CN111217667B - Synthetic method of tetrabromocyclooctane - Google Patents
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Abstract
The invention relates to a synthetic method of tetrabromocyclooctane, which solves the technical problems of complex synthetic process, poor product purity, difficult solvent recovery, low product yield, more byproducts, poor thermal stability, influence on flame retardant property and environmental pollution of the synthetic method of tetrabromocyclooctane in the prior art. A synthetic method of tetrabromocyclooctane comprises the following steps: 1) adding a catalyst into an organic solvent, cooling to below 30 ℃, and adding bromine to prepare a brominating agent; 2) adding a mixed solvent of aliphatic alcohol and halogenated alkane into a reaction device, controlling the temperature not to exceed 40 ℃, simultaneously dropwise adding the brominating agent prepared in the step 1) and 1, 5-cyclooctadiene into the reaction device under a stirring state, heating until a system is subjected to reflux reaction, and crystallizing and separating out tetrabromocyclooctane; 3) recovering the catalyst for reuse; 4) and desolventizing and drying the tetrabromocyclooctane. The invention is widely applied to the technical field of flame retardant synthesis.
Description
Technical Field
The invention belongs to the technical field of flame retardant synthesis, and particularly relates to a synthetic method of tetrabromocyclooctane.
Background
Tetrabromocyclooctane is also called as 1,2,5,6 tetrabromocyclooctane and is an important organic brominated flame retardant, the American jabo chemical product is of the brand number BC-48, and the flame retardant is mainly applied to the flame retardance of products such as expanded polystyrene, crystal and HIPS, SAN resin, adhesive, coating, fabric processing polyurethane and the like. Is a novel flame retardant with great development prospect and is one of the most active fields for researching and developing flame retardants.
At present, the main production method of tetrabromocyclooctane is to directly bromize trichloromethane as a solvent and bromine and cyclooctadiene as raw materials to obtain a product. Adding trichloromethane into a reaction kettle, cooling to below 0 ℃, simultaneously dripping cyclooctadiene and bromine, preserving heat for 5 hours at low temperature, heating to 30 ℃, preserving heat for 5 hours, desolventizing and drying materials to obtain a tetrabromocyclooctane product. The method has the advantages of difficult reaction post-treatment, consumption of a large amount of organic solvent, higher equipment requirement, direct use of bromine as a brominating reagent, more product impurities, low yield and poor thermal stability, and seriously influences the flame retardant property of the product.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide the synthesis method of the tetrabromocyclooctane, which has the advantages of simple reaction path, high yield, less impurity content, simple and feasible product post-treatment method, high thermal stability, cost saving and environmental protection.
The technical scheme adopted by the invention for solving the technical problem is as follows:
a synthetic method of tetrabromocyclooctane comprises the following steps:
1) synthesis of brominating agent:
adding a certain amount of catalyst into an organic solvent, cooling to below 30 ℃, and adding a certain amount of bromine into the system to prepare a brominating agent;
2) synthesis of tetrabromocyclooctane:
adding a mixed solvent of aliphatic alcohol and halogenated alkane into a reaction device, controlling the reaction temperature to be not more than 40 ℃, simultaneously dropwise adding the brominating agent prepared in the step 1) and 1, 5-Cyclooctadiene (COD) into the reaction device under a stirring state, after dropwise adding, heating until a system is subjected to reflux reaction, and crystallizing and separating out a tetrabromocyclooctane product as a white solid along with the reaction;
3) recycling the catalyst:
adding quantitative water into the tetrabromocyclooctane system prepared in the step 2), and recycling the water-soluble catalyst after dehydration and drying;
4) desolventizing and drying tetrabromocyclooctane:
washing the semi-finished tetrabromocyclooctane prepared in the step 3) with water to remove impurities, distilling the solvent by adopting steam under a vacuum condition at a certain temperature, evaporating residual water under reduced pressure, crystallizing and separating out the product in a white particle form, and then drying in vacuum at 100 ℃ to obtain the finished product.
Preferably, in the step 1), the organic solvent is a halogenated alkane solvent, and the organic solvent is one or more of dichloromethane, dichloroethane, chloroform and carbon tetrachloride; the mass ratio of the organic solvent to the bromine is 5-10: 1.
Preferably, in the step 1), the catalyst is a quaternary ammonium salt phase transfer catalyst, the quaternary ammonium salt is one of tetramethylammonium chloride, tetramethylammonium bromide, tetraethylammonium bromide, tetrabutylammonium bromide, benzyltriethylammonium chloride and hexadecyltrimethylammonium bromide, and the molar mass ratio of the addition amount of the quaternary ammonium salt to the addition amount of the bromine in the step 1) is 3-5: 1.
Preferably, in the step 2), the mixed solvent is a mixed solvent of fatty alcohol and halogenated alkane, the fatty alcohol is long-chain fatty alcohol with solubility lower than 20% in water, and is one or more of n-butanol, isobutanol, n-hexanol and isooctanol; the halogenated alkane is one or more of dichloromethane, dichloroethane, trichloromethane and carbon tetrachloride, and the halogenated alkane is consistent with the organic solvent in the step 1); the mass ratio of the aliphatic alcohol to the halogenated alkane in the mixed solvent is 1-5:1, and the addition amount of the mixed solvent is 10-20 times of the addition amount of the 1, 5-Cyclooctadiene (COD) in the step 2).
Preferably, in the step 2), the molar mass ratio of the brominating agent to 1, 5-Cyclooctadiene (COD) is 2-3: 1.
Preferably, in the step 3), the mass ratio of the water used for washing and recovering the catalyst to the catalyst is 1-3: 1.
Preferably, in the step 4), the temperature for removing the solvent by steam distillation under the vacuum condition is 110-140 ℃.
The invention has the beneficial effects that:
(1) the synthetic method of tetrabromocyclooctane provided by the invention has the advantages of simple reaction path, high yield phase, less impurity content, cost saving, environment-friendly production process, simple and feasible product post-treatment method and high thermal stability.
(2) According to the synthesis method of tetrabromocyclooctane, the self-made mild brominating agent is used, so that the thermal stability of the product is obviously improved, and the comprehensive utilization rate of bromine is high; by using the heat stabilizer, the heat stability of the product is greatly improved, and the method is suitable for industrial production; the catalyst can be recycled, and the green environmental protection concept is met.
(3) The synthetic method of tetrabromocyclooctane has the advantages of small harm to the environment, high product yield and good product quality.
Detailed Description
The present invention will be further described with reference to specific examples to assist understanding of the invention. The method used in the invention is a conventional production method if no special provisions are made; the starting materials used, unless otherwise specified, are conventional commercial products.
Example one
The method for synthesizing tetrabromocyclooctane comprises the following steps:
1) synthesis of brominating agent:
adding 369g of quaternary ammonium salt tetramethyl ammonium bromide into 480g of organic solvent dichloromethane, cooling to below 30 ℃, and dropwise adding 96g of bromine Br into the system2Dissolving the brominating agent completely to prepare a brominating agent;
2) synthesis of tetrabromocyclooctane:
adding 583g of mixed solvent of n-butanol and dichloromethane into a reaction device, wherein the n-butanol is 437g, the dichloromethane is 146g, controlling the reaction temperature to be lower than 40 ℃, simultaneously dropwise adding the brominating agent prepared in the step 1) and 32.4g of 1, 5-cyclooctadiene into the reaction device under the stirring state, after dropwise adding, heating until the system is subjected to reflux reaction, and crystallizing and separating out a tetrabromocyclooctane product as a white solid along with the reaction;
3) recycling and reusing the catalyst:
960g of water is added into the tetrabromocyclooctane system prepared in the step 2), and the water-soluble quaternary ammonium tetramethylammonium bromide is recycled after dehydration and drying;
4) desolventizing and drying tetrabromocyclooctane:
washing the semi-finished product of tetrabromocyclooctane prepared in the step 3) to remove impurities, taking an organic phase, and removing a solvent by adopting steam distillation under a vacuum condition: under the vacuum condition, controlling the vacuum degree at-0.9 Mpa and the temperature at 120 ℃, slowly introducing steam, removing the organic solvent by gas, decompressing and distilling off residual moisture, crystallizing and separating out the product in the form of white particles, and drying at 100 ℃ in vacuum to obtain the finished product with the yield of 97.8 percent, the purity of 98.9 percent and the purity of 5 percent WLT210 ℃.
Example 2
The method for synthesizing tetrabromocyclooctane comprises the following steps:
1) synthesis of brominating agent:
adding 504g of quaternary ammonium salt tetraethylammonium bromide into 960g of organic solvent dichloroethane, cooling to below 30 ℃, and dropwise adding 96g of bromine Br2 into the system to completely dissolve the bromine Br2 to prepare a brominating agent;
2) synthesis of tetrabromocyclooctane:
adding 270g of mixed solvent of isooctanol and dichloroethane into a reaction device, wherein the isooctanol is 135g, the dichloroethane is 135g, controlling the reaction temperature to be lower than 40 ℃, simultaneously dripping the brominating agent prepared in the step 1) and 27g of 1, 5-cyclooctadiene into the reaction device under the stirring state, heating until the system is subjected to reflux reaction after dripping is finished, and crystallizing and separating out a white solid product along with the reaction of the tetrabromocyclooctane product;
3) recycling the catalyst:
1008g of water is added into the tetrabromocyclooctane system prepared in the step 2), and the water-soluble quaternary ammonium salt tetraethylammonium bromide is recycled after dehydration and drying;
4) desolventizing and drying tetrabromocyclooctane:
washing the semi-finished product of tetrabromocyclooctane prepared in the step 3) to remove impurities, taking an organic phase, and removing a solvent by adopting steam distillation under a vacuum condition: under the vacuum condition, controlling the vacuum degree at-0.9 Mpa and the temperature at 130 ℃, slowly introducing steam, removing the organic solvent by gas, decompressing and distilling off residual moisture, crystallizing and separating out the product in the form of white particles, and drying in vacuum at 100 ℃ to obtain the finished product with the yield of 98.7 percent, the purity of 99.0 percent and the purity of 5 percent WLT210 ℃.
Example 3
The method for synthesizing tetrabromocyclooctane comprises the following steps:
1) synthesis of brominating agent:
adding 966g of quaternary ammonium salt tetrabutylammonium bromide into 672g of organic solvent trichloromethane, cooling to below 30 ℃, dropwise adding 96g of bromine Br2 into the system, and completely dissolving to prepare a brominating agent;
2) synthesis of tetrabromocyclooctane:
adding 500g of mixed solvent of n-hexanol and trichloromethane into a reaction device, wherein the n-hexanol is 417g, the trichloromethane is 83g, controlling the reaction temperature to be lower than 40 ℃, simultaneously dropwise adding the brominating agent prepared in the step 1) and 25g of 1, 5-cyclooctadiene into the reaction device under the stirring state, after the dropwise adding is finished, heating the system to perform reflux reaction, and crystallizing and separating out a white solid from a tetrabromocyclooctane product along with the reaction;
3) recycling and reusing the catalyst:
adding 966g of water into the tetrabromocyclooctane system prepared in the step 2), and recycling the water-soluble quaternary ammonium salt tetrabutylammonium bromide for recycling after dehydration and drying;
4) desolventizing and drying tetrabromocyclooctane:
washing the semi-finished tetrabromocyclooctane prepared in the step 3) to remove impurities, taking an organic phase, and distilling by adopting water vapor under a vacuum condition to remove a solvent: under the vacuum condition, controlling the vacuum degree at-0.9 Mpa and the temperature at 110 ℃, slowly introducing steam, removing the organic solvent by gas, decompressing and distilling off residual moisture, crystallizing and separating out the product in the form of white particles, and drying in vacuum at 100 ℃ to obtain the finished product with the yield of 98.3 percent, the purity of 99.1 percent and the purity of 5 percent WLT210 ℃.
Example 4
The method for synthesizing tetrabromocyclooctane comprises the following steps:
1) synthesis of brominating agent:
adding 411g of quaternary ammonium salt benzyltriethylammonium chloride into 672g of organic solvent carbon tetrachloride, cooling to below 30 ℃, and dropwise adding 96g of bromine Br2 into the system to completely dissolve the bromine, thereby preparing a brominating agent;
2) synthesis of tetrabromocyclooctane:
adding 480g of mixed solvent of isooctanol and carbon tetrachloride into a reaction device, wherein the isooctanol is 384g, the carbon tetrachloride is 96g, controlling the reaction temperature to be lower than 40 ℃, simultaneously dripping the brominating agent prepared in the step 1) and 30g of 1, 5-cyclooctadiene into the reaction device under the stirring state, heating until the system is subjected to reflux reaction after dripping is finished, and crystallizing and separating out a tetrabromocyclooctane product as white solid along with the reaction;
3) recycling and reusing the catalyst:
adding 1233g of water into the tetrabromocyclooctane system prepared in the step 2), and recycling the water-soluble quaternary ammonium benzyltriethylammonium chloride for recycling after dehydration and drying;
4) desolventizing and drying tetrabromocyclooctane:
washing the semi-finished tetrabromocyclooctane prepared in the step 3) to remove impurities, taking an organic phase, and distilling by adopting water vapor under a vacuum condition to remove a solvent: under the vacuum condition, controlling the vacuum degree to be-0.9 Mpa and the temperature to be 110 ℃, slowly introducing steam, removing the organic solvent by gas, decompressing and steaming out residual moisture, crystallizing and separating out the product in the form of white particles, and drying in vacuum at 100 ℃ to obtain the finished product with the yield of 97.8 percent, the purity of 98.5 percent and the purity of 5 percent WLT210 ℃.
Example 5
The method for synthesizing tetrabromocyclooctane comprises the following steps:
1) synthesis of brominating agent:
adding 873g of quaternary ammonium salt hexadecyl trimethyl ammonium bromide into 672g of organic solvent dichloroethane and trichloromethane, cooling to below 30 ℃, and dropwise adding 96g of bromine Br2 into the system to completely dissolve the bromine Br2 to prepare a brominating agent;
2) synthesis of tetrabromocyclooctane:
324g of mixed solvent of isobutanol, dichloroethane and chloroform is added into a reaction device, wherein 216g of isobutanol is added, 108g of dichloroethane and chloroform are added, the reaction temperature is controlled to be lower than 40 ℃, the brominating agent prepared in the step 1) and 21.6g of 1, 5-cyclooctadiene are simultaneously dripped into the reaction device under the stirring state, after dripping is finished, the temperature is raised until the system performs reflux reaction, and a tetrabromocyclooctane product is crystallized and separated out as white solid along with the reaction;
3) recycling and reusing the catalyst:
960g of water is added into the tetrabromocyclooctane system prepared in the step 2), and the water-soluble quaternary ammonium salt cetyl trimethyl ammonium bromide is recycled after dehydration and drying;
4) desolventizing and drying tetrabromocyclooctane:
washing the semi-finished product of tetrabromocyclooctane prepared in the step 3) to remove impurities, taking an organic phase, and removing a solvent by adopting steam distillation under a vacuum condition: under the vacuum condition, controlling the vacuum degree at-0.9 Mpa and the temperature at 140 ℃, slowly introducing steam, removing the organic solvent by gas, decompressing and distilling off residual moisture, crystallizing and separating out the product in the form of white particles, and drying in vacuum at 100 ℃ to obtain the finished product with the yield of 98.6 percent, the purity of 99.3 percent and the purity of 5 percent WLT210 ℃.
The following further analysis of the data from the above examples 1-5 is summarized below:
the synthesis method of tetrabromocyclooctane provided by the invention adopts a completely different synthesis method, the self-made brominating agent used in the method improves the thermal stability of the product, and the comprehensive utilization rate of bromine is high; the preparation method has the advantages of small harm to the environment, high product yield and good product quality.
The halogenated alkane is selected as the raw material of the brominating agent, so that the reaction rate of the product can be controlled, and a good dissolving effect can be achieved.
Double bond on 1, 5-Cyclooctadiene (COD) and bromine Br without catalyst2An electrophilic addition reaction can be generated, but due to bromine Br2Is a strong brominating reagent when bromine Br2When the amount is large, the product has yellow color, increased acid value and poor thermal stability, and when the bromine Br is used2In the case of an insufficient amount, the product yield is lowered and crystallization is difficult. According to the synthetic method of tetrabromocyclooctane, a special mild bromination system is prepared according to the requirement, so that the full reaction of raw materials can be ensured, the generation of byproducts can be inhibited, and the excellent thermal stability of the product is ensured. The quaternary ammonium salt may be combined with bromineThe quaternary ammonium salt is a mild brominating reagent, and after bromine is transferred to double bonds to realize addition reaction, the quaternary ammonium salt does not participate in the main reaction and is only used as a transfer medium of the bromine, so that the method has extremely beneficial effects, obviously promotes the improvement of the thermal stability and yield of the product, and is simple and feasible in crystallization. Therefore, the quaternary ammonium salt is one of tetramethylammonium chloride, tetramethylammonium bromide, tetraethylammonium bromide, tetrabutylammonium bromide, benzyltriethylammonium chloride and hexadecyltrimethylammonium bromide.
From the viewpoint of chemical kinetics, the mediation of quaternary ammonium salt is comprehensively considered, in order to avoid bromine Br in the reaction process2Directly brominating and combining with double bonds on 1, 5-Cyclooctadiene (COD) to obtain quaternary ammonium salt and bromine Br2The proportion of (A) is optimally selected. Preferably, the quaternary ammonium salt is reacted with bromine Br2The molar mass ratio of (A) to (B) is 3-5: 1.
The appropriate excess of brominating agent can ensure the full reaction of 1, 5-Cyclooctadiene (COD) raw material. Thus, bromine Br in the brominating agent2The molar ratio of the 1, 5-Cyclooctadiene (COD) to the 1, 5-cyclooctadiene (I) is 2-3: 1.
The quaternary ammonium salt is used as a relatively expensive medium auxiliary agent, and does not change before and after the reaction, and the feasibility of the process is determined by a reasonable recovery mode. The quaternary ammonium salt has high solubility in water and is hardly dissolved in the halogenated alkane. Therefore, the quaternary ammonium salt is recycled and reused in a water washing mode, is environment-friendly, energy-saving and remarkably cost-saving, is suitable for production of modern industry, accords with the green energy-saving and environment-friendly concept pursued by the modern society, and is beneficial to sustainable development.
The mixed solvent of the fatty alcohol and the halogenated hydrocarbon is selected as the reaction solvent, because the existence of 1, 5-Cyclooctadiene (COD) double bond leads the reaction of the product to be violent, the reaction rate can not be well controlled by common solvent, and the color of the reaction product is greatly influenced, therefore, the invention adopts the method of double solvents, which can delay the reaction rate of the product, simultaneously can play a good dissolving effect, and the appearance effect of the prepared product is good.
Tetrabromocyclooctane has extremely high solubility in halogenated alkane solvents, and the product can be changed into a highly viscous state even in the presence of a small amount of solvent along with the increase of temperature, and the separation of the solvent is one of the difficulties in the industrialization of the product. The general method adopts an anti-solvent mode to realize the crystallization separation of the product, but the introduction of a new organic solvent causes great difficulty for the reasonable separation of the solvent and the natural environment, and simultaneously, in a mixed solvent, the product can not be completely crystallized and separated out, thereby greatly influencing the yield of the product. In the synthesis method of tetrabromocyclooctane, the principle that halogenated alkane and water are azeotropic but immiscible is fully utilized, and negative pressure is assisted to realize the crystallization separation of the product.
However, the above description is only an embodiment of the present invention, and the scope of the present invention should not be limited by this, and all equivalent changes and modifications made in the claims of the present invention should be covered by the present invention.
Claims (7)
1. A synthetic method of tetrabromocyclooctane is characterized by comprising the following steps:
1) synthesis of brominating agent:
adding a certain amount of catalyst into an organic solvent, cooling to below 30 ℃, and adding a certain amount of bromine into the system to prepare a brominating agent; the organic solvent is a halogenated alkane solvent; the catalyst is a quaternary ammonium salt phase transfer catalyst, and the molar mass ratio of the addition amount of the quaternary ammonium salt to the addition amount of the bromine in the step 1) is 3-5: 1;
2) synthesis of tetrabromocyclooctane:
adding a mixed solvent of aliphatic alcohol and halogenated alkane into a reaction device, controlling the reaction temperature to be not more than 40 ℃, simultaneously dropwise adding the brominating agent prepared in the step 1) and 1, 5-Cyclooctadiene (COD) into the reaction device under a stirring state, after dropwise adding, heating until a system is subjected to reflux reaction, and crystallizing and separating out a tetrabromocyclooctane product as a white solid along with the reaction; the fatty alcohol is long-chain fatty alcohol with the solubility lower than 20 percent in water;
3) recycling and reusing the catalyst:
adding quantitative water into the tetrabromocyclooctane system prepared in the step 2), and recycling the water-soluble catalyst after dehydration and drying;
4) desolventizing and drying tetrabromocyclooctane:
washing the semi-finished tetrabromocyclooctane prepared in the step 3) with water to remove impurities, distilling the solvent by adopting steam under a vacuum condition at a certain temperature, evaporating residual water under reduced pressure, crystallizing and separating out the product in a white particle form, and then drying in vacuum at 100 ℃ to obtain the finished product.
2. The method for synthesizing tetrabromocyclooctane according to claim 1, wherein in step 1), the organic solvent is one or more of dichloromethane, dichloroethane, chloroform and carbon tetrachloride; the mass ratio of the organic solvent to the bromine is 5-10: 1.
3. The method as claimed in claim 1, wherein in step 1), the quaternary ammonium salt is one of tetramethylammonium chloride, tetramethylammonium bromide, tetraethylammonium bromide, tetrabutylammonium bromide, benzyltriethylammonium chloride and hexadecyltrimethylammonium bromide.
4. The method for synthesizing tetrabromocyclooctane according to claim 1, wherein in step 2), the mixed solvent is a mixed solvent of aliphatic alcohol and halogenated alkane, and is one or more of n-butanol, isobutanol, n-hexanol and isooctanol; the halogenated alkane is one or more of dichloromethane, dichloroethane, trichloromethane and carbon tetrachloride, and the halogenated alkane is consistent with the organic solvent in the step 1); the mass ratio of the aliphatic alcohol to the halogenated alkane in the mixed solvent is 1-5:1, and the addition amount of the mixed solvent is 10-20 times of the addition amount of the 1, 5-Cyclooctadiene (COD) in the step 2).
5. The method for synthesizing tetrabromocyclooctane according to claim 1, wherein the molar mass ratio of the brominating agent to 1, 5-Cyclooctadiene (COD) in step 2) is 2-3: 1.
6. The method for synthesizing tetrabromocyclooctane according to claim 1, wherein the mass ratio of water used for washing and recovering the catalyst to the catalyst in step 3) is 1-3: 1.
7. The method as claimed in claim 6, wherein the temperature for removing the solvent by steam distillation under vacuum in step 4) is 110-140 ℃.
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| US3652688A (en) * | 1968-12-30 | 1972-03-28 | Cities Service Co | Halogenation of unsaturated hydrocarbons |
| GB1449976A (en) * | 1974-08-28 | 1976-09-15 | Cities Service Co | Bromination of unsaturated hydrocarbons in mixed solvents |
| CS197633B1 (en) * | 1977-08-23 | 1980-05-30 | Jiri Hajek | Process for preparing burning retarders based on mixture of brominated cycloalkanes containing 8-12 carbon atoms |
| CN101139245A (en) * | 2007-09-18 | 2008-03-12 | 淮海工学院 | Novel process for producing hexabromocyclododecane |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3652688A (en) * | 1968-12-30 | 1972-03-28 | Cities Service Co | Halogenation of unsaturated hydrocarbons |
| GB1449976A (en) * | 1974-08-28 | 1976-09-15 | Cities Service Co | Bromination of unsaturated hydrocarbons in mixed solvents |
| CS197633B1 (en) * | 1977-08-23 | 1980-05-30 | Jiri Hajek | Process for preparing burning retarders based on mixture of brominated cycloalkanes containing 8-12 carbon atoms |
| CN101139245A (en) * | 2007-09-18 | 2008-03-12 | 淮海工学院 | Novel process for producing hexabromocyclododecane |
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