EP0109273A1
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EP
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Peroxide compositions based on tungsten and phosphorus or arsenic, and a process for preparing the same
Assignee: Montedison SpA
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Filing: 1983-11-10
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Granted: —
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Expires: 2003-11-10
Abstract
Abstract There are described compositions of formula wherein: Q represents a cation of an onium salt; X is either a P or As atom, and n is 0, 1 or 2. Such compositions may be prepared by reacting an oxygenated tungsten (VI) derivative, an oxygenated P (V) or As (V) derivative and hydrogen peroxide, in an aqueous acid phase, with a onium salt or a precursor thereof, optionally contained in an organic phase immiscible with the aqueous phase, at substantially room temperature. The oxygenated compounds of W (VI), P (V) or As (V) may be prepared in situ underthe conditions of the reaction. Compositions (I), which may be solids or viscous oils, find use as oxidizing agents in general in oxidation processes, and especially as epoxydation catalysts for olefinic compounds.
Inventors
- 👤 Carlo Venturello
- 👤 Rino D'aloisio
- 👤 Marco Ricci
Bibliographic Details
Application Number
—
Jurisdiction
EP
Data Source
google_patents
Last Synchronized
2026-11-09 04:36
CPC Classifications
C; C07; C07F; C07F9/00; C07F9/02; C07F9/28; C07F9/54; C07D; C07D301/00; C07D301/02; C07D301/03; C07D301/12
Claims Analysis
Total Claims: 48
Claim 1
Independent Claim
35 words
A peroxidic composition, characterized by having the following formula (I): . wherein Q represents a cation of a quaternary onium salt, X represents a P or As atom, and n is 0, 1 or 2.
Claim 2
Dependent Claim
35 words
A peroxidic composition, characterized by having the following formula (I): . wherein Q represents a cation of a quaternary onium salt, X represents a P or As atom, and n is 0, 1 or 2.
Claim 3
Dependent Claim
89 words
A peroxidic composition as claimed in claim 1, characterized in that the cation of the quaternary onium salt Q is a cation of a salt having the formula (II): wherein M represents a pentavalent element of Group VA of the Periodic System; Y represents an inorganic anion; and R 1 , R 2 , R 3 and R 4 , which may be the same as or different from each other, each represent a hydrogen atom or a monovalent hydrocarbon-group having up to a total of 70 carbon atoms.
Claim 4
Dependent Claim
25 words
A peroxidic composition as claimed in claim 2, characterized in that Y - is C1 - , HSO 4 - or NO 3 - .
Claim 5
Dependent Claim
34 words
A peroxidic composition as claimed in claim 2 or 3, characterized in that R 1 , R 2 , R 3 and R 4 have a total of from 25 to 40 carbon atoms.
Claim 6
Dependent Claim
7 words
A peroxidic composition of the formula: or
Claim 7
Dependent Claim
7 words
A peroxidic composition of the formula: or
Claim 8
Dependent Claim
7 words
A peroxidic composition of the formula: or
Claim 9
Dependent Claim
7 words
A peroxidic composition of the formula: or
Claim 10
Dependent Claim
7 words
A peroxidic composition of the formula: or
Claim 11
Dependent Claim
7 words
A peroxidic composition of the formula: or
Claim 12
Dependent Claim
7 words
A peroxidic composition of the formula: or
Claim 13
Dependent Claim
7 words
A peroxidic composition of the formula: or
Claim 14
Dependent Claim
7 words
A peroxidic composition of the formula: or
Claim 15
Dependent Claim
7 words
A peroxidic composition of the formula: or
Claim 16
Dependent Claim
7 words
A peroxidic composition of the formula: or
Claim 17
Dependent Claim
7 words
A peroxidic composition of the formula: or
Claim 18
Dependent Claim
7 words
A peroxidic composition of the formula: or
Claim 19
Dependent Claim
7 words
A peroxidic composition of the formula: or
Claim 20
Dependent Claim
7 words
A peroxidic composition of the formula: or
Claim 21
Dependent Claim
7 words
A peroxidic composition of the formula: or
Claim 22
Dependent Claim
53 words
A process for the preparation of a peroxidic composition of formula (I) as defined in claim 1, characterized in that an oxygenated derivative of tungsten and an oxygenated derivative of P or As and hydrogen peroxide, contained in an acid aqueous phase, are reacted with an onium salt or with a precursor thereof.
Claim 23
Dependent Claim
22 words
A process as claimed in claim 13, characterized in that the reaction is carried out at a temperature from 20°C to 80°C.
Claim 24
Dependent Claim
28 words
A process as claimed in claim 13 or 14, characterized in that there is used an oxygenated hexavalent tungsten compound selected from tungstic acid and its alkaline salts.
Claim 25
Dependent Claim
60 words
A process as claimed in claim 15, characterized in that the oxygenated hexavalent tungsten derivative is prepaned in situ , under the conditions of the reaction, starting from a tungsten derivative selected from WO 2 , W 2 O 5 , WO 3 , WS 2 , WS 3 . W oxychloride, W chloride, W-hexacarbonyl or starting from metallic tungsten.
Claim 26
Dependent Claim
31 words
A process as claimed in any of claims 13 to 16, characterized in that there is used an oxygenated compound of pentavalent P selected from phosphoric acid and its alkaline salts.
Claim 27
Dependent Claim
51 words
A process as claimed in claim 17, characterized in that the oxygenated derivative of pentavalent P is prepared in situ , under the conditions of the reaction, starting from a P derivative selected from P 2 O 5 , PCl 5 , POCl 3 , polyphosphoric acid and its alkaline salts.
Claim 28
Dependent Claim
31 words
A process as claimed in any of claims 13 to 16, characterized in that there is used an oxygenated compound of pentavalent As selected from arsenic acid and its alkaline salts.
Claim 29
Dependent Claim
44 words
A process as claimed in claim 19, characterized in that the oxygenated derivative of pentavalent As is prepared in situ , under the conditions of the reaction, starting from a derivative selected from As 2 O 5 , AsCl 5 and AsOCl 3 .
Claim 30
Dependent Claim
85 words
A process as claimed in any of claims 13 to 20, characterized in that a quaternary onium salt is of formula (II) : wherein M represents a pentavalent element of Group VA of the Periodic System; Y - represents an inorganic anion; and R 1 , R 2 , R 3 and R 4 , which may be the same as or different from each other, each represent a hydrogen atom or a monovalent hydrocarbon group having up to a total of 70 carbon atoms.
Claim 31
Dependent Claim
24 words
A process as claimed in claim 21, characterized in that Y - is Cl - , HSO 4 - or NO 3 - .
Claim 32
Dependent Claim
32 words
A process as claimed in claim 21 or 22, characterized in that R 1 , R 2 , R 3 and R 4 have in total from 25 to 40 carbon atoms.
Claim 33
Dependent Claim
41 words
A process as claimed in any of claims 21 to 23, characterized in that, for M = N in the formula (II), the quaternary ammonium salt is prepared in situ under the conditions of the reaction, starting from the equivalent amine.
Claim 34
Dependent Claim
25 words
A process as claimed in any of claims 13 to 24, characterized in that the pH value in the aqueous phase is maintained below 4.
Claim 35
Dependent Claim
21 words
A process as claimed in claim 25, characterized in that the pH value in the aqueous phase is maintained below 2.
Claim 36
Dependent Claim
32 words
A process as claimed in claim 25 or 26, characterized in that the pH value in the aqueous phase is maintained below the said value by the addition of a mineral acid.
Claim 37
Dependent Claim
29 words
A process as claimed in any of claims 13 to 27, characterized in that the onium salt or its precursor is used dissolved in a substantially water-immiscible organic phase.
Claim 38
Dependent Claim
32 words
A process as claimed in claim 28, characterized in that the organic phase substantially immiscible with the aqueous phase consists of a solvent selected from aromatic and chlorinated hydrocarbons and mixtures thereof.
Claim 39
Dependent Claim
27 words
A process as claimed in claim 29, characterized in that the said organic solvent is selected from benzene, toluene, xylenes, dichloromethane, dichloroethane, trichloroethane, chlorobenzene and mixtures thereof.
Claim 40
Dependent Claim
75 words
A process as claimed in any of claims 13 to 30, characterized in that for each mol of the P or As compound, expressed as P or As, there are used at least 4 mols of the tungsten compound, expressed as W, and up to 2 mols of onium salt, and in that there are used from 2.5 to 6 mols of H 2 O 2 for each mol of W ( VI ) compound.
Claim 41
Dependent Claim
29 words
A process as claimed in claim 31, characterized in that there is used an excess of H202 for the oxidation of W compound having a valence lower than VI.
Claim 42
Dependent Claim
59 words
An epoxidation catalyst for olefines, fixed on a polymeric macroporous polystyrenic or silicone resin, characterized in that the said catalyst is prepared by reaction of an oxygenated derivative of tungsten, an oxygenated derivative of P or As and hydrogen peroxide, contained in an acid aqueous phase, and an onium salt fixed on a macroporous polymeric polystyrenic or silicone resin.
Claim 43
Dependent Claim
59 words
An epoxidation catalyst for olefines, fixed on a polymeric macroporous polystyrenic or silicone resin, characterized in that the said catalyst is prepared by reaction of an oxygenated derivative of tungsten, an oxygenated derivative of P or As and hydrogen peroxide, contained in an acid aqueous phase, and an onium salt fixed on a macroporous polymeric polystyrenic or silicone resin.
Claim 44
Dependent Claim
65 words
A process for the preparation of an epoxidation catalyst fixed on a polymeric macroporous polystyrenic or silicone resin according to claim 33, characterized in that an oxygenated tungsten derivative, and an oxygenated derivative of P or As and hydrogen peroxide, contained in an aqueous phase having a pH below 4, are reacted with an onium salt fixed on a polymeric macroporous polystyrenic or silicone resin.
Claim 45
Dependent Claim
19 words
A process as claimed in claim 35, characterized in that the said aqueous phase has a pH below 2.
Claim 46
Dependent Claim
27 words
Use of the compositions of formula (I) as defined in any of claims from 1 to 12, as oxidation. agents, preferably in epoxidation reactions for olefinic compounds.
Claim 47
Dependent Claim
48 words
Use of the compositions of formula (I) as defined in any of claims from 1 to 12, and of the catalysts fixed on resins as defined in any of claims 33 to 35, as epoxidation catalysts for olefinic compounds in reactions conducted with H 2 O 2 .
Claim 48
Dependent Claim
49 words
Use, as expoxidation catalysts for olefinic compounds epoxidized with hydrogen peroxide, of compositions of formula (I) as defined in any of claims 1 to 12, supported on inert materials selected from clays, bauxites, kieselgur, alumina, pumice, zeolites, according to a catalyst/carrier ratio of from 0.01:1 to 0.05:1 by weight.
References Cited (Backward Citations)
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