DE2018365A1 - Fluorocarbon-containing compounds and methods for making oil and water repellent to textiles, paper, leather and the like - Google Patents

Description

Sch / Gl 'Case I.

RIMAR S.ρ.Α., Trissino (Vicenza), Italy

Fluorocarbon-containing compounds and methods for Oil and water repellent rendering of textile, paper, leather

and the same

The invention relates to making oil and water repellent of substrates such as textiles, paper, leather or the like, by treating such substrates, with compounds which have perfluoroalkyl chains. ]

In particular, the invention is concerned with compounds in which a perfluoroalkyl chain is linked to an active part of the molecule which is capable of a possibly permanent bond between the chain and to create the substrate. Representative examples of this

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_ ρ -

/ like "known compounds are Perf luoracylaz.iridine, Perfluoroacyl polyamines and certain fluorocarbon urethanes, the latter being obtained in such a way that an organic isocyanate is reacted with a compound, which is a sulfonamide group, a perfluoroalkylene end group and contains a group to which an active hydrogen sits.

A disadvantage of the previously known compounds of the character described above is that they are insoluble in organic solvents (most of these compounds are used in the form of aqueous emulsions) or are only soluble in certain solvents or in certain solvent mixtures, which are either expensive or are difficult to recover (e.g. fluorinated solvents), or are flammable or highly toxic. The aim of the invention is therefore to create perfluoroacyl compounds which are capable of making substrates oil and water repellent in a permanent manner, these compounds being used in chlorinated hydrocarbon solvents such as those commonly used, for example tetrachlorethylene and Trichlorethylene, are soluble, and ■, ■ where these properties are not achieved for long periods of time by rubbing, washing, dry cleaning and similar treatments of goods made with these compounds ^:

fertilize have been treated.

Another disadvantage of the compounds known to date is that relatively large amounts are necessary in order to be effective Oil and water repellent coatings on a J Apply substrate. Furthermore, the known compounds afflicted with the disadvantage that these compounds are not able to produce woolen goods (for example, wollene

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_ 3 -

and yarns and knitted goods partly made of wool) to impart real shrink resistance properties, wherein these latter properties are to be understood in the sense as defined by the International Wool, Secretariat (an area shrinkage not exceeding 4 ^). In the

"The scope of the invention therefore also includes the creation of perfl.uoracy ! compounds capable of doing this, woolen goods both oil and water repellent as well as shrink-proof

^xi do. . ■

The compounds according to the invention correspond to the general ones formula

Y -N- (CHa) - I. CO -π- (CH ₂ ) _c - · 1 j _ ^Rf .J _n - 1 - wherein - _.

GO

ρ J

(D

ta

X is -H, -OCH ₅ Z-OC ₂ H ₅ ^ -OC ₅ H ₇ or -OCH (CH ₅ ) _£ Y is -H, -CH ₅ -, " ⁰ ^ ¹ V ~ ° 3 ^H 7 ^or - ^GE (° ^E ^ 2 ^divided

~ ° 3 ^H 7 ^or -

represent

Rf is a perfluorinated hydrocarbon chain ~ Q

represents , where ζ is an integer from 5-11, a, "b and .c are integers from 2-10, η symbolizes an integer from 1-10 and preferably from 3 to 10, · m an integer from 1 - 10 is
ρ stands for an integer from 1 to 5, q is an integer from 0 to 5 "and

[51 is a polyester or polyether polyurethane chain, which carries the number ρ of KCO groups given in the formula are, '■

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where the number average molecular weight M is the Connections does not exceed 60,000 (M is the international Symbol for number average molecular weight, see Encyclopedia of Polymer Science [and Technology, Volume 3, page 653 and Volume 9, page 182).

The scope of the invention also includes precursors compounds defined above in which the KGO groups temporarily blocked by phenol or other suitable blocking agent.

Preferably the number average molecular weight is of the compounds according to the invention at least 35iOO. ;;

If q stands for 0 in the formula I, then it is the Compound around a straight-chain polymer in which the ■ η-segments, which contain the perfluoroalkyl group Rf, and the m-segments, which contain the polyurethane chain, are distributed in the polymer chain in any order, where the remainder X sits on one of the m-segments and the remainder Y on one of the η-segments.

In typical. Way, however, q makes a value of at least 1 from, the compound of formula I being; is a branched polymer, which can have, for example, one of the structures given below:

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N- (CH ₂ ) _a - N- (GH ₂ )

CO

.Rf

-N-GH ₂ -GH ₂ CO

-N- (CH ₂ ) _b - X ι
CO '

[Zl (NGO) ₁

Cn)

N- (CHp) _a - N-GH ₂ ) _e ~ - H ι co I. Rf CO 1 - NH r 'I. N- (CH ₂ ) NH H I. co CO I. a " ^N - ( ^GH ₂ ) _C - Rf -N- (CH ₂ I. co I. NH- [] ~ ¹ . '■ - N- (CH ₂ I. co I. NH- -Π

(NGO)

(in)

(NGO) ₁

The compounds of the formula I can according to various Process are produced, namely j_e according to the respective Type of intermediate products used as starting materials. The molecule of formula I is more obvious Way formed from the following components:

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a) An aliphatic polyamine of the type: 1. Linear polyamine ■

where R is an aliphatic alkyl radical containing 1-6 carbon atoms, ζ is 2 - 6 and η 1 -! 8 ■ can be,

2. polyethyleneimine

ITH / η produced by the polymerization of ethyleneimine

can be produced (compare Encyclopedia of Polymer Science and Technology, Volume 1, page 737, J. Wiley & S., M.Y.). ■

The best results will be using polyamines received under 2).

b) Perfluorinated acyl groups of the type ^ _Fp.-GO-, where ζ = 5 - 11. "

ψ c) A polyester or Polyätherpolyiirethan prepolymer, the 3 - ·. Contains 6 free -HCO groups in the molecule and has been obtained in a known manner (High Polymers, Volume XIII, Part I, J. Wiley & Sons, HT) - on the basis of the reaction of:

1. A polyether of the aliphatic or aromatic Ty.ps »of the 3-6 free -OH groups of the alcoholic · Type as the only reactive end groups contains, by reaction of ethylene oxide or propylene oxide with polyols, for example glycerine, 1,1,1-trimethylol

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propane or mannitol, -or one Polyesters of the aliphatic or aromatic type, - The 3 - 6 free -OH groups of the alcoholic type as contains only terminal reactive groups and by condensation of a polyol such as Gly cerin, 1,1,1-trimethylolpropane or pentaerythritol, with an aliphatic or aromatic polycarboxylic acid, such as "for example malonic acid, succinic acid, adipic acid, glutaric acid, sebacic acid, azelaic acid, phthalic acid, Terephthalic acid, isophthalic acid, and ethylene or propylene glycol using

2. an aliphatic or aromatic di- or triisocyanate des 3iyps

1a) OClT-C ₂ H ₂₂ -MCO, where ζ = 4 - 10 (alkylene diisocyanate)

2a) OCN - ^ \ - CH ₅ (2,4-tolylene diisocyanate)

OGN

3a) CH ₅ - - {? % (2,6-idolylene diisocyanate)

4a) OCN - (/ ^ - CHpV - f ^ - NCO (4,4'-diphenylmethane

diisocyanate)

5a) Oci ~ / A-; cff; - / ~ \ - NCO (4,4 ', 4 "-triphenyl-

methane triisocyanate)

NGO

CH ₂ -O- CONH- C ₂ H ₂₂ - NGO 6a) E - - ^ C - 0 - COMI - C ₂ H ₉ - 1100 - 0 - COlIH - C _V E * J ~ - KCO

_BATH ORIGINAL

■ 3

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where ζ = 4-10 and R = H, CH ~ or C ₂ H ₅ ), preferably of type 1a), 3a) and 6a) and in particular of type 1a) and 6a), ie aliphatic di- and triisocyanates.

Each of the 3-6 free hydroxyl groups of the polyester or polyether reacts with the excess di- or triisocyanate in the following way:

Polyester - OH + OCU - J> ->

> Polyester - 0 - CO - NH -]> - NCO

wherein a urethane prepolymer of the polyether or polyester type having 3-6 free NCO-G groups in the molecule is obtained, and wherein]> is an alkyl, aryl, alkylaryl or aryl] alkyl chain which is in the starting di ™ or triisocyanate is present as a link between the -NGO groups contained therein. In case 1a), \> stands for -C Hr ,,, -, while, for example, im. Trap 3a) J>. CH ^ means.

The number of free -NGO -Grupjjen in the polyester or End groups formed from polyether chains can be formed, for example, by n-G groups in the polyether chains or by n groups in polyester chains of the type

- (CH ₂ ) _X - 0 - (OH ₂ ) - 0 - CO - NH - J> -

-O- CO ₂ - (CH ₂ ) - CO-O- (CHp) -O - CO - NH - ') ^> - Ji

ORIGINAL BATHROOM

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are represented, where η = 3-6, if the free hydroxyl groups of the polyether or polyester are reacted with a diisocyanate, and η; = 2 - 3, if the free hydroxyl groups of the polyether or polyester are reacted with a triisocyanate, and ; whereby .

χ = 1 - 6 and '_.

y - = 2 - 8.

The compounds according to the invention can be prepared from a polyether or polyester urethane prepolymer with a number average molecular weight of 30000 ~ 15,000, which contains at least three free isocyanate groups in the molecule and is capable of doing so, with the formation of substituted ureas or urethanes to react, as well as : from a polyamine which contains Rf-CO groups (perfluoroacylamido-N "-alkylamine) and has been obtained by reacting an ester or halide of a perfluorinated carboxylic acid having 6-12 carbon atoms with an aliphatic polyamine according to a) , getting produced.

One modification is to use a halide or a To implement ester of a perfluorinated acid with an excess of an aziridih, somehow attached to the two carbon atoms is substituted and is capable of polymerization enter into. In this palle there is also an amide of an N-alky! amine.

Another method of making the erfindungsgeraässen Compounds consists in using the polyester or polyether prepolymer, that's just one reactive isocyanate group in the chain, while the other groups are temporarily blocked by phenol (or by a

BAD ORiGiWAL

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other suitable agent, such as acetylacetone or dimethyl malonate), to react with a polyamine according to a) and then the compound obtained with such an amount of an ester or halide of a perfluoric acid which contains 6-12 carbon atoms for the reaction; which is less than or equal to the amount of free NH groups present »The compound obtained is then ^{heated to 140-150 °} C. in order to liberate the temporarily blocked isocyanate groups. The latter step can be prepared by heating the product after application to the surface to be protected for a period of several minutes to 135-150 ⁰ C are avoided (see Saunders Irish "Polyurethanes ¹¹ - I ₅₁ hawks Interscience).

The compounds according to the invention make surfaces to which they have been applied SiBd ₅ , oil- and water-repellent, without the need for binding substances. Distribute compounds evenly and permanently on these surfaces. In particular, it is applied to wool / artificial and synthetic fibers * leather or paper in embossing ». .

Further, the compounds of this invention are to j able wool yarns or woven fabrics shrink resistant to make 'and to impart dimensional stability woolen goods, in particular _s äann when the polyester or polyetherurethane ICette [2] (MCO) p has a number average molecular j has weights of 3,000-15,000.

It should be pointed out that the number averages of the "Molecular weights for both the polyester and polyether urethane prepolymers as well as for the compounds of formula I are determined in such a way that the isocyanate

BATH

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groups are titrated with an excess of dibutylamine, whereupon the whole mis bluing is diluted with ethyl alcohol and the excess of dibutylamine is titrated with 0.1u aqueous HGl (indicator: bromophenol blue). In this context, reference should also be made to "Encyclopedia of Polymer Science and Technology", Volume 5, page 653 ff. And Volume 9, page 182. The number averages of the molecular weights of the []>] (NCO) groups in the formula I are classified in such a way that they correspond to the number average values of the molecular weight of the parent compounds (polyester or polyether urethane prepolymers)

The following facts show that the inventive Compounds not mixtures of the products used in their manufacture are:

1. The solubility of the compound is different from the solubility of the starting products.

It is known that the polyamines, which are the compounds form, not soluble in common chlorinated solvents are, and not even after partial amidation with a derivative of a perfluorocarboxylic acid.

After a reaction in a mixture of at least two Solvents, one of which is partially fluorinated, such as for example 1,1,2-trichlorotrifluoroethane or trichlorofluoromethane or benzotrifluoride or alkyl or aryl chlorofluoro derivatives, while the other solvent is a polar organic solvent (with a high dielectric constant), such as a Ze ton, an alleyl ester of an aliphatic acid, dimethylformamide, Tetrahydrofuran, dioxane, dimethyl sulfoxide or the like., however, a compound is obtained that is found in chlorinated lo-

BAD ORlGiNAL

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smigsmittel, such as "for example" 3? richlo.rathyle: n ₉ tetrachlorethylene, chloroform., methyl chloroform, carbon tetrachloride or the like, is completely soluble, provided that the process according to the invention is used,

2 ". A fundamental method of determining the structure of chemical Connections is the IK spectrometry ,,

• With absorption measurements you can see the port stepping of the Track the reaction, and do so in such a way that the decrease

- T
the band at 2263 cm is measured as a result of an asymmetrical stretching of the N = C = O bond (compare Colthup, DaIy, Wiberley - Introduction to Infrared and Raman Spectroscopy, page 203, Academic Press, 1964) when the intermediate product containing free isocyanate groups is reacted with the polyamine after partial amidation with halides or esters of perfluorocarboxylic acids.

As mentioned above, the perfluorinated chain Ef can contain 5-11 carbon atoms. The chain initially belongs to its corresponding perfluorinated acid C 3? «..- COOH or to its corresponding halide GP _2. -COX '(where X' stands for fluorine, chlorine or bromine) or to an ester ^G z ^{] F} 2z + 1 ~ ^{C! 00R} (™ ^{ονΐΏ R denotes} methyl, ethyl, propyl or isopropyl), the halide or the ester being used according to the invention for the synthesis of the compounds I. Already at 55 = 5 ", compounds of the formula I are obtained which, when applied from solutions with an approximately 2 weight concentration (with respect to the fluorinated groups Hf), give the surface to be protected with sufficient anti-stain properties (oil and water repellency) Such properties can be improved in such a way that the amount on the substrate is increased, which is, however,

BAD ORIGIN "<

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Economically, the disadvantage is when z = 7 (perfluorooctanecarboxylic acid), the results are decidedly better and correspond to the economic requirements. The application of a solution containing 0.10% by weight of the fluorinated part Ef is sufficient. With ζ = 9 the results are improved even further. Perfluorocarboxylic acids having at least 8 carbon atoms are therefore preferred. ■ "·

The relationships outlined above are made possible by the attached drawing explained in more detail. This drawing is a graph obtained under conditions under which the concentration of the fluorinated part Ef in the to be applied Solution is kept constant (1.5 g / l). The values of oil repellency OE are given according to the DuPont scale, while the water repellency values SE according to the AATCO Spray Test 22-1952, respectively as a function of ζ (axis of the abscissa).

The following table summarizes the values that in determining the oil repellency according to DuPont system, relative to the surface tension of the test liquid.

Test liquid surface tension,
Dvn / cm » 31.45 DuPont scale Nujol (Plow Inc.) 30.00 2 75/25 nujol / n-hexadecane 29.05. 3 50/50 fujol / n-hexadecane 26.35 4th n-tetradecane. 24.70 5 · n-dodecane 23.50 6th n-decane 21.40 7th n-octane 19.75 8th n-IIeptane 9

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The polyamines can be amidated by means of a halide of an ester of an acid according to the previous definition. If you work with an excess of alcohol in the presence of an acidic catalyst, such as the HpSO * .EP ₇ system, the methyl , Ethyl, propyl and isopropyl esters quickly and with a high throughput (over 90 fo) ₉ although it is possible to carry out cyclizations.These esters react quantitatively with the primary polyamido groups, both in bulk and in anhydrous solvents , olme that there is a reaction with the secondary polyamido groups "

Are polyether or polyester polyurethane prepolymers with isocyanate groups of the ixjltyps used ₉ are compounds of the formula I obtained _? the

- with a 'concentration of only Q _? 15% by weight of the j fluorinated groups Rf in the applied solution impart oil repellency,

- make water repellent _s -

- make wool yarn shrink-proof? if the concentration of the [ZE.] (NöO) p-fractions in the applied solution is at least '[ 0.8% by weight ^ ·'.

- and are soluble in common chlorinated organic solvents if the number average molecular weight the [^] (NOO) content is at least 3,000.

If polyether or polyester polyurethane prepolymers having isocyanate groups of the aliphatic type are used, then Compounds of formula I obtained, the

- give a pronounced oil repellency, namely r even if they are applied from solutions, that only 0.1% by weight of the fluorinated parts Rf contain,

~ * 15 -

~ make water repellent, '

-Wool yarns mid woven goods to make them shrink-proof when the Concentration of the [*>] (MOO) components in the Solution is at least 0.8 weight ^ and the number through ~ -cut of the molecular weight of the proportions between 3000 and 15 000 fluctuates, and

- are readily soluble in common chlorinated solvents.

However, since it has been found that the compounds of the formula I obtained from polyether or polyester polyurethane torpolymers with aryl isoeyanate groups are susceptible to decomposition and form precipitates or a coagulum, the compounds are preferred according to the invention which are made from polyether or Polyester polyurethane prepolymers having isocyanate groups of the aliphatic type, where the ~ P> part is an alkylene chain, are available.

A surprising fact is that a polyester or polyether polyurethane prepolymer with isocyanate groups with aliphatic character as such a substrate neither gives oil- and water-repellent properties, while the Perfluoracylamido — H-alkylamine, oil- and not water-repellent are. The connections according to the invention are in contrast highly oil and water repellent.

The ■? The table below shows that the compounds have excellent properties that cannot be derived from the properties of the individual components.

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2QIi

ι fr * ψ *

'© 5

1.6

table I.

Oil repellent
vexmögen • water repellent
ability solubility Pplyamine with per-
fluorinated chains ■ 6-7 0 '= 50 no Polyester or
Polyether prepoly
meres with reactive
= 100 groups
Compound I. 0
7-8 0 - 5.0.
8jO - 90: Yes
Yes Remarks;

Concentrations: 0.15% by weight of fluorinated parts

- solubility:

0.8 weight ^ polyester or polyether chains

In chlorinated solvents ■]

- Values of the oil repellency according to the DuPont scale and values of water repellency according to the AAIOC spray test 22-1952 '; -

- values obtained from tests carried out using specimens made of woolen yarns and woven goods became.

Method.n for the synthesis of the products:

To carry out the examples described below, Uses polyester and polyether urethane prepolymers, which contain 3-6 free -NCO groups of the aliphatic type per chain and a number average molecular j weigh between 3,000 and 15,000. ]

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.- ■ "- ■.;. ■■ - - - 17.-.- ■: ■■■■■. The prepolymers are as follows

(A) Bin Polyätherurethan-Vörpol ^ meres with a number average molecular weight of 5000, which contains 3 free -NGO groups and "by reaction of 1,1,1-crimethylolpropane, CH ~ -CH ₂ -C (CII ₂ -OHW. 'with propylene oxide' and subsequent reaction of the resulting polyether polyfing with hexamethylene diisoeyanate in thy lace tat. "

(B) A polyether urethane prepolymer with a ZahCLe ^ ndureh- 'section of the Molelmlargewaöhts of 9000,.' The 4 free -1T0Ö - " contains 2 groups and by reaction ύοιι pentaerythritol, j C (CH ₂ OH) *, with propylene oxide and subsequent reaction of the polyether polymer obtained with hexaraethylene diisoeyanate in ethyl acetate has been obtained,

(C) A polyester urethane polymer with a number average molecular weight of 15,000 _s that contains 6 free -NCO groups and is produced by esterification of 1,1,1-trimethylolpropane with adipic acid and propylene glycol and subsequent reaction of the polyester polymer obtained with! 3 mol! Diisocyanate of the formula O ₂ H ₅ -C (CH ₂ -O-CO-NH-C ₆ H ₁₂ ~ 1TCO) ~ has been obtained.

Example 1 ^; ^

44.2 g of C ₇ F ₁₅ -COOC ₂ H _5. (0.1 mol) and 8.6 g of aziridine (0.2 mol),. » which has previously been ^{cooled to 0 0} G are at the same time slowly poured into a 250 ml flask which is provided with a stirrer and is cooled from the outside by means of a bath made of ice and water.

Me iCemperatur is allowed to rise during the feed period not exceeding 5 ⁰ C.

.109017 / 2223

SatsMem clis "giaJFuhr Iseeaast -.is, the oil temperature is slowly increased BUf 3C) ⁰ G * The initially flp.Me colorless reaction PSOctect becomes, sllaiäfclicii ifislcoBer iis tanned" Sine

iqiiaatl active Bes tirnaraag des _W 3 on - Oa ^ uQ-w & rä 400) as well as eise

Ter-nfeäöki ^ g fiss Esters j aacl

^ ' ^{? s} r. Page 315 ₃ Aa

' ^ff ' O33 ilem Bea & tiüiisproäiikt-tiii? d_ GoH-OlL that arises as Mep ■., cterah Sxtx-aktio :: .. with .3 PortioBeii out of 50 each

removed " "

Balasi weMes 4S g eixsss diireiisiclitigsa fluiae monetary received ο Tuck © Product is in iCr-i chlor äthyleneng? Kojaleastoff ₉ öhloroform _s Setrachlorathylenj. Methyl-

ώβ-ο. Setrseliloifätlian is soluble. Is dissolves in acetone ρ Biatliylatlieir ^ Metl ^ Xalkoholy Ethyl alcohol and Iso ~ propy! Alcohol only to a small extent "

48 g of purified product are dissolved in a mixture of acetone and 1 _s 1 _s 2-Srichlortrifluoräthaii (50? Volume ~ 50) ^, \ mi® EoasentEatisn dez? Zösvms- Mira increased to 200 g / l. J.

300 g of the ^ o ^ atherns-etham-VorpolyiEerea (A) ₅ dissolved-in O ₅ 5 1 J 1 ₉ i-jS-SrichlortrifliiOEätljaiSg will »a three-necked 3! Flask S'iigeeetaiV des? Stranding with a slider is »Ausserdea the IColbea © i ^ sa Heismaat ©! and one. Reflux condenser to ₀ -

- - 19 - '

After heating the solution to boiling temperature, it will turn ice previously prepared polymer solution tropfemfeis.e from one Squibb · funnel exposed. Mach finishing the addition will 'taking the' solution for a period of 30 minutes Maintained reflux and allowed to drain into the mixer.

The polymer obtained in the reaction can be obtained by first distilling off 450 & 1 1 »1,2-3? Richlortrifluoroethane, whereupon the solution is concentrated for a period of 40 minutes at 38 ° G under reduced pressure« a CaGlp palle is used in 1 of the vacuum line. 350 g of a transparent, syrupy, straw-yellow polymer are obtained, the viscosity of which increases on cooling. However, the product does not solidify at 18 ° C. The polymer has a number average molecular weight of 27,000 and contains 16 isocyanate groups in the molecule. isopropyl alcohol, ethyl acetate, irichloräthylen, 2! etrachloräthylen, methyl chloroform, Ietrachlorkohlenstoff and Te trachloräthan soluble. . ·

The solution obtained in the above-described procedure, which contains 350 g of the polymer per liter contains, to 1670 ml by adding setrachlorethylene diluted.

use

72 ml of the solution prepared in the manner described above are 1 1 trichlorethylene at room temperature to adjust a concentration of about 15 g des Added polymers per liter.

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, 2018385

-.20 -

This solution containing 1.72 g fluorinated Rf shares per liter "] solution to treat a · knitted woolen goods are used both by dipping and spraying, after which the goods will be wrung anschilessend. In spring Palle is a . 100 follow impregnation achieved Werdie the "treated samples under the following conditions dried, then no difference in water" · is - and oil repellency and the shrinkage determined resistance:

a) for a period of 48 hours at a temperature of 20 J - 6O ⁰ O, _f

b) for a period of 10 minutes at 9O ⁰ C, "

c) for a period of 5 minutes

The test results are summarized below:

Initial After 5 Chemical Uach -n 5 Wet Cleaners worth washing

Oil repellency 8 7 7

Water repellency. 80-90 70-80 70

Shrinking surface, - '

Io 2.0 2.0 2.5

Example 2 .

88-4 g of C ₇ P ₁₅ COOC ₂ H ₅ (0.2 mol) and 17.2 g of aziridine (0.4 mol) are reacted in the manner described in Example 1. After extraction of the ethyl alcohol, 96.2 g of a transparent fluid yellowish compound are obtained. The product is in trichlorethylene, carbon tetrachloride, chloroform, methyl chloroform, tetrachlorethylene and tetrachloro- I _äthan and insoluble in acetone, Diäthylather ,. Methyl alcohol, ethyl alcohol and isopropyl alcohol are sparingly soluble. j

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48 g of the received]! Product with 150 g of the polyether urethane prepolymer (A), 'dissolved in 0.5 1 1,1,2-trichlorotrifluoroethane, implemented. \ ·

The polymer obtained in the reaction can be separated off in this way be that first 400 ml 1,1,2-Triehlortri.-fluoroethane, are distilled off, whereupon the solution for 40 minutes at 38 ° G under reduced Pressure is distilled. An Oaleiumchlorid-Palle is used used in the Valoium line. After cooling down man197 g of a transparent, viscous, straw-yellow polymer with a count average molecular weight j of 20,000. The polymer contains 4 isocyanate groups per] Molecule and is in acetone, 1, i, 2-3? Richlortrifluoroethane, Ethyl acetate, irichlorethylene, 3-jetrachlorethylene, methylchloroform, Carbon tetrachloride and tetrachloroethane soluble.

For use, the solution obtained in the manner described above, the 197 g ^it contains polymers pr.o liter diluted at 1670 ml by the addition of tetrachlorethylene. It is applied to identical samples in the manner described in the previous example. J

The concentration of the fluorinated Ef components is 1." 72 g / l as in Example 1. The results are below specified:; . · ■ '- ■■' ■.

Initial iiach 5 Chemical After 5 hate · · worth relnigungen washes

Oil Repellency Water Repellency Shrinkage area,

8th : T 7 ' 80-90 y 70-80 70 β 10 12th

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Example 3

If the product is not intended to impart any shrinkage properties, then smaller amounts of free -IGO groups are sufficient. 44 ₃ 2 g of G ₇ F ₁₅ OQOO ₂ H _5. (0.1 mol) and 6.4 g of ethyleneimine (0.15 mol) are reacted in the manner described in Example 1. The product obtained is washed with 3 portions of ₁ \ from each 50 ml CGl and then at a period of 25 minutes, 40 ⁰ O dried under reduced pressure "46 g of a transparent and fluiöen hellge1, Li2S. ! Polymers are obtained-. has _o JM "IH spectrum shows that under _s öorartigen conditions & d £ button" of perfluorier th ■ Sä'are completely reacted, "" Bas polymers is in Sriclilcr- j äthvleBgCGl ,, Chol ^ ₉ methyl chloroform, 'O? _s etrachioräthylen Ί Setraohlo2? Ethane _& ethyl alcohol and isopropyl alcohol insoluble and in ether _s acetone tmö .1- _f 1 _P 2 ~ Srichlprtrifluoräthan : slightly soluble ,, "

25 g of the polymer obtained are treated with 100 ml of the solution "treated with 50 ¥ ol * umen ~ ^ 1 _ΰ 1 _B 2- & iehlortrifluoroethane and acetone with 225 g of des.Polyätherurethan-Vorpolmeren (A), dissolved in 200 ml 1 ., 1 _β 2-3! Richlortrifluoroethane, contains. '

By processing according to the manner described in Example ■ 1, a slightly viscous and straw-yellow solution is obtained which! ], After cooling by Zngßb® \ ^r is diluted al iCrichloräthylen to 380, synthesized in the manner described above polymers can be obtained by first 300 ml 1 ₉ 1,2-i ³ are distilled off in riclilortr'ifluoräthan OCE manner, whereupon the remaining Xiösunjg; itte.l under reduced Drucis Si: evaporated at 53 ⁰ O · over a period of 40 minutes in the "beselirieibeBen in the preceding examples 33ab®i © rkält MAN 46 horny transparent mbkossB _s _ j?

lit

and light straw yellow "polymers. The polymer is soluble in trichlorethylene, letrac & lorethane, tetrachlorethylene, chloroform, methyl chloroform, GGIt ₃ 1.1 _s 2-5richlorotrifluoroethane _J acetone, ethyl alcohol and xsopropyl alcohol and has a number average molecular weight of 14,000 it contains 4 isocyanate groups per molecule.

Use .. "* - ■

33 ml of the solution which contains the non-separated polymer are diluted with 1 l of oxychlorethylene to set a polymer concentration of 3 _} 5 g / l. In comparison to the use tests given in Example T, one of the same concentrations of fluorinated content (1.72 g / l) is used. '

Comparative tests are made using goods made from natural and synthetic 3? aers carried out.

Wool

oil removal water removal

cotton
Oil repulsion Water repulsion

Plachs
Oil repulsion Yiasser repulsion

Initial Uach 5 chemical Uach 5 hate worth cleaning ivas urged

7 7 7 7

80-90 80-90 70-80 80

6 6 6 6 ■
70 70 60-70 70

7 7 7 7
70-80 80 70 70-80

AWAY-

6-7 6 70 70

5-6 5 50-60 50-70

6-7 7 50-70 70

1 0 9 317/2 22 3

- At first-
value After 5 chemically
clean 7th
70 B. After 5 wet
was chung: en B. 7 I ■; AWAY A- 7-8
70-80 A. 6th
70 .Polyester 7th
70 6th
70 Oil repellency '
Water repellency 7 7
80-90 80 7th
80-90 6-7
80 6-7
70 polyamide
Oil repellency
Water repellency 7-8 7
80 ■ 80-90 7-8
70-80 6th
80 7]
70 6th
70 Aery! Materials
Oil repellency
Water drainage 7 7 7
80-90 80-90 70-80 6-7
60-70 6th
50-70 acetate 6th
70-80 ν
Oil repellency
Water repellency 7-8 7 "
70-80 80 7th
80 7th
50-70 Chlorovinyl,
Oil repellency
Water repellency 7-8 7
80 80-90 7th
70

A = product that has been manufactured according to example 1.] * B = product that has been manufactured according to example 3 J

In the preceding examples, the tests to determine the oil and water repellency as well as the shrinkage resistance are used and dry cleaning and wet washing were performed 100 hours after the samples were treated. ]

Example 4 '

'21, 7 g of C ₂ H ₅ - (NH-C ₂ H ₄ -) ₄ -M ₂ (0.1 mol) are placed in a 500 ml flask equipped with a stirrer and a condenser, whereupon then 45.6 g of Cr, F _1c -COOCH (CH ^) p

109817/2223

0.1 mol) are introduced slowly.

. After the addition of the Eeaktanten heating is continued on the water bath at 4O ⁰ C for about 2 hours. A yellow-brown syrupy mass is obtained. Gas very omatographic and spectrophotometric investigations confirm that the ester reacted practically quantitatively. - -

The reaction product is then mixed with 3 portions of 500 ml CCl each to remove the isopropanol formed washed. In this way, 61.2 g of a yellowish-brown syrupy compound are obtained, which in Trichlorethylene, tetrachlorethylene, carbon tetrachloride, Chloroform and methylehloroform is insoluble and dissolves in Ether, acetone and 1,1,2-trichlorotrifluoroethane partially dissolves. This compound is dissolved in 890 ml. Of a solvent, " which consists of 1,1,2-trichlorotrifluoroethane and acetone (50 volume ^ ige mixture).

1500 g of the polyester-urethane-Yorpolymeren (C), dissolved in 1 1.1 j2-trichlorotrifluoroethane, are placed in a three-necked flask Filled in, which is provided with a stirrer and a cooler and protected against moisture by CaClg traps is. The solution is heated to its boiling point and then added dropwise with the one previously prepared Mixed solution of the perfluoroacylamido-N-alkylamine. the Solution is refluxed for a period of approximately 30 minutes. After cooling down, it becomes transparent and straw yellow viscous liquid obtained.

The synthesized in the manner described above Polymers can be separated in such a way that first

109817/2223

1200 ml of 1,1,2-trichlorotrifluoroethane are distilled, whereupon the remaining solvent at 38 ° G for a period of 90 minutes in the same manner as in the preceding Examples described is evaporated. This gives 1560 g a transparent, highly viscous and straw-yellow polymer. This polymer dissolves in chlorinated and non-chlorinated Solvents as mentioned in the previous examples became. It has a number average molecular weight of 60,000 and contains 8 free isocyanate groups per Molecule.

The liquid containing the non-trimmed polymer is diluted to 5900 ml by adding perchlorethylene. 'An analysis of the free -NGO groups by titration with Bibutylamine confirms that there are 8 free -HGO groups per molecule present "·

223 ml of the solution prepared in the above manner are diluted to 1 liter using perchlorethylene. This. results in the adjustment of a polymer concentration of approximately 59 g / l. Knitted woolen goods are then treated with this solution, both by dipping and spraying. The viars are then wrung out. In any case, a 150 consecutive impregnation is achieved «,

The samples are ^{dried at 80 °} C. for a period of 20 minutes. The test results are summarized in the following 'Table !: ' / ,. '.

Initial- After 5 Chemical- After. 5 wet cleaning washes

Oil repellency 8 - 9 8th '7-8 Water repellency 80-90 80 70-80 Shrinkage area, 5 ^f o 1.5 1.5 2.0 Example 5

Compared to example 4, this example seems to show that the lack of free isocyanate groups in the macromolecules is a main reason for the lack of shrinkage resistance in the treated woolen garrT ~ is.

1 -

i: ■. ■

45.6 g of G ₇ P ₁₅ COOOH (CH ₃ ) ₂ (0.1 mol) are reacted with 21.7 g (0.1 mol) of C ₂ H ₅ (1nH-O ₂ H ₄ ) ₄ -HH ₂ . The product is washed in the manner described in Example 4.

41 g of a viscous and yellowish-brown compound of the formula C ₂ H ₅ (IiH-G ₂ H ^) ₄ -ITH-GO Rf are obtained and dissolved in 890 ml of a solvent consisting of 1,1,2-tri-chlorotrifluoroethane and acetone (50 Yolumen - $> mixture). This solution is reacted with 1000 g of the polyester urethane prepolymer (G) dissolved in 500 ml of 1,1,2-liter-enriched trifluoroethane. After 800 ml of 1,1,2-trichlorotrifluoroethane have been distilled off and the remaining solvent has been removed by evaporation / at 38 ° C. for a period of 90 minutes in the manner described above, 1060 g of a transparent, viscous one are obtained and straw yellow polymers. This polymer is soluble in chlorinated and non-chlorinated solvents as mentioned in the previous examples. However, there are no free isocyanate groups in the solution. This latter fact is underlined by IR spectrophotoinetry and volumetric analysis

109817/2223

Confirmed use of dibutylamine. "The polymer is then ^{heated to 100-120 - HO - 180-20O 0} C. At any temperature, a volumetric test for possible 4ICO groups gives a negative result. This polymer is also indefinitely stable against moisture and heat. A solution of the Polymers, as it has been described above, is diluted to 5900 ml by adding perchlorethylene and applied to identical samples in the manner described in Example 4. The concentration of the fluorinated components is kept at 1.72 g / l. results are summarized below:

Initially after 5 chemical after 5 hatred worth cleaning what cjgiinz

Oil repellency 8-9 8 7-8

Water repellency 80-90 80 70-80 Shrinkage area, i <> As with the untreated samples

Example 6 '

150 g (0.01 mol) of the polyesterirethane prepolymer (C), dissolved .in 100 ml of anhydrous ethyl acetate, 4.7 g Phenol mixed and the solution refluxed for a period of 4 hours. The solution to the Polymer is then analyzed. In doing so, one poses states that the prepolymer still has 1 free isocyanate group contains per chain.

This solution is placed in a three-necked 1 l flask, which is equipped with a stirrer and a reflux condenser and is protected against moisture by CaCl _o traps: V ^ T. The solution drips with 2, 15 g. Ethylenimine (0.05 Hol) mixed. The reaction is exothermic and is made on cooling

BAD ORiGfWAL

109817/2223

kept under control with water and ice. Stirring is carried out over a period of 1 hour, after which 17.28 g of G ₇ P ₁₅ GOGl (0.04 mol), dissolved in 200 ml of an anhydrous 1,1,2-trifluoroethane, are added dropwise! will. The solution is refluxed for a period of 10 hours until no more HGl is released. Then it is cooled and diluted to 590 ml by adding methyl chloroform.

The polymer obtained in the manner described above can be separated off in such a way that 180 ml of 1,1,2-trichlorotrifluoroethane are distilled off at 42 ° C. over a period of 90 minutes. The result consists of 173 g of a transparent, viscous and yellow polymer with a! Number average molecular weight of 42,000 containing 12 isocyanate groups protected by phenol. It is soluble in trichlorethylene, tetrachlorethylene, chloroform, kethychloroform, carbon tetrachloride, tetrachloroethane, dietary ether, 1, 1, .2-trichlorotrifluoroethane, ethyl acetate, and acetone. 22 g of such polymers are post-] successively to 130 - 160 ⁰ G heated during a / period of 10 minutes - 140 - 150th The possible presence of free -NGO groups is examined at each temperature. .] [. . ■ -:

After heating to 150 ^° C., a sample of the polymer is dissolved in 50 ml of a mixture of 1,1,2-trichlorotrifluoroethane and acetone (50 volumes), whereupon the solution obtained is mixed with a known excess amount of dibutylamine in an anhydrous chlorobenzene is treated. The excess is then titrated with 0.1N HCl, bromophenol blue dissolved in CpH ₁ -OH being used as an indicator. · The analysis shows that, at 15O ⁰ C all -NCO groups which are blocked by phenol, are übergejgangen back into its original state.

BAD ORlQiNAL

109817/2223

use

52 ml of the solution containing the non-separated in the above Contains polymers prepared as described, are diluted at room temperature with 1 liter of Methylchiorofor ία. The polymer concentration ″ is 15 g / l.

Samples of knitted woolen goods are treated with this solution by dipping and spraying and then wrung out. In both cases a 130 consecutive impregnation is achieved. After drying at 70.degree. C. for a period of 1 hour, a heat treatment at 150.degree. C. for a period of 5 minutes is necessary in order to liberate the phenolic groups. The '; Test results are summarized below in tabular form;

Initially after 5 chemical washings after 5 wet cleanings

Oil repellency 8th 7-8 7th Water repellency 80-90 80 70-80 Shrinkage area, # 2.0 2.0 - 2.3 ' Example 7

8.5 g of aziridine (0.2 mol) are added dropwise to a 100 ml flask containing _{44.2 g of G 7} F _{15 COOG 2} H ₅ (0.1 mol). The mixture is held at -28 ° C for 48 hours with stirring.

A white polymer is obtained which is slightly viscous at room temperature. "The ethanol produced by the reaction is then made by washing 3 servings each

109817/222?

20 ml of methyl chloroform removed. This gives 48.1 g Perfluoraeylamido-lT-alkylamine, which is found in trichlorethylene, tetrachlorethylene, Tetrachloroethane, chloroform, methyl chloroform and carbon tetrachloride insoluble and in acetone, 1,1,2-tri- " chlorotrifluoroethane, ethyl ether, ethyl acetate, ethyl alcohol and isopropyl alcohol. is soluble. This amount is in 240 ml a mixture of 1,1,2-trichlorotrifluoroethane and ethyl acetate (59 volume- ^) solved in such a way that a polymer concentration of 200 g / l is achieved.

The solution prepared in the manner described above j is added dropwise 300 g of the polyether urethane prepolymer (A), dissolved in 0.5 ml of 1,1,2-trichlorotrifluoroethane, added under reflux and with stirring, in a 2 l flask. -

After the addition is complete, the reflux treatment is continued for a period of 30-35 minutes. A dilution with trichlorethylene to 1670 ml gives an oily, light yellow solution. The polymer is separated from the solution in such a way that first 500 ml of 1, 1, 2r-Triehlortrif luoroethane are distilled off. The remaining solvent is then evaporated at A5 ° 0 over a period of 40 minutes under reduced pressure. This gives 350 g of a slightly viscous, straw-yellow polymer. The polymer is soluble in chlorinated solvents (in which the perfluoroacylamido- ~ N-alkylamine of this example is insoluble) and also dissolves in ethyl acetate, 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: -j of this product, its use so / ie y

10 9 8 17/2223. BATH ORIGINAL

the results obtained agree with the relevant facts of the product obtained according to Example 1, match.

Example 8 ■.

12.9 g of aziridine (0.3 mol) and 21 g of triethylamine, dissolved in 3060 ml of ethyl ether, are fed into a three-necked 1 liter flask. The solution is carefully cooled to -30 ⁰ C and slowly mixed with 86.5 g O ₇ P ₁₅ cool (0.2 "mole) of a Squibb funnel, care being taken that the temperature to a value above - 25 ° 0 increases.

After the amidation reaction has ended, the triethylamine hydrochloride formed as a by-product is quickly filtered off, whereupon the ether is removed by evaporation under reduced pressure. This gives 92 g of a syrupy yellow-brown mass which is dissolved in 500 ml of a mixture of 1,1,2-trichlorotrifluoroethane and acetone (50 vol. ^) is dissolved. The mass is in trichlorethylene, tetrachlorethylene, tetrachlorethylene, Methyl chloroform, chloroform and carbon tetrachloride are insoluble and partially dissolve in 1 ,. 1,2-trichlorotrifluoroethane, Acetone, diethyl ether and ethyl acetate.

fc 1500 g of the polyester urethane prepolymer (C) are in 1 1 1,1, 2-Trichlorotr.ifluoroethane dissolved, whereupon the solution in a 3 1 flask equipped with a stirrer and opposed to the ingress of moisture through calcium chloride palleii is protected, is refluxed.

The solution prepared in the manner described above of the perfluoroacylamido-H-alkylamine is then added dropwise added, the Yorpolymerenlüaung under reflux is held. ! When the addition is complete, the reflux

109817/2 2 23

- ■ 33 -

treatment continued for a period of 30 minutes. By means of IR spectrophotometry, the decrease in the band at 2263 cm ~, which is to be rubbed on the -NGO -G group, can be ascertained with the passage of time. By distilling off 1,200 ml of 1,1,2-trichlorotrifluoroethane and ansohliessendes waste 'evaporation of the residual solvent for a period of 90 minutes at 38 ° C under reduced pressure gives, 1590 £ viscous a strong and deep yellow polymers. Its average molecular weight is 27,000. The polymer is soluble in all chlorinated solvents mentioned above in this example and also dissolves in ethyl alcohol, isopropyl alcohol, acetone, ethyl acetate and ethyl ether.

The solution of the prepared in the manner described above Polymer is adjusted to 3080 ml by adding perchlorethylene.

Use ■

46.5 ml of that obtained in the manner described above Solution v / earth dissolved in 1 l of perchlorethylene at room temperature, in such a way that a polymer con- "j ■." concentration of 24 g / l is obtained.

There are carried out tests using wool samples in the eispielen in the? 1, 4 and 7 described above. The results are summarized in the following table:

Initial after 5 chemical cleaning _{after 5 wet cleaning with} washes

ülabrückung Vfenserabrückung shrinkage area, ° / o

8th 7th 7th 80-90 80 70-80 2.0 2.0 2.4

109817/2223

Example 9

300 g of the polyether urethane prepolymer (A), dissolved in 250 ml of an anhydrous ethyl acetate, are added to 18.8 g of phenol, whereupon the solution is refluxed for a period of 4 hours. The solution of the prepolymer is analyzed and it is found that they are still. J1 contains iscyanate group in the molecule.

8.8 g of GH ₅ NHGBI ₂ CH ₂ NH ₂ (O, 1 mol) in 25 ml Mgroin are supplied under vigorous stirring ψ a three-necked 1-1-IColben, which is provided with a stirrer and a condenser. The dispersion prepared hex 'in the manner described above, which has been cooled to -23 ° 0 using a brine, is mixed with the solution of the polyether urethane prepolymer (A) in which the -NGO groups are partially blocked by phenol, mixed.

After 3 hours, the reaction mixture is refluxed, whereupon 43j2 g of G ₇ P ₁₅ GOCl (0.1 mol), dissolved in 200 ml of an anhydrous 1,1,2-trichlorotrifluoroethane, are added dropwise with vigorous stirring.

The reflux treatment with vigorous stirring is continued for as long continued until no more HCl is released. ! laugh cooling the solution to 1670 ml. Addition of perchlorethylene diluted.

The polymer containing two isocyanate groups protected by phenol obtained in the manner described above • are separated in such a way that 160 ml 1,1,2-. Trichlorotrifluoroethane are distilled off, whereupon the remaining solvent under reduced pressure in the same

BATH

109817/2223

Way like. in Example 6 is evaporated.

This gives 365 g of a slightly viscous pale yellow polymer with a number average molecular weight of 3500, which is in trichlorethylene, tetrachloroethane, perchlorethylene, methylchloroforin, chloroform, CCl., Ethyl ether, 1,1,2-tri - '' chlorotrifluoroethane, ethyl acetate and acetone is soluble! In the presence of moisture this polymer remains unchanged indefinitely. The tests using knitted "woolen goods are carried out in such a way that the goods are ' ^{treated with a solution 1} ". - which contains 15 g of the polymer per liter of solvent (perehloroethylene) The tests are carried out in the manner described in Example 6. The results are summarized in the following table:

• ■■ "■ Initial Bach 5 Chemical - ITach 5 '! Let-

v / ert cleanings wakens

Oil repellency 8th 7th 7th Water repellency 80-90 80 70-80 Area of contraction, i <> 2.0 ; '; 2.0 ■ • 2.4 - ^: - Example 10- ■ ■ "■■ -«. " '

21.7 g of C ₂ H ₅ - (KH-C ₂ H _{4) 4} -in the ₂ (0.1 mol) are slowly added under stirring with 47.8 g GgIV ₇ COOGH ,, (0.1 mol) at 40 ^u C implemented. After the reaction has ended, the yellowish and highly viscous product is _{washed with 3 portions of 50 ml of GCl 4} to remove the methanol formed. In this way one obtains 66 g of a white substance with a pasty consistency, "which is insoluble in trichlorethylene, tetrachloroethane, perchlorethylene, CGI / and GHGl ^ and is soluble in 1,1,2-trichlorotrifluoride, acetone and ethyl acetate This amount of fluoracylamide of the formula Rf-COHIT- (C ₂ H ₇₁ KH) ₄ -C ₂ H ₅ , dissolved

ORIGINAL BATHROOM 109817/2223 -

-56 -

in 240 ml of a solvent consisting of f, 1,2-n? ri ~ " chlorotr'ifluoroethane and acetone (50 volume- ^), with 1500 g the polyester urethane prepolymer (C), dissolved in 1 1 1,1,2- 'Irichlorotrifluoräthylen, in the one described in Example 4 Wise implemented.

The result is a slightly viscous yellow solution which is diluted by 6800 ml ^l "addition of Triohloräthylen on. The polymers can erhaltane v separated in the manner / ground that first 1 1 1,1,2-trichlorotrifluoroethane was distilled off, whereupon the remaining solvent is evaporated off under reduced pressure until a constant weight has been reached. Evaporation is carried out in the manner described above. 1565 g of a highly viscous yellow polymer with a number average molecular weight of 60,000, which is 8 contains free isocyanate groups per molecule. It is soluble in chlorinated and non-chlorinated solvents such as those mentioned above in this example. In the presence of moisture, this polymer is slowly converted into an increasingly viscous mass for as long , until the mass has taken on a rubber-like appearance and (even with raised doors) in all v above-mentioned solvents is insoluble.

Usage

200 ml of a solution in the manner described above Polymers produced are with methyl chloroform to 1 1 diluted in such a way that a polymer concentration of 46 g / l is achieved.

. . BATH ORIGINAL

109817/2 2 23

Woven samples are processed using this solution, both by immersion and by spraying and then wringing out in such a way Way that a 100 $ impregnation is achieved.

The samples are ^{dried at 100 °} C. for a period of 10 minutes. The test results obtained are summarized below in tabular form:

Initial washing after 5 chemical washing after 5 hatred value cleanings

Oil repellency 8th 7th 7th What s erabs tossung 80-90 80 70-80 Area of shrinkage, ° / o 2.2 2.4 2.9 Example 11

96.5 g of C ₈ F ₁₇ COCl (0.2 mol) slowly at -30 ⁰ C with 12.9 g of aziridine (0.3 mol) and 21 g Iriäthylamin dispersed in ethyl ether, in the manner described in Example 8 implemented. After filtering off the TriäthylaniinhydrοChlorids and after removing the ether by evaporation in vacuo, 102 g of a waxy whitish product is obtained, which is dissolved in 500 ml of a mixture of acetone and C ₂ Ol ^ F, (50 volume ^) '. The product is insoluble in the solvents given in the preceding examples and partially dissolves in 1,1,2-triochlorotrifluoroethane, acetone and ethyl acetate. This solution is mixed dropwise into 1500 g of the polyester urethane prepolymer (C), dissolved in 1 l of CpCl ^ F ^, at the reflux temperature of the latter. After the addition is complete, the reflux treatment is continued for a period of 30 minutes. If the procedure described in Example 8 is adhered to, 1600 g are obtained

BAD ORIGfNAL 109817/2223

of a bright white and highly viscous polymer with a number average molecular weight of 27,000 Polymer contains 7 free isocyanate groups in the molecule and becomes increasingly viscous in the presence of moisture at room temperature until it is in * a polyamide resin has been converted, which in all tested Solvent is insoluble, even at elevated temperature. A solution of the polymer contained in the ■ '■> - has been obtained in the manner described above . . . diluted to 4000 ml by adding perchlorethylene.

use

52 ml of the solution v / earth at room temperature in 1 1 Tri-. chloromethylene to adjust a polymer concentration of approximately 21 g / l and a concentration of the fluorinated portion of 1.6 g / l. The tests using knitted woolen goods are carried out in ¹ as described in the previous examples. The results are summarized below in tabular form:

Initially after 5 dry cleanings after 5 wet washes

Oil repellency 8 7

Wassi-repulsion 80-90 80 70-80

Shrink area, fo 2.2 2.4 2.9

Example 12

If the product is not supposed to have any shrinkage resistance, then Smaller amounts of free -NCO groups are sufficient.

96.5 g of CqF ₁₅ COCI (0.2 mol) are slowly dispersed at -28 ° C. with 12.9 g of aziridine (0.3 mol) and 21 g of triethylamine

109817/2223

■: - 39 -

in ethyl ether, implemented in the manner described in Example 8.

After filtering off the triethylamine hydrochloride and removing the ether by evaporation under reduced pressure, 102 g of the waxy white product mentioned in the first part of Example 11 are obtained. This product is dissolved in 500 ml of a mixture of acetone and CpCl ^ i ¹ * * (50 volumes- ^).

This solution is added dropwise to 300 g of the polyether urethane polymer (B), dissolved in 500 ml of CH ₂ Cl ₇ I? ^, At reflux temperature. After the addition is complete, the reflux treatment is continued for a further 30 minutes. To separate the polymer formed, 700 ml of 1,1,2-trichlorotrifluoroethane are first distilled off, after which the remainder of the solvent is then evaporated off under reduced pressure. 200 g of a light yellow, highly viscous polymer with a number average molecular weight of 13,500 are obtained. is soluble in the solvents mentioned in the preceding example and contains 1 isocyanate group per molecule. ■; . . .

This polymer solidifies in the presence of moisture to a polyamide resin, which is in all tested solvents is insoluble even at elevated "temperatures. The solution of the polymer (not separated) is. by adding a mixture of trichlorethylene and 1,1,2-trichlorotrifluoroethane (50 volume- ^) diluted to 1 liter.

use

11.5 ώί ^: the solution is dissolved in 1 1 trichlorethylene s.,

10 9 8 17/2223 BAD ORIGFNAL

/ and do it in such a way that the same concentration of the fluorinated component as in Example 11 and a polyraene concentration of 200 g / l is achieved.

Comparative tests using goods made from natural and synthetic fibers are carried out. The results are summarized below in tabular form:

Wool At first-
value • After 5 chemical
cleanings B. after 5 measures
washes Q B. * Oil repellency
Water repellency Away' '■ .- ■ A A. 7th
70-80 cotton 6-7
80 6th
70-80 Oil repellency
Water repellency 8 7-8
80-90 90 7th
80 6-7
70-80 flax 6th
70 6th
70 Oil repellency
Water repellency 7-8 _ _: fif-
90 '90 7th
80 6-7
70 polyester
Oil repellency
Water repellency 6th
60-70 6-7
70 6th
50-70 polyamide
Oil repellency
Viasserabs tossung 7-8 8 7th
70-80 6th
70 6th
60-70 5-6
70 acrylic
Oil repellency
.Water repellency 7-8; "· - ■ ^-: 'T ^
80 80-9 &; >: _, 6-7 6-7
80 6th
50-70 6th
70 8 7-8
80-90 90 1 --- I.
'""*'. 7th
70 6th
80 5
70 7-8 7
80-90 90 6-7
70-80

109817/2223

A. - 41 - Ί 2018 365 B. AWAY At first
value 80-90 8th B. After 5 chemical after 5 barrel
cleansing washes 6th 6 6 80 7th A. 70-80 50-70 70 ■ acetate 80-90 Oil repellency 8th 6-7 6th 7 5 -Water off-
shock 80 60-70 70 70 50-70 Chlorovinyl Oil repellency 7th Water'ab ^
shock 70-80

A = product which has been produced according to example 11 B = product which has been produced according to example 12

Example 13 · ~ "..'-. /.

54.2 g of C ₉ P ₁₉ COOu ₂ H ₅ (0.1 mol), previously ^{cooled to O 0} C, are slowly reacted with 8.6 g of aziridine (0.2 mol), with an increase in the temperature to one Value above 5 ⁰ C is avoided. After the addition, the temperature · door is slowly increased to 30 ⁰ C. »

The initially viscous white reaction product gradually turns yellow and takes on a waxy consistency. It is washed with 3 portions of 50 ml each of carbon tetrachloride to remove the C ₂ HcOH formed, which occurs as a by-product. This gives 58 g of a waxy, light and white solid which slowly turns yellow at room temperature. This compound is insoluble in the chlorinated solvents mentioned in the preceding examples and partially dissolves in 1,1,2-trichlorotrifluoroethane, acetone, ethyl acetate and ethyl ether. It is in 200 ml

109817/2223.

a mixture of acetone and CpOT.,]?., (50 volume-? ») dissolved and dissolved with 500 g of the polyether prepolymer (A) in 0.5 1 1,1,2-trichlorotfifluoroethane, according to the example 1 described method of operation implemented.

The polymer formed by the reaction can be separated from its preparation solution in the manner described in Example 1. In this way, 5% of an opaque and highly viscous yellow-brown polymer with a number average molecular weight of 32,500 is obtained. This polymer contains 18 free isocyanate groups per molecule and dissolves in ethyl acetate, acetone, 1,1,2-trichloro-trifluoroethane, Isopropyl alcohol, trichlorethylene, tetrachlorethylene ,. OCl., GHCl ₅ and CH ₅ CCl ₅ .

The volume of the preparation solution is determined by adding a mixture of 1,1,2-trichlorotrifluoroethane and trichlorethylene (50 volumes - ^) diluted to 1790 ml.

use

. 50 ml of the solution are dissolved in 1 l of trichlorethylene at room temperature dissolved, in excess of that a polymer concentration of 10 g / l is achieved. Wool samples are treated "with 90% impregnation". Drying takes place at a temperature of 12O ° G during a period of 8 minutes. The test results are summarized below

Initial After 5 Chemicals After 5 Wet · Worth ■ Cleanings Washes

oil repellency Water repellency, shrinking surface, 36

8-9 8th 7-8 90-100 80-90 80-90 2.3 2.5 2.5

109817/2223

Example 14

300 g of the polyether polymer (A) dissolved in 250 ml of an anhydrous ethyl acetate are mixed with 18.8 g of phenol, and the solution is refluxed for a period of 4 hours. The prepolymer obtained still contains -1-ITOO groups per chain and is reacted with 8.8 g of C ₂ H ₅ -I ¹ TH-G ₂ H-NH ₂ in the manner described in Example 9.

The reaction mixture is refluxed and, with vigorous stirring, is dissolved with 53.2 g of CqF ^ qGOGI (0.1 mol) in 200ml 1,1,2-trichlorotrifluoroethane, mixed.

The reflux treatment is continued until the decomposition of the HGl occurring as a lift product has ended is. Then the solution is cooled and by adding Methyl chloroform diluted to 1780 ml.

The polymer obtained in the manner described above, the 2 phenol-protected isocyanate groups per molecule contains, is separated off in such a way that 160 ml of T, 1,2-i0riehlortrifluoroethane are first distilled off, whereupon the remaining solvent under reduced pressure in the manner described in Example 6 is separated. Man receives 376 g of a highly viscous yellow polymer with a Number average molecular weight of 3600 obtained in the solvents mentioned in the previous example is soluble. The polymer can be stored indefinitely, even in the presence of moisture.

109817/2223

use

The treatment is carried out in such a way that the in The concentrations and measures given in the example presented are observed. The results are practically the same.

_t , example 15

8.6 g of aziridine (0.2 mol) are added dropwise to a 100 ml flask containing 52.4 g of C ₉ I ₁ QGOOG ₂ H ₅ (0.1 mol). The mixture is kept at -28 ° 0 with stirring for a period of 48 hours. Then was the temperature to 5O ⁰ O allowed to rise. A yellowish-brown, waxy solid substance is obtained. _{The CpH 1} -OH which occurs as a by-product in the reaction is removed by extraction with 3 portions of 25 DiI CH ^ CCl each. 58 g of a waxy, solid, dark yellow polymer are obtained. This amount is dissolved in 300 ml of a mixture of 1,1,2-trichlorotrifluoroethane and acetone (50 volume? »). The polymer is insoluble in the chlorinated solvents already mentioned repeatedly and dissolves easily in 1,1,2-trichlorotrifluoroethane, acetone, isopropyl alcohol and ethyl acetate. The solution prepared in the above manner is added dropwise to 300 g of the polyether urethane prepolymer (A) dissolved in 0.5 1 1 of 1,2-trichlorotrifluoroethane under reflux in a 2 1 flask with stirring. After the addition is complete, the reflux treatment is continued for a period of about 30 minutes, after which it is diluted to 1780 ml using 1,1,2-trichlorotrifluoroethane and trichlorethylene (50 volume - ^ - ratio). • This gives a slightly viscous dark yellow solution. The polymer can be separated from the solution in the manner described in Example 7 prior to dilution. Man

10 9817/2223

receives 36Og of a highly viscous yellow polymer with a Number average molecular weight of 32,000 containing 18 free isocyanate groups per molecule. This polymer dissolves in 1,1,2-trichlorotrifluoroethane, trichlorethylene, Perchlorethylene, methylchloroform, acetone and CCl ,.

The behavior of this product, the way it is used as well the results obtained coincide with the corresponding packages of Example 13.

Example 16 /

If the product is not intended to be shrink-proof, then smaller amounts of free NGO groups are sufficient. In a 100 ml flask containing 54.2 g of CqF ^ qCOOC ^ (0.1 mol) will be dropwise 8.6 g of aziridine (0.2 mole) in the above in the manner described in Example 15 introduced.

The solution, which 58 g of the product obtained in the above manner in 300 ml of a mixture of 1,1,2-trichlorotrifluoroethane and acetone (50 volumes- ^) contains will-dropwise 150 g of the polyether urethane prepolymer (A), dissolved in 0.3 1 CpCl ^ P ^, under reflux and with stirring in one 1! - »Piston clogged. When the addition is complete, the Reflux treatment for a period of about 30 Continued for minutes, followed by a dilution to 830 ml using a mixture of 1,1,2-trichlorotrifluoroethane and trichlorethylene (50 volume mixture). A yellow viscous solution is obtained. In in this case the polymer can also be separated in this way * that first 450 ml of 1,1,2-trichlorotrifluoroethane distilled off v / ground, whereupon the remaining solvent in the in Example 7 is removed in the manner described. One receives 205 g

109817/222 3

of a highly viscous and yellow polymer with a number average value the molecular weight of 17,000, which contains 4 isocyanate groups per molecule and in the chlorinated ones and non-chlorinated solvents, which in the example above. The polymer is in the presence of moisture as well as during one prolonged exposure to heat unstable and thus resembles the

^l "according to Example 15 synthesized polymers. It is long-

sam converted into a solid, rubber-like mass that can be used in all solvents tested (even at elevated temperatures ) is insoluble.

use

21.2 ml of the yellow viscous solution obtained in the above V / ice are diluted with 1 l of trichlorethylene, and in the sense that a polymer concentration of 10 g / l is obtained, which corresponds to the concentrations of the examples 13, 14 and 15 is similar. The concentration on that fluorinated content is adjusted to 1.39 g / l.

There are comparative tests made using goods natural and synthetic fibers. * The results are; summarized below

109817/2233

■ - 47 - v- ^;

.:. Initial- After 5 Chemical- After 5 Wet

value cleanings washes

• A £ ä £ - AI

Wool - ■. '■■:;

• Oil repellency '8 8 Water repellency 100 100

cotton

Oil repellency 8 7-8
Water repellency 90-100 100 80-90 90

Flax . · "■ '" .-

Oil repellent 8 8

"Water repellency 90-100

Polyester .. '.

Oil repellency 8 7-8 Water repellency 90-100 90-100

Polyami d

Oil repellency 8-9 8

V / ater repulsion 100

Acrylic materials

Oil repellency 8 7-8

Water repellency 90-100

Ace _: did

Oil repellency 8 8 V / water repellency 90-100

Chlorinated vinyl ~

Oil repulsion 8 8 Viasser repulsion 100

A = product, produced according to example I5 B. = Product manufactured according to example 16

109817/2223

7-8
90-100 7-8
90-100 6th
80-90 7th
80-90 7th
80-90 7th
90 7th
80 6-7
80 7th
90 7th
80-90 7th 7th
80-90 7th
90 6-7
90 • .7
80-90 6-7
80-90 7-8
80-90 7th
90-100 7th
80-90 7-τ8.
80-90 7th
90 7th
80-90 7th
80. 7th
80 7th
90 7th
90 7th
80-90 6-7
80 · 7th
90 7th
90 7th
80-90 6-7
80

It should be pointed out that 'if goods with the Products are treated. To give the wool fibers contained in these goods a shrinkage resistance to lend, the goods also become crease-resistant to a considerable extent.

In the treatment of goods from synthetic fibers no inventive products should be used, which blocked with phenol isocyanate groups as (C 15O ⁰⁾ would occur a destruction of the fibers at the high temperatures that are required to liberate phenol.

All of the above examples provide polymeric products that differ in terms of their properties from clearly distinguish the output connections, namely regarding

- solubility in common chlorinated solvents,

- the high oil repellency, "

- the good water repellency as well as

- the excellent shrinkage strengths that the treated Goods are loaned out. Such properties

have never been united in previously known products.

The following examples are intended to show that if the precise manufacturing conditions are not complied with, the desired products are not obtained or substantially are ineffective. '. .

Example 17

29.2 g of G ₄ F ₉ -COOC ₂ H ₅ (0.1 mol) and 8.6 g of aziridine (0.2 mol) are reacted with one another, care being taken

109817/2223

becomes that the temperature exceeds ^{5 0 O.} The reaction product is with 3 portions of 20 ml of COl-. washed _{to remove the C 2} H ₁ -OH occurring as by-products. * This gives 33 g of an oily yellowish product which dissolves in a mixture of acetone and CpCl.,] ?, (50 volume mixture). The product is insoluble in the chlorinated solvents described in the preceding examples and dissolves somewhat in 1,1,2-trichlorotrifluoroethane, benzotrifluoride, acetone and ethyl acetate. It is then reacted with 300 g of the polyether urethane prepolymer (A) in the manner repeatedly described above.

A light yellow solution is obtained which, after removal of the solvent, gives 333 g of a slightly viscous polymer with a number average molecular weight of 28,500. This polymer contains 17 isocyanate groups in the molecule. The polymer is unstable over time and turns into a compact yellow mass that is insoluble in all solvents tested. The results of the processing of knitted wool products by immersion in a Irichloräthylenlösung, wringing up to, would take $ 100 and heat treatment at 120 ⁰ C for a period of 10 minutes .are summarized below. The concentrations in the processing bath are as follows:

- Polymer content: 43 g / l

- Concentration of fluorinated parts: 3 g / l.

109817/2223

At the beginning, after 5 chemical washes, after 5 wet cleaning

Oil repellency none none no water repellency 0-50 0-50 0-50 shrinkage area ₃ fo 0.8 1.0 1.2

Example 18

\ 44.2 g of G P _{7 15} COOG ₂ H ₅ (0 ₉ 1 mol) and 8.6 g (0.2 mol) Äthyleniniin are reacted according to the procedure described in Example 1 "Method P ''.

The product obtained, which is insoluble in the chlorinated solvents mentioned repeatedly in the above examples, is dissolved in a solution of 1,1,2-trichlorotrifluoroethane and acetone with 16.8 g of hexamethylene diisocyanate, 00K- (OH ₂ Jg-NOO, -aas' is dissolved in a similar manner in C ₂ Cl ₅ P ₅ , reacted and brought to boiling temperature. This gives a liquid bispersion _s which is insoluble in chlorinated solvents ₀ In addition, the dispersion is unstable are insoluble in all tested solvents and their mixtures,) even at elevated temperatures.

Example 1 ^: 9

12-9 g of asiridine and 86 ₉ 5 g of C ₇ E ₁₅ OOCl are reacted in the ^{manner described in Beispi v} ? JL 5.

The product obtained, which is in solution in 1,1,2-trichloro-trifluoroethane and acetone, is reacted with an ethyl acetate solution of 25 g of phenyl methane-4 »4 ^f -diSQcyanat. As the reaction proceeds, a powdery precipitate is formed, which is found in all solvents tested

109817 / 222.3

-51 - '.- ■■■■■■ -

* is insoluble.

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

.- ■■ '■ - NGO

- -GH ₂ -O-GO-SH- / Y-CH,

or with 17 _f 5 g TolTiol-2,4-diisocyanate, leads to products which become unstable over time and decompose to polyurethane rubbers which are insoluble in all common solvents. They can only be dispersed in the chlorinated solvents already mentioned. -

The dispersions are also unstable with simple stirring and provide agglomerates which are insoluble in all solvents tested or mixtures thereof, and even at elevated temperatures. ■ -.- ■ "

working conditions

1, Rf-COOR + aziridine reaction

The response requires:

a) The two reagents must be fed to the reactor at the same time, so that a satisfactory structural Regularity is achieved in the polymer.

b) The temperature must not exceed 5 ⁰ G, in order to avoid heat and color degradation of the polymer.

c) The stirring must be vigorous to avoid local overheating avoided due to the strongly exothermic character the two reactions (amidation and polymerization) are due.

109817/2223

If only one of the three conditions outlined above ' If this is not observed, then the subsequent reaction of perfluoroacylamido-N-alkylamine and prepolymers leads to the free -NCO groups, easily 2U rubbery or unstable products.

2. Rf-COCl + aziridine reaction

. The response requires:

a) The temperature must not ^{exceed -25 0} C, so that a sharp polymerization of the imide formed is avoided.

b) It must be stirred vigorously so that local overheating is avoided, which would lead to polymerization of the existing Selenimine would lead to the formation of the monomeric imide.

c) Filtration of the iriethylamine hydrochloride by-product must be carried out at a temperature not exceeding -25 ° C. The precipitation should be beneficial Way to be washed with (ΟΗ, ΟΗρ) ρΟ, previously set to -3O ° C has cooled down.

w If these conditions are not met, it is to be expected that the end product will become rubbery or unstable over time.

3. Rf-COOR and aziridine reactions

After the amidation reactions have ended, the alcohol released as the reaction product should be completely removed in order to avoid possible secondary reactions with the -NCO groups and the formation of rubber and urethane foams .

109817/2223

4. Reaction of perfluoroacylamido-N-alkylamine with a prepolymer containing ITOO groups

This response requires: ■

* A) To set homogeneous phase reaction conditions should both the perfluoroacylamido-N-alkylamine and the prepolymer, which contains free -NCO groups,

• 'j - in a mixture of at least two solvents . that are resolved from

a) a fluorochlorinated organic solvent in an amount of 50 - 80 volume ^ (such as 1,1,2-Tr.ichlorotrifluoräthan) and

b) a polar organic solvent in an amount of 20 - 50 volume ^ (for example acetone, ethyl acetate, methyl ethyl ketone or the like) consists,

B) The mixture of solvents should absolutely be anhydrous so that partial hydrolysis of the -NGO - groups in -NH ₂ groups is avoided, and so that the reaction with the remaining -NCO groups, which leads to the formation of insoluble ones, is avoided Rubbers and polyurethane foams. ■

C) The perfluoracyi-N-alkylamine solution should slowly be the

, refluxing solution of the prepolymer, wel-

-i "ches free -NCO groups can be added. It ■„>'■■
- should not be done the other way around. Otherwise, inter- and intramolecular bridges will be formed, making the product rubber-like and unstable over time.

1098 17/2223

5. Reaction of the prepolymer containing -MGO groups which are partially blocked by phenol and polyamines "

Requirements:

A) The response should be in a misctamg; ' from at least two solvents are carried out, which consist of the following components ":

a) A fluorochlorinated organic solvent in an amount of 50 - 80 volume jS (such as "for example 1,1,2-trichloride if luoroethane),

b) a polar organic solvent in an amount to 20-50 volume ^, such as acetone, ethyl acetate, Methyläthy ketone!.

B) The mixture of solvents should absolutely be anhydrous so that a partial hydrolysis of the -UCO groups in -NHp groups with the consequences already described is avoided.

*. C) The solution of the polyester or polyether polymer with the partially phenol-blocked -HGO groups should be slowly prepared for the polyamine solution. It should not be done the other way around. Otherwise, -IH groups of the polyamine would react with available -NGO groups, the subsequent reaction with RfGOX leading to a product of the formula I in which m = O ₀

Try dining

Below are the terms and conditions for completeness described under which the tests were carried out

109817/2225

the results of which are given in the preceding examples are:

.1. Treatment of the goods :

1.1. Treatment by spraying : the tests are carried out using balanced strips of fabric 100-170 cm long and 20 cm wide. The strips are passed between three groups of nozzles spraying one side while two groups of nozzles spray the other The nozzle bore is 0.5 nanometers in diameter, while the spray cone angle is 90 °. The solution to be sprayed is fed to the nozzles under a pressure of 4 Atm. The speed of the goods is regulated in such a way in each case, that the product is evenly and thoroughly wetted after spraying, but not dripping, ie that the absorption is about 120-150 Ge-weight ^ or about 80-100 volume- ^.

Speed abs orpti on

Woolen cloth 8 m / minute 80 vol .-? * -

Carded woolen cloth - 5 m / minute 105 vol .- #

Acrylic goods 7 m / minute 102 V.ol.-jS

Cotton cloth 5 m / minute 100 vol .- $

Cotton / polyester cloth 10 m / minute 80 Vol.-Ji.

After spraying, the fabric is weighed to be precise the absorption, based on the weight, to determine what the goods on a rack for drying and hardening of the su polymer to be tested.

109817/2223

. - 56.-

1.2 Treatment by immersion : In this case, be

• also weighed strips of goods with a length of

100 - 170 cm and a width of 20 cm are used. Each strip is fed through "a four-roller pad ironer ". and gently wrung out (pressure: 0.2-0.5 kg / cm). Huh

the impregnation are weighed the strips for precise loading • ". mood of the amount absorbed. The drying and curing * are performed on a frame as in 1.1.

2. Treatment of yarns and knitted goods:

2.1 Treatment by spraying: A conventional dry cleaning drum device is used in which a spray nozzle is provided at the entrance to which the material to be processed is fed. The material is weighed, introduced into the device and washed in the latter before treatment. The treatment solution contains the amount of polymer to be applied to the material, dissolved in a certain amount of the solvent which is twice the weight of the material; is equivalent to. The solution is the nozzle under pressure. P · of 4 atm while the drum of the device is running. When the spraying is finished, the drum will turn for a further 10 minutes.

* leave so that the solution evenly penetrates the material ^ impregnated. Subsequently, the solvent is evaporated and a heat setting is carried out, namely under Use of heating equipment included in the Device are installed.

2.2 Treatment by impregnation : The same device is used as in case 2.1. The material will

109817/2223

- ■■■ 57 -

weighed, inserted into the device and prior to treatment •washed. Then - the impregnation solution in the device is filled, whereupon the drum during a Is allowed to rotate for a period of 30 minutes. After this When the drum is stopped, the excess solution is pumped back into the storage tank. Without switching off the pump it will rotated the drum at washing speed for a period of 1 minute, for a period of Switched off for 1 minute and again for a period of. Let it spin for 1 minute. The pump is stopped and the drum is set in motion again to allow drying and to effect heat setting by heating devices, which are built into the device.

Paintings

The compounds of the invention are also suitable as. Additives for paints. The tests are performed using Paints carried out on an acrylic, vinyl, epoxy and melamine basis. .

The quantities imported vary between $ 0.5 and $ 2 by weight, based on the total dry weight. The paints mixed with the compounds can be used in very Evenly distribute over the surface to be protected (glass or metal) and form a PiIm with improved Adhesion, with increased evenness and with increased compactness. ■ -

The compounds are added to paints that have a pigment contained in a dispersed porm, then the parbend brilliance ' elevated. .

1098 17/2223

■ '- 58 leather and paper

Leather and hides obtained by spraying with solutions of the compounds according to the invention in chlorinated organic Solvents treated generally take a pronounced fastness to water and corrosive agents. -

The coating of paper is of particular interest when packaging materials for food are made should be asked. Though, the treated paper retains its porosity, it is particularly resistant and effectively protected against water.

109817/2223

Claims (1)

Claims 00 where ·, '■ X for a hydrogen atom, a methoxy group, ethoxy group, Propoxy group or isopropoxy group, 7. a hydrogen, torn, a methyl group, xthyl group, propyl group or isopropyl group, Rf is a perfluorinated hydrocarbon chain -C ₂ Fp- ^, in which s is an integer from 5 - 11j a, b and c is integers from 2- Are 10, η is an integer from 1-10,. . m is an integer of 1 τ 10, ρ is a whole number from 1 - 5, q is an integer from O - ■ 5 and _.'.-.-..-- S represents a polyester or a polyether polyurethane chain, which is the AB number ρ of the -NGO groups in the formula are indicated, with the number average molecular weight of the compound not exceeding 60,000, and precursors thereof. Compounds in which the -ITCO r groups are "temporarily" blocked. 2. connection according to claim -1, characterized by gelcennzeiehnet, that their number average molecular weight at least 3500 is. 109817/2223 3. Compounds according to claim 1, characterized in that their number average molecular weight is at least 3500 while ζ is at least 7. 4- connections according to claim 1, 2 or 3, characterized in that that the [^] (NGO) part is a number average of the . Molecular weight of 3,000-15,000. 5; Compounds according to claim 1, 2 or 3, characterized gekennzeich- ψ net that the NGO groups are linked in the [^] (NGO) moiety with alkylene chains, the latter being the chains are originally in the di- or Iriisocyanat that led to the formation of the share. 6. Compounds according to claim 1, 2 or 3, characterized in that that the [^ T] (NGO) portion is a number average the molecular weight of 3000-15000 and the NCO groups in the []>] (NCO) -Anteil mit'Alkylenketten linked the latter being those chains originally present in the di- or triisocyanate used to form of the share-led. .7. Method of making a solid oil or water repellant • organic or inorganic surface., Characterized that on the surface a solution of a connection or ■ its precursor according to claim 1, 2 or 3 is applied. 8. Method of making an iDextile material repellent to oil and water, characterized in that the material with a solution of a compound or its precursor according to claim 1, 2 or 3 is treated. 109817/2223 ■ '■ - 61 - 9. -'Procedure according to. Claim 8, characterized in that the connection or the ■ predecessor continues to be characterized by that the [^>] (NGO) portion is a number average the molecular weight of 3,000-15,000 and the NCO groups linked to alkylene chains in the [^] (NGO) part are, the latter being those chains that were originally were present in the di- or triisocyanate, which for Formation of the proportion led, 10. The method according to claim 8 or 9, characterized in that that the solvent in the solution consists predominantly of an organic one chlorinated solvent. 11. Textile material, characterized in that it is with a Compound or its precursor according to claim 1, 2 or 3 has been treated. 12. Textile material, characterized in that it is with a Compound or its precursor according to claim 1, 2 or 3 has been treated, wherein the. [^> ] (NGO) p component has a number average ■ molecular weight of 3000 - 15,000 and the NGO groups in the [21 (HGO) moiety with alkylene chains are linked-, "the latter being the chains that were originally in the di- or triisocyanate, which led to the formation of the share. 109817/222 3 L e r s e J t e