Photo-curable pyridinium active monomer as well as preparation method and application thereof

Abstract

The invention discloses a photocurable pyridinium active monomer as well as a preparation method and application thereof. The preparation method comprises the following steps: adding diisocyanate, a solvent and a catalyst into a container, uniformly stirring, dropwise adding an alcohol compound, uniformly adding an acrylic monomer after stirring for reaction, and stirring for reaction to obtain isocyanate-acrylate; the method comprises the following steps: uniformly adding a pyridine monomer into isocyanate-acrylate, reacting for 2-4 hours, adding an alkylating reagent, reacting for 8-12 hours, and carrying out reduced pressure distillation separation to obtain the photocurable pyridinium active monomer. And uniformly mixing the photocurable pyridinium active monomer, the photoinitiator, the active diluent and the acrylate oligomer to obtain the 3D printing photosensitive resin. The method disclosed by the invention is sufficient in reaction, relatively simple in process and easy to implement, the photocurable pyridinium salt monomers with different functions can be designed according to material requirements, and the antibacterial and antistatic effects of the 3D printing material are good.

Description

Technical Field

[0001] This invention belongs to the field of new materials technology, and relates to a photocurable pyridine salt active monomer, its preparation method and application. Background Technology

[0002] Photopolymer 3D printing technology primarily uses liquid resin as a raw material. Due to limitations in raw materials, samples printed from photosensitive resin often exhibit poor mechanical properties, failing to meet production expectations. Therefore, it's necessary to modify the photosensitive resin by adding functional molecules to improve its mechanical properties. Furthermore, bacteria can easily grow on the surface of 3D-printed objects during storage, transportation, and use, potentially posing adverse health risks. Additionally, the surface of polymeric materials is prone to static electricity, which limits the precision and stability of 3D-printed objects used in tooling, fixtures, and electronic products. Therefore, improving the mechanical properties of photosensitive resin has spurred research into antibacterial and antistatic agents, leading to the addition of these functional materials to photosensitive resin to meet market demands.

[0003] In recent years, various pyridine salt materials have appeared on the market. These materials are commonly used as antibacterial and antistatic agents. Their bactericidal principle is "contact sterilization," meaning that the nitrogen in the pyridine salt molecule... + N + By binding to negatively charged microbial cell membranes, membrane protein hydrolysates, and other negatively charged molecules, the polymer's hydrophobic tail integrates into the bacterial hydrophobic membrane core, denaturing structural proteins and enzymes, thereby disrupting the cell membrane and ultimately killing the microorganism. Furthermore, N... + It can interact with negatively charged particles in the air to neutralize static electricity, absorb moisture from the air, and form conductive channels, thereby effectively removing charges and achieving an antistatic effect. Although pyridine salt antibacterial agents have antibacterial effects, they also have drawbacks in practical use, such as low chemical activity, low stability, or volatility. Therefore, it is hoped that a chemically stable pyridine salt molecule with good and long-lasting antibacterial and antistatic effects can be developed and added to photosensitive resins to effectively improve the mechanical properties of photosensitive resins. Summary of the Invention

[0004] One object of the present invention is to provide a photocurable pyridine salt reactive monomer, the structural formula of which is as follows: ; R1 is , , or ; R2 is or ; R3 is , or ; R4 is , , , , or ; This indicates the bond position in the molecule.

[0005] Another object of the present invention is to provide a method for preparing the photocurable pyridine salt active monomer.

[0006] Step (1) Under an ice-water bath, add diisocyanate, solvent and catalyst to the container, stir evenly, add alcohol compound dropwise over 1 to 3 hours, stir and react for 2 to 3 hours, then add acrylic monomer evenly over 3 to 5 hours, stir and react for 1 to 2 hours to obtain isocyanate-acrylate.

[0007] The molar ratio of alcohol to diisocyanate in the reaction system is 1:2.8 to 1:3.2, the molar ratio of diisocyanate to acrylic acid monomer is 3:1, and the amount of catalyst added is 0.05 to 0.5 wt% of the total amount of diisocyanate and acrylic acid monomer.

[0008] Furthermore, the diisocyanate is toluene diisocyanate (TDI), isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), or diphenylmethane diisocyanate (MDI).

[0009] Furthermore, the solvent is N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAc), N,N-methylpyrrolidone (NMP), or dimethyl sulfoxide (DMSO).

[0010] Furthermore, the catalyst is triethylamine, dibutyltin dilaurate, bismuth isooctanoate, bismuth dilaurate, or bismuth neodecanoate.

[0011] Furthermore, the alcohol compound is trimethylolpropane or glycerol.

[0012] Furthermore, the acrylic monomer is hydroxyethyl methacrylate, dipentaerythritol triacrylate, dipentaerythritol pentaacrylate, or cyclotrimethylolpropane methyl acetal acrylate.

[0013] In step (2), under an ice-water bath, pyridine monomers are uniformly added to isocyanate-acrylate and reacted at 25-45°C for 2-4 hours. Then, alkylating agents are added to the intermediate product after the reaction and reacted at 25-45°C for 8-12 hours. The transparent liquid obtained after the reaction is separated by vacuum distillation to obtain photocurable pyridine salt active monomers.

[0014] The molar ratio of the added pyridine monomer to the diisocyanate added in step (1) is 1:1.5 to 1:2, and the molar ratio of the added alkylating agent to the pyridine monomer is 1:1.

[0015] Furthermore, the pyridine monomer is 2-aminopyridine, 3-aminopyridine, 4-aminopyridine, 2-pyridinemethanol, 3-pyridinemethanol or 4-pyridinemethanol.

[0016] Furthermore, the alkylating agent is iodomethane, bromoethane, pentafluorobenzyl bromide, dimethyl sulfate, or methyl p-toluenesulfonate.

[0017] The third objective of this invention is the application of photocurable pyridine salt active monomers as antibacterial and antistatic 3D printing materials.

[0018] A photocurable pyridinium salt reactive monomer, a photoinitiator, a reactive diluent, and an acrylate oligomer were uniformly mixed to obtain a 3D printing photosensitive resin. The mass percentage of each substance in the composition is as follows: Photocurable pyridine salt active monomers 10-30%; 40-60% reactive diluent; 10-40% acrylate oligomers; Photoinitiator 0.5-3%.

[0019] Furthermore, the active diluent is acrylomorpholine, hydroxyethyl methacrylate, isobornyl acrylate, isobornyl methacrylate, or N,N-dimethylacrylamide; Furthermore, the photoinitiator is 2,4,6-trimethylbenzoyl diphenylphosphine oxide, phenyl bis(2,4,6-trimethylbenzoyl)phosphine oxide, or 2-hydroxy-2-methyl-1-phenyl-1-propanone; Furthermore, the acrylate oligomers are epoxy acrylates, aliphatic polyurethane acrylates, polyester polyurethane acrylates, polyether polyurethane acrylates, hyperbranched unsaturated resins, or organosilicon polyether acrylates.

[0020] The application of the photocurable pyridine salt active monomer as an antibacterial and antistatic 3D printing material is characterized in that the 3D printing includes printing using SLA, DLP or LCD 3D printing equipment, and post-curing treatment after printing.

[0021] The method of this invention has a full reaction, a relatively simple process, and is easy to implement. Different functionalities of photocurable pyridine salt monomers can be designed according to material requirements, and the 3D printing materials show good antibacterial and antistatic effects. Attached Figure Description

[0022] Figure 1This is a schematic diagram of the photocurable pyridine salt active monomer 1H NMR spectrum detection in Example 1. Detailed Implementation

[0023] The present invention will now be described in detail with reference to specific embodiments. These embodiments will help those skilled in the art to further understand the present invention, but do not limit the invention in any way. It should be noted that, unless otherwise specified, the embodiments and features described in the embodiments of the present invention can be combined with each other.

[0024] Example 1. Step (1) In an ice-water bath, add 66.66 g (0.3 mol) of isophorone diisocyanate IPDI, 150 mL of N,N-dimethylformamide (DMF) and 0.16 g of catalyst dibutyltin dilaurate to a container. After stirring evenly, add 13.41 g (0.1 mol) of trimethylolpropane dropwise over 2 hours. After stirring and reacting for 2 hours, add 13.01 g (0.1 mol) of hydroxyethyl methacrylate evenly over another 3.5 hours. Stir and react for 1 hour to obtain isocyanate-acrylate. In step (2), 18.82 g (0.2 mol) of 4-aminopyridine was uniformly added to isocyanate-acrylate under an ice-water bath and reacted at 30°C for 3 hours. Then, 28.38 g (0.2 mol) of iodomethane was added to the intermediate product after the reaction and reacted at 30°C for 10 hours. The transparent liquid obtained after the reaction was separated by vacuum distillation to obtain the photocurable pyridine salt active monomer.

[0025] Simplified structural formula of a single unit: Its nuclear magnetic resonance hydrogen spectrum detection is as follows: Figure 1 As shown.

[0026] Example 2. Step (1): Under an ice-water bath, add 62.22 g (0.28 mol) of isophorone diisocyanate IPDI, 150 mL of dimethyl sulfoxide (DMSO) and 0.049 g of triethylamine catalyst to a container. After stirring evenly, add 9.21 g (0.1 mol) of glycerol dropwise over 1 hour. After stirring and reacting for 2.5 hours, add 12.14 g (0.093 mol) of hydroxyethyl methacrylate evenly over another 3 hours. Stir and react for 1.5 hours to obtain isocyanate-acrylate. In step (2), 16.94 g (0.18 mol) of 2-aminopyridine was uniformly added to isocyanate-acrylate under an ice-water bath and reacted at 25°C for 4 hours. Then, 19.61 g (0.18 mol) of bromoethane was added to the intermediate product after the reaction and reacted at 25°C for 12 hours. The transparent liquid obtained after the reaction was separated by vacuum distillation to obtain the photocurable pyridine salt active monomer.

[0027] Simplified structural formula of a single unit: .

[0028] Example 3. Step (1) In an ice-water bath, add 55.73 g (0.32 mol) of hexamethylene diisocyanate (HDI), 200 mL of N,N-dimethylformamide (DMF), and 0.75 g of bismuth isooctanoate catalyst to a container. After stirring evenly, add 13.41 g (0.1 mol) of trimethylolpropane dropwise over 3 hours. After stirring and reacting for 3 hours, add 31.81 g (0.107 mol) of dipentaerythritol triacrylate evenly over another 4.5 hours. Stir and react for 1.5 hours to obtain isocyanate-acrylate. In step (2), 17.88 g (0.19 mol) of 3-aminopyridine was uniformly added to isocyanate-acrylate under an ice-water bath and reacted at 30°C for 3.5 hours. Then, 49.58 g (0.19 mol) of pentafluorobenzyl bromide was added to the intermediate product after the reaction and reacted at 30°C for 11 hours. The transparent liquid obtained after the reaction was separated by vacuum distillation to obtain the photocurable pyridine salt active monomer.

[0029] Simplified structural formula of a single unit: .

[0030] Example 4. Step (1) In an ice-water bath, add 52.13 g (0.31 mol) of toluene diisocyanate (TDI), 200 mL of dimethyl sulfoxide (DMSO), and 0.28 g of bismuth dilaurate catalyst to a container. After stirring evenly, add 9.21 g (0.1 mol) of glycerol dropwise over 1 hour. After stirring and reacting for 2 hours, add 30.82 g (0.103 mol) of dipentaerythritol triacrylate evenly over another 4 hours. Stir and react for 1.5 hours to obtain isocyanate-acrylate. In step (2), 18.55 g (0.17 mol) of 2-pyridinemethanol was uniformly added to isocyanate-acrylate under an ice-water bath and reacted at 35°C for 3 hours. Then, 31.65 g (0.17 mol) of methyl p-toluenesulfonate was added to the intermediate product after the reaction and reacted at 35°C for 10 hours. The transparent liquid obtained after the reaction was separated by vacuum distillation to obtain the photocurable pyridine salt active monomer.

[0031] Simplified structural formula of a single unit: .

[0032] Example 5. Step (1) In an ice-water bath, add 72.57 g (0.29 mol) of diphenylmethane diisocyanate MDI, 250 mL of N,N-dimethylacetamide (DMAc) and 0.22 g of catalyst bismuth neodecanoate to a container. After stirring evenly, add 9.21 g (0.1 mol) of glycerol dropwise over 2 hours. After stirring and reacting for 2.5 hours, add 50.70 g (0.097 mol) of dipentaerythritol pentaacrylate evenly over another 5 hours. Stir and react for 2 hours to obtain isocyanate-acrylate. In step (2), 16.36 g (0.15 mol) of 3-pyridinemethanol was uniformly added to isocyanate-acrylate under an ice-water bath and reacted at 40°C for 2.5 hours. Then, 18.91 g (0.15 mol) of dimethyl sulfate was added to the intermediate product after the reaction and reacted at 25-40°C for 9 hours. The transparent liquid obtained after the reaction was separated by vacuum distillation to obtain the photocurable pyridine salt active monomer.

[0033] Simplified structural formula of a single unit: .

[0034] Example 6. Step (1) Under an ice-water bath, add 66.66 g (0.3 mol) of isophorone diisocyanate IPDI, 300 mL of NN-methylpyrrolidone (NMP) and 0.67 g of catalyst dibutyltin dilaurate to a container. After stirring evenly, add 13.41 g (0.1 mol) of trimethylolpropane dropwise over 3 hours. After stirring and reacting for 3 hours, add 52.45 g (0.1 mol) of dipentaerythritol pentaacrylate evenly over another 5 hours. Stir and react for 2 hours to obtain isocyanate-acrylate. In step (2), 16.36 g (0.15 mol) of 4-pyridinemethanol was uniformly added to isocyanate-acrylate under an ice-water bath and reacted at 45°C for 2 hours. Then, 21.29 g (0.15 mol) of iodomethane was added to the intermediate product after the reaction and reacted at 45°C for 8 hours. The transparent liquid obtained after the reaction was separated by vacuum distillation to obtain the photocurable pyridine salt active monomer.

[0035] Simplified structural formula of a single unit: .

[0036] Example 7. Take 60g of the photocurable pyridine salt active monomer prepared in Example 1, 20g of epoxy acrylate (2-functionality, CN104NS, Sartomer), 88g of acryloylmorpholine and 2g of 2,4,6-trimethylbenzoyl diphenylphosphine oxide and mix them evenly to obtain a photothermal dual-curing 3D printing resin.

[0037] The 3D printing resin composition obtained in this embodiment was placed in a photopolymerization 3D printer SLA equipment and cured layer by layer to form a three-dimensional product. After cleaning the surface of the three-dimensional product with alcohol to remove residual resin, it was transferred to a UV curing chamber for curing for 5 minutes to obtain the final product. The product was tested for tensile strength, elongation at break, antibacterial properties and antistatic properties, and the results are shown in the table below. Example 8. Take 50g of the photocurable pyridine salt active monomer prepared in Example 2, 66g of aliphatic polyurethane acrylate (6-functionality, CN9006NS, Sartomer), 80g of hydroxyethyl methacrylate and 4g of 2,4,6-trimethylbenzoyl diphenylphosphine oxide and mix them evenly to obtain a photothermal dual-curing 3D printing resin.

[0038] The 3D printing resin composition obtained in this embodiment was placed in a photopolymerization 3D printer SLA equipment and cured layer by layer to form a three-dimensional product. After cleaning the surface of the three-dimensional product with alcohol to remove residual resin, it was transferred to a UV curing chamber for curing for 5 minutes to obtain the final product. The product was tested for tensile strength, elongation at break, antibacterial properties and antistatic properties, and the results are shown in the table below. Example 9. Take 40g of the photocurable pyridine salt active monomer prepared in Example 3, 47g (6-functionality, Allnex EBECRYL830, Zhanjiang, USA), 110g of isobornyl acrylate and 3g of phenyl bis(2,4,6-trimethylbenzoyl)phosphine oxide and mix them evenly to obtain a photothermal dual-curing 3D printing resin.

[0039] The 3D printing resin composition obtained in this embodiment was placed in a DLP (Digital Permeable Light) 3D printer and cured layer by layer to obtain a three-dimensional product. After cleaning the surface of the three-dimensional product with alcohol to remove residual resin, it was transferred to a UV curing chamber and cured for 5 minutes to obtain the final product. The product was tested for tensile strength, elongation at break, antibacterial properties, and antistatic properties. The results are shown in the table below. Example 10. Take 30g of the photocurable pyridine salt active monomer prepared in Example 4, 80g of polyether polyurethane acrylate (2-functionality, BR-930D, Bomar), 88g of acrylamide morpholine and 2g of phenyl bis(2,4,6-trimethylbenzoyl)phosphine oxide and mix them evenly to obtain a photothermal dual-curing 3D printing resin.

[0040] The 3D printing resin composition obtained in this embodiment was placed in a DLP (Digital Permeable Light) 3D printer and cured layer by layer to obtain a three-dimensional product. After cleaning the surface of the three-dimensional product with alcohol to remove residual resin, it was transferred to a UV curing chamber and cured for 5 minutes to obtain the final product. The product was tested for tensile strength, elongation at break, antibacterial properties, and antistatic properties. The results are shown in the table below. Example 11. Take 20 grams of the photocurable pyridine salt active monomer prepared in Example 5, 54 grams of hyperbranched unsaturated resin (10 functionality, HUP-102, Wuhan Hyperbranched Resin Technology Co., Ltd.), 120 grams of isobornyl methacrylate and 6 grams of 2-hydroxy-2-methyl-1-phenyl-1-propanone, mix them evenly to obtain a photothermal dual-curing 3D printing resin.

[0041] The 3D printing resin composition obtained in this embodiment was placed in the LCD device of a photopolymer 3D printer and cured layer by layer to form a three-dimensional product. After cleaning the surface of the three-dimensional product with alcohol to remove residual resin, it was transferred to a UV curing chamber and cured for 5 minutes to obtain the final product. The product was tested for tensile strength, elongation at break, antibacterial properties and antistatic properties, and the results are shown in the table below. Example 12. Take 50g of the photocurable pyridine salt active monomer prepared in Example 6, 69g of organosilicon polyether acrylate (2-functionality, BRS-14320S, Bomar), 80g of N,N-dimethylacrylamide and 1g of 2-hydroxy-2-methyl-1-phenyl-1-propanone and mix them evenly to obtain a photothermal dual-curing 3D printing resin.

[0042] The 3D printing resin composition obtained in this embodiment was placed in the LCD device of a photopolymer 3D printer and cured layer by layer to form a three-dimensional product. After cleaning the surface of the three-dimensional product with alcohol to remove residual resin, it was transferred to a UV curing chamber and cured for 5 minutes to obtain the final product. The product was tested for tensile strength, elongation at break, antibacterial properties and antistatic properties, and the results are shown in the table below. Antibacterial performance evaluation: The antibacterial properties of the antibacterial 3D printing materials obtained in Examples 7-12 were tested according to GB / T31402-2015 Antibacterial Properties of Plastic Surfaces. The tests were conducted by the third-party testing agency, CTI. After the tests, the viable bacteria count on the surface of the materials in Examples 7-12 was less than 0.6 CFU / cm³. 3 It exhibits strong antibacterial ability, with antibacterial rates of over 98% and 99% against Staphylococcus aureus and Escherichia coli, respectively.

[0043] The above are merely preferred embodiments of the present invention, but the present invention is not limited to the above embodiments. Any simple substitutions or improvements made based on the above embodiments should be covered within the protection scope of the present invention.

Claims

1. A photocurable pyridinium salt reactive monomer, characterized in that, The simplified structure is as follows: ； R1 is , , or ; R2 is or ; R3 is , or ; R4 is , , , , or ; This indicates the bond position in the molecule.

2. The method for preparing the photocurable pyridinium salt active monomer as described in claim 1, characterized in that: Step (1) Under an ice-water bath, add diisocyanate, solvent and catalyst to a container, stir evenly, add alcohol compound dropwise over 1 to 3 hours, stir and react for 2 to 3 hours, then add acrylic monomer evenly over 3 to 5 hours, stir and react for 1 to 2 hours to obtain isocyanate-acrylate. The molar ratio of alcohol to diisocyanate in the reaction system is 1:2.8 to 1:3.2, the molar ratio of diisocyanate to acrylic acid monomer is 3:1, and the amount of catalyst added is 0.05 to 0.5 wt% of the total amount of diisocyanate and acrylic acid monomer. In step (2), under an ice-water bath, pyridine monomers are uniformly added to isocyanate-acrylate and reacted at 25-45°C for 2-4 hours. Then, alkylating agents are added to the intermediate product after the reaction and reacted at 25-45°C for 8-12 hours. The transparent liquid obtained after the reaction is separated by vacuum distillation to obtain photocurable pyridine salt active monomers. The molar ratio of the added pyridine monomer to the diisocyanate added in step (1) is 1:1.5 to 1:2, and the molar ratio of the added alkylating agent to the pyridine monomer is 1:

1.

3. The method for preparing photocurable pyridinium salt active monomers as described in claim 2, characterized in that: The diisocyanate mentioned is toluene diisocyanate (TDI), isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), or diphenylmethane diisocyanate (MDI). The alcohol compound mentioned is trimethylolpropane or glycerol; The acrylic monomers mentioned are hydroxyethyl methacrylate, dipentaerythritol triacrylate, or dipentaerythritol pentaacrylate; The pyridine monomers are 2-aminopyridine, 3-aminopyridine, 4-aminopyridine, 2-pyridinemethanol, 3-pyridinemethanol or 4-pyridinemethanol.

4. The method for preparing photocurable pyridinium salt active monomers as described in claim 2, characterized in that: The solvent is N,N-dimethylformamide, N,N-dimethylacetamide, N,N-methylpyrrolidone, or dimethyl sulfoxide; The catalyst is triethylamine, dibutyltin dilaurate, bismuth isooctanoate, bismuth dilaurate, or bismuth neodecanoate; The alkylating agent is iodomethane, bromoethane, pentafluorobenzyl bromide, dimethyl sulfate, or methyl p-toluenesulfonate.

5. The application of the photocurable pyridine salt active monomer as described in claim 1 as an antibacterial and antistatic 3D printing material.

6. The application of the photocurable pyridinium salt active monomer as described in claim 5 as an antibacterial and antistatic 3D printing material, characterized in that: A photocurable pyridinium salt reactive monomer, a photoinitiator, a reactive diluent, and an acrylate oligomer were uniformly mixed to obtain a 3D printing photosensitive resin. The mass percentage of each substance in the composition is as follows: Photocurable pyridine salt active monomers 10-30%; 40-60% reactive diluent; 10-40% acrylate oligomers; Photoinitiator 0.5-3%.

7. The application of the photocurable pyridinium salt active monomer as described in claim 6 as an antibacterial and antistatic 3D printing material, characterized in that: The active diluent is acrylomorpholine, hydroxyethyl methacrylate, isobornyl acrylate, isobornyl methacrylate, or N,N-dimethylacrylamide; The photoinitiator is 2,4,6-trimethylbenzoyl diphenylphosphine oxide, phenyl bis(2,4,6-trimethylbenzoyl)phosphine oxide, or 2-hydroxy-2-methyl-1-phenyl-1-propanone; The acrylate oligomers mentioned are epoxy acrylates, aliphatic polyurethane acrylates, polyester polyurethane acrylates, polyether polyurethane acrylates, hyperbranched unsaturated resins, or organosilicon polyether acrylates.

8. The application of the photocurable pyridinium salt active monomer as described in any one of claims 5-7 as an antibacterial and antistatic 3D printing material, characterized in that, The 3D printing mentioned includes printing using SLA, DLP or LCD 3D printing equipment, followed by post-curing treatment after printing.

Images