US3535247A - Fiber reactive and fiber non-reactive fluoro-alkylacetals of dialdehydes and materials treated therewith - Google Patents

Description

United States Patent 3,535,247 FIBER REACTIVE AND FIBER NON-REACTIVE FLUORO-ALKYLACETALS 0F DIALDEHYDES AND MATERTALS TREATED THEREWITH Domenick Donald Gagliardi, 185 Howland Road, East Greenwich, RI. 02818 No Drawing. Continuation of application Ser. No.

583,429, Sept. 30, 1966, which is a continuation-inpart of application Ser. No. 295,507, July 16, 1963. This application July 7, 1969, Ser. No. 845,641 Int. Cl. Ctl7c 43/30 U.S. Cl. 260-65 8 Claims ABSTRACT OF THE DISCLOSURE Perfiuro diacetals of dialdehydes are provided which are useful for treating substrates in order to obtain oil and water repellent finishes thereon. Of the four ether groups present in the molecule at least one contains a C to C alkyl having a terminal CHF or CF grouping and wherein at least 70% of the normally present hydrogen atoms of the alkyl have been replaced by fluorine atoms. The remaining ether groups may be either similar or different perfluoro alkyl moieties of 3 to 22 carbon atoms or alkyl of 1 to carbon atoms. Where two of the ether groupings on the same carbon atom are alkyl of 1 to 4 carbon atoms, the compounds are reactive with substrates containing active hydrogen therein, e.g. cellulose. The diacetals of this invention are either liquids or high-melting waxes depending upon the molecular weight of the product.

This application is a continuation of application S.N. 583,429, filed Sept. 30, 1966 and now abandoned which is in turn a continuation-in-part of application SN. 295,507, filed July 16, 1963.

The present invention relates to the preparation of fiber reactive and non-reactive fluoroalkylacetals of di aldehydes and to textile materials and other substrates to which said fluoroalkylacetals are affixed.

The treatment of textile materials to endow the textile with an ability to shed water or repel water dates from at least the early nineteenth century when Macintosh presented to the world his treated cloth having a sufficient water-repellency that his name was used to designate a group of garments known as Macintoshes. From the time of Macintosh to 1935 to 1940 textile materials were coated with various compositions such as rubber, linseed oil-rubber mixtures, synthetic dopes, and other whimsically strange compositions which formed a continuous coating on the woven material and prevented the penetration of water.

Without understanding the basic principles of surface free energy, contact angle and spreading coefficient several unrelated practical developments emerged during the years 1935 to 1940 which changed the art of textile waterproofing. In Germany, especially at Chemische Fabrike Pfereze, a series of parafiin wax emulsions was developed which, when padded onto textiles, produced a high contact angle of water drops on the treated surface and a high degree of shower resistance without changing the porosity or air-permeability of the textile material. The treated fabrics were not wetted by water or water-borne liquids and stains because of the change in free energy of the surfaces of the fiber and not be cause of closing or plugging the interstices of the fabric.

By use of the new wax emulsion-metallic salts compositions, it was then possible to produce fabrics which were water repellent and had the feel and appearance of conventional textiles but did not look like oil-cloths ice or rubberized coated fabrics. The only practical limitation of such compositions was the durability to washing and dry cleaning. Such wax emulsion-metallic salts compositions usually contain (1) paraflin wax or mixtures of vegetable wax esters such as carnauba, candelilla, or sugar cane wax; (2) an emulsifying agent, generally glue, gelatin and rosin soaps; and (3) an aluminum or Zirconium salt usually the formate or acetate. The primary function of the salts is to insolubilize the glue and other emulisfiers after the emulsion is deposited on the fibers.

A large variety of such products are still used as lowcost, non-durable water repellents for textiles. Other than water repellency for rainwear fabrics, such compositions produce fabrics which have a fair degree of spotand stain-repellency against water-borne stains.

The search for durable or permanent water repellents, especially for cellulosic fibers, was initiated by the deficiencies of the previously discussed wax emulsion-metallic salt products.

The first important development was the use of octodecyloxymethyl pyridinium-chloride available in England under the trade name Velan. Velan is a quaternary ammonium compound made by the chloromethylation of octadecanol followed by quaternization with pyridine to yield a composition corresponding to the formula:

CISTIKIO CHQN C This structure, unlike other quaternaries, is unstable and under acid conditions reacts with surfaces containing active hydrogen, e.g., the hydrogen of the hydroxyl group of cellulose fibers. This, if Z is the base of the cellulose molecule then the reaction may be represented by the equation Fabrics treated with such a compound are durably Water repellent, are porous, soft, and appear like untreated fabrics. A major improvement in this product was made by du Font and Warwick Chemical Company, who produced the stearamidomethyl analog of Velan having a composition corresponding to the formula Cl7l'I3500NIICI'I2N O known commercially as Zelan and Norane R. The advantages of the stearamide product is its greater initial water repellency and greater durability to washing. Such products are still in the forefront of the leaders in rainwear fabrics finishes.

The search for fiber reactive or durable water-repellent textile finishes continues. Other classes of water-repellent textile finishes have been introduced to the textile finishing art of which silicone water-repellents methylolstearamide compositions (Pernielj Ahcovel NW), hydrophobic resins (Norane GG, Ranedare R, Argus DWR), octadecylketene dimer (Aquapel) and others are representative.

While durable water repellents, such as those briefly mentioned hereinbefore, had been initially designed for outerwear and raincoat type applications, in the period from 1950 to 1956 the use of such products as finishes for mens suitings, dress goods, and upholstery materials become almost common place. In these uses, promotional emphasis was placed not upon water-repellency but upon resistance to spotting and staining. It was subsequently observed that fabrics treated with such water-repellents had a high degree of resistance to soiling by water-borne soils and strains and were easier to launder. The only limitation of such finishes was that they appeared to attract oily soils and the fabrics treated with these finishes were not stain repellent against oily materials such as oils, greases, gravy, mayonnaise, and the like.

While resistance to soiling by water-borne soils and stains, e.g., coffee is of considerable importance, the development of finishes which resist staining by oil-borne stains such as mayonnaise and, particularly finishes which do not attract oily particulate-soil open-up an entirely new field of textile finishing. For example, the cocktail party and the canapes served therewith does not concomitantly include the need to dry clean the rugs. Of even greater importance, is the ability of a finish to shed rather than attract oily particulate-soil. The incidence of staining a shirt-front with mayonnaise is only once or twice a day but the dust, i.e., particulate-soil of the environment and the oily exudations of the human skin which deposit on the neckband and wrist-end of the cuffs of mens shirts is always present during each minute of the hours during which the shirt is worn. Thus, it is manifest that, while the disadvantage of these durable waterrepellents when used as finishes for mens suitings, dress goods, upholstery and the like may not seem too important upon cursory consideration, after more profound review the boon of finishes which repel not only oil-borne stains but in addition repel rather than attract oily particulate-soil becomes self-evident. Such particulate-soil repellent finishes are provided by the present novel perfiuoroalkylacetals of dialdehydes of the present invention.

The novel perfiuoroalkylacetals of dialdehydes of the present invention provide finishes for textile materials of two relatively durable classes, i.e., one class of the present perfluoroalkyl acetals is non-reactive with the fiber, the other class of the present perfiuoroalkylacetals is reactive with active hydrogen contained in the surface of the fiber.

NON-REACTIVE PERFLUOROACETALS The perfiuoroalkylacetals of the present invention which are non-reactive with the fiber have compositions corresponding to the formula omoHanofi Q02 OQ3 I Where Q is the residue of an alcohol having 3 to 22 carbon atoms, having either a terminal -CHF group or, preferably, a terminal --CF group in which at least 70 percent of the hydrogen atoms of the alkyl group of the parent alcohol are replaced with fluorine atoms and the alkyl chain is straight or branched and n is zero to 22, and the other Qs are similar to Q or an aliphatic chain containing at least 6 uninterrupted carbon atoms, and preferably alkyl of 6 to 30 carbon atoms.

REACTIVE PERFLUOROACETALS The perfiuoroacetals of the present invention which are reactive with active hydrogen contained in the surface of the fiber have compositions corresponding to the formula Z Y II where Q and n have the significance given hereinbefore, X and Y together may represent =0 (i.e., an aldehyde) or may be independently OR wherein R is alkyl of 1 to 4 carbons, and Z may be OQ1, 0R or CR where R is an aliphatic chain containing at least 5 uninterrupted carbon atoms. These fiber-reactive-perfiuoroacetals react with the active hydrogen contained in the surface in a manner corresponding to that indicated by the following equation in which Z(OI-I) represents cellulose having in active hydrogen atoms in the surface no 0 ntonano mo (gnaw-L mo n The perfiuoroalkylacetals of dialdchydes of the present invention are either liquids or high melting waxes depending on the value of (n) and on the chain length of the fiuoroalcohol (Q OH).

The preparation of dialdhyde diacetals is described in US. Pat. No. 2,556,312. The patentee discloses that the initial overall reaction between an orthoformic ester and open chain alkenyl alkyl ether is a diacetal of malondialdehyde having a structure illustrated by the following formula RO OR III R0 OR OHCR INOE RO OR IV wherein at least one of the Rs is lower alkyl, e.g., methyl, ethyl, isopropyl, n-propyl, isobutyl, n-butyl and the others independently among alkyl, e.g., C to C and R and R are as indicated above in Formula III.

Specific acetals as illustrative only of Formula IV include:

, ,2,2-tetraethoxyethane ,3,3-tetraethoxypropane ,4,4-tetraethoxybutane ,5,5-tetraethoxypentane ,2,2-tetraisopropoxyethane ,6,6-tetraisopropoxyhexane ,l0,IO-tetraisopropoxydecane l2,12-tetraisopropoxydodecane ,16,16-tetraisopropoxyhexadecane ,20,20-tetraisopropoxyeicosane ,20,20-tetraethoxyeicosane -diethoxy-2,Z-diisopropoxyethane -diethoxy-2,2-di-decyloxyethane -diethoxy-2,Z-di-dodecyloxybutane 1,1-diethoxy-2,2-di-n-butoxydecane 1, 1,2-triethoxy-Z-decyloxyethane l-ethoxy-l,2,2-tri-dodecyloxyethane 1,1-tetraethoxy-4,4-di-n-octyloxybutane 1,1-tetraethoxy-3,3-di(hexyloxyhexyloxy)pentane The following fluoroalcohols are illustrative of those Q OH compounds which are contemplated herein:

. 1H,1H,3H-periluoro-1-octanol The preparation of tetra-acetals of glyoxal is described in US. Pat. No. 2,360,957. This patentee states that glyoxal tetra-acetals are prepared in economic yields by direct reaction at elevated temperatures of glyoxal with a lower, chloroalkanol to produce the tetra-acetals having a composition represented by the formula In US. Pat. No. 2,681,370 the preparation of perfluoroalkylaldehydealkylhemiacetals having the generic formu la ORCl in which each n is an integer from 1 to 12, by direct photochlorination of alcohols having the general formula H(CF CF CI-IOH, in which n has the same meaning as before, at temperatures of from C. to 80 C. using from 0.1 to 0.5 mol of chlorine per mol of alcohol.

The dialdehyde diacetals described in U.S. Pat. No. 2,556,312 are said to be useful as pharmaceutical intermediates. The tetra-acetals of glyoxal described in U.S. Pat. No. 2,360,957 are said to possess merit as an addition agent for extreme pressure lubricants, in making rubber-like products by condensation with polysulfide compounds, and its plurality of chlorine atoms makes it a valuable intermediate for the synthesis of many compounds of unusual structure and properties.

The only use suggested for the perfluoroalkylaldehyde alkylhemiacetals in US. Pat. No. 2,681,370 is a commercially valuable way of transporting the corresponding fluorocarbon aldehyde compounds in pure form.

The fluorinated hemiacetals described in US. Pat. No.

2,842,601 are said to be readily converted to the corresponding aldehydes and this makes them valuable as a convenient storage source of aldehydes.

It is also stated that, by chlorination, the omega-chloroomega'-hydroperfluoro aliphatic hydrocarbons are pro duced which are known to be useful as intermediates in the preparation of surface active agents and treating agents for paper, textiles, and the like and highly fluorinated compounds useful as heat transfer media and the like as described in US. Pats. Nos. 2,790,815 and 2,551,573.

It will be observed that none of the disclosures of the US. patents discussed briefly hereinbefore have any discussion of endowing textile materials with the capability to repel rather than attract particulate-soil.

Yet, as emphasized hereinbefore, probably the most important characteristic of a finish for textile materials such as dress goods, mens suitings, floor coverings, upholstery, and the like is the capability to repel rather than attract particulate-soil.

The perfiuoroalkylacetals of dialdehydes can be applied from aqueous emulsions thereof or from solutions thereof in organic solvent. The fabric to which the acetal is to be afiixed is contacted with the aqueous emulsion or the solution of the acetal to at least eighty to ninety percent wet pick-up of a solution containing at least one percent solids. Generally below about 0.8% by weight perfluoro compound based on the weight of the fabric does not give optimum results although as little as 0.1% is effective. Up to 10% by weight may be used but preferably not more than about 5% gives maximum benefits. The treated fabric is then cured at a temperature in the range of from room temperature to about 375 F. for a period of time, e.g., five to ten minutes at 300 F.

The perfiuoroalkanols, having a terminal CF H or a terminal CF group can be reacted with other polyaldehydes such as polyaldehyde starch, condensed acrolein aldehyde. The novel perfluoroalkylketals can be prepared by transetherification of methyl, ethyl, or propyl ketals of the polyaldehydes of starch, condensed acrolein and the like or by direct reaction of the perfiuoroalkanol and the polyaldehyde.

EXAMPLE 1 Illustrative of the capability of the fluoroalkylacetals of dialdehydes to endow textile materials to which the fluoroalkylacetals are aflixed with capability to shed particulate soil and to repel waterand oil-borne stains are the data presented in Table I.

Exemplary of the perfluoroalkylacetals of dialdehydes is that prepared from trihydrohonafluoroalcohol [H (C1 CH OH see US. Pat. 2,917,409, Example 1] and malonalde- B.Bcfore washing as described hereinafter. A.Atter washing as described hereinafter.

EXAMPLE 2 Example 1 is repeated using the following acetals in dimethylformamide at the indicated concentrations and drying at room temperature.

Conc. Reference to Formula I Q1 and QF 2)6 z-; Q3 and Q4 lauryl and 11:0

B. 1% Q and Q H(CF CH Q and Q isooctyl and n=1 In all instances excellent oil repelleney and soil resistance comparable to Example 1 are obtained. The treated textiles also are characterized by good water-repellent properties.

EXAMPLE 3 Example 2 is repeated except that the treated textiles are cured for 5 minutes at 300 F. Similar results are obtained.

EXAMPLE 4 Example 2 is repeated using the following compounds:

Cone. Reference to Formula II A. 1% Q and Z F(CF CH X and Y together are and 11:0

B. 1% Q1 and Z F(CF CH X and Y together are 0) and 11:1

C, 1% Q and Z F(CF CH X and Y:ethyl and 11:0

D. 1% Q and #F(CF CH X and Y:iso-

propyl and 11:1

E. 3% Q and Z=F(CF CH X:ethyl; Y:

lauryl and 11:0

F. 3% Q=H(CF CH Z:decyl; X and Y:

ethyl and 11:0

G. 4% Q=H(CF CH Z:octyl; X and Y together are 0) and 11:0

H. Q and X and Y:ethyl and 11:0

and Y together are (=0) and 11:0

Illustrative of the preparation of the perfiuoroalkylacetals of dialdehydes is that of the C trihydrofluoroacetal of tetraethoxypropane. Sixty-four grams of C trihydrofluoroalcohol [F I-IC(CF CH OH], about 0.12 mol, were reacted with seven grams of tetraethoxypropane (C H O) C H about 0.032 mol, dissolved in fifty grams of dimethylformamide and 1.0 gram of concentrated sulfuric acid. The mixture was held at 100 C. for two hours, then the ethanol produced and unreacted ethoxypropane were removed under a vacuum. Thereafter at a higher temperature dimethylformamide 3% ClCHzCllzCHzCHzCHzO ClClIzOHzCHzOHgOHzO was removed by distillation under a vacuum. A residue of 67.3 grams of a waxy solid.

where Q is the perfiuoroalkyl radical of the C trihydrofiuoroaleohol, F CH(CF CH were obtained.

The foregoing reaction is illustrative of the preparation of the perfluoroalkylacetals of dialdehydes by transetherification. However, these perfluoroalkylacetals of dialdehydes can also be made by direct reaction of the perfluoroalkanol and a dialdehyde.

EXAMPLE 5 Employing the compounds and concentrations described in Example 2, dispersions are prepared using 0.5% sodium lauryl sulfate as the emulsifier. Concentrated solutions of compounds in dimethylformamide are emulsified in water with the aforementioned emulsifying agent. These emulsions are then applied and dried at room temperature. Excellent soil and Water-proofing is obtained. Illustrative of the water-proofing characteristics, the textiles treated with compound 2D has a spray rating of (as hereinafter described). Compounds 2F, 2H, 2] and 2M also give 100 ratings.

EXAMPLE 6 Example 1 is repeated except that in place of the fluoroalcohol used there, 2 mols of trifluoroethanol are used. Textiles treated with this reaction product exhibit no oil or Water-repellency and no soil resistance.

EXAMPLE 7 The procedures of Examples 2 and 3 are repeated using the following acetals in the indicated concentrations.

A. 1% n-hexyl-O O -u-hexy1 C H C H n-hexyl-O O -n-hcxyl B. 5% 2-etl1yl hexyl-O O-Z-ethyl hcxyl C II C H 2-otl1yl hoxyl-O 0-2-ethyl llcxyl C. 3% n-hexyl-O 0 C 2115 C H-C II n-hoxyl-O O C2115 D; 1% 0211 0 0 C2H5 C H 0 I11 C 11 E. 3% (llCallit) OCzIltUl C 11 (J H2 C II ClC21I4O OCzIIiCl In no case do the treated textiles exhibit any oil or soil repellency as tested herein or any noticeable waterrepellency.

EMMPLE 8 An emulsion is prepared as follows:

2g. of normal-no oonnoFmF CI-I(CH2)22CH mornaorno oar-moron is dissolved in 10 g. of dimethylformamide and then the solution is added to a solution (120 F.) of 1 g. of a non-ionic surfactant (dinonyl phenol +10 ethylene oxide condensate) in 100 g. water while Stirring vigorously. Separate swatches of a cotton textile, an acetate textile, a nylon textile, a Dacron textile, and a wool textile are treated with the aforementioned emulsion and the swatches are dried at room temperature. All of the materials exhibit excellent oil-, soiland water-repellency.

The particulate-soil repellency of the textile materials to which the non-reactive or reactive perfiuoroalkylketals of polyaldehydes have been afiixed is determined by a particulate-soil repellency test. A synthetic soil is used to determine the efficacy of a finish. The recommended composition of this synthetic oily particulate soil is given below:

Ingredient: Percent by weight Peat moss 38 Cement 17 Kaolin clay 1 17 Silica, 200 mesh 2 17 Furnace black 3 1.75 Red iron oxide 4 0.50 Mineral oil 8.75

R. T. Vanderbi1tPeer1ess Davidson Chemical 00.

== Benny & Smith Co.Mo1iacco 4 C. K. Williams Co.

The dry ingredients are blended thoroughly, dried in a forced draft convection oven for eight hours at 50 C., milled twenty-five hours with ceramic balls, and stored in a polyethylene bag.

GRC PARTICULATE SOIL TEST Fifteen to twenty 6" x 8" numbered specimens (usually 80 x 80 cotton) including at least one untreated control are tumbled for thirty minutes with 10 percent of the aforedescribed oily particulate soil based on the weight of the fabric. The tumbling is carried out in a liter capacity Five Minute Homer Cleaner at 44 r.p.m. Six No. 8 Neoprene rubber stoppers are distributed among the specimens to increase the mechanical action. At the end of the tumbling, the specimens are removed and each shaken up and down fifteen times by hand to remove surface dirt, i.e., loosely adherent or non-adherent dirt.

The specimens are then cut in two to provide two 4" x 3 pieces. One-half is washed with 50 grams of Fab in a cotton cycle with a S-pound dummy load, hung to dry, and lightly ironed under a clean cloth.

The degree of soiling is determined with the Photovolt Reflectance Meter (Iri Blue Filter). The arithmetic average of six reflectance readings is reported as the reflectance of the specimen. The higher the reflectance the less particulate-soil has adhered to the specimen.

Water repellency-Resistance to Wetting (Spray Test), AATCC Standard. T est Method 22-1952: This test method is applicable to any textile fabric. It measures the resistance of fabrics to wetting by a Water spray and the results depend primarily on the degree of hydrophobicity inherent in the fibers and subsequent treatments applied. Water is sprayed against the taut surface of a test specimen. Evaluation of the wetted pattern is readily made by comparing the wetted pattern with standard wetting pattern picture: 100No sticking or wetting of the upper surface.

Slight random sticking or wetting of the upper surface.

80Wetting of the upper surface at spray points.

7 0-Partial wetting of the whole of the upper surface.

50Complete wetting of the whole of the upper surface.

0Complete wetting of the whole of the upper and the lower surfaces.

The test specimen, fastened securely and wrinkle-free in a metal hoop having a diameter of about 6 inches is placed and centered 6 inches under a standard spray nozzle at an angle of 45 degrees to the horizontal. Two hundred and fifty milliliters of water at 80 2 F. is poured into a funnel attached above the spray nozzle. The spray lasts twenty-five to thirty seconds at the end of which time the hoop is taken by one edge and the opposite edge tapped smartly once against a solid object with the wet side facing the solid; this procedure is repeated with the hoop reversed 180 degrees.

Oil repellency-3M Oil Repellency Test: 3M Textile Chemicals Appendix A Test Methods, page 1: This Minnesota Mining and Manufacturing oil repellency test is based on the different penetrating properties of two hydrocarbon liquids, mineral, e.g. Nujol a liquid paraffin having a density in the range of 0.83 to 0.905, and nheptane. The Nujol-heptane proportions for each rating Were selected by 3M to give oily stain resistance somewhat comparable to the water-borne stain resistance corresponding to each of the spray ratings of the AATCC Standard Test Method 22-1952.

Percent heptane Percent Nujol Oil repellency rating by volume by volume 1 No hold out of Nujol.

The standard oil-heptane mixtures are contained in small stoppered medicine dropper bottles. A drop of each mixture is placed on the fabric to be tested. The appearance of the test oil is observed through the drop. Note is made Whether wetting or penetration occurs. The number corresponding to that mixture containing the highest percentage of heptane which does not penetrate or wet the fabric after three minutes is considered the oil repellency rating of the system. V

The change in the optical refractivity of the drop is often an indication of wetting. In some cases wetting can be better determined by observing the other side of the fabric. In reporting oil/heptane rating the symbol 0+ is indicative of a modicum of resistance to wetting by oil.

From the foregoing those skilled in the art will recognize that the foregoing discussion has provided a description of novel perfluoroalkylketals and perfluoroalkylhemiketals of polyaldehydes having at least two aldehyde groups. In addition, there is provided a description of the improved resistance to soiling by particulate-soil imparted to textile materials such as dress goods, mens suitings, floor coverings, and the like by these perfluoroalkylketals reactive with or non-reactive with active hydrogen contained in the surface of the textile fiber.

I claim: 1. Compounds of the formulae:

l 3 CH(CH2)nCH Q2 Q4 and II. Q10 0R1 /0H(0H2)..OE Z 0R1 (1) wherein Q is an alkyl group of from 3 to 22, said alkyl having a terminal group selected from the group consisting of CHF and -CF and said alkyl having at least 70 percent of the hydrogen atoms thereof replaced by fluorine atoms,

(2) Q Q and Q; are independently selected from the group consisting of Q fluoroalkyls and alkyl of 6 to 30 carbon atoms,

(3) the Rfs are independently alkyl of 1 to 4 carbon atoms,

(4) Z is selected from the group consisting of OQ and alkoxy of 1 to 30 carbon atoms, and

(5) n has a value of from 0 to 22.

2. Compounds as defined in claim 1 of Formula I.

3. Compounds as defined in claim 1 of Formula II.

4. Compounds as defined in claim 2 wherein Q Q and Q; are Q fluoroalkyls.

5. Compounds as defined in claim 2 wherein Q is a Q fiuoroalkyl and Q and Q; are alkyl.

6. Compounds as defined in claim 3 wherein Z is OQ 1 2 7. Compounds as defined in claim 3 wherein Z is alkoxy of 1 to 4 carbon atoms.

8. Compounds as defined in claim 3 wherein Z is alkoxy of 5 to 30 carbon atoms.

References Cited UNITED STATES PATENTS HOWARD T. MARS, Primary Examiner U.S. Cl. X.R.