DE2231147A1 - LAUGATING AND MERCERIZING SOLUTIONS - Google Patents

Description

FARBWERKE iIOECHST AG formerly Meister Lucius & DrüninK _{A rt}

2231U7

File number: "- HOE 72 / F Ϊ84

Date: I9. June 1972 Dr. Gr / stl caustic and mercerisior solutions

During mercerising and causticising, alkali lyes have a detrimental effect Strength is adapted to the requirements, on the goods. So that the process runs as quickly as possible and one Continuous and efficient operation is allowed, it is necessary that the goods quickly and evenly with the alkaline solution is soaked. To this end, one uses add wetting agents to the solutions. Such wetting agents should be easily soluble in the lye, the maximum in the shortest possible time Cause shrinkage of the cellulose fiber and also after The lyes remain dissolved after long periods of storage.

It is known, for example, to use alkyl sulfates, alkanesulfonates, alkylarylsulfonates, Lignosulfonic acids, sulfated terpene derivatives, use alkylated naphthalenesulfonic acids and similar compounds as wetting agents in mercerising liquors. Furthermore, in the German Auslegeschrift 1 Ql ^ O67 the application of Mixtures of such mono- and polysulfonic acids or their salts in mercerizing and caustic baths are described. These Compounds were made by sulfochlorination of aliphatic or cycloaliphatic hydrocarbons rait 10 to 20 Obtained carbon atoms.

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The wetting agents are usually mixed with other auxiliaries combined which the mercerization of the fiber

detached products, such as cellulose degradation compounds or

Sizing residues, disperse and keep in suspension.

At the same time, these auxiliary substances act synergistically on the Wetting defects in the wetting agent. The application is well known

of low molecular weight alcohols such as isopropanol, butanols,

Alkanolamines, glycols and their derivatives, polyglycols

and other compounds, which, inter alia, in Lindner "Tenside, Textilhilfsiiiittel, Waschrohstoffe", Vol. II, 1964, pages 1476

to 1478 are described.

The products in use up to now do not meet all of them Requirements of practice at the same time. Either they wet the fiber very quickly, but then they have to be higher Concentrations are applied, or they are not sufficiently long-term stable in the alkaline solutions, lose their effectiveness or fail. In many cases, their strong foaming also interferes.

It has now been found that caustic and flake solutions with excellent irritant effect and high resistance can be obtained if these solutions containing 10 to 400 g / l sodium, Potassium or lithium hydroxide or mixtures of these alkalis contain 0.1 to '5 g / l of phosphinic acids or as wetting agents their alkali salts of the general formula

R.

R ₂ -

_{1 is} a methyl or ethyl radical and

p is an aliphatic unbranched, branched or

cyclic hydrocarbon rust with Ί to 12 carbon atoms, preferably nil 6 to 10 carbon atoms means, ηu, '/ ?. · .- · .ηt?; .t.

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The phosphinic acids or their alkali salts to be used as wetting agents according to the invention can be prepared by various methods getting produced. The implementation is known, for example of the sodium salt of Hethanphosphonsäure-monoethylester with Grdgnard compounds (K..A. Petrov et. Al., Z. obsc. Chim. 30 ■ 1964-8 (1960); Approx. _5_5, 6363b (196I)). Particularly preferred is the process according to patent applications P 1 963 01 «.9, P 2 043 52O.5 and P 2 100 779.4. Thereafter, dialkylphosphinic acid alkyl esters are used the general formula

- OR,

wherein R ^ is an alkyl group having 2 to 22 carbon atoms and R and R alkyl groups with 1 to 22 carbon atoms mean by addition of olefins with 2 to 22 carbon atoms on phosphonous acid alkyl ester the formula

Ϊ -

R ₂ -P- 0.R ₃

made / R and R-. have the meaning given above. For the reaction can be used as alkyl phosphonate, for example: methyl methanephosphonate, ethyl methanephosphonate, Octane phosphonous acid ethyester. The dialkylphosphinic acid esters can be prepared by known methods which produce salts or acids. It is advisable to carry out ■ an alkaline saponification.

The phosphinic acids to be used according to the invention and their salts are easily and clearly soluble and have alkaline properties Area such an excellent network understanding that compared to conventional ! 3et '/. !! aids worked with smaller amounts of ice ■ can vercien. The applications are between 0.1 and 5 g /; i Lautier- ooder / Iercerising solution. As a result, these are

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Connections are not only very economical, they also hardly pollute the wastewater. In addition, Inventive · _t reniäß practically form to be used phosphinic acids and their salts in alkaline solutions no foam. The saturation capacity does not decrease even when the alkaline solutions are stored. A preferred field of application is mercerized lye, which has a high content of about 150 to 300 g, preferably 200 to 250 g of sodium, potassium or lithium hydroxide or mixtures of these alkalis per liter.

Due to the per se known additions of lower alcohols e.g. isopropanol or butanol, or alkanolamines] !, such as e.g. Butyl diethanolamine can be used to further improve the wetting ability.

The composition of the caustic and mercerising solutions, in which the phosphinic acids or their salts are used according to the invention are known per se. The solutions contain generally 10 to 400 g of sodium, potassium or lithium hydroxide or mixtures of these alkalis per liter and if necessary the usual_ auxiliaries; they are at temperatures used between about 0 and 25 ° C. Regarding their further composition, please refer to Lindner, "Tenside, Textilhilfsmitteü, Waschrohstofffe ", Volume II 1964, pages 1 * 176 to 1 * 178, and Ulimanns Encyclopadie der technischen Chemie, 3rd edition, Volume 17, 1966, pages 176-177.

In addition, it is not necessary under all circumstances, according to patent applications P 1 963 01 * 1.9, P 2 0 * 13 520.5 and P 2 100 779. ^ Dialkylphoshnhinsäureester produced initially to convert into the corresponding acids or alkali salts in order to use them in the manner according to the invention. It is also possible, the ester directly to the caustic; and icing solutions add, since the esters are soon hydrolyzed to the salts in the alkaline liquid.

In the following examples, the advantage of the erfinuungsgerriß - /, u. veri'ciy ^ nden Pho.'nhiri '>. "ur> M).

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2231U7

and their salts are explained in more detail, without the application being restricted to these mercerising liquors.

Since the wetting ability of strongly alkaline liquids cannot be measured with the usual devices according to DIN 53 9Ul, the shrinkage of cotton in this liquor is used as a measure for the wetting ability of a mercerising liquor. A tester for mercerising liquors according to Hintzmann was used for the experiments. Dies.es device is described in detail in "HeHiand Textile Reports" (1968) Heft 3, pages 311 to 315 · 4 and booklet pages 450 to 456. Worked was measured at 20 ⁰ C with a capacity of 250 cirr at 33 g load. Cotton strands (70/2 fold) 27.4 cm in length were used for the measurements. The shrinkage that occurred was measured when the alkali was left to act for 5, 10, 20, 30, 45, 60, 75 and 90 seconds. The shrinkage rates in mm / sec were calculated from the shrinkage values obtained in mm. calculated.

All mercerising liquors tested contained 220 g of sodium hydroxide per liter plus those listed below. Wetting agents and auxiliary materials.

Lye No. 1: 0.3 g / l methyloctylphosphinic acid 0.4 g / l isopropanol

Lye No. 2: 1 g / l methyloctylphosphinic acid Lye No. 3: 5 g / l methyloctylphosphinic acid Lye No. 4: 2.5 g / l methylcyclohexylphosphinic acid

Lye No. 5- 1> 5 g / l methyloctylphosphinic acid

1.2 g / l isobutyl diethanolanine 0.05 g / l triisobutyl phosphate ₅ 0.5 g / l n-butanol

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Lye No. 6: 1.5 g / 1 paraffin polysulfate (from η-paraffin

with a Xettenlänco of 1 ^J i - 18 C-Atoiaen) (level of 1.2 g / l Iscbutyldiäthariolamin

Technology) 0.05 g / l triisobutyl phosphate

0.5 g / l n-butanol

The measurement results are summarized in Table I.

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Tabel

Time
sec

Shrinkage mm

Shrinkage speed mm / see

Lye Lye Lye Lye Lye Lye Lye 1 2 3 3 4 5 ^ί 6

η.24h lye lye lye lye lye lye 1 2 3 3 4 5 β

η.24h

O 5 22nd 13 ' 58 57 3 47 4th CD 10 74 50 92 88 36 90 14th CX) 20th 119 90 98 98 71 97 34 -Ο 30th 126 95 99 99 75 99 51 ΡΟ 45 129 98 99 100 78 101 64 60 130 99 100 100 80 102 75 75 130 100 101 101 81 102 80 90 132 101 101 101 82 103 84

22nd 13th 58 57 3 47 4th 52 37 34 31 33 43 10 45 40 6th 10 35 7th 20th 7th 5 ' 1 1 4th 2 17th 3 3 0 1 3 2 13th 1 1 1 O 2 1 11 0 1 Ι 1 1 O 5 2 1 Ο O 1 1 4th

NJ NJ CO

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The table values convincingly demonstrate the advantage of the phosphinic acids and their alkali salts to be used according to the invention. The net capacity of the mercerising liquors according to the invention, which is still unchanged after 24 hours, can be seen from the knife vessels with the lye j5. For further explanation, the values of the shrinkage as a function of time when using alkaline solutions No. 1, 5 and in FIG. 1 are shown. FIG. II shows the associated V / er of the shrinkage speed in ^{1 as a} function of time.

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Claims (3)

Claims ■ 1. .Lauging and mercerising solutions, which 10 to 400 g / l Contain sodium, potassium or lithium hydroxide or mixtures of these alkalis, characterized by a content of 0.1 to 5 g / l of phosphinic acids or their alkali salts general formula , ^ F - OH * C ■ - where R. is a methyl or ethyl radical and R "is an aliphatic unbranched > branched or cyclic hydrocarbon radical with 4 to 12 carbon atoms, preferably 6 to 10 carbon atoms. 2. Use of phosphinic acids or their alkali salts general formula P-OH, wherein R. is a methyl or ethyl radical and Rp is an aliphatic unbranched, branched or cyclic hydrocarbon radical with 4 to 12 carbon atoms, preferably with 6 to 10 carbon atoms means as a wetting agent in caustic and mercerising solutions. 3 .. Process for leaching and mercerising cellulose fiber material, characterized in that the fiber materials are treated with leaching and mercerising solutions which, as wetting agents, contain phosphinic acids or their alkali salts of the general formula
0 - OH, ^R 2 wherein R _{1 is} a methyl or ethyl radical and Rp is an aliphatic unbranched, branched or cycliaci-icn hydrocarbon residue with 4 to 12 carbon atoms, preferably having 6 to 10 carbon atoms. 309884/1260 BATH