阅读说明：本技术 一种联产四甲基十二炔二醇和二甲基庚炔醇的方法 (Method for coproducing tetramethyldodecynediol and dimethylheptynediol ) 是由 王南 张鸿 曾健 王林生 李果 孔林 李代军 于 2021-09-27 设计创作，主要内容包括：一种联产四甲基十二炔二醇(2,5,8,11-四甲基-6-十二炔-5,8-二醇)和二甲基庚炔醇(3,6-二甲基-1-庚炔-3-醇)的方法,以5-甲基-2-己酮和乙炔作原料,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5-甲基-2-己酮与常压或低压的乙炔在较低温度下反应生成二甲基庚炔醇-催化剂络合物,再将其与5-甲基-2-己酮混合后快速通过高温反应管反应生成四甲基十二炔二醇-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用量少等特点。(A process for coproducing tetramethyl dodecynediol (2, 5,8, 11-tetramethyl-6-dodecyne-5, 8-diol) and dimethyl heptynol (3, 6-dimethyl-1-heptynol-3-ol) includes such steps as reaction between 5-methyl-2-hexanone and acetylene as raw materials, reaction between potassium hydroxide or potassium isobutanolate or potassium tert-butoxide as catalyst, mixing it with 5-methyl-2-hexanone at low temp to obtain dimethyl heptynol-catalyst complex, and high-temp reaction to obtain tetramethyl dodecynediol-catalyst complex. 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 co-producing tetramethyldodecyne-diol (chemical name 2,5,8, 11-tetramethyl-6-dodecyne-5, 8-diol) and dimethylheptynol (chemical name 3, 6-dimethyl-1-heptyn-3-ol), 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 acetylene-catalyst complex suspended slurry;

(2) preparation of active dimethyl heptyne alcohol solution by first stage reaction

Adding a first section of 5-methyl-2-hexanone into the suspension slurry, and simultaneously continuously introducing acetylene until the reaction conversion of the 5-methyl-2-hexanone reaches more than 90 percent to generate a solution mainly containing active dimethyl heptynol, namely dimethyl heptynol-catalyst complex;

(3) second-stage reaction for preparing tetramethyl dodecyne diol

Adding the second section of 5-methyl-2-hexanone into the active dimethyl heptyne alcohol solution under normal pressure without introducing acetylene, uniformly mixing, pumping the mixed material into a tubular reactor for reaction to generate a tetramethyldodecynediol-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 material together with water solution to perform hydrolysis reaction, hydrolyzing the tetramethyldodecynediol-catalyst complex and the dimethylheptynol-catalyst complex to decompose the tetramethyldodecynediol, the dimethylheptynol and the potassium hydroxide, wherein the potassium hydroxide is dissolved into the water phase, the tetramethyldodecynediol and the dimethylheptynol are still remained in the oil phase liquid, and separating oil phase from 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, 6-dimethyl-1-heptyne-3-ol with the distillation temperature of 168-170 ℃ under the atmospheric pressure and the fraction 2,5,8, 11-tetramethyl-6-dodecyne-5, 8-diol with the distillation temperature of 267-270 ℃ under the atmospheric pressure.

2. The method for coproducing tetramethyldodecynediol and dimethylheptynediol as claimed in claim 1, wherein the organic solvent used in step (1) simultaneously satisfies the following three conditions:

boiling point of the solvent is required to be lower than 269 ℃ of boiling point of 2,5,8, 11-tetramethyl-6-dodecyne-5, 8-diol and higher than 80 ℃;

secondly, the raw material 5-methyl-2-hexanone and the reaction product 3, 6-dimethyl-1-heptyne-3-ol and 2,5,8, 11-tetramethyl-6-dodecyne-5, 8-diol have larger dissolubility 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-pentyl ether, isoamyl ether, n-hexyl ether, ethylene glycol dibutyl ether, and the like.

3. The method for co-producing tetramethyldodecynediol and dimethylheptynediol as claimed in claim 1, wherein in the step (1), the catalyst is potassium hydroxide, potassium isobutanolate or potassium tert-butoxide with an industrial grade 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: 39-1: 12, further, the weight ratio of the pure potassium hydroxide to the organic solvent is preferably =1: 25-1: 15, 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: 19-1: 5, further, the weight ratio of the pure potassium alkoxide to the organic solvent is preferably =1: 12-1: 7;

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 20-25 ℃; 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 tetramethyldodecynediol and dimethylheptynediol as claimed in claim 1, wherein in the step (2) and the step (3), the total amount of 5-methyl-2-hexanone in the two steps is controlled to satisfy a molar ratio of 5-methyl-2-hexanone to catalyst = 2.0:1 to 1.4:1, and further preferably a molar ratio of 5-methyl-2-hexanone to catalyst =1.8:1 to 1.6: 1; wherein, in the first stage 5-methyl-2-hexanone to catalyst =1:1 to 1.2:1 molar ratio in step (2), all of the remaining 5-methyl-2-hexanone is added in step (3).

5. The method for co-producing tetramethyldodecynediol and dimethylheptynediol as claimed in claim 1, wherein in the step (2), the reaction temperature is controlled in the range of 20 ℃ to 45 ℃; 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 4-6 hours.

6. The method for co-producing tetramethyldodecynediol and dimethylheptynediol as claimed in claim 1, wherein in the step (3), the end-point material obtained in the step (2) is mixed with the second-stage 5-methyl-2-hexanone and then directly pressed into the reaction tube for reaction without introducing acetylene, wherein 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 tetramethyldodecynediol and dimethylheptynediol as claimed in claim 1, wherein in the step (3), the amount of the clear water used for terminating the reaction is 2-3 times of the amount of the initial catalyst.

8. The method for co-producing tetramethyldodecynediol and dimethylheptynediol as claimed in claim 1, wherein in the 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 method for synthesizing chemical substances 2,5,8, 11-tetramethyl-6-dodecyne-5, 8-diol and 3, 6-dimethyl-1-heptyne-3-ol.

Background

Tetramethyldodecyne-diol (chemical name 2,5,8, 11-tetramethyl-6-dodecyne-5, 8-diol) and dimethylheptyne-ol (chemical name 3, 6-dimethyl-1-heptyne-3-ol), both of which have excellent surface activity, are used alone or as one of the components, and are also upstream 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 the molecular structures of the two chemical substances show that the tetramethyldodecynediol and the dimethylheptynediol can be prepared from 5-methyl-2-hexanone and acetylene by a Reppe method production process, but the molecular structures of the raw materials have large steric hindrance, and the reaction process needs higher temperature and longer reaction time, which inevitably causes side reactions such as polymerization of reaction products under a long-term high-temperature environment, and simultaneously 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 jointly producing tetramethyldodecyne diol (chemical name is 2,5,8, 11-tetramethyl-6-dodecyne-5, 8-diol) and dimethylheptyne alcohol (chemical name is 3, 6-dimethyl-1-heptyne-3-ol) with low reaction temperature, short reaction time, less side reactions and low catalyst consumption.

The invention adopts the following technical scheme:

the production and synthesis of tetramethyldodecyne diol (chemical name is 2,5,8, 11-tetramethyl-6-dodecyne-5, 8-diol) and dimethylheptyne alcohol (chemical name is 3, 6-dimethyl-1-heptyne-3-ol) are carried out according to the following technical scheme by taking 5-methyl-2-hexanone and acetylene as initial 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 lower than the boiling point (269 ℃) of 2,5,8, 11-tetramethyl-6-dodecyne-5, 8-diol and higher than 80 ℃ (reaction temperature);

(2) the raw materials of 5-methyl-2-hexanone and the reaction products of 3, 6-dimethyl-1-heptyne-3-ol and 2,5,8, 11-tetramethyl-6-dodecyne-5, 8-diol have larger dissolubility and small intersolubility with water;

(3) is stable to strong alkali.

Meanwhile, the organic solvent satisfying the above conditions includes ether solvents such as n-propyl ether, ethyl butyl ether, n-pentyl ether, isopentyl ether, n-hexyl ether, and ethylene glycol dibutyl ether.

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: 39-1: 12 (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: 25-1: 15 (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: 19-1: 5 (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: 12-1: 7 (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 20-25 ℃; 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. Preparation of active dimethyl heptyne alcohol solution by first stage reaction

Continuously introducing acetylene, simultaneously uniformly and slowly adding the first section of 5-methyl-2-hexanone into the active acetylene suspension slurry, and continuously reacting until the reaction conversion of the 5-methyl-2-hexanone reaches more than 90 percent to generate a solution of active dimethyl heptynol (dimethyl heptynol-catalyst complex).

The total adding amount of the 5-methyl-2-hexanone in the first stage reaction operation and the second stage reaction operation is controlled to meet the molar ratio of 5-methyl-2-hexanone to catalyst (pure) = 2.0: 1-1.4: 1, and preferably 5-methyl-2-hexanone to catalyst (pure) =1.8: 1-1.6: 1. Wherein, in the first stage of the reaction, the molar ratio of 5-methyl-2-hexanone to catalyst (pure) =1: 1-1.2: 1 is controlled. The remaining 5-methyl-2-hexanone was added in the second stage of the reaction.

In the operation, the time for feeding the 5-methyl-2-hexanone is controlled to be 1.5-2.5 hours, and the total reaction time is 4-6 hours; the reaction temperature is controlled within the range of 20-45 (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 tetramethyl dodecyne diol

And (2) adding the second section of 5-methyl-2-hexanone 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 tetramethyldodecynediol-catalyst complex, and immediately feeding 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 5-methyl-2-hexanone of this section is short of amount, and reaction temperature is higher, and 5-methyl-2-hexanone basically finishes reacting after the reaction mass passes 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 tetramethyldodecynediol-catalyst complex and dimethylheptynol-catalyst complex.

4. Hydrolysis separation dealkalization

Stirring the materials (together with water) at the end of the reaction for hydrolysis reaction, hydrolyzing the tetramethyldodecynediol-catalyst complex and the dimethylheptynol-catalyst complex to obtain tetramethyldodecynediol, dimethylheptynol and potassium hydroxide, wherein the potassium hydroxide is dissolved into the water phase, and the tetramethyldodecynediol and the dimethylheptynol 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 carrying out reduced pressure or atmospheric pressure fractionation on the oil phase liquid, and respectively collecting a fraction (3, 6-dimethyl-1-heptyne-3-ol) with the distillation temperature of 168-170 ℃ under the atmospheric pressure and a fraction (2, 5,8, 11-tetramethyl-6-dodecyne-5, 8-diol) with the distillation temperature of 267-270 ℃ under the atmospheric pressure.

The technical method of the invention can achieve the following effects:

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 5-methyl-2-hexanone is controlled in the first-stage reaction, the reaction is mainly carried out to generate the dimethyl heptynol, 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 dimethylheptynol and is not beneficial to the generation of side reaction. The second-stage reaction temperature is high, the generation of the tetramethyldodecynediol is facilitated, 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 5-methyl-2-hexanone can reach more than 92%.

4. The residual raw material 5-methyl-2-hexanone 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 tetramethyl dodecyne diol and the dimethyl heptynol are co-produced, wherein the tetramethyl dodecyne diol is mainly used as a product, and the weight ratio of the tetramethyl dodecyne diol to the dimethyl heptynol is = 9: 1-3: 1.

Detailed Description

Example 1:

(1) adding 2000g of solvent n-butyl ether and 110g of potassium hydroxide (industrial grade, purity is 94%) 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 20-25 ℃ for control. And introducing acetylene gas, keeping the acetylene pressure within the range of 0.08-0.1 MPa, and reacting for 1.5 hours.

(2) 5-methyl-2-hexanone (industrial grade, purity 99.5%) 410g is uniformly and slowly added into a reaction kettle from an overhead tank, the addition is controlled to be completed within 110-130 minutes, and the acetylene pressure is kept within the range of 008 MPa-0.1 MPa for reaction. After the addition of 5-methyl-2-hexanone, the reaction temperature was gradually raised to 43-45 ℃ at a rate of 2-3 ℃ every 10 minutes and then maintained. The reaction is carried out for about 4.5 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 reaction initial mixture, 5-methyl-2-hexanone to potassium hydroxide (pure) =1.1:1 (molar ratio).

(3) Adding 260g of 5-methyl-2-hexanone into a reaction kettle, uniformly mixing, pumping the mixed material into a tubular reactor, controlling the flow speed of the material in the 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 5-methyl-2-hexanone added in two times is potassium hydroxide (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 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 to terminate the reaction was about 250 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, 6-dimethyl-1-heptyne-3-ol) with the distillation temperature of 168-170 ℃ under normal pressure and a fraction (2, 5,8, 11-tetramethyl-6-dodecene-5, 8-diol) with the distillation temperature of 267-270 ℃ under normal pressure.

The 3, 6-dimethyl-1-heptyn-3-ol fraction (purity 97.6%) was obtained by fractional distillation in an amount of 53.9g, and 2,5,8, 11-tetramethyl-6-dodecyn-5, 8-diol (purity 96.2%) in an amount of 364.3g was obtained. The product was calculated to yield a total of 403.1g of 3, 6-dimethyl-1-heptyn-3-ol and 86.9% of 2,5,8, 11-tetramethyl-6-dodecyn-5, 8-diol.

Example 2:

the procedure was followed as in example 1, wherein: the solvent of the feeding material in the operation step (1) is 1900g of ethyl butyl ether, and the catalyst is 210g of potassium tert-butoxide (technical grade, purity 98%). The acetylene pressure is 0.1MPa to 0.12 MPa.

In the operation step (2), 415g of 5-methyl-2-hexanone (industrial grade, purity 99.5%) is charged, which corresponds to 5-methyl-2-hexanone: potassium tert-butoxide (pure) =1.16:1 (molar ratio). The acetylene pressure is 0.1MPa to 0.12 MPa.

In the operation step (3), 250g of 5-methyl-2-hexanone (industrial grade, purity 99.5%) is fed, and the total amount of 5-methyl-2-hexanone fed in two times is potassium tert-butoxide (pure) =1.85:1 (molar ratio). 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 450 g.

The 3, 6-dimethyl-1-heptyn-3-ol fraction (purity 97.1%) was obtained by fractional distillation, 41.4g, and 384.7g of 2,5,8, 11-tetramethyl-6-dodecyn-5, 8-diol (purity 96.8%) was obtained. The product purity was calculated to be 412.6g, wherein 3, 6-dimethyl-1-heptyn-3-ol accounted for 9.7%, and 2,5,8, 11-tetramethyl-6-dodecyn-5, 8-diol accounted for 90.3%.

Example 3:

the procedure was followed as in example 1, wherein: the feeding in the operation step (1) is 1800g of solvent ethylene glycol dibutyl ether, and the catalyst is 210g of potassium isobutyl alcohol (self-made, purity 97.5%). The acetylene pressure is 0.12MPa to 0.14 MPa.

In the operation step (2), 440g of 5-methyl-2-hexanone (industrial grade, purity 99.5%) is charged, which corresponds to 5-methyl-2-hexanone and potassium isobutanolate (pure) =1.19:1 (molar ratio). The acetylene pressure is 0.12MPa to 0.14 MPa.

In the operation step (3), 260g of 5-methyl-2-hexanone (industrial grade, purity 99.5%) is fed, and the total amount of 5-methyl-2-hexanone fed in two times is that potassium isobutanolate (pure) =1.9:1 (molar ratio). Controlling the entering temperature of the aqueous medium at 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 450 g.

The 3, 6-dimethyl-1-heptyn-3-ol fraction (purity 97.1%) was obtained by fractional distillation, and 400.7g of 2,5,8, 11-tetramethyl-6-dodecyn-5, 8-diol (purity 96.8%) was obtained. The product was calculated to yield 414.2g of pure product, of which 3, 6-dimethyl-1-heptyn-3-ol accounted for 6.3%, and 2,5,8, 11-tetramethyl-6-dodecyn-5, 8-diol accounted for 93.7%.