CN-122011268-A - Continuous preparation method of high-dispersity polyglycidyl methacrylate microspheres based on microfluidic technology

Abstract

The invention discloses a continuous preparation method of high-dispersity Poly Glycidyl Methacrylate (PGMA) microspheres based on a microfluidic technology, and aims to solve the core difficulties of unstable system, limited flow rate range, difficult precise control of microsphere particle size and morphology uniformity and the like in the existing preparation process. The method has the advantages of energy conservation, high efficiency and batch synthesis by constructing a disperse phase system with methylene dichloride as a core, optimizing micro-fluidic operation parameters and adopting a staged ultraviolet polymerization curing process, and the prepared PGMA microsphere has wide application prospect in the fields of protein separation, sewage treatment, drug delivery, biosensor construction and the like because of uniform particle size, regular morphology, controllable pore structure and abundant epoxy functional groups on the surface.

Inventors

• LEI JIANDU
• WANG JIAMIN

Assignees

• 北京林业大学

Dates

Publication Date

20260512

Application Date

20260205

Claims (2)

1. 1. The continuous preparation method of the high-dispersity polyglycidyl methacrylate (PGMA) microspheres based on the microfluidic technology is characterized by comprising the following steps of: (1) Preparing a disperse phase, namely dissolving Glycidyl Methacrylate (GMA), a cross-linking agent, a pore-forming agent and a photoinitiator in a mixed solvent system taking dichloromethane as a core, and stirring and mixing until the mixture is uniform to obtain the disperse phase; The mass concentration of the GMA is 20 wt% -35% wt%, and the cross-linking agent is at least one of Ethylene Glycol Dimethacrylate (EGDMA), divinylbenzene (DVB) and N, N-Methylenebisacrylamide (MBA) and is 5% -wt% -40 wt%. The pore-forming agent is at least one of dodecanol, n-octanol and cyclohexanol, the mass concentration is 1 wt-20 wt%, the photoinitiator is at least one of 2, 2-dimethoxy-2-phenyl acetophenone (BDK) and 2,4, 6-trimethylbenzoyl-diphenyl phosphine oxide (TPO), the mass concentration is 1 wt-4 wt% of the total mass of the monomer and the cross-linking agent, and the mass concentration of dichloromethane in the mixed solvent is 30 wt-60 wt%; (2) Preparing a continuous phase, namely dissolving polyvinyl alcohol and a surfactant in deionized water, heating and stirring until the polyvinyl alcohol and the surfactant are completely dissolved to obtain the continuous phase; Wherein the surfactant is at least one of Span 80, tween 80 and Sodium Dodecyl Sulfate (SDS), and the mass concentration is 1 wt% -4 wt%; (3) Fixing an injector for loading a continuous phase and a disperse phase on a microinjection pump, and accurately controlling the flow rate ratio of the continuous phase to 10 mL/h-50 mL/h and the flow rate of the disperse phase to 0.5 mL/h-5 mL/h to enable the two phases to flow into a flow focusing type micro-channel, so that continuous and stable generation of the emulsion containing the high monodisperse micro-droplets is realized by utilizing the shearing action of the continuous relative disperse phase; (4) The method comprises the steps of carrying out staged ultraviolet polymerization curing and post-treatment, namely enabling the emulsion containing the high-monodispersity micro-droplets to flow through a transparent tube, carrying out rapid initial curing through a 254 nm ultraviolet region to enable the surfaces of the micro-droplets to be rapidly crosslinked and shaped to form primary microspheres with complete spherical shells, carrying out deep crosslinking reaction on the primary microspheres in a 365nm ultraviolet region to achieve final curing of polymers, forming and deep curing of the microspheres in a single flow system, and filtering, washing and drying a cured product to obtain the PGMA microspheres with high monodispersity.
2. 2. The method of claim 1, wherein the precise flow rate control in step (3) cooperates with the flow-focused microchannel to ensure that the PGMA microspheres are highly monodisperse while maintaining high throughput production of individual microfluidic units.

Description

Continuous preparation method of high-dispersity polyglycidyl methacrylate microspheres based on microfluidic technology Technical Field The invention belongs to the technical field of organic materials, and relates to a continuous preparation method of high-dispersity polyglycidyl methacrylate microspheres based on a microfluidic technology. Background The micron-sized porous polymer microsphere is used as a novel functional material with excellent performance, and has become a research hot spot in the field of high polymer materials in recent years. Glycidyl Methacrylate (GMA) is an ester compound with acrylate double bonds and epoxy groups, the structure of the Glycidyl Methacrylate (GMA) is shown in a formula 1, the glycidyl methacrylate is low in cost and insoluble in water, is easily dissolved in an organic solvent, contains epoxy groups in molecules, contains carbon-carbon double bonds with relatively strong reaction in molecular structures, can polymerize other functional monomers, and can also perform self-polymerization. The epoxy groups in the side chains have high reactivity, good hydrophilicity, biocompatibility and innocuity, and are widely applied in the fields of chromatographic separation, industrial catalysis and controlled release carriers of biological materials. Currently, researchers wish to prepare micron-sized polyglycidyl methacrylate (PGMA) microspheres with uniform particle size distribution and controllable surface characteristics by studying the influencing factors of microsphere shape, particle size and pore size during polymerization. However, the preparation process of microspheres is complex and is affected by various influencing factors. How to accurately control the particle size according to the requirements is still a hot spot and a difficult problem in the field. 1 (1) Microfluidic technology is a technology that precisely controls and processes microscale fluids within microchannels (tens to hundreds of microns) where droplets are formed by extruding or shearing an immiscible dispersed and continuous phase at an interface. The method has the advantages that the particle size of the microsphere can be accurately controlled by changing the flow rate and the proportion of two phases and the diameter of a channel, and meanwhile, the rapid mixing, the reaction and the separation of micro liquid drops can be realized in the micro channel, so that the cross mixing among samples is effectively prevented, the reaction time is greatly shortened, the integration capability is high, the stable, uniform and dispersed microsphere is easy to prepare, and the method has high sensitivity, high accuracy and repeatability. Based on the core advantages of accurate diameter control, low pollution, high efficiency, high speed, high repeatability and the like, the microfluidic technology provides powerful support for large-scale preparation and cross-field application of functional polymer microspheres. Aiming at the problems of difficult precise control of particle size, poor shape uniformity and the like in the existing PGMA microsphere preparation process, the invention adopts a microfluidic technology to prepare monodisperse liquid drops containing photosensitive monomers, and the liquid drops are quickly solidified into shells to form solid microspheres after ultraviolet irradiation initiates polymerization crosslinking reaction. The prepared microsphere has uniform and stable morphology and uniform particle size due to the short-time high efficiency of the curing process, and the process has energy-saving and high-efficiency batch synthesis potential, and can be widely applied to the fields of protein separation, sewage treatment, drug delivery, biosensor construction and the like. Disclosure of Invention The invention aims to solve the problems of discontinuous preparation process, poor monodispersity (CV value) of the microsphere, low curing efficiency, difficult control of an internal structure and the like existing in the preparation of the Poly Glycidyl Methacrylate (PGMA) microsphere by adopting a microfluidic technology in the prior art, and provides a continuous preparation method of the high monodispersity PGMA microsphere based on the microfluidic technology. The method realizes the efficient, continuous and stable preparation of PGMA microspheres with highly uniform particle size, regular morphology and controllable aperture by constructing a disperse phase system with dichloromethane as a core, optimizing microfluidic operation parameters and adopting a staged ultraviolet polymerization curing process. In order to achieve the above purpose, the invention adopts the following technical scheme: a continuous preparation method of high-monodispersity Poly Glycidyl Methacrylate (PGMA) microspheres based on a microfluidic technology, which is characterized by comprising the following steps: (1) Preparing a disperse phase, namely dissolving Glycidyl Methacrylate (GMA), a cross-lin