CN104524995A - Stable-structure separation film and preparation method thereof - Google Patents
Stable-structure separation film and preparation method thereof Download PDFInfo
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- CN104524995A CN104524995A CN201410821808.6A CN201410821808A CN104524995A CN 104524995 A CN104524995 A CN 104524995A CN 201410821808 A CN201410821808 A CN 201410821808A CN 104524995 A CN104524995 A CN 104524995A
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Abstract
The invention relates to a stable-structure separation film and a preparation method thereof and belongs to the technical field of membrane separation. The stable-structure separation film is prepared by treating a polymer film at the temperature of 150 to 500 DEG C in an oxidizing atmosphere for at least 0.1 hour, wherein the polymer refers to a thermoplastic polymer with a linear molecular structure. The invention provides a stable-structure separation film with thermal rigidity, and the separation film is stable in chemical performance and excellent in gas separation performance and has wide application prospects in the field of gas and liquid separation.
Description
Technical field
The present invention relates to a kind of Stable structure diffusion barrier and preparation method thereof, particularly a kind of have polymer separation film of thermic rigidity Stable structure and preparation method thereof, belongs to technical field of membrane separation.
Background technology
UF membrane is the selective penetrated property according to film, diffusion barrier is made wall, under the motive force of pressure differential, concentration difference or potential difference, different through the speed of film by means of component each in fluid mixture, make it the enrichment respectively in the both sides of film, with the object reaching separation, refine, concentrate and recycle.Energy-efficient as one, the eco-friendly new separation technology of UF membrane is one of guardian technique solving the increasingly serious significant problem such as the energy, resources and environment.At present, membrane technology is widely used in desalinization, food concentrates, prepared by oxygen-enriched air, prepared by the enrichment of carbon dioxide and recovery, gas and separation of hydrocarbons, pure water and ultra-pure water, the aspect such as environmental protection and sewage disposal.
Up to the present, the gas separation membrane material of commercial applications mainly polymeric film material.But, these polymeric film material or gas-selectively is higher, but gas permeability is very low, as polysulfones, polyether sulfone, polyimides or polyetherimides membrane material; Gas permeability is high and selective lower, as silicone rubber kinds membrane material, particularly polymer film also exist the poor problem of heat resistance, solvent resistance.Along with market is to the raising day by day of gas separation membrane performance requirement (high osmosis and high selectivity, high temperature resistant, solvent resistant), these defects of polymer film show especially out gradually, are difficult to meet growing market demands.Heat-resisting, the solvent-proof ability how improving polymer film has become the focus that technical field of membrane is paid close attention to.
The effective ways of heat-resisting, the solvent resistant characteristic of polymer film are considered to improve by the structure polymer that to be cross-linked the polymer conversion with linear structure be three-dimensional-structure.Chemical crosslinking is method conventional at present.In recent years, heat cross-linking method attracts attention, people (the J.Membr.Sci. such as Nurul Islam, 2005,261:17-26) sulfonated polyimide is adopted to prepare polymer film, and be heated to 450 DEG C in a nitrogen atmosphere and carry out pyrolysis, the low temperature pyrogenation film obtained maintains the good pliability of polymer film, improves its heat endurance and solvent resistance.The people such as Park (Science, 2007,318:254-258) carry out irreversible thermic molecular rearrangement reaction the polyimide polymer film containing-OH and-SH group at the temperature of 350-450 DEG C, also improve the heat endurance of polymer film.But the reaction of this thermal rearrangement has certain limitation, must be containing can the polymer of induced reactions group occurring in molecular structure, and the heat of this polymer and chemical stability poor, the condition of rearrangement reaction is harsher.In addition, containing can the synthesis technique more complicated of polymer of induced reactions group, production cost be higher, is unfavorable for its industrial applications.
Summary of the invention
The deficiencies such as the present invention aims to provide that a kind of steady chemical structure, separating property are excellent, the preparation method of the polymer separation film (being called for short thermic rigidity diffusion barrier) with thermic rigidity Stable structure, and existing polymer separation film material separating property is limited, temperature tolerance is poor to solve and to make up, easy plasticizing, structural instability in use procedure, service life are short.The present invention adopts the polymer with linear molecule structure to be precursor power polymer film, through oxidizing atmosphere thermic rigid treatment, makes the separation membrane material obtained have stable rigid molecular structure.
A kind of Stable structure diffusion barrier, is by polymer film in an oxidizing atmosphere, processes at least 0.1h gained in 150 ~ 500 DEG C,
Wherein, described polymer is the thermoplastic polymer with linearity molecular structure.
" polymer film " of the present invention refers to the film be made up of polymer, and described polymer is the thermoplastic polymer with linearity molecular structure, and it business can be buied or obtain by method disclosed in prior art.The preferred described polymer of the present invention is one or more in polyacrylonitrile, polysulfones, polyether sulfone, PEI, polyimides, polyethersulfone ketone, PAEK, polyethers nitrile ketone, polyether sulphone, phenolic resins, benzoxazine colophony, cyanate ester resin base polymer.
It is the polymer film forming component that polymer film of the present invention is preferably by one or more in polyacrylonitrile, polysulfones, polyether sulfone, PEI, polyimides, polyethersulfone ketone, PAEK, polyether sulphone, polyethers nitrile ketone, phenolic resins, benzoxazine colophony, cyanate ester resin base polymer.
The thickness of the preferred described polymer film of the present invention is 10 ~ 100 μm.
Oxidizing atmosphere of the present invention, preferably by providing containing oxygen gas mixture, to be describedly made up of the oxidizing gas of 5 ~ 50% (V/V) and surplus carrier gas containing oxygen gas mixture; Preferential oxidation gas is one or more in oxygen, air or ozone; Preferred described carrier gas is inert gas, as nitrogen, argon gas etc.
The flow velocity of the preferred described oxidizing gas of the present invention is 5 ~ 500mL/min.
The preferred described Stable structure diffusion barrier of the present invention is by polymer film in an oxidizing atmosphere, in 150 ~ 500 DEG C of process 0.1 ~ 24h gained, and heating rate 1 ~ 20 DEG C/min.
Another object of the present invention is to provide the preparation method of above-mentioned diffusion barrier.
Prepare a method for described diffusion barrier, by polymer film in an oxidizing atmosphere, process at least 0.1h in 150 ~ 500 DEG C
Wherein, described polymer is the thermoplastic polymer with linearity molecular structure.
The preferred described polymer of the present invention is one or more in polyacrylonitrile, polysulfones, polyether sulfone, PEI, polyimides, polyethersulfone ketone, PAEK, polyether sulphone, polyethers nitrile ketone, phenolic resins, benzoxazine colophony, cyanate ester resin base polymer.
The thickness of the preferred described polymer film of the present invention is 10 ~ 100 μm.
Oxidizing atmosphere of the present invention, preferably by providing containing oxygen gas mixture, to be describedly made up of the oxidizing gas of 5 ~ 50% (V/V) and surplus carrier gas containing oxygen gas mixture; Preferential oxidation gas is one or more in oxygen, air or ozone; Preferred described carrier gas is inert gas, as nitrogen, argon gas etc.
The flow velocity of the preferred described oxidizing gas of the present invention is 5 ~ 500mL/min.
The preparation method of the preferred described diffusion barrier of the present invention, comprises the steps: by polymer film in an oxidizing atmosphere, in 150 ~ 500 DEG C of process 0.1 ~ 24h gained, and heating rate 1 ~ 20 DEG C/min.
Beneficial effect of the present invention is:
The present invention proposes a kind of preparation method with the diffusion barrier of thermic rigidity Stable structure, what this method avoids expensive and hot and poor chemical stability can the use of polymer of thermal rearrangement, technique is simple, with low cost, applied widely, resulting materials stable chemical performance, gas separating property are excellent, will have broad application prospects in gas, fluid separation applications field.
Accompanying drawing explanation
Fig. 1 is the photo of the undressed polyacrylonitrile film of embodiment 1;
Fig. 2 is the photo of the thermic rigidity diffusion barrier after embodiment 1 processes;
Fig. 3 is the photo of the thermic rigidity diffusion barrier after embodiment 1 processes, and as can be seen from Figure 3, prepared Stable structure diffusion barrier not only has good rigidity, has good pliability and mechanical strength simultaneously.
Detailed description of the invention
Following non-limiting example can make the present invention of those of ordinary skill in the art's comprehend, but does not limit the present invention in any way.
Test method described in following embodiment, if no special instructions, is conventional method; Described reagent and material, if no special instructions, all can obtain from commercial channels.
Concentration in gaseous mixture involved by lower embodiment is volumetric concentration % (V/V).
Embodiment 1
Polyacrylonitrile film is placed in atmosphere furnace, repeatedly inflate/degassed 3 times after, gaseous mixture (by forming of 5% ozone and 95% nitrogen) is passed into the flow velocity of 500mL/min in stove, furnace temperature is warmed up to 350 DEG C with the speed of 3 DEG C/min, and maintain 1 hour at such a temperature, obtain thermic rigidity diffusion barrier.
Embodiment 2
According to the method described in embodiment 1, polyacrylonitrile film is replaced with polyimide film or PS membrane, pass into gaseous mixture (by forming of 15% ozone and 85% nitrogen), flow velocity is 50mL/min, furnace temperature is warmed up to 300 DEG C with the speed of 5 DEG C/min, and maintain 0.1 hour at such a temperature, obtain thermic rigidity diffusion barrier.
Embodiment 3
According to the method described in embodiment 1, polyacrylonitrile film is replaced with polyamide acid film, polyethersulfone ketone film or PAEK film, pass into gaseous mixture (by forming of 5% ozone and 95% nitrogen), flow velocity is 250mL/min, furnace temperature is warmed up to 150 DEG C with the speed of 1 DEG C/min, and maintain 24 hours at such a temperature, obtain thermic rigidity diffusion barrier.
Embodiment 4
According to the method described in embodiment 1, pass into gaseous mixture (by forming of 5% oxygen and 95% argon gas), flow velocity is 50mL/min, and furnace temperature is warmed up to 450 DEG C with the speed of 10 DEG C/min, and maintain 2 hours at such a temperature, obtain thermic rigidity diffusion barrier.
Embodiment 5
According to the method described in embodiment 1, polyacrylonitrile film is replaced with polyamide acid film, polyethersulfone ketone film or PAEK film, pass into gaseous mixture (by forming of 50% oxygen and 50% argon gas), flow velocity is 10mL/min, furnace temperature is warmed up to 250 DEG C with the speed of 2 DEG C/min, and maintain 12 hours at such a temperature, obtain thermic rigidity diffusion barrier.
Embodiment 6
According to the method described in embodiment 1, polyacrylonitrile film is replaced with polyimide film or PS membrane, pass into gaseous mixture (by forming of 15% oxygen and 85% nitrogen), flow velocity is 150mL/min, furnace temperature is warmed up to 350 DEG C with the speed of 3 DEG C/min, and maintain 6 hours at such a temperature, obtain thermic rigidity diffusion barrier.
Embodiment 7
According to the method described in embodiment 1, pass into gaseous mixture (by forming of 5% air and 95% argon gas), flow velocity is 250mL/min, furnace temperature is warmed up to 450 DEG C with the speed of 10 DEG C/min, and maintains 2 hours at such a temperature, obtains thermic rigidity diffusion barrier.
Embodiment 8
According to the method described in embodiment 1, polyacrylonitrile film is replaced with polyamide acid film, polyethersulfone ketone film or PAEK film, pass into gaseous mixture (by forming of 50% air and 50% nitrogen), flow velocity is 100mL/min, furnace temperature is warmed up to 500 DEG C with the speed of 2 DEG C/min, and maintain 18 hours at such a temperature, obtain thermic rigidity diffusion barrier.
Embodiment 9
According to the method described in embodiment 1, polyacrylonitrile film is replaced with polyimide film or PS membrane, pass into gaseous mixture (by forming of 15% air and 85% nitrogen), flow velocity is 350mL/min, furnace temperature is warmed up to 450 DEG C with the speed of 3 DEG C/min, and maintain 9 hours at such a temperature, obtain thermic rigidity diffusion barrier.
The thermic rigidity diffusion barrier of above-described embodiment 1 ~ 9 gained and former film are placed in multiple organic solvent respectively, and its solubility property is as shown in table 1:
Table 1
The thermic rigidity diffusion barrier of above-described embodiment 1 ~ 9 gained and former film are placed in respectively diluted acid and diluted alkaline 24 hours, its stability is as shown in table 2:
Table 2
In embodiment 1 ~ 9, the gas separaion character of the listed former film of polymer is as shown in table 3:
Table 3
1Barrer＝1×10
-10cm
3(STP)·cm/(cm
2·s·cm Hg)
The gas separaion character of the thermic rigidity diffusion barrier of embodiment 1 ~ 9 gained is as shown in table 4:
Table 4
1Barrer＝1×10
-10cm
3(STP)·cm/(cm
2·s·cm Hg)
Claims (6)
1. a Stable structure diffusion barrier is by polymer film in an oxidizing atmosphere, processes at least 0.1h gained in 150 ~ 500 DEG C,
Wherein, described polymer is the thermoplastic polymer with linearity molecular structure.
2. diffusion barrier according to claim 1, is characterized in that: described polymer is one or more in polyacrylonitrile, polysulfones, polyether sulfone, PEI, polyimides, polyethersulfone ketone, PAEK, polyether sulphone, polyethers eyeball ketone, phenolic resins, Bing oxazine resin, cyanate ester resin base polymer.
3. diffusion barrier according to claim 1, is characterized in that: oxidizing atmosphere, by providing containing oxygen gas mixture, to be describedly made up of the oxidizing gas of 5 ~ 50% (V/V) and surplus carrier gas containing oxygen gas mixture.
4. diffusion barrier according to claim 1, is characterized in that: described oxidizing gas is oxygen, air or ozone.
5. diffusion barrier according to claim 1, is characterized in that: be by polymer film in an oxidizing atmosphere, in 150 ~ 500 DEG C of process 0.1 ~ 24h gained, and heating rate 1 ~ 20 DEG C/min.
6. prepare a method for diffusion barrier described in claim 1, it is characterized in that: by polymer film in an oxidizing atmosphere, process at least 0.1h in 150 ~ 500 DEG C,
Wherein, described polymer is the thermoplastic polymer with linearity molecular structure.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105921037A (en) * | 2016-06-22 | 2016-09-07 | 辽宁科技大学 | Method for preparing porous gas separation membrane material with thermally-induced rigid structure |
| CN107362702A (en) * | 2017-09-11 | 2017-11-21 | 大连理工大学 | It is a kind of that there is heat-resisting and mixed substrate membrane containing nano-grade molecular sieve of solvent resistance and its preparation method and application |
| CN108034059A (en) * | 2017-12-13 | 2018-05-15 | 大连理工大学 | A kind of method for judging thermoplastic polymer heat cross-linking processing range |
| CN108499376A (en) * | 2018-03-22 | 2018-09-07 | 南京工业大学 | A kind of hydrophilic modifying polyacrylonitrile-based membrane, preparation method and application |
| CN110711505A (en) * | 2019-09-30 | 2020-01-21 | 大连理工大学 | Preparation method of high-permeability heat cross-linking membrane |
| CN115725076A (en) * | 2021-09-01 | 2023-03-03 | 中国科学院大连化学物理研究所 | Block copolymer, preparation method thereof and application thereof in gas separation membrane |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5152894A (en) * | 1989-02-02 | 1992-10-06 | Hoechst Aktiengesellschaft | Semipermeable membrane made from a homogeneously miscible polymer blend |
| US20050029186A1 (en) * | 2000-11-13 | 2005-02-10 | Heinz-Joachim Muller | Modified membranes |
| CN103338845A (en) * | 2011-06-20 | 2013-10-02 | Lg化学株式会社 | Reverse osmosis membrane having superior salt rejection and permeate flow, and method for manufacturing same |
| CN103816816A (en) * | 2014-02-28 | 2014-05-28 | 中国科学院长春应用化学研究所 | A polymer film material and a preparation method thereof |
-
2014
- 2014-12-23 CN CN201410821808.6A patent/CN104524995B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5152894A (en) * | 1989-02-02 | 1992-10-06 | Hoechst Aktiengesellschaft | Semipermeable membrane made from a homogeneously miscible polymer blend |
| US20050029186A1 (en) * | 2000-11-13 | 2005-02-10 | Heinz-Joachim Muller | Modified membranes |
| CN103338845A (en) * | 2011-06-20 | 2013-10-02 | Lg化学株式会社 | Reverse osmosis membrane having superior salt rejection and permeate flow, and method for manufacturing same |
| CN103816816A (en) * | 2014-02-28 | 2014-05-28 | 中国科学院长春应用化学研究所 | A polymer film material and a preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| HO BUM PARK ET AL.: "Polymers with Cavities Tuned for Fast Selective Transport of Small Molecules and Ions", 《SCIENCE》, vol. 318, 12 October 2007 (2007-10-12), pages 254 - 258 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105921037A (en) * | 2016-06-22 | 2016-09-07 | 辽宁科技大学 | Method for preparing porous gas separation membrane material with thermally-induced rigid structure |
| CN107362702A (en) * | 2017-09-11 | 2017-11-21 | 大连理工大学 | It is a kind of that there is heat-resisting and mixed substrate membrane containing nano-grade molecular sieve of solvent resistance and its preparation method and application |
| CN108034059A (en) * | 2017-12-13 | 2018-05-15 | 大连理工大学 | A kind of method for judging thermoplastic polymer heat cross-linking processing range |
| CN108034059B (en) * | 2017-12-13 | 2020-09-29 | 大连理工大学 | Method for judging thermal crosslinking process range of thermoplastic polymer |
| CN108499376A (en) * | 2018-03-22 | 2018-09-07 | 南京工业大学 | A kind of hydrophilic modifying polyacrylonitrile-based membrane, preparation method and application |
| CN110711505A (en) * | 2019-09-30 | 2020-01-21 | 大连理工大学 | Preparation method of high-permeability heat cross-linking membrane |
| CN115725076A (en) * | 2021-09-01 | 2023-03-03 | 中国科学院大连化学物理研究所 | Block copolymer, preparation method thereof and application thereof in gas separation membrane |
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