CN101537334A - Hollow polymer capsule with shell layer containing mesopores and preparation method thereof - Google Patents
Hollow polymer capsule with shell layer containing mesopores and preparation method thereof Download PDFInfo
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- CN101537334A CN101537334A CN200910097288A CN200910097288A CN101537334A CN 101537334 A CN101537334 A CN 101537334A CN 200910097288 A CN200910097288 A CN 200910097288A CN 200910097288 A CN200910097288 A CN 200910097288A CN 101537334 A CN101537334 A CN 101537334A
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Abstract
The invention discloses a hollow polymer capsule with a shell layer containing mesopores and a preparation method thereof. The shell layer of the hollow polymer capsule is made of mesoporous materials, the pore diameter of the mesoporous materials is 6-10nm, the outer diameter of the shell layer is 100-200nm, the thickness of the shell layer is 10-30nm, the total specific surface area of the hollow polymer capsule is 106.2-649.5m<2>/g, and the total pore volume of the hollow polymer capsule is 0.4438-1.062cm<3>/g. The invention takes mini-emulsion droplets as a micro-reactor for preparing the hollow polymer capsule with the shell layer containing the mesopores, the process is simple and the prepared hollow capsule has small size and uniform distribution of the pore diameter of the shell layer. The hollow polymer capsule with the shell layer containing the mesopores effectively increases the specific surface area of the materials and is more conducive to improving the reserve volume of guest molecules.
Description
Technical field
The present invention relates to hollow polymer capsule of a kind of shell layer containing mesopores and preparation method thereof.
Background technology
The mesoporous nano material has high specific area, and regularly arranged and regulatable duct (2～50nm), make it at catalytic chemistry, adsorbing separation, medicament slow release, sensing technology, enzyme immobilization and ecology and field of nanometer material technology have a lot of potential using values, become present research focus.Mesoporous material has the pore passage structure of bigger specific area and rule, makes it have very high activity and great adsorption capacity, and the research and development of nano material is that mesoporous material has increased many new purposes.In recent years, the research of mesoporous material mainly concentrates on preparation and the modification aspect to M41S, SBA-15 series mesopore molecular sieve, but because the silicon species condensation in the mesoporous molecular sieve framework is incomplete, hole wall is in amorphous state and hole wall surface and the inner non-polymeric surface silanol groups in a large number that exist, caused mesoporous molecular water heat endurance relatively poor, and most catalytic reactions, enzyme immobilization and bio-separation are all carried out under hydrothermal condition.Therefore, the mesoporous nano material of preparation high hydrothermal stability has become the research focus in the synthetic field of present preparation mesoporous nano material.And in the synthetic field of traditional molecular sieve, it be raw material that mesopore molecular sieve is normally used ethyl orthosilicate (TEOS), silica and surfactant etc., obtains by long reaction, synthesizes with high costs.Operating process of the present invention is easy, and synthesis technique is simple, can overcome the shortcoming of at present existing technology effectively.Simultaneously all need bigger cavity in fields such as medicament slow release and bio-separation and realize these processes, therefore from using, shell is the application that the hollow nano capsule of mesoporous material has been widened single mesoporous material and Nano capsule greatly.
Summary of the invention
The objective of the invention is to overcome the deficiencies in the prior art, hollow polymer capsule of a kind of shell layer containing mesopores and preparation method thereof is provided.
The shell of the hollow polymer capsule of shell layer containing mesopores is a mesoporous material, and the aperture of mesoporous material is 6～10nm, and the thickness of shell is 10～30nm through being 100～200nm for shell outer, and total specific area of hollow polymer capsule is 106.2～649.5m
2/ g, total pore volume of hollow polymer capsule is: 0.4438～1.062cm
3/ g.
The preparation method of the hollow polymer capsule of shell layer containing mesopores comprises the steps:
1) poly-(methyl methacrylate-b-methacryloxypropyl trimethyl silane) and 1～10 weight portion assistant for emulsifying agent with 10 weight portions joins in the organic solvent of 50～400 weight portions, mixes, and forms oil solution;
2) ionic emulsifying agent of 9～20 weight portions and the nonionic of 45～100 weight portions are dissolved in the water of 900～2000 weight portions, form the aqueous solution;
3) with above-mentioned oil solution and aqueous solution, after the high shear field effect, pulverize, make miniemulsion;
4) miniemulsion is moved in the container of sealing, drip as template with miniemulsion, preparing shell afterwards by poly-(methyl methacrylate-b-methacryloxypropyl trimethyl silane) solgel reaction in small droplet is the mesoporous material hollow capsules.
Described high shear field effect is provided by strong shearing liquid-liquid dispersing apparatus.Strong shearing liquid-liquid dispersing apparatus is ultrasonic wave pulverizer, high-pressure homogenizer or super gravity field generating means.Organic solvent is: toluene, ethylbenzene, isopropylbenzene, paraxylene, ortho-xylene, carrene or dioxane six alkane.The number-average molecular weight of the methyl methacrylate segment in poly-(methyl methacrylate-b-methacryloxypropyl trimethyl silane) is 0～15000, and the number-average molecular weight of the methacryloxypropyl trimethyl silane segment in poly-(methyl methacrylate-b-methacryloxypropyl trimethyl silane) is 10000～40000.
The beneficial effect that the present invention compared with prior art has:
1) adopt miniemulsion to drip for microreactor prepares the hollow capsules that shell is a mesoporous material, technology is simple, and the hollow capsules size that makes is little, shell pore-size distribution homogeneous.
2) the hollow capsules particle diameter is in 100～200nm scope, and shell thickness is 10～30nm, and pore diameter range is 6～10nm, and shell is that the specific area scope of the hollow capsules of mesoporous material is 106.2～649.5m
2/ g, the pore volume scope is: 0.4438～1.062cm
3/ g, shell are that the hollow capsules of mesoporous material has effectively increased the material specific area, more help improving the reserves of guest molecule.
Description of drawings
Fig. 1 is the transmission electron microscope TEM photo of the hollow polymer capsule of the shell layer containing mesopores that obtains of the embodiment of the invention 1;
Fig. 2 is the scanning electron microscope sem photo of the hollow polymer capsule of the shell layer containing mesopores that obtains of the embodiment of the invention 1;
Fig. 3 is the resulting isothermal adsorption desorption of the isothermal nitrogen adsorption desorption method working sample curve of the hollow polymer capsule of the shell layer containing mesopores that obtains of the embodiment of the invention 1;
Fig. 4 is the resulting pore size distribution curve of isothermal nitrogen adsorption desorption method working sample of the hollow polymer capsule of the shell layer containing mesopores that obtains of the embodiment of the invention 1.
The specific embodiment
The shell of the hollow polymer capsule of shell layer containing mesopores is a mesoporous material, and the aperture of mesoporous material is 6～10nm, and the thickness of shell is 10～30nm through being 100～200nm for shell outer, and total specific area of hollow polymer capsule is 106.2～649.5m
2/ g, total pore volume of hollow polymer capsule is: 0.4438～1.062cm
3/ g.
The preparation method of the hollow polymer capsule of described a kind of shell layer containing mesopores, it is characterized in that: the number-average molecular weight of the methyl methacrylate segment in described poly-(methyl methacrylate-b-methacryloxypropyl trimethyl silane) is 0～15000, and the number-average molecular weight of the methacryloxypropyl trimethyl silane segment in poly-(methyl methacrylate-b-methacryloxypropyl trimethyl silane) is 10000～40000.
Embodiment 1:
PEO with 0.36g SDS and 1.8g
40NE is dissolved in the 36g deionized water.The pH value of water is fixed on 7 to the pH value with the ammonium dihydrogen phosphate (ADP) and the sodium hydrogen phosphate of equivalent.Then with 0.2gHD and 0.4g poly-(methyl methacrylate-b-methacryloxypropyl trimethyl silane), wherein the mean molecule quantity of methyl methacrylate segment is 15000, the mean molecule quantity of methacryloxypropyl trimethyl silane segment is 40000, is dissolved in the toluene of 4g.Be under 75% the condition 0 ℃ of intensity then with ultrasonic disintegrator (KS600), ultrasonic 15 minutes.Add SDS 0.36g after the ultrasonic end, in the medical vials with the miniemulsion transferase 12 50ml of gained, sealing is preserved at last.In sample, add NH after 4 days
4OH.After 5 days that above-mentioned four groups of samples are centrifugal with methyl alcohol breakdown of emulsion precipitation, and with centrifugal again after the washed with methanol, triplicate is with the flush away emulsifying agent.After washing with the sample that obtains as under 50 ℃ of conditions of vacuum drying oven dry 24 hours.
Embodiment 2:
PEO with 1.6g SDS and 8g
40NE is dissolved in the 160g deionized water.The pH value of water is fixed on 7 to the pH value with the ammonium dihydrogen phosphate (ADP) and the sodium hydrogen phosphate of equivalent.Then with 0.08gHD and 0.08g poly-(methyl methacrylate-b-methacryloxypropyl trimethyl silane), wherein the mean molecule quantity of methyl methacrylate segment is 150000, the mean molecule quantity of methacryloxypropyl trimethyl silane segment is 1000, is dissolved in the toluene of 4g.Be under 75% the condition 0 ℃ of intensity then with ultrasonic disintegrator (KS600), ultrasonic 15 minutes.Add SDS 0.36g after the ultrasonic end, in the medical vials with the miniemulsion transferase 12 50m1 of gained, sealing is preserved at last.In sample, add NH after 4 days
4OH.After 5 days that above-mentioned four groups of samples are centrifugal with methyl alcohol breakdown of emulsion precipitation, and with centrifugal again after the washed with methanol, triplicate is with the flush away emulsifying agent.After washing with the sample that obtains as under 50 ℃ of conditions of vacuum drying oven dry 24 hours.
Embodiment 3:
PEO with 0.36g SDS and 1.8g
40NE is dissolved in the 36g deionized water.The pH value of water is fixed on 7 to the pH value with the ammonium dihydrogen phosphate (ADP) and the sodium hydrogen phosphate of equivalent.Then with 0.4g HD and 0.4g poly-(methyl methacrylate-b-methacryloxypropyl trimethyl silane), wherein the mean molecule quantity of methyl methacrylate segment is 200, the mean molecule quantity of methacryloxypropyl trimethyl silane segment is 100000, is dissolved in the toluene of 4g.Be under 75% the condition 0 ℃ of intensity then with ultrasonic disintegrator (KS600), ultrasonic 15 minutes.Add SDS 0.36g after the ultrasonic end, in the medical vials with the miniemulsion transferase 12 50ml of gained, sealing is preserved at last.In sample, add NH after 4 days
4OH.After 5 days that above-mentioned four groups of samples are centrifugal with methyl alcohol breakdown of emulsion precipitation, and with centrifugal again after the washed with methanol, triplicate is with the flush away emulsifying agent.After washing with the sample that obtains as under 50 ℃ of conditions of vacuum drying oven dry 24 hours.
Embodiment 4:
PEO with 0.36g SDS and 1.8g
40NE is dissolved in the 36g deionized water.The pH value of water is fixed on 7 to the pH value with the ammonium dihydrogen phosphate (ADP) and the sodium hydrogen phosphate of equivalent.With 0.2gHD and 0.4g polymethyl acyl-oxygen oxypropyl trimethyl silane, mean molecule quantity is 28000, is dissolved in the toluene of 4g then.Be under 75% the condition 0 ℃ of intensity then with ultrasonic disintegrator (KS600), ultrasonic 15 minutes.Add SDS 0.36g after the ultrasonic end, in the medical vials with the miniemulsion transferase 12 50ml of gained, sealing is preserved at last.In sample, add NH after 4 days
4OH.After 5 days that above-mentioned four groups of samples are centrifugal with methyl alcohol breakdown of emulsion precipitation, and with centrifugal again after the washed with methanol, triplicate is with the flush away emulsifying agent.After washing with the sample that obtains as under 50 ℃ of conditions of vacuum drying oven dry 24 hours.
Embodiment 5
1) poly-(methyl methacrylate-b-methacryloxypropyl trimethyl silane) and the 1 weight portion assistant for emulsifying agent with 10 weight portions joins in the ethylbenzene of 50 weight portions, mixes, and forms oil solution;
2) ionic emulsifying agent of 9 weight portions and the nonionic of 45 weight portions are dissolved in the water of 900 weight portions, form the aqueous solution;
3) with above-mentioned oil solution and aqueous solution, pulverize through the ultrasonic wave pulverizer, make miniemulsion;
4) miniemulsion is moved in the container of sealing, drip as template with miniemulsion, preparing shell afterwards by poly-(methyl methacrylate-b-methacryloxypropyl trimethyl silane) solgel reaction in small droplet is the mesoporous material hollow capsules.
Embodiment 6
1) poly-(methyl methacrylate-b-methacryloxypropyl trimethyl silane) and the 10 weight portion assistant for emulsifying agents with 10 weight portions join in dioxane six alkane of 400 weight portions, mix, and form oil solution;
2) ionic emulsifying agent of 20 weight portions and the nonionic of 100 weight portions are dissolved in the water of 2000 weight portions, form the aqueous solution;
3) with above-mentioned oil solution and aqueous solution, pulverize through high-pressure homogenizer, make miniemulsion;
4) miniemulsion is moved in the container of sealing, drip as template with miniemulsion, preparing shell afterwards by poly-(methyl methacrylate-b-methacryloxypropyl trimethyl silane) solgel reaction in small droplet is the mesoporous material hollow capsules.
Claims (6)
1. the hollow polymer capsule of a shell layer containing mesopores, it is characterized in that: the shell of hollow polymer capsule is a mesoporous material, the aperture of mesoporous material is 6～10nm, shell outer through being 100～200nm, the thickness of shell is 10～30nm, and total specific area of hollow polymer capsule is 106.2～649.5m
2/ g, total pore volume of hollow polymer capsule is: 0.4438～1.062cm
3/ g.
2. the preparation method according to the hollow polymer capsule of the described shell layer containing mesopores of claim 1 is characterized in that comprising the steps:
1) poly-(methyl methacrylate-b-methacryloxypropyl trimethyl silane) and 1～10 weight portion assistant for emulsifying agent with 10 weight portions joins in the organic solvent of 50～400 weight portions, mixes, and forms oil solution;
2) ionic emulsifying agent of 9～20 weight portions and the nonionic of 45～100 weight portions are dissolved in the water of 900～2000 weight portions, form the aqueous solution;
3) with above-mentioned oil solution and aqueous solution, after the high shear field effect, pulverize, make miniemulsion;
4) miniemulsion is moved in the container of sealing, drip as template with miniemulsion, preparing shell afterwards by poly-(methyl methacrylate-b-methacryloxypropyl trimethyl silane) solgel reaction in small droplet is the mesoporous material hollow capsules.
3. the preparation method of the hollow polymer capsule of a kind of shell layer containing mesopores according to claim 2, it is characterized in that: described high shear field effect is provided by strong shearing liquid-liquid dispersing apparatus.
4. the preparation method of the hollow polymer capsule of a kind of shell layer containing mesopores according to claim 3, it is characterized in that: described strong shearing liquid-liquid dispersing apparatus is ultrasonic wave pulverizer, high-pressure homogenizer, miniflow dispersing apparatus or super gravity field generating means.
5. the preparation method of the hollow polymer capsule of a kind of shell layer containing mesopores according to claim 2, it is characterized in that: described organic solvent is: toluene, ethylbenzene, isopropylbenzene, paraxylene, ortho-xylene, carrene or dioxane six alkane.
6. the preparation method of the hollow polymer capsule of a kind of shell layer containing mesopores according to claim 2, it is characterized in that: the number-average molecular weight of the methyl methacrylate segment in described poly-(methyl methacrylate-b-methacryloxypropyl trimethyl silane) is 200～150000, and the number-average molecular weight of the methacryloxypropyl trimethyl silane segment in poly-(methyl methacrylate-b-methacryloxypropyl trimethyl silane) is 1000～100000.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102504326A (en) * | 2011-09-28 | 2012-06-20 | 浙江大学 | Method for preparing super thermal isolation polymer materials from polymer nanometer hollow capsules |
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2009
- 2009-04-02 CN CN200910097288A patent/CN101537334A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102504326A (en) * | 2011-09-28 | 2012-06-20 | 浙江大学 | Method for preparing super thermal isolation polymer materials from polymer nanometer hollow capsules |
| CN102504326B (en) * | 2011-09-28 | 2013-08-07 | 浙江大学 | Method for preparing super thermal isolation polymer materials from polymer nanometer hollow capsules |
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Open date: 20090923 |