Hyperbranched polymer, preparation method and application

Abstract

A hyperbranched polymer and a preparation method and application thereof, belonging to the technical field of polymer preparation. The hyperbranched polymer is copolymerized by a first functional monomer, maleic anhydride and a second functional monomer; the structural formula of the first functional monomer is: the structural formula of the second functional monomer is: the hyperbranched polymer of the present invention has excellent scale inhibition and antibacterial properties, and the scale inhibition performance is stable, and can be used in high Ca 2+ Used in high concentration and high mineralization environments.

Description

Technical Field

[0001] The invention belongs to the technical field of polymer preparation, and in particular relates to a hyperbranched polymer, a preparation method and application. Background Art

[0002] Hyperbranched polymers are a class of highly branched three-dimensional macromolecules, belonging to an important subclass in the field of dendritic polymers. Due to their unique molecular structure, asymmetric random branches, rich terminal functional groups, and easy modification of molecular structure, they are widely used in ink coatings, biomedicine, plastics and rubber, petrochemicals, water treatment and other fields. For example, coating curing agents, toughening agents, dispersants, etc., plastic lubricants, etc., flocculants, demulsifiers, scale inhibitors, heavy metal water treatment agents, etc.

[0003] At present, hyperbranched polymers used as scale inhibitors for water treatment are mainly divided into four types according to functional groups: hyperbranched polycarboxylic acids, hyperbranched polyamide-amines, hyperbranched polyesters, and modified hyperbranched structures. In general, most of the existing hyperbranched polymer scale inhibitors can only have a good scale inhibition effect on some metal salts, such as only calcium carbonate or calcium sulfate, or the scale inhibition performance is unstable. When the water contains Ca 2+ When the mass concentration is not higher than 500 mg / L, the scale inhibitor shows better scale inhibition performance, but in high Ca 2+ In application scenarios with high concentration (greater than 1000 mg / L) and high mineralization (i.e. the total mass concentration of various ions in the system is greater than 10000 mg / L), the scale inhibition effect will be significantly reduced.

[0004] Patent CN105820291A discloses a hyperbranched polycarboxylic acid polymer scale inhibitor and its preparation method, but there are disadvantages such as excessive usage and being greatly affected by pH, and it is difficult to have a practical and good application prospect. Patent CN106146819A discloses a carboxyl-terminated hyperbranched polymer scale inhibitor and scale preventer and a synthesis method, and a carboxyl-terminated hyperbranched polymer scale inhibitor and scale preventer is synthesized by a "double monomer method" and a "single monomer method". Its molecular structure is a hyperbranched structure with a carboxyl group at the end, and the molecule contains ester groups or amide groups or ester groups and amide groups. However, since it only contains a single carboxylic acid group, it is difficult to have a good scale inhibition effect on a variety of metal salts, and the stability of its scale inhibition performance is not good. Summary of the invention

[0005] In view of the shortcomings of the prior art, the present invention aims to provide a hyperbranched polymer and a preparation method and application thereof, wherein the hyperbranched polymer has excellent scale inhibition and antibacterial properties, and the scale inhibition performance is stable, and can be used in high Ca 2+ Used in high concentration and high mineralization environments.

[0006] In order to achieve the above object, according to one aspect of the present invention, a hyperbranched polymer is provided, wherein the hyperbranched polymer is copolymerized by a first functional monomer, maleic anhydride and a second functional monomer;

[0007] Wherein, the structural formula of the first functional monomer is:

[0008] The structural formula of the second functional monomer is:

[0009] In some embodiments, the hyperbranched polymer has a number average molecular weight of 5000-8000 and a degree of branching of 0.4-0.6.

[0010] According to another aspect of the present invention, there is also provided a method for preparing the above-mentioned hyperbranched polymer, comprising the following steps:

[0011] (1) Synthesizing the first functional monomer: subjecting allyl alcohol and maleic anhydride to a monoesterification reaction under the protection of benzoquinone to obtain the first functional monomer;

[0012] (2) Synthesizing the second functional monomer: dissolving dimethylaminoethyl methacrylate and a polymerization inhibitor in acetone to obtain a mixed solution, adding dropwise an acetone solution of 1,3-propyl sultone to the mixed solution to carry out a reaction, cooling the reaction product and crystallizing it to obtain the second functional monomer;

[0013] (3) respectively adding the DMF solution of the first functional monomer, the DMF solution of the second functional monomer and the DMF solution of the initiator dropwise into the DMF solution of maleic anhydride to react, removing unreacted monomers, and drying to obtain a hyperbranched polymer product.

[0014] In some embodiments, in step (1), the reaction temperature is 45-55°C, and the reaction time is 24-36h.

[0015] In some embodiments, in step (1), the molar ratio of the addition of propylene alcohol and maleic anhydride is 1:1-2.

[0016] In some embodiments, in step (2), the added molar ratio of dimethylaminoethyl methacrylate and 1,3-propyl sultone is 1.1-1.3:1.

[0017] In some embodiments, in step (2), the reaction temperature is 38-42°C, and the reaction time is 20-24h.

[0018] In some embodiments, in step (3), the specific conditions of the reaction are: under nitrogen protection, maleic anhydride is dissolved in solvent DMF, the temperature is raised to 60-65°C, and the DMF solutions of the first functional monomer, the second functional monomer and the DMF solution of the initiator benzoyl peroxide are slowly added dropwise, respectively, and after the addition is completed, the reaction is kept at 60-65°C for 18-20 hours.

[0019] In some embodiments, in step (3), the molar ratio of the first functional monomer to maleic anhydride is 1-1.3:1; the amount of the second functional monomer is 2-2.5% of the total mass of the first functional monomer and maleic anhydride; and the amount of the initiator benzoyl peroxide is 5%-6% of the total mass of the monomers.

[0020] According to another aspect of the present invention, there is also provided application of the hyperbranched polymer or the hyperbranched polymer prepared according to the preparation method in water scale inhibition and sterilization.

[0021] Compared with the prior art, the present invention has the following beneficial effects:

[0022] (1) The present invention provides a hyperbranched polymer. By designing the molecular structure of the hyperbranched polymer, a monomer containing a carboxyl group, a quaternary amine group and a sulfonic acid group is introduced, so that the molecular structure contains a large number of carboxyl groups and part of the quaternary amine groups and sulfonic acid groups. The groups act synergistically, so that the hyperbranched polymer has excellent scale inhibition and antibacterial properties, and the scale inhibition performance is stable, and can be used in high Ca 2+ Used in high concentration and high mineralization environments.

[0023] (2) The preparation method of the hyperbranched polymer of the present invention is simple, the product has uniform performance, and has good industrial application prospects. DETAILED DESCRIPTION

[0024] In order to enable those skilled in the art to understand the characteristics and effects of the present invention, the following is a general description and definition of the terms and expressions mentioned in the specification and claims. Unless otherwise specified, all technical and scientific terms used in the text are the common meanings understood by those skilled in the art for the present invention. In the event of a conflict, the definition in this specification shall prevail.

[0025] The theories or mechanisms described and disclosed herein, whether correct or incorrect, should not limit the scope of the present invention in any way, that is, the present invention can be implemented without being limited by any specific theory or mechanism.

[0026] Herein, when describing embodiments or examples, it should be understood that they are not used to limit the present invention to these embodiments or examples. On the contrary, all substitutes, improvements and equivalents of the methods and materials described in the present invention can be included in the scope limited by the claims.

[0027] In this document, in order to make the description concise, not all possible combinations of various technical features in various embodiments or examples are described. Therefore, as long as there is no contradiction in the combination of these technical features, the various technical features in various embodiments or examples can be combined arbitrarily, and all possible combinations should be considered to be within the scope of this specification.

[0028] The present invention provides a hyperbranched polymer, which is copolymerized by a first functional monomer, maleic anhydride and a second functional monomer;

[0029] Wherein, the structural formula of the first functional monomer is:

[0030] The structural formula of the second functional monomer is:

[0031] In the present invention, a large number of carboxyl groups and part of quaternary amine and sulfonic acid groups are terminated at the end of the hyperbranched polymer molecules by molecular design, and the groups act synergistically, so that the hyperbranched polymer has excellent scale inhibition and antibacterial properties, and the scale inhibition performance is stable, and can be used in high Ca 2+ On the one hand, the carboxyl group can react with Ca 2+ Chelation occurs, allowing Ca 2+ Difficult to deal with SO4 2- 、CO3 2- The formation of crystal nuclei reduces the precipitation of calcium carbonate and calcium sulfate. On the other hand, the sulfonic acid group and quaternary ammonium group can make the generated calcium carbonate and calcium sulfate crystal nuclei less likely to aggregate, slowing down the growth of crystals. In addition, the zwitterionic functional groups in the hyperbranched polymer structure can interact with the surface active points of the crystal nuclei through electrostatic forces. When the spatial arrangement of the functional groups matches the ion spacing related to the crystal surface, a strong adsorption behavior will occur, which hinders the SO4 2- 、CO3 2- Normal binding to calcium ions, therefore, in high Ca 2+ The scale inhibition performance can remain stable in high concentration and high mineralization environments.

[0032] In some embodiments, the number average molecular weight of the hyperbranched polymer is 5000-8000, and the degree of branching is 0.4-0.6. The inventors of the present invention have found that the molecular weight has a certain influence on the scale inhibition and antibacterial properties of the hyperbranched polymer. If the molecular weight is too small, the number of functional groups is too small, the branched molecular structure is imperfect, the specific surface area is small, and the chelated Ca 2+ If the number is too small, the scale inhibition effect is low; if the molecular weight is too large, the molecular chain will be entangled, some functional groups may be wrapped inside the molecule, and the number of effective functional groups exposed to the outside is reduced, so the scale inhibition effect will also be reduced. The present invention controls the number average molecular weight of the hyperbranched polymer within a certain range, and the obtained three-dimensional structure of the hyperbranched molecule can make more terminal units distributed on the periphery of the molecule, and the effective internal specific area of ​​the molecule is increased, thereby ensuring excellent scale inhibition and antibacterial effects.

[0033] According to another aspect of the present invention, there is also provided a method for preparing the above-mentioned hyperbranched polymer, comprising the following steps:

[0034] (1) Synthesizing the first functional monomer: subjecting allyl alcohol and maleic anhydride to a monoesterification reaction under the protection of benzoquinone to obtain the first functional monomer;

[0035] (2) Synthesizing the second functional monomer: dissolving dimethylaminoethyl methacrylate and a polymerization inhibitor in acetone to obtain a mixed solution, adding dropwise an acetone solution of 1,3-propyl sultone to the mixed solution to carry out a reaction, cooling the reaction product and crystallizing it to obtain the second functional monomer;

[0036] (3) respectively adding the DMF solution of the first functional monomer, the DMF solution of the second functional monomer and the DMF solution of the initiator dropwise into the DMF solution of maleic anhydride to react, removing unreacted monomers, and drying to obtain a hyperbranched polymer product.

[0037] In the present invention, acryl alcohol and maleic anhydride are used to carry out a monoesterification reaction under the protection of benzoquinone to synthesize the first functional monomer. Specifically, acryl alcohol, maleic anhydride and benzoquinone are added to a four-necked flask, and the reaction is carried out under the protection of anhydrous CaCl2 to obtain the first functional monomer. In some embodiments, in step (1), the reaction temperature is 45-55°C, preferably 50°C; the reaction time is 24-36h, preferably 24-30h, and more preferably 24h. In some embodiments, in step (1), the addition molar ratio of acryl alcohol and maleic anhydride is 1:1-2, preferably 1:1-1.5. In some embodiments, the product obtained after the reaction can preferably be purified, for example, the unreacted monomer can be removed in a vacuum rotary evaporator to obtain the purified first functional monomer.

[0038] In the present invention, dimethylaminoethyl methacrylate and a polymerization inhibitor are dissolved in acetone to obtain a mixed solution, an acetone solution of 1,3-propyl sultone is added dropwise to the mixed solution to react, and the reaction product is cooled and crystallized to obtain the second functional monomer. Specifically, dimethylaminoethyl methacrylate and a polymerization inhibitor are dissolved in acetone to obtain a mixed solution, an acetone solution of 1,3-propyl sultone is added dropwise to the mixed solution under continuous stirring, and the mixture is reacted at a certain temperature for a period of time. After the reaction is completed, the reaction product is cooled and crystallized to obtain the second functional monomer. In some embodiments, in step (2), the addition molar ratio of dimethylaminoethyl methacrylate and 1,3-propyl sultone is 1.1-1.3:1, preferably 1.1:1. In some embodiments, the polymerization inhibitor can be a conventional polymerization inhibitor in the art, such as hydroquinone, and the amount of the polymerization inhibitor used can be the conventional amount used in the art, such as 0.01-0.1% of the monomer mass. In some embodiments, in step (2), the reaction temperature is 38-42°C, preferably 40°C; the reaction time is 20-24h, preferably 22h. In some embodiments, cooling the reaction product for crystallization can be cooling the reaction product for crystallization in an ice water bath, and the purpose of cooling crystallization is to remove unreacted monomers and other impurities.

[0039] In the present invention, the DMF solution of the first functional monomer, the DMF solution of the second functional monomer and the DMF solution of the initiator are respectively added dropwise to the DMF solution of maleic anhydride, reacted, unreacted monomers are removed, and the product hyperbranched polymer is obtained after drying. In some embodiments, in step (3), the specific conditions of the reaction are: under nitrogen protection, maleic anhydride is dissolved in the solvent DMF, the temperature is raised to 60-65°C, and the DMF solution of the first functional monomer, the second functional monomer and the DMF solution of the initiator benzoyl peroxide are slowly added dropwise, and after the addition is completed, the reaction is kept at 60-65°C for 18-20h. In some embodiments, the specific steps of removing unreacted monomers are: using reduced pressure to evaporate the solvent, and then dialyzing with a dialysis bag to remove unreacted monomers. In some embodiments, in step (3), the molar ratio of the first functional monomer to maleic anhydride is 1-1.3:1, preferably 1:1; the amount of the second functional monomer is 2-2.5% of the total mass of the first functional monomer and maleic anhydride; the amount of the initiator benzoyl peroxide is 5-6% of the total mass of the monomers. In the present invention, there is no special restriction on the amount of solvent DMF, as long as it can ensure that the monomer and the initiator can be fully dissolved.

[0040] According to another aspect of the present invention, there is also provided application of the hyperbranched polymer or the hyperbranched polymer prepared according to the preparation method in water scale inhibition and sterilization.

[0041] The present invention will be described in detail below by way of examples. It should be understood that the following examples are only used to further explain and illustrate the content of the present invention by way of example, and are not intended to limit the present invention.

[0042] Unless otherwise specified, the raw materials in the examples and comparative examples of the present invention are all commercially available, and the specific information is as follows:

[0043] Maleic anhydride, allyl alcohol, N,N-dimethylformamide, hydroquinone (AR), Chengdu Kelon Chemical Reagent Factory; 1,3-propyl sultone, Hubei Hongjing Chemical Co., Ltd.; dimethylaminoethyl methacrylate, benzoyl peroxide BPO, sodium vinyl sulfonate (mass fraction 25%), 2-acrylamide-2-methylpropanesulfonic acid (AR), Shanghai Aladdin Technology Co., Ltd.

[0044] Synthesis of the first functional monomer:

[0045]

[0046] Synthesis of the second functional monomer:

[0047]

[0048] Synthesis of Hyperbranched Polymers:

[0049]

[0050] Example 1

[0051] The method for preparing the hyperbranched polymer described in this embodiment comprises the following steps:

[0052] (1) Synthesis of the first functional monomer: Add 10 mL of allyl alcohol, 15 g of maleic anhydride and 0.01 g of benzodiquinone into a 50 mL four-necked flask, stir to dissolve, react at 50° C. for 24 h under the protection of anhydrous CaCl2, remove the unreacted maleic anhydride and allyl alcohol in a vacuum rotary evaporator, and obtain the first functional monomer;

[0053] (2) Synthesis of the second functional monomer: 0.11 mol of dimethylaminoethyl methacrylate and 0.01 g of inhibitor hydroquinone were dissolved in 60 mL of acetone to obtain a mixed solution; 0.1 mol of 1,3-propyl sultone was dissolved in 40 mL of acetone to obtain an acetone solution of 1,3-propyl sultone, which was added to a constant pressure dropping funnel and added dropwise to the mixed solution under constant stirring for 2 h. The reaction was carried out at 40° C. for 20 h. The reaction product was cooled and crystallized in an ice water bath to obtain the second functional monomer;

[0054] (3) Under nitrogen protection, 0.2 mol of maleic anhydride was dissolved in 40 mL of DMF, and the temperature was raised to 60° C. Then, 0.2 mol of the first functional monomer, 10 mL of a DMF solution containing 1 g of the second functional monomer, and 10 mL of a DMF solution containing 2.6 g of an initiator benzoyl peroxide were slowly added dropwise for 2 h. After the addition was completed, the mixture was kept at 60° C. for 18 h. After the reaction was completed, the solvent was evaporated under reduced pressure, and then the unreacted monomers were removed by dialysis. After drying, the product hyperbranched polymer was obtained.

[0055] Example 2

[0056] The method for preparing the hyperbranched polymer described in this embodiment comprises the following steps:

[0057] (1) Synthesis of the first functional monomer: 6.8 mL of allyl alcohol, 15 g of maleic anhydride and 0.01 g of benzodiquinone were added to a 50 mL four-necked flask, stirred to dissolve, reacted at 45° C. for 30 h under the protection of anhydrous CaCl2, and the unreacted maleic anhydride and allyl alcohol were removed in a vacuum rotary evaporator to obtain the first functional monomer;

[0058] (2) Synthesis of the second functional monomer: 0.12 mol of dimethylaminoethyl methacrylate and 0.01 g of inhibitor hydroquinone were dissolved in 60 mL of acetone to obtain a mixed solution; 0.1 mol of 1,3-propyl sultone was dissolved in 40 mL of acetone to obtain an acetone solution of 1,3-propyl sultone, which was added to a constant pressure dropping funnel and added dropwise to the mixed solution under constant stirring for 2 h. The reaction was carried out at 38° C. for 22 h. The reaction product was cooled in an ice water bath for crystallization to obtain the second functional monomer;

[0059] (3) Under nitrogen protection, 0.2 mol of maleic anhydride was dissolved in 40 mL of DMF solvent, the temperature was raised to 60° C., and 0.22 mol of the first functional monomer, 10 mL of DMF solution containing 1.2 g of the second functional monomer, and 10 mL of DMF solution containing 2.8 g of initiator benzoyl peroxide were slowly added dropwise for 2 h. After the addition was completed, the mixture was kept at 65° C. for 20 h. After the reaction was completed, the solvent was evaporated under reduced pressure, and then the unreacted monomers were removed by dialysis. After drying, the product hyperbranched polymer was obtained.

[0060] Example 3

[0061] The method for preparing the hyperbranched polymer described in this embodiment comprises the following steps:

[0062] (1) Synthesis of the first functional monomer: 6.8 mL of allyl alcohol, 20 g of maleic anhydride and 0.02 g of benzodiquinone were added to a 50 mL four-necked flask, stirred to dissolve, reacted at 55° C. for 36 h under the protection of anhydrous CaCl2, and the unreacted maleic anhydride and allyl alcohol were removed in a vacuum rotary evaporator to obtain the first functional monomer;

[0063] (2) Synthesis of the second functional monomer: 0.13 mol of dimethylaminoethyl methacrylate and 0.01 g of inhibitor hydroquinone were dissolved in 60 mL of acetone to obtain a mixed solution; 0.1 mol of 1,3-propyl sultone was dissolved in 40 mL of acetone to obtain an acetone solution of 1,3-propyl sultone, which was added to a constant pressure dropping funnel and added dropwise to the mixed solution under continuous stirring for 2.5 hours. The mixture was reacted at 42° C. for 24 hours, and the reaction product was cooled in an ice water bath for crystallization to obtain the second functional monomer;

[0064] (3) Under nitrogen protection, 0.2 mol of maleic anhydride was dissolved in 40 mL of DMF solvent, the temperature was raised to 60° C., and 0.26 mol of the first functional monomer, 10 mL of DMF solution containing 1.5 g of the second functional monomer, and 10 mL of DMF solution containing 3.7 g of initiator benzoyl peroxide were slowly added dropwise for 2 h. After the addition was completed, the mixture was kept at 60° C. for 18 h. After the reaction was completed, the solvent was evaporated under reduced pressure, and then the unreacted monomers were removed by dialysis. After drying, the product hyperbranched polymer was obtained.

[0065] Example 4

[0066] The method for preparing the hyperbranched polymer described in this embodiment comprises the following steps:

[0067] (1) Synthesis of the first functional monomer: Add 10 mL of allyl alcohol, 15 g of maleic anhydride and 0.01 g of benzodiquinone into a 50 mL four-necked flask, stir to dissolve, react at 50° C. for 24 h under the protection of anhydrous CaCl2, remove the unreacted maleic anhydride and allyl alcohol in a vacuum rotary evaporator, and obtain the first functional monomer;

[0068] (2) Synthesis of the second functional monomer: 0.11 mol of dimethylaminoethyl methacrylate and 0.01 g of inhibitor hydroquinone were dissolved in 60 mL of acetone to obtain a mixed solution; 0.1 mol of 1,3-propyl sultone was dissolved in 40 mL of acetone to obtain an acetone solution of 1,3-propyl sultone, which was added to a constant pressure dropping funnel and added dropwise to the mixed solution under constant stirring for 2 h. The reaction was carried out at 40° C. for 20 h. The reaction product was cooled and crystallized in an ice water bath to obtain the second functional monomer;

[0069] (3) Under nitrogen protection, 0.2 mol of maleic anhydride was dissolved in 40 mL of DMF solvent, the temperature was raised to 60° C., and 0.2 mol of the first functional monomer, 10 mL of DMF solution containing 0.5 g of the second functional monomer, and 10 mL of DMF solution containing 2.6 g of initiator benzoyl peroxide were slowly added dropwise for 2 h. After the addition was completed, the mixture was kept at 60° C. for 12 h. After the reaction was completed, the solvent was evaporated under reduced pressure, and then the unreacted monomers were removed by dialysis. After drying, the product hyperbranched polymer was obtained.

[0070] Example 5

[0071] The method for preparing the hyperbranched polymer described in this embodiment comprises the following steps:

[0072] (1) Synthesis of the first functional monomer: Add 10 mL of allyl alcohol, 15 g of maleic anhydride and 0.01 g of benzodiquinone into a 50 mL four-necked flask, stir to dissolve, react at 50° C. for 24 h under the protection of anhydrous CaCl2, remove the unreacted maleic anhydride and allyl alcohol in a vacuum rotary evaporator, and obtain the first functional monomer;

[0073] (2) Synthesis of the second functional monomer: 0.11 mol of dimethylaminoethyl methacrylate and 0.01 g of inhibitor hydroquinone were dissolved in 60 mL of acetone to obtain a mixed solution; 0.1 mol of 1,3-propyl sultone was dissolved in 40 mL of acetone to obtain an acetone solution of 1,3-propyl sultone, which was added to a constant pressure dropping funnel and added dropwise to the mixed solution under constant stirring for 2 h. The reaction was carried out at 40° C. for 20 h. The reaction product was cooled and crystallized in an ice water bath to obtain the second functional monomer;

[0074] (3) Under nitrogen protection, 0.2 mol of maleic anhydride was dissolved in 40 mL of DMF solvent, the temperature was raised to 60° C., and 0.2 mol of the first functional monomer, 20 mL of DMF solution containing 2 g of the second functional monomer, and 10 mL of DMF solution containing 2.7 g of initiator benzoyl peroxide were slowly added dropwise for 2.5 h. After the addition was completed, the mixture was kept at 60° C. for 24 h. After the reaction was completed, the solvent was evaporated under reduced pressure, and then the unreacted monomers were removed by dialysis. After drying, the product hyperbranched polymer was obtained.

[0075] Comparative Example 1

[0076] The preparation method of this comparative example is the same as that of Example 1, except that there is no second functional monomer.

[0077] Comparative Example 2

[0078] The preparation method of this comparative example is the same as that of Example 1, except that 1 g of the second functional monomer is replaced by 1 g of 2-acrylamide-2-methylpropanesulfonic acid.

[0079] Comparative Example 3

[0080] The preparation method of this comparative example is the same as that of Example 1, except that 1 g of the second functional monomer is replaced by 1 g of sodium vinyl sulfonate.

[0081] Performance Testing

[0082] The hyperbranched polymers described in Examples 1-5 of the present invention and Comparative Examples 1-3 were subjected to performance tests according to the following test methods. The specific performance indicators are shown in Table 1.

[0083] The number average molecular weight Mn was determined using an Agilent PL-GPC50 gel permeation chromatograph (GPC).

[0084] Degree of branching: 13 The degree of branching was calculated by CNMR spectrum analysis.

[0085] Calcium carbonate inhibition performance evaluation: Tested according to SY / T-5673-1993, with different Ca 2+ Concentration and mineralization of solutions A and B, Ca in solution A 2+ 、HCO3 - The mass concentrations were 300 and 430 mg / L, respectively, the mineralization was 988 mg / L, and the pH value was 7.2; the Ca in solution B 2+ 、HCO3 - The mass concentrations were 1654 and 2672 mg / L respectively, the mineralization was 42146 mg / L, and the pH value was 7.2; the experimental temperature and time were 70°C and 24h, and the hyperbranched polymer concentration was 10 mg / L.

[0086] Calcium sulfate inhibition performance evaluation: Tested according to SY / T5673-1993, with different Ca 2+ Concentration and mineralization of solutions A and B, Ca in solution A 2+ 、SO4 2- The mass concentrations were 300 and 430 mg / L, respectively, the mineralization was 988 mg / L, and the pH value was 7.2; the Ca in solution B 2+ 、SO4 2- The mass concentrations were 3000 and 3520 mg / L respectively, the mineralization was 45400 mg / L, and the pH value was 7.2; the experimental temperature and time were 70°C and 24h, and the hyperbranched polymer concentration was 10 mg / L.

[0087] Dispersion performance evaluation: Prepare solution, where Ca 2+ , HCO3 - and Fe 2+The concentrations were 300 mg / L, 534 mg / L and 10 mg / L respectively. 10 mg / L of different hyperbranched polymers were added to the solution and stirred for 30 minutes. After keeping the temperature in a water bath for 5 hours, a small amount of the above clear solution was taken into a 3 cm cuvette and its transmittance was measured at a wavelength of 420 nm using a 721 type UV-visible spectrophotometer. In addition, a certain amount of the solution was taken and its Zeta potential value was measured using a Zeta potential meter.

[0088] Antibacterial experiment: Different hyperbranched polymers were prepared into solutions with a concentration of 100 μg / mL, and the size of the antibacterial zone on the agar medium against Escherichia coli was tested by the Oxford cup method. The Oxford cups were scattered on the agar medium inoculated with Escherichia coli, and the hyperbranched polymer solutions of different concentrations were added respectively. After constant temperature cultivation at 37°C for 18 hours, the diameter of the antibacterial zone of each sample was measured with a ruler.

[0089] Table 1 Performance data of the hyperbranched polymers described in Examples 1-5 and Comparative Examples 1-3

[0090]

[0091]

[0092] Note: The blank group was distilled water.

[0093] It can be seen from Table 1 that the hyperbranched polymers in Examples 1-5 of the present invention have a high Ca 2+ The scale inhibition rate of calcium carbonate and calcium sulfate under the conditions of high concentration and high mineralization degree is maintained at more than 93%; at the same time, the absolute value of Zeta potential is large and the transmittance is low, indicating that the solution containing the hyperbranched polymer described in the embodiment of the present invention has good dispersion stability and strong stability of the solution; from the results of the antibacterial experiment, it can be seen that the hyperbranched polymer in the embodiment of the present application has excellent antibacterial effect. It can be seen from Example 1 and Comparative Examples 1-3 that the hyperbranched polymer structure in Comparative Example 1 does not contain the second functional monomer described in the present invention, and its low Ca 2+ The scale inhibition performance of calcium carbonate and calcium sulfate is better under the conditions of high concentration and low mineralization, but 2+ Under the conditions of high concentration and high mineralization, its scale inhibition performance is significantly reduced; the second functional monomer in the hyperbranched polymer molecules in Comparative Examples 2 and 3 contains only sulfonic acid groups and no quaternary amine group structure. Similarly, under high Ca 2+ Under the conditions of high concentration and high mineralization, its scale inhibition performance decreased significantly, indicating that there is a synergistic effect between the quaternary ammonium group and the sulfonic acid group and the carboxyl group, which can ensure the stability of the scale inhibition performance.

[0094] In summary, the present invention designs the molecular structure of the hyperbranched polymer so that the molecular structure contains a large number of carboxyl groups and part of the quaternary amine and sulfonic acid groups at the same time. The synergistic effect of each group makes the hyperbranched polymer have excellent scale inhibition and antibacterial properties, and the scale inhibition performance is stable, and it can be used in high mineralization, high Ca 2+ Used in concentration environments.

[0095] Obviously, the above embodiments of the present invention are only examples for clearly illustrating the present invention, and are not limitations on the implementation methods of the present invention. For ordinary technicians in the relevant field, other different forms of changes or modifications can be made on the basis of the above description. It is impossible to list all the implementation methods here. All obvious changes or modifications derived from the technical solution of the present invention are still within the protection scope of the present invention.

Claims

1. A hyperbranched polymer, characterized in that The hyperbranched polymer is copolymerized by a first functional monomer, maleic anhydride and a second functional monomer; Wherein, the structural formula of the first functional monomer is: ; The structural formula of the second functional monomer is: ; The hyperbranched polymer has a number average molecular weight of 5000-8000 and a degree of branching of 0.4-0.6; The preparation method of the hyperbranched polymer comprises the following steps: (1) Synthesis of the first functional monomer: subjecting allyl alcohol and maleic anhydride to a monoesterification reaction under the protection of benzoquinone to obtain the first functional monomer; (2) Synthesizing the second functional monomer: dissolving dimethylaminoethyl methacrylate and a polymerization inhibitor in acetone to obtain a mixed solution, adding dropwise an acetone solution of 1,3-propyl sultone to the mixed solution to react, cooling the reaction product to crystallize, and obtaining the second functional monomer; (3) respectively adding the DMF solution of the first functional monomer, the DMF solution of the second functional monomer and the DMF solution of the initiator dropwise into the DMF solution of maleic anhydride to react, removing unreacted monomers, and drying to obtain a hyperbranched polymer product; In step (3), the specific conditions of the reaction are as follows: under nitrogen protection, maleic anhydride is dissolved in a solvent DMF, the temperature is raised to 60-65°C, and the DMF solutions of the first functional monomer and the second functional monomer and the DMF solution of the initiator benzoyl peroxide are slowly added dropwise, and after the addition is completed, the temperature is kept at 60-65°C for 18-20 hours; The molar ratio of the first functional monomer to maleic anhydride is 1-1.3:1; the amount of the second functional monomer is 2-2.5% of the total mass of the first functional monomer and maleic anhydride; and the amount of the initiator benzoyl peroxide is 5-6% of the total mass of the monomers.

2. A method for preparing a hyperbranched polymer according to claim 1, characterized in that: The steps include: (1) Synthesis of the first functional monomer: subjecting allyl alcohol and maleic anhydride to a monoesterification reaction under the protection of benzoquinone to obtain the first functional monomer; (2) Synthesizing the second functional monomer: dissolving dimethylaminoethyl methacrylate and a polymerization inhibitor in acetone to obtain a mixed solution, adding dropwise an acetone solution of 1,3-propyl sultone to the mixed solution to react, cooling the reaction product to crystallize, and obtaining the second functional monomer; (3) respectively adding the DMF solution of the first functional monomer, the DMF solution of the second functional monomer and the DMF solution of the initiator dropwise into the DMF solution of maleic anhydride to react, removing unreacted monomers, and drying to obtain a hyperbranched polymer product.

3. The method for preparing a hyperbranched polymer according to claim 2, characterized in that In step (1), the reaction temperature is 45-55°C and the reaction time is 24-36h.

4. The method for preparing a hyperbranched polymer according to claim 2, wherein In step (1), the molar ratio of the addition of the propenol and maleic anhydride is 1:1-2.

5. The method for preparing a hyperbranched polymer according to claim 2, characterized in that: In step (2), the added molar ratio of dimethylaminoethyl methacrylate and 1,3-propyl sultone is 1.1-1.3:

1.

6. The method for preparing a hyperbranched polymer according to claim 2, characterized in that: In step (2), the reaction temperature is 38-42°C and the reaction time is 20-24h.

7. Use of the hyperbranched polymer according to claim 1 or the hyperbranched polymer prepared by the preparation method according to any one of claims 2 to 6 in water scale inhibition and sterilization.

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