Biquaternary ammonium salt resin as well as preparation method and application thereof

Abstract

The invention discloses biquaternary ammonium salt resin as well as a preparation method and application thereof, and belongs to the technical field of resin. The preparation method comprises the following steps: carrying out two independent quaternization reactions on aminated spheres of an acrylic resin skeleton and alkyl halide containing alkyl groups with different chain lengths, and covalently grafting a long alkyl chain quaternary ammonium group with a sterilization function and a short alkyl chain quaternary ammonium group with an exchange adsorption function on the surface and internal pore channels of the resin respectively; the resin provided by the invention is endowed with efficient sterilization and pollutant purification functions. The biquaternary ammonium salt resin disclosed by the invention can synchronously meet the disinfection and purification requirements of drinking water, has the advantages of stable performance, long service life and reusability, and can be applied to direct drinking water treatment.

Description

Technical Field

[0001] The invention belongs to the technical field of resin materials, and more specifically, relates to a diquaternary ammonium salt resin and a preparation method and application thereof. Background Art

[0002] At present, the removal of microorganisms in water mainly relies on chlorine disinfection, chlorine dioxide disinfection, ozone disinfection, etc. The above chemical disinfectants will react with pollutants in water to generate disinfection by-products such as trihalomethanes, carbon tetrachloride, halogenated acetic acid, bromate and nitrosamines, showing dominant genetic toxicity and carcinogenic risks, threatening the safety of drinking water. The residues of chemical disinfectants in water bodies also bring discomfort in terms of safety, odor and taste, making it difficult to meet the demand for direct drinking water.

[0003] In order to solve the problems of disinfection byproducts, residual toxicity and resistant bacteria of water-soluble bactericides, the present invention makes a water-insoluble solid bactericidal material by grafting a quaternary ammonium salt monomer compound on a resin material by covalent bonds. The advantages of this bactericidal material are that ① the bactericidal group is concentrated and efficient, ② the water-insoluble solid property will not cause secondary pollution of the water body, and ③ the solid-liquid separation can be achieved in time to shorten the disinfection stress time and reduce the probability of the generation of resistant bacteria. Different from the existing additive antibacterial resin (such as patents CN1280771A and CN102933648A, the quaternary ammonium salt bactericide described therein is impregnated and fixed in the resin, which is easy to migrate and lose, and the bactericidal time is short), the resin bactericidal material of the present invention belongs to a structural antibacterial resin, the bactericidal group contained in it is covalently bonded to the resin, the bactericidal performance is stable, the service life is long, it can be recycled and reused, and it has the characteristics of environmental protection, long-term effect and low cost. Summary of the invention

[0004] Solve the problems of disinfection by-products, residual toxins and resistant bacteria produced by existing chemical disinfection methods such as chlorine disinfection of drinking water, chlorine dioxide disinfection, and ozone disinfection.

[0005] Solve the problems of bactericide shedding toxicity, migration loss and short effectiveness in added antibacterial resin.

[0006] The problem that existing bactericidal resins have low efficiency and poor anti-interference ability and cannot meet the disinfection application in complex component systems of natural water bodies is solved.

[0007] Solve the problem of removing microorganisms and non-biological pollutants in water bodies, simultaneously complete water disinfection and purification, and obtain high-quality drinking water.

[0008] The present invention provides a diquaternary ammonium salt resin and a preparation method and application thereof. The resin of the present invention has the advantages of high efficiency in removing pathogenic microorganisms, no residual toxicity of disinfection byproducts and resistant bacteria, long-term effectiveness and cyclic reuse. The present invention also provides a disinfection and purification application of the diquaternary ammonium salt resin in drinking water.

[0009] In order to solve the above problems, the technical solution adopted by the present invention is as follows: A diquaternary ammonium salt resin of the present invention has a basic structure as shown in formula (I), Formula (I), In formula (I), Y is a resin ball skeleton having a structure as shown in formula (101); N a A quaternary ammonium group containing a long-chain alkyl group and containing at least one decyl group (C 10 ), N b It is a short-chain alkyl quaternary ammonium group; Formula (101); Wherein, R0 is H or a hydrocarbon group, and the number of carbon atoms of R0 ranges from 0 to 10; m is the number of repeating units, and the numerical range is 300 to 3000; m is preferably 500 to 3000, more preferably 500 to 2500, and most preferably 1000 to 2000.

[0010] When R0 is a hydrocarbon group, the number of carbon atoms in R0 is preferably 1 to 10, more preferably 1 to 8, and most preferably 1 to 5.

[0011] Preferably, the N a and N b is one or both of formula (201) and formula (202), Formula (201) Formula (202); Where X is Cl - Br - ,I - OH - 、SO4 2- 、HCO3 - 、CO3 2- any one of; n is the number of repeating units, and the value ranges from 0 to 10; R1, R2, R3, R4, R5, R6, R7 and R8 are respectively one of H or a hydrocarbon group, and the number of carbon atoms of R1, R2, R3, R4, R5, R6, R7 and R8 is in the range of 0 to 20.

[0012] Preferably, the quaternary ammonium group N a Content and quaternary ammonium group N b The content ratio is 1: (5~199).

[0013] Preferably, the quaternary ammonium group N a The content accounts for 0.5%~20.0% of the total amount of quaternary ammonium groups in the resin. bThe content accounts for 80.0%~99.5% of the total amount of quaternary ammonium groups in the resin, where the total amount of quaternary ammonium groups in the resin is equal to the quaternary ammonium groups N on the surface of the resin. a The content is related to the quaternary ammonium group N b The sum of contents.

[0014] More preferably, the quaternary ammonium group N a The content accounts for 2.0%~10.0% of the total amount of quaternary ammonium groups in the resin. b The content accounts for 80.0%~98.0% of the total quaternary ammonium groups of the resin.

[0015] Preferably, the particle size of the resin is 30-3000 µm, preferably 30-2000 µm, more preferably 50-1000 µm, and most preferably 50-500 µm.

[0016] Preferably, the strong base exchange capacity of the resin is 1.0-6.0 mmol / g, more preferably 2.0-5.0 mmol / g, and most preferably 3.0-5.0 mmol / g.

[0017] The present invention discloses a method for preparing a diquaternary ammonium salt resin having formula (I), comprising a first quaternization reaction: adding an aminated resin and a haloalkyl reagent containing a long-chain alkyl group, stirring, and performing a quaternization reaction to obtain a first quaternary ammonium salt resin containing a long-chain alkyl group; and a second quaternization reaction: adding the obtained first quaternary ammonium salt resin and a haloalkyl reagent containing a short-chain alkyl group, stirring, and performing a quaternization reaction to obtain a second quaternary ammonium salt resin. The mass ratio of the aminated resin to the first quaternary ammonium reagent is (2-4): 1, and the mass ratio of the first quaternary ammonium salt resin to the second quaternary ammonium reagent is (0.5-2): 1. The structure of the resin aminated ball contains one or more monomers of formula (101).

[0018] Preferably, the reaction temperature of the quaternization reaction is 50° C. to 150° C., the stirring speed is 200 to 400 rpm, and the reaction time is 4 to 24 h.

[0019] The invention discloses an application of a diquaternary ammonium salt resin in water treatment, wherein the diquaternary ammonium salt resin or the diquaternary ammonium salt resin prepared by the preparation method is used to remove microorganisms in water for sterilization, and simultaneously purify pollutants.

[0020] Compared with the prior art, the present invention has the following beneficial effects: (1) A diquaternary ammonium salt resin of the present invention achieves both excellent long-term bactericidal function and higher pollutant purification and removal ability by covalently grafting a long-chain alkyl-containing high-efficiency bactericidal quaternary ammonium group only on the resin surface and covalently grafting a short-chain alkyl-type quaternary ammonium group with less steric hindrance on the resin interior through secondary quaternization; (2) The diquaternary ammonium salt resin of the present invention can meet the disinfection requirements of natural water bodies in real environments. The total colony count index of the water quality after disinfection meets the requirements of the national standard GB 5749-2022, providing new technical support for the disinfection process of drinking water. At the same time, after being treated with the resin of the present invention, the chemical oxygen demand (CODcr) in the water can be effectively removed, with a removal rate of about 56-68%, and negatively charged pollutants such as total phosphorus, total nitrogen and sulfate can be removed, with a removal rate of more than 90%, which can significantly improve the quality of drinking water. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] Figure 1 This is a diagram showing the bactericidal effects of different quaternary ammonium salt resins on Pseudomonas aeruginosa in a pure water system in Example 3 of the present invention; Figure 2 This is a diagram showing the bactericidal effects of different quaternary ammonium salt resins on Pseudomonas aeruginosa in natural water bodies in Example 4 of the present invention; Figure 3 This is a diagram showing the removal effects of different quaternary ammonium salt resins on non-biological pollutants in natural water bodies in Example 4 of the present invention. Implementation

[0022] The present invention is further described below in conjunction with specific embodiments. Example

[0023] A method for preparing a diquaternary ammonium salt resin having formula (I) of the present embodiment comprises the following steps: (1) 100 g of methyl acrylate resin aminated balls having the formula (101), 25 g of a long-chain alkyl halide reagent (1-bromodecane) as the first quaternary ammonium reagent, and 200 mL of N,N-dimethylformamide were added to a 500 mL three-necked flask, stirred, and the reaction temperature was controlled at 150°C, the stirring speed was 400 rpm / min, and the condensation reflux was maintained for 4 h; after cooling, the mixture was filtered, and the residual reaction reagent was removed by Soxhlet extraction. Methanol was selected as the extraction solvent to obtain the first quaternary ammonium salt resin A1-1; 100 g of the obtained first quaternary ammonium salt resin A1-1, 50 g of a short-chain alkyl halide reagent (1-bromoethane) as a second quaternization reagent, and 200 mL of anhydrous ethanol were added into a 1000 mL three-necked flask, stirred, and the reaction temperature was controlled at 50°C, the stirring speed was 200 rpm / min, and the condensation reflux was maintained for 24 h; after cooling, it was filtered and the residual reaction reagent was removed by Soxhlet extraction. The extraction solvents were methanol, ethanol, and acetone in sequence, and then it was fully rinsed with deionized water for 5 times to obtain the second quaternary ammonium salt resin A1-2; finally, the resin was transformed into a chlorine type with 15% sodium chloride solution.

[0024] Among them, the strong base exchange capacity of the A1-2 resin obtained in this example is 4.61 mmol / g, and the bactericidal quaternary ammonium group N a The content is 0.37 mmol / g, accounting for 8.03% of the total quaternary ammonium groups of the resin.

[0025] The basic content of this comparative example is the same as that of Example 1, except that: only 6-bromodecane in Example 1 is used as the quaternizing agent, and the resin surface and interior are quaternized once without any secondary quaternization step.

[0026] A method for preparing a quaternary ammonium resin in this comparative example comprises the following steps: 100 g of methyl acrylate resin aminated balls having the formula (101), 200 g of a long-chain alkyl halide reagent (6-bromodecane) as a quaternizing agent, and 200 mL of N,N-dimethylformamide were added into a 500 mL three-necked flask, stirred, and the reaction temperature was controlled at 150°C, the stirring speed was 400 rpm / min, and the condensation reflux was maintained for 24 h; after cooling, the mixture was filtered and the residual reaction reagent was removed by Soxhlet extraction. The extraction solvent was selected from methanol, ethanol, and acetone, and then the mixture was fully rinsed with deionized water for 3 times to obtain the quaternized resin A1-Con1; finally, the resin was transformed into a chlorine type with a 15% sodium chloride solution.

[0027] Among them, the strong base exchange capacity of the A1-Con1 resin obtained in this comparative example is 2.56 mmol / g, and the bactericidal quaternary ammonium group N a The content is 0.27 mmol / g, accounting for 10.55% of the total quaternary ammonium groups of the resin.

[0028] The basic content of this comparative example is the same as that of Example 1, except that: only 1-bromoethane in Example 1 is used as the quaternizing agent, and the surface and the interior of the resin are quaternized once without any secondary quaternization step.

[0029] A method for preparing a quaternary ammonium resin in this comparative example comprises the following steps: 100 g of methyl acrylate resin aminated balls having the formula (101), 200 g of a short-chain alkyl halide reagent (1-bromoethane) as a quaternizing agent, and 200 mL of N,N-dimethylformamide were added into a 500 mL three-necked flask, stirred, and the reaction temperature was controlled at 150°C, the stirring speed was 400 rpm / min, and the condensation reflux was maintained for 24 h; after cooling, the mixture was filtered and the residual reaction reagent was removed by Soxhlet extraction. The extraction solvent was selected from methanol, ethanol, and acetone, and then the mixture was fully rinsed with deionized water for 3 times to obtain the quaternized resin A1-Con2; finally, the resin was transformed into a chlorine type with a 15% sodium chloride solution.

[0030] Among them, the strong base exchange capacity of the A1-Con2 resin obtained in this comparative example is 4.97mmol / g, and the bactericidal quaternary ammonium group N a The content is 0.46 mmol / g, accounting for 9.26% of the total quaternary ammonium groups of the resin. Example

[0031] A method for preparing a diquaternary ammonium salt resin having formula (I) of the present embodiment comprises the following steps: (1) 100 g of methyl acrylate resin aminated balls having the formula (101), 50 g of a long-chain alkyl halide reagent (25 g of 1-chlorodecane and 25 g of 1-iododecane) as the first quaternization reagent, and 200 mL of N,N-dimethylformamide were added into a 500 mL three-necked flask, and stirred. The reaction temperature was controlled at 50°C, the stirring speed was 200 rpm / min, and the condensation reflux was maintained. The reaction was reacted for 24 h. After cooling, the mixture was filtered and the residual reaction reagent was removed by Soxhlet extraction. Methanol was selected as the extraction solvent to obtain the first quaternary ammonium salt resin A2-1. 100 g of the obtained first quaternary ammonium salt resin B1-1, 200 g of a short-chain alkyl halide reagent (1-iodomethane) as a second quaternization reagent, and 100 mL of anhydrous ethanol were added into a 1000 mL three-necked flask, stirred, and the reaction temperature was controlled at 150°C, the stirring speed was 200 rpm / min, and the condensation reflux was maintained for 4 h; after cooling, it was filtered and the residual reaction reagent was removed by Soxhlet extraction. The extraction solvents were methanol, ethanol, and acetone in sequence, and then it was fully rinsed with deionized water for 5 times to obtain the second quaternary ammonium salt resin B1-2; finally, the resin was transformed into a chlorine type with 15% sodium chloride solution.

[0032] Among them, the strong base exchange capacity of the B1-2 resin obtained in this example is 4.88 mmol / g, and the bactericidal quaternary ammonium group N a The content is 0.44 mmol / g, accounting for 9.02% of the total quaternary ammonium groups of the resin.

[0033] Table 1 Characteristic parameters of different quaternary ammonium salt resins Resin name Particle size (mesh) Total amount of quaternary ammonium groups (mmol / g) Surface quaternary ammonium group content (mmol / g) <![CDATA[Surface quaternary ammonium group N a Proportion]]> <![CDATA[A1-Con1]]> 80-100 2.56 0.27 10.55% <![CDATA[A1-Con2]]> 80-100 4.97 0.46 9.26% <![CDATA[A1-2]]> 80-100 4.61 0.37 8.03% <![CDATA[B1-2]]> 80-100 4.88 0.44 9.02% Example

[0034] This example mainly examines the bactericidal performance of the diquaternary ammonium salt resin of Example 1-2 and the single quaternary ammonium salt resin of Comparative Example 1-2 on a laboratory pure water system.

[0035] Pseudomonas aeruginosa PAO1 was selected and cultured in nutrient broth and diluted with sterile pure water to prepare 10 6CFU / mL colony count; 100 mL of the experimental bacterial solution was transferred to a 250 mL conical flask, and 0.5 g of each of the resins A1-Con1 and A1-Con2 obtained in Comparative Example 1-2 and the resins A1-2 and B1-2 obtained in Example 1-2 were added, and then placed in a constant temperature air bath shaker at 20±1°C and 200 rpm for 30 min, and the experiment was carried out with no resin added as a blank control group; finally, 50 µl of the experimental bacterial solution was taken for plate coating and counting, and the bactericidal efficiency of each resin was calculated. The measurement results are shown in Figure 1 shown.

[0036] Depend on Figure 1 It can be seen that the diquaternary ammonium salt resins A1-2 and B1-2 of Examples 1 and 2 both have a high efficiency bactericidal performance higher than 99.99%; the bactericidal effects of Examples 1 and 2 are better than those of Comparative Examples 1 and 2, indicating that the diquaternary ammonium salt resins of the present invention are superior to the traditional single quaternary ammonium salt resins A1-Con1 in bactericidal performance, and the resin structure design and preparation process of the present invention are helpful to improve the bactericidal performance of the resin. Example

[0037] This example mainly examines the bactericidal performance of the diquaternary ammonium salt resin of Example 1-2 and the single quaternary ammonium salt resin of Comparative Example 1-2 on natural water bodies. The natural water body involved in this example is selected from a section of the Yangtze River in Nanjing. The water quality parameters after filtration through a 0.45 um fiber membrane are as follows: CODcr is 18.9 mg / L, total nitrogen is 1.26 mg / L, total phosphorus is 0.078 mg / L, SO4 2- 63 mg / L, Cl - It is 59 mg / L.

[0038] Pseudomonas aeruginosa PAO1 was selected and cultured in nutrient broth and diluted with sterile pure water to prepare 10 4 CFU / mL colony count; 100 mL of the experimental bacterial solution was transferred to a 250 mL conical flask, and 0.5 g of each of the resins A1-Con1 and A1-Con2 obtained in Comparative Example 1-2 and the resins A1-2 and B1-2 obtained in Example 1-2 were added, and then placed in a constant temperature air bath shaker at 20±1°C and 200 rpm for 30 min, and the experiment was carried out with no resin added as a blank control group; finally, 50 µl of the experimental bacterial solution was taken for plate coating and counting, and the bactericidal efficiency of each resin was calculated. The measurement results are shown in Figure 2 After being treated with different quaternary ammonium salt resins prepared in the examples and comparative examples, the CODcr, total nitrogen, total phosphorus and SO4 in the water body 2- The indicator changes such as Figure 3 shown.

[0039] The number of live bacteria in the water treated with resins A1-2 and B1-2 were 13 CFU / mL and 2 CFU / mL, respectively, which can meet the disinfection and sterilization requirements of the national drinking water standard 5749-2022 (≤100 CFU / mL). The bactericidal rate of resin B1-2 is higher than that of A1-2 (>99.95%), which is much higher than the bactericidal effects of resins A1-Con1 and A1-Con2 in the comparative example (5~22%). The anti-interference ability of the diquaternary ammonium salt resin in natural actual water bodies is significantly better than that of the single quaternary ammonium salt resin in the comparative example, and it has high-efficiency bactericidal performance. At the same time, after the selected research water samples were treated with resins A1-2 and B1-2, CODcr, total nitrogen, total phosphorus and SO4 2- The removal rates are 56%-68%, 97-99%, 91-94% and 91-95% respectively, which are better than 8%, 19%, 16% and 33% of the traditional bactericidal resin A1-Con1, indicating that the diquaternary ammonium salt resin of the present invention can significantly remove pollutants such as soluble organic matter, total phosphorus, total nitrogen and sulfate in drinking water, and can significantly improve the quality of drinking water.

Claims

1. A diquaternary ammonium salt resin, characterized in that: The basic structure of the resin is shown in formula (I), Formula (I), Wherein, Y is a resin ball skeleton having a structure as shown in formula (101); N a A quaternary ammonium group containing a long-chain alkyl group and containing at least one decyl group (C 10 ), N b It is a short-chain alkyl quaternary ammonium group; Formula (101); Wherein, R0 is H or a hydrocarbon group, and the number of carbon atoms of R0 ranges from 0 to 10; m is the number of repeating units, and the numerical range is 300 to 3000.

2. A diquaternary ammonium salt resin according to claim 1, characterized in that: The N a and N b is one or both of formula (201) or formula (202), N a A quaternary ammonium group containing a long-chain alkyl group and containing at least one decyl group (C 10 ), N b It is a short-chain alkyl quaternary ammonium group. Formula (201) Formula (202); Where X is Cl - Br - ,I - OH - 、SO4 2- 、HCO3 - 、CO3 2- any one of; n is the number of repeating units, and the value ranges from 0 to 10; R1, R2, R3, R4, R5, R6, R7 and R8 are respectively one of H or a hydrocarbon group, and the number of carbon atoms of R1, R2, R3, R4, R5, R6, R7 and R8 is in the range of 0 to 20.

3. A diquaternary ammonium salt resin according to claim 1, characterized in that: The quaternary ammonium group N of the resin a The content of quaternary ammonium group N b The content ratio is 1: (5~199).

4. A method for preparing a diquaternary ammonium salt resin of formula (I), characterized in that: The resin quaternization process includes two independent quaternization steps, which are respectively grafting long-chain alkyl quaternary ammonium groups N a and containing short chain alkyl quaternary ammonium groups N b ; wherein the structure of the resin white ball contains one or more monomers of formula (101).

5. A method for preparing a diquaternary ammonium salt resin having formula (I) according to claim 4, characterized in that: The reaction temperature of the quaternization reaction is 50° C. to 150° C., the stirring speed is 200 to 400 rpm, and the reaction time is 2 to 24 hours.

6. Application of a diquaternary ammonium salt resin in water treatment, characterized in that: The diquaternary ammonium salt resin described in any one of claims 1 to 3 or the diquaternary ammonium salt resin prepared by the preparation method described in any one of claims 4 to 5 is used to remove biological pollution and non-biological pollutants in water.

Images