DE1468253A1 - Perfluoroalkyl-substituted alkanols and processes for their preparation - Google Patents

Description

U68253

fi JLvit%. <ν \ Χ-ζ- <~ I. Like Jd. ■

M 1392

Minnesota Mining and Manufacturing "Company, St. Paul, Minnesota, V.St.A.

Perfluoroalkyl-substituted alkanols and processes for their preparation.

The invention relates to a process for the preparation of a CJ -perfluoroalkyl-substituted alkanol in which several methylene groups are arranged between an alcohol group and the perfluoroalkyl group, which has 3 to 12 carbon atoms. These alkanols can be represented by the following general formula:

in R ~ a perfluoroalkyl group with 3 to 12 carbon atoms and m is an integer from 2 to 12.

Known from * the USA patent specification 2,666,797, perfluoro-

209811/1821 *; "uu UiUerlagen ivt7 ir subscription no. Ι em 3 <n" Xnd * mn _O 3fle ". v. 4. ·. do »

U68253

carboxylic acids or their derivatives with LiAlH. to perfluoro groups
to reduce carrying primary alkanols, which however ' between the functional alcoholic hydroxyl group and the
Perfluoroalkyl chain have only one methylene group. i

Fluorine-containing alkanols with one or more methylene groups
were made by reacting perfluoroethylene with primary or
secondary alkanols obtained (UÜA patent specification 2,559,628).
However, these alkanols do not contain a perfluoroalkyl group, but rather a hydrogen atom in one position, and they differ
therefore, in terms of their properties, they are essentially different from alkanols containing perfluoro groups.

Furthermore, the one having the perfluoromethyl group is secondary
Alkanol 1,1,1-trifluoropropan-2-ol by hydrogenation of
Trifluoroacetone (British patent
621 654). j

The inventive method is characterized in that
man.eine addition compound that is formed by reacting an organic; see a perf luoralkylgruppe with 3-12 carbon atoms ': having halides with j

(a) an alkenol:

(b) an alkene carboxylic acid

(d) a carboxylic acid ester of an alkenol or

(e) an ester of an alkene carboxylic acid; has been prepared, a reducing reaction: throws and the product obtained saponified if necessary. ^;

The invention leads to a class of new compounds with novel and unexpected properties. With these is the
fully fluorinated end group for the fluorocarbon proper; responsible (such as oil and water repellency). These j compounds have compared to fluoroalkylalkanols that between! the fluoroalkyl group and hydroxyl group is not at least two · '

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Methylene groups have different properties.

Compared to the previously known perfluoroalkyl groups primary alkanols. through the methylene chain adjacent to the alcoholic hydroxyl, (which consists of at least two methylene groups exists), it is possible to convert the compounds according to the invention into 1,2-unsaturated compounds by splitting off water.

It goes without saying that there are significant differences compared with secondary alkanols with perfluoroalkyl groups, both in terms of their reactivity, for example when reacting with isocyanates or diisocyanates or when converting to alkyl halides containing perfluoro groups, e.g. bromides, and in principle, such as for example in the case of oxidation with Na ₉ Cr ₅ O ₁ *.

The perfluoroalkylalkanols according to the invention are excellent, to reduce the surface tension in aqueous! Systems. These surface-active properties are lacking. | previously known Perfluoroalkylalkanblen, which between the ' functional alcoholic hydroxyl group and the perfluoroalkyl chain show only a single methylene group. ;

Among the novel invention tu -Perfluoralkylalkanolen j includes many compounds which are useful in the production of various products as intermediates' ■ ,; eg as intermediate products for the production of the corresponding | Perfluoroalkyl acrylates, perfluoroalkyl methacrylates and the polymers available from them »for the production of certain! perfluoroalkyl-substituted! Triazines and condensation products of these compounds with formaldehyde, for the preparation of certain perfluoroalkylvinyl compounds, certain perfluoroalkyl-substituted halomethyl ethers and that of

209811/1821.

Quaternary ammonium salts derived from these compounds., of carbamates by reaction of the alkanols with isocyanates, certain perfluoroalkyl-substituted textile treatment agents, from thermosetting polymers that are both oil and also have water-repellent properties, of surface treatment agents with improved b'l- and water-repellent properties ! Properties of curing agents for epoxy resins that increase the oil and water repellent properties of these resins, etc.

The compounds according to the invention which have several methylene groups between the perfluoroalkyl group and the hydroxyl group are obtainable by first adding a perfluoroalkylsulfonyl halide or a perfluoroalkyl halide with a _; Alkenol, which has a terminal double bond to the hydroxyl group, or is reacted with a corresponding terminally olefinically unsaturated carboxylic acid or with esters of such alkenols or such unsaturated carboxylic acids, the reaction with the perfluoroalkylsulfonyl halide under. J Desulfonylation proceeds. The reaction product obtained is then subjected to reductive dehydrohalogenation and, if necessary, to saponification. The CO -perfluoro-: alkyl-substituted alkanols can be obtained from the corresponding carboxylic acids prepared as above by reduction.

Examples of reactions which lead to the alkanols of the invention * in accordance with the above information can be shown schematically are represented by the following equations, where R- is as defined above and R is usually a Hydrocarbon radical, preferably a lower alkyl group having no more than about 6 carbon atoms, is:

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Kataly-R _x SO ₂ Cl + OH ₂ ^ CH (CH ₂ ) ^ ₁₀ OH R _f CH ₂ CHCl (CH ₂ J _1-

Cataly- + CH ₂ = CH (CHg) ₁ ^ ₁₀ OH 22 & 2Σ $ * R _x CHgCHJ (CHg) ^ ₁

Catalyst R _£ S0gCl + CH ₂ -CH (CHg) _1-9 CO ₂ H oator ,, ^ R ^ HgCHCl (CHg) ^

Kataly- · + CH ₂ -CH (CHg) _1-9 COgH aator ν

Kataly-R _f SOgCl + CHg-CH (CHg) _1-9 COgR sator ' R _x CHgCHCl (CHg) _1-9 COgR

J + CH ₂ -CH (CHg) _1-9 CO ₂ R fttor ^ H _x CHgCHJ (CHg) _1-9 COgR -

n (c * ri \ cm H ₉ , copper «/ _rw \. λλ t> Raneynickel 'R _x (CHg) _4-12 OH ^ 2' _{ο1ιΓΟΐη11?} R _x (CHg) _3-11 COgR ^

0 cataly *

R _x SOgCl + CH ₂ -CH (CH ₂ ) _1-10 0CR R _x CH ₂ CHCl (CHg) ₁ OC

2 catalysis,

+ CH ₂ -CH (CHg) _1-10 OCR flat or> R _x CHgCHJ (CHg) _1-10 OCR-

0 ^H 2 °

KOH; Zn ₉ HCl Rf (OHg) _3-12 OCR <

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In a "special embodiment of the invention is made from an addition compound of a perfluoroalkyl iodide containing 3 - having Ί2 carbon atoms, and an ester of an alkenol reductively cleaved hydriodic acid and saponifying the resulting product to the desired Perfluoralkylalkanol In particular, this method is for the preparation of erfindungsgeraäßen CJ. Perfluoroalkylalkanols in that one (1) brings an ester of a terminally or OJ -unsaturated lower alkanol (which has previously been treated with a base and distilled) to a solution of a small amount of azobisisobutyronitrile in a perfluoroalkyl iodide, that one (2 ) the mixture is moderately heated in order to bring about the addition reaction to an adduct of the perfluoroalkyl iodide on the ester, that ¹ (3) the adduct is separated from the mixture, e.g. by distillation, that (4) the adduct is hydrogenated, that (5) the ester obtained is saponified and that (6) the desired alkanol is isolated, for example by Desti llation. Carboxylic acid esters of unsaturated lower alcohols suitable as starting substances for this embodiment of the process according to the invention include vinyl acetate, allyl acetate, allyl propionate and other esters of alfenols with lower aliphatic acids.

For the implementation of the perfluoroalkanesulfonyl chloride or perfluoro alkyl iodides with the unsaturated compound are suitable Catalysts are, for example, organic and inorganic peroxides, azo compounds, actinic light and the like, although the like The desired result can often also be achieved by heating the reactants for a longer period of time alone.

Among the alkanols that can be prepared according to the invention are the called the following:

2- (perfluoropropyl) ethanol-1

2- (Perfluorhejk) tyl) -äthanül-1

2- (perfluorododeoyl) ethanol-1

3- (perfluorobutyl) propanol-1

3- (perfluorooctyl) propanol-1

2 0 9 8 T 1/1 8 2 1

U68253

3- (Perfluorododecyl) -propanol-1 4- (Perfluorooct ₍ y "l) -outanul-1

5- (perfluorobutyl) -pentanul-1 iJ-CPerfluorooctyiJ-pentanol-i 5- (perfluorododec, yi) -pentanol-1 6- (perfluorodecyl} -hexanul-1 7 - (- t ^> fluoroctyl) -heptanol-1 b- (Perfluorobut ^ ^r l) -octanol-1 8- (Perfluoi'Octyl) -octanul-1 8- (Pex ^ fluardodecyl) -uctanul-1 11 - (Perf luurbut _< yl) -unde oanol-1 11- (Perfluorooctyl) -undecanul-1 11- (perfluorodüaecyl) -undecanul-1 -11- (perfluor-4-ath, yl-cyclohexyl) -unaecanol-1 12- (P.erfluorDut, / i) -doaecanul-1 12- (perfluorooctyl) -äoaecanül-1 12- (perfluordoüecyl) ~ doaecanül-1 and the like.

The invention is further developed by the following examples

! purifies, aie not as a limitation of the scope of the invention to

are to be included, all parts mean - unless otherwise stated - parts by weight.

! 'jeisüiel

ι ■ *

Production of alcohols according to the invention by reaction of a perfluoroalkanesulfonylchloride with an alkanol and subsequent Reductive nalOtien hydrocarbon cleavage:

Perfluorooctanesulfone / lchluria and ullyl alcohol: C ₀ F ^ r ₇ CH ₀ UIiClCH _n UiI and an approximately 4-fold molar excess of sodium hyaroxide are dissolved in a mixture of equal parts water and ethanol. The solution is worked out together with Raney

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H68253

nickel as a catalyst placed in a shaking hydrogenation autoclave. The hydrogenation takes place at a temperature of about 13ü ° C

carried out with hydrogen of 176 kg / cm. The catalyst is filtered off from the reduction mixture and the filtrate is evaporated to remove the solvent. The residue is dissolved in ether and the ethereal solution is washed with dilute hydrochloric acid and dried. The vacuum distillation delivers -.3- (Pe:
9 - "10 mm Hg.

supplies> - (perfluorooctyl) propanol, boiling point 105 - 112 ⁰ C /

5 - (Perfluorooctyl) pentanol is made by reacting perfluorooctanesulfonyl chloride and penten-4-01-1 in the presence of di- tert-butyl peroxide followed by catalytic hydrogen halide uff AD cleavage established.

Example 2

Production of alcohols according to the invention by reacting a perfluoroalkanesulfonyl chloride with an olefinically unsaturated carboxylic acid, subsequent reductive elimination of hydrogen halide to produce the ^ - (perfluoroalkyl) alkanoic acid, and subsequent reduction of the functional

Acid group for the corresponding alcohol: j

A mixture of 26.8 g (0.052 mol) of perfluorooctanesulphonyl chloride and 5) g (0.050 kol) of 4-pentenoic acid (allylacetic acid) is given in the presence of a catalytic amount (1-, O g) of di-tert-dutyl peroxide heated under reflux for four hours at about 120-145 ° C. The reaction mixture is fractionally distilled under reduced pressure and collect the 0.01 mm Hg under pressure at about 1Ou ⁰ C boiling fraction of a ftach Umkristallißation; Mixture of chloroform and carbon disulfide melts the i prepared 4-chloro-5- (perfluorooctyl) -pentanoic acid j at about 89 - '9O ⁰ C. i

The 4-chloro-5- (perfluorooctyl) - prepared in this way

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Pentanoic acid is hydrogenated by adding a solution of 8.00 g (0.0145 moles) of the acid and 2.5 g (0.062 moles) of sodium hydroxide

"in a mixture of 30 ecm of water and 30 ecm of ethanol in the presence of 4 g of Raney oil as a catalyst for 3 hours at 14u G in a shaking hydrogenation autoclave with hydrogen of 176 kg / cm. After removal of the catalyst and evaporation to dryness an amorphous residue is obtained, which consists of the sodium salt of 5 * ~ (perfluorooctyl) pentanoic acid. By dissolving this residue in water and acidifying the resulting solution, the 5- (perfluorooctyl) pentanoic acid is obtained in the form of a waxy, lingering solid substance which can be distilled under 0.02 mm Hg pressure at 100 ⁰ C \ i iaeh Umkristallisati.on of carbon disulfide melts the acid at about 86.5 -. 87.3 ⁰ C.

A suspension of 30 parts of 5- (perfluorooctyl) pentanoic acid in ether is added to a solution of 3 parts of lithium aluminum hydride in about 200 parts of anhydrous ether. That The reaction mixture is stirred for about 48 hours, then treated with water and neutralized with sulfuric acid The reaction mixture is extracted several times with ether. The ether extracts are combined, dried and fractionated in Vacuum distilled. 5- (Perfluorooctyl) pentanol is obtained, which boils at about 108 ° C. under 2.5 mm Hg pressure.

Do the same using 10-undecanoic acid instead of allylacetic acid for the preparation of perfluoric acid 11- (perfluorooctyl) -undecanoic acid obtained in the reduction yields 11- (perfluorooctyl) -undecanul which boils at about 122-126 ° C / 0.10-u.15 mm Hg.

By repeating the above procedure using perfluoro-n-pentanesulfonyl chloride and perfluorododecanesulfonyl chloride instead of perfluorooctanesulfonylchloride, 5 - ('± ^> erfiuorpentyl) pentanoic acid or 5 - (- perfluoraodecyl) pentanoic acid are obtained. Similarly, using

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formation of 3-butenoic acid, 6-heptenic acid and 1u-undecenoic acid instead of 4-pentanoic acid, to carry out the process of this example 4- (perfluorooctyl) butyric acid, 7- (perfluor- j οctyl) -heptanoic acid and H-CPerfluoroocty ^ -hendecanoic acid. During the reduction, these acids provide the corresponding alcohols 5- (perfluoropentyl) pentanol, 5- (perfluorododecyl) pentanol, 4- (Perfluorooctyl) -butanol, 7- (Per: Lluorooctyl) -heptanol or, 11- (perfluorooctyl) hendecanül.

Example 3

Preparation of alcohols by reaction erfindungsgemäi3en \ a Perfluoralkansulfonylohlorids with a prime an alkenol, reductive elimination of hydrogen halide and hydrolysis to give the corresponding alcohol:

Is added to a mixture of 8UE g Perfluorooctanesulfonyl and 31 g of allyl acetate, about 3 g of di-tert-butyl peroxide was added and the reaction mixture is slowly heated to about 80 C, wherein a spontaneous rise in temperature takes place at about 130 ⁰ C, wachuem the reaction subsided , a further amount of di-tert-butyl peroxide is added. iSs will continue

ο '

Heated for about 14 hours to about 110 C, where after about 8 hours of heating, a further addition of peroxide takes place. The reaction mixture is then fractionally distilled in vacuo and the 2-chloro-3- (perfluorooctyl) propyl acetate is collected as a fraction boiling at about 153-15 ° C./37 mm Hg. To a solution of 5UE, 5 of this substance g in 50 cc of anhydrous i methanol containing "phenolphthalein as an indicator, is in;. Optionally methanolic solution slightly more than the theoretical amount \ of sodium methylate The lieaktionsgemisch pink and sodium chloride precipitates turns from weak After standing for about 48 hours at room temperature, the reaction mixture is treated with about 10 ecm of water and a further small amount of sodium methate and then heated for about 4 hours to about 5 μg. The organic phase is then removed and fractionated.

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distilled, the fraction boiling within the range of 129-141 ⁰ C / 37 ram Hg being collected. The 3- (perfluorooctyl) allyl alcohol prepared in this way possesses

23
a refractive index of n ^ = 1.3328. ifiin mixture of 42 g · 3- (Perfluuruot _s yl) -aliylalii: Uaul, 1.8 g Haneynickel, 45 cc of "tlianul and 1 g Kaliumh / druxyd is gegeüen in an autoclave una ./asserotoff introduced below about 150 atmospheres pressure. The ii, yurieruiig to the corresponding saturated alcohol shows itself on üiueni within about an otundue pressure drop. The iieaktionsgemisch is filtered from the autoclave herau3 _tJ enummeii and the filtrate uestiiliert fractionated in vacuo. 3- (Perfluorooctyl) -propanol is obtained, which is about 13 <i - 143 G / 38 mm Hg and has a refractive index of n ^ = 1.3312. The infrared spectrogram of the substance shows that it consists entirely of the saturated product.

Example 4

Production of the alcohols according to the invention by reaction of a perfluoroalkyl iodine with an ester of an alkenol, reductive elimination of hydrogen halide and saponification to give the corresponding alcohol:

To a solution of υ, 656 g (u, uu4 mol) of azobisisobutyronitrile in 99.2 g (υ, 2 i, .OL) 1-Jodperfluorheptan 17.2 g (u, 2 Kioi vinyl acetate ge _ä Eden, aas to remove of the polymerization inhibitor had previously been ^{treated with potassium hydroxide at Iu 0} C and distilled. The heat is slowly heated. At 8 ° - 9 ° C, an exothermic reaction takes place, ax the tempers door for about 1u; ..in minutes to 11u - 116 be removed 8u C - C brings the JSS is a further 2 to otuncieii du ° C erwurmt, vionach unreacted vinyl acetate una 1-Juaperfluorheptan (47.6 g) from the reaction rate '■ mixing under a pressure of 2 -. 5 mm Hg at 7υ , jis uieiuen 57.7 g of the resting product C ₇ F, cCHpCHJOCOCHt back. * '

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BATH ORIGINAL

H68253

A slurry of 7.45 g (υ, 196 mol) of lithium aluminum hydride in 75 ecm of anhydrous ether is kept under moderate reflux while stirring rapidly, while 80.0 g (0.138 mul) of the crude adduct from the above is kept within 1.5 hours described implementation in 75 ecm anhydrous ether are added. The reaction mixture is stirred for about 17 hours and maintained at reflux and then cooled to 10 ⁰ C. 25 ecm of ethyl acetate and then 75 ecm of 3% sulfuric acid are added. The viscous mixture is refluxed for 3 hours and the ether layer is separated off, washed twice with 25 ml of 5% aqueous sodium bisulfite solution and dried over magnesium sulfate. Vacuum distillation through a 1.

n _D = 1.3212. Gas-liquid chromatography shows that the distillate consists of 76.2 ^ of a lower-boiling component and about 23% of a slightly higher-boiling component. 34 g of distillate are refluxed for 2 hours in 100% strength alcoholic potassium hydroxide solution. The mixture is then neutralized with 10% aqueous sodium hydroxide solution. Sodium chloride is added until the solution is saturated. The phases are separated and the organic phase is diluted with ether and dried over magnesium sulfate. The vacuum distillation yields 25.0 g of distillate with a boiling point of 84 ° C./10 mm Hg;

25th
No. = 1.3186. Gas-liquid chromatography shows that the low boiling component is 99 # C ₇ F ₁₅ CHpCH ₂ OH.

Example 5

Production of alcohols according to the invention in which m = 3 is, according to the following series of reactions:

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U68253

Il Il fl Il

• IUG-Ü-C _O H_ + CHX-UCH-, -> RX-CH ₀ C-UCH-,

O 0 / ^H 2 '

H ρ (j ng η fc5

Eprr_nTT_p_nprr Λ c- ? tj ρ pit / " ¹ Hf ¹ XJ ΗαϋβΥΙΐΙΟΚβΙ

₂ ,
Raney nickel

"LiAlH
H _f (CH ₂ ) ₂ C-üCH ₃

3- (Perfluorpropyl) -propanol is made from ethyl perfluorobutyrate such as prepared as follows: About equimolar amounts of ethyl perfluorobutyrate, methyl acetate, and sodium methoxide are used. The ethyl perfluorobutyrate is added with constant cooling to a cooled solution of sodium methoxide in absolute ether, After stirring this mixture for about 2 hours, the methyl acetate is added, a clear solution being formed. The solution is stirred for about 16 hours and then under reduced pressure Pressure distilled to remove solvents and methyl 3- (perfluoropropyl) -3-ketopropionate as the main product to obtain. The ketoester obtained in this way is about 2% in an ethereal solution with Raney nickel as a catalyst Hydrogenated under pressure for hours. The catalyst is filtered off and the filtrate is fractionally distilled in vacuo, with Methyl 3- (perfluoropropyl) -3-hydroxypropionate is obtained, which boils at about ö5 ° C / 15 mm Hg and has a refractive index of njp = 1.3513. About 157 parts of the on this V / eise obtained hyuroxy ester and 175 parts of phosphorus pentoxide mixed together and left to stand for about 15 hours, with a rather violent exotherm shortly after mixing Implementation is to be determined. The reaction mixture is then filtered and the filtrate purified by fractional distillation.

209811/1821 0AD ORIQlNA !.

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Methyl 3- (perfluoropropyl) acrylate is obtained, which under 732 mm Hg pressure at 121 - 124 C boils and a refractive

25th
has an index of n ^ = 1.3362. The acrylic acid ester is hydrogenated in an ethereal solution using Raneyniotcel as a catalyst under customary conditions at high pressure. The reaction mixture is filtered and the filtrate is fractionally distilled under reduced pressure. The corresponding saturated ester, methyl 3- (perfluoropropyl) propionate, is obtained, which boils at 42 ° C. and 12 mm Hg pressure

25th
has a refractive index of n ^ = 1.3276. To a solution of 7.6 g (0.2 mol) of lithium aluminum hydride in 500 ecm of ether, 49 g (0.191 mol) of methyl 3- (perfluoropropyl) propionate, dissolved in 100 ecm of ether, are added at such a rate that the reaction mixture is kept under high reflux. The mixture is then stirred for a further 1 hour and an excess of methanol is added in order to hydrolyze the complex. The reaction mixture is then acidified with dilute sulfuric acid. Bie-Jtt her layer is separated and the aqueous layer extracted with about the same volume of ether. The combined ether extracts are evaporated and the residue is fractionally distilled. The 3- (heptafluoropropyl) propanol obtained sieaet at about 140 141 ° G / 745 mm Hg and has a refractive index of n = 1.3270j

-Patent claims-

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Claims (3)

H68253 i -15 patent claims! 1. A process for the preparation of a perfluoroalkyl-substituted: alkanol, characterized in that for the preparation I of an oz-perfluoroalkyl-substituted alkanol, the perfluoroalkyl group of which has 3-12 carbon atoms, a. ^: Addition compound, which is created by converting an organic a perfluoroalkyl group having 3-12 carbon atoms having halides (a) an alkenol (b) an alkene carboxylic acid (d) a carboxylic acid ester of an alkenol or (e) an ester of an alkene carboxylic acid has been produced, a reducing reaction under-; throws and saponified the product obtained if necessary. 2. The method according to claim 1, characterized in that one j is an addition compound of 3-12 carbon atoms
containing perfluoroalkyl iodide and a carboxylic acid ester i of an alkenol and that the product obtained j is saponified. | 3. Perfluoroalkyl-substituted alkanol in which between the alcoholic hydroxyl group and the perfluoroalkyl group
a plurality of methylene groups are arranged, represented by the following formula wherein R _{f is} a perfluoroalkyl group having 3 to 12 carbon atoms
means and m is an integer from 2-12. , 209811/1821