SU490298A3 - Method for oil and water repellent textile materials - Google Patents

Description

(cr,), - (s-n

/ -L / SNZ

) 1 1 - H-CO- -CH „-YAN- | And h1

la use aqueous dispersions of products, copolymerisation, and also solutions of organic solutions:) solution: gogel) 1l, as a mixture of ethylmethyloxy, acetone, or in a mixture of molecules with an fluorine-hydrogen fluoride and; 2-triftr-1,2,2-trichloroethane and isopropyl alcohol left. Aqueous dispersions of the product1: to1 copolymerisation panos t pa textile maji-lbUi where a is 4–70 s

1 orgapic solvents pa material: Y: DOMESTIC spraying, and on the material, t 0.39 --- 3.00 wt.% N mostly 0.77 iicc. % products co-polymerization. Then the material is dried and heat treated, for example, with loOC.

The products of co-polymerization are obtained by reciprocating 1 mo; P) ethyleyimine obCh and -0-CO-BN / 3+. СН, 0.5-5.0 mol of ethyleneimine of the general formula VW NH-CO-NC I

where n - 3-1; w-1-2,

in a solution of inert organic solvents, ort} Orktol with the addition of trifluoride boom or; one of the solutions; eral NOY

acid by 55YUO- S.

Example 1. 14 g {0.08 mol) of toluenendpisoctapapate are dissolved; Greek solvent 2.4 is mixed with a solution of 100 g (0.15 mol) of ethylene dimethyl of the formula C-, F, 5-CK.-0-CO-NH- / V

Ethyleneimnp is obtained by the interaction of ecoimol quantities of tolunlediisocyanate, predominantly its 2,4-isomer, 1,1-dihydroperfluorooctanol, and ethylene 1in in 100 ml of acetone.

The above mixture of very strong agitation and a temperature of 70-90 ° C is introduced over 4 hours into a solution consisting of 600 ml of water, 8 ml of 35% hydrochloric acid and 18 g of polyethylene glycol with a mol. in her. 1000. As the process progresses, acetone is continuously distilled off, the total amount of which after the reaction is 195 ml.

As a result of the reaction, a very fluid dispersion is obtained with a solid content of 26% in it. The fluorine content in the resulting product is 22% (see product A in the table).

Example 2. Proceed as indicated in example 1, but using the following amounts of starting materials, g (mol):

Toluene diisocyanate21 (0.13)

5.5 (0.13)

the isomer of this diisocyanate in 100 ml of acetone and mix the resulting solution with 3.5 g (0.08 mol) of ethylenimine in a nitrogen atmosphere at 10-20 ° C.

At a stand of stirring at a temperature of 30--40 ° C, 80 g (0.08 mol) of polyethylene glycol with a mol. weight. 1000. The resulting solution of the formula

- CH,

NH-CO-N

one ,-

CH /

Polyethylene glycol

with mol. weight. 1000130 (0.13)

Fluorinated

typeymatin75 (0.11)

The solution obtained as indicated in Example 1, after the introduction of fluorine-containing ethyepimine, is introduced into a solution containing 690 ml of water, 15 ml of 35% hydrochloric acid and 21 g of ethylene glycol mol. weight. 1000 under the conditions of Example 1. A dispersion of an active product content of 26.4% is obtained with a content of 13.7% in the active product (I eat product B in the table).

Example 3. Operate as described in example 1, but using the following amounts of starting components, g (mol):

Toluene diisocyanate14 (0.08)

Ethylenimine 3.5 (0.08)

Polyethylene glycol

with mol. weight. 100080 (0.08)

Fluorinated

ethyleneia200 (0.3)

The reaction mixture is added to a solution containing 900 ml of water, 30 ml of 35% hydrochloric acid and 27 g of polyethylene glycol with a mol. weight. 1000 as described in Example 1. A dispersion is obtained with an active product content of 26%. The active product contains 28.5% fluorine (see product C in the table).

Example 4. Get the reaction mixture according to example 1 using the following quantities of the original Komon GG, g (mol):

Toluylene endiocyanate 11.4 (0.066)

Ethylenimine 2.8 (0.066)

Polyethylene glycol

with mol. weight 2060135 (0.066)

Fluorine-containing ethyleneimine150 (0.22)

Or

; I} -CO-NH

,) - wvi-r

BN-CO-0-CH,) „-N

The resulting solution is placed with a solution of 62.5 g (0.158 mol) containing a mixture of ethylene. Mines of the formula

, - (№,), chsn,), - o-so-w /, ..

where ha 5, 7 and 9;

and a mixture of fluorinated alcohols containing alcohols mol. weight 413.5, corresponding to the formulas,%:

 N-СбР1з (СН2) 20Н21.8

H-C8R17 (CH,) 20P56.8

H-CioF2i (CH2) 20H21.4

With a strong transfer, the mixture is stirred at a temperature of 70-80 ° C for 3 hours in a solution containing 400 ml of water, 6 ml of 35% hydrochloric acid and 15 g of nolystilen glycol with a mol. weight 1000. Pz of the reaction mixture is continuously distilled acetone. As a result of the reaction, a flowable dispersion containing 26% of solid vendetva is obtained. The fluorine content in the active product is 15.4% (see product E in the table).

Example 6. 50 g (0.075 mol) of the product of the interaction of toluene diisocyanate, mainly its 2,4-isomer, with n1, 1, 2, 2-tetrahydroperfluorodecanol — 1 and ethyleneimine in equimole quantities and 50 g (0.042 mol) of the product borrowing diylocyanate with polyethylene glycol mol. weight 1000 and ethyleneimine in equimolar amounts in 100 g of acetone. As a result of the interaction, almost complete dissolution of these compounds occurs. The solution is shifted from 0.5 g of VRZ - dioxane and maintained at 50 ° C for 5 hours. After separation of the acetone, a yellowish, sticky powder is obtained, and the acetone-soluble solution and mixtures of 1,1,2-trifluoro-1,2,2-trichloroethane are buried. The reaction mixture is added to a solution containing 900 ml of water, 30 ml of 35% hydrochloric acid and 54 g of polyethylene glycol mol. weight 2060. As a result of the reaction, a dispersion is obtained with a content of active product of 27.5%.

The fluorine content in the active product is 19.5% (see product D in the table).

Example 5. Dissolve 13.6 g (0.078 mol) of toluylene diisocyanate, preferably its 2.4 isomer, in 100 ppm of acetone. Mix the obtained solution. 1O solution with 3.4 g (0.078 mol) of ethyleneimine at 10--20 ° C in a nitrogen atmosphere. In the case of a constant variation and a temperature of 30--40 ° C, 47 g (0.078 mol) of ethylene glycol with mol. weight 600. Get a solution of the product corresponding to the formula

-} ffl-co-: f i sn ,.

on with isopropyl alcohol (see product K

in the table).

Example 7. Samples of fabric from the mixture of cotton and polyethylene glycol terephthalate are plus an aqueous dispersion of the copolymerization products of L – E given in the table.

The concentration of the copolymerization products in the aqueous dispersion is 1%. Then the samples are dried and heat treated at 150 ° C for 5 minutes. As a result of processing, from 0.9 to 1% of copolymerization products are applied to the fabric.

Example 8. A sample of fabric from a mixture of cotton with polyethylene glycol terephthalate 50: 50 is sprayed with a 0.2% solution of the sonolymerization product K (see table) in a mixture of 1. 1,2-trifluoro-1,2,2-trichloroethane with isoprone, 015th alcohol.m; a ratio of 1: 1 to the content of the specified product on the fabric 0.77 weight. %, which corresponds to a fluorine content of 0.2 wt.%. Then the sample is heat treated at 150 ° C for 5 minutes.

Tkapi samples, according to examples 7 and 8, are bored with oil and water repellent properties, and the finishing effect is resistant to five-fold washing.

PREPARATION AND RESULTS

A method of oil- and water-repellent finishing of textile materials from natural and synthetic fibers by applying an aqueous disnersion or solution in organic solvents derived from condensates of fluorinated fatty alcohols with toluene diisocyanate and ethyleneimine followed by heat treatment, characterized in that, in order to increase the effect of H- ( 0-CH „-CH, a-0-С (СГ,) п-1г, Н,), -0-С-К /

where: a has a value from 4 to 70; n - from 3 to 11; t - from 1 to 2.

Papers, as derivatives of the condensates use the products of copolymerization of monomers of the general formula I and II

CH:

.

A1 H-CO-CH, -CH

1 - WI-CO- -OH, -CH7

when the ratio of these comonomers in

5 copolymer molecule, respectively, from

1: 0.5 to 1: 5.0, and applied to the material

0.39-3.00 weight. % of copolymerization products.