US3719698A - Polyfluorinated esters of acids containing silicon and amino groups - Google Patents

Polyfluorinated esters of acids containing silicon and amino groups Download PDF

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US3719698A
US3719698A US00685946A US3719698DA US3719698A US 3719698 A US3719698 A US 3719698A US 00685946 A US00685946 A US 00685946A US 3719698D A US3719698D A US 3719698DA US 3719698 A US3719698 A US 3719698A
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G Tesoro
R Ring
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JP Stevens and Co Inc
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D203/00—Heterocyclic compounds containing three-membered rings with one nitrogen atom as the only ring hetero atom
    • C07D203/04—Heterocyclic compounds containing three-membered rings with one nitrogen atom as the only ring hetero atom not condensed with other rings
    • C07D203/06—Heterocyclic compounds containing three-membered rings with one nitrogen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
    • C07D203/08—Heterocyclic compounds containing three-membered rings with one nitrogen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring nitrogen atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/06—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
    • C07D213/16—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom containing only one pyridine ring
    • C07D213/20—Quaternary compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
    • C07F7/1804—Compounds having Si-O-C linkages
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
    • D06M13/325—Amines
    • D06M13/342—Amino-carboxylic acids; Betaines; Aminosulfonic acids; Sulfo-betaines
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
    • D06M13/487—Aziridinylphosphines; Aziridinylphosphine-oxides or sulfides; Carbonylaziridinyl or carbonylbisaziridinyl compounds; Sulfonylaziridinyl or sulfonylbisaziridinyl compounds
    • D06M13/493—Aziridinylphosphines; Aziridinylphosphine-oxides or sulfides; Carbonylaziridinyl or carbonylbisaziridinyl compounds; Sulfonylaziridinyl or sulfonylbisaziridinyl compounds perfluorinated

Definitions

  • This invention relates to polyfluorinated nitrogencontaining esters which are useful inter alia as finishing agents or intermediates for preparing finishing agents.
  • this invention concerns the abovementioned esters which can be employed as oil and water repellents, soil or stain releasing agents, as intermediates for preparing these agents, and as acrylate donors of improved solubility for modifying cellulose and wool.
  • novel compositions of this invention are included within the formu l a V wherein R, is a polyfluorinated hydrocarbon radical containing at least three fluorine atoms and up to carbon atoms, preferably selected from aliphatic and aromatic radicals; A is an alkylene radical of up to six carbon atoms; Z is a residue of an amine or amine salt after at least one or two hydrogens have been removed, and q is either the integer l or 2.
  • the preferred group comprises those compounds represented in the structural formula where R; is polyfluorinated aliphatic radicals having from three to 11 carbon atoms and six to 21 fluorine atoms. These compositions are useful finishing agents and can be prepared readily from available materials.
  • a more specific object of this invention is the preparation of the above esters useful as organic intermediates and as intermediates for the preparation of textile finishing agents such as soil release agents and oil and water repellents.
  • an acrylic-type ester of a polyfluorinated alcohol is directly reacted with an amine containing at least one reactive hydrogen atom. Addition takes place across the site of unsaturation as shown by the illustrative reactions below:
  • both aliphatic and aromatic polyfluorinated unsaturated esters lend themselves to the preparation of the inventive products by the described process.
  • the amine reactant can be acyclic, carbocyclic or heterocyclic.
  • the chain as well as the ring may contain one or more heteroatoms (as oxygen or silicon). Branching and/or unsaturation may occur.
  • Another more indirect procedure to prepare the unsaturated ester reactants is resorted to when the desired ester is to be synthesized from a polyfluoro alcoholin which halogen and hydroxyl are attached to the same acryloyl chloride to undergo metathesis to form the desired ester and cesium salt as the by-product.
  • halopropionic acid such as 3-chloropropionic acid is reacted with a polyfluorinated anhydride such as trifluoroacetic anhydride to form the 3-chloropropionic trifluoroacetic anhydride, which is then reacted in situ with a polyfluorinated alcohol of the type:
  • Suitable illustrative polyfluorinated alcohols include the following:
  • Durability to Laundering Home-type machine, low (ll-gallon) water level, 4-pound load, detergent, normal agitation, 12-minute wash cycle at 60 C, rinse at 43 i 3 C, normal rinse and spin cycle, and tumble-dry at 74 C.
  • Oil Repellency Swatches of fabric were placed flat on a table, with edges held down by weights. Drops of mineral oil were placed onto the surface of the fabric at various places, and the effect was observed. Oil repellency was shown if no penetration, wetting, or darkening occurred as the drops remained undisturbed for 3 minutes. Specifications on the mineral oil: Saybolt Viscosity of 360 to 390 at F (377/9 C) and a specific gravity of 0.880 to 0.900 at 60 F (155/9 C). Oil and Water Repellent Concentration: An oil and water repellent concentration as used herein refers to that quantity of polyfluorinated ester reagent which will prevent substantial penetration of the glass or cellulosic substrate by oil or water.
  • This concentration is a variable dependent upon the type of substrate to be protected and the reagent employed. Experimentally it has been determined that satisfactory repellency can ordinarily be obtained at concentrations of reagents ranging from about 0.1 percent by weight of reagent and above based upon the weight of substrate to be protected. Preferably, the reagent applied will be in the concentration range of from about 0.5 percent by weight and above based upon the weight of the substrate. The upper limit of these concentrations is primarily limited by costs.
  • OWB On the weight of the bath.
  • OWF 0n the weight of the fabric.
  • EXAMPLE 5 The following compounds were measured into a 125- ml. flask equipped with a magnetic stirrer: 9.08 grams (0.02 mole) of 1H,1l-l-pentadecafluorooctyl acrylate and 30 ml. of ethyl ether. Stirring was started, and a solution of 2.21 grams (0.01 mole) of 3-(triethoxysilyl)-propylamine in 20 ml. of ethyl ether was added. Stirring was discontinued, the flask was corked, and the solution was allowed to stand at room temperature for approximately 16 hours. Ethyl ether and other volatile material were removed by distillation. The remaining viscous liquid weighed 10.5 grams.
  • EXAMPLE 8 Preparation of 1-[2-( ll-l,1l-l,1 ll-l-Eicosafluoroundecyloxy )ethyl]-pyridinium Chloride of 63 hours, by which time the reaction had gone 66 percent to completion, based on the amount of chloride ion produced. Methanol and unreacted pyridine were removed by distillation at approximately 25 torrs while the mixture was kept warmed at room temperature.
  • EXAMPLE 9 Preparation of 1l-1,1H,1ll-l-Eicosafluoroundecyl 3- 1-Aziridinyl)propionate H(CFz)1uCH2O
  • ⁇ CH CH 11mm mornmoirroocnzommrrz
  • the addition reaction was effected with the following compounds, using the apparatus and procedure of EX- AMPLE 4: 11.72 grams (0.02 mole) of 1H,1H,11H- eicosafluoroundecyl acrylate in 40 ml. of ethyl ether, and 0.86 gram (0.02 mole) of ethylenimine.
  • the adduct obtained weighed 12.5 grams, a virtually quantitative yield.
  • EXAMPLE 1 1 Preparation of lH,ll-l,7H-Dodecafluoroheptyl 2-(1- Aziridinyl)propionate This compound was prepared from ethylenimine and 1H,lH,71-l-dodecafluoroheptyl acrylate by the procedure outlined in EXAMPLE 9. The product obtained was purified by distillation. Yield 88%, hp 78-92 C/O.4mm. Equivalent weight determined by potentiometric titration: Calcd.: 429; Found: 460.
  • reaction mixture was cooled to 0 C, and a total of 0.5 liter of cold water was added during a period of 20 minutes while the temperature was kept at 10 C. Then stirring was stopped and the mixture separated into layers. The lower layer was isolated and diluted by 0.5 liter of dichloromethane. That solution was washed by five 150-ml. portions of water, and then dried by standing over anhydrous sodium sulfate. Approximately 0.1 gram of hydroquinone was added to the dry liquid (separated from the drying agent), and the liquid was subjected to fractional distillation at reduced pressure. The acrylate of 2H-hexafluoro-2- propanol was collected between 38 and 42 C at 140 torrs. The normal boiling point was approximately 88 C. The distilled ester weighed grams (40 percent of the theoretical yield). The infrared spectrum confirmed the identity of this ester.
  • the reaction mixture was cooled to 0 C, and a total of 100 ml. of water was added slowly with stirring while the temperature was kept below C. Finally the mixture was allowed to separate into layers. The lower layer was isolated. It was washed with five 50-ml. portions of cold water, and dried by standing over anhydrous sodium sulfate. The dry liquid was fractionally distilled at reduced pressure. The 3-chloropropionate of 2l-l-hexafluoro-2-propanol was collected at 61 C at 40 torrs; 54.1 grams (48.5 percent yield).
  • EXAMPLE 16 Preparation of 2,2,2-Trifluorol (trifluoromethyl)ethyl 3-( l-Aziridinyl)propionate Using a method similar to that of EXAMPLE 4 (except that the time allowed was 4 days), an addition reaction was carried out with the following compounds: 5.6 grams (0.025 mole) of the acrylate of 2l-l-hexafluoro-2-propanol dissolved in 30 ml. of ethyl ether, and 1.1 gram (0.025 mole) of ethylenimine dissolved in 20 ml. of ethyl ether. At the end of the reaction period, volatile compounds were removed by distillation at atmospheric pressure while the pot temperature was raised to 70 C.
  • EXAMPLE 17 Using a method similar to that of EXAMPLE 4 (except that the time allowed was four days), an addition reaction was carried out with the following compounds: 5.6 grams (0.025 mole) of the acrylate of ZH-heirafluoro-2-propanol dissolved in 30 ml. of ethyl ether, and 2.8 grams (0.0125 mole) of 3-(triethoxysily1)propylarnine dissolved in 20 ml. of ethyl ether. At the end of the reaction period, volatile material was removed by distillation at atmospheric pressure while the pot temperature was raised to C.
  • EXAMPLE 20 illustrates the usefulness of this new composition having the molecular formula C H ,F NO-,Si as a water-repellent finish for cotton fabric.
  • the use of this polyfluoroalkyl ester of N-substituted beta-alanine to increase oil repellency of glass fabrics is shown in EXAMPLES 21 and 22.
  • EXAMPLE 18 Preparation of 1 ,2,2,2-' letrafluoro-2- (trifluoromethyl)ethyl Acrylate
  • Cesium fluoride 126 grams, 0.75 mole
  • 360 ml. of redistilled bis(2-methoxyethyl) ether were cooled to 78 C in a l-liter, 3-neck round-bottom flask which had been flame dried and fitted with a condenser, stirrer, gas inlet tube, and thermometer.
  • a total of 138 grams (0.84 mole) of hexafluoroacetone was bubbled into the mixture.
  • EXAMPLE 19 Use of the Adduct of EXAMPLE 12 as a Water- Repellent Finish on Cotton Fabric
  • 100 percent cotton fabric 8 ounces per square yard in a twill weave
  • the relative humidity at 65 i- 2 percent (21 2*: 1 C) and weighed to the nearest milligram.
  • Each sample was padded with a solution of bis(ll-l,lH,111-1- eicosafluoroundecyl) N-[3-(triethoxysilyl)propyl]- 3,3'-iminodipropionate (the product of EXAMPLE 12, C H F NO Si) in bis(2-methoxyethyl) ether.
  • the concentration of the reagent in the pad bath was 5.0 percent for Samples K and L, and 1.8 percent for Samples M and N.
  • the wet pick-up was 62 percent.
  • Other quantitative details are in the accompanying table.
  • EXAMPLE 21 Use of the Adduct of EXAMPLE 17 (Applied from Solution) as an Oil-Repellent Finish on Glass Fabric A glass fabric was selected which was of a style popular for draperies, having a thread count of 56 X 54.
  • Wct pick-up from the aqueous pad bath was approximately EXAMPLE 20 Use of the Adduct of EXAMPLE 17 as a Water- Repellent Finish on Cotton Fabric

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

Polyfluorinated esters of the formula WHEREIN Rf is a polyfluorinated hydrocarbon radical containing at least three fluorine atoms and up to 20 carbon atoms, A is an alkylene radical of up to six carbon atoms, Z is the residue of an amine component selected from the group consisting of amines and amine slats which have had at least one hydrogen atom removed, and q is an integer selected from 1 and 2, useful as textile finishing agents.

Description

United States Patent 11 1 Tesoro et a].
[54] POLYFLUORINATED ESTERS OF 1 ACIDS CONTAINING SILICON AND AMINO GROUPS [75] Inventors: Giuliana C. Tesoro, Dobbs Ferry,
N.Y.; Richard Ring, Wood-Ridge,
[73 A ssignee: J. P. Stevens & (20., Inc., New York,
[22] Filed: Nov. 27, 1967 [21] Appl. No.: 685,946
Related U.S. Application Data [63] Continuation-impart of Ser. No. 178,572, March 9,
1962, Pat. No. 3,575,961.
[52] U.S. Cl ..260/448.8 R, 8/116.2 R, 8/128 R, 117/123 D, 117/1355, 260/239 E, 260/295 R, 260/468 R, 260/479 S, 260/482 R,
260/633 [51] Int. Cl ..C07c 101/20, C07d 23/06, C07f 7/13 [58] Field of Search ..260/239 E, 448.8, 448.2
[ 5] March 6, 1973 [56] References Cited UNITED STATES PATENTS 3,504,998 4/1970 Speier ..260/448.8 3,457,349 7/1969 Jelinek ..260/239 E Primary Examiner-Alton D. Rollins Attorney-J. Bradley Cohn and Bernard Marlowe [57] ABSTRACT Polyfluorinated esters of the formula RrOCA qZ 4 Claims, No Drawings POLYFLUORINATED ESTERS OF ACIDS CONTAINING SILICON AND AMINO GROUPS This application is a continuation-in-part of our copending application Ser. No. 178,572, filed Mar. 9, 1962, now US. Pat. No. 3,575,961.
This invention relates to polyfluorinated nitrogencontaining esters which are useful inter alia as finishing agents or intermediates for preparing finishing agents.
More particularly, this invention concerns the abovementioned esters which can be employed as oil and water repellents, soil or stain releasing agents, as intermediates for preparing these agents, and as acrylate donors of improved solubility for modifying cellulose and wool.
The novel compositions of this invention are included within the formu l a V wherein R, is a polyfluorinated hydrocarbon radical containing at least three fluorine atoms and up to carbon atoms, preferably selected from aliphatic and aromatic radicals; A is an alkylene radical of up to six carbon atoms; Z is a residue of an amine or amine salt after at least one or two hydrogens have been removed, and q is either the integer l or 2.
While all of the above compounds are useful, as in any large group, some members of the group are preferred compared to the group at large. In this instance the preferred group comprises those compounds represented in the structural formula where R; is polyfluorinated aliphatic radicals having from three to 11 carbon atoms and six to 21 fluorine atoms. These compositions are useful finishing agents and can be prepared readily from available materials.
It is an object of this invention among others to prepare useful novel polyfluorinated esters containing at least three fluorine atoms and no more than one nitrogen atom per molecule.
A more specific object of this invention is the preparation of the above esters useful as organic intermediates and as intermediates for the preparation of textile finishing agents such as soil release agents and oil and water repellents.
Further objects will become apparent to those skilled in the art after a perusal of this invention.
In practice the above objects are achieved by the utilization of the aforementioned esters formed by several different processes.
In one process, an acrylic-type ester of a polyfluorinated alcohol is directly reacted with an amine containing at least one reactive hydrogen atom. Addition takes place across the site of unsaturation as shown by the illustrative reactions below:
A'Jn be seerifrom an examination of the above illustrative embodiments, both aliphatic and aromatic polyfluorinated unsaturated esters lend themselves to the preparation of the inventive products by the described process. Similarly, the amine reactant can be acyclic, carbocyclic or heterocyclic. Furthermore, the chain as well as the ring may contain one or more heteroatoms (as oxygen or silicon). Branching and/or unsaturation may occur.
A list of illustrative amines and amine salts which can be employed is as follows:
A list of illustrative polyfluorinated unsaturated esters which can be employed is supplied below:
mas stave raiymiariaateanssmaea Esters 0 o racnco iicH=cHg, F3c 2c0ii-cH:cH1,
l V l i I? (FsC)zCOC-C=CH, (F;C)1C-OCC=CH:,
III OH; T (:HP
0 o no no rictrz-oiicnalcm, 11 0 no mmxnoiimnxnn,
monoluncrnoommn, F CGUOi Cll Cflq C3115 CH3 I I (mamas,
is first formed, which upon addition of the fluorinated alcohol esterfies the alcohol to form the desired fluorinated, unsaturated ester.
Another more indirect procedure to prepare the unsaturated ester reactants is resorted to when the desired ester is to be synthesized from a polyfluoro alcoholin which halogen and hydroxyl are attached to the same acryloyl chloride to undergo metathesis to form the desired ester and cesium salt as the by-product.
In another procedure used to prepare the inventive composition, a more indirect preparative method is a saturated employed. In one favored variant,
polyfluorinated ester halide of the type r RJOCAX wherein R, and A are as defined previously and X is a reactive halogen, is formed and reacted with an amine or amine salt of the type described supra, to give the inventive products.
ll H(CFz)aCH2OCCH2CHzN During the course of this procedure a halopropionic acid such as 3-chloropropionic acid is reacted with a polyfluorinated anhydride such as trifluoroacetic anhydride to form the 3-chloropropionic trifluoroacetic anhydride, which is then reacted in situ with a polyfluorinated alcohol of the type:
R AOH patent of Hollander et al., US. Pat. No. 3,177,185 (1965).
Suitable illustrative polyfluorinated alcohols include the following:
tafluoropropionic trifluoroacetic anhydride.
To illustrate the workings of this invention in the greatest possible detail, the following illustrative embodiments are submitted. Preceding the examples is a brief description of the test methods used.
TEST METHODS AND WORKING EXAMPLES Vinyl, CH =CH: Determined by means of l dodecanethiol according to the procedure described on page 61 of Chemistry of Acrylonitrile (The American Cyanamid Company, New York, 1959, second edition). For the determination of a water-soluble vinyl compound, the reagent was 2-mercaptoethanol in the presence of excess base.
Water Repellency Spray Rating: AATCC Test Method 22-l 964, Manual of the American Association of Textile Chemists and Colorists, 1964 edition, pages B-l30-31.
Durability to Laundering: Home-type machine, low (ll-gallon) water level, 4-pound load, detergent, normal agitation, 12-minute wash cycle at 60 C, rinse at 43 i 3 C, normal rinse and spin cycle, and tumble-dry at 74 C.
Durability to Dry Cleaning: Commercial equipment and formulation.
Oil Repellency: Swatches of fabric were placed flat on a table, with edges held down by weights. Drops of mineral oil were placed onto the surface of the fabric at various places, and the effect was observed. Oil repellency was shown if no penetration, wetting, or darkening occurred as the drops remained undisturbed for 3 minutes. Specifications on the mineral oil: Saybolt Viscosity of 360 to 390 at F (377/9 C) and a specific gravity of 0.880 to 0.900 at 60 F (155/9 C). Oil and Water Repellent Concentration: An oil and water repellent concentration as used herein refers to that quantity of polyfluorinated ester reagent which will prevent substantial penetration of the glass or cellulosic substrate by oil or water. This concentration is a variable dependent upon the type of substrate to be protected and the reagent employed. Experimentally it has been determined that satisfactory repellency can ordinarily be obtained at concentrations of reagents ranging from about 0.1 percent by weight of reagent and above based upon the weight of substrate to be protected. Preferably, the reagent applied will be in the concentration range of from about 0.5 percent by weight and above based upon the weight of the substrate. The upper limit of these concentrations is primarily limited by costs.
OWB: On the weight of the bath. OWF: 0n the weight of the fabric.
EXAMPLE 1 Preparation of 1H,1H'Pentadecafluoroocty1 Acrylate i? [F 0 C] 0 Acrylic acid grams, 0.14 mole) was cooled to 10 C in a 250-ml. flask. While stirring, a total of 30 grams (0.14 mole) of trifluoroacetic anhydride was added dropwise at 10 to C. Then a total of 50 grams (0.11 mole) of 1H,ll'l-pentadecafluoro-l-octanol was added dropwise while the temperature was kept below 30 C. Upon completion of the addition, the reaction mixture was stirred for 2 hours at room temperature. Next, a total of 30 ml. of water was added slowly with stirring while the temperature was kept below 50 C. Finally the mixture was allowed to separate into layers. The lower layer was isolated and distilled. The fraction distilling between 53 and 56 C at 2 torrs weighed 42 grams. It had a vinyl content of 5.92 percent by analysis. The vinyl content theoretically required for 111,1 l-l-pentadecafluorooctyl acrylate is 5.95 percent.
EXAMPLE 2 Preparation of 1H,ll-l-Pentadecafluorooctyl 3- A total of 67.2 grams (0.32 mole) of trifluoroacetic anhydride was added slowly with stirring to 33.6 grams (0.3] mole) of 3-chl0ropropionic acid kept just below 15 C in a 250-ml., 3-neck flask equipped with a dropping funnel, stirrer, and thermometer. The reaction mixture was stirred at 10 to 15 C for 15 minutes after all the anhydride had been added in order to allow for completion of the formation of 3-chloropropionic trifluoroacetic anhydride. Then a total of 120 grams (0.30 mole) of molten 1H,ll-l-pentadecafluoro-1-octanol was added while the temperature was kept between 10 and 30 C. Upon completion of the addition, the reaction mixture was stirred for 2 hours at 25 .to 30 C. Next, the reaction mixture was cooled to 10 C, and a -ml. portion of cold water was added while the temperature was kept just below 15 C. Then stirring was stopped and the mixture separated into layers. The lower layer was separated. The operation of adding a 75-ml. portion of cold water was repeated two times on the lower layer. The final lower layer was diluted with 250 ml. of ethyl ether, then dried by standing 16 hours over anhydrous sodium sulfate. After filtering to remove the drying agent, the liquid was subjected to fractional distillation at reduced pressure. The 3- chloropropionate of 1H,lH-pentadecafluoro-l-octanol was collected between 62 and 66 C at 0.1 torr. The distilled ester weighed 86 grams. The identity of the product was confirmed by the infrared spectrum and by the following analytical values.
Preparation of l- 2-[(1H,lH-Pentadecafluorooctyloxy)carbonyl]ethyl -pyridinium Chloride The following compounds were measured into a 250- ml. 3-neck flask fitted with a thermometer, stirrer, and reflux condenser: 24.5 grams (0.05 mole) of lI-1,ll-lpentadecafluorooctyl 3-chloropropionate,4.0 grams (0.0506 mole) of pyridine, and 50 ml. of methanol. The mixture was stirred and heated to refluxing for a total of 63 hours, by which time the reaction had gone 67 percent to completion, based on the determination of chloride ion. Methanol and unreacted pyridine were removed by distillation at approximately 25 torrs while the mixture was kept at 45 C. The resulting product, 21 grams, mainly 1- 2-[(1H,1H-pentadecafluorooctyloxy)carbonyl]ethyl -pyridinium chloride, gave the following results upon analysis: chloride ion, 4.18 percent; latent vinyl corresponding to an actual vinyl content of 6.25 percent. (Vinyl content was determined by means of 2-mercaptoethanol in the presence of excess base.) The adduct, a quaternary ammonium salt, was very soluble in water, despite the pentadecafluorooctyl moiety in the cation. This product is useful as an acrylate donor (for chemically bonding pentadecafluorooctyl through a bridging group to cellulose or wool) because of its solubility property.
EXAMPLE 4 Preparation of ll-l,ll-l-Pentadecafluorooctyl 3-( 1- Aziridinyl)propionate F (CF)1cH1Oc' oH cn, nxr; 11 cm 1*(0 whom-0r cmcmsorm m,
1 weighed 9.4 grams. It had a nitrogen content of 2.40
percent (2.82 percent by theory). The infrared spectrum confirmed that the adduct was 1H,1H-pentadecafluorooctyl 3-( l-aziridinyl)propionate. Titration with hydrochloric acid indicated an aziridinyl content of 7.05 percent (8.48 percent by theory).
EXAMPLE 5 The following compounds were measured into a 125- ml. flask equipped with a magnetic stirrer: 9.08 grams (0.02 mole) of 1H,1l-l-pentadecafluorooctyl acrylate and 30 ml. of ethyl ether. Stirring was started, and a solution of 2.21 grams (0.01 mole) of 3-(triethoxysilyl)-propylamine in 20 ml. of ethyl ether was added. Stirring was discontinued, the flask was corked, and the solution was allowed to stand at room temperature for approximately 16 hours. Ethyl ether and other volatile material were removed by distillation. The remaining viscous liquid weighed 10.5 grams. It had a nitrogen content of 1.35 percent (1.24 percent by theory) and an infrared spectrum which confirmed that the adduct was bis( 1H 1 l-l-pentadecafluorooctyl) N-[ S-(triethoxysilyl )propyl]-3 ,3 -iminodipropionate.
Preparation of Acrylate H020 CH=CH Acrylic acid 15.1 grams, 0.21 mole) and 0.1 gram of hydroquinone (to inhibit polymerization) were put into a 250-ml. flask fitted with a stirrer, a dropping funnel, and a thermometer. While stirring and cooling, a total of 46.2 grams (0.22 mole) of trifluoroacetic anhydride was added portionwise at to C. Then a total of 106.4 grams (0.20 mole) of 1H,1l-l,l1l-l-eicosa.fluorol-undecanol was added while the temperature was kept below 30 C. Upon completion of the addition, the reaction mixture was stirred for 2 hours at room temperature. Next, a total of 50 ml. of water was added slowly with stirring while the temperature was kept below 15 C. Some solidification occurred, so a 250-ml. portion of ethyl ether was added. The organic layer was washed with -ml. portions of 5 percent sodium carbonate until an added portion remained pink to phenolphthalein. Then the organic layer was washed with water and dried over anhydrous magnesium sulfate. Solvent was removed by distillation. That left the ester as a white solid. It was recrystallized from alcohol to which water was added. The product weighed 75.5 grams and melted at 44.0 to 445 C. It had a vinyl content of 4.60 percent by analysis. The vinyl content theoretically required for 1H,1H,1 lH-eisosafluoroundecyl acrylate is 4.68 percent.
EXAMPLE 7 Preparation of 1H,1H,llH-Eicosafluoroundecyl 3- Chloropropionate o I ll H020 0112011201 Frag-0430112011291 A total of 46.2 grams (0.22 mole) of trifluoroacetic anhydride was added slowly with stirring at 10 to 15 C to 22.8 grams (0.21 mole) of 3-chloropropionic acid in a 500-ml. flask. After the addition, the reaction mixture 7 was stirred for 15 minutes (still at 10 to 15 C) to allow for completion of the formation of 3-chloropropionic trifluoroacetic anhydride. Then, a total of 106.4 grams was added, and stirring was continued for an additional period of 3 hours, during which time the temperature was allowed to rise to 29 C as the ester formed. Next, the reaction'mixture was cooled to 15 C, and a 250-ml. portion of cold water was added. After the mixture had been stirred for 15 minutes, the white precipitate was collected by filtration. The product was dissolved in ethanol, and recrystallized from aqueous ethanol. The yield of 1H l H, 1 ll-l-eicosafluoroundecyl 3- chloropropionate was 93 grams (76 percent yield) melting at 60-61 C. The identity of this ester was established by its infrared spectrum and the following analytical results.
c 11 c1 F Analysis (in Found: 26.03 1.25 5.27 57.69
Required for c,.1-1,c11-',,0,= 27.00 1.13 5.70 61.22
EXAMPLE 8 Preparation of 1-[2-( ll-l,1l-l,1 ll-l-Eicosafluoroundecyloxy )ethyl]-pyridinium Chloride of 63 hours, by which time the reaction had gone 66 percent to completion, based on the amount of chloride ion produced. Methanol and unreacted pyridine were removed by distillation at approximately 25 torrs while the mixture was kept warmed at room temperature. The resulting product, 28 grams, mainly l-[ 2( 1l-1,1H,l 1l-l-eicosafluoroundecyloxy)ethyl] pyridinium chloride, gave the following results upon analysis: chloride ion, 3.33 percent; latent vinyl corresponding to an actual vinyl content of 4.33 percent. (Vinyl content was determined by means of 2-mercaptoethanol in the presence of excess base.) The adduct, a quaternary ammonium salt, was a waxy solid, virtually insoluble in water because of the eicosafluoroundecyl moiety in the cation.
EXAMPLE 9 Preparation of 1l-1,1H,1ll-l-Eicosafluoroundecyl 3- 1-Aziridinyl)propionate H(CFz)1uCH2O|1|}CH=CH 11mm mornmoirroocnzommrrz The addition reaction was effected with the following compounds, using the apparatus and procedure of EX- AMPLE 4: 11.72 grams (0.02 mole) of 1H,1H,11H- eicosafluoroundecyl acrylate in 40 ml. of ethyl ether, and 0.86 gram (0.02 mole) of ethylenimine. The adduct obtained weighed 12.5 grams, a virtually quantitative yield. It was a waxy solid; N: found, 2.4 percent; required for C H F NO 2.1 percent. Titration with hydrochloric acid indicated an aziridinyl content of 5 .98 percent (6.68 percent by theory), confirming that the adduct was the ester, 1H,ll-l,1 lH-eicosafluoroundecyl 3-( 1-azirdinyl)propionate.
EXAMPLE EXAMPLE 1 1 Preparation of lH,ll-l,7H-Dodecafluoroheptyl 2-(1- Aziridinyl)propionate This compound was prepared from ethylenimine and 1H,lH,71-l-dodecafluoroheptyl acrylate by the procedure outlined in EXAMPLE 9. The product obtained was purified by distillation. Yield 88%, hp 78-92 C/O.4mm. Equivalent weight determined by potentiometric titration: Calcd.: 429; Found: 460.
EXAMPLE 12 Preparation of Bis( 1H,1H,l ll-I-eicosafluoroundecyl) N 3-(Triethoxysily1)propyl ]-3 ,3 -iminodipropionate 2mm meur-oficumiom umomomon,sic-00,115
EXAMPLE 13 Preparation of (trifluoromethyl)ethyl Acrylate 2,2,2-Trifluoro- 1 FaCCO2H A solution consisting of grams of 96 percentpure acrylic acid and 0.8 gram of hydroquinone was added slowly to 454 grams of trifluoroacetic anhydride at 0 to 10 C in a 2-1iter 3-neck flask fitted 'with a thermometer, stirrer, and dropping funnel with a drying tube. Then a total of 330 grams of 2H-hexafluoro-2- propanol was added while the temperature was kept between 10 and 20 C. Upon completion of the addition, the reaction mixture was stirred for 1.5 hours at 25 to 30 C and for an additional 2 hours at 40 C. Next, the reaction mixture was cooled to 0 C, and a total of 0.5 liter of cold water was added during a period of 20 minutes while the temperature was kept at 10 C. Then stirring was stopped and the mixture separated into layers. The lower layer was isolated and diluted by 0.5 liter of dichloromethane. That solution was washed by five 150-ml. portions of water, and then dried by standing over anhydrous sodium sulfate. Approximately 0.1 gram of hydroquinone was added to the dry liquid (separated from the drying agent), and the liquid was subjected to fractional distillation at reduced pressure. The acrylate of 2H-hexafluoro-2- propanol was collected between 38 and 42 C at 140 torrs. The normal boiling point was approximately 88 C. The distilled ester weighed grams (40 percent of the theoretical yield). The infrared spectrum confirmed the identity of this ester.
EXAMPLE 14 Preparation of 2,2,2-Trifluoro- 1 (trifluoromethyl)ethyl 3-Chloropropionate I H (FaChC-OCCHzCIhCl A total of 51.6 grams of 3-chloropropionic acid was added slowly with stirring to 100 grams of trifluoroacetic anhydride at C in a 500-ml. flask fitted with a thermometer, stirrer, and a dropping funnel with a drying tube. Then the temperature was raised to 10 C, and 2l-l-hexafluoro-2-propanol was added dropwise with stirring. Upon completion of the addition, the reaction mixture was stirred for 5 hours as the temperature rose gradually to 40 C. The reaction mixture was cooled to 0 C, and a total of 100 ml. of water was added slowly with stirring while the temperature was kept below C. Finally the mixture was allowed to separate into layers. The lower layer was isolated. It was washed with five 50-ml. portions of cold water, and dried by standing over anhydrous sodium sulfate. The dry liquid was fractionally distilled at reduced pressure. The 3-chloropropionate of 2l-l-hexafluoro-2-propanol was collected at 61 C at 40 torrs; 54.1 grams (48.5 percent yield).
Using apparatus and general procedure both similar to those of EXAMPLE 4, an addition reaction was carried out with the following compounds: 11.1 grams (0.05 mole) of the acrylate of 2l-l-hexafluoro-2- propanol dissolved in 30 ml. of ethyl ether, and 5.0 grams (0.05 mole) of diallylamine dissolved in 20 ml.
of ethyl ether. After processing, the yield of the 3-(diallylamino)propionate of 2l-l-hexafluoro-2-propanol which distilled between 46 and 47 C at 0.4 torr was 10.2 grams (63.3 percent). The structure of the adduct was confirmed by its infrared spectrum and by nitrogen content: found, 4.40 percent; required for C I-1 E, N0 4.39 percent.
EXAMPLE 16 Preparation of 2,2,2-Trifluorol (trifluoromethyl)ethyl 3-( l-Aziridinyl)propionate Using a method similar to that of EXAMPLE 4 (except that the time allowed was 4 days), an addition reaction was carried out with the following compounds: 5.6 grams (0.025 mole) of the acrylate of 2l-l-hexafluoro-2-propanol dissolved in 30 ml. of ethyl ether, and 1.1 gram (0.025 mole) of ethylenimine dissolved in 20 ml. of ethyl ether. At the end of the reaction period, volatile compounds were removed by distillation at atmospheric pressure while the pot temperature was raised to 70 C. Then the 3-( l-aziridinyl)propionate of 2H-hexafluoro-2-propan0l was isolated by distillation at reduced pressure as a fraction collected between 54 and 55 C at 10 torrs; n 1.3541. The yield of the adduct was 5.0 grams (75 percent).
Aziri- C H F N dine Analysis (in Found: 36.11 3.53 38.90 6.55 14.3 Required for C,,H.F,N0,= 36.24 3.42 42.99 5.28 15.9
* The method of determination used is described in Schaefer et al., Journal American Chemical Society, Vol. 77, 5918-5922 (1955).
EXAMPLE 17 Using a method similar to that of EXAMPLE 4 (except that the time allowed was four days), an addition reaction was carried out with the following compounds: 5.6 grams (0.025 mole) of the acrylate of ZH-heirafluoro-2-propanol dissolved in 30 ml. of ethyl ether, and 2.8 grams (0.0125 mole) of 3-(triethoxysily1)propylarnine dissolved in 20 ml. of ethyl ether. At the end of the reaction period, volatile material was removed by distillation at atmospheric pressure while the pot temperature was raised to C. A quantitative yield was obtained of the adduct, the N-[3-(triethoxysily1)propyl]-3,3'-iminodipropionate of 2l-l-hexafluoro-2-propanol, the structure being in accord with the infrared spectrum. EXAMPLE 20 illustrates the usefulness of this new composition having the molecular formula C H ,F NO-,Si as a water-repellent finish for cotton fabric. The use of this polyfluoroalkyl ester of N-substituted beta-alanine to increase oil repellency of glass fabrics is shown in EXAMPLES 21 and 22.
EXAMPLE 18 Preparation of 1 ,2,2,2-' letrafluoro-2- (trifluoromethyl)ethyl Acrylate Cesium fluoride (126 grams, 0.75 mole) and 360 ml. of redistilled bis(2-methoxyethyl) ether were cooled to 78 C in a l-liter, 3-neck round-bottom flask which had been flame dried and fitted with a condenser, stirrer, gas inlet tube, and thermometer. A total of 138 grams (0.84 mole) of hexafluoroacetone was bubbled into the mixture. Then the mixture containing the cesium derivative of heptafluoro-Z-propanol was warmed to room temperature and re-chilled to 10 C. Acryloyl chloride (75.2 grams, 0.75 mole) was added dropwise during a 20-minute period. Next, the mixture was stirred for 1 hour at room temperature, and for 1 hour at 50 C. It was cooled and filtered to remove cesium chloride. The filtrate, diluted by 250 ml. of ethyl ether, was poured into 1 liter of cold water. The lower layer C H F Analysis (in%). Found: 29.95 1.24 54.56 Required for C,,l-l- ,F-,O,: 30.00 1.25 55.40
EXAMPLE 19 Use of the Adduct of EXAMPLE 12 as a Water- Repellent Finish on Cotton Fabric Four samples of 100 percent cotton fabric (8 ounces per square yard in a twill weave) were conditioned with the relative humidity at 65 i- 2 percent (21 2*: 1 C) and weighed to the nearest milligram. Each sample was padded with a solution of bis(ll-l,lH,111-1- eicosafluoroundecyl) N-[3-(triethoxysilyl)propyl]- 3,3'-iminodipropionate (the product of EXAMPLE 12, C H F NO Si) in bis(2-methoxyethyl) ether. The concentration of the reagent in the pad bath was 5.0 percent for Samples K and L, and 1.8 percent for Samples M and N. For each padding of the reagent, the wet pick-up was 62 percent. Other quantitative details are in the accompanying table.
The fabric samples were dried at approximately 50 C. Samples L and N were overpadded with an aqueous dispersion of a mixed catalyst, as noted in the table, and re-dried as before. The same curing conditions were applied to each sample, viz., 5 minutes at approximately 177 C. Next each sample was rinsed in bis(2- methoxyethyl) ether, and then in water containing approximately 0.1 percent of a nonionic detergent, namely p-( l l ,3 ,3-tetramethylbutyl)-phenoxynonaethoxyethanol. After drying, the samples were re-conditioned and re-weighed as before. Even small amounts of the finish, an amine adduct of a polyfluoroalkyl acrylate, provided water repellency, as shown in the table.
" TABLE FOR EXAMPLE m m trifluoro- 1 -(trifluoromethyl )ethyl] N-[ 3-( triethoxysily1)propyl]-3,3'-iminodipropionate (the product of EXAMPLE l7, C ,H F, NO Si) in p-dioxane. The concentration of the reagent in the pad bath was 4.0 percent for Samples A, B, C, D, and H, and 1.5 percent for Samples E, F, and G. For each padding of the reagent, the wet pick-up was 62 i 1 percent. Other quantitative details are in the accompanying table.
The fabric samples were dried at approximately 65 C. Samples B through G were overpadded with an aqueous dispersion of a catalyst, as noted in the table. (Before using Catalyst 81 and 128, the pH of the aqueous dispersion was fixed at 6.5 i 0.5 by means of acetic acid if previously above that range.) For Sample H, benzoyl peroxide was applied with the reagent from pdioxane. Samples of overpadded fabric were re-dried as before. The same curing conditions were applied to each sample, viz., 5 minutes at approximately 177 C. Next, each sample was rinsed in bis(2-methoxyethyl) ether, and then in water. After drying, the samples were reconditioned and reweighed as before. Results in the table show that the finish, an amine adduct of a polyfluoroalkyl acrylate, provided water repellency.
TABLE FOR EXAMPLE 20 Reagent, Catalysts, OWB Water repelleney C11H31F12N07Sl percent spray rating Organo- Metal tuncorg. After OWB OWF, tional, salt, Orlgllaunderpercent percent Type 81 Type 128 nally ing Sample A 4. 0 2. 5 None None 50/70 0/60 4. 0 2. 5 0. 1 None 70 4. 0 2. 5 None 0. 6 70 50 D 4. 0 2. 5 0. 1 0. 6 50/70 70 E 1. 5 0. 9 0. 1 None 70 50 F 1. 5 0.9 None 0.6 50/70 50/70 G 1. 5 0. 9 0. 1 0. 6 50/70 0/5() H 4. 0 2. 7 None None 50 50 Control (the untreated cotton fabric) 0 0 Catalysts: See footnote to table for Example 19. "For Sample H, benzoyl peroxide (1.3% OWB) was applied with the reagent from p-dioxane.
EXAMPLE 21 Use of the Adduct of EXAMPLE 17 (Applied from Solution) as an Oil-Repellent Finish on Glass Fabric A glass fabric was selected which was of a style popular for draperies, having a thread count of 56 X 54. The adduct of EXAMPLE l7, namely bis[2,2,2-trifluoro-l- Catalysts: Products 01 Dow Corning Corp. (50% solids and pyridine carrier for Type 81; 28% solids [or Type 128). Wct pick-up from the aqueous pad bath was approximately EXAMPLE 20 Use of the Adduct of EXAMPLE 17 as a Water- Repellent Finish on Cotton Fabric Eight samples of percent cotton fabric of the type used in EXAMPLE 19, each 8 by 12 inches, were conditioned and weighed as described in that example. Each sample was padded with a solution of bis[2,2,2-
(trifluoromethyl )ethyl] N- 3-(triethoxysilyl )propyl 3,3-iminodipropionate, was diluted to 5 percent in ethanol and applied as a finish to the glass fabric by a 65 padding operation. That is, the cloth, impregnated with the solution, was squeezed as it passed between two pad rollers. The wet pick-up was approximately 30 percent. The padded fabric was cut into seven specimens,
each of which was dried under a different set of conditions, as indicated in the accompanying table. For each set of drying conditions, the oil repeller of this invention was effective in the test in preventing mineral oil from penetrating the fabric. Without the adduct,
mineral oil penetrated promptly. That is, the fabric had nooil repellency prior to treatment with the addition compound made from 3-(triethoxysilyl)propylamine and the acrylate of 2H-hexafluoro-2-propanol.
Use of the Adduct of EXAMPLE l7 (Applied as Vapor) as an Oil-Repellent Finish on Glass Fabric The adduct of EXAMPLE l7, C H F No Si, was applied in the form of vapor (instead of being padded on) to a heat-cleaned, casement-style glass fabric. The equipment for vapor-phase application consisted of an insulated chamber which could be heated to 180 C. The glass fabric was draped over steel racks inside the chamber. A IO-ml. portion of the adduct of EXAMPLE 17 was allowed to drip from a dropping funnel into the otherwise sealed chamber. Each drop struck a hot trough inside as the chamber and its contents were being heated at 170 2': 10 C. The addition and vaporization were carried out at atmospheric pressure over a period of 15 minutes. Whereas a portion of the original (control) fabric was promptly penetrated by 16 mineral oil (i.e., the fabric had no oil repellency), the finish of this invention prevented penetration or wetting of the treated fabric in the test for oil repellency, although the amount of C H F NO Si condensed on the fibers was of the order of only 0.01 percent of the weight of the fabric.
As the various examples and suggested embodiments indicate, numerous changes can be made in reaction conditions and reactants without departing from the inventive concept. The metes and bounds of this invention are best indicated by the claims which follow.
What is claimed is:
1 Polyfluorinated esters of the formula 0 II (moccmcm momomcmsuo(1 in wherein R, is a polyfluorinated hydrocarbon radical free of olefinic or acetylenic unsaturation and containing at least three fluorine atoms and up to 20 carbon atoms. 2.

Claims (1)

1. Polyfluorinated esters of the formula wherein Rf is a polyfluorinated hydrocarbon radical free of olefinic or acetylenic unsaturation and containing at least three fluorine atoms and up to 20 carbon atoms. 2. 3.
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