CN101544587B

CN101544587B - Preparation method of alpha, alpha'-bis(tert-butyl peroxy) diisopropylbenzene

Info

Publication number: CN101544587B
Application number: CN 200910043267
Authority: CN
Inventors: 李玉新; 单文伟
Original assignee: HUNAN YIXIANG TECHNOLOGY Co Ltd
Current assignee: HUNAN YIXIANG TECHNOLOGY Co Ltd
Priority date: 2009-04-30
Filing date: 2009-04-30
Publication date: 2013-06-05
Anticipated expiration: 2029-04-30
Also published as: CN101544587A

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 by the compositions of mixtures 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 prepared by tertbutyl peroxide (being called for short TBHP) and alcohol reaction in the prior art, this reaction is mainly 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 " the 22nd the 6th phase of volume in 2000, 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 ").Existing preparation method generally will use a large amount of liquid strong acid to promote the carrying out of reaction, reacts complete rear mineral acid and does not consume, and also need the residue acid solution is processed, and the treating method of commonly using at present is neutralization; From economy and environmental angle, processing by neutralization is all 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, have be easy to separate, can be recycled, on environment without impact and to equipment without advantages such as corrosion, present, heteropolyacid particularly is applied aspect catalytic esterification in the organic synthesis field.the also report of the synthetic organo-peroxide of useful heteropoly acid catalysis in recent years, comprise that the reaction of 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, 315 (2006) 150-152), but not yet see the relevant report of using heteropoly acid catalysis synthetic environment-friendly crosslinking agent B IPB.

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), comprise the following steps: be 0.8～1.9 tertbutyl peroxide hydrate and α with mass ratio, α '-dihydroxyl-p-Diisopropylbenzene (being called for short DC) is placed in organic solvent, add heteropolyacid and make catalyzer, stir and react, filter after reaction 15～25h, filtrate is after decompression removes described organic solvent, raffinate is cooled to below 30 ℃ and solidifies, obtain product α, α '-two (tert-butyl peroxy base) diisopropylbenzene(DIPB).

In 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.

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

In 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.

In 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) diisopropylbenzene(DIPB) preparation feedback, and the processing parameter in preparation process is optimized and revised, and then synthesize fast, easily target product α, α '-two (tert-butyl peroxy base) diisopropylbenzene(DIPB).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 having used a kind of new heteropolyacid catalyst, not only simplified the operating process of existing technique, and greatly alleviated pollution to environment, avoided the corrosion to production unit, greatly reduce the production cost of existing technique, a kind ofly can effectively make α, the process for cleanly preparing of α '-two (tert-butyl peroxy base) diisopropylbenzene(DIPB).

Embodiment

Embodiment 1

Add successively hexanaphthene 150g, catalyzer 4.5g, TBHP80% hydrate (commercially available) 21.2g and DC 19.5g in the 250mL there-necked flask, mixed material is stirring reaction 20h at 30 ℃ of temperature, then suction filtration, filtrate underpressure distillation under 50 ℃～60 ℃ conditions is to solvent-free distillating; Raffinate after distillation is cooled to below 25 ℃, namely 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, namely HPLC measures).

Embodiment 2

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

Embodiment 3

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

Embodiment 4

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

The Dawson type structure that above each embodiment catalyzer used obtains for self-control contains the phosphorus heteropoly tungstic acid of crystal water, and its molecular formula is H ₆P ₂W ₁₈O ₆₂NH ₂O (value of n is 8～15), the preparation method of this catalyzer is with reference to " Li Shuigen etc.: " Dawson structure Catalyzed by Phosphotungstic Acid synthesizing tetrahydrofuran ", " Chinese Tungsten Industry " the 22nd the 4th phase of volume in 2007, the 36th page ".

Claims

1. α, the preparation method of α '-two (tert-butyl peroxy base) diisopropylbenzene(DIPB), comprise the following steps: be 0.8～1.9 tertbutyl peroxide hydrate and α with mass ratio, α '-dihydroxyl-p-Diisopropylbenzene is placed in organic solvent, add heteropolyacid and make catalyzer, stir and react, the temperature of reaction is controlled at 0 ℃～50 ℃, filter after reaction 15～25h, 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); 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; Described catalyzer and α, the mass ratio of α '-dihydroxyl-p-Diisopropylbenzene are 1: 10～10: 1; Described organic solvent is di-t-butyl peroxide, hexanaphthene or methylene dichloride, and the consumption of this organic solvent is described α, 5～10 times of α '-dihydroxyl-p-Diisopropylbenzene quality.

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

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

4. preparation method according to claim 1, it is characterized in that: the temperature of described reaction is controlled at 15 ℃～35 ℃.