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A preparation method of high specific surface area polymer-based hierarchical pore structure interlocking microcapsules

A high specific surface area, polymer technology, applied in the preparation of microspheres, microcapsule preparations, etc., can solve the problems of shrinkage cavities, high molecular weight requirements, limiting the application of dual-template methods, etc.

Inactive Publication Date: 2016-02-03
HEBEI UNIV OF TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Its limitations are: (1) In the double-template method, the template should have obvious interfacial interaction or form a strong interaction force (such as hydrogen bond) with the skeleton material, complete self-assembly in the skeleton material, and remove the template Pores can be formed. At present, polymer compounds with special structures are mostly used in the dual-template method. This type of polymer has high requirements for the composition of segmental structural units and molecular weight, and the preparation is cumbersome and expensive. At the same time, the skeleton material can be melamine, etc. Forming polymers with strong hydrogen bonding, these greatly limit the application of the double-template method in the preparation of polymer-based porous materials; (2) for the emulsion polymerization method, the suitable surfactant and ratio are The key to determining the size of the pores, and the pores synthesized by using liquid droplets as templates are prone to collapse and shrinkage, and the pore structure is unstable.
[0006] At present, there is no relevant report on the preparation method of a high specific surface area polymer-based hierarchical pore structure interlocking microcapsules that combines surface-initiated atom transfer radical polymerization, double bond radical polymerization and Friedel-Crafts cross-linking porogenic technology.

Method used

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  • A preparation method of high specific surface area polymer-based hierarchical pore structure interlocking microcapsules
  • A preparation method of high specific surface area polymer-based hierarchical pore structure interlocking microcapsules
  • A preparation method of high specific surface area polymer-based hierarchical pore structure interlocking microcapsules

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Experimental program
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Effect test

Embodiment 1

[0063] (1) Preparation of 600nm silica colloidal crystal template

[0064] Add 145g of absolute ethanol, 34.1g of ammonia water with a mass fraction of 25%, and 35.0g of deionized water to a 500mL three-necked bottle equipped with mechanical stirring at room temperature. After stirring evenly, quickly add 15.4g of orthosilicon Acid ethyl ester, reacted at room temperature for 8h. Transfer the obtained suspension into a beaker, wait for the solvent to volatilize completely naturally, and obtain a colloidal silica template with an average particle size of 600nm, and finally sinter the template in a muffle furnace at 500°C for 3 hours, and slowly lower it to room temperature to obtain A silica colloidal crystal template in which silica microspheres with an average particle size of 600nm are adhered to each other;

[0065] (2) Surface modification of silica colloidal crystal template

[0066] Silane coupling agent [3-(2-bromoisobutyryl)aminopropyl]-triethoxysilane (BITS) modifie...

example 1

[0076] The surface area measured by the material obtained in Example 1 with the model MicromeriticsASAP2020M+C full-automatic specific surface area analyzer can reach 1000m 2 g -1 .

[0077] Description: the preparation method of silane coupling agent [3-(2-bromoisobutyryl) aminopropyl]-triethoxysilane in step (2) of the present invention is as follows: (other embodiments are the same)

[0078] Add 40.0mL toluene, 16.0mL (3-aminopropyl)triethoxysilane (APTS), 9.40mL triethylamine (TEA) into a 250mL three-necked flask, stir in an ice-water bath, and dissolve 8.40mL 2-bromoiso Dissolve butyryl bromide in 40mL of toluene, add the mixture dropwise into a three-necked flask, drop it for 1 hour, stir in an ice bath for 3 hours, then stir at room temperature for 10 hours to obtain a solid-liquid mixture, filter the mixture, and remove the filtrate by distillation under reduced pressure The unreacted TEA and solvent toluene can be used to obtain the surface modifier BITS, and the sy...

Embodiment 2

[0080] (1) The preparation of 600nm silica colloidal crystal template is the same as the first step of embodiment;

[0081] (2) Surface modification of silica colloidal crystal template

[0082] γ-methacryloyloxypropyltrimethoxysilane (MPS) modified silica colloidal crystal template, put 0.3g of dried and sintered silica colloidal crystal template into a 250mL three-necked bottle, add 100ml of ethanol , distilled water 2.5mL, ammonia water 0.25mL, stirred mechanically at 25°C, added γ-methacryloxypropyltrimethoxysilane (MPS) 1.5mL, condensed and refluxed at room temperature for 24h. Stop stirring after the reaction, discard the liquid, wash and replace with absolute ethanol three times, and finally vacuum-dry at 25°C for 12 hours to obtain an MPS-modified silica colloidal crystal template with an average particle size of 600nm;

[0083] (3) Silica colloidal crystal template controllable grafting of polymer segments

[0084] Add 0.03 g of MPS-modified silica colloidal crystal...

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Abstract

The invention discloses a preparation method of interlocking micro-capsules based on a polymer with a high specific surface area and having a hierarchical porous structure. The method comprises the following steps: modifying a silicon dioxide colloid crystal template, performing controlled graft of a polymer chain segment by surface-initiated atom transfer radical polymerization and double-bond radical polymerization, crosslinking a linear polymer chain segment by using a friedel-crafts crosslinking method, and removing the silicon dioxide colloid crystal template, thus preparing interlocking micro-capsules based on a polymer with a high specific surface area and having a hierarchical porous structure. Through a controlled graft polymer layer, a certain gap is formed in an area which is fully filled before, thereby reducing the mass and forming more mass transfer ways. By adopting a friedel-crafts crosslinking and pore-forming technology, capsule walls made of a polymer material are cross-linked to form micro-pores and meso-pores; the material formed by adopting a friedel-crafts self-crosslinking technology is high in specific surface area, thereby greatly improving the application performance; the capsule cavities at micro-pore, meso-pore and large-pore levels, communication windows formed among interlocking micro-capsules and gaps among the micro-capsules present a hierarchical porous interlocking structure on the whole.

Description

technical field [0001] The technical solution of the invention relates to the field of polymer materials, in particular to a method for preparing interlocking microcapsules with polymer-based hierarchical pore structure with high specific surface area. Background technique [0002] Microcapsule refers to a micro-container with a hollow structure and a shell made of polymer materials, inorganic materials or organic-inorganic hybrid materials. Microcapsules have the functions of protecting the core material in the capsule core, changing the weight, volume, state and surface properties of the material, isolating active ingredients, and controlling the slow release of the core material. In the late 1970s, Narty et al. (NartyJJ, OppenheimRC, SpeiserP.Nanoparticlesanewcolloidaldrugdeliveringsystem.PharmaceuticaActaHelvetiae, 1978,53:17-23.) proposed the concept of nanocapsules (Nanocapsules), expanding microcapsules into a new material with nanometer dimensions . 近年来微囊发展迅速,目前在响应性...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): B01J13/14C08F292/00C08F8/24C08J9/28C08J3/24
Inventor 王小梅田磊张旭吴翠红杨碧微刘盘阁
Owner HEBEI UNIV OF TECH
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