CN102336695A - Production method of di(tert-butylperoxy)ketal - Google Patents
Production method of di(tert-butylperoxy)ketal Download PDFInfo
- Publication number
- CN102336695A CN102336695A CN2010102381809A CN201010238180A CN102336695A CN 102336695 A CN102336695 A CN 102336695A CN 2010102381809 A CN2010102381809 A CN 2010102381809A CN 201010238180 A CN201010238180 A CN 201010238180A CN 102336695 A CN102336695 A CN 102336695A
- Authority
- CN
- China
- Prior art keywords
- butylperoxy
- acid
- bis
- ketal
- solvent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention relates to a production method of di(tert-butylperoxy)ketal, and mainly solves the problems of low product content, low yield, deep color and low production safety caused by violent side reaction in the previous technique. In the invention, R1 selected from cyclohexanone, 3,3,5-trimethylcyclohexanone or butyl levulinate and R2 tert-butyl hydroperoxide, which are used as raw materials, react in the presence of solvent at -20-40 DEG C under normal pressure for 0.5-10 hours to obtain the corresponding product 1,1-di(tert-butylperoxy)cyclohexane, 1,1-di(tert-butylperoxy)-3,3,5-trimethylcyclohexanone or 4,4,-di(tert-butylperoxy)-n-butyl valerate, wherein the mol ratio of R2 to R1 is (2-10):1, the weight ratio of solvent to R1 is (0.01-0.50):1, and the amount of the solvent accounts for 20-80% of the total weight of the reactants R1 and R2; and the catalyst is selected from at least one of sulfuric acid, phosphoric acid, hydrochloric acid, perchloric acid, p-methylbenzenesulfonic acid, nitric acid or acetic acid. The technical scheme provided by the invention solves the problems in the previous technique, and can be used for industrial production of di(tert-butylperoxy)ketal.
Description
Technical field
The present invention relates to a kind of working method of bis(t-butylperoxy) ketal.
Background technology
The organo-peroxide linking agent is a kind of important auxiliary agent of organic high molecular polymer; It can be converted into the organic polymer chain of branched chain type line style or slight tridimensional network with between the restriction macromolecular chain and the relative movement between the macromolecular chain interior chain, thereby improves some performance of organic high molecular polymer.Some organic high molecular polymer can significantly improve performances such as thermotolerance, oil-proofness, wear resistance, mechanical strength through after crosslinked; Also some organic high molecular polymer like rubber, must pass through the crosslinked actual use value that just has.
Normally used organo-peroxide linking agent is Di Cumyl Peroxide 99 (being called for short DCP); But be to use this superoxide as linking agent; Generation has the methyl phenyl ketone of bad smell when crosslinked, and stays in the finished product, and therefore this peroxide cross-linking agent can not be used in many cases.The substitute of using at present is two-t-butylperoxy ketal compounds, as 1, and 1-bis(t-butylperoxy) cyclohexane, 1,1-bis(t-butylperoxy)-3,3,5-trimethyl-cyclohexane and 4,4-bis(t-butylperoxy) n-butyl pentanoate.This type linking agent half life of decomposition temperature is all low than DCP, so crosslinking temperature is lower, and the product stink is little, but has the effectiveness identical with DCP in other properties.
1,1-bis(t-butylperoxy) cyclohexane (being called for short BPC), molecular formula C
14H
28O
4, molecular weight 260.BPC is colourless to weak yellow liquid, 55 ℃/0.1mmHg of boiling point, theoretical active oxygen amount 12.3%, activation energy 147.9kJ/mol, decomposition temperature 153 ℃ of (1 minute transformation period), 95 ℃ (10 hours transformation period).BPC is water insoluble, dissolves in common organic solvents such as ether, sherwood oil, benzene, hexane, chloroform, ethanol.
1,1-bis(t-butylperoxy)-3,3,5-trimethyl-cyclohexane (being called for short BPMC), molecular formula C
17H
34O
4, molecular weight 302.BPMC is colourless to weak yellow liquid, specific density 0.9039,70 ℃ of critical temperatures; 57 ℃ of flash-points, 154 ℃ of burning-points, 86 ℃/1mmHg of boiling point; Theoretical active oxygen amount 10.6%, activation energy 148.68kJ/mol, decomposition temperature 153 ℃ of (1 minute transformation period), 96 ℃ (10 hours transformation period).BPMC is water insoluble, dissolves in most of organic solvents such as ether, sherwood oil, benzene, hexane, chloroform, ethanol.
4,4-bis(t-butylperoxy) n-butyl pentanoate (being called for short BBPV), molecular formula C
17H
34O
6, molecular weight 334.BBPV is colourless to weak yellow liquid, 71 ℃ of flash-points, 163 ℃ of burning-points, theoretical active oxygen amount 9.58%, activation energy 155.4kJ/mol, decomposition temperature 165 ℃ of (1 minute transformation period), 108 ℃ (10 hours transformation period).BBPV is water insoluble, dissolves in most of organic solvent.
The working method of bis(t-butylperoxy) ketal mainly is the acid catalysis synthesis method under the situation of not using solvent at present.Document US 4365086, GB1047830 and US4328360 disclose 4; The compound method of 4-bis(t-butylperoxy) n-butyl pentanoate (being called for short BBPV); Under 23～32 ° of F (5～0 ℃) condition; Sulfuric acid with 378 grams 77% is catalyzer, and 3.5 moles of levulinic acid butyl esters and 7.7 moles of tertbutyl peroxide reactions generate BBPV.Document " 1, the trial-production of 1-cyclohexane di-tert-butyl peroxide, Zhanjiang Normal University's journal (natural science edition), 1996, Vol.17, No.2,97～100 " discloses synthetic BPC under the acid catalyst effect.But because this acid catalyzed process do not use solvent, high-load peroxy ketal product is prone to the violent acid of generation with a large amount of acid catalysts and reduces side reaction, and causes that product yield is low, color is dark; Even, produce dangerous because of a large amount of heat releases cause an explosion accident.Document US 4052464 discloses 1,1-bis(t-butylperoxy)-3,3, and the compound method of 5-trimethyl-cyclohexane (being called for short BPMC), under an acidic catalyst effect, 30～80 ℃, it is under reduced pressure synthetic with the method for azeotropic band water to make solvent with ethylbenzene.This method complex operation needs decompression operation, and solvent loss is big, and the content of superoxide and yield are not high yet.
Summary of the invention
Technical problem to be solved by this invention is to exist side reaction violent in the technology in the past, causes that product content is low, yield is low, color and luster is dark, produces unsafe problem, and a kind of working method of new bis(t-butylperoxy) ketal is provided.This method has that reaction temperature is high with, product content, high, the coloury characteristics of yield.
For solving the problems of the technologies described above, the technical scheme that the present invention adopts is following: a kind of working method of bis(t-butylperoxy) ketal, to be selected from pimelinketone, 3; 3, a kind of R1 and tertbutyl peroxide R2 in 5-trimethylcyclohexanone or the levulinic acid butyl ester are raw material, in the presence of solvent; At normal pressure, temperature of reaction is-20～40 ℃, and the mol ratio of R2 and R1 is 2～10: 1; The weight ratio of catalyzer and R1 is 0.01～0.50: 1, the consumption of solvent be reacted under 20～80% conditions of reactant R1 and R2 gross weight 0.5～10 hour corresponding product 1,1-bis(t-butylperoxy) cyclohexane, 1; 1-bis(t-butylperoxy)-3; 3,5-trimethyl-cyclohexane or 4,4-bis(t-butylperoxy) n-butyl pentanoate; Wherein said catalyzer is selected from least a in sulfuric acid, phosphoric acid, hydrochloric acid, perchloric acid, p-methyl benzenesulfonic acid, nitric acid or the acetic acid.
In the technique scheme, said solvent preferred version is for being selected from C
4～C
19Straight-chain paraffin, C
4～C
10Naphthenic hydrocarbon, C
6～C
10Aromatic hydrocarbon, C
2～C
6Ether or ETHYLE ACETATE at least a, more preferably scheme is to be selected from least a in normal butane, Skellysolve A, normal hexane, octane-iso, n-dodecane, NSC 77136, tetramethylene, pentamethylene, hexanaphthene, YLENE, toluene, ether or the ETHYLE ACETATE.The temperature of reaction preferable range is-15～35 ℃; The reaction times preferable range is 1.5～6 hours; The mol ratio preferable range of R2 and R1 is 2～5: 1, and the weight ratio preferable range of catalyzer and R1 is 0.05～0.40: 1, and the consumption preferable range of solvent is 40～60% of R1 and a R2 gross weight.Said catalyzer preferred version is for being selected from sulfuric acid, and more preferably scheme is H
2SO
4With remove H
2SO
4Outside the mixture of sour M, wherein sour M is selected from least a in phosphoric acid, hydrochloric acid, perchloric acid, p-methyl benzenesulfonic acid, nitric acid or the acetic acid.H
2SO
4With the weight ratio preferable range of sour M be H
28O
4: M=0.5～15: 1, more preferably scope is H
2SO
4: M=1～12: 1.The adding method preferred version of said catalyzer adds in reactant for being divided into twice at least, and more preferably scheme adds in reactant for being equally divided into twice at least.
The inventor is surprised to find, and carries out reacting balance because the inventive method adopts to be reflected in the solvent; The acid that has reduced peroxide product and an acidic catalyst reduces side reaction; Make that product content is high, yield is high, color and luster good, exothermic heat of reaction is little simultaneously, and production security is high.The inventive method is preferably used mixed-acid catalyst, has significantly reduced sour consumption, has reduced corrosion on Equipment.The mode that the adding mode of catalyzer preferably takes gradation to add is emitted the reaction heat gradation, makes reaction carry out to such an extent that steadily relax, and has guaranteed the security of producing; Reduced the severe of peroxide reactions simultaneously, further guaranteed product color, peroxide level is brought up to more than 90% by 60～70%.Adopt the inventive method synthetic bis(t-butylperoxy) ketal content high in addition, Heat stability is good, after 6 hours, content still can reach more than 90%, has obtained better technical effect 80 ℃ of insulations.
Through embodiment the present invention is done further elaboration below.
Embodiment
[embodiment 1～17]
1, the preparation of 1-bis(t-butylperoxy) cyclohexane (BPC)
Under normal pressure, solvent, pimelinketone R1 and tertbutyl peroxide R2 adding are furnished with in the reaction kettle of electric mixer, TM, reflux exchanger.Open and stir, add catalyzer, reacted 4 hours, obtain the BPC reaction solution.Through alkali cleaning, washing, obtain neutral reaction liquid, obtain colourless liquid through underpressure distillation and be the BPC product.Each proportion of raw materials, the composition of catalyzer, content, adding mode, solvent types, consumption, temperature of reaction, the content of reaction times and product, yield are specifically seen table 1.
[comparative example 1]
Under normal pressure, pimelinketone R1 and tertbutyl peroxide R2 adding are furnished with in the reaction kettle of electric mixer, TM, reflux exchanger.Open and stir, add 77 weight % sulfuric acid, reacted 4 hours, obtain the BPC reaction solution.Through alkali cleaning, washing, obtain neutral reaction liquid, obtain yellow liquid through underpressure distillation and be the BPC product.Each proportion of raw materials, catalyst consumption, temperature of reaction, the content of reaction times and product, yield are specifically seen table 1.
[embodiment 18～34]
1,1-bis(t-butylperoxy)-3,3, the preparation of 5-trimethyl-cyclohexane (BPMC)
Under normal pressure, with solvent, 3,3,5-trimethylcyclohexanone R1 and tertbutyl peroxide R2 adding are furnished with in the reaction kettle of electric mixer, TM, reflux exchanger.Open and stir, add catalyzer, reacted 4 hours, obtain the BPMC reaction solution.Through alkali cleaning, washing, obtain neutral reaction liquid, obtain colourless liquid through underpressure distillation and be the BPMC product.Each proportion of raw materials, the composition of catalyzer, content, adding mode, solvent types, consumption and temperature of reaction, reaction times are specifically seen table 2.
[comparative example 2]
Under normal pressure, with 3,3,5-trimethylcyclohexanone R1 and tertbutyl peroxide R2 adding are furnished with in the reaction kettle of electric mixer, TM, reflux exchanger.Open and stir, add 77 weight % sulfuric acid, reacted 4 hours, obtain the BPMC reaction solution.Through alkali cleaning, washing, obtain neutral reaction liquid, obtain yellow liquid through underpressure distillation and be the BPMC product.Each proportion of raw materials, catalyst consumption, temperature of reaction, the content of reaction times and product, yield are specifically seen table 2.
[embodiment 35～51]
4, the preparation of 4-bis(t-butylperoxy) n-butyl pentanoate (BBPV)
Under normal pressure, solvent, levulinic acid butyl ester R1 and tertbutyl peroxide R2 adding are furnished with in the reaction kettle of electric mixer, TM, reflux exchanger.Open and stir, add catalyzer, reacted 4 hours, obtain the BBPV reaction solution.Through alkali cleaning, washing, obtain neutral reaction liquid, obtain colourless liquid through underpressure distillation and be the BBPV product.Each proportion of raw materials, the composition of catalyzer, content, adding mode, solvent types, consumption and temperature of reaction, reaction times are specifically seen table 3.
[comparative example 3]
Under normal pressure, with solvent, 3,3,5-trimethylcyclohexanone R1 and tertbutyl peroxide R2 adding are furnished with in the reaction kettle of electric mixer, TM, reflux exchanger.Open and stir, add 77 weight % sulfuric acid, reacted 4 hours, obtain the BPMC reaction solution.Through alkali cleaning, washing, obtain neutral reaction liquid, obtain yellow liquid through underpressure distillation and be the BBPV product.Each proportion of raw materials, catalyst consumption, temperature of reaction, the content of reaction times and product, yield are specifically seen table 3.
[embodiment 52]
With [embodiment 1] synthetic BPC, [embodiment 18] synthetic BPMC, [embodiment 35] synthetic BBPV carries out application test, result such as table 4 to crosslinked chlorinatedpolyethylene (CPE).
[comparative example 4]
With Di Cumyl Peroxide 99 (DCP), BPC and Di Cumyl Peroxide 99 (DCP) are mixed with BBPV or BPMC, and (CPE) carries out application test, result such as table 4 to crosslinked chlorinatedpolyethylene.
Table 4
See from above data contrast:
1, BPC, BPMC, BBPV vulcanize CPE, its physical and mechanical properties and the no significant difference of DCP sulfuration.
2, do not have DCP with the cross-linked rubber of BBPV, BPMC, BPC and vulcanize special stink.
3, BPC, BPMC, BBPV influence close with DCP to the mooney viscosity
of sizing material.
4, see from the sulfurizing point data: the half life temperature of BBPV is lower 8～9 ℃ than DCP, and the half life temperature of BPMC is lower 14～16 ℃ than DCP, and the half life temperature of BPC is lower 18 ℃ than DCP.
5, see from coke burning performance: BBPV is almost identical with DCP, and BPC and BPMC are also only fast 35% than DCP, so as long as extrusion temperature is controlled at below 90 ℃, the coke burning performance of safe enough is arranged all with BBPV and BPMC peroxide vuleanization CPE.
6, if BBPV or BPMC and DCP are mixed, from still being all to be feasible on the process safety economically, another advantage of mixing is that the stink of DCP is reduced greatly.
[embodiment 53]
With [embodiment 1] synthetic BPC, [embodiment 18] synthetic BPMC, [embodiment 35] synthetic BBPV carry out the thermostability experiment.
In 250 milliliters of round-bottomed flasks, take by weighing superoxide BPC, BPMC or BBPV 150 grams, and the lid bottle stopper; Be heated to 60,70,80 ℃ in the constant temperature oil bath; And be incubated 6 hours at each temperature, observe the superoxide color and luster and change, and carry out chemical iodometric titrationiodimetry titration analysis in sampling at each temperature.The result sees table 5～table 7 respectively.
Table 5BPC thermostability experimental result
Table 6BPMC thermostability experimental result
Table 7BBPV thermostability experimental result
Claims (9)
1. the working method of a bis(t-butylperoxy) ketal is to be selected from pimelinketone, 3,3; A kind of R1 and tertbutyl peroxide R2 in 5-trimethylcyclohexanone or the levulinic acid butyl ester are raw material, in the presence of solvent, at normal pressure; Temperature of reaction is-20～40 ℃, and the mol ratio of R2 and R1 is 2～10: 1, and the weight ratio of catalyzer and R1 is 0.01～0.50: 1; The consumption of solvent be reacted under 20～80% conditions of reactant R1 and R2 gross weight 0.5～10 hour corresponding product 1,1-bis(t-butylperoxy) cyclohexane, 1,1-bis(t-butylperoxy)-3; 3,5-trimethyl-cyclohexane or 4,4-bis(t-butylperoxy) n-butyl pentanoate; Wherein said catalyzer is selected from least a in sulfuric acid, phosphoric acid, hydrochloric acid, perchloric acid, p-methyl benzenesulfonic acid, nitric acid or the acetic acid.
2. according to the working method of said pair-t-butylperoxy ketal of claim 1, it is characterized in that said solvent is selected from C
4～C
19Straight-chain paraffin, C
4～C
10Naphthenic hydrocarbon, C
6～C
10Aromatic hydrocarbon, C
2～C
6Ether or ETHYLE ACETATE at least a.
3. according to the working method of the said bis(t-butylperoxy) ketal of claim 2, it is characterized in that said solvent is selected from least a in normal butane, Skellysolve A, normal hexane, octane-iso, n-dodecane, NSC 77136, tetramethylene, pentamethylene, hexanaphthene, YLENE, toluene, ether or the ETHYLE ACETATE.
4. according to the working method of the said bis(t-butylperoxy) ketal of claim 1; It is characterized in that temperature of reaction is-15～35 ℃; Reaction times is 1.5～6 hours; The mol ratio of R2 and R1 is 2～5: 1, and the weight ratio of catalyzer and R1 is 0.05～0.40: 1, and the consumption of solvent is 40～60% of R1 and a R2 gross weight.
5. according to the working method of the said bis(t-butylperoxy) ketal of claim 1, it is characterized in that said catalyzer is selected from sulfuric acid.
6. according to the working method of the said bis(t-butylperoxy) ketal of claim 1, it is characterized in that said catalyzer is H
2SO
4With remove H
2SO
4Outside the mixture of sour M, its weight ratio is H
2SO
4: M=0.5～15: 1; Wherein sour M is selected from least a in phosphoric acid, hydrochloric acid, perchloric acid, p-methyl benzenesulfonic acid, nitric acid or the acetic acid.
7. according to the working method of the said bis(t-butylperoxy) ketal of claim 6, it is characterized in that H
28O
4With the weight ratio of sour M be H
28O
4: M=1～12: 1.
8. according to the working method of the said bis(t-butylperoxy) ketal of claim 1, it is characterized in that said catalyzer is divided at least twice and adds in the reactant.
9. the working method of said according to Claim 8 bis(t-butylperoxy) ketal is characterized in that said catalyzer is equally divided at least twice and adds in the reactant.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010238180.9A CN102336695B (en) | 2010-07-27 | 2010-07-27 | Production method of di(tert-butylperoxy)ketal |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010238180.9A CN102336695B (en) | 2010-07-27 | 2010-07-27 | Production method of di(tert-butylperoxy)ketal |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102336695A true CN102336695A (en) | 2012-02-01 |
| CN102336695B CN102336695B (en) | 2014-12-03 |
Family
ID=45512695
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201010238180.9A Active CN102336695B (en) | 2010-07-27 | 2010-07-27 | Production method of di(tert-butylperoxy)ketal |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102336695B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102850249A (en) * | 2012-09-21 | 2013-01-02 | 江苏强盛功能化学股份有限公司 | Preparation method of 1, 1-bis(t-butyl peroxy)-3, 3, 5-trimethylcyclohexane |
| CN103360623A (en) * | 2013-07-07 | 2013-10-23 | 天长市天广有机玻璃有限公司 | Preparation method of peroxide poly-hybrid ketal solution |
| CN103421209A (en) * | 2013-07-07 | 2013-12-04 | 天长市天广有机玻璃有限公司 | Medium temperature curing initiator suitable for unsaturated resin products |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3308163A (en) * | 1964-03-09 | 1967-03-07 | Wallace & Tiernan Inc | Process for preparing peroxy compounds |
| US4052464A (en) * | 1975-07-21 | 1977-10-04 | The Dow Chemical Company | Process for the manufacture of di-t-butylperoxy ketals |
-
2010
- 2010-07-27 CN CN201010238180.9A patent/CN102336695B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3308163A (en) * | 1964-03-09 | 1967-03-07 | Wallace & Tiernan Inc | Process for preparing peroxy compounds |
| US4052464A (en) * | 1975-07-21 | 1977-10-04 | The Dow Chemical Company | Process for the manufacture of di-t-butylperoxy ketals |
Non-Patent Citations (2)
| Title |
|---|
| KAZUO MATSUYAMA ET AL: "Substituent Effects on the Decomposition of Bis ( tert-buty1peroxy)cycloalkanes", 《J. ORG. CHEM.》, vol. 58, no. 7, 31 March 1993 (1993-03-31) * |
| 张亚兰: "1，1-二叔丁基过氧化环己烷的试制", 《湛江师范学院学报(自然科学版)》, vol. 17, no. 02, 15 December 1996 (1996-12-15) * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102850249A (en) * | 2012-09-21 | 2013-01-02 | 江苏强盛功能化学股份有限公司 | Preparation method of 1, 1-bis(t-butyl peroxy)-3, 3, 5-trimethylcyclohexane |
| CN103360623A (en) * | 2013-07-07 | 2013-10-23 | 天长市天广有机玻璃有限公司 | Preparation method of peroxide poly-hybrid ketal solution |
| CN103421209A (en) * | 2013-07-07 | 2013-12-04 | 天长市天广有机玻璃有限公司 | Medium temperature curing initiator suitable for unsaturated resin products |
| CN103421209B (en) * | 2013-07-07 | 2015-03-25 | 天长市天广有机玻璃有限公司 | Medium temperature curing initiator suitable for unsaturated resin products |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102336695B (en) | 2014-12-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102336694B (en) | The synthetic method of bis(t-butylperoxy) ketal | |
| Lyu et al. | Natural-sourced benzoxazine resins, homopolymers, blends and composites: A review of their synthesis, manufacturing and applications | |
| Rao et al. | Synthesis of bio based low temperature curable liquid epoxy, benzoxazine monomer system from cardanol: Thermal and viscoelastic properties | |
| Zhang et al. | Cleavage of lignin C–O bonds over a heterogeneous rhenium catalyst through hydrogen transfer reactions | |
| JP5360719B2 (en) | Method for producing solid acid catalyst comprising sulfonic acid group-containing carbonaceous material and use thereof | |
| CN106866331B (en) | Method for preparing cyclopentadiene or dicyclopentadiene from furfuryl alcohol | |
| Katritzky et al. | Aqueous high-temperature chemistry of carbo-and heterocycles. 21. Reactions of sulfur-containing compounds in supercritical water at 460. degree. C | |
| CN107235829A (en) | The method that a kind of selective hydrogenolysis of lignin prepares 4 ethyl -phenols | |
| CN102336695B (en) | Production method of di(tert-butylperoxy)ketal | |
| CN105503540A (en) | Method for preparation of benzene ring phenol compound from alkali lignin | |
| CN104003847A (en) | Directional synthetic method of 2, 5-di tertiary butyl hydroquinone | |
| CN106866364A (en) | A kind of method that 1,3- ring pentanediols are prepared by furfuryl alcohol | |
| CN102527436A (en) | Method for preparing novel epoxidation catalyst of cyclohexene | |
| CN108117475A (en) | A kind of method that JP-10 aviation fuel is prepared by furfuryl alcohol | |
| CN101381333B (en) | Method for preparing corresponding thiophenol by reduction of aromatic sulfonic acid or derivates thereof | |
| CN101544587B (en) | Preparation method of alpha, alpha'-bis(tert-butyl peroxy) diisopropylbenzene | |
| CN101219922A (en) | Process for producing cyclohexylbenzene | |
| CN113277930B (en) | Method for preparing cresol by utilizing lignocellulose biomass | |
| CN106673971A (en) | Method for catalytically depolymerizing lignin by using MTO (Methyltrioxorhenium) under microwave promoted condition | |
| CN106220464B (en) | A kind of method for being catalyzed australene dimerization reaction | |
| CN113912478A (en) | Synthetic method of 4, 4' -biphenol | |
| CA2727375A1 (en) | Method for producing 1,2-propanediol by hydrogenolysis of glycerin | |
| CN106512981A (en) | Vanadium-based catalyst for preparation of phenol through direct oxidation of benzene and preparation method thereof | |
| CN108117474A (en) | A kind of method that furfuryl alcohol prepares JP-10 aviation fuel | |
| CN112299959A (en) | Method for preparing diethoxymethane by solid superacid catalysis |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |