CA2268139A1

CA2268139A1 - Fiber-reactive brighteners of bis-s-triazinylaminostilbene

Info

Publication number: CA2268139A1
Application number: CA002268139A
Authority: CA
Inventors: Ronald P. Pedemonte; Thomas S. Phillips
Original assignee: Individual
Current assignee: Dystar LP
Priority date: 1996-10-02
Filing date: 1997-06-26
Publication date: 1998-04-09
Also published as: AU3409597A; JP2001507725A; EP0929532A1; WO1998014435A1; KR20000048764A; TR199900720T2

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.
Back4round The bis-s-triazinylaminostilbene 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;
~5 Williamson, R.; Elsevier Scientific Publishing Co., Amsterdam, The Netherlands (1980). Traditional optical brighteners, which are not fiber-reactive, are typically applied to celiulosic 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 2o 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:
/ IR3la N
[W - S02Y] b and 'f 5 (CH2)X S02Y
wherein:

2 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 alkyiene groups in combination, e.g. arylene - alkylene or 1o 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;

3 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 fabrics. 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 ~5 (0.1-2.0% on weight of goods) to effect whiteness. It wouid 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.

4

5 PCT/US97/10948 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:
NH\ /N\ /G
G HOsS ~ ~'H
~ _ D NON
N N C C'H

~N HN
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 ~ 5 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:
NH\ /N\ /G
G H03 ~' '~S
~ H~ O NON
N"N C=C\
H
~ S03H Q
' 'N HN
Q
Formula 1 wherein:
G represents alkoxy substituent of one to four carbon atoms, hydroxylalkoxy, hydroxy, cyanamide, halogen, substituted or

6 unsubstituted phenoxy, the formula Q, or a substituted or unsubstituted aliphatic or aromatic amino group of the formula:
,R1 -N

in which R~ and Rz are independently selected from hydrogen, a tower 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 Rz together represent the ~5 radical of a saturated, heterocyclic moiety e.g. the piperidino, hexamethyfeneimino or morpholino moiety, and methyl substituted or ethyl substituted derivatives thereof.
Q is a group of the formula (2a) or (2b):

7 / ~R3)a N
\ ~ - S02Y) b (2a) ( CHz)X S02Y
(2b) wherein:
~o 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 ~5 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

8 carboxy. The alkyl moiety may be substituted by substituents such as halogen, (CI, F) Br), carboxy, hydroxy, cyano) sulfamoyl, 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, sulfamoyl, 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 ~5 carbon atoms. The aryiene 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-, -SOZ-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 2o covalent bond.

9 Suitable substituents for the arylene group include halogen (CI, F, Br), hydroxy, C~ to C4 alkyl, C~ to C4 alkoxy, sulfo, carboxy) cyanamide, vitro, amino, cyano, sulfato, phosphato, etc.
Suitable substituents for the alkylene group include halogen (Cl, F, Br), hydroxy) C~ to C4 alkoxy) cyano, vitro, 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 ~5 particular the 2-sulfatoethyl group, a is the number zero or 1 and b is the number 1 or 2,

10 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-(SOZ-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 ~ 5 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 20 temperatures from 30-80 ~C. Preferably the brighteners are applied

11 WO 98l14435 PCT/US97/10948 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 carriedout preferably is at temperatures between 0-10 C, the secondstep 10-40 C) and at the third step at 50-80 C. The reactions carriedout in an acidic are to alkaline pH range.
~ 5 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.
Exam,~le 1:
2o 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

12 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 1o 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 - CHZ - OH)z and Q is:
\NH

13 Exam Ip a 2:
This product was prepared as described for example 1, except that 1 aminobenzene-4-(2-suffatoethyl)-suffone 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-~5 aminobenzene-2-methoxy-5-methyl-4-{2-sulfatoethyl)-sulfone replaced the 1-aminobenzene-3-{2-sulfatoethyl)-sulfone in the last condensation.
Exam Ip a 5:
This product was prepared as described for example 1, except that 1 2o aminobenzene-2,5-dimethoxy-4-(2-sulfatoethyl)-sulfone replaced the 1 aminobenzene-3-(2-sulfatoethyl)-sulfone in the last condensation.

14 xam I
This product was prepared as described for example 1, except that N-phenyl-2-(2-sulfatoethyl)-ethylamine replaced the 1 aminobenzene-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-1o described procedures.
NHYN\ /G
G H03 ~S
H
__ O NO N
N N C C'H
~ S03H Q
"N HN
Q
Formula 1

15 Table 1: Further Optical Brightener Examples Exam~l_e G
7 NHCN ~H
I / SO=CH,CH=OSO,H

I
SOjCHiCHyOSOyH
g N .;H
C~ I
/ SOICH~CHiOSO,H
N NH
I/
c~ \

SO=CHZCfIiOSO,H
11 NH ''H
\ I
/ so~cH,cH,oso,H
NH hH
\
I
/
/ so,cH~cnjosoya 13 Nt~ .H
\
I / SO=CH:CH=OSO,H
SO,H

16 X 1'1't I S2 CH~CH3 sH
N
CHZC~-~3 SOiCHiCHiOSO,H

N I\
~CH2CH3 /
so~cHIcHjoso,H

17 OCH3 '"
/ SOzCHICH=OSO;H
OC~..~3 NH
I
SOiCHiCHzOSO;H
19 NH .H
SO~H \
SO=CHiCH=OSO~H
H;OS

SO;H \
H;OS
SO_CH;CHiOSO;H
21 N NH~SO~OS03H
O

N'~/SO~OS03H
W

Example Sz 23 N N ~50z~0503Fi c~

24 ~pH N~SOZ~/\OSO3H
N
i 25 NH \H
\ I \
S02CH1CH,OSO,H SOICHiCHiOSO,H

\ ' \
I / /
SOiCHzCHiOSO,H S02CHICH;OSO,H
27 ~a vH
I / I / so=cH,cH,oso,H
SOzCHiCH=OSO~H
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

18 WO 98l14435 PCT/US97110948 following tables compare the compositions of the invention to CI 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.
Optical 0.10% 0.20% 0.40% 0.80%
Brightener C. 7. 28 125.3 131.6 136.2 138.7 Example 1 136.3 140.8 134.5 124.9 Note; Example 1 has less whiteness than C.I. 28 at 0.40 and 0.80% depths due to saturation of the brightener on the cotton, therefore creating a yellowing effect.
~o Table 3: Comparison of Whiteness Values for C.I. Optical Brightener 28 versus Example 1 at 140 ~F with alkali.
Optical 0.10% 0.20% 0.40% 0.80%
Brightener C. I. 28 125.2 129.5 131.3 127.2 Example 1 130 132.1 132.2 121.5 ~5 * 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. 1. Optical Brightener 28 versus Example 1 at 160 ~F with alkali.
Optical 0.10% 0.20% 0.40% 0.80%
Brightener C. I. 28 124.9 128 128.8 125.5 Example 1 134 135.7 134.5 128.6 Table 5: Comparison of Whiteness Values for C. I. Optical Brightener 28 versus Example 1 at 175 ~F with alkali.
Optical 0.10% 0.20% 0.40% 0.80%
Brightener C. I. 28 130.1 131.5 136.3 128.5 Example 1 131.4 135.9 133.4 131.6

19 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 chioro 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-suffatoethyl)-sulfone, respectively.
Table 6: Comparison of Whiteness Values for Ackermann 425 Brightener versus Examples 7 and 8 at 140 ~F with alkali.
Optical 0.10% 0.20% 0.40% 0.80%

Brightener 425 99.4 103.2 103.3 108.2 Example 123.7 126.4 126.5 119 Example 121.9 124.6 122.4 117.7 As can be seen from the above data, the composition of the invention consistently give higher whiteness values over the prior art at lower ~ 5 concentrations and at lower application temperature which results in lower material, energy, and environmental (waste water clean-up) costs.

Claims

page 21

Claim 1:
An optical brightener of the bis-s-triazinylaminostilbene series having at least one fibre-reactive group of the vinylsulfone series corresponding to the formula (1) or (2) wherein:
R3 is hydrogen, substituted or unsubstituted phenyl, substituted or unsubstituted (C1 to C4)-alkyl, substituted or unsubstituted (C1 to C4)-alkoxy or substituted or unsubstituted cyclohexyl;
W is substituted or unsubstituted alkylene of 1 to 8 carbon atoms which may be interrupted by N, S or O, or is substituted or unsubstituted meta-phenylene or is substituted or unsubstituted naphthylene or is a combination of said alkylene and phenylene or of said alkylene and naphthylene where the alkylene and phenylene, respectively naphthylene, may be linked with one another by a covalent group or by -SO2- , -CO-, -SO2-NH- or -CO-NH- ;
Y is vinyl, 2-sulfatoethyl, 2-thiosulfatoethyl, 2-phosphatoethyl or 2-alkanoyloxy-ethyl with a 2 to 5 carbon alkanoyl moiety;
a is zero or 1 and b is 1 or 2 with the proviso that the sum of (a + b) is 2 ;

page 22 x is a number selected from 1 to 8;
X and N form together a bivalent radical of a heterocyclic ring 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.
Claim 2:
An optical brightener according to claim 1, wherein Y is 2-sulfatoethyl.
Claim 3:
An optical brightener according to claim 1, wherein Y is vinyl.
Claim 4:
An optical brightener according to claim 1, having the formula wherein:
Q is a group of the formula (1) or (2) defined in claim 1;
G is (C1 to C4)-alkoxy, hydroxyalkoxy, hydroxy, cyanamide, halogen, substituted ur unsubstituted phenoxy or a group page 23 of the formula (1) or (2), or is a substituted or unsubstituted ammo group or a substituted or unsubstituted aliphatic amino group or a saturated heterocyclic moiety selected from piperidino, hexamethyleneimino, morpholino or methyl or ethyl derivatives thereof. ,
Claim 5:
An optical brightener according to claim 4, wherein G is di-(2-hydroxy-ethyl) amino.
Claim 6:
An optical brightener according to claim 5, wherein Q is 3-(2'-sulfatoethyl-sulfonyl)-phenylamino or an alkali metal salt thereof.
Claim 7:
An optical brightener according to claim 4, wherein Q is 3-(2'-sulfatoethyl-sulfonyl)-phenylamino or an alkali metal salt thereof.
Claim 8:
An optical brightener according to claim 4, wherein G is a group of the formula <IMG >

page 24 in which R1 and R2 are independently selected from hydrogen, (C1 to C4)-alkyl, (C1 to C4)-alkoxy, (C2 to C4)-hydoxyalkyl, cyano, phenyl, phenyl substituted by one or two independently selected substituents consisting of chlorine, hydroxy, (C1 to C4)-alkoxy, sulfo and carboxy.
Claim 9:
An optical brightener according to calim 8, wherein R1 and R2 together are piperidino, hexamethyleneimino, morpholino, or a methyl or ethyl substituted derivative thereof.