DE2004676A1 - Process for the preparation of a detergent - Google Patents

Description

Badische Anilin- & Soda-Fabrik AG

Our reference: O.Z. 26 594 Rt / Wnz 6700 Ludwigshafen, February 2, 1970

Method of making a sizing agent

In the textile industry it is customary to contain yarns, and in particular warp yarns, made of cotton or other cellulose fibers To treat staple fiber yarns with hot, i.e. almost boiling, aqueous preparations of corn or potato starch, before they are processed on the loom. This yarn pretreatment, which is known in technical terms as sizing, is made to glue the webs in itself and to increase their mechanical resistance, so that they withstand the high stresses of the weaving process better than in the raw and untreated state. Except the natural ones Plant starches are also chemically modified starch products used for sizing cotton that are lighter are digested than the usual starches and result in liquors with a relatively low viscosity. As additives to size liquors, the main component of which is starch especially fats such as beef tallow are used. The aim is to improve the sliding properties of the threads by adding Pett and avoid excessive embrittlement. Before the further finishing processes, these finishing agents must be in general again to be removed from the tissues, what only (Thanks to the action of enzyme-based auxiliaries for several hours, the results are reasonably satisfactory.

Cotton is sporadic; the other delluloaefauergarne .-jach with »'lUntnuzen, - ^ Mch i i ■ · h t; e t,' lie by chemical modification '/ on Ceiiuloüö be won. This subheading belongs OeLLulo ;; rather, such as O-irboxymethylcel 1 uLose or MethylcelLulone. These; 5ubn dance, are ιιη, -ϊ ntens in the form of powders the market, which "I only stand in water for a long time, can be converted into colloidal aqueous solutions by vigorous stirring or kneading, or by heating. These solutions

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are generally not homogeneous, but rather cloudy and proportionate highly viscous. Often these powders also contain larger ones due to the chemical reaction on the cellulose Quantities of table salt. However, as is well known, a salt content of the size easily leads to corrosion of the metal parts of the weaving harness. Products based on carboxymethyl cellulose also usually have to be brought to the thread from a hot liquor which, in addition to high steam consumption, also causes some damage to the yarns (loss of elasticity) Has. By sizing with cellulose ethers, only relatively weak streaks are obtained on cellulose fiber yarns tea effects and thus only minor improvements in the mechanical yarn properties. The result of such arbitrations are often too soft threads.

Attempts have also been made to use synthetic polymers as Use sizing agents for staple fiber yarns made from Cellulose fibers or acrylonitrile polymer fibers consist or contain these. So is the US patent 2,819,189 have already been proposed to settle Yarns made from continuous fibers and staple fiber yarns of various types to use copolymers, the free, or contain carboxyl groups and nitrile groups bound to sodium, potassium or ammonium in a molar ratio of 0.3: 1 to 0.75: 1, in aqueous, 5 percent solution at 60 C a p., - value between 5 and 9 and a viscosity between 5 and 200 cP. It is particularly emphasized that in order to achieve the appropriate sizing results, compliance the specified molar ratios is essential. this will described as particularly important because the coating properties are already at the limits of the specified molar ratios of the polymer in question drop noticeably. A crucial one Disadvantage of this, essentially neutral polymer is n? J te but is the fact that they are only partially soluble in water are. Some of these polymers, especially those with a high nitrile content, is only colloidal in water soluble or even insoluble and is then in the form of aqueous dispersions. Some of these are so unstable that they are often already coagulate during their production and thus become unusable

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become cash. Sizing agents of this type that are not complete Are soluble in water, are naturally also not as easily washed out of the fabrics as water-soluble polymers.

It is also known from German Offenlegungsschrift 1 594 905 that staple fiber yarns which consist of cellulose fibers and / or acrylonitrile polymer fibers or which contain them in amounts of at least 30 percent by weight can be sized if water-soluble copolymers are used as the sizing agent, which a) acrylonitrile and b) acrylic acid and its sodium or ammonium salts in a molar ratio (a: b) is between 1: 1.5 and 1: 7, preferably between 1: 2 and 1: 6 as polymerized units, and in 10 percent aqueous solution at 20 ⁰ C a Viscosity between 20 and 2000 cP and a p "value between 2.5 and 6.5, preferably between 3 and 5.5.

Although these sizing agents are generally extremely effective, they have certain disadvantages which are bothersome can make noticeable. Above all, the fiber coatings produced with them are more hygroscopic the closer the p "value their solutions lie at the neutral point; In a humid climate, therefore, those that are only slightly acidic with such solutions tend to be Yarn to stick together. If you want to avoid this disadvantage, you have to use the size fleet set more acidic; however, this increases the corrosion of the sizing machine and shortens its service life. Furthermore, it has been found that the sizing agents known from the above-mentioned laid-open specification do not are sufficiently compatible with all starch sizes. Occasionally it has also been shown that these are known Sizing agents could only be washed out incompletely after heat treatment of the sized material as a result of a chemical reaction of their carboxyl groups with reactive groups on the fiber material.

There has now been a new process for the production of a

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improved sizing agent, which does not have the above-mentioned disadvantages or no longer has a disruptive extent, by polymerization found of acrylonitrile with acrylic acid. The new process is characterized in that (a) acrylonitrile and (b) $ 20 to $ 60, preferably 25 to 45% with Alkali or ammonium ions, preferably with sodium or unsubstituted ammonium ions, acrylic acid neutralized in polymerized aqueous solution in the molar ratio a: b of 1: 0.8 to 1: 1.4 and the resulting aqueous polymer solution a p "value between 6 and 8, preferably between 6 and 7, L \ nplaces.

In addition to components a and b, up to 20 percent by weight, based on the total amount, can be used in the process of the invention of the monomers, of other, at least partially water-soluble monomers, such as acrylamide, methacrylamide, methyl acrylate, Methacrylic acid and its alkali and ammonium salts, maleic acid and its salts and half esters, methacrylonitrile and vinylpyrrolidone, polymerize into the sizing agent

For the partial neutralization of acrylic acid, all compounds can be used that are capable of removing the proton replace acrylic acid with alkali or ammonium ions, especially alkali and ammonium hydroxides, but also alkali and Ammonium salts of weak, volatile acids, e.g. the carbonates.

The polymerization is otherwise carried out in a manner known per se, preferably as a solution polymerization with additional use carried out by an initiator.

The process according to the invention gives clear, homogeneous and non-corrosive copolymer solutions which are stable in storage act on the sizing machine and do not tend to coagulate. On the other hand, the acrylic acid is pre-neutralized the polymerization completely or not at all, unusable products are obtained: in the first case, cloudy, inhomogeneous solutions that are not stable in storage and for

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Tend to stratify. In the second case, the batches usually coagulate before the end of the polymerization.

The copolymers obtained by this invention have a 10-percent aqueous solution at 2O ⁰ C a viscosity from 30 to 3000 cps as measured with a falling ball viscometer in accordance with Höppler in accordance with DIN 53,015th

Aqueous solutions of the polymers obtained according to the invention are suitable for sizing a wide variety of staple fiber yarns Art. The size coatings are characterized by their particularly low hygroscopicity. Staple fiber yarn that is sized can be, for example those from natural and / or regenerated Cellulose fibers such as cotton, rayon, linen and their blends with each other and with other staple fibers, such as polyester, polyamide and acrylonitrile polymer fibers, as well as yarns made from pure acrylonitrile polymer fibers. Under Acrylonitrile polymer fibers are both fibers made from homopolymers of acrylonitrile and those made from copolymers of acrylonitrile with up to about 20 percent by weight of other monomers. The ones used for finishing Aqueous liquors preferably contain 0.5 to 20 percent by weight of the polymers. Have particularly proven themselves the following concentrations: for rayon and linen 0.5 to 5> for cotton 3 to 10 and for acrylonitrile polymer staple fibers 5 to 15 percent by weight.

In addition to the polymers obtained according to the invention, the size liquors can also contain customary sizes and / or size auxiliaries contain, e.g. starch, chemically modified starch, carboxymethyl cellulose, methyl cellulose, polyvinyl alcohol and emulsified fats; In this connection, special mention should be made of the very good compatibility of the polymers with native ones and modified plant strengths.

Due to the good water solubility of the sizing agents according to the invention obtained the recognized with them liquors can be applied to the yarns at temperatures between 0 and 10O ⁰ C

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will. In many cases, however, it can be particularly advantageous to work with a liquor whose temperature is between 10 and 30 ^° C., that is to say close to room temperature. The polymer solutions can, however, also be processed at higher temperatures, which, owing to the associated decrease in viscosity, allows processing in higher concentrations.

The size is applied to the yarns in the usual way, i.e. primarily with the known machines for Wide finishing of chains. However, it can also be done by sizing individual threads, e.g. on the cheese. One The size can also be applied to bobbins or warp beams using dyeing equipment.

The parts and percentages given in the following examples are parts and percentages by weight. The Garnprüfungen were (20 ⁰ C, 65 # rel. Humidity) in a normal climate performed. The mechanical values given in the tables are mean values from 15 or 20 individual determinations. The rub rate is the average number of rubs until the thread breaks. It has been measured on the device described by E. Kenk in Textil-Praxis 7 (1952), 9, 698.

example 1

1,250 parts of water are ^{heated to 80 °} C. under nitrogen in a polymerization vessel. 230 parts of a 2 percent aqueous ^ SgOg solution are now added and a mixture of 1,450 parts of water, 600 parts of acrylic acid (98 percent), 322 parts of acrylonitrile and X parts of ΝΗ, ΟΗ (25 percent) with stirring over the course of 4 hours added dropwise at 75 ° C. After a further hour , a further 140 parts of a 2 percent KpSpOg-Ijö'eung are added to complete the polymerization and polymerization is continued for 1.5 hours. After cooling to room temperature, the p n value of the solution is _{adjusted to 6.5 with NH 4} OH (25 percent).

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The table below shows the results as a function of the degree of neutralization of the acrylic acid before the polymerization compiled:

No. X parts of the neutralization result NH ₄ OH, 25 degrees [#]

Coagulation

very cloudy solution with thick flakes slightly cloudy solution very clear solution slightly cloudy solution slightly cloudy solution cloudy solution

very cloudy solution, separation

The product d has a pesticide content of 25 1 ° and is a pale yellow, very clear solution. The viscosity of the 10 percent solution is 370 cP ^{at 20 ° C.}

Example 2

a 0 0 b 56.6 10 C. 113.3 20th d 170.0 30th e 283.3 50 f 340.0 60 G 510.0 90 H 566.6 100

496 parts of water are ^{heated to 80 °} C. under nitrogen in a polymerization vessel. Now 90 parts of a 2 percent aqueous KpSpOg solution are added and a mixture of 450 parts of water, 198 parts of acrylic acid (98 percent), 162 parts of acrylonitrile and X parts of ΝΗ, ΟΗ (25 percent) with stirring over the course of 4 hours at 75 ° C added dropwise. After a further hour the polymerization once 54 parts of a 2 percent K ₂ S ₂ O _ö solution was added and polymerization was continued 1.5 hours to complete. After cooling to room temperature, the _pH value is set (25 percent) to 6.5 of the solution with NH.OH.

The following table shows the results as a function

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summarized by the degree of neutralization of acrylic acid before polymerization:

No. X parts of the neutralization result NH ₄ OH, 25 degrees [%]

Coagulation Coagulation slightly cloudy solution very clear solution slightly cloudy solution cloudy solution

very cloudy solution, separation

Product d is a clear, yellow solution and has a pesticide content of 25 #. The viscosity of the 10 percent solution is 330 cP ^{at 20 ° C.}

Example 3

a 0 0 b 18.7 10 C. 37.4 20th d 56.1 30th 93.5 50 f 130.9 70 G 187.0 100

Of 75 parts water, 5 parts of potato starch and 2.5 parts of the 25 percent solution of d of Example 1 by injecting direct steam in the pressure cooker at 12O ⁰ C 100 parts of a sizing liquor are obtained. Even if this liquor stored for several hours at this temperature under pressure, it shows an unchanged viscosity according to DIN 53 211 with a 4 mm nozzle at 8O ⁰ C measured results in approximately 55 seconds flow time.

Example 4

From 55 parts of water, 10 parts of a water-soluble starch ether and 20 parts of the 25 percent solution d from Example 2 are obtained by introducing direct steam and boiling a Sizing liquor which, measured according to the information in Example 3, has a flow time of 52 seconds; the run-out time is also

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unchanged after a cooking time of 6 hours.

Example 5

A sizing agent which was produced according to the information in Example 1 under d, but in which the neutralization was carried out with sodium hydroxide solution, is applied to raw cotton yarn on a sizing machine. The yarn is heated hour at 14O ⁰ C. The size can then be removed practically completely on the yarn by simply washing it out.

Example 6

Using a laboratory sizing machine, a cotton yarn Nm 68/1 is sized with a sizing liquor at 80 ⁰ C. Composition and preparation of the size liquor: 400 parts of the 25 percent strength polymer solution from Example 1d are diluted with 600 parts of water by simply stirring together. The resulting liquor is colorless, clear, neutral and homogeneous.

The yarn sized with an application amount of 12.5 percent by weight (based on raw yarn weight = 100 %) is subjected to an abrasion test. The abrasion index 955 is determined; the untreated cotton, on the other hand, only has a rub rate of 100.

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Claims (4)

2Ü04676 - ¹⁰ - O.ζ. 26 594 Claims 1,. A method of making an improved sizing agent by the polymerization of acrylonitrile with acrylic acid, characterized gekennzeichne t that (a) acrylonitrile and (b) about 20 to 60 $> neutralized with alkali metal or ammonium ion acrylic acid in aqueous solution in the molar ratio a: b of 1 : 0.8 to 1: 1.4 polymerized and the aqueous polymer solution obtained is adjusted to a p n value between 6 and b. 2. The method according to claim 1, characterized in that an acrylic acid neutralized to 25 to 45 $> is used as component (b). 3. The method according to claim 1 or 2, characterized in that the aqueous polymer solution is adjusted to a p "value between 6 and 7. 4. The method according to any one of claims 1 to 3 » characterized in that the partial neutralization of the acrylic acid is carried out with sodium or unsubstituted ammonium ions. Badische Anilin- & Soda-Fabrik AG _ 109833/1935