CN114349598A - Method for preparing 3-methylene-1, 5-pentanediol and 3-methyl-2-pentene-1, 5-diol - Google Patents
Method for preparing 3-methylene-1, 5-pentanediol and 3-methyl-2-pentene-1, 5-diol Download PDFInfo
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Abstract
The present invention relates to a process for the preparation of 3-methylene-1, 5-pentanediol and 3-methyl-2-pentene-1, 5-diol. The method comprises the following steps: injecting a mixture of 3-methyl-3-buten-1-ol, formaldehyde, an aminobenzene sulfonic acid aluminum compound and an inert solvent into a microchannel reactor for reaction. The equipment investment is obviously reduced, the continuous production can be realized, the safe operation can be ensured, the required reaction residence time is short, the reaction conversion rate is not less than 90 percent, and the selectivity is not less than 98 percent.
Description
Technical Field
The invention relates to the field of synthesis of olefin-1, 5-diol, in particular to a method for preparing a mixture of 3-methylene-1, 5-pentanediol and (E/Z) -3-methyl-2-pentene-1, 5-diol by taking 3-methyl-3-butene-1-ol and formaldehyde as raw materials through a condensation reaction.
Background
Olefin-1, 5-diols have wide applications in the field of organic synthesis, particularly the direct hydrogenation thereof to obtain saturated diols, which are widely applied to polymers, resins, plasticizers and synthetic lubricants, and are also important intermediates for the preparation of 3-methyl-valerolactone.
Among them, 3-methylene-1, 5-pentanediol and (E/Z) -3-methyl-2-pentene-1, 5-diol can directly obtain 3-methyl-1, 5-pentanediol (hereinafter abbreviated as MPD) having a variety of unique properties such as non-crystallinity after hydrogenation, and are widely used for preparing polyester resins, alkyd resins for coatings, and the like having special properties, and provide polyurethane with excellent flexibility, high transparency and compatibility.
In the process (U.S. Pat. No. 3,3574773) for preparing 3-methyl-3-buten-1-ol from isobutene and formaldehyde under high temperature and high pressure conditions, a small amount of 3-methylene-1, 5-pentanediol and (E/Z) -3-methyl-2-pentene-1, 5-diol are inevitably produced as by-products, the three types of olefin diols are enriched in a tower kettle after passing through a rectification system, factors such as low content, recovery cost and the like are comprehensively considered, and the industrial device often uses the olefin diols and other components as waste liquid to be subjected to centralized incineration treatment, so that the value of further utilization is lost.
BE817722A discloses a synthesis process for preparing 3-methylene-1, 5-pentanediol by reacting formaldehyde aqueous solution with isobutene at 180-250 ℃ and pH 4-7, wherein the yield can reach a level of 80%.
US4254289 further optimizes the synthesis process, adds two-stage recovery equipment except a core reactor, and additionally adds isobutene and a buffering agent in a reaction system taking 3-methyl-2-pentene-1, 5-diol and formaldehyde as raw materials, wherein the purpose of adding the buffering agent is to keep the pH value of the system at 5.0-6.0.
The process technology for synthesizing 3-methylene-1, 5-pentanediol and (E/Z) -3-methyl-2-pentene-1, 5-diol by the method has good application potential, but still has a plurality of defects: (1) the reaction temperature is basically over 200 ℃, the reaction pressure is over 10MPa, the reaction time is longer, generally more than 30 minutes, more than 1 hour, side reactions are increased, impurities are more, the reaction selectivity is poor, (2) the molar ratio of the isobutene to the formaldehyde can reach 10:1 or even higher, the effective utilization rate of equipment is low, and the energy consumption is increased.
In the prior art, the core reaction device adopts a conventional reactor, such as a high-pressure stirring tank type or a tubular fixed bed type or a slurry bed reactor, and various problems exist in heat and substance transfer, so that a plurality of difficulties are caused.
The superposition of the factors often leads to larger reactor volume required in large-scale production, and under the harsh conditions, the equipment investment is large and the safe operation of the process has higher danger.
Disclosure of Invention
In order to solve the technical difficulties in the aspects of process, engineering equipment and the like in the prior art, the invention provides a method for preparing a mixture of 3-methylene-1, 5-pentanediol and (E/Z) -3-methyl-2-pentene-1, 5-diol by taking 3-methyl-3-butene-1-ol and formaldehyde as raw materials and carrying out condensation reaction by using a microchannel reactor.
A process for preparing a mixture of 3-methylene-1, 5-pentanediol and (E/Z) -3-methyl-2-pentene-1, 5-diol, comprising the steps of: injecting a mixture of 3-methyl-3-buten-1-ol, formaldehyde, an aminobenzenesulfonic acid-based aluminum compound and an inert solvent into a microchannel reactor for reaction to prepare a mixture of 3-methylene-1, 5-pentanediol and (E/Z) -3-methyl-2-pentene-1, 5-diol.
The inner diameter of the microchannel reactor is 10-100 mm.
The reaction temperature is 120-180 ℃; the pressure of the reaction is 1-6 Mpa.
In the reaction of the invention, the retention time of the reaction materials in the microchannel reactor is 5-30 min.
The formaldehyde according to the invention can be in the form of a formaldehyde polymer or an aqueous formaldehyde solution, the molar ratio of the formaldehyde component to the 3-methyl-3-buten-1-ol being from 1:1 to 5: 1.
The aminobenzenesulfonic acid-based aluminum compound of the present invention is used in an amount of 1 to 5 mol% based on the molar amount of aluminum atoms in the compound, based on the molar amount of 3-methyl-3-buten-1-ol.
The aminobenzenesulfonic acid based aluminum compound comprises aminobenzenesulfonic acid and an aluminum compound R3The Al is prepared, and the molar ratio of the aminobenzenesulfonic acid to the aluminum compound is 1-3: 1.
The aminobenzenesulfonic acid includes but is not limited to 3-aminobenzenesulfonic acid, sulfanilic acid, and 2, 4-diaminobenzenesulfonic acid.
The R is3In Al, R is a C1-C5 alkyl group, preferably an ethyl group.
The preparation method of the aminobenzenesulfonic acid based aluminum compound comprises the following steps:
(1) dissolving aminobenzenesulfonic acid in an inert solvent under an inert atmosphere to obtain an aminobenzenesulfonic acid solution;
(2) diluting an aluminum compound by using an inert solvent to obtain an aluminum compound solution;
(3) according to the proportion, the aluminum compound solution is slowly dripped into the aminobenzene sulfonic acid solution to form the catalyst solution.
The catalyst aminobenzenesulfonic acid-based aluminum compound is introduced into the reaction system, so that the carbon-hydrogen bond at the end position of the 3-methyl-3-butene-1-ol can be activated, the activation energy of the condensation reaction is reduced, the 3-methyl-3-butene-1-ol and formaldehyde are easier to react under relatively mild conditions, the reaction speed is accelerated, the occurrence of side reactions is favorably reduced, and the selectivity of the main reaction is improved.
The inert solvent is selected from one or more of alkane, aromatic hydrocarbon, halogenated hydrocarbon, ether and ester solvents, and the mass ratio of the solvent to the 3-methyl-3-butene-1-ol is 1:1 to 10: 1.
The microchannel reactor is made of stainless steel or quartz.
The reaction conversion rate is not lower than 90%, and the selectivity is not lower than 98%.
The invention provides a novel method for preparing a mixture of 3-methylene-1, 5-pentanediol and (E/Z) -3-methyl-2-pentene-1, 5-diol, which has the advantages of obviously reduced equipment investment, realization of continuous production, guaranteed safe operation, short required reaction retention time, high yield of the 3-methylene-1, 5-pentanediol and (E/Z) -3-methyl-2-pentene-1, 5-diol, greatly simplified post-treatment and better industrial application prospect.
Detailed Description
The following examples are intended to illustrate the invention without limiting it in any way:
the analysis method comprises the following steps:
gas chromatograph: agilent7890, chromatography column wax (conversion, selectivity determination), injection port temperature: 300 ℃; the split ratio is 50: 1; the carrier gas flow is 52.8 ml/min; temperature rising procedure: at 150 ℃ for 10min, increasing to 260 ℃ at a rate of 10 ℃/min, for 5min, detector temperature: 280 ℃.
The use of the medicine:
98 wt% of 3-methyl-3-buten-1-ol, Allatin reagent Co.Ltd;
aqueous formaldehyde solution, 50 wt%, Aladdin reagent, Inc.;
98 wt% of 3-aminobenzenesulfonic acid, Aladdin reagent Co., Ltd;
98 wt% of sulfanilic acid, avastin reagent, ltd;
98 wt% of 2, 4-diaminobenzenesulfonic acid, Aladdin reagent Co., Ltd;
triethylaluminum, 99.99 wt%, Aladdin reagent, Inc.;
toluene, 99 wt%, Aladdin reagent, Inc.;
ethyl acetate, 99 wt%, alatin reagent, ltd.
Example 1
A toluene solution containing 0.11g of triethylaluminum was slowly dropped into a toluene solution containing 0.18g of 3-aminobenzenesulfonic acid under an inert atmosphere to prepare a toluene solution containing 0.20g of 3-aminobenzenesulfonic acid.
Injecting a reaction raw material of a toluene solution of 3-aminobenzene aluminum sulfonate, 8.79g of 3-methyl-3-butene-1-ol, 6g of a formaldehyde aqueous solution and additionally added toluene (the total amount of toluene is 8.79g) into a quartz microchannel reactor with the inner diameter of 10mm through a high-pressure pump, controlling the reaction temperature to be 180 ℃, the reaction pressure to be 4Mpa and the retention time to be 20min, collecting a reaction product, and analyzing by using a gas chromatography, wherein the result is shown in Table 1.
Example 2
An ethyl acetate solution containing 0.34g of triethylaluminum was slowly dropped into an ethyl acetate solution containing 1.06g of sulfanilic acid under an inert atmosphere to prepare an ethyl acetate solution containing 1.11g of aluminum p-aminobenzenesulfonate.
Injecting reaction raw materials of ethyl aluminum sulfanilate, 8.789g of 3-methyl-3-butene-1-ol, 12.01g of formaldehyde water solution and supplemented ethyl acetate (the total amount of ethyl acetate is 26.37g) into a quartz microchannel reactor with the inner diameter of 30mm through a high-pressure pump, controlling the reaction temperature to be 190 ℃, the reaction pressure to be 6Mpa and the retention time to be 10min, collecting reaction products, and analyzing by using gas chromatography, wherein the result is shown in table 1.
Example 3
A toluene solution containing 0.57g of triethylaluminum was slowly dropped into a toluene solution containing 2.88g of 2, 4-diaminobenzenesulfonic acid under an inert atmosphere to prepare a toluene solution containing 2.94g of aluminum 2, 4-diaminobenzenesulfonate.
Injecting a toluene solution of 2, 4-diaminobenzene sulfonic acid aluminum, 8.789g of 3-methyl-3-butene-1-ol, 18.02g of formaldehyde solution and a reaction raw material supplemented with toluene (43.94 g of toluene total amount) into a stainless steel microchannel reactor with the inner diameter of 60mm through a high-pressure pump, controlling the reaction temperature at 150 ℃, the reaction pressure at 10MPa and the retention time at 30min, collecting a reaction product, and analyzing by using gas chromatography, wherein the result is shown in table 1.
Example 4
An ethyl acetate solution containing 0.23g of triethylaluminum was slowly dropped into an ethyl acetate solution containing 0.53g of 3-aminobenzenesulfonic acid under an inert atmosphere to prepare an ethyl acetate solution containing 0.57g of 3-aminobenzenesulfonic acid.
Injecting a 3-aminobenzenesulfonic acid aluminum ethyl acetate solution, 8.789g of 3-methyl-3-buten-1-ol, 30.03g of formaldehyde aqueous solution and a reaction raw material supplemented with ethyl acetate (the total amount of ethyl acetate is 61.52g) into a quartz microchannel reactor with the inner diameter of 80mm through a high-pressure pump, controlling the reaction temperature to be 170 ℃, the reaction pressure to be 8Mpa and the retention time to be 5min, collecting a reaction product, and analyzing by using gas chromatography, wherein the result is shown in Table 1.
Example 5
A toluene solution containing 0.46g of triethylaluminum was slowly dropped into a toluene solution containing 1.92g of 2, 4-diaminobenzenesulfonic acid under an inert atmosphere to prepare a toluene solution containing 1.98g of aluminum 2, 4-diaminobenzenesulfonate.
Injecting reaction raw materials of 2, 4-diaminobenzene sulfonic acid aluminum toluene solution, 8.789g of 3-methyl-3-butene-1-ol, 24.02g of formaldehyde solution and additional toluene (the total amount of toluene is 87.89g) into a stainless steel microchannel reactor with the inner diameter of 100mm through a high-pressure pump, controlling the reaction temperature to be 200 ℃, the reaction pressure to be 1Mpa and the retention time to be 25min, collecting reaction products, and analyzing by using gas chromatography, wherein the results are shown in Table 1.
Comparative example 1
8.789g of 3-methyl-3-butene-1-ol, 18.02g of formaldehyde aqueous solution and 43.94g of toluene are prepared into reaction raw materials in advance in an inert atmosphere, the reaction raw materials are injected into a stainless steel microchannel reactor with the inner diameter of 60mm through a high-pressure pump, the reaction temperature is controlled to be 150 ℃, the reaction pressure is controlled to be 10Mpa, the retention time is 30min, reaction products are collected, and the results are shown in table 1 by utilizing gas chromatography analysis.
Comparative example 2
Under an inert atmosphere, 1.11kg of 3-methyl-3-buten-1-ol, 230g of 36.5 wt% aqueous formaldehyde solution, 700g of isopropanol, 3.5g of disodium hydrogen phosphate and 1.3 g of glycolic acid are transferred to a 3.7L autoclave, the pH is controlled to be 5.9, stirring is started, the temperature is increased to 215 ℃, 701g of 36.5 wt% aqueous formaldehyde solution is additionally added through a pump at a certain flow rate, the reaction temperature is kept at 215 ℃, the pressure is kept at 300-500 psig, the reaction is stopped after 65min of reaction, and the temperature is reduced and the pressure is reduced. The results of the analysis by gas chromatography are shown in Table 1.
Comparative example 3
Under an inert atmosphere, 2.88g of 2, 4-diaminobenzenesulfonic acid, 8.789g of 3-methyl-3-buten-1-ol, 18.02g of formaldehyde aqueous solution and 43.94g of toluene are prepared into reaction raw materials in advance, the reaction raw materials are injected into a stainless steel microchannel reactor with the inner diameter of 60mm through a high-pressure pump, the reaction temperature is controlled at 150 ℃, the reaction pressure is 10Mpa, the retention time is 30min, reaction products are collected, and the results are shown in table 1 by utilizing gas chromatography analysis.
Comparative example 4
Under an inert atmosphere, 0.57g of triethylaluminum, 8.789g of 3-methyl-3-buten-1-ol, 18.02g of formaldehyde aqueous solution and 43.94g of toluene were prepared in advance as reaction raw materials, which were injected into a stainless steel microchannel reactor having an inner diameter of 60mm by means of a high-pressure pump, the reaction temperature was controlled at 150 ℃, the reaction pressure was controlled at 10Mpa, the residence time was 30min, and the reaction product was collected and analyzed by gas chromatography, with the results shown in table 1.
TABLE 1 results of the reaction
The alkene-1, 5-diol means 3-methylene-1, 5-pentanediol and (E/Z) -3-methyl-2-pentene-1, 5-diol.
Claims (10)
1. A process for the preparation of 3-methylene-1, 5-pentanediol and 3-methyl-2-pentene-1, 5-diol comprising the steps of: injecting a mixture of 3-methyl-3-buten-1-ol, formaldehyde, an aminobenzenesulfonic acid-based aluminum compound and an inert solvent into a microchannel reactor for reaction to prepare a mixture of 3-methylene-1, 5-pentanediol and 3-methyl-2-pentene-1, 5-diol.
2. The method according to claim 1, wherein the aminobenzenesulfonic acid-based aluminum compound is used in an amount of 1 to 5 mol% based on the molar amount of aluminum atoms in the compound, based on the molar amount of 3-methyl-3-buten-1-ol.
3. The method as claimed in claim 1, wherein said aminobenzenesulfonic acid-based aluminum compound comprises aminobenzenesulfonic acid and aluminum compound R3The Al is prepared, and the molar ratio of the aminobenzenesulfonic acid to the aluminum compound is 1-3: 1.
4. The method of claim 3, wherein said aminobenzenesulfonic acid is selected from the group consisting of 3-aminobenzenesulfonic acid, sulfanilic acid, and 2, 4-diaminobenzenesulfonic acid.
5. Process according to claim 3, characterized in that the aluminium compound R3In Al, R is a C1-C5 alkyl group, preferably an ethyl group.
6. The method according to any one of claims 1 to 5, wherein the method for preparing the aminobenzenesulfonic acid based aluminum compound comprises the following steps:
(1) dissolving aminobenzenesulfonic acid in an inert solvent under an inert atmosphere to obtain an aminobenzenesulfonic acid solution;
(2) diluting an aluminum compound by using an inert solvent to obtain an aluminum compound solution;
(3) according to the proportion, the aluminum compound solution is slowly dripped into the aminobenzene sulfonic acid solution to form the catalyst solution.
7. The method according to claim 1, wherein the reaction temperature is 120-180 ℃; the pressure of the reaction is 1-6 Mpa.
8. The method of claim 1, wherein the microchannel reactor has an inner diameter of 10 to 100 mm.
9. The method of claim 1, wherein the residence time of the reaction mass in the microchannel reactor is 5 to 30 min.
10. The method of claim 1, wherein the formaldehyde is a formaldehyde polymer or an aqueous solution of formaldehyde, and the molar ratio of the formaldehyde to the 3-methyl-3-buten-1-ol is 1:1 to 5: 1.
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Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1458097A (en) * | 1973-07-16 | 1976-12-08 | Chevron Res | Process for the production of alkene-1,5-diols |
US4254289A (en) * | 1977-01-12 | 1981-03-03 | Chevron Research Company | Process for the production of alkene-1,5-diols |
RU2744099C1 (en) * | 2020-09-15 | 2021-03-02 | Общество с ограниченной ответственностью "Научно-производственное объединение ЕВРОХИМ" | Method for producing 3-methyl-3-buten-1-ol |
CN112495430A (en) * | 2020-11-13 | 2021-03-16 | 万华化学集团股份有限公司 | Modified molecular sieve catalyst and application thereof in treatment of high-concentration wastewater of 3-methyl-3-buten-1-ol |
US20220169586A1 (en) * | 2019-03-21 | 2022-06-02 | Basf Se | Process to recover 3-methyl-but-3-en-1-ol |
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- 2022-01-18 CN CN202210054456.0A patent/CN114349598B/en active Active
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1458097A (en) * | 1973-07-16 | 1976-12-08 | Chevron Res | Process for the production of alkene-1,5-diols |
US4254289A (en) * | 1977-01-12 | 1981-03-03 | Chevron Research Company | Process for the production of alkene-1,5-diols |
US20220169586A1 (en) * | 2019-03-21 | 2022-06-02 | Basf Se | Process to recover 3-methyl-but-3-en-1-ol |
RU2744099C1 (en) * | 2020-09-15 | 2021-03-02 | Общество с ограниченной ответственностью "Научно-производственное объединение ЕВРОХИМ" | Method for producing 3-methyl-3-buten-1-ol |
CN112495430A (en) * | 2020-11-13 | 2021-03-16 | 万华化学集团股份有限公司 | Modified molecular sieve catalyst and application thereof in treatment of high-concentration wastewater of 3-methyl-3-buten-1-ol |
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