Antibacterial modified nano SiO2 grafted polystyrene composite material and preparation method thereof

Abstract

The invention relates to the technical field of high polymer materials, and discloses an antibacterial modified nano SiO2 grafted polystyrene composite material, styrene and an allyl amide imidazole monomer are used as polymerization monomers, imidazole-based polystyrene with a molecular side chain containing an imidazole functional group is obtained through polymerization, bromine atoms and tertiary amine of imidazole are subjected to a quaternization reaction, and the antibacterial modified nano SiO2 grafted polystyrene composite material is obtained. According to the preparation method, alkyl bromide modified SiO2 and imidazolyl polystyrene are subjected to quaternization reaction, so that long-chain alkyl imidazole quaternary ammonium salt is generated between the alkyl bromide modified SiO2 and imidazolyl polystyrene, polystyrene and nano SiO2 are organically combined through imidazole quaternary ammonium salt ionic bonds, the compatibility between polystyrene and nano SiO2 is improved, the problem of agglomeration of nano SiO2 is effectively solved, and the reinforcing effect of nano SiO2 can be better exerted; and the long-chain alkyl imidazole quaternary ammonium salt between the nano SiO2 and the polystyrene has excellent antibacterial property, so that the polystyrene material is endowed with excellent antibacterial property.

Description

Technical Field

[0001] The invention relates to the technical field of polymer materials, in particular to an antibacterial modified nano-SiO2 grafted polystyrene composite material and a preparation method thereof. Background Art

[0002] Antimicrobial agents mainly include quaternary ammonium salts, imidazoles, guanidines and other antimicrobial agents. Among them, quaternary ammonium salt antimicrobial agents have the advantages of high antimicrobial activity, low toxicity and non-irritation, and are widely used in medical and health fields. Patent CN107114366B "A preparation method and application of photosensitive antibacterial silica microspheres" discloses fluorine-containing quaternary ammonium salt functionalized silica microspheres, which are applied to the field of photocurable polymer coatings to enhance the antibacterial properties of the coatings, and can give play to the nano-size effect of nano-silica to improve the comprehensive performance of the coatings.

[0003] Polystyrene is a common polymer material with the advantages of good thermal insulation, excellent electrical properties, high mechanical properties, etc. It is widely used in thermal insulation materials, containers and utensils, etc. However, polystyrene does not have antibacterial properties, which limits its application in industrial development. Therefore, it is of great significance to modify polystyrene for antibacterial purposes. The quaternary ammonium antibacterial agent is modified onto the surface of inorganic nanomaterials, such as nano-silica, for functional modification, and then the polystyrene is modified, which can simultaneously exert the antibacterial properties of the antibacterial agent and the enhanced properties of nano-silica. Summary of the invention

[0004] In view of the deficiencies of the prior art, the present invention provides an antibacterial modified nano-SiO2 grafted polystyrene composite material and a preparation method, which improves the dispersibility of nano-SiO2 and gives polystyrene excellent antibacterial properties.

[0005] To achieve the above object, the present invention provides the following technical solution: an antibacterial modified nano-SiO2 grafted polystyrene composite material, the preparation method of the antibacterial modified nano-SiO2 grafted polystyrene composite material is as follows: (1) Disperse nano-SiO2 uniformly in toluene solvent, add toluene diisocyanate, heat to 80-100 °C, react for 6-12 h, centrifuge after reaction, wash with acetone, and dry to obtain isocyanate-modified SiO2.

[0006] (2) The isocyanate-modified SiO2 is uniformly dispersed in chloroform solvent, 12-bromo-1-dodecanol and a catalyst dibutyltin dilaurate are added, and the reaction is refluxed under heating. After the reaction, the reaction is centrifuged, washed with chloroform and acetone, and dried to obtain alkyl bromide-modified SiO2.

[0007] (3) Add styrene and allyl amide imidazole monomer (C8H11 N3O), dispersant polyvinyl alcohol, stir evenly, add initiator azobisisobutyronitrile, heat to 55-75 ℃, polymerize for 24-48 hours, centrifuge after reaction, wash with distilled water and ethanol, and dry to obtain imidazole polystyrene.

[0008] (4) Alkyl bromide-modified SiO2 is uniformly dispersed in dimethyl sulfoxide solvent, and imidazole polystyrene is added. After stirring and dissolving, a reaction occurs. After the reaction, distilled water is added for precipitation. The solvent is filtered, and the mixture is washed with distilled water and ethanol. After drying, the modified nano-SiO2 grafted polystyrene is obtained.

[0009] (5) Add modified nano-SiO2 grafted polystyrene, antioxidant 1010, and plasticizer dibutyl phthalate into a twin-screw extruder for melt extrusion to obtain an antibacterial modified nano-SiO2 grafted polystyrene composite material.

[0010] Preferably, in step (2), the weight proportions of isocyanate-modified SiO2 are 100 parts, 12-bromo-1-dodecanol are 60-200 parts, and dibutyltin dilaurate are 0.5-2.5 parts.

[0011] Preferably, the reaction in step (2) is carried out at 60-75° C. for 18-36 h.

[0012] Preferably, in step (3), the weight proportions of styrene are 100 parts, allylamide imidazole is 1.5-6 parts, polyvinyl alcohol is 6-10 parts, and azobisisobutyronitrile is 1.5-4 parts.

[0013] Preferably, the weight proportion of the alkyl bromide-modified SiO2 in step (4) is 0.5-3 parts, and the weight proportion of the imidazole polystyrene is 100 parts.

[0014] Preferably, the reaction in step (4) is carried out at 60-90° C. for 10-30 h.

[0015] Compared with the prior art, the present invention has the following beneficial technical effects: The antibacterial modified nano-SiO2 grafted polystyrene composite material uses toluene diisocyanate to modify the nano-SiO2, modifies the isocyanate group on the surface, and then reacts with the hydroxyl group of 12-bromo-1-dodecanol to obtain alkyl bromide-modified SiO2, thereby chemically modifying the bromoalkyl long chain on the surface of the nano-SiO2, thereby realizing the functional modification of the nano-SiO2. Styrene and allylamide imidazole monomers are used as polymerization monomers to obtain imidazole-based polystyrene with imidazole functional groups in the molecular side chain. The quaternization reaction is carried out by using bromine atoms and tertiary amines of imidazole, and the alkyl bromide-modified SiO2 and the imidazole-based polystyrene are subjected to quaternization reaction, thereby generating a long-chain alkyl imidazole quaternary ammonium salt between the polystyrene and the nano-SiO2. The polystyrene and the nano-SiO2 are organically combined through the ionic bond of the imidazole quaternary ammonium salt, thereby improving the compatibility between the two, effectively overcoming the agglomeration problem of the nano-SiO2, and better exerting the enhancement effect of the nano-SiO2. The long-chain alkyl imidazole quaternary ammonium salt between the nano-SiO2 and the polystyrene has excellent antibacterial properties, and has obvious antibacterial effects on bacteria such as Staphylococcus aureus, thereby giving the polystyrene material excellent antibacterial properties and expanding the actual industrial production and application of the material. BRIEF DESCRIPTION OF THE DRAWINGS

[0016] Figure 1 It is the structural formula of allyl amide imidazole monomer. DETAILED DESCRIPTION

[0017] To achieve the above object, the present invention provides the following embodiments and examples: An antibacterial modified nano-SiO2 grafted polystyrene composite material, the preparation method is as follows: (1) Disperse nano-SiO2 uniformly in toluene solvent, add toluene diisocyanate, heat to 80-100 °C, react for 6-12 h, centrifuge after reaction, wash with acetone, and dry to obtain isocyanate-modified SiO2.

[0018] (2) Disperse 100 parts by weight of isocyanate-modified SiO2 uniformly in chloroform solvent, add 60-200 parts of 12-bromo-1-dodecanol and 0.5-2.5 parts of catalyst dibutyltin dilaurate, heat to 60-75°C, reflux to react for 18-36 hours, centrifuge after the reaction, wash with chloroform and acetone, and dry to obtain alkyl bromide-modified SiO2.

[0019] (3) Add 100 parts by weight of styrene and 1.5-6 parts by weight of allyl amide imidazole monomer (C8H 11 N3O), 6-10 parts of dispersant polyvinyl alcohol, stir evenly, add 1.5-4 parts of initiator azobisisobutyronitrile, heat to 55-75 ℃, polymerize for 24-48 hours, centrifuge after reaction, wash with distilled water and ethanol, and dry to obtain imidazole polystyrene.

[0020] (4) Disperse 0.5-3 parts by weight of alkyl bromide-modified SiO2 uniformly in dimethyl sulfoxide solvent, add 100 parts of imidazole polystyrene, stir to dissolve, and react at 60-90 °C for 10-30 h. After the reaction, add distilled water for precipitation, filter the solvent, wash with distilled water and ethanol, and dry to obtain modified nano-SiO2 grafted polystyrene.

[0021] (5) Add modified nano-SiO2 grafted polystyrene, antioxidant 1010, and plasticizer dibutyl phthalate into a twin-screw extruder for melt extrusion to obtain an antibacterial modified nano-SiO2 grafted polystyrene composite material. Example 1

[0022] (1) Disperse 0.5 g of nano-SiO2 uniformly in 20 mL of toluene solvent, add 0.2 g of toluene diisocyanate, heat to 80 °C, react for 6 h, centrifuge after reaction, wash with acetone, and dry to obtain isocyanate-modified SiO2.

[0023] (2) Disperse 1 g of isocyanate-modified SiO2 evenly in 50 mL of chloroform solvent, add 0.6 g of 12-bromo-1-dodecanol and 0.005 g of catalyst dibutyltin dilaurate, heat to 60 °C, reflux for reaction for 18 h, centrifuge after reaction, wash with chloroform and acetone, and dry to obtain alkyl bromide-modified SiO2.

[0024] (3) To a mixed solvent of 2 mL of distilled water and 40 mL of ethanol, add 5 g of styrene, 0.075 g of allyl amide imidazole monomer, and 0.3 g of dispersant polyvinyl alcohol. Stir evenly and then add 0.08 g of initiator azobisisobutyronitrile. Heat to 55 °C and allow the polymerization to react for 24 h. After the reaction, centrifuge, wash with distilled water and ethanol, and dry to obtain imidazole-based polystyrene.

[0025] (4) Disperse 0.05 g of alkyl bromide-modified SiO2 evenly in 200 mL of dimethyl sulfoxide solvent, add 10 g of imidazole polystyrene, stir to dissolve, and react at 60 °C for 10 h. After the reaction, add distilled water for precipitation, filter the solvent, wash with distilled water and ethanol, and dry to obtain modified nano-SiO2 grafted polystyrene.

[0026] (5) 10 g of modified nano-SiO2 grafted polystyrene, 0.03 g of antioxidant 1010, and 0.15 g of plasticizer dibutyl phthalate were added into a twin-screw extruder for melt extrusion to obtain an antibacterial modified nano-SiO2 grafted polystyrene composite material. Example 2

[0027] (1) Disperse 0.5 g of nano-SiO2 uniformly in 30 mL of toluene solvent, add 0.3 g of toluene diisocyanate, heat to 80 °C, react for 12 h, centrifuge after reaction, wash with acetone, and dry to obtain isocyanate-modified SiO2.

[0028] (2) Disperse 1 g of isocyanate-modified SiO2 evenly in 80 mL of chloroform solvent, add 1 g of 12-bromo-1-dodecanol and 0.01 g of catalyst dibutyltin dilaurate, heat to 70 °C, reflux for 24 h, centrifuge after reaction, wash with chloroform and acetone, and dry to obtain alkyl bromide-modified SiO2.

[0029] (3) To a mixed solvent of 3 mL of distilled water and 50 mL of ethanol, add 5 g of styrene, 0.12 g of allyl amide imidazole monomer, and 0.35 g of dispersant polyvinyl alcohol. Stir evenly and then add 0.1 g of initiator azobisisobutyronitrile. Heat to 60 °C and polymerize for 36 h. After the reaction, centrifuge, wash with distilled water and ethanol, and dry to obtain imidazole polystyrene.

[0030] (4) Disperse 0.12 g of alkyl bromide-modified SiO2 evenly in 300 mL of dimethyl sulfoxide solvent, add 10 g of imidazole polystyrene, stir to dissolve and react at 80 °C for 10 h. After the reaction, add distilled water for precipitation, filter the solvent, wash with distilled water and ethanol, and dry to obtain modified nano-SiO2 grafted polystyrene.

[0031] (5) 10 g of modified nano-SiO2 grafted polystyrene, 0.04 g of antioxidant 1010, and 0.2 g of plasticizer dibutyl phthalate were added into a twin-screw extruder for melt extrusion to obtain an antibacterial modified nano-SiO2 grafted polystyrene composite material. Example 3

[0032] (1) Disperse 0.5 g of nano-SiO2 uniformly in 40 mL of toluene solvent, add 0.4 g of toluene diisocyanate, heat to 70 °C, react for 10 h, centrifuge after the reaction, wash with acetone, and dry to obtain isocyanate-modified SiO2.

[0033] (2) Disperse 1 g of isocyanate-modified SiO2 evenly in 100 mL of chloroform solvent, add 1.2 g of 12-bromo-1-dodecanol and 0.015 g of catalyst dibutyltin dilaurate, heat to 70 °C, reflux for reaction for 24 h, centrifuge after reaction, wash with chloroform and acetone, and dry to obtain alkyl bromide-modified SiO2.

[0034] (3) To a mixed solvent of 3 mL of distilled water and 60 mL of ethanol, add 5 g of styrene, 0.15 g of allyl amide imidazole monomer, and 0.4 g of dispersant polyvinyl alcohol. Stir evenly and then add 0.12 g of initiator azobisisobutyronitrile. Heat to 65 °C and polymerize for 36 h. After the reaction, centrifuge, wash with distilled water and ethanol, and dry to obtain imidazole polystyrene.

[0035] (4) Disperse 0.18 g of alkyl bromide-modified SiO2 evenly in 350 mL of dimethyl sulfoxide solvent, add 10 g of imidazole polystyrene, stir to dissolve and react at 70 °C for 18 h. After the reaction, add distilled water for precipitation, filter the solvent, wash with distilled water and ethanol, and dry to obtain modified nano-SiO2 grafted polystyrene.

[0036] (5) 10 g of modified nano-SiO2 grafted polystyrene, 0.05 g of antioxidant 1010, and 0.2 g of plasticizer dibutyl phthalate were added into a twin-screw extruder for melt extrusion to obtain an antibacterial modified nano-SiO2 grafted polystyrene composite material. Example 4

[0037] (1) Disperse 0.5 g of nano-SiO2 evenly in 40 mL of toluene solvent, add 0.5 g of toluene diisocyanate, heat to 80 °C, react for 12 h, centrifuge after reaction, wash with acetone, and dry to obtain isocyanate-modified SiO2.

[0038] (2) Disperse 1 g of isocyanate-modified SiO2 evenly in 200 mL of chloroform solvent, add 1.7 g of 12-bromo-1-dodecanol and 0.02 g of catalyst dibutyltin dilaurate, heat to 75 °C, reflux for reaction for 24 h, centrifuge after reaction, wash with chloroform and acetone, and dry to obtain alkyl bromide-modified SiO2.

[0039] (3) To a mixed solvent of 5 mL of distilled water and 70 mL of ethanol, add 5 g of styrene, 0.25 g of allyl amide imidazole monomer, and 0.45 g of dispersant polyvinyl alcohol. Stir evenly and then add 0.16 g of initiator azobisisobutyronitrile. Heat to 65 °C and polymerize for 36 h. After the reaction, centrifuge, wash with distilled water and ethanol, and dry to obtain imidazole polystyrene.

[0040] (4) Disperse 0.25 g of alkyl bromide-modified SiO2 evenly in 500 mL of dimethyl sulfoxide solvent, add 10 g of imidazole polystyrene, stir to dissolve and react at 80 °C for 24 h. After the reaction, add distilled water for precipitation, filter the solvent, wash with distilled water and ethanol, and dry to obtain modified nano-SiO2 grafted polystyrene.

[0041] (5) 10 g of modified nano-SiO2 grafted polystyrene, 0.07 g of antioxidant 1010, and 0.26 g of plasticizer dibutyl phthalate were added into a twin-screw extruder for melt extrusion to obtain an antibacterial modified nano-SiO2 grafted polystyrene composite material. Example 5

[0042] (1) Disperse 0.5 g of nano-SiO2 uniformly in 50 mL of toluene solvent, add 0.6 g of toluene diisocyanate, heat to 100 °C, react for 12 h, centrifuge after the reaction, wash with acetone, and dry to obtain isocyanate-modified SiO2.

[0043] (2) Disperse 1 g of isocyanate-modified SiO2 evenly in 200 mL of chloroform solvent, add 2 g of 12-bromo-1-dodecanol and 0.025 g of catalyst dibutyltin dilaurate, heat to 75 °C, reflux for 36 h, centrifuge after reaction, wash with chloroform and acetone, and dry to obtain alkyl bromide-modified SiO2.

[0044] (3) To a mixed solvent of 5 mL of distilled water and 80 mL of ethanol, add 5 g of styrene, 0.3 g of allyl amide imidazole monomer, and 0.5 g of dispersant polyvinyl alcohol. Stir well and add 0.2 g of initiator azobisisobutyronitrile. Heat to 75 °C and allow the polymerization to react for 48 h. After the reaction, centrifuge, wash with distilled water and ethanol, and dry to obtain imidazole-based polystyrene.

[0045] (4) Disperse 0.3 g of alkyl bromide-modified SiO2 evenly in 500 mL of dimethyl sulfoxide solvent, add 10 g of imidazole polystyrene, stir to dissolve and react at 90 °C for 30 h. After the reaction, add distilled water for precipitation, filter the solvent, wash with distilled water and ethanol, and dry to obtain modified nano-SiO2 grafted polystyrene.

[0046] (5) 10 g of modified nano-SiO2 grafted polystyrene, 0.08 g of antioxidant 1010, and 0.3 g of plasticizer dibutyl phthalate were added into a twin-screw extruder for melt extrusion to obtain an antibacterial modified nano-SiO2 grafted polystyrene composite material.

[0047] Comparative Example 1 (1) To a mixed solvent of 5 mL of distilled water and 60 mL of ethanol, add 5 g of styrene, 0.2 g of allyl amide imidazole monomer, and 0.45 g of dispersant polyvinyl alcohol. Stir evenly and then add 0.15 g of initiator azobisisobutyronitrile. Heat to 60 °C and polymerize for 36 h. After the reaction, centrifuge, wash with distilled water and ethanol, and dry to obtain imidazole polystyrene.

[0048] (5) 10 g of modified nano-SiO2 grafted polystyrene, 0.15 g of nano-SiO2, 0.06 g of antioxidant 1010, and 0.2 g of plasticizer dibutyl phthalate were added into a twin-screw extruder and melt-extruded to obtain a nano-SiO2-polystyrene composite material.

[0049] The antibacterial modified nano-SiO2 grafted polystyrene composite material and nano-SiO2-polystyrene composite material were made into membrane materials with a radius of 1 cm and a thickness of 2 mm, respectively, and placed in sterile culture dishes, and a concentration of 1×10 6 CFU / mL of Staphylococcus aureus suspension was added to agar medium, shaken evenly, and then the culture dish was placed in a constant temperature incubator for cultivation. The antibacterial properties were characterized by the inhibition zone method.

[0050]

Claims

1. An antibacterial modified nano-SiO2 grafted polystyrene composite material, characterized in that: The preparation method of the antibacterial modified nano-SiO2 grafted polystyrene composite material is as follows: (1) Disperse nano-SiO2 uniformly in toluene solvent, add toluene diisocyanate, heat to 80-100 °C, react for 6-12 h, and obtain isocyanate-modified SiO2; (2) Dispersing the isocyanate-modified SiO2 uniformly in chloroform solvent, adding 12-bromo-1-dodecanol and catalyst dibutyltin dilaurate, heating under reflux to react, and obtaining alkyl bromide-modified SiO2; (3) Add styrene and allyl amide imidazole monomer (C8H 11 N3O), dispersant polyvinyl alcohol, stir evenly, add initiator azobisisobutyronitrile, heat to 55-75 ℃, and polymerize for 24-48 hours to obtain imidazole polystyrene; (4) Dispersing the alkyl bromide-modified SiO2 uniformly in a dimethyl sulfoxide solvent, adding imidazole polystyrene, stirring and dissolving to react, thereby obtaining modified nano-SiO2 grafted polystyrene; (5) Add modified nano-SiO2 grafted polystyrene, antioxidant 1010, and plasticizer dibutyl phthalate into a twin-screw extruder for melt extrusion to obtain an antibacterial modified nano-SiO2 grafted polystyrene composite material.

2. The antibacterial modified nano-SiO2 grafted polystyrene composite material according to claim 1, characterized in that: The weight proportions of isocyanate-modified SiO2 in step (2) are 100 parts, 12-bromo-1-dodecanol is 60-200 parts, and dibutyltin dilaurate is 0.5-2.5 parts.

3. The antibacterial modified nano-SiO2 grafted polystyrene composite material according to claim 1, characterized in that: The reaction in step (2) is carried out at 60-75° C. for 18-36 h.

4. The antibacterial modified nano-SiO2 grafted polystyrene composite material according to claim 1, characterized in that: In the step (3), the weight proportions of styrene are 100 parts, allylamide imidazole is 1.5-6 parts, polyvinyl alcohol is 6-10 parts, and azobisisobutyronitrile is 1.5-4 parts.

5. The antibacterial modified nano-SiO2 grafted polystyrene composite material according to claim 1, characterized in that: In the step (4), the weight proportion of alkyl bromide-modified SiO2 is 0.5-3 parts, and the weight proportion of imidazole polystyrene is 100 parts.

6. The antibacterial modified nano-SiO2 grafted polystyrene composite material according to claim 1, characterized in that: The reaction in step (4) is carried out at 60-90° C. for 10-30 h.

Images