CN103788398B - The preparation method of the order mesoporous film of a kind of segmented copolymer - Google Patents
The preparation method of the order mesoporous film of a kind of segmented copolymer Download PDFInfo
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- CN103788398B CN103788398B CN201410036588.6A CN201410036588A CN103788398B CN 103788398 B CN103788398 B CN 103788398B CN 201410036588 A CN201410036588 A CN 201410036588A CN 103788398 B CN103788398 B CN 103788398B
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Abstract
The invention provides the preparation method of the order mesoporous film of a kind of segmented copolymer, belong to mesopore film preparation method field.Polystyrene-b-poly 4 vinyl pyridine is dissolved in mixed solvent by the method, after at room temperature sealing ageing, namely the order mesoporous film of segmented copolymer is obtained by spin-coating method film, the number-average molecular weight of described segmented copolymer polystyrene-b-poly 4 vinyl pyridine is 10000 ~ 100000, the composition mark of polystyrene section be segmented copolymer overall 0.4 ~ 0.6.The method forms meso-hole structure by making it to the ageing of block copolymer solution in painting membrane process, and the content of inorganic salt is added by adjustment, prepare the mesopore film of different hole dimension, and prior art compares, method technique of the present invention is simple, mild condition, cost are low.Experimental result shows: the mesopore film that method of the present invention prepares is regular Hexagonal packing ordered structure, and hole dimension is 20 ~ 50nm.
Description
Technical field
The present invention relates to a kind of method for manufacturing thin film of Material Field, be specifically related to the preparation method of the order mesoporous film of a kind of segmented copolymer.
Background technology
Mesoporous material refers to the poroid material of the solid of aperture between 2-50nm.Due to its have larger specific surface area and pore volume, relative thermostability preferably, larger and adjustable aperture and hole surface easy modified and in chemistry, biology, life science and Materials science etc., be subject to people pay close attention to greatly.Wherein, mesopore film overcomes the inferior position of direction, conventional powder shape mesoporous material duct indefiniteness, is all widely used in the arrangement etc. of optics, optoelectronic device, separatory membrane, microreactor and micromodules.
Traditional inorganic materials mesopore film is not easily processed, surface group is single, homopolymer mesopore film non-refractory, easily softens, and therefore selects a kind of excellent property and the material being easy to process just seems most important.The advantageous property of multiple polymers can combine by segmented copolymer, molecular weight is controlled, molecular weight distribution is narrower, molecular structure and composition can design, in theoretical investigation and practical application, have important meaning.Meanwhile, the multiple ordered structure of the 10-100nm size that the distinctive microphase-separated of segmented copolymer is formed, becomes a kind of new tool manufacturing mesopore film.The method utilizing segmented copolymer to prepare mesopore film common at present comprises polymer degradation method and polymer surfaces settling process etc., but these methods have processing charges expensive, process the limitation such as length consuming time, the course of processing be irreversible.
Summary of the invention
The object of the invention is to solve that the existing method preparing segmented copolymer mesopore film is complicated, processing charges is expensive and processing the problem of length consuming time, and the preparation method of the order mesoporous film of a kind of segmented copolymer is provided.
The invention provides the preparation method of the order mesoporous film of a kind of segmented copolymer, comprising:
Segmented copolymer polystyrene-b-poly 4 vinyl pyridine is dissolved in mixed solvent, after at room temperature sealing ageing, namely the order mesoporous film of segmented copolymer is obtained by spin-coating method film, the number-average molecular weight of described segmented copolymer polystyrene-b-poly 4 vinyl pyridine is 10000 ~ 100000, the composition mark of polystyrene section is the overall 0.4-0.6 of segmented copolymer, and described digestion time is more than two months.
Preferably, described mixed solvent is the solvent of dissolved polystyrene and the solvent of dissolving poly 4 vinyl pyridine.
Preferably, in described mixed solvent, the solvent of dissolved polystyrene and the solvent volume per-cent of dissolving poly 4 vinyl pyridine are (90% ~ 99%): (1% ~ 10%).
Preferably, the solvent of described dissolved polystyrene is toluene.
Preferably, the solvent of described dissolving poly 4 vinyl pyridine is methyl alcohol or ethanol.
Preferably, described is dissolved in solvent by segmented copolymer polystyrene-b-poly 4 vinyl pyridine, inorganic salt are dissolved in solvent, then by two kinds of solution mixing, after at room temperature sealing ageing, namely the order mesoporous film of segmented copolymer of different hole dimension is obtained by spin-coating method film, the number-average molecular weight of described segmented copolymer polystyrene-b-poly 4 vinyl pyridine is 10000 ~ 100000, the composition mark of polystyrene section be segmented copolymer overall 0.4 ~ 0.6, described digestion time is more than two months.
Preferably, described inorganic salt are cadmium acetate or Cadmium chloride fine powder.
Preferably, the consumption of described inorganic salt is the 0.1%-5% of block copolymerization amount.
Preferably, the concentration of described polystyrene-b-poly 4 vinyl pyridine is 0.1mg/mL-10mg/mL.
Preferably, described digestion time is three months to six months.
Beneficial effect of the present invention
The invention provides the preparation method of the order mesoporous film of a kind of segmented copolymer, polystyrene-b-poly 4 vinyl pyridine is dissolved in mixed solvent by the method, after at room temperature sealing ageing, namely the order mesoporous film of segmented copolymer is obtained by spin-coating method film, the number-average molecular weight of described segmented copolymer polystyrene-b-poly 4 vinyl pyridine is 10000 ~ 100000, the composition mark of polystyrene section be segmented copolymer overall 0.4 ~ 0.6.The method forms meso-hole structure by making it to the ageing of block copolymer solution in painting membrane process, and the content of inorganic salt can be added by adjustment, prepare the mesopore film of different hole dimension, and prior art compares, method technique of the present invention is simple, mild condition, cost are low.Experimental result shows: the mesopore film that method of the present invention prepares is regular Hexagonal packing ordered structure, and hole dimension is 20 ~ 50nm.
Accompanying drawing explanation
Fig. 1 is order mesoporous film atomic force microscope height map (a) of polystyrene-b-poly 4 vinyl pyridine and the phase diagram (b) of the embodiment of the present invention 1 preparation;
Fig. 2 is polystyrene-b-poly 4 vinyl pyridine order mesoporous film glancing incidence synchrotron radiation X-ray scattering X-Y scheme prepared by the embodiment of the present invention 2;
Fig. 3 is order mesoporous film atomic force microscope height map (a) of polystyrene-b-poly 4 vinyl pyridine/cadmium acetate and the phase diagram (b) of the embodiment of the present invention 3 preparation;
Fig. 4 is order mesoporous film atomic force microscope height map (a) of polystyrene-b-poly 4 vinyl pyridine/cadmium acetate and the phase diagram (b) of the embodiment of the present invention 4 preparation.
Fig. 5 embodiment of the present invention 1,3,4 obtains order mesoporous membrane pores dimensioned drawing;
Fig. 6 is polystyrene-b-poly 4 vinyl pyridine/cadmium acetate order mesoporous film transmission electron microscope contrast figure prepared by the embodiment of the present invention 5.
Embodiment
The invention provides the preparation method of the order mesoporous film of a kind of segmented copolymer, comprising:
Segmented copolymer polystyrene-b-poly 4 vinyl pyridine is dissolved in mixed solvent, after at room temperature sealing ageing, namely the order mesoporous film of segmented copolymer is obtained by spin-coating method film, the number-average molecular weight of described segmented copolymer polystyrene-b-poly 4 vinyl pyridine is 10000 ~ 100000, the composition mark of polystyrene section be segmented copolymer overall 0.4 ~ 0.6, be preferably 0.5, described digestion time is more than two months.
According to the present invention, described mixed solvent is preferably the solvent of dissolved polystyrene and dissolves the solvent of poly 4 vinyl pyridine.In described mixed solvent, the solvent of dissolved polystyrene and the solvent volume per-cent of dissolving poly 4 vinyl pyridine are preferably (90% ~ 99%): (1% ~ 10%).The solvent of described dissolved polystyrene is preferably toluene.The solvent of described dissolving poly 4 vinyl pyridine is preferably methyl alcohol or ethanol.
According to the present invention, in order to the order mesoporous film of the segmented copolymer obtaining different hole dimension, preferably in accordance with the following methods: segmented copolymer polystyrene-b-poly 4 vinyl pyridine is dissolved in solvent, inorganic salt are dissolved in solvent, then by two kinds of solution mixing, after at room temperature sealing ageing, namely the order mesoporous film of segmented copolymer of different hole dimension is obtained by spin-coating method film, the number-average molecular weight of described segmented copolymer polystyrene-b-poly 4 vinyl pyridine is 10000 ~ 100000, the composition mark of polystyrene section be segmented copolymer overall 0.4 ~ 0.6, be preferably 0.5, described digestion time is more than two months.
According to the present invention, in the described solvent for dissolving segmented copolymer polystyrene-b-poly 4 vinyl pyridine, select the selective solvent for polystyrene, be preferably toluene, select another kind of dissolution with solvents inorganic salt simultaneously, polystyrene-b-poly 4 vinyl pyridine solution and inorganic salt solution are preferably (90% ~ 99%) according to volume percent: (1% ~ 10%) mixes by particular methanol or ethanol.
According to the present invention, the number-average molecular weight of described segmented copolymer polystyrene-b-poly 4 vinyl pyridine is 10000 ~ 100000, be preferably 30000 ~ 80000, number-average molecular weight lower than 10000 time, microphase-separated forms structural instability, number-average molecular weight higher than 100000 time, the pore structure size of formation is greater than 50nm, does not belong to mesoporous yardstick.
According to the present invention, be not particularly limited described inorganic salt, be preferably cadmium acetate or Cadmium chloride fine powder, the consumption of described inorganic salt is preferably the 0.1%-5% of block copolymerization amount, is more preferably 0.5%-2%.Because inorganic salt are with the pyridine groups complexing on 4-vinylpridine segment, enhance the uncompatibility between two blocks, thus affect the mesopore size of microphase-separated formation, with the increase of inorganic salt consumption, meso-hole structure hole dimension reduces; When the molecular weight of polystyrene-b-poly 4 vinyl pyridine is fixed, the order mesoporous film of segmented copolymer of different hole dimension can be obtained by the content controlling inorganic salt.
According to the present invention, segmented copolymer polystyrene-b-poly 4 vinyl pyridine is dissolved in after in mixed solvent, in order to better dissolving, preferably at 20 ~ 24 DEG C, stirs 3 ~ 4h, be then warmed up to 70 ~ 80 DEG C of reaction 1 ~ 2h.
According to the present invention, the concentration of described polystyrene-b-poly 4 vinyl pyridine is preferably 0.1mg/mL-10mg/mL, is more preferably 1mg/mL-5mg/mL.
According to the present invention, described Aging Temperature is room temperature, is preferably 18-25 DEG C, is more preferably 20-24 DEG C; Described digestion time is more than at least two months, block copolymer micelle shell molecular chain of the present invention fully stretches in sufficiently long ageing process, the stability of micella weakens, under the effect of shearing force, micella breaks and microphase-separated occurs, while microphase-separated, save again the order that original micella is arranged on substrate, thus form orderly mesopore film.Therefore, must to ensure sufficiently long digestion time in preparation process, when ensureing that the intact strength of solution of sealing is constant, digestion time at least should reach two months.Be two months to eight months between preferred narrative tense, be more preferably three months to six months.Block copolymer solution is carried out ageing by the present invention, makes it in painting membrane process, form meso-hole structure.
According to the present invention, described spin-coating method film is the method that this area is commonly used, and be not particularly limited, described spin speed is preferably 1000-3500rpm, is more preferably 2000rpm, and spin-coating time is preferably 60s.
Morphology characterization is carried out to the order mesoporous film of segmented copolymer prepared by the present invention, with atomic force microscope (SPA300HV/SPI3800N), elliptic polarization spectrometer (JOBINYVON-SPEXHR460) and synchrotron radiation Grazing Incidence X-Ray scattering (BeamlineBW4atHASYLAB) viewing film structure and measurement thickness; The HF aqueous solution is used the film drift on silicon chip to be descended and pass through transmission electron microscope (JEOL-2000) viewing film pattern.
Do further detailed description below in conjunction with embodiment to the present invention, the raw material related in embodiment is commercially available.
Embodiment 1
By polystyrene-b-poly 4 vinyl pyridine, (number-average molecular weight is 44000, the composition mark of polystyrene section be segmented copolymer overall 0.5) be dissolved in toluene/ethanol (volume ratio is 95:5), polymer concentration is 1mg/mL, stir at room temperature 20 DEG C after 4 hours and be warming up to 70 DEG C of heating 2 hours, after polymkeric substance dissolves completely, solution is cooled to room temperature, and sealing and standing four months at this temperature, after four months, use sol evenning machine spin-coating film in silicon wafer substrate, rotating speed is 2000rpm, spin-coating time is 60s, obtain the order mesoporous film of polystyrene-b-poly 4 vinyl pyridine.
Fig. 1 is order mesoporous film atomic force microscope height map (a) of polystyrene-b-poly 4 vinyl pyridine and the phase diagram (b) of the embodiment of the present invention 1 preparation, as can be seen from the figure, the present invention has successfully prepared segmented copolymer mesopore film, mesopore film is regular Hexagonal packing ordered structure, hole dimension is about 47nm, as shown in a point in Fig. 5.
Embodiment 2
By polystyrene-b-poly 4 vinyl pyridine, (number-average molecular weight is 62000, the composition mark of polystyrene section be segmented copolymer overall 0.5) be dissolved in toluene and methanol (volume ratio is 90:10), polymer concentration is 2mg/mL, stir at room temperature 22 DEG C after 4 hours and be warming up to 70 DEG C of heating 2 hours, after polymkeric substance dissolves completely, solution is cooled to room temperature, and sealing and standing eight months at this temperature, after eight months, use sol evenning machine spin-coating film in silicon wafer substrate, rotating speed is 2500rpm, spin-coating time is 60s, obtain the order mesoporous film of polystyrene-b-poly 4 vinyl pyridine.
Order mesoporous film embodiment 2 obtained characterizes through atomic force microscope, confirms to generate segmented copolymer mesopore film, and mesopore film is regular Hexagonal packing ordered structure, and hole dimension is about 45nm.
Fig. 2 is polystyrene-b-poly 4 vinyl pyridine order mesoporous film glancing incidence synchrotron radiation X-ray scattering X-Y scheme prepared by the embodiment of the present invention 2; As can be seen from Figure 2, q is prolonged
zthe scattering peak that direction extends confirms the meso-hole structure perpendicular to substrate.
Embodiment 3
By polystyrene-b-poly 4 vinyl pyridine (number-average molecular weight is 44000, the composition mark of polystyrene section be segmented copolymer overall 0.5) be dissolved in toluene, stir at room temperature 20 DEG C after 4 hours and be warming up to 70 DEG C of heating two hours; Cadmium acetate is dissolved in ethanol, after dissolving completely and be cooled to room temperature, above-mentioned two kinds of solution mix and continue stirring 24 hours by 95:5 by volume, polymer concentration is 1mg/mL, cadmium acetate consumption is 0.5% of polystyrene-b-poly 4 vinyl pyridine quality, this mixing solutions leaves standstill four months at room temperature 20 DEG C of lower seals, after four months, use sol evenning machine spin-coating film in silicon wafer substrate, rotating speed is 1500rpm, spin-coating time is 60s, obtains the order mesoporous film of polystyrene-b-poly 4 vinyl pyridine/cadmium acetate.
Fig. 3 is order mesoporous film atomic force microscope height map (a) of polystyrene-b-poly 4 vinyl pyridine/cadmium acetate and the phase diagram (b) of the embodiment of the present invention 3 preparation, as can be seen from the figure, the present invention has successfully prepared segmented copolymer mesopore film, mesopore film is regular Hexagonal packing ordered structure, hole dimension is about 42nm, as shown in the b point in Fig. 5.
Embodiment 4
By polystyrene-b-poly 4 vinyl pyridine (number-average molecular weight is 44000, the composition mark of polystyrene section be segmented copolymer overall 0.5) be dissolved in toluene, stir at room temperature 23 DEG C after 4 hours and be warming up to 70 DEG C of heating two hours; Cadmium acetate is dissolved in methyl alcohol, after dissolving completely and be cooled to room temperature, above-mentioned two kinds of solution mix and continue stirring 24 hours by 90:10 by volume, polymer concentration is 3mg/mL, cadmium acetate consumption is 1.0% of polystyrene-b-poly 4 vinyl pyridine quality, this mixing solutions leaves standstill two months at room temperature 23 DEG C of lower seals, after two months, use sol evenning machine spin-coating film in silicon wafer substrate, rotating speed is 2000rpm, spin-coating time is 60s, obtains the order mesoporous film of polystyrene-b-poly 4 vinyl pyridine/cadmium acetate.
Fig. 4 is order mesoporous film atomic force microscope height map (a) of polystyrene-b-poly 4 vinyl pyridine/cadmium acetate and the phase diagram (b) of the embodiment of the present invention 4 preparation, as can be seen from the figure, the present invention has successfully prepared segmented copolymer mesopore film, mesopore film is regular Hexagonal packing ordered structure, hole dimension is about 37nm, as shown in the c point in Fig. 5.
Embodiment 5
By polystyrene-b-poly 4 vinyl pyridine (number-average molecular weight is 44000, the composition mark of polystyrene section be segmented copolymer overall 0.5) be dissolved in toluene, stir at room temperature 20 DEG C after 4 hours and be warming up to 70 DEG C of heating two hours; Cadmium acetate is dissolved in ethanol, after dissolving completely and be cooled to room temperature, above-mentioned two kinds of solution mix and continue stirring 24 hours by 95:5 by volume, polymer concentration is 5mg/mL, cadmium acetate consumption is 2% of polystyrene-b-poly 4 vinyl pyridine quality, this mixing solutions leaves standstill six months at room temperature 20 DEG C of lower seals, after six months, use sol evenning machine spin-coating film in silicon wafer substrate, rotating speed is 3000rpm, spin-coating time is 60s, obtains the order mesoporous film of polystyrene-b-poly 4 vinyl pyridine/cadmium acetate.
Fig. 6 is polystyrene-b-poly 4 vinyl pyridine/cadmium acetate order mesoporous film transmission electron microscope contrast figure prepared by the embodiment of the present invention 5, and Fig. 6 describes the present invention and successfully prepared segmented copolymer mesopore film, and hole dimension is about 33nm.
Embodiment 7
By polystyrene-b-poly 4 vinyl pyridine (number-average molecular weight is 30000, the composition mark of polystyrene section be segmented copolymer overall 0.5) be dissolved in toluene, stir at room temperature 22 DEG C after 4 hours and be warming up to 70 DEG C of heating two hours; Cadmium chloride fine powder is dissolved in ethanol, after dissolving completely and be cooled to room temperature, above-mentioned two kinds of solution mix and continue stirring 24 hours by 90:10 by volume, polymer concentration is 1mg/mL, Cadmium chloride fine powder consumption is 0.3% of polystyrene-b-poly 4 vinyl pyridine quality, this mixing solutions leaves standstill five months at room temperature 22 DEG C of lower seals, after five months, use sol evenning machine spin-coating film in silicon wafer substrate, rotating speed is 1500rpm, spin-coating time is 60s, obtains the order mesoporous film of polystyrene-b-poly 4 vinyl pyridine/Cadmium chloride fine powder.
Order mesoporous film embodiment 7 obtained characterizes through atomic force microscope, confirms to generate segmented copolymer mesopore film, and mesopore film is regular Hexagonal packing ordered structure, and hole dimension is about 45nm.
The explanation of above embodiment just understands method of the present invention and core concept thereof for helping.It should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention, can also carry out some improvement and modification to the present invention, these improve and modify and also fall in the protection domain of the claims in the present invention.
To the above-mentioned explanation of the disclosed embodiments, professional and technical personnel in the field are realized or uses the present invention.To be apparent for those skilled in the art to the multiple amendment of these embodiments, General Principle as defined herein can without departing from the spirit or scope of the present invention, realize in other embodiments.Therefore, the present invention can not be restricted to these embodiments shown in this article, but will meet the widest scope consistent with principle disclosed herein and features of novelty.
Claims (9)
1. a preparation method for the order mesoporous film of segmented copolymer, is characterized in that, comprising:
Segmented copolymer polystyrene-b-poly 4 vinyl pyridine is dissolved in mixed solvent, after at room temperature sealing ageing, namely the order mesoporous film of segmented copolymer is obtained by spin-coating method film, the number-average molecular weight of described segmented copolymer polystyrene-b-poly 4 vinyl pyridine is 10000 ~ 100000, the composition mark of polystyrene section is the overall 0.4-0.6 of segmented copolymer, and described digestion time is more than two months.
2. the preparation method of the order mesoporous film of a kind of segmented copolymer according to claim 1, is characterized in that, described mixed solvent is the solvent of dissolved polystyrene and the solvent of dissolving poly 4 vinyl pyridine.
3. the preparation method of the order mesoporous film of a kind of segmented copolymer according to claim 2, it is characterized in that, in described mixed solvent, the solvent of dissolved polystyrene and the solvent volume per-cent of dissolving poly 4 vinyl pyridine are (90% ~ 99%): (1% ~ 10%).
4., according to the preparation method of a kind of segmented copolymer order mesoporous film of claim 2-3 described in any one, it is characterized in that, the solvent of described dissolved polystyrene is toluene.
5., according to the preparation method of a kind of segmented copolymer order mesoporous film of claim 2-3 described in any one, it is characterized in that, the solvent of described dissolving poly 4 vinyl pyridine is methyl alcohol or ethanol.
6. the preparation method of the order mesoporous film of a kind of segmented copolymer according to claim 1, it is characterized in that, segmented copolymer polystyrene-b-poly 4 vinyl pyridine is dissolved in solvent, inorganic salt are dissolved in solvent, then by two kinds of solution mixing, after at room temperature sealing ageing, namely the order mesoporous film of segmented copolymer of different hole dimension is obtained by spin-coating method film, the number-average molecular weight of described segmented copolymer polystyrene-b-poly 4 vinyl pyridine is 10000 ~ 100000, the composition mark of polystyrene section be segmented copolymer overall 0.4 ~ 0.6, described digestion time is more than two months, the consumption of described inorganic salt is the 0.1%-5% of block copolymerization amount.
7. the preparation method of the order mesoporous film of a kind of segmented copolymer according to claim 6, is characterized in that, described inorganic salt are cadmium acetate or Cadmium chloride fine powder.
8. the preparation method of the order mesoporous film of a kind of segmented copolymer according to claim 1, is characterized in that, the concentration of described polystyrene-b-poly 4 vinyl pyridine is 0.1mg/mL-10mg/mL.
9. the preparation method of the order mesoporous film of a kind of segmented copolymer according to claim 1 or 6, is characterized in that, described digestion time is three months to six months.
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