DE2034155A1 - Fluoroalkyl sulfonamidoalkyl esters composed of segments. Process for their preparation and their use - Google Patents

Description

PATENT LAWYERS MUNICH 2
■ VAL 33
TEL. 0811 / 226SM
295051
CABLES: THOPATENT
TELEX: TO FOLLOW Dipi-chem. Dr D. Thomsen DipUn * H. Tiedtke
Dipi-chem. G. Bühling 2034155 FRANKFURT (MAtN) SO
FUCHSHOHL 71
TEL 0811/514666 Dipi-ing. W.Weinkauff

Reply requested to: Please reply to:

8000 München2 July 9, 1970 case lovine et al 2-52F / T 27CO

National Starch and Chemical Corporation New "York / USA

• Constructed from segments

Fluoroalkylsulfonamidoalkyl esters, process for their preparation and their use

The invention relates to new fluorine-containing monomers and homo- and derived therefrom. Mixed polymers. The invention also relates to * fabrics or other articles, which are "tempered" or coated with such polymers.

The object of the invention is to provide novel, monomeric fluoroalkylsulfonamidoalkyl acrylates built up from segments and methacrylates to create that when applied conventional polymerization processes either alone or in the presence of other vinyl monomeric vinyl polymerization reactions can enter.

009883/2297

■ - 2 -

It is also an object of the invention, proceeding from the mentioned fluorine-containing acrylates and / or To create methacrylates, homopolymers or copolymers, which, when used for the treatment of substrates with either fibrous, porous or more or less smooth surfaces, these substrates are excellent Give water, oil and water repellency.

In the case of the new, monomeric, fluorine-containing acrylic acid and methacrylic acid esters !! acts according to the invention they are those of the formula

Hf-Z-SO ₂ -JI-XOO

what mean!

_{Ef is a ReSt 5} having 3 to 20 carbon atoms inclusive, consisting of a straight or branched atom which is optionally substituted in the perfluoro group by at least one hydrogen, chlorine, bromine or iodine atom; chain perfluoroalkyl radical j cyclic ali- j

phatic perfluoro group or polycyclic aliphatic perfluoro group;

Z is an alkylene, alkenylene or cycloalkyl radical, a cycloalkyl radical with a bridge bond, a polycyclic alkyl radical, a polycyclic alkyl radical with a bridge bond, or a radical

009383/2297

'ORIGINAL INSPECTED

of the formulas:

- CH) _n - and - (CH * C) _n -,. R "R"

in which R "is a hydrogen atom, a saturated or unsaturated hydrocarbon off rest with 1 to 20 carbon atoms, a cycloalkyl radical, a cycloalkyl radical with a back bond, a polycyclic radical Alkyl radical, a polycyclic alkyl radical with a bridge bond, an aryl or aralkyl radical represents and η = an integer of 1 to 20 inclusive;

«■ '■ R with a hydrogen atom or an alkyl radical

1 to 6 carbon atoms;
X is a straight or branched-chain alkylene radical of the formula: (CHg), in which m ■ = an integer from 2 to 14 inclusive, a cycloaliphatic radical, a cycloaliphatic radical with a back bond, an aralkyl radical, an aryl radical or a di-alkylene oxide radical and

R ^{1 is} a hydrogen atom or a methyl radical.

Examples of those corresponding to the formula given, monomeric pluoroalkylsulfonamidoalkylacrylic acid and methacrylic acid built up from segments

009883/2297

. BATH ORIGINAL

acid esters are:

a) N-methyl-N-acryloxyethyl-2-perfluoroheptyl-ethyl-isulfonamide;

b) N-ethyl-N-acryloxyethyl-2-perfluoroheptyl-ethan-isulfonamide;

c) JT-methyl-N-acryloxyisopropyl-2-perfluoroheptylethane-1-sulfonamide;

d) N-ethyl-N-acryloxyätliyl - ^ - perfluorlieptyl-butan-isulfonamid;

e) N-methyl-N-C ^ -acryloxybuty ^^ - perfluorloptylethane-i-sulfonamide;

f) N-methyl-N-methacryloxyethyl-δ-perfluoroheptylnorbornyl-methanesulfonamide;

g) N-methyl-N-acryloxyethyl-11-perfluoropropyl-undecane-1-sulfonamide;

h) N-methyl-N-acryloxyethyl-2-octachloro-octafluor »

octylethane-1-sulfonamide; ' i) N-ithyl-N-acryloxyethyl - ^ - perfluoroheptyl-allyl-i-

sulfonamide; ·

J) N-Acryloxyäthyl - ^ - perfluorpropyl-cyclohexan-

sulfonamide; . ■ ·

k) N-methyl-N-acryloxyethyl ^ -perfluoropropyl-ethane-i-

sulfonaraid;
1) N-methyl-N-acryloxyethyl-4-perfluoroheptyl-butane-1-

sulfonamide; ,.

m) N-methyl-N-acryloxyethyl-16-perflüoroctyl-hexad-

can-1-sulfonamide; -. ,; _;

ARiGlMAL INSPECTED

0 0 98 8 3/2297 original

η) H-methyl-N-acryloxyethyl-perf luorcyclohexyl-methylene-.

sulfonamide and ■

ο) N-ethyl-N-acryloxyäthyl.-2-perfluorisononyl-ätliaii-1-sulfonamiü. .

In the fluoroalkyl monomers made up of segments according to the invention, the fluorocarbon radical Rf is linked to the sulfur atom of the sulfonamido ^{radical by means of a bridging hydrocarbon radical Z, which is referred to below as the “segment-forming} radical”. The nitrogen atom of the sulfonamido radical is in turn linked to an alcoholic radical esterified by either acrylic or methacrylic acid.

The presence of the hydrocarbon residue, i.e. the so-called "segment-forming" radical, which connects the fluorocarbon radical with the sulfur atom of the sulfonamido radical linked, increases the oil and water repellency of the new compounds according to the invention in comparison to known analogous compounds, in which such segment-forming residues are absent, quite considerably. When the oil and water repellent properties of the new connections built up from segments according to recognized test procedures with the corresponding properties of analog connections, in which However, the segment-forming residues are absent, to be compared do the new connections indicate perno'I? consistent with the invention a considerably better rating.

00988.3 / 2297

The new monomers according to the invention can be prepared according to one of two basic processes produce. The first of these procedures is

1. a reaction of a particular fluoroalkylsulfonyl halide made up of segments with Ammonia, ammonium carbonate, or a primary amine;

2. a reaction of the product obtained in step 1 with an alkylene oxide or a Gj-haloalcohol to form one composed of segments Fluoroalkylsulfonamidohydroxyl compound and '

3. an esterification of the latter, composed of segments, of the fluoroalkylsulfonamidohydroxyl compound with either acrylic or methacrylic acid to the desired monomer.

The for · preparation of the new monomers according to The second sequence of actions applicable to the invention * consists in

1. a reaction of a particular fluoroalkylsulfonyl halide made up of segments with an amino alcohol for the direct preparation of a segmented fluoroalkylsulfonamidohydroxyl compound and

2. a subsequent esterification of the formed ,, segmented fluoroalkyl sulfonamido hydroxyl compound with either acrylic or

009883/2297

"Methacrylic acid for the production of the desired monomer.

The new fluorine-containing acrylate or methacrylate monomers according to the invention can be thereupon either polymerize to homopolymers or with a or more other ethylenically unsaturated monomers copolymerize to form copolymers.

In the case of the starting compounds used as starting compounds for the preparation of the new monomers according to the invention, Fluoroalkylsulfonyl halides built up from segments are compounds of the formula:

Rf- Z - SO ₂ - Y ..---. Ι

where Rf and Z have the given meaning and Y stands for a halogen atom consisting of a chlorine, uromic or iodine atom. These connections are in the USA patent application of serial no. 755 814, üei the preparation of these segmented fluoroalkylsulfonyl halides suitable fluoroalkyl halides built up from segments are sulfonated and the obtained Reaction products according to known halogenation processes converted into the desired halide compounds. Sulfonating agents that can be used here are, for example, alkali metal sulfites, alkali metal bisulfites, Sulfuric acid, sulfur dioxide, sulfuryl chloride and chlorosulfonic acid. In a typical procedure, 1 mole of the segmented fluoroalkyl halide is included

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203A155

1 to 2 moles of a mixed Alkalitnetallsulfits and then heated for about 1 to 30 hours at a temperature of about 100 ° to 200 ⁰ C. The reaction takes place either in water or in a mixture of water and a water-miscible solvent.

When carrying out the first of the described reaction sequences for the preparation of the new monomers According to the invention, the respective fluoroalkylsulfonyl halide is initially mixed with a nitrogenous Connection, e.g. B. liquid or gaseous ammonia, ammonium carbonate or a primary alkylamine with 1 to 6 carbon atoms to the corresponding sulfonamide compound implemented. The method of operation that can be used here is known to the person skilled in the art. As a rule, When carrying out this amination process, a large molar excess of the nitrogen-containing one Compound with the respective segmented fluoroalkyl halide at room temperature or a temperature slightly above room temperature approximately. / Implemented for 2 to 4 hours. For example, in the production of the sulfonamides, if gaseous ammonia is used as the aminating agent, the ammonia is carried out a solution of the halide in question in an inert one Solvent about 25 to 40 minutes or until completion the implementation left pearls.

The sulfonamide compound obtained is then added with an alkylene oxide, e.g. ethyleneo>: id, propylene oxide.

0 0 9863/2297

BATH ORIGINAL

or butylene oxide, or rait an ω-halogen alcohol, for example. Ethylene chlorohydrin, propylene chlorohydrin or 4-chloro-1-butanol converted to the corresponding »sulfonamido compound having a terminal, functional hydroxy radical. The sulfonamides are reacted with the alkylene oxide using equimolar concentrations of the two reactants in an organic solvent, e.g. ethanol, in the presence of a basic catalyst, e.g. potassium hydroxide, in a concentration of about 0.1 to 5%, based on weight of the suIfonaraid made up of segments, should be available. The reaction is carried out in a closed vessel for about 1 to 24 hrs bei'einer temperature of about 60 ° to 120 ⁰ C. Typically the reaction occurs under an intrinsic pressure of no more than about 35 kg / cm (500 psi).

The sulfonamide, which is composed of segments, is reacted with the respective Cu-haloalcohol in the presence of a proton acceptor at atmospheric pressure or a pressure slightly above atmospheric pressure. Usually you work on implementing that in one organic solvents such as ethanol, 1-propanol or tetrahydrofuran is carried out with against a molar excess of w-haloalcohol the sulfonamides Suitable proton acceptors are alkali metal hydroxides, such as sodium or potassium hydroxide, Alkali metal alkoxides, such as sodium methylate, or alkali '»

009883/2297

metal carbonates, such as potassium carbonate. The latter reaction is carried out for about 1 hr to 24 at a temperature of about 75 ° to 15O ⁰ C.

When carrying out the second of the described reaction sequences for the preparation of the hydroy $ containing sulfonamide derivatives used as starting materials, the respective fluoroalkylsulfonyl halide composed of segments is reacted with a molar excess, in the order of magnitude of about 5 to 100% by weight, of an amino alcohol dissolved in water . Suitable. Amino alcohols are, for example, ethanolamine, propanolamine or butanolamine. The reaction is allowed to proceed std usually about 1 to 24 at a temperature of about 35 ° C ⁰ 100 his. To neutralize the acid formed during the reaction, a proton acceptor, such as, for example, triethylarain, or an excess of the amino alcohol in question is added to the reaction, g'emi, sch. This proton acceptor

k should be based on approximately equimolar concentrations the weight of the segmented sulfonyl

halides, can be used.

Which consist of segments and prepared by a \ of the two described Reaktionsfolßen. Fluoroalkylsulfonaraido alcohols are compounds which are insoluble in water and which can be isolated from the resulting reaction and purified by conventional extraction or crystallization processes.

009883/2297

BATH

Both of the described reaction sequences lead to the. Formation of a segmented fluoroalkylsulfonamido compound of the formula:

Rf-Z-SO ₂ - N - X - OH.

wherein Rf, Z, R and X have the meaning given. The latter compounds are colorless Liquids or low-melting, white or matt-white solids with characteristic melting points. Jtsei these compounds are new compounds, either as starting materials in the preparation of the new monomers according to the invention or per se as compounds that repel oil and water and also as starting materials or intermediates for a wide variety of other organic products Reactions typical of alcoholic compounds and are characteristic, can be used.

The acrylic acid and methacrylic acid esters of the fluoroalkylsulfonamidohydroxy starting compounds mentioned, composed of segments or intermediates, i.e. the new monomers according to the invention by reacting the respective starting material or intermediate with either an acrylic or Prepare methacrylic acid esterification agents by any of the known and suitable esterification processes. ·

0098 83/2297

For example, crystalline (glacial) acrylic or methacrylic acid can be reacted with the respective starting material or intermediate by placing the two reactants in the presence of about 0.1 to $ ^, based on the weight of the hydroxyl-containing sulfonamido compound, of a strong acid , for example sulfuric acid or benzenesulfonic acid, heated to reflux temperature. The removal of the 7 / water formed during the reaction by azeotropic distillation completes the formation of the desired ester. In general, in the implementation of a molar excess, in the order of about 20 to 100 wt.% _R, used acrylic or methacrylic acid. The reaction is allowed to proceed std at temperatures of about 80 ° to 150 ⁰ C to about 20. 2 -

In another method, acrylyl or methacrylyl chloride can be reacted with the respective segmented fluoroalkylsulfonamidohydroxy starting material or intermediate. The reactants should be used in approximately equimolar amounts in an organic solvent such as, for example, chloroform, diethyl ether or benzene. This reaction can be carried out about 2 to 20 hours at temperatures of about 55 ° to 100 ⁰ C.

In another method, a C ^ -bis C ^ alkyl esters of acrylic or methacrylic acid directly with the respective pluoroalkyl-

009883/2297

-13 - ■ ■■■■■■: ■■:

sulfonamidoalkoholausgaiigsmaterial or -intermediate product are transesterified in either acidic or alkaline, aqueous medium. Alkyl acrylates and alkyl methacrylates which are suitable for such uresterification reactions are, for example, methyl acrylate, ethyl acrylate and the corresponding methacrylates. The two reactants can be used in approximately equimolar amounts, although the alkyl ester should as a rule preferably be used in a molar excess, on the order of 20 to 100% by weight. The reaction temperatures employed are .Bereich of about 75 ° to 150 ⁰ C. The reaction tents be about 2 to 20 hours.

Although some preferred process parameters are given, it should be the preparation chemist do not cause any difficulties for the production of one or the other of the new acrylic acid or Methacrylic acid ester according to the invention to determine the most suitable conditions.

The new acrylic and methacrylic esters obtained are usually heavy oils or white or matt white solids with low Melting point. They usually resolve themselves in usual organic solvents such as benzene, Toluene, acetone, ethanol, isopropanol, chloroform and methylene chloride. It should be noted that let these derivatives be used as such as oil and water repellants «

009883/2297

When using the described, new, composed of segments fluoroalkylsulfonamidoacrylate and methacrylate monomers for manufacture. of homo- and random copolymers all customary, known and for each homo- or to be produced. Mixed polymers especially suitable vinyl polymerization processes can be used. Such polymers can, for example, according to processes triggered by free radicals, for example by bulk, suspension, solution or emulsion polymer ion processes, by ion-catalyzed polymerization processes or by means of stereospecific catalysts, for example catalysts of the Ziegler type, produced v / ground.

In the case of the ethylenically unsaturated derivatives mentioned for the preparation of the segments existing, fluorine-containing copolymers according to the invention usable comonomers are any, '-. ethylenically unsaturated monomers,

such as styrene, C-methylstyrene, acrylic and methacrylic acid esters of aliphatic alcohols, e.g. of methyl, ethyl, propyl, butyl, isobutyl, amyl, fiexyl, 2-ethylhexyl, octyl, lauryl or stearyl alcohol ', Acrylic acid, methacrylic acid, isoprene, acrylamide, methacrylamide, acrylonitrile, methacrylonitrile, Butadiene, vinyl propionate, dibutyl fumarate, dibutyl tnaleate, Diallyl phthalate, vinylidene chloride, vinyl chloride, vinyl

009883/2297

■■■ - 15 -

fluoride, vinyl acetate »ethylene, propylene and the like. All of these monomers can either be used alone or in combination with one another, together with one or more of the fluorine-containing acrylate or methacrylate monomers mentioned are polymerized according to the invention.

The new homopolymers and copolymers according to the invention thus contain building blocks, i.e. recurring ones Structural units, the formula:

R '- (CH ₂ -C) - R

0 «COX-II- SC) ₂ - Z - Rf

in which the individual radicals have the meaning given. ·

The new copolymers according to the invention should have at least about 1% by weight of units of one or more of the described, segmented, fluoralkylsulfonamide acrylate or methacrylate monomers derive included.

The polymers defined in this way are clear, colorless, water- and oil repellent solids. It doesn't need to be specially to be emphasized "that they are practically insoluble in water. They dissolve, however, relatively well in organic ones

009883/2297

Solvents such as acetone, benzene, chloroform and trichlorotrifluoroethane.

The new polymer compositions according to the invention are effective for treating any solid material, regardless of whether it is fibrous, have porous or more or less smooth surfaces, use. Such materials are, for example, textiles made of wool, cotton, polyester, nylon, polyacrylonitrile and other synthetic fibers, glass, paper, wood, leather, fur, asbestos, brick, concrete, metal, ceramic materials, plastics as well as painted or plastered surfaces. Taking this into account Materials mean the terms "to apply" or "Treat" both a coating and / or impregnation of porous substrates and the coating of impermeable substrates Substrates.

The latter materials can be treated by all known and suitable methods. Let it be Textiles are typically made using a "padding process", in which the textile material is replaced by an organic Solution of a fluorine-containing polymer guided according to the invention, then squeezed through a gap and finally heated briefly to evaporate the solvent, treat. Typical organic solvents are here isopropanol, acetone, methyl ethyl ketone and the like. The treated textile material is then through Heat at a temperature for about 5 to 10 minutes

009883/2297

BATH

cured from about 60 ° to 180 ⁰ C, wherein the full water and ülabstoßungsfghigkeit forms ..- 'Äshrend the curing may conveniently be a Lewis acid catalyst such as aluminum chloride, to be present to accelerate and complete the curing process. In addition, a surface coating method, such as a spraying or brushing method, can also be used to deposit a film of the water and oil repellent agent on the surface of the substrate.

The amount of additive required to provide adequate water, oil and soil repellency depends on the particular fluorine-containing polymer used, the particular substrate, and the particular intended use of the substrate being treated. As a rule, when only about 0.1% of the additive is used, based on the weight of the substrate, an "appropriately improved" water and oil repellency is achieved. On the other hand, it was found that the use of more than about 6 % of the water and oil repellent rendering agent, based on the weight of the substrate, no longer offers any particular advantage, since the improvement in repellency that can be achieved thereby is more than offset by the increased costs .

Finally, it was also possible to establish that the polymer measures according to the invention apply to the

009883/2297

desired substrates also in the form of an aqueous Emulsion can be applied.

The following examples are intended to illustrate the invention in more detail. In all of the examples, the term “parts” means “parts by weight ¹¹ ” unless otherwise stated.

example 1

This example illustrates the preparation of a typical segmented fluoroalkyl sulfonamide starting material or intermediate product for use in the subsequent manufacture of the new Monomers according to the invention.

A reaction vessel equipped with a reflux condenser, an acid trap and a device for mechanical agitation was charged with 40 parts of a 40% strength by weight aqueous methylamine solution. To this solution, which was kept at room temperature, 40 parts of 2-perfluoroheptyl-ethane-1-sulfonyl chloride dissolved in 50 parts of diethyl ether were slowly added over a period of about 1 hour. The reaction vessel was cooled in order to keep its temperature at about 35 ^° C. When the addition was complete, the mixture was refluxed for about 1 hour and then cooled to room temperature. The ether layer separated from the aqueous phase was washed with water,

009883/2297

until it was neutral to litmus, and then dried over anhydrous sodium sulfate. The dried ether solution was distilled under reduced pressure to remove the diethyl ether. It remained as 87% - ge yield a white solid with a melting zone of 87.5 ° to 89.2 ⁰ O back, the 2-perfluoroheptyl-ethane-1-sulfonamide N-methyl-consisted of.

Corresponding 'built up from segments Fluoroalkyl sulfonamides could be made, though in the process described instead of 2-perfluoroheptyl-ethane-1-sulfonyl chloride the following segmented fluoroalkylsulfonyl halides are used v / urdeh:

a) 4-perfluoroheptyl-butane-i-sulfonyl chloride; -

b) e-Perfluoroheptyl-norbornyl-methanesulfonyl chloride ';

c) 4-perfluoropropyl cyclohexanesulfonyl chloride;

d) 2-perfluoroheptyl-ethane-1-sulfonyl chloride and

e) 3-perfluoroheptyl-allyl-i-sulfonyl chloride.

Example 2

This example illustrates another Process for the production of a built up from segments Fluoroalkyl sulfonamide starting material or intermediate from its corresponding sulfonyl chloride.

One with a gas inlet pipe, a distilla-. ' ' facility and a facility; ζυτη mechanical

009883/2297

BATH ORIGINAL

2Ü34155

A reaction vessel equipped with this was charged with 40 parts of eenzene and 13 parts of 2-perfluoroheptylethane-1-sulfonyl chloride. Then was introduced into the system, gaseous anhydrous ammonia at a rate sufficient to keep the temperature of the system between .40 ° and 50 ⁰ C. This process was continued for 30 "minutes, after which the mixture was filtered and the reaction product was washed with water to remove residual ammonium chloride. The product was then dried and recrystallized from water to give a white solid with a melting point of 98 ° in 80% yield to 104 ⁰ O, ordering from 2-perfluoroheptyl-ethane-1-sulfonamide was obtained.

• Example 3

This example illustrates the preparation of a segmented fluoroalkylsulfonamidoalkylacrylic acid ester according to the invention.

Part A;

A pressure-tight reaction vessel equipped with heating, cooling and stirring devices was connected to the 30 parts of N-Methy1-2-perfluorheptyl-ethane-i-sulfonaraid, 9 »6 parts of ethylene chlorohydrin, 6.7 parts pulverized ^ tem potassium hydroxide and 80 parts of ethyl alcohol charged. The temperature of the reaction system was slowly increased, so that the contents of the vessel for about 2 hours on one

009883/2297

BATH ORIGINAL

■ .. ■■ - 21 -

2 O 3 A155

Heated Tenroeratur of 12O ⁰ C and was then held at this Tenroeratur about std long. 6 A pressure of about 5.25 to about 5.60 kg / cm ² (75 to 80 psi) developed within the reaction vessel. After the required heating time had elapsed, the contents of the vessel were cooled to room temperature and filtered.

The ethanolic solution was evaporated to dryness and the solid residue in dietary ether dissolved again. The ether solution was washed with water until the wash water was neutral to litmus, and then dried over sodium sulfate. The dried ither solution was used to remove the Distilled ether, an orange, solid residue was obtained. When recrystallizing from 25 parts of N-methyl-N-hydroxyethyl-2-perfluoroheptyl-ethane-i-sulfonamide were added to a methanol / water mixture in the form of a brownish * -yellow solid with a Melting point of 84 ° to 87 ° C obtained. -

Part B;

One with a stirring device, a template for receiving an azeotropic distillate, a cooler and a thermometer equipped reaction vessel with 32.5 parts of N-methyl-N-hydroxyethyl-2-perfluoroheptyl-ethane-i-eulfonamide, the preparation of which was described in Part A, 8 »7 parts crystalline Acrylic acid, 0.4 part benzenesulfonic acid, 0.4 part

0098 83/2297 bad original

Hydroquinone and 60 parts of toluene charged. The mixture obtained was about at reflux temperature Stirred for 6 hours. About 1.3 parts of water collected in the still.

The refluxed mixture was then washed with water and dilute sodium hydroxide to remove therefrom the unreacted acrylic acid and the unreacted hydroquinone. The toluene solution was then dried over sodium sulfate and then 0.005 part of the polymerization inhibitor hydroquinone methyl ether was added. The toluene was then distilled off at reduced pressure (12 mm Hg column) and a temperature of JO ^{0 C.} From N-methyl-W-acryloxyäthyl-2-perfluoroheptyl-ethane-isulfonamid existing product yield was obtained in the form of a matt white solid having a melting point of '47 to 4-9 ° C in 96% ^0.

ί Example 4

This example illustrates the preparation of other segmented fluoroalkylsulfonaraidoacrylic and methacrylic acid esters according to the invention.

Following the procedure described in Part A of Example 3, three more "segments prepared fluoroalkylsulfonamidoalkanols.

009883/2297 or _(GIN al, mspected

Each of the segmented fluoroalkyl sulfonamides listed in Table I below vairde with ethylene chlorohydrin in.den amounts given in the table and under the reaction conditions listed in the table 'for the preparation of the corresponding Fluoroalkylsulfonamidoalkanol starting compounds built up from segments respectively.' - Intermediate connections implemented.

Table I.

Parts connection; No.

Components and other information

N-Ke thy Ιτ-4-perf luorheptylbutane-1-sulfonamide

N-methyl-2-perfluoropropylethane sulfonamide

N-methyl-6-perfluoroheptylnorbornyl-methane-sulfonamide ethylene chloronydrin potassium hydroxide
Ethanol
Reaction temperature ^{in 0 C}

Total reaction time in hours. Melting point of the alkanol in ⁰ C% yield

5i5

12.2

6.9 5.6 1.5 4.8 1.6 1.0 40 1.2 15th Reflux
temperature 10 120 18th 120 8th 76-80 52-55 8th 92 ,! pasty 5 68 83

009883/22

ORIGINAL INSPECTED

The compound Kr. 1 was prepared using the intermediate compound N-methyl-N-hydroxyethyl-4-perfluoroheptyl-butane-1-sulfonamid by esterifying 5.5 parts of the same with one part of acrylyl chloride in 20 parts of chloroform with heating for 8 hours Esterification mixture prepared at reflux temperature. After the end of the heating, the mixture was washed with water and dilute aqueous alkali and the solvent was distilled off under reduced pressure. The chamfered Rohester was then purified by recrystallization to give pure N-methyl-N-acryloxyäthyl-4-perfluorheptylbutan-1-sulphonamide was obtained as a white Peststoffes having a melting point of 68 ° to 73 ⁰ C in shape.

Compounds 2 and 3 were prepared by esterifying those given in Table II below Intermediate products according to the procedure described in Part B of Example 3 using the methods described in FIG Table II indicated reactants, amounts and reaction times prepared.

009883 / 22.97

ORIGINAL INSPECTED

Table II

Components and further information

203A155

Parts

Connection ur.

N-methyl-N-hydroxyethyl-perfluoropropyl-ethane-1-sulfonamide

N-methyl-N-hydroxyethyl-6-perfluoroheptyl-norbornyi-methane-sulfonamide Crystalline acrylic acid Crystalline methacrylic acid toluene

Total reaction time in hours. Melting point of the ester in ⁰ C

% yield

CVJ 18. ' 15th 8th 9 pasty viscose
liquid

83.5 91.7

Example 5

This example illustrates the usage one of the new monomers according to the invention in the Production of a copolymer by a solvent polymerization process. The copolymer obtained consisted of a K-methyl-N-acryloxyöthyl-2-perfluoroheptyl-ethane-1-sulfonamide / n-butyl acrylate / N-methylolacrylamide (97: 2: 1) terpolymers.

Those given in Table III below Ingredients were put into one with a septum, a thermometer, a condenser, a gas inlet tube and a device for mechanical movement.

009883/2297

equipped reactor introduced,

Table III -

. Components ] parts

Water 31.80

Dimethylstearylamine 0.36

Glacial acetic acid 0.07

Acetone · '12.30

"N-methyl-N-acryloxyethyl-2-perfl-uor-

heptyl-ethane-1-sulfonamide. 10.00

n-butyl acrylate "0.22

Azodiisobutyramidine dihydrochloride 0.03

The mixture was made using a "freeze-thaw" technique (freeze thaw technique) degassed, then heated to a temperature of 65 ° C and below slightly stirred under positive nitrogen pressure. After the polymerization reaction had started, which was indicated by a showed greater turbidity, 0.05 parts of a 40% ethanol solution of N-methylolacrylamide, which was dissolved in 1 part of acetone, slowly added to the reaction mixture within 1 hour. After heating and stirring the reaction mixture for a total of 5 hours, the desired aqueous Terpolymer emulsion with a degree of conversion of got about 88%.

00 98 837 22 97

Example 6 '

This example illustrates the use of another novel monomer in accordance with the invention the production of a copolymer by a solvent polymerization process.

The ingredients given in Table IV below were put into a thermometer, a cooler and a gas inlet pipe and a device for mechanical agitation equipped reactor filled.

Table IV Components - Parts

N-methyl-N- (A-- acryloxybutyl) -2-perf luor-

heptyl-ethane-1-sulfonaraid. 10.00

n-butyl acrylate ^; 0.50

Azobisisobutyronitrile. $ 0.0

Acetone 10.00

The mixture was made according to the "freeze-thaw" technique degassed and then under slightly positive

Heated to reflux temperature under nitrogen pressure. After this the polymerization reaction had started what indicated by an increase in viscosity, 0.02 parts of a 40% iprene ethanoic solution were added

009883/2297

of N-methylolacrylamide, which in one part acetone, was dissolved, slowly added to the reaction mixture within 1 hour admitted. After a reaction time of 6 hours, a further 0.03 part of azobisisobutyronitrile was added admitted. After the addition of azobisisobutyronitrile, the reaction mixture was refluxed for a further hour heated, whereupon it cooled and the polymer obtained with trichlorotrifluoroethane on a 20 wt .-% resin content was diluted. The degree of conversion in the desired terpolymer was 99%

Example ?

This example illustrates the preparation of various homo- and mixed polymers from the new ones Monomers according to the invention.

The ingredients listed in Table V below were also included in the table 'Listed reaction conditions with the specified Results used for the production of homo- and mixed polymers.

009883/2297

Table V

Part of polymer no.

components and further information

N-LIethyl-N-acryloxyethyl-2-perfluoroheptyl-ethane-1-sulfonamide

N-Methy 1-Nr- (4Acryloxybutyl) -2-perfluoroheptyl-ethane-1-sulfonamide

N-methyl-N-acryloxyethyl-2-perfluoropropyl-ethane-1-sulphide

100 150

100

n-butyl acrylate 51.5 0.6 2.6 0.4 2-ethylhexyl acrylate 0.4 150 70 Azobisisobutyronitrile 155 0.5 acetone 4th 60 105 60 N-methylol acrylamide 60 18th 0.2 8th Reaction temperature in O 8th 99 60 80 Total reaction time in hours 98 8.5 % conversion 99

In each case the polymer was made by loading one with a reflux condenser and equipment for mechanical movement equipped reactor with the specified components, heating of the received, Tenten mixture with stirring for the specified period of time, allow the reactor contents to cool and discharge of the reactor contents produced from the reactor.

009883/2297

ORIGINAL IMSPECTED

- 50 -

Example 8

This example illustrates the excellent water and oil repellency properties of treated with the new polymers according to the invention Fabric substrates ,,

In order to demonstrate the excellent water and oil repellency properties of the new polymers according to the invention, the test procedures described below were used. In each case, which was used as the textile testing printed cotton cloth according to the "block method" treated, wherein the specimen through a solution of each derivative in a solvent mixture of a portion of isopropanol and a portion Toluol.geführt _s then to evaporate the solvent at a low temperature heated and finally the fabric treated in the manner described was heated ^{to a temperature of 150 0 G for curing for 5 min.}

Examination of the C

The oil repellency of the treated cotton fabrics was measured according to the 3M Oil RepeXlency 'Tesf' method described ^{in the magazine .Textile Research Journal 11} * April 1962, page 323 in align details about 3§ _$ 4 OT (3 inch χ 10 ineh) - large swatch dea treated © a BawnwoXlge-w @ fa @ i ₀

QG9883 / 2297 "

BATH

4 h at a temperature of 21.1 ⁰ G (7O ⁰ F) and a relative humidity of 65% had been conditioned, mounted on a tire having a diameter of 12.7 cm (5 inches) to provide a smooth, wrinkle-free surface to accomplish. Individual drops of test oils, which consisted of various mixtures of mineral oil and n-heptane, were then very lightly applied to the fabric. After 3 minutes, the respective tissue was examined visually to determine the extent of wetting and penetration. Each fabric was then rated for oil repellency as shown in the following table. The evaluation is based on the composition of the respective oil mixture with the highest heptane content, which did not penetrate or wet the fabric.

. Table VI Volume % Evaluation of the oil Volume % Heptane repulsive ability mineral oil 70 120 30th 60 110 40 50 100 50 40 90 60 30th 80 70 20th 70 80 0 . 50 100 rstandsf ähicr crecen 0 (not wide

Mineral oil)

009 883/229?

It should be noted that Ee 'evaluation results from 70 and above an effective oil show slack or bump.

Judgment on the ability to repel water;

The water repellency of the treated cotton fabrics was measured according to the "Standard Spray Test" of the American Association of Textile Chemists and Colorists (AATCG No. 22-1964-). Oil Repellency Test "happened, made. The swatch was then stretched onto a hoop about 15 »2 cm (6 inches) in diameter to present a smooth, wrinkle-free surface. The sample was then placed under a 4-5 ⁰ angle with its center directly opposite a spray nozzle, so that, consequently, was flush the center of the spray pattern from the nozzle at the center of the pattern portion. 250 ml of distilled water were then sprayed onto the test specimen within 25 to 30 seconds. The moisture pattern formed on the surface of the test piece was compared with a number of standard moisture patterns evaluated. Each test sample was then assigned the rating of the standard sample which came closest to the sample on the test piece. The standard samples were evaluated according to the following scheme:

009883/2297

BATH ORIGINAL

- No sticking or no moistening of the top; - minor sticking or minor

Moistening in arbitrary places on the top; - partial moistening of the entire top; - complete humidification of the whole

Top; and O- complete moistening of the upper and

Bottom.

Me results of these determinations are in the Table VII below. ·

009883/2297

Table VII

Evaluation of the water and oil repellency of representative polymers according to the invention

Polymer

Applied 'evaluation of the amount in #, oil-water related to repulsion repulsion the weight
de-s tissue

Mixed polymer of
Example 7 0.5 100 90 Mixed polymer of
Example 9, No. 1 0.5 110 100 Homopolymer of
Example 9-, No. 2 0.5 120 90 Mixed polymer of
Example 9, Mr. J 0.5 110
f 90 Homopolymer of
Example 9, no. 4th 0.5 70 80 Comparative sample
(untreated tree
wool sample) 0 0

The results of the table clearly show the excellent oil and water repellency of the new polymers according to the invention.

In summary, it can be seen that according to the invention new, segmented pluoroalkylsulfonamidoalkyl acrylate and methacrylate monomers can be produced, which can be homopolymers and copolymers with excellent oil and water repellency properties can be processed further.

009883/2297

Claims (1)

Patent claims U) / Fluoroalkylsulfonamidoalkyl esters built up from segments the formula Rf - Z - SO ₂ -HXOGC -CH ₂ R OR ¹ where mean: Rf a 5 up to and including 20 carbon Atoms-containing residue, consisting of a optionally in der'Perfluorgruppe through at least one hydrogen, chlorine, erom or iodine atom substituted, straight or branched chain perfluoroalkyl radical; cyclic aliphatic perfluoro radical or polycyclic aliphatic perfluoro radical; Z is an alkylene, alkenylene or cycloalkyl radical, a cycloalkyl radical with a bridge bond, a polycyclic alkyl radical, a polycyclic alkyl radical with a bridge bond, or a radical of the formulas: - (CHp - CH) _n - and (CH-Ck ι I R "R" 0098 83/22 97 in which R "is a hydrogen atom, a saturated one or unsaturated hydrocarbon residue with 1 to 20 carbon atoms, a cycloalkyl radical, a cycloalkyl radical with a bridge bond, a polycyelic one Alkyl radical, a polycyclic alkyl radical with a bridge bond, represents an aryl or aralkyl radical and η · = an integer of 1 to 20 inclusive; W R denotes a hydrogen atom or an alkyl radical 1 to 6 carbon atoms; X is a straight or verssweigtkettigen alkyl enrest of the formula I (CHp) ₂ - * ^ ⁿ which m 'is an integer from 2 through 14, a cycloaliphatischsn radical, a cycloaliphatic Best with bonding, an aralkyl _$ an aryl group or a di-alkylene ~ oxide residue and "R ^{1 is} a hydrogen atom or a methyl radical. 2.) Pluoralkylsulfonamidoalkylester according to claim 1, characterized in that it consists of N-methyl-N-acryloxyethyl-2- »perfluoroheptyl-ethane = -isulfonamide; ' N-ethyl-N-acrylo2rate] iyl-2-peri ^> liioriieptyl-ethhaa »1» sulfonamide; N-methyl-N-acryloxyisopropyl-S-perfluoroheptyl-ethane-1-sulfonamide; • 009883/229? - 57 - N-ethyl-N-acryloxyethyl-4-perfluoroheptyl-butane-1-sulfonamide N-methyl-N- (4-acryloxybutyl) -2-perfluoroheptyl-ethane-1-sulfonamide; N-methyl-N-methac ^ loxyethyl-e-perfluoroheptyl-norbornylmethane-sulfonamide; N-methyl-N-acryloxyät3ayl-il1 -perf luorpropyl-undecaii-1-sulfonamide; N-methyl-N-acryloxyethyl-2-octacilor-octafluoro-octylethane-1-sulfonamide; N-ethyl-N-acryloxyethyl-I-perfluoroheptyl-allyl-isulfonamide; N-Acryloxyäthyl - ^ - perfluorpropyl-cyclohexane-sulfonamidj N-Methy1-K-acryloxyäthy1-2-perfluoropropyl-ethane-1-sulfonamide; N-methyl-N-acryloxyethyl-A-perfluoroheptyl-butane-1 ~ sulfonamide; N-methyl-N-acrylöxyäthyl-iö-perfluorooctyl-hexadecane-i- sulfonamide; · N-methyl-N-acryloxyethyl-perfiuorcyclohexyl-methanesulfonamide; and N-ethyl-N-acryloxyethyl-perfluorisononyl-ethane-isulfonamide "exist. 5.) Fluoroalkylsulfonamidohydroxy compound built up from segments the molded ice Rf · - Z - SOg - N - X - OH ■ .-. ".; ■■. 009883/2297 where mean: Rf a hest containing 5 to 20 carbon atoms inclusive _? consisting of a straight or branched chain perfluoroalkyl radical optionally substituted in the perfluoro group by at least one hydrogen, chlorine, bromine or iodine atom; cyclic aliphatic perfluoro group or polycyclic aliphatic perfluoro group; ' Z is an alkylene alkylene E? · Or cycloalkyl radical, a Cycloälkylrest with a bridge bond, a polycyclic alkyl radical “a polycyclic - r • An alkyl radical with a primitive bond, or a radical the Pormelns _n - and - (GH C) - R ^l! -R " in which E "a hydrogen atom ₅ a saturated or migesaturated hydrocarbon radical with 1 to 20 carbon atoms, a cycloalkyl radical, a cycloalkyl radical with a Brüßken bond ₉ a polycycliseliea with r © st represents uiid a α eis © gaas © 1 to eiascJalitiliefe 20 § 00 ^ 9-8 8-37 2297 1 "to 6 carbon atoms j X is a straight or branched chain alkylene. remainder of the form 1 ': (CH ₂ ) J _n * in which m - an integer from 2 to 14 inclusive, a cycloaliphatic radical, a cycloaliphatic radical with a bridge bond, an aralkyl radical, an aryl radical or a di-alkylene oxide radical. 4 ·.) Process for the preparation of fluoroalkylsulfonamidoalkyl esters built up from segments according to Claims 1 or 2, characterized in that • a.) A fluoroalkylsulfonylhalogemld built up from segments the formula; Rf-Z - SO ₂ - γ where Rf and Z have the meaning given and V stands for a chlorine, bromine or iodine atom, with a nitrogen-containing one Compound consisting of ammonia, ammonium carbonate or a primary CL- to Cc-amine, to one converts fluoroalkylsulfonamide composed of segments; b.) the fluoroalkylsulfonamide formed, composed of segments, with an alkylene oxide or ω-halogen alcohol reacted in the presence of a base to form a fluoroalkylsulfonamidohydroxyl compound built up from segments and 00988 3/2297 c.) the formed, built up from segments. Fluoroalkylsulfonamido hydroxyl compound esterified with acrylic acid, methacrylic acid, acrylyl chloride, methacrylic chloride, a G * - C ^ alkyl acrylic acid ester or a C ^ - C ^ -alkyl methacrylic acid ester. 5.) Process for the preparation of fluoroalkylsulfonamidoalkyl esters built up from segments according to claims 1 or 2, characterized in that · one a.) a fluoroalkyl sulfonyl halide built up from segments the formula: where Rf and Z have the meaning given and ι stands for a chlorine, bromine or iodine atom, with an amino alcohol in the presence of a proton acceptor a fluoroalkylsulfonamidohydroxyl compound built up from segments and b.) the fluoroalkylsulfonamidohydrocyclic compound formed from segments with acrylic acid, methacrylic acid, acrylyl chloride, methacrylyl chloride _s a Gy. - C ^ alkyl acrylic acid ester or a methacrylic acid ester esterified. 6.) Use of fluoroalkylsulfonamidoalkyl esters derived from segments aaefe Assi 2 ale building blocks of 9883/2 2 97 7.) Use at least one of each Fluoroalkylsulfonamidoalkyl esters built up according to segments Claims 1 or 2 as a building block of random copolymers. 8.) Use of fluoroalkylsulfonamidoalky esters built up from segments according to claims 1 or 2 as Building blocks of homopolymers for the formation of coatings on at least one surface of solid substrates for the production water and oil repellent properties. 9.) Use of in each case at least one fluoroalkylsulfonamidoalkyl ester built up from segments according to claims 1 or 2 as a component of arbitrary copolymers for the formation of coatings on at least one surface of solid substrates to produce water and oil repellent Properties. 0Ö98S3 / 2297 - "bad original