CN114292408B - Hyperbranched phosphorus-free water treatment agent containing tertiary amine and preparation method and application thereof - Google Patents
Hyperbranched phosphorus-free water treatment agent containing tertiary amine and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a hyperbranched phosphorus-free water treatment agent containing tertiary amine and a preparation method and application thereof, wherein epoxy alcohol compounds and unsaturated esters containing tertiary amine structures are subjected to heating reaction at the temperature lower than 90 ℃ to obtain hyperbranched polyether intermediates, then acid substance solutions are added under the action of catalysts to perform carboxylation reaction at the temperature lower than 90 ℃, and the phosphorus-free water treatment agent containing tertiary amine structures is prepared after post-treatment; the unsaturated ester containing tertiary amine structure is acrylic acid dimethylamino ethyl ester or dimethylamino propyl acrylamide; the catalyst is concentrated sulfuric acid; the acidic substance solution is a DMF solution containing acid anhydride. The water treatment agent prepared by the invention has excellent flocculation, scale inhibition and antibacterial effects under the condition of small dosage; the water treatment agent is used for water treatment in a reverse osmosis membrane system, has wide pH application range, not only has excellent water purification effect, but also avoids the mutual restriction and antagonism when the traditional water treatment agents with various different purposes are compounded and used, and is a green environment-friendly water treatment agent.
Description
Technical Field
The invention relates to the technical field of water treatment agent synthesis, in particular to a hyperbranched phosphorus-free water treatment agent containing tertiary amine and a preparation method and application thereof.
Background
The reverse osmosis method has the advantages of high desalination rate, small occupied area, high automation degree, environmental protection and the like, and is widely applied to the fields of food, medicine, chemical industry, sewage treatment, pure water preparation, seawater desalination and the like. The reverse osmosis membrane is an important component in membrane separation technology, and has very excellent interception and filtration capacity on impurities such as inorganic matters, organic matters, colloid, metal ions and the like in water.
However, in the reverse osmosis membrane operation system, excessive deposition of harmful substances such as corrosives, metal ions, colloids, and microorganisms in water may destroy the integrity of the membrane, affect the filtration efficiency of the reverse osmosis device, and greatly reduce the service life of the membrane. Therefore, in the actual use process, various water treatment agents such as corrosion inhibitors, water treatment agents, bactericides, flocculating agents, purifying agents, cleaning agents, pre-filming agents and the like are added to obtain the civil or industrial water meeting the standard.
However, the existing water treatment agents with different functions, different structures and different use conditions often cause the restriction effect among the components due to improper combination, thereby seriously reducing the use effect. Moreover, most of the traditional scale inhibition and dispersion agents are organic phosphorus composite water treatment agents, and although the traditional scale inhibition and dispersion agents have excellent flocculation and scale inhibition effects, the traditional scale inhibition and dispersion agents can provide nutrient sources for bacteria and algae in water bodies, promote the growth of the bacteria and the algae and aggravate the eutrophication of the water bodies. Therefore, the development of environment-friendly multi-effect phosphorus-free water treatment agent is always a hotspot and difficulty for industrial research and development.
Disclosure of Invention
In order to solve the technical problem of water eutrophication caused by the organic phosphorus composite water treatment agent, a hyperbranched non-phosphorus water treatment agent containing tertiary amine and a preparation method and application thereof are provided. The phosphorus-free water treatment agent disclosed by the invention is a multi-effect phosphorus-free green hyperbranched scale-inhibiting dispersant, and has good antibacterial, flocculation and scale-inhibiting effects.
In order to achieve the purpose, the invention is realized by the following technical scheme:
a preparation method of a hyperbranched phosphorus-free water treatment agent containing tertiary amine comprises the following steps:
heating epoxy alcohol compounds and unsaturated esters containing tertiary amine structures at a temperature lower than 90 ℃ to react to obtain hyperbranched polyether intermediates, adding an acidic substance solution under the action of a catalyst to perform a carboxylation reaction at a temperature lower than 90 ℃, and performing post-treatment to obtain the phosphorus-free water treatment agent containing tertiary amine structures.
Further, the epoxy alcohol compound is epoxy propanol; the unsaturated ester containing a tertiary amine structure is dimethylaminoethyl acrylate (DMAEA) or dimethylaminopropyl acrylamide (DMAPAA); the catalyst is concentrated sulfuric acid with the mass fraction of more than or equal to 70%; the acidic substance solution is DMF solution containing acid anhydride, and the molar volume ratio of the acid anhydride to the DMF is (0.05-0.15) mol/10mL.
Still further, the acid anhydride is succinic anhydride or maleic anhydride.
Still further, the mol ratio of the epoxypropanol, the unsaturated ester containing a tertiary amine structure and the acid anhydride is (3-5): 5 (1).
Further, the reaction temperature of the heating reaction is 70-80 ℃, and the reaction time is 40-60min; the reaction temperature of the carboxylation reaction is 70-80 ℃, and the reaction time is 3-4h.
Further, the post-treatment process comprises the steps of adopting glacial ethyl ether to settle products after the carboxylation reaction is finished, collecting precipitates, respectively carrying out dissolving/settling operations with methanol/ethyl ether for 2-3 times, and finally drying the collected precipitates at 30 ℃.
The invention also provides the hyperbranched phosphorus-free water treatment agent containing the tertiary amine prepared by the preparation method.
The last aspect of the invention provides application of the hyperbranched non-phosphorus water treatment agent containing tertiary amine in a reverse osmosis membrane system, wherein the adding amount of the hyperbranched non-phosphorus water treatment agent containing tertiary amine in water to be treated is 2-30mg/L, and the pH value of the water to be treated is 2-12.
The beneficial technical effects are as follows:
the phosphorus-free water treatment agent synthesized by the invention has tertiary amine groups and a hyperbranched structure, and both the hyperbranched chains and the chain ends have reactive functional groups (carboxyl, hydroxyl, double bonds and the like) for reaction, so that the effects of all the groups on flocculation, scale inhibition and sterilization can be exerted to the maximum extent. Meanwhile, the method has extremely remarkable effect on reducing the chemical oxygen index and the biological oxygen index in the water body.
The phosphorus-free water treatment agent prepared by the invention has a large amount of carboxyl, can effectively flocculate calcium, magnesium, zinc, iron and other ions in water by matching with a hyperbranched structure, prevents ions which are easy to scale from depositing on a reverse osmosis membrane system, and prolongs the service life.
The tertiary amine structure contained in the phosphorus-free water treatment agent prepared by the invention can form nanoparticles in water, and can effectively inhibit the growth of fungi and algae in the water on a reverse osmosis membrane system for a long time. Moreover, the water treatment agent disclosed by the invention is phosphorus-free and sulfur-free in chemical structure, does not cause water body enrichment, and greatly reduces environmental pollution.
The phosphorus-free water treatment agent prepared by the invention has wider use weather resistance, can play a role in wider use temperature and pH value range, and can be well compounded with other water treatment agents to play a synergistic effect.
The phosphorus-free water treatment agent disclosed by the invention is simple in preparation method, short in production period and greatly reduced in production cost, and is prepared by a one-pot method.
Drawings
FIG. 1 is an FTIR spectrum of the product of hyperbranched non-phosphorus water treatment agent containing tertiary amine of example 2 before and after the occurrence of carboxylation reaction.
FIG. 2 is an FTIR spectrum of the product of the hyperbranched non-phosphorus water treatment agent containing tertiary amine of example 4 before and after the occurrence of carboxylation reaction.
FIG. 3 is a graph of an antibacterial experiment using the hyperbranched phosphorus-free water treatment agent containing tertiary amine of example 3, measured by an agar dilution method at different feed concentrations.
FIG. 4 is the chemical structure of the hyperbranched phosphorus-free water treatment agent II obtained in example 2 1 H-NMR spectrum.
FIG. 5 is the chemical structure of the hyperbranched phosphorus-free water treatment agent IV of example 4 1 H-NMR spectrum.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention and the accompanying drawings, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. The following description of at least one exemplary embodiment is merely illustrative in nature and is in no way intended to limit the invention, its application, or uses. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Unless specifically stated otherwise, the numerical values set forth in these examples do not limit the scope of the invention. Techniques, methods known to those of ordinary skill in the relevant art may not be discussed in detail, but are intended to be part of the specification where appropriate. In all examples shown and discussed herein, any particular value should be construed as merely illustrative, and not limiting. Thus, other examples of the exemplary embodiments may have different values.
Example 1
A preparation method of a hyperbranched phosphorus-free water treatment agent containing tertiary amine comprises the following steps:
2.22g (0.03 mol) of epoxy propanol and 1.996g (0.01 mol) of dimethylaminoethyl acrylate are added at room temperature and are placed at 80 ℃ for reaction for 40min to obtain a hyperbranched polyether intermediate with a chemical structure shown in the formula I, and the reaction equation of the process is as follows:
then adding 8mL of N, N-dimethylformamide, 6g (0.06 mol) of succinic anhydride and 0.11g of concentrated sulfuric acid into the reaction system of the hyperbranched polyether intermediate, stirring until a uniform solution is formed, carrying out a carboxylation reaction for 4 hours at 70 ℃, and obtaining a reaction solution containing a product after the reaction is finished, wherein the product is the hyperbranched non-phosphorus water treatment agent containing the tertiary amine and having the chemical structure of the formula II, and the reaction equation of the process is as follows:
and (3) dripping the reaction liquid containing the product into glacial ethyl ether for sedimentation, collecting the formed precipitate, respectively dissolving the precipitate by using methanol/ethyl ether and then performing sedimentation for 2-3 times, and finally drying the collected precipitate in a drying oven at 30 ℃ for 24 hours to obtain the hyperbranched non-phosphorus water treatment agent containing the tertiary amine and having the chemical structure of the formula II, wherein the yield of the product reaches 92.8wt%.
Setting the feeding amount to be 20mg/L, and measuring LSI to be-6.978 under the environment of 25 ℃; caCO was carried out at 90 ℃ and pH =10 3 Testing the scale inhibition performance to obtain CaCO according to GB/T16632-2008 3 The scale inhibition rate is 78.3%; caSO at 60 ℃ and pH =11 4 Scale inhibition experiment, according to GB/T2889-2008, caSO is measured 4 The scale inhibition rate is 74.9%; the Escherichia coli bacteriostasis rate is 90.8 measured according to GB/T4789.2-2010 dilution plate method％。
Example 2
A preparation method of a hyperbranched phosphorus-free water treatment agent containing tertiary amine comprises the following steps:
2.96g (0.04 mol) of epoxy propanol and 1.996g (0.01 mol) of dimethylaminoethyl acrylate are added at room temperature and placed at 70 ℃ for reaction for 60min to obtain a hyperbranched polyether intermediate with a chemical structure shown in the formula I, and the reaction equation of the process is the same as that of the example 1; then adding 10mL of N, N-dimethylformamide, 8g (0.08 mol) of succinic anhydride and 0.24g of concentrated sulfuric acid into the reaction system of the hyperbranched polyether intermediate, stirring until a uniform solution is formed, performing carboxylation reaction for 3 hours at 80 ℃, and obtaining a reaction solution containing a product after the reaction is finished, wherein the product is the hyperbranched non-phosphorus water treatment agent containing tertiary amine and having a chemical structure as shown in a formula II, and the reaction equation of the process is the same as that of the example 1; and (3) dripping the reaction liquid containing the product into glacial ethyl ether for sedimentation, collecting the formed precipitate, respectively dissolving the precipitate by using methanol/ethyl ether and then performing precipitation for 2-3 times, and finally, collecting the obtained precipitate, and drying the precipitate in a drying oven at the temperature of 30 ℃ for 24 hours to obtain the hyperbranched phosphorus-free water treatment agent containing the tertiary amine and having the chemical structure of the formula II, wherein the yield of the product reaches 90.1wt%.
The products before and after carboxylation are hyperbranched polyether intermediate with a chemical structure shown in formula I and hyperbranched non-phosphorus water treatment agent containing tertiary amine with a chemical structure shown in formula II respectively, FTIR spectrograms of the hyperbranched polyether intermediate and the hyperbranched non-phosphorus water treatment agent are shown in figure 1, wherein I is the polyether intermediate, II is the non-phosphorus water treatment agent, and as can be seen from figure 1, the wave number in the curve of the non-phosphorus water treatment agent II is 1740cm -1 The peak is a carbonyl absorption peak of the ester, and the peak intensity is stronger compared with that in a curve of the polyether intermediate I, so that more carbonyl carbon is generated in the phosphorus-free water treatment agent II; the wave number of the curve of the phosphorus-free water treatment agent II is 1640cm -1 The peak is a carbonyl absorption peak of carboxylic acid and the peak intensity is stronger, which indicates that the phosphorus-free water treatment agent II has more carboxyl; 1000-1250cm in curve of phosphorus-free water treatment agent II -1 The peak is the strong stretching vibration peak of the C-O-C ether bond. The infrared spectrum of the product in example 1 is the same as that in example 2.
The product after carboxylation is the hyperbranched phosphate-free water with the chemical structure of the formula IIPhysical therapy agent 1 An H-NMR spectrogram is shown in figure 4, a peak at the chemical shift of 3.11-3.85 ppm is a characteristic absorption peak of hydrogen on polyether methylene, which indicates a hyperbranched polyether structure in the phosphorus-free water treatment agent II, and chemical shifts of 2.51-2.60 ppm and 2.11-2.23 ppm are hydrogen on methylene after a double bond reacts with hydroxyl and hydrogen on methyl connected with tertiary amine respectively, which indicates that the phosphorus-free water treatment agent II contains a tertiary amine structure; chemical shifts are characteristic absorption peaks of hydrogen on methylene clearly connected with ester groups at 4.16-4.31 ppm, and the compounds contain carboxyl structures. The nuclear magnetic hydrogen spectrum of the product in example 1 is the same as that in example 2.
And (3) performance testing: setting the feeding amount to be 20mg/L, and measuring LSI to be-7.120 under the environment of 25 ℃; caCO was carried out at 50 ℃ and pH =9 3 Testing the scale inhibition performance according to GB/T16632-2008 to obtain CaCO 3 The scale inhibition rate is 86.3 percent; caSO at 80 ℃ and pH =8 4 Scale inhibition experiment, according to GB/T2889-2008, caSO is measured 4 The scale inhibition rate is 88.5 percent; the Escherichia coli inhibition rate is 93.5% according to GB/T4789.2-2010 dilution plate method.
Example 3
A preparation method of a hyperbranched phosphorus-free water treatment agent containing tertiary amine comprises the following steps:
2.96g (0.04 mol) of epoxy propanol and 1.56g (0.01 mol) of dimethylaminopropyl acrylamide are added at room temperature and placed at 70 ℃ for reaction for 60min to obtain a hyperbranched polyether intermediate with a chemical structure shown in a formula III, and the reaction equation of the process is as follows:
then adding 10mL of N, N-dimethylformamide, 9g (0.09 mol) of succinic anhydride and 0.17g of concentrated sulfuric acid into the reaction system of the hyperbranched polyether intermediate, stirring until a uniform solution is formed, performing carboxylation reaction for 4 hours at 70 ℃, and obtaining a reaction solution containing a product after the reaction is finished, wherein the product is the hyperbranched non-phosphorus water treatment agent containing the tertiary amine and having the chemical structure shown in the formula IV, and the reaction equation of the process is as follows:
and (3) dripping the reaction liquid containing the product into glacial ethyl ether for sedimentation, collecting the formed precipitate, respectively dissolving the precipitate by using methanol/ethyl ether and then performing sedimentation for 2-3 times, and finally drying the collected precipitate in a drying oven at 30 ℃ for 24 hours to obtain the hyperbranched non-phosphorus water treatment agent containing the tertiary amine and having the chemical structure shown in the formula IV, wherein the yield of the product reaches 89.1wt%.
And (3) performance testing: setting the feeding amount to be 20mg/L, and measuring LSI to be-7.198 at the temperature of 25 ℃; caCO was carried out at 80 ℃ and pH =7 3 Testing the scale inhibition performance to obtain CaCO according to GB/T16632-2008 3 The scale inhibition rate is 95.3%; caSO is carried out at 60 ℃ and pH =7 4 Scale inhibition experiment, according to GB/T2889-2008, caSO is measured 4 The scale inhibition rate is 93.1%; the Escherichia coli inhibition rate is 99.8% according to GB/T4789.2-2010 dilution plate method.
Example 4
A preparation method of a hyperbranched phosphorus-free water treatment agent containing tertiary amine comprises the following steps:
adding 3.32g (0.05 mol) of epoxy propanol and 1.56g (0.01 mol) of dimethylaminopropyl acrylamide at room temperature, and reacting at 70 ℃ for 50min to obtain a hyperbranched polyether intermediate with a chemical structure shown in a formula III, wherein the reaction equation of the process is the same as that of the example 3; then adding 10mL of N, N-dimethylformamide, 11g (0.11 mol) of succinic anhydride and 0.2g of concentrated sulfuric acid into the reaction system of the hyperbranched polyether intermediate, stirring until a uniform solution is formed, performing carboxylation reaction for 3 hours at 80 ℃, and obtaining a reaction solution containing a product after the reaction is finished, wherein the product is the hyperbranched non-phosphorus water treatment agent containing tertiary amine and having a chemical structure shown in a formula IV, and the reaction equation of the process is the same as that of the example 3; and (3) dripping the reaction liquid containing the product into glacial ethyl ether for sedimentation, collecting the formed precipitate, respectively dissolving the precipitate by using methanol/ethyl ether and then performing sedimentation for 2-3 times, and finally drying the collected precipitate in a drying oven at 30 ℃ for 24 hours to obtain the hyperbranched non-phosphorus water treatment agent containing the tertiary amine and having the chemical structure shown in the formula IV, wherein the yield of the product reaches 88.9wt%.
The products before and after the carboxylation are respectively hyperbranched polyether intermediate with a chemical structure shown in the formula III and hyperbranched phosphorus-free water treatment agent containing tertiary amine with a chemical structure shown in the formula IV, FTIR spectrograms of the hyperbranched polyether intermediate and the hyperbranched phosphorus-free water treatment agent are shown in figure 2, wherein III is the polyether intermediate, IV is the phosphorus-free water treatment agent, and as can be seen from figure 2, the wave number in the curve of the phosphorus-free water treatment agent IV is 1740cm -1 The peak is a carbonyl absorption peak of the ester, and the peak intensity is stronger compared with that of a polyether intermediate III curve, so that more carbonyl carbon is generated in the phosphorus-free water treatment agent IV; the wave number in the IV curve of the phosphorus-free water treatment agent is 1640cm -1 The peak is a carbonyl absorption peak of carboxylic acid and the peak intensity is stronger, which indicates that the phosphorus-free water treatment agent IV has more carboxyl groups; 1000-1250cm in IV curve of phosphorus-free water treatment agent -1 The peak is the strong stretching vibration peak of the C-O-C ether bond. The infrared spectrum of the product in example 3 is the same as that in example 4.
The product after carboxylation, namely hyperbranched non-phosphorus water treatment agent with the chemical structure of formula IV 1 An H-NMR spectrogram is shown in figure 5, a peak at the chemical shift of 3.11-3.85 ppm is a characteristic absorption peak of hydrogen on polyether methylene, which indicates a hyperbranched polyether structure in the phosphorus-free water treatment agent II, and chemical shifts at 2.51-2.60 ppm and 2.23-2.25 ppm are hydrogen on methylene after a double bond reacts with hydroxyl and hydrogen on methyl connected with tertiary amine respectively, which indicates that the phosphorus-free water treatment agent II contains a tertiary amine structure; the chemical shift is a characteristic absorption peak of hydrogen on methylene connected with ester group at 4.13-4.28 ppm, which indicates that the carboxyl structure is contained. The nuclear magnetic hydrogen spectrum of the product in example 3 is the same as that in example 4.
And (3) performance testing: setting the feeding amount to be 20mg/L, and measuring LSI to be-7.021 at the temperature of 25 ℃; caCO was carried out at 50 ℃ and pH =3 3 Testing the scale inhibition performance to obtain CaCO according to GB/T16632-2008 3 The scale inhibition rate is 96.3 percent; caSO is carried out at 70 ℃ and pH =4 4 Scale inhibition experiment, according to GB/T2889-2008, caSO is measured 4 The scale inhibition rate is 93.3%; the Escherichia coli bacteriostasis rate is 97.3 percent according to GB/T4789.2-2010 dilution plate method.
The data show that the hyperbranched polyether phosphate-free water treatment agent with tertiary amine synthesized by the invention has wider use conditions in water, namely, the pH and the temperature during treatment have better effects on sewage treatment.
When the feeding amount of the phosphorus-free water treatment agents II and IV in the above embodiments is 5-30mg/L, the scale inhibition and antibacterial properties are shown in Table 1. The phosphorus-free water treatment agent II was a product of example 1 and example 2, and the products of example 1 and example 2 were each averaged after performance testing in the following Table 1. The phosphorus-free water treatment agent IV is the product of example 3 and example 4, and the products of example 3 and example 4 are respectively averaged after performance tests in the following table 1.
TABLE 1 Scale inhibition and antibacterial Properties of non-phosphorus water treatment agents II and IV
Note: LSI is a Langerial index, an index that measures the tendency of calcium carbonate to dissolve in water, with positive values indicating a tendency for calcium carbonate to precipitate and negative values indicating a tendency to dissolve.
As can be seen from Table 1, the hyperbranched polyether phosphorus-free water treatment agent with tertiary amine synthesized by the invention has good treatment effect under neutral condition, and the scale inhibition effect and the bacteriostatic effect reach the maximum value and are gradually gentle after the content of the water treatment agent is added to 20 mg/L.
The performance data of the phosphorus-free water treatment agents II and IV for inhibiting escherichia coli are shown in the table 2. FIG. 3 is an antibacterial experiment picture of the phosphorus-free water treatment agent with the structure shown in formula IV, which is determined by an agar dilution method under the feeding amounts of 10mg/L, 20mg/L and 30mg/L respectively.
TABLE 2 Escherichia coli inhibiting performance of phosphorus-free water treatment agents II and IV
As can be seen from Table 2 and FIG. 3, the phosphorus-free water treatment agent of the present invention has a good antibacterial performance, and the Escherichia coli inhibition rate reaches 93.6% when the feeding amount is 10 mg/L.
The flocculation effect of the water treatment agent in the above example was tested by taking four portions of raw water, each portion of which had a Sludge Density Index (SDI) of 10 and a volume of 1L. 20mg of the water treatment agent prepared in examples 1 to 4 was added to the raw water, and after stirring for 2 minutes, the water was filtered to measure the SDI index. The data are shown in Table 2.
TABLE 3 flocculation Effect of Water treatment Agents in examples
| SDI index | |
| Example 1 | 0.7 |
| Example 2 | 0.6 |
| Example 3 | 0.3 |
| Example 4 | 0.5 |
It is well known that the SDI index of well water is about 1.0 and does not require any pretreatment for removing colloidal fouling. As can be seen from Table 3, the phosphorus-free water treatment agent of the present invention can meet the water inlet requirements of a reverse osmosis system for sewage treatment.
The invention relates to a one-pot method for preparing a phosphorus-free green water treatment agent with the triple effects of flocculation, scale inhibition and antibiosis. The water treatment agent prepared by the invention can simultaneously have excellent flocculation, scale inhibition and antibacterial effects under the condition of extremely small using amount. The water treatment agent does not need to be compounded by adding acid, LSI index can reach-7.2, and the water treatment agent has great inhibition effect on scale formation; the dosage is as low as 20mg/L, so that the SDI value of the raw water sludge density index can be reduced from 10 to 0.3-0.7. The water treatment agent is a hyperbranched macromolecular structure water treatment agent with an antibacterial effect, forms antibacterial nano particles in water, and has an efficient, broad-spectrum and rapid antibacterial effect. The pH application range of the phosphorus-free water treatment agent is 2-12, so that the phosphorus-free water treatment agent has an excellent water purification effect, avoids the mutual restriction and antagonism when the traditional water treatment agents with various purposes are compounded and used, and is an environment-friendly water treatment agent.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (7)
1. A preparation method of a hyperbranched phosphorus-free water treatment agent containing tertiary amine is characterized by comprising the following steps: heating and reacting epoxy propanol and unsaturated ester containing a tertiary amine structure at the temperature lower than 90 ℃ to obtain a hyperbranched polyether intermediate, adding an acid substance solution under the action of a catalyst to perform a carboxylation reaction at the temperature lower than 90 ℃, and performing post-treatment to obtain a phosphorus-free water treatment agent containing a tertiary amine structure;
the unsaturated ester containing the tertiary amine structure is dimethylaminoethyl acrylate or dimethylaminopropyl acrylamide; the acid substance solution contains acid anhydride, and the acid anhydride is succinic anhydride or maleic anhydride.
2. The method for preparing a hyperbranched phosphorus-free water treatment agent containing tertiary amine according to claim 1, wherein the catalyst is concentrated sulfuric acid with a mass fraction of 70% or more; the acidic substance solution is DMF solution containing acid anhydride, and the molar volume ratio of the acid anhydride to the DMF is (0.05-0.15) mol/10mL.
3. The preparation method of the hyperbranched phosphorus-free water treatment agent containing tertiary amine according to claim 1, wherein the molar ratio of the epoxypropanol, the unsaturated ester containing tertiary amine structure and the acid anhydride is (3-5): (1): (5-15), and the dosage of the catalyst is 4-8% of the mass of the epoxypropanol.
4. The method for preparing a hyperbranched phosphorus-free water treatment agent containing tertiary amine according to claim 1, wherein the reaction temperature of the heating reaction is 70-80 ℃ and the reaction time is 40-60min; the reaction temperature of the carboxylation reaction is 70-80 ℃, and the reaction time is 3-4h.
5. The preparation method of the hyperbranched phosphorus-free water treatment agent containing tertiary amine according to claim 1, wherein the post-treatment process comprises the steps of adopting glacial ethyl ether to settle products after the carboxylation reaction is finished, collecting precipitates, respectively carrying out dissolving/settling operations with methanol/ethyl ether for 2-3 times, and finally drying the collected precipitates at 30 ℃.
6. A hyperbranched phosphorus-free water treatment agent containing tertiary amine prepared by the preparation method according to any one of claims 1 to 5.
7. The application of the hyperbranched phosphorus-free water treatment agent containing tertiary amine prepared by the preparation method according to any one of claims 1 to 5 in a reverse osmosis membrane system is characterized in that the addition amount of the hyperbranched phosphorus-free water treatment agent containing tertiary amine in water to be treated is 2-30mg/L, and the pH value of the water to be treated is 2-12.
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