Preparation process of coating containing quaternary ammonium salt cross-linked acrylic resin

Abstract

The invention relates to the technical field of acrylic resin, and discloses a preparation process of a quaternary ammonium salt-containing cross-linked acrylic resin coating. Butyl acrylate, methyl methacrylate, methyl acrylate, methacrylic acid, hydroxyethyl acrylate, a diacrylate quaternary ammonium salt monomer, a chain transfer agent and the like are used as raw materials; the quaternary ammonium salt-containing cross-linked acrylic resin coating is prepared, so that the cross-linking degree of the acrylic resin is improved, and the mechanical properties such as pencil hardness and impact resistance are improved; meanwhile, an acrylic resin paint film forms a compact and stable chemical cross-linked network, and corrosive media such as water and salt are difficult to enter a paint film matrix, so that the water resistance and the corrosion resistance of the paint film are improved. The biquaternary ammonium salt antibacterial agent is bonded into an acrylic resin molecular chain, and the antibacterial agent does not migrate or separate out in the long-term use process, so that the acrylic resin coating has long-acting antibacterial performance.

Description

Technical Field

[0001] The invention relates to the technical field of acrylic resins, in particular to a preparation process of a quaternary ammonium salt-containing cross-linked acrylic resin coating. Background Art

[0002] Antimicrobial coatings are widely used in wood products, furniture, medical devices, etc. Traditional antimicrobial coatings are made by adding antimicrobial agents to the coatings. However, as time goes by, the antimicrobial agents will slowly precipitate and release from the coatings, and the long-term antimicrobial performance is poor. Structural antimicrobial coatings are made by chemically bonding antimicrobial agents to polymer materials, giving the coatings long-term antimicrobial properties.

[0003] Acrylic resin is a polymer compound obtained by the polymerization of monomers such as acrylic acid. It is widely used in coatings, paints and other fields. Traditional acrylic resin coatings do not have antibacterial properties, and have poor hardness and impact resistance. Quaternary ammonium antibacterial agent is a non-toxic, environmentally friendly antibacterial agent with good antibacterial effect. It has broad application prospects in the field of coatings. Bonding quaternary ammonium antibacterial agent to acrylic resin is an effective method to give acrylic resin coatings long-lasting antibacterial properties. Summary of the invention

[0004] The technical problem solved by the invention is: preparing a quaternary ammonium salt-containing cross-linked acrylic resin coating with high hardness, impact resistance and antibacterial properties.

[0005] The technical solution provided by the present invention is: a preparation process of a quaternary ammonium salt-containing cross-linked acrylic resin coating, comprising the following steps: (1) Add butyl acrylate, methyl methacrylate, methyl acrylate, methacrylic acid, hydroxyethyl acrylate, diacrylate quaternary ammonium salt monomer, chain transfer agent, sodium dodecyl sulfate and water into a flask and stir for 30-60 minutes to obtain a monomer solution; dissolve ammonium persulfate in water to obtain an ammonium persulfate solution; (2) Add the monomer solution and ammonium persulfate solution dropwise into a flask at 75-85°C, stir and react for 2-3 hours, cool, add ammonia water dropwise to adjust the pH to neutral, add a defoamer and a dispersant, stir and disperse, and obtain a quaternary ammonium salt-containing cross-linked acrylic resin coating.

[0006] Furthermore, the chain transfer agent is mercaptoethanol or dodecanethiol.

[0007] Furthermore, the preparation method of the diacrylate quaternary ammonium salt monomer is: (1) Add N,N-dimethylformamide, N,N'-bis(2-hydroxyethyl)ethylenediamine and benzyl chloride into a flask to carry out quaternization reaction, concentrate under reduced pressure, and recrystallize the product with ethanol to obtain N,N'-bis(2-hydroxyethyl)diquaternary ammonium salt.

[0008] (2) Toluene, N,N'-bis(2-hydroxyethyl)diquaternary ammonium salt, acrylic acid and p-toluenesulfonic acid are added into a flask to carry out esterification reaction, and the product is concentrated under reduced pressure. The product is recrystallized with ethanol to obtain a diacrylate quaternary ammonium salt monomer.

[0009] Furthermore, the mass of N,N'-bis(2-hydroxyethyl)ethylenediamine in (1) is 45-60% of that of benzyl chloride.

[0010] Furthermore, the temperature of the quaternization reaction in (1) is 100-140° C. and the time is 36-60 h.

[0011] Furthermore, the mass of acrylic acid and p-toluenesulfonic acid in (2) is 30-45% and 35-48% of N,N'-bis(2-hydroxyethyl)diquaternary ammonium salt, respectively.

[0012] Furthermore, the esterification reaction temperature in (2) is 80-100° C. and the reaction time is 10-20 h.

[0013] The technical effect of the present invention is that: a diacrylate quaternary ammonium salt monomer containing a diene group is cross-linked and copolymerized with monomers such as butyl acrylate to obtain a quaternary ammonium salt-containing cross-linked acrylic resin coating, thereby increasing the cross-linking degree of the acrylic resin and improving mechanical properties such as pencil hardness and impact resistance; at the same time, the acrylic resin paint film forms a tight and stable chemical cross-linking network, and corrosive media such as water and salt are difficult to enter the interior of the paint film matrix, thereby improving the water resistance and corrosion resistance of the paint film.

[0014] The present invention bonds the diquaternary ammonium salt antibacterial agent to the acrylic resin molecular chain. During long-term use, the antibacterial agent will not migrate or precipitate, thereby making the acrylic resin coating have long-lasting antibacterial performance. DETAILED DESCRIPTION

[0015] In order to make the above-mentioned purpose, features and advantages of the present invention more obvious and easy to understand, the specific embodiments of the present invention are described in detail below. In the following description, many specific details are set forth to facilitate a full understanding of the present invention. However, the present invention can be implemented in many other ways different from those described herein, and those skilled in the art can make similar improvements without violating the connotation of the present invention, so the present invention is not limited by the specific embodiments disclosed below.

[0016] Example 1 (1) Add 1500 parts of N,N-dimethylformamide, 50 parts of N,N'-bis(2-hydroxyethyl)ethylenediamine and 100 parts of benzyl chloride into a flask, react at 100°C for 60 h, concentrate under reduced pressure, and recrystallize the product from ethanol to obtain N,N'-bis(2-hydroxyethyl)diquaternary ammonium salt.

[0017] (2) Add 2500 parts of toluene, 100 parts of N,N'-bis(2-hydroxyethyl)diquaternary ammonium salt, 45 parts of acrylic acid, and 42 parts of p-toluenesulfonic acid into a flask, react at 100°C for 12 h, and concentrate under reduced pressure. The product is recrystallized from ethanol to obtain a diacrylate quaternary ammonium salt monomer.

[0018] (3) Add 56 parts by weight of butyl acrylate, 22 parts by weight of methyl methacrylate, 15 parts by weight of methyl acrylate, 4 parts by weight of methacrylic acid, 3 parts by weight of hydroxyethyl acrylate, 0.5 parts by weight of diacrylate quaternary ammonium salt monomer, chain transfer agent mercaptoethanol, 1.5 parts by weight of sodium dodecyl sulfate, and 120 parts by weight of water into a flask and stir for 30 minutes to obtain a monomer solution; dissolve 0.8 parts by weight of ammonium persulfate in 50 parts by weight of water to obtain an ammonium persulfate solution; (4) The monomer solution and ammonium persulfate solution were added dropwise to a flask at 85 °C, stirred for reaction for 2 h, cooled, and ammonia water was added dropwise to adjust the pH to neutral. 0.5 parts of defoamer DF-98 and 0.3 parts of dispersant Efka-1101 were added, stirred and dispersed, and a quaternary ammonium salt-containing cross-linked acrylic resin coating was obtained.

[0019] Example 2 (1) Add 2000 parts of N,N-dimethylformamide, 60 parts of N,N'-bis(2-hydroxyethyl)ethylenediamine and 100 parts of benzyl chloride into a flask, react at 140°C for 36 h, concentrate under reduced pressure, and recrystallize the product from ethanol to obtain N,N'-bis(2-hydroxyethyl)diquaternary ammonium salt.

[0020] (2) Add 2000 parts of toluene, 100 parts of N,N'-bis(2-hydroxyethyl)diquaternary ammonium salt, 35 parts of acrylic acid, and 40 parts of p-toluenesulfonic acid into a flask, react at 80°C for 20 h, and concentrate under reduced pressure. The product is recrystallized from ethanol to obtain a diacrylate quaternary ammonium salt monomer.

[0021] (3) Add 56 parts by weight of butyl acrylate, 22 parts by weight of methyl methacrylate, 15 parts by weight of methyl acrylate, 4 parts by weight of methacrylic acid, 3 parts by weight of hydroxyethyl acrylate, 1.5 parts by weight of diacrylate quaternary ammonium salt monomer, chain transfer agent dodecanethiol, 1.5 parts by weight of sodium dodecyl sulfate, and 120 parts by weight of water into a flask and stir for 60 minutes to obtain a monomer solution; dissolve 0.8 parts by weight of ammonium persulfate in 50 parts by weight of water to obtain an ammonium persulfate solution; (4) The monomer solution and ammonium persulfate solution were added dropwise into a flask at 80 °C, stirred for reaction for 3 h, cooled, and ammonia water was added dropwise to adjust the pH to neutral. 0.5 parts of defoamer DF-98 and 0.3 parts of dispersant Efka-1101 were added, stirred and dispersed, and a quaternary ammonium salt-containing cross-linked acrylic resin coating was obtained.

[0022] Example 3 (1) Add 1500 parts of N,N-dimethylformamide, 45 parts of N,N'-bis(2-hydroxyethyl)ethylenediamine and 100 parts of benzyl chloride into a flask, react at 140°C for 48 h, concentrate under reduced pressure, and recrystallize the product from ethanol to obtain N,N'-bis(2-hydroxyethyl)diquaternary ammonium salt.

[0023] (2) Add 2000 parts of toluene, 100 parts of N,N'-bis(2-hydroxyethyl)diquaternary ammonium salt, 38 parts of acrylic acid, and 40 parts of p-toluenesulfonic acid into a flask, react at 90°C for 12 h, and concentrate under reduced pressure. The product is recrystallized from ethanol to obtain a diacrylate quaternary ammonium salt monomer.

[0024] (3) 56 parts by weight of butyl acrylate, 22 parts by weight of methyl methacrylate, 15 parts by weight of methyl acrylate, 4 parts by weight of methacrylic acid, 3 parts by weight of hydroxyethyl acrylate, 3.5 parts by weight of diacrylate quaternary ammonium salt monomer, chain transfer agent mercaptoethanol, 1.5 parts by weight of sodium dodecyl sulfate, and 120 parts by weight of water were added to a flask and stirred for 60 minutes to obtain a monomer solution; 0.8 parts by weight of ammonium persulfate was dissolved in 50 parts by weight of water to obtain an ammonium persulfate solution; (4) The monomer solution and ammonium persulfate solution were added dropwise to a flask at 75 °C, stirred for reaction for 3 h, cooled, and ammonia water was added dropwise to adjust the pH to neutral. 0.5 parts of defoamer DF-98 and 0.3 parts of dispersant Efka-1101 were added, stirred and dispersed, and a quaternary ammonium salt-containing cross-linked acrylic resin coating was obtained.

[0025] Example 4 (1) Add 2000 parts of N,N-dimethylformamide, 50 parts of N,N'-bis(2-hydroxyethyl)ethylenediamine and 100 parts of benzyl chloride into a flask, react at 120°C for 60 h, concentrate under reduced pressure, and recrystallize the product from ethanol to obtain N,N'-bis(2-hydroxyethyl)diquaternary ammonium salt.

[0026] (2) Add 1500 parts of toluene, 100 parts of N,N'-bis(2-hydroxyethyl)diquaternary ammonium salt, 30 parts of acrylic acid, and 35 parts of p-toluenesulfonic acid into a flask, react at 100°C for 10 h, and concentrate under reduced pressure. The product is recrystallized from ethanol to obtain a diacrylate quaternary ammonium salt monomer.

[0027] (3) 56 parts by weight of butyl acrylate, 22 parts by weight of methyl methacrylate, 15 parts by weight of methyl acrylate, 4 parts by weight of methacrylic acid, 3 parts by weight of hydroxyethyl acrylate, 5 parts by weight of diacrylate quaternary ammonium salt monomer, chain transfer agent mercaptoethanol, 1.5 parts by weight of sodium dodecyl sulfate, and 120 parts by weight of water were added to a flask and stirred for 60 minutes to obtain a monomer solution; 0.8 parts by weight of ammonium persulfate was dissolved in 50 parts by weight of water to obtain an ammonium persulfate solution; (4) The monomer solution and ammonium persulfate solution were added dropwise into a flask at 80 °C, stirred for reaction for 2 h, cooled, and ammonia water was added dropwise to adjust the pH to neutral. 0.5 parts of defoamer DF-98 and 0.3 parts of dispersant Efka-1101 were added, stirred and dispersed, and a quaternary ammonium salt-containing cross-linked acrylic resin coating was obtained.

[0028] Comparative Example 1 The difference between this comparative example and Example 1 is that there are no steps (1) and (2). In step (3), no diacrylate quaternary ammonium salt monomer is added.

[0029] 56 parts by weight of butyl acrylate, 22 parts by weight of methyl methacrylate, 15 parts by weight of methyl acrylate, 4 parts by weight of methacrylic acid, 3 parts by weight of hydroxyethyl acrylate, chain transfer agent mercaptoethanol, 1.5 parts by weight of sodium lauryl sulfate, and 120 parts by weight of water were added to a flask and stirred for 30 minutes to obtain a monomer solution; 0.8 parts by weight of ammonium persulfate was dissolved in 50 parts by weight of water to obtain an ammonium persulfate solution; The monomer solution and ammonium persulfate solution were added dropwise to a flask at 85°C, stirred for reaction for 2 h, cooled, and ammonia water was added dropwise to adjust the pH to neutral. 0.5 parts of defoamer DF-98 and 0.3 parts of dispersant Efka-1101 were added, stirred and dispersed to obtain an acrylic resin coating.

[0030] The performance test of acrylic resin coating is shown in the following table.

[0031] Compared with Comparative Example 1, in Examples 1-4, as the amount of diacrylate quaternary ammonium salt monomer increases, the crosslinking degree of the acrylic resin increases, the pencil hardness increases, the impact resistance increases first and then decreases, and the water resistance and salt spray resistance are significantly improved.

[0032] The acrylic resin coatings prepared in the examples and comparative examples were cured to form paint films; 0.5 mL of Staphylococcus aureus or Escherichia coli bacterial solution (10 8 CFU / mL) on the surface of a clean and sterilized sample, then cover the surface of the sample with the paint film, and culture it at 37℃ and relative humidity>90% for 24 h. Rinse the surface of the solidified paint film with 20 mL of eluent, collect the eluent, and place it in an agar medium, and culture it at 37℃ for 24 h to count the number of colonies.

[0033] Antibacterial rate = (AB) / A×100%.

[0034] A is the average number of recovered bacteria in the blank control group, CFU / piece.

[0035] B is the average number of recovered bacteria in the experimental group, CFU / piece.

[0036] In Examples 1-4, as the amount of diacrylate quaternary ammonium salt monomer increases, the antibacterial rate against Staphylococcus aureus and Escherichia coli increases.

[0037] The acrylic resin coating prepared in Comparative Example 1 does not contain diacrylate quaternary ammonium salt monomers, does not contain diquaternary ammonium salt antibacterial groups, and has the worst antibacterial performance.

[0038] The above-mentioned embodiments only express several implementation methods of the present invention, and the descriptions thereof are relatively specific and detailed, but they cannot be understood as limiting the scope of the invention patent. It should be pointed out that, for ordinary technicians in this field, several variations and improvements can be made without departing from the concept of the present invention, and these all belong to the protection scope of the present invention. Therefore, the protection scope of the patent of the present invention shall be subject to the attached claims.

Claims

1. A preparation process for a quaternary ammonium salt-containing cross-linked acrylic resin coating, characterized in that: The steps include: (1) Add butyl acrylate, methyl methacrylate, methyl acrylate, methacrylic acid, hydroxyethyl acrylate, diacrylate quaternary ammonium salt monomer, chain transfer agent, sodium dodecyl sulfate and water into a flask and stir for 30-60 minutes to obtain a monomer solution; dissolve ammonium persulfate in water to obtain an ammonium persulfate solution; (2) Add the monomer solution and ammonium persulfate solution dropwise into a flask at 75-85°C, stir and react for 2-3 hours, cool, add ammonia water dropwise to adjust the pH to neutral, add a defoamer and a dispersant, stir and disperse, and obtain a quaternary ammonium salt-containing cross-linked acrylic resin coating.

2. The preparation process of the cross-linked acrylic resin coating containing quaternary ammonium salt according to claim 1, characterized in that: The chain transfer agent is mercaptoethanol or dodecanethiol.

3. The preparation process of the cross-linked acrylic resin coating containing quaternary ammonium salt according to claim 1, characterized in that: The preparation method of the diacrylate quaternary ammonium salt monomer is: (1) Add N,N-dimethylformamide, N,N'-bis(2-hydroxyethyl)ethylenediamine and benzyl chloride into a flask to carry out quaternization reaction, concentrate under reduced pressure, and recrystallize the product with ethanol to obtain N,N'-bis(2-hydroxyethyl)diquaternary ammonium salt; (2) Toluene, N,N'-bis(2-hydroxyethyl)diquaternary ammonium salt, acrylic acid and p-toluenesulfonic acid are added into a flask to carry out esterification reaction, and the product is concentrated under reduced pressure. The product is recrystallized with ethanol to obtain a diacrylate quaternary ammonium salt monomer.

4. The preparation process of the quaternary ammonium salt-containing cross-linked acrylic resin coating according to claim 3, characterized in that: The mass of N,N'-bis(2-hydroxyethyl)ethylenediamine in (1) is 45-60% of that of benzyl chloride.

5. The preparation process of the cross-linked acrylic resin coating containing quaternary ammonium salt according to claim 3, characterized in that: The temperature of the quaternization reaction in (1) is 100-140° C. and the time is 36-60 h.

6. The process for preparing the cross-linked acrylic resin coating containing quaternary ammonium salt according to claim 3, characterized in that: The mass of acrylic acid and p-toluenesulfonic acid in (2) is 30-45% and 35-48% of N,N'-bis(2-hydroxyethyl)diquaternary ammonium salt respectively.

7. The process for preparing the cross-linked acrylic resin coating containing quaternary ammonium salt according to claim 3, characterized in that: The esterification reaction temperature in (2) is 80-100°C and the reaction time is 10-20 h.

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