CA1071225A - Outerwear fabric treatment - Google Patents

Abstract

ABSTRACT

It is known to treat material so it becomes resistant to staining. However, the treatments presently known have a limited resistance to staining and limited life span. The present invention seeks to overcome this drawback by providing a novel fabric treatment compound which is a solvent-soluble fluoroaliphatic radical-containing carbodiimide consisting essentially of from 1 to a plurality of carbo-diimide groups, terminal organic radicals free from isocyanante-reactive hydrogen atoms and connected to carbodiimide and, when two or more carbodiimide groups are present, polyvalent organic linking groups free from isocyanate-reactive hydrogen atoms linking successive carbodiimides;
at least a portion of said terminal organic radicals or organic linking groups including fluorosliphatic groups of 3 to 20 carbon atoms in a amounts such that said carbodiimide as a whole including form 15 to 45% by weight of carbon-bonded fluorine and said carbodiimide as a whole exclusive of fluoroaliphatic radicals containing at least 12% by weight of carbodiimide groups

Description

107~ZZ5 This application is a divisional application from applicants co-pending Canadian Patent Application serial number 185,022 filed November 5, 1973.
The afore said patent application relates to textile materials and, in particular, to the class of materials including those known as outerwear fabrics which consist essentially of hydrophobic synthetic fibers. More particularly Canadian patent application serial number 185/022 relates to processes for treating synthetic fiber-containing materials to impart durable water and oil repellency and materials so protected.
As a result of the development of polymers containing fluoroali-phatic radicals, a variety of methods for treating fabrics to provide resist-ance to aqueous and oily stains has been developed. Depending upon the intended field of use, these treatments have been more or less durable and have conferred varying degrees of resistance to abrasion, laundering, dry cleaning and such other conditions as are encountered by the fabric during its use. In general, each particular type of abric and each particular use has required a somewhat different treatment, sometimes involving different treating resins, for optimum economic performance.
In particular, excellent durable treatments have been provided for fabrics consisting of blends of synthetic and cellulosic fibers in which the treating materials includes both a fluoroaliphatic radical-containing polymer and an aminoplast resin of the sort typified by the conventional durable-press resins described in United States Patents Nos. 2,783,231 and

2,974,432. Typically, such fabrics have contained from between 25 to 75% of each fiber component. The aminoplast resin deposits primarily upon the cellulosic fibers during treatment and seems to have served to provide improved durability of the fluorochemical treatment toward laundering and dry cleaning.
Recently fabrics consisting substantially completely of hydrophobic synthetic fibers, typically those based on polyamides ~e.g. , nylon) and polyesters ~e.g., polyethyleneglycol terephthalate) have become popular for outerwear, light-weight, brightly colored garments particularly useul in .

~07~ZZ5 sports wear, such as ski jackets, wind breakers, and the like. Such garments obviously encounter a variety of soils, are worn in the rain and under adverse conditions, and should advantageously display the highest resistance to water as well as to staining and soiling conditions. Such garments also require frequent cleaning, and such cleaning may be either laundering or dry cleaning, depending primarily upon the whims of the user.
Heretofore, there has been no satisfactory method for providing such fabrics with the combination of soil and stain resistance with a high level of water repellency which would be durable under the ordinary cleaning procedures.
Durable-press resins applied in sufficient concentration to provide durability produce a hand that is harsh and stiff and completely unacceptable to the customer, perhaps because of the lack of hydrophilic fibers in the fabric.
Other materials such as upholstery and carpet fabrics may also be made of 100% synthetic fibers.
The afore said Canadian Patent Application relates to a process in which durably launderable and dry-cleanable oil and water repellency can be conferred on fabrics consisting essentially of hydrophobic synthetic fibers by applying to said fabric a blend of a fluoroaliphatic group-containing material and a carbodiimide in proportions of from 10:90 to 95:5 and prefer-ably rom 20:80 to 80:20 fluoroaliphatic radical-containing material to carbodiimide. The blend may be applied as a suspension or solution in either aqueous or non-aqueous media.
The afore said Canadian Patent application also pertains to the process or conferring durably launderable and dry-cleanable repellency to oil and water on fabrics consisting substantially completely of hydrophobic synthetic ibers consisting essentially o applying to said fabric a blend, in volatile aqueous or non-aqueous medium, of at least 0.3% by weight of from about 10 to 95 parts of ~A) fluoroaliphatic radical-containing substantially linear vinyl polymer containing from 10 to 60 percent by weight thereof fluorine in the form of fluoroaliphatic groups terminating in CF3 groups, said fluoroaliphatic groups, each containing at least three fully fluorinated carbon atoms and from about 90 to 5 parts of (B) a solvent-soluble carbodiimide consisting essentially of from 1 to a plurality of carbodiimide groups, wherein the carbodiimide groups form at least 12% of the molecule except for:
Cl) terminal and pendent fluoroaliphatic groups when present;
~ 2) terminal organic radicals connected to carbodiimide groups, said terminal organic radicals being free from isocyanate-reactive hydrogen atoms and being substituted or unsubstituted by a fluoroaliphatic radical; and ~ 3) when two or more carbodiimide groups are present polyvalent organic groups, or residues of polyisocyanates linking successive carbodiimide groups, said polyvalent organic groups or said residues of polyisocyanates being substituted or unsubstituted by a fluoroaliphatic group, and thereafter vaporizing said medium whereby a coating of said blend is deposited on said synthetic fibers.
Furthermore the aforesaid Canadian Patent application pertains to a durably launderable and dry-cleanable, oil and water repellent fabric con-sisting substantially completely of hydrophobic synthetic fibers having a coating thereon of a blend, in proportions of from about 10:90 to 95:5, of tA) fluoroaliphatic radical-containing substantially linear vinyl poly-mer containing from 10 to 60 percent by weight thereof of fluorine in the form of fluoroaliphatic groups terminating in CF3 groups, said fluoroaliphatic groups each containing at least three fully fluorinated carbon atoms, and (B) a carbodiimide consisting essentially of from 1 to a plurality of carbodiimide groups, wherein the carbodiimide groups form at least 12% of the molecule except for:
~1) terminal and pendent fluoroaliphatic groups when present;
t2) terminal organic radicals connected to carbodiimide groups, said terminsl organic radicals being free from isocyanate-reactive hydrogen atoms and being substituted or unsubstituted by a fluoroaliphatic radical; and ~3) when two or more carbodiimide groups are present polyvalent organic groups, or residues of polyisocyanates linking successive carbodiimide groups, said polyvalent organic groups or said residues of polyisocyanates being substituted or unsubstituted by a fluoroaliphatic group, said coating being in amount to provide from 0.02 to 0.5% by weight of carbon-bonded fluorine on the fabric.
Additionally the aforesaid Canadian Patent application provides a blend, in proportions of from about lO:90 to 95:5, in volatile aqueous or non~aqueous medium of a total of at least 0.3% by weight of ~ A) fluoroaliphatic radical-containing substantially linear vinyl polymer containing from 10 to 60 percent by weight thereof of fluorine in the form of fluoroaliphatic groups terminating in CF3 groups, said fluoroaliphatic groups each containing at ieast three fully fluorinated carbon atoms, and (B) a carbodiimide consisting essentially of from 1 to a plurality of carbodiimide groups, wherein the carbodiimide groups form at least 12% of the molecule except for:
Cl) terminal and pendent fluoroaliphatic groups when present;
C2) terminal organic radicals connected to carbodiimide groups, said terminal organic radicals being free from isocyanate-reactive hydrogen atoms and being substituted or unsubstituted by a fluoroaliphatic radical; and C3) when two or more carbodiimide groups are present polyvalent organic groups, or residues of polyisocyanates linking successive carbodiimide groups, said polyvalent organic groups or said residues of polyisocyanates being substituted or unsubstituted by a fluoroaliphatic group.
A preferred fluoroaliphatic radical-containing material is a substantially linear vinyl polymer containing from 10 to 60 percent by weight of the polymer of fluorine in the form of fluoroaliphatic groups terminating in CF3 groups and containing at least three fully fluorinated carbon atoms and preferably 3 to 18 fully fluoronated carbon atoms. Acrylates and meth-acrylates are readily available and very convenient vinyl polymers and are particularly preferred.
The carbodiimides consist essentially of from l to a plurality, preferably not over 20, of carbodiimide groups, terminal organic radicals free from isocyanate-reactive hydrogen atoms connected to carbodiimide and, when two or more corbodiimide groups are present, also polyvalent, preferably .

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divalent, organic linking groups which are residues of a polyisocyanate between successive carbodiimide groups. Fluoroaliphatic groups may form parts of terminal or linking groups.
The treating solution ;s applied by padding, spraying or other conventional means and the vehicle or solvent is vaporized to leave a coating of the blend on the fibers. The components can be applied in a series of applications, or, more conveniently, as a single blend. A blend of vinyl polymer and carbodiimide combined in a ratio of 10:90 to 95:5 may be prepared in the desired aqueous or nonaqueous medium and diluted as needed to form the treating solution. The abric is found to be oil and water repellent, launder-able and dry-cleanable with substantial retention of repellent properties and to possessa pleasant hand.
Any of the art-recognized fluoroaliphatic radical-containing poly-mers useful for the treatment of fabrics to obtain oil and water-born stain repellency can be used including condensation polymers such as polyesters, polyamides, polyepoxides and the like, and vinyl polymers such as acrylates, methacrylates, polyvinyl ethers and the like. Many of these are disclosed in the reference in Table 1.
The preferred class of fluoroaliphatic radical-containing vinyl polymers is composed of the acrylate and methacrylate polymers and random copolymers. In any event, it is essential that the vinyl polymer contain a fluoroaliphatic radical terminating in a CF3 group and containing at least three fully fluorinated carbon atoms, preferably a perfluoroalkyl group. The polymer may contain as little as 10% of its weight of fluorine in the form of fluoroaliphatic radicals, and as much as 60% for maximum resistance to dry cleaning. It is preferred that the polymer contain from about 15% to 45% by weight of fluorine. The fluoroaliphatic polymer is applied to the treated fabric so as to provide between 0.02 and 0.5% by weight of carbon-bonded fluorine on the fabric, preferably 0.05,- 0.25% by weight. Although higher levels of fluorine can be applied to provide useful products, the increased cost is not usually warranted by increase in performance.

1~71Z25 TABLE I
InventorsU. S. Pat. No. Title Ahlbrecht,2,642,416 Fluorinated Acrylates Reid and Husted and Polymers Ahlbrecht,2,803,615 Fluorocarbon Acrylate and Brown and Smith Methacrylate Esters and Polymers Bovey and Abere 2,826,564 Fluorinated Acrylate and Polymers Ahlbrecht and 3,102,103 Perfluoroalkyl Acrylate Smith Polymers and a Process of Producing a Latex thereof Johnson and3,256,230 Polymeric Water and Oil Raynolds Repellents Johnson and3,256,231 Polymeric Water and Oil :
Raynolds Repellents Fasick and3,282,905 Fluorine Containing Esters Raynolds and Polymers thereof Smith and3,329,661 Compositions and Treated Sherman Articles thereof Smith and3,356,628 Copolymers of Perfluoro Sherman Acrylates and Hydroxy Alkyl Acrylates Farah and3,407,183 Acrylate and Methacrylate Gi.lbert Esters and Polymers thereof Kleiner 3,412,179 Polymers of Acrylyl Per-fluorohydroxamates Sweeny and3,420,697 Perfluoroalky-substituted Llauw Polyamide Oil-repellency Compound and Textile Mat-erials Treated therewith Pacini 3,445,491 Perfluoroalkylamido-alkylthio Methacrylates and Acrylates and Intermediates therefor Eygen and3,470,124 New Fluorinated Compounds Carpentier and Their Preparation Brace 3,544,537 Poly(perfluoroalkoxy)-polyfluoroalkylacrylate-type Esters and Their Polymers Tandy 3,546,187 Oil and Water Repellent Polymeric Compositions 1~)71Z2~i Carbodiimides are conveniently obtained by condensation of isocyanates in the presence of suitable catalysts as described, for example, in the patents of Table 2 and by Campbell et al,, J. Org. Chem., Vol. 28, pages 2069-2075 ~1963).
.
Table 2 , Bal on 2, 85 3, 518 Chemi. cal Pro ces s Campbell and 2,853,473 Production of Carbodiimides Verbanc Campbell 2,941,966 Carbodiimide Polymers Smeltz 2,941~983 Urethane-Terminated Polycarbodiimides Hoeschele 3,450,562 Cellulosic Materials Coated with An Organic Polycarbodiimide British 1,224,635 Stabilized Polyester Patent Shaped Articles The carbodiimides employed in the aforesaid Canadian Patent Application can be of more or less conventional types including terminal hydrocarbon radicals or they may include fluoroaliphatic radicals as noted above. Fluoroaliphatic radical-containing carbodiimides were not known heretofore and are particularly useful in fabric treatments. The carbon-bond-ed fluorine of these polymers which ranges from about 15 to about 45 percent is included within the totals of fluorine applied to the fabric, i.e., 0.02 to 0.5% by weight.
The present invention is a solvent-soluble fluoroaliphatic radical-containing carbodii~ide consisting essentially of from 1 to a plurality of carbodiimide groups, terminal organic radicals free from isocyanate-reactive hydrogen atoms and connected to carbodiimide and, when two or more carbodiimide groups are present, polyvalent organic linking groups free from isocyanate-reactive hydrogen atoms linking successive carbodiimides; at least a portion of said terminal organic radicals or organic linking groups including fluoro-aliphatic groups of 3 to 20 carbon atoms in amounts such that said carbodiimide as a whole including from 15 to 45 % by weight of carbon-bonded fluorine and said carbodiimide as a whole exclusive of fluoroaliphatic radicals containing ~ _ 7 _ .

at least 12% by weight of carbodiimide groups.
The present invention also provides a fluoroaliphat;c radical-containing carbodiimide as above of the general formula: -B -~N=C=N-A3--nN=C=N-B
wherein n is 0 or an integer from 1 to 20, A is a divalent organic linking group and B is a monovalent organic terminal group at least one of A and B
including fluoroaliphatic radicals with terminal CF3 groups of from 3 to 20 fully fluorinated carbon atoms.
A preferred embodiment of the present invention is a solvent-soluble fluoroaliphatic radical-containing carbodiimide consisting essentially of from 1 to a plurality of carbodiimide groups, terminal organic radicals derived from mono- or polyisocyanate and free from isocyanate-reactive hydrogen atoms and connected to carbodiimide and, when two or more carbodi-imide groups are present, polyvalent organ-c linking groups derived from organic polyisocyanate and free from isocyanate-reactive hydrogen atoms link-ing successive carbodiimide groups; fluoroaliphatic groups of 3 to 20 carbon atoms forming a part of said terminal organic radicals or organic linking groups in amounts such that said carbodiimide as a whole includes from 15 to 45% by weight of carbon-bonded fluorine and said carbodiimide as a whole exclusive of fluoroaliphatic radicals contains at least 12% by weight of car-bodiimide groups.
A further preferred embodiment of the present invention is a fluoroaliphatic radical-containing carbodiimide as above of the general formula:
B ~ N-C=N-A~nN~C~N-B
wherein n is 0 or an integer from 1 to 20, A is a divalent organic linking group d0rived from diisocyanate and B is a monovalent organic terminal group derived from mono- or diisocyanate; fluoroaliphatic radicals with terminal CF3 groups of from 3 to 20 fully fluorinated carbon atoms forming a part of at least one of A and B.

.ZZ5 In general, carbodiimides formed from di-isocya-nates with or without monoisoc~anates are represented for convenience by the general formula:
B (N=C=N-A ~ =C=N-B
where n is 0 or an integer from l to at least 20 and preferably from l to lO. A and B are as defined below.
The A groups or B groups may each be the same or different.
Carbodiimides in which n is 20 and higher are useful but offer no known advantages.
In the above general formula, A is a divalent organic groupwhich may include pendent fluoroaliphatic radicals linking successive carbodiimide groups when n is l or more. Illustrative linking groups include alky-lene, such as ethylene, isobutylene, and the like of 2 to about lO carbon atoms, aralkylene, such as -CH2C6H4CH2-, of up to 10 carbon atoms, arylene, such as tolylene, -C6H3(CH3)-, of up to about 10 carbon atoms, polyoxaalky-lene such as -(C2H40)xC2H4-, containing up to about 5 oxa groups and combinations of the various types. It will be recognized that the A group is the residue of an organic diisocyanate, that is, the divalent radical obtained by removal of the isocyanate group from an organic diisocyanate.
Sultable organic diisocyanates may be simple, e.g., toluene diisocyanate, or complex, as formed by the reaction of a simple diisocyanate with a di- or polyol in proportions to give an isocyanate terminated polyurethane.
Although carbodiimides generally and preferably include divalent A groups, some of the A groups can be, for example trivalent or tetravalent derived from - , ~ . .

tr~lsocyanates or tetraisocyanates such as polymethylene-polyphenyl isocyanates, e.g., OCNC~H4CH2C~H3(NCO)CH2C~H4NCO.
When A is trivalent or tetravalent) branched or even cross-linked polycarbodiimides result. A mixture of A groups containlng some t~ivalent groups can be used to provide branched polycarbodiimides which retain the deslrable solubility and thermoplasticity of the linear carbodiimides resulting from carbodiimides having divalent A groups.
J The carbodiimide groups (-N=C=N-) should represent at least 12% of the molecule except for terminal and pend-ent fluoroaliphatic radicals present.
Substituents may be present in A groups provided they contain no isocyanate-reactive hydrogen atomsj that is, groups such as -OH are normally excluded. Simple un-substituted organic linking groups free from non-aromatic unsaturation are preferred. The organic linking group depends on the polyisocyanate compound employed such as:

- CH2- ~ -CH2 - ,CH
C, eFl7 ~Y
~2 or -CeH3(CH3)NHCO2C2H4~C2H402CHN(CH3)C~H3 10712~:~

The terminal groups, or E-groups, are preferably monovalent radicals of monoisocyanate compounds which may be allphatlc as C4H9-, aralkyl as C6H5CH2-, aryl as C6H5-, and preferably fluoroaliphatic such as C4FgC2H4-l and C7Fl5CH202CNHC6H4(CH3)-, (deri~ed from tolylene dilsocya-nate and 1,1-dihydroperfluorooctanol)0 Numerous other terminal groups are operable in the compounds and process of the invention. When only diisocyanates are used to form the polycarbodilmides, the B groups are monovalent radicals derived from diisocyanates and include an isocya-nate group (or an hydrolysis product of such a group).
The terminal B groups may be the same or different.
Because the monoisocyanate terminates the carbodii-mide molecule, the relative proportion of monolsocyanate to diisocyanate used in the reaction determines the average value of n in the above formula, 0 when no diisocyanate is used upwards so that with about 10 mole percent of mono-isocyanate and 90 percent of diisocyanate n wlll average about 20 as will be readily apparent.
The invention is more particularly described hereinbelow by examples of the preparation of suitable components for the process of the invention and by examples showing the effectiveness of the process of the invention in provlding oil and water repellency durable to washine and/or drycleaning. In these examples, all parts are by weight. The testlng procedures employed in these examples are as follows:

_10--f .

Synthetic fabrics of 100~ filament nylon and 100~ spun and 100~ filament po~yester are treated with the blended formulat~on at a predetermined level of fluoro-aliphatlc component on the fabric. This level is convenlently set to give a particular weight of carbon-bonded fluorine on the fabric, usually of the order of 0005 to about 0.5 by weight~
The water repellency of the tested fabrics is measured by Standard Test Number 22-52, published in the 1952 Technlcal Manual and Yearbook of the American Associ-ation of Textlle Chemists and Colorists, Vol. 28, page 136.
The spray rating is expressed on a O to 100 scale where 100 i8 the highest possible ratingO For outerwear fabrics particularlyJ a spray rating of 70 or higher is considered desirable.
The oil repellency test American Association of Textile Chemlsts and Colorists Standard Test 118-196 is based on the resistance to penetration of oils of varying viscositiesO Treated fabrics resistant only to Nu~ol ,a common type of mineral oil, and the least penetrating of the test oils, are glven a rating of 1, whereas fabrics re-sistant to heptane, the most penetrating of the test oils, are glven a value of 8. Other intermediate ~alues are de~
termined by use of other pure substances. The oil repellency corresponds to the oil which does not penetrate or wet the fabric after 3 mlnutes contact. Higher numbers lndlcate better oll repellency. In general, an oil repellency of 3 or greater is desirable.

.
Trade Mark lO~Z2S

The laundering cycle employed is as follows:
The treated fabrics are laundered in a mechanically agitated automatic washin~ machine capable of containing a 4 kg. load, using water at 60C. and a commercial detergent and then tumble-dried in an automatic dryer ~or 20 minutes at 88C. before being tested. They are not ironed after drying.
Drycleaning is performed by a commercial dry-cleaning establishment and the fabrics are not pressed or heated after the drycleaning process. Perchloroethylene (C2C14) is the solvent used for the drycleaning procedure.
Carbodiimides are usually made from diisocyanates and monoisocyanates in an inert solvent such as methyl lsobutyl ketone, conveniently at a concentration of about 40% of dissolved materials, to which is added about 1% of the weight of the materials of a phospholine oxide or other suitable catalyst. The reaction mixture is prepared so that any water is removed before addition of isocyanates and ls heated until reaction is essentially complete. The reaction mixture can be emulsified in water and further diluted with water before application. The fabric treating solution can be prepared by blending emulsions of carbodii-mide and fluoroaliphatic radical-containing polymers to-gether with any desired compatible ad~uvents. Alternatively, the polycarbodiimide and fluoroaliphatic radical containing polymer can be prepared in solution and the solution blended, diluted if necessary and applied, for example, to fabrics that would be undesirably affected by water. The proportions depend on the amount needed to give a treating solution which .:

107~2ZS
will provide the correct concentration of solids, carbodi-imides plus fluoroaliphatic-radical containing polymer, to attain the desired weight of treatment at the level of wet pickup chosen. This level is herein set at 50% where not otherwise denominated to give comparability of results. Thus for 50% wet pickup, a 0.3% concentration provides 0.15% solids pickup which at 50% fluorine content gives 0.075% ~luorine on .-the fabric. The latter fluorine content is used in these examples, unless otherwise indicated, to permit ready com-parisons.
Example 1 A solution of 101.6 parts (0.17 mol) of C8F17SO2N(CH2CH2OH)2 in 265 parts of methyl isobutyl ketone (MIBK) is first dried by distilling 30 parts of the solvent. Then 54 parts (0.31 mol) f 2,4-toluene diisocyanate are added and the solution re-fluxed for 2 hours to form a prepolymer diisocyanate. The solution is then cooled to 65-75~C., and 1 part of 3-methyl-l-phenyl-3-phospholine-1-oxide is added followed by 3 hours further refluxing. A film cast from this solution is weak and brittle and contains the characteristic corbodiimide infrared absorption peak at 4.69 microns. The solution con-talns the carbodiimide designated Polymer A which is pre-dominantly represented by the formula:

OCN- H3 ~ ~ ~ -NCO

H4 ~ H NHCO2 2H4 ~H 0~C H C8F172S-2 4 2 ~ ~HCO 2H4 -N=C=N- ~

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It will be seen that this structure corresponds to the general formula above in which the group designated as "A" is:

4~--NC02CH:~CHellCll~ 02~?3 and the "B" group is -A-NC0.
To 100 parts of this polycarbodiimide in 121 parts of MIBK is added 4 parts of polyoxyethylene sorbitan monoo-leate emulsifier, 4 parts of C8Fl7S02N(CH3)C2H4N(CH3)3pl emulsifier and 225 parts of distilled water. The mixture is then emulsified using a high shear mixer. The emulsion is employed in fabric treatments.

Example 2 A solution of 90 parts (0.15 mol) of CaFl7S02N(C2Hs)CH2CH20H
in 320 parts of methyl isobutyl ketone is first dried by distilling and discarding 24 parts of the solvent and 82.4 parts (0.473 mol) of 2,4-toluene diisocyanate are added and the solution is refluxed for 3 hours. After cooling the solution to 65 - 75 C., and adding 1.8 parts of

3-methyl-1-phenyl-3-phospholine-1-oxlde to it, the solution is refluxed for a further 3 hours A film cast from this ~07~225 soluti.on i~.weak and brittle and contains the characteristic .
carbodiimide absorption peak at 4.79 micro~s. The solution contains the carbodiimide designated as Polymer B which is represented by the formula: CH3 ~ Z ~ E=~)~-OCH2CH8~O2SCE~F17 ln which it will be seen that the "A'! group is -C~H3CH3-and the "B" group is C8F17S02N(C2H5)-C2H40'2CNHC8H3(CH3)-.
To 100 parts of thls polycarbodiimide in 138 parts of methyl isobutyl ketone is added 2.5 parts of polyoxyethylene sorbi-tan monooleate emulsifier (available under the Trademark Tween 80), 2,5 parts of C8Fl7S02N(CH3)C2H4N(CH3)3Cl and 265 parts of dlstilled water. The mixture is then emulsified, Example 3 To a solution of 27 parts of CBFl7SO2N(CH3) C2H402CC (CH3)=CH2, 2.85 parts of ethylhexyl methacrylate and 0.15 parts of glycldyl me~hacrylate in 12 parts of acetone and 48 parts of water are added 1.5 parts of polyethoxylated quaternary ammonium chlorlde emulsifier, 0.05 parts t-dodecyl mercap-tan and 0.05 pRrts of potassium persulfate. The mixture is dega~sed, blanketed under nitrogen and then heated to 65 C., and the polymerization allowed to proceed wlth agitation for 16 hours. A fllm cast from this materlal is hard and brittle.
The random copoly,mer having pendent fluoroaliphatic groups is designated Polymer C.

Example 4 The procedure o~ Example 2 is repeated using -.
C8Fl7SO2N(CH3)C2H40H and a lower amount (27.5 parts; 0.1~ mol) of tolylene diisocyanate. The resultant carbodiimide desig-nated Polymer D is represented by the structure:

C8Fl7S02~C2H402CNH~

~ -CH3 C8Fl7SO2NC2H402C

A further series of fluoroaliphatic carbodiimides i8 prepared by the above procedures using the materials and molar proportions indicated in Table III and designated a~ shown there.

~:' 11D7 ~ZZ5 ~.

Z ~ ~ ~
. 0 V ~ ~ V _l ; H _ O :~
H ~ N ~ .o 1:~$ + + + + + ~
O ~ I
l ~ C ~
U) N U1 ~5U D N 11~ N 11'1 N
V ~ VP~ ~ 0 N I N I N I N ItU I ~ _I
~ z C)--z ~z C3~ C~E: .p O O æ O O e ~ ~ ~¢ ~ ~ o ~q C~ U ~ ~ ~

l ~ 0 s~
h ~ O O O
O U~ ~ O
P- ~ C~ 2 c 0~

='L~i i071; :25 5~

I I O O ~
o C ~ 3~"~ ~ ~

0 ~ 1 ~o ~ ~ c ~ +
+ E~ ~ + + ~ I ' C
o + ~ o o e~
a) ~1 ~i o , ,, 0 ~ , 0 0 ~
h C ~ , a 0 0 C: 0 0 a~ ~ Q~ a) a u~

~ O O
O O O
O
b a ~ z o 2~

~ o 0 ,, ,~

107~225 For purposes of providing fluoroaliphatic poly-mers, a number of materlals are prepared or obtained commercially. These also are designated by letters.
Polymer U designates a commerclally available material believed to be a 50/50 blend of poly(2-ethyl-hexyl methacrylate) and poly(l,l,2,2-tetrahydroperfluoro-alkyl methacrylate) in whlch the alkyl group has an average composition of about 10 carbon atoms. Thls is available under the Trademark Zepel D.
Polymer V designates a 50/50 blend of two poly-mers. One is made by emulsion polymerizin~ for 16 hours at 50 C. a mixture of 50 parts methyl methacrylate and 60 parts of tridecyl acrylate in 126 parts of water and 54 parts of acetone in the presence of 2 parts of C8F17SO2N(CH3)C2H4N(CH3)2HCl as emulsifier and 3 parts of a commercial polyoxyethylene lauryl ether as another emulsifier and uslng 0.2 parts of potassium persulfate as catalyst. The other polymer is prepared, using the same amounts of emulsifier and catalyst and same reaction conditions, from 93.5 parts of C8Fl7S02N(C2H5)C2H40COC(CH3)=CH
and 605 parts of isoprene in 144 parts of water and 36 parts of acetone wlth the addition of 0.75 parts of t-dodecyl mercaptan.
Polymer W is like the latter polymer used ln Polymer V, but prepared from equal amounts of C8F17SO2-N(C2H5)C2H40COC(CH3)=CH2 and chloroprene as described in E~ample III D of U, S. Patent No. 3,068,187.

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Polymer X is prepared as in the above procedures, heating a reaction mixture of 90 parts C8Fl7S0zN(CH3)C2H4_ OCOO(CH3)=CH2, and lO parts butyl~crylate in 160 parts water and 40 parts acetone with 0.2 parts t-dodecyl mer-captan and 0.2 parts potassium persulfate using 5 parts of a commercial polyethoxylated quaternary ammonium chloride emulsifier at 65 C. for 16 hours.
As noted hereinabove, fabrics of lO0~ filament nylon and both 100% spun and 100% filament polyester are treated by standard procedures with various blends of fluoro-aliphatic vinyl polymers and carbodiimides and rated for oil and uater repellency after treatment and again after 5 launderings and in some cases also after 5 drycleanings.
The data are presented in the following tables in which Nylon= 100~ fllament nylon Polyester F= 100% filament polyester Polyester S= 100% spun polyester Initial = data before laundering etc.
Laundered= data after 5 launderings Drycleaned= data after 5 drycleanings.
Except as noted, the fabrics are treated to contain 0.075~ carbon bonded fluorine. Proportlons of polymers blended together are indicated as, e.g., 65C + ~5B, and for controls or comparisons where there is no blend, as e.g., lOOC.
The ratings are given for conciseness as a fractlon, e.g., 5/100, ln which the numerator (5) is oil rating and denominator (lO0) is spray ra~ing.

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Example 24 To a 25 gallon glass-lined kettle equipped with agitator, condenser, and provision for heating and cooling, are added 58 parts of C8Fl,S02N(C2H5)C4H80H and 135 parts of MIBK solvent.
The solution is heated to about 115 C. and 25 parts of solvent removed by distillation to ensure anhydrous conditions. The kettle is cooled to about 90 C., 52 parts of 2,4-toluene diisocy-anate added and the solution heated to 115 C. for a further 3 hours. The solution is next coo~ed to 50 C. and 5 parts of a 20% by weight solution of 2,2,~,4,4-pentamethyl-1-phenylphos-phetane oxide in methylene chloride added, and the solution is then again slowly heated to 115 C., care being taken to avoid excessive foaming. The solution is maintained at 115 C., with agitation for about 3 hours, or until the isocyanate groups are essentially completely reacted as indicated by the infra-red ab-sorption spectrum. The product is a 40% by weight solution of:
CH3 _ CH3 --C~Fl7So2~-C4H8o~H~3 ~N=C=N4~ ~0C4H8~02$C8Fl7 zHs _ = 2 2Hs A fabric-treating concentrate is prepared by dissolving 90 parts of a fluoroaliphatic radical-containlng methacrylate copolymer (35% fluorine in the form of fluoroaliphatic radicals~
in 115 parts of MI~K and 260 parts of C2F3Cl3, and adding 25 25 parts of the above polycarbodiimide product solution.
For treatment of fabrics whose structure would be damaged by exposure to ~ter, such as textured or velvet uphol-stry fabrics, a solvent system is preferred For treatment of a medium-weight 100 percent nylon velvet, for example, the above concentrate, is diluted to about 0,4~ solids with trichloroethylene. Improved water resistance can be ob-tained by the addition of a fluorine-free water repellant, such as 001% by weight of the solution of a stearatO-chrome complex. The fabric is sprayed in a ventilated spray booth with the dilute solution to about 50% wet pick up, then dried in a circulating air oven at 110 C. for about 3 min-utes, until the solvent has evaporated and the fabric has reached oven temperature, The resultlng treated fabric has an oil ratlng of 6 and a spray rating of 75. The stain re-sistance remain~ even after extensive abrasion.

- f ~071225 Example 25 A branched polycarbodlimide is prepared by adding to 57.5 parts of dry MIBK (Methyl Isobutyl Ketone) C8Fl,S02N(CzH5)C2H40H j 28.6 parts 2,4_Toluene diisocyanate 7.8 parts OCNC~H4CH2C~H3(NCO)CH2C~H4NC0 2.1 parts The solution is refluxed for 3 hours, then cooled to 90 C. and 1.7 parts of a 22~ by welght solution of pentamethyl-l-phenylphosphetane oxide added. The resulting solution is heated to reflux and maintained there for t~o hours. A further o.86 parts of catalyst solution is added because the presence of unreacted -NC0 is shown by infrared absorption and refluxing is continued for an additional hour. The resultlng clear solution is free from -NC0, but exhibits the characteriStiC absorption peak of carbodiimide at 4.69 microns. Emulsions and solutions containing this polycarbodlimide product and a fluoroaliphatic group con-taining acrylate copolymer confer durable oil and water resistance on treated fabrlcs.

Claims (4)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A solvent-soluble fluoroaliphatic radical-containing carbodiimide consisting essentially of from 1 to a plurality of carbodiimide groups, ter-minal organic radicals free from isocyanate-reactive hydrogen atoms and connected to carbodiimide and, when two or more carbodiimide groups are present, polyvalent organic linking groups free from isocyanate-reactive hydrogen atoms linking successive carbodiimides; at least a portion of said terminal organic radicals or organic linking groups including fluoroaliphatic groups of 3 to 20 carbon atoms in amounts such that said carbodiimide as a whole including from 15 to 45 % by weight of carbon-bonded fluorine and said carbodiimide as a whole exclusive of fluoroaliphatic radicals containing at least 12% by weight of carbodiimide groups.

2. A fluoroaliphatic radical-containing carbodiimide according to Claim 1 of the general formula:
B -(N=C=N-A)-nN=C=N-B
wherein n is O or an integer from 1 to 20, A is a divalent organic linking group and B is a monovalent organic terminal group at least one of A and B
including fluoroaliphatic radicals with terminal CF3 groups of from 3 to 20 fully fluorinated carbon atoms.

3. A solvent-soluble fluoroaliphatic radical-containing carbodiimide consisting essentially of from 1 to a plurality of carbodiimide groups ter-minal organic radicals derived from mono- or polyisocyanate and free from isocyanate-reactive hydrogen atoms and connected to carbodiimide and, when two or more carbodiimide groups are present, polyvalent organic linking groups derived from organic polyisocyanate and free from isocyanate-reactive hydrogen atoms linking successive carbodiimide groups; fluoroaliphatic groups of 3 to 20 carbon atoms forming a part of said terminal organic radicals or organic linking groups in amounts such that said carbodiimide as a whole includes from 15 to 45% by weight of carbon-bonded fluorine and said carbodiimide as a whole exclusive of fluoroaliphatic radicals contains at least 12% by weight of carbodiimide groups.

4. A fluoroaliphatic radical-containing carbodiimide according to claim 3 of the general formula:
B-(-N=C=N-A-)-nN=C=N-B
wherein n is 0 or an integer from 1 to 20, A is a divalent organic linking group derived from diisocyanate and B is a monovalent organic terminal group derived from mono- or diisocyanate; fluoroaliphatic radicals with terminal CF3 groups of from 3 to 20 fully fluorinated carbon atoms forming a part of at least one of A and B.