DE2017399A1 - Polyfluorisoalkoxyalkanamide derivatives and their use - Google Patents

Description

Priority: v. April 14, 1969 in USA Serial No, ι 8I6 OI3

The invention relates to N-methylol derivatives and N-halomethyl derivatives of fluorocarbon amides and their sub-f> substituted ammonium salts. The invention is particularly concerned with N-methylol and N-halomethyl derivatives of Polyfluorieoalkoxyalkanamides and their substituted Ammonium salts, which are used as oil repellants and Water-repellent machan are useful »

Quaternary ammonium compounds of N-halomethylamides of fluorocarboxylic acids are known to have oil-repellent and water-repellent properties. For example, U.S. Patent No. 3 describes 14? Ο65 quaternary compounds of the formula

...... / ■. 0098 / »2/1 991

2 -

R - R - CONH - CH ₂ Q ⁺ X "

where R _{f is} a perfluoroalkyl group with h to 12 carbon atoms, R is an alkylene group of the formula -CH ₂ CHCl (CH ₂ ) - or - (CH ₂ ) -, where m is an integer from 1 to 10 and η is an integer of 3 to 12 denotes, Q denotes a radical of a tertiary nitrogen base and X denotes chlorine or bromine. These compounds impart moderate oil-repellent properties to cellulose materials, such as cotton cloth, but completely inadequate water-repellent properties when applied comparatively heavily.

The US A-Pa tent "their if t 3 137 066 describes quaternary compounds the formula

R - SO NR (CH ₉ ) -CONH - CH_Q ⁺ X ~

where R _{f is} a perfluoroalkyl group having 4 to 12 carbon atoms, m is an integer from 2 to 12, R is an alkyl group having 1 to 6 carbon atoms, Q is the radical of a tertiary nitrogen base and X is a chlorine atom or bromine atom. These compounds give cellulose materials good oil-repellent properties, but poor water-repellent properties. Quaternary ammonium compounds, which are substituted with long-chain alkyl groups instead of perfluoroalkylene end groups, give fabrics water-repellent properties but not oil-repellent properties. Thus, in general, compositions containing more than one quaternary ammonium compound have been required to produce textiles and the like. simultaneously

009842/19 91 "3-

to impart water-repellent * and oil-repellent properties. Known connections are also deficient in their durability, i.e. in their ability to develop their Maintain effectiveness after repeated washing and / or dry cleaning. The elaborated compositions have heretofore required an increase in cost in making oil repellent and water repellent Cellulose pads, and therefore, have been around for a long time Looking for compounds that make it permanently oil-repellent and water-repellent. '

A main aim of the present invention was:; therefore, Get compounds that when applied on give a substrate oil-repellent and water-repellent properties. Another goal is the discovery of such compounds, the cellulosic materials give these properties. Yet another goal is to make it oil repellent and water repellent To obtain funds for fabrics that are effective even with frequent washing and dry cleaning keep. Yet another object of the invention is Obtain compounds that can be used as both internal and external agents for paper, to make it oil-repellent and ink-repellent. Further objects of the invention will follow from the the description apparently.

The new compounds according to the invention are N-methylol

009842/1991

and N-halomethyl derivatives of amides of fluorocarbon säurön and their substituted ammonium salts formula

C-P

π ₂ pc

-O-

i R

C-P

² I ^Z 3 ^X l ^X 3 '

. - -NHCH ₂

wherein R- and R ₂ independently of one another can denote fluorine atoms, chlorine atoms or perfluoroalkyl groups or taken together a cyclic perfluoroalkylene group, but with the proviso that both groups R ₁ and R 2 cannot be chlorine atoms, Z-, Z ", Z" and Zjl fluorine -, chlorine or hydrogen atoms with the proviso that no more than two of the groups Z ₁ to Z. are chlorine atoms, X-, X ₂ , X_ and X. mean chlorine, fluorine or hydrogen atoms under the hatred, that no more than one of the groups X to X ^ is a chlorine atom, r is an integer from 1 to 2, in and η are integers from 0 to 75,

009842/1991 "

the sum of m and η is 0 to 75, ρ is an integer represents from O to 1, Y represents a hydrogen atom or a fluorine atom and W represents a hydroxyl group, a halogen atom or the group QA denotes in which Q is the remainder of a nitrogen-containing quaternizing agent is that at least contains a positively charged nitrogen atom, and A contains at least one negatively charged halogen atom among the Precondition means that the number of negatively charged halogen atoms in A is equal to the number of positively charged ones Is nitrogen atoms, and t is an integer equal to the number of positively charged nitrogen atoms.

The critical point in the structure of the compounds described above is the polyfluoroisoalkoxyalkyl tail portion of the molecule, wherein an ether oxygen atom connects a fluorinated carbon atom linked to two fluoroalkyl groups with at least one -CF ₂ group.

The amide starting materials useful in the invention have the following formula:

'- 6 r

00 9 8 4: 2/1 9 91 ORIGINAL INSPECTED

C-P

PC- O (CP ₂ ) _r (C -

Ζ— Χ «Χ_

ι 3 | 1 | 3

• r;

C-P

where R

-, R ₂ , Z- to Zr, X to X ^, Y ^- , r, .m, n and ρ have the above meanings.

The amides of formula (2) can be made from polyfluoroisoalkoxy tetrafluoroethyl iodides of the formula

^j \: ■■

P - C -, 0 -

^R l

C-P

are prepared, in which R, and H. have the above meaning have «These iodides are activated by the implementation of a g © Katons with an ionizable Flworidsals »like bai-

CsF or KP to form eleventh fluorinated

0098Α2 / 199Γ "." - 7 "

'WSPECTED

organic salts - those with tetrafluoroethylene and iodine is implemented.

The iodides of the formula (3) can be _{mixed with unsaturated compounds of the formula Z 1} Z ₂ C = CZ Zj, and / or the formula XX C = CX X ^, where Z to Z ^ and X ₁ to X ^ are as defined above, be reacted to obtain polyfluorosoalkoxyalkyl iodides of higher molecular weight. Suitable unsaturated compounds are, for example, ethylene, difluoroethylene, Difluprchloräthylen, trifluoroethylene, tetrafluoroethylene, etc. These reactions can be initiated by heat, such as temperatures from about 100 to about 450 C, preferably from about 150 to 200 C, or they can be by a Initiator can be initiated with free radicals, such as azobisisobutyronitrile, benzoylperodide and the like.

The following series of reaction equations serves to further explain the preparation of the iodides, in which R ₁ , R ₂ , Z ₁ to Zr, X ₁ to X ^, m and η have the above meanings. >

00984-2 / 1991 - ₈

BATH ORIGINAL

C.- P ο »ο + KP - )

R.

P - C R,

C-F

- 0 ~ Κ ^Ί

C-P

C-P

¹ X

C-P

R.

P- C- 0 ~ Κ + CP ₂ = CF ₂ +

C-. - P

r F CP CO- CF ₂ CF ₂ - I *

AI

.C-P

C - P

R ₁

ρ.-c-0- CP ₂ CP ₂ I +. InZ ₁ Z ₂ C CP

R.

R. r;

F. Ri

'C-P

-C-O-

CF ₀ CF (C-C) I

²² I i ^m

• ^Z 2. ^

r;

0098A2 / 1991 ORIGINAL INSPECTED - 9 -

_ 9 -

Ri

^Λ 2

P- C

C-P

² I ^Z ι- ¹ t

-O- CP ₀ CP ₀ (C - C) I + nXyX ^ C

- P *

R,

R.

¹ V

C - P

P - C

- O

- GP ₂ CP ₂ (C -

C -

If m and / or η is O, the telomerization equations 3 and / or k are omitted.

The amides are conventionally derived from their corresponding Carboxylic acids derived;

The preferred class of carboxylic acid precursors to the amides, which are useful in accordance with the invention has the following formula

Io -

009842/1991 ''

ORIGINAL INSPECTED

- ^lo

C-F

ρ - σ

R.

-O -

(Ci ^? ₂ ) _r (CF ₂ CF ₂ ) _m (CH ₂ CH2) _n (CY ₂ ) _p COOH

C-P

and R ₂ flupratorae, chlorine atoms or perfluoro-

wherein

can mean alkyl groups with 1 to 2 carbon atoms, provided

m and η are integers from 0 to 10 and Y, r and ρ have the above meanings.

and R _? do not mean both chlorine atoms,

The preferred methods of preparing the acid precursors of the amides from the polyfluprisoalkoxyalkyl iodides vary depending on the values of m, n _s ρ and τ.

Carboxylic acids of the formula (5) »" in which r is 2, m has the above meaning, ρ is 0 and η is at least 1, can be obtained by reacting a suitable iodide of the formula (k) with a in © r end group -CH ₂ I with a water-soluble matalloyanide has been prepared with the formation of the corresponding nitrile

- 11 -

009842/1991

ORIGINAL INSPECTED

free acid can be hydrolyzed.

Carboxylic acids of the formula (5), in which r means 2w, m and η have the above meaning and ρ is 0, can be obtained by reacting an iodide of the formula (4) with at least one end group -CH ₂ CH ₂ I with elimination of HI from the end group be prepared with the aid of a strong base, forming the corresponding terminal olefin, which is oxidized to the carboxylic acid with a conventional oxidizing agent such as permanganate or dichromate.

Carboxylic acids of the formula (5) »in which r is 2, m has the above meaning, η is at least 1, ρ is 0 or 1 and T is a hydrogen atom, can be prepared in such a way that a suitable iodide of the formula (k ) reacts with a terminally unsaturated carboxylic acid or a corresponding ester in the presence of an initiator with free radicals and thus wins the corresponding iodocarboxylic acid or the corresponding ester. The iodocarboxylic acid can be reduced to the free acid in a conventional manner, such as with zinc in alcohol. The ester can be hydrolyzed to the free acid in a known manner. Alternatively, the iodine ester can be dehydrohalogenated in a known manner, for example with alkali, to give the corresponding alkene carboxylic acid and, for example, with hydrogen in the presence of a catalyst such as platinum oxide, to give the corresponding carboxylic acid

009842/1991 ""

acid to be hydrogenated.

Carboxylic acids of the formula (5) ι in which η and ρ are O, r is 2 and m is as defined above, can be prepared in such a way that a suitable iodide of the formula (4) is mixed with (CN) ₂ under a pressure of 20 to 200 at at temperatures of 300 C or more with the formation of the corresponding nitrile. The nitrile can be hydrolyzed to the free acid in a conventional manner.

Carboxylic acids of the formula (5) _f in which either or is 1 and m, η and ρ are 0, or in which r is 2, η is at least 1, ρ 1, Y is a hydrogen atom and m is as described above, can be prepared in this way by reacting a suitable iodide with SO_ to form the pyrosulfate or with oleum to form the hydrosulfite and hydrolyzing the pyrosulfate or hydrosulfate to the corresponding alcohol. The alcohol can then be oxidized to the free carboxylic acid with conventional oxidizing agents.

Carboxylic acids of formula (5) wherein r is 2, η is 0, ρ Is 1, Y is a hydrogen atom or fluorine atom and m has the above meaning can be taken from the corresponding Alcoholι where η is 1 and X. and X. are hydrogen atoms mean, are produced by oxidation, as described above.

009842/1991

ORlGiMAL INSPECTED

Carboxylic acids of the formula (5) »in which r is 2, η Ο is, ρ is 1, Y is a hydrogen atom and that Carbon atom in the ß-position with respect to the caroxyl group is substituted with two riuoratomen, can by Oxidation of the fluoroolefin with a terminal ethylene group of the general formula ,,

ρ- C - O - GP ^ CP ₆ (GF ₅ GF ^ LcH ^ CH «CH ₀

. ti dd 2 Hl 2 2 ■ ■

wherein R-, R ₂ and m have the above meanings, are preparedί These fluoroolefins can be prepared by reacting a suitable iodide with, allyl alcohol; at a temperature between about 100 and 450 C, are preferably obtained between 150 and 300 C, at Überätmosphärendruck · The terminal can in Äthylehgrüppe herkbmmlicher ¥ else to Carboneäure oxidized "

Carboxylic acids of the * ^ © riä # 3 · | 5i »where V 2 ί-βΙ» ^{n is} 0, m has the above «meaning, ρ is 1 and Y is a fluorine atom« ut * ti ^ can be given by .VmuiiitWWg · § » #> ■ g * «ignited iodides

§01141 / 111! ίΰ '^ - 14 *

^BA n QBlGINAL

with sulfur trioxide at a temperature of 50 to 175 C, preferably from 100 to 150 C, with formation of the corresponding acid fluoride and fluoropyrosulphate and hydrolysis of the fluoropyrosulphate u'Ad / or acid e'f Iu or id «, desired acid by refluxing with water to the corresponding ester by refluxing with an alcohol. Instead, kanniaan the corresponding acid salts by reaction of the acid- .. fluoride and / or fluoropyrosulfate with alkali hydroxide and acidic acids with aqueous mineral acid. ■ -. V

Carboxylic acids of the formula (5), in which r is 2 and m, η and. ■ -; ■ ρ 0, can be obtained from the polsfluörisoalkoxytetrafluoroethyl iodide of the formula (3) by reaction with a Grignard reagent to form a magnesium halide adduct, Implementation of this adduct with CO ₃ to form the magnesium halide salt 'urid acidification of the salt with a mineral acid'. The reactions with the Grignard reagent are preferably carried out at a temperature below about 0 ° C.

The carboxylic acids described above can also be prepared in other ways , as is known to those skilled in the art .

The amides can be obtained from the carboxylic acids described in a conventional manner by reacting their low molecular weight alkyl esters or acid chlorides with ammonia ,

001142/1991 "

* "". ORIGINAL INSPECTED

The N-methylol derivatives according to the invention can be through Reaction of an amide of the formula (2) with formaldehyde produce .. At least 1 mole of formaldehyde is required to complete the reaction, but in general, an excess of the formaldehyde of used up to about 5 moles. The ReaktLon can in the presence or absence of an inert solvent such as Benzene, xylene, Trifluprtrickloreitkylen and the like., Carried out will. A basic catalyst such as sodium bicarbonate or sodium carbonate can also be used if so desired, but it is not necessary. Good results can also be achieved without Use of a solvent or catalyst.

The reaction is generally carried out at temperatures of about 70 to 15O ⁰ C, but this is not critical, and, if desired, higher or lower temperatures can be used. When the reaction is carried out in the absence of a solvent, the temperature is usually maintained above the melting point of the amide reactant.

The N-halomethylamides according to the invention can be prepared by reacting an amide of the formula (2) with a hydrogen halide or thionyl halide and formaldehyde. The reaction can conveniently be carried out by adding the hydrogen halide to a solution of the amide and formaldehyde in an inert solution * -

0098A2 / 1991

INSPECTED

. ^: * ~ ■ "'" ■■ "-" ■■■■. -. "■ ■■.: .. ■ - ■ - ■" £

medium at a temperature from about room temperature to added to about 100 ° C. Suitable solvents are, for example aromatic hydrocarbons such as benzene, toluene, xylene and the like.

In the production of N-methylol or N-halomethyl compounds any source of formaldehyde can be used, such as formaldehyde, paraformaldehyde, and trioxane. the anhydrous form of these compounds is preferred.

Known condensing agents such as metal halides can be used to increase the reaction rate including zinc chloride, lithium chloride and the like. These are generally used in amounts of 0.1 to 1 mole per mole of amide used.

Suitable halogenating agents are, for example, hydrogen chloride, Hydrogen fluoride, hydrogen bromide, hydrogen iodide, thionyl chloride, thionyl bromide and the like.

At least 1 mole of formaldehyde and 1 mole of halide are required for a complete reaction with 1 mole of the amide, however, an excess of formaldehyde on the order of 1.5 to 2.0 moles per mole will generally be used Amide used. Larger amounts can also be used if desired. When a gaseous Halogenierungsmittelöl is used, it can be convenient to bubble this into the reaction mixture until the reaction

009842/1991

is complete.

The reaction proceeds easily at room temperature, however higher or lower temperatures can also be used if desired, such as temperatures between 0 C and reflux temperature.

Instead, the N-halomethylamides can also be obtained from the N-methylolamides are prepared by reacting the N-methylolamide with a halogenating agent in solution, as described above.

The N-halomethyl and N-methylol compounds according to the Invention can be used as such or, if desired, be further cleaned in a conventional manner, such as by distillation, recrystallization or trituration with a suitable solvent such as the Is known to those skilled in the art.

The substituted ammonium derivatives according to the invention can by implementing the N-halogen methy! compounds of the invention with the quaternizing agent, either Thiourea or a tertiary nitrogen base *. This reaction can conveniently be carried out at room temperature, but higher can also be carried out or lower temperatures on the order of 0 up to about 70 C if desired. The reaction is generally over in a short time,

- 18 -

9842/1991

i.e. within 5 minutes to 1 hour.

Instead, the substituted ammonium salts can also be prepared directly from the amides by reacting the amide, formaldehyde and a hydrohalide salt of a tertiary nitrogen base in a suitable solvent. This can make the use of the corrosive hydrogen halide gases superfluous. An excess of the nitrogen base used can act as the solvent for the reaction. Generally, an excess of the formaldehyde and amine salt is used, on the order of 2 to K moles per mole of amide. The reaction can be carried out at temperatures of about 25 to 100 G, but preferably at about 60 to 80 C. Preferably, the reactants for several hours, conveniently 18 to 20 hours, heated to ensure a vollständig® reaction.

JiJs can be j @ d © known tertiary Stickstoffbas® for preparing the quaternary ammonium compounds according to the invention used when it is in the lag © ₉ to form ® ± n or salt 'is a quaternary ammonium derivative. Goeignete bases include trialkyl amines κ wia Trimsthylamin, 'Triäthylamln, Triisobutylaain ,, tridodecylamine Methyldiäthyiamisi, DimethyIhexylamin, Methyläthylhexylamin u.dergl _ei cycloalkylamines such as "* - ■■ -'. Trieyelohoxylamin, Propyldioyclohexylamin u.dergl '," aromatic amines, such as diraethylaniline, benzyidlistethylamine, di «·

0098 A2 / 1 991 " ¹⁹

ethylaniline and the like, hydroxya <- yl-substituted amines such as triethanolamine, dimethylethanolamine and the like, heterocyclic amines such as pyridine, lutidines, quinoline, isoquinoline, acridine, 2, k, 6-collidine and the like. Polyfunctional amines can also be used, and in such a case more than 1 mole of an N-halomethyl compound described above can react with 1 mole of the amine to produce quaternary ammonium compounds having more than one positively charged nitrogen atom . Suitable polyfunctional amines are, for example, N, N, N ¹ , N ¹ -tetramethyl-1,3-pi'opanediamine, aziridine polymers and the like. Thiourea is also a satisfactory quaternizing agent. Pyridine is preferred for the manufacture of textile treatment agents because of its low cost and easy availability,

^ The quaternization can be done using an excess of the amine can be carried out as a solvent, or a different solvent can be added such as benzene, toluene or trichlorotrifluoroethane. The substituted ammonium compounds can be removed by evaporating the solvent, adding a non-solvent, such as ether, or in a similar manner known to the person skilled in the art. The product can if desired, further by recrystallization from a suitable solvent such as acetonitrile or chloroform,

or by rubbing with an inert solvent such as ether.

- 2o -

0098 42/1991

BATH ORIGINAL

- 2ο -

The compounds' * · according to the invention are useful as oleophobic agents and can be applied to a variety applied from substrates, such as paper, cellulose films, wood, leather, textile fibers, Yarns and fabrics, metals, glass and the like. The resulting articles or treated substrates are oil repellent and also dirt, water and grease repellent «

The substituted ammonium salts according to the invention are water-soluble and therefore particularly useful for impregnation. nation of papers and as a textile treatment agent ♦ Also, these connections are very permanent, and treated Fabrics retain their oil-repellent and water-repellent properties Properties even after frequent washing and / or dry cleaning. This permanence can in some Cases can be improved by curing, such as by heatinga, to the reaction between the compounds to promote according to the invention and the fabric substrate, or by using a catalyst to cause the compounds to bond to the fabric substrate after the earth bond to facilitate.

In the treatment of tissues, the compounds according to the invention can be used alone or in combination with known ones Fabric treatment agents are used, such as with mildew preventers, Moth repellants, anti-crease agents, lubricants, plasticizers, glues, fire retardants Agents, antistatic agents, dye fixatives

GQ9842 / 1991

BATH

2Q17399

and the like When treating paper, the compounds according to the invention alone or as a component in a wax, in starch, casein, an elastomer or added to a moisture-proof resin. The connections according to the invention can in conventional Wise by dipping, coating, spraying, brushing, etc. Like. From organic or aqueous solution or from aqueous suspension are applied, vüe, the person skilled in the art is known.

The invention is further illustrated by means of the examples. In the examples, all represent parts and percentages Parts by weight and percentages by weight, if nothing else is specified.

example 1

6-Heptafluoroisopropoxy-perfluorohexyl iodide (50.2 parts), (CF) ₂ CF0 (CF CF ₂ ) I and 26.2 parts of liquid sulfur oxide were introduced into a glass-lined pressure vessel equipped with a pressure control device and a stirrer and was associated with one case with dry ice and acetone. The kettle was purged with nitrogen, sealed and heated to about 140 ° C. for 34 hours. The kettle was then cooled to room temperature, ventilated and the product mixture was discharged. The product was a mixture of 7/6 parts of the acid fluoride (CF_) _o CF0 (CF _o CF _o LCF _o COF and 7.5 parts of the pyroeulfuryl fluoride. (CF) _o CF0 (CF _o CF _o ) "0S0 _o 0S0" F.

- 22

8 4 2/19 9 T original inspected

A mixture of 12.2 parts of (CF_) CFO (CF „) _K COF and 10.8ΐ parts of (CF) ₂ CFO (CF ₂ CF ₂ ) OSO ₂ OSO ₂ F, which were prepared as above; filled into a kettle equipped with a reflux condenser and a dropping funnel. The mixture was cooled to 0 C and 26 parts of methanol were added over 20 minutes. The mixture was refluxed for 19 hours, cooled to room temperature and washed with ice water. The organic layer was dried over anhydrous sodium sulfate and distilled under reduced pressure.

The corresponding methyl ester (CF “) ₂ CF0 (CF ₂ ) C00CH_ was obtained.

A solution of 18.5 parts of the methyl ester prepared as above in 50 parts by volume of ethyl ether was cooled to 0.degree. Gaseous ammonia was slowly bubbled into the solution until saturation was complete, W (about h hour) and the mixture was warmed to room temperature. Volatile constituents boiling up to 69 ° C. were distilled off and the product mixture was then further evaporated at room temperature under reduced pressure of 20 mm Hg.

6-Heptafluoroisopropoxyperfluorohexanamide, (CF „)„ CFO (CP) _K - CONH (18 parts) with a melting point of 65 to 67 ° C. was obtained in this way.

00 98 4 2V1991

The amide prepared as above (2.39 parts) and 0.30 Parts of paraformaldehyde were heated to about 90 C during 20 Heated minutes, then cooled and dissolved in 10 parts by volume of trifluorotrichloroethane. Zinc chloride (0.68 parts) were added and the mixture was five minutes touched. Anhydrous hydrogen chloride was added to the mixture bubbled over 2.5 hours and the mixture was filtered. The solvent was evaporated and gave a yellow, viscous liquid which was triturated with ether. The product was dried under vacuum.

A 76% exfoliation (2.0 parts) of 6-heptafluprisopropoxyperfluorohexanamidomethyl chloride was released the formula

(CF) CFO (CF-) 'C0NHCH_ Cl j £ 4 * j d.

obtain. The structure was confirmed by infrared analysis, the amide absorption bands at 3.0, 5.85 and 6.5 up to 6.55 microns, C-F absorption bands at 7.5 to 9.0 microns, and an ether absorption band at 10.1 microns revealed.

Elemental analysis calculated for CF_H ClNO ₂ 1 C-22.8; F 61.2; H 0.6; Cl 6.7; N 2.7; found " C 21.9; F 59.7l H 0.8; Cl 6.8; N 2.6. .

Example 2

ü; a solution of 10.55 parts of 6-heptafluoroisopropoxyperfluorohexanamidomethylchlorld, produced according to example 1

009842/199 1,

2017 339

had been made, in 50 parts by volume of trifluorotrichloroethane was treated with 1.58 parts of pyridine. After evaporation of the solvent, the product was triturated with petroleum ether.
*

A 60 $ yield (7.4 parts) of 1- (6-heptafluoroisopropoxyperfluorohexanamidomethyl) pyridinium chloride was obtained the formula

+
(CP ₃ ) ₂ CPO (CP ₂ ) ₅ CONHCH ₂ N

This compound was soluble in water. The structure was confirmed by infrared analysis, the pyridinium absorption bands at 6.15 and 6.75 microns, amide absorption bands at 3> 3 »5.8 and 6.5 microns, a C-F absorption band at 7 x 5 to 9.0 microns and an ether absorption band at 10.1 microns.

Elemental analysis calculated for Cj-F.-HgClN.O; C 29.45 F 53.2; H 1.35 Cl 5.9; N 4.6; Found: C 29.7ί F 50.95 H 1.5; ei 5.5; N 4.7.

Example 3

A solution of 10.55 parts of 6-heptafluoroisopropoxyperfluorohexanamidotietliyl chloride, which had been prepared according to Example 1, in 100 parts by volume of trifluorotrichloroethane was with 1.30 parts of N, N, N ', N'-Tetramethyl-If3-propanediamine treated as a quaternizing agent.

0 0 9842/1991 -25-

BATH ORIGINAL

A 100 50 yield (1.1.7 parts) was obtained Ν, Ν, Ν ', Ν'— Tetramethyl-N, N'-bis— (o-heptafluQrisopropoxyperf luorohexanamidomethyl) propane-1,3-diammonium chloride the formula. '

2Cl " ^!

) ₂ CP0 (CP

The structure was confirmed by infrared analysis, the CH absorption bands at 6.8 and 6.9 microns, amide absorption bands at 3 »3v 5> 8 and 6.5 to 6.6 microns, a CF absorption band at 7.5 up to 9.0 microns and an ether absorption band at 10.1 microns. The connection was legible in water. '

Elemental analysis, calculated for C ₂ -F .H "IC ₂ NjO. j C 27.3; F 5 ^, 2! H 2, Of Cl, 6.0; N 4.75 Found $ C 26.8; F 53.0; H 2.3; Cl 5 »1; N 4.5.

Example 4

A mixture of 23.95 parts of 6-heptafluoroisopropoxyperfluprhexanamide, which had been prepared according to Example 1, and 3 »0 parts of paraformaldehyde was heated to about 80 ° C. for five hours. A clear yellow, viscous liquid was obtained (20.6 parts) which was triturated with petroleum ether »

009842/1991 ',' .. ''' ^{$ 2}

BATH ORIGINAL

It became N-methylol-o-heptafluoroisopropaxyperfluorohexanamide the structure

(CP_) _ CPO (CP_) _K CONHCH _D OH

obtained. · The structure was confirmed by infrared analysis be that an absorption at 3, O microns -NH and -OH, Amidabsorptionsbanden at 5 »85 and 6.55 to 6.6 microns, a CF absorption band at 7» 5 up to 9.0 microns and an ether absorption band at 10.1 microns.

Elemental analysis for C ₁₀ F ₁₇ H 1 NO ₃ SC 23.6; F 63.4; H 0.8; found i G 23.65 F 63.3? H 0.7.

Example 5

An ester of the formula

(CF ₃ ) _{2 2 1; L3}

was prepared according to the procedure of Example 1 using the corresponding iodide. Dae appropriate Amid -wurd © obtained by reaction with ammonia »

A mixture of 1.95 parts of the resulting 12-hepta »fluprlsopropoxyperfluordodeoanamids and O ₈ 15 T @ il © n Para»

Formaldehyde was increased to 100 ° C. in less than an hour. "The product was through!" gareinig.to

009842/19 9.1

A 60 # yield (1.2 parts) of N-methylol-12-heptafluorisppropoxy-perfluorododecanamide was obtained the formula

(CF ₃ ) ₂ CF0 (CF ₂ ) ^ CONHCH ₂ OH

as a white solid with a melting point of up to 45 ° C. The structure was confirmed by infrared analysis.

Example 6

Zinc chloride (0.09 part) was added to a solution of 0.5 part of the N-methylolamide (CF_) CFO (CF) ^ ONHCHgOH, which had been prepared according to Example 5, in 15 parts by volume of trifluorotrichloroethane. The mixture was stirred for five minutes and then anhydrous hydrogen chloride was bubbled in over two hours. ¹ The mixture was filtered and the solvent evaporated. The soft, white and solid product was further purified by triturating with ether and drying.

An 80% yield (0.40 parts) of 12-heptafluoroisopropoxyperfluorododecanamidomethyl chloride was obtained the formula

(cf ₃ ) ₂ cfo (cf ₂ ) _{1: l} gonhch ₂ ci. .

The structure was confirmed by infrared analysis. Example 7

A mixture of 5 »0 parts of 12-heptafluoroisopropoxyperfluorododecanamide, which was produced according to example 2,

- 28 -

009842/199 1

2.9 parts of pyridine hydrochloride, 0.6 parts of paraforraaldehyde and 30 parts by volume of pyridine was stored at 65 to - 0 ° C Heated for 18 hours. The solid product was made with ether ground and dried. -

i
Manj ¹ received! - (^ - n ^ ptafluorisopropoxyperflufirciadecan-

ami | domethyl) -pyridiiiiumchlorxd of the formula

^ wüic ^^ tConhch ^ ) ei

as a water-soluble solid with a melting point of 59 to 64 C. The structure was determined by infrared analysis confirmed.

Example 8 ■, »

,) ,, "! ■ ■ III '* *

618 parts (CPJ ₂ CPO (CP ₂ CP ₂₎ I ₁ 184 parts Methylundeoenoat and 4.1 parts of azobisisobutyronitrile were charged into a flask equipped with a stirrer, thermometer and condensate or boiler ^ and heated to 70 to 80 ° C. There was a The mixture was kept for 1 hour at 70 to 80 ° C. and for a further 4 hours at 90 to 95 ° C. The unreacted ether iodide was distilled off

An ester of the formula was obtained

(CF ₃ ) ₂ CF0 (CF ₂ CF ₂ J ₃ CH ₂ CHI (CH ₂ CHg) ₄ COOCH ₃ .

- 29

0 098Α2 / 199Ί _BAD

The ester was added dropwise over about 1.5 hours added to a kettle containing 1500 parts by volume of acetic acid, which was heated to 110 to 115 ° C, and contained 65 parts of zinc dust. After about half of the ester has been added ' an additional 65 parts of zinc dust was added. Now A further 20 parts of zinc dust were added, and the mixture was thickened Heated under reflux for 5 hours. The mixture was poured into 3,000 parts of water and the layers separated. The aqueous layer was washed with ether, and the washing liquids were combined with the organic layer. The organic layer was then washed with water, dried over magnesium sulfate and distilled.

There was a 5% yield of an ester of the formula

CF ₃ J ₂ CFo (CF ₂ CF ₂ ) ^ CH ₂ CH ₂ J ₅ COOCH ₃

with a boiling point of 18 to 15 ^ C / l-, 5 nao Hg. This ester was hydrolyzed to the free acid by treating it with 32 parts of sodium hydroxide in 300 parts by volume of alcohol and 100 parts by volume of water on a steam bath for 3 hours heated © and neutralized. The acid product was recrystallized from petroleum ether. (CF J ₂ CFO (CF ₂ CF ₂ J ₃ (CH ₂ CH ₂ ) COOK with a melting point of oil to 65 ^° C.) was obtained.

The acid prepared as above (63.5 parts) was in 25 Dissolved parts by volume of methylene chloride and heated to 35 ° C

ιΐϊίοη

009842/199 1

warms «12 parts of thionyl chloride were added dropwise®

\ "3ο-

- 3ο

sets "and ■ the mixture was refluxed for 3 hours. The solvent and excess thionyl chloride were evaporated under vacuum. A quantitative expansion® of the acid chloride »■ was obtained. . ■

The SäuwreeJalorid was dissolved in 50 parts by volume of methylene chloride dissolved ,, and the solution was Langsan to a, mixture of 8 parts of trieth-ylamine, 4 parts of ammonia and 100 parts by volume of methylene chloride, which had been cooled to 0 ° C.-5 ° C., were added. Ks formed a precipitate » The mud was 2 hours at room temperature stirred * 50 part® water was stirred with vigorous stirring added The precipitate was filtered, with cold ' Washed with water and dried “The raw® amide product was recrystallized from fe @ ißom xthane oil. ■

There was a sl $ -iga yield (29 »-5 parts) of an amide dar For & al

₃ ) - ₂ CPO (CP ₂ CP ₂ )

obtained with a melting point of 93 ^ is $> 5 C, läletaen- taranalys © _f calculated for C ₂₀ H ₂₂ P ₁₉ NO ₂ ^ C 3 ^ _t 2 | -H-3t3 »

β '

P 5 ^ -, Qs N 2 "1§ gef» 8 C 36, Z \ H 3.1 »P 5%, 4i N 2.0.

Bas like ΟΪ3ΘΚ made® Amid Paraf orinalc ^ foyd and 5 'part® im 15 © ¥ alwa®nt © il © a Pyridiia

, 8 parts), 1.5 Φ egg

Pyx'id liquid chloride 6 stems on SO C-

Q0S842 / 19S1

BATH ORIGINAL

was cooled to -30 C. The quaternized product was filtered, washed with cold acetone and urakristallisie ^ t from acetone.

17-heptafluprisopropoxy-12,1a, 13,13- »14,14,15,15, 16,16,17,17-dodecafluprheptadecanamidomethylpyridinium chloride were obtained (25.4 parts) of the formula

Cl "

N>

with a melting point of 120 to 122 C. The structure, was confirmed by infrared analysis which showed bands at 6.0 and 6.5 microns which are characteristic of are a secondary amide.

Elemental analysis calculated for C ^ / P. ^ qCITHJO '. C 39.2; H 3.5? Cl 4.5s N 3.5; found j G 37.2; H 4.5; Cl 3.7; N 2.6.

Example 9

An amide of the formula

was following the procedure of Example 1, but using the corresponding iodide as starting material, manufactured.

A mixture of 61.5 parts of the amido, 3.2 parts of paraformaldehyde and 10 parts of dry pyridinium chloride in 300 parts by volume of pyridine were reacted as in Example 1.

0 0 9 8 4 2/1991 - 32 -

The crude product was isolated and recrystallized from acetone.

19-heptafluprisopropoxy-12,12,13 »13,14,14,15,15,16,16, -17,17,18,18,19,19-hexadecaf luornonadecanainidome thylpyridinium chloride (47 parts) of the formula

[) ₂ CP0 (CP ₂ CP ₂ ) ^ (CH ₂ CHg) ₅ CONHCH ₂ N ^N ) Cl "

obtained with a melting point of 128 to 130 C. The structure was confirmed by infrared analysis.

^{Elemental analysis} calculated for ^C 28 ^F 23 ^H 28 ClN 2 ° 2 ^IC H 3.2j N 3.1; Found: C 35.6; H 4.6; N 4.7.

Example 10

An amide of the formula (CF 1) _GFO (CF ₀ CF ₀ ) _O (CH_CH ₀ ) _K C ⁴ ^ - NH ₀ was prepared according to the procedure of Example 1, but using the corresponding iodide as starting material.

A mixture of 34.2 parts of the amide, 2.4 parts of paraformaldehyde and 7 »5 parts dry pyridinium chloride in 225 parts by volume of pyridine was following the procedure of Example 1 implemented. The product was as in example 1 isolated and recrystallized from acetone.

15-Hoptaflu © r ± sopropoxy-12,12,13,13,14 _t 14, -

0 0 9 8 4 2/1991 ~

15 »15-octafluoropentadecanamidomethylpyridinium chloride (22 parts) of the formula

■ Ο-

with a melting point of 118 to 120 C. The structure was confirmed by infrared analysis.

Elemental analysis calculated for ^C 24 ^F 1 ^t 1 ^H 28 Cl 5.1 »N 4.0; Found: C 42.0; Cl 4.9; N 4.1.

Example 11

This example demonstrates the use of a typical substituted ammonium compound according to the invention as an internal impregnating agent for paper.

Papers were naoh the following test as to their oil-repellent and water-repellent properties investigated »The water-repellent properties of treated papers were determined according to the standard test T 44I-OS-63 of the Technical Association of the Pulp and Paper Industry (Cobb test). This test-determined the amount of water absorbed by the paper after 2 minutes became. The value shows from 20 to 25 or less. excellent water resistance.

The oil resistance of treated papers becomes as follows determined: A series of 12 solutions of different Quantities of castor oil, toluene and heptane was

00 9 8-4 2/1991

compiled according to the table below. A value of voxi 12 shows superior oil repellency.

Series parts by volume parts by volume parts by volume

No ₀ s castor oil toluene heptane

10 20 30 40 50 60 70 80 90 100 110

1 200 0 2 180 10 3 l60 20th 4th 140 30th 5 120 4o 6th 100 50 7th 80 60 8th 60 70 9 40 80 10 : 20 90 11 0 100 12th 0 90

The series number is the highest numbered solution that remains on the surface to be examined, in the form of a drop, for 15 seconds without the solution penetrating, ie. without the area under the drop darkening.

The ink resistance is as follows: K 1 square with 3 "8 cm made of treated paper ¹ is" og © "folds ₉ that all® Karat®" on tjerdosso 3a "square

■ QÖ9842 / 199 1 " - ³ⁱ

is made to swim on a standard writing ink. The time, in seconds, that it takes for the ink to run out evenly-penetrates to the top surface of the paper, is referred to as the ink penetration. A time of 900 seconds or more means excellent ink resistance.

19-heptafluoroisopropoxy-12,12,13,13,14,14,15,15,16,16,17,17, - 18,18,19,19-hexadecafluoronadecanamidomethylpyridinium chloride, which was prepared according to Example 9, was in various amounts in a 3 $ -igen cationic starch » solution (Cato-15, a product of National Starch and Chemical Co.) dispersed. A mixture of bleached softwood and hardwood wrapping paper pulps (5οί5θ) was in Water stirred for 3 to 5 minutes, and the starch solution was added. Stirring was continued for an additional 3 to 5 minutes continued, and handbows were formed and dried. The treated sheets were checked for oil resistance, water * resistance and ink resistance immediately after curing of the sheets for 48 hours at 110 ° C it's correct. The results obtained are summarized below.

Concentration series swimming on Cobb value $ No. Ink, seconds

1.0 12 ^> 900 22.8

^r -, 0.5 12> 900 27.6

0.25 10> 900 4o, 4

- 36 -

009842/1991

BATH ORIGINAL

It can be seen that the compounds of the invention when used as internal impregnating agents for paper this excellent oil resistance, water resistance and impart ink resistance.

Example 12

This example demonstrates the use of a typical substituted ammonium compound in accordance with the invention as an external impregnating agent for paper.

Different sets of _,

(CF,) ₅ CF0 (CF _o CF "). (CH ₀ CH ₀ ), -CONHCH ₅ N) Cl"

prepared as in Example 9, were in a mixture of 7: 1 parts by volume of xsopropanol trichlorotrifluoroethane dissolved. Paper handsheets thus formed were immersed in the solutions, dried at 115 ° C for 10 minutes, and treated with Tested for oil resistance, water resistance and ink resistance. The results are as follows compiled.

Concentration series swimming on Cobb value

ia No. Ink, seconds

0.5 12> 900 21.6

0.25 7 I50 24.0

0 0 9 8 4 2/1331

Example 13

This example demonstrates the use of typical N-halomethyl and N-methylol derivatives according to the invention as a treatment agent for textiles. Pieces of printed cotton cloth were mixed with a solution or emulsion soaked the test compound and air dried. That treated textile piece was then treated with regard to oil repellency tested according to the method given on pages 323: to 324 in Textile Research Journal, April .196 * 2 *. According to this procedure, drops of mixtures are made of mineral oil and n-heptane in different proportions carefully applied to the treated tissue and left to stand for 3 minutes. During this time there is the moistening and the penetration of the drops into the tissue observed. The number corresponding to the mixture with the highest proportion of heptane that does not penetrate or that Fabric not wetted is considered the oil repellency of the treated Tissue taken. A® number of 90 or more becomes regarded as excellent.

Compound solution evaluation of oil

repellent own - clinging

F ₂ ) CONHCH ₂ Cl 3.3 # in acetone 130 (CF J ₂ CFO (CF ₂ J ₅ CONHCH ₂ OH 3.3 # in acetone 130

(GF_J ₂ CFO (CF ₂ ) CONHCH ₂ OH 0.1 # in water

with a content of

$ 4.8, strength and

0.1 # Nalan *. 110

* waeserahweieendmaohendee means from E.I.duPont de Nemoura & Co.

00 9842/199 1

Example l4

This example demonstrates the use of typical substituted ammonium compounds according to the invention as a treatment agent for textiles. The compounds were dissolved in water ($ 2 solution), and cotton cloth was immersed in the solution, squeezed to remove excess liquid, and left in air dried. The treated wipes were followed by the procedure of Example 13 for oil repellency and according to AATGC Test Method 22-1952 for Tested for water repellency. The values are listed below.

link

Evaluation of the water repellency rating. Oil repellency

( ¹ CP ₃ ) gCFO (CF ₂ )

• fr

<9 ^H 2> 3 , N (OHJ

3 2

120 110

Example 15

) ₂ CFO (CF ₂

which had been prepared as in example 6 , was dissolved in water (3s 3 $ UigQ solution) »Protsen τοπ cotton tudi were soaked 8 meows with this solution« on paper

9 8 4 2/1991

towels!! spread out, air-dried for 1 hour and cured at 115 ° C for 8 minutes. The treated cloth had a water repellency rating of? Ö and a Rating of oil repellency of 120.

Example 16

This example illustrates the excellent durability of the compounds of the invention to repeated dry cleaning and washing.

¹ ^ (CFg) ₂ CFO (CF ₂ CP ₂ ) (CH ₂ CH ₂ ) ₅ CONHCH ₂ N Λ Cl "

which had been prepared as in Example 1, was dissolved in hot acetone (0.75 $ solution) and placed on dry cotton cloth up to a total of 0.4 $>. based on the dry weight of the fabric. The cloth was air dried and cured at 160 ° C for 2 minutes. The treated cloth was then rinsed in warm water, dried for 10 minutes at 80 ° C, ironed, cooled to room temperature and tested for water repellency and oil repellency. The cloth was then washed in a standard washing machine with detergent and then dried in an automatic dryer. The cloth was also subjected to five commercial dry cleanings. The values are summarized below;

00 98 42 / Ί 99 1

- ko -

Evaluation of the rating of the oil repellency water repellency

Initial test 130 100

after 5-maiigöEtt

Washing 130 100

after 15 times

Wash, 130 80+

after 5 times

Dry cleaning 130 100-

Example 17

■ · ../ - _cl -

the BaurawolltucJh. applied from an aqueous emulsion, by dissolving three parts of the compound in 20 parts by volume of hot isopropanol and adding 130 parts by volume of hot (50 ° C) 2 ^ aqueous starch solution had been made. The total uptake by the cloth on a dry basis was adjusted to $ 0.35. The results are summarized below 1

Evaluation of the
Oil repellency Evaluation of the
Water repellency Initial test 130 100 after washing 5 times 130 100 after 15 washes 130 80+

0 0 8 8 4 2/1991

- kl -

Examples 18-28.

Further illustrative examples are given below. These products were made as above but using the corresponding fluorinated amides and quaternizing agents manufactured.

Example 18.

ifCP ₃ ) ₂ CF0CCP ₂ CP ₂ ) 2CH ₂ CH ₂ CONHCK ₂ N (CH ₃ )

Example I?

.cp.

; Y ■ ² N.

I (CK) ₃ P ^ O -

O (CP ₂ CP ₂ ) ₃ (CH ₂ 9H ₂ ) ₃ CONHCH ₂ N ^(CH 2 ^CH 2 ^OH ^ ^oi

₂ CP ₂ ) ₃ (CH ₂ 9H ₂ ) ₃

Example 20

CP

CP.

P -i - O - "CF ₂ CH ₂ CONHCH ₂

• C - P

Example. 21st

CF ₂ c:

- F

.1
P - C - O _{(CF 2} CF ₂ ) ₂ CH _{2 CONHCH 2}

- F

00 98A2 / 1991

ORIGINAL INSPECTED ^

Example 22

«Ν

P- ¹ C-O-CP ₂ CONH;

- ι

Example 23

-P

p-fc-, 0- CF ₂ CP ₂ CP ₂ CPCI (GH ₂ Ch ₂ J ₅ CONHCH ₂ ^ C - P ■ "-... · ■; .. ■" ·.: ■■■ ~ ■

Cl "

Example 2k

CH.

'(CP ^ J ₀ CPOCF ₉ CP ₉ Ch ₂ CH ₂ CONHCH ₂ N _v

.Cl

0 0 9 8 4 2/1991

Example 25 Example 26

g _T S - C

- NH

Example 27

(GF J ₂ CS ¹ OGPgCHgCONHCHgN "^ P"; ■ Example 28

CHgCHgOH

0 0 9 8 4 2/1991

ORiGiNAL INSPECTED

Claims (1)

where R- and R independently of one another mean fluorine atoms, chlorine atoms or perfluoroalkyl groups or taken together a cyclic perfluoroalkylene group, where both groups R ₁ and R "cannot be chlorine atoms at the same time, Z, Z, Z and Z. independently of one another fluorine, chlorine or hydrogen atoms denote, where no more than two of the groups Z ₁ to Zr denote chlorine atoms, X., X_, X_ and X ^ independently of one another denote fluorine, chlorine or hydrogen atoms, with no more than one of the groups X. to X. Is chlorine atom, r is an integer from 1 to 2, m and η are integers from 0 to 75, the sum of in and η is 0 to 75, Y is a hydrogen atom or fluorine atom, ρ is 0 or 1 and W is a hydroxyl group, a halogen atom or the group QA, where Q is the residue of a nitrogen-containing quaternization HJitt © Is with at least one positively charged nitrogen atom where A means at least ® ± n negatively g © Iad © n © 8 Hal © genet © ni, where the ZaIaI the negative ■ '00 98 A 2/1991, - 45 - BATH ORIGINAL charged halogen atoms of A is equal to the number of positively charged nitrogen atoms, and t is an integer, that of the number of positively charged nitrogen atoms is equal to. 2.) A compound according to claim 1, characterized in that m and η are integers from 0 to 10. 3.) Connection according to Ansprüh 1, characterized by the general formula W t ρ. C -; O (CP ₂ ) _r (CP ₂ CP ₂ ) _ffl (CH ₂ OH ₂ . . c p where R. and R independently of one another mean fluorine atoms, chlorine atoms or perfluoroalkyl groups with 1 to 2 carbon atoms, where R ₁ and R _{2 are} not both chlorine atoms at the same time, m and η mean integers from 0 to 10 and v _f Y, p, V and T have the above meanings. k.) A compound according to claim 3, characterized in that V denotes a hydroxyl group and t denotes 1 « 5 ·) Compound according to claim 4, characterized duroh the formula - k6 009842/1991 CONHCH ₂ OH. 6.J compound according to claim 4, characterized by the formula (cf ₃ ) ₂ cfo (cf ₂ ) _{i; l} conhch ₂ oh. 7 ·) Connection according to claim 3, characterized in that Tf represents a halogen atom and t represents 1. 8.) A compound according to claim 7> characterized by the formula 9 ·) Connection according to claim 7 · characterized by formula (CF J ₂ CFO (CF ₂ J ₁₁ CONHCH ₂ Cl. 10.J compound according to claim 3, characterized in that W denotes the group QA, in which Q and A have the above meanings. 11.J compound according to claim 10, characterized in that Q is the heat of a tertiary nitrogen atom and A is a chlorine atom or a bromine atom. 12.J compound according to claim 11, characterized in that Q is the residue of a trialkylamine, cycloalkylamine, aromatic amine or heterocyclic amine. 00 98A2 / 1991 bad original 13.) A compound according to claim 10, characterized in that QA means pyridinium chloride. lh.) Compound according to claim 10, characterized by the formula ) ₂ CP0 (CP 15 ·) Compound according to claim 10, characterized by the formula , *, * -,) CPO (CP ₀ ) CONHCH ^ (CH ₀ ) _ (CP,) pCPO (CP.) -CONHCH ₀ H ' nv-:. ₂ ) ^ '2Cl 16.) A compound according to claim 10, characterized by the Formula. 17 ·) Compound according to claim 10, characterized by the Formula ', V vif ^ / ^ Wi? U VwJt? P ^ / J? _ / «V (w» nÄV / il_y _£ -UUtMiltrtl ^ W_ ν CX 009842/1991 ORIGINAL INSPECTED 18.) Compound according to claim 10, characterized by the formula 19 ··) Connection according to claim 10, characterized by the formula 20.) Use of a compound according to claim 1 to 19 for , Making cellulosic materials oil repellent. 21.) Use according to claim 20, characterized in that a compound is used in which Ii is group QA means in which Q and A are as defined above. 0 09842/1991