Abstract
A method of preparing an alkyl phosphate compound based on a micro-reaction system. The micro-reaction system includes a feed pump, a first micro-mixer, a second micro-mixer, a first micro-channel reactor, a second micro-channel reactor and a back-pressure device, where the first micro-mixer, the second micro-mixer, the first micro-channel reactor, the second micro-channel reactor and the back-pressure device are sequentially connected. The method includes the following steps. An alkylamine compound and an acid-binding agent are simultaneously fed to a first micro-mixer for mixing and then to the first micro-channel reactor for pre-reaction to obtain a pre-reaction solution. The pre-reaction solution and a phosphate or phosphite are simultaneously fed to the second micro-mixer for mixing to obtain a first reaction mixture. The first reaction mixture is fed to the second micro-channel reactor to carry out a condensation reaction under a back pressure condition and is concentrated to obtain the final product.
Claims
1. A method of preparing an alkyl phosphate compound based on a micro-reaction system, the micro-reaction system comprising a feed pump, a first micro-mixer, a second micro-mixer, a first micro-channel reactor, a second micro-channel reactor and a back-pressure device; the first micro-mixer, the second micro-mixer, the first micro-channel reactor, the second micro-channel reactor and the back-pressure device being sequentially connected; and the method comprising: (1) simultaneously feeding a solution of an alkylamine compound of formula (I) in a first solvent and a solution of an acid-binding agent in a second solvent to a first micro-mixer for mixing followed by pre-reaction in the first micro-channel reactor to obtain a pre-reaction solution; (2) simultaneously feeding the pre-reaction solution and a solution of a phosphate of formula (II) or a phosphite of formula (III) in a third solvent to the second micro-mixer for mixing to obtain a first reaction mixture; (3) feeding the first reaction mixture to the second micro-channel reactor to carry out a condensation reaction under a back pressure condition set by the back pressure device to obtain a second reaction mixture; (4) collecting the second reaction mixture by a storage tank for concentration to obtain an alkyl phosphate ester compound of formula (IV) or formula (V); ##STR00002## wherein R1 is selected from the group consisting of hydrogen, a C.sub.1-C.sub.12 alkyl, COOH, CH.sub.2COOH, and a C.sub.2-C.sub.12 alkylcarboxylic acid; R.sub.2 is selected from the group consisting of hydrogen, a C.sub.1-C.sub.12 alkyl, and a C.sub.3-C.sub.6 cycloalkyl; R.sub.3 is selected from the group consisting of hydrogen, OCH.sub.3, OCH.sub.2CH.sub.3, a C.sub.2-C.sub.12 alkoxy, trifluoromethyl, trifluoromethoxy, and 2-oxocyclopentylidenemethylidene; R.sub.4 is selected from the group consisting of hydrogen, carbonyl, a C.sub.1-C.sub.12 alkyl, and a C.sub.3-C.sub.6 cycloalkyl; R.sub.5 and R.sub.6 are each selected from the group consisting of hydrogen, a C.sub.1-C.sub.12 alkyl, a C.sub.3-C.sub.6 cycloalkyl, and a C.sub.2-C.sub.12 alkoxy; and R.sub.7 and R.sub.8 are each selected from the group consisting of hydrogen, OCH.sub.3, OCH.sub.2CH.sub.3, a C.sub.2-C.sub.12 alkoxy, trifluoromethyl, trifluoromethoxy, and 2-oxocyclopentylidene.
2. The method of claim 1, wherein the acid-binding agent is selected from the group consisting of triethylamine, tributylamine, trimethylamine, diisopropylethylamine (DIPEA), lithium formate, sodium formate, potassium formate, ammonium formate, R.sub.2COOLi, R.sub.2COONa, R.sub.2COOK, R.sub.2COONH.sub.4, pyridine, and 2,6-dimethylpyridine; and the first solvent is the same as the second solvent, and is selected from pentanol, butanol, isobutanol, tert-butanol, propanol, isopropanol, ethanol, methanol, methyl tert-butyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, acetone, butanone, and methyl isobutyl ketone.
3. The method of claim 1, wherein the acid-binding agent is selected from the group consisting of triethylamine, trimethylamine, tributylamine, diethylamine, DIPEA, p-dimethylaminopyridine, pyridine, N, N-diisopropylethylamine, and a combination thereof.
4. The method of claim 1, wherein the pre-reaction in the first micro-channel reactor is performed at 30-60 C. for 2-15 min; and the condensation reaction in the second micro-channel reactor is performed at 40-100 C. for 5-20 min.
5. The method of claim 1, wherein a back pressure of the back pressure device is 10-100 bar.
6. The method of claim 1, wherein the first micro-mixer and second micro-mixer are each selected from a T-type micro-mixer, a Y-type micro-mixer, a Z-type micro-mixer, an X-type micro-mixer, a SK-type micro-mixer, a SX-type micro-mixer, a SV-type micro-mixer, and a serpentine plate-type micro-mixer.
7. The method of claim 6, wherein the serpentine plate type micro-mixer is provided with a channel; a serpentine pipeline is provided in the channel; angular projections are staggeredly provided in the serpentine pipeline; one end of the serpentine pipeline is provided with a feeding port, and the other end of the serpentine pipeline is provided with a discharging port; a circulating liquid channel is provided between an outer side of the serpentine pipeline and a wall of the channel; and one end of the circulating liquid channel is provided with a circulating liquid outlet, and the other end of the circulating liquid channel is provided with a circulating liquid inlet.
8. The method of claim 6, wherein the first micro-mixer and the second micro-mixer are each provided with an inlet, an outlet and a mixing chamber; a diameter of the inlet and the outlet is 1.0 mm-6.0 mm; a diameter of the mixing chamber is 1.0 mm-20 mm; and a height of the mixing chamber is 1.0 mm-40 mm.
9. The method of claim 1, wherein the first micro-channel reactor and the second micro-channel reactor are each a tubular micro-channel reactor with a water droplet configuration; the tubular micro-channel reactor is provided with a microchannel arranged in a plurality of S-shaped rows; water droplet components are uniformly provided on an inner wall of the microchannel; one end of the microchannel is provided with a feeding port, and the other end of the microchannel is provided with a discharging port; an outer layer of the microchannel is configured as a circulating liquid channel for circulation a circulating liquid; and one end of the circulating liquid channel is provided with a circulating liquid outlet, and the other end of the circulating liquid channel is provided with a circulating liquid inlet.
10. The method of claim 7, wherein an inner diameter of the microchannel is 0.1-50 mm, and a length of the microchannel is 10-100 m.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
[0029] FIG. 1 is a block diagram of a structure of a micro-reaction system according to an embodiment of the present disclosure;
[0030] FIG. 2 is a schematic diagram of a structure of a serpentine plate-type micro-mixer according to an embodiment of the present disclosure; and
[0031] FIG. 3 is a schematic diagram of a structure of a tubular microchannel reactor with water droplet configuration according to an embodiment of the present disclosure.
[0032] In the drawings:
[0033] 1, feeding port; 2, discharging port; 3, circulating fluid outlet; 4, circulating fluid inlet; 5, serpentine micro-channel mixer; 6, projection; 7, inlet; 8, circulating fluid outlet; 9, water droplet component; 10, outlet; and 11, circulating fluid inlet.
DETAILED DESCRIPTION OF EMBODIMENTS
[0034] The present disclosure will be described in further detail below with reference to embodiments.
Example 1
[0035] Provided herein was a method of condensation of an alkyl amine with a phosphate and a phosphite ester using a micro-reaction system. The micro-reaction system was as shown in FIG. 1. A methanol solution of alkyl compound of formula (I) with R.sub.1 as CH.sub.2COOH, R.sub.2 as CH.sub.3, R.sub.3 as OCH.sub.2CH.sub.3 was pumped into a Y-type micro-mixer 1 through a plunger pump 1, and an acid-binding agent (triethylamine) was simultaneously pumped into the Y-type micro-mixer 1 through a pump 2 for mixing to obtain a mixture solution. The mixture solution was fed to a tubular microchannel reactor 1 for pre-reaction at 45 C. for 5 min to obtain a pre-reaction solution. The pre-reaction solution and a methanol solution of phosphate of formula (II) with R.sub.4 as hydrogen, R.sub.5 as OCH.sub.3, and R.sub.6 as OCH.sub.2CH.sub.3 were simultaneously pumped into the Y-type micro-mixer 2 through a pump 3 for mixing to obtain a reaction mixture. The reaction mixture was fed to a tubular micro-channel reactor 2 for condensation reaction at 80 C. and 20 bar for 8 min, and the reaction solution was concentrated to obtain an alkyl phosphate ester of formula (IV) with a one-way feedstock conversion of 80%, a yield of 78%, and a product quality purity of 99.1%.
Example 2
[0036] Provided herein was a method of condensation of an alkyl amine with a phosphate and a phosphite ester using a micro-reaction system. The micro-reaction system was as shown in FIG. 1. A methanol solution of alkyl compound of formula (I) with R.sub.1 as CH.sub.2COOH, R.sub.2 as CH.sub.3, R.sub.3 as OCH.sub.2CH.sub.3 was pumped into an X-type micro-mixer 1 through a plunger pump 1, and an acid-binding agent (triethylamine) was simultaneously pumped into the X-type micro-mixer 1 through a pump 2 for mixing to obtain a mixture solution. The mixture solution was fed to a tubular microchannel reactor 1 for pre-reaction at 45 C. for 5 min to obtain a pre-reaction solution. The pre-reaction solution and a methanolic solution of phosphate of formula (II) with R.sub.4 as hydrogen, R.sub.5 as OCH.sub.3, and R.sub.6 as OCH.sub.2CH.sub.3 were simultaneously pumped into the X-type micro-mixer 2 through a pump 3 for mixing to obtain a reaction mixture. The reaction mixture was fed to a tubular micro-channel reactor 2 for condensation reaction at 80 C. and 20 bar for 8 min, and the reaction solution was concentrated to obtain an alkyl phosphate ester of formula (IV) with a one-way feedstock conversion of 84%, a yield of 80%, and a product quality purity of 99.2%.
Example 3
[0037] Provided herein was a method of condensation of an alkyl amine with a phosphate and a phosphite ester using a micro-reaction system. The micro-reaction system was as shown in FIG. 1. A methanol solution of alkyl compound of formula (I) with R.sub.1 as CH.sub.2COOH, R.sub.2 as CH.sub.3, R.sub.3 as OCH.sub.2CH.sub.3 was pumped into an SV-type micro-mixer 1 through a plunger pump 1, and an acid-binding agent (triethylamine) was simultaneously pumped into the SV-type micro-mixer 1 through a pump 2 for mixing to obtain a mixture solution. The mixture solution was fed to a tubular microchannel reactor 1 for pre-reaction at 45 C. for 5 min to obtain a pre-reaction solution. The pre-reaction solution and a methanolic solution of phosphate of formula (II) with R.sub.4 as hydrogen, R.sub.5 as OCH.sub.3, and R.sub.6 as OCH.sub.2CH.sub.3 were simultaneously pumped into the SV-type micro-mixer 2 through a pump 3 for mixing to obtain a reaction mixture. The reaction mixture was fed to a tubular micro-channel reactor 2 for condensation reaction at 80 C. and 20 bar for 8 min, and the reaction solution was concentrated to obtain an alkyl phosphate ester of formula (IV) with a one-way feedstock conversion of 85%, a yield of 81.5%, and a product quality purity of 99.0%.
Example 4
[0038] Provided herein was a method of condensation of an alkyl amine with a phosphate and a phosphite ester using a micro-reaction system. The micro-reaction system was as shown in FIG. 1. A methanol solution of alkyl compound of formula (I) with R.sub.1 as CH.sub.2COOH, R.sub.2 as CH.sub.3, R.sub.3 as OCH.sub.2CH.sub.3 was pumped into a first serpentine plate-type micro-mixer 1 through a plunger pump 1, and an acid-binding agent (triethylamine) was simultaneously pumped into the first serpentine plate-type 1 through a pump 2 for mixing to obtain a mixture solution. The first serpentine plate micro-mixer 1 had a serpentine channel. The serpentine channel had a square cross section with a side length of 800 m. A folding angle of the serpentine channel was 120, and the distance between the former folding angle and the latter folding angle was 10 mm. Two equilateral triangles with a side length of 300 m were provided on the channel wall at the 10 mm spacing, and two equilateral triangles with a side length of 300 m were likewise provided on the opposing channel wall, which was used for enhancing the fluid mixing efficiency. The mixture solution was fed to a tubular microchannel reactor 1 for pre-reaction at 45 C. for 5 min to obtain a pre-reaction solution. The pre-reaction solution and a methanolic solution of phosphate of formula (II) with R.sub.4 as hydrogen, R.sub.5 as OCH.sub.3, and R.sub.6 as OCH.sub.2CH.sub.3 were simultaneously pumped into the serpentine-type micro-mixer 2 through a pump 3 for mixing to obtain a reaction mixture. The reaction mixture was fed to a tubular micro-channel reactor 2 for condensation reaction at 80 C. and 20 bar for 8 min, and the reaction solution was concentrated to obtain an alkyl phosphate ester of formula (IV) with a one-way feedstock conversion of 94%, a yield of 91.5%, and a product quality purity of 99.4%.
Example 5
[0039] Provided herein was a method of condensation of an alkyl amine with a phosphate and a phosphite ester using a micro-reaction system. The micro-reaction system was as shown in FIG. 1. A methanol solution of alkyl compound of formula (I) with R.sub.1 as CH.sub.2COOH, R.sub.2 as CH.sub.3, R.sub.3 as OCH.sub.2CH.sub.3 was pumped into a first serpentine plate-type micro-mixer 1 through a plunger pump 1, and an acid-binding agent (triethylamine) was simultaneously pumped into the first serpentine plate-type 1 through a pump 2 for mixing to obtain a mixture solution. The mixture solution was fed to a tubular microchannel reactor 1 with water droplet configuration for pre-reaction at 45 C. for 5 min to obtain a pre-reaction solution, where an inner diameter of an inlet and an outlet of the channel of the tubular microchannel reactor 1 was 1.6 mm, and balls with a diameter of 500 m were placed on the channel wall every 10 mm to enhance fluid mixing. The pre-reaction solution and a methanol solution of phosphate of formula (II) with R.sub.4 as hydrogen, R.sub.5 as OCH.sub.3, and R.sub.6 as OCH.sub.2CH.sub.3 were simultaneously pumped into a second serpentine-type micro-mixer 2 through a pump 3 for mixing to obtain a reaction mixture. The reaction mixture was fed to a second tubular micro-channel reactor 2 with water droplet configuration for condensation reaction at 80 C. and 20 bar for 8 min, and the reaction solution was concentrated to obtain an alkyl phosphate ester of formula (IV) with a one-way feedstock conversion of 98%, a yield of 95%, and a product quality purity of 99.6%.
Example 6
[0040] Provided herein was a method of condensation of an alkyl amine with a phosphate and a phosphite ester using a micro-reaction system. The micro-reaction system was as shown in FIG. 1. A methanol solution of alkyl compound of formula (I) with R.sub.1 as CH.sub.2COOH, R.sub.2 as hydrogen, R.sub.3 as OCH.sub.2CH.sub.3 was pumped into a first serpentine plate-type micro-mixer 1 through a plunger pump 1, and an acid-binding agent (triethylamine) was simultaneously pumped into the first serpentine plate-type 1 through a pump 2 for mixing to obtain a mixture solution. The mixture solution was fed to a first tubular microchannel reactor 1 with water droplet configuration for pre-reaction at 45 C. for 2 min to obtain a pre-reaction solution. The pre-reaction solution and a methanol solution of phosphate of formula (II) with R.sub.4 as CH.sub.3, R.sub.5 as OCH.sub.3, and R.sub.6 as OCH.sub.2CH.sub.3 were simultaneously pumped into a second serpentine-type micro-mixer 2 through a pump 3 for mixing to obtain a reaction mixture. The reaction mixture was fed to a second tubular micro-channel reactor 2 with water droplet configuration for condensation reaction at 55 C. and 20 bar for 8 min, and the reaction solution was concentrated to obtain an alkyl phosphate ester of formula (IV) with a one-way feedstock conversion of 98%, a yield of 96%, and a product quality purity of 99.3%.
Example 7
[0041] Provided herein was a method of condensation of an alkyl amine with a phosphate and a phosphite ester using a micro-reaction system. The micro-reaction system was as shown in FIG. 1. A methanol solution of alkyl compound of formula (I) with R.sub.1 as COOH, R.sub.2 as hydrogen, R.sub.3 as OCH.sub.2CH.sub.3 was pumped into a first serpentine plate-type micro-mixer 1 through a plunger pump 1, and an acid-binding agent (triethylamine) was simultaneously pumped into the first serpentine plate-type 1 through a pump 2 for mixing to obtain a mixture solution. The mixture solution was fed to a first tubular microchannel reactor 1 with water droplet configuration for pre-reaction at 45 C. for 2 min to obtain a pre-reaction solution. The pre-reaction solution and a methanolic solution of phosphite ester of formula (III) with R.sub.7 as OCH.sub.3, and R.sub.8 as OCH.sub.2CH.sub.3 were simultaneously pumped into a second serpentine-type micro-mixer 2 through a pump 3 for mixing to obtain a reaction mixture. The reaction mixture was fed to a second tubular micro-channel reactor 2 with water droplet configuration for condensation reaction at 55 C. and 20 bar for 8 min, and the reaction solution was concentrated to obtain an alkyl phosphate ester of formula (V) with a one-way feedstock conversion of 96%, a yield of 94.5%, and a product quality purity of 99.7%.
Example 8
[0042] Provided herein was a method of condensation of an alkyl amine with a phosphate and a phosphite ester using a micro-reaction system. The micro-reaction system was as shown in FIG. 1. A methanol solution of alkyl compound of formula (I) with R.sub.1 as COOH, R.sub.2 as CH.sub.3, R.sub.3 as OCH.sub.2CH.sub.3 was pumped into a first serpentine plate-type micro-mixer 1 through a plunger pump 1, and an acid-binding agent (trimethylamine) was simultaneously pumped into the first serpentine plate-type 1 through a pump 2 for mixing to obtain a mixture solution. The mixture solution was fed to a first tubular microchannel reactor 1 with water droplet configuration for pre-reaction at 50 C. for 5 min to obtain a pre-reaction solution. The pre-reaction solution and a methanolic solution of phosphate of formula (II) with R.sub.4 as CH.sub.3, R.sub.5 as OCH.sub.3, and R.sub.6 as OCH.sub.2CH.sub.3 were simultaneously pumped into a second serpentine-type micro-mixer 2 through a pump 3 for mixing to obtain a reaction mixture. The reaction mixture was fed to a second tubular micro-channel reactor 2 with water droplet configuration for condensation reaction at 70 C. and 25 bar for 10 min, and the reaction solution was concentrated to obtain an alkyl phosphate ester of formula (IV) with a one-way feedstock conversion of 97%, a yield of 95%, and a product quality purity of 99.1%.
Example 9
[0043] Provided herein was a method of condensation of an alkyl amine with a phosphate and a phosphite ester using a micro-reaction system. The micro-reaction system was as shown in FIG. 1. A methanol solution of alkyl compound of formula (I) with R.sub.1 as CH.sub.2COOH, R.sub.2 as CH.sub.3, R.sub.3 as OCH.sub.2CH.sub.3 was pumped into a first serpentine plate-type micro-mixer 1 through a plunger pump 1, and an acid-binding agent (triethylamine) was simultaneously pumped into the first serpentine plate-type 1 through a pump 2 for mixing to obtain a mixture solution. The mixture solution was fed to a first tubular microchannel reactor 1 with water droplet configuration for pre-reaction at 45 C. for 5 min to obtain a pre-reaction solution. The pre-reaction solution and a methanolic solution of phosphate of formula (II) with R.sub.4 as hydrogen, R.sub.5 as OCH.sub.3, and R.sub.6 as OCH.sub.3 were simultaneously pumped into a second serpentine-type micro-mixer 2 through a pump 3 for mixing to obtain a reaction mixture. The reaction mixture was fed to a second tubular micro-channel reactor 2 with water droplet configuration for condensation reaction at 80 C. and 20 bar for 8 min, and the reaction solution was concentrated to obtain an alkyl phosphate ester of formula (IV) with a one-way feedstock conversion of 98%, a yield of 95.8%, and a product quality purity of 99.6%.
Example 10
[0044] Provided herein was a method of condensation of an alkyl amine with a phosphate and a phosphite ester using a micro-reaction system. The micro-reaction system was as shown in FIG. 1. A methanol solution of alkyl compound of formula (I) with R.sub.1 as CH.sub.2COOH, R.sub.2 as CH.sub.3, R.sub.3 as OCH.sub.2CH.sub.3 was pumped into a first serpentine plate-type micro-mixer 1 through a plunger pump 1, and an acid-binding agent (tributylamine) was simultaneously pumped into the first serpentine plate-type 1 through a pump 2 for mixing to obtain a mixture solution. The mixture solution was fed to a first tubular microchannel reactor 1 with water droplet configuration for pre-reaction at 35 C. for 5 min to obtain a pre-reaction solution. The pre-reaction solution and a methanolic solution of phosphate of formula (II) with R.sub.4 as hydrogen, R.sub.5 as OCH.sub.3, and R.sub.6 as OCH.sub.2CH.sub.3 were simultaneously pumped into a second serpentine-type micro-mixer 2 through a pump 3 for mixing to obtain a reaction mixture. The reaction mixture was fed to a second tubular micro-channel reactor 2 with water droplet configuration for condensation reaction at 70 C. and 28 bar for 7 min, and the reaction solution was concentrated to obtain an alkyl phosphate ester of formula (IV) with a one-way feedstock conversion of 97%, a yield of 95%, and a product quality purity of 99.0%.
Example 11
[0045] Provided herein was a method of condensation of an alkyl amine with a phosphate and a phosphite ester using a micro-reaction system. The micro-reaction system was as shown in FIG. 1. An isopropanol solution of alkyl compound of formula (I) with R.sub.1 as CH.sub.2COOH, R.sub.2 as CH.sub.3, R.sub.3 as OCH.sub.2CH.sub.3 was pumped into a first serpentine plate-type micro-mixer 1 through a plunger pump 1, and an acid-binding agent (triethylamine) was simultaneously pumped into the first serpentine plate-type 1 through a pump 2 for mixing to obtain a mixture solution. The mixture solution was fed to a first tubular microchannel reactor 1 with water droplet configuration for pre-reaction at 45 C. for 5 min to obtain a pre-reaction solution. The pre-reaction solution and an isopropanol solution of phosphate of formula (II) with R.sub.4 as CH.sub.2CH.sub.3, R.sub.5 as OCH.sub.3, and R.sub.6 as OCH.sub.3 were simultaneously pumped into a second serpentine-type micro-mixer 2 through a pump 3 for mixing to obtain a reaction mixture. The reaction mixture was fed to a second tubular micro-channel reactor 2 with water droplet configuration for condensation reaction at 80 C. and 35 bar for 10 min, and the reaction solution was concentrated to obtain an alkyl phosphate ester of formula (IV) with a one-way feedstock conversion of 95%, a yield of 93.8%, and a product quality purity of 99.2%.
Example 12
[0046] Provided herein was a method of condensation of an alkyl amine with a phosphate and a phosphite ester using a micro-reaction system. The micro-reaction system was as shown in FIG. 1. An ethanol solution of alkyl compound of formula (I) with R.sub.1 as CH.sub.2COOH, R.sub.2 as CH.sub.3, R.sub.3 as OCH.sub.2CH.sub.3 was pumped into a first serpentine plate-type micro-mixer 1 through a plunger pump 1, and an acid-binding agent (triethylamine) was simultaneously pumped into the first serpentine plate-type 1 through a pump 2 for mixing to obtain a mixture solution. The mixture solution was fed to a first tubular microchannel reactor 1 with water droplet configuration for pre-reaction at 40 C. for 8 min to obtain a pre-reaction solution. The pre-reaction solution and an ethanol solution of phosphite ester of formula (III) with R.sub.7 as OCH.sub.3, and R.sub.8 as OCH.sub.2CH.sub.3 were simultaneously pumped into a second serpentine-type micro-mixer 2 through a pump 3 for mixing to obtain a reaction mixture. The reaction mixture was fed to a second tubular micro-channel reactor 2 with water droplet configuration for condensation reaction at 65 C. and 30 bar for 15 min, and the reaction solution was concentrated to obtain an alkyl phosphate ester of formula (V) with a one-way feedstock conversion of 96%, a yield of 94.8%, and a product quality purity of 99.8%.
Example 13
[0047] Provided herein was a method of condensation of an alkyl amine with a phosphate and a phosphite ester using a micro-reaction system. The micro-reaction system was as shown in FIG. 1. An ethanol solution of alkyl compound of formula (I) with R.sub.1 as CH.sub.2COOH, R.sub.2 as CH.sub.3, R.sub.3 as OCH.sub.2CH.sub.3 was pumped into a first serpentine plate-type micro-mixer 1 through a plunger pump 1, and an acid-binding agent (triethylamine) was simultaneously pumped into the first serpentine plate-type 1 through a pump 2 for mixing to obtain a mixture solution. The mixture solution was fed to a first tubular microchannel reactor 1 with water droplet configuration for pre-reaction at 40 C. for 8 min to obtain a pre-reaction solution. The pre-reaction solution and an ethanol solution of phosphite ester of formula (III) with R.sub.7 as OCH.sub.2CH.sub.3, and R.sub.8 as OCH.sub.2CH.sub.3 were simultaneously pumped into a second serpentine-type micro-mixer 2 through a pump 3 for mixing to obtain a reaction mixture. The reaction mixture was fed to a second tubular micro-channel reactor 2 with water droplet configuration for condensation reaction at 65 C. and 30 bar for 12 min, and the reaction solution was concentrated to obtain an alkyl phosphate ester of formula (V) with a one-way feedstock conversion of 97%, a yield of 96.2%, and a product quality purity of 99.1%.
Example 14
[0048] Provided herein was a method of condensation of an alkyl amine with a phosphate and a phosphite ester using a micro-reaction system. The micro-reaction system was as shown in FIG. 1. An ethanol solution of alkyl compound of formula (I) with R.sub.1 as COOH, R.sub.2 as CH.sub.2CH.sub.3, R.sub.3 as OCH.sub.2CH.sub.3 was pumped into a first serpentine plate-type micro-mixer 1 through a plunger pump 1, and an acid-binding agent (triethylamine) was simultaneously pumped into the first serpentine plate-type 1 through a pump 2 for mixing to obtain a mixture solution. The mixture solution was fed to a first tubular microchannel reactor 1 with water droplet configuration for pre-reaction at 40 C. for 8 min to obtain a pre-reaction solution. The pre-reaction solution and an ethanol solution of phosphite ester of formula (III) with R.sub.7 as OCH.sub.2CH.sub.3, and R.sub.8 as hydrogen were simultaneously pumped into a second serpentine-type micro-mixer 2 through a pump 3 for mixing to obtain a reaction mixture. The reaction mixture was fed to a second tubular micro-channel reactor 2 with water droplet configuration for condensation reaction at 65 C. and 30 bar for 12 min, and the reaction solution was concentrated to obtain an alkyl phosphate ester of formula (V) with a one-way feedstock conversion of 98%, a yield of 95.2%, and a product quality purity of 99.8%.
Example 15
[0049] Provided herein was a method of condensation of an alkyl amine with a phosphate and a phosphite ester using a micro-reaction system. The micro-reaction system was as shown in FIG. 1. A methanol solution of alkyl compound of formula (I) with R.sub.1 as CH.sub.2COOH, R.sub.2 as CH.sub.3, R.sub.3 as OCH.sub.2CH.sub.3 was pumped into a first serpentine plate-type micro-mixer 1 through a plunger pump 1, and an acid-binding agent (triethylamine) was simultaneously pumped into the first serpentine plate-type 1 through a pump 2 for mixing to obtain a mixture solution. The mixture solution was fed to a first tubular microchannel reactor 1 with water droplet configuration for pre-reaction at 45 C. for 5 min to obtain a pre-reaction solution. The pre-reaction solution and a methanolic solution of phosphate of formula (II) with R.sub.4 as carbonyl, R.sub.5 as OCH.sub.3, and R.sub.6 as OCH.sub.3 were simultaneously pumped into a second serpentine-type micro-mixer 2 through a pump 3 for mixing to obtain a reaction mixture. The reaction mixture was fed to a second tubular micro-channel reactor 2 with water droplet configuration for condensation reaction at 80 C. and 20 bar for 8 min, and the reaction solution was concentrated to obtain an alkyl phosphate ester of formula (IV) with a one-way feedstock conversion of 99%, a yield of 97.8%, and a product quality purity of 99.3%.
