DE2942786A1 - METHOD FOR PRODUCING A POLYDIORGANOSILOXANE - Google Patents

Description

^ 94,786

PFENNING MAAS

MEINIG-Mockery

SCHI EISSHEIMERSTR. 299

tfOOO MUNICH 40

MS-P

Dow Corning Limited, London, England Process for the preparation of a polydiorganosiloxane

The invention relates to organosilicon polymers, to preparations made from such polymers and to the use of these preparations for treating textiles.

From DE-OS 26 21 460, preparations for treating wool in order to make it shrink-proof are known, and these preparations consist of (A) a polydiorganosiloxane mi; terminal radicals OX, in which X is hydrogen, alkyl or alkoxyalkyl, silicon-bonded substituents which contain at least two amino groups and of (B) an organosiloxane with at least three silicon-bonded hydrogen atoms in its molecule are also present in this polydiorganosiloxane. The preferred polydiorganosiloxanes (A) are those obtained by reacting a silanol-terminated polydiorganosiloxane which does not contain any amino-containing substituents of the specified type with a silane of the formula CH ₃ (XO) ₂ SiZ, where Z is a monovalent radical containing at least two amino groups, getting produced. A polydiorganosiloxane of this type, which is described in detail in the above DE-OS

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for example the polydiorganosiloxane, which is obtained by reacting the silanol-terminated polymer with 0.75 percent by weight of the silane. Such a polydiorganosiloxane, when used as a component, gives a corresponding one The shrink-proof preparation gives a satisfactory result, but has the disadvantage that its viscosity increases on storage. This change in viscosity is a very important disadvantage, in particular if the respective polydiorganosiloxane is stored before a corresponding emulsification or want to send.

According to the invention, it has now been found that amino-substituted ones Have polydiorganosiloxanes produced with improved viscosity stability during storage, if the silanes and polydiorganosiloxanes required as reactants are used in certain proportions with one another implements.

The invention accordingly relates to a method for producing a polydiorganosxloxane by

(A) a silanol terminated polydiorganosiloxane having a molecular weight of at least 10,000 in which at least 50% of the total silicon-bonded organic substituents are methyl groups and any remaining organic substituents from monovalent hydrocarbon groups consist of 2 to 20 carbon atoms, and

(B) a silane of the general formula CH, (XO) "SiZ, in which X represents alkyl or alkoxyalkyl with up to 5 carbon atoms and Z is one of carbon, hydrogen, nitrogen and optionally oxygen represents a composite monovalent group containing at least two amino groups and is bonded to silicon via a silicon-carbon bond, reacts with one another,

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which is characterized in that the reaction of components (A) and (B) under a ratio of 1.75 b: s 3.5 moles of component (B) per mole of component (A).

Polydiorganosiloxanes which have a hydroxyl group on each terminal silicon atom and a molecular weight of at least 10,000 are used as component (A) in the preparation of the copolymers according to the invention. At least 50% of the total silicon-bonded substituents in this polydiorganosiloxane should be methyl groups, with the remaining substituents being monovalent hydrocarbon radicals having 2 to 20 carbon atoms, such as ethyl, propyl, 2,4,4-trimethylpentyl, cyclohexyl, vinyl or phenyl. These polydiorganosiloxanes are preferably polydimethylsiloxanes, with polydimethylsiloxanes having molecular weights in the range from 20,000 to 60,000 (namely a kinematic viscosity between approximately 1000 and 10,000 mm ² / s at 25 ^° C.) being most preferred.

In the general formula for the silanes to be used as component (B), X can represent an alkyl group of 1 to 5 carbon atoms or one. Alkoxyalkyl groups with up to 5 carbon atoms, where X is preferably methyl or is ethyl. The group Z can, for example, for

- (CH ₂ J ₃ NHCH ₂ CH ₂ CH (CH ₂ ) ₃ NH ₂ or

- (CH ₂ ) ₃ NH (CH ₂ ) ₂ NHCH ₂ COOCH ₃

but preferably means

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₃₂₂₂ , ₂₄₂ CH ₂ NH ₂ or

(CH ₃ ) CH

The reaction between component (A) and component (F) can be achieved by simply mixing these two ingredients together at room temperature. To accelerate the reaction by heating the respective mixture of components (A) and (B) but preferably Ueter a period of 30 minutes to 3 hours to 6C to 160 ⁰ C. If desired, this reaction a catalyst for the reaction may also be in the presence of of = SiOX groups, but the reaction usually proceeds at a sufficient rate even in the absence of such a catalyst. In general, at least 1.75 moles of silane (B) are reacted per mole of polydiorganosiloxane (A), but the preferred range is 1.5 to 2.5 moles of silane (B) per mole of polydiorganosiloxane (A).

The polymers produced by the process according to the invention can be used in exactly the same way as is apparent from DE-OS 26 21 460, namely for the formation of preparations to: · Treatment of keratin fibers, such as wool, in order to make such fibers shrink-proof. You can according to DE-OS 27 28 597 can also be used for the production of preparations with which cellulose and synthetic fibers, such as nylon, polyester as well as mixtures of polyester and cotton, have it treated in order to prevent the restoration and / or to improve the crease resistance of such fibers.

The invention further relates to a preparation of (i) one; Polydiorganosiloxane and (ii) an organosiloxane with at least three silicon-bonded hydrogen atoms in the Molecule in which the organic substituents are alkyl groups

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with fewer than 19 carbon atoms are the result is characterized in that the polydiorganosiloxane (i) has been prepared by the process according to the invention.

Preparations of the above type can be in the form of solutions in organic solvents or preferably in In the form of aqueous emulsions for the treatment of a wide variety of textiles, these particular desirable ones To give properties. So can with such preparations For example, keratin fibers are treated, especially woolen clothes, in order to give them a significant amount To provide resistance to shrinkage during washing. If you move the preparations from (i) and (ii) also with a siloxane curing catalyst (iii), then this results in preparations, which is particularly suitable for the treatment of cellulose fibers and / or synthetic fibers are suitable to improve their resilience and / or crease resistance. To this end A wide variety of known siloxane curing catalysts can be used, including, for example Acids, bases and organometallic compounds. The preferred catalysts are metal carboxylates such as lead 2-ethylhexoate, Zinc naphthenate, tin (II) octoate, dibutyltin dioctoate, di-n-octyltin diacetate or dibutyltin di (isooctylthioglycollate), Diorganotin alkoxides, such as dibutyltin diethoxide or dioctyltin dimethoxide, and titanium alkoxides, such as butyl titanate, Octylene glycol titanate or triethanolamine titanate. The most preferred catalysts are the organotin compounds.

As component (ii) in the preparations according to the invention organosiloxanes present are generally known materials. You can choose from one or more Organosiloxanes exist that contain at least three silicon-bonded hydrogen atoms in the molecule. they provide are preferably linear siloxane polymers, can be desired

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if necessary, however, also be cyclic or branched. In the Organic substituents present in these organosiloxanes are preferably methyl groups, although others are also present Alkyl radicals with fewer than 19 carbon atoms present such as ethyl or 2,4,4-trimethylpentyl. That Organosiloxane can, for example, also be a copolymer of dimethylsiloxane units and methylhydrogensiloxane units and trimethylsiloxane units, or it is preferably a trimethylsiloxy endblocked polymethylhydrogensiloxane.

The proportions in which components (i) and (ii) are used to produce the preparation according to the invention are not critical. Based on the weight of component (i), up to about 20 percent by weight or more of component (ii) are worked. In general, however, the siloxane (i) is preferably in one Amount of 0.5 to 10 percent by weight, based on the weight of the polydiorganosiloxane (i), used. Contains the preparation according to the invention also has a catalyst as component (iii), then this should preferably be in in an amount of from 0.25 to 10 percent by weight based on the total weight of components (i) and (ii) be.

If the present preparations are used in the form of a solution in an organic solvent, then can for this purpose use as a carrier any suitable volatile solvent such as toluene, xylene, white spirit or Perchlorethylene. All suitable for this purpose can be used to produce aqueous emulsions from the present preparation Use emulsifier. However, nonionic or cationic emulsifiers, such as polyethoxy ethers, are preferred of nonylphenol and octylphenol, trimethylnonyl ethers of polyethylene glycols, monoesters of alcohols and fatty acids such as glycerol monostearate or ethoxylated amines.

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The preparations according to the invention can be applied to appropriate textiles by customary techniques, such as padding, dipping or spraying. The drying of the treated fibers and curing the applied Siloxanzubereitung can under normal ambient temperatures, namely temperatures of about 15 to 25 ⁰ C, over periods of up to 4 days or carried out over it. In general, however, the drying and / or hardening process is accelerated by bringing the treated fibers to an elevated temperature for this purpose, preferably to a temperature of 50 to 170 ^° C.

The invention is further illustrated below with the aid of examples. Understand all of the information contained therein in weight information.

example 1

In a flask equipped with a stirrer and nitrogen purge mix the silane of the formula

CH ₃ (CH ₃ O) ₂ Si (CH ₂ ) ₃ NHCH ₂ CH ₂ NH ₂

(14 parts) (2 mol) and a polydimethylsiloxane (1000 parts) (1 mol), which has a hydroxyl group on each terminal silicon atom and has a viscosity of about 4500 mm ² / s at 25 ^° C. (molecular weight about 46,000) together. The reaction mixture is then heated for 1.5 hours I35 ⁰ C with stirring and under nitrogen atmosphere. The resulting siloxane polymer (polymer A) has a kinematic viscosity of about 6500 mm ² / s at 25 ° C.

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Part of this polymer is kept at 22 ^° C. and its viscosity is measured periodically over a period of 6 months.

For comparison, similar viscosity measurements are also carried out on the basis of a siloxane polymer (polymer B) which is prepared in the same way as above, but with an amount of siloxane of 1.25 mol per mol of the polydimethylsiloxane. The polymer obtained in this way has an initial viscosity of about 7000 mm ² / s at 25 ^° C.

The results obtained in the above tests are shown in Table I below.

Tabel

Siloxane A.
B. Beginning viscosity (at 25 ⁰ C) 6 months 6500
7000 2 months 4 months 20,000
52,000 Polymer
polymer 9000
13,000 13,000
29,000

May gives Polymer A (33.3 parts) immediately after its manufacture ! ling and, before appropriate storage, gradually turning into a mixture of 3.33 parts of a non-ionic emulsifying agent (Tergitol TMN-6) and from water (7.30 parts). The resulting mixture is stirred for 1 hour by a Ko loidmühle sent and then verdüj with water (56.0 parts) to form an aqueous emulsion (Emulsion X) nt.

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Using a similar procedure, an aqueous emulsion (Emulsion Y) from a trxmethylsiloxyendblockxerten polymethylhydrogensiloxane (viscosity 30 mm ² / s at 25 ⁰ C) was prepared from 33.3 parts of the siloxane, 0.86 parts of an ethoxylated fatty amine as an emulsifier, 1, 65 parts of a nonionic emulsifier (Tergitol TMN) and 63.5 parts of water.

The emulsion X (4.6 parts) and the emulsion Y (0.06 part) are then mixed with 2040 parts of water in which 10.2 parts of sodium sulfate and 1.0 part of 50 percent aqueous acetic acid are dissolved. A piece of Botany wool fabric (60 g) is then dipped into the mixture obtained, the temperature of the mixture is increased to 40 ^° C. and the wool is moved in it. After about 30 minutes the liquid mixture has become clear, indicating that the siloxane has settled on the fabric. The tissue is therefore removed from the liquid mixture, ^{dried for about 6 minutes at 80 °} C. and then exposed to the surrounding atmosphere (60% RH, 20 ^° C.) for 3 days.

The wool sample treated in the above manner is then examined for its shrinkage resistance by the method of International Woool Secretariat, Specification WSS 128, test method 185 using a wash time of 1 hour. This results in a shrinkage of the wool sample only 0.3%.

Example 2

Using the emulsion X and the emulsion Y, each prepared according to Example 1, the treatment is carried out in the following manner Nylon fabric. Emulsion X (3 parts), Emulsion Y (0.5 part), a 20 percent strength by weight aqueous emulsion of

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Dibutyltin di (isooctyl thioglycollate) (0.1 part) and a aqueous solution (0.1 parts) containing triethanolamine titanate Contains (50 percent by weight) and zinc acetate (11 percent by weight), separated into 2000 parts of water with stirring.

In the above-obtained aqueous mixture then is immersed a piece of nylon fabric (100 g), keeping the mixture to a 25 ⁰ C. After a treatment time of about 30 minutes, the treatment liquid has become clear, which shows that the siloxane has settled on the fabric. The fabric is therefore removed from the treatment bath, ^{dried at 100 °} C. and finally placed in an oven heated ^{to 150 ° C. for 3 minutes to harden the siloxane.} The treated fabric is then examined by the method of British Standard Specification 3086 for its crease recovery angle, which gives a value of 156 °. The corresponding value for the untreated fabric is 110 °.

Example 3

According to the method described in Example 1, the silane CH ₃ (CH ₃ O) ₂ Si (CH ₃ ) ₃ NHCH ₂ CH ₂ NH ₂ (15.4 parts) (2.2 mol) is reacted with a silanol-terminated polydimethylsiloxane which has a viscosity of about 4000 mm ² / s at 25 ^° C. In this manner is obtained as the product of a siloxane polymer (polymer C) having a kinematic viscosity of 6450 mm ² / s at 25 ⁰ C.

The above polymer is stored in a sealed container at normal ambient temperature and over a period of time examined for its viscosity at certain intervals over a period of several months.

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For comparison purposes, corresponding viscosity measurements are also made on a siloxane polymer (polymer D), which has been prepared by an identical process, but using 1.25 moles of silane per mole Polydimethylsiloxane.

The results obtained in the above tests are shown in Table II below.

Table II

Siloxane viscosity (at 25 ⁰ C)

Start 2 months 5 months

Polymer C 6450 8200 11 500

Polymer D 7600 19 800 41 400

Example 4

To prepare a siloxane polymer, proceed as described in Example 1, increasing the amount of silane but from 14 to 21 parts.

8.7 parts of the siloxane polymer obtained and 0.11 part of a trimethylsiloxy-endblocked methylhydrogen polysiloxane are dissolved in 750 parts of perchlorethylene and the resulting solution is then used to treat specimens of a knitted Shetland wool fabric (coverage factor 0.85) by padding, the siloxane absorption being 3 percent by weight based on the weight of the wool. The wool thus obtained pieces are then dried at 80 ⁰ C, heated 15 minutes at 80 ⁰ C for curing of the siloxane and finally removed 3 days prior to their examination.

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The samples obtained are then examined with regard to their shrinkage during washing according to that in Example 1 described .Verfahren, whereby after a washing time of 1 hour a value of -1.2% and after a Washing time of 3 hours gives a value of -0.5%.

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Claims (7)

Claims 1. Process for the production of a polydiorganosiloxane, by (A) a silanol terminated polydiorganosiloxane having a molecular weight of at least 10,000 in which at least 50% of the total silicon-bonded organic substituents are methyl groups and any remaining organic substituents from monovalent hydrocarbon groups consist of 2 to 20 carbon atoms, and (B) a silane of the general formula CH ₃ (XO) -SiZ, where X is alkyl or alkoxyalkyl with up to 5 carbon atoms and Z is a monovalent group composed of carbon, hydrogen, nitrogen and optionally oxygen which contains at least two amino groups and is bonded to silicon via a silicon-carbon bond, reacts with one another, characterized in that the reaction of components (A) and (B) under a ratio from 1.75 to 3.5 moles of component (B) per mole of component (A). 2. The method according to claim 1, characterized in that the polydiorganol siloxane (A) has a molecular weight in the range of 20,000 to 60,000. 3. Preparation of (i) a polydiorganosiloxane and (ii) an organosiloxane with at least three silicon-bonded Hydrogen atoms in the molecule in which the organic 030021 / 06U ORIGINAL INSPECTED Substituent alkyl groups with fewer than 19 carbon atoms are, characterized in that the polydiorganosiloxane (i) by the method of Claim 1 and / or 2 has been produced. 4. Preparation according to claim 3, characterized characterized in that it is in the form of an aqueous emulsion. 5. Preparation according to claim 3 or 4, since - characterized in that it also contains a SxloxanhSrtungskatalysator. 6. Method of treating textiles by Application of a siloxane additive to the respective textile and subsequent hardening of the applied SiIoxane, characterized in that a preparation according to claim is used as the siloxane additive 3 to 5 used. 7. Siloxane-treated textiles, characterized in that they are after the process of claim 6 have been dealt with. 0021 / 06U