Lo Monaco, Sergio (Vicenza, IT)
Guerrato, Alfredo (Trissino, IT)
Fabbro, Dario (Trissino, IT)
Donadello, Graziello (Valdagno, IT)

05/026263

06/20/1972

04/07/1970

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528/70

528/44, 528/61, 528/73, 528/80, 528/45, 8/127.600, 528/76

C08G18/10; C08G18/83; C08G73/02; D06M15/576; D06M15/61; C08G18/00; C08G73/00; D06M15/37; C08G53/16; D06M15/52; C08G22/04

260/77.5AM,75NH,77.5R,75TN,77.5CH,2EN,77.5KP

Czaja, Donald E.

Cockeram H. S.

We claim

1. A polymeric compound containing randomly repeating units, said units being represented by the formulas: ##SPC7##

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 [Σ](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 [Σ](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 above is illustrated by the appended drawing showing a diagram obtained under conditions in which the concentration of the fluorinated part Rf in 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 water-repellency values SR are expressed according to the AATCC Spray Test 22-1952, both as a function of z (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 of the test liquid.

Test Liquid Surface tension Du Pont dyne/cm scale ____________________________________________________________ ______________ Nujol (Plough Inc.) 31.45 2 75/25 Nujol/n-hexadecane 30.00 3 50/50 Nujol/n-hexadecane 29.05 4 n-tetradecane 26.35 5 n-dodecane 24.70 6 n-decane 23.50 7 n-octane 21.40 8 n-heptane 19.75 9 ____________________________________________________________ ______________

The polyamines can be amidated 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 ₂ SO ₄ ^. BF ₃ 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 Rf in the solution being applied;

impart water-repellency;

impart shrink-proofness properties to wool yarn when the concentration of the [Σ](NCO) _p 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 [Σ](NCO) _p 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 [Σ](NCO) _p 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 15,000;

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 oil- or 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 oil- and 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- Solu- pellency pellency bility ____________________________________________________________ ______________ Polyamine with per- fluorinated chains 6-7 0-50 NO Polyester or polyether prepolymer with reactive -NCO groups 0 0-50 YES Compound (I) 7-8 80-90 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 1,1,1-trimethylolpropane CH ₃ --CH ₂ --C(CH ₂ --OH) ₃ 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 ₂ OH) ₄ 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 free --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 ₂ H ₅ --C(CH ₂ --O--CO--NH--C ₆ H ₁₂ --NCO) ₃ .

EXAMPLE 1

44.2 g C ₇ F ₁₅ --COOC ₂ H ₅ (0.1 mols) and 8.6 g aziridine (0.2 mols) previously cooled to 0° 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 cm ^{- 1} ascribed to the carbonyl stretching of the ester of the perfluoro acid according to Colthup, Daly, Wiberley--Introduction to Infrared and Raman Spectroscopy, page 315 -- Academic Press, 1964, showed that the ester had reacted almost quantitatively.

From the reaction product C ₂ H ₅ 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 three-necked 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 ₂ trap in the vacuum line, thereby obtaining 350 g of a transparent syrupy straw-yellow polymer which on cooling increase in viscosity without, however, being solid at 18° C. The polymer is of a number-average 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 100 percent impregnation. No difference was ascertained in oil- and water-repellency and shrink-proofness when the treated specimens were dried under the following conditions:

a. during 48 hours at a temperature: of 20°-60° C;

b. during 10 minutes at 90° C;

c. during 5 minutes at 150° c.

The test results are summarized hereafter.

After 5 After 5 Initial dry-cleaning wet washing value processes processes ____________________________________________________________ ______________ Oil-repellency 8 7 7 Water-repellency 80-90 70-80 70 Shrinkage area % 2.0 2.0 2.5 ____________________________________________________________ ______________

EXAMPLE 2

88.4 g C ₇ F ₁₅ COOC ₂ H ₅ (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 1,1,2-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 of a 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:

After 5 After 5 Initial cleaning wet washing value processes processes ____________________________________________________________ ______________ Oil-repellency 8 7 7 Water-repellency 80-90 70-80 70 Shrinkage area % 6 10 12 ____________________________________________________________ ______________

EXAMPLE 3

When the product is not required to impart shrink-proofness properties, smaller proportions of free --NCO groups are sufficient. Thus, 44.2 g C ₇ F ₁₅ COOC ₂ H ₅ (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 ₄ , 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, CCl ₄ , CHCl ₃ , methylchloroform, 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 trichlorotrifluoroethane 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, methylchloroform, CCl ₄ , 1,1,2 trichlorotrifluoroethane, acetone, ethyl and isopropyl alcohol, being of a number-average molecular weight of 14,000 and containing four isocyanate groups per molecule.

USE

33 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.

Initial After 5 dry After 5 wet value cleaning washing processes processes ____________________________________________________________ ______________ A B A B A B

wool Oil-repellency 7 7 7 7 6-7 6 Water-repellency 80-90 80-90 70-80 80 70 70

Cotton Oil-repellency 6 6 6 6 5-6 5 Water-repellency 70 70 60-70 70 50-60 50-70

Flax Oil-repellency 7 7 7 7 6-7 6 Water-repellency 70-80 80 70 70-80 50-70 70

Polyester Oil-repellency 7 7 7 7 6-7 6 Water-repellency 80-90 80 80-90 70 70 70

Polyamide Oil-repellency 7-8 7 7-8 6-7 7 6 Water-repellency 80 80-90 70-80 80 70 70

Acrylics Oil-repellency 7 7 7 6 6-7 6 Water-repellency 80-90 80-90 70-80 80 60-70 70

Acetate Oil-repellency 7-8 7 7 6 7 6 Water-repellency 70-80 80 70 70-80 50-70 70

Chlorovinyl Oil-repellency 7-8 7 7-8 7 7 6 Water-repellency 80 80-90 70-80 80 70 50-70 ____________________________________________________________ ______________

A = product prepared according to Example 1

B = product prepared according to Example 3.

In the above and preceding examples the tests for oil- and water-repellency, shrink-proofness and dry cleaning and wet washing were effected 100 hours after treatment of the specimens.

EXAMPLE 4

21.7 g C ₂ H ₅ --(NH--C ₂ H ₄ --) ₄ --NH ₂ (0.1 mols) were charged to a 500 ml flask provided with a stirrer and cooler, subsequently 45.6 g C ₇ F ₁₅ COOCH(CH ₃ ) ₂ (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 ₄ 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, 1,1,2 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 ₂ 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 dibutylamine 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 afford in every case a 150 percent impregnation.

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

Initial After 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 % 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 shrink-proofness in the treated wool yarn.

45.6 g C ₇ F ₁₅ COOCH(CH ₃ ) ₂ (0.1 mols) were reacted with 21.7 g (0.1 mols) of C ₂ H ₅ (NH--C ₂ H ₄ ) ₄ --NH ₂ , the product being washed as previously described in Example 4.

41g of a viscous yellow-brown compound of the formula C ₂ H ₅ (NH--C ₂ H ₄ ) ₄ --NH--CO Rf were obtained and dissolved in 890 ml of a solvent consisting of 1,1,2 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. After initially distilling 800 ml 1,1,2 trichlorotrifluoroethane and removing the remaining solvent by evaporation at 38° C during 90 minutes in the previously described manner, 1,060 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 IR spectrophotometry and volumetric analysis by means of dibutylamine. The polymer was subsequently heated to 100°-120°-140°-180°-200° 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:

Initial After 5 dry After 5 wet value cleaning washing processes processes ____________________________________________________________ ______________ Oil-repellency 8-9 8 7-8 Hydro repellency 80-90 80 70-80 Shrinkage area % As in non-treated specimens ____________________________________________________________ ______________

EXAMPLE 6

150g (0.01 mols) of the polyester urethane prepolymer (C) dissolved in 100 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 CaCl ₂ traps and admixed dropwise with 2.15 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 ₇ F ₁₅ COCl (0.04 mols) dissolved in 200 ml anhydrous 1,1,2trichlorotrifluoroethane were added dropwise. The solution was refluxed during 10 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 1,1,2-trichlorotrifluoroethane at 42° C during 90 minutes. The result is 173 g of a transparent viscous yellow polymer 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, 1,1,2 trichlorotrifluoroethane, ethyl acetate, acetone. 22 g of such polymer were subsequently heated to 130°- 140°- 150°- 160° 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 1,1,2 trichlorotrifluoroethane and acetone and the resulting solution 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 ₂ H ₅ OH was employed as indicator. The analysis showed that at 150° C all --NCO groups blocked by phenol has been re-established.

USE

52 ml of the solution containing the non-recovered polymer prepared as described above, were diluted at room temperature with 1 liter methylchoroform, whereby the polymer concentration was 15 g/liter.

Specimens of woollen knitted were were treated with this solution by dipping and by spraying and subsequent wringing, to effect in both cases a 130 percent impregnation. After drying at 70° C during 1 hour a heat treatment at 150° C during 5 minutes was necessary in order to set the phenol groups free. The test results are tabulated hereunder:

Initial After 5 dry After 5 wet value cleaning washing processes processes ____________________________________________________________ ______________ Oil-repellency 8 7-8 7 Water-repellency 80-90 80 70-80 Shrinkage area % 2.0 2.0 2.3 ____________________________________________________________ ______________

EXAMPLE 7

8.5 aziridine (0.2 mols) were added dropwise to a 100 ml flask containing 44.2 g C ₇ F ₁₅ COOC ₂ H ₅ (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 perfluoroacylamido, 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-trichlorotrifluoroethane 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 1,1,2 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, 1,1,2-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 1.

EXAMPLE 8

12.9 g aziridine (0.3mols) and 21 g triethylamine dissolved in 360 ml ether were charged to a three-necked 1 liter flask. The solution was carefully cooled to -30° C and slowly admixed with 86.5 g C ₇ F ₁₅ COCl (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-brown mass were obtained which was dissolved in 500 ml of the 50percent by volume mixture of 1,1,2-trichlorotrifluoroethane and acetone. The mass proved to be insoluble in trichloroethylene, tetrachloroethane, tetrachloroethylene, methylchloroform, chloroform and carbon tetrachloride, and partly soluble in 1,1,2-trichlorotrifluoroethane, acetone, diethylether, ethyl acetate.

1,500 g of the polyester urethane prepolymer (C) were dissolved in 1 liter 1,1,2-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 IR spectrophotometry the decrease in time of the band at 2,263 cm-1 belonging to the --NCO group could be checked. By distillation of 1,200 ml 1,1,2-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 number-average 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 % 2.0 2.0 2.4 ____________________________________________________________ ______________

EXAMPLE 9

300 g of the polyether urethane prepolymer (A) dissolved in 250 ml anhydrous ethyl acetate were added to 18.8 g phenol and the solution was refluxed during 4 hours. The solution of the prepolymer was analyzed and was found to still contain 1 isocyanate group in the molecule.

8.8 g CH ₃ NHCH ₂ CH ₂ NH ₂ (0.1 mols) in 25 mol ligroin were charged while vigorously stirring to a three-necked 1-liter flask equipped with a stirrer and cooler. The dispersion prepared as above and cooled with brine at -28° C was admixed 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 ₇ F ₁₅ COCl (0.1 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 160 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 of a number-average molecular weight of 3,500 soluble in trichloroethylene, tetrachloroethane, perchloroethylene, methylchloroform, chloroform, CC1 ₄ , 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:

Initial After 5 dry After 5 wet valve cleaning washing processes processes ____________________________________________________________ ______________ Oil-repellency 8 7 7 Water-repellency 80-90 80 70-80 Shrinkage area % 2.0 2.0 2.4 ____________________________________________________________ ______________

EXAMPLE 10

21.7 g C ₂ H ₅ --(NH--C ₂ H ₄ ) ₄ --NH ₂ (0.1 mols) were slowly reacted while stirring with 47.8 g C ₈ F ₁₇ COOCH ₃ (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 ₄ 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 ₄ , CHCl ₃ , CH _C Cl ₃ , partly soluble in 1,1,2-trichlorotrifluoroethane, acetone, ethylacetate. This quantity of perfluoroacylamide of the formula Rf--COHN--)C ₂ H ₄ NH) ₄ --C ₂ H ₅ dissolved in 240 ml of the solvent consisting of 1,1,2-trichlorotrifluoroethane and acetone in a 50percent 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 of a 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 100percent impregnation.

The specimens were dried at 100° C during 10 minutes. The tests 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 % 2.2 2.4 2.9 ____________________________________________________________ ______________

EXAMPLE 11

96.5 g C ₈ F ₁₇ 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 ₂ Cl ₃ F ₃ . (The product is insoluble in the chlorinated solvents recited in the preceding examples and is partly soluble in 1,1,2-trichlorotrifluoroethane, acetone, ethylacetate). This solution was admixed dropwise to 1,500 g of the polyester urethane prepolymer (C), dissolved in one liter C ₂ Cl ₃ F ₃ , 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 of a 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 examples. 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 % 2.2 2.4 2.9 ____________________________________________________________ ______________

E EXAMPLE 12

Where the product is not required to impart shrink-proofness properties, smaller proportions of free --NCO groups are sufficient.

Thus, 96.5 g C ₈ F ₁₅ COCl (0.2 mols) were slowly reacted at -28° 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 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 ₂ Cl ₃ F ₃ .

This solution was added dropwise to 300 g of the polyether urethane prepolymer (B) dissolved in 500 ml C ₂ Cl ₃ F ₃ at reflux temperature. On completion of addition refluxing was continued during 30 further minutes. To recover the polymer formed, 700 ml 1,1,2 trichlorotrifluoroethane are initially distilled, the remaining solvent being subsequently evaporated at reduced pressure. The result is 200 g of a 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 1,1,2 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 80-90 90 80 80 70-80 70-80

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 80-90 70-80 60-70 70 50-70

Polyester Oil-repellency 7-8 7 6-7 6 6-7 5-6 Water-repellency 80 80-90 70-80 70 70 70

Polyamide Oil-repellency 8 7-8 7 6-7 6 6 Water-repellency 80-90 90 70 80 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 6 Water-repellency 80 80-90 60-70 70-80 50-70 70 Chlorovinyl Oil-repellency 8 7 7 6 7 5 Water-repellency 80 80-90 70-80 70 70 50-70 ____________________________________________________________ ______________

A = product prepared according to Example 11

B = product prepared according to Example 12.

EXAMPLE 13

54.2 g C ₉ F ₁₉ COOC ₂ H ₅ (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 30° C.

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 ₂ H ₅ OH 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 ₂ Cl ₃ F ₃ and was reacted with 300 g of the polyether prepolymer (A) dissolved in 0.5 l 1,1,2-trichlorotrifluoroethane by the process according to Example 1.

The polymer yielded by the reaction may be segregated from its forming solution by the process described in Example 1, thereby obtaining 360 g of an opaque highly viscous yellow-brown polymer of a number-average molecular weight of 32,000 containing 18 free isocyanate groups in the molecule and soluble in ethylacetate, acetone, 1,1,2-trichlorotrifluoroethane, isopropyl alcohol, trichloroethylene, tetrachloroethylene, CCl ₄ , CHCl ₃ CH ₃ CCl ₃ .

The final volume of the forming solution was diluted to 1,790 ml by adding a 50percent by volume mixture of 1,1,2 trichlorotrifluoroethane and trichloroethylene.

USE

50 ml of the solution were dissolved in 1 liter trichloroethylene at room temperature to obtain a polymer concentration of 10 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-repellency 8-9 8 7-8 Water-repellency 90-100 80-90 80-90 Shrinkage area % 2.3 2.5 2.5 ____________________________________________________________ ______________

EXAMPLE 14

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 ₂ H ₅ --NH--C ₂ H.varies.--NH ₂ in the manner described in Example 9.

The reaction mixture was refluxed and admixed while vigorously stirring with 53.2 g C ₉ F ₁₉ COCl (0.1 mols) dissolved in 200 ml 1,1,2-trichlorotrifluoroethane.

Refluxing was pursued till the HCl 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 1,1,2-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 15

8.6 g aziridine (0.2 mole) were added dropwise to a 100 ml flask containing 54.2 g C ₉ F ₁₉ COOC ₂ H ₅ (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 ₂ H ₅ OH was removed by extraction with 3 portions each of 25 ml of CH ₃ CCl ₃ , thereby obtaining 58g of a waxy solid dark-yellow polymer. This quantity was dissolved in 300 ml of a 50percent by volume mixture of 1,1,2-trichlorotrifluoroethane and acetone, the polymer proving to be insoluble in the already repeatedly mentioned chlorinated solvents and to be slightly soluble in 1,1,2-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 1,1,2-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 1,780 ml was effected by 1,1,2-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 1,1,2-trichlorotrifluoroethane, trichloroethylene, perchloroethylene, methylchloroform, acetone and CCl ₄ .

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 100 ml flask containing 54.2 g C ₉ F ₁₉ COOC ₂ H ₅ (0.1 mols) was supplied dropwise with 8.6 g aziridine (0.2 mols) as previously described in Example 15.

The solution containing 58 g of the product obtained as above in 300 ml of a 50percent by volume mixture of 1,1,2-trichlorotrifluoroethane and acetone was added dropwise to 150 g of the polyether urethane prepolymer (A) dissolved in 0.3 l CCl ₃ F ₃ under reflux while stirring in a 1-liter flask. On completion of addition refluxing was continued during about 30 minutes, followed by dilution to 830 ml with 1,1,2-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 1,1,2-trichlorotrifluoroethane, the remaining solvent being removed as previously described in Example 7. The result was 205 g highly viscous yellow polymer of a number-average molecular weight of 17,000 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

21.2 ml of the yellow viscous solution obtained as above were diluted with 1 liter trichloroethylene to obtain a polymer concentration of 10 g/liter similarly to the processing tests given in Examples 13, 14, 15 and a fluorinated moiety concentration amounting to 1.39 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 100 100 90-100 90-100 80-90 80-90 Cotton Oil-repellency 8 7-8 7 7 7 6-7 Water-repellency 90-100 100 80-90 90 80 80 Flax Oil-repellency 8 8 7 7 7 7 Water-repellency 90-100 100 90 80-90 80 80-90 Polyester Oil-repellency 8 7-8 7 6-7 7 6-7 Water-repellency 90-100 90-100 90 90 80-90 80-90 Polyamide Oil-repellency 8-9 8 7-8 7 7 7-8 Water-repellency 100 100 80-90 90-100 80-90 80-90 Acrylics Oil-repellency 8 7-8 7 7 7 7 Water-repellency 90-100 100 90 80-90 80 80 Acetate Oil-repellency 8 8 7 7 7 6-7 Water-repellency 90-100 100 90 90 80-90 80 Chlorovinyl Oil-repellency 8 8 7 7 7 6-7 Water-repellency 100 100 90 90 80-90 80 ____________________________________________________________ ______________

A = product prepared as in Example 15

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.

In 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 17

29.2 g C ₄ F ₉ --COOC ₂ H ₅ (0.1 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 ₄ in order to remove the reaction by-product C ₂ H H ₅ OH, thereby obtaining 33 g of an oily yellowish product which was dissolved in a 50percent by volume mixture of acetone and C ₂ Cl ₃ F ₃ . The product was found to be insoluble in the chlorinated solvents mentioned in the preceding examples, slightly soluble in 1,1,2-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, 100percent wringing and heat-treating at 120° C during 10 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-repellency none none none Water-repellency 0-50 0-50 0-50 Shrinkage area % 0.8 1.0 1.2 ____________________________________________________________ ______________

EXAMPLE 18

44.2 g C ₇ F ₁₅ COOC ₂ H ₅ (0.1 mols) and 8.6 g (0.2 mols) ethylenimine were reacted as previously described in Example 1.

The resulting product, which was insoluble in the chlorinated solvents repeatedly mentioned in the preceding examples, was reacted, in a solution of 1,1,2-trichlorotrifluoroethane and acetone, with 16.8 g hemamethylene-diisocyanate OCN-(CH ₂ ) ₆ --NCO similarly dissolved in C ₂ Cl ₃ F ₃ and brought to boiling temperature. The result was a liquid dispersion which was insoluble in chlorinated solvents; moreover, the dispersion was unstable and when stirred gave rise to agglomerates insoluble in all tested solvents and their mixtures, even at elevated temperature.

EXAMPLE 19

12.9 g aziridine and 86.5 g C ₇ F ₁₅ COCl were reacted as previously described in Example 5.

The resulting product, in a solution of 1,1,2-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: ##SPC6##

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;

c. 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-COCl + 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 ₃ CH ₂ ) ₂ O 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 perfluoroacylamido 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 50-80percent by volume (such as 1,1,2-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 ₂ groups, and ensuing reaction with the remaining --NCO groups leading to the formation of insoluble rubbers and polyurethane foams;

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, inter- and 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 solvents formed as follows:

a. a fluorochlorinated organic solvent in a proportion of 50-80percent by volume (such as 1,1,2-trichlorotrifluoroethane)

b. a polar organic solvent in a proportion of 20-50percent 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 ₂ 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 100-170 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 atm. 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 120-150percent by weight or about 80-100percent by volume, more particularly:

rate of feed absorption ____________________________________________________________ ______________ wool cloth 8 m/min. 80% vol. carded wool cloth 5 m/min. 105% vol. acrylic fabric 7 m/min. 102% vol. cotton cloth 5 m/min 100% vol. cotton/polyester cloth 10 m/min. 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.

1.2 -- Treatment by dipping: In this case also weighed fabric strips 100-170 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 ² ). 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:

2.1 -- 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 10 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 2.1 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 1 minute, stopped during 1 minute and run again during 1 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 2percent 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 of improved 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

Leather and hides and skins treated by spraying with solutions of the instant compounds in chlorinated organic solvents acquired a considerable fastness against water and corrosive agents generally.

Coating of paper was found to be of particular interest in respect of packaging material for food. Though the treated paper maintained its porosity, it proved to be particularly fast against smearing and effectively protected against water.