Online continuous flow process for the preparation of organic peroxides direct from alcohols or alkanes
10919849 · 2021-02-16
Assignee
Inventors
Cpc classification
C07C409/22
CHEMISTRY; METALLURGY
B01J19/00
PERFORMING OPERATIONS; TRANSPORTING
C07C409/38
CHEMISTRY; METALLURGY
C07C409/32
CHEMISTRY; METALLURGY
C07C409/22
CHEMISTRY; METALLURGY
C07C409/38
CHEMISTRY; METALLURGY
C07C409/08
CHEMISTRY; METALLURGY
C07C409/02
CHEMISTRY; METALLURGY
B01J19/0006
PERFORMING OPERATIONS; TRANSPORTING
C07C407/003
CHEMISTRY; METALLURGY
C07C409/08
CHEMISTRY; METALLURGY
International classification
B01J19/00
PERFORMING OPERATIONS; TRANSPORTING
Abstract
A continuous flow production process for preparing organic peroxides directly from alcohols or alkanes takes very safe alcohols or alkanes as starting materials, and directly reacts to obtain designated peroxides. The production process is carried out in an integrated continuous flow reactor, and a safe starting source of alcohol or alkane is continuously added at the feed inlet of the integrated continuous flow reactor, and continuously provided with a designated peroxide at the discharge port of the integrated continuous flow reactor.
Claims
1. An online continuous flow production method for the preparation of organic peroxides direct from alcohols or alkanes, comprising: feeding reaction substrate, oxidant and condensation agent into inlets of an integrated continuous flow reactor; and obtaining an organic peroxide by oxidation condensation and workup; wherein the organic peroxides are selected from the group consisting of carboxylate peroxide, carbonate peroxide, and ketal peroxide; the reaction substrate is alcohol or alkane, and the condensation agent is alkali liquor and acyl compound during the production of carboxylate peroxide and carbamate peroxide; in the production of ketal peroxide, the reaction substrate is acid solution and condensation raw material, and the condensation raw material is alcohol or ketone; the general formula of a production process in the integrated continuous flow reactor is as follows: ##STR00005## wherein, A.sub.1 is alcohol or alkane; A.sub.2 is selected from the group consisting of acyl chloride, chloroformate, alcohol and ketone, oxidant is selected from the group consisting of hydrogen peroxide and oxygen; C is selected from the group consisting of carboxylate peroxide, carbonate peroxide and ketal peroxide.
2. The online continuous flow production method according to claim 1, wherein when A.sub.1 is alcohol, the general formula of A.sub.1 is R(OH).sub.n, where n=an integer greater than 0; when A.sub.1 is alkane, the general formula of A.sub.1 is R(H).sub.n, where n=an integer greater than 0; when A.sub.2 is acyl chloride, the general formula of A.sub.2 is R.sup.1COCl; when A.sub.2 is chloroformate, the general formula of A.sub.2 is R.sup.2OCOCl; when A.sub.2 is alcohol, the general formula of A.sub.2 is R.sup.3(OH).sub.m, where m=an integer greater than 0; when A.sub.2 is ketone, the general formula of A.sub.2 is R.sup.4R.sup.4(CO) or R.sup.4(CO) (cyclohexanone); n, m is a positive integer; when C is carboxylate peroxide, the general formula of C is R(OOOCR.sup.1).sub.n, where n=an integer greater than 0; when C is carbonate peroxide, the general formula of C is R(OOOCOR.sup.2).sub.n, where n=an integer greater than 0; when C is ketal peroxide, the general formula of C is R.sup.4(OOR).sub.2, where n=1; when C is ketal peroxide, the general formula of C is R.sup.3(OOR).sub.m, where n=1, m=an integer greater than 0; when C is ketal peroxide, the general formula of C is R(OOR.sup.3).sub.n, where m=1, n=an integer greater than 0; n and m are positive integers; R is selected from the group consisting of saturated or unsaturated C.sub.1-C.sub.12 alkyl, unsubstituted or substituted aryl, unsubstituted or substituted heterocyclic aryl, unsubstituted or substituted saturated heterocyclic alkyl, unsubstituted or substituted partially saturated heterocyclic alkyl, unsubstituted or substituted cycloalkyl; R.sup.1 is selected from the group consisting of saturated or unsaturated C.sub.1-C.sub.20 alkyl, unsubstituted or substituted aryl, unsubstituted or substituted heterocyclic aryl; R.sup.2 is selected from the group consisting of saturated or unsaturated C.sub.1-C.sub.20 alkyl group, unsubstituted or substituted aryl group, unsubstituted or substituted heterocyclic aryl group, unsubstituted or substituted saturated heterocyclic alkyl group, unsubstituted or substituted partially saturated heterocyclic alkyl group, unsubstituted or substituted cycloalkyl group; R.sup.3 is selected from the group consisting of saturated or unsaturated C.sub.1-C.sub.12 alkyl group, unsubstituted or substituted aryl group, unsubstituted or substituted heterocyclic aryl group, unsubstituted or substituted saturated heterocyclic alkyl group, unsubstituted or substituted partially saturated heterocyclic alkyl group, unsubstituted or substituted cycloalkyl group; R.sup.4 or R.sup.4 is selected from the group consisting of saturated or unsaturated C.sub.1-C.sub.12 alkyl, unsubstituted or substituted aryl, unsubstituted or substituted heterocyclic aryl, unsubstituted or substituted saturated heterocyclic alkyl, unsubstituted or substituted partially saturated heterocyclic alkyl, unsubstituted or substituted cycloalkyl; R(OH).sub.n is selected from the group consisting of tert-butanol, tert-amyl alcohol, 2,4,4-trimethyl-2-pentanol, 2,5-dimethyl-2,5-dihydroxyhexane, dihydroxy-1,4-diisopropylbenzene and dihydroxy-1,3-diisopropylbenzene; R(H).sub.n is selected from the group consisting of cumene, 1,4-diisopropylbenzene and 1,3-diisopropylbenzene; R.sup.1COCl is selected from the group consisting of acetyl chloride, propionyl chloride, butyryl chloride, isobutyryl chloride, valeryl chloride, 2-methylbutyryl chloride, neopentyl chloride, 2-methylvaleryl chloride, 2-ethylbutyryl chloride, 2-ethylhexyl chloride, nonyl chloride, 2,4,4-trimethylvaleryl chloride, 3,5,5-trimethylhexyl chloride, neodecanoyl chloride, decanoyl chloride, lauroyl chloride, benzoyl chloride, 2-methylbenzoyl chloride, 4-methylbenzoyl chloride, 4-chlorobenzoyl chloride, 2,4-di chlorobenzoyl chloride, naphthyl chloride; R.sup.2OCOCl is selected from the group consisting of methyl chloroformate, ethyl chloroformate, n-propyl chloroformate, isopropyl chloroformate, n-butyl chloroformate, sec-butyl chloroformate, 2-ethylhexyl chloroformate, isotridecyl chloroformate, stearyl chloroformate, cyclohexyl chloroformate, 4-tert-butyl cyclohexyl chloroformate, benzyl chloroformate and 2-phenoxyethyl chloroformate; R.sup.3(OH).sub.n is selected from the group consisting of tert-butanol, tert-amyl alcohol, 2,4,4-trimethyl-2-pentanol, 2,5-dimethyl-2,5-dihydroxyhexane, dihydroxy-1,4-diisopropylbenzene and dihydroxy-1,3-diisopropylbenzene; R.sup.4R.sup.4(CO) is selected from the group consisting of methyl ethyl ketone; R.sup.4(CO) is selected from cyclohexanone, 3,3,5-trimethylcyclohexanone.
3. The online continuous flow production method according to claim 1, wherein the organic peroxide C is selected from the group consisting of: t-butyl peroxybenzoate CAS No.: 614-45-9, t-amyl peroxybenzoate CAS No.: 4511-39-1, t-butyl peroxyacetate CAS No.: 107-71-1, t-butyl terephentate peroxide CAS No.: 927-07-1, t-amyl terephentate peroxide CAS No.: 29240-17-3, t-butyl peroxyneodecanoate CAS No.: 26748-41-4, t-amyl peroxyneodecanoate CAS No.: 68299-16-1, t-butyl peroxide 2-ethylcaproate CAS No.: 3006-82-4, t-amyl peroxide 2-ethylcaproate CAS No.: 686-31-7, t-butyl isobutyrate peroxide CAS No.: 109-13-7, t-butyl neoheptanoate peroxide CAS No.: 26748-38-9, t-butyl 3,5,5-trimethylhexanoate peroxide CAS No.: 13122-18-4, t-butyl 2-ethylhexanoate peroxide CAS No.: 34443-12-4, t-butyl 2-ethylhexanoate peroxide t-amyl carbonate CAS No.: 70833-40-8, 1,1-di-tert-butyl peroxide-3,3,5-trimethylcyclohexane CAS No.: 6731-36-8, 1,1-di(tert-butyl peroxide) cyclohexane CAS No.: 3006-86-8, 2,2-di(tert-butyl peroxide) butane CAS No.: 2167-23-9, isopropylphenyl peroxyneodecanoate CAS No.: 26748-47-0, 1,1,3,3-tetramethylbutyl peroxyneodecanoate CAS No.: 51240-95-0 1,1,3,3-tetramethylbutyl peroxypivalate CAS No.: 22288-41-1, 1,1,3,3-tetramethyl-butyl peroxy-2-ethylhexanoate CAS No.: 22288-43-3, 1,1-bis (tert-amty peroxy) cyclohexane CAS No.: 15667-10-4, t-amyl acetate peroxide CAS No.: 690-83-5, t-butyl isopropyl carbonate peroxide CAS No.: 2372-21-6, and t-butyl peroxide isopropylbenzene CAS No.: 3457-61-2.
4. The online continuous flow production method according to claim 1, wherein the production method has no macroscopical accumulation, purification and stagnation of alkyl peroxides.
5. The online continuous flow production method according to claim 4, wherein the general formula of the alkyl peroxide is R(OOH).sub.n, wherein R is selected from the group consisting of saturated or unsaturated C.sub.1-C.sub.12 alkyl, unsubstituted or substituted aryl, unsubstituted or substituted heterocyclic aryl, unsubstituted or substituted saturated heterocyclic group, unsubstituted or substituted partially saturated heterocyclic group, and unsubstituted or substituted cyclic Alkyl, n1, n is a positive integer; the alkyl peroxide is selected from the group consisting of: t-butyl hydroperoxide CAS No.: 75-91-2, t-amyl hydroperoxide CAS No.: 3425-61-4, CAS No.: 4212-43-5, 1,1,3,3-tetramethyl-butyl hydroperoxide CAS No.: 5809-08-5, cumene hydroperoxide CAS No.: 80-15-9, 2,5-dimethyl-2,5-bis (hydroperoxides) hexane CAS No.: 3025-88-5, and dihydroxy-1,4-diisopropylbenzene CAS No.: 3159-98-6.
6. The online continuous flow production method according to claim 1, wherein the content of chloride ion in the target organic peroxide is 0.05 wt %, the content of other organic peroxide impurities is 0.1 wt %, and the other organic peroxide impurities are any one or more of H.sub.2O.sub.2, alkyl peroxide and dialkyl peroxide.
7. The online continuous flow production method according to claim 1, wherein the production time of the method is 15 min.
8. The online continuous flow production method according to claim 1, wherein the yield of the organic peroxide is 64%.
9. The online continuous flow production method according to claim 1, wherein the content of the organic peroxide is 77%.
10. The online continuous flow production method according to claim 1, wherein the temperature of the oxidative condensation method is 0-200 C.
11. The online continuous flow production method according to claim 1, wherein the workup temperature is 0 to 60 C.
12. 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 and water-soluble metal phosphate.
13. The online continuous flow production method according to claim 1, wherein the mass concentration of the alkali liquor is 5% to 45%.
14. The online continuous flow production method according to claim 1, wherein the acid is selected from the group consisting of sulfuric acid, phosphoric acid and trifluoroacetic acid.
15. The online continuous flow production method according to claim 1, wherein the mass concentration of the acid solution is 50% to 90%.
16. The online continuous flow production method according to claim 1, wherein the oxidant is hydrogen peroxide or oxygen.
17. The online continuous flow production method according to claim 1, wherein the reaction substrate is selected from the group consisting of tert-butanol, tert-amyl alcohol, isopropyl benzene, 1,4-diisopropylbenzene, p-mengane, pinane, tetrahydronaphthalene, 2,4,4-trimethyl-2-pentanol, 1,3-diisopropylbenzene, dihydroxy-1,4-diisopropylbenzene, dihydroxy-1,3-diisopropylbenzene.
18. The online continuous flow production method according to claim 1, wherein the acyl compounds in the condensation agent are selected from acetyl chloride, propionyl chloride, butyryl chloride, isobutyryl chloride, valeryl chloride, 2-methylbutyryl chloride, neopentyl chloride, 2-methylpentyl chloride, 2-ethylbutyryl chloride, 2-ethylhexyl chloride, nonyl chloride, 2,4,4-trimethylpentyl chloride, 3,5,5-trimethyl hexyl chloride, neodecanoyl chloride, decanoyl chloride, lauroyl chloride, benzoyl chloride, 2-methylbenzoyl chloride, 4-methylbenzoyl chloride, 4-chlorobenzoyl chloride, 2,4-dichlorobenzoyl chloride, naphthoyl chloride, methyl chloroformate, ethyl chloroformate, n-propyl chloroformate, isopropyl chloroformate, n-butyl chloroformate, sec-butyl chloroformate, 2-ethylhexyl chloroformate, isotridecyl chloroformate ester, stearyl chloroformate, cyclohexyl chloroformate, 4-tert-butyl cyclohexyl chloroformate, benzyl chloroformate and 2-phenoxyethyl chloroformate; the alcohol in the condensation agent is selected from the group consisting of tert-butanol and tert-amyl alcohol; the ketone in the condensation agent is selected from the group consisting of cyclohexanone, 3,3,5-trimethylcyclohexanone and methyl ethyl ketone.
19. The online continuous flow production method according to claim 1, wherein the molar ratio of acid and reaction substrate is 0.3:1 to 1.5:1.
20. The online continuous flow production method according to claim 1, wherein the molar ratio of oxidant and reaction substrate is 0.8:1 to 2.2:1.
21. The online continuous flow production method according to claim 1, wherein the molar ratio of alkali and reaction substrate is 0.7:1 to 2:1.
22. The online continuous flow production method according to claim 1, wherein the molar ratio of acyl compound and reaction substrate is 0.5:1 to 1.2:1.
23. The online continuous flow production method according to claim 1, wherein the molar ratio of the raw condensation material and the reaction substrate is 0.5:1 to 1.2:1.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
(1)
(2)
DETAILED DESCRIPTION OF THE DISCLOSURE
(3) The following examples, illustrating the disclosure further, are not to be constructed as being limitations thereon. It will be appreciated that all kinds of improvements, modifications and alternatives based on the disclosure by person skilled in the art after reading the descriptions of the disclosure, which are all equivalents of the disclosure, do not depart from the broad inventive concept thereof.
(4) The following abbreviations are used in the example:
(5) TBA: tert-butyl alcohol
(6) TAA: tertiary amyl alcohol
(7) NDCl: neodecanoyl chloride
(8) 2-EHCF: 2-ethylhexyl chloroformate
(9) CYC: cyclohexanone
(10) CBO: benzoyl chloride
(11) Cumene: cumene
(12) NSC904: 2,4,4-trimethyl-2-pentanol
(13) PVCL: pivaloyl chloride
(14) 2-CHC: 2-ethylhexyl chloride
(15) IBCL: isobutyric chloride
(16) U535: heptanyl chloride
(17) INCL: 3,5,5-trimethylhexyl chloride
(18) 335TCYC: 3,3,5-trimethylcyclohexanone
(19) MEK: methyl ethyl ketone
(20) IPCF: isopropyl chloroformate
(21) ACL: acetyl chloride
(22) The concentrations in the examples of the disclosure are all mass concentrations. The content of the target product is measured by the effective oxygen content titration (iodometry), the chloride ion content is detected by the ion detector, and other organic peroxides are detected by the high performance liquid chromatography (HPLC). The chloride ion content in the target product of the disclosure is 0.03-0.05%, and other organic peroxides are 0.05-0.1% His organic peroxide impurities are selected from any one or more of H.sub.2O.sub.2, alkyl peroxide and dialky peroxide. There is no need to delay the pipeline in the reactor.
(23) It should be noted that the reaction substrate, oxidant and condensation agent used in actual production (including laboratory, pilot test and actual production process) have a deviation of 2 percentage points in mass concentration, a deviation of 3 C. in temperature zone and a deviation of 5 s in production time.
Examples 1-12 are the Preparation of Tert-Butyl Peroxyneodecanoate
(24) As shown in
(25) TABLE-US-00001 Examples Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 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 H.sub.2SO.sub.4/H.sub.2O weight % 70 70 70 60 80 70 L/h 2.56 1.83 1.28 2.66 1.12 1.28 Feed rate 2 Property TBA/H.sub.2O 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 94.3 L/h 5.2 2.6 2.6 2.6 2.6 2.6 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 H.sub.2O.sub.2/H.sub.2O weight % 50 50 30 50 50 30 L/h 3.7 1.54 2.3 1.23 1.54 2.3 Feed rate 4 Property KOH/H.sub.2O KOH/H.sub.2O KOH/H.sub.2O KOH/H.sub.2O KOH/H.sub.2O KOH/H.sub.2O weight % 20 5 20 45 30 35 L/h 8 20.4 4.0 2.27 3.4 4.0 Feed rate 5 Property NDCl NDCl NDCl NDCl NDCl NDCl weight % 98 98 98 98 98 98 L/h 5.26 2.63 2.63 2.63 2.63 2.63 Total feed L/h 24.72 29 12.81 10.63 11.35 12.81 Temperature C. 70 60 40 30 20 5 zone 1 Temperature C. 160 130 120 110 100 90 zone 2 Temperature C. 40 30 20 5 0 30 zone 3 Temperature C. 90 80 70 60 50 40 zone 4 Temperature C. 50 40 30 20 5 0 zone 5 Temperature C. 50 40 30 20 5 0 zone 6 TBA:H.sub.2SO.sub.4:H.sub.2O.sub.2:KOH:NDCL 1:0.5:1.2:1.2:0.7 1:0.8:1:1.2:0.7 1:0.6:0.9:1.2:0.7 1:1:0.8:1.2:0.7 1:0.6:1:1.2:0.7 1:0.6:0.9:1.2:0.7 mole ratio Production time min 3.3 3.0 6.0 6.7 6.64 6.0 Total yield % 73.5 71.5 70 68.5 81.5 73 Content % 91.5 90.3 90.4 90.6 89.4 90.4 Examples Example 7 Example 8 Example 9 Example 10 Example 11 Example 12 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 H.sub.2SO.sub.4/H.sub.2O weight % 70 50 70 90 70 70 L/h 2.74 1.77 1.28 0.72 1.28 38.4 Feed rate 2 Property TBA/H.sub.2O 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 94.3 L/h 2.6 2 2.6 1.87 2.6 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 H.sub.2O.sub.2/H.sub.2O weight % 50 50 50 50 30 30 L/h 1.54 1.19 1.54 1.17 2.57 77.1 Feed rate 4 Property KOH/H.sub.2O KOH/H.sub.2O KOH/H.sub.2O KOH/H.sub.2O KOH/H.sub.2O KOH/H.sub.2O weight % 15 20 20 20 20 20 L/h 6.8 13.06 4.3 3.3 5.3 159 Feed rate 5 Property NDCl NDCl NDCl NDCl NDCl NDCl weight % 98 98 98 98 98 98 L/h 2.1 2.7 2.63 1.89 3.33 99.9 Total feed L/h 15.78 9.84 12.35 8.4 12.75 382.5 Temperature C. 5 5 5 5 5 5 zone 1 Temperature C. 80 70 60 50 40 40 zone 2 Temperature C. 20 20 5 20 5 5 zone 3 Temperature C. 30 20 50 60 60 60 zone 4 Temperature C. 5 5 30 5 20 20 zone 5 Temperature C. 5 5 5 5 5 5 zone 6 TBA:H.sub.2SO.sub.4:H.sub.2O.sub.2:KOH:NDCL 1:1.3:1:1.2:0.6 1:0.5:1.5:0.9:1.1 1:0.5:1:1.3:0.7 1:0.3:1.05:1.4:0.5 1:0.6:1:1.6:0.9 1:0.6:1:1.6:0.9 mole ratio Production time Min 5.0 8.0 6.31 9.0 6.12 6.12 Total yield % 68.6 80.3 79.7 71.3 80 80 Content % 89.6 89.3 88.4 88.1 87.9 87.9
Example 13-14 are the Preparation of Tert-Amyl Peroxybenzoate
(26) Operation method of example 1 to 12 is adopted.
(27) TABLE-US-00002 Example Example 13 Example 14 Feed rate 1 Property CF.sub.3COOH/H.sub.2O H.sub.2SO.sub.4/H.sub.2O weight % 70 70 L/h 1.72 1.6 Feed rate 2 Property TAA/H.sub.2O TAA/H.sub.2O weight % 98 98 L/h 2.22 2.02 Feed rate 3 Property H.sub.2SO.sub.4/H.sub.2O H.sub.2SO.sub.4/H.sub.2O weight % 50 50 L/h 1.28 1.16 Feed rate 4 Property KOH/H.sub.2O KOH/H.sub.2O weight % 20 20 L/h 3.05 2.78 Feed rate 5 Property CB0 CB0 weight % 98 98 L/h 1.79 1.63 Total Feed L/h 9.7 9.19 Temperature C. 5 5 zone 1 Temperature C. 90 80 zone 2 Temperature C. 40 30 zone 3 Temperature C. 90 80 zone 4 Temperature C. 30 30 zone 5 Temperature C. 30 30 zone 6 TBA:H.sub.2SO.sub.4:H.sub.2O.sub.2:KOH:CBO 1:0.6:1:1.2:0.7 1:0.6:1:1.2:0.7 mole ratio Production min 7.0 8.0 time Total yield % 72.3 76.4 Content % 78.8 79.4
Example 15-26 are the Preparation of Tert-Butyl Peroxide-2-Ethylhexyl Carbonate
(28) The operation methods of examples 1 to 12 are adopted.
(29) TABLE-US-00003 Examples Example 15 Example 16 Example 17 Example 18 Example 19 Example 20 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 H.sub.2SO.sub.4/H.sub.2O weight % 70 70 60 70 70 60 L/h 3.66 1.5 1.49 2.1 1.28 1.49 Feed rate 2 Property TBA/H.sub.2O 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 94.3 L/h 5.2 1.72 2.6 2.0 2.6 2.6 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 H.sub.2O.sub.2/H.sub.2O weight % 30 50 50 50 50 50 L/h 4.12 0.91 1.54 1.18 2 1.54 Feed rate 4 Property KOH/H.sub.2O KOH/H.sub.2O KOH/H.sub.2O KOH/H.sub.2O KOH/H.sub.2O KOH/H.sub.2O weight % 20 20 5 45 30 20 L/h 8 2.84 23.46 3.33 3.4 4.6 Feed rate 5 Property 2-EHCF 2-EHCF 2-EHCF 2-EHCF 2-EHCF 2-EHCF weight % 98 98 98 98 98 98 L/h 5.3 1.75 2.65 2.16 2.65 2.65 Total Rate L/h 26.28 8.7 31.74 8.76 11.93 12.85 Temperature C. 70 60 40 30 20 5 zone 1 Temperature C. 160 130 120 110 100 90 zone 2 Temperature C. 40 30 20 5 0 5 zone 3 Temperature C. 90 80 70 60 50 40 zone 4 Temperature C. 50 40 30 20 5 0 zone 5 Temperature C. 50 40 30 20 5 0 zone 6 TBA:H.sub.2SO.sub.4:H.sub.2O.sub.2:KOH:2-EHCF 1:0.8:0.8:1.2:0.7 1:1:0.9:1.3:0.7 1:0.5:1:1.4:0.7 1:1.2:1:0.9:0.9 1:0.5:1.3:1.2:0.7 1:0.5:1:1.6:0.7 mole ratio Production time Min 3.2 9.0 3.0 8.0 7.0 6.5 Total yield % 81.37 72.5 71.88 71.38 71.1 71.88 Content % 96.2 97.0 97.1 96.9 95.6 97.1 Examples Example 21 Example 22 Example 23 Example 24 Example 25 Example 26 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 H.sub.2SO.sub.4/H.sub.2O weight % 70 50 70 90 80 80 L/h 1.28 2.24 1.28 2.1 1.12 33.6 Feed rate 2 Property TBA/H.sub.2O 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 94.3 L/h 2.6 2.0 2.6 4.2 2.6 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 H.sub.2O.sub.2/H.sub.2O weight % 50 50 50 30 30 30 L/h 2.16 1.77 1.67 2.48 1.54 46.2 Feed rate 4 Property KOH/H.sub.2O KOH/H.sub.2O KOH/H.sub.2O KOH/H.sub.2O KOH/H.sub.2O KOH/H.sub.2O weight % 15 20 20 30 20 20 L/h 6.8 3.08 6.8 6.47 4.0 120 Feed rate 5 Property 2-EHCF 2-EHCF 2-EHCF 2-EHCF 2-EHCF 2-EHCF weight % 98 98 98 98 98 98 L/h 2.65 2.88 2.78 3.6 3.46 103.8 Total feed L/h 15.48 11.97 14.8 18.85 12.74 382.2 Temperature C. 5 5 5 5 5 5 zone 1 Temperature C. 80 70 60 50 40 40 zone 2 Temperature C. 5 5 5 5 5 5 zone 3 Temperature C. 30 20 20 60 50 50 zone 4 Temperature C. 5 5 5 5 5 5 zone 5 Temperature C. 5 5 5 5 5 5 zone 6 TBA:H.sub.2SO.sub.4:H.sub.2O.sub.2:KOH:2-EHCF 1:0.3:1.4:1.2:0.7 1:1.3:1.5:1.2:1.1 1:0.5:1.05:1.6:0.9 1:0.6:1:1.2:0.5 1:0.5:1:1.2:0.9 1:0.5:1:1.2:0.9 mole ratio Production time min 5.0 7.37 6.0 4.0 6.12 6.12 Total yield % 81.5 71.5 81.38 80.38 70.1 71.1 Content % 97.0 96.6 96.3 96.0 97.1 97.0
Example 27-28 are the Preparation of 1,1-Di (Tert-Butyl Peroxide) Cyclohexane
(30) As shown in
(31) TABLE-US-00004 Examples Example 27 Example 28 Feed rate 1 Property H.sub.2SO.sub.4/H.sub.2O H.sub.3PO.sub.4/H.sub.2O weight % 70 70 L/h 1.28 1.26 Feed rate 2 Property TBA/H.sub.2O TBA/H.sub.2O weight % 94.3 94.3 L/h 2.6 2.6 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 1.54 1.54 Feed rate 4 Property H.sub.2SO.sub.4/H.sub.2O H.sub.2SO.sub.4/H.sub.2O weight % 70 70 L/h 0.57 0.57 Feed rate 5 Property CYC CYC weight % 98 98 L/h 0.66 0.66 Total feed L/h 6.65 6.63 Temperature C. 0 5 zone 1 Temperature C. 90 80 zone 2 Temperature C. 20 50 zone 3 Temperature C. 65 75 zone 4 Temperature C. 30 30 zone 5 Temperature C. 30 30 zone 6 TBA:H.sub.2SO.sub.4:H.sub.2O.sub.2:H.sub.2SO.sub.4:CYC 1:0.5:1:0.5:0.5 1:0.6:1:0.5:0.5 mole ratio Production min 6.0 6.0 time Total yield % 65.4 67.5 Content % 80.5 81.1
Example 29-38 are the Preparation of Isopropyl Neodecanoate Peroxide
(32) As shown in
(33) TABLE-US-00005 Examples Example 29 Example 30 Example 31 Example 32 Example 33 Feed rate 1 Property Na.sub.2CO.sub.3/H.sub.2O Na.sub.2CO.sub.3/H.sub.2O Na.sub.2CO.sub.3/H.sub.2O Na.sub.2CO.sub.3/H.sub.2O Na.sub.2CO.sub.3/H.sub.2O weight % 10 10 10 10 10 L/h 0.6 0.64 0.6 0.6 0.6 Feed rate 2 Property Cumene Cumene Cumene Cumene Cumene weight % 100 100 100 100 100 L/h 1.56 1.67 1.56 1.56 1.56 Feed rate 3 Property O.sub.2 O.sub.2 O.sub.2 O.sub.2 O.sub.2 weight % 100 100 100 100 100 L/h 0.5 0.57 0.55 0.38 0.33 Feed rate 4 Property NaOH/H.sub.2O NaOH/H.sub.2O NaOH/H.sub.2O NaOH/H.sub.2O NaOH/H.sub.2O weight % 20 20 20 45 30 L/h 1.6 1.85 2 1.18 2 Feed rate 5 Property NDCl NDCl NDCl NDCl NDCl weight % 98 98 98 98 98 L/h 1.6 2.46 1.38 1.15 2.16 Total feed L/h 5.86 7.19 6.09 4.88 6.65 Temperature C. 80 70 60 40 30 zone 1 Temperature C. 180 150 130 120 110 zone 2 Temperature C. 50 40 30 20 5 zone 3 Temperature C. 100 80 60 50 40 zone 4 Temperature C. 50 40 30 20 5 zone 5 Temperature C. 50 40 30 20 5 zone 6 Cumene:Na.sub.2CO.sub.3:O.sub.2:NaOH:NDCL 1:0.5:2:1:0.7 1:0.5:2.1:1.3:1.1 1:0.5:2.2:1.5:0.6 1:0.6:1.5:1.6:0.5 1:0.6:1.3:1.8:0.9 Mole Ratio Production time min 8.57 7.0 8.0 9.0 8.0 Total yield % 79.76 80.2 81.1 80.4 79.7 Content % 89.5 89.2 89.1 94.2 89.52 Examples Example 34 Example 35 Example 36 Example 37 Example 38 Feed rate 1 Property Na.sub.2CO.sub.3/H.sub.2O Na.sub.2CO.sub.3/H.sub.2O Na.sub.2CO.sub.3/H.sub.2O Na.sub.2CO.sub.3/H.sub.2O Na.sub.2CO.sub.3/H.sub.2O weight % 10 10 10 10 10 L/h 0.6 1.47 0.6 1.1 33 Feed rate 2 Property Cumene Cumene Cumene Cumene Cumene weight % 100 100 100 100 100 L/h 1.56 3.8 1.56 2.87 86.1 Feed rate 3 Property O.sub.2 O.sub.2 O.sub.2 O.sub.2 O.sub.2 weight % 100 100 100 100 100 L/h 0.5 1.23 0.5 0.92 27.6 Feed rate 4 Property NaOH/H.sub.2O NaOH/H.sub.2O NaOH/H.sub.2O NaOH/H.sub.2O NaOH/H.sub.2O weight % 15 20 5 20 20 L/h 3.33 4.9 10 3.68 110.4 Feed rate 5 Property NDCl NDCl NDCl NDCl NDCl weight % 98 98 98 98 98 L/h 2.16 5.29 2.16 3.97 119.7 Total feed L/h 8.15 16.71 14.82 12.55 376.5 Temperature C. 20 10 0 60 60 zone 1 Temperature C. 100 90 80 60 60 zone 2 Temperature C. 0 20 20 20 20 zone 3 Temperature C. 30 20 10 60 60 zone 4 Temperature C. 0 5 5 5 5 zone 5 Temperature C. 0 5 5 5 5 zone 6 Cumene:Na.sub.2CO.sub.3:O.sub.2:NaOH:NDCL 1:0.6:0.8:1.5:0.9 1:0.6:2.1:1.5:0.9 1:0.6:2:1.5:0.9 1:0.5:2:1.5:0.9 1:0.6:2:1.5:0.9 mole ratio Production time min 6.17 3.0 3.4 4.0 8.17 Total yield % 80.3 81.0 80.7 81.2 81.4 Content % 89.5 89.7 93.2 89.0 89.2
Example 39-50 are the Preparation of Neodecanoic Acid-1,1,3,3-Tetramethyl Butyl Peroxide
(34) Operation method of example 1 to 12 are adopted.
(35) TABLE-US-00006 Examples Example 39 Example 40 Example 41 Example 42 Example 43 Example 44 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 H.sub.2SO.sub.4/H.sub.2O weight % 70 70 60 70 80 70 L/h 0.55 2.57 1.49 3.06 1.45 0.55 Feed rate 2 Property NSC904 NSC904 NSC904 NSC904 NSC904 NSC904 weight % 95 95 95 95 95 95 L/h 3.87 11.34 4.5 8.9 4.5 3.87 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 H.sub.2O.sub.2/H.sub.2O weight % 50 50 50 50 50 50 L/h 1.32 3.88 1.54 4.12 2.22 1.32 Feed rate 4 Property KOH/H.sub.2O KOH/H.sub.2O KOH/H.sub.2O KOH/H.sub.2O KOH/H.sub.2O KOH/H.sub.2O weight % 20 20 5 45 30 20 L/h 3.44 10.08 20 4.52 4.5 3.44 Feed rate 5 Property NDCl NDCl NDCl NDCl NDCl NDCl weight % 98 98 98 98 98 98 L/h 2.26 6.63 2.63 5.23 2.63 2.26 Total feed L/h 11.45 34.5 29.02 25.89 15.41 11.45 Temperature C. 70 60 40 30 20 5 zone 1 Temperature C. 160 130 120 110 100 90 zone 2 Temperature C. 40 30 20 5 0 5 zone 3 Temperature C. 90 80 70 60 50 40 zone 4 Temperature C. 50 40 30 20 5 0 zone 5 Temperature C. 50 40 30 20 5 0 zone 6 NSC904:H.sub.2SO.sub.4:H.sub.2O.sub.2:KOH:NDCL 1:0.3:1:1.2:0.9 1:0.8:1.1:1.2:0.7 1:1:1:1.2:1 1:1.2:1.4:1.2:0.9 1:1.3:1.5:1.6:0.9 1:0.5:1.04:1.2:0.9 mole ratio Production time min 9.0 3.0 3.6 4.0 6.67 9.0 Total yield % 67.3 66.5 65.7 66.8 65.5 67.3 Content % 88.9 90.4 80.1 90.8 81.3 88.9 Examples Example 45 Example 46 Example 47 Example 48 Example 49 Example 50 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 H.sub.2SO.sub.4/H.sub.2O weight % 70 50 70 90 70 70 L/h 1.28 2.04 1.28 1 1.28 38.4 Feed rate 2 Property NSC904 NSC904 NSC904 NSC904 NSC904 NSC904 weight % 95 95 95 95 95 95 L/h 4.5 7.07 4.5 4.5 4.5 135 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 H.sub.2O.sub.2/H.sub.2O weight % 50 50 30 50 50 50 L/h 1.18 2.09 2.46 1.78 1.93 57.9 Feed rate 4 Property KOH/H.sub.2O KOH/H.sub.2O KOH/H.sub.2O KOH/H.sub.2O KOH/H.sub.2O KOH/H.sub.2O weight % 15 20 20 20 20 20 L/h 3 5.23 4 4.33 4.67 140.1 Feed rate 5 Property NDCl NDCl NDCl NDCl NDCl NDCl weight % 98 98 98 98 98 98 L/h 3.08 3.52 2.63 2.8 2.1 63 Total feed L/h 13.04 20.7 14.89 14.41 14.48 434.4 Temperature C. 5 5 5 5 5 5 zone 1 Temperature C. 80 70 60 50 40 40 zone 2 Temperature C. 5 5 5 5 5 5 zone 3 Temperature C. 30 20 20 60 50 50 zone 4 Temperature C. 5 5 5 5 5 5 zone 5 Temperature C. 5 5 5 5 5 5 zone 6 NSC904:H.sub.2SO.sub.4:H.sub.2O.sub.2:KOH:NDCL 1:1:0.8:0.9:1.1 1:1:0.9:1:0.8 1:1:1:1.2:0.9 1:1:1.2:1.3:1 1:1:1.3:1.4:0.7 1:1:1.3:1.4:0.7 mole ratio Production time min 7.94 5.0 7.15 7.18 7.0 7.0 Total yield % 70.3 65.8 65.2 66.2 68.5 68.5 Content % 85.6 87.5 81.4 86.4 81.8 81.8
Example 51-62 are the Preparation of Tert-Butyl Peroxyisopropylcarbonate
(36) The operation methods of embodiments 1 to 12 are adopted.
(37) TABLE-US-00007 Examples Example 51 Example 52 Example 53 Example 54 Example 55 Example 56 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 H.sub.2SO.sub.4/H.sub.2O weight % 70 70 60 70 70 60 L/h 3.66 1.5 1.49 2.1 1.28 1.49 Feed rate 2 Property TBA/H.sub.2O 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 94.3 L/h 5.2 1.72 2.6 2.0 2.6 2.6 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 H.sub.2O.sub.2/H.sub.2O weight % 30 50 50 50 50 50 L/h 4.12 0.91 1.54 1.18 2 1.54 Feed rate 4 Property KOH/H.sub.2O KOH/H.sub.2O KOH/H.sub.2O KOH/H.sub.2O KOH/H.sub.2O KOH/H.sub.2O weight % 20 20 5 45 30 20 L/h 8 2.84 23.46 3.33 3.4 4.6 Feed rate 5 Property IPCF IPCF IPCF IPCF IPCF IPCF weight % 98 98 98 98 98 98 L/h 2.85 0.94 1.42 1.16 1.43 1.43 Total feed L/h 23.83 7.91 30.51 9.77 10.71 11.66 Temperature C. 70 60 40 30 20 5 zone 1 Temperature C. 160 130 120 110 100 90 zone 2 Temperature C. 40 30 20 5 0 5 zone 3 Temperature C. 90 80 70 60 50 40 zone 4 Temperature C. 50 40 30 20 5 0 zone 5 Temperature C. 50 40 30 20 5 0 zone 6 TBA:H.sub.2SO.sub.4:H.sub.2O.sub.2:KOH:IPCF 1:0.8:0.8:1.2:0.7 1:1:0.9:1.3:0.7 1:0.5:1:1.4:0.7 1:1.2:1:0.9:0.9 1:0.5:1.3:1.2:0.7 1:0.5:1:1.6:0.7 mole ratio Production time min 3.2 9.0 3.0 8.0 7.0 6.5 Total yield % 81.37 72.5 71.88 71.38 71.1 71.88 Content % 96.2 97.0 97.1 96.9 95.6 97.1 Examples Example 57 Example 58 Example 59 Example 60 Example 61 Example 62 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 H.sub.2SO.sub.4/H.sub.2O weight % 70 50 70 90 80 80 L/h 1.28 2.24 1.28 2.1 1.12 33.6 Feed rate 2 Property TBA/H.sub.2O 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 94.3 L/h 2.6 2.0 2.6 4.2 2.6 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 H.sub.2O.sub.2/H.sub.2O weight % 50 50 50 30 30 30 L/h 2.16 1.77 1.67 2.48 1.54 46.2 Feed rate 4 Property KOH/H.sub.2O KOH/H.sub.2O KOH/H.sub.2O KOH/H.sub.2O KOH/H.sub.2O KOH/H.sub.2O weight % 15 20 20 30 20 20 L/h 6.8 3.08 6.8 6.47 4.0 120 Feed rate 5 Property IPCF IPCF IPCF IPCF IPCF IPCF weight % 98 98 98 98 98 98 L/h 1.43 1.55 1.49 1.94 1.86 55.8 Total feed L/h 14.27 10.64 13.84 17.19 11.12 333.6 Temperature C. 5 5 5 5 5 5 zone 1 Temperature C. 80 70 60 50 40 40 zone 2 Temperature C. 5 5 5 5 5 5 zone 3 Temperature C. 30 20 20 60 50 50 zone 4 Temperature C. 5 5 5 5 5 5 zone 5 Temperature C. 5 5 5 5 5 5 zone 6 TBA:H.sub.2SO.sub.4:H.sub.2O.sub.2:KOH:IPCF 1:0.3:1.4:1.2:0.7 1:1.3:1.5:1.2:1.1 1:0.5:1.05:1.6:0.9 1:0.6:1:1.2:0.5 1:0.5:1:1.2:0.9 1:0.5:1:1.2:0.9 mole ratio Production time min 5.0 7.37 6.0 4.0 6.12 6.12 Total yield % 80.5 71.5 81.8 80.3 70.5 71.1 Content % 97.0 97.6 96.9 98.0 98.1 97.9
Example 63-74 are the Preparation of Tert-Amyl Peroxide 2-Ethylhexyl Carbonate
(38) The operation methods of embodiments 1 to 12 are adopted.
(39) TABLE-US-00008 Examples Example 63 Example 64 Example 65 Example 66 Example 67 Example 68 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 H.sub.2SO.sub.4/H.sub.2O weight % 70 70 60 70 70 60 L/h 3.66 1.5 1.49 2.1 1.28 1.49 Feed rate 2 Property TAA TAA TAA TAA TAA TAA weight % 98 98 98 98 98 98 L/h 5.7 1.89 2.86 2.2 2.86 2.86 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 H.sub.2O.sub.2/H.sub.2O weight % 30 50 50 50 50 50 L/h 4.12 0.91 1.54 1.18 2 1.54 Feed rate 4 Property KOH/H.sub.2O KOH/H.sub.2O KOH/H.sub.2O KOH/H.sub.2O KOH/H.sub.2O KOH/H.sub.2O weight % 20 20 5 45 30 20 L/h 8 2.84 23.46 3.33 3.4 4.6 Feed rate 5 Property 2-EHCF 2-EHCF 2-EHCF 2-EHCF 2-EHCF 2-EHCF weight % 98 98 98 98 98 98 L/h 5.3 1.75 2.65 2.16 2.65 2.65 Total feed L/h 26.78 8.89 32 10.97 12.19 13.14 Temperature C. 70 60 40 30 20 5 zone 1 Temperature C. 160 130 120 110 100 90 zone 2 Temperature C. 40 30 20 5 0 5 zone 3 Temperature C. 90 80 70 60 50 40 zone 4 Temperature C. 50 40 30 20 5 0 zone 5 Temperature C. 50 40 30 20 5 0 zone 6 TAA:H.sub.2SO.sub.4:H.sub.2O.sub.2:KOH:2-EHCF 1:0.8:0.8:1.2:0.7 1:1:0.9:1.3:0.7 1:0.5:1:1.4:0.7 1:1.2:1:0.9:0.9 1:0.5:1.3:1.2:0.7 1:0.5:1:1.6:0.7 mole ratio Production time min 3.2 9.0 3.0 8.0 7.0 6.5 Total yield % 81.3 72.5 71.8 71.3 71.6 71.88 Content % 95.8 96.7 97.3 97.9 95.6 97.3 Examples Example 69 Example 70 Example 71 Example 72 Example 73 Example 74 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 H.sub.2SO.sub.4/H.sub.2O weight % 70 50 70 90 80 80 L/h 1.28 2.24 1.28 2.1 1.12 33.6 Feed rate 2 Property TAA TAA TAA TAA TAA TAA weight % 98 98 98 98 98 98 L/h 2.86 2.2 2.86 4.62 2.86 85.8 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 H.sub.2O.sub.2/H.sub.2O weight % 50 50 50 30 30 30 L/h 2.16 1.77 1.67 2.48 1.54 46.2 Feed rate 4 Property KOH/H.sub.2O KOH/H.sub.2O KOH/H.sub.2O KOH/H.sub.2O KOH/H.sub.2O KOH/H.sub.2O weight % 15 20 20 30 20 20 L/h 6.8 3.08 6.8 6.47 4.0 120 Feed rate 5 Property 2-EHCF 2-EHCF 2-EHCF 2-EHCF 2-EHCF 2-EHCF weight % 98 98 98 98 98 98 L/h 2.65 2.88 2.78 3.6 3.46 103.8 Total feed L/h 15.75 12.17 15.39 18.85 12.98 389.4 Temperature C. 5 5 5 5 5 5 zone 1 Temperature C. 80 70 60 50 40 40 zone 2 Temperature C. 5 5 5 5 5 5 zone 3 Temperature C. 30 20 20 60 50 50 zone 4 Temperature C. 5 5 5 5 5 5 zone 5 Temperature C. 5 5 5 5 5 5 zone 6 TAA:H.sub.2SO.sub.4:H.sub.2O.sub.2:KOH::2-EHCF 1:0.3:1.4:1.2:0.7 1:1.3:1.5:1.2:1.1 1:0.5:1.05:1.6:0.9 1:0.6:1:1.2:0.5 1:0.5:1:1.2:0.9 1:0.5:1:1.2:0.9 mole ratio Production time min 5.0 7.37 6.0 4.0 6.12 6.12 Total yield % 81.5 71.5 81.8 80.38 70.8 71.0 Content % 96.0 96.7 96.0 96.0 96.1 97.0
Examples 75-77 are the Preparation of Cumene Peroxide with Tert-Butyl
(40) The operation method of embodiments 29-38 is adopted.
(41) TABLE-US-00009 Examples Example 75 Example 76 Example 77 Feed rate 1 Property Na.sub.2CO.sub.3/H.sub.2O Na.sub.2CO.sub.3/H.sub.2O Na.sub.2CO.sub.3/H.sub.2O weight % 10 10 10 L/h 0.6 0.6 18 Feed rate 2 Property Cumene Cumene Cumene weight % 100 100 100 L/h 1.56 1.56 46.8 Feed rate 3 Property O.sub.2 O.sub.2 O.sub.2 weight % 100 100 100 L/h 0.5 0.5 15 Feed rate 4 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 weight % 70 70 70 L/h 2 2 60 Feed rate 5 Property TBA TBA TBA weight % 94.3 94.3 94.3 L/h 2.16 2.16 64.8 Total feed L/h 8.14 8.14 8.14 Temperature C. 40 30 30 zone 1 Temperature C. 200 80 80 zone 2 Temperature C. 20 20 20 zone 3 Temperature C. 70 80 80 zone 4 Temperature C. 30 30 30 zone 5 Temperature C. 30 30 30 zone 6 TBA:H.sub.2SO.sub.4:H.sub.2O.sub.2: 1::0.6::1::0.5:1 1::0.6::1::0.5:1 1::0.6::1::0.5:1 H.sub.2SO.sub.4:TBA mole ratio Production Min 8.33 8.33 8.33 time Total yield % 79.76 81.7 81.0 Content % 78.4 78.4 78.1
Examples 78-92
(42) The corresponding organic peroxides of specific examples are as follows: examples 84 and 85 adopt the operation methods of examples 27-28, examples 78-83 and 86-92 adopt the operation methods of examples 1-12.
(43) TABLE-US-00010 Examples 78 79 80 81 Product tert-butyl tert-butyl tert-butyl tert-butyl name peroxybenzoate peroxyvalerate peroxide 2- peroxyisobutyrate ethylhexanoate Examples 82 83 84 85 Product tert-butyl tert-butyl 3,5,5- 1,1-di(tert-butyl 2,2-di(tert-butyl name peroxyneoheptanate trimethylhexanoate peroxide)-3,3,5- peroxide) butane peroxide trimethylcyclohexane Examples 86 87 88 89 Product tert-butyl tert-amyl tert-amyl tert-amyl-2- name peroxyacetate peroxyvalerate peroxyacetate ethylhexanoate peroxide Examples 90 91 92 Product 1,1,3,3- 2-ethylhexanoate- 2-ethylhexanoate- name tetramethyl butyl 1,1,3,3- 1,1,3,3- peroxide tetramethylbutyl tetramethylbutyl peroxide peroxide Examples Example 78 Example 79 Example 80 Example 81 Example 82 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 80 70 50 L/h 1.28 1.28 1.12 1.28 1.78 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 2.6 2.6 2.6 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 30 50 50 L/h 1.54 1.54 2.54 1.54 1.54 Feed rate 4 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 KOH/H.sub.2O weight % 20 20 15 20 20 L/h 4.2 4.6 2.4 4.0 4.0 Feed rate 5 Property CBO PVCL 2-EHC IBCL U535 weight % 98 98 98 98 98 L/h 1.51 1.6 2.15 1.36 1.98 Total feed L/h 11.13 11.62 11.07 10.78 11.9 Temperature C. 5 20 30 5 5 zone 1 Temperature C. 70 80 90 80 80 zone 2 Temperature C. 20 5 20 20 20 zone 3 Temperature C. 80 60 50 60 20 zone 4 Temperature C. 30 30 30 30 5 zone 5 Temperature C. 30 5 5 5 5 zone 6 TBA:H.sub.2SO.sub.4:H.sub.2O.sub.2:KOH:(CBO/ 1:0.6:1.:1.2:0.9 1:0.6:1:1.2:0.9 1:0.6:1:1.2:0.9 1:0.6:1:1.2:0.9 1:0.6:1:1.2:0.9 PVCL/2-EHC/IBCL/U535) mole ratio Production time min 6.63 6.44 7.16 6.37 6.61 Total yield % 69.3 70.5 73.2 67.8 71.5 Content % 87.5 85.1 83.1 80.5 81.0 Examples Example 83 Example 84 Example 85 Example 86 Example 87 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 50 70 80 70 L/h 1.28 1.78 1.28 1.12 0.92 Feed rate 2 Property TBA/H.sub.2O TBA/H.sub.2O TBA/H.sub.2O TBA/H.sub.2O TAA/H.sub.2O weight % 94.3 94.3 94.3 94.3 98 L/h 2.6 2.6 2.6 2.6 1.16 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 1.54 1.54 2.54 0.67 Feed rate 4 Property KOH/H.sub.2O H.sub.2SO.sub.4/H.sub.2O H.sub.2SO.sub.4/H.sub.2O KOH/H.sub.2O KOH/H.sub.2O weight % 20 70 70 20 5 L/h 4.0 0.57 0.57 4.0 8.13 Feed rate 5 Property INCL 335TCYC MEK ACL PVCL weight % 98 98 98 98 98 L/h 1.9 1.03 0.58 0.92 0.97 Total feed L/h 11.32 7.52 6.57 11.24 11.85 Temperature C. 5 5 5 5 5 zone 1 Temperature C. 85 85 75 85 85 zone 2 Temperature C. 20 30 20 0 30 zone 3 Temperature C. 80 90 80 80 50 zone 4 Temperature C. 20 20 5 5 20 zone 5 Temperature C. 5 5 5 5 5 zone 6 TBA:H.sub.2SO.sub.4:H.sub.2O.sub.2:KOH/H.sub.2SO:(INCL/ 1:0.6:1:1.2::0.9 1:0.6:1:0.5::0.5 1:0.6:1:0.5::0.5 1:0.6:1:1.2::0.9 1:1:1.1:1.2::0.9 335TCYC/MEK/ACL) mole ratio Production time min 6.83 7.42 7.64 6.13 6.14 Total yield % 65.3 64.5 67.5 70.4 72.5 Content % 79.5 80.1 80.3 79.0 79.5 Examples Example 88 Example 89 Example 90 Example 91 Example 92 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 70 70 L/h 1.76 2.05 1.28 1.28 38.4 Feed rate 2 Property TAA/H.sub.2O TAA/H.sub.2O NSC904 NSC904 NSC904 weight % 98 98 95 95 95 L/h 2.22 2.22 4.5 4.5 135 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 30 50 50 L/h 1.28 1.28 2.54 1.54 46.2 Feed rate 4 Property KOH/H.sub.2O KOH/H.sub.2O KOH/H.sub.2O KOH/H.sub.2O KOH/H.sub.2O weight % 35 20 20 20 20 L/h 2.22 3.05 4 4 120 Feed rate 5 Property ACL 2-EHC PVCl 2-EHC 2-EHC weight % 98 98 98 98 98 L/h 1.07 2.6 1.6 2.25 67.5 Total feed L/h 9.38 11.2 13.92 13.57 412.5 Temperature C. 5 5 5 5 5 zone 1 Temperature C. 85 85 80 80 80 zone 2 Temperature C. 20 20 5 20 20 zone 3 Temperature C. 80 70 40 50 50 zone 4 Temperature C. 20 20 5 30 30 zone 5 Temperature C. 5 5 5 5 5 zone 6 TAA/NSC904:H.sub.2SO.sub.4:H.sub.2O.sub.2:KOH:(PVCL/ 1:1:1.1:1.2:0.9 1:1:1.1:1.2:0.9 1:1:1.1:1.2:0.9 1:1:1.1:1.2:0.9 1:1:1.1:1.2:0.9 ACL/2-EHC/PVCL) mole ratio Production time min 6.71 6.23 6.05 6.67 6.7 Total yield % 74.5 73.3 67.3 67.6 67.4 Content % 80.1 78.5 80.3 79.4 77.9
(44) It can be seen from the above examples that the continuous production of organic peroxides of the disclosure has a huge advantage in reaction time, which is shortened from several hours or even 10 hours of the existing process to less than 10 minutes, and the overall yield and content are improved to a certain extent compared with the prior art. At the same time, it can be seen from embodiments 11 and 12, 25 and 26, 37 and 38, 49 and 50, 61 and 62, 73 and 74, 76 and 77, 91 and 92 that the yield is not changed and the production time is not increased after the scale-up, indicating that there is no amplification effect in the disclosure.