EP1073630A1

EP1073630A1 - Novel sulphonated and oxy- or polyalkylene diphenol derivatives and their corresponding salts

Info

Publication number: EP1073630A1
Application number: EP99914628A
Authority: EP
Inventors: Virginie Pevere; Przemyslaw Szczecinski; Jean-Roger Desmurs; Jean-Claude Galliot; Françoise LARTIGUE-PEYROU
Original assignee: Rhodia Chimie SAS
Current assignee: Rhodia Chimie SAS
Priority date: 1998-04-20
Filing date: 1999-04-20
Publication date: 2001-02-07
Also published as: JP2002512219A; AU3337099A; WO1999054292A1

Abstract

The invention concerns novel sulphonated and oxy- or polyalkylene diphenol derivatives and their corresponding salts corresponding to general formulae (Ia and Ib) wherein Y1 and Y2 are such as defined in Claim 1.

Description

1

NEW SULPHONATED AND OXY- OR POLYOXYALKYLENE DIPHENOL DERIVATIVES AND THEIR CORRESPONDING SALTS.

The subject of the present invention is new derivatives of sulfonated and oxy- or polyoxyalkylenated diphenols and their corresponding salts.

In many technical fields, we are looking for new molecules in order to appreciate their potential in different applications.

New derivatives of sulphonated and oxy- or polyoxyakylene derivatives and their corresponding salts corresponding to the following general formulas (la) and (Ib) have now been found.

HO ₃ S

H0 ₃ s ^{S0 H} (la) ^S ° 3 ^H (Ib)

in said formulas (la) and (Ib), Y and Y ₂ , identical or different, represent a group

^~ Rl ^R 2 ^~ l I

- CH CH-C-i H

- ^~ in which the radicals R ₁ and R ₂ , identical or different, represent a hydrogen atom, a methyl or ethyl radical: when one of the radicals R ₁ or R ₂ is a methyl or ethyl radical, the other radical R ₁ or R is then a hydrogen atom, - n is a number between 1 and 50.

The present invention therefore relates to diphenol derivatives such as pyrocatechin (la) and resorcinol (Ib).

The invention also includes the diphenol derivatives corresponding to formulas (la) or (Ib) in which the aromatic nucleus carries one or two substituents symbolized by R.

The substituents can be of any nature but the preferred substituents are linear or branched alkyl groups having for example from 1 to 18 carbon atoms, preferably methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert -butyl, dodecyl, hexadecyl, 2 octadecyl; acyl groups of type R'-CO- in which R 'represents a linear or branched alkyl group having from 1 to 17 carbon atoms such as in particular acetyl, lauroyl, palmitoyl, stearoyl.

The invention relates to sulphonated and oxy- or polyoxyakylene derivatives of pyrocatechin whose sulphonic groups are in salified form, preferably in the form of an alkali, alkaline-earth metal or an ammonium group.

The invention also relates to sulphonated and oxy- or polyoxyakylene derivatives of resorcinol, the sulphonic groups of which are in salified form, preferably in the form of an alkali, alkaline-earth metal or an ammonium group.

By alkali metal is meant an element chosen from the group of elements in column 1 A of the periodic table and their mixtures, preferably alkali metals such as lithium, sodium, potassium, rubidium, cesium.

By alkaline earth metal is meant an element chosen from the group of elements of column 2A and their mixtures, preferably the alien earth metals such as beryllium, magnesium, calcium, strontium, barium.

For the definition of the elements, reference is made below to the Periodic Table of the Elements published in the Bulletin of the Chemical Society of France, n ° 1 (1966).

The preferred compounds of the invention more particularly correspond to the formulas (la-,) and (lb _n ):

OY, OY,

OY,

M0 ₃ S

M0 ₃ s -

OY ₂

S0 ₃ M _(la1) S0 ₃ M _{(l b1)} in said formulas (la.,) And (Ib-i), M represents an alkali metal, preferably sodium and potassium or an ammonium group and Y ₁ and Y ₂ having the meaning given above.

As regards the radical R ₂ involved in the new compounds according to the invention, it preferably represents a hydrogen atom or a methyl radical. As for the radical R., it preferably represents a hydrogen atom.

The number of oxyalkylenated units can vary widely between 1 and 50, but it is preferably between 1 and 20. 3

Another variant of the invention are the compounds of formula (la) and (Ib) which are characterized by the fact that they comprise both oxyethylenated units and oxypropylenated units: the said units being distributed in a statistical manner or sequenced. They are more preferably represented by the formulas (la) or (la-i),

(Ib) or (Ibi) in which Y- | and Y ₂ represent a group:

CH ₃ ^~ - CH ₂ - CH O CH ₂ ^~ CH ₂ -0-— H

^{~ ~} P ^~ q in which p and q are numbers such as:

- p + q = n, - p + q ≠ 1, - p is between 0 and 5,

- q is between 0 and 10.

Another object of the process of the invention resides in the process for obtaining derivatives of sulfonated and oxy- or polyoxyakylene diphenols corresponding to the general formula (la) and (Ib).

They are obtained according to a process which essentially consists in reacting: - the sulfonated diphenol or its corresponding salts of formula (IIa) or (Mb):

OH OH

OH

HO ₃ S - HO ₃ S -

OH ^S03H (Ha) ^S ° ^3H (Mb)

- and an alkylene oxide of formula (III):

^R 1 ^ ^R 2

^H ^ r O, ^H (III) in said formula (III), the radicals R ₁ and R ₂ have the meaning given above.

The compound of formula (IIa) or (Mb) can also carry one or two substituents on the aromatic ring such as R.

The compound of formula (Ha) or (Mb) is preferably used in salified form, and more particularly in the form of the sodium or potassium salt. 4

Preferably, the radicals R- ₎ and R ₂ represent a hydrogen atom where one of the radicals R- | and R ₂ represents a methyl radical, the other being a hydrogen atom.

As regards the reagent of formula (III), use is preferably made of ethylene oxide, propylene oxide, butylene oxide or their mixtures. Ethylene oxide, propylene oxide or mixtures thereof are preferred.

The quantity of reagents to be brought into contact can vary widely.

The amount of alkylene oxide is generally in excess relative to the amount of diphenol of formula (IIa) or (IIb). The ratio between the number of moles of alkylene oxide and the number of moles of sulfonated diphenol of formula (IIa) or (IIb) varies between 2 and 50, and more preferably between 2 and 12.

The reaction is carried out in the presence of an effective amount of a catalyst.

Mention may be made, as preferred catalysts, of catalysts based on divalent metals, and more particularly on alkaline earth metals, preferably calcium or magnesium.

The metallic elements can be provided in the form of an inorganic derivative such as an oxide or a hydroxide. It is possible to use a mineral salt preferably, nitrate, sulfate, oxysulfate, halide, oxyhalide, silicate, carbonate, orthophosphate or an organic derivative, preferably oxalate, acetylacetonate; alcoholate and even more preferably methyiate or ethylate; carboxylate and even more preferably acetate.

Preferably, use is made of the oxides, hydroxides, chlorides and / or sulfates of the alkaline earth metals, preferably calcium or magnesium.

As examples of preferred catalysts, mention may be made of calcium chloride.

As regards the quantity of catalyst to be used, it is expressed in molar% relative to the alkylene oxide of formula (III). Most often, 0.1% to 10% by mol are used, preferably 2 to 5% by mol.

The reaction is carried out in water and / or in an organic solvent. Preferably, an aliphatic or cycloaliphatic alcohol is used and most often methanol or ethanol is chosen.

The weight concentration of the sulfonated diphenol most often represents 5 to 30%, preferably about 20% of the weight of the reaction mixture.

The reaction temperature is chosen so that it is sufficient to allow the reaction to take place. 5

The reaction temperature is preferably chosen between 50 and 100 ° C, and even more preferably between 50 and 80 ° C.

The reaction is preferably carried out under an atmosphere of an inert gas which may be nitrogen, a rare gas, preferably argon or carbon tenoxide. The reaction takes place at atmospheric pressure or at a pressure lower or higher than this. Thus, the reaction can be carried out under reduced pressure, for example, between 200 and 700 mm of mercury (2.7.10 ⁴ to 9.3.10 ⁴ Pa) or overpressure, the pressure can be between 1 and 4 bar. Generally, it is preferred to work at the autogenous pressure of the reactants.

From a practical point of view, the method according to the invention is simple to implement.

A preferred embodiment of the invention consists in charging the sulfonated diphenol of formula (IIa) or (IIb) and the catalyst then establishing the atmosphere of inert gas.

The reaction medium is cooled to a temperature preferably between 0 ° C and 10 ° C.

The alkylene oxide is then introduced, under an inert atmosphere or under reduced pressure. The reaction medium is brought to the desired temperature.

In the case where a mixed compound is prepared, containing different oxyalkylene units, in the case of block units, the alkylene oxides of different nature are introduced successively and in the case of statistical units, all the alkylene oxides at the same time. At the end of the reaction, the sulfonated and oxy- or polyoxyalkylenated diphenol derivative of formula (la) or (Ib) is obtained. The product obtained is in liquid form and or in pasty form: its consistency depending on the number of oxyalkylene units.

The product obtained can be recovered in a conventional manner, for example by removal of the excess alkylene oxide by heating, from the substrate which has not reacted by filtration and isolation of the product according to a common technique, in particular recrystallization. in an appropriate solvent, of alcohol or ketone type, preferably methanol and / or acetone.

The products of the invention can be used as surfactants to prepare emulsions and dispersions.

Examples of the invention are given below.

These examples are given by way of illustration and without limitation. Example 1

Synthesis of sodium 4.5-bis (2-hydroxyethoxy) benzene-1.3-disulfonate:

100 g of 4,5-dihydroxybenzene-1, 3-sodium disulfonate, 4 g of calcium chloride dissolved in 320 ml of water are placed in a 2-liter reactor.

The mixture is cooled to 2 ° C and 200 ml of ethylene oxide are added.

The medium is then heated for 24 h at 50 ° C. under autogenous pressure.

The excess ethylene oxide (77 ml) is then removed at 60 ° C.

The reaction medium is filtered and the water is evaporated under reduced pressure (90 ° C under 30 mm of mercury).

The residue obtained is diluted with 100 ml of methanol, then this mixture is heated to reflux, then cooled to room temperature.

The white crystals formed are filtered, washed with 10 ml of methanol and dried for 10 h at 90 ° C under atmospheric pressure and then 3 h at 170 ° C under reduced pressure (0.3 mm of mercury).

89 g of sodium 2,3-bis (2-hydroxyethoxy) benzene-1,5-disulfonate are obtained, ie a yield of 69.5%.

The NMR characteristics of the product obtained are as follows: 1 H NMR (D ₂ O): 3.8 ppm (m, 4p), 1 ppm (t, 2p), 4.25 pm (t, 2p), 7.45 ppm (d, 1p), 7.65 ppm (d, 1p).

A second fraction of the product (11 g of solid corresponding to the previous analysis) can be obtained by crystallizing the previous filtrate with an acetone / methanol mixture.

Example 2

Synthesis of sodium 4.5-bis (2-hydroxy-1-propoxy) benzene-1.3-disulfonate:

2.5 g of sodium 4,5-dihydroxybenzene-1, 3-disulfonate, 8 ml of water, 0.1 g of calcium chloride and 5 ml of propylene oxide are charged to a reactor. The reactor is closed and placed in an oil bath.

The biphasic reaction medium is heated at this temperature for 72 h.

After 30 h, 1 ml of propylene oxide is added. The reaction medium is filtered and air-dried, the solid obtained at 130 ° C. 0.3 g of a monosubstituted product is obtained.

The filtrate is evaporated to dryness and the residue obtained is diluted with isopropanol. 7

The precipitated crystals are filtered, washed with isopropanol and acetone and dried at 130 ° C.

2 g of sodium 4,5-bis (2-hydroxy-1-propoxy) benzene-1,3-disulfonate are obtained. The NMR characteristics of the product obtained are as follows:

1 H NMR (D ₂ O): 7.65 ppm - 7.44 ppm (2s, 2H), 3.8 ppm - 4.2 ppm (m, 6H), 1.03 ppm - 1.04 ppm (d , 6H).

Example 3 Synthesis of sodium 4.6-bis (2-hydroxyethoxy) benzene-1.3-disulfonate:

1 - Step 1: synthesis of sodium 4,6-dihydroxy-1,3-benzenedisulfonate:

22 g of resorcinol are dissolved in 100 ml of concentrated sulfuric acid (95%) and the mixture and heated 15 min at 65 ° C.

The solution is cooled to 5 ° C and the precipitate formed is filtered and then dried to protect from ^moisture.

The analysis is carried out on a sample after neutralization with sodium hydrogencarbonate. 1 H NMR (D ₂ O): 6.5 ppm (s, 1p), 7.95 ppm (s, 1p)

2 - Step 2: ethoxylation The product obtained according to step 1 is introduced into a 500 ml reactor and

0.2 g of calcium chloride in solution in 100 g of water.

The mixture is cooled to 2 ° C and 9.2 ml of ethylene oxide are added. The medium is then heated for 24 h at 50 ° C. under autogenous pressure. The ^excess ethylene oxide was then removed at 60 ° C. The reaction medium is filtered and the water is evaporated under reduced pressure

(90 ° C under 30 mm of mercury).

13 g of sodium 4,6-bis (2-hydroxyethoxy) benzene-1,3-disulfonate are obtained in the form of a white solid.

The NMR characteristics of the product obtained are as follows: 1 H NMR (D ₂ O): 3.85 ppm (t, 4p), 4.21 ppm (t, 4p), 6.74 ppm (s, 1 p), 8.1 ppm (s, 1 p).

Claims

8

1 - New derivatives of sulphonated and oxy- or polyoxyakylene diphenols and their corresponding salts corresponding to the following general formulas (la) and (Ib):

OY, OY,

OY

HO, S- HO ₃ S

'3 "^ OY„

^S ° 3 ^H (la) S0 ₃ H (Ib)

in which Y ^ and Y ₂ , identical or different, represent a group

^R 1 ^R 2

CH - CH-0 H n in which the radicals R ₁ and R ₂ , identical or different, represent a hydrogen atom, a methyl or ethyl radical: when one of the radicals R- _| or R ₂ is a methyl or ethyl radical, the other radical R ₁ or

R ₂ is then a hydrogen atom, - n is a number between 1 and 50.

2 - New derivatives according to claim 1 characterized in that they correspond to formulas (la) and (Ib) in which the aromatic ring additionally carries one or two substituents R.

3 - New derivatives according to claim 2 characterized in that they correspond to formulas (la) or (Ib) in which the aromatic nucleus carries one or two substituents R which may be linear or branched alkyl groups having from 1 to 18 carbon atoms; acyl groups of type R'-CO- in which R 'represents a linear or branched alkyl group having from 1 to 17 carbon atoms.

4 - New derivatives according to one of claims 1 to 3 characterized in that the sulfonic groups are in salified form, preferably in the form of an alkali metal, alkaline earth metal or an ammonium group.

5 - New derivatives according to one of claims 1 to 4 characterized in that they correspond to the formulas (lai) and (lb ₁ ): OY, OY,

.OY

M0 ₃ S - _^ ^M ° 3 ^S

OY,

^S ° ^3M ( ^| _aι ) ^S ° ^3M (Ib in said formulas (la-i) and (Ib ^, M represents an alkali metal, preferably sodium and potassium or an ammonium group and Y ₁ and Y having the meaning given in claim 1.

6 - New derivatives according to claim 5 characterized in that they correspond to the formulas (la-,) and (Ib ^ in which the radical R intervening in the groups Y ₁ and Y represents a hydrogen atom or a methyl radical and the radical R. represents a hydrogen atom.

7 - New derivatives according to one of claims 1 to 6 characterized in that they correspond to formulas (la) or (la-i) and (Ib) or (lb- in which the number of oxyalkylenated units varies between 1 and 50 and preferably between 1 and 20.

8 - New derivatives according to one of claims 1 to 6 characterized in that they correspond to the formula (la) or (la-i) and (Ib) or (Ib ^ in which Y ₁ and Y represent a group :

CH ₃ ^~ - CH ₂ - CH O CH ₂ - CH ₂ -0 - H

^~ P q in which p and q are numbers such that: - p + q = n,

- p + q ≠ 1,

- p is between 0 and 5,

- q is between 0 and 10.

9 - New derivatives according to one of claims 1 to 8 characterized in that they are:

- sodium 4,5-bis (2-hydroxyethoxy) benzene-1, 3-disulfonate

- 4,5-bis (2-hydroxy-1-propoxy) benzene-1, 3-sodium disulfonate

- 4,6-bis (2-hydroxyethoxy) benzene-1, 3-sodium disulfonate.

10 - Process for the preparation of the sulfonated and oxy- or polyoxyakylene derivatives of diphenols corresponding to the general formulas (la) or (lai) and (Ib) or (Ib-,) 10 described in one of claims 1 to 9 characterized in that it consists in reacting:

- the sulfonated diphenol or its corresponding salts of formula (IIa) or (IIb):

OH

H0 ₃ S - HO ₃ S -

OH

^S0 3 ^H (lia) ^S0 3 ^H (llb)

- and an alkylene oxide of formula (III):

^R 1 - ^R 2

^H n

⁰ (m) in said formula (III), the radicals R ₁ and R ₂ have the meaning given previously in claims 1 to 9.

11 - Process according to claim 10 characterized in that the compound of formula (lla) or (llb) carries one or two substituents on the aromatic ring such as R.

12 - Method according to one of claims 10 and 11 characterized in that the compound of formula (Ha) or (llb) used is preferably in salified form, and more preferably in the form of the sodium salt or potassium.

13 - Method according to one of claims 10 to 12 characterized in that the radical R ₂ involved in the groups Y ₁ and Y represents a hydrogen atom or a methyl radical and the radical R .. represents an atom of hydrogen.

14 - Process according to claim 10 characterized in that the reagent of formula (III) is ethylene oxide, propylene oxide, butylene oxide or their mixtures, preferably ethylene oxide , propylene oxide or their mixtures.

15 - Process according to claim 14 characterized in that the ratio between the number of moles of alkylene oxide and the number of moles of diphenol 1 1 sulfonated of formula (IIa) or (IIb) varies between 2 and 50, and more preferably between 2 and 12.

16 - Process according to claim 10 characterized in that the reaction is carried out in the presence of an effective amount of a catalyst.

17 - Process according to claim 16 characterized in that the catalyst based on divalent metals is a catalyst based on alkaline earth metals, preferably calcium or magnesium.

18 - Method according to one of claims 16 and 17 characterized in that the metal elements are provided in the form of an inorganic derivative, preferably an oxide or a hydroxide or a mineral salt preferably, nitrate, sulfate, oxysulfate, halide, oxyhalide, silicate, carbonate, orthophosphate or an organic derivative, preferably oxalate, acetylacetonate; alcoholate and even more preferably methylate or ethylate; carboxylate and even more preferably acetate.

19 - Method according to one of claims 16 to 18 characterized in that the amount of catalyst to be used expressed in molar% relative to the alkylene oxide of formula (III) varies from 0.1% to 10 mol%, preferably 2 to 5 mol%.

20 - Method according to one of claims 10 to 19 characterized in that the reaction is carried out in water and / or in an organic solvent, preferably in an aliphatic or cycloaliphatic alcohol and more preferably in methanol or l ethanol.

21 - Method according to one of claims 10 to 20 characterized in that the reaction temperature is preferably chosen between 50 and 100 ° C, and even more preferably between 50 and 80 ° C.

22 - Method according to one of claims 10 to 21 characterized in that the reaction is preferably carried out under an atmosphere of an inert gas.