CN108659213B - Method for preparing polyether carboxylate by adopting micro-flow field reaction technology - Google Patents

Method for preparing polyether carboxylate by adopting micro-flow field reaction technology Download PDF

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CN108659213B
CN108659213B CN201810658618.5A CN201810658618A CN108659213B CN 108659213 B CN108659213 B CN 108659213B CN 201810658618 A CN201810658618 A CN 201810658618A CN 108659213 B CN108659213 B CN 108659213B
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polyether polyol
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CN108659213A (en
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郭凯
崔玉声
邱江凯
方正
覃龙州
欧阳平凯
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Nanjing Tech University
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    • C—CHEMISTRY; METALLURGY
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    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/321—Polymers modified by chemical after-treatment with inorganic compounds
    • C08G65/324—Polymers modified by chemical after-treatment with inorganic compounds containing oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
    • C08G65/48—Polymers modified by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G2650/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterized by the type of post-polymerisation functionalisation
    • C08G2650/10—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterized by the type of post-polymerisation functionalisation characterized by the catalyst used in the post-polymerisation functionalisation step

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Abstract

The invention discloses a method for preparing polyether carboxylate by adopting a micro-flow field reaction technology, which comprises the following steps: (1) dissolving polyether polyol, a catalyst, a sodium hypochlorite aqueous solution and inorganic base by using a solvent, mixing the solution by using a first micro mixer of a micro-channel modular reaction device, and injecting the mixture into a first micro-structure reactor of the micro-channel modular reaction device for reaction; (2) mixing the mixed system obtained in the step (1) with sodium chlorite buffer solution through a second micro mixer of the microchannel modular reaction device, and injecting the mixture into a second micro-structure reactor of the microchannel modular reaction device for reaction; (3) and (3) introducing the mixed system obtained in the step (2) into a product collector in a microchannel modular reaction device, and performing aftertreatment to obtain polyether carboxylate. The method has the advantages of safety, environmental protection, low price and easy obtainment of raw materials, no residue of highly toxic reactants, high reaction speed, high efficiency, high acidification degree of the prepared polyether carboxylate and the like.

Description

Method for preparing polyether carboxylate by adopting micro-flow field reaction technology
Technical Field
The invention belongs to the field of chemical synthesis, and particularly relates to a method for preparing polyether carboxylate by a micro-flow field reaction technology.
Background
Polyether carboxylate is a novel anionic surfactant, is modified by a nonionic surfactant, has the characteristics that other anionic surfactants do not have, such as strong temperature resistance and salt resistance, low toxicity, easy biodegradation, low surface tension, good compatibility with other surfactants and the like, and is a multifunctional green surfactant, because a certain addition number of epoxy groups, such as propylene oxide and ethylene oxide, are embedded between a hydrophobic group and a hydrophilic group. Due to their special properties, surfactants of the polyether carboxylates have found wide application in the fields of cosmetics, detergents, biochemistry, plastics, leather, pharmaceuticals, food processing and the petroleum industry.
The methods for preparing polyether carboxylate surfactants mainly include the carboxymethylation method and the oxidation method. The carboxymethyl method is most applied, relatively speaking, the method has easily obtained raw materials and simple operation, but the preparation process is influenced by the problems of product purity, chloroacetic acid residue and the like, and the practical application is greatly limited; the oxidation process being by means of airOr oxidizing the terminal-CH by direct oxidation with oxygen or by oxidation with nitric acid or chromic acid2OH is oxidized to-COOH. The method is to oxidize polyether polyol under the alkaline condition and the action of a catalyst by using air or oxygen to prepare polyether carboxylate. The main method comprises the following steps: nitroxide radical (TEMPO) catalytic oxidation and noble metal catalytic oxidation. 1. Nitroxide radical catalytic oxidation: the nitroxide radical is used as oxidation catalyst, and the method is firstly proposed by Rozautsev and Rassat et al, and the nitroxide radical catalytic oxidation can be divided into 3 types according to the catalytic system of the reaction: nitroxide radical + nitric acid + oxygen, nitroxide radical + hypochlorite, nitroxide radical + nitric acid + co-catalyst + oxygen. Polyether contains a large number of ether bonds, is easy to break during oxidation, must be reacted under mild conditions by using a catalyst with higher selectivity, and the nitroxide free radicals used for the reaction are generally very stable, so that the yield of the obtained product is high, but the reaction process is more complex. 2. Noble metal catalytic oxidation: in the 20 th century and 50 s, a great deal of literature reports that rare metals catalyze the oxidation reaction of alcohols, and the specific preparation process comprises the following steps: putting a certain amount of polyether, sodium hydroxide, water and noble metal catalyst into a reaction kettle, heating to a certain temperature under stirring, and introducing O2And (3) replacing, then keeping a certain pressure in the reaction kettle for reaction, keeping the pressure in the reaction kettle for a certain time when the pressure in the reaction kettle is not reduced, and filtering to remove the catalyst to obtain the product. Compared with other process routes, the noble metal catalytic oxidation method has the advantages of short process flow, mild reaction conditions, high conversion rate, no other impurities and the like, but the noble metal catalytic oxidation method still restricts the popularization and the application of the noble metal catalyst due to the problems of high price, short service life of the catalyst, complex operation, heavy metal residue, engineering application and the like of the noble metal catalyst.
US7208118 discloses a method for preparing alcohol ether carboxylate by taking block ethylene oxide propylene oxide alcohol ether as raw material and reacting with chloroacetic acid in the presence of solvent, and the method has the disadvantages of high system viscosity and difficult engineering amplification. Meanwhile, due to the hydrolysis of sodium chloroacetate, the conversion rate of a substrate is generally 60-80%, and the product contains by-product sodium chloride and sodium chloroacetate and sodium dichloroacetate residues which are irritant to human bodies. After the reaction is finished, dilute sulfuric acid is used for post-treatment, and waste salt and waste acid liquor are generated. US8304575 provides a method for synthesizing alcohol ether carboxylate without unpleasant odor by carboxymethylation method using alcohol ether as raw material. The innovation of the invention is that the acid used for the neutralization termination reaction is special carboxylic acid, such as citric acid, malic acid and the like, but the defects of low conversion rate, incapability of continuous production and the like of the carboxymethylation method can not be solved. JP5096516 discloses a patent for synthesizing alcohol ether carboxylate by noble metal catalytic oxidation, wherein the reaction temperature is 100-270 ℃, and air and oxygen-containing gas are used as oxidants to synthesize the alcohol ether carboxylate. CN101357333A discloses a method for preparing alcohol ether carboxylate by using Pd/C as a catalyst, which adopts noble metal as a catalyst and air and oxygen-containing gas as oxidants to prepare alcohol ether carboxylate, and the method can solve the problems of difficult engineering amplification, toxic residue in products and the like of a carboxymethylation method, but has the problems of high price of the noble metal catalyst, short service life of the catalyst, complex operation, heavy metal residue, engineering application and the like, and restricts the popularization and application of the method.
Disclosure of Invention
The invention aims to solve the technical problem of providing a method for preparing high-quality polyether carboxylate by adopting a micro-flow field reaction technology, and aims to solve the problems of overhigh preparation cost, low efficiency, difficult engineering amplification, high toxic substance residue in a product and the like in the preparation of polyether carboxylate in the prior art.
In order to solve the problems, the technical scheme adopted by the invention is as follows:
(1) dissolving polyether polyol, a catalyst, a sodium hypochlorite aqueous solution and inorganic base by using a solvent, mixing the solution by using a first micro mixer of a micro-channel modular reaction device, and injecting the mixture into a first micro-structure reactor of the micro-channel modular reaction device for reaction;
(2) mixing the mixed system obtained in the step (1) with a sodium chlorite solution through a second micro mixer of the micro-channel modular reaction device, and injecting the mixture into a second micro-structure reactor of the micro-channel modular reaction device for reaction;
(3) and (3) introducing the mixed system obtained in the step (2) into a product collector in a microchannel modular reaction device, and carrying out aftertreatment to obtain polyether carboxylate.
In the step (1), dissolving polyether polyol and a catalyst by using a solvent to obtain a polyether polyol catalyst mixed solution, dissolving a sodium hypochlorite aqueous solution and an inorganic base by using a solvent to obtain a sodium hypochlorite aqueous solution and an inorganic base mixed solution, respectively and simultaneously pumping the polyether polyol catalyst mixed solution and the sodium hypochlorite aqueous solution and the inorganic base mixed solution into a first micro-mixer of a microchannel modular reaction device for mixing, and then injecting into a first microstructure reactor of the microchannel modular reaction device for reaction.
In the step (1), the catalyst is a noble metal catalyst, a Lewis acid compound, a nitroxide free radical compound or a halogen compound, and the dosage of the catalyst is 1-10% of the molar weight of the polyether polyol.
The noble metal catalyst is preferably one or more of ruthenium, osmium, cobalt, rhodium, iridium, nickel, platinum and palladium, and the Lewis acid compound is preferably one or more of boron trifluoride, aluminum chloride, ferric chloride and antimony pentafluoride. The nitroxide radical compound is preferably one or more of piperidine nitroxide radical, pyrrolidine nitroxide radical, oxazolidine nitroxide radical and proxyl nitroxide radical. The halogen compound is preferably one or more of sodium chloride, sodium bromide, sodium iodide, potassium chloride, potassium bromide and potassium iodide.
In the step (1), sodium hypochlorite is an aqueous solution with an effective chlorine content of 5-10%, and the molar ratio of polyether polyol to sodium hypochlorite is 1: 1-10.
In the step (1), the inorganic base is sodium carbonate, potassium carbonate, sodium chloride, potassium bromide or sodium bromide, and the addition amount of the inorganic base is 5-20% of the molar weight of the polyether polyol.
In the step (1), the solvent is ethyl acetate, toluene, acetonitrile, dichloroethane, dichloromethane, acetic acid, n-hexane or water, preferably water.
In the step (1), the reaction temperature of a first micro-structure reactor of the micro-channel modular reaction device is 0-80 ℃, the reaction retention time is 5-30 min, the flow rate of a mixed solution obtained after mixing by a first micro-mixer is 0.1-5 mL/min, and the volume of the first micro-structure reactor is 10-50 mL.
In the step (2), the preparation method of the sodium chlorite solution comprises the following steps: dissolving sodium chlorite in a solvent, and fully stirring, wherein the solvent is deionized water, a sodium bicarbonate solution, a sodium chloride solution, a phosphoric acid buffer solution or an acetic acid buffer solution, preferably the phosphoric acid buffer solution, and the molar ratio of the sodium chlorite to the polyether polyol is 1: 1-10.
In the step (2), the reaction temperature of a second micro-structure reactor of the micro-channel modular reaction device is 0-100 ℃, the reaction residence time is 5-30 min, the flow rate of the mixed system obtained in the step (1) and the sodium chlorite solution after being mixed by a second micro-mixer is 0.1-5 mL/min, and the volume of the second micro-structure reactor is 10-50 mL.
In the step (3), the post-treatment comprises the following steps: pouring the product into dilute hydrochloric acid, heating the acidic aqueous solution to promote the separation of an organic phase and a water phase; and collecting the organic phase, washing the organic phase for 3-5 times by using deionized water, and neutralizing the organic phase by using inorganic base until the pH value is 8.5-9.5 to obtain the polyether carboxylate. The inorganic base is preferably an aqueous solution of sodium hydroxide or potassium hydroxide.
The microchannel module reaction device comprises a first micro mixer, a first micro-structure reactor, a second micro mixer, a second micro-structure reactor and a product collector which are sequentially connected through pipelines: wherein, a first raw material storage tank (filled with polyether polyol and catalyst) and a second raw material storage tank (filled with sodium hypochlorite aqueous solution and inorganic base) are respectively connected with a feed inlet of the first micro mixer, and a third raw material storage tank (filled with sodium chlorite solution) is connected with a feed inlet of the second micro mixer.
Has the advantages that: compared with the prior art for preparing polyether carboxylate, the method has the advantages of safety, environmental protection, low price and easy obtainment of raw materials, no residue of highly toxic reactants, high reaction speed, high efficiency and the like.
Drawings
FIG. 1 is a schematic structural diagram of a microchannel modular reaction apparatus.
Detailed Description
In the following embodiments, the microchannel modular reaction apparatus is shown in fig. 1, and comprises a feed liquid inlet 1 and a feed liquid inlet 2, which are respectively connected in series with a micro mixer 1 through a pipeline, the micro mixer 1 is connected with a micro-structure reactor 1 through a pipeline, a discharge port and a feed liquid inlet 3 of the micro-structure reactor 1 are respectively connected with the micro mixer 2 through a pipeline, the micro mixer 2 is respectively connected in series with the micro-structure reactor 2 and a product collector through pipelines, a raw material storage tank 1 containing polyether polyol and catalyst and a raw material storage tank 2 containing sodium hypochlorite aqueous solution and inorganic base are respectively connected with a feed port of the micro mixer 1, and a raw material storage tank 3 containing sodium chlorite solution is connected with a feed port of a second micro mixer: the reaction raw materials and products are fed by a precise and low-pulsation syringe pump. The reaction raw materials are input into the micro mixer and the subsequent equipment through a low-pulsation pump (such as an HPLC pump or an injection pump), so that the materials can continuously pass through the microchannel reaction device and the residence time of the materials is controlled.
Wherein the micromixer is slit plate mixer LH25(Hastelloy C); purchased from Ehrfeld Mikrotechnik BTS GmbH, model 0109-4-0004F.
The microstructure reactor is a meander reactor HC, a sandwich reactor HC, a fixed bed meanderrea reactor HC and a Hastelloy capillary: preferably a sandwich reactiver HC, available from Ehrfeld MikrotechnikBT S GmbH and having models of 0211-2-0314-F, respectively; 0213-1-0004-F; 0222-2-2004-F.
The sodium hypochlorite used below is an aqueous solution with 5-10% available chlorine content available on the market. The sodium chlorite solution used below is prepared by dissolving a commercially available solid sodium chlorite in a suitable solvent (deionized water, sodium bicarbonate solution, sodium chloride solution, phosphoric acid buffer solution, or acetic acid buffer solution) and stirring the solution thoroughly to obtain a sodium chlorite solution.
The specific steps for determining the acidification degree are as follows: accurately weighing 1-2 g (accurately)To 0.0001g) sample W1Adding 20mL of absolute ethyl alcohol and 50mL of distilled water into a 250mL eggplant-shaped bottle, dissolving, using phenolphthalein as an indicator, titrating by using 0.1mol/L sodium hydroxide solution until the reaction system is pink (keeping 15S fadeless), and recording the amount V consumed by sodium hydroxide titrationNaOH(mL)。
Organic acid content (%) ═ cxvNaOHX 10-3 XM-samples/W1×100
Wherein, C: concentration (mol/L) of sodium hydroxide standard solution; and (5) M sample: sample molecular weight; w1: sample weight (g)
Note: the method is to eliminate the influence of free inorganic acid hydrochloric acid as much as possible, otherwise, the result is high.
Example 1
Fully mixing a raw material storage tank 1 containing aqueous solution of palladium carbon and polyether glycol and a raw material storage tank 2 containing aqueous solution of sodium hypochlorite and sodium bromide through a micro mixer 1, injecting the mixture into a micro-structure reactor 1 of a micro-channel modular reaction device, wherein the content of a catalyst is 10% of the molar weight of polyether glycol, the content of a cocatalyst sodium bromide is 10% of the molar weight of polyether glycol, the molar ratio of polyether glycol to sodium hypochlorite is 1: 5, standing the mixture at 30 ℃ for 15min, the flow rate of the mixed solution is 0.6mL/min, and the volume of the micro-structure reactor 1 is 5 mL; the discharge of the microstructure reactor 1 is mixed with sodium chlorite phosphoric acid buffer solution and then passes through a micro mixer 2 and the microstructure reactor 2 in sequence, wherein the molar ratio of polyether polyol to sodium chlorite is controlled to be 1: 5, the flow rate of the discharge of the microstructure reactor 1 is 0.9mL/min, and the volume of the microstructure reactor 2 is 5 mL. Staying at 80 ℃ for 5min, discharging the material from the microstructure reactor 2, introducing the material into a product collector, quickly pouring the product into a dilute hydrochloric acid solution, and heating the acidic aqueous solution to promote the separation of an organic phase and a water phase; and collecting the organic phase, washing the organic phase with deionized water for multiple times, and neutralizing the organic phase with a sodium hydroxide solution until the pH value is 8.5-9.5 to obtain the fatty alcohol ether sodium carboxylate product. A small amount of sample is taken for acidification, the acidification degree is 91.5 percent, and the conversion rate of polyether polyol is 96.3 percent.
Example 2
Fully mixing a raw material storage tank 1 containing an aqueous solution of catalyst TEMPO and polyether polyol and a raw material storage tank 2 containing an aqueous solution of sodium hypochlorite and sodium bromide through a micro mixer 1, injecting the mixture into a micro-structural reactor 1 of a micro-channel modular reaction device, wherein the content of the catalyst is 5% of the molar weight of polyether polyol, the content of the cocatalyst sodium bromide is 10% of the molar weight of the polyether polyol, the molar ratio of the polyether polyol to the sodium hypochlorite is 1: 2, standing at 10 ℃ for 15min, the flow rate of the mixed solution is 0.6mL/min, and the volume of the micro-structural reactor 1 is 5 mE; the discharge of the microstructure reactor 1 is mixed with sodium chlorite phosphoric acid buffer solution and then passes through a micro mixer 2 and the microstructure reactor 2 in sequence, wherein the molar ratio of polyether polyol to sodium chlorite is controlled to be 1: 5, the flow rate of the discharge of the microstructure reactor 1 is 0.9mL/min, and the volume of the microstructure reactor 2 is 5 mL. Staying at 80 deg.C for 5min, introducing the discharge of the microstructure reactor 2 into a product collector, rapidly pouring the product into dilute hydrochloric acid solution, heating the acidic aqueous solution to promote separation of organic phase and water phase; and collecting the organic phase, washing the organic phase with deionized water for multiple times, and neutralizing the organic phase with a sodium hydroxide solution until the pH value is 8.5-9.5 to obtain the fatty alcohol ether sodium carboxylate product. A small amount of sample was taken and acidified to obtain a degree of acidification of 79.5% and a conversion of polyether polyol of 89.6%.
Example 3
Fully mixing a raw material storage tank 1 containing a catalyst TEMPO and a water solution of polyether polyol and a raw material storage tank 2 containing a water solution of sodium hypochlorite and sodium bromide through a micro mixer 1, injecting the mixture into a micro-structure reactor 1 of a micro-channel modular reaction device, wherein the content of the catalyst is 15% of the molar weight of polyether polyol, the content of the cocatalyst sodium bromide is 10% of the molar weight of polyether polyol, the molar ratio of the polyether polyol to the sodium hypochlorite is 1: 3, standing the mixture at 20 ℃ for 20min, the flow rate of the mixed solution is 0.4mL/min, and the volume of the micro-structure reactor 1 is 5 mL; the discharge of the microstructure reactor 1 is mixed with sodium chlorite phosphoric acid buffer solution and then passes through a micro mixer 2 and the microstructure reactor 2 in sequence, wherein the molar ratio of polyether polyol to sodium chlorite is controlled to be 1: 5, the flow rate of the discharge of the microstructure reactor 1 is 0.6mL/min, and the volume of the microstructure reactor 2 is 5 mL. Staying at 80 deg.C for 8min, introducing the discharge of the microstructure reactor 2 into a product collector, rapidly pouring the product into dilute hydrochloric acid solution, heating the acidic aqueous solution to promote separation of organic phase and water phase; and collecting the organic phase, washing the organic phase with deionized water for multiple times, and neutralizing the organic phase with a sodium hydroxide solution until the pH value is 8.5-9.5 to obtain the fatty alcohol ether sodium carboxylate product. A small amount of sample is taken for acidification, the acidification degree is 86.1 percent, and the conversion rate of polyether polyol is 90.6 percent.
Example 4
Fully mixing a raw material storage tank 1 containing an aqueous solution of catalyst TEMPO and polyether polyol and a raw material storage tank 2 containing an aqueous solution of sodium hypochlorite and sodium bromide through a micro mixer 1, injecting the mixture into a micro-structure reactor 1 of a micro-channel modular reaction device, wherein the content of the catalyst is 10% of the molar weight of polyether polyol, the content of the cocatalyst sodium bromide is 10% of the molar weight of the polyether polyol, the molar ratio of the polyether polyol to the sodium hypochlorite is 1: 4, standing the mixture at 30 ℃ for 15min, the flow rate of the mixed solution is 0.3mL/min, and the volume of the micro-structure reactor 1 is 5 mL; the discharge of the microstructure reactor 1 is mixed with sodium chlorite phosphoric acid buffer solution and then passes through a micro mixer 2 and the microstructure reactor 2 in sequence, wherein the molar ratio of polyether polyol to sodium chlorite is controlled to be 1: 5, the flow rate of the discharge of the microstructure reactor 1 is 0.45mL/min, and the volume of the microstructure reactor 2 is 5 mL. Staying at 80 deg.C for 11min, introducing the discharge of the microstructure reactor 2 into a product collector, rapidly pouring the product into dilute hydrochloric acid solution, heating the acidic aqueous solution to promote separation of organic phase and water phase; and collecting the organic phase, washing the organic phase with deionized water for multiple times, and neutralizing the organic phase with a sodium hydroxide solution until the pH value is 8.5-9.5 to obtain the fatty alcohol ether sodium carboxylate product. A small amount of sample was taken and acidified to obtain an acidification degree of 87.9% and a conversion rate of polyether polyol of 93.8%.
Example 5
Fully mixing a raw material storage tank 1 containing an aqueous solution of catalyst TEMPO and polyether polyol and a raw material storage tank 2 containing an aqueous solution of sodium hypochlorite and sodium bromide through a micro mixer 1, injecting the mixture into a micro-structure reactor 1 of a micro-channel modular reaction device, wherein the content of the catalyst is 10% of the molar weight of polyether polyol, the content of the cocatalyst sodium bromide is 5% of the molar weight of the polyether polyol, the molar ratio of the polyether polyol to the sodium hypochlorite is 1: 5, standing the mixture at 30 ℃ for 15min, the flow rate of the mixed solution is 0.3mL/min, and the volume of the micro-structure reactor 1 is 5 mL; the discharge of the microstructure reactor 1 is mixed with sodium chlorite phosphoric acid buffer solution and then passes through a micro mixer 2 and the microstructure reactor 2 in sequence, wherein the molar ratio of polyether polyol to sodium chlorite is controlled to be 1: 5, the flow rate of the discharge of the microstructure reactor 1 is 0.45mL/min, and the volume of the microstructure reactor 2 is 5 mL. Standing at 70 deg.C for 11min, introducing the discharge of the microstructure reactor 2 into a product collector, rapidly pouring the product into dilute hydrochloric acid solution, heating the acidic aqueous solution to separate organic phase and water phase; and collecting the organic phase, washing the organic phase with deionized water for multiple times, and neutralizing the organic phase with a sodium hydroxide solution until the pH value is 8.5-9.5 to obtain the fatty alcohol ether sodium carboxylate product. A small amount of sample is taken for acidification, the acidification degree is 85.3 percent, and the conversion rate of polyether polyol is 91.6 percent.
Example 6
Fully mixing a raw material storage tank 1 containing an aqueous solution of catalyst TEMPO and polyether polyol and a raw material storage tank 2 containing an aqueous solution of sodium hypochlorite and sodium bromide through a micro mixer 1, injecting the mixture into a micro-structure reactor 1 of a micro-channel modular reaction device, wherein the content of the catalyst is 3% of the molar weight of polyether polyol, the content of the cocatalyst sodium bromide is 10% of the molar weight of the polyether polyol, the molar ratio of the polyether polyol to the sodium hypochlorite is 1: 5, standing at 50 ℃ for 20min, the flow rate of the mixed solution is 0.26mL/min, and the volume of the micro-structure reactor 1 is 5 mL; mixing the discharge of the microstructure reactor 1 with a sodium chlorite phosphoric acid buffer solution, and then respectively passing through a micro mixer 2 and the microstructure reactor 2 in sequence, wherein the molar ratio of polyether polyol to sodium chlorite is controlled to be 1: 5, the flow rate of the discharge of the microstructure reactor 1 is 0.39mL/min, the volume of the microstructure reactor 2 is 5mL, the mixture stays for 13min at 70 ℃, the discharge of the microstructure reactor 2 is led into a product collector, a product is quickly poured into a dilute hydrochloric acid solution, and the acidic aqueous solution is heated to promote the separation of an organic phase and a water phase; and collecting the organic phase, washing the organic phase with deionized water for multiple times, and neutralizing the organic phase with a sodium hydroxide solution until the pH value is 8.5-9.5 to obtain the fatty alcohol ether sodium carboxylate product. A small amount of sample is taken for acidification, the acidification degree is 89.5 percent, and the conversion rate of polyether polyol is 96.1 percent.
Example 7
Fully mixing a raw material storage tank 1 containing an aqueous solution of catalyst TEMPO and polyether polyol and a raw material storage tank 2 containing an aqueous solution of sodium hypochlorite and sodium bromide through a micro mixer 1, injecting the mixture into a micro-structure reactor 1 of a micro-channel modular reaction device, wherein the content of the catalyst is 8% of the molar weight of polyether polyol, the content of the cocatalyst sodium bromide is 10% of the molar weight of the polyether polyol, the molar ratio of the polyether polyol to the sodium hypochlorite is 1: 5, standing at 50 ℃ for 20min, the flow rate of the mixed solution is 0.26mL/min, and the volume of the micro-structure reactor 1 is 5 mL; mixing the discharge of the microstructure reactor 1 with a sodium chlorite phosphoric acid buffer solution, and then respectively passing through a micro mixer 2 and the microstructure reactor 2 in sequence, wherein the molar ratio of polyether polyol to sodium chlorite is controlled to be 1: 5, the flow rate of the discharge of the microstructure reactor 1 is 0.39mL/min, the volume of the microstructure reactor 2 is 5mL, the mixture stays for 13min at 90 ℃, the discharge of the microstructure reactor 2 is led into a product collector, a product is quickly poured into a dilute hydrochloric acid solution, and the acidic aqueous solution is heated to promote the separation of an organic phase and a water phase; and collecting the organic phase, washing the organic phase with deionized water for multiple times, and neutralizing the organic phase with a sodium hydroxide solution until the pH value is 8.5-9.5 to obtain the fatty alcohol ether sodium carboxylate product. A small amount of sample is taken for acidification, the acidification degree is 89.8 percent, and the conversion rate of polyether polyol is 96.1 percent.
Example 8
Fully mixing a raw material storage tank 1 containing an aqueous solution of catalyst TEMPO and polyether polyol and a raw material storage tank 2 containing an aqueous solution of sodium hypochlorite and sodium bromide through a micro mixer 1, injecting the mixture into a micro-structure reactor 1 of a micro-channel modular reaction device, wherein the content of the catalyst is 6% of the molar weight of polyether polyol, the content of the cocatalyst sodium bromide is 5% of the molar weight of the polyether polyol, the molar ratio of the polyether polyol to the sodium hypochlorite is 1: 5, standing at 50 ℃ for 20min, the flow rate of the mixed solution is 0.26mL/min, and the volume of the micro-structure reactor 1 is 5 mL; mixing the discharge of the microstructure reactor 1 with a sodium chlorite phosphoric acid buffer solution, and then respectively passing through a micro mixer 2 and the microstructure reactor 2 in sequence, wherein the molar ratio of polyether polyol to sodium chlorite is controlled to be 1: 5, the flow rate of the discharge of the microstructure reactor 1 is 0.39mL/min, the volume of the microstructure reactor 2 is 5mL, the mixture stays for 13min at 90 ℃, the discharge of the microstructure reactor 2 is led into a product collector, a product is quickly poured into a dilute hydrochloric acid solution, and the acidic aqueous solution is heated to promote the separation of an organic phase and a water phase; and collecting the organic phase, washing the organic phase with deionized water for multiple times, and neutralizing the organic phase with a sodium hydroxide solution until the pH value is 8.5-9.5 to obtain the fatty alcohol ether sodium carboxylate product. A small amount of sample is taken for acidification, the acidification degree is 88.6 percent, and the conversion rate of polyether polyol is 96.3 percent.
Example 9
Fully mixing a raw material storage tank 1 containing a catalyst TEMPO and a water solution of polyether polyol and a raw material storage tank 2 containing a water solution of sodium hypochlorite and sodium bromide through a micro mixer 1, and injecting the mixture into a micro-structure reactor 1 of a micro-channel modular reaction device, wherein the content of the catalyst is 10% of the molar weight of polyether polyol, the content of the cocatalyst sodium bromide is 20% of the molar weight of polyether polyol, the molar ratio of the polyether polyol to the sodium hypochlorite is 1: 8, the mixture stays for 20min at 50 ℃, the flow rate of the mixed solution is 0.26mL/min, and the volume of the micro-structure reactor 1 is 5 mL; mixing the discharge of the microstructure reactor 1 with a sodium chlorite phosphoric acid buffer solution, and then respectively passing through a micro mixer 2 and the microstructure reactor 2 in sequence, wherein the molar ratio of polyether polyol to sodium chlorite is controlled to be 1: 5, the flow rate of the discharge of the microstructure reactor 1 is 0.39mL/min, the volume of the microstructure reactor 2 is 5mL, the mixture stays for 13min at the temperature of 60 ℃, the discharge of the microstructure reactor 2 is led into a product collector, a product is quickly poured into a dilute hydrochloric acid solution, and the acidic aqueous solution is heated to promote the separation of an organic phase and a water phase; and collecting the organic phase, washing the organic phase with deionized water for multiple times, and neutralizing the organic phase with a sodium hydroxide solution until the pH value is 8.5-9.5 to obtain the fatty alcohol ether sodium carboxylate product. A small amount of sample was taken and acidified to obtain a degree of acidification of 79.3% and a conversion of polyether polyol of 86.5%.
Example 10
Fully mixing a raw material storage tank 1 containing a catalyst TEMPO and a water solution of polyether polyol and a raw material storage tank 2 containing a water solution of sodium hypochlorite and sodium bromide through a micro mixer 1, injecting the mixture into a micro-structure reactor 1 of a micro-channel modular reaction device, wherein the content of the catalyst is 10% of the molar weight of polyether polyol, the content of the cocatalyst sodium bromide is 20% of the molar weight of polyether polyol, the molar ratio of the polyether polyol to the sodium hypochlorite is 1: 7, standing at 30 ℃ for 10min, the flow rate of the mixed solution is 0.5mL/min, and the volume of the micro-structure reactor 1 is 5 mL; mixing the discharge of the microstructure reactor 1 with a sodium chlorite phosphoric acid buffer solution, and then respectively passing through a micro mixer 2 and the microstructure reactor 2 in sequence, wherein the molar ratio of polyether polyol to sodium chlorite is controlled to be 1: 5, the flow rate of the discharge of the microstructure reactor 1 is 0.75mL/min, the volume of the microstructure reactor 2 is 5mL, the discharge of the microstructure reactor 2 is kept for 6min at 80 ℃, the discharge of the microstructure reactor 2 is led into a product collector, a product is quickly poured into a dilute hydrochloric acid solution, and the acidic aqueous solution is heated to promote the separation of an organic phase and an aqueous phase; and collecting the organic phase, washing the organic phase with deionized water for multiple times, and neutralizing the organic phase with a sodium hydroxide solution until the pH value is 8.5-9.5 to obtain the fatty alcohol ether sodium carboxylate product. A small amount of sample is taken for acidification, the acidification degree is 83.6 percent, and the conversion rate of polyether polyol is 89.6 percent.

Claims (8)

1. A method for preparing polyether carboxylate by adopting a micro-flow field reaction technology is characterized by comprising the following steps:
(1) dissolving polyether polyol, a catalyst, a sodium hypochlorite aqueous solution and inorganic base by using a solvent, mixing the solution by using a first micro mixer of a micro-channel modular reaction device, and injecting the mixture into a first micro-structure reactor of the micro-channel modular reaction device for reaction; the reaction temperature of a first micro-structure reactor of the micro-channel modular reaction device is 0-80 ℃, the reaction residence time is 5-30 min, the flow rate of a mixed solution obtained after mixing through a first micro-mixer is 0.1-5 mL/min, and the volume of the first micro-structure reactor is 10-50 mL; the using amount of the catalyst is 1-10% of the molar weight of the polyether polyol, the sodium hypochlorite is an aqueous solution with the effective chlorine content of 5-10%, and the molar ratio of the polyether polyol to the sodium hypochlorite is 1 (1-10); the addition amount of the inorganic base is 5-20% of the molar weight of the polyether polyol;
(2) mixing the mixed system obtained in the step (1) with a sodium chlorite solution through a second micro mixer of the micro-channel modular reaction device, and injecting the mixture into a second micro-structure reactor of the micro-channel modular reaction device for reaction; the reaction temperature of a second micro-structure reactor of the micro-channel modular reaction device is 0-100 ℃, the reaction residence time is 5-30 min, the flow rate of the mixed system obtained in the step (1) and the sodium chlorite solution after being mixed by a second micro-mixer is 0.1-5 mL/min, and the volume of the second micro-structure reactor is 10-50 mL; the molar ratio of the sodium chlorite to the polyether polyol is 1 (1-10);
(3) and (3) introducing the mixed system obtained in the step (2) into a product collector in a microchannel modular reaction device, and carrying out aftertreatment to obtain polyether carboxylate.
2. The method according to claim 1, wherein in the step (1), the catalyst is a noble metal-based catalyst or a nitroxide radical-based compound.
3. The method of claim 2, wherein in step (1), the noble metal catalyst is one or more of ruthenium, osmium, cobalt, rhodium, iridium, nickel, platinum and palladium, and the nitroxide radical compound is one or more of piperidine nitroxide radical, pyrrolidine nitroxide radical, oxazolidine nitroxide radical and proxyl nitroxide radical.
4. The method according to claim 1, wherein in step (1), the inorganic base is sodium carbonate or potassium carbonate.
5. The method according to claim 1, wherein in step (1), the inorganic base is replaced with any one of the following substances: sodium chloride, potassium bromide or sodium bromide.
6. The method according to claim 1, wherein in the step (1), the solvent is ethyl acetate, toluene, acetonitrile, dichloroethane, dichloromethane, acetic acid, n-hexane or water.
7. The method according to claim 1, wherein in step (2), the sodium chlorite solution is prepared by: dissolving sodium chlorite in deionized water, sodium bicarbonate solution, sodium chloride solution, phosphoric acid buffering solution or acetic acid buffering solution while stirring.
8. The method of claim 1, wherein the microchannel module reaction apparatus comprises a first micromixer, a first micro-structured reactor, a second micromixer, a second micro-structured reactor, and a product collector, which are connected in sequence by a pipeline: the first raw material storage tank and the second raw material storage tank are respectively connected with a feeding port of the first micro mixer, and the third raw material storage tank is connected with a feeding port of the second micro mixer.
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