Quaternary ammonium salt bactericide based on mannich reaction and its synthesis method
Patent Information
- Application Number
- CN202610709992.8
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2026-05-22
- Publication Date
- 2026-08-28
AI Technical Summary
[0004]本发明的目的在于提供一种基于曼尼希反应的季铵盐杀菌剂及其合成方法，以解决上述背景技术中提出的问题：传统季铵盐结构较为单一，分子空间结构稳定性不足；曼尼希反应过程中易出现副缩聚反应，影响结构均一性；季铵化反应中局部传质效率较低，容易产生局部热聚集；常规线性反应体系难以兼顾反应效率与结构稳定性；后处理过程中副产物及无机盐残留较高，导致最终产物纯度与一致性受到限制
（1）采用“曼尼希反应—季铵化反应—疏水接枝反应”连续耦合技术路线，形成多级复合季铵盐结构，区别于传统单一步骤季铵盐体系。
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Abstract
Description
Technical Field
[0001] This invention relates to the field of bactericidal material synthesis technology, and more specifically, to a quaternary ammonium salt bactericide based on the Mannich reaction and its synthesis method. Background Technology
[0002] With the development of nitrogen-containing organic bactericidal materials, quaternary ammonium salt bactericides have been widely used in water treatment, medical materials, and surface antibacterial fields due to their stable structure, high synthesis efficiency, and wide applicability. In existing technologies, researchers have gradually introduced the Mannich reaction into the quaternary ammonium salt synthesis system, constructing intermediates containing tertiary amine structures through the Mannich reaction, followed by further quaternization modification, thereby improving the designability of molecular structures and the controllability of reactions. Subsequently, the regulation of hydrophobic segments, the introduction of siloxane structures, and the enhancement of reaction processes have gradually developed, leading to the evolution of quaternary ammonium salt systems towards composite, structured, and continuous processes.
[0003] However, existing technologies still have certain shortcomings: traditional quaternary ammonium salts have relatively simple structures and insufficient molecular spatial structure stability; side condensation reactions are prone to occur during the Mannich reaction, affecting structural uniformity; local mass transfer efficiency is low in the quaternization reaction, and local thermal aggregation is easy to occur; conventional linear reaction systems cannot balance reaction efficiency and structural stability; and the high residues of by-products and inorganic salts during post-processing limit the purity and consistency of the final product. Summary of the Invention
[0004] The purpose of this invention is to provide a quaternary ammonium salt bactericide based on the Mannich reaction and its synthesis method, in order to solve the problems mentioned in the background art: traditional quaternary ammonium salts have relatively simple structures and insufficient molecular spatial structure stability; side condensation reactions are prone to occur during the Mannich reaction, affecting structural uniformity; the local mass transfer efficiency in the quaternization reaction is low, and local thermal aggregation is easy to occur; conventional linear reaction systems cannot balance reaction efficiency and structural stability; and the high residue of by-products and inorganic salts in the post-processing process limits the purity and consistency of the final product.
[0005] Technical solution: A quaternary ammonium salt bactericide component based on the Mannich reaction includes a Mannich quaternary ammonium salt main structure, a hydrophobic regulating segment structure, and a siloxane bridging structure; The main structure of Mannich quaternary ammonium salt is formed by the Mannich reaction of phenolic compounds, aliphatic amine compounds containing primary amine structures and formaldehyde donor compounds to form Mannich tertiary amine intermediates, followed by quaternization reaction with quaternizing reagents. The hydrophobic regulating chain segment structure is grafted onto the periphery of the Mannich quaternary ammonium salt main structure; The siloxane bridging structure is embedded between the Mannich quaternary ammonium salt main structure and the hydrophobic regulating chain segment structure; The phenolic compound is selected from one of phenol, p-tert-butylphenol, nonylphenol, and resorcinol; The aliphatic amine compound containing a primary amine structure is selected from one of dodecylamine, tetradecylamine, hexadecylamine, and octadecylamine; The formaldehyde donor compound is selected from paraformaldehyde and triformaldehyde; The quaternizing agent is selected from one of chloroalkanes, bromoalkanes, and benzyl chloride; The hydrophobic regulating segment structure is formed by a hydrophobic regulating compound containing a double bond structure; The hydrophobic modifying compound containing a double bond structure is selected from one of dodecyl methacrylate, octadecyl methacrylate, and allyl glycidyl ether. The siloxane bridging structure is formed from 3-chloropropyltrimethoxysilane; The molar ratio of nitrogen atoms to carbon atoms in the main structure of the Mannich quaternary ammonium salt is 1:(12-28). The quaternary ammonium cation density of the Mannich reaction-based quaternary ammonium salt bactericide is 2.0–6.5 mmol / g; The number-average molecular weight of the quaternary ammonium salt bactericide based on the Mannich reaction is 1200-12000.
[0006] Preferably, the tertiary amine substitution sites in the Mannich tertiary amine intermediate are located adjacent to the phenolic hydroxyl group and are distributed intermittently along the main structure of the Mannich quaternary ammonium salt.
[0007] Preferably, the alkyl chain length in the quaternizing agent is C4-C18; The anion of the quaternary ammonium cation is selected from one of chloride ions and bromide ions; The hydrophobic regulating chain segment structure accounts for 8%–32% of the total mass of the Mannich reaction-based quaternary ammonium salt bactericide.
[0008] Preferably, the siloxane bridging structure forms a cross-linked network distribution along the main structure of the Mannich quaternary ammonium salt; The density of silicon-oxygen bonds in the cross-linked network distribution is 0.8–3.5 mmol / g.
[0009] Preferably, the method for preparing a quaternary ammonium salt bactericide based on the Mannich reaction includes the following steps: S1. Phenolic compounds and aliphatic amine compounds containing primary amine structures are premixed in a closed reactor. Then, formaldehyde donor compounds are added to the system in stages, and the Mannich reaction is carried out under nitrogen atmosphere to obtain Mannich tertiary amine intermediates. The molar ratio of the phenolic compound, the aliphatic amine compound containing a primary amine structure, and the formaldehyde donor compound is 1:(0.8-1.5):(1.0-2.5). The oxygen content in the nitrogen environment is less than 0.8%; The Mannich reaction temperature is 70-110℃; The phased addition includes adding 35%-55% of the total mass in the first stage and adding the remaining mass in the second stage; S2. The Mannich tertiary amine intermediate is transported into a double-helix circulating flow channel reaction structure, and a quaternizing agent is added to the double-helix circulating flow channel reaction structure. The quaternization reaction is carried out in a microwave-coupled ultrasonic reaction environment to obtain the main structure of the Mannich quaternary ammonium salt. The double-helix circulating flow channel reaction structure includes an inner circulating flow channel and an outer circulating flow channel. The inner circulation channel is used to transport the Mannich tertiary amine intermediate; The outer circulation channel is used to transport the quaternization reagent; An ultrasonic cavitation zone is set at the intersection of the inner circulation channel and the outer circulation channel; The microwave frequency in the microwave-coupled ultrasonic reaction environment is 2450MHz; The ultrasonic frequency in the microwave-coupled ultrasonic reaction environment is 20-45kHz. The ultrasonic energy density is 0.3–1.8 W / mL; The quaternization reaction temperature is 85-135℃; The microwave-coupled ultrasonic reaction environment adopts a pulsed microwave input method; The pulsed microwave input method includes a microwave on-time of 10-25s and a microwave off-time of 5-15s; S3. Add 3-chloropropyltrimethoxysilane to the main structure of the Mannich quaternary ammonium salt to carry out a pre-assembly reaction, and control the water content of the system to be 0.3%-2.5% to obtain a bridged pre-assembly system; S4. Add a hydrophobic regulating compound containing a double bond structure and a free radical initiator to the bridged pre-assembly system, and carry out a grafting reaction by gradient heating to obtain the quaternary ammonium salt bactericide based on the Mannich reaction. The free radical initiator is selected from one of azobisisobutyronitrile and benzoyl peroxide; The gradient heating method includes a first stage temperature of 65-75℃, a second stage temperature of 76-85℃, and a third stage temperature of 86-95℃; S5. The quaternary ammonium salt bactericide based on the Mannich reaction is subjected to continuous vacuum removal and ion exchange purification treatment; The continuous decompression removal process is used to remove low-boiling-point byproducts. The ion exchange purification process uses a strongly acidic cation exchange resin.
[0010] Preferably, the ultrasonic cavitation zones in S2 are arranged in an array along the axial direction of the double-helix circulating flow channel reaction structure; the spacing between two adjacent ultrasonic cavitation zones is 15-60 mm.
[0011] Preferably, the double-helix circulating flow channel reaction structure in S2 is provided with flow-guiding disturbance blades; the flow-guiding disturbance blades are inclined along the helical direction; the inclination angle of the flow-guiding disturbance blades is 15°-45°.
[0012] Preferably, the bridging pre-assembly system in S3 uses a polar solvent as the dispersion medium; The polar solvent is selected from ethanol, isopropanol, and N-methylpyrrolidone.
[0013] Preferably, the grafting reaction in S4 is carried out by continuous nitrogen purging; the flow rate of the continuous nitrogen purging is 0.2-1.5 L / min.
[0014] Preferably, the pressure of the continuous decompression removal process in S5 is 5-35 kPa; the temperature of the continuous decompression removal process is 45-80°C; and the salt content after the ion exchange purification process is less than 0.3%.
[0015] Compared with the prior art, the advantages of this invention are: (1) The continuous coupling technology route of “Mannich reaction - quaternization reaction - hydrophobic grafting reaction” is adopted to form a multi-level composite quaternary ammonium salt structure, which is different from the traditional single-step quaternary ammonium salt system.
[0016] (2) The hydrophobic regulating chain segment structure is introduced around the main structure of the Mannich quaternary ammonium salt to form a hydrophilic-hydrophobic synergistic distribution structure.
[0017] (3) Construct the siloxane bridging structure between the main structure of the Mannich quaternary ammonium salt and the hydrophobic regulating segment structure to improve the overall structural stability.
[0018] (4) The mass transfer efficiency and reaction uniformity in the quaternization reaction process are enhanced by using the double helix circulating flow channel reaction structure combined with the ultrasonic cavitation zone.
[0019] (5) The quaternization reaction is carried out in a microwave-coupled ultrasonic reaction environment to reduce local heat accumulation and improve reaction efficiency.
[0020] (6) The side polycondensation reaction in the Mannich reaction process is reduced by adding the formaldehyde donor compound in stages.
[0021] (7) Gradient heating grafting process is adopted to reduce the problem of uneven chain segment structure caused by free radical aggregation.
[0022] (8) Continuous decompression removal and ion exchange purification are adopted to improve the purity and structural consistency of the product. Attached Figure Description
[0023] Figure 1 This is a schematic diagram of the overall process for synthesizing a quaternary ammonium salt bactericide component based on the Mannich reaction according to the present invention. Detailed Implementation
[0024] Example
[0025] Examples 1-3: Example 1. A quaternary ammonium salt bactericide component based on the Mannich reaction includes a Mannich quaternary ammonium salt main structure, a hydrophobic regulating segment structure, and a siloxane bridging structure; The main structure of Mannich quaternary ammonium salt is formed by the Mannich reaction of phenolic compounds, aliphatic amine compounds containing primary amine structures and formaldehyde donor compounds to form Mannich tertiary amine intermediates, followed by quaternization reaction with quaternizing reagents. The hydrophobic regulating chain segment structure is grafted onto the periphery of the Mannich quaternary ammonium salt main structure; The siloxane bridging structure is embedded between the Mannich quaternary ammonium salt main structure and the hydrophobic regulating chain segment structure; The phenolic compounds are selected from one of phenol, p-tert-butylphenol, nonylphenol, and resorcinol; The aliphatic amine compound containing a primary amine structure is selected from one of dodecylamine, tetradecylamine, hexadecylamine, and octadecylamine; The formaldehyde donor compound is selected from paraformaldehyde and triformaldehyde; The quaternizing agent is selected from one of chloroalkanes, bromoalkanes, and benzyl chloride; The hydrophobic regulatory segment structure is formed by a hydrophobic regulatory compound containing a double bond structure; The hydrophobic modifying compound containing a double bond structure is selected from one of dodecyl methacrylate, octadecyl methacrylate, and allyl glycidyl ether; The siloxane bridging structure is formed by 3-chloropropyltrimethoxysilane; The molar ratio of nitrogen atoms to carbon atoms in the main structure of the Mannich quaternary ammonium salt is 1:(12-28). The quaternary ammonium cation density of Mannich-based quaternary ammonium bactericides is 2.0–6.5 mmol / g; The number average molecular weight of quaternary ammonium salt bactericides based on the Mannich reaction is 1200-12000.
[0026] The tertiary amine substitution sites in the Mannich tertiary amine intermediate are located ortho to the phenolic hydroxyl group and are distributed intermittently along the main structure of the Mannich quaternary ammonium salt.
[0027] The alkyl chain length in the quaternizing reagent is C4-C18; The anion of the quaternary ammonium cation is selected from either chloride or bromide ions; Hydrophobic modulating chain segments account for 8%–32% of the total mass of quaternary ammonium salt bactericides based on the Mannich reaction.
[0028] The siloxane bridging structure forms a cross-linked network distribution along the main structure of the Mannich quaternary ammonium salt; The density of silicon-oxygen bonds in the cross-linked network distribution is 0.8–3.5 mmol / g.
[0029] A method for preparing a quaternary ammonium salt bactericide based on the Mannich reaction includes the following steps: S1. Phenolic compounds and aliphatic amine compounds containing primary amine structures are premixed in a closed reactor. Then, formaldehyde donor compounds are added to the system in stages, and the Mannich reaction is carried out under nitrogen atmosphere to obtain Mannich tertiary amine intermediates. The molar ratio of phenolic compounds, aliphatic amine compounds containing primary amine structures, and formaldehyde donor compounds is 1:(0.8-1.5):(1.0-2.5). The oxygen content in a nitrogen atmosphere is less than 0.8%; The Mannich reaction temperature is 70-110℃; The phased addition includes adding 35%–55% of the total mass in the first phase and adding the remaining mass in the second phase. S2. The Mannich tertiary amine intermediate is delivered into the double helix circulating flow channel reaction structure, and a quaternizing agent is added to the double helix circulating flow channel reaction structure. The quaternization reaction is carried out in a microwave-coupled ultrasonic reaction environment to obtain the main structure of the Mannich quaternary ammonium salt. The double-helix circulating flow channel reaction structure includes an inner circulating flow channel and an outer circulating flow channel. The inner circulation channel is used to transport Mannich tertiary amine intermediates; The outer circulation channel is used to transport quaternizing reagents; An ultrasonic cavitation zone is set at the intersection of the inner and outer circulation channels; The microwave frequency in the microwave-coupled ultrasonic reaction environment is 2450MHz; The ultrasonic frequency in a microwave-coupled ultrasonic reaction environment is 20-45kHz. The ultrasonic energy density is 0.3–1.8 W / mL; The quaternization reaction temperature is 85-135℃; The microwave-coupled ultrasonic response environment uses a pulsed microwave input method; The pulsed microwave input method includes a microwave on-time of 10-25 seconds and a microwave off-time of 5-15 seconds; S3. 3-Chloropropyltrimethoxysilane was added to the main structure of the Mannich quaternary ammonium salt to carry out a pre-assembly reaction, and the water content of the system was controlled to be 0.3%-2.5% to obtain a bridged pre-assembly system. S4. Add a hydrophobic regulating compound containing a double bond structure and a free radical initiator to the bridged pre-assembly system, and carry out the grafting reaction by gradient heating to obtain a quaternary ammonium salt bactericide based on the Mannich reaction. The free radical initiator is selected from one of azobisisobutyronitrile and benzoyl peroxide; The gradient heating method includes a first stage temperature of 65-75℃, a second stage temperature of 76-85℃, and a third stage temperature of 86-95℃; S5. The quaternary ammonium salt bactericide based on the Mannich reaction is subjected to continuous vacuum removal and ion exchange purification. Among them, continuous vacuum removal is used to remove low-boiling-point byproducts; Ion exchange purification was performed using a strongly acidic cation exchange resin.
[0030] The ultrasonic cavitation zones in S2 are arranged in an array along the axial direction of the double-helix circulating flow channel reaction structure; the spacing between two adjacent ultrasonic cavitation zones is 15-60 mm.
[0031] The double-helix circulating flow channel reaction structure in S2 is equipped with flow-guiding and disturbance blades; the flow-guiding and disturbance blades are inclined along the helical direction; the inclination angle of the flow-guiding and disturbance blades is 15°-45°.
[0032] The bridging pre-assembly system in S3 uses a polar solvent as the dispersion medium; The polar solvent is selected from ethanol, isopropanol, and N-methylpyrrolidone.
[0033] The grafting reaction in S4 is carried out by continuous nitrogen purging; the flow rate of continuous nitrogen purging is 0.2-1.5 L / min.
[0034] The pressure of the continuous vacuum removal process in S5 is 5-35 kPa; the temperature of the continuous vacuum removal process is 45-80℃; and the salt content after ion exchange purification is less than 0.3%.
[0035] Example 2.S1. Weigh 100g of nonylphenol and 118g of tetradecylamine and add them to a sealed reactor. Premix them under nitrogen atmosphere and control the oxygen content to 0.5%. Then add 82g of paraformaldehyde in two stages, 45g in the first stage and 37g in the second stage. Control the Mannich reaction temperature to 88°C and react for 4 hours to obtain the Mannich tertiary amine intermediate.
[0036] S2. The Mannich tertiary amine intermediate is fed into a double-helix circulating flow channel reaction structure, and 96g of benzyl chloride is added to the outer circulating flow channel; the microwave frequency is controlled at 2450MHz, the ultrasonic frequency at 32kHz, the ultrasonic energy density at 0.9W / mL, and the quaternization reaction temperature at 108℃; the microwave is turned on for 18s and stopped for 10s; the ultrasonic cavitation zone spacing is 30mm; the tilt angle of the flow-guiding disturbance blades is 28°; after 3h of reaction, the main structure of the Mannich quaternary ammonium salt is obtained.
[0037] S3. Add 45g of 3-chloropropyltrimethoxysilane to the main structure of the Mannich quaternary ammonium salt, and use ethanol as the dispersion medium to control the water content of the system to 1.2%. React for 1.5h to obtain the bridged pre-assembled system.
[0038] S4. Add 55g of octadecyl methacrylate and 4g of azobisisobutyronitrile to the bridged pre-assembly system, and carry out the grafting reaction by continuous nitrogen purging at a nitrogen flow rate of 0.8L / min; the gradient temperature conditions are 70℃, 82℃ and 92℃ respectively, and each stage of the reaction is 1h.
[0039] S5. The obtained product was subjected to continuous vacuum removal treatment at 18 kPa and 65 °C for 2 h, followed by ion exchange purification using a strong acid cation exchange resin to obtain the quaternary ammonium salt bactericide based on the Mannich reaction; the density of quaternary ammonium cations was found to be 4.8 mmol / g, the density of silicon-oxygen bonds was 2.1 mmol / g, and the number average molecular weight was 6200.
[0040] Example 3.S1. Weigh 120g of p-tert-butylphenol and 146g of hexadecylamine and add them to a sealed reactor. Premix them under a nitrogen atmosphere with an oxygen content of 0.3%. Then add 96g of paraformaldehyde in stages, with 50g added in the first stage and 46g added in the second stage. Control the Mannich reaction temperature at 95°C and react for 5 hours to obtain the Mannich tertiary amine intermediate.
[0041] S2. The Mannich tertiary amine intermediate is transported to the double-helix circulating flow channel reaction structure, and 110g of bromododecane is added; the ultrasonic frequency is controlled at 40kHz, the ultrasonic energy density is 1.4W / mL, and the quaternization reaction temperature is 120℃; the microwave is turned on for 22s and stopped for 8s; the ultrasonic cavitation zone spacing is 22mm; and the guide disturbance blade tilt angle is 35°.
[0042] S3. Add 52g of 3-chloropropyltrimethoxysilane and use N-methylpyrrolidone as the dispersion medium to control the water content of the system to 2.0%.
[0043] S4. Add 48g of allyl glycidyl ether and 5g of benzoyl peroxide, and increase the temperature gradient to 72℃, 84℃, and 94℃; the nitrogen purging flow rate is 1.2L / min.
[0044] S5. The product was subjected to continuous vacuum removal at 10 kPa and 72 °C, followed by ion exchange purification. The quaternary ammonium cation density of the obtained product was 5.6 mmol / g, and the number average molecular weight was 8700.
[0045] Comparative example; Comparative Examples 1-3: Comparative Example 1. Compared with Example 1, the difference is that: in S2, the double helix circulating flow channel reaction structure was not used, and the ultrasonic cavitation zone was not set. Instead, a conventional stirred reactor was used for the quaternization reaction. The remaining steps and parameters were the same as in Example 1.
[0046] The resulting product exhibited localized gelation, uneven molecular weight distribution, and a decrease in the density of quaternary ammonium cations.
[0047] Comparative Example 2. Compared with Example 1, the difference is that: in S2, a microwave-coupled ultrasonic reaction environment was not used, but a traditional oil bath heating method was used for the quaternization reaction. The remaining steps and parameters are the same as in Example 1.
[0048] The quaternization reaction time of the obtained product is prolonged, the content of by-products increases, and the salt content increases after purification.
[0049] Comparative Example 3. Compared with Example 1, the difference is that 3-chloropropyltrimethoxysilane was not added in S3, and the remaining steps and parameters were the same as in Example 1.
[0050] The resulting product did not form a stable siloxane bridging network structure and exhibited stratification during storage.
[0051] Comparative Example 4. Compared with Example 1, the difference is that: in S4, the gradient heating method was not used, but the grafting reaction was carried out under a constant temperature condition of 90°C. The remaining steps and parameters are the same as those in Example 1.
[0052] The resulting product has uneven distribution of grafted segments and increased fluctuations in number-average molecular weight.
[0053] To determine the differences between the examples and the comparative examples in terms of structural stability, reaction uniformity, and product purity, the following comparative experiment was designed, and the experimental steps are as follows: Preparation of experimental materials: Take 100g of each of the quaternary ammonium salt bactericide samples based on the Mannich reaction prepared in Example 1, Example 2, Example 3, Comparative Example 1, Comparative Example 2, Comparative Example 3 and Comparative Example 4. Prepare a thermostatic magnetic stirrer, a dynamic light scattering particle size analyzer, a gel permeation chromatograph, an ion chromatograph, a rotational viscometer, and a thermostatic storage box; Prepare a 0.9% sodium chloride solution, sterile deionized water, and ethanol.
[0054] Experimental steps: S1. Weigh 10g of each group of samples, add them to 90mL of sterile deionized water, and stir at 25℃ for 30min to prepare a sample dispersion with a mass fraction of 10%.
[0055] S2. Place the dispersions of each group of samples in a dynamic light scattering particle size analyzer to determine the particle size distribution and dispersion uniformity; then use a rotational viscometer to determine the viscosity fluctuation of the system.
[0056] S3. The number-average molecular weight and molecular weight distribution index of each group of samples were determined by gel permeation chromatography to assess the reaction homogeneity and chain segment stability.
[0057] S4. The residual inorganic salt content and by-product content in each group of samples were detected by ion chromatography to evaluate the post-processing purification effect.
[0058] S5. Place each group of samples in a 40℃ constant temperature storage box for 14 days. Observe the samples every 48 hours to see if there is stratification, gelation and sedimentation, and record the stability of the system.
[0059] S6. Add the dispersion of each group of samples to a 0.9% sodium chloride solution, let stand for 24 hours, and observe the transparency and precipitation of the system to evaluate the structural stability.
[0060] The experimental data are shown in Table 1:
[0061] Experimental conclusion analysis: The experimental results show that Examples 1-3 all exhibited low molecular weight distribution index and high quaternary ammonium cation density, indicating that the use of double helix circulating flow channel reaction structure, microwave coupled ultrasonic reaction environment and gradient temperature grafting process can improve the uniformity of quaternization reaction and grafting stability.
[0062] Among them, Comparative Example 1, due to the lack of a double-helix circulating flow channel reaction structure and ultrasonic cavitation zone, resulted in insufficient local mass transfer and obvious gelation of the system; Comparative Example 2, due to the lack of a microwave-coupled ultrasonic reaction environment, showed a significant increase in the amount of by-product residue; Comparative Example 3, due to the lack of a siloxane bridging structure, showed obvious stratification during storage; Comparative Example 4, due to the lack of a gradient heating method, resulted in uneven distribution of grafted chain segments.
[0063] Comprehensive experimental results show that the present invention can effectively improve reaction uniformity, structural stability and product purity through the synergistic effect of the double-helix circulating flow channel reaction structure, microwave coupled ultrasonic reaction environment, siloxane bridging structure and gradient temperature grafting process.
[0064] To determine the differences in salt tolerance and long-term storage stability between the examples and the comparative examples, the following comparative experiment was designed, and the experimental steps are as follows: Preparation of experimental materials: Take 80g of each of the quaternary ammonium salt bactericide samples based on the Mannich reaction prepared in Example 1, Example 2, Example 3, Comparative Example 1, Comparative Example 2, Comparative Example 3 and Comparative Example 4. Prepare a constant temperature shaker, an ultraviolet spectrophotometer, a centrifuge, a conductivity meter, and a constant temperature aging chamber; Prepare sodium chloride solutions with mass fractions of 1%, 3%, 5%, and 8% respectively; Prepare buffer solutions with pH values of 5, 7, and 9.
[0065] Experimental steps: S1. Weigh 5g of each group of samples and add them to 45mL of deionized water to prepare a sample solution with a mass fraction of 10%.
[0066] S2. Add equal volumes of sodium chloride solutions with mass fractions of 1%, 3%, 5%, and 8% to each group of sample solutions, and shake at 25°C for 30 minutes.
[0067] S3. The transmittance of each group of sample solutions at a wavelength of 600 nm was measured using an ultraviolet spectrophotometer, and the turbidity was recorded. Then, the solution was centrifuged at 3000 r / min for 10 min to observe whether there was any precipitation.
[0068] S4. Place each group of sample solutions in buffer solutions with pH values of 5, 7, and 9 respectively, and keep them at 40°C for 72 hours. Use a conductivity meter to detect the changes in conductivity of the system and record the stable state of the system.
[0069] S5. Place each group of samples in a 60℃ constant temperature aging chamber for 14 days. Detect the viscosity change rate of the samples every 2 days and observe the color change, layering and flow state.
[0070] S6. After the experiment, the salt stability rate, viscosity retention rate and stratification after aging of each group of samples were statistically analyzed.
[0071] The specific experimental data are shown in Table 2:
[0072] Experimental conclusion analysis: The experimental results show that Examples 1-3 maintain high transmittance and viscosity retention under high salt environment and high temperature aging conditions, indicating that the siloxane bridging network structure and hydrophobic regulating chain segment structure formed in this invention can improve the salt resistance stability and long-term storage stability of the system.
[0073] Among them, Comparative Example 1, due to the lack of a double-helix circulating flow channel reaction structure and ultrasonic cavitation zone, resulted in a decrease in the uniformity of the system structure, making it prone to local aggregation under high salt conditions; Comparative Example 2, due to the lack of a microwave-coupled ultrasonic reaction environment, had more by-product residues, leading to a decrease in salt stability; Comparative Example 3, due to the lack of a siloxane bridging structure, showed obvious stratification during the aging process; Comparative Example 4, due to the lack of a gradient temperature grafting process, had unstable grafted chain segment distribution, leading to aggregation under high salt conditions.
[0074] The overall results show that the present invention can effectively improve the salt resistance, thermal stability and long-term storage stability of quaternary ammonium salt bactericides based on the Mannich reaction.
[0075] The foregoing has shown and described the basic principles, main features, and advantages of the present invention. Those skilled in the art should understand that the present invention is not limited to the above embodiments. The embodiments and descriptions in the specification are merely preferred examples of the present invention and are not intended to limit the present invention. Various changes and modifications can be made to the present invention without departing from the spirit and scope thereof, and all such changes and modifications fall within the scope of the present invention as claimed. The scope of protection of the present invention is defined by the appended claims and their equivalents.
Claims
1. A quaternary ammonium salt bactericide based on the Mannich reaction, characterized in that, The aforementioned quaternary ammonium salt bactericide composition based on the Mannich reaction includes a Mannich quaternary ammonium salt main structure, a hydrophobic regulating segment structure, and a siloxane bridging structure. The main structure of Mannich quaternary ammonium salt is formed by the Mannich reaction of phenolic compounds, aliphatic amine compounds containing primary amine structures and formaldehyde donor compounds to form Mannich tertiary amine intermediates, followed by quaternization reaction with quaternizing reagents. The hydrophobic regulating chain segment structure is grafted onto the periphery of the Mannich quaternary ammonium salt main structure; The siloxane bridging structure is embedded between the Mannich quaternary ammonium salt main structure and the hydrophobic regulating chain segment structure; The phenolic compound is selected from one of phenol, p-tert-butylphenol, nonylphenol, and resorcinol; The aliphatic amine compound containing a primary amine structure is selected from one of dodecylamine, tetradecylamine, hexadecylamine, and octadecylamine; The formaldehyde donor compound is selected from paraformaldehyde and triformaldehyde; The quaternizing agent is selected from one of chloroalkanes, bromoalkanes, and benzyl chloride; The hydrophobic regulating segment structure is formed by a hydrophobic regulating compound containing a double bond structure; The hydrophobic modifying compound containing a double bond structure is selected from one of dodecyl methacrylate, octadecyl methacrylate, and allyl glycidyl ether. The siloxane bridging structure is formed from 3-chloropropyltrimethoxysilane; The molar ratio of nitrogen atoms to carbon atoms in the main structure of the Mannich quaternary ammonium salt is 1:(12-28). The quaternary ammonium cation density of the Mannich reaction-based quaternary ammonium salt bactericide is 2.0–6.5 mmol / g; The number-average molecular weight of the quaternary ammonium salt bactericide based on the Mannich reaction is 1200-12000.
2. The quaternary ammonium salt bactericide based on the Mannich reaction according to claim 1, characterized in that, The tertiary amine substitution sites in the Mannich tertiary amine intermediate are located ortho to the phenolic hydroxyl group and are distributed intermittently along the main structure of the Mannich quaternary ammonium salt.
3. The quaternary ammonium salt bactericide based on the Mannich reaction according to claim 1, characterized in that, The alkyl chain length in the quaternizing agent is C4-C18; The anion of the quaternary ammonium cation is selected from one of chloride ions and bromide ions; The hydrophobic regulating chain segment structure accounts for 8%–32% of the total mass of the Mannich reaction-based quaternary ammonium salt bactericide.
4. The quaternary ammonium salt bactericide based on the Mannich reaction according to claim 1, characterized in that, The siloxane bridging structure forms a cross-linked network distributed along the main structure of the Mannich quaternary ammonium salt; The density of silicon-oxygen bonds in the cross-linked network distribution is 0.8–3.5 mmol / g.
5. A method for preparing a quaternary ammonium salt bactericide based on the Mannich reaction, characterized in that, The method for preparing a quaternary ammonium salt bactericide based on the Mannich reaction includes the following steps: S1. Phenolic compounds and aliphatic amine compounds containing primary amine structures are premixed in a closed reactor. Then, formaldehyde donor compounds are added to the system in stages, and the Mannich reaction is carried out under nitrogen atmosphere to obtain Mannich tertiary amine intermediates. The molar ratio of the phenolic compound, the aliphatic amine compound containing a primary amine structure, and the formaldehyde donor compound is 1:(0.8-1.5):(1.0-2.5). The oxygen content in the nitrogen environment is less than 0.8%; The Mannich reaction temperature is 70-110℃; The phased addition includes adding 35%-55% of the total mass in the first stage and adding the remaining mass in the second stage; S2. The Mannich tertiary amine intermediate is transported into a double-helix circulating flow channel reaction structure, and a quaternizing agent is added to the double-helix circulating flow channel reaction structure. The quaternization reaction is carried out in a microwave-coupled ultrasonic reaction environment to obtain the main structure of the Mannich quaternary ammonium salt. The double-helix circulating flow channel reaction structure includes an inner circulating flow channel and an outer circulating flow channel. The inner circulation channel is used to transport the Mannich tertiary amine intermediate; The outer circulation channel is used to transport the quaternization reagent; An ultrasonic cavitation zone is set at the intersection of the inner circulation channel and the outer circulation channel; The microwave frequency in the microwave-coupled ultrasonic reaction environment is 2450MHz; The ultrasonic frequency in the microwave-coupled ultrasonic reaction environment is 20-45kHz. The ultrasonic energy density is 0.3–1.8 W / mL; The quaternization reaction temperature is 85-135℃; The microwave-coupled ultrasonic reaction environment adopts a pulsed microwave input method; The pulsed microwave input method includes a microwave on-time of 10-25s and a microwave off-time of 5-15s; S3. Add 3-chloropropyltrimethoxysilane to the main structure of the Mannich quaternary ammonium salt to carry out a pre-assembly reaction, and control the water content of the system to be 0.3%-2.5% to obtain a bridged pre-assembly system; S4. Add a hydrophobic regulating compound containing a double bond structure and a free radical initiator to the bridged pre-assembly system, and carry out a grafting reaction by gradient heating to obtain the quaternary ammonium salt bactericide based on the Mannich reaction. The free radical initiator is selected from one of azobisisobutyronitrile and benzoyl peroxide; The gradient heating method includes a first stage temperature of 65-75℃, a second stage temperature of 76-85℃, and a third stage temperature of 86-95℃; S5. The quaternary ammonium salt bactericide based on the Mannich reaction is subjected to continuous vacuum removal and ion exchange purification treatment; The continuous decompression removal process is used to remove low-boiling-point byproducts. The ion exchange purification process uses a strongly acidic cation exchange resin.
6. The method for preparing a quaternary ammonium salt bactericide based on the Mannich reaction according to claim 5, characterized in that, The ultrasonic cavitation zones in S2 are arranged in an array along the axial direction of the double-helix circulating flow channel reaction structure; the distance between two adjacent ultrasonic cavitation zones is 15-60 mm.
7. The method for preparing a quaternary ammonium salt bactericide based on the Mannich reaction according to claim 5, characterized in that, The double-helix circulating flow channel reaction structure in S2 is provided with flow-guiding disturbance blades; the flow-guiding disturbance blades are inclined along the helical direction; the inclination angle of the flow-guiding disturbance blades is 15°-45°.
8. The method for preparing a quaternary ammonium salt bactericide based on the Mannich reaction according to claim 5, characterized in that, The bridging pre-assembly system in S3 uses a polar solvent as the dispersion medium; The polar solvent is selected from ethanol, isopropanol, and N-methylpyrrolidone.
9. The method for preparing a quaternary ammonium salt bactericide based on the Mannich reaction according to claim 5, characterized in that, The grafting reaction in S4 is carried out using a continuous nitrogen purging method; the flow rate of the continuous nitrogen purging method is 0.2-1.5 L / min.
10. The method for preparing a quaternary ammonium salt bactericide based on the Mannich reaction according to claim 5, characterized in that, The pressure of the continuous decompression removal process in S5 is 5-35 kPa; the temperature of the continuous decompression removal process is 45-80℃; and the salt content after the ion exchange purification process is less than 0.3%.