Porous membrane based on aminated copolymer microspheres and polyacetal and preparation method of porous membrane

Abstract

The invention relates to a preparation method for a porous membrane based on aminated copolymer microspheres and polyacetal. The preparation method mainly comprises the steps that 1, styrene-acrylatecopolymer microspheres are prepared to serve as precursor microspheres; 2, diamine is added into a precursor microsphere solution, and surface aminated microspheres are prepared; 3, polymers with opposite charges are alternatively assembled on a substrate to serve as a buffer layer, and then a microsphere layer formed by the surface aminated microspheres and the polyacetal continues to be alternatively assembled; 4, under the action of an external cross-linking agent and a catalyst, the substrate with the buffer layer and the microsphere layer continues to react under the protection of nitrogen, after the reaction is finished, a thin membrane is removed from the substrate, and then the porous membrane can be obtained. According to the preparation method, the uniform large-sized copolymer microspheres synthesized through polymerization of a soap-free emulsion are subjected to surface amination, and then the surface aminated copolymer microspheres and the polyacetal liquid are alternatively mutually assembled to form layers of regular microsphere layer membranes, the microsphere layer membranes are put into a solvent for hypercrosslinking to form the porous membrane, and the method for preparing the regular porous membrane with the controllable thickness is greatly simplified.

Description

technical field

[0001] The invention specifically relates to a porous membrane based on aminated copolymerized microspheres and polyaldehyde and a preparation method thereof, belonging to the field of polymer materials. Background technique

[0002] In recent years, porous membranes have played an increasingly important role in the systematic study of structure-property relationships, as they are suitable for various applications such as storage\separation and heterogeneous catalysis. The preparation of porous membranes from organic and inorganic or organic-inorganic hybrid materials, with different pore sizes ranging from nanometer to micrometer, has been extensively studied. Among all porous materials, microspheres of hypercrosslinked polymers (HCPs), originally discovered by Davankov, are purely organic porous materials such as COFs with permanent pores due to extensive crosslinking reactions that prevent polymer chains from collapsing. Furthermore, good thermal stabilit...

Examples

Embodiment 1

[0042] The preparation method of the porous membrane based on aminated copolymerized microspheres and polyaldehyde, the specific steps are as follows:

[0043] 1. Synthesis of precursor microspheres

[0044] Styrene (St) and butyl acrylate (BA) are used as monomers, and the molar ratio of the two is 8:1. First add water as a solvent 100ml, and the total amount of monomers added is 10wt% of the solvent, and then add the total amount of monomers Mass 1wt% cross-linking agent divinylbenzene (DVB), add 1wt% initiator potassium persulfate (KPS) of the total mass of the monomers, then react at a constant temperature of 70°C for 8h, and wash and centrifuge repeatedly with alcohol and water at the end of the reaction The solid product, namely the precursor microspheres P(St-BA), was ultrasonically dispersed in methanol to prepare a microsphere solution with a mass fraction of 10%;

[0045] 2. Preparation of Surface Aminated Microspheres

[0046] Add ethylenediamine to the precursor ...

Embodiment 2

[0063] The difference between embodiment 2 and embodiment 1 is that embodiment 2 changes the monomer type of acrylates in the mixed monomer, and replaces butyl acrylate monomer with hydroxyethyl methacrylate (HEMA), thereby exploring The effect of different acrylate monomers on aminolysis and the effect of hypercrosslinking on different monomers.

[0064] Such as figure 2 As shown, the peak of 1542cm-1 amino groups by FT-IR indicates that after surface amination, amino groups that did not appear before surface amination appear on the copolymerized microspheres, which proves that different acrylate monomers have no effect on surface amination.

[0065] Such as Figure 8B As shown, it can be seen by SEM that the morphology of the side of the self-assembled microsphere layer P (St-HEMA) microspheres is smooth, and the microspheres are stacked layer by layer.

[0066] Such as Figure 9B As shown, it can be seen through SEM that the morphology of the side surface of the layer-by...

Embodiment 3

[0068] The difference between embodiment 3 and embodiment 1 is: embodiment 2 has removed the benzene cycloalkene in the mixed monomer, and the benzene cycloalkene monomer is changed into methyl methacrylate (MMA), and butyl acrylate mono While changing the proportion of the total amount of monomers to the solvent, the influence of non-benzenecycloolefin monomers on the copolymerized microspheres and the influence of the super-crosslinked film on the film morphology were discussed.

[0069] Such as image 3 As shown, the mass percentage of the total amount of monomer relative to the solvent analyzed by the particle size data is 10%, 20%, and 30%, and the size of the P(MMA-BA) microspheres varies from small to large, which proves that the total amount of monomer is relative to the solvent. The higher the mass percentage, the larger the particle size of the microspheres.

[0070] Such as Figure 8C As shown, it can be seen by SEM that the morphology of the side of the P(MMA-BA)...

technical field

[0001] The invention specifically relates to a porous membrane based on aminated copolymerized microspheres and polyaldehyde and a preparation method thereof, belonging to the field of polymer materials. Background technique

[0002] In recent years, porous membranes have played an increasingly important role in the systematic study of structure-property relationships, as they are suitable for various applications such as storage\separation and heterogeneous catalysis. The preparation of porous membranes from organic and inorganic or organic-inorganic hybrid materials, with different pore sizes ranging from nanometer to micrometer, has been extensively studied. Among all porous materials, microspheres of hypercrosslinked polymers (HCPs), originally discovered by Davankov, are purely organic porous materials such as COFs with permanent pores due to extensive crosslinking reactions that prevent polymer chains from collapsing. Furthermore, good thermal stabilit...

Examples

Embodiment 1

[0042] The preparation method of the porous membrane based on aminated copolymerized microspheres and polyaldehyde, the specific steps are as follows:

[0043] 1. Synthesis of precursor microspheres

[0044] Styrene (St) and butyl acrylate (BA) are used as monomers, and the molar ratio of the two is 8:1. First add water as a solvent 100ml, and the total amount of monomers added is 10wt% of the solvent, and then add the total amount of monomers Mass 1wt% cross-linking agent divinylbenzene (DVB), add 1wt% initiator potassium persulfate (KPS) of the total mass of the monomers, then react at a constant temperature of 70°C for 8h, and wash and centrifuge repeatedly with alcohol and water at the end of the reaction The solid product, namely the precursor microspheres P(St-BA), was ultrasonically dispersed in methanol to prepare a microsphere solution with a mass fraction of 10%;

[0045] 2. Preparation of Surface Aminated Microspheres

[0046] Add ethylenediamine to the precursor ...

Embodiment 2

[0063] The difference between embodiment 2 and embodiment 1 is that embodiment 2 changes the monomer type of acrylates in the mixed monomer, and replaces butyl acrylate monomer with hydroxyethyl methacrylate (HEMA), thereby exploring The effect of different acrylate monomers on aminolysis and the effect of hypercrosslinking on different monomers.

[0064] Such as figure 2 As shown, the peak of 1542cm-1 amino groups by FT-IR indicates that after surface amination, amino groups that did not appear before surface amination appear on the copolymerized microspheres, which proves that different acrylate monomers have no effect on surface amination.

[0065] Such as Figure 8B As shown, it can be seen by SEM that the morphology of the side of the self-assembled microsphere layer P (St-HEMA) microspheres is smooth, and the microspheres are stacked layer by layer.

[0066] Such as Figure 9B As shown, it can be seen through SEM that the morphology of the side surface of the layer-by...

Embodiment 3

[0068] The difference between embodiment 3 and embodiment 1 is: embodiment 2 has removed the benzene cycloalkene in the mixed monomer, and the benzene cycloalkene monomer is changed into methyl methacrylate (MMA), and butyl acrylate mono While changing the proportion of the total amount of monomers to the solvent, the influence of non-benzenecycloolefin monomers on the copolymerized microspheres and the influence of the super-crosslinked film on the film morphology were discussed.

[0069] Such as image 3 As shown, the mass percentage of the total amount of monomer relative to the solvent analyzed by the particle size data is 10%, 20%, and 30%, and the size of the P(MMA-BA) microspheres varies from small to large, which proves that the total amount of monomer is relative to the solvent. The higher the mass percentage, the larger the particle size of the microspheres.

[0070] Such as Figure 8C As shown, it can be seen by SEM that the morphology of the side of the P(MMA-BA)...

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