Method for preparing organic peroxides
09758479 · 2017-09-12
Assignee
Inventors
Cpc classification
C07C407/003
CHEMISTRY; METALLURGY
C07C409/16
CHEMISTRY; METALLURGY
C07C409/16
CHEMISTRY; METALLURGY
B01J31/0225
PERFORMING OPERATIONS; TRANSPORTING
International classification
C07C409/16
CHEMISTRY; METALLURGY
Abstract
A method for preparing peroxide, including a step of treating, in a reaction medium, a component having at least one tertiary alcohol grouping with a compound having at least one tertiary hydroperoxide function in the presence of a catalyst, said method being characterized in that the catalyst includes a sulphonic acid and a inorganic acid, the molar ratio between the sulphonic acid and the aforementioned component including at least one tertiary alcohol grouping ranges from 0.05 to 0.8, and the molar ratio between the inorganic acid and the aforementioned component including at least one tertiary alcohol grouping ranges from 0.05 to 0.8. Also, to the peroxide resulting directly from said preparation method.
Claims
1. A process for preparing peroxide, comprising a step of placing in contact in a reaction medium a component containing at least one tertiary alcohol group with a compound containing at least one tertiary hydroperoxide function in the presence of a catalyst, wherein: the catalyst comprises a sulfonic acid and a mineral acid, the mole ratio between the sulfonic acid and said component comprising at least one tertiary alcohol group is between 0.05 and 0.8, and the mole ratio between the mineral acid and said component comprising at least one tertiary alcohol group is between 0.05 and 0.8.
2. The process as claimed in claim 1, wherein the mole ratio between the sulfonic acid and the component comprising at least one tertiary alcohol group is between 0.1 and 0.6.
3. The process as claimed in claim 1 wherein the mole ratio between the mineral acid and the component comprising at least one tertiary alcohol group is between 0.1 and 0.6.
4. The process as claimed in claim 1, wherein the process is performed at atmospheric pressure (±0.2 bar).
5. The process as claimed in claim 1, wherein said component and/or said compound comprises one or more aromatic functions such that the peroxide comprises at least one aromatic function.
6. The process as claimed in claim 1, wherein said compound comprising a hydroperoxide group is selected from the group consisting of tert-butyl hydroperoxide, tert-amyl hydroperoxide, 1-methylcyclohexyl hydroperoxide and 1-methylcyclopentyl hydroperoxide.
7. The process as claimed in claim 1, wherein said compound comprising a hydroperoxide group is selected from the group consisting of 2,5-dimethyl-2,5-dihydroperoxy-3-hexyne and 2,5-dimethyl-2,5-dihydroperoxyhexane.
8. The process as claimed in claim 1, wherein said component comprising an alcohol group is selected from the group consisting of tert-butanol, tert-amyl alcohol, cumyl alcohol, 1-methylcyclohexanol and 1-methylcyclopentanol.
9. The process as claimed in claim 1, wherein said component comprising an alcohol group is selected from the group consisting of α,α′-dihydroxydiisopropylbenzene, 2,5-dimethyl-2,5-dihydroxy-3-hexyne and 2,5-dimethyl-2,5-dihydroxyhexane.
10. The process as claimed in claim 1, wherein the sulfonic acid is selected from the group consisting of alkyl sulfonic acid, aryl sulfonic acid, and mixtures thereof.
11. The process as claimed in claim 1, wherein the mineral acid is selected from the group consisting of sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid and perchloric acid, and mixtures thereof.
12. The process as claimed in claim 1, wherein the stoichiometric excess between the reagents, namely between said compound comprising at least one tertiary hydroperoxide group and said compound containing at least one tertiary alcohol function, is between 0.01 and 1.
13. The process as claimed in claim 1, wherein the step of placing in contact is performed at a temperature of between 10° C. and 60° C.
14. The process as claimed in claim 1, wherein it comprises a step prior to said step of placing in contact in the reaction medium, consisting of a step of mixing the mineral acid with the sulfonic acid outside said reaction medium.
15. The process as claimed in claim 1, wherein the catalyst consists solely of the sulfonic acid and the mineral acid.
Description
DETAILED DESCRIPTION OF THE INVENTION
(1) The invention relates to a process for producing peroxide, comprising a step of placing a compound comprising at least one tertiary alcohol group in contact with a compound containing at least one tertiary hydroperoxide function in the presence of a catalyst. The compound comprising at least one tertiary alcohol group reacts by condensation with a compound containing at least one tertiary hydroperoxide function via acid catalysis.
(2) The peroxides produced according to the process of the invention are dialkyl peroxides that may contain up to two O—O (oxygen-oxygen) peroxide functions.
(3) As regards the compounds comprising at least one tertiary alcohol group, they may be tert-butyl alcohol, tert-amyl alcohol, cumyl alcohol, 1-methylcyclohexanol, 1-methylcyclopentanol, α,α′-dihydroxydiisopropylbenzene, 2,5-dimethyl-3-hexyne-2,5diol or 2,5-dimethyl-2,5-hexanediol.
(4) As regards the compound containing at least one tertiary hydroperoxide function, it may be tert-butyl hydroperoxide, tert-amyl hydroperoxide, 1-methylcyclohexyl hydroperoxide, 1-methylcyclopentyl hydroperoxide, 2,5-dimethyl-2,5dihydroperoxy-3-hexyne or 2,5-dimethyl-2,5-dihydroperoxyhexane.
(5) The process for producing organic dialkyl peroxide according to the invention is performed by placing an alcohol in contact with a hydroperoxide in the presence of a catalyst.
(6) The process according to the invention comprises the use of a catalyst comprising a combination of a mineral acid and a sulfonic acid. Only these two components (mineral and sulfonic acids) are required to perform the invention (to solve the technical problems), but it may optionally be envisaged to combine other components to constitute the catalyst.
(7) As regards the mineral acids, they may be sulfuric acid, hydrochloric acid, perchloric acid, nitric acid or phosphoric acid, and mixtures thereof.
(8) As regards the sulfonic acids, they may be alkyl sulfonic acids such as methanesulfonic acid, fluoroalkyl sulfonic acids such as trifluoromethanesulfonic acid, aromatic sulfonic acids such as benzenesulfonic acid, para-toluenesulfonic acid, para-phenolsulfonic acid, naphthalenesulfonic acid, xylenesulfonic acid or cumenesulfonic acid, and mixtures thereof.
(9) The mineral acid and the sulfonic acid according to the process of the invention may be added separately or may be premixed before introduction into the reaction medium.
(10) The process according to the invention is preferably performed in the presence of an organic solvent. Solvents that may be mentioned include pentane, hexane, heptane, benzene, toluene, xylenes, cumene and chlorinated hydrocarbons.
(11) TABLE-US-00001 Peroxide formula Hydroperoxide formula Alcohol formula Di-tert-butyl peroxide:
(12) The process according to the invention does not require removal, azeotropically or by other means, of the water formed by the condensation reaction gradually as the peroxide production reaction proceeds.
(13) Once the peroxide has been obtained, at least a final step of removal of the aqueous phase after decantation is conventionally envisaged, along with steps well known to those skilled in the art, such as steps of basic neutralization of the catalyst, aqueous washing, removal of the reaction solvent and purification.
(14) Examples of implementation of the preparation process according to the invention are presented hereinbelow. These examples are illustrated with the production of the mixture of meta and para isomers of α,α′-bis(tert-butylperoxy)diisopropylbenzene.
(15) However, experiments were conducted on all the peroxides listed in this table.
(16) It emerges that the production of peroxides comprising at least one aromatic nucleus is particularly suited to the preparation process according to the invention (at least one of the reagents, conventionally the component bearing the alcohol function, comprising an aromatic nucleus).
(17) However, the production of aliphatic peroxides, including peroxides comprising saturated rings, is also advantageously performed via the preparation process according to the invention and makes it possible to solve virtually all, or even all, of the technical problems encountered with the preparation processes of the prior art.
Example 1 (According to the Invention): Implementation of the Synthetic Process According to the Invention
(18) 66.5 grams (g) of a tert-butyl hydroperoxide (TBHP) solution at 40.5 wt % (the term “wt %” means the “weight percent”) in heptane and 27.8 g of a mixture of isomers (meta/para) of α,α′-dihydroxy-diisopropylbenzene at 93 wt % (diol) are placed in a 250 milliliter (ml) reactor equipped with a bottom valve, a stirrer, a temperature probe and a reflux condenser. The mixture is heated to 30° C. while stirring under nitrogen. At this temperature, 8.6 g of a cumylsulfonic acid solution (65 wt %) are added in a single injection. 8 grams (g) of a sulfuric acid solution (70 wt %) are then gradually added over about two (2) minutes. The temperature of the medium rises to 37-40° C. When the addition of the acids is complete, the temperature is maintained at 40° C. for a time of 115 min (minutes) while stirring the medium.
(19) After this period, the stirring is stopped while maintaining the reactor at 40° C. Two phases separate on settling. The lower phase (aqueous—25.6 g) is removed from the reactor via the bottom valve.
(20) While resuming the stirring, the upper phase (organic) is washed at 40° C. with 63.2 g of water. After (5) minutes of washing, the stirring is stopped to separate two phases. The lower phase (aqueous—63.8 g) is removed via the bottom valve.
(21) While resuming the stirring, the upper phase (organic) is washed at 40° C. with 62.4 g of aqueous sodium hydroxide solution (15 wt %). After 5 minutes of washing, the stirring is stopped to separate two phases. The lower phase (aqueous—64.2 g) is removed via the bottom valve.
(22) The process is completed with a final wash at 40° C. of the upper phase (organic) with 60.7 g of water. After 5 min of washing, the stirring is stopped to separate two phases. A lower phase (aqueous: 61.2 g) and an upper phase (organic: 77.3 g) are recovered.
(23) After analysis, the organic solution contains 41.2 g of α,α′-bis(tert-butylperoxy)diisopropylbenzene (C.sub.20H.sub.34O.sub.4), 0.35 g of α-(tert-butylperoxy)-α′-hydroxyisopropylbenzene (C.sub.16H.sub.26O.sub.3) and 0.43 g of α-(tert-butylperoxy)-α′-isopropenylbenzene (C.sub.16H.sub.24O.sub.2) corresponding, respectively, to the sum of the meta and para isomers of each of the compounds. This represents a yield of α,α′-bis(tert-butylperoxy)diisopropylbenzene of 92% relative to the diol engaged. The material balance on these three aromatic products is 93% relative to the diol engaged.
Example 1bis
(24) The process is performed in the same manner as in Example 1, but using cumyl alcohol as tertiary alcohol and the operating conditions described in the table below.
(25) TABLE-US-00002 Example 1bis Sulfonic acid CUSA Temperature ° C. 30 Reaction time min 30 TBHP/cumyl alcohol ratio mol 1.2 [Sulfonic acid] Weight % 65 [H.sub.2SO.sub.4] Weight % 70 Sulfonic acid/cumyl alcohol ratio mol 0.1 H.sub.2SO.sub.4/diol ratio mol 0.19 Aromatic balance mol % 97 tert-Butylcumyl peroxide yield mol % 96.6
Example 1ter
(26) The process is performed in the same manner as in Example 1, but using cumyl alcohol as tertiary alcohol, cumyl hydroperoxide as tertiary hydroperoxide and cumene as solvent, and the operating conditions described in the table below.
(27) TABLE-US-00003 Example 1ter Sulfonic acid CUSA Temperature ° C. 30 Reaction time Min 30 Cumyl hydroperoxide/cumyl alcohol ratio Mol 1.2 [Sulfonic acid] Weight % 65 [H.sub.2SO.sub.4] Weight % 70 Sulfonic acid/cumyl alcohol ratio mol 0.1 H.sub.2SO.sub.4/cumyl alcohol ratio mol 0.16 Aromatic balance mol % 95 Dicumyl peroxide yield mol % 82
Example 1 Quatro
(28) The process is performed in the same manner as in Example 1, but using tert-amyl alcohol as tertiary alcohol, tert-amyl hydroperoxide as tertiary hydroperoxide and methanesulfonic acid (MSA), and the operating conditions described in the table below.
(29) It will be noted here that this Example 1 quatro corresponds to the definition of the main claim (claim 1), but not to the dependent claims 2 and 3.
(30) TABLE-US-00004 Example 1 quatro Sulfonic acid MSA Temperature ° C. 30 Reaction time min 120 tert-Amyl hydroperoxide/tert-amyl alcohol ratio Mol 1.1 [Sulfonic acid] Weight % 68 [H.sub.2SO.sub.4] Weight % 70 Sulfonic acid/tert-amyl alcohol ratio mol 0.37 H.sub.2SO.sub.4/tert-amyl alcohol ratio mol 0.75 Di-tert-amyl peroxide yield mol % 75
Counter-Examples 2 and 3
(31) The process is performed in the same manner as in Example 1, but using each of the two acids separately.
(32) TABLE-US-00005 Counter-examples 2 3 Acid CUSA H.sub.2SO.sub.4 Temperature ° C. 40 40 Reaction time min 120 120 TBHP/diol ratio mol 2.2 2.3 [acid] Weight % 65 70 Acid/diol ratio mol 0.21 0.32 Aromatic balance mol 97 86 C.sub.20H.sub.34O.sub.4 yield mol 58.3 8.4
(33) It is found that the use of only one acid, whether a sulfonic acid or a mineral acid, in the proportions described in Example 1, does not make it possible to achieve the same yield of peroxide desired and remains much lower than that obtained by combining the two acids.
(34) Combining the two acids also leads to a better result (in terms of yield) than the sum of the results obtained by using each acid in isolation, thus reflecting a synergistic effect of the two acids.
(35) It may be noted that the material balance of the aromatic species degrades on using sulfuric acid alone under the conditions mentioned. This phenomenon is not observed on combining a sulfonic acid, which also constitutes one of the advantages of this invention.
Counter-Examples 2bis and 3bis
(36) The process is performed in the same manner as in Example 1bis, but using each of the two acids separately.
(37) TABLE-US-00006 Counter-examples 2 bis 3 bis Acid CUSA H.sub.2SO.sub.4 Temperature ° C. 30 30 Reaction time min 30 30 TBHP/cumyl alcohol ratio mol 1.2 1.2 [acid] Weight % 65 70 Acid/cumyl alcohol ratio mol 0.1 0.19 Aromatic balance Mol % 98 86 tert-Butylcumyl peroxide yield Mol % 34.4 41.3
Counter-Examples 2ter and 3ter
(38) The process is performed in the same manner as in Example 1ter, but using each of the two acids separately.
(39) TABLE-US-00007 Counter-examples 1ter 1ter Acid CUSA H.sub.2SO.sub.4 Temperature ° C. 30 30 Reaction time g/min 30 30 Cumyl hydroperoxide/cumyl alcohol ratio mol 1.2 1.2 [acid] Weight % 65 70 Acid/cumyl alcohol ratio mol 0.1 0.2 Aromatic balance Mol % 95 87 Dicumyl peroxide yield Mol % 32 31
Counter-Examples 2quatro and 3quatro
(40) The process is performed in the same manner as in Example 1quatro, but using each of the two acids separately.
(41) TABLE-US-00008 Counter-examples 2 quatro 3quatro Acid MSA H.sub.2SO.sub.4 Temperature ° C. 30 30 Reaction time min 120 120 tert-Amyl hydroperoxide/tert-amyl mol 1.2 1.2 alcohol ratio [acid] Weight % 68 68 Acid/tert-amyl alcohol ratio mol 0.39 0.73 Di-tert-amyl peroxide yield Mol % 3.7 23.5
Examples 4 to 6 (According to the Invention)
(42) The process is performed in the same manner as in Example 1, but changing the nature of the sulfonic acid used: para-toluenesulfonic acid (PTSA), benzenesulfonic acid (BSA), phenolsulfonic acid (PPSA).
(43) TABLE-US-00009 Example 4 5 6 Sulfonic acid PTSA BSA PPSA Temperature ° C. 40 40 40 Reaction time min 120 120 120 TBHP/diol ratio mol 2.2 2.3 2.3 [Sulfonic acid] Weight % 70 70 65 [H.sub.2SO.sub.4] Weight % 70 70 70 Sulfonic acid/diol ratio mol 0.209 0.209 0.213 H.sub.2SO.sub.4/diol ratio mol 0.498 0.433 0.433 Aromatic balance mol % 97.7 95.4 100.3 C.sub.20H.sub.34O.sub.4 yield mol 89.3 87.5 76.9
(44) The use of the mixture of sulfonic acid with sulfuric acid according to the invention makes it possible to achieve yields of α,α′-bis(tert-butylperoxy)diisopropylbenzene of greater than or equal to 75% in not more than two hours of reaction.
Counter-Example 7
(45) The process is performed in the same manner as in the preceding example, but using PTSA alone, not in combination with sulfuric acid.
(46) TABLE-US-00010 Counter-examples 7 Acid PTSA Temperature ° C. 40 Reaction time min 120 TBHP/diol ratio mol 2.2 [acid] Weight % 65 Acid/diol ratio mol 0.21 Aromatic balance mol 98 C.sub.20H.sub.34O.sub.4 yield mol 41.7
(47) It is found that the use of the sulfonic acid alone, in the proportions described, does not lead to a satisfactory yield (<75%).
Examples 8 to 16 (According to the Invention)
(48) The process is performed in the same manner as in Example 1, but changing the reaction parameters (ratios, concentrations).
(49) TABLE-US-00011 Example 8 9 10 11 12 13 14 15 16 Sulfonic acid CUSA CUSA CUSA CUSA CUSA CUSA CUSA CUSA CUSA Temperature ° C. 40 40 40 40 40 40 40 30 50 Reaction time min 94 90 111 120 150 120 90 120 129 TBHP/diol mol 2.2 2.4 2.2 2.2 2.4 2.2 2.2 2.4 2.4 ratio [Sulfonic Weight % 65 65 65 65 65 65 65 65 65 acid] [H.sub.2SO.sub.4] Weight % 96 96 80 70 70 70 70 96 96 Sulfuric mol 0.129 0.17 0.127 0.21 0.126 0.17 0.128 0.169 0.137 acid/diol ratio H.sub.2SO.sub.4/diol mol 0.345 0.346 0.344 0.428 0.348 0.345 0.346 0.345 0.136 ratio Aromatic mol 97.6 97.2 94.8 98.3 101 95.8 90.3 96.9 90.8 balance C.sub.20H.sub.34O.sub.4 mol 87.4 89.7 85.6 91.6 93.6 88.9 84.3 89.4 59.8 yield
(50) High yields of the desired peroxide are found in all the tests performed.
(51) The synergistic effect is found by comparing the results obtained with those of Counter-examples 17 to 19 performed with only one acid.
(52) TABLE-US-00012 Counter-examples 17 18 19 Sulfonic acid CUSA CUSA CUSA Temperature ° C. 40 40 40 Reaction time min 120 120 120 TBHP/diol ratio mol 2.2 2.4 2.2 [Sulfonic acid] Weight % 65 65 65 Sulfonic acid/diol ratio mol 0.13 0.17 0.21 Aromatic balance mol C.sub.20H.sub.34O.sub.4 yield mol 41.8 50.7 58.3