CN111848672B - Continuous synthesis process of phosphonic acid tetramethyl succinate - Google Patents
Continuous synthesis process of phosphonic acid tetramethyl succinate Download PDFInfo
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- CN111848672B CN111848672B CN202010873252.0A CN202010873252A CN111848672B CN 111848672 B CN111848672 B CN 111848672B CN 202010873252 A CN202010873252 A CN 202010873252A CN 111848672 B CN111848672 B CN 111848672B
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- C07—ORGANIC CHEMISTRY
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- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- 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, i.e. RP(=X)(XH)2 (X = S, 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
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- 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
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids RP(=O)(OH)2; Thiophosphonic acids, i.e. RP(=X)(XH)2 (X = S, 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
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- 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
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Abstract
The invention discloses a continuous synthesis process of phosphonic acid tetramethyl succinate, which comprises the following steps: continuously conveying the dimethyl maleate and the dimethyl phosphite into a premixer for sufficient premixing at a molar ratio of 1:1.02-1.20, standing for 20-40 s, mixing with a sodium methoxide catalyst, and introducing into a tubular reactor through a pipeline for preliminary reaction; then enters the reactor from the bottom of the kettle reactor; the retention time of the materials in the tubular reactor is 6-12 min; the reaction temperature is 25-35 ℃; after preliminary pipelining reaction, the materials are connected in series and sequentially enter each kettle-type reactor, and a sodium methoxide catalyst is added to ensure the reaction rate; the retention time of the materials in the kettle type reactors connected in series is 0.5-1.0 h; the reaction temperature is 25-35 ℃; and (3) obtaining a reaction product of phosphonic acid tetramethyl succinate in the kettle type reactor. The invention not only increases the production efficiency, but also effectively controls the reaction temperature, solves the heat exchange problem which is difficult to solve by the strong exothermic reaction, and has stable product quality.
Description
Technical Field
The invention relates to the field of chemical synthesis, in particular to phosphonic acid tetramethyl succinate and a synthesis process thereof, and particularly relates to an addition reaction for continuously synthesizing phosphonic acid tetramethyl succinate from dimethyl maleate and dimethyl phosphite.
Background
The phosphonic acid butanedioic acid tetramethyl ester is also called phosphonic acid butanedioic acid tetraalkyl ester, is yellow viscous liquid, and can be used as an important synthetic raw material and an intermediate of the water treatment agent PBTCA.
According to the traditional production method of phosphonic acid tetramethyl succinate, dimethyl maleate and dimethyl phosphite are mostly used as raw materials, an addition reaction is carried out in a kettle type reactor under the catalytic action of sodium methoxide by dropwise adding sodium methoxide-methanol solution, the reaction time is about 15 hours, a large amount of heat is released in the reaction process, the reaction temperature is difficult to control stably, a large amount of side reactions are generated, and the environmental pollution is caused.
In order to control the reaction temperature, a number of measures have been taken by the predecessors, both in terms of process and engineering. However, these measures have not solved the problem fundamentally and have respective disadvantages and drawbacks. For example, it is common in industry to dilute the reaction mixture using large amounts of solvent. And a material is dripped, but the solvent is distilled and recovered after the reaction, so that the production energy consumption is increased, and the like.
At present, no related disclosed preparation method for continuously preparing phosphonic acid tetramethyl succinate by using dimethyl maleate and dimethyl phosphite as raw materials under the catalytic action of sodium methoxide serving as catalysts exists.
Disclosure of Invention
Therefore, the technical problem to be solved by the invention is to provide a method for continuously synthesizing phosphonic acid tetramethyl succinate by using dimethyl maleate and dimethyl phosphite, so that side reactions are reduced, and the reaction time is shortened.
The technical scheme of the invention is that a continuous synthesis process of phosphonic acid tetramethyl succinate comprises the following steps:
1) continuously conveying the dimethyl maleate and the dimethyl phosphite into a premixer for full premixing in a molar ratio of 1:1.02-1.20, and then mixing with a sodium methoxide catalyst to enter a tubular reactor through a pipeline for preliminary reaction; then enters the reactor from the bottom of the kettle reactor; the flow rate of the maleic acid dimethyl ester is 25-45L/h, the flow rate of the dimethyl phosphite is 18-35L/h, and the volume ratio of the catalyst to the raw material is 0.5-1%; the retention time of the materials in the tubular reactor is 6-12 min; the reaction temperature is 25-35 ℃;
2) after the materials are subjected to preliminary channelization reaction, the materials are serially connected into a first kettle type reactor, and a sodium methoxide catalyst is added to ensure the reaction rate; the retention time of the materials in the first kettle type reactors connected in series is 0.5-1.0 h; the reaction temperature is 25-35 ℃; the volume ratio of the catalyst to the raw material is 0.5-1%;
3) the reaction solution enters a second kettle type reactor in series, and a sodium methoxide catalyst is added to ensure the reaction rate; the residence time of the materials in the second kettle type reactors connected in series is 0.5-1.0 h; the reaction temperature is 25-35 ℃; the volume ratio of the catalyst to the raw material is 1-3%; and (3) obtaining a reaction product of phosphonic acid tetramethyl succinate in the kettle type reactor.
According to the continuous synthesis process of phosphonic acid tetramethyl succinate, the residence time of the materials in the tubular reactor in the step 1) is preferably 6-12 min.
According to the continuous synthesis process of phosphonic acid tetramethylsuccinate, the preferable retention time of the materials in the step 2) in the serially connected kettle-type reactors is 0.5-1 h. In the step 3), the materials stay in the second kettle type reactors connected in series for 0.5-1 h.
According to the continuous synthesis process of the phosphonic acid tetramethyl succinate, the synthesis process is preferably characterized in that the sodium methoxide catalyst in the step 1) and the step 2) is methanol solution of sodium methoxide.
Further, the mass concentration of sodium methoxide in the methanol solution of sodium methoxide is 20-35%.
According to the continuous synthesis process of phosphonic acid tetramethyl succinate, a stirrer is preferably arranged in the tank reactor in the step 2). The stirring speed is preferably 60 r/min to 180 r/min.
According to the continuous synthesis process of phosphonic acid tetramethylsuccinate, the heat exchange coil is preferably arranged in the tubular reactor, the coil is of a steel tube spiral structure, and industrial chilled water passes through the coil; the kettle type reactor is internally provided with a heat exchange interlayer, and industrial chilled water is introduced for heat exchange.
In order to remove the reaction heat in time, a special heat exchange coil is arranged in the tubular reactor, the coil is of a stainless steel pipe spiral structure, industrial chilled water passes through the coil at the temperature of-5-4 ℃, and the heat generated by the reaction is taken away; the kettle type reactor is internally provided with a heat exchange interlayer, industrial chilled water can be introduced at a temperature of-5 to 4 ℃ for heat exchange, an external heat exchange device can be additionally arranged according to the exothermic condition of the reaction, the reactor is controlled to react at a temperature of 25 to 35 ℃, the reaction selectivity is improved, and the reaction selectivity is improved from the original 90 to 93 percent to 97 to 99 percent.
According to the continuous synthesis process of the phosphonic acid tetramethyl succinate, the residence time of the maleic acid dimethyl ester and the dimethyl phosphite in the premixer in the step 1) is preferably 10-50 s.
According to the continuous synthesis process of phosphonic acid tetramethyl succinate, the flow rate of the catalyst in the step 1) is preferably 0.2-0.8L/h; the flow rate of the catalyst in the first kettle type reactor in the step 2) is 0.2-0.8L/h; the flow rate of the catalyst in the second tank reactor is 0.4-2.4L/h.
Aiming at the defects of the prior art, in order to realize the continuous synthesis of the phosphonic acid tetramethyl succinate from the dimethyl maleate and the dimethyl phosphite, effectively control the reaction temperature, avoid the generation of side reaction, reduce the reaction production time and increase the production efficiency, the invention provides the process for continuously synthesizing the phosphonic acid tetramethyl succinate, which adopts a plurality of different reactors in series connection in a form, and the reaction materials react in stages. The production efficiency is improved, the operation and production are simplified, and the environmental pollution caused by starting and stopping the vehicle is inhibited.
The invention has the beneficial effects that:
compared with the traditional production process, the continuous synthesis of the phosphonic acid tetramethylsuccinate not only increases the production efficiency, but also effectively controls the reaction temperature, solves the heat exchange problem which is difficult to solve by the strong exothermic reaction, avoids the self addition reaction of the maleic acid dimethylester under the high-temperature condition, and has stable product quality. The product yield is improved to 93-98% from the original 80-85%, and the selectivity is improved to 97-99% from 90-93%. Meanwhile, the reaction residence time is reduced, the total reaction time is reduced to 2-4h from the original 15h, and the productivity in unit time is improved. Reduces the production cost and the environmental pollution, and is suitable for industrial production.
Drawings
FIG. 1 is a schematic view of the present invention.
In the figure, 1 is a premixer, 2 is a tubular reactor, 3 is a first kettle reactor, and 4 is a second kettle reactor.
Detailed Description
Example 1
Dimethyl maleate is premixed by a premixer according to the flow rate of 45L/h and dimethyl phosphite according to the flow rate of 36L/h, the molar ratio is 1:1.20, the residence time of the premixer is about 20s, the premixed material enters a tubular reactor, then a catalyst sodium methoxide solution is added into the tubular reactor according to the flow rate of 0.2L/h for reaction, the reaction temperature of the tubular reactor is 25 ℃, the residence time is 6min, the conversion rate of dimethyl maleate is about 47%, the concentration of tetramethyl phosphonate succinate is 41% (wt), then a raw material liquid enters a kettle type reactor 1, a sodium methoxide solution catalyst is additionally added, the flow rate is 0.2L/h, the residence time is about 0.5h, the reaction temperature is 25 ℃, the conversion rate of dimethyl maleate is 97%, the concentration of tetramethyl phosphonate is 89.5% (wt), then the liquid enters a kettle type reactor 2, sodium methoxide solution catalyst is added, the flow rate is 2.4L/h, the retention time is about 0.5h, the reaction temperature is 25 ℃, the conversion rate of the maleic acid dimethyl ester is 99%, the concentration of the phosphonic acid tetramethyl succinate is 93% (wt), the selectivity is 99%, and the maleic acid dimethyl ester in the raw materials is completely converted.
Example 2
Dimethyl maleate is premixed through a premixer according to the flow rate of 45L/h and dimethyl phosphite according to the flow rate of 31L/h, the molar ratio is 1:1.02, the residence time is about 25s, the mixture enters a tubular reactor, then a catalyst sodium methoxide solution is added into the tubular reactor according to the flow rate of 0.8L/h for reaction, the reaction temperature of the tubular reactor is 35 ℃, the residence time is 7min, the conversion rate of dimethyl maleate is about 75%, the concentration of tetramethyl phosphonate succinate is 65.9% (wt), then a raw material liquid enters a kettle type reactor 1, a sodium methoxide solution catalyst is additionally added, the flow rate is 0.8L/h, the residence time is about 0.5h, the reaction temperature is 35 ℃, the conversion rate of dimethyl maleate is 99%, the concentration of tetramethyl phosphonate is 91.5% (wt), then the liquid enters a kettle type reactor 2, the flow rate of a catalyst added with sodium methoxide solution is 0.4L/h, the retention time is about 1h, the reaction temperature is 28 ℃, the conversion rate of the maleic acid dimethyl ester is 100%, the concentration of the phosphonic acid tetramethyl succinate is 98% (wt), the selectivity is 99%, and the maleic acid dimethyl ester in the raw materials is completely converted.
Example 3
Dimethyl maleate is premixed through a premixer according to the flow rate of 25L/h and dimethyl phosphite according to the flow rate of 18L/h, the molar ratio is 1:1.06, the residence time is about 40s, the mixture enters a tubular reactor, then a catalyst sodium methoxide solution is added into the tubular reactor according to the flow rate of 0.2L/h for reaction, the reaction temperature of the tubular reactor is 26 ℃, the residence time is 12min, the conversion rate of dimethyl maleate is about 65%, the concentration of tetramethyl phosphonate succinate is 57.9% (wt), then a raw material liquid enters a kettle type reactor 1, a sodium methoxide solution catalyst is additionally added, the flow rate is 0.2L/h, the residence time is about 1.0h, the reaction temperature is 26 ℃, the conversion rate of dimethyl maleate is 87%, the concentration of tetramethyl phosphonate is 83.5% (wt), then the liquid enters a kettle type reactor 2, the flow rate of a sodium methoxide solution catalyst is added additionally for 1.5L/h, the retention time is about 1h, the reaction temperature is 28 ℃, the conversion rate of the maleic acid dimethyl ester is 100%, the concentration of the phosphonic acid tetramethyl succinate is 97% (wt), the selectivity is 97%, and the maleic acid dimethyl ester in the raw materials is completely converted.
Example 4
Dimethyl maleate is premixed through a premixer according to the flow rate of 38L/h and dimethyl phosphite according to the flow rate of 29L/h, the molar ratio is 1:1.13, the residence time is about 25s, the mixture enters a tubular reactor, then a catalyst sodium methoxide solution is added into the tubular reactor according to the flow rate of 0.6L/h for reaction, the reaction temperature of the tubular reactor is 32 ℃, the residence time is 8min, the conversion rate of dimethyl maleate is about 54 percent, the concentration of tetramethyl phosphonate succinate is 48.3 percent (wt), then a raw material liquid enters a kettle type reactor 1, a sodium methoxide solution catalyst is additionally added, the flow rate is 0.6L/h, the residence time is about 0.6h, the reaction temperature is 33 ℃, the conversion rate of dimethyl maleate is 87 percent, the concentration of tetramethyl phosphonate is 80.4 percent (wt), then the liquid enters a kettle type reactor 2, the flow rate of a sodium methoxide solution catalyst is added for supplement, the flow rate is 1.8L/h, the retention time is about 0.6h, the reaction temperature is 31 ℃, the conversion rate of the maleic acid dimethyl ester is 99%, the concentration of the phosphonic acid tetramethyl succinate is 95% (wt), the selectivity is 98%, and the maleic acid dimethyl ester in the raw materials is completely converted.
Example 5
Dimethyl maleate is premixed through a premixer according to the flow rate of 28L/h and dimethyl phosphite according to the flow rate of 21L/h, the molar ratio is 1:1.11, the residence time is about 35s, the mixture enters a tubular reactor, then a catalyst sodium methoxide solution is added into the tubular reactor according to the flow rate of 0.5L/h for reaction, the reaction temperature of the tubular reactor is 31 ℃, the residence time is 10min, the conversion rate of dimethyl maleate is about 49%, the concentration of tetramethyl phosphonate succinate is 43.2% (wt), then a raw material liquid enters a kettle type reactor 1, a sodium methoxide solution catalyst is additionally added, the flow rate is 0.5L/h, the residence time is about 0.8h, the reaction temperature is 30 ℃, the conversion rate of dimethyl maleate is 87%, the concentration of tetramethyl phosphonate is 80.4% (wt), then the liquid enters a kettle type reactor 2, the flow rate of a sodium methoxide solution catalyst is added for supplement, the flow rate is 1.3L/h, the retention time is about 0.8h, the reaction temperature is 30 ℃, the conversion rate of the maleic acid dimethyl ester is 99%, the concentration of the phosphonic acid tetramethyl succinate is 96% (wt), the selectivity is 97%, and the maleic acid dimethyl ester in the raw materials is completely converted.
Example 6
Dimethyl maleate is premixed through a premixer according to the flow rate of 33L/h and dimethyl phosphite according to the flow rate of 24L/h, the molar ratio is 1:1.07, the residence time is about 28s, the premixed material enters a tubular reactor, then a catalyst sodium methoxide solution is added into the tubular reactor according to the flow rate of 0.2L/h for reaction, the reaction temperature of the tubular reactor is 25 ℃, the residence time is 9min, the conversion rate of dimethyl maleate is about 53 percent, the concentration of tetramethyl phosphonate succinate is 48.7 percent (wt), then a raw material liquid enters a kettle type reactor 1, a sodium methoxide solution catalyst is additionally added, the flow rate is 0.4L/h, the residence time is about 0.7h, the reaction temperature is 28 ℃, the conversion rate of dimethyl maleate is 79 percent, the concentration of tetramethyl phosphonate is 72.5 percent (wt), then the liquid enters a kettle type reactor 2, the flow rate of a sodium methoxide solution catalyst is added for supplement, the flow rate is 1.6L/h, the retention time is about 0.7h, the reaction temperature is 28 ℃, the conversion rate of the maleic acid dimethyl ester is 99%, the concentration of the phosphonic acid tetramethyl succinate is 97% (wt), the selectivity is 99%, and the maleic acid dimethyl ester in the raw materials is completely converted.
Claims (9)
1. A continuous synthesis process of phosphonic acid tetramethyl succinate is characterized in that: the method comprises the following steps:
1) continuously conveying the dimethyl maleate and the dimethyl phosphite into a premixer for sufficient premixing at a molar ratio of 1:1.02-1.20, standing for 20-40 s, mixing with a sodium methoxide catalyst, and introducing into a tubular reactor through a pipeline for preliminary reaction; then enters the reactor from the bottom of the kettle reactor; the flow rate of the maleic acid dimethyl ester is 25-45L/h, the flow rate of the dimethyl phosphite is 18-36L/h, and the volume ratio of the catalyst to the raw material is 0.5-1%; the retention time of the materials in the tubular reactor is 6-12 min; the reaction temperature is 25-35 ℃;
2) after the materials are subjected to preliminary channelization reaction, the materials are serially connected into a first kettle type reactor, and a sodium methoxide catalyst is added to ensure the reaction rate; the residence time of the materials in the first kettle type reactors connected in series is 0.5-1.0 h; the reaction temperature is 25-35 ℃; the volume ratio of the catalyst to the raw material is 0.5-1%;
3) the reaction solution enters a second kettle type reactor in series, and a sodium methoxide catalyst is added to ensure the reaction rate; the residence time of the materials in the second kettle type reactors connected in series is 0.5-1.0 h; the reaction temperature is 25-35 ℃; the volume ratio of the catalyst to the raw material is 1-3%; and (3) obtaining a reaction product of phosphonic acid tetramethyl succinate in the kettle type reactor.
2. The continuous synthesis process of phosphonic acid tetramethylsuccinate as claimed in claim 1, characterized in that: in the step 1), the retention time of the materials in the tubular reactor is 7-12 min.
3. The continuous synthesis process of phosphonic acid tetramethylsuccinate as claimed in claim 1, characterized in that: in the step 2), the retention time of the materials in the serially connected kettle type reactors is 0.6-1 h; in the step 3), the materials stay in the second kettle type reactors connected in series for 0.6-1 h.
4. The continuous synthesis process of phosphonic acid tetramethylsuccinate as claimed in claim 1, characterized in that: the sodium methoxide catalyst in the step 1) and the step 2) is a methanol solution of sodium methoxide.
5. The continuous synthesis process of phosphonic acid tetramethylsuccinate as claimed in claim 4, characterized in that: the mass concentration of sodium methoxide in the methanol solution of sodium methoxide is 20-35%.
6. The continuous synthesis process of phosphonic acid tetramethylsuccinate as claimed in claim 1, characterized in that: a stirrer is arranged in the kettle type reactor in the step 2).
7. The continuous synthesis process of phosphonic acid tetramethylsuccinate as claimed in claim 1, characterized in that: a heat exchange coil is arranged in the tubular reactor, the coil is of a steel pipe spiral structure, and industrial chilled water passes through the coil; the kettle type reactor is internally provided with a heat exchange interlayer, and industrial chilled water is introduced for heat exchange.
8. The continuous synthesis process of phosphonic acid tetramethylsuccinate as claimed in claim 1, characterized in that: the residence time of the dimethyl maleate and the dimethyl phosphite in the premixer in the step 1) is 20-35 s.
9. The continuous synthesis process of phosphonic acid tetramethylsuccinate as claimed in claim 1, characterized in that: the flow rate of the catalyst in the step 1) is 0.2-0.8L/h; the flow rate of the catalyst in the first kettle type reactor in the step 2) is 0.2-0.8L/h; the flow rate of the catalyst in the second tank reactor is 0.4-2.4L/h.
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