DE2062816B2 - Process for the preparation of organosilicon compounds containing branched perfluoroalkyl radicals - Google Patents

Description

F-C C-OH

I!

CF ₃ CF ₃
or its alkali salt is used.

The USA.-Patent 3 331813 teaches the analogue, the structural unit with trifunctional

Position of fluorine-containing organosilicon losers silicon atom can be represented as follows:

20th

SiO,.,

Y I

/ '(CH ₂ L

-si I

\ 25 O

^R "CF ₂ X-CF-CF ₂ X '

bonds of the formula

CF ₂ X

FC-O- (CH ₂ ) "
CF ₁ X '

In this formula, X and X 'are each a halogen radical, Y is a halogen radical, an alkoxy or an arvxy group, R is a hydrogen radical or a monovalent hydrocarbon group which may optionally be halogenated, m is 2 or 3, η is 1 or 2, ρ is 1, 2 or 3, q is 0, 1 or 2 and the sum of η, ρ and q is 4.

In the aforementioned USA patent specification are also polymeric organosilicon compounds which can be obtained in that one compounds of the general formula

40

CF ₂ X

FC-O- (CH ₂ L-CF ₂ X '

which contain two or three hydrolyzable groups, optionally hydrolyzed together with other hydrolyzable organosilicon compounds and condensed. The resulting polymer molecule contains, depending on the functionality, the organosilicon Starting compounds mono-, di- and optionally trifunctional silicon units. the The structural unit with a difunctional silicon atom has the following formula

—Si— Ο—
(CH ₂ L
O
CF ₂ X-CF -CF ₂ X

As a general formula for a polymer built up from different functional silicon units is can be the following formula

SiO,
(CH ₂ L
O
CF ₂ X-CF-CF ₂ X '

are considered representative. In this formula, a has an average value from O to \, b one

average value from 1 to 1.5, c an average value from 1 to 2 where the sum of a + 2b + c = 4.

US Pat. No. 3,331,813 also reveals that the monomeric and polymeric organosilicon compounds containing fluoroalkyl radicals, when applied to fiber-containing materials, give them good oleophobicity combined with good hydrophobicity. The combination of oleophobicity and hydrophobicity achieved with these compounds is sufficient for many applications. However, it is sometimes desirable to achieve an even higher degree of oleophobicity. This is an object of the present invention.
From the Offenlegungsschrift 1 568 600 is a ver

drive to the production of perfluorinated, tertiary alcohols of the general formula

F-C-

R'r
C-OH

CF ₃ R?
known, wherein R ' _f and R ² _r perfluorinated alkyl radicals

with 1 to 3 carbon atoms. Perfluorinated ketones are used according to this procedure the general formula

C = O

wherein Rf and R ² _{r have} the above meaning, initially with potassium, rubidium or cesium fluoride in an inert polar solvent, whereupon the resulting reaction mixture with hexafluoropropylene of the formula

CF ₃ -CF = CF ₂

further reacted and hydrolyzed the compound obtained.

in Offenlegungsschrift 1 595 696 is now a Process described in which one of compounds of the formula

CP ₁ CF,
FC C-OMe

The process essentially takes place in two stages. First is the branched, perfluorinated Alcohol or the alcoholate of the formula

CF ₃ CF ₃

F-C C-OM

I I

CF ₃ CF ₃

.

with allyl halide, excluding allyl fluoride, in implemented in a known manner. In a second process step, the allyl ether obtained is with implemented an organosilicon compound, wel-

before at least one SiH group. The addition reaction proceeds using catalysts known for this purpose, such as, for example, hexachloroplatinic acid. The organosilicon compound can be monomeric or polymeric. Examples of suitable monomeric organosilicon compounds, that is to say silanes with SiH groups, are HSiCl ₃ , CH ₃ HSiCl ₂ , H ₂ SiCl ₂ . Examples of polymeric siloxanes which contain one or more SiH groups are

CF ₃ CF ₃

goes out and this reacts with an acrylic acid halide.

The connections made in this way are said to be particularly different from the known equipment characterized by an improved oil repellant fleece. The compounds also have a higher softening point than the known products. However, a disadvantage of these compounds is their susceptibility to hydrolysis. Also lend they give the fibrous substrates treated with them an undesirable hard feel.

A further object of the present invention is therefore to provide fluorine-containing organosilicon Finding compounds with excellent hydrophobicity and oleophobicity of the with Textiles equipped with them give them a soft feel at the same time and in the interests of durability of the equipment are stable to hydrolysis.

Surprisingly, it has now been found that certain organosilicon, branched perfluoroalkyl radicals containing compounds meet these requirements. The present invention therefore relates to a process for the production of organosilicon containing branched perfluoroalkyl radicals Compounds by reacting a branched, perfluorinated alcohol or alcoholate with allyl chloride, bromide or iodide and addition of one containing at least one SiH group organosilicon compound to the allyl ether obtained and is characterized by that one as branched, perfluorinated alcohol

CF ₃ CF ₃
FC C-OH

I I

CF ₃ CF ₃
or its alkali salt is used.

R —O -

CH ₃

Si — O—

= 2 to 200, preferably> 30

R-O-

CH ₃
Si-O-

R '

Si-O-O

CH ₃ -SiH

ι
O

R = (CH ₃ I ₃ Si, alkyl with 1 to 3 carbon atoms. H, CH, -C -

' 1! ο

R '= CH ₃ or H, a = 1 to 100, b = 0 to 10

as well as compounds of the bath composition or with units of the formula

CH ₃

Si-O-

H
- Si-O

X = Cl, CH ₃ -CO-

⁰ έ

The fibrous substrates can be treated with both the monomeric and the pt / lymeren organosilicon compounds are carried out.

The monomeric compounds can be in the form of vapors, or in the form of pure liquids applied from solution in an inert volatile solvent to the fiber material. It may be advantageous to use chlorine atoms that are known per se instead of the chlorine atoms bonded to the silicon atom Way to provide alkoxy residues. This avoids acid loading of the tissue. When applying The binding of the monomers to the fiber material takes place through the conversion of the reactive ones Groups of the monomer with the reactive sites in the fibers. One can further assume that at the same time the polymerization of the monomer occurs in situ on the fibers, and that such polymerization due to the moisture inherent in all fiber materials is present, is accelerated. About the binding of the monomer and the in situ polymerization of the same To accelerate, it is recommended to harden the treated fiber substrate, for example 2 to 60 minutes at 50 to 160C. To speed up the hardening process, one can use an egg known Curing catalysts, such as. B. zinc octoate, dibutyltin diacetate or dilaurate. Triethanolamine titanate, Triethanolamine zirconate, zirconium acetate. Zirconium oxychloride, Zirconium or titanium esters of alkanols such as tetrabutyl titanate and zinc perfluorobutyrate. admit.

When using the polymeric compounds, the polymer is usually dissolved in an inert, volatile solvent such as (trifluoromethyl) benzene, 1,3-bis-trifluoromethylbenzene or trichlorotrifluoroethane. The resulting solution is applied to the fiber material using known immersion or padding methods. By varying the concentration of the polymer in the solution and the degree of blocking, the amount of polymer that is deposited on the material can be varied. Typically, the amount of polymer can be 0.1 to 20 percent by weight, based on the weight of the fiber material. Usually, when treating textiles such as fabrics, the amount of polymer is limited to 0.1 to 5 percent by weight in order to achieve the desired repellency and at the same time to maintain the soft feel of the textile. It is also possible. to apply the polymers in the form of an aqueous emulsion to the fiber material. After the polymers have been applied, it is also expedient to carry out a hardening treatment using the catalysts described above. The polymeric compounds can be obtained by adding the allyl ethers to polymeric SiH compounds or by hydrolysis condensation of the monomeric addition compounds. In such a hydrolysis condensation, other monomeric silanes can be added to increase the degree of crosslinking or degree of polymerization or to improve the reactivity of the polymeric materials with fibrous substrates. Examples of such silanes are SiCl ₄ . HSiCl ₃ , with HSiCI being preferred. since SiH atoms remain in the hydrolysis condensate, which improve the recording capability on the fiber. Dicst: hydrolysis condensation is preferably carried out in fluorinated solvents such as trifluorotrichloroethane. carried out. The silanes used for hydrolysis, such as SiCl ₄ or HSiCl ₃ . should be reduced in at most equimolar amounts, preferably half equimolar amounts.

A large number of suitable fibrous substrates are suitable of materials such as paper, cotton, linen, hemp, jute, ramie, sisal, cellulose acetate-rayon, Cellulose acetate / butyrate rayon, saponified acetate rayon, viscose rayon, copper ammonium rayon, Ethyl cellulose, fibers made from amylose, algins or pectins, wool, silk, animal Hair, mohair, leather, furs, made from casein, soybean peanut proteins, zein, gluten, egg albumin, Fibers made from collagen or keratin, polyamide fibers, polyurethane fibers, polyester fibers, such as polyalkylene terephthalate, fibers based on polyacrylonitrile or fibers of inorganic origin, like asbestos or glass fibers. The invention can find application to textile materials that are present in the form of loose fibers, threads, yarns, twisted threads, slivers, fiber bundles, braids, cords, ribbons, Woven or knitted goods, felts and other non-blown goods Nonwovens, articles of clothing or parts thereof.

Fiber materials. which have been treated with compounds prepared according to the invention, have an increased oil and water repellency on. Of particular importance is the equipment's resistance to repeated k-m Washing or chemical cleaning. It is also important that the strengthening of the oil repellency is possible without affecting the other liyenschaflen of the textile material is achieved. Indeed, the feel of the treated textile material is insofar improved as it becomes softer and more pliable.

example 1

a) Addition of allyl chloride

374 g (1 m) potassium perfluoro-2,3-dimethyl-butanolate- (2)

CF, CP,

FC C-O-K

j I

CF ₃ CF ₃

(prepared analogously to Offenlcgungsschrift 1 568 600. Example 1) are stirred in 200 ml of dimethyl diglycol. 114.8 g (1.5 m) of allyl chloride are then added. This mixture is heated to 75 to 90 ° C. while stirring, during which potassium chloride separates out. To The potassium chloride is filtered off for 24 hours and the filter cake with dimethyl diglycol after washing.

The filtrate is mixed with 950 ml of water. The lower fluorocarbon phase is separated three times washed with water and dried over sodium sulfate.

Subsequently, the Ally'äthcr with sodium hydride treated. Om him from remnants of the starting alcohol to free. The [Pcrnuor-2,3-dimethylbutyl- (2)] - allyl ether showed the iodine number:

practically 66.0

theoretically 67.5

b) Reaction with SiH-containing silane

188 g (0.5 m) of the allyl ether are mixed with 67.7 g (0.5 m) HSiCl.

This mixture is added to a stirred heated to I ¹ OO C solution of 90 mg (IfiOmg.val

Sill) l'yridine- (Älhvlen) -l '((I, in K) (ImI dried Toluene dripped. The temperature shouldn't drop below 90'C depends on the reflux that occurs. After the end of the dropping, the mixture is left still further 12 lines under rejection conditions react. Then the volatile constituents graze up to a sump temperature of 170 (. '. The residue has a chlorine content of 20.43%. Theory: 20.75% Cl.

c) reaction with siloxane containing siloxane
64.05 g (~ 1 mol sill) of a siloxane of the lormel

Si-O

CII,

Si O

Si (CTI ₁ ),

are mixed with 2 (X) ml of toluene and 188 g (0.5 m) of the allyl ether from Example 1. This mixture is added dropwise with stirring to a solution, heated to 105 ° C., of 90 mg of pyridine- (ethylene) -Pi ('l ₂ in 2 (X) ml of dried toluene. The temperature should not drop below 95 ° C. after the addition of the The reaction mixture is allowed to react for a further 12 hours at KX) C. The residue freed from toluene in vacuo has an SiH content of 0.82%. Theory: 0.78%.

Comparative example 1

51.15 g (0.1 m) of the prepared according to Example I. Paragraph b - / - [Pcrfluoro-d.l.Z-trimethylpropoxy-J-propyltrichlorosilanes are in 100 ml of a mixture of equal parts by volume of toluene and 1,1,2-trifluorotrichloroethane solved. This mixture is stirred vigorously at room temperature within 55 to 60 minutes in a solution of 27.8 g of NaHCO, (0.3 m + 10% excess) in 300 ml of water. After dropping, it is immediately diluted with 50 ml of ether. The organic phase is washed up with water

l'rocliikl des

Vcrplcichsbcispicls

I. I. 1 I.

Nichi according to the invention
comparison

(I all the I
l% 2_

0.5
0.5
1.0
1.0
0.5
0.5
1.0
1.0
1.2

Nii πμ

/ irkiinhiilKxkl

washed to a neutral reaction, dried over sodium sulfate and the ether distilled off in vacuo.

Comparative example 2

. B produced 102.3 g (0.2 m) of the Example I, Section - [PerlluoM ll, 2-lrimcthylpropoxy -) '| -propyltrichloi silane and 13.5g (0.1 m) SiHCI ₃ are in KX) ml of dried and I oluol 300ml dried 1.1,2-Trilluortriehloräthan dissolved.

While stirring vigorously, this solution is added dropwise to a mixture of 74 g NaHCO ₃ (0.8 m + 10% excess) in 6 (X) ml water, 250 ml toluene and KX) ml 1.1.2-irifluorotrichloroethane within 3 hours.

When the dropwise addition is complete, it is immediately diluted with 2 (X) ml of ether and the organic phase is diluted several times washed with water, dried over sodium sulfate and the ether was distilled off in vacuo.

The hydrolysis condensates of the comparative examples 1 and 2 are diluted with 1.1.2-trifluorotrichloroethane, so that 0.5 or 1% solutions are formed. Cotton popcline pieces c are soaked in these solutions by dipping for 10 minutes. After 24 hours Drying in air is cured at 150 ° C. for 5 minutes.

Similar impregnation solutions with an addition of 15% Zr- (OBu) ₄ , based on the used! lydrolysis condensal. were also made.

To compare the properties of the same tissue pieces were soaked with 1.2% igcn solutions of a product put on the market, dried and cured in the air for 5 minutes at 150 ⁰ C. The comparison product was an acrylic acid ester polymer. which has been esterified by esterification of acrylic acid with perfluorinated alcohol having a carbon number of predominantly 8 to 10 carbon atoms and subsequently polymerized.

The fabrics were tested for their oil repellency according to the AATfX-Tcst: 118 to 1966 T. for their water repellency according to the AATCC spray test: 22-1964 and examined for their grip. The results are summarized in the following table:

GrilT

Rin comparison of the properties of textiles which have been obtained with the polymers of Comparative Examples 1 and 2, with which those obtained by a recognized good commercial product 90
100
100
100

90
100
100
100
100

7th 6 7

6-7
5-6

very soft
very soft
very soft
very soft
very soft
very soft
very soft
very soft
significantly less soft than with
Example 1 and 2

shows that despite the higher content of the solutions in active substance with the same water repellency the oil repellency and the grip are clearly deteriorated.

409539/365

Claims (1)

Claim: Process for the production of organosilicon compounds containing branched perfluoroalkyl radicals by reacting a branched, perfluorinated alcohol or alcoholate with allyl chloride, bromide or iodide and adding an organosilicon compound containing at least one SiH group to the erbal IO ten allyl leaves, characterized that one as branched, perfluorinated alcohol CF ₃ CF ₃