CN101544587A

CN101544587A - Preparation method of alpha, alpha'-bis(tert-butyl peroxy) diisopropylbenzene

Info

Publication number: CN101544587A
Application number: CN200910043267A
Authority: CN
Inventors: 李玉新; 单文伟
Original assignee: HUNAN YIXIANG CHEMICAL INDUSTRIAL Co Ltd
Current assignee: HUNAN YIXIANG CHEMICAL INDUSTRIAL Co Ltd
Priority date: 2009-04-30
Filing date: 2009-04-30
Publication date: 2009-09-30
Anticipated expiration: 2029-04-30
Also published as: CN101544587B

Abstract

The present invention discloses a preparation method of alpha, alpha'-bis(tert-butyl peroxy) diisopropylbenzene, including the following steps: put tert-butyl peroxyhydrate and alpha, alpha'-dihydroxy-p- diisopropylbenzene (mass ratio: 0.8-1.9) into an organic solvent, add heteropoly acid as catalyst, react under agitation at room temperature, filter the material 15-25h later, remove the organic solvent from filtrate through decompression, cool down residual solution to below 30 DEG C to solidify it, and obtain product alpha, alpha'-bis(tert-butyl peroxy) diisopropylbenzene. The present invention is characterized by simple process, easy operation, low cost, high safety and effective reduction of environmental pollution and equipment corrosion.

Description

α, the preparation method of α '-two (tert-butyl peroxy base) diisopropylbenzene(DIPB)

Technical field

The present invention relates to a kind of synthesis technique of organo-peroxide, relate in particular to a kind of preparation technology of two (tert-butyl peroxy base) diisopropylbenzene(DIPB)s.

Background technology

α, α '-two (tert-butyl peroxy base) diisopropylbenzene(DIPB) (being called for short BIPB or two BP) is a kind of alternative dicumyl peroxide new and effective pollution-free linking agent of (being called for short DCP), main linking agent as polyethylene, unsaturated polyester, silicon rubber, paracril, ethylene-propylene rubber(EPR) and urethane, be particularly suitable for the occasion that indoor goods and toy for children, food utensil etc. are had relatively high expectations, having improved the stink of general crosslink agent DCP, is a kind of broad-spectrum good linking agent.The BIPB product mainly is made up of the mixture of a position and para-isomeride, is white powder, molecular weight 338.49, theoretical active oxygen 9.45%, activation energy 36.1 kcal/mol, 10 hours/120 ℃ of transformation period, 45～50 ℃ of fusing points.

BIPB is as a kind of tert-butyl peroxide, normally obtain with pure prepared in reaction in the prior art by tertbutyl peroxide (being called for short TBHP), this reaction mainly is as catalyzer with strong acid, as sulfuric acid, perchloric acid etc. (referring to " ChenBing Zhi etc.: " improvement of peroxy tert-butyl alcohol and ditertiary butyl peroxide synthetic method "; " chemical reagent " 2000 the 22nd the 6th phase of volume, the 368th page "; " fourth eastwards: " study on the synthesis of the two BP of linking agent ", " Anhui chemical industry " the 6th phase in 2006, the 30th page ").Prior preparation method generally will use a large amount of liquid strong acid to promote the carrying out of reaction, and mineral acid did not consume after reaction finished, and also need the residue acid solution is handled, and treating method commonly used at present is neutralization; From economy and environmental angle, handling by neutralization all is a kind of method of being accepted and promoting of being difficult to, and operating process is also cumbersome.

Heteropolyacid substitutes liquid strong acid as catalyzer, has to be easy to separate, to can be recycled, environment is not had influence and equipment do not had advantage such as corrosion, and present, heteropolyacid particularly is applied aspect catalytic esterification in the organic synthesis field.The report of the synthetic organo-peroxide of also useful in recent years heteropoly acid catalysis, the reaction that comprises the TBHP and the trimethyl carbinol is (referring to M.K.Faraj, US 5288919,1994, Preparation of dialkyl peroxides), TBHP and α, (the A.Tarlani such as reaction of alpha-alpha-dimethyl benzylalcohol, Catalytic condensation process for the preparation of organic peroxides from tert-butylhydroperoxide and benzylic alcohols, Applied Catalysis A:General, but do not see the relevant report of using heteropoly acid catalysis synthetic environment-friendly crosslinking agent B IPB as yet 315 (2006) 150-152).

Summary of the invention

The technical problem to be solved in the present invention is to overcome the deficiencies in the prior art, provide that a kind of technological process is simple, easy to operate, cost is low, security good and can effectively reduce the α of environmental pollution and equipment corrosion, the preparation method of α '-two (tert-butyl peroxy base) diisopropylbenzene(DIPB).

For solving the problems of the technologies described above, the technical scheme that the present invention proposes is a kind of α, the preparation method of α '-two (tert-butyl peroxy base) diisopropylbenzene(DIPB), may further comprise the steps: be 0.8～1.9 tertbutyl peroxide hydrate and α with mass ratio, α '-dihydroxyl-p-Diisopropylbenzene (being called for short DC) places organic solvent, add heteropolyacid and make catalyzer, stir and react, reaction 15～25h after-filtration, filtrate is after decompression removes described organic solvent, raffinate is cooled to below 30 ℃ and solidifies, and obtains product α, α '-two (tert-butyl peroxy base) diisopropylbenzene(DIPB).

Among the above-mentioned preparation method, described catalyzer is preferably the phosphorus heteropoly tungstic acid that Dawson type structure contains crystal water, and its molecular formula is H ₆P ₂W ₁₈O ₆₂NH ₂O, the value of n is 8～15.Described catalyzer and α, the mass ratio of α '-dihydroxyl-p-Diisopropylbenzene can be 1:10～10:1, is preferably 1:5～1:1.

Among the above-mentioned preparation method, described tertbutyl peroxide hydrate and α, the mass ratio of α '-dihydroxyl-p-Diisopropylbenzene is preferably 1.1～1.4.

Among the above-mentioned preparation method, described organic solvent is preferably di-t-butyl peroxide (be called for short DTBP), hexanaphthene or methylene dichloride, and the consumption of this organic solvent is preferably described α, 5～10 times of α '-dihydroxyl-p-Diisopropylbenzene quality.

Among the above-mentioned preparation method, the suggestion of the temperature of described reaction is controlled at 0 ℃～50 ℃, preferably is controlled at 15 ℃～35 ℃.

Compared with prior art, the invention has the advantages that: substitute sulfuric acid commonly used as α with heteropolyacid, catalyzer in α '-two (tert-butyl peroxy base) the diisopropylbenzene(DIPB) preparation feedback, and the processing parameter in the preparation process optimized and revised, and then synthesize target product α, α '-two (tert-butyl peroxy base) diisopropylbenzene(DIPB) fast, easily.Preparation method of the present invention can carry out preparation feedback at normal temperatures, greatly reduces energy consumption, has improved the security of superoxide; Owing to used a kind of new heteropolyacid catalyst, not only simplified the operating process of existing technology, and alleviated pollution greatly to environment, avoided corrosion to production unit, greatly reduce the production cost of existing technology, be a kind ofly can effectively make α, the process for cleanly preparing of α '-two (tert-butyl peroxy base) diisopropylbenzene(DIPB).

Embodiment

Embodiment 1

In the 250mL there-necked flask, add hexanaphthene 150g, catalyzer 4.5g, TBHP80% hydrate (commercially available) 21.2g and DC19.5g successively, mixed material is stirring reaction 20h under 30 ℃ of temperature, suction filtration then, filtrate underpressure distillation under 50 ℃～60 ℃ conditions is to solvent-free distillating; Raffinate after the distillation is cooled to below 25 ℃, promptly obtains the solid product BIPB of 20.8g, and yield is 60.8% (in DC), and content reaches 98.5% (adopt high efficiency liquid phase chromatographic analysis method to measure, promptly HPLC measures).

Embodiment 2

In the 250mL there-necked flask, add methylene dichloride 100g, catalyzer 18.5g, TBHP80% hydrate 26.5g and DC19.5g successively, mixed material is stirring reaction 16h under 45 ℃ of temperature, suction filtration then, filtrate underpressure distillation under 50 ℃～55 ℃ conditions is to solvent-free distillating; Raffinate after the distillation is cooled to below 25 ℃, promptly obtains the solid product BIPB of 17.5g, and yield is 50.8% (in DC), and content reaches 98.2% (HPLC assay determination).

Embodiment 3

In the 250mL there-necked flask, add di-t-butyl peroxide 150g, catalyzer 9.8g, TBHP80% hydrate 21.5g and DC19.5g successively, mixed material is stirring reaction 20h under 45 ℃ of temperature, suction filtration then, filtrate underpressure distillation under 55 ℃～60 ℃ conditions is to solvent-free distillating; Vinasse is cooled to below 25 ℃, promptly obtains the solid product BIPB of 18.3g, and yield is 54.0% (in DC), and content reaches 99.1% (HPLC assay determination).

Embodiment 4

In the 100L glassed steel reaction vessels, add hexanaphthene 55kg, catalyzer 7.2kg, TBHP80% hydrate 8.4kg and DC7.8kg successively, mixed material is stirring reaction 25h under 30 ℃ of temperature, suction filtration then, filtrate underpressure distillation under 50 ℃～60 ℃ conditions is to solvent-free distillating; Vinasse is cooled to below 25 ℃, promptly obtains the solid product BIPB of 9.1kg, and yield is 65.7% (in DC), and content reaches 98.9% (HPLC assay determination).

More than the used catalyzer of each embodiment contain the phosphorus heteropoly tungstic acid of crystal water for the Dawson type structure that obtains of self-control, its molecular formula is H ₆P ₂W ₁₈O ₆₂NH ₂O (value of n is 8～15), this Preparation of catalysts method is with reference to " Li Shuigen etc.: " Dawson structure phosphorus heteropoly tungstic acid catalysis synthesizing tetrahydrofuran ", " Chinese tungsten industry " the 22nd the 4th phase of volume in 2007, the 36th page ".

Claims

1, a kind of α, the preparation method of α '-two (tert-butyl peroxy base) diisopropylbenzene(DIPB), may further comprise the steps: with mass ratio is 0.8～1.9 tertbutyl peroxide hydrate and α, and α '-dihydroxyl-p-Diisopropylbenzene places organic solvent, adds heteropolyacid and makes catalyzer, stir and react, reaction 15～25h after-filtration, filtrate is after decompression removes described organic solvent, and raffinate is cooled to below 30 ℃ and solidifies, obtain product α, α '-two (tert-butyl peroxy base) diisopropylbenzene(DIPB).

2, preparation method according to claim 1 is characterized in that: described catalyzer is the phosphorus heteropoly tungstic acid that Dawson type structure contains crystal water, and its molecular formula is H ₆P ₂W ₁₈O ₆₂NH ₂O, the value of n is 8～15.

3, preparation method according to claim 2 is characterized in that: described catalyzer and α, the mass ratio of α '-dihydroxyl-p-Diisopropylbenzene are 1:10～10:1.

4, preparation method according to claim 3 is characterized in that: described catalyzer and α, the mass ratio of α '-dihydroxyl-p-Diisopropylbenzene are 1:5～1:1.

5, preparation method according to claim 1 is characterized in that: described tertbutyl peroxide hydrate and α, the mass ratio of α '-dihydroxyl-p-Diisopropylbenzene are 1.1～1.4.

6, according to each described preparation method in the claim 1～5, it is characterized in that: described organic solvent is di-t-butyl peroxide, hexanaphthene or methylene dichloride, the consumption of this organic solvent is described α, 5～10 times of α '-dihydroxyl-p-Diisopropylbenzene quality.

7, according to each described preparation method in the claim 1～5, it is characterized in that: the temperature of described reaction is controlled at 0 ℃～50 ℃.

8, preparation method according to claim 6 is characterized in that: the temperature of described reaction is controlled at 15 ℃～35 ℃.