CO2 response polymer hollow microsphere and preparation method thereof

Abstract

The invention provides a preparation method of CO2 response polymer hollow microspheres. The preparation method comprises the following steps: firstly, enabling a monomer, namely styrene, methyl methacrylate, tert-butyl methacrylate, butyl acrylate or hydroxyl styrene, to react with an initiator and an emulsifier, so as to obtain a seed microsphere emulsion; secondly, simultaneously dropping a mixture of a compound A and a crosslinking agent, and the initiator into the seed microsphere emulsion, and carrying out a reaction so as to obtain a core-shell microsphere emulsion; mixing the core-shell microsphere emulsion with organic solvents, namely tetrahydrofuran (THF), chloroform, ethyl acetate, methylbenzene and the like, and carrying out selective etching. By adopting the preparation method, intelligent hollow microspheres of hollow structures with CO2 response are prepared, irritation residue-free and environmental-friendly response modes of a hollow microsphere material can be achieved, and in addition, the microspheres are controllable in morphology and CO2 irritation response.

Description

technical field

[0001] The invention belongs to the field of intelligent polymer microspheres, in particular to a CO 2 Responsive microspheres and methods for their preparation. Background technique

[0002] Polymer hollow microspheres with stimuli-responsive properties are a new material that can sense changes in the external environment and achieve changes in permeability and size through self-response and adjustment. This excellent performance endows it with potential applications in many fields, such as chemical catalysis, energy storage, and sensors, especially for drug delivery and disease treatment in biomedical engineering. The currently reported stimuli-response methods for constructing smart hollow microspheres are mainly temperature, ionic strength, magnetic field, and pH. Especially in the pH response mode, due to the continuous addition of acid and base alternately, the inorganic salts generated by the acid-base reaction will continue to accumulate in the syst...

Examples

Embodiment 1

[0038] (1) First transfer 2.95g of styrene (St) monomer to the dropping funnel, then dissolve 0.07g of APS in deionized water to obtain an initiator solution, and continuously pass nitrogen gas into the solution for 0.5h to remove oxygen at room temperature. 0.08 g of emulsifier SDS was dissolved in 105 g of pure water to obtain an emulsifier solution. in N 2 Under the condition of protection and 70°C, the styrene monomer and the initiator solution were simultaneously added dropwise to the emulsifier solution, and stirred for 7 hours. After the reaction, the slag was removed by filtration to obtain the seed microsphere emulsion.

[0039] (2) Stir 5.03g monomer dimethylaminoethyl methacrylate (DEAEMA) and 0.16g crosslinking agent divinylbenzene (DVB) evenly and record it as mixed monomer. 0.04g ACVA was stirred and mixed with deionized water to prepare the initiator solution. in N 2 Protect and drop the mixed monomer and initiator solution into the seed emulsion obtained in ...

Embodiment 2

[0042] (1) Transfer 2.96g of styrene (St) monomer to the dropping funnel, dissolve 0.07g of APS in deionized water to obtain an initiator solution, and continuously pass nitrogen gas into the solution for 0.5h to remove oxygen at room temperature. 0.10 g of emulsifier SDS was dissolved in 105 g of pure water to obtain an emulsifier solution. in N 2 The styrene monomer and the initiator solution were simultaneously added dropwise into the emulsifier solution under the condition of protection and 70° C., and stirred for 7 hours. After the reaction, the slag was removed by filtration to obtain the seed microsphere emulsion.

[0043] (2) Stir 5.02g monomer dimethylaminoethyl methacrylate (DEAEMA), 0.50g styrene (St) and 0.21g cross-linking agent divinylbenzene (DVB) and record it as a mixed monomer; 0.10g Stirring and mixing of APS and deionized water is recorded as the initiator solution; 2 Protect and drop the mixed monomer and initiator solution into the seed emulsion obtaine...

Embodiment 3

[0046] (1) Transfer 2.99 g of styrene (St) monomer to the dropping funnel, dissolve 0.07 g of APS in deionized water to obtain an initiator solution, and continuously pass nitrogen gas into the solution for 0.5 h to remove oxygen at room temperature. 0.10 g of emulsifier SDS was dissolved in 100 g of pure water to obtain an emulsifier solution. in N 2 The styrene monomer and the initiator solution were simultaneously added dropwise into the emulsifier solution under the condition of protection and 70° C., and stirred for 7 hours. After the reaction, the slag was removed by filtration to obtain the seed microsphere emulsion.

[0047] (2) Stir 5.04g monomer dimethylaminoethyl methacrylate (DEAEMA), 0.60g styrene (St) and 0.46g cross-linking agent divinylbenzene (DVB) evenly and record it as mixed monomer, 0.10g APS was stirred and mixed with deionized water and recorded as initiator solution. in N 2 Protect and drop the mixed monomer and initiator solution into the seed emuls...

technical field

[0001] The invention belongs to the field of intelligent polymer microspheres, in particular to a CO 2 Responsive microspheres and methods for their preparation. Background technique

[0002] Polymer hollow microspheres with stimuli-responsive properties are a new material that can sense changes in the external environment and achieve changes in permeability and size through self-response and adjustment. This excellent performance endows it with potential applications in many fields, such as chemical catalysis, energy storage, and sensors, especially for drug delivery and disease treatment in biomedical engineering. The currently reported stimuli-response methods for constructing smart hollow microspheres are mainly temperature, ionic strength, magnetic field, and pH. Especially in the pH response mode, due to the continuous addition of acid and base alternately, the inorganic salts generated by the acid-base reaction will continue to accumulate in the syst...

Examples

Embodiment 1

[0038] (1) First transfer 2.95g of styrene (St) monomer to the dropping funnel, then dissolve 0.07g of APS in deionized water to obtain an initiator solution, and continuously pass nitrogen gas into the solution for 0.5h to remove oxygen at room temperature. 0.08 g of emulsifier SDS was dissolved in 105 g of pure water to obtain an emulsifier solution. in N 2 Under the condition of protection and 70°C, the styrene monomer and the initiator solution were simultaneously added dropwise to the emulsifier solution, and stirred for 7 hours. After the reaction, the slag was removed by filtration to obtain the seed microsphere emulsion.

[0039] (2) Stir 5.03g monomer dimethylaminoethyl methacrylate (DEAEMA) and 0.16g crosslinking agent divinylbenzene (DVB) evenly and record it as mixed monomer. 0.04g ACVA was stirred and mixed with deionized water to prepare the initiator solution. in N 2 Protect and drop the mixed monomer and initiator solution into the seed emulsion obtained in ...

Embodiment 2

[0042] (1) Transfer 2.96g of styrene (St) monomer to the dropping funnel, dissolve 0.07g of APS in deionized water to obtain an initiator solution, and continuously pass nitrogen gas into the solution for 0.5h to remove oxygen at room temperature. 0.10 g of emulsifier SDS was dissolved in 105 g of pure water to obtain an emulsifier solution. in N 2 The styrene monomer and the initiator solution were simultaneously added dropwise into the emulsifier solution under the condition of protection and 70° C., and stirred for 7 hours. After the reaction, the slag was removed by filtration to obtain the seed microsphere emulsion.

[0043] (2) Stir 5.02g monomer dimethylaminoethyl methacrylate (DEAEMA), 0.50g styrene (St) and 0.21g cross-linking agent divinylbenzene (DVB) and record it as a mixed monomer; 0.10g Stirring and mixing of APS and deionized water is recorded as the initiator solution; 2 Protect and drop the mixed monomer and initiator solution into the seed emulsion obtaine...

Embodiment 3

[0046] (1) Transfer 2.99 g of styrene (St) monomer to the dropping funnel, dissolve 0.07 g of APS in deionized water to obtain an initiator solution, and continuously pass nitrogen gas into the solution for 0.5 h to remove oxygen at room temperature. 0.10 g of emulsifier SDS was dissolved in 100 g of pure water to obtain an emulsifier solution. in N 2 The styrene monomer and the initiator solution were simultaneously added dropwise into the emulsifier solution under the condition of protection and 70° C., and stirred for 7 hours. After the reaction, the slag was removed by filtration to obtain the seed microsphere emulsion.

[0047] (2) Stir 5.04g monomer dimethylaminoethyl methacrylate (DEAEMA), 0.60g styrene (St) and 0.46g cross-linking agent divinylbenzene (DVB) evenly and record it as mixed monomer, 0.10g APS was stirred and mixed with deionized water and recorded as initiator solution. in N 2 Protect and drop the mixed monomer and initiator solution into the seed emuls...

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