DE1670498A1 - New N-Perfluoroalkene- (1) -yl-aziridines - Google Patents

Description

New, complete ones intended for the printing of the disclosure pamphlet Registration documents.

U.Z .: 21 256-BB / H Ι

U.Z .: 21 256-BB / H

CIBA AKTIENGESELLSCHAFT, BASEL (SWITZERLAND)

Case 6093 / E

Germany

New N-Perfluoroalkene- (l) -yl-aziridines

The present application relates to new N-perfluoroalkene- (l) -yl-aziridines of the formula

X
OH

OH ₂

New Un ₁

licrk- -. :} Ρ t ⁹ ' ⁸ »ΒΑ. 2 I.?iA da.XndfuWÖW.v. # ■ U- 19C

wherein. X denotes a hydrogen atom or a methyl group and B denotes a branched or unbranched perfluoroalken- (l) ^{) -yl radical with 3 Dis} 18 carbon atoms or a perfluorocyclohexen- (l) -yl radical.

N-Perfluoroalkene- (l) -yl-aziridines are preferred the formula

CH

-N

GH,

⁰ (! (2-n) ^F 2 (i (2-n) + l

where X is a hydrogen atom or a methyl group, R, the addition to a perfluorocyclohexene ring, m, ρ and q each one Whole positive numbers from 1 to 16 and η 1 or 2 mean, m + p + q must not be greater than 18.

Among these compounds, N-perfluoroalkene- (l) -yl-aziridines of the formula are particularly suitable

R "CH ₂ ^ C = CN _n
J, CH "

109809/1941

wherein R ₂ and R ₂ , each a fluorine atom or a branched or unbranched perfluoroalkyl ^{radical with 2 to 1} J carbon atoms in the alkyl radical and R-. a branched or unbranched perfluoroalkyl radical having 2 to 7 carbon atoms, the sum of the carbon atoms in R ₂ , R, and Rj, should be 2 to 7, mean.

N-Perfluoroalkene- (l) -yl-aziridines take a preferred position here the formula

(4) R - CF = CP-N

/ ^H 2

one in which R- is a straight or branched perfluoroalkyl radical means having 2 to 7 carbon atoms. A compound of the formula (4) with particularly advantageous Properties is the aziridine of the formula

(5) F, C (CF ₀ ). - CF = CF - N j £ 4 \

XIH ₂

Aziridine is the N-perfluorocyclohexen- (l) -yl-aziridine the formula

mentioned·

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Both the compound of the formula (5) and the compound of the formula (6) are colorless ones which can be distilled OeI.

The new N-Perfluoroalkene- (l) -yl-aziridines der
Formulas (l) to (6) are formed by condensation of an aziridine of the formula χ

CH,

Η — Ν

CH,

wherein X has the meaning given, with a branched one or unbranched perfluoroalkene with 3 to 18 carbon atoms or perfluorocyclohexene, with elimination of hydrogen fluoride obtain.

In this reaction, perfluoroalkenes of the formula are advantageous

ä ^ J

s]

-C-F

Il
-C

^C q (2-n) ^F 2q (2-n

wherein R ₁ , m, η, ρ and q have the meaning given, is used.

109809/19 4

For the production of the new perfluoroalkene- (l) -ylaziridines of formula (3) is ethyleneimine with a compound of formula

N ⁴

wherein Rp, R ^ and R ^, have the meaning given, implemented. Compounds of the formula (4) are made by reacting ethyleneimine with a perfluoroalkene (l) of the formula

(10) * R ₃ - CF = CF ₂ , where R-. has the meaning given. For example, the perfluoro-n-hepten-1 is used here. In addition to the ethyleneimine, 2-methylaziridine can also be used for condensation with a perfluoroalkene. (

In addition to the linear perfluoroalkenes, e.g. the Dekafluoreyelohexen can be reacted with an aziridine.

The N-perfluoroalkene- (l) -yl-aziridines of the formula (l) tend to be spontaneous, slow when stored in glass vessels Polymerization. Depending on their constitution, these homopolymers fall as colorless oils or colorless, waah-like to hard substances.

Solid polymers can be melted and in water and all common solvents also in the heat

109809/1941

practically insoluble. Melted thinly on glass plates, hard and well-adhering films result after cooling. which for the most part repel oil as well as water. Additions of cationic catalysts, e.g. boron fluoride etherate or glacial acetic acid cause rapid polymerization. The polymerization can be in solution as well as in particular can also be carried out in substance "

The N-perfluoroalkene- (l) -yl-aziridines of the formula (1) can be polymerized not only with itself but also with another N-perfluoroalkene- (l) -yl-aziridine of the formula (l).

Both the monomeric and polymeric ones according to the invention Perfluorocompounds can usually be used for the oleophobic treatment of textiles. The textiles can can be treated with solutions such as dispersions or emulsions of the perfluorocompounds. The monomers can be applied e.g. from a solution with an organic solvent to wool or cotton and thermally fix on the fabric after evaporation. The addition of small amounts of 100% acetic acid favors this Fixability. Polymers can be made from benzotrifluoride, for example apply as a solvent to wool and cotton.

In addition to wool and cotton, synthetic polyamide fibers, polyacrylonitrile fibers, cellulose fibers,

109809/1941

generated cellulose or polyester fibers are treated with the new perfluorocompounds. The textiles can in the form of fibers, threads, flakes, but preferably of woven or knitted fabrics.

The so treated fabrics show an oil-repellent effect, combined with a water-repellent effect, the quality of both effects is characterized as very good loading λ may be.

Parts and percentages in the following examples are units by weight, parts by volume are related to parts by weight as ml to g.

1 09809/1941

- 8 Example 1

25 parts of Dekafluor-eyelohexen are dissolved in 150 parts by volume of dry ether. In addition one can under cooling at 10 ° C successively first 15.2 parts of triethylamine and then 4.31 parts of ethyleneimine [dissolved in 10 volume parts of dry ether W] are added dropwise and stirred for a further 1 1/2 hours at room temperature. The semi-solid precipitate is filtered off and the piltrate is shaken in succession with 100 vol. Luminous 2N sulfuric acid and then thoroughly with water and dry with sodium sulfate. After the ether has been distilled off, an oily residue is obtained which is distilled over a short column in a water jet vacuum. This gives 20.4 parts [79 $ of theory] a colorless ÖIS of boiling point 30 till 31 ⁰ C / 14 mm Hg
Analysis:

Calculated: C 33.7 H 1.4 N 4.9 F 60.0 found: C 33.8 H 1.5 N 5.0 P 59.4.

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Example 2

15 parts of n-perfluorheptene (l) are dissolved in 100 parts by volume of dry ether. For this one leaves under Cooling at 0 to 5 ° C, first 6.07 parts of triethylamine in succession and then 1.76 parts of ethyleneimine [dissolved in 15 vol.

by lumen parts of dry ether]. The mixture is stirred for a further 4 hours at room temperature and then decanted from the greasy precipitate. The decantate is made with 100 parts by volume Shaken water and acidified well with in-sulfuric acid. The ethereal phase is shaken with 50 parts by volume Water and makes it with 5 # sodium hydrogen carbonate solution alkaline. Then the ethereal phase is washed twice with water, dried with sodium sulfate and distills off the ether. The resulting oily residue is twice over a short column in a water jet vacuum distilled, giving 10.7 parts [71 $ of theory] of a colorless. OeIs receives. Boiling point: 56 to 59.5 ° C / 14 mm Hg. Analysis:

Calculated: C 29.0 H 1.1 N 3.8 P 66.2 Found: C 28.9 H 1.2 N 3.9 P 66.4

The substance is probably a mixture of cis and trans isomers.

1 09809/1941

Example 3

10 parts of a compound of the formula

! F = CP-GP ₂ —CF-CP_

[Boiling point 118.5 ° C.] are dissolved in 50 parts by volume of absolute ether. Then 2.5 parts are added within 10 minutes Triethylamine is added dropwise at a temperature of 5 ° C. In the course of 15 minutes, 0.86 parts of ethyleneimine are dissolved in 3.2 parts by volume Ether is added dropwise at a temperature of 4 to 8 ° C. Then the reaction is completed for 6 hours at room temperature.

The ethereal phase is extracted once with 10 parts by volume of cold 2N sulfuric acid, twice with 50 parts by volume of water, once with 50 parts by volume of 5 # strength potassium hydrogen carbonate solution, dried and distilled, 3 * 6 parts [yield: 3 ^ * 3 # äer theory] of one yellow product.
Boiling point: 65 to 66 ° C / 11 mm Hg.
Analysis: C ^ H ^ NF ^

Calculated: C 30.75 H 0.73 P 66.0 N 2.55
found: C 3Q, 84 H 0.79 P 64.9 N 2.71.

Mass spectrum: M 5 ^ 7 = parent peak. t ^C Ti |. ^H 4 ^NP 3a3

Nuclear magnetic resonance spectrum: There is a mixture of 2 substances *, namely

109809/1941

! F = C — CF ₀ —Ci * —CF, I 2 ι 3

I.
CF

, 0-OH ₂

and

CF = CF-CF ₀ -CF-CF, 2 ι 3

N CH,

H ₂ C

CF,

Example 4

10 ¹ I- parts of perfluorononene-isomer mixture [the mixture of isomers * was obtained according to US Patent 2,918 501 by trimerization of perfluoropropylene] dry ether are dissolved in 500 parts by volume. For this purpose, first 28 parts of triethylamine and then 9.95 parts of ethyleneimine are allowed to drip at 0 to 5 ° C. The mixture is stirred for a further hour at room temperature and the precipitated triethylamine hydrofluoride is filtered off. The filtrate is shaken with water and acidified with ln-sulfuric acid. The ethereal phase is separated off and shaken with fresh water, making it slightly alkaline with 5% sodium hydrogen carbonate solution. One dries the essential

! N $ PEC7H>

Phase with sodium sulfate, the ether is distilled off and fractionated in a water jet vacuum. 45 parts are obtained (4O, 5 # theory) of a colorless oil with a boiling point of 62 to 72 ° C / 15 mm Hg.

Analysis:

Calculated: C 27.9 H 0.8 N 3.0 found: C 28.2 H 0.7 N 3.5

This substance is a mixture of isomers of the general constitution

^E \

ff

CH,

C = C-N

with

^CH 2

Example 5

If the monomer from Example 1 is left to stand closed in glass vessels for a few weeks, it polymerizes from even slowly through. A colorless, hard wax-like to hard substance with a melting point of 15 ^ to 157 ° C. is obtained Substance is also formed in a strongly exothermic reaction when the monomer according to Example 1 is dissolved in carbon tetrachloride or added catalytic amounts of boron fluoride ether without a solvent.

109809/1941

Example 6

If the monomer from Example 2 is left to stand closed in glass vessels for a few days or weeks and then distilled it then remains up to $ 15 of a thick, oily, yellowish, polymer residue back. This does not dissolve in the usual organic solvents; however, he is easily soluble in cold benzotrifluoride.

Example 7

The monomer from Example 4 is in carbon tetrachloride dissolved and the addition of some boron fluoride etherate sets in the polymerization. The polymer falls as OeI,

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- 14 Example 8

13 parts of the monomer from Example 2 are dissolved in 30 parts by volume of chloroform. With thorough stirring, 1 part by volume of boron fluoride etherate is added over the course of 30 minutes and the mixture is then stirred for a further 30 minutes. The viscous, sticky precipitate is decanted off. After standing overnight, the precipitate has become pulverizable and hard. After drying, 9.5 parts (73 # of theory) are obtained. For cleaning, the polymer is dissolved in 15 parts by volume of boiling benzotrifluoride. When it cools down, it sometimes turns out flaky again. To complete the precipitation, 50 parts by volume of carbon tetrachloride are added, the mixture is filtered and washed thoroughly with carbon tetrachloride. After several hours of drying in a high vacuum at 50 ° C., a pulverizable material is obtained. The substance softens glass-like at 90 to 130 ⁰ G.

The polymer is also formed as a flaky precipitate when the monomer from Example 2 is dissolved in carbon tetrachloride, crosslinked with catalytic amounts of 100% acetic acid and left to stand for several hours. Furthermore, the monomer from Example 2 polymerizes after the addition of small amounts of 100% acetic acid when heated to 100 ° C. for several hours.

109809/1941 BADOWNAt

- 15 Example 9

5 parts of the monomer according to Example 1 and 5 parts of the monomer according to Example 2 are combined in 50 parts by volume Carbon tetrachloride dissolved. While stirring well, 1 part of boron trifluoride etherate is slowly added, with the copolymer precipitates as a sticky precipitate. The mixture is stirred for a further hour, decanted from the precipitate and washed him well with carbon tetrachloride. You dry for an hour at 50 ° C in a vacuum. 8 parts of a tough, hard mass are obtained.

, Example 10

, '· Oleophobic treatment of cotton and wool with the monomers according to example 2 and the polymer according to example 6.

These two substances, the following solutions are turned ^-: set: '-

Solution A: 2.0 % monomer, 97.8 # benzene, 0.2 # acetic acid 100 # solution B: 5.0 % monomer, 9 ^, 5 # benzene, 0.5 # acetic acid 100 # solution C: 2, 0 % polymer, 97.856 benzotrifluoride, 0, #

Acetic acid $ 100

Solution D: 5.0 # polymer, 94.5 # benzotrifluoride, 0.5 #

Acetic acid 100 #.

>'- ■: ■ - * ■■■ 109809/194 1

With these solutions samples of cotton poplin resp. Soaked wool gabardine [slightly changed] dried on filter paper at room temperature and kept for one hour at 100 ° C fixed in a closed glass vessel.

The oil-repellent effect was assessed according to the so-called "3 M oil repel.lency test" [Crajeok, Petersen, Textile Research Journal 22, 320-331 (196I). In this rating, 150 means the best attainable grade Results are summarized in Table I.

Example 11

Oleophobic treatment of cotton and wool with polymer ge ^ mass example 8,

One provides a 2.0 # and a 5 * above solution from Prepare polymer in boiling benzotrifluoride [solution E or P]. These solutions are used to prepare samples of cotton poplin and wool gabardine soaked hot, dried on filter paper at room temperature and then in the drying cabinet Heated to 100 ° C for 15 minutes. The oleophobic effect is assessed as above and summarized in Table I.

BATH ORIGINAL

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Table I.

Substrate Weight gain solution Monomers B. Polymers 0 D. S. P. Cotton-
poplin more oil-repellent
effect A. + 3 # 5 ft + 4 # Wool
gabardine Weight gain + 140 140 150 120 140 more oil-repellent
Effect '. 140 + + 3 Ji + IJi + 150 150 150 100 110 150

Remarks:

+ means: The change in weight of the The fabric through the equipment is only very insignificant.

109809/1941

- 18 Example 12

Cotton poplin fabric is impregnated bath consisting of 5 $ monomeric perfluorocompound according to the example 2, 94.4 # benzene and 0.556 acetic acid 100ji moved and dried at room temperature, then it is fixed at 100 ° C. for 60 minutes in a drying cabinet.

The beading effect [water absorption] of the fabric treated in this way is 7

; . Example 13

Cotton poplin fabric is impregnated bath consisting of 5 $ polymer fluorine compound according to the example 6, 94.5 # benzotrifluoride and 0.5 # 100 # acetic acid moved and dried at room temperature. Then

; is still at 100 ° C for 60 minutes in the drying cabinet

• i fixed.

, j. The beading effect [water absorption] of the so nimble 1- ;! th fabric is 6.75 ^

ORIGINAL INSPECTED 10 9 8 0 9/19 Λ 1

Example l4

Wool gabardine or cotton poplin fabrics are oleophobicized as follows with preparations of the monomer according to Example 2:
a)

Wool gabardine is made with a solution of 5 # monomers! according to Example 2 and $ 0.5 perfluorocaprylic acid in Soaked in chloroform, squeezed off and air dried. In a loosely closed glass vessel is then fixed at 95 ° C. for one hour.

Cotton poplin is treated in the same way as under a).

Wool gabardine is made with a solution of 5 # monomers) according to Example 2 and 0.5 # perfluorocaprylic acid in Acetone, which has previously been stored closed for 15 hours, soaked, squeezed off and on the Air dried. It is then fixed as described under a).

d) Cotton poplin is mixed with a solution of 5 $ monomer according to Example 2, -0.25 # perfluorocaprylic acid and 0.25 #

in chloroform
Acetic acid 100J6 / ge drank, squeezed off and air-dried. It is then fixed in a loosely closed glass vessel at 95 ° C. for 3 hours.

The oil-repellent effect is assessed in the same way as described in Example 10.

treatment

a)
b)
c)

d)

grade

140
130
140
130
'

1 941

Claims (1)

Claims New N-perfluoroalkene- (l) -yl-aziridines of the formula 2
CH / I CH ₂ where X is a hydrogen atom or a methyl group and B is a branched or unbranched perfluoroalkene- (l) -yl radical with 3 to 18 carbon atoms or a perfluorcyclo hexen- (l) -yl radical. New N-perfluoroalkene- (l) -yl-aziridines of the formula CH / I -C-N CH, -C .1 [ ^C q (2-n) ^F 2q (2-n) + l] where X is a hydrogen atom or a methyl group, R. the addition to a Perflüorcyclohexenring, m, ρ and q each one Whole positive number from 1 to 16 and η 1 or 2, where the sum of m + ρ + q must not be greater than 18. 3. New N-perfluoroalkene- (l) -yl-aziridines of the formula R ₂ 109 ^ 09/1941 wherein Rp and Rj, each a fluorine atom or a branched or unbranched perfluoroalkyl radical with 2 to 7 carbon atoms in the alkyl radical and R., a branched or unbranched perfluoroalkyl radical with 2 to 7 carbon atoms, the sum of the carbon atoms in R ₂ , R, and Rj, 2 to ; Should be 7. 4. New N-perfluoroalkene- (l) -yl-aziridines of the formula R - CP = CF-N / ^H 2 wherein R-. a branched or unbranched perfluoroalkyl radical means having 2 to 7 carbon atoms. "<5. New N-perfluoroalkene- (l) -yl-aziridine of the formula 6. New N-perfluoroalkene- (l) -yl-aziridine of the formula CH ₂ F ₃ C (CF ₂ ) ₄ -CF = CF-H 109809/19 * 1 qr _IS , _N au _NSPECTED