GB2150569A

GB2150569A - Sulphate esters of bis-phenol methane compounds

Info

Publication number: GB2150569A
Application number: GB08430447A
Authority: GB
Inventors: Hans-Peter Baumann
Original assignee: Sandoz AG
Current assignee: Sandoz AG
Priority date: 1983-12-05
Filing date: 1984-12-03
Publication date: 1985-07-03
Also published as: FR2555986B1; CH666480A5; JPH0461865B2; IT8449240A0; IT1199230B; HK191A; JPS60132947A; FR2555986A1; GB8430447D0; IT8449240A1; GB2150569B

Abstract

Compounds of formula I <IMAGE> in which R1 is isooctyl, nonyl or dodecyl, R2 is H or -SO3R6, R3 is &lparstr& A-O &rparstr& m R5 where each A, independently, is -C2H4-, -C3H6- or -C4H8-, R4 is &lparstr& B-O &rparstr& n R5 where each B, independently, is -C2H4-, -C3H6- or -C4H8-, R5 is H or -SO3R6, provided that at least one R5 is -SO3R6, R6 is H, an alkali metal, an equivalent of an alkali earth metal or optionally substituted ammonium, m is 1, 2 or 3 and n is 0, 1 or 2, provided that m + n is at most 4, when n=0 then R5 is H and m = 1, when only one group R5 is -SO3R6 and n = 1 or 2 then both R2's are H, are useful as emulsifying and dispersing agents, especially as dyeing or printing assistants for dyeing or printing a substrate dyeable with anionic or disperse dyes.

Description

SPECIFICATION Improvements in or relating to organic compounds The present invention relates to bis-phenol-methane derivatives useful as dispersing or emulsifying agents.

According to the invention, there are provided compounds of formula I

in which each R1, independently, is isooctyl, nonyl or dodecyl each R2, independently, is hydrogen or -S03R6 Rs isfA - OtmRs where each A, independently is -CH2H4-, -C3H6 or -C4H8 R4 is+B - OtnRs where each B independently, is -C2H4-, -C3H6- or -C4H8 each R, independently, is hydrogen or -SO3R6, provided that at least one R5 is -S03R6 each R6, independently, is hydrogen, an alkali metal, an equivalent of an alkal earth metal, ammonium or substituted ammonium, m is1,2or 3, and nisO,1 or2 with the provisos that the total sum m + n is at most 4, that when n = 0 then R5 in R4 is hydrogen and m is 1 and that when only one group R5 is -SO3R6 and n = 1 or 2 then both R2's are hydrogen.

In the compounds of formula I, the symbols R1 are preferably identical and are more preferably nonyl.

When n = O or each F3 and R4 contain a terminal -SO3R6 group, one symbol R2 is preferably hydrogen and the other is hydrogen or -S03R6, preferably -S03R6.

R3 or R4 may also be a mixed chain containing -C2H4-, -C3H6- and/or -C4H8- in any sequence. When n = 1 or 2, F3 and R4 may contain an identical or different alkylene oxide addition chain. Preferably R3 is distinct from R4.

R3 is preferably

R4 is preferably

more preferably n isO and this case R4 is H and m is 1.

Substituted ammonium as F6 is an ammonium substituted by up to four C14alkyI or up to three fr, y- or o-hydroxy-C2 4alkyl, e.g. dimethylammonium, trimethylammonium or mono-, di- or triethanolammonium, or cycloimmonium. The latter is an ammonium group incorporated in a cyclic system which may contain further hetero atoms. When F6 is cycloimmonium it is preferably morpholinium.

F6 is preferably hydrogen, sodium, potassium, ammonium or monoethanolammonium, more preferably monoethanolammonium. The R6,s symbols are preferably all identical in the molecule.

The sum m + n is preferably 1 or 2, particularly 1.

Preferred compounds of formula I are those in which the R1's are nonyl, at least one R2 is hydrogen, R3 is #CH2CH2-O#mR5 or+C3H6-O+rnFs, R4 is#CH2CH2-O#nR5 or+C3H6-OtnR5, at least one F5 is -SO3R6, the R6's are hydrogen, sodium, potassium, ammonium or monoethanolammonium, m is 1,2 or 3 and n is0, 1 or 2, the total sum m + n being 1,2,3 or 4 with the above indicated provisos.

More preferred compounds of formula I are those in which the Rr's are nonyl, one R2 is hydrogen and the other is -SO3R6, R3 is

where Rg is -S03F6, R4 is hydrogen, the F6,s are hydrogen, sodium, potassium, ammonium or monoethanolammonium, and m is 1.

The compounds of formula I are prepared by reacting a compound of formula II

in which R7 isfA-O-f,H R8 is+BOtnH and A, B, R1, m and n are as defined above, provided that the total sum m + n is at most 4 and when n is O then m is 1 with sulphurtrioxide, sulphuric acid, oleum, aminosulphonic acid or chlorosulphonic acid in a mole ratio of 1:1.5-2 and, where desired, converting the free sulphonic acid group(s) into an alkali metal, alkali earth metal, ammonium or substituted ammonium salt form.

The sulphation/sulphonation reaction is carried out in accordance with known methods. In this reaction, the terminal hydroxy group of the alkylene oxide chain(s) is first sulphated. If the sulphating agent is present in excess, then the benzene rings are sulphonated. Depending on the presence of one or two of such terminal hydroxy groups and on the amount of sulphurtrioxide oleum, sulphuric acid or amino- or chlorosulphonic acid used, there can be produced compounds of formula I containing one or two sulphuric acid semi-ester groups (one Rs or both R5's) and, provided that no unsulphonated alkylene hydroxy group is present, up to two sulphuric acid groups on the benzene rings and mixtures thereof.

Chlorosulphonic acid is preferred as a sulphating agent and optionally as a sulphonating agent.

The compounds of formula I in free acid form can be converted into the salt form by neutralization with an organic or inorganic base, e.g. an alkali metal hydroxide, an alkali earth metal hydroxide, ammonia or a basic amine.

The compounds of formula II may be prepared by analogy with known methods, e.g. by condensing an iso-octyl, nonyl- or dodecyl-phenol with formaldehyde at a mole ratio 2:1, preferably in the presence of an acid catalyst. The resulting binuclear compounds are then alkoxylated with 1-4 moles ethylene oxide, propylene oxide and/or butylene oxide.

The compounds of formula I are useful emulsifying and dispersing agents. They are particularly suitable as dyeing or printing assistants, e.g. as levelling agents.

Dyeing and printing in the presence of compounds of formula I as levelling agents may be carried out in accordance with known methods for dyeing or printing textile substrates dyeable with an anionic or disperse dyestuff. The amount of compound of formula I employed in the dyeing or printing paste will depend on the textile substrate, the dyestuff employed, the pH of the bath and the treatment time. In general suitable amounts are in the range of from 0.02 to 20 % by weight, preferably 0.1 to 15% by weight based on the weight of the substrate.

The preferred substrates are those comprising natural or synthetic polyamides, polyesters or cellulose acetate or mixtures thereof. The compounds of formula I result in level dyeings especially in the case of stripy nylon.

The compounds of formula I may also be used as assistants for dyeing leather. They are also valuabie dispersing or emulsifying agents for the preparation of agrochemical formulations or for use in the paper industry.

When the compounds of formula I are employed as dispersing or emulsifying agents, they are employed in accordance with known methods and in conventional amounts.

The compounds of formula I in which at least one R2 is -S03R6 are also useful as stabilizing agents for peroxides in peroxide bleaching. They are particularly suitable for stabilizing hydrogen peroxide, preferably in admixture with a silicate.

The compounds of formula I may have a low solubility in water depending on their sulphation and sulphonation rate and their salt form. For example, sodium salts are less hydrosoluble than the monoethanolammonium salts.

The compounds of formula I are conveniently used in admixture with a co-surfactant and such compositions form also part of the invention. Suitable co-surfactants include aliphatic C3 6 alcohols and their ethers, e.g. isopropanol, cyclohexanol, butanol, isobutanol, 2-methyl-2,4-pentanediol, 1-butoxy-2hydroxyethane, butyleneglycol, butyldiglycol and mixtures thereof. The weight ratio of the compound of formula i to the co-surfactant may vary from 3:17 to 17:3, preferably from 3:2 to 4:1. Preferred co-surfactants are butanol, isobutanol, butyleneglycol or butyldiglycol. Such mixtures are readily dilutable with water.

The present invention further provides a composition comprising a compound of formula 1, a co-surfactant and water. Preferred compositions are those containing from 15 to 30% by weight of a compound of formula I, 5 to 30% by weight of a co-surfactant and water up to 100%.

The following Examples further serve to illustrate the invention. In the Examples all parts are by weight and all temperatures are in degrees Centigrade.

Example 1 880 Parts nonylphenol are put into a flask and heated with stirring and introduction of a nitrogen stream to 50 . There are then added a solution of 13.2 parts oxalic acid dihydrate in 8.4 parts demineralised water, 4.4 parts sodium dodecylbenzenesulphonate and, finally, portionwise 63.2 parts paraformaldehyde at such a rate that the temperature in the flask rises to 85 - 95 . The resulting mixture is slowly heated to 120-125 and the water contained in the mixture is removed by distillation at approx. 5 mm Hg. The mixture is further heated to 1 60" and stirred at this temperature for 3 hours. The vacuum is broken by feeding in nitrogen, 5 parts solid sodium hydroxide are slowly added to the mixture and, while the pressure is reduced to approx.

18 mm Hg, 264 parts ethylene oxide are introduced under the surface.

584 Parts of the addition product obtained above are put into a flask. To this product are added 861 parts methylene chloride with stirring and the mixture is cooled to 2-5 .233 Parts chlorosulphonic acid are then added slowly to the mixture at such a rate that the temperature does not exceed 20 . The gaseous hydrogen chloride formed is absorbed by an aqueous sodium hydroxide solution.After completion of the chlorosulphonic acid addition, the resulting mixture is further stirred for about 3 hours, brought to room temperature and then added slowly to 190 parts monoethanolamine cooled to 2-5 , at such a rate that the temperature does not exceed 20 . After further stirring for 2 hours at room temperature, the methylene chloride is distilled off at approx. 65" while reducing the pressure to 60 mm Hg.

There are obtained 590 parts of the compound of formula

The compound is mixed with 300 parts isobutanol and stirred at approx. 40 to give a clear solution.

Instead of the 190 parts monoethanolamine, equimolar amounts of di- or triethanolamine, morpholine or ammonia may be used for the neutralisation to the salt form.

By following the same procedure but using the compounds of the Table in the indicated mole amounts, further compounds of formula I may be prepared. In each Example, the alkylphenol is reacted with formaldehyde art a mole ratio of 2:1.

TABLE Ex. No R, Mole Mole Alkyleneoxide Chlorosulphonic acid 2 Nonyl 3-Propyleneoxide 2 3 Dodecyl 3 Ethyleneoxide 2 4 Nonyl 2 Ethyleneoxide 2 5 do. 1 Ethyleneoxide 1,5 6 Nonyl 1 Propyleneoxide 2,25 7 do. 4 Ethyleneoxide 2 8 do. 4 Propyleneoxide 2 9 do. 3 Propyleneoxide 2,5 10 do. 1 Ethyleneoxide 2 11 Dodecyl 2 Ethyleneoxide 1,5 12 do. do. 2 13 Isooctyl do. 1,5 14 do. do. 2 15 Nonyl 1 Propyleneoxide + 2 2 Ethylenoxide 16 do. do. 2,5 17 do. 2 Propyleneoxide + 2 Ethyleneoxide 2 18 do. do. 1,5 19 do. 1 Propyleneoxide + 3 Ethyleneoxide 2 20 do. do. 2,5 21 do. do. 1,5 22 do. 1 Butyleneoxide 2,25 The resulting compounds are then admixed with isobutanol as disclosed in Example 1.

Application Example A 100 Parts stripy nylon 6 fabric are added to 1500 parts of a dyebath containing monosodium phosphate and tetrasodium pyrophosphate to adjust the bath pH to 8 0.6 parts of the dye C.I. Acid Red 57, and 2.0 parts of the compound of Example 6 in monoethanolamine salt form and treated with this dyebath at the boil for 90 minutes. The substrate is then rinsed and dried. A level red dyeing is obtained.

By repeating the procedure but replacing the dyestuff C.l. Acid Red 57 by C.l. Acid Blue 80, C.I. Acid Orange 148, C.l. Acid Orange 127, the same good results are obtained.

Application Example B 100 Parts of a 60:40 nylon 6/wool blended fabric are added to 3000 parts of a dyebath adjusted to pH 8 and containing 1 part of the dyestuff C.I. Acid Blue 80 and 4 parts of the compound of Example 1 in the monoethanolamine salt form, and dyed at 98" for 90 minutes. The substrate is then rinsed and dried. An excellent level deep blue dyeing is obtained.

In the above procedure, the compound of Example 1 may be replaced by the compound of Example 8 or 10 in an equivalent amount.

By repeating the procedure but replacing the dyestuff C.l. Acid Blue 80 by C.l. Acid Orange 145, C.l. Acid Orange 127, C.l. Acid Red 299, C.I. Acid Red 57, C.l. Acid Red 263, C.l. Acid Violet 48, C.l. Acid Blue 126 or C.l.

Acid Blue 271, the same good results are obtained.

Application Example C A polyester fabric is dyed with 0.5% of the dyestuff C.l. Disperse Red 13 with the addition of 2 g/l ammoniumsulphate and 2 g/l of the compound of Example 6 at pH 5 (adjusted with formic acid). The liquor to goods ratio is 20:1. The dyeing is effected at 130"for 20 minutes. The substrate is washed and rinsed. A level dyeing is obtained.

In Examples A-C, the compound of formula I is used in admixture with isobutanol as disclosed in Example 1. The isobutanol may also be replaced by an equivalent amount of butyldiglycol.

Claims

1. Acompound oftheformula I

in which each F1, independently, is isooctyl, nonyl or dodecyl each R2, independently, is hydrogen or -SO3R6 R3 isfA - OAmR5 where each A, independently, is -C2H4-, -C3H6- or -C4H8- R4 is+B - Oinks where each B, independently, is -C2H4-, -C3H6- or -C4H8 each Rs, independently, is hydrogen or -SO3R6, provided that at least one Rg is -So3R6 each R6, independently, is hydrogen, an alkali metal, an equivalent of an alkal earth metal, ammonium or substituted ammonium, mis 1,2 or3, and nisO,1 or2 with the provisos that the total sum m + n is at most 4, that when n = 0 then Rs in R4 is hydrogen and m is 1 and that when only one group Rs is -SO3R6 and n = 1 or 2 then both R2,s are hydrogen.

2. A compound according to Claim 1, in which R4 is+CH2CH2-OinRs or

3. A compound according to Claim 1 or 2, in which when F6 is substituted ammonium it is an ammonium substituted by up to four C1.4alkyl or up to three t3-, -or -hydroxy-C2.4 alkyl or cycloimmonium.

4. A compound according to any one of the preceding claims, in which F6 is hydrogen, sodium, potassium, ammonium or monoethanolammonium.

5. A compound according to any one of the preceding claims, in which F3 is

6. A compound according to any one of the preceding claims in which n is0.

7. A compound according to any one of the preceding claims in which the sum m + n is 1 or 2.

8. A compound according to Claim 7 in which the sum m + n is 1.

9. A compound according to any of the preceding claims, in which the Rl's are nonyl, one R2 is hydrogen and the other is hydrogen or -SO3R6, R3 is+CH2CH2-OtmR5 or tC3H6-OtmR5, R4 iSfCH2CH2-0tnR5 ortC3H6-OtnR5, each R5, independently is hydrogen or -SO3R6 provided that at least one Rg is -S03R6, the F6,s are hydrogen, sodium, potassium, ammonium or monethanolammonium, m is 1,2 or 3 and n is 1 or 2, with the provisos that the total sum m + n is 1,2,3 or 4 that when n = 0 then R in R4 is hydrogen and m is 1 and that when only one group Rg is -SO3R6 and n = 1 or 2, then both F2,s are hydrogen.

10. A compound according to Claim 9, in which the R1,s are nonyl, one R2 is hydrogen and the other is -SO3R6, R3 is

where Rg is -SO3R6, R4 is hydrogen, the R6,s are hydrogen, sodium, potassium, ammonium or monoethanolammonium, and m is 1.

11. A compound of formula I as defined in Claim 1 substantially as hereinbefore described with reference to Examples 1 to 22.

12. A process for the production of a compound of formula I as stated in Claim 1,which process comprises reacting a compound of formula li

in which R7 isA - O+rnH R8 isB - O+nH and A, B, R1, m and n are as defined in Claim 1 the total sum m + n being at most 4 and m = 1 when n is0 with sulphurtrioxide, sulphuric acid, oleum, aminosulphonic acid or chlorosulphonic acid in a mole ratio of 1:1.5-2 and, where desired, converting the free sulphonic acid group(s) into an alkali metal, alkali earth metal, ammonium or substituted ammonium salt form.

13. A process for the production of a compound of formula I as defined in Claim 1, substantially as hereinbefore described with reference to Examples 1 to 22.

14. A process for dyeing or printing a substrate dyeable with anionic dyestuffs or a substrate dyeable with disperse dyestuffs comprising employing a compound of formula I according to Claim 1 as dyeing or printing assistant.

15. A process according to Claim 14 in which the compound of formula lisa compound as stated in any one of Claims 2 to 11.

16. A process according to Claim 14 or 15, in which the amount of compound of formula I is from 0.2 to 20% by weight of the substrate.

17. A process according to any one of Claims 14 to 16, in which the substrate consists of or comprises cellulose acetate, polyester or natural or synthetic polyamides.

18. A process according to any one of Claims 14 to 17, in which the compound of formula I is mixed with an aliphatic C3 6 alcohol oran etherthereof.

19. A process for dyeing or printing a substrate dyeable with anionic or disperse dyestuffs, substantially as hereinbefore described with reference to any one of Examples A two C.

20. A dyed or printed substrate whenever obtained by a process according to any one of Claims 15 to 19.

21. A process for dyeing leather comprising employing a compound of formula I according to Claim 1 as dyeing assistant.

22. A composition comprising a compound of formula I as stated in Claim 1 in admixture with a co-su rfactant.

23. A composition according to Claim 22, in which the co-surfactant is an aliphatic C3-6 alcohol or an ether thereof.

24. A composition according to Claim 23, in which the co-surfactant is selected from isopropanol, cyclohexanol, butanol, isobutanol, 2-methyl-2,4-pentanediol, 1 -butoxy-2-hydroxyethane, butyleneglycol, butyldiglycol and mixtures thereof.

25. A composition according to any one of Claims 22 to 24 in which the weight ratio of the compound of formula I to the co-surfactant is from 3:17 to 17:3.

26. A composition according to Claim 25, in which the weight ratio of the compound of formula I to the co-surfactant is from 3:2 to 4:1.

27. A composition according to any one of Claims 22 to 26 containing from 15 to 30% by weight of a compound of formula I as stated in Claim 1,5 to 30% by weight of a co-surfactant and water up to 100%.

28. A composition substantially as hereinbefore defined with reference to any one of Examples 1 to 22.