US3671493A

US3671493A - Fluorocarbon-containing compounds and method of imparting oil-and water-repellency to textiles,paper,leather and the like

Info

Publication number: US3671493A
Application number: US26263A
Authority: US
Inventors: Sergio Lo Monaco; Alfredo Guerrato; Dario Fabbro; Graziello Donadello
Original assignee: Individual
Current assignee: Individual
Priority date: 1969-04-16
Filing date: 1970-04-07
Publication date: 1972-06-20
Anticipated expiration: 1989-06-20
Also published as: GB1310823A; FR2043347A5; DE2018365A1

Abstract

The compounds of formula (I) may be obtained by different processes depending upon the different nature of the starting chemical intermediates. Obviously, the molecule as represented by formule (I) is formed by:

WHEREIN: X is bonded to an alkylene group and is selected from the group consisting of -H, -OCH3, -OC2H5, -OC3H7 and -OCH(CH3)2; Y is bonded to an N atom and is selected from the group consisting of -H, -CH3, -C2H5, -C3H7 and -CH(CH3)2; Rf is a perfluorinated hydrocarbon chain -CzF2z 1 in which z is an integer from 5 to 11; a, b and c are integers from 2 to 10; n is an integer from 1 to 10, preferably from 3 to 10; m is an integer from 1 to 10; p is an integer from 1 to 5; g is an integer from 0 to 5; ( Sigma ) is a polyester- or a polyether-polyurethane chain carrying the number p of the NCO groups indicated in the formula; the number-average molecular weight (international symbol Mn; Encyclopedia of Polymer Science and Technology, VOL. 3 page 653 and Vol. 9 page 182) of the compound not exceeding 60,000. This invention also covers precursors of the compounds as defined above, wherein the NCO groups are temporarily blocked by phenol or other suitable blocking agents. Advantageously, the number-average molecular weight of the compounds according to this invention amounts to at least 3,500. When, in the formula (I), q is zero, the compound will be a straight chain polymer, in which the n segments containing the perfluoroalkyl group Rf and the m segments containing the polyurethane chain will be distributed in the polymer chain in any order, with X radical being attached to one of the m segments and the Y radical being attached to one of the n segments. Typically, however, q will amount at least to 1, whereby the compound of formula (I) will be a branched chain polymer, having for example one of the following structures:

COMPRISING A PERFLUORINATED HYDROCARBON CHAIN Rf and a polyester- or polyether urethane chain ( Sigma ) carrying free NCO groups; and precursors of said compounds, wherein the -NCO groups are temporarily blocked by phenol or another suitable blocking agent. This invention relates to the art of imparting oil-and waterrepellency properties to substrates such as textiles, paper, leather and the like by treating such substrates with compounds comprising perfluoroalkyl chains. More particularly, the invention relates to compounds wherein a perfluoroalkyl chain is affixed to an active part of the molecule capable of providing for a possibly durable bond between the said chain and the substrate. Representative examples of such compounds, known in the art, are perfluoroacyl-aziridines, perfluoroacyl-polyamines and certain fluorocarbon urethanes, the latter being obtained by reacting an organic isocyanate with a compound containing a sulphonomide group, a perfluoroalkyl terminal group and a group containing an active hydrogen. A drawback of hitherto known compounds of the character just set forth above resides in that they are insoluble in organic solvents (actually, most of them are used in the form of aqueous emulsions) or are soluble in special solvents or specific mixtures of solvents only, which are either expensive and difficult to recover (e.g., fluorinated solvents) or inflammable or strongly poisonous. It is therefore an object of this invention to provide perfluoroacyl compounds capable of durably imparting oil- and water-repellency properties to substrates, said compounds being soluble in chlorinated hydrocarbon solvents common in the art, such as tetrachloroethylene and trichloroethylene, and said properties being practically unaffected for long time by rubbing, washing, dry-cleaning and similar treatments of fabrics treated with these compounds. A further drawback of prior art compounds resides in that relatively high amounts thereof are necessary to provide effective oil- and water-repellent coatings on a substrate, while a still further drawback resides in that the said compounds are unable to impart to woollens (e.g., woollen- and part-woollen yarn and knitted were) true shrink-proofness properties, the latter being here understood in the sense established by International Wool Secretariat (area shrinkage not exceeding 4 percent). Thus, a further object of this invention is to provide perfluoracyl compounds capable of imparting both oil- and waterrepellency and shrink-proofness to wollens. Further objects and advantages will become evident to those skilled in the art from the following description. The polymeric compounds according to this invention may be represented by randomly repeating units having the general formulas:

Compounds represented by a formula:

Description

United States Patent Lo Monaco et al.

[ -June 20, 1972 FLUOROCARBON-CONTAINING COMPOUNDS AND METHOD OF IMPARTING OIL- AND WATER- REPELLENCY TO TEXTILES, PAPER, LEATHER AND THE LIKE inventors: Sergio Lo Monaco, Piazzale Roma l3, Vicenza; Alfredo Guerrato, Via Panisacco 2; Dario I-abbro, Via Verdis 3, both of Trissino; Gralleilo Donadello, Via S. Christoforo 9 B, Valdagno, all of Italy Filed: April 7, 1970 Appi. No.: 26,263

Foreign Application Priority Data April I6, 1969 Italy ..s1444 N69 us. Cl ..260/75 NH, 8/] 15.5, 8/l28,

117/1386, zoo/77.5 AM Int. c|. ..C08g 22/04. C083 5 3/1 6, 006m 15/52 Field of Search ..260/77.5 AM, 75 NH, 17.5 R,

260/75 TN, 77.5 CH, 2 EN, 77.5 KP

Primary E.\'aminerDonaid E. Czaja Assistant Emminer-H. S. Cockeram Attorney-Sughrue, Rothwell, Mion, Zinn & Macpeak [57] ABSTRACT Compounds represented by a formula:

comprising a perfluorinated hydrocarbon chain Rl' and a polyesteror polyether urethane chain [2] carrying free -NCO groups; and precursors of said compounds, wherein the NCO groups are temporarily blocked by phenol or another suitable blocking agent.

6 Claims, I Drawing figure wherein a perfluoroalky] chain is affixed to an active part of m the molecule capable of providing for a possibly durable bond between the said chain and the substrate. Representative examples of such compounds, known in the art, are perfluoroacyl-aziridines, perfluoroacyl-polyamines and certain fluorocarbon urethanes, the latter being obtained by reacting an organic isocyanate with a compound containing a sulphonomide group, a perfluoroalkyl terminal group and a group containing an active hydrogen.

A drawback of hitherto known compounds of the character just set forth above resides in that they are insoluble in organic solvents (actually, most of them are used in the form of aqueous emulsions) or are soluble in special solvents or specific mixtures of solvents only, which are either expensive and difficult to recover (e.g., fluorinated solvents) or inflammable or strongly poisonous. It is therefore an object of this invention to provide perfluoroacyl compounds capable of durably imparting oil and water-repellency properties to substrates, said compounds being soluble in chlorinated hydrocarbon solvents common in the art, such as tetrachloroethylene and trichloroethylene, and said properties being practically unaffected for long time by rubbing, washing, dry-cleaning and similar treatments of fabrics treated with these compounds.

A further drawback of prior art compounds resides in that relatively high amounts thereof are necessary to provide eflective oiland water-repellent coatings on a substrate, while a still further drawback resides in that the said compounds are unable to impart to woollens (e.g., woollenand part-woollen yarn and knitted were) true shrink-proofness properties, the latter being here understood in the sense established by lnter national Wool Secretariat (area shrinkage not exceeding 4 percent). Thus, a further object of this invention is to provide perfluoracyl compounds capable of imparting both oiland waterrepellency and shrink-proofness to wollens. Further ob jects and advantages will become evident to those skilled in the art from the following description.

The polymeric compounds according to this invention may be represented by randomly repeating units having the general formulas:

wherein:

X is bonded to an alkylene group and is selected from the group consisting of --H, OCH=, OC,H,, OC,H and OCHlCHal-zY is bonded to an N atom and is selected from the group consisting of H. -CH=;. CzH.-,, C.1H1 and :il2;

Rf is a perfluorinated hydrocarbon chain C,l",, in which z is an integer from 5 to l l;

a, b and c are integers from 2 to ID;

n is an integer from 1 to 10, preferably from 3 to l0;

m is an integer from I to p is an integer from I to 5;

g is an integer from 0 to 5;

[2] is a polyesteror a polyether-polyurethane chain carrying the number p of the NCO groups indicated in the formula;

the number-average molecular weight (international symbol M,,; Encyclopedia of Polymer Science and Technology, VOL. 3 page 653 and Vol. 9 page 182) of the compound not exceeding 60,000.

This invention also covers precursors of the compounds as defined above, wherein the NCO groups are temporarily blocked by phenol or other suitable blocking agents.

Advantageously, the number-average molecular weight of the compounds according to this invention amounts to at least 3,500.

When, in the formula (I), q is zero, the compound will be a straight chain polymer, in which the n segments containing the perfluoroalkyl group Rf and the m segments containing the polyurethane chain will be distributed in the polymer chain in any order, with X radical being attached to one of the m segments and the Y radical being attached to one of the n seg ments.

Typically, however, q will amount at least to l, whereby the compound of formula (I) will be a branched chain polymer, having for example one of the following structures:

so C14.

, as may be obtained from polymerization of ethyleneimine (Encyclopedia of Polymer Science and Technology, Vol. I,

page 137, .I.Wiley & s., N.Y.).

Best results are obtained by using polyamines sub 2.

b. Perfluorinated acyl groups of the type C,F,, --CO, wherein z 5-H.

c. A polyester or polyether polyurethane prepolymer containing three to six free NCO groups in the molecule, ob tained in a manner known per se in the general polyurethane technique (High Polymers, VoLXlll, Part I, .I.Wiley & Sons, N.Y.), based on the reaction of:

I. a polyether of aliphatic or aromatic type containing three to six free OH groups of the alcoholic type, as the only reactive terminals, which may be obtained through reaction of ethylene oxide or propylene oxide with polyols such as glycerine, l,l,l trimethylolproparie, mannitol; or of a polyester of aliphatic or aromatic type containing three to six free OH groups of alcoholic type, as the only reactive terminals, obtained by condensation of a polyol such as glycerol, l,l,l trimethylolpropane, or pen taerythrol, with a polycarboxylic aliphatic or aromatic acid, such as malonic, succinic, adipic, glutaric, sebacic, azelaic, phthalic, terephthalic, isophthalic acid; and of ethylene or propylene glycol; with: 2. analiphatic or aromatic dior tri-isocyanate of the type l.av OCNC,H,,NCO wherein z 4-10 (alkylene diisocyanate) O C N CH; (2.4-toly1ene dllsocyanate) (3a) 0 O N C Hr Q (2.6-tolylene dllsocyanate) l 0 C N (wherein -=-i-10 an R=H, OH; or 02115) preferentially of the type la, 3a, 6a, more particularly of the type la and 6a, i.e., aliphatic diand tri- -isocyanates. Each of the three to six free hydroxyl groups of the polyester or polyether reacts with the excess dior tri-isocyanate in the following manner:

Polyester OH OCN j Polyester 0 c0 NH j NCO giving thereby a urethane prepolymer of the polyether or polyester type having three to six free NCO groups in the molecule and wherein is an alkyl, aryl, alkylaryl 0r arylalkyl chain, present in the starting dior tri-isocyanate as a link between the NCO groups therein contained. Thus, in the case la,

is C,H whereas, for example, in case wherein n 3-6 if the free hydroxyl groups of the polyether or polyester are reacted with a diisocyanate and n 2-3 if the free hydroxyl groups of the polyether or polyester are reacted with a tri-isocyanate, and wherein:

x I to 6 y 2 to 8.

The compounds according to the invention may be prepared from a polyether or polyester urethane prepolymer of a number-average molecular weight of 3,000 to l5,000 containing at least three free isocyanate groups in the molecule, capable of reacting to yield substituted ureas or urethanes, and from a polyamine containing Rf-CO-groups (perfluoroacylamido- N alkylamine), obtained by reacting an ester or a halide of a perfluorinated carboxylic acid containing 6 to l2 C atoms with an aliphatic polyamine as per item a hereinbefore.

A modification consists in reacting a halide or an ester of a perfluorinated acid with excess aziridine anyhow substituted at the two C atoms, capable of polymerizing. In this case also an amide of an N-alkylamine is obtained.

A further manner of obtaining the compounds according to the invention consists in reacting the polyester or polyether prepolymer, containing one reactive isocyanate group in the chain only, the others being temporarily blocked by phenol (or by another suitable agent, such as for example acetylacetone or dimethylmalonate), with a polyamine as per item a, then reacting the resulting compound with a quantity lower than or equal to the free N-H groups present of an ester or halide of a perfluoro acid containing 6 to l2 C atoms. The resulting compound is then heated to l40-l50 C in order to set free the temporarily blocked isocyanate groups; the latter step may be avoided by heating the product, upon coating on the surface to be protected, during a few minutes to l35-l 50 C (compares Saunders Frisch Polyurethanes" Part I, lnterscience).

The compounds according to the invention confer oiland water-repellency to surfaces onto which they are deposited without requiring the use of any substances of a binding character for uniformly and durably distributing them over said surfaces, more particularly on wool, artificial and synthetic fibers leather or paper.

They are moreover capable of imparting shrinloproofness to wool yarn and knitted were, and dimensionally stabilizing wool fabrics, particularly when the polyester or polyether urethane chain [2] (NCO), is of a number-average molecular weight 0 3,000 to l5,000.

Note: The number-average molecular weights have been determined, both in respect of polyester and polyether urethane prepolymers and of compounds of formula (I), by titrating the isocyanate groups with excess dibutylamine, then diluting the whole mixture with ethyl alcohol and titrating the excess dibutylamine with aqueous HCl 0.lN (indicator bromophenol blue). Compare in this respect Encyclopedia of Polymer Science and Technology, Vol. 3, page 653 and sequentia, Vol. 9 page 182. The number-average molecular weight of the [2] (NCO),groups in formula (I) was assumed as equal to the number-average molecular weight of their parent (polyester or polyether methane prepolyrners).

The following facts evidence that the compounds according to the invention are not mixtures of the products employed for preparing them.

I. The solubility of the compound is other than the solubility of the starting products.

As is well known, the polyamines forming the compound are not soluble in conventional chlorinated solvents and are not so even after a partial amidation with a derivative ofa perfluorocarboxylic acid.

However, after reaction in a mixture of at least two solvents, one of which is part-fluorinated, such as, for example, 1,1,2- trichloro-trifluoroethane or trichlorofluoromethane or benzotrifluoride of alkyl or aryl chlorofluoro derivatives, and the other is a polar organic solvent (with a high dielectric constant) such as a ketone, an alkyl ester of an aliphatic acid, dimethyl forrnamide, tetrahydrofuran, dioxane, dimethysulfoxide, etc., a compound which is fully soluble in chlorinated solvents such as trichloroethylene, tetrachloroethylene, chloroform, methylchloroform, carbon tetrachloride, etc. is obtained by operating according to the method of the inven tion.

2. As is well known, one fundamental method of investigating and defining the structures of the chemical compounds is IR spectrometry.

By operating by absorption, the progress of the reaction may be followed by ascertaining the decrease with time of the band at 2,263 cm: due to asymmetric stretching of the N=C=O bond (compare Colthup, Daly, Wiberley Introduction to Infrared and Raman Spectroscopy, page 203, Academic Press, 1964), when the free isocyanate group-containing intermediate is reacted with the polyamine after partial amidation with halides or esters of perfluorocarboxylic acids.

As mentioned above, the perfluorinated chain Rf may contain 5 to II carbon atoms. The chain initially belongs to its corresponding perfluorinated acid C,F,,,,COOI-I or to halide C,F,,,,-COX (wherein X is fluorine, chlorine or bromine or to an ester C,F,,,,-COOR (wherein R is methyl, ethyl, propyl or isopropyl), the halide or ester being employed according to the invention for the synthesis of compounds (I). Already with z 5 compounds (I) are obtained which, when applied from solutions at about 2 percent by weight concentration (with respect to the fluorinated groups Rf) confer to the surface to be protected fair anti-spot properties (oiland water-repellency); such properties may be improved by increasing the quantity of the compound on the substrate, which is, however, detrimental to economy. With 1 7 (perfluorooctanoic acid) the results are decidedly better and consistent with economy of the preparing and applying process; application of a solution containing 0.10 percent by weight fluorinated part Rf will be sufficient. With 1 9 the results are further improved. Perfluorocarboxylic acids with at least eight C atoms are therefore preferred.

The above is illustrated by the appended drawing showing a diagram obtained under conditions in which the concentration of the fluorinated part Rfin the solution being applied is maintained constant (1.5 g/liter). The oil-repellency values OR are expressed according to the Du Pont scale, and the waterrepellency values SR are expressed according to the AATCC Spray Test 22-1952, both as a function ofz (axis of the abscissae).

The following table summarizes the values employed by the Du Pont system in respect of oil-repellency relatively to the surface tension ofthe test liquid.

Test Liquid Surface tension Du Pont dyne/cm scale Nujol (Plough Inc.) 3I.45 2 75/25 Nujol/n-hexadecsne 30.00 3 50/50 NujoI/nhexadecane 29.05 4 n-tetradecane 26.35 5 n-dodecsne 24.70 6 n decane 23.50 7 n-octane 2] .40 B 19.75 9

mheptane Lil The polyamines can be am idated by means of a halide of an ester of an acid, as defined above. When operating with excess alcohol in the presence of an acid catalyst, such as the H,SO,- BF; system, preparation of the methyl, ethyl, propyl and isopropyl esters proceeds rapidly and with a high output (over 90 percent) with recycling possibilities. These esters quantitatively react with the primary polyamido groups both in bulk and in anhydrous solvents, without reacting with the secondary polyamido groups.

When employing polyether or polyester polyurethane prepolymers with isocyanate groups of the aryl type, compounds of formula (I) are obtained which:

impart oil-repellency at a concentration as low as 0.15 percent by weight of the fluorinated groups Rfin the solution being applied; impart water-repellency; impart shrink-proofness properties to wool yarn when the concentration of the [21(NCO), moieties in the solution being applied amounts to 0.8 percent by weight at least;

are soluble in conventional chlorinated organic solvents when the number-average molecular weight of the -](N- CO moiety amounts to 3,000 at least.

When employing polyether or polyester polyurethane prepolymers with isocyanate groups of the aliphatic type, compounds of formula (I) are obtained which:

impart high oil-repellency even when applied from solutions containing 0.1 percent by weight only of fluorinated moieties Rf;

impart water-repellency;

impart shrink-proofness properties to wool yarn and knitted ware when the concentration of the [21(NCO), moieties in the solution being applied amounts to 0.8 percent by weight at least, the number-average molecular weight of said moieties being 3,000 to I5,000;

are thoroughly soluble in conventional chlorinated solvents.

However, since it has been found that the compounds of formula (I) obtained from polyether or polyester polyurethane prepolymers with aryl isocyanate groups are easily liable to degrade and form precipitates or coagulum, the preferred compounds according to this invention are the compounds obtainable from polyether or polyester polyurethane prepolymers with isocyanate groups of the aliphatic type, in

which the part is an alkylene chain.

A surprising circumstance is that a polyester or polyether polyurethane prepolymer with isocyanate groups of aliphatic character does not per se impart to a substrate either oilor water-repellency, whereas the perfluoro-acylamido-N-alkylamines are oil-repellent and not water-repellent, and whereas the compounds according to this invention are strongly oiland water-repellent.

The following table shows that the compounds exhibit surprising properties which are not derived from the properties of the individual components.

TABLE 1 Oil re- Water re- Solupellency pellency bility Polyamine with perl'luorinated chains 6-7 050 NO Polyester or polyether prepolymer with reactive -NCO groups 0 0-50 YES Compound (I) 743 -90 YES Note:

concentrations fluorinated moieties 0.15 percent by weight polyester or polyether chains 0.8 percent by weight;

solubility in chlorinated solvents;

oil-repellency values according to the Du Pont scale and water-repellency values according to AATCC Spray Test 22-1952;

data derived from tests carried out on wool yarn and knitted were specimens.

METHODS OF SYNTHESIS OF THE PRODUCT The Examples described hereafter employ polyester and polyether urethane prepolymers containing three to six free NCO groups of aliphatic type per chain, of a numbers-average molecular weight of 3,000 to 15,000.

The prepolymers are:

A. Polyether urethane prepolymer of a number-average molecular weight of 3,000 containing three free -NCO groups, obtained by reacting 1,1,l-trimethylolpropane CH;CH,C(CH,-OH); with propylene oxide and subsequently reacting the resulting polyether polymer with hexamethylene diisocyanate in ethyl acetate.

B. Polyether urethane prepolymer of a number-average molecular weight of 9,000 containing four free NCO groups, obtained by reacting the pentaerythrol C(CH,OH) with propylene oxide and subsequently reacting the obtained polyether polymer with hexamethylene diisocyanate in ethyl acetate.

C. Polyester urethane prepolymer of a number-average molecular weight of 15,000 containing six Iree NCO groups obtained by esterifying 1,1,1 trimethylolpropane with adipic acid and propylene glycol and subsequently reacting the resulting polyester polymer with three mols of the triisocyanate of the formula: C,l-1,-C(Cl-l,-O CONHC,H,,NCO);.

EXAMPLE 1 44.2 g C,F,,COOC,H,(0.1 mols) and 8.6 g aziridine (0.2 mols) previously cooled to C were simultaneously slowly conveyed to a 250 ml flask provided with a stirrer and cooled by an external ice and water bath.

The temperature was prevented from exceeding 5 C during the full supply period.

On completion of supply the temperature was slowly raised to 30 C. The initially fluid colorless reaction product gradually became more viscous and yellowish. The gas chromatographic analysis (quantitative determination of the ethyl ester of the perfluoroacid on Carbowax 400) and spectrophotometric analysis (disappearance of the band at 1,780 emf ascribed to the carbonyl stretching of the ester of the perlluoro acid according to Colthup, Daly, Wiberley-lntroduction to Infrared and Raman Spectroscopy, page 315 Academic Press, 1964, showed that the ester had reacted almost quantitatively.

From the reaction product C,H,OH obtained as a side product was removed by extracting with 3 portions each of 50 ml of carbon tetrachloride.

48 g of a transparent fluid yellowish polymer were obtained. This product is insoluble in trichloroethylene, carbon tetrachloride, chloroform, tetrachloroethylene, methylchloroform and tetrachloroethane; it is of low solubility in acetone, diethylether, methylalcohol, ethyl and isopropyl alcohol.

The 48 g purified product were dissolved in a 50 percent by volume mixture of acetone and 1,1,2 trichlorotrifluoroethane, the concentration of the solution being raised to 200 g/l.

300 g polyether urethane prepolymer (A) dissolved in 0.5 liters 1,1,2 trichlorotrifluoroethane were charged to a threenecked 3 liter flask equipped with a stirred, heating jacket and reflux cooler.

After heating the solution to boiling temperature a previously prepared polymer solution was added by drops from a Squibb funnel. On completion of the addition, the solution was refluxed during 30 minutes, then allowed to cool.

The polymer obtained from the reaction may be recovered by initially distilling 450 ml 1,1,2 trichlorotrifluoroethane, then concentrating the solution during 40 minutes at 38 C at reduced pressure while employing a CaCl, trap in the vacuum line, thereby obtaining 350 g of a transparent syrupy strawyellow polymer which on cooling increase in viscosity without, however, being solid at 18 C. The polymer is of a numberaverage molecular weight of 27,000 contains 16 isocyanate groups in the molecule and is soluble in acetone, 1,1,2 trichlorotrifluoroethane, diethyl ether, ethyl alcohol, isopropyl alcohol, ethyl acetate, trichloroethylene, tetrachloroethylene, methylchloroform, carbon tetrachloride and tetrachloroethane.

For use the solution obtained as above containing 350 g polymer/liter was diluted to 1,670 ml by adding tetrachloroethylene.

USE

72 ml of the solution prepared as above were added at room temperature to 1 liter trichloroethylene to establish a concentration of about 15 g polymer/liter.

This solution containing 1.72 g fluorinated moieties Rf per liter solution was used for treating woollen knitted were by dipping as well as by spraying and subsequent wringing to achieve in any case a percent impregnation. No difference was ascertained in oiland water-repellency and shrink-proofness when the treated specimens were dried under the following conditions:

a. during 48 hours at a temperature: of 2060 C;

b. during 10 minutes at 90 C;

c. during 5 minutes at c.

The test results are summarized hereafter.

88.4 g CJ COOCJ-I, (0.2 mols) and 17.2 g aziridine (0.4 mols) were reacted as described in Example 1 whereby upon extraction of the ethyl alcohol 96.2 g of a transparent fluid yellowish compound were obtained. The product was found to be insoluble in trichloroethylene, carbon tetrachloride, chloroform, methylchloroform, tetrachloroethylene and tetrachloroethane and slightly soluble in acetone,

diethylether, methyl alcohol, ethyl alcohol and isopropyl alcohol.

48 g of the resulting product were reacted with 150g of the polyether urethane prepolymer (A) dissolved in 0.5 liters l l ,Z-trichlorotrifluoroethane.

The polymer resulting from the reaction may be recovered by initially distilling 400 mm 1,1,2 trichlorotrifluoroethane, then concentrating the solution during 40 minutes at 38 C at reduced pressure while employing a calcium chloride trap in the vacuum line. After cooling, 197 g ofa transparent viscous straw-yellow polymer were obtained, of a number-average molecular weight of 20.000. The polymer contains four isocyanic groups per molecule and is soluble in acetone, 1,1,2- trichlorotrifluoroethane, ethyl acetate, trichloroethylene, tetrachloroethylene, methylchloroform, carbon tetrachloride and tetrachloroethane.

For use the solution obtained as above containing 197 g polymer per liter was diluted to 1,670 ml by adding tetrachloroethylene. it was applied to identical specimens and in the same manner as described in the preceding example.

The concentration of the fluorinated moieties Rf was 1.72 g/liter as in Example 1. The test results are given hereafter:

When the product is not required to impart shrink-proofness properties, smaller proportions of free NCO groups are sufficient. Thus, 44.2 g C-,F,,COOC,l-l, (0,1 mols) and 6.4 g ethyleneimine (0.15 mols) were reacted as previously described in Example 1. The resulting product was washed with 3 portions each of 50 ml of CCL, then dried at 40 C during 25 minutes at reduced pressure. 46 g of a transparent fluid pale yellow polymer were obtained. The IR spectrum denoted that under such conditions the ester of the perfluorinated acid was fully reacted. The polymer was found to be insoluble in trichloroethylene, CC1., CHCl,, methylchlorofonn, tetrachloroethylene, tetrachloroethane, ethyl and isopropyl alcohol and of low solubility in ether, acetone, 1,1,2 trichlorotrifluoroethane.

23g of the resulting polymer were treated with 100 ml of the solution containing 50 percent by volume of 1,1,2 trichlorotn'fluoroethane and acetone with 225 g of the polyether urethane prepolymer (A) dissolved in 200 ml 1,1,2 trichlorotrifluoroethane.

By proceeding as described in Example 1 a transparent slightly viscous straw-yellow solution was obtained which upon cooling was diluted to 380 ml by adding trichloroethylene. The polymer synthesized as above may be recovered by initially distilling 300 ml 1,1,2 trichlorotrifluoroethane, then evaporating the remaining solvent at reduced pressure at 38 C during 40 minutes in the manner described in the preceding Examples, whereby 46g of a transparent viscous pale straw yellow polymer are obtained, the polymer being soluble in trichloroethylene, tetrachloroethane, tetrachloroethylene, chloroform, methylchloroforrn, CCL, 1,1,2 trichlorotrifluoroethane, acetone, ethyl and isopropyl alcohol, being of a numberaverage molecular weight of 14,000 and containing four isocyanate groups per molecule.

USE

3 3 ml of the solution containing the non-recovered polymer were diluted with 1 liter trichloroethylene to reach a polymer concentration of 3.5 g/liter. As compared with the tests of use given in Example 1 a solution of the same fluorinated moiety concentration 1.72 g/liter) was employed.

Comparative results on fabrics of natural and man-made fibers are given hereafter.

Polyamide Oil-repellency 7-8 7 7-8 6-7 7 6 Water-repellency 80-9070-80 80 70 70 Acrylics Oil-repellency 7 7 7 6 6-7 6 Water-repellency 80-90 80-9070-80 80 60-70 70 Acetate Oil-repellency 7-8 7 7 6 7 6 Water-repellency 70-80 80 70 70-8050-70 70 Chlorovinyl Oil-repellency 7-8 7 7-8 7 7 6 Water-repellency 80 80-9070-80 80 70 50-70 A= product prepared according to Example 1 B= product prepared according to Example 3.

1n the above and preceding examples the tests for oiland water-repellency, shrink-proofness and dry cleaning and wet washing were efiected hours after treatment of the specimens.

EXAMPLE 4 21.7 g CJfi-(NH-CJ-L-L-NH, (0.! mols) were charged to a 500 ml flask provided with a stirrer and cooler, subsequently 45.6 g C,F,,COOCH(Cl-l,) (0.1 mols) were slowly introduced.

After addition of the reactant heating on water bath at 40 C during about 2 hours yielded a yellow-brown syrupy mass. Gaschromatographic and spectrophotometric investigations confirmed that the ester was reacted almost quantitatively.

Subsequently, the reaction product was washed with 3 portions each of 500 ml of CCL in order to remove the isopropanol formed, thereby yielding 61.2 g of a yellow-brown syrupy compound, insoluble in trichloroethylene, tetrachloroethylene, carbon tetrachloride, chloroform, methylchloroform, partly soluble in ether, acetone, 1, l ,2 trichlorotrifluoroethane. This compound was dissolved in 890 ml of a solvent consisting of 1,1,2 trichlorotrifluoroethane and acetone in a 50 percent by volume mixture.

1,500 g of the polyester urethane prepolymer (C) dissolved in 1 liter 1,1,2 trichlorotrifluoroethane were charged to a three-necked flask provided with a stirrer, cooler and protected against moisture by CaCl, traps. The solution was heated to its boiling point, then admixed dropwise with the previously prepared solution of perfluoroacylamido N-alkylamine. The solution was refluxed during about 30 minutes and yielded after cooling a transparent straw-yellow viscous liquid.

The polymer synthesized as above may be recovered by initially distilling 1,200 ml 1,1,2 trichlorotrifluoroethane, whereupon the remaining solvent is evaporated at 38 C during 90 minutes in the same manner as described in the preceding examples, thereby yielding 1,560 g of a transparent highly viscous straw-yellow polymer. This was found to be soluble in chlorinated and non-chlorinated solvents mentioned in the preceding examples, was of a number-average molecular weight of 60,000 and contained eight free isocyanate groups in the molecule.

The liquid containing the non-recovered polymer was diluted to 5,900 ml by addition of perchloroethylene. Analysis of the free NCO groups by titration with dibutylarnine confirmed the presence of eight free --NCO groups per molecule.

USE

223 ml of the solution prepared as above were diluted to 1 liter with perchloroethylene, this resulting in a polymer concentration of about 59 g/liter. Knitted woollens were treated with this solution both by dipping and spraying and subsequent wringing to afiord in every case a percent impregnadon.

The specimens were dried at 80 C during 20 minutes; the test results are summarized in the following table.

Initial Met 5 dry After 5 wet value cleaning washing processes processes Oil-repellency 8-9 8 7-8 Water-repellency 80-90 80 70-80 Shrinkage area b 1.5 1.5 2.0

EXAMPLE 5 As compared with Example 4, this example seems to show that the absence of free isocyanate groups in the macromolecules is a primary cause for the absence of shrinkproofness in the treated wool yarn.

45.6 g C,F, .,COOCH(CH,), (0.] mols) were reacted with 21.7 g (0.l mols) of C,H,( NHC,H ),-NH,, the product being washed as previously described in Example 4.

41g of a viscous yellow-brown compound of the formula C,H NHC,H ),NH--CO Rfwere obtained and dissolved in 890 ml of a solvent consisting of l,l,2 trichlorotrifluoroethane and acetone in a 50 percent by volume mixture. This solution was reacted with 1,000 g of the polyester urethane prepolymer (C) dissolved in 500 ml of 1,1,2 trichlorotrifluoroethane. Afier initially distilling 800 ml 1,1,2 trichlorotrifluoroethanc and removing the remaining solvent by evaporation at 38 C during 90 minutes in the previously described manner, L060 g of a transparent viscous straw-yellow polymer were obtained. This polymer was found to be soluble in chlorinated and non-chlorinated solvents mentioned in the preceding examples; however, no free isocyanate group was present in its solution. The latter circumstance was supported by [R spectrophotometry and volumetric analysis by means of dibutylamine. The polymer was subsequently heated to l-l20l40-180200 C; at each temperature the volumetric investigation of possible NCO groups proved negative. This polymer proved moreover to be indefinitely stable towards moisture and heat. A solution of the polymer, as previously described, was diluted to 5,900 ml by adding perchloroethylene and was applied to identical specimens and in the same manner as in Example 4, the concentration of the fluorinated moieties being maintained at 1.72 g/liter. The results are given hereafter:

Shrinkage area I: As in non-treated specimens EXAMPLE 6 150g (0.0l mols) of the polyester urethane prepolymer (C) dissolved in I00 ml anhydrous ethylacetate were admixed with 4.7 g phenol, the solution being refluxed during 4 hours. The solution of the prepolymer was then analyzed and the prepolymer was found to still contain one free isocyanate group per chain.

This solution was placed into a three-necked 1 liter flask provided with a stirrer and reflux cooler and protected against moisture by C30, traps and admixed dropwise with 2.l5 g ethyleneimine (0.05 mols). The reaction is exothermic and care was taken to cool with water and ice. Stirring was carried out during 1 hour, whereupon 17.28 g C,F,,COCI (0.04 mols) dissolved in 200 ml anhydrous l,l,2trichlorotrifluoroethane were added dropwise. The solution was refluxed during hours till HCl no longer evolved, cooled and diluted to 590 ml by adding methylchloroform.

The polymer obtained as above, may be recovered by initially distilling 180 ml l,l,2-trichlorotrifluoroethane at 42 C during 90 minutes. The result is I73 g of a transparent viscous yellow polymef of a number-average molecular weight of 42,000 containing 12 isocyanate groups protected by phenol.

It is soluble in trichloroethylene, tetrachloroethylene, chloroform, methylchloroform, carbon tetrachloride, tetrachloroethane, diethylether, l ,l ,2

trichlorotrifluoroethane, ethyl acetate, acetone. 22 g of such polymer were subsequently heated to l30- l40- C during 10 minutes and the possible presence of free -NCO groups was determined at each temperature.

After heating to 150 C a sample of the polymer was dissolved in 50 ml of a 50 percent by volume mixture of l,1,2 trichlorotrifluoroethane and acetone and the resulting solu tion was treated with a known excess-amount dibutylamine in anhydrous chlorobenzene. The excess was then titrated with HCl 0.1 N and bromophenol blue dissolved in C,H,OH was employed as indicator. The analysis showed that at 150 C all NCO groups blocked by phenol has been re-established.

USE

Initial After 5 dry Afler 5 wet value cleaning washing processes processes Oil rcpellency 8 7-8 7 Water-repellency 80-90 80 70-80 Shrinkage area it: 2.0 2.0 2.3

EXAMPLE 7 8.5 aziridine (0.2 mols) were added dropwise to a I00 ml flask containing 44.2 g C F, COOC,H, (0.1 mols); the mixture was maintained at 28 C during 48 hours while stirring.

A white polymer was obtained, which was slightly viscous at room temperature. The ethanol produced by the reaction was subsequently removed by washing with 3 portions each of 20 ml of methylchloroform, thereby yielding 48.1 g perfluoroacylarnido, N-alkylamine insoluble in trichloroethylene, tetrachloroethylene, tetrachloroethane, chloroform, methylchloroform, carbon tetrachloride, slightly soluble in acetone, 1,1,2 trichlorotrifluoroethane, ethyl ether, ethyl acetate, ethyl alcohol and isopropyl alcohol. This quantity was dissolved in 240 ml of the 50 percent by volume mixture of 1,1,2 trichlorotrifluoroethane and ethylacetate so as to obtain a polymer concentration of 200 g/l.

The solution prepared as above was added dropwise to 300 g of the polyether urethane prepolymer (A) dissolved in 0.5 1,1,2-tfichlorotrifluoroethane under reflux while stirring in 2 liter flask.

On completion of addition refluxing was continued during 30-35 minutes, whereupon a dilution with trichloroethylene to 1,670 ml gave an oily pale-yellow solution. The polymer was recovered from the solution by initially distilling 500 ml l, l ,2 trichlorotrifluoroethane, then evaporating the remaining solvent at 45 C during 40 minutes at reduced pressure, whereby 350 g slightly viscous straw-yellow polymer were obtained. The polymer is soluble in chlorinated solvents (in which the perfluoroacylamido, N-alkylamine of the instant example was insoluble), moreover in ethylacetate, l,l,2- trichlorotrifluoroethane, diethyl ether and acetone. The polymer has a number-average molecular weight of 27,000 and contains 16 isocyanate groups in the molecule.

The behavior of this product, its manner of use as well as the results practically coincide with those of the product obtained in Example l.

EXAMPLE 8 12.9 g aziridine (0.3mols) and 21 g triethylamine dissolved in 360 ml ether were charged to a three-necked l liter flask. The solution was carefully cooled to 30 C and slowly admixed with 86.5 g C F COCI (0.2 mols) from a Squibb funnel while care was taken to prevent the temperature from rising above 25 C.

Upon completion of the amidation reaction, the triethylamine hydrochloride formed as by-product was rapidly filtered-off and the ether was removed by evaporation at reduced pressure whereby 92 g of a syrupy yellow-brwn mass were obtained which was dissolved in 500 ml of the SOpercent by volume mixture of 1,l,2-trichlorotrifluoroethane and acetone. The mass proved to be insoluble in trichloroethylene, tetrachloroethane, tetrachloroethylene, methylchloroform, chloroform and carbon tetrachloride, and partly soluble in 1,l,2-trichlorotrifluoroethane, acetone, diethylether, ethyl acetate.

1,500 g of the polyester urethane prepolymer (C) were dissolved in 1 liter 1,l ,2-trichlorotrifluoroethane and the solution was refluxed in a three-liter flask equipped with a stirrer and protected against moisture by means of calcium chloride traps.

The previously prepared solution of perfluoroacylamido, N alkylamine was then added dropwise, while the prepolymer solution was being refluxed. On completion of the addition refluxing was continued during 30 further minutes. By [R spectrophotometry the decrease in time of the band at 2,263 cml belonging to the -NCO group could be checked. By distillation of 1,200 ml l,l,2-trichlorotrifluoroethane and subsequent evaporation of the remaining solvent during 90 minutes at 38 C at reduced pressure, 1,590 g of a highly viscous deep-yellow polymer were recovered. its numberaverage molecular weight was 27,000 and the polymer was soluble in all chlorinated solvents previously mentioned in the instant example, moreover in ethyl alcohol, isopropyl alcohol, acetone, ethyl acetate and ethyl ether.

A solution of the polymer prepared in the above described manner was adjusted to 3,080 ml by adding perchloroethylene.

USE

46.5 ml of the solution obtained as above were dissolved at room temperature in 1 liter perchloroethylene so as to obtain a polymer concentration of 24 g/liter.

Tests of processing woollen specimens were carried out in the manner described in Example 1,4 and 7. The results are tabulated hereunder:

Initial After 5 dry After 5 wet value cleaning washing processes processes Oil-repellency 8 7 7 Water-repellency 80-90 80 70-80 Shrinkage area b 2.0 2.0 2.4

EXAMPLE 9 mixed with the solution of the polyether urethane prepolymer (A) with the NCO groups blocked in part by phenol.

After 3 hours the reaction mixture was refluxed and 43.2 g C-,F,,,COCl (0.] mols) dissolved in 200 ml anhydrous 1,1,2 trichlorotrifluoroethane were added dropwise while vigorously stirring.

Refluxing while vigorously stirring was continued till HCl no longer evolved. After cooling the solution was diluted to 1,670 ml by adding perchloroethylene.

The polymer containing two isocyanate groups protected by phenol, obtained as above, was recovered by initially distilling-off ml 1,1,2-trichlorotrifluoroethane, then evaporating the remaining solvent at reduced pressure in the same manner as in Example 6.

The result was 365 g of a slightly viscous pale-yellow polymer ofa number-average molecular weight of 3,500 soluble in trichloroethylene, tetrachloroethane, perchloroethylene, methylchloroform, chloroform, CCl ethyl ether, 1,1,2-trichlorotrifluoroethane, ethyl acetate and acetone. in the presence of moisture this polymer remained indefinitely unaltered. The tests on woollen knitted were treated with a solution containing 15 g polymer per liter of solvent (perchloroethylene) were carried out in the manner described in Example 6. The results are tabulated hereunder:

21.7 g C,H (NH-C,H NH, (0.1 mols) were slowly reacted while stirring with 47.8 g C,,F,,CO0CH (0.1 mols) at 40 C. Upon completion of the reaction the yellowish highly viscous product was washed with 3 portions of 50 ml CCl in order to remove the methanol formed, thereby obtaining 66 g of a whitish substance of a pasty nature, insoluble in trichloroethylene, tetrachloroethane, perchloroethylene, CCL CHCl CH Cl partly soluble in l,l,2- trichlorotrifluoroethane, acetone, ethylacetate. This quantity of perfluoroacylamide of the formula Rf-COHN-)C, H,NH), C,H dissolved in 240 ml of the solvent consisting of 1,l,2-trichlorotrifluoroethane and acetone in a SOpercent by volume proportion was reacted with 1,500 g of the polyester urethane prepolymer (C) dissolved in 1 liter 1,1,2- trichlorotrifluoroethylene in the manner described in Example 4.

The result was a slightly viscous yellow solution, which was diluted to 6,800 ml by adding trichloroethylene. The obtained polymer may be recovered by initially distilling one liter 1,1,2 trichlorotrifluoroethane and evaporating the remaining solvent at reduced pressure till constant weight is reached, in the manner previously described. The result is 1,565 g ofa highly viscous yellow polymer of a number average molecular weight of 60,000 containing eight free isocyanate groups in the molecule, soluble in chlorinated and non-chlorinated solvents previously mentioned in this example. In the precence of moisture this polymer is slowly converted to an increasingly viscous mass till it takes a rubber-like aspect and is insoluble (even at elevated temperature) in all solvents mentioned hereinbefore.

USE

200 ml of a solution of the polymer prepared as above were diluted to 1 liter with methylchloroform to reach a polymer concentration of 46 g/liter.

Knitted were specimens were processed with this solution by immersion as well as by spraying and subsequent wringing so as to reach a l00percent impregnation.

The specimens were dried at 100C during minutes. The tests results are tabulated hereunder:

96.5 g C F COCl (0.2 mols) were slowly reacted at 30 C with 12.9 g aziridine (0.3 mols) and 21 g triethylamine dispersed in ethyl ether in the manner described in Example 8. After filtering off the triethylamine hydrochloride and removing the ether by evaporation in vacuum, 102 g of a waxy whitish product were obtained which was dissolved in 500 ml of the 50percent by volume mixture of acetone and C,Cl F (The product is insoluble in the chlorinated solvents recited in the preceding examples and is partly soluble in l,l,2- trichlorotrifluoroethane, acetone, ethylacetate). This solution was admixed dropwise to 1,500 g of the polyester urethane prepolymer (C), dissolved in one liter C,CI;,F at the reflux temperature of the latter. On completion of the addition refluxing was continued during 30 minutes. By proceeding as described in Example 8, 1,600 g ofa pale-white highly viscous polymer of a number-average molecular weight of 27,000 could be obtained. The polymer contained seven free isocyanate groups in the molecule and became increasingly viscous in the presence of moisture and at room temperature till it was converted to a polyamide resin insoluble in all tested solvents, even at elevated temperature. A solution of the polymer obtained as above was diluted to 4,000 ml by adding perchloroethylene.

USE

52 ml of the solution were dissolved at room temperature in one liter trichloroethylene to obtain a polymer concentration of about 21 g/liter and a fluorinated moiety concentration of 1.6 g/liter. The tests of processing woollen knitted were were carried out in the manner described in the preceding exam- Where the product is not required to impart shrink-proofness properties, smaller proportions of free NCO groups are sufficient.

Thus, 96.5 g C,F,,COC1 (0.2 mols) were slowly reacted at 28C with 12.9 g aziridine (0.3 mols) and 21 g triethylamine dispersed in ethyl ether in the manner described in Example 8.

After filtering ofi the triethylamine hydrochloride and removing ether by evaporation at reduced pressure, 102 g of the waxy white product mentioned in the first part of Example 11 were obtained. This was dissolved in 500 ml of the 50percent by volume mixture od acetone and C,Cl,F,

This solution was added dropwise to 300 g of the polyether urethane prepolymer (B) dissolved in 500 ml C,Cl,F, at reflux temperature. On completion of addition refluxing was continued during 30 further minutes. To recover the polymer fonned, 700 ml l,l,2 trichlorotrifluoroethane are initially distilled, the remaining solvent being subsequently evaporated at reduced pressure. The result is 200 g ofa pale-yellow highly viscous polymer of a number-average molecular weight of 13,500 soluble in the solvents mentioned in the preceding example and containing one isocyanate group in the molecule.

In the presence of moisture this polymer solidifies to a polyamide resin insoluble in all tested solvents even at elevated temperature. The solution of the said polymer (unrecovered) was diluted to 1 liter by adding a 50percent by volume mixture of trichloroethylene and l ,1 ,2 trichlorotrifluoroethane.

USE

11.5 ml of the solution were dissolved in 1 liter trichloroethylene to reach the same fluorinated moiety concentration as in Example 11 and a polymer concentration of 200 g/liter.

Comparative results on natural and man-made fiber fabrics are tabulated hereunder.

Initial After 5 dry After 5 wet value cleaning washing processes processes A B A B A B Wool Oil-repellency 8 7-8 7 6-7 7 6 Water-repellency -90 80 80 70-80 70-30 Cotton Oil-repellency 7-8 7 7 6 6-7 6 Water-repellency 90 90 80 70 70-80 70 Flax Oil-repellency 7-8 8 7 6 6-7 6 Water-repellency 80 80-9070-80 60-7070 50-70 Polyester Oil-repellency 7-8 7 6-7 6 6-7 5-6 Water-repellency 80 80-9070-80 70 70 70 Polyamide Oil-repellency 8 7-8 7 6-7 6 6 Water-repellency 80-90 90 70 B0 60-70 70 Acrylics Oil-repellency 7-8 7 6-7 6 6 5 Water-repellency 80-90 90 70-80 80 50-70 70 Acetate Oil-repellency 8 7 6-7 6 6 Water-repellency 80 80-9060-70 70-8050-70 70 Chlorovinyl Oil-repellency 8 7 7 6 7 5 Water-repellency 80 80-9070-80 70 70 50-70 A Product prepared according to Example I l B Product prepared according to Example 12.

EXAMPLE 13 54.2 g C,F,,COOC,H,, (0.1 mols) previously cooled to 0 C were slowly reacted with 8.6 g aziridine (0.2 mols) preventing the temperature from exceeding 5 C. On completion of addition the temperature was slowly raised to 30C.

The initially viscous white reaction product gradually became yellow and of a waxy consistency. It was washed with 3 portions each of 50 ml of carbon tetrachloride in order to remove C,H 0H formed as a reaction by-product, thereby obtaining 58 of a waxy pale white solid which slowly becomes yellow at room temperature. This compound is insoluble in chlorinated solvents mentioned in the preceding examples and is partly soluble in 1,1,2 trichlorotrifluoroethane, acetone, ethylacetate and ethyl ether. it was dissolved in 200 ml of the 50percent by volume mixture of acetone and C,Cl,F, and was reacted with 300 g of the polyether prepolymer (A) dissolved in 0.5 l l,l,2-trichlorotrifiuoroethane by the process according to Example 1.

min. rum

USE

50 ml of the solution were dissolved in 1 liter trichloroethylene at room temperature to obtain a polymer concentration of IO g/liter. The woollen specimens were treated by a 90percent impregnation. Drying was effected at 120 C during 8 minutes. The test results are tabulated hereunder:

Initial After 5 dry After 5 wet value cleaning washing processes processes Oil-tepellency 8-9 8 7-8 Water-repellency 90-l00 80-90 80-90 Shrinkage area 2.3 2.5 2.5

EXAMPLE [4 300 g of the polyether polymer (A) dissolved in 250 ml anhydrous ethyl acetate were admixed with 18.8 g phenol, the solution being refluxed during 4 hours. The resulting prepolymer still containing one NCO group per chain was reacted with 8.8 g C,H NHC,H NH, in the manner described in Example 9.

The reaction mixture was refluxed and admixed while vigorously stirring with 53.2 g C,F,,COCl (0.l mols) dissolved in 200 ml l,l ,2-trichlorotrifluoroethane.

Refluxing was pursued till the BC] by-product had thoroughly evolved, whereupon the solution was cooled and diluted to 1,780 ml by adding methylchloroform.

The polymer containing 2 phenol-protected isocyanate groups per molecule, obtained as above, was recovered by initially distilling 160 ml l,l,2-trichlorotrifluoroethane, then evaporating the remaining solvent at reduced pressure in the same manner as described in Example 6. The result was 376 g of a highly viscous yellow polymer of a number-average molecular weight of 3,600 soluble in the solvents mentioned in the preceding example. The polymer could be indefinitely preserved even in the presence of moisture.

USE

Treatment was effected by adopting the concentrations and procedure described in the preceding Example. The results almost coincided.

EXAMPLE l5 8.6 g aziridine (0.2 mole) were added dropwise to a 100 ml flask containing 54.2 g C,F,,C0OC,l-l, (0.1 mols), the mixture being maintained while stirring at 28 C during 48 hours. Then the temperature was allowed to rise to 50 C, thereby obtaining a yellow-brown waxy solid substance. The reaction by-product C,H,,OH was removed by extraction with 3 portions each of 25 ml of CH,CCI, thereby obtaining 58g of a waxy solid dark-yellow polymer. This quantity was dissolved in 300 ml of a 50percent by volume mixture of 1,I,2- trichlorotrifluoroethane and acetone, the polymer proving to be insoluble in the already repeatedly mentioned chlorinated solvents and to be slightly soluble in l,l,2- trichlorotrifluoroethane, acetone, isopropyl alcohol and ethyl acetate. The solution prepared as above was added dropwise to 300 g of the polyether urethane prepolymer (A) dissolved in 0.5 l l,l,2-trichlorotrifluoroethane under reflux in a 2 liter flask and stirring. On completion of addition refluxing was continued during about 30 minutes, whereupon dilution up to l,780 ml was effected by l,l,2-trichlorotrifluoroethane and trichloroethylene in a 50percent by volume proportion, whereby a slightly viscous dark-yellow solution was obtained. The polymer could be separated from the solution, before dilution, by proceeding as described in Example 7. The result was 360 g highly viscous yellow polymer of a number-average molecular weight of 32,000 containing 18 free isocyanate groups in the molecule, soluble in l,1,2- trichlorotrifluoroethane, trichloroethylene, perchloroethylene, methylchloroform, acetone and CCl,

The behavior of this product, manner of use and results obtained coincide with those in Example 13.

EXAMPLE 16 Where the product is not required to confer shrink-proofness properties, smaller proportions of free NCO groups are sufficient. Thus, a I00 ml flask containing 54.2 g C,F,,COOC, H (0.! mols) was supplied dropwise with 8.6 g aziridine (0.2 mols) as previously described in Example IS.

The solution containing 58 g of the product obtained as above in 300 ml of a 50percent by volume mixture of l,l,2- trichlorotrifluoroethane and acetone was added dropwise to 150 g of the polyether urethane prepolymer (A) dissolved in 0.3 l CCl F, under reflux while stirring in a l-liter flask. On completion of addition refluxing was continued during about 30 minutes, followed by dilution to 830 ml with l,l,2- trichlorotrifluoroethane and trichloroethylene in a 50percent by volume proportion yielding a yellow viscous solution. In this case also the polymer was recoverable by initially distilling 450 ml l,1,2-trichlorotrifluoroethane, the remaining solvent being removed as previously described in Example 7. The result was 205 g highly viscous yellow polymer of a numberaverage molecular weight of l7,000 containing four isocyanate group in the molecule, soluble in the chlorinated and non-chlorinated solvents of the preceding example. The polymer was found to be unstable in the presence of moisure and under prolonged action of heat, similarly to the polymer synthesized in Example 15, and slowly converted to a consistent solid rubber-like mass insoluble in all tested solvents even at elevated temperature.

USE

2|.2 ml of the yellow viscous solution obtained as above were diluted with l liter trichloroethylene to obtain a polymer concentration of 10 g/liter similarly to the processing tests given in Examples l3, 14, 15 and a fluorinated moiety concentration amounting to L39 g/liter.

Comparative test results on natural and man-made fiber fabrics are tabulated hereunder:

Initial After 5 dry After 5 wet value cleaning washing processes processes A B A B A B Wool Oil-repellency 8 8 7-8 7-8 6 7 Water-repellency I00 10090-100 90-l00 -90 80-90 Cotton Oil-repellency 8 7-8 7 7 7 6-7 Water-repellency l 00 l0080-90 90 80 80 Flax Oil-repellency 8 8 7 7 7 7 Water-repellency 90-100 10090 80-90 80 80-90 Polyester Oil-repellency 8 7-8 7 6-7 7 -7 Water-repellency 90-100 90-l00 90 90 80-90 80-90 Polyamide Oil-repellency 8-9 8 7-8 7 7 7-8 Water-repellency I00 l0080-90 90- l 00 80-90 80-90 Acrylics Oil-repellency B 7-8 7 7 7 7 Water-repellency 90-100 90 80-90 80 80 Acetate Oil-repellency 8 8 'I 7 7 6-7 Water-repellency 90-l00 I 90 90 80-90 80 Chlorovinyl Oil-repellency 8 8 7 7 7 6-7 Water-repellency I00 |0090 90 80-90 80 A product prepared as in Example l B product prepared as in Example 16 it should be emphasized that, where fabrics are treated with products of this invention to impart shrink-proofness properties to woollen fibers contained therein, the fabrics also acquire a considerable crease-proofness.

ln treating man-made fiber fabrics, products of this invention should be avoided which contain phenol blocked isocyanate groups, as the high temperature required to set free phenol (150 C) would damage the fibers,

All the examples described hereinbefore yield polymeric products having novel sharply differing from those of the starting compounds, namely:

solubility in conventional chlorinated solvents high oil-repellency fair water-repellency excellent shrink-proofness, when desired, whereas such properties did not cumulate in a single product among those known in the art.

Examples shall now be described to show that, where the correct preparation conditions are not complied with, the desired products are not obtained or are seriously ineffective.

EXAMPLE 1'! 29.2 g C,F,COOC,H,, (0.l mols) and 8.6 g aziridine (0.2 mols) were reacted preventing the temperature from exceeding 5 C. The reaction product was washed with 3 portions each of 20 ml of CCl, in order to remove the reaction byproduct C,H H,,OH, thereby obtaining 33 g of an oily yellowish product which was dissolved in a SOpercent by volume mixture of acetone and C,CI;,F The product was found to be insoluble in the chlorinated solvents mentioned in the preceding examples, slightly soluble in l,l ,2- trichlorotrifluoroethane, benzotrifluoride, acetone and ethylacetate. It was subsequently reacted with 300 g of polyether urethane prepolymer (A) in the hereinbefore repeatedly described manner.

The result was a pale yellow solution which, on removal of the solvent, yielded 333 g of a slightly viscous polymer of a number-average molecular weight of 28,500 containing 17 isocyanate groups in the molecule. The polymer was found to be unstable with time and changed to a compact yellow mass insoluble in all tested solvents. The results of processing woollen knitted were by dipping into a trichloroethylene solution, lOOpercent wringing and heat-treating at 120 C during minutes are summarized hereafter. The concentrations in the processing bath were as follows:

polymer content 43 g/l fluorinated moiety concentration 3 g/l Initial After 5 dry After 5 wet value cleaning washing processes processes Oil-repelleney none none none Waterrepellency 050 0-50 0-50 Shrinkage area 0.8 L0 L2 EXAMPLE l8 EXAMPLE l9 12.9 g aziridine and 86.5 g C-,F, C0Cl were reacted as 0 previously described in Example 5.

The resulting product, in a solution of l,l,2- trichlorotrifluoroethane and acetone, was reacted with an ethyl acetate solution of 25 g diphenylmethane 4.4'-diisocyanate. During the progress of the reaction a powdery precipitate was formed, which was insoluble in all tested solvents.

A similar reaction effected with 60 g of the isocyanate of the following formula:

IIICO or with 17.5 toluene 2.4-diisocyanate led to products unstable with time and degradable to polyurethane rubbers insoluble in all conventional solvents and which could only be dispersed in the already repeatedly mentioned chlorinated solvents.

The dispersions are further unstable simply on stirring and yield agglomerates insoluble in all tested solvents or their mixtures, even at elevated temperature.

OPERATIONAL CONDITIONS 1. Rf-COOR aziridine reaction The reaction requires:

a. the two reagents to be simultaneously admitted to the reactor for the sake of a satisfactory structural regularity in the polymer;

b. the temperature not to exceed 5 C to avoid thermal and chromatic degradations of the polymer;

0. stirring to be vigorous in order to avoid local superheating on account of the high exothermic character of the two reactions (amidation and polymerization).

Where one only of the above three conditions is not met the subsequent reaction of perfluoroacylamido N-alkylamine and prepolymer containing the free -NCO groups easily leads to rubbery or unstable products.

2. Rf-COCI aziridine reaction The reaction requires:

a. the temperature not to exceed 25 C in order to avoid a sharp polymerization of the imide formed;

b. stirring to be vigorous in order to avoid local super-heating which would promptly result in polymerization of the ethyleneimine present before formation of the monomeric imide;

c. filtering of triethylamine hydrochloride by-product to be carried out at a temperature not exceeding 25 C. The precipitate shall be advantageously washed with (CH,CH,)B2O previously cooled to 30 C.

If these conditions are not complied with the end product can be expected to be rubbery or unstable with time.

3. RfCOOR and aziridine reactions Upon completion of the amidation reactions the alcohol set free as a reaction product should be fully removed in order to avoid possible secondary reactions with the --NCO groups and formation of rubbers and urethane foams.

4. Reaction of pertluoroacylamido N-alkylamine and NCO groups containing prepolymer This reaction requires:

A. to obtain homogeneous phase reaction conditions, both perfluoroacylamido N-alkylamine and the prepolymer containing free NCO groups should be dissolved in a mixture of at least two solvents consisting of:

a. a fluorochlorinated organic solvent in a proportion of 5080percent by volume (such as l,l,2- trichlorotrifluoroethane) b. a polar organic solvent in a proportion of 20-50percent by volume (such as acetone, ethylacetate, methylethylketone,etc.);

B. the mixture of the solvents to be strictly anhydrous in order to avoid part hydrolysis of the NCO groups to NH, groups, and ensuing reaction with the remaining NCO groups leading to the formation of insoluble rubbers and polyurethane foam s;

C. the perfluoroacyl N-alkylamine solution to be slowly added to the solution being refluxed of the prepolymer containing the free NCO groups, and not vice-versa. Otherwise, interand intra-molecular bridges are formed, the product being rubber-like and unstable with time.

5. Reaction of the prepolymer containing NCO groups partly blocked by phenol and polyamines Requirements:

A. the reaction should occur in a mixture of at least two so]- vents formed as follows:

a. a fluorochlorinated organic solvent in a proportion of 5080percent by volume (such as 1,l,2- trichlorotrifluoroethane) b. a polar organic solvent in a proportion of ZO-SOpercent by volume, such a acetone, ethylacetate, methylethylketone.

B. the mixture of the solvents should be strictly anhydrous in order to avoid part hydrolysis of the -NCO groups to NH groups with the already described consequences;

C. the solution of polyester or polyether prepolymer with the partly phenol-blocked NCO groups should be slowly added to the polyamine solution and not vice-versa. Otherwise, reaction of the -NH groups of the polyamine with the available NCO groups would occur and subsequent reaction with RfCOX would lead to a product in which in formula (I) m 0.

TEST CONDITIONS For the sake of completeness the conditions shall now be briefly described under which the tests were carried out, the results of which are given in the preceding examples.

1. Treatment of fabrics:

1.1. Treatment by spraying The tests were carried out on weighed fabric strips l-l 70 cm long and 20 cm wide. The strips were caused to travel between three nozzle sets spraying one side and two nozzle sets spraing the other side of the strip, the nozzle bore being 0.5 mm in diameter and the spray cone angle being of 90. The solution to be sprayed was fed to the nozzles at a pressure of 4 atrn. The rate of feed of the fabric was in every instance adjusted so that after spraying the fabric was thoroughly and uniformly wetted but was free from dripping, that is, its absorption was about i20-l SOpercent by weight or about SO-IOOpercent by volume, more particularly:

rate of feed absorption wool cloth 8 mlmin. 80% vol. carded wool cloth 5 m/min. l05% vol. acrylic fabric 7 m/min. 102% vol. cotton cloth 5 m/min 100% vol. cotton/polyester cloth l0 mlmin. 80% vol.

After spraying the fabric was weighed to accuratedly determine the absorption by weight, then placed on a tenter for drying and setting the polymer being tested.

l.2 Treatment by dipping: In this case also weighed fabric strips l00-l 70 cm long and 20 cm wide were used. Each strip was fed once through a four-roller padding mangle and slightly wrung (pressure 0.2 0.5 Kg/cm).

After impregnation the strips were weighed in order to accurately determine the absorption. Drying and setting were carried out on a tenter as in case 1.1.

2. Treatment of yarn and knitted wear:

2.] Treatment by spraying A machine of the conventional dry cleaning drum-type was employed with the addition of a spray nozzle secured to the charging door for the material to be processed. The material was weighed, introduced into the machine and washed in the latter before treatment. The treating solution contained the quantity of polymer to be deposited on the material dissolved in a quantity of solvent equalling twice the weight of the material. The solution was fed to the nozzle at a pressure of 4 atm, while the machine drum was kept running. On completion of spraying the drum was rotated during further it) minutes to cause the solution to uniformly impregnate the material, whereupon the solvent was evaporated and thermosetting was carried out by the heating means incorporated by the machine.

2.2 Treatment by impregnation The same machine was employed as in case 2.] The material was weighed, introduced into the machine and washed before treatment. Subsequently, the impregnating solution was filled into the machine and the drum was run during 3 minutes. On stoppage of the drum the excess solution was pumped back to the reservoir. Without disconnecting the pump the drum was run at the wash rate during l minute, stopped during l minute and run again during l further minute. The pump was stopped and the drum again operated in order to effect drying and thermosetting by the heating means incorporated by the machine,

PAINTS The compounds according to the invention have been employed as an additive for paints. The tests were carried out on paints of the acrylic, vinylic, epoxy and melamine type.

The quantities introduced range between 0.5 and Zpercent by weight of the overall dry weight. The paints admixed with the compounds very evenly distributed over the surface to be protected (glass and metal) and formed a film ofimproved adherence, uniformity and compactness.

When adding the compounds to paints having a pigment dispersed therein, the brilliancy of the color was enhanced.

LEATHER AND PAPER X is bonded to an alkylene chain of one of said units and is selected from the group consisting of a hydrogen atom, a methoxy-, ethoxy-, propoxyand isopropoxy group;

Y is bonded to a nitrogen atom of one of said units and is selected from the group consisting of a hydrogen atom, methyl, ethyl, propyl and isopropyl groups;

Rf is a perfluon'nated hydrocarbon chain C,F, in which 2 is an integer from 5 to 11;

a, b and c are integers from 2 to l0;

n is an integer from I to It);

m is an integer from I to 10; p is an integer from 1 to 5; q is an integer from to Z is a polyesteror a polyether-polyurethane chain carrying the numberp of the NCO groups indicated in the formula; the number-average molecular weight of the compound not exceeding 60,000; and precursors of said compounds wherein the NCO groups are temporarily blocked. 2. Compounds as claimed in claim 1, having a numberaverage molecular weight of at least 3,500.

3. Compounds as claimed in claim I, having a numberaverage molecular weight of at least 3,500 and wherein z is at least 7.

4. Compounds as claimed in claim I, wherein the [ERN- CO moiety has a number-average molecular weight of from 3,000 to 15,000.

5. Compounds as claimed in claim 1, wherein the NCO groups in the {2](NCO), moiety are attached to alkylene chains, the latter being the chains originally present in the dior tri-isocyanate.

6. Compounds as claimed in claim 1, wherein:

the {2](NCO), moiety has a number-average molecular weight of from 3,000 to l5,000;

the NCO groups in the {2](NCO), moiety are attached to alkylene chains, the latter being the chains originally present in the dior tri-isocyanate.

Claims

2. Compounds as claimed in claim 1, having a number-average molecular weight of at least 3,500.
3. Compounds as claimed in claim 1, having a number-average molecular weight of at least 3,500 and wherein z is at least 7.
4. Compounds as claimed in claim 1, wherein the ( Sigma )(NCO)p moiety has a number-average molecular weight of from 3,000 to 15, 000.
5. Compounds as claimed in claim 1, wherein the NCO groups in the ( Sigma )(NCO)p moiety are attached to alkylene chains, the latter being the chains originally present in the di- or tri-isocyanate.
6. Compounds as claimed in claim 1, wherein: the ( Sigma )(NCO)p moiety has a number-average molecular weight of from 3,000 to 15,000; the NCO groups in the ( Sigma )(NCO)p moiety are attached to alkylene chains, the latter being the chains originally present in the di- or tri-isocyanate.