阅读说明：本技术 一种联产二甲基癸炔二醇和甲基己炔醇的方法 (Method for coproducing dimethyl decyne diol and methyl hexine alcohol ) 是由 王南 王林生 李果 张鸿 曾健 孔林 李代军 于 2021-09-27 设计创作，主要内容包括：一种联产二甲基癸炔二醇(4,7-二甲基-5-癸炔-4,7-二醇)和甲基己炔醇(3-甲基-1-己炔-3-醇)的方法,以2-戊酮和乙炔作原料,氢氧化钾或异丁醇钾或叔丁醇钾作催化剂,有机溶剂作分散剂,先将2-戊酮与常压或低压的乙炔在较低温度下反应生成甲基己炔醇-催化剂络合物,再将其与2-戊酮混合后快速通过高温反应管反应生成二甲基癸炔二醇-催化剂络合物。反应产物水解脱除氢氧化钾后,分馏收取各组分。本发明具有反应温度低、反应时间短、副反应少以及催化剂耗量少等特点。(A process for coproducing dimethyl decyne diol (4, 7-dimethyl-5-decyne-4, 7-diol) and methyl hexine alcohol (3-methyl-1-hexine-3-alcohol) includes such steps as reaction between 2-pentanone and acetylene at low temp to obtain methyl hexine alcohol-catalyst complex, mixing it with 2-pentanone, and quickly reacting in high-temp reaction tube to obtain dimethyl decyne diol-catalyst complex, and features simple process, low cost, and high output rate of product. After the reaction product is hydrolyzed to remove potassium hydroxide, the components are collected by fractional distillation. The method has the characteristics of low reaction temperature, short reaction time, less side reaction, less catalyst consumption and the like.)

1. A method for coproducing dimethyldecyndiol and methylhexadecyndiol, comprising the steps of:

(1) preparation of active acetylene suspension slurry

Grinding the catalyst and the organic solvent into slurry, stirring and heating the slurry to enable the slurry to be nearly transparent or semitransparent, cooling the slurry to enable the catalyst to be in a suspended particulate state, and introducing acetylene to react to prepare active acetylene suspended slurry, namely an acetylene-catalyst complex;

(2) first stage reaction for preparing active methyl hexyne alcohol solution

Adding a first section of 2-pentanone into the suspension slurry, and continuously introducing acetylene to ensure that the 2-pentanone reaction conversion reaches more than 90 percent to generate a solution mainly containing active methylhexaynol, namely a methylhexaynol-catalyst complex;

(3) preparation of Dimethyldecynediol by the second stage reaction

Adding the second-stage 2-pentanone into the active methylhexayne alcohol solution under normal pressure without introducing acetylene, uniformly mixing, pumping the mixed material into a tubular reactor for reaction to generate a dimethyl decyndiol-catalyst complex, and immediately introducing the reaction material into stirred clear water after flowing out of the reaction tube to terminate the reaction;

(4) hydrolysis separation dealkalization

Stirring the reaction end point material together with water solution to carry out hydrolysis reaction, hydrolyzing the dimethyl decyne glycol-catalyst complex and the methylhexaynol-catalyst complex, and decomposing into dimethyl decyne glycol, methylhexaynol and potassium hydroxide, wherein the potassium hydroxide is dissolved into the water phase, the dimethyl decyne glycol and the methylhexaynol are still remained in the oil phase liquid, and separating oil phase and water phase;

(5) fractionating to recover the product

And carrying out reduced pressure or atmospheric pressure fractionation on the oil phase liquid, and respectively collecting the fraction 3-methyl-1-hexyne-3-ol with the distillation temperature of 136-138 ℃ under the atmospheric pressure and the fraction 4, 7-dimethyl-5-decyne-4, 7-diol with the distillation temperature of 227-229 ℃ under the atmospheric pressure.

2. The method for coproducing the dimethyl decyne glycol and the methyl hexine alcohol according to the claim 1, wherein in the step (1), the used organic solvent simultaneously satisfies the following three conditions:

boiling point of the solvent is required to be lower than 229 ℃ of boiling point of 4, 7-dimethyl-5-decyne-4, 7-diol and higher than 80 ℃ of reaction temperature;

secondly, the raw material 2-pentanone and the reaction products 3-methyl-1-hexyne-3-ol and 4, 7-dimethyl-5-decyne-4, 7-diol have larger solubility and small intersolubility with water;

③ the strong base is stable;

further, the organic solvent selected in the step (1) is an ether solvent such as n-propyl ether, ethyl butyl ether, n-amyl ether, isoamyl ether, n-hexyl ether, ethylene glycol dibutyl ether and the like, and an aromatic hydrocarbon solvent such as toluene, xylene, ethylbenzene, diethylbenzene, propylbenzene, isopropylbenzene and the like.

3. The method for coproducing dimethyl decyne glycol and methyl hexynol according to claim 1, wherein in the step (1), the catalyst is industrial-grade potassium hydroxide, potassium isobutyl alkoxide or potassium tert-butyl alkoxide with purity of 92-94%; the feeding proportion of the catalyst and the organic solvent is determined according to the type of the used catalyst, when potassium hydroxide is selected as the catalyst, the weight ratio of the pure potassium hydroxide to the organic solvent is =1: 30-1: 9, further, preferably, the weight ratio of the pure potassium hydroxide to the organic solvent is =1: 19-1: 11, when potassium isobutyl alkoxide or potassium tert-butoxide is selected as the catalyst, the weight ratio of the pure potassium alkoxide to the organic solvent is =1: 14-1: 4, further, preferably, the weight ratio of the pure potassium alkoxide to the organic solvent is =1: 9-1: 5;

the temperature for preparing the catalyst suspension by heating is 60-80 ℃, and the reaction temperature for preparing the active acetylene suspension slurry by introducing acetylene is 15-20 ℃; the acetylene pressure is less than or equal to 0.15MPa, and further preferably 0.08MPa to 0.15 MPa; the reaction time is 1-2 hours.

4. The method for co-producing dimethyldecyne glycol and methylhexadecyne alcohol according to claim 1, wherein the total amount of 2-pentanone in step (2) and step (3) is controlled to satisfy 2-pentanone: catalyst = 2.0: 1-1.4: 1 molar ratio, and further preferably 2-pentanone: catalyst = 1.8: 1-1.6: 1 molar ratio, wherein the first stage 2-pentanone: catalyst =1: 1-1.2: 1 molar ratio in step (2) and the total amount of the remaining 2-pentanone is added in step (3).

5. The method for coproducing dimethyl decyne glycol and methyl hexine alcohol according to claim 1, wherein in the step (2), the reaction temperature is controlled within a range of 15 ℃ to 35 ℃; the acetylene pressure is always kept to be less than or equal to 0.15MPa, and further preferably 0.08MPa to 0.15MPa in the reaction process; the total reaction time is 3-5 hours.

6. The method for co-producing the dimethyl decyne glycol and the methyl hexine alcohol according to the claim 1, wherein in the step (3), the acetylene is not introduced any more, but the end material of the step (2) is mixed with the second-stage 2-pentanone and then directly pressed into the reaction tube for reaction;

the inner diameter of the reaction tube is 5 mm-20 mm, and the length of the reaction tube is 60 m-100 m; the temperature of a heat transfer medium outside the reaction tube is 60-80 ℃; the reaction materials stay in the reaction tube for 1-3 minutes.

7. The method for co-producing dimethyldecyndiol and methylhexadecynol as claimed in claim 1, wherein in step (3), the amount of clean water used for terminating the reaction is 2-3 times the amount of the initial catalyst.

8. The method for co-producing dimethyldecyndiol and methylhexaynol according to claim 1, wherein in step (4), the hydrolysis reaction temperature is 30-50 ℃ and the hydrolysis reaction time is 30-60 minutes.

Technical Field

The invention relates to a synthesis method of chemical substances 4, 7-dimethyl-5-decyne-4, 7-diol and 3-methyl-1-hexyne-3-ol.

Background

Dimethyldecyndiol (4, 7-dimethyl-5-decyne-4, 7-diol) and methylhexaynol (3-methyl-1-hexyn-3-ol) are chemical intermediates, have excellent surface activity, are used alone or as one of the components, and are also upstream starting materials for further synthesis of nonionic surfactants with unique properties. At present, few disclosures are available on the industrial synthesis of the two chemical substances, and it is known from the molecular structures of the two chemical substances that dimethyl decyne glycol and methyl hexynol can be prepared from 2-pentanone and acetylene by a Reppe method production process, but the molecular structures of the raw materials have large steric hindrance, and the reaction process requires higher temperature and longer reaction time, which inevitably leads to side reactions such as polymerization of reaction products under a long-term high-temperature environment, and also wraps the catalyst to inactivate the catalyst, thereby greatly increasing the consumption of the catalyst.

Disclosure of Invention

The invention aims to provide a technical method for coproducing and synthesizing dimethyl decyne diol (4, 7-dimethyl-5-decyne-4, 7-diol) and methyl hexynol (3-methyl-1-hexynl-3-ol) with low reaction temperature, short reaction time, less side reaction and less catalyst consumption.

The invention adopts the following technical scheme:

the production and synthesis of dimethyl decyne diol (chemical name of 4, 7-dimethyl-5-decyne-4, 7-diol) and methyl hexynol (chemical name of 3-methyl-1-hexynl-3-ol) are carried out according to the following technical scheme by taking 2-pentanone and acetylene as starting raw materials, potassium hydroxide or potassium alkoxide as a catalyst and an organic solvent as a dispersing agent.

1. Preparation of active acetylene suspension slurry

Grinding an organic solvent and a catalyst into slurry in grinding equipment, then transferring the slurry into reaction equipment, stirring and heating the slurry to 60-80 ℃, keeping the temperature for 0.5-1 hour, and continuing stirring and slowly cooling the slurry to 15-20 ℃ after the material is in a transparent or nearly transparent state, namely the catalyst is completely or mostly dissolved in the organic solvent. After the temperature is reduced, the organic solution is in a semitransparent state, and the catalyst is uniformly dispersed in the organic solution in the form of fine suspended particles in a partially dissolved part.

After the catalyst suspension slurry is prepared, the catalyst suspension slurry is continuously stirred, and acetylene is introduced for reaction to prepare active acetylene (acetylene-catalyst complex) suspension slurry.

The organic solvent selected in the operation simultaneously satisfies the following three conditions:

(1) the boiling point of the solvent is required to be lower than that of 4, 7-dimethyl-5-decyne-4, 7-diol (229 ℃) and higher than 80 ℃ (reaction temperature);

(2) 2-pentanone as a raw material and 3-methyl-1-hexyne-3-ol and 4, 7-dimethyl-5-decyne-4, 7-diol as reaction products both have high solubility and low intersolubility with water;

(3) is stable to strong alkali.

Meanwhile, examples of the organic solvent satisfying the above conditions include ether solvents such as n-propyl ether, ethyl butyl ether, n-pentyl ether, isopentyl ether, n-hexyl ether, and ethylene glycol dibutyl ether, and aromatic hydrocarbon solvents such as toluene, xylene, ethylbenzene, diethylbenzene, propylbenzene, and isopropylbenzene.

In the operation, the catalyst is potassium hydroxide (industrial grade, purity is 92% -94%), potassium isobutyl alkoxide or potassium tert-butyl alkoxide, and any one of the above can be used.

The feeding proportion of the catalyst and the organic solvent is determined according to the type of the used catalyst, when potassium hydroxide is selected as the catalyst, the content of the potassium hydroxide (pure substance) in the organic solvent =1: 30-1: 9 (weight ratio) is 10% -30% corresponding to the product content in the oil phase liquid of the final reaction material, preferably, the content of the potassium hydroxide (pure substance) in the organic solvent =1: 19-1: 11 (weight ratio) is 15% -25% corresponding to the product content in the oil phase liquid of the final reaction material. When potassium isobutyl alkoxide or potassium tert-butoxide is selected as the catalyst, the content of the potassium alkoxide (pure) in the organic solvent =1: 14-1: 4 (weight ratio) is 10-30% corresponding to the product in the oil phase liquid of the final reaction material, and preferably the content of the potassium alkoxide (pure) in the organic solvent =1: 9-1: 5 (weight ratio) is 15-25% corresponding to the product in the oil phase liquid of the final reaction material.

In the operation of the step, the reaction temperature for preparing the active acetylene suspension slurry by introducing acetylene is 15-20 ℃; the acetylene pressure is less than or equal to 0.15MPa, preferably 0.08MPa to 0.15 MPa. (ii) a The reaction time is 1-2 hours.

2. First stage reaction for preparing active methyl hexyne alcohol solution

Continuously introducing acetylene, simultaneously uniformly and slowly adding the first section of 2-pentanone into the active acetylene suspension slurry, and then continuously reacting to ensure that the 2-pentanone reaction conversion reaches more than 90 percent, thereby generating a solution of active methylhexanol (methylhexanol-catalyst complex).

The total amount of 2-pentanone added in the first stage reaction operation and the second stage reaction operation is controlled to satisfy 2-pentanone: catalyst (pure) = 2.0: 1-1.4: 1 (molar ratio), preferably 2-pentanone: catalyst (pure) = 1.8: 1-1.6: 1 (molar ratio). In the first stage of the reaction, 2-pentanone and catalyst (pure) =1: 1-1.2: 1 (molar ratio) are controlled. The remaining 2-pentanone is added in the second stage of the reaction.

In the operation, the time of adding 2-pentanone is controlled to be 1-2 hours, and the total reaction time is 3-5 hours; the reaction temperature is controlled within the range of 15-35 (low temperature and high temperature in the early stage of the reaction); the acetylene pressure is always kept less than or equal to 0.15MPa, preferably 0.08MPa to 0.15MPa in the reaction process.

3. Second stage reaction for synthesizing dimethyl decyne diol

And (2) adding the second-stage 2-pentanone into the active methylhexayne alcohol solution under normal pressure without introducing acetylene, uniformly mixing, pumping the mixed material into a tubular reactor for reaction to generate a dimethyl decyne glycol-catalyst complex, and immediately introducing the reaction material into stirred clear water after flowing out of the reaction tube to terminate the reaction.

This reaction operation is carried out in a tubular reactor. The inner diameter of the reaction tube is 5 mm-20 mm, and the length of the reaction tube is 60 m-100 m; the temperature of a heat transfer medium outside the reaction tube is 60-80 ℃; the reaction materials stay in the reaction tube for 1-3 minutes.

The feeding amount of clear water for terminating the reaction is 2-3 times of the feeding amount of the initial catalyst.

The raw material 2-pentanone of the section is insufficient, the reaction temperature is high, and the 2-pentanone basically finishes the reaction after the reaction materials pass through the reaction tube. Because the reaction materials have short residence time in the reaction tube, the side reaction is effectively inhibited, and the reaction products mainly comprise a dimethyl decyne glycol-catalyst complex and a methylhexaynol-catalyst complex.

4. Hydrolysis separation dealkalization

And stirring the materials at the end of the reaction (together with the water liquid) to perform hydrolysis reaction, wherein the dimethyl decyne glycol-catalyst complex and the methylhexaynol-catalyst complex are hydrolyzed and decomposed into dimethyl decyne glycol, methylhexaynol and potassium hydroxide, wherein the potassium hydroxide is dissolved into the water phase, and the dimethyl decyne glycol and the methylhexaynol materials are still remained in the oil phase liquid. After the hydrolyzed material is kept stand for layering, oil and water phases are separated.

In this step, the hydrolysis temperature is 30 ℃ to 50 ℃. The hydrolysis reaction time is 30-60 minutes.

5. Fractionating to recover the product

And (3) carrying out reduced pressure or atmospheric pressure fractionation on the oil phase liquid, and respectively collecting a fraction (3-methyl-1-hexyne-3-ol) with the distillation temperature of 136-138 ℃ and a fraction (4, 7-dimethyl-5-decyne-4, 7-diol) with the distillation temperature of 227-230 ℃ under atmospheric pressure.

The invention has the following characteristics and advantages:

1. the synthetic reaction is divided into two sections to be carried out, the two-step reaction process of the reaction is met, the feeding proportion of the raw material 2-pentanone and the reaction temperature are controlled in the first-stage reaction, the reaction mainly generates the methylhexaynol, the viscosity of the obtained product solution is low, and the catalyst is prepared into the suspension slurry and the active acetylene suspension slurry in advance, so that the catalyst can be fully utilized, and the consumption of the catalyst only reaches 1.1-1.2 times of the theoretical consumption.

2. The acetylene in the first stage is at normal pressure or low pressure, and the second stage does not need normal pressure, so that the requirement on reaction equipment is low.

3. The first stage of the method has low reaction temperature, is beneficial to the generation of the methylhexaynol and is not beneficial to the generation of side reactions. The high reaction temperature of the second stage is beneficial to the generation of the dimethyl decyne diol, the reaction is terminated after the reaction material stays for only 1-3 minutes, the side reaction is effectively inhibited, and the yield of the total reaction product corresponding to the raw material 2-pentanone can reach more than 95.

4. The residual raw material 2-pentanone in the reaction end product is little and less than 0.5 percent, and the recovery treatment of the residual raw material is not needed.

5. The production efficiency can be improved, and the dimethyl decyne glycol and the methylhexaynol are co-produced, wherein the product mainly comprises dimethyl decyne glycol, and the weight ratio of dimethyl decyne glycol to dimethyl hexynol is = 9: 1-3: 1.

Detailed Description

Example 1:

(1) adding 1750g of solvent ethyl butyl ether and 250g of potassium tert-butoxide (industrial grade, purity 98%) into a grinder in sequence, grinding into slurry, transferring into a reaction kettle, starting stirring, heating to 70-80 ℃, keeping for 1 hour, and then cooling to 15-20 ℃ for control. And introducing acetylene gas, keeping the acetylene pressure within the range of 0.1-0.12 MPa, and reacting for 1.5 hours.

(2) 360g of 2-pentanone (industrial grade, purity 99.5%) is uniformly and slowly added into the reaction kettle from the elevated tank, the addition is finished within 80-100 minutes, and the acetylene pressure is kept within the range of 01-0.12 MPa for reaction. After the addition of 2-pentanone, the reaction temperature was gradually raised to 33 to 35 ℃ at a rate of 1 to 2 ℃ every 10 minutes, and then maintained. The reaction is carried out for about 3.5 hours, the residual 5-methyl-2-hexanone in the reaction material is sampled and detected to be less than 8 percent, and the acetylene is stopped being introduced after about half an hour of sampling and detecting.

In the initial mixture of the reaction, 2-pentanone: potassium tert-butoxide (pure) =1.16:1 (molar ratio).

(3) Adding 200g of 2-pentanone into a reaction kettle, uniformly mixing, pumping the mixed material into a tubular reactor, controlling the flow speed of the material in a reaction tube, and immediately feeding the material flowing out of the reaction tube into stirred clear water to terminate the reaction.

In this example, the total amount of 2-pentanone added in two times is potassium tert-butoxide (pure) = 1.8:1 (molar ratio), the inner diameter of the reaction tube is 12mm, and the length of the tube is 80 m; the outer shell of the reaction tube uses water as a heat transfer medium, and flows reversely with the reaction material, and the entering temperature of the water medium is controlled to be 68-72 ℃; and controlling the residence time of the reaction materials in the reaction tube to be 1.5-2 minutes.

The total amount of clear water used for terminating the reaction was about 500 g.

(4) Stirring the reaction material (together with the water solution) at 30-40 ℃ for 0.5 h, standing for layering, separating the lower-layer (containing potassium hydroxide) water phase solution, and neutralizing the oil phase material by using dilute sulfuric acid solution to pH 5.5-6.

(5) Transferring the oil phase liquid to an experimental rectifying tower for carrying out reduced pressure or normal pressure fractionation, and respectively collecting a fraction (3-methyl-1-hexyne-3-ol) with the distillation temperature of 136-138 ℃ under normal pressure and a fraction (4, 7-dimethyl-5-decyne-4, 7-diol) with the distillation temperature of 227-230 ℃ under normal pressure.

The 3-methyl-1-hexyne-3-ol fraction (purity 96.9%) was obtained by fractional distillation, 54.1g, and 336.5g of 4, 7-dimethyl-5-decyne-4, 7-diol (purity 96.2%) was obtained. The product was calculated to yield 376.1g of pure product, 13.9% 3-methyl-1-hexyn-3-ol and 86.1% 4, 7-dimethyl-5-decyne-4, 7-diol.

Example 2:

the procedure was followed as in example 1, wherein: the feeding in the operation step (1) is 2000g of solvent n-butyl ether, and the catalyst is 140g of potassium hydroxide (industrial grade, purity 94%). The acetylene pressure is 0.1MPa to 0.12 MPa.

The charge in operation (2) was 370g of 2-pentanone (technical grade, purity 99.5%), corresponding to 2-pentanone: potassium hydroxide (pure) =1.1:1 (molar ratio). The acetylene pressure is 0.12MPa to 0.14 MPa.

In the operation step (3), 268g of 2-pentanone (industrial grade, purity 99.5%) is fed, and the total amount of 2-pentanone fed in two times is calculated, wherein the molar ratio of potassium hydroxide (pure) =1.9: 1. Controlling the entering temperature of the aqueous medium at 78-80 ℃; and controlling the residence time of the reaction materials in the reaction tube to be 1-1.5 minutes. The total amount of clear water used for terminating the reaction was about 300 g.

30.3g of 3-methyl-1-hexyne-3-ol fraction (purity 97.5%) and 407.7g of 4, 7-dimethyl-5-decyne-4, 7-diol (purity 96.7%) were obtained by fractional distillation. The product purity was calculated to be 423.7g total, with 3-methyl-1-hexyn-3-ol accounting for 6.9% and 4, 7-dimethyl-5-decyne-4, 7-diol accounting for 93.1%.

Example 3:

the procedure was followed as in example 1, wherein: the material charge in the operation step (1) is 1800g of solvent xylene, and the catalyst is 260g of potassium isobutyl alcohol (self-made, purity 97.5%). The acetylene pressure is 0.1MPa to 0.12 MPa.

The charge in operation step (2) was 390g of 2-pentanone (technical grade, purity 99.5%), which corresponds to 2-pentanone: potassium isobutanol (pure) =1.21:1 (molar ratio). The acetylene pressure is 0.08MPa to 0.1 MPa.

In the operation step (3), 208g of 2-pentanone (industrial grade, purity 99.5%) is fed, and the total amount of 2-pentanone fed in two times is cumulative, wherein the molar ratio of potassium isobutanolate (pure) =1.85: 1. Controlling the entering temperature of the aqueous medium at 62-64 ℃; and controlling the residence time of the reaction materials in the reaction tube to be 2.5-3 minutes. The total amount of clear water used for terminating the reaction was about 550 g.

The 3-methyl-1-hexyne-3-ol fraction (purity 97.2%) was obtained by fractional distillation, 41.5g, and 371.5g of 4, 7-dimethyl-5-decyne-4, 7-diol (purity 96.5%) was obtained. The product purity was calculated to be 398.8g total, of which 3-methyl-1-hexyn-3-ol accounted for 10.1% and 4, 7-dimethyl-5-decyne-4, 7-diol accounted for 89.9%.