CN105879726A - Polyether block amide gel film with sandwich structure and preparation method thereof - Google Patents
Polyether block amide gel film with sandwich structure and preparation method thereof Download PDFInfo
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- CN105879726A CN105879726A CN201410784259.XA CN201410784259A CN105879726A CN 105879726 A CN105879726 A CN 105879726A CN 201410784259 A CN201410784259 A CN 201410784259A CN 105879726 A CN105879726 A CN 105879726A
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- gel film
- polyether block
- block amide
- sandwich structure
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- 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
Abstract
The invention belongs to the technical field of film separation and relates to a polyether block amide gel film with a sandwich structure and a preparation method thereof. The film is characterized in that the film has the sandwich structure, the upper and lower surface layers are arranged as cross-linked surfaces and a gel layer is arranged in the middle. The preparation method comprises the following steps: (1) uniformly mixing polyether block amide, functional carrier and solvent under a certain temperature, paving on a polytetrafluoroethylene plate, and drying to remove the solvent to obtain a gel film; (2) soaking the gel film in the solution containing the cross-linking agent for 0.5-12 hours and performing the surface cross-linking reaction on the gel film; (3) drying the cross-linked gel film in air for 24 hours, and then transferring into a vacuum drying oven, and processing for 24 hours at 30 DEG C, thereby acquiring the polyether block amide gel film with the sandwich structure. According to the preparation method provided by the invention, the upper and lower surfaces of the film are cross-linked, so that the polyether block amide gel film with the sandwich structure is formed, the functional carrier is difficult to run off, the lasting stability of the physical structure and property of the film is ensured and the preparation method is fit for the separating of the carbon dioxide in the mixed gas and the recycling of the organic steam.
Description
Technical field
The invention belongs to technical field of membrane separation, particularly relate to a kind of sandwich structure polyether block amide gel film and preparation side thereof
Method.
Background technology
CO in current atmospheric2Concentration constantly rises, and greenhouse effect increasingly sharpens, and the ecological environment depending on the mankind for existence causes
Serious threat.Conventional CO2Isolation technics, such as amine aqueous solution absorption process, separation by deep refrigeration and pressure swing adsorption method, is realizing
Along with high energy consumption, high operating cost or the possibility that there is secondary pollution during gas separation.Therefore, there is economy, height
The membrane separation technique of the plurality of advantages such as effect, environmental protection receives more and more attention at gas separation field.
Gel film is the novel film materials of rising in recent years, high molecular polymer and functional vector collectively constitute.Polymer divides
Son forms spacial framework by effects such as crystallization, crosslinking or hydrogen bonds, holds onto liquid function carrier so that it is be uniformly dispersed
In the hole of network structure thus form stable self-supporting system.As a kind of between solid-state with the particular matter of liquid, solidifying
Glued membrane has the high stability of polymeric film, and the high pass of liquid film concurrently, is separating CO2Aspect has a good application prospect.
A kind of nonionic surfactant gel gas separation membrane disclosed in Chinese patent CN102489182A and preparation method thereof, institute
Selecting functional vector is polysorbas20, Tween 80 etc., has obtained the gel film that gas permselective property can be good.Chinese patent
CN103599707A and CN103657441A discloses the preparation method of several support ionic liquid gel film, also obtains
Relatively high permeating flux and the gel film of separation selectivity.But it is poor generally to there is mechanical property in existing gel film, structural instability,
The problems such as functional vector easily spilling, are unfavorable for the industrial applications of reality.
Summary of the invention
It is an object of the invention to the deficiency overcoming existing gel film at gas separation field, it is provided that a kind of sandwich structure polyethers is embedding
Section acrylamide gel film and preparation method thereof.The present invention is anti-by the active hydrogen on gel film top layer and isocyanate groups are carried out addition
Should, it is achieved the surface cross linking of gel film, form sandwich structure.Keeping its high permeating flux and high score from selective basis
On, be obviously improved the mechanical property of film, prepare have high permeating flux, high separation selectivity and excellent mechanical performances and
The cross-linked gel film of stability, great commercial Application potentiality.
A kind of sandwich structure polyether block amide gel film that the present invention proposes and preparation method thereof, it is characterised in that include as follows
Step:
A is flat after polyether block amide 10-20 part, solvent 70-80 part and functional vector 10-20 part uniformly being mixed at 70-90 DEG C
It is layered on polyfluortetraethylene plate, dry out solvent, prepares gel film；
1-5 part cross-linking agent is dissolved in 95-99 part normal hexane formation cross-linking agent solution by B, described gel film is immersed in this cross-linking agent molten
In liquid 0.5～12 hour, carry out gel film surface cross linking；
Gel film after crosslinking is dried 24 hours by C in atmosphere, then proceeds in vacuum drying oven, processes 24 hours at 30 DEG C,
Obtain sandwich structure polyether block amide gel film.
Preferably, described functional vector is ethylene glycol phenyl ether, ethylene glycol mono-ether, propandiol butyl ether or butyl.
Preferably, described cross-linking agent is methyl diphenylene diisocyanate, isophorone diisocyanate, hexa-methylene two isocyanide
Acid esters or toluene di-isocyanate(TDI).
Preferably, described polyether block amide is made up of polyether segment and polyamide segment, and wherein polyether segment is poly(ethylene oxide),
Polyamide segment is nylon 6, and both mass ratioes are 2: 3 or 3: 2.
Preferably, described solvent be formic acid, mass ratio be 7: 3 n-propanol/water mixed solvent or n-butyl alcohol that mass ratio is 8: 2/
Water mixed solvent.
The sandwich structure polyether block amide gel film that the present invention provides has three-decker, and upper layer is cross-linked layer, thickness
Between 2-10 micron；Centre is gel layer, and thickness is between 60-90 micron.
Polymeric matrix selected by the present invention is polyether block amide, and this material is by rigid chain segment polyamide and chain segment polyether group
Becoming, wherein polyamide segment provides mechanical strength, and polyether segment provides bigger free volume, is a kind of preferably gas separation material
Material.Selected function carrier has strong adsorptivity to carbon dioxide, good with the polyether block amide compatibility, the most cheap.This
The sandwich structure polyether block amide gel film that invention prepares has high permeation flux and separation selectivity, simultaneously mechanical performance
Well, stability is excellent.
In sum, sandwich structure polyether block amide gel film of the present invention and preparation method thereof has the advantage that
1, the functional vector that the present invention uses has strong adsorptivity to carbon dioxide, good with the polyether block amide compatibility, same to current price
Lattice are cheap.
2, the present invention prepares the method for gel film is solvent evaporation method, and technique is simple, easy to operate, favorable repeatability.
3, the cross-linking process of inventive gel film relates to interfacial reaction, and top layer is cross-linked layer, and even compact improves good mechanics
Performance and stability；Centre is gel layer, is full of functional vector, it is provided that high permeating flux and separation selectivity.
Detailed description of the invention:
The following is the embodiment of sandwich structure polyether block amide gel film and preparation method thereof, but described embodiment do not constitute right
The restriction of the present invention.
Embodiment one:
(1) gel film is prepared:
By 10 parts of polyether block amides (wherein the mass ratio of poly(ethylene oxide) segment and Nylon 6 Chains section is 3: 2), 70 parts of formic acid
It is laid on polyfluortetraethylene plate after mix homogeneously at 70 DEG C with 20 parts of ethylene glycol phenyl ethers, dry out solvent, prepares gel film.
(2) film top layer cross-links again:
Above-mentioned made gel film is immersed in 1 part of methyl diphenylene diisocyanate and 99 parts of hexane solutions, when controlling submergence
Between be 0.5 hour, carry out gel film surface cross linking.
(3) post processing:
Gel film after crosslinking is dried 24 hours in atmosphere, then proceeds in vacuum drying oven, process 24 hours at 30 DEG C,
Obtain sandwich structure polyether block amide gel film.
Above-mentioned sandwich structure polyether block amide gel film is used for CO2/N2Separate, in the test strip of 30 DEG C He 0.06MPa
Under part, CO2Infiltration coefficient be 280barrer, CO2/N2Ideal selectivity be 82.34.
Embodiment two:
(1) gel film is prepared:
By 15 parts of polyether block amides (wherein the mass ratio of poly(ethylene oxide) segment and Nylon 6 Chains section is 2: 3), 70 parts of quality
At 85 DEG C, it is laid in polyfluortetraethylene plate after mix homogeneously than n-propanol/water mixed solvent and the 15 parts of ethylene glycol mono-ethers being 7: 3
On, dry out solvent, prepare gel film.
(2) film top layer cross-links again:
Above-mentioned made gel film is immersed in 3 parts of isophorone diisocyanate and 97 parts of hexane solutions, controls Immersion time
It is 1 hour, carries out gel film surface cross linking.
(3) post processing:
Gel film after crosslinking is dried 24 hours in atmosphere, then proceeds in vacuum drying oven, process 24 hours at 30 DEG C,
Obtain sandwich structure polyether block amide gel film.
Above-mentioned sandwich structure polyether block amide gel film is used for CO2/N2Separate, in the test strip of 30 DEG C He 0.06MPa
Under part, CO2Infiltration coefficient be 224barrer, CO2/N2Ideal selectivity be 76.02.
Embodiment three:
(1) gel film is prepared:
By 15 parts of polyether block amides (wherein the mass ratio of poly(ethylene oxide) segment and Nylon 6 Chains section is 3: 2), 75 parts of quality
At 80 DEG C, it is laid in polyfluortetraethylene plate after mix homogeneously than n-butanol/water mixed solvent and the 10 parts of propandiol butyl ethers being 8: 2
On, dry out solvent, prepare gel film.
(2) film top layer cross-links again:
Being immersed in by above-mentioned made gel film in 2 parts of toluene di-isocyanate(TDI)s and 98 parts of hexane solutions, controlling Immersion time is 2
Hour, carry out gel film surface cross linking.
(3) post processing:
Gel film after crosslinking is dried 24 hours in atmosphere, then proceeds in vacuum drying oven, process 24 hours at 30 DEG C,
Obtain sandwich structure polyether block amide gel film.
Above-mentioned sandwich structure polyether block amide gel film is used for CO2/N2Separate, in the test strip of 30 DEG C He 0.06MPa
Under part, CO2Infiltration coefficient be 187barrer, CO2/N2Ideal selectivity be 55.96.
Embodiment four:
(1) gel film is prepared:
By 20 parts of polyether block amides (wherein the mass ratio of poly(ethylene oxide) segment and Nylon 6 Chains section is 3: 2), 70 parts of quality
At 90 DEG C, it is laid in politef after mix homogeneously than n-propanol/water mixed solvent and the 10 parts of butyl being 7: 3
On plate, dry out solvent, prepare gel film.
(2) film top layer cross-links again:
Being immersed in by above-mentioned made gel film in 5 parts of toluene di-isocyanate(TDI)s and 95 parts of hexane solutions, controlling Immersion time is 5
Hour, carry out gel film surface cross linking.
(3) post processing:
Gel film after crosslinking is dried 24 hours in atmosphere, then proceeds in vacuum drying oven, process 24 hours at 30 DEG C,
Obtain sandwich structure polyether block amide gel film.
Above-mentioned sandwich structure polyether block amide gel film is used for CO2/N2Separate, in the test strip of 30 DEG C He 0.06MPa
Under part, CO2Infiltration coefficient be 153barrer, CO2/N2Ideal selectivity be 61.38.
Embodiment five:
(1) gel film is prepared:
By 10 parts of polyether block amides (wherein the mass ratio of poly(ethylene oxide) segment and Nylon 6 Chains section is 2: 3), 80 parts of formic acid
It is laid on polyfluortetraethylene plate after mix homogeneously at 75 DEG C with 10 parts of ethylene glycol phenyl ethers, dry out solvent, prepares gel film.
(2) film top layer cross-links again:
Above-mentioned made gel film is immersed in 4 parts of hexamethylene diisocyanates and 96 parts of hexane solutions, controls Immersion time
It is 3 hours, carries out gel film surface cross linking.
(3) post processing:
Gel film after crosslinking is dried 24 hours in atmosphere, then proceeds in vacuum drying oven, process 24 hours at 30 DEG C,
Obtain sandwich structure polyether block amide gel film.
Above-mentioned sandwich structure polyether block amide gel film is used for CO2/N2Separate, in the test strip of 30 DEG C He 0.06MPa
Under part, CO2Infiltration coefficient be 208barrer, CO2/N2Ideal selectivity be 84.17.
Embodiment six:
(1) gel film is prepared:
By 10 parts of polyether block amides (wherein the mass ratio of poly(ethylene oxide) segment and Nylon 6 Chains section is 2: 3), 75 parts of quality
At 85 DEG C, it is laid in polyfluortetraethylene plate after mix homogeneously than n-butanol/water mixed solvent and the 15 parts of propandiol butyl ethers being 8: 2
On, dry out solvent, prepare gel film.
(2) film top layer cross-links again:
Above-mentioned made gel film is immersed in 3 parts of methyl diphenylene diisocyanates and 97 parts of hexane solutions, when controlling submergence
Between be 12 hours, carry out gel film surface cross linking.
(3) post processing:
Gel film after crosslinking is dried 24 hours in atmosphere, then proceeds in vacuum drying oven, process 24 hours at 30 DEG C,
Obtain sandwich structure polyether block amide gel film.
Above-mentioned sandwich structure polyether block amide gel film is used for CO2/N2Separate, in the test strip of 30 DEG C He 0.06MPa
Under part, CO2Infiltration coefficient be 113barrer, CO2/N2Ideal selectivity be 92.56.
The description of above-described embodiment should be considered explanation, it is easy to is understood by, can be without departing from illustrating the most in detail in the claims
The present invention in the case of use many changes and the combination of feature described above, this kind of change has been not to be regarded as a departure from this
Bright spirit and scope, and all such change be included in the range of claims below.
Claims (6)
1. the preparation method of a sandwich structure polyether block amide gel film, it is characterised in that comprise the steps:
A is flat after polyether block amide 10-20 part, solvent 70-80 part and functional vector 10-20 part uniformly being mixed at 70-90 DEG C
It is layered on polyfluortetraethylene plate, dry out solvent, prepares gel film；
1-5 part cross-linking agent is dissolved in 95-99 part normal hexane formation cross-linking agent solution by B, above-mentioned gel film is immersed in this cross-linking agent molten
In liquid 0.5～12 hour, carry out gel film surface cross linking；
Gel film after crosslinking is dried 24 hours by C in atmosphere, then proceeds in vacuum drying oven, processes 24 hours at 30 DEG C,
Obtain sandwich structure polyether block amide gel film.
The preparation method of sandwich structure polyether block amide gel film the most according to claim 1, it is characterised in that described function
Property carrier is ethylene glycol phenyl ether, ethylene glycol mono-ether, propandiol butyl ether or butyl.
3. according to the preparation method of sandwich structure polyether block amide gel film described in claim 1-2, it is characterised in that described friendship
Connection agent is methyl diphenylene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate or toluene diisocynate
Ester.
4. according to the preparation method of sandwich structure polyether block amide gel film described in claim 1-3, it is characterised in that described poly-
Ether block amides is made up of polyether segment and polyamide segment, and wherein polyether segment is poly(ethylene oxide), and polyamide segment is nylon
6, and both mass ratioes are 2: 3 or 3: 2.
5. according to the preparation method of sandwich structure polyether block amide gel film described in claim 1-4, it is characterised in that described molten
Agent be formic acid, mass ratio be the n-propanol/water mixed solvent of 7: 3 or n-butanol/water mixed solvent that mass ratio is 8: 2.
6. a sandwich structure polyether block amide gel film, it is characterised in that described gel film has three-decker, upper layer
For cross-linked layer, thickness is between 2-10 micron；Centre is gel layer, and thickness is between 60-90 micron.
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| CN201410784259.XA CN105879726B (en) | 2014-12-16 | 2014-12-16 | A kind of sandwich structure polyether block amide gel mould and preparation method thereof |
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| CN201410784259.XA CN105879726B (en) | 2014-12-16 | 2014-12-16 | A kind of sandwich structure polyether block amide gel mould and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111032199A (en) * | 2017-08-30 | 2020-04-17 | 沙特阿拉伯石油公司 | Crosslinked polymer blend membranes for gas separation |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102137709A (en) * | 2008-06-25 | 2011-07-27 | 亥姆霍兹中心吉斯达赫特材料及海岸研究中心有限责任公司 | Polymer membrane |
| CN103665832A (en) * | 2013-11-08 | 2014-03-26 | 江南大学 | Polyether block amide/polyion liquid semi-interpenetrating polymer network film and photocuring preparation method thereof |
-
2014
- 2014-12-16 CN CN201410784259.XA patent/CN105879726B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102137709A (en) * | 2008-06-25 | 2011-07-27 | 亥姆霍兹中心吉斯达赫特材料及海岸研究中心有限责任公司 | Polymer membrane |
| CN103665832A (en) * | 2013-11-08 | 2014-03-26 | 江南大学 | Polyether block amide/polyion liquid semi-interpenetrating polymer network film and photocuring preparation method thereof |
Non-Patent Citations (4)
| Title |
|---|
| K.SUNITHA ET AL: "Separation of NMP/water mixtures by nanocomposite PEBA membrane: Part I. Membrane synthesis, characterization and pervaporation performance", 《DESALINATION》 * |
| S.SRIDHAR ET AL: "Development of crosslinked poy(ether-block-amide) membrane for CO2/CH4 separation", 《COLLOIDS AND SURFACE A : PHYSICOCHEM.ENG.ASPECTS》 * |
| 张影: "PEBA / EPH 热可逆凝胶膜的制备及其气体分离性能", 《应用化工》 * |
| 贾红兵等: "《高分子材料》", 30 November 2009 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111032199A (en) * | 2017-08-30 | 2020-04-17 | 沙特阿拉伯石油公司 | Crosslinked polymer blend membranes for gas separation |
| CN111032199B (en) * | 2017-08-30 | 2021-08-13 | 沙特阿拉伯石油公司 | Crosslinked polymer blend membranes for gas separation |
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