CN116063345B - Phosphonic acid group monomer and preparation method thereof - Google Patents
Phosphonic acid group monomer and preparation method thereof Download PDFInfo
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- CN116063345B CN116063345B CN202111278554.4A CN202111278554A CN116063345B CN 116063345 B CN116063345 B CN 116063345B CN 202111278554 A CN202111278554 A CN 202111278554A CN 116063345 B CN116063345 B CN 116063345B
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- C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
- C07F9/3804—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)] not used, see subgroups
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- C08F30/00—Homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
- C08F30/02—Homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing phosphorus
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Abstract
The invention discloses a phosphonic acid group monomer and a preparation method thereof, wherein the molecular formula of the phosphonic acid group monomer is at least one of XRC7H12NO3PM2、XRC7H12NO3PL、(XRC7H12NO3P)3Z2、(XRC7H12NO3P)2Y、X2C2R1R2R3R4R5(C7H12NO3P)2M4、X2C2R1R2R3R4R5(C7H12NO3P)2L2、(X2C2R1R2R3R4R5(C7H12NO3P)2)3Z4、X2C2R1R2R3R4R5(C7H12NO3P)2Y, X is halogen, R, R 1、R2、R3、R4、R5 is alkyl, and M, L, Z, Y is at least one of monovalent metal, divalent metal, trivalent metal and tetravalent metal respectively. The preparation method comprises the steps of preparing diallyl amino methyl phosphonate, and then reacting the diallyl amino methyl phosphonate with halogenated hydrocarbon and a solvent to obtain a phosphonic acid group monomer. The preparation method has the advantages of high product yield, high product purity, short preparation process, environment friendliness, no pollution, easy industrial production and the like.
Description
Technical Field
The invention belongs to the technical field of polymer organic synthesis, and particularly relates to a phosphonic acid group monomer and a preparation method thereof.
Background
The compounds commonly used in the drilling fluid at present are mainly inorganic treating agents, organic treating agents and surfactants, wherein the inorganic treating agents mainly comprise sodium chloride, potassium chloride, sodium hydroxide, lime and the like, and the organic treating agents mainly comprise synthetic polymers, asphalt, starch, humic acid, cellulose and the like.
The quaternary ammonium salt is also a compound commonly used in drilling fluid, is often used as a surfactant, and can be widely used as an oilfield auxiliary agent in the processes of drilling, fracturing, oil extraction and the like. The quaternary ammonium salt is also called as quaternary ammonium salt, and is a quaternary ammonium cation salt formed by substituting 4 hydrogen ions in ammonium ions with hydrocarbyl groups. The quaternary ammonium salt has 4 carbon atoms directly connected with nitrogen atoms through covalent bonds, and the anion is connected with the nitrogen atoms through ionic bonds. The peculiar molecular structure of the quaternary ammonium salt endows the quaternary ammonium salt with a series of physical and chemical effects such as emulsification, dispersion, solubilization, washing, wetting, lubrication, foaming, defoaming, sterilization, corrosion prevention, static resistance and the like, and corresponding practical application.
CN1510101a discloses the use of a single molecule mono-quaternary ammonium salt and a single molecule poly-quaternary ammonium salt. The device can automatically strip crude oil from the surface of the rock, so that the recovery ratio of the crude oil can be improved, and the device can have self-organizing demulsification effect on the extracted crude oil; and proved by simulation experiments and field experiments, the method has strong operability, simple operation process, wide application range and high oil displacement efficiency. In addition, the single-molecule single-quaternary ammonium salt and the single-molecule multi-quaternary ammonium salt provided by the invention have self-organizing demulsification effect, so that the treatment cost of the oilfield produced fluid can be obviously reduced, the production cost is reduced, and the economic benefit is obvious. In particular, the method is not limited by the influences of factors such as formation temperature, formation water mineralization degree and the like, and the injection process and the ground flow are very simple; the method has the advantages of no environmental pollution and no damage to stratum, and can be repeatedly applied to the same well.
Disclosure of Invention
Aiming at the problems existing in the prior art, the main purpose of the invention is to provide a phosphonic acid group monomer and a preparation method thereof. The phosphonic acid group monomer is a quaternary ammonium salt, can be used as a surfactant, and can be widely applied to the fields of oilfield chemicals, water treatment, paper industry, fiber industry, paint industry, water-absorbing materials, printing and dyeing auxiliary agents, biological medicines and the like. The preparation method has the advantages of high product yield, high product purity, short preparation process, environment friendliness, no pollution, easy industrial production and the like.
The first aspect of the invention provides a phosphonic acid group monomer, wherein the molecular formula of the phosphonic acid group monomer is at least one of XRC7H12NO3PM2、XRC7H12NO3PL、(XRC7H12NO3P)3Z2、(XRC7H12NO3P)2Y、X2C2R1R2R3R4R5(C7H12NO3P)2M4、X2C2R1R2R3R4R5(C7H12NO3P)2L2、(X2C2R1R2R3R4R5(C7H12NO3P)2)3Z4、X2C2R1R2R3R4R5(C7H12NO3P)2Y, XR is monohalogenated hydrocarbon, X 2C2R1R2R3R4R5 is dihalohydrocarbon, X is halogen, and the phosphonic acid group monomer can be at least one of fluorine, chlorine, bromine and iodine; r represents a hydrocarbon group having 2 to 35 carbon atoms, preferably a hydrocarbon group having 3 to 18 carbon atoms; the hydrocarbyl group may be selected from at least one of alkyl, alkenyl, alkynyl, aryl, cycloalkyl; r 1、R2、R4、R5 represents a hydrocarbon group having 0 to 33 carbon atoms, and the hydrocarbon group may be at least one selected from alkyl, alkenyl, alkynyl, aryl, and cycloalkyl; r 1、R2、R4、R5 is a hydrogen atom when the number of carbon atoms is 0, R 3 is a hydrocarbon group with the number of carbon atoms of 0-33, and the hydrocarbon group can be at least one selected from alkyl, alkenyl, alkynyl, aryl and cycloalkyl; the total number of carbon atoms of R 1、R2、R3、R4、R5 is more than or equal to 0 and less than or equal to 33 and R 1+R2+R3+R4+R5; m is one or more of monovalent metals, particularly one or more of group IA metals, preferably sodium and/or potassium, more preferably sodium; l is one or more of divalent metals, and can be selected from one or more of magnesium, calcium, copper and ferrous iron; z is one or more of trivalent metals, and can be selected from one or more of iron and aluminum; y is one or more of tetravalent metals, and can be specifically selected from one or more of titanium and zirconium.
Further, the phosphonic acid group monomer has a structural formula of any one of the formula (1), the formula (2), the formula (3), the formula (4), the formula (5), the formula (6), the formula (7) and the formula (8);
Wherein X is halogen, and can be at least one of fluorine, chlorine, bromine and iodine; r represents a hydrocarbon group having 2 to 35 carbon atoms, preferably a hydrocarbon group having 3 to 18 carbon atoms; the hydrocarbyl group may be selected from at least one of alkyl, alkenyl, alkynyl, aryl, cycloalkyl; r 1、R2、R4、R5 represents a hydrocarbon group having 0 to 33 carbon atoms, and the hydrocarbon group may be at least one selected from alkyl, alkenyl, alkynyl, aryl, and cycloalkyl; r 1、R2、R4、R5 is a hydrogen atom when the number of carbon atoms is 0, R 3 is a hydrocarbon group with the number of carbon atoms of 0-33, and the hydrocarbon group can be at least one selected from alkyl, alkenyl, alkynyl, aryl and cycloalkyl; the total number of carbon atoms of R 1、R2、R3、R4、R5 is more than or equal to 0 and less than or equal to 33 and R 1+R2+R3+R4+R5; m is one or more of monovalent metals, particularly one or more of group IA metals, preferably sodium and/or potassium, more preferably sodium; l is one or more of divalent metals, and can be selected from one or more of magnesium, calcium, copper and ferrous iron; z is one or more of trivalent metals, and can be selected from one or more of iron and aluminum; y is one or more of tetravalent metals, and can be specifically selected from one or more of titanium and zirconium.
Further, the phosphate monomer is a water-soluble monomer, and belongs to quaternary ammonium salt.
The second aspect of the present invention provides a method for preparing a phosphate-based monomer, comprising the steps of:
s1: under the mixing condition, uniformly mixing an organic solvent and phosphorous acid, and obtaining a material flow A after uniform mixing;
S2: regulating and controlling the pH value of the material flow A obtained in the step S1 to be not more than 7, and introducing diallylamine to react to obtain a material flow B after the reaction;
S3: slowly introducing aldehyde into the material flow B obtained in the step S2 to react, and obtaining a material flow C after the reaction;
s4: regulating the pH value of the material flow C obtained in the step S3 to be 6-8, continuing the reaction, and drying a solid phase obtained by separating a reaction product to obtain a material flow D;
S5: and (3) mixing the material flow D obtained in the step (S3), halogenated hydrocarbon and solvent for reaction, and washing and drying the material obtained after the reaction to obtain the phosphonic acid group monomer.
Further, in the preparation method of the phosphate monomer, the volume ratio of the organic solvent to the phosphorous acid in the step S1 is 1-1: 1 to 15, preferably 1 to 2:1 to 8.
Further, in the above preparation method of the phosphate monomer, the organic solvent in step S1 may be at least one of alcohol, ester, ether, and ketone; further, the alcohol, ester, ether, and ketone may have 1 to 12 carbon atoms.
Further, in the above preparation method of the phosphate monomer, the organic solvent in step S1 may be one or more selected from methanol, ethanol, butanol, ethyl acetate, butyl acetate, isoamyl acetate, diethyl ether, butyl ether, acetone, and methyl ethyl ketone.
Further, in the above-mentioned method for producing a phosphate-based monomer, in the step S2, the pH of the stream A obtained in the step S1 is adjusted to 1 to 6.8, preferably to 1 to 4, and more preferably to 1 to 3.
Further, in the above preparation method of the phosphate monomer, in step S2, the pH value of the stream a obtained in step S1 may be adjusted by adding an acidic material, and the acidic material may be an inorganic acid and/or an organic acid, and specifically may be at least one selected from hydrochloric acid, sulfuric acid, nitric acid, oxalic acid, glacial acetic acid, carbonic acid, hydrofluoric acid, citric acid, malic acid, tartaric acid, succinic acid, and the like.
Further, in the above-mentioned method for producing a phosphoric acid-based monomer, the reaction temperature in step S2 is-20 to 10℃and preferably-10 to 5 ℃.
In the preparation method of the phosphate monomer, in the step S2, the diallylamine is introduced by a slow adding mode, for example, a dripping mode can be adopted, and more specifically, the dripping rate can be controlled between 10mL/h and 200mL/h.
Further, in the above-mentioned method for preparing a phosphoric acid-based monomer, the aldehyde in step S3 may be at least one of formaldehyde, dimeric formaldehyde, trimeric formaldehyde and paraformaldehyde, and preferably formaldehyde.
Further, in the above-mentioned method for producing a phosphoric acid-based monomer, the reaction temperature in step S3 is-20 to 10℃and preferably-10 to 5 ℃.
Further, in the above-mentioned preparation method of the phosphoric acid-based monomer, the aldehyde in step S3 is introduced in a liquid form, for example, when formaldehyde is used, it may be directly introduced in a liquid form; when dimeric formaldehyde, trioxymethylene and paraformaldehyde are adopted, the dimeric formaldehyde and the paraformaldehyde can be firstly dissolved in an organic solvent and then added in a liquid form, wherein the organic solvent can be one or more of alcohol, ester, ether and ketone; further, the carbon number of the alcohol, the ester, the ether and the ketone can be 1-12, and specifically can be one or more selected from methanol, ethanol, butanol, ethyl acetate, butyl acetate, isoamyl acetate, diethyl ether, butyl ether, acetone and methyl ethyl ketone.
Furthermore, in the preparation method of the phosphate monomer, the slow introduction of aldehyde in the step S3 can adopt a dropwise adding mode, and further, the dropwise adding speed can be controlled within a range of 10mL/h to 200 mL/h.
Further, in the preparation method of the phosphate monomer, the reaction temperature in the step S4 is 0-90 ℃, preferably 20-40 ℃; the reaction time is 0.5 to 6 hours, preferably 1 to 3 hours.
Further, in the above-mentioned preparation method of the phosphate-based monomer, in the step S4, an alkaline substance may be added to regulate the pH of the stream C obtained in the step S3 to 6 to 8, the alkaline substance may be an inorganic base and/or an alkaline inorganic salt, and the metal element in the inorganic base and/or the alkaline inorganic salt is one or more selected from monovalent, divalent, trivalent and tetravalent metals, more specifically, one or more selected from sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, magnesium hydroxide, magnesium carbonate, calcium hydroxide, iron hydroxide, copper hydroxide, titanium hydroxide, zirconium hydroxide and the like, and preferably one or more selected from sodium hydroxide and potassium hydroxide.
Further, in the preparation method of the phosphate monomer, the reaction temperature in the step S4 is 0-90 ℃, preferably 20-40 ℃; the reaction time is 0.5 to 6 hours, preferably 1 to 3 hours.
Further, in the preparation method of the phosphate monomer, the separation mentioned in the step S4 is solid-liquid separation, the solid-liquid separation may be any means capable of realizing solid-liquid two-phase separation, the selection of the separation means belongs to the basic skills of those skilled in the art, and the separation may be reasonably selected according to actual situations, and specifically, one or more modes of filtration separation, centrifugal separation and the like may be adopted.
In the preparation method of the phosphate monomer, the liquid phase separated in the step S4 can be recycled to the step S1 for continuous use, and the reaction is continued after other raw materials are supplemented.
Further, in the preparation method of the phosphate monomer, the drying conditions in step S4 are as follows: the drying temperature is 60-120 ℃ and the drying time is 6-12 h.
Further, in the above-mentioned preparation method of the phosphoric acid-based monomer, the stream D obtained in the step S4 is diallylaminomethyl phosphonate.
Further, in the above-mentioned method for preparing a phosphoric acid-based monomer, the halogenated hydrocarbon in step S5 may be at least one of a monohalogenated hydrocarbon and a dihalogenated hydrocarbon, and preferably is a monohalogenated hydrocarbon; can be at least one of fluorohydrocarbon, chlorohydrocarbon, bromohydrocarbon and iodohydrocarbon; the halogenated hydrocarbon is a hydrocarbon group having 2 to 35 carbon atoms, preferably a hydrocarbon group having 3 to 18 carbon atoms; the hydrocarbon group may be at least one of alkyl, alkenyl, alkynyl, aryl, cycloalkyl; x is halogen, and can be at least one of fluorine, chlorine, bromine and iodine.
Further, in the above preparation method of the phosphate-based monomer, in the step S5, the halogenated hydrocarbon may be bromoethane, bromopropane, bromobutane, bromopentane, bromohexane, bromoheptane, bromooctane, bromononane, bromodecane, bromoundecane, bromododecane, bromotridecane, bromotetradecane, bromopentadecane, bromohexadecane, bromoheptadecane, bromooctadecane, bromononadecane, bromoeicosane, bromoheneicosane, bromodocosyl, bromotricosyl, bromotetracosyl, bromopentacosyl, bromohexacosyl, bromoheptacosyl, bromooctacosyl, bromononacosyl, bromotriacontyl, bromotetracosyl, and bromotriacontyl; Iodoethane, iodopropane, iodobutane, iodopentane, iodohexane, iodoheptane, iodooctane, iodononane, iodosunflower, iodoundecane, iodododecane iodotridecane, iodotetradecane, iodopentadecane, iodohexadecane, iodoheptadecane, iodooctadecane, iodononadecane, iodoicosane, iodohexadecane iodine eicosane, iodine docosane, iodine tricosane, iodine tetracosane, iodine pentacosane, iodine hexacosane, iodine heptacosane, iodine octacosane, iodine nonacosane, iodine triacontane, iodine tetratriacontane, and iodine pentatriacontane; chloroethane, chloropropane, chlorobutane, chloropentane, chlorohexane, chloroheptane, chlorooctane, chlorononane, chlorodecanoe, chloroundecane, chlorododecane, chlorotridecane, chlorotetradecane, chloropentadecane, chlorohexadecane, chloroheptadecane, chlorooctadecane, chlorononadecane, chloroeicosane, chlorodocosane, chlorotricosane, chlorotetracosane, chloropentacosane, chlorohexacosane, chloroheptadecane, chlorooctacosane, chlorononadecane, chlorotriacontane; Fluoropropane, fluorobutane, fluoropentane, fluorohexane, fluoroheptane, fluorooctane, fluorononane, fluorodecane, fluoroundecane, fluorododecane, fluorotridecane, fluorotetradecane, fluoropentadecane, fluorohexadecane, fluoroheptadecane, fluorooctadecane, fluorononadecane, fluoroeicosane, fluorodocosyne, fluorotricosane, fluorotetracosane, fluoropentacosane, fluorohexacosane, fluoroheptadecane, fluorooctacosane, fluorononadecane, fluorotriacontane, fluorotetracosane, fluorotriacontane; 2-bromopropene, 3-bromopropene, 2-butenyl bromide, 4-bromobutene, 1-bromo-3-methyl-2-butene, 5-bromo-1-pentene, 6-bromo-1-hexene, 7-bromo-1-heptene, 8-bromo-1-octene, 9-bromo-1-nonene, 10-bromo-1-decene, 11-bromo-1-undecene, 12-bromo-1-dodecene, 13-bromo-1-tridecene, 14-bromo-1-tetradecene, 15-bromo-1-pentadecene, 16-bromo-1-hexadecene, 17-bromo-1-heptadecene, 18-bromo-1-octadecene, 19-bromo-1-nonadecene, 20-bromo-1-eicosene, 21-bromo-1-eicosene, 22-bromo-1-docosene, 23-bromo-1-tricosene, 24-bromo-1-tetracosene, 25-bromo-1-pentacosene; 2-chloropropene, 3-chloropropene, 2-butenyl chloride, 4-chlorobutene, 1-chloro-3-methyl-2-butene, 5-chloro-1-pentene, 6-chloro-1-hexene, 7-chloro-1-heptene, 8-chloro-1-octene, 9-chloro-1-nonene, 10-chloro-1-decene, 11-chloro-1-undecene, 12-chloro-1-dodecene, 13-chloro-1-tridecene, 14-chloro-1-tetradecene, 15-chloro-1-pentadecene, 16-chloro-1-hexadecene, 17-chloro-1-heptadecene, 18-chloro-1-octadecene, 19-chloro-1-nonadecene, 20-chloro-1-eicosene, 21-chloro-1-eicosene, 22-chloro-1-docosene, 23-chloro-1-tricosene, 24-chloro-1-tetracosene, 25-chloro-1-pentacosene; 2-iodopropylene, 3-iodopropylene, 2-butenyl iodide, 4-iodobutene, 1-iodo-3-methyl-2-butene, 5-iodo-1-pentene, 6-iodo-1-hexene, 7-iodo-1-heptene, 8-iodo-1-octene, 9-iodo-1-nonene, 10-iodo-1-decene, 11-iodo-1-undecene, 12-iodo-1-dodecene, 13-iodo-1-tridecene, 14-iodo-1-tetradecene, 15-iodo-1-pentadecene, 16-iodo-1-hexadecene, 17-iodo-1-heptadecene, 18-iodo-1-octadecene, 19-iodo-1-nonadecene, 20-iodo-1-eicosene, 21-iodo-1-eicosene, 22-iodo-1-docosene, 23-iodo-1-tricosene, 24-iodo-1-tetracosene, 25-iodo-1-pentacosene; 2-fluoropropene, 3-fluoropropene, 2-butenyl-fluoro, 4-fluorobutene, 1-fluoro-3-methyl-2-butene, 5-fluoro-1-pentene, 6-fluoro-1-hexene, 7-fluoro-1-heptene, 8-fluoro-1-octene, 9-fluoro-1-nonene, 10-fluoro-1-decene, 11-fluoro-1-undecene, 12-fluoro-1-dodecene, 13-fluoro-1-tridecene, 14-fluoro-1-tetradecene, 15-fluoro-1-pentadecene, 16-fluoro-1-hexadecene, 17-fluoro-1-heptadecene, 18-fluoro-1-octadecene, 19-fluoro-1-nonadecene, 20-fluoro-1-eicosene, 21-fluoro-1-eicosene, 22-fluoro-1-docosene, 23-fluoro-1-tricosene, 24-fluoro-1-tetracosene, 25-fluoro-1-pentacosene; 1, 2-dichloroethane, 1, 2-dichloropropane, 1, 3-dichloropropane, 1, 2-dichlorobutane, 1, 3-dichlorobutane, 1, 4-dichlorobutane, 1, 2-dichloropentane, 1, 3-dichloropentane, 1, 4-dichloropentane, 1, 5-dichloropentane, 1, 2-dichlorohexane, 1, 3-dichlorohexane, 1, 4-dichlorohexane, 1, 5-dichlorohexane, 1, 6-dichlorohexane, 1, 2-dichloroheptane, 1, 3-dichloroheptane, 1, 4-dichloroheptane, 1, 5-dichloroheptane, 1, 6-dichloroheptane, 1, 7-dichloroheptane, 1, 2-dichlorooctane, 1, 3-dichlorooctane, 1, 4-dichlorooctane, 1, 5-dichlorooctane, 1, 6-dichlorooctane, 1, 7-dichlorooctane, 1, 8-dichlorooctane, 1, 2-dichlorononane, 1, 3-dichlorononane, 1, 4-dichlorononane, 1, 5-dichlorononane, 1, 6-dichlorononane, 1, 7-dichlorononane, 1, 8-dichlorononane, 1, 9-dichlorononane, 1, 2-dichlorosunflower, 1, 3-dichlorosunflower, 1, 4-dichlorosunflower, 1, 5-dichlorosunflower, 1, 6-dichlorosunflower, 1, 7-dichlorosunflower, 1, 8-dichlorosunflower, 1, 9-dichlorosunflower, 1, 10-dichlorosunflower; 1, 2-Diiodoethane, 1, 2-diiodopropane, 1, 3-diiodopropane, 1, 2-diiodobutane, 1, 3-diiodobutane, 1, 4-diiodobutane, 1, 2-diiodopentane, 1, 3-diiodopentane, 1, 4-diiodopentane, 1, 5-diiodopentane, 1, 2-diiodohexane, 1, 3-diiodohexane, 1, 4-diiodohexane, 1, 5-diiodohexane, 1, 6-diiodohexane, 1, 2-diiodoheptane, 1, 3-diiodoheptane, 1, 4-diiodoheptane, 1, 5-diiodoheptane, 1, 6-diiodoheptane, 1, 7-diiodoheptane, 1, 2-diiodooctane, 1, 3-diiodooctane, 1, 4-diiodooctane, 1, 5-diiodooctane, 1, 6-diiodooctane, 1, 7-diiodooctane, 1, 8-diiodooctane, 1, 2-diiodononane, 1, 3-diiodononane, 1, 4-diiodononane, 1, 5-diiodononane, 1, 6-diiodononane, 1, 7-diiodononane, 1, 8-diiodononane, 1, 9-diiodononane, 1, 2-diiodononane, 1, 3-diiododecanone, 1, 4-diiodononane, 1, 5-diiododecanone, 1, 6-diiododecanone, 1, 7-diiodononane, 1, 8-diiodononane, 1, 9-diiodononane, 1, 10-diiodononane; 1, 2-dibromoethane, 1, 2-dibromopropane, 1, 3-dibromopropane, 1, 2-dibromobutane, 1, 3-dibromobutane, 1, 4-dibromobutane, 1, 2-dibromopentane, 1, 3-dibromopentane, 1, 4-dibromopentane, 1, 5-dibromopentane, 1, 2-dibromohexane, 1, 3-dibromohexane, 1, 4-dibromohexane, 1, 5-dibromohexane, 1, 6-dibromohexane, 1, 2-dibromoheptane, 1, 3-dibromoheptane, 1, 4-dibromoheptane, 1, 5-dibromoheptane, 1, 6-dibromoheptane, 1, 7-dibromoheptane, 1, 2-dibromooctane, 1, 3-dibromooctane, 1, 4-dibromooctane, 1, 5-dibromooctane, 1, 6-dibromooctane, 1, 7-dibromooctane, 1, 8-dibromooctane, 1, 2-dibromononane, 1, 3-dibromononane, 1, 4-dibromononane, 1, 5-dibromononane, 1, 6-dibromononane, 1, 7-dibromononane, 1, 8-dibromononane, 1, 9-dibromononane, 1, 2-dibromo-sunflower, 1, 3-dibromo-sunflower, 1, 4-dibromo-sunflower, 1, 5-dibromo-sunflower, 1, 6-dibromo-sunflower, 1, 7-dibromo-sunflower, 1, 8-dibromo-sunflower, 1, 9-dibromo-sunflower, 1, 10-dibromo-sunflower; 1, 2-difluoroethane, 1, 2-difluoropropane, 1, 3-difluoropropane, 1, 2-difluorobutane, 1, 3-difluorobutane, 1, 4-difluorobutane, 1, 2-difluoropentane, 1, 3-difluoropentane, 1, 4-difluoropentane, 1, 5-difluoropentane, 1, 2-difluorohexane, 1, 3-difluorohexane, 1, 4-difluorohexane, 1, 5-difluorohexane, 1, 6-difluorohexane, 1, 2-difluoroheptane, 1, 3-difluoroheptane, 1, 4-difluoroheptane, 1, 5-difluoroheptane, 1, 6-difluoroheptane, 1, 7-difluoroheptane, 1, 2-difluorooctane, 1, 3-difluorooctane, 1, 4-difluorooctane, 1, 5-difluorooctane, 1, 6-difluorooctane, 1, 7-difluorooctane, 1, 8-difluorooctane, 1, 2-difluorononane, 1, 3-difluorononane, 1, 4-difluorononane, 1, 5-difluorononane, 1, 6-difluorononane, 1, 7-difluorononane, 1, 8-difluorononane, 1, 9-difluorononane, 1, 2-difluorosunflower, 1, 3-difluorosunflower, 1, 4-difluorosunflower, 1, 5-difluorosunflower, 1, 6-difluorosunflower, 1, 7-difluorosunflower, 1, 8-difluorosunflower, 1, 9-difluorosunflower, 1, 10-difluorosunflower; 1, 4-dichloro-2-butene, 1, 5-dichloro-3-pentene, 1, 6-dichloro-3-hexene, 1, 7-dichloro-4-heptene, 1, 8-dichloro-4-octene, 1, 9-dichloro-4-nonene, 1, 10-dichloro-5-decene, 1, 11-dichloro-5-undecene, 1, 12-dichloro-6-dodecene, 1, 13-dichloro-6-tridecene, 1, 14-dichloro-7-tetradecene, 1, 15-dichloro-7-pentadecene, 1, 16-dichloro-8-hexadecene, 1, 17-dichloro-8-heptadecene, 1, 18-dichloro-9-octadecene, 1, 19-dichloro-9-nonadecene, 1, 20-dichloro-10-eicosene, 1, 21-dichloro-10-eicosene, 1, 22-dichloro-11-docosene, 1, 23-dichloro-11-tricosene, 1, 24-dichloro-12-tetracosene, 1, 25-dichloro-12-pentacosene; 1, 4-dibromo-2-butene, 1, 5-dibromo-3-pentene, 1, 6-dibromo-3-hexene, 1, 7-dibromo-4-heptene, 1, 8-dibromo-4-octene, 1, 9-dibromo-4-nonene, 1, 10-dibromo-5-decene, 1, 11-dibromo-5-undecene, 1, 12-dibromo-6-dodecene, 1, 13-dibromo-6-tridecene, 1, 14-dibromo-7-tetradecene, 1, 15-dibromo-7-pentadecene, 1, 16-dibromo-8-hexadecene, 1, 17-dibromo-8-heptadecene, 1, 18-dibromo-9-octadecene, 1, 19-dibromo-9-nineteen-carbene, 1, 20-dibromo-10-eicosene, 1, 21-dibromo-10-eicosene, 1, 22-dibromo-11-docosene, 1, 23-dibromo-11-tricosene, 1, 24-dibromo-12-tetracosene, 1, 25-dibromo-12-pentacosene; 1, 4-diiodo-2-butene, 1, 5-diiodo-3-pentene, 1, 6-diiodo-3-hexene, 1, 7-diiodo-4-heptene, 1, 8-diiodo-4-octene, 1, 9-diiodo-4-nonene, 1, 10-diiodo-5-decene, 1, 11-diiodo-5-undecene, 1, 12-diiodo-6-dodecene, 1, 13-diiodo-6-tridecene, 1, 14-diiodo-7-tetradecene, 1, 15-diiodo-7-pentadecene, 1, 16-diiodo-8-hexadecene, 1, 17-diiodo-8-heptadecene, 1, 18-diiodo-9-octadecene, 1, 19-diiodo-9-nineteen-ene, 1, 20-diiodo-10-eicosene, 1, 21-diiodo-10-eicosene, 1, 22-diiodo-11-docosene, 1, 23-diiodo-11-tricosene, 1, 24-diiodo-12-tetracosene, 1, 25-diiodo-12-pentacosene; 1, 4-difluoro-2-butene, 1, 5-difluoro-3-pentene, 1, 6-difluoro-3-hexene, 1, 7-difluoro-4-heptene, 1, 8-difluoro-4-octene, 1, 9-difluoro-4-nonene, 1, 10-difluoro-5-decene, 1, 11-difluoro-5-undecene, 1, 12-difluoro-6-dodecene, 1, 13-difluoro-6-tridecene, 1, 14-difluoro-7-tetradecene, 1, 15-difluoro-7-pentadecene, 1, 16-difluoro-8-hexadecene, 1, 17-difluoro-8-heptadecene, 1, 18-difluoro-9-octadecene, At least one of 1, 19-difluoro-9-nineteen-ene, 1, 20-difluoro-10-eicosene, 1, 21-difluoro-10-eicosene, 1, 22-difluoro-11-docosene, 1, 23-difluoro-11-tricosene, 1, 24-difluoro-12-tetracosene, 1, 25-difluoro-12-pentacosene.
Further, in the above preparation method of the phosphate monomer, the organic solvent in step S5 may be at least one of alcohol, ester, ether, and ketone; further, the alcohol, ester, ether, and ketone may have 1 to 12 carbon atoms.
In the preparation method of the phosphate monomer, the solvent in the step S5 is an organic solvent or a mixture of the organic solvent and water, and the mass fraction of the organic solvent in the mixture of the organic solvent and water is 50% -99.5%. The organic solvent can be one or more selected from methanol, ethanol, butanol, ethyl acetate, butyl acetate, isoamyl acetate, diethyl ether, butyl ether, acetone, and methyl ethyl ketone. The organic solvent is the same as or different from the organic solvent in step S1, preferably the same.
Further, in the above-mentioned method for producing a phosphoric acid-based monomer, the sum of the mass of the stream D and the mass of the halogenated hydrocarbon is 20 to 80% of the mass of the solvent.
Further, in the preparation method of the phosphate monomer, the molar ratio of the diallylamine to the phosphorous acid to the aldehyde to the halogenated hydrocarbon is that the diallylamine: phosphorous acid: aldehyde: halogenated hydrocarbon = 1: 1-2: 1-2: 0.5 to 1.2, preferably 1:1 to 1.5:1 to 1.5:0.6 to 1.2.
The third aspect of the invention provides a phosphonic acid based monomer obtained by the preparation method.
The phosphonic acid group monomer provided by the invention can be used as a monomer for preparing polymers for oil fields, such as polymers for oil displacement, recovery ratio improvement, viscosity reduction, water shutoff profile control, well drilling and completion, and the fields of water treatment, paper industry, fiber industry, paint industry, water-absorbing materials, printing and dyeing auxiliary agents, biological medicines and the like.
Compared with the prior art, the phosphonic acid group monomer and the preparation method thereof have the following advantages:
1. The invention prepares a novel phosphonic acid group monomer which is water-soluble solid powder, is easy to dissolve in water and slightly soluble in most organic solvents, is a quaternary ammonium salt containing double bonds, and can be used as an oilfield auxiliary agent by generating a polymer through addition polymerization reaction of free radical polymerization and other monomers or self, wherein the phosphonic acid group monomer has a hydrophobic group after long-chain halohydrocarbon is introduced, and can be used as a cationic surfactant.
2. The phosphate monomer synthesized by the method has high conversion rate, particularly, the organic solvent is used as the reaction solvent in the preparation process of the material flow D (diallyl amino methyl phosphonate), the reaction process can be carried out under anhydrous condition, the reaction efficiency can be improved, the occurrence of side reaction can be reduced, the purity of the obtained product can be improved, and after the reaction is finished, crystals can be formed to be separated out or separated out after the reaction is carried out at low temperature by rotary evaporation, so that the separation process is simpler, and the industrialization is easy to realize.
3. In the preparation method of the novel phosphonic acid group monomer, the phosphonic acid group monomer serving as a target product is water-soluble, an organic solvent reaction system is used in the preparation, the subsequent separation of the product is facilitated, the clear separation of the product can be realized by adopting conventional separation means such as filtration or centrifugal separation, and the target product can be obtained by further drying at low temperature, so that the whole process is green, pollution-free, nontoxic and harmless.
4. The preparation method of the novel phosphonic acid group monomer provided by the invention is a step-by-step one-pot reaction, has low energy consumption in the reaction process and short flow, and is easy to realize large-scale production. And the filtrate obtained by liquid-solid separation can be supplemented with new materials and then recycled, so that the production cost is greatly reduced and the economy of the whole process is improved.
Drawings
FIG. 1 is an infrared spectrum of a sample prepared in example 1 of the present invention.
Detailed Description
In the examples and comparative examples of the present invention, the yield was calculated from the theoretical value calculated as 100% conversion of diallylamine, and the calculation is shown as follows: yield, wt% = (actual weight of product/theoretical weight of product) ×100%. The purity is obtained by liquid chromatography.
Example 1
Adding 5.7g of phosphorous acid and 7mL of absolute ethyl alcohol into a reaction container, adding 2mL of concentrated sulfuric acid (with the concentration of 98 wt%) to adjust the pH value of the system to 1, placing the reaction container into an ice-water bath, dropwise adding 8.6mL of diallylamine through a constant dropping funnel, controlling the dropwise adding within 45min, continuing to reflux react for 2h after the dropwise adding is finished, adding a mixed material of 12.6g of paraformaldehyde and 7mL of absolute ethyl alcohol through the constant dropping funnel, dropwise adding and controlling the dropwise adding to be finished within 20min, continuing to reflux react for 3h after the dropwise adding, adding 5.6g of NaOH into the system, adjusting the pH value of the system to 7, reacting at 20 ℃ for 1h, further centrifugally separating by a centrifuge, drying the obtained solid material at 80 ℃ for 10h to obtain an intermediate product, sequentially adding the intermediate product and 10g of bromobutane into a mixed solution of 40g of absolute ethyl alcohol and 40g of water, heating to 60 ℃ for reacting for 3h, performing spin-steaming to obtain solid powder, washing, and drying for a final product with the purity of 97.0% after suction and drying for 97.0%. The outer spectrum of sample fuchsin is shown in figure 1.
Example 2
5.7G of phosphorous acid and 7mL of methanol are added into a reaction vessel, then 7mL of oxalic acid is added to adjust the pH value of the system to 2, then the reaction vessel is placed into an ice-water bath, 8.6mL of diallylamine is dropwise added through a constant dropping funnel, the dropwise addition is controlled to be completed within 45min, and reflux reaction is continued for 2h after the dropwise addition is completed. Then, a mixture of 6.3g of paraformaldehyde and 3.5mL of methanol was added to the mixture via a constant dropping funnel, the mixture was dropped dropwise and was controlled to be within 10min, and the reflux reaction was continued for 1.5h after the completion of the dropping. Then adding 5.6g of NaOH into the system, regulating the pH value of the system to 7, reacting for 2 hours at 20 ℃, further centrifugally separating by a centrifugal machine, further drying the obtained solid phase material at 80 ℃ for 10 hours to obtain an intermediate product, then sequentially adding the intermediate product and 11g of bromopentane into 80g of absolute ethyl alcohol, heating to 60 ℃ for reacting for 3 hours, then performing rotary evaporation to obtain solid powder, washing with acetone for several times, and performing suction filtration and drying to obtain a final product. Yield 85.3% and purity 97.0%.
Example 3
11.4G of phosphorous acid and 7mL of absolute ethyl alcohol are sequentially added into a reaction container, then 3mL of concentrated nitric acid (with the concentration of 70 wt%) is added to adjust the pH value of the system to 1, then the reaction container is placed into an ice water bath, 8.6mL of diallylamine is dropwise added through a constant dropping funnel, the dropwise addition is controlled to be completed within 45min, and the reflux reaction is continued for 2.5h after the dropwise addition is completed. Then, a mixture of 6.3g of paraformaldehyde and 7mL of absolute ethyl alcohol is added into a constant dropping funnel, the mixture is dropwise added and controlled to be added for 10min, and the reflux reaction is continued for 1.5h after the addition is completed. Then adding 5.6g of KOH to the system to adjust the pH value of the system to 7, reacting for 2.5 hours at 20 ℃, further centrifugally separating by a centrifugal machine, further drying the obtained solid phase material at 80 ℃ for 10 hours to obtain an intermediate product, then sequentially adding the intermediate product and 8.5g of chlorohexane into a mixed solution of 50g of methanol and 15g of water, heating to 65 ℃ to react for 3 hours, performing rotary evaporation to obtain solid powder, washing with acetone for several times, and performing suction filtration and drying to obtain a final product. Yield 85.1% and purity 97.2%.
Example 4
11.4G of phosphorous acid and 7mL of butanol are sequentially added into a reaction container, 7mL of oxalic acid is added to adjust the pH value of the system to 2, then the reaction container is placed into an ice-water bath, 8.6mL of diallylamine is dropwise added through a constant dropping funnel, the adding is controlled to be completed within 45min, and reflux reaction is continued for 2.5h after the adding is completed. Subsequently, a mixture of 12.6g of paraformaldehyde and 7mL of butanol was added via a constant dropping funnel, and the addition was gradually dropped and controlled to be completed at 10 min. And after the dripping is finished, continuing to reflux and react for 1.5 hours, adding 5.6g of NaOH into the system, adjusting the pH value of the system to 7, reacting for 2.5 hours at 20 ℃, further centrifugally separating by a centrifugal machine, further drying the obtained solid material at 80 ℃ for 10 hours to obtain an intermediate product, sequentially adding the intermediate product and 10g of 4-bromobutene into 75g of methanol, heating to 70 ℃ to react for 3 hours, performing rotary evaporation to obtain solid powder, washing with acetone for several times, and performing suction filtration and drying to obtain the final product. Yield 85.5% and purity 97.1%.
Example 5
5.7G of phosphorous acid and 7mL of ethyl acetate are sequentially added into a reaction vessel, then 2mL of concentrated sulfuric acid (with the concentration of 98 wt%) is added to adjust the pH value of the system to 1, then the reaction vessel is placed into a water bath with the temperature of minus 15 ℃, 8.6mL of diallylamine is dropwise added through a constant dropping funnel, and the addition is completed within 30 min. And continuously refluxing for 2 hours after the dripping is finished. Then, a mixture of 12.6g of paraformaldehyde and 7mL of ethyl acetate was added to the constant dropping funnel, and the mixture was gradually dropped and controlled to be added over 20 minutes, and after the completion of the dropping, the reflux reaction was continued for 3 hours. Then adding 5.6g of NaOH into the system, regulating the pH value of the system to 7, reacting for 1h at 20 ℃, further centrifugally separating by a centrifugal machine, further drying the obtained solid phase material at 80 ℃ for 10h to obtain an intermediate product, then sequentially adding the intermediate product and 12g of 6-bromo-1-hexene into 50g of absolute ethyl alcohol, heating to 65 ℃ for reacting for 3h, performing rotary evaporation to obtain solid powder, washing with acetone for several times, and performing suction filtration and drying to obtain a final product. Yield 86.2% and purity 97.4%.
Example 6
15G of phosphorous acid, 14mL of absolute ethyl alcohol and 6mL of concentrated nitric acid (70 wt%) are sequentially added into a reaction vessel, the pH value of the system is regulated to 1, the reaction vessel is placed into an ice water bath, 8.6mL of diallylamine is dropwise added through a constant dropping funnel, and the addition is completed within 45 min. And after the dripping is finished, reflux reaction is continued for 3 hours. Subsequently, a mixture of 15g of trioxymethylene and 14mL of absolute ethanol was added to a constant dropping funnel, and the mixture was added dropwise and completed at 40 minutes. Reflux is continued for 3.5h after the completion of the dropwise addition. Adding 11.5g of NaOH into the system to adjust the pH value of the system to 6, reacting for 1h at 20 ℃, further centrifugally separating by a centrifugal machine, further drying the obtained solid phase material at 80 ℃ for 10h to obtain an intermediate product, sequentially adding the intermediate product and 5.5g of 1, 2-dichloropropane into a mixed solution of 30g of absolute ethyl alcohol and 20g of water, heating to 65 ℃ for reacting for 4h, performing rotary evaporation to obtain solid powder, washing with acetone for several times, filtering and drying to obtain the final product with the yield of 85.3% and the purity of 95.0%.
Example 7
5.7G of phosphorous acid and 7mL of methanol are added into a reaction vessel, then 4mL of glacial acetic acid is added to adjust the pH value of the system to 4.5, then the reaction vessel is placed into an ice water bath, 7.5mL of diallylamine is dropwise added through a constant dropping funnel, the dropwise addition is controlled to be completed within 40min, and reflux reaction is continued for 2h after the dropwise addition is completed. Then adding a mixture of 7g of paraformaldehyde and 5mL of methanol into a constant dropping funnel, dropwise adding the mixture dropwise and controlling the mixture within 10min, and continuing to reflux for 1.5h after the dropwise adding is finished. Then adding 2 g of Ca (OH) into the system, regulating the pH value of the system to 7.5, reacting for 2 hours at 20 ℃, further centrifugally separating by a centrifugal machine, further drying the obtained solid phase material at 80 ℃ for 10 hours to obtain an intermediate product, then sequentially adding the intermediate product and 6g of 1, 2-dichlorobutane into 55g of acetone solution, heating to 65 ℃ for reacting for 3 hours, then performing rotary evaporation to obtain solid powder, washing with acetone for several times, filtering and drying to obtain the final product with the yield of 85.2% and the purity of 96.0%.
Example 8
11.4G of phosphorous acid and 7mL of butanol are sequentially added into a reaction container, 5mL of oxalic acid is added to adjust the pH value of the system to 3, then the reaction container is placed into an ice-water bath, 8.6mL of diallylamine is dropwise added through a constant dropping funnel, the adding is controlled to be completed within 45min, and reflux reaction is continued for 2.5h after the adding is completed. Subsequently, a mixture of 10.6g of paraformaldehyde and 7mL of butanol was added via a constant dropping funnel, and the addition was gradually dropped and controlled to be completed at 10 min. Reflux reaction is continued for 1.5h after the dripping is finished, then Mg (OH) 2 8.8.8 g is added into the system, the pH value of the system is regulated to 7.5, the system reacts for 2.5h at 20 ℃, centrifugal separation is further carried out by a centrifugal machine, the obtained solid phase material is further dried for 10h at 80 ℃ to obtain an intermediate product, then the intermediate product and 9.5g of 1, 2-dibromoethane are sequentially added into 60g of butanol, the temperature is increased to 70 ℃ for 3h, then solid powder is obtained after rotary evaporation, and then acetone is used for washing for several times, suction filtration and drying are carried out to obtain the final product, and the yield is 86.1% and the purity is 97.1%.
Comparative example 1 (reaction with Water as solvent)
5.7G of phosphorous acid and 7mL of water are sequentially added into a reaction vessel, then 3mL of concentrated nitric acid (with the concentration of 70 wt%) is added to adjust the pH value of the system to 1, then the reaction vessel is placed into an ice-water bath, 8.6mL of diallylamine is dropwise added through a constant dropping funnel, the addition is controlled to be completed within 45min, and reflux reaction is continued for 2h after the dropwise addition is completed. Then, a mixture of 12.6g of paraformaldehyde and 7mL of water was added to the constant dropping funnel, and the addition was gradually dropped and controlled to be completed at 40 minutes. After the completion of the dropwise addition, the reflux reaction was continued for 2 hours. Adding 5.6g of NaOH into the system to adjust the pH value of the system to 7, reacting for 1h at 20 ℃, further centrifugally separating by a centrifugal machine, further drying the obtained solid phase material at 80 ℃ for 10h to obtain an intermediate product, sequentially adding the intermediate product and 10g of bromobutane into a mixed solution of 40g of absolute ethyl alcohol and 40g of water, heating to 60 ℃ to react for 3h, performing rotary evaporation to obtain solid powder, washing with acetone for several times, and performing suction filtration and drying to obtain a final product. Yield 80.3% and purity 80.2%.
Comparative example 2 (reaction Using Water and Ethyl acetate Mixed System as solvent)
5.7G of phosphorous acid, 3.5mL of water and 3.5mL of ethyl acetate are added into a reaction vessel, 4mL of glacial acetic acid is added, the mixture is placed in an ice-water bath, 8.6mL of diallylamine is slowly added dropwise into the mixture, the dropwise addition is controlled to be completed within 45min, and reflux reaction is continued for 3h. Then, a mixture of 12.6g of paraformaldehyde, 3.5mL of water and 3.5mL of ethyl acetate was added to the system in proportion for 60 minutes. The mixture was refluxed for a further 4h. Adding 5.6g of NaOH into the system to adjust the pH value of the system to 7, reacting for 1h at 20 ℃, further centrifugally separating by a centrifugal machine, further drying the obtained solid phase material at 80 ℃ for 10h to obtain an intermediate product, sequentially adding the intermediate product and 11g of bromopentane into a mixed solution of 50g of absolute ethyl alcohol and 30g of water, heating to 60 ℃ to react for 3h, performing rotary evaporation to obtain solid powder, washing with acetone for several times, and performing suction filtration and drying to obtain a final product. Yield 80.8% and purity 82.2%.
Claims (31)
1. A preparation method of a phosphonic acid group monomer is characterized by comprising the following steps: the method comprises the following steps:
s1: under the mixing condition, uniformly mixing an organic solvent and phosphorous acid, and obtaining a material flow A after uniform mixing;
s2: regulating and controlling the pH value of the material flow A obtained in the step S1 to be not more than 7, and introducing diallylamine to react to obtain a material flow B after the reaction;
S3: slowly introducing aldehyde into the material flow B obtained in the step S2 to react, and obtaining a material flow C after the reaction;
S4: regulating the pH value of the material flow C obtained in the step S3 to be 6-8, continuing the reaction, and drying a solid phase obtained by separating a reaction product to obtain a material flow D;
S5: mixing the material flow D obtained in the step S3, halogenated hydrocarbon and solvent for reaction, and washing and drying the material obtained after the reaction to obtain a phosphonic acid group monomer;
in the step S4, alkaline substances are added to regulate and control the pH value of the material flow C obtained in the step S3 to be 6-8; the alkaline substance is selected from one or more of sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, magnesium hydroxide, magnesium carbonate, calcium hydroxide, ferric hydroxide, cupric hydroxide, titanium hydroxide and zirconium hydroxide;
the phosphonic acid group monomer has a structural formula of any one of a formula (1), a formula (2), a formula (3), a formula (4), a formula (5), a formula (6), a formula (7) and a formula (8);
(1)
(2)
(3)
(4)
(5)
(6)
(7)
(8)
Wherein X is halogen, and is selected from at least one of fluorine, chlorine, bromine and iodine; r represents a hydrocarbon group with 2-35 carbon atoms, and the hydrocarbon group is selected from at least one of alkyl, alkenyl, alkynyl, aryl and cycloalkyl; r 1、R2、R4、R5 represents a hydrocarbon group having 0 to 33 carbon atoms, and the hydrocarbon group is at least one selected from alkyl, alkenyl, alkynyl, aryl and cycloalkyl; r 1、R2、R4、R5 is a hydrogen atom when the number of carbon atoms is 0, R 3 is a hydrocarbon group with the number of carbon atoms of 0-33, and the hydrocarbon group is at least one selected from alkyl, alkenyl, alkynyl, aryl and cycloalkyl; the total number of carbon atoms of R 1、R2、R3、R4、R5 is more than or equal to 0 and less than or equal to 33 and R 1+R2+R3+R4+R5; m is one or more of monovalent metals, L is one or more of divalent metals, Z is one or more of trivalent metals, and Y is one or more of tetravalent metals.
2. The process for producing a phosphonic acid based monomer according to claim 1, characterized in that: r represents a hydrocarbon group having 3 to 18 carbon atoms; m is selected from one or more of group IA metals; l is one or more selected from magnesium, calcium, copper and ferrous iron; z is selected from one or more of iron and aluminum; y is selected from one or more of titanium and zirconium.
3. The process for producing a phosphonic acid based monomer according to claim 2, characterized in that: m is sodium and/or potassium.
4. The process for producing a phosphonic acid based monomer according to claim 1, characterized in that: in the step S1, the volume ratio of the organic solvent to the phosphorous acid is 1-1: 1 to 15.
5. A process for preparing phosphonic acid based monomers as defined in claim 4, wherein: in the step S1, the volume ratio of the organic solvent to the phosphorous acid is 1-2: 1 to 8.
6. The process for producing a phosphonic acid based monomer according to claim 1, characterized in that: the organic solvent in the step S1 is at least one of alcohol, ester, ether and ketone.
7. A process for preparing a phosphonic acid based monomer as defined in claim 6, wherein: the alcohol, ester, ether and ketone have 1 to 12 carbon atoms.
8. The process for producing a phosphonic acid based monomer according to claim 1, characterized in that: the organic solvent in step S1 is selected from one or more of methanol, ethanol, butanol, ethyl acetate, butyl acetate, isoamyl acetate, diethyl ether, butyl ether, acetone, and methyl ethyl ketone.
9. The process for producing a phosphonic acid based monomer according to claim 1, characterized in that: in the step S2, the pH value of the material flow A obtained in the step S1 is regulated to be 1-6.8.
10. The process for producing a phosphonic acid based monomer according to claim 9, characterized in that: in the step S2, the pH value of the material flow A obtained in the step S1 is regulated to be 1-4.
11. The process for producing a phosphonic acid based monomer according to claim 9, characterized in that: in the step S2, the pH value of the material flow A obtained in the step S1 is regulated to be 1-3.
12. The process for producing a phosphonic acid based monomer according to claim 1, characterized in that: in the step S2, an acidic substance is added to regulate the pH value of the material flow A obtained in the step S1, wherein the acidic substance is inorganic acid and/or organic acid and is selected from at least one of hydrochloric acid, sulfuric acid, nitric acid, oxalic acid, glacial acetic acid, carbonic acid, hydrofluoric acid, citric acid, malic acid, tartaric acid and succinic acid.
13. The process for producing a phosphonic acid based monomer according to claim 1, characterized in that: the reaction temperature in the step S2 is-20-10 ℃.
14. The process for producing a phosphonic acid based monomer according to claim 13, characterized in that: the reaction temperature in the step S2 is-10-5 ℃.
15. The process for producing a phosphonic acid based monomer according to claim 1, characterized in that: the aldehyde in the step S3 is at least one of formaldehyde, dimeric formaldehyde, trioxymethylene and paraformaldehyde.
16. The process for producing a phosphonic acid based monomer according to claim 1, characterized in that: the reaction temperature in the step S3 is-20-10 ℃.
17. The process for producing a phosphonic acid based monomer according to claim 16, characterized in that: the reaction temperature in the step S3 is-10-5 ℃.
18. The process for producing a phosphonic acid based monomer according to claim 1, characterized in that: the reaction temperature in the step S4 is 0-90 ℃; the reaction time is 0.5-6 h.
19. The process for preparing a phosphonic acid based monomer as recited in claim 18, wherein: the reaction temperature in the step S4 is 20-40 ℃; the reaction time is 1-3 h.
20. The process for producing a phosphonic acid based monomer according to claim 1, characterized in that: the liquid phase separated in the step S4 is recycled to the step S1 for continuous use, and the reaction is continued after other raw materials are supplemented.
21. The process for producing a phosphonic acid based monomer according to claim 1, characterized in that: the drying conditions in step S4 are: the drying temperature is 60-120 ℃ and the drying time is 6-12 h.
22. The process for producing a phosphonic acid based monomer according to claim 1, characterized in that: the halohydrocarbon in the step S5 is at least one of monohalohydrocarbon and dihalocarbon; the halohydrocarbon is at least one of fluorohydrocarbon, chlorohydrocarbon, bromohydrocarbon and iodohydrocarbon; the halohydrocarbon is hydrocarbon with 2-35 carbon atoms, and the hydrocarbon is at least one of alkyl, alkenyl, alkynyl, aryl and cycloalkyl.
23. The process for preparing a phosphonic acid based monomer as recited in claim 22, wherein: the halogenated hydrocarbon is a hydrocarbon group having 3 to 18 carbon atoms.
24. The process for producing a phosphonic acid based monomer according to claim 1, characterized in that: the organic solvent in the step S5 is at least one of alcohol, ester, ether and ketone.
25. The process for preparing a phosphonic acid based monomer as recited in claim 24, wherein: the carbon number of the alcohol, the ester, the ether and the ketone is 1-12.
26. The process for producing a phosphonic acid based monomer according to claim 1, characterized in that: in step S5, the solvent is an organic solvent or a mixture of an organic solvent and water.
27. The process for producing a phosphonic acid based monomer as recited in claim 26, wherein: the mass fraction of the organic solvent in the mixture of the organic solvent and water is 50-99.5%.
28. The process for producing a phosphonic acid based monomer according to claim 1, characterized in that: the sum of the mass of the stream D and the mass of the halogenated hydrocarbon is 20-80% of the mass of the solvent.
29. The process for producing a phosphonic acid based monomer as recited in claim 26, wherein: the organic solvent is selected from one or more of methanol, ethanol, butanol, ethyl acetate, butyl acetate, isoamyl acetate, diethyl ether, butyl ether, acetone, and methyl ethyl ketone.
30. The process for producing a phosphonic acid based monomer according to claim 1, characterized in that: the molar ratio of the diallylamine to the phosphorous acid to the aldehyde to the halogenated hydrocarbon is that the diallylamine: phosphorous acid: aldehyde: halogenated hydrocarbon = 1: 1-2: 1-2: 0.5 to 1.2.
31. The process for producing a phosphonic acid based monomer as recited in claim 30, wherein: the molar ratio of the diallylamine to the phosphorous acid to the aldehyde to the halogenated hydrocarbon is that the diallylamine: phosphorous acid: aldehyde: halogenated hydrocarbon = 1:1 to 1.5:1 to 1.5:0.6 to 1.2.
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