US3427332A - Perfluoroalkyl amide derivatives of polyoxyalkylene carbamates - Google Patents

Perfluoroalkyl amide derivatives of polyoxyalkylene carbamates Download PDF

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US3427332A
US3427332A US665245A US66524567A US3427332A US 3427332 A US3427332 A US 3427332A US 665245 A US665245 A US 665245A US 66524567 A US66524567 A US 66524567A US 3427332 A US3427332 A US 3427332A
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fabric
mole
stain
grams
repellancy
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Thomas Clark Allen
Robert Charles Koestler
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Pennwalt Corp
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Pennsalt Chemical Corp
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Priority to US665245A priority Critical patent/US3427332A/en
Priority to GB40490/68A priority patent/GB1242448A/en
Priority to FR1582274D priority patent/FR1582274A/fr
Priority to NL6812695.A priority patent/NL162635C/xx
Priority to DE1793357A priority patent/DE1793357C3/de
Priority to BE720406D priority patent/BE720406A/xx
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    • 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
    • D06M13/402—Amides imides, sulfamic acids
    • D06M13/425—Carbamic or thiocarbamic acids or derivatives thereof, e.g. urethanes
    • D06M13/428—Carbamic or thiocarbamic acids or derivatives thereof, e.g. urethanes containing fluorine atoms
    • 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
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/564—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them
    • D06M15/568—Reaction products of isocyanates with polyethers
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03D—APPARATUS FOR PROCESSING EXPOSED PHOTOGRAPHIC MATERIALS; ACCESSORIES THEREFOR
    • G03D13/00—Processing apparatus or accessories therefor, not covered by groups G11B3/00 - G11B11/00
    • G03D13/02—Containers; Holding-devices
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03D—APPARATUS FOR PROCESSING EXPOSED PHOTOGRAPHIC MATERIALS; ACCESSORIES THEREFOR
    • G03D15/00—Apparatus for treating processed material
    • G03D15/02—Drying; Glazing
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01P—WAVEGUIDES; RESONATORS, LINES, OR OTHER DEVICES OF THE WAVEGUIDE TYPE
    • H01P5/00—Coupling devices of the waveguide type
    • H01P5/08—Coupling devices of the waveguide type for linking dissimilar lines or devices
    • H01P5/10—Coupling devices of the waveguide type for linking dissimilar lines or devices for coupling balanced lines or devices with unbalanced lines or devices
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01Q—ANTENNAS, i.e. RADIO AERIALS
    • H01Q15/00—Devices for reflection, refraction, diffraction or polarisation of waves radiated from an antenna, e.g. quasi-optical devices
    • H01Q15/14—Reflecting surfaces; Equivalent structures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01Q—ANTENNAS, i.e. RADIO AERIALS
    • H01Q21/00—Antenna arrays or systems

Definitions

  • This invention relates to novel fiuorinated compounds of particular utility for the treatment of textiles and other fibrous substrates to impart highly desirable stain repellancy and stain release properties.
  • the chromium complextype materials have relatively poor hydrolyticstability and accordingly have relatively poor resistance to laundering. For this reason, their use has been confined mainly to the treatment of leather, paper, upholstery finishes and the like where resistance to laundering is not a requirement.
  • stain release is meant the readiness with which soils are removed from the textile on laundering or drycleaning.
  • soiling of textiles can occur in two ways. The first is by a wicking action of the fabric in which oily or aqueous materials are carried into the fabric by capillary action.
  • the second soiling mechanism is that in which materials are rubbed into the fabric under pressure or deposited during laundering after being removed from the same or another fabric.
  • Treatment of the fabric with fiuorinated acrylate polymers is quite effective in reducing soiling by the former mechanism since the fabric is rendered repellant both to oil and water soil carriers. Because of the repellancy properties imparted to the fabric, the oil or water-borne soil dies not penetrate and therefore soiling does not occur. However, the repellancy imparted by the acrylate polymers does not prevent soils from being rubbed into the fabric. Once this occurs, they become quite difficult to remove. In fact, experience has shown that soil that has been ground into fabrics that have been treated with fiuorinated acrylate polymers are considerably more difficult to remove than from untreated fabrics.
  • the second disadvantage of the fiuorinated acrylate polymers is their poor compatability and stability with normal textile mill finishing baths.
  • the fiuorinated acrylate polymers are applied to the fabric as aqueous latexes containing a variety of ingredients such as surfactants, initiators, cornonomers, modifiers, electrolytes and the like which must be present in an emulsion polymerization recipe.
  • the latex being an emulsion, can be coagulatcd by certain textile bath additives particularly if the ionic species are not the same.
  • a third disadvantage of the fiuorinated acrylate polymers is the tendency of the latex to coagulate and deposit a gummy mass in the bath, on the squeeze rolls, and even on the surface of the fabric due to the shearing forces caused by the mechanical action of the fabric passing through the bath and the rolls.
  • the latex polymer particles are easily coagulated in storage by any of a number of conditions such as exposure to light, low or high temperatures, a drastic change in pH or contamination with a variety of chemicals.
  • the compounds of the invention when applied to the fabric, overcome the poor stain release characteristics resulting from the durable press treatment, producing a fabric having durable press properties, good oil and water repellancy properties, and in addition, excellent stain release properties superior in many cases even tothose possessed by the untreated fabric.
  • the compounds of this invention can also be used in conjunction with the fiuorinated acrylate polymers to impart stain release properties to fabric so treated.
  • An important advantage of the new compounds embodied herein is their compatability with the aqueous media normally used in textile treating operations.
  • Many of the compounds are water-soluble viscous liquids, while the others are either solids or viscous liquids which are readily soluble in water-miscible organic liquids such as methanol or acetone, which solution is easily dispersed in Water to form very fine colloidal-like suspensions.
  • the stain release agents compatibility with water makes it possible to apply the compound to the substrate treated therewith in a uniform amount throughout, and eliminates other difiiculties such as coagulation caused by ionic species, mechanical shear, chemical contamination and changes in temperature or pH.
  • the new compounds of the invention are fluorine-containing carbamates and their methylolated derivatives in which the fiuorinated portion of the molecule is a perfiuoroalkyl group.
  • the fluorinated carbamates and their methylol derivatives may be represented by the generic formula:
  • R is a perfluoroalkyl radical (straight chain or branched chain) having from 4 to 15 carbon atoms, preferably 6 to 12 carbon atoms;
  • R is hydrogen or a lower alkyl radical (i.e. an open chain or cycloalkyl radical having about 1 to 6 carbon atoms) or a group;
  • x is an integer from 1 to 1 00 inclusive and referably from 1 to 20 inclusive;
  • R is a lower alkylene radical, straight or branched chain, having from two to about six carbon atoms and Y and Z (which may be the same or different) may be hydrogen, or the CH O-R group where R is hydrogen or a lower alkyl radical (i.e.
  • alkylene radical R can be the same or different in the repeating units in the chain as in the groups:
  • the fluorinated carbamates of the invention (which may be converted to the methylolated derivatives) may be represented by the general formula:
  • R;, R and x are as defined above and where A is hydrogen, lower alkyl or a group.
  • a particularly preferred group of compounds within the general class defined above are the mono or dimethylolated carbamates of the general formula:
  • the above carbamates may be converted to mono or dimethylolated derivatives by techniques which are in themselves well-known, such as reaction with formaldehyde.
  • the monomethylol derivative can be made to predominate, or on the other hand a mixture of the mono and dimethylol derivatives or a product consisting mostly of the dimethylol derivative can be produced.
  • the alkoxymethyl derivatives can be obtained by concurrent or subsequent etherification of the methylol group with lower alkanols such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, amyl, isoamyl alcohol or similar lower alkanols.
  • Exemplary methylol derivatives of the carbamates of the invention 6 derived Lfrom the first compound listed above are the following:
  • a preferred procedure for preparing the new compounds of the invention involves as the first step the reaction of a perfluoroalkyl acid fluoride if RICF where R; is as above defined with a primary or secondary amino alcohol to form an amido alcohol.
  • An alternate route to the amido alcohol is the preparation of the amide 0 Ri -NEE where R: and R are as defined above followed by reaction of the amide with an alkylene oxide such as ethylene oxide.
  • additional oxyalkylene groups (RO) are desired, the amido alcohol may be reacted with an alkylene oxide such as ethylene oxide or propylene oxide forming a longer chain amido alcohol with repeating oxyalkylene groups, e.g. ethylene oxide groups: (CH CH O)
  • the resulting amido alcohol is then converted in a second step to the ca-rbamate by any one of several alternative procedures.
  • the carbamate may then be converted in a third step to a methyl derivative preferably by reaction with formaldehyde. If alkoxymethylol derivatives are desired the methylolation is carried out in the presence of an alkanol or alternatively the methylolated product may be reacted with an alkanol in a separate step.
  • the reaction of the amino alcohol with the perfluoroalkyl acid fluoride H RICE may be conveniently carried out at temperatures of from about 10 C. to about 60 C. and preferably from 10 C. to 20 C. in a solvent such as chloroform or methylene chloride employing mole ratios of amino alcohol to perfluoroalkyl fluoride of from about 2:1 to 4:1 and preferably 2:1 to 2.5 :1.
  • the alcoholic hydroxyl group thereof may be reacted with an alkylene oxide such as ethylene oxide or propylene oxide if it is desired to add one or more repeating oxyalkylene groups to the molecule.
  • the addition of the alkylene oxide may be conveniently carried out at temperatures of about 20 C. to 150 C. and preferably 100 C. to 130 C. Generally the addition is carried out in a sealed vessel in the absence of a solvent using a basic catalyst such as sodium hydroxide, sodium methoxide or the like.
  • One suitable method is the reaction of the amido alcohol with sodium cyanate and trifluoroacetic acid in an aromatic solvent following the carbamylation technique of Loev and Kormendy, J. Org. Chem. 28 p. 3421 (1963).
  • a second carbamylation technique is the reaction of the amido alcohol with an excess of urea in the presence of a small amount of a catalyst such as zirconium acetylacetonate or zinc acetate dihydrate, generally at temperatures of from about 120 C. to 220 C.
  • a catalyst such as zirconium acetylacetonate or zinc acetate dihydrate
  • a third and often preferred carbamylation method is the reaction of the amido alcohol with an alkyl carbamate such as ethyl carbamate,
  • the ethanol formed as a byproduct is preferably continuously removed from the reaction mixture e.g. by distillation.
  • R.l'; (R'o tNH. is conveniently carried out by reaction of the carbamate with formaldehyde preferably in basic methanol solution or basic aqueous solutionpThe completeness of methylolation depends on the reaction conditions. Excess formaldehyde, higher temperatures, longer reaction times and high pH values in general favor more complete methylolation.
  • the methylolation is carried out at temperatures of from 30 C. to 100 C. and preferably from 60 C. to 80 0., mole ratios of formaldehyde to carbamate of from 1:1 to 10:1 and preferably 1:1 to 5:1, and at a pH ranging from 6 to 12 and preferably from to 11, and for reaction periods ranging from 10 minutes to 24 hours and preferably from 2 to 3 hours.
  • one or both of the hydrogens of the carbamate group i --ONH2 may be replaced by methylol groups CH OH.
  • the methylolation is ran in the desired alkanol solvent at an alkaline pH followed by etherification by adjusting the pH to a relatively low acid pH, e.g. pH of 1 or 2.
  • Example 1A -Preparation of I II 0 F920 F (CFzhil-Ifi-CEDCHEO CHzCHzOC-NHs parts by weight of is added to a solution of 40 par-ts (all parts are by weight) of diglycolamine alcohol (NH C H OC;H OH) in 330 parts of chloroform under a nitrogen blanket at a temperature of 20 to 25 C.
  • the reaction is carried out with agitation at this temperature for one hour to give a clear solution which is then washed with an aqueous solution containing 5% NaCl and 5% HCl, followed by two more washings with 5% aqueous NaCl solution.
  • the organic layer is separated and the chloroform is stripped from the organic layer to yield the solid amido alcohol product M.P. 45-46.5 C.
  • Example 1B Preparation of 32.5 parts (0.05 mole) of the amido alcohol prepared according to Example 1A, six parts (0.06 mole) of urea and 0.5 part zinc acetate dihydrate are mixed and stirred for five hours at ISO- C. The reaction mixture is taken up in acetone and the solution filtered. Evaporation of the acetone and recrystallization of the crude product from benzene yields the carbamate,
  • Example 1C Preparation of 65.1 parts (0.1 mole) of the amido alcohol prepared in Example 1A, 10.7 parts (0.12 mole) of ethyl carbamate, and 50 parts of toluene are brought to reflux and about 4 parts of distillate are taken off to ensure an anhydrous system. 0.3 part of tetraisopropyl orthotitanate is added and the mixture is refluxed for about 4 hours during which time the ethanol lay-product is taken off as an ethanol-toluene azeotrope. 50 to 75% of the toluene is distilled off and the residue is poured into a dish where it solidifies and is air dried to yield the carbamate,
  • Example 2 Preparation of The acid fluoride (33.9 g., 0.058 mole) is dissolved in 300 milliliters of anhydrous ether and cooled in an ice bath. Diglycol amine alcohol (H NC H OC H OH) (12 g., 0.116 mole) is added slowly while stirring under a nitrogen blanket. The mixture is then refluxed for 13 hours.
  • H NC H OC H OH Diglycol amine alcohol
  • a precipitate forms which is filtered 011 and the ether is evaporated from the filtrate to give 36.2 grams (95% yield) of a white waxy solid having a melting point of 74-77 C., the infrared spectrum of which shows no ester peak, which is the amido alcohol
  • the amido alcohol prepared as described above (35.4 grams, 0.0471 mole) and 6.1 grams (0.0942 mole) of sodium cyanate are stirred at reflux in 150 milliliters of benzene.
  • Trifluoroacetic acid (10.7 grams, 0.0942 mole) is added dropwise and the reaction refluxed for /2 hour. Water is added and the benzene and water layer is decanted from the product.
  • the product is then taken up in a mixture of 100 milliliters of hot water and 50 milliliters of hot ace-tone. The layers are separated and the solvent evaporated from the organic layer. The carbamate is obtained as a white crystalline solid (32.3 grams, 86%
  • Example 3 Preparation of O H i 920 F (C MC-g-CzHMO CzHrO--NHz
  • the amido alcohol is prepared by the reaction of the acid fluoride crude product. Recrystallization of the crude product from toluene gives the carbamate 0 0 ll 1 0 F920 F c Fmo-ig-omomo omomo-d-mn having a melting point of 84-86" C.
  • Example 4 Preparation of The acid fluoride (36.6 grams, 0.1 mole) is added dropwise to diglycol amine alcohol, H NCH CH OCH CH OH, (23.1 grams, 0.22 mole) while stirring and cooling with an ice bath. After standing 1 hour and warming to room temperature, 50 milliliters of 15% HCl and 50 milliliters of trichlorotrifluoroethane are added to the reaction mixture. The layers which form are separated. The organic layer is washed with 10% sodium bicarbonate. The layers are then separated and the organic layer is dried over anhydrous sodium sulfate. Removal of the trichlorofluoroethane solvent by heating to 140 C. gives 34.7 grams (77% yield) of a clear colorless liquid, the infrared spectrum of which is free from ester bands, and which is the amido alcohol:
  • amido alcohol prepared as described above (34.7 grams, 0.077 mole) and sodium cyanate (10.0 grams, 0.154 mole) are stirred in milliliters of methylene chloride.
  • Trifluoroacetic acid (17.6 grams, 0.154 mole) is added dropwise at room temperature. The mixture is stirred for 1 hour. The water is added and the layers separated. The organic layer is dried over anhydrous sodium sulfate and the solvent evaporated. There is obtained 22.8 grams 60% yield) of a white crystalline solid which after recrystallization from toluene has a melting point of 62- 64 C.
  • Example 5 --Preparation of A mixture of acid fluoride consisting of 70% by weight of the acid fluoride and 30% by weight of (CFa)2CF(CF2) CF is added dropwise to a mixture of a polyglycolamine alcohol of the formula H N(C H O),.H, where x has the value of 10-11, in an equal weight of methylene chloride at room temperature.
  • the acid fluoride is added to the polyglycolamine alcohol in a molar ratio of 1 mole of acid fluoride to 2 moles of polyglycolamine alcohol. After stirring for 1 hour, water is added and the aqueous and organic layers separated. The organic layer is washed with and is obtained.
  • Ethanol amine, H NCH CH OH, (427 grams, 7.0 moles) is suspended in 4.0 liters dry ethyl acetate, cooled by an ice bath.
  • amido alcohol prepared as described above (60.7 grams, 0.1 mole) and sodium cyanate (13.0 grams, 0.2 mole) are stirred and warmed in a mixture of 85 milliliters of trichlorotrifluoroethane and 165 milliliters of benzene.
  • Trifluoroacetic acid (22.8 grams, 0.2 mole) is added dropwise. A precipitate is formed and is filtered off. The precipitate is then taken up in 200 milliliters of acetone and poured into ice water. The product is filtered off and air dried. After recrystallization from a 3:1 tolueneacetone mixture there is obtained (52 grams, 80% yield) of the carbamate having a melting point of 109-111 C.
  • Trifluoroacetic acid (4.56 grams, 0.04 mole) is added rapidly to the mixture which is then heated at 80 C. for 10 minutes and then stirred for 1 hour at 25 C. Water and acetone are added and the mixture is heated to dissolve all lumps. The mixture is then cooled and the layers separated. The organic layer is washed with water and dried over sodium sulfate. The benzene is evaporated to give 7.6 grams of white solid (57% yield) which upon recrystallization from benzene has a melting point of 84- 85.5 C.
  • amido alcohol prepared as described above (20 grams, 0.0308 mole) is heated with urea (5.0 grams, 0.083 mole) at 150 to C. with stirring for 3 hours in the presence of 0.3 grams of zirconium acetylacetonate as a catalyst.
  • a thick grease is obtained in 82% yield, the infiared spectrum of which confirms the carbamate:
  • the product which is obtained as a 20% solution in methanol consists mostly of the dimethylol derivative having the structure 20.0 grams (0.0337 mole) of the carbamate of the above structure prepared in accordance with Example 3, is mixed with 11.0 grams of a 37% aqueous formaldehyde solution (containing 0.135mole CH O). A few drops of NaOH solution is added and the mixture is stirred and warmed to 60 C. for 18 hours. A soft, watersoluble grease is obtained containing 65% solids which consists mostly of the dimethylol derivative having the structure:
  • the compounds of the invention have the valuable property of imparting both stain repellancy and stain release characteristics to fabrics and other fibrous substrates. They are elfective on fabrics and other substrates composed of both natural and synthetic materials such for example as cellulosic materials, polyamides, acrylics, polyesters, glass fibers etc.
  • the compounds of the invention are especially suitable for application to cellulosic fabrics, i.e., fabrics, whether woven or not woven, containing cellulosic fiber, such as cotton fabrics, mercerized cotton fabrics, rayon fabrics, linen, flax, cellulose acetate or the like, as well as blends of such cellulosic fibers with other materials such as wool, nylon, acrylic fibers, polyolefin fibers, glass fibers, polyester fibers and the like.
  • cellulosic fabrics i.e., fabrics, whether woven or not woven, containing cellulosic fiber, such as cotton fabrics, mercerized cotton fabrics, rayon fabrics, linen, flax, cellulose acetate or the like, as well as blends of such cellulosic fibers with other materials such as wool, nylon, acrylic fibers, polyolefin fibers, glass fibers, polyester fibers and the like.
  • Desirable properties may also be imparted to other fibrous substrates such as leather, paper, hemp, wood or the like.
  • the compounds of the invention may be applied to the fabric or the substrate by contact with an aqueous or organic solution, or dispersion of the compound.
  • Application to fabrics is preferably by the commonly employed technique of padding.
  • Application from aqueous pad baths is generally preferred; however, other pad bath media containing organic solvents such as alcohols, ke tones, halogenated hydrocarbons, aromatic or aliphatic hydrocarbons may be used.
  • the pad bath mixture will generally contain from about 0.05 to 10% and preferably from about 0.1% to 1% by weight of the compound of the invention, preferably together with a curing agent to promote the fixation of the compound on the fabric such as magnesium chloride, zinc chloride, zinc nitrate, aluminum chloride, ammonium chloride, zinc fluoro borate, magnesium fluoroborate, dimethylaminomethylamine hydrochloride, hydroxyacetic acid, magnesium hydrogen phosphate, citric acid, oxalic acid, 2-methyl-2- aminopropanol hydrochloride, magnesium nitrate, strontium nitrate, zinc acetate, or similar agents known in the art.
  • a curing agent will generally be added to the pad bath in amounts ranging e.g. from 10% to 50% by weight based on the weight of the compound.
  • the amount of the compound deposited on the fabric as it travels through the pad bath can be controlled by well-known techniques such as the concentration of the compound in the pad bath media, the amount of excess of the .pad bath which is squeezed out of the fabric by passage through the squeeze rolls and the like. It will be generally advantageous to control the add-on to the fabric such that the treated fabric is impregnated with about 0.05 to 10 and preferably from about 0.1 to 1% by weight of the compound of the invention based on the weight of the dry fabric.
  • the pad bath containing the compound of the invention may also contain other pad bath additives for imparting particular properties to the fabric, such as durable press agents, optical brighteners, stiifeners, softeners, abrasion protectors, biocides, biostats and the like.
  • other pad bath additives for imparting particular properties to the fabric, such as durable press agents, optical brighteners, stiifeners, softeners, abrasion protectors, biocides, biostats and the like.
  • a prime advantage of the compounds of the invention is that they are generally stable in the presence of these other bath additives, providing bath stability and ease of operation.
  • a particularly advantageous use of the compounds of the invention is the treatment of fabric, particularly cellulosic fabric, in combination with the so-called durable press chemicals which are used to impart wrinkle recovery and crease retention properties to the fabric.
  • the compounds of the invention are applied simultaneously from the same pad bath containing such durable press agents.
  • Such agents include, e.g. formaldehyde, the reaction products of formaldehyde with urea and substituted ureas such as 2-imidazolidinonc, 4,5-dihydroxy-2-imidazolidinone, tetrahydro-2 pyrimidinone, 5-(u-hydroxyethyl)tetrahydro-s-triazin-2-one, tetrahydro-l,3,5-oxadizin-4-one, and the like, the reaction products of formaldehyde with s-triazines such as melamine and the like, the reaction products of formaldehyde with hydrocarbon esters of carbamic acid such as methyl carbamate, hydroxyethyl carbamate, methoxyethyl carbamate and the like.
  • formaldehyde the reaction products of formaldehyde with urea and substituted ureas such as 2-imidazolidinonc, 4,5-dihydroxy-2-imidazolidinone
  • the impregnated textile or other material is subjected to drying; and may also be subjected to a curing operation to fix the impregnants on the fabric.
  • drying at temperatures e.g. from 25 to 170 C. for about 1 to 60 minutes
  • the impregnated material is subjected to curing temperatures of e.g. from 120 to 180 C. for about 1 to 25 minutes, with longer curing times being employed at the lower temperatures and conversely.
  • the final properties of the treated fabric are dependent to some degree upon the paddnig and curing conditions employed, particularly the type of durable press agent, the type of curing catalyst and the curing temperatures.
  • the water repellancy of the fabric may be varied from relatively low values where this is desirable (such as in shirt fabrics where low water repellancy for wearer comfort is desired) to relatively higher water repellancies where this is the desired characteristics.
  • the preferred compounds of the invention for producing a combinationof stain repellancy and stain release effects on textiles and other fiber substrates are the methylol derivatives of the carbamates of the invention, particularly the methylolated derivatives containing one or more methylol (CH OH) groups. Included in the term methylolated derivatives are also the alkoxy methyl derivatives, i.e. those containing a CH OR group where R is a lower alkyl group as previously defined.
  • the methylolated derivatives containing the free methylol (i.e. the unetherified) methylol groups are preferred since these have higher water solubility and are thus more compatible with aqueous padding baths.
  • the methylolated derivatives of the carbamates are in general preferred over the carbamates themselves for stain repellancy and stain release applications in that, in general, they give somewhat higher stain repellancy and stain release ratings and also because the textiles so treated retain these properties over a longer series of laundering and/or dry cleaning. It is believed that the methylolated derivatives have fiber reactive properties, particularly with respect to cellulosic textiles by reaction of the methylol or alkoxy methylol gruops with the fiber substrate.
  • carbamates themselves have useful stain repellancy and stain release properties when applied to textiles and the like and thus have a direct use for this purpose. Also the carbamates are, of course, the intermediates for the preparation of the methylolated derivatives.
  • Reduced water repellancy may be desirable for some applications, e.g., for the treatment of shirt fabrics where a high degree of water repellancy is not desirable because of wearer-comfort considerations and the like.
  • pad bath A has the following compositions:
  • the pieces of test fabric are then evaluated for Hydrocarbon Repellancy Rating, Stain Repellancy Rating and Stain Release Rating. These evaluations are carried out as follows:
  • Hydrocarbon repellancy rating In this test, the repellancy of the fabric pieces to oily liquids is tested using the A.A.T.C.C. Tentative Test Method 119-1966 T, Oil Repellancy, Hydrocarbon Resistance Test. According to this test, drops of standard test liquids consisting of a selected series of hydrocarbons with varying surface tension, are placed on the fabric surface. The Hydrocarbon Repellancy Rating is defined as the highest number test liquid which does not wet the fabric surface. The higher the Hydrocarbon Repellancy Rating therefore, the better the repellancy of the fabric to oily materials. Wetting of the fabric is normally indicated by a darkening of the fabric at the liquid-fabric interface. The following standard test liquids and rating system are employed:
  • Test liquid Hydrocarbon repellancy rating Fabric wetted by mineral oil 1 0 Fabric not wetted by mineral oil 1 1 Fabric not wetted by 65:35 mixture of mineral oil: n-hexadecane 2 Fabric not wetted by n-hexadecane 3 Fabric not wetted by n-tetradecane 4 Fabric not wetted by n-dodecane 5 Fabric not wetted by n-decane 6 Fabric not wetted by n-octane 7 Fabric not wetted by n-heptane 8 1 Saybolt viscosity 360/390 at F., sp. gr. 0880/0900 at 60 F. (e.g. Nujol).
  • Stain repellancy rating In this test, a series of eight staining materials is employed including both oil base and water-based materials viz., (1) SAE 30 motor oil; (2) spaghetti sauce; (3) French dressing; (4) bacon grease; (5) Vaseline hair tonic; (6) Mazola corn oil; (7) mayonnaise; (8) mustard.
  • the test fabric is placed on blotting paper and three drops of each stain are dropped onto the fabric from a height of about one foot. The stain is allowed to stand one minute and all that has not penetrated is then carefully scraped off with a spatula.
  • stain impact area is then rubbed lightly with a soft paper tissue, following which the stain re contrast, in Examples B through K inclusive, wherein 1% by weight of various compounds of the invention were incorporated in the standard durable press pad bath, good to excellent repellancy ratings were obtained both in the hydrocarbon repellancy and stain repellancy tests.
  • Stain release rating static soils.
  • the same eight staining materials used in connection with the stain repellancy rating test above are employed.
  • the fabric is placed on blotting paper and three drops of each stain are dropped onto the fabric from a height of one foot.
  • the stain is allowed to stand one minute and all that has not penetrated is carefully scraped off with a spatula after which the stain impact area is rubbed lightly with a soft paper tissue.
  • the test fabrics, after standing for at least one hour, are then washed under normal laundering conditions (a hot wash followed by a warm rinse in an automatic home laundering machine using 0.25% of a standard household detergent (ALL).
  • ALL standard household detergent
  • the laundered fabrics are then evaluated according to the same rating scale used in determining Stain Repellancy Rating using as the standard for comparison an untreated fabric speciman (no Pad Bath A treatment) which has been stained as described above, but which has not been laundered. According to the above rating system, a perfect score of 40 (8X5) is obtained if all of the stains are completely removed.
  • Example A which shows the results obtained with no additive in the standard durable press pad bath, it may be seen that very low hydrocarbon repellancy and stain repellancy ratings are obtained, indicating essentially no repellancy characteristics imparted by the durable press pad bath.
  • the stain release rating obtained in Example A shows further that the launderability of the fabrics was quite poor, i.e. most of the stains that entered the fabric were not washed out in the laundering, but were retained on the fabric.
  • Examples C through K gave relatively higher repellancy and stain release ratings than the unmethylolated carbamate used in Example B.
  • test fabric The pieces of test fabric were evaluated for hydrocarbon repellancy rating following the test procedure described above and then were evaluated for stain release with respect to ground in soils according to the following test procedure:
  • Stain release rating ground in soils.
  • Stain release rating ground in soils
  • Each fabric specimen is placed on blotting paper and three drops of each stain are dropped onto the fabric from a height of one foot.
  • the stain is then ground into the fabric with a spatula, overcoming any repellancy, until the stain penetrates to the blotting paper on the other side.
  • the stained fabric is washed under normal laundering conditions [hot wash followed by a warm rinse in a standard household automatic washing machine using 0.25% of standard household detergent (A LL)]. After tumble drying the fabric specimens are then evaluated for removal of the stain using the same rating system as described in connection with the stain release rating for static soils.
  • Example II shows the results of evaluations conducted in the above manner on a series of fabric specimens.
  • Example L the fabric was treated with the durable press agent only (Pad Bath A) and similar stain repellancy ratings and stain release ratings were obtained as in the previous series of tests (Table I).
  • Example M a standard commercial fluorocarbon latex produced by the copolymerization of a fiuorinated acrylate with a non-fiuorinated repellancy rating, and the stain release rating actually underwent a substantial increase.
  • the fabric specimen displayed an excellent stain repellancy rating, but a poor stain release rating. That is, although the fabric repelled soils that were dropped on rather than ground into the fabric, the ground in soils were largely retained by the fabric after washing. As can be seen, the fluorocarbon latex treated fabric showed very little improvement in stain release properties over the fabric of Example L containing only the durable press pad bath. In contrast, in Examples N to X inclusive, wheresmall amounts of the compounds of the invention were included, good to excellent repellancy ratings were obtained in each case while at the same time, greatly improved stain release ratings were obtained.
  • Example N shows the beneficial effect of incorporating a small amount of a compound of the invention in combination with a fluorocarbon latex. As shown in Table II, the stain release rating in Example N is greatly improved over that in Example M.
  • the stain repellancy and stain release properties imparted by the compounds of the invention are in many cases retained in large measure after repeated launderings or dry cleanings. Retention of these properties on repeated laundering is particularly characteristic of the methylolated derivatives of the fiuorinated carbamates of the invention, and retention of these properties may be enhanced by use of relatively strong curing agents and curing conditions.
  • a typical pad bath formulation which has been found to promote excellent retention of stain repellancy and stain release properties after repeated launderings is the following: Ingredient Percent by wt.
  • R is a perfluoroalkyl radical having from 4 to 15 carbon atoms; R is hydrogen, or a lower alkyl radical or a 0 -(RO);( 1N
  • x is an integer from 1 to R is a lower alkylene radical having from two to about 6 carbon atoms; and Y and Z, which may be the same or different, are hydrogen, or a CH OR group where R is hydrogen or a lower alkyl radical.
  • R has from 6 to 12 carbon atoms.
  • R is an alkylene group having from two to three carbon atoms.
  • R is a perfiuoroalkyl radical having from 4 to 15 carbon atoms
  • A is hydrogen, a lower alkyl radical or a group
  • R is a lower alkylene radical having from 2 to about 6 carbon atoms and x is an integer from 1 to 100.
  • R contains from 6 to 12 carbon atoms.
  • a compound of the formula: 14 The compound 0 CHZOH ll H I H H II RIC''N(CH2CH20 xC' N ⁇ RzCNOH2CHzOC-NH2 Z 5 and their methylolated derivatives
  • R is a perfluowhere R is a perfluoroalkyl group having from 6 to 12 roalkyl group having from 6 to 12 Carbon atoms' carbon atoms; where x is an integer from 1 to 15; and

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electromagnetism (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
US665245A 1967-09-05 1967-09-05 Perfluoroalkyl amide derivatives of polyoxyalkylene carbamates Expired - Lifetime US3427332A (en)

Priority Applications (6)

Application Number Priority Date Filing Date Title
US665245A US3427332A (en) 1967-09-05 1967-09-05 Perfluoroalkyl amide derivatives of polyoxyalkylene carbamates
GB40490/68A GB1242448A (en) 1967-09-05 1968-08-23 Fluorinated amidocarbamates
FR1582274D FR1582274A (xx) 1967-09-05 1968-09-04
NL6812695.A NL162635C (nl) 1967-09-05 1968-09-05 Werkwijze ter bereiding van vlekafstotende en vleklos- makende verbindingen, alsmede werkwijze ter bereiding van vlekafstotende en vleklosmakende preparaten en werkwijze voor het behandelen van textielprodukten en andere vezelvormige substraten.
DE1793357A DE1793357C3 (de) 1967-09-05 1968-09-05 Verfahren zur Verbesserung der Fleckenbefreiungs- und Fleckenabweisungseigenschaften von Textilien und anderen faserigen Substraten
BE720406D BE720406A (xx) 1967-09-05 1968-09-05

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BE (1) BE720406A (xx)
DE (1) DE1793357C3 (xx)
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3897208A (en) * 1969-06-09 1975-07-29 Ici America Inc Textile treating compositions, process of treating textiles, and textile articles
US3970687A (en) * 1968-11-18 1976-07-20 E. I. Du Pont De Nemours And Company Polyesters with substituted amine end groups
US20080004394A1 (en) * 2006-06-30 2008-01-03 Stefan Reinartz Method of providing repellency

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2556146A (en) * 1948-11-05 1951-06-05 Gen Aniline & Film Corp Di-(beta-hydroxyalkyl)-2-(alkyl carbamyl-oxy)- alkylamines

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2556146A (en) * 1948-11-05 1951-06-05 Gen Aniline & Film Corp Di-(beta-hydroxyalkyl)-2-(alkyl carbamyl-oxy)- alkylamines

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3970687A (en) * 1968-11-18 1976-07-20 E. I. Du Pont De Nemours And Company Polyesters with substituted amine end groups
US3897208A (en) * 1969-06-09 1975-07-29 Ici America Inc Textile treating compositions, process of treating textiles, and textile articles
US3925009A (en) * 1969-06-09 1975-12-09 Ici America Inc Fatty group containing methylolated, polyoxyalkylene carbamates and textile materials softened by treatment therewith
US20080004394A1 (en) * 2006-06-30 2008-01-03 Stefan Reinartz Method of providing repellency

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DE1793357A1 (de) 1972-02-03
DE1793357C3 (de) 1980-08-28
NL162635C (nl) 1980-06-16
DE1793357B2 (de) 1979-12-20
NL6812695A (xx) 1969-03-07
NL162635B (nl) 1980-01-15
BE720406A (xx) 1969-03-05
FR1582274A (xx) 1969-09-26
GB1242448A (en) 1971-08-11

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