DE2929599A1 - MIXTURES OF OPTICAL BRIGHTENERS, THEIR PRODUCTION AND USE - Google Patents

Description

HOECHST AKTIENGESELLSCHAFT HOE 79 / F 197 Dr.CT / St

Mixtures of optical brighteners, their manufacture and use

From German patents 913 734, 1 108 219 and 1 112 072, Belgian patent 655 114 and British Patent Nos. 913,735 and 916,610 is already known that the compounds of the formulas

CH = CH

-CH = CH-C V-CH = CH

suitable as optical brighteners, the first-mentioned compound only due to its very green shade Has found little importance while the last-mentioned compound is an important commercial product. It has now been found that the action of these compounds as optical brighteners can be significantly improved can, if you do not use these compounds as a single substance, but in their mixture with each other and used together with the corresponding o. p-di-cyano isomer.

The invention thus relates to a mixture consisting of
0 to 80% by weight of the compound of formula 1

CN-C V-CH = CH-C V-CH = CH-C V-CN (-j)

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20 to 100% by weight of the compound of formula 2

VS-PH = HH- / y (2)

CN and 0 to 80% by weight of the compound of formula 3

CN CN

The proportion of the individual compounds 1 to 3 in the Mixture can vary within the specified limits, preference being given to those mixtures which have the Compounds 1 and 3 contain in approximately equal proportions. From the limits given above for the weight ratios of compounds 1 to 3 it follows that the proportion of compounds 1 and 3 can be 0% and the proportion of compound 2 can be 100%. In this case lies the pure compound 2, which is also the subject of the present invention.

Mixtures of the following composition are advantageous:

5 to 35% by weight of compound 1,

30 to 90% by weight of compound 2 and 5 to 35% by weight of compound 3.

Mixtures of the following composition are particularly preferred:

15 to 28% by weight of compound 1,

15 to 28% by weight of the compound 2 and

44 to 70% by weight of compound 3, the proportion of formations 1 and 3 should be approximately the same. It goes without saying that the composition of the mixtures is within the various limits indicated above is chosen so that the sum of all individual connections is 100%.

The invention also relates to a process for the preparation of such mixtures, characterized in that

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- ys-

that one mole equivalent of a compound of the formula

with a total of 2 molar equivalents of a mixture of the compounds

nc- / Vq (5)

and

if W

(6)

implements.

The ratio of compounds 5 and 6 determines the composition of the mixture according to the invention. If the proportion of 5 is higher, the proportion of compound 1 increases at the expense of connection 3, if the proportion of connection 6 is higher, the proportion of connection 3 is in Mixtures higher than 1.

It is advantageous to implement 4 with one each To carry out molar equivalent of compounds 5 and 6, with an excess of 5 and 6 up to 10% possible, but is not beneficial. In formulas 4-6, one of the symbols X or Q means an aldehyde group and the other symbol is a group of formulas

? ^ OR
-CH ₉ -PC ^ (7a)

^^ OR

S ^ R

-CH - P, ^ (7b)

OR

(7c)

^ y ^R.

-CH = P ^ - R (7d)

* R

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where R is an optionally substituted alkyl radical with preferably 1-6 carbon atoms, preferably an aryl radical Phenyl, a cycloalkyl radical or an aralkyl radical, preferably benzyl.

A preferred variant of the method is that a compound of formula 4, where X is an aldehyde group, with compounds of formulas 5 and 6, where Q is a group of the formula 7a with R = C, - alkyl stands, implements.

The process is preferably carried out in solvents in the presence of a proton acceptor.

Examples of solvents that may be mentioned are hydrocarbons such as toluene, xylene, alcohols such as methanol, ethanol, isopropanol, butanol, glycols, hexanols, cyclohexanols, also ethers such as diisopropyl ether, tetrahydrofuran, dioxane and dimethyl sulfoxide. Particularly polar organic solvents such as formamide, dimethylformamide and N-methylpyrrolidone are suitable, Particularly noteworthy is dimethylformamide.

Primarily basic compounds, such as alkali or alkaline earth hydroxides, are suitable as proton acceptors, alcoholates or amides, strongly basic amines and anion exchange resins in the hydroxyl form. Preferred is the use of alkali hydroxides, especially potassium hydroxide.

The reaction temperature depends on the type of components to be converted, in particular on the type of organic compound containing carbonyl groups and the oxtonene acceptor? it is between -10 ° and + 100 ⁰ C, preferably between 0 ^Q - 50 ⁰ C. A preferred embodiment is to add together the reactants at lower temperatures and to carry out the reaction at a higher temperature at an end.

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-y-1.

The claimed process can be carried out, for example, in such a way that the proton acceptor is in the solvent presented and a solution of the reaction components 4-6 is added dropwise in the solvent, but it is also possible to submit the compounds 4-6 and the Admit proton acceptor. Another embodiment consists in submitting the compounds 4 or 5 and 6, in which X or Q is a group of the formulas 7 a-d, then first add the proton acceptor and then the aldehyde component. Implementation is in progress generally with a strong development of heat, so that you may have to cool. The processing of the The reaction mixture is carried out in a known manner, e.g. by adding methanol or ethanol and separating it off of the unusual products. The product mixtures obtained in this way can be determined by HPLC (high pressure liquid chromatography) analyze and characterize.

The starting compounds of the formulas 4-6 are known or can be prepared by known processes.

In principle, it is also possible to present compounds 1, 2 and 3 in pure form and then mix them down. The compounds of the formulas 1 and 3 are already known; the compound of the formula 2 can be used obtained for example in the following way according to methods known per se:

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NC-

-COOH

Thionyl chloride

(8th)

VV-CH = HW- / Λ-

(9)

Reduction according to Rosenmund

-CHO

(10)

NC

RO
RO

/ P-CH ₂

(11)

N /

(12)

The mixture of the compounds 1-3 according to the invention can for example, without any restriction being expressed by the following overview, for Lightening of the following groups of organic materials / if optical lightening is possible, can be used.

In detail are mentioned

I. Synthetic organic high molecular materials:

a) Polymerization products based on at least one polymerizable carbon-carbon double bond containing organic compounds, i.e. their homo- or copolymers and their aftertreatment products such as crosslinking, grafting or degradation products, polymer

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cuts or products obtained by modifying reactive groups, for example polymers based on et, ß-unsaturated carboxylic acids or derivatives of such carboxylic acids, especially of acrylic compounds (such as acrylic esters, acrylic acid, Acrylonitrile, acrylamides and their derivatives or their methacrylic analogs), of olefin hydrocarbons (such as ethylene, propylene, styrenes or dienes, also so-called ABS polymers), polymers Based on vinyl and vinylidene compounds (such as vinyl chloride, vinyl alcohol, vinylidene chloride),

b) polymerization products obtainable by ring opening, e.g. polyamides of the polycaprolactam type, also polymers that are available both via polyaddition and polycondensation, such as polyethers or polyacetals,

c) Polycondensation products or precondensates based on bi- or polyfunctional compounds with condensable groups, their homo- and mixed condensation products and post-treatment products such as polyester, especially saturated (e.g. ethylene glycol terephthalic acid polyester) or unsaturated (e.g. maleic acid dialcohol polycondensates and their crosslinking products with polymerizable vinyl monomers), unbranched and branched (also based on higher alcohols such as alkyd resins), polyesters, polyamides, (e.g.

Hexamethylenediamine adipate), maleic resins, melamine resins, their precondensates and analogues, polycarbonates, silicones,

d) Polyaddition products such as polyurethanes (crosslinked and uncrosslinked), epoxy resins.

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II. Semi-synthetic organic materials, e.g. cellulose esters of various degrees of esterification (so-called 2 1/2 acetate, triacetate) or cellulose ether, regenerated cellulose (viscose, copper ammonia cellulose) or their aftertreatment products, casein plastics.

III. Natural organic materials of animal or vegetable origin, for example based of cellulose or proteins such as cotton, wool, linen, silk, natural lacquer resins, starch, casein.

The organic materials to be optically brightened can belong to the most diverse processing states (raw materials, semi-finished products or finished products). On the other hand, they can be in the form of a wide variety of shaped structures, i.e., for example as predominantly three-dimensionally extended bodies such as plates, profiles, injection moldings, various types Workpieces, chips, granules or foams, also as predominantly two-dimensional formed bodies such as films, foils, lacquers, coatings, impregnations and coatings or as predominantly one-dimensional bodies such as threads, fibers, flakes, wires. The said materials can on the other hand also in unformed states in the most varied of homogeneous or inhomogeneous Distribution forms, e.g. as powders, solutions, emulsions, dispersions, latices, pastes or waxes are present.

Fiber materials can be, for example, as endless threads (drawn or undrawn), staple fibers, Flakes, hanks, textile threads, yarns, twisted threads, nonwovens, felts, wadding, flocking structures or as textile fabrics or textile composites, knitted fabrics and as papers, cardboard or paper pulps.

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The compounds to be used according to the invention are, inter alia, important for the treatment of textile organic Materials, especially textile fabrics, such as powders, solutions, emulsions, dispersions, latices, Pastes or waxes are present.

Fiber materials can be, for example, as endless threads (drawn or undrawn), staple fibers, flakes, Hank goods, textile threads, yarns, twisted threads, nonwovens, felts, wadding, flocking structures or as textile fabrics or textile composites, knitted fabrics and as papers, cardboards or paper pulps.

The compounds to be used according to the invention include, inter alia

Significance for the treatment of textile organic materials, especially textile fabrics, too. Provided Fibers, which as staple fibers or filaments, in the form of strands, woven fabrics, knitted fabrics, fleeces, flocked substrates or composites may be present that are to be optically brightened according to the invention, this is done with advantage in an aqueous medium, in which the compounds in question in finely divided form (suspensions, so-called microdispersions, if necessary, solutions) are available. If necessary, dispersing, stabilizing wetting agents can be used during the treatment. and other auxiliaries can be added.

Depending on the type of brightener compound used, it may prove advantageous to work in a neutral or alkaline or acid bath. The treatment is (C about 90 ^0), usually carried out at temperatures of about 20 to 140 ° C, for example at the boiling point of the bath or in the vicinity thereof. Solutions or emulsions in organic solvents can also be used for the inventive finishing of textile substrates, as is practiced in dyeing practice in what is known as solvent dyeing (padding thermofixing application, exhaust dyeing process in dyeing machines).

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2929593 - vT- ^.

The new optical brightening agents according to the present invention can also be added to the materials before or during whose deformation is added or incorporated. For example, you can use them in the production of > Films, foils (e.g. rolling in polyvinyl chloride in the heat) or moldings of the molding compound or injection molding compound add.

If the shaping of fully or semi-synthetic organic materials by spinning or over Spinning mass takes place, the optical brighteners can be applied using the following methods:

- addition to the starting substances (e.g. monomers) or intermediate products (e.g. precondensates, prepolymers), i.e. before or during the polymerization, polycondensation or polyaddition,

- powdering onto polymer chips or granules for spinning masses,

- bath coloring of polymer chips or granulates for spinning masses,

- dosed addition to spinning melts or spinning solutions, ~ application to tow before drawing.

The new optical brightening agents according to the present invention can, for example, also be used in the following forms can be used:

a) Mixtures with dyes (nuances) or pigments (color or especially e.g. white pigments) or as an additive to dye baths, printing, etching or reserve pastes. Also for the post-treatment of dyeings, Printing or etching printing,

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b) in mixtures with so-called "carriers", wetting agents, Plasticizers, swelling agents, antioxidants, light stabilizers, heat stabilizers, chemical bleaching agents (Chloride bleach, bleach bath additives),

c) in a mixture with crosslinkers, finishing agents (e.g.

Starch or synthetic finishes) as well as in combination with various textile finishing processes, in particular synthetic resin finishes (e.g. crease-resistant finishes such as "wash and wear", "permanent-press", "non-iron"), furthermore flame-resistant, soft-grip dirt removal ("anti-soiling") - or Antistatic equipment or antimicrobial equipment,

d) Incorporation of the optical brightening agents into polymers

Carrier materials (polymerization, polycondensation or polyaddition products) in dissolved or dispersed Form for use e.g. in coating, impregnating or binding agents (solutions, dispersions, Emulsions) for textiles, fleece, paper, leather,

e) as additives to so-called "master batches",

f) as additives to a wide variety of industrial products, to make them more marketable (e.g.

Aspect improvements of soaps, detergents, pigments),

g) in combination with other, optically brightening substances,

h) in spin bath preparations, i.e. as additives to spin baths, as used to improve the sliding properties of synthetic fibers or from a special bath before the fiber is drawn,

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i) as scintillators, for various photographic purposes, such as electrophotographic Pure production or supersensitization,

j) depending on the substitution as laser dyes.

If the whitening process is combined with textile treatment or finishing methods, the combined Treatment in many cases advantageously take place with the help of appropriate permanent preparations, which contain the optically brightening compounds in such a concentration that the desired brightening effect is achieved will.

In certain cases, the brighteners are brought to their full effect by a post-treatment. This can represent, for example, a chemical (eg acid treatment), a thermal (eg heat) or a combined chemical / thermal treatment. Thus, the procedure for example in the optical brightening of a number of fibrous substrates, such as polyester fibers, with the inventive brighteners useful in the way that these fibers with the aqueous dispersions (optionally also solutions) of the brightening agent at temperatures below 75 ⁰ C, for example at Room temperature, impregnated and subjected to a dry heat treatment at temperatures above 100 ^° C., it being generally advisable to dry the fiber material beforehand at a moderately elevated temperature, for example at least 60 ^° C. to about 130 ^{° C.}

The heat treatment in the dry state is then advantageously carried out by heating in a drying chamber Iron in the specified temperature range or by treating with dry, superheated steam. the Drying and dry heat treatment can also be carried out immediately one after the other or in a single one Operation can be merged.

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The amount of new to be used in accordance with the invention Optical brighteners, based on the material to be optically brightened, can vary within wide limits. Already with very small amounts, in certain cases e.g. 0.001 percent by weight, can be a clearer and more durable Effect can be achieved. However, amounts of up to about 0.8 percent by weight and optionally up to about 2 percent by weight are used. For most practical purposes, quantities are preferred between 0.005 and 2, preferably 0.1 to 0.5 weight percent of interest.

For various reasons it is often advisable not to use the brighteners as such, i.e. pure, but rather mixed with a wide variety of auxiliaries and accessories, such as anhydrous sodium sulfate, sodium sulfate decahydrate, sodium chloride, sodium carbonate, Alkali metal phosphates such as sodium or potassium orthophosphate. Sodium or potassium pyrophosphate and sodium or potassium tripolyphosphates or alkali metal silicates.

The new optical brighteners have the particular advantage that they can also be used in the presence of active chlorine donors, such as hypochlorite, are effective and without significant loss of the effects in washing baths with non-ionogenic Detergents such as alkylphenol polyglycol ethers can be used.

In the following examples, percentages are always weight - percent; Unless otherwise noted, melting and boiling points are uncorrected:

Example 1 a;

10.8 g of sodium methylate powder are added to 200 ml of dimethylformamide (DMF) presented and with cooling at an internal temperature of 0 ° -5 ° C within 30 min a Solution of 23 g of the compound

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NC- / ^ -CH = CH- / ^ -CHO (10)

and 28 g of the compound

0-C ₂ H ₅

(11 a>

0-C ₂ H ₅

added dropwise in 200 ml of DMF. Then for 1 hour at 0 ° - 5 ° C, then stirred overnight at 30 ⁰ C, 500 ml of methanol, stirred for 1 hour, filtered off, washed with methanol and water and dried. 27.5 g (83% of theory) of the δ: bond are obtained

MM »» MM * » MM ^ V

(2)

- / V-CH = CH- / ^ -CH =

which after recrystallization from methyl glycol under clarifying with Terkohle at 204 ° - 205 ⁰ C melts.

Example 1b:

In 400 ml of xylene are 15 ₄ g of a catalyst in the form of 5% Pd on BaSO at 120 ⁰ C with hydrogen pre-reduced, then with 1 ml of a 10% quinoline / sulfur solution in xylene poisoned, 53 g of the compound 9

entered and ^{reduced with hydrogen at 120 °} C. until no more HCl can be detected in the exhaust gas. The catalyst is filtered off while hot and, after cooling to 20 ^° C., the product is filtered off with suction, washed with methanol and dried.

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This gives 34.5 g (75% of theory) of the compound 10 in the form of a light yellow powder, which at 200 ° - 202 ⁰ C and melts can be further reacted without purification.

Example 1c:

100 g of 4'-cyano-stilbene-4-carboxylic acid are g in 1500 ml toluene with 1 DMF and 100 g of thionyl chloride reflux for 3 hours reacted, followed by distilling off the excess thionyl chloride, filtered with suction at 2O ⁰ C, washed with hexane and dried under exclusion of moisture .

This gives 96 g (90% of theory) of compound 9 as a light yellow powder of melting point 190 ° - 192 ⁰ C, which can be reacted further without purification.

Example 2:

5 ⁰ C under N ₂ atmosphere 7.7 g of terephthalaldehyde and 12.6 g of the compounds - in 100 ml DMF at 0 ° to

and

? ^ OC ₂ H ₅
-CH ₂ - P <T ^{Λ 3} (14)

₂
N = ^ OC ₂ H

₂ H ₅

submitted and added over 30 minutes 22 g of sodium methylate powder in portions, followed by a further 1 h at 0 ° -... then stirred 5 ° C, 18 hours at 25 ° C and 5 h at 50 ⁰ C, diluted with 100 ml of methanol, 1 Stirred for hours, filtered off with suction while cold and dried. 27.6 g (83% of theory) of a mixture of compounds 1-3 are obtained

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Composition according to HPLC

Verb. 1 25th , 3 Verb. 2 30th ,1 Verb. 3 44 , 7 Example 3:

In 10 ml of DMF under N ₂ atmosphere at 0 ° - 5 ⁰ C 11.2 g of KOH powder and submitted over 45 minutes a solution of 3.85 g of terephthalaldehyde, 6.3 g and 6.3 g Jl_3 TA in 40 ml of DMF were added dropwise, stirred for 1 hour at 0 ^° C., 20 hours at 25 ^° C. and 3 hours at 50 ^° C., diluted with 100 ml of methanol, stirred for 1 hour, filtered off with suction while cold, washed with methanol and dried. 7.9 g (95% of theory) of a light yellow powder with the composition are obtained:

Verb. 1 27 ,1 Verb. 2 45 ,1 Verb. 3 27 , 7

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Claims (6)

hoe 79 / f 197 claims: 1. Mixture consisting of 0 to 80% by weight of the compound of formula 1 NC- / V -CH = CH- / V ^ -CH = CH- / \ cN (1) 20 to 100% by weight of the compound of formula 2 -JO NC- / ^ -CH = CH- / ^ -CH = CH- / ^ (2) CN and 0 to 80% by weight of the compound of formula 3 \ / ~ ^{CH = CH} ~ \ ^ -CH = CH- / \ (3) CN CN 2. Optical brightener according to claim 1 consisting of 5 to 35 wt .-% of compound 1, 30 to 90% by weight of compound 2 and 5 to 35% by weight of compound 3. 3- Optical brightener according to claim 1, consisting of 15 to 28% by weight of compound 1, 15 to 28% by weight of compound 2 and 44 to 70% by weight of compound 3. 4. Optical brightener according to claim 1 consisting of 100% by weight of compound 2. 5. A method for producing the optical brightener according to claim 1, characterized in that one 1 mole equivalent of the compound of the formula Χ- / Λ-Κ 030086/0341 with a total of 2 molar equivalents of a mixture of the compounds of the formulas ^NC \ / ^{Q and} \ / ^Q . CN reacts, where either X is an aldehyde group and Q is a group of the formula ? OR ° R JJr f ^ -CH ₀ -P ^ ~ ^CH 9 ~ ^P T ^^ R OR OR R or vice versa and R is an optionally substituted alkyl radical with 1-6 carbon atoms, an aryl radical, denotes a cycloalkyl radical or an aralkyl radical. 6. Use of the mixture according to claim 1 as an optical Brightener. 030066/0341