DE2117455A1 - Crystalline forms of the 4,4-bis-square bracket to ^ anilino-o-morpholino-l ^, 5-triazin-2-yl) -amino square bracket to -stilbene-2,2-disulfonic acid, process for their preparation and their use - Google Patents

Description

f? j * - ^. A "Ti * ¹ i'y

Ti * ¹ i'y & CH 4000 Base! 21 (Switzerland O 1 1 "7 / CC

I «^" M *. zj | / 4bb

Case 3A-3263 / G0 449

Germany

Crystalline forms of 4, 4 ^l -Bis- ^ ~ (4-e.nilirio-6-morpholi.tio-.11 3- »5-triazin-2-yl) -amino7" -stilberL-2, 2 '-disulfonic acid , Process for their preparation and their use.

The use of II, K'-bis-triazinyl derivatives of 4 _} 4'-oleaminostilbene-2,2'-disulfonic acid for brightening substrates based on cellulose and polyamides has been known for a long time and has been widely used in flucres - applied to the knowledge of textiles. Today, fluorescent manufacturing is not only carried out by the manufacturers of the fabrics or textiles, including the manufacturers of the basic synthetic products, but increasingly also by the housewife who does her laundry with detergents and / or soaps, the flucrescicrende In order to improve the whitening effect and to intensify / cd er ·, fluorescent whitening agents are therefore incorporated into the detergents during their manufacture.

In an effort to give the laundry a more white "appearance lend, the v / ash manufacturers have a similar identity to theirs Fluorescent Weifirnacher products added to

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increases. The use of relatively large concentrations of whitening agent, namely around 2 to 10 kg of whitening agent per ton of detergent, however, often resulted in significant discoloration, and this undesirable discoloration often intensifies when the detergents (detergents, soaps and other detergents) are stored in a more or less pronounced manner damp environment. The lack of just such a discoloration of the detergent powder during the various stages of manufacture is the manufacturer as a control option when making desired progress of the respective W gen production levels. On the other hand, such control of the production progress is difficult or even impossible if the mixture containing the fluorescent whitening agent is causing discoloration during the production of the product.

The Canadian patent 783,566 relates to a salt of ^{4,4 l} -bis- (4-anilino-6-raorpholino-s-triazine-2-ylaaiiiio) -2,2'-stilbene-disulfonic acid and in particular a new crystalline form of the Disodium salt of this acid. This new crystalline

-Product is due to improved properties than optical Labeled bleach.

The sodium salt, i.e. the disodium-4> 4'-bis- (4-anilino-6-morpholino-s-triazin-2-ylatnino) -2,2 '-stilbene disulfonate is a well-known compound that has valuable properties as has fluorescent optical bleaching agent and as a whitening agent and brighteners in detergents for washing textiles.

109845/1936 " ⁵ ^

is set. However, it has been found that this known product is disadvantageous because of its photosensitivity and that this sensitivity to light is particularly detrimental when the product is mixed with white detergents.

According to the manufacturing process described in Canadian patent 783,566, Dinatriuaa-4>4'-bis (4-anilino-6-morpholino-striazin-2-ylamino) -2 »2 '.-Stilbene-disulfonate in the form c is pure ο colored needle-shaped crystals are obtained, and these crystals are distinguished by excellent stability against the effects of light. The process for the preparation of this new crystalline product according to this patent consists in stiiling amorphous disodium-4,4'-bis- (4-anilino-6-morpholino-s-triazin-2-ylarcino) -2,2'- -disulfonate with 1/2 to 5 molecular fractions of aniline or morpholine in an aqueous medium with an initial pH of about 8 to 12 heated to a temperature between about 50 to 20 ° C, to about 80 to 100 $ of disodium 4, 4 ' -bis- (4-anilino-6-morpholino-s-triaz, in-2-ylamino) -2,2'-stilbene-disulfonais are converted into the form of crystalline needles. However, the new crystalline product is also -with a PQ serious The disadvantage is that it is not suitable for use in detergents or detergent products for low temperatures. In addition, the curing effect of practically all fluorescent whitening agents is substantially reduced at low temperatures. Finally, low temperature whitening agents in detergents give yellow stains when the detergents are placed in a spray tower

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recovered for reuse.

The present invention relates to new crystalline forms of 4,4 ^f -3is - / ("4-anilino-6-morpholino-1, 3, 5-triazin-2-yl) -ami: stilbene-2,2'-disulfonic acid with the sum formula C.qH ^ and the following structural formula: ■ ·

The new crystalline product has unusual and completely surprising properties. While, as indicated above, the effectiveness of most flucrescent whitening agents is significantly reduced at low temperatures, the fluorescent whitening effect of the new crystalline forms of the 4, 4 '-BJ s- ^ 4-anil: Lnc-6-iiiorpholino- 1 ₁ 3,5-triazin-2 ~ yl) -amino / ' ^P -stilbene-2,2'-disulfonic acid practically unchanged at low temperatures. In addition to the above-mentioned unexpected property of producing an extremely high whitening effect at low temperatures, the novel crystalline product according to the invention is characterized by a

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-5-

characterized bleaching stability. In contrast to most of the prior art low temperature fluorescent whiteners, the novel crystalline product of the present invention does not cause yellow stains on recovery. He invention sgeniäßen novel crystalline forms of 4> 4 ^l -Bi8 - / ΊΓ4-anilino-6 · morpholino-1, 3, 5-triazine-2-yl) -amino7'-stilbene-2 _J 2 · -. Disulfonic acid thus has the rare and highly unusual combination of properties, namely (1) being a powder detergent with V / ei ß ma before properties _; (2) to bring about excellent fluorescent whitening effects even when used at low temperatures, (3) to have excellent bleaching stability and (4) not to give yellow spots.

The present invention further comprises the use of the fluorescent according to the invention described above Whiteners in detergents, soaps and other laundry products such as bleaches, water softeners, etc.

, The used for the production of the new products according to the invention Starting products are obtained by known processes similar to those obtained, for example, in the US patent 2,762,801. or in Swiss patent specification 321 109 are described. These methods consist in that a KoI disodium 4,4'-diaminostilbene-2,2'-disulfonate or the free Acid, i.e. 4,4'-diaminostilbene-2,2-disulfonic acid (DAS), with 2 moles of cyanuric acid chloride (CC) at a low temperature, i.e. a temperature between about -10 ° and + 10 ° C and before-, -

109845/1936 "**"

preferably between about -6 and + 5 ° C is condensed. A suitable solvent is used for the cyanuric acid chloride, for example, methyl ethyl ketone is used. That as an intermediate product resulting dinatriuin 4,4'-bis (4,6-dichloro-s-triazin-2-yl-amino) -2,2'-stilbene-disulfonate (CG / DAS) is then treated with aniline (2 moles to 1 mole DAS) at a temperature between about 5 ° and 50 ° C implemented, after which the remaining 2 chlorine atoms in

of 4> 4 ^l -Bis- / ~ 2 "-phenylamino-4" -chloro-s-triazinyl- (6 ") - ami stilbene-2,2'-disulfonic acid with morpholine by heating the ^ reaction mixture to a temperature between about 50 ° and

90 C are implemented. The steps described above are carried out continuously in the process, ie without isolating the intermediates. The new stage in the process according to the invention is that the reaction gel for obtaining the desired product, ie the 4,4'-bis- ^ C4-anilino-6-morpholino-1, 3, 5-triazin-2-yl) - amino / stilbene-2,2 ^f disulfonic acid, is acidified.

The novel crystalline forms of the 4> 4 '~ bis- ^^ ["4-anilino-6-morpholino-1,3,5-triazin-2-yl) -amino / - st practice 2,2'-disulfonic acid either as indicated above by acidifying the reaction mixture to a pH in the range between .about 2 and 6 and preferably between about 2 and 3 or, on the other hand, obtained by the fact that the dinatrium salt product obtained after the reaction with morphine is 4.4 ^f -Bis- ^ T4-anilino-6-morpholino-1,3y5-triazin-2-yl) -smino7-stilbene-2,2'-disulfonic acid from the reaction mixture using customary methods

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and is conveniently separated off by filtration, the The product is then washed and acidified to a pH between about 2 and, preferably, about 2 and 3. The stage the acidification of the Hatriuia salt is shown below:

On acidification, the desired product precipitates out of the solution and then by conventional methods such as filtration severed. The product is then dried.

The new crystalline products according to the present invention compare favorably with past fluorescent curing agents far superior properties in that they are unusual are, and are, excellent detergent whiteners low temperatures. In addition to this previously not

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Observed combination of properties form the invention new crystalline products in detergents do not have yellow spots and when they are recovered via a spray tower the products according to the invention also have an excellent one Bleach stability.

The crystalline products according to the invention also go dissolves extremely quickly and can therefore, at low temperatures, i.e. drawn onto fibers at temperatures between about 35 and 60 ° C. Since the products according to the invention thus are available in such quantities that they can be absorbed by the fabric, even at low temperatures, is theirs Effectiveness when washing in cold water is practically the same those when washing in warm water. Accordingly, the products of the invention are ideal for their use suitable for laundry in the household.

Solid detergents including soaps and similar detergent products, to which the fluorescent whiteners according to the invention more likely to be added during each stage of their manufacturing process include anionic detergents such as the alkali salts of alkyl aryl faulfonates, especially alkyl benzene and Alkylnaphthalene sulfonates, alkali salts of sulfates of higher Fatty alcohols or alkali salts of higher fatty acids in which the cationic part consists essentially of sodium ions. in the The following is a typical composition of an anionic Detergent reproduced:

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16 $ liatriUEadodecylbenzenesulfonate

$ 35 sodium tripolyphosphate

$ 5 tetrasodium pyrophosphate

6 fi sodium silicate
• 5 $ V / water

0.5 ^ carboxymethyl cellulose

Remainder to $ 100 i Katriuinsulphate (excluding additives).

The fluorescent whitening agent according to the invention can also be used in non-ionic detergents are incorporated. A typical one Composition of such a product is as follows:

8 fo nonylphenol polyethylene glycol ether r

■ $ 35 sodium tripolyphosphate

$ 5 TetranatriuKpyrophosphat

6 io sodium silicate
8 io water

0.5 9 δ carboxyethyl cellulose Remainder on $ 100: Sodium Sulphate (excluding additives).

The amount of the fluorescent whitening agent added is general "at least about 0.1 to about 1.0 $ by weight the detergent, the soap, the softener or the like. Washing product.

The present invention is illustrated in further detail by the following examples. Unless otherwise indicated, parts are by weight and temperatures than ⁰ C.

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Example I. Production of 4> 4 '-Bis-ZT ^ snilino-D-corpholino-i, 3, 5-triazine-

■ 2,2'-disulfonic acid

100 parts of the I) disodium salt of 4,4'-bismorpholino-1,3, 5-triazin-2-yl) -amino / '- st üben-2,2'-disulfonic acid and 4000 parts v / ater are heated to 00 ° C. with stirring. To this end, 260 parts of a 1.8 normal solution of hydrochloric acid in water are added in one shot so that a pH of 2.5 is established. The mixture is then filtered hot and the precipitate washed with 2000 parts of hot water. The moist material is then vacuumed at 100 ° C

dried, giving the desired product in crystalline form r

is obtained.

The crystalline product of this example is shown by an X-ray diffraction diagram characterized, which shows the following characteristic lines, indicated in ° 2 Θ:

Fairly strong lines at 5.3; 3.9; 11-4; 15.5; 19.8; 21.2 and * 25.8.

The X-ray diagram for this crystalline product is shown in FIG. 1 attached.

Example II

400 parts of water / water are heated to a temperature of 80 ° C. with stirring. For this purpose, a solution of 20 parts of the disodium salt of 4.4 ^l -Bis- ^ r4-anilino-6-morpholino-1,3,5-

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triazin-2-yl) -amino7-stilbene-2,2'-disulfonic acid in 400 parts Water added. Simultaneously, a 1.0 normal solution of hydrochloric acid in water is released at such a rate added that the pH of the resulting solution is kept at 6. After adding the brightener solution, the temperature will rise for a further hour at 80 ° C and the pH is kept at 6. The reaction mixture is then cooled to room temperature and filtered. The precipitate is removed with cold water of salt gcv / ash and then dried in vacuo at 100 ° C, whereby the desired crystalline product is obtained will.

The crystalline product is diffracted by an X-ray diffraction gram characterized, which has the following characteristic lines, expressed in ° 2 Θ:

A strong line at 9 »3; a pretty strong line at 10.1; a strong line at 16.3; pretty strong lines at 18.8; 19.3; 20.0; 23.3 and 24.6} a strong line at 25.5 and one pretty strong line at 28.1.

The X-ray diagram of this crystalline product is - reproduced in figure 3 enclosed.

Example III

The procedure of Example II is repeated except that the pH is maintained at 2 instead of 6.

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The crystalline product obtained is shown by an X-ray diffraction diagram characterized, which has characteristic lines, expressed in ° 2 Θ, as follows:

Pretty strong lines at 3, 4 and 5? 1 ; a strong line 8.9 and pretty strong lines at 9.7; -10.6; 15.9; 16.6; 18.5; 20.4; 21.5; 22.6 and 25.4.

The X-ray diagram of this crystalline product is in the accompanying Figure 2 reproduced.

Example IV

700 parts by weight of cyanuric acid chloride become 200 parts by weight Methyl ethyl ketone and 6000 parts by weight of sis water

give. In-the obtained suspension of the cyanuric acid chloride is at a temperature of 0.5 ° C with stirring within one A solution of 785 parts by weight of the sodium salt of the hour 4,4'-diamino beet-2,2'-disulfonic acid and 200 parts by weight Sodium carbonate poured into 6000 parts by weight of steep water. Then 355 parts by weight of aniline are added in one shot, after which the pH is maintained at 6 to 8 by adding 155 parts by weight of sodium hydroxide dissolved in 155 parts by weight of water will. The yellowish suspension is then stirred and opened Heated at 50 C until all the aniline has reacted. Be afterwards 655 weight steeply morpholine was added and the reaction mixture ons heated with stirring to the methyl ethyl ketone at a temperature distill off from about 100 ° C. The reaction mixture is left then cool to 85 ° to 90 ° C and maintain this temperature while 300 parts by weight of sulfuric acid (98 pounds) within

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from one hour with stirring and adjustment of the pH to 2 to be added. The yellow slurry is cooled and the Pesticide filtered off. The moist product is then dried at 100 ° C in a vacuum, whereby the desired product, the 4,4'-bis - / [4-anilino-6-morpholino-1,3,5-triazin-2-yl) -aminoy £ - stilbene-2,2'-disulfonic acid is obtained.

The crystalline product is indicated by an X-ray diffraction diagram characterized, which is identical to that of Example I.

The product obtained was examined for its waseh-whitening properties. For this purpose, measured concentrations of the white flour product obtained above were added to a typical anionic detergent for washing under difficult conditions; such detergents are discussed above; for this purpose, the detergent and the whitening agent were slurried with about 111 sodium hydroxide solution to form a smooth, homogeneous paste. The paste was dried in a gravity convection oven at 105 ° C. and the resulting dried detergent cake was ground through a sieve with a mesh size corresponding to 20 meshes. The powder was sieved through a 60 mesh screen and the fines were discarded. The detergent powder was then allowed to stand overnight at a relative humidity of about 85 °, after which a parb measurement was carried out. The hue of the powder was

-14-

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determined in a Hunter Color Difference Meter, Model D-25, with "L", "a" and "b" units ending / ending. A "whiteness value" was calculated according to the equation W = L + 5a-3b (see PS Stensby, "Soap and Chemical Specialties, April, May, July, August, September 1967 issue"), the higher the value , the greater the "whiteness ^{11 of} the powder. Hur whitening values with a value above 75 can be called "white." to be viewed as.

"All wash tests were performed in a Terg-O-Tometer (150 rpm)

a treatment time of 10 Hinuten performed with 600 ml of water, 20 g of cotton fabric and 1 g of detergent (containing 0.4 i <> a whitening agent full strength) or- 60 seconds before addition of the fabric bleaching were pre-dissolved. In the bleach tests, the wash liquor was exposed to 200 ppm FaOCl before adding the fabric. The washed fabrics are washed out under running tap water and dried in the dark by draining. The tissue fluorescence was below

\ Measured using a Lumetron colorimeter, which is connected to a

-Equipped with a mercury lamp and an injection device is; fabric color was measured using a Hunter Color Difference Meter certainly.

The characteristics of the product of the above. Example IV were with a commercially available whitener for low Temperatures compared.

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Wash-white reacher effect

Whitener A *

Product according to Example IV performance ability

Hunt guessed

LI a) b I L + 5ä-5b 95.1 -2, ö 8.1 63.0

94.3 0.3 3.7

84.2

Whitener, 13 A * 0 ° P Lumetron 392 I »I Hun ter values L + 3a-3b Hunt got values b L + 3a-3b (54 ^ C) Product according to
game IV values 171 94.8 a D. 122.4 a -5.9 122.4 Whitener, 80
(25 * C) 392 420 95.0 3.3 -5.9 -126.2 3.3 -2.3 106.4 A * At- 420 261 3.6 -6.8 1.5 -6.8 ■ 126.2 Product according to
game IV ⁰ 1 94.7 120.2 3.6 -4.0 114.0 Bleaching stability 367 95.2 3.1 -5.4 125.5 2.3 r
Whitener At- 401 3.5 -6.6 A * ITaOCl lunte tron- (200 ppm) values 94.8 Product according to
Example IV - 95.0 + 95.0 95.1 +

* = Commercially available whitening agent 4,4'-bis- / J4- anilino-6- ^ b "is- (2-hydroxyethyl) -amino7 ~ 1,3,5-triazin-2-yl7-aminostilbene-2,2 '-disulfonic acid.

Fie ckenbil ^f clung

Compared to other low temperature whiteners currently on the market, the crystalline one is preferable Product according to Example IV no yellow staining of the detergent a when it is recovered by spray drying.

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As indicated above, the new crystalline product according to the present invention is also the disodium-4,4'-bis- (4-anilino-6-morpholirio-s-triazin-2-ylaniino) -2,2 ^! - stilbene disulfonate according to the Canadian patent 783,566 to the effect that the last-mentioned product is not suitable as a whitening agent in detergents and laundry detergent products for low temperatures. The above comparison data clearly show the superiority of the crystalline product according to the invention both with regard to the washing-whitening effect, the effectiveness at high and low temperatures as well as with regard to the bleaching stability.

Uie X-ray diagrams of the crystalline according to the invention Product were determined according to known methods of determination for powder obtained, for example, from Krug and Alexander in "X-ray Diffraction Procedures for Polycrystalline and Amorphous Materials ", John Wiley and Sons, New York, N.Y. (1954), particularly" Pages 235 et seq .; a goniometer equipped with a "proportional counter" from the company U.V. Philips G-loeilampen Fabrieken, Eindhoven, Holland used. The instrument records the actual intensity of the deflected rays along the vertical axis relative to the Diffraction angle 2Θ using a CuK ^ radiation. The interplanar distances d were subsequently given in Angstrom units from the diffraction avoids using the Bragg equation n.?^=2d. sin θ is calculated. The values obtained are accurate in the $ 2 range, and for the most part, in particular for d-values of less than 10 A, the -17-

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Fluctuation less than $ 1. This range of fluctuation is therefore ■ when interpreting the description and the following To consider claims.

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Claims (1)

Patent claims: ■ ΐ. Crystalline 4,4 '-bis- _/! fC4-anilino-6-morpholino-1,3,5-triazine 2,2'-disulfonic acid. 2. Crystalline 4.4 ^l -Bis- _/ /T4-anilino-6-morph.olino~1,3,5-triazin-2-yi)-aminoJ7--stilbene~2,2'-disulfonic acid according to claim 1, characterized by an X-ray diffraction diagram with the following characteristic lines, expressed in ° 2 Θ: Fairly strong lines at 5.3; 8.9; 11.4; 15.5; 19.8; 21.2 and 25.8. 5. Crystalline 4,4'-bis- / r4-anilino-6-morpholino-1,3,5-trJazin-2-yl) -amino / '- stil'ben-2,2 · -Disulfonic acid according to claim 1 or 2, characterized by an X-ray diffraction slide » gram according to Figure 1. 4. Crystalline 4,4 ^r -Bis- ^ f4-anilino-6 ~ niorpholino-1,3,5-triazin-2-yl) -amino7-stilbene ^ 2,2'-disulfonic acid according to claim 1, characterized by an X-ray diffraction diagram with the following characteristic lines, expressed in ° 2 et A strong line at 9.3; a pretty strong line at 10.1; a strong line at 16.3} pretty strong Line at 18.3; 19.3; 20.0; 23.3 and 24.6; a strong Line at -25.5 and a pretty strong line at 28.1. 109845/1936 5. Crystalline 4.4 ^l -3is- ₍ / j4-arilino-6-morpholino-1, 3s5-triazin-2-yl) -amino7-stilbene-2,2'-disulfonic acid according to claims 1 and 4, characterized by a Höntgen ray diffraction diagram according to Figure 3 • 6. Crystalline 4 * 4'-bis- / r4-anilino-6-morpholino-1,3,5-triazin-2-yl) -amino / -stilbene-2,2'-disulfonic acid according to claim 1, characterized by a Röntgenatrahlendiffraktionsdiagramm with the following charaktei ¹ istic lines, expressed in 2 Θ: Fairly strong lines at 3, 4, and 5.1; a strong Line at 8.9 and fairly strong lines at 9.7; 10.6; 15.1; 16.6; 18.5; 20.4; 21.5; 22.6 and 25.4 7. Crystalline 4.4 ^l -bis- _/ / j4-anilino-6-morpholino-1,3,5-triazin-2-yl) amine £ 7'-stilbene-2,2'-clisulfonic acid according to claims 1 and 6, characterized by an X-ray diffraction diagram according to FIG. 2. 8. Process for the preparation of crystalline 4,4'-bis- / T4-anilino-6-morpholino-1,3,5-triazin-2-yl ) -amino_7-stilbene-2,2'-disulfonic acid according to claims up to 7 by reacting cyanuric acid chloride with 4,4'-diaminostiiben-2,2'-disulfonic acid or an alkali salt thereof, reaction of the product obtained with aniline and in a subsequent one Stage with morpholine, characterized in that the obtained Disodium salt of 4,4'-bic- ^ r4-anilino-6-morpho- 109845/1936. lino-1,3,5-triazin-2-yl) -amino7-stilT3erx ~ 2,2'-disulfonic acid is acidified. . 9 · The method according to claim 8, characterized in that the disodium salt of disulfonic acid obtained as an intermediate product separated from the reaction mixture and then acidified to form the desired product. 10. The method according to claim 8, characterized in, ö.aß | · The reaction mixture to form the desired product is acidified. - · ■ - Process according to claims 8 to 10, characterized in that that the acidification takes place to a pH between about 2 and 6. 12. The method according to claims 8 to 11, characterized in that that the acidification is carried out using a mineral or an organic acid. 13. The method according to claims 8 to 12, characterized in, that the mineral acid used is sulfuric acid or hydrochloric acid. 14. Process according to Claims 8 to 12, characterized in that that als.organische acid formic acid or acetic acid is used. 10984S / 1936 15 · Process according to claims 8 to 14> characterized in that that the acidification to a pH between etv / a 2 and 3 takes place. 16. Use of crystalline 4,4'-bis- £ [4 ~ anilino- · 6-morphülino-1,3j5 ~ tria2in-2-yl) -amino / ^r -stilüen ~ 2,2 '~ disulfonic acid according to claims 1 to 7 as optical brighteners, preferably in detergents. 17 · A detergent, soap or V / a schmitt egg product, labeled by a content of at least $ 0.1 of a compound according to parts 1 to 7 109845/1936 ι Ml ■ Blank page