CN104028124B - Polyoxyethylene type high polymer-inorganic hybrid membrane as well as preparation method and application of membrane - Google Patents
Polyoxyethylene type high polymer-inorganic hybrid membrane as well as preparation method and application of membrane Download PDFInfo
- Publication number
- CN104028124B CN104028124B CN201410273487.0A CN201410273487A CN104028124B CN 104028124 B CN104028124 B CN 104028124B CN 201410273487 A CN201410273487 A CN 201410273487A CN 104028124 B CN104028124 B CN 104028124B
- Authority
- CN
- China
- Prior art keywords
- protamine
- polyethylene glycol
- inorganic hybrid
- hybrid membrane
- macromolecule
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/40—Capture or disposal of greenhouse gases of CO2
Landscapes
- Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
The invention discloses a polyoxyethylene type high polymer-inorganic hybrid membrane which takes polyoxyethylene type high polymer as a high polymer main body and takes a compound which induces the mineralization of tetraethyl orthosilicate by protamine as filler, wherein the thickness of the hybrid membrane is 85-105 micrometers. The preparation method comprises the following steps: adding a certain amount of polyether-polyamide block copolymer into an ethanol-water solution with the mass ratio being 70 to 30 to prepare high polymer solution with the mass percentage being 2-8%; adding protamine and aqueous solution of tetraethyl orthosilicate into the high polymer solution in sequence, uniformly stirring to prepare a membrane casting liquid; drying the membrane casting liquid to prepare the homogeneous hybrid membrane. The preparation process is simple and controllable and the condition is moderate; the polyoxyethylene type high polymer-inorganic hybrid membrane is used for gas separation and is particularly suitable for separation of CO2/CH4; the selectivity is 19.5-66 and the permeability is 84-281barrrer.
Description
Technical field
The present invention relates to a kind of polyethylene glycol macromolecule-inorganic hybrid membrane and preparation method and application, belong to gas film
Separation technology field.
Background technology
Macromolecular-inorganic hybrid membrane is with macromolecular material as continuous phase, with the material containing inorganic component as dispersion phase
The general designation of the big class membrane material being formed, due to having the advantage of polymeric membrane and inoranic membrane concurrently, opened since the nineties in 20th century
Begin to become an important branch of membrane technology.The preparation of macromolecular-inorganic hybrid membrane generally adopts blending method and in-situ synthesized.
Blending method is that inorganic nano-particle and macromolecule are directly blended film forming, and preparation is easy, regulation and control are flexible, but nanoparticle is easily sent out
Raw reunion, forms micron particles；Though permeability of the membrane can be improved, because inorganic particulate is distributed not homogeneous, film in film
Selectivity often poor.In-situ synthesized is to be dissolved in macromolecule casting solution being formed by inorganic precursor intending homogeneous phase solution, front
Drive body and form nanoparticle in polymer matrix after acid base catalysator effect issues raw hydrolysis condensation reaction, nanoparticle exists
It is uniformly dispersed in film, but preparation condition is harsh, poor controllability.Realizing the controllable standby under temperate condition will become macromolecule-no
Machine hybridized film research and development focus.
In nature, many animals and plants respectively go out, by biogenic mineral process system, the height that a large amount of delicate structure have superior function
Molecule-inorganic hybrid material, inorganic particulate is uniform in size, and is in nanoscale.Based on biomineralization principle in temperate condition
The lower inorganic nano material preparing pattern, structure-controllable, has become very active research field in recent years.Silicon oxide is research
One of most inorganic material, it by natural biological macromole (such as protamine, gelatin, lysozyme, shitosan) or can close
(such as poly- polypeptide, polycaprolactam polyamine induction mineralising is obtained to become macromolecule.But carry out the inorganic nano-particle that biomimetic mineralization obtains in the solution
It is susceptible to tightly packed, form the granule of micro-meter scale.It is contemplated that, if biomimetic mineralization system can be passed through in restricted clearance
Standby inorganic nano-particle, on the one hand can avoid the reunion of inorganic particulate, on the other hand can pass through the big ditty in Control constraints space
The size of section inorganic particulate and pattern, thus realize the preparation of high performance polymer-inorganic hybrid membrane.
Work before this seminar and show, protamine plays during induction sodium silicate generates silicon oxide and urges in the solution
Change and template action.Protamine is the protein extracting from Fish sperm nucleus, and molecular weight is in 5kda.Protamine molecule about by
30 aminoacid compositions, wherein more than 2/3 is arginine, and therefore its isoelectric point, IP is 10-12, positively charged in neutral conditions.By
This, in sodium silicate solution, each protamine molecule all can be by as spherical glue core, and silicon oxide can be given birth in its molecular surface
Long, with the carrying out of silicic acid polycondensation reaction, also polycondensation can occur between the silicone hydroxyl of adjacent protamine molecular surface so that being combined
The size of thing constantly increases, and forms unbodied protamine/silica nano particle.Protamine is dispersed in polyoxy by this research
In vinyl polymer, it is subsequently adding the formation of silicon source presoma induction regulating controlling silicon oxide in restricted clearance.By regulating and controlling silicon
The content regulation and control of source presoma generate the size of inorganic nano-particle.Investigate inorganic nano-particle to hybridized film physicalchemical structure
The impact regulating and controlling with free volume, and the impact to gas separating property.Up to the present, polyethylene glycol macromolecule-no
Machine hybridized film is used for gas separation and has no document report.
Content of the invention
It is an object of the invention to provide a kind of polyethylene glycol macromolecule-inorganic hybrid membrane, by polyoxyethylene of the present invention
Type macromolecular-inorganic hybrid membrane as gas separation membrane, for separating co2/ch4Mixture, has preferable separating effect.
Polyethylene glycol macromolecule-inorganic hybrid membrane of the present invention is by polyethylene glycol macromolecule, protamine and positive silicic acid
Ethyl ester is constituted, and with polyethylene glycol macromolecule for macromolecule main body, induces the complex of tetraethyl orthosilicate mineralising with protamine
For implant, protamine simultaneously works as template and the effect of catalyst；The thickness of this polyethylene glycol macromolecule-inorganic hybrid membrane
Spend for 85～105 microns；The mass ratio of polyethylene glycol macromolecule and protamine is 1:(0～0.3), tetraethyl orthosilicate and fish
The mass ratio of protamine is (0.5～8): 1；Described polyethylene glycol macromolecule is in polyether-polyamide block copolymer
Kind；Wherein, polyether segment is polyoxyethylene segment, and mass fraction is 55～80%；Polyamide segment is polycaprolactam or poly-
Lauramide segment, mass fraction is 20～45%.
The preparation method of polyethylene glycol macromolecule-inorganic hybrid membrane of the present invention, comprises the following steps:
Step 1, the polyether-polyamide block copolymer of certain mass is added the ethanol-water solution of mass ratio 70:30
In, it is heated to reflux 0.5～4h at 80 DEG C, is cooled to room temperature, prepared mass fraction is 2～8% macromolecular solution；
Sequentially add protamine and tetraethyl orthosilicate aqueous solution in step 2, the macromolecular solution being obtained to step 1, stir
Mix uniformly, prepared casting solution；Wherein, the addition of protamine be high molecule mass 0～30%, tetraethyl orthosilicate water-soluble
The concentration of liquid is 30mm/l, and the mass ratio of tetraethyl orthosilicate and protamine is between 0.5～8；
Step 3, above-mentioned casting solution is poured in politef culture dish, is dried under room temperature, makes the polyoxy of homogenizing
Ethylene type macromolecular-inorganic hybrid membrane.
It is used for gas with polyethylene glycol macromolecule-inorganic hybrid membrane of the present invention to separate, be particularly well-suited to co2/ch4Point
From.Selectivity is 19.5～66, and permeability is 84～281barrer.
It is an advantage of the current invention that: preparation process simplicity is controlled, and raw material is easy to get, mild condition, and prepared hybridized film is applied
Separate in gas, there is excellent combination property.
Brief description
Fig. 1 is the section local sem figure of polyethylene glycol macromolecule-inorganic hybrid membrane that embodiment 1 is obtained；
Fig. 2 is the section local sem figure of polyethylene glycol macromolecule-inorganic hybrid membrane that embodiment 2 is obtained；
Fig. 3 is the section local sem figure of polyethylene glycol macromolecule-inorganic hybrid membrane that embodiment 3 is obtained；
Fig. 4 is the section local sem figure of polyethylene glycol macromolecule-inorganic hybrid membrane that embodiment 4 is obtained；
Fig. 5 is the section local sem figure of polyethylene glycol macromolecule-inorganic hybrid membrane that embodiment 5 is obtained；
Fig. 6 is the section local sem figure of the pure polyethylene glycol macromolecule film that comparative example 1 is obtained；
Fig. 7 is the section local sem figure of polyethylene glycol macromolecule-inorganic hybrid membrane that comparative example 2 is obtained.
Specific embodiment
Tell about the detailed content of the present invention by the following examples, provide the convenience that embodiment is to understand, definitely not
Limit the present invention.
Embodiment 1: prepare polyethylene glycol macromolecule-inorganic hybrid membrane that thickness is about 80 microns.
This polyethylene glycol macromolecule-inorganic hybrid membrane is by polyethylene glycol macromolecule, protamine and tetraethyl orthosilicate
Constitute, with polyethylene glycol macromolecule for macromolecule main body, the complex of tetraethyl orthosilicate mineralising is induced for filling out with protamine
Fill thing, protamine simultaneously works as template and the effect of catalyst；The thickness of this polyethylene glycol macromolecule-inorganic hybrid membrane is
80 microns；Wherein, polyethylene glycol macromolecule and the mass ratio of protamine are 10:1, the matter of tetraethyl orthosilicate and protamine
Amount ratio is (0.5～8): 1；Described polyethylene glycol macromolecule is trade name1657 macromolecule.
The preparation method that this prepares polyethylene glycol macromolecule-inorganic hybrid membrane is as follows:
Step 1): weigh 0.6g trade name1657 macromolecule, 6g deionized water and 14g dehydrated alcohol add
In there-necked flask with condensing tube, it is placed in 80 DEG C of water bath with thermostatic control, the lower 2h that flows back of 500r/min stirring, make macromolecule all molten
Solution, be cooled to room temperature, prepared mass fraction be 5% macromolecular solution standby；
Step 2): weigh 0.06g protamine, be added to above-mentioned macromolecular solution, after protamine is completely dissolved, use
Liquid-transfering gun is added dropwise over the aqueous solution of the tetraethyl orthosilicate of 30mm/l, control the addition of the aqueous solution of tetraethyl orthosilicate so that
The mass ratio of tetraethyl orthosilicate and protamine is 0.5:1；Stop stirring after 60min, filtered with copper mesh, stand 1h deaeration, obtain
To casting solution；
Step 3): by above-mentioned steps 2) casting solution that obtains is poured over the politef culture dish (φ 100mm) of cleaning
In, 24h more than is dried under room temperature, obtains the polyethylene glycol macromolecule-inorganic hybrid membrane of thick about 80 μm of homogenizing.
Fig. 1 be embodiment 1 be obtained polyethylene glycol macromolecule-inorganic hybrid membrane section local sem figure, room temperature,
Carry out pure co under the conditions of 1bar2With pure ch4Permeance property is tested, co2And ch4Infiltration coefficient be respectively 84barrer and
1.5barrer (1barrer=10-10cm3(stp)cm/(cm2S cmhg)), co2/ch4Ideal selectivity is 56.
Embodiment 2: prepare polyethylene glycol macromolecule-inorganic hybrid membrane that thickness is about 85 microns.
The difference is that only with embodiment 1 hybridized film: tetraethyl orthosilicate is 1:1 with the mass ratio of protamine；This is miscellaneous
The preparation method difference from Example 1 changing film is: step 2) in, control the addition of the aqueous solution of tetraethyl orthosilicate,
The mass ratio making tetraethyl orthosilicate and protamine is 1:1；Finally give polyethylene glycol macromolecule that thickness is 85 microns-
Inorganic hybrid membrane.
Fig. 2 be embodiment 2 be obtained polyethylene glycol macromolecule-inorganic hybrid membrane section local sem figure, room temperature,
Carry out pure co under the conditions of 1bar2With pure ch4Permeance property is tested, co2And ch4Infiltration coefficient be respectively 161.5barrer and
2.47barrer, co2/ch4Ideal selectivity is 65.5.
Embodiment 3: prepare polyethylene glycol macromolecule-inorganic hybrid membrane that thickness is about 90 microns.
The difference is that only with embodiment 1 hybridized film: tetraethyl orthosilicate is 2:1 with the mass ratio of protamine；With reality
Apply example 1 hydridization membrane preparation method difference from Example 2 to be: step 2) in, control tetraethyl orthosilicate aqueous solution plus
Enter amount so that the mass ratio of tetraethyl orthosilicate and protamine is 2:1；Finally give the polyoxyethylene-type that thickness is 90 microns high
Molecule-inorganic hybrid membrane.
Fig. 3 be embodiment 3 be obtained polyethylene glycol macromolecule-inorganic hybrid membrane section local sem figure, room temperature,
Carry out pure co under the conditions of 1bar2With pure ch4Permeance property is tested, co2And ch4Infiltration coefficient be respectively 196barrer and
4.91barrer, co2/ch4Ideal selectivity is 39.9.
Embodiment 4: prepare polyethylene glycol macromolecule-inorganic hybrid membrane that thickness is 93 microns.
The difference is that only with embodiment 1 hybridized film: tetraethyl orthosilicate is 4:1 with the mass ratio of protamine；With reality
Apply example 1 hydridization membrane preparation method difference from Example 2 to be: step 2) in, control tetraethyl orthosilicate aqueous solution plus
Enter amount so that the mass ratio of tetraethyl orthosilicate and protamine is 4:1；Finally give the polyoxyethylene-type that thickness is 93 microns high
Molecule-inorganic hybrid membrane.
Fig. 4 be embodiment 4 be obtained polyethylene glycol macromolecule-inorganic hybrid membrane section local sem figure, room temperature,
Carry out pure co under the conditions of 1bar2With pure ch4Permeance property is tested, co2And ch4Infiltration coefficient be respectively 231barrer and
7.40barrer, co2/ch4Ideal selectivity is 31.2.
Embodiment 5: prepare polyethylene glycol macromolecule-inorganic hybrid membrane that thickness is about 96 microns.
The difference is that only with embodiment 1 hybridized film: tetraethyl orthosilicate is 8:1 with the mass ratio of protamine；With reality
Apply example 1 hydridization membrane preparation method difference from Example 2 to be: step 2) in, control tetraethyl orthosilicate aqueous solution plus
Enter amount so that the mass ratio of tetraethyl orthosilicate and protamine is 8:1；Finally give the polyoxyethylene-type that thickness is 96 microns high
Molecule-inorganic hybrid membrane.
Fig. 5 be embodiment 5 be obtained polyethylene glycol macromolecule-inorganic hybrid membrane section local sem figure, room temperature,
Carry out pure co under the conditions of 1bar2With pure ch4Permeance property is tested, co2And ch4Infiltration coefficient be respectively 281barrer and
14.4barrer, co2/ch4Ideal selectivity is 19.5.
Comparative example 1: the pure polyether-polyamide block copolymer film that thick about 85 microns of preparation.
Weigh 0.6g trade name pebaxMacromolecule, 6g water and 14g ethanol add the there-necked flask with condensing tube
In, it is placed in 80 DEG C of water bath with thermostatic control, the lower 2h that flows back of 500r/min stirring, so that macromolecule is all dissolved, filtered with copper mesh, standing
1h deaeration, is then poured in the politef culture dish (φ 100mm) of cleaning, 24h more than is dried, obtains thickness about under room temperature
The pure polyether-polyamide block copolymer film of 85 μm of homogenizing.
Fig. 6 be comparative example 1 be obtained pure polyether-polyamide block copolymer film section local sem figure, room temperature,
Carry out pure co under the conditions of 1bar2With pure ch4Permeance property is tested, co2And ch4Infiltration coefficient be respectively 116.6barrer and
6.63barrer, co2/ch4Ideal selectivity is 17.6.
Comparative example 2: prepare polyethylene glycol macromolecule-inorganic hybrid membrane that thickness is about 90 microns.
The macromolecule, 6g water and the 14g ethanol that weigh 0.6g trade name pebax 1657 add the there-necked flask with condensing tube
In, it is placed in 80 DEG C of water bath with thermostatic control, the lower 2h that flows back of 500r/min stirring, so that macromolecule is all dissolved, be subsequently cooled to room temperature
Standby.Weigh 0.06g protamine, add above-mentioned macromolecular solution, after protamine is completely dissolved, stops stirring, use copper
Net filtration, stands 1h deaeration, is poured in the politef culture dish (φ 100mm) of cleaning, 24h more than is dried under room temperature,
Obtain the polyethylene glycol macromolecule-inorganic hybrid membrane of thick about 90 μm of homogenizing.
Fig. 7 is a kind of section local sem figure of polyethylene glycol macromolecule-inorganic hybrid membrane that comparative example 2 is obtained, in room
Carry out pure co under the conditions of temperature, 10bar2With pure ch4Permeance property is tested, co2And ch4Infiltration coefficient be respectively 41.5barrer and
0.93barrer, co2/ch4Ideal selectivity is 44.
As Fig. 1 to Fig. 7, from comparative example 1, comparative example 2, embodiment 1, embodiment 2, embodiment 3, embodiment 4 and embodiment 5
As can be seen that compared with the pure polyether-polyamide block copolymer film of homogenizing more smooth in comparative example 1, if in comparative example 1
On the basis of increase have protamine, can have little particle in film, as depicted in figs. 1 and 2；Lure in filling protamine
Lead in the tetraethyl orthosilicate hybridized film of mineralising, then armorphous nano aggregate structure occurs, and with tetraethyl orthosilicate content
Increase, the particle diameter of Micelle-like Nano-structure of Two increases, as shown in Fig. 3 to Fig. 7, by Micelle-like Nano-structure of Two size adjustment granule in film from
By volume, thus adjusting permeability in film for the gas and selectivity, find, embodiment 2 has gas the most excellent by contrast
Body separating property.
Although above in conjunction with figure, invention has been described, the invention is not limited in above-mentioned specific embodiment party
Formula, above-mentioned specific embodiment is only schematically, rather than restricted, and those of ordinary skill in the art is at this
Under bright enlightenment, without deviating from the spirit of the invention, many variations can also be made, these belong to the guarantor of the present invention
Within shield.
Claims (3)
1. a kind of polyethylene glycol macromolecule-inorganic hybrid membrane it is characterised in that:
It is made up of polyethylene glycol macromolecule, protamine and tetraethyl orthosilicate, with polyethylene glycol macromolecule as polymeric main
Body, induces the complex of tetraethyl orthosilicate mineralising as implant with protamine, protamine simultaneously works as template and catalyst
Effect；The thickness of this polyethylene glycol macromolecule-inorganic hybrid membrane is 85～105 microns；
Polyethylene glycol macromolecule is 1:(0～0.3 with the mass ratio of protamine), and the content of protamine is not 0, positive silicon
Acetoacetic ester is (0.5～8) with the mass ratio of protamine: 1；
Described polyethylene glycol macromolecule is one kind of polyether-polyamide block copolymer, and wherein, polyether segment is polyoxyethylene
Segment, mass fraction is 55～80%；Polyamide segment be polycaprolactam or poly-lauramide segment, mass fraction be 20～
45%.
2. according to claim 1 polyethylene glycol macromolecule-inorganic hybrid membrane preparation method it is characterised in that include
Following steps:
Step 1, by polyether-polyamide block copolymer add mass ratio 70:30 ethanol-water solution in, heat back at 80 DEG C
Stream 0.5～4h, is cooled to room temperature, prepared mass fraction is 2～8% macromolecular solution；
The aqueous solution of protamine and tetraethyl orthosilicate, stirring is sequentially added in step 2, the macromolecular solution being obtained to step 1
Uniformly, prepared preparation liquid；Wherein, the addition of protamine is the 0～30% of high molecule mass, and the content of protamine is not
For 0, the concentration of the aqueous solution of tetraethyl orthosilicate is 30mm/l, and the mass ratio of tetraethyl orthosilicate and protamine is in (0.5～8): 1
Between；
Step 3, above-mentioned preparation liquid is poured in politef culture dish, is dried under room temperature, makes homogenizing hybridized film.
3. a kind of application of polyethylene glycol macromolecule-inorganic hybrid membrane as claimed in claim 1, described polyoxyethylene-type is high
Molecule-inorganic hybrid membrane is used for co2/ch4Separation, selectivity be 19.5～66, permeability be 84～281barrer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410273487.0A CN104028124B (en) | 2014-06-18 | 2014-06-18 | Polyoxyethylene type high polymer-inorganic hybrid membrane as well as preparation method and application of membrane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410273487.0A CN104028124B (en) | 2014-06-18 | 2014-06-18 | Polyoxyethylene type high polymer-inorganic hybrid membrane as well as preparation method and application of membrane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104028124A CN104028124A (en) | 2014-09-10 |
| CN104028124B true CN104028124B (en) | 2017-01-25 |
Family
ID=51459255
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410273487.0A Expired - Fee Related CN104028124B (en) | 2014-06-18 | 2014-06-18 | Polyoxyethylene type high polymer-inorganic hybrid membrane as well as preparation method and application of membrane |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104028124B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111013409B (en) * | 2019-12-27 | 2021-12-21 | 天津工业大学 | Mixed matrix membrane filled with lanthanide fluoride porous nanosheets and preparation method and application thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8187678B2 (en) * | 2006-02-13 | 2012-05-29 | Stc.Unm | Ultra-thin microporous/hybrid materials |
| CN101948620B (en) * | 2010-09-09 | 2012-05-23 | 天津大学 | Polydimethylsiloxane/silicon dioxide hybrid membrane and preparation method thereof |
| CN103055727B (en) * | 2013-01-11 | 2014-11-26 | 浙江工商大学 | Preparation method of gas separation hybrid membrane containing nanometer SiO2 particles |
-
2014
- 2014-06-18 CN CN201410273487.0A patent/CN104028124B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN104028124A (en) | 2014-09-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5802821B2 (en) | Method for producing microcapsules | |
| Niu et al. | Synthesis of nano/microstructures at fluid interfaces | |
| CN102247765B (en) | Hollow mesoporous silica bead-polymer hybrid ultrafiltration membrane and preparation method thereof | |
| CN101695634B (en) | Preparation method of hybrid hollow fiber film of ultrahigh molecular weight polyethylene/inorganic particles | |
| CN103450487B (en) | The Nano-meter SiO_2 that a kind of hydrophilic and hydrophobic is adjustable 2powder | |
| WO2013012268A2 (en) | Volume production method for uniformly sized silica nanoparticles | |
| CN103613101A (en) | Preparation method of mesoporous silica nanosphere having dendrimer-like open-framework structure | |
| CN103923248A (en) | Stable methylacryloyl cage type silsesquioxane emulsion with Pickering effect and preparation thereof | |
| CN103011182A (en) | Synthesis method of vesicular mesoporous silicon dioxide | |
| WO2014057976A1 (en) | Core-shell silica nanoparticles and production method thereof, hollow silica nanoparticle production method using same, and hollow silica nanoparticles obtained by said production method | |
| CN101857675B (en) | Preparation method of high-purity spherical full-pore silica gel particles | |
| CN104028124B (en) | Polyoxyethylene type high polymer-inorganic hybrid membrane as well as preparation method and application of membrane | |
| CN113480740B (en) | Preparation method of adjustable amphiphobic filler for silicone rubber and preparation of silicone rubber membrane | |
| CN104209023A (en) | Sulfonated poly(ether ether ketone)-sulfonated silicon dioxide microsphere hybrid membrane, as well as preparation and application of membrane | |
| JP6102393B2 (en) | Method for producing hollow silica nanoparticles | |
| CN104212154B (en) | Sulfonated polyether-ether-ketone-amination silicon dioxide microsphere hybridized film and preparation and application | |
| CN104028121B (en) | Sulfonated polyether-ether-ketone-amido modified titanium nanotube hybridized film and preparation and application | |
| CN105642130B (en) | Ionic Liquid Modified mesopore molecular sieve/composite membrane of polymer and its preparation and application | |
| CN101388267B (en) | Silicon dioxide magnetic composite particle and preparation | |
| CN108905501B (en) | Liquid material with porous structure and preparation method thereof | |
| CN105233529B (en) | A kind of high sulfur-containing natural gas purification single dispersing hydrophobic titanium dioxide silicon defoaming agent | |
| JP5377265B2 (en) | Polymer / tartaric acid crystalline nanocomposite and method for producing the same | |
| CN112354382A (en) | Three-dimensional covalent organic framework hybrid membrane loaded with ionic liquid, and preparation method and application thereof | |
| CN103601201A (en) | Monodispersed mesoporous silica nanoparticles and synthetic method thereof | |
| CN107325322A (en) | Modifying agent comprising nano material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20170125 Termination date: 20200618 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |