EP0238446B1 - Mélanges d'agents de blanchiment optique - Google Patents

Mélanges d'agents de blanchiment optique Download PDF

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Publication number
EP0238446B1
EP0238446B1 EP87810151A EP87810151A EP0238446B1 EP 0238446 B1 EP0238446 B1 EP 0238446B1 EP 87810151 A EP87810151 A EP 87810151A EP 87810151 A EP87810151 A EP 87810151A EP 0238446 B1 EP0238446 B1 EP 0238446B1
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EP
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Prior art keywords
mixtures
weight
benzonitrile
formula
benzene
Prior art date
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EP87810151A
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German (de)
English (en)
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EP0238446A1 (fr
Inventor
Leonardo Dr. Guglielmetti
Hans Rudolf Dr. Meyer
Dieter Dr. Reinehr
Kurt Dr. Weber
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF Schweiz AG
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Ciba Geigy AG
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Classifications

    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06L—DRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
    • D06L4/00—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs
    • D06L4/60—Optical bleaching or brightening
    • D06L4/65—Optical bleaching or brightening with mixtures of optical brighteners

Definitions

  • Optical brighteners are often used as mixtures of two or more different types because such mixtures have a synergistic effect in that the degree of whiteness of the mixture is higher than the degree of whiteness of the same amount of the individual components.
  • EP-A-30917 discloses mixtures of optical brighteners composed of 51 to 99% by weight of an asymmetrically substituted 1,4-bis (styryl) benzene with 49 to 1% by weight of a symmetrically substituted 1,4-bis - (Styryl) benzene already known. Cyan and / or a carboxylic acid ester group are mentioned as substituents.
  • EP-B-0 064 303 Special mixtures of bis (cyanstyryl) benzenes are described in EP-B-0 064 303, e.g. a mixture of about 60% o, m'-bis (cyanstyryl) benzene and 40% o, p'-bis (cyanstyryl) benzene.
  • EP-A-0 023 027 describes mixtures of bis (cyanstyryl) benzenes which consist of o, p'-bis (cyanstyryl) benzene with o, o'-bis (cyanstyryl) benzene and / or p, p'-bis (cyanstyryl) benzene.
  • EP-A-0 032 254 proposes a process using a solvent (preferably methyl glycol acetate) in which the monocondensation product precipitates.
  • the present invention now relates to mixtures of optical brighteners with improved properties consisting of 75 to 85% by weight of a first compound of the formula (2) or (4). and 25 to 15% by weight of a second compound of the formula (3)
  • the mixtures of optical brighteners according to the invention are prepared by condensing terephthalaldehyde with a di-C1-C4-alkylphosphonomethyl-benzonitrile and the cyan-4-formylstilbene of the formula formed either directly or after its isolation further condensed with at least one other di-C1-Cph-alkylphosphonomethyl-benzonitrile.
  • the reaction of terephthalaldehyde is carried out with a di-C1-C4-alkylphosphonomethyl-benzonitrile in the presence of alkali metal hydroxide and water and the precipitated cyan-4-formylstilbene of the formula 5 is separated off.
  • terephthalaldehyde is condensed with a 4-di-C1-C4-alkyl-phosphonomethylbenzonitrile and the 4-cyan-4'-formylstilbene formed is condensed with 3-di-C1-C4-alkylphosphonomethyl- benzonitrile and 2-di-C1-C4-alkylphosphonomethyl-benzonitrile further.
  • the process for the preparation of mixtures of the compounds of the formulas 4 and 3 is a variant of the above process by using terephthalaldehyde, 2-di-C1-C4-alkylphosphonomethyl-benzonitrile and 4-di-C1-C4-alkylphosphonomethyl-benzonitrile condensed with each other at the same time.
  • the intermediate compounds of the formula can be produced in particularly good yield and purity by condensation of terephthalaldehyde with dialkylphosphonomethyl-benzonitriles by using aqueous alkali metal hydroxides, such as sodium and in particular potassium hydroxide, as proton acceptor.
  • aqueous alkali metal hydroxides such as sodium and in particular potassium hydroxide
  • the presence of water makes the reaction particularly selective with regard to monocondensation to cyan-4-formyl-stilbenes by largely preventing further condensation to the symmetrical di- (cyanostyryl) -benzene, which means an advantage over the alkali alcoholates commonly used.
  • terephthalaldehyde An excess of terephthalaldehyde is not necessary, ie approximately molar amounts of terephthalaldehyde and phosphonate are used.
  • the reaction temperature is kept in the range from 0 to 30 ° C and the amount of alkali between 1 to 2 moles per mole of terephthalaldehyde.
  • the water content of the alkali metal hydroxide to be used is in a wide range, preferably between 1 and 80%.
  • the 4-cyan-4'-formylstilbene can be prepared particularly well by this method.
  • the present invention further relates to the use of the mixtures of 75 to 85% by weight of a first compound of the formula (2) or (4) and 25 to 15% by weight of a second compound of the formula (3) for optically brightening polyester fibers, and an agent containing this mixture for optically brightening polyester fibers.
  • the individual components can be dispersed in a liquid medium, e.g. Water to be brought into the commercial form. You can disperse the individual components and then add the dispersions together. However, the individual components can also be mixed together in bulk and then dispersed together. This dispersing process takes place in the usual way in ball mills, colloid mills, bead mills or the like.
  • the mixtures according to the invention or the compositions containing them are outstandingly suitable for lightening textile material made of linear polyesters. However, these mixtures or agents can also be used in blended fabrics which contain linear polyester fibers.
  • the mixtures according to the invention are applied under the conditions customary for the use of optical brighteners, such as, for example, using the pull-out dyeing process in dyeing machines or by padding heat-setting application.
  • the treatment is advantageously carried out in an aqueous medium in which the compounds are present in finely divided form as suspensions, so-called microdispersions or, if appropriate, solutions. If necessary, dispersants, stabilizers, wetting agents and other auxiliaries can be added during the treatment.
  • the treatment is usually carried out at temperatures of about 20 to 140 ° C, for example at the boiling point of the bath or in the vicinity.
  • W / V means weight / volume and HPLC means high performance liquid chromatography.
  • Example 1 134.1 g of terephthalaldehyde, 455.8 g of 2-diethylphosphonomethyl-benzonitrile and 50.6 g of 4-diethylphosphonomethyl-benzonitrile are dissolved in 750 ml of dimethylformamide at room temperature. Then 396 g of sodium methylate solution (30% strength) are added dropwise over the course of about 1 hour in such a way that the reaction temperature does not exceed 45.degree. The resulting yellow suspension is stirred for 4 1/2 hours, the temperature gradually falling from 45 ° C to 25 ° C (volume approx. 1800 ml). After cooling to 0 to 5 ° C, 700 ml of methanol and 30 ml of acetic acid are added.
  • Example 2 67.5 g of terephthalaldehyde and 127 g of 4-diethylphosphonomethyl-benzonitrile are condensed in 500 ml of methanol with 70 g of potassium hydroxide powder (88% strength) as a condensing agent to give 4-cyan-4'-formyl-stilbene, which is isolated with 118 without , 5 g of 3-diethyl-phosphonomethylbenzonitrile and 28.5 g of 2-diethylphosphonomethyl-benzonitrile is further condensed.
  • Example 3 isolation of the intermediate: 6.7 g of terephthalaldehyde are added in portions to a mixture of 6.2 ml of aqueous potassium hydroxide solution 50% w / v and 40 ml of methanol, with stirring, cooling and passing over nitrogen, so that the Temperature does not rise above 22 ° C. A solution of 12.7 g of p-diethylphosphonomethyl-benzonitrile (content 99.5%) in 10 ml of methanol is added dropwise to the resulting solution at 10 ° C. in the course of 1/2 hour. The reaction product soon begins to fail.
  • Example 4 isolation of the intermediate: 6.7 g of terephthalaldehyde are added 12.8 g of m-diethylphosphonomethyl-benzonitrile (content 99.2%) according to Example 1 ⁇ m, but initially keeps the reaction temperature at 0-5 ° C. for 1/2 hour and allows it to rise to 22 ° C. overnight. After working up according to Example 1, but without dilution with water, 8.0 g of 3-cyanostilben-4'-aldehyde containing 2% 1,4-di (m-cyanostyryl) benzene are obtained.
  • Example 5 70 g of potassium hydroxide powder (content 88%) are placed in 800 ml of methanol at 2 ° C. with stirring. Then 134 g of terephthalaldehyde are added and 253 g of 4-diethylphosphonomethylbenzonitrile dissolved in 200 ml of methanol are added dropwise at 2 ° C. within 1 1/4 hours. The yellow thick slurry is stirred for a further 2 hours at 2 ° C, at 25 ° C and at 40 ° C. After cooling to 0 ° C., 300 ml of methanol are added, the crystallized 4-cyan-4'-formyl-stilbene is filtered off with suction and washed with 500 ml of methanol.
  • the well-suctioned filter cake is then suspended in 800 ml of dimethylformamide with stirring at 40 ° C., 204 g of 3-diethylphosphonomethyl-benzonitrile and 52 g of 2-diethylphosphonomethyl-benzonitrile are added, and then 198 g of methanolic sodium methylate solution (30% content) are added dropwise within 40 minutes. the temperature being kept below 45 ° C. by cooling with ice water.
  • the suspension is stirred for a further 4 hours at 40 ° C., mixed with 800 ml of methanol, neutralized with formic acid, cooled to 0 ° C., suction filtered, washed twice with 500 ml of methanol each time and dried under vacuum.

Landscapes

  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Detergent Compositions (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
  • Luminescent Compositions (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Paper (AREA)

Claims (5)

  1. Mélanges d'agents de blanchiment optique, caractérisés en ce qu'ils sont constitués de 75 à 85 % en poids d'un premier composé de formule (2) ou (4) :
    Figure imgb0023
     et de 25 à 15 % en poids d'un second composé de formule (3) :
    Figure imgb0024
  2. Mélanges conformes à la revendication 1, caractérisés en ce qu'ils sont constitués de 75 à 85 % en poids d'un composé de formule (4) :
    Figure imgb0025
     et de 25 à 15 % en poids d'un composé de formule (3) :
    Figure imgb0026
  3. Mélanges conformes à la revendication 1, caractérisés en ce qu'ils sont constitués de 75 à 85% enpoids d'un composé de formule (2) :
    Figure imgb0027
     et de 25 à 15 % en poids d'un composé de formule (3) :
    Figure imgb0028
  4. Utilisation d'un mélange conforme à la revendication 1, pour le blanchiment optique de fibres de polyester.
  5. Agent de blanchiment optique pour fibres de polyester, caractérisé en ce qu'il contient de 75 à 85 % en poids d'un premier composé de formule (2) ou (4) :
    Figure imgb0029
     et de 25 à 15 % en poids d'un second composé de formule (3) :
    Figure imgb0030
EP87810151A 1986-03-21 1987-03-16 Mélanges d'agents de blanchiment optique Expired - Lifetime EP0238446B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CH1142/86 1986-03-21
CH114286 1986-03-21

Publications (2)

Publication Number Publication Date
EP0238446A1 EP0238446A1 (fr) 1987-09-23
EP0238446B1 true EP0238446B1 (fr) 1995-11-15

Family

ID=4203472

Family Applications (1)

Application Number Title Priority Date Filing Date
EP87810151A Expired - Lifetime EP0238446B1 (fr) 1986-03-21 1987-03-16 Mélanges d'agents de blanchiment optique

Country Status (7)

Country Link
US (2) US4778622A (fr)
EP (1) EP0238446B1 (fr)
JP (1) JP2578108B2 (fr)
BR (1) BR8701260A (fr)
CA (1) CA1340088C (fr)
DE (1) DE3751594D1 (fr)
MX (1) MX168413B (fr)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CH671956A5 (fr) * 1987-01-29 1989-10-13 Ciba Geigy Ag
DE4219772A1 (de) * 1992-06-17 1993-12-23 Hoechst Ag Mischungen aus 1,4-Bis-(cyanostyryl)-benzolen
DE4330968A1 (de) * 1993-09-13 1995-03-16 Basf Ag Aufhellermischungen auf Basis von Bisstyrylverbindungen
DE19609956A1 (de) * 1995-03-24 1996-09-26 Basf Ag Mischungen von optischen Aufhellern auf Basis von Bisstyrylverbindungen
TWI250237B (en) * 1999-10-25 2006-03-01 Ciba Sc Holding Ag Mixtures of fluorescent whitening agents

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1469821B2 (de) * 1959-06-24 1972-03-23 Badische Anilin & Soda Fabrik AG, 6700 Ludwigshafen Optische Aufheller für makromolekulare organische Stoffe
FR1415977A (fr) * 1963-10-31 1965-10-29 Basf Ag Procédé pour l'azurage optique de matériaux en polyesters et en polyamides synthétiques
DE1444003A1 (fr) * 1963-10-31 1970-03-12
DE2420473A1 (de) * 1974-04-27 1975-12-11 Bayer Ag Weisstoenen von polyesterfasern
DE2929591A1 (de) * 1979-07-21 1981-02-05 Hoechst Ag Mischungen von optischen aufhellern
DE2929687A1 (de) * 1979-07-21 1981-02-12 Hoechst Ag Mischungen von optischen aufhellern
DE2929599A1 (de) * 1979-07-21 1981-02-05 Hoechst Ag Mischungen von optischen aufhellern, deren herstellung und verwendung
US4363744A (en) * 1979-09-10 1982-12-14 Hoechst Aktiengesellschaft Mixtures of optical brighteners and their use for the optical brightening
EP0030917B2 (fr) * 1979-12-13 1991-03-20 Ciba-Geigy Ag Agents de blanchiment optique de la série des bistyrylbenzènes, procédé pour leur préparation et leur utilisation
CH650792A5 (en) * 1979-12-13 1985-08-15 Ciba Geigy Ag Optical brighteners from bisstyrylbenzene compounds and preparation thereof
DE3001065A1 (de) * 1980-01-12 1981-07-16 Basf Ag, 6700 Ludwigshafen Verfahren zur herstellung von optischen aufhellern

Also Published As

Publication number Publication date
US4891153A (en) 1990-01-02
EP0238446A1 (fr) 1987-09-23
DE3751594D1 (de) 1995-12-21
US4778622A (en) 1988-10-18
MX168413B (es) 1993-05-24
JP2578108B2 (ja) 1997-02-05
JPS62232464A (ja) 1987-10-12
CA1340088C (fr) 1998-10-20
BR8701260A (pt) 1988-01-05

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