CN104524995B - A kind of Stable structure separation film and preparation method thereof - Google Patents
A kind of Stable structure separation film and preparation method thereof Download PDFInfo
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- CN104524995B CN104524995B CN201410821808.6A CN201410821808A CN104524995B CN 104524995 B CN104524995 B CN 104524995B CN 201410821808 A CN201410821808 A CN 201410821808A CN 104524995 B CN104524995 B CN 104524995B
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Abstract
The present invention relates to a kind of Stable structure separation film and preparation method thereof, belong to technical field of membrane separation.A kind of Stable structure separation film, is by polymeric film in an oxidizing atmosphere, processes at least 0.1h gained in 150～500 DEG C, and wherein, described polymer is the thermoplastic polymer with linearity molecular structure.The present invention proposes a kind of separation film with thermic rigidity Stable structure, and this separation film stable chemical performance, gas separating property are excellent, will have broad application prospects at gas, liquid separation field.
Description
Technical field
The present invention relates to a kind of Stable structure separation film and preparation method thereof, particularly to one, there is thermic rigidity stable state
Polymer separation film of structure and preparation method thereof, belongs to technical field of membrane separation.
Background technology
Membrance separation is based on the selective penetrated property of film, and separation film is made wall, in pressure differential, concentration difference or potential difference
Under motive force, different through the speed of film by means of component each in fluid mixture, it is allowed to be enriched with respectively in the both sides of film, to reach point
From, the purpose that refines, concentrate and recycle.Membrance separation, as a kind of new separation technology energy-efficient, eco-friendly, is
Solve one of guardian techniques of significant problem such as the increasingly serious energy, resource and environment.At present, membrane technology is widely used in
Desalinization, food concentrate, prepared by oxygen-enriched air, the enrichment of carbon dioxide and recovery, gas and separation of hydrocarbons, pure water and
Prepared by ultra-pure water, the aspect such as environmental conservation and sewage disposal.
Up to the present, the gas separation membrane material having been commercialized application is mainly polymeric film material.But, these gather
Compound film material or gas-selectively is higher, but gas permeability is the lowest, such as polysulfones, polyether sulfone, polyimides or polyethers
Acid imide membrane material；Gas permeability is high and selectivity is relatively low, as silicone rubber kinds membrane material, particularly polymeric film are deposited
In the problem that thermostability, solvent resistance are poor.Along with market is to gas separation membrane performance requirement (high osmosis and high selection
Property, high temperature resistant, solvent resistant) raising day by day, these defects of polymeric film gradually show especially out, it is difficult to meet growing
Market demands.The ability heat-resisting, solvent-proof how improving polymeric film has become as the focus that technical field of membrane is paid close attention to.
Being cross-linked the polymer that polymer conversion is three-dimensional-structure with linear structure by structure is considered as to improve
Heat-resisting, the effective ways of solvent resistant characteristic of polymeric film.Chemical crosslinking is the most conventional method.In recent years, heat cross-linking method
Attracting attention, Nurul Islam et al. (J.Membr.Sci., 2005,261:17-26) uses sulfonated polyimide
Preparing polymeric film, and be heated to 450 DEG C in a nitrogen atmosphere and be pyrolyzed, the low temperature pyrogenation film obtained maintains polymeric film
Good pliability, improves its heat stability and solvent resistance.Park et al. (Science, 2007,318:254-258)
Polyimide polymer film containing-OH and-SH group carries out irreversible thermic molecular rearrangement at a temperature of 350-450 DEG C
Reaction, also improves the heat stability of polymeric film.But the reaction of this thermal rearrangement has certain limitation, it is necessary to be molecule knot
Containing can the polymer of induced reactions group occurring in structure, and the thermally and chemically less stable of this polymer, heavily
The condition of row's reaction is harsher.Additionally, containing can the synthesis technique of polymer of induced reactions group more complicated, produce into
This is higher, is unfavorable for its industrial applications.
Summary of the invention
It is desirable to provide a kind of steady chemical structure, separating property are excellent, have the poly-of thermic rigidity Stable structure
The preparation method of compound separation film (being called for short thermic rigidity separation film), to solve and to make up existing polymer separation film material separation
Limited performance, temperature tolerance be poor, easily plasticizing, use during the deficiencies such as structural instability, service life is short.The present invention uses to be had
The polymer of linear molecule structure is that presoma prepares polymeric film, through oxidizing atmosphere thermic rigid treatment so as to get point
From membrane material, there is stable rigid molecular structure.
A kind of Stable structure separation film, is by polymeric film in an oxidizing atmosphere, processes at least in 150～500 DEG C
0.1h gained,
Wherein, described polymer is the thermoplastic polymer with linearity molecular structure.
" polymeric film " of the present invention refers to that the film being made up of polymer, described polymer are to have linearity molecular structure
Thermoplastic polymer, it is commercially available or method as disclosed in prior art prepares.The preferred described polymer of the present invention is poly-
Acrylonitrile, polysulfones, polyether sulfone, Polyetherimide, polyimides, polyethersulfone ketone, PAEK, polyethers nitrile ketone, polyether sulphone, phenol
One or more in urea formaldehyde, benzoxazine resins, cyanate ester resin base polymer.
Polymeric film of the present invention is preferably by polyacrylonitrile, polysulfones, polyether sulfone, Polyetherimide, polyimides, gathers
In ether sulfone ketone, PAEK, polyether sulphone, polyethers nitrile ketone, phenolic resin, benzoxazine resins, cyanate ester resin base polymer
One or more be constitute component polymeric film.
The thickness of the preferred described polymeric film of the present invention is 10～100 μm.
Oxidizing atmosphere of the present invention is preferably provided by containing oxygen gas mixture, described containing oxygen gas mixture by 5～50% (V/V)
Oxidizing gas and surplus carrier gas composition；Preferential oxidation gas is one or more in oxygen, air or ozone；Preferably
Described carrier gas is noble gas, such as nitrogen, argon etc..
The flow velocity of the preferred described oxidizing gas of the present invention is 5～500mL/min.
The preferred described Stable structure separation film of the present invention is by polymeric film in an oxidizing atmosphere, at 150～500 DEG C
Reason 0.1～24h gained, heating rate 1～20 DEG C/min.
It is a further object of the present invention to provide the preparation method of above-mentioned separation film.
A kind of method preparing described separation film, by polymeric film in an oxidizing atmosphere, processes extremely in 150～500 DEG C
Few 0.1h
Wherein, described polymer is the thermoplastic polymer with linearity molecular structure.
The preferred described polymer of the present invention is polyacrylonitrile, polysulfones, polyether sulfone, Polyetherimide, polyimides, polyether sulfone
In ketone, PAEK, polyether sulphone, polyethers nitrile ketone, phenolic resin, benzoxazine resins, cyanate ester resin base polymer one
Plant or multiple.
The thickness of the preferred described polymeric film of the present invention is 10～100 μm.
Oxidizing atmosphere of the present invention is preferably provided by containing oxygen gas mixture, described containing oxygen gas mixture by 5～50% (V/V)
Oxidizing gas and surplus carrier gas composition；Preferential oxidation gas is one or more in oxygen, air or ozone；Preferably
Described carrier gas is noble gas, such as nitrogen, argon 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 separation film of the present invention, comprises the steps: by polymeric film in an oxidizing atmosphere,
0.1～24h gained, heating rate 1～20 DEG C/min is processed in 150～500 DEG C.
The invention have the benefit that
The present invention proposes a kind of preparation method separating film with thermic rigidity Stable structure, this method avoids price
Expensive and thermally and chemically poor stability can the use of polymer of thermal rearrangement, technique is simple, with low cost, the scope of application
Extensively, resulting materials stable chemical performance, gas separating property are excellent, will have wide application at gas, liquid separation field
Prospect.
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 separation film after embodiment 1 processes；
Fig. 3 is the photo of the thermic rigidity separation film after embodiment 1 processes, from figure 3, it can be seen that prepared stable state knot
Structure separation film not only has good rigidity, has good pliability and mechanical strength simultaneously.
Detailed description of the invention
Following non-limiting example can make those of ordinary skill in the art that the present invention be more fully understood, but not with
Any mode limits the present invention.
Test method described in following embodiment, if no special instructions, is conventional method；Described reagent and material, as
Without specified otherwise, the most commercially obtain.
Concentration in gaseous mixture involved by lower embodiment is volumetric concentration % (V/V).
Embodiment 1
Being placed in atmosphere furnace by polyacrylonitrile film, after repeatedly inflating/deaerate 3 times, in stove, the flow velocity with 500mL/min leads to
Entering gaseous mixture (by forming of 5% ozone and 95% nitrogen), furnace temperature is warmed up to 350 DEG C with the speed of 3 DEG C/min, and in this temperature
Lower maintenance 1 hour, obtains thermic rigidity separation film.
Embodiment 2
According to the method described in embodiment 1, polyacrylonitrile film is replaced with polyimide film or polysulfone membrane, is passed through mixing
Gas (by forming of 15% ozone and 85% nitrogen), flow velocity is 50mL/min, and 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 separation film.
Embodiment 3
According to the method described in embodiment 1, polyacrylonitrile film is replaced with polyamide acid film, polyethersulfone ketone film or poly-virtue
Ether ketone film, is passed through gaseous mixture (by forming of 5% ozone and 95% nitrogen), and flow velocity is 250mL/min, and furnace temperature is with 1 DEG C/min's
Speed is warmed up to 150 DEG C, and maintains 24 hours at such a temperature, obtains thermic rigidity separation film.
Embodiment 4
According to the method described in embodiment 1, being passed through gaseous mixture (by forming of 5% oxygen and 95% argon), flow velocity is
50mL/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 and divides
From film.
Embodiment 5
According to the method described in embodiment 1, polyacrylonitrile film is replaced with polyamide acid film, polyethersulfone ketone film or poly-virtue
Ether ketone film, is passed through gaseous mixture (by forming of 50% oxygen and 50% argon), and flow velocity is 10mL/min, and furnace temperature is with 2 DEG C/min's
Speed is warmed up to 250 DEG C, and maintains 12 hours at such a temperature, obtains thermic rigidity separation film.
Embodiment 6
According to the method described in embodiment 1, polyacrylonitrile film is replaced with polyimide film or polysulfone membrane, is passed through mixing
Gas (by forming of 15% oxygen and 85% nitrogen), flow velocity is 150mL/min, and furnace temperature is warmed up to 350 with the speed of 3 DEG C/min
DEG C, and maintain 6 hours at such a temperature, obtain thermic rigidity separation film.
Embodiment 7
According to the method described in embodiment 1, it is passed through gaseous mixture (by forming of 5% air and 95% argon), 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
Separate film.
Embodiment 8
According to the method described in embodiment 1, polyacrylonitrile film is replaced with polyamide acid film, polyethersulfone ketone film or poly-virtue
Ether ketone film, is passed through gaseous mixture (by forming of 50% air and 50% nitrogen), and flow velocity is 100mL/min, and furnace temperature is with 2 DEG C/min's
Speed is warmed up to 500 DEG C, and maintains 18 hours at such a temperature, obtains thermic rigidity separation film.
Embodiment 9
According to the method described in embodiment 1, polyacrylonitrile film is replaced with polyimide film or polysulfone membrane, is passed through mixing
Gas (by forming of 15% air and 85% nitrogen), flow velocity is 350mL/min, and furnace temperature is warmed up to 450 with the speed of 3 DEG C/min
DEG C, and maintain 9 hours at such a temperature, obtain thermic rigidity separation film.
Thermic rigidity separation film and the former film of above-described embodiment 1～9 gained being respectively placed in multiple organic solvent, it is molten
Solution performance is as shown in table 1:
Table 1
The thermic rigidity separation film of above-described embodiment 1～9 gained and former film are respectively placed in diluted acid and diluted alkaline 24 hours,
Its stability is as shown in table 2:
Table 2
In embodiment 1～9, the gas permeability matter of the listed former film of polymer is as shown in table 3:
Table 3
1Barrer=1 × 10-10cm3(STP)·cm/(cm2·s·cm Hg)
The gas permeability matter of the thermic rigidity separation film of embodiment 1～9 gained is as shown in table 4:
Table 4
1Barrer=1 × 10-10cm3(STP)·cm/(cm2·s·cm Hg)。
Claims (5)
1. a Stable structure separation film, is by polymeric film in an oxidizing atmosphere, processes at least 0.1h in 150～500 DEG C
Gained,
Wherein, described polymer is polyacrylonitrile, polysulfones, polyether sulfone, Polyetherimide, polyimides, polyethersulfone ketone, polyarylether
One or more in ketone, polyether sulphone, polyethers nitrile ketone, phenolic resin piperazine resin, cyanate ester resin base polymer.
Separation film the most according to claim 1, it is characterised in that: oxidizing atmosphere is provided by containing oxygen gas mixture, described contains
Oxygen gas mixture is made up of 5～the oxidizing gas of 50% (V/V) and surplus carrier gas.
Separation film the most according to claim 1, it is characterised in that: described oxidizing gas is oxygen, air or ozone.
Separation film the most according to claim 1, it is characterised in that: be by polymeric film in an oxidizing atmosphere, in 150～
500 DEG C process 0.1～24h gained, heating rate 1～20 DEG C/min.
5. prepare the method separating film described in claim 1 for one kind, it is characterised in that: by polymeric film in an oxidizing atmosphere,
At least 0.1h is processed in 150～500 DEG C,
Wherein, described polymer is polyacrylonitrile, polysulfones, polyether sulfone, Polyetherimide, polyimides, polyethersulfone ketone, polyarylether
One or more in ketone, polyether sulphone, polyethers nitrile ketone, phenolic resin piperazine resin, cyanate ester resin base polymer.
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| CN105921037B (en) * | 2016-06-22 | 2018-03-30 | 辽宁科技大学 | A kind of preparation method of the porous gas separation membrane material with thermic rigid structure |
| CN107362702B (en) * | 2017-09-11 | 2020-04-14 | 大连理工大学 | Mixed matrix membrane with heat resistance and solvent resistance as well as preparation method and application thereof |
| 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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| US5152894A (en) * | 1989-02-02 | 1992-10-06 | Hoechst Aktiengesellschaft | Semipermeable membrane made from a homogeneously miscible polymer blend |
| 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 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| AUPR143400A0 (en) * | 2000-11-13 | 2000-12-07 | Usf Filtration And Separations Group Inc. | Modified membranes |
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2014
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|---|---|---|---|---|
| US5152894A (en) * | 1989-02-02 | 1992-10-06 | Hoechst Aktiengesellschaft | Semipermeable membrane made from a homogeneously miscible polymer blend |
| 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 |
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