CN108586525B - Preparation method of n-hexyl phosphoric acid - Google Patents
Preparation method of n-hexyl phosphoric acid Download PDFInfo
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- CN108586525B CN108586525B CN201810176209.1A CN201810176209A CN108586525B CN 108586525 B CN108586525 B CN 108586525B CN 201810176209 A CN201810176209 A CN 201810176209A CN 108586525 B CN108586525 B CN 108586525B
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- PHNWGDTYCJFUGZ-UHFFFAOYSA-N hexyl dihydrogen phosphate Chemical compound CCCCCCOP(O)(O)=O PHNWGDTYCJFUGZ-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 90
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 66
- 238000001816 cooling Methods 0.000 claims abstract description 27
- 238000010438 heat treatment Methods 0.000 claims abstract description 26
- 238000010992 reflux Methods 0.000 claims abstract description 26
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000004821 distillation Methods 0.000 claims abstract description 16
- 239000002994 raw material Substances 0.000 claims abstract description 16
- 238000005406 washing Methods 0.000 claims abstract description 12
- 239000008367 deionised water Substances 0.000 claims abstract description 11
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical compound CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims description 35
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 13
- 238000001914 filtration Methods 0.000 claims description 11
- 238000000605 extraction Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 4
- 238000005086 pumping Methods 0.000 claims 3
- 238000003756 stirring Methods 0.000 claims 3
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 238000009776 industrial production Methods 0.000 abstract description 4
- 238000002156 mixing Methods 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 239000012043 crude product Substances 0.000 abstract 2
- 239000003960 organic solvent Substances 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- 238000001308 synthesis method Methods 0.000 description 5
- WTVNABTWDZCYCN-UHFFFAOYSA-N hexane;hydrobromide Chemical compound Br.CCCCCC WTVNABTWDZCYCN-UHFFFAOYSA-N 0.000 description 4
- 239000012776 electronic material Substances 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000000654 additive Substances 0.000 description 2
- IYYIVELXUANFED-UHFFFAOYSA-N bromo(trimethyl)silane Chemical compound C[Si](C)(C)Br IYYIVELXUANFED-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- LXCYSACZTOKNNS-UHFFFAOYSA-N diethoxy(oxo)phosphanium Chemical compound CCO[P+](=O)OCC LXCYSACZTOKNNS-UHFFFAOYSA-N 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- MNDIARAMWBIKFW-UHFFFAOYSA-N 1-bromohexane Chemical compound CCCCCCBr MNDIARAMWBIKFW-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- XONPDZSGENTBNJ-UHFFFAOYSA-N molecular hydrogen;sodium Chemical compound [Na].[H][H] XONPDZSGENTBNJ-UHFFFAOYSA-N 0.000 description 1
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
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
- C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
- C07F9/3804—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)] not used, see subgroups
- C07F9/3826—Acyclic unsaturated acids
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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 relates to the technical field of organic chemical industry preparation, in particular to a preparation method of electronic grade novel n-hexyl phosphoric acid, which comprises the steps of mixing n-bromohexane and triethyl phosphite, heating to 130-150 ℃, reacting for 5-10 hours, cooling, and removing redundant raw materials through reduced pressure distillation to obtain n-hexyl phosphate; adding a proper amount of hydrochloric acid, heating and refluxing for 24-48 hours, cooling, extracting with toluene, decoloring a toluene layer with activated carbon, washing with deionized water and hydrochloric acid, and concentrating to obtain a crude product; and (3) crystallizing and purifying the crude product obtained in the last step by using an organic solvent to obtain the electronic grade n-hexylphosphoric acid with the metal ion content of less than 1 ppm. The invention provides a novel n-hexylphosphoric acid preparation method which has the advantages of easily obtained raw materials, low cost, safe and convenient operation, suitability for industrial production and production efficiency improvement.
Description
Technical Field
The invention relates to the technical field of organic chemical preparation, in particular to a preparation method of electronic grade novel n-hexyl phosphoric acid.
Background
N-hexyl phosphoric acid is an important raw material for synthesizing a medical intermediate and is also an important additive of an electronic material. However, the existing technology for preparing n-hexylphosphoric acid is difficult to meet the requirement of electronic materials on low metal content of additives, so that n-hexylphosphoric acid is not applied to electronic materials in a large scale. At present, the synthesis methods of n-hexylphosphoric acid reported in the literature mainly include the following two methods:
(1) first Synthesis method
The method comprises the following steps of using n-bromo-hexane and diethyl phosphite as raw materials, dehydrogenating diethyl phosphite with sodium hydrogen, carrying out nucleophilic substitution reaction, and hydrolyzing with hydrochloric acid to obtain a target compound, wherein the synthetic route is as follows:
in the synthesis method, hazardous sodium and hydrogen are used as raw materials, the production risk coefficient is increased, the operation steps are complicated, and the method is not suitable for large-scale production.
(2) Second Synthesis method
The method comprises the following steps of taking n-bromohexane as a raw material, firstly forming ester with triethyl phosphite at a high temperature, and then hydrolyzing with trimethyl bromosilane or hydrochloric acid to obtain a target compound, wherein the synthetic route is as follows:
the synthesis method adopts trimethyl bromosilane for hydrolysis, so that the cost is high and the post-treatment process is complex.
Therefore, a novel n-hexylphosphoric acid preparation method which has the advantages of easily obtained raw materials, low cost, safe and convenient operation, suitability for industrial production and production efficiency improvement is needed.
Disclosure of Invention
In view of the above problems, the invention provides a novel n-hexylphosphoric acid preparation method which has the advantages of easily available raw materials, low cost, safe and convenient operation, suitability for industrial production and production efficiency improvement.
In order to achieve the above object, the present invention provides the following technical solutions:
the preparation method of the novel n-hexyl phosphoric acid comprises the following steps:
s1: mixing and heating n-bromohexane and triethyl phosphite in proportion, controlling the temperature at 130-150 ℃, and reacting for 5-10 hours in a heat preservation manner;
s2: after the reaction of the step S1 is finished, cooling to below 80 ℃, removing redundant raw materials by reduced pressure distillation, and stopping distillation until the temperature is 150 ℃;
s3: after the step S2 is finished, cooling to below 60 ℃, adding a proper amount of hydrochloric acid, and heating and refluxing for 24-48 hours;
s4: after the reaction of step S3, cooling to below 50 ℃, extracting with toluene for 2 times, combining the toluene for 2 times, adding activated carbon, heating to 40-60 ℃, preserving heat for 1 hour, and filtering;
s5: washing the decolored toluene for 7-10 times by using deionized water and hydrochloric acid, wherein the washing temperature is 40-60 ℃;
s6: after the step S5 is finished, removing toluene by reduced pressure distillation;
s7: and cooling, adding n-hexane for crystallization, filtering and drying to obtain the qualified n-hexylphosphoric acid.
The molar ratio of the n-hexane bromide to the triethyl phosphite in the step S1 is 1: 1.18 to 1.5.
The content of metal ions in the hydrochloric acid in the step S3 and the step S5 is less than 10ppm, and the concentration is 30-37%.
In the step S5, the weight ratio of the added deionized water to the n-bromo-hexane in the system is 1:1, and the resistivity of the deionized water is greater than 12 omega m.
In the step S3, the weight ratio of the added hydrochloric acid to the n-bromo-hexane in the system is 2: 1-4: 1.
In the step S4, the amount of the added active carbon is 1-2% of the amount of the n-hexane bromide in the system.
In the step S5, deionized water and hydrochloric acid are added according to a weight ratio of 1.25-2.5: 100.
In the step S7, the weight ratio of the amount of n-hexane added to the amount of bromo-n-hexane in the system is 0.5-1: 1, and the crystallization temperature is 5-10 ℃.
The invention has the advantages and beneficial effects that: provides a novel n-hexyl phosphoric acid preparation method which has the advantages of easily obtained raw materials, low cost, safe and convenient operation and suitability for industrial production. The invention adopts a two-step continuous one-pot reaction, thereby improving the production efficiency.
Detailed Description
The following further describes embodiments of the present invention with reference to examples. The following examples are only for illustrating the technical solutions of the present invention more clearly, and the protection scope of the present invention is not limited thereby.
Example 1
400kg of n-bromohexane and 472kg of triethyl phosphite were introduced into a 2000L reactor under vacuum, stirred, slowly heated to 150 ℃ and reacted for 5 hours. After the reaction, the reaction mixture was cooled to 80 ℃ or lower, and the excess raw material was removed by distillation under reduced pressure, and the distillation was stopped at 150 ℃. After the distillation is finished, cooling to below 60 ℃, and adding 400kg of 30% hydrochloric acid into the reaction kettle; heating to reflux reaction for 8 hours, continuously adding 400kg of 30% hydrochloric acid, heating to reflux reaction for 8 hours, adding again 400kg of 30% hydrochloric acid, and refluxing to react for 8 hours. After the reaction is finished, cooling to 50 ℃, adding 400kg of toluene for extraction twice, combining toluene layers, adding 3kg of activated carbon for decoloring at 50 ℃ for 1 hour, and filtering. The toluene layer was washed with 400kg of deionized water and 10kg of hydrochloric acid at 50 ℃ for 10 times. After the completion of washing, the toluene layer was concentrated under reduced pressure. After the concentration, the mixture was cooled to 40 ℃, 400kg of n-hexane was added, and after heating and refluxing for 30 minutes, the mixture was cooled to 5 ℃, filtered and dried to obtain 163kg of a white solid. The purity is higher than 99 percent, and the metal ions detected by ICP are less than 1 ppm.
Example 2
Into a 2000L reactor, 400kg of n-hexane bromide and 480kg of triethyl phosphite were pumped in under vacuum, stirred, slowly heated to 150 ℃ and reacted for 5 hours. After the reaction, the reaction mixture was cooled to 80 ℃ or lower, and the excess raw material was removed by distillation under reduced pressure, and the distillation was stopped at 150 ℃. After the distillation is finished, cooling to below 60 ℃, and adding 400kg of 30% hydrochloric acid into the reaction kettle; heating to reflux reaction for 10 hours, continuously adding 400kg of 30% hydrochloric acid, heating to reflux reaction for 10 hours, adding 400kg of 30% hydrochloric acid again, and refluxing to react for 10 hours. After the reaction is finished, cooling to 50 ℃, adding 400kg of toluene for extraction twice, combining toluene layers, adding 3kg of activated carbon for decoloring at 50 ℃ for 1 hour, and filtering. The toluene layer was washed with 400kg of deionized water and 10kg of hydrochloric acid at 40 ℃ for 10 times. After the completion of washing, the toluene layer was concentrated under reduced pressure. After the concentration, the mixture was cooled to 40 ℃, 400kg of n-hexane was added, and after heating and refluxing for 30 minutes, the mixture was cooled to 5 ℃, filtered and dried to obtain 166kg of a white solid. The purity is higher than 99 percent, and the metal ions detected by ICP are less than 1 ppm.
Example 3
Into a 2000L reactor, 400kg of n-hexane bromide and 480kg of triethyl phosphite were pumped in under vacuum, stirred, slowly heated to 150 ℃ and reacted for 5 hours. After the reaction, the reaction mixture was cooled to 80 ℃ or lower, and the excess raw material was removed by distillation under reduced pressure, and the distillation was stopped at 150 ℃. After the distillation is finished, cooling to below 60 ℃, and adding 400kg of 30% hydrochloric acid into the reaction kettle; heating to reflux reaction for 10 hours, continuously adding 400kg of 30% hydrochloric acid, heating to reflux reaction for 10 hours, adding 400kg of 30% hydrochloric acid again, and refluxing to react for 10 hours. After the reaction is finished, cooling to 50 ℃, adding 400kg of toluene for extraction twice, combining toluene layers, adding 3kg of activated carbon for decoloring at 50 ℃ for 1 hour, and filtering. The toluene layer was washed with 400kg of deionized water and 10kg of hydrochloric acid at 40 ℃ for 9 times. After the completion of washing, the toluene layer was concentrated under reduced pressure. After the concentration, the mixture was cooled to 40 ℃, 400kg of n-hexane was added, and after heating and refluxing for 30 minutes, the mixture was cooled to 5 ℃, filtered and dried to obtain 170kg of a white solid. The purity is higher than 99 percent, and the metal ions detected by ICP are less than 1 ppm.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (3)
1. The preparation method of n-hexyl phosphoric acid is characterized by comprising the following steps: pumping 400kg of n-bromohexane and 472kg of triethyl phosphite into a 2000L reaction kettle in vacuum, stirring, slowly heating to 150 ℃, and reacting for 5 hours; after the reaction is finished, cooling to below 80 ℃, distilling under reduced pressure to remove redundant raw materials, and stopping distilling to 150 ℃; after the distillation is finished, cooling to below 60 ℃, and adding 400kg of 30% hydrochloric acid into the reaction kettle; heating to reflux reaction for 8 hours, continuously adding 400kg of 30% hydrochloric acid, heating to reflux reaction for 8 hours, adding again 400kg of 30% hydrochloric acid, and refluxing to react for 8 hours; after the reaction is finished, cooling to 50 ℃, adding 400kg of toluene for extraction twice, combining toluene layers, adding 3kg of activated carbon for decoloring at 50 ℃ for 1 hour, and filtering; washing the toluene layer with 400kg of deionized water and 10kg of hydrochloric acid at 50 ℃ for 10 times; after washing, concentrating the toluene layer under reduced pressure; cooling to 40 ℃ after concentration, adding 400kg of normal hexane, heating and refluxing for 30 minutes, cooling to 5 ℃, filtering, and drying to obtain 163kg of n-hexylphosphoric acid; the purity is higher than 99 percent, and the metal ions detected by ICP are less than 1 ppm.
2. The preparation method of n-hexyl phosphoric acid is characterized by comprising the following steps: pumping 400kg of n-bromo hexane and 480kg of triethyl phosphite into a 2000L reaction kettle in vacuum, stirring, slowly heating to 150 ℃, and reacting for 5 hours; after the reaction is finished, cooling to below 80 ℃, distilling under reduced pressure to remove redundant raw materials, and stopping distilling to 150 ℃; after the distillation is finished, cooling to below 60 ℃, and adding 400kg of 30% hydrochloric acid into the reaction kettle; heating to reflux reaction for 10 hours, continuously adding 400kg of 30% hydrochloric acid, heating to reflux reaction for 10 hours, adding 400kg of 30% hydrochloric acid again, and refluxing to react for 10 hours; after the reaction is finished, cooling to 50 ℃, adding 400kg of toluene for extraction twice, combining toluene layers, adding 3kg of activated carbon for decoloring at 50 ℃ for 1 hour, and filtering; washing the toluene layer with 400kg of deionized water and 10kg of hydrochloric acid at 40 ℃ for 10 times; after washing, concentrating the toluene layer under reduced pressure; after the concentration, cooling to 40 ℃, adding 400kg of normal hexane, heating and refluxing for 30 minutes, cooling to 5 ℃, filtering, and drying to obtain 166kg of n-hexylphosphoric acid; the purity is higher than 99 percent, and the metal ions detected by ICP are less than 1 ppm.
3. The preparation method of n-hexyl phosphoric acid is characterized by comprising the following steps: pumping 400kg of n-bromo hexane and 480kg of triethyl phosphite into a 2000L reaction kettle in vacuum, stirring, slowly heating to 150 ℃, and reacting for 5 hours; after the reaction is finished, cooling to below 80 ℃, distilling under reduced pressure to remove redundant raw materials, and stopping distilling to 150 ℃; after the distillation is finished, cooling to below 60 ℃, and adding 400kg of 30% hydrochloric acid into the reaction kettle; heating to reflux reaction for 10 hours, continuously adding 400kg of 30% hydrochloric acid, heating to reflux reaction for 10 hours, adding 400kg of 30% hydrochloric acid again, and refluxing to react for 10 hours; after the reaction is finished, cooling to 50 ℃, adding 400kg of toluene for extraction twice, combining toluene layers, adding 3kg of activated carbon for decoloring at 50 ℃ for 1 hour, and filtering; washing the toluene layer with 400kg of deionized water and 10kg of hydrochloric acid at 40 ℃ for 9 times; after washing, concentrating the toluene layer under reduced pressure; after the concentration, cooling to 40 ℃, adding 400kg of normal hexane, heating and refluxing for 30 minutes, cooling to 5 ℃, filtering, and drying to obtain 170kg of n-hexylphosphoric acid; the purity is higher than 99 percent, and the metal ions detected by ICP are less than 1 ppm.
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| CN201810176209.1A CN108586525B (en) | 2018-03-02 | 2018-03-02 | Preparation method of n-hexyl phosphoric acid |
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0734151A (en) * | 1993-07-20 | 1995-02-03 | Mitsui Mining & Smelting Co Ltd | Extraction agent for rare earth metal and method for separating and refining rare earth metal |
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2018
- 2018-03-02 CN CN201810176209.1A patent/CN108586525B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0734151A (en) * | 1993-07-20 | 1995-02-03 | Mitsui Mining & Smelting Co Ltd | Extraction agent for rare earth metal and method for separating and refining rare earth metal |
Non-Patent Citations (3)
| Title |
|---|
| Aqueous dispersion of multiwall carbon nanotubes with phosphonic acid derivatives;C. Oueiny等;《Colloids and Surfaces A: Physicochem. Eng. Aspects》;20160122;第493卷;第41-51页 * |
| Copper(II) n-Alkylphosphonates Used as Nanofillers: Single Crystal, Powder Structure Studies and Influence of the Alkyl Chain Length on the Magnetic Properties;Sophie Chausson等;《Eur. J. Inorg. Chem》;20120315;2193-2202 * |
| Synthesis and Polymerization Kinetics of Acrylamide Phosphonic Acids and Esters as New Dentine Adhesives;V. Besse等;《JOURNAL OF POLYMER SCIENCE PART A: POLYMER CHEMISTRY》;20120911;第51卷;第149-157页 * |
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