CN108586525A - A kind of novel n-hexyl phosphoric acid preparation method - Google Patents
A kind of novel n-hexyl phosphoric acid preparation method Download PDFInfo
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- CN108586525A CN108586525A CN201810176209.1A CN201810176209A CN108586525A CN 108586525 A CN108586525 A CN 108586525A CN 201810176209 A CN201810176209 A CN 201810176209A CN 108586525 A CN108586525 A CN 108586525A
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- Prior art keywords
- phosphoric acid
- novel
- hexane
- hexyl phosphoric
- added
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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 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 63
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 42
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- 239000002994 raw material Substances 0.000 claims abstract description 13
- MNDIARAMWBIKFW-UHFFFAOYSA-N 1-bromohexane Chemical compound CCCCCCBr MNDIARAMWBIKFW-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000008367 deionised water Substances 0.000 claims abstract description 12
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000010992 reflux Methods 0.000 claims abstract description 10
- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical compound CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000005292 vacuum distillation Methods 0.000 claims abstract description 8
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 6
- 238000002425 crystallisation Methods 0.000 claims abstract description 5
- 230000008025 crystallization Effects 0.000 claims abstract description 5
- 239000002253 acid Substances 0.000 claims abstract description 4
- 238000001816 cooling Methods 0.000 claims abstract description 4
- 238000010828 elution Methods 0.000 claims abstract description 3
- 150000003839 salts Chemical class 0.000 claims abstract description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N methyl pentane Natural products CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 24
- 238000001914 filtration Methods 0.000 claims description 10
- 238000004821 distillation Methods 0.000 claims description 8
- -1 Bromo n-hexane Chemical compound 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims 1
- 229910052794 bromium Inorganic materials 0.000 claims 1
- 238000004321 preservation Methods 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 10
- 239000000126 substance Substances 0.000 abstract description 2
- 239000012043 crude product Substances 0.000 abstract 2
- 238000000605 extraction Methods 0.000 abstract 1
- 239000003960 organic solvent Substances 0.000 abstract 1
- 238000010189 synthetic method Methods 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 125000001246 bromo group Chemical group Br* 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 239000012776 electronic material Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000000654 additive Substances 0.000 description 2
- 239000003610 charcoal Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- LXCYSACZTOKNNS-UHFFFAOYSA-N diethoxy(oxo)phosphanium Chemical compound CCO[P+](=O)OCC LXCYSACZTOKNNS-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- XONPDZSGENTBNJ-UHFFFAOYSA-N molecular hydrogen;sodium Chemical compound [Na].[H][H] XONPDZSGENTBNJ-UHFFFAOYSA-N 0.000 description 2
- ZDGSIQDOHOSTCA-UHFFFAOYSA-N CCCCCC[P] Chemical compound CCCCCC[P] ZDGSIQDOHOSTCA-UHFFFAOYSA-N 0.000 description 1
- OATWCNSODQAOQC-UHFFFAOYSA-N [SiH4].Br Chemical compound [SiH4].Br OATWCNSODQAOQC-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- IYYIVELXUANFED-UHFFFAOYSA-N bromo(trimethyl)silane Chemical compound C[Si](C)(C)Br IYYIVELXUANFED-UHFFFAOYSA-N 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000686 essence Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- DKAGJZJALZXOOV-UHFFFAOYSA-N hydrate;hydrochloride Chemical compound O.Cl DKAGJZJALZXOOV-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 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 present invention relates to organic chemical industry's preparing technical fields, more particularly to the preparation method of a kind of novel n-hexyl phosphoric acid of electronics rank, after bromo n-hexane, triethyl phosphite are mixed, it is heated to 130~150 DEG C, reaction 5~10 hours, cooling, vacuum distillation removes extra raw material, obtains n-hexyl phosphate；The hydrochloric acid of appropriate amount is added, is heated to reflux 24~48 hours, cooling, toluene extraction, toluene layer, with deionized water and salt acid elution, is then concentrated to give crude product after activated carbon decolorizing；Crude product obtained in the previous step is carried out crystallization with organic solvent to purify, obtains the electron level n-hexyl phosphoric acid that metal ion content is less than 1ppm.The present invention provides a kind of raw materials to be easy to get, at low cost, easy-to-operate, is suitble to industrialized production, improves the novel n-hexyl phosphoric acid preparation method of production efficiency.
Description
Technical field
The present invention relates to organic chemical industry's preparing technical field, more particularly to the system of a kind of novel n-hexyl phosphoric acid of electronics rank
Preparation Method.
Background technology
N-hexyl phosphoric acid is the important source material of synthesis medicine intermediate, while being also the important additives of electronic material.But
The existing technology for preparing n-hexyl phosphoric acid is difficult to meet requirement of the electronic material to additive low-metal content, causes n-hexyl phosphorus
Acid does not obtain large-scale application in electronic material.Currently, the synthetic method of the n-hexyl phosphoric acid of document report, mainly have with
Lower two kinds：
(1) the first synthetic method
Use bromo n-hexane and diethyl phosphite for raw material, after diethyl phosphite first uses sodium hydrogen dehydrogenation, into
Row nucleophilic substitution obtains target compound, synthetic route is as follows by persalt hydrolysis：
In this synthetic method, raw material uses dangerous material sodium hydrogen, and production danger coefficient increases, complex for operation step, is not suitable for
Amplification production.
(2) second of synthetic method
Use bromo n-hexane for raw material, at ester under first and triethyl phosphite hot conditions, then, by front three bromide
Silane or hydrochloric acid water solution obtain target compound, and synthetic route is as follows：
It is hydrolyzed using bromotrimethylsilane in this synthetic method, cost is higher, and aftertreatment technology is complicated.
Therefore need a kind of raw material be easy to get, be at low cost, easy-to-operate, it is suitble to industrialized production, improves production efficiency
Novel n-hexyl phosphoric acid preparation method.
Invention content
In view of problem above, the present invention provides a kind of raw materials to be easy to get, at low cost, easy-to-operate, is suitble to industrialization
Production, improves the novel n-hexyl phosphoric acid preparation method of production efficiency.
In order to achieve the above-mentioned object of the invention, the present invention provides following technical scheme：
A kind of novel n-hexyl phosphoric acid preparation method in the present invention, includes the following steps：
S1：Bromo n-hexane and triethyl phosphite are mixed in proportion, heated, control temperature is protected at 130~150 DEG C
Temperature reaction 5~10 hours；
S2：Step S1 after reaction, is cooled to 80 DEG C hereinafter, vacuum distillation removes extra raw material, distillation to temperature
150 DEG C of stoppings；
S3：After step S2, be cooled to 60 DEG C hereinafter, be added appropriate amount hydrochloric acid, be heated to reflux 24~48 hours；
S4：Step S3 after reaction, is cooled to 50 DEG C hereinafter, being extracted 2 times with toluene, activity is added in 2 toluene of merging
Charcoal is heated to 40~60 DEG C and keeps the temperature 1 hour, filtering；
S5：Toluene deionized water after decoloration and salt acid elution 7~10 times, wash temperature is 40~60 DEG C；
S6：After step S5, vacuum distillation removal toluene；
S7：Cooling, addition n-hexane crystallization, filtering, drying obtain qualified n-hexyl phosphoric acid.
The molar ratio of bromo n-hexane and triethyl phosphite is 1 in the step S1：1.18~1.5.
In the step S3 and step S5 the metal ion content of hydrochloric acid be less than 10ppm, a concentration of 30~37%.
In the step S5, the weight ratio that deionized water dosage and bromo n-hexane in system is added is 1:1, deionized water
Resistivity is more than 12 Ω m.
In the step S3, the weight ratio of bromo n-hexane is 2 in the hydrochloric acid content and system of addition:1~4:1.
In the step S4,1~2% that activated carbon dosage is bromo n-hexane in system is added.
In the step S5, the weight ratio that deionized water and hydrochloric acid is added is 1.25~2.5:100.
In the step S7, the weight ratio that bromo n-hexane in the amount and system of n-hexane is added is 0.5~1:1, it is described
The temperature of crystallization is 5~10 DEG C.
The advantages of the present invention are：There is provided a kind of raw material be easy to get, be at low cost, easy-to-operate, be suitble to
The novel n-hexyl phosphoric acid preparation method of industrialized production.The present invention uses a kind of reaction of the continuous cooking-pot type of two step, improves
Production efficiency.
Specific implementation mode
With reference to embodiment, the specific embodiment of the present invention is further described.Following embodiment is only used for more
Add and clearly demonstrate technical scheme of the present invention, and not intended to limit the protection scope of the present invention.
Embodiment 1
Into the reaction kettle of 2000L, vacuum is pumped into 400kg bromos n-hexane, 472kg triethyl phosphites, stirs, slowly
150 DEG C are heated to, is reacted 5 hours.After reaction, 80 DEG C are cooled to hereinafter, vacuum distillation removes extra raw material, distillation is extremely
150 DEG C of stoppings of temperature.Distillation terminates, and is cooled to 60 DEG C hereinafter, 30% hydrochloric acid of 400kg is added into reaction kettle；It is heated to flowing back
Reaction 8 hours, continuously adds 400kg30% hydrochloric acid, and 30% hydrochloric acid of 400kg, reflux is added in heating reflux reaction 8 hours again
Reaction 8 hours.Reaction terminates, and cools to 50 DEG C, and 400kg toluene is added and is extracted twice, and combining methylbenzene layer is added 3kg and lives
Property 50 DEG C of charcoal decolourize 1 hour, filtering.Toluene layer is washed with deionized water 400kg and hydrochloric acid 10kg, 50 DEG C of wash temperature, washing
10 times.After washing, toluene layer is concentrated under reduced pressure.It has concentrated and has been cooled to 40 DEG C, n-hexane 400kg is added, is heated to reflux 30 points
Zhong Hou, is cooled to 5 DEG C, and filtering is dried to obtain white solid 163kg.Purity is less than higher than 99%, ICP detection metal ions
1ppm。
Embodiment 2
Into the reaction kettle of 2000L, vacuum is pumped into 400kg bromos n-hexane, 480kg triethyl phosphites, stirs, slowly
150 DEG C are heated to, is reacted 5 hours.After reaction, 80 DEG C are cooled to hereinafter, vacuum distillation removes extra raw material, distillation is extremely
150 DEG C of stoppings of temperature.Distillation terminates, and is cooled to 60 DEG C hereinafter, 30% hydrochloric acid of 400kg is added into reaction kettle；It is heated to flowing back
Reaction 10 hours continuously adds 30% hydrochloric acid of 400kg, and heating reflux reaction 10 hours, again plus 400kg enters 30% hydrochloric acid, returns
Stream reaction 10 hours.Reaction terminates, and cools to 50 DEG C, and 400kg toluene is added and is extracted twice, and 3kg is added in combining methylbenzene layer
50 DEG C of activated carbon decolourizes 1 hour, filtering.Toluene layer is washed with deionized water 400kg and hydrochloric acid 10kg, and 40 DEG C of wash temperature is washed
It washs 10 times.After washing, toluene layer is concentrated under reduced pressure.It has concentrated and has been cooled to 40 DEG C, n-hexane 400kg is added, is heated to reflux 30
After minute, 5 DEG C are cooled to, filtering is dried to obtain white solid 166kg.Purity is less than higher than 99%, ICP detection metal ions
1ppm。
Embodiment 3
Into the reaction kettle of 2000L, vacuum is pumped into 400kg bromos n-hexane, 480kg triethyl phosphites, stirs, slowly
150 DEG C are heated to, is reacted 5 hours.After reaction, 80 DEG C are cooled to hereinafter, vacuum distillation removes extra raw material, distillation is extremely
150 DEG C of stoppings of temperature.Distillation terminates, and is cooled to 60 DEG C hereinafter, 30% hydrochloric acid of 400kg is added into reaction kettle；It is heated to flowing back
Reaction 10 hours continuously adds 30% hydrochloric acid of 400kg, and 30% hydrochloric acid of 400kg is added in heating reflux reaction 10 hours again,
Back flow reaction 10 hours.Reaction terminates, and cools to 50 DEG C, and 400kg toluene is added and is extracted twice, and combining methylbenzene layer is added
50 DEG C of 3kg activated carbons decolourize 1 hour, filtering.Toluene layer is washed with deionized water 400kg and hydrochloric acid 10kg, 40 DEG C of wash temperature,
Washing 9 times.After washing, toluene layer is concentrated under reduced pressure.It has concentrated and has been cooled to 40 DEG C, n-hexane 400kg is added, is heated to reflux 30
After minute, 5 DEG C are cooled to, filtering is dried to obtain white solid 170kg.Purity is less than higher than 99%, ICP detection metal ions
1ppm。
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all essences in the present invention
With within principle, any modification, equivalent replacement, improvement and so on should all be included in the protection scope of the present invention god.
Claims (8)
1. a kind of novel n-hexyl phosphoric acid preparation method, which is characterized in that include the following steps：
S1：Bromo n-hexane and triethyl phosphite are mixed in proportion, heated, for control temperature at 130~150 DEG C, heat preservation is anti-
It answers 5~10 hours；
S2：Step S1 after reaction, is cooled to 80 DEG C hereinafter, vacuum distillation removes extra raw material, distillation to 150 DEG C of temperature
Stop；
S3：After step S2, be cooled to 60 DEG C hereinafter, be added appropriate amount hydrochloric acid, be heated to reflux 24~48 hours；
S4：Step S3 after reaction, is cooled to 50 DEG C hereinafter, being extracted 2 times with toluene, and activated carbon is added in 2 toluene of merging,
It is heated to 40~60 DEG C and keeps the temperature 1 hour, filtering；
S5：Toluene deionized water after decoloration and salt acid elution 7~10 times, wash temperature is 40~60 DEG C；
S6：After step S5, vacuum distillation removal toluene；
S7：Cooling, addition n-hexane crystallization, filtering, drying obtain qualified n-hexyl phosphoric acid.
2. a kind of novel n-hexyl phosphoric acid preparation method according to claim 1, which is characterized in that bromine in the step S1
It is 1 for the molar ratio of n-hexane and triethyl phosphite：1.18~1.5.
3. a kind of novel n-hexyl phosphoric acid preparation method according to claim 1, which is characterized in that the step S3 and step
The metal ion content of hydrochloric acid is less than 10ppm in rapid S5, and a concentration of 30~37%.
4. a kind of novel n-hexyl phosphoric acid preparation method according to claim 1, which is characterized in that in the step S5,
The weight ratio that deionized water dosage and bromo n-hexane in system is added is 1:1, deionized water resistivity is more than 12 Ω m.
5. a kind of novel n-hexyl phosphoric acid preparation method according to claim 1, which is characterized in that in the step S3,
The weight ratio of bromo n-hexane is 2 in the hydrochloric acid content and system of addition:1~4:1.
6. a kind of novel n-hexyl phosphoric acid preparation method according to claim 1, which is characterized in that in the step S4,
1~2% that activated carbon dosage is bromo n-hexane in system is added.
7. a kind of novel n-hexyl phosphoric acid preparation method according to claim 1, which is characterized in that in the step S5,
The weight ratio that deionized water and hydrochloric acid is added is 1.25~2.5:100.
8. a kind of novel n-hexyl phosphoric acid preparation method according to claim 1, which is characterized in that in the step S7,
The weight ratio that bromo n-hexane in the amount and system of n-hexane is added is 0.5~1:1, the temperature of the crystallization is 5~10 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810176209.1A CN108586525B (en) | 2018-03-02 | 2018-03-02 | Preparation method of n-hexyl phosphoric acid |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810176209.1A CN108586525B (en) | 2018-03-02 | 2018-03-02 | Preparation method of n-hexyl phosphoric acid |
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| Publication Number | Publication Date |
|---|---|
| CN108586525A true CN108586525A (en) | 2018-09-28 |
| CN108586525B CN108586525B (en) | 2020-09-25 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
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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 |
-
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 |
|---|
| C. OUEINY等: "Aqueous dispersion of multiwall carbon nanotubes with phosphonic acid derivatives", 《COLLOIDS AND SURFACES A: PHYSICOCHEM. ENG. ASPECTS》 * |
| SOPHIE CHAUSSON等: "Copper(II) n-Alkylphosphonates Used as Nanofillers: Single Crystal, Powder Structure Studies and Influence of the Alkyl Chain Length on the Magnetic Properties", 《EUR. J. INORG. CHEM》 * |
| V. BESSE等: "Synthesis and Polymerization Kinetics of Acrylamide Phosphonic Acids and Esters as New Dentine Adhesives", 《JOURNAL OF POLYMER SCIENCE PART A: POLYMER CHEMISTRY》 * |
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