Online continuous flow process for the synthesis of organic peroxides using hydrogen peroxide as raw material

Abstract

An online continuous flow production process for directly preparing organic peroxides by using hydrogen peroxide as a raw material. This production process uses hydrogen peroxide, catalyst, and an oxidation substrate as a raw material. Substrate will be turned to designated peroxides sequentially through oxidation and workup. This process is performed in a plug-and-produce integrated continuous flow reactor, and the raw materials are continuously fed to the reactor. So, specified peroxide can be continuously obtained at the outlet of the plug-and-produce integrated continuous flow reactor.

Claims

1. An online continuous flow production method for the direct synthesis of organic peroxide, comprising feeding raw material including hydrogen peroxide, a catalyst and an oxidized substrate continuously into inlets of a plug-and-produce integrated continuous flow reactor; wherein the plug-and-produce integrated continuous flow reactor comprises an oxidation unit and a workup unit; and obtaining organic peroxide at outlets of the plug-and-produce integrated continuous flow reactor; wherein the catalyst is acid or alkali, and the organic peroxide is selected from the group consisting of alkyl peroxide oxide, dialkyl peroxide, peroxycarboxylic acid, diacyl peroxide, peroxydicarbonate, and peroxyketal; wherein the oxidized substrate is selected from the group consisting of alcohol, carboxylic acid, anhydride, ketone, acyl chloride, and chloroformate; wherein a general formula of a production process inside the plug-and-produce integrated continuous flow reactor is as follows: ##STR00003## wherein A is the oxidation substrate, including alcohol, carboxylic acid, anhydride, ketone, acyl chloride and chloroformate; and C is alkyl peroxide, dialkyl peroxide, peroxycarboxylic acid, diacyl peroxide, peroxydicarbonate and peroxyketal.

2. The online continuous flow production method according to claim 1, wherein when A is acid chloride, the general formula is R.sup.1COCl; when A is chloroformate, the general formula is R.sup.2OCOCl; when A is alcohol, the general formula is R.sup.3(OH)n, wherein n is an integer greater than 0; when A is ketone, the general formula is R.sup.4R.sup.4(CO) or R.sup.4(CO) (Cyclone); when A is carboxylic acid, the general formula is R.sup.5COOH; when A is carboxylic anhydride, the general formula is (R.sup.5CO).sub.2O or R.sup.5(CO).sub.2O (cyclic anhydride); when C is a diacyl peroxide, the general formula is R.sup.1(COO).sub.2; when C is a peroxydicarbonate, the general formula is R.sup.2(OCOO).sub.2; when C is an alkyl peroxide, the general formula is R.sup.3(OOH).sub.n, wherein n is an integer greater than 0; when C is a dialkyl peroxide, the general formula is R.sup.3OOR.sup.3, where n=1; when C is a diketal peroxide, the general formula is R.sup.4(OOOH).sub.2; when C is a peroxycarboxylic acid, the general formula is R.sup.5OOOH; R.sup.1 is selected from C.sub.1-C.sub.20 saturated or unsaturated alkyl, unsubstituted or substituted aryl, unsubstituted or substituted heterocyclic aryl, unsubstituted or substituted saturated heterocycloalkyl, unsubstituted or substituted partially saturated heterocycloalkyl, unsubstituted or substituted cycloalkyl; R.sup.2 is selected from C.sub.1-C.sub.20 saturated or unsaturated alkyl, unsubstituted or substituted aryl, unsubstituted or substituted heterocyclic aryl, unsubstituted or substituted saturated heterocycloalkyl, unsubstituted or substituted partially saturated heterocycloalkyl, unsubstituted or substituted cycloalkyl; R.sup.3 is selected from C.sub.1-C.sub.12 saturated or unsaturated alkyl, unsubstituted or substituted aryl, unsubstituted or substituted heterocyclic aryl, unsubstituted or substituted saturated heterocycloalkyl, unsubstituted or substituted partially saturated heterocycloalkyl, unsubstituted or substituted cycloalkyl; R.sup.4 or R.sup.4 is selected from C.sub.1-C.sub.12 saturated or unsaturated alkyl, unsubstituted or substituted aryl, unsubstituted or substituted heterocyclic aryl, unsubstituted or substituted saturated heterocycloalkyl, unsubstituted or substituted partially saturated heterocycloalkyl, unsubstituted or substituted cycloalkyl; R.sup.5 is selected from C.sub.1-C.sub.12 saturated or unsaturated alkyl, unsubstituted or substituted aryl, unsubstituted or substituted heterocyclic aryl, unsubstituted or substituted saturated heterocycloalkyl, unsubstituted or substituted partially saturated heterocycloalkyl, unsubstituted or substituted cycloalkyl.

3. The online continuous flow production method according to claim 1, where in the organic peroxide is selected from the group consisting of diisobutyrylperoxide CAS NO: 3437-84-1, bis(3-methoxybutyl) peroxydicarbonate CAS NO: 52238-68-3, bis(ethoxyhexane) ester CAS NO: 763-69-9, diisopropyl peroxide dicarbonate CAS NO: 105-64-6, dibutyl peroxide dicarbonate CAS NO: 16215-49-9, di (3,5,5-trimethylhexanoyl) peroxide CAS NO: 3851-87-4, bis(2-ethylhexyl) peroxydicarbonate CAS NO: 16111-62-9, methyl ethyl ketone peroxide CAS NO: 1338-23-4, acetylacetone peroxide CAS NO: 37187-22-7, methyl isobutyl ketone peroxide CAS NO: 37206-20-5, tert-butyl hydroperoxide CAS NO: 75-91-2, di-tert-butyl peroxide CAS NO: 110-05-4, tert-amyl hydroperoxide CAS NO: 3425-61-4, di-tert-amyl peroxide CAS NO: 10508-09-5, peracetic acid CAS NO: 79-21-0, and 1,1,3,3-tetramethylbutyl hydroperoxide CAS NO: 5809-08-5.

4. The online continuous flow production method according to claim 1, wherein when an alkyl peroxide or a dialkylperoxide is produced, the oxidization substrate is an alcohol; a peroxycarboxylic acid is produced when the oxidation substrate is carboxylic acid; diacyl peroxide is produced when the oxidized substrate is acid chloride; peroxydicarbonate is produced when the oxidized substrate is chloroformate; biketal peroxide is produced when the oxidized substrate is ketone.

5. The online continuous flow production method according to claim 1, wherein the production time of the production process is equal to or less than 6 min.

6. The online continuous flow production method according to claim 1, wherein the target product organic peroxide is selected from the group consisting of diacyl peroxide and peroxydicarbonate; the content of chloride ion in the organic peroxide is 0.05 wt. %, and the content of H.sub.2O.sub.2 is 0.1 wt. %.

7. The online continuous flow production method according to claim 1, wherein the organic peroxide of the target product is the alkyl peroxide, and the content of H.sub.2O.sub.2 and di tert-butyl hydroperoxides in the alkyl peroxide is 0.1 wt. %.

8. The online continuous flow production method according to claim 1, wherein the organic peroxide of the target product is selected from the group consisting of dialkylperoxide, peroxycarboxylic acid and peroxyketal, and the content of H.sub.2O.sub.2 in the organic peroxide of the target product is 0.1 wt. %.

9. The online continuous flow production method according to claim 1, wherein the temperature of the oxidation process is 0 to 110 C.

10. The online continuous flow production method according to claim 1, wherein the temperature of the workup process is 0 to 50 C.

11. The online continuous flow production method according to claim 1, wherein the alkali is selected from the group consisting of water-soluble metal hydroxide, water-soluble quaternary ammonium hydroxide, water-soluble tertiary amine, water-soluble metal carbonate or water-soluble metal phosphate.

12. The online continuous flow production method according to claim 1, wherein the mass concentration of the acid solution is 50 to 90 wt. %.

13. The online continuous flow production method according to claim 1, wherein the concentration of the hydrogen peroxide is 30 to 50 wt. %.

14. The online continuous flow production method according to claim 1, wherein the molar ratio of acid to oxidation substrate is 0.5:1 to 1.1:1.

15. The online continuous flow production method according to claim 1, wherein the molar ratio of hydrogen peroxide to oxidation substrate is 0.5:1 to 2.5:1.

16. The online continuous flow production method according to claim 1, wherein the molar ratio of alkali to oxidization substrate is 1:1 to 1.4:1.

17. The online continuous flow production method according to claim 1, the oxidation unit at least comprises a first temperature zone, a second temperature zone and a third temperature zone being connected in series; the workup unit at least comprises a fourth temperature zone.

18. The online continuous flow production method according to claim 17, wherein the temperature in the first temperature zone is 0 to 60 C.; the temperature in the second temperature zone is 30 to 110 C.; the temperature in the third temperature zone is 0 to 50 C.; the temperature in the fourth temperature zone is 0 to 50 C.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 is a diagram of a continuous flow production process according to the disclosure.

(2) FIG. 2 is a schematic diagram of an integrated reactor according to the disclosure.

DETAILED DESCRIPTION OF THE DISCLOSURE

(3) The present disclosure will be further described with reference to specific cases. It should be claimed that these examples are only used to illustrate present disclosure and not to limit the its scope. In addition, it should be understood that when people make any changes or modifications according to the present disclosure after reading the present disclosure, these equivalent forms also fall within the scope defined by the appended claims of the present disclosure.

(4) The concentration in the examples of the present disclosure is the mass concentration. The product content is measured by effective oxygen titration (iodometric method). The chloride ion content is detected by an ion-detector. Other organic peroxides are analyzed by high performance liquid chromatography (HPLC) or effective oxygen titration (iodometric method). Content of alkyl peroxide products and other organic peroxides (H.sub.2O.sub.2 and dialkyl peroxide) in the present disclosure is 0.05 to 0.1 wt. %. The H.sub.2O.sub.2 content of products, such as alkyl peroxide, carbon peroxide and diketone peroxide, is 0.05 to 0.1 wt. %. For xylene peroxide and peroxydicarbonate products, chloride ion content is 0.02 wt. % to 0.05 wt. %, and H.sub.2O.sub.2 content is 0.05 wt. % to 0.1 wt. %. No delay line is required in the reactor.

(5) It should be noted that the mass concentration of hydrogen peroxide, catalyst and oxidized substrate used in actual production (including laboratory, pilot test, and actual production process) will have deviations of 2%. The temperature will have a deviation of 3 C. And production time will have a deviation of 5 s.

USED ABBREVIATIONS

(6) TBA: tert-Butanol

(7) TAA: tert-amyl alcohol

(8) 2-EHCF: 2-ethylhexyl chloroformate

(9) NSC904: 2,4,4-trimethyl-2-pentanol

(10) IBCL: isobutyrylchloride

(11) TMHC: 3,5,5-trimethylhexanoyl chloride

(12) MEK: methyl ethyl ketone

(13) IPCF: isopropyl chloroformate

(14) ACAC: acetylacetone

(15) 3-MOCF: 3-methoxybutyl chloroformate

(16) 2-EOCF: 2-ethoxyethyl chloroformate

(17) BCF: butyl chlorocarbonate

(18) MIBK: methyl isobutyl ketone

EXAMPLES 1-8 PREPARATION OF bis(3,5,5-trimethylhexanoyl) peroxide

(19) As shown in FIGS. 1 and 2, raw material 1 (aqueous hydrogen peroxide solution), raw material 2 (alkali solution), and raw material 3 (oxidized substrate) are successively fed into a continuous reactor by a constant flow pump. They sequentially flow from temperature zone 1 to temperature zone 3 during which the reaction is complete. Then reaction liquid flows out of the temperature zone 3 and enters the temperature zone 4 for workup, after which the final product would be obtained. Feed rate 1 represents the feed rate of raw material 1, Feed rate 2 represents the feed rate of raw material 2, and feed rate 3 represents the feed rate of raw material 3.

(20) TABLE-US-00001 Examples Example 1 Example 2 Example 3 Example 4 Feed rate 1 Property H.sub.2O.sub.2/H.sub.2O H.sub.2O.sub.2/H.sub.2O H.sub.2O.sub.2/H.sub.2O H.sub.2O.sub.2/H.sub.2O Weight % 30 30 30 30 L/h 0.55 2.04 10.7 0.92 Feed rate 2 Property KOH/H.sub.2O KOH/H.sub.2O KOH/H.sub.2O KOH/H.sub.2O Weight % 35 20 20 45 L/h 1.36 7.18 3.66 1.65 Feed rate 3 Property TMHC TMHC TMHC TMHC Weight % 98 98 98 98 L/h 2.02 6.75 3.29 2.42 Total feed L/h 4.04 15.97 8.02 5.05 rate Temperature C. 0 5 5 5 zone 1 Temperature C. 30 40 50 60 zone 2 Temperature C. 0 5 10 20 zone 3 Temperature C. 0 5 10 20 zone 4 KOH:H.sub.2O.sub.2:TMHC 1:0.5:1 1.15:0.55:1 1.2:0.6:1 1.3:0.7:1 Production min 3.6 1.0 2.0 2.66 time Yield % 91.8 92.3 92.0 92.1 Content % 93 92.2 91.6 91.0 Examples Example 5 Example 6 Example 7 Example 8 Feed rate 1 Property H.sub.2O.sub.2/H.sub.2O H.sub.2O.sub.2/H.sub.2O H.sub.2O.sub.2/H.sub.2O H.sub.2O.sub.2/H.sub.2O Weight % 30 50 30 30 L/h 0.83 0.53 0.48 24.9 Feed rate 2 Property KOH/H.sub.2O KOH/H.sub.2O KOH/H.sub.2O KOH/H.sub.2O Weight % 15 5 20 15 L/h 4.43 10.4 1.77 132.9 Feed rate 3 Property TMHC TMHC TMHC TMHC Weight % 98 98 98 98 L/h 2.02 2.02 1.74 60.6 Total feed L/h 7.28 12.95 3.99 218.4 rate Temperature C. 0 10 20 0 zone 1 Temperature C. 70 80 90 70 zone 2 Temperature C. 30 40 10 30 zone 3 Temperature C. 30 40 10 30 zone 4 KOH:H2O.sub.2:TMHC 1.4:0.75:1 1.1:0.8:1 1.1:0.5:1 1.4:0.75:1 Production min 2.2 1.23 4.0 2.2 time Yield % 91.8 92.1 92.0 91.7 Content % 91.5 91.2 91.0 91.6

EXAMPLES 9-18 PREPARATION OF tert-butyl hydroperoxide

(21) As shown in FIGS. 1 and 2, raw material 1 (acidic solution), raw material 2 (oxidized substrate), and raw material 3 (aqueous hydrogen peroxide solution) are successively fed into a continuous reactor by a constant flow pump. They sequentially flow from temperature zone 1 to temperature zone 3 during which the reaction is complete. Then reaction liquid flows out of the temperature zone 3 and enters the temperature zone 4 for workup, after which the final product would be obtained. Feed rate 1 represents the feed rate of raw material 1, Feed rate 2 represents the feed rate of raw material 2, and feed rate 3 represents the feed rate of raw material 3.

(22) TABLE-US-00002 Examples Example 9 Example 10 Example 11 Example 12 Example 13 Feed rate 1 Property H.sub.2SO.sub.4/H.sub.2O H.sub.2SO.sub.4/H.sub.2O H.sub.2SO.sub.4/H.sub.2O H.sub.2SO.sub.4/H.sub.2O H.sub.2SO.sub.4/H.sub.2O Weight % 50 70 70 80 70 L/h 1.79 2.06 1.14 1.17 2.11 Feed rate 2 Property TBA/H.sub.2O TBA/H.sub.2O TBA/H.sub.2O TBA/H.sub.2O TBA/H.sub.2O Weight % 94.3 94.3 94.3 94.3 94.3 L/h 2.6 2.6 2.17 2.17 4.29 Feed rate 3 Property H.sub.2O.sub.2/H.sub.2O H.sub.2O.sub.2/H.sub.2O H.sub.2O.sub.2/H.sub.2O H.sub.2O.sub.2/H.sub.2O H.sub.2O.sub.2/H.sub.2O Weight % 50 50 50 30 50 L/h 1.54 1.17 1.1 2.03 2.66 Total feed L/h 5.93 5.83 4.41 5.37 9.06 rate Temperature C. 5 20 30 40 0 zone 1 Temperature C. 85 40 50 60 85 zone 2 Temperature C. 5 30 40 10 0 zone 3 Temperature C. 5 30 40 10 0 zone 4 H.sub.2SO.sub.4:H.sub.2O.sub.2:TBA 0.5:1.05:1 1:0.8:1 0.6:0.9:1 0.7:1:1 0.6:1.1:1 Production min 2.9 3.0 4.0 3.3 2.0 time Yield % 75.4 72.4 72.6 71.3 75.4 Content % 83 80.6 80.5 81.1 80 Examples Example 14 Example 15 Example 16 Example 17 Example 18 Feed rate 1 Property H.sub.2SO.sub.4/H.sub.2O H.sub.2SO.sub.4/H.sub.2O H.sub.2SO.sub.4/H.sub.2O H.sub.2SO.sub.4/H.sub.2O H.sub.2SO.sub.4/H.sub.2O Weight % 60 70 70 90 50 L/h 1.49 2.06 4.22 1.04 53.7 Feed rate 2 Property TBA/H.sub.2O TBA/H.sub.2O TBA/H.sub.2O TBA/H.sub.2O TBA/H.sub.2O Weight % 94.3 94.3 94.3 94.3 94.3 L/h 2.6 2.6 8.58 2.17 78 Feed rate 3 Property H.sub.2O.sub.2/H.sub.2O H.sub.2O.sub.2/H.sub.2O H.sub.2O.sub.2/H.sub.2O H.sub.2O.sub.2/H.sub.2O H.sub.2O.sub.2/H.sub.2O Weight % 50 50 50 50 50 L/h 1.76 1.54 5.32 1.28 46.2 Total feed L/h 5.84 6.2 18.12 4.49 177.9 rate Temperature C. 0 10 5 5 5 zone 1 Temperature C. 70 90 100 80 85 zone 2 Temperature C. 20 30 10 5 5 zone 3 Temperature C. 20 30 10 5 5 zone 4 H.sub.2SO.sub.4:H.sub.2O.sub.2:TBA 0.5:1.2:1 0.9:1.05:1 0.6:1.05:1 0.7:1.05:1 0.5:1.05:1 Production min 3.2 2.89 1.0 3.73 2.9 time Yield % 75.4 72.4 72.6 71.3 75.8 Content % 84 80.6 82.5 81.1 83.2

EXAMPLES 19-28 PREPARATION OF tert-amyl hydrogen peroxide

Operating as Examples 9-18

(23) TABLE-US-00003 Examples Example 19 Example 20 Example 21 Example 22 Example 23 Feed rate 1 Property H.sub.2SO.sub.4/H.sub.2O H.sub.2SO.sub.4/H.sub.2O H.sub.2SO.sub.4/H.sub.2O H.sub.2SO.sub.4/H.sub.2O H.sub.2SO.sub.4/H.sub.2O Weight % 70 60 70 80 50 L/h 1.76 1.87 1.41 1.4 2.7 Feed rate 2 Property TAA/H.sub.2O TAA/H.sub.2O TAA/H.sub.2O TAA/H.sub.2O TAA/H.sub.2O Weight % 98 98 98 98 98 L/h 2.22 2.02 1.78 2.02 2.22 Feed rate 3 Property H.sub.2O.sub.2/H.sub.2O H.sub.2O.sub.2/H.sub.2O H.sub.2O.sub.2/H.sub.2O H.sub.2O.sub.2/H.sub.2O H.sub.2O.sub.2/H.sub.2O Weight % 50 30 50 50 50 L/h 1.28 1.53 0.9 1.16 1.35 Total feed L/h 5.26 5.42 4.08 4.58 6.29 rate Temperature C. 5 10 20 30 40 zone 1 Temperature C. 85 90 100 70 80 zone 2 Temperature C. 30 5 10 20 30 zone 3 Temperature C. 30 5 10 20 30 zone 4 H.sub.2SO.sub.4:H.sub.2O.sub.2:TAA 1:1.14:1 1:0.9:1 1:1:1 1:1.14:1 1.1:1.2:1 Production min 3.1 3.0 4.0 3.4 2.6 time Yield % 79.3 77.4 74.6 73.3 79.3 Content % 84.2 84.0 83.9 84.4 84.2 Examples Example 24 Example 25 Example 26 Example 27 Example 28 Feed rate 1 Property H.sub.2SO.sub.4/H.sub.2O H.sub.2SO.sub.4/H.sub.2O H.sub.2SO.sub.4/H.sub.2O H.sub.2SO.sub.4/H.sub.2O H.sub.2SO.sub.4/H.sub.2O Weight % 70 70 90 70 70 L/h 1.76 4.52 1.23 2.63 52.8 Feed rate 2 Property TAA/H.sub.2O TAA/H.sub.2O TAA/H.sub.2O TAA/H.sub.2O TAA/H.sub.2O Weight % 98 98 98 98 98 L/h 2.22 7.13 2.22 3.5 66.6 Feed rate 3 Property H.sub.2O.sub.2/H.sub.2O H.sub.2O.sub.2/H.sub.2O H.sub.2O.sub.2/H.sub.2O H.sub.2O.sub.2/H.sub.2O H.sub.2O.sub.2/H.sub.2O Weight % 50 50 50 50 50 L/h 1.7 4.66 1.28 2 38.4 Total feed L/h 5.38 16.31 4.73 8.13 157.8 rate Temperature C. 0 10 10 5 5 zone 1 Temperature C. 85 40 50 60 85 zone 2 Temperature C. 40 0 10 30 30 zone 3 Temperature C. 40 0 10 30 30 zone 4 H.sub.2SO.sub.4:H.sub.2O.sub.2:TAA 1:1.25:1 0.8:1.3:1 0.9:1.14:1 0.95:1.14:1 1:1.14:1 Production min 3.0 1.0 3.5 2.0 3.0 time Yield % 79.3 77.4 74.6 73.3 79.6 Content % 84.2 84.0 83.9 84.4 84.6

EXAMPLES 29-36 PREPARATION OF bis(2-ethylhexyl) peroxydicarbonate

Operating as Examples 1-8

(24) TABLE-US-00004 Examples Example 29 Example 30 Example 31 Example 32 Feed rate 1 Property H.sub.2O.sub.2/H.sub.2O H.sub.2O.sub.2/H.sub.2O H.sub.2O.sub.2/H.sub.2O H.sub.2O.sub.2/H.sub.2O Weight % 30 30 30 50 L/h 0.55 2.54 0.88 0.48 Feed rate 2 Property Na.sub.2CO.sub.3/H.sub.2O K.sub.2CO.sub.3/H.sub.2O LiOH/H.sub.2O KOH/H.sub.2O Weight % 20 20 15 5 L/h 2.33 9.8 2.9 9.8 Feed rate 3 Property 2-EHCF 2-EHCF 2-EHCF 2-EHCF Weight % 98 98 98 98 L/h 2.03 7.82 2.3 1.83 Total feed L/h 4.8 20.2 6.09 4.23 rate Temperature C. 0 5 10 20 zone 1 Temperature C. 10 15 20 30 zone 2 Temperature C. 0 5 10 20 zone 3 Temperature C. 0 5 10 20 zone 4 Alkali:H.sub.2O.sub.2:2-EHCF 1.2:0.5:1 1.2:0.6:1 1.4:0.7:1 1.15:0.8:1 Production min 3.71 1.0 3.0 4.0 time Yield % 90.4 88.6 87.8 86.5 Content % 96.2 95.8 96.0 95.6 Examples Example 33 Example 34 Example 35 Example 36 Feed rate 1 Property H.sub.2O.sub.2/H.sub.2O H.sub.2O.sub.2/H.sub.2O H.sub.2O.sub.2/H.sub.2O H.sub.2O.sub.2/H.sub.2O Weight % 30 30 30 30 L/h 0.55 1.09 0.75 22.5 Feed rate 2 Property KOH/H.sub.2O KOH/H.sub.2O KOH/H.sub.2O KOH/H.sub.2O Weight % 25.5 25.5 45 45 L/h 2.4 3.95 1.04 31.2 Feed rate 3 Property 2-EHCF 2-EHCF 2-EHCF 2-EHCF Weight % 98 98 98 98 L/h 2.03 3.6 1.83 54.9 Total feed L/h 4.98 8.7 3.61 108.3 rate Temperature C. 5 10 5 5 zone 1 Temperature C. 35 40 30 30 zone 2 Temperature C. 5 5 5 5 zone 3 Temperature C. 5 5 5 5 zone 4 KOH:H.sub.2O.sub.2:2-EHCF 1.3:0.5:1 1.2:0.55:1 1.1:0.75:1 1.1:0.75:1 Production min 3.47 2.0 4.72 4.72 time Yield % 90.1 88.9 87.9 87.4 Content % 95.2 95.6 96.6 96.2

EXAMPLES 37-38 PREPARATION OF 1,1,3,3-tetramethyl butyl hydroperoxide

Operating as Examples 9-18

(25) TABLE-US-00005 Examples Example 37 Example 38 Feed rate 1 Property H.sub.2SO.sub.4/H.sub.2O H.sub.2SO.sub.4/H.sub.2O Weight % 80 90 L/h 0.79 0.7 Feed rate 2 Property NSC904 NSC904 Weight % 95 95 L/h 3.15 3.15 Feed rate 3 Property H.sub.2O.sub.2/H.sub.2O H.sub.2O.sub.2/H.sub.2O Weight % 50 50 L/h 1.08 1.08 Total feed L/h 5.02 4.93 rate Temperature C. 5 5 zone 1 Temperature C. 110 70 zone 2 Temperature C. 30 30 zone 3 Temperature C. 30 30 zone 4 H.sub.2SO.sub.4:H.sub.2O.sub.2:NSC904 0.56:1.04:1 0.56:1.04:1 Production min 3.2 3.26 time Yield % 76.4 73.4 Content % 79.3 79.6

EXAMPLES 39-43

Operating as Examples 9-18

(26) TABLE-US-00006 Examples Example 39 Example 40 Example 41 Example 42 Example 43 Feed rate 1 Property CF.sub.3COOH/H.sub.2O H.sub.2SO.sub.4/H.sub.2O H.sub.2SO.sub.4/H.sub.2O H.sub.3PO.sub.4/H.sub.2O H.sub.2SO.sub.4/H.sub.2O Weight % 70 50 60 70 70 L/h 2.46 2.46 2.05 1.7 1.65 Feed rate 2 Property TBA/H.sub.2O TAA/H.sub.2O MEK MIBK ACAC Weight % 94.3 98 98 98 98 L/h 2.6 2.22 1.83 2.43 1.97 Feed rate 3 Property H.sub.2O.sub.2/H.sub.2O H.sub.2O.sub.2/H.sub.2O H.sub.2O.sub.2/H.sub.2O H.sub.2O.sub.2/H.sub.2O H.sub.2O.sub.2/H.sub.2O Weight % 50 50 50 50 50 L/h 0.74 0.56 2.04 2.43 1.92 Total feed L/h 5.8 5.24 5.92 6.56 5.54 rate Temperature C. 5 5 5 5 5 zone 1 Temperature C. 90 90 85 80 85 zone 2 Temperature C. 30 20 10 40 50 zone 3 Temperature C. 30 20 10 40 50 zone 4 Acid:H.sub.2O.sub.2:TBA/TAA/ 1:1:0.5 1:1:0.6 1:1:2 1:1:2.5 1:1:2 MEK/MIBK/ACAC Production min 3.5 3.76 3.33 3 3.56 time Yield % 94.3 93.6 73.2 74.7 75.5 Content % 93.4 95.4 80.5 82.3 83.1

EXAMPLES 44-48

Operating as Examples 1-8

(27) TABLE-US-00007 Examples Example 44 Example 45 Example 46 Example 47 Example 48 Feed rate 1 Property H.sub.2O.sub.2/H.sub.2O H.sub.2O.sub.2/H.sub.2O H.sub.2O.sub.2/H.sub.2O H.sub.2O.sub.2/H.sub.2O H.sub.2O.sub.2/H.sub.2O Weight % 30 30 30 30 30 L/h 0.55 0.55 0.55 0.55 0.66 Feed rate 2 Property KOH/H.sub.2O KOH/H.sub.2O KOH/H.sub.2O KOH/H.sub.2O KOH/H.sub.2O Weight % 15 20 30 35 45 L/h 3.47 2.83 2.04 1.89 1.51 Feed rate 3 Property IBCL 3-MOCF 2-EOCF IPCF BCF Weight % 98 98 98 98 98 L/h 1.08 1.54 1.37 1.42 1.57 Total feed L/h 5.1 4.92 3.96 3.86 3.74 rate Temperature C. 5 5 5 5 5 zone 1 Temperature C. 30 30 40 50 30 zone 2 Temperature C. 5 5 5 5 0 zone 3 Temperature C. 5 5 5 5 0 zone 4 KOH:H2O.sub.2:IBCL/3-MOCF/ 1.1:0.5:1 1.2:0.5:1 1.3:0.5:1 1.4:0.5:1 1.2:0.5:1 2EOCF/IPCF/BCF Production min 3.5 3.63 4.5 4.6 4.7 time Yield % 94.3 93.6 73.2 74.7 75.5 Content % 91.3 90.2 80.5 81.5 83.2

EXAMPLE 49

Operating as Examples 9-18

(28) TABLE-US-00008 Examples Example 49 Feed rate 1 Property H.sub.2SO.sub.4 Weight % 90 L/h 0.03 Feed rate 2 Property AC.sub.2O Weight % 98 L/h 1.73 Feed rate 3 Property H.sub.2O.sub.2/H.sub.2O Weight % 50 L/h 0.74 Total feed L/h 2.5 rate Temperature C. 30 zone 1 Temperature C. 50 zone 2 70 Temperature C. 5 zone 3 Temperature C. 5 zone 4 H.sub.2SO.sub.4:H.sub.2O.sub.2:AC.sub.2O 1:2:1 Production min 3.2 time Yield % 76.7 Content % 80

(29) It can be seen from the above examples that the continuous flow synthesis of organic peroxides according to the present disclosure has a huge advantage in time, which has been shortened from several hours in the existing process to 6 minutes, and the overall yield and content are significantly improved. At the same time, it can be seen from Examples 5 and 8, 9 and 18, 19 and 28, 35 and 36 that the yield did not change after scale-up and the reaction time did not increase, indicating that the present disclosure does not have a magnifying effect.

Comparative Example 1 Preparation of Bis(3,5,5-trimethylhexanoyl) peroxide

(30) TABLE-US-00009 Comparative Chinese patent Example 1 CN101287704A Present disclosure Process Mix first, complete Mix, reaction, and heat reaction within exchange are performed a certain retention simultaneously, the volume after heat reaction is maintained exchange to a proper for a certain residence temperature time Temperature/ C. 10-25 30-90 Reaction Time(not 3.5-10 0.63 include workup time)/min yield % 92 91.8-92.5 Content % 91 91-93

(31) As can be seen from the above comparative Example 1, the process of the present disclosure is essentially different from the Chinese patent CN101287704A. The reaction can be completed at a higher temperature and in a shorter time. The yield and content remain unchanged and the reaction time is shortened by more than 82%.