CN113956287A - Process for the preparation of orthophosphoric acid esters - Google Patents
Process for the preparation of orthophosphoric acid esters Download PDFInfo
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- CN113956287A CN113956287A CN202111341881.XA CN202111341881A CN113956287A CN 113956287 A CN113956287 A CN 113956287A CN 202111341881 A CN202111341881 A CN 202111341881A CN 113956287 A CN113956287 A CN 113956287A
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- 238000000034 method Methods 0.000 title claims abstract description 49
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical class OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 title abstract description 4
- 238000002360 preparation method Methods 0.000 title description 6
- 238000006243 chemical reaction Methods 0.000 claims abstract description 93
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims abstract description 43
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 208000012839 conversion disease Diseases 0.000 claims abstract description 5
- 230000014759 maintenance of location Effects 0.000 claims abstract description 4
- 125000001340 2-chloroethyl group Chemical group [H]C([H])(Cl)C([H])([H])* 0.000 claims description 7
- 239000003054 catalyst Substances 0.000 claims description 7
- 150000004713 phosphodiesters Chemical class 0.000 claims description 7
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 4
- LUVCTYHBTXSAMX-UHFFFAOYSA-N tris(2-chloroethyl) phosphite Chemical compound ClCCOP(OCCCl)OCCCl LUVCTYHBTXSAMX-UHFFFAOYSA-N 0.000 claims description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 4
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims description 2
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 2
- 235000011147 magnesium chloride Nutrition 0.000 claims description 2
- 229910001510 metal chloride Inorganic materials 0.000 claims description 2
- 239000001119 stannous chloride Substances 0.000 claims description 2
- 235000011150 stannous chloride Nutrition 0.000 claims description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 2
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- 235000005074 zinc chloride Nutrition 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- -1 orthophosphoric acid ortho ester Chemical class 0.000 abstract description 3
- 230000035484 reaction time Effects 0.000 abstract description 3
- 235000011007 phosphoric acid Nutrition 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 14
- 230000008707 rearrangement Effects 0.000 description 13
- 239000003507 refrigerant Substances 0.000 description 13
- 230000001276 controlling effect Effects 0.000 description 12
- 239000000463 material Substances 0.000 description 10
- 239000007788 liquid Substances 0.000 description 9
- UDPGUMQDCGORJQ-UHFFFAOYSA-N (2-chloroethyl)phosphonic acid Chemical compound OP(O)(=O)CCCl UDPGUMQDCGORJQ-UHFFFAOYSA-N 0.000 description 8
- 239000005976 Ethephon Substances 0.000 description 8
- 150000002148 esters Chemical class 0.000 description 8
- 238000005886 esterification reaction Methods 0.000 description 7
- 238000005086 pumping Methods 0.000 description 7
- 238000006462 rearrangement reaction Methods 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 238000005481 NMR spectroscopy Methods 0.000 description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 239000011574 phosphorus Substances 0.000 description 6
- 229910052698 phosphorus Inorganic materials 0.000 description 6
- 238000004611 spectroscopical analysis Methods 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 230000032050 esterification Effects 0.000 description 5
- 230000006578 abscission Effects 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 125000005678 ethenylene group Chemical group [H]C([*:1])=C([H])[*:2] 0.000 description 4
- 150000005690 diesters Chemical class 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 230000004345 fruit ripening Effects 0.000 description 3
- 150000002905 orthoesters Chemical class 0.000 description 3
- 230000002829 reductive effect Effects 0.000 description 3
- 108090000790 Enzymes Proteins 0.000 description 2
- 102000004190 Enzymes Human genes 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 229940088598 enzyme Drugs 0.000 description 2
- 239000013067 intermediate product Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- 108010059892 Cellulase Proteins 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 102000004160 Phosphoric Monoester Hydrolases Human genes 0.000 description 1
- 108090000608 Phosphoric Monoester Hydrolases Proteins 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229940106157 cellulase Drugs 0.000 description 1
- 230000005465 channeling Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- NVJBFARDFTXOTO-UHFFFAOYSA-N diethyl sulfite Chemical compound CCOS(=O)OCC NVJBFARDFTXOTO-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000010606 normalization Methods 0.000 description 1
- 210000000056 organ Anatomy 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 239000005648 plant growth regulator Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000001243 protein synthesis Methods 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 229920002477 rna polymer Polymers 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 230000004936 stimulating effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 230000014616 translation Effects 0.000 description 1
- 229920001567 vinyl ester resin Polymers 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)]
- C07F9/40—Esters thereof
- C07F9/4071—Esters thereof the ester moiety containing a substituent or a structure which is considered as characteristic
- C07F9/4075—Esters with hydroxyalkyl compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
- C07F9/40—Esters thereof
- C07F9/4003—Esters thereof the acid moiety containing a substituent or a structure which is considered as characteristic
- C07F9/4006—Esters of acyclic acids which can have further substituents on alkyl
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)
Abstract
A process for preparing orthophosphoric acid ortho ester is disclosed, which comprises providing a reaction system comprising three series-connected reactors; inputting raw materials of phosphorus trichloride and ethylene oxide into an inlet of a first-stage reactor, wherein the molar ratio of the phosphorus trichloride to the ethylene oxide is 1: 3.0-3.2; controlling the reaction temperature T of the first stage reactor1At 5-50 ℃ for a residence time t15-10 min, so that the reaction conversion rate is 50-80%; controlling the reaction temperature of the second stage reactor to be a temperature rise process and an outlet temperature T2The range is 50-80 ℃; controlling the reaction temperature T of the third stage reactor3The range is 180-210 ℃, and the retention time t is3The reaction time is 50-100 min, and the product is obtained.
Description
Technical Field
The invention relates to a method for preparing phosphoric acid ortho-ester (di- (2-chloroethyl) phosphoric acid diester, short for ortho-ester), in particular to a method for continuously preparing the ortho-ester, and the ortho-ester prepared by the method can be used as a raw material for preparing ethephon.
Background
Ethephon is a high-quality and high-efficiency plant growth regulator with the following structure, and has the effects of promoting fruit ripening, stimulating wound flow, regulating the sex transformation of partial plants and the like, wherein the ethephon has the following structure:
it mainly enhances the ability of synthesizing ribonucleic acid in cells and promotes the synthesis of protein. In the abscission zone of plant such as petiole, carpopodium and petal base, the increase of protein synthesis promotes the re-synthesis of cellulase in abscission layer, because the abscission layer formation is accelerated, and the organ abscission is caused. Ethephon can enhance the activity of enzyme, and can activate phosphatase and other enzymes related to fruit ripening to promote fruit ripening.
There are various methods for preparing ethephon, including a diethyl sulfite route, an ethylene oxide route, an ethylene route, a dichloroethane route, etc., and among them, the ethylene oxide route is widely favored because of low production requirements.
The ethylene oxide route mainly comprises the following three process sections:
1) phosphorus trichloride reacts with ethylene oxide to form tris- (2-chloroethyl) phosphite ester (called vinylester for short, and the reaction is called esterification for short), the reaction is a strong exothermic reaction, and the reaction heat is 450KJ/mol phosphorus trichloride:
2) intramolecular rearrangement of the diester to produce an intermediate (n-ester for short, and rearrangement for short):
the reaction is strongly exothermic, and the reaction heat is 190KJ/mol of the sub-ester; and
3) and (4) carrying out acidolysis on the intermediate.
The prior art has conducted many studies on the above-mentioned first-step and second-step reactions, respectively. For example,
for esterification reaction, CN104119374A discloses a method for continuously producing vinylene, which takes phosphorus trichloride and ethylene oxide as raw materials to react in a microchannel reaction system formed by a microchannel reaction device coupled with a pipeline type premixer and a refrigerant cooling device, comprising: firstly, continuously pumping phosphorus trichloride and ethylene oxide into a pipeline type premixer for premixing (the mixing pressure is 0.01 MPa-2.00 MPa); then introducing the premixed mixed solution of phosphorus trichloride and ethylene oxide into a microchannel reaction device, simultaneously starting a refrigerant cooling device of a microchannel reaction system, and collecting effluent liquid of the microchannel reaction device after the reaction is completed, wherein the effluent liquid is a product with the purity of the vinylene being more than 98%. The microchannel reactor adopted by the method is formed by connecting 4-6 groups of microchannel reactors in series, and each group of microchannel reactor is formed by 200 pipelines with the diameter of phi 4mm multiplied by 2000 mm.
Although the single pipe of the method can continuously and stably obtain the highest flow rate of 4kg/h and the product purity of more than 98 percent, and the reaction time is shortened to more than ten minutes, each pipeline of the microchannel reactor is a straight pipe, has defects on the fineness of temperature control and has adverse effect on the reaction.
For rearrangement reaction, CN103819507B discloses a method of using a tubular rearrangement reactor and a kettle type rearrangement reactor in series, which can effectively increase the yield of n-ester (the n-ester content can reach 95%), the method comprises: the vinylene firstly enters a stirring reaction kettle for rearrangement reaction, and then flows into a vertical tubular rearrangement device for heat preservation reaction. Wherein the flow rate of the material is controlled at 0.6m3H; the reaction temperature of the stirring type reaction kettle is controlled to be 140-170 ℃; the stirring speed of the stirring type reaction kettle is controlled at 135 r/min; the reaction temperature of the vertical tube type rearrangement reactor is controlled to be 150-180 ℃. The ethephon rearrangement process disclosed in the document is originalA set of stirring reaction kettle is added in front of a material inlet of some vertical tube type rearrangers, so that rearrangement reaction is more complete and more complete, heat transfer is more uniform and effective, a series of problems that the temperature of the traditional rearrangers is not easy to control, the temperature is frequently raised, material flushing and back mixing occur and the like are effectively solved, the temperature of the rearrangers is more easily controlled, the unit consumption of the process is reduced, the conversion rate and the yield of the n-ester are increased, and the production is more stable. However, the method adopts the technical scheme that a set of stirring reaction kettle is added in front of the material inlet of the original vertical tubular rearrangement device, and a series of problems that the temperature of the traditional rearrangement device is not easy to control, the temperature is frequently raised, the materials are flushed and backmixed and the like can be partially solved, but the backmixing phenomenon of the stirring reaction kettle still exists, and the reaction efficiency and the heat transfer efficiency are not high.
CN108479653 discloses an integrated microchannel reaction device and a method for preparing normal ester by using the same. The integrated microchannel reaction device consists of 5-9 stages of microchannel reactors which are connected in series, wherein one stage is a preheating section, and the rest are rearrangement reaction sections; each stage of micro-channel reactor comprises a plurality of annular pipelines. The tris (2-chloroethyl) phosphite ester material is preheated by a micro-channel preheating section and enters a micro-channel rearrangement reaction section for rearrangement reaction. The annular microchannel adopted in the document has the characteristics of thin material layer, good mass and heat transfer efficiency (the single-tube reactor can stably and continuously obtain the diester and the n-ester with the highest flow of 4 kg/h), stable temperature and high n-ester yield (the n-ester content can reach 98%). However, the annular pipeline has the defects of difficult processing and installation, easy generation of dead angles and formation of channeling or short circuit when materials flow in the annular gap, and accordingly reduced heat transfer efficiency and product quality.
The current method for preparing the vinylene intermediate ester and the normal ester mainly has the following problems:
a) the esterification and rearrangement are independently controlled, and frequent material cooling and heating operations lead to high energy consumption and high unit consumption;
b) both esterification and rearrangement reactions are strongly exothermic reactions, and the problem of formation of byproducts by intermolecular high-temperature rearrangement exists in the reaction process.
Therefore, inhibiting the side reactions of each reaction process and improving the heat transfer capacity of each reaction process are two major problems that must be faced in the industrial production of ethephon.
Disclosure of Invention
The invention aims to solve the problems in the esterification link and the rearrangement link in the process of preparing ethephon, in particular to the problems of complicated operation, high energy consumption, high unit consumption and the like in the step-by-step completion of esterification and rearrangement.
Accordingly, one aspect of the present invention relates to a process for the preparation of bis- (2-chloroethyl) phosphodiester having the general formula:
it includes:
providing a reaction system comprising three reactors connected in series;
inputting raw materials of phosphorus trichloride and ethylene oxide into an inlet of a first-stage reactor, wherein the dosage ratio (molar ratio) of the phosphorus trichloride to the ethylene oxide is 1: 3.0-3.2;
controlling the reaction temperature T of the first stage reactor1At 5-50 ℃ for a residence time t11-5min, so that the reaction conversion rate is 50-80%;
controlling the reaction temperature of the second stage reactor to be a temperature rise process and an outlet temperature T2The range is 50-80 ℃;
controlling the reaction temperature T of the third stage reactor3The range is 180-210 ℃, and the retention time t is3Is 50-100 min.
Detailed Description
If the esterification reaction is further refined, the formation of tris- (2-chloroethyl) phosphite from the reaction of phosphorus trichloride with ethylene oxide involves: phosphorus trichloride first forms a first intermediate product (for short, monoester) with one ethylene oxide molecule, then forms a second intermediate product (for short, diester) with two ethylene oxide molecules, and forms a product of addition of three ethylene oxide molecules.
The inventors of the present invention have found, through studies, that when bis- (2-chloroethyl) phosphodiester is directly prepared from phosphorus trichloride and ethylene oxide by a three-stage reaction, the highest yield of bis- (2-chloroethyl) phosphodiester can be obtained if the conversion rate is controlled to 50 to 80%, preferably 68 to 78%, during the first stage reaction. The present invention has been completed based on this finding.
In the present invention, the term "conversion" means the molar ratio of phosphorus-chlorine bonds consumed by the reaction to the original phosphorus-chlorine bonds.
Accordingly, one aspect of the present invention relates to a process for the preparation of di- (2-chloroethyl) phosphodiester (n-ester) using a three-stage reactor. The method comprises the following steps:
1. providing a reaction system comprising three reactors connected in series
The three-stage series reactor used in the reaction system of the present invention is not particularly limited per se, and may be conventional reactors known in the art, and they may each be a plug flow reactor, a microchannel reactor, or the like.
In one embodiment of the present invention, the reactor used in the first stage reaction is a pipe reactor and/or microchannel reactor with a pipe diameter of 0.5-3 mm, preferably 0.6-1.5mm, more preferably 0.6-1mm, and a pipe length of 20-200 m, preferably 30-190m, more preferably 40-180 m. After reading the present disclosure, one of ordinary skill in the art can readily adjust the length of each reactor, i.e., the liquid holdup volume, and modify the residence time of the reaction to achieve more optimal results.
In one example of the invention, the reactor used in the second stage reaction is a pipeline reactor and/or a microchannel reactor provided with a three-dimensional structural inner member with a mixing effect. Pipeline reactors equipped with three-dimensional internal structures with mixing effects suitable for the process of the invention are known from the prior art, and may be, for example, the high-efficiency mixing pipeline reactor disclosed in CN204999665U or the pipeline reactor with built-in flyover and other static mixing element combinations disclosed in CN 101596441.
In one example of the invention, the microchannel reactor is a micro-nano reactor which is processed by a femtosecond laser technology and has the characteristics of high heat transfer coefficient, high specific surface, low flow channel resistance and the like.
2. Inputting raw materials of phosphorus trichloride and ethylene oxide into an inlet of a first-stage reactor, wherein the molar ratio of the phosphorus trichloride to the ethylene oxide is 1: 3.0-3.2
The method of feeding the phosphorus trichloride and the ethylene oxide as raw materials to the reactor is not particularly limited, and may be a conventional feeding method known in the art.
In one embodiment of the present invention, the feeding molar ratio of the phosphorus trichloride to the ethylene oxide is 1:3.0 to 3.1, preferably 1:3.0 to 3.05.
Reaction temperature T of the first stage reactor1The temperature is controlled to be 5-50 ℃, preferably 10-45 ℃, and more preferably 15-40 ℃.
Residence time t of the first stage reactor1The reaction time is controlled to be 1-5min, preferably 2-3.5min, so that the reaction conversion rate is 50-80%, preferably 68-78%.
The method of the invention controls the reaction temperature and the residence time of the first stage reactor, thereby controlling the reaction conversion rate (the molar ratio of the consumed phosphorus-chlorine bond to the original phosphorus-chlorine bond) to be 50-80%, preferably 55-78%, more preferably 60-77%, preferably 65-75%, and finally obtaining the highest yield of the bis- (2-chloroethyl) phosphodiester.
The process of the invention may optionally employ a catalyst in the reactor. The catalyst suitable for the process of the present invention is not particularly limited and may be a conventional catalyst known in the art. In one embodiment of the invention, the catalyst is selected from metal chlorides or combinations thereof, such as titanium tetrachloride, titanium trichloride, aluminum trichloride, magnesium chloride, zinc chloride, stannous chloride, and the like.
The method for determining the conversion rate of the reaction is not particularly limited, and a test method conventional in the art may be employed. In one embodiment of the invention, the percentage of each product obtained by the reaction is calculated by nuclear magnetic resonance phosphorus spectroscopy, and the conversion is calculated by area normalization.
3. Controlling the reaction temperature of the second stage reactor as the temperature rise process and the outlet temperatureDegree T2In one embodiment of the present invention, the outlet temperature of the second stage reactor is controlled to be 50-80 deg.C, preferably 55-75 deg.C, more preferably 58-72 deg.C.
In one embodiment of the invention, the residence time in the second stage reactor is from 4 to 10 minutes, preferably from 4.5 to 9 minutes, more preferably from 5 to 8 minutes.
4. Controlling the reaction temperature T of the third stage reactor3The range is 180-210 ℃, and the retention time t is3Is 50-100 min.
In one embodiment of the present invention, the reaction temperature in the third stage reactor is preferably controlled at 185-.
In one embodiment of the present invention, the residence time in the third stage is preferably controlled to 55 to 95 minutes, more preferably 60 to 90 minutes.
In one embodiment of the invention, the plug flow reactors used are three stages in series, the first reactor is a microchannel (equivalent diameter 1.6mm) reactor with coolant control, and the second and third reactors are composed of pipes with inner diameters of 2mm and 4mm, respectively. Continuously pumping phosphorus trichloride and ethylene oxide into a mixer by using a pump, and controlling the mass flow of the phosphorus trichloride to be 3.00kg/h and the mass flow of the ethylene oxide to be 3.02 kg/h; and the mixed liquid of phosphorus trichloride and ethylene oxide enters a three-stage series reaction device, the refrigerant of each reactor is started for cooling, the outlet temperature of each stage of reactor is controlled to be about 20 ℃ in the first stage, about 50 ℃ in the second stage and about 180 ℃ in the third stage, and the n-ester product is continuously obtained at the outlet of the last stage of reactor.
In one embodiment of the invention, the method adopts a specially designed technical idea of combining one-step completion with segmented control, and if three sections of reaction temperatures are taken as a whole, the method is a temperature rise control process as a whole. The integral temperature rise is combined with a plug flow type first-stage reactor with lower operating temperature, a second-stage reactor for enhancing the reaction rate and the heat transfer efficiency and a simple third-stage reactor, so that the remarkable technical effects are achieved: the content of the target product can reach more than 99 percent; unit consumption and energy consumption are obviously reduced.
In a preferred embodiment of the invention, the preparation method of the bis- (2-chloroethyl) phosphodiester adopts phosphorus trichloride and ethylene oxide as raw materials for direct preparation, the molar ratio of the phosphorus trichloride to the ethylene oxide is 1: 3.0-3.2, the method adopts three-step continuous flow reaction steps connected in series, the three-step reaction steps are integrally in a temperature rise state, the second-stage reaction temperature is controlled to be an adiabatic temperature rise process, and the outlet temperature range is T2100～150℃。
In one embodiment of the invention, the first stage reactor realizes the positive and reverse flow alternate control of the heat conducting oil, and the material is discharged from the first stage reactor to reach a certain reaction degree, namely the conversion rate is 50-80% mainly through the control of proper reaction temperature or temperature distribution and residence time.
The invention will be further described with reference to specific examples, but the scope of the invention is not limited thereto.
Example 1
The plug flow reaction device is connected in series in three stages, the first reactor is a micro-channel (equivalent diameter is 1.6mm) reactor containing refrigerant control, and the second reactor and the third reactor are respectively composed of pipelines with the inner diameters of 2mm and 4 mm.
Continuously pumping phosphorus trichloride and ethylene oxide into a mixer by using a pump, and controlling the mass flow of the phosphorus trichloride to be 3.00kg/h and the mass flow of the ethylene oxide to be 3.02 kg/h; and the mixed liquid of phosphorus trichloride and ethylene oxide enters a three-stage series reaction device, the refrigerants of all reactors are started to be cooled, the outlet temperature of the first reactor is controlled to be 20 ℃, the outlet temperature of the second reactor is controlled to be 50 ℃, the outlet temperature of the third reactor is controlled to be 180 ℃, the conversion rate of the first reactor is measured to be 75% by adopting a nuclear magnetic resonance phosphorus spectrometry, and the outlet of the last stage reactor can stably and continuously obtain a normal ester product with the content of 98.5%.
Example 2
The plug flow reaction device is connected in series in three stages, the first reactor is a micro-channel (equivalent diameter is 1.6mm) reactor containing refrigerant control, and the second reactor and the third reactor are respectively composed of pipelines with the inner diameters of 2mm and 4 mm.
Continuously pumping phosphorus trichloride and ethylene oxide into a mixer by using a pump, and controlling the mass flow of the phosphorus trichloride to be 3.00kg/h and the mass flow of the ethylene oxide to be 3.02 kg/h; and the mixed liquid of phosphorus trichloride and ethylene oxide enters a three-stage series reaction device, the refrigerants of all reactors are started to be cooled, the outlet temperature of the first reactor is controlled to be 25 ℃, the outlet temperature of the second reactor is controlled to be 50 ℃, the outlet temperature of the third reactor is controlled to be 180 ℃, the conversion rate of the first reactor is measured to be 76% by adopting a nuclear magnetic resonance phosphorus spectrometry, and the outlet of the last stage reactor can stably and continuously obtain a normal ester product with the content of 98.6%.
Example 3
The plug flow reaction device is connected in series in three stages, the first reactor is a micro-channel (equivalent diameter is 1.6mm) reactor containing refrigerant control, and the second reactor and the third reactor are respectively composed of pipelines with the inner diameters of 2mm and 4 mm.
Continuously pumping phosphorus trichloride and ethylene oxide into a mixer by using a pump, and controlling the mass flow of the phosphorus trichloride to be 3.00kg/h and the mass flow of the ethylene oxide to be 3.02 kg/h; and the mixed liquid of phosphorus trichloride and ethylene oxide enters a three-stage series reaction device, the refrigerants of all reactors are started to be cooled, the outlet temperature of the first reactor is controlled to be 25 ℃, the outlet temperature of the second reactor is controlled to be 55 ℃, the outlet temperature of the third reactor is controlled to be 180 ℃, the conversion rate of the first reactor is measured to be 76% by adopting a nuclear magnetic resonance phosphorus spectrometry, and the outlet of the last stage reactor can stably and continuously obtain a normal ester product with the content of 98.7%.
Example 4
The plug flow reaction device is connected in series in three stages, the first reactor is a micro-channel (equivalent diameter is 1.6mm) reactor containing refrigerant control, and the second reactor and the third reactor are respectively composed of pipelines with the inner diameters of 2mm and 4 mm.
Continuously pumping phosphorus trichloride and ethylene oxide into a mixer by using a pump, and controlling the mass flow of the phosphorus trichloride to be 3.00kg/h and the mass flow of the ethylene oxide to be 3.02 kg/h; and the mixed liquid of phosphorus trichloride and ethylene oxide enters a three-stage series reaction device, the refrigerants of all reactors are started to be cooled, the outlet temperature of the first reactor is controlled to be 25 ℃, the outlet temperature of the second reactor is controlled to be 55 ℃, the outlet temperature of the third reactor is controlled to be 180 ℃, the conversion rate of the first reactor is 77% by adopting a nuclear magnetic resonance phosphorus spectrometry, and the outlet of the last stage reactor can stably and continuously obtain a normal ester product with the content of 98.8%.
Example 5
The plug flow reaction device is connected in series in three stages, the first reactor is a micro-channel (equivalent diameter is 1.6mm) reactor containing refrigerant control, and the second reactor and the third reactor are respectively composed of pipelines with the inner diameters of 2mm and 4 mm.
Continuously pumping phosphorus trichloride and ethylene oxide into a mixer by using a pump, and controlling the mass flow of the phosphorus trichloride to be 3.00kg/h and the mass flow of the ethylene oxide to be 3.02 kg/h; and the mixed liquid of phosphorus trichloride and ethylene oxide enters a three-stage series reaction device, the refrigerants of all reactors are started to be cooled, the outlet temperature of the first reactor is controlled to be 35 ℃, the outlet temperature of the second reactor is controlled to be 55 ℃, the outlet temperature of the third reactor is controlled to be 180 ℃, the conversion rate of the first reactor is measured to be 78% by adopting a nuclear magnetic resonance phosphorus spectrometry, and the outlet of the last stage reactor can stably and continuously obtain a normal ester product with the content of 98.9%.
Comparative examples 6, 10 and 14
The same procedure as in example 1 was used, but the process conditions shown in the following table were used to prepare n-ester products, respectively, and the results are shown in the following table.
Examples 7 to 9 and 10 to 13
The same procedure as in example 1 was used to prepare the n-ester product, but using the process conditions shown in the following table, respectively, and the results are shown in the following table (wherein the catalysts of examples 8-10 were introduced into the reaction system by dissolution into phosphorus trichloride).
Claims (8)
1. A method for preparing bis- (2-chloroethyl) phosphodiester with the following formula by adopting a three-section reactor,
it includes:
providing a reaction system comprising three reactors connected in series;
inputting raw materials of phosphorus trichloride and ethylene oxide into an inlet of a first-stage reactor, wherein the molar ratio of the phosphorus trichloride to the ethylene oxide is 1: 3.0-3.2;
controlling the reaction temperature T of the first stage reactor1At 5-50 ℃ for a residence time t11-5min, so that the reaction conversion rate is 50-80%;
controlling the reaction temperature of the second stage reactor to be a temperature rise process and an outlet temperature T2The range is 50-80 ℃;
controlling the reaction temperature T of the third stage reactor3The range is 180-210 ℃, and the retention time t is3Is 50-100 min.
2. The process according to claim 1, wherein the molar ratio of phosphorus trichloride to ethylene oxide is 1:3.0 to 3.1, preferably 1:3.0 to 3.05.
3. The process according to claim 1 or 2, wherein the reaction temperature T of the first stage reactor is1Controlling the temperature at 10-45 ℃, preferably 15-40 ℃;
residence time t of the first stage reactor1Controlling for 1-5min, preferably 2-3.5 min.
4. The process according to claim 1 or 2, characterized in that the reaction temperature in the second stage reactor is 55-75 ℃, preferably 58-72 ℃;
the residence time in the second stage reactor is from 4 to 10 minutes, preferably from 4.5 to 9 minutes, more preferably from 5 to 8 minutes.
5. The method as claimed in claim 1 or 2, wherein the reaction temperature of the third stage reactor is preferably controlled at 185-205 ℃, more preferably 190-200 ℃;
the residence time in the third stage is preferably controlled to be 55 to 95 minutes, more preferably 60 to 90 minutes.
6. The method of claim 1 or 2, wherein the reaction system is optionally supplemented with a catalyst.
7. The process of claim 6, wherein the catalyst is selected from the group consisting of metal chlorides and combinations thereof, such as titanium tetrachloride, titanium trichloride, aluminum trichloride, magnesium chloride, zinc chloride, stannous chloride, and the like.
8. The process according to claim 1 or 2, wherein the conversion of tris- (2-chloroethyl) phosphite in the first stage reactor is 55-78%, preferably 60-77%, preferably 65-75%.
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| CN108840884A (en) * | 2018-07-17 | 2018-11-20 | 常州大学 | A kind of method of the continuous synthesizing phosphorous acid dialkyl ester of micro passage reaction |
| CN113522217A (en) * | 2021-07-07 | 2021-10-22 | 上海试四赫维化工有限公司 | Plate-fin structure reactor and application thereof in preparation of bis- (2-chloroethyl) phosphodiester |
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| US3803272A (en) * | 1972-08-25 | 1974-04-09 | Olin Corp | Process for preparing tetrakis(2-haloalkyl)alkylene diphosphates |
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