CN113429437A - Synthesis method of tris (hydroxymethyl) phosphine oxide - Google Patents
Synthesis method of tris (hydroxymethyl) phosphine oxide Download PDFInfo
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- CN113429437A CN113429437A CN202110738537.8A CN202110738537A CN113429437A CN 113429437 A CN113429437 A CN 113429437A CN 202110738537 A CN202110738537 A CN 202110738537A CN 113429437 A CN113429437 A CN 113429437A
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- phosphine oxide
- hydroxymethyl
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- MRVZORUPSXTRHD-UHFFFAOYSA-N bis(hydroxymethyl)phosphorylmethanol Chemical compound OCP(=O)(CO)CO MRVZORUPSXTRHD-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 238000001308 synthesis method Methods 0.000 title description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 33
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 17
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 13
- DKRWGRQBYLWNKR-UHFFFAOYSA-N OC(O)(O)[PH2]=O Chemical compound OC(O)(O)[PH2]=O DKRWGRQBYLWNKR-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000003960 organic solvent Substances 0.000 claims abstract description 10
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 8
- AIRPJJGSWHWBKS-UHFFFAOYSA-N hydroxymethylphosphanium;chloride Chemical compound [Cl-].OC[PH3+] AIRPJJGSWHWBKS-UHFFFAOYSA-N 0.000 claims abstract description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 27
- 239000000243 solution Substances 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 18
- 239000003513 alkali Substances 0.000 claims description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 238000001914 filtration Methods 0.000 claims description 14
- 150000003839 salts Chemical class 0.000 claims description 14
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
- 239000012046 mixed solvent Substances 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 7
- 238000000605 extraction Methods 0.000 claims description 7
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 2
- 239000000920 calcium hydroxide Substances 0.000 claims description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 9
- 230000015572 biosynthetic process Effects 0.000 abstract description 8
- 239000002904 solvent Substances 0.000 abstract description 7
- 239000007800 oxidant agent Substances 0.000 abstract description 4
- 229920002635 polyurethane Polymers 0.000 abstract description 4
- 239000004814 polyurethane Substances 0.000 abstract description 4
- 239000004721 Polyphenylene oxide Substances 0.000 abstract description 3
- 230000001590 oxidative effect Effects 0.000 abstract description 3
- 229920000570 polyether Polymers 0.000 abstract description 3
- 229920005862 polyol Polymers 0.000 abstract description 3
- 150000003077 polyols Chemical class 0.000 abstract description 3
- 239000000853 adhesive Substances 0.000 abstract description 2
- 230000001070 adhesive effect Effects 0.000 abstract description 2
- 239000003054 catalyst Substances 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 abstract description 2
- 239000006260 foam Substances 0.000 abstract description 2
- 238000009413 insulation Methods 0.000 abstract description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 abstract 2
- 239000012670 alkaline solution Substances 0.000 abstract 1
- 239000006227 byproduct Substances 0.000 abstract 1
- 239000003814 drug Substances 0.000 abstract 1
- 229940079593 drug Drugs 0.000 abstract 1
- 239000000047 product Substances 0.000 abstract 1
- 238000007670 refining Methods 0.000 abstract 1
- 239000011780 sodium chloride Substances 0.000 abstract 1
- 230000001954 sterilising effect Effects 0.000 abstract 1
- 238000004659 sterilization and disinfection Methods 0.000 abstract 1
- 238000001704 evaporation Methods 0.000 description 10
- 239000003063 flame retardant Substances 0.000 description 9
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 6
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 5
- YTVQIZRDLKWECQ-UHFFFAOYSA-N 2-benzoylcyclohexan-1-one Chemical compound C=1C=CC=CC=1C(=O)C1CCCCC1=O YTVQIZRDLKWECQ-UHFFFAOYSA-N 0.000 description 5
- 239000000706 filtrate Substances 0.000 description 5
- 229910052698 phosphorus Inorganic materials 0.000 description 5
- 239000011574 phosphorus Substances 0.000 description 5
- 239000007789 gas Substances 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 241000282414 Homo sapiens Species 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 229910000039 hydrogen halide Inorganic materials 0.000 description 2
- 239000012433 hydrogen halide Substances 0.000 description 2
- ULDUOODSZHJSKE-UHFFFAOYSA-N hydroxymethylphosphanium;hydroxide Chemical compound [OH-].OC[PH3+] ULDUOODSZHJSKE-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- 150000001450 anions Chemical group 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- -1 hydroxymethyl anions Chemical class 0.000 description 1
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- IZCXEXNXJRMUKJ-UHFFFAOYSA-N phosphanylmethanetriol Chemical compound OC(O)(O)P IZCXEXNXJRMUKJ-UHFFFAOYSA-N 0.000 description 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- 150000004714 phosphonium salts Chemical group 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
Images
Classifications
-
- 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
- C07F9/50—Organo-phosphines
- C07F9/53—Organo-phosphine oxides; Organo-phosphine thioxides
- C07F9/5304—Acyclic saturated phosphine oxides or thioxides
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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)
Abstract
The invention discloses a method for synthesizing trihydroxymethyl phosphine oxide, which takes tetrakis hydroxymethyl phosphonium chloride as a raw material, adds alkaline solution and heats for reaction, and then uses organic solvent to desalt and purify the product to obtain refined trihydroxymethyl phosphine oxide. The reaction has the advantages of simple synthesis process, mild reaction conditions and high yield. No catalyst or oxidant is used in the reaction system, the byproducts are sodium chloride and methanol, the solvent used in the refining process can be recovered, and the whole process is green, environment-friendly and pollution-free. The tris (hydroxymethyl) phosphine oxide is a halogen-free compound with flame retardance and sterilization, can be used as a solvent, a raw material for synthesizing polyether polyol and a drug intermediate at present, and is applied to various fields of flame retardance of polyurethane hard foam insulation boards, flame retardance of polyurethane adhesives and the like.
Description
Technical Field
The invention belongs to the technical field of chemical synthesis, and particularly relates to a method for synthesizing trihydroxymethyl phosphine oxide.
Background
The flame retardant is applied to various aspects in production and life. At present, a part of flame retardants produced in China are halogen-containing flame retardants. Although the flame retardant effect is remarkable and the influence on the performance of the material is small, corrosive hydrogen halide gas is easily released, and the generated large amount of hydrogen halide poses serious threats to the environment and human beings. For this reason, safety and environmental protection are important factors affecting the development of flame retardants. At present, the organic phosphorus flame retardant has the advantages of small addition amount, small harm to the environment, low toxicity, low smoke, low halogen, low pollution and the like. The tris (hydroxymethyl) phosphine oxide belongs to an organic phosphorus flame retardant, and is widely applied to flame retardance of polyurethane rigid foam insulation boards and polyurethane adhesives for external walls. The compound does not contain halogen, has higher phosphorus content than common phosphorus flame retardants, does not contain a phosphate ester bond in the structure but combines the phosphate ester bond with the phosphorus carbon bond, and has the advantages of good thermal stability, hydrolysis resistance, no toxicity and the like. The polyether polyol can be used as a flame retardant and also can be used as an intermediate for synthesizing polyether polyol. Currently, tris (hydroxymethyl) phosphine oxide is synthesized from phosphine gas or quaternary phosphonium salt as a raw material. For example, the invention of CN104230989B discloses a process for synthesizing tris (hydroxymethyl) phosphine oxide, which uses phosphine gas and formaldehyde for reaction, but both phosphine gas and formaldehyde are harmful to human body and environment. The reaction is to generate the trihydroxymethyl phosphine firstly and to carry out oxidation reaction by adding an oxidant to finally obtain the trihydroxymethyl phosphine oxide. The invention of CN103980313A discloses a scheme for synthesizing tris (hydroxymethyl) phosphine oxide by using quaternary phosphorus salt as a raw material, but the reaction also needs oxidizing agent for oxidation to obtain a final product, and simultaneously increases the difficulty in the separation and purification process.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a simple, safe, high-efficiency and environment-friendly method for synthesizing the trihydroxymethyl phosphine oxide, wherein the method selects tetrakis hydroxymethyl phosphonium chloride as a raw material, and the refined trihydroxymethyl phosphine oxide is obtained through design, synthesis, separation and purification. According to the scheme, the trihydroxymethyl phosphine oxide can be obtained by only one-step synthesis, and the final product can be obtained without oxidation reaction again, so that the reaction synthesis process is simpler and more convenient, and the yield and the purity are relatively higher.
The invention adopts the following technical scheme for solving the technical problems, and the synthesis method of the tris (hydroxymethyl) phosphine oxide is characterized by comprising the following specific steps:
step S1: adding an alkali solution into tetrakis hydroxymethyl phosphonium chloride serving as a raw material, heating to 60-98 ℃ for reaction, cooling to room temperature after the reaction is finished, adding a hydrochloric acid solution, adjusting the pH value of a mixed system to 2-3, concentrating to separate out salt, filtering, adding an organic solvent to separate out the salt for the second time, and filtering to obtain crude tris (hydroxymethyl) phosphine oxide;
step S2: and (4) adding the crude trimethylol phosphine oxide obtained in the step (S1) into an organic solvent for extraction, and distilling the extract under reduced pressure to obtain refined trimethylol phosphine oxide.
Further limiting, the alkali in the alkali solution in the step S1 is sodium hydroxide, potassium hydroxide or calcium hydroxide, the molar ratio of the tetrakis hydroxymethyl phosphonium chloride to the alkali is 1: 1-2, and the concentration of the alkali solution is 10wt% -30 wt%.
Further limiting, the reaction time in the step S1 is 8-10 h.
Further, the concentration of the hydrochloric acid solution in the step S1 is 6 mol/L.
Further limiting, in the step S1, the organic solvent is methanol or ethanol, and in the step S2, the organic solvent is a mixed solvent of methanol and ethyl acetate in a volume ratio of 1: 1-3 or a mixed solvent of ethanol and ethyl acetate in a volume ratio of 1: 2-3.
Compared with the prior art, the invention has the following beneficial effects: in the synthesis process, the quaternary phosphate is used as a raw material, and the trihydroxymethyl phosphine oxide can be obtained by one-step reaction without using a catalyst and an oxidant by controlling the reaction conditions, so that the synthesis process is simpler, the secondary oxidation treatment is not required, the yield is high, and impurities are few. The organic solvent used in the separation and purification process can be recycled, is safe, efficient, environment-friendly and pollution-free, and is more economicAnd (5) protecting. The synthesis mechanism of the synthesis process is that the alkali solution is added into the reaction system to generate the tetrakis hydroxymethyl phosphonium hydroxide, and the tetrakis hydroxymethyl phosphonium hydroxide is reacted with OH in the reaction system-Increase in concentration, OH under weak base conditions-The ions attack the phosphorus to remove the hydroxymethyl anions, so that the trihydroxy phosphine oxide is generated and the removed hydroxymethyl anions form methanol.
Drawings
FIG. 1 is a schematic view of a tris (hydroxymethyl) phosphine oxide synthesized in example 2 of the present invention1H NMR chart in FIG. 1, the abscissa represents chemical shift (ppm) and the ordinate represents absorption peak intensity.
FIG. 2 is a photograph of a tris (hydroxymethyl) phosphine oxide synthesized in example 2 of the present invention13C NMR chart in FIG. 2, the abscissa represents chemical shift (ppm) and the ordinate represents absorption peak intensity.
FIG. 3 is a photograph of a tris (hydroxymethyl) phosphine oxide synthesized in example 2 of the present invention31In the P NMR chart, the abscissa represents chemical shift (ppm) and the ordinate represents absorption peak intensity in FIG. 3.
FIG. 4 is a reaction scheme for synthesizing tris (hydroxymethyl) phosphine oxide according to the present invention.
Detailed Description
The present invention is described in further detail below with reference to examples, but it should not be construed that the scope of the above subject matter of the present invention is limited to the following examples, and that all the technologies realized based on the above subject matter of the present invention belong to the scope of the present invention.
Example 1
500g of tetrakis (hydroxymethyl) phosphonium chloride was put in a four-neck flask equipped with a thermometer, a spherical condenser and a constant pressure dropping funnel, 85g of potassium hydroxide was weighed to prepare a 10wt% aqueous alkali and was slowly dropped in the four-neck flask for 2 hours. Then heated to 60 ℃ for reaction for 9 h. And cooling to room temperature, adding a 6mol/L hydrochloric acid solution to adjust the pH value of the mixed system to 2-3, evaporating the solvent by using a rotary evaporator to separate out salt generated in the reaction system, and filtering. And adding an ethanol solution, standing overnight until salt is fully precipitated twice, filtering, adding the filtrate into a mixed solvent of ethanol and ethyl acetate with the volume ratio of 1:2 for twice extraction, and evaporating the extract under reduced pressure to obtain the refined trihydroxymethyl phosphine oxide.
Example 2
500g of tetrakis (hydroxymethyl) phosphonium chloride was put in a four-necked flask equipped with a thermometer, a spherical condenser and a constant pressure dropping funnel, 85g of potassium hydroxide was weighed to prepare a 20wt% aqueous alkali and was slowly dropped in the four-necked flask for 2.5 hours. Then heated to 80 ℃ for reaction for 8 h. And cooling to room temperature, adding a 6mol/L hydrochloric acid solution to adjust the pH value of the mixed system to 2-3, evaporating the solvent by using a rotary evaporator to separate out salt generated in the reaction system, and filtering. And adding an ethanol solution, standing overnight until salt is fully precipitated twice, filtering, adding the filtrate into a mixed solvent of ethanol and ethyl acetate with the volume ratio of 1:3 for twice extraction, and evaporating the extract under reduced pressure to obtain the refined trihydroxymethyl phosphine oxide.
Example 3
500g of tetrakis (hydroxymethyl) phosphonium chloride was put in a four-neck flask equipped with a thermometer, a spherical condenser and a constant pressure dropping funnel, 85g of sodium hydroxide was weighed to prepare a 30wt% aqueous alkali and was slowly dropped in the four-neck flask for 3 hours. Then heated to 98 ℃ for reaction for 10 h. And cooling to room temperature, adding a 6mol/L hydrochloric acid solution to adjust the pH value of the mixed system to 2-3, evaporating the solvent by using a rotary evaporator to separate out salt generated in the reaction system, and filtering. And adding an ethanol solution, standing overnight until salt is fully precipitated twice, filtering, adding the filtrate into a mixed solvent of methanol and ethyl acetate with the volume ratio of 1:1 for twice extraction, and evaporating the extract under reduced pressure to obtain the refined tris (hydroxymethyl) phosphine oxide.
Example 4
500g of tetrakis (hydroxymethyl) phosphonium chloride was put in a four-neck flask equipped with a thermometer, a spherical condenser and a constant pressure dropping funnel, 100g of sodium hydroxide was weighed to prepare a 20wt% aqueous alkali and was slowly dropped in the four-neck flask for 2 hours. Then heated to 82 ℃ for reaction for 5 h. And cooling to room temperature, adding a 6mol/L hydrochloric acid solution to adjust the pH value of the mixed system to 2-3, evaporating the solvent by using a rotary evaporator to separate out salt generated in the reaction system, and filtering. And adding a methanol solution, standing overnight until salt is fully precipitated twice, filtering, adding the filtrate into a mixed solvent of methanol and ethyl acetate with the volume ratio of 1:2 for twice extraction, and evaporating the extract under reduced pressure to obtain the refined tris (hydroxymethyl) phosphine oxide.
Example 5
500g of tetrakis (hydroxymethyl) phosphonium chloride was put in a four-neck flask equipped with a thermometer, a spherical condenser and a constant pressure dropping funnel, and 170g of sodium hydroxide was weighed to prepare a 20wt% aqueous alkali and slowly dropped in the four-neck flask for 2 hours. Then heated to 86 ℃ for reaction for 5 h. And cooling to room temperature, adding a 6mol/L hydrochloric acid solution to adjust the pH value of the mixed system to 2-3, evaporating the solvent by using a rotary evaporator to separate out salt generated in the reaction system, and filtering. And adding a methanol solution, standing overnight until salt is fully precipitated twice, filtering, adding the filtrate into a mixed solvent of methanol and ethyl acetate with the volume ratio of 1:3 for twice extraction, and evaporating the extract under reduced pressure to obtain the refined tris (hydroxymethyl) phosphine oxide.
The foregoing embodiments illustrate the principles, principal features and advantages of the invention, and it will be understood by those skilled in the art that the invention is not limited to the foregoing embodiments, which are merely illustrative of the principles of the invention, and that various changes and modifications may be made therein without departing from the scope of the principles of the invention.
Claims (5)
1. A method for synthesizing trihydroxymethyl phosphine oxide is characterized by comprising the following specific steps:
step S1: adding an alkali solution into tetrakis hydroxymethyl phosphonium chloride serving as a raw material, heating to 60-98 ℃ for reaction, cooling to room temperature after the reaction is finished, adding a hydrochloric acid solution, adjusting the pH value of a mixed system to 2-3, concentrating to separate out salt, filtering, adding an organic solvent to separate out the salt for the second time, and filtering to obtain crude tris (hydroxymethyl) phosphine oxide;
step S2: and (4) adding the crude trimethylol phosphine oxide obtained in the step (S1) into an organic solvent for extraction, and distilling the extract under reduced pressure to obtain refined trimethylol phosphine oxide.
2. The method for synthesizing tris (hydroxymethyl) phosphine oxide according to claim 1, wherein: in the step S1, the alkali in the alkali solution is sodium hydroxide, potassium hydroxide or calcium hydroxide, the molar ratio of the tetrakis hydroxymethyl phosphonium chloride to the alkali is 1: 1-2, and the concentration of the alkali solution is 10-30 wt%.
3. The method for synthesizing tris (hydroxymethyl) phosphine oxide according to claim 1, wherein: the reaction time in the step S1 is 8-10 h.
4. The method for synthesizing tris (hydroxymethyl) phosphine oxide according to claim 1, wherein: the concentration of the hydrochloric acid solution in the step S1 is 6 mol/L.
5. The method for synthesizing tris (hydroxymethyl) phosphine oxide according to claim 1, wherein: the organic solvent in the step S1 is methanol or ethanol, and the organic solvent in the step S2 is a mixed solvent of methanol and ethyl acetate in a volume ratio of 1: 1-3 or a mixed solvent of ethanol and ethyl acetate in a volume ratio of 1: 2-3.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114230608A (en) * | 2021-12-07 | 2022-03-25 | 湖北省兴发磷化工研究院有限公司 | Production process of reactive flame retardant THPO |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103980313A (en) * | 2014-05-23 | 2014-08-13 | 厦门大学 | Phosphorus-nitrogen synergistic flame-retardant polyalcohol and preparation method thereof |
-
2021
- 2021-06-30 CN CN202110738537.8A patent/CN113429437A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103980313A (en) * | 2014-05-23 | 2014-08-13 | 厦门大学 | Phosphorus-nitrogen synergistic flame-retardant polyalcohol and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| MARTIN. GRAYSON: "Phosphonium Compounds. III. Mechanism of Hydroxide Cleavage of Tetrakis(hydroxymethyl)phosphonium Chloride", 《J. AM. CHEM. SOC.》, 1 January 1963 (1963-01-01), pages 79 - 83, XP002582991 * |
| ZHIWEI TAN等: "Phosphorus-containing polymers from tetrakis-(hydroxymethyl)phosphonium sulfate III. A new hydrolysis-resistant tris(allyloxymethyl)phosphine oxide and its thiol-ene reaction under ultraviolet irradiation", 《RSC ADV.》, 13 August 2014 (2014-08-13), pages 41705 - 41713 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114230608A (en) * | 2021-12-07 | 2022-03-25 | 湖北省兴发磷化工研究院有限公司 | Production process of reactive flame retardant THPO |
| CN114230608B (en) * | 2021-12-07 | 2024-03-15 | 湖北省兴发磷化工研究院有限公司 | Production process of reactive flame retardant THPO |
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Application publication date: 20210924 |