CN109516940B - Method for synthesizing dialkyl peroxide - Google Patents
Method for synthesizing dialkyl peroxide Download PDFInfo
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- CN109516940B CN109516940B CN201811386024.XA CN201811386024A CN109516940B CN 109516940 B CN109516940 B CN 109516940B CN 201811386024 A CN201811386024 A CN 201811386024A CN 109516940 B CN109516940 B CN 109516940B
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- peroxide
- polyvinyl alcohol
- amino acid
- compound
- reaction
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- QIVBCDIJIAJPQS-UHFFFAOYSA-N Tryptophan Natural products C1=CC=C2C(CC(N)C(O)=O)=CNC2=C1 QIVBCDIJIAJPQS-UHFFFAOYSA-N 0.000 description 1
- KZSNJWFQEVHDMF-UHFFFAOYSA-N Valine Natural products CC(C)C(N)C(O)=O KZSNJWFQEVHDMF-UHFFFAOYSA-N 0.000 description 1
- 235000004279 alanine Nutrition 0.000 description 1
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- 150000001298 alcohols Chemical class 0.000 description 1
- 125000005233 alkylalcohol group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
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- 238000006701 autoxidation reaction Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011942 biocatalyst Substances 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 235000004554 glutamine Nutrition 0.000 description 1
- ZDXPYRJPNDTMRX-UHFFFAOYSA-N glutamine Natural products OC(=O)C(N)CCC(N)=O ZDXPYRJPNDTMRX-UHFFFAOYSA-N 0.000 description 1
- 229960002743 glutamine Drugs 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 229960000310 isoleucine Drugs 0.000 description 1
- AGPKZVBTJJNPAG-UHFFFAOYSA-N isoleucine Natural products CCC(C)C(N)C(O)=O AGPKZVBTJJNPAG-UHFFFAOYSA-N 0.000 description 1
- 235000014705 isoleucine Nutrition 0.000 description 1
- 235000005772 leucine Nutrition 0.000 description 1
- 229960003136 leucine Drugs 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 235000018977 lysine Nutrition 0.000 description 1
- 229960003646 lysine Drugs 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 235000006109 methionine Nutrition 0.000 description 1
- 229930182817 methionine Natural products 0.000 description 1
- 229960004452 methionine Drugs 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 235000008729 phenylalanine Nutrition 0.000 description 1
- 229960005190 phenylalanine Drugs 0.000 description 1
- COLNVLDHVKWLRT-UHFFFAOYSA-N phenylalanine Natural products OC(=O)C(N)CC1=CC=CC=C1 COLNVLDHVKWLRT-UHFFFAOYSA-N 0.000 description 1
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000028043 self proteolysis Effects 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- KUCOHFSKRZZVRO-UHFFFAOYSA-N terephthalaldehyde Chemical compound O=CC1=CC=C(C=O)C=C1 KUCOHFSKRZZVRO-UHFFFAOYSA-N 0.000 description 1
- 229960002898 threonine Drugs 0.000 description 1
- 235000008521 threonine Nutrition 0.000 description 1
- 229960004799 tryptophan Drugs 0.000 description 1
- 229960004295 valine Drugs 0.000 description 1
- 239000004474 valine Substances 0.000 description 1
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- 235000013311 vegetables Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C407/00—Preparation of peroxy compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
-
- B01J35/51—
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to the technical field of chemical synthesis, and particularly relates to a synthesis method of dialkyl peroxide. Adding an alkyl alcohol compound, a compound containing a peroxide bond and a polyvinyl alcohol composite amino acid catalyst into an organic solvent, and stirring and dehydrating to synthesize dialkyl peroxide; the polyvinyl alcohol composite amino acid catalyst is obtained by polymerizing a spherical polyvinyl alcohol matrix and composite amino acid. In the peroxide production process, the method avoids using chemical raw materials, namely sulfuric acid or sodium hydroxide with certain corrosiveness, optimizes the synthesis process of the peroxide and reduces the discharge of wastewater containing the sulfuric acid or the sodium hydroxide in the industrial production process.
Description
Technical Field
The invention belongs to the technical field of chemical synthesis, and particularly relates to a synthesis method of dialkyl peroxide.
Background
Dialkyl peroxides are industrially important initiators for high-molecular polymerization, particularly for polyacrylates, polyethylenes, polyvinyl chlorides and polystyrenics. Commercially, dialkyl peroxides are prepared from hydrogen peroxide and the corresponding alkyl alcohol. In the prior art, the synthesis methods of dialkyl peroxides are many, and there are a base catalytic synthesis method, an acid catalytic synthesis method, a metal ion catalytic method, an autoxidation method and the like. For example, in the acid catalytic synthesis method, tert-butyl alcohol and hydrogen peroxide are used as raw materials, and sulfuric acid is used as a catalyst to synthesize di-tert-butyl peroxide.
CN107311906A discloses a production process of di-tert-butyl peroxide, hydrogen peroxide and tert-butyl alcohol react under the catalysis of sulfuric acid to obtain the di-tert-butyl peroxide in one step, so that the production period is shortened, the energy consumption is reduced, and the generation of waste sulfuric acid is reduced.
CN104557652A discloses a preparation method of tert-butyl peroxide, which comprises the steps of taking tert-butyl alcohol and hydrogen peroxide as raw materials, taking acidic ion exchange resin as a catalyst, carrying out reflux reaction, cooling, standing and separating to obtain separated oil phase and water phase; and (3) carrying out alkali washing and water washing on the oil phase to obtain a di-tert-butyl peroxide solution.
CN101298429A discloses a method for preparing tert-butyl hydroperoxide and di-tert-butyl peroxide, which comprises mixing sulfuric acid, hydrogen peroxide and phosphotungstic acid at certain concentration, and adding tert-butyl alcohol into the mixed solution, or adding the mixed solution into tert-butyl alcohol; reacting for 0.5-5 h at 20-60 ℃, and separating the crude reaction product to obtain an oil phase; the oil phase is rectified under reduced pressure to obtain tert-butyl hydroperoxide and di-tert-butyl peroxide products.
CN107056670A discloses a preparation method of di-tert-butyl peroxide, which is to return tert-butyl alcohol, hydrogen peroxide and a catalyst to a micro-reaction device in a continuous manner, so that the tert-butyl alcohol and the hydrogen peroxide are subjected to peroxidation to prepare a material flow containing di-tert-butyl peroxide, then the material flow containing the di-tert-butyl peroxide is led out from the micro-reaction device, and the di-tert-butyl peroxide is obtained through separation, water washing and drying.
CN105523982A discloses a preparation method of tert-butyl hydroperoxide, which comprises peroxidation and condensation reaction, concentrated sulfuric acid is used as a catalyst, hydrogen peroxide and tert-butyl alcohol are used for reaction for 0.5-4 h at 10-50 ℃, an organic phase of a reaction crude product is an intermediate product of tert-butyl hydroperoxide and a byproduct of di-tert-butyl peroxide, and the byproduct of di-tert-butyl peroxide is removed by a salt formation technology; adding 2-ethylhexyl chloroformate and sodium hydroxide solution as a catalyst into the inorganic phase, and reacting at 10-50 ℃ for 1.0-6 h to obtain tert-butyl peroxy-2-ethylhexyl carbonate.
CN105237453A discloses a method for preparing methyl ethyl ketone peroxide by using acidic ion exchange resin as a catalyst, which is to use butanone and hydrogen peroxide as raw materials, use acidic ion exchange resin as a catalyst, use dibutyl phthalate as a diluent, stir at a constant temperature for reaction, stand for separation, and obtain an oil phase, namely methyl ethyl ketone peroxide.
CN1871358A discloses a method for producing hydrocarbons and oxygen-containing compounds from biomass for carbohydrate substrates of vegetable originFermentation of the material to produce C1～C5Alcohols and synthesis of higher alcohols and other oxygenates. The synthetic raw materials are prepared biogas and C2～C5Alcohols in which the amino acids leucine, isoleucine and valine or mixtures thereof, optionally obtained from yeast autolysis, are used as biocatalysts during the fermentation stage.
The above method has the disadvantage that the raw material sulfuric acid or alkali (sodium hydroxide) is a chemical raw material with certain corrosiveness, and can cause corrosive substances to be formed in the using process. But also presents environmental problems in the form of sulfates or similar waste during use.
Disclosure of Invention
The invention aims to provide a method for synthesizing dialkyl peroxide, which is scientific, reasonable, simple and feasible, avoids using chemical raw materials such as sulfuric acid or sodium hydroxide with certain corrosivity, and has good environmental protection effect.
The synthesis method of the dialkyl peroxide comprises the following steps:
adding an alkyl alcohol compound, a compound containing a peroxide bond and a polyvinyl alcohol composite amino acid catalyst into an organic solvent, and stirring and dehydrating to synthesize dialkyl peroxide;
the polyvinyl alcohol composite amino acid catalyst is obtained by polymerizing a spherical polyvinyl alcohol matrix and composite amino acid.
The spherical polyvinyl alcohol matrix is obtained by crosslinking polyvinyl alcohol and a crosslinking agent.
The polyvinyl alcohol is available in many grades, products such as 0588, 0599, 1788, 1799, 2088, 2099, 2488 and 2499 are generally selected, products such as 1788, 1799, 2088 and 2099 are preferably used, and 1799 polyvinyl alcohol is more preferably used.
The cross-linking agent is one or more of glutaraldehyde, terephthaldehyde or formaldehyde. As glutaraldehyde as the cross-linking agent has the advantages of high cross-linking speed, large cross-linking network, low toxicity and the like, glutaraldehyde is preferably used as the cross-linking agent in the invention.
The compound amino acid is two or more of cysteine, phenylalanine, alanine, methionine, glycine, glutamic acid, glutamine, arginine, lysine, tyrosine, leucine, aspartic acid, asparagine, proline, tryptophan, serine, threonine, valine, isoleucine or histidine; the preferable compound amino acid is two or more of cysteine, glutamic acid, arginine, aspartic acid, proline, glycine, tyrosine, histidine or serine.
More preferred complex amino acids of the invention are mixtures of cysteine, glutamic acid, arginine, aspartic acid and proline.
More preferred complex amino acids of the invention are mixtures of cysteine, glycine, tyrosine, proline and histidine.
More preferred complex amino acids of the invention are a mixture of cysteine, glutamic acid, arginine, serine and histidine.
The addition amount of the polyvinyl alcohol composite amino acid catalyst is 1-100% of the mass of the compound containing the peroxide bond.
The amount of polyvinyl alcohol complex amino acid catalyst added depends on several factors known to those skilled in the art of peroxide reaction, including reactivity between a compound containing a peroxide bond and an alkyl compound; reaction conditions such as temperature and reaction time, and stirring speed, etc. In the present invention, the polyvinyl alcohol composite amino acid catalyst is added in an amount of preferably 5 to 50% by mass, more preferably 15 to 25% by mass, based on the mass of the compound having a peroxide bond added.
The specific preparation steps of the polyvinyl alcohol compound amino acid catalyst are as follows:
(1) dissolving polyvinyl alcohol in distilled water, stirring for 5 hours in a water bath at 100 ℃, cooling to room temperature, adding a cross-linking agent, and stirring to obtain a raw material A;
(2) adding a surfactant span80 into cyclohexane, and uniformly stirring to obtain a raw material B;
(3) adding the raw material A into a three-necked bottle, adding a hydrochloric acid solution, uniformly stirring, adding the raw material B, controlling the stirring speed at 400-600 r/min, reacting at room temperature for 4h, slowly heating to 70 ℃ for reacting for 4h, cooling, filtering, and washing to obtain a spherical polyvinyl alcohol matrix for later use.
(4) Adding dimethyl sulfoxide and a spherical polyvinyl alcohol matrix into a three-necked bottle, adding a compound amino acid, uniformly mixing, stirring and reacting for 8 hours at a constant temperature of 90-110 ℃, cooling, performing suction filtration, washing twice with ethanol, and drying to obtain the spherical polyvinyl alcohol compound amino acid catalyst with a catalytic active group.
The polyvinyl alcohol composite amino acid catalyst is prepared by taking polyvinyl alcohol as a raw material, utilizing a cross-linking agent to obtain spherical polyvinyl alcohol through inverse polymerization, and reacting the spherical polyvinyl alcohol with composite amino acid.
The organic solvent is petroleum ether or pentane.
The structural formula of the alkyl alcohol compound is R-OH, wherein R group is straight chain or branched chain or C with aromatic ring1～C16A group. The R group can be, but is not limited to, methyl, ethyl, propyl, butyl, isobutyl, t-butyl, pentyl, isopentyl, t-pentyl, cyclopentyl, cyclohexyl, phenyl, benzyl, phenethyl, phenylpropyl, isooctyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, and the like.
The compound containing peroxide bonds is hydrogen peroxide or 2, 5-dimethyl n-hexane-2, 5-dimethylhydroxyperoxide.
The molar ratio of the compound containing a peroxide bond to the alkyl alcohol compound is 1: 10-5: 1.
Generally, the reaction of the compound having a peroxide bond with the alkyl alcohol compound may be carried out in a wide range of molar ratios in order to increase the yield of the reaction product. In the method of the present invention, the compound having a peroxide bond is preferably reacted with the alkyl alcohol compound at a molar ratio of 1: 2.
The reaction temperature is-20-120 ℃, and the reaction time is 1-24 h.
According to the process of the present invention, the peroxide reaction can be carried out over a wide temperature range. The reaction temperature is usually controlled to be between-20 ℃ and 120 ℃, preferably between 0 ℃ and 60 ℃, more preferably between 20 ℃ and 40 ℃. The reaction temperature is usually varied according to the physicochemical properties of the product itself. The preferable reaction time is 4-8 h.
The dehydration is carried out by azeotropic distillation, molecular distillation, stripping with dry air or stripping with inert gas.
In the chemical reaction process for producing a dialkyl peroxide by reacting a compound having a peroxide bond with an alkyl alcohol compound, reaction water is produced. The reaction water is removed from the reaction mixture in time, for example by azeotropic distillation, molecular distillation, stripping with dry air or inert gas such as nitrogen for dehydration; azeotropic distillation, dry air or inert gas stripping such as nitrogen is preferred in the present invention; more preferably, the water of reaction is removed by azeotropic distillation.
The solvent for removing the reaction water by azeotropic distillation is benzene, toluene, xylene, ethylbenzene, butane, pentane, hexane, heptane, isoheptane, octane, isooctane, cyclopentane, cyclohexane, methylcyclopentane, methylcyclohexane, petroleum ether or light gasoline; preferably the solvents toluene, xylene, pentane, hexane, cyclopentane, cyclohexane, petroleum ether or light petrol; more preferably the solvent is pentane or petroleum ether.
The invention relates to a method for preparing dialkyl peroxide by leading alkyl alcohol compound and compound containing peroxide bond to react under the action of polyvinyl alcohol compound amino acid catalyst. Dialkyl peroxides such as di-t-butyl peroxide and the like.
The document "synthesis, structure and heavy metal chelating function of amino acid-containing epoxidized crosslinked polyvinyl alcohol" (Zhejiang university school report, 2009, 37(5): 515-. The invention firstly applies the polyvinyl alcohol compound amino acid catalyst in the field of catalytic synthesis of peroxide, and has innovation.
In the present invention, the amino acid-containing polyvinyl alcohols are all the same as the amino acid-containing polyvinyl alcohols of the prior art documents, but the chemical structures of the amino acid-containing polyvinyl alcohols are completely different from those of the prior art documents. The polyvinyl alcohol high-molecular chelating agent disclosed in the document 'synthesis, structure and heavy metal chelating function of amino acid-containing epoxidized crosslinked polyvinyl alcohol' is formed by connecting polyvinyl alcohol and amino acid together through epichlorohydrin.
The invention discloses a novel method for synthesizing a peroxide by using polyethylene spheres containing a specific combination of amino acids. Compared with amino acid or amino acid mixture, the combination of the combined amino acid and polyvinyl alcohol is the key of the catalysis of the polyethylene ball containing the specific combined amino acid, and the preferable combination of several amino acids has the synergistic catalysis effect of amino, carboxyl, hydroxyl and sulfydryl contained in the catalyst ball in a special space to catalyze the synthesis of peroxide.
The invention has the following beneficial effects:
in the peroxide production process, the method avoids using chemical raw materials, namely sulfuric acid or sodium hydroxide with certain corrosiveness, optimizes the synthesis process of the peroxide and reduces the discharge of wastewater containing the sulfuric acid or the sodium hydroxide in the industrial production process.
Detailed Description
The present invention is further described below with reference to examples.
And 5, mixing one part of each of five amino acids including cysteine, glutamic acid, arginine, aspartic acid and proline to obtain the compound amino acid A.
And (3) mixing one part of each of five amino acids of cysteine, glycine, tyrosine, proline and histidine to obtain the compound amino acid B.
And mixing one part of each of five amino acids including cysteine, glutamic acid, arginine, serine and histidine to obtain the compound amino acid C.
The polyvinyl alcohol compound amino acid catalyst is synthesized by the following method:
(1) dissolving 10g of polyvinyl alcohol (1799) in 200ml of distilled water, stirring for 5 hours in a water bath at 100 ℃, cooling to room temperature, adding 2.1ml of glutaraldehyde solution (50 percent), and stirring to obtain a raw material A;
(2) adding 4g of surfactant span80 into 600ml of cyclohexane, and uniformly stirring to obtain a raw material B;
(3) adding the raw material A into a 2000ml three-necked bottle, adding 14ml hydrochloric acid solution (0.1mol/L), uniformly stirring, adding the raw material B, controlling the stirring speed at 400-600 r/min, reacting at room temperature for 4h, slowly heating to 70 ℃ for reacting for 4h, cooling, filtering, and washing to obtain spherical polyvinyl alcohol for later use.
(4) Adding 200mL of dimethyl sulfoxide and 10g of spherical polyvinyl alcohol into a 500mL three-necked bottle, adding 5.1g of compound amino acid A, uniformly mixing, stirring and reacting for 8 hours at a constant temperature of 90-110 ℃, cooling, performing suction filtration, washing twice with ethanol, and drying to obtain the spherical polyvinyl alcohol compound amino acid catalyst A with a catalytic active group.
(5) Adding 200mL of dimethyl sulfoxide and 10g of spherical polyvinyl alcohol into a 500mL three-necked bottle, adding 4.8g of compound amino acid B, uniformly mixing, stirring and reacting at a constant temperature of 90-110 ℃ for 8h, cooling, performing suction filtration, washing with ethanol twice, and drying to obtain the spherical polyvinyl alcohol compound amino acid catalyst B with a catalytic active group.
(6) Adding 100mL of dimethyl sulfoxide and 10g of spherical polyvinyl alcohol into a 500mL three-necked bottle, adding 5.2g of compound amino acid C, uniformly mixing, stirring at a constant temperature of 90-110 ℃ for reacting for 8 hours, cooling, performing suction filtration, washing with ethanol twice, and drying to obtain the spherical polyvinyl alcohol compound amino acid catalyst C with a catalytic active group.
Example 1
Adding 200ml of petroleum ether (60-90 ℃) into a 500ml three-neck bottle, adding 60g of hydrogen peroxide with the purity of 27.5%, adding 72g of tert-butyl alcohol, and adding 6g of spherical polyvinyl alcohol compound amino acid A. Stirring the reaction mixture and heating to reflux temperature of 70-80 ℃. After azeotropic distillation, the distillate was cooled and the water of reaction was removed in a water separator. The petroleum ether is separated off and returned to the reaction vessel. After 4h of reaction, the product yield of di-tert-butyl peroxide was 95.3% by gas chromatography.
Example 2
Adding 200ml of petroleum ether (60-90 ℃) into a 500ml three-neck bottle, adding 60g of hydrogen peroxide with the purity of 27.5%, adding 72g of tert-butyl alcohol, and adding 4g of spherical polyvinyl alcohol compound amino acid B. Stirring the reaction mixture and heating to reflux temperature of 70-80 ℃. After azeotropic distillation, the distillate was cooled and the water of reaction was removed in a water separator. The petroleum ether is separated off and returned to the reaction vessel. After 4h of reaction, the product yield of di-tert-butyl peroxide was 89.4% by gas chromatography.
Example 3
Adding 200ml of petroleum ether (60-90 ℃) into a 500ml three-neck bottle, adding 60g of hydrogen peroxide with the purity of 27.5%, adding 72g of tert-butyl alcohol, and adding 2g of spherical polyvinyl alcohol compound amino acid C. Stirring the reaction mixture and heating to reflux temperature of 70-80 ℃. After azeotropic distillation, the distillate was cooled and the water of reaction was removed in a water separator. The petroleum ether is separated off and returned to the reaction vessel. After 8h of reaction, the yield of di-tert-butyl peroxide product was 74.2% by gas chromatography.
Example 4
200ml of pentane is added into a 500ml three-necked flask, 35g of hydrogen peroxide with the purity of 27.5 percent is added, 77g of phenyl isopropyl alcohol is added, and 3g of spherical polyvinyl alcohol compound amino acid A is added. Stirring the reaction mixture and heating to reflux temperature of 70-80 ℃. After azeotropic distillation, the distillate was cooled and the water of reaction was removed in a water separator. The pentane is separated off and returned back to the reaction vessel. After 8h of reaction, the yield of diisopropylbenzene peroxide product was 83.1% as shown by gas chromatography.
Example 5
200ml of pentane is added into a 500ml three-necked flask, 35g of hydrogen peroxide with the purity of 27.5 percent is added, 77g of phenyl isopropyl alcohol is added, and 6g of spherical polyvinyl alcohol compound amino acid B is added. Stirring the reaction mixture and heating to reflux temperature of 70-80 ℃. After azeotropic distillation, the distillate was cooled and the water of reaction was removed in a water separator. The pentane is separated off and returned back to the reaction vessel. After 8h of reaction, the yield of diisopropylbenzene peroxide product was 91.7% as shown by gas chromatography.
Example 6
200ml of pentane is added into a 500ml three-necked flask, 35g of hydrogen peroxide with the purity of 27.5 percent is added, 77g of phenyl isopropyl alcohol is added, and 9g of spherical polyvinyl alcohol compound amino acid B is added. Stirring the reaction mixture and heating to reflux temperature of 70-80 ℃. After azeotropic distillation, the distillate was cooled and the water of reaction was removed in a water separator. The pentane is separated off and returned back to the reaction vessel. After 8h of reaction, the yield of diisopropylbenzene peroxide product was 94.7% as shown by gas chromatography.
Example 7
200ml of pentane is added into a 500ml three-necked bottle, 50g of 2, 5-dimethyl n-hexane-2, 5-dimethylhydroxyperoxide is added, 42g of tert-butyl alcohol is added, and 3g of spherical polyvinyl alcohol composite amino acid A is added. Stirring the reaction mixture and heating to reflux temperature of 70-80 ℃. After azeotropic distillation, the distillate was cooled and the water of reaction was removed in a water separator. The pentane is separated off and returned back to the reaction vessel. After 8h of reaction, the yield of 2, 5-dimethyl-2, 5-di (tert-butylperoxy) hexane was 83.6% as determined by gas chromatography.
Example 8
200ml of pentane is added into a 500ml three-necked bottle, 50g of 2, 5-dimethyl n-hexane-2, 5-dimethylhydroxyperoxide is added, 42g of tert-butyl alcohol is added, and 5g of spherical polyvinyl alcohol composite amino acid B is added. Stirring the reaction mixture and heating to reflux temperature of 70-80 ℃. After azeotropic distillation, the distillate was cooled and the water of reaction was removed in a water separator. The pentane is separated off and returned back to the reaction vessel. After 8h of reaction, the yield of 2, 5-dimethyl-2, 5-di (tert-butylperoxy) hexane was 80.5% by gas chromatography analysis.
Example 9
200ml of pentane is added into a 500ml three-necked bottle, 50g of 2, 5-dimethyl n-hexane-2, 5-dimethylhydroxyperoxide is added, 42g of tert-butyl alcohol is added, and 8g of spherical polyvinyl alcohol composite amino acid C is added. Stirring the reaction mixture and heating to reflux temperature of 70-80 ℃. After azeotropic distillation, the distillate was cooled and the water of reaction was removed in a water separator. The pentane is separated off and returned back to the reaction vessel. After 8h of reaction, the yield of 2, 5-dimethyl-2, 5-di (tert-butylperoxy) hexane was 94.3% as determined by gas chromatography.
Comparative example 1
222g of t-butanol and 140g of 70% sulfuric acid were added to a 2000ml reaction flask equipped with a stirrer, a thermometer and a dropping funnel, and the mixture was cooled to-2 to-8 ℃ with stirring. 126g of 27% hydrogen peroxide and 400g of concentrated sulfuric acid were slowly added dropwise over about 1.5 h. After the addition, the reaction was continued for 3 hours with stirring. Separating out an oil layer, washing with water, washing with 30% sodium hydroxide solution to remove tert-butyl hydroperoxide, washing with water, drying with anhydrous magnesium sulfate, and filtering to obtain di-tert-butyl peroxide.
Claims (5)
1. A method for synthesizing dialkyl peroxide is characterized by comprising the following steps:
adding an alkyl alcohol compound, a compound containing a peroxide bond and a polyvinyl alcohol composite amino acid catalyst into an organic solvent, and stirring and dehydrating to synthesize dialkyl peroxide;
the polyvinyl alcohol composite amino acid catalyst is obtained by polymerizing a spherical polyvinyl alcohol matrix and composite amino acid;
the spherical polyvinyl alcohol matrix is obtained by crosslinking polyvinyl alcohol and a crosslinking agent;
the cross-linking agent is glutaraldehyde;
the compound amino acid is a mixture of cysteine, glutamic acid, arginine, aspartic acid and proline, or a mixture of cysteine, glycine, tyrosine, proline and histidine, or a mixture of cysteine, glutamic acid, arginine, serine and histidine;
the structural formula of the alkyl alcohol compound is R-OH, wherein the R group is methyl, ethyl, propyl, butyl, isobutyl, tert-butyl, pentyl, isopentyl, tert-pentyl, cyclopentyl, cyclohexyl, phenyl, benzyl, phenethyl, phenylpropyl, isooctyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl and hexadecyl;
the compound containing peroxide bonds is hydrogen peroxide or 2, 5-dimethyl n-hexane-2, 5-dimethylhydroxyperoxide.
2. The method for synthesizing a dialkyl peroxide according to claim 1, wherein the amount of the polyvinyl alcohol/amino acid composite catalyst added is 1 to 100% by mass of the compound having a peroxide bond.
3. The process for the synthesis of dialkyl peroxides according to claim 1, characterized in that the organic solvent is petroleum ether or pentane.
4. The method for synthesizing a dialkyl peroxide according to claim 1, wherein the molar ratio of the compound having a peroxide bond to the alkyl alcohol compound is 1:10 to 5: 1.
5. The method for synthesizing dialkyl peroxide according to claim 1, wherein the reaction temperature is-20 to 120 ℃ and the reaction time is 1 to 24 hours.
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| CN201811386024.XA CN109516940B (en) | 2018-11-20 | 2018-11-20 | Method for synthesizing dialkyl peroxide |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104557652A (en) * | 2014-12-22 | 2015-04-29 | 西北师范大学 | Preparation method of tert-butyl peroxide |
| CN105523982A (en) * | 2014-10-23 | 2016-04-27 | 茅海强 | Method for preparing tert-butyl hydroperoxide |
| CN107311906A (en) * | 2017-07-26 | 2017-11-03 | 江苏道明化学有限公司 | A kind of production technology of di-tert-butyl peroxide |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105523982A (en) * | 2014-10-23 | 2016-04-27 | 茅海强 | Method for preparing tert-butyl hydroperoxide |
| CN104557652A (en) * | 2014-12-22 | 2015-04-29 | 西北师范大学 | Preparation method of tert-butyl peroxide |
| CN107311906A (en) * | 2017-07-26 | 2017-11-03 | 江苏道明化学有限公司 | A kind of production technology of di-tert-butyl peroxide |
Non-Patent Citations (1)
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| 含氨基酸环氧交联聚乙烯醇的合成、结构和螯合重金属功能;金漫彤;《浙江工业大学学报》;20091031;第37卷(第5期);第515-519页 * |
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