WO1998014435A1

WO1998014435A1 - Fiber-reactive brighteners of bis-s-triazinylaminostilbene

Info

Publication number: WO1998014435A1
Application number: PCT/US1997/010948
Authority: WO
Inventors: Ronald P. Pedemonte; Thomas S. Phillips
Original assignee: Dystar, L., P.
Priority date: 1996-10-02
Filing date: 1997-06-26
Publication date: 1998-04-09
Also published as: CA2268139A1; TR199900720T2; EP0929532A1; KR20000048764A; JP2001507725A; AU3409597A

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

Fiber-Reactive Brighteners of Bis-s-Triazinylaminostilbene

BACKGROUND OF THE INVENTION

Technical Field

The invention relates to the technical field of optical brighteners of the

bis-s-triazinlyaminostilbene series which are substituted on the triazinyl rings by

vinyl sulfone containing fiber-reactive substituents.

Background

The bis-s-triazinyiaminostilbene based brighteners represent the largest

class of optical brighteners in the market today. US Patent No. 3,723,425 to

Ackermann et al discloses the use and preparation of this class of brighteners.

The chemistry and use of optical brighteners is well known, see e.g. Textile

Science and Technology, Vol. 4, Fluorescent Optical Brightening Agents;

Williamson, R.; Elsevier Scientific Publishing Co., Amsterdam, The Netherlands

(1980). Traditional optical brighteners, which are not fiber-reactive, are typically

applied to cellulosic substrates in neutral or alkaline baths by continuous or

exhaust applications. Application of the optical brightener from an alkaline

bath in the presence of a bleaching agent (i.e. peroxide) is preferred from an

economic standpoint. Although, non-fiber reactive optical brighteners are

typically applied in relatively low concentrations (0.1-2.0% on weight of goods) to effect whiteness, it would be economically and environmentally

advantageous if significantly lower

amounts of brightener could be used to achieve similar whiteness. This

invention provides these advantages.

SUMMARY OF THE INVENTION

This invention is that of an optical brightener of the bis-s-

triazinylaminostilbene series having at least one fiber reactive vinyl sulfone

substituent selected from:

and

wherein: R₃ is selected from hydrogen, a substituted or unsubstituted phenyl, a

substituted or unsubstituted alkyl of one to four carbons, a substituted or

unsubstituted alkoxy of one to four carbons and a substituted or

unsubstituted cyclohexyl substituent;

W is selected from a substituted or unsubstituted arylene, e.g. phenylene

and naphthylene; a substituted or unsubstituted alkylene of 1 to about 8

carbons, e.g. methylene, ethylene and propylene, or two or three of said

arylene and alkylene groups in combination, e.g. arylene - alkylene or

arylene -alkylene - arylene or alkylene - arylene - alkylene; etc.

Y is selected from vinyl, 2-sulfatoethyl, 2-thiosulfatoethyl, 2-

phosphatoethyl, and 2-alkanoyloxyethyl wherein said alkanoyl has 2 to 5

carbon atoms.

a is a number selected from 0 and 1 ;

b is a number selected from 1 and 2; with the proviso that the sum of a +

b is 2; The moiety X 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 hetero atom (N, 0, S); and

x is a number selected from 1 to 8.

The compounds of the invention are useful in the optical brightening of

organic materials and especially useful in textile fibers and fabπcs. The optical

brighteners of the invention provide equivalent whiteness as the prior art at one

fourth the concentration.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

Optical brighteners are typically applied in relatively low concentrations

(0.1-2.0% on weight of goods) to effect whiteness. It would be economically

and environmentally advantageous if significantly lower amounts of brightener

could be used to achieve similar whiteness This invention provides such

advantages; i.e. compounds of the invention provide essentially the same

degree of whiteness as the prior art brighteners at one fourth the concentration. Optical brightener of the prior art of the 4,4' bis-s-triazinylaminostilbene

type are well known as is their preparation and use; see e.g. U.S. No.

3,723,425. These compounds, in their free acid form, have the following

general formula:

wherein:

the 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, hexamethylaneimino, morpholino, and halogen.

Generally the groups G and B are such that the compounds are

symmetrical in that the G and B substituents are the same on both sides

of the molecule, but they may be different. Typical substituents on said

aromatic and aliphatic amines are hydrogen, cyano, phenoxy,

substituted and unsubstituted C, to C₄ alkyl, substituted and

unsubstituted C-, to C₄ alkoxyl, a substituted or unsubstituted alkoxyalkyl of 3 to 8 carbons or a phenyl substituent which may be substituted by

one or two substituents selected from chlorine, sulfo, C^ to C₄ alkyl, C, to

C₄ hydroxyalkyl, C, to C₄ alkoxy, etc. U.S. Patent No. 3,018,287 to Fleck

is another example of the prior art bis-s-triazinylaminostilbene

brighteners.

Novel fiber-reactive brighteners which may be used in significantly lower

amounts than the prior have now been discovered 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 alkoxy substituent of one to four carbon atoms,

hydroxylalkoxy, hydroxy, cyanamide, halogen, substituted or unsubstituted phenoxy, the formula Q, or a substituted or unsubstituted

aliphatic or aromatic amino group of the formula:

in which R^ and R₂ are independently selected from hydrogen, a lower

alkyl of one to four carbon atoms, a lower alkoxy of one to four carbons,

a hydroxyalkyl group of two to four carbon atoms, an alkoxyalkyl group

of three to eight carbon atoms, wherein the oxygen atom and the

nitrogen atom are not bounded to the same carbon atom, cyano, or a

phenyl group which may be substituted by one to two independently

selected substituents such as chlorine, hydroxy lower alkyl of one to four

carbon atoms, alkoxy of one to four carbons, sulfo carboxy and

combinations of such substituents, or R^ and R₂ together represent the

radical of a saturated, heterocyclic moiety e.g. the piperidino,

hexamethyleneimino or morpholino moiety, and methyl substituted or

ethyl substituted derivatives thereof.

Q is a group of the formula (2a) or (2b):

wherein:

R₃ is selected from hydrogen, an unsubstituted or substituted phenyl

group, or an unsubstituted or substituted alkyl group of 1 to 4 carbon

atoms; e.g. methyl or ethyl. The phenyl moiety may be substituted by

one or two substituents independently selected from halogen, (e.g.

chlorine and bromine), alkoxy of 1 to 4 carbon atoms, (e.g. methoxy and

ethoxy), alkyl of 1 to 4 carbon atoms, (e.g. methyl), sulfo, carboxy, and

cyclohexyl which may be substituted by halogen, (e.g. chlorine and

fluorine), alkoxy having 1 to 4 carbon atoms, (e.g. methoxy and ethoxy),

alkyl having 1 to 4 carbon atoms, (e.g. methyl and ethyl), sulfo and carboxy. The alkyl moiety may be substituted by substituents such as

halogen, (Cl, F, Br), carboxy, hydroxy, cyano, sulfamoyi, sulfo, sulfato, or

a substituted or unsubstituted phenyl moiety, as described above The

alkyl moiety may also be substituted by C, to C₄ alkoxy, hydroxyl, cyano,

an alkoxy having 1 to 4 carbon atoms, (e g methoxy and ethoxy), which

may be substituted by carboxy, hydroxy, cyano, sulfamoyi, sulfo, sulfato

or a substituted or unsubstituted phenyl moiety

W is selected from a substituted or unsubstituted arylene radical, e g

phenylene and naphthylene or a substituted or unsubstituted alkylene or

combinations thereof, e g an alkylene-arylene moiety or arylene-

alkylene moiety or alkylene-arylene-alkylene or arylene-alkylene-arylene

radical The term "alkylene" is intended to mean a branched or straight

chained moiety 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,

such as 1 or 2, hetero groups, such as nitrogen, or oxygen or sulfur

atoms or groups of the formula -S0₂-, -CO-, -S0₂-NH- or -CO-NH-, and

the alkylene and arylene portions in the combined alkylene/arylene

radicals can in each case be joined together by such a group or a

covalent bond Suitable substituents for the arylene group include halogen (Cl, F, Br),

hydroxy, C^ to C₄ alkyl, C, to C₄ alkoxy, sulfo, carboxy, cyanamide, nitro,

amino, cyano, sulfato, phosphato, etc.

Suitable substituents for the alkylene group include halogen (Cl, F, Br),

hydroxy, C., to C₄ alkoxy, cyano, nitro, amino, sulfo, carboxy, phenyl,

sulfato, etc.

Y is the vinyl group or a 2-sulfatoethyl, 2-thiosulfatoethyl or 2-

phosphatoethyl group or a 2 alkanoyloxy-ethyl group having 2 to 5

carbon atoms in the alkanoyl radical, such as the 2 -acetoxyethyl group,

or the 2-benzoyloxy-ethyl, 2-(sulfobenzoyloxy)-ethyl or 2-(p-

toluenesulfonyloxy)-ethyl group or a 2-haloethyl group, such as the 2

bromoethyl or 2-chloroethyl group, preferably the vinyl group and in

particular the 2-sulfatoethyl group,

a is the number zero or 1 and

is the number 1 or 2, in which the sum of (a+b) equals the number 2, and in which in the case

where B is 2, the groups of the formula -W-(S0₂-Y) can have the same

meaning as one another or a different meaning to one another,

X, together with the N atom, form a bivalent radical of a heterocyclic ring

with 1 or 2 alkylene groups having 1 to 5 carbon atoms and if

appropriate 1 or 2 hetero atoms, such as, N, S, O to a group such as the

piperazin-1 ,4-ylene or a piperidinylene radical.

The brighteners of this invention are suitable for the optical

brightening of organic materials, especially such materials made from

cellulose and from natural or synthetic polyamides. These materials may

be in the form of fibers such as cotton staple fiber, rayon, wool and nylon

fibers, or in other forms such as paper, fleeces, etc. They are applied to

cellulose fibers in an exhaust or continuous process; preferably by the

exhaust method. In the exhaust method, the brighteners are applied at

a ratio of goods to liquor of 1 :10-1 :50, at concentration of 0.1-0.4% on

weight of goods brightener and 1.0-5.0 g/L alkali (such as caustic soda,

potassium hydroxide, sodium carbonate, and sodium bicarbonate) at

temperatures from 30-80 °C. Preferably the brighteners are applied under alkaline conditions and in combination with bleaching agents such

as hydrogen peroxide.

Compounds of the invention are produced by reacting 2 moles of

2,4,6-trichloro-1 ,3,5-triazine, in the first or second synthesis stage, with

one mole of 4,4'-diaminostilbene-2,2'-disulfonic acid, or of an alkali metal

salt or alkaline-earth metal salt thereof. Two moles of each G and Q,

where both G and Q are described above, are then reacted in any

desired sequence, but preferably in the sequence in which G precedes

Q. The first step of the reaction is carried out preferably 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 in an acidic to

alkaline pH range.

The following examples are intended to illustrate the invention in its

preferred embodiments wherein the parts are parts by weight, percentages are

weight percent and degree are centigrade unless otherwise noted.

Example 1 :

A dilute solution of 11.1 parts diethanolamine was added dropwise into a

slurry containing 18.4 parts of cyanuric chloride, 50 parts ice, and 100 parts water. The reaction mixture was kept weakly basic throughout the

condensation with a dilute sodium carbonate solution. After 3-5 hours, a

neutral, aqueous solution of 18.9 parts of 4,4'diaminostilbene-2,2'-disulfonic

acid was added dropwise to the weakly basic diethanolamine-dichlorotriazine

condensation product at 30-45 °C. The reaction mixture pH was kept weakly

acidic until the condensation was complete with dilute sodium carbonate

solution. The final fiber-reactive optical brightener was obtained by adding 39.1

parts of 1-aminobenzene-3-(2-sulfatoethyl)-sulfone and heating to 70-75 °C

under acidic conditions. The final product was obtained by evaporating the

brightener solution in a low temperature oven. The quality of the final product was 75% (area) by HPLC. This product has the structure set forth in Formula 1

in which G is -- N (CH₂ - CH₂ - OH)₂ and Q is:

Example 2:

This product was prepared as described for example 1 , except that 1-

aminobenzene-4-(2-sulfatoethyl)-sulfone replaced the 1-aminobenzene-3-(2-

sulfatoethyl)-sulfone in the last condensation.

Example 3:

This product was prepared as described for example 1 except that 1-

aminobenzene-2-methoxy-5-(2-sulfatoethyl)-sulfone replaced the 1-

aminobenzene-3-(2-sulfatoethyl)-sulfone in the last condensation.

Example 4:

This product was prepared as described for example 1 , except that 1-

aminobenzene-2-methoxy-5-methyl-4-(2-sulfatoethyl)-sulfone replaced the 1-

aminobenzene-3-(2-sulfatoethyl)-sulfone in the last condensation.

Example 5:

This product was prepared as described for example 1 , except that 1-

aminobenzene-2,5-dimethoxy-4-(2-sulfatoethyl)-sulfone replaced the 1-

aminobenzene-3-(2-sulfatoethyl)-sulfone in the last condensation. Example 6:

This product was prepared as described for example 1 , except that N-

phenyl-2-(2-sulfatoethyl)-ethylamine replaced the 1aminobenzene-3-(2-

sulfatoethyl)-sulfone in the last condensation.

Other examples that illustrate the invention are listed below in the

following Table 1 , where the Q and G moieties of the Formula 1 are as

described below. These brighteners can be synthesized by the above-

described procedures.

Formula 1

Table 1: Further Optical Brightener Examples

The optical brightener of the invention was applied to cotton fabric gray

goods under the conditions and concentrations set forth in the following tables

and the whiteness was measured using the AATCC Test Method 110 - 1994,

"Whiteness of Textiles". The strength of the brighteners of the invention were

standardized to 100% using Color Index Brightener 28 as a standard. The following tables compare the compositions of the invention to Cl Brightener 28,

a widely used commercial optical brightener.

Table 2: Comparison of Whiteness Values for C.I. Optical Brightener 28 versus Example 1 at 105 °F with alkali.

Note: Example 1 has less whiteness than Cl. 28 at 0.40 and 0.80% depths due to saturation of the brightener on the cotton, therefore creating a yellowing effect.

Table 3: Comparison of Whiteness Values for C.I. Optical Brightener 28 versus Example 1 at 140 °F with alkali.

* One whiteness value of 136.2 was obtained but this result could not be reproduced and is considered unreliable.

Table 4: Comparison of Whiteness Values for C. I. Optical Brightener 28 versus Example 1 at 160 °F with alkali.

Table 5: Comparison of Whiteness Values for C. I. Optical Brightener 28 versus Example 1 at 175 °F with alkali.

The following Table 6 compares compositions of the invention,

Examples 7 and 8, with other compositions of the prior art as exemplified in

U.S. Patent No. 3,723,425 to Ackermann, (the '425 Brightener). In the

Ackermann composition the substituents G and Q are cyanamide and chloro,

respectively. In Examples 7 and 8 which exemplify the invention, the chloro

group of Ackermann is replaced by the fiber-reactive moieties of this invention;

i.e. the reactive groups derived from aminobenzene-3-(2-sulfatoethyl)-sulfone

and aminobenzene-4-(2-sulfatoethyl)-sulfone, respectively.

Table 6: Comparison of Whiteness Values for Ackermann 425 Brightener versus Examples 7 and 8 at 140 °F with alkali.

As can be seen from the above data, the composition of the invention

consistently give higher whiteness values over the prior art at lower

concentrations and at lower application temperature which results in lower material, energy, and environmental (waste water clean-up) costs.

Claims

WE CLAIM:

Claim 1 :

An optical brightener of the bis-s-triazinylaminostilbene series having at

least one fiber reactive vinyl sulfone substituent selected from:

and

wherein:

R₃ is selected from hydrogen, a substituted or unsubstituted

phenyl, a substituted or unsubstituted C to C₄ alkyl, a substituted

or unsubstituted C₁ to C₄ alkoxyl and a substituted or

unsubstituted cyclo hexyl substituent; W is selected from a substituted or unsubstituted alkylene which

may be interrupted by a hetero atom selected from N,S,0; a

substituted or unsubstituted arylene wherein the ring of arylene

may be 1 to 3 hetero atoms selected from N,S,0, two to three

groups selected said arylene and said alkylene groups which are

joined together by covalent bond or a linking group selected from

-S0₂-, -CO-, -S0₂-NH- and -CONH-;

Y is independently selected from vinyl, 2-sulfatoethyl,

2-thiosulfatoethyl, 2-phosphatoethyl and 2-alkanoyloxyethyl

having a 2 to 5 carbon alkanoyl moiety;

a is selected from the numbers 0 and 1 and b is selected from the

number 1 and 2 with the proviso that the sum of a + b equals 2;

X together with N form a bivalent radical of a heterocyclic ring

consisting of 1 to 2 alkylene group of 1 to 5 carbon atoms which

may be optionally interrupted by a hetero atom selected from S,

O, and N and the alkali metal salts of said optical brightener. Claim 2:

An optical brightener according to Claim 1 wherein Y is sulfatoethyl.

Claim 3:

An optical brightener according to Claim 1 wherein Y is vinyl.

Claim 4:

An optical brightener according to Claim 1 wherein said brightener has

at least two fiber reactive vinyl sulfone substituents.

Claim 5:

An optical brightener according to Claim 1 having the formula:

wherein: Q represents the vinyl sulfone group of claim 1 ; and G is selected from

the group consisting of a C₁ to C₄ alkoxy group; a C., to C₄ hydroxy group;

cyanamide; halogen; a substituent or unsubstituted phenoxy group; Q as

defined in claim 1 ; a substituted or unsubstituted aromatic amino group; a

substituent or unsubstituted aliphatic amino group and a saturated heterocyclic

moiety selected from piperidino, hexamethylaneimino, morpholino, and methyl

and ethyl derivatives thereof.

Claim 6:

An optical brightener according to Claim 5 wherein the moiety G is:

Claim 7:

An optical brightener according to Claim 6 wherein Q is:

or an alkali metal salt thereof. Claim 8;

An optical brightener according to Claim 5 wherein Q is:

and the alkali metal salts thereof.

Claim 9:

An optical brightener according to claim 5 wherein G is a substituted or

unsubstituted aliphatic or aromatic amino group of the formula:

in which R and R₂ are independently selected from hydrogen, a C^ to C₄ alkyl

group, a C₁ to C₄ alkoxy group, a C₂ to C₄ hydroxyalkyi group a C₃ to C₈ alkoxy

alkyl wherein the oxygen atom and the nitrogen atom are not bounded to the

same carbon atom, a cyano group, a phenyl group which maybe substituted by

one to two independently selected substituents such as chlorine, hydroxy a C₁

to C₄ alkyl group, a C₁ to C₄ alkoxdy group, a sulfo carboxy group and

combinations of such substituents. Claim 10:

An optical brightener according to claim 9 wherein R and R₂ together

represent the radical of a saturated, heterocyclic moiety selected form the

group consisting of piperidino, hexamethyleneimino moiety, a morpholino

moiety and methyl substituted or ethyl substituted derivative thereof.