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Publication numberUS3825534 A
Publication typeGrant
Publication dateJul 23, 1974
Filing dateJul 19, 1971
Priority dateJul 23, 1970
Also published asCA945552A1, DE2135139A1, DE2135139B2, DE2135139C3
Publication numberUS 3825534 A, US 3825534A, US-A-3825534, US3825534 A, US3825534A
InventorsC Luethi, K Weber
Original AssigneeCiba Geigy Ag
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Styryl compounds,processes for their manufacture and their use
US 3825534 A
Abstract  available in
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Claims  available in
Description  (OCR text may contain errors)

3,825,534 STYRYL COMPOUNDS, PROCESSES FOR THEIR MANUFACTURE AND THEIR USE Kurt Weber, Basel, and Christian Luethi, Muenchenstein,

Switzerland, assignors to Ciba-Geigy AG, Basel, Switzerland No Drawing. Filed July 19, 1971, Ser. No. 164,051 Claims priority, application Switzerland, July 23, 1970, 11,171/70 Int. Cl. C09 b 23/00 US. Cl. 260-240 CA Claims ABSTRACTOF THE DISCLOSURE The invention provides new fluorescent compounds of the formula wherein either (a) one, two or three of the symbols R R R or R represent halogen atoms of the group fluorine, chlorine or bromine, whilst the remainder of these symbols denote hydrogen, or

(b) one or two of the symbols R R R or R represent a halogen atom of the group fluorine, chlorine or bromine, whilst another of the symbols R R R or R denotes an alkyl group with 1 to 4 carbon atoms or an alkoxy group with 1 to 4 carbon atoms, or two of the symbols mentioned together represent a methylene dioxy group, and the remaining symbols denote hydrogen.

The defined compounds are valuable optical brightening agents especially for polyamides polyvinyl chloride and polystyrene.

The present invention relates to selected distyryl compounds of diphenyl, processes for their manufacture, and their use as optical brighteners for organic materials.

The new compounds are symmetrically substituted relative to the diphenyl grouping and correspond to the formula wherein either (a) one, two or three of the symbols R R R or R represent halogen atoms of the group fluorine, chlorine or bromine, whilst the remainder of these symbols denote hydrogen, or

(b) one or two of the symbols R R R or R, represent a halogen atom of the group fluorine, chlorine or bromine, whilst another of the symbols R R R or R denotes an alkyl group with 1 to 4 carbon atoms or an alkoxy group with 1 to 4 carbon atoms, or two of the symbols mentioned together represent a methyl- 3,825,534 Patented July 23, 1974 enedioxy group, and the remaining symbols denote hydrogen.

Compounds of preferred importance within the framework of the above definition are those of the following formulae:

wherein either (a) one, two or three of the symbols, R R R and R represent halogen atoms of the group fluorine, chlorine or bromine, whilst the remainder of these symbols denote hydrogen, or

(b) one of the symbols R R R or R represents a halogen atom of the group fluorine, chlorine or bromine whilst another of the symbols R R R or R denotes an alkyl group with 1 to 4 carbon atoms, a methoxy group of an ethoxy group, or two of the symbols mentioned together represent a methylenedioxy group, and the remaining symbols denote hydro- (11)) R4 R"i orr=on nlzll R1]! I 1 R1,! R21! wherein either (a) two or three of the symbols R R R and R represent halogen atoms of the group fluorine, chlorine or bromine, whilst the remainder of these symbols denote hydrogen, or

(b) one of the symbols R R R or R represents a halogen atom of the group fluorine, chlorine or bromine whilst another of the symbols R R R or R denotes an alkyl group with 1 to 4 carbon atoms or an alkoxy group with 1 to 4 carbon atoms, or two of the symbols mentioned together represent a methylenedioxy group and the remaining symbols denote hydrogen.

wherein two or three of the symbols R R R and R represent a halogen atom from the group fluorine, chlorine or bromine, whilst the remaining symbols denote hydrogen.

3 The compounds of the formula -CH=CH -on=on X X wherein the chlorine indicated in the formula is preferably in position 2.

The compounds defined above can be manufactured analogously to processes which are in themselves known. A preferred procedure is to react, in a molecular ratio of 1:2, compounds of the formula with compounds of the formula wherein, in these formulae, R R R and R have the above-mentioned meaning and one of the symbols Z and Z denotes a O=CH group and the other denotes one of the groupings of the formulae wherein R represents an optionally substituted alkyl radical (preferably with up to 6 C atoms), an optionally substituted phenyl radical, a cyclohexyl radical or an aralkyl radical.

Accordingly, it is for example possible to react 1 mol equivalent of the dialdehyde of the formula with two mol equivalents of a monofunctional compound of the formula or to react one mol equivalent of a compound of the formula with 2 mol equivalents of an aldehyde of the formula RT CHO wherein V denotes a substituent of the formulae (5a) to (5d). The compounds according to formulae (la), (1b), (2), (3) and (3a) are manufactured entirely analogously.

The reaction is in both cases carried out by allowing the components to react in the presence of a strongly basic alkali compound and in the presence of a preferably hydrophilic, strongly polar solvent, and in the case where alkali hydroxides are used as the strongly basic alkali compound, these alkali hydroxides can contain up to 25% of water.

Toluene, xylene, chlorobenzene or alcohols such as, for example, ethanol, ethylene glycol monomethyl ether, and also N-methylpyrrolidone, diethylformamide, dimethylacetamide and preferably dimethylformamide or dimethylsulphoxide, may, for example, be mentioned as solvents for the process described above for the manufacture of compounds of the formula (1).

The temperature at which the reaction is carried out can vary within wide limits. It is determined (a) by the stability to the reactants of the solvent used, especially to the strongly basic alkali compounds, (5) by the reactivity of the condensation components and ('y) by the effectiveness of the solvent-base combination as a condensation agent. Preferably the temperature lies approximately in the range of 30 to 60 C., but in many cases satisfactory results are already achievable at room temperature (about 20 C.) on the one hand, or, on the other, at temperatures of C., and even at the boiling point of the solvent, if this is desired for reasons of saving time or employing a less active but cheaper condensation agent. In principle, reaction temperatures in the range of 10 to C. are thus also possible.

Strongly basic alkali compounds which can be used are above all the hydroxides, amides and alcoholates (preferably those of primary alcohols containing 1 to 4 carbon atoms) of the alkali metals, and for economic reasons those of lithium, sodium and potassium are of predominant interest. In principle, and in special cases, it is however also possible successfully to use alkali sulphides and alkali carbonates, arylalkali compounds, such as, for example, phenyl-lithium, or strongly basic amines (including ammonium bases, for example trialkylammonium hydroxides).

The new compounds defined above possess a more or less pronounced fluorescence in the dissolved or finely divided state. They can be used for the optical brightening of the most diverse synthetic, semi-synthetic or natural organic materials or substances which contain such organic materials.

The following groups of organic materials, Where optical brightening thereof is relevant, may be mentioned as examples of the above, without the survey given below being intended to express any restriction thereto:

(I) Synthetic organic high molecular materials:

(a) Polymerisation products based on organic compounds containing at least one polymerisable carbon-carbon double bond, that is to say their homopolymers or copolymers as well as their after-treatment products such as, for example, cross-linking, grafting or degradation products, polymer blends, products obtained by modification of reactive groups, and the like, for example polymers based on cap-unsaturated carboxylic acids or derivatives of such carboxylic acids, especially on acrylic compounds (such as, for example, acrylic esters, acrylic acid, acrylonitrile, acrylamides and their derivatives or their methacryl analogues) and polymers based on vinyl and vinylidene compounds (such as, for example, vinyl alcohol),

(b) Polymerisation products such as are, for example, obtainable by ring opening, for example, polyamides of the polycaprolactam type, and also polymers which are obtainable both via polyaddition and via polycondensati on, such as polyethers or polyacetals,

(c) Polycondensation products or precondensates based on bifunctional or polyfunctional compounds possessing condensable groups, their homocondensation and co-condensation products, and after-treatment products, such as, for example, polyamides (for example hexamethylenediamine adipate), maleate resins, melamine resins, their precondensates and analogues, polycarbonates and silicones,

'(d) Polyaddition products such as polyurethanes (crosslinked and non-crosslinked) and epoxide resins.

(II) Semi-synthetic organic materials such as, for example cellulose esters of varying degrees of esterification (acetate or triacetate) or cellulose ethers, regenerated cellulose (viscose or cuprammonium cellulose), or their after-treatment products, and casein plastics.

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

The organic materials to be optically brightened can be in the most diverse states of processing (raw materials, semi-finished goods or finished goods). On the other hand, they can be in the form of structures of the most diverse shapes, say for example predominantly three-dimensional bodies such as sheets, profiles, injection mouldings, various machined articles, chips, granules or foams, and also as predominantly two-dimensional bodies such as films, foils, lacquers, coatings, impregnations and coatings, or as predominantly one-dimensional bodies such as filaments, fibres, flocks and wires. The said materials can, on the other hand, also be in an unshaped state, in the most diverse homogeneous or inhomogeneous forms of division, such as, for example, in the form of powders, solutions, emulsions, dispersions, latices, pastes or waxes and the like.

Fibre materials can, for example, be in the form of endless filaments (stretched or unstretched), staple fibres, flocks, hanks, textile filaments, yarns, threads, fibre fleeces, felts, waddings, flock structures or woven textile fabrics, textile laminates, knitted fabrics and papers, cardboards or paper compositions, and the like.

The compounds to be used according to the invention are of importance, inter alia, for the treatment of organic textile materials, especially woven textile fabrics. Where fibres, which can be in the form of staple fibres or endless filaments or in the form of hanks, woven fabrics, knitted fabrics, fleeces, flock substrates or laminates, are to be optically brightened according to the invention, this is advantageously effected in an aqueous medium, wherein the compounds in question are present in a finely divided form, suspensions or possibly solutions. If desired, dispersing agents, stabilisers, wetting agents and further auxiliaries can be added during the treatment. Depending on the type of brightener compound used, it may prove advantageous preferably to carry out the treatment in a neutral or alkaline or acid bath. The treatment is usually carried out at temperatures of about 20 to 140 C., for example at the boiling point of the bath or near it (about 90 C.). Solutions or emulsions in organic solvents can also be used for the finishing, according to the invention, of textile substrates, as is practised in the dyeing trade in so-called solvent dyeing (pad-thermofix application, or exhaustion dyeing processes in dyeing machines).

The new optical brighteners according to the present invention can further be added to, or incorporated in, the materials before or during their shaping. Thus they can for example be added to the compression moulding composition or injection moulding composition duringthe manufacture of films, foils or mouldings.

Where fully synthetic or'semi-synthetic organic materials are being shaped by spinning processes or via spinning compositions, theoptical brighteners can be applied in 'acc'ordance'with the following processes: 7 Addition to the starting substances (for example monomers) or intermediates (for example precondensatesor prepolymers), that is to say before or during the polymerisation, polycondensation or polyaddition,

Powdering onto polymers chips or granules for spinning compositions,

Bath dyeing of polymer chips or granules for spinning compositions,

Metered addition to spinning melts or spinning solutions, and

Application to the tow before stretching.

The new optical brighteners according to the present invention can, for example, also be employed in the following use forms:

(a) Mixed with dyestuffs (shading) or pigments (for example white pigments), or as an additive to dye baths, printing pastes, discharge pastes or reserve pastes, or for the after-treatment of dyeings, prints or discharge prints.

(b) Mixed with so-called carriers, wetting agents, plasticisers, swelling agents, anti-oxidants, light protection agents, heat stabilisers and chemical bleaching agents (bleaching bath additives).

(c) Mixed with crosslinking agents or finishes (for example starch or synthetic finishes), and in combination with the most diverse textile finishing processes, especially synthetic resin finishes (for example creaseproof finishes such as wash-and-wear, permanent-press or no-iron), as well as flameproof finishes, soft handle finishes or antistatic finishes, or antimicrobial finishes.

(d) Incorporation of the optical brighteners into polymeric carriers (polymerisation, polycondensation or polyaddition products), in a dissolved or dispersed form, for use, for example, in coating compositions, impregnated compositions or binders (solutions, dispersions and emulsions) for textiles, fleeces, paper and leather.

(e) As additives to so-called master batches.

(f) As additives to the most diverse industrial products in order to render these more marketable (for example improving the appearance of soaps, detergent, pigments and the like).

(3) In combination with other optically brightening substances.

(h) In spinning bath preparations, that is to say as additives to spinning baths such as are used for improving the slip for the further processing of synthetic fibres, or from a special bath before the esterification of the fibre.

(i) As scintillators for various purposes of a photographic nature, such as, for example, for electrophotographic reproduction or supersentitisation.

If the brightening process is combined with textile treatment methods or finishing methods, the combined treatment can in many cases advantageously be carried out with the aid of appropriate stable preparations, which contain the optically brightening compounds in such concentration that the desired brightening effect is achieved.

In certain cases, the brighteners are made fully effective by an after-treatment. This can, for example, represent a chemical treatment (for example acid treatment), a thermal treatment (for example heat) or a combined chemical/ thermal treatment. Thus, for example, the appropriate procedure to follow in optically brightening a series of fibre substrates with the brighteners according to the invention is to impregnate these fibres with the aqueous dispersions or solutions of the brighteners at temperatures below 75 (3., for example at room temperature, and to subject them to a dry heat treatment at temperatures above 100 C.,.it beingfgenerally advisable.additionally to dry the fibre material beforehand at a moderately 'elevated temperature, for, example at not less than 60.?" C. and-pp to about130 C. The heat treatment. in the dr'y state is then advantageously carried out at temperatures between 120 and 200 C., for example by heating in a drying chamber, by ironing within the specified temperature range or by treatment with dry, superheated steam. The drying and dry heat treatment can also be carried out in immediate succession or be combined in a single process stage.

The amount of the new optical brighteners to be used according to the invention, relative to the material to be optically brightened, can vary within wide limits. A distinct and durable effect is already achievable with very small amounts, in certain cases, for example, amounts of 0.0001 percent by weight. However, amounts of up to about 0.8 percent by weight and above can also be employed. For most practical purposes, amounts between 0.0005 and 0.5 percent by weight are of preferred interest.

In the examples, the parts, unless otherwise stated, are always parts by weight and the percentages are always percentages by weight. Unless otherwise stated, melting points and boiling points are uncorrected.

EXAMPLE 1 A solution of 79.6 g. of 4,4'-bis-(dimethoxyphosphonomethyl)-diphenyl of the formula (10) CH3O O O OCH;

CH3 0 CH3 and 57.4 g. of 2-chlorobenzaldehyde (98% strength) in 300 ml. of anhydrous dimethylformamide, warmed to approx. 60 C., is added dropwise, over the course of 20 minutes, to a suspension of 26.2 g. of sodium methylate (98.8% strength) in 200 ml. of anhydrous dimethylformamide, with good stirring. In the course thereof, the reaction temperature rises from 23 C. to 45 C., and provision is made, by cooling with icewater, that this temperature is not exceeded. The pale yellow suspension is stirred for a further 2 hours at 40 to 45 C., cooled to room temperature, diluted with 330 ml. of desalinated water and cooled to 5 C., and the product which crystallises out is filtered off, washed with about 2.5 litres of desalinated water until the wash water reacts neutral, and dried in vacuo at 100 to 110 C.

84.4 g. (98.8% of theory) of the compound of the formula are obtained as a light yellow crystal powder of melting point 196.5 to 199 C. Recrystallisation thereof from toluene yields 56.8 g. (67.3% of theory) of a pale yellow crystal powder of melting point 209 to 210 C. After repeated recrystallisation from toluene, the melting point is 211 to 212 C.

Instead of the 4,4'-bis-(dimethoxyphosphonomethyl)- diphenyl of the formula used above, the equivalent amount of 4,4' bis-(diethoxyphosphonomethyl)-diphenyl can also be used with equal success for the manufacture of the compound (11). Instead of sodium methylate,-potassium hydroxide (KOH content about 90%) can equally well be used as thealkaline. condensation agent.

4,4-bis-(dimethoxyphosphonomethyl)-diphenyl and 2- chlorobenzaldehyde can also be initially introduced as a solution in dimethylformamide, and the sodium methylate introduced at the reaction temperature, either as asolid or as a suspension in dimethylformamide.

Equally, instead of using solid sodium methylate, a solution thereof in methanol can be used. Finally, dimethylsulph oxide also suitable for iise as a solvent instead of dimethylformamide.

'disty yldiphenyl compoundso fthe formula in l g b e below can be prepared in a similar manne Niiinber" R Melting point, 0.

1s or N f 246-247 .,:L

" omomornom 1 h I EXAMPLE 2 18 g.. of sodium methylate are dissolved in 75 ml. of

anhydrous dimethylformamide. To this solution, at 20 to 40 C., is added dropwise,.over the course of half an hour, a solution of 51.8 g. of 4,4-bis-(dimethoxyphosphonomethyl)-diphenyl and 40.2 g. of 4-methyl-2/3- chlorobenzaldehyde (isomer mixture ofthe 2-c hloro-/3- chloro derivative in the molar ratio of 45 :55) dissolved in 200. ml. of anhydrous dimethylformamide, which is at 60 C., and thereafter the whole. is warmed to ,40' 45 C. After 3 hours at this temperature,,the mixture is poured out into 800 ml. of. water and the small excess CH=CH CH3 CH=CH CHa The chloro-methyl-benzaldehyde used as the starting product is obtained by partial oxidation of o-chloro-pxylene according to J. Org. Chem., 27, 3705 (1962), the aldehydediacetate being saponified directly, without purification, to give the aldehyde isomer mixture. Purification is effected by steam distillation, with subsequent distillation (boiling point =105-112 C.).

EXAMPLE 3 A polyester fabric (for example Dracron) is padded at room temperature (about 20 C.) with an aqueous dispersion which per litre contains 031 to 1 g. of one of the compounds of the formula (1'1), 13), (I14), (15), (16), (17), (18), (20), (21) or (22) and 1 g. of an addition product of about 35 mols of ethylene oxide to 1 mol of octadecyl alcohol, and dried at about 100 C. The dry material is subsequently subjected to a heat treatment at about 220 C. for seconds. The polyester fabric treated in this way shows a strong optical brightening effect.

"EXAMPLE 4 10,000 g. of a polyamide, manufactured in a known manner from hexamethylenediamine adipate, in chip form are mixed with 30 g. of titanium dioxide (rutile modification) and 5 g. of one of the compounds of the formula (11), (13), 14) or ('15) in a tumbler vessel for 12 hours. The chips treated in this way are fused in a kettle, heated by oil or diphenyl vapour to 300'310 C., after having displaced the atmospheric oxygen by steam, and the melt is stirred for half an hour. It is then extruded through a spinneret under a nitrogen pressure of 5 atmospheres gauge, and the filament spun in this way is cooled and wound on a spinning bobbin. The filaments produced show an excellent brightening effect of good fastness to washing and to light.

If, instead of a polyamide manufactured from hexamethylenediamine adipate, a polyamide manufactured from ecaprolactam is used, similarly good results are obtained.

1 0 EXAMPLE 5 '100 g. of polyester granules of terephthalic acid e-thylene glycol polyester are intimately mixed with 0.05 g. of one of the compounds of the formula (111), 13), (14), ('15) or ('16) and the mixture is fused at 285 C., whilst stirring. After spinning through customary spinnerets, strongly brightened polyester fibres are obtained.

EXAMPLE 6 An intimate mixture of parts of polyvinyl chloride, 3 parts of st'abiliser (Advastat ED 100; Ba/Cd complex), 2 parts of titanium dioxide, 59 parts of dioctyl phthalate and 0.01 to 0.2 part of one of the compounds of the formula (I11), (15) or (16) is rolled to give a film on a calender at to C. The opaque polyvinyl chloride film thus obtained has a substantially higher white content than a film which does not contain the optical brightener.

EXAMPLE 7 100 parts of polystyrene and 0.1 part of one of the compounds of the formula (11), (14) or (1 8) are fused for 20 minutes at 210 C. in a tube of 1 cm. diameter, with exclusion of air. After cooling, an optically brightened polystyrene composition of good fastness to light is obtained.

What is claimed is:

1. A new styryl compound, symmetrically substituted relative to the diphenylyl grouping, of the formula wherein one, two or three of the symbols R R R and R represent halogen atoms of the group fluorine, chlorine or bromine, whilst the remainder of these symbols denote hydrogen.

2. A new styryl compound according to claim 1, which corresponds to the formula I R1 R2 wherein one, two or three of the symbols R R R and R represent halogen atoms of the group fluorine, ch10- rine or bromine, whilst the remainder of these symbols -11 denote hydrogen, characterised in that a compound of the formula is reacted in a solvent and in the presence of a strongly basic alkali compound, in a molecular ratio of 1:2, with a compound of the formula wherein, in these formulae, R R R and R have the above-mentioned meaning and one of the symbols Z and Z denotes a O=CH- group and the other denotes one of the groupings of the formulae References Cited in which the in which the UNITED STATES PATENTS 3,177,153 4/1965 Pommer a a1. 2s2 301.2 w 3,177,208 4/1965 Stilz et a1. 260240 CA OTHER REFERENCES Siegrist et al.: Helv. Chim. Acta, vol. 52, pp. 2521-2530 (1969).

JOHN D. RANDOLPH, Primary Examiner US. Cl. X.R.

8-93, 94; 961 R, 1.5, 1.6; 10 6-137, 148, 176; 117 33.5 R, 33.5 T, 137, 139.4, 139.5 R; 162-162; 252 132, 301.2 W, 399, 407; 260-2 R, 13, 15, 41 B, 41 C, 41 R, 46.5 R, R, 77.5 R, 78 R, 80R, 80.3 R, 613 A, 649

Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US3873311 *Feb 19, 1974Mar 25, 1975Eastman Kodak CoAggregate photoconductive compositions and elements containing a styryl amino group containing photoconductor
US3873312 *Feb 19, 1974Mar 25, 1975Eastman Kodak CoPhotoconductive composition and elements containing a styryl amino group containing photoconductor
US3912697 *Apr 27, 1973Oct 14, 1975Eastman Kodak CoLight-sensitive polymers
US3991049 *Sep 16, 1974Nov 9, 1976Ciba-Geigy AgAromatic compounds containing ethylene double bonds, processes for their manufacture and use
US4177347 *May 23, 1978Dec 4, 1979Ciba-Geigy CorporationOptical brighteners for detergents
US4610807 *Oct 18, 1984Sep 9, 1986Bayer AktiengesellschaftDistyryl compounds
US4859556 *Aug 9, 1988Aug 22, 1989Ricoh Company, Ltd.Multilayer; electroconductive support with photosensitive material
US5118874 *Jun 20, 1991Jun 2, 1992Hoechst AktiengesellschaftPartially fluorinated biphenyls, processes for their preparation and their use
Classifications
U.S. Classification549/435, 106/124.8, 524/468, 524/462, 528/271, 106/170.55, 570/199, 570/182, 106/169.13, 106/195.1, 106/170.14, 430/70, 106/156.4, 106/175.1, 8/648, 106/188.1, 106/170.15, 252/407, 568/643, 106/174.1, 570/128, 106/150.1, 430/572, 252/399, 106/169.53, 570/143, 510/461, 252/301.21, 162/162
International ClassificationG03C1/28, G03C1/815, C08K5/04, C09B23/14, C07D317/50, C07C17/26, G03G5/05, C07C25/24, C08K5/03
Cooperative ClassificationC07D317/50, G03C1/8155, G03G5/0517, C08K5/03, C07C17/2635, C09B23/141, C08K5/04, C07C25/24, G03C1/28
European ClassificationC07C17/263D, C08K5/03, G03C1/28, G03C1/815C, C07C25/24, C09B23/14B, C07D317/50, G03G5/05A4D, C08K5/04