Method for preparing nanometer antibacterial core-shell polymer microsphere through emulsion polymerization

Abstract

The invention relates to a method for preparing a core-shell nanometer antibacterial polymer microsphere through emulsion polymerization by using a polymerizable Viologen surfactant. The method uses a Viologen dication polymerizable surfactant which is provided with a surface activity functional group, a polymerizable double bond functional group and an antibacterial functional group as a comonomer to perform stable emulsion polymerization in water or a reaction medium of the water and an organic solvent, and prepares the nanometer core-shell polymer microsphere with a surface covalent bond connected with an antibacterial group through one-step charging or sectional charging. The preparation method is simple, the nanometer polymer microsphere can be obtained by the method, the shell layerof the microsphere has antibacterial function, and the surface of the microsphere is clean with uniformly distributed particle sizes, thus the method is applicable in the fields of biological medicines, environmental protection, water treatment and the like.

Description

Technical field:

[0001] The invention adopts a soap-free emulsion copolymerization method to prepare nano-polymer microspheres with antibacterial groups bonded on the surface, provides a simple method for preparing antibacterial nano-polymer microspheres, and relates to the soap-free emulsion polymerization technology. Background technique:

[0002] Bleachable biocides often contain heavy metals such as antibiotics, phenols, iodine, quaternary ammonium compounds, or silver, which can detach from material surfaces, reducing their durability and useful life, while the biocides are released into or interact with the environment The reaction of organic impurities to produce toxic by-products can cause environmental problems. An effective way to solve this problem is to fix the bactericide or antibacterial agent on the surface of the substrate by chemical bonds, such as being fixed on polymer film (Zhilong Shi, K.G.Neoh, E.T.Kang.Biomaterials, 2005, 26:501-508), glass ( Jinyu Hu...

Examples

Embodiment 1

[0069] In the reactor equipped with stirring device, nitrogen device, condensing device and feeding port, add 1.25ml (0.05, with the volume ratio of reaction medium, the following examples are the same) styrene (St), 0.05g (0.044, with The mass ratio of the main monomer, the following examples are the same as) N-hexyl-N'-(4-vinylbenzyl)-4,4'-bipyridine bisalt bromide chloride (HVV) and 23ml water, nitrogen removal Oxygen, stirring to form a uniform mixed solution; 0.02g (0.018, with the mass ratio of the main monomer, the same as in the following examples) 2,2'-azobisisobutylsulfinium hydrochloride (AIBA) was dissolved in 2ml water, After the temperature of the reactor rose to 70°C, AIBA aqueous solution was added to initiate the St polymerization reaction for 10 hours to obtain a stable latex; the obtained latex was centrifuged at 15000r / min for 30 minutes, washed repeatedly with water and methanol, and then dried at room temperature to obtain a powder polymer microspheres. ...

Embodiment 2

[0071] Same as specific implementation

[0072] Embodiment 1, only the added monomer is 1.25ml (0.05) styrene (St), 0.05ml (0.04, the volume ratio with the main monomer, the following examples are the same) acrylic acid. SEM observation and analysis microsphere particle size is 108nm, coefficient of variation is 4.5%, TEM observation analysis shell thickness is 17nm, antibacterial test observed the formation of obvious bacteriostatic zone.

Embodiment 3

[0074] Same as specific implementation

[0075] Example 1, except that the added monomers are 1.25ml (0.05) styrene (St), 0.02ml (0.016) N-isopropylacrylamide. SEM observation and analysis microsphere particle size is 116nm, coefficient of variation is 5.1%, TEM observation analysis shell thickness is 23nm, antibacterial test observed the formation of obvious bacteriostatic zone.

Technical field:

[0001] The invention adopts a soap-free emulsion copolymerization method to prepare nano-polymer microspheres with antibacterial groups bonded on the surface, provides a simple method for preparing antibacterial nano-polymer microspheres, and relates to the soap-free emulsion polymerization technology. Background technique:

[0002] Bleachable biocides often contain heavy metals such as antibiotics, phenols, iodine, quaternary ammonium compounds, or silver, which can detach from material surfaces, reducing their durability and useful life, while the biocides are released into or interact with the environment The reaction of organic impurities to produce toxic by-products can cause environmental problems. An effective way to solve this problem is to fix the bactericide or antibacterial agent on the surface of the substrate by chemical bonds, such as being fixed on polymer film (Zhilong Shi, K.G.Neoh, E.T.Kang.Biomaterials, 2005, 26:501-508), glass ( Jinyu Hu...

Examples

Embodiment 1

[0069] In the reactor equipped with stirring device, nitrogen device, condensing device and feeding port, add 1.25ml (0.05, with the volume ratio of reaction medium, the following examples are the same) styrene (St), 0.05g (0.044, with The mass ratio of the main monomer, the following examples are the same as) N-hexyl-N'-(4-vinylbenzyl)-4,4'-bipyridine bisalt bromide chloride (HVV) and 23ml water, nitrogen removal Oxygen, stirring to form a uniform mixed solution; 0.02g (0.018, with the mass ratio of the main monomer, the same as in the following examples) 2,2'-azobisisobutylsulfinium hydrochloride (AIBA) was dissolved in 2ml water, After the temperature of the reactor rose to 70°C, AIBA aqueous solution was added to initiate the St polymerization reaction for 10 hours to obtain a stable latex; the obtained latex was centrifuged at 15000r / min for 30 minutes, washed repeatedly with water and methanol, and then dried at room temperature to obtain a powder polymer microspheres. ...

Embodiment 2

[0071] Same as specific implementation

[0072] Embodiment 1, only the added monomer is 1.25ml (0.05) styrene (St), 0.05ml (0.04, the volume ratio with the main monomer, the following examples are the same) acrylic acid. SEM observation and analysis microsphere particle size is 108nm, coefficient of variation is 4.5%, TEM observation analysis shell thickness is 17nm, antibacterial test observed the formation of obvious bacteriostatic zone.

Embodiment 3

[0074] Same as specific implementation

[0075] Example 1, except that the added monomers are 1.25ml (0.05) styrene (St), 0.02ml (0.016) N-isopropylacrylamide. SEM observation and analysis microsphere particle size is 116nm, coefficient of variation is 5.1%, TEM observation analysis shell thickness is 23nm, antibacterial test observed the formation of obvious bacteriostatic zone.

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