CN110655531A - Synthetic method of triisooctyl phosphate - Google Patents
Synthetic method of triisooctyl phosphate Download PDFInfo
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- CN110655531A CN110655531A CN201810686423.1A CN201810686423A CN110655531A CN 110655531 A CN110655531 A CN 110655531A CN 201810686423 A CN201810686423 A CN 201810686423A CN 110655531 A CN110655531 A CN 110655531A
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- phosphorus oxychloride
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/08—Esters of oxyacids of phosphorus
- C07F9/09—Esters of phosphoric acids
- C07F9/11—Esters of phosphoric acids with hydroxyalkyl compounds without further substituents on alkyl
Abstract
The invention discloses a synthesis method of triisooctyl phosphate, which comprises the following steps of reacting phosphorus oxychloride and isooctanol under the conditions of negative pressure, catalyst and N-dimethylaniline as an acid-binding agent, wherein the molar ratio of the phosphorus oxychloride to the isooctanol is 1:3 ~ 1:5, the vacuum degree is controlled to be-0.075 MPa ~ -0.085 MPa in the reaction process, the phosphorus oxychloride is added in a dropwise manner, the temperature of a reaction liquid is controlled to be ~ 40 ℃ in the phosphorus oxychloride dropwise addition process, after the phosphorus oxychloride dropwise addition is finished, the reaction liquid is heated to 110 ℃ ~ 140 ℃, the heat preservation reaction is carried out for 3 ~ 8 hours, after the reaction is finished, the reaction liquid is filtered to obtain tertiary amine hydrochloride and filtrate, and the filtrate is purified and rectified through alkaline washing and high vacuum negative pressure to obtain the product of triisooctyl phosphate.
Description
Technical Field
The invention relates to the technical field of synthesis of triisooctyl phosphate.
Background
Triisooctyl phosphate, molecular formula: c24H5104P, molecular weight: 434.
the triisooctyl phosphate can be used for the separation of nonferrous metals, the purification of rare earth elements, the separation of rare earth and non-rare earth elements, the treatment of phenol-containing wastewater and the like. Triisooctyl phosphate is also a good flame retardant and plasticizer, and is widely applied to vinyl resin, phenolic resin, polyurethane, synthetic rubber and the like.
The triisooctyl phosphate is synthesized by directly esterifying isooctyl alcohol and phosphorus oxychloride serving as raw materials, a large amount of hydrogen chloride can be generated in the reaction process, and the hydrogen chloride and the isooctyl alcohol can easily generate a byproduct of chloroisooctane, so that the content and the yield of a target product are reduced. In order to inhibit the hydrogen chloride from continuing to react with the alcohol, a higher vacuum and a lower reaction temperature are generally controlled, which results in lower product yields and lower recovery of isooctanol.
In the chinese patent CN103435642, phosphorus oxychloride is added in batches under negative pressure, which reduces the generation of chloroisooctane to a certain extent, but the hydrogen chloride gas dissolved in the reaction solution reacts with isooctanol to generate chloroisooctane, and the content of by-products is relatively high.
Disclosure of Invention
The purpose of the invention is: provides a synthesis method of triisooctyl phosphate, hydrogen chloride generated by the reaction can be effectively removed, side reactions are less, and the product purity is high.
In order to achieve the purpose, the technical scheme includes that the synthesis method of triisooctyl phosphate comprises the following steps of reacting phosphorus oxychloride and isooctyl alcohol under the conditions of negative pressure and catalyst and N-dimethylaniline as an acid-binding agent, wherein the molar ratio of the phosphorus oxychloride to the isooctyl alcohol is 1:3 ~ 1:5, the vacuum degree is controlled to be-0.075 MPa ~ -0.085 MPa in the reaction process, the phosphorus oxychloride is added in a dropwise manner, the temperature of a reaction liquid is controlled to be ~ 40 ℃ in the dropwise adding process, the temperature of the reaction liquid is increased to be 110 ℃ ~ 140 ℃ after the dropwise adding of the phosphorus oxychloride is finished, carrying out heat preservation reaction for 3 ~ 8 hours, filtering the reaction liquid after the reaction is finished to obtain tertiary amine hydrochloride and filtrate, and carrying out alkali washing, high-vacuum negative-pressure rectification on the filtrate to obtain the product triisooctyl phosphate.
Further, the synthesis method of triisooctyl phosphate is characterized in that the catalyst is Lewis acid, the Lewis acid comprises titanium tetrachloride, magnesium chloride and aluminum trichloride, and the dosage of the catalyst is ~ 1% of the total mass of the reaction liquid by 0.5%.
Further, in the synthesis method of triisooctyl phosphate, the molar ratio of phosphorus oxychloride to isooctanol is preferably 1: 4.
Further, in the method for synthesizing triisooctyl phosphate, after the phosphorus oxychloride is added, the reaction solution is preferably raised to 120 ℃.
Further, in the method for synthesizing triisooctyl phosphate, after the phosphorus oxychloride is added dropwise, the reaction is preferably performed for 4 hours under heat preservation.
Further, the synthesis method of triisooctyl phosphate comprises the steps of filtering reaction liquid after reaction to obtain filtrate, performing alkali washing by using a sodium carbonate aqueous solution with the mass concentration of 10%, separating liquid to obtain an oil phase, washing the oil phase by using deionized water, and then performing high-vacuum negative-pressure rectification and purification to obtain triisooctyl phosphate, wherein the vacuum degree of the high-vacuum negative-pressure rectification is controlled to be-0098 MPa ~ -0.1 MPa.
Further, in the method for synthesizing triisooctyl phosphate, after the reaction is finished, the reaction solution is filtered to obtain NH for tertiary amine hydrochloride3-NH4And regenerating the CL saturated solution to obtain the N-N dimethylaniline.
The invention has the advantages that: firstly, the reaction is carried out under the conditions of negative pressure and acid binding agent, and the hydrogen chloride generated by the reaction can be removed out of the reaction system in time under the action of the negative pressure, thereby greatly reducing the dissolution in the reaction systemSecondly, phosphorus oxychloride is fed in a dropwise manner, the temperature of the reaction liquid is controlled to be 10 ℃ ~ 40 ℃ in the dropwise process, so that the side reaction can be effectively avoided, and the reaction yield is further improved3-NH4And the Cl saturated solution is regenerated, and the obtained high-concentration N, N-dimethylaniline is recycled as an acid-binding agent, so that the emission of solid waste of the ammonia salt is reduced, and the production cost can be effectively saved.
Detailed Description
The synthesis method of triisooctyl phosphate according to the present invention will be described in detail below.
The synthesis method of triisooctyl phosphate comprises the following steps of reacting phosphorus oxychloride and isooctanol under the conditions of negative pressure, a catalyst and N-N dimethylaniline as an acid-binding agent, wherein the molar ratio of the phosphorus oxychloride to isooctanol is 1:3 ~: 5, preferably 1:4, the catalyst is Lewis acid, the Lewis acid comprises titanium tetrachloride, magnesium chloride and aluminum trichloride, the dosage of the catalyst is 0.5% ~% of the total mass of a reaction liquid, the vacuum degree is controlled to be-0.075 MPa ~ -0.085 MPa in the reaction process, the phosphorus oxychloride is added in a dropping manner, the temperature of the reaction liquid is controlled to be 10 ℃ ~ ℃ in the dropping process of the phosphorus oxychloride, the temperature is controlled to reduce side reactions, after the dropping of the phosphorus oxychloride is finished, the reaction liquid is raised to 110 ℃ ~ ℃, preferably the reaction liquid is raised to 120 ℃, the heat preservation reaction is carried out for 3 ~ hours, preferably 4 hours, after the reaction is finished, the tertiary amine and the filtrate are obtained by filtering the reaction liquid, the filtrate is firstly distilled by using a 10% mass concentration aqueous solution, washing the triisooctyl phosphate with water, and after the vacuum separation of the oil phase is carried out, the high-pressure separation is controlled, the high-00591.
And (3) regenerating the tertiary amine hydrochloride by using a saturated solution of NH3-NH4Cl to obtain the N, N-dimethylaniline. This aims to: the catalyst is recycled, the production cost is reduced, and the emission of ammonia salt solid waste is reduced.
The present invention will be described in further detail with reference to specific examples.
The first embodiment is as follows:
respectively putting 520 g (4 mol) of isooctanol, 6.8 g of aluminum trichloride and 363 g (3 mol) of N-dimethylaniline into a 2-liter three-neck flask, starting a machine for stirring, controlling the temperature of a reaction solution to be about 10 ℃ and the vacuum degree to be-0.08 MPa, then dropwise adding 153 g (1 mol) of phosphorus oxychloride within 2 hours, controlling the temperature of the reaction solution to be 10 ℃ ~ 40 ℃ in the dropwise adding process, raising the temperature of the reaction solution to 120 ℃ after the dropwise adding is finished, preserving the temperature for 4 hours, finishing the reaction, rapidly removing hydrogen chloride generated in the reaction process under the action of negative pressure in the reaction process, cooling the reaction solution, filtering to obtain tertiary amine hydrochloride and filtrate, performing alkaline washing on the filtrate by using a sodium carbonate aqueous solution with the mass concentration of 10%, taking an oil phase after liquid separation, washing the oil phase by using deionized water, keeping the oil phase, controlling the vacuum degree to be-0098 MPa ~ -0.1 MPa under the high vacuum condition, and performing negative pressure rectification and purification on the oil phase to obtain triisooctyl3-NH4And (3) regenerating the Cl saturated solution to obtain high-purity N-N dimethylaniline, wherein the N-N dimethylaniline is used as an acid-binding agent for recycling.
Example two:
respectively adding 650 g (5 mol) of isooctanol, 8 g of titanium tetrachloride and 363 g (3 mol) of N-dimethylaniline into a 2L three-neck flask, starting a machine for stirring, controlling the temperature of a reaction solution to be about 10 ℃ and the vacuum degree to be-0.08 MPa, then dropwise adding 153 g (1 mol) of phosphorus oxychloride for 2 hours, controlling the temperature of the reaction solution to be 10 ℃ ~ 40 ℃ in the dropwise adding process, raising the temperature of the reaction solution to be 130 ℃ after the dropwise adding is finished, preserving the temperature for 4 hours, finishing the reaction, rapidly removing hydrogen chloride generated in the reaction process under the action of negative pressure in the reaction process, cooling the reaction solution, filtering to obtain tertiary amine hydrochloride and filtrate, carrying out alkaline washing on the filtrate by using a sodium carbonate aqueous solution with the mass concentration of 10%, taking an oil phase after the liquid separation, washing the oil phase by using deionized water for the liquid separation, keeping the oil phase, controlling the vacuum degree to be-00 ~ -0.1 MPa underOil phase to obtain triisooctyl phosphate with the content of more than 99 percent. NH for tertiary amine hydrochloride3-NH4And (3) regenerating the Cl saturated solution to obtain high-purity N-N dimethylaniline, wherein the N-N dimethylaniline is used as an acid-binding agent for recycling.
Example three:
respectively putting 390 g (3 mol) of isooctyl alcohol, 6 g of magnesium chloride and 363 g (3 mol) of N-dimethylaniline into a 2L three-neck flask, starting a machine for stirring, controlling the temperature of a reaction solution to be about 10 ℃ and the vacuum degree to be-0.08 MPa, then dropwise adding 153 g (1 mol) of phosphorus oxychloride for 2 hours, controlling the temperature of the reaction solution to be 10 ℃ ~ 40 ℃ in the dropwise adding process, raising the temperature of the reaction solution to be 120 ℃ after the dropwise adding is finished, preserving the temperature for 6 hours, finishing the reaction, rapidly removing hydrogen chloride generated in the reaction process under the action of negative pressure in the reaction process, cooling the reaction solution, filtering to obtain tertiary amine hydrochloride and filtrate, performing alkaline washing on the filtrate by using a sodium carbonate aqueous solution with the mass concentration of 10%, taking an oil phase after liquid separation, washing the oil phase by using deionized water, keeping the oil phase, controlling the vacuum degree to be-0098 MPa ~ -0.1 MPa under the high vacuum condition, and purifying the oil phase by negative pressure rectification to obtain triisooctyl phosphate3-NH4And (3) regenerating the Cl saturated solution to obtain high-purity N-N dimethylaniline, wherein the N-N dimethylaniline is used as an acid-binding agent for recycling.
The synthesis method of triisooctyl phosphate has the advantages that firstly, the reaction is carried out under the conditions of negative pressure and an acid-binding agent, the hydrogen chloride generated by the reaction can be timely removed out of a reaction system under the action of the negative pressure, so that the amount of the hydrogen chloride dissolved in a reaction liquid is greatly reduced, the acid-binding agent further effectively prevents the hydrogen chloride dissolved in the reaction liquid from carrying out side reaction with isooctyl alcohol, the side reaction can be effectively reduced under the conditions of the negative pressure and the acid-binding agent, so that the yield is greatly improved, secondly, phosphorus oxychloride is fed in a dropwise adding mode, in addition, the temperature of the reaction liquid is controlled at 10 ℃ of ~ 40 ℃ in the dropwise adding process, so that the side reaction can be effectively avoided, the reaction yield is further improved, and thirdly, tertiary amine hydrochloride obtained after the reaction is finished is subjected to NH 8940 DEG C3-NH4Regenerating Cl saturated solution to obtain high-concentration N-The N-dimethylaniline is used as an acid-binding agent for recycling, so that the emission of ammonia salt solid waste is reduced, and the production cost can be effectively saved.
Claims (7)
1. The synthesis method of triisooctyl phosphate is characterized by comprising the following steps of reacting phosphorus oxychloride and isooctanol under the conditions of negative pressure, catalyst and N-dimethylaniline as acid-binding agents, wherein the molar ratio of the phosphorus oxychloride to the isooctanol is 1:3 ~ 1:5, the vacuum degree is controlled to be-0.075 MPa ~ -0.085 MPa in the reaction process, the phosphorus oxychloride is added in a dropwise manner, the temperature of a reaction liquid is controlled to be ~ 40 ℃ in the phosphorus oxychloride dropwise addition process, after the phosphorus oxychloride dropwise addition is finished, the reaction liquid is heated to 110 ℃ ~ 140 ℃, the heat preservation reaction is carried out for 3 ~ 8 hours, after the reaction is finished, the reaction liquid is filtered to obtain tertiary amine hydrochloride and filtrate, and the filtrate is subjected to alkali washing, high-vacuum negative pressure rectification to obtain the product triisooctyl phosphate.
2. The method for synthesizing triisooctyl phosphate according to claim 1, wherein the catalyst is Lewis acid, the Lewis acid comprises titanium tetrachloride, magnesium chloride and aluminum trichloride, and the amount of the catalyst is ~ 1% of the total mass of the reaction solution by 0.5%.
3. The method of synthesizing triisooctyl phosphate according to claim 1, characterized in that: the preferred molar ratio of phosphorus oxychloride to isooctanol feed is 1: 4.
4. The method of synthesizing triisooctyl phosphate according to claim 1, characterized in that: after the addition of phosphorus oxychloride is complete, the reaction mixture is preferably raised to 120 ℃.
5. The method of synthesizing triisooctyl phosphate according to claim 1, characterized in that: after the addition of the phosphorus oxychloride is finished, the reaction is preferably kept for 4 hours.
6. The synthesis method of triisooctyl phosphate according to claim 1, 2, 3, 4 or 5, characterized in that after the reaction is finished, the reaction solution is filtered to obtain filtrate, sodium carbonate aqueous solution with the mass concentration of 10% is firstly used for carrying out alkali washing, liquid separation is carried out to obtain oil phase, the oil phase is washed by deionized water and then is rectified and purified in high vacuum and negative pressure to obtain the triisooctyl phosphate product, and the vacuum degree of the high vacuum and negative pressure rectification is controlled to be-0098 MPa ~ -0.1 MPa.
7. The method of synthesizing triisooctyl phosphate according to claim 1 or 2 or 3 or 4 or 5, characterized in that: after the reaction is finished, filtering the reaction liquid to obtain NH for tertiary amine hydrochloride3-NH4And regenerating the CL saturated solution to obtain the N-N dimethylaniline.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115974914A (en) * | 2022-12-15 | 2023-04-18 | 广西兴达精细化工有限公司 | Synthetic method of trioctyl phosphate |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102875593A (en) * | 2012-10-22 | 2013-01-16 | 吉林省九新实业集团化工有限公司 | Triisotridecanol phosphite and preparation technique thereof |
| CN103435642A (en) * | 2013-09-02 | 2013-12-11 | 杭州潜阳科技有限公司 | Production method of trioctyl phosphate |
| CN103467513A (en) * | 2013-08-29 | 2013-12-25 | 深圳新宙邦科技股份有限公司 | Preparation method of triallyl phosphate |
| CN105503941A (en) * | 2015-12-11 | 2016-04-20 | 三门峡中达化工有限公司 | Catalytic synthesis method of tri-iso-octyl phosphate |
| CN106380481A (en) * | 2016-08-24 | 2017-02-08 | 浙江万盛股份有限公司 | Preparation method of tri-iso-octyl phosphate |
-
2018
- 2018-06-28 CN CN201810686423.1A patent/CN110655531A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102875593A (en) * | 2012-10-22 | 2013-01-16 | 吉林省九新实业集团化工有限公司 | Triisotridecanol phosphite and preparation technique thereof |
| CN103467513A (en) * | 2013-08-29 | 2013-12-25 | 深圳新宙邦科技股份有限公司 | Preparation method of triallyl phosphate |
| CN103435642A (en) * | 2013-09-02 | 2013-12-11 | 杭州潜阳科技有限公司 | Production method of trioctyl phosphate |
| CN105503941A (en) * | 2015-12-11 | 2016-04-20 | 三门峡中达化工有限公司 | Catalytic synthesis method of tri-iso-octyl phosphate |
| CN106380481A (en) * | 2016-08-24 | 2017-02-08 | 浙江万盛股份有限公司 | Preparation method of tri-iso-octyl phosphate |
Non-Patent Citations (1)
| Title |
|---|
| 尹志刚 主编: "《有机磷化合物 (第1版)》", 31 March 2011, 北京：化学工业出版社 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115974914A (en) * | 2022-12-15 | 2023-04-18 | 广西兴达精细化工有限公司 | Synthetic method of trioctyl phosphate |
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