CN116284123A - Synthesis method of 2-ethylhexyl phosphate mono (2-ethylhexyl) ester - Google Patents
Synthesis method of 2-ethylhexyl phosphate mono (2-ethylhexyl) ester Download PDFInfo
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- SEGLCEQVOFDUPX-UHFFFAOYSA-N di-(2-ethylhexyl)phosphoric acid Chemical compound CCCCC(CC)COP(O)(=O)OCC(CC)CCCC SEGLCEQVOFDUPX-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 238000001308 synthesis method Methods 0.000 title abstract description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 60
- 238000006243 chemical reaction Methods 0.000 claims abstract description 50
- 238000010438 heat treatment Methods 0.000 claims abstract description 33
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 24
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 24
- MJMQIMYDFATMEH-UHFFFAOYSA-N 2-chloro-2,4,4-trimethylpentane Chemical compound CC(C)(C)CC(C)(C)Cl MJMQIMYDFATMEH-UHFFFAOYSA-N 0.000 claims abstract description 21
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 19
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 17
- ZLMKQJQJURXYLC-UHFFFAOYSA-N bis(2-ethylhexoxy)-oxophosphanium Chemical compound CCCCC(CC)CO[P+](=O)OCC(CC)CCCC ZLMKQJQJURXYLC-UHFFFAOYSA-N 0.000 claims abstract description 12
- CZHYKKAKFWLGJO-UHFFFAOYSA-N dimethyl phosphite Chemical compound COP([O-])OC CZHYKKAKFWLGJO-UHFFFAOYSA-N 0.000 claims abstract description 10
- DBVXWVMCVDCFEO-UHFFFAOYSA-N 5,8-diethyldodecan-6-yl dihydrogen phosphate Chemical compound CCCCC(CC)CC(OP(O)(O)=O)C(CC)CCCC DBVXWVMCVDCFEO-UHFFFAOYSA-N 0.000 claims abstract description 9
- GTVWRXDRKAHEAD-UHFFFAOYSA-N Tris(2-ethylhexyl) phosphate Chemical compound CCCCC(CC)COP(=O)(OCC(CC)CCCC)OCC(CC)CCCC GTVWRXDRKAHEAD-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000007787 solid Substances 0.000 claims abstract description 9
- 239000003444 phase transfer catalyst Substances 0.000 claims abstract description 8
- 239000003054 catalyst Substances 0.000 claims abstract description 7
- 238000001816 cooling Methods 0.000 claims abstract description 7
- 239000012074 organic phase Substances 0.000 claims abstract description 7
- 239000008346 aqueous phase Substances 0.000 claims abstract description 5
- 230000002194 synthesizing effect Effects 0.000 claims description 14
- 238000010025 steaming Methods 0.000 claims description 13
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 12
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 12
- 230000020477 pH reduction Effects 0.000 claims description 12
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 claims description 6
- HTZCNXWZYVXIMZ-UHFFFAOYSA-M benzyl(triethyl)azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC1=CC=CC=C1 HTZCNXWZYVXIMZ-UHFFFAOYSA-M 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 claims description 6
- GYBMSOFSBPZKCX-UHFFFAOYSA-N sodium;ethanol;ethanolate Chemical compound [Na+].CCO.CC[O-] GYBMSOFSBPZKCX-UHFFFAOYSA-N 0.000 claims description 4
- SUBJHSREKVAVAR-UHFFFAOYSA-N sodium;methanol;methanolate Chemical compound [Na+].OC.[O-]C SUBJHSREKVAVAR-UHFFFAOYSA-N 0.000 claims description 4
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 4
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 3
- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 claims description 3
- 150000008301 phosphite esters Chemical class 0.000 claims description 3
- 159000000000 sodium salts Chemical class 0.000 claims description 3
- 239000012295 chemical reaction liquid Substances 0.000 claims description 2
- 238000001704 evaporation Methods 0.000 claims description 2
- LJKDOMVGKKPJBH-UHFFFAOYSA-N 2-ethylhexyl dihydrogen phosphate Chemical compound CCCCC(CC)COP(O)(O)=O LJKDOMVGKKPJBH-UHFFFAOYSA-N 0.000 abstract description 9
- -1 2-ethylhexyl Chemical group 0.000 abstract description 8
- 238000010924 continuous production Methods 0.000 abstract description 3
- 238000003912 environmental pollution Methods 0.000 abstract description 2
- 239000002253 acid Substances 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000005903 acid hydrolysis reaction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- PSLVOISYPFAVKQ-UHFFFAOYSA-N bis(2-ethylhexyl)-trihydroxy-$l^{5}-phosphane Chemical compound CCCCC(CC)CP(O)(O)(O)CC(CC)CCCC PSLVOISYPFAVKQ-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
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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 Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
- C07F9/40—Esters thereof
- C07F9/4071—Esters thereof the ester moiety containing a substituent or a structure which is considered as characteristic
- C07F9/4075—Esters with hydroxyalkyl compounds
-
- 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 Table
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/08—Esters of oxyacids of phosphorus
- C07F9/141—Esters of phosphorous acids
- C07F9/142—Esters of phosphorous acids with hydroxyalkyl compounds without further substituents on alkyl
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a synthesis method of 2-ethylhexyl phosphoric acid mono (2-ethylhexyl) ester, which comprises the following steps: adding dimethyl phosphite, a catalyst and 2-ethylhexanol into a container, mixing, heating and reacting; heating to evaporate methanol to obtain bis (2-ethylhexyl) phosphite; adding methanol or ethanol solution into bis (2-ethylhexyl) phosphite ester, and heating to evaporate methanol or ethanol; adding a phase transfer catalyst and chloroisooctane, and heating for reaction; distilling off chloroisooctane to obtain 2-ethylhexyl phosphate bis (2-ethylhexyl) ester; adding solid sodium hydroxide into the 2-ethylhexyl phosphate bis (2-ethylhexyl), heating to react, and cooling; acidifying with hydrochloric acid, separating to obtain aqueous phase, and collecting the organic phase as 2-ethylhexyl phosphate mono (2-ethylhexyl) ester. The method can avoid high temperature reaction in the process, can avoid environmental pollution, has continuous whole reaction process and less post-treatment, and can realize continuous production.
Description
Technical Field
The invention belongs to the technical field of chemical synthesis, and particularly relates to a synthesis method of 2-ethylhexyl phosphate mono (2-ethylhexyl).
Background
The product name of the 2-ethylhexyl phosphate mono (2-ethylhexyl) is P507, which is an acidic phosphine type extractant used for rare earth and nonferrous metals, and can also be used for recovering lithium and other metals in lithium batteries, and the application is very wide.
At present, most of the existing production processes of 2-ethylhexyl phosphate mono (2-ethylhexyl) are that 2-ethylhexanol reacts with phosphorus trichloride, bis (2-ethylhexyl) phosphorous acid is generated at high temperature, and then the bis (2-ethylhexyl) phosphate is generated by reacting with chloroisooctane, and then the bis (2-ethylhexyl) phosphate is hydrolyzed by hydrochloric acid to obtain the product. The phosphorus trichloride used in the production process generates a large amount of hydrogen chloride gas during reaction, and has a small amount of dissipation after absorption, thus having great harm to the environment. The second step of reaction needs high temperature and has high equipment requirement. In the third step, hydrolysis products are easy to generate and difficult to control in the acid hydrolysis process.
Therefore, research and development of a method for synthesizing 2-ethylhexyl phosphate mono (2-ethylhexyl) ester, which avoids high-temperature reaction in the process, does not pollute the environment, and has less continuous post-treatment in the reaction process, has important significance.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a method for synthesizing 2-ethylhexyl phosphate mono (2-ethylhexyl) ester, which can avoid high-temperature reaction in the process, avoid environmental pollution, and has the advantages of continuous whole reaction process, less post-treatment and continuous production.
In order to achieve the above purpose, the technical scheme of the invention is as follows:
a method for synthesizing 2-ethylhexyl phosphoric acid mono (2-ethylhexyl) ester, which comprises the following steps:
sequentially adding dimethyl phosphite, a catalyst and 2-ethylhexanol into a reaction container for mixing, and heating the mixture to 60-70 ℃ for reaction for 4 hours; continuously heating to 90-110 ℃, and steaming out methanol generated by the reaction to obtain bis (2-ethylhexyl) phosphite ester reaction liquid;
step two, adding sodium methoxide methanol solution or sodium ethoxide ethanol solution into the bis (2-ethylhexyl) phosphite reaction solution obtained in the step one, heating to 65-75 ℃, and steaming out methanol or ethanol; then, sequentially adding a phase transfer catalyst and chloroisooctane into the reaction system, and heating to 115-125 ℃ for reaction for 6-6.5 hours; evaporating unreacted chloro-isooctane under reduced pressure to obtain 2-ethylhexyl phosphate bis (2-ethylhexyl) ester reaction solution;
adding solid sodium hydroxide into the 2-ethylhexyl phosphate bis (2-ethylhexyl) ester reaction solution obtained in the step two, heating to 115-125 ℃ for reaction, and cooling to room temperature after the reaction is finished; then adding a sufficient amount of hydrochloric acid for acidification, directly separating liquid after acidification, and separating out an aqueous phase, wherein the remained organic phase is 2-ethylhexyl phosphoric acid mono (2-ethylhexyl) ester.
In the above synthesis method of 2-ethylhexyl phosphate mono (2-ethylhexyl), in step 1), the catalyst is one of organic base, triethylamine, diisopropylethylamine or tetramethyl ethylenediamine.
In the above synthesis method of 2-ethylhexyl phosphoric acid mono (2-ethylhexyl) ester, in step 1), the molar ratio of dimethyl phosphite, catalyst and 2-ethylhexanol is 1:0.001:2.36 to 2.6.
In the above synthesis method of 2-ethylhexyl phosphoric acid mono (2-ethylhexyl) ester, in step 2), the phase transfer catalyst is used to accelerate the reaction of sodium salt of phosphite ester and chloroisooctane; which is one of tetrabutylammonium bromide, dodecyltrimethylammonium chloride or benzyltriethylammonium chloride.
In the above synthesis method of 2-ethylhexyl phosphate mono (2-ethylhexyl) ester, in step 2), the mass of sodium methoxide in the sodium methoxide methanol solution is 32% -36% of the mass of methanol; the mass of sodium ethoxide in the sodium ethoxide ethanol solution is 40-46% of the mass of ethanol.
In the above synthesis method of 2-ethylhexyl phosphoric acid mono (2-ethylhexyl) ester, in the step 2), the molar ratio of the chloroisooctane to the phase transfer catalyst is 1.8-2: 0.001.
the synthetic method of the 2-ethylhexyl phosphoric acid mono (2-ethylhexyl) ester comprises the steps of: 1.8 to 2.
The invention has the technical effects and advantages that:
according to the synthesis method of the 2-ethylhexyl phosphate mono (2-ethylhexyl) ester, dimethyl phosphite is used as a raw material, bis (2-ethylhexyl) phosphite is obtained through transesterification, methanol generated in the reaction process can be recovered, and environmental hazard can be effectively avoided. And in the second step, a phase transfer catalyst is added to accelerate the reaction speed of sodium salt of phosphite ester and chloroisooctane, so that the reaction temperature can be effectively reduced. And in the third step, the reaction uses alkali hydrolysis, and solid alkali is directly added, so that the hydrolysis can be quantitatively performed, the control is easy, and the amount of wastewater is small. The whole reaction process is continuous, the post-treatment is less, and the continuous production can be realized.
Drawings
FIG. 1 is a diagram of the synthesis of mono (2-ethylhexyl) 2-ethylhexyl phosphate according to this invention.
Detailed Description
The examples given below illustrate the invention in further detail.
Example 1
In this embodiment, the method for synthesizing 2-ethylhexyl phosphate mono (2-ethylhexyl) ester comprises the following steps:
step one, adding 100g of dimethyl phosphite into a 1000ml three-mouth bottle, adding 0.1g of triethylamine, adding 260g of 2-ethylhexanol, heating the mixture to 60-70 ℃, reacting for 4 hours, heating to 100 ℃, and steaming out methanol generated by the reaction to obtain bis (2-ethylhexyl) phosphite; the next step is directly carried out without treatment.
And step two, adding a methanol solution of sodium methoxide (54 g of sodium methoxide is dissolved in 200ml of methanol) into the bis (2-ethylhexyl) phosphite obtained in the step one, heating to 70 ℃, steaming out methanol, adding 0.1g of tetrabutylammonium bromide into a reaction system, adding 200g of chloroisooctane, heating to 120 ℃, reacting for 6 hours, and steaming out unreacted chloroisooctane under reduced pressure to obtain the 2-ethylhexyl phosphate bis (2-ethylhexyl) with the yield of 80%.
And step three, adding 40g of solid sodium hydroxide into the 2-ethylhexyl phosphate bis (2-ethylhexyl) ester obtained in the step two, heating to 120 ℃, cooling to room temperature after the reaction is finished, adding 3mol/L hydrochloric acid for acidification, directly separating liquid after acidification, and separating an acid water phase and an organic phase which are products, wherein the yield is about 80%.
Example 2
In this embodiment, the method for synthesizing 2-ethylhexyl phosphate mono (2-ethylhexyl) ester comprises the following steps:
step one, adding 100g of dimethyl phosphite into a 1000ml three-mouth bottle, adding 0.1g of diisopropylethylamine, adding 236g of 2-ethylhexanol, heating the mixture to 60-70 ℃ for reaction for 4 hours, heating to 100 ℃, and distilling methanol generated by the reaction. The next step is directly carried out without treatment.
Step two, adding a methanol solution of sodium methoxide (49 g of sodium methoxide is dissolved in 180ml of methanol) into the bis (2-ethylhexyl) phosphite obtained in the step one, heating to 70 ℃, steaming out methanol, adding 0.1g of tetrabutylammonium bromide into a reaction system, adding 180g of chloroisooctane, heating to 120 ℃, reacting for 6 hours, and steaming out unreacted chloroisooctane under reduced pressure to obtain 2-ethylhexyl phosphoric acid bis (2-ethylhexyl) ester, wherein the yield is 78%.
And step three, adding 38g of solid sodium hydroxide into the 2-ethylhexyl phosphate bis (2-ethylhexyl) ester obtained in the step two, heating to 120 ℃, cooling to room temperature after the reaction is finished, adding 3mol/L hydrochloric acid for acidification, directly separating liquid after acidification, and separating an acid water phase and an organic phase to obtain the product with the yield of 80%.
Example 3
In this embodiment, the method for synthesizing 2-ethylhexyl phosphate mono (2-ethylhexyl) ester comprises the following steps:
step one, adding 100g of dimethyl phosphite into a 1000ml three-mouth bottle, adding 0.1g of tetramethyl ethylenediamine, adding 236g of 2-ethylhexanol, heating the mixture to 60-70 ℃ for reaction for 4 hours, heating to 100 ℃, and distilling off methanol generated by the reaction. The next step is directly carried out without treatment.
Step two, adding an ethanol solution of sodium ethoxide (62 g of sodium ethoxide is dissolved in 180ml of ethanol) into the bis (2-ethylhexyl) phosphite obtained in the step one, heating to 70 ℃, steaming out ethanol, adding 0.1g of dodecyl trimethyl ammonium chloride into a reaction system, adding 180g of chloroisooctane, heating to 120 ℃, reacting for 6 hours, and steaming out unreacted chloroisooctane under reduced pressure to obtain the 2-ethylhexyl phosphate bis (2-ethylhexyl) with the yield of 75%.
And step three, adding 36g of solid sodium hydroxide into the 2-ethylhexyl phosphate bis (2-ethylhexyl) ester obtained in the step two, heating to 120 ℃, cooling to room temperature after the reaction is finished, adding 3mol/L hydrochloric acid for acidification, directly separating liquid after acidification, and separating an acid aqueous phase and an organic phase to obtain the product with the yield of 77%.
Example 4
In this embodiment, the method for synthesizing 2-ethylhexyl phosphate mono (2-ethylhexyl) ester comprises the following steps:
step one, 100g of dimethyl phosphite is added into a 1000ml three-mouth bottle, 0.1g of triethylamine is added, 236g of 2-ethylhexanol is added, the mixture is heated to 60-70 ℃ for reaction for 4 hours, the temperature is raised to 100 ℃, and methanol generated by the reaction is distilled off. The next step is directly carried out without treatment.
Step two, adding an ethanol solution of sodium ethoxide (62 g of sodium ethoxide is dissolved in 180ml of ethanol) into the bis (2-ethylhexyl) phosphite obtained in the step one, heating to 70 ℃, steaming out ethanol, adding 0.1g of benzyl triethyl ammonium chloride into a reaction system, adding 180g of chloroisooctane, heating to 120 ℃, reacting for 6 hours, and steaming out unreacted chloroisooctane under reduced pressure to obtain 2-ethylhexyl phosphate bis (2-ethylhexyl) with a yield of 72%.
And step three, adding 34g of solid sodium hydroxide into the 2-ethylhexyl phosphate bis (2-ethylhexyl) ester obtained in the step two, heating to 120 ℃, cooling to room temperature after the reaction is finished, adding 3mol/L hydrochloric acid for acidification, directly separating liquid after acidification, and separating an acid aqueous phase and an organic phase to obtain the product with the yield of 75%.
The foregoing is merely a preferred embodiment of the present invention, and it should be noted that modifications and improvements could be made by those skilled in the art without departing from the inventive concept, which falls within the scope of the present invention.
Claims (7)
1. A method for synthesizing 2-ethylhexyl phosphoric acid mono (2-ethylhexyl) ester, which is characterized by comprising the following steps:
sequentially adding dimethyl phosphite, a catalyst and 2-ethylhexanol into a reaction container for mixing, and heating the mixture to 60-70 ℃ for reaction for 4 hours; continuously heating to 90-110 ℃, and steaming out methanol generated by the reaction to obtain bis (2-ethylhexyl) phosphite ester reaction liquid;
step two, adding sodium methoxide methanol solution or sodium ethoxide ethanol solution into the bis (2-ethylhexyl) phosphite reaction solution obtained in the step one, heating to 65-75 ℃, and steaming out methanol or ethanol; then, sequentially adding a phase transfer catalyst and chloroisooctane into the reaction system, and heating to 115-125 ℃ for reaction for 6-6.5 h; evaporating unreacted chloro-isooctane under reduced pressure to obtain 2-ethylhexyl phosphate bis (2-ethylhexyl) ester reaction solution;
adding solid sodium hydroxide into the 2-ethylhexyl phosphate bis (2-ethylhexyl) ester reaction solution obtained in the step two, heating to 115-125 ℃ for reaction, and cooling to room temperature after the reaction is finished; then adding a sufficient amount of hydrochloric acid for acidification, directly separating liquid after acidification, and separating out an aqueous phase, wherein the remained organic phase is 2-ethylhexyl phosphoric acid mono (2-ethylhexyl) ester.
2. The method for synthesizing 2-ethylhexyl phosphate mono (2-ethylhexyl) ester according to claim 1, wherein: the catalyst in the step 1) is one of organic alkali, triethylamine, diisopropylethylamine or tetramethyl ethylenediamine.
3. The method for synthesizing 2-ethylhexyl phosphate mono (2-ethylhexyl) ester according to claim 1, wherein: in the step 1), the molar ratio of the dimethyl phosphite to the catalyst to the 2-ethylhexanol is 1:0.001:2.36 to 2.6.
4. The method for synthesizing 2-ethylhexyl phosphate mono (2-ethylhexyl) ester according to claim 1, wherein: in step 2), the phase transfer catalyst is used for accelerating the reaction of sodium salt of phosphite ester and chloroisooctane; which is one of tetrabutylammonium bromide, dodecyltrimethylammonium chloride or benzyltriethylammonium chloride.
5. The method for synthesizing 2-ethylhexyl phosphate mono (2-ethylhexyl) ester according to claim 1, wherein: in the step 2), the mass of sodium methoxide in the sodium methoxide methanol solution is 32-36% of the mass of methanol; the mass of sodium ethoxide in the sodium ethoxide ethanol solution is 40-46% of the mass of ethanol.
6. The method for synthesizing 2-ethylhexyl phosphate mono (2-ethylhexyl) ester according to claim 1, wherein: in the step 2), the molar ratio of the chloroisooctane to the phase transfer catalyst is 1.8-2: 0.001.
7. the method for synthesizing 2-ethylhexyl phosphate mono (2-ethylhexyl) ester according to claim 6, wherein: the mole ratio of the solid sodium hydroxide to the chloroisooctane is 0.34-0.4: 1.8 to 2.
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| CN115028660A (en) * | 2022-06-20 | 2022-09-09 | 三门峡中达化工有限公司 | Method for synthesizing 2-ethylhexyl phosphonic acid di (2-ethyl) hexyl ester by taking 2-ethylhexyl sodium alkoxide as alkali |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115028660A (en) * | 2022-06-20 | 2022-09-09 | 三门峡中达化工有限公司 | Method for synthesizing 2-ethylhexyl phosphonic acid di (2-ethyl) hexyl ester by taking 2-ethylhexyl sodium alkoxide as alkali |
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