CN102391416A - Preparation method of porous material based on inorganic nanoparticles for stabilizing high internal phase emulsion - Google Patents
Preparation method of porous material based on inorganic nanoparticles for stabilizing high internal phase emulsion Download PDFInfo
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- CN102391416A CN102391416A CN2011102577255A CN201110257725A CN102391416A CN 102391416 A CN102391416 A CN 102391416A CN 2011102577255 A CN2011102577255 A CN 2011102577255A CN 201110257725 A CN201110257725 A CN 201110257725A CN 102391416 A CN102391416 A CN 102391416A
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Abstract
The invention discloses a method which uses inorganic nanoparticles, namely titanium dioxide, to stabilize oil-in-water type high internal phase emulsion and uses the emulsion as a template for polymerization so as to get a hydrophilic polymer porous material. The steps are as follows: adding water-soluble monomers, a water-soluble cross-linking agent, an electrolyte and an initiator into aqueous dispersion of nano-titanium dioxide, stirring, dissolving, subsequently further dripping into a hydrophobic organic solvent and stirring so as to form the oil-in-water type emulsion. The monomers in the emulsion are heated and initialized for reaction so as to get the hydrophilic polymer porous material. The preparation method is simple and easy to operate, the hydrophilic polymer porous material without an emulsifier can be obtained, the density is 0.05-0.25g/cm<3>, the pore diameter is 25-250 microns, and the materials in various shapes from thin films to blocks can be prepared according to the shape of a polymerization mold.
Description
Technical field
The present invention relates to a kind of preparation method of hydrophilic polymer porous material, being specifically related to adopt nano titanium dioxide water-dispersion liquid is water, prepares the method for water-soluble polymers porous material through the emulsion oil-in-water template.
Background technology
Polymer porous material has high porosity, low density, bigger serface and good advantage such as mass transport ability, absorption with separate, aspects such as catalysis, bioengineered tissue and environmental science have very high using value therefore to cause the great interest of people.The preparation method of polymer porous material has multiple appearing in the newspapers, as adopting supercutical fluid, air-blowing, the assembling of colloid template, polybenzazole precursor template and High Internal Phase Emulsion template.Wherein the macropore diameter and the pore size distribution of the polymer porous material that makes of High Internal Phase Emulsion template are adjustable; Pore volume is big; The products appearance pattern can be according to the mould random molding, has certain mechanical stability and the surface thereof can be according to advantages such as different environment for use functionalization.These advantages make the research of the polymer porous material that the High Internal Phase Emulsion template makes and preparation have great significance for scientific research and production practice.So far, the polymer porous material of High Internal Phase Emulsion template preparation is being showed wide application prospect like a plurality of fields such as biotechnology support, support of the catalyst, ion exchange resin and electrochemical sensors to people.High Internal Phase Emulsion is the disperse phase percent by volume more than or equal to 74.05% emulsion.This emulsion is since 60 years reported first of twentieth century; As the template for preparing opening polymer material; Numerous bibliographical informations has been arranged; The a series of articles that equal in USP (US Pat 6,147,131) and the Ka Meilong of application in 2000, than Si Mai and Zhang Shengmiao like Dow Chemical Company to deliver on the polymkeric substance magazine etc.Yet being operated in of having appeared in the newspapers prepares the mixture that the emulsifying agent that adopts in the High Internal Phase Emulsion process also only limits to nonionic emulsifier or nonionic emulsifier and a spot of ionic emulsifying agent; And the consumption of nonionic emulsifier is very big; Account for 5～50% of monomer consumption in the system, the existence of a large amount of emulsifying agents had both improved the cost of material, made its application receive a lot of restrictions again; Reduce the mechanical property of material, and caused the pollution of environment easily.
Adopting nanoparticle to replace the stable emulsion of emulsifying agent is the existing report of Pickering emulsion, and this type emulsion has and promptly do not contain emulsifying agent characteristics such as good stability again.Yet the disperse phase volume(tric)fraction of the emulsion that the nanoparticle that has appeared in the newspapers is stable can not be used to prepare polymer porous material less than 70%.
In recent years, only Zhang Shengmiao etc. successfully adopts sub-stabilized oil-in-water of polymer nanocomposite and water-in-oil-type High Internal Phase Emulsion, and has prepared wetting ability and hydrophobic polymer porous material (CN101735389A, CN101735369A, CN101054423A).So far, adopt inorganic nano-particle stabilised oil-in-water High Internal Phase Emulsion that the report of success is not then arranged as yet.
The invention discloses a kind of employing inorganic nano-particle titanium dioxide water-dispersion liquid is water; Add water-soluble monomer and water-soluble cross-linker toward aqueous phase again; With the titanium dioxide nano-particle stabilised oil-in-water High Internal Phase Emulsion of aqueous phase, cause the monomer of aqueous phase and the method that the linking agent polymerization obtains hydrophilic polymer porous material.Realized that hydrophilic polymer porous material prepares the agalasisa of process (soap) and changes.
Summary of the invention
The technical issues that need to address of the present invention are the emulsion template methods that disclose a kind of new preparation soap free hydrophilic polymer porous material, adopt nonionic emulsifier to stablize the above-mentioned defective that this technology of High Internal Phase Emulsion exists to overcome.
The emulsion template method of preparation soap free hydrophilic polymer porous material of the present invention comprises the steps:
Water-soluble monomer, water-soluble cross-linker, ionogen and initiator are joined in the nano titanium dioxide water-dispersion liquid with certain solid content, stir, thing dissolving to be added finishes; It as water, as oil phase, is added water with organic solvent lentamente; Stirring, form emulsion oil-in-water, is reactant with this emulsion again; Be placed in 25～70 ℃ water-bath, reacted 12～48 hours, the product oven dry is just obtained wetting ability soap-free polymerization thing porous material.
Said water-soluble monomer is acrylic amide, vinylformic acid or their mixture;
Said water-soluble cross-linker is a N ' N-methylene diacrylamine;
Water-soluble monomer and water-soluble cross-linker are at the total mass concentration of aqueous phase: 20～50%;
The mass ratio of monomer and linking agent is 0～1: 1～0;
Described nano titanium dioxide water-dispersion liquid, its solid content mass percent is 1～5%; Nano titanium dioxide water-dispersion liquid is dispersed in the deionized water by the nano titanium oxide (model P25) of goldschmidt chemical corporation and obtains;
Said ionogen is one or more the mixture in sodium-chlor, calcium chloride, the sodium sulfate, is 0.05～1% with respect to the mass percent of water;
Said initiator is ammonium persulphate or Potassium Persulphate, and initiator is 1～2% in the mass concentration of aqueous phase;
Water accounts for the whole mass percent of emulsion: 10～25%;
Said organic solvent is Yellow Protopet 2A or hexanaphthene, and its massfraction shared in emulsion is 75～90%.
Adopt the hole shape looks of ESEM (SEM) S-4800 (Japanese JEOL company) observation polymer porous material, and measure its aperture; The porous material apparent density by sample quality divided by its volume calculation gained.
Preparing method of the present invention is simple; Through conventional Raolical polymerizable; Can obtain the aperture at 25～250 microns, density between every cubic centimetre of 0.05～0.25 gram, and can make from film to blocky various body materials according to the shape of polymerization mould.
Embodiment
Embodiment 1
It is in 1% the nano titanium dioxide water-dispersion liquid that 0.25 gram ammonium persulphate, 0.31 gram sodium-chlor, 4.5 gram acrylic amides and 0.5 gram N ' N-methylene diacrylamine are joined 25 gram solid contents, stirs, and the dissolving back constitutes water; When continue stirring water, be that oil phase slowly adds water with the cyclohexane give of 75 grams, after the stable emulsion to be formed; Again this emulsion is injected in the beaker as the template thing; Be warming up to 50 ℃, reacted 24 hours, question response finishes; Polymkeric substance is dry, just obtain required porous material.
The mean pore size of gained porous material is 250 microns, and density is every cubic centimetre of 0.13 gram.
Embodiment 2
The solid content that 0.2 gram ammonium persulphate, 0.04 gram calcium chloride, 1.8 gram acrylic amides and 0.2 gram N ' N-methylene diacrylamine are joined 10 grams is in 5% the nano titanium dioxide water-dispersion liquid, to stir, and the dissolving back constitutes water; When continue stirring water, the Yellow Protopet 2A of 90 grams is slowly added water as oil phase, after the stable emulsion to be formed; Again this emulsion is injected in the beaker as the template thing; Be warming up to 70 ℃, reacted 12 hours, question response finishes; Polymkeric substance is dry, just obtain required porous material.
The mean pore size of gained porous material is 110 microns, and density is every cubic centimetre of 0.05 gram.
Embodiment 3
It is in 5% the nano titanium dioxide water-dispersion liquid that 0.2 gram ammonium persulphate, 0.018 gram sodium sulfate, 9.5 gram acrylic amides and 0.5 gram N ' N-methylene diacrylamine are joined 25 gram solid contents, stirs, and the dissolving back constitutes water; When continuing to stir water; The Yellow Protopet 2A of 75 grams is slowly added water as oil phase, after the stable emulsion to be formed, again this emulsion is injected in the beaker as the template thing; Place under 25 ℃; React after 48 hours, polymkeric substance is dry, just obtain required porous material.
The mean pore size of gained porous material is 25 microns, and density is every cubic centimetre of 0.13 gram.
Embodiment 4
It is in 3% the nano titanium dioxide water-dispersion liquid that 0.4 gram ammonium persulphate, 0.04 gram sodium-chlor, 8 gram acrylic amides and 0.4 gram N ' N-methylene diacrylamine are joined 20 gram solid contents, stirs, and the dissolving back constitutes water; When continue stirring water, be that oil phase slowly adds aqueous phase with the cyclohexane give of 80 grams, after the stable emulsion to be formed; Again this emulsion is injected in the beaker as the template thing; Be warming up to 50 ℃, reacted 24 hours, question response finishes; Polymkeric substance is dry, just obtain required porous material.
The mean pore size of gained porous material is 50 microns, and density is every cubic centimetre of 0.16 gram.
Embodiment 5
It is in 4% the nano titanium dioxide water-dispersion liquid that 0.4 gram ammonium persulphate, 0.04 gram sodium-chlor and 8 gram acrylic amides are joined 20 gram solid contents, stirs, and the dissolving back constitutes water; When continue stirring water, the Yellow Protopet 2A of 80 grams is slowly added aqueous phase as oil phase, after the stable emulsion to be formed; Again this emulsion is injected in the beaker as the template thing, is warming up to 40 ℃, reacted 36 hours; Question response finishes, and polymkeric substance is dry, just obtains required porous material.
The mean pore size of gained porous material is 150 microns, and density is every cubic centimetre of 0.11 gram.
Claims (3)
1. stablize the porous material preparation method of High Internal Phase Emulsion based on inorganic nano-particle for one kind, it is characterized in that, comprise the steps:
Join water-soluble monomer, water-soluble cross-linker, ionogen and initiator in the nano titanium dioxide water-dispersion liquid in proportion; After the stirring and dissolving as water; Again hydrophobic organic solvent is added dropwise to water as oil phase, continues to stir, form the oil-in-water-type High Internal Phase Emulsion; With this emulsion is reactant, adds thermal initiation water-soluble monomer and water-soluble cross-linker polymerization wherein and obtains hydrophilic polymer porous material;
Said water-soluble monomer is acrylic amide, vinylformic acid or their mixture;
Said water-soluble cross-linker is a N ' N-methylene diacrylamine;
Water-soluble monomer and water-soluble cross-linker are at the total mass concentration of aqueous phase: 20～50%;
The mass ratio of monomer and linking agent is 0～1: 1～0;
Described nano titanium dioxide water-dispersion liquid, its solid content mass percent is 1～5%;
Said ionogen is one or more the mixture in sodium-chlor, calcium chloride, the sodium sulfate, is 0.05～1% with respect to the mass percent of water;
Said initiator is ammonium persulphate or Potassium Persulphate, and initiator is 1～2% in the mass concentration of aqueous phase;
Water accounts for the whole mass percent of emulsion: 10～25%;
Said organic solvent is Yellow Protopet 2A or hexanaphthene, and its massfraction shared in emulsion is 75～90%.
2. stablize the porous material preparation method of High Internal Phase Emulsion based on inorganic nano-particle described in the right 1, the reaction times of its reactant is characterised in that, is controlled between 12 hours to 48 hours.
3. stablize the porous material preparation method of High Internal Phase Emulsion based on inorganic nano-particle described in the right 1, the temperature of reaction of its reactant is characterised in that, is controlled between 25 ℃ to 70 ℃.
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103613704A (en) * | 2013-10-10 | 2014-03-05 | 华东理工大学 | Photocatalyst nanopacticle-loaded polymer porous bead carrier material preparation method |
| FR2996848A1 (en) * | 2012-10-16 | 2014-04-18 | Agronomique Inst Nat Rech | COMPOSITION COMPRISING AN INTERNAL PHASE DISPERSE IN A HYDROPHILIC CONTINUOUS PHASE |
| CN106552606A (en) * | 2016-12-02 | 2017-04-05 | 华东理工大学 | A kind of method that porous ion-exchange resin is prepared based on click chemistry reaction |
| CN107142255A (en) * | 2017-05-31 | 2017-09-08 | 桂林理工大学 | A kind of method of the phase pickering emulsions as templated synthesis immobilised enzymes material using in height |
| CN107778408A (en) * | 2017-11-23 | 2018-03-09 | 福州大学 | A kind of method that High Internal Phase Emulsion template prepares porous polymer materials |
| CN110975845A (en) * | 2019-12-18 | 2020-04-10 | 华东理工大学 | Preparation method of porous material loaded with lithium ion sieve |
| CN112006923A (en) * | 2020-08-21 | 2020-12-01 | 中国日用化学研究院有限公司 | High internal phase emulsion stabilized by low-content surfactant and preparation method thereof |
| CN112048097A (en) * | 2020-08-24 | 2020-12-08 | 华南农业大学 | Metal-loaded porous polymer foam with catalytic function and preparation method and application thereof |
| CN113929814A (en) * | 2021-09-24 | 2022-01-14 | 湖北大学 | Preparation method and application of polyacrylonitrile/silicon dioxide porous composite material |
| CN114409953A (en) * | 2021-11-04 | 2022-04-29 | 中国科学院长春应用化学研究所 | Hydrophilic porous structure polymer and preparation method and application thereof |
| CN115215961A (en) * | 2022-08-09 | 2022-10-21 | 武汉理工大学 | Water-absorbing foam based on double emulsifiers and preparation method thereof |
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| CN101735389A (en) * | 2009-12-17 | 2010-06-16 | 华东理工大学 | Emulsion template method for preparing soap free hydrophilic polymer porous material |
| CN101735369A (en) * | 2009-12-17 | 2010-06-16 | 华东理工大学 | Reverse phase emulsion template method for preparing soap free hydrophobic polymer porous material |
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| CN101735389A (en) * | 2009-12-17 | 2010-06-16 | 华东理工大学 | Emulsion template method for preparing soap free hydrophilic polymer porous material |
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Cited By (17)
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| US9789456B2 (en) | 2012-10-16 | 2017-10-17 | Institut National De La Recherche Agronomique—Inra | Composition comprising an internal phase dispersed in a hydrophilic continuous phase |
| FR2996848A1 (en) * | 2012-10-16 | 2014-04-18 | Agronomique Inst Nat Rech | COMPOSITION COMPRISING AN INTERNAL PHASE DISPERSE IN A HYDROPHILIC CONTINUOUS PHASE |
| WO2014060697A1 (en) * | 2012-10-16 | 2014-04-24 | Institut National De La Recherche Agronomique - Inra | Composition comprising an internal phase dispersed in a hydrophilic continuous phase |
| CN103613704B (en) * | 2013-10-10 | 2015-11-25 | 华东理工大学 | A kind of preparation method being loaded with the polyalcohol stephanoporate bead carrier material of photocatalyst nanoparticle |
| CN103613704A (en) * | 2013-10-10 | 2014-03-05 | 华东理工大学 | Photocatalyst nanopacticle-loaded polymer porous bead carrier material preparation method |
| CN106552606B (en) * | 2016-12-02 | 2019-01-11 | 华东理工大学 | A method of porous ion-exchange resin is prepared based on click chemistry reaction |
| CN106552606A (en) * | 2016-12-02 | 2017-04-05 | 华东理工大学 | A kind of method that porous ion-exchange resin is prepared based on click chemistry reaction |
| CN107142255A (en) * | 2017-05-31 | 2017-09-08 | 桂林理工大学 | A kind of method of the phase pickering emulsions as templated synthesis immobilised enzymes material using in height |
| CN107778408A (en) * | 2017-11-23 | 2018-03-09 | 福州大学 | A kind of method that High Internal Phase Emulsion template prepares porous polymer materials |
| CN110975845A (en) * | 2019-12-18 | 2020-04-10 | 华东理工大学 | Preparation method of porous material loaded with lithium ion sieve |
| CN112006923A (en) * | 2020-08-21 | 2020-12-01 | 中国日用化学研究院有限公司 | High internal phase emulsion stabilized by low-content surfactant and preparation method thereof |
| CN112048097A (en) * | 2020-08-24 | 2020-12-08 | 华南农业大学 | Metal-loaded porous polymer foam with catalytic function and preparation method and application thereof |
| CN113929814A (en) * | 2021-09-24 | 2022-01-14 | 湖北大学 | Preparation method and application of polyacrylonitrile/silicon dioxide porous composite material |
| CN113929814B (en) * | 2021-09-24 | 2023-03-03 | 湖北大学 | Preparation method and application of polyacrylonitrile/silicon dioxide porous composite material |
| CN114409953A (en) * | 2021-11-04 | 2022-04-29 | 中国科学院长春应用化学研究所 | Hydrophilic porous structure polymer and preparation method and application thereof |
| CN115215961A (en) * | 2022-08-09 | 2022-10-21 | 武汉理工大学 | Water-absorbing foam based on double emulsifiers and preparation method thereof |
| CN115215961B (en) * | 2022-08-09 | 2023-07-25 | 武汉理工大学 | Double-emulsifier-based water-absorbing foam and preparation method thereof |
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Application publication date: 20120328 |