MXPA99003207A - Fiber-reactive brighteners of bis-s-triazinylaminostilbene - Google Patents

Abstract

An optical brightener of the bis-s-triazinylaminostilbene series having at least one fiber reactive vinyl sulfone substituent. The compounds of the invention provide high whiteness at low application levels.

Description

BIS-S-TRIAZINILAMINOESTILBEN POLISHERS REACTVOS A FIBRAS BACKGROUND OF THE INVENTION TECHNICAL FIELD This invention relates to the technical field of optical brighteners of bis-s-triazinylaminostelbene series which are substituted in the triazinyl rings by vinylsulfone containing reactive substituents to fibers.

BACKGROUND Bis-s-triazianylaminosilbene based polishes represent the largest class of optical brighteners on the market today. The patent of E.U.A. No. 3,723,425 to Ackermann et al. Describes the use and preparation of this class of brighteners. The chemistry and use of optical brighteners are well known, see for example Textile Science and Technology, Vol. 4, Fluorescent Optical Brightening Agent, Williamson, R.: Elsevier Scientific Publishing Co. Amsterdam. The Netherlands (1980). Traditional optical brighteners, which are not reactive to fibers, are typically applied to cellulosic substrates in neutral or alkaline baths by continuous or exhaust applications. The application of the optical brightener of an alkaline bath in the presence of a bleaching agent (for example, peroxide) is preferred from an economic point of view. Although, optical brighteners not reactive to fibers are typically applied in relatively low concentrations (0.1-2.0% by weight of products) to effect bleaching, it would be advantageous both economically and for the environment if significantly lower amounts of brightener could be used for achieve similar bleaching. This invention provides these advantages.

BRIEF DESCRIPTION OF THE INVENTION This invention relates to an optical brightener of the bis-s-treazinylaminostilbene series having at least one vinylsulfone substituent reactive to fibers selected from: N (CH2)? - SO2Y wherein R3 is selected from hydrogen, an unsubstituted substituted phenyl, a substituted or unsubstituted alkyl of 1 to 4 carbons, a substituted or unsubstituted alkoxy of 1 to 4 carbons and a substituted or unsubstituted cyclohexyl substituent. W is selected from a substituted or unsubstituted arylene, for example, feline and naphthylene; a substituted or unsubstituted alkylene of 1 to about 8 carbons, for example, methylene, ethylene and propylene, or 2 or 3 of said arylene and alkylene groups in combination, for example, arylene-alkylene or arylene-alkylene-arylene or alkylene -arylene-alkylene; etc. And it is selected from vinyl, 2-sulfatoethyl, 2-thiosulfatoethyl, 2-phosphate-ethyl, and 2-alkyanoxy-oxyethyl where said alkanoyl has from 2 to 5 carbon atoms. a is a selected number of 0 and 1; b is a selected number of 1 and 2, with the proviso that the sum of a + b is 2; The X portion together with the N atom is a bivalent heterocyclic ring formed from 1 to 2 alkylene groups of 1 to 5 carbons which may contain a heteroatom (N, O, S); and x is a selected number from 1 to 8. The compounds of the invention are useful in the optical brightening of organic materials especially useful in fibers and textile fabrics.

The optical brighteners of the invention provide equivalent whiteness as the prior art in a quarter of the concentration.

DESCRIPTION OF THE PREFERRED MODALITIES Optical brighteners are typically applied in relatively low concentrations (0.1-2.0% by weight of products) to effect whiteness. It would be advantageous both economically and for the environment if significantly lower amounts of brighteners could be used to achieve a similar whiteness. This invention provides such advantages; for example, compounds of the invention provide essentially the same degree of whiteness as the prior art brighteners in a quarter of the concentration. Prior art optical brighteners of the type 4,4 'bi-s-triazinylaminostilbene are well known as is their preparation and use; see for example document of U.S.A. No. 3,723,425. These compounds, in their acid form have the following general formula: wherein: Groups G and B are independently selected from substituted and unsubstituted aromatic and aliphatic amines, substituted and unsubstituted alkoxy, substituted and unsubstituted phenoxy, hydroxy cyanamide, piperidino, hexamethylamino, morpholino and halogen. Generally, groups G and B are where the compounds are symmetrical and in which substituents G and B are the same on both sides of the molecule, but may be different. Typical substituents in said aromatic and aliphatic amines are hydrogen, cyano, phenoxy, and substituted and unsubstituted C 1 to C 4 alkyl, substituted and unsubstituted C 1 to C 4 alkoxy, a substituted and unsubstituted alkoxy of 3 to 8 carbon atoms or a phenyl substituent which can be substituted by one or two substituents selected from chlorine, sulfo, C1 to C4 alkyl, hydroxyalkyl of C1 to C4, alkoxy of C1 to C4, etc.

The patent of E.U.A. do not. 3,018,287 to Fleck is another example of the bis-s-triazinylaminostilbene brighteners of the prior art. Now we have discovered the new reactive brighteners to fibers that can be used in significantly lower amounts than the previous ones and represent the present invention. According to the invention, the compounds in their free acid form have the following formula: FORMULA 1 wherein: G represents a substituent of alkoxy of 1 to 4 carbon atoms, hydroxyalkoxy, hydroxy, cyanamide, halogen, substituted or unsubstituted phenoxy, the formula Q, or a substituted or unsubstituted aliphatic or aromatic amino group of the formula: wherein Ri and R2 are independently selected from hydrogen, a lower alkyl of 1 to 4 carbon atoms, a lower alkoxy of 1 to 4 carbons, a hydroxyalkyl group of 2 to 4 carbon atoms, an alkoxyalkyl group of 3 to 8 carbon atoms, where the oxygen atom and the nitrogen atom are not linked to the same carbon atom, cyano or a phenyl group which can be substituted by 1 or 2 substituents independently selected as chloro, hydroxy lower alkyl of 1 to 4 carbon atoms carbon, alkoxy of 1 to 4 carbons, sulfo, carboxy and combinations of said substituents, or Ri and R2 together represent the radical of a saturated heterocyclic moiety, for example the piperidino, hexamethylene imino or morpholino moiety and substituted methyl derivatives or ethyl sub-substituted thereof. Q is a group of formula (2a) or (2b): (2a) N X- - (CH2) X SO Y (2b) wherein: R3 is selected from hydrogen, a substituted or unsubstituted phenyl group, or an unsubstituted and substituted alkyl group of 1 to 4 carbon atoms, for example methyl or ethyl. The phenyl portion can be substituted by 1 or 2 substituents independently selected from halogen, (for example, chlorine and bromine), alkoxy of 1 to 4 carbon atoms, (for example, methoxy and ethoxy), alkyl of 1 to 4 carbon atoms (for example, methyl), sulfo, carboxy and cyclohexyl which can be substituted by halogen (for example, chloro and fluoro), alkoxy having from 1 to 4 carbon atoms, (for example, methoxy and ethoxy), alkyl having 1 to 4 carbon atoms (for example, methyl and ethyl), sulfo and carboxy. The alkyl portion can be substituted by substituents such as halogen, (Cl, F, Br), carboxy, hydroxy, cyano, sulfamoyl, sulfo, sulfate or a substituted or unsubstituted phenyl portion as described above. The alkyl portion may also be substituted by Ci to C4 alkoxy, hydroxyl, cyano, alkoxy having from 1 to 4 carbon atoms (for example, methoxy and ethoxy), which may be substituted by carboxy, hydroxy, cyano, sulphamoyl, sulfo, sulfate or a substituted or unsubstituted phenyl portion. W is selected from a substituted or unsubstituted arylene radical, for example, phenylene and naphthylene or a substituted or unsubstituted alkylene or combinations thereof, for example an alkylene-arylene moiety or an arylene-alkylene moiety or an alkylene-arylene moiety -alkylene or arylene-alkylene-arylene radical. The term "alkylene" is intended to mean a direct or branched chain portion having 1 to 8, preferably 2 to 6 and in particular 2 to 4 carbon atoms. The arylene radicals can be interrupted by 1 or more atoms or groups such as 1 or 2, hetero groups, such as nitrogen or oxygen or sulfur of the formula -SO2-, -CO-, -SO2-NH- or CO-NH-, and the Alkylene and arylene portions in the combined alkylene / arylene radicals can be linked in each case by said group or a covalent bond. Suitable substituents for the arylene group include halogen (Cl, F, Br), hydroxy, Ci to C4 alkyl, Ci to C4 alkoxy, suifo, carboxy, cyanamide, nitro, amino, cyano, sulfate, phosphate, etc. Suitable substituents for the alkylene group include halogen (Cl, F, Br), hydroxy, alkoxy, cyano, nitro, amino, sulfo, carboxy, phenyl, sulfate, Ci to C4 etc.

Y is the vinyl group or a 2-sulfatoetiio, 2-thiosulfatoetilo or 2-fosfatoetilo or a 2 alkanoyloxy-ethyl group having 2 to 5 carbon atoms in the alkanoyl radical, such as the 2-acetoxyethyl group or group 2 -benzoyloxy-ethyl, 2- (sulfobenzoyloxy) -ethyl or 2- (p-toluenesulfoni-Ioxy) -ethyl or a 2-haloethyl group, such as the 2-bromoethyl or 2-chloroethyl group, preferably the vinyl group and in particular the 2-suifatoethyl group. a is the number of 0 or 1 and b is the number of 1 or 2. in which the sum of (a + b) is equal to number 2 and in which case B is 2, the groups of formulas -W- (SO -Y) can have the same meaning as one another or a different meaning from another, X, together with the N atom, forms a bivalent radial of a heterocyclic ring with 1 or 2 alkylene groups having 1 to 5 carbon atoms. carbon and if appropriate 1 to 2 heteroatoms, such as N, S, O to a group such as the piperazin-1,4-ylene radical or a piperidinylene radical. The brighteners of this invention are suitable for the optical brightening of organic materials, especially said materials made of cellulose and synthetic natural polyamides. These materials can be in the form of fibers such as basic cotton fibers, rayon, wool and nylon fiber or in other forms such as paper, fleece fabrics, etc. Cellulose fibers are applied in an exhaust or continuous process preferably by the exhaust method. In the exhaust method, the brighteners are applied in a ratio of products to the solution of 1: 10- 1:50 in concentration of 0.1-0.4% by weight of product brightener and 1.0-5.0 g / L of alkali (such as caustic sodium carbonate, potassium hydroxide, sodium carbonate and sodium bicarbonate) at temperatures of 30-80 ° C. Preferably, the brighteners are applied under alkaline conditions and in combination with bleached agents such as hydrogen peroxide. The compounds of the invention are produced by reacting 2 moles of 2,4,6-trichloro-1, 3,5-triazine in the first or second synthetic step, with one mole of 4,4'-diamino-ethylbenzene- 2,2'-disulfone, or an alkali metal salt or an alkaline earth metal salt thereof. Two moles of each G and Q, which are described above, are subsequently reacted in any desired sequence, but preferably in the sequence in which G precedes Q. The first step of the reaction is preferably carried out at temperatures between 0. -10 ° C, the second step at 10-40 ° C and the third step at 50-80 ° C. The reactions are carried out on an acidic scale at an alkaline pH. The following examples are intended to illustrate the invention in the preferred embodiments, where the parts are parts by weight, the percentages are in percent by weight and the degrees are degrees centigrade, unless otherwise specified.

EXAMPLE 1 : A dilute solution of 1.1 parts of diethanolamine in a solution containing 18.4 parts of cyanuric chloride, 50 parts of ice and 100 parts of water is added dropwise. The reaction mixture is kept basic weakly throughout the condensation with a dilute sodium carbonate solution. After 3-5 hours, an aqueous, neutral solution of 18.9 parts of 4,4'-diaminoesitiIbeno-2,2'-disulfonic acid is added dropwise to the weakly basic condensation product of diethanolamine-dichlorotriazine at 30-45 °. C. The pH of the reaction mixture remains weakly acidic until the condensation is complete with the dilute sodium carbonate solution. The final fiber reactive optical brightener is obtained by adding 39.1 parts of 1-aminobenzene-3- (2-sulfatoethyl) -sulphone and heating to 70-75 ° C under acidic conditions. The final product is obtained by evaporating the polishing solution in a low temperature oven. The quality of the final product was 75% (area) by HPLC. This product in the structure established in formula 1, wherein G is -N (CH2-CH2-OH) 2 and Q is EXAMPLE 2: This product was prepared as described in example 1, except that 1-aminobenzene-4- (2-sulfatoethyl) -sulfone replaced 1-aminobenzene-3- (2-sulfatoethyl) -sulphone in the last condensation.

EXAMPLE 3: This product was prepared as described in example 1 except that 1-aminobenzene-2-methoxy-5- (2-sulfatoethyl) -sulfone replaced 1-aminobenzene-3- (2-sulfatoethyl) -sulphone in the last condensation.

EXAMPLE 4: This product was prepared as described in Example 1, except that 1-aminobenzene-2-methoxy-5-methyl-4- (2-sulfatoethyl) -sulfone replaced 1-aminobenzene-3- (2-sulfatoethyl) -sulfone. in the last condensation.

EXAMPLE 5: This product was prepared as described in example 1, except that 1-aminobenzene-2,5-dimethoxy-4- (2-sulfatoethyl) -sulfone replaced 1-aminobenzene-3- (2-sulfatoethyl) -sulfone in the last condensation.

EXAMPLE 6: This product was prepared as described in the example except that N-phenyl-2- (2-sulfatoethyl) -ethylamine replaced 1-aminobenzene-3- (2-sulfatoethyl) -sulfone in the last condensation. Other examples illustrating the invention are listed in the following Table 1, wherein the portions Q and G of formula 1 are as described below. These brighteners can be synthesized by the procedures described above.

Formula 1 TABLE 1 More examples of optical brighteners Example Q. 12 NH so, a?, CH, os? Ji? Example , OSOjll, 0S03H Example Q The optical brightener of the invention was applied to gray products of cotton fabrics under the conditions and concentrations set out in the following tables and the whiteness was measured using the AATCC Test Method 110 - 1994, "Whiteness of Textiles". The strength of the brighteners the invention was 100% standardized using the Color Index Brightener 28 as a standard. The following tables compare the compositions of the invention to a Cl 28 brightener, a widely used commercial optical brightener.

TABLE 2 Comparison of whiteness values for optical brightener C.L 28 vs. the example 1 to 40.5 ° C with alkali Optical Brightener 0.10% 0.20% 0.40% 0.80% C.l: 28 125.3 131.6 136.2 138.7 Example 1 136.3 140.8 134.5 124.9 Note: Example 1 has lower whiteness than C.l: 28 in the dark of 0.40 and 0.80% due to the saturation of the brightener in the cotton, therefore creating a yellowish effect.

TABLE 3 Comparison of whiteness values for optical brightener C.l. 28 vs. the example 1 to 60 ° C with alkali Optical Brightener 0.10% 0.20% 0.40% 0.80% C.l. 28 125.2 129.5 131.3 127.2 Example I 130 132.1 132.2 121.5 * A whiteness value of 136.2 was obtained, but this result was not reproduced and was considered not reliable.

TABLE 4 Comparison of whiteness values for optical brightener C: l: 28 vs. the example 1 to 71.1 ° C with alkali Optical Brightener 0.10% 0.20% 0.40% 0.80% C.l. 28 124.9 128 128.8 125.5 Example 1 134 135.7 134.5 128.6 TABLE 5 Comparison of whiteness values for optical brightener C.L 28 vs. Example 1 to 79.4 ° C with alkali Optical Brightener 0.10% 0.20% 0.40% 0.80% C.l. 28 130.1 131.5 136.3 128.5 Example 1 131.4 135.9 133.4 131.6 The following Table 6 compares compositions of the invention, examples 7 and 8 with other prior art compositions as illustrated in the patent of E.U.A. do not. 3,723,425 to Ackermann, (the brightener 425). In the composition of Ackermann the substituents G and Q are cyanamide and chlorine, respectively. In Examples 7 and 8 illustrating the invention, the Ackermann chlorine group is replaced by the fiber reactive portions of this invention. invention; for example the reactive groups derived from aminobenzene-3- (2-sulfatoethyl) -sulfone and aminobenzene-4- (2-suyfatoethyl) -sulfone, respectively.

TABLE 6 Comparison of whiteness values for Ackermann 425 brightener vs. Examples 7 and 8 at 60 ° C with alkali Optical Brightener 0.10% 0.20% 0.40% 0.80% 425 99.4 103.2 103.3 108.2 Example 7 123.7 126.4 126.5 119 Example 8 121.9 124.6 122.4 117.7 As can be seen from the above information, the composition of the invention consistently gives higher values of whiteness over the prior art at lower concentrations and at a lower application temperature which results in lower costs in material, energy and environment (water cleaning) of waste).

Claims (9)

NOVELTY OF THE INVENTION CLAIMS

1. - An optical brightener of the bis-s-triazinylaminostilbene series having at least one fiber reactive group of the vinylsulfone series corresponding to formula (1) or (2) jFßla (i) N X (CH2)? - SO2Y (2) wherein R 3 is hydrogen, substituted or unsubstituted phenyl, unsubstituted and substituted alkyl of C 1 to C 4 substituted or unsubstituted C 1 to C 40 alkoxy; W is substituted or unsubstituted alkylene of 1 to 8 carbon atoms which can be interrupted by N, S or 0 or is substituted or unsubstituted metaphenylene or is naphthylene or is a combination of said alkylene and phenylene or of said alkylene and naphthylene where the alkylene and naphthylene, respectively, can be linked to each other by a covalent group or by -SO2-, -CO-, -SO2-NH- or CO-NH-, and is vinyl, 2-sulfatoethyl, 2-thiosulfatoethyl or 2- phosphate or 2 alkanoyloxy-ethyl with a 2 to 5 carbon alkanoyl portion; a is 0 or 1 and b is the number of 1 or

2. With the proviso that the sum of (a + b) is 2; x is a selected number from 1 to 8; X and N together form a bivalent radial of a heterocyclic ring with 1 or 2 alkylene groups consisting of 1 to 5 carbon atoms, which may be optionally interrupted by S, O or N and the alkali metal salts of said optical brightener. 2. An optical brightener according to claim 1, further characterized in that Y is 2-sulfatoethyl.

3. An optical brightener according to claim 1, further characterized in that Y is vinyl.

4. An optical brightener according to claim 1, having the formula: where Q is a group of formula (1) or (2) according to claim 1; G is alkoxy, hydroxyalkoxy, hydroxy, cyanamide, halogen, substituted or unsubstituted phenoxy, from C1 to C4 or a group of formula (1) or (2) or is a substituted or unsubstituted amino group or an aliphatic amino group or a portion saturated heterocyclic selected from piperidino, hexamethyleneimino, morpholino or methyl or ethyl derivatives thereof.

5. An optical brightener according to claim 4, further characterized in that G is di- (2-hydroxy-ethyl) amino.

6. An optical brightener according to claim 5, further characterized in that Q is 3- (2'-sulfatoethyl-sulphonyl) -phenylamino or an alkali metal salt thereof.

7. An optical brightener according to claim 4, further characterized in that Q is 3- (2'-sulfatoethyl-sulfonyl) -phenylamino or an alkali metal salt thereof.

8. An optical brightener according to claim 4, further characterized in that G is a group of formula wherein Ri and R2 are independently selected from hydrogen, alkyl Ci and C4, Ci and C4 alkoxy, hydroxyalkyl, cyano, phenyl substituted by 1 or 2 independently selected substituents consisting of chloro, hydroxy, alkoxy, sulfo and carboxy of C-i and C4.

9. An optical brightener according to claim 8, further characterized in that Ri and R together are piperidino, hexamethyleneimino, morpholino, or a substituted methyl or ethyl derivative thereof.