CN102276645B - Preparation method of diethyl N,N-bis(2- hydroxyethyl) aminomethylphosphonate - Google Patents
Preparation method of diethyl N,N-bis(2- hydroxyethyl) aminomethylphosphonate Download PDFInfo
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Abstract
The invention provides a preparation method of diethyl N,N-bis(2- hydroxyethyl) aminomethylphosphonate, comprising the following steps: (1) carrying out depolymerization on paraformaldehyde; (2) carrying out ring formation on formaldehyde and diethanol amine to prepare 3-(2- hydroxyethyl)-1,3-oxazolidine; (3) reacting 3-(2- hydroxyethyl)-1,3-oxazolidine with diethyl phosphite in the presence of anhydrous Lewis acid catalysts; and (4) filtering and recovering the catalysts to obtain a yellow transparent liquid product. The overall yield of the whole process reaches more than 99 %, and the content of diethyl N,N-bis(2- hydroxyethyl) aminomethylphosphonate in the product is 94 %-96 %. The preparation method disclosed in the invention is simple and efficient, has the advantages of high product yield, high content of effective components in the product, reduction of temperature in dehydration process, shortening of time, and low energy consumption, reduces the water content of the final product to 0.1-0.2 %, and reduces the dosage of the catalysts by 20-50%. The preparation method is suitable for large-scale industrial production.
Description
Technical field:
The present invention relates to a kind of preparation method of phosphorous acid esters halogen-free flame retardants, a kind of N specifically, the preparation method of two (2-hydroxyethyl) the AminomethylphosphoniAcid Acid diethyl esters of N-.
Background technology:
Along with the development of synthetic material industry, fire-retardantization become an important content of synthetic materials modification, and research Ye Bei world's scientific research scholar of fire retardant material pays close attention to.At present, the most frequently used fire retardant in the whole world is halogen containing flame-retardant, especially bromide fire retardant, its addition is less, flame retarding efficiency is high, but while burning due to it, emit a large amount of toxic smogs and corrosive gases, cause environmental pollution and harm humans life security, so its range of application is more and more restricted.In recent years, the bittern-free flame-proof material of high flame retardant, high safety, low toxicity, low cigarette, non-corrosiveness γ-ray emission becomes one of research emphasis in fire-retardant science.N, two (2-hydroxyethyl) the AminomethylphosphoniAcid Acid diethyl esters (structure is as shown in I) of N-, as a kind of non-halogen environmental protection reactive flame retardant, not only accord with
Close the trend of fire retardant future development, and it can be compound on polymer molecular chain by chemical reaction in the preparation process of polymkeric substance, less to the Effect on Mechanical Properties of material, flame retardant effect is lasting.N, two (2-hydroxyethyl) the AminomethylphosphoniAcid Acid diethyl esters of N-are mainly used in flame retardant of plastic, are particularly suitable for preparing urethane foam.
The general synthetic route of this compound is as follows:
Publication number is that the United States Patent (USP) of US3076010 discloses N, the detailed preparation method of two (2-hydroxyethyl) the AminomethylphosphoniAcid Acid diethyl esters of N-, this synthetic method is that addition reaction generation intermediate water solution occurs for (1) diethanolamine and formaldehyde (37% the aqueous solution); (2) this intermediate water solution is reacted with diethyl phosphite; (3) by extracted with diethyl ether; (4) the separated N that obtains of underpressure distillation, two (2-hydroxyethyl) the AminomethylphosphoniAcid Acid diethyl esters of N-, product yield is 88%.The shortcoming of the method is in intermediate preparation process, to have a large amount of water, and the annulation of diethanolamine and formaldehyde is reversible reaction, and water is one of raw material of reversed reaction, and the existence of therefore large water gaging is very unfavorable to the generation of intermediate.In addition, when large water gaging exists, diethyl phosphite more easily decomposes, and then causes a series of side reactions, causes product purity low, separation difficulty.Described in this patent, use the method to prepare N, two (2-hydroxyethyl) the AminomethylphosphoniAcid Acid diethyl ester product yields of N-are low, N, the purity of two (2-hydroxyethyl) the AminomethylphosphoniAcid Acid diethyl esters of N-is not high yet.
Publication number is that the Chinese patent of CN 1583768A is to N, the preparation technology of two (2-hydroxyethyl) the AminomethylphosphoniAcid Acid diethyl esters of N-improves, concrete preparation method comprises the following steps: in (1) reactor, add 165 parts (by weight, 37～40% formalin down together), 206 parts of diethanolamine that add melting in advance under stirring, keep temperature of reaction at 30 to 50 ℃, react 0.5～1.5 hour; (2) 50～60 ℃ and 60～80 ℃ of twice underpressure distillation, steam moisture, obtain 3-(2-hydroxyethyl)-1,3-oxazolidine; (3) 0.3 to 2.5 part of anhydrous solid acid catalyst and 271 parts of diethyl phosphites are added to 3-(2-hydroxyethyl)-1,3-oxazolidine, reacts 1 to 6 hour at 20 ℃ at 80 ℃; (4) reaction mass cools to room temperature, and filtering recovering catalyst obtains yellow transparent liquid product.This technique first adopts the way of underpressure distillation to remove the moisture in reaction system when the first step reaction finishes, and has avoided to a certain extent the hydrolysis of diethyl phosphite; In second step reaction, add solid acid catalyst simultaneously, improved the yield of product and the purity of product.But this technique has been used the formaldehyde solution containing large water gaging equally, generation to intermediate is unfavorable, the reacted high temperature dehydration link of the first step water removal effect is poor, even be also difficult to, the moisture in whole system is reduced to rational scope at 80 ℃, and the existence of moisture will directly affect the carrying out of the next step, affect quality and the later stage application of product.If extend high temperature, dewater the time, not only can affect the quality of intermediate, and can increase energy consumption in production process, be unfavorable for suitability for industrialized production.
Summary of the invention:
The object of the present invention is to provide a kind of N, the preparation method of two (2-hydroxyethyl) the AminomethylphosphoniAcid Acid diethyl esters of N-, eliminated the impact that moisture is prepared intermediate, and make the water content in product be reduced to rational level, improved N in the yield of product and product, the content of two (2-hydroxyethyl) the AminomethylphosphoniAcid Acid diethyl esters of N-, has realized the optimization to whole technical process efficiency, has effectively improved quality product.
For reaching above object, technical scheme of the present invention is as follows:
A N, the preparation method of two (2-hydroxyethyl) the AminomethylphosphoniAcid Acid diethyl esters of N-, comprises the following steps:
(1) in reactor, add solvent and paraformaldehyde solid, the mol ratio of solvent and paraformaldehyde (take formaldehyde) is 0.5～2.0, preferably 0.8～1.5, more preferably 0.9～1.2, under certain temperature and pH value condition, paraformaldehyde solid is dissolved completely;
Temperature described in step (1) is 60～80 ℃, preferably 65～75 ℃, the pH value of solution is 8～12, and the pH that preferably adopts sodium hydroxide solution regulator solution is 9～11, and described solvent is ethanol, n-propyl alcohol, Virahol, isopropylcarbinol, propyl carbinol, Pentyl alcohol or primary isoamyl alcohol.Preferred n-propyl alcohol, Virahol or propyl carbinol.
(2) solution of (1) step is cooled to 25～40 ℃, and adds siccative in reactor, under stirring, add the diethanolamine of melting, control temperature of reaction at 25～50 ℃, preferably 30～40 ℃, react 0.5～2 hour, preferably 1～1.5 hour, remove by filter siccative;
Wherein, the mol ratio of paraformaldehyde and diethanolamine is 0.9～1.4: 1, preferably 1～1.2: 1, and described siccative is one or two or more in anhydrous sodium sulphate, anhydrous magnesium sulfate, anhydrous calciumsulphate or calcium oxide mixture in any proportion; The mol ratio of diethanolamine and siccative is 1: 0.1～0.3, and during filtration, temperature is 30～40 ℃.
(3) the reaction solution underpressure distillation (2) step being obtained, except desolventizing, utilizes solvent and water azeotropic to dewater simultaneously, obtains 3-(2-hydroxyethyl)-1,3-oxazolidine (intermediate);
Wherein, underpressure distillation vacuum tightness >=0.095MPa, temperature is 45～50 ℃, intermediate yield 99～99.8%, 3-in gas phase analysis intermediate (2-hydroxyethyl)-1,3-oxazolidine content 99.6～99.9%, measures by karl-Fischer method, 3-(2-hydroxyethyl)-1,3-oxazolidine water-content is 0.2～0.4%.
(4) be cooled to 40～50 ℃, in reactor, add anhydrous lewis acid catalyst, be warming up to 40～80 ℃, preferably 50～60 ℃, drip while stirring diethyl phosphite, after being added dropwise to complete, at this temperature, continue reaction 1～6 hour, preferably 2～3 hours;
Wherein, the diethyl phosphite consumption adding meets: intermediate 3-(2-hydroxyethyl)-1, the mol ratio of 3-oxazolidine and diethyl phosphite is 0.8～1.2: 1, preferably 1～1.2: 1, more preferably 1～1.1: 1, described anhydrous lewis acid catalyst is aluminum trichloride (anhydrous), Calcium Chloride Powder Anhydrous, iron trichloride, one or two or more in titanium tetrachloride or magnesium chloride mixture in any proportion, preferred aluminum trichloride (anhydrous) or iron trichloride, the add-on of catalyzer is 3-(2-hydroxyethyl)-1, 0.05～0.4% of 3-oxazolidine and diethyl phosphite gross weight, preferably 0.15～0.3%.
(5) reaction mass temperature is down to room temperature, filtering recovering catalyst, obtains yellow transparent liquid product.Yield 99～99.6%, N in gas phase analysis product, the content of two (2-hydroxyethyl) the AminomethylphosphoniAcid Acid diethyl esters of N-is 91～96%.Water-content is 0.1%～0.2%.
The present invention's siccative, solvent and catalyzer used can be recycled, and reduced the pollution to environment, is conducive to reduce production costs.
Positively effect of the present invention is:
(1) by adopting paraformaldehyde to replace formalin, the formaldehyde that formaldehyde depolymerization is generated reacts with diethanolamine, has eliminated the impact that moisture is prepared intermediate.
(2) adopt ethanol, n-propyl alcohol, Virahol, isopropylcarbinol, propyl carbinol, Pentyl alcohol or primary isoamyl alcohol as the solvent of paraformaldehyde depolymerization, solvent can with water azeotropic water removing, be conducive to removing of water in intermediate preparation feedback, make the temperature of underpressure distillation low, time is short, avoided the decomposition of the intermediate that pyrogenic distillation causes, intermediate yield is up to 99～99.8%, 3-in gas phase analysis intermediate (2-hydroxyethyl)-1,3-oxazolidine content 99.6～99.9%, reduced energy consumption, the colourity of the finished product is low simultaneously.Solvent is recoverable also.Adopt siccative water suction to solve the problem that independent employing underpressure distillation cannot effectively dewater simultaneously, make the water content in product be reduced to rational level; By karl-Fischer method, measure, 3-(2-hydroxyethyl)-1,3-oxazolidine water-content is 0.2～0.4%, the moisture in the finished product is 0.1%～0.2%, meets the requirement of preparation polyurethane foam to raw material moisture far away.
(3) catalyst levels is few, and compared with the prior art, catalyst levels can reduce 20～50%, is applicable to large-scale industrial production.
(4) product yield is high, and yield can reach N more than 99% and in product, and the content of two (2-hydroxyethyl) the AminomethylphosphoniAcid Acid diethyl esters of N-can reach 94～96%.
Accompanying drawing explanation
Fig. 1 is the nuclear magnetic spectrogram of embodiment 1 product.
Fig. 2 is the GC-MS spectrogram of embodiment 1 product.
Fig. 3 is the infrared spectrogram of embodiment 1 product.
Embodiment
Below in conjunction with embodiment, the present invention is further illustrated, it should be noted that, embodiment does not form the restriction to the claimed scope of the present invention.
1. take 360 parts of n-propyl alcohols in the 2L there-necked flask with magnetic stirring apparatus, constant pressure funnel and thermometer, be warming up to 70 ℃, add 180 parts of paraformaldehyde solids, with sodium hydroxide solution, regulating the pH of paraformaldehyde solution is 9～11, until paraformaldehyde all dissolves, be cooled to 30 ℃.
2. take 78 parts of anhydrous sodium sulphate and join in there-necked flask, take 573 parts of diethanolamine in constant pressure funnel, under stirring, slowly add diethanolamine, reaction is thermopositive reaction, controls temperature of reaction at 40 ℃, after diethanolamine is added dropwise to complete, be incubated 40 ℃, continue reaction 1 hour.Then be cooled to 30 ℃, remove by filter the sodium sulfate after planar water.
3. be warming up to 45～50 ℃, in vacuum tightness, be not less than under the condition of 0.095Mpa, underpressure distillation removes desolventizing n-propyl alcohol, and utilizes n-propyl alcohol and water azeotropic to remove and react the water generating, underpressure distillation 2 hours, obtain 3-(2-hydroxyethyl)-1,3-oxazolidine, yield 99.8%, 3-in gas phase analysis intermediate (2-hydroxyethyl)-1,3-oxazolidine content 99.9%, measures by karl-Fischer method, water-content 0.23%.
4. by vacuum distillation apparatus, change back reaction unit, be cooled to 40 ℃, add 2.8 parts of aluminum trichloride (anhydrous)s as catalyzer, take 730.6 parts of diethyl phosphites in constant pressure funnel, under stirring, slowly join in there-necked flask, control temperature of reaction at 40～50 ℃, after being added dropwise to complete, be warming up to 60 ℃, continue reaction 2 hours.
5. reaction mass temperature is down to room temperature, filtering recovering catalyst, obtains light yellow transparent liquid product N, two (2-hydroxyethyl) the AminomethylphosphoniAcid Acid diethyl esters of N-, yield is 99.4%, N in gas phase analysis product, and the content of two (2-hydroxyethyl) the AminomethylphosphoniAcid Acid diethyl esters of N-is 96%.It is 0.12% that karl-Fischer method records moisture content in product.Above-described part is mass parts, as follows.
Through nuclear-magnetism, GC-MS and infrared spectra, product is analyzed, see respectively Fig. 1-3, product main component is N, two (2-hydroxyethyl) the AminomethylphosphoniAcid Acid diethyl esters of N-, N in gas phase analysis proof product, the content of two (2-hydroxyethyl) the AminomethylphosphoniAcid Acid diethyl esters of N-is 96%.Gas phase analysis condition is: chromatographic column is DB-17, column length 30m, and post footpath 0.25mm, the thick 0.25m μ of liquid film, 50 ℃ keep 2 minutes, with 5 ℃/min, are warming up to 80 ℃, keep 5min, and 20 ℃/min is warming up to 260 ℃, keeps 10 minutes.Injector temperature is 280 ℃, 300 ℃ of sensing chamber, and hydrogen flame detector, solvent is ethanol.
Product
1h NMR data: (CDCl
3for solvent, TMS is interior mark): 1.33～1.37 (t, 6H ,-CH
3), 2.83～2.86 (t, 4H ,-NCH
2-), 3.02～3.05 (d, 2H, P-CH
2-N), 3.64～3.66 (t, 4H ,-CH
2oH), 4.14～4.19 (m, 4H ,-OCH
2-).
Makings detected result shows that molecular weight of product is 255, and theoretical molecular is 255.
Infrared spectra detected result (KBr, σ/cm
-1): 3386.79 (ν
-OH), 2928.92 (ν
-PCH2), 2946.2～2983.71 (ν
-CH2-CH3), 1212.37 (ν
-P=O), 1163.36 (ν
-C-N), 1024.01 (ν
-P-O)
Comparative example 1 (with reference to method in patent CN 1583768A)
(1) in reactor, add the formalin of 459 parts (by weight, lower with) 37%, be heated to 30 ℃, under stirring, add 573 parts of the diethanolamine of melting in advance, keep temperature of reaction at 30 ℃, react 1 hour.
(2) change reaction unit into vacuum distillation apparatus, in vacuum tightness, be not less than under the condition of 0.095MPa, 50 ℃ of decompressions steam moisture, then at 80 ℃, continue underpressure distillation 2 hours, obtain 3-(2-hydroxyethyl)-1,3-oxazolidine, yield 100%, 3-in gas phase analysis intermediate (2-hydroxyethyl)-1,3-oxazolidine content 95.32%, by karl-Fischer method, measure water-content 23.65%.
(3) by this water distilling apparatus, change back reaction unit, and cool to 40 ℃, add 4.6 parts of aluminum trichloride (anhydrous)s as catalyzer, under stirring, 730.6 parts of diethyl phosphites are added to 3-(2-hydroxyethyl)-1 in 1 hour, 3-oxazolidine, control temperature of reaction at 40～50 ℃, after being added dropwise to complete, be warming up to 60 ℃, continue reaction 2 hours.
(4) reaction mass temperature is down to room temperature, filtering recovering catalyst, obtain deep yellow transparent liquid product N, two (2-hydroxyethyl) the AminomethylphosphoniAcid Acid diethyl esters of N-, yield is 96%, N in gas phase analysis product, the content of two (2-hydroxyethyl) the AminomethylphosphoniAcid Acid diethyl esters of N-is 90%.It is 11.37% that karl-Fischer method records moisture content in product.
1. take 222 parts of propyl carbinols in the 2L there-necked flask with magnetic stirring apparatus, constant pressure funnel and thermometer, be warming up to 80 ℃, add 180 parts of paraformaldehyde solids, with sodium hydroxide solution, regulating the pH of paraformaldehyde solution is 9～11, until paraformaldehyde all dissolves, be cooled to 30 ℃.
2. take 100 parts of calcium oxide and join in there-necked flask, take 623.8 parts of diethanolamine in constant pressure funnel, under stirring, slowly add diethanolamine, reaction is thermopositive reaction, controls temperature of reaction at 40 ℃, after diethanolamine is added dropwise to complete, be warming up to 50 ℃, continue reaction 0.5 hour.Then be cooled to 30 ℃, remove by filter the calcium oxide after planar water.
3. be warming up to 45～50 ℃, in vacuum tightness, be not less than under the condition of 0.095MPa, solvent, n-butanol is removed in underpressure distillation, and utilizes propyl carbinol and water azeotropic to remove and react the water generating, underpressure distillation 2 hours, obtain 3-(2-hydroxyethyl)-1,3-oxazolidine, yield 99.8%, 3-in gas phase analysis intermediate (2-hydroxyethyl)-1,3-oxazolidine content 99.6%, measures by karl-Fischer method, water-content 0.28%.
4. by vacuum distillation apparatus, change back reaction unit, be cooled to 40 ℃, add 1 part of aluminum trichloride (anhydrous) as catalyzer, take 730.6 parts of diethyl phosphites in constant pressure funnel, under stirring, slowly join in there-necked flask, control temperature of reaction at 60 ℃, after being added dropwise to complete, be warming up to 80 ℃, continue reaction 1 hour.
5. reaction mass temperature is down to room temperature, filtered and recycled solid acid catalyst, obtain yellow transparent liquid product N, two (2-hydroxyethyl) the AminomethylphosphoniAcid Acid diethyl esters of N-, yield is 99.4%, N in gas phase analysis product, the content of two (2-hydroxyethyl) the AminomethylphosphoniAcid Acid diethyl esters of N-is 94%.It is 0.14% that karl-Fischer method records moisture content in product.
Embodiment 3
1. take 700 parts of Virahols in the 2L there-necked flask with magnetic stirring apparatus, constant pressure funnel and thermometer, be warming up to 60 ℃, add 180 parts of paraformaldehyde solids, with sodium hydroxide solution, regulating the pH of paraformaldehyde solution is 9～11, until paraformaldehyde all dissolves, be cooled to 30 ℃.
2. take 80 parts of anhydrous calciumsulphates and join in there-necked flask, take 519.8 parts of diethanolamine in constant pressure funnel, under stirring, slowly add diethanolamine, reaction is thermopositive reaction, controls temperature of reaction at 30 ℃, after diethanolamine is added dropwise to complete, be incubated 30 ℃, continue reaction 2 hours.Remove by filter the calcium sulfate after planar water.
3. be warming up to 45～50 ℃, in vacuum tightness, be not less than under the condition of 0.095MPa, underpressure distillation removes desolventizing Virahol, and utilizes Virahol and water azeotropic to remove and react the water generating, underpressure distillation 2 hours, obtain 3-(2-hydroxyethyl)-1,3-oxazolidine, yield 99.7%, 3-in gas phase analysis intermediate (2-hydroxyethyl)-1,3-oxazolidine content 99.8%, measures by karl-Fischer method, water-content 0.23%.
4. by vacuum distillation apparatus, change back reaction unit, be cooled to 40 ℃, add 5.0 parts of aluminum trichloride (anhydrous)s as catalyzer, take 669.8 parts of diethyl phosphites in constant pressure funnel, under stirring, slowly join in there-necked flask, control temperature of reaction at 50 ℃, be added dropwise to complete 50 ℃ of rear insulations, continue reaction 5 hours.
5. reaction mass temperature is down to room temperature, filtered and recycled solid acid catalyst, obtain yellow transparent liquid product N, two (2-hydroxyethyl) the AminomethylphosphoniAcid Acid diethyl esters of N-, yield is 99.3%, N in gas phase analysis product, the content of two (2-hydroxyethyl) the AminomethylphosphoniAcid Acid diethyl esters of N-is 95%.It is 0.11% that karl-Fischer method records moisture content in product.
Embodiment 4
1. take 360 parts of n-propyl alcohols in the 2L there-necked flask with magnetic stirring apparatus, constant pressure funnel and thermometer, be warming up to 70 ℃, add 180 parts of paraformaldehyde solids, with sodium hydroxide solution, regulating the pH of paraformaldehyde solution is 9～11, until paraformaldehyde all dissolves, be cooled to 30 ℃.
2. take 78 parts of anhydrous sodium sulphate and join in there-necked flask, take 573 parts of diethanolamine in constant pressure funnel, under stirring, slowly add diethanolamine, reaction is thermopositive reaction, controls temperature of reaction at 40 ℃, after diethanolamine is added dropwise to complete, be incubated 40 ℃, continue reaction 1 hour.Then be cooled to 30 ℃, remove by filter the sodium sulfate after planar water.
3. be warming up to 45～50 ℃, in vacuum tightness, be not less than under the condition of 0.095MPa, underpressure distillation removes desolventizing n-propyl alcohol, and utilizes n-propyl alcohol and water azeotropic to remove and react the water generating, underpressure distillation 2 hours, obtain 3-(2-hydroxyethyl)-1,3-oxazolidine, yield 99.5%, 3-in gas phase analysis intermediate (2-hydroxyethyl)-1,3-oxazolidine content 99.7%, measures by karl-Fischer method, water-content 0.25%.
4. by vacuum distillation apparatus, change back reaction unit, be cooled to 40 ℃, add 2.8 parts of aluminum trichloride (anhydrous)s and iron trichloride mixed catalyst, blending ratio is 1: 1, take 730.6 parts of diethyl phosphites in constant pressure funnel, under stirring, slowly join in there-necked flask, control temperature of reaction at 40～50 ℃, after being added dropwise to complete, be warming up to 60 ℃, continue reaction 2 hours.
5. reaction mass temperature is down to room temperature, filtered and recycled solid acid catalyst, obtain light yellow transparent liquid product N, two (2-hydroxyethyl) the AminomethylphosphoniAcid Acid diethyl esters of N-, yield is 99.3%, N in gas phase analysis product, the content of two (2-hydroxyethyl) the AminomethylphosphoniAcid Acid diethyl esters of N-is 94%.It is 0.14% that karl-Fischer method records moisture content in product.
Claims (10)
1. a N, the preparation method of two (2-hydroxyethyl) the AminomethylphosphoniAcid Acid diethyl esters of N-, comprises the following steps:
(1) in reactor, add solvent and paraformaldehyde solid, the mol ratio of solvent and paraformaldehyde is 0.5～2.0, in formaldehyde, under certain temperature and pH value condition, paraformaldehyde solid is dissolved completely;
(2) solution of (1) step is cooled to 25～40 ℃, and adds siccative in reactor, under stirring, add the diethanolamine of melting, control temperature of reaction 25～50 ℃ of reactions 0.5～2 hour, remove by filter siccative;
(3) the reaction solution underpressure distillation (2) step being obtained, except desolventizing, utilizes solvent and water azeotropic to dewater simultaneously, obtains 3-(2-hydroxyethyl)-1,3-oxazolidine;
(4) be cooled to 40～50 ℃, in reactor, add anhydrous lewis acid catalyst, be warming up to 40～80 ℃, drip while stirring diethyl phosphite, after being added dropwise to complete, at this temperature, continue reaction 1～6 hour;
In step (1), temperature is 60～80 ℃, and pH value is 8～12, and described solvent is ethanol, n-propyl alcohol, Virahol, isopropylcarbinol, propyl carbinol, Pentyl alcohol or primary isoamyl alcohol.
2. method according to claim 1, is characterized in that: in step (1), temperature is 65～75 ℃, and adopting sodium hydroxide solution to regulate the pH of reaction soln is 9～11, and the mol ratio of solvent and paraformaldehyde is 0.8～1.5, in formaldehyde.
3. according to the method described in any one in claim 1-2, it is characterized in that: the siccative described in step (2) is one or two or more in anhydrous sodium sulphate, anhydrous magnesium sulfate, anhydrous calciumsulphate or calcium oxide mixture in any proportion; The mol ratio of diethanolamine and siccative is 1:0.1～0.3, and during filtration drying agent, temperature is 30～40 ℃.
4. according to the method described in any one in claim 1-2, it is characterized in that: in step (2), temperature of reaction is 30～40 ℃, and the reaction times is 1～1.5 hour.
5. method according to claim 4, it is characterized in that: the mol ratio of paraformaldehyde and diethanolamine is 0.9～1.4:1, in formaldehyde, the diethyl phosphite consumption adding in step (4) meets: intermediate 3-(2-hydroxyethyl)-1, and the mol ratio of 3-oxazolidine and diethyl phosphite is 0.8～1.2:1.
6. N according to claim 5, the preparation method of two (2-hydroxyethyl) the AminomethylphosphoniAcid Acid diethyl esters of N-, is characterized in that: underpressure distillation vacuum tightness >=0.095MPa in step (3), is warming up to 45～50 ℃.
7. N according to claim 6, the preparation method of two (2-hydroxyethyl) the AminomethylphosphoniAcid Acid diethyl esters of N-, it is characterized in that: in step (4), anhydrous lewis acid catalyst is aluminum trichloride (anhydrous), Calcium Chloride Powder Anhydrous, iron trichloride the mixture in any proportion of the one or two or more in titanium tetrachloride or magnesium chloride.
8. N according to claim 7, the preparation method of two (2-hydroxyethyl) the AminomethylphosphoniAcid Acid diethyl esters of N-, it is characterized in that: in step (4), the add-on of anhydrous lewis acid catalyst is 3-(2-hydroxyethyl)-1,0.05～0.4% of 3-oxazolidine and diethyl phosphite gross weight.
9. N according to claim 8, the preparation method of two (2-hydroxyethyl) the AminomethylphosphoniAcid Acid diethyl esters of N-, it is characterized in that: in step (4), the add-on of anhydrous lewis acid catalyst is 3-(2-hydroxyethyl)-1,0.15～0.3% of 3-oxazolidine and diethyl phosphite gross weight.
10. N according to claim 8, the preparation method of two (2-hydroxyethyl) the AminomethylphosphoniAcid Acid diethyl esters of N-, is characterized in that: in step (4), temperature of reaction is 50～60 ℃, and the reaction times is 2～3 hours.
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| CN104130287A (en) * | 2014-06-23 | 2014-11-05 | 浙江中科恒泰新材料科技有限公司 | Toughening flame retardant, preparation method thereof, and composition prepared from toughening flame retardant |
| CN106432740B (en) * | 2016-09-08 | 2020-06-09 | 四川大学 | Hydroxyl-containing polyphosphonate flame retardant and preparation method and application thereof |
| US10072032B2 (en) * | 2016-09-19 | 2018-09-11 | Afton Chemical Corporation | AminoBisPhosphonate antiwear additives |
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