CN113388851B - Electrochemical method for synthesizing 1,10-decanediol - Google Patents

Electrochemical method for synthesizing 1,10-decanediol Download PDF

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CN113388851B
CN113388851B CN202110635361.3A CN202110635361A CN113388851B CN 113388851 B CN113388851 B CN 113388851B CN 202110635361 A CN202110635361 A CN 202110635361A CN 113388851 B CN113388851 B CN 113388851B
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caprolactone
reaction
epsilon
decanediol
electrode
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CN113388851A (en
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栾谨鑫
杜旺明
钱向阳
张永振
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Wanhua Chemical Group Co Ltd
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Abstract

The invention provides an electrochemical method for synthesizing 1,10-decanediol, which comprises the following steps: 1) mixing epsilon-caprolactone, alkaline electrolyte, organic solvent and water, and then heating and stirring to perform hydrolysis reaction on the epsilon-caprolactone in the system to generate 6-hydroxycaproic salt; 2) adding sodium carbonate, sodium formate and water into the hydrolyzed system in the step 1), stirring and dissolving, then carrying out electrolytic reaction, and obtaining the 1,10-decanediol after the reaction is finished. The method can solve the problems of low product total yield, large equipment investment, high operation risk, harsh reaction conditions, prominent three-waste problem and the like of the traditional synthesis process. Meanwhile, the problems of instability, easy self-polymerization and the like in the existing electrochemical method can be effectively avoided.

Description

Electrochemical method for synthesizing 1,10-decanediol
Technical Field
The invention belongs to the field of organic synthesis, and relates to an electrochemical method for synthesizing 1, 10-decanediol.
Background
1,10-Decanediol (1, 10-decadiol) is also called 1, 10-dihydroxydecane, is a fine chemical raw material and a medical intermediate, is mainly used for manufacturing medicines and fine chemical products, such as producing diiododecane to prepare medicines such as antibacterial and antifungal drugs (bis) clonidine and octenidine, has more and more applications in the fields of novel polyurethane, polyester, plasticizer, pesticide, lubricant additive and the like, and is mainly used for improving the mechanical strength of products and improving the hydrolysis resistance, heat resistance, chemical corrosion resistance and other properties of the products.
The conventional production process of 1,10-decanediol is as follows: firstly, ricinoleic acid is pyrolyzed at high temperature to prepare 1, 10-decanedioic acid, decanedioic acid is esterified with methanol to generate dimethyl decanedioate, then 1,10-decanediol is prepared by hydrogenation, and finally a pure product is obtained by rectification and purification, wherein esterification and hydrogenation reduction processes are very mature, so that the preparation of the decanedioic acid by pyrolyzing the castor oil at high temperature in the whole process is the key point and difficulty of the production process. The preparation of sebacic acid by pyrolysis of castor oil comprises the following steps: castor oil is first catalyzed and hydrolyzed or saponified with alkali to produce ricinoleic acid, and then phenol is used as diluent to produce disodium sebacate, octanol, hydrogen and small amount of sodium sebacate via alkali cracking at 280 deg.c. Dissolving the disodium sebacate in water, neutralizing with sulfuric acid to obtain monosodium sebacate, decolorizing with resin and active carbon, and acidifying with sulfuric acid to obtain sebacic acid. The industrial grade sebacic acid is obtained through the steps of cooling, crystallization, separation, washing, drying and the like.
The above-mentioned manufacturing method has several problems as follows: long production period, poor product quality, toxic phenols, corrosion to equipment and environmental pollution. About 2.2 tons of castor oil, 1.68 tons of 98 percent concentrated sulfuric acid and 1.17 tons of concentrated alkali liquor are consumed for producing one ton of sebacic acid, and more than 30 tons of phenol-containing wastewater and a large amount of wastewater and waste residues are generated, wherein the pH value of the wastewater is 2-3, and the concentration of phenolic substances is 2000-3000 ppm. The phenol substance has high toxicity, the phenol-containing waste water is difficult to treat, and the pollution to the environment is great, so the method is the primary problem restricting the development of the industry.
At present, the electrochemical synthesis of dimethyl sebacate is reported in documents, 1,10-decanediol is synthesized by only adopting electrochemical synthesis, the inventor synthesizes the 1,10-decanediol by adopting a document method for synthesizing the dimethyl sebacate, and the inventor surprisingly finds that the 6-hydroxycaproic acid salt used as a raw material for synthesizing the 1,10-decanediol is unstable in the electrolytic process, is easy to generate needle-shaped precipitates by self-polymerization, and is attached to the surface of an electrode and the inner wall of an electrolytic bath to cause electrolytic voltage fluctuation. Meanwhile, 6-hydroxy caproate can generate side reaction at the anode to generate adipate, and the reaction selectivity and the current efficiency are reduced. Therefore, the electrochemical method for synthesizing 1,10-decanediol is to be further developed.
Disclosure of Invention
The invention provides an electrochemical method for synthesizing 1,10-decanediol, which can solve the problems of low product total yield, large equipment investment, high operation risk, harsh reaction conditions, outstanding three-waste problem and the like in the traditional synthesis process. Meanwhile, the problems of instability, easy self-polymerization and the like in the existing electrochemical method can be effectively avoided.
In order to solve the technical problems, the invention is realized by the following technical scheme:
an electrochemical process for the synthesis of 1,10-decanediol, comprising the steps of:
1) mixing epsilon-caprolactone, alkaline electrolyte, organic solvent and water, and then heating and stirring to perform hydrolysis reaction on the epsilon-caprolactone in the system to generate 6-hydroxycaproic salt;
2) adding sodium carbonate, sodium formate and water into the hydrolyzed system in the step 1), stirring and dissolving, then carrying out electrolytic reaction, and obtaining the 1,10-decanediol after the reaction is finished.
In step 1) of the present invention, the amount of the alkaline electrolyte is 15 to 30% by mole, such as 15%, 20%, 22%, 25%, 28%, 30%, preferably 20 to 25% of the mole of epsilon-caprolactone;
the alkaline electrolyte is any one or combination of at least two of potassium methoxide, sodium methoxide, potassium hydroxide, sodium hydroxide and triethylamine, and preferably potassium methoxide and/or potassium hydroxide.
In the step 1) of the invention, the mass ratio of the epsilon-caprolactone to the organic solvent is 0.5:1-2:1, preferably 1:1-1.2: 1;
the organic solvent adopted by the electrolytic system is selected conventionally in the field, no special requirement exists, and all organic solvents which can effectively dissolve adipate raw materials and do not have any adverse effect on the electrolytic system can be selected as the organic solvent of the electrolytic system; preferably, the organic solvent is any one or a combination of at least two of benzene, pyridine, nitrile and alcohol solvents, and more preferably any one or a combination of at least two of benzene, pyridine, acetonitrile, methanol, ethanol and propanol.
In step 1) of the invention, the addition amount of the water is 5-30%, preferably 10-20% of the mass of the epsilon-caprolactone.
In the step 1), the hydrolysis reaction is carried out at the reaction temperature of 60-100 ℃, preferably 80-90 ℃; the reaction time is 0.5-2h, preferably 1-1.5 h.
In the step 2), the molar ratio of the sodium carbonate to the epsilon-caprolactone in the step 1) is 0.3-0.6: 1, preferably 0.4 to 0.5: 1;
the molar ratio of the sodium formate to the epsilon-caprolactone in the step 1) is 0.2-0.4: 1, preferably 0.2 to 0.3: 1.
in step 2) of the present invention, water is added for dissolving sodium carbonate and sodium formate, and the amount of water added is not particularly limited, and it is preferable that the sodium carbonate and sodium formate added to the system can be completely dissolved. In step 2) of the present inventionThe electrolytic reaction is carried out in an electrolytic potential range of 2 to 3V, for example, 2.0V, 2.2V, 2.4V, 2.5V, 2.8V, 2.9V, 3V, preferably 2.5 to 2.8V; the electrolytic current density is 1200-2000A/m2For example 1200A/m2、1400A/m2、1500A/m2、1600A/m2、1700A/m2、1800A/m2、1900A/m2、2000A/m2Preferably 1600-1800A/m2。
In step 2) of the present invention, the temperature of the electrolyte in the electrolysis reaction is 40-60 deg.C, such as 40 deg.C, 45 deg.C, 50 deg.C, 55 deg.C, 60 deg.C, preferably 50-60 deg.C;
the electrolysis reaction is carried out for 5 to 20 hours, such as 5 hours, 10 hours, 15 hours and 20 hours, and preferably 10 to 15 hours;
and the pH value of the electrolyte is 8-10 in the electrolytic reaction.
In step 2) of the present invention, the electrolytic reaction is carried out in an electrolytic cell comprising an anode and a cathode;
preferably, the anode is a platinum electrode, a platinum titanium electrode or a DSA electrode, preferably a Ti-based PbO electrode2、IrO2、RuO2Or a tin antimony oxide electrode;
preferably, the cathode is Pb/Ag/TiO2Composite metal electrode, more preferably, the Pb/Ag/TiO2The composite metal electrode is prepared by the following method:
(1) graphite as cathode and titanium as anode are put into acetic acid solution containing HF for oxidation reaction under constant voltage, and after the reaction is finished, the solution is washed with water, dried and roasted to obtain TiO2An electrode;
(2) TiO obtained in the step (1)2The electrode is a working electrode, the Pb-Ag electrode is a counter electrode, and the current density in the electroplating solution composed of lead methane sulfonate, silver methane sulfonate, sulfonic acid and water is 10-60mA/cm2After the bottom deposition is carried out for 30 to 180 seconds, the Pb/Ag/TiO is prepared2A composite metal electrode.
In the step (1), the graphite cathode and the titanium anode are in the same shape and size, the shape and size of the electrode are not particularly required, and in some examples, the shapes such as a circle, a rectangle and a rhombus are preferably adopted; the size is preferably 3 x 3-5 x 5 cm.
In the step (1), the acetic acid aqueous solution containing HF comprises the following components in percentage by mass: 5-20% of acetic acid, 0.02-0.1% of HF and the balance of water (deionized water); preferably, the weight percentage composition is as follows: 10-15% of acetic acid, 0.04-0.08% of HF and the balance of water (deionized water).
In the step (1), the oxidation reaction is carried out at the temperature of 20-50 ℃, preferably 30-40 ℃ for 1-3h, preferably 1.5-2 h;
preferably, the voltage applied in the oxidation process is 25-50V, preferably 30-40V; the current density is 5-10mA/cm2Preferably 6-8mA/cm2；
Preferably, the distance between the two electrodes is 0.5-2.5 cm.
In the step (1), the titanium anode is polished until the surface of the anode has no scratch, and the anode is placed into water (deionized water) for ultrasonic cleaning for 10-30min and dried for use.
In the preparation method, in the step (1), after the reaction is finished, washing, drying and roasting are conventional operations in the field, for example, deionized water is adopted for washing and drying, and then the reaction product is placed in a muffle furnace for roasting; forming a layer of TiO on the surface of the titanium metal anode substrate after roasting treatment2Nanotube array films or nanoparticle films;
preferably, the roasting temperature is 300-700 ℃, preferably 500-600 ℃, the time is 1-5h, preferably 2-3h, and the temperature rise rate is 2-20 ℃/min, preferably 5-10 ℃/min.
In the step (2), the concentration of Pb ions in the electroplating solution is 0.3-0.4mol/L, the concentration of Ag ions in the electroplating solution is 0.2-0.3mol/L, the content of sulfonic acid is 14-20 wt%, and the balance is water.
The invention does not limit the shape and arrangement of the electrodes in the electrolytic bath, and all the shapes and cathode and anode arrangements of the electrodes which can realize the electrolysis function are covered in the method of the invention.
In step 2), after the electrolysis reaction is finished, the obtained reaction system contains a mixture of 1,10-decanediol and 1,10-decanediol diformate, and preferably, the method comprises hydrolyzing and converting the 1,10-decanediol diformate into 1,10-decanediol through a hydrolysis reaction;
preferably, the hydrolysis reaction is carried out at the hydrolysis temperature of 80-100 ℃ for 0.5-2 h;
preferably, after the electrolysis reaction is finished, the post-treatment processes such as desolventizing, dehydrogenation and de-weighting are also included, for the conventional operation in the field, for example, in some examples, the reaction solution obtained from the hydrolysis reaction is preferably sequentially passed through a desolventizing tower, a dehydrogenation tower and a de-weighting tower to obtain the 1, 10-decanediol.
The invention introduces sodium formate and sodium carbonate into the electrolytic system at the same time, and the addition of sodium carbonate and sodium formate mainly aims at controlling the pH of the electrolytic reaction system and inhibiting the self-polymerization reaction of 6-hydroxy caproate in the electrolytic process. The inventor unexpectedly finds that the pH value of the electrolyte is controlled to be 8-10 in the step 2) electrolysis reaction, so that the self-polymerization reaction of the 6-hydroxycaproic acid salt can be effectively inhibited, and therefore, an alkaline medium needs to be added into the 6-hydroxycaproic acid salt solution obtained in the step A, if sodium carbonate and sodium formate are used as the alkaline medium, the addition of sodium formate can reduce the oxidation side reaction of the 6-hydroxycaproic acid salt on the anode, and on the other hand, the sodium formate and the 6-hydroxycaproic acid salt react in the anode area to generate the 6-formyloxy caproic acid salt, and the 6-formyloxy caproic acid salt is further electrolyzed to generate the 1, 10-decanedioic acid ester. In addition, the sodium carbonate added into the electrolytic system can inhibit the self-polymerization reaction of the 6-hydroxyhexanoate in the electrolytic process, and the sodium carbonate is reduced at the cathode to generate sodium formate, so that the loss of the sodium formate is reduced.
The invention adopts an electrochemical method to synthesize 1,10-decanediol, uses epsilon-caprolactone as a raw material, firstly hydrolyzes to generate 6-hydroxycaproic acid salt, then generates a mixture of 1,10-decanediol and 1,10-decanediol diformate through an electrolytic reaction, and the 1,10-decanediol diformate is further hydrolyzed to generate the 1, 10-decanediol. The sodium carbonate is added into an electrolytic reaction system, so that the self-polymerization reaction of the 6-hydroxycaproic acid salt in the electrolytic process is inhibited, the problem of electrolytic voltage fluctuation caused by the fact that precipitates generated by self-polymerization are attached to the surface of an electrode and the inner wall of an electrolytic cell is solved, the stability in the electrolytic process is good, and the reaction selectivity and the current efficiency are high.
Compared with the traditional synthesis process, the method has the advantages of high total product yield, small equipment investment, low operation risk and mild reaction conditions, and is suitable for wide industrial application.
Detailed Description
The present invention is further illustrated by the following specific examples, which are intended to be illustrative of the invention and are not to be construed as limiting the scope of the invention.
The main raw material information is as follows:
epsilon-caprolactone, Shanghai Michelin Biochemical technology Limited, product Specification > 99%;
potassium methoxide, Shanghai Michelin Biochemical technology Limited, product specification > 95%;
sodium methoxide, Beijing Bailingwei science and technology Limited, product specification > 95%;
potassium hydroxide, Beijing Bailingwei science and technology Limited, product specification > 85%;
sodium hydroxide, Beijing Bailingwei science and technology Limited, product specification > 85%;
lead methane sulfonate, Shanghai Michelin Biochemical technology, Inc., 50 wt% aqueous solution of product specification;
silver methane sulfonate, Shanghai Allantin Biotechnology Limited, product Specification > 98%;
sulfonic acid, Shanghai Aladdin Biotechnology Limited, product Specification > 98%;
Pb-Ag electrode, Xinlixing nonferrous alloys Co., Ltd, Shenyang, under the designation PbAg1.0;
a platinum titanium electrode, Siam Tai gold, Inc., with a plating thickness of 1 μm;
ti radical IrO2An anode, Jiangsu Yianteng special electrode Co., Ltd., an iridium titanium mesh 50 x 100;
ti-based PbO2Anode, Jiangsu Yianteng special electrode Co., Ltd., lead-titanium mesh 50X 100;
ti-based RuO2An anode, Jiangsu Yianteng Special electrode Co., Ltd,ruthenium titanium mesh 50 x 100.
Other raw materials or reagents are commercially available unless otherwise specified.
The hydrogen spectra of 1,10-decanediol in the following examples were characterized by NMR spectroscopy (Brucker ARX-400).
Example 1
Preparation of Pb/Ag/TiO2A composite metal electrode:
polishing a titanium metal anode (round and 3cm in diameter) until the surface is free of scratches, putting the titanium metal anode into deionized water, ultrasonically cleaning for 10min, and drying for later use;
preparing an acetic acid aqueous solution containing HF, wherein the acetic acid aqueous solution comprises the following components in percentage by mass: 5% of acetic acid, 0.02% of HF and the balance of deionized water for later use;
the electroplating solution is composed of mixed solution of lead methane sulfonate, silver methane sulfonate, sulfonic acid and water, wherein: the concentration of Pb ions of the lead methane sulfonate is 0.3mol/L, the concentration of Ag ions of the silver methane sulfonate is 0.2mol/L, the content of the sulfonic acid is 14 wt%, and the balance is deionized water.
(1) Graphite with the same shape and size is used as a cathode, titanium metal is used as an anode, the anode is placed into acetic acid aqueous solution containing HF, the distance between the two electrodes is 2.5cm, and the graphite is placed under the conditions of constant voltage of 25V and current density of 5mA/cm2Then oxidation reaction is carried out, reaction is carried out for 3h at 20 ℃, deionized water is used for washing and drying after the reaction is finished, and the obtained product is placed in a muffle furnace, heated to 300 ℃ at a speed of 2 ℃/min and roasted for 5h to obtain TiO2An electrode;
(2) TiO obtained in the step (1)2The electrode is a working electrode, the Pb-Ag electrode is a counter electrode, and the current density in the electroplating solution is 10mA/cm2Depositing for 180s to obtain Pb/Ag/TiO2A composite metal electrode.
Example 2
Preparation of Pb/Ag/TiO2A composite metal electrode:
polishing a titanium metal anode (rectangular and 4 x 4cm in size) until the surface is free of scratches, putting the titanium metal anode into deionized water, ultrasonically cleaning for 10min, and drying for later use;
preparing an acetic acid aqueous solution containing HF, wherein the acetic acid aqueous solution comprises the following components in percentage by mass: 10% of acetic acid, 0.04% of HF and the balance of deionized water for later use;
the electroplating solution is composed of mixed solution of lead methane sulfonate, silver methane sulfonate, sulfonic acid and water, wherein: the concentration of Pb ions of the lead methane sulfonate is 0.4mol/L, the concentration of Ag ions of the silver methane sulfonate is 0.3mol/L, the content of the sulfonic acid is 17 wt%, and the balance is deionized water.
(1) Graphite with the same area is used as a cathode, titanium metal is used as an anode, the graphite and the titanium metal are placed into acetic acid aqueous solution containing HF, the distance between the two electrodes is 2cm, and the graphite and the titanium metal are placed under the conditions that the constant voltage is 30V and the current density is 6mA/cm2Then oxidation reaction is carried out for 2h at 30 ℃, deionized water is used for washing and drying after the reaction is finished, and the mixture is placed in a muffle furnace for heating to 500 ℃ at the speed of 5 ℃/min and then is roasted for 3h to obtain TiO2An electrode;
(2) TiO obtained in the step (1)2The electrode is a working electrode, the Pb-Ag electrode is a counter electrode, and the current density in the electroplating solution is 30mA/cm2Depositing for 120s to obtain Pb/Ag/TiO2A composite metal electrode.
Example 3
Preparation of Pb/Ag/TiO2Composite metal nano-electrode:
polishing a titanium metal anode (diamond, size 5 x 5cm), putting the titanium metal anode into deionized water, ultrasonically cleaning for 10min, and drying for later use;
preparing an acetic acid aqueous solution containing HF, wherein the acetic acid aqueous solution comprises the following components in percentage by mass: 15% of acetic acid, 0.08% of HF and the balance of deionized water for later use;
the electroplating solution is composed of mixed solution of lead methane sulfonate, silver methane sulfonate, sulfonic acid and water, wherein: the concentration of Pb ions of the lead methane sulfonate is 0.3mol/L, the concentration of Ag ions of the silver methane sulfonate is 0.3mol/L, the content of the sulfonic acid is 20 wt%, and the balance is deionized water.
(1) Graphite with the same area is used as a cathode, titanium metal is used as an anode, the graphite and the titanium metal are placed into acetic acid aqueous solution containing HF, the distance between the two electrodes is 1cm, and the graphite and the titanium metal are placed under the conditions of constant voltage of 40V and current density of 8mA/cm2Then oxidation reaction is carried out for 1.5h at 40 ℃, deionized water is used for washing and drying after the reaction is finished, and the mixture is placed in a muffle furnace for heating up to 600 ℃ at a speed of 10 ℃/min and then roasted for 2h to obtain TiO2An electrode;
(2) TiO obtained in the step (1)2The electrode is a working electrode, the Pb-Ag electrode is a counter electrode, and the current density in the electroplating solution is 50mA/cm2After depositing for 60s, Pb/Ag/TiO is prepared2A composite metal electrode.
Example 4
Preparation of Pb/Ag/TiO2Composite metal nano-electrode:
polishing a titanium metal anode (circular, 5 x 5cm in size) until the surface has no scratch, putting the titanium metal anode into deionized water, ultrasonically cleaning for 10min, and drying for later use;
preparing an acetic acid aqueous solution containing HF, wherein the acetic acid aqueous solution comprises the following components in percentage by mass: 20% of acetic acid, 0.1% of HF and the balance of deionized water for later use;
the electroplating solution is composed of mixed solution of lead methane sulfonate, silver methane sulfonate, sulfonic acid and water, wherein: the concentration of Pb ions of the lead methane sulfonate is 0.4mol/L, the concentration of Ag ions of the silver methane sulfonate is 0.2mol/L, the content of the sulfonic acid is 20 wt%, and the balance is deionized water.
(1) Graphite with the same area is used as a cathode, titanium metal is used as an anode, the graphite and the titanium metal are placed into acetic acid aqueous solution containing HF, the distance between the two electrodes is 0.5cm, and the graphite and the titanium metal are placed under the conditions that the constant voltage is 50V and the current density is 10mA/cm2Then carrying out oxidation reaction for 1h at 50 ℃, washing with deionized water after the reaction is finished, drying, placing in a muffle furnace for heating to 700 ℃ at a speed of 20 ℃/min, and roasting for 1h to obtain TiO2An electrode;
(2) TiO obtained in the step (1)2The electrode is a working electrode, the Pb-Ag electrode is a counter electrode, and the current density in the electroplating solution is 60mA/cm2Depositing for 30s to obtain Pb/Ag/TiO2A composite metal electrode.
Example 5
Electrochemical preparation of 1, 10-decanediol:
1) 115g (1mol) of epsilon-caprolactone, 230g of benzene, 10.5g (0.15mol) of potassium methoxide and 5.75g of water are uniformly mixed, wherein the mass ratio of the epsilon-caprolactone to the organic solvent benzene in the reaction system is 0.5:1, the addition amount of electrolyte potassium methoxide accounts for 15% of the molar amount of the epsilon-caprolactone, and the addition amount of water accounts for 5% of the mass of the epsilon-caprolactone. Then stirring and heating to 60 ℃ for hydrolysis reaction for 2h to generate 6-hydroxycaproic acid salt, wherein the nuclear magnetic hydrogen spectrum data is as follows:
1H NMR(600MHz,CDCl3)：δ8.04(1H)，4.21(2H)，1.29(2H)，1.52(2H)，2.30(2H)，1.62(2H)。
2) adding 31.8g (0.3mol) of sodium carbonate and 21.2g (0.4mol) of sodium formate into the hydrolyzed system in the step 1), adding 20g of water, stirring until the sodium carbonate and the epsilon-caprolactone are completely dissolved, wherein the molar ratio of the added amount of the sodium carbonate to the epsilon-caprolactone is 0.3: 1, the molar ratio of the sodium formate addition amount to epsilon-caprolactone is 0.4: 1, the pH of the electrolyte was controlled to 10. The mixed material was transferred to an electrolytic cell using a platinum titanium anode and a Pb/Ag/TiO cathode as prepared in example 12A composite metal electrode. Electrolytic reaction is carried out for 20 hours at the temperature of 40 ℃, and the current density of an electrolytic cell is 1200A/m2And an electrolytic potential of 2V. After the electrolysis reaction is finished, the obtained reaction system contains a mixture of 1,10-decanediol and 1,10-decanediol diformate (the selectivity of the 1,10-decanediol is 42.2 percent), then the mixture is hydrolyzed at 100 ℃ for 0.5h, then the materials sequentially pass through a desolventizing tower, a dehydrogenation tower and a de-heavy tower, and a pure product of the 1,10-decanediol is obtained by collection, wherein the nuclear magnetic hydrogen spectrum data is as follows:
1H NMR(600MHz,CDCl3)：δ3.65(2H)，3.50(4H)，1.53(4H)，1.43(4H)，1.29(8H)。
in this example, the conversion rate of the raw material epsilon-caprolactone is 90.8%, the selectivity of the synthesized 1,10-decanediol is 89.0%, the current efficiency is 81.2%, the selectivity of the 6-hydroxycaproic acid salt from the polymerization product is 3.1%, and the electrolytic voltage rising rate is 0.01V/h.
Example 6
Electrochemical preparation of 1, 10-decanediol:
1) 115g (1mol) of epsilon-caprolactone, 192g of pyridine, 10.8g (0.2mol) of sodium methoxide and 9.2g of water are uniformly mixed, wherein the mass ratio of the epsilon-caprolactone to the organic solvent pyridine in the reaction system is 0.6:1, the addition amount of the sodium methoxide serving as an electrolyte accounts for 20 mol percent of the epsilon-caprolactone, and the addition amount of the water accounts for 8mol percent of the epsilon-caprolactone. Then stirring and heating to 70 ℃ for hydrolysis reaction for 1.5h to generate 6-hydroxycaproic acid salt.
2) Go to stepAdding 31.8g (0.3mol) of sodium carbonate and 27.2g (0.4mol) of sodium formate into the hydrolyzed system in the step 1), adding 20g of water, stirring until the sodium carbonate and the epsilon-caprolactone are completely dissolved, wherein the mol ratio of the added amount of the sodium carbonate to the epsilon-caprolactone is 0.3: 1, the molar ratio of the addition amount of sodium formate to epsilon-caprolactone is 0.4: 1, the pH of the electrolyte was controlled to 9.5. The mixed material was transferred to an electrolytic cell using a platinum titanium anode and a Pb/Ag/TiO cathode as prepared in example 22A composite metal electrode. The electrolytic reaction is carried out for 15 hours at the temperature of 45 ℃, and the current density of an electrolytic cell is 1400A/m2And the electrolytic potential is 2.2V. After the electrolysis reaction is finished, the obtained reaction system contains a mixture of 1,10-decanediol and 1,10-decanediol diformate (the selectivity of the 1,10-decanediol is 43.1 percent), then the mixture is hydrolyzed at 90 ℃ for 1h, and the materials sequentially pass through a desolventizing tower, a dehydrogenation tower and a de-heavy tower to be collected to obtain a pure product of the 1, 10-decanediol.
In this example, the conversion rate of the raw material epsilon-caprolactone is 85.6%, the selectivity of the synthesized 1,10-decanediol is 91.2%, the current efficiency is 83.9%, the selectivity of the 6-hydroxycaproic acid salt from the polymerization product is 4.2%, and the electrolytic voltage rising rate is 0.02V/h.
Example 7
Electrochemical preparation of 1, 10-decanediol:
1) 115g (1mol) of epsilon-caprolactone, 144g of acetonitrile, 12.3g (0.22mol) of potassium hydroxide and 11.5g of water are uniformly mixed, wherein the mass ratio of the epsilon-caprolactone to the organic solvent acetonitrile in the reaction system is 0.8:1, the addition amount of electrolyte potassium hydroxide is 22 percent of the mole amount of the epsilon-caprolactone according to the mole amount, and the addition amount of the water is 10 percent of the mass of the epsilon-caprolactone. Then stirring and heating to 80 ℃ for hydrolysis reaction for 1h to generate 6-hydroxycaproic acid salt.
2) Adding 42.4g (0.4mol) of sodium carbonate and 20.4g (0.3mol) of sodium formate into the hydrolyzed system in the step 1), adding 20g of water, stirring until the sodium carbonate and the epsilon-caprolactone are completely dissolved, wherein the molar ratio of the added amount of the sodium carbonate to the epsilon-caprolactone is 0.4: 1, the molar ratio of the addition amount of sodium formate to epsilon-caprolactone is 0.3: 1, the pH of the electrolyte was controlled to 9.0. Transferring the mixed materials into an electrolytic cell, wherein the anode of the electrolytic cell adopts Ti-based PbO2The anode and the cathode adopt the Pb/Ag/TiO prepared in example 32CompoundingAnd a metal electrode. Electrolytic reaction is carried out for 10 hours at the temperature of 50 ℃, and the current density of an electrolytic cell is 1500A/m2And the electrolytic potential is 2.4V. After the electrolysis reaction is finished, the obtained reaction system contains a mixture of 1,10-decanediol and 1,10-decanediol diformate (the selectivity of the 1,10-decanediol is 46.5 percent), then the mixture is hydrolyzed at 80 ℃ for 2 hours, and the materials sequentially pass through a desolventizing tower, a dehydrogenation tower and a de-heavy tower to be collected to obtain a pure product of the 1, 10-decanediol.
In this example, the conversion rate of the raw material epsilon-caprolactone is 90.1%, the selectivity of the synthesized 1,10-decanediol is 86.9%, the current efficiency is 80.5%, the selectivity of the 6-hydroxycaproic acid salt from the polymerization product is 2.8%, and the electrolytic voltage rising rate is 0.01V/h.
Example 8
Electrochemical preparation of 1, 10-decanediol:
1) 115g (1mol) of epsilon-caprolactone, 115g of methanol, 10g (0.25mol) of potassium hydroxide and 17.25g of water are uniformly mixed, wherein the mass ratio of the epsilon-caprolactone to the organic solvent methanol in the reaction system is 1:1, the addition amount of electrolyte potassium hydroxide is 25 percent of the molar amount of the epsilon-caprolactone according to the molar amount, and the addition amount of the water is 15 percent of the mass of the epsilon-caprolactone. Then stirring and heating to 90 ℃ for hydrolysis reaction for 1h to generate 6-hydroxycaproic acid salt.
2) Adding 42.4g (0.4mol) of sodium carbonate and 20.4g (0.3mol) of sodium formate into the hydrolyzed system in the step 1), adding 20g of water, stirring until the sodium carbonate and the epsilon-caprolactone are completely dissolved, wherein the molar ratio of the addition amount of the sodium carbonate to the epsilon-caprolactone is 0.4: 1, the molar ratio of the addition amount of sodium formate to epsilon-caprolactone is 0.3: 1, controlling the pH value of the electrolyte to be 8.5. Transferring the mixed materials into an electrolytic cell, wherein the anode of the electrolytic cell adopts Ti-based RuO2The anode and the cathode adopt the Pb/Ag/TiO prepared in example 42A composite metal electrode. Electrolytic reaction is carried out for 5 hours at the temperature of 55 ℃, and the current density of an electrolytic cell is 1600A/m2And the electrolytic potential is 2.5V. After the electrolysis reaction is finished, the obtained reaction system contains a mixture of 1,10-decanediol and 1,10-decanediol diformate (the selectivity of the 1,10-decanediol is 42.9 percent), then the mixture is hydrolyzed at 100 ℃ for 0.5h, and then the materials sequentially pass through a desolventizing tower, a dehydrogenation tower and a de-heavy tower, and the pure 1,10-decanediol is obtained after collection.
In this example, the conversion rate of the raw material epsilon-caprolactone is 92.5%, the selectivity of the synthesized 1,10-decanediol is 91%, the current efficiency is 81.8%, the selectivity of the 6-hydroxycaproic acid salt to the polymeric product is 3.4%, and the electrolytic voltage rising rate is 0.02V/h.
Example 9
Electrochemical preparation of 1, 10-decanediol:
1) 115g (1mol) of epsilon-caprolactone, 95.8g of ethanol, 28.3g (0.28mol) of triethylamine and 23g of water are uniformly mixed, wherein the mass ratio of the epsilon-caprolactone to the organic solvent ethanol in a reaction system is 1.2:1, the addition amount of triethylamine serving as an electrolyte accounts for 28mol percent of the epsilon-caprolactone, and the addition amount of the water accounts for 20 mol percent of the epsilon-caprolactone. Then stirring and heating to 100 ℃, and carrying out hydrolysis reaction for 0.5h to generate 6-hydroxycaproic acid salt.
2) Adding 53g (0.5mol) of sodium carbonate and 13.6g (0.2mol) of sodium formate into the hydrolyzed system in the step 1), adding 20g of water, stirring until the sodium carbonate and the epsilon-caprolactone are completely dissolved, wherein the molar ratio of the addition amount of the sodium carbonate to the epsilon-caprolactone is 0.5:1, the molar ratio of the addition amount of sodium formate to epsilon-caprolactone is 0.2: 1, controlling the pH value of the electrolyte to be 8.0. The mixed material was transferred to an electrolytic cell using a platinum titanium anode and a Pb/Ag/TiO cathode as prepared in example 12A composite metal electrode. Electrolytic reaction is carried out for 15 hours at the temperature of 60 ℃, and the current density of an electrolytic cell is 1700A/m2And the electrolytic potential is 2.8V. After the electrolysis reaction is finished, the obtained reaction system contains a mixture of 1,10-decanediol and 1,10-decanediol diformate (the selectivity of the 1,10-decanediol is 45.2 percent), then the mixture is hydrolyzed at 90 ℃ for 1h, and the materials sequentially pass through a desolventizing tower, a dehydrogenation tower and a de-heavy tower to be collected to obtain a pure product of the 1, 10-decanediol.
In this example, the conversion rate of the raw material epsilon-caprolactone is 90.8%, the selectivity of the synthesized 1,10-decanediol is 91.4%, the current efficiency is 82.1%, the selectivity of the 6-hydroxycaproic acid salt from the polymerization product is 2.7%, and the electrolytic voltage rising rate is 0.01V/h.
Example 10
Electrochemical preparation of 1, 10-decanediol:
1) 115g (1mol) of epsilon-caprolactone, 76.7g of propanol, 30.3g (0.3mol) of triethylamine and 28.75g of water are uniformly mixed, wherein the mass ratio of the epsilon-caprolactone to the organic solvent propanol in a reaction system is 1.5:1, the addition amount of electrolyte triethylamine is 30% of the mole amount of the epsilon-caprolactone according to the mole amount, and the addition amount of the water is 25% of the mass of the epsilon-caprolactone. Then stirring and heating to 80 ℃ for hydrolysis reaction for 1.5h to generate 6-hydroxycaproic acid salt.
2) Adding 53g (0.5mol) of sodium carbonate and 13.6g (0.2mol) of sodium formate into the hydrolyzed system in the step 1), adding 20g of water, stirring until the sodium carbonate and the epsilon-caprolactone are completely dissolved, wherein the molar ratio of the addition amount of the sodium carbonate to the epsilon-caprolactone is 0.5:1, the molar ratio of the addition amount of sodium formate to epsilon-caprolactone is 0.2: 1, controlling the pH value of the electrolyte to be 8.0. The mixed material was transferred to an electrolytic cell using a platinum titanium anode and a Pb/Ag/TiO cathode as prepared in example 12A composite metal nano-electrode. Electrolytic reaction is carried out for 15 hours at the temperature of 50 ℃, and the current density of an electrolytic cell is 1800A/m2And the electrolytic potential is 2.9V. After the electrolysis reaction is finished, the obtained reaction system contains a mixture of 1,10-decanediol and 1,10-decanediol diformate (the selectivity of the 1,10-decanediol is 44.7 percent), then the mixture is hydrolyzed at 80 ℃ for 2 hours, and the materials sequentially pass through a desolventizing tower, a dehydrogenation tower and a de-heavy tower to be collected to obtain a pure product of the 1, 10-decanediol.
In this example, the conversion rate of the raw material epsilon-caprolactone is 90.3%, the selectivity of the synthesized 1,10-decanediol is 90.2%, the current efficiency is 81.4%, the selectivity of the 6-hydroxycaproic acid salt is 1.8%, and the electrolytic voltage rising rate is 0.01V/h.
Example 11
Electrochemical preparation of 1, 10-decanediol:
1) 115g (1mol) of epsilon-caprolactone, 57.5g of benzene, 10g (0.25mol) of sodium hydroxide and 34.5g of water are uniformly mixed, wherein the mass ratio of the epsilon-caprolactone to the organic solvent benzene in the reaction system is 2:1, the addition amount of electrolyte sodium hydroxide is 25 percent of the molar amount of the epsilon-caprolactone according to the molar amount, and the addition amount of the water is 30 percent of the mass of the epsilon-caprolactone. Then stirring and heating to 80 ℃ for hydrolysis reaction for 1.5h to generate 6-hydroxycaproic acid salt.
2) Adding into the system hydrolyzed in the step 1)63.6g (0.6mol) of sodium carbonate and 13.6g (0.2mol) of sodium formate, 20g of water is added, and the mixture is stirred until the sodium carbonate and the epsilon-caprolactone are completely dissolved, wherein the molar ratio of the added amount of the sodium carbonate to the epsilon-caprolactone is 0.6:1, the molar ratio of the addition amount of sodium formate to epsilon-caprolactone is 0.2: 1, controlling the pH value of the electrolyte to be 9.0. The mixed material was transferred to an electrolytic cell using a platinum titanium anode and a Pb/Ag/TiO cathode as prepared in example 12A composite metal electrode. The electrolytic reaction is carried out for 15 hours at the temperature of 50 ℃, and the current density of an electrolytic cell is 2000A/m2And the electrolytic potential is 3.0V. After the electrolysis reaction is finished, the obtained reaction system contains a mixture of 1,10-decanediol and 1,10-decanediol diformate (the selectivity of the 1,10-decanediol is 43.6 percent), then the mixture is hydrolyzed at 90 ℃ for 1h, and the materials sequentially pass through a desolventizing tower, a dehydrogenation tower and a de-heavy tower to be collected to obtain a pure product of the 1, 10-decanediol.
In this example, the conversion rate of the raw material epsilon-caprolactone is 89.9%, the selectivity of the synthesized 1,10-decanediol is 93.1%, the current efficiency is 83.2%, the selectivity of the 6-hydroxycaproic acid salt from the polymerization product is 2.5%, and the electrolytic voltage rising rate is 0.01V/h.
Comparative example 1
1,10-decanediol was prepared according to the method and process conditions of example 8, with the only difference that: the epsilon-caprolactone, the methanol, the potassium hydroxide and the water are uniformly mixed and are not hydrolyzed by the temperature rise in the step 1), and other operations are the same as those in the example 8.
In this comparative example, the conversion of the raw material ε -caprolactone was 69.5%, the selectivity of the synthesized 1,10-decanediol was 58.1%, the current efficiency was 41.9%, the selectivity of the 6-hydroxycaproic acid salt for the polymerization product was 28.0%, and the electrolytic voltage increase rate was 0.29V/h.
Comparative example 2
1,10-decanediol was prepared according to the method and process conditions of example 8, with the only difference that: sodium carbonate was not added in step 2), and the other operations were the same as in example 8.
In this comparative example, the conversion of the raw material epsilon-caprolactone was 85.2%, the selectivity of the synthesized 1,10-decanediol was 31.5%, the current efficiency was 19.6%, the selectivity of the 6-hydroxycaproic acid salt for the polymerization product was 47.2%, and the electrolytic voltage rise rate was 0.96V/h.
Comparative example 3
1,10-decanediol was prepared according to the method and process conditions of example 8, with the only difference that: no sodium formate was added in step 2), and the other operations were the same as in example 8.
In this comparative example, the conversion of the raw material epsilon-caprolactone was 45.2%, the selectivity of the synthesized 1,10-decanediol was 23.8%, the current efficiency was 11.3%, the selectivity of the 6-hydroxycaproic acid salt for the polymerization product was 64.3%, and the electrolytic voltage rise rate was 2.16V/h.
Comparative example 4
1,10-decanediol was prepared according to the method and process conditions of example 8, with the only difference that: the sodium carbonate in step 2) was replaced with sodium hydroxide, and the other operations were the same as in example 8.
In this comparative example, the conversion of the raw material ε -caprolactone was 87.6%, the selectivity of the synthesized 1,10-decanediol was 34.2%, the current efficiency was 21.5%, the selectivity of the 6-hydroxycaproic acid salt for the polymerization product was 44.1%, and the electrolytic voltage increase rate was 1.21V/h.
Comparative example 5
1,10-decanediol was prepared according to the method and process conditions of example 8, with the only difference that: in step 2), sodium formate was replaced with sodium acetate, and the other operations were the same as in example 8.
In this comparative example, the conversion of the raw material epsilon-caprolactone was 80.2%, the selectivity of the synthesized 1,10-decanediol was 65.2%, the current efficiency was 45.3%, the selectivity of the 6-hydroxycaproic acid salt for the polymerization product was 21.1%, and the electrolytic voltage rise rate was 0.35V/h.
Comparative example 6
1,10-decanediol was prepared according to the method and process conditions of example 8, with the only difference that: the cathode was replaced with a Ti electrode and the other operations were the same as in example 8.
In this comparative example, the conversion of the raw material epsilon-caprolactone was 73.2%, the selectivity of the synthesized 1,10-decanediol was 75.8%, the current efficiency was 60.9%, the selectivity of the 6-hydroxycaproic acid salt for the polymerization product was 11.9%, and the electrolytic voltage rise rate was 0.25V/h.
Comparative example 7
1,10-decanediol was prepared according to the method and process conditions of example 8, with the only difference that: the cathode was replaced with a Pb-Ag electrode, and the other operations were the same as in example 8.
In this comparative example, the conversion of the raw material epsilon-caprolactone was 70.6%, the selectivity of the synthesized 1,10-decanediol was 78.1%, the current efficiency was 61.5%, the selectivity of the 6-hydroxycaproic acid salt for the polymerization product was 10.1%, and the electrolytic voltage rise rate was 0.21V/h.
Comparative example 8
1,10-decanediol was prepared according to the method and process conditions of example 8, with the only difference that: replacement of the cathode by Pb/TiO2The electrode and other operations were the same as in example 8.
In this comparative example, the conversion of the raw material ε -caprolactone was 77.5%, the selectivity of the synthesized 1,10-decanediol was 71.0%, the current efficiency was 57.9%, the selectivity of the 6-hydroxycaproic acid salt for the polymerization product was 12.6%, and the electrolytic voltage increase rate was 0.19V/h.
Comparative example 9
1,10-decanediol was prepared according to the method and process conditions of example 8, with the only difference that: cathode is replaced by Ag/TiO2The electrode and other operations were the same as in example 8.
In this comparative example, the conversion of the raw material epsilon-caprolactone was 68.9%, the selectivity of the synthesized 1,10-decanediol was 68.3%, the current efficiency was 43.7%, the selectivity of the 6-hydroxycaproic acid salt for the polymerization product was 22.9%, and the electrolytic voltage rise rate was 0.48V/h.
The above description is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, several modifications and additions can be made without departing from the method of the present invention, and these modifications and additions should also be regarded as the protection scope of the present invention.

Claims (18)

1. An electrochemical process for the synthesis of 1,10-decanediol, comprising the steps of:
1) mixing epsilon-caprolactone, alkaline electrolyte, organic solvent and water, and then heating and stirring to perform hydrolysis reaction on the epsilon-caprolactone in the system to generate 6-hydroxycaproic salt;
2) adding sodium carbonate, sodium formate and water into the hydrolyzed system in the step 1), stirring and dissolving, then carrying out electrolytic reaction, and obtaining the 1,10-decanediol after the reaction is finished.
2. The method according to claim 1, wherein in step 1), the alkaline electrolyte is added in an amount of 15 to 30% by mole based on the mole of epsilon-caprolactone;
the alkaline electrolyte is any one or the combination of at least two of potassium methoxide, sodium methoxide, potassium hydroxide, sodium hydroxide and triethylamine;
the mass ratio of the epsilon-caprolactone to the organic solvent is 0.5:1-2: 1;
the organic solvent is any one or the combination of at least two of benzene solvents, pyridine solvents, nitrile solvents and alcohol solvents;
the addition amount of the water is 5-30% of the mass of the epsilon-caprolactone.
3. The method according to claim 2, wherein in step 1), the alkaline electrolyte is added in an amount of 20 to 25% by mole based on the mole of epsilon-caprolactone;
the mass ratio of the epsilon-caprolactone to the organic solvent is 1:1-1.2: 1;
the addition amount of the water is 10-20% of the mass of the epsilon-caprolactone.
4. The method according to claim 2, wherein in step 1), the alkaline electrolyte is potassium methoxide or potassium hydroxide;
the organic solvent is any one or the combination of at least two of benzene, pyridine, acetonitrile, methanol, ethanol and propanol.
5. The method as claimed in claim 1, wherein in the step 1), the hydrolysis reaction is carried out at a temperature of 60-100 ℃ for 0.5-2 h.
6. The method as claimed in claim 5, wherein in the step 1), the hydrolysis reaction is carried out at a temperature of 80-90 ℃ for 1-1.5 h.
7. The process according to claim 1, wherein in step 2) the molar ratio of sodium carbonate to epsilon-caprolactone in step 1) is 0.3-0.6: 1;
the molar ratio of the sodium formate to the epsilon-caprolactone in the step 1) is 0.2-0.4: 1.
8. the process according to claim 7, wherein in step 2) the molar ratio of sodium carbonate to epsilon-caprolactone in step 1) is 0.4-0.5: 1;
the molar ratio of the sodium formate to the epsilon-caprolactone in the step 1) is 0.2-0.3: 1.
9. the method as claimed in claim 1, wherein in step 2), the electrolysis reaction is carried out at an electrolysis potential interval of 2-3V and an electrolysis current density of 1200-2000A/m2。
Carrying out the electrolytic reaction, wherein the temperature of the electrolyte is 40-60 ℃, and the electrolytic time is 5-20 h;
and the pH value of the electrolyte is 8-10 in the electrolytic reaction.
10. The method as claimed in claim 9, wherein in the step 2), the electrolysis reaction has an electrolysis potential range of 2.5-2.8V and an electrolysis current density of 1600-1800A/m2。
And carrying out the electrolytic reaction, wherein the temperature of the electrolyte is 50-60 ℃, and the electrolytic time is 10-15 h.
11. The method according to claim 1, wherein in step 2), the electrolytic reaction is carried out in an electrolytic cell comprising an anode and a cathode;
the anode is a platinum electrode, a platinum titanium electrode or a DSA electrode;
the cathode is Pb/Ag/TiO2A composite metal electrode.
12. The method of claim 11, wherein the DSA electrode is Ti-based PbO2、IrO2、RuO2Or a tin antimony oxide electrode.
13. The method of claim 11, wherein the Pb/Ag/TiO is2The composite metal electrode is prepared by the following method:
(1) graphite as cathode and titanium as anode are put into acetic acid solution containing HF for oxidation reaction under constant voltage, and after the reaction is finished, the solution is washed with water, dried and roasted to obtain TiO2An electrode;
(2) TiO obtained in the step (1)2The electrode is a working electrode, the Pb-Ag electrode is a counter electrode, and the current density in the electroplating solution composed of lead methane sulfonate, silver methane sulfonate, sulfonic acid and water is 10-60mA/cm2After the bottom deposition is carried out for 30 to 180 seconds, the Pb/Ag/TiO is prepared2A composite metal electrode.
14. The method of claim 13, wherein in step (1), the graphite cathode and the titanium metal anode are of the same shape and size;
the acetic acid aqueous solution containing HF comprises the following components in percentage by mass: 5-20% of acetic acid, 0.02-0.1% of HF and the balance of water;
the oxidation reaction is carried out at the temperature of 20-50 ℃ for 1-3 h;
the voltage adopted in the oxidation process is 25-50V, and the current density is 5-10mA/cm2；
The distance between the graphite cathode and the titanium metal anode is 0.5-2.5 cm;
the roasting is carried out at the temperature of 300-700 ℃, the time of 1-5h and the heating rate of 2-20 ℃/min.
15. The method of claim 14, wherein the graphite cathode and the titanium metal anode are circular, rectangular or diamond-shaped;
the acetic acid aqueous solution containing HF comprises the following components in percentage by mass: 10-15% of acetic acid, 0.04-0.08% of HF and the balance of water;
the oxidation reaction is carried out at the temperature of 30-40 ℃ for 1.5-2 h;
the voltage adopted in the oxidation process is 30-40V, and the current density is 6-8mA/cm2；
The roasting is carried out at the temperature of 500-600 ℃, the time of 2-3h and the heating rate of 5-10 ℃/min.
16. The method as claimed in claim 13, wherein in the step (2), the plating solution contains 0.3 to 0.4mol/L of lead methanesulfonate in terms of Pb ion concentration and 0.2 to 0.3mol/L of silver methanesulfonate in terms of Ag ion concentration, wherein the sulfonic acid content is 14 to 20 wt%, and the balance is water.
17. The method as claimed in claim 1, wherein in the step 2), after the electrolysis reaction is finished, the obtained reaction system contains a mixture of 1,10-decanediol and 1,10-decanediol diformate, and the hydrolysis reaction is used for hydrolyzing and converting the 1,10-decanediol diformate into 1, 10-decanediol.
18. The method of claim 17, wherein the hydrolysis reaction is carried out at a temperature of 80-100 ℃ for 0.5-2 hours.
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