CA1291488C

CA1291488C - Modified fluorocarbonylimino biurets

Info

Publication number: CA1291488C
Application number: CA000485667A
Authority: CA
Inventors: Engelbert Pechhold
Original assignee: EI Du Pont de Nemours and Co
Current assignee: EIDP Inc
Priority date: 1984-08-24
Filing date: 1985-06-27
Publication date: 1991-10-29
Anticipated expiration: 2008-10-29
Also published as: EP0172717A3; ATE87908T1; MX167460B; DK385585D0; AU4654385A; EP0383365A2; JPH0251547B2; ZA856430B; US4958039A; EP0172717B1; EP0172717A2; DE3587245D1; BR8504030A; AU591634B2; JPS6165860A; JPH02242974A; DE3587245T2; DK385585A; EP0383365A3

Abstract

TITLE
MODIFIED FLUOROCARBONYLIMINO BIURETS

ABSTRACT OF THE DISCLOSURE
Fluorocarbonylimino biurets derived from a tris(isocyanotoalkane)biuret, a fluoroaliphatic alcohol and a modifier group imports oil/water repel-lency, soil-release properties.

Description

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TITLE
MODIFIED FLUOROCARBONYLIMINO BIURETS
FIELD OF THE INVENTION
The present invention relates to novel modified fluorocarbonylimino biurets and their use to provide oil/water repellen~y, soil-release properties.
BACKGROUND OF THE ART
U.S. 3,987,227 discloses carpets having a stain-repellent and soil-resistant coating formed by a combination of a water-insoluble fluoroaliphatic radical containing urethane adduct and a water insoluble urethane adduct free from fluoroaliphatic radicals.
U.S. 4,264,484 discloses treating carpets with a combination of:
(a) a water-insoluble addition polymer derived from polymerizable ethylenically unsatu-rated monomer; and (b) a water-insoluble fluo~oaliphatic radical and aliphatic chlorine-containing carboxylic or carbamic ester.
U.S. 4,340,749 discloses treating carpets to render them soil-resis~ant and stain-repellent with a carboxylic or carbamic ester of a fluoro-aliphatic radical- and aliphatic chlorine-containing alcoholc U.S. 4,401,780 discloses treating textiles with a fluorochemical composition comprising a mix-ture of:
(a~ a water-insoluble fluoroaliphatic radical and aliphatic chlorine-containing ester, ~b) a water-insoluble fluoroaliphatic radical-containing polymer; and (c) water insoluble fluoroaliphatic radical-~ , .

containing compound selected from carbonyl-imino compounds and imine compounds.
Br. 1,241,505 discloses tertiary amine salts of fluorocarbamates which are useful as oil-repellents for treating fabrics.
German Patentschrift 1,794,356 and EPO
application olO3752 both disclose various fluorocarbamates having anti-soiling properties.
BACKGROUND AND SUMMARY OF THE INVENTION
.
The present invention describes novel fluorocompounds which when applied onto fibers and fabrics provide durable finishes with antisoiling properties.
Fluorocarbamates from mono- and diiso-cyanates have been described previously in various references, such as the references cited above, for improving oil and water resistance of textile sur-faces. ~owever, during processing such as washing and drying, a major part of these compounds is 105t to the atmosphere and treatment medium, which may cause pollution and operating problems. These problems can be overcome by using reaction products of fluoroalcohols with the biurets of aliphatic or cycloaliphatic isocyanates which give rise to non-volatile and fairly durable textile finishes.
Tris(isocyanato alkane)biurets as used in the invention and their method of preparation are described in U.S. 3,124,605 and 3,~01,372. It is believed that the unique biuret structure provide~
strong hydrogen bonding to the fiber substrate.
Further improvement in durability has been achieved by incorporation of a modifier group (R' or R" below) in the reaction product of 1uoroalcohols and tris(isocyanato alkane)biurets. A modifier group may be an aromatic, aliphatic, alicyclic compound or i2~4~31B

mixture of compounds with one or more Zerevitinov~
active hydrogen atoms e.g. any fluorine-free mono-meric alcohol or any substituted or unsubstituted fluorine-containing or fluorine-free diol, triol, tetrol, polyol, amine, diamine, triamine, tetramine, polyamine, hydroxyamine, aminothiol, thiol, di~hiol, trithiol, ~etrathiol, polythiol, hydroxythiol, carboxythiol, monocarboxylic acid, dicarboxylic acid, tricarboxylic acid, aminocarboxylic acid, etc.
The novel compounds of this invention impart high oil/water repellency and good soil resis-tance when applied onto nylon or polyester fiber or fabric. Similar improvements may be achieved when applied to other synthetic or natural fibers or their blends.
The compounds as described in this inven-tion can be applied onto the substrate pure or in combination with other textile or fluoro-fi~ishes, proces~ing aids, lubricants, anti-stains, etc., either from organic solutions or aqueous dispersions by any of the customary procedures such as spraying, dipping, padding, foaming, etc. The compounds can also be blended with other agents which have oil/water repellency and soil releas~ properties and applied to fibers or fabrics.

____________-__ Zerevitinov determination is the reaction of an organic compound containing active hydrogen atoms, e.g., -OH, -COOH, -NH, etc., with methylmagnesium halide to yive methane which is collected and determined volumetrically.

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DETAI LED DESC RI PTI ON
.
The novel compounds of the present inven~
tion are oligomers of the formula Rf-~A~mB-o]pz~ R~lq and (Rf-(A)mB-Olr ~ Z-X~ -R~
[R'-X]s /
_ _ t wherein Z is a tris(carbonylimino)biuret radical of the general formula O O
C~ R~ C-.-N--R-NH-C-C-N~- R-NEI-C -o in which R is an aliphatic or cycloali-phatic residue having at leas~ 4 and not more than 20 carbon atoms, with only alkyl, alkoxy or no substituents, especially an alkyl cr cycloalkyl residue and most preferably -(CH2)6-.
Rf is a fully-fluorinated straight or branched alipha~ic radical which can be interrupted by oxygen atoms. Preferably, Rf contains at least 3 and not more than 20 carbon atoms.
A is a divalent radical selected from -SO2NR3-r or -CONR3-, where R3 is H or a Cl_6 alkyl radical.

B is a divalent linear hydrocarbon radical -CnH2n- which can be end capped by ,CH3 CH2Cl ~OCH2CH2-~z, ~OCH2-CH~z, ~OCH2-CH~z or -C~OCH2CH~z where n is o to 12, R4 CH2Cl z is 1 to 50, and R4 is H or lower alkyl;
X is O, S or NR5, where R5 is H or a lower alkyl;
R' is a monovalent fluorine-free aliphatic, alicyclic, aromatic or heterocyclic hydrocarbon radical substituted with one or more of the following:
-Cl, -Br, OR6, -Si(OR6)3, -N(R6)3 or vicinal -OH/-Cl, -OH/-Br, where R6 is alkyl of 1 to 18 carbon atoms;
R" is any substitued or unsubstituted fluorine-containing or fluorine-free aliphatic, alicyclic, aromatic or heterocyclic hydro-carbon radical with a valency of at least 2 and not more than 100;
m is zero or l;
p is 1 or 2;
q is (3-p), i.e., either 2 or 1;
r is 1 or 2;
s is (2-r) i.e., either 1 or 0; and t is an integer of 2 to 100.
Preferred in view of the ease of manufacture and their properties are the compounds of the following formula:[Rf-~A)m-B-O]pz-[X-R'lq wherein r~ 6-.,~;, --7~
O O
~ n C-NH- (CH2)6-NH-C
O
Z is N~(CH2)6-NH-C~

C-NH- (CH2) 6-N~I-C-O O
Rf is a fully-fluorinated straight or branched aliphatic radical ~f 3 to 20 carbon atoms which ~an be interruptecl by oxygen atoms, more preferably, -CnF2n~l- where n is 3 to 14;
A is a divalent radical selected from -S02N~ -, or -CONR3-, where ~ is ~ or a Cl_6 alkyl radical9 preferably A is S02NC~3- or -S02NC2H5-;
B is a-divalent linear hydrocarbon radical -CnH2n- which can be end capped by C~3 CH2C~
C~2c~2tz~ tOCH2-C~t%, tOCH2-CHtz or ~4 -C~ OCE12CHt z R4 C~2Cl where n is O to 12, z is 1 to 50, and R4 is ~ or lower alkyl, preferably B is ~Cn~2n- where n is 2 to 6;
X i5 0 ~ S ~ or N ~ , where R~ is ~ or lvwer alkyl, preferably O or NH;
R' is a monovalent fluorine-free aliphatic, alicyclic, aromatic or~heterocyclic hydro-carbon radical substituted with one or more of the following:
C 1 - ar, - OR6 ~ - C02 R6 ~ - S i I OR6 ) 3 ~ ( 6 3 , ,.A~ .

12~l4B8 . .
-B-or vicinal -OH/-Cl, -OH/-Br, where R6 is alkyl oE 1 to 18 carbon atoms, preferably an aliphacic radical;
m is zero or 1, preferably 0;
p is 1 or 2; and q is (3 -p), i . e ., ei ther 1 or 2 .
Also preferred are compounds of the follow-ing formula:
L f ~ ]~ Z X3 R

wher ein O O
.. ..
C-N~-(C~2)6-NH-C-O
z is N - (CH2)6-N~-C-\
C-NH-(C~2)6 NH-C
O -- O
R~ is -CnF~n~1, wher e n is 3 to 14;
~n~2n~' where n ls 2 to 6 X is 0 ar N~; and R~ is any subs~ituted or unsubstituted ~luorine-con~alning or fluor~t~e-free ~liphaticr ali~y~l~c, aro~atic or hete~o-cycLic hydrocarbon radical with a ~alen~y of 2~
The modifie~ fluorocarbonylimino biurets described in this i~vention can be pr~pared by react-ing a fiuoroalcohol with a stoichiometric excess of a tris(isocyanato alkane)biuret at 50-~0C in the presence of a catalyst , e.g. dibutyltin dilaurate.
The amount of catalyst used will depend upon the charge, but is usually only a few drops, e.g., 0.02 to 0~04 parts per mole of reactants. The reaction can be carried out neat or in the presence of a dry . . ~

g solven~ , e.g. methyl isobutyl ketone. After 2 to 5 hours reaction is usually complete at which point the free isocyanate (NC0) is determined by the di-n-butylamine ti~ration method~ Based on this determination the appropriate amount of modifier is added, to react the residual isocyanate, usually as a solution in an organic solvent, e.g. methyl iso-butyl ketone. To allow for completion of the reac-tion, the mixture is heated for another 8 to 16 hours and then diluted to a 50 to 70 wt ~ solution with an organic solvent , e.~. methyl isobutyl ketone.
The solution of the modi~Eied fluorocar-bonylimino biurets can be dispersed in water in the usual fashion by using a surfactant which can be anionic, cationic, or nonionic or a combination o surfactants can be used.
Representative fluoroaliphatic alcohols that can be used in the reaction wi~h tris(isocyanato alkane~biurets are:
n l F2 n ~ + l ( c~2 ) m ~
where n' is 3 to 14 and m' is 1 to 12;
(CF3)2CF0(CF2cF2)p'cH2c~2oH
where p' is 1 to 5;
Cn,F2n.+lCON(~ CE~2)m'0H
where ~ is B or lower alkyl~ n' is 3 to 14, m' is 1 to l2;
Cn,F2n+ls02N(R3) (C~2)m'~d where R3, n' and m' are described above;

Cn~F2n~+lso2N(R3)-c O-CH2-C~ 0 R4 CH2C r' where R3, n', m' are described above and ~4 is ~ or lower alkyl, r' is 1 to 5.
Some of the representative modifiers R' or RY that can be used to make the fluorocarbonylimino biurets of this invention are:

_g_ ~9~

H2N- (CH2) 3 Si ~OC2H5) 3;

H2N- (CH2 ) 2~NH- (CH2 ~ 3-Si (OCH3 ) 3;

Cl Cl ~:O-CH2-C~:2-0- ~ -- Cl;

Cl Cl Cl N~ H
C-NH--C-C 3;
H

HO- (CH2)p"-OH;

H2N- (CH2 ) pl. NH2;

~293L~L88 H2N~ (CH2) pn~OH
where p" is 2 to 12;

HO-(CH2-CH2-O)qn-H
where q~ is 2 to 70;

H2N-CH-CH2- (0-CH2-CH2 ) y~~CH2~CH~NH2 where y is l to 70;

HO-CH~-CH-CH2Cl;
OH

C~2Rf ~o CH2-CR~ H
w where w is l to 4;

HO-CH2-C~-CH2Br;
0~

HO-CH2-CH-CH2-CO2CH3;
OH

H2-cH-cH2-c6~5;
0~
c,~3 HO-CH2-C-CH20H;
CO2~ ~NH(C2~5)3 H CH3C2e Ho-cH2-cH2-N-c~2-c~2-OH;

HO-CH2-CH-CH2-OH;
OH

~L%~L4~3~

HO-C~2-CH-CH2-CH2-CH2 ~C~2-OH;
O~i C2H5-C--CH2-OH;

C ( CH2 -OH ) ,,~; or E10-CH2-C~-C~-CH-CH-CH2-OH .
OH O~ O~ OH

BX~PLBS
Com~arative Example 1 Two moles of a mixture o fluoroalcohols of the formula ~-~CF2-CF2)n,-C~2CH2OH where n' is predominantly 5, 4, and 3, is charged to a reac-tion vessel and under nitrogen atmosphere heat~l to 50-60C. A`75 wt~ ~ solution of one mole of toluene diisocyanate in methyl isobutyl ketone is added to the fluoroalcohol and the resulting reaction mixture : is agitated and allowed to cool to about 45C at which point a catalytic amount of dibutyltin dilaurate (0.02-0.04 9) is added. An exotherm occurs, ~fter t~e exotherm the reaction mixture is agitated at 85C for four hours at which time it is diluted to 67 wt. % ~olids and allowed ~o cool.
Com~arative Exam~le 2 Three moles of the fluoroalcohol used in the above example are charged to a reaction vessel and under a nitrogen atmosphere heated to 60-70C. A
75 wt. ~ solution of one mole of 1,3,5-tris~6-iso-cyanatohexyl~biuret in methyl isobutyl ketone is added to the fluoroalcohol and the resultin~ reaction mixture is agitated and allowed to cool to about 50C
at which point a catalytic amount of dibutyltin dilaurate is added. An exotherm occurs. ~fter the ~ . `Sl,~

~9~L~31!!3 exotherm subsides, the reaction mixture is agitated at 85C for four hours at which time it is diluted to 67 wt. ~ solids and allowed to cool.
Exa~e 1 .
Two moles of a mixture of fluoroalcohols of the for~ula F(CF2CF2)n,CH2CH2OH where n' is predomi-nantly 5, 4, and 3, is charged to a reaction vessel and under a nitrogen atmosphere heated to 50-70C.
A 75 w~. ~ solution of one mole of 1,3,5-tris(6-iso-cyanatohexyl)biuret having the structure ( 2)6 NH C \
(C~2)6-NCO
OCN-(C~2)6-NH-C ~
O
in methyl isobutyl ketone is added to ~he fluoroalcohol and the resul~ing reaction mixture is agitated and allowed to cool to about 50C at which point a catalytic amount of dibutyltin dilaurate ir added. ~n exotherm occurs. After the exotherm the reaction mixture is agitated at 85C for three and one half hours, at which point one half mole of butane-diol-1,4 is added. The reac~ion mixture is hea~ed at 85C and agitated an additional 12 hours at which time it is diluted to 67 wt. % solids and allowed to cool.
Example 2 Two moles of the fluoroalcohol used in Example 1 are charged to a reaction vesse~ and under a nitrogen atmosphere heated to 60~-70C. A 75 wt. ~
solution of one mole of 1,3,5-~ris(6-isocyanatohexyl)-biuret in methyl isobutyl ketone is added to the fluoroalcohol and the resulting reaction mixture is agitated and allowed to cool to about 50C at which point a cat~lytic amount o dibutyltin dilaurate is added. An exotherm occurs. After the exotherm sub-sides, the reaction mixture is agitated an additional .. .

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four hours at 80C and one third mole of trimethylol-propane C2H5C(CH2OH)3 is added. The reaction mixture is heated at 85C and agitated for an addi-tional 12 hours at which ti~e it is diluted to 67 wt. ~ solids with methyl isobutyl ketone and allowed to cool.
Example 3 Two moles of the fluoroalcohol of Example 1 ~ are charged to a reaction vessel and under a nitrogen 10 atmosphere heated to 60C-70C. A 75 wt. ~ solution of one ~ole of 1,3,5-tris(6-isocyanàtohexyl)biuret in methyl isobutyl ketone is added to the fluoroalcohol and the reaction mixture is agitated and allowed to cool to about 50C at which point a catalytic amount of dibutyltin dilaurate is addedO An exotherm occurs. After the exotherm subsides the reaction mixture is agitated an additional four hours at 85~
and one half mole of the triethylamine salt of dimethylolpropionic acid C~2 +NH(c2~5~3 ~O-C~2-CH-CH2-OH
is added. ~he reaction mixture is heated at 85C an additional 12 hours at which time it is diluted to 67 wt. ~ solids with methyl isobutyl ketone and allowed to cool.
xample Two moles of the fluoroalcohol used in Example 1 are charged to a reaction vessel and under a nitrogen atmosphere heated to 60-70C. A 75 wt. ~
~olution of one mole of 1,3,5-tris(6-isocyanatohexyl~-biuret in ~ethyl isobutyl ketone is added to the fluoroalcohol and the resulting reaction mixture is agitated and allowed to cool to about 50C at which point a catalytic amount of di~utyltin dilaurate is added. An exotherm occurs. After the exotherm sub-sides the reaction mixture is agitated an addi~ional ,~
.~., . 1, , ~;29~

three and one half hours at 85C and one half mole of N-methyl diethanolamine is added. The reaction mix-ture is hea~ed at 85C for an additional 12 hours at which time one half mole of acetic acid is added. It is then diluted to 67 wt. ~ solids with methyl iso-butyl ketone and allowed to cool.
Example S
Two moles of the fluoroalcohol used in Example 1 are charged to a reaction vessel and under a nitrogen atmosphere heated to 60-70C. A 75 wt. %
solution of one mole 1,3,5-tris(6-isocyanatohexyl)-biuret in methyl isobutyl ketone is ~dded to the fluoroalcohol and the resulting reaction mixture is agitated and allowed to cool to about 50C at which a catalytic amount of dibutyltin dilaurate is added. An exotherm occurs. After the exotherm subsides the reaction mixture is agitated an additional four hours at 85C and one hal mole of polyoxyalkylene diamine such as ~2NC~C~2(OC~zCH2)yO-CH2C~-NH2 where y is 18 is added. The reaction mixture s heated at 85~C and agitated an additional 12 hours at which time it is diluted to 67 wt. % solids and allowed to cool.
Example 6 Two ~nd one half moles of the ~luoroalcohol used in Example 1 are charged to a reaction vessel and under a nitrogen atmosphere heated to 60~-70C.
30 A 75 wt. ~ solution of one mole of 1,3,5-tris(6-iso-cyanatohexyl)biuret in methyl isobutyl ketone is added to the fluoroalcohol and the resulting reaction mixture is agitated and allowed to cool to about 50C
at which point a catalytic amount of dibutyltin dilaurate is added. An exotherm occurs. After the exotherm subsides, the reaction mixture is agitated ,~.
. , . , ~

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an addi~ional four hours at 85C and one half mole of 3~chloro-1/2-propanediol is added. The reaction mix-tuxe is heated at B5C and agitated an additional 12 hours at which time it is diluted to 67 wt. ~ solids with ~ethyl isobutyl ketone and allowed to cool. The product is a ~ixture which may have the idealized ~tructure 6hown below:

o o 10 3~2)n ~--CH2~C--NH~CH216~ C\ o OE~
N (CH2) ~jNHC~CH2C~ CH2Cl ". 3~2 n 2 2 ~2~ 6 N~
and n o 15 ~Y3~c~2~nc~2-c~2~ ~C~2t6N~-C \ O

~,~ Y1~2)6NHC~2~2t~2)rlcF3 cF3~C~2t-c~2 ~ 2~c ~ffC~2~6N~C~

~wo moles of the fluoro~lcohol used in ~xample 1 are charged to a reaction vessel and heated to 60-70~C under a nitrogen Dtmosphere. A 75 wt.
solution of one mole of 1,3,5-tr~s(6-lsocyanato-hexyl)biuret ln methyl ~sobutyl ketone ~ ~dded to tbe fluoroalcohol ~nd the resultlng m$xture i6 agitated and allowed to coo} to about 50 at ~hich point a catalytic amount of dibutyltin dil~urate ~8 added. An exotherm occurs. After the exotherm sub-sides, the resction m~xture i~ agitated an additlonal four hours at 85C and one mole of ~ aminopropyl~ri-Y ne ~2N(C~2)3si~0C2~5)3 ~s added. ~he reaction ~ixture is heated at 85C and ~gltated an additional 12 hours at which ti~e it is diluted ~o 67 wt. ~ solids with methyl isobutyl ketone and ~llowed .

~s~
, . .

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to cool.
The stability and durability of the fluoro~
compounds of this inver.tion are illustrated in Table I. Nylon-66 knit fabric was padded with an aqueous anionic dispersion of the fluorocompounds so as to allow a coverage of about 0.1 wt. ~ fluorine by weight of dry fabric. The air dried samples were tested for oil and water repellency as described below~ Part of the air dried samples were annealed for two minutes in a circulating air oven at 200C
and again tested for oil/water repellency. The above annealed samples were then subjected to five standard home washing cycles and retested.
The home washes were carried out in a ~enmoreU washing machine at 40C, employing 28 9 o~
~Tide~ detergent per washload, followed by drying for 30 minutes in an automatic dryer at medium setting.
Oiland Water-Repellency Tests ~Adapted From AATCC Test Method 118) A piece of fabric, treated with a solution or aqueous dispersion of the polymers of this i~vention, is conditioned for a minimum of 2 hours at 23 + 2 and 65 ~ 10% relative humidity. The repe}-lency of carpet samples should be ~easured on the side of the yarn, not on the tips of the tufts.
Beginning with the lowest numbered test liquid ~Repellency Rating No. 1), one drop (approxi~ately S mm diameter or 0~05-ml volume) is placed on each of three locations at least S mm apart. The drops are observed for 10 seconds for the water-repellency test, 30 seconds for the oil-repellency test. I, at the end of those periods of time, two of the three drops are still spherical to hemispherical in shape with no wicking around the drops, three drops of the next higher numbered test liquid are placed on adjacent sites and observed again for the specified periods of time. The procedure is continued until * trade marks -17-.

. .

~;~9~4~
one of the test liquids results in two of the three drops failing to remain spherical or hemispherical, or wetting or wicking occurs. The oil-repellency rating and the water-repellency rating of the yarn, fabric or carpet each is the highest numbered test liquid for which two of three drops remain spherical or hemispherical with no wicking for the specified time.
STANDARD WATER TEST LIQUIDS
- ComPosition (Volume ~6 ) - Water-Repellency Isopropanol Distilled ~atin~ Number (Reagent Grade) H~O
} 2 98 3~ 7Q
Dry Soiling Test Treated and untreated carpets are exposed simultaneously to floor traffic for 10 ,000 footsteps.
They are then removed from the floor and vacuumed.
Then a class rating to indicate degree of retained soil is assigned to the treated carpets using the untreated carpet as the basis for comparison.
Wet Soiling Test A slurry of dirt and water is prepared. A
shoe sole is dipped into the slurry and then pressed down in the same manner on each of the treated and untreated carpets to be tested. Following air drying and vacuuming, a class rating is assigned exactly as in Dry Soiling (above).

-~8-:

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Scale of V
Ratln~ Appearance Compared to Control 1 W Worse 0 Control 1 Slightly Better 2 Better 3 Much Better 4 Significantly Better Best - Completely Unsoiled STANDARD OIL TEST LIQUIDS
Oil-Repellency Rating Number_ _ Composition .. ...
1 ~Nujol~*
2 65/35 ~ujol~/n-hexadecane by volume at 21C
3 n-hexadecane 4 ` n-tetradecane n-dodecane 6 n-decane ________ ___________ ~Nujol" is the trademark of Plough, Inc., for a mineral oil which has a Saybolt viscosity of 360/390 at 38 and a specific gravity of 0.880/0.900 at 15Co TABLE I
2 Min at 200C
Air Dried 2 Min, at 200C 5 E~ome Washinqs O i l/Wa t e r oi 17Wa~ter oi 17Water Comparative Example 1 2/3 0/3 0/0 Compar a t iv e Example 2 0/2 6/5 0/4 Example 1 0/3 6/5 6/5 Example 4* 6/5 6/5 6/5 Example 6 0/1 6/5 6/5 Example 7 0/2 6~5 6/5 ________~__________ * Self-dispersing - no surfactant The soil release performance of several of the above exemplified fluorocompounds is tested and compared with an untreated fabric as well as three known soil repellents. The soil repellents are applied to the carpet by padding with the nip rolls set so that after drying 0.075 wt. % of carbon-bonded fluorine remain on the carpet. ~he carpet used is a standard yellow 30 oz./sq. yard (1.07 Rg/m2) carpet. The results are reported in Table II.

~::

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TABLE II
oi 1 Water Dry Wet Soil Repellency Repellency Soil Soil Repellent Test Test Test Test Ex 2 4 5 5 5 Ex 3 Ex 6 4 4-5 5 5 Ex 7 3 5 4-5 5 Commercial Compound A 4 4 2-3 4 Co~mercial Compound B 2 4 2-3 5-4 Commercial Compound C 2 4 2-3 5 Control 0 1 0 O
(untreated fabric)

Claims

1. A fluorocarbonylimino biuret of the formula:

(Rf-(A)?B-O)?Z-[X-R']q or wherein Z is a tris(carbonylimino)biuret radical of the general formula in which R is an aliphatic or cycloali-phatic residue of 4 to 20 carbon atoms, optionally substituted with alkyl or alkoxy substituents;
Rf is a fully-fluorinated straight or branched aliphatic radical of 3 to 20 carbon atoms which can be interrupted by oxygen atoms;
A is a divalent radical consisting of -SO2NR3-, or -CONR3-, where R3 is H or alkyl of 1 to 6 carbon atoms;
B is a divalent linear hydrocarbon radical -CnH2n- which can be end capped by where n is 0 to 12, z is 1 to 50, and R4 is H or lower alkyl;
X is 0, S or NR5, where R5 is H or lower alkyl;
R' is a monovalent fluorine-free aliphatic, alicyclic, aromatic or heterocyclyic hydrocarbon radical substituted with one of more of the following:
-Cl, -Br, -OR6, -CO2R6, -Si(OR6)3, ?
-N(R6)3 or vicinal -OH/-Cl, -OH/-Br, where R6 is alkyl of 1 to 18 carbon atoms;
R" is any unsubstituted fluorine-containing or fluorine-free aliphatic, alicyclic, aromatic or heterocyclic hydrocarbon radical with a valency of at least 2 and not more than 100 or any such radical substituted with one or more of the following:
-Cl, -Br, -OR6, -CO2R6, -Si(OR6)3, -N?(R6)3 or vicinal -OH/-Cl, -OH/-Br, where R6 is alkyl of 1 to 18 carbon atoms;
m is zero or l;
p is 1 or 2;
q is (3-p), ie., either 2 or 17 r is 1 or 2;
s is (2-r); and t is an integer of 2 to 100

2. A f luorocarbonylimino biuret of the formula-[Rf-(A)m-B-O]pZ-[X-R']q wherein Z is Rf is a fully-fluorinated straight or branched aliphatic radical of 3 to 20 carbon atoms which can be interrupted by oxygen atoms;
A is a divalent radical selected from -SO2NR3-, or -CONR3-, where R3 is H or alkyl of 1 to 6 carbon atoms;
B is a divalent linear hydrocarbon radical -CnH2n- which can be end capped by ?OCH2CH2?z, , or where n is 0 to 12, z is 1 to 50, and R4 is H or lower alkyl;
X is O, S, or NR5, where R5 is H or lower alkyl;
R' is a monovalent fluorine-free aliphatic, alicyclic, aromatic or heterocyclic hydro-carbon radical substituted with one or more of the following:
-Cl, -Br, -OR6, -CO2R6, -Si(OR6)3, -?(R6)3 or vicinal -OH/Cl, -OH/-Br, where R6 is alkyl of 1 to 18 carbon atoms;
m is 0 or 1;

p is 1 or 2; and q is (3-p)-

3. A fluorocarbonylimino biuret according to claim 2 wherein Rf is -CnF2n+1, where n is 3 to 14;
A is -SO2NCH3- or -SO2NC2H5-;
B is -CnH2n-, where n is 2 to 6;
X is O or NH; and R' is aliphatic.

4. A fluorocarbonylimino biuret according to claim 3 wherein m is zero; p is 2; and q is 1.

5. A fluorocarbonylimino biuret according to claim 4 wherein R' is and X is oxygen.

6. A fluorocarbonylimino biuret according to claim 4 wherein R' is and X is oxygen.

7. A fluorocarbonylimino biuret according to claim 4 wherein R' is -(CH2)3-Si(OC2N5)3 and X is NH.

8. A fluorocarbonylimino biuret according to claim 4 wherein R' is and X is oxygen.

9. A fluorocarbonylimino biuret of the formula wherein Z is Rf is -CnF2n+1, where n is 3 to 14;
B is -CnH2n-, where n is 2 to 6;
X is O or NH; and R" is any unsubstituted fluorine-containing or fluorine-free aliphatic, alicyclic, aromatic or hetero- cyclic hydrocarbon radical with a valency of 2, or any such radical substituted with one or more of the following:
-Cl, -Br, -OR6, -Si(OR6)3, -N?(R6)3 or vicinal -OH/-Cl, -OH/-Br, where R6 is alkyl of 1 to 18 carbon atoms;

10. A fluorocarbonylimino biuret according to Claim 9 wherein X is oxygen and R" is -(CH2)4-.

11. A fluorocarbonylimino biuret according to Claim 9 wherein X is oxygen and R" is in which Rf is a fluorinated aliphatic radical of at least four fully fluorinated carbon atoms and w is 1 to 4.

12. A fluoracarbonylimino biuret according to Claim 9 where in X is oxygen and R" is

13. A fluorocarbonylimino biuret according to Claim 9 wherein R" is X is NH; and Y is 18.

14. A fluorocarbonylimino biuret comprising a mixture of:

and where n is 3, 4, 5 or mixtures thereo.

15. A synthetic or natural fiber or fabric treated with a fluorocarbonylimino biuret according to Claim 1 to impart oil/water repellency and soil resistance.

16. A synthetic or natural fiber or fabric treated with a fluorocarboylimino biuret according to Claim 2 to impart oil/water repellency and soil resistance.

17. A synthetic or natural fiber or fabric treated with a fluorocarbonylimino biuret according to Claim 9 to impart oil/water repellency and soil resistance.

18. A nylon or polyester fiber or fabric treated with a blend of a fluorochemical according to Claim 1 to impart oil/water repellency and soil resistance.

19. A nylon or polyester fiber or fabric treated with a fluorocarbonylimino biuret according to Claim 2 to impart oil/water repellency and soil resistance.

20. A nylon or polyester fiber or fabric treated with a fluorocarbonylimino biuret according to Claim 9 to impart oil/water repellency and soil resistance.

21. A nylon or polyester fiber or fabric treated with a blend of a fluorochemical according to Claim 1 and other textile finishing agents to impart oil/water repellency and soil resistance.

22. A fluorocarbonylimino biuret comprising the compound.