FR2555986A1 - NOVEL PHENOLIC COMPOUNDS, THEIR PREPARATION AND THEIR USE AS DISPERSION AGENTS AND EMULSIFIERS - Google Patents

Abstract

THE SUBJECT OF THE PRESENT INVENTION IS THE COMPOUNDS OF FORMULA I: (CF DRAWING IN BOPI) IN WHICH R REPRESENTS AN ISOOCTYL, NONYL OR DODECYL GROUP, R REPRESENTS HYDROGEN OR A -SOR GROUP, R REPRESENTS - (AO-) R IN WHICH EACH A REPRESENTS A -CH, -CH- OR -CH-, R GROUP REPRESENTS - (BO-) R IN WHICH EACH B REPRESENTS A -CH-, -CH- OR -CH- GROUP, R REPRESENTS HYDROGEN OR A -SOR GROUP, AT LEAST ONE OF R TO MEAN A -SOR GROUP, R REPRESENTS HYDROGEN, AN ALKALINE METAL, AN EQUIVALENT OF AN ALKALINO-EARTH METAL OR AN AMMONIUM GROUP POSSIBLY SUBSTITUTED, M MEANS 1, 2 OR 3 AND N MEANS 0, 1 OR 2, MN SHOULD NOT BE GREATER THAN 4, R IN R SHOULD MEAN HYDROGEN AND M MEAN 1 WHEN N 0, THE TWO R SYMBOLS SHOULD MEAN HYDROGEN WHEN A SINGLE R MEANS ONE GROUP -SOR AND NO. 1 OR 2. THESE COMPOUNDS MAY BE USED AS DISPERSING AGENTS OR EMULSIFIERS.

Description

The subject of the present invention is new phenolic derivatives, their

  preparation and their use as agents of

dispersion or emulsifiers.

  The present invention more particularly relates to the compounds of formula I

R1 R

R2 CH22 (I)

OR3 OR4

  wherein each R1 independently represents an isooctyl, nonyl or dodecyl group, each R2 independently represents hydrogen or a group

-S03R6,

  R3 is -A-O-mR5 wherein each A is independently -C2H4-, -C3H6- or -C4H8-, R4 is -B-Oj-nR5 wherein each B is independently -C2H4-, -C3H6- or

-C4H8-,

  each R5 independently represents hydrogen or a group -SO3R6, at least one of R5 to mean a group

-S03R6,

  each R6 independently represents hydrogen, an alkali metal, an equivalent of an alkaline earth metal, an ammonium group or a substituted ammonium group, m is 1, 2 or 3, and n is 0, 1 or 2, the sum total m + n must not be greater than 4, R5 in the substituent R4 must mean hydrogen and m mean 1 when n = 0, the two symbols R2 must mean hydrogen when one

  symbol R5 means a group -SO3R6 and n = 1 or 2.

  In the compounds of formula I, the symbols R 1 are preferably identical and more preferably signify a nonyl group. When n = 0 or when each symbol R3 and R4 contains a group -SO3R6 terminal, one of the symbols R2 preferably means hydrogen and the other signifies hydrogen or a group

  -SO3R6, preferably a group -SO3R6.

  R3 or R4 can also be a mixed chain containing a

  -C2H4-, -C3H6- and / or -C4H8- group in any sequence.

  When n = i or 2, R3 and R4 can each represent a chain

  identical or different alkyleneoxy.

  R3 is preferably - (-CH-CH2-O-hnR5-.

  CH3 R4 is preferably - <- CH2CH2-oO-R5 or #CH-CH-O tR; CH3 n is more preferably 0 and in this case R4 means

hydrogen and m means 1.

  The substituted ammonium group represented by R 6 is an ammonium group substituted with a maximum of 4 C 1 -C 4 alkyl groups or a maximum of 3 C 3 -C 4, 3- or 4-hydroxyalkyl groups, e.g. dimethylammonium, trimethylammonium or mono-, di- or triethanolammonium or cycloimmonium. The latter is an ammonium group incorporated in a cyclic system which can contain

  other heteroatoms. When R6 represents a cyclo-

  immonium, it is preferably the morpholinium group.

2555986.

  R6 preferably means hydrogen, sodium, potassium, ammonium group or monoethanolammonium group, more preferably monoethanolammonium group. R6 symbols are

  preferably all identical in the molecule.

  The sum m + n is preferably equal to 1 or 2, more

preferably 1.

  The preferred compounds of formula I are those in which the symbols R 1 signify a nonyl group, at least one substituent R 2 signifies hydrogen, R 3 signifies - (CH 2 CH 2 -OtmR 5 or - (- C 3 H 6 -OtmR 5, R 4 signifies - (rCH 2 CH 2 O -hnR5 or - {C3H6-O} -nR5, at least one substituent R5 is -SO3R6, R6 is hydrogen, sodium, potassium, ammonium or monoethanolammonium, m is 1, 2 or 3 and n is 0, 1 or 2, the total sum m + n being equal to 1, 2, 3 or 4

  with the above conditions.

  Particularly preferred compounds of formula I are those in which the symbols R1 signify a nonyl group, one of the symbols R2 signifies hydrogen and the other signifies a group -SO3R6, R3 signifies -t CH-CH2-0-). mRs in which R5 means a

CH3

  -S03R6 group, R4 stands for hydrogen, R6 stands for hydrogen, sodium, potassium, ammonium group or

  monoethanolammonium group, and m is 1.

  According to the process of the invention for preparing compounds of formula I a compound of formula II is reacted

R1 R

31 CH2

  OR7 op8 OR8 wherein R7 is - (- AO -0 H R8 is - + BO --nH and A, B, R1, m and n are as defined above, the sum total m + n not to be greater than at 4 and m being 1 when n is 0 with sulfur trioxide, sulfuric acid, oleum, aminosulphonic acid or chlorosulfonic acid in a molar ratio of 1: 1.5-2 and if necessary, the transformation of the group or groups

  sulpho in their alkali metal salts, alkali metal

  earthy, ammonium or substituted ammonium.

  The sulfation / sulfonation reaction is carried out according to known methods. In this reaction, the terminal hydroxy group of the alkyleneoxy chain or chains is first sulfated. If the sulphating agent is present in excess, then the benzene rings are sulphonated. Depending on the presence of one or two terminal hydroxyl groups of this type and the amount of sulfur trioxide, oleum, sulfuric acid or amino or chlorosulfonic acid used, compounds of formula I containing one or two semi-ester residues of sulfuric acid (one of R5 or both of R5) and, provided that no unsulfonated hydroxyalkylene group is present, a maximum of two sulfo groups on the benzene rings, and mixtures of these compounds. Chlorosulfonic acid is preferred as a

  sulfation and optionally as sulfonating agent.

  The compounds of formula I in free acid form can be converted into salts by neutralization with an organic or inorganic base, for example with an alkali metal hydroxide, an alkaline earth metal hydroxide, ammonia or a

basic amine.

2555986 '

  The compounds of formula II may be prepared in a manner analogous to known methods, for example by condensation of an iso-octyl-, nonyl- or dodecylphenol with formaldehyde in a molar ratio of 2: 1, preferably in the presence of a acid catalyst. The resulting binuclear compounds are then alkoxylated with from 1 to 4 moles of ethylene oxide, propylene oxide and / or

of butylene oxide.

  The compounds of formula I are useful as emulsifying and dispersing agents. They are particularly suitable as auxiliary dyeing or printing, for example as

unison agents.

  Dyeing and printing in the presence of the compounds of formula I as unison agents can be carried out according to known methods for dyeing or printing textile substrates dyeable with anionic dyes or dispersion. The amount of the compound of formula I used in the dyebaths or printing pastes will depend on the textile substrate, the dye used, the bath pH and the treatment time. In general, the appropriate amounts are between 0.02 and 20% by weight, preferably between 0.1 and 15% by weight.

relative to the weight of the substrate.

  Preferred substrates are those consisting, in whole or in part, of natural or synthetic polyamides, polyesters, cellulose acetate or mixtures thereof. The compounds of formula I give solid dyes especially in the case of barred nylon. The compounds of formula I can also be used as auxiliaries for dyeing leather. They are also suitable as dispersing agents or emulsifiers for the preparation of agrochemical formulations or for use in

the paper industry.

  When the compounds of formula I are used as emulsifying or dispersing agents, they are used according to the

  known methods and in usual quantities.

  Compounds of formula I wherein at least one substituent R2 is -SO3R6 are also useful as peroxidic stabilizers 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 according to their sulfation and sulpho

  nation and the salt in the form of which they present themselves. For example, sodium salts are less water soluble than

monethanolammonium.

  The compounds of formula I are advantageously used in admixture with a co-surfactant; such compositions are also part of the invention. Suitable co-surfactants include C 3 -C 6 aliphatic alcohols and their ethers, for example isopropanol, cyclohexanol, butanol, isobutanol

  2-methyl-2,4-pentanediol, 1-butoxy-2-hydroxyethane, butylene

  glycol, 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. The preferred co-surfactants are butanol, isobutanol, butylene glycol and butyldiglycol. Of

  such mixtures can be easily diluted with water.

  The present invention also relates to a composition

  comprising a compound of formula I, a co-surfactant and water.

  Preferred compositions are those containing from 15 to 30% by weight of a compound of formula I, from 5 to 30% by weight of a

  co-surfactant and water to complete 100%.

  The following examples illustrate the present invention without in any way limiting its scope. In these examples, the parties

  are by weight and the temperatures are in degrees Celsius.

Example 1

  880 parts of nonylphenol are poured into a flask and

  heated with stirring at 50 and a stream of nitrogen.

  A solution of 13.2 parts of oxalic acid dihydrate in 8.4 parts of demineralised water, 4.4 parts of sodium dodecylbenzenesulphonate and finally, in portions, 63.2 parts of paraformaidhyde at a rate such as the temperature of the balloon rises to 85-95. The resulting mixture is slowly heated to between 120 and 125 and the water in the mixture is distilled off at about 1 mm Hg. The mixture is further heated to 160 and stirred at this temperature for 3 hours. It is brought back to atmospheric pressure by introducing nitrogen, 5 parts of solid sodium hydroxide are slowly added to the mixture and while the pressure is reduced to about 18 mmHg, 264 parts of ethylene oxide are introduced.

the surface.

  584 parts of the adduct obtained above are poured into a flask. To this product, 861 parts of methylene chloride are added with stirring and the mixture is cooled to 2-5. We

  then slowly added to this mixture 233 parts of chlorinated

  sulphonic at a rate such that the temperature does not exceed. The gaseous hydrochloric acid which is evolved is absorbed by an aqueous solution of sodium hydroxide. After the addition of chlorosulfonic acid, the resulting mixture is stirred for a further 3 hours, brought to room temperature and added slowly to 190 parts of monoethanolamine cooled to between 2 and 5 at room temperature. a rate such that the temperature does not exceed 20. After stirring for a further 2 hours at room temperature, the methylene chloride is distilled off at about 65 while reducing the

pressure at 60 mm Hg.

  590 parts of the compound of formula

9H19 C9H19

OCH2 X

OCH2CH20SO3 NH3CH2CH20H

O (CH2CH2O) 2SO3 + H3CH2CHPOH

  The compound is mixed with 300 parts of isobutanol and

  The mixture is stirred at about 40 ° to give a clear solution.

  In place of the 190 parts of monoethanolamine, equimolar amounts of di- or triethanolamine, morpholine or ammonia may be used for salt formation by neutralization. By proceeding in an analogous manner, but using the compounds of the following table in the molar amounts indicated, other compounds of formula I can be prepared. In each example, the alkylphenol is reacted with formaldehyde in a solution.

molar ratio of 2: 1.

// x x

BOARD

  Ex.No. R1 Mole oxide Mole chlorosulfonic acid alkylene 5 .... 2 Nonyle 3 propylene oxide. 2 3 Dodecyl 3 ethylene oxide 2 4 Nonyle 2 ethylene oxide 2 do. 1 ethylene oxide 1.5 6 Nonyle 1 propylene oxide 2.25 7 do. 4 ethylene oxide 28 d. 4 propylene oxide 2 9 do. 3 propylene oxide 2.5 do. 1 ethylene oxide 2 he Dodecyl 2 ethylene oxide 1.5 12 do. do. 2 13 Isooctyle do. 1.5 14 do. do. 2 Nylon 1 propylene oxide + 2 2 ethylene oxide 16 do. do. 2.5 17 do. 2 propylene oxide + 2 ethylene oxide 2 18 do. do. 1.5 19 do. 1 propylene oxide + 3 ethylene oxide 2 do. do. 2.5 21 do. do. 1.5 22 do. Butylene oxide 2.25 The resulting compounds are then blended with

  isobutanol, as described in Example 1.

255598 6

  Example of Application A 100 parts of a striped nylon 6 fabric is added to 1500 parts of a bath containing

  monosodium phosphate and tetrasodium pyrophosphate

  to adjust the pH of the bath to 8.0 parts of CI Acid Red 57, and 2.0 parts of the compound of Example 6 in salt form with monoethanolamine, and treated for 90 minutes at room temperature. boiling by this dye bath. Rinsed and then dried the substrate. We get a

solid red dye.

  By proceeding in the same way but replacing

  C.I. Acid Red stain 57 by C.I. Acid blue stain 80, C.I.

  Acid Orange 148 or C.I. Acid Orange 127, we get the same good

results.

  Application Example B 100 parts of nylon 6 / wool blended fabric: 40 to 3000 parts of a pH 8 dye bath containing 1 part of Acid Blue 80 dye and 4 parts of the compound of Example 1 are added as a salt with monoethanolamine, and dyed at 98 for 90 minutes. Rinsed and then dried the substrate. We

  gets a dark blue dye with excellent unison.

  In the process described above, the compound of Example 1 can be replaced by the compound of Example 8 or 10

equivalent quantity.

  By proceeding in an analogous manner but replacing the Acid Blue 80 CI dye with CI Acid Orange 145, CI Acid Orange 127, CI Acid Red 299, CI Acid Red 57, CI Acid Red 263, CI Acid Violet 48, CI Acid Blue 126 or CI Acid Blue

  271, we obtain the same good results.

  Application Example C A polyester fabric is dyed with 0.5% C.I. Disperse Red 13 by addition of 2 g / liter of sulfate

2555986;

  ammonium and 2 g / liter of the compound of Example 6 at pH 5 (adjusted with formic acid). The bath ratio is 1:20. Dyeing is done at 130 for 20 minutes. We wash and rinse

  the substrate. A solid dye is obtained.

  In Examples A to C, the compound of

  Formula I mixed with isobutanol as described in Example 1.

  Isobutanol can also be replaced by an equivalent amount

butyldiglycol.

Claims (20)

  1. A phenolic compound of formula I R1 R R. i CH2 2 R2 2 OR3 OR4   wherein each R1 independently represents an isooctyl, nonyl or dodecyl group, each R2 independently represents hydrogen or a group -S03R6,   R3 represents -t A - O tmRs wherein each A is independently -C2H4-, -C3H6- or -C4H8-, R4 is -B-O-nR5 wherein each B is independently -C2H4-, - C3H6- or -C4H8-,   each R5 independently represents hydrogen or a group -SO3R6, at least one of R5 to mean a group -S03R6,   each R6 independently represents hydrogen, an alkali metal, an equivalent of an alkaline earth metal, an ammonium group or a substituted ammonium group, m is 1, 2 or 3, and n is O, 1 or 2, the sum total m + n not to be greater than v 4, R5 in the substituent R4 to mean hydrogen and m to mean 1 when n = O, and the two symbols R2 to mean hydrogen when one   symbol R5 means a group -SO3R6 and n = 1 or 2.   2. A compound according to claim 1, characterized 2555986;   what R4 is -CH2CH2-0O t R or --CH-CH2-0-tR5. CH3   3. A compound according to any of the claims   1 or 2, characterized in that R6 denotes hydrogen, sodium, potassium, ammonium group or monoethanolammonium group.   4. A compound according to any one of the claims   1 to 3, characterized in that R3 is - (- tCH-CH2-O- - R5. CH3   5. A compound according to any of the claims   1 to 4, characterized in that n is 0.   6. A compound according to any one of the claims   1 to 5, characterized in that the sum m + n is equal to 1 or 2.   7. A compound according to any of the claims   i to 6, characterized in that the symbols R1 signify a nonyl group, one of the substituents R2 signifies hydrogen and the other signifies hydrogen or -SO3R6, R3 signifies - (- CH2CH2-OTmR5 or t-C3H6- MR5, R4 is - (-CH2CH2-O-) TnRS or - {C3H6-OhTR5, each substituent R5 is independently hydrogen or -SO3R6 at least one R5 to be -S03R6, the symbols R6 is hydrogen, sodium, potassium, ammonium group or monoethanolammonium group, m is 1, 2 or 3 and n is 0, 1 or 2, the total sum m + n being 1, 2 , 3 or 4, - R5 in the substituent R4 to mean hydrogen and m to mean I when n = 0, and - the two symbols R2 to mean hydrogen when one   substituent R5 means a group -SO3R6 and n = 1 or 2.   8. A compound according to claim 7, characterized in that the symbols R1 signify a nonyl group, a substituent R2 signifies hydrogen and the other signifies -S03R6, R3 signifies -CH -CH2 -0-R5 in which R5 means -S03R6, R4 is hydrogen, R6 is hydrogen, sodium,   potassium, the ammonium group or the monoethanol- ammonium and m is 1.   9. A process for preparing a compound of formula I as specified in claim 1, characterized in that a compound of formula II is reacted R1 R1   wherein R7 is - + A- -OH R8 is -BO -O-H n and A, B, R1, and n are as defined in claim 1, the total sum m + n not to be greater than 4 and m to mean when n is 0, with sulfur trioxide, sulfuric acid, oleum, aminosulfonic acid or chlorosulfonic acid in a molar ratio of 1: 1.5 -2 and, if necessary, the transformation of the free sulpho group (s) into their metal alkali metal salts   alkaline earth, ammonium or substituted ammonium.   10. The use of the phenolic compounds specified in   any of claims 1 to 8 as emulsifiers or dispersion.   11. The use of the phenolic compounds specified in   any of claims 1 to 8, as auxiliaries of dyeing or printing.   12. The use of the phenolic compounds specified in   any of claims i to 8 as auxiliaries for the leather dyeing.   A process for dyeing or printing a substrate capable of being dyed with anionic dyes or with dispersion dyes, characterized in that the substrate is dyed or printed in the presence of a phenolic compound such as specified at   any of claims i to 8.   14. A process according to claim 13, characterized in that the amount of phenolic compound is between 0.02 and % by weight of the substrate.   15. A process according to claim 13 or 14, characterized in that the substrate comprises, in whole or in part, cellulose acetate, polyester or polyamides. natural or synthetic.   16. A method according to any one of the claims   13 to 15, characterized in that the phenolic compound is mixed   with a C3-C6 aliphatic alcohol or an ether thereof.   17. A substrate dyed or printed when obtained   according to the method specified in any one of claims 13 to   16. 18. A composition comprising a phenolic compound such   specified in claims 1 to 8, in association with a   surfactant. 19. A composition according to claim 18, characterized in that the co-surfactant is an aliphatic alcohol.   C3-C6 or an ether of this alcohol.   20. A composition according to claim 19, characterized in that the co-surfactant is chosen from isopropanol, cyclohexanol, butanol, isobutanol   2-methyl-2,4-pentanediol, 1-butoxy-2-hydroxyethane, butylene   glycol, butyldiglycol and mixtures thereof.   21. A composition according to any one of   Claims 18 to 20, characterized in that the weight ratio   from phenol compound to co-surfactant is from 3:17 to 17: 3. 22. A composition according to any one of   Claims 18 to 21 containing 15 to 30% by weight of a compound   phenolic compound as specified in any one of claims 1 to 8, from 5 to 30% by weight of a co-surfactant and water for complete to 100%.