阅读说明：本技术 一种环十二醇的制备方法 (Preparation method of cyclododecanol ) 是由 冯传密 史文涛 吴昊 吕金昆 王聪 刘新伟 杨克俭 于 2019-11-06 设计创作，主要内容包括：本发明提供了一种环十二醇的制备方法,包括以下步骤,1)将环十二烯、有机溶剂、水、催化剂搅拌混合；所述催化剂为固体酸；环十二烯、有机溶剂、水、催化剂的重量比为1：(0.1～10)：(0.1～2)：(0.01～10)；2)通入气体至一定压力,在气体氛围下逐渐升高至一定温度；气体压力维持0.01～10MPa；反应温度为100～250℃。本发明可以实现水合高收率制备环十二醇,收率达64～91％,催化剂循环套用50次无明显变化。(The invention provides a preparation method of cyclododecanol, which comprises the following steps of 1) stirring and mixing cyclododecene, an organic solvent, water and a catalyst; the catalyst is a solid acid; the weight ratio of cyclododecene to organic solvent to water to catalyst is 1: (0.1-10): (0.1-2): (0.01-10); 2) introducing gas to a certain pressure, and gradually increasing the temperature to a certain temperature in a gas atmosphere; the gas pressure is maintained at 0.01-10 MPa; the reaction temperature is 100-250 ℃. The method can prepare cyclododecanol with high yield by hydration, the yield reaches 64-91%, and the catalyst is recycled for 50 times without obvious change.)

1. A method for preparing cyclododecanol is characterized in that: comprises the following steps of (a) carrying out,

1) mixing cyclododecene, organic solvent, water and catalyst; the catalyst is a solid acid; the weight ratio of cyclododecene to organic solvent to water to catalyst is 1: (0.1-10): (0.1-2): (0.01-10);

2) introducing gas to a certain pressure, and gradually increasing the temperature to a certain temperature in a gas atmosphere; the gas pressure is maintained at 0.01-10 MPa; the reaction temperature is 100-250 ℃.

2. The process for producing cyclododecanol according to claim 1, characterized in that: the organic solvent is one or more than two of isopropanol, tert-butyl alcohol, tert-amyl alcohol, polyethylene glycol dimethyl ether, N-dimethylformamide, N-dimethylacetamide, N-dimethylpropionamide, dimethyl sulfoxide, sulfolane, diethyl sulfoxide, acetone, butanone, methyl tert-butanone, acetonitrile, formic acid, acetic acid, propionic acid, N-butyric acid and pivalic acid; preferably, tert-butanol.

3. The process for producing cyclododecanol according to claim 1, characterized in that: the catalyst is H-ZSM-5, H-beta molecular sieve, macroporous sulfonic acid resin, silicotungstic acid (H)₄[Si(W₃O₁₀)₄]·26H₂O), solid super acidic SO₄ ^2－/ZrO₂Preferably H-ZSM-5.

4. The process for producing cyclododecanol according to claim 1, characterized in that: the weight ratio of cyclododecene to solvent to water to catalyst is 1: (0.5-0.6): (0.3-0.5): (0.05-0.1).

5. The process for producing cyclododecanol according to claim 1, characterized in that: the gas is one or more of nitrogen, argon, carbon monoxide and carbon dioxide, preferably carbon dioxide.

6. The process for producing cyclododecanol according to claim 1, characterized in that: in the step 2), the reaction pressure is 0.1-0.2 Mpa, and the reaction temperature is 200-250 ℃.

Technical Field

The invention belongs to the technical field of chemical materials, and particularly relates to a preparation method of cyclododecanol.

Background

Cyclododecanol is a key intermediate for preparing macrocyclic muskone and long carbon chain special nylon, and specific products such as 3-methyl cyclopentadecanone, racemic muskone, cyclopentadecanone lactone, 5-cyclohexadecanone, cyclopentadecanone, 12-methyl-14-carbonyl bicyclo [9, 3, 1] pentadecane, dodecanedioic acid, dodecanediamine, nylon 12, nylon 1212, nylon 612, nylon 12T and nylon 1012.

The first industrial route of cyclododecanol employs cyclododecene to react with an oxidant to prepare epoxycyclododecane, followed by a hydrogenation process. The patent of US 4469860 reports that the conversion rate of raw materials and the selectivity of products are both lower than 85 percent by using metal borate as a catalyst and oxygen as an oxygen source to perform the epoxidation reaction process of cyclododecane; JP2004002234 uses vanadium carrier to catalyze the epoxidation reaction of cyclododecene, and although the selectivity reaches over 90%, the conversion rate of raw materials is low. In EP1411050, a 20% excess of hydrogen peroxide is reacted with cyclododecene to form epoxycyclododecane. CN10465007 based on the reaction of tert-butyl hydroperoxide with cyclododecene to prepare epoxycyclododecane, although high selectivity and high conversion rate can be achieved to prepare epoxycyclododecane, there is still a high risk of using organic peroxide.

The cyclododecanol is prepared by oxidizing cyclododecane, boric acid, metaboric acid, cobalt and manganese salts can be used as catalysts for cyclododecane oxidation in US3419615, the preparation of a mixture of cyclododecanol and cyclododecanone from cyclododecane can be realized under the air condition, but the conversion rate is only 5-25%, a large amount of idling is needed in a reaction system for raw materials, and the energy consumption is high; meanwhile, the high-temperature reaction in which oxygen participates has strict requirements on reaction conditions and has higher reaction risk.

The third industrial route of cyclododecanol adopts cyclododecene epoxidation to prepare epoxy cyclododecadiene, and cyclododecanol is prepared by subsequent hydrogenation. In EP0033763, cyclododecene and hydrogen peroxide react in a formic acid system to prepare epoxy cyclododecadiene, 50-70% of hydrogen peroxide is preferably used in the reaction, and the high-concentration hydrogen peroxide not only increases the industrialization difficulty, but also is not beneficial to the safety control of the reaction system. In US6043383, cyclododecene and hydrogen peroxide are subjected to epoxidation reaction under a specific weak acid condition, the oxidation system is difficult to consider the utilization rate and selectivity of the hydrogen peroxide in the oxidation reaction, and meanwhile, the explosion risk of peroxides exists. And by-product diepoxide and other high boiling point products adversely affect the separation and purification.

Disclosure of Invention

In view of the above, the present invention aims to provide a method for preparing cyclododecanol, which shortens the synthetic process route of cyclododecanol, and not only reduces the production cost by preparing corresponding alcohol through the reaction of unsaturated carbon-carbon double bond and water; meanwhile, the use of peroxide and oxygen can be effectively avoided, and the potential safety hazard is effectively reduced.

In order to achieve the purpose, the technical scheme of the invention is realized as follows:

a preparation method of cyclododecanol comprises the following steps,

1) mixing cyclododecene, organic solvent, water and catalyst; the catalyst is a solid acid; the weight ratio of cyclododecene to organic solvent to water to catalyst is 1: (0.1-10): (0.1-2): (0.01-10);

2) introducing gas to a certain pressure, and gradually increasing the temperature to a certain temperature in a gas atmosphere; the gas pressure is maintained at 0.01-10 MPa; the reaction temperature is 100-250 ℃.

The equation for the reaction of cyclododecene with water is as follows:

the invention adopts a hydration scheme to replace the prior peroxide oxidation scheme, uses a solvent to dilute materials, leads cyclododecene to react with water and fully mix, increases the intersolubility of oil and water, uses gas to promote the reaction in the reaction, particularly leads carbon dioxide gas to form a carbonate intermediate in the reaction process, and leads cyclododecanol product after the carbon dioxide is separated; on the other hand, the gas is filled, so that the reduction of the material partial pressure can be avoided, the concentration in the gas phase is reduced, and the complete conversion is promoted.

After the reaction is finished, oil-water separation is carried out, and then unreacted cyclododecene and crude products are removed through decompression, wherein the temperature is not higher than 100 ℃, otherwise, side reaction is caused.

Preferably, the organic solvent is one or more of isopropanol, tert-butanol, tert-amyl alcohol, polyethylene glycol dimethyl ether, N-dimethylformamide, N-dimethylacetamide, N-dimethylpropionamide, dimethyl sulfoxide, sulfolane, diethyl sulfoxide, acetone, butanone, methyl tert-butanone, acetonitrile, formic acid, acetic acid, propionic acid, N-butyric acid and pivalic acid; preferably, tert-butanol.

Preferably, the catalyst is H-ZSM-5, H-beta molecular sieve, macroporous sulfonic acid resin, silicotungstic acid (H)₄[Si(W₃O₁₀)₄]·26H₂O), solid super acidic SO₄ ^2－/ZrO₂Preferably H-ZSM-5.

Preferably, the weight ratio of cyclododecene to solvent to water to catalyst is 1: (0.5-0.6): (0.3-0.5): (0.05-0.1).

Preferably, the gas is one or more of nitrogen, argon, carbon monoxide and carbon dioxide, and preferably, carbon dioxide.

Preferably, in the step 2), the reaction pressure is 0.1-0.2 Mpa, and the reaction temperature is 200-250 ℃.

Compared with the prior art, the preparation method of cyclododecanol has the following advantages:

(1) the preparation method has simple process route, and cyclododecene is taken as a raw material to complete the reaction in one step;

(2) according to the preparation method, the hydration scheme is adopted to replace the existing peroxide oxidation scheme, so that the use of peroxide is avoided, the production cost is reduced, and the safe operation of chemical production is facilitated;

(3) the solid acid catalyst is adopted, so that the continuous and stable application of the catalyst can be realized, and the reaction process is green and environment-friendly;

(4) according to the preparation method, gas is used for promoting the reaction in the reaction, the conversion rate is 40-75%, and the reaction yield is 84-91%.

(5) The preparation method can realize repeated and cyclic use of catalysis for more than 50 times, and has no obvious influence on the yield and the conversion rate of the product.

Detailed Description

Unless defined otherwise, technical terms used in the following examples have the same meanings as commonly understood by one of ordinary skill in the art to which the present invention belongs. The test reagents used in the following examples, unless otherwise specified, are all conventional biochemical reagents; the experimental methods are conventional methods unless otherwise specified.

The present invention will be described in detail with reference to examples.