WO1999054292A1 - Nouveaux derives de diphenols sulfones et oxy- ou polyoxyalkylenes et leurs sels correspondants - Google Patents
Nouveaux derives de diphenols sulfones et oxy- ou polyoxyalkylenes et leurs sels correspondants Download PDFInfo
- Publication number
- WO1999054292A1 WO1999054292A1 PCT/FR1999/000933 FR9900933W WO9954292A1 WO 1999054292 A1 WO1999054292 A1 WO 1999054292A1 FR 9900933 W FR9900933 W FR 9900933W WO 9954292 A1 WO9954292 A1 WO 9954292A1
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- formula
- radical
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- new derivatives
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
- C07C309/01—Sulfonic acids
- C07C309/28—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
- C07C309/41—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing singly-bound oxygen atoms bound to the carbon skeleton
- C07C309/42—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing singly-bound oxygen atoms bound to the carbon skeleton having the sulfo groups bound to carbon atoms of non-condensed six-membered aromatic rings
Definitions
- the subject of the present invention is new derivatives of sulfonated and oxy- or polyoxyalkylenated diphenols and their corresponding salts.
- Y and Y 2 identical or different, represent a group
- 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.
- alkali metal 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.
- 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.
- the preferred compounds of the invention more particularly correspond to the formulas (la-,) and (lb n ):
- M represents an alkali metal, preferably sodium and potassium or an ammonium group and Y 1 and Y 2 having the meaning given above.
- radical R 2 involved in the new compounds according to the invention preferably represents a hydrogen atom or a methyl radical.
- 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),
- 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).
- 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
- the radicals R- ) and R 2 represent a hydrogen atom where one of the radicals R-
- 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.
- 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.
- 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.
- the quantity of catalyst to be used 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.
- 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.
- 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.
- 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.
- the alkylene oxides of different nature are introduced successively and in the case of statistical units, all the alkylene oxides at the same time.
- 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.
- 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.
- reaction medium is filtered and the water is evaporated under reduced pressure (90 ° C under 30 mm of mercury).
- 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).
- 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.
- the biphasic reaction medium is heated at this temperature for 72 h.
- the precipitated crystals are filtered, washed with isopropanol and acetone and dried at 130 ° C.
- the solution is cooled to 5 ° C and the precipitate formed is filtered and then dried to protect from moisture.
- Step 2 ethoxylation
- the product obtained according to step 1 is introduced into a 500 ml reactor and
- 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
- 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).
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Polyethers (AREA)
Abstract
Description
Claims
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2000544633A JP2002512219A (ja) | 1998-04-20 | 1999-04-20 | 新規なスルホン化されたオキシアルキレン化ジフェノール誘導体およびスルホン化されたポリアルキレン化ジフェノール誘導体ならびそれらに対応する塩 |
EP99914628A EP1073630A1 (fr) | 1998-04-20 | 1999-04-20 | Nouveaux derives de diphenols sulfones et oxy- ou polyoxyalkylenes et leurs sels correspondants |
AU33370/99A AU3337099A (en) | 1998-04-20 | 1999-04-20 | Novel sulphonated and oxy- or polyalkylene diphenol derivatives and their corresponding salts |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR9804919A FR2777564B1 (fr) | 1998-04-20 | 1998-04-20 | Nouveaux derives de la resorcine sulfones et polyoxyalkylenes et leurs sels correspondants |
FR98/04918 | 1998-04-20 | ||
FR9804918A FR2777563B1 (fr) | 1998-04-20 | 1998-04-20 | Nouveaux derives de la pyrocatechine sulfones et oxy- ou polyoxyalkylenes et leurs sels correspondants |
FR98/04919 | 1998-04-20 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1999054292A1 true WO1999054292A1 (fr) | 1999-10-28 |
Family
ID=26234277
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/FR1999/000933 WO1999054292A1 (fr) | 1998-04-20 | 1999-04-20 | Nouveaux derives de diphenols sulfones et oxy- ou polyoxyalkylenes et leurs sels correspondants |
Country Status (4)
Country | Link |
---|---|
EP (1) | EP1073630A1 (fr) |
JP (1) | JP2002512219A (fr) |
AU (1) | AU3337099A (fr) |
WO (1) | WO1999054292A1 (fr) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2001055053A1 (fr) * | 2000-01-28 | 2001-08-02 | Rhodia Chimie | Compositions a base de derives phenoliques et leur utilisation comme adjuvants des liants mineraux |
FR2902096A1 (fr) * | 2006-06-13 | 2007-12-14 | Rhodia Recherches & Tech | Procede de preparation de dihydroxybenzenedisulfonates metalliques |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2178830A (en) * | 1938-04-26 | 1939-11-07 | Rohm & Haas | Aromatic polyalkylene ether sulphonates |
US2675411A (en) * | 1951-04-11 | 1954-04-13 | Eastman Kodak Co | Bis(4-beta-hydroxyalkoxyphenyl) ketones and process of preparation |
EP0339870A1 (fr) * | 1988-04-29 | 1989-11-02 | Minnesota Mining And Manufacturing Company | Nouveau agent anti-voile pour des sensibilisateurs polyalkylène glycole |
JPH0726417A (ja) * | 1993-07-06 | 1995-01-27 | Teijin Ltd | 改善された常温ソイルリリース性を有するポリエステル繊維 |
-
1999
- 1999-04-20 AU AU33370/99A patent/AU3337099A/en not_active Abandoned
- 1999-04-20 EP EP99914628A patent/EP1073630A1/fr not_active Withdrawn
- 1999-04-20 JP JP2000544633A patent/JP2002512219A/ja not_active Withdrawn
- 1999-04-20 WO PCT/FR1999/000933 patent/WO1999054292A1/fr not_active Application Discontinuation
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2178830A (en) * | 1938-04-26 | 1939-11-07 | Rohm & Haas | Aromatic polyalkylene ether sulphonates |
US2675411A (en) * | 1951-04-11 | 1954-04-13 | Eastman Kodak Co | Bis(4-beta-hydroxyalkoxyphenyl) ketones and process of preparation |
EP0339870A1 (fr) * | 1988-04-29 | 1989-11-02 | Minnesota Mining And Manufacturing Company | Nouveau agent anti-voile pour des sensibilisateurs polyalkylène glycole |
JPH0726417A (ja) * | 1993-07-06 | 1995-01-27 | Teijin Ltd | 改善された常温ソイルリリース性を有するポリエステル繊維 |
Non-Patent Citations (3)
Title |
---|
CHEMICAL ABSTRACTS, vol. 122, no. 24, 12 June 1995, Columbus, Ohio, US; abstract no. 293319y, page 129; XP002092836 * |
DATABASE CHEMABS CHEMICAL ABSTRACTS SERVICE, COLUMBUS, OHIO, US; XP002092837 * |
R.E. RINDFUSZ, ET AL.: "Synthesis of chromanes and coumaranes. II", JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, vol. 42, no. 1, 1 January 1920 (1920-01-01), Washington, DC, US, pages 157 - 165, XP002087841 * |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2001055053A1 (fr) * | 2000-01-28 | 2001-08-02 | Rhodia Chimie | Compositions a base de derives phenoliques et leur utilisation comme adjuvants des liants mineraux |
FR2804424A1 (fr) * | 2000-01-28 | 2001-08-03 | Rhodia Chimie Sa | Compositions a base de derives phenoliques et leur utilisation comme adjuvants des liants mineraux |
FR2902096A1 (fr) * | 2006-06-13 | 2007-12-14 | Rhodia Recherches & Tech | Procede de preparation de dihydroxybenzenedisulfonates metalliques |
WO2007144344A1 (fr) * | 2006-06-13 | 2007-12-21 | Rhodia Operations | Procede de preparation de dihydroxybenzenedisulfonates metalliques |
US8263803B2 (en) | 2006-06-13 | 2012-09-11 | Rhodia Operations | Preparation of metallic dihydroxybenzene-disulfonates |
RU2468004C2 (ru) * | 2006-06-13 | 2012-11-27 | Родиа Операсьон | Способ получения дигидроксибензолдисульфонатов металлов |
Also Published As
Publication number | Publication date |
---|---|
JP2002512219A (ja) | 2002-04-23 |
EP1073630A1 (fr) | 2001-02-07 |
AU3337099A (en) | 1999-11-08 |
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