CN103214611B - Preparation method for monodisperse nanometre pore-foaming agent with template agent - Google Patents
Preparation method for monodisperse nanometre pore-foaming agent with template agent Download PDFInfo
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- CN103214611B CN103214611B CN201310176864.4A CN201310176864A CN103214611B CN 103214611 B CN103214611 B CN 103214611B CN 201310176864 A CN201310176864 A CN 201310176864A CN 103214611 B CN103214611 B CN 103214611B
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Abstract
The invention discloses a preparation method for a monodisperse nanometre pore-foaming agent with a template agent. The preparation method comprises the following steps of: adding a surfactant, an inorganic salt and a cosurfactant in a certain ratio in a monomer; adding all the materials in a certain amount of distilled water; stirring, emulsifying and standing to obtain oil-in-water type micro-emulsion; adding a certain concentration of water-soluble initiator monomer in the micro-emulsion; charging N2 to protect, mechanically stirring, and heating; and performing polymerization reaction for a certain time, then dripping alkaline liquor in the system, and adjusting the pH value to be 8-10, so as to obtain a special pore-foaming agent with a certain hydrophilic-lipophilic balance value, monodisperse particle size distribution, and a size range of 20-500 nm. The pore-foaming agent obtained by the preparation method disclosed by the invention is uniform in particle size, monodisperse in distribution, and capable of giving uniform pores/cavities to the nanometre porous material prepared from the pore-foaming agent.
Description
Technical field
The invention belongs to synthesis of polymer material and modification field, be specifically related to a kind of preparation method carrying the single dispersing type nanometer pore-creating agent of template.
Background technology
Receiving bore material (nanoporous materials) is the special porous material of a class, and its aperture size, within the scope of nanoscale, is generally 1 ~ 200nm.Because such material has relatively large specific surface area, relatively homogeneous aperture, special passage (duct), it has a wide range of applications in fields such as dielectric, optics, magnetics, new forms of energy, chemical engineering, biotechnology, military and national defense, has become the study hotspot of multiple subject in global range.
The method preparing receiving bore material has multiple, as secondary deposition method, sol-gel method, thermal decomposition method, supercritical foaming method, electrochemical etching method, pore-creating agent method etc.The aperture size often heterogeneity of gained receiving bore material, cannot meet application needs in some special dimension (as nano molecular sieve etc.).
Pore-creating agent legal system for receiving bore material have simple to operate, do not rely on the advantages such as specific installation.Its basic step is: mixed in dispersion agent with a certain proportion of pore-creating agent by body material, removing dispersion agent, setting, utilize the method removing pore-creating agent of thermal degradation or solvent extraction, in body material, namely leave the hole/hole corresponding with pore-creating agent.Visible, pore-creating agent legal system is subject to the direct control of pore-creating agent for receiving bore material products obtained therefrom aperture, can think receiving bore size and pore-creating agent approximately equal, and thus pore-creating agent is most important for the performance preparing receiving bore material in this way.
Existing pore-creating agent aperture heterogeneity; Surface Template-free method, is easy to reunite; Oldered array cannot be formed.This type of pore-creating agent is utilized to prepare receiving bore material aperture uneven, the reason of reuniting due to pore-creating agent makes part bore hole size in prepared material far beyond the scope (thus can the part even distinctive electricity of total loss receiving bore material, magnetics, mechanics, thermal property) of nanoscale, and the arrangement in hole also cannot form ordered arrangement.Therefore need to provide novel method to prepare the pore-creating agent that can overcome above-mentioned defect.
Summary of the invention
The object of this invention is to provide a kind of preparation method carrying the single dispersing type nanometer pore-creating agent of template, solve the problem that existing preparation method causes pore-creating agent aperture heterogeneity, is easy to reunion, cannot forms oldered array.
Technical scheme of the present invention is: a kind of preparation method carrying the single dispersing type nanometer pore-creating agent of template, its preparation process is: in monomer, add a certain proportion of tensio-active agent, inorganic salt and cosurfactant, join together again in a certain amount of distilled water, stirring, emulsification, staticly obtain oil-in-water microemulsion, certain density water soluble starter monomer is added, logical N in this microemulsion
2protection, mechanical stirring, intensification; after carrying out polyreaction certain hour; in system, drip alkali lye, adjust ph is 8 ~ 10, obtain having certain hydrophile-lipophile balance value, size distribution is that monodispersed, size range prepares special pore-creating agent at the receiving bore material of 20 ~ 500nm.
Further, described monomer is made up of hydrophobic monomer and hydrophilic monomer; Wherein the mass percent of hydrophobic monomer is 60% ~ 99%, and the mass percent of hydrophilic monomer is 40% ~ 1%.
Further, described hydrophobic monomer is the one in vinylbenzene, methyl methacrylate, Propylene glycol monoacrylate, Hydroxyethyl acrylate or vinyl cyanide; Described hydrophilic monomer is the one in vinylformic acid, acrylamide, oleic acid, linolic acid or linolenic acid.
Further, described tensio-active agent is: sodium lauryl sulphate, Sodium dodecylbenzene sulfonate, polyoxyethylene sorbitan monooleate 85(Tween85), polyoxyethylene sorbitan monooleate 83(Tween83), polyoxyethylene sorbitan monooleate 80(Tween80), polyoxyethylene sorbitan monooleate 65(Tween65), polyoxyethylene sorbitan monooleate 60(Tween60), polyoxyethylene sorbitan monooleate 40(Tween40), polyoxyethylene sorbitan monooleate 20(Tween20), polyoxyethylene nonylphenol ether 10, sorbitan fatty(acid)ester 85(Span85), sorbitan fatty(acid)ester 83(Span83), sorbitan fatty(acid)ester 80(Span80), sorbitan fatty(acid)ester 65(Span65), sorbitan fatty(acid)ester 60(Span60), sorbitan fatty(acid)ester 40(Span40), sorbitan fatty(acid)ester 20(Span20), polyoxyethylenated alcohol sodium sulfate (AES), peregal, one in turkey red oil or alginate propylene glycol.
Further, described cosurfactant is the one in propyl carbinol, Virahol or isopropylcarbinol.
Further, described inorganic salt are the one in sodium-chlor, Repone K, sodium sulfate, potassium sulfate, SODIUMNITRATE or saltpetre.
Further, described water soluble starter is the one in Sodium Persulfate, ammonium persulphate or Potassium Persulphate.
Further, described dosage of surfactant is 30% ~ 150% of monomer mass mark; Cosurfactant consumption is 10% ~ 80% of monomer mass mark.
Further, described alkali lye is the aqueous solution of the organic amines such as triethylamine, diethylamine, Monomethylamine, dimethylamine, quadrol, and mass concentration is 5% ~ 15%.Described organic amine includes but not limited to above-mentioned five kinds.Or the highly basic such as NaOH, KOH, mass concentration is 5% ~ 25%.
Further, the temperature of reaction of carrying out polyreaction described in is 50 ~ 95 DEG C; Reaction times is 5 ~ 35h.
If containing impurity such as stoppers in monomer, then need to purify, the method for purification is: be first the NaOH solution cleaning monomer several of 10% by isopyknic mass concentration, till washings is colourless.Neutrality is washed till with deionized water.Then underpressure distillation is carried out with after anhydrous sodium sulfate dehydration process.Be 1 ~ 50 kPa in vacuum tightness, start to steam liquid when bath temperature is 45 ~ 95 DEG C.In order to ensure the high purity of monomer, twice underpressure distillation is carried out to it, take the method for " leaving out the beginning and the end ", namely each distillation is divided into three portion collection, collect distillation cut in early stage (a small amount of liquid steamed when distillation starts respectively, account for about 15% of whole original monomer volume to be distilled), distillation cut in mid-term and distillation later stage cut (a small amount of liquid that distillation is remaining when nearly completing accounts for about 15% of whole original monomer volume to be distilled).The cut of distillation part in mid-term is the highly purified MMA monomer of polyreaction needs.
The present invention compared with prior art has following beneficial effect:
Gained pore-creating agent size of the present invention is homogeneous, distributes, can give and prepare the homogeneous hole/hole of gained receiving bore material with this pore-creating agent in monodispersity.This pore-creating agent shape is spherical, any surface finish, thus gained receiving bore material hole inwall is smooth.The method gained pore-creating agent material of main part tool hydrophobic nature, the surperficial template submissive with some amount molecule segment, give the wetting ability that it is certain, can form at thermoplastic polymer in dispersion agent (as water) array distributed according to certain rules, the material containing orderly nano pore structure can be prepared according to this.
Accompanying drawing explanation
Fig. 1 is the structural representation of pore-creating agent prepared by embodiment 2;
Fig. 2 is the structural representation of pore-creating agent prepared by embodiment 3.
Embodiment
embodiment 1:100ml distilled water, vinylbenzene, 5mL oleic acid, 8.5g Span 80,10.5 g Tween 80,5g propyl carbinol, the 3.5g NaCl of 30mL through purifying is added in the beaker of 500mL, the emulsified 3min of mechanical stirring 15min, 25000rpm under 1000rpm rotating speed.Static one hour, obtain the microemulsion of reaction mass.Above-mentioned material is added in the reactor of 250ml, and the latter is placed in the water-bath under room temperature, continue to pass into N in reactor
2with excluding air, under 400rpm rotating speed, continued mechanical stirs; In reaction mass system, add 1.25g water soluble starter Potassium Persulphate, regulate bath temperature to 75 DEG C, reaction 15h; Terminate rear mass concentration be 10% NaOH solution regulate material pH to be 9.5, namely obtain particle diameter and be about spherical holing agent that is 250nm, monodispersed, that carry template.
embodiment 2:100ml distilled water, vinylbenzene, 2mL vinylformic acid, 3.5g Span 60,5.6 g Sodium dodecylbenzene sulfonate, 2g propyl carbinol, the 1.2g NaCl of 15mL through purifying is added in the beaker of 500mL, the emulsified 3min of mechanical stirring 15min, 25000rpm under 1000rpm rotating speed.Static one hour, obtain the microemulsion of reaction mass.Above-mentioned material is added in the reactor of 250ml, and the latter is placed in the water-bath under room temperature, continue to pass into N in reactor
2with excluding air, under 400rpm rotating speed, continued mechanical stirs; In reaction mass system, add 0.6g water soluble starter ammonium persulphate, regulate bath temperature to 55 DEG C, reaction 35h; Terminate rear mass concentration be 15% NaOH solution regulate material pH to be 9, namely obtain particle diameter and be about spherical holing agent that is 70nm, monodispersed, that carry template.
embodiment 3:100ml distilled water, methyl methacrylate, 2mL acrylamide, 2.6g Span 40,3.5 g Tween 40,1.5g propyl carbinol, the 0.8g KCl of 10mL through purifying is added in the beaker of 500mL, the emulsified 3min of mechanical stirring 15min, 25000rpm under 1000rpm rotating speed.Static one hour, obtain the microemulsion of reaction mass.Above-mentioned material is added in the reactor of 250ml, and the latter is placed in the water-bath under room temperature, continue to pass into N in reactor
2with excluding air, under 400rpm rotating speed, continued mechanical stirs; In reaction mass system, add 0.6g water soluble starter ammonium persulphate, regulate bath temperature to 80 DEG C, reaction 24h; Terminate rear mass concentration be 10% ethylenediamine solution regulate material pH to be 9, namely obtain particle diameter and be about spherical holing agent that is 40nm, monodispersed, that carry template.
Claims (1)
1. one kind carries the preparation method of the single dispersing type nanometer pore-creating agent of template, it is characterized in that: its preparation process is: in monomer, add a certain proportion of tensio-active agent, inorganic salt and cosurfactant, join together again in a certain amount of distilled water, stirring, emulsification, staticly obtain oil-in-water microemulsion, certain density water soluble starter monomer is added, logical N in this microemulsion
2protection, mechanical stirring, intensification, after carrying out polyreaction certain hour, in system, drip alkali lye, adjust ph is 8 ~ 10, obtain having certain hydrophile-lipophile balance value, size distribution is that monodispersed, size range prepares special pore-creating agent at the receiving bore material of 20 ~ 500nm; Described monomer is made up of hydrophobic monomer and hydrophilic monomer mixing; Wherein the mass percent of hydrophobic monomer is 60% ~ 99%, and the mass percent of hydrophilic monomer is 40% ~ 1%; Described hydrophobic monomer is the one in vinylbenzene, methyl methacrylate, Propylene glycol monoacrylate, Hydroxyethyl acrylate or vinyl cyanide; Described hydrophilic monomer is the one in oleic acid, linolic acid or linolenic acid.
2. a kind of preparation method carrying the single dispersing type nanometer pore-creating agent of template according to claim 1, is characterized in that: described tensio-active agent is: sodium lauryl sulphate, Sodium dodecylbenzene sulfonate, polyoxyethylene sorbitan monooleate 85(Tween85), polyoxyethylene sorbitan monooleate 83(Tween83), polyoxyethylene sorbitan monooleate 80(Tween80), polyoxyethylene sorbitan monooleate 65(Tween65), polyoxyethylene sorbitan monooleate 60(Tween60), polyoxyethylene sorbitan monooleate 40(Tween40), polyoxyethylene sorbitan monooleate 20(Tween20), polyoxyethylene nonylphenol ether 10, sorbitan fatty(acid)ester 85(Span85), sorbitan fatty(acid)ester 83(Span83), sorbitan fatty(acid)ester 80(Span80), sorbitan fatty(acid)ester 65(Span65), sorbitan fatty(acid)ester 60(Span60), sorbitan fatty(acid)ester 40(Span40), sorbitan fatty(acid)ester 20(Span20), polyoxyethylenated alcohol sodium sulfate (AES), peregal, one in turkey red oil or alginate propylene glycol.
3. a kind of preparation method carrying the single dispersing type nanometer pore-creating agent of template according to claim 1, is characterized in that: described cosurfactant is the one in propyl carbinol, Virahol or isopropylcarbinol.
4. a kind of preparation method carrying the single dispersing type nanometer pore-creating agent of template according to claim 1, is characterized in that: described inorganic salt are the one in sodium-chlor, Repone K, sodium sulfate, potassium sulfate, SODIUMNITRATE or saltpetre.
5. a kind of preparation method carrying the single dispersing type nanometer pore-creating agent of template according to claim 1, is characterized in that: described water soluble starter is the one in Sodium Persulfate, ammonium persulphate or Potassium Persulphate.
6. a kind of preparation method carrying the single dispersing type nanometer pore-creating agent of template according to claim 1, is characterized in that: described dosage of surfactant is 30% ~ 150% of monomer mass mark; Cosurfactant consumption is 10% ~ 80% of monomer mass mark.
7. a kind of preparation method carrying the single dispersing type nanometer pore-creating agent of template according to claim 1, is characterized in that: described in carry out polyreaction temperature of reaction be 50 ~ 95 DEG C; Reaction times is 5 ~ 35h.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102311732A (en) * | 2010-07-08 | 2012-01-11 | 西北工业大学 | Porous zinc oxide electroluminescent material |
| CN102760579A (en) * | 2011-04-29 | 2012-10-31 | 中国科学院过程工程研究所 | Titanium dioxide thin-film electrode material for dye-sensitized solar cell and method for preparing titanium oxide thin-film electrode material |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102311732A (en) * | 2010-07-08 | 2012-01-11 | 西北工业大学 | Porous zinc oxide electroluminescent material |
| CN102760579A (en) * | 2011-04-29 | 2012-10-31 | 中国科学院过程工程研究所 | Titanium dioxide thin-film electrode material for dye-sensitized solar cell and method for preparing titanium oxide thin-film electrode material |
Non-Patent Citations (1)
| Title |
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| "非离子表面活性剂微乳液中苯乙烯聚合";史修启等;《化学试剂》;20050928;第27卷(第9期);第516~518页 * |
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