (2.52 g, 0.018 mole), and methanol (3.00 g) were combined resulting in a mild exotherm and allowed to set at room temperature for 3 hours. The resultant mixture was dried at 100.degree. C./0/02 mm Hg and ground up to yield 5.70 g product (90.9% of theory) as a yellow solid.

Analysis for fluorine: Calc.: F, 41.29. Found: F, 42.56.

The following perfluoroalkylthioethyl ethers and derivatives can be prepared by procedures similar to those given on Examples 1-10. __________________________________________________________________________ Further Reaction R.sub.f -thiol       Vinyl Ether    With __________________________________________________________________________ (CF.sub.3).sub.2 CFOCF.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 SH CH.sub.2 .dbd.CHOCH.sub.3 None (CF.sub.3).sub.2 CFOCF.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 SH CH.sub.2 .dbd.CHOC.sub.16 H.sub.33 None C.sub.6 F.sub.13 CH.sub.2 CH.sub.2 SH CH.sub.2 .dbd.CHOCH.sub.2 CH.sub.2 OH None C.sub.6 F.sub.13 CH.sub.2 CH.sub.2 SH CH.sub.2 .dbd.CHOCH.sub.2 CH.sub.2 N(CH.sub.3).sub.2 None CF.sub.3 CF.sub.2 CH.sub.2 SH CH.sub.2 .dbd.CHOCH.sub.2 CH.sub.2 N(CH.sub.3).sub.2 CH.sub.3 I CF.sub.3 CF.sub.2 CH.sub.2 SH CH.sub.2 .dbd.CHOCH.sub.2 CH.sub.2 N(C.sub.2 H.sub.5).sub.2 1,3- propane sultone C.sub.8 F.sub.17 (CH.sub.2).sub.4 SH CH.sub.2 .dbd.CHOC.sub.6 H.sub.5 None C.sub.8 F.sub.17 (CH.sub.2).sub.4 SH CH.sub.2 .dbd.CHOC.sub.2 H.sub.4 OCH.dbd. Noneub.2 C.sub.8 F.sub.17 CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 CH.sub.2 SH CH.sub.2 .dbd.CHO(CH.sub.2).sub.4 OH None 20. C.sub.8 F.sub.17 CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 CH.sub.2 SH CH.sub.2 .dbd.CHO(CH.sub.2).sub.4 OH C.sub.6 H.sub.5 N.dbd.C.dbd.O C.sub.8 F.sub.17 CH.sub.2 CH.sub.2 N(CH.sub.3)CH.sub.2 CH.sub.2 CH.sub.2 SH        CH.sub.2 .dbd.CHO(CH.sub.2).sub.2 OH CH.sub.3 COCl C.sub.8 F.sub.17 CH.sub.2 CH.sub.2 N(CH.sub.3)CH.sub.2 CH.sub.2 CH.sub.2 SH        CH.sub.2 .dbd.CHO(CH.sub.2).sub.2 OH (CH.sub.3 CO).sub.2 O R.sub.f CH.sub.2 CH.sub.2 SH CH.sub.2 .dbd.CHO(CH.sub.2).sub.2 OH None __________________________________________________________________________

The subject fluorochemicals have special utility as oil spill collecting agents, as described in a copending application. Preferred candidates are low viscosity fluids which form insoluble monolayers with high spreading pressures, and have a persistent oil film clearing ability and durability. Maximum Spreading Pressure Clearing Example   State    ,dynes/cm     Durability ______________________________________ 5         liquid   57            excellent 23        liquid   56            excellent 1         solid    57 (in solvent) -- 3         solid    57 (in solvent) -- 2         solid    insoluble     -- 4         solid    54 (in solvent) -- ______________________________________ Surface Properties of Selected Examples Surface Concentration at Concentration Example    0.1%   0.01%      0.001% 0.00% ______________________________________ 7          20.8   31.5       43.2 10.sup.a          24.8       42.7  57.3 10.sup.b          24.5       45.5  54.6 ______________________________________ .sup.a R.sub.f -distribution C.sub.6,C.sub.8,C.sub.10,C.sub.12 -40,40,13, .sup.b R.sub.f -distribution C.sub.6,C.sub.6,C.sub.10,C.sub.12 -32,36,22, 

## Claims

1. A perfluoroalkylthioethylether of the formula wherein atoms, or said perfluoroalkyl substituted by perfluoroalkoxy of 2 to 6 carbon atoms; alkylenethioalkylene of 2 to 12 carbon atoms, alkyleneoxyalkylene of 2 to 12 carbon atoms, or alkyleneiminoalkylene of 2 to 12 carbon atoms where the imino nitrogen atom contains as a third substituent hydrogen or alkyl of 1 to 6 carbon atoms; phenylene; and where R.sub.2 is hydrogen, alkyl of 1 to 24 carbon atoms, alkanoyl of 2 to 24 carbon atoms, alkenoyl of 3 to 24 carbon atoms.

2. A compound according to claim 1, wherein R.sub.f is perfluoroalkyl of 6 to 12 carbon atoms, R.sub.1 is alkylene of 2 to 8 carbon atoms, alkylenethioalkylene of 2 to 8 carbon atoms, alkyleneoxyalkylene of 2 to 8 carbon atoms or alkyleneiminoalkylene of 2 to 8 carbon atoms wherein the imino nitrogen contains hydrogen or methyl as the third substituent; atoms, alkanoyl of 2 to 24 carbon atoms, alkenoyl of 3 to 24 carbon atoms.

3. A compound according to claim 1, wherein R.sub.f is perfluoroalkyl of 6 to 12 carbon atoms; R.sub.1 is alkylene of 2 to 4 carbon atoms; T is alkylene of 2 to 12 carbon atoms; and Z is --OR.sub.2 wherein R.sub.2 is hydrogen or alkyl of 1 to 12 carbons.

4. A compound according to claim 1 of the formula wherein perfluoroalkoxyperfluoroalkyl of 4 to 12 carbon atoms.

5. A compound according to claim 1 wherein Z is --H.

6. A compound according to claim 1, wherein Z is --OR.sub.2.

7. A compound according to claim 2, wherein Z is --H.

8. A compound according to claim 2, wherein Z is --OR.sub.2.