CN101735369B - Reverse phase emulsion template method for preparing soap free hydrophobic polymer porous material - Google Patents
Reverse phase emulsion template method for preparing soap free hydrophobic polymer porous material Download PDFInfo
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- CN101735369B CN101735369B CN2009102013096A CN200910201309A CN101735369B CN 101735369 B CN101735369 B CN 101735369B CN 2009102013096 A CN2009102013096 A CN 2009102013096A CN 200910201309 A CN200910201309 A CN 200910201309A CN 101735369 B CN101735369 B CN 101735369B
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Abstract
The invention discloses a method for preparing a soap free hydrophobic polymer porous material. In the method, water dispersion solution of polyurethane is used for stabilizing a soap free oil-in-water type emulsion, and the emulsion is used as a template to perform polymerization to obtain the hydrophobic polymer porous material. The method comprises the following steps of: dropwise adding polyurethane water dispersion serving as a water phase into an oil phase formed by a hydrophobic monomer and a hydrophobic crosslinking agent and placed at the temperature of between 60 and 90 DEG C, and stirring the mixed solution to obtain form the oil-in-water type emulsion; and initializing the reaction of the monomer in the emulsion to obtain the hydrophobic polymer porous material. The method is simple and can be easily carried out, and the soap free hydrophobic polymer porous material can be formed by the common reverse phase emulsion polymerization reaction, the pore size of macropores of the material is 25 to 250 micrometers, and the pore volume is 1.0 to 14ml/g, and according to a shape of a polymerization mould, the material can be made into various shapes from a film to a block.
Description
Technical field
The present invention relates to a kind of preparation method of hydrophobic polymer porous material, being specifically related to adopt polyurethane aqueous dispersion is water, prepares the method for polymer porous material by reverse phase emulsion template method.
Background technology
Polymer porous material is a kind of material with extensive use, as the polystyrene porous material, has obtained numerous application at numerous areas such as preparation tissue culture support, ion exchange resin and support of the catalyst.
The preparation method of polymer porous material has caused that people pay close attention to widely.The disperse phase percent by volume more than or equal to 74.05% super-thick emulsion (claiming High Internal Phase Emulsion again) since 60 years reported first of twentieth century, prepare opening polymer material as template, numerous bibliographical informations has been arranged, as United States Patent (USP) (the US Pat 6 of Dow Chemical Company in application in 2000,147,131) and Ka Meilong, equal a series of articles of delivering on the polymkeric substance magazine etc. than this wheat.
Although but to be in the news first be things before decades to High Internal Phase Emulsion, the emulsifying agent that scientist adopts in preparation High Internal Phase Emulsion process still only limits to the mixture of 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, make its application be subjected to 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 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%.
The invention discloses a kind of employing ionic polyurethanes aqueous dispersions is water, with hydrophobic monomer and hydrophobicity linking agent is oil phase, with the anti-phase no soap High Internal Phase Emulsion of aqueous polyurethane emulsion particle stabilize oil water-in type of aqueous phase, cause the preparation method that the oil phase polymerization obtains the soap free hydrophobic polymer porous material.Realized agalasisa (soap) change of hydrophobic polymer porous material preparation process.
Summary of the invention
The technical issues that need to address of the present invention are to disclose a kind of reverse phase emulsion template method for preparing soap free hydrophobic polymer porous material, adopt nonionic emulsifier to stablize the above-mentioned defective that this technology of High Internal Phase Emulsion exists to overcome.
The reverse phase emulsion template method of preparation soap free hydrophobic polymer porous material of the present invention comprises the steps:
In 60～90 ℃ of mixtures that polyurethane aqueous dispersion joined hydrophobic monomer and hydrophobicity linking agent, stir, form the reversed-phase emulsion of water-in-oil-type, be template with this emulsion again, be placed in 25～90 ℃ water-bath, reacted 12～48 hours, the product oven dry is just obtained hydrophobicity soap-free polymerization thing porous material.
Said polyurethane aqueous dispersion is the ionic polyurethanes aqueous dispersions, its solid content: 0.25～25% ionic polyurethanes aqueous dispersions is by dibasic alcohol deutero-polyester polyol, poly-hexanodioic acid neopentyl glycol, 2, the 2-dimethylol propionic acid is different, Buddhist and ketone vulcabond react in the presence of the catalyzer dibutyl tin laurate and obtain prepolymer, is obtained by the triethylamine chain extension again.
In the reaction system, polyurethane aqueous dispersion accounts for the mass percent of system: 75～93.3%.
Said ionogen is one or more the mixture in sodium-chlor, calcium chloride, the sodium sulfate, and ionogen is 0.01～0.40 mol in the concentration of aqueous phase;
Said hydrophobic monomer is a kind of in vinylbenzene or the butyl acrylate or their mixture; The mass percent of the shared oil phase of hydrophobic monomer is 0～100%
Said hydrophobicity linking agent is a Vinylstyrene, ethylene glycol dimethyl double methacrylate or their mixture, and the mass percent of the shared oil phase of hydrophobicity linking agent is 100～0%.
Said initiator is water soluble starter ammonium persulphate, Potassium Persulphate or both mixtures; or be oil-soluble initiator azo-bis-isobutyl cyanide, dibenzoyl peroxide or both mixtures; when using water soluble starter; water soluble starter is 1～2% in the mass concentration of aqueous phase; when using oil-soluble initiator, the mass concentration of oil-soluble initiator in oil phase is 1～2%.
Adopt the hole shape looks of scanning electron microscope (SEM) JSM-6360LV (Japanese JEOL company) observation polymer porous material, and measure its aperture; Measure the pore volume of porous material with densimetry.
Preparation method of the present invention is simple, through conventional Raolical polymerizable, can obtain the aperture between 25～250 microns, the hydrophobic polymer porous material of pore volume between 1.0～14 milliliters/gram, and can make from film to blocky various body materials according to the shape of polymerization mould.
Description of drawings:
Fig. 1 is the stereoscan photograph of the polymer porous material of embodiment 1
Fig. 2 is the stereoscan photograph of the polymer porous material of embodiment 2
Fig. 3 is the stereoscan photograph of the polymer porous material of embodiment 3
Fig. 4 is the stereoscan photograph of the polymer porous material of embodiment 4
Fig. 5 is the stereoscan photograph of the polymer porous material of embodiment 5
Embodiment
Embodiment 1
0.03 gram azo-bis-isobutyl cyanide, 2.7 gram vinylbenzene and 0.3 Vinylstyrenes are joined as oil phase in 100 milliliters the flask, beaker is placed 70 ℃; To contain sodium-chlor 0.2 mol, solid content is 0.25% polyurethane aqueous dispersion, under the condition of stirring that remains a constant speed, be added drop-wise in the flask, behind the stable reversed-phase emulsion to be formed, again this reversed-phase emulsion be injected in the mould, be warming up to 90 ℃, reacted 24 hours, question response finishes, with the polymkeric substance deionized water wash, vacuum-drying more just obtains required porous material.
The gained pore volume is 8.5 a milliliters/gram, and big bore dia is 115.2 microns.
Embodiment 2
0.15 gram azo-bis-isobutyl cyanide and 7.5 gram vinylbenzene are joined as oil phase in 100 milliliters the flask, beaker is placed 70 ℃; To contain sodium-chlor 0.4 mol, solid content is 22.5 milliliters of 25% polyurethane aqueous dispersions, under the condition of stirring that remains a constant speed, be added drop-wise in the flask, behind the stable reversed-phase emulsion to be formed, again this reversed-phase emulsion be injected in the mould, be warming up to 70 ℃, reacted 24 hours, question response finishes, with the polymkeric substance deionized water wash, vacuum-drying more just obtains required porous material.
The gained pore volume is 3.5 a milliliters/gram, and big bore dia is 25.2 microns.
Embodiment 3
3 gram Vinylstyrenes are joined as oil phase in 100 milliliters the flask, beaker is placed 60 ℃; To contain calcium chloride 0.01 mol, ammonium persulphate mass concentration 1%, solid content is 12%, 27 milliliters of polyurethane aqueous dispersions, under the condition of stirring that remains a constant speed, be added drop-wise in the flask, behind the stable reversed-phase emulsion to be formed, again this reversed-phase emulsion is injected in the mould, at room temperature react 2 months after, with the polymkeric substance deionized water wash, vacuum-drying more just obtains required porous material.
The gained pore volume is 5.5 a milliliters/gram, and big bore dia is 82 microns.
Embodiment 4
1.8 gram vinylbenzene and 0.2 gram Vinylstyrene join as oil phase in 100 milliliters the flask, and beaker is placed 70 ℃; To contain calcium chloride 0.01 mol, Potassium Persulphate mass concentration 0.02%, solid content are 28 milliliters of 8% polyurethane aqueous dispersions, are added drop-wise in the flask under the condition of stirring that remains a constant speed, behind the stable reversed-phase emulsion to be formed, again this reversed-phase emulsion is injected in the mould, is warming up to 70 ℃, reacted 24 hours, question response finishes, with the polymkeric substance deionized water wash, vacuum-drying more just obtains required porous material.
The gained pore volume is 14 a milliliters/gram, and big bore dia is 248 microns.
Embodiment 5
0.03 gram azo-bis-isobutyl cyanide, 2.7 gram butyl acrylates and 0.3 gram ethylene glycol dimethyl double methacrylate vinylbenzene joined as oil phase in 100 milliliters the flask, beaker is placed 70 ℃; To contain sodium-chlor 0.2 mol, solid content is 27 milliliters of 12% polyurethane aqueous dispersions, under the condition of stirring that remains a constant speed, be added drop-wise in the flask, behind the stable reversed-phase emulsion to be formed, again this reversed-phase emulsion be injected in the mould, be warming up to 70 ℃, reacted 24 hours, question response finishes, with the polymkeric substance deionized water wash, vacuum-drying more just obtains required porous material.
The gained pore volume is 7.5 a milliliters/gram, and big bore dia is 151 microns.
Claims (1)
1. a reverse phase emulsion template method for preparing soap free hydrophobic polymer porous material is characterized in that, comprises the steps:
Under 60～90 ℃, be water to contain electrolytical ionic polyurethanes aqueous dispersions, it is joined in the oil phase of being made up of hydrophobic monomer and hydrophobicity linking agent, stir, form reversed-phase emulsion; With this emulsion is template, adds hydrophobic monomer and hydrophobicity linking agent in initiator, the control reaction temperature initiation emulsion, and polymerization obtains the soap free hydrophobic polymer porous material;
Said ionogen is one or more the mixture in sodium-chlor, calcium chloride, the sodium sulfate, and based on polyurethane aqueous dispersion, the ionogen consumption is 0.01～0.40 mol;
Said hydrophobic monomer is a vinylbenzene, and the massfraction of the shared oil phase of hydrophobic monomer is 0～100%;
Said hydrophobicity linking agent is a Vinylstyrene, and the massfraction of the shared oil phase of hydrophobicity linking agent is 100～0%;
Said initiator is ammonium persulphate, Potassium Persulphate, Diisopropyl azodicarboxylate or dibenzoyl peroxide, and the massfraction that initiator amount accounts for monomer and the total consumption of linking agent is 1～2%;
Described temperature of reaction is characterized in that, is controlled between 25 ℃ to 90 ℃;
The quality solid content of ionic polyurethanes aqueous dispersions: 0.25～25%; Polyurethane aqueous dispersion accounts for system quality percentage ratio: 75～93.3%, and the oil phase that hydrophobic monomer and hydrophobicity linking agent are formed accounts for system quality percentage ratio: 6.7～25%.
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| CN102585252B (en) * | 2011-01-10 | 2013-11-27 | 中国科学院大连化学物理研究所 | Method for synthesizing nonspherical polymer microparticles |
| CN102391416A (en) * | 2011-09-02 | 2012-03-28 | 华东理工大学 | Preparation method of porous material based on inorganic nanoparticles for stabilizing high internal phase emulsion |
| CN102838774B (en) * | 2012-09-26 | 2014-05-28 | 华东理工大学 | Preparation method for porous material based on water-in-oil type high internal phase emulsion with stable polymer macromolecules |
| CN102838773B (en) * | 2012-09-26 | 2014-05-28 | 华东理工大学 | Preparation method for porous material based on water-in-oil type high internal phase emulsion with stable polymer nanoparticles |
| CN107337745A (en) * | 2017-08-04 | 2017-11-10 | 西北工业大学 | A kind of preparation method of water-in-oil type polymer microcapsule |
| CN109455710A (en) * | 2018-12-29 | 2019-03-12 | 西北大学 | A method of the functional monomer polymeric modification graphene based on non-covalent bond |
| CN110511324A (en) * | 2019-09-19 | 2019-11-29 | 湖北工业大学 | A kind of Concentrated Emulsion Polymerization object preparation method containing sulfonic group alkyl |
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| US5980738A (en) * | 1995-10-04 | 1999-11-09 | Monsanta Company | Porous polymeric biosupports |
| EP1687341A2 (en) * | 2003-11-28 | 2006-08-09 | Commissariat A L'energie Atomique | Very low density polymer foams and method for the production thereof |
| CN101054423A (en) * | 2007-04-16 | 2007-10-17 | 华东理工大学 | Reversed phase emulsion template method for preparing opening polymer material |
| CN101497704A (en) * | 2009-02-25 | 2009-08-05 | 厦门大学 | High temperature resistant, ultra-hydrophile polystyrene porous membrane material and preparation thereof |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5980738A (en) * | 1995-10-04 | 1999-11-09 | Monsanta Company | Porous polymeric biosupports |
| EP1687341A2 (en) * | 2003-11-28 | 2006-08-09 | Commissariat A L'energie Atomique | Very low density polymer foams and method for the production thereof |
| CN101054423A (en) * | 2007-04-16 | 2007-10-17 | 华东理工大学 | Reversed phase emulsion template method for preparing opening polymer material |
| CN101497704A (en) * | 2009-02-25 | 2009-08-05 | 厦门大学 | High temperature resistant, ultra-hydrophile polystyrene porous membrane material and preparation thereof |
Non-Patent Citations (1)
| Title |
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| 李晓, 夏声平, 张卫英等.甲基丙烯酸甲酯/丙烯酸/水反相无皂微乳液体系的聚合.《化工学报》.2006,第57卷(第7期),1582-1587. * |
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