CN104710554A - Preparation method of interpenetrating network porous polymer composite material - Google Patents
Preparation method of interpenetrating network porous polymer composite material Download PDFInfo
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Abstract
The invention discloses a preparation method of an interpenetrating network porous polymer composite material, which comprises the following steps: mixing a vinyl monomer, an organosilicon monomer, a cross-linking agent, and a high-molecular emulsifier to a continuous phase, dissolving inorganic salt, a water-soluble initiator and a particle emulsifier into a disperse phase, dropping the disperse phase into the continuous phase under stirring, continuously stirring for 10 minutes to form a high internal-phase ratio emulsion, transferring into a plastic reactor, reacting for 12 hours in a water-bath under 65 DEG C, cutting the prepared solid materials into block shape, extracting absolute ethyl alcohol for 5-8 hours in a soxhlet extractor; and placing the extracted material in a vacuum baking oven under 80 DEG C and drying for 4-6 hours to obtain the porous polymer composite material. Under the prerequisite that the aperture and distribution of the porous polymeric material are controllable, the toughness and mechanical property are greatly increased.
Description
Technical field
The present invention relates to technical field of composite materials, be specially a kind of interpenetrating(polymer)networks porous polymer matrix material and preparation method thereof.
Background technology
Porous polymer material has the performance of many excellences, as low density, highly porous, high-ratio surface sum high absorption property etc., have a wide range of applications in fields such as life science, chemical catalysis, fractionation by adsorption, stratographic analysis, ion-exchanges, be subject to people and more and more pay close attention to.
In recent years, in the research of porous polymer material preparation method, high internal phase ratio emulsions mould plate technique causes people and studies interest greatly.High internal phase ratio emulsions refers to the emulsion of volume fraction more than 74% of interior phase (disperse phase), and 74% is maximum volume mark when monodispersed dispersed phase drop is tightly packed in emulsion.This definition is proposed in the sixties in 20th century by Lissant the earliest.In ordinary emulsion system, the volume fraction of disperse phase is generally 30% ~ 40%, reaches as high as about 50%, and now dispersed phase drop is disjunctly spherically dispersed in external phase with mutual; When dispersed phase drop is tightly packed with isodiametric spheroid, its volume fraction is 74%; Along with the volume of disperse phase increases further, owing to mutually extruding the polyhedron-shaped vacuole become by the external phase film isolation containing tensio-active agent between drop.If with polymerisable monomer composition external phase, make it be polymerized under certain condition, product, through extracting, drying, defines hole as after the dispersed phase drop gasification of template, can obtain porous polymer material.The porous polymer material adopting high internal phase emulsion as template to prepare has second hole structure: first, and dispersed phase drop template can form micron-sized abscess after removing, and also can form micron-sized interconnective aperture between adjacent abscess; Secondly, cell wall can form nano level pore.Pore structure special above makes this porous polymer material have higher specific surface area.In addition, by adjusting process parameter, as the kind of emulsifying agent and consumption, the volume fraction of disperse phase, polymerization temperature and stir speed (S.S.) etc. accurately can control aperture and distribution, the porosity etc. of porous polymer material.
Since last century the seventies, although people prepare porous polymer material to high internal phase emulsion as template carried out research extensively and profoundly, have developed very eurypalynous porous material, but the application that these toughnesss of material are very low, fragility is large, frangible, mechanical property is poor shortcoming greatly limit it.Up to now, also product capable of being industrialized is not succeeded in developing.Therefore, the porous polymer material that preparation has higher toughness and a higher mechanical strength becomes the biggest problem that this problem faces.
Interpenetrating net polymer (Interpenetrating Po1ymer Network, IPN) is that two kinds of polymer molecular chains are run through and mutually with each self-crosslinking of the mode of chemical bond and the polymer materials of a class uniqueness of being tangled by network interpenetrating and being formed.IPN has been widely used in the preparation of anti-ballistic materials, is a kind of emerging matrix material technology of preparing.The inierpeneirating network structure of polymkeric substance makes it have unique excellent properties, and as good toughness, physical strength is high.Therefore interpenetrating net polymer technology of preparing is applied in high internal phase emulsion as template and prepares in porous polymer matrix material by this patent, adopt macromolecule emulsifier, silicone comonomer is added in the external phase of high internal phase ratio emulsions, prepared the interpenetrating(polymer)networks porous polymer matrix material that configuration of surface is controlled, its toughness and physical strength all have and significantly improve.
Summary of the invention
The object of the invention is to overcome that porous polymer material toughness is in the past low, the shortcoming of bad mechanical property, a kind of preparation method of new porous polymer material is provided, make the porous polymer material obtained under the prerequisite that its pore size and distribution is controlled, its toughness and mechanical property all can have lifting by a relatively large margin.
The technical solution adopted for the present invention to solve the technical problems is: a kind of preparation method of interpenetrating(polymer)networks porous polymer matrix material, and it comprises following steps:
Vinyl monomer, organosilane monomer, linking agent, macromolecule emulsifier are mixed composition external phase by a certain percentage, and their quality is respectively 40 ~ 60%, 20 ~ 30%, 10 ~ 20%, 5 ~ 10% of external phase total mass;
Inorganic salt, water soluble starter, particle emulsifying agents are dissolved in distilled water and form disperse phase, after dissolving completes, be: inorganic salt concentration is 1.0 ~ 2.5g/L that the concentration of water soluble starter is 2.0 ~ 5.0g/L to the final concentration of composition, the concentration of particle emulsifying agents is 1.0 ~ 3.0g/L;
With continuous stirring disperse phase solution is slowly added drop-wise in external phase, within about 40 ~ 60 minutes, dropwises;
Continue stirring 10 minutes, form the high internal phase ratio emulsions of stable and uniform, disperse phase quality accounts for 75 ~ 90% of emulsion total mass;
Then emulsion is transferred in plastics reactor, be placed in the water-bath of 65 DEG C and react 12 hours, more obtained solid material is cut into bulk, with dehydrated alcohol extracting 5 ~ 8 hours in apparatus,Soxhlet's;
Finally the material that extracting is good to be placed in the vacuum drying oven of 80 DEG C dry 4 ~ 6 hours, porous polymer matrix material can be obtained.
Described vinyl monomer is the combination of one or more in vinylbenzene, ethyl propenoate, butyl acrylate, ethyl acrylate, polyalkylene glycol acrylate methoxyl group ester.
Described organosilane monomer is the one in octyl group Trimethoxy silane, octamethylcyclotetrasiloxane, in propyl trimethoxy silicane, hexadecyl trimethoxy silane.
Described linking agent is the one in TEGDMA, Vinylstyrene.
Described macromolecule emulsifier is the one in HypermerB-246sf, Hypermer1038sf, Hypermer B210, Hypemer1031.
Described inorganic salt are calcium chloride, Repone K or potassium sulfate.
Described water soluble starter is the one in Potassium Persulphate, ammonium persulphate.
Described particle emulsifying agents is nano SiO 2 particle.
According to porous polymer matrix material prepared by aforesaid method, aperture is between 1 ~ 8 micron, and porosity is between 73 ~ 85%.
The invention has the beneficial effects as follows: the configuration of surface adopting scanning electron microscope observation porous polymer matrix material, analyze the pattern in hole, measure the diameter in hole, adopt hold-up method to measure the practical porosity of porous polymer material.
Porous polymer matrix material prepared by the present invention has the following advantages:
A. the present invention's high-molecular block copolymer is emulsifying agent, and emulsion intercalation method is strong, and the porous polymer matrix material of preparation has the vesicular structure of comparatively rule, and its pore structure control effectively by preparation technology parameter;
B. in addition, the porous polymer matrix material of preparation has organic and inorganic inierpeneirating network structure, its toughness and physical strength higher.
Accompanying drawing explanation
Fig. 1 is the stereoscan photograph of the porous polymer matrix material of embodiment 1;
Fig. 2 is the stereoscan photograph of the porous polymer matrix material of embodiment 2;
Fig. 3 is the stereoscan photograph of the porous polymer matrix material of embodiment 3;
Fig. 4 is the stereoscan photograph of the porous polymer matrix material of embodiment 4;
Fig. 5 is the stereoscan photograph of the porous polymer matrix material of embodiment 5.
Embodiment
Embodiment 1
By vinylbenzene 12 grams, butyl acrylate 3 grams, octyl group Trimethoxy silane 5 grams, Vinylstyrene 2.5 grams, emulsifying agent HypermerB-246sf 2.5 grams mixes composition external phase; Calcium chloride 0.10g, Potassium Persulphate 0.37g, Nano particles of silicon dioxide 0.15g are dissolved in 75ml water and form disperse phase.At room temperature, dispersion fluid is slowly added drop-wise in external phase, and constantly stirs, within about 40 minutes, dropwise.Continue stirring 10 minutes, form the high internal phase ratio emulsions of stable and uniform.Then emulsion is transferred in plastics reactor, react 12 hours in the water-bath of 65 DEG C, obtained solid material is cut into bulk, with dehydrated alcohol extracting 10 hours in apparatus,Soxhlet's.Finally the material that extracting is good to be placed in the vacuum drying oven of 80 DEG C dry 4 hours, just to obtain porous polymer matrix material.The cell diameter of gained porous polymer matrix material is 1 ~ 4 μm, and porosity is about 74%.
Embodiment 2
By vinylbenzene 9 grams, ethyl acrylate 3 grams, octamethylcyclotetrasiloxane 8 grams, Vinylstyrene 2.5 grams, emulsifying agent HypermerB210 2.5 grams mixes composition external phase; Calcium chloride 0.1g, Potassium Persulphate 0.37g, Nano particles of silicon dioxide 0.15g are dissolved in 75ml water and form disperse phase.At room temperature, dispersion fluid is slowly added drop-wise in external phase, and constantly stirs, within about 40 minutes, dropwise.Continue stirring 10 minutes, form the high internal phase ratio emulsions of stable and uniform.Then emulsion is transferred in plastics reactor, react 12 hours in the water-bath of 65 DEG C, obtained solid material is cut into bulk, with dehydrated alcohol extracting 10 hours in apparatus,Soxhlet's.Finally the material that extracting is good to be placed in the vacuum drying oven of 80 DEG C dry 4 hours, just to obtain porous polymer matrix material.The cell diameter of gained porous polymer matrix material is 2 ~ 5 μm, and porosity is about 73%.
Embodiment 3
By vinylbenzene 7 grams, ethyl acrylate 4 grams, octamethylcyclotetrasiloxane 4.5 grams, Vinylstyrene 2 grams, emulsifying agent Hypemer1031 2.5 grams mixes composition external phase; Repone K 0.15g, Potassium Persulphate 0.32g, Nano particles of silicon dioxide 0.20g are dissolved in 80ml water and form disperse phase.At room temperature, dispersion fluid is slowly added drop-wise in external phase, and constantly stirs, within about 50 minutes, dropwise.Continue stirring 10 minutes, form the high internal phase ratio emulsions of stable and uniform.Then emulsion is transferred in plastics reactor, react 12 hours in the water-bath of 65 DEG C, obtained solid material is cut into bulk, with dehydrated alcohol extracting 7 hours in apparatus,Soxhlet's.Finally the material that extracting is good to be placed in the vacuum drying oven of 80 DEG C dry 6 hours, just to obtain porous polymer matrix material.The cell diameter of gained porous polymer matrix material is 2 ~ 6 μm, and porosity is about 77%.
Embodiment 4
By vinylbenzene 7 grams, polyalkylene glycol acrylate methoxyl group ester 4 grams, propyl trimethoxy silicane 4.5 grams, Vinylstyrene 2 grams, emulsifying agent Hypermer1038sf 2.5 grams mixes composition external phase; Calcium chloride 0.15g, ammonium persulphate 0.32g, Nano particles of silicon dioxide 0.20g are dissolved in 80ml water and form disperse phase.At room temperature, dispersion fluid is slowly added drop-wise in external phase, and constantly stirs, within about 50 minutes, dropwise.Continue stirring 10 minutes, form the high internal phase ratio emulsions of stable and uniform.Then emulsion is transferred in plastics reactor, react 12 hours in the water-bath of 65 DEG C, obtained solid material is cut into bulk, with dehydrated alcohol extracting 8 hours in apparatus,Soxhlet's.Finally the material that extracting is good to be placed in the vacuum drying oven of 80 DEG C dry 5 hours, just to obtain porous polymer matrix material.The cell diameter of gained porous polymer matrix material is 3 ~ 7 μm, and porosity is about 77%.
Embodiment 5
By vinylbenzene 3 grams, polyalkylene glycol acrylate methoxyl group ester 2 grams, hexadecyl trimethoxy silane 2.5 grams, TEGDMA 1 gram, emulsifying agent Hypermer1038sf 2 grams mixes composition external phase; Potassium sulfate 0.20g, ammonium persulphate 0.25g, Nano particles of silicon dioxide 0.25g are dissolved in 90ml water and form disperse phase.At room temperature, dispersion fluid is slowly added drop-wise in external phase, and constantly stirs, within about 60 minutes, dropwise.Continue stirring 10 minutes, form the high internal phase ratio emulsions of stable and uniform.Then emulsion is transferred in plastics reactor, react 12 hours in the water-bath of 65 DEG C, obtained solid material is cut into bulk, with dehydrated alcohol extracting 5 hours in apparatus,Soxhlet's.Finally the material that extracting is good to be placed in the vacuum drying oven of 80 DEG C dry 4 hours, just to obtain porous polymer matrix material.The cell diameter of gained porous polymer matrix material is 3 ~ 8 μm, and porosity is about 85%.
Certainly, above-mentioned explanation is not limitation of the present invention, and the present invention is also not limited in above-mentioned citing, and the change that those skilled in the art make in essential scope of the present invention, remodeling, interpolation or replacement also should belong to protection scope of the present invention.
Claims (9)
1. a preparation method for interpenetrating(polymer)networks porous polymer matrix material, is characterized in that, it comprises following steps:
Vinyl monomer, organosilane monomer, linking agent, macromolecule emulsifier are mixed composition external phase by a certain percentage, and their quality is respectively 40 ~ 60%, 20 ~ 30%, 10 ~ 20%, 5 ~ 10% of external phase total mass;
Inorganic salt, water soluble starter, particle emulsifying agents are dissolved in distilled water and form disperse phase, after dissolving completes, be: inorganic salt concentration is 1.0 ~ 2.5g/L that the concentration of water soluble starter is 2.0 ~ 5.0g/L to the final concentration of composition, the concentration of particle emulsifying agents is 1.0 ~ 3.0g/L;
With continuous stirring disperse phase solution is slowly added drop-wise in external phase, within about 40 ~ 60 minutes, dropwises;
Continue stirring 10 minutes, form the high internal phase ratio emulsions of stable and uniform;
Then emulsion is transferred in plastics reactor, be placed in the water-bath of 65 DEG C and react 12 hours, more obtained solid material is cut into bulk, with dehydrated alcohol extracting 5 ~ 8 hours in apparatus,Soxhlet's;
Finally the material that extracting is good to be placed in the vacuum drying oven of 80 DEG C dry 4 ~ 6 hours, porous polymer matrix material can be obtained.
2. the preparation method of a kind of interpenetrating(polymer)networks porous polymer matrix material according to claim 1, is characterized in that: described vinyl monomer is one or both in vinylbenzene, ethyl propenoate, butyl acrylate, ethyl acrylate, polyalkylene glycol acrylate methoxyl group ester.
3. the preparation method of a kind of interpenetrating(polymer)networks porous polymer matrix material according to claim 1, is characterized in that: described organosilane monomer is the one in octyl group Trimethoxy silane, octamethylcyclotetrasiloxane, in propyl trimethoxy silicane, hexadecyl trimethoxy silane.
4. the preparation method of a kind of interpenetrating(polymer)networks porous polymer matrix material according to claim 1, is characterized in that: described linking agent is the one in TEGDMA, Vinylstyrene.
5. the preparation method of a kind of interpenetrating(polymer)networks porous polymer matrix material according to claim 1, is characterized in that: described macromolecule emulsifier is the one in HypermerB-246sf, Hypermer1038sf, Hypermer B210, Hypemer1031.
6. the preparation method of a kind of interpenetrating(polymer)networks porous polymer matrix material according to claim 1, is characterized in that: described inorganic salt are calcium chloride, Repone K or potassium sulfate.
7. the preparation method of a kind of interpenetrating(polymer)networks porous polymer matrix material according to claim 1, is characterized in that: described water soluble starter is the one in Potassium Persulphate, ammonium persulphate.
8. the preparation method of a kind of interpenetrating(polymer)networks porous polymer matrix material according to claim 1, is characterized in that: described particle emulsifying agents is nano SiO 2 particle.
9. the porous polymer matrix material prepared of method according to claim 1, is characterized in that: aperture is between 1 ~ 8 micron, and porosity is between 73 ~ 85%.
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Cited By (6)
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| CN105013490A (en) * | 2015-07-03 | 2015-11-04 | 湘潭大学 | Metal nanoparticle-foamy carbon catalyst, and preparation method and application thereof |
| CN105489867A (en) * | 2016-01-21 | 2016-04-13 | 泰山医学院 | Porous carbon and silicon material and preparation method thereof |
| CN106478866A (en) * | 2016-10-07 | 2017-03-08 | 琼州学院 | A kind of preparation method of organic porous material |
| CN108299829A (en) * | 2018-03-16 | 2018-07-20 | 武汉大学 | Organosilicon interpenetrating net polymer and preparation method thereof |
| CN109776716A (en) * | 2019-01-18 | 2019-05-21 | 上海巴德富实业有限公司 | A kind of composite porous material and preparation method thereof |
| CN114369190A (en) * | 2022-01-24 | 2022-04-19 | 西南石油大学 | Preparation method of high-elasticity super-hydrophobic polystyrene porous material |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105013490A (en) * | 2015-07-03 | 2015-11-04 | 湘潭大学 | Metal nanoparticle-foamy carbon catalyst, and preparation method and application thereof |
| CN105489867A (en) * | 2016-01-21 | 2016-04-13 | 泰山医学院 | Porous carbon and silicon material and preparation method thereof |
| CN106478866A (en) * | 2016-10-07 | 2017-03-08 | 琼州学院 | A kind of preparation method of organic porous material |
| CN108299829A (en) * | 2018-03-16 | 2018-07-20 | 武汉大学 | Organosilicon interpenetrating net polymer and preparation method thereof |
| CN109776716A (en) * | 2019-01-18 | 2019-05-21 | 上海巴德富实业有限公司 | A kind of composite porous material and preparation method thereof |
| CN114369190A (en) * | 2022-01-24 | 2022-04-19 | 西南石油大学 | Preparation method of high-elasticity super-hydrophobic polystyrene porous material |
| CN114369190B (en) * | 2022-01-24 | 2023-09-22 | 西南石油大学 | Preparation method of high-elasticity super-hydrophobic polystyrene porous material |
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Application publication date: 20150617 |