A method for preparing a soluble copper organophosphonate

Abstract

The application provides a preparation method of soluble organic copper phosphonate, in particular to a water-soluble organic copper phosphonate complex salt prepared by the reaction of unsaturated quaternary ammonium cation organic phosphonate betaine containing glycidyl in the molecular structure and water-soluble inorganic copper salt, which can be used as a free radical grafting functional monomer on the surface of polyolefin and other high molecular materials, or mixed into the copolymerization of acrylate, acrylonitrile or other olefin monomers, and can also impart the obtained high molecular material with the functional effects of organic copper phosphonate, quaternary ammonium ionization, hydrophilicity, antibacterial property, antifouling property and the like; and can also be used for the ring-opening grafting modification of high molecular materials such as starch, cellulose, polyurethane, polyamide and the like containing amino or hydroxyl in the structure, and the chemical stability of the new functional high molecular material prepared thereby in the weak alkaline water environment is high.

Description

TECHNICAL FIELD

[0001] The present application relates to a preparation method of a soluble organic copper phosphonate complex salt, in particular to an organic copper phosphonate complex salt prepared by a metathesis reaction using an unsaturated quaternary ammonium cation organic phosphonate betaine containing a glycidyl group in the molecular structure and a water-soluble inorganic copper salt as raw materials, which can be used as an aqueous ionic monomer for the preparation or functional modification of ionic polymer materials, and belongs to the field of functional polymer materials. TECHNICAL BACKGROUND

[0002] Since 2008, when organotin marine antifouling coatings were completely banned, people began to use Cu + or Cu 2+ as a cheap bactericide in marine antifouling systems. Related Cu + or Cu 2+ is often mechanically mixed into antibacterial coatings in the form of Cu2O or CuO, and such marine antifouling coatings account for more than 80% of the market share of antifouling coatings. However, because Cu2O or CuO has very low solubility in seawater, in order to obtain a coating with a high and stable Cu + or Cu 2+ release rate for a long-lasting antifouling effect, an excessive amount of Cu2O particles or CuO is often added, which in turn leads to a high Cu + or Cu 2+ release rate on the surface of marine engineering equipment in the early stage, and some of it has already been lost into the seawater before it has even been used, resulting in an excessively high Cu + or Cu 2+ content in the nearby waters, which destroys the marine ecological environment. It is of great significance to develop a low-copper antifouling agent with high efficiency, broad spectrum, slow release, and long-term effect while ensuring the high antibacterial and antifouling efficiency of the coating.

[0003] Phosphorus-containing functional polymer materials not only have chelation and solidification effects on heavy metal ions, but also can realize the enrichment and extraction separation of low-concentration noble and heavy metal ions or rare earth elements. In addition, they have the functions of flame retardation and biological activity, and are used as flame-retardant polymer materials, antibacterial polymer materials, and biological polymer materials. At present, unsaturated phosphoric acid or unsaturated phosphonic acid and their derivatives are mainly used as phosphine-containing functional monomers, such as vinyl or allyl phosphoric acid and its derivatives, or vinyl or allyl phosphonic acid and its derivatives. Such phosphorus-containing monomers have single function and few varieties. Phosphonate or quaternary phosphonium salt derived from acrylate or acrylamide as a polymerizable monomer is also a research object of the current phosphine-containing functional monomers. However, the chemical stability of such phosphine-containing functional monomers is relatively low, and the price is high, so they are limited in practical application. Meanwhile, it is well known to professionals that inorganic copper phosphate and copper phosphonate are insoluble in water, and their pKsp is between 17 and 37. Some organic copper salts such as ethyl copper phosphonate, phenyl copper phosphonate or diethyl copper hypophosphite also have low solubility in water, and their pKsp is between 7 and 15. The insolubility of copper salt in water creates conditions for the establishment of organic polymer copper salt with slow-release copper ions. How to realize the polymerization of water-insoluble copper salt is the substantial feature of the present invention.

[0004] The existing research results and application practices show that the zwitterionic polymer has equal amounts of anions and cations on the polymer chain, and the whole is electrically neutral. Through the water-solubilization of anions and cations and the hydrogen bond effect, a dense and stable hydration layer is formed, which produces physical and energy contact barriers to the adhesion of bacteria, reduces the adhesion of bacteria on the surface of metal, ceramic, glass and polymer materials, and further inhibits the formation of biofilm, so as to achieve the effect of antibacterial and antifouling. The zwitterionic monomers with relatively high usage rate are sulfobetaine, carboxybetaine and phosphorylcholine. Relatively speaking, there are few varieties of organic phosphonic betaine, and the probability of occurrence in literature and patents is not high.

[0005] Therefore, on the basis of analyzing the application characteristics and application requirements of existing copper-containing antibacterial agents, the research and application results of grafting modification of the surface of polymer materials by phosphine-containing functional monomers and quaternary ammonium cation monomers, and the previous research results of the surface grafting modification of aromatic polyamide composite membranes by the research group, the present invention provides an unsaturated quaternary ammonium cation organic copper phosphonate complex salt containing glycidyl groups with high chemical stability, high biocidal and antibacterial biological activity, and high hydrophilicity in weak alkaline water environment, which is used as Cu 2+A copper-containing functional monomer with good sustained-release effect, synergistic and long-lasting antibacterial efficacy, high hydrophilicity and significant chlorine resistance. Professionals are well aware that copper ethylphosphonate, copper diethylphosphinate or copper phenylphosphonate are all organic copper phosphonates that are insoluble in water or sparingly soluble in water. The inventors are utilizing the characteristics of copper ethylphosphonate, copper diethylphosphinate or copper phenyl phosphate that are insoluble in water or sparingly soluble in water to form a mechanism for slow-release copper ions in water, and in combination with an organic phosphonic acid betaine disclosed in CN202411427199.6, a complex salt with the structural characteristics of a zwitterionic monomer. It is an unsaturated quaternary ammonium cation organic copper phosphonate complex salt prepared by double decomposition reaction using the organic phosphonic acid betaine and a water-soluble inorganic copper salt as raw materials, and the complex salt has certain water solubility and broad spectrum and high antibacterial properties. Summary of the Invention

[0006] The present invention provides a soluble organic copper phosphonate having a chemical structure shown in general formula (I):

[0007]

[0008] Wherein R1 in the general formula (Ⅰ) is selected from C1~C 18 Hydrocarbon, R2 is selected from C1~C 18 Hydrocarbyl or hydroxyl, said X 2- Refers to 2Cl - ,2NO3 - or SO4 2- One of them, n is a natural number from 1 to 12.

[0009] The soluble organic copper phosphonate of the present invention is a water-soluble organic copper phosphonate complex salt prepared by reacting an unsaturated quaternary ammonium cation organic phosphonate betaine containing a glycidyl group in its molecular structure with a water-soluble inorganic copper salt. The specific preparation method is as follows: 2-(N-glycidyl-N-alkyl-N-allylammonium)ethylphosphonic acid inner salt is weighed and dissolved in water with a pH of 7.0 to 8.5 to prepare a 2-(N-glycidyl-N-alkyl-N-allylammonium)ethylphosphonic acid inner salt aqueous solution; then, a water-soluble copper salt is weighed and dissolved in water with a pH of 5. At room temperature, the 2-(N-glycidyl-N-alkyl-N-allylammonium)ethylphosphonate aqueous solution and the copper salt aqueous solution are slowly added to the reactor while stirring for reaction. After the addition is completed, the temperature of the materials in the reactor is raised to 50-90° C. and the reaction is carried out for 2-12 hours. After that, negative pressure concentration is performed to evaporate most of the water in the reactor. The temperature of the reaction product system is then lowered to -15-5° C. and stored for 2-20 hours. The soluble organic copper phosphonate is obtained by filtering, washing, and vacuum drying.

[0010] The amount of the 2-(N-glycidyl-N-hydrocarbyl-N-allyl ammonium) ethyl organic phosphonic acid inner salt is 2.0-2.2 times the molar amount of the water-soluble copper salt, and the amount of water is 0.25-2.5 times the mass of the 2-(N-glycidyl-N-hydrocarbyl-N-allyl ammonium) ethyl phosphonic acid inner salt and 0.2-2.0 times the mass of the water-soluble copper salt, respectively.

[0011] The 2-(N-glycidyl-N-hydrocarbyl-N-allyl ammonium) ethyl phosphonic acid inner salt is prepared by the method disclosed in CN202411427199.6 and has a chemical structure shown in general formula (II):

[0012]

[0013] In the general formula (II), R1 is selected from C1-C6 hydrocarbyl, R2 is selected from C1-C6 hydrocarbyl or hydroxyl, and X is selected from Cl, Br or I. 18 hydrocarbyl, R2 is selected from C1-C6 hydrocarbyl or hydroxyl; and the water-soluble copper salt refers to one of copper sulfate pentahydrate, copper nitrate trihydrate or copper chloride dihydrate. 18

[0014] The soluble organic copper phosphonate provided by the present application has the following beneficial effects:

[0015] ① The soluble organic copper phosphonate of the general formula (I) provided by the present application is a soluble organic copper phosphonate salt with the characteristics of slow release of Cu2+, which can be used as a water-based functional monomer for surface grafting modification of high molecular materials such as polyolefins, and can also be mixed into copolymerization of acrylate, acrylonitrile or other olefin monomers, thereby imparting the obtained high molecular material with the functional effects of organic copper phosphonate, quaternary ammonium cationization, hydrophilicity, long-acting antibacterial property, antifouling property and the like. 2+

[0016] ② The soluble organic copper phosphonate of the general formula (I) provided by the present application can be used for ring-opening grafting modification of high molecular materials such as starch, cellulose, polyurethane and polyamide containing amino groups or hydroxyl groups, and the new functional high molecular material thus prepared has high chemical stability in a weak alkaline water environment.

[0017] ③ The soluble organic copper phosphonate of the general formula (I) provided by the present application has solubility in water or small molecular alcohols, and the grafting process of the high molecular material can be completed in an aqueous phase, thereby avoiding the generation of VOCs in the grafting process.

[0018] ④ The preparation method of the soluble organic copper phosphonate of the general formula (I) provided by the present application is simple, and the process is safe and efficient.

[0019] ⑤ The soluble organic copper phosphonate of the general formula (I) provided by the present application has scientific structure design, comprehensive functions, optimized technology and superior performance when used as a water-based functional monomer. DETAILED DESCRIPTION ​​

[0020] The soluble organic copper phosphonate and its preparation method provided by the present invention are further illustrated by the following examples, the purpose of which is to provide a better understanding of the present invention.

[0021] Example 1 Preparation of soluble organic copper phosphonate (1)

[0022] 20 g of 2-(N-glycidyl-N,N-diallylammonium)ethylphosphonic acid inner salt of formula ① was weighed and dissolved in 60 g of alkaline aqueous solution with a pH of 7.5 to 8.0. 9 g of copper sulfate pentahydrate was weighed and dissolved in 30 g of acidic aqueous solution with a pH of 5.0 to 5.5. The two aqueous solutions were then slowly added to a reactor at room temperature. After the addition was completed, the temperature of the material in the reactor was increased to 50 to 60° C. and the reaction was carried out for 4 hours. The reaction was concentrated by vacuum distillation. After about 60 to 70 g of water was evaporated, the temperature of the reaction product system was lowered to 0 to 5° C. and allowed to stand for 4 hours. Thereafter, a dark blue solid product was collected by filtration, and the dark blue solid product was recrystallized using methanol. The product was then placed in a vacuum drying oven and dried to constant weight to obtain 27.3 g of soluble organic copper phosphonate (1) dark blue product. The product yield was 96.1% based on copper sulfate pentahydrate. The elemental analysis of the soluble organic copper phosphonate (1) product is as follows: C32.89%, H6.66%, N3.48%, Cu8.01%, which is consistent with the molecular formula C 22 H 52 CuN2O 18 The calculated values ​​of P2S are C33.44%, H6.63%, N3.55%, and Cu8.04%, which are consistent with the above-mentioned product. The infrared spectrum data of the product is: 3372 cm -1 The characteristic absorption peak of hydroxyl group OH, 3037cm -1 Characteristic absorption peaks of C=CH, 2924 and 2873 cm -1 Characteristic absorption peaks of methyl and methylene, 1642 and 1446 cm -1 is the characteristic absorption peak of C=C, 1338cm -1 is the characteristic absorption peak of CN, 1232 cm -1 Characteristic absorption peaks of P=O double bond, 1138, 1056, 1002 cm -1 The absorption peaks are those of PO or COC.

[0023] The above analysis and characterization confirmed that the chemical name of the soluble organic copper phosphonate (1) product is hexahydrated bis(2-(N-glycidyl-N,N-diallylammonium)ethylphosphonate) copper sulfate, which has the structural characteristics of formula (1):

[0024]

[0025] Wherein the 2-(N-glycidyl-N,N-diallyl ammonium) ethyl phosphonic acid inner salt of formula 1 is prepared by the method of CN202411427199.6 Example 1, specifically by the following steps:

[0026] Step one, preparation of 2-(N,N-diallyl amino) ethyl phosphonic acid diethyl ester

[0027] Take 30 grams of ethanol, 18 grams of diallylamine and 18 grams of vinyl phosphonic acid diethyl ester in the reaction kettle, increase the temperature of the material in the reaction kettle to 45-50℃, after stirring for 16 hours, negative pressure rotary evaporation of ethanol and unreacted diallylamine, the analysis of the residue is 29.7 grams, 2-(N,N-diallyl amino) ethyl phosphonic acid diethyl ester content is 94.9%, the yield of 2-(N,N-diallyl amino) ethyl phosphonic acid diethyl ester is calculated to be 98.4%.

[0028] Step two, preparation of 2-(N-glycidyl-N,N-diallyl ammonium) ethyl phosphonic acid di(trimethylsilyl) ester

[0029] In the reaction kettle, add 45 grams of dichloromethane to completely dissolve 29.7 grams of 2-(N,N-diallyl amino) ethyl phosphonic acid diethyl ester, slowly add 31.5 grams of trimethylsilyl bromide to the reaction kettle at room temperature, stir for 24 hours, rotary evaporation of dichloromethane and unreacted trimethylsilyl bromide, then add 70 grams of epichlorohydrin to the reaction kettle, stir to mix evenly, then increase the temperature of the material in the reaction kettle to 50-55℃, stir for 48 hours to complete the quaternary ammonium salt reaction, then rotary evaporation to remove dichloromethane and excess epichlorohydrin, add 35 grams of tert-butyl alcohol to the reaction kettle, recrystallize the residue in the reaction kettle, and dry to constant weight to obtain 2-(N-glycidyl-N,N-diallyl ammonium) ethyl phosphonic acid di(trimethylsilyl) ester.

[0030] Step three, preparation of 2-(N-glycidyl-N-hydrocarbyl-N-allyl ammonium) ethyl phosphonic acid inner salt

[0031] The 2-(N-glycidyl-N-hydrocarbyl-N-allyl ammonium) ethyl phosphonate inner salt product was obtained by adding 50 g of t-butanol and 40 g of D301 weak basic ion exchange resin into a reaction kettle at room temperature, gradually adding 15 g of deionized water, stirring for 4 hours, and then filtering the mother liquor after the ion exchange resin was removed. The solid product was obtained by cooling the mother liquor to -20 to -10 °C. The solid product was washed by soaking in t-butanol, and then dried in a vacuum drying oven until the weight was constant. The yield of the 2-(N-glycidyl-N-hydrocarbyl-N-allyl ammonium) ethyl phosphonate inner salt product was 20.3 g, which was 70.9% based on diethyl vinylphosphonate. The melting point of the product was 108.5 °C (thermal decomposition). The infrared spectrum data (KBr pellet) of the 2-(N-glycidyl-N-hydrocarbyl-N-allyl ammonium) ethyl phosphonate inner salt product were as follows: 3447 cm-1 was the characteristic absorption peak of O-H, 3029 cm-1 was the characteristic absorption peak of C=C-H, 2937 cm-1 and 2874 cm-1 were the characteristic absorption peaks of methylene, 1642 cm-1 and 1442 cm-1 were the characteristic absorption peaks of C=C or C-N, 1252 cm-1 was the characteristic absorption peak of P=O double bond, 1128 cm-1, 1041 cm-1 and 997 cm-1 were the characteristic absorption peaks of C-O-C and P-O. -1 3029 cm-1 was the characteristic absorption peak of C=C-H, 2937 cm-1 and 2874 cm-1 were the characteristic absorption peaks of methylene, 1642 cm-1 and 1442 cm-1 were the characteristic absorption peaks of C=C or C-N, 1252 cm-1 was the characteristic absorption peak of P=O double bond, 1128 cm-1, 1041 cm-1 and 997 cm-1 were the characteristic absorption peaks of C-O-C and P-O. -1 3029 cm-1 was the characteristic absorption peak of C=C-H, 2937 cm-1 and 2874 cm-1 were the characteristic absorption peaks of methylene, 1642 cm-1 and 1442 cm-1 were the characteristic absorption peaks of C=C or C-N, 1252 cm-1 was the characteristic absorption peak of P=O double bond, 1128 cm-1, 1041 cm-1 and 997 cm-1 were the characteristic absorption peaks of C-O-C and P-O. -1 3029 cm-1 was the characteristic absorption peak of C=C-H, 2937 cm-1 and 2874 cm-1 were the characteristic absorption peaks of methylene, 1642 cm-1 and 1442 cm-1 were the characteristic absorption peaks of C=C or C-N, 1252 cm-1 was the characteristic absorption peak of P=O double bond, 1128 cm-1, 1041 cm-1 and 997 cm-1 were the characteristic absorption peaks of C-O-C and P-O. -1 3029 cm-1 was the characteristic absorption peak of C=C-H, 2937 cm-1 and 2874 cm-1 were the characteristic absorption peaks of methylene, 1642 cm-1 and 1442 cm-1 were the characteristic absorption peaks of C=C or C-N, 1252 cm-1 was the characteristic absorption peak of P=O double bond, 1128 cm-1, 1041 cm-1 and 997 cm-1 were the characteristic absorption peaks of C-O-C and P-O. -1 3029 cm-1 was the characteristic absorption peak of C=C-H, 2937 cm-1 and 2874 cm-1 were the characteristic absorption peaks of methylene, 1642 cm-1 and 1442 cm-1 were the characteristic absorption peaks of C=C or C-N, 1252 cm-1 was the characteristic absorption peak of P=O double bond, 1128 cm-1, 1041 cm-1 and 997 cm-1 were the characteristic absorption peaks of C-O-C and P-O. 1 3029 cm-1 was the characteristic absorption peak of C=C-H, 2937 cm-1 and 2874 cm-1 were the characteristic absorption peaks of methylene, 1642 cm-1 and 1442 cm-1 were the characteristic absorption peaks of C=C or C-N, 1252 cm-1 was the characteristic absorption peak of P=O double bond, 1128 cm-1, 1041 cm-1 and 997 cm-1 were the characteristic absorption peaks of C-O-C and P-O.

[0032]

[0033] Preparation of soluble copper organophosphonate (2) of Example 2

[0034] According to the preparation method and operation steps of Example 1, replace "2-(N-glycidyl-N, N-diallyl ammonium) ethyl phosphonic acid inner salt" in the formula ① with "2-(N-glycidyl-N-benzyl-N-allyl ammonium) ethyl phosphonic acid inner salt" in the formula ②, and replace "9 grams of copper sulfate pentahydrate is dissolved in 30 grams of acidic aqueous solution with pH of 5.0-5.5" with "4.9 grams of copper chloride dihydrate is dissolved in 20 grams of acidic aqueous solution with pH of 5.0-5.5". A dark blue product of soluble organic copper phosphonate (2) is prepared, and through elemental analysis and instrument analysis, it is confirmed that the chemical name of the soluble organic copper phosphonate (2) product is bis(2-(N-glycidyl-N-benzyl-N-allyl ammonium) ethyl phosphonic acid) copper chloride tetrahydrate, which has the structural characteristics of formula (2):

[0035]

[0036] The 2-(N-glycidyl-N-benzyl-N-allyl ammonium) ethyl phosphonic acid inner salt is prepared by the method of CN202411427199.6 Example 2, and the specific preparation method and steps are similar to Example 1. Replace the diallyl amine in Step 1 of Example 1 of the present application with N-benzyl-N-allyl amine, and 2-(N-glycidyl-N-benzyl-N-allyl ammonium) ethyl phosphonic acid inner salt of formula ② can be prepared:

[0037]

[0038] Properties of soluble organic copper phosphonate of Example 3

[0039] At a constant temperature of 25±0.5℃, gradually add the soluble organic copper phosphonate of Example 1 or Example 2 to 10 grams of deionized water, stir and dissolve for 2 hours until saturation is reached, and calculate the solubility of the soluble organic copper phosphonate of Example 1 or Example 2 in deionized water. Dilute the aqueous solution of the soluble phosphonate copper of Example 1 or Example 2 with water according to the dilution ratio of 1:2, 1:10, 1:50, 1:100, 1:1000, 1:10000, mix 2mL of the aqueous solution of the soluble organic copper phosphonate of Example 1-2 with 10mL of culture medium, add 2 drops of pathogenic bacteria suspension, mix thoroughly, and incubate in a 37℃ incubator for 24 hours; observe the growth of the pathogenic bacteria, calculate the minimum inhibitory concentration (MIC), and the test results are shown in Table 1.

[0040] Properties of water-soluble organic copper phosphonate

[0041]

[0042] As can be seen from the experimental test results in Table 1, the organic copper phosphonate described in the present application embodiment 1 or embodiment 2 belongs to water-soluble organic copper phosphonate complex salt. Compared with insoluble or hardly soluble organic copper phosphonate such as copper ethyl phosphonate, copper propyl phosphonate, copper phenyl phosphonate and the like, the water solubility of the organic copper phosphonate described in the present application embodiment 1-2 is quite high, which is due to the fact that the hydrophilic modification by the quaternary ammonium cation greatly improves the solubility and dispersibility thereof in water. The experimental test results in Table 1 show that the soluble organic copper phosphonate described in the present application embodiment 1 or embodiment 2 has high antibacterial activity, which may be due to the synergistic antibacterial effect of the quaternary ammonium cation, the alkylene oxide and the copper ion in the molecular structure of the soluble organic copper phosphonate described in the present application.

Claims

1. A method for preparing a soluble organic copper phosphonate, characterized in that The method is as follows: weighing 2-(N-glycidyl-N-alkyl-N-allylammonium)ethylphosphonic acid inner salt and dissolving it in water with a pH of 7.0 to 8.5 to prepare a 2-(N-glycidyl-N-alkyl-N-allylammonium)ethylphosphonic acid inner salt aqueous solution; then weighing a water-soluble copper salt and dissolving it in water with a pH of 5.5 to 6.5 to prepare a copper salt aqueous solution; and slowly adding the 2-(N-glycidyl-N-alkyl-N-allylammonium)ethylphosphonic acid inner salt aqueous solution and the copper salt aqueous solution to a reactor at room temperature, stirring the reaction while adding the materials, raising the temperature of the materials in the reactor to 50 to 90° C. and allowing the reaction to proceed for 2 to 12 hours, then performing negative pressure concentration to evaporate most of the water in the reactor, and then lowering the temperature of the reaction product system to -15 to 5° C. and storing it for 2 to 20 hours. The reaction product is filtered, washed, and vacuum dried to obtain a soluble organic copper phosphonate having the chemical structure shown in the general formula (I): Wherein R1 in the general formula (Ⅰ) is selected from C1~C 18 Hydrocarbon, R2 is selected from C1~C 18 Hydrocarbyl or hydroxyl, said X 2- Refers to 2Cl - ,2NO3 - or SO4 2- One of the following, n is a natural number from 1 to 12; The 2-(N-glycidyl-N-alkyl-N-allylammonium)ethylphosphonic acid inner salt has a chemical structure shown in the general formula (II): Wherein R1 in the general formula (II) is selected from C1~C 18 Hydrocarbon, R2 is selected from C1~C 18 Hydrocarbyl or hydroxyl groups; The amount of the 2-(N-glycidyl-N-alkyl-N-allylammonium)ethyl organic phosphonic acid inner salt is 2.0 to 2.2 times the molar amount of the water-soluble copper salt, and the amount of water is 0.25 to 2.5 times the mass of the 2-(N-glycidyl-N-alkyl-N-allylammonium)ethyl phosphonic acid inner salt and 0.2 to 2.0 times the mass of the water-soluble copper salt.

2. The method for preparing a soluble organic copper phosphonate according to claim 1, characterized in that The water-soluble copper salt refers to one of copper sulfate pentahydrate, copper nitrate trihydrate or copper chloride dihydrate.

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