DD249267A5 - PERCUSSIONAL CYL AND EPICHLORHYDRIN GROUPS CONTAINING URETHANES, WAFERDING DISPERSIONS CONTAINING THESE URETHANES AND THEIR USE - Google Patents

Abstract

The new urethanes correspond to the following formula I, in which a is a number from 5 to 17 and b is a number from 1 to 7. These urethanes are prepared by reacting the corresponding perfluoroalkylethanol-epichlorohydrin adducts with toluene diisocyanates. The new aqueous dispersions consist essentially of the new urethanes, cationic or betainic and nonionic emulsifiers, water-insoluble carboxylic acid and / or dicarboxylic acid esters and alkanediols or polyalkanediols, which may have been etherified on one or both sides, in water. The new urethanes and the new aqueous dispersions are used for the oleophobic and hydrophobic treatment of textiles, leather and furs. They are also suitable for the treatment of unpainted wood, such as unpainted furniture. Formula I

Description

67 289 18

AP G 07 C / 29 3 937.0

Process for the preparation of perfluoroalkyl and. Epichlorohydrin-containing urethanes

Field of application of the invention

The invention relates to novel perfluoroalkyl- and epichlorohydrin-group-containing urethanes, to these novel urethane-containing aqueous dispersions, and to the use of these urethanes and dispersions.

Characteristic of the known technical solutions

US Pat. Nos. 4,264,484, 4,340,749 and 4,468 describe urethanes containing perfluoroalkyl and epichlorohydrin groups and have the following formula (compare formulas I, V and VIII of said patents),

R ₁ 0

ι ¹ ί!

in which mean

R. £ a fluoroaliphatic radical,

Q is a divalent group which is free from epoxy-reactive and isocyanate-reactive groups, for example a -CO-, -COM-, -SO ₂ KR-, -SO ₂ ----, -C _n Hp _n -, - G ₆ H ₄ -, -C ₆ H ₃ Cl- or -OC ₂ H ₄ -GrUpPe or combinations thereof, where R is a hydrogen atom or an alkyl radical having 1 to 6 carbonatora and η 1 to 20,

butadder 1, R _{1 is} a hydrogen atom or a lower alkyl radical,

, 1 r

R _{2 is} a hydrogen atom, a lower alkyl radical or an aryl radical having 6 to 12 carbon atoms, or R ₁ and R ₂ are joined together to form an aromatic or cycloaliphatic structure, ρ is a number having a small value, for example 1 to 5,

o a number which is equal to the number of isocyanate groups in the isocyanate, for example 2 to 5, and

R _{3 is} the isocyanate-free radical of an organic polyisocyanate, such as 2,4-tolylene diisocyanate.

These urethanes are recommended as a means of treating textiles.

Purpose of the invention

It is intended to provide novel and particularly effective perfluoroalkyl and epichlorohydrin-containing urethanes as agents for the treatment of textiles, leather and furs.

Explanation of the essence of the invention

It has now been found that urethanes of the formula given above, then have particularly advantageous properties with regard to the treatment of textiles, leather and fur, if R ^ / Qr rn, R _1, R ₂ ρ, ο and R ₃ special meanings or Namely assume numerical values, namely, when R _{f is} a selected fluoroaliphatic radical, namely a straight-chain perfluoroalkyl radical, Q is -CH ₂ -, m 1, R ₁ and R _{2 are} H, ρ is 1 to 7, preferably 1 to 3, ο 2 and R _{3 is} the 2,4- or 2,6-tolylene diisocyanate residue.

The invention therefore relates to compounds of the following formula I,

O CF ₃ - (CF ₂ ) _a -CH ₂ -CH ₂ -O- (CH ₂ -CH-O) _h -CNH

²

O Il /

CF ₃ - (CF _{2) a} -CH ₂ -CH ₂ -0- (CH ₂ -CH-O) _b ~ CNH

CH ₂ Cl

in the a is a number from 5 to 17, preferably 7 to 15, and b is a number from 1 to 7, preferably 1 to 3, mean.

The preparation of the urethanes according to the invention, which are bis [perf luoralkylethoxy- (chloroethylethoxy) carbonylamino] -toluenes, is preferably carried out in such a way that first the perfluoroalkylethanol-epichlorohydrin adduct is prepared, and this adduct is reacted with tolylene diisocyanate.

For the preparation of the perfluoroalkylethanol-epichlorohydrin adduct, the procedure is preferably such that a perfluoroalkylethanol of the following formula II

CF ₃ - (CF ₂ ) _a -CH ₂ -CH ₂ -OH,

wherein a has the abovementioned meaning, or a mixture of such perfluoroalkylethanols with epichlorohydrin in the presence of Lewis acids as catalyst at a temperature of 50 to 150 ⁰ C, preferably 70 to 90 ⁰ C reacted. The following reaction equations, in which a and b have the abovementioned meaning, are intended to illustrate this:

CF 3 - (CF 2) _a -CH ₂ -CH 2 -OH + b CH ₂ -CH-CH ₂ Cl->

No

CF ₃ - (CF ₂ U-CH ₂ -CH ₂ -O- (CH ₂ -CH-O) _h -H

I

CH ₂ Cl

The perfluoroalkylethanol is generally inexpensive, commercially available mixtures in which the average of a is preferably 8 to 12. The nature of the Lewis acid is not critical. Preference is given to BF ₃ , boron trifluoride diethyl etherate, SnCl 4 / SbCl ₅ , TiCl ₄ , FeCl ₃ , PF ₅ and / or dibutyltin dilaurate, boron trifluoride diethyl etherate being particularly preferred. The amount of catalyst is generally from 0.01 to

-A-

5 wt .-%, preferably 0.1 to 1 wt .-%, based on perfluoroalkylethanol. The reaction is preferably carried out with stirring and at the pressure which is obtained, the liquid epichlorohydrin (boiling point under normal conditions 116 ^° C.) being added to the initially introduced alcohol. The reaction time is in the range of about 0.5 to 7 hours. It may be appropriate to use a solvent. Preferred solvents are halogenated hydrocarbons such as carbon tetrachloride, trichlorethylene, 1,2-dichloroethane, trichloroethane, pentafluoromonochloroethane and trifluorodichloroethane; Ketones such as methyl ethyl ketone and cyclohexanone; Ethers such as diisopropyl ether and tetrahydrofuran; Dimethylformamide and N-methylpyrrolidone.

The implementation in question is proceeding quantitatively. In the resulting reaction product, the solvent optionally used is distilled off, wherein any volatile components present such as unreacted epichlorohydrin are removed. For convenience, distillation may also be carried out under vacuum (water jet

> vacuum). The Lewis acid used as a catalyst, which does not interfere with the subsequent reaction with tolylene diisocyanate per se, can be washed out or neutralized with the aid of alkaline agents, preferably with the aid of an aqueous sodium bicarbonate solution or an amine such as triethylamine.

For reacting the perfluoroalkylethanol-epichlorohydrin adduct with toluene diisocyanate, the procedure is preferably such that initially introducing the adduct compound (by heating melts), at a temperature of 50 to 150 ⁰ C, preferably 70 to 120 ⁰ C, the toluylene diisocyanate and in the above Allow the temperature to react. This reaction is also preferably carried out with stirring and at the pressure which is established. The

2 4 9 2ο /

Implementation time is in the range of 1 to 15 hours. If appropriate, the abovementioned solvents can also be used here. Suitable tolylene diisocyanate are 2,4- and / or 2,6-tolylene diisocyanate, preferably in the form of a commercial product containing about 80% by weight of 2,4-tolylene diisocyanate and about 20% by weight of 2,6-tolylene diisocyanate contains. The reaction of the perfluoroalkylethanol-epichlorohydrin adduct with toluene diisocyanate proceeds quantitatively and gives the urethanes according to the invention as solid (waxy) products of the desired purity.

The compounds according to the invention are surprisingly good treatment agents for textiles, leather and fur (fur velor) and for unpainted wood, in particular for textiles, leather and furs. Above all, they give these articles excellent hydrophobicity and oleophobicity. They also have, to an unexpectedly high degree, the property of withstanding the severe stresses to which the finished textiles and leather and furs are subjected, such as stretching, texturing, dyeing and laundering, without any loss of effect ,

The textile material may be natural and / or synthetic nature. It is preferably made of polyamide, polyester and / or polyacrylonitrile, with polyamide being particularly preferred. The textile material can be present in any desired form, for example as thread, fiber, yarn, flake, fabric, knitted fabric, knitted fabric, carpet or fleece. The amount applied to the compound of the invention is selected so that 0.02 to 1 wt .-% fluorine, preferably 0.04 to 0.4 wt .-% fluorine, are present on the textile material, calculated from the amount of fluorine in the inventive Connection; Weight percentages based on the treated textile material. The type of leather and fur is not critical. The leather may be, for example, a beef, goat, sheep or pork leather and the like. The fur may be, for example, sheep's velor, mink, raccoon or similar noble fur.

The amount applied to the compound according to the invention is selected so that 0.05 to 1.5 wt .-% fluorine, preferably 0.1 to 1 wt .-% fluorine, are present on the leather or fur, calculated from the amount of fluorine in the compound of the invention; Weight percentages based on the treated material (leather or fur).

It has been found that the above-mentioned effects of the novel perfluoroalkyl- and epichlorohydrin-containing urethanes of the abovementioned formula I are achieved, above all, when they are used in the form of a specific aqueous dispersion.

The aqueous dispersions of the invention consist essentially of

A) from 5 to 30% by weight, preferably from 10 to 25% by weight, percentages by weight, based on the aqueous dispersion, of at least one compound of the formula I as active ingredient,

B) 1 to 10% by weight, preferably 3 to 7% by weight, percentages by weight, based on the amount of active ingredient, of at least one cationic or betaine emulsifier containing at least one perfluoroalkyl radical,

C) 0 to 20% by weight, preferably 5 to 14% by weight, based on the amount of active ingredient, of at least one nonionic emulsifier,

D) 50 to 120 wt .-%, preferably 80 to 110 wt .-%, weight percent, based on the amount of active ingredient, of at least one water-insoluble carboxylic acid or dicarboxylic acid ester having 5 to 16 carbon atoms, preferably 6 to 14 carbon atoms, the at 20 ⁰ C and is liquid at normal pressure has a boiling point of at least .100 ⁰ C,

E) 15 to 60 wt .-%, preferably 20 to 40 wt .-%, weight percent based on the amount of active ingredient, of at least one water-soluble alkanediol or polyalkanediol having 2 to 20 carbon atoms, wherein the alkanediol and the polyalkanediol with 1 or 2 alkyl groups having 1 to 4 carbon atoms can be etherified, and

F) as much water or of a water-in-oil emulsion with at least 50 wt .-% water, based on the emulsion that 100 wt .-% aqueous dispersion are present.

As component A), preference is given to using those compounds of the formula I which result if a is a number from 7 to 15 and b is a number from 1 to 3. The following compounds in which the perfluoroalkyl radical R 1 [corresponds to the radical CF ₃ - (CF ₂ ) of the formula I]

x. a ~

C ₈ F ₁₇ to Ci ₆ F ₃₃ , in the form of the individual compound or in the form of technical mixtures, and b 1,2

especially> to 2.4 / "5Tncl

O CH ₂ Cl

NHC (0-CH-CHζ) _b -O-CH ₂ -CH ₂ -R _'f

0 CH ₂ Cl

CH ₃ XNHC- (O-CH-CH ₂ ), -O-CH ₂ -CH ₂ -R '

As component B) are preferably cationic and betaine emulsifiers of the formula

R ⁴ R ⁴

[R "-CF =CH-CH ₂ -NR ⁶ ] ^Θ Χ ^Θ or R" -CF = CH-CH ₂ -N- (CH ₂ ) ₃ Sof

used in which R ¹ I is a perfluoroalkyl radical having 5 to 13 carbon atoms, which may contain a terminal CF ₂ H group, preferably C ₅ F ₁₁ , C ₇ F ₁ S, C ₉ F ₁₉ , Ci ₁ F _23th and C ₁₃ F ₂₇ , R ⁴ , R ⁵ and R ⁶ , which may be the same or different, is an alkyl group having 1 to 4 carbon atoms which may be substituted by hydroxyl, and X is a monovalent anion, preferably chloride, Bromide, sulfate or alkyl sulfate with 1 to 2 C atoms. The compounds listed below in which R " _{f is} C ₅ F ₁₁ , C ₇ F ₁₅ , C ₉ F ₁₉ , C ₁₁ F ₂₃ or C ₁₃ F ₂₇ are particularly preferred cationic emulsifiers:

[R '| -CF = CH-CH ₂ -N (CH ₃ ) ₃ ] ⁹ SO ₄ CH ₃ ⁹ [R ¹ ^ -CF = CH-CH ₂ -N (CH ₃ ) 3] ®C ^{e e} [R' | -CF = CH-CH ₂ -N (C ₂ H ₅ ) ₂ CH ₃ ] ®SO ₄ CH ₃ ⁹

[R 1 -CF = CH-CH ₂ -N (C ₂ Hs) ₂ CH ₃ ] ⁸ Cl ⁹ [R '| -CF = CH-CH ₂ -N (C 3 H 7) ₂ CH 3] ® S0 4CH 3 ^θ [R 1 -CF = CH-CH ₂ -N (C ₄ H ₉ ) ₂ CH ₃ ] ⁹ SO ₄ CH ₃ ⁶ [R ¹ -CF = CH-CH ₂ -N (CH ₃ ) ₂ CH ₂ CH ₂ OH] ⁶ SO ₄ CH ₃ ⁶ [R 1 -CF = CH-CH ₂ -N (CH ₃ ) ₂ CH ₂ CH ₂ OH] CC 1 ⁶ [R 1 -CF =CH-CH ₂ -NH-CH ₂ -CH ₂ Oh] ®C1 ⁶

[R ¹ -CF = CH-CH ₂ -N

CH ₂ OH

CH;

R ¹ ICF = CH-CH ζ -N-CH ₃

Cl

These emulsifiers can be used as such or dissolved in a solvent; As solvents, preferably lower alkanols such as methanol, ethanol, propanol and / or isopropanol, optionally together with water, are used. The cationic emulsifiers are preferred.

As component C) it is preferred to use nonionic emulsifiers of the polyoxethylenesorbitan monooleate or polyoxethylenesorbitan monostearate type having 10 to 30 ethylene oxide units. Particularly preferred are polyoxyethylene sorbitan monooleates having from 10 to 30 ethylene oxide units, for example polyoxyethylene sorbitan monooleate having 20 ethylene oxide units, which is known under the trade name Tween 80.

As component D) it is preferred to use butyl acetate, ethyl propionate, methyl butyrate, glycol bisacetate, propanediol bisacetate, diethyl succinate, dimethyl adipate, dibutyl adipate, individually or mixed with one another. Particularly preferred is a mixture of a monocarboxylic acid ester, preferably butyl acetate, and a dicarboxylic acid ester, preferably adipic acid

-S

dibutyl; the ratio of monocarboxylic acid ester to dicarboxylic acid ester is 1: 1 to 1: 5, preferably 1: 2.

Monoethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, pentaethylene glycol, the corresponding propylene glycols, the (C 1 -C 4) monoalkyl or dialkyl ethers of these ethylene and propylene glycols are preferably used as component E), with diethylene glycol dimethyl ether and dipropylene glycol monomethyl ether being particularly preferred.

The compounds corresponding to components B) to E) are commercially available. They can also be used in the form of their technical mixtures, which usually contain several compounds of the type mentioned (homolog mixtures).

In addition to the components A) to F), the aqueous dispersions according to the invention may also contain further suitable components. Thus, the dispersion may contain a water-insoluble or sparingly soluble, aliphatic ketone having a boiling point above 100 ⁰ C; Examples include aliphatic ketones having 5 to 8 carbon atoms such as diethyl ketone, methyl propyl ketone, methyl isobutyl ketone and the like. These ketones are used in an amount of preferably 5 to 10% by weight, based on the weight of the aqueous dispersion, and can replace a corresponding part of component D).

The preparation of the aqueous dispersions according to the invention is carried out by mixing together the individual components. In this case, the procedure is preferably such that the components A), B), C), D) and E) are dispersed in water (component F) while supplying a relatively large amount of energy. The proportions for the

Components are chosen so that after dispersing the specified composition for the dispersion is achieved. It has proved to be advantageous that the component A) (that is, the compound of the invention, the active ingredient) at least in a part of the applied amount of component D) and E) is predispersed and used in this form. It has also proved to be advantageous to divide the preparation of the aqueous dispersion into two substeps and to first carry out a predispersion and then a fine dispersion. Predispersion is conveniently carried out by the use of high shear forces, such as are present when using a high-speed stirrer, such as an Ultraturrax type stirrer (dispersing machine), and the predispersion (crude dispersion) obtained is then conveniently subjected to ultrasonic treatment or treatment in a high-pressure homogenizer , After completion of this treatment, the particle size in the dispersion is more than 80%, preferably more than 35 %, at or below 1 pm (fine dispersion).

The invention finally relates to the use of the described aqueous dispersions. They are used according to the invention for the treatment of textiles, leather and fur and of unpainted wood (preferably unpainted furniture). They give these articles excellent hydrophobic and oleophobic finish. When applied to textiles, the aqueous dispersions can be used in the form in which they are obtained in the production. Normally, however, they will be adjusted with water to a solids content of 1 to 10% by weight, preferably 1.5 to 5% by weight (percentages by weight based on the aqueous dispersion), and used in this more diluted form.

To coat pre-broached leathers and furs, the aqueous dispersions can be used directly and without further predilution in the form in which they are obtained in the preparation in the case of bath application. However, for the finishing of dry leathers and furs by the spray application method, they are normally adjusted beforehand with water to a solids content of 1 to 10% by weight, preferably 4 to 5% by weight (percentages by weight based on the aqueous dispersion) use in this diluted form.

I: ,; 5 / - 11 -

The aqueous dispersions of the invention meet all the requirements of practice and in particular show excellent long-term stability at temperatures of -20 to + 40 ⁰ C. Although they freeze at minus temperatures, but the dispersion is retained after thawing. In addition to the excellent oleophobization and hydrophobing, a general dirt repellency and also a conductivity improvement is achieved. The aqueous dispersions described can be used both alone for the equipment in question, as well as in combination with, for example, conventional spin finishes or other finishing agents such as antistatic agents, optical brighteners, glyoxal-based or derivative-based textile resins, plasticizers and dispersions of polyvinyl alcohol and ethylene-vinyl acetate polymers, mineral and synthetic tanning agents and resin and polymer tanning agents.

Regarding the nature and form of the textile material used for the treatment, the above applies. The textile material can therefore be natural or synthetic nature. The aqueous dispersions are particularly advantageous in a textile material of polyamide, polyester and / or polyacrylonitrile, in particular of polyamide. The textile material may be in any form; usually it will be threads, fibers, fabrics or carpets. The treatment of textile material with the aqueous dispersions according to the invention is carried out by customary methods, for example by spraying, dipping, patting, padding and the like. The amount applied is chosen so that the amount of fluorine of the active ingredient (compound of the invention) on the textile material 0.02 to 1 wt .-%, preferably 0.04 to 0.4 wt .-%, percentages by weight based on the treated textile material , After application to the textile material to be treated, drying at temperatures up to about 120 ⁰ C, for example at 100 to 120 ⁰ C, and then a heat treatment at temperatures of about 130 to 190 ⁰ C, preferably 140 to 180 ^0th C, which normally takes about 30 seconds to about 4 minutes (unless drying and heat treatment are carried out in the course of the production of the textile material anyway).

As mentioned above, there are no restrictions on the type and origin of the leathers and furs to be finished. However, before treatment with the aqueous dispersion, they should as far as possible not be covered with highly water-repellent agents, such as a polyurethane coating, in order to achieve safe and uniform penetration.

The treatment of the leather and furs with the aqueous dispersions according to the invention is carried out by the customary methods, for example in the bath, by dipping, brushing or spray application. The order amount is chosen so that the amount of fluorine offered of the active ingredient (compound of the invention) for the leather and fur material 0.05 to 1.5 wt .-%, preferably 0.1 to 1 wt .-%, based on weight percent the leather and fur material to be treated. After treatment with the aqueous dispersion according to the invention, the leather and fur material can be dried and finished as usual. The treatment with the aqueous dispersion according to the invention does not affect the color or the feel of the treated leather and furs, nor is the free play of the wool and hair of furs impaired by the bonding of the same.

The invention will now be explained in more detail by way of examples.

Embodiment e

Compounds of the Invention 1. Preparation of perfluoroalkylethanol-epichlorohydrin adducts

example 1

1.5 kg (2.78 mol) of a commercially available perfluoroalkyl ethanol mixture (perfluoroalkyl = C ₆ F ₁₃ to C ₁₄ F ₂₉ ; -value = 104), 450 ml of 1,2,2-trifluorotrichloroethane (CFCl ₂ -CF ₂ Cl; Kp = 48 ⁰ C) as the solvent and 15 g of boron trifluoride diethyl etherate as the catalyst (these are 1 wt .-% of catalyst, based on perfluoroalkylethanol ) submitted. 309 g (3.34 mol) of epichlorohydrin were added dropwise at 50 ^° C. (under cooling) to this solution, followed by stirring for 2 hours at the boiling point of the solvent. Now, the contents of the flask to remove the catalyst with 1 1 one

- T 3 - / ί 4 y

Washed 4 wt .-% aqueous sodium bicarbonate solution, then washed twice with water and distilled to remove the solvent in vacuo (water jet vacuum).

The obtained perfluoroalkylethanol-epichlorohydrin adduct (1.77 kg, yield: 97.6% by weight of theory) was a solid (waxy), yellow-colored product (OH number 85.9); its gross composition corresponds to the formula (molar ratio of perfluoroalkylethanol to epichlorohydrin = 1: 1.2):

(C ₆ Fi 3 "C _{1 4} F ₂₉ J-CH ₂ CH ₂ O- (CH ₂ -CHO) i, ₂ -H.

CH ₂ Cl

Example 2

In a 250 ml flask equipped with stirrer, reflux condenser, thermometer, dropping funnel and heating bath, 150 g (0.28 mol) perfluoroalkylethanol commercially available mixture (perfluoroalkyl = C ₈ Fw to Ci ₆ F ₃₃ , OH number = 105.4 ), by heating to 70 ⁰ C melted and mixed with 1.3 g of boron trifluoride diethyl etherate as a catalyst, whereupon at a temperature of 70 to 90 ⁰ C 36.5 g (0.40 mol) of epichlorohydrin were added. The mixture was then reacted for 3 hours at 75 ⁰ C. The contents of the flask were then added to neutralize the catalyst with 0.9 g of triethylamine and then distilled to remove volatile components at 75 ° C and 15 mbar. A solid (waxy) yellow colored product (186.8 g, yield: 99.4% by weight of theory, OH number = 79.7) was obtained. Its gross composition corresponds to the formula (molar ratio of perfluoroalkylethanol to epichlorohydrin = 1: 1.4):

(C ₈ F ₁ 7-C 1 ₆ F ₃₃ J-CH ₂ CH ₂ O- (CH ₂ CHO) _1/4 -H.

CH ₂ Cl

Examples 3 to 6

The procedure was in each case analogous to Example 2, the perfluoroalkylethanol and the epichlorohydrin being used in the downstream

example 3 1 : 1, 6 example 4 1 : 1.8 example 5 1 : 2.0 example 6 1 : 2.4

standing summarized molar ratios were used. The summary also includes the yield and OH number of the resulting perfluoroalkylethanol-epichlorohydrin adducts.

Molar ratio of perfluoro OH number

alkylethanol to epichlorohy- (wt%)

in it

99.0 78.1

99.1 76.3 98.7 75.4

Example 6 1: 2.4 99.2 72.2

The gross composition of the compounds obtained according to Examples 3 to 6 corresponds to the formula of the compound of Example 2 with the exception that instead of the index 1.4, the indices are 1.6, 1.8, 2.0 and 2.4, respectively.

2. Preparation of diurethane compounds according to the invention

Example 7

In a 11 flask equipped with stirrer, condenser with drying tube, thermometer, and heating bath 548.5 g (0.84 mol) perfluoroalkylethanol epichlorohydrin adduct from Example 1 at 80 ⁰ C were submitted melted. To this was added dropwise 73.1 g (0.42 mol) of toluene diisocyanate, specifically a mixture of 80% by weight of 2,4-tolylene diisocyanate and 20% by weight of 2,6-tolylene diisocyanate (commercial product), followed by 5 hours was stirred at 110 ⁰ C. The resulting diurethane compound (614 g, yield: 98.8% by weight of theory) was a solid (waxy) yellow-colored product having a fluorine content of 51.4% by weight. Its gross composition corresponds to the formula

CH ₂ Cl

(C ₆ F ₁₃ -C

4F ₂ S) -CH ₂ CH ₂ O- (CH ₂ -CHO) _{t 2} -CNH

I /

CH ₂ Cl

Examples 8 to 12

The procedure was analogous to Example 7, wherein the perfluoroalkylethanol-epichlorohydrin adducts of Examples 2 to 6 were reacted with toluene diisocyanate in a molar ratio of 2: 1. The respective yield and the fluorine content of the compounds obtained are summarized below:

8th Perfluoroalkylethanol-epichlorohydrin adduct from Example Yield (% by weight) Fluorine content (wt%) example 9 2 97.3 50.3 example 10 3 98.5 49.3 example 11 4 99.1 48.1 example 12 5 97.7 47.0 example 6 99.6 46.0

The gross composition of the invention obtained according to Examples 8 to 12. Compounds correspond to the formula of the compound of Example 7 with the exception that instead of the radical C ₆ F ₁₃ - C ₁₄ F _{29 is} the radical C ₃ F ₁₇ C ₁₆ F ₃₃ and instead of the index 1,2, the indices 1,4, 1.6, 8.1, 2.0 and 2.4, respectively.

Aqueous dispersions according to the invention

Example 13

10 kg of aqueous dispersion according to the invention were prepared by mixing together the following components A) to F):

A) 1.74 kg of the compound (active substance) according to the invention according to Example 10,

B) 0.10 kg of cationic emulsifier (in 0.14 kg of isopropanol and 0.02 kg of water as solvent) of the formula below

[C ₉ F ₁ S-CF = CH-CH ₂ -N (C ₂ Hs) ₂ CH ₃ ] ⁹ SO ₄ CH ₃ ⁹

C) 0.20 kg polyoxethylenesorbitan monooleate with 20 oxyethylene units (commercial product Tween 80) as nonionic emulsifier,

D) 1.50 kg of adipic acid dibutyl ester (1.0 kg) and butyl acetate (0.5 kg),

E) 0.50 kg of diethylene glycol dimethyl ether, and F) 5.80 kg of water.

The sum of A) to F) plus solvent for component B) is 10.00 kg. If the amount of active substance and the amount of water on the aqueous dispersion and the amount of components B) to E) are respectively based on the active substance, the weight percentages given below for components A) to F) are as follows: A) 17, 4% by weight

B) 5.7% by weight

C) 11.5% by weight

D) 86.2% by weight

E) 28.7% by weight

F) 58.0 wt .-%.

The preparation of the dispersion according to the invention was carried out in detail as follows:

5.8 kg of water (component F) and 0.25 kg of a 40% strength by weight solution of the cationic emulsifier (component B) were stirred in 90% strength by weight aqueous isopropanol in a 20 l nozzle 0.1 kg of cationic emulsifier and 0.16 kg of solvent from 0.14 kg of propanol and 0.02 kg of water introduced). In this mixture at room temperature was under the strong shearing action of a dispersing machine of the type Ultraturrax eine80 ⁰ C hot solution of 1.74 kg of active ingredient (component A) in 0.2 kg Polyoxethylensorbitanmonooleat 20 Oxethylen-Einheiteh (component C), 1.0 kg Adipinsauredibutylester and 0.5 kg of butyl acetate (component D) and 0.5 kg diethylene glycol dimethyl ether (component E) stirred, the temperature in the template to 35 ⁰ C increased. The coarse dispersion was further treated for about 30 minutes with the Ultraturrax, the temperature rising to 40 to 45 ⁰ C. This was already an externally appealing emulsion, but in this form is not stable in storage, but would soon settle.

The crude dispersion obtained was then subjected to a final fine dispersion by sonication by means of an ultrasound machine (Branson Sonifier type) until at least 90% of the particles had reached or fallen below an average size of 1 .mu.m. In order to achieve the best efficiency of the ultrasound machine and an optimal sound, pumping best, the raw dispersion by the tempered at 40 ⁰ C acoustic chamber (the temperature of the acoustic chamber is achieved by means of a regulated by a thermostat water bath) until the necessary fine distribution is present, which may require a second and a third pass, if necessary; Throughput speed 10 l / h

 This gives 10 kg of a very fine milky opaque dispersion containing 8% by weight of active fluorine.

-18- <- i -: ο s

(calculated from the amount of active substance in the dispersion), which is still stable storage at -20 ⁰ C and + 40 ⁰ C.

Example 14

The procedure was as in Example 13, wherein as component A) 1.51 kg of the inventive compound (active substance) were used according to Example 7. It was adjusted as in Example 13 to 10 kg of aqueous dispersion using an appropriate amount of water. There was a beautiful, stable dispersion with an effective fluorine content of 8% by weight. The dispersion thus consisted of A) 1.51 kg; B) 1.10 kg with a total of 0.16 kg of solvent; C) 0.20 kg; D) 1.50 kg;

E) 0.50 kg; and F) 6.03 kg.

If the amount of active substance and the amount of water on the aqueous dispersion and the amount of components B) to E) are in each case based on the active substance, the weight percentages given below for components A) to F) are as follows:

A) 15.1% by weight

B) 6.6% by weight

C) 13.2% by weight

D) 1.00.0% by weight E) 33.1% by weight

F) 60.3 wt .-%.

Example 15

The procedure was as in Example 13, wherein 1.76 kg of the inventive compound (active substance) were used according to Example 11 as component A). It was adjusted as in Example 13 to 10 kg of aqueous dispersion using an appropriate amount of water. There was a beautiful, stable dispersion with an effective fluorine content of 8% by weight.

Due to the small difference between 1.74 kg of component A) in Example 13 and the 1.76 kg in this example, the amounts of components A) to F) in percentages by weight, based on the active substance or on the aqueous dispersion, are almost equal the corresponding amounts in Example 13

Example 16

The procedure was as in Example 13, wherein 1.77 kg of the inventive compound (active substance) were used according to Example 12 as component A). As in Example 13, 10 kg of a beautiful, stable aqueous dispersion having an effective fluorine content of 8% by weight was obtained.

With regard to the amounts of components A) to F) in percentages by weight, based on active substance or on aqueous dispersion, the statements made at the end of Example 15 also apply to this example.

0 Application examples for textiles Examples 17 to 20

The compounds according to the invention of Examples 8 to 11 were tested. The compounds were applied to a nylon-6 filament web using a padder and a pick-up of 30-40% by weight. The amount of compound (active substance) according to the invention in the liquor was in each case selected such that each time about 0.05% by weight of fluorine (active fluorine) was present on the fabric after the condensation (percentages by weight based on the weight of the fabric) , The liquor consisted of about 1.2 g of the compound according to the invention in 250 ml of acetone (acetone liquor). The acetone wet tissues were first air dried and then condensed (fixed) at 160 ^° C. for 1 minute.

On the fabrics thus obtained, the oil repellency values were determined according to AATCC Test Standard 118-1978, according to the

Condensation and after 3 h treatment with an alkaline cooking wash consisting of 1 1 of water, 1 g of trisodium phosphate and 2 g of a fatty acid polyglycol ester, which was obtained by oxethylation of 1,4-butanediol with 15 moles of ethylene oxide and subsequent esterification of the oxyethylate with 1 mol of oleic acid , Further, the fluoro-overlay (F-pad in% by weight, based on the weight of the fabric) was determined after condensation and after alkaline cooking wash. The results are summarized in the table below:

Connectivity Ölabwei- Ölabwei- F Pad F Pad F-retention from after after after after the Bei the condenses the chef Konden Cottons play sation Laundry sation (Wt .-%) (Wt .-%) (Wt .-%) - 4 0.056 0.028 8th 4-5 4 0,055 0.031 50 9 4-5 5 0,060 0.027 56 10 5 3-4 0,060 0.023 45 11 5 39 Examples 21 to 24

The novel aqueous dispersions of Examples 13 to 16 were tested. The dispersions were diluted with water to a solids content of 2 to 4% by weight. The diluted dispersions (liquors) were applied to a woven fabric of polyamide 6 filaments by means of a padder and with a liquor pick-up of 30 to 40 wt .-%, so that each time about 0.05 wt .-% support of fluorine ( effective fluorine) on the tissue after condensation (percentages by weight of the weight of the tissue). The wet-wet fabrics were first dried at temperatures up to 120 ⁰ C and then condensed for 3 minutes at 200 ⁰ C. On the fabrics thus obtained, the oil repellency values were determined according to the AATCC Test Standard 118-1978, namely

2 49

Condensation and after 3 h of treatment with the above-mentioned alkaline cooking wash. Further, the fluoro-overlay (F-pad in% by weight, based on the weight of the fabric) was determined after condensation and after alkaline cooking wash. The results are summarized in the table below:

Aqueous Dis- Oilseed Oilseed F-Pad F-Pad F-Retention persion from solution to after after

the cooking-Konden- cooking laundry

laundry sation

(Wt .-%)

the example of condensation

(Wt .-%)

(Wt .-%)

13 5 5 0,051 0,025 49 14 5 3 0,049 0,021 43 15 5 3 0.048 0,020 42 16 5 5 0,050 0.023. 46 Comparative example

The US patents cited at the outset particularly recommend urethanes containing such perfluoroalkyl and epichlorohydrin groups which, in contrast to the urethanes according to the invention, contain an -SO ₂ NR group (see the examples of the US patents). In this comparative example, the following compound described in Example 4 of the US patents was tested:

C ₈ F ₁₇ -SO ₂ N (CH ₃ ) CH ₂ -Ch ₂ -O- (CH ₂ -CH-O) _{1 #}

CH ₂ Cl

C ₈ F ₁₇ -SO ₂ N (CH ₃ ) CH ₂ -CH ₂ -O- (CH ₂ -Ch-O) ^ ₁ -CNH

CH ₂ Cl

The procedure was as in Examples 17 to 20. On the after treatment with the acetone fleet

and condensation at 160 ^° C., as well as in Examples 17 to 20, the oil repellency values after the condensation and after 3 hours of treatment with the alkaline cooking wash were determined. Further, the fluorine coverage (F-weight percent based on the weight of the fabric) was determined after condensation and after alkaline cooking wash. The results are summarized below:

Oil Repellency Oil Repellent F-Pad F-Pad F-Retention

after the after the after the

Condensation cooking linen condensation cooking linen

(Wt.-Z) (wt. -7.) (Wt.%)

5 1 0.092 0.065 71

As the results show, with the compounds according to the invention substantially higher oil repellency values are achieved after cooking, that is to say that the compounds according to the invention have, inter alia, the particularly important property of being able to withstand the extremely high stresses in the cooking laundry.

Application examples for leather and furs

Examples 25 to 28

The compounds according to the invention of Examples 8 to 11 were tested. The compounds were applied by spraying onto untrimmed leather. The amount of compound (active ingredient) according to the invention applied was in each case selected such that about 0.5 to 0.6 g of fluorine per m ^{2 of} leather surface were applied. The order was carried out in each case as 0.5% strength by weight acetone active substance solution. After evaporation of the solvent and one-day storage of the thus treated leather, the water-repellent effect was measured by means of water trench morphine (measurement of the time that elapses until the

Absorption of an attached drop of water of a defined size by the leather).

While the applied water droplet was absorbed on untreated leather after 2 to 5 minutes, on the leather finished with the inventive compounds of Examples 8 to 11 residence times of the added water droplets until absorption of more than 1 h, usually from 2 to 3 h is watching. 10

Examples 29 to 32

The novel aqueous dispersions of Examples 13 to 16 were tested.

The application of the dispersions on untreated leather was carried out both after the injection process and after the bath process.

For application by spraying, the aqueous dispersions according to the invention were diluted with water to solids contents of 4 to 8% by weight. With the spray gun in each case about 1.6 g of fluorine / m ² leather were applied. After drying, milling or brushing, the water repellency by means of the waterdrop sample and the oil repellency were tested by the AATCC test 118.

While a non-equipped comparative sample reached less than 5 minutes in the water drop test and only 1 oil repellency in the AATCC test, the leathers treated with the aqueous dispersions according to the invention achieved more than 8 hours life and oil repellency values of 5 and greater after the water drop sample.

For the equipment of the leather in the bath, the aqueous dispersions of the invention - in the usual process 35

? A ν

the leather production after chrome tanning, retanning, dyeing and fatliquoring - the Fettungsbad (which had a fleet of 150 wt .-% water, based on Lederfalzgewicht) undiluted in an amount of 0.3 wt .-% fluorine, based on Lederfalzgewicht added ,

After drying and customary finishing of the leather, the water-repellent effect after the water-drop sample and the oil-repellent effect were tested according to the AATCC test mentioned

 The waterdrop sample of the leathers treated in this way resulted in service lives until the absorption of the applied water droplets of more than 8 hours, and oil repellency values of 5 and greater were achieved.

As the results of the application examples show, the compounds according to the invention and aqueous dispersions are excellent finishing agents for leathers and furs.

Claims (1)

invention claim 1. A process for the preparation of perfluoroalkyl- and epichlorohydrin-containing urethanes of formula I below CF ₃ - (CF ₂ ) _a -CH _a -CH ₂ -O- (CH ₂ -CH-OK-CNH I ^u . * CH, Cl CF, - (CF ₁ ) _a -CH ₂ -CH ₂ -O- (CH ₂ -CH-O) _b - CNH CH ₂ Cl in which a is a number from 5 to 17 and b is a number from 1 to 7, characterized in that 1 mol perfluoroalkvlethanol of the following formula II CF ₃ - (CF ₂ ) -CH ₂ -CH ₂ -OH,
a wherein a has the abovementioned meaning, with b mol epichlorohydrin, where b has the abovementioned meaning, in the presence of Lewis acids as a catalyst at a temperature of 50 to 150 ⁰ C and the Perfluoalkylethanol-epichlorohydrin adduct with toluene diisocyanate at a temperature also converted from 50 to 150 ⁰ C to the anoestrebten Urethanverbinduna. / Λ Λ