DD145017A3 - PROCESS FOR PREPARING STYLENE-based lightening agents - Google Patents

Abstract

The invention relates to brightening agents based on stilbene in the β-crystalline form. It already is at 20 ° C to the intermediate of cyanuric chloride, 4,4'-diaminostilbene-2,2'-disulfonic acid and Aniline per mole of 2 mol of morpholine or aniline added and with sodium hydroxide solution to a pH of 12 set. In a closed vessel under autogenous pressure is heated in it, to 110 to 130 ° C and the Leave reaction mixture in this temperature range for about an hour. This procedure brings the brightener in the ß-form in good yield at high utilization of the apparatus and against the previous methods with significant time savings. The brightener serves as an additive to detergents

Description

^ ¥ 5

VEB CHEMIEKOIiBINAT BITTERIi ¹ ELD Bitterfeld, 9. 6 »1977

1899

Process for the preparation of stilbene based lightening agents

Μίί £ §ί ^^

The invention relates to a process for the preparation of derivatives of 4 _s 4 ^f ~ bis- ~ ~ triazinyl amino-2,2 ^f -disulf oic acid in the B-crystalline form according to the following formula

f?

C = N ^ / Γ ~ Λ NC

N C-HH-V V- ^{CH = GH-} V \> - MI - C ^ N

wherein R represents a Morph.olin ™ or Anilinrest «, These compounds are used as optical brighteners in Waschmittelη.

Charact er is t i.k the b eka η nt e η t ep h n c h ict s solving

Stilbene compounds of the above formula occur in two different crystal forms, which vary in color and color

- 2 - 177 ^ i ι 1899

differ from the X-ray diffraction diagrams. From the detergent manufacturer, the use of the white B-crystalline Eorm is preferred, since the use of the yellow & C form leads to a significant discoloration of the detergent, which can be exacerbated by unfavorable storage of the powder. ,

In DL-IB 115 299 a method is described in which initially in a known manner, the replacement of the chlorine atoms of cyanuric chloride in 3 Einzelstiif s at the temperature ranges 0 to 5 ⁰ G, 20 ⁰ C and 70 to 90 ⁰ G while maintaining certain pH Value conditions by reaction with 4,4 ^f -Diaminostilben ~ 2,2 ⁱ -disulfonic acid, aniline and morpholine or aniline again. Taking into account the reaction times which are sometimes up to several hours for large-scale production, there is initially an amorphous to slightly crystalline yellow suspension, which is then without intermediate isolation of the optical brightener at temperatures from 110 to 120 ^° C. while adjusting to a pH of about 11 is converted into the white, crystalline ß-form. In practice, so when working in large stirred vessels, additional difficulties by strong foaming, which has a very negative impact on optimal equipment utilization, on the exact maintenance of the required pH conditions and on the reaction times, especially the last implementation and the Swap out ".

Object of the invention

The object of the invention was to develop a process which allows a more favorable space-time yield while the product is otherwise at least of the same quality.

presentation; of the essence of the invention

It has now surprisingly been found that the process for the preparation of the optical brightener of the above

199 51

- 3 - * * * 1899

Formula in the ß ~ form abbreviate sharply and thus can make more rational, if, after completion of the second reaction stage, the cyanuric _s 4 <.4 ⁵ ~ diaminostilbene ~ 2j2 ^f -disulfonic acid and aniline prepared in a known manner in an aqueous phase intermediate compound , 4 -'-BiS- /. 2 ^t '-phenyl-amino ~

fonsäure per mole with 2 moles of morpholine or aniline and sit sodium hydroxide solution until a pH of 12 at 20 ⁰ O added5 then heated rapidly in a closed vessel under autogenous pressure to 110 to l30 G and in this temperature range with further charges about 1 Hour is left.

In evaluating the production process described so far in the literature, the possibility of such a reaction was not expected, since in the resulting strongly alkaline reaction medium at least partial hydrolysis of the chlorine atoms of the above-mentioned intermediate to undesirable by-products is expected, in which one or both chlorine atoms be replaced by one or two hydroxyl groups "However, contrary to expectations, this does not occur"

The yields of the optical brighteners obtained by the new process are surprisingly higher in very good quality than those achieved in the DL-PS II5 299 Example 1, "The new space-time yields clearly show advantages" So it is possible ., To reduce the hitherto necessary reaction times for the total synthesis uru 20 % while increasing the production batch by 30 % * The fact that the necessary for the pressure stage pH of 12 is already set at 'room temperature, as a further advantage of the apparatus already at 20 ^ C are closed and the 3 =. Reaction _step that is, the reaction with morpholine or aniline, together with the conversion reaction in the ß-form in a manufacturing process run, with no "foaming occurs. This in turn allows the Aoparate much, be utilized to a greater extent. Also .ist

 - 4? in 1899

the new reaction procedure also in terms of compliance with the necessary health and safety regulations much cheaper, since. No need for sampling at elevated reaction temperature for analytical purposes.

embodiment

To further illustrate the invention serve the following example:

In the 10 nr stirring apparatus, 1 200 1 of water, 3 200 kg of ice, 200 kg of cyanuric chloride and 15 1 Protektollösung 10% ig (Ligninsulfonsäurelösung) submitted and at 0 to 5 C 2 510 1 4,4- ¹ -Diaminostilben-2 _? 2 ^f -disulfonic added in a concentration of 62/1 with stirring in 30 minutes. At 0 to 5 ⁰ C in about 30 minutes ca _o 530 1 10% sodium carbonate solution is added so that the pH does not rise above 5. At this temperature the suspension is stirred for 60 minutes. Thereafter, the completion of the reaction by diazotization and coupling reaction of a sample taken is checked. Now allowed at 5 "run to 10 ⁰ G via a measuring vessel 97j3 kg of aniline. The pH value falls thereby to be 3 to 4 weight by re-feed of a 10% sodium carbonate solution (500 to 55O 1) in about 30 minutes, the _o pH regulated to 6 and the suspension is heated to 20 ⁰ G. After stirring for 60 minutes, the completeness of the reaction is controlled. then allowed to run 97 "3 kg of morpholine and 120.1 concentrated sodium hydroxide solution over measuring vessels, checks the pH ( it must be 12), the stirring apparatus closes and heated with stirring, the suspension rapidly to 110 C. After one hour of reaction time, the brightener suspension is filtered after sampling for operation control at a temperature of 100 ⁰ G and washed free of mother liquor by means of saline 9 ^ 0 to 950 kg paste on white

triazinyl received ~ (6 ^H) -amino_7 'stilbene disulfonate 2.2 ^J, corresponding to a yield of 96% of th _e.

Claims (1)

1899 Pa t e Qt a ηsp.ruc h Process for the preparation of stilbene based tanning agents of the formula tv "GH = SO Na NH -G _x / M = O _x wherein R is a morpholine or an aniline radical, in the B-crystalline Opm _s, characterized in that the prepared from cyanuric chloride, 4 _s 4'-Diairiinostilben-2,2 ^f -disulfonic acid and aniline in a known manner in aqueous phase Zwisciienverbindung ^ί ^ J4 ^! - · Up ™ / ~ 2 ^lt -.phenylaülino - ^ i ^'s "chlorine" 1 ^ϊ! _s 3 ^ί! J5 ⁿ · triazinyl ~ (6 ^M) -aniiDü _ / - _s * offset stilbene "2 2 -disulf oic acid per mole with" 2 moles of morpholine or aniline and with sodium hydroxide until reaching a pH of 12 at 20 ⁰ G, then heated rapidly in a closed vessel with stirring under autogenous pressure to 110 to I30 ⁰ C and left in this temperature range with further stirring for about an hour v / ird. Ebg / Ä k