US 3894992 A
An adduct is prepared by heating together, in the presence of an acid catalyst, (1) a perfluoroalkyl alcohol of formula Rf(CH2)n-OH such as perfluoroalkylethyl alcohol; (2) a polyalkylene glycol such as polyethylene glycol having a molecular weight of about 1000; and (3) a poly(alkoxymethyl)melamine such as hexa(methoxymethyl)melamine. These adducts are effective in promoting oil and water repellency and oily soil release from textiles.
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Description (OCR text may contain errors)
United States Patent Raynolds July 15, 1975 54] FLUORINATED OILY SOIL RELEASE 3,503,915 3/1970 Peterson 260/849 AGENTS 3,510,455 5/1970 Olson 260/676 R Inventor: Stuart Raynolds, Wilmington. Del.
E. I. du Pont de Nemours & Company, Wilmington, Del.
Filed: Nov. 24, 1972 Appl. No.: 309,449
References Cited UNITED STATES PATENTS 4/l964 Wear et al. 260/2496 l/l967 Gagliardi 260/2496 FOREIGN PATENTS OR APPLICATIONS 1,233,970 6/1971 United Kingdom Primary ExaminerJohn C. Bleutge 5 7] ABSTRACT An adduct is prepared by heating together, in the presence of an acid catalyst, (l) a perfluoroalkyl alcohol of formula R,(CH ),,OH such as perfluoroalkylethyl alcohol; (2) a polyalkylene glycol such as polyethylene glycol having a molecular weight of about 1000; and (3) a poly(alkoxymethyl)melamine such as hexa(methoxymethyl)melamine. These adducts are effective in promoting oil and water repellency and oily soil release from textiles.
7 Claims, N0 Drawings FLUORINATED OILY SOIL RELEASE AGENTS SUMMARY In summary, this invention is directed to an adduct prepared by condensing in the presence of an acid cata- This invention relates to new compositions which 5 lyst when applied to textile substrates confer oil and water repellency and improved washability to said substrates, enhancing the removal therefrom of oily stains. More particularly this invention is directed to the adducts formed by the reaction of a perfluoroalkyl alcohol, a polyalkylene glycol and a poly(alkoxymethyl)melamine and the use of such adducts as oily soil release agents for textiles.
2. Prior Art Textiles are routinely treated to enhance desirable properties and minimize undesirable properties. Synthetic fabrics and fabrics composed of blends of natural and synthetic fibers have good strength and resistance to abrasion, and also sufficient resilience to allow shape retention when worn or otherwise distorted in use. Such fabrics are often treated with finishing agents to give them a softer hand or feel. Cotton fabrics normally have a good hand but are often treated to in crease fiber resilience and crease resistance.
Fabrics, particularly cotton containing fabrics, are often treated with thermosetting organic resins to give them permanent press characteristics. In addition to the thermosetting resin, catalysts and various modifying additives or finishing agents such as softeners, antistatic agents, etc. are also used to provide suitable commercial fabrics. Many of such treated fabrics have good wearing characteristics but the tendency of the fiber to accept oily stains is increased, and the ability of the material to release such stains upon laundering is usually reduced. Wicking or diffusion of the stain into the bulk of the fabric makes the stain even more difficult to remove. An improvement in the resistance of the fabric to staining can be provided through treatment with agents which impart oil and water repellency. However, oily stains can still occur despite these treatments, when oil or oily materials are forced into the fabric, such as may result from pressure or prolonged contact. The ability of the material to release this sort of stain is inhibited by the fluorochemical treating agents. The most serious problem with wash and wear and permanent press fabrics is the permanent kind of stain which cannot be removed by conventional home laundering.
Thus the prior art treatments for promoting oily soil release suffer from various shortcomings. Some treatments are effective for a while but do not retain their effectiveness through repeated Iaunderings. The cost of any such treatment must, of course, be weighed against the value of improvement attained.
An object of this invention is to provide a composition for treating fabrics to endow said fabrics with greater oily stain release on laundering. A further object of the invention is to provide textile treating agents which confer oil and water repellency in normal wear, are durable and stable to repeated launderings, and
which release oily stains and soil during laundering of 6 the treated fabric. Other objects will become evident from our disclosure.
A. an alcohol of the formula 1. R,(CH ),,OI-I
wherein R, is perfluoroalkyl of from 4 through 16 carbon atoms; n is an integer from 1 through about 16; v B. a polyalkylene glycol of the formula I 2. HO(CH CI-IR-O),,.I-I
wherein R is hydrogen or methyl, and m is 8 to 450; I and having a molecular weightbetween about 400 and about 20,000; and C. a poly(alkoxymethyl)melamine of the formula DESCRIPTION OF THE INVENTION Components The adducts of this invention are derived from the three classes of functional compounds referred to above. The reactivity of alkoxymethylmelamines is well known. These compounds react readily with compounds containing active hydrogens to produce the al- 0 cohol corresponding to the alkoxy group and a condensate incorporating the melamine residue. The adducts of this invention are produced by reacting, under conditions promoting the removal of the alcohol product, an (alkoxymethyl)melamine, a polyfluoroalkyl alcohol and a polyalkylene glycol. The adducts produced contain segments terminating in perfluoroalkyl groups. Polyether groups are believed to link some melamine residues. The adducts possess, therefore, qualities of oil and water repellency due to the pendant oleophobic perfluoroalkyl groups, and also hydrophilic properties associated with the polyalkylene oxide chains. When applied to a substrate, as for example a synthetic textile such as a polyester garment or cloth in conjunction with a crease resistant resin, the adducts of this invention improve not only oil and water repellency but also the easy removal by normal laundering procedures of oily stains which are present.
Among the useful alkoxymethylmelamines are the alkyl ethers of trimethylol melamine and hexamethylol melamine. Alkyl groups of from 1 to about 5 carbon atoms can be conveniently employed, a practical consideration being the ease or difficulty with which the corresponding alcohol can be removed from the reaction in which the adduct is formed. The preferred melamine derivatives are the hexa(alkoxymethyl)melamines where the alkyl groups have from 1 to 4 carbon atoms, and most preferred is hexa(methoxymethyl)- melamine, which is commercially available.
The polyalkylene glycols are also commercially available in a variety of molecular weights. Both polyethylene glycols and polypropylene glycols are commercially available and can be employed in the adducts of the invention in molecular weights of from about 400 to about 20,000. Polyethylene glycols of molecular weight from 400 to 4,000 are preferred, while polyethylene glycol of molecular weight about 1,000 is most preferred.
As polyfluoroalcohols, there may be used compounds containing perfluorinated alkyl groups of 4 to 16 carbon atoms. A general formula for useful alcohols is shown above as formula (1). Preferred alcohols are those where n is about 1 to 4, most preferably 2, and the perfluoroalkyl groups are straight or branched chain alkyls of 4 to 14 carbons. The most preferred polyfluoroalcohol is R,--CH CH -OH where R, is a mixture of perfluorinated straight chain alkyl groups of 6-14 carbon atoms with an average molecular weight of 470. These alcohols are produced as described in US. Pat. Nos. 2,965,659, 3,145,222, 3,171,861 and 3,283,012.
Additionally polyfluoroalcohols where inert groups are present between R; and (CH can be employed. Examples of these are R where R, is perfluorinated C to C alkyl, R is C, to C alkyl and m is l to 3.
When an alkoxymethylmelamine is heated with an alcohol in the presence of an acid catalyst, an ether interchange reaction occurs with the elimination of the alcohol corresponding to the alkyl group. The reaction is disclosed in US. Pat. No. 3,296,264 where hexa( methoxymethyl)melamine and pentadecafluorooctyl alcohol are heated in equimolar proportions with a little orthophosphoric acid as catalyst to yield pentadecafluoromethyl penta(methoxymethyl)- melamine and methanol. The polyalkylene glycols react with alkoxymethylmelamines in the same way, except that each glycol molecule can react with 2 alkoxymethylmelamine molecules instead of one.
Useful products are obtained with a wide variation in the amounts of the three primary ingredients employed. It is preferred to use a slight excess of the alkoxymethylmelamine compound in terms of its reactivity with active hydrogens available in the polyfluoroalcohol and the polyalkylene glycol. In these reactions, a hexa(alkoxymethyl)melamine molecule can react stoichiometrically with 6 equivalents of an active hydrogen containing molecule. A polyalkylene glycol molecule can react with 2 equivalents of a compound susceptible to reacting with an active hydrogen, while a polyfluoroalcohol is monoequivalent, offering only one active hydrogen for reaction. Thus for example, 1 mole (6 equivalents) of hexa(methoxymethyl)melamine can react with 2 moles of a polyethylene glycol (4 equivalents) plus 2 moles of polyfluoroalcohol (2 equivalents). It is preferred to employ the alkoxymethyl melamine reactant in an approximately stoichiometrically equivalent amount, plus or minus about 10%, most preferably with a stoichiometric excess of about 5%.
While a very wide range of proportions of polyfluoroalcohol to polyalkylene glycol can be used, it is preferred to employ about 1 to 20 equivalents of the polyfluoroalcohol to 1 equivalent of polyalkylene glycol. The most preferred mixture for producing an adduct of the invention contains about 5 equivalents of perfluoroalcohol, about 2 equivalents of polyalkylene glycol and about 7.5 equivalents of poly(alkoxymethyl)melamine.
Polyalkylene glycols in large measure confer functional performance (as hydrophilic or hydrophobic) in proportion to the weight employed whether the molecular weight is high or low. The weight proportion of polyfluoroalcohol to polyalkylene glycol is therefore of significance also, and a favored ratio is about parts of polyfluoroalcohol to about 30 parts of polyethylene glycol.
Reactions which occur produce the following types CH OCH CH OCH CH OCH CH OCH the mixture but takes no part in the reaction. The inert solvent or diluent can be a mixture of compounds and CH OCH The product of (2) can condense to form is chosen not only for its fluidization properties but also In the adducts of the invention most, if not all of the alkoxy groups of the hexa(alkoxymethyl)melamine have reacted so that nearly all have been converted to linkages of the type illustrated in l (2), or (3) above.
As stated above, the polyalkylene glycol can react at more than one of the methoxy group linkages. Thus linking of the segments as shown in"(3) can occur through reaction of the hydroxy group at the other end of the already linked polyalkylene oxide unit. The products of the reaction include, therefore, a number of molecular species with different proportions of polyfluoroalcohol and polyalkylene glycol substitution on the melamine rings, and varying degress of linking of the rings through the polyalkylene oxide chains. The polyfluoroalcohol and polyalkylene glycol units do not link with each other under the conditions employed.
In preparing the products, the dry reactants are charged to a vessel equipped with an agitator and fitted for fractional distillation. Also charged to the vessel is an acidic material serving as a catalyst and optionally a reaction solvent or diluent which maintains fluidity in for its boiling point, which is preferably from about 50C. to C. so that it can be distilled or partially distilled from the mixtures after the desired reaction is finished. Most preferred are diluents which form azeotropes with the alcohol by-product of the reaction and can thereby facilitate its removal.
The mixture is stirred at reflux temperature and the distillate containing alcohol of reaction removed. When the desired amount of alcohol has been removed, the acidity conferred by the catalyst is neutralized with a base such as sodium bicarbonate or ammonia, and water is gradually added as distillation is continued until all of the solvent or diluent has been removed by steam distillation. Distillation can be carried out at atmospheric pressure or under vacuum. Sufficient water is added tomaintain a stirrable viscosity in the reaction mixture. The solid content of the final mixture will preferably be about 20-25%. The cooled mixture is stirred, optionally in a high-shear mixer, to prepare a stable dispersion. The dispersion is best diluted to 10 to 15% solids for maximum stability, while a small 7 amount of isopropanol, such as -10% of total dispersion weight also improves the stability of the dispersion. Too much isopropanol, such as 20% or more, may completely dissolve the solid material.
Among materials suitable for use as inert diluents are hydrocarbons such as benzene, toluene and xylene; halogenated hydrocarbons such as monochlorobenzene, 1,1,2,2-tetrachloro-l,2-difluroethane and carbon tetra chloride; and ketones and ethers of suitable boiling point.
Compounds suitable for use as reaction catalysts are acidic materials such as p-toluenesulfonic acid, phosphoric acid and even sulfuric or hydrochloric acid if a very small amount is used.
For treating textiles, it is unnecessary to isolate the solid products of the reaction. Because of the aqueous solubility of the adducts of this invention, the improved properties they confer on textile substrates do not have the desired durability unless the adducts are coapplied with a permanent press or crease resistant resin. The adduct and resin can be conveniently coapplied from an aqueous emulsion by dipping the textile material into a bath, by spraying or calendar coating. The permanent press or crease resistant resin is accompanied by the usual resin catalyst, usually an acidic material such as zinc nitrate, magnesium chloride, an amine hydrochloride or an organic acid. The treated material is dried at about 120C., then cured at the prescribed resin curing temperature and time, usually about 165C. for about 3 to 5 minutes. The resin and adduct are thus fixed to the fabric, and the functional attributes of the adduct persist through a number of launderings.
Permanent press and crease resistant resins are well known in the textile art. As an example of a permanent press resin, there may be mentioned 1,3- bis(hydroxymethyl)-4,5-dihydroxy 2-imidazolidinone. Crease resistant resins are exemplified by compounds such as tetramethylolacetylenediurea, dimethylol [cyclic]ethylene urea, melamine-uron compositions, hexamethylol melamine and the dimethyl ether of trimethylol melamine.
All of these products are useful as textile treating resins and when properly applied and cured are fixed durably to textile material. They are broadly described as aminoplast resins. Their use has been largely on textiles composed of polyester-cotton blends and on cotton itself. The adducts of the invention are useful on polyester-cotton blends and on polyester textiles, especially knitted goods.
The oil and water repellency and soil release properties obtained by coapplication of the adducts of this invention along with permanent press or crease resistant resins are not shown by textiles treated with the resins only.
The amount of the adduct of the invention usefully deposited on textile material can range from about 0.1 to 5.0% based on weight of dry fiber. Preferably the amount will be from about 0.2 to 2.0%. The amount of aminoplast resin coapplied can range from about 0.1 to 10.0% of the resin based on weight of dry fiber. Since these products are normally sold in a diluted form, usually at 50% concentration, the amount of commercial resin formulation used can be much higher. Preferably the amount of actual aminoplast resin codeposited will be from about .0.1 to 1.0%,as this, amount will ordinarily serve, to durabilize .the'properties conferred by the adduct of the invention. Where a crease-proofing treatment is being applied, much larger amounts of crease-proofing resin can be coapplied with the adduct of the invention. Treatment baths can also include other textile treating agents such as softeners, static eliminators, snag resistant agents and the like.
As mentioned before, the adducts of this invention can be conveniently applied by dipping, or by spraying an aqueous emulsion of the adducts onto the textile. Solutions of the adducts and resins in organic solvents can also be used.
The following examples illustrate this invention. Parts and percentages referred to therein are by weight unless otherwise indicated.
EXAMPLE 1 Into a suitable vessel were charged 140.1 parts of R,CH CH Ol-l where R, is a mixed perfluoroalkyl of 4 to 14 carbon atoms, the average molecular weight being 470, 60.0 parts of HO(CH CH O) H (Carbowax, 1000, Union Carbide Co.), 28.7 parts of hexa(methoxymethyl)melamine (Cymel 300, American Cyanamid Co.), 129.9 parts of toluene, 120.1 parts of methylisobutyl ketone and 0.15 parts of p-toluenesulfonic acid monohydrate. This ratio of reactants corresponds to 0.3 equivalent of polyfluoroalcohol, 0.12 equivalent of polyethylene glycol and 0.441 equivalent of hexa(methoxymethyl)melamine. The vessel was fitted with an agitator, a thermometer and a fractionating column with refluxing distillation head.
The reaction mass was stirred and heated at reflux, removing the methanol product as an azeotropic distillate; 15.4 parts of methanol were collected, slightly more than theorized, probably due to presence of a little methanol in the hexa(methoxymethyl)melamine. When the mass became rather viscous at the end of the reaction, about 0.48 part of 10% ammonium hydroxide solution was added to neutralize the catalyst. All of the solvent material was then removed by distillation as water was added at a rate sufficient to keep the mass stirrable. The solids content when all solvent material had been removed was 20-25%. The mass was removed from the reaction vessel and vigorously agitated in a high shear blender to give a stable dispersion of the solid product in water. lsopropanol was added to aid the dispersion, the final composition containing 1 1.4% solids and 8% isopropanol. The 1 1.4% polymer suspension can be applied to polyester and polyester-cotton textiles as described hereinafter.
The composition was applied to polyester double knit fabric from an aqueous bath at a treatment level of 0.31% dry adduct on the textile material along with 1.0% melamineuron crease resistant resin composition (Aerotex 23 Special of American Cyanamid Co.) and 0.2% resin catalyst (Accelerator MX, MgCl solution of American Cyanamid Co.) The treated fabric samples were dried 4 minutes at 250F. and cured for 3 minutes at 320F. Results of tests applied initially to fabrics as treated and also to treated fabrics after 5 home washes are shown in Table 1 below.
Water Repellency Explanation of the tests is given in the next examples.
EXAMPLES 2-7 A series of preparations were made employing the general procedure of Example 1, but varying the mol ratio of the three primary constituents as used in that example and also using l,l,2,2-tetrachloro-l,2- difluoroethane in place of the toluene and methylisobutylketone used in Example 1. The amounts of the various reactants used, the amount of product obtained, and the equivalents ratio of the polyfluoro reactant (A) to polyalkylene glycol reactant (B) are shown below in Textile Chemist and Colourist" 3 No. 10, October (1971). .T he soil release values given herein are expressed as 1000 X W, the soiling value of the washed fabric of the reference article. The lower the number, the more easily the soil is removed in the wash test.
The soil release numbers have no absolute value but are compared, in every case, with an untreated blank subjected to the same soiling treatment.
To prepare a bath for applying the textile treating agents it was first determined how much of the liquid dispersion was retained on a standard size cloth sample when it was dipped and wrung twice. The bath was then prepared by adding weighed amounts of the reaction product Aerotex 23 Special and Aerotex catalyst, Accelerator MX MgCl solution, to water, mixing and diluting to a standard volume. Weight was adjusted so that each treated and dried cloth sample had taken up, based on its dry weight, a known amount of the solid reaction product, 1.0% of the commercial Aerotex 23 Special Product and 0.2% of the commercial catalyst. In the present examples the bath contained also 2.0% of its weight of isopropanol.
After dipping and wringing, the test cloths each were dried for 4 minutes at 250F., then cured for 3 minutes Table I1.
TABLE II Example No. 2 3 4 5 6 7 moles .l .1 .1 .l .l .l A) Fluoroalcohol [equiv .1 .l .l .1 .l .1 parts 46.7 46.7 46.7 46.7 46.7 46.7 moles .031 .031 .02 .02 .011 .01 1 B) Carbowax 1000 equiv. .062 .062 .04 .04 .022 .022
parts 31.1 31.1 20.0 20.0 10.7 10.7 moles .027 .021 .023 .019 .020 .016 C) Hexa(methoxymethyl)- equiv. .162 .126 .138 .1 14 .120 .096
melamine parts 10.5 8.4 9.1 7.6 7 9 6.3 I 1.6 1.6 s 2.5 4.5 4.5 Equivalent ratio A/B 1 0 1.0 1.0 W 1 1 p-Toluenesulfonic acid .05 .05 .05 .05 O5 05 monohydrate, parts 1,1,2,2-Tetrachloro- 163.7 163.7 163.7 163.7 163.7 163.7
1,2-difluoroethane. parts Solid product, parts 56.6 56.5 54.5 44.7 46.7 41
Each of the above products was applied to polyestercotton fabric samples (designated 224R-2) along with Aerotex 23 Special, a commercial crease resistant resin (melamine-uron composition), dried and cured. The treated fabric was tested for oil repellency, water repellency and soil release.
The Oil Repellency Test is the American Association of Textile Chemists and Colourists Standard Test Method 118-1966.,The Water Repellency Test is the American Association of Textile Chemists and Colourists Standard Test Method 22-l952 (ASTM D58363). The Soil Release Test is that described in at 320F. The treated cloth pieces were tested as treated, and again after 5 home washes.
A standard wash consisted of a complete wash and spin dry cycle in a conventional automatic washing machine (Sears-Roebuck Kenmore Model 600) using about 18 gallons of water, 90.0 g. AATCC detergent number 124 and a 4 lb. load of textile material. Temperature of washing was 140F. The load was tumble dried at up to 180F. in the companion clothes drying machine (Kenmore 600).
Results of the tests for Examples 2-7 are listed below in Table III.
TABLE III Reaction Product Oil Repellency Water Repellency Soil Release on wt. of After After After Example cloth Initial Washes Initial 5 Washes Initial 5 Washes 2 .31 6 3 70 6 1o 3 .31 5 3 50 70 7 l3 4 .286 6 4 70 9 5 5 .286 5 3 70 8O 23 14 6 .265 2 2 70 80 40 45 7 .265 6 5 70 7O 1 1 31 Untreated 0 0 70 0 530 524 1 1 EXAMPLES 8-10 1n this series of examples, preparation of the composition of the invention was carried out in the manner described for Examples 2-7. The equivalents ratio of Treatment baths were prepared for each of the three samples and the compositions were applied to 100% polyester double knit fabric designated Chem. 224112. Each test cloth took up, in addition to the polyfluoro the polyfluofo reactant t the P y y g y 5 adduct as of dry fabric weight, 1.0% melamine-uron was Val'led from permanent press resin composition (Aerotex 23 Special of American Cyanamid Co.) and 0.2% resin catalyst (*Accelerator MX MgCl solution of American Cyanamid Co.). The treated test cloths were dried 4 minutes at 250F., then cured for 3 minutes at 320F. Materials used for each preparation are shown in Table d tested a d scribed for examples 2-7. IV. 1 Test results are shown in Table V below.
TABLE IV A) Fluoroalcohol moles .1 .1 .1 equivalents .1 l .1 parts 46.7 46.7 46.7 B) Carbowax 1000 moles .031 .02 .01 equivalents .062 .04 .02 parts 31.1 20.0 10.7 C) Hexa(methoxymethyl)melamine moles .032 .028 .024 equivalents .195 .168 .146 parts 12.6 10.9 9.5 Equivalents ratio A/B 1.0 1 O l O p-Toluenesulfonic acid .05 .05 .05
monohydrate, parts 1,1,2,2-Tetrach1oro-1.2- 163.7 163.7 163.7
difluoroethane, parts Solid product, pans 84 59.4 58.4
TABLE V Reaction Product Oil Repellency Water Repellency Soil 9 on wt. of After After After Example cloth Initial 5 Washes Initial 5 Washes Initial 5 Washes 8 .31 2-3 0 7O 48 64 9 .285 5 2 70 70 17 29 10 .265 7 l 70 70 6 27 Untreated 0 0 70 70 128 TABLE VI Example No. 1 1 12 13 A) Fluoroalcohol moles .1 .1 l [equivalents .1 .1 .1 parts 46.7 46.7 46.7 B) Carbowax" 1540 moles .02 .013 .007 equivalents .04 .026 .014 parts 31.1 20.0 10.7 C) Hexa(methoxymethyhmelamme moles .028 .025 .023 equivalents .168 .15 137 parts 10 9 9.8 8.9 Equivalent ratio A/B 2.5 3.8 7.1
1 1 1 p-Toluenesulfonic acid 0.05 0.05 0.05 monohydrate. parts 1,1 ,2,2-Tetrach1oro-1,2- 163.7 163.7 163.7
difluoroethane, parts Solid product. parts 68 68.8 53.0
for Examples 810. Results of the tests are shown in Table VII.
EXAMPLES 14-16 Preparation of the compositions in these examples was again carried out as in the previous examples. These three examples employed polyethylene glycol having a molecular weight of 4000. Materials used for each preparation are shown in Table VIII.
The products were applied and tested as described for the previous six examples. Results of the tests are 10 shown in Table IX.
TABLE VII Reaction Product Oil Repellency Water Repellency Soil Release on wt. of After After After Example cloth Initial Washes Initial 5 Washes Initial 5 Washes 1 l .31 7 2 70 7O 1 1 19 12 .285 6 1 70 70 9 70 13 .265 6 0 70 70 15 30 Untreated 0 0 70 70 128 165 TABLE VIII Example No. 14 15 16 A) Fluoroalcohol moles .1 .1 .1 equivalents .1 .1 .1 parts 46.7 46.7 46.7 B) Carbowax 4000 moles .0078 .005 .00265 equivalents .0156 .01 .0053 parts 31.1 20.0 10.6 C) Hexa(methoxymethyl)me1amine moles .0231 .022 .021 equivalents .1387 .132 .126 parts 9.0 8.6 8.2 Equivalents ratio A/B 6,4 18,8
1 1 1 p-Toluenesulfonic acid .05 .05 .05
monohydrate, parts 1.l,2,2-Tetrachloro-l,2- 163.7 163.7 163.7
difluoroethane. parts Solid product, parts 79 68.7 59.5
TABLE IX Reaction Product Oil Repellency Water-Repellency Soil Release on wt. of After After After Example cloth Initial 5 Washes Initial 5 Washes Initial 5 Washes 14 .308 4 1 5O 70 21 26 .280 4 0 70 70 27 9 16 .265 3 0 70 70 17 Untreated 0 0 70 128 TABLE X Example No. l7 18 19 A) Fluoroalcohol moles .1 .1 .1 equivalents .1 .1 .1 parts 46.7 46.7 47.7 B) Carbowax" 200 moles 0.1 .058 .026 equivalents .2 .1 17 .052 parts 20.0 1 1.7 5.2 C Hexa(methoxymethy1)melamine moles .074 .064 .038 equivalents .45 .325 .228 parts 29.2 21.1 14.8 Equivalents ratio A/B 0.50 0.86 1.9
l 1 1 p-Toluenesulfonic acid ()5 .05 .05
monohydrate, grams 1.l,2,2-Tetrachloro l ,2- 163.7 163.7 163.7
difluoroethane, grams Solid product, grams 84.2 66.7 61.8
TABLE XI Reaction Product Oil Repellency Water Repellency Soil Release 70 on wt. of After After After Example cloth Initial S Washes Initial 5 Washes Initial 5 Washes 17 .27 0 0 70 70 54 104 18 .245 O 0 70 70 113 114 19 .229 0 0 7O 70 217 174 Untreated 0 0 0 0 226 449 TABLE x11 Example No. 20 2'1 22 i A) Fluoroalcohol moles .l .1 l .-l
[equivalents .l .1 w, l parts 46.7 46.7 46.7 B) Carbowax" 600 moles .033 .0195 0.0085
equivalents .067 .0389 .017" parts 20.0 1 1.7 5.2 C) Hexa( methoxymethyl )melamme moles .041 .034 .029 equivalents .25 I .208 .176 parts 6.3 13.6 1 1.4 Equivalents ratio A/B 1.5 2.6 5 .9
l p-Toluenesulfonic acid .05 .05 .05
monohydrate, parts 1,l,2,2-Tetrachloro-1,2- 163.7 163.7 163 7 difluoroethane, parts i I Solid product, parts 63.0 67.4 59.0
TABLE XIII Reaction Product Oil Repellency Water Repellency Soil Release on wt. of After After After Example cloth Initial 5 Washes Initial 5 Washes Initial 5 Washes .252 4 2 70 70 I8 2 21 .235 3 l 70 7O 9 65 22 .220 2 l 70 70 I 36 282 Untreated 0 0 0 0 226 449 EXAMPLES l7-19 Preparation of the compositions was again carried out as in the previous examples. The three comparative examples employed polyethylene glycol having a molecular weight of 200, which is below the lower limits of this invention. Materials used for the preparation are shown in Table X.
The products were applied and tested as for the previous 9 examples. Results of the tests are shown in Table XI.
EXAMPLES 20-22 Preparation of the composition was carried out as in the previous examples. These three examples employed polyethylene glycol having a molecular weight of 600. Materials used for the preparation are shown in Table XII.
The products were applied and tested as described for the previous 12 examples. Results of the tests are shown in Table XIII.
EXAMPLES 23-28 Into a suitable vessel, equipped with a column for fractional distillation, there was charged 63 parts of the polyfluoroalcohol RKIH CI'I OH where R, is a mixed perfluoroalkyl of 4 to 14 carbon atoms where average molecular weight of the alcohol was 470, 27 parts of polyethylene glycol of 1000 molecular weight, 0.069 parts of p-toluenesulfonic acid monohydrate and 300 parts of 1,1,2,2-tetrachloro-l,2-difluoroethane. The mixture was heated to reflux and a distillate of water and halogenated diluent removed until no more water appeared in the distillate. The diluent was separated from the water and returned to the reaction vessel. In a separate vessel 12.8 parts of hexa(methoxymethyl) melamine was similarly dried, and was then charged to the first vessel with the other reactants. The entire charge was then heated to reflux and the methanol reaction product was removed by fractionation. At the end of the reaction the temperature at the top of the fractionating column reached 93C., the boiling point of the diluent. The mass was cooled at 50 60C. and a solution of 63 parts of sodium bicarbonate, 1720 parts of water was added. Sufficient additional water was added to provide a 25% solids mixture on a diluent free basis. The temperature of the mass was again raised and the halogenated diluent removed by distillation under reduced pressure. Temperature in the reaction vessel was not allowed to go above C. When all of the diluent had been removed, the charge was cooled to 2530C. About 315 parts of isopropanol were then added for each 454 parts of solids in the charge, and sufficient water was added to bring the solids content to 17.0%. The mass was homogenized in a high shear mixer. A stable dispersion resulted which was water extendable, and finally water was added to bring the solids content to 11.4%.
The adduct was coapplied to polyester double knit textile samples with 6 representative commercial crease resistant resins shown below in Table XIV. Aqueous baths were prepared to contain the adduct, the commercial resin and a 2 part catalyst, one-half zinc nitrate and one-half aluminum glycollate glycollic acid mixture. The amount of each commercial product used was 0.5% of the product as sold on the weight of dry textile. In each test there was deposited on the fabric 0.45 6% of its weight of the solid adduct prepared above.
24 Karaset 1452 carbamate TABLE XIV-Continued TABLE XVIl Example Commercial Resin Chemical Type Materials 25 Cymer' 300 hexa(methoxymethyn' A) Fluoroalcohol moles 0.30
melamine equlvalents 0.30 26 Aerotex Reactant 23 melamtne-uron pans 140" Special B Pol ro lene lcol moles 0.0296 27 Permafresh I83 dihyclroxydimethylolg? y equivalents 0059 ethylene ur ea pans 600 28 Permafresh I68 dihydroxydtmethylol- C) fl th th l) m 0 2 ethylene urea 10 melamine equivalents 0.377
- .parts 24.5 p-Toluenesulfonic acid I 0.3 parts i l, l ,2,2,-T hl -l ,Z-d'fl h 49l 115 In each test there was also deposited on the fabric Solid 32i? 90 51 0.1% of a resin catalyst,
Sunkem Catalyst X4 (zinc nitrate solution) After dipping the test fabric pieces and wringing to the proper wet pick-up, the pieces were dried at 250F. for 4 minutes then cured at 320F. for 3 minutes.
The pieces were tested for oil and water repellency and for soil release both initially and after 5 home washes as already described herein. Results obtained are shown in TableXV below.
EXAMPLE 31 The preparation of this adduct was carried out as in example 29. Materials are shown in Table XVIII below.
TABLE XV Oil Repellency Water Repellency Soil Release After After After Example Initial 5 Washes Initial 5 Washes Initial 5 Washes v i 26 5 3-4 70 70 7 I 27 6 4 7O 70 I3 67 28 6 4 70 70 2 Untreated 0 0 70 70 700 I072 TABLE xv111 EXAMPLE 29 p Materials Preparation of the adduct was carried out as in the 40 A) Fluoroalcohol moles 0.30 previous examples using polypropylene glycol 1n place [equivalents 030 of polyethylene glycol. Materials used for the prepara- P I h l I I p g- 0 yet y ene g yco mo es t1on are shown in Table XVI below. ("10L wt 20,000) equivalents 0006 parts 60.0 C) Hexa(methoxymethyl)- moles 0.0536 melamine equivalents 0.323
45 parts 208 TABLE XVI pToluenesulfonic acid 0.3 v
- 1,1 2,2-Tetrachloro-l,Z-difluoroethane 491 parts Materials Sohd product 212.7 parts A) Fluoroalcohol moles 0.30 1
equivalents 0.30 50 EXAMPLE 32 r parts 140.1 B) polypropylqne glycol moles Q0535 Preparatlon of thls adduct was carried out as n ex (mol. wt. 1025) equivalents 0.107 ample 29, but usmg hexa(butoxymethybmelamme in parts 60.0 C) Hexflmethoxymethyu moles 007] place of hexa(methoxymethyDmelarmne. Materials are melamine [equivalents 0.426 shown In Table XIX below- Pam TABLE XIX Equivalent ratio A/B 5 .6
1.0 p-Toluenesulfonic acid 0.3 parts l,l,2.2-Tetrachloro-l,Z-difluoroethane 491 parts Mama's Solid Pwduc Parts I A) Fluoroalcohol moles 0.30 equivalents 0 30 parts 140.]
B) Polyethylene glycol moles 0.06 (mol. wt. I000) equivalents 0.12
parts 60.0 C) Hexa(butoxymethyl)- moles 0.0748
melamine equivalents 0.447 parts 48.0 EXAMPLE 3O p-Toluenesulfonic acid 0.3 parts I,l,2,2-Tetrachloro-l,Z-difluoroethane 491 parts Solid product 215 parts Materials used are shown in Table XVII below. Preparation of this adduct was carried out as described in example 29.
Samples from the previous four examples, 29-3 2, were tested for oil and water repellency and soil release quality on 100% polyester double knit fabric. In each instance an emulsion was prepared to contain 11.4 parts of the solid adduct, 8.0 parts of isopropyl alcohol, 11.4 parts of l,1,2,2-tetrachloro-1,2-difluoroethane, II I 50.0 parts of water and 1.14 parts of octadecyl- 5 i trimethyl ammonium chloride. The mixture for each emulsion was agitated in a high shear mixer and pH ad- H, justed to 8.0 0.2 with sodium bicarbonate. Sufficient water was finally added to bring the total weight of each emulsion to 100 parts except for the product of wherein example 31 which required more water to achieve a R is alkyl of one to 5 carbon atoms; reasonably low viscosity. The emulsion from example n has a value of 0 to 2; and 31 contained 9-75% of the P p adduct m has a value of O to 3 with the limitation that n Aqueous baths were prepared to contain sufficient m Cannot exceed a value f 3;
adduct in each case to deposit 142570 of the adduct 0h wherein the equivalents ratio of A to B is from about the dry weight of test fabrics. From the same bath was 1/2() to /1 d h equivalents ratio f A B to C i deposited in each case 1.0% of Aerotex 23 Special f about 5/1 to 1 5/1 crease resistant resin and 0.2% of Accelerator MX An adduct f Claim 1 wherein the po|y(alkoxymecatalyst as previously described. The wet treated test thynmelamine is hexa(methoxymethyl)me1amine Pieces were dried at for 4 minutes cured 20 3. An adduct of claim 2 wherein the alcohol has the for 3 minutes at 325F' formula R,-CH Cl-l Ol-i and R; is perfluoroalkyl of Test results are shown in Table XX below. 4 through 14 carbon atoms.
The embodiments of the invention in which an exclu- 4. An adduct of claim 3 wherein the polyalkylene glysive property or privilege is claimed are defined as folcol is a polyethylene glycol having a molecular weight lows: of from 400 to 4000 1. An adduct prepared by the condensation, in the 5. An adduct of claim 4 wherein the alcohol has an presence of an acid catalyst and under temperature and average molecular weight of about 470 and the formula pressure conditions that result in the removal of alco- 4O R CH CH -OH wherein R; is a mixture of per-fi dhOl formed y the condensation, of nated straight chain alkyl groups of 6 through 14 car- A. an alcohol of the formula bon atoms 2)11 wherein is perfluoroalkyl of 6. An adduct of claim 5 wherein the polyethylene glyfrom 4 through 16 carbon atoms; and n is an inteco] has a molecular weight f about 1()()() S from 1 through about 7. An adduct of claim 1 prepared by condensing in a P y y glycol of the formula the presence of an acid catalyst 2 A. about 5 equivalents of the alcohol;
wherein R is hydrogen or methyl; and B. About 2 equivalents of the polyalkylene glycol;
m is an integer from about 8 through about and 450; C. about 7.5 equivalents of the poly(alkoxymethyl)- and having a molecular weight between about melamine po|y(alkoxymethy])melamine 400 and about 20,000; and C. a poly(alkoxymethyl)melamine of the formula