CN113754691B - Preparation method of tri (1, 3-dichloroisopropyl) phosphate - Google Patents
Preparation method of tri (1, 3-dichloroisopropyl) phosphate Download PDFInfo
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- CN113754691B CN113754691B CN202010482638.9A CN202010482638A CN113754691B CN 113754691 B CN113754691 B CN 113754691B CN 202010482638 A CN202010482638 A CN 202010482638A CN 113754691 B CN113754691 B CN 113754691B
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- dichloro
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- 229910019142 PO4 Inorganic materials 0.000 title claims abstract description 14
- 239000010452 phosphate Substances 0.000 title claims abstract description 14
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title abstract description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 40
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims abstract description 31
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229940051269 1,3-dichloro-2-propanol Drugs 0.000 claims abstract description 21
- DEWLEGDTCGBNGU-UHFFFAOYSA-N 1,3-dichloropropan-2-ol Chemical compound ClCC(O)CCl DEWLEGDTCGBNGU-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 20
- 239000003054 catalyst Substances 0.000 claims abstract description 17
- 238000010025 steaming Methods 0.000 claims abstract description 7
- 239000008096 xylene Substances 0.000 claims abstract description 7
- 238000001914 filtration Methods 0.000 claims abstract description 6
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 5
- 239000011964 heteropoly acid Substances 0.000 claims abstract description 3
- 238000003756 stirring Methods 0.000 claims description 13
- 238000001704 evaporation Methods 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 7
- 239000012295 chemical reaction liquid Substances 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 239000000440 bentonite Substances 0.000 claims description 5
- 229910000278 bentonite Inorganic materials 0.000 claims description 5
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 230000008020 evaporation Effects 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000012074 organic phase Substances 0.000 claims description 5
- 238000004321 preservation Methods 0.000 claims description 5
- 238000004821 distillation Methods 0.000 claims 1
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 abstract description 16
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 239000002994 raw material Substances 0.000 abstract description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 abstract description 3
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 abstract description 3
- 229910000041 hydrogen chloride Inorganic materials 0.000 abstract description 3
- 238000005886 esterification reaction Methods 0.000 abstract description 2
- 238000006555 catalytic reaction Methods 0.000 abstract 1
- 238000005406 washing Methods 0.000 abstract 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 12
- 239000012535 impurity Substances 0.000 description 12
- 238000004064 recycling Methods 0.000 description 12
- -1 mono-phosphorus ester Chemical class 0.000 description 8
- 239000012071 phase Substances 0.000 description 8
- 229910052698 phosphorus Inorganic materials 0.000 description 8
- 239000011574 phosphorus Substances 0.000 description 8
- 238000005086 pumping Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- CLBRCZAHAHECKY-UHFFFAOYSA-N [Co].[Pt] Chemical compound [Co].[Pt] CLBRCZAHAHECKY-UHFFFAOYSA-N 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 230000005484 gravity Effects 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- 239000002918 waste heat Substances 0.000 description 4
- 239000008346 aqueous phase Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- ASLWPAWFJZFCKF-UHFFFAOYSA-N tris(1,3-dichloropropan-2-yl) phosphate Chemical compound ClCC(CCl)OP(=O)(OC(CCl)CCl)OC(CCl)CCl ASLWPAWFJZFCKF-UHFFFAOYSA-N 0.000 description 3
- 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 2
- ABKDZANKXKCXKG-UHFFFAOYSA-B P(=O)([O-])([O-])[O-].[W+4].P(=O)([O-])([O-])[O-].P(=O)([O-])([O-])[O-].P(=O)([O-])([O-])[O-].[W+4].[W+4] Chemical compound P(=O)([O-])([O-])[O-].[W+4].P(=O)([O-])([O-])[O-].P(=O)([O-])([O-])[O-].P(=O)([O-])([O-])[O-].[W+4].[W+4] ABKDZANKXKCXKG-UHFFFAOYSA-B 0.000 description 2
- 150000003983 crown ethers Chemical class 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 229910003074 TiCl4 Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000007344 nucleophilic reaction Methods 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000003444 phase transfer catalyst Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic 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 System
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/08—Esters of oxyacids of phosphorus
- C07F9/09—Esters of phosphoric acids
- C07F9/091—Esters of phosphoric acids with hydroxyalkyl compounds with 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Landscapes
- 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 preparation method of tri (1, 3-dichloro isopropyl) phosphate, which specifically uses phosphoric acid and 1, 3-dichloro-2-propanol as raw materials, xylene as a water-carrying agent, and performs esterification reaction under the catalysis of heteropolyacid, and the tri (1, 3-dichloro isopropyl) phosphate is obtained through external steaming, water washing and filtration. The invention adopts phosphoric acid to replace phosphorus oxychloride for reaction, thereby not only reducing the cost of raw materials, but also improving the intrinsic safety of production; the raw materials and the catalyst can be recycled, so that the output of hydrogen chloride is avoided in the production process, the cost is reduced, and the environment is protected.
Description
Technical Field
The invention relates to the technical field of fine chemicals, in particular to a preparation method of tri (1, 3-dichloroisopropyl) phosphate.
Background
The tri (1, 3-dichloro isopropyl) phosphate is a good flame retardant and flame retardant plasticizer, is widely applied to manufacturing of novel organic polymer materials, and is also an important medical intermediate.
The tri (1, 3-dichloro isopropyl) phosphate is synthesized by nucleophilic reaction of phosphorus oxychloride and epoxy chloropropane/1, 3-dichloro-2-propanol under the action of catalyst. Currently, research focused on the synthesis of tris (1, 3-dichloroisopropyl) phosphate is on the choice of catalyst. Patent CN102863468A, CN107556338A, CN102807581B describes a preparation method using epichlorohydrin and phosphorus oxychloride as raw materials and using TiCl4, alCl3 or Lewis acid as catalyst, respectively. Patent CN109438506a provides a process for preparing tris (1, 3-dichloroisopropyl) phosphate from phosphorus oxychloride and 1, 3-dichloro-2-propanol in a catalyst-free environment.
The phosphorus oxychloride is used as the raw material in the method, and the phosphorus oxychloride has the advantages of easy volatilization, strong pungent smell, easy hydrolysis, large quantity of heat release and hydrogen chloride release, and strong corrosiveness. The characteristic of phosphorus oxychloride determines the harsh reaction conditions, has intrinsic safety hidden trouble in production, and is not easy to meet the current safety and environmental protection requirements. In view of the above problems, the present invention provides a method for preparing tris (1, 3-dichloroisopropyl) phosphate using phosphoric acid and 1, 3-dichloro-2-propanol under the condition of a catalyst.
Disclosure of Invention
The invention provides a preparation method of tri (1, 3-dichloro isopropyl) phosphate, which mainly comprises the following steps:
wherein, the phosphoric acid in the step (1) is added in the form of phosphoric acid aqueous solution with the mass fraction more than or equal to 80 percent, and the mole ratio of the phosphoric acid, the 1, 3-dichloro-2-propanol and the dimethylbenzene is 1 (3-4): (0.5-2).
Wherein the molar ratio of phosphoric acid to 1, 3-dichloro-2-propanol is preferably 1:3.5-4,1,3-dichloro-2-propanol excess.
Wherein the catalyst in the step (1) is heteropolyacid, which can be dodecaphosphotungstic acid and dodecasilicotungstic acid, and the dosage is 1-10% of the total mass of phosphoric acid, preferably 5-10%.
Wherein, in the step (2), the negative pressure range is-0.1 MPa to-0.05 MPa.
Wherein the pure water dosage in the step (3) is 0.5-1 times of the reaction liquid mass after external steaming.
Wherein the decoloring agent in the step (3) is bentonite or activated carbon, and the dosage is 1-5 per mill of the total mass of the product.
The related chemical formula is:
in the invention, the two phases are respectively an aqueous phase and an alcohol phase, tungsten phosphate is used as a phase transfer catalyst and an esterification catalyst, the reaction place is the aqueous phase, dimethylbenzene is mainly used as an organic solvent and a water-carrying agent, and 1, 3-dichloro-2-propanol is dispersed and diluted, and an azeotropic system is formed with water. After most of water is carried out by the dimethylbenzene, the dimethylbenzene can be regarded as single-phase reaction, at the moment, the water in the system is little, the temperature of the system is increased, and the reaction is promoted to generate the ternary ester; the reaction can be regarded as an end point as the reaction temperature of the system reaches about 135 ℃.
The 1, 3-dichloro-2-propanol has high boiling point, is insoluble in water, does not azeotropy with water, and finally has insufficient reaction. After the dimethylbenzene is added, the reaction is complete, and the yield of the ternary ester can be greatly improved.
More, tungsten phosphate is insoluble in xylene, and does not affect subsequent catalyst recovery.
The beneficial effects of the invention are:
the invention adopts phosphoric acid to replace phosphorus oxychloride for reaction, thereby not only reducing the cost of raw materials, but also improving the intrinsic safety of production; the two-phase reaction, the raw materials and the catalyst are respectively recovered and reused, the output of hydrogen chloride is avoided in the production process, the cost is reduced, and the method is environment-friendly.
Detailed Description
The invention is described in detail below by way of examples which are illustrative only and are not meant to limit the scope of applicability of the invention, as the skilled artisan will be able to modify the reagents, catalysts and reaction process conditions within the scope of the invention in light of the disclosure herein. All equivalent changes or modifications made in accordance with the spirit of the present invention should be construed to be included in the scope of the present invention.
All examples which follow were carried out with 1, 3-dichloro-2-propanol of 99.2% purity (self-produced by the company).
Example 1
Step one: 1152kg of 85% phosphoric acid aqueous solution, 4551kg of 1, 3-dichloro-2-propanol, 1060kg of dimethylbenzene and 49kg of dodecaphosphotungstic acid are sequentially added into the reaction kettle, stirring is started, the temperature is raised to 92+/-2 ℃, external water evaporation is started, dimethylbenzene flows back into the kettle, the temperature in the reaction kettle is gradually raised, the temperature in the kettle is raised to 124 ℃ after 3 hours, and heat preservation is continued for 1 hour.
Step two: and (3) evaporating the xylene solvent outside by utilizing waste heat under the pressure of-0.05 MPa for recycling, gradually increasing the negative pressure to-0.1 MPa, and externally evaporating the residual 1, 3-dichloro-2-propanol for recycling.
Step three: cooling the rest reaction liquid to 48 ℃, adding 2500kg of pure water into a reaction kettle, stirring for 20min, standing for layering for 2h, transferring the lower organic phase into a decoloring tank, adding 10kg of bentonite, stirring for 30min, filtering into a product storage tank by a diaphragm pump, pumping the rest water phase containing the catalyst into an external steaming kettle, concentrating, and drying for recycling.
The quality of the obtained product of tri (1, 3-dichloro isopropyl) phosphate is 4259.3kg.
Yield: 95.6%; chromaticity (platinum cobalt): 33; viscosity: 1879; specific gravity: 1.496; water content: 0.03%.
The content of the detected impurity is 3.27%, and the mono-phosphorus ester and the di-phosphorus ester are main impurities (in the impurities, the mono-phosphorus ester accounts for 2.7%, and the di-phosphorus ester accounts for 96.9%).
Example 2
Step one: 1224kg of 80% phosphoric acid aqueous solution, 5201kg of 1, 3-dichloro-2-propanol, 1060kg of dimethylbenzene and 98kg of dodecaphosphotungstic acid are sequentially added into a reaction kettle, stirring and heating are started to 90+/-2 ℃, external water evaporation is started, dimethylbenzene flows back into the kettle, the temperature in the reaction kettle is gradually increased, the temperature in the kettle is increased to 130 ℃ after 3 hours, and heat preservation is continued for 1 hour.
Step two: and (3) evaporating the xylene solvent outside by utilizing waste heat under the pressure of-0.05 MPa for recycling, gradually increasing the negative pressure to-0.1 MPa, and externally evaporating the residual 1, 3-dichloro-2-propanol for recycling.
Step three: cooling the rest reaction liquid to 50 ℃, adding 2500kg of pure water into a reaction kettle, stirring for 20min, standing for layering for 2h, transferring the lower organic phase into a decoloring tank, adding 5kg of active carbon, stirring for 30min, pumping and filtering to a product storage tank by a diaphragm pump, pumping the rest water phase containing the catalyst into an external steaming kettle, concentrating, and drying for recycling.
The quality of the obtained product of tri (1, 3-dichloro isopropyl) phosphate is 4266.7kg.
Yield: 96.2%; chromaticity (platinum cobalt): 35; viscosity: 1890; specific gravity: 1.498; water content: 0.05%.
The content of the detected impurity is 2.83%, and the mono-phosphorus ester and the di-phosphorus ester are main impurities (among the impurities, the mono-phosphorus ester accounts for 1.4%, and the di-phosphorus ester accounts for 98.3%).
Comparative example 1
Step one: 1152kg of 85% phosphoric acid aqueous solution, 4551kg of 1, 3-dichloro-2-propanol, 741kg of diethyl ether and 49kg of dodecaphosphotungstic acid are sequentially added into the reaction kettle, stirring is started, the temperature is raised to 33+/-1 ℃, external water evaporation is started, diethyl ether flows back into the kettle, the temperature in the reaction kettle is not obviously raised, and after 3 hours, the temperature in the kettle is 35+/-1 ℃, and the heat preservation is continued for 1 hour.
Step two: and (3) evaporating diethyl ether solvent for recycling under the pressure of-0.05 MPa by utilizing waste heat, gradually increasing the negative pressure to-0.1 MPa, and heating to evaporate the residual 1, 3-dichloro-2-propanol for recycling.
Step three: cooling the rest reaction liquid to 48 ℃, adding 2500kg of pure water into a reaction kettle, stirring for 20min, standing for layering for 2h, transferring the lower organic phase into a decoloring tank, adding 10kg of bentonite, stirring for 30min, filtering into a product storage tank by a diaphragm pump, pumping the rest water phase containing the catalyst into an external steaming kettle, concentrating, and drying for recycling.
The quality of the obtained product of tri (1, 3-dichloro isopropyl) phosphate is 3544.7kg.
Yield: 61.6%; chromaticity (platinum cobalt): 33; viscosity: 1879; specific gravity: 1.387; water content: 0.03%. The content of the detected impurity is 25.1%, the mono-phosphorus ester and the di-phosphorus ester are main impurities (in the impurity, the mono-phosphorus ester accounts for 57.4%, the di-phosphorus ester accounts for 31.6%, and the phosphoric acid accounts for 10.7%).
The reaction temperature of diethyl ether is too low, so that the reaction is difficult to reach high temperature and incomplete. Instead of using solvents, only the aqueous phase was refluxed and the reaction was vigorous, and it was difficult to control the safety (comparative examples were not made here for safety).
Comparative example 2
Step one: 1152kg of 85% phosphoric acid aqueous solution, 4551kg of 1, 3-dichloro-2-propanol, 1060kg of dimethylbenzene, 49kg of p-toluenesulfonic acid and 49kg of crown ether are sequentially added into the reaction kettle, stirring and heating are started to 92+/-2 ℃, external water evaporation is started, dimethylbenzene flows back into the kettle, the temperature in the reaction kettle is gradually increased, the temperature in the kettle is increased to 120 ℃ after 3 hours, and heat preservation is continued for 1 hour.
Step two: and (3) evaporating the xylene solvent outside by utilizing waste heat under the pressure of-0.05 MPa for recycling, gradually increasing the negative pressure to-0.1 MPa, and externally evaporating the residual 1, 3-dichloro-2-propanol for recycling.
Step three: cooling the rest reaction liquid to 46 ℃, adding 2500kg of pure water into a reaction kettle, stirring for 20min, standing for layering for 2h, transferring the lower organic phase into a decoloring tank, adding 10kg of bentonite, stirring for 30min, filtering into a product storage tank by a diaphragm pump, pumping the rest water phase containing the catalyst into an external steaming kettle, concentrating, and drying for recycling.
The quality of the obtained product of tri (1, 3-dichloro isopropyl) phosphate is 3956.2kg.
Yield: 79.4%; chromaticity (platinum cobalt): 33; viscosity: 1879; specific gravity: 1.419; water content: 0.03%. The content of the detected impurities is 13.5%, and the mono-phosphorus ester and the di-phosphorus ester are main impurities (among the impurities, the mono-phosphorus ester accounts for 33.9%, the di-phosphorus ester accounts for 61.9%, and the phosphoric acid accounts for 2.3%). (crown ethers are extremely toxic per se, and are used as little as possible or even preferably not used in industrial production).
Claims (8)
1. A method for preparing tri (1, 3-dichloroisopropyl) phosphate, which is characterized by comprising the following steps:
(1) Adding phosphoric acid, 1, 3-dichloro-2-propanol, dimethylbenzene and a catalyst into a reaction kettle, heating to 92+/-1 ℃ for reaction, gradually heating to 120-140 ℃ in the reaction process, and continuing to perform heat preservation reaction for 1-2 hours;
(2) Cooling the reaction liquid after external steaming to below 50 ℃, adding pure water, stirring and layering, adding a quantitative decoloring agent into a lower organic phase for decoloring, and filtering to obtain the tri (1, 3-dichloroisopropyl) phosphate.
2. The method according to claim 1, wherein the phosphoric acid in the step (1) is added in the form of an aqueous solution of phosphoric acid having a mass fraction of 80% or more.
3. The method according to claim 1, wherein the molar ratio of phosphoric acid, 1, 3-dichloro-2-propanol and xylene is 1:3-4: 0.5 to 2.
4. The method according to claim 1, wherein the catalyst is heteropolyacid, such as dodecaphosphotungstic acid and dodecasilicotungstic acid, and the amount is 1-10% of the total mass of phosphoric acid.
5. The method according to claim 1, wherein the pure water in the step (2) is used in an amount of 0.5 to 1 time by mass of the reaction liquid after external evaporation.
6. The method according to claim 1, wherein the decolorizing agent in the step (2) is bentonite or activated carbon, and the amount is 1-5% of the total mass of the product.
7. The process of claim 1, wherein the excess 1, 3-dichloro-2-propanol and xylene is recovered by means of negative pressure distillation.
8. The method of claim 1, wherein the water layer in step (2) is recycled by recovering the concentrated catalyst.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108997416A (en) * | 2018-08-28 | 2018-12-14 | 山东泰和水处理科技股份有限公司 | A kind of preparation method of phosphonic acids three (the chloro- 2- propyl of 1,3- bis-) ester |
| CN109232639A (en) * | 2018-10-11 | 2019-01-18 | 山东泰和水处理科技股份有限公司 | A kind of preparation method of phosphonic acids three (bis- chloropropyl of 1,3-) ester |
| CN109438506A (en) * | 2018-12-06 | 2019-03-08 | 山东泰和水处理科技股份有限公司 | A method of preparing tricresyl phosphate (bis- chloropropyl of 1,3-) ester |
-
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108997416A (en) * | 2018-08-28 | 2018-12-14 | 山东泰和水处理科技股份有限公司 | A kind of preparation method of phosphonic acids three (the chloro- 2- propyl of 1,3- bis-) ester |
| CN109232639A (en) * | 2018-10-11 | 2019-01-18 | 山东泰和水处理科技股份有限公司 | A kind of preparation method of phosphonic acids three (bis- chloropropyl of 1,3-) ester |
| CN109438506A (en) * | 2018-12-06 | 2019-03-08 | 山东泰和水处理科技股份有限公司 | A method of preparing tricresyl phosphate (bis- chloropropyl of 1,3-) ester |
Non-Patent Citations (2)
| Title |
|---|
| Preparation and properties of 2-chloroalkyl esters of boric, silicic, and phosphoric acids;Jones, W. J.等;《Journal of the Chemical Society》;第824-827页 * |
| 稀土固体超强酸SO4 2-/TiO2-Al2O3/La3+催化合成磷酸三 (1,3-二氯丙基)酯;于春红等;《南京师范大学学报（工程技术版）》;第第9卷卷(第第1期期);第57-60页 * |
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