DE1642977C - Process for making fiber materials water repellent - Google Patents

Description

3 4

moderately, in the case of the reaction products from titanium tinue devices which are used for the treatment of

alcoholates lower quantities and in the case of bulk goods with organic solutions according to the

Settlement products made from zirconium and aluminum foulard principle are suitable. But also the

alcoholates larger amounts of metal soaps in chemical cleaning for re-impregnation

set. 5 are machines used by clothing

The manufacture of those used according to the invention can be used. Treatment can eventually too

Silicone hardener is achieved by simply spraying the liquor on for 5 to 20 minutes,
term heating of the three starting components on

Reflux condenser. The reaction product obtained, Example 1

is then expediently with the same weight io 200 g of a 50% solution of zirconium tetra-

amount of a (chlorinated hydrocarbon, such as n-propylate in n-propanol, 60 g paraformaldehyde and

Tetrachlorethylene, diluted and cooled. Equal to 15 g of tin octoate are stirred for 10 minutes

good products are obtained if only the metal reflux condenser is heated to the boil and with 75 g

alcoholate and paraformaldehyde on the reflux tetrachlorethylene to a storage-stable, clear

cooler heat! are then diluted the metal soap 15 50% solution and cooled,

is added and then stirred for so long. 15 g of this product and 25 g of hydrogen poly-

until a clear or opalescent solution is obtained, siloxane (»72ο · c = 20 to 30 cP; S ₂₀ -c = 0.99 to 1.01)

which are then also useful with tetrachlorethylene are stable with tetrachlorethylene to 1 liter

and the like is diluted and cooled. Also the un- fleet was replenished. With this solution a cotton

diluted reaction products are stable and »o tissue (square meter weight: 160 g) padded to 100%

useful. A dilution of the same is, however, squeezed off, dried ^{at 100 ° C. for 15 minutes and}

better handling is advantageous, especially if ^{condenses at 140 °} C. for 5 minutes. The thus obtained

the pure alcoholates are assumed. Tissue shows up after 10 minutes of sprinkling

When using 5 to 25 g / l of the federal man, a water absorption of only 50% catalyst solution together with 20 to 25 14% and a still very good beading effect. Use 40 g / l organopolysiloxane (100%) in gasoline or, instead of the hydrogen polysiloxane, use a dissolved, padded chlorinated hydrocarbon. Mixture of equal parts of hydrogen polysiloxane to 80 to 120%, then 10 to 20 mi and methyl polysiloxane, then equally good results are dried at 100 ° C. and 5 minutes at nisse. When using pure methyl-140 ⁰ C condenses. The result is excellent water-polysiloxane, on the other hand, the results obtained are fabric repellent, with practically no yellowing, which is somewhat worse.

The organopolysiloxanes are hydrogen B ers ρ 1 w 1 2
polysiloxanes and mixtures thereof with methyl 200 g of a 50% solution of zirconium tetrapolysiloxanes are particularly useful. Less than 35 n-propylate in tetrachlorethylene, 30 g of paraformaldehyde are pure methylpolysiloxanes. and 20 g of zinc octoate are heated to boiling with stirring, 10 ml examples for suitable, completely etherified Alnuts on the reflux condenser and then alcoholates, which are also partially polymerized, are cooled. Both the solution obtained and the can, are those of zirconium and titanium. Finishing fluids produced with them are khre, η - propanol, iso - propanol, η - butanediol, iso-durable solutions.

Butanol, η - amyl alcohol, propanediol - (1.2), Bu- 15 g of this reaction product and 25 g of a tanediol (1,4) or butanediol (1,3), glycol monobutyl copolymer of dimethylsiloxane and water ether, glycol monohexyl ether or the Alcoholates of the substance methylsiloxane 4: 1 (»720 ° c about 100 cP; S2o · c about aluminum with propanediol (1,2), butanediol (1,4), 0.98) are mixed with methylene chloride to 1 liter of a glycol monobutyl ether, 2 - methylpentanediol - (2,4) 45 stable liquor made up. With this solution and propylene glycol n-butyl ether. Especially good overall a Baumwollpopelinegewebe (sqm weight about 180 g) is the alcoholates of zirconium and titanium are padded, squeezed to 90%, for 10 minutes at low, aliphatic, saturated alcohols and the 90 ⁰ C and dried for 5 minutes at 14O ⁰ C condensate alcoholates of aluminum with dihydric alcohols. The fabric obtained in this way shows a water uptake of 6 to 8 per group of monoalkyl ethers of only 15.5% and excellent carbon atoms in the 10-Mi- or monoalkyl ethers of these bivalent alcohols, 5 ° groove sprinkling according to Bundesmann. Mixtures of such metal beading effects,
alcoholates are useful. Example 3

The organically soluble metal soaps used

derive from fatty acids with 6 to 18 carbon atoms and 55 150 g of a 50% solution of zirconium tetra-

2-, 3- or 4-valent metals. Examples of such n-propylate in n-propanol, 30 g paraformaldehyde,

Metal soaps are: aluminum, barium, magne- 30 g aluminum tristearate and 60 g butyl acetate as

sium, lead, tin, zinc octoate, barium, calcium, solubilizer for the metal soap used

Manganoleate, calcium, zinc laurate and aluminum are refluxed for 10 minutes with stirring

Magnesium, tin, titanium and zinc stearate. 60 heated to the boil and then immediately cooled,

are the metal soaps of magnesium, tin, titanium The practically clear solution obtained is a good one

and zinc most suitable. '' Curing catalyst for organopolysiloxanes.

With the Im- 20 g of this reaction product and 35 g of one prepared as described above

Tissues made of cellulose or copolymers of dimethylsiloxane and methyl-

Segenerat cellulose fibers and mixed fabrics, especially 65 hydrogen siloxane 6: 1 (»720 · c about 4OcP; S2o« c about

Cotton-polyester blended fabrics, water-repellent made of 0.98) are mixed with white spirit (boiling range 120 to

be prepared. 16O ⁰ C) made up to 1 liter of a stable liquor. With

The equipment used for the application is the condensation of this liquor is a cotton-polyester blend

5 6

35/65 soaked, drained to 85% liquor pick-up. The fabric treated in this way shows a slight

squeezed, dried, and 4 minutes at 150 ⁰ C con- water absorption and a good water-repellent effect of the büi

condensed. The fabric treated in this way shows only slight 10-minute sprinkling according to Bundesmarn.

Water absorption and good beading effect with the 10- B ice ο ⁵ e 1 7

Minute sprinkling according to Bundesmann. 5 ^v '

95 g of 100% titanium tetra-n-propylate, 70 g of ParaExample 4 formaldehyde and 10 g magnesium octoate are used

150 g of a 50%. Solution of zirconium tetra-n-pro with stirring for 10 minutes on the reflux condenser for

pylate in n-propanol. 45 g of paraformaldehyde and 70 g of boiling heated and the resulting solution with perchloric

Titanium tetrastearate is diluted to 50% in ethylene for 10 minutes while stirring. A catalyst is obtained

The reflux condenser is heated to the boil, then 115 g of tetra- tor with similar properties as in the previous ones

chlorethylene added and cooled. The examples described are obtained.

a good, stable curing catalyst, which is the same material as in Example 6 in the

treated together with organopolysiloxanes in gasoline or in the same manner as described there, wherein

to clarify chlorinated hydrocarbons, but durable 15 according to this ice cream: 1 produced hardening

Can be diluted impregnation liquor. · Catalyst is used, one also obtains

17 g of this reaction product and 30 g of water - an extremely water-repellent fabric polysiloxane (7/20 ¹ C = 20 to 30 cP; S2o »c = 0.99 fabric.

up to 1.01) with tetrachlorethylene to 1 liter of an example 8

stable fleet replenished. Will this fleet be an ao

Cell wool (m2 weight approx. 186 g) corresponding to 95 g of 100% titanium tetra-n-propylate and 60 g of parades Treated details in Example 1, the formaldehyde is 10 minutes with stirring on tissue obtained a low water absorption and reflux condenser heated to 95 ° C, then 40 g of titanium very good beading effect. tetrastearate added, stirring continued until clear . . . »5 solution has formed, diluted with tetrachlorethylene to 50% b e 1 s ρ 1 e 1 3 and cooled. The catalyst obtained

! 50 g of a 50% solution of zirconium tetra solution has similar properties to the previously used

wrote n-propylate in n-propanol and 15 g paraformaldehyde.

15 g of this reaction product and 25 g of the im

heats, then added 20 g of zinc laurate, 5 minutes further 3 ° Example 2 used composite polymer from di-

stirred until an almost clear solution is formed, with methyl and ^{water r} stoffmethylsiloxan be with

35 g of tatrachlorethylene diluted and then cooled. White spirit (boiling range 120 to 16O ⁰ C) to 1 liter

The catalyst solution obtained has similar properties to a stable liquor. Will with this fleet

shafts like those previously described. a cotton fabric (square meter weight 160 g) accordingly

20 g of this reaction product and 25 g of water - the information in Example 1 (liquor uptake only material polysiloxane (data see Example 1) are treated with 90%), the fabric obtained has 1 liter of a stable liquor in the case of tetrachlorethylene. Filled minute sprinkling according to Bundesmann. With this liquor, a cellulose fabric with a water absorption of only 16% and a very (square meter weight approx. 151 g) is foulaid on a liquor-good beading effect.
uptake of 100% squeezed, 15 minutes at 40.
100 ° C and finally 3 minutes in Example 9
150 ⁰ C condensed. The fabric obtained in this way shows 123 g of pure aluminum triisobulylate and 220 g of the Bundesmann's 10-minute rate until a clear effect. 45 solution has arisen. After cooling down

Example ⁶ ^ 0 S Paraformaldehyde and 35 g zinc octoate added

and with stirring for 10 minutes on the reflux condenser

95 g of 100% titanium tetra-n-propylate, 40 g of para-100 ^° C. heated. A roughly 25% clear solution is obtained

formaldehyde and 30 g lead octoate are used directly as a curing catalyst under solution

ER- stirring 10 minutes to the reflux condenser to 100 ⁰ C can be fiftieth

heats and tetrachlorethylene to a 50% solution of 30 g of this reaction product and 25 g of dimethyl solution diluted, which have similar properties as the prepolysiloxane (data see example 6) are made with Tetraher has described. Chlorethylene made up to 1 liter of a stable liquor.

20 g of this reaction product and 20 g of prostitute with this liquor is a polyester / cotton fabric

thylpolysiloxane (7720 ° c = 750 cSt, S ₂ JC = 0.97) 55 65/35 (qm-weight 133 g) are padded to about 120%

squeezed off with tetrachlorethylene to 1 liter of a stable liquor and dried in the usual way

filled up. With this liquor a cotton poly and condensation is completed. The one so equipped

amid mixed fabric 80/20 (m2 weight 112 g) soaked, fabric shows up after 10 minutes of sprinkling

Squeezed to 100% Flottenauuiahme, 15 minutes federal man a water absorption of only

dried at 100 ⁰ C and 5 minutes at 140 ⁰ C con- 60 12% and a good beading effect.

Claims (3)

of fiber materials by impregnation with organic patent claims: polysiloxanes and curing catalysts in organic solution, drying and curing, found that 1. Process for making fibers water-repellent - does not have the deficiencies listed above and that materials by impregnation with organopoly 5 is characterized in that one is used as hardening siloxanes and curing catalysts used in organic catalysts, the solution, drying and hardening, characterized by heating alcoholates of titanium, aluminum, that one as hardening miniums or zirconium with saturated, aliphatic Catalysts reaction products used, the monohydric or dihydric alcohols with 2 to 6 carbon through Heating of alcoholates of titanium, aluminum atoms or monoalkyl ethers of these bivalent ones miniums or zircon with saturated, aliphatic alcohols, each monoalkyl ether group ins-1- or bivalent alcohols with 2 to 6 carbons - has a total of 4 to "8 carbon atoms, with para - Substance atoms or with monoalkyl ethers this 2wer- formaldehyde at reflux, with alcohols prior to heating, with each monoalkyl ether group or subsequently organically soluble metal soaps having a total of 4 to 8 carbon atoms, with »5 fatty acids with 6 to 18 carbon atoms and 2-, 3- Paraformaldehyde at reflux, whereby before the er- or tetravalent metals are added, with heating or then organically soluble metal at least 1 valence of the metal by fatty acids metal soaps from fatty acids with 6 to 18 carbon bonds and the molar ratio / on alcoholate to atoms and 2-, 3- or 4-valent metals added paraformaldehyde to metal soap 1: 1: 0.06 to 1:10: 1, with at least 1 valence of the Me- ao, have been produced. When organically soluble tails are bound by fatty acids and the molar metal soap is preferably used, the ratio of alcoholate to paraformaldehyde in which all valences of the metal due to fatty acids metal soap is 1: 1: 0.06 to 1: 10: 1 are used. are bound
have been asked. The hardening catalysts used according to the invention 2. The method as claimed in claim 1, characterized in that they are produced by simple heating draws that zirconium tetra-n-propylate and para is possible on the reflux condenser, are characterized by formaldehyde heats up and metal octoates at the same time - excellent storage stability, and also those at the same time or added afterwards. organic im- 3. The method according to claim 1, characterized in that the impregnation liquors are stable for several days, d. h., it shows that organically soluble metal soaps do not decompose when exposed to moisture in which all valences of the metal separate from basic salts. It is with the are bound by fatty acids. products used according to the invention so the It is not necessary to add a complexing agent, as the products themselves result in stable liquors. From it 35 it follows that the inventively used Products have a completely different constitution than the known ones, due to the conversion of carbon It is known that titanium alcoholates, especially those acidic and metal alcoholates obtainable from monovalent, aliphatic, saturated alkoxides, 40 according to the products used, are derived from monovalent, aliphatic, saturated products that are used to react with paraformaldehyde and to use the products obtained with the impregnation liquors of organopolysiloxanes as silicone curing agents. and the hardening used according to the invention. The reaction with 1 to 7 moles of paraform catalysts takes place very good hydrophobic effects without aldehyde per mole of titanium alcoholate at temperatures of significant yellowing of the fabric,
about 85 to 115 ° C, so that the resulting easily distilled off volatile components against stabilization with desmotropic. The reaction solvents result in the products used according to the invention then, together with siloxanes, become substantially more stable liquors. In the case of preferably organic methylpolysiloxanes for use on textiles, solutions are used for leather treatment. These hydro-impregnating liquors, which are very good together with organopolysiloxanes, are, however, not very stable in storage. Furthermore, there is a tendency for deposits to occur, and when the solutions are used the greater resistance of the solutions to the finishing of fabrics results in a clearly and consistently stain-free finish, as occurs with a sta yellowing. bilization with desmotropic solvents is not It is also known that dry water repellency is guaranteed. It also instructs the application medium, i.e. those which, in organic solution, are the most important of desmotropic solvents be used by converting aluminum to the disadvantage that by the technical pro-alcoholates with low and high aliphatic ducts unavoidable traces of iron a red carboxylic acids to manufacture. This carboxylic acid aluminum coloration of the products by the formation of iron complexes However, minium alcoholates are already present in traces. decomposed by moisture. It is therefore in the tech- 60 The molar ratios for the invention to yer · Niche use of the same or their solutions will curing catalysts can be used in a wide range «It is necessary to vary the shelf life immediately after the limit. This is how you get a mole position by adding a complex-forming curse ratio of metal alcoholate to paraformaldehyde term organic compound, such as acetylacetone, to metal soap of 1: 1: 0.06 good catalysts, Acetoacetic ester among other things against the humidity 65 and still with reaction products with a MoI-zu Stabilize, which through the textile material in the ratio of 1: 10: 1 become usable Kataly-Liquor is introduced. get 'sators. Preferred is a molar ratio of A method of hydrophobing 1: 3: 0.06 to 1: 8: 0.5 was now used. In general it is useful