DE1811715A1 - Triazinylaminostilbene derivatives - Google Patents

Description

. ■■ ': ■■' ;: ρ- ■

FARBENFABRIKENBAYERAG

TEVERKUSEN-BaytHmk Patent department “My / Rb

Nov 28, 1968

Triazinylaminos tilbene derivatives

The present invention iet the style-en * Getting Connected the formula

R _n - cf ^ C-HH- ^ ^ - ■:? »= .- 'JK S V. Γ" ^{J <} ^ C - R.

II ^Vi \ ^ -r i (D

N (GH ₂ CH ₂ OHJ ₂ H (CH ₂ CH ₂ OH) ₂

where R for the thatch -HH - ^^ - SO, H and

R ₁ for the thatch -NH-

stands, Bowie their SaIae and mixtures of compounds of the formula I with Vei. Findings of the formula

R ₁ -C C-HH- ^ VcH = CH-f V / iH-C ^ CR _n ? II)

^L » ti \ / \ J u ι 1

SO, H SO ₃ H κ κ

LeA 11905 009825/2110

BATH ORIGINAL

and the formula

R-C C-HH-P NVCH = CH- ^ \ VNH-C ^ C - R

NH SO, HS (I ₁ HN »

H (CHpCH ₂ OH) ₂ N (CH ₂ CH ₂ OH) ₂

and their salts, where R and R-. are as defined in formula (I), in particular by reaction of cyanuric chloride in a molar ratio of about 1:. 1 with a mixture of p-aminobenzenesulfonic acid and m-aminobenzenesulfonic acid, especially a mixture of 30 to 25 wt% of m-aminobenzenesulfonic acid and 70 to 75 wt. ^ C p-aminobenzenesulfonic acid, subsequent reaction in a molar ratio of about 2: 1 "with 4.4 ^l -diaminostilbene-2,2'-diBulfonic acid or its salts and further reaction in a molar ratio of about 1: 2 Hit diethanolamine in an Mixtures obtained in a known manner, as well as their use as brightening agents, in particular in combination Hit high-finishing agents from acidic and saline aqueous liquors.

Suitable salts are in particular the alkali salts, especially the Ha and K salts and also alkanolamine salts, for example Ethanolamine salts.

The preparation of the mixtures of the compounds (I), (II) and (III) takes place in a manner known per se, for example

009825/2110

J.025-242 disulfonic acid, by the process of the French Patent Kr. I.I55.932 or U.S. Pat. No. by reaction of cyanuric chloride with Aminobenzoisu'folsäure, 4,4'-diaminostilbene ?, 2 'and Methanolamine,

Stilbene compounds of the formula ill) Bind already from aer French patent no. «..} 35 · ° 32 began, such of the formula (III), for example, also from the US patent

No. 3.O25.242-. The mentioned- i-style combinations are ™

used as optical brighteners, but have the disadvantage that their aqueous acidic solutions, especially at pH values below 5.5 and the presence of salts, become unstable after a short time and show precipitates.

The consequence of this is that such solutions are immediately followed Their production must be used, otherwise lower lightening effects are achieved - for example in the simultaneous optical brightening and refinement.

■■ · ■ ■ ■ ■■■ - ■■■ - ·., ... ,. .

Such disadvantages are surprisingly shown. Mixtures of the stilbene compounds I to III, provided they are through. Mixed condensation of cyanuric chloride with a mixture of 3 / Ό to 25 wt., 5t m-Aannobenzclsüifonicäure and. 70 to -75 .Qew · ^ ■ p-Amin.o-ben-.z.olsulfonic acid or their. Salts in a molar ratio of about 1: 1, subsequent reaction with 1 , 4 '-Diaminoatilben --- ¹ , ^' -disulphonic acid or .ieren-Balzen, 4.-. , Moivertälnis of about 2: 1 and following

": ??: = ■ 2 '1 b

BATH ORIGINAL

Reaction with diethanolamine in a molar ratio of about Is2 were made, not. Both mixtures of separately prepared compounds (II) or (III) and the pure ones Compounds (II) or (III) and by co-condensation of m-aminobenzenesulfonic acid and p-aminobenzenesulfonic acid or their salts in mixtures obtainable in other than the proportions given above show this surprising Acid and salt stability not.

With the simultaneous optical brightening and high refinement of textile materials are aqueous preparations. of compounds such as methylol urea, dimethylol urea, Dimethylolethylene urea, dimethylol dihydroxyethylene urea, Tetramethylol acetylenurea, dimethylolpropylenurea, Polymethylolmelaminen, Dimethyloltriazinonen, Alkylen-biemethylolurethanen, butadiene diepoxide, diglycidäthera, Divinyl sulfone, or compounds that are subject to condensation \ conditions divinyl sulfone, together with optical Brighteners applied to the fiber materials and then in the presence of acidic catalysts; such as ammonium chloride, zinc chloride, magnesium chloride, zinc nitrate, ammonium nitrate, Hydrochloric acid or sulfuric acid thermally fixed.

Such processes are for example in the Austrian patent specification 196 343, SVP (Fachorgan für Textilveredelung), Volume 19, 1964, pages 459-465 and Pischer-Bob "sien, Internationales Lexikon, 1966, page 1487).

ΟΟ982 .; 5 _? /: 2; 1Λ _: α,. ■ - 4 -

example 1

In a fine dispersion of 250 g of cyanuric chloride in 1800 ml of water at about 5 ⁰ G is allowed with stirring over ca. voti 3NC minutes, a potassium hydroxide solution fflit pk 7 eiftgeätellte solution of 176 g p-lttinbbett20lsülfönsa "IIRE üiid Ö3 g ifl-Attitiöbenzbisüifbhsäure run in * whereby the ifcetjöiöratür rises from Ϊ5 to ¹ 25 ⁰ G. Mäh leads 1 hour at 25 ⁰ C area efhitit to 60 ⁰ C and iflit SödalöMÜhg feitieÜ i) M-tert of 7 putty. Now there is niätx in the course of about 30 minutes with fine tfatföiilaüge on ρίί 7 geötellte Aqueous lööiihi voué 220 g of 4,4'-Diaffiinostilben ^2J2-f -diöüifonaäür§ and 112 g Hätriümbicarbonat to, said mixture is heated to ÖÖ to 85 ^0C. it holds 1 would in this (temperature, sets 212 g tiiäthanoiäffliti and ISO g Nätriütiibibärböti & t * heated äüf 9Ö ^east C ütld fifth 1 hour at this temperature. ÖIE resulting solution is clarified, äüf at 70 ⁰ C with hydrochloric acid bli 4 * 2 provided and abgeöaügt the precipitated free booze asl TTIT 3 $ ±% & t itoinsaizlösüti g iewäscheti. M & feüöhte jpfödukt wifd iti barrels dispersed and with tfätfbnläfe eitt pk-teft tone 7 einfe-. represents. The iiä-ilfiüiilääiz düröh ffööMeä is isolated from this active. One obtains äö 75Qg tfbckeües ffddükt (A).

009828/2110 ORIGINAL BATHROOM

181171B

Product A represents one of the following compounds B, C and D represent: '....- "

~. CH = CH

/ - »left

H ^

äüä ä- U

örhalten tääii äie

JMoÜ sfisiö

g f

üdbn ϊ §ίτί§ΐί

BATH

Compounds of the formula B or C.

Testing of acid stability and whitening effect

2 g of each of the brighteners A, B and C make up one liter added to an aqueous liquor containing the following additives:

13 g of magnesium chloride

95 ecm of an aqueous polypropylene urea solution (4Ο-Ί5 ^ ig of the average molar weight: 360; N ₂ content 13.9 ** »)

15 ecm of an aqueous gr-r. Polyacrylate suspension (40 20 ccai of an aqueous polyethylene sun board (30

and adjusted to pH 5 with acetic acid. From the liquors with the brighteners B and C, the brighteners partially separate out after a short time. The liquor with the brightener A is stable for at least 12 hours B. In the case of the refinement and lightening of cotton, which is carried out in the usual way with the liquors, liquor A results in clearer and more brilliant lightening * than liquors B and C.

Le A 11 905 CC 98 25 '21 10

BATH ORIGINAL

Claims (1)

Claims The otilbene compound of the formula NH-G C-R N (CH ₂ CH ₂ OH) ₂
where R for the remainder -Nrf - ^^ - S0, H and N N N (CH ₂ CH ₂ OH) ₂ for the rest -NH- stands and their salts. Mixtures of stilbene compounds of the formulas ^R i- ^X C-NH- / ^) - CH = CH N., N N (CH ₂ CH ₂ OH) ₂ 50, H SO ₃ H NH-C NN »N (CH ₂ CH ₂ OH) ₂ ■ ρ _ r
R ₁ -. C-MI - // VCH = CK - (/> HH-C ι MV ⁷ 1 NN SO ₃ H SO ₃ HN N (CH ₂ CH ₂ OH) ₂ N (CH ₂ CH ₂ OH) ₂ 009825/2110 Ie A I! QC5 BATH Air "'· - ■ ii-yf'- -: RIGMC R - C ^ '^ C-NH- / ^ CH = CH- / VnH-C ^ N 0O ₅ H SCi ₅ HN ^ j N (CH ₂ CH ₂ OH) ₂ N (CH ₂ CH ₂ OH) ₂ wherein R stands for the radical -IH-f7-S0, H and R ₁ for the remainder -NH- ^ ~ ^
or their salts. 3) By the reaction of cyanuric chloride in Molverhältnisnis of about 1: 1 with a mixture of 30 to 25 wt ^ m-aminobenzenesulfonic acid and 70 to 75% by weight of p-aminobenzenesulfonic acid or salts thereof, followed by reaction with 4,4'-diaminostilbene.. 2,2'-disulfonic acid or salts thereof in a molar ratio of about 2: 1, and following reaction with di- M ethanolamine in a molar ratio of about 1: 2 brightening agent obtained. 4) Process for the preparation of the stilbene compounds of claim 2, characterized in that one cyanuric chloride Reacts in a molar ratio of about 1: 1 with a mixture of m- and p-aminobenzenesulfonic acid or its salts, the reaction product in a molar ratio of about 2: 1 with 4,4'-diaminostilbene-2,2'-disulfonic acid or theirs 0 0 9 8 25/2110 Le A 11 905 - 9 - CONSTRUCTION ORIGINAL 181171 F Brings salts to react and the resulting reaction product Reacts amine in a molar ratio of about 1: 2 with diethanol. 5) Process according to claim 4, characterized in that a mixture of 30 to 25 wt. # M-aminobenzenesulfonic acid and 70 to 75% by weight of p-amynobenzenesulfonic acid or their salts are used. 6) Use of Stilbenverbindungen.der claims 2 and 3 as a lightening agent. 7) Use of the stilbene compounds of the claims 2 and 3 for simultaneous optical brightening and high-quality finishing of textile materials. Le A 11 905 ^ 10- 009825/2110 BAD ORfGINAL