CN107129431B - Synthetic method of tribromoneopentyl alcohol - Google Patents
Synthetic method of tribromoneopentyl alcohol Download PDFInfo
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- CN107129431B CN107129431B CN201710401445.4A CN201710401445A CN107129431B CN 107129431 B CN107129431 B CN 107129431B CN 201710401445 A CN201710401445 A CN 201710401445A CN 107129431 B CN107129431 B CN 107129431B
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- pentaerythritol
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/09—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/28—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group
- C07C67/287—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group by introduction of halogen; by substitution of halogen atoms by other halogen atoms
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Abstract
The invention discloses a synthetic method of tribromoneopentyl alcohol, belonging to the technical field of flame retardant synthesis, which takes pentaerythritol, a reducing agent and bromine as initial raw materials, and prepares tribromoneopentyl alcohol through two steps of bromination and deesterification.
Description
Technical Field
The invention relates to a synthetic method of tribromoneopentyl alcohol, belonging to the technical field of flame retardant synthesis.
Background
Tribromoneopentanol is a flame retardant containing bromine, has a bromine content of 73.79%, belongs to fatty bromine, has high bromine content and special stability, and has particularly outstanding hydrolysis resistance and light stability, and can be used as a reaction intermediate of a high-molecular-weight flame retardant or a reaction type flame retardant due to the fact that the tribromoneopentanol contains a reactive functional group hydroxyl. The tribromoneopentyl alcohol is used as a reaction type intermediate of a high molecular weight flame retardant, can be effectively combined with phosphorus due to high solubility of the tribromoneopentyl alcohol, is used as a reaction type flame retardant of polyurethane, has high bromine content and good intermiscibility, and can improve the flame retardant grade of the polyurethane when being applied to hard or soft polyurethane; tribromoneopentanol can produce flame-retardant elastomers with ethyl carbamate groups through the monohydroxy reaction of tribromoneopentanol; in addition, the tribromoneopentyl alcohol can be combined with the dibromoneopentyl alcohol for use, so that the hydroxyl functions of the tribromoneopentyl alcohol and the dibromoneopentyl alcohol are fully utilized; tribromoneopentanol is widely used as a reactive flame retardant in elastomers, coatings and foams.
The traditional method for producing tribromoneopentanol generally adopts a sulfuric acid gas phase method, namely sulfuric acid is dripped into low-concentration hydrobromic acid liquid and then reacts with pentaerythritol, and the product obtained by the method has the advantages of deep color, low yield, large waste acid amount, environmental pollution and no contribution to industrial production.
Disclosure of Invention
The invention provides a synthetic method of tribromoneopentyl alcohol, which is simple, mild in reaction condition, easy to control, easy for industrial production, high in product quality and environment-friendly.
In order to achieve the purpose, the invention adopts the following technical scheme:
the method for synthesizing tribromoneopentanol is characterized by comprising the following steps:
(1) adding pentaerythritol and a reducing agent into an organic solvent, and heating until the pentaerythritol and the reducing agent are completely dissolved;
(2) dropwise adding bromine under a reflux state, continuously refluxing and preserving heat for 8-10h after dropwise adding is finished, reacting the bromine with a reducing agent to obtain hydrogen bromide in the process, and performing substitution reaction on pentaerythritol and the hydrogen bromide;
(3) distilling to 140-150 ℃ after the reaction is finished, and evaporating the organic solvent, the unreacted hydrogen bromide and the water generated by the reaction;
(4) cooling to 80 ℃, adding a catalyst into the residual liquid after distillation, introducing alcohol gas, and reacting for 4-6 h;
(5) after the reaction is finished, cooling the mixture to 50 ℃, adding a dispersing agent, and adjusting the pH to be neutral by using a 5-10% sodium carbonate aqueous solution;
(6) and adding the obtained mixed organic matter into water, crystallizing, washing with water, drying and slicing to obtain the product.
Preferably, the molar ratio of pentaerythritol to reducing agent is 1: 2-4, the molar ratio of the bromine to the pentaerythritol is 2-4:1, the adding amount of the catalyst is 2-5% of the mass of the residual liquid, and the molar ratio of the alcohol gas to the pentaerythritol is 2-4:1, the addition amount of the dispersant is 0.5 to 1 percent of the mass of the mixture.
Preferably, the reducing agent is one or more of urea, ammonia water and hydrazine hydrate.
Preferably, the organic solvent is one or more of formic acid, acetic acid, propionic acid, benzoic acid and boric acid.
Preferably, the molar ratio of the organic solvent to the pentaerythritol is 2-4: 1.
Preferably, the catalyst is one or more of benzenesulfonic acid, tetrabutyl titanate, tetraisopropyl titanate and tin tetrachloride.
Preferably, the dispersant is one or more of OP-10, fatty alcohol ether phosphate, phenol ether phosphate, hydroxyethyl cellulose and sodium dodecyl benzene sulfonate.
Preferably, the alcohol is one or more of isopropanol and isooctanol.
Preferably, the temperature for the reaction by introducing the alcohol gas in the step (4) is 100-180 ℃.
Preferably, the crystallization temperature in the step (6) is 5-20 ℃, and the drying temperature is 85-105 ℃.
The beneficial technical effects of the invention are as follows: pentaerythritol, a reducing agent and bromine are used as initial raw materials, tribromoneopentanol is prepared through two steps of bromination and deesterification, a brand new operation step of a production process is adopted, the reaction yield can reach more than 95 percent at most, the cost is low, the product quality is high, the reaction condition is mild, the control is easy, and the method is environment-friendly.
Detailed Description
The present invention will be further described with reference to the following specific examples.
Example 1
A synthetic method of tribromoneopentanol comprises the following steps:
(1) adding 136g of pentaerythritol and 125g of reducing agent urea into 220g of organic solvent acetic acid, and heating to 140 ℃ to completely dissolve the pentaerythritol and the reducing agent urea;
(2) adding 320g of bromine dropwise in a reflux state, continuing refluxing and preserving heat for 10h after the addition of the bromine is finished, reacting the bromine with reducing agent urea to obtain hydrogen bromide in the process, and performing substitution reaction on pentaerythritol and the hydrogen bromide;
(3) distilling to 150 ℃ after the reaction is finished, and distilling out acetic acid, unreacted hydrogen bromide and water generated by the reaction;
(4) cooling to 80 ℃, adding 8g of catalyst tetrabutyl titanate into the distilled residual liquid, introducing 180g of isopropanol, reacting for 5 hours at the temperature of 160 ℃, and recovering the isopropanol and the generated propyl acetate in the intermediate process;
(5) after the reaction is finished, cooling to 50 ℃, adding 2g of dispersant fatty alcohol ether phosphate, stirring until the mixture is mixed and dissolved, and then adjusting the pH value to be neutral by using a 5% sodium carbonate aqueous solution;
(6) adding the obtained mixed organic matter into 2000g of water for dispersion, crystallizing, washing, drying and slicing to obtain the product, wherein the crystallization temperature is 10 ℃, and the drying temperature is 95 ℃.
Example 2
A synthetic method of tribromoneopentanol comprises the following steps:
(1) adding 136g of pentaerythritol and 140g of reducing agent ammonia water into 240g of organic solvent acetic acid, and heating to 140 ℃ to completely dissolve the pentaerythritol and the reducing agent ammonia water;
(2) dripping 639g of bromine under a reflux state, continuing refluxing and preserving heat for 9 hours after dripping is finished, reacting the bromine with reducing agent urea to obtain hydrogen bromide in the process, and performing substitution reaction on pentaerythritol and the hydrogen bromide;
(3) distilling to 150 ℃ after the reaction is finished, and distilling out acetic acid, unreacted hydrogen bromide and water generated by the reaction;
(4) cooling to 80 ℃, adding 16g of catalyst tetrabutyl titanate into the distilled residual liquid, introducing 240g of isopropanol, reacting for 6 hours at the temperature of 160 ℃, and recovering the isopropanol and the generated propyl acetate in the intermediate process;
(5) after the reaction is finished, cooling to 50 ℃, adding 6g of dispersant fatty alcohol ether phosphate, stirring until the mixture is mixed and dissolved, and then adjusting the pH value to be neutral by using a 5% sodium carbonate aqueous solution;
(6) and adding the obtained mixed organic matter into 4000g of water for dispersion, crystallizing, washing, drying and slicing to obtain a product, wherein the crystallization temperature is 15 ℃, and the drying temperature is 100 ℃.
Example 3
A synthetic method of tribromoneopentanol comprises the following steps:
(1) adding 136g of pentaerythritol and 135g of reducing agent urea into 180g of organic solvent acetic acid, and heating to 140 ℃ to completely dissolve the pentaerythritol and the reducing agent urea;
(2) 480g of bromine is dripped in a reflux state, the reflux and heat preservation are continued for 8 hours after the dripping is finished, in the process, the bromine reacts with reducing agent urea to obtain hydrogen bromide, and pentaerythritol reacts with the hydrogen bromide for substitution reaction;
(3) distilling to 150 ℃ after the reaction is finished, and distilling out acetic acid, unreacted hydrogen bromide and water generated by the reaction;
(4) cooling to 80 ℃, adding 11g of catalyst tetrabutyl titanate into the distilled residual liquid, introducing 180g of isopropanol, reacting for 5 hours at the temperature of 160 ℃, and recovering the isopropanol and the generated propyl acetate in the intermediate process;
(5) after the reaction is finished, cooling to 50 ℃, adding 4g of dispersant fatty alcohol ether phosphate, stirring until the mixture is mixed and dissolved, and then adjusting the pH value to be neutral by using a 5% sodium carbonate aqueous solution;
(6) and adding the obtained mixed organic matter into 3000g of water for dispersion, crystallizing, washing, drying and slicing to obtain the product, wherein the crystallization temperature is 20 ℃, and the drying temperature is 90 ℃.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and various modifications and variations which do not require inventive efforts and are made by those skilled in the art are still within the scope of the present invention.
Claims (7)
1. The method for synthesizing tribromoneopentanol is characterized by comprising the following steps:
(1) adding pentaerythritol and a reducing agent into an organic solvent, and heating until the pentaerythritol and the reducing agent are completely dissolved;
(2) dropwise adding bromine under a reflux state, continuously refluxing and preserving heat for 8-10h after dropwise adding is finished, reacting the bromine with a reducing agent to obtain hydrogen bromide in the process, and performing substitution reaction on pentaerythritol and the hydrogen bromide;
(3) distilling to 140-150 ℃ after the reaction is finished, and evaporating the organic solvent, the unreacted hydrogen bromide and the water generated by the reaction;
(4) cooling to 80 ℃, adding a catalyst into the residual liquid after distillation, introducing alcohol gas, and reacting for 4-6 h;
(5) after the reaction is finished, cooling the mixture to 50 ℃, adding a dispersing agent, and adjusting the pH to be neutral by using a 5-10% sodium carbonate aqueous solution;
(6) adding the obtained mixed organic matter into water, crystallizing, washing with water, drying, and slicing to obtain a product;
the reducing agent is one or more of urea, ammonia water and hydrazine hydrate;
the catalyst is one or more of benzenesulfonic acid, tetrabutyl titanate, tetraisopropyl titanate and stannic chloride;
the dispersing agent is one or more of OP-10, fatty alcohol ether phosphate, phenol ether phosphate, hydroxyethyl cellulose and sodium dodecyl benzene sulfonate.
2. The method for synthesizing tribromoneopentanol according to claim 1, wherein the molar ratio of pentaerythritol to the reducing agent is 1: 2-4, the molar ratio of the bromine to the pentaerythritol is 2-4:1, the adding amount of the catalyst is 2-5% of the mass of the residual liquid, and the molar ratio of the alcohol gas to the pentaerythritol is 2-4:1, the addition amount of the dispersant is 0.5 to 1 percent of the mass of the mixture.
3. The method for synthesizing tribromoneopentanol according to claim 1, wherein the organic solvent is one or more of formic acid, acetic acid, propionic acid, benzoic acid and boric acid.
4. The method for synthesizing tribromoneopentanol according to claim 1, wherein the molar ratio of the organic solvent to the pentaerythritol is 2-4: 1.
5. The method for synthesizing tribromoneopentanol according to claim 1, wherein the alcohol is one or more of isopropanol and isooctanol.
6. The method for synthesizing tribromoneopentanol according to claim 1, wherein the temperature for the reaction of introducing alcohol gas in step (4) is 100-180 ℃.
7. A synthesis process of tribromoneopentanol according to claim 1, characterized in that the crystallization temperature in step (6) is 5-20 ℃ and the drying temperature is 85-105 ℃.
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| CN110903163B (en) * | 2019-09-17 | 2023-01-03 | 丛强 | Preparation method of tribromoneopentyl alcohol |
| CN110903188B (en) * | 2019-09-17 | 2023-01-03 | 丛强 | Method for preparing tribromoneopentanol acetate |
| CN112778356B (en) * | 2020-12-26 | 2022-07-01 | 山东日兴新材料股份有限公司 | One-pot synthesis process of tri (tribromoneopentyl) phosphate flame retardant |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4929775A (en) * | 1989-05-30 | 1990-05-29 | Ethyl Corporation | Process for preparing brominated pentaerythritols |
| CN101016227A (en) * | 2007-02-08 | 2007-08-15 | 宜兴市中正化工有限公司 | Synthetic method and refining for tribromoneoamyl alcohol |
| CN101979390A (en) * | 2010-09-14 | 2011-02-23 | 华东理工大学 | Bithiazole derivates and use thereof |
| CN106589189A (en) * | 2016-11-18 | 2017-04-26 | 寿光市泰源化工有限公司 | Polypentabromobenzyl acrylate and tribromoneopentyl alcohol co-preparation method suitable for industrial production |
-
2017
- 2017-05-31 CN CN201710401445.4A patent/CN107129431B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4929775A (en) * | 1989-05-30 | 1990-05-29 | Ethyl Corporation | Process for preparing brominated pentaerythritols |
| CN101016227A (en) * | 2007-02-08 | 2007-08-15 | 宜兴市中正化工有限公司 | Synthetic method and refining for tribromoneoamyl alcohol |
| CN101979390A (en) * | 2010-09-14 | 2011-02-23 | 华东理工大学 | Bithiazole derivates and use thereof |
| CN106589189A (en) * | 2016-11-18 | 2017-04-26 | 寿光市泰源化工有限公司 | Polypentabromobenzyl acrylate and tribromoneopentyl alcohol co-preparation method suitable for industrial production |
Non-Patent Citations (1)
| Title |
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| 液相法合成二溴新戊二醇;马丽锋等;《广东化工》;20101231;第37卷(第5期);148-149 * |
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Denomination of invention: A synthetic method of tribromo neopentyl alcohol Effective date of registration: 20211022 Granted publication date: 20200724 Pledgee: Postal Savings Bank of China Limited Shouguang sub branch Pledgor: SHANDONG RIXING NEW MATERIAL CO.,LTD. Registration number: Y2021980011152 |