CN112169718A - Preparation method and application of polyimide hollow nano-microspheres - Google Patents
Preparation method and application of polyimide hollow nano-microspheres Download PDFInfo
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- CN112169718A CN112169718A CN202011093271.8A CN202011093271A CN112169718A CN 112169718 A CN112169718 A CN 112169718A CN 202011093271 A CN202011093271 A CN 202011093271A CN 112169718 A CN112169718 A CN 112169718A
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- 239000004005 microsphere Substances 0.000 title claims abstract description 39
- 239000004642 Polyimide Substances 0.000 title claims abstract description 28
- 229920001721 polyimide Polymers 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000000926 separation method Methods 0.000 claims abstract description 14
- 239000004530 micro-emulsion Substances 0.000 claims abstract description 12
- 239000012528 membrane Substances 0.000 claims abstract description 11
- 239000000178 monomer Substances 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000002904 solvent Substances 0.000 claims abstract description 7
- 238000001704 evaporation Methods 0.000 claims abstract description 4
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 4
- 238000003756 stirring Methods 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims abstract description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 18
- 239000003921 oil Substances 0.000 claims description 11
- 239000011248 coating agent Substances 0.000 claims description 9
- 238000000576 coating method Methods 0.000 claims description 9
- 239000002131 composite material Substances 0.000 claims description 6
- 239000004697 Polyetherimide Substances 0.000 claims description 5
- 229920001601 polyetherimide Polymers 0.000 claims description 5
- 229920002379 silicone rubber Polymers 0.000 claims description 5
- 239000003431 cross linking reagent Substances 0.000 claims description 4
- 239000004941 mixed matrix membrane Substances 0.000 claims description 4
- -1 polydimethylsiloxane Polymers 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 230000035699 permeability Effects 0.000 claims description 3
- 239000000243 solution Substances 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 11
- 239000002086 nanomaterial Substances 0.000 abstract description 2
- 150000004985 diamines Chemical class 0.000 abstract 2
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 abstract 1
- 150000001263 acyl chlorides Chemical class 0.000 abstract 1
- 239000012752 auxiliary agent Substances 0.000 abstract 1
- 238000005406 washing Methods 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 7
- 229920002545 silicone oil Polymers 0.000 description 3
- 239000004952 Polyamide Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000002077 nanosphere Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- BMXJGXKWZQEUAI-UHFFFAOYSA-N 5-phenylcyclohex-4-ene-1,1,3,3-tetracarbonyl chloride Chemical compound C=1(CC(CC(C=1)(C(=O)Cl)C(=O)Cl)(C(=O)Cl)C(=O)Cl)C1=CC=CC=C1 BMXJGXKWZQEUAI-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003937 drug carrier Substances 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 238000005373 pervaporation Methods 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
- B01D53/228—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion characterised by specific membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/58—Other polymers having nitrogen in the main chain, with or without oxygen or carbon only
- B01D71/62—Polycondensates having nitrogen-containing heterocyclic rings in the main chain
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Dispersion Chemistry (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention relates to the preparation of nano materials, in particular to a preparation method and application of polyimide hollow nano microspheres. The preparation process can be carried out according to the following method: dissolving diamine and other monomers in ethanol, dissolving a certain amount of oil-soluble acyl chloride monomer in a certain amount of oil-soluble solvent, mixing an ethanol solution containing diamine with an oil phase solvent and an auxiliary agent to form a water-in-oil type microemulsion, slowly dripping a pyromellitic dianhydride solution into a microemulsion system, stirring and polymerizing for a period of time at 25 ℃, evaporating to remove part of the solvent and water, washing with ethanol, and then putting into a vacuum oven to heat for 3 hours at 230 ℃ for imidization to obtain the polyimide hollow nano-microsphere. The polyimide hollow nano-microsphere can be used for preparing gas separation membranes.
Description
Technical Field
The invention relates to nanotechnology, in particular to a polyimide hollow nano microsphere, a preparation method and application thereof.
Background
So far, various nanomaterials have been the subject of research by many researchers, and polymer hollow microspheres have attracted much attention by researchers because of their advantages such as large specific surface area, small density, and good light scattering property. The hollow nano-microsphere has a larger hollow structure and can store gas, so that the dissolution coefficient is increased; the appearance of the cavity structure reduces the mass transfer resistance of the gas in the film, reduces the transmission path and increases the diffusion speed of the gas in the film; the dense layer of the microspheres can maintain selectivity to different gases.
Polyimide has high heat resistance, high mechanical strength, good dielectric property, good toxicity and high corrosion resistance, and is focused in the fields of aviation, chemical engineering, microelectronics and the like. The hollow polyimide microsphere has the characteristics of polyimide, and also has the advantages of strong adsorbability, large cohesion and the like of the polymer microsphere. Therefore, the method is widely applied to the fields of catalyst carriers, separation and purification, drug carriers and the like. The preparation of polyimide microspheres is much less visible in the few reports of hollow forms reported in the literature. The preparation methods reported are as follows: (1) hard template method: the hollow polyimide nano microspheres can be obtained by taking high polymer or inorganic microspheres as templates, wrapping polyimide on the templates, and removing the templates by some physical or chemical means. The method can ensure the uniformity of the aperture of the microsphere, but is difficult to remove the template. (2) An electrospray method: firstly, polyamide acid microdroplets are synthesized, and the content of the silicone oil is gradually increased from the surface layer of the microdroplets while the N-methyl pyrrolidone and the silicone oil are mutually diffused. Thus, upon contact with heated silicone oil, which is a poor solvent, polyamide microcasts are formed at the droplet interface, which are then thermally imidized to form a hard polyimide shell. The method has the advantages of simple device, easy control of experimental conditions and low cost. However, the particle size of the prepared microsphere is difficult to control, the operation temperature is high, and the microsphere is not suitable for temperature-sensitive polymers.
The invention mainly relates to a simple and convenient method for preparing polyimide hollow nano microspheres and application thereof, wherein the microspheres are blended with other polymers to prepare a film. The operation is simple, and the method can be used for gas separation membranes.
Disclosure of Invention
The invention aims to provide a simple method for preparing polyimide hollow nano microspheres and a preparation method and application thereof. The preparation scheme is as follows:
preparing 5% of ethanol solution of 4, 4- (9-fluorenylidene) -diamine, and preparing water-in-oil microemulsion from the ethanol solution, dichloromethane and water according to the mass ratio of 1: 2.2: 3.4; dissolving 0.026g of oil phase monomer (10% of the mass of dichloromethane in the microemulsion) in the microemulsion, stirring and polymerizing for a period of time at 25 ℃, evaporating to remove part of solvent and water, cleaning with ethanol, and heating in a vacuum oven at 230 ℃ for 3h for imidization to form the polyimide hollow microspheres.
The obtained polyimide hollow nano-microsphere is used as a dispersion phase to be blended with other polymers, and can be used for preparing a gas separation membrane.
The invention has the following advantages: the hollow nano-microsphere is generated by reaction in a microemulsion system, and the method is simple. Less steps and less time consumption. The microspheres are relatively uniform in size. The polymer microsphere is used as a disperse phase, and the compatibility between the disperse phase and the matrix is good, so that the permeability coefficient of the mixed matrix membrane is high.
Description of the drawings:
the following description is made in further detail with reference to the accompanying drawings and embodiments of the present invention.
FIG. 1 scanning electron (a) and transmission electron (b) photographs of hollow nanospheres prepared from 4, 4' - (9-fluorenylidene) -diamine and pyromellitic chloride in example 1.
FIG. 2 is an electron micrograph of a polyimide hollow nanosphere/silicone rubber mixed matrix film in example 2, wherein (a) is a surface photograph and (b) is a cross-sectional photograph.
The specific implementation method comprises the following steps:
the present invention will be described in detail with reference to specific examples, but the present invention is not limited to the examples.
Example 1:
preparing 5% of ethanol solution of 4, 4- (9-fluorenylidene) -diamine, and preparing water-in-oil microemulsion from the ethanol solution, dichloromethane and water according to the mass ratio of 1: 2.2: 3.4; dissolving 0.026g of oil phase monomer (10% of the mass of dichloromethane in the microemulsion) in the microemulsion, stirring and polymerizing for a period of time at 25 ℃, evaporating to remove part of solvent and water, cleaning with ethanol, and heating in a vacuum oven at 230 ℃ for 3h for imidization to form the polyimide hollow microspheres. The particle size is shown in table 1.
Watch 1
| Oil phase monomer | Outer diameter (nm) | Inner diameter (nm) |
| 1, 2, 4, 5-pyromellitic dianhydride | 60 | 40 |
| 3, 3, 5, 5-biphenyltetracarboxylic acid chloride | 55 | 22 |
Example 2:
adding the microspheres, a certain amount of polydimethylsiloxane and a certain amount of crosslinking agent (the mass ratio of the monomer to the crosslinking agent is 10: 1), adding the polyimide hollow nano microspheres, uniformly mixing, defoaming, placing in a polytetrafluoroethylene culture dish, and drying to obtain a mixed matrix membrane, wherein the properties of the mixed matrix membrane are shown in Table 2. Compared with no microspheres, O2The permeation rate of the catalyst is increased by about 2 times, and the gas separation coefficient is kept stable.
TABLE 2
| Microsphere content (wt.%) | O2Permeability coefficient (Barrer) | O2/N2Coefficient of separation |
| 0 | 786 | 2.01 |
| 3 | 1664 | 2.28 |
Example 3:
adding a certain amount of polyimide hollow nano microspheres into a silicon rubber solution to prepare a coating solution, pretreating the prepared coating solution, and coating the pretreated coating solution on the surface of a polyetherimide membrane to prepare the polyetherimide composite membrane.
Testing the gas separation performance of the composite membrane: o is2Permeability coefficient 2653GPU, N2Has a permeability coefficient of 1396GPU, O2/N2The separation factor was 1.9.
Example 4:
adding a certain amount of polyimide hollow microspheres into a silicon rubber solution to prepare a coating solution, performing vacuum defoamation on the prepared solution in a vacuum drying oven, pouring the solution onto a self-made polyvinylidene fluoride membrane, and using the prepared composite membrane for pervaporation separation of an ethanol/water system. The results show that the separation factor of the composite membrane is up to 15.6, and the permeation flux is 248 g/(m)2·h)。
Claims (3)
1. A preparation method of polyimide hollow nano-microspheres is characterized by comprising the following steps: preparing 5% of ethanol solution of 4, 4- (9-fluorenylidene) -diamine, and preparing water-in-oil microemulsion from the ethanol solution, dichloromethane and water according to the mass ratio of 1: 2.2: 3.4; dissolving 0.026g of oil phase monomer (10% of the mass of dichloromethane in the microemulsion) in the microemulsion, stirring and polymerizing for a period of time at 25 ℃, evaporating to remove part of solvent and water, cleaning with ethanol, and heating in a vacuum oven at 230 ℃ for 3h for imidization to form the polyimide hollow microspheres.
When the oil phase monomer of the oil phase is 1, 2, 4, 5-pyromellitic dianhydride, the outer diameter of the product is 60nm, and the inner diameter is 40 nm;
when the oil phase monomer of the oil phase is 3, 3, 5, 5-biphenyl tetracarboxyl chloride, the outer diameter of the product is 55nm, and the inner diameter of the product is 30 nm.
2. Adding the microspheres, a certain amount of polydimethylsiloxane and a certain amount of cross-linking agent (the mass ratio of the monomer to the cross-linking agent is 10: 1), adding the polyimide hollow nano microspheres, uniformly mixing, defoaming, placing in a polytetrafluoroethylene culture dish, and drying to obtain the mixed matrix membrane. Compared with pure film of silicon rubber, O2The permeation rate of the catalyst is increased by about 2 times, and the gas separation coefficient is kept stable.
When the load of the polyimide hollow nano-microspheres is 0 wt.%, O2Permeability coefficient of 786, O2/N2The separation coefficient was 2.01;
when the load capacity of the polyimide hollow nano microspheres is 3 wt.%, O2Permeability coefficient 1664, O2/N2The separation factor was 2.28.
3. Adding a certain amount of polyimide hollow nano microspheres into a silicon rubber solution to prepare a coating solution, pretreating the prepared coating solution, and coating the pretreated coating solution on the surface of a polyetherimide membrane to prepare the polyetherimide composite membrane.
O of the polyetherimide composite film2Permeability coefficient 2653GPU, N2Has a permeability coefficient of 1396GPU, O2/N2The separation factor was 1.9.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202011093271.8A CN112169718A (en) | 2020-10-14 | 2020-10-14 | Preparation method and application of polyimide hollow nano-microspheres |
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| CN202011093271.8A CN112169718A (en) | 2020-10-14 | 2020-10-14 | Preparation method and application of polyimide hollow nano-microspheres |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113649069A (en) * | 2021-08-02 | 2021-11-16 | 青海大学 | Photocatalytic material sulfur-doped polyimide hollow sphere and preparation method thereof |
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2020
- 2020-10-14 CN CN202011093271.8A patent/CN112169718A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113649069A (en) * | 2021-08-02 | 2021-11-16 | 青海大学 | Photocatalytic material sulfur-doped polyimide hollow sphere and preparation method thereof |
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