Preparation method and application of acrylic resin containing quaternary ammonium salt and zwitterions

Abstract

The invention belongs to the technical field of marine functional polymer materials, and particularly relates to a preparation method and application of acrylic resin containing quaternary ammonium salt and zwitterions. The zwitter-ion acrylic resin containing quaternary ammonium salt and sulfobetaine synthesized by the invention is environment-friendly antifouling resin, raw materials are easily available, the zwitter-ion acrylic resin has excellent bacteriostasis and algal inhibition performance, the antifouling performance of the resin is improved by introducing the zwitter-ion acrylic resin into the acrylic resin, and meanwhile, through a dynamic water skiing test, the antibacterial and algal inhibition performance of the resin is greatly improved. The resin is not easy to fall off from the surface of a base material, and has good mechanical properties. According to the national standard 'Shallow Sea Soaking Test Method for Antifouling Paint Template' (GB / T 5370-2007), the anti-fouling performance test of the amphoteric ion acrylic resin containing quaternary ammonium salt and sulfo betaine is carried out in Qingdao Shandong, and the test result shows that the coating has a static real sea anti-fouling effect for more than 70 days.

Description

Technical Field

[0001] The invention belongs to the technical field of marine functional polymer materials, and specifically relates to a preparation method of acrylic resin containing quaternary ammonium salt and zwitterion and application thereof. Background Art

[0002] Since humans began to explore the ocean, the problem of biofouling has always existed. In order to solve these problems caused by marine fouling organisms, the commonly used marine antifouling technologies mainly include chlorine gas, seawater electrolysis, heavy metal electrolysis, antifouling coating, mechanical removal and conductive coating. Among these technologies, antifouling coating is still the most economical and effective way to solve the problem of marine biofouling. In the early 19th century, people began to add cuprous oxide or copper sulfate to base resins such as chlorinated rubber and rosin to achieve the purpose of antifouling. This is also the earliest antifouling coating in history. Until the advent of tributyltin (TBT) with broad-spectrum antifouling properties, it immediately became the most effective solution to the problem of marine biofouling at that time. According to statistics, in the 1980s, 60% to 70% of ships in the world were using this self-polishing TBT antifouling coating. However, because TBT can cause reduced spawning and poor development of marine organisms, which harms the marine environment, the International Maritime Organization finally banned the appearance of TBT in antifouling coatings in 2008. With the improvement of people's environmental awareness, green and environmentally friendly marine anti-fouling technology has become a research hotspot and will also be the future development trend of the industry.

[0003] In recent years, researchers have isolated a variety of active substances from many natural organisms to replace toxic antifouling agents. The focus of marine antifouling is no longer just on antifouling performance alone, but has begun to consider the combination of antifouling performance and environmental protection.

[0004] Environmentally friendly marine antifouling agents are a type of product that can reduce or avoid the adverse effects of traditional antifouling agents on the marine ecosystem. They are specially designed for use on the surface of ship hulls, marine equipment, and marine structures to prevent marine organisms from attaching, thereby reducing equipment resistance and fuel consumption. This type of antifouling agent achieves its antifouling effect through environmentally friendly materials, natural ingredients, or low-toxic chemicals, usually replacing traditional toxic ingredients. Summary of the invention

[0005] In order to solve the above technical problems, the present invention provides an environmentally friendly method for preparing a quaternary ammonium salt and zwitterion acrylic resin and its application, which are used in the field of environmentally friendly marine protection.

[0006] In order to achieve the above object, the present invention adopts the following technical solution:

[0007] A quaternary ammonium salt and zwitterionic acrylic resin, wherein the structural formula of the quaternary ammonium salt and zwitterionic acrylic resin is as follows:

[0008]

[0009] Where:

[0010] R1 is -H or -CH3;

[0011] R2 is -CH3;

[0012] R3 is -H or -CH3;

[0013] R4 is -CH2CH3, -CH2CH2CH2CH3, -CH2(CH2)6CH3 or -CH2(CH2)8CH3;

[0014] R5 is -H or -CH3;

[0015] R6 is

[0016] The present invention provides a method for preparing a quaternary ammonium salt and zwitterionic acrylic resin, comprising the following steps:

[0017] A. Preparation of different alkyl quaternary ammonium salt monomers (Q)

[0018] Add dimethylaminoethyl methacrylate into a three-necked flask equipped with a stirrer, fix the three-necked flask in an oil bath, raise the temperature to 45-60°C, introduce nitrogen into the system for 5 minutes, then add alkyl bromide dropwise into the three-necked flask, wherein the molar ratio of dimethylaminoethyl methacrylate to alkyl bromide is 1:1.2-2, stir and react for 8-24 hours, wash the product three times with ether / acetone, and dry in vacuo to obtain methacrylate-N,N-dimethylaminoethyl ester-alkyl bromide quaternary ammonium salt (Q).

[0019] B. Preparation of sulfobetaine structure zwitterionic compounds

[0020] (1) Preparation of 2-(N-(2-(methacryloyloxy)ethyl)-N,N-dimethylammonio)ethyl sulfate (M-1)

[0021] In a three-necked flask, add dimethylaminoethyl methacrylate and 1,3,2-dioxathiazolidine 2,2-dioxide (molar ratio of 1.1:1-2), dissolve in 60-80 mL of acetonitrile, stir at 40-60°C for 30-50 h, cool the reaction mixture at -80 to -25°C, precipitate a solid, filter, wash with acetonitrile, and vacuum dry to obtain M-1 as a colorless powder.

[0022] (2) Preparation of 3-pyridyl-2-methacryloyloxypropane-1-sulfonate (M-2)

[0023] In a three-necked flask, add sodium 3-chloro-2-hydroxypropane sulfonate and pyridine (molar ratio of 1:4-5), use water as solvent, stir and react at 80-90°C for 65-80h; add 8-10mL pyridine again and continue to react for 46-50h. Add mixed ion exchange resin to the reaction mixture and stir until no white precipitate is precipitated in the suspension in 0.1M silver nitrate aqueous solution. Filter, dehydrate the obtained liquid by vacuum distillation, and dry the product under vacuum at room temperature to finally obtain the intermediate 3-pyridyl-2-hydroxypropane-1-sulfonate.

[0024] In a three-necked flask, add 3-pyridyl-2-hydroxypropane-1-sulfonate and trifluoroacetic acid as solvent, stir in an ice bath, and add freshly distilled methacryloyl chloride (3-pyridyl-2-hydroxypropane-1-sulfonate / methacryloyl chloride molar ratio is 1:5) dropwise within 45 minutes. After removing the ice bath, continue stirring at room temperature for 48 to 50 hours. Wash the mixture with anhydrous ether several times, filter and separate the precipitate to obtain M-2 as a colorless powder.

[0025] C. Synthesis of zwitterionic acrylic resin containing quaternary ammonium salt and sulfonate betaine

[0026] In a three-necked flask, 150% to 200% of the total weight of the reactants (acrylate base monomer, methacrylic acid, acrylic acid mixed monomer) are added with solvent, 0.3% to 2.0% of the chain transfer agent, and 0.5% to 1.5% of the initiator are added; 15% to 18% of the weight of the mixture of functional monomers (quaternary ammonium salt monomer (Q) and sulfonate betaine zwitterion monomer (M-1) or (M-2), the molar ratio is 1:0.25 to 5) is added. The reaction temperature is controlled at 75° C. to 110° C. The remaining initiator, resin base monomer, and functional monomer mixture are evenly divided into 9 to 15 portions, and one portion is added every 10 to 20 minutes. The reaction is carried out for 4 to 8 hours under the above conditions to obtain a clear, transparent, and viscous acrylic resin containing quaternary ammonium salt and sulfonate betaine zwitterion.

[0027] According to a preferred embodiment of the present invention, in step A, the alkyl bromide is ethyl bromide, propyl bromide, n-butyl bromide, 1-bromopentane, 1-bromohexane, 1-bromoheptane, 1-bromooctane, 1-bromononane, or n-decane bromide.

[0028] Preferably, the heating temperature in step A is 45° C. If the oil bath temperature is lower than 45° C., the reaction time will be prolonged and the reaction will not be complete. If the temperature is too high, when the temperature is higher than 60° C., the reaction will be too intense and polymerization will occur in a short time. To avoid polymerization, an appropriate inhibitor needs to be added. In addition, because the alkyl chain lengths of the alkyl bromides are different, the reaction time varies. As the alkyl chain length increases, the reaction time increases.

[0029] In the synthesis of M-1 in step B, the molar ratio of dimethylaminoethyl methacrylate to 1,3,2-dioxathiazolidine 2,2-dioxide is 1.1:1-2, stirred at 40-60°C for 30-50h, and then frozen at -80°C to -25°C for 24h-72h, a white solid will precipitate. Since the frozen precipitated white solid is easy to melt at room temperature, it needs to be quickly washed with acetonitrile after being taken out from the low temperature.

[0030] In the synthesis of M-2 in step B, when water is used as the solvent, the heating temperature should not be too high to prevent water from volatilizing; the mixed ion exchange resin is added to remove the byproduct NaCl generated in the reaction, and in order to ensure that the NaCl is completely removed, a silver nitrate standard solution is used for detection until no white precipitate is generated, indicating that the NaCl has been completely removed; when trifluoroacetic acid is used as the solvent, the addition of methacryloyl chloride during stirring needs to be carried out in an ice bath environment in order to slow down the reaction rate of methacryloyl chloride and 3-pyridyl-2-hydroxypropane-1-sulfonate to prevent the reaction from being too intense, and at the same time, the methacryloyl chloride should be excessive to allow the reaction to proceed thoroughly.

[0031] In step C, the molar ratio of the acrylic ester base monomer, methacrylic acid and acrylic acid monomer used in the synthetic acrylic resin is 1-3:0.3-1:0.3-1.

[0032] In step C, the initiator is selected from one or more of azobisisobutyronitrile, azobisisoheptanenitrile, dimethyl azobisisobutyrate, ammonium persulfate or potassium persulfate.

[0033] The solvent described in step C is selected from one or more of toluene, xylene, n-butanol, butyl acetate, and ethyl acetate.

[0034] In step C, the chain transfer agent is n-dodecyl mercaptan, tert-dodecyl mercaptan or aliphatic mercaptan chain transfer agent.

[0035] In the step C, 0.5% to 1.5% of the total weight of the monomer mixture is added with an initiator, and the reaction temperature of the reaction mixture is controlled at 75°C to 110°C. The quaternary ammonium salt and the sulfonated betaine zwitterionic monomer have a variety of molar ratios of 1:0.25 to 5. When the initiator content is less than 0.5% of the total weight of the monomer mixture, it is not conducive to initiating the polymerization reaction of the monomer. When the initiator content is higher than 1.5% of the total weight of the monomer mixture, it is easy to cause violent polymerization. The optimal content of the added initiator is 0.8% to 1.3% of the total weight of the monomer mixture. When the reaction temperature is lower than 75°C, the reaction polymerization rate is slow, which is not conducive to initiating the polymerization reaction of the monomer. When the temperature is higher than 110°C, the reaction polymerization rate is too fast to easily lead to violent polymerization and produce other unnecessary by-products. Therefore, the reaction temperature is controlled at 75°C to 110°C, and the preferred temperature range is 80°C to 90°C.

[0036] In the step C, the remaining initiator and monomer mixture are evenly divided into 9 to 15 portions, and one portion is added every 10 to 20 minutes. Adding the materials in batches can prevent the stirring from being unsmooth due to excessive addition, and on the other hand, the heat generated by the reaction of the materials added in the previous batch can be dispersed. The reaction is carried out for 4 to 8 hours under the described conditions because free radical polymerization requires appropriate reaction time to ensure that the steps of chain initiation, chain growth and chain termination are carried out at the optimal rate, so as to obtain the desired polymer structure and molecular weight. Free radical polymerization is a highly exothermic reaction. The reaction time of 4 to 8 hours is conducive to better control of temperature, avoiding side reactions or reducing polymer quality due to excessive temperature. The preferred reaction time is 5 hours.

[0037] On the other hand, the present invention provides a method for preparing a quaternary ammonium salt and a zwitterionic acrylic resin, comprising the following steps:

[0038] A. Preparation of methacrylate-N,N-dimethylaminoethyl ester-alkyl bromide quaternary ammonium salt

[0039] Add dimethylaminoethyl methacrylate into a three-necked flask equipped with a stirrer, fix the three-necked flask in an oil bath, raise the temperature to 45-60°C, introduce nitrogen into the system for 5 minutes, then drop alkyl bromide into the three-necked flask, wherein the molar ratio of dimethylaminoethyl methacrylate to alkyl bromide is 1:1.2-2, stir and react for 8-24 hours, wash the product with acetone / ether three times, and vacuum dry to obtain methacrylate-N,N-dimethylaminoethyl ester-alkyl bromide quaternary ammonium salt;

[0040] B. Synthesis of acrylic resin containing [2-(methacryloyloxy)ethyl]dimethyl-(3-sulfonic acid propyl)ammonium hydroxide (SPE) and quaternary ammonium salt monomer obtained in step A

[0041] In a three-necked flask, add a solvent of a mixture of xylene and n-butanol (weight ratio 3:1), add acrylate base monomer, methacrylic acid, and acrylic acid in a molar ratio of 1-3:0.3-1:0.3-1, add 0.8% of dodecanethiol and 0.8% of azobisisobutyronitrile based on the total weight of the reactants, add [2-(methacryloyloxy)ethyl]dimethyl-(3-sulfonic acid propyl)ammonium hydroxide and the quaternary ammonium salt monomer obtained in step A, wherein the molar ratio of the two is 1:0.25-5. The mixture was stirred evenly, and the reaction temperature of the reaction mixture was controlled at 80-85° C. The remaining initiator, SPE and methacrylate-N,N-dimethylaminoethyl ester-alkyl bromide quaternary ammonium salt monomer were evenly divided into 10 portions, and one portion was added every 15 minutes. The mixture was reacted for 5 hours under the conditions described above to obtain a clear, transparent and viscous acrylic resin containing methacrylate-N,N-dimethylaminoethyl ester-alkyl bromide quaternary ammonium salt monomer and [2-(methacryloyloxy)ethyl]dimethyl-(3-sulfonic acid propyl) ammonium hydroxide (SPE).

[0042] The present invention also provides the use of the above acrylic resin containing quaternary ammonium salt and zwitterion in preparing marine antifouling coating.

[0043] The beneficial effects of the present invention are:

[0044] The synthesized zwitterionic acrylic resin containing quaternary ammonium salt and sulfonated betaine is an environmentally friendly antifouling resin, the raw materials are easily available, and the resin has excellent antibacterial and antialgae properties. The resin is introduced into the acrylic resin to improve the antifouling performance of the resin. At the same time, through the dynamic paddling test, it is found that the resin is not easy to fall off from the surface of the substrate and has good mechanical properties. According to the national standard "Antifouling Paint Sample Shallow Sea Immersion Test Method" (GB / T 5370-2007), the antifouling performance test of the zwitterionic acrylic resin containing quaternary ammonium salt and sulfonated betaine is carried out in Qingdao, Shandong. The test results show that the coating has a static real sea antifouling effect of more than 70 days. BRIEF DESCRIPTION OF THE DRAWINGS

[0045] Figure 1 The infrared spectrum of the resin containing methacrylate-N,N-dimethylaminoethyl ester-alkyl bromide quaternary ammonium salt and [2-(methacryloyloxy)ethyl]dimethyl-(3-sulfonic acid propyl) ammonium hydroxide (SPE) structure in Example 1-3;

[0046] Figure 2The infrared spectrum of the resin containing the structure of methacrylate-N,N-dimethylaminoethyl ester-bromooctane quaternary ammonium salt and 2-(N-(2-(methacryloyloxy)ethyl)-N,N-dimethylammonium)ethyl sulfate (M-1) / methacrylate-N,N-dimethylaminoethyl ester-bromooctane quaternary ammonium salt and 3-pyridyl-2-methacryloyloxypropane-1-sulfonate (M-2) in Example 4-5;

[0047] Figure 3 The growth of E. coli containing quaternary ammonium salt and sulfobetaine zwitterionic acrylic resin;

[0048] Figure 4 This is a graph showing the results of actual sea testing of Examples 1-6 in the Yellow Sea area of ​​Qingdao City, Shandong Province. DETAILED DESCRIPTION

[0049] The present invention will be better understood through the following examples.

[0050] Example 1: Synthesis of acrylic resin containing [2-(methacryloyloxy)ethyl]dimethyl-(3-sulfonic acid propyl) ammonium hydroxide (SPE) and methacrylate-N,N-dimethylaminoethyl ester-bromobutane quaternary ammonium salt monomers

[0051] The implementation steps of this embodiment are as follows:

[0052] A. Preparation of methacrylate-N,N-dimethylaminoethyl ester-bromobutane quaternary ammonium salt

[0053] In a three-necked flask equipped with a stirrer, add dimethylaminoethyl methacrylate, fix the three-necked flask in an oil bath, raise the temperature to 45-60°C, introduce nitrogen into the system for 5 minutes, then add 1-bromobutane (dimethylaminoethyl methacrylate and 1-bromobutane, the molar ratio is 1:1.2-2) dropwise into the three-necked flask, stir and react for 8-10 hours, wash the product with acetone three times, and vacuum dry to obtain trialkyl methacrylate acyloxyethyl ethyl ester-bromobutane quaternary ammonium salt monomer.

[0054] B. Synthesis of acrylic resin containing [2-(methacryloyloxy)ethyl]dimethyl-(3-sulfonic acid propyl) ammonium hydroxide (SPE) and methacrylate-N,N-dimethylaminoethyl ester-bromobutane quaternary ammonium salt monomers

[0055] In a three-necked flask, a solvent of a mixture of xylene and n-butanol (weight ratio 3:1) is added, and acrylate base monomers, methacrylic acid, and acrylic acid are added in a molar ratio of 1-3:0.3-1:0.3-1. According to the total weight of the reactants, 0.8% of dodecanethiol is added, 0.8% of azobisisobutyronitrile is added, [2-(methacryloyloxy)ethyl]dimethyl-(3-sulfonic acid propyl)ammonium hydroxide (SPE, purchased from Shanghai MacLean Biochemical Technology Co., Ltd.) and methacrylate-N,N-dimethylaminoethyl ester-bromobutyl quaternary ammonium salt monomers obtained in step A are added (molar ratio of 1:0.25-5). The mixture was stirred evenly, and the reaction temperature of the reaction mixture was controlled at 80-85° C. The remaining initiator, SPE and methacrylate-N,N-dimethylaminoethyl ester-bromobutyl quaternary ammonium salt monomer were evenly divided into 10 portions, and one portion was added every 15 minutes. The mixture was reacted for 5 hours under the conditions described above to obtain a clear, transparent and viscous acrylic resin containing methacrylate-N,N-dimethylaminoethyl ester-bromobutyl quaternary ammonium salt monomer and [2-(methacryloyloxy)ethyl]dimethyl-(3-sulfonic acid propyl) ammonium hydroxide (SPE).

[0056] Attached Figure 1 This is the infrared image of acrylic resin containing methacrylate-N,N-dimethylaminoethyl ester-bromobutyl quaternary ammonium salt monomer and [2-(methacryloyloxy)ethyl]dimethyl-(3-sulfonic acid propyl)ammonium hydroxide (SPE).

[0057] Example 2: Synthesis of acrylic resin containing [2-(methacryloyloxy)ethyl]dimethyl-(3-sulfonic acid propyl) ammonium hydroxide (SPE) and methacrylate-N,N-dimethylaminoethyl ester-bromooctane quaternary ammonium salt monomers

[0058] The implementation steps of this embodiment are as follows:

[0059] A. Preparation of methacrylate-N,N-dimethylaminoethyl ester-bromooctane quaternary ammonium salt

[0060] In a three-necked flask equipped with a stirrer, add dimethylaminoethyl methacrylate, fix the three-necked flask in an oil bath, raise the temperature to 45-60°C, introduce nitrogen into the system for 5 minutes, then titrate 1-bromooctane (dimethylaminoethyl methacrylate and 1-bromooctane, the molar ratio of alkane is 1:1.2-2) into the three-necked flask, stir and react for 18-20 hours, wash the product with acetone three times, and vacuum dry to obtain methacrylate-N,N-dimethylaminoethyl ester-bromooctane quaternary ammonium salt monomer.

[0061] B. Synthesis of acrylic resin containing [2-(methacryloyloxy)ethyl]dimethyl-(3-sulfonic acid propyl) ammonium hydroxide (SPE) and methacrylate-N,N-dimethylaminoethyl ester-bromooctane quaternary ammonium salt monomers

[0062] In a three-necked flask, a solvent of a mixture of xylene and n-butanol (weight ratio 3:1) is added, and acrylate base monomer, methacrylic acid, and acrylic acid are added in a molar ratio of 1-3:0.3-1:0.3-1. According to the total weight of the reactants, 0.8% of dodecanethiol is added, 0.8% of azobisisobutyronitrile is added, [2-(methacryloyloxy)ethyl]dimethyl-(3-sulfonic acid propyl)ammonium hydroxide (SPE, purchased from Shanghai MacLean Biochemical Technology Co., Ltd.) and methacrylate-N,N-dimethylaminoethyl ester-bromooctane quaternary ammonium salt monomer obtained in step A are added (the molar ratio of the two is 1:0.25-5). The mixture was stirred evenly, and the reaction temperature was controlled at 80-85° C. The remaining initiator, [2-(methacryloyloxy)ethyl]dimethyl-(3-sulfonic acid propyl)ammonium hydroxide (SPE, purchased from Shanghai MacLean Biochemical Technology Co., Ltd.) and methacrylate-N,N-dimethylaminoethyl ester-bromooctane quaternary ammonium salt monomer were evenly divided into 10 portions, and one portion was added every 15 minutes. The mixture was reacted for 5 hours under the conditions described above to obtain a clear, transparent, viscous acrylic resin containing methacrylate-N,N-dimethylaminoethyl ester-bromooctane quaternary ammonium salt monomer and [2-(methacryloyloxy)ethyl]dimethyl-(3-sulfonic acid propyl)ammonium hydroxide (SPE).

[0063] Attached Figure 1 This is the infrared image of acrylic resin containing methacrylate-N,N-dimethylaminoethyl ester-bromooctane quaternary ammonium salt monomer and [2-(methacryloyloxy)ethyl]dimethyl-(3-sulfonic acid propyl)ammonium hydroxide (SPE).

[0064] Example 3: Synthesis of acrylic resin containing [2-(methacryloyloxy)ethyl]dimethyl-(3-sulfonic acid propyl) ammonium hydroxide (SPE) and methacrylate-N,N-dimethylaminoethyl ester-bromodecane quaternary ammonium salt monomers

[0065] The implementation steps of this embodiment are as follows:

[0066] A. Preparation of methacrylate-N,N-dimethylaminoethyl ester-bromodecane quaternary ammonium salt

[0067] In a three-necked flask equipped with a stirrer, add dimethylaminoethyl methacrylate, fix the three-necked flask in an oil bath, raise the temperature to 45-60°C, introduce nitrogen into the system for 5 minutes, then add n-decyl bromide (dimethylaminoethyl methacrylate and n-decyl bromide, the molar ratio is 1:1.2-2) dropwise into the three-necked flask, stir and react for 20-24 hours, wash the product with acetone three times, and vacuum dry to obtain methacrylate-N,N-dimethylaminoethyl ester-bromodecane quaternary ammonium salt monomer.

[0068] B. Synthesis of acrylic resin containing [2-(methacryloyloxy)ethyl]dimethyl-(3-sulfonic acid propyl) ammonium hydroxide (SPE) and methacrylate-N,N-dimethylaminoethyl ester-bromodecane quaternary ammonium salt monomers

[0069] In a three-necked flask, add a solvent of a mixture of xylene and n-butanol (weight ratio 3:1), add acrylate base monomer, methacrylic acid, and acrylic acid in a molar ratio of 1-3:0.3-1:0.3-1, add 0.8% of dodecanethiol and 0.8% of azobisisobutyronitrile based on the total weight of the reactants; add [2-(methacryloyloxy)ethyl]dimethyl-(3-sulfonic acid propyl)ammonium hydroxide (SPE, purchased from Shanghai MacLean Biochemical Technology Co., Ltd.) and methacrylate-N,N-dimethylaminoethyl ester-bromodecane quaternary ammonium salt monomer obtained in step A (the molar ratio of the two is 1:0.25-5), and stir evenly. The reaction temperature of the reaction mixture is controlled at 80-85° C. The remaining initiator and [2-(methacryloyloxy)ethyl]dimethyl-(3-sulfonic acid propyl)ammonium hydroxide (SPE, purchased from Shanghai MacLean Biochemical Technology Co., Ltd.) and methacrylate-N,N-dimethylaminoethyl ester-bromodecane quaternary ammonium salt monomer are evenly divided into 10 portions, one portion is added every 15 minutes, and the reaction is carried out under the conditions for 5 hours to obtain a clear, transparent and viscous acrylic resin containing methacrylate-N,N-dimethylaminoethyl ester-bromodecane quaternary ammonium salt monomer and [2-(methacryloyloxy)ethyl]dimethyl-(3-sulfonic acid propyl)ammonium hydroxide (SPE).

[0070] Attached Figure 1 This is the infrared image of acrylic resin containing methacrylate-N,N-dimethylaminoethyl ester-bromodecane quaternary ammonium salt monomer and [2-(methacryloyloxy)ethyl]dimethyl-(3-sulfonic acid propyl)ammonium hydroxide (SPE).

[0071] Example 4: Synthesis of acrylic resin containing 2-(N-(2-(methacryloyloxy)ethyl)-N,N-dimethylammonium)ethyl sulfate (M-1) and methacrylate-N,N-dimethylaminoethyl ester-bromooctane quaternary ammonium salt monomers

[0072] The implementation steps of this embodiment are as follows:

[0073] A. Preparation of 2-(N-(2-(methacryloyloxy)ethyl)-N,N-dimethylammonio)ethyl sulfate (M-1)

[0074] In a three-necked flask, add dimethylaminoethyl methacrylate and 1,3,2-dioxathiazolidine 2,2-dioxide (the molar ratio of the two is 1.1:1-2), dissolve in 60-80 mL of acetonitrile, stir at 40-60°C for 30-50 hours, cool the reaction mixture at -80 to -25°C, precipitate solid, filter, wash with acetonitrile, and vacuum dry to obtain M-1 as a colorless powder.

[0075] B. Preparation of methacrylate-N,N-dimethylaminoethyl ester-bromooctane quaternary ammonium salt

[0076] Add dimethylaminoethyl methacrylate into a three-necked flask equipped with a stirrer, fix the three-necked flask in an oil bath, raise the temperature to 45-60°C, introduce nitrogen into the system for 5 minutes, then add 1-bromooctane (dimethylaminoethyl methacrylate and 1-bromooctane, the molar ratio of 1:1.2-2) dropwise into the three-necked flask, stir and react for 18-20 hours, wash the product with acetone three times, and vacuum dry to obtain methacrylate-N,N-dimethylaminoethyl ester-bromooctane quaternary ammonium salt monomer.

[0077] C. Synthesis of acrylic resin containing 2-(N-(2-(methacryloyloxy)ethyl)-N,N-dimethylammonium) ethyl sulfate (M-1) and methacrylate-N,N-dimethylaminoethyl ester-bromooctane quaternary ammonium salt monomers

[0078] In a three-necked flask, add a solvent of a mixture of xylene and n-butanol (weight ratio 3:1), add acrylate base monomer, methacrylic acid, and acrylic acid in a molar ratio of 1-3:0.3-1:0.3-1, add 0.8% of dodecanethiol and 0.8% of azobisisobutyronitrile based on the total weight of the reactants; add 2-(N-(2-(methacryloyloxy)ethyl)-N,N-dimethylammonium)ethyl sulfate (M-1) obtained in step A and methacrylate-N,N-dimethylaminoethyl-bromooctane quaternary ammonium salt monomer obtained in step B (the molar ratio of the two is 1:0.25-5). The mixture was stirred evenly and the reaction temperature was controlled at 80-85° C. The remaining initiator and 2-(N-(2-(methacryloyloxy)ethyl)-N,N-dimethylammonium)ethyl sulfate (M-1) and methacrylate-N,N-dimethylaminoethyl-bromooctane quaternary ammonium salt monomer were evenly divided into 10 portions, and one portion was added every 15 minutes. The mixture was reacted for 5 hours under the conditions described above to obtain a clear, transparent and viscous acrylic resin containing methacrylate-N,N-dimethylaminoethyl-bromooctane quaternary ammonium salt monomer and 2-(N-(2-(methacryloyloxy)ethyl)-N,N-dimethylammonium)ethyl sulfate (M-1).

[0079] Attached Figure 2This is the infrared image of acrylic resin containing methacrylate-N,N-dimethylaminoethyl ester-bromooctane quaternary ammonium salt monomer and 2-(N-(2-(methacryloyloxy)ethyl)-N,N-dimethylammonium)ethyl sulfate (M-1).

[0080] Example 5: Synthesis of acrylic resin containing 3-pyridyl-2-methacryloyloxypropane-1-sulfonate (M-2) and methacrylate-N,N-dimethylaminoethyl ester-bromooctane quaternary ammonium salt monomers

[0081] The implementation steps of this embodiment are as follows:

[0082] A. Preparation of 3-pyridyl-2-methacryloyloxypropane-1-sulfonate (M-2)

[0083] In a three-necked flask, add sodium 3-chloro-2-hydroxypropane sulfonate and pyridine (molar ratio of 1:4-5), use water as solvent, stir and react at 80-90°C for 65-80h; add 8-10mL pyridine again, continue to react for 46-50h, add mixed ion exchange resin to the reaction mixture, stir until no white precipitate is precipitated in the suspension in 0.1M silver nitrate aqueous solution. Filter, distill the obtained liquid under reduced pressure to remove water, and vacuum dry the product at room temperature to finally obtain the intermediate 3-pyridyl-2-hydroxypropane-1-sulfonate.

[0084] In a three-necked flask, add 3-pyridyl-2-hydroxypropane-1-sulfonate and trifluoroacetic acid as solvent, stir in an ice bath, and dropwise add freshly distilled methacryloyl chloride (3-pyridyl-2-hydroxypropane-1-sulfonate / methacryloyl chloride molar ratio is 1:5) within 45 minutes. After removing the ice bath, continue stirring at room temperature for 48 to 50 hours. Wash the mixture with anhydrous ether several times, filter and separate the precipitate to obtain M-2 as a colorless powder.

[0085] B. Preparation of methacrylate-N,N-dimethylaminoethyl ester-bromooctane quaternary ammonium salt

[0086] Add dimethylaminoethyl methacrylate into a three-necked flask equipped with a stirrer, fix the three-necked flask in an oil bath, raise the temperature to 45-60°C, introduce nitrogen into the system for 5 minutes, then add 1-bromooctane (dimethylaminoethyl methacrylate and 1-bromooctane, the molar ratio of 1:1.2-2) dropwise into the three-necked flask, stir and react for 18-20 hours, wash the product with acetone three times, and vacuum dry to obtain methacrylate-N,N-dimethylaminoethyl ester-bromooctane quaternary ammonium salt monomer.

[0087] C. Synthesis of acrylic resin containing 3-pyridyl-2-methacryloyloxypropane-1-sulfonate (M-2) and methacrylate-N,N-dimethylaminoethyl ester-bromooctane quaternary ammonium salt monomers

[0088] In a three-necked flask, add a solvent of a mixture of xylene and n-butanol (weight ratio 3:1), add acrylate base monomer, methacrylic acid, and acrylic acid in a molar ratio of 1-3:0.3-1:0.3-1, add 0.8% of dodecanethiol and 0.8% of azobisisobutyronitrile based on the total weight of the reactants; add 3-pyridyl-2-methacryloyloxypropane-1-sulfonate (M-2) obtained in step A and methacrylate-N,N-dimethylaminoethyl ester-bromooctane quaternary ammonium salt monomer obtained in step B (the molar ratio of the two is 1:0.25-5). The mixture was stirred evenly, and the reaction temperature of the reaction mixture was controlled at 85°C. The remaining initiator, 3-pyridyl-2-methacryloyloxypropane-1-sulfonate (M-2) and methacrylate-N,N-dimethylaminoethyl ester-bromooctane quaternary ammonium salt monomer were evenly divided into 10 parts, and one part was added every 15 minutes. The mixture was reacted for 5 hours under the conditions described above to obtain a clear, transparent and viscous acrylic resin containing methacrylate-N,N-dimethylaminoethyl ester-bromooctane quaternary ammonium salt monomer and 3-pyridyl-2-methacryloyloxypropane-1-sulfonate (M-2).

[0089] Attached Figure 2 This is the infrared image of acrylic resin containing methacrylate-N,N-dimethylaminoethyl ester-bromooctane quaternary ammonium salt monomer and 3-pyridyl-2-methacryloyloxypropane-1-sulfonate (M-2).

[0090] Example 6: Preparation of ordinary acrylic resin

[0091] The implementation steps of this embodiment are as follows:

[0092] The acrylate base monomer, methacrylic acid and acrylic acid are mixed in a molar ratio of 1-3:0.3-1:0.3-1 to obtain a base monomer mixture of a common resin;

[0093] Add 0.8% of azobisisobutyronitrile based on the weight of the monomer mixture into a three-necked flask, add a solvent of a mixture of xylene and n-butanol (weight ratio 3:1), add 0.4% of dodecanethiol based on the total weight of the reactants, and add 15% of the obtained monomer mixture containing azobisisobutyronitrile; stir evenly, control the reaction temperature at 80-85° C., divide the remaining monomer mixture into 10 parts, add one part every 15 minutes, react for 5 hours under the conditions, and obtain a clear, transparent and viscous ordinary acrylic resin.

[0094] Example 7: Antibacterial performance test of zwitterionic acrylic resin containing quaternary ammonium salt and sulfonate betaine

[0095] The implementation steps of this embodiment are as follows:

[0096] Experimental method: dilution plate spreading method;

[0097] Escherichia coli (Gram-negative bacteria) was provided by the Microbiology Laboratory of the College of Marine Life Sciences, Ocean University of China;

[0098] The culture medium for bacterial activation consists of: agar, a solid culture medium sold by Beijing Luqiao Technology Co., Ltd.;

[0099] Bacteria activation culture conditions: constant temperature, shaking;

[0100] Liquid culture medium: liquid culture medium sold by Beijing Luqiao Technology Co., Ltd.;

[0101] Constant temperature incubator: a product sold by Qingdao Chuanghesheng Science and Education Instrument Equipment Co., Ltd. under the trade name of full temperature oscillator;

[0102] Constant Temperature Oscillating Incubator: A product sold by Harbin Donglian Company under the trade name Constant Temperature Oscillating Incubator;

[0103] Test sample: zwitterionic acrylic resin containing quaternary ammonium salt and sulfonate betaine prepared in Examples 1-5;

[0104] Control sample: ordinary acrylic resin prepared in Example 6;

[0105] The zwitterionic acrylic resins containing quaternary ammonium salt and sulfonate betaine prepared in Examples 1-6 were respectively applied on 5×5 cm ABS boards, and dried in air for one week for later use.

[0106] The strains stored on the slant at low temperature (0-4°C) were transferred to a shaking incubator (37±1°C) for activation for 20 hours, and then the strains were transferred from the slant culture medium to the liquid culture medium using an inoculation loop, and then the strains were transferred to the liquid culture medium using an inoculation loop and cultured in a shaking incubator (37±1°C) for 24 hours. The suspension of the bacteria was about 10^ 8 CFU / mL. Use a pipette to draw 1 mL of bacterial solution, then spread it on an ABS plate coated with acrylic resin of different functional monomers, put it in a culture dish, and culture it in a shaking incubator for 20 hours.

[0107] Then, wash the ABS plate with 10 mL of sterile 0.9 wt.% NaCl solution to remove loosely attached bacteria, transfer it to a 20 mL centrifuge tube, then add 0.3 mL of the above-mentioned test bacterial suspension and 2.7 mL of saline to the first 5 mL centrifuge tube, shake evenly, take 0.3 mL of the liquid in the first centrifuge tube and 2.7 mL of saline and add them to the second centrifuge tube, and dilute them 5 times in sequence. Take 100 μL of the solution in the centrifuge tube diluted to an appropriate concentration and add it to the culture dish containing the solid culture medium, then use a sterile triangular rod to evenly spread it until it is completely absorbed, put the solid culture medium in an incubator (37 ± 1 ° C) and culture it for 16 hours, and take pictures and record.

[0108] The calculation method of bacterial inhibition rate is as follows:

[0109] Relative inhibition rate

[0110] Where T0 represents the number of bacteria on the blank glass plate, T n Represents the number of bacteria on the Han functional monomer resin coating.

[0111] The antibacterial performance test results of zwitterionic acrylic resin containing quaternary ammonium salt and sulfonate betaine are shown in the attached Figure 3 .

[0112] By the attached Figure 3 It can be known that both the blank group and the control group (embodiment 6) have a large amount of Escherichia coli colonies, and the number of Escherichia coli in the acrylic resin sample containing quaternary ammonium salt and sulfo-betaine zwitter ion is significantly reduced. By comparing Example 1, Example 2 and Example 3, it can be found that when containing methacrylic acid-N, N-dimethylaminoethyl ester-bromooctane quaternary ammonium salt in resin, the number of Escherichia coli on agar plate is minimum, which is better than the antibacterial effect containing other alkyl chain quaternary ammonium salt resins. When the fixed quaternary ammonium salt monomer is methacrylic acid-N, N-dimethylaminoethyl ester-bromooctane quaternary ammonium salt, the zwitter ion monomer type is changed, and it can be obtained that when the zwitter ion monomer is [2-(methacryloyloxy) ethyl] dimethyl-(3-sulfonic acid propyl) ammonium hydroxide (SPE), the quaternary ammonium salt monomer is methacrylic acid-N, N-dimethylaminoethyl ester-bromooctane quaternary ammonium salt, and its inhibitory effect on Escherichia coli growth is best.

[0113] Example 8: Marine real environment antifouling performance test of zwitterionic acrylic resin containing quaternary ammonium salt and sulfonate betaine The implementation steps of this example are as follows:

[0114] Test sample: zwitterionic acrylic resin containing quaternary ammonium salt and sulfonate betaine prepared in Examples 1-5;

[0115] Control sample: ordinary acrylic resin prepared in Example 6;

[0116] Blank sampleBlank;

[0117] The evaluation of antifouling performance in real sea is the most intuitive and effective evaluation method for testing the actual application performance of antifouling products. This paper refers to the national standard GB / T 5370-2007 "Shallow Sea Immersion Test Method for Antifouling Paint Samples" to test the antifouling performance of synthetic antifouling resin samples in real sea. Both sides of the PVC substrate board are polished, cleaned and dried, and evenly divided into 12 painting areas (150mm×150mm×30mm), leaving blank and control sample areas, and the synthetic resin is evenly painted on each painting area. The coating thickness is about 150-200μm and ventilated and dried in a natural environment. The coated PVC board is placed 1.5 meters underwater on the real sea floating antifouling test platform. The sea area is the Qingdao Port, Shandong Province (36°N, 121°E). The PVC panel is regularly salvaged from the sea area to take photos and record the growth of fouling organisms and the surface condition of the resin coating. Then the PVC panel is placed in the seawater and the original position continues to experiment.

[0118] The antifouling performance test results of the acrylic resin marine antifouling material containing functional monomers of the present invention are listed in the attached Figure 4 .Depend on Figure 4 It can be seen that after 30 days of real sea testing, the surfaces of the blank sample and the control sample (Example 6) were covered with a large number of algae, while the surfaces of the zwitterionic acrylic resin coating containing quaternary ammonium salts and sulfonated betaine synthesized in Examples 1-5 had a small amount of algae and other marine microorganisms. After 70 days of real sea testing, the surfaces of the blank sample and the control sample (Example 6) were covered with marine microorganisms, algae, and a large number of shellfish pots, while the surfaces of the zwitterionic acrylic resin coating containing quaternary ammonium salts and sulfonated betaine also had algae attached, but relatively few, still showing excellent marine antifouling effect.

[0119] These experimental results show that compared with common acrylic resin, the marine antifouling material containing quaternary ammonium salt and sulfonic acid betaine zwitterionic acrylic resin prepared by the present invention has excellent antifouling performance.

Claims

1. A quaternary ammonium salt and zwitterionic acrylic resin, characterized in that: The structural formula of the a kind of quaternary ammonium salt and zwitterionic acrylic resin is as follows: Where: R1 is -H or -CH3; R2 is -CH3; R3 is -H or -CH3; R4 is -CH2CH3, -CH2CH2CH2CH3, -CH2(CH2)6CH3 or -CH2(CH2)8CH3; R5 is -H or -CH3; R6 is 2. A method for preparing a quaternary ammonium salt and a zwitterionic acrylic resin, characterized in that: The following steps are involved: A. Preparation of different alkyl quaternary ammonium salt monomers (Q) Add dimethylaminoethyl methacrylate into a three-necked flask equipped with a stirrer, fix the three-necked flask in an oil bath, raise the temperature to 45-60°C, introduce nitrogen into the system for 5 minutes, then add alkyl bromide dropwise into the three-necked flask, wherein the molar ratio of dimethylaminoethyl methacrylate to alkyl bromide is 1:1.2-2, stir and react for 8-24 hours, wash the product three times with ether / acetone, and dry in vacuo to obtain methacrylate-N,N-dimethylaminoethyl ester-alkyl bromide quaternary ammonium salt (Q). B. Preparation of sulfobetaine structure zwitterionic compounds (1) Preparation of 2-(N-(2-(methacryloyloxy)ethyl)-N,N-dimethylammonio)ethyl sulfate (M-1) In a three-necked flask, add dimethylaminoethyl methacrylate and 1,3,2-dioxathiazolidine 2,2-dioxide (molar ratio of 1.1:1-2), dissolve in 60-80 mL of acetonitrile, stir at 40-60°C for 30-50 h, cool the reaction mixture at -80 to -25°C, precipitate a solid, filter, wash with acetonitrile, and vacuum dry to obtain M-1 as a colorless powder. (2) Preparation of 3-pyridyl-2-methacryloyloxypropane-1-sulfonate (M-2) In a three-necked flask, add sodium 3-chloro-2-hydroxypropane sulfonate and pyridine (molar ratio of 1:4-5), use water as solvent, stir and react at 80-90°C for 65-80h; add 8-10mL pyridine again and continue to react for 46-50h. Add mixed ion exchange resin to the reaction mixture and stir until no white precipitate is precipitated in the suspension in 0.1M silver nitrate aqueous solution. Filter, dehydrate the obtained liquid by vacuum distillation, and dry the product under vacuum at room temperature to finally obtain the intermediate 3-pyridyl-2-hydroxypropane-1-sulfonate. In a three-necked flask, add 3-pyridyl-2-hydroxypropane-1-sulfonate and trifluoroacetic acid as solvent, stir in an ice bath, and add freshly distilled methacryloyl chloride (3-pyridyl-2-hydroxypropane-1-sulfonate / methacryloyl chloride molar ratio is 1:5) dropwise within 45 minutes. After removing the ice bath, continue stirring at room temperature for 48 to 50 hours. Wash the mixture with anhydrous ether several times, filter and separate the precipitate to obtain M-2 as a colorless powder. C. Synthesis of zwitterionic acrylic resin containing quaternary ammonium salt and sulfonate betaine In a three-necked flask, according to the total weight of the reactants (acrylate base monomer, methacrylic acid, acrylic acid mixed monomer), 150% to 200% of the solvent, 0.3% to 2.0% of the chain transfer agent, and 0.5% to 1.5% of the initiator are added; the functional monomer quaternary ammonium salt monomer (Q) and sulfonate betaine zwitterion monomer (M-1) or (M-2) are added in a molar ratio of 1:0.25 to 5, and the weight of the mixture is 15% to 18%. The reaction temperature is controlled at 75°C to 110°C, and the remaining initiator, resin base monomer and functional monomer mixture are evenly divided into 9 to 15 parts, and one part is added every 10 to 20 minutes. The reaction is carried out for 4 to 8 hours under the above conditions to obtain a clear, transparent and viscous quaternary ammonium salt and sulfonate betaine zwitterion acrylic resin.

3. A method for preparing a quaternary ammonium salt and zwitterionic acrylic resin as claimed in claim 2, characterized in that: In step A, the alkyl bromide is ethyl bromide, propyl bromide, n-butyl bromide, 1-pentane bromide, 1-hexane bromide, 1-heptane bromide, 1-octane bromide, 1-nonane bromide and decane bromide.

4. A method for preparing a quaternary ammonium salt and zwitterionic acrylic resin as claimed in claim 2, characterized in that: In step C, the molar ratio of the acrylic ester base monomer, methacrylic acid and acrylic acid monomer used in the synthetic acrylic resin is 1-3:0.3-1:0.3-1.

5. A method for preparing a quaternary ammonium salt and zwitterionic acrylic resin as claimed in claim 2, characterized in that: In step C, the initiator is selected from one or more of azobisisobutyronitrile, azobisisoheptanenitrile, dimethyl azobisisobutyrate, ammonium persulfate or potassium persulfate.

6. A method for preparing a quaternary ammonium salt and zwitterionic acrylic resin as claimed in claim 2, characterized in that: The solvent described in step C is selected from one or more of toluene, xylene, n-butanol, butyl acetate, and ethyl acetate.

7. A method for preparing a quaternary ammonium salt and zwitterionic acrylic resin as claimed in claim 2, characterized in that: In step C, the chain transfer agent is n-dodecyl mercaptan, tert-dodecyl mercaptan or aliphatic mercaptan chain transfer agent.

8. A method for preparing a quaternary ammonium salt and zwitterionic acrylic resin, characterized in that , including the following steps: A. Preparation of methacrylate-N,N-dimethylaminoethyl ester-alkyl bromide quaternary ammonium salt Add dimethylaminoethyl methacrylate into a three-necked flask equipped with a stirrer, fix the three-necked flask in an oil bath, raise the temperature to 45-60°C, introduce nitrogen into the system for 5 minutes, then drop alkyl bromide into the three-necked flask, wherein the molar ratio of dimethylaminoethyl methacrylate to alkyl bromide is 1:1.2-2, stir and react for 8-24 hours, wash the product with acetone / ether three times, and vacuum dry to obtain methacrylate-N,N-dimethylaminoethyl ester-alkyl bromide quaternary ammonium salt; B. Synthesis of acrylic resin containing [2-(methacryloyloxy)ethyl]dimethyl-(3-sulfonic acid propyl)ammonium hydroxide (SPE) and quaternary ammonium salt monomer obtained in step A In a three-necked flask, add a solvent of a mixture of xylene and n-butanol (weight ratio 3:1), add acrylate base monomer, methacrylic acid, and acrylic acid in a molar ratio of 1-3:0.3-1:0.3-1, add 0.8% of dodecanethiol and 0.8% of azobisisobutyronitrile based on the total weight of the reactants, add [2-(methacryloyloxy)ethyl]dimethyl-(3-sulfonic acid propyl)ammonium hydroxide and the quaternary ammonium salt monomer obtained in step A, wherein the molar ratio of the two is 1:0.25-5. The mixture was stirred evenly, and the reaction temperature of the reaction mixture was controlled at 80-85° C. The remaining initiator, SPE and methacrylate-N,N-dimethylaminoethyl ester-alkyl bromide quaternary ammonium salt monomer were evenly divided into 10 portions, and one portion was added every 15 minutes. The mixture was reacted for 5 hours under the conditions described above to obtain a clear, transparent and viscous acrylic resin containing methacrylate-N,N-dimethylaminoethyl ester-alkyl bromide quaternary ammonium salt monomer and [2-(methacryloyloxy)ethyl]dimethyl-(3-sulfonic acid propyl) ammonium hydroxide (SPE).

9. Use of the quaternary ammonium salt- and zwitterionic resin according to claim 1 in marine antifouling coatings.

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