DE2542090A1 - CONDENSATION PRODUCTS - Google Patents

Description

It has been found that valuable condensation products are obtained if cycloalkanones with formaldehyde and alkali metal bisulfite are used condensed in aqueous solution in a molar ratio of 1: 2-3: 0.7-1.1. The condensation products have excellent Effect as a dispersant.

Condensation products from ketones, formaldehyde and alkali salts of sulphurous acid are already known. The uses these products depend on the molar ratio of the reactants. From DT-PS 870 031 are tannins known by the condensation of aliphatic ketones with formaldehyde and sulfonic acid group-supplying compounds can be obtained.

In DT-OS 1 720 729 condensation products are mentioned that are formed by the reaction of cycloalkanones ^ formaldehyde and alkali salts the sulphurous acid can be produced. According to the examples of this laid-open specification, compounds are obtained which contain up to 0.5 moles of sulfo groups per mole of cyclohexanone and have a good tanning effect. they show but not the good dispersing effect of the new products. From the DDR-PS 84 962 connections are known through

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Condensation of acetone, formaldehyde and sodium bisulfite or Sodium sulfite obtained, for example, in a molar ratio of 1: 2: 1 will. These condensation products are easily soluble in water and have dispersant properties. A big technical one The disadvantage, however, is their strong red-brown to black-brown inherent color. They are therefore unsuitable for formation of light disperse dyes or optical brighteners, especially if these are to be applied to polyamide. The weakly absorbing dispersant is drowned out its own color dye and brightener.

In contrast, it is surprising that dispersants based on cycloalkanones in a simple manner as pale pale yellow Colored solutions can be obtained, which can be achieved with little technical effort, e.g. by working under nitrogen atmosphere can be obtained colorless by bleaching with hydrogen peroxide or adding phosphites or borates can. These additional measures have to be taken in the case of acetone condensation products no success in terms of whitening.

Cycloalkanones, cyclo-pentanone and cyclohexanone, and their mono-, di-, tri- or tetralkyl derivatives such as 1-methylcyclohexanone or 1,3, S-trimethylcyclohexanone-S, are preferred. Alkyl is preferably a C ₁ -C -alkyl radical.

In particular, sodium or potassium bisulfite in a 35-40% strength aqueous solution are used as bisulfites.

The reaction temperatures are at 20 - 120 ° C, preferably at 70 - 11O ⁰ C. The condensation is carried out at pH values above 8. It is generally initiated by elevated temperature and adding a little aqueous liquor. The pH value of the reaction solution changes during the course of the reaction without further addition of caustic to a stronger alkalinity (pH 10 - 12),

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to return to the weaker alkaline area towards the end of the reaction to return.

The condensation is exothermic. However, it can be easily controlled and controlled. Therefore, the manufacturing process is easy to carry out technically. For the technical implementation in a closed system only increases in temperature of 100 ⁰ C are observed at about 125 ° C.

The reaction can therefore be carried out safely even with only slightly dilute reactants. In this way, highly concentrated ones are obtained Solutions that can be adjusted to 40 - 50% without affecting the condensation products or any accompanying salts crystallize. The solutions can be evaporated to dry, fluffy powders that are not hygroscopic.

The temporary formation of bisulfite addition products has the great advantage that the sparingly water-soluble ketones are soluble and the easily soluble ones are not deposited by the salts (bisulfite). After the condensation, the keto group is im IR spectrum at 5.9 / u can be detected again in full strength.

The condensation products obtained are largely free of extraneous salts due to the use of bisulfites, which are concentrated in the case of concentrated Solutions or many areas of application, e.g. emulsion polymerizations, lead to malfunctions.

The molecular weights of the condensation products are used for solubility reasons determined in water. With the help of an ultracentrifuge, molar weights of the hydrated product are determined with a Distribution from 16,000 to 27,000 in particular was found.

The products are particularly suitable for dispersing inorganic and organic pigments, disperse dyes,

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poorly soluble anionic dyes, e.g. acid or chromium complex dyes, optical brighteners, sparingly soluble cationic dyes, lime soaps in detergents (reinforcement detergency instead of sodium polyphosphate) and pesticides, especially wettable powder.

The effectiveness is outstanding when used in the boiling dye bath, e.g. when dyeing polyester materials with dispers ion s dyes.

The products can also be used to advantage for dispersing synthetic and natural latices, since the low intrinsic color, unusual light stability and the extremely low foreign salt content, trouble-free production and Guarantee usage.

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example 1

260 g of sodium bisulfite solution (40%; 1 mol) and 520 g of water are mixed with 109 g (1.3 mol) of cyclopentanone at 60.degree. A clear solution is obtained by increasing the temperature to 80.degree. After adding 260 g of formaldehyde solution (30%; 2.6 mol), the pH is adjusted to about 9 with sodium hydroxide solution. About 15g sodium hydroxide solution, 45%, are consumed within one hour. ^{The temperature rises to 100 102 °} C. as a result of self-heating. After 3 hours, the mixture is cooled. From the pale yellowish solution, water is distilled off in vacuo until 500 g of an aqueous solution remain as residue, which is 50% active ingredient. The solution is only weakly colored and is also stable at OC.

This dispersant solution is excellently suited to be added to the dyebath in a dye works via metering systems.

When dyeing polyester fibers with pigment dyes, 2 ecm - 4 ecm of dispersant solution per liter of dye bath * a flocculation of the pigments and thus the formation of spots on the polyester completely.

Example 2

260 g sodium bisulfite solution (40%; 1 mol) and 180 g water mixed with 128 g of cyclohexanone (1.3 mol) at 60 ° C. and stirred well. The temperature rises to 80 C and some of the The bisulfite additive product formed is crystallized out. Only when adding 260 g of formaldehyde solution (30%; 2.6 mol) and heating to 80 ° C everything goes back into solution. Approx. 15 g of sodium hydroxide solution are slowly added to bring the pH to approx. 9-11 to obtain. After a while, a rise in temperature

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A reaction is indicated when the temperature rises to 100 - 104 ° C. The reaction mixture is kept at 100-102 ° C. for a further 3 hours. the The slightly yellowish solution is suctioned off through a suction filter for clarification. This dispersant solution can be used in this form Liquefying of pigment suction cake can be used, the then, for example, can be passed through a sand mill for pigment grinding.

The 20% solution has an iodine color number of 5 (a 20% solution of the dispersant made of acetone-formaldehyde-bisulfite shows an iodine color number of over 1100).

The color number can be reduced to 1-2 if the condensation is carried out under nitrogen or substances such as dimethyl phosphite, boric acid and others in amounts of O, O5 - 1% can be added.

The following comparisons show the excellent dispersing effect emerge:

10 g of a finely divided zinc oxide are mixed with increasing amounts of a 1% dispersant solution until it becomes thin Grinding is obtained. There were 18 ecm 1% dispersant solution of this example consumed. From a 1% solution of the known condensation product from naphthalene sulf onic acid and formaldehyde are consumed 28-30 ecm.

The herbicide Diuron '^ is in a grinding device, e.g. Jet mill, ground in the following composition: 80% active ingredient, 5% dispersant, 1.25% dibutylnaphthalene sulphate, 4% Silkasil S, 9.5% clay. The test of dispersibility according to the WHO regulation is fulfilled. In a 1% Dispersion in water 5 ° d. Hardness settles after 30 minutes less than 25% of the active ingredient.

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The insecticide 'Lebayeid ' \ -J is ground in the following formulation: 40% active ingredient, 4% dispersant, 0.5% dibutylnaphthalene sulfonate, 55.5% Silkasil. In the WHO test for dispersibility, the powder is well wetted and the 1% dispersion in water 5 ° d. Hardness shows less than 30% of the active ingredient as sediment after 30 minutes.

Example 3

From 260 g sodium bisulfite solution (40%; 1 mol), 260 g water, 146 grams (1.3 moles) of methylcyclohexanone and 260 grams of formaldehyde solution (30%; 2.6 mol), a reaction solution is prepared according to the method of the preceding examples, which by adding is kept at pH 9-11 by approx. 15 g sodium hydroxide solution. The heat of reaction After a while, the batch is heated to 100 ° C. The mixture is then stirred at 100 ° C. after 2 hours, and the paragraph is filtered off evaporate to dryness in a suitable apparatus. A light yellowish colored, loose powder is obtained, which too shows no clumping when lying in a humid atmosphere.

Example 4

To a mixture of 230 g sodium bisulfite solution (40%; 0.9 mol) and 130 g of formaldehyde solution (30%; 1.3 mol) are added while stirring 110 g (1.12 mol) of cyclohexanone. The initially two-phase The reaction mixture becomes homogeneous at approx. 90 ° C. after 30-40 minutes. Add 110 g of formaldehyde solution (30%; 1.1 mol) and adjusts the pH value to 9-10 with approx. 10 ecm sodium hydroxide solution. The temperature rises to 105 ° C. It will take 2 hours 100-105 C stirred. Subsequently, while cooling down the pH is adjusted to 7 by adding hydrochloric acid. In this order of addition of the reaction

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partner an excellent dispersant. Despite higher concentrations no violent reaction is observed.

The property, the thixotropy of dye-pigment presscakes Breaking through with small amounts of 0.05 to about 0.3 percent is particularly pronounced with this product, so that it has proven particularly useful in bead mill grinding.

3 kg of a powder of the dye CI.Dispersblue 71 are with 10 kg of a 30% solution of the dispersant were stirred homogeneously and pre-comminuted by means of a toothed rotor-stator colloid mill and in a high-speed agitator mill with glass grinding media the grain size 0.4-0.6 mm is filled, crushed with a dwell time of 50 minutes. The suspension obtained shows good storage stability and application properties.

Equally good results are obtained if than to be dispersed Substance to be used CI. Dispersyellow 60, CI. Vatbrown 3, copper phthalocyanine of the cC modification according to the example 1 of DT-PS 1 136 303, the dispersion brightener according to Example 1 of DT-PS 1 080 963 or titanium dioxide (rutile).

10 kg of an 18% filter cake of the dye CI. Dispersion blue 71 are liquefied with the addition of 1.8 kg of the dispersant with a high-speed stirrer and then wet-ground in a tendon agitator mill containing Ottawa sand (grain size 0.5-0.8 mm) with a residence time of 40 minutes. After a further addition of 8 kg of a 30% strength solution of the claimed dispersant and subsequent spray drying at an air inlet temperature of 180 ° and an air outlet temperature of 80 °, a setting which is easily dispersible in water is obtained which shows good application properties.

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Equally good results are obtained if CI is used as the substance to be dispersed. Dispersyellow 60, CI Vatbrown 3, copper phthalocyanine of the cC modification according to Example 1 of DT-PS 1 136 303, the dispersion brightener according to Example 1 of DT-PS 1 080 963 or titanium dioxide (rutile).

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Claims (7)

Claims 1), 'Condensation products from cycloalkanones formaldehyde and alkali bisulfite obtained by condensation in a molar ratio of 1: 2-3: 0.7-1.1 in aqueous solution. 2) condensation products according to claim 1, characterized in that that cyclopentanone or cyclohexanone is used as cycloalkanone. 3) condensation products according to claim 1, characterized in that
the. net that they are obtained by condensation at 20 - 130 4) Process for the preparation of condensation products from cycloalkanones formaldehyde and alkali bisulfite, characterized in that that the reactants are reacted in a molar ratio of 1: 2-3: 0.7-1.1. 5) Method according to claim 4, characterized in that the Implementation at 20-130 ° C is carried out. 6) Use of condensation products according to claim 1 as Dispersants. 7) dispersants, characterized in that they are condensation products according to claim 1 included. Le A 16 641 - 10 - .7098 * 3/0833