DE2011916B2 - Quaternary 1,2.4-triazol-l-yl derivatives of the stilbene series, process for their preparation and their use as optical brightening agents - Google Patents

Description

CH = CH

in which A has the meaning given above, in the presence of inert organic solvents with quaternizing agents of the formula R — An CH = N

--R

To ^e

Alkyl group and An denote a colorless anion. 2. Process for making the compounds according to claim 1, characterized in that 1,2,4-triazole derivatives of the general formula II

N = CH

CH = N

at temperatures from about i 00 to 250'C.

3. Use of the compounds according to claim 1 as optical brighteners.

In DE-OS 19 19 209, inter alia, compounds of the general formula II

has been proposed in which A is a fused benzo, naphtho [1,2] or acenaphtheno [4,5] ring means, where an existing benzotriazole radical in the 5- and / or 6-position is replaced by one or two lower alkyl or alkoxy groups are substituted, R is a lower alkyl group and An is a colorless anion.

In contrast, the invention relates to corresponding compounds which are in the Η-position of the nitrogen atom 1,2,4-Triazol-1-yl radicals with a lower alkyl group are quaternized. The anion is a colorless anion.

The compounds according to the invention are prepared by the process according to claim 2 above. The compounds of the general formula II proposed in DE-OS 19 19 209, which are used as starting materials, are according to there specified procedure-accessible.

The following can be used as quaternizing agents, for example: alkyl halides such as methylene chloride, methyl bromide, ethyl chloride, ethyl bromide, propyl bromide and n-butyl bromide, and also sulfuric acid or Arylsulfonic acid esters such as dimethyl sulfate, diethyl sulfate, benzenesulfonic acid methyl ester, toluenesulfonic acid methyl ester and toluenesulfonic acid ethyl ester.

Inert organic solvents which can be used are, for example: o-dichlorobenzene, 1,2,4-trichlorobenzene, T. dichlorobenzene mixtures, Λ-methylnaphthalene and Λ-chopmaphthalene.

In the dissolved state, the compounds according to the invention show a more or less pronounced one Fluorescence and are suitable for the optical brightening of a wide variety of organic materials. The compounds according to the invention are particularly suitable for the optical brightening of copolymers

ile with a minimum content of approx. 85% polyacrylonitrile. They show excellent results on these materials Whiteness levels, preferably in the acidic range on polyacrylonitrile fibers, at pH values between about 2 and 6, in particular about 3 to about 4, can be used.

The compounds according to the invention are distinguished by their stability in sodium chlorite bleach flotites. With these connections it is possible to use the

4>! Combined use with sodium chlorite as a bleaching agent on polyacrylonitrile fibers, excellent degrees of whiteness to achieve. It can be used both at temperatures below the boiling point of water and at ! higher temperatures (so-called HT conditions)

■) () be worked.

Compounds according to the invention which are sparingly soluble in water can be used dissolved in suitable organic solvents or in aqueous solvents Dispersion, preferably with the aid of a

•> i dispersants are used. As a dispersant, for example soaps, Polyglycol ethers of fatty alcohols, fatty amines or alkylphenols, cellulose sulfite waste liquors or condensation products of optionally alkylated naphtha

colin sulfonic acids can be used with formaldehyde.

The compounds according to the invention can furthermore contain high molecular weight organic materials or are added during their deformation. So you can use them in the production of films, foils, tapes

b => or add molded bodies to the molding compound or dissolve in the spinning compound before spinning. Suitable compounds can also be used before the polycondensation, as in the case of polyamide-6,6 or the polymerization

are added to the low molecular weight starting materials.

The amount of the compounds of the general formula I ₁ to be used according to the invention, based on the material to be optically brightened, can vary within wide limits. It can easily be determined by preliminary tests and is generally between 0.01 and 1%.

The compounds according to the invention can also be mixed with dyes, chemical bleaches, Finishing agents, softeners, detergents and, in particular, cationic laundry aftertreatment agents are used.

example 1

A fabric consisting of at least 85% polyacrylonitrile was in a dye jigger with a Treated bleaching liquor, which per liter is 3 g of sodium chlorite as bleach and 14 g of sodium nitrate as Corrosion protection, formic acid to adjust pH 3.5 and 0.1% of the fabric weight of the Compound IH (table)

The liquor was ^{heated to 85 3} C in 30 minutes and held at this temperature for a further 60 minutes. The mixture was then heated to boiling within 15 minutes, left at the boiling temperature for 30 minutes and then slowly ^{cooled to 50 °} C., the temperature being reduced by about 1 ° C. per minute.

The material treated in this way showed an excellent degree of whiteness of after rinsing and drying neutral shade.

The compound III (table) was prepared in the following way:

41.4 parts by weight of 4- (l, 2,4-triazol-1-yl) -4 '- (naphtho [1.2-d] triazol-2-yl) stilbene were in 1000 parts by volume of 1,2,4- Stir in trichlorobenzene and brought into solution by heating to 150 ° C. Then it was added dropwise at this temperature

20th

25th half an hour 21 parts by volume of dimethyl sulfate, the quaternary product precipitated as a light yellow, finely crystalline precipitate. The mixture was stirred for a further three hours at 150 ^° C. and the reaction mixture was then allowed to cool to room temperature with stirring. The precipitated product was filtered off with suction, washed with trichlorobenzene and benzene and dried. After drying, 53.2 parts by weight of compound III were obtained as a pale yellow powder with a decomposition point of 266-267 ° C

Example 2

A strand yarn material consisting of at least 85% polyacrylonitrile was used in a dyeing machine conventional design treated with a liquor, which oxalic acid to adjust pH 4 and 0.1% des Weight of the compound HI (table).

The liquor was up within 45 minutes 100'C heated and the goods for 45 minutes this temperature was then slowly cooled to 50 ° C., the temperature being reduced was lowered about 1 ° C per minute. The material treated in this way showed one after winding and drying excellent whiteness of bluish fluorescence.

Compound V (table) was prepared - analogously to the compound described in Example I - by dissolving 42.4 parts by weight of 4- (1,2,4-triazol-1-yl) -4 '- (5,6-dimethoxy -benzotriazot-2-yl) -stilbene in trichlorobenzene and reaction with 21 parts by volume of dimethyl sulfate at 170 ⁰ C.

After suctioning off, washing and drying, 56 parts by weight of a greenish yellow powder were obtained Decomposition point 284 ° C. The compounds IV and VI (table) were in the same way in the Solubility corresponding temperatures of 150 resp. 160 ° C.

N = CH

CH == N

CH ₃ CHj-O-SOj

AT-

Zerjelzungspunkl ° C

Absorption / _, in πΐμ ('· ΙΟ " ⁴ )

Fluorescence in dimethylformamide

266-267 369 (7.39)

reddish bluu

N -

290-291 376 (too difficult to dissolve) greenish blue

continuation

Decomposition point ° C absorption X _mMX in m / i

( _f · ΙΟ " ⁴ )

Fluorescence in dimethylformamide

CH ₃ O

X>

278 365 (6.44)

greenish blue

CH ₃

284

369 (7.22)

reddish blue

Comparative experiments

The lightening effect of the following compounds was compared

1. Compound of formula III

2. Compound of formula VII

-SO ₂ - NH- (CH ₂ J ₃ - N ^ä (CH ₃ ) ₃ CH ₃ -OSOj

Commercially available brightener for brightening polyacrylonitrile

1. Development of PAN75

Fabric made from staple fibers of the PAN 75 type was heated in the liquor ratio for 45 minutes at 98 ° C 1:40 treated with

a) 0.1% by weight (based on the weight of the goods) of the compound III

2 g / l sodium chlorite

1 g / l bleaching aid

2 g / l potassium hydrogen tartrate 4 ml / I acetic acid

b) 0.1% by weight (based on the weight of the goods) of the 4-, Compound VII

1 g / 1 potassium hydrogen tartrate

After rinsing and drying, the whiteness obtained were measured on a colorimeter correct and calculated according to the formulas of Berger and Stensby. The following values were obtained:

WG Berger WG Stensby

Compound III (Model IA) 137 135

Compound VII (sample IB) 130 130

The untreated raw material (sample R 1) has the following

Whiteness: Berger 74; Stensby 79 the same recipe was used as above under a) for Brightener III, i.e. Brightener VII was also used here together with a bleach used. The following degrees of whiteness were measured:

V / G Berger WG Stensby

Compound 1 (sample 2 A) 124 127

Connection 2 (sample 2 B) 106 113

Raw material (sample R 2) 67 74

3. Lightening of PAN 16 / PAN 36 50/50 (Mixture of basic and acid modified polyacrylonitrile)

The lightening was carried out according to the method described under 1., with both brighteners together with a bleach according to recipe a) were used. The following degrees of whiteness were obtained measured:

WG Berger WG Stensby

2. Lightening of high-bulk polyacrylonitrile fabric

Compound III (sample 3 A) Compound VII (sample 3 A) Two fabric samples made from high-rise polyacrylonitrile 05 raw material (Must 'r R 3)

were analogous to that described under 1. above

Procedure healed, whereby 1 panel with 9 patterns was laid out for both brighteners.

98 108 73 89 35 53

Claims (1)

Claims: 1. Quaternary 1,2,4-triazol-l-yl-stilbenes of the general formula I. N = CH CH = CH where A is a fused benzo, naphtho [1,2] or acenaphtheno [4,5] ring, where a Benzotriazole residue present in the 5- and / or 6-position by one or two lower alkyl or Alkoxy groups is substituted, R is a lower one