Fluorochemical piperazine carboxamides

Abstract

The present invention provides a novel partially fluorinated piperazine carboxamide compound, and polymer composition comprising the fluorinated compound and a thermoplastic or thermoset polymer. The polymer composition is useful in preparing shaped articles such as fibers and films which have desirable oil- and water repellency properties.

Claims

1. A fluorochemical compound of the formula: ##STR00012## where R.sub.f is a perfluorinated group; R is a fluorinated or non-fluorinated C.sub.2-C.sub.40 (hetero)hydrocarbyl group; and subscript x is 1 to 3.

2. The fluorochemical compounds of claim 1 wherein R.sub.f is a perfluorinated group having an average of 3 to 5 carbon atoms.

3. The fluorinated compounds of claim 1 wherein R is R.sub.f.sup.1 and where R.sub.f.sup.1 is a fully- or partially fluorinated alkyl group.

4. The fluorinated compounds of claim 1 wherein R is R.sub.f.sup.1 and where R.sub.f.sup.1 is of the formula C.sub.aF.sub.bH.sub.c, where a is at least one, b is at least one, and c is at least may be zero.

5. The fluorinated compounds of claim 4 wherein b>c.

6. The fluorochemical compounds of claim 1 wherein R.sub.f is selected contains at least 95% linear C.sub.3-C.sub.5 groups.

7. The fluorochemical compounds of claim 1 wherein R is an alkyl or alkylene group.

8. The fluorochemical compounds of claim 1 wherein R is an aryl group.

9. The fluorochemical compounds of claim 1 wherein R is a heterohydrocarbyl alkylene.

10. The fluorochemical compounds of claim 9 wherein R is a poly(alkylene oxide) group.

11. The fluorochemical compounds of claim 1 wherein R is a fully- or partially fluorinated alkyl group.

12. The fluorochemical compounds of claim 1 of the formula: ##STR00013## where R.sub.f is a perfluorinated group; and R.sub.f.sup.2 is a perfluorinated group having 1-8 carbon atoms.

13. A composition comprising a thermoplastic polymer and an additive fluorochemical compound of claim 1.

14. The composition of claim 13 wherein said thermoplastic polymers are selected from the group consisting of polyamides, polyesters, polyurethanes, epoxides, epoxy resins, (meth)acrylates, polystyrenes, silicones and polyolefins.

15. The composition of claim 13 wherein said additive comprises from 0.1 to 5 weight percent of said composition.

16. The composition of claim 13 wherein R is a C.sub.2-C.sub.40 alkyl or alkylene.

17. The composition of claim 13 wherein R is a C.sub.2-C.sub.18 alkyl or alkylene.

18. The composition of claim 13 wherein R is an aryl or arylene.

19. The composition of claim 18 wherein the aryl group is selected from phenyl, napthyl, anthracenyl, phenanthanenylbenzonapthanenyl, or fluorenyl.

20. A shaped article comprising the composition of claim 13.

21. The shaped article of claim 20 selected from the group of films, sheets, fibers, woven or nonwoven fabrics.

Description

DETAILED DESCRIPTION

(1) This invention provides fluorochemical piperazine carboxamide compounds having at least one group of the formula:

(2) ##STR00002##
wherein

(3) R.sub.f is a perfluorinated group, preferably a perfluoroalkyl group, most preferably a perfluoroalkyl group having an average of 3 to 5 carbon atoms.

(4) In some embodiments, this disclosure provides fluorochemical compound of the formula:

(5) ##STR00003##
where

(6) R.sub.f is a perfluorinated group, preferably having an average of 3 to 5 carbon atoms;

(7) R is a fluorinated or non-fluorinated C.sub.2-C.sub.40 (hetero)hydrocarbyl group; and

(8) subscript x is 1 to 3.

(9) This invention provides fluorochemical compositions comprising a thermoplastic or thermoset polymer and at least one partially fluorinated piperazine carboxamide compounds of Formulas I-II.

(10) In some preferred embodiments, the present fluorinated piperazine carboxamide compounds and compositions thereof provide the necessary performance even with the shorter C.sub.3-C.sub.5 perfluoroalkyl groups. Furthermore, the short chain perfluorocarboxylic acids (the presumed intermediate degradation products) are less toxic and less bioaccumulative than the longer chain (C.sub.8) homologues. For these reasons, the R.sub.f groups are selected from C.sub.3-C.sub.5 perfluoroalkyl groups. In preferred embodiments, R.sub.f is selected contains at least 95% linear C.sub.3-C.sub.5 groups and less than 5% of other perfluoroalkyl groups.

(11) When R is selected as a non-fluorinated hydrocarbyl moiety, R in may be a linear or branched chain, saturated or unsaturated, cyclic or acyclic (or any combination thereof) alkyl or alkylene group having from 1 to 40 carbon atoms and 1 to 20 in-chain oxygen atoms. Alternatively R may contain aryl or arylene groups. The range of structures contemplated for the organic moiety R will be better understood with reference to the compounds suitable for use in steps of the Reaction Schemes described in detail below.

(12) In some embodiments R is a linear or branched alkyl group of 1 to 40, preferably 2 to 30, and most preferably 2 to 10 carbon atoms of the formula C.sub.nH.sub.2n+1, where n is 1 to 40, preferably 2 to 30, and most preferably 2 to 20. The alkyl or alkylene groups may be further substituted by one or more aryl groups, i.e. an aralkylene. In other embodiments, R is a divalent alkylene of the formula C.sub.nH.sub.2n, or a trivalent alkylene of the formula C.sub.nH.sub.2n1 where n is 1 to 40, preferably 2 to 30, and most preferably 2 to 20. In such embodiments, R may be designated as R.sup.Alkyl in Formula II.

(13) In other embodiments, R is an aryl group having a valence of 1-3, including phenyl, napthyl, anthracenyl, phenanthanenyl, benzonapthanenyl, and fluorenyl. The aryl groups may be further substituted with one or more alkyl groups, i.e. an alkarylene group. In such embodiments, R may be designated as R.sup.Aryl in Formula II.

(14) In some embodiments R may be selected as a heterohydrocarbyl, linear or branched alkylene having 2 to 30 carbon atoms and 1 to 15 in-chain oxygen atoms; e.g. a poly(alkylene oxide) group, including poly(ethylene oxide), poly(propylene oxide) and combinations thereof. In such embodiments, R may be designated as R.sup.PEG in Formula II.

(15) In some embodiments, R may be selected as a fully- or partially fluorinated alkyl group, which may be designated as R.sub.f.sup.1 in Formula II. R.sub.f.sup.1 may be of the formula C.sub.aF.sub.bH.sub.c, where a is at least one, b is at least one, and c may be zero. Preferably b>c.

(16) The fluorochemical piperazine compounds can be prepared using known organic reactions, such as those disclosed in U.S. Pat. No. 5,451,622 (Boardman et al, incorporated herein by reference. A preferred method of preparation is by the reaction of fluoroaliphatic radical-containing sulfonyl fluorides, R.sub.fSO.sub.2F, with piperazine followed by reaction of the resulting fluoroaliphatic radical-containing carboxamido piperazine with various organic reactants.

(17) Representative reaction schemes for the preparation of fluorine-containing piperazine compounds are outlined below where R.sub.f is as described above for Formulas I and II where X is a leaving group such as halogen, tosylate, alkoxy or CH.sub.2CF.sub.3, and R is a fluorinated or non-fluorinated C.sub.2-C.sub.40 (hetero)hydrocarbyl group. In one embodiment a perfluoroalkylsulfonylpiperazine is reacted with an oxalate to yield the mono- and/or dipiperazine product. In another embodiment a di- or triamine may be reacted with an oxalate to form a bis-oxalate, followed by reaction with a perfluoroalkylsulfonylpiperazine. In another embodiment, a mono oxalate of a perfluoroalkylsulfonyl piperazine is reacted with a mon-, di- or triamine. In yet another embodiment, excess piperazine may be reacted with a dioxalate to form a bis-peperazino axamide, followed by reaction with a perfluoroalkylsulfonate compound.

(18) ##STR00004##

(19) It may be noted that when X may be selected as derived from a partially fluorinated alcohol, such as R.sub.f.sup.2CH.sub.2OH, partial substitution yields compounds of Formula III:

(20) ##STR00005##
where R.sub.f.sup.2 is a perfluorinated group, preferably a perfluoroalkyl group having 1-8 carbon atoms.

(21) As it is preferred that the R.sub.f groups are linear perfluoroalkyl groups, and have less than 5 mole % non-linear isomers, the perfluroalkylsulfonyl halide starting material is desirable prepared by electrochemical fluorination (ECF) of a linear C.sub.3-C.sub.5 sulfonyl fluoride, preferably a linear C.sub.4 sulfonyl fluoride. With longer chain sulfonyl fluorides, the electrochemical fluorination yields a complex mixture of linear and branched isomers, as well as higher and lower homologues. ECF of linear C.sub.3-C.sub.5 alkyl sulfonyl fluorides yields predominantly linear products with minor amounts of homologues.

(22) The present invention provides a synthetic organic polymer composition comprising the one or more of the fluorinated compounds of Formulas I and/or II and a thermoplastic or thermoset organic polymer. The compounds of Formula II are useful as polymer melt additives to impart desirable low surface energy properties to the thermoplastic or thermoset polymer.

(23) Useful polymers include both thermoplastic and thermoset polymers and include polyamides, e.g., nylon-6 and nylon-66, polyesters, e.g., polyethylene terephthalate, polyurethanes, epoxides, epoxy resins, (meth)acrylates, polystyrenes, silicones and polyolefins, e.g., polyethylene and polypropylene. Thermoplastic polymers such as polyolefins are preferred. The resultant articles, due to the presence of the fluorochemical additive, have improved oil- and water-repellency, low surface energy and a resistance to soiling.

(24) Shaped articles (e.g., fibers, films and molded or extruded articles) of this invention can be made, e.g., by blending or otherwise uniformly mixing the alkylated fluorochemical oligomer and the polymer, for example by intimately mixing the oligomer with pelletized or powdered polymer, and melt extruding the mixture into shaped articles such as pellets, fibers, or films by known methods. The additive can be mixed per se with the polymer or can be mixed with the polymer in the form of a masterbatch (concentrate) of the additive in the polymer. Masterbatches typically contain from about 10% to about 25% by weight of the fluorochemical additive. Also, an organic solution of the additive may be mixed with the powdered or pelletized polymer, the mixture dried to remove solvent, then melted and extruded into the desired shaped article. Alternatively, molten additive (as a compound(s) or masterbatch) can be injected into a molten polymer stream to form a blend just prior to extrusion into the desired shaped article.

(25) When using thermoset resins, such as epoxy resins, urethanes and acrylates, the fluorochemical oligomer may be mixed with the resin and cured by application of heat. Preferably such thermoset resins may be processed by reactive extrusion techniques such as are taught in U.S. Pat. No. 4,619,976 (Kotnour) and U.S. Pat. No. 4,843,134 (Kotnour).

(26) The thermoplastic composition containing the compounds of Formula I-III may be used to provide oil and water repellency to fibers. The fluorochemical additives are melt processible, i.e., suffer substantially no degradation under the melt processing conditions used to form the fibers.

(27) The amount of fluorochemical compound in the composition is that amount sufficient to produce a shaped article having a surface with the desired properties of oil and water repellency and/or soiling resistance. Preferably, the amount of fluorochemical compound will be that amount which provides from about 100 to 10,000 ppm fluorine, more preferably 200 to 5000 ppm, most preferably 400 to 3000 ppm fluorine, based on the weight of the shaped article.

(28) After melt extrusion of a fiber, film or extruded article, an annealing step may be carried out to enhance oil and water repellency. Annealing apparently allows the fluorochemical additive to migrate to the surface of the thermoplastic polymer with a resultant increase in repellency properties, reduced surface activity, improved solvent resistance and improved release properties. The fiber or film is annealed for at a temperature and for a time sufficient to increase the amount of fluorochemical additive at the surface. Effective time and temperature will bear an inverse relationship to one another and a wide variety of conditions will be suitable. Using polypropylene, for example, the annealing process can be conducted below the melt temperature at about 50 to 120 C. for a period of about 30 seconds to 10 minutes. Annealing may also be effected by contact with heated rolls, such as embossing rolls, at 50 C. to 160 C. for periods of about 1 to 30 seconds. In some cases, the presence of moisture during annealing, e.g., by using an autoclave to anneal, can improve the effectiveness of the fluorochemical additive. The annealing method may also serve to reduce the amount of additive necessary by maximizing fluorine content at the surface of the polymer.

(29) In addition to their use in modifying the properties of fibers, the polymer composition of the invention is also useful in preparing blown microfibers for non-woven fabrics having low surface energy, oil and water repellency and/or soiling resistance. The resin, such as polypropylene, used to form the melt blown microfibers should be substantially free from materials such as antistatic agents which could increase the electrical conductivity or otherwise interfere with the ability of the fibers to accept and hold electrostatic charges. When the fluorochemical compounds of the invention are used as additives to melt blown microfibers, the additive is preferably present in amounts of about 0.2 to 10 weight percent, more preferably from 0.5 to 5 weight percent and most preferably 0.5 to 2 weight percent.

(30) As used herein, the terms fiber and fibrous refer to particulate matter, generally thermoplastic resin, wherein the length to diameter ratio of the particulate matter is greater than or equal to about 10. Fiber diameters may range from about 0.5 micron up to at least 1,000 microns. Each fiber may have a variety of cross-sectional geometries, may be solid or hollow, and may be colored by, e.g., incorporating dye or pigment into the polymer melt prior to extrusion.

(31) The non-woven webs of fibers of thermoplastic olefinic polymer for use in this invention include non-woven webs manufactured by any of the commonly known processes for producing non-woven webs. For example, the fibrous non-woven web can be made by spunbonding techniques or melt-blowing techniques or combinations of the two. Spunbonded fibers are typically small diameter fibers which are formed by extruding molten thermoplastic polymer as filaments from a plurality of fine, usually circular capillaries of a spinneret with the diameter of the extruded fibers being rapidly reduced. Meltblown fibers are typically formed by extruding the molten thermoplastic material through a plurality of fine, usually circular, die capillaries as molten threads or filaments into a high velocity, usually heated gas (e.g. air) stream which attenuates the filaments of molten thermoplastic material to reduce their diameter. Thereafter, the meltblown fibers are carried by the high velocity gas stream and are deposited on a collecting surface to form a web of randomly disbursed meltblown fibers. Any of the non-woven webs may be made from a single type of fiber or two or more fibers which differ in the type of thermoplastic olefinic polymer and/or thickness. Alternatively, sheath-core fibers can be extruded, containing different polymer compositions in each layer or containing the same polymer composition in each layer but employing the more expensive fluorochemical component in the outer sheath layer.

(32) The melt blown polypropylene microfibers useful in the present invention can be prepared as described in Van Wente, A., Superfine Thermoplastic Fibers, Industrial Engineering Chemistry, vol. 48, pp. 1342-1346 (1956) and in Report No. 4364 of the Naval Research Laboratories, published May 25, 1954, entitled Manufacture of Super Fine Organic Fibers by Van Wente et al. or from microfiber webs containing particulate matter such as those disclosed, for example, in U.S. Pat. No. 3,971,373 (Braun), U.S. Pat. No. 4,100,324 (Anderson) and U.S. Pat. No. 4,429,001 (Kolpin et al.). Multilayer constructions of nonwoven fabrics enjoy wide industrial and commercial utility and include uses such as fabrics for medical gowns and drapes. The nature of the constituent layers of such multilayer constructions can be varied according to the desired end use characteristics, and can comprise two of more layers of melt-blown and spun-bond webs in may useful combinations such as described in U.S. Pat. Nos. 5,145,727 and 5,149,576. The filtering efficiency of a melt-blown microfiber web can be improved by a factor of two or more when the melt-blown fibers are bombarded as they issue from the orifices with electrically charged particles such as electrons or ions, thus making the fibrous web an electret. Similarly, the web can be made an electret by exposure to a corona after it is collected. Melt-blown polypropylene microfibers are especially useful, while other polymers may also be used such as polycarbonates and polyhalocarbons that may be melt-blown and have appropriate volume-resistivities under expected environmental conditions.

(33) Any of a wide variety of constructions, especially multilayer constructions such as SMS (spunbond/meltblown/spunbond) constructions, may be made from the above-described fibers and fabrics, and such constructions will find utility in any application where some level of hydrophobicity, oleophobicity (or other fluid repellency, such as to bodily fluids) is required. The fibers prepared from the synthetic organic polymer composition of the invention may be used in woven and nonwoven medical fabrics (such as drapes, gowns and masks), industrial apparel, outdoor fabrics (such as umbrellas, awning, tents, etc), raincoats and other outdoor apparel, as well as home furnishings such as table linens and shower curtains, and in myriad other related uses.

(34) Preferably, the filter media is annealed, i.e., heated for a sufficient time at a sufficient temperature to cause the fluorochemical additive to bloom to the surface of the fibers. Generally, about 1 to 10 minutes at about 140 deg. C. is sufficient although shorter times may be used at higher temperatures and longer times may be required at lower temperatures.

(35) Blown microfibers for fibrous electret filters of the invention typically have an effective fiber diameter of from about 5 to 30 micrometers, preferably from about 7 to 10 micrometers, as calculated according to the method set forth in Davies, C. N., The Separation of Airborne Dust and Particles, Institution of Mechanical Engineers, London, Proceedings 1B, 1952.

(36) The electret filter media of the present invention preferably has a basis weight in the range of about 10 to 500 g/m.sup.2, more preferably about 10 to 100 g/m.sup.2. In making melt-blown microfiber webs, the basis weight can be controlled, for example, by changing either the collector speed or the die throughput. The thickness of the filter media is preferably about 0.25 to 20 mm, more preferably about 0.5 to 2 mm. The electret filter media and the polypropylene resin from which it is produced should not be subjected to any unnecessary treatment which might increase its electrical conductivity, e.g., exposure to gamma rays, ultraviolet irradiation, pyrolysis, oxidation, etc.

(37) The melt-blown microfibers or fibrillated fibers of the electret filters of the invention can be electrostatically charged by a process described in U.S. Pat. No. Re. 30,782 (van Turnhout) or Re. 31,285 (van Turnhout) or by other conventional methods for charging or polarizing electrets, e.g., by a process of U.S. Pat. No. 4,375,718 (Wadsworth et al.); U.S. Pat. No. 4,588,537 (Klasse et al.); or U.S. Pat. No. 4,592,815 (Nakao). In general, the charging process involves subjecting the material to corona discharge or pulsed high voltage.

(38) Films prepared from the composition of this invention can be made which are useful, for example, for grease-resistant packaging, release liners and microporous film applications. These films can be used to make multi-layer constructions in which one, more than one, or all layers contain the fluorochemical additive.

(39) This invention is illustrated by, but is not intended to be limited to, the following examples. Unless otherwise specified, all percentages shown in the examples and test methods, which follow, are percentages by weight.

EXAMPLES

(40) Materials

(41) Unless otherwise indicated all chemicals were obtained or are commonly available from chemical companies such as Sigma-Aldridge Chemical Company, St. Louis, Mo.

(42) KAYDOL Mineral Oil was obtained from Sonneborn, Inc., Parsippany, N.J. under trade designation KAYDOL White Mineral Oil.

(43) C18 Diester (C.sub.4F.sub.9SO.sub.2N(CH.sub.3)CH.sub.2CH.sub.2OOC(CH.sub.2).sub.16COOCH.sub.2CH.sub.2(CH.sub.3)NSO.sub.2C.sub.4F.sub.9), was prepared by following the process described in F-4 of U.S. Pat. No. 7,396,866 B2.

(44) Methods

(45) Method for Water Repellency Test

(46) To run the Water Repellency Test, film samples prepared according to the Examples and Comparative Examples described below were placed on a flat, horizontal surface. Five small drops of water or a water/isopropyl alcohol (IPA) mixture were gently placed at points at least two inches (about 5 cm) apart on the film samples. If, after observing for ten seconds at a 45 angle, four of the five drops were visible as a sphere or a hemisphere, the film sample was deemed to pass the test. The reported water repellency rating corresponds to the highest numbered water or water/IPA mixture for which the film sample passed the above described test. It is desirable to have a water repellency rating of at least 4, preferably at least 6. The water repellency ratings and the corresponding water/IPA mixtures are shown in Table 1, below:

(47) TABLE-US-00001 TABLE 1 Water Repellence Rating Water/IPA Blend (% volume) 0 100/0 1 90/10 2 80/20 3 70/30 4 60/40 5 50/50 6 40/60 7 30/70 8 20/80 9 10/90 10 0/100
Method for Oil Repellency Test

(48) The Oil Repellency Test was run in the same manner as the Water Repellency Test described above except that the film samples were challenged to penetration by oil or oil mixtures of varying surface tensions. The reported oil repellency rating corresponds to the oil or oil mixture for which the film sample passed the described test. It is desirable to have an oil repellency rating of at least 1, preferably at least 3. The oil repellency ratings and the corresponding oil or oil mixtures are shown in Table 2, below:

(49) TABLE-US-00002 TABLE 2 Oil Repellency Testing Oil Composition 0 Fails KAYDOL Mineral Oil 1 KAYDOL Mineral Oil 2 65/35 (vol/vol) KAYDOL Mineral Oil/n-hexadecane 3 n-hexadecane 4 n-tetradecane 5 n-dodecane 6 n-decane 7 n-octane 8 n-heptane
Method for Forming Polymer Films

(50) To prepare the sample films according the Examples and Comparative Examples described below, a film forming polymer (PET, Nylon-6, polypropylene, etc.) and a fluorochemical additive were simultaneously melted and mixed as the mixture was conveyed through an extruder by a rotating screw or screws and then was forced out through a slot or flat die where the film was quenched. The films were optionally oriented prior to quenching by drawing or stretching the film at elevated temperatures. The to extruder for PET used was a KraussMaffei Berstorff 25MM counter-rotating conical twin screw extruder (obtained from KraussMaffei Berstorff GmbH & Co., Munich Germany) maximum extrusion temperature of approximately 275 C. and with the distance to the collector of approximately 11 inches (about 28 cm). The extruder used for Nylon-6 was a Leistritz 15MM counter-rotating conical twin screw extruder (obtained from Leistritz GmbH & Co., Nuremberg Germany) with maximum extrusion temperature of approximately 230 C. and with the distance to the collector of approximately 11 inches (about 28 cm).

(51) The fluorochemical additive and thermoplastic polymer were each weighed and mixed in a plastic container in a desired ratio. Then using a mixer head affixed to a hand drill they were mixed for about one minute until a visually homogeneous mixture was obtained. This mixture was then added to the extruder hopper. The process conditions for each mixture were the same, including the film die construction and the thickness of the film (50 micrometers). The extrusion temperature was approximately 230-275 C. depending on the polymer. The polymer throughput rate was about 7.5 lbs/h (about 3.40 kg/h)

Preparative Example 1 (PE1)

(52) ##STR00006##

(53) 1-(1,1,2,2,3,3,4,4,4-nonafluorobutylsulfonyl)piperazine (10 g, 27.158 mmol, 1 equiv.), in ethylacetate (100 mL) was added to a 500 mL round bottom flask containing bis-(trifluoroethyldioxalate) (22.7 mL, 136 mmol, 5 equiv.) equipped with a magnetic stir bar and reflux condenser. The mixture was allowed to stir at reflux for 16 h. Trifluoroethanol and ethylacetate were distilled off followed by excess dioxolate to afford 2,2,2-trifluoroethyl 2-[4-(1,1,2,2,3,3,4,4,4-nonafluorobutylsulfonyl)piperazin-1-yl]-2-oxoacetate) (14.2 g, 27.2 mmol, >99% yield) as an off-white solid. The identity of the material was confirmed by LC/MS and NMR techniques.

Preparative Example 2 (PE2)

(54) ##STR00007##

(55) 1-(1,1,2,2,3,3,4,4,4-nonafluorobutylsulfonyl)piperazine (45.21 g, 122.78 mmol, 2.01 equiv.), bis(2,2,2-trifluoroethyl) 2,2-(ethane-1,2-diylbis(azanediyl))bis(2-oxoacetate) (22.49 g, 61.08 mmol) and ethylacetate (100 mL) were added to a 500 mL round bottom flask equipped with a magnetic stir bar and reflux condenser. The mixture was allowed to stir at reflux for 16 h. The reaction mixture was cooled to room temperature (r.t.), the solid collected via filtration and dried under vacuum to afford N,N-(ethane-1,2-diyl)bis(2-oxo-2-(4-((perfluorobutyl)sulfonyl)piperazin-1-yl)acetamide) (52.2 g, 57.71 mmol, 94% yield) as a white solid. The identity of the material was confirmed by LC/MS and NMR techniques.

Preparative Example 3 (PE3)

(56) ##STR00008##

(57) 1-(1,1,2,2,3,3,4,4,4-nonafluorobutylsulfonyl)piperazine (47.64 g, 129.37 mmol, 2.01 equiv.), bis(2,2,2-trifluoroethyl) 2,2-(propane-1,3-diylbis(azanediyl))bis(2-oxoacetate) (24.6 g, 64.36 mmol) and ethylacetate (100 mL) were added to a 500 mL round bottom flask equipped with a magnetic stir bar and reflux condenser. The mixture was allowed to stir at reflux for 16 h. The reaction mixture was cooled to r.t., the solid collected via filtration and dried under vacuum to afford N,N-(propane-1,3-diyl)bis(2-oxo-2-(4-((perfluorobutyl)sulfonyl)piperazin-1-yl)acetamide) (56.9 g, 61.94 mmol, 96% yield) as a white solid. The identity of the material was confirmed by LC/MS and NMR techniques.

Preparative Example 4 (PE4)

(58) ##STR00009##

(59) 1-(1,1,2,2,3,3,4,4,4-nonafluorobutylsulfonyl)piperazine (45 g, 122.21 mmol, 2.01 equiv.), bis(2,2,2-trifluoroethyl) 2,2-(hexane-1,6-diylbis(azanediyl))bis(2-oxoacetate) (11.25 g, 60.80 mmol) and ethylacetate (100 mL) were added to a 500 mL round bottom flask equipped with a magnetic stir bar and reflux condenser. The mixture was allowed to stir at reflux for 16 h. The reaction mixture was cooled to r.t., the solid collected via filtration and dried under vacuum to afford N,N-(hexane-1,6-diyl)bis(2-oxo-2-(4-((perfluorobutyl)sulfonyl)piperazin-1-yl)acetamide) (21 g, 21.86 mmol, 34% yield) as a white solid. The identity of the material was confirmed by LC/MS and NMR techniques.

Preparative Example 5 (PE5)

(60) ##STR00010##

(61) 1-(1,1,2,2,3,3,4,4,4-nonafluorobutylsulfonyl)piperazine (45 g, 122.21 mmol, 2.01 equiv.), bis(2,2,2-trifluoroethyl) 2,2-((1,3-phenylenebis(methylene))bis(azanediyl))bis(2-oxoacetate) (27.01 g, 60.80 mmol) and ethylacetate (100 mL) were added to a 500 mL round bottom flask equipped with a magnetic stir bar and reflux condenser. The mixture was allowed to stir at reflux for 16 h. The reaction mixture was cooled to r.t., the solid collected via filtration and dried under vacuum to afford N,N-(1,3-phenylenebis(methylene))bis(2-oxo-2-(4-((perfluorobutyl)sulfonyl)piperazin-1-yl)acetamide) (51.50 g, 86.37 mmol, 86% yield) as a white solid. The identity of the material was confirmed by LC/MS and NMR techniques.

Preparative Example 6 (PE6)

(62) ##STR00011##

(63) 2,2,2-trifluoroethyl 2-[4-(1,1,2,2,3,3,4,4,4-nonafluorobutylsulfonyl)piperazin-1-yl]-2-oxo-acetate) (1 g, 1.92 mmol, 1 equiv.) and octadecylamine (0.67 g, 2.5 mmol, 1.3 equiv.) and dichloromethane (5 mL) were added to a 16 mL vial equipped with a magnetic stir bar. The mixture was allowed to stir for 16 h. Solvent was removed via rotary evaporator and the material was triturated with 10 mL of ether. The product was collected via filtration to afford 2-[4-(1,1,2,2,3,3,4,4,4-nonafluorobutylsulfonyl)piperazin-1-yl]-N-octadecyl-2-oxo-acetamide (0.8 g, 1 mmol, 60% yield) as a white solid. The identity of the material was confirmed by LC/MS and NMR techniques.

Examples 1-5 (EX1-EX5) and Comparative Examples 6-7 (CE6-CE7)

(64) To prepare EX1-EX5, either PET or a Nylon-6 polymer were co-extruded with a 1.5 wt. % fluorochemical additive prepared in PE2-PE6, respectively, using the process described above in Method for Forming Polymer Films. The resulting films were annealed at 110 C. for 10 min (PET) or 120 C. for 20 min (Nylon-6).

(65) CE6 was prepared in the same manner as EX1-EX5 described above except that C.sub.4F.sub.9SO.sub.2N(CH.sub.3)CH.sub.2CH.sub.2OOC(CH.sub.2).sub.16COOCH.sub.2CH.sub.2(CH.sub.3)NSO.sub.2C.sub.4F.sub.9 was the fluorochemical additive.

(66) CE7 was prepared in the same manner as EX1-EX5 described above, except that no fluorochemical additive was present.

(67) The resulting EX1-EX5 and CE6-CE7 film samples were tested for their water and oil repellency using the test methods described above. The results are reported in Table 3, below.

(68) TABLE-US-00003 TABLE 3 Water Repellency Oil Repellency Rating rating Example Additive PET Nylon-6 PET Nylon-6 EX1 PE2 10 7 8 8 EX2 PE3 10 10 8 8 EX3 PE4 4 10 7 8 EX4 PE5 6 10 6 8 CE6 C18 Diester 8 4 8 1.5 CE7 None 2 2 0 0