DE2062816A1 - Perfluoralkylated organosilicon cpds - used as oil and water repellent finishes for textiles - Google Patents

Abstract

Alcohols or alcoholates of formula F-C(CF3)2-C(CF3)2- OM (where M is H or alkali metal) are reacted with allyl chloride, -bromide or -iodide to form an allyl ether on to which an organosilicon cpd. contg. >=1 SiH-gp. is added to form branched perfluoalkyl gp.-contg. organosilicon cpds., useful as oil- and water-repellent finishes for natural and synthetic textiles, paper, leather and other fibre materials. Finishes also impart soft handle and resist hydrolysis, repeated washing and dry-cleaning.

Description

Process for the preparation of branched perfluoroalkyl radicals containing Organosilicon Compounds The invention relates to a process for the preparation of organosilicon compounds containing branched perfluoroalkyl radicals 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.

U.S. Patent 3,331,813 teaches the preparation of fluorine-containing organosilicon compounds of the formula In this formula, X and X 'are each a halogen radical, Y is a halogen radical, an alkoxy or an aroxy group, R is a hydrogen radical or a monovalent hydrocarbon group which can optionally be halogenated, m is 2 or 3, n is 1 or 2 , p is 1, 2 or 3, q is 0, 1 or 2, and the sum of n, p and q is 4.

The aforementioned US patent also describes polymeric organosilicon compounds which can be obtained by using compounds of the general formula which contain two or dYei hydrolyzable groups, optionally hydrolyzed and condensed together with other hydrolyzable organosilicon compounds.

Depending on the functionality, the resulting polymer molecule contains the organosilicon starting compounds mono-, di- and optionally trifunctional Silicon units.

The structural unit with a difunctional silicon atom has the following formula Similarly, the structural unit with a trifunctional silicon atom can be represented as follows: The following formula can be used as a general formula for a polymer which is built up from different functional silicon units are considered representative. In this formula, an average value of 0 to 1, b has an average value of 1 to 1.5, c has an average value of 1 to 2, where the sum of at2bec = 4.

The above-mentioned US Pat. No. 3,331,813 can also be found that the monomeric and polymeric fluoroalkyl radicals containing organosilicon Compounds applied to fibrous materials, these good oleophobicity, connected with good hydrophobicity. This is sufficient for many applications Compounds achieved combination of oleophobicity and hydrophobicity. Sometimes is however, it is desirable to achieve an even higher degree of oleophobicity. This is an object of the present invention.

The laid-open specification 1 568 600 describes a process for the preparation of perfluorinated, tertiary alcohols of the general formula known, in which Rf1 and Rf2 are perfluorinated alkyl radicals having 1 to 3 carbon atoms. According to this procedure, perfluorinated ketones of the general formula are used where Rf1 and Rf2 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 CF3 - CF = CF2 is further reacted and the compound obtained is hydrolyzed.

The laid-open specification 1 595 696 describes a process in which compounds of the formula goes out and this reacts with an acrylic acid halide.

The compounds produced in this way should -si-ch compared to the known Equipment is primarily characterized by an improved oil repellant effect. The compounds also have a higher level than the known products Softening point. However, a disadvantage of these compounds is their susceptibility to hydrolysis. In addition, they impart an undesirable appearance to the fibrous substrates treated with them hard grip.

Another object of the present invention is therefore to Find organosilicon compounds containing fluorine, which at excellent The hydrophobicity and oleophobicity of the textiles finished with them simultaneously give a soft feel and in the interest of the durability of the equipment are stable to hydrolysis.

Surprisingly, it has now been found that certain organosilicon compounds containing branched perfluoroalkyl radicals meet these requirements. The present invention therefore relates to a 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 allyl ether obtained and is thereby characterized in that the branched, perfluorinated alcohol is a compound of the general formula wherein M is hydrogen or alkali is used.

The process essentially takes place in two stages. First, the branched, perfluorinated alcohol or the alcoholate of the formula with allyl halide, with the exception of allyl fluoride, reacted in a manner known per se. In a second process step, the allyl ether obtained is reacted with an organosilicon compound which has 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 HSiCl3, CH3HSiCl2, H2S iCl2. Examples of polymeric siloxanes which contain one or more SiH groups are n = 2 to 200, preferably> 30 R = ¢ CH3) 3Si, alkyl with 1 to 3 carbon atoms H, R '= CH3 or H, a = 1 to 100, b = 0 to 10 and compounds with the overall composition or with units of the formula The treatment of the fibrous substrates can be carried out both with the monomeric and with the polymeric organosilicon compounds.

The monomeric compounds can be in the form of vapors, in the form of more pure Liquids or from solution in an inert volatile solvent the fiber material are applied. Instead of the am To provide chlorine atoms bonded to silicon atoms in a manner known per se. This avoids acid loading of the tissue. When applying the monomers The binding to the fiber material takes place through the conversion of the reactive Groups of the monomer with the reactive sites in the fibers. One can go further assume that at the same time the polymerization of the monomer in situ on the Fibers enters, and that such polymerization due to the moisture that naturally present in all fiber materials, 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 1600C. To speed up the hardening, one of the known curing catalysts, e.g.

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.

When using the polymeric compounds, the polymer is usually in an inert, volatile solvent such as (trifluoromethyl) benzene, 1,3-bis-trifluoromethylbenzene or trichlorotrifluoroethane, dissolved. The resulting solution is on the fiber material applied by means of known dipping or padding methods. By varying the concentration of the polymer in the solution and the degree of blocking can be the amount of polymer, deposited on the material can be varied. Typically, the Amount of polymer 0.1 to 20% by weight, based on the weight of the fiber material, be. Usually when treating textiles, such as fabrics, the Amount of polymer limited to 0.1 to 5% by weight in order to achieve the desired properties and at the same time to maintain the soft feel of the textile. It is it is also possible to apply the polymers to the tasermaterlal in the form of an aqueous emulsion to raise. It also expediently closes after the polymers have been applied a curing treatment using the catalysts described above. The polymeric compounds can be formed by adding the allyl ethers to polymers SiH connections or ~ also obtained by hydrolysis condensation of the monomeric addition compounds will. In such a hydrolysis condensation, other monomeric silanes can be used To increase the degree of crosslinking or degree of polymerization or to improve it added to the reactivity of the polymeric materials with fibrous substrates. Examples of such silanes are SiC14, HSiC13, with HSiC13 being preferred because SiH atoms remain in the hydrolysis condensate, which increases the ability of the fiber to be absorbed to enhance. This hydrolysis condensation is preferably carried out in fluorinated solvents, such as trifluorotrichloroethane carried out. The silanes used for hydrolysis, such as SiC14 or HSiC13, should be in at most equimolar amounts, preferably half-squimolar amounts Quantities, are used.

A variety of materials are suitable as fibrous substrates, such as paper; Cotton; Linen; Hemp; Jute; Ramie; Sisal; Cellulose acetate rayon; Cellulose acetate / butyrate rayon; saponified acetate rayon; Viscose rayon; Copper arumonium rayon; Ethyl cellulose; from amylose, algins or pectins manufactured fibers; Wool; Silk; animal hair; Mohair; Leather; Furs; from casein, Soybean peanut proteins, zein, gluten, egg albumin, collagen or keratins manufactured fibers; Polyamide fibers, polyurethane fibers, polyester fibers such as polyethylene terephthalate; Fibers based on polyacrylonitrile; or fibers of inorganic origin, such as asbestos or Glass fibers, etc. The invention can be applied to textile materials which present in the form of loose fibers, threads, yarns, twisted threads, slivers, fiber bundles, Trims, cords, ribbons, woven or knitted fabrics, felts and other non-woven fabrics Nonwovens, articles of clothing or parts thereof.

Fiber materials made with the compounds produced according to the invention have been treated have an increased 51 and water repellency. Of particular importance is the equipment's resistance to repetition Washing or dry cleaning. It is also important that the reinforcement of the b-repellency without impairing the other properties of the textile material is achieved. Indeed, the handle of the treated textile material becomes insofar improved as it becomes softer and more pliable.

The following examples are intended to explain the process according to the invention and the properties of the products according to the invention in more detail: Example 1 374 g (1 m) potassium perfluoro-2,3-dimethyl butanolate (2) (prepared analogously to laid-open specification 1 568 600, Example 1) are stirred into 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. with stirring, during which potassium chloride separates out. After 24 hours of reaction, the potassium chloride is filtered off and the filter cake is washed with dimethyl diglycol.

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

The allyl ether is then treated with sodium hydride to make it to remove residues of the starting alcohol.

The rPefluoro-2,3-dimethyl-butyl- (2> 1-allyl ether showed the iodine number: practical: 66.0 theoretical: 67.5 Example 2 188 g -t0.5 m) des Allyl ethers prepared in Example 1 are mixed with 67.7 g (0.5 m) HSiCl3.

This mixture becomes a solution heated to 1000C with stirring of 90 mg (180 mg / eq SiH) pyridine- (ethylene) -PtC12 in 100 ml dried toluene dripped. The temperature should not drop below 900C. The dropping speed depends on the reflux that occurs.

After the end of the dropwise addition, the mixture is left for more React for 12 hours under reflux conditions. After that, the volatile components distilled off up to a bottom temperature of 1700C.

The residue has a chlorine content of 20.43%.

Theory: 20.75% C1.

Example 3 64.05 g (s 1 mol SiH) of a siloxane of the formula are mixed with 200 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) PtCl2 in 200 ml of dried toluene.

The temperature must not drop below 95 ° C. After adding the reaction mixture is allowed to react for a further 12 hours at 100.degree. The one from toluene The residue freed in vacuo has an SiH value of 0.82%. Theory: 0.78%.

Example 4 51.15 g 10.1 m) of the y [perfluoro- (1,1,2-trimethylpropoxy-)] propyltrichlorosilane prepared in Example 2 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 from 55 to 60 minutes in a solution of 27.8 g NaHC03 (0.3 m + 10% excess) dropped into 300 ml of water. After the dropwise addition, it is immediately diluted with 150 ml of ether. The organic phase is washed with water until the reaction is neutral, over sodium sulfate dried and the ether was distilled off in vacuo.

Example 5 102.3 g (0.2 m) γ [perfluoro (1,1,2-trimethylpropoxy -)] propyltrichlorosilane and 13.5 g (0.1 m) SiHC13 are in 100 ml of dried toluene and 300 ml of dried Dissolved 1,1, 2-trifluorotrichloroethane.

While stirring vigorously, this solution becomes a mixture of 74 g of NaHCO3 (0.8 m + io e excess) in 600 ml of water, 250 ml of toluene and 100 ml of 1,1,2-trifluorotrichloroethane added dropwise within 3 hours; After completion of the m dropping, immediately add 200 ml diluted ether, the organic phase washed several times with water over sodium sulfate dried and the ether is distilled off in vacuo.

Example 6 The hydrolysis condensates of Examples 5 and 6 are with 1,1,2-trifluorotrichloroethane diluted, so that 0.5 or 1% solutions are formed. Cotton poplins are soaked in these solutions by immersing them for 10 minutes.

After drying in air for 24 hours, curing is carried out at 150 ° C. for 5 minutes.

Analog impregnation solutions with an addition of 15% Zr-tOBu) 4, based on on the hydrolysis condensate used were also produced.

The fabrics were examined for their oil repellency according to the AATCC test: 118-1966 T, for their water repellency according to the AATCC spray test: 22-1964 and for their feel. The results are summarized in the following table: Product content d. Zircon, water, oil, handle Solution butoxide differ- Solution sung Example 4 0.5 - 90 7 very soft Example 4 0.5 + 100 7 very soft Example 4 1.0-100 7 very soft Example 4 1.0 + 100 6 - 7 very soft Example 5 0.5 - 90 7 very soft Example 5 0.5 + 100 7 very soft Example 5 1.0-100 7 very soft Example 5 1.0 + 100 6 - 7 very soft

Claims (1)

A process for the preparation of branched organosilicon compounds containing perfluoroalkyl radicals by reacting a branched, perfluorinated alcohol or alcoholate with allyl chloride, bromide or iodide and addition of an organosilicon compound containing at least one SiH group to the allyl ether obtained, characterized in that one is called branched , perfluorinated alcohol a compound of the general formula wherein M is hydrogen or alkali is used.