DE1111631B - Process for increasing the solubility of organic N-chlorine compounds - Google Patents

Description

The technical importance of organic N-chlorine compounds containing active chlorine as bleach and disinfectants are generally characterized by the poor solubility of these compounds in aqueous or aqueous-alkaline solutions significantly impaired. This is especially true for connections from of the type of azochloramide, of N-chlorohydantoin and its derivatives, of N-chloro-acetylenediureide, of N-chloro-cyanuric acid and its salts, N-chlorinated triazine derivatives, N-chloro-biguanide and similar compounds, which have recently gained importance as disinfectants and bleaches.

If such compounds have a small number of N-chlorine groups in the molecule, i.e. also a low content of active chlorine, they are generally soluble in the range of the concentration to be used, but the solubility of the organic compounds decreases very quickly with increasing active chlorine content. For example, while monochloromelamin, whose active chlorine content is 43.8%, provides a solution with a content of 282 mg active chlorine per liter in water (maximum chlorine content of the saturated solution at 20 ° C in mg Cl ₂ per liter after 10 minutes) the active chlorine content of the hexachloromelamine is 127%> but the chlorine content per liter of the aqueous solution under the same conditions is only 86 mg. This fact is important for technology insofar as the organic base of such compounds, i.e. the non-chlorinated compound or the compound released during hydrolysis of the chlorinated compound, is only a carrier material and is therefore used as ballast as soon as the required active compound is used Chlorine has been split off. It is therefore desirable in technology to use compounds which have a high content of active chlorine, as far as possible, since they contain only a relatively small amount of organic base material as a carrier material with the highest degree of effectiveness. However, this objective cannot be achieved by adding equivalent or nearly equivalent amounts of non-chlorinated or slightly chlorinated compounds to the highly chlorinated compound. This process then only corresponds to the use of low or medium chlorinated products.

It has now been found that the solubility and thus the efficiency and application range of organic, in particular highly chlorinated organic N-chlorine compounds can be increased significantly if the procedure according to the invention is used. This consists in following the method of increasing solubility
of organic N-chlorine compounds

Applicant:

Henkel & Cie. GmbH.,
Düsseldorf-Holthausen, Henkelstr. 67

Dr. Valentin Habernickel, Bergheim / Sieg,

and Dr. Friedrich Weldes, Düsseldorf-Benrath,

have been named as inventors

aqueous solutions of the organic N-chlorine compounds in the presence of water-soluble ones that do not react with the organic N-chlorine compound Subjecting alkali salts to spray drying, the amount of alkali salt used being at least 5% preferably 10 to 30 percent by weight, based on the organic N-chlorine compound.

The alkali salts used are in particular the water-soluble sulfates, halides, phosphates and silicates and carbonates and here again preferably the sodium and potassium salts in question. Suitable Compounds are thus for example sodium sulfate, sodium chloride, potassium chloride, primary or secondary sodium phosphate, sodium carbonate, sodium silicates or the corresponding potassium salts.

This list by no means makes any claim

Completeness. It is advisable to use those alkali salts which react neutrally or whose pH in 1% solution is in the range from 4.5 to 9. If you work in a neutral solution, you lose the known organic N-chlorine compounds in the spray process almost no active chlorine. When adding slightly alkaline salts, slight chlorine losses can occur however, practically does not affect the process.

For the method according to the invention come

The following list does not claim to be exhaustive, especially the one below listed N-chlorine compounds in question;

Azochloramide and its various chlorination products, such as mono-, di-, tri- and teirachlorazo-

109 649/430

3 4

dicarbonamidine. Cyanuric acid, - like that. Mono-, the organic N-chloro-di- or trichloro compound and the corresponding compounds in the presence of alkali salts

Alkali and alkaline earth salts. Chlorination products of drying and then crushing led

Acetylenediureide with 1 to 4 N-chlorine groups. Partly - for that reason alone unsatisfactory results,

substituted N-alkyl and N-aryl derivatives of Ver 5 because considerable losses are incurred in this procedure

bonds of the general formula active chlorine occurred.

The inventive method is used in the following

, NR '- CR - NR' the examples below. The parts in the following

q_q / ^ c = O ^ ^en examples ^{smc * parts by} weight; the percentages are

\ / ίο weight percent.

NR'-CR-NR '_. . ,,

example 1

R is either hydrogen or in a solution of 20 parts of tripolyphosphate,

an alkyl or aryl radical, R 'each hydrogen, 40 parts of sodium sulfate and 10 parts of pyrophosphate

an alkyl or aryl radical and at least one * 5 (all substances anhydrous) in 700 parts of water

If chlorine, the molecule has 1 to 4 chlorine atoms, 10 parts of trichloroazodicarboxamide

may contain. (107% active chlorine content) suspended and the

Corresponding N-chlorotriazines with 1 to 6 chlorine atoms and mixed at 90 to 95 ° C by hot spraying Derivatives, derived from melamine, dries. About 80 parts of spray product are obtained as Derive Amelin and Amelid. N-chloro-hydantoin 20 anhydrous mixture with a content of 12.5% or N-alkyl or N-aryl chlorohydantoins and an N-chlorine compound. The active chlorine content of this also mono- and dichlorobiguanides. Mixture is 13.0% (theoretical 13.37%).

The compounds can be used either individually or as an aqueous solution saturated at 20.degree

are used in a mixture. Spray product contains 3940 mg of active chlorine im

The amount of additives according to the invention to 25 liters, while a mechanical mixture of the same

water-soluble, with the organic N-chlorine constituents a solution with 233 mg of active chlorine

bonds of non-reacting alkali salts to those in the liter,

aqueous solution or suspension of organic N-chlorine example 2
Connections before the spraying process can be any

can be varied and depends on the use 30 20 parts by weight of dichloroazodicarboxamide, the purpose of the mixture obtained after spray drying, with 60 parts of anhydrous sodium sulfate. However, it is necessary to mix at least 5% by weight, based on the organic water, with vigorous stirring in 250 parts. Spray drying at 100 ° C N-chlorine compounds to use. Preferably 88 parts dry powder provides 17.3%, amounts of 10 to 30% by weight in 35 active chlorine (theoretical 17.5%). The chlorine consideration. However, larger amounts can also be used after 6 weeks of storage when turning rooms, with a natural limit given by this, unchanged at 17.3%.
is that a minimum content of active chlorine in the end A saturated at 20 ° C aqueous solution of this product, based on the mixture, be present spray product contains 2713 mg of active chlorine in the must, which is above the 40 liters according to known methods, during a mechanical mixture of the same solubility increase achievable content of active constituents is a solution with 146 mg of active chlorine per liter of water. delivers in the liter.

The alkali salts mentioned can not only be used alone, Example 3
but, which is often expedient, also as mixtures

Find application. The 45 40 parts of NjN'-dichloro-QC'-dimethyl-acetylene-

spraying solution or suspension further in the final diureide, 30 parts of sodium pyrophosphate and 30 parts

Additives desired for the product, especially wash-proof water glass (molar ratio SiO ₂ : Na ₂ O = 3.35: 1)

active connections. During the process, 500 parts of water are slurried and at

spray such solutions or suspensions, which sprayed 95 ° C. About 100 parts of dry

takes place according to known methods, the temperature is 50 product with 19.4% active chlorine (theoretical 19.9%).

temperatures are generally between 80 and 15O ⁰ C. The chlorine content after 30 days at room

It has proven to be useful, preferably at 19.30% temperature.

Temperatures from 85 to 120 ° C to work. An aqueous solution of a saturated at 20 ° C

The method according to the invention results in the mechanical mixture having the above composition

Solubility of the organic, active chlorine containing 55 contains about 300 mg of active chlorine per liter. That

Organic N-chlorine compounds by a multiple of the spray product according to Example 3, on the other hand, provides a

increased, as well as from the saturated solution below, which contains 8770 mg of active chlorine in the

Examples given is evident. Contains liters of water.

Comparative tests have also shown that

the better solubility of the organic N-chlorine- 60 Example 4
compounds not solely on the atomization

fine distribution or comminution of the In the same way as described in Example 3,

Mixtures is due. So show z. B. in a 40 parts of dichloroacetylenediureide, 30 parts of tri-

Colloid mill crushed particles also in counter-polyphosphate, 30 parts water glass (molar ratio

were the same water-soluble alkali salts after 65 SiO ₂ : Na ₂ O = 3.35: 1), 60 parts of sodium sulfate and

Mixing nowhere near the solubility of the 1 part fatty alcohol sulfate sprayed ^{at 90 to 100 0 C,}

Mixtures according to the invention, which is surprising. About 160 parts of spray product with 16.7%

is to be seen. Also attempts aimed at using active chlorine.

Dissolve in 1 liter of water at 25 ° C after 10 minutes 14.34 g, based on dichloroacetylenediureide. With a mechanical mixture of the same composition go under the same conditions only 0.462 g of the organic N-chlorine compound in Solution. The active chlorine content of the solutions was accordingly 2.1 and 0.07 g / l.

Example 5

In the table below are a number of mixtures of organic N-chlorine compounds as well as the alkali salts claimed in the application, together with the results, which in terms of solubility on the one hand by the claimed process (spray drying) and on the other hand were obtained with mechanical mixing of the comminuted components. The solubility the organic N-chlorine compounds were calculated from the chlorine content of the solutions. the individual columns of the table, unless otherwise specified, contain the following information or numerical values:

Column 1:

Column 2: "/" - content of inorganic salts, based on the total mixture, namely under number

a)% content of sodium sulphate,

b)% content of sodium pyrophosphate,

c)% content of sodium silicate (molar ratio of SiO ₂ : Na ₂ O = 3.35: 1).

Column 3: active chlorine content of the mixture in%.
Column 4:

mg of active chlorine per liter of water at 2O ⁰ C after mixing for 10 minutes (saturated solution)
a) for the spray product,

b) for the mechanical mixed product.

Column 5: Solubility of the organic N-chlorine compound (grams per liter), calculated from the chlorine content the solution,

a) in the case of the spray product according to the invention,

b) for the mechanical mixed product.

Type of organic N-chlorine compound as well as 25 The mixtures that are subjected to spray drying in brackets% active chlorine content of these ver were, according to the procedure of Example 1 binding. manufactured.

1 a) 2
b) c) 3 ι
a)
Spray
Per
duct \
b)
Mixed
Per
duct a)
Spray
product 5
b)
Mixed
product Monochloroazodicarboxamide (47.3) \ 50
50
50 20th 20th 23.6
14.2
14.2 2400
2676
2830 189
201
211 4.32
5.61
5.98 0.3900
0.4250
0.4450 Dichloroazodicarboxylic acid (77.0) I. 30th
30th 20th Z 53.9
38.5 3030
3852 156
181 3.95
5.01 0.2100
0.2350 Trichloroazodicarboxylic acid (97.5) < 50
20th 50
20th 10 48.5
48.5
48.5 2600
2900
3362 101
202
203 2.68
2.99
3.47 0.1040
0.2400
0.2450 Dichloroacetylenediureide (66.7) j 20th
20th 10 - 53.4
46.7 4832
8376 248
296 7.23
12.56 0.3720
0.4440 Tetrachloroacetylenediureide (100.0) j 30th
30th
10 10
30th 10 70.0
50.0
60.0 3160
5281
5994 102
164
162 3.16
5.28
5.99 0.1020
0.1640
0.1620 Dichlorohydantoin (71.3) j 50
30th 20th ■ 35.6
35.6 1326
5159 286
312 1.86
7.24 0.4015
0.4380 Dichloromelamine (72.2) 20th - - 57.7 982 196 1.36 0.2710 Tetrachloro melamine (106.0) 10 10 10 74.2 1781 126 1.68 0.1186

The above comparative values show that the solubility of the organic N-chlorine compounds is increased considerably by the method according to the invention.

Claims (3)

PATENT CLAIMS: 60 1. A process for increasing the solubility of organic N-chlorine compounds, characterized in that the aqueous solutions of the organic N-chlorine compounds in the presence of water-soluble alkali salts which do not react with the organic N-chlorine compound are subjected to spray drying, the Amount of the alkali salt used is at least 5%, preferably 10 to 30 percent by weight, based on the organic N-chlorine compound. 2. The method according to claim 1, characterized in that one carries out the spray drying at temperatures of 85 to 12O ⁰ C. 3. The method according to claim 1 and 2, characterized in that such water-soluble alkali salts are used whose 1% i§ ^e aqueous solutions have a ρκ range of 4.5 to 9.0. © 109 649/430 7.61